IIT Delhi

Refinery and Technology

(Petroleum Refining Technology and Economics, by
James H. Gary, Glenn E. Handwerk, Mark J. Kaiser)

Prof. Abhijeet Raj

[email protected]
Dept. of Chemical Engineering, Block III-
3B-14
Indian Institute of Technology Delhi
Hauz Khas, Delhi
110016
Crude Oil
 Crude Oil: Occurrence and
Composition
 Occurrence -Earth’s crust, more homogeneous than coal mostly in sedimentary
rocks.
 Color – Light brown to dark brown or black
 Composition – Mostly hydrocarbons namely paraffins, naphthenes, and aromatics.
Main elements :
C (84%-86%)
H2 (11-14%)
O2, N2, S (rarely constitute 8%)
Metals Traces
 Crude Oil: Composition
Sulphur compounds: 0.05-10 wt%, but generally in the range 1-4 wt%. Crude with less
than 1 wt% sulphur – sweet.

Mercaptans (R-SH), sulfides and disulfides (R-S-R and R-S-S-R’), Thiophenes.

Oxygen compounds: Alcohols, ethers, carboxylic acids, anhydrides, carboxylic acid

esters, Ketones, Furans, Benzofuran.

Nitrogen compounds: pyridines (C2H5N), quinoline (C9H7N), isoquinoline (C9H7N),

pyrroles

Metallic compounds: Chlorides and sulphates of Na, K, Mg and Ca. Zn, Ti, Ca and Mg
appear in the form of organometallic soaps. Va, Ni, Cu and Fe are present as oil-soluble
compounds.
Crude Oil: Composition
 Crude Oil: Origin
Abiogenetic origin
 CaC2 + 2H2O  C2H2 + Ca(OH)2
Al4C3 + 12 H2O  3 CH4 + 4 Al(OH)3
Mendeleev and Berthelot explained that these carbides present in the earth’s crust are the
origin for petroleum.
 HC vapors present in cosmic clouds lead to precipitation of these clouds under favorable
conditions. HCs adsorbed and entrapped by earth’s crust
Biogenetic origin: Biomass from dead organisms were buried in a sedimentary basin and
subjected to diagenesis through prolonged exposure to microbial decay followed by increasing
temperatures and pressures that led to oil and gas formation. (Demaison and Moore 1980)
Crude Oil: Occurrence and
Composition
 Oil Refinery
Goal of Oil Refining
 Production of fuels for transportation, power generation, and heating purposes

 Production of specialty chemicals such as solvents and lube oils

 Production of intermediates (for chemical industry)

Complex Architecture (Physical and
Chemical)
 Varying properties of the crude oil delivered

 Requirements of the market

 Environmental considerations (Changing regulation)

 Oil Refinery
Chemical processes
Physical processes
Thermal Catalytic
Desalting Vis-breaking Hydrotreating
Dehydration Delayed Coking Catalytic reforming
Distillation Flexi-coking Catalytic Cracking
Solvent extraction Hydrocracking
Solvent de-asphalting Catalytic dewaxing
Solvent dewaxing Alkylation
Blending Polymerization
Isomerization
 Desalting and Dehydration
Crude: Water, Inorganic Salts, Suspended solids, water soluble trace metals
Impact on System: Corrosion, Plugging, Fouling of equipment, Poisoning of catalysts
Process: Mixing with heated water and surfactant to dissolve salts like NaCl, CaCl , MgCl and
2 2
followed by phase separation using electric field. Sometimes, NaOH is also added oil to convert CaCl2,
MgCl2 in oil to NaCl since at high temperatures, CaCl2, MgCl2 can react with H2O to form HCl and
corrode equipment. NaCl doesn’t undergo hydrolysis easily.
Process flow diagram for single stage
desalter
 Desalting and Dehydration
Electrical desalting: Water-crude interface level in the separators should be kept constant; any changes will
upset the electrical field and influence electrical coalescence of water drops, hence poor performance may
lead to waste products of crude oil; be carried away with separated water.

