Académique Documents
Professionnel Documents
Culture Documents
29
but the general situation is
Climate, Allowable mximum Climate, Allowable mximum
F Reid vapor pressure F Reid vapor pressure
60 12.7 100 7.0
70 11.0 110 6.0
80 9.4 120 5.3
90 8.0
.
Vapor pressure also governs storage and handling losses,
30
particularly
at high altitudes. The relative tank-filling losses for an 8.5 R.v.p, (Reid
vapor pressure) gasoline at 80F at diferent altitudes is somewhat as
follows:
Altitude
Relative loss
Sea leve!... ..... 1.0
5,000 ft... ........ 1.5
10,000 ft... ........ 2.3
15,000 ft... ........ 5.5
20,000 ft... ........ T11.0
With the advent of bigh-compression motors, the tendency of a fuel to
spark-knock or detonate violently has attracted much attention. Knock- ing
is thought to be due to autoignition of part of the charge in front of the
flame. Mild knocking has little effect on the performance of the engine, but
severe knock may result in loss of power and 'damage to pistons or
bearings. Certain substances such as lead tetraethyl,
31
iron pentacarbonyl,
32
etc.,
32
tend to prevent knocking. All hydrocarbons have different antiknock
properties, and certain of these, such as benzol
33
and
18
Brown, G. G., The Volatility of Motor Fuels, Eng. Research Bull. 14, University of
Michigan, 1930, p. 7.
* Good Gasoline, Nati. Bur. <Standard* Letter Circ. 551, Apr. 19, 1939.
10
Nelson, W. L., Evaporation Losses at High Altitudes, O Gas J., Dee. 9, 1944, p. 83.
11
Midgley, Thomas, Jr., Tetraethyl Lead Poison Hazard, Ind. Eng. Chem., 17, 827 (1925).
81
Gaylor, P. J., Patent Trends in Petroleum Refining-gasolines, Nati. Pet. News, Aug. 7,
1946, p. R-584.
Campbell, Lovell, and Boyd, Standard Fuel for Anti-knock Quality, Oil Gas J., Jan. 23,
1930, p. 42,
those in cracked gasoline, are useful in suppressing knocking. Octane
number is greatly affected by altitude.
34,35
The octane number may be about
three units lower for each 1,000 ft of elevation at elevations near sea level
(growing to 7.5 per 1,000 ft at 12,000-ft elevation). Thus, if an octane
number of 67.5 is necessary at sea level, 50 is satisfactory at 6,000-ft
elevation, and at 12,000-ft elevation even 20 is satisfactory.
Knocking occurs
27,89
in average cars somewhat as indicated in Table 3-9
for a polyform gasoline that was rich in olefin and aromatic hydrocarbons.
TABLE 3-9. OCTANE NUMBER REQUIRED TO PREVENT KNOCKING
Motor
method
Approximate percentage of cars that
knock
octane
number
Approx. Approx. Approx.
15 mph 40 mph 60 mph
60
80 50
65 80 54 28
70 68 30 8
75 50 10
80 25
85 5
TABLE 3-10. Appkoximate OCTANE NUMBERS REQUIRED TO SATISFT 10, 50, AND 90 PER CENT OF NINE
1953 MAKES OF CARS OPERATINQ ON FULL-BOILING-RANGE GASOLINES .
Car
make
No. cars
testcd
Research octane number to satisfy
10 % of cars 50 % of cars 90 % of cars
1 28 88 93 96
2 24 86 91.5 95
3 27 87.5 91.5 95
. 4 . 24 87.5 92 94.5
5 28 84 88.5 94.5
6 22 85 89.5 93
7 30 83 86 93
8
1
27 84 87 91.5
9 25 78 85.5 90
TABLE 3-11. APPBOXIMATE LEAD SUSCEPTIBILITY OF GASOLINES
AND HTDBOCARBONS
a
*
Type of gasoline Octane Increase in Motor o.n. with Number
number 1 cc 2 cc 3 cc 4 cc 6 cc of tests
n-Heptane* ............................... 0.0 10.1 29.1 43.0
.
1
Catalytically desulfurized
straight run
d
..............................
54.5 14.9 21.3 25.2 27.9 31.8 20
Catalytically desulfurized
natural'
1
.....................................
61.6 13.6 19.6 23.1 25.5 28.9 6
Straight run, low sulfur, low
octane ......................... * ...........
43.4 10.7 16.9 21.1 24.0 28.2 12
Straight run, low sulfur, regular
octane ....................... i ..............
55.9 9.7 14.6 17.7 19.8 22.9 26
Straight run, low sulfur, high
octane .......................................
64.0 9.4 13.9 16.6 18.5 21.1 28
Straight run, low sulfur ............. 71.6 8.0 11.8 13.8 15.3 17.4 12
Natural gasoline ........................ 65.7 8.4 12.4 14.8 16.8 18.8 38
Straight run, high sulfur.... 55.9 7.5 11.3 13.7 15.3 17.7 23
Catalytically desulfurized
cracked*
1
..................................
69.9
8.3
10.4 11.7 12.6 13.7 6
Isooctane mixes* ......... ............ 83.0 8.1 11.6 14.1 16.2 18.4 8*
Cracked, low octane ................. 57.5 8.1 12.2 14.7 16.5 18.9 4
Cracked, regular octane.... 64.5 6.5 9.5 11.3 12.6 14.4 38
Cracked, high octane ................ 71.6 4.0 5.8 6.9 7.6 8.6 16
Aromatic gasolines ................... 72.6 6.2 9.0 10.6 11.6 13.2 13
Methylcyclohexane* ................. 73.0 2.5 9.6 12.2
. . .
1
Houdry catalytic ........................ 75.8 5.9 8.5 9.9 10.9 12.4 30
Catalytically cracked ................ 78.4 5.0 6.6 7.5
. . .
9.5 38
Polymer, catalytic ..................... 82.5 2.0 2.9 3.4
. . . .
4.3 9
Diisobutylene* .......................... 84.3 2.2 2.7 3.2
1
Isooctane
6
................................. 100.0 3.8 6.9 8.9
m m m m
. . . .
1
Toluene* ................................... 105.3 1.8 3.2 3.2
. . . . a
1
a
Nelson, W. L., Lead Response, Oil Gas Oct. 6, p. 106; Oct. 13, p. 137, 1945.
b
Buerstetta and
Warren, Oil Gas J., Nov. 21, 1955, p. 142. Numbers over 100
based on: R.o.n. = 128 2,800 -5- P. N.
0
Taken from Oil Gas J., Nov, 27, 1941, p. 70.
d
Desulfurized at high temperature with
bauxite or clay.
The octane number required by cars of even the same make ranges by at
least 7 to 12 Research octane units (see Table 3-10).
37
Although addi-
tional power can be developed by the use of high-octane fuels in suitable
engines, the extra power or mileage obtained by the use of high-octane-
*
T
GRC Octane Number Requirement Survey, 1953.
number fuels in current vehicles is not impressive
38
or conclusive. Under
some conditions of operation a 10 per cent increase in mileage
33
appears to
be possible by increasing the octane number from 68 to 83, but tests on
some vehicles indicated no improvement or even a decrease in mieage.
High-octane fuels do provide smoother, more satisfactory performance.
TABLE 3-12. APPROXIMATE LEAD SUSCEPTIBILITIES OF* VARIOUS TYPES OF GASOLINES AS A FUNCTION OF CLEAR
OCTANE NTJMBEH
Clear
lacrease in octane number with 3 CC TEL
octane
number, Straight Reformed Reformed Thermal Catalytic
Motor, or run* (catalytic) (tbermal) cracked cracked
Research, as
applicable*
Motor Res. Motor Rea. Motor Rea. Motor Res. Motor Res. Motor Re,
30 26.0 26.0
35 25.0 25.0
j.
49 23.5 23,0 * * *
..... 23.5 23.5
45 22.0 21.5 25.0 26.5 21.5 21.0
50 21.0 20.0 23.0 24.5 19.5 20.0
55 20.0 18,5 20.0 22.0 17.0 18.0 16.0 17.0
60 19.0 17,0 18.0 20.0 15.0 16.5 14,0 15.5
65 17.5 15.5 6.5 18.0 13.0 15.5 11.5 13.5
70 16.5 14.5 14.5 16.5 11.0 14.0 8.5 10.5 10,G-
75 15.5
a
12.5 11.5 14.5 8.5 11.5 5.5 7.5 8.5 . . . * i e.S'
80 m * 11.0 9.5 12.0 6,5* 10.0 * * 6.0 10.0 4.0
85
l t i # i
7.0 10.0
8.5 V m m
m
4.0 8. 0 2.5
e
8.5
90 * *
m m
5.0 8.0
7.0 M. . *
*
*
6.5
6.5
95 *
>
m
6.0
. . . . . . . * *
.
*
*
4,0 . . . . 4.5
* Uae Motor method with Motor octane columna and Research with Research columna.
* Gasolines that contain 0.10.3% sulfur are lesa susceptible {about 4 imite); Nelson, W. L., Oil Gas Oct.
13, 2945, p. 145, CatalyticaLly desulfurized gasolines are more susceptible (about 3 units); Nel- Bon, W.
L., Oil Gas J., Oct. 27, 1945, p, 127.
* Eitrapolated. These are extremes, seldom encountered.
The susceptibility of fuels to tetraethyllead is not uniform. The octane
number is increased greatly if (1) the clear or unleaded octane number is
low, (2) the sulfur content (particularly mercaptans, monosulfides, and
disulfides) is low, and (3) the percentage of olefin hydrocarbons (cracked
gasolines) is low. Although variations are great, the general situation is
indicated in Table 3-11,
40
which is an average of about 327 tests. Table 3-
12 can be used to estimate the effect of tetraethyllead on the octane
,s
Nelson, W. L., Power versus Octane Number, Oil Gas Nov. 16, 1946, p. 317.
19
Van Hartlesveldt and Field, Knocking Octanes, Pe. Refiner, June, 1940, p. 93.
10
Nelson, W. L., Lead Responso, Oil Gas J., Oct. 6, p. 106; Oct. 13, p. 137, 1945.
number of various types of gasoline. A substantially straight line resulta
when the octane numbers of leaded gasolines are plotted on charts such as
Fig. 3-4.
7
The Performance Number shown on the right-hand seale of Fig.
3-4 represents the approximate relative amount of power that can be
developed.
In summary, our motor fuels consist of butanes and natural gasoline for
front-end volatity, cracked or polymer gasolines and antiknock agents for
allaying knocking, inhibitors for the delaying of gum for- mation, and
straight-run gasoline. Thermally eracked gasolines are desirable in motor
fuels because of their good low engine-speed performance, The low-
boiling olefin hydrocarbons cause such performance. At high speeds the
aromatic hydrocarbons found in catalytically cracked gasolines provide
superior performance. Thus a mixture of the two kinds of fuels is advisable,
particularly so that the L-head engines which knock at high speeds and the
valve-in-head engines which knock at low speeds are both satisfied.
