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Патент USA US2408626

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0¢f- l, 1946-
w. R. GRAHAM, JR., E-rm.
Filed June s, 1942
_ 2,498,625
Patented Oct. 1, 1946y
William R. Graham, Jr., Kansas City, -and George
0. Kohler, Mission, Kans., and Richard D.
Hoover, Kansas City, Mo., assigner: to Ameri
can Dairies Incorporated, Kansas City, Mo., a
corporation of Maryland, and The Quaker Oats
Company, Chicago, lll., a corporation of New
Application Jane 5, 1942, sensi No. 445,958
4 Claims. (el. 21o-8.5)
Our invention relates to a method ofand alJ- l
paratus for separating and concentratingcaro
tene, vitamins, xanthophyll, and other fat solu
ble organic material from chlorophyll and other
nondialyzable solutes in plants such as grass, al-falfa, spinach, or other vegetable matter. The
process may alsol be employed to separate and
concentrate the carotene, vitamins. xanthophyll
and other iat soluble organic material from other
non-dialyzable materials in plants containing n'o
chlorophyll such as carrots or sweet potatoes.
We have found that certain fractions of a fat
soluble extract from plants will dialyze through a
covery systems must be used and the total quan
tity-oi solvents is disproportionatelylarge. An
other difiiculty with this process is that the ñrst
extraction is notsuñlciently “selective" and con
siderable amounts oi chlorophyll are extracted
with the carotene.
We have discovered a method of separating
chlorophyll from vitamins which requires the
use of only one solvent. A suitable plant mate-`
rial, such as grass, alfalfa or spinach, which con
tains vitamins and chlorophyll, is treated in this
manner. The plant material is iirst partially
dried to remove a substantial part of the natu
plant cells. The
. ral moisture content from the
rubber or synthetic rubberv membrane while other 15 dried material is pulverized and> then extracted
fat soluble fractions in the solution will not. For
with a fat solvent such aspentana'hexane, hep
instance, if all of the fat soluble materials are
tane, petroleum ether, benzene, acetone, butyl al
extracted from a suitable plant material. the
cohol, ethylene dichloride, or other fat solvents
carotene, vitamins and certain other materials
or mixtures of such solvents. This solution, pref
will pass through the membrane while the chloro
erably in relatively concentrated form, is then ,
phyll and certain other materials will not dii 20 dialyzed through a membrane madekof rubber,
fuse through the membrane. When extracting
synthetic rubber, or the like, into a fresh solvent.
carotene, vitamin K, xanthophyll, and-other fat
The carotene, vitamins, lxanthophyll and other
soluble material from the plant material, it is de
iat soluble materials pass through the mem
sirable to remove the chlorophyll for the reason 25 brane into the fresh lsolvent while the bulk oi the
that chlorophyll. while harmless. imparts an un
chlorophyll remains behind.
,desirable green color 'to the vitamin solution.
. An important object of our invention, there
Also, when isolated in its pure form, chlorophyll
fore, is the provision of a novel method of sepa
is a valuable byproduct.
rating carotene, vitamins and other fat soluble
Sterols both from plant and animal sources 30 materials from chlorophyll and other materials
will also pass through the rubberv or Synthetic
that requires the use of but one solvent.
rubber membrane. Thus. this method may also
Another object of our invention is the provi
be used to separate sterols from other iat solu
sion of a method of the above mentioned charac
ble materials.
ter that may be easily yand inexpensively prac
Many of the materials in the chloroplastV are 35
labile and are destroyed or altered by addition oi
Other objects and advantages of vour inven
certain chemicals. This characteristic of these A tion will be apparent during the course oi the fol
materials has made their separation and isolation
lowing description.
a difficult task.
_' In the drawing forming a part of this specifica
' In the past, theSchertz process has been ex 40 tion and wherein like numerals are employed totensively used. A description of this process may
designate like parts throughout the same:
be found in volume 30, page 1073 of Industrial 8:
Fig. 1 is a side elevation of an apparatus that
Engineering Chemistry, published in 1930. The
may be used to practice our process, parts of the
Schertz process employs a hydrocarbon solvent
apparatus being shown in section for clearness of
to extract the carotene leaving the bulk of the 45
^ chlorophyll in the cake. Then an 85% acetone
Fig. 2 isa side elevation of another form vof. ap
extraction is employed to remove the chlorophyll.
paratus that may be used to practice our process.
One disadvantage of this method is that it re
parts being shown in section and parts in eleva
quires two separate extractions of the meal with
different'solvents. ,Thus two separate solvent vre
Referring'now to the apparatus shown in Fig.
