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Патент USA US2411989

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Patented Dec. 3, 1946
2,411,989
umi‘Eo' STATES PATENT OFFICE
PAPER Cosmo
HenryV. Dunham, Bainbridze, N. Y., assignor to
H The Borden Company, New York, N. Y., acor
poration of ‘New Jersey
'-
No Drawing. Application February 5, 1942,
'
1
.
Serial N0. 429,680
.9 Claims.
This invention has for its object the use ofv
.certain well de?ned constituents present in seeds
of relatively high protein content,_such as for
example soybean, peanut, cottonseed, sun?ower
and the like in the manufacture of coated paper,
tein seed'meals. One method is known as'the
extraction process, where the seeds are crushed
and extracted with a highly volatile oil solvent
such as hexane. Another process, known as the
‘ hydraulic process, relates to crushing the beans or
wall papers and the like. I have found that such
products derived from certain portions of high
protein seeds are very’suitable for use in the ,
making of coated papers, wall papers and /the
like, e. g., the sizing of coated paper in connection 10
with mineral ?llers and pigments.
_
(Cl. 117-156)
‘
seeds, heating to various degrees, and compress
ing with an hydraulic press toremove ‘the oil.
A third process isv of the expeller type, wherein
the beans or seeds are run through an expeller at
various degrees of . temperature. Under the ex-.
peller process high pressure is applied to the seeds
One object of this invention is to utilize a high protein seed residue which has been substantially
increased in protein content above the protein
content of the unenriched seed meal as ordinarily 15
by means of a screw in the expeller chamber,
with the result that the oil is pressed from the
seeds and the relatively oil-free meal expelled
from the expeller. In general, a solvent extracted
obtained.
meal will analyze very low in oil, only about 0.5%
Another object is to utilize for paper coating
in many cases‘ remaining in the meal. By the
purposes a seed residue of relatively high protein
hydraulic or expeller processes the resulting meals
content as distinguished from the seed residue
may contain from 4 to perhaps 7 to 8% oil re
prior to its enrichment as heretofore used in 20 maining in the meal. Any .of the meals resulting
coating. The’ process is sharply distinguished
from the above mentioned‘ processes are suitable
from the use of chemically isolated seed meal
for utilization in my invention, although I pre
proteins, several processes for which have been
fer seed meals resulting from low temperature
heretofore proposed.
treatment of the seed rather than high tempera
A further object is to provide a means for uti
lizing the product of this invention in a simple
and easy manner.
Another object is the utilization of the seed
reduce of increased protein content for paper
25 ture.
In the utilization of products relating to this
invention, I ?nd that products produced from
cottonseed, peanut, or sun?ower meal usually re
sult in producing a rather dark colored product.
coating, without greatly changing the charac 30 Often for the purposes of this invention a light
ter and properties of the major portion of the
colored material is desired. ‘Because of the above,
protein present in the seed substance, as would
occur by chemical reaction.
.in most cases ‘I use soybean meal of light color
'
as the starting material. In some types of coated
A still further object is to obtain greater ad
paper it would be undesirable to use these dark
hesive values for paper coating over and. above 35 colored products because of color, although for
the adhesive values of the raw material hereto
dark coated papers this would not be objection
able.
'
fore employed in utilization of seed meal prod
ucts for paper ‘coating.
In‘ general, my invention consists in the use
Other objects will be apparent to those skilled
of a high protein seed substance from which a
in the art.
_
40 major portion of substances soluble in weak acid
In describing the'process and its results for
solutions, and in solutions of certain types of
the purpose of this application, I shall refer to
salts, as mentioned below, have been removed,
products made from commercially de-oiled, rela
and these substances which are removed with
tively high protein content soybean meal as the
such solutions I shall refer to as “gummy sub- _
raw material used in many of ‘my tests in develop
ing this process, although in general, the same
methods may be used and similar results secured,
using other high protein seed substances such as
peanut meal, cottonseed meal, sun?ower seed
meal and the like. In all cases, the object of this
process is to utilize, as a starting material, the
45 stances.” After the gummy substances have been
removed from the seed residue, the degummed
material may be dried or washed and dried, and
?nally ground when it is ready to be used as a
glue or adhesive for paper coating purposes.
Many acids, acid salts, and‘ some normal or neu
tral salts, when used in very weak solutions in
water, have the property of retarding or pre
de-oiled commercial high protein seed meals,
The process of de-oiling seed meals is well
venting solution or undue swelling of the major
known in the art. There are three commercially
portion of the protein (including water-soluble
used methods for removing the oil from high pro 55 protein and water-insoluble protein) present in
2,411,989
the de—oiled seed residue, but permit certain sub
stances (gummy substances) in the seed residues to dissolve without dissolving the major
portion of the protein material present in the
meal. Thus, it is quite simple in commercial
operations to remove the major portion of these
gummy substances from the seed residue, without
dissolving much of the proteins therefrom. This
treated product is preferably then dried and
grounii. The ‘product is then in an excellent
physical condition for handling (drying) in com
mercial operations. It is not in a sticky, exces
sively swollen condition as would be the case
if water were substituted for the extracting solu
4
removal of fibrous material can be accomplished
later on, after the degumming process.
