IIT Delhi
Refinery and Technology
Prof. Abhijeet Raj
[email protected] Dept. of Chemical Engineering, Block III-
3B-14
Indian Institute of Technology Delhi
Hauz Khas, Delhi
110016
Thermal Processes
Thermal Processes: When heating a hydrocarbon to a sufficiently high temperature, thermal cracking
takes place.
The free radical chain reaction starts with breaking the weakest C-C bond in the reactant alkane (R-H) to
form two free radicals R1 and R2, each with one unpaired electron resulting from the homolysis of the C-C
bond (initiation). Once formed by the initiation step, each free radical can go through two different
propagation reactions:
1. Hydrogen abstraction
2. Beta (β) scission: The β scission refers to the
breaking of covalent bond in the β position relative
to the position of the unpaired electron.
The principal end result of the free radical chain reactions in
thermal cracking is to produce from long chain alkanes
shorter-chain alkanes, light olefins, and some aromatic
compounds. One important feature of free radical reactions
is that isomerization reactions, e.g., shifting of the unpaired
electron site from an edge atom of a molecule to the interior
atoms (as shown in Figure 6.1), are not favored reactions. In
other words, isomerization reactions take place at a slower
rate than other propagation reactions, e.g., β scission
reaction. The critical importance of this observation is that
the thermal cracking reactions produce shorter straight-
chain alkanes and olefins without any significant formation
of branched-chain (or iso-alkanes). This is the reason why
catalytic cracking processes have virtually replaced thermal
Thermal Processes
Thermal Management: Management of thermal reactivity is important in thermal cracking processes for
optimum conversion of the feeds with a wide boiling range.
A heavy gas oil feedstock with a wide boiling range
is fed to a fractionator to separate the feed into a
light oil and a heavy oil fraction depending on the
desired cut points. Light oil (which would have a
relatively low thermal reactivity) is heated in a
separate furnace to higher temperatures so that the
cracking takes place in a vapor phase. Heavy oil
fraction (with a high thermal reactivity) is heated to
a lower temperature for cracking in the liquid
phase. The heated feed streams are combined in a
soak drum to provide sufficient time for the
completion of the cracking reactions. After the
soaker, the products are sent to a flash separator to
separate the heavy end as a side product (fuel oil)
and the lighter products are sent to the fractionator
for separation into LGO, gasoline and the gaseous
products. Separating the feed into two fractions will
avoid heating the reactive longer alkane chains to
high temperatures to keep coke formation and gas
Thermal Processes-Visbreaking
Visbreaking: Visbreaking is a mild thermal cracking process applied to reduce the viscosity of VDR to
produce fuel oil and some light products to increase the distillate yield in a refinery. Depending on the
feedstock properties and thermal severity in the reactor, the process will typically achieve 10–25% of
conversion of the heavy ends to gas, gasoline, and distillates while producing fuel oil with the desired
specifications.
Thermal Processes-Visbreaking
Visbreaking: Depending on the process objectives and feedstock characteristics, reaction temperatures
range from 450°C to 485°C and pressures range from 3 to 10 bar. Higher temperatures and lower
residence times are used in the coil visbreaking process.
Thermal Processes-Coking
Coking: Coking is the most severe thermal process used in the refinery to treat the very bottom-of-the-
barrel of crude oil, i.e., vacuum residue. Because of the high severity of thermal cracking during
coking, the residue feed is completely converted to gas, light and medium distillates, and coke with
no production of residual oil.
Three different coking processes are used in the refineries:
1) Delayed coking,
2) fluid coking, and
3) flexi-coking (a variation of fluid coking)
The common objective of the three coking processes is to maximize the yield of distillate products in a
refinery by rejecting large quantities of carbon in the residue as solid coke, known as petroleum coke.
The bottoms from the fractionator, including the heavy ends of the
vacuum residue feed with heavy coker gas oil recycle, are mixed
with steam and sent to the tubular heater in the furnace to be
heated to approximately 475°C at a pressure of 10-30 psi. Steam is
added to prevent coking in the heater and the heated feed is
introduced from the bottom of one of the coke drums. The coking
takes place in the insulated coke drum as the drum fills up for a
period of 16–18 h. While drum A is being filled up, drum B is
decoked by using hydraulic cutters and the drilling stem and the
coke is removed from the bottom of the drum. All of the heat
necessary for coking is provided in the heater, whereas coking
Thermal Processes-Delayed Coking
Coking: The delayed coking operating variables:
• heater outlet temperature,
• pressure,
• recycle ratio, and
• cycle time.
