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Патент USA US2117572

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Patented May 17,- 1938
2,117,572
UNITED STATES PATENT OFFICE
2,117,572
METHOD OF REFINING ROSIN ANl) ROSIN
ESTERS
Lanning Parke Rankin, Lawrence, Kans., assignor
to Hercules Powder Company, Wilmington,
Del., a corporation of Delaware
No Drawing. Application April 25, 1936,
Serial No. 76,393
n
I
16
Claims.
(01. ail-2) . '
This invention relates to an improved method
of re?ning rosin and rosin esters and more par- '
ticularly to an improved method for removing
color bodies froin low-grade rosin and from es
5
ters of low-grade rosin.
‘
As is well known, both unre?ned wood and low
grade gum rosins contain both visible and latent
color bodies which render the rosin undesirable
‘for use in connection with the production of
10 various products where a light color is desired.
Heretofore, it has been known to re?ne rosin and
rosin esters by treatment with a selective solvent
for the visible and latent color bodies contained
in the rosin or rosin ester, ‘and a wide variety of
suitable selective solvents have been found for the
purpose; Thus, rosin has been dissolved in a
suitable solvent therefore, and the solution so
formed treated with an immiscible selective sol—
vent for the color bodies. After this treatment,
20 the rosin solution is separated from the selective
solvent and the color bodies and dark rosin dis
solved therein, and a light colored rosin recovered
by the evaporation of the solvent from the rosin
solution. Gasoline has been found to be a suit
able solvent for this re?ning treatment and has
25 been widely used for the purpose.
in petroleum ether and gasoline, so that selec
tive solvents extract the color bodies from rosin
solutions in normally gaseous hydrocarbons by
the method in accordance with this invention,
more e?iciently than from rosin solutions in pe
troleum ether or gasoline by the methods of the
prior art. A further advantage in the use of gas
eous hydrocarbons in accordance with this in
vention is completeness and ease with which
the hydrocarbon solvent may be removed from 10
the rosin after the re?ning operation.
Any grade of wood or gum rosin containing vis
ible and/or latent color bodies may be re?ned by
the method in accordance with this invention.
Likewise, esters of such rosins containing visible 15
and/or latent color bodies, with either monohy~
dric or polyhydric alcohols may be so re?ned.
Thus, esters of rosin with monohydric alcohols,
such as, for example, methanol, ethanol, propa
nol, butanol, amyl alcohol, cetyl alcohol, lauryl 20
alcohol,‘ stearyl alcohol,'furfuryl alcohol, hydro
furfuryl alcohol, abietanol, hydroabietanol, phe
nol, benzyl alcohol, etc., or with polyhydric alco
hols, such as, for example, ethylene glycol, di
. ethylene glycol, triethylene glycol, glycerol, sor
bitol, mannitol, erythritol. pentaerythritol, etc.,' 25
may be re?ned by my new method.
The object of this invention is to provide an im
The normally gaseous hydrocarbons which I
proved method vfor re?ning rosin‘ and rosin es
ters by treatment with the various selective color may use as solvents in the re?ning treatment in
body solvents known to the art, whereby a paler accordance with this invention are saturated and
30 rosin can be produced in a given yield, than has , ole?nic hydrocarbons containing two, three, and 30
been produced heretofore, or, if desired, a higher four carbon atoms, or mixtures thereof, such as,
yield obtained for a given improvement in color. for example, ethane, propane, butane, isobutane,
ethylene, propylene, butylene, isobutylene, and
Now, in accordance with my invention, I pro
vide a method for re?ning rosin, whereby a rosin mixtures thereof. In general, I prefer to use the
35 or a rosin ester is subjected to the solvent action
saturated hydrocarbons, propane, butane, isobu as
of a normally gaseous hydrocarbon or hydrocar
bon mixture {under conditions of temperature and
pressure such that the gaseous hydrocarbon is
held substantially in the liquid phase and to the
40 solvent action of a selective color body solvent
‘capable of immiscibility with the hydrocarbon,
and the solution of the re?ned rosin or rosin ester
in the hydrocarbon or hydrocarbon mixture sep
arated from the solution of color bodies in the se
45 lective solvent. Re?ned rosin or rosin esters may
be recovered from the hydrocarbon solution by
the evaporation of the hydrocarbon solvent. The
color bodies and dark rosin or-dark rosin ester
may be recovered from the selective solvent solu
50 tion by the evaporation of the selective solvent.
