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Патент USA US2113808

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2,113,808
Patented Apr-.12, 1938, > 7
'
comm STATES PATENT OFFICE
' anasos
mrrnon or REFINING AND HYDROGEN
ATING ROSIN AND PRODUCT THEREOF .
, Irvin W. Humphrey, Wiimington,_Del., assignor
to Hercules Powder Company, Wilmington, Del.
a corporation of Delaware
'
_
.
'
I‘
No Drawing. Application June 20, 1935,
Serial No. 27,579
31 Claims.
This invention relates to a method for re?ning
and hydrogenating rosin land to product thereof.
The method in accordance with this'invention
is applicable to rosins generally and is effective
Cl for the hydrogenation of unsaturated rosin acids,
such as abietic acid, pyroabietic acid,~ pim'aric
acid, etc. and to the refining of rosins, more
‘particularly, for improvement of color and in cer
(CL 87-2)
metal catalysts, such as palladium, and base
metal catalysts, such as nickel as regards the
necessity for employing high pressure where a
base metal catalyst is used. The Ellis patent does
not-disclose the use of any pressure in excess of 5
10 pounds, and' Brooks does not suggest any
specific pressure.
'
-
The speci?c methods described by the Brooks
and Ellis patents referred to are of no practical
tain cases for reducing the deleterious effects‘ of "
value whatever when using either base metal or 10
'10 color bodies. '
The method in accordance with this invention noble catalysts and made no‘ impression on the
art.
will be adaptable for the hydrogenating and re?n
Now in accordance with this invention it was
ing of gum~rosin, such as is obtained from living
that rosins generally could be‘hydrogenated
pine trees and ‘also to the hydrogenation and re ‘found
to a‘high degree 'of saturation of the rosin acids, 15
?nement of wood rosin, such as is obtained by
say, for example, saturation oi’ 50%-95% of the
‘extraction from dead pine stump wood, down theoretical
for the two double bonds of an un
wood, and the like. The method in accordance
rosin acid, as abietic, rendering them
with this invention will be effective to produce a saturated
high degree of saturation with hydrogen of the adaptable and highly advantageous for various ,
commercial uses, such asv in the production oi
o unsaturated rosin acids contained in resins and. . hydrogenated esters, for use as ingredients in gloss 20
at the same time, will be e?ective ,to improve the oils, ingredients in varnishes, etc., and in soap
color of rosins by combinationof hydrogen with
making. Further,_it was .found in accordance
visible color bodies contained by resins.
with
this-invention that, by hydrogenation, wood
More particularly, where the method is applied
rosin containing not only visible but latent color 25
. to the treatment oi'_ wood ‘rosin, which is known
bodies could be re?ned to a high degree with
to often contain certain color bodies generally reference
not only to a lightening 01’ its color, but
termed latent color bodies, which are normally also to a decreasing of the deleterious e?ect oi the
invisible, but which darken under certain condié presence of latent color bodies. ‘ -.
' ' tions, as when exposed to air in the presence of
The method in accordance with this invention 30
an. alkali, as where the rosin, is made into ‘a
comprises essentially treatment of a rosin, com
sodium 803D, particular advantage will be ob
tained in that not only will the visible color of prising ‘chie?y, for example, abietic acid, pyro
acid, pimaric acid, or the‘ like, or mixtures
the rosin be improved, but any latent. color bodies abietic
thereofand small proportions of resenes, color
will be combined with hydrogen and their darken
bodies and other components, as oxidized resin
ing under certain conditions will be inhibited.
which can be hydrogenated, with hydrogen
Brier to the concepts comprising this invention acids‘
1 various attempts have been made to hydrogenate in the presence of a base metal hydrogenation
rosins. Thus, for example, the patent to Ellis catalyst, as nickel, cobalt, etc., or activated mix
thereof, as‘nickel-cobalt, nickel-copper, etc.
.No. ‘1,249,050, dated December 4, 1917, discloses tures
under high hydrogen pressure and at an elevated' 40
an
alleged
method
of
eiiecting
the
hydrogenation
40
'
4
oi’ rosin by treatment of rosin with hydrogen in temperature.
More
speci?cally,
the
method
in accordance
the presence of a‘ nickel catalyst under about 10
pounds‘pressure. ‘Main, the patent to Brooks with this invention involves the treatment 01' a
rosin with hydrogen in the presence of an acti- ,
No. l,16'l,264,_dated January 4, 1916, discloses a
' method of hydrogenating rosin by the treatment vated base metal hydrogenation catalyst under a 45
of resin with hydrogen in {the presence of- a pressure within the range 200-l5,000 pounds per
square inch and at. a temperature within the
catalyst, indicated as nickel, _or the like, or pal
range of about 125° C». to about 225° C. Pro
ladium, .or the like. Both of these patents evi
dently refer to the treatment of gum" rosin, since vcedure under a pressure of less than 200 pounds
at the time of illing_oi' the application thereior,
’ wood rosin was little known. The Brooks patent
per- square inch will not be, productive 0! any 50 '
- e?ective reduction in the unsaturation, oi' the -
in distinction from the Ellis patent", does not dis ; double bonds or the rosin acid and it will be es
close procedure involving the use of any speci?c " sential that the contact of the rosin-with hydro-l
super'atmospheric hydrogen pressure, and neither
Y . makes nor suggests any distinction betweennoble
gen and the base metal catalyst be carried out
\ under a hydrogen pressurewithin the range 200- a‘
2
2,1 18,808
15,000 pounds, or within the narrower range
about 1,000-8,000 pounds, and generally, in the
average case, the treatment will be carried out
under a pressure within‘ the range about 2,000
5,000 pounds.
