Look at two main types
Explain mechanisms
Explain prevention of cracking
Three main types
1 Carbon cracking
2 Boudouard carbon formation
3 CO reduction
Common poisons include
Sulfur
Chlorides and other halides
Metals including arsenic, vanadium, mercury, alkali metals (including potassium)
Phosphates
Organo-metalics
1. Introduction reasons for purification, types of poisons, and typical systems
2. Hydrogenation
3. Dechlorination
4. Sulfur Removal
5. Purification system start-up and shut-down
Reactor Arrangement for Continuous Vapor Phase ChlorinationGerard B. Hawkins
Reactor Arrangement for Continuous Vapor Phase Chlorination
CONTENTS
1 BACKGROUND
2 REACTOR
3 CHEMICAL SYSTEM
4 PROCESS CHEMISTRY
5 KINETICS EXPERIMENTS AND MODELING
6 INTERPRETATION OF KINETICS INFORMATION
7 OPERATING CONDITIONS AND REACTOR DESIGN
8 REACTOR STABILITY AND CONTROL
FIGURES
1 POSTULATED REACTION PATHS FOR PROGRESSIVE CHLORINATION OF B-PICOLINE 3
2 CHLORINATION OF b-PICOLINE: MODEL PREDICTIONS OF PRODUCT DISTRIBUTION IN FULLY-MIXED REACTOR
3 TWO-STAGE REACTOR: RATE OF CHLORINATION OF b-PICOLINE
DOCUMENTS REFERRED TO IN THIS PROCESS ENGINEERING GUIDE
Look at two main types
Explain mechanisms
Explain prevention of cracking
Three main types
1 Carbon cracking
2 Boudouard carbon formation
3 CO reduction
Common poisons include
Sulfur
Chlorides and other halides
Metals including arsenic, vanadium, mercury, alkali metals (including potassium)
Phosphates
Organo-metalics
1. Introduction reasons for purification, types of poisons, and typical systems
2. Hydrogenation
3. Dechlorination
4. Sulfur Removal
5. Purification system start-up and shut-down
Reactor Arrangement for Continuous Vapor Phase ChlorinationGerard B. Hawkins
Reactor Arrangement for Continuous Vapor Phase Chlorination
CONTENTS
1 BACKGROUND
2 REACTOR
3 CHEMICAL SYSTEM
4 PROCESS CHEMISTRY
5 KINETICS EXPERIMENTS AND MODELING
6 INTERPRETATION OF KINETICS INFORMATION
7 OPERATING CONDITIONS AND REACTOR DESIGN
8 REACTOR STABILITY AND CONTROL
FIGURES
1 POSTULATED REACTION PATHS FOR PROGRESSIVE CHLORINATION OF B-PICOLINE 3
2 CHLORINATION OF b-PICOLINE: MODEL PREDICTIONS OF PRODUCT DISTRIBUTION IN FULLY-MIXED REACTOR
3 TWO-STAGE REACTOR: RATE OF CHLORINATION OF b-PICOLINE
DOCUMENTS REFERRED TO IN THIS PROCESS ENGINEERING GUIDE
Theory of Carbon Formation in Steam Reforming
Contents
1 Introduction
2 Underpinning Theory
2.1 Conceptualization
2.2 Reforming Reactions
2.3 Carbon Formation Chemistry
2.3.1 Natural Gas
2.3.2 Carbon Formation for Naphtha Feeds
2.3.3 Carbon Gasification
2.4 Heat Transfer
3 Causes
3.1 Effects of Carbon Formation
3.2 Types of Carbon
4 What are the Effects of Carbon Formation?
4.1 Why does Carbon Formation Get Worse?
4.1.1 So what is the Next Step?
4.2 Consequences of Carbon Formation
4.3 Why does Carbon Form where it does?
4.3.1 Effect on Process Gas Temperature
4.4 Why does Carbon Formation Propagate Down the Tube?
4.4.1 Effect on Radiation on the Fluegas Side
4.5 Why does Carbon Formation propagate Up the Tube?
5 How do we Prevent Carbon Formation
5.1 The Role of Potash
5.2 Inclusion of Pre-reformer
5.3 Primary Reformer Catalyst Parameters
5.3.1 Activity
5.3.2 Heat Transfer
5.3.3 Increased Steam to Carbon Ratio
6 Steam Out
6.1 Why does increasing the Steam to Carbon Ratio Not Work?
6.2 Why does reducing the Feed Rate not help?
6.3 Fundamental Principles of Steam Outs
TABLES
1 Heat Transfer Coefficients in a Typical Reformer
2 Typical Catalyst Loading Options
FIGURES
1 Hot Bands
2 Conceptual Pellet
3 Naphtha Carbon Formation
4 Heat Transfer within an Reformer
5 Types of Carbon Formation
6 Effect of Carbon on Nickel Crystallites
7 Absorption of Heat
8 Comparison of "Base Case" v Carbon Forming Tube
9 Carbon Formation Vicious Circle
10 Temperature Profiles
11 Carbon Pinch Point
12 Carbon Formation
13 Effect on Process Gas Temperature
14 How does Carbon Propagate into an Unaffected Zone?
15 Movement of the Carbon Forming Region
16 Effect of Hot Bands on Radiative Heat Transfer
17 Effect of Potash on Carbon Formation
18 Application of a Pre-reformer
19 Effect of Activity on Carbon Formation
Purpose
Key to good performance
Problem Areas
Catalysts, heat shields and plant up-rates
Burner Guns
Development of High Intensity Ring Burner
Case Studies
Conclusions
Reformer Tube design principles
- Larsen Miller Plot
- Larsen Miller & Tube Design
- Design Margins - Stress Data Used
- Max Allowable & Design Temperature
- Tube Life
- Effect of Temperature on Life
- Material Types
HK40: 25 Cr / 20 Ni
HP Modified: 25 Cr / 35 Ni + Nb
Microalloy: 25 Cr / 35 Ni + Nb + Ti
- Alloy Developments
- Comparison of Alloys
Manufacturing Technology
- Welds
Failure mechanisms
- Failure Mechanisms - Creep
- Creep Propagation
- Common Failure Modes
- Uncommon Failure Modes
- Failure by Creep
- Creep Rupture - Cross Section
- Failure at Weld
Actions to Take if Tube Fails
- Pigtail Nipping
Inspection techniques
Classification of Problems
- Visual Examination
- Girth Measurement
- Ultrasonic Attenuation
- Radiography
Eddy Current Measurement
LOTIS Tube Inspection
LOTIS Compared to External Inspection
Getting the Most Out of Your Refinery Hydrogen PlantGerard B. Hawkins
Getting the Most Out of Your Refinery Hydrogen Plant
Contents
Summary
1 Introduction
2 "On-purpose" Hydrogen Production
3 Operational Aspects
4 Uprating Options on the Steam Reformer
4.1 Steam Reforming Catalysts and Tube Metallurgy
4.2 Oxygen-blown Secondary Reformer
4.3 Pre-reforming
4.4 Post-reforming
5 Downstream Units
6 Summary of Uprating Options
7 Conclusions
High Temperature Shift Catalyst Reduction ProcedureGerard B. Hawkins
High Temperature Shift Catalyst Reduction Procedure
The catalyst, as supplied, is Fe2O3. This reduces to the active form, Fe3O4, in the presence of hydrogen when process gas is admitted to the reactor.
1. The mildly exothermic reactions are:
3 Fe2O3 + H2 ========= 2 Fe3O4 + H2O
3 Fe2O3 + CO ========= 2 Fe3O4 + CO2
Reactor and Catalyst Design
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
4 CATALYST DESIGN
4.1 Equivalent Pellet Diameter
4.2 Voidage
4.3 Pellet Density
5 REACTOR DESIGN
6 CATALYST SUPPORT
6.1 Choice of Support
TABLES
1 CATALYST SUPPORT SHAPES
2 SECONDARY REFORMER SPREADSHEET
FIGURES
1 GRAPH OF EFFECTIVENESS v THIELE MODULUS
2 VARIATION OF COSTS WITH CATALYST SIZE
3 VARIATION OF COSTS WITH CATALYST BED VOIDAGE
4 VARIATION OF COSTS WITH VESSEL DIAMETER
Catalyst poisons & fouling mechanisms the impact on catalyst performance Gerard B. Hawkins
Primary Effects
Secondary Effects
Typical Poisons in hydrocarbon processing
Permanent Poisons
- Arsenic, lead, mercury, cadmium…
- Silica, Iron Oxide….
Temporary Poisons
- Sulfur, Chlorides, Carbon
Boiler Feed water impurities
Heavy Metals
Foulants
THE NATURE OF CARBON DEPOSITS FORMED ON CATALYSTS
- CARBON FORMATION
Type A, B, C
- FEEDSTOCK COMPOSITION EFFECTS
COMMERCIAL’ CARBON DEPOSITS
- CARBON BURNING IN AIR
- CARBON REMOVAL BY STEAMING
- CARBON BURN CONTROL METHODS
- CATALYST – REACTION WITH STEAM
- MAXIMUM OXYGEN CONCENTRATION
- TEMPERATURE OF THE CATALYST SURFACE DURING CARBON BURNS
- CONDITIONS TO BURN OFF CARBON COATED CATALYST
- EFFECT OF CARBON FORMATION
Natural Gas (from a natural reservoir or associated to a crude production) can contain acid gas (H2S and/or CO2)..
The Gas Sweetening Process aims to remove part or all of the acid gas.
Project of Introduction to Petroleum and Gas Engineering and Explanation of the cracking process and types.Cracking, as the name suggests, is a process in which large hydrocarbon molecules are broken down into smaller and more useful ones,The cracking products, such as ethene, propene, buta-1,3-diene and C4 alkenes, are used to make many important chemicals. Others such as branched and cyclic alkanes are added to the gasoline fraction obtained from the distillation of crude oil to enhance the octane rating.
High level introduction
Mainstream syngas = steam reforming processes
Ammonia; methanol; hydrogen/HyCO
Town gas
Steam reforming; low pressure cyclic
Direct reduction iron (DRI)
