Patented Dec. 2-1, ‘1937 Q
”
' 2.103.153
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i_
uNiTEo .s'r
Ties
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PATENT'J". *
2,103,153
.
CASEIN cotrroUNn AND rnoonsslor ~
1 Henry momma; Bilinbl'llllO, my. f
'‘
~_ No ‘Drawing. ~ ppllcation April as, 1935, ‘semi
No. 18,435. In Great
-
Britain‘? December '8'I 5 j.
1934 »
' » .r'zj?oiaims. "(cacao-e)
This‘iinven'tion relates to the production‘oi' more or less.‘ The pressur'ecanjberegulated‘l by
1 compounds of casein with metal hydroxides’ and
w-s'alts, or with'ammonium salts, particularly ‘those . varying the size: of‘ theholesin the-gridand the
';'salts which are acidicfor neutral, or those'metal _, extrusion outlets, so; as,to give a pressure in the
*5 hydroxides so; feebly alkaline that ‘they dov not ’ kneading compartment 1 of ‘two, tons per] ‘square,
inch, dried.
‘more or less. ‘,Thelextrudedlmaterial isv 5
act as solvents for 'casein in the ‘presence of water. ‘jthenll
.
I
The present application is in part a continua
_
_I,ca_ll attention-to thefact that the
amount of water in the mixtureiis comparatively
tion of: my. co-pending application 644,752 ‘filed ‘ small
which isan advantage in the dryinggopera
- November-.28, 1932 (now Patent 2,005,730);
jtions
10
In‘ accordance‘ with the present invention, the ‘
'
'
-
~
-'
The following tanner; will'serveitoéjillustrate 10 '
- casein may be provided inv a’moist condition, con- .
the invention.
taining an‘ amount of water which is preferably
substantially less than the amount of actual case
,
in, for example containing 15 to 30%, of water.
.
'
-
-
,'
Example
1v
'
~ To~~100 parts of air-dried1 casein, containing.
15 This is ?rst roughly mixed with the salt or com
about 10% moisture‘ are added .20 parts of cold 15
pound of the metal. The mixture is then thor
water and the mixture allowed to stand for about . -
_ oughly ‘kneaded together under high pressure,
and is extruded in the form of a relatively thin
an hour, during which time thecasein absorbs the
whole of the water, forming a mass having a mm =
piece or pieces. Finally the extruded material is' sistency resemblingwet ‘corn meal. Then 8 parts.
20 dried and preferably’ pulverized or otherwise ~ of ferric hydroxide (containing 15% of water),
comminuted. If dry casein constitutes the start
are added and the mass mixedby agitation for 10 20
ing material, it can be ?rst mixed with a small, minutes. The mixture is then run through the
amount of water or'aqueous‘ liquid, and allowed extruding machine, with external heating. The
' to stand for a time, to absorb thes'aid liquid and extrudedjribbon is dried in an oven,_and.then
then mixed with the metal compound. Or if the ‘ground to a coarse powder. 'This product,‘ which
metal compound is soluble, it maybe dissolved contains ‘about 4.57% “Fe is‘ dark brownin color. 25
in water, and the casein soaked in the solution, It is‘, insoluble in water but‘ readily-‘soluble m
the amount of waterbeing as stated above. 'In aikalis. ‘ It is useful for medicinal purposes. .
addition to the above mentioned metal com
‘
' pounds or salts, a small amount of alkaline mate
rial, preferably a mild'a'lkali such as sodium bi‘
carbonate or borax may also be vadded to ‘the
initial material if desired. ,
i
.
