Page 1 of 20 Application Work AW IC US6-0167-012013 Trace Level Halides in Coal by Metrohm Combustion IC Branch General analytical chemistry; energy, power plants; environmental protection Keywords IC 881 / Metrosep A Supp 5 - 150/4.0 / MMS 5000 / 920 / Absorber Module / Combustion Module / combustion ion chromatography / CIC / Coal / matrix elimination / fluoride / chloride / bromide / branch 16; branch 1; branch 2 Summary The application work describes the determination of trace (μg/g) levels of halides in coal samples using Metrohm Combustion IC system. Mercury is highly volatile and a neurotoxin. Coal power stations are responsible for the highest amount of mercury emissions in Germany, the US and worldwide. They emit the poisonous metal, also known as quicksilver, into the atmosphere and it can eventually make its way into the food chain. Mercury is only found in coal in small amounts, but coal is burned around the world and in large quantities. The United Nations Environment Program estimates that internationally coal power plants emit some 500 tons of mercury a year - Germany is responsible for more than five tons, the US for almost 50 tons and China for more than 100 tons 1 . Mercury is released when coal is burned and takes three forms in the flue gas: elemental, oxidized, and particulate. Oxidized and particulate mercury can be controlled by abatement equipment. However, elemental mercury is gaseous at combustion temperatures and is difficult to capture. Therefore, chemical additives have been developed to oxidize the elemental mercury in the flue gas, converting it to a form which can be captured by current abatement equipment. Calcium bromide is effective in reducing total mercury emissions by oxidizing elemental mercury that is then captured by the abatement equipment. Brominated powdered activated carbon has been demonstrated to capture over 90 per cent of mercury emissions from coal fired plants 2,3,4 , operating at high temperatures and capturing the metal in concrete-friendly, non-leaching forms to help tackle a rising global health threat. Bromine and iodine in atmospheric particles or coal can cause environmental problems such as destruction of ozone in the atmosphere; therefore, the presence of these compounds has recently received increased attention. Fluorine occurs in trace amounts in most coals. It is typically associated with minerals of the apatite group, principally fluorapatite and clays, and with fluorite, tourmaline, topaz, amphiboles and micas. The average fluorine content of US coal is, according to the tabulation of Swanson, er al, 74 μg/g. In the United States, the lowest average fluorine concentration of 30 μg/g is found in coals from Eastern Kentucky and the highest average value of 160 μg/g is found in coals from Wyoming and New Mexico. The concentration range of fluorine in European coals is similar to that found in the US while the average fluorine content of Australian coals ranges from 15 to 500 μg/g. Fluorine and chlorine is released into the atmosphere during the combustion of coal. Because of its effect upon environmental quality and health, fluorine and chlorine have been classified as elements of concern in the development of the coal resource. With the increased utilization of this energy resource, it is important to be able to reliably determine these halides content in coals and coal by-products. In this application work trace level of fluoride, chloride and bromide are determined in various coal samples using Metrohm Combustion IC. The Repeatability and reproducibility was tested and the resulting precision is summarized. Reagents Sodium carbonate , CAS 497-19-8 Sodium bicarbonate, 144-55-8 Sulfuric acid, CAS 7664-93-9 Fluoride standard stock solution, β(F -) = 1 g/L; Sigma Aldrich 77365 Chloride standard stock solution, β(Cl -) = 1 g/L; Sigma Aldrich 39883 Bromide β(Br-) = 1 g/L in H2O, No. 43147 Sulfate standard stock solution, β(SO4-2) = 1 g/L; Sigma Aldrich 90071 Ultrapure water, resistivity >18 MΩ·cm (25 °C), type I grade (ASTM D1193) Multicomponent Anion Standard in H2O -IC1- 100 μg/mL Hydrogenperoxide, 30% H2O2, TraceCert®, from Sigma Aldrich 16911 Instruments 881 Compact IC pro – Anion – MCS 2.881.0030 IC conductivity detector 2.850.9010 Combustion Module 2.136.0700 Autosampler MMS 5000 2.136.0800 Kit for solid sampling 6.7302.000 920 Absorber Module 2.920.0010 MagIC Net TM 2.4 Compact 6.6059.241 Metrosep A Supp 5 - 150/4.0 6.1006.520
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Trace Level Halides in Coal by Metrohm Combustion IC
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Application Work AW IC US6-0167-012013
Trace Level Halides in Coal by Metrohm Combustion IC
Branch
General analytical chemistry; energy, power plants; environmental protection
The application work describes the determination of trace (μg/g) levels of halides in coal samples using Metrohm Combustion IC system.
