FEDERAL UNIVERSITY OF PETROLEUM RESOURCES, EFFURUN

DEPARTMENT OF PETROLEUM ENGINEERING

B.ENG. (CHEMICAL ENGINEERING)

LECTURE NOTES

FOR

UNIT PROCESSES IN PETROLEUM REFINING (CHE 417)

MODULE II
,

2.0 STANDARD TEST METHODS

Standard Tests are conducted on petroleum crude oils with a view to evaluate its quality
and suitability for the production of certain types of products. The Tests include oAPI
Gravity, Sulphur content (wt. %), Pour point ( oF or oC), Carbon residue and Salt content.
Others are Nitrogen content and distillation range of petroleum crude oil.

Petroleum Crude Distillation Curves

Standard distillation and processing data are required to determine the most desirable
processing sequence to obtain the required products. In such instances the true boiling
point (TBP) and gravity-mid percent curves are developed using U.S. Bureau of Mines
crude oil petroleum analysis data sheets.

TBP Assay
TBP Assay is normally conducted to generate distillation data and to study the
variations of some key properties throughout the distillation range. Refiners use TBP to
determine the most desirable processing sequence to obtain products from crude oil.
3.0 CRUDE DISTILLATION

Petroleum crude oils are refined in distillation columns (stills), which are the major
processing units in refineries. Crude stills are used to separate crude oils by distillation
into fractions based on boiling points. The fractions so produced serve as feedstocks to
processing units downstream.

Higher efficiencies and lower costs are achieved by conducting distillation in two steps,
namely, Atmospheric and Vacuum Distillation Stills. Thus, the fresh crude is first
fractionated in atmospheric still and the high-boiling bottom fraction (residue) is routed
to the vacuum still for further fractionation. Fractionation in a vacuum still is important to
prevent:

 Loss to dry gas

 Discolouration of products
 Fouling of equipment due to coke formation.

3.1 Preliminary Treatment and Heating of Crude Oil

Crude oil comes from sub-surface reservoirs and is mixed with variety of substances
like gases, water, minerals etc. Impurities in crude oil are either oleophobic or oleophilic.
Oleophobic impurities include salt (mainly chlorides of Na, K, Ca and Mg), sediments
such as salt, sand, mud, iron oxide, iron sulphide, etc., and water, present as soluble
emulsified and / or finely dispersed water. Oleophilic impurities are soluble in crude oil;
they include S-, N- and O-containing compounds as well as organo-metallic
compounds, Ni, V, Fe and As, and naphthenic acids. Pre-treatment of crude oil removes
oleophobic impurities.

Pre-treatment of crude oil ensures that it is effectively transported, its processing does
not give rise to fouling and corrosion in subsequent operations (distillation, catalytic
reforming and secondary conversion processes). Petroleum crude oils are normally
subjected to preliminary treatment before fractionation in Atmospheric and Vacuum
Distillation Stills. The preliminary treatment are Field separation and Desalting.

Field separation

Field separation involves the removal of gases, water and dirt entrained in the crude
from the reservoirs and is located near the oil wells. The operation involves gravity
separation of three phases, namely, gases, crude oil and water.

Desalting

Crude desalting is a water-washing operation performed at the refinery and it involves

the removal of water-soluble minerals and entrained solids (impurities). There are two
types of desalting: Single- and Multi-stage Desalting.

Commercial crudes contain salt in the range of 10-200 ppb; refiners now aim at
achieving 5 ppb or less (1-2 ppb). This is not possible with single-stage desalting,
hence, two-stage desalting is used for effectiveness.

Desalting process consists of three main stages, namely, heating, mixing and settling. It
involves emulsifying the crude followed by the separation of water containing salt. The
resulting two phases (water/oil) are separated either by using chemicals to break down
the emulsion or by passing high potential electric current.

Another importance of the desalting process is the removal of suspended solids from
the crude oil.

In the desalting process oil and water phases are separated in a settling vessel either
by adding chemicals to break the emulsion or developing a high potential electrical field
across the vessel to coalesce the droplets of salty water more rapidly. Either AC or DC
currents may be used and potentials of 12,000 – 35,000 volts are used to promote
coalescence. Single-stage desalting units Have efficiencies of 90-95 %, while 2-stage
units achieve 99 % and above.

