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Combustion Ion Chromatography Beyond the horizon – the world of combustion Dr. Christian Emmenegger Metrohm International Headquarters

Combustion Ion Chromatography Beyond the horizon – the world of combustion Dr. Christian Emmenegger Metrohm International Headquarters

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Combustion Ion Chromatography

Beyond the horizon – the world of combustion

Dr. Christian EmmeneggerMetrohm International Headquarters

Combustion Ion Chromatography 2

Combustion ICTopics

Why Combustion IC? – Regulations Different combustion methods The Mitsubishi Combustion System Applications USP

Combustion Ion Chromatography 3

RegulationsWhy do we need “halogen-free” products?

Address the fast and global increase of consumer electronics wasteReduce damage to people and environment

Restriction for the use of hazardous materials mostly in various electronic and electrical equipment:

Europe: Waste Electrical and Electronic Equipment Directive (WEEE) 2002/96/EC Restriction of Hazardous Substances Directive (RoHS) 2002/95/EC (polybrominated biphenyls PBB, polybrominated diphenyl ether PBDE, Pb, Hg, Cd, Cr (VI))

Combustion Ion Chromatography 4

RegulationsHalogen-free Definition

JPCA (Japan Printed Circuit Association): JPCA-ES-01-2003 Br < 900ppm Cl < 900ppm

IEC (International Electrotechnical Commission): IEC 60502-1 Br < 900ppm Cl < 900ppm Total halogens < 1500ppm

IPC (Association Connecting Electronic Industries): IEC 61249-2-21 Br < 900ppm Cl < 900ppm Total halogens < 1500ppm

Other VIIA group halogens are not included in the definition (F, I)

www.ipc.org www.iec.ch www.jpca.net www.halogenfree.org

Combustion Ion Chromatography 5

RegulationsRegulations

Apple (069-1857-A) Br<900ppm Cl<900ppm Total halogens<1500ppm

Sony Ericsson 2/034 01-LXE 108 239 Uen Br<900ppm Cl<900ppm Total halogens<1500ppm

Samsung Electronics Br<900ppm Cl<900ppm

Combustion Ion Chromatography 6

RegulationsVarious Test Methods

ASTM D 7359 –08 Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatoghraphy Detection

Combustion Ion Chromatography 7

RegulationsFuel and Petrol Industry

Low sulfur contents reduce air pollutants in the air

Low sulfur contents increase performance of emissions cleaning systemes in automobiles

European Union, Japan… continously reduced sulfur content

DIN EN 228 for automobile max. 10 ppm Sulfur

Combustion Ion Chromatography 8

Application FieldsWhich industries are applicable to CIC?

Environmentally relevant oil, plastic waste, acitvated substances: carbon …

Electronic components: printed circuit boards, resins, cables, insulating materials …

Fuels: gasoline, kerosene, crude oil, heating oil, coal, catalysts …

Plastics: polymers such as polyethylene, polypropylene …

Dyestuffs: pigments, paints … Pharmaceutical products: raw substances, intermediates,

finished products

Combustion Ion Chromatography 9

Potentional CustomersWho does not use electronical parts?

Combustion Ion Chromatography 10

Potentional CustomersWho does not use electronical parts?

Combustion Ion Chromatography 11

Sample Combustion MethodsTypical Combustion Setups

Offline: Schöniger Flask Wickbold - Apparatus

Parr-Bomb with Na2O2

Oxygen-Bomb Microwave-induced combustion

Online: Mitsubishi AQF

Combustion Ion Chromatography 12

Schöniger FlaskCombustion by Kurt Schöniger

Closed system to determine halogens and sulfur in organic compounds:

Closed system Compounds on a filter are burned

in a flask filled with oxygen and adsorbed.

