Handbook of Spent Hydroprocessing Catalysts

This handbook serves scientists and researchers interested in any aspect of spent hydroprocessing catalysts. Its aim is to assist in the analysis and assessment of refined catalyst byproducts and processing options, to determine whether spent catalysts can be processed into productive resources. For non-regenerable spent catalysts, the book takes into consideration both safety and ecological implications of utilizing landfill and other waste options.

• Provides comprehensive guidance and assistance to those making decisions on the fate of spent catalysts, radically improving strategic options for refining organisations
• Offers solutions that maximize procedural, regulatory, safety, and preparedness benefits
• Contains detailed information on hazardous characteristics of spent and regenerated catalysts with deployment recommendations, and acts as a benchmark document for establishing threshold limits of regulated species as well as for developing procedures for handling spent catalysts to ensure environmental acceptance

This work will be of interest to academic institutions specializing in petroleum research, petroleum companies, and petroleum research institutes, as well as to catalyst regenerators, catalyst manufacturers, metal reclaiming companies, and governments and agencies involved in regulatory affairs.

  1. INTRODUCTION

2. DEVELOPMENT IN PETROLEUM REFINING
2.1. Conventional Refineries
2.2. Revamped conventional refineries
2.3. Advanced Refineries

3. HYDROPROCESSING OF PETROLEUM
3.1. Feeds for Hydroprocessing
3.1.1. Light feeds
3.1.2. Medium heavy feeds
3.1.3. Heavy and extra heavy feeds
3.2. Hydroprocessing reactions
3.3. Hydroprocessing Catalysts
3.3.1. Structure and chemical composition
3.3.1.1. Co(Ni)-Mo(W)-S phase
3.3.1.2. Brim site model
3.3.1.3. Co-Mo-S© phase
3.3.1.4. Effect of support
3.3.1.5. Physical properties
3.3.1.6.Improved hydroprocessing catalysts
3.4. Hydroprocessing Reactors and Processes
3.4.1. Fixed bed reactor systems
3.4.1.1. Unibon process
3.4.1.2. ARDS and Hyvahl processes
3.4.2. Moving and ebullated bed reactors.
3.4.3. Comparison of hydroprocessing reactors

4. CATALYST DEACTIVATION
4.1. Deactivation Due to Structural Change of Catalyst
4.2. Deactivation by Coke and Nitrogen Bases
4.3. Combined Effect of Coke and Metals on Deactivation
4.4. Effect of Temperature and Hydrogen Pressure
4.5. Effect of Mechanical Properties of Catalyst
4.6. Mechanism of Catalyst  Deactivation
4.6.1. Mechanism of coke formation
4.6.1.1. Chemical aspects
4.6.1.2. Physical aspects
4.6.2. Mechanism of metal deposition
4.6.2.1. Deposition of inorganic solids
4.6.2.2. Deposits of organometallic origin
4.6.2.2.1. Vanadium deposits
4.6.2.2.2. Nickel and mixed deposits
4.7. Modeling of Deactivation Process

5. ENVIRONMENTAL AND SAFETY ASPECTS OF SPENT HYDROPROCESSING CATALYSTS
5.1. Regulatory Affairs
5.1.1. Classification of spent hydroprocessing catalysts
5.1.2. Transportation of spent catalysts
5.1.3. Recycling and disposal of spent catalysts
5.1.4. Handling of Spent Catalysts on Refinery Site
5.1.5. Cradle-to-grave approach to spent catalyst management
5.2. Hazardous Characteristics of Spent Hydroprocessing Catalysts
5.2.1. Exposure to air
5.2.2. Reactions of air with coke
5.2.3. Reactions of air with catalyst
5.2.4. Leachability
5.3. Pretreatment of Spent Catalysts for Disposal

6. REGENERATION
6.1. Regenerability of Spent Hydroprocessing Catalysts
6.2. Oxidative Regeneration
6.2.1. Mechanism of oxidative regeneration
6.2.1.1. Oxidation of coke
6.2.1.2. Involvement of metals
6.2.2. Kinetics of oxidative regeneration
6.2.2.1. Chemically controlled kinetics
6.2.2.2. Diffusion controlled kinetics
6.2.3. Modeling of oxidative regeneration
6.2.4. Characterization of regenerated catalyst
6.2.4.1. Surface properties
6.2.4.2. Activity of regenerated catalysts
6.2.4.3. Chemical structure
6.2.5. Safety and environmental aspects of oxidative regeneration
6.2.6. Other oxidation agents
6.3. Other Regeneration Methods
6.3.1. Regeneration in H2O and CO2
6.3.2. Regeneration with nitrogen oxides
6.3.3. Reactivation
6.3.4. Regeneration Aided by Radiation Treatment
6.3.5. Reductive Regeneration
6.3.6. Regeneration by Attrition and Abrasion
6.3.7. Resulfiding of Regenerated Catalysts
6.4. Industrial Regeneration
6.4.1. In-situ regeneration
6.4.2. Off-site regeneration
6.4.3. Mechanical separation of spent catalysts
6.4.4. Commercial regeneration processes
6.4.4.1. Porocel-Belt regeneration process
6.4.4.2. TRICAT regeneration process
6.2.4.3. Eurecat process
6.2.4.4. REACT process
6.2.4.5. ReFRESH process
6.2.4.6. Rotary kilns
6.4.5. Comparison of regeneration processes

