Debottlenecking Claus Sulfur Recovery Units: An Investigation of the application of Zinc Titanates
1 Executive Summary
2 Claus Process
2.1 Partial Combustion Claus
2.2 Split Flow Claus
2.3 Sulfur Recycle Claus
3 Zinc Titanates
4 Application of Zinc Titanate to Debottleneck Partial Combustion Claus by 10%
4.1 Process
4.2 ASPEN Modeling Results
4.3 Cost of Zinc Titanate Bed Installation
4.3.1 Basis of Costing
4.3.2 Zinc Titanate Beds
4.3.3 Regen Cooler
4.3.4 Blowers
4.3.5 Results
4.4 Alternative Debottlenecking Technology for Partial Combustion Claus
4.5 Cost of 10% Debottlenecking Using COPE Process
5 Debottlenecking Claus Split Flow System by 10% with Zinc Titanates
6 Debottlenecking Claus Sulfur Recycle System With Zinc Titanate
7 Effect of Zinc Titanate Debottlenecking on Existing Tail; Gas Treatment Systems
7.1 Selectox
7.2 SuperClaus99
7.3 Superclaus 99.5
7.4 SCOT Process
7.5 Zinc Titanate as a Claus Tail Gas Treatment
7.6 H2S Removal Efficiency With Zinc Titanate
8 Effects on COS and CS2 Formation
9 Questions for further Investigation
FIGURES
Figure 1 Claus Unit and TGCU
Figure 2 Claus Process
Figure 3 Typical Claus Sulfur Recovery Unit
Figure 4 Two-Stage Claus SRU
Figure 5 The Super Claus Process
Figure 6 SCOT
Figure 7 SCOT/BSR-MDEA (or clone) TGCU
REFERENCES: PATENTS
US4333855_PROMOTED_ZINC_TITANATE_CATALYTIC_AGENT
US4394297_ZINC_TITANATE_CATALYST
US6338794B1_DESULFURIZATION_ZINC_TITANATE_SORBENTS
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
Introduction and Theoretical Aspects
Catalyst Reduction and Start-up
Normal Operation and Troubleshooting
Shutdown and Catalyst Discharge
Nickel Carbonyl Hazard
Modern Methanation Catalyst Requirements
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
Introduction and Theoretical Aspects
Catalyst Reduction and Start-up
Normal Operation and Troubleshooting
Shutdown and Catalyst Discharge
Nickel Carbonyl Hazard
Modern Methanation Catalyst Requirements
Catalytic Reactions in Catalytic Reforming
Catalytic Reforming Reactions
Sulfur Related Problems
Effects of Sulfur in Catalytic Reforming
Reactions in Catalytic Reforming
Catalytic Reforming Catalysts
Effect of Sulfur on Catalytic Reforming Catalysts
Catalytic Reformer Efficiency
VULCAN Sulfur Guards
VULCAN Sulfur Guards for Catalytic Reformers
VULCAN Guard Installation Protects Isomerization Catalysts
Liquid Phase vs Gas Phase: Relative Advantages
Liquid Phase Treating
Which active metal is best?
Thiophenes and Nickel Sulfur Guards
Sulfiding mechanisms with reduced metals
Thiophene adsorption on nickel
Advantages of Cu/Zn Over Nickel Sulfur Guards
Copper oxide vs Nickel
Nickel Sulfur Guards
Manganese Sulfur Guards
In the plant, ammonia is produced from synthesis gas containing hydrogen and nitrogen in the ratio of approximately 3:1. Besides these components, the synthesis gas contains inert gases such as argon and methane to a limited extent. The source of H2 is demineralized water and the hydrocarbons in the natural gas. The source of N2 is the atmospheric air. The source of CO2 is the hydrocarbons in the natural gas feed. Product ammonia and CO2 is sent to urea plant. The present article intended the description of ammonia plant for natural gas based plants and the possible material balance of some section.
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
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.
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
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.
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
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
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
Synthesis Gas and Refinery Hydrogen Applications
Support balls or more accurately, support balls and hold-down balls will at times need to be specified to our customers. Advice may also be needed opposite the usage of meshes and hold-down screens. This brief report focuses on some key aspects to consider.
1. Support Balls
2. Hold-down Balls
3. Meshes over Exit Collector & Exit Screen
4. Hold-down Screens
5. Support and Hold-down Ball Compositions and Applications
6. High Surface Area Dust Collectors
Look at two main types
Explain mechanisms
Explain prevention of cracking
Three main types
1 Carbon cracking
2 Boudouard carbon formation
3 CO reduction
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.
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
Catalytic Reactions in Catalytic Reforming
Catalytic Reforming Reactions
Sulfur Related Problems
Effects of Sulfur in Catalytic Reforming
Reactions in Catalytic Reforming
Catalytic Reforming Catalysts
Effect of Sulfur on Catalytic Reforming Catalysts
Catalytic Reformer Efficiency
VULCAN Sulfur Guards
VULCAN Sulfur Guards for Catalytic Reformers
VULCAN Guard Installation Protects Isomerization Catalysts
Liquid Phase vs Gas Phase: Relative Advantages
Liquid Phase Treating
Which active metal is best?
Thiophenes and Nickel Sulfur Guards
Sulfiding mechanisms with reduced metals
Thiophene adsorption on nickel
Advantages of Cu/Zn Over Nickel Sulfur Guards
Copper oxide vs Nickel
Nickel Sulfur Guards
Manganese Sulfur Guards
In the plant, ammonia is produced from synthesis gas containing hydrogen and nitrogen in the ratio of approximately 3:1. Besides these components, the synthesis gas contains inert gases such as argon and methane to a limited extent. The source of H2 is demineralized water and the hydrocarbons in the natural gas. The source of N2 is the atmospheric air. The source of CO2 is the hydrocarbons in the natural gas feed. Product ammonia and CO2 is sent to urea plant. The present article intended the description of ammonia plant for natural gas based plants and the possible material balance of some section.
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
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.
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
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.
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
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
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
Synthesis Gas and Refinery Hydrogen Applications
Support balls or more accurately, support balls and hold-down balls will at times need to be specified to our customers. Advice may also be needed opposite the usage of meshes and hold-down screens. This brief report focuses on some key aspects to consider.
1. Support Balls
2. Hold-down Balls
3. Meshes over Exit Collector & Exit Screen
4. Hold-down Screens
5. Support and Hold-down Ball Compositions and Applications
6. High Surface Area Dust Collectors
Look at two main types
Explain mechanisms
Explain prevention of cracking
Three main types
1 Carbon cracking
2 Boudouard carbon formation
3 CO reduction
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.
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
Determination of Oxygen in Anhydrous Ammonia
SCOPE AND FIELD OF APPLICATION
This method is suitable for the determination of trace amounts of oxygen in Liquefied anhydrous ammonia.
The trace oxygen analyzer provides for trace oxygen analysis in decade steps ranging from 0 - 10 to 0 - 10,000 ppm v/v (full scale).
