In the absence of the author, Mr. S.N.

Gundu Rao presented the following

paper.
n

Paper
CHEMICAL REACTIONS I N THE SETTLING OF LIMED
CANE JUICES

West Indies Sugar Corporation, 60 East, 42nd Street,

New Yorlc, 17, N. Y.
"Repeated generalities without quantitativg foundations are
employed frequently in technical discussions, but sweeping
statements never assist in technological progress".
From the Lessons of an Old Professor.
INTRODUCTION

A number of important reactions occur in the settling of cane juices. These

reactions become of greater importance with the introduction of continuous
clarifiers compared to the old system of intermittent subsiders.
586 SYMPOSIUM CANE JUICE CLARIFICATION
TABLE I1
Temperature Relative velocity Temperature Relative velocity
in "C. of inversion in OC. of inversion
(rate of inversion (rate of inversion
at 100°C. =100) at 100°C.=lOO)

Fig. 1. Representing the relation between pH and inversion per sucrose hour
the sucrose present at different timperatures.
 PIETBR HONIC3

The sucrose inversion is calculated as folows :

1. Take the determined p H of the juice (syrup or liquor) and read this
pH value on the abscissa.
2. Determine where this pH value crosses the temperature line (the
temperature to which the juice has been subjected).
3. Read on the ordinate the corresponding value for the percentual inversion
per hour.
4. Multiply this inversion value with the number of hours the juice has
been kept at the determined p H and temperature.
DECOMPOSITION OF REDUCING SUGARS
In the settling process there is also a change in the reducing sugars. lf
a clarified juice is subjected to higher temperaturzs at a sufficiently high pH (pH
over 7), it can be observed that there is a loss in the concentration of reducing
sugars as deterrKned with Fehling solution.
The explanations for these reactions are several, but there is a good reason
to assume that at high temperatures and at higher pHvalues the reducing sugars
react with amino acids, which reaction results in a loss of the reducing power of
the reacting reducing sugars.
The magnitude of this change is not exceptionally great, but it bas been
found that clarified juice heated at 100°C. for 3 hours can show a loss in,reducing
power of Bbout 4% of the reducing power originally present. This change in
reducing power in reducing sugars is greater at a high pH value. If we ar&working
under abnormal conditions as for instance clarified juices of a pH of 8 to 8.3,
the loss in reducing power can be as high as 3 to 4% per hour.
ACID FORMATION IN CLARIFIERS
One of the most important reactions in clarification is the change in the pH
of juice when it is heated for a longer time. This drop in pH in the settling process
is well-known to all sugar technologists. This reaction results occasionally in a
pH value of the clarified juice from the bottom compartments of continuous
subsiders as low as 5.0.
An opinion expressed by technologists not only in discussions but also
mentionea in the literature is that the change in reaction would be the result of a
kind of microbiological action of the mud and a ferinentation process, but this
assumption is undoubtedly wrong. Experiments show that the change in pH
value increases with an increase in temperature. The higher the temperature
to which juice with suspended non-sugars is subjected, the greater is the drop in
pH value. This change in p H is a chemical reaction. The reactions causing a
change in pH of juices subjected to settling are of a different nature.
The following reactions in the development of acidity respectively and
the formation of acids have to be distinguished :
(a) The transformation of CaHPO, into Ca,(P04),
2 CaHPO4+Ca"+Ca,(PO4),+2H'
588 SYMPOSIUM CANE JUICBCLARIFICATION

This acid formation can be considerable. In particular if juices have been

I
limed to a too low pH value (under 7.0) the original precipitate consists to a great
extent of CaHPO,. This reaction in juices that have been limed to an unsatisfactory ,
level can cause a severe drop in the p H during settling.
Assuming that the amount of precipitable P20, in average mixed juices
lies between 150 to 250 mg. per litre, the acid formation per litre of mixed juice
may be equivalent as a maximum to 15 to 30 ml. 0.1 normal. This is an extremely
high quantity of acid. If a juice has been limed to a pH of 7.6 to 7.8, it has been
found that after bringing this juice to the boiling point approximately 70 to 80%
of the P20, has been precipitated as,Ca,(PO,), and Mg, (PO,),. It is in particular
the time of heating and the temperature to which the juices have teen subjected in
the juice heaters, combined with the p H of the juice, which will determine the
amount of phosphates precipitated as tertiary calcium phoshate, which does not
show any change in composition in the settling process.
(b) Among the phosphates showing a change in composition with the
formation of H-ions the hexose-phosphates have to t e mentioned. The
hexosephosphates are unstable at high temperatures and dissociate according
to the general equation :
OH' OH'

