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Патент USA US2108250

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27,108,250
Patented Feb. 15, 1938
UNITED ‘STATES PATENT OFFICE
_
aioslzso \
_
nYnnoGENA'rEn HEAVY on.
William H.0armody, Pittsburgh, Pa., assignor to
The Neville Company, a corporation or Penn-_
sylvania
No Drawing. Application November 28, 1936,
Serial No. 113,260-
clear, colorless heavy oil free ‘from its original
This invention relates to‘ the treatment of phe- '
nolic'heavy oil.
‘
phenolic odor. It had a faint alcoholic odorpre
-
In the production of phenol-modi?ed resins of
, ' This
sembling
strongly
cyclohexanol
hydrogenated
andheavy
related
oil is
compounds.‘
not, haw- \
the coumarone-type, by conducting in a mixture
ever, ‘a solvent for cellulose acetate.
5 of crude solvent naphtha and phenolic reagent
Apparently '
the severity of the treatment resulted in aromatic
tion involving the phenolic substance, the result-~ ring and double bond saturation‘, with the forma
simultaneous polymerization reaction and reac
tion of an alcohol group instead of a phenolic
ant phenol-modi?ed coumarone resin has in its
content phenol-modi?ed polymers in different
group.
_
‘
‘
_
_
-
.
‘Upon further investigation, I have discovered
10 stages of polymerization. By suitable procedure,
such as steam distillation, subsequent to the
resin-forming reactions, the resinous products
are separated into a solid, alcohol-soluble resin
that I can, by hydrogenation, very substantially
improve the color and odor of the phenolic heavy
oil without detriment to its solvency ‘for cellulose
acetate.
_ and a soft ?uid substance consisting oi polymeri
This I do by hydrogenating _. the heavy
J" ized and ‘phenol-modi?ed products of,_ indene, ‘oil to an extent equal to but a small proportion
coumarone, dicyclopentadiene, or the like, which ’
heavy oil is when gently heated a solvent, for cel
lulose acetate.
I
-
of the theoretically possible. To effect this pur
pose, I operated with a decreased-{quantity .of
~ catalyst, and under decreased severity in the con
p
The vundesirable qualities of this phenolic
20 heavy oil are arelatively dark color and an un
pleasant odor. I have greatly improved the color
and odorof the phenolic heavy oil by hydrogena
on.
In‘ initially attempting, by hydrogenation, to
ditions of temperature and pressure. A typical
example of my satisfactory conditions may be
given as follows:
'
1
.
1‘ -
Example No. 1 "
‘Heavy oil ______ _;_ 460 grams charged into
Q5 improve the color and odor'of the phenolic‘heavy Nickel catalyst__ 48 grams ‘, drogenator
oil, I subjected it to hydrogenation under condi
tions suitable for hydrogenation of a "‘couma-_,
hy-‘
i
all, ,
'No solvent
Operating conditions '
/
ro'ne” heavy all without phenolic modi?cation.
One hundred'pounds of hydrogen were charged
That is, I introduced the heavy oil, together with - into the hydrogenator at normal room‘ tempera
30 a solvent and a substantial quantity of Raney ture, and the hydrogenator was, gently heated.
nickel catalyst, into a pressure bomb'arranged for At a temperature of 60° C. (absorption was rapid,
agitation of its contents. Under heat, and with and entire absorption occurred at a temperature
agitation, hydrogen was introduced under such
pressure and for such time period as to e?ect hy
35 drogenation of the heavy oil to a substantial de
gree. A typical ‘procedure of this sort may be
given as follows:
'
-
of 85° 0. Upon cooling to'normal room temper?
ature therewas a zero pressurein the hydrogen
ator. The heavy oil showed improvement-in both
its color and odor, but both were still noticeable
and of typical sort.