Combustion Ion Chromatography 13

Wickbold Combustion ApparatusOxyhydrogen Gas Blowpipe Combustion

Open system mainly for sulfur and chlorine analysis in petroleum products:

Substance is evaporated in oxygen stream Burned in a cooled quartztube in

oxyhydrogengas Absorption in solution

Combustion Ion Chromatography 14

Parr-Bomb – Oxygen BombClassical Methodolgy

Closed system for combustion in a sealed, pressure-stable environment:

Parr Bomb: Oxydation e.g. by Na2O2 at elevated temperatures

thermal excitation (slow, hours) Microwave-induced Combustion (fast, several minutes)

Oxygen Bomb: @ 25 - 40 bar O2 the sample is ingnited byelectrodes

oxygen bomb

AW UK6-0226-052008 Determination of F -, Cl -, PO4

2- and SO42- combusted oil sample

Combustion Ion Chromatography 15

Mitsubishi Combustion SystemComplete Prep Station for Ion Chromatography

Open system for fast halogen and sulfur analysis:

Sample is automatically inserted into furnace and incrementally burned in oxygen/argon gas stream

Absorption in H2O2 solution

Combustion Ion Chromatography 16

Which Ions are measured?Combustion and Absorption Principles

Sulfur and halogen compounds are combusted under Ar/O2 gas and oxidized by H2O2

Sample in combustion gas in absorption solvent S SO2, SO3 SO4

2-

X (F, Cl, Br, I) HX, X2 X-

Internal standard (e.g. Phosphate, Tartaric Acid, Citric Acid…) is added to the absorption solvent to correct for the absorption volume

N/A for the following compounds: N NO, NO2 (bad recovery)

P P2O5 (non-volatile)

M (Metal) MO (metal oxides are non-volatile)

Combustion Ion Chromatography 17

Specifications for SamplesImportant numbers for Mitsubishi Combustion IC

Solid and Non-Aqueous Liquid Samples

Solid sample 1-100 mg (typically 20-30 mg)

Liquid Sample 5-100 L (typically 30-50 L) Absorbent Volume

3-10 mL (extendable up to 20 mL) Furnace Temperature max 1100°C Combustion Time about 3-7 minutes

Combustion Ion Chromatography 18

Sample PreparationIs sample preparation required?

Inhomogenous, bulky and large samples need sample preparation:

Smaller size by scissors, cutter Dissolve in solvent Powdering by grinder, mill Freeze milling

Combustion Ion Chromatography 19

Flowpath Combustion ICSchematic of the CIC system

Common Conditions: Inlet Temperature: 900°C Outlet Temperature: 1000 °C

Ar/O2 flow: 200 mL/min

O2 flow: 450 mL/min

WS-100 Ar flow: 150 mL/min

Combustion Ion Chromatography 20

Burn ProcessMultistage Combustion Process (gradually)

1. Home Positon (Prepare Sample)

The combustion process is divided into the following steps for the sample boat:

2. 1st position (preheating)

3. 2nd position

7. Home position (Absorption Time)

4. 3rd position

6. Cooling position

5. End position (oxydation)

Combustion Ion Chromatography 21

Combustion ProgramSample combustion and absorption programs

Combustion must be optimized for each sample for a slow pyrolysis process! Otherwise incomplete combustion!

Combustion Ion Chromatography 22

Time ProgramEfficient Time Schedule for Combustion and IC

The analysis time schedule is optimized and synchronized:

Cleaning Combustion Ion Chromatography

3 min 5 min 15 min1st sample

Cleaning Combustion Ion Chromatography

3 min 5 min 15 min2nd sample

3rd sample

Cleaning Combustion

3 min 5 min

Combustion Ion Chromatography 23

Multiple CombustionSample Accumulation with multiple combustion

Multiple Combustion time schedule for low concentrations:

Cleaning Combustion Combustion Combustion Ion Chromatography

3 min 5 min 5 min 5 min 15 min

R2 = 0.9988

R2 = 0.9988

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

0 1 2 3 4 5

Number of Combustions

Co

nc

en

tra

tio

n i

n

ab

so

rpti

on

so

luti

on

[p

pm

]

sulphate

chloride

Sulphate and Chloride concentration in absorption solvent correlate well

Combustion Ion Chromatography 24

Combustion TemperaturesTemperatures for ideal combustion

Typical combustion temperatures for following compound types:

Organic 900/1000 °C Organic with inorganic 1000/1100 °C Inorganic 1100/1100 °C

Combustion Ion Chromatography 25

Combustion ImproverProtects equipment and increases recovery

Recovery is low when target is inorganic salt or sample matrix has inorganics

Also effective against corrosion of quartz glass Typical improvers are:

tungsten oxide (effective for alkaline/alkaline earth metal: Na, Ca, …) copper oxide (halogen analysis in silica compound, glass) iron oxide (halogen analysis in silica compound, glass)

Cannot prevent corrosion by fluorine

Combustion Ion Chromatography 26

Combustion Improver EffectEffect of Combustion Improver

Prevent corrosion of quartz glass

CaO + H2O Ca(OH)2 deteriorates tube

CaO + H2O + WO3 CaWO4 + H2O lightens deterioration

Improves e.g. sulfur recovery:

CaSO4 + WO3 Ca WO4 + SO3

Na2SO4 + WO3 Na2WO4 + SO3

Combustion Ion Chromatography 27

Sample Boat TypesSeveral kinds of boats are available

Boat for ABC quartz boat: organic sample without residual ceramic disposable boat: with improver or sample

has residue which cannot be cleaned out

Boat for auto sampler ceramic boat: organic sample without residual. nickel inner disposable boat: with improver or

residue which cannot be cleaned out. Only for halogen (sulfur has low recovery)

quartz boat

ceramic disposable boat

ceramic boat

nickel inner disposable boat

Combustion Ion Chromatography 28

Pyrolysis TubeHandling and Use

Quartz tube can be deteriorated by fluorine, alkaline and alkaline earth metal. Frequently washing necessary. (deteriorating samples are: sodium sulfonic acid, sodium sulfate, barium sulfate, sodium salt, potassium salt, alakline earth metal. High fluorine)

Alternative: ceramic inner tube

Combustion Ion Chromatography 29

Mitsubishi System Configurations ICombinations for AQF-100

Basic Units necessary: GA-100 (gas absorption unit) AQF-100 (furnace) WS-100 (water supplier)

Absorption Parts: Absorption Tube for Low Concentration

(10 mL) Absorption Tube for High Concentration

(20 mL, 20 und 5 L Sampling Loops, Trap Column)

Sample Injectors for combustion: for liquids: ABC-100 or

combo ABC-100 + ASC150L for solids: ABC-100 or ASC-120S

Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis

Combustion Ion Chromatography 30

Mitsubishi System Configurations IICombinations for AQF-100

Basic Units necessary: GA-100 (gas absorption unit) AQF-100 (furnace) WS-100 (water supplier)

Absorption Parts: Absorption Tube for Low Concentration (10 mL) Absorption Tube for High Concentration (20 mL, 20 und 5 L Sampling Loops, Trap Column)

Sample Injectors for combustion: for liquids: ABC-100 or combo ABC-100 + ASC150L for solids: ABC-100 or ASC-120S

Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis

Combustion Ion Chromatography 31

Mitsubishi System Configurations IIICombinations for AQF-100

Basic Units necessary: GA-100 (gas absorption unit) AQF-100 (furnace) WS-100 (water supplier)

Absorption Parts: Absorption Tube for Low Concentration (10 mL) Absorption Tube for High Concentration

(20 mL, 20 und 5 L Sampling Loops, Trap Column)

Sample Injectors for combustion: for liquids: ABC-100 or combo ABC-100 + ASC150L for solids: ABC-100 or ASC-120S

Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis

ASC150L 50 samples

ASC-120S20 samples

ABC-100

Combustion Ion Chromatography 32

The Metrohm-Mitsubishi CombinationSetup with IC Net

Combination with Compact 761/861 Compact IC 761 need to have an analog output 771 synchronizes the two systems MagIC Net can be added to such a system (database features)

There is a package available for the 771 and MagIC Net (2.771.0110).

Part No. Description Use

6.2134.140 Cable 771 (analog) – 819 Connection of analog and start signals to 771

2.771.0010 IC Compact Interface Receives and records the analog signal of the IC system. Further it receives the contact closure signal of the Mitsubishi instrument and starts the IC instrument.