These variables are selected based on feed properties such as the characterization factor, asphaltene
content, and Conradson Carbon Residue (CCR ) to ensure that coking in tubular heaters is minimized
and liquid product yield is maximized. The recycle ratio, which is typically 3–5%, is used to control the
endpoint of the coker heavy gas oil. The coke yield can vary from 20% to 30% depending on the feed
properties and coking conditions.
• The formation of shot coke is usually troublesome.
• Niche applications such as in titanium dioxide (TiO 2)
production
• Sponge coke is used as solid fuel, and manufacturing
anodes for aluminum production
• Needle coke is a specialty coke produced mostly from
coking of a highly aromatic FCC decant oil.
• Low coefficient of thermal expansion, a low puffing
(sudden volume expansion) tendency during graphitization
because of lower nitrogen and sulfur contents, and high
mechanical strength.
Thermal Processes-Fluid coking
Coking: Fluid coking and flexi-coking are fluid-bed processes developed from the basic principles of FCC, with close integration of
endothermic (cracking, coking, or gasification) and exothermic (coke burning) reactions. In fluid coking and flexi-coking processes,
part of the coke product is burned to provide the heat necessary for coking reactions to convert vacuum residua into gasses,
distillate liquids, and coke. Flexi-coking, as a variation of fluid coking, provides the options of partial or complete gasification of the
coke product to produce a fuel gas with some or no coke in the product slate. Different from the bulk liquid-phase coking in
delayed coking, coking takes place on the surface of circulating coke particles of coke heated by burning the surface layers of
accumulated coke in a separate burner. A schematic flow diagram of the fluid coking process. The preheated vacuum residue is
sprayed onto the hot coke particles heated in the burner by partial combustion of coke produced in the previous cycle. Using fluid
beds in the reactor and burner provides efficient heat transfer and fast coking on a collectively large surface area of the small coke
particles circulating between the reactor and burner. The products of coking are sent to a fractionator (similar to that used in
delayed coking after recovery of fine coke particles). Steam is also added at the bottom of the reactor (not shown in the figure) in a
scrubber to strip heavy liquids sticking to the surface of coke particles before they are sent to the burner. This steam also provides
fluidization of coke particles in the reactor. The reactor and the burner operate at temperatures of 510–570°C and 595–675°C,
respectively.
Thermal Processes-Flexi coking
Coking: A gasifier is added for conversion of some or all coke produced in the coker in reaction with air
and steam to produce a synthesis gas. The hot coke particles from the combustor are circulated back
to the coking reactor to provide the heat necessary for coking. The distillate products from the coker
are sent to the fractionator, as is done in the fluid coking process. On the gasifier outlet, after
removing the fine particles from the gas by cyclones, the gas is cooled in a direct-contact cooler to
condense the sour water and recover the flexi-gas. The product gas can be used as fuel gas in the
refinery. Depending on the demand, the flexi-coking process can produce both fluid coke and fuel gas,
or gasify all the coke to produce only fuel gas.
Higher temperatures and short residence times in the reactor lead to higher liquid and lower coke
yields compared with those of delayed coking.
Catalytic Cracking
Catalytic Cracking: As opposed to thermal cracking governed by free radicals, catalytic cracking
proceeds through the formation of ionic species on catalyst surfaces, and produces shorter, but
branched-chain (not straight-chain) alkanes by cracking the long straight-chain alkanes.
Catalytic Cracking: Proceeds via two ionic species: Carbocations are formed from hydrocarbons on two
acid sites:
Carbenium ion or
Carbonium Ion Bronsted acid sites
Lewis acid sites
Catalytic Cracking
Catalytic Cracking: High concentration of iso-alkane, aromatic product and no olefins larger then C 4
Why higher isomerization in cat cracking?
Why higher hydrocarbon product in cat cracking?
Catalytic Cracking
Other reactions during catalytic cracking include dehydrocyclization and dehydrogenation reactions to
produce aromatic compounds. One should note that thermal cracking reactions also take place during
catalytic cracking because of the sufficiently high temperatures used in the process.
Catalytic Cracking
Catalytic Cracking
Catalytic Cracking
FCC unit video
Catalytic Cracking
What is Octane
Number?
What is Cetane
number?
What is RON and MON?
Guidelines to determine
the order of RON and
MON?
Catalytic Hydrocracking
The principal objective of hydrocracking is to decrease the molecular weight and boiling point of
heavy oils to produce saturated hydrocarbons (diesel and jet fuel) from highly aromatic feedstocks
(e.g., LCO from FCC) and distillation residua.
The hydrocracking process has two dimensions:
• Hydrogenation of aromatic rings
• Cracking of aliphatic compounds
Catalytic Hydrocracking
The two different reaction systems in hydrocracking, hydrogenation and cracking, are supported by bi-
functional catalyst formulations.
