Antos George J., Aitani Abdullah M. Catalytic Naphtha Reforming

2nd ed., rev&expanded. - Marcel Dekker, Inc. 2004. - 602 p.
The use of catalytic naphtha reforming as a process to produce high-octane gasoline is as important now as it has been for over the 45 years of its commercial use. The catalytic reformer occupies a key position in a refinery, providing high value-added reformate for the gasoline pool; hydrogen for feedstock improvement by the hydrogen-consuming hydrotreatment processes; and frequently benzene, toluene, and xylene aromatics for petrochemical uses. The technology has even further impact in the refinery complex. The processes of hydrogenation, dehydrogenation, and isomerization have all benefited from the catalyst, reactor, and feed treatment technologies invented for catalytic reforming processes.Part I: Naphtha Reforming Chemistry

Compositional Analysis of Naphtha and Reformate
Rune Prestvik, Kjell Moljord, Knut Grande, and Anders HolmenIntroduction
The Naphtha Fraction
Origin from Crude Oil Distillation and Processing
Naphtha Composition
Hydrocarbons
Heteroatomic Organic Compounds, Water, and Metallic Constituents
Effect Of Naphtha Composition On Process Performance And Product Quality In Catalytic Reforming
Gasoline Quality Requirements
The Octane Number
Catalytic Reforming Process
Effect of Naphtha Hydrocarbon Composition
Effect of Naphtha Boiling Range
Effect of Naphtha Sulfur Content
Analysis Methods
Hydrocarbon Composition
Distillation Range
Sulfur and Nitrogen Analysis
Octane Number DeterminationBasic Reactions of Reforming on Metal Catalysts
Zolta´n Paa´lPossible Mechanisms Of The Reactions
Catalysts And Their Active Sites
Relationship Between Reactant Structure And Reactivity
Effect Of Second Components On The Active Sites Of The Catalysts
Metallic Components
Nonmetallic Components
Sulfur and Nitrogen
Carbon
Oxygen
Hydrogen
Concluding Remarks On The Possible Active Sites In Metal Catalyzed ReactionsChemistry of Bifunctional Metal–Acid Catalysis
Jose´ M. Parera and Nora S. Fı´goliIntroduction
Thermodynamics
Change of Standard Free Energy of Reaction
Equilibrium Constant
Influence of Temperature on the Equilibrium Constant
Influence of Total Pressure and Composition on Equilibrium
Reactions
Mechanisms Of Reaction
Classical Metal–Acid Bifunctional Reaction Mechanism
Intermediates, Reaction Sequences, and Conversions
Thermodynamics
Mass Transport
Selectivity
Other Metal–Acid Bifunctional Reaction Mechanisms
Other Types of Bifunctional Catalysts
NomenclatureNaphtha Hydrotreatment
Syed Ahmed AliIntroduction
Reformer Feedstocks: Genesis And Constitution
Straight-Run Naphthas
Cracked Naphthas
Visbreaker Naphtha
Coker Naphtha
FCC Naphtha
Hydrocracked Naphtha
Sulfur Species in Naphthas
Hydrotreating Reactions: Reactivities, Thermodynamics, And Kinetics
Hydrotreating Reactions and Reactivities
Thermodynamics of Hydrotreating Reactions
Hydrodesulfurization
Hydrodenitrogenation
Recombination Reaction
Reaction Kinetics
Hydrotreating catalysts
Active Components
Catalyst Structure
Catalyst Deactivation and Poisoning
Arsenic
Sodium
Hydrogen Sulfide
Catalyst Regeneration
Process scheme and operating conditions
Process Flow Scheme
Operating Parameters
Temperature
Space Velocity
Hydrogen Partial Pressure
Future OutlookPart II: Reforming Catalysts

Preparation of Reforming Catalysts
J. R. Regalbuto and George J. AntosIntroduction
Reforming Catalyst Supports
γ- and η-Al₂O₃
Surface Acidity
Influence of Halogen on Alumina Acidity
