Petrochemical &

Petroleum Refining Technology

The Refining Process
(Conversion : Unification)
 THE REFINING PROCESS
Change the size and/or structure of hydrocarbon
molecules

1. Decomposition (dividing)
- thermal & catalytic cracking

2. Unification (combining)
- alkylation & polymerization

3. Alteration (rearranging)
- isomerization & catalytic reforming
 THE REFINING PROCESS
UNIFICATION

Processes to make gasoline components from

materials that are too light to otherwise be in
gasoline
• Alkylation
• Polymerization
Cracking + Polymerization + Alkylation = Gasoline yield representing 70
percent of the starting crude oil.
Alkylation

In alkylation small molecules produced from other

processes are recombined in the presence of a catalyst.

• Chief sources of olefins are

catalytic cracking and coking
operations
• Most common olefins used:
butene and propene,
sometimes pentene included

The product can be made to fall within the

gasoline boiling range with MON from 88-94
& RON from 94-99
Alkylation

Combination of low molecular weight olefins

(propylene and butylene) with an isoparaffin
(isobutane) in the presence of a catalyst (sulfuric
acid or hydrofluoric acid) to form higher molecular
weight isoparaffins.
Isoparaffin Olefins HF /H2SO4 Isoparaffins
(Isobutane) (Propylene/Butylene) (ALKYLATE)

By products:
1. Polypropylene (polymerization
of propylene) – lower product
octane & increase acid
consumption
2. Ester (reaction with H2SO4 ) –
very corrosive, require
treatment

ALKYLATE
Excellent blending
MON 90-95 component for gasoline
RON 93-98
 Alkylation Reaction
• Isobutane is normally used in Alkylation process…WHY?

Isobutane has a sufficiently high octane number and low

vapor pressure to allow it to be effectively blended directly
into finished gasoline.
• Process using sulfuric acid as a catalyst is much more
sensitive to T than hydrofluoric acid process.
• With Sulfuric Acid it is necessary to carry out the reactions
at 40-70oF (5-21oC) or lower
 minimize oxidation reduction reactions…
• Hence, will result in the formation of tars, sulfur dioxide,
ester
• When anhydrous hydrofluoric acid is the catalyst, the
temperature usually limited to 100oF (38oC) or below.

• The volume of acid employed is about equal to that of the

liquid HC charge & sufficient P is maintained on the system to
keep the HC & acid in the liquid state.

• High isoparaffin/olefin ratios (4:1 to 15:1) are used to :

 minimize side reaction polymerization (reduce by product)
 to increase product octane number.

• Efficient agitation:
 to promote contact between the acid and HC phases is
 to obtain high product quality & yields.
• The yield, volatility & octane no. of the product is regulated
by adjusting the temperature, acid/HC ratio &
isoparaffin/olefin ratio.

• In practice however, the plants are operated at different

conditions & the products will be different

• Important variables in alkylation unit:

 Reaction temperature
 Acid strength & Composition
 Isobutane concentration
 Olefin type (ratio of butylene/propylene)
 Olefin space velocity
 Alkylation Reaction

Reaction of isobutane with an olefin to form a high

molecular weight isoparaffin  Alkylate

The olefin used is butylene and propylene, which

combines with isobutane to yield iso-octane and
isoheptane.
 Alkylation Reaction
Another significant reaction of propylene alkylation is:

Propylene + Isobutane  Propane + Isobutylene

Isobutylene + Isobutane  2,2,4-trimethylpentane (isooctane)

HF /H2SO4

HF /H2SO4
Alkylation Chemistry
Alkylation Chemistry
Alkylation

Sulfuric Acid Alkylation Unit

 Reaction Variables
1. Reaction Temperature

• Greater effect in Sulfuric Acid processes than

Hydrofluoric Acid
• Low T (-4 to 20oC) for Sulfuric Acid: higher quality
where the octane number may increase from one to
three (depending on efficiency of mixing in reactor)
• Higher T for Sulfuric Acid may affect the decreased of
octane number
• In Hydrofluoric acid alkylation, T range is 21-38oC
• Higher T for Hydrofluoric acid may degrades the
quality about three octane number
• Sulfuric acid alkylation : low T caused the acid
viscosity to increase, uniform mixing & separation of
emulsion will be difficult.
• T>21oC : polymerization of the olefins is increased,
yields are decreased. Normal sulfuric acid reactor T is
from 5oC to 10oC
• Max T: 21oC
• Min T: -1oC
 Reaction Variables
2. Acid Strength & Composition