v
.r
In carrying out the process, thejmolstjmixture‘
35 is run through a suitable. extruding'machine,
which contains a conveyer screw rotating within
a cylindrical casing, preferably surrounded bya
jacket through which'heating or cooling ?uids
may pass, or a plurality of jackets, some of which
49 may cool the mixture and others may heat the
mixture, depending upon what special materials
are being employed. Near the discharge end of
the extruding device is a grid or series of grids,
7 through ‘which the charge is'fo'rced, in orderto
45 thoroughly knead the ingredients together, and
maintain the desired amount of pressure upon
,
'iExanrp‘le 2
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f
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0
‘Another casein-iron preparation maybe made 3
in a similar manner bymixing 5 parts of casein
and 1 part‘. of water, later adding 1 part of iron '
‘
lactate, ‘kneading. andi extruding.-~ Thislproducti ', l
is insoluble‘ in water but soluble in ,alkalis. It may 35 '
be ground to a fine powder, ‘mixed with 1.5 parts 1
of water and 0.72 ‘partgofv. sodium. bicarbonate
and again passed throughithe extruding machine,’ ,
and dried. . The ?nal dry product, which isIsoluble < ‘
in water, contains‘tjaboutj 3% Fe.
_ ‘ , '1
'
i
40
"Example 3.
A casein-copper product can bemade by mix
ing a solution of 12.5}parts of pure, copper :sul-
I
phate in’ 40 parts of ‘water with about 160 parts 45 '
the materials in the convolutions of the screw.
of casein andtreating the, mixture in the extrud
As-the mixture-passes through the screw'press
grinding the product, nnxmgj‘wuh 21' parts of
ing machine, 'dryingif desired, and thereafter
_ heat may be; generatedby- the reaction and/or
00 heat maybe supplied by the jackets referred to ' sodium2 bicarbonate in'about 40pm; 'ofwater, re
in the extruding j'_ ‘achine and finally 5°
above. The stiff mixture isforced out at theend treating‘
drying. ’The end product 'cont‘ains’about 2% Cu '
of the extrusion machinein the form say of a rib.
v
bon which maybeasixteenthofan inch thick more
The- “parts” throughout the examples are by I
or less,~or in the form of a number of small wires
Cl Oi or worms, say a sixteenth of an inch in diameter,‘ weight, and the above examples-are given merely " Y‘
byway of illustration.
~ ’
55
andissolubleinwaterrf“
"
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7 2,103,153
In Table~ No. 1, below, I give the properties
soluble in water but soluble in such casein sol
vents as borax, trisodium phosphate and caustic
of a considerable number of compounds made in
accordance with the present invention. In col
umn A is shown the amount of the particular
metal compound .used in eachcase with 100. parts
soda. The compounds of cobalt carbonate, cal- cium acetate, manganese citrate and strontium
salicylate are also completely. soluble in a 10% '
of casein and 20 parts of water to prepare the
mixture to be charged into the extruding ma
other compounds listed-and casein itself are not
chine.
soluble.
aqueous solution of sodium acetate while ‘the
In column F, are recorded the relative I
I
t
d
v
_'
_
.
.
viscositiesof solutions of the ?nished products in ' ' Some of the compounds may ‘be used with‘ ad
vantage‘in place of casein for making glues while
10 a given amount of ammonia‘diluted with su?i
cient water to bring the viscosity within prac-.
tical range at 70° F. ‘The amount of water added
others are unsuitable for this purpose.
A com
parative test in a typical casein glue formula 7
varies with the character of- thedi?erent come _ was made as follows: The dry‘ingredients of the
pounds, a very viscous solution such as thatv :jcasein glue consist of,75 parts casein, 12 parts '
15 obtained with the aluminum borate compound “ ‘hydratedvlime, 6 _ parts trisodium phosphate
requiring a greater amount of water to bring it ‘ and 7 parts ‘sodium fluoride. 100 parts of this]
to a thin consistency thanfdoes a ‘thin-flowing
solution obtained‘ for instance ‘with the am
monium acetate compound, ‘which requires no
dry mixture are mixed with 200 parts of water,
initially at ya temperature of about. 60° F. and
well stirred for‘, 20 minutes. At this stage the
20 dilution.
In each case 100 parts of the dry viscosity of the liquid glue is taken on the Stoer
powder were mixed with '7 parts‘of ammonia - mer- viscosimeter. .‘I The»: glue is‘ then allowed to.