20 into ñask 2|. About ñve hours is required
pass 250 ml. of solution through the
1, Athe numeral I0 designates a separating tank
adapted to be filled with a fat solvent such as
heptane. Flask II also contains a quantity of the
All oi' the vitamins will not -be extracted from
selected solvent. The contents of the flask are ci
the plant solution the first time It passes through'
heated by an electric element I2. When the sol
the apparatus. Therefore, after the ilrst pass,
vent in flask II is heated, the vapors rise through
we remove the diil'usate from flask II and illl the
tube I3 and into the upper portion of tube I4
flask with fresh solvent. The dialyzate in flask .
which extends through a condenser I5. As the
2 I, which is a dark green color and contains prac~
vapors enter tube I4 they condense and gravi
tate downwardly through the lower portion of '.
the tube which extends into and has its lower end
` near the bottom of separating tank I8. Thus,
flask II will continuously supply tank III with
fresh solvent. An overflow tube I6, having a
trap portion I6a, connects the upper end of tank _
I0 with tube I3. The overflow tube is preferably
tilted slightly from the horizontal so that overflow
liquid from tank I8 will pass through tube -I6
into pipe I3 and back into ilask II. A concen 20
trated solution of plant material is introduced at
'the separatory funnel I1- and -is conducted
through connecting pipe I8 to a rubber or syn
thetic~ rubber tube coil I9. Neoprene tubes are
conventional and satisfactory.
The lower or discharge end of the> coiled tube
I9 is connected to tube 20 which discharges ,into
a flask 2|. Container III and ñask I I are equipped
with suitable Stoppers assuring liquid tight con
nections around th'e inlet and discharge tubes.
Introduction of the plant concentrate to the sys
tern is controlled by valve 22.
tically all of the chlorophyll, is then poured backinto separatory funnel I1. Satisfactory results
are obtalnedif th'e plant material is passed ap
proximately six times through the apparatus.
The following table shows the results of an
actual experiment conducted as outlined above.
Total in
` Chlorophyll
’ - T mlm
p yl to
fraâtëon, recovery imágen, recovery carotene
1st distinta-.
2nd dinusate__
64. s
23. 4
21. 5
2. c
a. 1
1. 9c
2. 5s
3rd difrusate- .
15. s
2. 2
2. 47
4th ditrusata _
5th difrusate. _
6th diffusera..
-. 5s. a
33. s
19. 3
i1. 2
a. 2
2. 9
2. 95
s. os
7.25 .
ates ....... -_
13. 2
4. 4
4, 536
s4. 1
343. oo
Total (Iilïus
Dialyzate. .
It should be noted that 95.6 per cent of the
carotene (pro-vitamin A) in the solution was re
covered, while` only 15.9 per cent'of the chloro
As a typical example of the method as prac
phyll diifusate passed through tube 19. A bio
ticed in the apparatus shown in Fig. 1, a quan
tity of alfalfa was passed through a drum type 35 logicaichick assay indicated that 98.5 per cent of
the total vitamin K present was recovered in the
dryer having an intake temperature of approxl.
dlfl‘usate. Qualitative analyses have demon
mately 1600° F. and an outlet temperature of ap
strated that a high percentage of the xanthophyll
proximately 250° F. 'I'he green plant material
also diffuses through tube I9.
remained in the dryer only sufllciently long to
Explaining now the operation of the apparatus
remove a substantial amount of the natural 40
shown in Fig. 2, wherein a series of membranous
plant moisture without material discoloration or
sheets or films are used in place of the neoprene
charring of the chlorophyll. This preliminary
tube I9 in Fig. l. This apparatus operates
drying step is not essential but we have found
more rapidly and handles greater quantitiesl of
that it facilitates the later separation of the
plant material than> the apparatus shown in Fig.
chlorophyll fraction from the other fat soluble
1. Describing now the portion of the apparatus
that permits a constant circulation of liquid sol
'I'he dried plant material was then passed
vent. An essentially rectangular tank 23 is dl
through a hammer mill and ground to a flne
vided into chambers“, 25,4 26, 21, and 28 by
powder. After grinding, th'e powdered plant ma
membranes 29 of rubber or synthetic rubber. A
terial or pigment was mixed with sufficient hep- flask 30 is heated by an electrical heating element
tane to dissolve the fat soluble materials from
A tube 32 extends from flask 30 and con
the plants. This solution was then passed
nects with a pipe 33. The upper portion of pipe
through a still to remove part of the solvent leav
33 is enclosed by a condenser 34 and the lower
ing the solution in relatively concentrated form.
portion of the pipe extends into chamber 24. I
250 ml. of this concentrated solution was then
Siphon tube 35 connects chamber 24 with cham
poured into separatory funnel I1. Valve 22 was
ber 26 and siphon tube 36 connects chamber 26
opened and the concentrate permitted to flow
with chamber 28. A siphon tube 31 connects
slowly through tube I8 and coiled tube I9. Sl
chamber 28 with a constant level device 38.
multaneously fres 'solvent was introduced to the
Liquid discharged ‘into the constant level 'device
bottom of the tank I8 through pipe I4 and was
flows through trap 39a in tube 39 to flask 38.