Forming of Alumina Macroparticles
Platinum-Containing CatalystsKey FeaturesIndustrial Impregnation
Impregnation
Fundamental Phenomena of Impregnation
Coordination Chemistry of Dissolved and Adsorbed Pt Complexes from CPA
Pt uptake in Zeolites and MAPSO and SAPO Zeotypes
Drying, Oxidation, and Reduction of the Impregnated Support
Bimetallic Catalysts
Platinum–Rhenium
Mineral Compounds
Organometallic Compounds
Platinum–Tin
Coimpregnation
Impregnation of Tin Derivatives on Alumina-Supported Platinum
Platinum–Iridium
Platinum–Germanium
Other Bimetallic and Multimetallic Catalysts
Metal Profiles In Catalyst Pellets
ConclusionCharacterization of Naphtha-Reforming Catalysts
Burtron H. Davis and George J. AntosIntroduction
Alumina Supports
Surface Area and Porosity
Acidity
Infrared Spectroscopy
Calorimetry
Chlorided Catalysts
Fluorided Alumina
Platinum–Alumina Catalysts
Dispersion
X-ray Diffraction
Transmission Electron Microscopy
Chemisorption Techniques
Titration Methods
Small-Angle X-ray Scattering
X-ray Absorption Fine-Structure Analysis
Extended XAFS
X-ray Absorption Near-Edge Structure
Nuclear Magnetic Resonance
Temperature-Programmed Desorption or Reduction
X-ray or Ultraviolet Photoelectron Spectroscopy; Electron Spectroscopy for Chemical Analysis (ESCA)
Auger Electron Spectroscopy
Ion Scattering Spectroscopy
Infrared Spectroscopy for Metallic Function
Calorimetry
Characterization Of Platinum–Rhenium Catalyst
Characterization Of Platinum–Tin–Alumina Catalysts
Characterization Of Other Bimetallic Catalysts
Group VIII or Group VIII/Group IB Bimetallics
Platinum and Partially Reduced Metal
Characterization Of Alkaline L-Zeolites–Pt
SummaryOptimization of Catalyst Pore Structure by Kinetics and Diffusion Analysis
Jerzy SzczygiełModels of Porous Structures
Optimization of Porous Structure Reported in Literature
Scope Of Chapter[/i]
Kinetics And Reaction Paths For Reforming
Previous Kinetic Modeling
Experiments and Methods
Discussion of Results
Heptane + Methylcyclohexane
n-Heptane
Naphtha Fraction (60–150°C)
Choice and Analysis of Kinetic Schemes
n-Heptane
n-Heptane + Methylcyclohexane
Naphtha Fraction
Models Based on an Analytical Description of Time-Related Variations in the Content of Reagents
Summarizing Comments
Diffusion Phenomena In The Bidispersive Grain Of The Catalyst
Tasks in Analyzing Diffusion Phenomena
Assumptions in the Description of Diffusion Phenomena
Examples of Calculations
Statistical Analysis
Properties of Bidispersive Catalytic Systems
Summary Comments on Diffusion Phenomena in the Grain of the Reforming Catalyst
Optimizing The Porous Structure Of The Reforming Catalyst
Scope of the Simulation of the Optimal Structure
Topological and Geometrical Representation of the Pore Space
Physicochemical Phenomena of the Reforming Process
Kinetics
Diffusion
Method and Scope of Model Analysis
Discussion of Results Obtained from Analysis of the Mathematical ModelExperimental Verification Of Theoretical Results
Method of Analysis
Experimental
Preparation of Support
Preparation of Catalyst
Activity Tests: Dehydrocyclization of n-Heptane
Analysis of ResultsThe New Generation of Commercial Catalytic
Naphtha-Reforming Catalysts
George J. Antos, Mark D. Moser, and Mark P. LapinskiIntroduction
Semiregenerative Reforming Catalysts
Recent Semiregenerative Catalyst Developments
Process ImprovementsRegenerative Reforming Processes And Catalysts
Cyclic and Continuous Units
Catalyst Advances
Cyclic Catalysts
Continuous Catalysts
Regenerator Advances