/
\
'
The method in accordance with this invention
will, as has been indicated, involve contacting of
the rosin with an activated base metal hydro
genation catalyst and with hydrogen under a
'10 pressure within the limits given and also at an
elevated temperature within the range about 125?’
C. to about 225° C. The requisite time ofv treat
ment will depend to an extent upon conditions
such'as pressurefparticular rosin treated, tem
perature of ‘contacting the reagents, degree of
activity of catalyst and the extent of hydrogena
tion, desired.
However, proceeding within the
limits of temperature and pressure essential in
accordance with this invention, the time of treat
20 ment will range from about 0.5 to about 5.0 hours
and generally within the range from about 1.0 to
about 2.0 hours.
‘
>
'
mercury, under' reduced ‘pressure with the in
jection of steamvor inert gas, extraction with a
selective color body solvent, as furfural, ?ltra~
tion, as through fuller’s earth, activated carbon, I
or the like, or otherwise, for'the removal to a 5
greater or less degree of various impurities, as
color bodies, visible and latent, oxidized resin
acids, etc., normally‘contained by rosins variously. ,
Again, the rosin before treatment with hydrogen
by the procedure in accordance with this inven
tion, may be subjected to distillation under vac—
uum for the removal of light ends with treatment of the residue or an intermediate fraction in
accordance with this invention. Likewise, ‘if
desired, the rosin, after treatment with hydro-.
gen by the procedure in accordance with this
invention, may be subjected to distillation under
a reduced pressure, say 5-30 mm. mercury,'or
under reduced pressure with'injection of steam
or inert gas, and a hydrogenated fraction orfrac
tions collected, and a hydrogenated residue ob
tained or refined with a selective solvent for col~
20
The product in accordance with this invention ’ or bodies, as furfural, phenol, etc., crystallization ,
will be radically distinguished from any products from
alcohol, etc.
I
known prior to the concept thereof where wood
The exact procedure precedent to or following 25
rosin ‘is treated or where a previously re?ned the treatment of ‘rosins with hydrogen will be,
wood or gum rosin is treated, by the fact that selected with reference to the particular charac
it will comprise a rosin, the double bonds of the teristics desired for the hydrogenated product. ’
rosin acid of which, as abieticE acid, pyroabietic Thus, for example, where maximum lightness. of
30 acid, pimaric acid, and the like, will be saturated
visible color and, where'present in the original
with hydrogen to at least 50% of theoretical and rosin, a maximum modi?cation in latent color 30
- desirably tooan extent of about 60%-95%, ‘and
bodies, as such, is desired, the rosin will desirably
generally within about the range 65%-85%. be given a re?ning treatment, as by selective sol
The high saturation with hydrogen characteris- - vent extraction with furfural, phenol, etc., crys
tic of products inaccordance with this invention , tallization from alcohol, or the like, before treat
will be a direct result of the procedure for effect
ment with hydrogen, under pressure in the pres
ing ‘hydrogenation of rosins in accordance with ence of a base metal hydrogenation catalyst, ~
this invention and in particular of the procedure which under such circumstances will not only
in' the presence of a base metal hydrogenation‘ effect the high degree of saturation of the rosin
40 catalyst under the essential pressure conditions
acids indicated, but will also eifectively convert 40
indicated.
.
residual visible, and, if present, latent color bodies.
The product in accordance with this invention
Where a hydrogenated product of increased
will be further characterized by the fact that melting point is desired, distillation of the rosin
most of the visible color bodies of the rosin will under‘ reduced pressure for the removal of low
45 be converted into color body-hydrogen combi
ends, may be accomplished before the treatment 45
nation products, which will be substantially col
With-hydrogen.’ Thus, for example, where .‘a
orless, and as a consequence the hydrogenated product of increased melting point is desired,
rosin, the product of this invention, will be dis- ' ' the original rosin may be ?rst distilled under a
tinguished by improved or lessened color. Fur
of 5-30 mm. mercury until about 5-15%
'50 ther and more particularly where the product pressure
of the original rosin has been distilled oi, and
in accordance with this invention is produced ‘the residue then‘ subjected to treatment with hy 50
through treatment of wood rosin’ by the method drogen or the distillation continued or one or
embodying this invention, it will be distinguished more cuts collected and subjected to hydrogena
not only by a high degree of saturation with tion, as-previously described.
55 hydrogen of the rosin acid and conversion of
Further, where products having particular‘
-visible color bodies into colorless products, but characteristics as, for example, melting point,
by the fact that any latent color bodies normally purity, or the like, are desired, the original rosin
contained by wood rosin will have ‘been convert
may be fractionated, as by distillation under re- .
ed into latent color body-hydrogen combination duced pressure, treatment with a selective color
products and the deleterious effect normally body solvent, as furfura'l, phenol, etc., or by crys
found from the presence of latent color‘ bodies tallization from a solvent, as methanol, acetone, v60
- i
will be largely inhibited.
.
