Petroleum Science and Technology

ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: http://www.tandfonline.com/loi/lpet20

Determination of wax content in crude oil

Mohammad Rehan, Abdul-Sattar Nizami, Osman Taylan, Basil Omar Al-Sasi

& Ayhan Demirbas

To cite this article: Mohammad Rehan, Abdul-Sattar Nizami, Osman Taylan, Basil Omar Al-
Sasi & Ayhan Demirbas (2016) Determination of wax content in crude oil, Petroleum Science and
Technology, 34:9, 799-804, DOI: 10.1080/10916466.2016.1169287

To link to this article: https://doi.org/10.1080/10916466.2016.1169287

Published online: 17 Jun 2016.

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 PETROLEUM SCIENCE AND TECHNOLOGY
, VOL. , NO. , –
http://dx.doi.org/./..

Determination of wax content in crude oil

Mohammad Rehana , Abdul-Sattar Nizamia , Osman Taylanb , Basil Omar Al-Sasib ,
and Ayhan Demirbasb
a
Faculty of Engineering, Department of Industrial Engineering, King Abdulaziz University, Jeddah, Saudi Arabia; b Center
of Excellence in Environmental Studies (CEES), King Abdulaziz University, Jeddah, Saudi Arabia

ABSTRACT KEYWORDS
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Wax deposition is one of the chronic problems in the petroleum industry. Crude oil; waxes; paraffins;
The various crude oils present in the world contain wax contents of up to solvent dewaxing; fractional
32.5%. Paraffin waxes consist of straight chain saturated hydrocarbons with car- precipitation
bons atoms ranging from C18 to C36. Paraffin wax consists mostly with normal
paraffin content (80–90%), while, the rest consists of branched paraffins (iso-
paraffins) and cycloparaffins. The sources of higher molecular weight waxes in
oils have not yet been proven and are under exploration. Waxes may precip-
itate as the temperature decreases and a solid phase may arise due to their
low solubility. For instance, paraffinic waxes can precipitate out when temper-
ature decreases during oil production, transportation through pipelines, and
oil storage. The process of solvent dewaxing is used to remove wax from either
distillate or residual feedstocks at any stage in the refining process. The solvents
used, methyl-ethyl ketone and toluene, can then be separated from dewaxed
oil filtrate stream by membrane process and recycled back to be used again in
solvent dewaxing process.

1. Introduction
Waxes are complex mixtures of high molecular weight or high carbon number alkanes that consist of
straight, branched, and cyclic chains (Demirbas, 2016). The aromatic rings contain 22 or more carbon
atoms. Waxes can be solid or liquid at room temperature; a unique property used in conventional deter-
mination of wax formation in crude oils (Demirbas et al., 2015a). For instance, oil is cooled to a specific
temperature and let the wax to precipitate under gravimetric techniques. The clean waxy crude contains
only hydrocarbons, and wax is present as a heavy organic component. The wax crystals are formed as
the clean waxy crude flows through a cold pipe or channel. While, the regular waxy crudes are not clean
and contain heavy organics such as asphaltenes and resins in addition to wax (Demirbas et al., 2015a;
Demirbas et al., 2015b).
Petroleum waxes are generally categorized into two groups, paraffin wax and microcrystalline wax,
present in petroleum distillates and residues. Paraffin waxes consist of straight chain saturated hydro-
carbons with carbon atoms ranging from C18 to C36 . Microcrystalline waxes are composed of branched
and cyclic hydrocarbons with carbon atoms ranging from C30 to C60 (Speight, 1991). Many crude oils
in the world contain significant quantities of wax (3–44%) that crystallizes during the oil production,
transportation, and storage (Kok and Saracoglu, 2000; Spiecker et al., 2003).
The reasons for high molecular weight or larger carbon number waxes in oils are still under explo-
ration. One possible explanation is that the larger carbon number waxes are composed of shorter carbon
number molecules produced at lower temperature reactions. For instance, C50 wax consists of two C25 s

CONTACT Ayhan Demirbas ayhandemirbas@hotmail.com Faculty of Engineering, Department of Industrial Engineering, King
Abdulaziz University, Jeddah, Saudi Arabia.
©  Taylor & Francis Group, LLC
 800 M. REHAN ET AL.

Figure . Main paraffinic wax structures.