Naphthas or Solvents. The enormous number of uses for specialty
materials intermedate or embracing parts of the boiling range of gasoline
and kerosene makes for confusion and overlapping of specifications. Tables
3-13 and 3-14 show the average properties and uses for 20 representativo
naphthas
8
grouped generally with respect to boiling range. Straight-run
petroleum naphthas contain only small amounts of aromatic hydrocarbons
and henee are not good solvents for some materials, notably nitrocellulose
lacquers, dry paint, or certain resins. High-solvency naphthas dissolve such
materials, and special sol ven cy tests
9
such as aniline poinfc, kauri butano!
number, and dilution ratios of nitrocellulose in ethyl or butyl acetate are
employed. The low-gravity naphthas of Tables 3-13 and 3-14, shown in
boldface type, are high-solvency naphthas produced by special processing
methods that increase the percentage of aromatic hydrocarbons. A 48.4 API
naphtha similar to No. 16 of Table 3-13, but containing 15 per cent of
aromatic hydrocarbons, is used to deweed crops of carrots, parsnips, dill,
or caraway.
Among the special requi remen ts of solvents may be white color; low
unsaturated and aromatic content for stability; high aromatic content for
solution of lacquers or synthetic resins; or low boiling for rapid vola-
tilizaron. In general, however, naphthas should be free from acidity,
noncorrosive by the copper-strip test, free from gums or suspended
matter, sweet smelling so that a petroleum odor is not imparted to the
7
Ethyl Corp. Research Laboratory Chart, Apr. 15, 1949.
** Nelson, W. L., Classification of Solyents and Naphthas, Oil Gas J., Apr. 15, 1943, p.
134.
Nelson, W. L., DUution Eatio Tests, Oil Gas J., June 30, 1945, p. 117.
Key number of solvent
JrToperty 1 2 3 4 5 6 7 8
API gravity........................... 75.1 75.5 74.6 53-70.5 71.5 40 64 62
I.B.P., F ............................... 95 145 125 160 105 179 195 205
10 per cent .......................... 115
. . .
t
136
i
9 < - * *
60 per cent .............. . ......... 135 150 ,162 175 ISO 191 200 210
90 per cent .......................... 156 * * * ' 188 195 220 245 210 220
E.P., F ................................. 186 160 206 210 260 275 215 240
Flash (Tag C.C,). F..,. -73
. .
1
-40
* - * 9' * * . . . . . * .
Kauri butano! No ............. . .
30.5 34.5 33.5-49 34 77 35.5 37.5
a
Solventa high in aromatic hydrocarbons (high solveney) are shown boldace.
TABLE 3-14. USES OF 20 REPRESENTATTVE
Boiling
range,
Key number of solvent with
Use of solvent
1
95
186
2
145
160
3
125
206
4
160
210
5
105
260
6
179
275
1 Perfume extrfWtio* . ...
T
............. ....... , , . . 160-260
x x
% Castor oil or fat extraction .......................... 125-300 #
X X X
3.
Toluene substitute, lacquer formulas, fast-
setting varnishes ............................ .............
179-275
160-300
l
x
4 Seed extraction ............................................
X
x
5.
6.
Rubber cementa, tire manufacture ..............
Lacquers, art leather, rotogravure ink,
adhesive tape ...............................................
95-370
95-370
X
x
X
X
.x
X
X
X
X
X
7.
Rosin extraction, shade cloth, rubber dip
goods.....; ............ . . .....................................
205-300
8.
Brake linings, leather degreasing, bone
degreasing .................................................. '.
125-400
X
x x
9.
10.
Printers ink, cellulose lacquer diluent..
Paints and varnishes, tbinners .....................
160-370
105-455
* ...
X X
*
11. Textile printing and proofing ....................... 160-410
X
12.
Paints and coa.tinga (aircraft), paint re-
mover and solvents ....................................
179-410
X
13.
Paint sbop rinsing and cleaning (aircraft)
Floor coverings, wax, polish, wash for
printing plates or rolls .......................... .
240-340
14. 200-410
15.
Dry cleaning, metal and machinery cleaning
......................................................................
200-400
16.
Zylol substitute (in many instances).,.. Fiat
finishes, rustproof compounds ....................
275-370
17. 300-455
18. Synthetic resin thinner... 357-410
19. Wood preserva ti ves ....... 312-650
Solventa high in aromatic hydrocarbons (high solveney) are shown boldface.
Key number of solvent
9 10 11 12 13 14 15 16 17 18 19 20
59.5 37-58 46 58 40 35 35-50 50 48 3050 45 40
200 200 225 220 240 275 303 312 325 357 350 320
210 215 V 230 - - 280 317 322 333 367 375 375
217 232 242 250 285 300 328 337 350 380 400 485
232 253 # 270 ' 330 352 368 370 397 430
247 286 280 300 340 360 376 380 400 410 455 650
25 25 m m m 45 , , , 80 99 . 115 136 142 145
38,5 39-69 54 38 72 73 35-63 33 35 31-65 32
NAPHTHAS AND SOLVENTS* (see Table 3-13)
boiling ranges, F
7
195
215
8
205
24$
9
200
247
10
200
285
11
225
280
12
220
300
13
240
340
14
275
360
15
300
370
16
312
380
17
325
400
18
357
410
19
350
455
20
320
650
X
X X
* m *
X
* i
X
*
* *
X
X
X
X
m m *
X
X
X
9 * * *
X
X
. . .
X X
* *
X
*
* X
X X X
. . .
X
.
*
X
. . ,
X X X
x
X
U 9 *
X
Y
X
*
X
. . .
X
X
X
X
* #
* * 1
X
X
*
* X X
X
*
X
X
X
X
X
1 * 1 . . . . . .
X
a * *
X
X
X
* * * * * *
X
* m
X
. . . *
X
. . . *
X
. . .
X X
*
X X
X
'
X
X
X
X
X
X
X
X
X
X
X
X
*
1
X
manufactured products, and well fractionated to elimnate as much of the
fire hazard a3 possible.
There is an increasing tendency to offer extremely narrow-boiling-
range naphthas (under 30F) which are superior for some services but
which can often be replaced by cheaper naphthas of wider or convencional
boiling range. Nearly pur hydrocarbons ranging from propane through
hexane are also being offered.
The mineral-oil solvents should not be considered as substitutes for
other solvents that are now used, because mineral solvents possess
properties that are unique and useful, and for many purposes they can be
selected because of their own merits.
Jet Fuels. The production of military jet fuels reached 95,000 bpd in
1953 and the expected demand in 1957 is about 250,000 bpd (2.9 per cent
of crude oil). Although a kerosene-like material (JP-1 Grade) was first used
and a similar high-boiling fuel (JP-5) is still supplied in limited quantities,
the main current fuels (JP-3 and JP-4) are wide-boiling-range materiais
which extend through gasoline and kerosene. Table 3-15 indi- cates the
kinds of fuels supplied and Table 3-16 shows
14
in detail the 1954
properties and the specifications of jet fuels. Production has bee# almost
totally straight-run material, but there are indications that small amounts of
cracked materiais and heavy alkylates or reformates can be incorpo- rated.
In the event of war, such materiais will have to be tolerated. The Smoke
Volatility Index of Table 3-16 is the IP smoke point plus
0, 42 times the per cent distilled at 400F. Its superiority as a means of
judging deposition tendencies over plain smoke point has not been com-
pietely established. The low freezing point of minuS 76F is a difficulty in
meeting specifications, and if certain naphthenic or aromatic crude oils are
processed, the gravity requirement becomes limiting.
Throughout the world, specification DERD-2482, which is an Eastern
Hemisphere kerosene, is used almost exclusively (1956), but some airlines
require a freeze point of 50F rather than 40F. .
Burning Oils. These oils, represented by kerosene, long-time burning
oil, lighthouse kerosene, and 300F mineral-seal oil, are used, as their
ames imply, in household, marine, passenger-coach, and railroad illumi-
nating lamps. Kerosene is the main product in the United States but ASTM
No. 1 Distillate has such similar properties that it is increasingly being sold
as kerosene. Likewise, Eastern Hemisphere kerosene is sold as jet fuel.
The 300F mineral-seal oil is a high-grade oil having a Cleveland open-cup
flash point of not less than 250F. Signal oil for railroad lamps is
compounded from 300F mineral-seal oil and lard or sperm oil. Long-time
burning oil is the finest grade, and in the burning test 650 cc of oil must not
be consumed in less than 120 hr-
The valu of kerosene is direetly dependent upon its behavior in the
burning or lamp test. An unsatisfaetory buming test is terminated by
smoking, by a white eloud on the chimney, or by a toadstool formation on
the wick. Smoking is due primarily to aromatic hydrocarbons; a white eloud
is probably produced by disulfides (over 0.01 per cent); and toadstools are
thought to be related to both aromatics and disulfides.
TABLE 3-15. CHARACTBRTSTICS OF JET FUELS, 1952-1956
No.
API
grav-
ity
Dist- temp., F Red Sul-
Aro-
matics,
vol. %
Gum
existen t
steam-
jet
Fuel
of
sam-
ples
10%
evap.
50%
evap.
90%
evap.
vapor
pres-
sure
fur,
wt
%
Avg. Grade JP-1:
1952 .............. ..
3 42.3 338 368 421 * 0.057 14.3
Avg, Grade JP-3:
1952 ..................
6 52.5 166 316 433 6.0 0.081 14,7
1954 ............... - ___ 4 56.5 160 265 421 5.7 0.089 10.3 1.5
1956....:. .................. 3 55.6 157 272 430 5.6 0.063 9.3 1.1
Avg, Grade JP-4:
1952 ......... .......
24 50.5 222 332 430 2.6 0.075 11.9
1954 ....................... 23 51.5 216 319 425 2.6 0.080 11.3 0.6
1956 ........................ 31 52.4 217 317 409 2.6 0.054 10.5 0.8
Avg. Grade JP-5:
1953 .................
1 37.3 397 432 491 0.5 0,46 8.3 2.0
1955 ........................ 3 39.8 . 392 428 485
0.167 12.0 0.9
1956*; ..................... 1 37.7 389 418 468
* *
0.26 10.0 1.0
1956* ...................... 1 39.3 386 422 472 0 0.18 12.8 0.5
a
Blade, O. C., National Annual Survey of Aviation Fuels, 1956, U.S. Bur. Mines Inform. Circ.
7782, March, 1957.
&
Both of two san pies are shown.
Although the Institute of Petroleum (British) smoke test
45
is not usually
specified in the United States, it is used widely throughout the world. The
smoke point is the height in millimeters of the fame that can be produced in
a standard lamp without causing smoking. Mid Continent kerosene exhibits
a smoke point of 21 to 24, and the smoke point of these materials is raised
to mdre than 30 by acid treating.
46
A smoke point of 17 is satisfactory for
most world trade.
jravity ...................................