`circulated around the exterior of the coiled tube
Ch'ambers 24, 25, 26, 21 and 28, constant level de
I9 overflowing from the tank through pipe I6
vices 38 and 45, and flask 38 are filled with a sol
back to flask II. Throughout the entire opera
vent such as heptane. When the apparatus is
tion, heater I2 causes a constant circulation of
set up, the siphon tubes 35, 36, 31, 43 and 44 are
solvent through the apparatus as previously ex
also ñlled with the solvent so that a siphoning
plained. As the plant extract passes slowly
action can take place. 'I'he liquid in flask 30 is
through’ _neoprene tube I9, the carotene, vitamin
K, xanthophyll, etc., diffuse through the wall of
the neoprene tube and into the heptane solvent
in tank I8. The dilfusate containing the vitamin
material overflows tank‘ I 0 through pipe I4 into
flask II.
'I'he chlorophyll and other non-dialyzable
materials are retained within neoprene tube I9
heated. Vapors passing olf through pipe 32 are
condensed and the condensate discharged into
chamber 24. As the liquid in chamber 24 tends
to rise, hydrostatic pressure forces liquidffrom
the bottom of the chamber to pass through
siphon tube'35 to chamber 26, from chamber 26
« the liquid passes through siphon tube 36 to cham-V
and are discharged as a dialyz‘ate through tube 75 ber 28, thence through siphon tube 31, constant
level 38 and pipe 39 to the flask 30.
amaca» '
cento! the chlorophyll was recovered with the
The crude plant extract or concentrate,
duced through separatory funnel 45, is allowed' to
lilow through tube 4I controlled by valve 42, into
chamber 21. A siphon tube 4I connects chamber
21 with' -chamber 25. A siphon tube 44 connectsV
We have tried man3 types of dialysis mem
branes but have found rubber or synthetic rubber
membranes to be most satisfactory. We have
found thata vulcanized rubber membrane stands
chamber >25 with a constant level device 45.
Liquid delivered to the constant level device 45
overiiows into tube. 45 which conducts it into a
up against the solvent longer lthan a natural rub
flask 41. .
ber such as latex. The following membranes
were tested and, in each instance, it was found
that very little,'if any, of the carotene or xantho
centrated heptane solution of plant material pre
paper parchment, animal parchment, “pliofllm,”
As an example of a typical operation, a con
phyll dialyzed through the membrane; collodion,
pared in the manner hereinbefore described was
»“lucite,” cellulose acetate, animal intestine, ani
placed in container 40. In actual practice, con
mal intestine (bile salts added) , fiber tubing,
tainer 40 is much larger than shown in the draw
paper impregnated with gelatin, and Cellophane.
ing. 'I'he heptane solvent was then placed in 15
A number of iat solvents have been found to
the apparatus as described above. A constant
be satisfactory. Among the solvents tested were
circulation of the solvent was effected by heating
-petroleum ether, acetone, ethylene dichloride,
element 3|. Valve 42 was opened suiliciently to
benzene, butyl alcohol, and various of the nor
permit the extract in container 40 to slowly enter
mally liquid homologs of hexane, including pen
chamber 21 through tube 4|. As the solution
tane, hexane, and heptane.
of plant material tends to rise in chamber 21,
It may thus be seen that we have accomplished
the carotene, vitamin K, xanthophyll, etc., dif
the objects of our invention. We have provided
fuse through rubber membranes 29 into cham
a highly eilicient method of separating carotene,
bers 26 and 28 while the chlorophyll and other
vitamins, xan-thophyll, etc. from a fat solvent
non-dialyzable materials will remain in cham 25 extract of plant materials. We have provided
ber 21 and be transferred to chamber 25 through
suitable apparatus for practicing the process.
siphon tube 43. vThe vitamins entering the sol
vThe process requires the use of but one solvent
vent in chamber 28 will pass through tubes I1
_and by using theone solvent a high percentage
and 39 into ñask 35. Vitamin materials dif
of vitamin yield is obtained. The process may be
fused into chamber 25 pass into chamber 28 30 easily and inexpensively practiced.