'
\
I then repeated the? dosage of hydrogen two»
0 Nckel catalyst..- 100 grains chgrged into by‘ ' additional times, in each step limiting the pres
eavy 011--..--" 100 grams -
>Cyclohexane_____‘ 200 cc._
A
A
rogenatot:
Conditions:
Total time: 2% hours.v
, Maximum Hz pressure: 10804‘; at beginning.
v45
Maximum temperature: 198° C. at end.
In operation, the hydrogen was admitted to
1080# and heat applied. At very moderate temé
40 ‘I
sure to a maximum of ‘100 pounds ‘and limiting
the temperature to a maximum of 92°C. The
total time of actual hydrogenating treatment was
approximately three hours, one hour being allot
ted to each dosage of hydrogen. '
'
'
‘ Results
The result of this step-by-step, and- rigidly»
peratures the pressure drripped to 320# at 170° C. - controlled, hydrogen modification was to produce 50
a clear and very light colored phenolic heavy oil
50 The bomb was rechargedv to '1080# and the pres
_
sure dropped to 470# .at 192° C. The third of greatly reduced odor.
The heavy oildid not suffer impairment in its
charge to 1080# proved to be su?icient with the
‘
pressure failing to drop below 630# at K195o c. capacity to dissolve cellulose acetate.
- when held there for approximately 30 minutes.
55
Comparing the weight of hydrogen introduced
56
The product obtained by this procedure was a . into the heavy-oil by this above-described pro
,
2,108,250
cedure with the weight of the unmodified heavy
resort is again desirably had to a step-by-step
oil, I found that I had introduced hydrogen in a
procedure, in order that the employment of ex
quantity equal to about 3% the quantity in which .cessive pressure may be avoided. .Generaliy, it
it might theoretically be introduced. The may be stated that any mode of hydrogen intro
problem was then to find how far hydrogenation duction is satisfactory, provided that it is com
. might be carried without impairing the solvency patible with reasonably accurate measurement
of the heavy oil for cellulose acetate. The fol
of thequantity of hydrogen which is introduced.
lowing example approximates optimum condi
' The utility of my invention is greatffor the
tions. '
. reason that cellulose acetate is a material iind-
vExample No. 2
Heavy oil _______ __‘_ 460 grams
' Nickel catalyst"..-
48 grams
'
-
charged into by
No 801vem
'
ing increased use in the arts. The phenolic 10
heavy oil, as such, is a good solvent for the cel
lulose acetate‘, but is, when unmodi?ed, an un
drogen'ator
desirable solvent for cellulose acetate ' in pre
paring cellulose acetate for many of its uses. By
EE
Procedure
freeing the phenolic heavy oil of its objectionable 16.
qualities, while retaining to the full its most valu
able property, I have succeeded in obtaining a
product of substantial conmier'cialaand technical
A
Similarly to procedure in Example 1, the
hydrogen was supplied in 100 pound dosages, the
‘pressure never exceeding a'maximum of 100
,pounds. r'I'he temperature at no time exceeded
‘ 100°
C.
I
w
value.
I
I_ claim. as my invention:
_
Instea’dof employing 3 successive dosages of
20
1. Asa composition of matter a heavy oil con
sisting primarily of the soft ?uid steam-volatile
hydrogen of 100 pounds each,'6 dosagesin'the - product of those ‘polymerizables found in crude
same quantity were employed, the pressure being solvent naphtha resulting from polymerization
permitted to fall to zero after each injection of ,and reaction of, those polymerizables with a
phenolic substance in a mixture of crude sol
‘hydrogen.
r
vent naphtha and a phenolic reactive and modi
-?ed further by hydrogenation up to a point at
' The phenolic heavyoil as-so hydrogen-modified ‘which hydrogen modi?cation serves to render
had an almost imperceptible coloration, and its the phenolic heavy oil approximately colorless 30
odor was only faintly reminiscent of phenol.
and odorless and below a point at which the
The heavy oil did not suffer impairment in its phenolic heavy oil loses its inherent capacity to
-
’
Results
» ‘capacity ‘to dissolve cellulose acetate.
