Patented Apr.

6, 1943

2,315,699"

UNITED STATES PATENT OFFlCE

2,315,699

CRYSTALLIZATION OF sormrror.
Rudolph Max Goepp, In, New Castle, Del., as
signor to Atlas Powder Company, Wilmington,
Del., a corporation of Delaware

No Drawing. Application July 27, 1939,

Serial No. 286,893
5 Claims. (Cl. 260-637)
The present invention relates to a method for
part of the crystallized mass being withdrawn
crystallizing sorbitol. More particularly the in
at a time for separation.
vention is concerned with the recovery of sor
One of the objects of the invention is to grow
bitol crystals from the technical process liquors
the crystals isothermally at a moderate eco
obtained by the catalytic hydrogenation or by
nomical temperature. The method may be car
the electrolytic reduction of monosaccharides
ried out as a batch procedure or it may be oper
and the like.
ated as a semi-continuous or continuous crystal
The principal object of the invention is to
lization.
control the crystallization of sorbitol from these
Another object is to decrease false grain, re
process liquors so as to produce a pure uniform
fuse solid phase and increase the dissolved phase
quality product which is dry and free ?owing.
by recycling, that is, withdrawing portions of the
The method comprises ?rst initiating crystal
crystallizing mass, heating to melt and dissolve
growth in the liquors; then controlling the
solids and returning to the mass from which it
progress of crystallization to produce the maxi
was withdrawn.
mum quantity of crystals of the largest possible 15
A further object consists in separating the
size and with the greatest possible amount of
crystals from the mother liquor by ?ltration
freedom from one another so as to give a readily
which removes both the mother liquor and the
separable mass of crystals; and lastly, separating
dissolved impurities.
the crystals so produced from the solvent or
As part of the separation of the crystals from
mother liquor.
20 the liquor, the cake obtained by ?ltering is dried
An object of the invention is to prepare 'seed
to remove remaining traces of solvent.
crystals upon which the sorbitol will later be
Finally, the dried crystals can be ground or

deposited.

A further object is to prepare a magma or

mass of seed crystals in syrup starting from dry,

solid sorbitol crystals and syrup by intimate mix
ing of the crystals and syrup accompanied by

otherwise prepared for use.

A further object of the invention is the con
version of puri?ed sorbitol dissolved in volatile

solvents to a dry free-running powder without

recourse to spray drying.

violent agitation to break up the crystals into a

Still another object is the stripping of sorbitol
large number of smaller ones.
from the process liquors from monosaccharide
Another object is to work up an initial batch 30 reductions to produce liquors containing mix
of magma by repeated dilutions and violent in
tures of sorbitol and related polyhydroxylic
termixings, until the necessary volume is at
compounds, which mixtures are suitable as an

tained.
ingredient in the preparation of mixtures of
Another object is the production of a magma
polyhydroxylic compounds distinguished by their
consisting of crystals and mother liquor which 35 high solubility in water, resistance to crystalliza
can be separated by ?ltration on a ?lter press
or in a centrifuge and freed of most of the

tion therefrom and suitability for conditioning

purposes and'other uses.

mother liquor (which contains most of the im

The above and other objects will be better un
purities) by washing. A particular object is to
derstood by reference to the following detailed
control the crystallization as to crystal size and 40 description of the preferred embodiments of the
as to the amount of solid phase in the crystal
invention. '
lizing magma. The invention embraces the
In the following description several terms are
method of growing crystals from either aqueous
repeatedly employed and it is here deemed ad
or alcoholic solutions.
visable to set out de?nitely the meaning of these
Another object is to provide a large mass of 45 terms as employd in this speci?cation and the
seed crystals and to keep the syrup and seed in
claims appended hereto.
constant slow motion so that crystal growth will
Magma refers to the mixture of crystals and
consist largely in increasing the size and thick
liquor.
ness of the seed crystals and so that only a minor
Concentration refers to the fraction by weight
part of the crystallization will arise from spon~ 50 of total solids in the magma, whether in crystal
taneous nucleation. In this connection the
form or in solution. Concentration may be de
method contemplates, in one aspect, a semi
termined by known direct methods such as dry
continuous procedure in which a large portion
ing on sand or ?lter paper or, more conveniently,
of a crystallized mass of syrup is left to seed
the next portion of uncrystallized syrup, only a .

a secondary standard may be employed, e. g. re

fractive index which may be converted quickly to

2,315,699

ture and sugar free). The pyridine number for

pure sorbitol is about 95. The preparation of
the sorbitol pyridine complex and its treatment
to free sorbitol therefrom is described by Strain

concentration by reading the corresponding value

on a standardized refractive index-concentration
curve. For the satisfactory working of the proc
ess it is necessary to know only approximately
the purity and absolute concentration of the
syrup. Analytical errors in determining these

in J. Am. Chem. Soc. vol. 56, page 1757 (1934).

The pyridine number of a sorbitol-containing
product is an index of its crystallizing tendency
from relatively highly concentrated aqueous so~

factors can readily be compensated by making

slight changes in the liquid content of the re
placement. The liquid content is determined by
a reproducible, if not absolutely accurate, test

lutions. The higher the pyridine number the

greater the crystallizing tendency. The greater
the complexity of the sorbitol-containing prod
not the less its crystallizing tendency and vice

such as refractive index. For methanolic mag

mas the concentration can be controlled syntheti-

versa.

cally, that is, in the mixing ofithe magma, o1?

analytically by a combined refractive index-den
sity-composition chart.
Total solids includes all constituents of the

Replacement is the fresh liquor added to re

place the vvithdrawal, in the process of continu
ous or semi-continuous crystallization.

Withdrawal is the removal of a portion of the

magma or solution other than the solvent used

crystallizing batch for further processing, and

also the portion withdrawn.

in the process. This is essentially the non-vola

tile portion.

Sorbitol has been one of the most dif?cultly

False grain refers to crystals of sorbitol dis

crystallizable of the hexahydrc alcohols. Com

mercial sorbitol produced by catalytic hydro

tinctly smaller than those of maximum size ob

tainable under normal conditions, and which

genation or electrolytic reduction of monosac

small crystals result from the breaking of larger

crystals or from spontaneously produced nuclei.

charides has generally been marketed in the

form of 50% aqueous solutions or lumps of

Overload is a measure of supersaturation of a

solution and is de?ned as the theoretical yield of

solids, based on original total dissolved solids, ob
tained in passing from a higher concentration
S1 to a lower concentration S2.
mathematically as

It is defined

solidi?ed semi-translucent gel containing ap

proximately 3 to 5% of water, or as a spray

dried powder containing all impurities originally

present. So far as is known, no one has yet
30 disclosed a practicable process for the large

scale crystallization of impure sorbitol before

the present invention.
It is known that, under certain hitherto im

where S1 is the initial concentration of the solu

tion being measured and S2 is the concentration
of a saturated solution at the temperature under

consideration.
Purgeability is the ease and completeness of
removal of mother liquor from a ?lter cake, and

by extension, the potential ?lterability of crys

tals in a magma.

Purity is the percentage of sorbitol in the total >

solids.

