Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world...
Transcript of Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world...
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Sachin Patil, Carl Fisher, and Jeff Rohrer
Thermo Fisher Scientific, Sunnyvale, CA, USA
Determination of total fluorine, chlorine, and sulfur in aromatic hydrocarbons by oxidative pyrolytic combustion followed by ion chromatography
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Analyte
Oragnization Reference Numbers Sample F Cl Br I S Remarks
ASTM D7359-14a Aromatic hydrocarbons and their mixtures X X X Active
ASTM D5987-96 Coal and coke X Active
ASTM UOP1001-14 Liquefied petroleum gases (LPG) X X Active
ASTM UOP991-13 Liquid organics X X X Active
ASTM UOP588-12 Hydrocarbons X Active
ASTM WK44683 Coal X X Work in progress
ASTM D7994-17 Liquefied petroleum gases (LPG) X X X Active (4/17)
ASTM WK22144 Graphite and carbon X X X Work in progress
DIN EN 62321-3-2 Polymers and electronics X Active
DIN 51727 (2001-06) Solid fuels X Active
ISO 19242 Rubber X Active
KSA KS M0180 Electric & electronic equipment X X X Active
IEC 61249-2-21 General definition X X X X Active
IEC 62321-3-2 Polymers and electronics X Active
IEC 60754-3 Cables X X X X Work in progress
IPC IPC-4101B General definition X X X X Active
JPCA JPCA-ES-01-1999 General definition X X Active
JEITA ET-7304 Soldering materials X X X X Active
Combustion Ion Chromatography (CIC) Reference Methods
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ASTM D7359 - 14a
Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their
Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatography Detection
(CIC)
The presence of fluorine, chlorine, and sulfur in aromatic hydrocarbon matrices can:
• Contribute to emissions
• Be harmful to many catalytic chemical processes - catalytic poisoning
• Lead to corrosion
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• Advantages
• Eliminates complex sample preparation
• Automated
• Easy to use
• Highly sensitive
• Produces fewer environmental
contaminants
Combustion Ion Chromatography
• Oxidative pyrohydrolytic combustion
followed by ion chromatography
detection (CIC)
• Standard test method for total
fluorine, chlorine, and sulfur in
aromatic hydrocarbons and their
mixtures
• Rapidly becoming the preferred
analytical technique for measuring
halides and sulfur
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Petrochemical production
• Feedstock: crude oil, ethylene, propylene
• Intermediates: naphthas, reformates
• Products: gasoline, diesel fuel, LPG
Power generation
• Coal
• Fuel Oil
• Natural Gas
Environmental
• Water Disinfection Byproducts
• Soils
• Organic waste disposal
• Plastic recycling
CIC: Markets and Samples
Pharmaceutical
• Solid products
• Solvents
Plastic production
• Additives
• Pigments
Samples can be solids, semi-
solids, liquids and even gasses
RoHS, WEEE compliance
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CIC Theory
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Thermo Scientific Combustion IC System
Ion
Chromatograph
Gas Absorption
UnitFurnace Solid/Liquid Autosampler
Mitsubishi AQF-2100H
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CIC Sample Changers
Mitsubishi ABC-210Automatic Boat Changer
• Feeds samples into
horizontal furnace
Mitsubishi ASC-240SSolid Sample Changer
• Solid & liquid* samples
• Solid – 150 mg
• liquid – 100 µL
• 40 position, ceramic
* For liquid samples,
this is manual
Mitsubishi ASC-250LLiquid Sample Changer
• Inj. vol. max. 150 µL
• 50 position in each
2, 4, 6 mL trays
Mitsubishi ASC-270LSLiquid/solid Sample Changer
• Switch between solid and
liquid samples by replacing
sample tray and head
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• Stainless steel sample injection loop with
heated expansion chamber
• Introduces multiple LPG sample injections
automatically, enabling calibration of the CIC
with a single LPG Standard
• ASTM D7994-17
Mitsubishi GI-260
• Gas/ LPG Injector
CIC Gas Injector
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Electric Furnace – Mitsubishi HF-210
• Hinged furnace design
• Easy open / close feature
• Allows easy access to pyrolysis tube
Easily inspect
and replace
pyrolysis tube
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Combustion Gas/Absorption Module
Injection
Valve
Drain
Pump
Syringe
Pump
Absorption
Tube
Mitsubishi GA-210
• Absorption tube
• Heat-resistant glass,
10 or 20 mL
