10.remediation of asphaltene.socar journal

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INTRODUCTIONArterial blockage in the petrolem indstry is mostly

de to the deposition of heavy organic molecles frompetrolem flids. Heavy organic molecles sch as

asphaltenes, asphaltogenic acids, diamondoids andderivatives, mercaptans, organometallics, paraffin /waxand resins exist in crde oils (fig.1) in varios qantitiesand forms [1, 2].

Sch componds cold separate ot of the crde oilsoltion de to varios mechanisms and deposit, casingfoling in the oil reservoir, in the well, in the pipelinesand in the oil prodction and processing facilities [1-6].Solid particles sspended in the crde oil may stick to thewalls of the condits and reservoirs (fig.2). The toghnessof the deposits has a lot to do whether there is asphaltenepresent in the crde oil even in minte qantities.

Asphaltene, which is a highly polar compond, generallyact as a gle and mortar in hardening the deposits and, asa reslt, casing barrier to the flow of oil [7-14].

Depositions of the heavy organics present in crde

oil happen de to varios cases depending on theirmoleclar natre. Mercaptans and organometallicsdepositions are de to dissociation, solbility effects, orattachment to srfaces. Diamondoids and paraffin/waxdeposit and form solid crystals de, mostly, to loweringof temperatre [15-17]. Resins are not known to depositon their own, bt they deposit together with asphaltenes[18]. The reasons for the asphaltenes and asphaltogenicacids deposition can be many factors inclding variationsof temperatre, pressre, pH, composition, flow regime,wall effect and electrokinetic phenomena. When severaldifferent heavy organic componds are present in a

In this report the methodologies and analysis for in sit remediation of heavy organics in petrolemprodction, transportation and processing indstries is presented. First the heavy organics which depositfrom petrolem flids are indentified and it is pointed ot that the more difficlt member of thesecomponds to deal with are asphaltenes. Six different in sit remediation methods are introdced whichinclde: (i) prodction scheme alteration techniqes; (ii) chemical treatment techniqes; (iii) external forcefiled techniqes; (iv) mechanical treatment techniqes; (v) thermal treatment techniqes; (vi) biologicalmethods. Also eight steps that appear to be necessary and effective in prevention and moderating theseverity of the deposition and remediation are introdced which inclde: (a) Predictive modeling andanalysis; (b) dal completion of oil wells; (c) compatibility tests of injection flids before applications; (d)consideration of the compositional gradient of heavy organics in reservoir in prodction scheme design;(e) application of mechanical removal technologies for deposits; (f) application of solvent for dissoltion

of deposits; (g) hot oil treatment of the in sit deposits; and (h) se of dispersant to stabilize the heavyorganics, specially asphaltenes from deposition. Overall, a proper rote to combat arterial blockage in theoil and gas indstry is to consider a combination of prediction modeling, experimentation and remediation.

Keywords: asphaltene, organic deposits, oil treatment, steric colloidAdress:[email protected]

UDC 52.47.23

REMEDIATION OF ASPHALTENE AND OTHER HEAVYORGANIC DEPOSITS IN OIL WELLS AND IN PIPELINES

G.Ali Mansoori

(university of Illinois)

Fig.1. Heavy organic molecules that depositfrom petroleum fluids

Fig.2. Asphaltene molecules are highly sticky andthey act as mortar which also cause other suspendedparticles stick to deposit cause fouling in petroleum

fluid arteries


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petrolem flid their interactive effects mst be alsoconsidered in order to nderstand the mechanisms oftheir collective deposition or lack of it. This is especiallyimportant when one of the interacting heavy organiccomponds is asphaltene. For example a reglar waxycrde containing minte amonts of asphaltene willbehave differently at low temperatres (below the clodpoint) compared with: (i) a clean waxy crde with noother heavy organics present in it; (ii) an asphalteniccrde containing some paraffin/wax or; (iii) a prelyasphaltenic crde containing no paraffin/wax [19, 16].

Deposition of heavy organics in petrolem flidsmay case formation of sspended particles. In general,sspended particles in a crde oil fall into two classes:basic sediment and filterable solids. Presence ofsspended particles in petrolem flids cold have asevere economic impact on petrolem indstry [5, 6].Carried along in the oil, they may case foling, foaming,erosion, and/or corrosion. Depending on the case,coaglants (moleclar weight < 10000) or flocclants(moleclar weight > 10000), may provide an indirect aidin sspended particles removal (fig.3).

Coaglants are molecles with strong polar charge

which act to disrpt charges on the srface of dropletsof an opposite phase or sspended solid particles thatwold otherwise prevent it from coalescence. Flocclents,act to coalesce colloidal particles, becase they attach tocolloids and they increase their size beyond the Brownianlaw of sspension [20, 21].