Distillation of petroleum crude oil involves the following processes:

 Crude receiving, crude filtration, crude pre-heating before desalting, desalting,

crude pre-heating, raising temperatures with direct-fired heaters (pipe-still);
 Atmospheric and Vacuum Distillation;
 Product routing.

Product streams are gaseous hydrocarbons, fuel gases, LPG, light gasoline, naphtha,
kerosene, diesel, heavy oil, bitumen, wax, lubricating oil.

3.2 Atmospheric Distillation Column (ADC)

Fractionation of desalted crude oil is carried out in the Atmospheric Still at 340-350 oC to
produce gases, LPG, gasoline, naphtha, kerosene, diesel and atmospheric residue (fuel
oil). The desalted crude is pre-heated in a series of heat exchangers and furnace to
raise temperature to about 400oC and routed to ADC, where the crude is fractionated
into different low boiling components.

ADC normally contains 30-50 fractionation trays. Separation of the complex mixtures in
crude oils is relatively easy and generally 5-8 trays are needed for each side stream
product. The same number of trays are above and below the feed plate. Thus, an ADC
with four liquid side-stream draw-offs will need from 30-42 trays.

Reflux is used in ADC and it is achieved by condensing the tower overhead vapours
and returning a portion of the liquid to the top of the tower using pump-around and
pump-back streams lower in the tower. Efficiency in energy usage in ADC is improved
by using pump-around reflux.

ADC Process Conditions

Parameters Top Flash

Temperature, oC 117-123 351-357
Pressure, kg/cm2 2.2-2.5 2.5-2.9
3.3 Vacuum Distillation Column (VDC)

Distillation of the residue from ADC is carried out to make it suitable for catalytic
cracking, hydrocracking or production of lubricating oils and a residue, which may be air
blown or further distilled for bitumen. The furnace outlet temperatures required for
atmospheric distillation of heavier fractions of crude oil are so high that thermal cracking
would occur, with resultant loss of product and equipment fouling. To avoid this
undesirable occurrence distillation of heavy residue from ADC is carried out under
vacuum. Secondly, the residue is distilled under vacuum because the boiling
temperature decreases with a lowering of the pressure. Distillation in VDC is carried out
with absolute pressures in tower flash zone of 25-40 mmHg. To improve vaporization,
the effective pressure is lowered even further to 10 mmHg or less by the addition of
steam to the furnace inlet and at the bottom of the vacuum tower. The latter step will
increase the furnace tube velocity and minimize coke formation, as well as decrease the
total hydrocarbon partial pressure in VDC.

VDC Process Conditions

Parameters Top Flash

Temperature, oC 70-80 390-395
Pressure, mmHg 70-90 130-150

4.0 OTHER REFINING PROCESSES

Other important refining processes are Hydro-treating, Isomerization, Catalytic

Reforming, Fluid Catalytic Cracking, Hydrocracking, Alkylation, Hydrogenation etc.

4.1 HYDRO-TREATING

Hydro-treating is a process in which petroleum products are catalytically stabilized and

objectionable elements such as sulphur, nitrogen, oxygen, halides and trace metals are
removed by reacting them with hydrogen. Stabilization usually involves the conversion
of unsaturated hydrocarbons (olefins and gum-forming di-olefins) to paraffins. Hydro-
treating is used applied to a wide-ranging feed-stocks, from naphtha to reduced crude.
When the process is used to specifically remove sulphur it is called
hydrodesulphurization (HDS); hydro-denitrogenation when the process is used to
remove nitrogen, and hydro-deoxygenation when used to remove oxygen-containing
hydrocarbons. Furthermore, aromatics content may also be reduced by hydrogenation
through conversion to paraffins to meet environmental limits.
The product to be hydrotreated is mixed with hydrogen-rich gas either before or after it
is preheated to the proper reactor inlet temperatue. Hydrotreating reactions are
generally out at temperatures below 800 oF (427oC) to minimize cracking, and the feed is
usually heated to 500-800oF (260-427oC).

