ANALYTICAL CHEMISTRY
1728 Table 1. Chemical Composition of Empire Cotton (7, 1 4 ) Constituent Cellulose Protein ( S X 6 . 2 5 ) Wax Pectic substances .4sh Other (sugars. organic acids. etr.)
Percentage (Dry Basis) 95 30 1.00 0.75 0.99 0.86 1 10
for much of the experimental and anal>tical x o r k reported in this paper. The electron microccope was used through the courtesy of Charity Hospital and Tulant. Cniversity Biophysics Department, N e x Orleans, La. LITERATURE CITED
(1) Anderson, D. B., and Kerr, T.. I n d . Eng. Chem., 30, 48 (1938).
( 2 ) Bailey, T . L. IT,,
ill “Matthen-s’ Textile Fibers,” H. hIauersberger, ed., 5th ed., S e w Tork, John TViley & Sons, 1947. (3) Balls, W,L., “Development and Properties of Raw Cotton,” London, Black 8- Co., 1915. (4) Balls, IT. L., “Studies of Quality in Cotton,” London, Macmillan Co.. 1928. ( 5 ) Catleit, M . S., Giuffria, R.. Moore, A. T., and Rollins. XI. L., Textile Research J . , 21, 880 (1961). (6) Flint. E. A , , Cambridge Phil. Soc. Bz’ol. Ret’., 25, 414 (1950). (7) Guthrie, J. D., Hoffpauir, C . L., Steiner. E. T., and Stansbury, .\I. F , I-. S.Dept. Agriculture, Pub. AIC-61 (Revised, 1949).
Hess. K., and Trogus, C., 2. physik. Chem.. B4, 321 (1929). Hock, C. W., Textile Research J., 20, 141 (1950). Hock, C. W.,Ramsay, R. C., and Harris, M., J . Research S a t l . B u r . Standards, 26, 93 (1941). Johansen, D. A , , “Plant Microtechnique,” New Tork, AlcGrawHill Book Co., 1940. Kerr, T.. Textile Research J., 16, 249 (1946). Kling, W.,and hlahl, H., Melliand Textilber., 33, 32 (1952). McCall, E. R., and Jurgens, J. F., Textile Research J., 21, 19 (1951). Mangenot, G., and Raison, lI., botan. Rec., 17, 555 (1951). Mitchell, R. L., Ind. Eng, Chem., 38, 843 (1946). hionier-Williams, G. IT., J . Chem. Soc., 119, 803 (1921). Morgan, W.T. J., and Elson, L. A , , Biochem. J . , 27, 1824 (1933); 28, 988 (1934) Muhlethaler, K., Biochim. et Biophys. Acta, 3, 15 (1949). Kickerson, R. F., Ind. Eng. C h e m . 32, 1464 (1940). Ranby, B., T a p p i , 35, 53 (1952). Reeves, R. E., J . Biol. Chem., 154, 49 (19441. Reid, J. D., Daul, G. C., and Reinhardt, R. bl., Tertile Research J . , 20, 657 (1950). Reid, J. D., Xielson, G. H., and Aronovsky. 6 . I., ISD. ENQ. CHEY.,AXAL.ED.. 12, 255 (1940). Roelofsen, P. A , Biochim. et Biophys. Acta, 7, 43 (1951). Rollins, M ,L., Testile Research J . . 15, 65 (1935). Stark, s. hl., -4N.4L. CHEM., 22, 1158 (1950). Tripp, V. IT.,Moore, A. T., and Rollins, .IT. L., Textile Research J . , 21, 886 (1951). Wyckoff, R. W.G., “Electro~iMicroscopy,” Sew Tork, Interscience Publishers, 1949. RECEIVED for review ,July 21, 1932. -4ccepted August 29. 1932. T h e Southern Regional Reseaich Laboratory is one of the laboratorieq.
