Argonne Premium Coal Sample

Analytical Data

Ultimate (Elemental) and Proximate Analyses

Calculation of As-received, maf and Dmmf values from Dry Data from CT&E

Coal UF WY IL PITT POC UT WV ND AR H2O 1.13 28.09 7.97 1.65 0.65 4.63 2.42 32.24 AR Ash 13.03 6.31 14.25 9.10 4.74 4.49 19.36 6.59 AR VM 27.14 32.17 36.86 37.20 18.48 43.72 29.44 30.45 AR S 2.29 0.45 4.45 2.15 0.66 0.59 0.69 0.54 AR Btu 13315 8426 10999 13404 14926 13280 11524 7454

Dry Ash 13.18 8.77 15.48 9.25 4.77 4.71 19.84 9.72 Dry VM 27.45 44.73 40.05 37.82 18.60 45.84 30.17 44.94 Dry S 2.32 0.63 4.83 2.19 0.66 0.62 0.71 0.80 Dry Btu 13467 11717 11951 13629 15024 13925 11810 11001

Dry C 74.23 68.43 65.65 75.50 86.71 76.89 66.20 65.85 Dry H 4.08 4.88 4.23 4.83 4.23 5.49 4.21 4.36 Dry N 1.35 1.02 1.16 1.49 1.27 1.50 1.25 1.04 Dry Cl 0.00 0.03 0.05 0.11 0.19 0.03 0.10 0.04 Dry F 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Pyritic S 1.77 0.17 2.81 1.37 0.15 0.24 0.16 0.14 Sulfate S 0.01 0.03 0.01 0.01 0.03 0.03 0.03 0.03 Organic S 0.54 0.43 2.01 0.81 0.48 0.35 0.52 0.63

MAF C 85.50 75.01 77.67 83.20 91.05 80.69 82.58 72.94 MAF H 4.70 5.35 5.00 5.32 4.44 5.76 5.25 4.83 MAF N 1.55 1.12 1.37 1.64 1.33 1.57 1.56 1.15 MAF Org S 0.74 0.47 2.38 0.89 0.50 0.37 0.65 0.70 MAF Cl 0.00 0.03 0.06 0.12 0.20 0.03 0.12 0.04 MAF F 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 MAF O 7.51 18.02 13.51 8.83 2.47 11.58 9.83 20.34 MAF Btu 15511 12843 14140 15018 15777 14613 14733 12185

Dmmf C 88.08 76.04 80.73 84.95 91.81 81.32 85.47 74.05 Dmmf H 4.84 5.42 5.20 5.43 4.48 5.81 5.44 4.90 Dmmf N 1.60 1.13 1.43 1.68 1.34 1.59 1.61 1.17 Dmmf Org 0.76 0.48 2.47 0.91 0.51 0.37 0.67 0.71 Dmmf Cl 0.00 0.03 0.06 0.12 0.20 0.03 0.13 0.04 Dmmf F 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Dmmf O 4.72 16.90 10.11 6.90 1.66 10.88 6.68 19.13 Dmmf Btu 15980 13020 14696 15336 15908 14728 15247 12370 Modified Parr Formula (used)
MM(dry) = 1.13 Ash + 0.47 Pyritic S(dry) + 0.50 Cl (dry)
Parr Formula (not used)
MM(dry) = 1.08 Ash(dry) + 0.55 S (total dry)

Abbreviations: UF = Upper Freeport seam; WY = Wyodak Anderson seam; IL = Illinois #6 seam; PITT = Pittsburgh seam; POC = Pocahontas #3 seam; UT = Blind Canyon seam; WV = Lewiston-Stockton seam; ND = Beulah-Zap seam; AR = As received; VM = volatile matter; MAF = moisture and ash-free; Dmmf = dry, mineral matter free

Coal "Formulae"

The Ultimate analysis data were used to calculate the relative amounts of carbon compared to hydrogen, oxygen, nitrogen, and organic sulfur using the MAF and Dmmf data. The results are given below.