Combining Semiregeneration with Continuous Regeneration
Zeolitic Reforming Catalysts
Reformate Processing
Aromatics from LPG
Aromatics from Naphtha
Future DevelopmentsPart III: Catalyst Deactivation and Regeneration

Naphtha Reforming Over Zeolite-Hybrid-Type Catalysts
Grigore PopCatalyst Preparation And Characterization
Evidence Of LD-HBS Mechanism
Reaction Pathways In N-Hexane Transformation
Commercial Naphtha Reforming Over Hybrid Catalysts
Heat Of Reaction For Naphtha Reforming
Demonstration Unit For Naphtha ReformingNomenclature
SubscriptsDeactivation by Coking
Octavio Novaro, Cheng-Lie Li, and Jin-An WangIntroduction
Coke Characterization Techniques
Temperature-Programmed Oxidation
Infrared Spectroscopy
¹³C NMR and ¹H NMR
Raman Spectroscopy
X-ray Diffraction
Transmission Electronic Microscopy
Localization And Distribution Of Coke
Locations and Distribution of the Coke on the Catalyst Surface
Coke Distribution Across the Catalyst Pellet
Coke Distribution Along the Catalyst Bed
Effects Of Catalysts And Operating Parameters On Coking
Metallic Platinum Content, Dispersion, and Ensemble Size
Metallic Additives
Tin Addition
Rhenium Addition
Interaction Between Platinum and Additives
Catalyst Support
Operating Conditions
Reaction Environment Factors
Circulating Hydrogen
Sulfur and Sulfurization
Chlorine and Water Content
Feed Compositions
Coking Mechanisms
Coking Kinetics
Effects Of Coking On Activity And Selectivity
Conclusions
SymbolsCatalyst Regeneration and Continuous Reforming Issues
Patricia K. Doolin, David J. Zalewski, and Soni O. OyekanIntroduction
Catalytic Reforming Processes
Semiregenerative Process
Cyclic Regenerative Process
Continuous Regenerative Process
Catalyst Regeneration
Reactor/Catalyst Purge
Coke Burn
Oxidation/Chlorination
Nitrogen Purge/Drying
Metals Reduction
Metals Sulfiding
Catalyst Properties Influencing Reforming Catalyst Activity And Performance
Surface Area Stability
Catalyst Attrition
Particle Crush Strength
Rotating Drum Test
Metal Redispersion
Regenerator TroubleshootingPart IV: Technology and Applications

Precious Metals Recovery from Spent Reforming Catalysts
Horst Meyer and Matthias GrehlIntroduction
Materials Handling At The Oil Refinery
Description Of Spent Catalysts
Form
Support Material
Precious Metal Content and Promoters
Distribution of the Precious Metals
Impurities
Weighing, Sieving, And Sampling Procedures
Assays Of Precious Metals And Rhenium
Sample Handling and Analysis
Accuracy, Splitting Limits, and Umpires
Treatment Routes
Removal of Halides, Hydrocarbons, and Carbon
Acidic and Alkaline Leach Processes
Utilization of Leach Products
Smelting
Precious Metals Separation And Purification
Dissolution of Leach Residue
Purification Process
Platinum Metal Production
Recovery Schemes for Palladium and Iridium
Rhenium Separation And Purification
Solvent Extraction or Ion Exchange
Purification of Ammonium Perrhenate and Perrhenic Acid
Commercial AspectsLicensed Reforming Processes
Abdullah M. AitaniIntroduction
Process Classification
Semiregenerative Process
Cyclic (Full Regeneration) Process
Continuous Catalyst Regeneration Process
Major Reforming Processes
UOP Platforming
CCR Platforming
RZ Platforming
Axens Reforming Technology–Octanizing and Aromizing Processes
Other Reforming Processes
Houdriforming Process
Magnaforming Process
Powerforming Process
Rheniforming Process
Ultraforming Process
Zeoforming Process
Commercial Reforming Catalysts
Concluding RemarksControl Systems for Commercial Reformers
Lee TurpinIntroduction
