Development and Evaluation of Combustion Ion Chromatography by the novel combination of Mitsubishis

1
Development and Evaluation of Combustion Ion
Chromatography by the novel combination of
Mitsubishis AQF/GA-100 Auto Quick Furnace/Gas
Adsorption Unit and Dionexs Regent Free Ion
Chromatography
Presented by

• Mark Manahan - Cosa Instruments, Houston, TX
• Kirk Chassaniol Dionex Corporation,Houston, TX
• Shouichi Suguira - Dia Instruments (Mitsubishi)

2
Evaluation Overview

• Evaluate the novel approach of Combustion Ion
  Chromatography (CIC) to analyze trace halogenated
  and sulfur compounds in petroleum, coal and
  chemical intermediates products. These elements
  are crucial since the compounds are
• A source of corrosion within various industrial
  processes.
• Poison expensive catalysts used in various
  industrial and chemical
  processes.
• Of concerned in industrial environmental
  monitoring.
• Criteria in product specification and QA/QC
  monitoring

3
Evaluation Overview

• Evaluate the components and function of the
  Combustion Ion Chromatography System for Sample
  Preparation
• Review the analytical results for various sample
  types

4
Breakdown of Typical Samples Analyzed for Halides
and Sulfur by Industry

• Petrochemical Production
• Feedstocks Crude oil, Ethylene, Propylene
• Intermediates Naphthas, Reformates, HF Alkylate,
  
• Products Gasoline, Diesel fuel, LPG, Solvents,
  Polymers, Rubber
• Power Generation
• Coal
• Fuel Oil
• Environmental
• Soils
• Organic Waste disposal
• Pharmaceutical
• Products
• Solvents

5
Breakdown of Samples by Conc. Range Common
Analytical Techniques
6
Sampling of Current ASTM Methods for Halide and
Sulfur Analysis
7
Technical Advantages
of Combustion IC

• Sub mg/L determinations
• Better process control
• Simultaneous total sulfur and total halides
  with one instrument
• Eliminate cell switching - less equilibration
  time
• More stable and reproducible results
• Coulometric cells have variable day-to-day
  performance

8
Technical Advantages
of Combustion IC

• Chromatographic Separations allow speciation
• Speciate Halides including F, Cl, Br I
• Time and precision comparable to other ASTM
  methods
• Time between reporting results 10-13 Minutes
• Results independent of sample matrix
• All sulfur converted to SO42-

9
Combustion IC Flow Diagram
10
DIA AQF/GA-100 (Automated Quick Furnace/Gas
Adsorption Unit)
11
DIA AQF/GA-100 the Dionex ICS90 Ion
Chromatogaph)
12
AQF/GA-100 Combustion and Absorption Unit Set-up
Configuration
Mitsubishi AQF-100 Solid/Liquid Autosampler,
Automatic Boat Controller, Furnace
and GA-100 Absorption Unit

• Operating Parameters
• Furnace temperature 1000 oC
• Ar flow 200 mL/min
• O2 flow 500mL/min
• For fluoride determinations POX (purgeable
  organic halides) unit was used to
  provide a pyrohydrolitic environment (humidity)
• Absorbing solution water/ 10ppm H2O2/ 0.5 ppm
  P (as PO4)

13
GA-100 Absorption Unit
14
Timing for Analysis
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Combustion IC Features

• Fully automated system
• combustion, absorption, injection
• Separate sipper- for calibration with
  inorganic aqueous samples
• Sample enrichment - achieved through single or
  multiple burns into a single absorbing
  solution
• Variable volume - for absorption solution
• Gas line wash - prior to injection
• Complete rinse - between runs - No Carryover

16
Summary of Dionex
Reagent Free IC System

• DX-320 with EG40
• AS11HC (4x250mm)
• Eluent 25mM KOH _at_ 1.3 mL/min
• ASRS-Ultra 100mA Recycle
• 200uL sample loop
• PeakNet 6.4
• Calibrated with 0.5 to 5 ppm solutions F, Cl
  SO4
• Internal standard 0.5ppm P as PO4

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Why Reagent Free IC

• Fluoride is an important analyte Minimal
  Water Dip
• Consistent - easy to make eluent is an important
  benefit to the petroleum testing laboratory
• Reagent Free IC is independent of operator
• Reagent Free IC is easy to use -Just add water!