[END OF 5TH ANNUAL SUMMER SYMPOSIUM]
Nonhydrocarbon Constituents of Petroleum
I
Papers presented before the Division of Petroleum Chemistry, Sj-mposinm on Nonhydrocarbon Constituents of Petroleum, at the l t l s t Meeting of the AMERICAN CHEMICAL SOCIETY. Milwaukee, Wis., March 30 to dpril3,1952
Determination of Trace Metals in Crudes and Other Petroleum Oils Analysis f o r Iron, Nickel, Vanadium, and Copper 0. I. MILNER, J . R . GLASS, J. P. KIRCHKER, A N D A . N. YURICK Research and Development D e p a r t m e n t , Socony- V a c u u m Laboratories, Paulsboro, N.
I
T HAS been found by various investigators that among the metallic elements present in t: pica1 crude oils are iron, nickel,
vanadium, aluminum, sodium, calcium, copper, magnesium, manganese, barium, silicon, chromium, tin, lead, molybdenum, strontium, cobalt, beryllium, lithium, rubidium, silver, bismuth, titanium, zinc, potassium, and gold ( 1 , 7 , 14, 15). .Z number of these elements-e.g., iron, nickel, vanadium, and copper-Then deposited on a cracking catalyst xyill reduce its activity. The petroleum industry has, therefore, become increasingly concerned with these metallic traces. The problem has been magnified by the increased use of crudes containing relatively high amounts of these harmful metals, particularly nickel and vanadium. Moreover, t h e advent of modern high temperature power generators, such as gas turbines which are particularly susceptible t o
J.
vanadium corrosion, has necessitated a more cribical examination of the vanadium content of certain petroleum stocks. As part of the above problems it has been necessary t o develop quantitative analytical methods for the determination of these metals. At the same time it has been required that these methods be applicable, not only t o crudes and residua containing relatively high concentrations of metals, but also t o distillates and cracking stocks where the metal content is of the order of less than 0.1 p.p.m. Several approaches t o the quantitative determination of one or more elements have been reported. Murray and Plagge (9) and Russell ( 1 0 ) describe seniiquantitative spectrographic methods for the determination of a number of metallic constituents in gas oils. The methods are limited in that results are accu-
V O L U M E 2 4 , N O . 11, N O V E M B E R 1 9 5 2 Increasing concern of the petroleum industry with metallic traces present in crude oils has necessitated the development of quantitative analytical methods. A procedure has been developed for the decomposition of petroleum oils and the analysis of the resulting ash for iron, nickel, vanadium, and copper. The method comprises a novel wet-ashing technique whereby crudes and petroleum fractions can he conveniently reduced to an inorganic residue with minimum risk of loss of metals. The ash is soluhilized, and separate aliquots of the solution are taken for the determination of the individual elements. Iron, nickel, and vanadium are determined photometrically after reaction with o-phenanthroline, di-
rate only t o &loo%. Anderson and Hughes ( 2 ) described a spectrographic method for vanadium alone. This method is designed primarily for application t o the ash of residual fuel oils, but can be applied t o other petroleum ashes containing a t least 1% vanadium. Rrightson (16) has described a spectrophotometric method for the determination of nickel, vanadium, and iron. The method is based on the reaction of aliquots of the solubilized ash with reagents more or less specific for the elements being determined. However, with the reactions and conditions chosen, the colors develop slovr-ly; in the case of iron, overnight standing is required. An accuracy of better than 5 1 0 % is indicated for quantities in the p.p.m. range. Other methods that have come t o t h e authors' attention depend on obtaining sufficient ash t o permit separations and determinations by classical wet-chemical means. It is obvious that in the case of certain crudes or overhead fractions, thousands of grams of sample I\-ould have t o be processed. ghtson method, the analytical scheme developed by the authors employs sensitive and specific spectrophotometric techniques for the determination of iron, nickel, and vanadium, hoxever, the reactions are practically instantaneous. Copper is determined polarographically Incorporation of a novel ashing method minimizes the possibility of metal loss during processing of the sample. COhlPARISOY OF A S H I l G PROCEDURES