Aver-
age
56.5
160
265
421
84
5.7 < 76 2.15 130.5 7,373 1.06
0.089
0.001
10.3 0.6
29.4 64.7
1.6
1.5
Grade JP-3
Distillation temp
10% evap., F ..................
50% evap., F ...................
90 % evap., F ...................
400F point, % evap...
End point, "F .....................
Eteid vapor pressure, psia.
Preeaing point, F..............
Viscosity, kinematic at 40F,,.,
^niline point,
e
F .............. . ................. .
\jailine gravity constant ...................
3romine No., wt % Br ........................
Sulfur
Total, wt % .......................................
Mercaptan; ........................ . ......... .
\jromatics, vol. % ........... . ................
Dlefin content. .................... .. ..............
Smoke point ................................... ....
Smoke Volatility Index. ...... ...............
jum
Ex 8ten t. . ............................. .
Air-jet, 400F mg/100 mi.... Steam-jet, 450F, mg/100 mi.
Grade JP-4
Specifica-
tion
6
45-63
400 max
600 max 5-7 76 max
30 max
0.4 max 0.005 max 25 max
10 max
Aver-
age
Specifica-
tion
6
51.5 45-57 .
216 250 max
319 370 max
425 470 max
82.5 (iiiiii
550 max
2.6 23
<-76 76 max
3.26
133.8
6,891 5,240 min
1.59 30 max
0.080 0.4 max
0.0016 0.005 max
11.3 25 max
1.3 5 max
28.7
63.4 54 min
1.3 7 max
0.6
Grade JP-3
Grade JP-4
Specifica-
tion
fc
Aver-
age
Specifica-
tion
4
Aver-
age
20 max
14 max
1.8 1.9 ' 18,715 0.168
2.5
18,678
0.1635
18,400 min
18,400 min
Accelerated ....................................
" Air-jet, 400F mg/100 mi.... Steam-jet, 450F, mg/100 m. leat of combustin, net Btu/lb.,
ydrogen-carbon ratio. ...... ................
Blade, O. C., Annual Surveya, U.S. Bur. Minea Rept. Invest. 5132, April, 1955.
* JP-3 and JP-4, MIL-F-5624, 1956; JP-5, MIL-F-79I4 (AER), Mar. 11, 1952. .
e
Only 2 fuels,
One fuel ia shown at left and the other at right.
d
British Miniatry of Supply. Kerosene used world wide in civil jet operations (1956). At 0F.
The Saybolt thermoviscosity is also used to indcate the behavior of the oil in a
lamp by means of the so-called Ring Number which is:
10 (46 minus API)
The viscosity usually ranges between 325 and 450. However, an oil may have a
proper viscosity and yet fail to bum satisfactorily. Kerosenes may have a gravity of
39 to 48 API and a flash point (Tag) of 120 to 180F. The initial boiling point is
usually under 370F, and the end point about 500F, although the government at
one time allowed an nd point of 620F. Although gravity is not important, many
refiners strve to produce a 41.5 to 43 API kerosene, and henee most of the
kerosene sold in the United States has this gravity. A small amount of light, material
(naphtha) is necessary in order to produce a high-quaiity bum- ing oil. For this
reason a little heavy gasoline must always be present in the kerosene, and henee
the boiling ranges of kerosene and gasoline (or naphtha) overlap to some ex ten t. If
the gasoline (or naphtha) and kerosene are too well fractionated, the flash point and
initial boiling point of the kerosene will be so high that it will not bum properly.
The color instability of some kerosenes has at times been a mysterious
difficulty. Several inhibitors and tests for color instability have been developed.
47
The properties of a few kerosenes and related producs- are given in Table 3-17.
Range oil has no cise specifications and is usually considered as an off-brand
kerosene that is too high in sulfur, has a bad odor, etc,
' Tractor fuel oil is discussed by A. T. Colwell,
48
but the motor fuel tax limitations,
the need for cheapness, and the wide variety of engines make clear-cut
specifications impossible. In general, the properties of fuels that have been
marketed are somewhat as follows:
Low to 115F
Flash point, min
176-422F 437-555F 480-600F 0.1-0.5
per cent temperature, min 95 per cent temperature, min End point temperature, max. Sulfur, per cent,
max
Distillate Fuels, Among these are stove gasoline (torches or lamps), tractor fuels,
domestic fuel oils (stove or furnace), industrial distilled fuels, spray oils,
insecticides, smudge oil, straw oil, absorption oil, and gas oil. Table 3-18 presents
the properties of these not closely specified oils. In northera New Jersey the
average quality of No. 2 heating oil has been
47
Hillman, McHatton, and Moerbeek, Proc. World Petroleum Gong., 2,704,708,713 and 721
(1933); and Rather and Beard, Ref. Nat. Gaso. Mfr., IB, 217 (1936).
48
Fuel Requirementa for Farm Tractors, Pe. Refiner, January, 1945, p, 124.
Dist. temp, F
Cor
ae of product Gravity,
API
Flash,
F
min
I.B.P.,
min
10%
recov
ered,
max
E.P.,
max
Sulfur %,
max
Smoke
point,
min
ro
sion,
cop-
per-
strip
S
ie:
-
al arctic export.
,1 or long-time
46-49 110-120 300-325 , 465-490 0.05-0.1
44-48 110-125 300-335 480-600 0.040.1 29-34
+2
rning oil
esto, 41-43,
w.w. estic, 44-46,
w.w.
ral, VV-K-21 la.
41-44 105-130 350-370 480-572 0.05-0.1 25-30
+ 1
44-46 110-130 350-370 470-572 0.03-0.1 26-32
115
572 0.13
7
mineral-seal... 36-39 250-260 480-540 600-700
+ 1
e oil ..................... 43 145
515
fuel, ASTM 215:
grade .................
347 465-
518**
1.0
1.0
Pasa
Pass
Pass
lar grade ..............
347-401 465-518
*
te, ASTM D396:
Grade No. 1....
35.2-48.5 114-185 317-396 350-420 487-586 0.018-0.5"
Grade No. 2.... 34.8-44.9 120-185 312-382 360-428 474-620 0.01-0.96*
Pass
fuel, RP-1 ........... 42-45 110 365-410 525 0.05 28 Pass
iperatures at 95 % recovered. sial aervices require 0.5 max.
as follows:
Year API Diesel
Index
Per cent
distilled at
440F
1938-1941 36.4 52.8 20.1
1942 35.9 52.0 15.9
1944 32.6 43.5 10.5
1945 32.9 44.5 13.0
Thermally and catalytically cracked distillates have not been entirely
satisfactory for the types of domestic burners now available, because of
carbonization. The kinds of domestic burners and the fuels rquired are:
Type of burner'
ASTM grade of
fuel required
Per cent of
salea (1947)
V&Dorizine tv>e ......................................
10.8
Natural d r a f t . _ * *...
Pot type, forced draft ........... .................
. .1 1 or 2
Vertical rotary, forced draft .................. . 1 or 2 11.0
Vertical rotary, atomizing ............................ 1 or 2
Atomizing-gun type:
Low pressure . ................... ...................
3 or 2 6.2
High pressure ............. ................ .. 2 or 3 71.7
The flash point of domestic fuels is limited because of safety, and an upper
liznit is imposed to ensure easy ignition in vaporizing-type burners. Carbn
residue on a 10 per cent ASTM residue indi cates something of the
tendency to produce coke in vaporizing-type burners, but the 90 per cent
distillation temperature is probably equally significante and a good correla-
tion is obtained only upon consideration of the carbon-hydrogen ratio,
49
Diesel Index, or aniline point. Viscosity naturally falls within propr limits,
but in general each atomizing-type burner exhibits a mximum capacity at
some intermedate viscosity.
110
Sulfur is normally of little significance; but,
for chieken brooder heaters, heat-treating, and glass or ceramics ware
furnaees, it may be specified. Color and odor are not vital, but purchasers
note them. The increasing use of cracked distillates or cycle stocks in
distillate fuels has helped the pur point but has intro- duced difficulties
with stability. Yariou additives are employed to
4
* Cauley and Delgass, Carbn Hydrogen Ratio of Catalytically Cracked Distillate Fuel
Oils, Oil Gas J., July 27, 1946, p. 166.
M
Glendenning and Sullivan, Characteristics of Fuel Oil, Nati. Pet. New, Aug. 21, 1936. d.
41.
Distillation, F
Flash
point,
Pour
point,
F
Su
API
Grade or ame
Max
10%
Max
E.P.
I.B.P.
90%
hter fluid" .... . ............
ive gasoline .................
TM No. 1, specifica-
64-70 6470
35 +
34.8- 44.9
26 +
25.8- 44.7 24.1-47.2
130
112
155 162
420 360-428
440
368-491
370-498
280
293
350
335
100 + 120-185
100 + 126-230 128-230
130 + 154-240 152-230 195 210
625 474-620
1956 range. ... . ...........
TM No. 2, specifica-
65 to zero 20
-60 to +20 -45 to 25
.20 -45 to 70 -30 to 25
312-382
440-554
675 451-630 457-650
0.01
L955 range ..................
1956 range ..................
TM No. 4, specifica-
300-460
312-457
487-708
491-714
0.03
0.05
.955 range ----- ....
.956 range .....................
a ol (gas enrichment) s oil (industrial uei) sorption o
12.8-35.9 8.7-36.3 33 30 45
37
351-504 375-528 302 440 344
482
630-748
635-730
447-544 438-620 460 475 386
518
686-842 655-840 700 + 800 + 505
630
0.1
0.23-
35
sorption oil.
ipper dish gum 2 max and Red vapor pressure 7 max.
jntistokes at 77F.
the 10% residue of an ASTM distillation. inematic t 100F.
Pour
point,
F,
max
Flash
point,
F
min
API
grav
ity
3
3
1.6
1.5
34
33
33
32
32 1.4 i
35
38
35
35
37
32
30
76
81
46
45-
37
33
170 170 140 110 190-200
159
32-41
40
40.3
41.3 40.5
122'
100
171
185
138*
143*
154'
125
150
199
160*
156'
130
36.5
34.8
36.8
35.9
33.5
32.6
25.3
27.3 22.5
), high quality .................
}, mdium quality ----
l, all-purpose, Army.. I, arctic grade, Army.
r. mise, samples .............
'M Grade 1-D:
)50, avg ..........................
)52, avg Eastern U.S. >54, avg Eastern.U.S. >56, avg Eastern U.S. >55, ASTM, D975.... M Grad 2-
D:
>50, avg zero pour ... 150, avg higher pour.. >56, avg Eastern U.S. >56, avg Central U.S.. >56, avg
Western U.S. )55, ASTM, D975..
ine (typical) .................. .
M Grade 4-D:
)50, avg ..........................
55, avg Eastern U.S. 156, avg Eastern U.S. )55, ASTM, D975....
