VULCAN VGP-1000 High Temperature Mn Sulfur Guard Technology

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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

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VULCAN VGP-1000 High Temperature Mn Sulfur Guard Technology

  1. 1. GBHE C2PT Catalyst Process Technology VULCAN VGP Series Purification Catalyst and Absorbents Gerard B. Hawkins Managing Director, C.E.O.
  2. 2. High Temperature Sulfur Removal in the Presence of Chlorides In Magnaforming Units
  3. 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. 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. 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. 6. Typical Process Flow Diagram Semi-Regenerative Unit
  7. 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. 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. 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. 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. 11. REFORMATE LPG Key : Vulcan Series S guard RECYCLE GAS MAKE GAS OFF GAS NAPHTHA FEED
  12. 12. Magnaforming - Reaction Section with Heaters - Semi-Regenerative - Semi-Cyclic
  13. 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.

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