'
ethyl alcohol, etc., and any desired or selected
In proceeding for the carryingout of the meth
fraction‘ or fractions subjected to treatment with
od in accordance with this invention for the 'pro
hydrogen. Where a product of high purity is
duction of products in accordance therewith, desired, as has been indicated, the rosin product
rosins as such, comprising largely abietic, plmaric, after treatment with hydrogen, may be subjected
and the like, rosin acids, or mixtures thereof and to fractionation, as by distillation under reduced
65
- resenes and also including appreciable amounts
of visible color bodies, oxidized resin acids,- and,
in the case of wood rosin, also, of latent color
bodies, etc., and other ingredients found nor
mally in rosins, such as wood- and gum rosin, may
V be treated directly.
the rosin may ?rst _
115
be subjected to a re?ning treatmenasuch as dis
tillation under
pressure, say 5-30 mm.
pressure, treatment with a selective color body sol
vent, as furfural, phenol, etc., or by crystallization
from a solvent; as methanol, acetone, ethyl alco 70
hol, etc. for the production of a hydrogenated
fraction or fractions having desired character
istics, or the hydrogenated product may be sub
jected to a re?ning treatment in solution with
activated carbon, fulier's earth, or the like, or 75
.
3
9,118,808
anate value of about a3, a melting point‘of 77.5"
with a C., an acid number of about 161 and will grade n
extraction in solution in 'a suitable solvent
v
selective color body solvent, as iurfural, etc., which ‘in color.
is substantially immiscible with the rosin solvent,
From the above comparison of characteristics
as gasoline, which re?ning procedure will be of the original rosin subjected to treatment with
facilitated by virtue of the conversion of'visible similar characteristics oi the hydrogenated prod
and, where present. latent color bodies, into uct, it will benot‘ed that color has been substan
color body-hydrogen products.
tially improved and that the melting point has
For procedure in accordance with the method. been slightly reduced. As indicated above, the
hydrogenation catalyst, such as nickel, cobalt,
product will show a saturation equal to about 10
54% or the theoretical for the two double bonds
etc., and activated mixtures thereof, as copper
of the abietic acid.
embodying this invention any suitable base metal
' nickel, nicke1-cobalt,,etc., supported or unsup
'
_ As -further speci?cally illustrative, for example,
ported and prepared by any well known method, , 200 parts of I grade wood rosin, procured by re
in an activated state may be used. The base met
?ning ordinary vFF‘ wood rosin with ‘turfural ‘ac 15
al catalyst will be used in suitable form or suit
cording to the procedure described in U. S.-P. No.
~
ably supportedr Thus, for example, the base
metal hydrogenation catalysts, pure or admixed
may be agitated in ?nely di
‘with their oxides,
vided state in admixture with hydrogen under
pressure and the rosin under treatment, or the
20
base metal catalyst may be supported on‘any
suitable support, such as pumice, kieselguhr, or’
the‘ like.v The rosin for treatmentvwill be in a
?uid state, to which it may be brought by the ap
plication oi! suitable temperature, or'where hy
25 drogenation is e?ected at a temperature'below
- that at which the rosin is desirably ?uid, by dis
solving it in any suitable solvent, such, for ex
ample, as certain petroleum hydrocarbon cuts
such as gasoline, light mineral naphtha, etc'., a '
'30 suitable alcohol, as ethyl, or in solution inether,
~ acetic acid, etc., or other suitable. solvent from
which the hydrogenated‘products may be recov
ered. For the rosin may be rendered ?uid by use
1,715,008, is agitated with 2% of an active, suit
ably supported nickel hydrogenation catalyst at
180-190’ C. in an atmosphere of hydrogen under ‘
1800-2200 pounds per sq. in. hydrogen pressure 20
for a period of 1.5 hours. The rosin when ?ltered
from the catalyst will grade N in color and will be
saturated to 61% of the theory required for two
double bonds. By hydrcgenating at 3000-3500 a
pounds per sq._in. pressure, a saturation of ‘70% 25
75% will be attained when using a‘ highly active
Ni catalyst. If the catalyst is not of high activity, '
considerably higher hydrogenation'pressures will
be required to attain the stated degrees of hydro
genation.
30
In practical adaptation of the method in, ac
cordance with this invention, rosins may be hy
drogenated by the procedure described in the
abpv'e examples with use, however, of increased
hydrogen pressures and for periods or about 0.5 to 35
of both heat and solvent. '
2.0 hours. Thus, proceeding at temperatures of
> As illustrative of practical procedure in accord- * about 125° C.-225° C. and contacting the rosin in '
-40
ance with the method embodying this invention a ?uid state with an active‘ base metal hydrogen-1
for, the hydrogenation of wood rosin, as such, or ation catalyst, with the use of hydrogen pressures
fractionated, or pretreated as indicated above, for in excess of 200 pounds, say, for example, pres-‘ 40
example, a‘ quantity of molten rosin is mixed with ' ‘ sures within the range 2,000-5,00'0 pounds per sq.
2% 01' active nickel hydrogenation catalyst sup
ported on 'kieselguhr. Hydrogen is then con
tasted with the molten rosin for a period of about
?ve hours, the resin being agitated by shaking
the reaction vessel‘ at a temperature of about 200°
45 C. and under a hydrogen pressure or about 200
in., the products‘ will be distinguished by hydrog
gen saturation of about 60% to about 80%, while
proceeding with the use of pressures in excess of
5,000 pounds the ‘products will be distinguished 45
pounds. During the treatment the molten rosin
and catalyst are agitated. ' On completion of the
treatment the catalyst is ?ltered from the rosin,
or separated by dissolving the resin with a sol
v50 vent, such' as ether and ?ltering, by distillation
by hydrogen saturation up to 95% of theory.