Desalting temperature: Temperature affects water droplet settling through its effect on oil physical properties,
in particular oil viscosity. Heavier crude oils require higher desalting temperatures in order to keep products on
specification and to minimize waste products.

Wash water ratio: Heavy crudes require a high wash water ratio to increase electrical coalescence otherwise,
residual products will be formed, containing higher salt ratio.

Pressure drop across the mixing valve: A high-pressure-drop operation results in a good mixing between wash
water and the emulsion leading to a decrease in the salt content in the bulk of the oil phase. On the other
hand, if the pressure drop is excessive, the formed emulsion may get very tight and hard to break. The
optimum pressure drop is estimated to be about 1.5 bar for light crudes and 0.5 bar for heavy crudes.

Types of de-emulsifiers: De-emulsifiers are added to aid in complete electrostatic coalescence and settling of
emulsified oil drops, hence and oil desalting. These de-emulsifiers are important to use, especially when heavy
crudes are processed. Recommended doses to use range between 3 and 10 ppm of the crude oil.
 Crude Distillation
Central Theme: central separation step in every refinery is the distillation of crude, which separates the various
fractions according to their Volatility.
Two Units:
1) Atmospheric DU
2) Vacuum DU

Operating Details:
3) Crude heating (700-750
F)
4) All distillate and 10-20%
of bottom evaporate.
5) Introduced in Flash region
Crude Distillation
A temperature gradient is established in the column
by removing heat from the overhead vapor. The
column condenses the naphtha fraction and sends a
portion of the liquid naphtha, as reflux, to the
column to achieve a good separation of the distillate
products drawn from the side of the distillation
column, such as kerosene, LGO, and HGO. Steam
strippers on the side of the column also provide
reflux to the main column to help with clean
separation of the distillate products. Additional reflux
is provided to the main column by pump around
loops associated with heat exchangers for
preheating the crude. Counter-current flow of vapor
and liquid streams through the contact stages (e.g.,
trays) in the main column, enabling good separation
of the distillate fractions. The temperature at the
bottom of CDU is limited to 700-750° F to prevent
cracking – breaking of the chemical bonds between
carbon atoms in the aliphatic hydrocarbons
constituting the crude oil. Cracking would cause
coking (accumulation of carbonaceous solids) on the
metal surfaces in the column and interferes with
fractionation in distillation. Vacuum distillation is
necessary to fractionate the heavy distillates
Crude Distillation
The atmospheric residue is reheated in a fired
furnace to 730-850° F before introduction into
the vacuum distillation unit (VDU). Furnace
outlet temperature is selected depending on
the thermal reactivity (or coking propensity of
crude oil, as will be discussed further) and the
desired level of separation in the column.
Steam ejectors, or, more recently, vacuum
pumps, are used to create vacuum for
evaporation of the light vacuum gas oil and
heavy vacuum gas oil fractions. The
temperature and pressure in VDU also depend
on whether steam is introduced, or the
separation is carried out without the steam
addition in “dry” towers, varying between 10
to 30 mmHg at the bottom of the tower. Lower
pressures and higher temperatures are used in
dry towers. To minimize the pressure
difference between the bottom and top of the
column, some special packing materials are
used instead of trays for providing contact
 Crude Distillation
To be on the safe side, the temperature in the
column should be lower than the lower
temperature line of the band. Crudes with high Kw
(paraffinic) should be heated to lower
temperatures in the column than crudes with lower
Kw (less paraffinic). Hydrocarbon composition is
closely related to thermal reactivity, since paraffins
could be more readily cracked than naphthenes,
whereas aromatic compounds are the most stable
hydrocarbons.