It will be observed, the quantity of heavy oil
treated being identical with the quantity treated
in Example Nonl, that the quantity of .hydroger
' . introduced- into‘the heavy oil is doubled.
The
actual hydrogenation effected was thus about 6% i
the theoretically possible.
Y
,
-
40v Having thus successfully modi?ed the phenolic
l~heavy oil, I experimented to see ‘how far hydro
lgenation might be carried without detracting
from the most valuable quality of the heavy oil.
_By_a series of ‘experiments I discovered that loss
~45 ;of solvency for heavy-oil ‘was suffered to a per
ceptible degree when the phenolic ‘heavy o? had
been hydrogemmodiiied to an extent equal to
dissolve cellulose acetate.
2. As a‘composition ‘of matter a heavy oil con
sisting primarily of the soft ?uid steam-volatile $5
product ‘of those polymerizables found in crude
solvent naphtha resulting‘from. polymerization
and reaction of ‘those polymerizables with a
phenolic substance in a mixture of crude solvent
naphtha and a phenolic reactive, said phenol
for cellulose acetate, and said heavy oil being
approximately colorless and odorless by virtue of
hydrogenation not greatly, in excess of 10% the .
theoretically possiblelhydrogenation of the heavy
oil.
-
'
“
3. As a composition. of matter a heavy oil con
‘10%, of the‘ theoretically possible. When intro _;sisting primarily of they soft ?uid steam-volatile
iducedin quantities exceeding 10%, ‘6f the theo- product of those po'lymerizables found in crude
50 reticalf‘hydrogenserved ‘increasingly to impair solvent naphtha resulting from polymerization
‘the solvent‘ power‘pf the phenolic heavy oil for and "reaction > of those polymerizables with a
:cellulose acetate. ; The conclusion was that hy
‘ drogenation/of the phenolic heavy oil should, not
,be continued to a point greatly exceeding 10%
-55 ‘the theoretically possible,’ and that the best re
' suits are attained when hydrogenating to an ex
tent equal to from 4% to 9% of complete theo
- retical hydrogenation.
- ‘ It should be explainedthat, in’ preparation for
each hydrogenation, the hydrogenator is ?ushed
free of air by hydrogen, so that a completely hy- '
drogen atmosphere exists within the hydroé
genator during actual hydrogenation. Also vit
40
modified heavy oil being when heated a solvent
50
phenolic substance in a mixture of crude solvent
naphtha and a phenolic'reactive, said phenol
modifled-heavy oil being when heated a solvent
for'eellulose acetate, and said phenol-modi?ed
heavy oil being approximately colorless and odor
less‘by virtue of‘hydrogenation‘v within the ap
proximate range of 4% ‘the theoretically possible
hydrogenation of theheavy oil and~9% thetheo
retically possible hydrogenationv of the heavy'oil.
80
4. As a composition of matter a heavy oil con
sisting primarily of the soft ?uid steam-volatile
product of those polymerizables found in crude
should‘ be understood that-the step-by-step pro;- _. solvent naphtha resulting from polymerization
cedurej given in the examples was - employed , and reaction of those polymerizables with a 65
chie?y as a convenience in feeling my way, phenolic substance in a mixture of crude solvent
after deciding that a substantially less than com
plete hydrogenation might cause substantial im
provement in the phenolic heavy‘ oil, without ‘in
70 practical effect lessening its utility. Thus, if the
naphtha and a phenolic reactive, said phenol
modi?ed'heavy oil beingwhen heated a solvent
for cellulose acetate, and said phenolic ‘heavy oil
having 'a' color depth and odor substantially re
quantity of heavy oil subjected 'to hydrogen modl duced by partial hydrogenationwithin‘ a range 70
i?cation be relatively small, all the" hydrogen
may be introduced at one charge. If, however,
the heavy oil‘is treated in relatively large batches, '
below about ‘10% the theoretically possible hydro
genation of the phenolic heavybil.
'
» ,
_
WILLIAM H. CARMODY._
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