The prodction and transportation of petrolem flidswill be severely affected by deposition of sspendedparticles (i.e. asphaltenes, diamondoids, paraffin/wax,sand, etc.) in prodction wells and/or transfer pipelines xxsome of my older papers. In certain instances the amontof precipitation is rather high casing complete foling ofthese condits. Therefore, it is important to nderstand

the behavior of sspended particles dring petrolemflow conditions. We recently introdced an analytical

model for the prefoling behavior of sspended particlescorresponding to petrolem flids prodction conditions[5, 6]. We predicted the rate of particle deposition dringvarios trblent flow regimes. The trblent bondarylayer theory and the concepts of mass transfer weretilized to model and calclate the particle depositionrates on the walls of flowing condits. The proposedmodel acconted for the eddy and Brownian diffsivitiesas well as for inertial effects. The analysis presentedshowed that rates of particle deposition dring petrolemprodction on the walls of the flowing channel de solelyto diffsion effects are negligible. It was also shown thatdeposition rates decrease with increasing particle size.However, when the process is momentm controlled(large particle sizes) higher deposition rates are expected.

Considering that the major barrier in a profitabledeposition-free oil prodction scheme is the presence ofasphaltenes in the crde the in sit remediation methodsof asphaltenes in the petrolem flids is discssed in thefollowing sections.

In Situ Field Remediation MethodsIn petrolem prodction initially it is necessary to

take any nmber of steps necessary to prevent thefoling problems. Heavy organics deposition cold beeliminated by modification of the prodction practices,rather than by chemical, mechanical, thermal or otherexternal means. This may redce the cost of prodctionoperation appreciably. This may be achieved by theoptimm design of the oil prodction and transportationsystems based on proper laboratory tests and implicationof deposition prediction models [22-25].

Heavy organic deposits re- slting from the presence

of asphaltenes in crde oils are qite hard to deal with.Asphaltenes may be destabilized in any area of the oilprodction and processing facilities from as far back asthe near wellbore area to as far down the system as in thepetrolem refinery (fig.4,5).

Asphaltenes, in addition to their highly stickycharacteristics which attach to solid srfaces, changetheir wettability [26], they cold also act as ncleationsites for paraffin/wax and diamondoids crystallizationwhich are often fond within the same deposits.

Heavy organics deposition de to asphalteneflocclation cold be controlled throgh the betterknowledge of the mechanisms that case their deposition

in the first place [9, 27]. Processes can be altered tominimize the deposition and chemicals can be sed

Fig.3. The role of coagulants and flocculants indeposition of a suspended particles

Fig.4. Locations (circled in green) where heavy organics deposition could occur most likely in the petroleum fluidsproduction and transportation systems


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[28] to possibly control the deposition when processalterations are not effective. Heavy organics depositionsand their remediation in petrolem flid systems maybe controlled sing varios techniqes which incldethe following six categories: prodction schemealterations, chemical treatment methods, external forcefields exertion, mechanical treatment methods, thermal

treatment techniqes and biological methods [3, 4]. Inwhat follows we briefly present the varios categories oftreatment methods.

I. Prodction scheme alterations techniqes: Theyare sed to control asphaltene and other heavy organicsdeposition and they inclde: (i) redction of shear(fig.6); (ii) elimination of incompatible materials fromasphaltenic crde oil streams (fig.7); (iii) minimization ofpressre-drops in the prodction facility (fig.8); and, (iv)minimization of mixing of lean feed stock liqids intoasphaltenic crde streams (fig.7), (v) netralization ofelectrostatic forces (fig.9).

II. Chemical treatment techniqes: They inclde:

Addition of dispersants, antifolants, coaglants,

flocclants and polar co-solvents which may be sed tocontrol asphaltene deposition in its varios stages.

II.1. Dispersants work by srronding the asphaltenemolecles forming steric colloids, similar to the natralresin materials (fig.10).

II.2. To inhibit the attachment and growth of depositson srfaces and walls they can be coated with antifolant

chemical componds (fig.11, 12). Teflon (fig.11) which

Fig.5. Locations where heavy organics deposition could most likely occurin the petroleum refining/processing systems [14]

Fig.6. Pipe flow with Shear

Fig.7. Incompatible miscible fluids flow and separationof heavy ends in the form of colloids, flocs and

attachment to the walls of conduits

Fig.8. Minimization of pressure-drops in the petroleumproduction facility causing separation of phases from

a miscible phase to oil, gas and heavy organics phase

Fig.9. Lack of neutralization of electrostatic forces maycause break up of asphaltene steric colloids, release

of sticky asphaltene particles and attachment to wallscausing fouling in petroleum fluid flow lines


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is polytetrafloroethylene (C2F4)n is one well-knownantifolant material sed for coating srfaces to preventorganic and inorganic materials from attachment to

srfaces [29].Organotin componds particlarly tribtyltinoxide (fig.12), are very effective as antifolants andhave been the antifolant of choice for many yearsin marine, agricltral, wood and plastics indstries.The effectiveness of TBTO is a reslt of the fact thatit gradally leaches from the hll killing the foling

organisms in the srronding area. However, it is fondto case health and environmental problems [30].

II.3. Coaglants, which are mostly polymers, havea role similar to resins which form steric colloids andthen flocclation of colloids in the form of flocs andprecipitation (fig.13, 14).