The oil feed combined with the hydrogen-rich gas enters the top of the Fixed-bed
reactor. In the presence of the metal-oxide catalyst hydrogen reacts with the oil to
produce H2S, NH3, saturated hydrocarbons, and free metals. The metals remain on the
surface of the catalyst, while the other products leave the reactor with the oil-hydrogen
stream. The reactor effluent stream is cooled before separation of the oil from the
hydrogen-rich gas. The oil product is stripped of any remaining H 2S and light ends in a
stripper. The gas may be treated to remove H 2S and recycled to the reactor.

Hydrotreating Catalysts

Catalysts generally used for hydrotreating include cobalt and molybdenum oxides on
alumina. Others are nickel oxide, nickel thiomolybdate, tungsten H 2S and nickel
sulphides, and vanadium oxide. The cobalt and molybdenum oxides on alumina
catalysts are most generally use today because they are highly selective, easy to
regenerate, and resistant to poisons. In processes where the removal of nitrogen is a
significant consideration catalysts composed of nickel-cobalt-molybdenum or nickel-
molybdenum oxides on alumina are more efficient. Nitrogen is usually more difficult to
remove from hydrocarbon streams than sulphur, hence any treatment which reduces
excess nitrogen concentration to a satisfactory level will effectively remove excess
sulphur. Cobalt-molybdenum catalysts are selective for sulphur removal, while nickel-
molybdenum catalysts are selective for nitrogen removal, although both catalysts will
remove sulphur and nitrogen. Furthermore, nickel-molybdenum catalysts have higher
hydrogenation activity than cobalt-molybdenum catalysts, which results under the same
operation conditions, in a greater saturation of aromatic rings. In other words where
nitrogen removal and or saturation of aromatic ring is desired nickel-molybdenum
catalyst is preferred.

Hydrotreating Reactions

Desulphurization

Mercaptans: RSH + H2 RH + H2S

Sulphides: R2S + 2H2 2RH + H2S
Disulphides: (RS)2 + 3H2 2RH + 2H2S
Thiophenes: C4H4S + 4H2 C4H10 + H2S
Denitrogenation

Pyrrole: C4H4NH + 4H2 C4H10 + NH3

Pyridine: C5H5N + 5H2 C5H12 + NH3

De-oxidation

Phenol: C6H5OH + H2 C6H6 + H2O

Peroxides: C7H13OOH + 3H2 C7H16 + 2H2O

De-halogenation

Chlorides: RCl + H2 RH + HCl

Hydrogenation:
Pentene: C5H10 + H2 C5H12

Hydrocracking: C10H22 + H2 C4H10 + C6H14

Figure 4.1.1 Hydro-desulphurizer

4.2 CATALYTIC REFORMING AND ISOMERIZATION

In catalytic reforming the hydrocarbon molecular structures of the stock are rearranged
to form higher-octane aromatics with only a minor amount of cracking. Thus, catalytic
reforming primarily increases the octane of motor gasoline rather than increasing its
yield.

Typical feedstocks to catalytic reformers are heavy straight-run (HSR) gasolines and
naphthas: 180-375oF (82-190oC), and heavy hydrocracker naphthas. They are
composed of four major hydrocarbon groups, namely, paraffins, olefins, naphthenes
and aromatics (PONA).

Component Feed Product

Paraffins 30-70 30-50
Olefins 0-2 0-2
Naphthenes 20-60 0-3
Aromatics 7-20 45-60

Paraffins and naphthenes undergo two types of reactions, namely, cyclization and
isomerization, to higher octane products. The ease and probability of either reaction
occurring increases with the number of carbon atoms in the molecule. As a result, only
HSR gasoline is used as feed for catalytic reformer. Light straight-run (LSR) gasoline is
on the other hand, not a good feed for catalytic reforming because it is largely
composed of lower molecular weight paraffins that tend to crack to butane and lighter
fractions.

In complex reaction systems, certain reactions may lead to desirable products, while
other reactions may give rise to undesirable products. In catalytic reforming desirable
reactions lead to the formation of aromatics and iso-paraffins as follows:

1. Paraffins are isomerized and to some extent converted to naphthenes; the

naphthenes are subsequently converted to aromatics.

