Aspeltenes in Crude Oil

Asphaltene
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Asphaltenes are molecular substances that are found in crude oil, along with resins, aromatic
hydrocarbons, and saturates (i.e. saturated hydrocarbons such as alkanes).[1][2] The word
"asphaltene" was coined by Boussingault in 1837 when he noticed that the distillation residue of
some bitumens had asphalt-like properties. Asphaltenes in the form of asphalt or bitumen products
from oil refineries are used as paving materials on roads, shingles for roofs, and waterproof
coatings on building foundations.
Contents
[hide]
 1 Composition
 2 Analysis
 3 Geochemistry
 4 Occurrence
 5 Measurement
 6 Production problems
 7 Heat exchanger fouling
 8 Asphaltene removal
 9 References
 10 External links
Composition[edit]
Asphaltenes consist primarily of carbon, hydrogen, nitrogen, oxygen, and sulfur, as well as trace
amounts of vanadium and nickel. The C:H ratio is approximately 1:1.2, depending on the
asphaltene source. Asphaltenes are defined operationally as the n-heptane (C 7H 16)-insoluble,
toluene (C 6H 5CH 3)-soluble component of a carbonaceous material such as crude oil, bitumen,
or coal. Asphaltenes have been shown to have a distribution of molecular masses in the range of
400 u to 1500 u, but the average and maximum values are difficult to determine due to aggregation
of the molecules in solution.[3]
Analysis[edit]
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Asphaltene after heating [4] are subdivided in: Nonvolatile (heterocyclic N and S species), and,
volatile (paraffin + olefins), benzenes, naphtalenes, phenanthrenes, several others). Speight [5]
reports a simplified representation of the separation of petroleum into the following six major
fractions: volatile saturates, volatile aromatics, nonvolatile saturates, nonvolatile aromatics, resins
and asphaltenes. He also reports arbitrarily defined physical boundaries for petroleum using
carbon-number and boiling point. The molecular structures proposed for the asphaltene (heavy
organic) molecules [6] includes carbon, hydrogen, oxygen, nitrogen, sulfur as well as polar and non-
polar groups.
The molecular structure of asphaltenes is difficult to determine because the molecules tend to stick
together in solution.[7] These materials are extremely complex mixtures containing hundreds or
even thousands of individual chemical species. Asphaltenes do not have a specific chemical
formula: individual molecules can vary in the number of atoms contained in the structure, and the
average chemical formula can depend on the source. Although they have been subjected to modern
analytical methods, including the well known SARA analysis, mass spectrometry, and nuclear
magnetic resonance, the exact molecular structures are difficult to determine. Given this limitation,
asphaltenes are composed mainly of polyaromatic carbon ring units with oxygen, nitrogen, and
sulfur heteroatoms, combined with trace amounts of heavy metals, particularly chelated vanadium
and nickel, and aliphatic side chains of various lengths.[8] Many asphaltenes from crude oils around
the world contain similar ring units, which are linked together to make highly diverse large
molecules.[9]
Geochemistry[edit]
Asphaltenes are today widely recognised as dispersed, chemically altered fragments of kerogen,
which migrated out of the source rock for the oil, during oil catagenesis. Asphaltenes had been
thought to be held in solution in oil by resins (similar structure and chemistry, but smaller), but
recent data shows that this is incorrect. Indeed, it has recently been suggested that asphaltenes are
nanocolloidally suspended in crude oil and in toluene solutions of sufficient concentrations. In any
event, for low surface tension liquids, such as alkanes and toluene, surfactants are not necessary
to maintain nanocolloidal suspensions of asphaltenes.
The nickel to vanadium contents of asphaltenes reflect the pH and Eh conditions of the paleo-
depositional environment of the source rock for oil (Lewan, 1980;1984), and this ratio is, therefore,
in use in the petroleum industry for oil-oil correlation and for identification of potential source
rocks for oil (oil exploration).
Occurrence[edit]
Heavy oils, oil sands, bitumen and biodegraded oils (as bacteria cannot assimilate asphalten[e]s,
but readily consume saturated hydrocarbons and certain aromatic hydrocarbon isomers –
enzymatically controlled) contain much higher proportions of asphaltenes than do medium-API
oils or light oils. Condensates are virtually devoid of asphaltenes.
Measurement[edit]
Asphaltene aggregation, precipitation or deposition can be predicted by modeling or artificial
intelligent methods.[10][11][12] It also can be measured using imaging methods or filtration.
Production problems[edit]
Asphaltenes impart high viscosity to crude oils, negatively impacting production, also the variable
asphaltene concentration in crude oils within individual reservoirs creates a myriad of production
problems.
Heat exchanger fouling[edit]