Mercury is highly volatile and a neurotoxin. Coal power stations are responsible for the highest amount of mercury emissions in Germany, the US and worldwide. They emit the poisonous metal, also known as quicksilver, into the atmosphere and it can eventually make its way into the food chain. Mercury is only found in coal in small amounts, but coal is burned around the world and in large quantities. The United Nations Environment Program estimates that internationally coal power plants emit some 500 tons of mercury a year - Germany is responsible for more than five tons, the US for almost 50 tons and China for more than 100 tons
1.
Mercury is released when coal is burned and takes three forms in the flue gas: elemental, oxidized, and particulate. Oxidized and particulate mercury can be controlled by abatement equipment. However, elemental mercury is gaseous at combustion temperatures and is difficult to capture. Therefore, chemical additives have been developed to oxidize the elemental mercury in the flue gas, converting it to a form which can be captured by current abatement equipment. Calcium bromide is effective in reducing total mercury emissions by oxidizing elemental mercury that is then captured by the abatement equipment. Brominated powdered activated carbon has been demonstrated to capture over 90 per cent of mercury emissions from coal fired plants
2,3,4, operating at high
temperatures and capturing the metal in concrete-friendly, non-leaching forms to help tackle a rising global health threat. Bromine and iodine in atmospheric particles or coal can cause environmental problems such as destruction of ozone in the atmosphere; therefore, the presence of these compounds has recently received increased attention.
Fluorine occurs in trace amounts in most coals. It is typically associated with minerals of the apatite group, principally fluorapatite and clays, and with fluorite, tourmaline, topaz, amphiboles and micas. The average fluorine content of US coal is, according to the tabulation of Swanson, er al, 74 µg/g. In the United States, the lowest average fluorine concentration of 30 µg/g is found in coals from Eastern Kentucky and the highest average value of 160 µg/g is found in coals from Wyoming and New Mexico. The concentration range of fluorine in
European coals is similar to that found in the US while the average fluorine content of Australian coals ranges from 15 to 500 µg/g.
Fluorine and chlorine is released into the atmosphere during the combustion of coal. Because of its effect upon environmental quality and health, fluorine and chlorine have been classified as elements of concern in the development of the coal resource. With the increased utilization of this energy resource, it is important to be able to reliably determine these halides content in coals and coal by-products.
In this application work trace level of fluoride, chloride and bromide are determined in various coal samples using Metrohm Combustion IC. The Repeatability and reproducibility was tested and the resulting precision is summarized.
sodium bicarbonate Eluent is prepared from the A Supp 5 Concentrate 20X (Metrohm USA number: REAIC1101) by the EPOD system. Alternatively eluent concentrate from Sigma-Aldrich (product number: 62414) can also be used. The 849 level sensor continuously monitors the eluent level and it triggers the eluent preparation when the level is less than full.
Alternatively for eluent preparation
Pour 1 full snip (REAIC1102) of Supp 5 eluent concentrate in a mobile phase reservoir and dilute it to 1 L with ultrapure water.
Regenerant for Suppressor: 100 mmol/L sulfuric acid
5.5 mL of concentrated sulfuric acid is transferred in a 1 L reagent bottle containing 0.5 L of water and diluted up to 1 L with ultrapure water.
Samples
1. Certified Reference Material for Chloride in coal
- BCR-180
2. Secondary Coal Standards provide by customer,
tested and verified by XRF technique
a. 14 ppm BRAY Coal
b. 24 ppm BRAY Coal
c. 82 ppm BRAY Coal
Standard
Mixed anion standard of 1 mg/L is prepared from 10 mg/L of multi anion high purity standard.
Method Description
About 20 to 40 mg of coal samples are weighed accurately on an analytical balance with 0.1 mg resolution. 10 mL Dosino connected to the Absorption solution empties out the absorption tube and adds 2 mL of absorption solution. The absorption solution volume is an important variable to achieve the sensitivity. For samples containing halides less than 100 mg/L, absorption solution of 2 mL is recommended. For samples containing high concentration of halides the absorption solution volume can be proportionately increased to a maximum of 8 mL. ABD feed starts and the combustion begins. The flame sensor measures the intensity of the light and controls the feed rate of the sample boat into the oven in proportion to
it. As a result, the duration of the combustion is optimized so that, firstly, combustion is always complete (no soot formation), and, secondly, there is no need for waiting times as a safety buffer. The automated combustion process eliminates the time consuming method development steps. ABD moves the quartz boat to annealing at the end position specified. Subprograms for water and absorption solution addition are carried out simultaneously and the total volume addition is calculated by MagICNet. For coal application 0.2 mL/min water and absorption solution addition is recommended. Accurate liquid addition by Dosino and total volume calculation by MagICNet eliminates the need for Phosphate internal standard which are typically used in combustion IC method. The remaining pyrolysis gases are burned in the O2 stream. The duration is specified as “Post Combustion Time” in MagICNet method. For coal it is recommended to use 180 s, which ensures the complete combustion.
Optimized IC and Combustion parameters are summarized below.
