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.Patented Jan. 7,1947v
2,413,676 '
Abraham Sidneyv Behrlnan, Chicago, Hildlng B.
Gnatafson, Bimdale, and James C. Healer, Chi
m0. 111., assignors to In?lco Incorporated, Chi
eago, 111., a corporation of Delaware
No Drawing. Application August 14, 1942,
Serial No. 454,874
5 Claims. ,(Cl. 127-46)
' carbon and “regenerate said beds for future use.
‘ This invention relates to the puri?cation of
The active carbon bed may be rinsed with water
after regeneration to remove excess alkali and
then a small quantity of acid such as sulfuric
aqueous solutions and has reference more par
ticularly to a process of re?ning or purifying
dextrose solutions containing contaminating me
or hydrochloric acid may be passed through the
active carbon bed to remove the last'traces of
tallic ions such as iron and copper.
In the acid conversion of starch products, a
slurry of starch is subjected to the action of hy
drochloric acid or other, inorganic acids to con
We have .found that the converter liquid not
only contains organic impurities which are non
vert the starch to dextrose. In the starch con
version process, there are produced a relatively 10 sugar in character, but also contains iron and
copper, and these metallic ions have a tendency
large number of complex organic bodies which
to accumulate in the bed of acid adsorption resin
are not dextrose and a conversion liquor is highly
and eventually interfere seriously with the re
acid by reason of the residual or remaining con
generation of said acid adsorbing bed by the
version acid not taken up by the hydrolysis re
15 means of the'alkaline solution. In view of the
fact that this converter liquid is highly acid and
,In the pending application of Henry A. Vallez
contains approximately 1500 P. P. M. of free acid
entitled “Process for refining and purifying of
{there was considerable doubt whether these metal
sugar juices.” Serial No. 396.083. ?led May 31.
ions could be removed prior to the treatment of
1941, now Patent No. 2,388 194. the proposal» iS
made that sucrose sugar ju‘ces be puri?ed by v '20 vthe converter liquid with the active carbon, by ‘
passing the solution through" a bed of hydrogen
carbonaceous zeolite, However, we have made
the surprising observation that these ions may be
removed from the converter liquid by passing the
?rst sub’ecting the raw‘sugar juice toa liming ‘
and carbonation process whereby the pH of the‘
juice is brought to approximately 7 or near neu
trality. The still relatively impure sugar juice
-is then passed through va bed of hydrogen ex
change material such as hydrogen carbonaceous
zeolite, then through a bed of activated carbon‘
liquid through abed of hydrocarbon carbonace
ous zeolite. provided the hydrogen carbonaceous
zeolite isisubsequently regenerated with a still‘
stronger acid than that present in the converter
. to remove certain colloidalmatter and colored
bodies, and then through a bed of acid adsorp
tion resin to remove the free acid in the juice 30
‘ which is liberated when the bases or metals are
In order to exemplify the process. we passed
approximately 500 ml. of converter liquid through
taken up by the hydrogen carbonaceous zeolite. . a 50 ml. bed of hydrogen carbonaceous zeolite
The resulting puri?ed juice is then sent to the
which had previously been regenerated with 300
evaporator for evaporation to a palatable syrup
ml. of half normal hydrochloric acid and washed.
or the production of granulated sugar by conven 35 The rate of- ?ow was equivalent to one gallon
tional methods.
' ' per square foot area per minute. Samples of
We have experimented with treating highly
the eiliuent were analyzed and compared wizh
acid converter liquid containing dextrose and
the in?uent content of copper and iron. The
complex organic impurities and ?nd that the acid
may be removed from thesolution by passing 40
. through a bed of acid adsorbing resin.
results obtained are indicated below:
It has
beenfound, however, that the non-sugar organic
P. P. M.
impurities of the converter liquid should be pre- .
viously removed by passing the» converter liquid
45 I'Iilueut ____________ -_. _____ -_
through a bed‘ of active carbon to remove the
organic impurities of a non-sugar character
E?luent .... ._' ............ -___
0.031 N.....
.031 N..-“
which would otherwise interfere with the regen
eration of the resin acid adsorbing bed. ‘After ,
the acid adsorbing bed is exhausted, it is regen
erated by ?rst rinsing out the acid adsorbing
' bed with water and then passing .a dilute solu
tion of sodium hydroxide or other alkali ?rst
through the acid adsorbing bed and then through
the bed of active carbon to remove impurities
‘ from both the acid adsorbing bed andrthe active
When‘ the removal of copper and iron from the
converter liquid was found to be feasible, a num- ~
ber of runs were made on a synthetic solution
containing no dextrose but containing the
amount of copper, iron and acid found in the
converter liquid.
The following table indicates _
‘as the results obtained in this experimental run us
ing a synthetic solution of iron, copper and acid,
but containing no dextrose, but containing the
amount of copper, iron and acid found in the
converter liquid.
and produced only slightly lower e?iciencies in re
moval of iron and copper ions by the hydrogen
carbonaceous zeolite. The sulfuric acid is slight
ly to be preferred for regeneration since hydro
chloric acid is extremely corrosive to iron and
In?uent characteristics
It‘ is obvious from the preceding description
Acidity _____________________ __ M31 N_ H31
that our improved procerswill operate satisfac
cu __________ __'_____________ __ 175
torily whether or not the solution being treated
130 P P M I 10 contains dextrose and organic impurities.‘ The
------------------- "
process may be applied to acid water vin general.