2. Olefins are saturated to form paraffins, which then react as in (1).

3. Naphthenes are converted to aromatics.
4. Aromatics are left essentially unchanged.

Undesirable reactions in catalytic reforming include:

1. Dealkylation of side chains on naphthenes and aromatics to form butane and

lighter paraffins.
2. Cracking of paraffins and naphthenes to form butane and lighter paraffins.
Four major reactions that take place in catalytic reforming are: Dehydrogenation of
naphthenes to aromatics; Dehydrocyclization of paraffins to aromatics; Isomerization;
Hydrocracking.

Dehydrogenation Reactions

The dehydrogenation reactions are highly endothermic, thus causing a decrease in

temperature as the reaction progresses. Secondly, dehydrogenation reactions have the
highest rates among reforming reactions, which necessitates the use of inter-heaters
between catalyst beds to keep the mixture at sufficiently high temperatures for the
reactions to proceed at practical rates. The major dehydrogenation reactions are:

 Dehydrogenation of alkylcyclohexanes to aromatics:

Methylcyclohexane Toluene (Methyibenzene) + 3H 2

 Dehydroisomerization of alkylcyclopentanes to aromatics:

Methylcyclopentane Cyclohexane Benzene + 3H 2

 Dehydrocyclization of paraffins to aromatics

n-Heptane Toluene + 4H2

The dehydrogenation of cyclohexane derivatives is a much faster reaction than either

dehydroisomerization of alkylcyclopentanes or dehydrocyclization of paraffins. However,
the three reactions take place simultaneously and are important to obtain the aromatic
concentration needed in the reformate product to give the needed octane improvement.
The yield of aromatics in the dehydrogenation reactions is increased by:

 High temp (which increases rate of reaction, but adversely affects equilibrium)
 Low pressure; it shifts chemical equilibrium to “the right”
 Low space velocity (promotes approach to equilibrium)
 Low H2/hydrocarbon mole ratio; it shifts chemical equilibrium to the right. Also
sufficient H2 partial pressure must be maintained to avoid excessive coke
formation.

Isomerization Reactions

Isomerization of paraffins and cyclopentanes usually results in a lower octane product

than does conversion to aromatics. However, the octane number of the isomerized
product is higher than for un-isomerized. Examples of isomerization reactions are:

 Isomerization of normal paraffins to isoparaffins:

 n-hexane iso-hexane

 Isomerization of alkylcyclopentanes to cyclohexanes, plus subsequent

conversion to benzene:
Methylcyclopentane cyclohexane benzene
91 RON 83 RON > 100 RON

Isomerization yield is increased by:

 High temperature; it increases rate of reaction

 Low space velocity
 Low pressure

Hydrocracking Reactions

Hydrocracking reactions are exothermic and result in the production of lighter liquid and
gas products. They are relatively slow reactions and therefore most of the
hydrocracking occurs in the last section of the reactor. Most hydrocracking reactions
involve the cracking and saturation of paraffins.

C10H22 + H2 iso-hexane + n-butane

The concentration of paraffins in the charge stock determines the extent of the
hydrocracking.

Catalytic Reforming Process Units

Reforming processes are classified as continuous, cyclic, or semi-regenerative

depending on the frequency of catalyst regeneration. Figure 4.2.1 shows the semi-
regenerative type Reforming Process Unit.
Figure 4.2.1 Catalytic Reforming Semi-regenerative Process

Continuous Unit

The continuous unit is designed to permit the removal and replacement of catalyst
during normal operation. As a result, the catalyst can be regenerated continuously and
maintained at a high activity. In continuous unit increased coke deposition and
thermodynamic equilibrium yields of reformate are both favoured by low pressure
operation. Thus, the ability to maintain high catalyst activities and selectivity by
continuous regeneration is the major advantage of the continuous unit. The major
demerit is the higher capital costs.