The amounts of hexose-phosphates in mixed juice expressed as organically

bound P,O, is approximately 20 to 60 mg. per litre. In juices from young cane
(Primavera cane of 10 months age) larger quantities of oragnic phosphates have
been found.
It has been observed that only a part of these hexose-phosphates are hydrolyzed
in the clarification. The hydrolysis is greatest at low pH values. The maximum
acidity, if all the hexose-phosphates would t e hydrolyzed, which can develop
by the decomposition of these organic phosphates, is as an average equaivalent
to 2 to 5 ml. 0.1 normal acid per litre of juice.
(c) A well known reaction is the decomposition of the reaction products of
reducing sugars formed in alkaline medium. It has been found that in normal mixed
juice 1 to 5% of the amount of reducing sugars present can be destroyed, depending
on the pH and the temperature to which the sugar juice hasbeen subjected
in the purification process. This destruction of reducing sugars is an extremely
complex reaction. It can be expressed a s the decrease in the reducing power of
Fehling solution ; it has been found that in a mixed sugar juice the destruction
of 1% of the reducing sugars corresponds with an acid formation of 2 to 10 ml.
0.1 normal acid per litre of juice. These acids are primarily very Weak acids. They
are present in sugar solutions as complex calcium organates or alkali organates, but
 PIBTEK HONIG 589

is known that if these decomposition products are subjected for several

ours to a temperature of 100 "C. that the decomposition goes on even in
and acid medium and that acids are formed with a lower molecular weight
and greater strength. It is for this reason that it has to be the endeavour to prevent
highalkalinities (pH values over 8.5 at temperatures over 60-65°C.) as any
liming will finally result in the formation of organic acids and a change