Despite progress in the direction of conducting quantitative analyses directly on the oil ( 3 ) , concentration of the inorganic components by preliminary reduction t o ash is still necessary for sensitive, precise analysis. The ash is generally prepared by either of tn-0 methods, dry-ashing or 11-et-oxidation. Although the possibility has been pointed out, fen data have appeared in the literature t o indicate the extent of metals lost by ignition or dry-ashing. llnderson and Hughes ( 2 ) present limited data showing t h a t the recovery of vanadium from a dry ash is the same as from a sulfated ash. Morgan and Turner (8) describe a series of experiments with radioactive tracers which shows that if combustion is carefully controlled and final ignition is a t less than 500' C., insignificant amounts of iron, calcium, and sodium (as naphthenates or salicylates) ale lost during a dry-ashing decomposition. Russell (11) also found in the ashing of crudes that there were no ash components lost by ignition, as compared a i t h sulfation. RIost other methods that have come t o the authors' attention use a dry-ashing procedure, n-ith final ignition in platinum. However, consistent reports of the appearance of metallic components in soot or fly ash suggest that the conditions under which t h e ignition is carried out, or possibly t h e nature of the sample, are factors Mhich influence t h e amount of metal lost in this manner. Indeed Morgan and Turner show t h a t high rates of combustion and t h e presence of traces of water in the oil cause variable and incomplete metal recovery.
1729 methy lglyoxime, and phosphotungstic acid, respectively. Copper is determined polarographically after preliminary isolation by microelectrodeposition. The effect of the ashing technique on the recovery of metals from representative stocks is discussed. Data are presented to establish the accuracy and precision of the recommended method when applied to metal concentrations as low as 0.1 p.p.m. The method has been applied to a number of typical petroleum stocks, and its effectiveness in determining material balances in refining processes is demonstrated. The values found for the iron, nickel, vanadium, and copper content of a number of crude oils are also included.
I n order t o attempt t o resolve these discrepancies, the authors decomposed a number of samples of crude oils, distillates, and residual fractions by both dry-aehing and net-osidation methods. The ashes were t,hen analyzed for nickel. vanadium, and iron. The dry-ashing procedure was as folloivs: The sample of the oil to be analyzed x a s ignited in a S'ycor vessel and allowed to burn freell- with occasional reignition until only a carbonaceous residue remained. The residue was then burned to an inorganic ash a t a temperature of 475" to 525" C'. in a muffle furnace. The net-oxidation method involved decomposition of the material with sulfuric acid 15-ithout any preliminary ignition. The method is described in detail under Recommended Procedure. Results are shown i n Tables I and 11. There is no difference in the values obtained for iron, nickel, and vanadium for crude oils or residual fractions. Hon-ever, in the case of various overheads, dry-ashing causes a significant loss of nickel and vanadium. This apparent discrepancy can be explained readily. Independent n-ork a t the authors' laborator>- has s h o m t h a t for typical stocks treated under representative refining conditions, only a Emall portion of the nickel and vanadium in the charge appears in overhead fractions. This indicates that only a minor percentage of the total metal content' of crude oils and residua is in the form of volatile compounds: therefore, even appreciable loss of the volatile components during ashing has little or no effect on the total metal recovery. On the other hand, t h e metal content of overhead fractions is largely in the form of volatile compounds, and if these are partly lost during ignition, the percentage of metal recovered is seriouslJ- affected.
Table I. Comparison of Ignited and Sulfated Ash Techniques for Crudes and Residual Fractions Stock California crude .I California crude B California crude C California residuum E. Texas crude Venezuela crude Gulf Coast crude West Texas crude S o . 6 fuel oil
Iron, P,P,AI. Ign. Sulf.
17.4 25.5 28.1 87
16 8 25.0 28.1 83
..
..
.. .. ..
32.5
31:3
, .