- Process effects of pre-reforming
- Process benefits of pre-reforming
- Effect of Pre-reformer Inlet Temp on Primary Reformer Efficiency
- Services for Pre-reforming
Pre-Reforming Problems
- Features: Impact of Sulfur
- High Temperature Operation
- Catalyst Deactivation
- Which is Better - High or Low Inlet Temperatures ?
- Pre Reformer Loading
- Pre-Reformer Installation
- Pre-reformer Startup
- Catalyst Drying
- Catalyst Heating
- Reduction
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
Low Temperature Shift Catalyst Reduction Procedure
VSG-C111 as supplied contains copper oxide; it is activated for the low temperature shift duty by reducing the copper oxide component to metallic copper with hydrogen. The reaction is highly exothermic. In order to achieve maximum activity, good performance and long life, it is essential that the reduction is conducted under correctly controlled conditions. Great care must be taken to avoid thermal damage during this critical operation.
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
Techniques for developing a cost-effective expansion will be presented. The key is advanced planning and evaluating constructability. The limiting large equipment capacity will be determined using process heat and material balance simulations and rating of the equipment. Once bottlenecks are determined, the rest of the facility can be revamped. Heat pinch will be used in the heat exchanger trains as heat input is usually the limiting item. A crude, vacuum and delayed coker complex expansion will be provided as an example.
Attendees will be provided with a step-by-step procedure on how to get more capacity, reduce energy usage or improve product quality from a unit or complex. Process simulations, equipment rating by computer evaluations, hydraulics, cost-estimates at the fel-0 conceptual, fel-1 factored and fel-2 take-off level will be provided. A process complex featuring three different types of units will be used as an example.
Process Design Engineer with 8.0 Years of experience in Oil & Gas and Refinery.ASHISH KUMAR
Involved in Detail and Basic engineering projects in Oil & Gas and Refinery. I have exposure to softwares like HTRI, HYSYS. Experience in Line and Control valve hydraulics, Pump hydraulics. Vendor offer checking of equipments, instrumnets amd compressors. Worked in Oil and gas projects as well as refinery projects. Exposure to API/Shell/ Saudi Aramco standards.
Process Synthesis
INTRODUCTION
1 A SUGGESTED GENERAL APPROACH
2 EXAMPLES OF PROCESS SELECTION
2.1 Harvesting and Thickening of Single Cell Protein
2.2 Dewatering of a Specialty Latex
3 REFERENCES
TABLES
1 THE ADVANTAGES AND DISADVANTAGES OF DIFFERENT RANGE OF PH FOR “PROTEIN” ORGANISM FLOCCULATION
2 THE ADVANTAGES AND DISADVANTAGES OF VARYING EXTENTS OF CELL BREAKAGES
3 PREDICTED AND OBSERVED FILTER CAKE SOLIDS CONTENTS FOR THE VARIOUS LATICES AFTER COAGULATION
FIGURES
1 THE “PROTEIN” BACTERIAL HARVESTING SYSTEM
2 PROCESS FOR MANUFACTURE OF CALCIUM CARBONATE FILTERS
3 H-ACID ISOLATION
4 A SUGGESTED APPROACH TO DETERMINING FEASIBLE PROCESS OPTIONS, AND OPERATING CONDITIONS FOR SEPARATION OF FINE SOLIDS FROM SUSPENSION
5 MODULI VERSUS SOLIDS CONTENT FORTYPICAL FORWARD FLOCCULATED “PROTEIN” SUSPENSIONS
6 DECISION TREE FOR SELECTION OF AS1 HARVESTING CONDITIONS WHEN PRINCIPAL CONSTRAINT CONCERNS THE DEGREE OF THICKENING REQUIRED IN THE CONCENTRATE
7 DECISION TREE FOR SELECTION OF AS1 HARVESTING CONDITIONS WHEN PRINCIPAL CONSTRAINT CONCERNS THE USE OF FLOTATION AS A UNIT OPERATION FOR THICKENING
8 DECISION TREE FOR SELECTION OF AS1 HARVESTING CONDITIONS WHEN PRINCIPAL CONSTRAINT CONCERNS THE QUALITY OF THE RECYCLED LIQUOR
9 MODULUS SOLIDS CONTENT CURVES FOR THEVARIOUS COAGULATED LATICES
Biological Systems: A Special Case
Up till now we have discussed various aspects of the separation and processing of fine solids without too much reference (except in the examples) to the specifics of the properties of the materials concerned. Though the material properties are the dominant influence on efficient process design and operation, it has been postulated that the necessary characteristics for process selection and optimization can be found fairly readily using easily-applicable rheological and other techniques. This underlying assumption also seems to hold good for biological suspensions; however, certain aspects of the behavior of these systems are sufficiently specialized for them to merit a separate discussion viz:
1 TYPES OF BIOLOGICAL SEPARATION
1.1 Whole-Organism Case
1.2 Part-Cell Separations
1.3 Isolation of Individual Molecular Species
2 SETTING ABOUT DEVISING AN EFFECTIVE
PROCESS FOR SEPARATION OF A BIOLOGICAL MATERIAL
2.1 Whole-Organism Case
2.1.1 Characterization of Biopolymers in the Liquor
2.1.2 Release of Internal Water
2.2 Part -Cell Separations
2.2.1 Selectivity
2.2.2 Cost
2.3 Isolation of Individual Molecular Species
3 Examples
3.1 Effective Design and Operation of a Process for Harvesting of Single Cell Protein
3.2 Harvesting of Mycoprotein for Human Consumption
3.3 Thickening of a Filamentous Organism Suspension
3.4 Separation of Poly-3-hydroxybutyrate Polymer (PHB) from Alcaligenes Eutrophus Biomass
3.5 Isolation of Organic Acid Produced by an Enzymatic Process
4 REFERENCES
Table
Figures
Determination of Hydrocarbons in Anhydrous Ammonia By Gas ChromatographyGerard B. Hawkins
Determination of Hydrocarbons in Anhydrous Ammonia By Gas Chromatography
SCOPE AND FIELD OF APPLICATION
The method is suitable for the determination of hydrocarbons from C1 to C4 (see 6.4.2) in gaseous ammonia, or in mixtures of ammonia and air. It is valid for concentrations in the range 10-10000 ppm.