• Syringe burette
Mitsubishi ES-210
• External solution selector
• Four aqueous
solutions/standards can be
injected without combustion
Channel
Indicator LED
Mitsubishi CM-210
• Combustion monitor
• Determines sample burn
rate by oxygen consumption
• Optimizes boat program
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Software-based Automation to Increase Productivity
• Established program controls total analysis
• Capable of starting combustion of next sample to reduce waiting time
1st Sample
Preparation Combustion Ion Chromatography
Preparation Combustion Ion Chromatography
Preparation Combustion
2nd Sample
3rd Sample
15 minutes 15 minutes
1st Sample 2nd sample 3rd sample 4th sample 5th sample
Analysis
time
25min (Data in
15+10 min)
40 min (Data in +15 min
instead of 15+10 min)
55 min (Data in +15 min
instead of 15+10 min)
@70min @85min and so
on…
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Data Management
* No manually prepared eluents or regenerants
ConductivityDetector
High-Pressure Non-Metallic Pump
Eluent Generator
KOH
WasteSample Inject(Autosampler)
Recycle Mode
Eluent Suppressor
Detection
H20
Separation
Anion Exchange Column
Reagent-Free™ IC System
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Pt Cathode
(2H2O + 2e– 2OH– + H2)
Cation-ExchangeConnector
HydroxideGeneration ChamberPump
H2O
Pt anode
(H2O 2H+ + ½O2 + 2e–)K+
ElectrolyteReservoir
K+
KOH + H2
KOH
H2
DegasUnit
[KOH] Current
Flow rateVent
CR-ATCAnion Trap
Electrolytic Generation of KOH Eluents
• Easy set-up and no need to prepare manual eluents
• Elimination of acid and base handling
• Longer-lasting pumps because they encounter only deionized water
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• The Thermo Scientific™ Dionex™ IonPac™ AS18-4µm column is a high-capacity column, which
allows injection of more-concentrated samples without overloading or peak broadening
• Through the use of smaller resin particles, the 4µm column offers the highest peak efficiency and
best resolution of common inorganic anions
• Available in three formats:
• 4 ×150 mm (analytical), 2 ×150 mm (microbore), 0.4 ×150 mm (capillary)
Dionex IonPac AS18-4µm Column
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The Thermo Scientific Dionex Ion Chromatography Product Line
RFIC
HPIC
Thermo Scientific™
Dionex™ Aquion™
IC System
Thermo Scientific™
Dionex™ Integrion™
HPIC™ System
Thermo Scientific™
Dionex™ ICS-4000
Capillary HPIC™ System
Thermo Scientific™ Dionex™
ICS-6000 Hybrid HPIC™ System
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Our Unique IC Strengths
Suppression Technologies (Anion & Cation)
Column Offerings (low to high capacities, 4 µm formats, …)
Eluent Generation Technology
Ease of Use with Thermo Scientific™ Chromeleon™ Chromatography Data System (CDS)
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Technical Advantages of Combustion IC
• Coulometric cells have variable day-to-day performance
Reproducible results
• Better process controlSub-mg/L
determinations
• Eliminate cell switching – less equilibration time
Total sulfur and halides with one instrument
• Speciation of halides including F, Cl, Br & IChromatographic
separation
• Comparable to other ASTM methodsTime and precision
• All sulfur converted to sulfateResults independent of
sample matrix
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Combustion Conditions
Parameter
Volume Combusted 50 µL
Furnace Inlet Temp. 900 ˚C
Furnace Outlet Temp. 1,000 ˚C
Argon Flow (Carrier) 200 mL/min
Oxygen Flow (Combustion Agent) 400 mL/min
Humidified Argon Flow 100 mL/min
Pyrolysis TubeQuartz tube with ceramic insert and
quartz wool
Sample Boat Quartz
Absorption Solution 30 ppm hydrogen peroxide
Absorption Solution Volume 3.5 mL
(High fluoride can
damage the tubing)
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IC Conditions
IC Conditions
Columns
Dionex IonPac AG18-4μm column, 4 × 30 mm,
and Dionex IonPac AS18-4μm column, 4 × 150
mm
Eluent SourceThermo Scientific™ Dionex™ EGC 500 KOH
Eluent Generator Cartridge
Eluent Concentration Variable
Flow Rate 1.0 mL/min
Column Temp. 30 ˚C
Inj. Volume 100 μL
Detection Suppressed conductivity, recycle mode
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IC Method Optimization: Isocratic Method
0.0 5.0 10.0 15.0-2.0
12.0
Anion standard
F- + Organic acids
SO42-
Cl-Br -
Carbonate
ClO2-
NO2-
Isocratic elution:
23 mM KOH
µS
Time (min)
Coelution of fluoride prevents use of isocratic method.
