Ha Noi University of Mining and Geology
Advanced Program Course 4
Technology and regeneration of catalyst in isomerization
Group 6:
Le Truong Anh Dung
Pham Thanh Duy
Pham Son Ha
Nguyen Cong Huy
Vu Cong Duy
Nguyen Van Ha
Isomerization Catalysts
Comparison of operating conditions of isomerization
UOP LLC
(Universal Oil Products)
A multi-national company developing and delivering technology to the petroleum refining, gas processing, petrochemical production, and major manufacturing industries
Products
Technology products
Physical products
Paraffin isomerization process technology
Penex
Butamer
Once-through paraffin isomerization (TIP)
Catalysts and associated feeds and processes

Definition of Penex process
A continuous catalytic process used in the refining of crude oil
It isomerizes light straight run naphtha (C5/C6) into higher-octane, branched C5/C6 molecules













Penex ‘s Process
Low Octane Value
high-quality gasoline
H2
Favorable
Condition
Limit The Side Effects
High Performance
The flow scheme for the Penex process.










H2
Dryer-Compressor
Chlorine
separator
Air Filtration Equipment
Corrodent
Separator
Penex process innovations
Hydrogen once-through (HOT) Penex process

Penex-Molex Process
The flow scheme of the HOT Penex
The removal of several major pieces of equipment
The Product performance remain the same

An economically attractive technology

The comparison between HOT and H2 recycle system











The cost savings resulting from the equipment reduction for the HOT system is roughly 15%. The lack of recycle gas also lowers utilities requirements so that the overall isomerization operation is more attractive.










_The economics of the HOT flow relative to a Penex unit with recycle gas.
_ The HOT scheme results in a 20% savings in capital and operating charges relative to the conventional flow.
_This development has resulted in unit costs for the HOT Penex process that are substantially more attractive than other methods of octane upgrading without loss of product performance.
Penex-Molex system
It is a system that the Molex process technology coupled with Penex isomerization using I-8 catalyst to produce a high-octane isomerate.
With the Penex process, the feedstock is subsequently passed through a Molex technology column, the end product typically has an octane rating of 88-91 (compare to 82 of only Penex process)
Allowing the selective removal in the Molex unit of normals from the reactor
effluent for recycle back to the Penex reactor to extinction


TIP Design improvement
(Once – through paraffin)

Feed of isomerization:
n-paraffin ( C5-C6 ) take up to 40% - 50%
Benzene is hydrogenated to Cyclohexane
2 different ways
The MOST QUANTITY of GASOLINE product
The HIGHEST OCTANE NUMBER
(the most quality of gasoline)
Order of the pathway
The mechanism of TIP
TIP used the adsorption to separate n-paraffin and branch paraffin.
n-paraffin will go out of the mixture and return to isomerization units
Branch paraffin which have high octane number will be mix with gasoline
This process also need Hydrogen to remove sulfur out off feed, so that we can remain catalytic activity
Depend on the conditions and requirements of the demand, the production decides to choose the suitable way
1. The first way
2. The second way
HOT Butamer

Hydrogen once-through
It is a quite similar flow scheme to the HOT Penex process.
the HOT Butamer scheme does offer an advantage in recovered yield if both the reaction section and stabilizer are considered.

Coprocessing of C4, C5, C6
Reducing the cost of both butane and LSR isomerization.
This technique results in a product rich in both i-C4 and high-octane C5 and C6 in a single low-cost process unit.
The coprocessing of C4, C5, and C6 hydrocarbons has been developed and commercialized by UOP.
Catalyst deactivation
Poisoning
Fouling and Coking
Thermal degradation
Vapor formation, vapor–solid and solid–solid reactions
Attrition
Poisoning Catalyst


Poisoning by Sulfur compounds
Poisoning by Nitrogen compounds
Poisoning by Metals



Definition: Strong chemisorption of species on catalytic sites which block sites for catalytic reaction
Poisoning Catalyst
Effect of Sulfur in Feed
Fouling, Coking and Carbon Deposition

Fouling is the physical (mechanical) deposition of species from the fluid phase onto the catalyst surface, which results in activity loss due to blockage of sites and/or pores.
Fouling catalyst
Fouling and Coking
The top right image depicts an enveloped catalyst pellet
The images to the top left and bottom right depict general fouling an a metal catalyst
The image on the bottom left depicts fouling which occurs on the inside of a catalyst
Thermal degradation
Definition: Thermally induced loss of catalytic surface area, support area, and active phase-support reactions
Temperature of the Reaction:
High Temperature increases Coke Deposition on the Catalyst ………. (Olefins are Coke precursors)
High Temperature increases the rate of Graphitization of Coke
Coke growth occurs mainly on the Support
Temperature doesn’t change the coke location, whether on the Support or on the Metal
Vapor formation, vapor–solid and solid–solid reactions
Vapor formation
Reaction of gas with catalyst phase to produce volatile compound
Vapor–solid and solid–solid reactions
Reaction of vapor, support, or promoter with catalytic phase to produce inactive phase
Attrition

Definition: Loss of catalytic material due to abrasion; loss of internal surface area due to mechanical-induced crushing of the catalyst particle
Regeneration of Deactivated Catalysts


Regeneration of Poisoned Catalysts

Regeneration of Sulfur-poisoned catalysts
The presence of both SO2 and H2S in the gaseous effluent suggests that the following reactions occur:
Ni-S + H2O → NiO + H2S
H2S + 2H2O → SO2 + 3H2

Regeneration of Poisoned Catalysts

Regeneration of Nitrogen-poisoned catalysts
Selective catalytic reduction (SCR):
4NH3 + 4NO + O2→4N2 + 6H2O
4NH3 + 2NO2 + O2→3N2 + 6H2O
Regeneration of Catalyst Deactivated by Coke or Carbon
Coke can be removed by gasification with O2, H2O, CO2, and H2
The order of decreasing reaction rate of O2 > H2O > H2
Air regeneration is used to remove coke from catalysts in catalytic cracking hydrotreating processes, and catalytic reforming
Coke burn-off
Source of information
Paraffin isomerization innovations
P.J. Kuchar*, J.C. Bricker, M.E. Reno and R.S. Haizmann
UOP, 25 East Algonquin Road, Des Plaines, IL 60017-5017 (USA)
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