In order to better illustrate this invention, and
to show how ‘the same can be performed, I give
herewith the following data and examples. Un
less otherwise speci?ed, all parts mentioned in
the examples are by weight.
Emu‘. I
The following ingredients are employed:
100 pounds of the so called “mechanically mill
re?ned” soybean mealv analyzing 54% protein,
which has been ?nely ground.
1000 pounds of degumming solution contain- -
tion referred to above. This step of removing 15 ing 4.5 pounds of dissolved ammonium bi?uoride.
the material which I refer to as gummy sub
stance from seeds of high protein content has
been referred to in the literature as a means
The procedure is as follows:
'
' Into a suitable mixer in which a rather slow
agitation is provided, say an agitator rotating
. at 30 to 60 R. P. M., I place the 1000 pounds of
of preparing such seed residues for the isolation
of protein. That is to say (in a prior process), 20 degumming solution, which may be at or below
room temperature. Thereafter I add the 100
after the degumming treatment, the material has
pounds of soybean meal, the mixer is started,
then been treated with a protein solvent in the
and the agitation continued without heating, the
presence of water to dissolve the protein portion
same, for approximately 30 minutes.v Thereafter
of the seed residue.‘ Thereafter the rather dilute
protein solution has been ?ltered or otherwise 25 the mixing apparatus is stopped, the material
allowed to settle for about an hour, after which
separated from the, ?nely suspended insoluble
time it will be found that a large portion of the
substance present in the seed residue substance,
insoluble residue or degummed material will have
and which is not dissolved by any of the protein
settled tolthe bottom of the mixer. The super
solvents. After removing all, or substantially
natant
liquid is drawn o? as much as possible
30
all, of the insoluble substance by means of a
without removing appreciable quantities of any
?lter press, a centrifugal, or some satisfactory
suspended degummed material. Thereafter the
mechanical means, the protein solution has been
balance of the material which contains the solids
dried by any of the convenient methods such as
or degummed material and a portion of the liq
spray drying and the like, or the solution has
been concentrated to a greater or less extent 35 uid degumming solution containing the gummy
substances may be run through a ?lter press or
(in vacuum, for example), and utilized in that
placed
in a hydraulic press, or may be put through
condition.. Furthermore, the protein has been
a centrifugal to remove the greater portion of
precipitated from such solutions by the action
the remaining gummy substances in the degum
of acids or acid salts. In the latter case, the
precipitate is allowed to settle out as much as 40 ming solution. The solid undissolved material
possible, the supernatant liquid removed, the pre
cipitated material pressed, dried and ground.
This latter product is commonly referred to as
can also be given a water ‘wash, if desired. The
liquid can be separated from the undissolved
degummed material in any suitable manner. The
resulting pressed cake of degummed material is
I make no claim for any of the procedures 45 broken up, preferably by putting it through an
ordinary casein picker which breaks the cake into
outlined above wherein the suspended insoluble
relatively small pieces in order that the same.
material is removed from the protein solution.
may dry rapidly.
Neither do I make any claim herein for the
The drying operation may be carried out by
process per se, of extracting the gummy sub
stances from seed residues by the utilization of 50 any convenient means, such as utilization of an
ordinary continuous casein drier, or the ma
any particular salt or acid. My invention in
a "chemically isolated precipitated protein."
terial may be dried in a casein tunnel drier,. or volves also the use of the degummed material
by any other suitable drying method. I prefer
as outlined above, preferably produced as de
that the material be dried at a temperature of
scribed herein, without the removal of the other
non-protein substances which are ordinarily re 55 not more than 150° F., although this exact tem
perature is not absolutely essential. After the",
moved only by dissolving the protein in a pro
degummed material is thoroughly dry it is
;tein solvent, and ?ltering or otherwise removing
ground to a powder, for example 80 mesh, or i
?ner if desired, when it is .ready to use as‘ an
centration or drying,vand the like, and the in 60 adhesive in paper coating compositions.
'the'suspended insoluble material therefrom, and 1
thereafter further treatment of the same by con
corporation thereof with fillers, pigments, etc.
It will be understood that in my present process,
the hulls or husks of the seeds are largely re
During the treatment with the degumming
solution, the gums,’sugars, some coloring matter.
and perhaps other substances, all of which are
herein included under the term "gummy mag.
moved at any suitable stage of the process. This
can in many cases be‘ accomplished prior to the 65 terial," are removed; but only very little of the 1
protein is removed from the seed material dur-'
de-oiling of the seed material.
ing the degumming treatment. Since the con
In-many cases the seed meal is "mechanically
stituents so removed appear to be largely car
mill refined" by purely mechanical operations in
bohydrates, the per cent of protein in the leached
cluding grinding, sieving and blowing operations,
and the like to‘ separate some of the ?brous mate 70 and dried residue will be found to have been
iggeased up to about 60 to 73% (usually 67 to
rial (which step may give an increase in the pro
0
tein content of the seed meal material say from
This dried material is then ready to be shipped.
40-44% up to 47-54% protein content, also giv
to a paper-coating mill, wall paper factory, etc.
ing a “protein-poor" materialthat may be suit
able as a stock feed).