- (26° Bé.) in 400 parts of’ water, heated to 160° F., ‘stand andthe viscosity again‘ determined atthe
cooled and‘dilute’d 'td'the ‘total water-content
end of 5 'hours and again at 24 hours.v The
shown in column ‘E, except that the ‘compound
vaIuesQbtalned are precordedgin columns G,'.H,
1made with antimony lactate‘ required ".10 parts ._and. I .ofTable 1. Inturther tests-375 parts of
of ammonia. t‘Thexviscosity walues recorded in . the selected -_ casein-compound;v was ' substituted
for. 75_ parts .of casein in ‘the above formula and
column F were determined ata standardtem¢
‘ perature of 70° F. on av Stoermer viscosimeter the mixtureustirredzin" the same manner with
‘(driven by a 500- gr. weight) and it is to be under ‘ the ‘same proportion of water as before, and ‘the -
-30
stood that the lower the reading, the higher is
viscosity: determined at 3 the’ same ,_ intervals : and ‘
the
recorded in the. respective columnsgin Table 1.
viscosity. ~
'
,
‘
7
.
Table 1
Eztruded product
.
‘
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-
.
40
‘
Metal compound, name .
used
"
7.63
'
g
comp.
-
_»26° Bé:
.
100
.
D t .
I
E
>100
.
100
100‘
i
7
7
7
i
v
.
500
8
800'
500
75
5
100
100
7
600
16
100
100
7
600
4
5. 46
100
100
7
500- -
6:6,
.100
100
7
000
7
400
100
100
6.78
100
100
7
400
112.02. 1
8.35
. 8.63
100
100
100
100
100
100
7
7
7
600'v
600
500
10.8‘» '
100
100
7
500
v10.1
100
100V
10
400
100
100
100
100
7
_7
600
400
100
'7‘
3. 52
6:82
5.84 -.
100
'
.
I
7
I
l 27
‘
1000
, 15
1000
" 24
0.2
.100
100-
7.
.1007
100
‘100
1100
100
100-
‘100
500
7
7
600
700
1001
,7
600
,110
7 20
1.‘ 1
______________ __
"29
____
l
_ __' ...... _.
{e11 ______ __
-
;
-
17,
_
718
' i‘
.. i.
,- 15
'
452
' 14
- 13
22 .
7.9.
‘100
100
» 7
500
"1'
ass
100
100
1
600
14
j
' 100
100
7
400
g 3
19
5.2 .
"100
100
7
600
I 8
~19
5.71
8.19
100
100
100
100
7
7
700
400
‘.13
> 2
v 34_
., ‘58V
7
500
20
100
l
70
10
15=
i
_
5_
"42
-’
42
28
11
~i‘ _.
‘7
,7
V31
15 "
7
1
1
24
7
-:
.,
‘20
100
500
j
_ 26
. ,"28
;.
‘16
3‘
i
1000-
. .j
‘
100
I‘
' 40
’
,~
100
v
.
3
100
3.70’
‘
H
~_
-32 "
34
.19
31
> i
7 ~13
'
1
-,.60
500
11.1
1
‘V
r 3
‘12.3
‘ 5.3
~
25hrs.
G T
-'
5. 22
"3.0
.
.
5hrs.
'
F
‘
.
>
20min.
ammonia
O
100
100
10.5
1:28]
cosity at 79°F“
'
water ‘
~
5.11
1.15
5. 46'
32.38‘
In glue {annular-vis
7
_
Casein
B
'
Unextruded casein ..... .;.
.
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A_
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Sn (ous) chloride _________ _-
_
- I .
Amounts used
asem,
amt.
~
.
.
C
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.
Ammoma test
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40
1
-
_
10
I
1011
.
Y
i=insolubla in this formula. j-slightly soluble but jells almost immediately. L The “metal.compounds”'given in the above list It willbenoted (see last line‘of table) that the
are not substances which, in the presence .‘of glue prepared‘from casein in its‘ natural condi;
vwater, act as solubilizing agents for casein.
tion ‘gave’ viscosity ‘values of '40; at 20 minutes,
' As indicated in Tablel, nearly all the casein
10 at »5 hours and was a‘ firm jell'at 24 hours.