HYL type processes; Midrex type processes
Theory of Carbon Formation in Steam Reforming
Contents
1 Introduction
2 Underpinning Theory
2.1 Conceptualization
2.2 Reforming Reactions
2.3 Carbon Formation Chemistry
2.3.1 Natural Gas
2.3.2 Carbon Formation for Naphtha Feeds
2.3.3 Carbon Gasification
2.4 Heat Transfer
3 Causes
3.1 Effects of Carbon Formation
3.2 Types of Carbon
4 What are the Effects of Carbon Formation?
4.1 Why does Carbon Formation Get Worse?
4.1.1 So what is the Next Step?
4.2 Consequences of Carbon Formation
4.3 Why does Carbon Form where it does?
4.3.1 Effect on Process Gas Temperature
4.4 Why does Carbon Formation Propagate Down the Tube?
4.4.1 Effect on Radiation on the Fluegas Side
4.5 Why does Carbon Formation propagate Up the Tube?
5 How do we Prevent Carbon Formation
5.1 The Role of Potash
5.2 Inclusion of Pre-reformer
5.3 Primary Reformer Catalyst Parameters
5.3.1 Activity
5.3.2 Heat Transfer
5.3.3 Increased Steam to Carbon Ratio
6 Steam Out
6.1 Why does increasing the Steam to Carbon Ratio Not Work?
6.2 Why does reducing the Feed Rate not help?
6.3 Fundamental Principles of Steam Outs
TABLES
1 Heat Transfer Coefficients in a Typical Reformer
2 Typical Catalyst Loading Options
FIGURES
1 Hot Bands
2 Conceptual Pellet
3 Naphtha Carbon Formation
4 Heat Transfer within an Reformer
5 Types of Carbon Formation
6 Effect of Carbon on Nickel Crystallites
7 Absorption of Heat
8 Comparison of "Base Case" v Carbon Forming Tube
9 Carbon Formation Vicious Circle
10 Temperature Profiles
11 Carbon Pinch Point
12 Carbon Formation
13 Effect on Process Gas Temperature
14 How does Carbon Propagate into an Unaffected Zone?
15 Movement of the Carbon Forming Region
16 Effect of Hot Bands on Radiative Heat Transfer
17 Effect of Potash on Carbon Formation
18 Application of a Pre-reformer
19 Effect of Activity on Carbon Formation
Purpose
Key to good performance
Problem Areas
Catalysts, heat shields and plant up-rates
Burner Guns
Development of High Intensity Ring Burner
Case Studies
Conclusions
Reformer Tube design principles
- Larsen Miller Plot
- Larsen Miller & Tube Design
- Design Margins - Stress Data Used
- Max Allowable & Design Temperature
- Tube Life
- Effect of Temperature on Life
- Material Types
HK40: 25 Cr / 20 Ni
HP Modified: 25 Cr / 35 Ni + Nb
Microalloy: 25 Cr / 35 Ni + Nb + Ti
- Alloy Developments
- Comparison of Alloys
Manufacturing Technology
- Welds
Failure mechanisms
- Failure Mechanisms - Creep
- Creep Propagation
- Common Failure Modes
- Uncommon Failure Modes
- Failure by Creep
- Creep Rupture - Cross Section
- Failure at Weld
Actions to Take if Tube Fails
- Pigtail Nipping
Inspection techniques
Classification of Problems
- Visual Examination
- Girth Measurement
- Ultrasonic Attenuation
- Radiography
Eddy Current Measurement
LOTIS Tube Inspection
LOTIS Compared to External Inspection
Getting the Most Out of Your Refinery Hydrogen PlantGerard B. Hawkins
Getting the Most Out of Your Refinery Hydrogen Plant
Contents
Summary
1 Introduction
2 "On-purpose" Hydrogen Production
3 Operational Aspects
4 Uprating Options on the Steam Reformer
4.1 Steam Reforming Catalysts and Tube Metallurgy
4.2 Oxygen-blown Secondary Reformer
4.3 Pre-reforming
4.4 Post-reforming
5 Downstream Units
6 Summary of Uprating Options
7 Conclusions
High Temperature Shift Catalyst Reduction ProcedureGerard B. Hawkins
High Temperature Shift Catalyst Reduction Procedure
The catalyst, as supplied, is Fe2O3. This reduces to the active form, Fe3O4, in the presence of hydrogen when process gas is admitted to the reactor.
1. The mildly exothermic reactions are:
3 Fe2O3 + H2 ========= 2 Fe3O4 + H2O
3 Fe2O3 + CO ========= 2 Fe3O4 + CO2
Reactor and Catalyst Design
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
4 CATALYST DESIGN
4.1 Equivalent Pellet Diameter
4.2 Voidage
4.3 Pellet Density
5 REACTOR DESIGN
6 CATALYST SUPPORT
6.1 Choice of Support
TABLES
1 CATALYST SUPPORT SHAPES
2 SECONDARY REFORMER SPREADSHEET
FIGURES
1 GRAPH OF EFFECTIVENESS v THIELE MODULUS
2 VARIATION OF COSTS WITH CATALYST SIZE
3 VARIATION OF COSTS WITH CATALYST BED VOIDAGE
4 VARIATION OF COSTS WITH VESSEL DIAMETER
Catalyst poisons & fouling mechanisms the impact on catalyst performance Gerard B. Hawkins
Primary Effects
Secondary Effects
Typical Poisons in hydrocarbon processing
Permanent Poisons
- Arsenic, lead, mercury, cadmium…
- Silica, Iron Oxide….
Temporary Poisons
- Sulfur, Chlorides, Carbon
Boiler Feed water impurities
Heavy Metals
Foulants
THE NATURE OF CARBON DEPOSITS FORMED ON CATALYSTS
- CARBON FORMATION
Type A, B, C
- FEEDSTOCK COMPOSITION EFFECTS
COMMERCIAL’ CARBON DEPOSITS
- CARBON BURNING IN AIR
- CARBON REMOVAL BY STEAMING
- CARBON BURN CONTROL METHODS
- CATALYST – REACTION WITH STEAM
- MAXIMUM OXYGEN CONCENTRATION
- TEMPERATURE OF THE CATALYST SURFACE DURING CARBON BURNS
- CONDITIONS TO BURN OFF CARBON COATED CATALYST
- EFFECT OF CARBON FORMATION
Natural Gas (from a natural reservoir or associated to a crude production) can contain acid gas (H2S and/or CO2)..
The Gas Sweetening Process aims to remove part or all of the acid gas.
Project of Introduction to Petroleum and Gas Engineering and Explanation of the cracking process and types.Cracking, as the name suggests, is a process in which large hydrocarbon molecules are broken down into smaller and more useful ones,The cracking products, such as ethene, propene, buta-1,3-diene and C4 alkenes, are used to make many important chemicals. Others such as branched and cyclic alkanes are added to the gasoline fraction obtained from the distillation of crude oil to enhance the octane rating.
High level introduction
Mainstream syngas = steam reforming processes
Ammonia; methanol; hydrogen/HyCO
Town gas
Steam reforming; low pressure cyclic
Direct reduction iron (DRI)
HYL type processes; Midrex type processes
DEACTIVATION OF METHANOL SYNTHESIS CATALYSTS
CONTENTS
1 INTRODUCTION
2 THERMAL SINTERING
3 CATALYST POISONING
4 REACTANT INDUCED DEACTIVATION
5 SUMMARY
TABLES
1 DEACTIVATION PROCESSES ON METHANOL SYNTHESIS CATALYSTS
2 MELTING POINT, HUTTIG AND TAMMANN TEMPERATURES OF COPPER, IRON AND NICKEL
3 SINTERING RATE CONSTANTS CALCULATED INLET AND OUTLET SIDE STREAM UNIT FOR VULCAN VSG-M101
4 COMPARISON BETWEEN CALCULATED S∞ AND DISCHARGED MEASUREMENTS ON VULCAN VSG-M101
5 EFFECT OF POSSIBLE CONTAMINANTS AND POISONS ON CU/ZNO/AL2O3 CATALYSTS FOR METHANOL SYNTHESIS
6 GUARD SCREENING TEST RESULTS ON METHANOL MICRO-REACTOR. EFFECT OF DEPOSITED METALS ON METHANOL ACTIVITY
FIGURES
1 THE HΫTTIG AND TAMMANN TEMPERATURES OF THE COMPONENTS OF A SYNTHESIS CATALYST
2 A SCHEMATIC REPRESENTATION OF TWO CATALYST SINTERING MECHANISMS
3 SIDE STREAM DATA FOR VULCAN VSG-M101. INLET TEMPERATURE 242 OC, PRESSURE 1500 PSI, GAS COMPOSITION 6% CO, 9.2% CO2, 66.9% H2, 2.5% N2 AND 15.4% CH4, SPACE VELOCITY 17,778 HR-1. MEAN OUTLET TEMPERATURE 280 OC
4 TEMPERATURE DEPENDENCE OF THE RATE OF SINTERING
5 MECHANISM OF SULFUR RETENTION
6 CORRELATION OF SULFUR CAPACITY WITH TOTAL SURFACE AREA
7 EFFECT OF DEPOSITED (NI+FE) PPM ON METHANOL SYNTHESIS CATALYST ACTIVITY
8 DISCHARGED (FE + NI) DEPOSITION LEVELS ON METHANOL SYNTHESIS PLANT SAMPLES
9 EPMA ANALYSIS OF DISCHARGED LABORATORY SAMPLE OF POISONED VULCAN VSG-M101
10 THE EFFECT OF CO2 ON SYNTHESIS CATALYST DEACTIVATION
REFERENCES
Development of
- Improved catalysts to be employed within existing production units for existing reactors
- Improved catalysts for existing reactors using new procedures calling for new equipment
- Integration of catalyst and reactor
Heat transfer and mass transport
- Integration of catalytic reaction and separation of reactants or reaction products
Catalytic distillation as an example : performing a catalytic reaction within a distillation column ......
Deactivation Modeling through Separable Kinetics of Coking On Ni/CZ Catalyst ...IOSR Journals
Abstract : Steam methane reforming (SMR) is a very significant technique to produce hydrogen from fossil fuels. In this particular work, nickel is used as the active metal and ceria-zirconia (CZ) bi-metallic oxide is used as the support. The foremost challenge to this process is sooting or coking over the catalyst surface and blocking the active sites. For the economic viability of the catalyst, it is very significant to make it coke deposition resistant. This is the reason that the kinetic modeling of the deactivation is very important. Therefore, this paper is aimed to model the deactivation and activity of the catalyst. A rate model of the deactivation process is also developed using separable kinetics. A comparison with commercial catalyst is also reported to show that the Ni/CZ catalyst is much more stable towards the coking. Keywords –Coking, Deactivation, Methane, Separable kinetics, Steam reforming.
Fischer-Tropsch Catalysts: Preparation, Thermal Pretreatment and Behavior Du...Gerard B. Hawkins
Fischer-Tropsch Process
Themes
Competitive Dissociative Adsorption
Reducibility of Metal Oxides
Feed Stock ofthe Fischer-Tropsch Process
Catalytic Partial Oxidation
Heats of Reaction
Direct vs Indirect Catalytic Partial Oxida.....
METHANOL PLANT - SHALE GAS FEED PRETREATMENT
CASE STUDY #091406
Case Background
A Methanol plant operator would like to examine the technical feasibility of using Shale Gas as a feedstock to their Methanol plant.
The first step in the Methanol production process is gas pretreatment. The purpose of gas pretreatment is to make the gas suitable for the downstream processes. There are two groups of compounds that are usually present in natural gas and that should be removed during pretreatment—the associate NGL and the sulfur-containing compounds. Some natural gas reservoirs may also have other trace components that must be removed, but these are not discussed here.
This case study examines the impact of CO2 (Carbon Dioxide) on the pre-treatment section design, performance and efficiency of ACME Methanol Plant’ feed gas pre-treatment section.
Case 1: Normal Shale Gas
Case 2: “Bad Gas”
