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Патент USA US3020238

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United States Patent
3,020,228
Patented Feb: 6.’ .1952
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3,020,228
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consisting of aluminarand thevoxides of molybdenum and
,
iron, the oxides being supported on the alumina, The
UPGRADING LUBRICATING OILS BY HYDRO
GENATION WITH A ‘THREE COMPONENT
catalyst may also contain the oxide of cobalt.
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The pressure may vary between 5 ats. and 70 ats., but
Jacques Demeester, Paris, France, assignor to The British 5 in practise one will use a pressure correspondingto the
Petroleum Company Limited, London, England, a ' pressure of the hydrogen-rich gases from catalytic reform
joint-stock corporation of Great Britain
ing processes which may be at. 20-30 ats, The hydrogen
' N0 Drawing. Filed Apr. 27, 1959, Ser. No. 808,862
CATALYST
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feed rate is also variable but low, beingtrom 5 to 150
Claims priority, application France May 2, 1958
vols. per vol. of oil under normal conditions. A preferred
22 ‘Claims. (Cl. 208-—264)
10 value is 23 vols. per vol. of oil. The feed rate can vary
This invention relates to the treatment of lubricating
from 0.5 to 6 vols. of oil per vol. of catalyst per hour,
oils.
‘
the higher values being suitable for solvent-re?ned oils. _ _
Catalytic reforming processes have made available
The process according to the invention gives oils. vof
to petroleum re?neries considerable quantities of gases
satisfactory colour, but also produces oils of a stability
rich in hydrogen, thus rendering economically attractive
methods of re?ning by means of hydrogen, in particular
very much superior to that obtained with the traditional
catalyst, consisting of the oxides of molybdenum and
the re?ning hydrogenation of lubricating oil fractions,
hereinafter referred to as hydro?nishing.
cobalt,
_ The catalyst
under the
consisting
same operating
of alumina
conditions.
and the oxides
_ of
.
Applicant has studied the hydro?nishing of lubricating
molybdenum and iron has the following preferred com:'
oils as a ?nal treatment for these oils in place of the 20 position, in terms of the content of the oxides and the
conventional treatment with clay. The object of this ?nal
treatment is to give the oil in the ?rst place a satisfactory
colour and appearance and in the second place a suitable
heat and storage stability. As in the case of clay treat
ment, there should be no important change in the molec 25
ular structure of the oil, in particular there should be
no appreciable drop in viscosity.
Numerous catalytic hydrogenation processes for lu
bricating oils are known; certain use conditions suffi
alumina individually as a percentage of the catalyst
weight:
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1
. Percent
IVIOCI';v
R2203
,
... _. _
._
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1.2
the oxides being‘supported on the alumina, preferably
gamma alumina, which forms the balance of, the catalyst;
ciently severe to change the structure ‘of the oil and pro 30 but the proportions of the two oxides may vary as fol
duce a drop in viscosity. It is possible at this price to
lows:
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obtain a satisfactory colour and stability. In particular,
at‘ temperatures above 340° C.,,one can hydrogenate
Percent
lubricating oils over a catalyst ‘consisting of the oxides of
M003
-Q
4->12
cobalt and molybdenum on alumina, and this hydrogena 35 F3203
tion ‘produces a suitable colour and stability with a more
or less appreciable drop in viscosity.
If the oxide of cobalt, C00, is added to the oxides of
If one wishes to avoid an appreciable drop in viscosity,
molybdenum and iron, the preferred composition, meas
it is necessary to work at temperatures below 340° (3.,
' '
and under .this condition hydrogenation with conventional 40 ured in the‘ same terms, is:
catalysts consisting of the oxides of cobalt and molybde
Percent
num on an alumina support easily gives the desired col
M003
9 to 10
our, but does not always give a su?‘icient stability.‘ This
C00
Fezog
2t0to 5
di?‘iculty is more apparent in the case of oils which have
not been solvent re?ned and which usually need to be
treated with sulphuric acid andclay. For present pur 45.