Description of fuel
0 0 -10 -50 Oto -35
60* 20
15
15
25
20
0
10 20* 20
Distillation range, F
I.B.P. 10% 90% E.P.
440
470
645
700
650
600
500-680
532
523 518
524
700
650
560-724
575
566
563
567
625
652
677
645
645
668
400-416
369
366
358
364
453-476
417
409
401
408
380
396
369
375
387
441
471
431
438
455
593
621
587
590
606
675
417
398
451
510
500
511
695
728
720
759
773
780
Visee
a
10C
On a 10 % ASTM distillation residue.
Diesel Index.
Centistokes.
War shortages forced reduction to 40 during 1944.
Minimum, not ayerage.
On entire material.
alleviate the clogging of screens, the formation of sediment or gum-like
materiais, deterioration in color, and corrosiveness.
25
Most middle-boiling-range material (400-900F) is cracked into gaso-
line, but in meeting the specifications of such materiais as kerosene, No. 1
Distillate, diesel fuel, and jet fuel, it is necessary to use mainly straight-run
material.
Diesel Fuels. The major performance characteristics of diesel fuels,
somewhat in the order of importance, are
1. Cleanlinesscarbn residue, B.S.W., sulfur, etc.
2. Ignition qualitycetane number or Diesel Index.
3. Fluidity and atomizationviscosity, pour point, etc.
4. Volatilityflash point, distillation, and carbn residue.
Even the small amount of dirt carfied in dusty air can pollute diesel fuel,
because the plunger of the injection pump is lapped to a toleran ce of
0. 00001 in. Excessively large amounts of sulfur are thought to
contribute to engine wear, and sulfur obviously can cause muffler and
exhaust-pipe corrosion. Good ignition quality, as measured by cetane
number or Diesel Index, assists in easy starting, starting at low
temperatures, low engine pressures, and smooth operation; whereas a fuel
with poor ignition quality promotes misfiring, varnish on pistons, engine dirt
or deposits, and rough operation. Fuel economy is slightly better for
mdium- or low- cetane-number fuels, but engine load is much more
important. High- viscosity, high-boiling-range fuels cause engine deposits,
smoke, and odor; but too low a viscosity may lead to a slightly lower
efficiency because of poor lubrication of the injectors, leakage, or the low
heating valu of such a fuel.
The approximate relationship among ignition quality properties is
indicated in Table 3-20. The most important of these is Diesel Index,
which is defined as the API gravity times the aniline point (in degrees
Fahrenheit) divided by 100. Ignition aecelerators, such as alkyl nitrates
(especially amyl nitrate) or nitrites, aldehydes, ketones, esters, ethers, and
peroxides, have been investigated.
10
A major difficulty has been the
incompatibility often encountered when two fuels are mixed. They tend to
produce sediment during storage. Anti-screen-clogging additives and
inhibitors of gum formation now permit refiners to blend straight-run and
catalytic cyele stocks
25
into diesel fuels.
Ease of starting, according to Shoemaker and Gadebusch,
11
depends
mainly upon ignition quality but also upon viscosity and pour point.
10
Bogan and Wilson, Ignition Aecelerators for Compression-ignition Engine Fuels, Pet.
Refiner, July, 1944.
' " Effect of Fuel Properties on Diesel Engine Performance, Oil Gas ./., Jan. 12, 1946, p. 74.
58 PETROLEUM REF1NERY ENGINEERING
*
Fuels more viscous than 550 sec Saybolt Universal at the starting temper-
ature cannot be handled by some fuel-ignition pumpa. Plugging of screens
or clth filters tends to occur at the eloud or haze pint, which is usually
about 10F above the pour point. Finally, the cetane number
TABLE 3-20. GOMPAHISON OF IGNITION QUALITT ANO OTHEK PROPERTIES (APPROXIMATE)
Cetane
number
Diesel
Index.
Blending
octane number
(Motor
method)
Character-
izaton
Factor
Boiling-
point
gravity
number*
30 26 51 11.05 201
35 34 43 11.25 196
40 42 35 11.45 191
45 49 27 11.6 187
50 56 19 11.8 . 183
55 64 11 12.0 180
60 72 2 12.2 178
* G B + (68 0.703#) log T, in which O API gravity, T C, and B = the constan t.
TABLE 3-21. PROPERTIES OF DIESEL FUELS FOR EAST STARTING
Air tem-
perature, F
Mximum
viscosity
Saybolt
Universal at
OO'F
Mximum pour
point,
, 0F
Cetane
number,
min
-20 42 30 90
-10 46 -20 83
0 50 -10 76
10 57 0 69
20 65 10 63
30 . 70 20 56
40 98 30 49
50
-
40 43
. 60 160 50 36
must be high enough to permit ignition when the air that is compressed is
coid. The properties required are somewhat as shown in Table 3-21.
Obviously viscosity gives little trouble. .
Lubricating OUsGeneral. There are so many uses for mineral oils that
a formidable array of ames, based on uses, has arisen. Several grades of
viscosity are useful for each general type of oil, but a relatively few types
of oils will satisfy most of the needs of industry, Table 3-22
Viacosity at
API
130*F
210F
10Q*F
90-185
185-293
40-65
62-80
80-155
80-85
100-145
75-90
200
70-100
50-100
40-100
90-100
60-100
40-70
40-70
24-30
22-28
20- 27
24- 28 23-25 23-25
22- 25
21- 23 20-22
25- 27 21-23 27-32 25-23
25-28
20-28
25-28
20-26
23- 28 23-28. 29-31
27- 30
28- 28
28- 30
20-25
20-27
29- 32
400-850
120-185
800-1,600
100-125
700-800'
140-170
300-325
135-185
175- 220 95-110
176- 220 85-75 65-80
120-175
175-340
475^525
55-65
400-500
200-300
65-140
ht ............ . .......................
tdium......... .......................
avy .... . ............................
agine, light. ...... ..............
agine, heavy ...................
;ine, Ughtest ...................
ine, heavieat ..................
lion oil. Ughtest ..............
ion oil, heavieat. d machine, apindle. d machine, heavieat
light .................................
heavy..............................
tLLs, unfiltered:
iueral ...............................
mineral ............................
ttnpoiinded ......................
ompouoded ...................
gine, mineral ...................
gine, compound....
. light ..............................
il, mdium.........
1, heavieat .....................
ier oil ...............................
avunmer .........................
winter ..............................
ame of oil
Engine or compresa or cyliaders
Marine enginea
Marine enginea
Steam turbines, dyna- moa, high a peed, etc.
Elctrica! transformen
Rough slow-speed bear- ings, crushera, etc.
Food manufacturing, textiles, paper, etc.
Automotive eng be Automotive engine Automotive engine Airplanea Airplanea Dieseis Dieseis Automobiles Automobilea Textiles, etc. Heavy
machinery Refrigeration, etc. Refrigeraion, etc.
Used for
vu-
cosity
Index
Flash
(open
cup)
Pour point Ci
re
360-400 -10 to 15 .(
400-450 Oto 25 0
440-510 Oto 25 0
400-425 10 to 0 0
476-500 0 to 30 1
330-350 10 to 10 0
390-410 Oto 20 0
300-420 -10 to 10
500+ Oto 30
320-350 Oto 30
376-400 Oto 30
310-360 20 mu
340-400 10 max
490-540 20 to 80 2
520-600 30 to 60 3
450-510 10 to 40 1
620-600 30 to 60 3
360-410 35 max
350-410 35 max
310-360 0 to 35 0.(
320-410 Oto 35 G.
350-450 35 max 0
275-325 60 to 30
Oto 30
20 to 0
*
260-380
' *
shows the properties of some of the major types of oils, and the approxi-
mate amounts sold during 1950 are shown in Table 3-23.
In general, oils may be grouped as follows:
1. Engine and Machine Oils. High viscosity Index oils are required for
aircraft engines and automotive engines operating in temperature and arctic
climates and for machinery or instruments tht are subject to wide
variations in temperature. Viscosity and Viscosity Index (see Fig. 4-2) are
important considerations.
TABLE 3-23
Type of oil Ttjousand bbl Percentage
Motor oil:
Straight............................................................
7,000 18.0
Premium .................................................. . 4,800
7,650
12.3
Heavy duty (2-104 B) .................................... 19.6
MIL -2104 .................................. . ................. 2,550 6.5
Total ........... ......... . ........................... 22,000 56.4
Industrial:
Straight...................................... .....................
9,700
2.250
2.250 150
24.8
Rust and oxidation inhibited. ........... .............. 5.8
Premium ...................................... . ........... . 5.8
Heavy duty ..................................................... 0.4
Railroad diesel ....... ...................................... . 450. 1.2
Total ..................................................... . 14,800 38.0
Gear oil and grease ...................... ................. 2,200 5.6
Total domestic ........................... ........... 39,000
14,200
100.0
Total export ............... ...........................
Mdium Viscosity Index oils are suitable for almost all industrial
machinery including stationary spark-ignition engines and automobiles in
temperate or warm climates.
Low Viscosity Index oils are suitable for most industrial lubrication and
for diesel engines. Except for poor starting characteristics, these oils are
thought to be best for general automotive service (except arctic) because of
their natural detergent properties. Others feel that a chemical deter- gent
should be added to the higher-viscosity-index oils to gain detergency
properties.
Obviously the entire range of viscosity of 60 sec at 100F to 250 vis-
cosity at 210F must be available to pro vid e service for the lightest
spindles (of zero clearance) and the heaviest machinery operating at high
temperatures. In general, the useful life of an oil is halved by each 15F
increase in operating temperature (above 140F). In conneetion with
gravity-eed systems, etc., it is usefi to recognize that the viscosity is
about halved by each 20F increase in temperature.
2. Compounded Oils. The addition of fatty oils such as lard, tallow,
rapeseed, castor, and sperm causes the oil to spread over and more thor-
oughly wt a metal surface, and they tend to permit the formation of
emulsions with water that will stick to the metal surface. Thus com-
pounding is practiced for steam engine, air compressor, quenching, cut-
ting, marine engine, and tempering oils. Fatty oils also mildly increase the
film strength. Tests for emulsibility, neutralization number, and percentage
of fatty oil are useful.
3. Turbine Oils. High-speed machinery, such as steam turbines and
dynamos, may cause emulsions with water; and henee the ASTM steam
emulsin number (DI57) and demulsibility test of the Federal government
(Method 320.13) are useful. Extreme stability, attained mainly by long
filtration through fulleras earth, is necessary because these oils may be
used for several years.
4. Coid Test Oils. Pour point, viscosity, and sometimes Viscosity Index
are important for oils used for refrigeration equipment, hydraulic
mechanisms, machine guns, instruments, or any machinery in arctic
climates.