Case 3: Low CO2
Case 4: High CO2
CONTENTS
1 SCOPE
2 PROPERTIES OF FLUID
2.1 General Properties of Sodium Hydroxide
2.2 Physical Properties of Sodium Hydroxide and its Solutions
2.3 Chemical Properties and uses of Sodium Hydroxide
2.4 Physiological effects of Sodium Hydroxide
2.5 Specifications of Commercial Caustic Soda Grades
3 CHOICE OF PUMP TYPE
3.1 Pump Duty
3.2 Pump Type
4 RECOMMENDED LINE DIAGRAMS
5 RECOMMENDED LAYOUT
6 CONSTRUCTION FEATURES
7 MATERIALS OF CONSTRUCTION
7.1 Nickel and Nickel Alloys
7.2 Austenitic Stainless Steel
7.3 Aluminium, Aluminium Alloys, etc.
7.4 Non-Metallic Materials
TABLES
1 PHYSICAL PROPERTIES (Solid Form)
2 PHYSICAL PROPERTIES (Solution Form)
3 CAUSTIC SODA GRADES
FIGURES
1.1 LINE DIAGRAM - HORIZONTAL GLANDED, GLANDLESS AND VERTICAL IN-LINE PUMPS
1.2 LINE DIAGRAM - VERTICAL SPINDLE CANTILEVER PUMPS
1.3 LINE DIAGRAM - SELF PRIMING PUMPS
1.4 LINE DIAGRAM - RECIPROCATING PLUNGER METERING PUMPS
1.5 LINE DIAGRAM - POSITIVE DISPLACEMENT DIAPHRAGM METERING PUMPS
1.6 WATER FLUSHING ARRANGEMENT FOR DOUBLE MECHANICAL SEAL
1.7 WATER FLUSH (QUENCH) ARRANGEMENT FOR SINGLE HARD FACED (CARBIDE) SEAL AND BACK-UP LIP SEAL
2 PHASE DIAGRAM OF NaOH-H2O
3 VISCOSITY OF AQUEOUS CAUSTIC SODA SOLUTIONS
4 VAPOR PRESSURE OF AQUEOUS CAUSTIC SODA SOLUTIONS
5 ENTHALPY CONCENTRATION FOR AQUEOUS CAUSTIC SODA SOLUTIONS
6 SPECIFIC GRAVITY FOR AQUEOUS CAUSTIC SODA SOLUTIONS
7 DILUTION OF CAUSTIC SODA LIQUOR
8 THERMAL CONDUCTIVITY OF AQUEOUS CAUSTIC SODA SOLUTIONS
9 SPECIFIC HEAT OF CAUSTIC SODA SOLUTIONS
10 BOILING POINTS OF STRONG CAUSTIC SODA SOLUTIONS AT REDUCED PRESSURE
11 COMMENCEMENT OF FREEZING OF CAUSTIC SODA SOLUTIONS (0 - 52% W/W)
12 TEMPERATURES ATTAINED ON DISSOLUTION OF ANHYDROUS CAUSTIC SODA
13 HEAT OF SOLUTION FOR ANHYDROUS CAUSTIC SODA
14 SOLUBILITY OF SODIUM CHLORIDE IN CAUSTIC SODA SOLUTIONS
15 DENSITY - CONCENTRATION TABLES FOR CAUSTIC SODA SOLUTIONS AT 600 F (15.5 0 C)
16 MATERIAL SELECTION CHART FOR CAUSTIC SODA HANDLING
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
Introduction High temperature shift Catalysts
Low temperature shift catalysts
Catalyst storage, handling, charging and discharging
Health and safety precautions
Reduction and start-up of high temperature shift catalysts
Operation of high temperature shift catalysts
Reduction and start-up of low temperature shift catalysts
Operation of low temperature shift catalysts
Avoiding Stress Corrosion Cracking of Carbon Low Alloy and Austenitic Stainl...Gerard B. Hawkins
Avoiding Stress Corrosion Cracking of Carbon Low Alloy and Austenitic Stainless Steels in Chloride and Caustic Environments
SYNOPSIS
This Maintenance Best Practice Guide is concerned with the performance of carbon and low alloy steels, and austenitic stainless steels, in chloride and caustic containing fluids. Those factors which are known to promote stress corrosion cracking are outlined, and service charts defining environmental boundaries for stress corrosion cracking in caustic and chloride containing fluids are presented.
General guidance on the avoidance of stress corrosion cracking is provided.
(AGRU) ACID GAS SOUR SHIFT: CASE STUDY IN REFINERY GAS TREATMENTGerard B. Hawkins
(AGRU) ACID GAS SOUR SHIFT: CASE STUDY IN REFINERY GAS TREATMENT; Case Study: #0978766GB/H
CASE STUDY OVERVIEW
Syn Gas Sour Shift: Process Flow Diagram
AGR: Acid Gas to VULCAN SYSTEMS Sour Gas Shift
DESIGN BASIS:
ACID GAS REACTOR CATALYST SPECIFICATION
SOUR SHIFT CASE
SHIFT REACTOR CATALYST SPECIFICATIONS
COS REACTOR CATALYST SPECIFICATIONS
SWEET SHIFT CASE
SHIFT REACTOR CATALYST SPECIFICATIONS
PERFORMANCE SIMULATION RESULTS
SOUR SHIFT SECTION
1 Cases Considered
2 Catalyst Used
3 Client Requirements
4 Oxygen and Olefins
5 HCN
6 NH3
7 Arsine
8 Input Data Sour Shift Unit
9 Activity (PROPRIETARY)
10 Results
ADIABATIC SWEET SHIFT SECTION: HTS Reactor followed by LTS Reactor
1 Catalyst Used
2 Inlet Operating Temperature HTS Reactor
3 Feed Flow Rate, Inlet Operating Pressure and Feed Composition HTS Reactor
4 Inlet Operating Conditions LTS Reactor
5 Client Requirements
6 Results: Standard Case as Presented to the Client
7 Results: Inlet Operating Pressure HTS Reactor = 25.2 bara
8 Results: Addition of 100 kmol/h N2
COS HYDROLYSIS SECTION FOR SWEET SHIFT CASE
1 Total Feed Flow Rate, Feed Composition, Direction of Flow, Inlet Operating Temperature, Inlet Operating Pressure
2 Inlet H2S and COS Levels
3 Equilibrium H2S and COS Levels (COS Hydrolysis Reaction)
4 Client Requirements
5 Results
H2S REMOVAL SECTION AFTER AGR UNIT
(2 Absorbent Beds (VULCAN VSG-EZ200) in Lead/Lag Arrangement)
1 Total Feed Flow Rate, Feed Composition, Direction of Flow, Inlet Operating Temperature, Inlet Operating Pressure
2 Inlet H2S and COS Levels
3 Client Requirements (All Cases)
4 Results
ISOTHERMAL SWEET SHIFT SECTION: Alternative Approach
VULCAN Simulation Input Data
1 Enthalpy method
2 Cases considered
3 Feed stream data
4 Kinetics
5 Catalyst
6 Catalyst Activity relative to standard
7 Catalyst size and packing details
8 Catalyst pressure drop parameters
9 Catalyst Volume
10 Standard die-off rate
11 BFW Rate
12 Vapor fraction
13 Steam Temperature
14 Steam Pressure
15 Boiling Model
16 Volumetric UA
Isothermal Shift Simulations Results
APPENDIX
Characteristics of Acid Gas Removal Technologies
Cast White Metal Bearings
1 SCOPE
2 BACKING MATERIAL
3 SURFACE
4 THICKNESS
5 CLEANING PROCEDURE
6 TINNING
7 WHITE METAL
8 BOND SOUNDNESS
9 WITNESSED INSPECTION
10 MACHINING
11 FINAL INSPECTION OF BOND FOR SEAL RINGS
APPENDIX
A - METHOD OF CALCULATING REFLECTANCE RATIO
Pumps for Hydrocarbon Service
1 SCOPE
2 HYDROCARBON PROPERTIES
2.1 General
2.2 Pure Hydrocarbons
2.3 Associated Compounds
2.4 Crude Oil
2.5 Toxicology
2.6 Cavitation
2.7 Velocity of Sound
3 FLAMMABILITY HAZARDS
3.1 General
3.2 Definitions
3.3 The Electrical Area Classification
4 CHOICE OF PUMP TYPE
5 LINE DIAGRAM (PROCESS)
6 LAYOUT
7 SHAFT SEALS
7.1 Selection
7.2 Engineering of Seals
8 CONSTRUCTION FEATURES
8.1 General
8.2 Effects of Low Density
9 MATERIALS OF CONSTRUCTION
9.1 Process Wetted Parts
9.2 Mechanical Components
9.3 Non Metallic’s
APPENDIX A - BARNARD & WEIR SEAL THEORY FIGURES
1 VAPOR PRESSURE OF HYDROCARBONS
2 VAPOR PRESSURE OF LIGHT HYDROCARBONS
3 VAPOR PRESSURE OF GASOLINES
4 SPECIFIC HEAT OF HYDROCARBON LIQUIDS
5 SPECIFIC GRAVITY OF OLEFINE, DI OLEFINES AND PARAFFINS
6 SPECIFIC GRAVITY OF AROMATICS
7 VISCOSITY - TEMPERATURE CHART FOR PARAFFINS, AROMATICS
AND PETROLEUM FRACTIONS
8 VISCOSITY - TEMPERATURE CHART FOR MINERAL LUBRICATING
OILS
TABLES
1 PURE HYDROCARBON PROPERTIES
2A CRUDE OILS PROPERTIES
2B NINIAN: PROPERTIES OF CRUDE OIL, NAPHTHAS AND KEROSENE
2C NINIAN: PROPERTIES OF GAS OILS AND RESIDUES
3 PURE HYROCARBON FLAMMABILITY PROPERTIES
BIBLIOGRAPHY
Pumps for Ammonium Nitrate Service
Engineering Design Guide: GBHE-EDG-MAC-1503
CONTENTS
1 SCOPE
SECTION ONE: INTEGRATION OF PUMPS INTO THE PROCESS
2 PROPERTIES OF FLUID
2.1 Decomposition
2.2 Combustion
2.3 Detonation
2.4 Deliquescence
2.5 Density
2.6 Viscosity
2.7 Vapor Pressure
2.8 Freezing Point
2.9 Specific Heat
2.10 Surface Tension
2.11 Thermal Conductivity
3 CALCULATION OF DUTY
3.1 Centrifugal Pumps
4 CHOICE OF PUMP TYPE
4.1 Centrifugal Pumps
4.2 Rotary Pumps
4.3 Reciprocating Pumps
5 LINE DIAGRAMS
5.1 Centrifugal Pumps with Mechanical Seals
5.2 Vertical Suspended Cantilever Shaft Pumps for
Melt Service
5.3 Horizontal Self-Priming Pumps
5.4 Reciprocating Pumps
5.5 Seal Water Supply System
6 LAYOUT
6.1 Vertical Cantilever Shaft Pumps - Tank Proportions
SECTION TWO: CONSTRUCTION FEATURES OF PUMPS
7 SEALS FOR CENTRIFUGAL PUMPS
7.1 Below 30% AN
7.2 30-45% AN
7.3 45-90% AN
7.4 Above 90% AN
8 PACKED GLANDS FOR RECIPROCATING PUMPS
8.1 Below 90% AN
9 SEAL WATER SUPPLY SYSTEMS
10 CONSTRUCTION FEATURES OF CENTRIFUGAL PUMPS
10.1 Casing
10.2 Rotor
10.3 Bearing Lubrication
10.4 Coupling
10.5 Baseplate
11 CONSTRUCTION FEATURES OF VERTICAL CANTILEVER SHAFT IMMERSED PUMPS
11.1 Motor
11.2 Insulation and Jacketing
11.3 Rotor
11.4 Bearing Lubrication
11.5 Preservation
12 CONSTRUCTION FEATURES OF RECIPROCATING PLUNGER PUMPS
12.1 Speed Limits
12.2 Casing and Gearbox
12.3 Couplings
13 MATERIALS OF CONSTRUCTION
13.1 Recommended Materials
13.2 Forbidden Materials
APPENDIX A: BEARING LUBRICANTS
FIGURES
2.5.1 DENSITY OF AMMONIUM NITRATE SOLUTIONS
2.5.2 DENSITY OF AMMONIUM NITRATE SOLUTIONS
2.6 KINEMATIC VISCOSITY OF AMMONIUM NITRATE SOLUTIONS
2.7.1 WATER VAPOR PRESSURE ABOVE AMMONIUM NITRATE SOLUTIONS
2.7.2 AMMONIA VAPOR PRESSURE FOR AM!AMMONIUM NITRATE MELT
2.8 FREEZING POINT OF AMMONIUM NITRATE SOLUTIONS
2.9 SPECIFIC HEAT OF AMMONIUM NITRATE SOLUTIONS
4 SELECTION OF PUMP TYPE
5. 1 RECOMMENDED LINE DIAGRAM CENTRIFUGAL PUMPS WITH MECHANICAL SEALS
5.2 RECOMMENDED LINE DIAGRAM: VERTICAL SUSPENDED CANTILEVER PUMPS
5.3 RECOMMENDED LINE DIAGRAM: HORIZONTAL SELF
PRIMING PUMPS
5.4 RECOMMENDED LINE DIAGRAM: RECIPROCATING PLUNGER PUMPS
5.5 RECOMMENDED LINE DIAGRAM SEAL: WATER PUMPS AND INJECTION PUMP SYSTEMS
7.2 TYPICAL ARRANGEMENT OF SEAL WITH NO INJECTION FLUSH
7.3 TYPICAL ARRANGEMENT OF CRANE TYPE 52B WITH 'J' SEAT INCORPORATING TETRALIPS INBOARD AND OUTBOARD
7.4 TYPICAL ARRANGEMENT OF LABYRINTH SEAL FOR VERTICAL SUSPENDED CANTILEVER SHAFT PUMPS
8.1 TYPICAL ARRANGEMENT OF SOFT PACKED GLAND FOR RECIPROCATING PLUNGER PUMPS FOR DELIVERY PRESSURES UP TO 10 BAR G.
12 TEMPERATURES ATTAINED ON DISSOLUTION OF ANHYDROUS CAUSTIC SODA
TABLES
13.1 MATERIALS OF CONSTRUCTION CENTRIFUGAL PUMPS
13.2 MATERIALS OF CONSTRUCTION VERTICAL CANTILEVER
SHAFT IMMERSED PUMPS
13.3 MATERIALS OF CONSTRUCTION RECIPROCATING PLUNGER PUMPS
Introduction
VULCAN Series VHT-S101
Catalyst storage, handling, charging
Health and safety precautions
Start-up of VHT-S101 hydrogenation catalyst
Operation of VHT-S101 hydrogenation catalyst
Shut-down of VHT-S101 hydrogenation catalyst
Sulfiding of hydrodesulfurization catalysts
Catalyst Discharge
Data Sources For Calculating Chemical Reaction EquilibriaGerard B. Hawkins
Data Sources For Calculating Chemical Reaction Equilibria
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
4 BACKGROUND TO THEORY
5 BIBLIOGRAPHY
Fixed Bed Reactor Scale-up Checklist
The purpose of this checklist is to identify the stages and potential problems associated with the scale up of fixed bed reactors from the drawing board to the full scale plant, and to determine how they should be checked.