The te°rm “a_ substantial quantity of free acid”
or “a strongly acid solution," which is used to
designate the type or solution being treated, in
1 (H
2 1.02.0
15 dicates a solution of the type speci?ed in the
example, namely, one of about .03 normal, which
2 @318;
5 4.0-5.0.
-6 20 acid, is used to designate the relative strength
of regenerating acid solution. It is believed oh
vious, as shown in the example, that the strength I
‘75 Q8198: _____ __
' ~.7
7.0-1.25 ..... -_
4 3 mzm-
is the equivalent of a solution with a pH of about
1.5. The term “materially stronger,” used in
connection with the strength of the regenerating
7-9 mm-
Emuent Aliquot: 7.25 1.
of the regenerating solution may be of the order
of a .-5 normal solution.
Regeneration: 300 ml. N/2 H01 Q
Cations recovered ..... -_ $§;,1,‘;_M-
Cations introduced, mgm ...........
Per cent removal cations 1 ...... .-
We would state in conclusion that while the ex
amples illustrated constitute practical embodi
ments of our invention, we do not wish to limit
93.0 127-0
ourselves precisely to these details, since mani
88:}, 128:8
festly, the same may be» considerably varied
94- 6
93-0 40 without departing from the spirit of the invention
as de?ned in the appended claims.
1 Determinedimm, ‘MW
Having thus described our invention, we claim
can?“ '“mduced
as new and desire to secure by Letters Patent:
It will be noted that an e?iciency of 941/2% was _
1- In the method of purifying 3' strongly acldic
obtained in the removal of the iron ion and an ef- 4” convert“ liquor contaiPmg dextrose and non‘
?ciency of 93% in the removal of copper ion,
which results were highly gratifying in View of
the fact that the converter liquid is so strongly
sugardmpurities includmg 9' trace of {Ion and
- copper, organic impurities andasubstantialquan
my 0f free acid, by treatment wlth an 931d ad
sorbing resin, the step of ?rst removing sub
In order to make certain that the hydrogen 50 stantialiy all of said iron and copper by passing
zeolite would continue to remove the copper and
said solution through a bed of hydrogen ex
iron ions with unimpaired e?iciency .over a long » change material prior to said treatment of said
period of time, a sample of hydrogen carbonasolution with the acid-adsorbing resin. . ‘
ceous zeolite was employed in an automatically _
2. The method of removing substantially all of
operated device wherein the zeolite was exhaust- 5*) the 11-011 and copper from a, dextrose convertor
ed and regenerated without interruption for a
liquor of a pH of the order of about 1.5 and con
‘ large number of cycles. The material was subtaming traces of iron and copper’ which com
jected to 50_ cycles of continuous regeneration
prises passing said liquor through a body of
and exhaustion. Each cycle consisted of regencation exchange material operating on the hy
eration with 300 ml. of N/2 hydrochloric acid and 60 dmgen cycle_
of_ exhaustion at 1'25 gaufm per square ,foot per
minilte rate on 3' synthetl'? wager solution con’
3. The method of treating convertor liquor of a
pH of the order of about 1.5 and containing traces
galgmfr or'ggpelitgglsfogfhlfg?zuicggoznaflngocogpéj
of iron ‘and copper to remove substantially all of
Aof sample
of the emuent ,water at different points 65 '?fe
gon is‘? I‘;03:62???“€Z$£Z§t$i£°§é2i§f
the bed exhaustion gave values of copper and
.ea mg S .
q r
g th
iron which agree closely with the results of the
nal operanpg on'the hydrogen We 6 and. ere‘
manual tests heretofore described in detail. At
after'trea'tmg the s°_pu??ed hquor with an
the termination of 50 cycles of 4 hours each, the 70 gggggizizlllgnge matenal operating on the hy'
material was again tested manually and it was
found that there was no falling oif in capacity
at the end of the 50 cycles. Tests were also made
using sulfuric acid for regeneration of the hydrogen carbonaceous zeolite and it was found that
the sulfuric acid could be used as a regenerant 75
4- The method of removing substantially an
of the mm and copper from a strongly 3cm 0°11‘
Vertor liquor ?onta-ining traces of iron and 00P
Per, which Comprises treating Said convertor
liquor with a hydrogen exchange material.
5. The method of purifying a strongly acid
convertor liquor‘containing dextrose, organic im
purities and traces of iron and ‘copper, which
comprises ?rst removing substantially all of the
iron and copper by passing said liquor through
a bed or hydrogen carbonaceous exchange ma
terial which has previously been regenerated
with an acid solution materially stronger than
the acidity of said convertor liquor, and then re
moving substantially all of the acidity therefrom
by passing said converter liquor through a bed
of anion exchange material.
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