MAF

Coal C H O N S

Pocahontas #3 100 58.5 2.03 1.25 .21

Upper Freeport 100 66.0 6.59 1.55 .32

Pittsburgh 100 76.7 7.96 1.69 .40

Lewiston-Stockton 100 76.3 8.93 1.62 .30

Blind Canyon 100 85.7 10.8 1.67 .17

Illinois #6 100 77.3 13.0 1.51 1.15

Wyodak-Anderson 100 85.6 18.0 1.28 .23

Beulah-Zap 100 79.5 20.9 1.35 .36 Dmmf

Coal C H O N S

Pocahontas #3 100 58.6 1.36 1.25 .21

Upper Freeport 100 65.9 4.02 1.56 .32

Pittsburgh 100 76.7 6.09 1.70 .40

Lewiston-Stockton 100 76.4 5.86 1.61 .29

Blind Canyon 100 85.7 10.0 1.68 .17

Illinois #6 100 77.3 9.39 1.52 1.15

Wyodak-Anderson 100 85.5 16.7 1.27 .24

Beulah-Zap 100 79.4 19.4 1.35 .36

Laboratories which participated in the different analyses indicated in this section include:

  1. Alberta Research Council
  2. Argonne National Laboratory Analytical Chemistry Laboratory
  3. Argonne National Laboratory Basic Coal Chemistry Group
  4. CANSPECS, a Canadian round robin of international laboratories>
  5. Commercial Testing and Engineering, Inc.**
  6. Illinois State Geological Survey
  7. Massachusetts Institute of Technology Energy Laboratory
  8. University of North Dakota Energy and Mineral Research Center

Major, Minor and Trace Elements in Ash

Major and Minor Elements in Ash (%)

UF WY IL PITT POC UT WV[**] ND[**]

Al2O3 24.1 15.5 18.3 25.2 20.1 16.6 31.35 10.22

BaO 0.05 0.5 .02 .84

CaO 4.2 15.1 7.9 2.6 12.8 9.9 .38 24.72

Fe2O3 17.3 10.2 18.0 19.5 15.8 10.0 2.89 8.00

K2O 2.7 0.8 2.9 2.1 0.6 1.2 2.92 .94

MgO 1.6 3.6 1.2 1.3 2.0 1.5 0.73 7.48

MnO 0.05 0.04 0.04* 0.14*

Na2O 0.0 1.5 0.0 0.0 2.0 3.6 0.34 7.76

P2O5 0.1 1.2 0.2 0.0 0.4 0.3 0.20 0.48

SO3 3.9 22.0 6.8 2.0 12.4 9.8 0.32 17.55

SiO2 44.8 28.7 43.7 45.9 32.0 45.9 58.26 18.40

SrO 0.05 0.4 0.05 1.12

TiO2 1.3 1.2 1.0 1.2 1.9 1.2 1.86 0.48

Undetermined 0.64 1.87

* = Mn3O4

The tables on the next three pages are taken from Ref. 317 to give a compilation of major and minor concentrations in the whole coal, and also the trace elements in the whole coal. To obtain the values of the major and minor elements in the ash, the following values of ash at 550 degrees C from Appendix 1 of the Open File Report for Ref. 317 should be used:

Coal Ash

UF 13.5

WY 8.5

IL 16.2

PITT 9.2

POC 5.3

UT 4.6

WV 19.4

ND 9.5

 The techniques used include:

DCAES = direct current atomic emission spectroscopy

ICAP-AES = inductively coupled argon plasma atomic emission spectroscopy

FAAS = flame atomic absorption spectroscopy

GFAAS = graphite furnace atomic absorption spectroscopy

WDXRF = wavelength dispersive x-ray fluorescence spectrometry

EDXRF = energy dispersive x-ray fluorescence spectrometry

INAA = instrumental neutron activation analysis

Abbreviations: UF = Upper Freeport seam; WY = Wyodak Anderson seam; IL = Illinois #6 seam; PITT = Pittsburgh seam; POC = Pocahontas #3 seam; UT = Blind Canyon seam; WV = Lewiston-Stockton seam; ND = Beulah-Zap seam

Major and Minor Elements in Ash (%)
Data from Ref. 317

Trace Elements (ppm)

Data from Ref. 317

Trace Elements (ppm)

Data from Ref. 317

Mineral Matter Analysis

Data from Illinois State Geological Survey, Richard Harvey

November 15, 1988

Results of Mineral Analyses

(dry coal basis)

