Paraffin / Wax

The wax present in petroleum crudes primarily consists of paraffin hydrocarbons (C18 - C36)
known as paraffin wax (Sudan oil) and naphthenic hydrocarbons (C30 - C60). Hydrocarbon
components of wax can exist in various states of matter (gas, liquid or solid) depending on their
temperature and pressure.

The hydrocarbon C31H64 is a typical component of paraffin wax.

Wax is a commonly occurring component of crude oil. It is generally characterized As consisting

of large n-parans that are solid at room temperature when isolated, Yet soluble in the crude oil
mixture at elevated temperatures.

Waxy Crude Oil

In general, petroleum fluids can be classified into four major fractions denoted as saturates,
aromatics, resins, and asphaltenes. Saturates are non-polar and consist of normal alkanes (n
paraffins), branched alkanes (iso-paraffins) and cyclo-alkanes (naphthenes). Examples of each of
these classes of chemicals along with the aromatics, resins and asphaltenes have been reported
elsewhere (McCain.,1990; Cruse et al., 1960; Lira-Galeana et al., 2000). Saturates are the largest
single source of hydrocarbon or petroleum waxes, which are generally classified as paraffin wax,
microcrystalline wax and/or petrolatum (Warth, 1956). Of these, the paraffin wax is the major
constituent of most solid deposits from crude oils.
Waxy crude oils are crude oils with relatively high amounts of wax suspended in them. A Waxy
crude usually consists of: i. A variety of light and intermediate hydrocarbons (paraffins,
aromatics, naphthenic, etc.). ii. Wax as defined above. iii. A variety of other heavy organic (non-

hydrocarbon) compounds, even though at very low conc entrations including resins, asphaltenes,
diamondoids, mercaptdans, organo- metallics, etc.
Once the waxy crude is cooled to below (wax appearance temperature) Twa, it may form an
viscoelastic gel, and much larger pressure drops are then required in order to ensure the same
flow rate.

The severity of paraffin deposition depends predominantly on the composition (wax content) of
the crude oil, the cloud-and pour-points, the ambient and operating temperatures, pressure drop
and pipe roughness

The process whereby wax precipitates deposit on pipeline walls. It is possible for waxes to
\deposit" on the inner surface of a pipe if the temperature of the pipe wall is below the cloud
point of the oil (or the wax appearance temperature Twa) .
This incipient wax layer is the _rst step towards deposition of the gel on the pipe wall.
The combined presence of spatial temperature gradients and dilution of wax-forming molecules
towards the cold wall has been shown to be responsible for the hardening of the wax deposits
closest to the pipeline wall. In addition to this, non-uniformity in cooling rates across a pipeline
can result in a spatially non-homogenous gel.

Figure: Diagram from Venkatesan et al. [202] showing the process whereby wax
layers \deposit" on pipe walls due to the presence of a temperature gradient.

Figure: Images from showing the Wax precipitates may have on a pipeline cross-section.

Figure: Image of a typical waxy crude oil below its wax appearance temperature
Twa (sample provided by Chevron). The material clearly holds its shape and does
not flow - behavior indicative of a yield stress fluid.

Wax Crystallization
The rheology of waxy crude oil is extremely sensitive to temperature, because at lowered
temperatures it is possible for wax to precipitate out of the crude oil mixture and form a samplespanning gel-like structure composed of crystallites with a high aspect ratio. The sample
spanning network formed by these crystallites is akin to a physical gel network in which the
correlation length has diverged towards innity and the high aspect ratio of the crystallites allows
for gelation to occur at low volume fractions of precipitated wax.
. The crystals formed of paraffin wax are known as macrocrystalline wax. Those formed from
naphthenes are known as microcrystalline wax

Macrocrystalline , Microcrystalline, and Crystal Deposit Network of Wax

An atomic force microscope image of the spiral growth of paraffin crystal (measuring
approximately 15 microns across). Inset shows orthorhombic arrangement (0.49nm x 0.84nm) of
chain ends of one of the crystal terraces.

Microscopy images of wax precipitates in a para_n gel reproduced in

(a). The precipitates appear as bright in this image, and have a needle like
shape. In (b), transmission electron microscopes of cryo-fractured wax precipitates.

Mechanism of Paraffin Wax Crystallization:

Paraffin waxes are semi-crystalline in nature and tend to crystallize/precipitate from crude oils at
and below the equilibrium solid-liquid temperature (thermodynamic cloud point). Crystallization
is the process whereby an ordered solid structure is produced from a disordered phase, such as a
melt or dilute solution (e.g. crude oil). It usually involves two distinct stages, namely nucleation
and growth which may be considered separately. These are described in earlier publication
(Hammami and Raines, 1999).

Figure : depicts three idealized models of paraffin wax crystallization,

namely (a) n-paraffins only, (b) n-paraffins + iso-paraffins and (c) n-paraffins + iso-paraffins +
cyclo-paraffins, to illustrate the effect of molecular structure and geometry on the nucleation
process and the resulting crystal stability. As can be seen in Figure 2 (a), the n-paraffins are
flexible hydrocarbon molecules and, hence, tend to align/cluster together upon cooling and
precipitate from crude oil as stable wax solids. The iso-paraffins are also flexible hydrocarbon
molecules; however, the corresponding side chains tend to delay the formation of wax nuclei
(i.e., depress the cloud point) and usually form unstable wax solids (crystals with defects) as
shown in Figure 2 (b). Cyclo-paraffins, also known as naphthenes, are stiff (least flexible) and
bulky in nature; they tend to disturb and/or disrupt the wax nucleation and growth processes. The
corresponding wax crystals are the least stable saturates (of the microcrystalline wax type) as
depicted in Figure 2 (c).

It is conceivable that most commercial wax inhibitors, which are polymeric in nature, are
specifically synthesized to be branched and/or contain some steric functional groups to help
interfere with the paraffin nucleation process and promote crystal imperfections; hence, less
stable and easy to dissolve (low heat of fusion) wax crystals are formed. The nucleation
temperature and, in turn, cloud point would be expected to shift further to the lower temperature
scale in the presence of low molecular weight paraffins (i.e., light ends) and aromatics which are
known to be adequate solvents for wax. Whereas, resins do not usually play a significant role on
wax precipitation, the presence of impurities and/or amorphous organic solids (such as
asphaltenes) in the oil usually induce wax nucleation process as they tend to lower the energy
barrier for forming the critical wax nucleus (Hammami and Raines, 1999).