through siphon tube l35. Vitamins remaining in
It is to be understood that the forms of the
chamber 21 pass into chamber 25 through tube
invention herewith shown and described are to be
43 where dialysis again takes place. In cham
taken as preferred examples of the same and that
ber 25, the carotene, xanthophyll and vitamins
changes may be made in the apparatus and
again diiluse through membranes 29 and are
method which do not depart from the spirit of
taken up by the solvent in chambers 24’and 25.
our invention or the scope- of the appended
The materials not diffused through the mem
branes pass off from chamber 25 through pipe
Having thus described our invention, we claim'
44 into constant level device 45, thence into flask
1. A method of separating fat soluble vitami.-- ~
41 through pipe 45. Thus, the carotene, xan 40 and pro-vitamins from extraneous organic ma
thophyll and vitamins accumulate in flask 30,
terial contained in a fat solvent extract of plant
while the chlorophyll and other non-dialyzable
materials by dialyzation utilizing a membrane
materials accumulate in ilask 41. Solvent in the
« capable of diffusing the vitamins and pro-vita
vitamin and chlorophyll solutions is then removed
mins, comprising the steps of passing the fat sol
by processes well known to the art as by passing
vent mixture and a relatively uncontaminated fat
live steam through the residue under Ivacuum
solvent on opposite sides of the membrane to se
after distillation. The greater membrane sur
lectively diffuse the vitamins and pro-vitamins
face of this apparatus greatly decreases the time
through the membrane into the uncontaminated
required to separate the crude chlorophyll from 50 solvent, separately removing the vitamin and pro
the other fat soluble materials. This appara
vitamin containing solvent and the solvent con
taining the organic materials, and recovering the
tus also permits the use of thinner membranes
vitamins and pro-vitamins from its solvent.
than is possible where a coiled tube is used to
2. A method of separating fat soluble vitamins
speed up dialysis. We have kfound that three
passes of the dialyzate are generally sumcìen't 55 and pro-vitamins from chlorophyll contained
therewith in a fat solvent extract of plant mate
to obtain a satisfactory separation. To recircu
rials by dialyzation utilizing a membrane capable
late the plant material, the dialyzate is removed
from flask 41 and returned to separatory funnel ` of diffusing the vitamins and pro-vitamins, com
prising the steps of passing the fat solvent mix
typical experiment using »
40. The results of a
’ ture and a relatively uncontaminated fat solvent
60 on opposite sides of the membrane to selectively
this apparatus are given
diffuse the vitamins and pro-vitamins through
the membrane into the uncontaminated solvent,
Total in Peroent Total Percent pnygitto
fmffàon' recovery fraction recovery carotene
separately removing the vitamin and pro-vitamin
containing solvent and the solvent containing
chlorophyll and recovering the vitamins and pro
vitamins from its solvent.
ist diflusate.-2nd diñusate--
3rd diñusate- -
48. 7
21. 6
102 ~
17. 7
rites ....... _-
506. 0
88. 0
Dialyzate. -.-_
68. 6
l2. 0
5. 8
3. 9
5. 0
1, 358
14. 7
7, 870
1. 9
2. 9
4. 6
2. 68
114. 6
It will be noted that 88 per cent of the carotene
was recovered in three passes of the plant solu
' .l
3. A method of separating fat soluble vitamins
and pro-vitamins from extraneous organic ma
terial" contained therewith in a fat solvent ex
tract of plant materials by dialyzation utilizing
a membrane selected from the class consisting of
rubber and synthetic rubber, comprising the steps
of passing the fat solvent mixture and a relative
ly uncontaminated fat solvent on opposite sides
tion through the apparatus and that only 14.7 per 75
of .the membrane «to selectively diiïuse the vita
mins and pro-vitamins .through the membrane
into the uncontaminated solvent, separately -re
moving the vitamin and pro-vitamin containing
solvent and the solvent containing the organicl
materials and recovering the vitamins and pro
vitamins from its solvent.
4. A method of separating fat soluble vitamins
and pro-vitamins from chlorophyll containedtherewith in a. fat solvent extract of plant ma.
terials by dialyz‘ation utilizing a, membrane se
lected from the class consisting of rubber and syn
thetic rubber. comprising the steps of passing the
fat solvent mixture and a relatively uncontami
nated fat solvent on opposite sides of the mem
brane to selectively diffuse the vitamins and pro
vitamins through the membrane into the uncon
taminated solvent, separately removing the vita
min and pro-vitamin containingsolvent and the
solvent containing chlorophyll and recovering the
vitamins and pro-vitamins from its solvent.
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