CHN-327 Petroleum Refining

Lecture 27

Dr. Hari Prakash Veluswamy

Assistant Professor
Depar tment of Chemi cal Engineering
IIT Roor kee

19 OCTOBER 2022
Outline of today’s lecture
 Deasphalting process
 Need
 Process
 Solubility concept
 Operating variables

CHN-327 PETROLEUM REFINING 2

 Deasphalting
• While distillation achieves separation/fractionation of the feed components with
respect to differences in their boiling point, deasphalting (as a solvent extraction
process) fractionates the feedstock, atmospheric, or more often vacuum distillation
residue (VDR), with respect to solubility/insolubility of molecular components in a
given solvent.
• A solvent fractionation scheme is used in laboratories to separate VDR into fractions
that are defined based on the solubility behavior
• VDR, which could be a solid at ambient temperature, is completely dissolved in
aromatic solvents such as benzene and toluene. The highest molecular weight
components of VDR classified as “asphaltene” can be separated by precipitation (as
solid material) when a light paraffin solvent is mixed with VDR solubilized in an
aromatic solvent (e.g., toluene)
• Paraffin solvent used (e.g., n-heptane) defines the identity of the separated
asphaltenes (e.g., toluene soluble and n-heptane insolubles)
• The portion of VDR that is soluble in the paraffin solvent is called maltenes, but also
labeled with respect to the solvent used in the separation, i.e., n-heptane maltenes
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 Deasphalting
• The n-heptane solubles can further be separated using n-pentane (a lighter and a
weaker solvent) into insoluble (hard resin) and soluble (n-pentane solubles) fractions.
• The n-pentane solubles can also be separated using a lighter solvent yet (propane) to
soft resin and oil products.
• In refinery practice, only one stage of separation is used using the lightest solvent
(e.g., propane) to produce asphalt and deasphalted oil (DAO) fractions
• Asphaltenes consist of high-molecular weight compounds with strong aromatic
character and contain highest concentrations of heteroatom (S, N, and metal) species.
• Because of the low H/C ratio of asphaltenes and resins, the deasphalting process can
be considered as a “carbon rejection” process, yielding a high H/C ratio product (i.e.,
oil) after removing the asphaltenes and resins, as, typically, lower value byproducts

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 Solvent fractionation of vacuum distillation residue

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 Gradient solubility model
• Because of the large disparity in structure and properties of asphaltenes and
oil fractions in VDR, it is surprising that VDR appears as a solution (one-phase
material) rather than a suspension of discrete asphaltene particles in VDR.
• A commonly accepted hypothesis to explain the single phase observed with
VDR is known as the gradient solubility model, illustrated in Figure

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 Gradient solubility model
• The gradient solubility model offers an explanation of how asphaltenes can be
forced out of the solution in VDR by solvent extraction.
• Briefly, the solubility of a compound in a given solvent depends on the strength of
the solvent that is measured by Hildebrand Solubility Parameters (HSP) for non-
polar solvents.
• The two definitions of HSP, indicating the dependence of the parameter values on
surface tension and molar volume of the solvent (1st Hildebrand parameter), or on
the energy of vaporization (heat necessary to evaporate the solvent under constant
volume conditions) and molar volume (2nd Hildebrand Parameter)
• Solubility parameter increases with the increasing density (decreasing molar
volume) and increasing surface tension, or increasing latent heat of vaporization.
• This explains why aromatic solvents have higher solvent power than aliphatic
hydrocarbons, and why the solvent power of paraffins decreases with the
decreasing carbon number.
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 Hildebrand Solubility Parameters

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 Deasphalting Process
• Deasphalting process in a refinery flow scheme as an intermediate process between
vacuum distillation and dewaxing processes, for producing the refinery output streams as
asphalt deasphalted oil (DAO), which can be directed to another separation process,
dewaxing, to produce lubricating oil base stock and wax, or can be sent to conversion units
such as hydrocracking to produce light and middle distillate fuels.