Or in some cases such 75
Various other methods for the degumming of
5
2,411,989
6
seed meals are given in the following examples,
together with tables showing analyses on the
Exunm: VI
Same procedure as in Example I, but using a
soybean meal showing a protein content of 49.7%,
the meal being prepared by what is known as
resulting products, etc. In every case the pro
tein ?gures appearing in the analyses are based
on calculating the nitrogen on a moisture-free
sample and multiplying by the conversion factor
the expeller process, showing a ?ber content of ..
6.25.
approximately 7%, and an oil content of about
'
.
In this and the other examples given, the de
0.5%.
'
gummed material prior to'drying may, if so de
EXAMPLE VII
sired, be washed with water to further remove 10
~ Same procedure as in Example I, with the
small amounts of the gummyvsubstances which
exception that a high grade 011 extracted peanut
would not be removed by simply pressing the '
meal was substituted for a soy product as the
degummed material in a ?lter press or by other
raw material.
'
means. This may be accomplished by any de
EXAMPLE VIII
sired means, as, for example, by use of continu 15
ous ?lters which are now on the market. Some
Same procedure as in Example I, with the
of these include a rotating ‘drum covered with
exception that a high grade cottonseed meal
cloth, and inside of which there is produced a
was substituted for the soybean meal as the raw
vacuum. The drum rotating in a suspension of
material.
the degummed material and the gummy solution, 20
EXAMPLE IX
that is, prior to any separation, picks up due to
Same procedure as in Example I, with the
exception that a South American pressed type
of sun?ower meal was used in place of soybean
the vacuum a uniform layer of the degummed
material, and as the drum slowly revolves, the
interior suction causes the solution of gummy
materials to be sucked away from the degummed 25 meal as the raw material. material, to the point where there is, e. g. about
EXAMPLE X
70% of moisture‘still present in the cake as it
Same procedure as in Example I with the ex
comes from the revolving drum. Now if one de
ception that the soybean meal was ?rst added to
sires, there may be applied a spray of water at
some point on this vacuum drum and thus wash 30 cold water in the'proportions indicated (1. e. 100
lbs. of meal to 1000' lbs. of water)‘, thoroughly
the degummed material. Of course other meth
mixed for about 5 minutes, and thereafter the
ods of separation and/or washing would be pos
dissolved ammonium bi?uoride, 4.5 pounds, was
sible. Thus in Example I, after removing the
1 added to the mixture, and the procedure con
supernatant liquid as described, a volume of wa
ter can be added, to wash the degummed ma 35 tinued as in Example I. I consider this pro
cedure to be less advisable than that given in
terial. Thereafter the degummed material can
be allowed to settle without becoming sticky or
gummy because of the removal of most of the
Example I.
-
>
By the above procedure, Example X, a consid
gummy substances. Then the wash water can
erable amount of the water soluble protein orig
be drawn off, and the resulting mass then 40 inally present in the raw material is dissolved in
pressed and dried in any suitable manner. Any
the water, since the solvent retarding degumming
chemical is not present in the mix at the begin
other suitable means may be used if desired for
washing the degummed material.
ning of the treatment, but after the addition
of the degumming chemical (ammonium bi?uo
It will be apparent that the removal of all the
gummy material, if no substantial amount of 45 ride) the water soluble protein as such appears
to be substantially all (or mostly) precipitated
proteins is removed, will increase the percentage
by the addition of degumming material and after
of protein in thegproduct, in contrast to the re
properly mixing and allowing the mix to stand.
moval of a part only of the gummy material.
At this stage the supernatant liquid is about the
EXAMPLE II
50 same in appearance as in Example I, but the set
Same procedure as indicated in Example I with
tling of the degummed material is somewhat less
the exception that a high grade soybean meal
rapid after the mixing operation than when the
was used as the raw material, analyzing 51.3%
degumming chemical is added to the water prior
protein, and showing a fiber content of approxi
to the addition of the material to be degummed,
mately 7%. This is a solvent extracted type 55 although there is no di?iculty encountered in ?l
meal, and the product used was in an unground
tering the degummed material or pressing out
form, that is to say, in a ?ake form.
the excess liquid as described in the operation
under Example I. As has been indicated, other
EXAMPLE III
degumming chemicals may be used, and the uti
Same procedure as in Example I, with the ex
lization of the ammonium bi?uoride in the exam
60
ception that the raw material used was unground
ples cited above are only by way of illustration.
?akes‘ of solvent-extracted soybean, showing a
The results as to increase in protein content
protein content of 49.2%.
over the raw material, raise of protein obtained’
EXAMPLE IV
by the treatment, yield of the degummed material
Same procedure as in Example I, with the 65 based on the raw material used, and per cent of
raw material retained in the treated degummed
exception that there was used a soybean meal
material appear in Table I, given below.
analyzing 51.8% protein, and which is believed
Many di?erent degumming chemicals have
to have been a solvent extracted type of meal.
been used in my researches, and the results have
EXAMPLE V
70 shown substantially the same quality of de
Same procedure as in Example I with the ex
gummed material from the standpoint of its sub
ception that a soybean meal was used showing by
sequent use as a sizing in coated paper. To more
analysis 57.5% protein, and a low ?ber content,
fully illustrate the results that may be obtained
namely approximately 0.5%. This was a solvent
with other degumming chemicals I give the fol
extracted meal.