Type of distillation
1. True Boiling Point Distillation (TBP)

2. ASTM Distillation (ASTM)

3. Equilibrium Flash Vaporization (EFV)

Crude Distillation

1) TBP distillation is used to characterize crude oils

and constitute a significant component of crude
essay.
2) ASTM methods are usually used for refinery
products and property calculations and
correlations for distillate fractions.
3) EFV provides useful data for flashing operations
in the refinery.
4) ASTM D86 (atmospheric distillation) and ASTM
D1160 (vacuum distillation) are used for low-
boiling, and high-boiling fractions, respectively.
 Crude Distillation
Cut Points: Using a crude TBP curve, cut points are defined as the temperatures that represent the
limits of a distillate fraction. For example, for kerosene, fraction Ta represents the lower cut point, and
Tb represents the upper cut point.

Distillate Product Boiling Range

Butanes and Lighter
Light SR Naphtha 90 - 190o F (32-88o C)
Heavy Naphtha 190 - 380o F (88 - 193o C)
Kerosene 380 - 520o F (193 -
271o C)
Light Gas Oil 520 - 610o F (271 -
321o C)
Heavy Gas Oil 610 - 800o F (321 -
425o C)
Light Vacuum Gas Oil 800 - 950o F (425 -
510o C)
Heavy Vacuum Gas Oil 950 - 1050o F (510 -
 Crude Distillation
Quality of separation: The quality of separation in fractional distillation can be calculated using the
designated cut points (at 5%vol and 95%vol) for the two adjacent fractions, termed as light and heavy.
The difference in temperature (ΔT) between 5% vol temperature of the heavy fraction and
95%vol temperature of the light fraction is used to define the quality of separation. A positive value of
ΔT (termed ASTM gap) indicates good separation, while a negative value of ΔT (termed ASTM overlap)
points to a bad separation.

The relationship between the ASTM distillation temperatures at 95% vol and 5% vol of two
adjacent fractions, light and heavy, respectively.

ASTM

5% vol T (heavy fraction) - 95% vol T (light fraction) = ∆T

(LGO) (kerosene)

if ∆T >0, called ASTM gap (good separation)

if ∆T<0, called ASTM overlap (bad separation)
 Solvent de-asphalting
Solvent De-asphalting: The coke-forming tendency of heavier distillation products can be reduced by removal
of asphaltenes' materials (large aromatic compound) by use of solvent extraction. Liquid propane is typically
used; but butane and pentane are also used.

Propane deashphalting is based on the solubility of hydrocarbons in propane (type of molecule not weight).

1. Produce asphalt - as final product.

2. Remove asphaltenes to prevent coke, or metal buildup on catalyst in further processing
of DAO.
rength of Non-polar solvent

1 =

√
𝑉
∆ 𝐻 − 𝑅𝑇
2
𝛿2=
𝑉  Aromatic solvents have higher solvent power than aliphatic
hydrocarbons, and
 Solvent power of paraffins decreases with the decreasing carbon
 Solvent de-asphalting

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. One
should point out here that the molecular composition of the asphaltenes would vary significantly along with the yield of asphaltenes.
As the yield of asphaltenes increases with the increasing S/R, lower molecular weight asphaltenes would be progressively included
in the separated asphaltenes.
 Dewaxing
Dewaxing: 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).
Volatility – should be low to keep oil in the
liquid phase during engine operation.

Viscosity– important to control because of

lubrication and heat transfer
considerations. Moderate viscosities are
desired.

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.
Solvent dewaxing - physical process; separation of wax by
Thermal Stability – High thermal stability
freezing and solvent
(or small degree of thermal degradation at
Catalytic dewaxing - chemical process; removal of wax by
high temperatures) is necessary to
selective reaction of long chain n-alkanes (wax).
minimize viscosity loss and coke
 Dewaxing
Dewaxing: 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.

Principal solvents in solvent dewaxing units:

Methyl ethyl ketone (MEK)
Propane.

Advantages of using propane as a solvent:

 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
The lowest temperature used in the refrigeration cascade depends on the desired pour point of the
lube oils base stock product