‘compounds listed are solubledn ammonia, while
‘Some of the casein compounds "(indicated by the
a few are insoluble even_._when.an excess of .am
letteriin columnG) did not dissolve in this
75 monia
employed“ All the compounds are in
formula',"while others (indicated'bythe letter 1')
2,103, 153
dissolved to somev extent forming a sti? mass
~whichl'did not‘ liquefysu?iciently for a viscosity
simple. mechanical mixture, of‘the same ingre
dients.
_
v
In some
e. g. ‘cases
in the‘case
the products
of
w are_ "of dif- _
determination to be made, showing thatthey are . ferent color,
cobalt ' carbonate
unsuitable for use in this formula but'not neces
sarily. unfit foruse
other glue formulas. It 'the'M mixture isof a light brown color while the -
extruded ‘product E isv brick red. 7
Cl
Table 2
.‘10..
5
' Compound used
t
Amt. of
Amt. of
used
used
compound
‘ .
Bi hydroxide ______________ __
~
-
‘
c
uspgd
Co carbonate"
_
Do _ _ _ _ .
'
M
9.48
D0 _ _ . _ _
.D
Kdicbromat
_
E
1.26
,-lma_y be noted thatithe glue made from the casein
compound of calcium carbonate, which in the
early stages has substantially the same consis
tency as that prepared from casein, remains ?uid
overnight which is an important advantage-for
some purposes, while the glue made'from the
.30 casein compound of nickel carbonate maintains
_ a more uniformvconsistency over the ?rst few
hours and also remains ?uid and usable over
night,_whereas the casein glue in the same period
of time has passed into an unusable condition.
.35 The compound with cadmium chloride-is insol
uble in ammonia and insoluble in the glue for
‘mula but it is soluble in-sodium carbonate solu
‘
. It is to be understood that the results recorded
40 in the above table are not‘ the same as would
.
7
20
'7
35
-
7.
4
7 _
7
I
800
.
7
_
‘600
/
.
.7
too
7
600
E
‘
I 600
- 60v
"
'
‘
~R
500 .
60”
'
E 180
,i
.41
7' ,
110
7
20"
2i
The differences between the viscosities 'ofythe,
ammoniacal solutions of the compounds in Table
2 and those of the corresponding solutionscom , *
taining the‘ same proportion of dr‘yjcompourrds ‘ > ’
and water in‘ Table 1 are due to ‘the di?erent
method used in making the solutions. - Ithas'been
stated-that in Table 1
I
the solutions weremade by
'_
?rst mixing 1 partfof dry'subs'tance' with”4 vparts
of water, heating and subsequently ‘diluting'with '
water to the required amount,-whilel~in Table 2
the full amount of water was .added initially.
' With some of the substances it made a difference '
whether the water
orjall in one step.
was ‘added'
severaljstep's
''On account of the widely different chemical
and physical properties of the compoun‘ds'listed ‘
be obtained by substituting for the‘ extruded
in Table 1 they are adapted fora wide, variety off
casein-compound an equal weight of a simple
mixture of its components (1. e. casein and the
for instance, when dissolved in presence of‘ani
respective salt) which has not been subjected to
45 the process of kneading and extrusion described
above. This is clearly shown inTable 2 in which
the viscosities of ammoniacal solutions of several
of‘ the casein-compounds are compared with
those obtained by‘similarly dissolving a propor
tionate mixture of the unextruded components.
The compositions of the respective casein-com
pounds are the same as in Table 1 but they are
stated here on a percentage basis for conven
ience. The parts are by weight. The amount of
salt used is recorded in the second column and
‘the amount of casein used in the third column,
these together making 100. One hundred parts
of ‘the mixture are dissolved directly in, the
amount of water shown in- the sixth column with
60 7, parts ‘of 26f’ Bé. ammonia added, heated to 160°
F. with stirring and cooled to 70° *F. The Stoer
mer viscosity of the solution at 70° F. is shown in
the last column- A like test was made with‘ 100
parts of the corresponding casein-compound dis
65 solved in the sameway.» In this table the letter
79
.