‘ In proceeding in accordance with the above ex
amples and with the use of pressures within the
range‘ 200—15,000 pounds per sq. in., indicated as
essential, the products will be distinguished by a 50
hydrogen saturation of 50%-95% and also by the
presence or color body-hydrogen combination
under reduced pressure, by combinations of dis
products, which, in the case of visible color body
solving, ?ltering and distilling, or in any other
hydrogen combination products will‘ result in im
proved color due to the lack of color of such prod 55
ucts and, in the case oi’ latent color body-hydro
gen products, will result in improved product due
to inhibition of the deleterious e?ects produced
convenient manner.
'
Following the above procedure under the con
:ditions of temperature and pressure. indicated
highly, active nickel hydrogena‘tior;
a u
by normal latent color bodies.
for the double bonds oi’ abietic acid and to be
“ v
The conditions given above with reference to
etc. will be generally ap
pressure, temperature,
60
of substantially improved color by virtue oi’ the _ plicable to procedure involving the hydrogena
conversion oi’ visible color bodies into colorless ‘tion of rosin‘ in solution and the hydrogenated
combination products. The
‘color body-hydrogen
distilled under 65
wood rosin product will, unless ‘it rosin product may, orii desired,'be
- hydrogenated
otherwise treated as de
reduced
pressure,
were very‘ thoroughly re?ned prior to hydrogena
scribed herein.
‘I
t
v
tion, ‘contain latent color body-hydrogen combi
The products produced by procedure in .ac
nation products.
,
'1 '
'
As more speci?cally illustrative of the product, cordance with this invention‘, for example,_as il
indicated, be‘ 70
assuming the original material to have been a lustrated above, may, as has beenby
distillation, .
re?ned wood rosin having, tor example, an iodine " subjected to further treatment, as
70 number (Hanus method)v of 290, a thiocyanate
under reduced pressure, fractionation under re
value of about 80, a melting point (drop method) duced pressure, extraction with a latent color body
of about 80° 0., an acid number oi’ about 165 and
grading I in color, the product will have an iodine
‘number (Hanul method)
of about 216, a thiocy- -
solvent, crystallization from alcohol, treatment
with activated carbon, Iuller's earth, and the like, 75
4
2,113,808
for the production of products of desired charac
teristics or improved purity.
the treatment with selective color body solvent
-
Thus, for example, the rosin having been
treated with hydrogen under the conditions indi
- cated, may be fractionated under reduced pres
sure and a fraction or fractions havinglimproved
10
color and desired boiling range characteristics
selected. Again, the rosin having been treated
with hydrogen, it may be re?ned by treatment in
will not only reduce the contentot visible color
bodies, but will also reduce any content of latent
color bodies ‘in the wood rosin.
'
The subsequent treatment with hydrogen will
not onlyresultin a product of high‘ saturation
with hydrogen, but'the treatment will be effective
to convert residual visible and latent color bodies
into color body-hydrogen combination ‘products
Solution with a selective color body solvent, such . with
the production of a product of substantially
'10
as furfural, furfuryl alcohol, liquid sulphur diox
ide, ethylene chlorohydrin, a suitable phenol, as higher color grade than- obtainable by the mere
. '
ordinary carbolic acid, etc. Thus, for example," extraction with a color'body solvent.
It follows that, if desired, rosin prior to treat
a light petroleum distillate solutionof the hydro
.15 genated rosin may be re?ned by shaking the solu
ment with hydrogenmay be dissolved in a suit
able solvent, as, for example, a light petroleum 15
tion with a quantity of furfuraL'permitting sepa
ration of the rosin solution and selective color - distillate, and the solution subjected to treatment
body solvent and drawing off the rosin'solution, with activated carbon or fuller’s earth, as by con
tacting with activated carbon or fuller’s' earth,
as more particularly described, for example, in and
?ltration.
.
.>
20 United States Letters Patent No. 1,715,088, dated
it will, now be appreciated that the method in
May 28, 1929, to Kaiser and Hancock.
The rosin having been ,treated with hydrogen,
subsequent re?ning-of the rosin may also be ac
complished by forming a solution of the treated
rosin in a suitable solvent, as a light petroleum
distillate, and contacting the'solution with acti
vated carbon, fuller’s earth, or the like, and iii
tering.
, accordance‘ with this invention involves essen
tially the treatmentlof a rosin, as such, or a iraction 'or residue thereof, or subjected ‘to prior
'
treatment for the removal of impurities, {with
hydrogen under a pressure of not less than 200 25
pounds in ‘the presence of an active base metal
hydrogenation catalyst, preferably nickel, and
If desired, the rosin before treatment with hy-' ' that thereby a product having .a high satura:
30 drogen, may be subjected
to distillation under any tion,fnot less than 50% saturation, of the’d'ouble
well known conditions for the distillation or a bonds ofv the rosin acid is obtained; and further 30
rosin without decomposition thereof, as under that the rosin‘ is, by thetreatment, re?ned in
reduced pressure, until say about 85% - of the that visible color bodies contained by the rosin, or
residual visible color bodies, if the rosin has been
rosin
over. The distillate is then sub
I 35 Jectedistodistilled
subjectedv to a re?ning treatment, are converted
treatment with hydrogen as exempli
?ed‘above. The advantage gained by distillation ' into bodies‘ with less color, thus improving the
under reduced pressure prior to treatment with visible color grade of the rosin; and that‘ likewise
where the rosin contains latent color- bodies, or
hydrogen under pressure will be especially notice
latent color bodies, such. are converted
able in the case of wood rosin, since the distillate . residual
into hydrogen combinationproducts and their .
