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Lecture 7A Slides

Catalytic reforming is a process that converts low-octane linear paraffins from naphtha into high-octane reformate, which is essential for gasoline production and aromatic chemical feedstock. The process involves multiple steps including feed preparation, catalytic reforming, and product separation, while managing undesired reactions like hydrocracking. Various reforming processes exist, including continuous and semi-regenerative methods, each with specific catalyst features and operational conditions to optimize yield and efficiency.

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Pooja Choudhari
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2 views

Lecture 7A Slides

Catalytic reforming is a process that converts low-octane linear paraffins from naphtha into high-octane reformate, which is essential for gasoline production and aromatic chemical feedstock. The process involves multiple steps including feed preparation, catalytic reforming, and product separation, while managing undesired reactions like hydrocracking. Various reforming processes exist, including continuous and semi-regenerative methods, each with specific catalyst features and operational conditions to optimize yield and efficiency.

Uploaded by

Pooja Choudhari
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Catalytic reforming is a process of transforming linear

paraffinic (C7-C10) hydrocarbons contained in crude unit


naphthas, with low octane ratings, are converted in a high
octane reformate containing.

These reformates are a premium blending stock for producing


high octane gasoline.

The reformate is also the main source of bulk aromatic


chemicals such as benzene, toluene, xylene, and ethylbenzene
which serve as feedstock in the manufacture of plastics.
The catalytic reformer is one of the major units for gasoline
production (37 wt% of the total gasoline pool).

The straight run naphtha from the crude distillation unit is


hydrotreated to remove sulphur, nitrogen and oxygen which can all
deactivate the reforming catalyst.

The hydrotreated naphtha (HTN) is fractionated into light naphtha


(LN), which is mainly C5-C6, and heavy naphtha (HN) which is mainly
C7-C10 hydrocarbons.

Light naphtha (LN) is isomerized in the isomerization unit. Light


naphtha can be cracked if introduced to the reformer.

Hydrogen, produced in the reformer can be recycled to the


naphtha hydrotreater, and the rest is sent to other units demanding
hydrogen.
 Highly endothermic process

 Operated in high severity mode to produce mainly


aromatics (80-90 vol%)

 A middle severity mode to produce high octane


gasoline (70% aromatics)

 Feeds are characterized by the Watson’s


characterization factor (K), naphthenes (N) vol% and
aromatics (A) in which (N+2A) must be defined.

 Also, IBP and EP must be characterized for the Feed.


Typical Heavy Naphtha Feedstocks

Mutineer-
Crude oil name Barrow Island CPC Blend Draugen
Exeter
Location Australia Kazakhstan[ North Sea
Australia
Initial boiling
149 140 149 150
point, °C
Final boiling
204 190 204 180
point, °C

Paraffins, liquid
46 62 57 38
volume %

Naphthenes,
42 32 27 45
liquid volume %

Aromatics,
12 6 16 17
liquid volume %
Low severity (relatively low octane) → low paraffin conversion
High severity → high paraffin conversion
Lean naphtha → high n-paraffinic content - difficult to process
Rich naphtha → low n-paraffinic (high naphthene) content - easy to
process

Feedstock: Heavy Naphtha Product: High Octane Gasoline

Paraffins ⇒ 45-55% Paraffins ⇒ 30-50%

Naphthenes ⇒ 30-40% Naphthenes ⇒ 5-10%

Aromatics ⇒ 5-10% Aromatics ⇒ 45-60%


Basic steps in catalytic reforming:
 Feed preparation: Naphtha Hydrotreatment: It
eliminates the impurities such as sulfur, nitrogen,
halogens, oxygen, water, olefins, di olefins, arsenic
and other metals presents in the naphtha feed stock
to have longer life catalyst.

 Preheating: Temperature Control

 Catalytic Reforming and Catalyst Circulation and


Regeneration in case of continuous reforming
process

 Product separation: Removal of gases and


Reformate by fractional Distillation

 Separation of aromatics in case of Aromatic


production
 The four major catalytic reforming reactions are:
 Reforming is a processing technique by which the molecular
structure of a hydrocarbon is rearranged to alter its properties.
The process is frequently applied to low-quality gasoline stocks
to improve their combustion characteristics.