onthe alumina support, preferably gamma alumina,
poses, stability is expressed by the index of reversion,
which forms the balance of the composition. '
v"
de?ned hereinafter for non solvent-re?ned oils, and by
One can vary the above values within the following
the B.A.M. oxidation test in the case of solvent-re?ned
oils (LP. Method No. 48).
limits:
Applicant has investigated the operating conditions and 50
the catalysts capable of effecting hydro?nishing to pro
duce oils of suitable colour which are also heat and stor
age stable, whether or not the oils have been previously
solvent re?ned, and without appreciable modi?cation of
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M003
Fe2O3
Percent
3 to 20
4 to 20
C00
1 to 12
the molecular structure of the oils, that is to say without '
, appreciable drop in viscosity.
in such a manner that the ratio by weight MoOQ/CoO is
The process has been studied particularly for the treat
about 3/1 and the content of Fe2O3 is as high as possible,
ment of distillate oils from crude petroleums of para?inic
compatible with the porosity of the catalyst support. ‘ In
or mixed base, but can equally be applied to oils from 60 any case, the ratio Moos/C00 should be above 2/1 when
other crude petroleums, bituminous shales and synthetic
oils.
According to the invention, these oils are re?ned with
- one uses 5% vof Fe2O3 andabove 1.5/1 when one uses
hydrogen at temperatures between 150° and 340°. 0.,
preferably between 250° and 320° C., using a catalyst 65
Of F6203.
-
-
In all-cases the catalyst according to the'invention can
be sulphurised before using.
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Applicant has also discovered that the method of prep
3,020,228
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aration of the catalyst is an important factor in determin
EXAMPLE 1
ing its activity.
In particular, catalysts prepared by the traditional
method by coprecipitation of the alumina and of the salts
Hydro?nishing of a dewaxed but non-solvent-re?ned
oil fraction
of the metals of iron, molybdenum and cobalt, have an
activity very much less than that obtained by the method
of preparation according to the invention. The same api
The oil treated had the following properties.
plies to the method of impregnation of the freshly pre
cipitated wet alumina gel with solutions of the above
10
salts.
According to a further feature of the invention, cata
lysts consisting of alumina and the oxides of molybde
num, iron and, if desired, cobalt, the oxides being sup
ported on the alumina, are prepared using granular alu
mina already calcined. The alumina is preferably an 15
activated alumina obtained by the calcination of hydrat
gillite at above 500° C. The macrostructure of this alu
mina should be relatively loose in order to permit the
impregnation therewith of a suflicient quantity of ferric
nitrate solution which is a di?icult matter.
Density, 15/l5° C__________________________ __ 0.910
Viscosity in cs.:
I
@ 37.8° C ___________________________ .._
50° C _____________________________ .._
23.7
14.6
Viscosity index _________ up _________________ _..
47
'Flashpoint, ‘’ C ____________________________ __
200
Pour point, ° C ____________________________ __ ‘~24
Acid index (rng. KOH/gr.) __________________ __
Sulphur, percent Wt ________________________ __
0.22
2.9
This oil was hydrogenated under the following conditions:
Hydrogen pressure _______ _. 20 ats.
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Hydrogen feed rate ______ _. 25 litres/litre of oil.
20
By way of non-limiting example, a suitable alumina
has pores of approximately 30 angstroms. Its active sur
face- is 250 square metres per gramme and the volume of
Space velocity___>_-___x____ l>vol./vol./hour.
Temperature ____________ __ Prom 250-340° C. by in
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crements of 25°
C.
pores 35 cubic metres per 100 grammes.
‘ The above alumina should ?rst of all be impregnated
with a solution of ferric nitrate, and the acidi?cation of
These conditions do not produce any appreciable drop
in viscosity and the yield of oil is always very near 100%.
The acid index of the hydrogenated oil is lowered to
this solution favours impregnation. This acidi?cation is
values of the order of 0.01.
