High Temperature Sulfur Removal in the Presence of Chlorides, for Magnaformers Catalytic Reforming Overview Commercial Catalytic Reforming Processes Application for Catalytic Reforming Sulfur Removal Magnaforming Overview

1. GBHE C2PT Catalyst Process Technology
VULCAN VGP Series Purification Catalyst and Absorbents
Gerard B. Hawkins
Managing Director, C.E.O.

2. High Temperature Sulfur Removal
in the Presence of Chlorides In
Magnaforming Units

3.  Catalytic reforming is a chemical process used to convert
petroleum refinery naphthas, typically having low octane ratings,
into high-octane liquid products called reformates which are
components of high-octane gasoline.
 Basically, the process re-arranges or re-structures the hydrocarbon
molecules in the naphtha feedstocks as well as breaking some of
the molecules into smaller molecules. The overall effect is that the
product reformate contains hydrocarbons with more complex
molecular shapes having higher octane values than the
hydrocarbons in the naphtha feedstock.
◦ Note: all of which utilize a platinum and/or a rhenium catalyst.

4.  Rheniforming: Developed by Chevron Oil Company.
 Powerforming: Developed by Esso Oil Company, now known as
ExxonMobil.
 Magnaforming; Developed by Engelhard Catalyst Company and
Atlantic Richfield Oil Company.
 Ultraforming: Developed by Standard Oil of Indiana, now a part of
the British Petroleum Company.
 Houdriforming: Developed by the Houdry Process Corporation.
 CCR Platforming: A Platforming version, designed for continuous
catalyst regeneration, developed by UOP.
 Octanizing: A catalytic reforming version developed by Axens, a
subsidiary of Institut Francais du petrole (IFP), designed for
continuous catalyst regeneration.
Catalytic Reforming Processes and Licensors

5. Licenser Process Name Commercial
Installations
Process Type
Universal Oil Products
(UOP) Process Division
Platforming Over 700 units ò Semi-regenerative
ò Continuous catalyst
regeneration
Institut Franτais du PΘtrole Catalytic
Reforming
90 unit
licensed (30
units continuous
regeneration
ò Semi-regenerative
ò Continuous catalyst
regeneration
Chevron Research Co. Rheniforming 73 units ò Semi-regenerative
Engelhard Corp. Magnaforming 150 units ò Semi-regenerative
ò Semi-cyclic
Exxon Research and
Engineering Co.
Powerforming 1.4 million
BPSD
ò Semi-regenerative or
cyclic
Amoco Oil Co. Ultraforming 150 units ò Cyclic or semi-
regenerative
Houdry Division of Air
Products and Chemicals, Inc.
Houdriforming 0.25 million
BPSD
ò Semi-regenerative

6. Typical Process Flow Diagram
Semi-Regenerative Unit

7. Sulfur Removal
 Catalyst commonly used in catalytic reforming contain noble metals such as
platinum and/or rhenium, which are very susceptible to poisoning by sulfur and
nitrogen compounds. Therefore, the naphtha feedstock to a catalytic reformer
is always pre-processed in a hydrodesulfurization unit which removes both the
sulfur and the nitrogen compounds.
 Sulfur is primarily a platinum function poison and its effect is similar to an over
chlorided catalyst. For operation at a constant octane the effect of sulfur
poisoning is to decrease the reformate yield, hydrogen make and reactor
temperatures, and increase the coking and hydrocracking rates.
 Catalyst regeneration is also more difficult if the catalyst has been
contaminated with sulfur. Sulfur on the catalyst and vessel surfaces is oxidized
during catalyst regeneration. The result is a regenerated catalyst with low
activity.

8.  This upstream hydrodesulfurization unit will remove most of the organic
sulfur in the naphtha feed, feed. However, there will still be ingress of
small amounts of sulfur to the reforming unit because. H2S will be
dissolved in the liquid naphtha because of inadequate stripping at the
hydrotreating stripper.
 Olefins and H2 S exit the hydrotreating reactor will recombine to form mercaptans, especially
at higher reactor temperatures towards the end of cycle.
 Feed/effluent exchanger leaks on the hydrotreating unit.
 Or as in some cases, recycle gas system has also been used as an alternative location by a
number of operators. Typically this location has been chosen when the operator has vessels
already available say for a recycle gas dryer.
Sulfur Removal

9. Application: High Temperature Sulfur Removal in the
Presence of Chlorides
 In Magnaforming Units, the high temperature recycle gas stream is
the location of choice for sulfur guards.
 This location offers a greater degree of sulfur removal because of
its multi-pass nature and hence quicker recovery from large sulfur
upsets.

10. HIGH SEVERITY OPERATION
0 0.2 0.4 0.6 0.8 1 1.2 1.4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
Feed sulphur ppm
C5+ yield vol% change
Pt only
Balanced
Skewed
LOW SEVERITY OPERATION
0 0.2 0.4 0.6 0.8 1 1.2 1.4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
Feed sulphur ppm
C5+ yield vol % change
Pt only
Balanced
Skewed

11. REFORMATE
LPG
Key : Vulcan Series S guard
RECYCLE
GAS
MAKE GAS OFF
GAS
NAPHTHA
FEED

12. Magnaforming - Reaction Section with Heaters
- Semi-Regenerative
- Semi-Cyclic

13. William C. Pfefferle
Invented Magnaforming, whilst Section head of Engelhard
Industries, Iselin, NJ, 1956–1969
Section Head. In charge of research on petrochemical processes.
Pioneered field of permeation mediated catalysis.
Patent # 3,3392,107
Issue Date: July 9, 1968
By 1988 150 Units were operating worldwide,
with HRI having installed units in Argentina, Algeria
and the USSR.