Percentage separated solids as used herein, is

the percentage of crystals separated, based on
total solids. This is mathematically equal to

Cm- Cl
100 X ~-Cm(1
_ of)

where
Cm=concentration of total solids of the magma
and
Cr =concentration of total solids of the ?ltrate
after removing the crystals from the
magma.
When crystallization of a given solution has

been carried to true equilibrium the percentage

separated solids has the same value as the over~

load.
Pyridine number (P. N.) as used herein is an

index of sorbitol content of sorbitol-containing

material. This index is determined by crystalliz
ing sorbitol from sorbitol-containing products in
the form of a sorbitol-pyridine complex, ?ltering
the crystalline complex, adding water to it to de
compose the complex into pyridine and sorbitol,
driving off the pyridine by vacuum distillation
with water, dehydrating the sorbitol residue and
weighing it as sorbitol. The procedure is speci?c
for sorbitol since no other polyhydric material,
such as sugar, mannitol, etc., exhibits the same
behavior with pyridine. The pyridine number is
the weight of sorbitol crystallized from anhy
drous pyridine as above multiplied by 100, and
divided by the weight of the sample (ash, mois

perfectly understood conditions, sorbitol crystal

lizes from certain types of concentrated aqueous

solution, particularly extracted sorb apple juice,

as long needles, which may be freed of mother
liquor by trituration with alcohol, and then re
crystallized, in small yield, from ethyl alcohol.
Even a few percent of impurities are su?cient to

change the crystallizing behavior of sorbitol

profoundly, so that, instead of separating from
ethyl alcohol as individual crystals, it comes out
as small droplets of sorbitol-rich solution. The

droplets then crystallize very imperfectly to give

clusters of microcrystals enclosing considerable
mother liquor. If methyl alcohol is used as the

solvent, pronounced supersaturation occurs, and

separation, when ?nally induced by the custom
ary methods of seeding and scratching, is in the
form of gelatinous masses. Similarly, if water
is used as the solvent, a supersaturated solution
of pure or impure sorbitol, at a concentration of
85% or more, at 25 C., either sets up to a stiff,

translucent gel, or, if the concentration is not

too great, a few very ?ne crystals are produced
spontaneously, which grow for a time, and then,
sooner or later are engulfed in a solid, virtually
un?lterable mass of very small crystals, sur

rounded by gelatinized syrup.

The unsatisfactory crystallizing behavior of

impure sorbitol is re?ected in the various meth
ods hitherto proposed for purifying it, such as
preparation of the benzal derivative and regen
eration therefrom, regeneration from the read

ily crystallized hexa-acetate by saponi?cation,

or from the well-crystallized pyridine-sorbitol
complex. All these methods are slow, require
expensive reagents, give low yields and are un
suited for the large scale economical puri?ca
tion and preparation of crystalline sorbitol.
The crystallization behavior of sorbitol 'in
impure solution is due, as I have found, to the

natural tendency of sorbitol to crystallize in rela

tively long needles. This characteristic crystal

2,315,699

habit is, in turn, due to the fact that the ends

the starting syrup below the necessary limits.
of the crystals grow much faster than the sides.
The reducing sugar in the crystals after the crys
As a result, supersaturated aqueous solutions of
tallization is generally about 0.3 of the reducing
sorbitol somewhat resemble solutions of starch
sugar
concentration of the starting syrup (dry
or gelatin, in their consistency when gelled. The
basis) and the ash content of the crystals is about
gelatinization is in all probability due to the
0.4 that of the starting syrup (dry basis). Also,
spontaneous formation of numerous nuclei,
if
the starting material is low in ash and reduc
which then proceed to grow almost entirely along
ing sugar then, providing the original P. N. is
one dimension, forming, in effect, tiny ?bers.
high enough (preferably above '79), two crops
These ?brous crystals grow very rapidly through 10 of
sorbitol can be taken out both of satisfactory
the solution, twisting and intertwining, thus
ash and sugar content.
forming a network of interlaced ?bers which
The preferred syrup for isothermal crystalliza

soon immobilize the interstitial liquor. In im

pure solutions, growth slows down due to ad
sorption of impurities on the crystal faces, so

tion at 25 0. should have a concentration of

about 75-82% of total solids depending on purity.

Such a syrup can be added to a heel of 6090% of

that crystallization soon comes to a halt, due

the original or a previous days batch, which heel

should contain for seed a high percentage, say
10 to 13 % separated sorbitol crystals based on the
total sorbitol in the heel. In the course of about

to coating of all faces of the crystals with im

purities, with only a few percent of crystals
separated. As a matter of experimental fact,
the separation of less than 3% of ?brous crystals 20 24 hours with constant temperature conditions
can immobilize an impure aqueous sorbitol
and stirring, the separated sorbitol crystal con~
syrup of 75% concentration at 25 C.
tent should be about 10 to 13% and a withdrawal
If the spontaneously crystallizing magma is
of 10-40% may be made if the semi-continuous
stirred, the effect is to accelerate very much the
process is followed. While such a syrup can be
rate of gelatinization without changing its
made to grow 10 to 13% of crystals at 25 C. the
character. This is due to the breakage of the
viscosity of the solution. is so high that the crys~
very slender and fragile sorbitol crystal by the
tals cannot be purged satisfactorily and it is nec
internal friction of the solution, thus increasing
essary to dilute the magma before ?ltering it, as
the number of active end surfaces, and hence
described hereinafter. This dilution is preferably
the number of crystals produced.
30 made with methanol, although ethanol may also
The present invention in its general form,
be used. The alcohol reduces the viscosity and
comprises the crystallization of sorbitol, in mo
hence increases the ?lterability of the sorbitol.
tion, from solutions in volatile solvents, with
Without the use of an alcohol diluent the ?lter
careful control of overload, and in the presence
cake from a straight aqueous magma contains a
of sufficient seed crystals, the amount of seed
very high percentage of mother liquor.
e.
crystals present being su?icient to prevent
syrup of P. N. 65-70 purged with an alcohol, a
gelatinization, but not enough to increase the
yield averaging 25 of a product which. averages
viscosity of the solution unduly, or to yield ex
close to P. N. 85 is obtained. The syrup remain~
cessive false grain. The invention produces
ing after the separation of crystals from the
crystals which are well formed, relatively strong 40 magma has a P. N. of about 60.

straight needles, not interlaced, and readily

In preparing a new crystallizinor run an initial

purgeable of the mother liquor. The magma

thus obtained may be freed of most of the
,mother liquor by ?ltration, and the product con
verted to dry, substantially moisture-free solid
crystalline sorbitol by drying in thin layers or

body of seed crystals is required and this may

be prepared as follows:

A small quantity of pure dry sorbitol, prepared

for instance by the method of Strain, J. A. C. S.
56, 3.757. is first taken and ground in a mortar.
or stirred with an egg beater or chopping type of

in a ?nely divided condition.