By the use of a normally gaseous hydrocarbon
I held in the liquid phase, ‘as a solvent in the selec_
tive solvent re?ning of rosin or a rosin ester, I
secure more e?lcient re?ning with a given selec
tive solvent than has been secured heretofore.
The reason for this appears to be that such hy
drocarbons are less active solvents for the visi
ble and latent color bodies of rosin or rosin esters,
60 than the higher boiling hydrocarbons contained
tane or mixtures thereof.
' The selective solvent for visible and latent color
bodies of rosin or of a rosin ester, which I use
in accordance with this invention may be any of
the various selective solvents for the color bodies
of rosin or of rosin esters used heretofore, which
are immiscible or substantially immiscible with
the hydrocarbon solvent. Thus. I may use fur
fural, furfuryl alcohol,'a substantially immiscible
chlorohydrin, as, ethylene chlorohydrin, propyl
ene chlorohydrin, etc., aniline, phenol, resorcinol,
ethylene glycol, propylene glycol, butylene glycol,
diethylene glycol, trimethylene glycol, glycerol,
butyl glycerol, ethyl formate, methyl acetate.
methyl formate, methyl orthonitrobenzoate,
-methyl furoate, allyl formate, monoacetin, di
acetin, triacetin, ethylene glycol monoacetate,
methanol, a hydroxyl alkyl amine, as trlethanol
amine, a solution of. oxalic acid in water or in
methanol, ethanol or other lower aliphatic alco
45
55
hol, ethylene glycol monoethyl ether, or' other
immiscible glycol ether, ethylene glycol mono
acetate, or other immiscible glycol ester. methyl
thiocyanate. ethyl thiocyanate, acetonitrile, acetic .9
2,117,572
The temperature at which this re?ning pro
acid, acetic anhydride, p-chloroaniline, resorcinol
plus hydrosulphite, a boron compound, ethylene
glycol diacetate, glycerol diacetate, resorcinol
monoacetate, resorcinol diacetate phenyl acetate,
furfuryl acetate, ethylidine diacetate, n-propyl
iuroate, ethyl glycollate, methyl‘ citrate, ethyl
tartrate, ethyl malonate, methyl maleate, dimeth—
cedure is carried out, may be any temperature
below the critical temperature of the normally
a gaseous hydrocarbon and below a temperature at
which substantial decomposition of the rosin oc Cl
curs. In general it will be found advantageous
to operate at normal room temperatures or below.
The use of temperatures below room temperature
yl phthalate, benzyl formate, monobutyrin, ethyl
is preferred since cooling renders the hydrocarbon
carbonate, methyl lactate, diethyl oxalate, methyl
10
adipate, hydroxyhydroquinone triacetate, methyl
chlorocarbonate, propylene glycol monoacetate,
16
hydroquinone diacetate, catechol monoacetate,
guaiacyl acetate, methyl glutarate, ethyl oxalate,
benzyl acetate, diethyl glutacoate, ethyl lactate,
diethyl phthalate, ethyl anisate, methyl salicylate,
methyl cinnamate, methyl mandelate, methyl
acrylate, ethyl oxamate, methyl succinate, ethyl
propiolate, methyl acrylate, ethyl malate, meth
-20
phase more immiscible with the selective solvent
phase. When desired, refrigeration can be ap
plied by external cooling, or by permitting a small
amount of the hydrocarbon to evaporate.
The method in accordance with this invention
may be carried out in a batch or in a continuous
process. In operating a continuous process, the
hydrocarbon phase and the selective solvent phase
oxybenzaldehyde, guaiacol, anisidin, nitroanisol,
may be contacted in concurrent or in counter
current ?ow as may be desired.
dichloroethyl ether, methoxy acetic acid, meth
yoxybenzyl alcohol, liquid sulfur dioxide, solutions
of amphoteric metallic halides, nitromethane,
may cite the following experimental procedure:
-As an illustration of the practical adaptation of
the method in accordance with this invention, I
Rosin and a selective solvent are placed in a
mixtures of such re?ning agents which are chem
ically non-reactive, etc.