Sickel, P.P.M. Vanadium, P.P.lL. Ign. Sulf. Ign. Sulf. 217 93 94 217 34
i.75 3 8 1.54 0 77 15.4
...
31
...
1.69 3.7 1.64
0.76 15.0
....
....
47
47
1.25 16.4 0.84
1.05 16.1 0.81
74
74
.... ....
..,.
....
Table 11. Comparison of Ignited and Sulfated .Ash Techniques for Overhead Fractions Kickel, P.P.M. Vanadium, P.P.hl. Stock Ign. Sulf. Ign. Sulf. California crude (molecular dist. overhead 1 ) 52 65 40 64 113 118 122 (molecular dist. overhead 1 ) 94 5,2 6.6 5.3 Crude 4 (flash vaporization 1 ) 4.0 2.0 4.9 5.1 6.7 Crude B (flash vaporization 1 ) 1.6 3.4 1.0 Crude B (flash vaporization 2) 2.3 0.31 0.32 0.09 C r u d e C (tarseparatoroverhead) 0 03
ANALYTICAL CHEMISTRY
1730 From the above data it is concluded that a sulfation or wetoxidation method must be used for distillate fractions, whereas simple ignition may be adequate for crudes and residual fractions. However, the authors use a sulfation method for all stocks. This not only minimizes the possibility of loss, but is actually more convenient, since excessive coking during a dry-ashing decomposition makes it extremely difficult to keep the sample burning and increases the time required for the final ignition. DETERMINATION OF ASH
Although ash requirements frequently appear in specifications, the difficulty of obtaining reproducible results and selecting optimum ignition temperatures is well recognized by analysts. Certainly in a mixture as complex as a typical crude, an ignited ash may contain oxides, sulfates, carbonates, etc., depending on the method, final ignition temperature, and possibly technique of the operator. The ash value could thus hardly be used for a meaningful material balance. On the other hand, where a SUIfated ash method is used, a knowledge of the elements present and of the decomposition temperatures of their sulfates, should permit the analyst t o select a final ignition temperature a t which a reproducible and predictable composition can be obtained. A sulfated ash would therefore be expected to be considerabiy more valid.
/L r 7-
Table 111. Element Added Vanadium
Ignition of Metallic Sulfates
Copper
Table IV.
Composite Metallic Sulfates Ignited at 750' C.
Iron Nickel
Element Added Iron Copper Nickel Van adi um
Iron Copper Nickel Vanadium
Calcd. as Sulfate, l l g . 82.8 113.1 71.5 53.3 199.6 50.2
Ash, Mg. C. 825' C. 35.6
Calcd. as Oxide, Mg. 35.7 48.8 28.6 25.7 96.4 25.0
Weight Of
600' C. 35.4
Calcd. a8 Oxide, Mg. Fez01 14.30 CuO 6.26 NiO 6.42 VZOK 8.92 Total 35.90 Fez08 7.15 CuO 6.26 19.26 Xi0 T'zOa 17.85 Total 50.52
Z8:8 54.1
48:8
750'
28:7 26.0
4816
.. ..
96: 1 25:1
Wt. of Ash Found, Mg.
35.7, 35.5
50.6, 511.6
for estimating the inorganic constituents. Spectrographic, photometric, polarographic, and even conventional volumetric and gravimetric methods can be used. Spectrographic methods are rapid, sensitive, and specific and have the advantage of permitting analysis for a number of different elements at the tiame time, but lack somewhat in precision and require extensive standardization. Gravimetric and volumetric methods generally require a larger quantity of material than is ordinarily available. Photometric and polarographic methods seem to be ideally suited.
INFRARED LAMP
VYCOR V E S S E L
II
I+AIR
1-
BATH
ek
HOT PLATE
Figure 1.