The checking can be done using various methods. These are:
• Literature data.
• Lab testing.
• Calculation.
• Modeling.
• Semi-tech testing.
• Piloting or Sidestream testing.
Identifying the stages that need to be addressed for a particular catalyst/reactor development will help in estimating the time needed for the development of the reactor
"SEDIMENTATION"
INTRODUCTION - THE PHENOMENON OF SEDIMENTATION
Sedimentation is the physical process whereby solid particles, of greater density than their suspending medium, will tend to separate into regions of higher concentration under the influence of gravity. As a solids/liquids separation technique it therefore possesses the great advantage of utilizing a natural, and therefore costless, driving force. This section of the suspension processing Guide is Intended to provide an Introduction to the science of the subject, and the means to judge where and how best to exploit sedimentation as a separation (or other processing) technique.
As a scientific discipline the subject of sedimentation is vast with perspectives ranging from the field of chemical engineering through to theoretical physics being covered In the literature [1-11]. Good reviews of the subject, with a bias towards the engineering aspects, have been written by Fitch and Koz [12, 13]. A short summary of some of the more relevant contributions from the literature is also provided in GBHE-SPG-PEG-302 “Basic Principles & Test Methods”, of the Suspensions Processing Guides.
.
The sedimentation process is traditionally divided into ..."
Mixing of Immiscible Liquids
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
4 EQUIPMENT
4.1 Agitated Tanks
4.2 Flow Mixers
4.3 'High Shear' Mixers
5 SYSTEM PHYSICAL PROPERTIES
5.1 Density
5.2 Viscosity
5.3 Interfacial Tension
6 STIRRED VESSELS
6.1 Design for Complete Dispersion
6.2 Prediction of Phase Inversion
6.3 Design for Mass Transfer
6.4 Design for Dispersed Phase Mixing
6.5 Hold-Up in Continuous Vessels
7 FLOW MIXERS
7.1 Design for Turbulent Conditions
7.2 Design for Laminar Conditions
TABLES
1 REYNOLDS NUMBER RANGES
FIGURES
1 STANDARD TANK CONFIGURATION
2 EXPERIMENTAL RELATIONSHIP BETWEEN MASS
TRANSFER COEFFICIENT AND POWER DENSITY
Design and Operation of NHT Strippers to Protect Catalytic Reformers Gerard B. Hawkins
Common Reformer Problems
Purpose of NHT Stripper
Typical Design
Instrumentation of NHT Stripper
Other Design Issues
Indications of Problems in the NHT
Response to Reformer Upsets
How to Use the GBHE Mixing Guides
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
4 THE MIXING GUIDES
4.1 Mixing Guides
4.2 GBHE Mixing and Agitation Manual
5 DEVICE SELECTION
6 MIXING QUESTIONNAIRE
6.1 What is being mixed?
6.2 Why is it being mixed?
6.3 How is it to be mixed?
6.4 Is Heat Transfer Important?
6.5 Is Mixing Time Important?
6.6 Is Inventory Important?
6.7 Is Subsequent Phase Separation Important?
6.8 What Quantities?
6.9 What are the Selection Criteria?
6.10 What Data are required?
7 BASICS
7.1 Bulk Movement
7.2 Shear and Elongation
7.3 Turbulent Diffusion
7.4 Molecular Diffusion
7.5 Mixing Mechanisms
APPENDICES
A ROTATING MIXING DEVICES
B MIXING DEVICES WITHOUT MOVING PARTS
Similar to VULCAN Catalytic Reaction Guide - (106) Heterogeneous Reaction Mechanisms (20)
Pressure Relief Systems Vol 2
Causes of Relief Situations
This Volume 2 is a guide to the qualitative identification of common causes of overpressure in process equipment. It cannot be exhaustive; the process engineer and relief systems team should look for any credible situation in addition to those given in this Part which could lead to a need for pressure relief (a relief situation).
Pressure Relief Systems
BACKGROUND TO RELIEF SYSTEM DESIGN Vol.1 of 6
The Guide has been written to advise those involved in the design and engineering of pressure relief systems. It takes the user from the initial identification of potential causes of overpressure or under pressure through the process design of relief systems to the detailed mechanical design. "Hazard Studies" and quantitative hazards analysis are not described; these are seen as complementary activities. Typical users of the Guide will use some Parts in detail and others in overview.
GAS DISPERSION - A Definitive Guide to Accidental Releases of Heavy GasesGerard B. Hawkins
GAS DISPERSION - A Definitive Guide to Accidental Releases of Heavy Gases
This Process Safety Guide has been written with the aim of assisting process engineers, hazard analysts and environmental advisers in carrying out gas dispersion calculations. The Guide aims to provide assistance by:
• Improving awareness of the range of dispersion models available within GBHE, and providing guidance in choosing the most appropriate model for a particular application.
• Providing guidance to ensure that source terms and other model inputs are correctly specified, and the models are used within their range of applicability.
• Providing guidance to deal with particular topics in gas dispersion such as dense gas dispersion, complex terrain, and modeling the chemistry of oxides of nitrogen.
• Providing general background on air quality and dispersion modeling issues such as meteorology and air quality standards.
• Providing example calculations for real practical problems.
SCOPE
The gas dispersion guide contains the following Parts:
1 Fundamentals of meteorology.
2 Overview of air quality standards.
3 Comparison between different air quality models.
4 Designing a stack.
5 Dense gas dispersion.
6 Calculation of source terms.
7 Building wake effects.
8 Overview of the chemistry of the oxides of nitrogen.
9 Overview of the ADMS complex terrain module.
10 Overview of the ADMS deposition module.
11 ADMS examples.
12 Modeling odorous releases.
13 Bibliography of useful gas dispersion books and reports.
14 Glossary of gas dispersion modeling terms.
Appendix A : Modeling Wind Generation of Particulates.
APPENDIX B TABLE OF PROPERTY VALUES FOR SPECIFIC CHEMICALS
Calculation of an Ammonia Plant Energy Consumption: Gerard B. Hawkins
Calculation of an Ammonia Plant Energy Consumption:
Case Study: #06023300
Plant Note Book Series: PNBS-0602
CONTENTS
0 SCOPE
1 CALCULATION OF NATURAL GAS PROCESS FEED CONSUMPTION
2 CALCULATION OF NATURAL GAS PROCESS FUEL CONSUMPTION
3 CALCULATION OF NATURAL GAS CONSUMPTION FOR PILOT BURNERS OF FLARES
4 CALCULATION OF DEMIN. WATER FROM DEMIN. UNIT
5 CALCULATION OF DEMIN. WATER TO PACKAGE BOILERS
6 CALCULATION OF MP STEAM EXPORT
7 CALCULATION OF LP STEAM IMPORT
8 DETERMINATION OF ELECTRIC POWER CONSUMPTION
9 DETERMINATION OF THE TOTAL ENERGY CONSUMPTION OF THE AMMONIA PLANT ISBL
10 ADJUSTMENT OF ELECTRIC POWER CONSUMPTION FOR TEST RUN CONDITIONS
11 CALCULATION OF AMMONIA SHARE IN MP STEAM CONSUMPTION IN UTILITIES
12 CALCULATION OF AMMONIA SHARE IN ELECTRIC POWER CONSUMPTION IN UTILITIES
13 DETERMINATION OF THE TOTAL ENERGY CONSUMPTION OF THE AMMONIA PLANT OSBL
14 DETERMINATION OF THE TOTAL ENERGY CONSUMPTION OF THE AMMONIA PLANT
Ammonia Plant Technology
Pre-Commissioning Best Practices
GBHE-APT-0102
PICKLING & PASSIVATION
CONTENTS
1 PURPOSE OF THE WORK
2 CHEMICAL CONCEPT
3 TECHNICAL CONCEPT
4 WASTES & SAFETY CONCEPT
5 TARGET RESULTS
6 THE GENERAL CLEANING SEQUENCE MANAGEMENT
6.6.1 Pre-cleaning or “Physical Cleaning
6.6.2 Pre-rinsing
6.6.3 Chemical Cleaning
6.6.4 Critical Factors in Cleaning Success
6.6.5 Rinsing
6.6.6 Inspection and Re-Cleaning, if Necessary
7 Systems to be treated by Pickling/Passivation
Ammonia Plant Technology
Pre-Commissioning Best Practices
Piping and Vessels Flushing and Cleaning Procedure
CONTENTS
1 Scope
2 Aim/purpose
3 Responsibilities
4 Procedure
4.1 Main cleaning methods
4.1.1 Mechanical cleaning
4.1.2 Cleaning with air
4.1.3 Cleaning with steam (for steam networks only)
4.1.4 Cleaning with water
4.2 Choice of the cleaning method
4.3 Cleaning preparation
4.4 Protection of the devices included in the network
4.5 Protection of devices in the vicinity of the network
4.6 Water flushing procedure
4.6.1 Specific problems of water flushing
4.6.2 Preparation for water flushing
4.6.3 Performing a water flush
4.6.4 Cleanliness criteria
4.7 Air blowing procedure
4.7.1 Specific problems of air blowing
4.7.2 Preparation for air blowing
4.7.3 Performing air blowing
4.7.4 Cleanliness checks
4.8 Steam blowing procedure
4.8.1 Specific problems of steam blowing
4.8.2 Preparation for steam blowing
4.8.3 Performing steam blowing
4.8.4 Cleanliness checks
4.9 Chemical cleaning procedure
4.9.1 Specific problems of cleaning with a chemical solution
4.9.2 Preparation for chemical cleaning
4.9.3 Performing a chemical cleaning
4.9.4 Cleanliness criteria
4.10 Re-assembly - general guideline
4.11 Preservation of flushed piping
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS Gerard B. Hawkins
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS
CONTENTS
1 INTRODUCTION
1.1 Purpose
1.2 Scope of this Guide
1.3 Use of the Guide
2 ENVIRONMENTAL ISSUES
2.1 Principal Concerns
2.2 Mechanisms for Ozone Formation
2.3 Photochemical Ozone Creation Potential
2.4 Health and Environmental Effects
2.5 Air Quality Standards for Ground Level Concentrations of Ozone, Targets for Reduction of VOC Discharges and Statutory Discharge Limits
3 VENTS REDUCTION PHILOSOPHY
3.1 Reduction at Source
3.2 End-of-pipe Treatment
4 METHODOLOGY FOR COLLECTION & ASSESSMENT OF PROCESS FLOW DATA
4.1 General
4.2 Identification of Vent Sources
4.3 Characterization of Vents
4.4 Quantification of Process Vent Flows
4.5 Component Flammability Data Collection
4.6 Identification of Operating Scenarios
4.7 Quantification of Flammability Characteristics for Combined Vents
4.8 Identification, Quantification and Assessment of Possibility of Air Ingress Routes
4.9 Tabulation of Data
4.10 Hazard Study and Risk Assessment
4.11 Note on Aqueous / Organic Wastes
4.12 Complexity of Systems
4.13 Summary
5 SAFE DESIGN OF VENT COLLECTION HEADER SYSTEMS
5.1 General
5.2 Process Design of Vent Headers
5.3 Liquid in Vent Headers
5.4 Materials of Construction
5.5 Static Electricity Hazard
5.6 Diversion Systems
5.7 Snuffing Systems