Combustion Ion Chromatography 33

The Metrohm-Mitsubishi CombinationSetup with MagIC Net

Compact IC pro 881 Scan for a contact closure signal on input line 2 ( *****1** )

Part No. Description Use

6.2148.010 Remote Box MSB Connect to MSB port of IC instrument.

6.2141.140 Cable 766/788/813/838 - 817 Connect to the Mitsubishi contact closure output with the open ends and with the 21 pin connector to the Remote box

Combustion Ion Chromatography 34

ApplicationsPerformance check upon installation:

S-Benzylthiuroniumsulfate

Check solution S-Benzylthiuroniumsulfate 25mg/25mL Ethanol

Absorbent 30 ppm H2O2, 1 ppm Phosphate

Calibrate IC SystemMeasure 30 L check solutionJudgment: within 92-108 % of theoretical value

AW CH6-0953-082008

Combustion Ion Chromatography 35

ERM-EC681kLow density Polyethylene pellet

Certified Reference Material A Supp 5 –150

H2O2 30 ppm, 1 ppm Phosphate

AW CH6-0954-082008

Combustion Ion Chromatography 36

FuelSulfur in Fuel

Various Fuel Measurements A Supp 5 –150 50 L injections Simultaneous Chloride determination

H2O2 30 ppm, 1 ppm Phosphate

AW CH6-0959-082008

Sample Chloride [ppm]

RSD [%] Sulfur [ppm]

RSD [%]

Bleifrei 95 (lead free) 7.9 2.3 10.8 1.0

Diesel 4.5 9.1 1.3 1.1

Migrol Greenlife Biodiesel 5.0 1.2 10.4 1.1

Rapeseedmethylester (RME) 4.9 3.1 3.8 1.5

Available Reference Material by ERM:

Combustion Ion Chromatography 37

Highly viscous oil samplesDetermination of Chloride

Crude oil with high content of Sulfur A Supp 5 –150 100 L injections

H2O2 300 ppm, 1 ppm Phosphate

AW CH6-0980-012009

Sample Chloride [ppm]

RSD [%]

Waxy distillate 36.5 4.3

HCR-Feed < LOQ 9.1

Migrol Greenlife Biodiesel 5.0 1.2

Rapeseedmethylester (RME) 4.9 3.1

Combustion Ion Chromatography 38

Residual solventsMatrix Elimination of H2O2 (no disturbance for F)

Determination of F, Cl,Br, S A Supp 5 –150 10 or 100 L injections

H2O2 900 ppm, 20 ppm Phosphate for high concentrated samples

H2O2 90 ppm, 1 ppm Phosphate for low concentrated samples

1P12497E THF/Toluene 150P760 Diversolvent

AW CH6-0984-022009

No.S

[%]Cl

[%] Br[%]

F[%]

1 n.d. 8.16 n.d. 13.802 n.d. 8.03 n.d. 13.593 n.d. 8.56 n.d. 14.58Avg - 8.25 n.d. 13.99RSD % - 1.2 n.d. 3.7

No.S

[ppm]Cl

[ppm]Br

[ppm]F

[ppm]1 2.4 14.8 20.6 n.d.

2 2.5 14.7 20.7 n.d.3 3.3 14.8 20.9 n.d.Avg 2.7 14.8 20.7 -RSD % 14.7 0.3 0.6 -

Combustion Ion Chromatography 39

Parameters are adjustableAdjustable parameters e.g. for lower concentration

Increase amount of sample for combustion Decrease absorbent volume Multiple combustion into one absorbent volume Increase injection loop

Combustion Ion Chromatography 40

USPAdvantages by Combustion IC

Full Automation with Mitsubishi setup Reduced analysis time Fast Sample throughput Simultaneous determination of sulfur and halogen compounds Halogens are speciated individually Analysis of solids and viscous substances! Analysis within the ppm range

New application fields for IC

Combustion Ion Chromatography

Beyond the horizon – the world of combustion sampling