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P6. Isomerization Process

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95 views27 pages

P6. Isomerization Process

Uploaded by

Chiến Phùng
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© © All Rights Reserved
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P6.

Isomerization Process

➢Isomer: Compounds with the same molecular


formula as another, but with a different structure.

➢Isomerization: The hydrocarbons are made


into isomers.

1
6.1 History of Isomerization

➢Developed during World War II to obtain higher


octane gasoline.
➢Initially isomerization units produced isobutane from
n-butane using aluminum chloride.
➢Today isomerization is mainly focused on the
upgrading of refinery naphtha(C5/C6) streams into
high-octane motor gasoline.

2
6.2 Isomerization Process in Petroleum Industry
➢ Isomerization Process is a:
-Fixed-bed catalytic process.
-Conducted in vapour phase at low temperatures in the
presence of hydrogen.

-Using a metal hydrogenation catalyst on a suitable support


material promoted by the injection of small amounts of organic
chloride.
➢ Convert low octane number(ON) C5/C6 streams into high ON
gasoline and C4 into i-C4

3
6.3 Feed stock

➢Usual feed-Light straight run naphtha (C5,C6 )

➢Condensate & light raffinate from aromatic extraction


units.
➢Benzene containing feeds.

4
Hydrocarbon octane values Butane or C4 compounds equilibrium

Pentane or C5 compounds equilibrium Hexane or C6 compounds equilibrium


If the goal is isomerization of paraffins, then the least desirable components –
normal butane, pentane, and hexane are favored at increasing
5
temperature
6.4 Reaction chemistry
➢ Convert linear paraffin (C4 through C6) into their isomers.
➢ Reactions involved :

6
Reaction chemistry 7
Reaction chemistry 8
6.5 Process parameters

The extent of isomerization depends on


- Reactor temperature,
- Space velocity,
- Operating pressure,
- H2/hydrocarbon ratio.

9
6.6 Isomerization catalysts
➢Catalyst Used
- Chlorinated Alumina
- Modern Zeolite
- Metal Oxide (mainly Sulfated Zirconia)
➢Basically dual functional -both metallic and acidic.
- Metallic sites catalyze hydrogenation
/dehydrogenation reactions.
- Acidic sites catalyze isomerization hydro cracking
reactions.

10
Isomerization catalysts 11
Isomerization catalysts 12
6.7 Catalyst activation

➢Fresh isomerization catalyst is not active for carrying


out the reactions.
➢Catalyst activated by treating with some of the
chlorinating agents such as AlCl3 or CCl4.
➢Small amounts of chlorinating agent or the activator
are also added during the operation cycle to maintain
the catalyst activity.

13
6.8 Catalyst poisons

➢Catalysts are sensitive to impurities makeup gas


such as sulphur, nitrogen and water.
➢Aromatics, olefins and naphthenes also act as
poisons.

14
6.10 Catalyst regeneration

➢Isomerization catalysts are prone to deactivation due


to coke lay down on the catalyst surface by hydro
cracking reactions.
➢Activity restored by carrying out in situ oxidative
regeneration.

15
Isomerization process scheme
6.11 Isomerization processes based on feed
1. Butane isomerization
- Occurs in vapour phase.
- Less platinum content catalyst required due to lower
hydrogen uptake.
- Isobutane product are used as feedstock for alkylation
MTBE units.
2. C5/C6 isomerization
- Mostly occurs in liquid phase
- Consumes more hydrogen due to benzene saturation
reactions.
16
6.12 Isomerization processes based on configuration

1. Once-through or Single-pass isomerization


- Only partial conversion
- No recycle resulting in lower ON (78-84)
2. Recycle isomerization
- Achieve higher ON (88-92)
- For attaining higher ON, complete recycle of all
n-paraffins is required.

17
6.13 Commercial Isomerization Processes
1. UOP Isomerization Processes
(i) Butamer Process (C4)
-Use dual functional isomerization catalyst.
(ii) TIP With IsoSiv Adsorption
-Increase the octane number by 20 units
(iii) Penex Process (C5/C6)
-Isomerization of light straight run naphtha stream containing C5,C6 mixtures.
(iv) Par-Isom Process
-Uses a regenerable and water tolerant nonchlorided alumina catalyst.

18
6.13 Commercial Isomerization Processes

2.Axens Isomerization Processes


- ON of 89 attained.
3. GTC Isomerization Technology
- Platinum based mixed oxide catalyst
system.
4. Axens Hexorb Isomerization Process
- Desorbs n-paraffins from the molecular sieves by
pressure swing technique.

19
6.13 Commercial Isomerization Processes

5. Shell Hysomer Process


-Metal-loaded molecular sieve zeolite catalyst with high
tolerance for impurities such as S, H2O.
6. BP Isomerization Process
-Utilize a flexible Pt-alumina catalyst treated with CCl4.
7. Axens Ipsorb Isomerization Process

20
6.14 Reactors

➢Carried out in trickle bed reactors


- Feed trickles down through catalyst bed co-currently with H2
gas.
➢Generally two reactors are used in series operation to
complete reactions.
- In 1st reactor exothermic benzene saturation reactions
occur, Temperature rise of about 10-50oC.
- Second reactor is operated at temperature of 110-
150oC.

21
6.15 Technologies

22
✓ Increasing C5/C6 naphtha cut octane numbers up to 92
✓ The isomerate product is free of sulfur, aromatics and olefins, making it an
excellent gasoline pool component
✓ Chlorinated alumina is a catalyst, operating at the lower reactor temperatures

Technologies 23
UOP Penex™ Process Once
throught. The light naphtha
passes through the
isomerization reactor only
once. Normal paraffins are
converted to iso paraffins but
the conversion is limited by
equilibrium. Typical product
octanes are in the 80-84 RON
range. (R1: 133oC, 35atm, R2:
120oC, 32 atm)

UOP Penex™ /DIH


A de-isohexanizer is used to
recover and recycle unconverted
normal hexane and low octane
hexane isomers to the reactor
system. RONC values of 87-89
can be achieved.

Technologies 24
✓ Completely adsorbs and converts all normal paraffins to isomers
✓ The difference is that methyl pentanes (RON 74) are also converted, affording
the highest possible octane for a C5-C6 feed (up to RON 92).

Technologies 25
6.16 New isomerization process technologies

✓ The process technology developed for the LPI-100 catalyst is the Par-Isom™
process.
✓ The fresh C5–C6 feed is combined with makeup and recycle hydrogen and
directed to the charge heat exchanger, where the reactants are heated to reaction
temperature.
✓ In a two-reactor system, the first reactor is operated at higher temperature (200–
220oC) to improve the reaction rate, and the second reactor is operated at a lower
temperature to take advantage of the more-favorable equilibrium distribution of
higher octane isomers.
26

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