_.
For each treating temperature, the colour of the oil
was measured as expressed by light absorption using a
the neighbourhood of 0. The impregnation should be
‘effected bysoaking the alumina in the ferric nitrate solu 30 photocolorimeter Benet-Maury through a Wratten screen
No.‘ 7. The stability was expressed by comparing the
tion or by wetting the alumina with the solution or by
colour of a sample efore and after arti?cial aging for
any other equivalent method.
preferably effected by means of nitric acid up to a pH in
The impregnation of the alumina is followed by drying
at 110° C., then by calcination at 550° C.
The alumina already impregnated with the oxide of
iron Fe2O3, is then impregnated with a solution of ammo
nium molybdate. The use of an ammoniacal solution
of ammonium molybdate is necessary to facilitate impreg
16 hours at 85" C. in the presence of air.
stability.
Index of reversion
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nation of this salt and avoid its precipitation in contact
with'the alumina. One dries at 110° C. and caicines 40
at 550° C.
The ratio
between the light absorptions gives what one calls the
“index of reversion” of the oil, an expression of its
v
Absorption of the arti?cially aged oil
Absorption of the fresh oil
If it is desired to introduce cobalt into the
For each catalyst studied under the above conditions,
catalyst, the impregnation with cobalt nitrate should be
one can plot by this method the graph of the index of
effected last, following the drying and calcination at
reversion as a function of the hydrogenation temperature.
550°‘ C. If desired, the calcination between the impreg
nation with the ammonium molybdate and with the cobalt 45 The lowest index of reversion (i.e. the maximum stability).
corresponding in each case to a temperature between
nitrate may be dispensed with but the catalyst then runs
275 and, 320° (3., has been shown in Table 1 as well as
the risk of being less homogeneous and less active.
the colour of the hydrogenated oil, expressed by its light
A catalyst prepared according to the invention as
absorption by the photocolorimeter.
described above is still not capable of giving the desired
Table 1 sets- out the results obtained with catalysts
results. In order that it may give its full effect in the 50
of the same granular form based upon the same gamma
process according to the invention, it is necessary to
alumina and comprising different proportions of the oxides
submit item a preliminary activation treatment which is
of molybdenum, iron and cobalt.
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most conveniently carried out in the hydrogenation reactor
The traditional catalysts consisting of the oxides of
in which it will be used.
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According to the invention, this activation treatment 55 molybdenum and cobalt, give a maximum stability
expressed by an index of reversion of 1.47 when the ratio
is effected by passing over the catalyst a mineral lubricat
Moos/COO is equal to 3/1 and with 20% total active
ing oil, preferably fluid and non-re?ned, undera pressure
of?hydrogen and at a temperature. above or equal to
The catalysts consisting of the oxides of molybdenum
300° C. for a period of at least 24 hours. Satisfactory
60 and iron give a maximum stability expressed by an index
conditions would be, for example:
oxides.
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of reversion of 1.38‘ with 20% total active oxidesof
Temperature ____________ _. 325° C.
which only 8% is M003, which shows the considerable
Space velocity of oil per
e?ect of Fe2O3 in place of C00.
Pressure _______________ __ 20 atmospheres.
.
.
The catalysts consisting of the oxides of molybdenum,
volume of catalyst ____ __ 1 yoL/voL/hr.
65 iron and cobalt give maximum stabilities always for a
Feed rate of hydrogen ____ _. 20 vol. per vol. of oil per
hour.
‘Duration _______________ __ 48 hours.
ratio of MoO3/CoO of about 3. The corresponding
indices of reversion are lower accordingv as the content '
of Fezoa is higher.
Percent Pesos:
‘Index of reversion
While the temperature of at least 300° C. is a critical 70.
condition, the other conditions can be varied within large
limits.
The invention will now be described by way of example
with reference to the hydro?nishing of lubricating oil
fractions from a Kuwait crude petroleum.