Semi-regenerative Unit

The semi-regenerative unit has the advantage of minimum capital costs, short
regeneration interval (3 to 24 months). Regeneration requires the unit to be taken off-
stream. High H2 recycle rates and operating pressures are utilized to minimize coke
deposition and eventual loss of catalyst activity.

Cyclic Unit

The cyclic unit is characterized by two reactors (the swing reactor and on-stream unit);
this design allows for catalyst regeneration in the on-stream reactor without shutting
down the process unit. When catalyst activity in on-stream reactor drops below desired
level it is isolated and replaced with the swing reactor. Subsequently, the catalyst in it is
regenerated by using hot air to burn off the coke deposits to prepare it for reuse later.
The major drawback of the cyclic unit is that regeneration is conducted on a 24- or 48-
hour cycle and another reactor is used to continue the processing. As a result cyclic
processes are more expensive, but they offer the advantages of low pressure operation
and higher yields of reformate at the same severity.

Reforming Catalysts

Catalysts normally used for reforming reactions are Pt/Al 2O3 base, Pt/Re/Al2O3 base.
Pt/Re/Al2O3 base is a more stable catalyst, which permits operation at lower pressures.
Pt is believed to serve as a catalytic site for hydrogenation and dehydrogenation
reactions, while chlorinated alumina provides an acid site for isomerization, cyclization
and hydrocracking reactions.

Reforming Reactors

Semi-regenerative and cyclic catalytic process units are fixed bed reactors.

4.2.2 Isomerization

Isomerization can improve the octane numbers of the light-straight run (LSR) naphtha
by converting normal paraffins to corresponding isomers. For instance, n-pentane (with
unleaded RON of 61.7 can be converted to iso-pentane (92.3 RON). In isomerization
reactions, temperatures of 200-400 oF (95-205oC) are preferred to higher temperatures
because equilibrium conversion to isomers is enhanced at low temperatures.

4.3 FLUID CATALYTIC CRACKING

Fluid catalytic cracking (FCC) is the most important and widely used refining process for
converting heavy oils into more valuable gasoline and lighter products, with about 10.6
MMBPD (over 1 million tons per day) produced globally. FCC is preferred over Thermal
cracking because it results in more gasoline having a higher octane and less heavy fuel
oils and lighter gases than the latter. In addition, the light gases produced by FCC
contain more olefins than Thermal Cracking.

The FCC is designed based on fluidized-bed catalytic reactor and there two basic types
in use today, namely, the “side-by-side” type (the reactor and regenerator are separate
vessels adjacent to each other) or “stacked” type (the reactor is mounted on top of the
regenerator).

4.3.1 Catalytic Cracking Reactions

Catalytic cracking reactions normally involved primary and secondary reactions. The
primary reactions involve the initial carbon-carbon bond scission and the immediate
neutralization of the carbonium ion. The primary reactions are:

Paraffins Paraffin + Olefin

Alkyl Naphthene Naphthene + Olefin

Alkyl Aromatic Aromatic + Olefin

Mechanism of the Catalyst Cracking

Catalytic cracking reactions of n-octane (n-C8H18) are shown below:

Step 1: Mild thermal cracking initiation reaction.

nC8H18 CH4 + R-CH=CH2 R = CH3CH2CH2CH2CH2-

Step 2: Proton shift

R-CH=CH2 + H2O + AlO3-Si R-C+H-CH3 + [HO-Al-O-Si]-

Step 3: Beta scission

R-C+H-CH3 CH3CH2=CH2 + C+H2CH2CH2CH3

Step 4: Rearrangement of carbonium ion toward more stable structure

Order of carbonium ion stability: tertiary > secondary > primary

C+H2CH2CH2CH3 CH3CH+CH2CH3 CH3C(CH3)HC+H2 CH3C+(CH3)-CH3

Step 5: Hydrogen ion transfer

CH3C+(CH3)-CH3 + nC8H18 i-C4H10 + CH3C+HCH2R

Thus, another large carbonium ion is formed for repeat of chain reaction.

