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GULF RESEARCH & DEVELOPMENT COMPANY PITTSBURGH, PENNSYLVANIA
PLAINTIFF'S EXHIBIT TEX-43
AMERICAN PETROLEUM INSTITUTE PROJECT PS-22-GRD(840)
"COMPREHENSIVE ANALYSIS OF PETROLEUM COKE PRODUCTS"
Willis C. Picking Project Manager
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Approved Date
Analytical Technology Department Report No. 553RL069 June 10, 1980
M. C. Bryson
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TABLE OF CONTENTS API PROJECT NO. PS-22-6RD(840)
1. Project Summary 2. Analytical Procedures 3. Data Tables 4. SEM Photomicrographs
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2-5 6-10 11-17
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"Com^ehenslve Analysis of Petroleum Coke Products"
Project Summary
Three samples of petroleum coke and one process water were analyzed for polynuclear aromatics (PNA) content and trace metals con- .. sidered to be toxic. Elemental analysis* x-ray diffraction studies for crystalline components, and scanning electron microscope studies for morphology were also performed on the three coke samples.
. ,
All eight metals In the water were determined to be below EPA
recommended standards for drinking water. Four PNAs were detected in the
water, but at extremely low levels - only one, benzo(a)pyrene, was present
at a concentration above one part per billion. Based on these analyses the
water should not be considered hazardous to handle, although drinking it
would not be recommended.
'
'
The three coke, samples consisted principally of carbon and '
hydrogen but contained in addition appreciable quantities of oxygen,
sulfur, and nitrogen. Two samples contained high concentrations of mercury
(56 and 113 ppm) while the third contained none at all (< 1 ppb). Arsenic
was not detected in any of the three, but selenium was found in low (0.7
5.3 ppm) concentrations. All three cokes contained appreciable quantities
of vanadium and nickel (60-410 ppm). No crystalline components were found
by Xf-ray .diffraction analysis.
- -.
,
'.
Benzene extract'!bles ranged from 0.15 to 9.94 weight percent.
These extracts also contained appreciable quantities of oxygen, sulfur, and
nitrogen. All three extracts contained polynuclear aromatics in the parts
per million range, two of the samples having fairly high concentrations
(11-544 ppm) and one having much lower concentrations (2-10 ppm). This `
suggests that cautious handling procedures should be employed to prevent
exposure to the carcinogenic properties indicated by the analysis.
SEM photomicrographs indicated two of the three coke samples f'were similar, showing a narrow size distribution of fairly smooth particles. The third sample had a broader size range, with a significant amount of
fines, and the particles were irregular, with sharp edges. Particle magnifications ranged from 1000X to 6000X.
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I 2.
! "Comprehensive Analysis of Petroleum Coke Products"
Analytical Procedures
.
Carbon, Gulf Method 1444 -
A Leco combustion procedure which measures carbon dioxide by absorption In a solution of potassium hydroxide.
.
Mineral Carbon, Gulf Method 1469 -
Leco combustion of the organic carbon remaining after hot
hydrochloric acid extraction of the carbonate carbon; cal
culation by difference.
.
Oxygen, Shutz-Unterzaucher Procedure -
.
.
Pyrolysis of sample in nitrogen at 1100C to produce carbon
monoxide, which is then oxidized to carbon dioxide, absorbed in Ascarite and weighed.
Sulfur, Gulf Method 1462 -
A Leco combustion procedure wherein sulfur is combusted at... .
. . high temperature .{~2800oF} in an induction, furnace.to.pro- :
`'
/ duce sulfur dioxide*, which is determined photometrically,
.based on its bleaching effect on starch-iodine solution.
Nitrogen, Gulf Method 811 -
A mercury-catalyzed Kjeldahl procedure wherein the sample Is digested in sulfuric acid to produce ammonium sulfate, which is then released by boiling with strong sodium hydroxide, absorbed in a solution of boric acid, and ^ titrated potentiometrically.
Silicon Dioxide, Gulf Method 1362 -
A gravimetric procedure based on sodium carbonate fusion of the ashed sample residue, followed by dissolution of the melt in hydrochloric acid, dehydration of the silica . with perchloric acid, filtration, volatilization of the silica in the precipitate with hydrofluoric acid, and calculation of the precipitate's loss in weight.
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Iron Oxide* Gulf Mel^id 1341 -
-
Iron In a sulfuric acid solution of the ashed sample is re duced to the ferrous state with hydroxylamine hydrochloride, buffered with sodium acetate, and reacted with 1,10-phenanthrollne to form an orange-red color, which Is measured photometrically at 510 nm and compared to a calibration curve.
Free Silica, Trostel + Wynne Method -
The potassium pyrosulfate fusion melt of a sample is dis
solved in hot water which is then neutralized with sodium
hydroxide, digested, and filtered through close texture
filter paper. The precipitate is washed with water and
hydrochloric acid, ignited in a platinum crucible and
weighed.
.
X-ray Diffraction -
Spectra, made on a Phillips Model 12045 X-ray Diffraction Unit, are examined and compared with library spectra to detect'and identify crystalline species.
Scanning Electron Microscopy -
Photomicrographs are made at high magnifications using a
-- JEOU Scanning Electron Microscope, Model :JSM U-3.
.
Ash, ASTM Method D_ 3174 -
Samples, in porcelain capsules, are heated gradually from - room temperature to constant weight at 750C, cooled, and
weighed.
Wet Digestion for Metals -
This is a closed system digestion procedure using sulfuric and nitric acids to destroy organic matter in a small amount of sample (1-5 grams). The final nitric acid-free sulfuric acid is diluted with water prior tp analysis for metals.
Arsenic, Gulf Method 1410 -
A spectrophotometric procedure wherein arsenic in sulfuric acid is evolved as arsine and reacted with silver diethylt-
dithiocarbamate to produce a red color, which is measured at 540 nm and converted to arsenic concentration by com parison with a calibration curve.