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and C70 consist of two C35 s. According to Ajayi (2013) and Pu et al. (2014), fossilized organic matter
shows waxes of C25 to C45 are produced from land plants and bacteria. This is one of the reasons that why
nonmarine oils contain more waxes than marine oils. Figure 1 shows main paraffin structures. Paraffin
wax is mainly composed of straight chain hydrocarbons (C20 –C30 ) with 80–90% normal paraffin con-
tents, while the rest is composed of branched paraffins (iso-paraffins) and cycloparaffins. Normal paraffin
is a saturated hydrocarbon with molecules containing carbon atoms linked in a straight (unbranched)
chain. Wax contents of crude oils range up to 32.5% (As’ad et al., 2015).

2. Wax deposition
Wax deposition is one of the chronic problems in petroleum applications (Kok et al., 2007). Both types of
waxes, paraffin and microcrystalline, occur generally in lubricating oil fractions from crude oil and neg-
atively influence the quality and applications of the oil (Ajayi, 2013). Wax contents of various crude oils
are given in Table 1. Wax is crystallized in crude oil upon cooling, leading to flow problems in produc-
tion and processing units and pipelines. Paraffin wax deposition occurs during petroleum transportation
(Kok and Saracoglu, 2000). Improper insulation and heating systems are the precursors of wax deposi-
tion of the clean waxy crudes (Paso, 2014; Demirbas et al., 2015b; Demirbas, 2016). When the heavy
paraffin hydrocarbons precipitate due to temperature change, a wax-oil gel is formed (Robustillo et al.,
2012). Therefore, temperature change is the main cause of wax appearance in the pipelines (Spiecker
et al., 2003).

Table . Wax contents of various crude oils.

Crude oil Wax content, wt% Reference

Eastern Egyptian .–. Abu El-Ella and Nassef ()

Venezuelan (Boscan) . Lu and Redelius ()
Russian .–. Lu and Redelius ()
Sudan . Chen et al. ()
Daqing . Chen et al. ()
Shengli . Chen et al. ()
Qiuling . Chen et al. ()
Malu Isan . Musser and Kilpatrick ()
South China Sea . Musser and Kilpatrick ()
Arab heavy . Musser and Kilpatrick ()
Arab Berri . Musser and Kilpatrick ()
Alaska North Slope . Musser and Kilpatrick ()
Maya . Musser and Kilpatrick ()
San Joaquin Valley . Musser and Kilpatrick ()
Alba . Musser and Kilpatrick ()
Gulf of Mexico . Musser and Kilpatrick ()
 PETROLEUM SCIENCE AND TECHNOLOGY 801

Wax deposition and its flowing behavior result in flow strings plugging, hydrocarbons loss, and overall
high production cost (Adesina et al., 2010; Pu et al., 2014). Up to 32.5% wax is present in worldwide crude
oils that crystallize during oil production, transportation, and storage. This causes significantly high oil
viscosity and pour point values and oil gelation that brings difficulties during oil transportation and oil
refining activities (Chen et al., 2004; Adesina et al., 2010; Pu et al., 2014). The increased viscosity reduces
the flow tendencies of the fluid mixtures, and it increases the cost of pumping that is necessary for the
fluid flow (Ajayi, 2013).
Wax depositions were examined in oil production systems, and the deposition mechanism seems to
be understood with relation of heat and mass transfer, dissolution of a mixture of hydrocarbons and
the temperature gradient between the wall of pipeline and the bulk fluid (Aiyejina et al., 2011; Huang
et al., 2011; Valinejad et al., 2013). Wax precipitation in oil creates an increase in the non-Newtonian
behavior of petroleum mixture and hence increased viscosity (Elsharkawy et al., 2013). Depending on
the temperature and pressure, hydrocarbon components of wax can exist in any states of matter. The wax
forms crystals on freezing. When the paraffin wax forms crystals, they are called macrocrystalline wax.
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3. Solvent dewaxing of crude oil