(Direct injection)
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IC Method Optimization: Step Change
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.50.40
0.62
F-
SO42-
Cl-
µS
Time (min)
Step change elution
4 mM KOH 0 to 2 min
18.5 mM KOH 2 to 10 min
4 mM KOH 10 to 14.5 min
Anion standards
(Combusted)
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Anions Present in Solvent Blank
0.0 5.0 10.0 14.50.4
0.8
Solvent (MeOH) blank
Associated
with H2O2
F-SO4
2-Cl-
Br -
µS
Time (min)
Step change elution
4 mM KOH 0 to 2 min
18.5 mM KOH 2 to 10 min
4 mM KOH 10 to 14.5 min
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Anion Standard Separation
0.0 5.0 10.0 14.50.4
0.8
0.5 ppm standard
Solvent (MeOH) blank
F-
SO42-
Cl-
Br -
µS
Time (min)
• H2O2 and solvent (methanol) purity is important
• Background anions affect LOQ
Step change elution
4 mM KOH 0 to 2 min
18.5 mM KOH 2 to 10 min
4 mM KOH 10 to 14.5 min
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CIC Calibration Linearity
0.0 5.0 10.0 14.50.2
1.3F-
SO42-
Cl-
µS
Time (min)
0.2 – 10 mg/L
(9 conc.)
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Method Validation: Calibration and Precision Data
Analyte
Ret.
Time
(min)
Linearity
Range
(mg/L)
Coeff. of
Determination
F 3.55 0.2 to 10 1.000
Cl 5.46 0.2 to 10 0.999
SO4 11.03 0.2 to 10 0.999
Standard
Conc
(mg/L)
Retention Time
RSDPeak Area RSD
F Cl SO4 F Cl SO4
0.2 0.11 0.02 0.02 3.65 3.56 2.54
0.5 0.11 0.04 0.01 2.57 2.01 1.15
2.5 0.16 0.03 0.02 0.49 0.45 0.11
Calibration Precision (n=7)
• Calibration linearity >0.999
• Good method precision < 4% RSD
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CIC Chromatogram of a Gasoline Sample (Premium)
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.50.2
0.6
µS
Time (min)
F-
SO42-
Cl-
?
?Br -
Separation of target analytes achieved in < 15 min
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Method Validation: Spike Recovery Results (Accuracy)
Spike
Conc
(mg/L)
F Cl SO4
Average
Amount
(mg/L)
%
Recovery
Average
Amount
(mg/L)
%
Recovery
Average
Amount
(mg/L)
%
Recovery
0
(Premium
Gasoline)
0.24 - 0.22 4.37 -
0.5 0.75 102.2 0.71 96.5 4.82 91.0
1 1.22 98.0 1.08 85.9 5.30 93.0
2 2.11 93.7 2.03 90.5 6.30 96.3
Spike recoveries are consistent with good method accuracy
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• CIC method based on ASTM D7359-14a to determine F, Cl, and S in aromatic hydrocarbons
• Good precision and accuracy with recovery ranging from 85–102% for premium gasoline
• CIC provides automated, matrix-independent determination of corrosive species
Conclusions
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AppsLab Library
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ApppsLab Library of Analytical Applications
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AppsLab Library of Analytical Applications
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Application and Technical Notes
AN72693 TN72211 AN72333
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