5. Transformer Oils. These and insulating oils must withstand large
electrical voltages, and henee the dielectric strength (usually 1-in. disks,
1-in, gap, 25,000 volts minimum) is important. The steam emulsin number
is usually specified in order to assure stability during several years of
service. ' ; ; , , ;
6. Color Oils. Such services as food, paper or textile manufacture, and
medicinal uses require a white or very light-colored oil. Lubrieant quality is
destroyed to a large extent by decolorization. The cheap black oils might
also be included here, because color is of no significan ce.
7. Corrosive Oils. Several services depend in part on the corrosiveness of
an oil at least in certain temperature ranges. Such oils as extreme-
pressure lubricants for hypoid or heavy-duty gears, and cutting oils require
the addition of sulfur, chlorine, or compounds of these. Suitable corrosion
tests and special performance tests are required for each service.
Sin ce nearly all industrial services can be met by the above se ven gen-
eral types of oils, it is doubtful if an attempt should be made to classify the
many specialties used as putty, leather, quenching, penetrating, pre-
servative, wire rope, chain, harness, floor, furniture polish, shoe polish, wax
mixtures, denaturing, wool, shock absorber, hydraulic, brake band, etc., oils.
The SAE viscosity classification of oils shown in Table 3-24 is most
widely used. The 10W and 20W grades are for winter service. Perhaps
SAE
V0GOO-
ity
number
Saybolt UmTersil, seo Redwood Engler Centietotea
OF 210"F OF 210*F 0*F 210*F 0*F 210F
5W
10W
20W
30
30
40
SO
Below 4, 000
5,000-12,000
12,000-
48,000
Below 3,500
5,350-10,500
10,500-
42,000
Below 115
172-344
344-1,378
Below 809
1,303-2,000
2,606-
10,423
5.73-9.62
9.62-12.94
12.84-16.77
16.77-22.68
40 min
45 ni
45-68
58 70
70-85
85-110
40.9-51.8
51.0-61.9
,61.9-75.2
75.2-97.5
1.401.S
1.8-2.12
2.12-2.52
2.52-3.19
a better (but more complicated) classification system is that of the Bureau
of Ships.
53
It consista of a seres of nurabers of four digits each, and a
detailed tabulation of the properties of the oils that have tKus far been
assigned numbers. The tabulation
63
of properties is too extensive for
publicatin here. The first digit designates the general kind of oil, and the
last three digits are used to show the numerical valu of the viscosity. The
kinds or types of oils adopted by the Navy are
Viscosity
Class measured at
lxxx Forced feed, high Viscosity Index {95-100) ............................ 210F
2xxx Forced feed, low Viscosity Index ............... ............................. 130F
3xxx Forced feed, mdium Viscosity Index (65-75) ......................... 21GF
4xxx Compounded marine engine .......................................... . 210F
5xxx Mineral cylinder .................. ......................... . ....................... 210F
6xxx Compounded steam cylinder (tallow) .............................. . 210F
7xxx Compounded steam cylinder (lard or tallow),. ............ ............ 210F
8xxx Compounded air cylinder ................................... . ..................... 130F
9xxx Diesel engine (heavy duty) ........................................................ 130F
As examples, 1042 is SAE 10W oil, and 3050 (or 9170) is SAE 20 oil.
Motor Oils. Spark-ignition and diesel-engine oils differ primarily because
the diesel oils must exhibt detergeney properties to keep carbn from
aceumulating in the engine after a few hours of operation. Naphthene-base
oils (low Viscosity Index) are somewhat satisfactory as diesel oils, but most
heavy-duty oils are made by introducing a detergeney additive to an oil
manufactured from paraffin or mixed-base crude oils.
Much importance has been attached to Viscosity Index
64
because it
measures the suitability of an oil to lubrcate properly at the elevated
w
N.B.S. 431, Lubricating Oil, Bureau of Ships, Navy Department, Washington, D.C.,
1942. .
*
4
See Figs. 4-1 and 4-2 for viscosity-temperature relationshipa.
temperatures of the engine and at the same time not to be too viscous for
operation during starting.
Easy starting is said to occur if the viscosity does not exceed 40,000 sec
Saybolt Universal at the starting temperature,
65
and, of course, the pour
point must be adequately low. Thus viscosity, Viscosity Index, and pour
point together govern ease of starting. The lowest temperatures at which
easy starting (quick-cranking) can occur are somewhat as follows:
Kind of oil Lowest easy starting temperature, F
40
Viscosity Index
60
Viscosity Index
100 Viscosity
Index
40 viscosity at 210F .................... -23 -25 -34
SAE 10W ........................................ -18 to -27 -19 to -29 -20 to -30
SAE 20W ........................................ 0 to -18 Oto -19 0 to -20
SAE 20 (thinnest) .......................... -2 -6 -12
SAE 30 (thinnest) .......................... 13 9 0
Obviously 10W and 20W oils of any base are satisfactory for normal winter
service. Zero Viscosity Index oils are not shown in the tabulation, because
such oils are not marketed. So called multigrade oils are being marketed
which meet the requirements of several or all SAE grades.
Viscosity in itself appears to be of little direct significance, and such
might be expected because the pistn rings scarcely push against the cylin-
der wall. The oil must be fluid enough during starting to flow through the
lubricatin system, but it may be quite thin (even diluted with kerosene) at
the engine temperature without causing excessive wear. Thinner and
thinner oils are being employed. ^Although thin oils may contribute to oil
consumption, less gasoline is used and the over-all cost of operation may
be less
56
or scarcely different. The factors tfrat
;
affect oil consumption are
(1) low-boiling or low-flash oils, (2) low-viscosity oils that allow blow-by,
(3) excessively high engine temperatures, (4) high engine speed or load, (5)
leaks at gaskets or rotating seis, (6) carbu- retor out of adjustment so that
crankcase dilution occurs, and (7) a worn engine.
67
Of these, a worn engine,
a poor carburetor adjustment,. or a high speed accounts for most cases of
excessive oil consumption.
Flash or fire point indicates little of engine performance, but it indi- cates
the source of the oil and whether it is a blend of low- and high-boiling
Otto, Miller, Blackwood, and Davis, Improved Motor Oils, Ref. Nat. Gaso. Mfr.,
November, 1934, p. 411.
* Nelson, W. L., Significance of Viscosity . . . , Oil Gas J., Nov. 23, 1939, p. 46.
ST
Nelson, W. L., Consumption of Engine Oil, Oil Gas J., Feb. 17, 1944. D. 73.,
oils. Sulfur has little direet effect, but Merrill, Moore, and Bray
68
find
inconclusive evidence that high-sulfur oils cause engine corrosionthat
the wear may have been caused by the different types of hydrocarbons in
the oils rather than by sulfur.
Carbn residue is not directly related to carbn formation in the engine.
The extremely high-carbon-residue Pennsylvania oils produce only a little
more carbn in the engine than do the low-carbon-residue naphthene-base
oils, but the paraffin-base carbn is much harder and is attached more
firmly to the cylinder parts.
69
Short-time engine tests such as the Lauson, Underwood, and Chevrolet
36-hr tests
60
and the Work Factor test of the Bureau of Ships
53
are neces-
sary in making real evaluations of oils. However, even such elabrate test
methods sometimes produce confusing results and they indcate clearly that
the results are a function of the way the engine is operated as well as of
the properties of the fuels or lubricants being tested.
Additives are now widely used to alter the properties of lubricating oils.
Pour-point depressants act differently on each oil, but on the average
cause reductions in pour point
1
about as follows:
Per cent
Average
lowering,
F
Range of
lowering,
0.1 11 1-21
0.3 22 5-39
0.5 30 17-44
1.0 38 24-53
Wax-naphthalene or w^-phenol condensation products and their poly-
mers are said to be effective as pour-point reducers.
26
Viscosity Index may
be improved by the addition of butene polymers or polymers of methacrylic
acid esters. Detergency additives are usually complex calcium or barium
sulfonates or phenates. Such additives tend to keep carbonaceous
sludgelike materiais from settling out of the oil and will even clean such
materiais from a dirty engine. When a detergency additive is used, the
crankcase oil almost immediately appears dark and dirty because the
sludge is carried in suspensin. When such an oil is first used in a dirty
engine, it loosens so much material that the oil should be changed at least
two extra times at 300- and 500-mile intervals to remove the debris.
1
Detergeney oils are necessary for diesel eigines, although straight
naphthene-base oils are reasonably good, and such oils are advisable for
heavy-duty spark-ignition engines. The engine temperatures in spark-
ignition and diesel engines are somewhat as follows:
Location Spark-ignition Diesel
Fiston head, F................................... 500-650 650-750
TOD rie. F ........ .......................... 475-500
Lower ring belt, F .................. . 200-325 350
Cylinder wall, F , i . . . . 300-350 350
pl, F_ .................................. . 160-250 170-250
These high temperatures tend to cause rapid oxidation of the oil on the
pistn head and top ring, with the formation of solid asphaltic material from
paraffin-base oils but only sludge
62
in the naphthene- or detergency- type
oils. Thus, when paraffinic oils are employed, varnishlike deposits tend to
cook down on the lower walls of spark-ignition pistons, and coke
deposits are formed around the top ring of diesel-engine pistons. Detergen
cy oils do not assist greatly in removing the varnishlike deposits of spark-
ignition engines, but they do suppress to a large extent the coking of diesel
engines by keeping_lhe carbonaceous material in suspensin.
TABLE 3-2'5. ESTMATE ANNUAL CONSUMPTION OF ADDITIVES FOR (MAINLT) AUTOMOTIVE LBRICANTS, 1955
Kind.
Dosage, per cent Millions of
pounds
Millions of
dolars
Detergents ............... ..................................
2-10 280-300 57
Antioxidantscorrosion inhibitors....
0.4-2 70-75 15
Viscosity Index improvers .........................
0.5-10 60-65* 15
Pour point depressants ..............................
0.1-1 5 2
Extreme pressure agents ..........................
5-10 60* 14
Defoamants ................................................
0.0002-0.07
Antirust agents ...........................................
0.1-1
Odor control ............................................... 0.001-0.005
6
Oiliness imparters ........................ . . ....... . 0.1
3
Larson, C. M-, Additives for Fuels and Lubricant3, Pe. Engr., March, 1955, p. C-44.
6
Used also as pour depressant.
* 60% automotive and 40% industrial usage,
* Faust, J., Aapbaltization Tests for Lubrieating Oil, Oil GasJan. 20,1944, p, 29,
Antioxidanl additives to alleviate oxidation, sludging, or eorrosion are
extensively used. An enormous number of agents have been recom-
mended or used; and a few are calcium petroleum sulfonates, sulfurized
terpenes or olefins, metal salts of phenol sulfides, phosphorus pentoxide-
treated terpenes, and zinc methylcyclohexylthiophosphate. Antifoam- ing
agents such as silieone compounds when used in minute amounts
effectively reduce the tendency to foam.
Lubrican ts. This term is applied primarily to greases, semisolid com-
positons, and gear oils, even though some of the materials are as much Iike
liquid oils as like solids. Most generally, greases may be grouped into three
classes.