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Selenium, APHA Standards Method -
An acid solution of the sample Is heated with potassium permanganate to oxidize selenium to selenate, after which It Is treated with potassium bromide and sodium peroxide, and distilled as selenium tetrabromide, Excess bromine is removed by precipitation as trlbromophenol, and quad rivalent selenium is determined photometrically after reaction with dlaminobenzidlne and subsequent toluene extraction of the yellow colored salt.
Mercury, EPA Procedure (Gulf Method 1261) -
A cold vapor atomic absorption procedure using aqueous samples oxidized with potassium permanganate, sulfuric, and nitric acids and then digested with potassium persulfate, followed by release of mercury vapors to the AA cell upon addition of stannous chloride.
'
Vanadium and Nickel, Gulf Method 1175A -
An X-ray fluorescence procedure based on measuring X-ray
intensity of the two elements after wet-ashing samples with
benzene sulfonic acid (manganese added as an internal stand
ard), Igniting to remove carbon, and washing the resultant
.
ash onto glass fibre filter discs with Isooctane: .
_-
.' Polynuclear Aromatics, Gulf Procedure - ' `
Column chromatography of benzene extractives using partially deactivated Woelm alumina and elution with isooctane and benzene.
Second stage column chromatography on the first stage fraction (PNA) of Interest using a more highly active adsorbent to yield several subfractions.
Each subfraction is evaporated, concentrated in ethanol and subjected to high-pressure liquid chromatography using Bondapak Cig/Corasil packing and water/methanol and tetrahydrofuran/methanol as carrier fluids. Peaks of interest are collected in cyclohexane according to monitoring at ,254 nm with a Variscan detector.
HPLC fractions of interest are extracted with water and the cyclohexane portions are concentrated and applied to a cellu lose acetate plate developed by a mobile phase consisting of ethanol, toluene and water. The fluorescent band of each desired component is removed, washed with hot methanol, con centrated in n-hexadecane and scanned for absorption in the 240-410 nm range. Identification and quantification are established by reference to prepared absorption spectra.
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PETROLEUM COKE ANALYSIS
API Sample No.
Elemental Analysis: Wt %
Carbon, Gulf 1431 Hydrogen, Gulf 1431 Oxygen, Micro Sulfur, Gulf 1462 Nitrogen, Gulf 811 Mineral Carbon, Gulf 1469
Free Silica Content: ppm
X-ray Diffraction Chemical
'
Chemical Analysis: Wt %
. Si02, Gulf .1362 . Fe203,. Gulf. 1341
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Trace Metals
Arsenic, Gulf 1410: ppb Selenium: ppm Mercury, Gulf 1261: PP Vanadium, Gulf 1175A: ppm Nickel, Gulf 1175A: ppm
Ash/ ASTM D 3174: Wt %
3-1-134 CtT'"
90.17 A. 26 1,06 3.45 1.02 3.86
NDa* 26
. 0.04 - 0.06 `
<1 0.7
56 120
60
0.24
4-1-140 Jjt *A
89.93 3.71 1.30 3.36 1.10
22.2
ND ,24
. 0.04 0.06
<1 4.5
<1 145
95
0.21
6-1-468 /4,: t
- 84.58 2.15 2.56 6.08 1.45
22.2 -
.
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ND 98
0.04 - . . . 0:i3 ;
<1 5.3
113 410 160
0.81
-
a. No crystalline components observed.
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ANALYSIS OF BENZENE EXTRACTIBLES
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API Sample No.
3-1-134
4-1-140
6-1-468
Elemental Analysis; Wfc %
Carbon, Gulf 1431 Hydrogen, Gulf 1431 Oxygen, Micro Sulfur, Gulf 1535 Nitrogen, Gulf 1258
Benzene Extractibles: Wt %
Polynuclear Aromatics: ppm (Gulf Methodology)
Benzo(a)pyrene
Benzo(e)pyrene
Benzo(g,h,i)perylene Benzo(a)anthracene Dibenzo(a,h)anthracene'
.
' Chrysene " . - *
..
' Pyrene-
- . '
Benzo(b)fluoranthene
Phenanthrene
Methyl Benzo(a)pyrene
Fluor ene
Benzo (g,h, i) fluoranthene
Benzo.fluorenes
Perylene Coronene
'
86.31 8.05 0.92 3.62 0.66
9.94
10 4 9 4 4
- 2, 8 ND ND ND ND ND ND ND ND
88.16 6.04 0.89
4.15 0.71
-
0r41 4I&
/*79
82.85 11.94
3.75 1.97 0.14
0.15
440
no
439 544 . ND* . ' 126 ' ND
ND ND ND 11 ND ND ND ND
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50 197 276
38 35 138 . 314 176 280 32
ND ND ND ND ND
* ND - Not detected.. Estimated lower detectability limit is 1 ppm,
based on sample size used.
.
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METALS IN WATER
(Petroleum Coke Process)
API Sample No.
7-1-100
Metals Analysis: ppb
(EPA Protocol for Drinking Water)
Arsenic . < 5
Barium '
600
Cadmium
<5
Chromium
. _ < 10
- ' Lead
' < 10
_
Mercury
<1
Selenium
< 10
Silver
<5
EPA Limits (Maximum)
. 50 1,000
10 50 50 '
2 10 50
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PETROLEUM COKE ANALYSIS
Scanning Electron Microscopy Samples API 3-1-134 and API 4-1-140 are similar, showing a narrow size distribution of fairly smooth particles. Sample API 6-1-468 is different. Particles are irregular and have sharp edges. The size range is broader and a significant amount of fines 1 micron) is present. Copies of SEM photomicrographs are attached.
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