7. REJUVENATION
7.1. Organic Agents
7.1.1. Mechanism of rejuvenation by organic agents
7.1.2. Kinetics of rejuvenation
7.1.3. Emissions from rejuvenation by organic agents
7.1.3.1. Gaseous emissions
7.1.3.2. Liquid emissions
7.1.3.3. Solid emissions
7.1.4. Rejuvenation process design
7.1.4.1. De-oiling
7.1.4.2. Mechanical separation
7.1.4.3. Metals leaching process
7.1.4.4. Decoking of leached catalysts
7.1.4.5. Other auxiliary processes
7.1.4.6. Design basis
7.2. Inorganic Agents
7.2.1. Acidic agents
7.2.2. Basic agents
7.2.3. Environmental and safety aspects
7.3. Solvent Extraction
7.4. Bio-rejuvenation
7.5. Non-Leaching Methods for Contaminant Metals Removal

8. CASCADING
8.1. Cascading of Spent Catalysts
8.2. Cascading of Regenerated Catalysts
8.3. Cascading of Rejuvenated Catalysts

9. NEW CATALYSTS FROM SPENT CATALYSTS
9.1. Petroleum Applications
9.1.1. Reprocessing
9.1.1.1. Procedure and analysis
9.1.1.2. Testing of coprocessed catalysts
9.1.1.3. Effect of hydrothermal treatment on reprocessed catalysts
9.1.2. Other preparation methods
9.1.3. Spent catalysts in slurry bed hydrocracking
9.2. Catalysts for Non-Petroleum Applications
9.3. Gas Treatment Sorbents
9.4. Preparation of Useful Materials from Spent Catalysts
9.4.1. Utilization in cement industry
9.4.2. Waster water treatment
9.4.3. Other materials
9.4.4. Abrasives and alloys
9.4.5. Ceramic materials
9.4.6. Synthetic aggregates
9.4.7. Bricks production

10. SPENT CATALYSTS FROM DEWAXING OPERATIONS
10.1. Conventional Catalysts
10.2. Dewaxing catalysts
10.2.1. Composition of dewaxing catalysts
10.2.2. Deactivation
10.2.3. Environmental and safety aspects
10.2.4. Regeneration
10.2.5. Metal reclamation

11. METAL RECLAMATION FROM SPENT CATALYSTS
11.1. Laboratory Studies on Metal Reclamation from Spent Hydroprocessing Catalysts
11.1.1. Leaching studies
11.1.1.1. Leaching with ammonia and ammonium salts solution
11.1.1.2. Leaching with acids
11.1.1.3. Inorganic acids
11.1.1.4. Organic acids
11.1.1.5. Alkali leaching 
11.1.1.6. Two-stage leaching
11.1.1.7. Bio-leaching
11.1.2. Roasting with Alkali Compounds
11.1.2.1. Roasting with sodium salts
11.1.2.2. Roasting with potassium salts
11.1.3. Chlorination
11.1.4. Metal recovery by carbothermic treatment
11.1.5. Metal recovery using electrolytic cells
11.1.6. Metal recovery by applying thermal plasma
11.1.7. Summary of laboratory studies
11.2. Separation of Metals from Solutions
11.3. Commercial Processes
11.3.1. Gulf Chemical & Metallurgical Process
11.3.2. CRI-MET Process
11.3.3. EURECAT  Process
11.3.4. Taiyo Koko Company Process
11.3.5. Full Yield Industry Process
11.3.6. Moxba-Metrex Process
11.3.7. Quanzhuo Jing-Tai Industry Process
11.3.8. Metallurg Vanadium Process
11.3.9. German Process
11.3.10. NIPPON Catalyst Cycle Process
12. MARKETS AND PRICE TRENDS FOR METALS IN SPENT HYDROPROCESSING CATALYSTS
12.1. Molybdenum
12.2. Tungsten
12.3. Nickel
12.4. Cobalt
12.5. Vanadium
12.6. Alumina

13. FUTURE  PERSPECTIVES

14. REFERENCES