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//XPREP-CIC 1 Introduction C-IC Principle of Operation TEIS Software Application & Standardization
//XPREP-CIC
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Introduction C-IC
Principle of Operation
TEIS Software
Application & Standardization
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Introduction Combustion-IC
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Combustion – IC
• Oxidative pyrohydrolitic combustion
followed by IC detection (C-IC)
• Speciated Halides (Fluor, Chlorine,
Bromine, Iodine) and Sulfur
determination by a single analysis
• Halogens are corrosive, poison
catalysts, damage industrial equipment,
harmful to the environment
Advantages C-IC
• Eliminates complex sample
preparation conventional methods
• Speciated analysis
• Automated, increased productivity
• Improved Limit of Detection
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Applications
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Petrochemical / Refineries • Petrochemicals • Organic Solvents• Fuels • Biofuels• LPG & Gas • Lubricants
Plastics • Polymers (PE, PP)• Additives • Pigments
Environmental Monitoring • Recycling • Waste disposal • Waste water treatment
Electronic Components • RoHS, WEEE compliance
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Why is C-IC Analaysis Required?
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Refineries, Petrochemical, Biofuels, Chemical Companies
Trace Elements of …
• Halogens cause corrosion of piping and equipment in production process
• Sulfur decreases lifetime of catalysts
• Sulfur contribute to emissions
• Halogens and Sulfur pollute the environment
• Halogens and Sulfur decrease quality of Commodity Specs
• Halogens and Sulfur are regulated in many countries
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Refinery – Halogens & Sulfur Analysis
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Analysis of Halogens & Sulfur in different products at different stages of Refining Process
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Why is C-IC Analysis Required?
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Plastics & Polymers…
• Halogenated Sulfur-containing Compounds added as Plasticizers, Flame retardants, and Heat Stabilizers to Plastics
Environmental Monitoring…
• Organo-Halogens are Toxic compounds - Monitoring and Control of Environmental Pollution
• AOX represents amount of Fluorine, Chlorine, and Bromine in Organic Compounds
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Why is C-IC Analysis Required?
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Electronic Components - Bromine & Chlorine analysis in Cables, PCB, Insulating Materials…
Fast and Global increase of Consumer Electronics Waste
• Reduce Damage to Environment! • Restriction for the use of Hazardous Materials
International Entities that focus on Electronic Component Analysis:
• WEEEE (Waste Electronical and Electronic Equipment Directive) • RoHS (Restriction of Hazardous Substances Directive)• JPCA (Japan Printed Circuit Association)• IEC (International Electrotechnical Commission)• IPC (Association Connection Electronic Industries)
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XPREP C-IC
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“World’s first Independent Sample Preparation System for C-IC analysis.”
Combustion Unit Fraction Collection Ion Chromatograph
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XPREP C-IC Key Features
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Speciated Halides and Sulfur analysis by any renowned IC!
Controlled Sample IntroductionCompatible with Direct Injection- and Boat Inlet System• Large sample volume, Low detection limit
65 position Fraction Collection Unit Immediate analysis or storage of combusted samples• Enables sample re-run
Small Footprint Save Bench space - Half the size compared to existing C-IC configurations
Integrated Sampling System Automated dosing of reagents and absorbance of samples
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Principle of Operation
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Sample Combustion Collection Detection IC
Sulfur SOx SO42-
Halogens H-X, X2 F-, Cl-, Br-, I-
Sample Introduction
Combustion Collection IC-Injection
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Principle - Sample Introduction
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Sample Introduction
Combustion Collection IC-Injection
Automated Sample Introduction
Robust Sampling Systems for Liquid, Viscous, Solid, Gas and LPG
Unique: Two introduction modules for Combustion!
• Conventional Boat-inlet System (Boat Module)• Optimized Direct Injection System (Liquids Module)
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Sample Introduction - Modules
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0
200
400
600
800
1000
1200
Boat Module
Liquids Modulebp <420 °C
GLS
Refinery Example - Sample Boiling Point vs Introduction Method
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Sample Introduction - Modules
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Switching between Introduction Modules <2 minutes• Flexibility with different Matrices!
Software Controlled Introduction Module Connections• No (hot) metal clamps required for glass part connections• Ease of use
C-IC related ASTM & UOP Test Methods• Boat-inlet system for all sample types…
XPREP C-IC Horizontal Furnace• Compatible with Boat-inlet system & Direct injection system!
