Refinery Processes

Catalytic Reformer
• Catalytic reforming converts low-octane straight run naphtha fractions (particularly heavy
naphtha that is rich in naphthenes) into a high-octane, low-sulfur reformate, which is a
major blending product for gasoline.
• The most valuable byproduct from catalytic reforming is hydrogen, which is needed in
refineries with increasing demand for hydrotreating and hydrocracking processes.
• Most reforming catalysts contain platinum supported on alumina, and some may contain
additional metals such as rhenium and tin in bi-, or tri-metallic catalyst formulations.
• Early reforming processes were called platforming in reference to reforming with a platinum
catalyst.
• In most cases for catalytic reforming, the naphtha feedstock needs to be hydrotreated before
reforming, to protect the platinum catalyst from poisoning by sulfur or nitrogen species.
• The principal reactions in catalytic reforming include dehydrogenation of naphthenes to
aromatics (with significant quantity of hydrogen as byproduct) and cracking/isomerization of
n-paraffins into i-paraffins.
• The principal product from catalytic reforming is called reformate, consisting of C4 to C10
hydrocarbons.
• Reformate has a high octane number because of high concentration of aromatic compounds
(benzene, toluene, and xylene) produced from naphthenes.
• With the more stringent requirements on benzene and total aromatics limit in US and Europe
(less than 1% benzene, 15% total aromatics), the amount of reformate that can be used in
gasoline blending has been limited, but the function of catalytic reforming as the only internal
source of hydrogen continues to be important for refineries.
 Catalytic Hydrotreatment
• As seen with the catalytic reforming in the previous section, catalytic hydrotreatment can be
used as a pretreatment step to protect catalysts from crude oil contaminants such as
heteroatom (S, N, O) compounds, as well as metals (mainly Ni, V).
• Hydrotreatment is also used as a major finishing process in a petroleum refinery.
• Shifting to the side stream products from the distillation column, kerosene and light gas oil
fractions can be hydrotreated to remove the heteroatoms to produce the final products of jet
fuel, and diesel fuel.
• Typical catalysts used for hydrotreating are Co and Mo compounds supported on alumina
(Al2O3).
 Conversion of Heavy Gas Oil
• Moving down on the side streams of the distillation column, heavy gas oil
(consisting of C20 to C25 hydrocarbons) constitutes the next fraction in line.
• These processes, aimed at reducing the molecular size or the boiling point of gas
oil compounds, involve thermal cracking or catalytic cracking.
• A mild thermal cracking process, called visbreaking, is applied to reduce the
viscosity of the feedstock, and it is more frequently applied to residual fractions,
such as vacuum distillation residue.
• A more severe thermal cracking of heavy gas oil can be used to produce LPG and
ethylene and light and middle distillates from heavy gas oil.
• A highly aromatic byproduct from thermal cracking is called ethylene tar. Ethylene
is an important petrochemical feedstock, while ethylene tar can be used as
feedstock to produce carbon blacks.
• Catalytic cracking is more frequently used for conversion of heavy gas oil to
gasoline.
Products and processes of heavy Gas
Oil Conversion
Start: Heavy Gas Oil (from atm
Distillation) > 20 – 25 Carbons goes to
Visbreaking (mild thermal treatment)
Fuel oil
Thermal Cracking
LPG, ethylene
Naphtha
Middle distillate (kerosene +light
gas oil)
Ethylene Tar
Catalytic Cracking
Produces branched chain alkanes
Slurry Oil
clarified
Clarified slurry oil
Products and Processes of FCC
Start: Heavy Gas Oil (HGO) goes to
FCC with Al3O3 + Zeolite catalysis
C2, LPG
Motor Gasoline
Light Cycle Oil (LCO)
FCC Slurry Oil
Decanting
Clarified Slurry Oil (CSO/Decant Oil)
Fuel Oil
Delayed Coking
Premium (needle) coke
Graphite electrodes

