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

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Presentation on theme: "Combustion Ion Chromatography Beyond the horizon – the world of combustion Dr. Christian Emmenegger Metrohm International Headquarters."— Presentation transcript:

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

2 Combustion Ion Chromatography2 Combustion IC Topics  Why Combustion IC? – Regulations  Different combustion methods  The Mitsubishi Combustion System  Applications  USP

3 Combustion Ion Chromatography3 Regulations Why do we need “halogen-free” products?  Address the fast and global increase of consumer electronics waste  Reduce 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))

4 Combustion Ion Chromatography4 Regulations Halogen-free Definition  JPCA (Japan Printed Circuit Association): JPCA-ES  Br < 900ppm Cl < 900ppm  IEC (International Electrotechnical Commission): IEC  Br < 900ppm Cl < 900ppm  Total halogens < 1500ppm  IPC (Association Connecting Electronic Industries): IEC  Br < 900ppm Cl < 900ppm  Total halogens < 1500ppm  Other VIIA group halogens are not included in the definition (F, I)

5 Combustion Ion Chromatography5 Regulations  Apple ( A)  Br<900ppm Cl<900ppm  Total halogens<1500ppm  Sony Ericsson 2/ LXE Uen  Br<900ppm Cl<900ppm  Total halogens<1500ppm  Samsung Electronics  Br<900ppm Cl<900ppm

6 Combustion Ion Chromatography6 Regulations Various Test Methods ASTM D 7359 –08Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatoghraphy Detection

7 Combustion Ion Chromatography7 Regulations Fuel 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

8 Combustion Ion Chromatography8 Application Fields Which industries are applicable to CIC?  Environmentally relevantoil, 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

9 Combustion Ion Chromatography9 Potentional Customers Who does not use electronical parts?

10 Combustion Ion Chromatography10 Potentional Customers Who does not use electronical parts?

11 Combustion Ion Chromatography11 Sample Combustion Methods Typical Combustion Setups Offline:  Schöniger Flask  Wickbold - Apparatus  Parr-Bomb with Na 2 O 2  Oxygen-Bomb  Microwave-induced combustion Online:  Mitsubishi AQF

12 Combustion Ion Chromatography12 Schöniger Flask Combustion 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.

13 Combustion Ion Chromatography13 Wickbold Combustion Apparatus Oxyhydrogen 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

14 Combustion Ion Chromatography14 Parr-Bomb – Oxygen Bomb Classical Methodolgy Closed system for combustion in a sealed, pressure-stable environment:  Parr Bomb: Oxydation e.g. by Na 2 O 2 at elevated temperatures  thermal excitation (slow, hours)  Microwave-induced Combustion (fast, several minutes)  Oxygen bar O 2 the sample is ingnited by electrodes oxygen bomb AW UK Determination of F -, Cl -, PO 4 2- and SO 4 2- combusted oil sample

15 Combustion Ion Chromatography15 Mitsubishi Combustion System Complete 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 H 2 O 2 solution

16 Combustion Ion Chromatography16 Which Ions are measured? Combustion and Absorption Principles  Sulfur and halogen compounds are combusted under Ar/O 2 gas and oxidized by H 2 O 2 Samplein combustion gasin absorption solvent S SO 2, SO 3 SO 4 2- X (F, Cl, Br, I) HX, X 2 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, NO 2 (bad recovery) P P 2 O 5 (non-volatile) M (Metal)MO (metal oxides are non-volatile)

17 Combustion Ion Chromatography17 Specifications for Samples Important numbers for Mitsubishi Combustion IC  Solid and Non-Aqueous Liquid Samples Solid sample mg (typically mg) Liquid Sample L (typically L)  Absorbent Volume 3-10 mL (extendable up to 20 mL)  Furnace Temperature max 1100°C  Combustion Time about 3-7 minutes

18 Combustion Ion Chromatography18 Sample Preparation Is 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

19 Combustion Ion Chromatography19 Flowpath Combustion IC Schematic of the CIC system Common Conditions:  Inlet Temperature: 900°C  Outlet Temperature: 1000 °C  Ar/O 2 flow: 200 mL/min  O 2 flow: 450 mL/min  WS-100 Ar flow: 150 mL/min

20 Combustion Ion Chromatography20 Burn Process Multistage Combustion Process (gradually) 1.Home Positon (Prepare Sample) The combustion process is divided into the following steps for the sample boat: 2.1 st position (preheating) 3.2 nd position 7.Home position (Absorption Time) 4.3 rd position 6.Cooling position 5.End position (oxydation)

21 Combustion Ion Chromatography21 Combustion Program Sample combustion and absorption programs Combustion must be optimized for each sample for a slow pyrolysis process! Otherwise incomplete combustion!