 1) The dehydrogenation of naphthenes to convert them into


aromatics as exemplified in the conversion methylcyclohexane (a
naphthene) to toluene (an aromatic), as shown below:

 2) The isomerization of normal paraffins to isoparaffins as


exemplified in the conversion of normal octane to 2,5-
Dimethylhexane (an isoparaffin), as shown below:
 3) The dehydrogenation and aromatization of paraffins to
aromatics (commonly called dehydrocyclization) as exemplified
in the conversion of normal heptane to toluene, as shown below:

 4) The hydrocracking of paraffins into smaller molecules as


exemplified by the cracking of normal heptane into isopentane
and ethane, as shown below:
Undesired Reactions IN REFORMER
Hydrocracking consumes hydrogen and decreases the reformate yield by producing
gaseous hydrocarbons. Hydrocracking reactions are exothermic, but they can still be
kinetically favored at high temperatures, high H2 pressures
Typically, reformers operate at pressures from 50 to 350 psig (345–2415 kPa), a hydrogen/
feed ratio of 3–8 mol H2/mol feed, and liquid hourly space velocities of 1–3 h-1. These
conditions are chosen to promote the desired conversion reactions and inhibit hydrocracking
while limiting coke deposition on the catalyst surfaces.

Hydrocracking
n-C10+H2 → n-C6+n-C4
to inhibit this reaction, use high T, high SV, Low H2 Pressure, Catalytic reformers are
normally run at low H2 pressure to inhibit hydrocracking!

Heats of Reactions:
paraffin to naphthene → 44 kJ/mol H2 - endothermic
naphthenes to aromatics → 71 kJ/mol H2 - endothermic
hydrocracking → -56 kJ/mol H2 - exothermic
Figure 1. Summary of Reformer reactions
The research octane number (RON) - The percentage
by volume of iso-octane in a mixture of iso-octane
(and n-heptane that knocks with the same intensity
as the test fuel. Variation of research octane number
Features

 Since endothermal reactions are dominant in Catalytic Reforming


reaction, multiple reactors are arranged in a series with a
reheating furnace to maintain the reaction rate for reforming
reaction. Catalytic Reforming processes are classified as
continuous, cyclic, or semi-regenerative depending upon the
frequency of catalyst regeneration. The equipment for the
continuous process is designed to permit the removal and
replacement of catalyst during normal operation.
 Semi-Regenerative

 Cyclic Regenerative
Fixed bed
Moving bed

 Continuous Cyclic Regenarative


Various Catalytic Reforming Processes
Process Licensor
Rheniforming Chevron oil
Power forming ESSO Oil/EXXON
Magna forming Atlantic Richfield oil
Ultra forming British petroleum
Houdriforming Houdry process Platforming Powerforming
CCR Plateforming UOP (UOP) (Exxon)

Octanising Axens
Magnaforming Catalytic
(Engelhard) reforming (IFP)

Rheniforming Ultra forming


(Chevron) (Amoco)
Features:
 Regeneration of catalyst in fixed bed reactors after
shut down by burning off the carbon formed on the
catalyst surface.

 Reaction like dehydrogenation of paraffins and


occur in the first reactor with high temp. drop.

 Reactions like paraffin isomerization and


naphthene dehydroisomerization occur in second
reactor with moderate temp. decline.

 Dehydrocyclization and hydrocracking occur in the


third giving low temperature decline.
Catalyst features:

1) Highest C5+ and H2 yields


2) Highest aromatic yields
3) Better catalyst stability
4) Extended cycle length
5) Lower rhenium content (0.25% Pt+0.025% -0.25%
Rh) – lower fill cost

Other features:
•Hydrogen partial pressure maintained such that
H2/HC is greater than 25 for monometallic catalyst.
•Light HCs (C1-C4) separated from reformate in
stabilizer.
Features:
 Modified semi-regenerative process
 Fourth fixed bed reactor added to semi-
regenerative process
 Avoids the shutting of whole unit during
regeneration
CYCLIC OPERATION OF
FIXED BED REACTORS
Utilizes continuous in-situ regeneration of a portion of
the catalyst in a special regenerator and the continuous
addition of this regenerated catalyst to the reactors.
 There are two primary licensors of CCR technology:
• UOP’s Platforming process
• Axens’ Octanizing Process

 The catalyst in a CCR reformer is usually an alumina


base sphere or extradite which is impregnated with
either platinum, rhenium, or a combination of both.
Features:
 UOP’s is called CCR Platforming
 3or 4 reactors are installed one on top of the
other.
 Effluent from each reactor is sent to common
furnace for heating
 Catalyst moves by gravity from 1st reactor
 Product from R4 sent to the stabilizer and gas
recovery.
 Process operated at lower H2 partial pressures (3
bar), with a reformate yield gain of nearly 10
vol%.
Comparison of the three reforming processes

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