Why have a Secondary Reformer ?
Need nitrogen to make ammonia
Wish to make primary as small as possible
Wish to minimise methane slip since methane is an inert in the ammonia synthesis loop
Other methods of achieving this
Braun Purifier process
Can address all these with an air blown secondary
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
Most modern ammonia processes are based on steam-reforming of natural gas or naphtha.
The 3 main technology suppliers are Uhde (Uhde/JM Partnership), Topsoe & KBR.
The process steps are very similar in all cases.
Other suppliers are Linde (LAC) & Ammonia Casale.
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
(HTS) High Temperature Shift Catalyst (VSG-F101) - Comprehensiev OverviewGerard B. Hawkins
The high temperature shift duty introduction and theory
HTS catalyst characteristics
developments over time
Typical HTS operational problems
Improved catalysts
VULCAN Series VSG-F101 Series
Summary
Why have a Secondary Reformer ?
Need nitrogen to make ammonia
Wish to make primary as small as possible
Wish to minimise methane slip since methane is an inert in the ammonia synthesis loop
Other methods of achieving this
Braun Purifier process
Can address all these with an air blown secondary
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
Most modern ammonia processes are based on steam-reforming of natural gas or naphtha.
The 3 main technology suppliers are Uhde (Uhde/JM Partnership), Topsoe & KBR.
The process steps are very similar in all cases.
Other suppliers are Linde (LAC) & Ammonia Casale.
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
(HTS) High Temperature Shift Catalyst (VSG-F101) - Comprehensiev OverviewGerard B. Hawkins
The high temperature shift duty introduction and theory
HTS catalyst characteristics
developments over time
Typical HTS operational problems
Improved catalysts
VULCAN Series VSG-F101 Series
Summary
Introduction and Theoretical Aspects
Catalyst Reduction and Start-up
Normal Operation and Troubleshooting
Shutdown and Catalyst Discharge
Nickel Carbonyl Hazard
Modern Methanation Catalyst Requirements
The Benefits and Disadvantages of Potash in Steam ReformingGerard B. Hawkins
Why do we include potash ?
What are the benefits ?
What are the disadvantages ?
Catalyst Deactivation
Carbon Deposition : Thermodynamics & Kinetics
Carbon formation margin
Reaction chemistry (Tube inlet)
Hydrocarbons undergo cracking reactions on hot surfaces at the tube inlet
Products of catalytic cracking reactions can form polymeric carbon
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
VULCAN Series VSG-Z101 Primary Reforming
Initial Catalyst Reduction
Activating (reducing) the catalyst involves changing the nickel oxide to nickel, represented by:
NiO + H2 <==========> Ni + H2O
Natural gas is typically used as the hydrogen source. When it is, the catalyst reduction and putting the reformer on-line are accompanied in the same step.
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 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
Equilibrium Effects
- Methane Steam
- Water Gas Shift
Relationship of Kp to Temperature
Relationship of WGS Kp to Temperature
Effect of Temperature on Methane Slip
Approach to Equilibrium
Reaction Path and Equilibrium
Effect of Pressure Increase
Operating Parameters
- Pressure
- Temperature
- Feed Rate
- Steam to Carbon
Effect of Exit Temperature Spread
Useful Tools
Calculating ATM
Introduction and Theoretical Aspects
Catalyst Reduction and Start-up
Normal Operation and Troubleshooting
Shutdown and Catalyst Discharge
Nickel Carbonyl Hazard
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).
Installation of S-50 ammonia synthesis converter along with waste heat boiler in downstream of existing S-200 ammonia synthesis converter is one of the major schemes of Energy Saving Project of Ammonia plant. The energy saving reported 0.18 G.Cal/T of Ammonia. Several ammonia plants have installed an additional ammonia synthesis converter in combination with a HP steam waste heat boiler, downstream of the existing ammonia converter. The result is increased conversion per pass, reduced compression requirements due to the smaller recycle gas stream, and improved waste heat recovery. Among the methodologies aimed at finding energy saving opportunities, pinch analysis linked to power and steam modeling has proved to be a powerful way for determining projects to improve the overall energy efficiency of industrial sites. This procedure has been applied successfully in many industrial facilities, allowing optimal energy recovery in the process and hence reduction of fuel consumption.