M
D0 _______________ __; ____________ _-
400
‘
800
M
_ _ . _ _ _ _ . __
371
38,
=
400
E
5.18
-
600
400‘
E
33
7
'400
.
M denotes the unextruded mixture and E the
corresponding,extrudedwmaterial. In every pair
of tests a wide difference of'viscos‘ity is observed,
and I believe that this indicates that a chemical
reaction takes place during the passage of the
material through the extrusion press, promoted
by'the kneading action, elevated pressure and
temperature and perhaps other causes. The
properties of the casein compounds thereby pro
duced are markedly different from those of a
10
‘ at 70° F.
7
-
,400
M
_ _ _ _ _ _ _ _ __
Do__; . _
-
M
-
-
600.
I
'
E
10.95
Do _ _ _ _ _
Na bisulphat
.Ca chloride._
M ,
_ _ _ _ _ _ _ 1 _ __
“used
500
'E
9.74
. _ . _ _
"
animouiai -,oi solution .
500
- M
_ _ _ _ _ _ _ _ _ __
'
.Aint..2b‘?, . Viscosity :.
.‘.used :.
.
5.18
'
water,
»_
. _ _ _ _ . _ _ _ -_
Mn citrate__
. 50'
‘ .
7.09
Zn carbonate
tion.
‘
Amt. 0i
mcgseiélnd 1533:‘
Do ________________ _; ____________ __
‘
20v
Amt.oi.'
casein
purposes.
,
The compound of aluminum borat'e,'. . ~
monia, with as much as 10 parts of water base
thickerconsistency or body-‘than the correspond
ing casein solution with only ‘5 parts ofwater,
and onaccount of this property of forming heavy
bodied solutions it can be used with ‘advantage ‘in
paper-coating, since'the-liquid coating ‘will lie
on the surfacerof the paperinstea'di" of '“sinking
deeply into the fibre. Combinations‘? of casein
with saltsof lead, mercury, arsenicycopper and
the like are useful in the making of insecticides.
They provide, a very satisfactory means or apply
ing to vegetation, asa spray, solution of poisonous
products which adhereto the foliage and-‘produce
the desired effects; or in a ?nelypulverized form
they can be applied as a dust with or without the
additionof a, small proportion of alkali so that ,
when the foliage is’sliglitly moist or becomes damp
‘‘
with dew the powdered compoundwill adherelto
60 I
the foliage sumciently' to be practical for aeust
insecticide.
I believe‘that some of thecornpounds will .havel '
particular value as fertilizers or plant-foods. iuvIt' I I
is known, for example,’ that certain 'typespf"vege_:¢
tatlon require a small amount of manganese, and _
the availability of ‘such material in the so'iliispf
great importance. In the casein-manganese com;
bin'ations the manganese is ‘present inA_-a_n,espe.-J
cially
available
form.v
‘
v
’
'
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‘
l
‘
The combinations of casein ‘with
made by this process; which are vsoluble in 'airi—»"
monia, when applied to'paper and dried form an
insoluble coating without the addition vof‘ any
other substance. ‘It may be 'hote'd‘in Table 2.
2,108,158
I that there is a wide. difference in the physical
consistency of the ammoniacalsolution of the ex
truded product and a mixture vof casein ‘with
potassium dichromate similarly dissolved with 8
parts of water, the viscosity of the former being 60
and that of the latter 500 which represents a
thin watery solution of less commercial value.
With a lesser proportionof .water the casein—
dichromate compound has a heavy, almost jelly
10
like consistency.
‘
‘
~
g
The above-mentioned casein; combinations with
lead hydroxide and bismuth hydroxide provide
glues in the glue-formula above described which
remain ?uid over a much longer period than those
15 ‘prepared directly from the casein.
I believe that some of the casein compounds
produced by this process e. g. those of bismuth
’ and iron have therapeutic value.
casein, said product being extruded under heavy‘
pressure while containing less water than casein,
such product being insolubleinwat'er but soluble
. in alkaline solution .