I. CRYSTALLIZATION FROM
SOLUTION

stirrer, with about ten times its weight of slightly

AQUEOUS

It has been found that sorbitol crystals can

be satisfactorily grown from water solutions.
As a starting material any suitable source of
sorbitol may be used, such as the syrup ob

supersaturated sorbitol solution which may be

50 made from the pure crystals or may be a less

pure technical syrup. Working at 25" 0., at which

temperature
concentration,pure
a feed
sorbitol
of 75%
is saturated
concentration
at
is
used corresponding to an overload of about 12?;
tained by the electrolysis or hydrogenation of 55 as determined by the formula
forth. above.
glucose, fructose. invert sugar, inverted lactose,
Material of S?-SGit purity such
may be ob
or by the extraction of toyon or mountain ash
tained by the hydrogenaticn of glucose or invert
berries with alcohol. Preferably the starting
sugar, would require a 76-78%
solids con_
material should have a P. N. of at least 65-70
centration, while a still less pure material would
with an ash content preferably not exceeding 60 need a total solids concentration up to
to 82 7?.
2%, although it is possible to conduct the proc
The strength of feed to be used
be calculated
ess with syrups of diiTerent purities. Thus a
from the overload formula after the saturation
syrup of P. N. 50 can be used but the rate of
concentration of the feed with respect to pure
crystal growth is slow and the product still rela
sorbitol has been determined at the oper ' g
tively impure.
ccncen~
65 temperature. The overload at any

To get proper growth from a syrup of low

tration will vary with the purity of the syrup so
purity. the overload must be increased and this
that
of
thethe
particular
saturation
syrup
or equilibrium
to be used as is d mus?r
increases the viscosity. A syrup of medium
purity, such as P. N. 77, crystallizes much faster
be determined with respect to pure sorbitcl. This
at a given overload than a material of P. N. 65. 70 saturation concentration may be determined by
The growth rate may be adjusted by changing
?nding the concentration of the syrup in which
the overload as described below. Since the proc
grow
pure larger.
sorbitol crystals will neither dissolve
ess accomplishes only a relative puri?cation, the
ash and reducing sugar of the ?nal product are
After grinding'or chopping

best controlled by keeping the ash and sugar of 75

vigorously
the magma
for be:
minutes, the seed takes hold, and

2,315,699

comes appreciably thicker than the original syrup.

It is then diluted with one to three times its total

weight of fresh syrup and stirred vigorously, pref

erably with a chopping stirrer, for 15-20 minutes
further, when the magma is again diluted with a
further one to three times its weight of addi
tional syrup, and the stirring continued. In this
way, starting with a few grains of pure sorbitol,

of well-formed crystals, thereby to limit further

separation of solids substantially to the forma
tion of additional well-formed crystals and to
the building up of the size of the crystals.
In this way, the crystals can be brought up
to an average maximum length of about 0.15 mm,
and a thickness of .002 mm. Any further at

tempt to increase the size of the crystal results

in breakage, with formation of shorter frag
successive additions of supersaturated syrup to 10 ments which grow out again rapidly to the limit
ing size.
the magma of chopped-up sorbitol crystals in the
In operating a batch method the magma pro
proportion of one to three times the weight of
duced by the above steps is separated all at once
syrup to the weight of magma. With each in
according to the procedure described herein
crease in size of the batch, unless the eiliciency
after. The separation should be made when the
of stirring is increased proportionally, the time
percentage separated solids has preferably
required to thicken sufficiently before the next
reached a value of 10-13% for an aqueous
addition becomes successively longer and longer.
magma at 25 C.
During this procedure tiny fragile crystals
With further increase of separated solids, the
have been produced which tend to grow into the
crystals tend to break up into smaller crystals
undesirable interlacing ?brous type. The vigor
which impair purgeability. The viscosity of the
ous chopping has broken up the free crystals and
a batch of any desired size can be built up by

clots or" intertwined crystals into numerous short

fragments to give a large amount of fast-grow

ing, end-face crystal area.

Agitation disperses

these fragments throughout the solution thus .

adequately seeding it and preventing spontaneous

nucleation. This solution tends to become im
mobile, however. Due to the elongated shape
and very small size of the crystals, a 76% sorbi
tol solution can tolerate only about 3% or" such ;.

solid material without becoming stiff and buttery.

The ?ne needle crystals at this point have a

magma also becomes higher and at say 30% sep

arated solids the magma is very difficult to stir
and purgeability of the crystals is so poor that

operation at such conditions is impracticable.

At temperatures above 25 C. the viscosities
of the magmas will be higher than at 25 be

cause, although increasing the temperature

lowers the viscosity of a solution of a given con

centration, the increase in solubility at the higher

temperatures demands a higher concentration
(which increases the viscosity) to produce an

length of about 0.03 mm. and a transverse di

equivalent overload.

mension of about 0.0001 mm.

below 25 C. viscosities will be lower. There

fore, when operating at temperatures other than

The solution is

therefore thinned out from time to time when ~~

necessary to prevent immobilization. The crys

tals are by this means allowed to grow sepa

rately without appreciable entanglement until

appreciable lateral growth is attained.

Instead of dilution, the volume of the batch
can be kept constant and a fraction of the batch
withdrawn, heated sufficiently to dissolve the
crystals and, after cooling to the temperature of
the batch, returned to the main portion. This
in effect reduces the number of crystals and
accomplishes the same eiiect as dilution, namely,
the production of a new mixture containing

chopped crystals from the preceding solution and

overloaded sorbitol solution, the proportion of
crystals in said new mixture being less than the I

proportion of crystals in the preceding chopped

mixture.
A point is ultimately reached where the
magma can be allowed to crystallize with only

gentle agitation, just enough to bring the crystals

into contact with fresh liquor. The reason for
this is that the crystals have now sui?cient
thickness and breadth to grow as separate, free
?owing needles instead of ?bers which bend and
interlace. This point has been reached when the 00

magma will tolerate about 8 to 10% separated

solids and the preparation of the seed crystals
is now completed.
This magma has present therein a sorbitol
solution having an overload sumcient to permit
crystallization and, in addition, crystals of sur?
cient size which are present in su?icient quan
tity so that additional crystallization may be
limited to the formation of well-formed, indi
vidual crystals without further formation of
?brous crystals.

In accordance with an em

bodiment of the present invention, this magma

is slowly moved in contact with the crystals, care
being taken to maintain the relationship of the

overload of the sorbitol solution to the quantity

Similarly at temperatures

25 C. the preferred values for percent separated

solids will be somewhat greater or less depend
ing on the temperature employed.

Obviously it is preferable not to have to repeat

this procedure in building up the seed crystals
very frequently, and hence a semi-continuous or

continuous process is preferable. These latter

processes involve the separation of only a portion
of the magma at a time so that a substantial

part of the magma remains to furnish seed crys

tals for the crystallization of further syrup.
The growing of the crystals can take place in
any suitable vessel at constant temperature and
with constant slow stirring. In order to increase
the size of the seed crystals, these crystals must
be contacted with large quantities of the mother
liquor and therefore constant stirring is needed.
At the same time the stirring produces breakage
of some of the crystals thereby furnishing fresh
growing surfaces. The rate of stirring is im

portant in that the breakage of large crystals

must not be excessive-a. large number of chips
and small crystals leading to excessive false
grain, raised viscosities, and di?cult purgeability.
In place of creating motion of the magma by in
ternal stirring, other means may be employed
such as rocking or tumbling the whole vessel in
which crystallization is taking place. It has been
found that such other ways of moving the liquid
produce breakage of crystals also, so that pre~
sumably the internal friction of the magma in
motion is a large factor in crystal breakage.
In general, the overload of a solution increases
as the temperature is lowered and this fact is

frequently employed in crystallizing where suiii

cient supersaturation is not available at given
temperature. However, it is diiiicult to control
supersaturation induced by cooling
solution
and since sorbitol solutions in either water or

alcohols may be readily obtained in suihciently

2,815,699
supersaturated conditions even at room tempera

ture to give satisfactory overloads, it is prefer

able and much simpler to conduct the crystalliza
tion at one temperature. In general it has been
found convenient to conduct the crystallization
at a temperature of 1540 C. and preferably 25
is selected as a mean of indoor temperature
which can be maintained with a- minimum of

quently, a high overload can be used and a

greater capacity achieved Without incurring the

risk of undue thickening and false grain forma
tion.