II.4. Polar co-solvents (sch as aromatic hydrocarbons)cold re-dissolve the asphaltene deposits and need tohave a high level polarity (aromaticity) to be effective(fig.15, 16).

When the concentration of polar solvents exceedsa certain level then asphaltene micelles will be formed

[31-34]:Organic material deposited into the prodction

installations of petrolem crde may case operational

problems. One may initially try to dissolve sch depositsby varios means like steam wash, diesel oil wash andheavy aromatics wash, etc. One may also consider sing

a system of specifically designed additives to stimlatethe wells. Sch additives are best to be a mixtre ofan inhibitor of asphaltene precipitation, an asphaltenedispersant and an antifoaming agent [35].

III. External force field techniqes: They inclde: (i)electrostatic force field; (ii) electrodynamic force field;and (iii) magnetic field; (iv) ltrasond techniqes;

Fig.10. Steric colloids of asphaltene (asphaltene floc core)and resins (red aromatic head with black paraffin tails)

Fig.11. A non-bio antifoulant:Teflon=polytetrafluoroethylene

Fig. 12. A bio-antifoulant:Tributyltin oxide An organotin

Fig.13. Flocculation of asphaltene due to increase inparaffin (nonpolar) content of petroleum [25, 32, 1]

Fig.14. Steric-colloid formation of asphaltene flocs(random aggregates) in the presence of excess amounts

of resins and paraffin hydrocarbons [25, 32, 1]

Fig.15. Aromatic hydrocarbons that could re-dissolveasphaltene deposits


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Fig.16. Asphaltene miclellization in the presenceof excess amounts of aromatic hydrocarbons [31-33]

Fig.17. Pipeline pigs[www.pipingguide.net/2007/11/pipeline-pigging.html]

(v) microwave techniqes. All these techniqes arepresently applicable for petrolem/laboratory operationsand mostly for small scales.

IV. Mechanical treatment techniqes: They inclde:(i) manal stripping, pigging, mechanical vibrations, etc.

Mechanical/manal stripping is probably the oldestmethod known for the removal of heavy hydrocarbondeposits. It is done by mechanically scraping the tbing.Pigging technology is well established, bt it is mostsitable for foams, waxy crde arteries and wax depositremoval (fig.17).

Pigging technology sccess for asphaltenic crdearteries is qestionable. Solble or insolble pigs areinjected into the oil arteries. The pigs wold remove aportion of the deposit bildp as they travel throghthe lines. Althogh this method may be effective forcleaning the tbing and lines, it is not effective in

removing the heavy organic deposits at the formation.There have been some advances in smart pigs which maytake advantage of remote visalization, control, localheating, etc. Mechanical removal of deposits may be acmbersome operation. In addition, the disposal of thedeposits sometimes cases difficlties.

V. Thermal treatment techniqes: They inclde: (i) insit combstion (fig.18); (ii) steam injection (fig.19); (iii)

hot water injection (fig.20); (iv) hot gas injection (fig.21);(v) hot chemicals injection; (vi) microwave techniqeof heating which is volmetric, sample-based (not thewhole region), and center of sample heated the mostverss the reglar heating which heats the srface; (vii)se of exothermic chemical reactions.

Removal of deposits by hot flid is performed bycirclating it into the well, condits, or by injection intothe formation to open p plgged areas. This methodworks by melting the organic deposits. Therefore, it isimportant to insre that the melted organics are notre-deposited in another part of the formation. Thishappens when the hot flid introdced to the formation

becomes satrated with melted paraffins, and when theformation temperatre is lower than the clod point of

Fig.18. In situcombustion

Fig.19. Steam injection [fossil.energy.gov]

Fig.20. Hot water injection [afcee.af.mil]


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the hot flid. under these circmstances precipitationwill occr and conseqently case permeability redctionand damage to the formation.

VI. Biological methods: These may inclde in sitapplication of (i) anaerobic bacteria; (ii) aerobic bacteria;(iii) other microorganisms inclding fngs, etc. Schbio-processes that may redce asphaltenes into lightermolecles is named biodegradation. Biodegredationmechanism of asphaltenes is perhaps the leastknown reaction mechanism for the biodegradationof a petrolem fraction. It appears that asphalteniccomponds are relatively inert to microorganismsattack, since they consist of complex strctres of sheetsof aromatic and alicyclic ring strctres with very shortalkyl side chains [36].

Varios types of microorganisms that are capableof oxidizing asphaltenic componds are widespreadin natre. However, they need to be identified,isolated and grown in the lab to make them capable ofbiodegradation of large amonts of asphaltenic deposits.Biodegradation, if made practical, is an important

mechanism for removing these non-volatile components.It is a relatively slow process and may reqire monthsto years for microorganisms to degrade a significantamont of asphaltenes. Dring sch biodegradation, theproper species of bacteria, fngi, etc. wold metabolizeasphaltenes as a sorce of carbon and energy. under

aerobic conditions, asphaltene wold decompose stepby step into water, carbon dioxide, nitrogen oxides, andslfr oxides.