6 SAFE DESIGN OF THERMAL OXIDISERS
6.1 Introduction
6.2 Design Basis
6.3 Types of High Temperature Thermal Oxidizer
6.4 Refractories
6.5 Flue Gas Treatment
6.6 Control and Safety Systems
6.7 Project Program
6.8 Commissioning
6.9 Operational and Maintenance Management
APPENDICES
A GLOSSARY
B FLAMMABILITY
C EXAMPLE PROFORMA
D REFERENCES
DOCUMENTS REFERRED TO IN THIS PROCESS GUIDE
TABLE
1 PHOTOCHEMICAL OZONE CREATION POTENTIAL REFERENCED
TO ETHYLENE AS UNITY
FIGURES
1 SCHEMATIC OF TYPICAL VENT COLLECTION AND THERMAL OXIDIZER SYSTEM
2 TYPICAL KNOCK-OUT POT WITH LUTED DRAIN
3 SCHEMATIC OF DIVERSION SYSTEM
4 CONVENTIONAL VERTICAL THERMAL OXIDIZER
5 CONVENTIONAL OXIDIZER WITH INTEGRAL WATER SPARGER
6 THERMAL OXIDIZER WITH STAGED AIR INJECTION
7 DOWN-FIRED UNIT WITH WATER BATH QUENCH
8 FLAMELESS THERMAL OXIDATION UNIT
9 THERMAL OXIDIZER WITH REGENERATIVE HEAT RECOVERY
10 TYPICAL PROJECT PROGRAM
11 TYPICAL FLAMMABILITY DIAGRAM
12 EFFECT OF DILUTION WITH AIR
13 EFFECT OF DILUTION WITH AIR ON 100 Rm³ OF FLAMMABLE GAS
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...Gerard B. Hawkins
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF AQUEOUS ORGANIC EFFLUENT STREAMS
CONTENTS
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
3.1 IPU
3.2 AOS
3.3 BODs
3.4 COD
3.5 TOC
3.6 Toxicity
3.7 Refractory Organics/Hard COD
3.8 Heavy Metals
3.9 EA
3.10 Biological Treatment Terms
3.11 BATNEEC
3.12 BPEO
3.13 EQS/LV
3.14 IPC
3.15 VOC
3.16 F/M Ratio
3.17 MLSS
3.18 MLVSS
4 DESIGN/ECONOMIC GUIDELINES
5 EUROPEAN LEGISLATION
5.1 General
5.2 Integrated Pollution Control (IPC)
5.3 Best Available Techniques Not Entailing Excessive Costs (BATNEEC)
5.4 Best Practicable Environmental Option (BPEO)
5.5 Environmental Quality Standards(EQS)
6 IPU EXIT CONCENTRATION
7 SITE/LOCAL REQUIREMENTS
8 PROCESS SELECTION PROCEDURE
8.1 Waste Minimization Techniques (WMT)
8.2 AOS Stream Definition
8.3 Technical Check List
8.4 Preliminary Selection of Suitable Technologies
8.5 Process Sequences
8.6 Economic Evaluation
8.7 Process Selection
APPENDICES
A DIRECTIVE 76/464/EEC - LIST 1
B DIRECTIVE 76/464/EEC - LIST 2
C THE EUROPEAN COMMISSION PRIORITY CANDIDATE LIST
D THE UK RED LIST
E CURRENT VALUES FOR EUROPEAN COMMUNITY ENVIRONMENTAL QUALITY STANDARDS AND CORRESPONDING LIMIT VALUES
F ESTABLISHED TECHNOLOGIES
G EMERGING TECHNOLOGY
H PROPRIETARY/LESS COMMON TECHNOLOGIES
J COMPARATIVE COST DATA
PRACTICAL GUIDE ON THE REDUCTION OF DISCHARGES TO ATMOSPHERE OF VOLATILE ORGA...Gerard B. Hawkins
PRACTICAL GUIDE ON THE REDUCTION OF DISCHARGES TO ATMOSPHERE OF VOLATILE ORGANIC COMPOUNDS (VOCs)
FOREWORD
CONTENTS
1 INTRODUCTION
2 THE NEED FOR VOC CONTROL
3 CONTROL AT SOURCE
3.1 Choice or Solvent
3.2 Venting Arrangements
3.3 Nitrogen Blanketing
3.4 Pump Versus Pneumatic Transfer
3.5 Batch Charging
3.6 Reduction of Volumetric Flow
3.7 Stock Tank Design
4 DISCHARGE MEASUREMENT
4.1 By Inference or Calculation
4.2 Flow Monitoring Equipment
4.3 Analytical Instruments
4.4 Vent Emissions Database
5 ABATEMENT TECHNOLOGY
5.1 Available Options
5.2 Selection of Preferred Option
5.3 Condensation
5.4 Adsorption
5.5 Absorption
5.6 Thermal Incineration
5.7 Catalytic Oxidation
5.8 Biological Filtration
5.9 Combinations of Process technologies
5.10 Processes Under Development
6 GLOSSARY OF TERMS
7 REFERENCES
Appendix 1. Photochemical Ozone Creation Potentials
Appendix 2. Examples of Adsorption Preliminary Calculations
Appendix 3. Example of Thermal Incineration Heat and Mass Balance
Appendix 4. Cost Correlations
EMERGENCY ISOLATION OF CHEMICAL PLANTS
CONTENTS
1 Introduction
2 When should Emergency Isolation Valves be Installed
3 Emergency Isolation Valves and Associated Equipment
3.1 Installations on existing plant
3.2 Actuators
3.3 Power to close or power to open
3.4 The need for testing
3.5 Hand operated Emergency Valves
3.6 The need to stop pumps in an emergency
3.7 Location of Operating Buttons
3.8 Use of control valves for Isolation
4 Detection of Leaks and Fires
5 Precautions during Maintenance
6 Training Operators to use Emergency Isolation Valves
7 Emergency Isolation when no remotely operated valve is available
References
Glossary
Appendix I Some Fires or Serious Escapes of Flammable Gases or Liquids that could have been controlled by Emergency Isolation Valves
Appendix II Some typical Installations
Amine Gas Treating Unit - Best Practices - Troubleshooting Guide Gerard B. Hawkins
Amine Gas Treating Unit Best Practices - Troubleshooting Guide for H2S/CO2 Amine Systems
Contents
Process Capabilities for gas treating process
Typical Amine Treating
Typical Amine System Improvements
Primary Equipment Overview
Inlet Gas Knockout
Absorber
Three Phase Flash Tank
Lean/Rich Heat Exchanger
Regenerator
Filtration
Amine Reclaimer
Operating Difficulties Overview
Foaming
Failure to Meet Gas Specification
Solvent Losses
Corrosion
Typical Amine System Improvements
Degradation of Amines and Alkanolamines during Sour Gas Treating
APPENDIX
Best Practices - Troubleshooting Guide
State of ICS and IoT Cyber Threat Landscape Report 2024 previewPrayukth K V
The IoT and OT threat landscape report has been prepared by the Threat Research Team at Sectrio using data from Sectrio, cyber threat intelligence farming facilities spread across over 85 cities around the world. In addition, Sectrio also runs AI-based advanced threat and payload engagement facilities that serve as sinks to attract and engage sophisticated threat actors, and newer malware including new variants and latent threats that are at an earlier stage of development.
The latest edition of the OT/ICS and IoT security Threat Landscape Report 2024 also covers:
State of global ICS asset and network exposure
Sectoral targets and attacks as well as the cost of ransom
Global APT activity, AI usage, actor and tactic profiles, and implications
Rise in volumes of AI-powered cyberattacks
Major cyber events in 2024
Malware and malicious payload trends
Cyberattack types and targets
Vulnerability exploit attempts on CVEs
Attacks on counties – USA
Expansion of bot farms – how, where, and why
In-depth analysis of the cyber threat landscape across North America, South America, Europe, APAC, and the Middle East
Why are attacks on smart factories rising?
Cyber risk predictions
Axis of attacks – Europe
Systemic attacks in the Middle East
Download the full report from here:
https://sectrio.com/resources/ot-threat-landscape-reports/sectrio-releases-ot-ics-and-iot-security-threat-landscape-report-2024/
Software Delivery At the Speed of AI: Inflectra Invests In AI-Powered QualityInflectra
In this insightful webinar, Inflectra explores how artificial intelligence (AI) is transforming software development and testing. Discover how AI-powered tools are revolutionizing every stage of the software development lifecycle (SDLC), from design and prototyping to testing, deployment, and monitoring.
Learn about:
• The Future of Testing: How AI is shifting testing towards verification, analysis, and higher-level skills, while reducing repetitive tasks.
• Test Automation: How AI-powered test case generation, optimization, and self-healing tests are making testing more efficient and effective.
• Visual Testing: Explore the emerging capabilities of AI in visual testing and how it's set to revolutionize UI verification.
• Inflectra's AI Solutions: See demonstrations of Inflectra's cutting-edge AI tools like the ChatGPT plugin and Azure Open AI platform, designed to streamline your testing process.
Whether you're a developer, tester, or QA professional, this webinar will give you valuable insights into how AI is shaping the future of software delivery.
Epistemic Interaction - tuning interfaces to provide information for AI supportAlan Dix
Paper presented at SYNERGY workshop at AVI 2024, Genoa, Italy. 3rd June 2024
https://alandix.com/academic/papers/synergy2024-epistemic/
As machine learning integrates deeper into human-computer interactions, the concept of epistemic interaction emerges, aiming to refine these interactions to enhance system adaptability. This approach encourages minor, intentional adjustments in user behaviour to enrich the data available for system learning. This paper introduces epistemic interaction within the context of human-system communication, illustrating how deliberate interaction design can improve system understanding and adaptation. Through concrete examples, we demonstrate the potential of epistemic interaction to significantly advance human-computer interaction by leveraging intuitive human communication strategies to inform system design and functionality, offering a novel pathway for enriching user-system engagements.
Slack (or Teams) Automation for Bonterra Impact Management (fka Social Soluti...Jeffrey Haguewood
Sidekick Solutions uses Bonterra Impact Management (fka Social Solutions Apricot) and automation solutions to integrate data for business workflows.
We believe integration and automation are essential to user experience and the promise of efficient work through technology. Automation is the critical ingredient to realizing that full vision. We develop integration products and services for Bonterra Case Management software to support the deployment of automations for a variety of use cases.
This video focuses on the notifications, alerts, and approval requests using Slack for Bonterra Impact Management. The solutions covered in this webinar can also be deployed for Microsoft Teams.
Interested in deploying notification automations for Bonterra Impact Management? Contact us at sales@sidekicksolutionsllc.com to discuss next steps.
Generating a custom Ruby SDK for your web service or Rails API using Smithyg2nightmarescribd
Have you ever wanted a Ruby client API to communicate with your web service? Smithy is a protocol-agnostic language for defining services and SDKs. Smithy Ruby is an implementation of Smithy that generates a Ruby SDK using a Smithy model. In this talk, we will explore Smithy and Smithy Ruby to learn how to generate custom feature-rich SDKs that can communicate with any web service, such as a Rails JSON API.