The semi-continuous withdrawal and replace

ment process is much better adapted to com
mercial operation than the batch process. The

equipment required for semi-continuous crystal

heating or cooling of the solution at any time.
lization is a slowly stirred crystallizer which can
With relatively impure syrups the viscosity 10 be maintained at a constant temperature, a mix
overload relationship favors operations at lower
ing tank, a centrifuge or ?lter press, and a dryer.
temperatures.
In this form of the invention there is no need
According to the preferred method, a portion
for continued use of small scale equipment as

of the magma prepared as previously described,

in the case of the batch process where the crys
is withdrawn for sparation and this portion is 15 tals must be built up from small quantities of
replaced with an equal quantity of fresh super
material. In the semi-continuous process the
saturated syrup. In practice the process is car
small depth of withdrawal and replacement make
ried on semi-continuously by the periodic re
for uniformity and homogeneity of the product
moval of a portion for separation and its re
despite fairly wide fluctuations in the purity of
placement by an equal quantity of fresh syrup. 20 the feed. The control of the process is very sim
The withdrawal of a portion of the magma at a

time when the growth of well-formed, readily

purgeable crystals has reached a maximum, and

ple, requiring only slight adjustment from time

to time in the concentration of the feed syrup to

raise or lower the overload to compensate for
the replacement with sorbitol syrup results in a
changes in purity. These advantages more than
decrease in the proportion of crystals in the
25 outweigh the disadvantages of getting a daily
magma and an increase in the percentage of the
yield of only a small fraction of the solids in
sorbitol in solution. The minor amount of
process.
breakage caused by the slow agitation is suffi
The semi-continuous, and also the continuous,
cient to provide fresh crystal surface for the
processes of this invention provide means for

promotion of crystal growth. This crystal growth

crystallizing sorbitol at the maximum obtainable

is thereby controlled so that it tends to take place 30 rate of growth compatible with production of
on the small broken crystals thereby preventing
purgeable crystals. The attenuated growing
the accumulation of a sui?ciently large amount
habit of the sorbitol crystals is such that in a
of small crystals which would render the magma
moving viscous solution breakage occurs at an
di?icult to purge, and further preventing spon
average length of 0.15 mm. The distribution of
taneous crystallization in amounts sufficient to
crystal sizes, therefore, varies, the majority of
immobilize the magma.
crystals being between 0.05 and .15 mm. in length
Since crystallization is preferably isothermal
and about 0.00'10.002 mm. in thickness and
the variable elements are only concentration of
width. There is a slight amount of false grain
replacement syrup, agitation, and amount and 40 and there are also a very few crystals substan
form of seed used. The amount of seed can be
tially thicker and a little longer than the others.
controlled by the frequency and depth (quantity)
At this particle size and distribution and under
of withdrawal, the amount of seed being what is
the preferred operating conditions, the crystals
left in the crystallizer after a withdrawal is made.
Amount of seed and also the form thereof can be

varied by recycling as before explained.

The replacement syrup has preferably 75-82%
total solids depending partly upon purity and
partly on the operating conditions in the crystal
lizer. If a test of the total solids of the magma

in the crystallizer shows that it is not holding

its own against periodic withdrawal and replace
ment, the concentration of the replacement is
increased until the magma reaches equilibrium.
Conversely, too high an actual overload leading
to undue false grain and lessened purgeability
is corrected by lowering the concentration of the
replacement. Another factor to be considered
in the choice of concentration is the viscosity of
the magma, since too high an overload makes the
magma di?icultly stirrable and. also leads to false

grain formation.

can increase in total amount from an initial 9%

(obtained from the seed) to 13% within 24 hours.

If the number of 0.15 mm. sorbitol crystals is in
creased much above 13% there is a tendency to

increase the rate of breakage and false grain for

mation with attendant impairment of purge
iability. Hence, with aqueous magmas at 25 C.
it is preferred to operate with not more than
about 13% separated solids present in the
magma.

Instead of growing the crystals in a semi-con

' tinuous manner and periodically removing por

tions of the magma, the method can be operated

continuously with high concentration syrup, say

80% total solids, feeding and withdrawing at con
stant rates.

Although the entire contents of the crystal

lizer in a batch process, or the withdrawal in the
semi-continuous or continuous process, may be
?ltered directly in a press if so desired, the re
moval of the viscous aqueous mother liquor from

The frequency and depth of withdrawal are

varied in accordance with the purity of the start
ing material since rate of crystal growth is de 65 the crystals is not complete and the puri?cation
pendent on purity, all other conditions being
achieved is not as good as may be desired for some
equal. With a syrup of P. N. '70 crystallized at
purposes. Accordingly, it has been found advan
78% concentration at 25 C. a satisfactory
tageous in most cases to thin the viscous aqueous
growth is maintained when 10% is removed every
mother liquor with a quantity of alcohol, either
12 hours. On processing with methanol as de 70 ethyl or methyl. The quantity and temperature
scribed below, a 22% yield is had. Less pure
of alcohol used is such as to reduce the viscosity
syrups crystallize more sluggishly so that longer
of the magma substantially but not enough to
growth periods are necessary. Purer materials
diminish the overload or to cause the formation
make it possible to withdraw larger amounts for
of two liquid phases. The ethyl alcohol maybe
separation, If withdrawals are made more fre
used in the form of a mixture with methyl alco

2,315,699
hol such as the denatured alcohol formula No. l.
Ethanol is much less satisfactory than methanol
due to formation of two liquid phases at certain
concentrations, that is to say, ethanol and aque
ous sorbitol solutions are not miscible in all con

centrations, particularly those obtained momen

fusion of water vapor from the interior of the

crystallizing mass.
The method of getting free running crystals
from magmas of relatively high purity has been
denominated magmatic drying and is similar
to the drying of damp ?lter cakes, the principal
difference being in the relative proportions of
crystallized and uncrystallized solids at the start

tarily when stirring the ethanol into the magma.