DISCUSSION AND RECOMMENDATIONSThe steps that appear to be necessary and effective

in prevention, moderating the severity of the depositionand remediation are the following:

(A). PREDICTIVE MODELLING AND ANALYSIS- Resoltion of the heavy organic deposition problemcalls for detailed analyses of heavy organic containingoils from the microscopic standpoint and development

of moleclar models which cold describe the behaviorof heavy organics in hydrocarbon mixtres [37-41].From the available laboratory, field, and refinerydata it is proven that the heavy organics whichexist in petrolem generally consist of very manyparticles having moleclar weights ranging from a few

hndred to several hndred thosands. As a resltdistribtion-fnction crves are sed to report theirmoleclar weight distribtion [42-44]. Some of theheavy organics present in the oil deposit de to phasetransitions from liqid to solid state. However, thisis not generally the case for asphaltene particles. Thehigh affinity of asphaltene particles to association withone another, their tendency to adsorb resins, and theirextensively wide range of size distribtion sggest that

asphaltenes are partly dissolved and partly in colloidalstate (in sspension) in oil peptized (or stabilized)primarily by resin molecles that are adsorbed onasphaltene srface [38].

Fig.21. In situ hot gas injection [sanleonenergy.com]

Fig.22. Static (PX) heavy organics deposition envelope(HODE) of a crude oil mixed with a miscible injectant(MI) at 60 oF but at various proportions and pressures.

In this figure L stands for liquid phase, L-V is theliquid-vapor two-phase region, L-S is the liquid-solid

two-phase region, and L-V-S is the liquid-vapor-solidthree-phase region

Figure 23. Dynamic (QX) heavy organics depositionenvelope (HODE) of a crude oil mixed with a miscibleinjectant (MI) at 60 oF but at various proportions and

pressures. In this figure Q=Uavg1.75

d0.75

/k, where Uavg (m/s)stands for crude average velocity in a cylindrical

conduit, d(m) is the conduit diameter and k(ohm-1/m)is the crude electrical conductivity. The area above each

curve represents the deposition region and under thecurve is the flow region with no deposition


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As a reslt, a realistic moleclar model for theinteraction of asphaltene and oil shold take intoaccont both the solbility in oil of one segment andsspension characteristic (de to resins) of anothersegment of the moleclar weight distribtion crve ofasphaltene [38, 23, 24, 1, 2].

Initially laboratory work may be necessary to qantifyand characterize the varios families of heavy organicspresent in a crde and in general shed light on the reasonsfor sch depositions [45-47]. Laboratory work joinedwith statistical mechanical pls kinetics modeling mayreslt in the constrction of heavy organics depositionenvelop (HODE) sch as the graph shown in figres 22and 23 which wold indicate the ranges of temperatreand pressre where the crde oil deposits ot heavyorganic componds at varios temperatres, pressres,compositions/blending, electrokinetic effects, and flow

conditions [41].(B). Dal Completion - It is reported [48] that the se

of standard well completion techniqes when heavyorganics deposition is likely has often reslted in costly

workovers for deposit removal in those wells. To combatthe heavy organics deposit formation the completingwells with a dal completion is necessary (fig.24).

This is with the prpose of: i) sing the inner tbingstrings for solvent or dispersant injection or circlation,ii) access for lowering prodction testing devices.Sometimes an inner tbing string is sed for prodctionto meet prodction qotas when the main string is sht-in for maintenance or heavy organics cleaning.

(C). COMPATIBILITY TESTS - It is sggestedthat all well stimlation, injection and enhanced oilrecovery flids shold be tested for static and dynamic

compatibility with the reservoir flids prior to operations,

Fig.24. A well with a dual completion

Fig.25. Phase envelops defining the compositionregions of the heavy organics separation at a given

temperature and pressure

Figure 26. Compositional gradient scheme

Figure 27. Wirelining


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especially where asphaltenic crdes are present [49]. It ispossible to perform certain experimental measrementsto prodce rather simple phase envelops like figre 25throgh which one can define the composition regionsof the heavy organics separation at certain temperatre

and pressres.Sch experimental compatibility tests may be costly ifone needs to stdy all the possible regions of compositionand pressre. However, static and dynamic compatibilitymodeling sing the advanced statistical and fliddynamic techniqes can be qite efficient and economical

for shedding light on the problemby constrcting heavy organicsdeposition envelopes (HODE) asshown by figres 22 and 23.

(D). composition gradient - Itis generally nderstood that thereis a composition gradient of heavyorganics in petrolem reservoirswith deeper zones having higherfractions of the heavy organics(fig.26). The decision to prodcefirst the top zone of the reservoir,which is generally less prone toheavy organics deposition, isalways preferred. Actally mostof the prodcing wells mst becompleted dal commingled.Prodction srveys wold showfrom which zone most of the oilwas being prodced.

( E ) . M E C H A N I C A L

REMOVAL TECHNIQuES- In certain circmstancesmechanical removal techniqes,especially wirelining may beeffective means of combatingthe heavy organics problems[49]. An economical stdy mayindicate whether mechanicalremoval methods of cleaningis preferred over cleaning bysing solvents. For exampleat the Hassi Messaod field,

Algeria, necessitated freqenttbing scrapings and washingsto maintain prodction [50, 51].Ctting the deposits from thetbing by wireline method wastoo time-consming and sometimes impractical, so a program ofwashing the tbing with a solventwas established.

