Petrochemical & Petroleum

Refining Technology
Conversion Process
(Alteration)
Conversion
 Change the size and/or 2. Unification (combining)
structure of hydrocarbon
molecules - alkylation & polymerization

1. Decomposition (dividing) 3. Alteration (rearranging)

- hydro, thermal & catalytic - isomerization & catalytic

cracking, coking and reforming
visbreaking
Alteration
 Catalytic reforming and isomerization are processes which rearrange
hydrocarbon molecules to produce products with different
characteristics.
 After cracking, some gasoline streams, although of the correct
molecular size, require further processing to improve their
performance, because they are deficient in some qualities, such as
octane number or sulphur content.
 Hydrogen (steam) reforming produces additional hydrogen for use in
hydrogenation processing.
Catalytic Reforming Process
Catalytic Reforming
 Catalytic reforming processes convert low-octane heavy naphthas into
aromatic hydrocarbons for petrochemical feedstocks and high-octane
gasoline components, called reformates, by molecular rearrangement
or dehydrogenation.
 Depending on the feedstock and catalysts, reformates can be
produced with very high concentrations of toluene, benzene, xylene
and other aromatics useful in gasoline blending and petrochemical
processing.
 Hydrogen, a significant by-product, is separated from the reformate
for recycling and use in other processes.
 The resultant product depends on reactor temperature and pressure,
the catalyst used and the hydrogen recycle rate.
Catalytic Reforming
 Some catalytic reformers operate at low pressure and others at high
pressure. Some catalytic reforming systems continuously regenerate the
catalyst, some facilities regenerate all of the reactors during
turnarounds, and others take one reactor at a time off stream for
catalyst regeneration.
 In catalytic reforming, naphtha feedstock is pretreated with hydrogen
to remove contaminants such as chlorine, sulphur and nitrogen
compounds, which could poison the catalyst.
 The product is flashed and fractionated in towers where the
remaining contaminants and gases are removed.
 The desulphurized naphtha feedstock is sent to the catalytic reformer,
where it is heated to a vapour and passed through a reactor with a
stationary bed of bi-metallic or metallic catalyst containing a small
amount of platinum, molybdenum, rhenium or other noble metals.
Catalytic Reforming
 The two primary reactions which occur are production of high-octane
aromatics by removing hydrogen from the feedstock molecules, and the
conversion of normal paraffins to branched-chain or isoparaffins.
 In platforming, another catalytic reforming process, feedstock which
has not been hydrodesulphurized is combined with recycle gas and first
passed over a less expensive catalyst.
 Any remaining impurities are converted to hydrogen sulphide and
ammonia, and removed before the stream passes over the platinum
catalyst.
 Hydrogen-rich vapour is recirculated to inhibit reactions which may
poison the catalyst. The reactor output is separated into liquid
reformate, which is sent to a stripping tower, and gas, which is
compressed and recycled.
Catalytic Reforming
 In catalytic reforming, HC molecular structures are rearranged to form
higher octane aromatics.
 Typical feedstocks & reformer products have the following PONA
analysis
Catalytic Reforming
 Reactions in catalytic reformer for the formation of aromatics &
isoparaffins are:

1. Paraffins  Naphthenes  Aromatics (isomerization)

2. Olefins are saturated  Paraffins
3. Naphthenes  Aromatics
4. Aromatics are left essentially unchanged
Catalytic Reforming
1. Dehydrogenation of Naphthenes to Aromatics
2. Dehydrocyclization of Paraffins to Aromatics
3. Isomerization
4. Hydrocracking
Catalytic Reforming
There are several major reforming processes in use today. These include
the:
1. Platforming processes licensed by UOP LLC
2. Powerforming (Exxon)
3. Ultraforming (Amoco)
4. Catalytic Reforming (Engelhard)
5. Magnaforming (ARCO)
6. Reforming (Institut Francais du Petrole, IFP)
7. Rheniforming (Chevron)
Catalytic Reforming