40 will be largely free from visible color bodies. -The
_
.
product of the treatment of .the distillate with deleterious effect modi?ed.‘
40.
The
hydrogenated
rosin‘
produced
in
-accord<
hydrogen in accordancewith this invention, how
ance
with
the
method
of
this
invention,
aside
from
. ever,‘ will usually be of improved visiblecolor over
its high saturation with hydrogen, i. e. ,50%-90%
that of the distillate and will, in addition to hav
of theory,
_
be peculiarly characterized where
1
ing the high saturation with hydrogen obtainable, the originalwill
rosin
comprised
‘wood
rosin,
by
the
contain latent color body-hydrogen combination presence of_ latent color bodies-hydrogen com
products. As will be ‘appreciated, rosin before
treatment with hydrogen in accordance with this - bination products. ~ Where the original rosin
comprised wood or gum rosinv which had been
invention, may be ?rst subjected to distillation
_
' previously subjected 'to a re?ning treatment, as
50 under vacuum for the removal of light ends and
then distilled under reduced pressure for the ob» by‘dis’tillation under reduced pressure, fractiona-,
taining of a fraction or of a plurality of fractions, tion under reduced pressure, treatment with a
selective solvent for color bodies, or other re?ning
which will then be treated with hydrogen as ex
treatment, 'or where subsequent to hydrogenation
ampli?ed above.
'
Prior to treatment of the rosin with hydrogen,
if desired, the rosin may be dissolved in a suitable
solvent, as for example, a light petroleum .dis-v
' I tillate, as gasoline,'and the solution extracted by
treatment with a latent color body solvent, such
60 as those mentionedabove, by, for example, pro- ‘
cedure outlined in United States Patent No.
1,715,088 to Kaiser and Hancock. The rosin solu
tion having been separated from the selective
color body solvent, an active base -metal hydro
65
genation catalyst, as nickel in powder form, or
‘ suitably supported, may be contacted ‘with the
solution and the treatment with hydrogen under,
for example, 1500‘ to 4000 pounds per sq. in. vpres
sure and ate.‘ temperature of, for example, 150
to 200° C. then carried out, or the re?ned rosin
may ?rst be recovered from the solution and
then hydrogenated in molten condition or re
dissolved in a suitable solvent, ‘as gasoline. The
advantage of such procedure will be especially
noticeable in the case or wood rosin inasmuch as
the hydrogenated rosin isv subjected to‘ distillation - '
under reduced pressure, fraétion‘ally distilling
undero reduced pressure, treatment with ‘a'selec
55
tive color body solvent, or other re?ning treat
ment, the hydrogenated rosin productT-will be
‘-. characterized by the fact that it will be substan
tially free ,from hydrogenated, ‘oxidized resin
acids, and the'hydrogenated rosin product will be '
very low in, petroleum ether and toluene insol
ubles. Further, the hydrogenated wood rosin
produced in accordance with the method of this
invention by hydrogenation of previously re?ned
rosin will be characterized by a thiocyanate value 05
(rhodanometric iodine value)‘ within about the
range 5-50 as compared with a thiocyanate value
within about the range 80-95 ,for non-hydro
genated rosin. The color- of the hydrogenated
rosin' product will be light’ and in certain cases 70
may be-at least as good, if_ not better, than that
of the WW grade.
'
-
a
It will be appreciated ‘that the product in ac!
cordance witht-his invention, will be a rosin.
5
2,118,808
“l a fraction, or residue thereof having a_ saturation
with hydrogen of 50% or more, will contain color
body-hydrogen combination products, and in the
case of incompletely re?ned wood rosin will also
contain latent color body-hydrogen combination
products. The product will be adaptableeand
within the range of about 200' to about 15,000 ‘
lbs. per sq. in, in the presence of an active base
metal hydrogenation catalyst and at an elevated
temperature adapted to effect addition of hydro
.gen to the unsaturated bonds of the rosin acid
until the rosin acid-1' is at least 50%, saturated -
hydrogen.
,
for a wide
variety of ’ com-' with
,
3. The method of re?ning and .hydrogenating' '
mercial uses, such as in the formation of hydro
a rosin,'which comprises subjecting a rosin to.
gen'ated rosin acid esters, as an ingredient of treatment with hydrogen under a pressure within
highly advantageous
gloss oils, varnishes, etc., for use‘in the making the range of about 200 to about 15,000 lbs. per
soaps, etc. '
- ‘
in. andat a temperature of about 125° _C. to
Bywayof illustration, for example, rosin after so.
about 225°C. in the presence of inactive base
hydrogenation to within about the range ‘.01 metal hydrogenation catalyst until the rosin acid
50%-90% of theory, and preferably supplementedv 1 ‘is at 'least.50% saturated with hydrogen. '
,
'
10
of
15
15 before or after‘ hydrogenation by a re?ning treat
, 4. The method of re?ning and hydrogenating
ment in the case of wood rosin, as by distillation; ‘a rosin, which comprises subjecting wood rosin ._ ,
under reduced pressure, fractionally distilling
to. treatment with hydrogen ‘under a pressure I
withir‘nthe range 'of about 200 to about 15,000
lbs. per’ sq. in.‘ and at a temperature‘ of about 20:
under reduced pressure, extraction with a selec- -
tive color body solvent, or otherwise, may be es
as
20 teri?ed by heating with a polyhydric alcohol,
glycol,
125° C. to about 225° C. in the presence of an’ , v
‘ ethylene glycol, propylene glycol, butylene
active baseimetal-hydrogenation catalyst until
glycerol, pentaerythrite,_,trimethylene glycol, di-_
saturated with '
the rosin acid is at least 50%
ethylene glycol, triethylene glycol, etcJorL esteri
hydrogen.