Smart TV Buyer Insights Survey 2024 by 91mobiles.pdf91mobiles
91mobiles recently conducted a Smart TV Buyer Insights Survey in which we asked over 3,000 respondents about the TV they own, aspects they look at on a new TV, and their TV buying preferences.
DevOps and Testing slides at DASA ConnectKari Kakkonen
My and Rik Marselis slides at 30.5.2024 DASA Connect conference. We discuss about what is testing, then what is agile testing and finally what is Testing in DevOps. Finally we had lovely workshop with the participants trying to find out different ways to think about quality and testing in different parts of the DevOps infinity loop.
UiPath Test Automation using UiPath Test Suite series, part 4DianaGray10
Welcome to UiPath Test Automation using UiPath Test Suite series part 4. In this session, we will cover Test Manager overview along with SAP heatmap.
The UiPath Test Manager overview with SAP heatmap webinar offers a concise yet comprehensive exploration of the role of a Test Manager within SAP environments, coupled with the utilization of heatmaps for effective testing strategies.
Participants will gain insights into the responsibilities, challenges, and best practices associated with test management in SAP projects. Additionally, the webinar delves into the significance of heatmaps as a visual aid for identifying testing priorities, areas of risk, and resource allocation within SAP landscapes. Through this session, attendees can expect to enhance their understanding of test management principles while learning practical approaches to optimize testing processes in SAP environments using heatmap visualization techniques
What will you get from this session?
1. Insights into SAP testing best practices
2. Heatmap utilization for testing
3. Optimization of testing processes
4. Demo
Topics covered:
Execution from the test manager
Orchestrator execution result
Defect reporting
SAP heatmap example with demo
Speaker:
Deepak Rai, Automation Practice Lead, Boundaryless Group and UiPath MVP
Dev Dives: Train smarter, not harder – active learning and UiPath LLMs for do...UiPathCommunity
💥 Speed, accuracy, and scaling – discover the superpowers of GenAI in action with UiPath Document Understanding and Communications Mining™:
See how to accelerate model training and optimize model performance with active learning
Learn about the latest enhancements to out-of-the-box document processing – with little to no training required
Get an exclusive demo of the new family of UiPath LLMs – GenAI models specialized for processing different types of documents and messages
This is a hands-on session specifically designed for automation developers and AI enthusiasts seeking to enhance their knowledge in leveraging the latest intelligent document processing capabilities offered by UiPath.
Speakers:
👨🏫 Andras Palfi, Senior Product Manager, UiPath
👩🏫 Lenka Dulovicova, Product Program Manager, UiPath
Securing your Kubernetes cluster_ a step-by-step guide to success !KatiaHIMEUR1
Today, after several years of existence, an extremely active community and an ultra-dynamic ecosystem, Kubernetes has established itself as the de facto standard in container orchestration. Thanks to a wide range of managed services, it has never been so easy to set up a ready-to-use Kubernetes cluster.
However, this ease of use means that the subject of security in Kubernetes is often left for later, or even neglected. This exposes companies to significant risks.
In this talk, I'll show you step-by-step how to secure your Kubernetes cluster for greater peace of mind and reliability.
Transcript: Selling digital books in 2024: Insights from industry leaders - T...BookNet Canada
The publishing industry has been selling digital audiobooks and ebooks for over a decade and has found its groove. What’s changed? What has stayed the same? Where do we go from here? Join a group of leading sales peers from across the industry for a conversation about the lessons learned since the popularization of digital books, best practices, digital book supply chain management, and more.
Link to video recording: https://bnctechforum.ca/sessions/selling-digital-books-in-2024-insights-from-industry-leaders/
Presented by BookNet Canada on May 28, 2024, with support from the Department of Canadian Heritage.
Connector Corner: Automate dynamic content and events by pushing a buttonDianaGray10
Here is something new! In our next Connector Corner webinar, we will demonstrate how you can use a single workflow to:
Create a campaign using Mailchimp with merge tags/fields
Send an interactive Slack channel message (using buttons)
Have the message received by managers and peers along with a test email for review
But there’s more:
In a second workflow supporting the same use case, you’ll see:
Your campaign sent to target colleagues for approval
If the “Approve” button is clicked, a Jira/Zendesk ticket is created for the marketing design team
But—if the “Reject” button is pushed, colleagues will be alerted via Slack message
Join us to learn more about this new, human-in-the-loop capability, brought to you by Integration Service connectors.
And...
Speakers:
Akshay Agnihotri, Product Manager
Charlie Greenberg, Host
1. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
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GBH Enterprises, Ltd.
VULCAN SYSTEMS
HETEROGENEOUS CATALYST
APPLICATIONS
Catalytic Reaction
Guide: (106)
Heterogeneous Reaction
Mechanisms
Process Disclaimer
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.
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HETEROGENEOUS REACTION CHEMISTRY
CONTENTS
0 HETEROGENEOUS POWDERED CATALYSTS
1 CHOICE OF METAL
2 CHOICE OF SUPPORT
3 MASS TRANSPORT AND REACTOR DESIGN
4 CATALYST DESIGN
5 CATALYST SEPARATION, FILTRATION
6 PROCESS ECONOMICS
6.1 Activated Carbon
6.2 Alumina
6.3 Calcium Carbonate
6.4 Barium Sulfate
6.5 Other Powdered Supports
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VULCAN Catalytic Reaction Guide
Chemistry Reactions
1. Hydrogenation 1-55
1.1 C-C Multiple Bonds 1-7
1.2 Aromatic Ring Compounds 8-14
1.3 Carbonyl Compounds 15-25
1.4 Nitro and Nitroso Compounds 28-35
1.5 Halonitroaromatics 36
1.6 Reductive Alkylation's 37 & 38
1.7 Imines 39-41
1.8 Nitriles 42-47
1.9 Oximes 48-49
1.10 Hydrogenolysis 50-54
1.11 Other 55
2. Dehydrogenation 56-60
3. Hydroformylation 61& 62
4. Carbonylation 63-68
5. Decarbonylation 69
6. Hydrosilylation 70 & 71
7. Cross Coupling 72-96
7.1 Heck 72-75
7.2 Suzuki 76
7.3 Buckwald-Hartwig 77 & 78
7.4 Organometallics 79-83
7.5 Sonogashira 84-87
7.6 Other 88-96
8. Cycloproportion 97
9. Selective Oxidation 98-106
9.1 Alcohols to Carbonyls 98-102
9.2 Dihydoxylation of Alkenes 103
9.3 Oxygen Insertion Reactions 104
9.4 Others 105-106
Catalytic Reaction Guide: (106) Heterogeneous Reaction Mechanisms
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0 HETEROGENEOUS POWDERED CATALYSTS
Supported precious metal catalysts are used for a variety of reactions
including hydrogenation, dehydrogenation, hydrogenolysis, oxidation,
disproportionation and isomerization. Many important organic
transformations are completed via catalytic hydrogenation. A large number
of these reactions are carried out in the liquid phase, using batch type
slurry processes and a supported heterogeneous platinum group metal
catalyst. Platinum group metal catalysts will reduce most organic
functional groups.
The selection of a catalyst or catalyst system for a new catalytic process
requires many important technical and economic considerations. The
process of selecting a precious metal catalyst can be broken down into
components. Key catalyst properties are high activity, high selectivity, high
recycle capability and filterability. Important process components include
choice of catalytic metal, choice of support, reactor design, heat and mass
transport, catalyst design, catalyst separation, and spent catalyst recovery
and refining.
1 CHOICE OF METAL
Catalyst performance is determined mainly by the precious metal
component. A metal is chosen based both on its ability to complete the
desired reaction and its inability to complete an unwanted reaction.
Palladium is typically the preferred metal for hydrogenation of acetylenes,
olefins, carbonyls in aromatic aldehydes and ketones, aromatic and
aliphatic nitro compounds, reductive alkylation, hydrogenolysis and
hydrodehalogenation reactions. Platinum is typically the preferred metal
for selective hydrogenation of halonitroaromatics and reductive
alkylations. Rhodium is used for the hydrogenation of aromatic rings and
olefins while ruthenium is used for the hydrogenation of aromatic rings and
aliphatic aldehydes and ketones.
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2 CHOICE OF SUPPORT
In general, a catalyst support should allow for a high degree of metal
dispersion. The choice of support is largely determined by the nature of
the reaction system. A support should be stable under reaction and
regeneration conditions, and not adversely interact with solvent, reactants
or reaction products. Common powdered supports include activated
carbon, alumina, silica, silica-alumina, carbon black, TiO2, ZrO2, CaCO3,
and BaSO4. The majority of precious metal catalysts are supported on
either carbon or alumina. Information on common powdered supports is
summarized on Page 5.
Figure 1. The Effect of Catalyst Support on Platinum Dispersion
A support can affect catalyst activity, selectivity, recycling, refining,
material handling and reproducibility. Critical properties of a support
include surface area, pore volume, pore size distribution, particle size,
attrition resistance, acidity, basicity, impurity levels, and the ability to
promote metal support interactions. Metal dispersion increases with
support surface area. The effect of increasing support surface area on
metal dispersion for a series of platinum catalysts prepared on activated
carbon, silica, alumina, carbon black, and graphite supports is shown in
Figure 1.
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Support porosity affects metal dispersion and distribution, metal sintering
resistance, and intraparticle diffusion of reactants, products and poisons.
Smaller support particle size increases catalytic activity but decreases
filterability. A support should have desirable mechanical properties,
attrition resistance and hardness. An attrition resistant support allows for
multiple catalyst recycling and rapid filtration. Support impurities may
deactivate the metal and enhance catalyst selectivity.
The concentration of precious metal deposited on a support is typically
between 1 and 10 weight percent. Practical metal concentration limits are
between 0.1 and 20 weight percent for activated carbon, and between 0.1
and 5 weight percent for alumina. Relative catalyst activity will generally
increase with decreasing metal concentration at constant metal loading.
3 MASS TRANSPORT AND REACTOR DESIGN
Liquid phase hydrogenations employing heterogeneous catalysts are
multiple phase (gas-liquid-solid) systems containing concentration and
temperature gradients. In order to obtain a true measure of catalytic
performance, heat transfer resistances and mass transfer resistances
need to be understood and minimized. Mass transfer effects can alter
reaction times, reaction selectivity, and product yields. The intrinsic rate of
a chemical reaction can be totally obscured when a reaction is mass
transport limited. For reaction to take place in a multi-phase system,
the following steps must occur: 1) transport of the gaseous reactant into
the liquid phase, 2) transport
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Figure 2. Concentration Gradients in Gas/Liquid/Solid Catalytic system
of the dissolved gaseous reactant through the bulk liquid to the surface of
a catalyst particle, 3) transport of the dissolved substrate through the liquid
to the surface of the catalyst particle, 4) diffusion of the reactants into the
pore structure of the catalyst particle, 5) chemisorption of reactants,
chemical reaction, desorption of products, and 6) diffusion of the products
out of the pore structure of the catalyst particle (Figure 2). Detailed rate
expressions have been developed for such systems.
Rate of reaction will be affected by different process variables, depending
on which step is rate-limiting. A reaction controlled by gas-liquid mass
transport, i.e. the rate of mass transport of the gaseous reactant into the
liquid, will be influenced mainly by reactor design, hydrogen pressure, and
agitation rate. A reaction controlled by liquid-solid mass transport, i.e. the
rate of mass transport of either gaseous reactant or substrate from the
bulk liquid to the external surface of the catalyst particle, will be influenced
mainly by gas or substrate concentration, weight of catalyst in reactor,
agitation and catalyst particle size distribution.