75
lowing examples:
-
8,411,”?
7
8
Exunu: XXIV
Same procedure as Example X, with ‘the excep
Same procedure as in Example I-with-the exa
tion that 3.7 pounds 01' sulphur dioxide gas were'
ception that the degumming solution was‘ made
substituted in this test for the ammonium bi
with 3.8 pounds oi hydrochloric acid having a
’ ?uoride indicated in Example X.
speci?c gravity of 1.18 to 1.19. ‘and 3.3 pounds 0!
tin chloride (stannous chloride) in place of the
EXAMPLE XII:
use of ammonium bi?uoride.
Same as Example I, with the exception that
ExmLsXXV
the degumming solution was made with 3 pounds 10
of phosphorous acid in place oi’ the ammonium
Same procedure as in Example x with the ex
ception that the degumming solution was made
bi?uoride.
'
v
_
EXAMPLE XIII
with '6 pounds of hydrochloric acid having a spe
citlc gravity 01' 1.18 to 1.19, said hydrochloric acid
Same as Example X except that the degum
being
saturated with calcium ?uoride prior to
ming solution was made with 4.4 pounds 01' com 15
its addition to the mixture oi’ meal and ‘water,
mercial hydrochloric acid having a speci?c grav
indicated in Example X, and this mixture was
ity of 1.18 to 1.19 in place of the ammonium bi
used as the degumming chemical.
?uoride as the degumming agent. It will be
noted that this gives hydrochloric acid solution
Exmu: XXVI
.
of about 0.155% to 0.17% strength.
20
Same procedure‘ as in Example I with the ex
Exmm XIV
ception that the degumming solution was made
with 12.5 pounds of saturated solution of citric
Same as Example 1, except that the degum
acid and lead chloride in which the ratio of the
ming solution was made with 4.2 pounds of gla
citric acid to the lead chloride was as 5 to 1. Said
cial acetic acid as the degumming chemical.
mixture of acid and the salt was added to the
Exmu: XV
diluting water in the proportions indicated in
, Same procedure as in Example I except that
Example I in place of the ammonium bi?uoride.
the degumming solution was made with 5 pounds
Exsxru XXVII
of tartaric acid as the degumming chemical in
30
Same
procedure
as in Example I, with the ex
place or the ammonium bi?uoride.
ception that the degumming solution was made
Exsuru: XVI
with 25 pounds of acetin and 6.3 pounds of glacial
Same procedure as in Example I excepting that
acetic acid in the place of the ammonium bi?uo
the degumming chemical used was 6 pounds of
ride used in Example X.
‘ '
EXAMPLE XI ‘
citric acid as the degumming chemical.
‘
35
' EXAIPLE xxvm
EXAMPLE XVII
Same procedure as in Example X with the ex
Same procedure as in Example I except that
ception that the- degumming solution was made
the degumming solution was made with 4 pounds
of oxalic acid in place of the ammonium bi?uo 40 with 8.5 pounds of a mixture of triethanolamine
and glacial acetic acid, the mixture being pre
ride.
pared by the addition of suillcient glacial acetic
ExAMPLn XVIII
acid to the triethanolamine so that the resulting
Same as Example I with the exception that
mixture had a ‘pl-I of 3.9, and this degumming
the degumming solution was made with 6 pounds
chemical was substituted for the ammonium bi
of tin chloride (stannous chloride) instead of
?uoride.
'
ammonium bi?uoride.
The analyses, yields, etc., resulting from ex
amples in to XXVIII inclusive, are indicated in
EXAMPLE XIX
Table II, given below. It should be noted that
Same procedure as in Example I with the ex
the .various examples listed above were made at a
ception that the degumming solution was made
temperature of approximately 60 to 70° F., room
with 10 pounds of magnesium chloride in place
temperature, 100 pounds of meal and 1000 pounds
of the ammonium bi?uoride.
‘
jams as Example X with the exception that
tii€desumming solution was made with 5 pounds
of calcium sulphate in place of the ammonium
bi?uoride.
EXAMPLE XXI
Other examples are given, however,
with different temperatures used during the de
summing process as illustrated by the following
I oi.’ water.
Exnnna XX
‘
Same as Example X with the exception that
the degumming solution was made with 5 pounds
of magnesium silico-?uoride in place of the am
monium bi?uoride.
examples.
ExsurLsXXIX
Same procedure as Example I, with the ex
ception that the degumming solution was made
with 2.1 pounds of sulphur dioxide gas, and the
degumming solution maintained at a temperature
of 110° F.
Exam?“ XXX
Same procedure as Example I with the ex
65 ception that the degumming solution was made
EXAMPLE IQIII
with 2 pounds of sulphur dioxide gas, and the de
Same as Example X with the exception that the
gumming solution was maintained at a tempera
degumming solution used was 5 pounds of mono
ture of 160° F.
calcium phosphate in place of the ammonium bi
Exmu XXXI
?uoride.