The method may be used for the analysis of the atmosphere from a ships hold After purging with ammonia and for the analysis of gasified liquid anhydrous ammonia during or after loading. In these cases, hydrocarbon contamination may arise from the previous cargo of the vessel, the nature of which should be ascertained prior to carrying out the analysis
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
GE / Texaco Gasifier Feed to a Lurgi Methanol Plant and its Effect on Methano...Gerard B. Hawkins
GE / Texaco Gasifier Feed to a Lurgi Methanol Plant and its Effect on Methanol Production
CONTENTS
0 Methanol Synthesis Introduction
1 Executive Summary
2 Design Basis
2.1.1 Train I Design Basis
2.1.2 Train II Design Basis
2.1.3 Train III Design Basis
2.2 Design Philosophy
2.2.1 Operability Review
2.3 Assumptions
2.4 Train IV Flowsheet
2.4.1 CO2 Removal
3 Discussion
3.1 Natural Gas Consumption Figures
3.1.1 Base Case
3.1.2 Case 1 – Coal Gasification in Service
3.1.3 Case 2 – Coal Gasification in Service – No CO2 Export
3.2 Methanol Production Figures
3.2.1 Base Case
3.2.2 Case 1 – Coal Gasification in Service
3.2.3 Case 2 – Coal Gasification in Service – No CO2 Export
3.3 85% Natural Gas Availability
3.4 100% Natural Gas Availability
3.5 CO2 Emissions
3.5.1 Base Case
3.5.2 Case 1 – Coal Gasification in Service
3.5.3 Case 2 – Coal Gasification in Service – No CO2 Export
3.6 Specific Consumption Figures
3.6.1 Base Case
3.6.2 Case 1 – Coal Gasification and CO2 Import
3.6.3 Case 2 – Coal Gasification and No CO2 Import
3.7 Train IV Synthesis Gas Composition
4 Further Work
5 Conclusion
APPENDIX
Important Stream Data – Material Balance Stream Data
Texaco Gasifier with HP Steam Raising Boiler
CHARACTERISTICS OF COAL
Material Balance Considerations
Methanation catalysts are almost always manufactured and transported in the oxidized form, and therefore they must be reduced in the reactor to give nickel metal in order to make them active. The reduction is usually carried out in process gas and occurs by the two reactions:
Integration of Special Purpose Reciprocating Compressors into a ProcessGerard B. Hawkins
1 SCOPE
2 CHOICE OF COMPRESSOR TYPE
2.1 Parameters
2.2 Preliminary Choice of Machine Type
2.3 Review of Other Types of Compressor
3 CHOICE OF NUMBER OF COMPRESSORS
3.1 Influence of Reliability Classification
3.2 Driver Considerations
3.3 Deterioration of Standby Machines
4 EFFECTS OF PROCESS GAS COMPOSITION
4.1 Particulate Contamination
4.2 Droplets in Suspension
4.3 Polymer Deposit
4.4 Molecular Weight Variation
4.5 Compressibility Variation
4.6 Gas Dryness
4.7 Gas Solution in Lubricating Oil for Cylinder and Gland
5 THROUGHPUT REGULATION
5.1 Inlet Line Throttle Valve
5.2 Inlet Line Cut-off Valve
5.3 Compressor Inlet Valve Lifter
5.4 Clearance Volume Variation
5.5 Speed Variation
5.6 Bypass
5.7 Hybrid Regulation Systems
6 PRINCIPAL FEATURES
6.1 Calculate Discharge Gas Temperature
6.2 Choice of Number of Stages
6.3 Configuration
6.4 Valve Operation Limit on Piston Speed
6.5 Limits for Mean Piston Speed
6.6 Estimation of Volumetric Efficiency
6.7 Estimation of Crankshaft Rotational Speed
6.8 Calculation of Piston Diameter
6.9 Choice of Number of Cylinders
7 DRIVER TYPE
7.1 Electric Motors
7.2 Steam Turbines
7.3 Special Drivers
8 VESSELS
APPENDICES
A RELIABILITY CLASSIFICATION
B CONDITIONS FOR LUBRICATED CYLINDERS AND GLANDS
C ESTIMATE OF LUBE OIL CONTAMINATION OF PROCESS GAS
D INFLUENCE OF GAS COMPOSITION AND MACHINE CONSTRUCTION
ON FILLED PTFE PISTON RING SEALS
E LIMITS ON GAS TEMPERATURES
FIGURES
1 SELECTION CHART
2 DESIGN SEQUENCE 1 - ESTIMATE NUMBER OF STAGES
3 DESIGN SEQUENCE 2 - ESTIMATE CYLINDER SIZES
(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
In pyrolysis gasoline hydrogenation there is a tendency to form polymeric materials on and in the catalyst bed. These are formed by condensation of gums and diolefins at local areas in the reactor .........
SYNGAS CONDITIONING UNIT FEASIBILITY CASE STUDY: COAL-TO-LIQUIDSGerard B. Hawkins
SYNGAS CONDITIONING UNIT FEASIBILITY CASE STUDY: COAL-TO-LIQUIDS
Case Study: #0953616GB/H
HT SHIFT REACTOR CATALYST SPECIFICATION
Process Specification
This process duty specification refers to a Syngas Conditioning Unit which utilizes HT Shift reaction technology on a slip stream of raw gas to produce a recombined gas stream with a H2:CO ratio of 1.57:1. This is an important consideration as the Shift reactor is not required to minimize CO at outlet, and this specification refers to the expected performance that can be achieved in a single stage reactor scheme.
The Syngas Conditioning Unit is part of a proposed coal-to-liquids complex in which synthesis gas is produced by gasification of coal for downstream processing in a Fischer Tropsch reactor and Hydrocracker unit.
Hydrogen Compressors
Engineering Design Guide
1 SCOPE
2 PHYSICAL ROPERTIES
2.1 Data for Pure Hydrogen
2.2 Influence of Impurities
3 MATERIALS OF CONSTRUCTION
3.1 Hydrogen from Electrolytic Cells
3.2 Pure Hydrogen
4 DESIGN
4.1 Pulsation
4.2 Bypass
5 TESTING OR COMMISSIONING RECIPROCATING COMPRESSORS
6 LUBRICATION
7 LAYOUT
8 REFERENCES
FIGURES
1 MOLLIER CHART - HYDROGEN
2 COMPRESSIBILITY CHART
3 NELSON DIAGRAM
4 WATER CONTENT IN HYDROGEN FOR OIL-LUBRICATED COMPRESSORS AS GRAMM/M2 SWEPT CYLINDER AREA
Determination of Carbon Dioxide, Ethane And Nitrogen in Natural Gas by Gas C...Gerard B. Hawkins
Determination of Carbon Dioxide, Ethane
And Nitrogen in Natural Gas by Gas Chromatography
1 SCOPE AND FIELD OF APPLICATION
This document is a method for the determination of carbon dioxide, ethane and nitrogen in natural gas in the range 0-10% v/v.
2 PRINCIPLE
The gas sample will be injected automatically by a ten port valve onto the poraplot U column. The nitrogen will elute first and be switched to the mole sieve column. The mole sieve column will be isolated and the poraplot column will elute the carbon dioxide and ethane via a restrictor column to the detector. After the elution of the carbon dioxide and ethane the poraplot column will be back flushed. Then the nitrogen will be allowed to elute from the mole sieve column (see figure 1.) ...
Methanol Casale Advanced Reactor Concept (ARC) Converter Retrofit CASE STUDY #10231406
For older methanol plants, efficiency is worse than for a modern plant
• To maximize profit we must improve either
– Plant efficiency
– Plant production rate
This case study highlights the revamp of a Middle Eastern Methanol Plant ARC converter with part IMC internals, to improve efficiency and production; with no CO2 addition to the Synloop, and with CO2 addition to the Synloop.