Coal 1 2 3 4 5 6 7 8

UF WY IL PIT POC UT WV ND

Total mineral matter

(%LTA) 15.3 8.7 18.1 10.9 5.5 5.3 21.6 8.7

Quartz 1.5 2.0 3.4 1.7 0.3 0.8 2.6 0.6 Pyrite 3.4 0.1 5.5 2.4 0.1 0.5 0.3 0.3 Calcite 1.0 0.4 1.9 0.5 1.7 1.3 0.3 1.7 Total clay

(diff.) 9.4 6.2 7.3 6.3 3.4 2.7 18.4 6.1 Illite p ? p p ? ? p ? Expandable p ? p p p ? p ? Kaolinite p p p p p ? p p

Gypsum m m m major Marcasite tr tr tr Siderite tr? Analcime tr-m Rutile tr Ca/Na feldspar tr

Unknown tr?

p = present, analysis in progress; m = minor amount; tr = trace amount;
blank = not detected

Mineral Constituents as a Percentage of Total Mineral Matter

Coal 1 2 3 4 5 6 7 8

UF WY IL PIT POC UT WV ND

Total mineral matter

(%LTA) 15.3 8.7 18.1 10.9 5.5 5.3 21.6 8.7

Quartz 10 23 19 16 5 15 12 7 Pyrite 22 1 30 22 2 9 1 3 Calcite 7 5 10 5 31 24 1 20 Total clay

(diff.) 61 71 41 57 62 52 86 70

Maceral Analyses

Data are given on a mineral-matter free basis in %.

UF WY IL PITT POC UT WV ND Lipt. 1 <1 5 7 1 5 12 - Vitr. 91 89 85 85 89 87 73 - Inert. 8 11 10 8 10 8 15 -

Abbreviations: UF = Upper Freeport seam; WY = Wyodak Anderson seam; IL = Illinois #6 seam; PITT = Pittsburgh seam; POC = Pocahontas #3 seam; UT = Blind Canyon seam; WV = Lewiston-Stockton seam; ND = Beulah-Zap seam

Optical Reflectance Measurements

The data are reported in terms of two types of measurements: The mean average and mean maximum reflectance. The procedure involves the measurement of the reflectance of a particular small spot on the sample using an oil immersion technique and light of a specified wavelength (546 nm). Because coals are anisotropic the reflectance values depend on the orientation of the light beam to the orientation of the particle. Rotation of the particle will result in variation of the measured reflectance. Thus, some workers report the average values as the mean average of the measurements, while others determine the maximum reflectance for each spot and report the mean maximum reflectance.

The data and comments from the University of Kentucky are given below. The values were obtained from -20 mesh samples prepared for reflected light microscopic analyses as per ASTM D2797. Mean-maximum reflectance readings were acquired utilizing a Leitz MPV Compact microscope photometer, in compliance with ASTM D2798 guidelines.

Table 1. Mean Maximum Vitrinite Reflectance

Coal Reflectance Std. Dev. Rank

Beulah-Zap 0.25 .04 lignite Wyodak 0.32 .05 subbit. Illinois #6 0.46 .05 subbit. Blind Canyon 0.57 .04 hvBb Pittsburgh 0.81 .05 hvAb Lew.-Stockton 0.89 .05 hvAb Upper Freeport 1.16 .05 mvb Pocahontas #3 1.68 .05 lvb

The workers indicate that there is actually no division between lignite and subbituminous coal based on the vitrinite (huminite) reflectivity; coals with measured reflectances of less than 0.47% are considered to be of subbituminous rank or lower (Davis, 1984). They correlated the reflectivity ranges with the ASTM coal-rank classes in accordance with Davis.

They also indicate that despite the apparent subbituminous rank, the microscopic appearance of the Illinois #6 coal is more consistent with a rank level in the high volatile bituminous range.

Reference: Davis, A. 1984, Coal Petrology and Petrographic Analysis, In Coal Geology and Coal Technology (Ed. by C. R. Ward) Blackwell Scientific, Melbourne, pp. 74-112.