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Organic Standards Used
For S Dibenzothiophene For F Fluorobenzoic
acid For Br Bromoacetanilide For Cl 1,3,5
trichlorophenol All standards prepared in
isooctane
19
Calibration Curve Fluoride
20
Calibration Curve Chloride
21
Calibration Curve Bromide
22
Calibration Curve Sulfur
23
Phosphate as Internal Standard
24
Precision and Recovery Data
25
Comparison ASTM Methods vs. CIC on Low Level
Sulfur Round Robin Samples
All Samples Concentrations in ppm wt./vol
26
Analysis of ASTM Coal Samples for Fluoride and
Chloride by CIC
Concentrations in ppm wt./wt
27
Analysis of Coal CRMs for Fluoride
Concentrations in ppm wt./wt
28
Reproducibility of Coal Samples
1 - 06_21_2002 7
1632b
ECD_1
2 - 06_21_2002 7
1632b
ECD_1
3 - 06_21_2002 8
1632b
ECD_1
100
µS
5 - 5.477
2 - Chloride - 3.687
80
60
4 - Sulfate - 4.824
40
20
1 - Fluoride - 2.470
7 - 7.027
6 - 6.654
8 - Phosphate - 11.430
3 - 4.213
3
2
1
min
-10
0.0
2.0
4.0
6.0
8.0
10.0
13.0
29
1.0 ppm Standard run
6.00
µS
Phosphate
5.00
4.00
Fluoride
3.00
Chloride
2.00
Sulfate
1.00
min
-0.50
0.0
2.0
4.0
6.0
8.0
10.0
13.0
30
Methanol Blank
4.00
µS
Phosphate
3.00
2.00
1.00
Fluoride
Chloride
Sulfate
min
-0.50
0.0
2.0
4.0
6.0
8.0
10.0
12.0
13.5
31
CIC Chromatogram0.6 ppm F, Cl, Br / 0.54 S
Standard
1
2
3
5.00
µS
6 - Phosphate - 11.973
4.00
3.00
1 - Fluoride - 2.943
2.00
4 - S-Sulfate - 5.623
2 - Chloride - 4.077
5 - Bromide - 6.937
1.00
3 - 4.673
3
2
1
min
-0.50
0.0
2.0
4.0
6.0
8.0
10.0
12.0
13.5
32
One burn vs. 3 burns 1.0 ppm Std
1
2
5.00
µS
1 - Fluoride - 2.950
7 - Phosphate - 11.957
4.00
3.00
2.00
4 - S-Sulfate - 5.630
2 - Chloride - 4.080
5 - Bromide - 6.930
1.00
3 - 4.610
6 - 7.293
2
1
min
-0.50
0.0
2.0
4.0
6.0
8.0
10.0
12.0
13.5
33
Multiple Injections
34
Conclusions

• The Mitsubishi/Dionex AQF/GA-100 Combustion IC
  System provides an integrated solution for
  automated combustion sample preparation and
  subsequent analysis by Ion Chromatography for a
  wide variety of sample matrices
• The Mitsubishi AQF/GA-100 Combustion/Gas
  Adsorption System used in conjunction with
  Dionexs New Reagent Free IC System can
  simultaneously quantify and measure total
  fluoride, chloride, bromide, iodide and sulfur
  with high accuracy.

35
Conclusions

• The Mitsubishi/Dionex AQF/GA-100 Combustion IC
  System is capable of determining sulfur and
  halogens levels down to 0.5 ppm with excellent
  reproducibility and in less time than other
  comparative techniques.
• Data strongly suggests the use of the accumulate
  feature of The Mitsubishi/Dionex AQF/GA-100
  Combustion IC System to collect multiple burns of
  the same sample will lower the systems detection
  limit below 0.1 ppm with acceptable RSD.

36
Conclusions Continued.......

• Preliminary discussions with customers indicate
  the Mitsubishi/Dionex AQF/GA-100 Combustion IC
  System will be a valuable tool for the
  determination of halogens and sulfur in a wide
  variety of sample matrices
• The Mitsubishi/Dionex AQF/GA-100 Combustion IC
  System can measure smple matrices which differ
  widely in concentrations of Fluoride, Chloride,
  Bromide and Sulfur
• i.e. 10 ppm F / Cl 1000 ppm Sulfur.

37
Conclusions Continued.......

• The Mitsubishi/Dionex AQF/GA-100 Combustion IC
  System for the measurement of Fluoride in LPG and
  alkylates seems to be of special interest in
  refineries. Present instrumentation and
  techniques are widely regarding are unreliable,
  cumbersome and inaccurate
• Regulatory Developments in the power generation
  and utility industry indicate a strong need and
  interest in measuring total fluoride and chloride
  followed by Ion Chromatography. The
  Mitsubishi/Dionex AQF/GA-100 Combustion IC System
  easily addresses this need.

38
Conclusions Continued.......

• COSA has scheduled 9 seminars during the next 5
  months in strategically geographic regions of the
  USA highlighting The Mitsubishi/Dionex AQF/GA-100
  Combustion IC System. Interest has been
  extremely high.
• Customer evaluations of the Mitsubishi/Dionex
  AQF/GA-100 Combustion IC System are ongoing and
  Cosa has received commitments to purchase
  multiple systems.

39
Conclusions Continued.......

• Cosa is Exhibiting at Booth 4271 and is
  displaying the new the Mitsubishi / Dionex
  AQF/GA-100 Combustion IC System with Dionexs New
  ICS 2000 Reagent Free IC.
• Cosa cordiually invites you to stop by and see if
  the Mitsubishi/Dionex AQF/GA-100 Combustion IC
  System is the solution to your analytical needs.