Liquids Module (direct injection) • Designed for Liquid Samples <420 °C bp • Compliant with ASTM D7359, ASTM 7994, UOP 991, UOP 1001
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Sample Introduction – Direct Injection System
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Auto Sampler Fully Controls• Syringe wash• Accurate sampling 5-100 µL• Introduction at µL/sec in heated Liquids Module (500 ºC)• High velocity carrier gas stream 100 mL/min
Samples (boiling point <420 °C)• Fuels • Aromatic Hydrocarbons• Liquid Organics • Organic Solvents • Gas & LPG
XPREP C-IC First ‘Direct Injection’ Solution!
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Sample Introduction – Direct Injection System
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Features Liquids Module Benefits compared with Boat Module Liquid samples <420 °C
Temperature Controlled (500°C)
Controlled Sample Dispense -
Typically 1 µL/s
• Controlled Evaporation • Controlled Sample Combustion
prevents Soot or Coke formation• Improves Repeatability • Eliminates the need for Boat
Program• Decreases Time of Analysis
Larger Sample Volume up to
100 µL
• Improves IC-detection limit
• Multiple Injections from same
sample for single IC analysis!
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Sample Introduction – Direct Injection System
TE Instruments
0 100 200 300 400 500 600
Direct Injection
Boat Inlet
Seconds
Intr
oduct
ion
Module
Improved Time of Analysis Boat-inlet vs. Direct Injection
Combustion sample 1 Combustion sample 2 Combustion sample 3
Boat Inlet
Volume 30 µL
Injections 1
Total Volume 30 µL
Time 8 minutes
Direct Injection
Volume 100 µL
Injections 3
Total Volume 300 µL
Time <6 minutes
LOD Improved!
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Sample Introduction – Boat Inlet System
TE Instruments 17
Liquids by Boat Module • Liquids, with Low and High Boiling Points• Small Boat Volume 30 – 50 µL• Quartz Wool• Compliant with C-IC International Test Methods
Software Controlled Boat Program• Can be customized per Application
Solids by Boat Introduction• Weighed-in sample max. 250 mg, application dependent• Weighed-in Organic Sample typically 30-50 mg • Plastics, Solid Organics, Oils, Fats, etc.
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Sample Introduction – Boat-Inlet System
Solids by Boat Module
• No Cup Accumulation • Clean Cup Container
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Sample Introduction – Gas & LPG
Sampling Pressurized Gas & LPG Samples
Sample Transferred by GLS autosampler into Liquids Module
Connection Needle Pierced through Septum
Safety Features • Gas Leakage Sensor• Automatic Safety Lock• Valved (Shut-off) Quick Connects
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Sample Introduction – Auto Samplers
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Sample Liquids
Volume 5 – 100 µL
Sample Positions 105, optionally 210
Optional Conditioned Sample Tray
Sample Pressurized Gas & LPG
Sample Loops 10 mL Gas, 100 µL Liquefied Gas
Max. pressure LPG 25 bar, 363 psiGas 50 bar, 725 psi
Optional Automatic Lock Option
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Sample Introduction – Auto Samplers
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Sample Solids
Sample positions 20, 40, 60
Sample amount 5 – 250 mg
Sample Non-pressurized Gas
Volume 10 – 1000 mL
Sample positions Up to 10 Tedlar® bags
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Sample Combustion
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Sample Introduction
Combustion Collection IC-Injection
• Pyrohydrolitic Combustion oxygen-rich environment at High Temperature
• Prevents loss of Fluorine in Combustion Tube
• All Glassware, e.g. Combustion Tubes and Introduction Modules, are designed, developed and manufactured by TE Instruments
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Sample Combustion
XPREP C-IC Combustion Tube – Oxidation Power & Flow Path Protection
• Collision Flow Technique
Powerful Combustion Capacity
• Single-Stage Capturing Filter
Protects Downstream Flow Path →
Internal Tubing & IC Column
• ‘Self-Cleaning’ Capturing Filter
Regenerates at High Temperature (1000 °C) and Oxygen Flow
• Cooling Mechanism for Boat Introduction Prevents Sample Evaporation during Loading Cooling prevents Sample
Combustion Furnace
• Uniform heat distribution
• Temperature Stability
• Proven Robustness
• 1150 °C max. – Typically set at 1000 °C
• 5 Year Warranty!