'
-
.
'
‘
'
"
._
l
5. ‘The method of re?ning and hydrogenating 25
' . ?ed by heating with a monohydric - alcohol, as
methanol, ethyl alcohol, a butyl alcohol, a propyl a rosin,.which comprises subjecting a-‘rosin to alcohol, an amyl alcohol, tetrahydro-furfuryl ' treatment with hydrogen under a. pressure,‘ within
alcohol, borneol, fenchyl alcohol, cyclohexanol,
stearol, lauryl, oleyl, hydrogenated abietyl alco
hol, also by_ the monoethyl -methyl or -butyl
> the range of about 200-to about 15,000 lbs. per
sq. in. and at a temperature of about 125°v Cato 30
about 225° C. in-the presence‘ of an active nickel
hydrogenation catalyst until'the rosin acid 'is at
ethers of ethylene or diethylene glycol, or by
30
other suitable alcohols.
f
.
, least 50% saturated with hydrogen. ’
In proceeding in accordance with this inven
a rosin, which comprises subjecting wood’ rosin -.
35 genation.
Further, rosin having been subjected
to hydrogenation the hydrogenated product may
be heat treated. Heat treatment, either before
or after hydrogenation, may be given irrespec
tive of other treatments, as re?ning, fractional
'
6. The method of re?ning and hydroeenatmg _
tion the rosin may be subjected to a preliminary
heat treatment before it is subjected to hydro
-
distillation, etc., to which the rosin or hydro
genated. product may be vsubjected as-desc'rlbed
herein. Heat treatment of the rosin, either be
to treatment with hydrogen under a'pressure 35
within the range of about .200 to about 15,000-v
lbs. per sq. inpandt at a‘ temperature ofabout
125° C. to about 225° .C. in the presence of an
active nickel» hydrogenation‘ catalyst until the (0 rosin, acid is at least 50% saturated with hydro
gen.
_
‘
-
'
7. Themethod of re?ning and hydrogenating .
a rosin, which comprises distilling oil.’ a light end
fore or after hydrogenation, will generally com- _ from a rosin and subjecting the residue to treat
'45
prise heating of the rosin or hydrogenated rosin
product at a temperature of, for-l example, from
about 275° C. to about 325° C., for a period of,
for example, from about 0.2,hour to about 3.0
hours under atmospheric or higher pressure.
ment with hydrogen under a pressure within
the range of about 200 to about 15,000 lbs. per .
sq. in: in the presence of an. activev base metal
. hydrogenation
catalyst" and at‘ an elevated tem- .
perature adapted to effect addition of hydrogen
The heating will desirably be carried out in an . to the unsaturated bonds of the rosin acid until
inert
atmosphere
as,
for
example,
an
atmosphere
50
‘the rosin acid is at least 50% saturatedwith
of carbon dioxide.
.
‘
As will be appreciated, the rosin may be heat
8. The method of re?ningand hydrogenating
treated before or after re?nement 'or before or
which comprises fractionating a resin
' a rosin,
after fractional distillation and then hydrogen
andsubjecting a fraction of the rosin to treat
55 ated, or the hydrogenated product may be heat ',ment with hydrogen under a pressure within the
treated after hydrogenation and either before
‘
200to about 15,000 lbs. per-sq. in‘.
_ range of about
or after fractional distillation.
' _
in the presence of an active 'base metal hydro
This application is a continuation in part of genation catalyst and-at an elevated temperaturev
my application Serial No. 419,748, ?led January ‘‘ adapted to effect addition of hydrogen to the,
60 9, 1930;
‘unsaturated bonds of the rosin acid until the.
What I claim and desire to protect by Letters rosin acid is at ‘least'50% saturated with‘ hy
hydrogen._
Patent
is:
-
.,
-
r
_ l. The method of re?ning and hydrogenating
a rosin, which comprises subjecting a rosin to
05 treatment with hydrogen under a pressurewithin
the range of about 200 toabout 15,000 lbs. per
sq. in. in the presence of an active base metal
drogen.
=
i
.
-
'
'
9. The method of re?ning and hydrogenating
a rosin, which comprisesseparating color bodies 65
from a rosin acid and subjecting the thus re?ned
rosin to treatment with hydrogen under a pres
sure within the range of about 200 to-about 15,000
hydrogenation catalyst and at an elevated tern-'
lbs. per sq. in. in the presence of an active base'
perature adapted to e?ect addition of hydrogen a metal
hydrogenation catalyst and at an elevated 70
of therosin acid until temperature adapted to effect addition of hydro
70 to the unsaturated bonds
the rosin acid” is at least 50% saturated with a gen to the unsaturated bonds oi' the rosin acid
hydrogen.
'
i 2. The method of re?ning and hydrogenating
a rosin, which comprises subjecting wood rosin
to treatment with hydrogen ,under a pressure
until the rosin acid is at least 50% saturated
with hydrogen.