Hydrocracking processes most commonly
include two reaction stages:
Hydrotreating to remove heteroatom (S,
N, O) species and Hydrocracking to
increase the H/C ratio of the
hydrocarbons in the feeds by
hydrogenation and to decrease their
molecular weight by cracking. In most
cases, the hydrotreating reactor (HT)
packed with cobalt-molybdenum
catalysts precedes the hydrocracking
(HC) reactor typically packed with nickel-
tungsten catalysts (for hydrogenation)
supported on alumina/silica (for
cracking).
Catalytic Hydrocracking
In a refinery, hydrocracking complements catalytic cracking by taking on the more aromatic
feedstocks that resist cracking, including the byproducts of FCC, such as light cycle oil (LCO).
Hydrocracking can also be used to upgrade residual fractions using different reactor configurations
and catalysts depending on the complexity of the upgrading tasks.
Catalytic Reforming
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 to satisfy the
increasing demand for hydrogen in hydrotreating and hydrocracking processes. Most reforming
catalysts contain platinum as the active metal supported on alumina, and some may contain
additional metals such as rhenium and tin in bi- or tri-metallic catalyst formulations.
Light naphtha from the naphtha fractionator, inherently a low-octane-number fraction, can be sent
directly to blending in gasoline pool after hydrotreating, if necessary, or sent to an isomerization
process to increase its octane number. The intended product from catalytic reforming is the high-
octane-number reformate and the most significant by-product is hydrogen gas.
Catalytic Reforming
Reactions of Interest
Product: High Octane
Feedstock: Heavy Naphtha
1. naphthenes → aromatics Gasoline
2. paraffins are isomerized Paraffins ⇒ 45-55%
Paraffins ⇒ 30-50%
3. aromatics are unchanged Naphthenes ⇒ 30-40%
Naphthenes ⇒ 5-10%
Aromatics ⇒ 5-10%
Aromatics ⇒ 45-60%
Catalysts Used
Platinum catalyst on metal oxide support
(platforming)
Pt/Al2O3
Bimetallic – Iridium or Rhenium
Pt-Re/Al2O3
Reactions Conditions
Low severity (relatively low octane) → low paraffin conversion
High severity → high paraffin conversion
Lean naphtha → high n-paraffinic content - difficult to process
Rich naphtha → low n-paraffinic (high naphthene) content - easy to process
Catalytic Reforming
The surfaces of metals (e.g., Pt) catalyze
dehydrogenation reactions, whereas the acid sites on the
support (e.g., alumina) catalyze isomerization and
cracking reactions. Metal and acid sites are involved in
the catalysis of hydrocracking reactions. Achieving the
principal objective of catalytic reforming—high yields
Research Octane Number [RON]: and high quality of reformate—can be achieved, to a
Reaction 1: from 75 to 110, Reaction 2: from 91 through 83 large extent, by controlling the activity of the catalysts
[cyclohexane] to 100, Reaction 3: from 0 to 110, and Reaction 4: and the balance between acidic and metallic sites to
Catalytic Reforming
Hydrocracking is an undesired side reaction in catalytic reforming because it consumes hydrogen
and decreases the reformate yield by producing gaseous hydrocarbons. Hydrocracking reactions are
exothermic, but they can still be kinetically favored at high temperatures, and favored, obviously, by
high hydrogen pressures. Below lists the heat of reactions for catalytic reforming reactions. Typically,
reformers operate at pressures from 50 to 350 psig (345–2415 kPa), a hydrogen/feed ratio of 3–8 mol
H2/mol feed, and liquid hourly space velocities of 1–3 h -1. These conditions are chosen to promote
the desired conversion reactions and inhibit hydrocracking while limiting coke deposition on the
catalyst surfaces.
Heats of Reactions:
Undesired Reactions in Catalytic Reforming paraffin to naphthene → 44 kJ/mol H2 - endothermic
Hydrocracking
n-C10+H2 → n-C6+n-C4 naphthenes to aromatics → 71 kJ/mol H -
2
endothermic
to inhibit this reaction, use
1.high T hydrocracking → -56 kJ/mol H2 - exothermic
2.high SV
3.Low H2 P
Catalytic reformers are normally run at low H 2 pressure to inhibit hydrocracking!
Reformer Catalyst video
Catalytic Reforming
Catalytic Reforming Processes Based on Catalyst Regeneration
1. Semi-regenerative (1949) – unit taken off-stream anywhere from every 3 to 24 months
2. Cyclic (1960) – involves swing reactor. Basically, operate 3 out of 4 and use extra reactor to take one
offline.