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Sample Combustion
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Sample Combustion
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Typical Settings Combustion Boat Inlet Direct Injection
Oxygen Flow 300 mL/min 300 mL/min
Argon Flow 100 mL/min 100 mL/min
Oxygen Collision Flow 100 mL/min 100 mL/min
UPW Dosing Speed 2 µL/s 2 µL/s
Furnace Temperature I 750 °C 1000 °C
Furnace Temperature II 1000 °C 1000 °C
Introduction Module Quartz Boat Module Liquids Module (500 °C)
Sample introduction speed Boat program 1 µL/s
Sample volume Combustion Unit 30 µL 100 µL
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Fraction Collection
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Sample Introduction
Combustion Collection IC-Injection
• Absorber medium is added to the output gas stream after combustion
• Complete Absorption of Analytes in Fraction Collection Unit
• H-X, X2 and SOx are converted to F-, Cl-, Br-, I- and SO42
• Halide and Sulfuate Anions are Separated on the IC column
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Fraction Collection
TE Instruments 27
• Temperature Controlled Condenser ensures
Complete condensation of Dosed Reagents
• Up to 65 combusted samples can be Absorbed and
Stored in the individual vials
• Disposable Sample Vials (PP), eliminates rinsing
between samples
• Immediate transfer to IC for analysis or storage of
Combusted Sample(s)
65 Position Fraction Collection Unit
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Conditioning Combustion Sample
Temperature Controlled Condenser
• Complete Condensation Dosed Reagents
before entering Fraction Collector
• Accurate and Repeatable Absorbent Dosing
• No need for Internal Standard (Phosphate)
Graphic Representation Temperature Controlled Condenser
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Fraction Collection
TE Instruments 29
• Low Maintenance Integrated Sampling System
• Operates with Dual Channel Needle
• Inner Channel for Dosing Reagents and Absorption
• Outer Channel for Sample Transfer to IC
Typical Parameters Fraction Collection
Absorption solution 100 mg/L hydrogen peroxide (H2O2)UPW water
Absorption tubes 23 mL – optional 40 mL
Typical volume absorption tubes 10 mL
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IC-Injection
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• Absorbent Containing Analytes is automatically transferred to any Renowned IC
• Internal Syringe Pumps of the Fraction Collection Unit load and rinse the IC sample loop
Sample Introduction
Combustion Collection IC-Injection
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IC-Injection
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Sample Loop
• Six-way-valve and 100 µL Sample Loop by default
integrated - Customizable (application dependent)
• Sample Loop loads Pre-Concentrator in the IC
• Sample Injection Valve automatically injects
aliquot of known volume into the IC
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XPREP C-IC
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Combustion Unit Fraction Collection Ion Chromatograph
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TEIS Software
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TEIS Software
Method ManagerUse default methods or create the perfect application settings
Visual DevicesReceive a status overview of every connected device
Remote control Configurable Remote Start/Stop
Dashboard Overview Auto Performance Evaluation
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Standardization C-IC
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Standard Method Range
ASTM D7359Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures
0.1 – 10 mg/kg (F, Cl, S)
ASTM D7994Total Fluorine, Chlorine, and Sulfur in Liquid Petroleum Gas (LPG)
1 – 300 mg/kg (F, Cl) 5 – 300 mg/kg (Cl)
UOP 1001Chloride and Fluoride in Liquefied Petroleum Gases (LPG) by Combustion Ion Chromatography (CIC)
1 – 1500 mg/kg (F, Cl)
UOP 991Trace Chloride, Fluoride, and Bromide in Liquid Organics by Combustion Ion Chromatography (CIC)
> 0.1 mg/kg (F, Cl)> 0.2 mg/kg (Br)
ASTM 8150 Standard Test Method for Determination of Organic Chloride Content in Crude Oil
> 1 µg/g (Cl)
Multiple standards
Compliant with the performance standards of international test methods like ASTM, UOP, ISO, DIN, EN, JIS, KS
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XPREP C-IC Summary
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Controlled Sample Introduction• Compatible with Direct injection- and Boat-inlet system• Low Detection Limit• Improved Time of Analysis • Software-controlled Exchange
65 position Fraction Collection Unit • Accurate & Repeatable Absorbent Dosing • Immediate Analysis or Storage of Combusted Samples • 65 Positions – No Continuous Rinsing required
Speciated Halides and Sulfur analysis by any renowned IC Accurate Injection of Combusted Sample into IC
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XPREP C-IC Summary
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Small Footprint Half the Size compared to existing C-IC configurations
Integrated Sampling System Fully controls Dosing of Reagents and Absorption
Automated Sample Introduction Robust Sampling Systems for all Matrices
Oxidative Pyrohydrolitic Combustion of Solids, Liquids, Gas and LPG• Robust Furnace• Specially Designed XPREP C-IC Combustion
Tube• Powerful Combustion Capacity
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Questions?
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