70
EXAMPLE XXIII
Same procedure as Example I with the excep
Same as Example X with the exception that ‘ tion that the degumming solution was made with
the degumming solution was made with 5 pounds
2 pounds of sulphur dioxide gas. and that the de
of neutral sodium ?uoride in place of the ammo
gumming solution'during the process was main
nium bi?uoride.
'
.
75 tained at a temperature of 180° 1".
9,41 1,989
9
I
.
10'
Exsurnr: XL
Exulru XXXII
Same procedure as indicated in Example X
.
Same procedure as in Example I, with the ex
ception that the degumming solution was made
was made with 5 pounds of hydrochloric acid 5 with 6 pounds of tin chloride (stannous chloride)
and 500 pounds of water.
having a specific gravity of 1.18 to 1.19, and that
The analysis, yields, etc., the washed products
the degumming solution was maintained
of Examples XXXVI to XL inclusive are indi
throughout at a temperature of 100° F, The de
with the exception that the degumming solution
gumming solution accordingly contains. about
0.18 to 0.19% H01.
.
ExAmrLa xxxm
Same as Example X, with the exception that
the degumming “solution was made with 3.4
cated in Table IV.
>
130° F.
.
.
_elieve it would be readily possible to use even
smaller amounts of water, in the degumming
treatment, e. g.,_400 of water to 100 of the seed
meal.
pounds of glacial acetic acid, and that the de 15
gumming was carried out at a temperature of
‘
1N Based on the above and other experiments, I
.
In order to demonstrate the improved adhesive
value of the degummed material from the stand
point of paper coating‘ the following results are
EXAMPLE XXXIV
given. The ?nely ground. degummed and dried" I
material which may be ground to any desired
Same procedure as Example X with the ex
ception that the degumming solution was made 20 mesh, for example 80 mesh or ?ner, and made
for instance according to the method described
with 5.6 pounds of glacial acetic acid, and that
in Example I, is mixed with cold water, the par
the degumming solution was maintained through
out the operations of degumming at a tempera-v . ticles thoroughly wetted, and the mixture may
be allowed to soak in water for a short time, say
ture of 190° F.
25 15 or 20 minutes. _(Here, as above, all parts are
_
.
'EXAMPLE XXXV
given by weight.) Thereafter an alkaline ma
Same procedure as Example X with ‘the excep
terial (or protein solvent as is the usual accepted
tion that the degumming'solution was made with
term for-such substances) .is added to this mix
5 pounds of ammonium-bi?uoride and that the
ture, the mixture then thoroughly stirred, and
degumming solution was maintained throughout 30 preferably heated to. about 120 or 130° F., while
the operations of degumming at a temperature of.
stirring to assist in' the dissolving. When the
180° F.
.
~
degummed substance is dissolved, with the ex
The Table III given below, is a tabulation of
ception of the suspended insoluble non-protein
the analyses, yields, etc., obtainedfrom the pro
material, it is ready to be used as a sizing for
cedure as described under Examples XXIX to 35 paper coatings;
XXXV, inclusive.
,
Generally, there appears to be no substantial
advantage now apparent in the useof tempera
tures above room temperature (60-80‘ F.) in the
degumming treatment. There are some disad
vantages in the use of heat‘ in this treatment,
notably that when the degumming treatment is
effected at 30° F., the ?nal coating solution has
somewhat better ?owing properties, when applied
The exact proportions in pre
paring the liquid size from the degummed mate
rial and in they preparation _of the regular seed
meal size, for comparative purposes, is as follows:
Parts
40 ‘ Degummed material _____________________ __ 100
Water
_____
'
-
_
500
10% solution of sodium hydroxide ________ __ 100
' Here, as will be noted, 100 parts'of a 10% so
to the paper.
lution of caustic soda is mixed with 500 parts of
It will be noted that in the examples thus far 45 water, to form a mild (1.67%) solution of caustic
given, the amount of water used was on the basis
soda which is used as the solvent or vehicle for
of approximately 1000 parts of water to 100 parts
the degummed material and pigmentary mate
of the meal to be treated. However, the water
rial.
ratio may be adjusted to obtain the most favor
For preparing the paper coating mixture,
able factory handling conditi ns during the de- 50 (which is ordinarily referred to as "coating color”
gumming process without in terially changing
whether the pigment and ?ller are colored or
the quality of the treated d summed seed ma
white) , the following formula was used:
terials. The following, exa ples illustrate the
,
Parts
use of less quantities of water during the degum
5 Clay ___________________________________ __ 100
ming process:
-
‘
EXAMPLE XXXVI
Water _________________ __~_ ____________ __
100
Liquid size ______________ __' ___________ _..~_.. 126
Same procedure as Example I except that the
The clay is added to the water and mixed until a
degumming solution was made with 3.2 pounds of
smooth slip is formed. The liquid size is then
sulphur dioxide gas added to 500 pounds of water. 60 introduced and mixed until smooth and until the
I ' clay is completely dispersed. The above propor
EXAMPLE IDIXVII
tions give a concentration of 18 parts of dry siz
Same procedure as Example 1 except that the
degumming solution was made with 2.5 pounds of
sulphur dioxide gas and 500 pounds of water.
EXAMPLE XXXVIII
Same procedure as in Example 1, with the ex
ing material to 100 parts of dry clay.