- 250 TPD CO2
- 500 TPD CO2
Hydrogenation Reactors
Stirred Vessels
Loop Reactors
Other reactor types
Appendix
- List of contact details for suppliers
- Information from supplier’s websites
Temperature excursions in hydrogenation reactors may have several causes, the most common ones being:-
i) Loss of recycle quench system. This could be either the liquid or gas stream. The condition is made worse if the make-up gas keeps flowing.
ii) Excessive temperatures. The loss of cooling medium ........
Gas Mixing
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
4 RECOMMENDATIONS FOR GAS MIXING:
PLUG FLOW
5 RECOMMENDATIONS FOR GAS MIXING:
BACKMIXED INITIAL ZONE
6 BIBLIOGRAPHY
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
Introduction
Catalyst breakage is a well known phenomena that occurs during operation and transients such as reformer trips, whether this be due to,
• Normal in service breakage,
• Breakage due to carbon formation/removal,
• Breakage due to steam condensation or carry over,
• Breakage during a trip.
The effect of catalyst breakage can be observed in a number of ways,
• Hot bands,
• Speckling and giraffe necking,
• Catalyst breakage and settling.
Design and Simulation of Continuous Distillation ColumnsGerard B. Hawkins
Design and Simulation of Continuous Distillation Columns
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
4 FRACTIONAL DISTILLATION
5 ROUGH METHOD OF COLUMN DESIGN
5.1 Sharp Separations
5.2 Sloppy Separations
6 DETAIL DESIGN USING THE CHEMCAD DISTILLATION PROGRAM
6.1 Sharp Separations
6.2 Sloppy Separations
7 COMPLEX COLUMNS
7.1 Multiple Feeds
7.2 Sidestream Take-Offs
8 DESIGN USING A LABORATORY COLUMN
SIMULATION
9 DESIGN USING ACTUAL PLANT DATA
9.1 Uprating or Debottlenecking Exercises
10 REFERENCES
APPENDICES
A WORKED EXAMPLE
B SLOPPY SEPARATIONS
C SIMULATION USING PLANT DATA : CASE HISTORIES
TABLES
Similar to Debottlenecking Claus Sulfur Recovery Units: An Investigation of the application of Zinc Titanates (20)
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
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
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
Burner Design, Operation and Maintenance on Ammonia PlantsGerard B. Hawkins
Burner Design, Operation and Maintenance on Ammonia Plants
Brief History
Reformer Burner Types/Design
Types of Reformers
Combustion Characteristics
Excess Air/Heater Efficiency
Maintenance, Good Practice
Low Nox Equipment
Summary
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
Catalyst Catastrophes in Syngas Production - II
Contents
Review of incidents by reactor
Primary reforming
Secondary reforming
HTS
LTS
Methanator
Reactor loading
Support media
Some general comments on alternative actions when a plant gets into abnormal operation
Catalyst Catastrophes in Syngas Production - I
The Hazards
Review incidents by reactor
Purification….
Through the various unit operations to
Ammonia synthesis
Nickel Carbonyl
Pre-reduced catalysts
Discharging catalysts
Conclusion
Integration of Special Purpose Centrifugal Pumps into a ProcessGerard B. Hawkins
Integration of Special Purpose Centrifugal Pumps into a Process
CONTENTS
1 SCOPE
2 PRELIMINARY CHOICE OF PUMP
SECTION A - INLET CONDITIONS
Al Calculation of Basic Nett Positive Suction Head (NPSH)
A2 Correction to Basic NPSH for Temperature Rise at Pump Inlet
A3 Correction to Basic NPSH for Acceleration Head
A4 Calculation of Available NPSH
A5 Correction to NPSH for Fluid Properties
A6 Calculation of Suction Specific Speed
A7 Priming
A8 Submergence
SECTION B – FLOW / HEAD RATING SEQUENCE
B1 Calculation of Static Head
B2 Calculation of Margins for Control
B3 Calculation of Q-H Duty
B4 Stability and Parallel Operation
B5 Corrections to Q-H Duty for Fluid Properties
B6 Guide to Pump Type and Speed
SECTION C – DRIVER POWER RATING
C1 Estimation of Pump Efficiency
C2 Calculation of Absorbed Power
C3 Calculation of Driver Power Rating
C4 Preliminary Power Ratings of Electric Motors
C5 Starting Conditions for Electric Motors
C6 Reverse Flow and Reverse Rotation
SECTION D - CASING PRESSURE RATING
D1 Calculation of Maximum Inlet Pressure
D2 Calculation of Differential Pressure
D3 Pressure Waves
D4 Pressure due to Liquid Thermal Expansion
D5 Casing Hydrostatic Test Pressure
SECTION E – SEALING CONSIDERATIONS
E1 Preliminary Choice of Seal
E2 Fluid Attributes
E3 Definition of Flushing Arrangements
APPENDICES
A RELIABILITY CLASSIFICATION
B SYMBOLS AND PREFERRED UNITS
DOCUMENTS REFERRED TO IN THIS ENGINEERING DESIGN GUIDE
Amines
Stereochemistry, Reaction Mechanisms, Catalysis, Production Processes and Applications
Contents
Historical perspective
Background
(MMA, DMA and TMA)
Stereochemistry and Structure
Reaction Mechanisms and Thermodynamics
CATALYSTS FOR AMINATION
Non-Zeolitic Catalysts for Amination
Mordinite (MOR) Catalysts for Amination
Zeolite Catalysts for Amination
Amines Production
Amines: Markets and Applications
Gas Separation
Conventional Amines Treating System
Amine System for Gas Sweetening
APPENDIX
Structures
Ethyleneamines Production
PHP Frameworks: I want to break free (IPC Berlin 2024)Ralf Eggert
In this presentation, we examine the challenges and limitations of relying too heavily on PHP frameworks in web development. We discuss the history of PHP and its frameworks to understand how this dependence has evolved. The focus will be on providing concrete tips and strategies to reduce reliance on these frameworks, based on real-world examples and practical considerations. The goal is to equip developers with the skills and knowledge to create more flexible and future-proof web applications. We'll explore the importance of maintaining autonomy in a rapidly changing tech landscape and how to make informed decisions in PHP development.
This talk is aimed at encouraging a more independent approach to using PHP frameworks, moving towards a more flexible and future-proof approach to PHP development.
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/
"Impact of front-end architecture on development cost", Viktor TurskyiFwdays
I have heard many times that architecture is not important for the front-end. Also, many times I have seen how developers implement features on the front-end just following the standard rules for a framework and think that this is enough to successfully launch the project, and then the project fails. How to prevent this and what approach to choose? I have launched dozens of complex projects and during the talk we will analyze which approaches have worked for me and which have not.
JMeter webinar - integration with InfluxDB and GrafanaRTTS
Watch this recorded webinar about real-time monitoring of application performance. See how to integrate Apache JMeter, the open-source leader in performance testing, with InfluxDB, the open-source time-series database, and Grafana, the open-source analytics and visualization application.
In this webinar, we will review the benefits of leveraging InfluxDB and Grafana when executing load tests and demonstrate how these tools are used to visualize performance metrics.