6
*
0. Admixtures of mineral oil and solid lubricant. ' Some of the common solid
lubrican ts are graphite, mica, tale, sulfur, and asbestos fibr. These
greases are invaluable in the lubrication of ill-fitting machine parts func-
tioning under heavy or intermitent loads. Examples of this type are
tractor-roller lbricants, lubricants for concrete mixers, ditch-digging
equipment, and railroad-car unloading devices. .
1. Blends of residuum, waxes, uncombined fats, rosin oils, and pilches, This
group is particularly suited to the lubrication of rock bits, steel cables,
water pumps, dredges and chains, and gears operating under water or
under exposed weather conditions.
2. Soap-thickened mineral oils. Common thickeners are sodium, calcium,
aluminum, lithium, and lead soaps. The soaps of these metis are prepared
by saponification of a fatty glyceride of either animal or vegetable origin,
This group is widely useful because a large variety of difierent-consistency
greases can be produced by selecting various metallic soaps, fatty
glycerides, and mineral oils.
There are also three general bases
64
used for manufacturing the
extreme- pressure lubricants now used almost exclusively for differential,
transmi ssion, and general gear lubrication.
1. Blends of saponiable oil containing chemically combined sulfur with
a suitable lubricating oilor mineral oils to which flowers of sulfur has
been added,
2. Blends of a sulfur chloride-treated saponifiable oil base and a lubri-
cating oil of suitable viscosityor chlorine combined directly with chosen
mineral-oil fractions.
3. Lubricants containing lead soaps of fatty or naphthenic acids and
sulfur. These may contain sulfur that has been added or only the sulfur that
is naturally presnt in the mineral oil. However, the most common
M
Simpson and Welch,- Manufacture of Grease, Ref. Nat. Gaso. Mfr., March, 1931, p. 77.
64
Ebaugh, I. A., Service Tests Must Determine Valu of Extreme Pressure Lubricants,
Prt 2, Nati. Pe. News, Jan. 15, 1936, p. 26.
practice in manufacturing gear lubes is to add a specific sulfur compound
such as dibenzyl disulfide, which is noncorrosive at room tempera- ture but
corrosive (to copper) at about 300F.
The general theory regarding sulfur and chloride lubricants is that iron
sulfide or iron chloride should be formed on the surfaces of the bearing or
shaft and that the films of these materiais are responsible in part for good
lubrication. Thus the extreme-pressure lubricants are somewhat corrosive
and probably should not be used on bearings that contain copper. Others
believe
65
that the high temperature generated at the gear-tooth surface
causes the rough or high points on the surface to be destroyed by
corrosion so that the surface is smoothed. In addition to customary tests,
gear oils for automotive transmissions are subjected to full-scale
u
shock
tests. In these an automobile is operated at a high speed; the clutch and
transmission are disengaged; and then, while the vehicle is still traveling
rapidly, the clutch is engaged. Gear lubricants, trans- mission oils, and
many rear-axle or steering-knuckle applcations
66
are furnished in the
following grades (with or without extreme-pressure additives), which are
generally similar to the SAE grades:
Grade Use Saybolt Univ. viscosity
75 Extreme low temperature 15,000 max at 0F
80 Winter Service 15,000-100,000 at 0F
90
75-120 at 210 F
140
120-200 at 210 F
250 Highest temperature service 200 min at 210F
* ASTM, Report of Committee D-2.
Most greases are soap-thickened mineral oils. The National Lubricating
Grease Institute Classification (1955) based on worked consistency is:
NLGI
number
Consistency
(D217)*
Description and use at
room tem per atine
0 355-385 Semifluid
1 310-340 Very soft, grease gun
2 265-295 Soft, grease gun
3 220-250 Grease cup
4 175-205 Grease cup
5 130-160 Grease cup and block
6 85-115 Block type
Nelson, W. L., Corrosion Tests of Gear Lubes, Oil Gas J.
t
Apr. 7, 1945, p. 97.
** Thompson, J. W., Varied E. P. Lube Specifications , . . , Nati. Pet. News, Sept. 30, 1936, p.
36.
Soap bus Calcium (general)
Calcimn resnate (ocld-
flat)
Sodium (general) Sodium, brick type Alumii
facture Buttery Buttery Fibrous or amootb Eard or brittle
Buttery, ru
strrngy bu
broas
hoppiag point, *F 220-226 276 300-460 300-460 200
(approx.)
Doadition after Kav- Separa tea Foams at 2Q0'F. Sep No chango if worlced No chance Changa ter
ing heated to melt*
rate upon pro-
cooiing bu
ing point
longed heating
separata e
melting po
Ja-rimiim tempera- 176 200 300-400 300-480 160 or per ha
ture, *F (caatinuoue
i enrice)
loftening upon work- Fair to poor Fair to poor VarieeexceOent to Variair to poor
/
Fair to poor
ing
poor
SSect of water ReshUnt Resistan t Susceptible Susceptible Reaistant
\imary u General-purpoas lubri- Eough heavy bearings Ball and rotler bear- Locomotive driving Application
cant for plaio bear- at alow peed, also ings up to mdium journalB and llmar adhesivent
inp and line ehaft- skida, track curvea, epeedi and light to service sistance to
ing. Pressure gun and
water pumpa
and wagn wheeli. Oil Md
and agricultura l
machinery
heavy loada, also wbeel
bearings and
fhMfttfl
gal forc
lotea Borne moisture lelt Cheapaeea is major NonnaUy does not Dficulty is suscep- Does not c
in grease. Certain factor chance!. Highest tibility to water. crustreadi
greaaea stabilixed
temperature service Smooth greases used alow flow
with chemicals in-
except strootium for antifriction bear- Relatively
stead o water can be
greaeeB iaga. Long-fiber
uoed at bigher tem
greases for chassig
peratura
.
lubrica tion
* Taken mainly from Greaaea Part II, "Lubrieilion," The Texas Co August, 1945.
An enormous number of combinations of oils and soaps is possible. Oil
content ranges from 42 (waterproof grease) to 93 per cent, oil viscosity
ranges from 90 at 100F (waterproof greases) to 220 at 210F, and
numerous metis and fats are employed. Thin oils are used in greases for
high-speed bearings,
Although soaps of barium, cerium, chromium, cobalt, i ron, lead, mag-
nesium, mercury, nickel, manganese, silver, strontium, tin, and zinc
67
have
been proposed for grease manufacture, the main greases and their
characteristics are as shown in Table 3-26.
68
Such metallic soaps as
calcium, aluminum, barium, and strontium produce greases resistant to
water; such soaps as those of barium, strontium, and lead are useful for
extremely heavy duty services; and the sodium and calcium (particularly
resnate) greases are relatively cheap. The National Lubricating Grease
Institute has been active in developing test methods, particularly the
Norman-Hoffman oxidation test,
69
and performance characteristics in
antifriction bearings at elevated temperatures.
69
Waxes* Paraffin and microcrystalline (petrolatura) waxes are used for so
many widely different services that not many specifications other than
melting point have been adopted. Microcrystalline waxes may contain
natural or additive substances that partly inhibit crystalline growth. This
generally tends to increase the flexibility or plasticity
70
of the wax, and in
fact paraffin wax can be added to some microcrystalline waxes without
destroying the flexibility. A common additive material to produce plasticity
is Vistanex or poly bu tenes. Paraffin waxes range in melting point from
about 105 to 155F, and the most common grades range in melting point
from 118 to 132F. . Petrolatum waxes from long- residuum stocks may
have a melting point as low as 106F. Regular petrolatum produces
microcrystalline waxes melting up to about 180F, whereas the highest
melting point microcrystalline waxes (195F) are produced from tank
bottoms. Some of the petrolatum or microcrystalline waxes on the market
are shown in Table 3-27. Color ranges from black to white in almost all
grades; and, of course, odor and somet mes taste are important properties.
Waxes are applied in two general ways, as a molten liquid or in the form
of a dispersin or emulsin in water stabilized with dispersing agents. John
C. Dean
71
discusses the many uses of waxes. Among these uses are
*
7
Boner, C. J., Metallic Soaps for Thickening Mineral Oila, Ind. Eng. Chem., 29, 58 (1937).
.
Taken mainly from Greases Part II, Lubrication, The Texas Co., August, 1945.
** Tech, Bvtt. 5 and 6, NLGI 164 Chandler St., Buffalo, N.Y.
70
Nelson and Stewart, Efect of Oil on Plstic Properties . , . , Ind. Eng. Chem. 41, 2231
(1949).
T1
Petroleum Waxes, Pet. Refiner, May, 1946, p. 87; and Processing Materials from
TABLE 3-27. MICROCRYSTALLINE AND PETROLATUM WAXES
Wax
Melting point,
F (DI 27)
Con-
sistency
(D217)
Needle
penetration
(D5)
Flash
point,
F
Gravity,
API
Petrolatum ...............
Petrolatum ...............
Petrolatum ...............
Microcrystalline...
Microcrystalline...
Microcrystalline...
Microcrystalline...
Microcrystalline...
106-118
112-124
127-137
155+
166+
170-175
185-190
190-197
200-240
160-200
170-200
25-35
15-25
10-20
5-15
2-10
360-370
410-430
360-370
460+
460+
460-500
470-500
480-500
36
36
37
21-22
* Variea widely. Gravity is a function of the properties of the parent crude oil.
adhesives; ammunition; bandages; burns; belting; candles; carbn paper;
cheese wrappers; coatings for drums or cans; cobblers wax; concrete mix-
tures; dental cavities; electrical condensers, cables, coils, transformers,
batteries, etc.; electrotyping; emulsions; food sealing; floor polishes; fuel
briquettes; foil coatings; illuminants; ink; insulations; glossing agent in
laundries; lipstick; lubricants; embalming prepara tions; matches; impreg-
nating cloth and paper; milk and liquid containers; modeling waxes; mois-
tureproofing paper coatings, candy wraps, laminated paper, bags, etc.;
paperboard for boxes, cartons, can substitutes, drinking cups, frozen-food
packages, milk cartons, etc.; pastes; pencils; pipelines for acid; plasticiz-
ers; polishes for shoes, leather, or furniture; pyrotechnics; plstic molding;
ropes; roofing; rubber blooming; rust preventatives; salves or ointments;
ski wax; stencils; stonework; surgery cavities or deformities; textiles for
bath curtains, canvas, tarps, felt hats, lubricated threads, shoelaces, yarn
finishes, waterproofing, etc.; toilet creams, pastes, etc.; washers; wire
coatings; and wood fillers.
Residues. The residual petroleum producs usually do not command a
high market price. Often they are merely by-products of the regular
refining operation. Some of the residual producs are residual fuel oil, fuel
oil for diesel power engines, road oil, spray oil, coke, and paving, roofing, or
paint asphalts.