(d) As acid forming components have also to be mentioned-the proteins

in mixed juice. A considerable percentage of the proteins is coagulated in the
purification, especially in the heating process, but the proteins as such cannot
be qualified as stable, inert, precipitated non-sugars. They are subject to
decomposition and1 hydrolysis with the formation of amino acids.
The ahounts of proteins precipitated in the clarification vary with normal
cane between 300 and 1000 mg. per litre of mixed juice. If these proteins are
subjected in a juice to a temperature of 100°C. for 3 to 5 hours, it has been found
that at averagebH values as met in practical sugar manufacture, the formed amino
acids are equivalent to 0.5 to 2 ml. 0.1 normal acid per litre of juice. These are
extremely weak acids and their presence can only be demonstrated by a
polentiometric titration; the amino acids show their acid character respectively
alkali binding power at a pH between 8.0 and 10.0.
(e) An extremely complicated reaction is the reaction between hexoses
and amino acids. The reaction product has the tendency to polymerize under
the formation of dark coloured substances, with the development of CO,*.
(f) In the clarification of cane juices we are also confronted with a small
amount of plant mucilage, what is usually described in the sugar literature as
gums and pectins. Also this group of non-sugars is not stable at a temperature of
100°C. and at the pH values as met in the clarification. This group of non-sugars
which is descriked in the biochemical literature under the general name of
poly-uronides can be decomposed with the foimation of complex organic acid
commonly called uronic acids or hexuronic acids or specifically galacturonic acid,
etc., having the general formula CHO. (CHOH),. COOH. This decolnposition
may be quantitatively small, but under certain conditions, especially if there is an
accumulation of precipitate in the clarifiers or if the clarifiers are not completely
emptied, it may be the cause of a difference in the p H between the clarified juice
and the juice resulting from the filtration of the cachaza, respectively the clarified
juice from the bottom compartment.
* The reaction between hexoses and amino acids does not only manifest itself by the
formation of acid reaction products, but also by the formation of coloured substances.
[See : M.L. Wolfrom, W.W. Binkley and J.N. Schumacher, Ind. Eng. Chem. 47, 1416
(1955)l
When a cane juice has been sujected to a high alkalinity (pH>8.5) at higher temperature
(temperature>75OC.) the reaction products are unstable at high temperature and are
transformed into products of greater acidity. Overliming is one of the main causes
sf abno~malacid formation in subsiders.
 (g) As a factor influencing changes in the pH has also to be mentioned-the
use of partly unslaked or nonhydrated lime. These lime particles will be included
in the precipitate and may dissolve slowly in the hot juice, not causing an
acidification but locally high alkalinities affecting the average pH of the filtered
juices. Eventually, if a considerable quantity of undaked lime particles are
present in the used milk of lime, it may result in an increase in the decomposition
of reducing sugars, with a c~rresponding increase in the decomposition of
reducing sugars, with a corresponding increase of the lime salt content of the juices,
respectively an increase of decomposition products, which are subjected to further
decomposition during the processing of the juices.
(h) A reaction not related with the milk of lime but which may cause an
increase in the lime content respectively an alkalination of the mud juice is the
decomposition of calcium silicate by reacting with sesquioxides according to the
equation :
n CaSi03+m Fe,03--t(SiO),(Fe,03)m+ n CaO
These eight reactions* are known to occur in the clarification of limed mixed
juices ; the combination of these reactions is responsible for the changes in pH we
can observe in our sugar mills.
It is possible to reduce the quantity of decompositi~nproducts by selecting
suitable operating conditions. This is a matter of proper equipment for mixing,
heating and adjusting the p H with reliable control equipment to regulate the pH
of the juices to belimed, to be heated and to be settled as uniform as possible.
HOW TO LIMIT ACID FORMATION TO A MINIMUM

The following general rules have to be laid down to obtain maximum results :
1. In the liming process is, regularity of the pH, a point that can neverbe
overemphasized. It is necessary that all the juices entering the juice heaters have
a pH of at least 7.3 to 7.6. The change in the p H in the heating process is
unpredictable. The endeavour has to be that the juice entering the clarifier has
a pH of 7.1 to 7.3. The drop in the p H in the clarification, if the juice has been
properly limed and heated, is usually less than 0.3 pH unit.
--
*There are undoubtedly still a number of other reactions in hot cane juice, leading to
the formaion of acids, respectively of COz. C 0 2 is formed in cane juices as a decomposition
product of organic non-sugars. In acid medium (pH 4.4-5.3) the decarboxylation of aconitic
acid as one of the sources of C 0 2 formation has been put forward by R. C. Henry and L. A.
Clifcorn, Ind. Eng. Chein. 41, 1427 (1949). I t appears that mineral non-sugars have a catalytic
effect on this reaction. I t is, however, certain that also other reactions are taking place producing
carbondioxide.
 PIETER HONIG 59 1

A large drop in pH in the clarifiers can be caused by different conditions.

