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Principles & Practices to Manage Cl lon Stabilizer
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Principles & Practices to Manage Cl lon Stabilizer

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Typical Stabilizer Chloride Management Problems …

Typical Stabilizer Chloride Management Problems
What Causes NH4Cl Salts?
Mitigating System Fouling
Operating practices
Problems with Water Injection
Design To Mitigate Salt Formation
Prevention
Remove Nitrogen from the feed
Remove chloride from stabilizer feed
Chloride Guard Bed
Caustic Injection
Water Wash
Summary

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  • 1. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries Web Site: www.GBHEnterprises.com GBHE Technical Bulletin CTB #52 Catalytic Reforming Principles & Practices to Manage Chloride on a Catalytic Reformer Stabilizer Information contained in this publication or as otherwise supplied to Users is believed to be accurate and correct at time of going to press, and is given in good faith, but it is for the User to satisfy itself of the suitability of the information for its own particular purpose. GBHE gives no warranty as to the fitness of this information for any particular purpose and any implied warranty or condition (statutory or otherwise) is excluded except to the extent that exclusion is prevented by law. GBHE accepts no liability resulting from reliance on this information. Freedom under Patent, Copyright and Designs cannot be assumed.
  • 2. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries Web Site: www.GBHEnterprises.com Table of Contents Typical Stabilizer Chloride Management Problems What Causes NH4Cl Salts? Mitigating System Fouling Operating practices Problems with Water Injection Design To Mitigate Salt Formation Prevention Remove Nitrogen from the feed Remove chloride from stabilizer feed Chloride Guard Bed Caustic Injection Water Wash Summary
  • 3. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries Web Site: www.GBHEnterprises.com Typical Stabilizer Chloride Management Problems Stabilizer feed system plugging –Control valves –Feed/bottoms exchangers Salt deposits in stabilizer tower –Reduced tower efficiency •Off spec product Employ What Causes NH4Cl Salts? HCl + NH3 -- NH4Cl – Chloride injection • Use to maintain catalyst chloride levels • Converted to HCl in the reformer – Nitrogen in hydrotreated feed • Typical reformer feed specification: 0.5 ppm • Actual numbers higher – Up to 2 ppmUpdate Mitigating System Fouling Plugging can be alleviated during normal operation – Water injection Operating practices – Inject until evidence of plugging is alleviated – Slump tower to wash salt deposits
  • 4. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries Web Site: www.GBHEnterprises.com Problems with Water Injection Water + HCl -- HCl acid formation – HCl present in stabilizer feed – Piping and equipment corrosion Minimize water injection rate Design To Mitigate Salt Formation Prevention –Remove Nitrogen from the feed Denitrogenation decreases with decreasing catalyst activity Increase in reformer feed nitrogen content due to more difficult to treat hydrotreater feed stock and limited operating severity –Remove chloride from stabilizer feed Chloride guard bed ahead of stabilizer tower Caustic injection/water wash system on stabilizer feed Feed water wash with overhead neutralization Chloride Guard Bed Advantages – Removal of chloride to specified levels upstream of stabilizer – Minimal operator monitoring/changes required Disadvantages – Cost – Disposal of spent guard material (waste) – Polymerization leading to “green oil” fouling – Difficult to monitor for breakthrough
  • 5. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries Web Site: www.GBHEnterprises.com Caustic Injection Advantages – Minimal new equipment required – Low cost – Simple monitoring of effectiveness with pH analysis Disadvantages – Operations intensive – Emulsion problems with over injection or high concentration caustic solution – If injection is not monitored – plugging and corrosion can occur Water Wash Advantages – Minimal new equipment required – Simple monitoring of effectiveness with pH analysis Disadvantages – Proper design is critical – metallurgy upgrades may be required – Stabilizer must operate above dew point of water to prevent tower corrosion – Overhead water wash must force dew point of water such that acid can be controlled and neutralized
  • 6. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries Web Site: www.GBHEnterprises.com Summary - NH4Cl salt formation resultant of chloride injection and feed nitrogen - Causes plugging and reduced tower efficiency - Water injection can reverse the effects of plugging - Mitigation methods include nitrogen and chloride removal from stabilizer feed - Water can be used to prevent salt formation but leads to a secondary problem: HCl corrosion - HCl corrosion can be mitigated with chemical injection or metallurgy upgrades
  • 7. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries Web Site: www.GBHEnterprises.com

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