There appear two solutions of different densi
of the drying process because no ?ltration step
ties, the heavier rich in sorbitol containing a
small amount of alcohol and water, the other 10 is interposed where the magma is dried directly.
For example, a soggy ?lter cake, which may con
consisting mainly of alcohol containing sorbitol
tain 40% crystalline or separated solids, 48%
and water. Droplets of this heavier solution in
dissolved solids and 12% volatiles can be dried
contact with the sorbitol crystals agglomerate
them into a sticky mass which is very difficult to

?lter. For this reason, ethanol gives a product

of lower purity which is much harder to dry than

the methanol purged crystals. However, it is to

readily under vacuum or in dry air if the overall

purity is 80% or better. Likewise, an un?ltered
magma of like purity, but having a greater per
centage of dissolved solids can be dried if spread
out into a thin layer or otherwise given a large

be understood that ethanol can be used to dilute

surface area and subjected to drying tempera
an aqueous magma prior to purging if so desired.
tures or placed in dry air.
The dilution is preferably made with the alco
The temperature used at the start in the mag
hol, and water ifenecessary, to give a mixture
matic drying should not exceed that used for
whose composition is 35% total solids in 52%
growing crystals in the magma, otherwise seed
alcohol and 13% water. It is essential to mix
crystals will be dissolved and gelled portions
the alcohol and the magma thoroughly so that
produced in the cake, which lose water only very
the dilution is complete and the resulting mother
slowly
and are very difficult to comminute. As
liquor is a homogeneous alcohol solution. Vigor
drying proceeds, the temperature may be raised.
ous stirring for several minutes is therefore used
Accordingly, the temperature used for growing
to insure this result.
magmas for magmatic drying should be as high
The diluted magma is thereupon ?ltered in a
centrifuge or other suitable ?ltering device. In 30 as possible so that the Volatile solvent can be re
moved as rapidly as possible without dissolving
the interest of uniformity it is desirable to main
any crystals in the mother liquor.
tain constant ?ltering termperatures. The ?lter
The apparatus and procedure used for grow
cake thus obtained may be dried readily either
ing the crystals in a magma to be separated by
in a vacuum dryer or in air of humidity less than
magmatic drying are similar to those used in the
50%. Vifhere atmospheric humidities above 50%
relative humidity are encountered, an enclosed
solvent centrifuge or a ?lter press are preferably
used. Where heat is employed in the drying, care

preparation of the magma for separation by ?l

tration. In preparing magma for magmatic dry
ing, however, the process should be started with

must be taken that the temperature is not high

enough to melt the crystals in the ?lter cake.
The dried product is a soft, readily comminuted
mass of very ?ne crystals having an impurities
content of less than 35% of that of the starting

ature gradually raised to LO-45 C., the temper

ature and concentration being controlled
throughout so that the magma is at all times
supersaturated with respect to sorbitol. The
preparation of a magma for magmatic drying

syrup.
The dilution and ?ltration are preferably con

ducted at the same temperature as the crystal

lization,
Dilution with alcohol is desirable to get good

puri?cation and rapid drying of the ?lter cake.

if after diluting the magma with alcohol any
considerable period of time is allowed to elapse
before ?ltering, considerable further crystalliza
tion takes place in the alcoholic magma. Hence,
the alcoholic magma can be used also as a growth

medium for a crystallizing process. As will be

seen below, even better crystallization results are
obtained where the crystals are grown in an alco

a cold, aqueous magma at 25 C. and the temper

can be advantageously conducted in a vacuum

pan which can be operated as a continuous crys

tallizer, using periodic withdrawal and replace

ment. When using a vacuum pan, agitation can

be provided by bubbles, so that mechanical

stirring is not necessary, but where this is done,
the feed should not be supersaturated, but should
be saturated or even less, i. e., it should contain
excess water, whose removal under vacuum sup

plies the bubbles necessary for agitation.

This magmatic process is particularly adapted
to the preparation of crystals from aqueous mag

mas due to the high concentration of sorbitol

in saturated aqueous solutions. At 35 C. an
87.5% solution of sorbitol is somewhat super
holic, preferably methanolic, magma.
Where it is desired to obtain a product of 60 saturated and has only 12.5% of volatile sub
stances to be removed by drying or evaporation.
greater purity than the starting solution it is
he rate at which drying should be done de
necessary to remove the mother liquor as a liq

uid to carry off the dissolved impurities. How

ever, when it is desired only to convert sorbitol
syrup to crystalline form without puri?cation,
then centrifuging and the alcohol dilution re
quired for the latter can both be dispensed with
and the liquor from a water crystallization dried
down to solid crystalline sorbitol. It has been
found that un?ltered aqueous magmas of high
purity will dry if they contain originally even as
low as 10% separated crystals, 20% volatiles as
water, and 70% uncrystallized or dissolved solids,
providing that the magmas are given a large sur

face area-tofacilitate evaporation and permit dif

pends primarily on the crystallizing power and

hence the purity of the syrup. If the evapora
tion of water is pushed too rapidly, the super
saturation will increase beyond the point Where
the seed crystals can control, so that gelatini'za
tion will take place due to the formation of the

?brous type of crystais.

The rate of agitation used in preparing a mag
ma for magmatic drying may conveniently be
greater than that for crystallizing a magma for
subsequent ?ltration, in order to break up crys
tals. Since purgeability is no object in magmatic
76 drying, andsince. it. is desirable to have crystalli

2,315,699
zation proceed as rapidly as possible to facilitate

quick drying, the maximum number of well

formed crystals should be produced in the mag

purer syrup, P. N. 76, and having 77.5% total

solids concentration. After 27 daily withdrawals

and replacements with the syrup of the above

ma, regardless of size and purgeability. This is
composition, the magma is of 77.5% total solids
best accomplished by vigorous agitation of a
concentration and substantially P. N. '76, the yield
rather thick magma, which produces numerous
from the 28th withdrawal is 25% and the ash
short fragments of well formed crystals. These
and reducing sugar impurities of the product 0.3
provide sufficient surface for crystallization dur
those of the original, while the purity of the
ing the magmatic drying and prevent the spon
product is increased to P. N. 86.
taneous nucleation which is associated with gel 10
Example 4
atinization caused by ?brous crystals.
By whichever steps the sorbitol is reduced to
150 lbs. of sorbitol syrup of P. N. 73, having a
crystalline form the dried material may be
concentration of 78.0% was introduced into a
comminuted or otherwise prepared in usable
crystallizing vessel capable of providing slow and
form.
15' continuous agitation, which contained 350 lbs. of
crystalline sorbitol magma of the same percent
EXAMPLES or (lRrs'rsLLIzArios lluoir. Aqueous
age of total solids as the fresh syrup. The
SOLUTION
amount of crystals in the heel was 13.6% of the
Example 1
sorbitol in the crystallizer before the addition of
50 g. of crystalline sorbitol, either pure or
the fresh syrup and was 9.5% after the addition.
obtained from a previous crystallization from
The amount of the heel or seed magma was 70%
impure syrup, and 300 g. of an 80% aqueous so
of the total batch after the addition of the fresh
syrup.
lution of sorbitol syrup, P. N. 65, are stirred at
25 C. with an egg beating type chopping stirrer
After stirring at 24 C. for 2-: hours the amount
of crystals had built up to 14.9% of the total
until the viscosity begins to increase, which re
sorbitol. 150 lbs. of magma or 30% of the con
quires 28-30 minutes. 1000 g. of fresh solution
tents of the crystallizer was thereupon withdrawn
are then added and the chopping process contin~
ued. Thereafter a further quantity of 3000 g.
fesh solution is added and the chopping and
.

ng again repeated.