The determination of wax percentage within crude oil is very important for petroleum industry, par-
ticularly for crude oil production, storage, and transportation. Various methods have been reported for
estimating the amount of wax present within crude oil. The wax precipitation has been a common prob-
lem for a wide range of petrochemical related industry for many years (Musser and Kilpatrick, 1998).
Xiaohu et al. (2008) have developed a simple test method to determine the percentage of wax in crude
oils including bitumen. For many years, natural waxes present in bitumen and their effect on the perfor-
mance of asphalt has been a hot topic for scientific debate. Currently the two European standard methods
used for wax content determination are EN 12606-1 (method by distillation) and 12606-2 (method by
extraction). However, these methods are generally very time consuming and may result in low accuracy
of estimated wax percentages (Nizami, 2016).
The recent technological advancement in laboratory equipment has greatly improved the analysis
of wide range of components in pipeline deposits (Zhang et al., 2014). The high-temperature gas chro-
matography (HTGC) and supercritical fluid chromatography (SFC) helps the detection of waxes of up to
100 carbon atoms as compared to the conventional detection limit of around 40 carbon atoms (Robustillo
et al., 2012). During the HTGC analysis, the higher boiling point compounds are also kept mobile because
the column is more stable even when heated to higher temperatures of 500°C as compared to conven-
tional analysis at 400°C. The waxes are analyzed by gas chromatography (GC) using a capillary column
of 12 m × 0.2 mm coated with nonpolar silicons such as SE-30, DC-200, and OV-1 (Shen et al., 2014).
Many researchers have correlated the performance of asphalt to the presence of natural waxes within
bitumen (McKay et al., 1995; Such et al., 2000; Richter, 2002). For example, a recently published study
reported that wax adversely affected the low temperature properties of asphalt; however these negative
impact on moisture susceptibility and wheel tracking resistance were not considered (Lu and Redelius,
2007).
Solvent dewaxing is a common method used to remove the wax from both distillates and residual
base stocks during distillation processes. Methyl-ethyl ketone (MEK) was used as a selective solvent to
dewax heavy crude oil at optimum conditions. The results indicated that MEK dewaxing performance
improved at higher mixing temperatures and it was found that a lower cooling temperature resulted in a
greater extraction of wax from the mixture (Musser and Kilpatrick, 1998).
The amount of wax increases due to several factors such as increase in initial weight of the crude
oil, decrease in temperature, increase of cooling time, and solvent ratio (Pu et al., 2014). Oil refineries
have exerted major efforts to develop methods for economic exploitation of the petroleum wax fractions,
spending huge money and time.
Extensive use of solvents for dewaxing progress over the last 25 years has resulted. Difficulties asphal-
tene emulsions and waxes are bound colloidal collection during oil recovery (Ebu El-Ella and Nassef,
2014). Petroleum colloids (waxes, resins, and asphaltenes) can be separated by elution processes on an
 802 M. REHAN ET AL.
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Figure . Sequential elution chromatography setup for separating petroleum colloids into waxes, resins, and asphaltenes.

activated silica gel column. Figure 2 shows the sequential elution chromatography setup for separating
petroleum colloids into asphaltenes (a), resins (b), and waxes (c), respectively.

4. Fractional precipitation of waxes and wax analysis

The wax precipitation within the crude oil streams may cause operational problems while transported
in undersea pipelines (Ajayi, 2013).
Generally the wax crystals are formed and separated with adsorbed resin and asphaltene as the tem-
peratures are lowered and thus the crude oil changes from liquid into suspension. Further decrease in
temperatures result in formation of a continuous phase of wax crystal lattice, whereas the remaining
liquid hydrocarbons turn into a dispersed phase (Musser and Kilpatrick, 1998; Abu El-Ella and Nassef;
2014).
The waxy crude oil has poor flow properties due to high viscosity and also normally high pour point.
The waxy crude oil is heated to enhance its flowability during transportation in pipelines. However, the
long distance pipelines are sometimes closed for maintenance or operational purpose or due to some
emergencies, resulting in a temperature drop in warm waxy crude oil, causing problems in its smooth
flow (Nizami, 2016).
Wax precipitation in crude oil is one of the most critical flow assurance problems leading to economic
losses (Kok et al., 2011). Wax has very low solubility and it precipitates out due to a decrease in tempera-
ture. Recently, an investigation was carried out to study the effect of various parameters, such as crude oil
 PETROLEUM SCIENCE AND TECHNOLOGY 803