Length: 30 minutes
Session Overview
-------------------------------------------
During this webinar, we will cover the following topics while demonstrating the integrations of JMeter, InfluxDB and Grafana:
- What out-of-the-box solutions are available for real-time monitoring JMeter tests?
- What are the benefits of integrating InfluxDB and Grafana into the load testing stack?
- Which features are provided by Grafana?
- Demonstration of InfluxDB and Grafana using a practice web application
To view the webinar recording, go to:
https://www.rttsweb.com/jmeter-integration-webinar
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
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.
GDG Cloud Southlake #33: Boule & Rebala: Effective AppSec in SDLC using Deplo...James Anderson
Effective Application Security in Software Delivery lifecycle using Deployment Firewall and DBOM
The modern software delivery process (or the CI/CD process) includes many tools, distributed teams, open-source code, and cloud platforms. Constant focus on speed to release software to market, along with the traditional slow and manual security checks has caused gaps in continuous security as an important piece in the software supply chain. Today organizations feel more susceptible to external and internal cyber threats due to the vast attack surface in their applications supply chain and the lack of end-to-end governance and risk management.
The software team must secure its software delivery process to avoid vulnerability and security breaches. This needs to be achieved with existing tool chains and without extensive rework of the delivery processes. This talk will present strategies and techniques for providing visibility into the true risk of the existing vulnerabilities, preventing the introduction of security issues in the software, resolving vulnerabilities in production environments quickly, and capturing the deployment bill of materials (DBOM).
Speakers:
Bob Boule
Robert Boule is a technology enthusiast with PASSION for technology and making things work along with a knack for helping others understand how things work. He comes with around 20 years of solution engineering experience in application security, software continuous delivery, and SaaS platforms. He is known for his dynamic presentations in CI/CD and application security integrated in software delivery lifecycle.
Gopinath Rebala
Gopinath Rebala is the CTO of OpsMx, where he has overall responsibility for the machine learning and data processing architectures for Secure Software Delivery. Gopi also has a strong connection with our customers, leading design and architecture for strategic implementations. Gopi is a frequent speaker and well-known leader in continuous delivery and integrating security into software delivery.
Neuro-symbolic is not enough, we need neuro-*semantic*Frank van Harmelen
Neuro-symbolic (NeSy) AI is on the rise. However, simply machine learning on just any symbolic structure is not sufficient to really harvest the gains of NeSy. These will only be gained when the symbolic structures have an actual semantics. I give an operational definition of semantics as “predictable inference”.
All of this illustrated with link prediction over knowledge graphs, but the argument is general.
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.
Slack (or Teams) Automation for Bonterra Impact Management (fka Social Soluti...
Debottlenecking Claus Sulfur Recovery Units: An Investigation of the application of Zinc Titanates
1. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
GBH Enterprises, Ltd.
Debottlenecking Claus Sulfur
Recovery Units: An Investigation of
the application of Zinc Titanates
Process Information 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 Product for
its own particular purpose. GBHE gives no warranty as to the fitness of the
Product 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 for loss, damage or personnel injury
caused or resulting from reliance on this information. Freedom under Patent,
Copyright and Designs cannot be assumed.
2. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Contents
1 Executive Summary
2 Claus Process
2.1 Partial Combustion Claus
2.2 Split Flow Claus
2.3 Sulfur Recycle Claus
3 Zinc Titanates
4 Application of Zinc Titanate to Debottleneck Partial Combustion Claus by
10%
4.1 Process
4.2 ASPEN Modeling Results
4.3 Cost of Zinc Titanate Bed Installation
4.3.1 Basis of Costing
4.3.2 Zinc Titanate Beds
4.3.3 Regen Cooler
4.3.4 Blowers
4.3.5 Results
4.4 Alternative Debottlenecking Technology for Partial Combustion Claus
4.5 Cost of 10% Debottlenecking Using COPE Process
5 Debottlenecking Claus Split Flow System by 10% with Zinc Titanates
6 Debottlenecking Claus Sulfur Recycle System With Zinc Titanate
7 Effect of Zinc Titanate Debottlenecking on Existing Tail; Gas Treatment
Systems
7.1 Selectox
7.2 SuperClaus99
7.3 Superclaus 99.5
7.4 SCOT Process
7.5 Zinc Titanate as a Claus Tail Gas Treatment
7.6 H2S Removal Efficiency With Zinc Titanate
8 Effects on COS and CS2 Formation
9 Questions for further Investigation
3. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
FIGURES
Figure 1 Claus Unit and TGCU
Figure 2 Claus Process
Figure 3 Typical Claus Sulfur Recovery Unit
Figure 4 Two-Stage Claus SRU
Figure 5 The Super Claus Process
Figure 6 SCOT
Figure 7 SCOT/BSR-MDEA (or clone) TGCU
REFERENCES: PATENTS
US4333855_PROMOTED_ZINC_TITANATE_CATALYTIC_AGENT
US4394297_ZINC_TITANATE_CATALYST
US6338794B1_DESULFURIZATION_ZINC_TITANATE_SORBENTS
4. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Figure 1 Claus Unit and TGCU
5. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
An Investigation of the application of Zinc Titanates For Debottlenecking of
Claus Sulfur Recovery Units
1. Executive Summary
Zinc titanates do not appear an attractive option for debottlenecking Claus
processes by ~10% because the capital cost of the installation is relatively high
(10% of Claus plant cost) compared to the cost of the alternative debottlenecking
technology of oxygen enrichment (COPE) which equates to 1-2% of plant cost
and is much simpler.
However zinc titanates may be attractive as a tail gas treatment process for
Claus because the H2S emissions will be reduced significantly and the capital
cost of zinc titanate bed installation would be less than many alternative tail gas
treatment options (SCOT, Selectox, etc.). Indeed if zinc titanate could be
demonstrated to remove H2S completely from the tail gas it may then become
attractive if legislation on Sulfur emissions tightens.
Since most Claus plants in USA and Western Europe already have tail gas
treatment plants installed, there is no cost advantage to be gained by
debottlenecking with zinc titanates, however, there could be significant benefit in
emerging markets, where Claus units haven no Tail Gas Treatment plants
installed.
2. Claus Process; Figure 2
6. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
2.1 Partial Combustion Claus
Claus Processes are used in refineries to convert the H2S recovered from
hydrotreaters and hydrocrackers into pure sulfur. The H2S is generally removed
from gas streams by absorption using an aqueous solution of alkanolamine. The
solution is then heated and stripped to give H2S gas. Generally on a refinery
there may be several sources of H2S which will be combined at the stripping
stage before being routed to the sulfur recovery stage.
The partial combustion Claus process is used for H2S rich gases with H2S
concentrations above ~50-60%. It consists of a thermal stage and several
catalytic stages for conversion of H2S to Sulfur. In the thermal stage the gas is
burnt with sufficient air to convert 1/3rd
of the H2S to SO2. This gives a product
with an H2S to SO2 ratio of 2:1 and is highly exothermic. A waste heat boiler
downstream of the furnace cools the gas by raising steam.