After this dilution the

and the crystallizer again ?lled up with fresh

syrup.
The portion of the magma withdrawn was
stirred up with methanol and water to give a mix

batch is transferred to a ?ve-gallon vertically

ture containing 42.8% sorbitol, the solvent being
s! and crystallizer, thermostated at 25 C. and
aqueous methanol 77% strength by weight. This
surreal at about 5 R. P. M. After 12 hours the
diluted mixture was then ?ltered on a centrifuge
resulting magma is diluted with a further quan
tity of 8000 g. of fresh solution, allowed to crys- r and spun for one hour. The wet cake contained
73.3% solids and after drying in a vacuum drier
tallize for 12 hours and then the crystallizer is
?lled up to a total of 30 kg.
yielded 32.8 lbs. of a dry, white, fluffy, friable
powder representing a yield of 27.4% dry basis.
After 24 hours the magma contains about 13%
The dry product contained 27% of the ash in the
separated solids as determined by a ?ltration test
at 25 C. and a 3 kg. withdrawal is taken and 40 original syrup and 31% of the original reducing
sugar. The dry product had a P. N. of 87 .8.
beaten at 25 C. with 3000 cc. of absolute meth
anol using a high speed turbine stirrer and add
II. CRYSTALLIZATION FROIVI ALCGHOLIC
ing the alcohol slowly over a period of five min
SCLUTIONS
utes to insure uniformity. The thin aqueous al
In
place
of
growing
the crystals in water solu
coholic magma is then centrifuged and dried par 45
tions and thereafter diluting with an alcohol to
tially by spinning for an hour, although the bulk
permit separation of the crystals from the moth
of the ?ltration is completed in 15 minutes. The
er liquor, it has been found advantageous to con
centrifuge cake is porous and dries readily to a
duct both the crystal growth and the separation
light friable microcrystalline mass. The yield is
in alcoholic solution. As solvent, either methanol
27% of original solids, the purity is about P. N. .
or ethanol may be used, but methanol is preferred
85. Since the yield of dry product usually ex
because of the fact that ethanol produces double
ceeds 25% and the separated solids before stir
layer or two liquid phase formation in many cases.
ring up are only 1013%, a substantial part of
Puri?cation is better with methanol than with
the crystallizing process takes place during the
ethanol. On the other hand, ethanol is some
stirring up, centrifuging and drying, the addi

what cheaper than methanol.

tional solids coming from the mother liquor.
Compared to the water solutions, the alcoholic
Example 3
solutions have much lower viscosities for the same
overload and therefore the alcoholic solutions are
A 3 kg. withdrawal of magma from the batch
more readily handled. High overloads are pos
of Example 1 is replaced with 3 kg. of fresh solu
tion and crystallization allowed to proceed 24 60 sible in alcoholic solutions at lower total solids
concentrations than are possible in aqueous solu
hours with constant stirring and at constant tem
tions giving the same overloads. Hence, more cli
perature. At the end of this period the sep
lute sources of sorbitol may be employed where
arated solids have returned to their original level
the crystal growth is to take place in alcoholic so
of 13%. A 3 kg. or 10% withdrawal is taken,
stirred up with 3 liters of absolute methanol, cen
trifuged and dried, giving a 28% yield of dried

lution. The crystals may be grown in a water

alcohol magma by starting with a supersaturated

product, P. N. 85.

alcoholic solution of sorbitol, withdrawing a por

tion of the magma and replacing it with solution.
The composition of the magma may be adjusted
to give supersat rations and growth rates com
patible with a suitable withdrawal schedule.

'

'

.
Example 3

A magma is built up at 25 C. in a 30 kg. crys

tallizer as described in Example 1, using a sorbitol

syrupof P. N. 68 at a concentration of total solids
of 79.5%. When 13% separated solids are
reached, as withdrawals are taken, proceeding as
in Example 1, replacements are made with a

The use of aqueous alcohol as a solvent carries

with it several advantages. The viscosity of the

'saturated, or moderately supersaturated, solu
tions of impure sorbitol in strong alcohol is much

2,315,699

lower than that of the corresponding aqueous so

lution, thus enabling a higher overload to be car
ried by the magma without increasing the vis

previous batch is not available, a seed magma

may be used which is built up as described

above with reference to crystallization from

aqueous solution and the magma thus grown may

be'diluted with alcohol before addition to the
syrup to bring it to equal alcoholic content. The
seeded magma is maintained in a crystallizer,
generally at constant temperature. and stirred
continuously for the period necessary to produce
be worked economically for puri?ed sorbitol. Be~ 10 the maximum crystal growth. As a rule the min
imum period for this growth is 24: hours and at
cause of low viscosity the replacement can be
the end of this time a withdrawal can be made
mixed into the batch much more quickly without
and the crystals seperaied from the mother
excessive power requirements and Without undue
liquor. As in the case of the aqueous crystalliza
crystal breakage and false grain formation.
tion care is taken to maintain the relationship
Also, much higher overloads can be used in
of the overload of the sorbitol solution to the
alcohol than in water without is r of gelatiniza

cosity unduly.

Also, with alcohol as solvent much more dilute

solutions or sorbitol can be used advantageously
so that a higher yield in proportion to total dis
solved solids can be obtained from an alcoholic
magma. Alcohol solutions of low purity can also

tion, enabling faster crystallization and higher

capacity for crystallizing equipment without sac

ri?cing purgeability and product quality unduly.

By comparison, the aqueous solutions must be
kept at relatively low overloads in order to re
tain the purgeablity of the crystals and there
fore crystallization is slower.
In the operation of an alcoholic crystallizing
method the equipment and procedure is modi
fled in accordance with known practice in other
chemical arts dealing with volatile and relatively
expensive solvents so that the solvent content
of the magma is kept constant despite evapora
tion and so that substantially all or" the solvent
is kept in process and not lost.

quantity of well-formed crystals thereby to

limit further separation of solids substantially

to the formation of additional well-formed crys

tals and the building up of the size of the crys
tals to an average length of 0.05 to 0.15 mm. and
an average thickness of 0.001 to 0.002 mm.

In

alcoholic solution the withdrawal can amount to

about 50% of the contents or" the crystalllzer,

- where the process is operated semi-continuous

ly. The depth and frequency of withdrawals and

replacements depend on the rate at which crys
tal growth proceeds and the form of crystals
produced. By observing the progress of the crys
tal content of the magma the operator will know
whether to increase the depth of frequency of

withdrawal or to decrease one or both. Thus.