The data from Woods Hole Oceanographic Institute are given below as the mean average vitrinite reflectance in oil (ne 1.518) @ 546 nm. The method involved mounting in a cold set epoxy resin, grinding and polishing to standard procedures (ICCP, 1963, 1971, 1975). The samples were examined in reflected and fluorescence light. Reflectance measurements in oil were determined on a Leitz MPV 3 microscope system, using a 50x oil immersion objective and mineral standards for photometer calibration. Vitrinite particles were carefully selected and measured using a 5 micron measuring diaphragm to give the mean reflectance (%Ro). Fluorescence examination was performed on all samples using a Zeiss Axiophot microscope fitted with a x40 oil immersion objective, a 100w HBO mercury bulb, and an LP520 BP450-90 filter set.

Table 2. Mean Average Vitrinite Reflectance Coal Reflectance # Std. Dev. Spore Mean % Ro Readings Fluorescence Color Beulah-Zap 0.28 49 .04 yellow (about 0.3 %Ro) Wyodak 0.31 50 .08 yellow/yellow orange (about 0.35 %Ro) Illinois #6 0.46 24 .05 yellow/yellow orange (about 0.45 %Ro) Blind Canyon 0.50 50 .05 light orange/light-mid orange (about 0.5-0.6%Ro) Pittsburgh 0.72 50 .04 mid orange (about 0.6-0.75 %Ro) Lew.-Stockton 0.77 50 .05 mid orange, moderate intensity (about 0.7-0.8 %Ro) Upper Freeport 0.99 50 .07 dark red brown trace weak intensity (about >=1.0 %Ro) Pocahontas #3 1.42 50 .06 spores no longer fluoresce. (>=1.1 %Ro)

The University of Kentucky workers provided reflectance distributions for each sample, reported as vitrinoid type (V-type) histograms. A vitrinoid-type of 1 represents reflectance values in the range of 0.10 to 0.19%, while V-Type 18 includes reflectances of 1.80 to 1.89%. These are given on the next page page.

Vitrinoid (V-type) Histograms of Reflectance of the Coals

Courtesy of University of Kentucky Center for Applied Energy Research

Ash Fusion Properties

Temperatures in degrees F.