The following reaction takes place during the thermal stage producing substantial
amounts of Sulfur:
2H2S + SO2 2H2O + 3S
The gas stream is then passed through a condenser to condense the elemental
sulfur before being reheated and passed to the first catalytic stage. Reheating is
carried out to maintain the gas at a higher temperature than the sulfur dew point
in the catalyst bed to prevent sulfur condensation which will rapidly deactivate the
catalyst.
The gas is then passed through 2-3 catalyst beds in series with sulfur
condensation stages and reheat between each catalyst bed. Two catalytic
stages will generally give 94-95% sulfur recovery while three stages will give 96-
97% recovery. A fourth stage is seldom used as it increase recovery by < 1%.
After the catalytic stage the gas stream is generally passed to an incinerator
where any remaining H2S is converted to SO2 before the gas is vented to
atmosphere. It should be noted that the levels of H2S/SO2 remaining in the gas
are still significant and with ever tightening emissions constraints it is often
necessary to add a Claus tail gas treatment system downstream of the catalytic
stage to meet emissions regulations. This will be discussed later.
The important thing to note about the Claus process is that the ratio of H2S to
SO2 must be as near to two as possible after the combustion stage to attain the
best sulfur recovery.
7. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
2.2 Split Flow Claus
The split flow Claus process is used when the H2S level is 10-50% in the feed
gas. The low H2S level means that partial combustion stage would be unstable
at the furnace so only 1/3 of the gas is fed to the furnace and combusted
completely to SO2 (which is much more stable). This combusted gas is then
mixed with the uncombusted gas stream to give H2S: SO2 = 2:1 before being
passed to the first catalytic stage. The catalytic stages are similar to the partial
combustion process.
2.3 Sulfur Recycle Claus
In cases where the H2S level is <10% the SO2 required for the Claus reaction is
produced by burning pure sulfur recovered from downstream to produce the SO2
required for the Claus reaction. Another option is to use a Selectox process to
recover the sulfur. Selectox is generally used as a Claus tail gas treatment
process and will be covered later.
3. Zinc Titanates
Zinc Titanate has the properties of absorbing H2S with the production of water if
H2S is passed through a bed of zinc titanate.
Zn2TiO4 + 2H2S 2ZnS + TiO2 + 2H2O
The zinc titanate bed can be regenerated by air (oxygen) via the following
exothermic reactions:
ZnS + 3/2O2 ZnO + SO2
2ZnO + TiO2 Zn2TiO4
Zinc titanates are formed by mixing Zinc Oxide and Titanium Dioxide solids at
high temperature. They have been patented in the past for use in sulfur
compound hydrolysis and absorption where the bed can be regenerated with air
giving off SO2.
8. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
4. Application of Zinc Titanate to Debottleneck Partial Combustion
Claus by 10%
4.1 Process
By adjusting the H2S to SO2 ratio in the furnace exit gas to greater than 2:1 this
will increase the conversion of the Claus reaction in the thermal and catalytic
stages due to the higher levels of H2S in the feed gas. The result is that all of the
SO2 will be converted but that an excess of H2S will remain. If a zinc titanate bed
were added downstream of the catalytic stages the H2S could be removed down
to 10-100 ppm.
The zinc titanate could be regenerated with air producing SO2 which could be
recycled to the beginning of the process. Both on-line and regeneration beds
would be necessary for continuous operation.
An Aspen model of the process has been constructed to assess whether a 10%
increase in throughput could be achieved by the addition of zinc titanate beds
downstream of the catalytic stage.
4.2 Aspen Modeling Results
As a basis the mass balance for a partial combustion Claus plant with 3 catalytic
stages producing 229.1 Te/day sulfur from Gas Conditioning and Processing
Chapter 9 p341 was modeled first. Reasonable agreement with the mass
balance was achieved by modeling each conversion stage as a kinetic reactor
however the predicted temperatures of the model were very inaccurate. This
was investigated with Aspen who concluded that the sulfur physical properties
were inaccurate within Aspen for this case and that the species of sulfur being
produced would have an effect. Literature indicates that S6 and S8 are likely to
be formed in the catalytic stages however Aspen doesn't have built in physical
properties for these species and I couldn't find any. For the moment the
temperatures of the model have been adjusted manually.
The results of the model with two zinc titanate beds ( online and regen beds) was
that a 10% increase in throughput was achieved for a reduction in air rate to the
furnace of 12%. Conversion of SO2 through the thermal and catalytic stages
was improved with all the SO2 converted by the end of the 2nd
catalytic stage
This is consistent with higher conversions predicted from literature for Superclaus
99 where the Claus unit is operated at higher than 2:1 H2S:SO2 ratio.
9. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
The H2S level entering the zinc titanate bed was about 6% of the feed to the
process. The zinc titanate regeneration was very exothermic and to control the
outlet temperature to around 5000
C (to avoid refractory lining the vessel) a
recycle loop was included around the bed with a cooler to control the outlet
temperature and a recycle blower to provide driving force. The configuration
chosen was to have one on-line zinc titanate bed and one regenerating bed with
the beds switching over after one hour. The net air rate to the process (furnace
+ regen) was increased by 9%. No purge flow between absorption and regen
cycles was included because there should be no hydrocarbons left present after
the furnace.
Purging is used when hydrocarbons present in the feed to zinc titanate beds in
other duties (not Claus processes) may accumulate in online bed and ignite
when regen air is introduced.
Sulfur recovery was as follows:
Thermal
Stage
Kmol/h
Cat Stage 1
Kmol/h
Cat Stage 2
Kmol/h
Cat Stage 3
Kmol/h
Base Case 184.6 85.4 23 4.8
Zinc Titanate
Case
208.6 100.5 23.9 0
The condenser duties were not accurately modeled by Aspen but it is apparent
that the third catalytic stage is redundant (subject to confirmation) and that the
first two condenser duties are significantly larger. This could be important as it is
essential that all sulfur is removed before entering the next catalyst bed to
prevent sulfur fouling of the catalyst (COPE increases condenser duties but
literature doesn't mention needing new condensers after debottlenecking using
COPE). The catalyst beds see 10% higher flow but since the H2S to SO2 ratio is
now >2:1 this should compensate for the reduced residence time.
10. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
4.3 Cost of Zinc Titanate Bed Installation
4.3.1 Basis of Costing
A very rough costing for the inclusion of two zinc titanate bed was derived using
historical cost information and cost indices. The additional equipment required
was as follows:
Item Number
Zinc Titanate Vessels 2
Regen Cooler 1
Regen Blower 1
Air Blower Revamp 1
Feed Blower Revamp 1
Assumptions:
a. The pressure drop through the plant will increase due to the 10% increase
in flow and also due to the inclusion of two titanate vessels. It has been
assumed that the 3rd
catalytic stage can be removed saving some
pressure drop and that the feed blower can be revamped to produce 10%
more flow at 1.8 bara rather than the current 1.55 bara.
b. It has been assumed that there is sufficient margin above the operating
pressures of the existing equipment to run at the new higher pressures. (if
not then the feed blower would remain untouched and a booster installed
between the catalytic stage outlet and the zinc titanate bed inlet)
c. The furnace air and regen air will be supplied from the existing blower
uprated to give 10% more air flow at 2 bara instead of 1.55 bara.
d. The furnace, condensers, reheaters and catalyst vessels are capable of
the new duties without modification.