Where the solvent is dilute aqueous alcohol,
if the magma is losing in crystal content or if
high sorbitol concentrations are necessary to
a large amount of false grain and undersize
produce the necessary supersaturation. On the
crystals appear, the depth of withdrawal can be
other hand, where strong alcohol is used, the
decreased so as to leave a larger heel to seed
sorbitol concentration for the necessary super
the replacement. The frequency of withdrawal
saturation is considerably less. In this latter
may be cut down to give the crystals more grow
case the volume of solution per unit quantity of
ing time to reach normal size, Excessive false
product obtained is larger than
such volume
per unit of product when dilute aqueous solu 40 grain can be remedied by lowering the actual
number of crystals in the magma by either dilut
tions are employed. The optimum composition
ing the magma with a fresh quantity of feed so
of solution is determined by balancing the cost
lution or by withdrawingr a portion of the magma,
of large equipment with the cost of recovering
heating the withdrawal suiliciently to dissolve the
the sorbitol from the ?ltrate since in the former
case where dilute aqueous alcohol is used a con 45 crystals therein and returning the withdrawal
to the magma from which it was taken. This
siderable quantity of sorbitol passes througl'i the
latter alternative in effect makes a new mixture
process unused and must be recovered from the
of the
in which the proportion of crys
?ltrate. It has been found preferable, in gen
tals to dissolved solids is lowered. Loss of crys
eral, to employ aqueous alcohol of 93% strength

50 tal content may also be overcome in many cases

by weight,
To prepare the alcoholic

for crystal

growth, a sorbitol syrup or the wet cake from a

previous ?ltration, or dry sorbitol, is mixed with

alcohol and water to prepare a syrup of the ole-

sired composition.

This sorbltol concentration

is adjusted to produce supersaturation or over

load in amount depending on the purity (P. N.)
of the corbitol used so that the magma at the
time of ?ltration will not be too thick. to handle

by increasing the overload of the replacement

syrup. Conversely, if the magma appears to
show an increase in normal crystal content,
larger withdrawals can be made and/or fre
quency of withdrawal increased until the maxi
mum yield is being taken, that is until further

increases produce injury either to the quantity

of crystals or to the form thereof.

The magma being already diluted with alcohol,

in pumps, pipes, ?ltering equipment, etc. in 60 it is only necessary to withdraw the desired por
tion and ?lter the same. The ?ltration can
the alcoholic crystallization, in contrast to the
therefore be carried out without the intermediate
aqueous process where resistance to ?ow is due
steps of diluting and mixing, which steps are
to viscosity, the alcoholic magmas are slightly
usually desirable Where the crystal growth took
thixotropic in that they set slightly when not
place in aqueous solution. The ?ltering can be
stirred and do not flow easily under low head.
performed in the same manner as described in
It has been found experimentally that
alca
holic sorbitol magma containing not more than
8% solid phase (wet basis) is as thick:
can

connection with aqueous magmas.

lviagmas containing

It has been found advantageous to the purity

of the product, although not to the yield, to wash

more than this amount of solid phase tend to clog

in constrictions, pipe bends, etc. This syrup is

the ?lter cake with a small quantity or alcohol.

This is equally true whether the crystals were

be conveniently handled.

seeded with a suitable seed

such as the
heel from a previous batch so that the actual

crystal content is equal to at least 1% or the

total sorbitol in the batch. If the heel from a

grown in aqueous or alcoholic solution.

Substan

tial increases in the P. N. of the product follow an

alcohol wash of the ?lter cake. The wash is used,
as, say, 4 to 5% of the quantity of magma ?ltered

2,315,699
although the quantity will be regulated by con-'
sidering; the results obtained by washing with
various sized portions.
The ?lter cake separated from alcoholic mother
liquor is readily dried to a white friable mass.

9.,

mixed with 91.5% methyl alcohol and heated to

dissolve the sorbitol. After cooling to 66 F. the
batch was seeded with 13.5 lbs. of wet press cake,
stirred up to a cream with ?ve gallons of the al
; coholic sorbitol solution. The mixture now had

the composition 15% sorbitol, 8.3% water vand

76.7% methanol. Of the sorbitol, about 2% of it
was in the form of individual seed crystals dis
Example 5
persed throughout the mixture.
7000 g. of a 25% solution by weight of P. N. 60 10' After stirring for 39 hours, during which time
sorbitol in 90% by weight methanol, is seeded
the temperature was gradually raised to 75 F.,
EXAMPLES OF CRYSTALLIZATION FROM ALcoHoLIo

SOLUTIONS

with a portion of aqueous magma containing

suflicient crystals to give a total crystal con-tent
of 1% in the methanol solution. This seeded
solution is maintained at 25 in a crystallizer and

is stirred continuously. The solution is allowed

to remain in the crystallizer for 3 days, after
which time the ?ltration and the recovery of a
10% withdrawal show a 22% yield, a value which
is not sensibly increased after several more days
crystallization without withdrawal. The with
drawal is replaced in each instance by an equal
quantity of solution of the same strength and

purity. Thereafter ?ve daily withdrawals are

made averaging 22% in yield. .The percentage

the mixture was ready to ?lter. Filtration on a

frame press at 40 lbs. per sq. inch pressure yielded
a press cake containing 35.9% solids which on

drying gave a white, friable product weighing 153

lbs, corresponding to a 56.5% yield. The re
covered crystals had a P. N. of 90.3.
The method of the present invention produces
from a sorbitol syrup of intermediate purity and
relatively low value, two products each of which
is more valuble than the starting syrup. A crys
talline product of improved purity and in dry
form is one of the products. The other product
is a syrup of lower sorbitol content which is of

of residual sugar and ash in the dried product are

, value in humectant and conditioning uses. Par

ticularly the syrups of low sorbitol content are of

about 35% those of the starting material, the P. N.

of the product being about 83.
Example 6

puri?cation of the syrup is a relative one, as seen

"7000 g. of an alcoholic magma arefmade up

from? an aqueous magma obtained as described
in Example 1. The alcohol used is specially. de-.
natured formula No. 1 ethyl alcohol which 'is'

substantially 4.5% methanol and 95% ethanol.

value because they are non-crystallizing. The

from the examples, and the quality of the crystal

line product obtained by one crystallization de
pends upon the quality of the starting syrup.
The crystalline product will contain a de?nite
fraction of the ash and reducing sugar content
found in the starting syrup. Likewise, the P. N.
of the product will be dependent upon the P. N.

The alcoholic magma as made up has a 51 % con-.

of the-starting syrup. Where the starting syrup

c'e'ntration of sorbitol of P. N. 65 in 66% alcohol

and the separated solids are 6-7 %. After stirring

is of intermediate or low purity, it is necessary to

24 hours at 25 C. in a crystallizer a 44.5% yield is

obtained on withdrawal. Two recyclings are

then made at 24 hour intervals, the ?rst 90%, the

second 50% of the magma. 24 hours after the

last recycling, a 10% withdrawal is made. A 33%

yield is obtained. The P. N. is 718 and the ash
and reducing sugar are half those of the original.
The i?ltered cake can be dried to a friable, semi
crystalline solid.