• A particular process of catalytic cracking, Fluid Catalytic Cracking, is almost exclusively used
worldwide in heavy gas oil and light vacuum gas oil conversion.
• This process produces high octane gasoline primarily, with important byproducts, including LPG,
light olefins and i-alkanes, light cycle oil (LCO), heavy cycle oil (HCO), and clarified slurry oil (also
called decant oil).
• LCO is used to produce diesel oil by hydrocracking, and decant oil can be used as fuel oil, feedstock
for carbon black manufacturing, and to produce a special type of petroleum coke called needle coke.
• Needle coke has a microstructure that makes it a good precursor to graphite electrodes that are used
in electric-arc furnaces to recycle scrap iron and steel.
• The manufacturing of graphite electrodes, using a byproduct from FCC used to produce gasoline, is
considered a principal interface between petroleum refining and the iron and steel industry.
 Conversion and Processing of Vacuum Gas Oils
• Moving to the vacuum distillation column, the vacuum distillates, light vacuum
gas oil (LVGO) and heavy vacuum gas oil (HVGO) can be processed by some
advanced FCC processes.
• However, hydrocracking is more frequently used to convert LVGO and HVGO into
light and middle distillates, using particular catalysts and hydrogen.
• Similar to LCO, the LVGO and HVGO fractions from vacuum distillation tend to
be highly aromatic.
• Catalytic hydrocracking combines hydrogenation and cracking to handle
feedstocks that are heavier than those that can be processed by FCC, because of
excessive coke deposition on the catalyst in the absence of hydrogen.
• Middle distillates (e.g., kerosene and diesel fuel) are the principal products of
hydrocracking. In addition to light and middle distillates, hydrocracking also
produces light distillates and LPG.
Schematic of Hydrocracking Light Vacuum Gas Oil (25-35 Carbon Chains).
The carbon molecules undergo hydrocracking in the presence of hydrogen gas. The
products come out as C3 and C4 molecules along with light and medium distillates. The
schematic also notes that the catalytic process includes hydrogenation (to saturate
aromatic rings) and the cracking of C-C bonds.
HVGO can also be used as a feedstock to produce lubricating oil base stock, through a
sequence of solvent extraction processes to remove aromatic hydrocarbons by furfural
extraction, and to remove long-chain paraffins by dewaxing.

Schematic of Hydrocracking Heavy Vacuum Gas Oil (25-35 Carbon Chains).

The Heavy vacuum gas oil goes into solvent extraction with furfural which extracts the
heavy aromatics. Then the products go into dewaxing which separates out long-chain
n-paraffins (wax). That yields lube oil base stock which becomes lubrication oils.
 Processing and Conversion of Vacuum Distillation
Residue
• The heaviest and the most contaminated component of crude oil is the vacuum distillation
residue (VDR), also referred to as the bottom-of-the-barrel.
• There are multiple processing paths to upgrade VDR into usable products. One process is
called deasphalting, which removes the heaviest fraction of VDR as asphalt that is used
mainly to pave roadways.
• The lighter fraction obtained in the deasphalting process, deasphalted oil (DAO), can be used
as fuel oil after hydrotreatment.
• Thermal processes, such as visbreaking and coking, also provide options for upgrading VDR,
which is normally a solid at ambient temperature.
• The visbreaking operation involves mild thermal cracking, with the primary purpose of
producing a relatively low grade fuel oil (with a much lower pour point than VDR) and
byproducts such as middle and light (naphtha) distillates and LPG.
• The yield of these byproducts would normally not exceed 10%wt of VDR.
• As a general rule in refinery conversion processes, producing a lighter product with a higher
H/C ratio (e.g., fuel oil, middle distillates, LPG) from a feedstock (e.g., VDR) would require
the simultaneous formation of a heavier product (e.g., coke) with a lower H/C ratio than the
feedstock.
• Clearly, this compensation is dictated by the hydrogen balance, or hydrogen distribution
among the products.
• With no external hydrogen entering the conversion unit (as it would in hydrogenation, or
hydrocracking reactions), making a product(s) with a higher H/C ratio than that of the feed
would require making other product(s) with a lower H/C ratio than that in the feedstock.
• In the case of visbreaking, what enables the production of lighter (or lower viscosity) fuel oil
and other products from VDR is the formation of small quantities of coke with an extremely
low H/C ratio.
• Hence, the term disproportination describes this unequal distribution of C or H in the
conversion products, or losing (rejecting) C in the coke that accumulates on reactor tubes and
is periodically burned out to clean the reactor tubes.
Visbreaking of VDR with mild thermal cracking yields C3 and C4 carbons, naphtha,
middle distillates and fuel oil. As a penalty it also produced coke (disproportionation!).
Coking of VDR with severe thermal cracking which yields light and middle distillates,
and sponge coke & fuel grade coke which becomes anode coke, (low sulfur metals)
which are used for aluminum production. This process also has some disproportionation.