Important in this connection are insufficient heating of the limed jsice a ~ d .
insufficient liming of the juice. If a juice has only been lime&to a pH of 7.0, the
drop in pH in the clarifier may be 1,argeand going down to 6.2 in the clarified juice.
11 We have to avoid as well overliming as underliming.
t
2. Overliming, meaning a lime addition to such an extent that the juice
leaving the juice heaters has a pH over 7.6, has to be avoided. The heated juice
with a pH of 7.5 has usually been subjected to a pH over 8.5 tefore liming and
although the formation of acids as a result of the decomposition of reducing sugars
will not show bythe presence of weak organic acids jn the juices directly after
heating, it is an undisputable fact that the decomposition products that ha] e t een
formed are liable to further disintegration at high temperatures and that they
have to be qualified as one of the main cayses of the continuous and creeping
acidi fication of bices in process.
3. The precipitated non-sugars have to be liquidated continuously from
the clarifiers. Any stagnation and accumulation of the precipitate will result
in an acidification of the clarified juice from the lower compartments.
The acid formation is an extremely complicated reaction. The result of
it is that especially in the lower compartments of the clarifier the pH value can
drop to such a level that we have the decomposition of the carbonates present
in the juices. The carbonates in cane juices are stable at a pH=8 and higher,
but Eelow a pH=8 we have the formation of bicarbonates and we have also
the formation of carbonic acid.
THE FORMATION OF COa IN CLARIFIERS
The equilibria between carbonic acid, bicarbonate and carbonate at different
pH values have been determined accurately at 25°C. Determinations at higher
temperatures are lacking but it is certain that similar equilibria exist at higher
temperatures. In Table I11 we give the equilibria between CO,, bicarbonate
and carbonate :
TABLE I11
--
PERCENTVAL FRACTION OF C O ~PRESENT AS HE,,
HCO~'AND C O ~ "
AT DIFFERENT pH VALUES AT 25OC.
-- -
VH H2CO3 HCOar' COBr'

- -
- p-

The solubility of CO, at higher temperatures is much less than it is at lower

temperatures as shown in Table IV.
 SYMPOSIUM CANE JUICE CLARIFICATION

TABLE IV
SOLUBILITY O F COz I N GM. PER LITRE O F WATER* AT ATMOSPHERIC
PRESSURE AT DIFFERENT TEMPERATURES
,-
Temperaure in OC. At atmospheric pressure ' , At a pressure of

20 1.69
1.05 kg.lcm.2

-
-
25 1.48 -
30 1.26 -
40 0.97 5.79
50 0.76 -
60 0.58 3.99
70 0.39 3.38
80 0.21 2.85
90 0.09 2.51
It can be observed occasionally in sugar mills that the clarified juice on the
bottom compartments, when the hydrostatic pressure is released, likerates a certain
amount of CO,, giving to the juice a milky character. This is especially the case
with juices of low pH's. It has also been found that if the air in the overflow tanks of
continuous subsiders is analyzed on the CO, content, that CO, precentages over
10% are not abnormal at all. A continuous subsides is a continuous producer
of CO,. Whether all the CO, is actually the result of the decomposition of
carbonates by a change in the equilibria between bicarbonate and CO, is not certain.
It is possible that also a certain amount of C02is formed at the same time as a result
of decomposition reacti~~ns.It has been shown the sugar solutions subjected to
*Sucrose decreases the solubility of CO,. The number of accurate determinations of the
CO, solubility in sucrose solutions mentioned in the literature is limited. Findlay and Shen
(J. Chem. Soc., London, 101, 1459 (1912)) give the following data :
Soll,hility of COz at 25'C: '/
Sucrose concentration in % g. C02/100 ml.
2.6 0.813
5.2 0.798
9.7 0.767
12.3 0.744
The effect of the temperature on the dissociation constants of COz, HC03' and CO," is as
follows :
pK at different temperatures in "C.
30" 50' 70'
First apparent dissociation constant

Second dissociation constant

The presence of sucrose has the tendency to increase the strength of carbonic acid as a dibasic.
I
PIBTER HONIG 593