Done By: Silver Group
School Name: Al Khor Independent School for Girls
Environmental Catalysis Module: Students examines different types of catalytic systems, including heterogeneous and homogeneous catalysis. Depending on the knowledge they gained during activities, the students are then asked to design their projects.
Our Project:
Converting carbon dioxide into oxygen using calcium oxide and metal catalyst
Factory’s smoke contains many harmful and dangerous materials for both human beings and the environment, this project will not only save our ozone layer but it will save many people in the future generation securing a breath full future for humanity.
Introduction and Theoretical Aspects
Catalyst Reduction and Start-up
Normal Operation and Troubleshooting
Shutdown and Catalyst Discharge
Nickel Carbonyl Hazard
Modern Methanation Catalyst Requirements
The Benefits and Disadvantages of Potash in Steam ReformingGerard B. Hawkins
Why do we include potash ?
What are the benefits ?
What are the disadvantages ?
Catalyst Deactivation
Carbon Deposition : Thermodynamics & Kinetics
Carbon formation margin
Reaction chemistry (Tube inlet)
Hydrocarbons undergo cracking reactions on hot surfaces at the tube inlet
Products of catalytic cracking reactions can form polymeric carbon
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
VULCAN Series VSG-Z101 Primary Reforming
Initial Catalyst Reduction
Activating (reducing) the catalyst involves changing the nickel oxide to nickel, represented by:
NiO + H2 <==========> Ni + H2O
Natural gas is typically used as the hydrogen source. When it is, the catalyst reduction and putting the reformer on-line are accompanied in the same step.
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 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
Equilibrium Effects
- Methane Steam
- Water Gas Shift
Relationship of Kp to Temperature
Relationship of WGS Kp to Temperature
Effect of Temperature on Methane Slip
Approach to Equilibrium
Reaction Path and Equilibrium
Effect of Pressure Increase
Operating Parameters
- Pressure
- Temperature
- Feed Rate
- Steam to Carbon
Effect of Exit Temperature Spread
Useful Tools
Calculating ATM
Introduction and Theoretical Aspects
Catalyst Reduction and Start-up
Normal Operation and Troubleshooting
Shutdown and Catalyst Discharge
Nickel Carbonyl Hazard
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).
Installation of S-50 ammonia synthesis converter along with waste heat boiler in downstream of existing S-200 ammonia synthesis converter is one of the major schemes of Energy Saving Project of Ammonia plant. The energy saving reported 0.18 G.Cal/T of Ammonia. Several ammonia plants have installed an additional ammonia synthesis converter in combination with a HP steam waste heat boiler, downstream of the existing ammonia converter. The result is increased conversion per pass, reduced compression requirements due to the smaller recycle gas stream, and improved waste heat recovery. Among the methodologies aimed at finding energy saving opportunities, pinch analysis linked to power and steam modeling has proved to be a powerful way for determining projects to improve the overall energy efficiency of industrial sites. This procedure has been applied successfully in many industrial facilities, allowing optimal energy recovery in the process and hence reduction of fuel consumption.
Done By: Silver Group
School Name: Al Khor Independent School for Girls
Environmental Catalysis Module: Students examines different types of catalytic systems, including heterogeneous and homogeneous catalysis. Depending on the knowledge they gained during activities, the students are then asked to design their projects.
Our Project:
Converting carbon dioxide into oxygen using calcium oxide and metal catalyst
Factory’s smoke contains many harmful and dangerous materials for both human beings and the environment, this project will not only save our ozone layer but it will save many people in the future generation securing a breath full future for humanity.
Description of the Exhaust system along with its components such as Exhaust manifold,catalytic converter ,muffler ,exhaust tubing and oxygen sensor.The working of some of these components is also explained.
Emission Control by Catalytic Converter, Jeevan B MJeevan B M
A catalytic converter is an emissions control device that converts toxic gases and pollutants in exhaust gas to less toxic pollutants. The catalytic converter was invented by Eugene Houdry, a French mechanical engineer and expert in catalytic oil refining. In the catalytic converter, there are two different types of catalyst at work, a reduction catalyst and an oxidation catalyst.
