Beruflich Dokumente
Kultur Dokumente
ID# UD3587SCH8551
Course:
INSTRUMENTAL METHODS : CHROMATOGRAPHY
Topic:
GAS CHROMATOGRAPHY AND ITS USE IN THE DETERMINATION OF OXALATES IN BAYER PROCESS
LIQUORS
Organic carbon enters the Bayer process liquors from bauxite in the form of
humic substances (Rao and Goyal, 2006)
5-10% of organic carbon is converted to Sodium Oxalate (Lever, 1983;
Grocott, 1988)
The recycling of Bayer liquor will result in oxalate build up and ultimate
preciptation as fine needles in the cooler parts of the circuit (Sipos, 2001).
Sodium oxalate has been shown to be harmful to alumina productivity and
size (Calalo and Tran, 1993; Brown and Cole, 1980) and so its control and
removal is critical to Bayer process productivity (The and Bush, 1987).
Effective Oxalate control requires its accurate determination in process liquor
streams. Chromatography can be used to facilitate the isolation and
determination of oxalates from the milieu of structurally similar impurities as
found in Bayer liquor.
This Presentation will look at the use of Gas Chromatography and its use in
the analysis of oxalate in Bayer liquor streams.
INTRODUCTION TO GAS CHROMATOGRAPHY
• Greater sensitivity
1. The sample solution is injected into the heated (250 oC) injection port where
it is rapidly volatilized
2. The volatilized sample is then swept via the carrier gas into the heated
column where volatile compounds separate and are eluted separately
where Z is the separation between peaks A and B; and Wa and Wb are the widths at the base of peaks A and B, respectively.
Acceptable resolution is on the order of Rs = 1.0, and baseline resolution between two peaks (as shown in the figure) requires an Rs > 1.5.
GC Components
• Gas supply
• Injection System
• Column
• Detector
• Oven
Gas Supply
• Inert gases are commonly used as the Mobile Phase for GC work
• In the packed column injector, ALL the vapourized sample enters onto
the column
• In the split/splitless injector the amount of vapourized sample that enters
onto the capillary column can be controlled
Injectors
•The oven consist of a wire coil that radiates into the inner volume of the
oven.Heat from the resistive wire source is spread in an even manner,
throughout the oven volume using a fan attached to an electric motor. A
thermocouple inside the oven is part of regulating the oven temperature
via the amount of heat released by the heating element.
• The GC oven is used to keep the column at temperatures between 40 to
350oC
•The peak height or peak area for the internal standard peak
in the chromatogram should be similar to those of
the components to be measured.
Monochloroacetic acid
-Used as an internal standard.Very similar in structure and has a different
retention time to the peaks of interest.Also,it is not present in the samples
Methanol
-The compounds are converted to the methyl esters using the methanol as
these have relatively simple structure, low boiling points, and can be easily
analyzed using FID detectors.
Sulphuric Acid
-Strong, pure acid is used to increase the ionic strength of the solution and increase
the partition coefficient between the aqueous and organic layers.
Chloroform
-The organic layer to which the methyl esters are extracted.Has the advantage of
being a low boiling point solvent, which allows the sample to be vapourized and
analyzed by GC FID.Also, it is not miscible with water.
Bayer Liquor Chromatogram from GC unit
(Oxalate elutes at 3.25 minutes)
Discussion and Conclusion
Barnett N W, Bowser T A and Russel R A (1995) Determination of oxalate in alumina process liquors by ion
chromatography. Analytical Proceedings and Communications, Vol 32, p57-59.
Brown N and Cole T J (1980) The behaviour of sodium oxalate in a Bayer alumina plant. Light Metals, 105-117.
Calalo R and Tran T (1993) Effects of sodium oxalate on the precipitation of alumina trihydrate from synthetic
sodium aluminate liquors. Light Metals, 125-133.
Grocott S C (1988) Bayer liquor impurities:measurement of organic carbon, oxalate and carbonate extraction from
bauxite digestion. Light Metals, 833-841.
Harris Daniel (1996) Exploring chemical analysis. W.H. Freeman and Company, New York.
Lever G (1978) Identification of organics in Bayer liquor (1978) Light Metals, 71-83.
Rao K V and Goyal R N (2006) Organic carbon in indian bauxites and its control in alumina plants. Light Metals,
71-74.
Sipos G (2001) The mechnism and action of sodium oxalate seed stabilizer molecules under Bayer conditions. PhD
Thesis, School of Applied Chemistry, Curtin University of Technology, Australia.
Skoog D A, Holler J F and Nieman T (1998) Principles of instrumental analysis. Harcourt and Saunders College
Publishing, Chicago.
The P J and Bush J F (1987) Solubility of sodium oxalate in Bayer liquor and a method of control. Light Metals, 5-
10.
Appendix
Ion Chromatogram of an Anion Standard Solution (Dionex, 1998)
(Oxalate elutes after 8 Minutes)
Acknowledgment