In carrying the method out in accordance with
25
this invention, the rosin or rosin ester to be re?ned
is dissolved in a normally gaseous hydrocarbon
under a pressure and temperature such that the
stainless steel alloy pressure tube, cooling the
tube until it is well below the boiling point of the
hydrocarbon solvent to be used as a solvent, and
then adding the hydrocarbon in liquid form to the
tube.
in the liquid phase, and treated with a selective
solvent for the latent and/or visible color bodies
of the rosin or rosin ester, having a capacity for
tained, say for a period of about an hour. The
tube is then supported in a vertical position and
the two phases allowed to separate, after which
they are slowly valved out of the pressure tube,
separation of the layers being made by observing
the color and action of the escaping material and
changing receivers when all of one phase has been
drained oil. The rosin from each phase is then
recovered by evaporating oif the solvent and re
substantially immiscibility with the hydrocarbon
solvent, for example, by agitation of the selective
solvent with the rosin solution.
The tube is then sealed, warmed to room
temperature and then agitated in a mechanical
shaker until equilibrium of phases has been at
gaseous hydrocarbon is maintained substantially
Alternately, the
rosin or rosin ester per se, if normally a solid
preferably in powdered form, is treated with a
mixture of the normally gaseous hydrocarbon and
the selective solvent capable of immiscibility
40 therewith, under pressure and temperature such
that the normally gaseous hydrocarbon is main
tained substantially in the liquid phase. The
pressure required to maintain the hydrocarbon
moving the last traces under vacuum.~
40
The details of a series of examples in which
the foregoing procedure was used to re?ne FF
grade wood .rosin, using 'furfural as a selective
solvent, and the properties of the products pro
duced thereby, are given in Table I, in comparison 45
with an example following prior art procedure in
which FF wood rosin was refined with furfural
I in the liquid phase will depend upon the particular
hydrocarbon chosen, and upon the temperature.
. Thus, for example, when carrying out the process
at a temperature of 70° F., a pressure of 22 lbs.
per sq. in. is necessary to keep butane in the - as a selective solvent, and a liquid petroleum frac
as a rosin solvent, and
liquid phase, while a pressure of 115 lbs. per sq. tion (V. M. & P. Naphtha)
products produced thereby. 50
in. is necessary to keep propane in the liquid the properties of the
phase.
Again, the rosin or rosin ester may be
.
Table I
dissolved in a selective solvent capable of sub
Example No ______ __
l
2
3
4
Prior art
55
55
t
used
for
.si?g ____________ -.
l
i
Butane
l e t
350
250
~ 250
37. 5
23. 3
25
37. 5
50.0
31.1
20
50
50
ygllovibogd rlaitiiaig) 80A+2R 80+3R 80A+6%R
80A+%R
80A+9R
r
0!
ucc
'
re 11
’
.
rosin ____________ __
55. 3%
69. 2%
72. 8%
23, 5%
Yield
of diarlr‘rosiri
rom
Ill‘ ura
phase ___________ __
42. 9%
25. 3%
22. 4%
73. 6%
stantial immiscibiiity with a normally gaseous
70 hydrocarbon held in liquid phase, and re?ned
rosin or rosin‘ ester extracted therefrom by treat
ment of this solution with a normally gaseous
hydrocarbon under a\\pressure and a temperature
‘such that it is maintained substantially in the
\\
V.naphtha
M. & P.
'
' 250
i d
-
Propane
'
Grams oi FF ado
wood rosin aged.-.
Grams oi iurlur
used ____________ __
liquid phase.
Butane
VD “me 000.331.?“
Color,
rosn of
65
Butane
'
'
250
37. 5 60
’
73. 1%
25. 6%
In Table I it will be observed that the re?ned
rosin produced in accordance with the procedure 70
of this invention is of. substantially better color
than that produced by the prior art procedure.
If desired, the solution of rosin in the normally
‘gaseous hydrocarbon may be given several suc
cessive treatments with, the selective solvent. For 76
2,117,072
3
use of successive treatments the procedure de
3. The method of re?ning a material from the
scribed above is followed, except that after the group consisting of rosin and rosin esters by the
phases are allowed to separate, the pressure tube. removal of color ‘bodies therefrom which in
is cooled below the boiling point of the hydro
cludes subjecting the material in solution in a
carbon solvent ‘and only the selective solvent hydrocarbon having a boiling point below about
layer is allowed to drain from the pressure tube 30°C. under conditions of temperature and pres
and a fresh lot of furfural added and ‘the mix
sure such that‘ the said hydrocarbon is main
ture agitated in a mechanical shaker until equi
tained substantially in the liquid phase, to treat
librium‘ is attained, the tube supported in a ver
ment with a liquid having a capacity for selec
it tical position and 'the two phases allowed to
tively dissolving color bodies in the material and
separate. The re?ned rosin ‘and the dark rosin which is capable of immiscibility with the hydro 10
from the selective solvent layer may then be carbon and separating the selective solvent phase
recovered as described above, or the procedure and the color bodies dissolved thereby from the
repeated for further treatments with fresh lots
hydrocarbon solution phase.
of the selectivesolvents.