Ashing Apparatus
T o evaluate the effect of igniting an ash containing iron, nickel, vanadium, and copper as the sulfates, various blends of pure salts were sulfated and ignited to constant weight in platinum, under controlled temperature conditions. Results are shown in Tables 111 and IV. It can be seen that a t a temperature of 600' C. the vanadium and iron are quantitatively converted to their oxides, but the copper and nickel remain essentially as the sulfates, However, a t a temperature of 750' to 825' C. all the iron, nickel, vanadium, and copper are quantitatively converted to their oxides; recovery is complete. Despite the fact that vanadium pentoxide melts a t 690' C., no vanadium is lost even a t a temperature of 825' C. The vanadium pentoxide does tend to dissociate into the tetroxide a t this temperature (6), but the dissociation constant is so low that it is analytically insignificant. It can be concluded that in so far as the above four metals are concerned, the inorganic residue may safely be ignited a t a temperature of 750' to 825' C. If there is any metal loss, it undoubtedly occurs during the decomposition of the sample. However, it is important to note that if a porcelain crucible is used for the ignition a t the above temperature, fusion of the metal oxides with the surface of the crucible may occur. Although this would not result in a low ash value, some of the metallic components would be lost for subsequent analysis. DISCUSSION OF CHEMICAL METHODS
Contrary t o the situation that exists in dealing with the ashing procedure, there is relatively little difficulty in selecting methods
'I
5"
Figure 2.
Air Bath
All parts 16-gage aluminum
I n the authors' laboratory inorganic components of crude oil fractions are usually determined by a combination of colorimetric (19) and polarographic techniques. The scheme used for iron, nickel, vanadium, and copper (the four elements moat frequently determined) is given in detail under Recommended Procedure. In general, the method is as follows:
1731
V O L U M E 2 4 , NO. 11, N O V E M B E R 1 9 5 2 The ash is solubilized either by treatment with hydrochloric acid or by fusion with sodium bisulfate and leaching. The solution is adjusted to volume, any silica or insoluble sulfates being removed by filtration. Aliquots are then taken for the determination of the individual elements, the size of each aliquot being governed by the expected content and the concentration range covered b the instrument calibration curve. Iron is dktermined colorimetrically as the ferrous o-phenanthroline complex; the method is free from interference by most common elements (4). An excess of nickel causes gradual fading of the color, but this can be overcome by making measurements immediately or by using a larger than theoretical amount of reagent (7, 12). Nickel is determined colorimetrically as the colloidal nickel dimethylglyoxime in ammoniacal citrate solution; none of the common elements in the ratios existing in crude oils interferes. Under the conditions chosen, the color develops immediately and is stable for about 1 hour. I n special cases, where the iron to nickel ratio may be exceedingly high, the iron citrate will absorb. sufficiently to cause a slight positive error in the nickel content. By independently measuring the absorbance of the solution in the absence of dimethylglyoxime but in the presence of all other a'lded reagents, the necessary correction can be determined. However, since the absorbance due to iron is only about 1/600th of t h a t due to nickel, this is rarely necessary. Vanadium is determined colorimetrically as the phosphotungstate complex. It was found that even a moderate excess of iron interferes; the iron is therefore first separated by electrolysis with a mercury cathode. Copper is determined polarographically (6) after isolation from the other metals by a microelectrodeposition. I n the absence of large amounts of other metals-e.g., in the analysis of cracking feed stocks-the copper can be determined directly without preliminary electrodeposition. The sensitivity of each of the determinations under the conditions selected is about 1 microgram. On the basis of a n aliquot representing 100 grams of the original sample this would correspond to 0.01 p.p.m. RECOMMENDED PROCEDURE