(F). Solvent treatment - Solventtreatment of the oil is consideredto be beneficial in some casesbecase it diltes the crde oil

and redces the tendency of theheavy organics to precipitate.Solvent treatments may not bevery sccessfl largely becasethe solvents which can be sedare limited to aromatic solvents(fig.15). Xylene is generally

the most common solvent selected to be sed in wellstimlations, workovers, and heavy organics inhibitionand cleaning. In some cases xylene injection throghthe non-prodcing string (inner tbings shown infig.24) actally may help to minimize the heavy organic

deposition problem. In oil fields with freqent need foraromatic wash it may be necessary to design an aromaticsolvent with stronger wash power and better economyfor the particlar deposit in mind [52].

Laboratory tests (fig.28) may be necessary to blendan appropriate aromatic solvent and/or dispersant for a

Crude oAPI

Resin,wt%

Asphaltene,wt%

Asphaltene

Resin

Canada, Atabasca 8.3 14.0 15.0 1.07

Venezela, Boscan 10.2 29.4 17.2 0.58

Canada, Cold Lake 10.2 25.0 13.0 0.52

Mexico, Pancon 11.7 26.0 12.5 0.48

uSA, MS, Baxterville 16.0 8.9 17.2 1.93

Rssia, Kalga 16.7 20.0 0.5 0.025

uSA, TX, Hold 19.7 12.0 0.5 0.04

Brazil, Campos,Atabasca 19.7 21.55 2.8 0.13uSA, CA,

Hntington Beach 26.2 19.0 4.0 0.21

Canada, Alberta 29.0 8.5 5.3 0.62

India, Mangala crde 29.28 20-30


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given oil field from the points of view of effectiveness,economy, and environmental concerns. Then specialformlas may be blended to achieve the goal of preventingor cleaning the heavy organics deposits which can besed by the field engineers.

[G). HOT OIL TREATMENT - Circlation with hotoil may be sed to avoid or redce the heavy organicsdeposition problem. A combination of solvent treatmentand reverse and normal circlation with hot oil havebeen tried in the past in some oil wells with mixedreslts [49, 3, 4].

(H). DISPERSANT uSE - Injection of dispersants orantifolants may be effective in certain crde oils wherethe ratio of resin to asphaltene is not high enogh toprevent asphaltene flocclation and as a reslt heavyorganics deposition. One thing which appears to haveniversal acceptance is that resins in the crde act asthe peptizing agents of the asphaltene particles. It is

generally a good practice to analyze a crde oil for itsasphaltene and resin content and ratio. In Table 1 schdata for a nmber of crde oils are reported verss theirAPI gravity. Crde oils with higher asphaltene to resinratios are more prone to heavy organics deposition. Ofcorse there are exception to this rle mostly de to thepossibility or presence of high amonts of aromaticsin the crde, variations in the moleclar strctres ofasphaltenes and resins, and the polydispersivity effects.For example, Boscan crde, which is second from the topof the list in Table 1, has had no deposition problem, whileTecoaminocan crde, which is close to the bottom of the

list, is a crde oil with freqent deposition problems.Actally in Boscan crde, in addition to having a lowasphaltene/resin ratio of 0.58 it has also a low satrates/aromatics ratio of 0.71.

High amonts of resins and aromaticity helps theasphaltene in this crde to stay in the soltion and/or

sspended withot deposition. Considering sch severeexceptions to the rle one shold not consider thisratio to be the only factor in evalating the depositionpotential of a crde oil. Other factors inclding the natreof hydrocarbons in the crde, the polydispersivitiesand polarities of asphaltene and resin, the presence ofsch componds as paraffin /wax, organometallics anddiamondoids, the natre of condit, hydrodynamicsand electrokinetics have also roles in the deposition.In order to qantify all these factors one has to se acomprehensive predictive model in which all theseeffects are incorporated [41].

ConclusionsInsofar as finding a rigoros niversal soltion to the

heavy organics deposition problem is concerned thereis still a long way to go. Asphaltene flocclation can becontrolled throgh better knowledge of the mechanismsthat case its flocclation in the first place. Processes canbe changed to minimize the asphaltene flocclation andchemical applications can be sed effectively to control

depositions when process changes are not cost effective.Since heavy organics deposition takes place dringprimary, secondary, and tertiary oil recovery, injectionof peptizing agents (i.e.: resins) in proper amontsand places may prevent, or at least control, the heavyorganics deposition problem. Frthermore, experimentscold be performed (i.e.: of the coreflood type) wherepeptizing agents are injected to stdy their effect oninhibition of heavy organics deposition or permeabilityredctions. However, se of sch additives to crde oilis economically qite prohibitive.