• Alkylate quality depends on the effectiveness:

a) reactor mixing
b) water content of the acid
• In Sulfuric Acid Alkylation: the best quality & highest yields
are obtained with
acid strengths:93-95%
1-2% water (remainder HC diluents)
• In hydrofluoric acid alkylation, acid strength of 86-90%
with less than 1% water to get the highest octane number
 Acid Strength & Composition
• The water concentration and HC diluents in the
acid lowers its catalytic activity thus an 88% acid
containing 5% water is less effective than 88% acid
containing 2% water.
• Poor mixing efficiency, higher acid strength is
required
• Increase acid strength 89-93% by weight increases
alkylate quality by 1-2 octane numbers.
 Reaction Variables
3. Isobutane Concentration

• Expressed in terms of isobutane/olefin ratio

• High isobutane/olefin ratios:

increase octane number & yield
reduce side reactions & acid consumption

• In industrial practice the isobutane/olefin ratio on

reactor charge varies from 5:1 to 15:1
 Reaction Variables
4. Olefin Space Velocity (SV)
• Defined as volume of charged per hour divided by
the volume of acid in the reactor
SV = Olefin in Reactor (bbl/hour)
Acid in Reactor (bbl)

Schematic Diagram of Sulfuric Acid Alkylation Process

 Olefin Space Velocity
• Lowering the olefin space velocity :
reduces the amount of high boiling HC produced
increases the product octane number
lowers acid consumption

• Olefin space velocity is one way of expressing reaction time

• Contact time : Residence time of the fresh feed & externally
recycled isobutane in the reactor.

HF acid alkylation : 5-25 minutes

Sulfuric acid alkylation : 5-40 minutes
 Correlating factor, F
The relationship is predicted based on a formula of a
correlating factor, F:

• This formula is useful in predicting trends in alkylate

quality
• The higher the value of F  better the alkylate quality
• Normal values of F: 10<F<40
 Alkylation Products

• Liquefied petroleum gas (LPG) grade, propane liquid

• Normal butane liquid
• C5 + alkylate
• Tar
• Other by products
 Alkylation Products

Product : Alkylate
- a mixture of high-octane, branched-
chain paraffinic hydrocarbons.

Premium blending stock

~ exceptional antiknock properties
~ clean burning
~ low vapor pressure
 Alkylation Products
• Premium blending stock
~ Exceptional antiknock properties
Research Octane Number (RON)
Motor Octane Number (MON): determined at 900 rpm
engine speed
- Essentially no olefins, benzene or aromatics
~ Clean burning
Low sulfur levels
~ Low vapor pressure
• Low vapour pressure, hard to change from liquid to
gas
• High vapor pressure, low boiling point, easy to change from
liquid to gas
 Catalyst
• Strong acids can catalyze the alkylation reaction
• Weaker acids can cause polymerization

• Therefore, acid strengths must be kept > 88% by

weight H2SO4 or HF
 to prevent excessive polymerization

• H2SO4 containing free SO3  caused undesired rxn

• H2SO4 concentrations > 99.3% not generally used
 Catalyst

~ Sulfuric acid : Sulfuric Plants for Butylene

~ Hydrofluoric acid : Hydrofluoric Plant for
Propylene

High octane alkylate gasoline

 Catalyst
Alkylation
Sulfuric (catalyst) plant is more favorable:
~ Butylene preferred
Produces the highest iso-octane levels
Resulting Research Octane Numbers of 93-95 (with isobutane)
RON and MON are about equal for alkylation
Amounts of butylene consumed per alkylate produced is the lowest
Side reactions are limited

~ Propylene less preferred

» Octane numbers are low (89-92 RON)
» Propylene & acid consumption are high
Alkylation Reactor
Alkylation
~ Acid settler
- separator
- acid drawn off bottom – recycled

~ Caustic Scrubber
- neutralizes Hydrocarbon
- using caustic solution (NaOH)
HF Alkylation Unit