initial weight, cooling time, and temperature, on amount of wax produced (Pu et al., 2014). It was found
that the amount of wax produced increased with decrease in crude oil initial weight and temperature and
increase in cooling time and solvent ratios. Normally, the wax precipitation occurs at lower temperatures
and the wax crystals adsorb resin and asphaltene, resulting in crude oil transformation from liquid in to
suspension (Majhi et al., 2015).
The waxy crudes are a worldwide issue and the major challenges, during their processing and trans-
portation, are not only precipitation of wax content at lower temperatures but also the formation of
deposits that cannot be completely removed by heating and pigging (Robustillo et al., 2012). Under-
standing wax and the wax-related process has been a subject of concentrated research for the develop-
ment of new solutions for deeper, colder, and longer fields as well as for field developments in arctic
and remote locations (Aiyejina et al., 2011). The viability of many of these new developments is strongly
linked to proven multiphase transport strategy technologically justified at prevailing economic realities.
The wax solidifies when the temperature of the hydrocarbon fluid drops below the wax crystallization
temperature, causing flow assurance problems (Kok et al., 2007).
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5. Membrane process for dewaxing

The membrane process is used for selective separation of solvent from the wax filtrate in solvent dewaxing
unit (SDU). The importance of dewaxing application leads to the development of first commercial scale
organic membrane process for liquid-liquid hydrocarbon separation in petrochemical based industry.
The solvents MEK and toluene used in the dewaxing process can be removed from the dewaxed oil
filtrate stream. The solvents are recovered close to dewaxing temperatures and recycled back to be used
again in the dewaxing process without further cooling.

6. Conclusions
Wax deposition is one of the most common flow assurance problems in the petroleum industry world-
wide. There are several methods including solvent dewaxing, used in industry to remove this wax from oil
stocks during its processing and transportation. Solvent dewaxing consists of several different processes
but all are based on the following general steps: (a) solvent mixed in feedstock, (b) chilling the mixture
to precipitate the wax, and (c) solvent recovery from wax and dewaxed oil for recycling by distillation
and stream stripping.
Most reservoirs fluids consist of heavy paraffin components that may precipitate out in solid form as
wax at lower temperatures. The waxes can be removed from crude oil by fractional precipitation and sol-
vent dewaxing methods. The deposition of wax in processing equipment and pipelines causes problems
in fluid handling and transportation. As the fluid temperature is lowered, higher weight hydrocarbon
molecules of wax become less soluble and precipitate out. Further cooling also results in lighter weight
hydrocarbon molecules to crystallize, increasing the solid wax fractions. The crystallization of wax is
not only controlled by temperature but also the composition of hydrocarbon molecules, especially the
lighter molecules.
The wax produced in oil can significantly influence its properties such as viscosity and pour point.
The solid waxes in sufficient amounts in steady state or slow flowing fluid conditions interact and result
in a matrix that entraps the liquid phase that effectively gels the fluid, lowering its flowability. This causes
serious problems during processing and transportation, including flow strings plugging, hydrocarbons
loss, and overall high production cost.

References
Abu El-Ella, R., and Nassef, E. (2014). Determination of wax content in Egyptian crude oils. Int. J. Eng. Trends Technol.
8:93–97.
Adesina, F., Anthony, A., Churchill, A., and Olawale, D. (2010). Modeling of wax deposition during oil production using a
two-phase flash calculation. Pet. Coal 52:193–202.
 804 M. REHAN ET AL.

Aiyejina, A., Chakrabarti, D. P., Pilgrim, A., and Sastry, M. (2011). Wax formation in oil pipelines: A critical review. Int. J.
Multiphase Flow 37:671–694.
Ajayi, O. E. (2013). Modelling of controlled wax deposition and loosening in oil and gas production systems. Master’s thesis,
Trondheim, Norway: Department of Energy and Process Engineering Norwegian University of Science and Technol-
ogy.
As’ad, A. M., Yeneneh, A. M., and Obanijesu, E. O. (2015). Solvent dewaxing of heavy crude oil with methyl ethyl ketone.
J. Pet. Environ. Biotechnol. 6:1–5.
Chen, J., Zhang, J., and Li, H. (2004). Determining the wax content of crude oils by using differential scanning calorimetry.
Thermochim. Acta 410:23–26.
Demirbas, A. (2016). Deposition and flocculation of asphaltenes from crude oils. Pet. Sci. Technol. 34:6–11.
Demirbas, A., Alidrisi, H., and Balubaid, M. A. (2015a). API gravity, sulfur content and desulfurization of crude oil. Pet.
Sci. Technol. 33:93–101.
Demirbas, A., Alsulami, H. E., and Hassanein, W. S. (2015b). Utilization of surfactant flooding processes for enhanced oil
recovery. Pet. Sci. Technol. 33:1331–1339.
Elsharkawy, A. M., Al-Sahhaf, T. A., and Fahim, M. A. (2000). Wax deposition from Middle East crudes. Fuel 79:1047–1055.
Huang, Z., Lu, Y., Hoffman, R., Amundsen, L., and Fogler, H. S. (2011). The effect of operating temperatures on wax
deposition. Energy Fuels 225:5180–5188.
Downloaded by [Chulalongkorn University] at 22:31 24 December 2017