Weigh a representative sample into a 700-ml. Vycor vessel (made by cutting off the rim of an 800-ml. beaker). The size of the sample is governed by the expected metal content; any quantity may be taken, but it is best to decompose large samples in 100-gram increments. Add 0.5 ml. of concentrated sulfuric acid for each gram of sample, place the vessel in an aluminum air bath (Figures 1 and 2) on a cold hot plate, and heat gently from the top with an infrared lamp. As the decomposition proceeds, gradually increase the heat of the lamp to maintain a steady evolution of fumes, finally progressively increasing the temperature of the hot plate until the sample is reduced to a carbonaceous ash. Place the sample in a muffle maintained a t 475' t o 525' C., introducing a stream of oxygen into the furnace to expedite the decomposition, and heat until the carbon is completely destroyed. If an ash value is required, carefully transfer the inorganic residue
to a platinum crucible, and ignite to constant weight a t 750' to $25' C. After determination of the ash, fuse with 2 grams of sodium bisulfate. (The potassium salt is avoided since large amounts of potassium interfere in the subsequent vanadium determination.) Leach with water, transfer to a 100-ml. volumetric flask, filtering if necessary, and adjust to volume. If a n ash value is not required, digest the residue in the vessel for 10 to 15 minutes with 10 ml. of 1 to 1 hydrochloric acid, and transfer directly to the volumetric flask, filtering if necessary. Determination of Iron. Transfer an aliquot containing between 0.01 and 0.08 mg. of iron to a 25-ml. volumetric flask, a t the same time adding an equal aliquot to a small Erlenmeyer flask. Titrate the latter with 0.5 M sodium acetate until the solution is alkaline to bromophenol blue. T o the portion of the solution in the volumetric flask add 0.2 ml. of 10% hydroxylamine hydrochloride solution, followed by 1 ml. of 0.1% o-phenanthroline solution. Add the amount of sodium acetate required (as determined by the separate titration), and adjust the volume. Measure the transmittance a t 520 mp, setting the instrument with a r e agent blank. Determination of Nickel. Transfer an aliquot containing between 0.0025 and 0.04 mg. of nickel to a 25-ml. volumetric flask. Dilute to approximately 15 ml. and add 0.5 gram of citric acid. Add 0.5 ml. of iodine solution (6.4 grams of iodine in 500 ml. of water containing 12.5 grams of dissolved potassium iodide), followed by 3.0 ml.'of concentrated ammonium hydroxide. Add 0.5 ml. of dimethylglyoxime solution (1% in alcohol) and adjust to volume. Measure the transmittance a t 540 mp, setting the instrument with a reagent blank.
J
NITROGEN INLET
JJ!7
fl
A/
NITROGEN OUTLET
.IDE
RUBBER STOPPER Figure 4.
PLAT I NUM ANODE NO. 20 W I R E
zk jMM--r/
Figure 3.
DIAPHRAGM NITROGEN S T I R R E R P L A T I N U M CATHODE 300 MM OF N 0 . 2 0 WIRE
Electrodeposition Cell
Micropolarographic Cell
Determination of Vanadium. Select an aliquot containing between 0.02 and 0.2 mg. of vanadium. If chlorides are present, first transfer to a 100-ml. beaker, add 1 ml. of concentrated sulfuric acid, and eliminate the chlorides by evaporating to sulfuric acid, Place in an electrolysis beaker containing a layer of clean mercury about 0.5 em. deep, holding the volume of the sample solution to about 50 ml. Electrolyze a t 5 to 6 volts and a current of l to 2 amperes for 15 minutes, stirring the mercury continuously. Without discontinuing the current, draw off the mercury. Filter the electrolyte, wash with water, and heat to boiling. Reoxidize the reduced vanadium by adding 0.1% sodium permanganate solution dropwise until a pink coloration ersists for several minutes. Reduce the excess permanganate g y adding 2 to 3 drops of 1 to 1 hydrochloric acid and boiling. Adjust the volume to about 10 ml. and, in succession, add 2.5 ml. of 2.5 M sulfuric acid, 0.8 ml. of 85y0 phosphoric acid, and 1.2 ml. of 0.5 M sodium tungstate. Heat just to boiling, then allow to cool. Transfer to a 25-ml. volumetric flask and adjust the volume. Within 1 hour determine the transmittance a t 420 mp, setting the instrument with a reagent blank. Determination of Copper. Transfer an aliquot containing 0.02 to 0.1 mg. of copper to the electrodeposition vessel (Figure 3).