3. As a product, a homogeneous vcombination
of acid-precipitated casein with a compound
selected from the group consisting of metal salts,
metal hydroxides and ammonium salts, said com
pound being not suf?ciently alkaline in reaction
to constitute a solubilizing agent for casein, to-“ 10
gether with an alkaline substance which renders
thejproduct soluble in water, and, which com
pound is capable of reacting with moist casein,
said product being extruded under heavy pressure
while ‘containing’ less water than'casein.
15
4. As a product, va. homogeneous combination
of acid-precipitated‘ casein with a compound
selected‘ from-the group of heavy metal com
Theca'sein used in these tests was a commercial pounds consisting of'metal salts, metal hydrox
20 grade made by precipitation with hydrochloric ides and ammonium salts, said compound being
acid, which type I have found to be more suit ' not su?iciently‘alkaline in reaction to constitute
able in the present process than the rennet casein a solubilizing agent ‘for casein, and which com
usually employed in the art of plastics but I may pound is capable of reacting with moist casein,
said product. being extruded under-heavy pres-1
also use. caseinprecipitated by otheracids.
25
For making, the tests of viscosity in ammoniacal sure, while containing less water than c‘a‘sein."_
_ 5.v As a productga dried homogeneous combi
solution the extruded and dried product was
ground .to pass through a standard 24 mesh wire nation of acid-‘precipitated caseinv with a corn
screen. The ‘materials used in the glue formula _ pound selected from the group consisting of metal
tests were ground to pass a 50 mesh wire screen in salts, metal hydroxides and ammonium salts, said
30 order to facilitate dissolving in the glue-mixing , compound being not su?iciently alkaline in re-'
operation which is conducted at ordinary room action to constitute‘ a solubilizing agent for
casein, andwhich compound is capable of retemperature. _
It mayin some cases be possible to omit the acting with moist casein, said product being'ex
drying and comminuting step, e. g. where the tru'ded under heavy pressure whilecontaining less
extruded material (say ribbon) is run directly
into an alkaline solution to dissolve the ‘casein
content and/or other alkali-soluble constituents
present.
.
a
Instead of drying the ribbon and then com
40 minuting the dry product, it may be feasible in
some cases, to comminute the ribbon, and to then
dry ‘the comminuted material, followed, if desired,
by further grinding.
.
The ?nal product will be ordinarily dissolved in
45 an alkaline solution before use.‘ But in some cases
alkali is added before the ?nal extrusion step,
and .the product can then be dissolved in water.
The term “not. strongly alkalinemas used in
the appended claims is intended to include not
50 only salts and compounds which in aqueous solu
tion or suspension, are neutral or acid to indi
cators like litmus, but also substances such as
lead hydroxide which. when suspended in water
may give a very slightly alkaline reaction, to
65 litmus, but are not su?lciently alkaline ‘to act
as solvents for casein.
I claim:
"
I
water
than, casein.
.
'
'
20.
I
,
80
'
'
6. As a product, a compound of acid-precipi
tated casein with a metal= salt, which, in'lthe
presence of water, does not constitute a casein
solvent, such product being soluble'inv caustic soda
solution, such product being extruded under high
pressure with an amount‘of water which is only
a minor fraction of the amount of said caséinJ
7. As a product, a composition of acid-precipi-,
tated casein combined with a metal salt, which,
in the presence of _'water,'does not constitute a 45
casein solvent, such product being soluble in vam
moniacal solution, such product being extruded
under high pressure with an amount of water
which is only a minor fraction of the amount of
said
casein.