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A reaction controlled by pore diffusion-chemical reaction, i.e. the rate of
reactant diffusion and chemical reaction within the catalyst particle, will be
influenced mainly by temperature, reactant concentration, percent metal
on the support, number and location of active catalytic sites, catalyst
particle size distribution and pore structure. To evaluate and rank catalysts
in order of intrinsic catalytic activity, it is necessary to operate under
conditions where mass transfer is not rate limiting. A reactor used for
liquid phase hydrogenations should provide for good gas-liquid and liquid-
solid mass transport, heat transport, and uniformly suspend the solid
catalyst.
4 CATALYST DESIGN
The size of the deposited precious metal particulates and their location on
the support material affect the properties and performance of a
heterogeneous catalyst. Increased metal dispersion and decreased metal
particle size generally result in increased catalyst activity. Metal location
and metal dispersion can be controlled during catalyst manufacture. Metal
particulates can be deposited preferentially at the exterior surface of the
support to give what is termed an “eggshell” or “surface-loaded” catalyst.
Catalysts with metal particulates evenly dispersed throughout the support
structure are referred to as having a “standard” or “uniform” metal
distribution (Figure 3).
Figure 3. Schematic of Metal Location
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particulates can be deposited preferentially at the exterior surface of the
support to give what is termed an “eggshell” or “surface-loaded” catalyst.
Catalysts with metal particulates evenly dispersed throughout the support
structure are referred to as having a “standard” or “uniform” metal
distribution (Figure 3).
Catalysts are designed with different metal locations for reactions which
take place under different conditions of pressure and temperature.
Hydrogenation reactions are generally first order with respect to hydrogen.
As such, standard catalysts with increased metal dispersions typically
exhibit greater relative activity at high hydrogen pressures. Eggshell
catalysts exhibit higher relative activity at low hydrogen pressures.
Hydrogenation of large molecules is generally carried out using eggshell
catalysts. Variation of metal location can also be used to alter catalyst
selectivity.
Location of catalytic metal deep into the pore structure of the support may
lead to significant reactant pore diffusion limitations. Such catalysts,
however, are generally more poison resistant because catalyst poisons
are typically of high molecular weight, and unlike smaller reactant
molecules, are unable to penetrate into the catalyst pore structure to
deactivate the catalytic metal.
Deposited metal may be either in a reduced or unreduced form.
Unreduced catalysts are readily reduced under the conditions of the
catalytic hydrogenation itself, and are often more active than reduced
catalysts.
Catalysts may be modified with compounds that promote or inhibit certain
reactions. Modifiers affect catalytic activity, selectivity and/or life.
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5 CATALYST SEPARATION, FILTRATION
A good powdered catalyst should be easy to separate from the reaction
mixture and final product. Catalyst filtration time should be minimized to
ensure maximum product throughput and production rates. Cycle time
advantages gained from a high activity catalyst can be lost if catalyst
filtration becomes an extended and time consuming step.
A catalyst should exhibit high attrition resistance to reduce catalyst losses
resulting from generation and loss of catalyst “fines”. The generation of
“fines” will also decrease the rate of filtration. There is often a trade-off
between catalyst performance and the rate of catalyst separation. Catalyst
filtration rate and attrition resistance are largely functions of particle size,
particle shape, pore volume, pore size distribution, surface area and raw
material source.
6 PROCESS ECONOMICS
It is important to consider the economic viability of a catalyst and catalytic
process early in the selection process. The economics of using a
supported precious metal catalyst depend critically on catalyst turnover
number, i.e. the amount of product produced per amount of catalyst used,
and on catalytic activity or turnovers per unit time. For supported catalysts
it is often convenient to calculate costs in terms of the weight of product
produced per weight of catalyst used, or catalyst productivity. Catalyst
productivity (P) is defined as:
P = nS/L
where n is the number of times a catalyst is used or recycled, S is reaction
selectivity as a weight percent (weight of desired product produced per
weight of feedstock), and L is catalyst loading as a weight percent (weight
of catalyst used per weight of feedstock). The cost of the catalyst per unit
weight of product can be determined by dividing the total cost of the
catalyst by the catalyst productivity.
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Typical catalyst costs include catalyst fabrication, spent catalyst refining or
disposal and precious metal charges. In the case of a catalyst returned for
refining and reclamation of the precious metal, the total metal charges
should include only metal irrecoverably lost during the catalytic process,
the refining process, and due to handling. If the maximum allowable
catalyst cost per unit weight of product is known, one can back calculate
to determine required reaction selectivity and/or the number of catalyst
recycles necessary to make a process economically feasible.
Most of the commonly used catalyst supports, particularly carbon and
alumina, are available in a wide range of particle sizes and surface areas.
6.1 Activated Carbon
Activated carbon powder is used principally as a support for
catalysts in liquid phase reactions. As carbon is derived from
naturally occurring materials, there are many variations, each type
having its own particular physical and chemical properties.
The surface areas of different carbons can range from 500 m2
g-1
to
over 1500 m2
g-1
.
Trace impurities that may be present in certain reaction systems
can occasionally poison catalysts. The high absorptive power of
carbons used as catalyst supports can enable such impurities to be
removed, leading to longer catalyst life and purer products.
6.2 Alumina
Activated alumina powder has a lower surface area than most
carbons, usually in the range of 75 m2
g-1
to 350 m2
g-1
. It is a more
easily characterized and less absorptive material than carbon. It is
also noncombustible. Alumina is used instead of carbon when
excessive loss of expensive reactants or products by absorption
must be prevented. When more than one reaction is possible, a
platinum group metal supported on alumina may prove to be more
selective than the same metal supported on carbon.
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6.3 Calcium Carbonate
Calcium carbonate is particularly suitable as a support for
palladium, especially when a selectively poisoned catalyst is
required. The surface area of calcium carbonate is low but it finds
application where a support of low absorption or of a basic nature is
required, for example to prevent the hydrogenolysis of carbon
oxygen bonds.
6.4 Barium Sulfate
Barium sulfate is another low surface area catalyst support. This
support is a dense material and requires powerful agitation of the
reaction system to assure uniform dispersal of the catalyst.
6.5 Other Powdered Supports
Silica is sometimes used when a support of low absorptive capacity
with a neutral, rather than basic or amphoteric character is
required. Silica-alumina can be used when an acidic support is
needed.
14. Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd > Pt > Rh
Rh = Ru = Ir
C > Al2O3 =
BaSO4 BaSO4 =
CaCO3
5-100 3-10 None or low
polarity solvent
Rh, Pt or Ru used for
stereoselective application. Pd
may cause isomerization
Pd C > Al203 20-100 1-10 None or low
polarity solvent
Pd very active under mild
conditions.
Pd CaCO3 > C
C > BaSO4
5-50 1-3 Low Polarity
Solvent
Doped Catalyst (Lindlar) under
mild conditions
Pt > Rh > Pd
Pd = Ru
C > AlO3 5-100 1-10 Neutral or acidic for
Cl, Br Neutral or
basic for others
X = OR, OCOR, Cl, Br, NHR, No
base with halogens; no acid with
others
Pd > Ru >Pt Al2O3 > C
C > CaCO3
5-100 1-3 None or a Polar
solvent
Pd most common catalyst.
Ir-40; Rh-93,
100; Ru-100
None 20-80 1-5 Various Least hindered double bond
reduced. Asymmetric
hydrogenation with chiral ligands
Pt > Pd > Rh C > Al2O3 50-150 3-10 None or low
polarity solvent
Pd may give disproportionation
1.1 C-C Multiple Bonds
VULCAN Catalytic Reaction Guide
15. Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Rh> Pt Pt =
Ru > Pd
C > Al2O3 50-150 3-50 No solvent Rh active under mild conditions.
Pd >> Rh Al203 > C 100-150Ɨ >
150Ŧ
1-50 None or low
polarity solvent
Basic promoters enhance activity /
selectivity.
Rh > Pd >
Ru
C > Al2O3 5-150 1-50 None or low
polarity solvent
Rh preferred - no selectivity
problems.
Pt >> Ir C >> Al2O3 5-150 1-50 Acidic solvent Acetic acid or alcohol/HCl
preferred.
Rh > Ru C > Al2O3 100-150 3-50 Acetic acid Pd most common catalyst.
Rh > Ru > Pt C > Al2O3 50-150 3-10 for Rh
> 50 for Ru
Low polarity
solvent
X = OH, OR, OCOR, NH2, NHR,
Rh preferred - no hydrogenolysis.
Product Reactant
Pt = Rh C >> Al2O3 30-150 3-50 None or alcohol Acetic acid may enhance activity.
1.2 Aromatic Ring Compounds
VULCAN Catalytic Reaction Guide
16. Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Ru > Pt C > Al2O3 5-100 1-50 Low polarity
solvent
Fe2+ or Sn2+ salts promote Pt.
Water promotes Ru.
Pt C > CaCO3 5-100 1-20 Non-polar or low
polarity solvent
Modifiers required, e.g. Base, Fe2+
or Zn2+ salts.
Pd C >> Al2O3 5-100 1-10 Neutral solvent Acid causes loss of OH
Ru > Rh > Pt C >> Al2O3 50-150 1-50 Polar solvent (e.g.
water)
Ru requires high pressure.
Rh -40, 92, 93,
100 Ru-42,
100
None 25-110 1-200 Various Asymmetric Hydrogenation possible
with chiral ligands. Reduction of the
ketone also possible via
hydrosilation.
Pt C >> Al2O3 5-150 1-10 Low polarity
solvent
Modifiers required, e.g. Base, Fe2+
or Zn2+ salts.
Pd C >> Al2O3 5-50 1-10 Low polarity
solvent
Acid promotes hydrogenolysis of OH
Rh >> Ru C >> Al2O3 5-100 1-50 Low polarity or
neutral solvent
Ru requires high temperaturesand
pressures.
Pd C > Al2O3 5-100 1-10 Acidic solvent Promoted by strong acids.
Rh/Mo or
Rh/Re
Al2O3 150-200 80-100 Ethers Works best with 2o or 3o amides.
Poor for 1o amides.
Ru C > Al2O3 200-280 200-300 None or an
alcoholic solvent
Promoted by Sn.
1.3 Carbonyl Compounds
VULCAN Catalytic Reaction Guide
17. Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd = Pt > Rh C 50-100 3-50 Low polarity
solvent
Bases often inhibit reaction. Prduct
amine may poison catalyst.
Reactant Product
Pd C >> Al2O3 5-100 1-10 Low polarity
solvent
Acids normally prevent dimer
formation.
Pd = Pt C > Al2O3 5-50 1-5 Various Neutral conditions
Pt > Pd = Ir CaCO3 > BaSO4
BaSO4 > Al2O3
5-100 1-5 Various Use N- or S- compounds as
moderators
Pt C 50-150 <1-3 Dilute H2SO4 The Benner process.
Pd > Pt > Ru C >> Al2O3 50-100 1-10 Polar or low
polarity solvent
In presence of base.
Pd >> Pt C 5-100 1-10 Low polarity
solvent
Acetic acid/mineral acid solvent
preferred
Pd = Pt C > Al2O3 5-50 1-10 Various Neutral or mildly acidic conditions
preferred
Pd > Pt > Rh C 5-100 1-10 Various Mineralacid/acetic acid or mineral
acid/alcohol
Pd >>Rh C >> Al2O3 5-100 1-10 Polar or low
polarity solvent
Many dissolved salts improve rate.
1.4 Nitro & Nitroso
VULCAN Catalytic Reaction Guide
18. Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pt >> Rh = Pd C 5-100 1-10 Low polarity
solvent
X = halogen F >> Cl > Br > I.
Stability to hydrogenolysis
1.5 Halonitroaromatics
VULCAN Catalytic Reaction Guide
19. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
Reactant Product (deg. C) (BAR)
Pd = Pt C >> Al2O3 50-150 3-50 Low polarity
solvent
Schiff base formulation catalysed
by acid.
