Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world...

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The world leader in serving science 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

Transcript of Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world...

Page 1: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

The world leader in serving science

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

Page 10: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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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

Page 21: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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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

Page 27: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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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

Page 28: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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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

Page 29: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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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

Page 30: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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Thermo Scientific™ AppsLab™ Library of Analytical Applications:

• On-line search engine for Thermo Scientific applications

• Comprehensive application information, ready-to-run analytical methods

• Central repository for Thermo Scientific chromatography and MS application information

AppsLab Library

https://appslab.thermofisher.com/

Page 31: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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ApppsLab Library of Analytical Applications

Page 32: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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AppsLab Library of Analytical Applications

Page 34: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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CIC Website

www.thermofisher.com/combustionic

Page 35: Determination of total fluorine, chlorine, and sulfur in aromatic … · 2018-11-07 · The world leader in serving science Sachin Patil, Carl Fisher, and Jeff Rohrer Thermo Fisher

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Thank You!