-
I
~
7
~
‘
8. As a product, an extruded reaction'product
of casein with a heavy metal compound3,'such
product being soluble in caustic soda solution,
such product being extruded under high pressure
with an amount of wateriwhich-is only a. minor
fraction of the amount of said'casein;
" 66
‘ ‘
' 9. As a product, an extruded reaction product
'
_
1. As a‘ product, a homogeneous combination
60 of acid-precipitated casein with a compound
selected from the group consistingof metal salts,
metal hydroxides and ammonium salts, said com
pound being not sui?ciently alkaline in reaction
to constitute a solubilizing agent for casein, and
of casein with a heavy metal compound, such
product being soluble in ammoniacal solution,_
such product being extruded under high ‘pressure
with an amount of water which is only'a minor
fraction of the amount of said casein.‘
Y I '1' '
.10. A process of making- a casein product of
thecharacter set forth, which comprises adding
65 which compound is capable of reacting with . to moist casein containing lessiwater'than casein,
moist casein, said product being extruded under a. compound which in'the' ‘presence of water is
heavy'pressure while containing less water than
casein.‘
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< 2. As a product,‘ a. homogeneous ‘combination
70 of ‘acid-precipitated casein with a compound
selected from the group consistingof metal salts,
metal hydroxides and‘ammonium salts, said com
pound being not sufficiently alkaline in reaction
to constitute a solubilizing agent. for casein, and
75.. which compound is capable of reacting with moist
not, a solubilizing agent for casein and which
compound is selected from the group‘ consisting
of metal salts, ammonium salts and metal hye
droxides, which are not su?lciently alkaline‘ in 70
reaction to constitute solvents‘for casein,‘_and
which are capable of reacting upon casein under
the conditions stated, well kneading the mixture .
under superatmospheric ‘pressure and ‘subsee
quently drying the kneaded mixture in the form 1
f s,
2,103,153
of pieces which have at least one small dimen
sion.
11. A process of making a casein product of
drying the kneaded mixture in the form of ‘pieces’ which have at leastone small dimension.
the character set forth, which comprises adding
the character set forth, which comprises adding ‘
to moist casein containing less'water than casein, '
a salt selected from the class. consisting of non
to moist acid-precipitated casein containing less
water than casein, a salt of a metal other than
an agent which, in the presence of much water
will render casein soluble, and which salt is
capable of reacting upon casein, well kneading
10 the mixture,'extruding the same through‘ a nar
row opening and drying the extruded material
in the fonn of pieces which have at least one
small dimension.
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12. A process of making a casein productof
15 the character set forth, which comprises adding
to moist casein containing less water than casein,
15. A process of making a casein product of T I
basic salts of metals and non-basic salts of am- '
monium, which‘ salt?is capable of reacting upon '
casein, well kneading the mixture under super
atmospheric pressure‘ and drying the'kneaded 10
mixture in the form of pieces which'have at
least- one small dimension."
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16. Process of claim 10, followed by vgrinding v '
the dried product.
1'7. A process of making a casein product of
the; character set forth, which comprises adding
a compound of a metal capable of reacting upon to moist casein containing less water than casein,
casein to form a water-insoluble compound, well a‘chemical compound selected from the herein
kneading the mixture, under superatmospheric ‘ described class consisting of non-alkalinesalts
pressure, and converting the kneaded mixture of heavy metals, hydroxides of heavy'metals, 20
into the form of pieces which have at least one
salts of- ammonium, calcium, strontium andvmag
small dimension.
13. A process of making a casein product of
the character set forth, which comprises adding
a heavy metal salt to moist acid-precipitated
casein containing less .water than casein, well
nesium which when mixed with water give liquids '
which are not strongly alkaline, and the salt of
these metals with organicacids; salts of anti-'
mony, aluminum and cadmium; soluble chro
kneading the mixture under superatmospheric , mates and dichromates; acid sodium salts .of
pressure, and drying the kneaded mixture in the mineral acids, lithium chloride andmixtures of
form of pieces which have at least one small the above, capable of reacting upon casein under
dimension.
the conditions stated, well ‘kneading the mixture 30
14. A process of making a casein product of under superatmospheric‘ pressure and subse-j
the character set forth, which comprises adding quently drying the kneaded mixture in the form
a hydroxide of a heavy metal to moist casein con
of pieces which‘have at leastone-small dimen-l
taining less water than casein, well kneading the
mixture under superatmospheric pressure and
HENRY V. DUNHAM. ~35.
sion.
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