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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 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