1
I
higher temperatures develop a certain amount of CO,. This can be as high as
1 to 5 mg. CO, per hour per 100 g. brix at llO°C.
A surprising reaction is always that the rate of acid formation increases
with an increase in H-ion concentration. The acid formation is accelerated as
the pH is dropping off. This reaction can be studied in a very simple way by filling
closed bottles with limed juice and heating them in a thermostat at 100°C. It
will be found that there is a continuous increase in pressure by the formation of
CO,, which reaction is always combined with a drop in pH.
It is also found that this drop i'n pH is greater when a limed juice is heated
together with its precipitate. The drop in p H of clarified juice subjected to heating
is less. If we like to give an explanation for this difference in behaviour, we have
to refer to the different types of reactions that are causing an acidification of limed
juices as given above.
Fundamental studies on the reaction rate of the different decomposition
and transformation reactions occurring in the handling of technical cane juices
have been done only in a few cases.
There are a number of methods to suppress acidification, which according
to my opinion are of no benefit and for which there is no foundation whatsoever.
One is the introduction of formalin in clarifiers. Another one is the chlorination
of sugar juices or other %d of disinfectants.
To prevent the undesirable effect of a low pH, as to the rate of inversion,
by the introduction of soda ash in the bottom compartments of clarifiers results
usually in an increased CO, formation which occasionally can result in an
accumulation of such a great amount of CO, in the bottom compartments that
when the CO, is released it upsets the whole performance of the clarifier. To
counteract this it is recommended to release the clarified juice, saturated with CO,,
from the bottom compartments periodically to have an undisturbed settling
process. .
But the principle to introduce carbonates,considering the equilibria between
CO, and bicarbonates as given in Table 111, is a practice that cannot be
recommended as the best panacea. If we wish to counteract the acid formation,
we should introduce an alkaline substance not leading to the formation of CO,.
But we can use just as well milk of lime, or, if we are afraidof secondary
precipitation reactions as a result of the introduction of the precipitating cation
Cat+, use a diluted solution of caustic soda diluted to a very low concentration.

DISCUSSION

Mr. Foster stated that in the preliminary experiments carried out by him on the liming
of cane juices at temperaturers of 100°F,,140°F. and at boiling temperature, for 5 minutes, 10
minutes and 20 minutes, and determiningP205 content CaO, content of the clarified juice
suggested that the reaction is a rapid one and not a slow one. He also observed that
Polyuronides are unstqble in the regios of 7.0 pH.
594 SYMPOSIUM CANE JUICE CLARIFICATION

Mr. Parashar referring to the development of acidity due to phosphates mentioned about
the variations from compartment to compartment. It was highest in the bottom most
compartment. As against the good effect of phosphates on clarification, the adverse effects of
mud volume and acidity developmeilt existed. One has to strike a proper balance.
Mr. F. H. C. Kelly posing the question what is pH, considered that the author had
overstepped the mark by claculating the inversion at pH 7.0. The pH at 100°C. would be
different. The effect of buffering has not been considered. I t is dangerous to say without
proper qualification that the rate of inversion is proportional to H+ ion concentration. Such over
simplification on which Table I is based i* not correct.
Dr. Douwes Dekker considered that Mr. Kelley's fears are exaggerated and referred to the
publications of the results of the Java Sugar Industry and the experiments at the Berlin Sugar
Research Institute, on which basis he believed Dr. Honig has prepared the tables.
Dr. K. S. G. Doss pointed to the nature of the graphs and observed that the graphs must
have been from actual data and interpolation.
Mr. Gundu Rao stated that it has not been possible to measure the pH of the juices at the
high temperature of the settler, without cooling.
Dr. Douwes Dekker referred in this connection to the work of Dr. Gross, who had measured
pH values at very high temperatures.

In the absence of the author, Mr. Nicklin presented the following paper.
Paper
SYSTEMS OF HEATING JUICES-PART I11

CHS. G. M. PERK
INTRODUCTION

Juices have to be heated on their way from the milling train to the clarifiers
and sometimes the juices are reheated before entering the first vessel of the
evaporator. These heating operations are carried out with the aid of juice
heaters.
The operational principle of juice heaters, and hence their design is markedly
similar to those of surface condensers. Surface condenser design is based on
the flow rate of the cooling water, a high flow rate being required for efficient
heat transmission. Although the higher the water velocity, the better the heat
transmission, such is limited by the high pumping power so necessitated to overcome
the consequent rise in frictional resistance and a velocity must, therefore, 'be
chosen suitable for both.
The same problem is encountered when designing juice heaters. Here
too the velocity must be high, not only for efficient heat transmission, but also
with a view to reduction of deposition of scale on the tubes. The limiting factor
is here less the increased pumping power* than the increased pressure on the
heater, when the juice velocity is raised.
----
*N.B. The total power consumption of a cane sugar factory is equivalent with 8.5%
of the total heat in steam or with 5+& of the heat in bagasse burnt, apprpximate.