Catalytic Cracking of Paraffins

Catalytic cracking of paraffins is characterized by high production of C 3 and C4

hydrocarbons in the cracked gases, reaction rates and products determined by size and
structure of paraffins, and isomerization to branched structures and aromatic
hydrocarbons formation resulting from secondary reactions involving olefins. The effect
of the catalyst on reaction rates is more pronounced as the number of carbon atoms in
the molecule increases; the effect is significant for C 6 and above carbon atoms.
Furthermore, the cracking rate is also influenced by the structure of the molecule, such
that molecules tend to neutralize each other on a one-to-one basis. For e.g. 2,2,4-
trimethylpentane (one tertiary and quaternary) cracks slightly faster than n-octane, while
2,2,4,6,6-pentamethylheptane (one tertiary and two quaternary) cracks at a slower rate
than does n-dodecane.

Catalytic Cracking of Olefins

Rates of catalytic cracking of olefinic hydrocarbons are much higher than those of
corresponding paraffins. The main reactions are:

 Carbon-carbon bond scissions

 Isomerization
 Polymerization
 Saturation, aromatization, and carbon formation.

Olefin isomerization followed by saturation and aromatization are responsible for the
high octane number and lead susceptibility of catalytically cracked gasolines. The
higher rate of hydrogen transfer reactions for branched olefins results in ratios of iso- to
normal paraffins higher than the equilibrium ratios of the parent olefins. In addition,
naphthenes act as hydrogen donors in transfer reactions with olefins to yield
isoparaffins and aromatics.

Catalytic Cracking of Naphthenes

The most important cracking reaction of naphthenes in the presence of a catalyst (silica-
alumina) is dehydrogenation to aromatics. There is also C-C scission in both the ring
and attached side chains, but at temperatures below 1000 oF (540oC) the
dehydrogenation reaction is significantly higher. Dehydrogenation is very extensive for
C9 and larger naphthenes resulting in high octane gasoline. The non-ring liquid products
and cracked gases resulting from naphthenic hydrocarbon cracking are more saturated
than those from catalytic cracking of paraffins.

Catalytic Cracking of Aromatics

Aromatic hydrocarbons with alkyl groups containing less than three carbon atoms are
not very reactive. The predominant reaction for aromatics with long alkyl chains is the
clean splitting off of side chains without breaking the ring. The C-C bond adjacent to the
ring is ruptured, and benzene compounds containing alkyl groups can be cracked.

4.3.2 Cracking Catalysts

Commercial cracking catalyst are of three types, namely:

 Acid-treated natural aluminosilicates

 Amorphous synthetic silica-alumina combinations
 Crystalline synthetic silica-alumina catalysts (zeolites or molecular sieves).

Most catalysts used in commercial units today are either zeolites or a mixture of zeolites
and amorphous synthetic silica-alumina.

The merits of zeolite catalysts over the natural and amorphous synthetic silica-alumina
are:

 Higher activity
 Higher gasoline yields at a given conversion
 Production of gasolines containing a larger percentage of paraffinic and aromatic
hydrocarbons.
 Lower coke yield (and therefore usually a larger throughput at a given conversion
level.
 Increased Isobutane production.
 Ability to go to higher conversions per pass without over cracking.

The high activity of zeolite catalysts in cracking permits short residence and has
resulted in most cracking units being adapted to riser cracking operations. In the latter
case the adverse effects of carbon deposits on catalytic activity and selectivity are
minimized because of the negligible amount of catalyst back mixing. In addition,
separate risers can be used for cracking the recycle stream and the fresh feed so that
each can be cracked at their own optimum conditions.

Basic nitrogen compounds, Fe, Ni, V, and Cu in crude oil act as poisons to cracking
catalysts. The nitrogen reacts with the acid centers on the catalyst and lowers the
catalyst activity. The metals deposit and accumulate on the catalyst and cause a
reduction in throughput by increasing coke formation and decreasing the amount of
coke burn-off per unit of air by catalysing coke combustion to CO 2 rather than to CO.
Apart from reducing catalyst activity Ni and V also promote very significantly the
formation of gas and coke as well as reduce gasoline yield at a given conversion level.
Figure 4.3.1 Fluid Catalytic Cracking Unit

Figure 4.3.2a,b Fluid Catalytic Cracking Units