75
These ?gures illustrate the considerable effect-of FeZOQ
on the stability of the oil.
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8,020,228
8
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Index of
EXAMPLE 1v
Method of'preparation:
Preparation of catalyst comprising the oxides of iron,
reversion
ferric nitrate. Impregnation with a solution
of ammonium molybdate and cobalt nitrate—
molybdenum and cobalt on alumina (Fe2O3: 12%,
M003: 8.5%, C00: 2.5%)
drying-calcination
corresponding nitrates.
This alumina has pores of 30 angstroms and an active
Drying-calcina
tion—-—granulation. impregnation with a so
surface of 250 square metres per gramme. The volume
of the pores is 35 cubic centimetres per 100 gr., which en
ables it to be impregnated easily with an appreciable
quantity of ferric nitrate solution.
This alumina was ?rst impregnated by soaking at am
bient temperature in an acid solution of pH approximately
0 of 45% by weight ferric nitrate (NO3)3Fe, 91-120. The
quantity of solution corresponds to an equal proportion
by weight of nitrate of iron and alumina. Soaking was
__________________ __ 1.50
Example VIII-Co-precipitation of the hydrox- ’
ides of iron, cobalt and aluminum from the
The catalyst support is a granular alumina of l to 3 mm.
obtained by the calcination of hydrargillite at 500° C.
lution of ammonium molybdate-—drying
1.90
calcination
Example IX--Impregnation of granular acti
vated alumina with a solution of ammonium
molybdate. Drying—impregnation with a so
lution of the nitrates of iron and cobalt
15
drying-calcination
an __________ _._. ____ ..
1.40
Example X-Mixture of hydroxides of iron, co
balt, molybdenum and aluminum freshly pre~
continued for 36 hours. The alumina Was allowed to
drain and then dried slowly below 100° C. then at 110° C.
20
It was ?nally calcined at 550° C.
cipitated and wet——drying—calcination——pel
leting
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1.50
carried out by soaking at ambient temperature in an am
Lastly, the importance of the ?nal activation of the cat
alyst prepared according to the invention is shown in the
moniacal solution of ammonium molybdate containing 80
following example.
impregnation with ammonium molybdate was then
grammes per litre, with about twice the theoretical quan
tity of molybdate and for a period of 6 hours. The alumi
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EXAMPLE XI
The same catalyst as in Example IV is placed in service
na was then allowed to drain, dried and calcined as above.
in the same plant which operates under the same condi
The impregnation with cobalt nitrate was ?nally carried.
tions and with the same feedstock, but from the begin
out by soaking at ambient temperature in a solution of
ning a temperature in the region of 275° C. was used,
cobalt nitrate containing 100 grammes per litre, with twice
without having activated for 48 hours at 325° C. The
30
the theoretical quantity of cobalt for a period of 18 hours.
oil thus treated had a colour stability expressed by an
The alumina was ?nally allowed to drain, dried and cal
index of reversion of 1.6.
cined as above.
tion:
IV.
Percent
Fego3
M003 .._.
_
CoO
I claim:
1. A process for re?ning a lubricating oil to produce
an oil of improved stability, which comprises contacting
1 8.5
1
____ __
_.__.______.__
.
The iron-containing catalysts used in Examples I to
III were prepared by the method described in .Example
The catalyst thus prepared had the following composi
2.6
the oil in the presence of hydrogen and at a temperature
40 of between about 150° and 340° C. with a catalyst con
on an alumina support.
sisting of alumina and the oxides of molybdenum, iron,
and cobalt; the oxides being supported on the alumina, and
the ratio, by weight, of molybdenum oxide to cobalt
oxide being at least equal to 15:1, the content of molyb
ditions:
45 denurn oxide being between about 3 and 20% by weight
of the total catalyst weight, and the minimum content of
Temperature ______ .. 325° C.
iron oxide being 10% of the total catalyst Weight when
Oil feed rate ______.__ 1 vol. per vol.'of catalyst per hour.
said ratio is equal to 1.521, progressively less than 10%
Pressure _________ __ 20 atmospheres.