4.,The methodof re?ning a material from the 15
group consisting of rosin and rosin esters by the
removal of color bodies therefrom which in
cludes subjecting rosin in solution in a normally
gaseous aliphatic hydrocarbon under conditions
of temperature‘ and. pressure such that the said 20
hydrocarbon is maintained substantially in the
liquid phase, to treatment with ‘a liquid having a
The details of a series of examples in which
the foregoing procedure was used to re?ne FF
20
grade wood rosin, using three successive treat
ments with furfural as a selective solvent, and the
properties of the products ‘produced thereby are
given in Table II in comparison with a similar
treatment of three ‘successive treatments follow
ing prior art procedure, in which FF grade wood
rosin was re?ned with furfural as a selective sol
vent and a liquid petroleum fraction (V. M; 8: P.
naphtha) as a rosin solvent, and the properties
of the products produced thereby.
capacity for selectively dissolving color bodies in
the material and which is capable of immisci_
bility with the hydrocarbon and separating the 25'
selective solvent phase and the color bodies dis
solved thereby from the hydrocarbon solution
phase.
Table II
Example N0.__._..._.__.____ ....
5
'
Solvent used for rosiunu _.___.
Butane
.
5. The method of re?ning a material from the
group consisting'of rosin and rosin esters by the
6
Prior art
Butane
V. M. & P.
removal of color bodies therefrom ‘which ineiudes 4
‘
‘
Volume of solvent used in cc .. ,
250
250
37. 5
25
.
naphtha.
, 250
Grams of FF grade wood rosin
used ....... . ., ______________ _.
Grams nffurfural use(l...._.._. .
37.5
50
20
50
27A
45A
75.-\
23. 2%
43. 2'1,
49. 3%
76. 8%
53. 2%
49. 1%
(‘olor of refined rosin produced
(Lnvibond rnting)...__..
.. _
Yield of re?ned rosin _________ ..
,
Yield of dark rosin from [urfural
40
phases ........ _; _______ .7 . ., .
subjecting the material in solution in butane un-‘
der conditions of temperature and pressure such
that the said hydrocarbon is maintained substan
tially in the liquid phase, to treatment with a
liquid having a capacity for selectively dissolv
ing color bodies in the material and which'is
capable of immiscibility with the hydrocarbon
and separating the selective solvent phase and
the color bodies dissolved thereby from the by?
drocarbon solution phase.
6. The method of re?ning a material‘ from the
group consisting of rosin and rosin esters by the
It will be understood that the above examples
are given by way of illustration only, and that
the scope of‘my invention as herein broadly de-'
scribed and claimed is in no way limited thereby. - removal of color bodies therefrom which includes
What I claim and desire to protect by Letters subjecting the material in solution in isobutane
Patent is:
“
1. The method of refining a material from the‘
group comprising rosin and rosin esters “by the
removal of color bodies therefrom, which com
prises subjecting the material to the solvent
action of a normally gaseous hydrocarbon under
conditions of temperature and pressure such that
the said hydrocarbon is maintained substantially
in the liquid. phase and to the solvent action of
an appreciably immiscible liquid having a ca
pacity for selectively dissolving color bodies there
‘from, and separating, the solution of re?ned ma
terial in the normally gaseous hydrocarbon phase
60 and the solution of color bodies in the selective
solvent phase.
,
2. The method of re?ning a material from the
group consisting of rosin and rosin esters by the
removal of color bodies therefrom which includes
subjecting the material in solution ‘in a normally
gaseous hydrocarbon under conditionsof tem
perature and pressure‘ such that the said hydro
carbon is maintained substantially in the liquid
phase. to treatment with a liquid having a ca
' under conditions of temperature and pressure
such that the said hydrocarbon is maintained
substantially in the liquid phase, to treatment
with a liquid having‘ a capacity for selectively
dissolving color bodies in the material and which
is capable of immisc'ibility with the hydrocarbon
and separating the selective solvent phase and
the color bodies dissolved thereby from the hy
drocarbon solution phase.