“
10. The method of re?ning and hydrogenating I
l
6
2,1 13,808
a rosin, which‘ Comprises subjecting a rosin in
solution to treatment with hydrogen undera
pressure within the range of about 200 to about
15,000 lbs. per sq. in. and at a temperature of
about 125° C. to about 225,” C. in the presence of
an active base metal hydrogenation catalyst until
the rosin acid is at least 50% saturated with hy
drogen.
'
v
11. The method of re?ning and hydrogena'ting
a ‘rosin, which comprises subjecting a rosin to
treatment with hydrogen under a pressure with
in the range of about 200 to about 15,000 lbs. per
sq. in. and at a temperature of about 125° C. to
then subjecting the rosin to treatment with hy
drogen under a pressure within the range of
about 200 to about 15,000 lbs. per sq. in. in' the
presence of an active base metal hydrogenation
catalyst and at an elevated temperature adapted
to effect addition of hydrogen to the unsaturated
bonds of the rosin acid until the rosin is at least‘
50% saturated with hydrogen.
20. The method of re?ning and hydrogenating
a rosin which comprises heating rosin to an ele
10
‘vated temperature in an inert atmosphere, main
taining the rosin at such temperature without
substantial distillation for a substantial period of
time, and then subjecting the‘rosin to treatment
with hydrogen under a pressure'within the range 15
of about 200 to about 15,000 lbs. per sq. in. in the
' about 225° C. in the presence of anactive base
15 metal hydrogenation catalyst until the rosin acid
is at least 50% saturated with hydrogen.‘ and
treating the ‘hydrogenated rosin for the separa
tion of color’ bodies therefrom.
12. The method of re?ning and hydrogenating
presence of an active base metal hydrogenation
catalyst until the rosin acid is at least 50% sat
urated with hydrogen.
20 a rosin, which comprises subjecting a rosin to
treatment with hydrogen under a pressure with-'
in the range of about 2,000 to about‘5,000 lbs. per
'
.
21., A product derived from a rosin containing 20
color-bodies and comprising a rosin acid which
has been subjected to a hydrogenation treatment
by which its unsaturation has been reduced at
‘sq. in. in’ the presence of an active base metal
hydrogenation catalyst and at an elevated tem
25 perature adapted to effect addition of hydrogen - least 50% by hydrogen, and which has been heat
to the unsaturated bonds of the rosin acid until
the rosin acid is at least 50% saturated with hy
drogen.
'
,
-_
13. The method of re?ning and hydrogenating
'30 rosin which comprises subjecting rosin at an ele
vated temperature to treatment with hydrogen
treated, in a treatment distinct .from the said
hydrogenation treatment.
-
22. A product derived from a rosin containing '
color-bodies which has been subjected to a hy
drogenation treatment by which its unsaturation
has been reduced at least 50%_by hydrogen and 30
which has been heat-treated for a period of from
under a pressure-within the range of about'200 about 0.2 hour to about 3 hours at a tempera
to about 15,000 lbs. per sq. in. in the presence of ‘ ture within the range ‘of about 275° C. to about
a-base metal catalyst until the rosin is at least
50% saturated with hydrogen and then subject
ing the hydrogenated rosin to distillation under
reduced pressure.
-l4.'A hydrogenated rosin derivative charac—'
terized by substantial freedom from hydrogenata
325° C., in a treatment distinct from the said
hydrogenation treatment. .
,
g
.
23. A hydrogenated rosin, the unsaturatlon of
which has been reduced by at least 50% of
theoretical for, two double bonds of its unsat
urated’ rosin acids by combination with hydro
'40 ed oxidized resin acids and by having its un- . gen.
.7
40
saturation reduced by at least 50% by hydrogen.
24. A hydrogenated wood rosin, the unsatura
15. A product derived from a re?ned-rosin con
tion of which has been reduced by at least 50% I
taining color bodies and comprising a rosin acid
the unsaturation of which is reduced at least
45 50% by hydrogen.
‘
of theoretical for two double bonds of its ‘unsat
urated rosin vacids by combination with hydro
gen.
1
gen.
v '60
_
.
16. A product derived from a re?ned rosin‘ con
25. A hydrogenated gum ros'in, the unsatura
taining color bodies and comprising a rosin acid . ‘tion
of which has been reduced by at least 50%
the unsaturation of which is reduced atleast
of
theoretical
for two double bonds oflits-unsat
50% by hydrogen and a substantially colorless
product of the combination of hydrogen with urated rosin‘acids by combination with hydro~ _
color bodies contained. in the rosin.
26. The method 01' hydrogenating a rosin
'17. A product derived from wood rosin con
which comprises subjecting a rosin to treatment
taining latent color bodies and comprising a rosin _ with hydrogen under a pressure within the range
acid the unsaturationof which is reduced at
about 1000 to about 8000 lbs. per sq. in. and
least 50% by hydrogen and'a product of the of
combination of hydrogen with-latent color bodies at a temperature of about 125° C. to about 225°
C. in the‘ presence of an active base metal hydro
contained in the wood rosin.'
genation catalyst until the rosin is at least 50%
18. The method of re?ning and hydrogenating saturated with hydrogen.
,
'
_
a rosin which comprises heating rosin to an ele
27.