The prepared paper coating color is preferably
65 strained through an 80 to 100 mesh wire screen .
and thereafter brushed on to the type or paper
ordinarily used in the paper coating industry. .or
applied to the paper by some coating machine
ception that the degumming solution was made
such as for example the laboratory coating ma
with 4.4 pounds of glacial acetic acid using-500
pounds of water instead of 1000 pounds of water. 70 chine known as the Martinson, wherein an ex
act amount of the coating color can be applied
EXAMPLE XXXIX
per unit area in each test. After the sheets of
paper have been coated they are allowed to dry
Same procedure as in Example I, except that
and to season for approximately 18 hours in an
the degumming solution was made by using 500
pounds of water instead of 1000 pounds of water. 75 air-conditioned room with a relative humidity of
aunties
11
-.
\ 50%, and a temperature of 70° F., in order to
maintain uniform conditions during the test pe
riod. After the proper aging. of the coated sheets
their relative qualities were tested. In mytests
I have employed the almost universal procedure
. known “the Dennison wax test, which may be
. described as follows:
The end of the wax stick is softened by hold
ing over. a flame. The softened end is then,
12
outside shell or hull of the bean, that the result
ing degummed dried material is thereafter ground
by any suitable mealre?ning method to remove
the major portion of the outside shells or husks
of the bean, and at the same time reduce the re
maining material to a relatively ?ne mesh, prei- '
erably 80 mesh or ?ner. This relatively ?ne
ground condition, in the ?nished product is im
portant from the standpoint of its use for-paper
pressed by hand against the coated surface to 10 coating purposes. The coarser the ?nished ma
terial may be, the more slowly will it dissolve or
be tested, using moderate pressure. The wax is
allowed to cool and harden. Then it is pulled
disperse in the alkaline solvent in the presence of
water when being prepared for paper coating
away from the surface of the paper. The wax
sticks are supplied in graduated degrees oi’ hard
purposes. I do not restrict the invention to the
particular alkali mentioned (numerous others.
ness, the lowest number being the softest and
including trisodium phosphate, ammonia,sodium
giving the least pull on the paper suri'a'ce,the
higher numbers becoming progressively harder
carbonate, etc., can be used). I do not restrict
and giving more pull to the surface. By applying
the invention to the use of clay, water and size
onlyfin the “coating. color" since colored pig
a series of the wax sticks to the paper, a point
will be found where no failure of the coating or 20 ments, dyes, etc., can be added, and the clay
paper stock takes place with a given wax stick,
can be substituted by satin white, calcium car
bonate, and other ?llers. ‘Such pigments, dyes
but when applying the next harder wax stick
and ?llers will hereinafter be referred to for
there will be failure. The end point ofthe test
brevity, as “a suspended pigmentary material."
(the number recorded to indicate the strength of
sizingin the coating) is the number oi‘ the hard 25 The degummed material made as described in
this speci?cation may if desired be mixed with
est wax which does not cause failure.
other adhesive materials for paper coating pur
Coated sheets were prepared and tested, as de
poses such as combinations of casein, animal glue,
scribed above, coated with colors prepared from
modi?ed starches, and the like in such propor
the products of several of the above examples as
the sizing material for the clay. Papers coated 80 tions as might be desired. 01 the proteinsol
vents mentioned, caustic alkali (e. g. NaOH)
with several untreated seed meals were tested for
seems to be better than the others tested.
=
comparison. The results of these tests are tabu
The above mentioned and similar seeds in their
lated and appear in Table V, below.
original condition include cellulose in two dis
It will be noted that there is a very large ‘in
crease in the ‘adhesive value of the sheets coated 35 tinct forms, namely (a) a hull or shell composed
of one or several layers, which hull is composed
with my degummed product as compared with
largely of cellulose in a relatively tough and use
the sheets coated-with the raw seed meals used
less condition and (b) cell walls in the interior
in preparing the degummed material.
or'kemel of the seed, which latter is softer, and
It will be understood that the above examples
oi’ paper coating are for the purposeof illustra 40 less tough in character. The former will be re
ferred toas “hull,” and the latter as “non-hull
tion only. I do not restrict the invention to
cellulose," for brevity. In the process of the pres
, grinding the degummed material to 80 mesh or
ent case, the “hull" is‘ all or substantially all re
?ner. Thusv in Example II, the product was
moved from the seed material during the process
treated by the degumming process in the un
ground or ?ake form. This coarser material has 45 ing, whereas the "non-hull cellulose” is not re
moved, at least to any considerable extent, and
the advantage that it does not tend to lumpor
remains in the treated dried product. In the
ball up when mixed with water and the acidic
process very little of the protein content of the
degumming material. Furthermore. after proper
seedmeal is dissolved out and very little of the
treatment, such coarse degummed ?ake material
settles from the. supernatant liquid more rapidly 50' "non-hull cellulose” is removed, and accordingly
the ratio of protein to non-hull cellulose, as orig
than a ?ner ground material would do. It should
inally existing in the seedmeal and in the me
be borne in mind, however, that if the unground
chanically mill re?ned material practicallyis sub
or‘?ake form of material has been treated either
stantially preserved throughout the treatment.
with or without a considerable proportion of the
TABLE I
Degumming treatment of various seed meals with
4.5 parts of ammonium bi?uoride per 100 parts
0;! meal and 1000 parts of water
Emmple
numbe'
Peroent pro- Percent pro
tein in raw
“in iilngg‘
material
gum
Raw material treated
material
Soybean meal ............... _.