_
7. The method of re?ning a material from the
group consisting of rosin and rosin esters, by the
removal of color bodies therefrom which includes
subjecting the material in solution in propane‘
under conditions of temperature and pressure
such that the saidhydrocarbon is maintained
substantially in the liquid phase, to treatment
with a liquid having’ a capacity for selectively
dissolving color bodies in the material and which
is capable of immiscibility with the hydrocarbon
and separating the selective solvent phase and
the color bodies dissolved thereby from the rosin 7
solution phase.
,
- 8. The method of refining a material from
the group consisting of rosin and rosin esters
‘by the removal of color bodies therefrom which 70
the material and which is capable of immisci
bility with the solvent for the material, and sepa~ {includes subjecting the material in solution ‘in a
rating the selective solvent phase and the color" 1’normally ‘gaseous hydrocarbon under conditions,
bodies dissolved thereby from the‘hydroc‘arbon of temperature and pressure such that the said‘
pacity for selectively dissolving color bodies in
solution phase.
hydrocarbon is maintained substantially in v‘the
liquid phase. to treatment with furfural, and
4
I
2,117,572
separating the furi'ural and the color bodies dis
solved thereby from the hydrocarbon solution. .
9. The method of re?ning a material from
the group consisting of rosin and rosin esters by
the removal of color bodies therefrom which in
cludes subjecting the material in solution in a
normally gaseous aliphatic hydrocarbon under
conditions of temperature and pressure such
that the said hydrocarbon is maintained sub
10 stantially in the liquid phase, to treatment with
furfural, and separating the furfural and the
color bodies dissolved thereby from the hydro
carbon solution.
15
20
25
'30
10. The method of re?ning a material from the
group consisting of rosin and rosin esters by the
removal of color-bodies therefrom which in
cludes subjecting the material to the solvent ac
tion of ‘butane under conditions of temperature
and pressure such that the butane is maintained
substantially in liquid phase, and to the solvent
action of furfural, and separating the Iurfural
and the color-bodies dissolved thereby from the
butane solution.
11. The method of re?ning a material-from the
group :consisting of rosin and rosin esters by the
removal of color-bodies therefrom which includes
subjecting the material to the solvent action of
isobutane under conditions of temperature and
pressure such that the isobutane is maintained
substantially in liquid phase, and to the solvent
action of furfural, and separating the furfural
and the color-bodies dissolved thereby from the
isobutane solution.
12. The method of re?ning a material from
35 the group consisting of rosin and rosin esters by
the removal of color-bodies therefrom which in
cludes subjecting the material to the solvent ac
tion of propane under conditions of temperature
and pressure such that the propane is maintained
40 substantially in liquid phase, and 'to the solvent
action of furfural, and separating the furfural
and the color-bodies dissolved thereby from ‘the
propane solution.
13. The method of re?ning a material from.
the group consisting of rosin and rosin esters by
the removal of color-bodies therefrom which in
cludes subjecting the material to the solvent ac
tion of a normally gaseous aliphatic hydrocarbon
under conditions of temperature and pressure
such that the said hydrocarbon is maintained
substantially in liquid phase, and to the solvent
action of a phenol, and separating the phenol and
the color bodies dissolved thereby from the hy
10
drocarbon solution.
14. The method of refining a material from the
group consisting of rosin and rosin esters by the
removal of color-bodies therefrom which includes
subjecting the material to the solvent action of
a normally gaseous aliphatic hydrocarbon under 15
conditions of temperature and pressure such that
the said hydrocarbon is maintained substantially
in liquid phase, and to the solvent action of
phenol, and separating the phenol and the color
bodies dissolved thereby from the hydrocarbon 20
solution.
15. The method of re?ning a material from the
group consisting of rosin and rosin esters by the
removal of color-bodies therefrom which in
cludes subjecting the material to the solvent ac 25
tion of a normally gaseous aliphatic hydrocarbon
under conditions of temperature and pressure
such that the said hydrocarbon is maintained
substantially in liquid phase, and to the solvent
action of an alkyl thiocyanate, separating the 30
alkyl thiocyanate and the color-bodies dissolved
thereby from the hydrocarbon solution.
16. The method of re?ning a material from the.
group consisting of rosin and rosin esters by the
removal of color-bodies therefrom which includes
subjecting the material to the solvent action of a
normally gaseous aliphatic hydrocarbon under
conditions of temperature and pressure such that
the said hydrocarbon is maintained substantially
,in liquid phase, and to ‘the solvent action of a 40
methyl thiocyanate, separating the methyl thio
cyanate and the color-bodies dissolved thereby
from the hydrocarbon solution.
.
vLANNING PARKE RANKIN.
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