The catalyst was then placed in service in a continuous
ly operating hydrogenation reactor, while feeding a Ku
wait spindle oil dewaxed only, under the following con
of the total catalyst weight as said ratio increases from
Hydrogen feed rate--. 20 vol. per vol. of oil per hr.
50 1.5:1 to 3:1, 4% of the total catalyst weight when said
Duration __.________ 48 hours.
ratio is in the region of 3:1, and progressively more than
4% of the total catalyst Weight as said ratio increases
above 3:1.
2. A process according to claim 1, wherein said ratio
of molybdenum oxide to cobalt oxide is 3:1.
3. A process according to claim 1, wherein the hydro
gen pressure is from 5 to 70 ats., the hydrogen feed rate
is from 5 to 150 vols. per vol. of oil treated, and the space
velocity is from 0.5 to 6 vols. of oil per vol. of catalyst.
4. A process according to claim 1, wherein the hydro
‘gen pressure is from 20 to 30 ats., the hydrogen feed
rate is from 5 to 150' vols. per vol. of oil treated, and the
space velocity is from 0.5 to 6 vols. of oil per vol. of
After this activation treatment, the temperature was
lowered to 275° C. and the treated oil then had a colour
stability expressed by an index of reversion of 1.28.
' The following are examples of preparing a catalyst of
the same composition as in Example TV but by di?'erent
methods from that according to the invention.
These catalysts were activated as in Example IV, by
hydrogenation of the same spindle oil at 325° C. and the
treatment of this oil was then carried out at 275° C.
giving the stabilities expressed by the indices of reversion
as follows.
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[Index of
Method of preparation:
reversion
Example V~—Co-precipita'tion of the oxide
catalyst.
Drying-calcination—granulating. Impreg
age of the total catalyst weight:
nitrate—drying-calcination ___________ __ 1.55
Example VI——Agglomeration of a powder con
sisting of a mixture of activated alumina and
of ammonium molybdate by means of a solu
tion of the nitrates of iron and cobalt-—dry
ing—~calcination
..__. __________________ -_
activated alumina by means of a solution of
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_
the content of the oxides and the alumina as a percent~
nation with ammonium molybdate and. cobalt
Example VII-Agglomeration of a powder of
‘
5. A process according to claim 1, wherein the cat
alyst has the following composition of oxides in terms of
of iron and of alumina from the nitrates.
70
M003
.
Fe2O3
_
_
C00
1.70 7
__
-1-
Percent
_... 3 to 20
1 to 12
_
4 to 20
6. A process according to claim 5, wherein the cat
75 alyst has the following composition of oxides in’ terms of
3,020,228
9
10
the content of the oxides and the alumina as a percent
molybdenum oxide to cobalt oxide being at least equal to
15:1, the content of molybdenum oxide being between
about 3 and 20% by weight of the total catalyst composif
tion weight, and the minimum content of iron oxide being
10% of the total catalyst composition weight, when said
age of the total catalyst weight:
Percent
M008
..
C00
Fe2O3
..___
9 to 10
2 to 5
_
10 to 12
ratio is equal to 1.5: 1, progressively less than 10% of the
7. A process according to claim 1, wherein the catalyst
total catalyst composition weight as said ratio increases
from 1.5 :1 to 3:1, at least 4% of the total catalyst com
has been activated, prior to contact with the oil to be re
position weight when said ratio is in the region of 3: 1, and
?ned, by contact in the presence of hydrogen with a
mineral oil having a high sulphur content at a tempera 10 progressively more than 4% of the total catalyst com
position weight as said ratio increases above 3:1.
ture of at least 300° C. for at least 24 hours.