IC Parameters
Eluent Flow 0.7 mL/min
Eluent Source EPOD
Column temperature 30°C
Absorber Solultion 100 mg/L H2O2
Sample loop 250 μL
Inj. Vol. (Standards) 5 - 200 μL
MSM Regenerent 100 mmol/L Sulfuric acid
MSM Rinsing water
Carbonate Suppressor ON
Combustion Parameter
Argon 100 mL/min
Oxygen 300 mL/min
Oven temperature 1050 °C
Time for post-combustion 180 sec
Initial volume of absorbing solution 2 mL
Water addition 0.2 mL/min
Absorbtion solution addition 0.2 mL/min
Boat Blank
It is important to bake the boats before using it for sample analysis in order to remove the ionic impurities present in it. The quartz boat is much cleaner compared to the ceramic boat and doesn’t leach out ionic impurities. For trace analysis it is essential to keep the boats and the pyrotubes clean. For trace analysis analyte concentration from the boat blank should be, ideally, less than 2 µg/L (ppb).
Sample analysis
20 mg to 40 mg of the coal sample is combusted. Depending on the expected bromine concentration about 100 μL to 200 μL of the combusted sample is preconcentrated and injected into the IC. A guide line
Application Work AW IC US6-0167-012013
Trace Level Halides in Coal by Metrohm Combustion IC
Page 3 of 20
correlating the analyte concentration to the sample weight and injection volume is provided in Appendix Tables.
Calculation
Automatic integration with MagIC Net 2.4 software using peak area for all analytes.
Time program
The time program was set up with sub-routines which are activated depending on the sample type (e.g. sample, standard, check standard and blank) defined in the determination series table.
Results
Linearity
IC is calibrated separately using mixed standard anions. Linearity is established by variable volume preconcentration using the 1 mg/L mixed anion standard.
Volume (μL) 200 100 40 20 10 5
Conc.(μg/mL) 1 0.5 0.2 0.1 0.05 0.025
A regression line was obtained by plotting the peak area verses concentration using the least square method. The relationship between the peak response and the concentration is linear with correlation coefficient (r
2) of
>0.999 for all the ions with a response factor RSD less than 3%. Results of linearity study is shown in below Table
Ions Range
(mg/L)
Correlation
Coeffiecnt (r2)
%RSD
Fluoride 0.025 to 1 0.99964 3.08
Chloride 0.025 to 1 0.99995 1.24
Bromide 0.025 to 1 0.99970 3.12
Example chromatogram for blank, boat blank, standards and the calibration details are provided in appendix.
Sample Results
Samples are run in triplicate and the average results in µg/g are shown in table below.
Ions BRAY
14 ppm
BRAY
24 ppm
BRAY
82 ppm
Fluoride 25.1 25.2 30.5
Chloride 9.4 6.8 7.3
Bromide 14.0 23.4 81.6
Detailed precision for individual samples are provided in appendix.
Detection Limit
Detection limit with respect to the coal sample weight was arrived out by analyzing the Bray 14 ppm Coal samples seven times. From the standard deviation (s) of replicate
analysis the detection limit is calculated, as per EPA method.
DL= s X 3.14
3.143 is the Student’s t value at a 99% confidence level
Calculated detection limit for Chloride, Fluoride and Bromide respectively are, 1.25, 4.08 and 1.25 µg/g.
Precision and Accuracy
Method performance was evaluated by analyzing the BRAY 14 ppm coal sample on two different days. Overall precision for seven replicate on two different days is less than 3%.
Results obtained by CIC are in agreement with the XRF method for all three BRAY coal samples for bromide. Recovery more than 95% was achieved for Bromide with CIC method for all the BRAY coal samples. Overall, recovery study indicates that the method performs well for the trace level halides determination in coal matrix.
Comments
Iodide cannot be determined using this method. Iodide gets converted to iodate and other oxide form during combustion in presence of oxygen. This conversion also facilitated by the presence of hydrogen peroxide. An alkaline absorption solution is needed for Iodide determination.
The recovery in all the cases is more than 95% and there is no need for catalyst such as tungsten or tungsten oxide.
Date
28*01*2013
Reference
1. http://www.dw.de/a-little-bromine-cuts-coals-
mercury-emissions/a-15830213-. Author: Ralph
Heinrich Ahrens / nh.Editor: Holly Fox
2. GEOBROM White paper final 081910-White Paper
on Calcium Bromide Technology for Mercury
Emissions Reductions
3. Mercury control evaluation of Calcium Bromide
injection into a prp-fired furnace with an SCR
4. Vosteen, B. et al., “Process for Removing Mercury
from Flue Gases,” United States Patent #
6,878,358
Authors
Dr. Hari Narayanan
Market Development Manager
Metrohm USA Inc.
Appendix
Instrumentation setup, calibration curves, chromatograms with results and tables.