One interesting qestion posed by previos

researchers [53, 50] is why there was asphaltic bitmendeposited at the bottom of the well considering that nophase change or any sbstantial temperatre or pressrechanges had taken place. The conclsion was that theqestion cold only be answered after considerablelight was thrown pon the natre of the asphalticbitmen prior to its separation from the crde oil in thewell. There were a few efforts to try to determine thesize and natre of asphaltene particles while they stillare in the original oil [53, 54].

Establishing the state of the asphaltene particles in theoriginal crde oil seems to be a basic bilding block inthe scientific qest to find a soltion to many irreversible

heavy organics deposition problems. Experimental andtheoretical modeling work towards this end has beenperformed [55, 9], bt more is needed. More experimentsneed to be done to dplicate Witherspoon et al.sltracentrifge work for different oils and possibly tilizeother contemporary experimental techniqes to establishthe state of asphaltenes in crde oils. Meanwhile, itappears that any modeling effort that describes the phasebehavior of asphaltenes in oil shold take into accont thelack of positive information on the strctre of asphaltenesin the original oil and their moleclar characteristics. Thishas been the philosophy followed in modeling activity [56,

38, 23, 12] proposed for predicting the deposition behaviorof heavy organics in petrolem flids.Acknowledgements: The athor appreciated the

contribtions of Dr. J.H.P. Sanchez in the initial stageof this research. This research was spported in part byPEMEX, IMP and Petrobras.

Figure 28. A laboratory model to test varioussolvents for heavy organics remediation [52]


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2.G.A.Mansoori.A nified perspective on the phase behavior of petrolem flids //InternationalJornal of Oil, Gas and Coal Technology. -2009(b). Vol.2(2). P.141-167.

3. J.H.P.Sanchez, G.A.Mansoori. Modeling the behavior of asphaltene micelle in petrolem flids//Proceedings of the Second International Symposim on Colloid Chemistry in Oil Prodction(ISCOP '97). Brazil: Rio de Janeiro. -1997. -Paper 12.

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7. G.A.Mansoori. Asphaltene Deposition: An Economic Challenge in Heavy Petrolem Crdeutilization and Processing //OPEC Review. -1988. P.103-113.

8.G.A.Mansoori. The occrance of asphaltene throghot prodction cycle //Proceedings of the 6thADIPEC. TX: Richardson. SPE. -1994. P.282-292.

9.G.A.Mansoori.Asphaltene, resin, and wax deposition from petrolem flids //The Arabian Jornal

of Science and Engineering. -1996(a). Vol.21(48). P.707-723.10.G.A.Mansoori.Arterial Blockage in the Petrolem and Natral Gas Indstries (Cases &Effects,Economic Implications, & Preventive Measres) //Proceedings of Controlling hydrates, asphaltenes andwax conference. IBC uK Conferences, Ltd. London. Gilmoora Hose. -1996(b). -Paper No 2.

11.G.A.Mansoori.Asphaltene, resin, and wax deposition from petrolem flids //The Arabian Jornalof Science and Engineering. -1996(c). Vol.21(48). P.707-723.

12.G.A.Mansoori.Modeling of asphaltene and other heavy organics depositions //Jornal of PetrolemScience and Engineering. -1997. Vol.17. P.101111.

13.G.A.Mansoori.Case and effect of deposition and foling of heavy organics and other compondsin fel and petrochemical processes //Ku International Jornal of Science & Technology. Transaction B.-2002(a). P.1-17.

14.G.A.Mansoori. Physicochemical basis of foling prediction and prevention in the process indstry

//Jornal of the Chinese Institte of Chemical Engineers. -2002(b). Vol.33(1). P.25-32.15.A.N.Afanasyev, V.A.Matishev, Z.I.Syunyaev, V.V.Farafonov. Melting and Crystallization of Paraffins//Chemistry and Technology of Fels and Oils. -1993. Vol.29. P.549-554

16.G.A.Mansoori, H.L.Barnes, G.M.Webster.Petrolem Waxes. //Chapter 19 in Fels and LbricantsHandbook. ASTM Int'l, West Conshohocken, PA, 2003. P.525-558.

17. G.A.Mansoori. Diamondoid Molecles //Advances in Chemical Physics. -2007. Vol.136.P.207-258.

18. J.P.Dickie, T.F.Yen.High resoltion mass spectral examination of the resin fraction of petrolemasphaltenes //American Chemical Society (ACS) Division of Petrolem Chemistry. -1968. Vol.13(2).P.140-148.

19.S.Himran, A.Suwono, G.A.Mansoori.Characterization of alkanes and paraffin waxes for applicationas phase change energy storage medim //Energy Sorces. -1994. Vol.16. P.117-128.

20. S.S.Schantz, P.L.Elliot. Economic implications of solids in crde and their ltimate fate in the

refining process //National Petrochemical & Refiners Association Annal Meeting. uSA: Texas. SanAntonio. -1994.

21. A.C.S.Ramos, L.Haraguchi, F.R.Notrispe etc. Interfacial and colloidal behavior of asphaltenesobtained from Brazilian crde oils //Jornal of Petrolem Science and Engineering. -2001. Vol.32(2-4).P.201-216.