4.3.2 Zinc Titanate Beds
The zinc titanate bed have been sized based on the process duty as it is the
higher gas flow. A GHSV of 2500 has been found in a relevant patent (Dr.
Floyd Farha - US4333855) and a Sulfur loading of 150 kgS/m3 has been
assumed. A bed volume of 10 m3 was calculated from the GHSV and a life of
2.2h was predicted. Since the bed is once-through, a bed on-line time of 1 hour
has been used.
11. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
The vessel was sized with an L/D ratio of 0.7 (absolute minimum) to reduce the
DP down to < 0.25 bar based upon 3-5 mm catalyst pellets. The vessel is sized
based upon a vertical cylindrical vessel 2.6m ID by 2.5 m H.
A cost of $1000K per vessel was arrived at by calculating the cost of a CS vessel
in 2009 ( correlation ) then multiplying by 3 to allow for using low alloy steel due
to the maximum temperature of 5000
C and adding a fabrication allowance. The
cost was escalated to present day prices using a factor of 1.6. (This cost may be
slightly pessimistic but even using a more accurate cost does not change the
conclusions significantly.)
The cost of the zinc titanate has been excluded.
4.3.3 Regen Cooler
The regen cooler has been sized as an air cooler based upon a cost from a
recent study. A cost of $54K was used.
4.3.4 Blowers
The process is low pressure and so it is believed that blowers rather than
compressors can be used. The recycle blower on the titanate regen recycle is a
new item. The cost was derived from a correlation which uses the predicted
power consumption to give a price and then converted to present day costs.
The prices for the air and feed blower upgrades were assumed to be 30% of the
cost of new blowers from the same correlation.
The costs were corrected by inflation to give present day costs since a cost
indice for 2009 couldn't be found.
4.3.5 Results
The total equipment cost was calculated to be $624K and an installation factor of
2,48 was used to give installed cost.
The total installed cost was estimated at $1,553K installed (excluding zinc
titanate costs)
12. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
A correlation from Petroleum Refining predicted a Claus plant installed cost of
$15.51M for the base case plant and so the 10% debottlenecking using zinc
titanate would cost ~10% of the plant installed cost.
4.4 Alternative Debottlenecking Technology For Partial Combustion
Claus
The main method of debottlenecking partial combustion Claus processes
appears to be oxygen enrichment (COPE). The air used to partially combust the
H2S is partially enriched with oxygen reducing the inert nitrogen level in the gas
passing through the process and allowing more feed to be processed with no
pressure drop penalty. The residence time in the catalyst beds remains
unchanged because the gas volume doesn't increase however the amount of
sulfur condensed in each condenser will increase which doesn't appear to cause
any problems.
There are three levels of enrichment:
Up to 28% enrichment will give an increase in plant capacity of 10-30% for
minimal capital cost. The limit of 28% oxygen is the upper limit before the
oxygen pipe work metallurgy and cleanliness become a problem.
28-40% oxygen will allow 50-60% capacity increase. In this process the oxygen
is not mixed with the air but is inserted into a new burner via a discrete oxygen
port. The limit on this system is that above 40% oxygen the temperature limit on
refractory lining of the furnace is exceeded. (COPE Phase 1)
40% to 100% enrichment is only possible with feeds above ~65% H2S in the feed
gas and requires a special burner and also the introduction of a recycle flow of
cool gas from downstream to moderate the furnace temperature. (COPE Phase
2- In about 30 percent of cases using COPE the furnace and waste heat boiler
need replacing). An alternative is SURE where a second combustion stage is
added upstream of the existing furnace to limit furnace temperatures.
For COPE quoted increase in processing rate of up to 150% can be achieved
using oxygen enrichment for a capital cost of between 5 and 25% of the capital
cost of the original plant for. I do not think that this cost takes account of the cost
of supplying oxygen to the system for enrichment. If oxygen is available on-site
then the cost is probably reasonable. If a dedicated oxygen supply (imported
liquid oxygen) the cost could be substantial.
13. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
For SURE the capital cost of a doubling of capacity appears to be about 50% of
the original plant cost excluding oxygen supply.
4.5 Cost of 10% Debottlenecking Using COPE Process
The capital cost of debottlenecking the plant would be minimal since only an
oxygen pipe break-in to the existing furnace air supply is necessary. Assuming
that oxygen is not available on-site, for a 10% debottleneck project the oxygen
requirement is insufficient to make an on-site air separation plant economical.
The oxygen would be supplied as liquid oxygen and storage etc will be required.
The plant operator would rent a suitable storage vessel for $1,600/month
(installation costs $8,910). For an increase in Claus capacity of 10% (requiring
9Te/day oxygen) oxygen would cost ~$79/Te. The total cost per hour of
operation for oxygen and tank rental and delivery would be $32.34/hour. The
annual operating cost would be ~$256K(excluding electric drives) and the capital
cost might be ~$82K so in comparison with zinc titanate the COPE process
would be cheaper and simpler to install. It would take 6 years before the zinc
titanate system started to show a saving over COPE.
5. Debottlenecking Claus Split Flow System by 10% With Zinc
Titanates
The Claus split flow system is for mid-level H2S concentrations (10-50%) and
could be debottlenecked by removing the furnace and waste heat boiler and
adding two zinc titanate beds at the outlet. The hot SO2 from the regen could
then be recycled to the beginning of the process and the heat recovered from the
regen recycle cooler could be used to preheat the feed before the first catalytic
stage. The use of a higher H2S to SO2 ratio would improve conversion and
eliminate SO2 from the product. The elimination of the waste heat boiler to some
degree balances the increase in pressure drop arising from the titanate bed and
the increase in capacity (10%) however a regen recycle blower and cooler would
be needed. The feed blower and air blower would probably need upgrading.
The capital cost of this modification is likely to be in the same order as the partial
combustion debottleneck case. (i.e., 10% of original plant cost)
The alternatives for debottlenecking split flow Claus are oxygen enrichment
(COPE). Mid level enrichment will probably be necessary to get the nitrogen flow
savings required. This requires a dedicated oxygen line and a new burner for the
furnace. The cost of oxygen would less than previously since the H2S level is
lower but the capital cost will be higher as a new burner is necessary.
14. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
It is still likely to be significantly cheaper than the zinc titanate option and the
lower oxygen usage will reduce operating costs further.
6. Debottlenecking Claus Sulfur Recycle System With Zinc Titanate
The Claus Sulfur recycle process is for low level H2S concentrations <10%. To
debottleneck using zinc titanate beds would require the elimination of the sulfur
burner and the recycle of SO2 from the titanate regen to give a H2S to SO2 ratio >
2 to improve conversion. Heat from the regen recycle could be used to preheat
the feed. No saving in pressure drop will be made since the sulfur burner is not
in the main process stream and it's elimination does not reduce pressure drop so
blowers/compressors will have to be upgraded.