A SHORT REVIEW ON ALUMINIUM ANODIZING: AN ECO-FRIENDLY METAL FINISHING PROCESSJournal For Research
Protection of aluminium alloys is most commonly done by forming anodic films. Anodic films can also be formed on metals like titanium, zinc, magnesium, niobium, and tantalum. Aluminium alloy parts are anodized to greatly increase the thickness of the natural oxide layer for corrosion resistance. A thin aluminium oxide film, that seals the aluminium from further oxidation when it is exposed to air. The anodizing process increases the thickness of the oxidized surface. Anodizing is accomplished by immersing the aluminium into an acid electrolyte bath and passing an electric current through the medium. In an anodizing cell, the aluminium work piece is made the anode by connecting it to the positive terminal of a dc power supply and the cathode is connected to the negative terminal of the dc source. Sealing is needed to seal the pores in oxide layer to prevent further corrosion. Oxide layer on the anodized aluminium has a highly ordered, porous structure that allows for secondary processes such as dyeing, printing and sealing. Nanowires and nanotubes can be made by using the pores in the oxide layer as templates.
Protection des métaux contre la corrosionCHTAOU Karim
Cette présentation présentent tout d’abord les principaux types de la corrosion et il présente une description détaillée des trois grandes méthodes, préventives et curatives, utilisées en anticorrosion.
This lecture describes the process of anodic oxidation of aluminium, which is one of the most unique and commonly used surface treatment techniques for aluminium; it illustrates the weathering behaviour of anodized surfaces. Some familiarity with the subject matter covered in TALAT This lectures 5101- 5104 is assumed.
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
Les types de bétons bitumineux pour couche de roulement sont nombreux. Selon leur formulation granulaire, la nature du liant d’enrobage et l’ajout éventuel d’additifs, les caractéristiques des mélanges obtenus présentent des propriétés spécifiques qui élargissent le domaine d’emploi des enrobés classiques.
DEBOTTLENECKING METALLURGICAL AND SULPHUR-BURNING SULPHURIC ACID PLANTS: CAPA...COBRAS
Guy Cooper presents general strategies for acid plants, as reduction of pressure drop by modifying or replacing plant equipment, increase of SO2 gas concentration, blower upgrades, steam system debottlenecking, and strategies to reduce emissions. Aspects specific to metallurgical acid plants such as: improvements to gas-cleaning, increasing blower suction pressure, control of air dilution to acid plant, and handling the variation of process conditions are discussed. Aspects specific to sulphur-burning plants such as sulphur handling and sulphur burning are also discussed.
Steam Reforming - The Basics of reforming, shapes and carbon:
Steam Reforming Catalysis :
Chemical reactions
Catalyst shape design
Catalyst chemistry
Carbon formation and removal
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
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
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
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
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
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
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5. Ammonia Chemistry
Reaction : (Exothermic)
N2 + 3H2 <=> 2NH3 H(@ 700K) = - 52kJ/mol
Reaction is favored by high pressure and low
temperature
Pressure governed by capital and operating
cost
Temperature balance of kinetics/equilibrium
6. Ammonia Synthesis Mechanism
Dissociative adsorption of H2
Dissociative adsorption of N2
• Believed to be the Rate Determining Step
(RDS)
Multi-step hydrogenation of adsorbed N2
Desorption of NH3
7. Effect of Temperature Pressure on
Ammonia Equilibrium Concentration
0
5
10
15
20
25
30
35
40
50 75 100 125 150
Pressure bara
NH3concentration%
380 C
400 C
420 C
8. Ammonia Equilibrium Diagram
300 350 400 450 500 550 600 650
0
10
20
30
40
Equilibrium
Max Rate
Temperature °C
Ammoniacontent%
9. Effect of Catchpot Temperature on
Ammonia VLE
0
2
4
6
8
10
12
50 75 100 125 150
Pressure bara
NH3concentration%
0 C
minus 20 C
10. Catalyst Requirements
High catalyst activity
Low sensitivity to
catalyst poisons
High thermal
resistance
Reasonable
reduction time
High mechanical
strength and
abrasion resistance
11. Catalyst Formulation
The source of iron is magnetite, Fe3O4,
chosen for its crystal structure
During reduction, oxygen is removed from
the crystal lattice without shrinkage
This produces metallic iron which is
extremely porous
A significant factor in achieving a high
activity catalyst
12. Incorporation of Promoters
Small amounts of certain metal oxides
promote activity and improves stability
Alumina and potash are the most important
• They produce ‘doubly-promoted’ catalyst
• Alumina is a ‘structural’ promoter
• Restricts growth of iron crystallites during
reduction and operation
• Increases thermal stability of the catalyst
13. Incorporation of Promoters
Alkali metals are ‘electronic promoters’ and
greatly increase the activity of the iron
particles; potassium is the most cost
effective
Other promoters include calcium oxide, silica
& magnesia
Contaminants in the raw magnetite must also
be taken into account during manufacture to
ensure the optimum concentration of
promoters in the finished catalyst
14. Effect of Promoters and Stabilizers
Conventional Catalysts
AI2O3 - stabilizes the internal surface
SiO2 - stabilizes the activity in presence of oxygen
compounds during normal operation and
reduction.