• As different from visbreaking, coking

involves severe thermal cracking with
intentional production of coke with a
low H/C, so that lighter fuels can be
obtained from VDR (by
disproportionation).
• The product coke obtained from VDR
with relatively low heteroatom
concepts, termed sponge coke, can be
used in manufacturing carbon anodes
that are used in electrolysis of alumina
(Al2O3) to produce aluminum metal.
• It should be clear from this quick tour of a refinery, that the most valuable products from a
refinery include light distillates (gasoline) and middle distillates (jet fuel and diesel).
• These products are mostly paraffinic and contain relatively short paraffin chains, or small
molecules, or, in other words, high H/C ratios.
• In this context, one could summarize the overall goal of petroleum refining as managing the
H/C ratio of the products for the optimum distribution of hydrogen into products to maximize
profits.
• Controlling the H/C ratio of the products would require either lowering the C content of the
products (i.e., carbon rejection), or increasing the H content (i.e., hydrogen addition).
• The processes, coking, solvent extraction (e.g., deasphalting), visbreaking, and catalytic
cracking reject carbon in the coke (carbonaceous) product so that lighter products (with high
H/C) ratios can be obtained in these processes.
• Carbon in the coke, or in the heavier product is considered to have been rejected (and
potentially lost) since the carbonaceous byproducts have much lower value in comparison to
those of the lighter products.
• In contrast, hydrogen addition, as in the processes of hydrogenation and hydrocracking,
enables the conversion of all the carbon present in heavy oil (or crude oil) to high value
products without rejecting, or sacrificing, any.
• One might ask, then, why would any refinery carry out any carbon rejection process instead of
hydrogen addition? A short answer to this question involves basic refinery economics; the
hydrogen addition processes cost much more than carbon rejection processes, because
producing hydrogen and the catalysts used in hydrogen addition processes are very expensive.
 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.
• Solvent fractionation is used 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).
• The 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.
• 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.

Figure. Solvent fractionation of vacuum distillation residue (VDR).

 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.
• The model claims that asphaltene molecules can be dissolved in resins and the resulting
solution can be dissolved in oil (wiggly lines), thus producing a single phase solution.
• Some model molecular structures proposed for asphaltenes are shown in below Figures.

Figure. Gradient-solubility model

to explain dissolution of
asphaltenes in crude oil.
Figure. Proposed molecular Figure. Another proposed molecular
structures for asphaltene structures for asphaltene molecules.
molecules.
• 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 are given in Figure 5.7, 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), respectively.
• These parameters correlate well with one another, and each can be used without any
preference to express the dissolving power of a solvent.
• 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.
• It is now possible to explain that using a large volume of a paraffin solvent, added to
dissolved VDR in a laboratory experiment, effectively disrupts the gradient solubility of
asphaltenes, and as a result, asphaltenes precipitate as solid particles and can be filtered out
for recovery.
• In refinery deasphalting process, however, e.g., in propane deasphalting, lower quantities of
solvent (or lower solvent to resid (S/R) ratio) is used to separate asphalt (asphaltenes + resins)
and deasphalted oil (DAO).
 Deasphalting Process
• The deasphalting process in a refinery is 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.

Figure. Configuration of deasphalting and dewaxing processes in a petroleum refinery.

The two objectives of the deasphalting process are:
1. Produce asphalt - as final product.
2. 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.
• Remember that 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.
 Simplified Flow Diagram of a Deasphalting Process
• As the 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:
1. Flocculation (& precipitation)
of asphaltenes
2. Asphalt decanting -
separation
3. Asphalt washing - to remove
entrained oil
4. Solvent recovery and recycle
 Asphaltene Yield
• Independent variables in the deasphalting process include the solvent used, pressure,
temperature, S/R, 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. Below figure shows, in qualitative plots, how
asphaltene yield varies as a function of the process parameters

Effect of solubility parameter on asphaltene

yield.

Effect of molecular weight on

asphaltene yield.
Effect of temperature on asphaltene yield.

Effect of contact time on asphaltene yield.