UF WY IL PITT POC UT WV ND

Reducing

Initial 2191 2050 1952 2039 2183 2012 2700+ 2246

h = w 2250 2120 1996 2098 2240 2079 2700+ 2310

h = l/w 2321 2185 2043 2190 2310 2154 2700+ 2349

fluid 2433 2230 2153 2416 2407 2202 2700+ 2394

Oxidizing

Initial - 2140 2341 2517 2400 2149 2700+ 2329

h = w - 2170 2375 2554 2414 2194 2700+ 2393

h = l/w - 2200 2425 2578 2422 2240 2700+ 2425

fluid - 2225 2510 2610 2487 2309 2700+ 2460

Particle Size Measurements

Particle Size Measurements -100 mesh UF WY IL PITT POC UT WV ND Size wt.% wt.% wt.% wt.% wt.% wt.% wt.% wt.% (microns) 500+ 3.00E-02 0.00E+00 1.80E-01 3.77E-01 1.17E-01 1.69E-02 5.50E-02 2.27E-01 500-425 1.92E-02 0.00E+00 1.29E-01 9.57E-02 1.02E-01 3.58E-02 6.89E-02 1.92E-01 425-355 6.87E-02 6.40E-03 2.27E-01 1.13E-01 1.72E-01 8.20E-02 1.52E-01 3.72E-01 355-300 9.86E-02 7.73E-03 3.64E-01 1.51E-01 3.21E-01 1.75E-01 2.24E-01 4.64E-01 300-250 1.63E-01 8.26E-03 4.21E-01 2.02E-01 3.65E-01 3.06E-01 2.65E-01 5.20E-01 250-212 2.53E-01 6.45E-02 5.61E-01 5.27E-01 6.00E-01 7.52E-01 5.57E-01 7.36E-01 212-180 3.18E-01 5.01E-02 5.43E-01 3.07E-01 4.19E-01 1.07E+00 4.69E-01 8.48E-01 180-150 1.20E+00 5.29E-01 7.29E-01 1.52E+00 6.26E-01 3.19E+00 2.00E+00 2.89E+00 150-125 3.30E+00 1.96E+00 4.08E+00 4.54E+00 9.44E-01 7.61E+00 5.28E+00 5.15E+00 125-106 5.77E+00 5.01E+00 6.09E+00 5.74E+00 1.69E+00 7.94E+00 6.87E+00 7.03E+00 106-90 8.08E+00 1.00E+01 1.02E+01 9.19E+00 3.56E+00 1.07E+01 8.64E+00 7.60E+00 90-75 1.03E+01 1.18E+01 9.36E+00 1.14E+01 5.96E+00 1.16E+01 9.97E+00 7.47E+00 75-63 6.33E+00 8.00E+00 6.22E+00 6.67E+00 5.01E+00 6.14E+00 6.00E+00 4.91E+00 63-53 7.99E+00 1.55E+01 1.21E+01 1.18E+01 1.01E+01 8.75E+00 9.07E+00 8.14E+00 53-45 1.31E+01 1.05E+01 7.25E+00 7.21E+00 7.99E+00 5.59E+00 6.19E+00 5.09E+00 45-38 6.25E+00 6.28E+00 1.04E+01 9.19E+00 7.87E+00 5.59E+00 5.27E+00 4.80E+00 38- 3.67E+01 3.03E+01 3.12E+01 3.09E+01 5.42E+01 3.05E+01 3.89E+01 4.36E+01 TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 -20 mesh UF WY IL PITT POC UT WV ND Size wt.% wt.% wt.% wt.% wt.% wt% wt.% wt.% (microns) 1000+ 1.43E-02 6.75E-03 9.71E-03 9.89E-01 0.00E+00 0.00E+00 1.51E-02 2.28E-01 1000-850 6.48E-03 9.31E-02 4.01E-02 2.77E-01 2.19E-02 1.14E-02 4.85E-02 1.11E-01 850-710 3.31E-02 4.33E-01 2.12E-01 4.64E-01 3.79E-02 8.83E-02 1.39E-01 2.15E-01 710-600 3.64E-02 1.64E+00 7.85E-01 6.98E-01 2.75E-01 3.97E-01 6.39E-01 7.00E-01 600-500 1.26E-01 4.30E+00 2.41E+00 1.28E+00 8.44E-01 1.41E+00 1.86E+00 2.89E+00 500-425 1.82E-01 4.81E+00 3.61E+00 1.79E+00 1.83E+00 3.07E+00 3.28E+00 4.34E+00 425-355 4.12E-01 7.17E+00 4.83E+00 2.48E+00 2.87E+00 4.85E+00 5.12E+00 6.76E+00 355-300 8.59E-01 8.22E+00 6.97E+00 4.71E+00 4.35E+00 7.45E+00 7.13E+00 9.34E+00 300-250 1.41E+00 8.29E+00 6.96E+00 4.93E+00 5.21E+00 8.20E+00 7.14E+00 8.00E+00 250-212 2.96E+00 1.03E+01 9.37E+00 7.08E+00 7.99E+00 1.08E+01 9.63E+00 8.86E+00 212-180 2.79E+00 5.44E+00 5.86E+00 5.90E+00 4.49E+00 6.27E+00 5.42E+00 4.75E+00 180-150 4.72E+00 6.51E+00 7.46E+00 7.82E+00 6.27E+00 4.71E+00 8.00E+00 7.30E+00 150-125 6.39E+00 5.83E+00 7.36E+00 7.91E+00 6.89E+00 1.11E+01 7.69E+00 5.72E+00 125-106 5.51E+00 4.90E+00 5.82E+00 6.23E+00 7.72E+00 7.01E+00 5.70E+00 4.30E+00 106-90 7.27E+00 4.54E+00 5.54E+00 6.01E+00 4.86E+00 5.77E+00 5.21E+00 3.72E+00 90-75 7.09E+00 2.45E+00 5.08E+00 7.35E+00 8.20E+00 5.79E+00 5.20E+00 3.90E+00 75-63 5.83E+00 2.66E+00 3.03E+00 2.74E+00 3.51E+00 3.66E+00 3.28E+00 3.11E+00 63-53 8.49E+00 3.28E+00 5.93E+00 3.66E+00 4.27E+00 3.86E+00 3.93E+00 2.28E+00 53-45 6.00E+00 3.34E+00 3.29E+00 6.13E+00 1.03E+01 3.86E+00 2.58E+00 2.40E+00 45-38 6.40E+00 1.72E+00 2.23E+00 3.63E+00 3.24E+00 2.32E+00 3.92E+00 2.24E+00 38- 3.35E+01 1.41E+01 1.32E+01 1.79E+01 1.69E+01 9.37E+00 1.41E+01 1.88E+01 TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Particle sizes are given in microns. Data courtesy of Alan Sayre at M. I. T.