Alternative debottlenecking schemes are unclear. I am not sure if COPE is an
option here since the amount of air combusted is so low. If it is viable I suspect
that the H2S level is so low that oxygen enrichment of the sulfur burner would
require higher than 28% oxygen levels so that dedicated oxygen line and a new
burner would be necessary. This area needs further investigation.
7. Effect of Zinc Titanate Debottlenecking on Existing Tail Gas
Treatment Systems
The advent of tighter emissions consent levels means that Claus plants alone
struggle to meet the emissions levels required. Typically Claus plants are
required to recover 99.8% of the sulfur feed while most Claus systems achieve
94-96%. To get around this tail gas treatment systems have been added to the
end of the Claus processes to polish the tail gas. They will generally reduce the
SO2 level to ~250ppm exit the tail gas system. If titanate beds are used
upstream to improve throughput what effect will it have on the tail gas treatment
systems. The processes are as follows:
7.1 Selectox
Selectox takes Claus tail gas (CO2 with low levels H2S and SO2) and initially
burns it with sub stoic air to form H2 & CO (reducing gas) which is fed to a CoMo
reactor to form H2S then cooled. It is then fed to the Selectox reactor generating
SO2 and S after which the S is condensed. 80% of the sulfur in the tail gas is
recovered.
15. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
By running the upstream Claus at a higher H2S to SO2 ratio to accommodate the
zinc titanate beds this will eliminate the SO2 and produce H2S in excess. The
H2S will be removed in the titanate beds and recycled as regenerated SO2. The
H2S level in the treated gas exiting the zinc titanate will be 10-100ppm(patent)
and there should be minimal SO2 so tail gas treatment shouldn't be necessary as
long as the gas is passed through an incinerator to convert the H2S to SO2 which
will be 10-100 ppm (lower than required by legislation). Thus the Selectox
process would be redundant.
7.2 SuperClaus99
Superclaus99 operates at a H2S to SO2 ratio of greater than 2:1 to convert all
the SO2 in the catalytic stages and leave H2S to pass into the SuperClaus reactor
where it is converted to sulfur by sub stoic combustion. The use of zinc titanate
upstream of the Superclaus reactor would remove the H2S making the
Superclaus reactor redundant as long as there was a downstream incinerator to
convert the H2S (10-100ppm) to SO2.
7.3 Superclaus 99.5
This version runs with H2S to SO2 ratio of 2:1 and uses a catalytic hydrogenation
reactor to convert all the remaining SO2 to H2S before passing it forward to the
superclaus reactor. This gives slightly better performance.
Zinc titanate beds upstream of the hydrogenation reactor could make Superclaus
redundant because only low levels of H2S (10-100ppm) would be coming forward
anyway which would be converted to SO2 by the downstream incinerator.
7.4 SCOT Process
In the SCOT tail gas process a small amount of hydrogen is added to the tail gas
which is passed through a hydrogenation convertor to convert CS2, COS etc into
H2S. The gas is cooled to ambient and the H2S absorbed by an amine system
before being recycled to the Claus process inlet.
The effects of zinc titanate beds for 10% increase in throughput are again to
make the SCOT process redundant. The low levels of H2S coming forward from
the zinc titanate bed will be converted to SO2 in the incinerator.
16. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
7.5 Zinc Titanate as a Claus Tail Gas Treatment
Zinc Titanate beds will give a much lower SO2 level going up the stack than the
current tail gas treatments. It could be installed on a Claus system for ~10% of
the Claus system cost and give 10% more throughput with improved emissions
levels. The operating costs of the zinc titanate system are associated with
electrical drives for blowers and fans.
7.6 H2S Removal Efficiency With Zinc Titanate
Typically the capital cost of a SCOT or Selectox tail gas system is 70-100% of
the capital cost of the Claus system and significant operating costs in the order
of $100/day per 100T sulfur product are incurred. Superclaus can be installed
around 10% of the cost of a Claus plant and is thus similar to the projected cost
of installing a zinc titanate tail gas treatment system.
For a company who already has a tail gas treatment system the savings in
operating costs would not be significant enough to justify switching to zinc
titanate beds. However for companies with no tail gas treatment there may be a
market for zinc titanates as a debottlenecking system cum tail gas treatment for
Claus plants. Most refineries in the US and Europe already appear to have tail
gas treatment plants installed on their Claus plants so there doesn’t appear to be
much of a market for this in the developed world. (Perhaps there is more of a
case in emerging markets.)
If we could demonstrate that the zinc titanate beds eliminate SO2 emissions
altogether (by consuming all SO2 in Claus reactors and reducing the H2S carry-
over from the zinc titanate beds to zero) this may be a better driver for replacing
conventional tail gas treatments with zinc titanate beds as environmental SO2
emissions limits tighten. If the zinc titanate beds replace an existing tail gas
treatment system there should be no issue over pressure drop as the available
pressure drop would suffice.
(What vessel sizes are used in tail gas treatment systems. Could the vessels be
re-used for zinc titanate? The high design temperature required for the titanate
vessels would probably prevent their reuse in a titanate system.)
17. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
8. Effects on COS and CS2 Formation
COS and CS2 can be formed in partial combustion processes in the furnace.
They can be hydrolyzed in the first catalytic stage of a Claus plant by operating it
at around 370C. In the split stream Claus process the complete combustion in
the furnace prevents formation of CS2 and COS. In Sulfur recycle no CS2/COS
should be formed in the sulfur burner.
NH3 can be formed in the sour water shift but generally it will be completely
combusted in the furnace by routing it to the main burner. It is unclear in split
flow/Sulfur recycle Claus systems how it is dealt with.
Using zinc titanates should have no impact on COS or CS2 formation based on
current information.
9. Questions for further investigation
9.1 How low will the outlet H2S concentration from a zinc titanate bed be?
9.2 What inlet temperature is necessary for the H2S removal bed and for the
regen bed of a zinc titanate bed.
9.3 What size are the vessels in tail gas treatment systems and what design
temperatures are they likely to have.
9.4 Is more detailed information/physical properties available about the
catalytic stages of the Claus process.
9.5 What proportion of Claus plants have tail gas treatment installed. What is
the split of types of tail gas systems used.
9.6 Cost of zinc titanate.
9.7 Life of zinc titanate.
9.8 Zinc titanates patent search for current patents which may restrict using
zinc titanates in Claus plants.
18. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Figure 3 Typical Claus Sulfur Recovery Unit
Figure 4 Two-Stage Claus SRU
19. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Figure 5 The Super Claus Process
The Super Claus process for producing sulfur:9 (1) main burner, (2,4,
6,8) condensers, (3,5) Claus reactors, (7) reactor with selective oxidation
catalyst.
Figure 6 SCOT
20. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Figure 7 SCOT/BSR-MDEA (or clone) TGCU