22. S.J.Park, T.K.Kwak, G.A.Mansoori. Statistical Mechanical Description of Spercritical FlidExtraction and Retrograde Condensation //Intertaional Jornal of Thermophysics. -1987. No.8.P.449-471.

23.S.J.Park, G.A.Mansoori. Aggregation and Deposition of Heavy Organics in Petrolem Crdes //InternationalJornal of Energy Sorces. -1988(a). No.10. P.109-125.

24. S.J.Park, G.A.Mansoori. Orgainc Deposition from Heavy Petrolem Crdes (A FRACTALAggregation Theory Approach) //Proceedings of the uNITAR/uNDP 4th International Conference on

Heavy Crdes and Tar Sands. Edmonton. Alberta. -1988(b).25.V.A.M.Branco, G.A.Mansoori, L.C.De Almeida Xavier etc.Asphaltene flocclation and collapse frompetrolem flids //Jornal of Petrolem Science and Engineering. -2001. Vol.32. P.217-230.

26.D.T.Kim, M.E.Boudh-Hir, G.A.Mansoori.The role of asphaltene in wettability reversal //Proceedingsof the 1990 SPE Annal Convention. TX: Richardson. 1990. P.120137 -Paper 20700.


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27.A.Eliassi, H.Modaress, G.A.Mansoori. Stdy of asphaltene flocclation sing particle contingmethod //Proceed. Filtech 2005 (International Conference & Exhibition for Filteration & Separation Tech),I. Germany: Weisbaden. 2005. P.506-511.

28.J.K.Borchardt. Chemicals used in Oil-Field Operations //Oil-Field Chemistry. Edited by BorchardtJK and Yen TF, ACS Symposim Series 396. Washington, DC, 1989.

29.A.C.Funderburg.Making Teflon stick //American Heritage of Invention and Technology. -2000.Vol.16(1). P.10-21.

30.R.C.Poller. The chemistry of organotin componds. London: Logos Pb, 1970.31.S.Priyanto, G.A.Mansoori, A.Suwono. Asphaltene micellization and its measrement //Proceedings

of the 3rd. International symposim on advanced and aerospace science and technology in Indonesia(ISASTI, 98). Jakarta. 1998. P.843-860.

32.S.Priyanto, G.A.Mansoori. A.Suwono. Strctre & Properties of Micelles and Micelle Coacervatesof Asphaltene Macromolecle //Nanotechnology Proceedings of 2001 AIChE Annal Meeting. -2001(a.)

33. S.Priyanto, G.A.Mansoori, A.Suwono. Measrement of property relationships of nano-strctremicelles and coacervates of asphaltene in a pre solvent //Chemical Engineering Science. -2001(b). Vol.56. P.6933-6939.

34.J.H.P.Sanchez, G.A.Mansoori. Prediction of the Phase Behavior of Asphaltene Micelle/AromaticHydrocarbon Systems //Jornal of Petrolem Science and Technology. -1998(b). Vol.16(3/4). P.377-394.

35. J.C.Chavez, A.Lory. Estdio sobre la depositacion de material organico en instalaciones deprodccion del area marina de Campeche //Revista del Institto Mexicano del Petroleo. -1991. Vol.22. P.55-67.

36.Z.X.Niu, S.H.Guo, F.M.Li etc.Bio-Degradation of Resin and Asphalt in Viscos-Oil ContaminatedSoil by Actonomyces //Jornal of Agro-Environment Science. -2005. Vol.24(4). P.771-774.37.L.G.Chorn, G.A.Mansoori. Mlticomponent Fractions Characterization: Principles and Theories

//in: C7+ Fraction Characterization. Advances In Thermodynamics Vol:1. New York, NY: Taylor &Francis Press, 1989. P.1-10.

38. S.Kawanaka, K.J.Leontaritis, S.J.Park, G.A.Mansoori. Thermodynamic and Colloidal Models ofAsphaltene flocclation //in "Oil Field Chemistry". ACS Symposim Series 396. Chapter 24. ACS. DC:Washington, 1989.

39. S.Kawanaka, S.J.Park, G.A.Mansoori. Organic Deposition from Reservoir Flids //SPE ReservoirEngineering Jornal. -1991. No.3. P.185-192.

40.H.Manafi, G.A.Mansoori, S.Ghotbi.Phase behavior prediction of petrolem flids with minimmcharacterization data //Jornal of Petrolem Science and Engineering. -1999. Vol.22. P.6793.

41.

G.A.Mansoori.ASPHRAC: A comprehensive package of compter programs and database whichcalclates varios properties of petrolem flids containing heavy organics //www.ic.ed/~mansoori/ASPHRAC_html. -2010.

42. K.J.Leontaritis, G.A.Mansoori. Fast crde-oil heavy-component characterization singcombination of ASTM, HPLC, and GPC methods //Jornal of Petrolem Science and Engineering.-1989. Vol.2(1). P.1-12.

43. G.A.Mansoori, D.Vazquez, M.Shariaty-Niassar. Polydispersity of heavy organics in crde oilsand their role in oil well foling //Jornal of Petrolem Science and Engineering. -2007. Vol.58(3-4).P.375-390.