Surface Area Measurements

BET Multipoint Analysis for Six Premium Coals in the Concentration Range 0.05 =<P/Po =< 0.35 for Nitrogen Adsorption

BET eq params wt.

Coal Mesh Weight slope inter corr monol. surface sp. area cept coeff N2, g area m**2/gm

UF -100 .6978 1697.3 64.89 .9994 5.675 1.98 2.48 WY -20 .5013 1096.9 24.22 .9995 8.919 3.11 6.20 IL -100 .5388 270.8 4.04 .9998 36.38 12.68 23.53 PITT -100 .6559 2128.4 104.74 .9968 4.478 1.56 2.38 POC -100 .5276 2294.6 92.53 .9993 4.189 1.46 2.77 ND -100 .6690 2717.0 95.12 .9997 3.556 1.24 1.85

Temperature = 77 K, measurements with a Quantasorb apparatus.

Wyodak and Illinois #6 samples were dried at 110 C under vacuum for 24 h; Beulah-Zap lignite was dried at 80-90 C. Samples were outgassed with heating for 2 h at the temperature at which they had been dried or by repetitive adsorption and desorption of N2.

Data from Ref. 63, Gumkowski, M.; Liu, Q. and Arnett, E. M., Energy & Fuels, 2 (3) 299 (1988)

Coal Mesh CO2 N2 m**2/g

WY -200/+230 206 5.0 -325/+400 208 5.0 PITT-200/+230 119 1.3 -325/+400 117 ND -200/+230 229 0.5 -325/+400 250 1.0

Values for Pittsburgh -200/+230 fraction:

Pore volume by Hg porosimetry: 0.43 m**3/g; N2: 0.012 and H2O: 0.031

Helium pycnometer density: 1.39 +/- 0.01 g/cm**3

Data from Ref. 46, Bartholomew, C. H. et al, Preprints, Fuel Chemistry Div. Am. Chem. Soc. 33 (3) 24 (1988)

Surface areas of Illinois #6 coal

Adsorbate Ads temp. Cross-sec. area BET surface K Sq. Angstroms m**2/g

Ar 77 16.2 14,15 CO2 178 25.3 132,132 Cyclopropane 203 25.2 36,31

Data from Ref. 15, Larsen, J. W. and Wernett, P., Preprints, Fuel Chemistry Div., AM. Chem. Soc., 32 (4) 232-236 (1987)

Free-Swelling Indices

UF WY IL PITT POC UT WV ND

FSI 8.5 0 2-4 - 8.0 1.5 3.5 -

Data courtesy of Commercial Testing & Engineering Co.

Plasticity and Dilatometry

Gieseler Plastometer Composite Data

Coal DDPM* Fluid Temp. Initial Soft. Solid. Range

UF 30,000 450 C 373 C 497 C 124 C WY Broke Free -- -- -- -- IL 86 417 367 444 77 PITT 29,267 430 381 472 91 POC 44 474 460 509 49 UT 3 409 396 438 42 WV to be measured

Courtesy of Commercial Testing and Engineering Co.

Arnu Dilatometer Composite Data

Coal Contract Expan Init Soft Max Cont Max Exp

UF -30 250 350 405 450 WY -10 -- 360 -- -- IL -20 -5 355 402 425 PITT -30 175 350 400 455 POC -30 30 408 453 500 UT -36 -- 375 -- -- WV to be measured ND to be measured

Data courtesy of Commercial Testing and Engineering, Inc.

UF = Upper Freeport, WY = Wyodak-Anderson, IL = Illinois #6, PITT = Pittsburgh, POC = Pocahontas #3, UT = Blind Canyon seam,

WV = Lewiston-Stockton, ND = Beulah-Zap seam

* DDPM = dial divisions per minute