1732
ANALYTICAL CHEMISTRY
Add 1 ml. of concentrated sulfuric acid, and evaporate t o gentle fumes. Add 15 ml. of water, and 4 ml. of 0.2 iM hydrazine sulfate. Stir by means of a current of air or nitrogen, and electrolyze overnight a t 3 volts. Without discontinuing the current, remove t h e electrolysis vessel, simultaneously flushing the cathode thoroughly with water. Remove the cathode, place it in a tared micropolarographic cell (Figure 4), and strip the copper by running 1 ml. of concentrated nitric acid dropwise down the platinum wire. Rinse the electrode with 2 or 3 ml. of water and eva orate the solution t o dryness. Add 0.5 ml. of 1 M tartaric a c i f a n d 0.4 ml. of water, and warm to dissolve. Add 1 drop of bromocresol-purple indicator and neutralize to a muddy green with 10 M sodium hydroxide (approximately 0.10 ml. is required). Add 0.02 ml. of 0.25% gelatin solution. Weigh the cell on an analytical balance and a d d water until the weight of the solution is 1.06 grams. Trace the polarogram.
Table VII.
,
ACCURACY AND P R E C I S I O N
Table V gives the results obtained by the over-all procedure on a series of synthetic standards, these consisted of portions of a highly refined petroleum oil t o which knoMn amounts of the four metal6 (as naphthenates) m-ere added in various ratios. Although significant amounts of other elements such as silicon, magnesium, aluminum, and calcium are present in crudes, they were not included in these control tests; however, companion experiment8 on inorganic blends containing these elements established that there was no interference in the polarographic and colorimetric procedures recommended Table VI shows the results obtained by check determinations on a number of representative stocks. These results, in all cases, represent samples processed a t different times and/or by different analysts. It might be mentioned that only small amounts of copper are present in most stocks and iron is often introduced by contamination in pipelines, stills, storage, etc. Therefore the authors’ studies on materials other than crudes have dealt primarily with nickel and vanadium. The accuracy of t h e method has been further confirmed by a number of material balances on various stocks. The results of several such balances are given in Table VII.
Flash Vaporization Material Balances for Nickel and Vanadium
Distillate Residuum Charge
88.5 11.5 100.0
0.09 5.6 0.74
Run 2 Distillate Residuum Charge
60.2 39.8 100.0
1.10 46.0 19.0
0.10 23.0 9.0
Run 3 Distillate Residuum Charge
80.8 19.2 100.0
3.70 82.0 19.0
0.20 47.0 9.0
0.32 26.1 3.35
0.08 Total C“r of charge
0.28
3.00 0.64 -~ 0.72 97.3
3.28 97.9
0.06
0.66 Total
‘3 of charge
9.15 _-__
18.31 __
18.97 99.8
9.21 102.0
2.99 0.16 15.74 _ _ _ - 9.02 Tots1 18.73 9 18 n0 of charge 98.6 102.0
Table VIII. Analysis of Various Crudes Crude
East Texas West Texas Mirando Jackson Scurry County Wilniington Santa Maria Kettleman Yentura Tibu-Petrolea Kuwait Mid-continent Kansas ~Iorocco Redwater
Fe, P.P.11. Xi P.P.M. Y, P.P.M.
3 2 31 7.6 4 4 3.4 28 17 24 31 1.6 0.7 3 8 5.8
3 ‘4
1.7 4.8 1.9 1.8 1.0 46 97 35 33 9 0 6.0 4.2 5.8 0.8 10.6
1.2 7.9 1.4 0.9
0.8 41 223 34 49 60 22.5 7.9 20.8 0.6 4.5
Cu, P . P . l I . 0.4 0.4 0.5 0.2 0.2 0.6 0.3 0.4 1.1 0.9 0.1 0 :3 0.4 0.1