Typical residual fuel oils and dusting oils exhibit the properties shown in
Table 3-28. Oils 1 and 4 are the 1955 standard (ASTM D396),
1
the older
oils (2 and 3 of 1933) are still representative,
72
and the average coal-spray
oils were taken from Technical Report 6 of Bituminous Coal Research,
Inc.
73
w
Nelson, W. L., Bunker Fuel Oil Specifications (1918-1946), Oil Gas July 27, 1946, p.
196.
TABLE 3-28. FUEL AKD DUSTING OILS
Oil
Flash
point,
F,
min
Water
and
sedi-
menfc,
max %
Pour
point,
F,
max
Mximum viscosity, sec
1. ASTM No. 5 .................... 130 1
40 Furol at 122F
130-306 0-0.8 -20 to +60 11-40 Furol at 122F
1956 range .................... 136-300 0-0.8 -30 to +50 11-40 Furol at 122F
2. Low viscosity, 1933... 150 1
-
100 Universal at 100F
3. Bunker B, 1933 ............... 150 1
100 Furol at 122F
4. ASTM No. 6 ............ 150 2
300 Furol at 122F
1955 range ............. 1. 150-430 0-1.8 5 to 80 51-295 Furol at 122F
1956 range .................... 140-420 0-1.6 0 to +60 28-292 Furol at 122F
5. Light dusting oil .............. 305-350
0 to -50
111-223 Universal at
100F
6. Heavy dusting oil ............ 300-365
5 to 20
246-599 Universal at
100F
a
U.S. Bur. Mines Inform. Circ. 7730, October, 1955.
All the oils should be free from rust, grit, acid, or fibrous material that
might clog or injure burner tips, and free from chemical agents (neutralizers
for corrosion) that will flux with the fireclay walls of furnace settings.
The very small amounts of vanadium and sodium found in- some oils
may lead to extreme corrosion when such fuels are burned in boilers or are
used as gas turbine fuels. This difficulty can be almost totally climinated by
the use of magnesium, calcium, zinc, etc., additives. The following
requirements (1953) of the General Electric Co.
74
for residual gas turbine
fuels illustrate how the additives are applied.
1. The amount of sodium should be under 10 ppm (preferably under 5 ppm). It can be
reduced by customary desalting operations, washings, centrifuging, etc.
2. The weight ratio of sodium to vanadium should be under 0.3. This may necessi- tate
more reduction of sodium, but f the vanadium is under 5 ppm, the Na/Va ratio
requirement may be ignored. i
3. The weight ratio of magnesium (additive) to vanadium should be adjusted to higher than
3.0. If the vanadium content ia lower than 2 ppm, magnesium is not needed.
4. Calcium should be under 10 ppm.
5. After the above adjustments, the total ash should not exceed 2,000 ppm.
Similar additive formulas are being developed for distillate or jet fuels.
Gravity is of little significance except that low-API-gravity fuels have
sliehtlv hicher heatinc vales. At eravities below 10 API. water and
sediment do not settle out of the oil and such oils cannot be displaced from
tanks by water. The heating valu of residual fuel ranges from about
6,260,000 to 6,450,000 Btu per bbl. Its main competitor is bituminous coal
(13,100 Btu per Ib). The parity priee O (dollars per bbl) of Bunker C fuel oil
may be computed from the cost of delivered coal C ($ per ton) by the
following formula
12
in which E
0
and E
e
are the thermal efficiencies at which
oil and coal can be fired, H
Q
and i/
c
are the heating vales of oil (Btu per
bbl) and coal (Btu per ton), and x is the ratio of operating costs for the year
under consideration to the cost during 1951.
(3-5a)
_ (E
a
/E
c
)C 0.165* H
c
/H
0
+
HJHo
or for average vales of the constants:
(3 ~bb)
Oil can be fired more cheaply than coal (about 16.5 cents per ton during
1951). Sulfur in fuels (oil, coal, or gas) requires higher cold-end tempera-
tures in the air preheaters or economizers of boilers
7
in order to prevent
corrosion and fouling of the tubes. A 6 per cent sulfur fuel requires a
temperature about 60F higher than a 2 per cent fuel.
A high pour or solid point is important in gravity-feed systems because
TABLE 3-29. Fuel-oil TEMPERATURE FOR BURNERS
71
Nelson, W. L., Oil Oa$ Sept. 13, 1954, p, 138.
Firiug temperature, F
Mechauical Steam
atomization atomization
130-182 97-130
136-191 103-136
143-199 108-143
148-205 113-148
161-216 123-161
171-226 132-171
179-333 139-179
184-239 145-184
193-248 154-193
200-254 160-200
204-259 164^204
210-265 170-210
Furol viBcosity at 122F
30 .................. .
35... .......... .......
40 Fuel 5 max 45 Fuel 6 min.
60 ....................
80 ..................
100... .........
1 20. . . . . . . . . . .
160.. ..................
200 ...............
240 ......................
300 Fuel 6 max
it may cause plugging of screena and filters. Viscosity is the single most
important property
77
because of diiculties in the handling and atomizing of
viscous oils (Table 3-29). Cracked fuel oils are desirable
78
as fuels because
they usually have a lower pour point, lower viscosity, and a slightly higher
heating valu than the residues from which they are produced. However,
certain cracked oils deposit carbonaceous material on steam heating coils;
79
and henee cutter stocks having a high solvent power such as low-aniline-
point extraets or cracked gas oils, rather than straight- run gas oils, should
be employed for redueing the viscosity of heavy cracked fuel oils. The
Naval Boiler and Turbine Laboratory heater test
80
may be used to
determine the stability of fuel blends.
Petroleum coke is used commereially as a refinery and commercial fuel
(often powdered); in the manufacture of carbn electrodes, brushes, plates,
etc.; in the manufacture of abrasives and artificial graphite; in the
manufacture of calcium carbide; as a metallurgical fuel; in paints and
pigments; in gas manufacture; and in the ceramics industries. The high
heating valu and freedom from clinker-forming substances and the small
quantity of ash make it a desirable industrial fuel. The hardness and
strength of coke increase as the volatile matter is reduced, but it is seldom
strong enough to be used for foundry cupolas. Until 1954, petroleum coke
was made by the delayed coking or chamber processes, but in the future
most coke will be made by a continuous process,
81
Such coke consists of
small pellets which can be handled by fluidizing techniques or air-activated
pneumatic transport systems, and accordingly it is called fluid coke.
Table 3-30 indicates the properties of some cokes,
82
The major uses
83
of petroleum asphaltic materials are indicated in Table
3-31. The properties of typical asphalts are shown in Table 3-32,
84
and a
few properties of other asphalts are shown in Table 3-33.
Consistency
85
(viscosity, penetration, and softening point) determines
the temperature required for use or application and the final hardness and
10
Nelson, W. L., Oil Gas J., Aug, 24,1946, jx 92; Sept. 14,1946, p. 95; Jan. 18, 1947, p.
89; and Feb. 15, 1947, p. 109.
78
Morrell and Egloff, The Congealing Temperature . . . of Cracked Residue, Ref. Na.
Gaso. MfrApril, 1923, p. 17.
79
Batchelder, A. H., The Stability of Residual Fuels, Oil Gas J., Nov. 12, 1936, p. 159.
80
Smith, F. h., Blending Residual Fuel Oil, Pet. Refiner, April, 1945, p. 95.
81
Barr and Jahnig, Fluid Coking and Fluid Coke, Chem. Eng. Prog., April, 1955, p. 167.
** Nelson, W. L., O Gas Nov. 28, 1955, p. 117.
8
* Shearon and Hoberg, Ind. Eng. Chem., 45, 2122 (1953).
84
Petroleum Asphalt, Lubrication/' The Texas Co., June, 1946.
Is
Roediger, J. C., Asphalts and Their Evaluation for Commercial Uses, AS3ME Meeting,
Tulsa, 1946-
TABLE 3-30. ANALYSES AND PROPERTIES OF PETROLEUM COKES
*
Early pet. cokes,
1930-1935
>7
Oven
Delayed Con-
tinuoua
Cracking
still
Coking
still
cokes procesa
cokes
or fluid
cokes
Moisture. wt % ............................ 0.15-3.3 0.3-1.8 0.3-2 Nil-0.5
Volatile combustible matter, wt %
.....................................................
8-18 2-13 0.6-7.4 8-18 3.7-5.3
Aah, wt ......................................... 0-1.6 0.5-1.2 0.2-1.8 0.5-1.6 0.1-2.8
Sulfur, wt % ..................... ........... 0.2 -4.2 0.5-1.2 0.8-1.5 0.5-4.2 1.4r-7.0
Bulk densitv. Ib Der cu ft ............... 56- -69 55-65
True or real density, g per ml..
1.28-1.42 1.5-1.6
Btu per Ib as recd ....................... 15,300
16,400
14,500
15,500
14,400
14,700
14,000
1.6-2.1
Hydrogen, wt % ...........................
Carbn, wt % ...............................
88.3-92.5
TABLE 3-31. PETROLEUM ASPHALTS (1951 and 1955
1
)
Uses
Short tona 1951 Per cent
1951
Short tona 1955*
Paving:
Asphalt cementa. ........ ..................................
4,574,112
4,124,564
216,247
35.6
Cutbacks and road oils. ......... ....................... 32.0
Pmulfiona
t
, ................................................. 1.7 . .
Total.... ..................................................
69 3 12,300,000
Roofing, waterproofing, and mastica:
Roofing and waterproofing ...............................
2,208,409
882,283
16,508
17.2
Flux fnr i-nnfipg. ...... ........... ................. 6.9
Mstic and mstic cake ................................. 0.1
Total ......................................................
24.2 3,400,000
200,000
Briquetting. . ....... . ........................................... 210,323
21,414
1.6
Specialties:
Blending with rubber .....................................
0.2
Pijip and metal COR+inga .............................
26,273
38,868
69,607
0.2
Molding compounds ...................................... 0.3
Paints, enamels, etc ...................................... 0.5
Miac. uses ...................................................... 475,469 3.7
Total ......................................................
4.9 400,000
Grand total ............................................. 12,864,077 100.0 16,300,000
* Shearon and Hoiberg, Ind. Eng. Chem., 45, 2122 (1953).
h
Estimated.
TABLE 3-32. TESTS ON TTPICAL ABPHALTS*
Payng
Roofing -
Floor-
ng
satu
ran!
u
Pene
tration
mme-
adam
AB-
p ha] tic
concreta
Shingle
saturan t
Shingle
coating
Built- up
roo!
mop-
ping
Water
proofing
Mineral
rnbber
Softening point, BAR,
oy
112 129 146 226 190 157 151 302
Ductility at 77F cm... 60+ 100+ 100 2.0 2.0 12 22 0
Penetration at 32
D
F.... 40 25 13 12 14 3 10 2
Penetrmtion at 77F ___ 135 64 33 18 30 20 27 4
Penetration at 115F... Soft 249 108 31 65 67 92 8
Evaporatioa (50 g, 5 br,
325F), per cent ............