• It is important to note that the deasphalting process is an upgrading process to transform

VDR into marketable products, and/or convert it to distillate fuels that command high
demands
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 Deasphalting Process
• The two objectives of the deasphalting process are:
• Produce asphalt - as final product.
• Remove asphaltenes to prevent coke, or metal buildup on catalyst in further processing of
DAO.
• Depending on the properties of the VDR and prevailing markets, the emphasis
could be placed on one of these objectives.
• Aromatic asphaltic crudes are more expensive to convert into distillate fuels
• Such crudes could be processed readily into making high yields of asphalt and
serve the asphalt market.
• With lighter crudes, the principal focus could be on removing the asphaltenes from
VDR so that DAO produced can be used in conversion processes with a lower extent
of problems caused by asphaltenes such as coke buildup, or metals buildup on
catalysts in, for example, hydrotreating or hydrocracking reactions.

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 Propane Deasphalting process

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 Propane Deasphalting process
• First step in deasphalting, residue (feedstock) is mixed with four to eight times
the volume of liquid propane.
• Heavier residua require a higher solvent to residue (S/R ) ratio for effective
separation of asphalt.
• Following the precipitation of asphalt, DAO and asphalt are separated, and
each stream is purified and flashed to recover and recycle the propane solvent
• The four-unit operations of deasphalting illustrated in the process flow diagram
are:
• Flocculation (& precipitation) of asphaltenes
• Asphalt decanting - separation
• Asphalt washing - to remove entrained oil
• Solvent recovery and recycle
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 Variables in Deasphalting process
• Independent variables in the deasphalting process include
• Solvent used
• Pressure
• Temperature
• Solvent/Residue (S/R) ratio and
• Contact time.
• These variables can be controlled to obtain the optimum conditions for the
desired separation in deasphalting.
• One of the important dependent variables in the process is the asphaltene
yield
• Qualitative plots of how asphaltene yield varies as a function of the process
parameters is provided

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 Asphaltene yield dependence on operating variables

• Solubility parameter of the solvent is a key a variable

that affects asphaltene yield • As temperature increases, solubility
• Asphaltene is completely soluble in toluene which parameter of the solvent decreases
has a high solubility parameter. Therefore, the
asphaltene yield with toluene will be zero
• Propane (C3,) which has the lowest solubility
parameter among the solvents given in the plot, will
give the highest asphaltene yield

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 Asphaltene yield dependence on contact time

• A sufficient amount of contact time with paraffin is

necessary for good asphaltene separation.

• The 8-10 h contact time refers to batch experiments

in laboratory.

• In flow systems of commercial deasphalting, the

contact time necessary for the desired separation of
asphalt is much shorter.

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 Asphaltene yield dependence on S/R ratio
• Asphaltene yield increases with the increasing solvent/residue ratio used in the process.
This is an unusual behavior for solvent extraction because, typically, the yield of an insoluble
fraction would decrease with the increasing quantity of solvent used in the extraction
behavior.
• The unusual behavior seen is termed as the “anti-solvent effect.”
• This relates to the gradient theory of asphaltene solubility in crude oil (or in VDR) such that
larger quantities of paraffin solvent used in the process more effectively disrupt the gradient
solubility by removing more oils from VDR, forcing the asphalt fraction (asphaltene+resin) to
separate out.
• Molecular composition of the asphaltenes would vary significantly along with the yield of
asphaltenes in the plot.
• As the yield of asphaltenes increases with the increasing S/R, lower molecular weight
asphaltenes would be progressively included in the separated asphaltenes. In other words,
for a given process, low yields of asphaltenes (obtained at low S/R) would contain the
highest molecular weight and highly aromatic compounds, whereas asphaltenes obtained at
high yield with high S/R ratio would include a broader range of molecular weight and
aromaticity in the separated asphaltenes.
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 Asphaltene yield dependence on S/R ratio

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 Asphaltene yield dependence on S/R ratio
• The consideration of variable asphaltene composition would also apply to
the asphaltenes separated with different paraffin solvents.
• In this case, lower yields of asphaltenes obtained with C7 (n-heptane) will be
associated with heavier and more aromatic asphaltenes than those obtained
with propane (C3).
• These observations relate to the absence of a precise molecular definition to
express the complex of asphaltenes, but the need to use an operational
definition on the basis of solubility/insolubility in a given solvent.
• It should, therefore, be remembered that the composition of the
asphaltenes, or asphalt produced in a refinery would not only depend on the
properties and composition of the parent crude oil, but also on the solvent,
as well as the S/R ratio used in the process among other factors, such as
temperature and pressure as they affect the solubility parameters of the
solvent
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