 Solubility Parameter of the Solvent
• Solubility parameter of the solvent is a key a variable that affects asphaltene yield. Asphaltene is completely
soluble in toluene which 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.
• 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 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.
• One should point out here that the 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 SR ratio
would include a broader range of molecular weight and aromaticity in the separated asphaltenes.
• 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.
• 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.
 Dewaxing
• Another important separation process in petroleum refining is removal of wax.
• The feedstocks to dewaxing include DAO from deasphalting, and HVGO from vacuum distillation as
shown in Figure along with some compositional characteristics of the feedstock and the dewaxing product.
• Note that wax (long-chain paraffins) obtained in dewaxing is a marketable by-product. Lubricating oil base
stock is the principal product of interest.
• The main purpose of dewaxing is to remove hydrocarbons that solidify readily (i.e., wax) for making
lubricating oil base stock with low pour points (-9 to 14°F).
In addition to low pour points, other important properties of lube oil base stocks include:
1. Volatility – should be low to keep oil in the liquid phase during engine operation.
Vapors are not good lubricants.
2. Viscosity– important to control because of lubrication and heat transfer considerations.
Moderate viscosities are desired. Low viscosity may not provide the required
lubrication and lead to high friction between metal parts. High viscosity causes loss of
energy.
3. Viscosity Index (change in viscosity with temperature) – small change in viscosity is
desired over a wide temperature oil, i.e., high viscosity index (HVI). HVI ensures that
the lube oil functions well at both cold start and at high temperatures generated by the
engines.
4. Thermal Stability – High thermal stability (or small degree of thermal degradation at
high temperatures) is necessary to minimize viscosity loss and coke deposition on metal
surfaces.
All of these properties depend on the molecular composition of the hydrocarbons
constituting the lubricating oil base stocks. Commercial engine oils and other commercial
lube oils are formulated with chemical additives that would enhance the performance of the
base stocks.
Two commercial methods of dewaxing are:
1. Solvent dewaxing - physical process; separation of wax by freezing and solvent
transport.
2. Catalytic dewaxing - chemical process; removal of wax by selective reaction of long
chain n-alkanes (wax).
 Solvent Dewaxing
• Upon refrigeration, wax compounds solidify to form crystals.
• Wax crystals are carried in the solvent to a rotary filter where wax is separated on a filter cloth
covering the rotating drum.
• The layer of wax (filter cake) on the drum is scraped from the filter by a blade and carried
away in a solvent stream to a steam-stripping unit to recover and recycle the solvent separated
from the wax product.
• The wax product, called slack wax, can be used to make paraffin wax for candles, microwax
used in the cosmetics industry, and petrolatum for petroleum jelly.
• The dewaxed oil from the filtration unit is also steam stripped to recover the solvent to
produce the lube oil base stock.
The two principal solvents used in solvent dewaxing units are methyl ethyl ketone
(MEK) and propane. Although the majority of dewaxing units in the U.S. refineries
use MEK), some advantages of using propane as a solvent compared to MEK include
the following:
• Propane is used both as a diluent and as a refrigerant
• Lower capital investment
• Refrigeration energy savings
• Higher filtration rates
• Rejection of asphaltenes and resins in the feed
• Higher VI than ketone dewaxing
 Catalytic Dewaxing
• Catalytic dewaxing is a low-severity conversion process involving a selective catalytic
cracking of n-paraffins.
• Because of removing wax (long chain n-paraffins) by chemical reaction, the process is
called dewaxing.
• The selective cracking of n-alkanes takes place in the pores of molecular sieve
catalysts (zeolites) with pore openings in the order of 0.6 nm, which keep i-paraffins out
because of their larger size due to branching in the hydrocarbon skeleton, as shown in
Figure A.
• This selective cracking increases the ratio of i-paraffins to n-paraffins in the product and
lowers its pour point.
• Hydrogen is introduced along with the feed to prevent coking on the catalyst surfaces
(Figure B). The cracking of n-paraffins produces distillate fuels such as gasoline as a
by-product from catalytic dewaxing.
The advantages of catalytic dewaxing include:
 production of lube base stock with lower pour point and in higher yield compared
to the product obtained from solvent dewaxing. Low yield from solvent dewaxing
results from the difficulty of separating the oil from the wax;
 lower capital investment;
 good product stability;
 flexibility to produce both lube oil base stock and light distillates.
Figure A. Chemistry of catalytic dewaxing inside molecular sieving zeolites, e.g.,
mordenite, the structure of which is shown in the figure.
Figure B. Catalytic dewaxing process.
 Thanks

n-gl.com