0.01 0.06 0.03 0.01 0.01 0.0 0.0 0.02
Flaeh, Cleveland open
cup, F ......... . ................
550 540 560 570 560 645 600 635
Solubilty in CCL, per
cent ................ . ........... .
99.8 99.8 99.8 99.7 99.8 99.8 99.8 99.8
* Petroleum Aaphalt, Lubricacin, The Texaa Co., June, 1946.
TABLE 3-33. OTHER ABPHALT MATERIALS
Materials
Penetration
at 77F -
Ductility at
77F
Melting point,
B <fc R
Paving binders:
Mstic foot pavements and floors ...............................
10-15
180-220
Asphnlt hlfinlfi ............... .................................. . , 10-25
20+
40+
50+
3+
45+
90+
100+ 40+
1 +
1 + 1 +
15+
Sheet aaphalt pavement ............................................... 25-40 105-140
Grout filiar - . . . . . . . . . . . . . . . . . . . . . . . . 40-70 113-140
Grout filler (blown type)...................... ........................ 30^50 150-230
Aaphalt concrete (aggregate sand> etc.)....... 30-70
70-150
113-150
Asphalt mftrndftTTi ................................. 104-113
Roofing asphalts:
Saturant for felt or paper ........................ . .......... .
75-140 110-120
Heavy saturant for felt and rgs ............................ 28-32 140-150
Roof coatings (blown) ........................... ...................... 10-50 160-260
Sealing:
Pipe sealing (sewera, etc.) ......................................... .
40-60 200-225
Pipe coatings ........................... ........... ............. .......... 10-15* 200-215
Waterproofing ............................. ................................ 25-50 140-170
Conaistency.
pliability of the finished product. Temperature susceptibility measures the
change in penetration (D5)
1
with temperature and also the ability of the
asphalt to with stand
1
,ading and shocks. Ductility (D113)
1
measures the
elongation or sUetch, suitability for paving purposes, and ability to resist
vibra ti on. Shock tests are also used for vibrational services, and pliability
tests are necessary for compositions used for wire coat- ing or for
laminated paper. Stain tests are often important. Solubility (D165)
1
in
carbn tetrachloride indicates inert material, asphaltenes, and diiculties
caused by overheating during manufacture or application.
TABLE 3-34. TESTS ON TYPICAL LIQUID ASPHALT MATERIALS*
Rapid
curing
RC-3
(D597)
Mdium
curing
MC-3
(D598)
Slow
curing
SC-3
Slow setting
emulsin SS-1
(D631)
Flash, F (Tag open cup) ............................. 90 170 230
Viscosity Saybolt Furol:
At 77F .................................................. ..
70
At 140F ...................... ............................ 350 350 350
Distillation (ASTM D402) per cent
distillate off: .
At 437F ...................................................
28 2' (D244)
At 500F ........................ .......................... 60 30
42
At 600F ........................ . ....................... 83 75
At 680F ...................... ........................... 100 100
Residue from distillation:
Per cent asphalt ......................... .............
74 76 90 58
Penetration at 77 F ................................. 100 200 Soft 150
Ductility at 77F ....................................... 100+
99.7
100+
99.7
100+
98.5
Solubility in CCL, per cent....... . 99.7
Asphalt, of 100 penetration, per cent.. 74
Petroleum Asphalt, "Lubrication, The Texas Co., June, 1946.
The ASTM
18
has published at least 30 specifications for the numerous
types of petroleum asphalts and road oils. The most fluid road oils of the
EC, MC, or SC grades are designated as No. 0 and the heaviest as No. 5.
The rapid curing (RC) grades contain a cutback of kerosene or distillate-
like material, whereas the slowest curing (SC) grades may consist of
asphalt and the heavy distillates that are naturally associated with asphalt in
erude oil.
CHEMICALS AND SPECIALTEES According to Synthetic Organic Chemicals,
U.S. Production and
TABLE 3-35. CRUDE PRODUCTS FROM PETROLEUM AND NATURAL Gas
Thousand pounds per year
1955 1953 1950
Aromatics:
Dstillates and solvents .........................
642,649 404,545
722,650 462,105 72,927
Cresyiic acid, crude ....................... . 24,470 16,080 16,080
Naphthenic acida ................................... 16,687 23,123 24,684
1,038,290 836,473 329,122
Xylenes, mixed ............... ........ ............. 699,455 749,010 449,587
Other ........................................ ............. 30,404 14,355 532,571
' Total aromatics ......................... .. . 3,174,605 2,505,691 1,424,961
Aliphatics: 131,527
445,214
144,6231 1,821,893
3,048,225 2,135,740/
2,007,140 1,366,175 998,842
Fropylene and C mixtures. .................. 1,331,475 1-222,622 694,047
1,411,285 1,152,197 610,056
n-Butane ................................................ 753,461 418,144 641,072
1,171,596 906,732
444,532 155,589
Isobutylene ............................................ 124,562
663,748
534,507
C
s
hydrocarbons .................................... 250,752 122,048
Diisobutylene .........................................
23,157 20,044
371,948 176,926
Nonene. ....... . . ............... ..................... 146,204 60,986 -
Derivatives. ........ ................................... 8,128 2,681
Other aliphatics ...................................... 694,560 219,242 336,625
Total aliphatics. .... ....................... 13,004,357 8,641,369 5,510,100
Grand total ........ .................................... 16,178,962 11,147,060 6,935,061
number of oil companies that particpate in the manufacture of chemicals
has rsen from a few in 1935 to 48 by 1944, and to 63 in 1955. At least 187
chemical, petroleum, etc., companies used petroleum or natural gas as the
raw stock for chemical manufacture during 1955, and the petro- chemical
production amounted to about 25 per cent
86
of all chemical manufacture. J.
C. Reidel
86
estimates that basic petrochemicals appear finally in the form of
7,000 end-use chemicals. The 1955 production, according to the U.S.
Tariff Commission, is indicated in Table 3-35, and the production
87
of
major chemicals produced largely from petroleum is shown in Table 3-36.
Some important chemicals are produced mainly from petroleum:
* Petrochemicals . , . Today and Tomorrow, Oil Gaa J.
t
Sept. 6, 1954. p, 83.
,T
Katzen, II., Pe. Refiner, December, 1954, p. 128.
Acetic acid ........................... ............. 96
Acetic anhydride.. ................ ............ 96
Acetona .............................. . ............ 95 Nylon ............................. .................... ... 60
............ 30
Acrylic plastics .................... .......... . 100 Phenolie plastics ............. .................. .. 50
............ 90 Polyethylene. ...... .............................. .. 100
Benzene .......... .................... _______ 36 . Polyester plastics ................... , .. 70
Butanols ............................... . .......... 53 Propylene, ...... ................................... .. 100
Butadiene ............................. ............ 100 Polystyrene .................................. . . . .. 50
Epoxi plstica....................... ............ 95 Styxene .............................................. ... 50
Ethanol ................................. _______ 83 Synthetic rubber .................. ............. .. 75
Ethylene.. ............................. ............ 99+ Toluene .............................................. .. 77
Ethylene glycol .................... ............ 80 Urea and melamine plastics.... .. 70
Ethylene oxide ..................... ............ 90 Vinyl plastics ...................................... .. 80
Formaldehyde .............. . ............ 90* Xylenes ............................ .................. .. 89
Glycerol... ............................. ............ 40
* Estimated.
TABLE 3*36. PRODUCTION AND CAPACITT POR MAJOR CHEMICALS OBTAINXD
FROM PETROCHBMICAL AND NONPBTROIJEUM SoUBCTS
Million pounda
Production
1955
Capacity
1955
Hydrocarbon intermedia tea:
Ethylene ............. .......................... 3,000 3,200
Propylene. ..................................... 1,500 1,600
Butylenes .............. .................. . . 2,200 2,000
Butadiene .................................... . 1,200 1,200
Acetylene ........................ ........... . 750 850
2,400 2,600
Toluene, .................... ......... ......... 1,300 1,350
1,100 1,100
1,000 1,000
Poly ethylene ................................ 350 400
Synthetic rubber ........................... 1,800 4,200
Phenol ........................................... 575 585
Ammonia ............... ....................... 6.000 6,800
Aphatic chemicals:
Formaldehyde ................... ......... . 550 600
Acetaldehyde ................................ 800 860
Methanol ....................................... 1,500 1,570
Ethanol .......................................... 1,800 2,250
Isopro panol ........................ ......... 1,200 1,200
Butanols .................................. ..... 400 450
Ethylene oxide .............................. 800 970
Ethylene glycol ............................. 750 850
Acrylonitrile .................................. 180 200
Acetic acid .................................... 550 650
Acetic anhy dride ......................... 800 900
600 700
Katzen. R.. Pet. Re/dner. December. 1954. n. 128
n f
D
!
J
??
tan
Nash
Brooks
>
and
Tizar, "The Science of Petroleum, 4 vols., xfrd University
Press, New York, 1938; also Neson, W. L., Refiner's Notebooks 108 and 132, Oil Gas J.,
Aug. 31, 1946, and Feb. 15, 1947.
18
Nelson, W. L.
f
Oil Gas J.
t
May 12, 1949, p. 116.
10
White No. 2-116; Fue! 72, No. 2-114A; All Purpose, No. 2-103B; Grade 80, AN-
F24; Grade 87, AN-F25; Grade 91/96, AN-F26; Grade 98/130, AN-F27; Grade 130, AN-
F28; and Grade 140, AN-F29, Superintendent of Documents, Washington, D.C.
34
MacCoull, Hollister, and Crone, Effect of Altitude on Anti-knock . . . , Ref.
Nal. Gaso. Mfr., November, 1937, p. 534.
36
Effect of Altitude on Knock Rating in CFR Engines, J. Research Nall. Bur. Stand
ares, 28, 713 (1942).
38
Offutt, Ostergard, Fogle, and Beuther, Naphtha Reforming with Gutside Gas, 26th Ann.
Meeting of API, Chicago, Nov. 12, 1946.
44
Blade, O. C., Annual Surveys, U.S. Bur. Mines Repl. Invesl. 5132, April, 1955.
41
IP 57/55, Standard Methods for Testing Petroleum and Its Products, 26 Port- land Place,
London, W.C.i, England.
41
Nelson, W. L., Smoke Point and Ring Number of Kerosenes, Oil Gas J,
t
June 14, 1954, p,
151.
58
Service Characteristica of Motor Oil, aa Related to Chemical Composition, Oil Gas J.,
June 13, 1935, p. 59.
68
Livingston and Grase, Carbn Deposits from Lubricating Oils, Ind. Eng. Chem., 31, 904
(1929).
80
Georgi, C. W., Subcommtee Report, SAE Journal, February, 1943, p. 52.
81
Nelson, W. L., Reducing with Depreasants,
Oil Gas J.
f
Dec. 30, 1944, p. 269. -
75
Nelson, W. L,, Oil Qas J.
t
Dec. 22, 1952, p. 353.