Rise in per- Percent yield Percent pro
cent of pro- on raw matein ro
am
ierial
tained I
53. 0
70. 3
17. 3
65. 0
._-..d
51.3
62.4
11.1
81.8
_-_._do- '
49. 2
63. 1
13. 9
78.0
.-___do_
...-.do.
51.8
57. 5
64.4
68. 6
12.6
11. 1
79.8
76. 1
..___do __________ _.
Peanut meal .......... ..
49.7
64. 2'
63.5
74. 3
13.8
l0. 1
76.5
84. 0
97.6
97. 3
48. 2
58. 8
l0. 6
80. 2
9s 0
_
Cottonseed meal ...... __
_
Soy
............... -.
1 Used 5.0 parts oi ammonium bi?uoride.
' Moisture contents disregarded in values.
40.3
53.8
53.0
69. 0
_
7.5
84.3
l6. 0
65. 1
8o. 2
99.6
1i!)
99.2
90. 9
_
01.7
85. 0
2,411,989
13
~
_
Tm: II
-
.
Deyumming treatment of soybean meal (from
the same lot) having 53.0 per cent protein with
various chemicals and chemical miztures
Dcgummlng Percent pro
chemical
Chemical used in degumming treatment
percent 01'
tcin in de-
mos]
ééhdtiliééiié'h'cié‘i?ii iii}
87916305 87916305
7042835
aving a
Rise in per Percent yield Percent otto
cent protein in do gummed tal protein in
raw material
produced
men]
retained
mw%wm .1 6G.750m392Q4n
376
376
68. 9
70'. 9
15.9
17. 9
64.5
83.0
68.0
62.0
88.3
.
.
82.9
TABLE III
Treatment of soybean meal of 53.0% protein con
tent with various chemicals and 1000 parts of
water to 100 parts of meal at higher tempera
tures
Chemical
used percent
of meal
Tmmt,mm
.r
046
8
sum1mm.mw m
Ppdoreimam
m amw nMad$61026
w
e,
RmanD.or rm
m
a
n
:mM7.5a?w&
to1
mm...“
1 nde.
UW_
m
mm
D "
86102
m
d
mm"7?%"a.5..&.ml?.
"60571
Hfor
m“n‘mwmw6.11“a0 0.
tnm"11
.
TABLE IV
Degumming treatment of soybean meal having
53.0 per cent protein with 500 parts of water
and 100 parts of meal and various chemicals
Chemical
per 100 of
meal
Chemical used
xx
XEXL0xxxxm. wmwmmm0.
a
f
m
I
_
.
degummed
mamamamamama
when
m
Teen: V
Parts
Parts
Wax test
Sizing material
Soybean meal (not treated)..-“
Product of Example I.
Product of Example X . _ .
Peanut meal (not treated).______
Peanut product (treated as m
Example I).
on meal
Percent of
protein re
tained in
degummed
I claim
1. In paper coating, the process which consists
in ?rst leaching a high protein content seedmeal
‘0 with about 4-to 10 times its own weight of an acid
aqueous solution having an acid content equal
to about 3.8 to 6 lbs. of hydrochloric acid solution
of sp. gr. 1.18 to 1.19, per 100 lbs. of said seedmeal,
said seedmeal material to a protein-denaturing
treatment, mixing the degummed seedmeal ma
18
18
100
100
Partial on 2.I
5.
1 No. 2 is lowest wax available.
The minimum wax test, for a coated paper, for
a useful product for being printed upon is about
4.5 (four and a half).
Percent yield
thereby dissolving and removing the bulk of the
'35 carbohydrate gums, and without subjecting the
Product of Example IX. _
Product of Example XIV
Product of Example xI.___..-.
Cottonseed meal (not treated)__
Cottonseed product (treated as
in Example I).
Rise in per
cent protein
3.24%16 2540 ,50287 1 6.5 L 50287 w .mn 03 8 .27 7089
phur dioxide._... .. __
KATs
Percent
protein
.
terial with an aqueous alkaline liquid of an alka
linity equal to about 1.67% of NaOH, and with
70 a pigmentary material, and coating paper with
said mixture.
2. A process as covered in claim 1, in which
the seedmeal material is one selected from the
group consisting of soybean, cottonseed, peanut,
75 sun?ower seed and mixtures thereof.