Pd = Pt C >> Al203 50-150 1-50 None or low
polarity solvent
Often add ketone and more
catalyst after nitro reduction
1.6 Reductive Alkylations
VULCAN Catalytic Reaction Guide
20. Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
Pt C >> Al2O3 50-150 3-50 Low polarity
solvent
Acidic conditions favored.
Product Reactant
Ir-93, Rh-93,
100, Ru-100
None 25-170 1-200 DMF, Ethanol Asymmetric hydrogenation possible
with chiral ligands.
Pt C 50-100 3-50 Various Acetic acid or ethanol best.
1.7 Imines
VULCAN Catalytic Reaction Guide
21. Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd = Rh > Pt C > > Al2O3 50-100 1-10 Acidic solvent or
additionof excess
ammonia.
Best Solvent is alcohol plus 1-2
equivalents of HCl or H2SO4
Rh C > > Al2O3 5-100 '1-10 Neutral solvent Rh gives good selectivity.
Pd > > Pt C >> Al2O3 5-100 1-10 Neutral solvent Pd gives best selectivity.
Pd C > Al2O3 5-100 1-10 Alcohol/acid or acetic
acid
Best solvents - acetic acid or alcohol
+ HCl or H2SO4
Pt > Pd C >> Al2O3 5-100 1-10 Low polarity solvent Use Neutral low polar solvents
Pd C 5-100 1-10 Alcohol with water &
acid
Imine intermediate hydrolyzed by
water.
1.8 Nitriles
VULCAN Catalytic Reaction Guide
22. Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Rh >> Pd C > > Al2O3 5-100 1-10 Various Alcohol + Acid or ammonia to
minimize coupling reactions
Pd > > Rh C >> Al2O3 5-100 1-10 Acidic solvent Mineral acid/acetic acid or mineral
acid/alcohol
1.9 Oximes
VULCAN Catalytic Reaction Guide
23. Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd C > > Al2O3 5-100 1-10 Low polarity solvent X = Cl, Br or I. Basic conditions
favored.
Pd C >BaSO4 5-50 1-3 Nonpolar solvent Reflux. Use N- or S- compounds as
modifiers + halogen aceptors.
Ru C > Al2O3 200-280 200-300 None or an alcoholic
solvent
Promoted by Sn.
Reactant Product
Pd > Pt
Pt = Ru > Rh
C > Al2O3
Al2O3 = CaCO3
50-150 3-50 Basic solvent for Cl &
Br; acidic for others
X = OR, OCOR, Cl, Br, NHR. With
halogens use alcoholic KOH or
NaOH, with others use alcoholic HCl
or acetic acid.
Pd C >> Al2O3 50-150 1-10 Acidic or neutral
solvent
X = OR, OCOR, Cl, Br, NHR. THF
Best for C-O cleavage. Aliphatic
carbonyls best for C-N cleavage.
1.10 Hydrogenolysis
VULCAN Catalytic Reaction Guide
24. Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd C >> Al2O3 50-100 3-50 Acidic solvent Organic base may promote
selectivity.
1.11 Other
VULCAN Catalytic Reaction Guide
25. Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd > Pt C >200 > 1 = 1 Various high
boiling point
solvents
Remove liberated H2 by N2 purge or
H2 acceptor in liquid phase.
Pd > Pt C > Al2O3 50-300 < 1 No solvent Pd is the only active catalyst.
Pd-62, 111 None 40-80 1-5 Methanol/water E = O, NH. Perform in presence of
reoxidant, e.g.Cu(Oac)2/O2.
Pd C 180-250 > 1 = 1 High Boiling Use dinitrotoluene as H2 acceptor.
Pd C > Al2O3 180-250 < 1 High Boiling
2. Dehydrogenation
VULCAN Catalytic Reaction Guide
26. Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Rh-42, 43, 50,
112
None 50-150 10-50 Aldehydes or
toluene
Higher normal to iso-aldehyde ratios
obtainable with Rh than with Co.
PPh3:Rh > 50:1 = 50:1
Pd-100, 111 None 50-150 10-50 Various. Base
promoted
X = Br, I R = aryl, benzyl, vinyl
Base promoted
3. Hydroformylation
VULCAN Catalytic Reaction Guide
27. Reactant Product Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pd-100, 101; Pt-100;
Rh-40, 112
None 50-150 10-50 Alcohol Use SnCl2 promoter for Pt and Pd.
Pt active for terminal alkenes only.
Pd-92, 100, 111 None 50-150 1-20 Various. Base
promoted
E = O, NH X = Br, I R = aryl,
benzyl, vinyl Base promoted
Pd-100, Rh-112,
RhI3
None 100-150 1-50 Carboxylic acids
(Rh) or ketones
(pd)
Iodide promotes Rh for !o alcohols.
Acidss promote Pd for 2o alcohols.
Product Reactant
Pd-100, 101, 111 None 25-100 1-10 Various Organic base such as Et3N, Bu3N
or inorganic bases such as
K2CO3. Ligand such as PPh3 also
required if Pd-111 is used.
Pd-100, 101 None 25-100 1-10 DMF Organic base such as Et3N, Bu3N
or inorganic bases such as
Pd-100, 111 None 50-150 1-20 Alcohol R = aryl Cu or Co promoted
4. Carbonylation
VULCAN Catalytic Reaction Guide
28. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Rh-100 None 50-150 ca. 1 Various Also possible to decarbonylate
some acyl alcohols.
5. Decarbonylation
VULCAN Catalytic Reaction Guide
29. Product Reactant Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Pt-92, 96, 112,
114
H2[PtCl6]
None 25-75 Ambient None,
hydrocarbons
Rh-93, 100 None 25 Ambient MeCN Z isomer obtained with EtOH or
propan-2-ol. PPh3 also requiredas
ligand when Rh-93 used.
6. Hydrosilylation
VULCAN Catalytic Reaction Guide
30. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-62, 92, 100, 101,
111
None -10-80 ca. 1 Various M = Li, Mg, Zn, Zr, B, Al, Sn, Si,
Ge, Hg, Ti, Cu, Ni.
Pd-92, 100, 111 None 50-150 1-3 Amine or toluene X = Br, I, Otf. Base required as HX
Scavenger.
Pd-92, 111 None 25-100 - Various Organic and inorganic bases can
be used. Various ligands can be
Pd-62, 92,101, 106,
111
None 25-100 - Various Phosphineligand required where
Pd-62, 92, 111 are used. Base
required.
7.1 Heck
VULCAN Catalytic Reaction Guide
31. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-92, 101, 111 None 25-100 - Various Base required, generally inorganic.
Various ligands can be used in
conjunction with Pd precursor e.g.
PPh3, P(o-to)3, t-Bu3P.
7.2 Suzuki
VULCAN Catalytic Reaction Guide
32. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-92,111, 106 None 80-100 - THF, toluene Base required, t-BuONa or
Cs2CO3. Ligand such as P(o-to)3,
t-Bu3P, BINAP required when Pd-
92 or Pd-111 used.
Pd-92, 111 None 80-100 - toluene Specialist ligand required. Base
such as K3PO4, NaOH required
when R'OH used as substrate.
7.3 Buckwald-Hartwig
VULCAN Catalytic Reaction Guide
33. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Reactant Product
Pd-100, 101, 103,
106
None 25-Reflux - THF, dioxane
Various Pd
precursors
None 25-100 - Various Base may be required in some
instances. M = Li, Mg, Zn, B, Al, Si, Hg
Pd-92, 111 None 25-100 - DMSO Pd-111 usually used in conjunction with
BINAP, Pd-92 in conjunction with dppf.
T-BuONa may be required.
Pd-62, 92, 100, 101,
111
None 25-100 - DMF, dioxane,
toluene, THF, NMP
Cu(I) may be needed as a co-catalyst.
Pd-92, 100, 101,
103, 105, 106,
None 25-100 - Various M = Li, MgX, ZnX, SnR3
7.4 Organometallics
VULCAN Catalytic Reaction Guide
34. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Reactant Product
Pd-100, 101 None 25-reflux - DMF, THF Addition of CuI as a co-catalyst
activates acetylene by formation of
copper acetylide. Organic base e.g.,
NR3 usually used.
Pd-111 None 25-100 - DMF Base required K2CO3 or Na2CO3,
Bu4NClalso required. Reaction
performed under phase transfer
conditions, hence the need for
B 4NCl
Pd-100 None 65 - THF Use Cul as additive.
Pd-62, 100, 111 None 25-reflux - NHEt2, NEt3 The addition of Cul as co-catalyst
activates the acetylene by formation of
a copper acetylide. Poor results are
obtained without Cul. The use of
amines is critical.
7.5 Sonogashira
VULCAN Catalytic Reaction Guide
35. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Reactant Product
Pd-62, 111 None 40-80 1-5 Methanol/water E = O, NH, Perform in presence of
reoxidant, e.g., Cu(Oac)2/O2
Pd-92, 111 None 25-100 - Toluene, THF,
dioxane
Base required NaOtBu, K3PO4
generally used Specialist ligand
Ru-120 + prop-2-yn-1-
ol, NaPF6 + P(Cy)3
None 25-80 Ambient Toluene,
dichloromethane
Pd-62 None 65 - THF Use LiCl as additive. Use of a mild
reoxidant such as benzoquinone is
required.
Pd-62, PdCl2 None 65 - THF Use NaCO3 or NaH as additives.
Product Reactant
PdCl2 None 80 - Acetonitrile
Pd-111, PdCl2 None 25-65 - THF Lithiation of the alcohol using n-
BuLi in THFis requried as the initial
step. Palladium precursor used in
conjunction with PPh3.
Pd-92,101,111 None 25-65 - THF Ligand required when using Pd-92
or Pd-111. Asymetric induction can
be achieved using a chiral ligand.
Pd-111 None 100 - DMF Base required, NBu4Cl. Ligand
such as PPh3 is also required.
7.6 Other
VULCAN Catalytic Reaction Guide
36. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-111; Rh-110, 115 None 20-50 ca. 1 Various Asymetric cyclopropanation
possible with chiral ligands.
8. Cyclopropanation
VULCAN Catalytic Reaction Guide
37. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Ru-100, 130 None 25-110 Ambient MeCN, PhCl,
toluene
dichloromethane
N-methyl-morpholine-N-oxide or
oxygen used as co-oxidant.
TEMPO also required as ligand
when Ru-100 used.
Pt, Pd, Ru C, Al2O3 30-70 1-3 Toluene,
hydrocarbons
Use air as oxidant.
Pt, Pd, Ru C, Al2O3 '30-70 1-3 Toluene,
hydrocarbons
Use air as oxidant.
Ru-100, 130 None 25-110 Ambient MeCN, PhCl,
toluene
dichloromethane
N-Methyl-morpholine-N-oxide
oroxygen used as co-catalyst.
TEMPO also required as ligand
when Ru-100 used.
Pt > Pd C 40-60 1-5 Aqueous Basic pH (8-10) essential.
9.1 Alcohols to Carbonyls
VULCAN Catalytic Reaction Guide
38. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
OsO4/
K2[OsO2(OH)4]
None 0-50 ca. 1 t-butanol, water,
THF
Oxidants such as N-
methylmorphine N-oxide or
K3Fe(CN)6 preferred. Asymetric
hydroxylation possible with chiral
ligands.
9.2 Dihydroxylation of Alkenes
VULCAN Catalytic Reaction Guide
39. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
Pd-111 None 20-50 1-5 Acetic acid or
alcohol
O2 or H2O2 used as oxidant.
Cu2+ co-catalyst.
9.3 Oxygen Insertion Reactions
VULCAN Catalytic Reaction Guide
40. Metal Support Reaction
Temp.
Reaction
Pressure
Solvents COMMENTS
(deg. C) (BAR)
Product Reactant
RuCl3, Ru-100 None 25-70 ca. 1 Various H2O2 or NaOCl oxidant.
PdCl2 None - - Water, DMF. Aq.
HCl
Use CuCl2/O2 as additives.
9.4 Other
VULCAN Catalytic Reaction Guide