17. A catalyst composition according to claim 16,
8. A process according to claim 7 wherein said min
wherein said ratio of molybdenum oxide to cobalt oxide
eral oil having a high sulphur content is an extract ob
is 3:1.
tained by the treatment of a mineral oil with a selective
15
18. A catalyst composition according to claim 16 hav
solvent.
ing the following composition of oxides in terms of con
9. A process for re?ning a lubricating oil to produce an
tent of the oxides and the alumina as a percentage of the
oil of improved stability, which comprises contacting the
total catalyst weight:
oil inthe presence of hydrogen and at a temperature of
150° to 340° C. with a catalyst consisting of alumina and
Percent
3 to 20
the oxides of molybdenum and iron, the oxides being 20 M003.“
C00‘
1 to 12
supported on the alumina, the total quantity ofsaid oxides
mo, __________________________________ _.. 4 to 20
being at least 10% of the total catalyst weight, and the
quantity of iron oxide being at least 6% of the total cat
19. A catalyst composition according to claim 18 hav
alyst weight.
10. A process according to claim 9, wherein the quan 25 ing the following composition of oxides in terms of content
of the oxides and the alumina as a percentage of the total
tity of iron oxide is at least equal to the quantity of molyb
catalyst weight:
denum oxide.
_
Percent
11. A process according to claim 9, wherein the hydro
9 to 10
gen pressure is from 5 to 70 ats., the hydrogen feed rate 30 M003"C002 to 5
is from 50 to 150 vols. per vol. of oil treated, and the
Fe2O3 ____ __
10 to 12
space velocity is from 0.5 to 6 vols. of oil per vol. of cat
alyst.
20. A catalyst composition for use in the hydrogenating
12. A process according to claim 9, wherein the hy
re?ning of lubricating oils, which consists of alumina and
drogen pressure is from 20 to 30 ats., the hydrogen feed 35 the oxides of molybdenum and iron, the oxides being sup
rate is from 5 to 150 vols. per vol. of oil treated, and the
ported on the alumina, the total quantity of said oxides
being at least 10% of the total catalyst composition weight,
space velocity is from 0.5 to 6 vols. of oil per vol. of
catalyst.
,
and the quantity of iron oxide being at least 6% of the
total catalyst composition weight.
13. A process according to claim 9, wherein the pro
portion of the oxide of molybdenum, M003, varies from 40 21. A catalyst composition according to claim 20,
4 to 12% of the total catalyst weight, and that of the
wherein the quantity of iron oxide is at least equal to the
quantity of molybdenum oxide.
oxide of iron, Fe2O3, varies from 6 to 20% of the total
catalyst weight, the optimum composition being M003, 8%
22. A catalyst composition according to claim 20,
wherein the quantity of the oxide of molybdenum, M003,
of the total catalyst weight, Fe2O3, 12% of the total cat
alyst weight.
.
.
45 varies from 4 to 12% of the total catalyst composition
14. A process according to claim 9, wherein the cat—
alyst has been activated, prior to contact with the oil to
be re?ned, by contact in the presence of hydrogen with a
mineral oil having a high sulphur content at a tempera
ture of at least 300° C. for at least 24 hours.
50
15. A process according to claim 14, wherein said
mineral oil having a high sulphur content is an extract
obtained by the treatment of a mineral oil with a se
lective solvent.
16. A catalyst composition for use in the hydrogenat
ing re?ning of lubricating oils, which consists of alumina
and the oxides of molybdenum, iron and cobalt, the oxides
being supported on the alumina, the ratio, by weight, of
weight, and that of the oxide of iron, Fe2O3, varies from
6 to 20% of the total catalyst composition weight, the
optimum quantity of M003 and F6203 in the catalyst com
position being MoO;, 8% of the total catalyst composition
weight, FezOa, 12% of the total catalyst composition
weight.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,654,696
2,739,132
2,799,661
2,880,171
La Porte _____________ -_ Oct. 6, 1953
Riedl ________________ _._ Mar. 20, 1956
De Rosset ____________ _- July 16, 1957
Flinn et a1 ____________ __ Mar. 31, 1959
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