LOW COST
-high H2 recycle rate & high operating P
to minimize coke lay down
to minimize consequent loss catalytic activity
 Continuous Catalyst Regeneration
(CCR Platforming)

EXPENSIVE
-catalyst regenerated continuously
Reforming Catalyst
 Platinum
 Platinum + other metal (alumina,silica, palladium, molybdenum,
rhenium)
 Rhenium + Pt  to form a more stable catalyst which
permits operation at lower P
Catalytic Reforming

Reformer Burner Reformer Reactor

Isomerization Process
Isomerization Process
 Transformation of one molecular structure into another (isomer)
whose component atoms are the same but arranged in a different
geometrical structure
Isomerization Process
 Isomerization converts n-butane, n-pentane and n-hexane into their
respective iso-paraffins.
 Some of the normal straight-chain paraffin components of light
straight-run naphtha are low in octane. These can be converted to high-
octane, branched-chain isomers by rearranging the bonds between
atoms, without changing the number or kinds of atoms. Isomerization is
similar to catalytic reforming in that the hydrocarbon molecules are
rearranged, but unlike catalytic reforming, isomerization just converts
normal paraffins to iso-paraffins.
 Isomerization uses a different catalyst than catalytic reforming.
 The two distinct isomerization processes are butane (C4) and
pentane/hexane. (C5/C6).
Isomerization Process
 Butane (C4) isomerization produces feedstock for alkylation.
 A lower-temperature process uses highly active aluminium chloride or
hydrogen chloride catalyst without fired heaters, to isomerize n-butane.
 The treated and preheated feedstock is added to the recycle stream,
mixed with HCl and passed through the reactor
C4 Isomerization
Isomerization Process
 Pentane/hexane isomerization is used to increase the octane number
by converting n-pentane and n-hexane.
 In a typical pentane/hexane isomerization process, dried and
desulphurized feedstock is mixed with a small amount of organic
chloride and recycled hydrogen, and heated to reactor temperature. It is
then passed over supported-metal catalyst in the first reactor, where
benzene and olefins are hydrogenated.
 The feed next goes to the isomerization reactor, where the paraffins
are catalytically isomerized to isoparaffins, cooled and passed to a
separator.
 Separator gas and hydrogen, with make-up hydrogen, is recycled.
 The liquid is neutralized with alkaline materials and sent to a stripper
column, where hydrogen chloride is recovered and recycled.
Isomerization Process
 Isomerization of n-butane to i-butane
Isomerization Process
N-pentane N-hexane
RON = 62 RON =25

2-methylbutane
RON = 92
2,2-dimethylbutane
RON =92

Isomerization of pentane/hexane into its

isomers
Isomerization Process

Schematic of C4 isomerization
Isomerization Process

Schematic of C5 and C6 isomerization

Isomerization Process
 At present the following hydro-isomerisation processes
are commercially available:

 UOP BUTAMER for butane isomerisation

 UOP PENEX for pentane/hexane isomerisation
 BP C4 isomerisation for butane isomerisation
 BP C5/C6 isomerisation for pentane/hexane isomerisation
 SHELL Hysomer for pentane/hexane isomerisation
Steam Reforming Process
Steam Reforming Process
 High-purity hydrogen (95 to 99%) is needed for
hydrodesulphurization, hydrogenation, hydrocracking and
petrochemical processes.
 If not enough hydrogen is produced as by-products of refinery
processes to meet the total refinery demand, the manufacture of
additional hydrogen is required.
 In hydrogen steam reforming, desulphurized gases are mixed with
superheated steam and reformed in tubes containing a nickel base
catalyst.
 The reformed gas, which consists of steam, hydrogen, carbon
monoxide and carbon dioxide, is cooled and passed through converters
where the carbon monoxide reacts with steam to form hydrogen and
carbon dioxide.
Steam Reforming Process
 The carbon dioxide is scrubbed with amine solutions and vented to
the atmosphere when the solutions are reactivated by heating.
 Any carbon monoxide remaining in the product stream is converted to
methane.
Thank You