Fundamental Control Systems For Commercial Reformers
Basic Regulatory Control Systems
Traditional Control Systems
Distributed Control Systems
Reformer Regulatory Control System
Regulatory Controls in a Catalytic Reformer
Auxiliary Control System
Emergency Shutdown Systems
Emergency Shutdown System–Initiating Events
Logic Tree for a Catalytic Reformer Emergency Shutdown System
Emergency Shutdown System and Overall Plant Safety
Process Equipment Safety Systems
Fired Heaters
Recycle Compressor and Drivers
Pressure Relief System
Catalyst Control Functions
Catalytic Reformer Performance Indicators
Catalyst Environment
Catalyst Deactivation
Advanced Process Control Of Catalytic Reformers
Instrumentation Requirements for APC
APC Application in the Reactor Section
Reformer Catalyst Deactivation Control with APC
APC of Reformer Fired Heaters
APC Application in the Separation Section
APC Special Case Applications
Coke Handling
Catalyst Regeneration
Integrated Feed Systems
Minimization of System Pressure
Inferred Properties
Research Octane Number
Reid Vapor Pressure
Stabilizer Overhead Composition
Feed Composition from Density
Coke Laydown Rate
Fired Heater Tubeskin Temperatures
Recycle H₂ Purity
On-line Analyzers
Recycle Hydrogen Purity Analyzers
Recycle Hydrogen Moisture Analyzers
Reformate Octane Analyzers
Stabilizer Component Analyzers
Reformer Feed Analyzers
Fired Heater O₂ Analyzers
Utility System On-line Analyzers
Regeneration System On-line Analyzers
Benefits from Application of APC to a Catalytic Reformer
Benefits from Minimizing Operating Costs with APC in a Reformer Unit
Benefits from Maximizing Yields with APC in a Reformer Unit
Benefits of Reducing Variability with APC in a Reformer Unit
Calculation of Benefits in a Reformer Operation
Expert Advisor Systems For Catalytic Reformers
Expert Advisor Functions in Catalytic Reforming
Expert Advisor Integration into the Control System
On-Line Optimization Of Catalytic Reformers
Defining the Catalytic Reformer Economic Envelope
Sources of Benefits
Economic Drivers in a Catalytic Reformer
Defining the Reformer Economic Envelope
The Reformer Optimization Statement
Product and Cost Pricing Coefficients
Mathematical Techniques for Real-Time Optimization
Using an LP for Real-Time Optimization
Optimization Using Statistical Regression Models
Optimization Using Kinetic Models
Model Solver Technology–Sequential Modular Calculations and Equation-Oriented Calculations
RT-OPT Frequency of Execution
Reformer Model Calibration
Instrumentation and Analyzer Requirements
Integration of a Reformer Optimization Project into the Control System
Operator Training
Support Issues with Real-Time Optimization of Reformers
The Danger in Being Overly Conservative in RT-OPT of Reformers
Implementation Plans for Real-Time Optimization
Project Analysis
Model Development
Model On-line Implementation
Ongoing Support and EvaluationModeling Catalytic Naphtha Reforming: Temperature Profile Selection and Benzene Reduction
Rafael Larraz and Raimundo ArveloIntroduction
Reforming Thermodynamic Equilibrium Calculations
Rigorous Methodology
Shortcut Method
Feed Characterization Technique
Feed Characterization Algorithm
NMR On-line Analyzers
Naphtha Reforming Kinetic Model
Reaction Mechanism
Reactor Model
Deactivation Function
Parameter Estimation
Flash Drum Separator Model
Model Applications
Reforming Model Performance
Naphtha Reforming Heat Needs
Benzene Reduction and Reformer Operation ConditionsSymbolsAppendix Fractals And Surfaces