Kok, M. V., Letoffe, J. M., and Clau, P. (2007). Comparative methods in the determination of wax content and pour points
of crude oils. J. Therm. Anal. Calorim. 90:827–831.
Kok, M. V., and Saracoglu, R. O. (2000). Mathematical modelling of wax deposition in crude oil pipelines (comparative
study). Pet. Sci. Technol. 18:1121–1145.
Lu, X., and Redelius, P. (2007). Effect of bitumen wax on asphalt mixture performance. Constr. Build. Mater. 21:1961–1970.
Majhi, A., Sharma, Y. K., Kukreti, V. S., Bhatt, K. P., and Khanna, R. (2015). Wax content of crude oil: A function of kinematic
viscosity and pour point. Pet. Sci. Technol. 33:381–387.
McKay, J. F., Branthaver, J. F., and Robertson, R. E. (1995). Isolation of waxes from asphalts and influence of waxes on
asphalt rheological properties. ACS 210, National Meeting of the American Chemical Society (ACS), Chicago, Illinois,
August 20–25.
Musser, B. J., and Kilpatrick, P. K. (1998). Molecular characterization of wax isolated from a variety of crude oils. Energy
Fuels 12:715–725.
Nizami, A. (2016). Waxes fraction of crude oil. Energy Ed. Sci. Technol.-C 8:55–62.
Paso, K. G. (2014). Comprehensive treatise on shut-in and restart of waxy oil pipelines. J. Dispers. Sci. Technol. 35:1060–
1085.
Pu, H., Ai, M., Miao, Q., and Yan, F. (2014). The structural characteristics of low-temperature waxy crude. Pet. Sci. Technol.
32:646–653.
Richter, F. (2002). Effect of waxes on bitumen quality. Oil Gas Eur. Mag. 2:35–38.
Robustillo, M. D., Coto, B., Martos, C., and Espada, J. J. (2012). Assessment of different methods to determine the total wax
content of crude oils. Energy Fuels 26:6352–6357.
Shen, F., Zhao, M., Lu, J., and Ding, Q. (2014). Study on performance of porous regenerative asphalt concrete. Energy Ed.
Sci. Technol.-A 32:5253–5258.
Speight, J. G. (1991). The Chemistry and Technology of Petroleum. New York: Marcel Dekker.
Spiecker, P. M., Gawrys, K. L., Trail, C. B., and Kilpatrick, P. K. (2003). Effects of petroleum resins on asphaltene aggregation
and water-in-oil emulsion formation. Colloids Surf., A: Physicochem. Eng. Aspects 220:9–27.
Such, C., Planque, L., Lombardi, B., Planche, J. P., Gillet, J. P., and Seive, A. (2000). Les paraffines dans les bitumes [Paraffins
in bitumes]. Second Eurasphalt & Eurobitume Congress, Barcelona, Spain, September 20–22.
Valinejad, R., and Nazar, A. R. S. (2013). An experimental design approach for investigating the effects of operating factors
on the wax deposition in pipelines. Fuel 106:843–850.
Xiaohu, L., Kalman, B., and Redelius, P. (2008). A simple test method for determination of waxes in crude oils and bitumens.
4th Eurasphalt and Eurobitume Congress, Copenhagen, Denmark, May 2008.
Zhang, M., Li, T., Tang, L., Han, Z., and Peng, Y. (2014). Evaluation of reservoir damage characteristics and countermeasures
in Jiyuan oilfield. Energy Ed. Sci. Technol.-A 32:5133–5140.