44.D.Vasquez, G.A.Mansoori.Identification and measrement of petrolem precipitates //Jornal ofPetrolem Science and Engineering. -2000. Vol.26(14). P.4956.

45.Y.F.Hu, S.Lib, N.Liub etc.Measrement and corresponding states modeling of asphaltene precipitationin Jilin reservoir oils //Jornal of Petrolem Science and Engineering. -2004. Vol.41. P.169182.

46. S.A.Mousavi-Dehghani, M.R.Riazi, M.Vafaie-Sefti, G.A.Mansoori. An analysis of methods fordetermination of onsets of asphaltene phase separations //Jornal of Petrolem Science and Engineering.-2004. Vol.42 (2-4). P.145-156.

47.D.Vasquez, J.Escobedo, G.A.Mansoori. Characterization of crde oils from sothern Mexican oilfields//Proceedings of the International Petrolem Technology Exhibition. Mexico: Mexico City. Placio de LosDeportes. -1998.

48.C.Von Albrecht, W.M.Salathiel, D.E.Nierode. Stimlation of asphaltic deep wells and shallow wells inLake Maracaibo, Venezela. Advances in Methods of Increasing Well Prodctivity and Injectivity //Jornalof Canadian Petrolem Technology. -1977. Oil Sands PD7(1). P.55-62.

49. R.N.Tuttle. High por-point and asphaltic crde oils in condensates //Jornal of PetrolemTechnology. -1983. No.6. P.1192-1196.

50.K.J.Leontaritis, G.A.Mansoori. Asphaltene Deposition: A Srvey of Field Experiences and Research

Approaches //Jornal of Petrolem Science and Engineering. -1988. Vol.1. P.229.51.C.E.Haskett, M.Tartera.A practical soltion to the problem of aspahltene deposits - Hassi MessaodField, Algeria //Jornal of Petrolem Technology. -1965. No.4. -P.387-391.

52.F.Garcia-Hernandez.Estdio sobre el control de la depositacion organica en pozos del area CretacicaChiapas-Tabasco //Ing. Pet. -1989. No.7. P39.


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53.D.H.Katz, K.E.Beu. Natre of asphaltic sbstances //Indstrial & Engineering Chemistry. -1945. Vol.37. P.195-200

54. P.A.Witherspoon. A stdy of the colloidal characteristics of petrolem sing the ltracentrifge//Jornal of Physical Chemistry. -1957. Vol.61. P.1296-1302.

55.T.F.Yen.Strctral differences between asphaltenes isolated from petrolem and from coal liqid//Advances in Chemistry Series 195. J.W.Bnger and N.C.Li, Editors. Chemistry of Asphaltenes, -1979.P.39-52.

56. K.J.Leontaritis, G.A.Mansoori. Asphaltene flocclation dring oil recovery and processing: athermodynamic-colloidal model //Proceedings of the SPE Symposim on Oil Field Chemistry. TX:Richardson. -1987. -Paper 16258.

57.J.Escobedo, G.A.Mansoori. Solid Particle Deposition Dring Trblent Flow Prodction Operations//Proceedings SPE Prodction Operation Symposim. OK: Oklahoma City. -1995. -Paper 29488.

. ( )

, . -, , , . - : (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . , -, : (a) ; (b) ; (c)

; (d) ; (e) -; (f) ; (g) ;(h) , . , - , .

Neft quyular v kmrlrind ar zvi knt v asfaltenlrin tmizlnmsi

G.Ali Mansuri(llinoys universiteti)

Xlas

Mqald neftin xarlmas, nqli v emal proseslrind ar zvi birlmlrin tmizlnmsisllarnn thlili tqdim edilir. lk olaraq neft mhslndan kn ar zvi birlmlr myynedilir v qeyd edilir ki, b trkiblrin n mrkkb komponentlri asfaltenlrdir. Lokal tmizlnmninalt mxtlif sllar qrp tqdim olnr: (i) neftxarma sxeminin dyimsi; (ii) kimyvi emal; (iii)xarici qvvnin tsiri; (iv) mexaniki emal; (v) istilik emal; (vi) bioloji emal. Hminin kntlrininqarsnn alnmas, intensivliyinin azaldlmas v tmizlnmsind zrri v smrli ola biln skkizmrhl tqdim edilir: (a) qabaqcadan proqnozladrma v thlil; (b) qynn iki mhsldar laydatamamlanmas; (c) ttbiq etmzdn vvl vrlan mayelrin ynlq testi; (d) neftxarma sxemininilnmsind laydak ar zvi birlmlrin trkibinin nzr alnmas; (e) kntlrin mexanikitmizlnm sllarnn tdbiqi; (f) kntlrin hll olnmas n hlledicilrinin ttbiq edilmsi;

(g) isti neft emal sllar; (h) ar zvi birlmlrin, xssil asfalten kntlrinin qabanalmag n dispersantlarn istifadsi. mmiyytl mbariznin dzqn yol - proqnozladrlmamodelldirilmsinin, eksperimentlrin v lv edilm sllarnn birlilmsinin thlilinddir.

10.remediation of asphaltene.socar journal

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