- .1

'

'

'

Example 7

A semi-continuous process was operated in

which sorbitol wascrystallized from an 18% solu

tion in 90 %' methyl alcohol in a 45 gallon hori
zontal aluminum crystallizer. The P. N. of the
original sorbitol was 80.5. Every 24 hours 45 to
50% of the contents of the crystallizer (135-170
lbs.) was removed and ?ltered. Fresh sorbitol
solution was added to the large heel in the crystal
lizer and after 24 hours another 50% withdrawal
and replacement were made. Twelve with

recrystallize the product to obtain high purity

crystals.
For many purposes the magmatic drying of an
aqueous magma produces satisfactory products.
This particular type of drying can be accom
plishedwhere the starting syrup is of relatively
high purity. Where this condition is met, a prod
_, not of the magmatic drying is a crystalline mass

capable of reduction to a powder, as distinguished

from the glasses normally produced by the evapo

ration of sorbitol solutions.
_. Finally,it is to be understood that the descrip
tion and instructions set forth above are for the
purpose of guiding those skilled in this art in the
crystallization of sorbitol. The adjustment of

concentrations, temperatures, rates of stirring

and the like will be determined by the conditions
of operation under which the crystallization
must be conducted. The examples are illustra
tive of some of the possible ways of controlling

the crystallization and are meant to be illustrative

only and not limiting.
drawals were made in all.
I claim:
The magma withdrawal was centrifuged and 60
1. The method of preparing crystalline sorbitol
washed with 90% methyl alcohol by weight in an
from an overloaded impure feed solution of sor
amount equal to 4.6% of the weight of the magma
bitol in water, said sorbitol being produced by the
?ltered. The wet cake contained an average of
hydrogenation of a sugar and having a pyridine
57% solids. After drying in a vacuum dryer, a

white friable product was obtained correspond

ing to an average yield of 43.5%. This material
was easily pulverized and screened. It had an
average P. N. of 90 indicating a purity of about

number not less than 50, which comprises slowly

mixing said solution at approximately constant
temperature with a seed magma consisting of a

water solution saturated with respect to sorbitol

94% and contained .32 and .14 respectively of the
and containing about 10 to 13% separated solids
percentage of ash and reducing sugar present in 70 as well-formed sorbitol seed crystals, said seed

the original sorbitol.

Example 8

266 lbs. of crystalline sorbitol as_a methanol

crystals

having

substantial

thickness

and

strength such that a gently stirred overloaded

sorbitol solution in water at 25 C. and contain
ing at least 8% of such crystals as separated

wet cake from a previous crystallization were 75 solids remains mobile, said seed magma being

16

2,315,699

present in an amount of at least 60% of the total

mixture; continuing said mixing until the amount
of well-formed sorbitol crystals in the total mix
ture increases to 10 to 13%; withdrawing a por
tion not exceeding 40% of the said total mix

ed sorbitol solution in water at 25 C. and cone

taining at least 8% of such crystals as: separated
solids remains mobile, said seed magma being
present in an amount of at least 60 %. of the total
mixture; continuing said mixing until the amount
of well-formed sorbitol crystals in the total mix

ture; separating the crystals in the withdrawn

ture increases to 10 to 13% ; Withdrawing a por
portion from the mother liquor; replacing. the
tion
not exceeding 40% of the said total mixture;
withdrawn portion. with an equal quantity of
diluting the withdrawn portion with a monohy
fresh overloaded impure feed solution of sorbitol
dric alcohol having not more than 2 carbon atoms
in water; and repeating the steps of mixing, with 10 in
a quantity to reduce substantially the viscosity
drawing, separating and replacing to continue
of the said withdrawn portion; ?ltering the with
the operation of the method.
drawn portion to separate the sorbitol crystals
2. The method of preparing crystalline sorbitol
from the mother liquor and diluting alcohol;
from an overloaded impure aqueous feed solution
replacing the withdrawn portion with an equal
containing about 75~82% sorbitol, said sorbitol
quantity of fresh overloaded impure feed solution
being produced by the hydrogenation of a sugar
of sorbitol in water; and repeating the steps of
and having a pyridine number not less than 65,
mixing,
withdrawing, separating, and replacing
which comprises slowly mixing said solution at
to
continue
the operation of the method.
approximately 25 C. with a seed magma con
a. The method of preparing crystalline sorbitol
sisting of a water solution saturated with respect 20 as in claim 5 wherein the monohydric alcohol
to sorbitol and containing about 10 to 13% sepa
used to dilute the withdrawn portion of the said
rated solids as well-formed sorbitol seed crystals,
total mixture is methanol.
said seed crystals having substantial thickness
5. The method of producing sorbitol seed
and strength such that a gently stirred overloaded
sorbitol solution in water at 25 C. and contain
ing at least 8% of such crystals as separated solids

remains mobile, said seed magma being present

in an amount of from 60 to 90% of the'total mix

crystals which comprises mixing pure dry sorbitol

with an overloaded water solution of sorbitol with
a pyridine number at least 65, the sorbitol content
of said solution being at least 75% and sufiicient
to constitute a substantial overload with respect

ture; continuing said mixing until the amount of

sorbitol; violently agitating said mixture to
well-formed sorbitol crystalsin the total mixture 30 to
chop and break up the sorbitol crystals to give a
increases to 10 to 13%; withdrawing a portion
large amount of fast-growing end-face crystal
of from 10 to 40% of the said total mixture; sepa
area, until the mixture becomes substantially
rating the crystals in the withdrawn portion from
thickened; thinning the thickened mixture by
the mother liquor; replacing the withdrawn por
dilution with several times its weight of fresh
tion with an equal quantity of fresh overloaded
overloaded water solution of sorbitol to prevent
impure aqueous feed solution of sorbitol; and
immobilization of the said thickened mixture;
repeating the steps of mixing, withdrawing, sepa
violently agitating the thinned mixture to chop
rating, and replacing to operate themethod semi
and break up the sorbitol crystals and to disperse
continuously.
3. The method of preparing crystalline sorbi 40 them throughout the mixture, until the diluted
mixture becomes substantially thickened; and
tol from an overloaded impure feed solution of
thereafter alternately thinning the mixture to
sorbitol in water, said sorbitol being produced by
prevent immobilization thereof and violently
the hydrogenation of a sugar and having a pyri
agitating the thinned mixture until the chopped
dine number not less than 50, which comprises
sorbitol crystals grow into strong well-formed
slowly mixing said solution at approximately con
seed crystals and the ?nal mixture of seed crystals
stant temperature with a seed magma consisting
of a water solution saturated with respect to
sorbitol and containing about 10 to 13% sepa
rated solids as well-formed sorbitol seed crystals,

said seed crystals having substantial thickness 50

and strength such that a gently stirred overload

and overloaded water solution of sorbitol con

tains at least 8% of seed crystals as separated
solids and is of mobile consistency.

RUDOLPH MAX GOEPP, JR.

'

CERTIFICATE OF CORRECTION.

Patent No. 2,515,699.

April 6, 1915.
RUDOLPH MAX GOEPP, JR.

It is hereby certified that error appears in the printed specification

of the above numbered patent requiring correction as follows: Page 1, sec

ond colunm, line 9-10, for "refuse" read -reduce-; page 5, first column,
line 15, for "sparation" read -separation--; page 8, first column; linen
"58, for "corbitol" read sorbitol--; page 10, second column, line 21, for
the claim reference numeral "5" read 5"; and that the said Letters Patent should be read with this correction therein that the same may conform
to the record of the case in the Patent Office.

Signed and sealed this 6th day of July, A. D. 19%.

Henry Van Arsdale,

(Seal)

Acting Commissioner of Patents.

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