22 Combustion Ion Chromatography22 Time Program Efficient Time Schedule for Combustion and IC  The analysis time schedule is optimized and synchronized: Cleaning Combustion Ion Chromatography 3 min 5 min 15 min 1 st sample Cleaning Combustion Ion Chromatography 3 min 5 min 15 min 2 nd sample 3 rd sample Cleaning Combustion 3 min 5 min

23 Combustion Ion Chromatography23 Multiple Combustion Sample 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  Sulphate and Chloride concentration in absorption solvent correlate well

24 Combustion Ion Chromatography24 Combustion Temperatures Temperatures for ideal combustion  Typical combustion temperatures for following compound types:  Organic 900/1000 °C  Organic with inorganic 1000/1100 °C  Inorganic 1100/1100 °C

25 Combustion Ion Chromatography25 Combustion Improver Protects 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

26 Combustion Ion Chromatography26 Combustion Improver Effect Effect of Combustion Improver  Prevent corrosion of quartz glass  CaO + H 2 OCa(OH) 2 deteriorates tube  CaO + H 2 O + WO 3 CaWO 4 + H 2 Olightens deterioration  Improves e.g. sulfur recovery:  CaSO 4 + WO 3 Ca WO 4 + SO 3  Na 2 SO 4 + WO 3 Na 2 WO 4 + SO 3

27 Combustion Ion Chromatography27 Sample Boat Types Several 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

28 Combustion Ion Chromatography28 Pyrolysis Tube Handling 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

29 Combustion Ion Chromatography29 Mitsubishi System Configurations I Combinations 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 ASC150L  for solids:ABC-100 or ASC-120S Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis

30 Combustion Ion Chromatography30 Mitsubishi System Configurations II Combinations 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 ASC150L  for solids:ABC-100 or ASC-120S Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis

31 Combustion Ion Chromatography31 Mitsubishi System Configurations III Combinations 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 ASC150L  for solids:ABC-100 or ASC-120S Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis ASC150L 50 samples ASC-120S 20 samples ABC-100

32 Combustion Ion Chromatography32 The Metrohm-Mitsubishi Combination Setup 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 ( ). Part No.DescriptionUse Cable 771 (analog) – 819Connection of analog and start signals to IC Compact InterfaceReceives 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.

33 Combustion Ion Chromatography33 The Metrohm-Mitsubishi Combination Setup with MagIC Net  Compact IC pro 881  Scan for a contact closure signal on input line 2 ( *****1** ) Part No.DescriptionUse Remote Box MSBConnect to MSB port of IC instrument Cable 766/788/813/ Connect to the Mitsubishi contact closure output with the open ends and with the 21 pin connector to the Remote box

34 Combustion Ion Chromatography34 Applications Performance check upon installation: S-Benzylthiuroniumsulfate  Check solution S-Benzylthiuroniumsulfate 25mg/25mL Ethanol  Absorbent 30 ppm H 2 O 2, 1 ppm Phosphate  Calibrate IC System  Measure 30 L check solution  Judgment: within % of theoretical value AW CH

35 Combustion Ion Chromatography35 ERM-EC681k Low density Polyethylene pellet  Certified Reference Material  A Supp 5 –150  H 2 O 2 30 ppm, 1 ppm Phosphate AW CH

36 Combustion Ion Chromatography36 Fuel Sulfur in Fuel  Various Fuel Measurements  A Supp 5 –150  50 L injections  Simultaneous Chloride determination  H 2 O 2 30 ppm, 1 ppm Phosphate AW CH SampleChloride [ppm] RSD [%] Sulfur [ppm] RSD [%] Bleifrei 95 (lead free) Diesel Migrol Greenlife Biodiesel Rapeseedmethylester (RME) Available Reference Material by ERM:

37 Combustion Ion Chromatography37 Highly viscous oil samples Determination of Chloride  Crude oil with high content of Sulfur  A Supp 5 –150  100 L injections  H 2 O ppm, 1 ppm Phosphate AW CH SampleChloride [ppm] RSD [%] Waxy distillate HCR-Feed< LOQ9.1 Migrol Greenlife Biodiesel Rapeseedmethylester (RME)4.93.1

38 Combustion Ion Chromatography38 Residual solvents Matrix Elimination of H 2 O 2 (no disturbance for F)  Determination of F, Cl,Br, S  A Supp 5 –150  10 or 100 L injections  H 2 O ppm, 20 ppm Phosphate for high concentrated samples  H 2 O 2 90 ppm, 1 ppm Phosphate for low concentrated samples 1P12497E THF/Toluene 150P760 Diversolvent AW CH No. S [%] Cl [%] Br [%] F [%] 1n.d.8.16n.d n.d.8.03n.d n.d.8.56n.d Avg-8.25n.d RSD %-1.2n.d.3.7 No. S [ppm] Cl [ppm] Br [ppm] F [ppm] n.d n.d n.d. Avg RSD %

39 Combustion Ion Chromatography39 Parameters are adjustable Adjustable parameters e.g. for lower concentration  Increase amount of sample for combustion  Decrease absorbent volume  Multiple combustion into one absorbent volume  Increase injection loop

40 Combustion Ion Chromatography40 USP Advantages 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

41 Combustion Ion Chromatography Beyond the horizon – the world of combustion sampling


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