Asphaltenes are known to be one of the largest causes of fouling in the heat exchangers of the
crude oil distillation preheat train. They are present within micelles in crude oil, which can be
broken down by reaction with paraffins under high temperature. Once the protective micelle has
been removed polar asphaltenes agglomerate and are transported to the tube walls, where they can
stick and form a foulant layer.
Asphaltene removal[edit]
Chemical treatments for removing asphaltene include:
1. solvents
2. dispersants/solvents
3. oil/dispersants/solvents
The dispersant/solvent approach is used for removing asphaltenes from formation minerals.
Continuous treating may be required to inhibit asphaltene deposition in the tubing. Batch
treatments are common for dehydration equipment and tank bottoms. There are also asphaltene
precipitation inhibitors that can be used by continuous treatment or squeeze treatments.[13]
References[edit]
1. Jump up ^ Mullins, O. C. et al. (eds.) (2007) Asphaltenes, Heavy Oils and Petroleomics,
Springer, New York.
2. Jump up ^ Asphaltene. uic.edu
3. Jump up ^ Podgorski, D. C. (2013). "Heavy Petroleum Composition. 5. Compositional and
Structural Continuum of Petroleum Revealed". Energy & Fuels. 27 (3): 1268–1276.
doi:10.1021/ef301737f.
4. Jump up ^ J.H. Pacheco-Sánchez, and G.A.Mansoori, (2013) Revista Mexicana de Física 59,
584-593.
5. Jump up ^ J.G. Speight, (1994). in the book Asphaltenes and Asphalts, 1, Developments in
Petroleum Science, 40 edited by Yen T. F. and G. V. Chilingarian, (Elsevier Science, New York
). Chapter: Chemical and physical studies of petroleum asphaltenes
6. Jump up ^ G.A. Mansoori, (2009). Int. J. Oil, Gas and Coal Technology 2 141.
7. Jump up ^ McKenna, A. M. (2013). "Heavy Petroleum Composition. 3. Asphaltene
Aggregation". Energy & Fuels. 27 (3): 1246–1256. doi:10.1021/ef3018578.
8. Jump up ^ Asomaning, S. (1997). Heat exchanger fouling by petroleum asphaltenes. Ph.D.
Thesis, University of British Columbia
9. Jump up ^ Rueda-Velasquez, R. I. (2013). "Characterization of Asphaltene Building Blocks by
Cracking under Favorable Hydrogenation Conditions". Energy & Fuels. 27 (4): 1817–1829.
doi:10.1021/ef301521q.
10. Jump up ^ Yang, Z.; Ma, C. -F.; Lin, X. -S.; Yang, J. -T.; Guo, T. -M. (1999). "Experimental and
modeling studies on the asphaltene precipitation in degassed and gas-injected reservoir oils".
Fluid Phase Equilibria. 157: 143. doi:10.1016/S0378-3812(99)00004-7.
11. Jump up ^ Rasuli Nokandeh, N.; Khishvand, M.; Naseri, A. (2012). "An artificial neural network
approach to predict asphaltene deposition test result". Fluid Phase Equilibria. 329: 32.
doi:10.1016/j.fluid.2012.06.001.
12. Jump up ^ Lei, H.; Pingping, S.; Ying, J.; Jigen, Y.; Shi, L.; Aifang, B. (2010). "Prediction of
asphaltene precipitation during CO2 injection". Petroleum Exploration and Development. 37 (3):
349. doi:10.1016/S1876-3804(10)60038-9.
13. Jump up ^ Understanding paraffin and asphaltene problems in oil and gas wells Archived
August 3, 2008, at the Wayback Machine., Petroleum Technology Transfer Council, South
Midcontinent Region, July 16, 2003 Workshop in Smackover, Arkansas at the Arkansas Natural
Resources Museum
External links[edit]
 An in-depth article on asphaltenes from OilfieldWiki.com, the oilfield encyclopedia
 Article regarding asphaltene fouling by Irwin A. Wiehe
 Asphaltene Aggregation from Crude Oils and Model Systems Studied by High-Pressure
NIR Spectroscopy (Source : American Chemical Society)
 A comprehensive website about asphaltene and its role in petroleum fouling by Prof. GA
Mansoori at the Univ. of Illinois at Chicago
 Asphalt

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