The
method
of
re?ning
and
hydrogenat
'vated temperature, maintaining the rosin at such ing a rosin, which comprises subjecting a rosin
temperature without substantial distillation for _to
treatment with hydrogen under a pressure __
a substantial periodo'f time, and then subject
ing the‘, rosin to treatment with hydrogen under
a pressure within the range of about 200v to about
65 15,000 lbs. per sq. in. in the. presence of an active
base metal hydrogenation catalyst and at an
elevated temperature adapted to e?ect addition
of hydrogen to the unsaturated bonds of the
rosin acid until the rosin acid is at least 50%
saturated with hydrogen.
'
.
,
' within the‘ range of about 200 to about 15,000 lbs. ~
per sq. in. and at a temperature within the range
of about 180° C. to about 190° C. in the presence
of an- active. base-metal hydrogenation catalyst 65
until the rosin acid is at least 50% saturated
with hydrogen.
'
I
28. A hydrogenated rosin, the unsaturation of
which hasbeen reduced to an extent within the '
range of about_50% to about 95% of theoretical
for two double bonds of its unsaturated rosin
19. The method of re?ning and hydrogenating
a rosin which comprises heating rosin to a tem
acids by combination with hydrogen. .
perature‘within the range of about 275° C. to'
The method of re?ning and hydrogenating
about 325° C., maintaining the rosin at such tem ,a 29.
rosin which comprises subjecting a rosin in
perature for from about 0.2 to about 3 hours, and solution, in a suitable
hydrocarbon solvent to
7
treatment with hydrogen under a. pressure with
in the range of about 200 to about 15,000 lbs. per
‘sq. in. and at a temperature 0! about 125° C. to
about 225° C. in the presence. of an active base
genation catalyst until the resin acid is at least
50% saturated with hydrogen.-
.
31. The method of re?ning and hydrogenat
ing a rosin which comprises subjecting a rosin
metal hydrogenation catalyst until the rosin acid ' in solution to treatment with hydrogen under a
pressure within the range of about 200 to about
is at least 50% saturated with hydrogen.
30. The method of re?ning 'and hydrogenating 15,000 lbs. per sq. in. and at a temperature '0!
a resin which comprises subjecting a resin in about 150° C. to about 200° C. in the ‘presence
of an active base metal hydrogenation catalyst
solution in a suitable alcohol to treatment with _
hydrogen under a pressure within the range 0! imtil the'rosin acid'is 'at‘least 50% saturated 10
‘
about 200 ‘to about 15,000 lbs. per sq. in. and at with hydrogen.'
mvm w.
a temperature of about 125° C. to about 225° C. -
in the presence of an- active base metal hydro-'
GERTIIFIGA‘I'E" or CORRECTION; ,
Patent no ,-~ 2,113 ,éoa .
'April 12, 1958. I
'IRVIN w. ‘mam.
Itfis hereby certifiedilithat error appears. _ in the - printed specification
,ofthe aboye numbered patent requiring correetionas follows: Page 1,- second
col‘unm,‘ line 11,-after.'!noble'_' insert theavord metal; page 2,‘ second c'olmi'm,
line Latter ‘mercury,’ insert or; and that the said Letters Patent should
be. read with ‘these -.co_r_re_ct1ons therein thanthe same mayeonform‘to the
record of the ‘case
Patent Office.
'
>
‘
'
I
351;»? and‘ aealedthis 1mm- day or JuneLAaD. 1933..
Hem-77 Van Arsdale',
Acting Commissieneref- ,Patentsr
7
treatment with hydrogen under a. pressure with
in the range of about 200 to about 15,000 lbs. per
‘sq. in. and at a temperature 0! about 125° C. to
about 225° C. in the presence. of an active base
genation catalyst until the resin acid is at least
50% saturated with hydrogen.-
.
31. The method of re?ning and hydrogenat
ing a rosin which comprises subjecting a rosin
metal hydrogenation catalyst until the rosin acid ' in solution to treatment with hydrogen under a
pressure within the range of about 200 to about
is at least 50% saturated with hydrogen.
30. The method of re?ning 'and hydrogenating 15,000 lbs. per sq. in. and at a temperature '0!
a resin which comprises subjecting a resin in about 150° C. to about 200° C. in the ‘presence
of an active base metal hydrogenation catalyst
solution in a suitable alcohol to treatment with _
hydrogen under a pressure within the range 0! imtil the'rosin acid'is 'at‘least 50% saturated 10
‘
about 200 ‘to about 15,000 lbs. per sq. in. and at with hydrogen.'
mvm w.
a temperature of about 125° C. to about 225° C. -
in the presence of an- active base metal hydro-'
GERTIIFIGA‘I'E" or CORRECTION; ,
Patent no ,-~ 2,113 ,éoa .
'April 12, 1958. I
'IRVIN w. ‘mam.
Itfis hereby certifiedilithat error appears. _ in the - printed specification
,ofthe aboye numbered patent requiring correetionas follows: Page 1,- second
col‘unm,‘ line 11,-after.'!noble'_' insert theavord metal; page 2,‘ second c'olmi'm,
line Latter ‘mercury,’ insert or; and that the said Letters Patent should
be. read with ‘these -.co_r_re_ct1ons therein thanthe same mayeonform‘to the
record of the ‘case
Patent Office.
'
>
‘
'
I
351;»? and‘ aealedthis 1mm- day or JuneLAaD. 1933..
Hem-77 Van Arsdale',
Acting Commissieneref- ,Patentsr
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