2,411,900
15v
-4
3. In the paper coating process of claim 1, the .
16
therefrom by means 0! an extremely dilute
addition of a water-washing step after the leach
aqueous solution of an acidulous material, which
ing operation.
ahueou's solution is not an effective protein sol
‘
‘
‘
in ?rst leaching a high protein‘ content seedmeal
vent, whereby a material richer in protein than '
the de-olled seed residue and low in water-soiuole _
with several times its own weight or an acid
aqueous solution having an acid content equal to
gums and vother soluble carbohydrates is pro
duced, and at some stage of the process removing
- 4. In paper coating, the pr
ess which consists
substantially all hull material, incorporating such
degummed seed meal with an‘ alkaline solution
therebyv dissolving and removing the bulk of the 10 which is an eil'ective protein solvent, and without
about 3.8 to 6_ lbs. of hydrochloric acid solution
of sp. gr. 1.18 to 1.19, per 100 lbs. of said seedmeal,
carbohydrate gums, and without subjecting the .
said seedmeal material to a protein-denaturing
thereafter removing the bulk of the swollen un
dissolved constituents, incorporating a paper
treatment, mixing the degummed seedmeal mate
coloring pigmentary material with the liquid
rial with an-aqueous liquid which is capable of
mass,‘ and applying the same as a coating on
dissolving the protein content of such material, 15 paper, and drying the same. 1
8. In the art of coating paper, the improvement
and with a pigmentary material, and coating
which comprises separating at least the principal
paper with such mixture.
part of the oil content from‘ proteinaceous oil
5. In paper coating, the process which consists
in ?rst leaching a high protein content seedmeal
bearing seed material, leaching the de-oiled ma*
with several times its own weight of an aqueous 20 terial with a dilute solution of a compound con
liquid which is a good solvent’for carbohydrate
taining an acid radical, which solution is a less
gums contained in ‘said seedmeal but which is
less active as a solvent for‘water soluble proteins
present in said seedmeal than is pure water,
effective solvent than water alone for water-sol
‘uble protein present in the seed residue, and
which is a good solvent for soluble carbohydrates
thereby dissolving and removing from said seed 25 including gummy substances, whereby a material
meal the water soluble carbohydrates including
richer in protein than the de-oiled seed residue
carbohydrate gums, and without denaturing the
and low in water-soluble gums and other water
soluble carbohydrates is produced, and at some
proteins present'in said seedmeal, thereafter mix
stage of the process removing substantially all
ing the degummed seedmeal residue with an
aqueous protein-solvent liquid and'with a pig 30 hull material, incorporating such degummed ma
mentary material, and coating a fully formed
terial in which material the proteins present re
paper with the resulting liquid.
main in substantially the same condition as in the
6. In the art of coating paper, the improvement
original seedmeal with an alkaline solution which
which comprises separating at least the principal
‘is an e?ective protein solvent, and without there- ,
part of the oil content of proteinaceous oil-bear 35 after removing the bulk of the swollen undissolved
ing- seed material, raising the protein content of
constituents, incorporating a paper-coloring, pig
the proteinaceous solid material by the removal - mentary material with the liquid mass, and apply-v
of cellulosic hull therefrom, leaching out gummy
material therefrom by means of an extremely
dilute aqueous solution of an acidulous material,‘ 40
corresponding in acidity to KC! solution of about
0.155 to 0.19%‘ strength, which solution is not an
effective protein solvent, but which is a solvent
for water soluble carbohydrates including gums,
whereby a material richer in protein than the 45
de-oiled seed residue and low in gums and other
soluble carbohydrates is produced, and at some
stage of the process removing substantially all
ing the same as a coating. on paper, and drying
the same.
9. In the art of coating paper, the improve
ment which comprises separating at least the
principal part of the oil content from protein
aceous oil-bearing material, leaching the de-oiled
material with a dilute solution in which water
soluble proteins are largely insoluble. and are for
the most part in the undissolved state and in a
condition readily soluble in alkaline casein sol
vents, whereby a material richer in protein than
the de-oiled seed residue and low in water-soluble
hull material, and drying the said material, while
still containing substantially all of the compo 50 gums and other water-soluble carbohydrates is
nents of the seed meal except those removed by
produced, and at some stage of the process re
the above steps, thereafter incorporating the de
‘ moving substantially all hull material, incorpo
gummed material with an alkaline solution which
rating such degummed material, while still con
is a protein solvent, and without thereafter re
moving the bulk .of the swollen but undissolved
constituents, incorporating a paper-coloring pig
_ mentary material with the liquid mass, and there
after applying the same as a coating on paper.
7. In the art of coating paper, the improvement
' taining substantially all of its protein in a chemi
cally unmodi?ed condition, with. an alkaline solu
tion which is an effective protein solvent, and
without thereafter removing the bulk of the
swollen undissolved constituents, incorporating a
paper-coloring pigmentary material with the
which comprises separating at least the principal 60 liquid mass, and applying the same as a coating
part o'i'the oil content of proteinaceous oil-bear- .
ing seed material, leaching out gummy material
on paper, and drying the same.
HENRY V. DUNHAI'.
1?
Certi?cate of Correction
Patent No. 2,411,989.-
-
18
_ December 3, 1946.
HENRY v. DUNHAM
It is hereby certi?ed that error appears in the printed speci?cation of the above
numbered patent requiring correction asfollows: Column 1, line 29, for the word
“reduce” read residue; and that the said Letters Patent should be read with this cor
réegion therein that the same may conform to the record of the case in the Patent
ce.
-
Signed and sealed this 11th day of November, A. D. 1947.
[81m]
THOMAS F. MURPHY,
Assistant Oommissioner of Patents.
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