K2O - increases the activity
- decreases the thermal stability and the
resistance against poisoning by oxygen
compounds
- minimizes the neutralization of K promoter
CaO - increases the stability against poisoning by
sulfur
15. Ammonia Synthesis - Catalyst
Parameters
Parameters as follows
Form Irregular particles
Production Method Melt, cool and grind
Size 1-3 mm
Magnetite % Balance %
Potash % 0.6-0.8 %
Calcium Oxide % 1.4-1.8 %
Alumina % 2.2-2.6 %
16. Ammonia Synthesis Catalyst
Production
Catalyst is unusual in that it is not made via
pelleting or extrusion
Unique manufacturing process
A mix is made of ingredients including
promoters
Feed is passed to an electric Arc furnace
Then milled to give correct shape distribution
17. Effect of Size on Activity
Particle Diameter (mm)
14121086420
RelativeActivity
120
100
80
60
40
0
20
18. Effect of Size on Activity
Smaller pellets = high activity
Therefore high production or small catalyst
volume
But pressure drop will rise
So must use either axial-radial or radial flow
beds to minimise pressure drop
Basis of many converter internal retrofits
19. Deactivation
Clean Gas
Thermal sintering
Contaminated Gas
Both Temporary and Permanent Poisons
• Oxygen induced sintering
• By water or CO and CO2
• Site blocking/Sintering
20. Uhde Converter Design
Uhde design a range of converters;
modern designs use radial flow with
inter-cooling & 'split converters' with
heat recovery between,
• Converter 1 : 2-bed, 1 interchanger
• Heat recovery (boiler)
• Converter 2 : 3rd bed
22. Gas inlet
Start up gas
Gas outlet
Second bed
First bed
Uhde Converter Design
Features of Krupp-Uhde
2-bed radial Ammonia Converters
• Easy withdrawal of the internal heat
exchanger without catalyst removal
• Comfortable access for catalyst
removal without removal of the
cartridge
• Access to all catalyst beds without
removal of intermediate heat
exchanger
• Reasonable transport dimensions
and weights even at high plant
capacities
23. Uhde Converter Design
Features of Krupp-Uhde
1-bed radial Ammonia
Converters
• One radial type catalyst bed
resulting in maximum
conversion rate, lower recycle
gas rate and low pressure drop
• Suitable large volumes of
catalyst with small grain size
• Simple and reliable design
• Comfortable access for catalyst
removal without removal of the
cartridge
• Reasonable transport
dimensions and weights even at
high plant capacities
Gas outlet
Gas inlet
Third bed
24. Ammonia Synthesis - Temperature
Profile
Equilibrium curve
% NH3
Heat exchanger type
Quench type
Temperature °C
500450400
0
5
10
15
20
27. Ammonia Synthesis - Performance
Monitoring
Monitor temperature profile
• Adjust accordingly to optimise production
Monitor pressure drop across converter
Monitor loop pressure
Monitor inert levels
• Helps identify upstream problems
28. Ammonia Synthesis - Problems
Ammonia Synthesis is a robust catalyst
• Delivers extremely long lives
• Performance is a function of converter and
catalyst
Must be aware of
• Effect of water
• Effect of CO and CO2
• Will poison the catalyst and therefore
reduce production