Pieter Honig 529

MANUFACTURING SECTION
SESSION-MONDAY; 11TH SEPTEMBER, 2.30 P.M.
E. G. POWELL, Chairmar:
Il~ opening the session 'the Chairman.' said that some alteration in the order
of papers, to be discussed had been considered desirable and the paper by Dr.
Honig would now be the first presented.
Paper
THE SCALING OF EVAPORATORS IN RAW-SUGAR MILLS
PIETER HONIG
West Indies Sugar Corporation, New York

THE COMPOSITION OF SCALES

The chemical composition of evaporator scales in raw-sugar mills shows a
considerable variation. This is evident not only in different mills, but at the same
mill from one year to another. It is assumed that the scale composition is given,
in the first place, by the eonoentration of'the scaling non-sugars present in the
juices to be evaporated. Theie are, however, some general rules forthe composition:
a. in a sugar mill a scale has never been found consisting of a single component;
all scaling non-sugars are present in incrustations to a certain degree;
b. the composition of scales in evaporators is chiefly inorganic;
c. the scale of different evaporator effects has' a' tendency to be highest in
phosphates in the first bodies and highest in sulphate in the last bodies;
d. magnesia is found chiefly in the scales of the first effects,

.4 Ca804
81 02

Fe203~
A1 20
3

60 brix.
15 20
. Ooncentration.
Figuo l.·--Tho relation between 'composition of scales and ooneenbrat.ion in evaporator bodies.
 530 M anufaeturing Section

Besides this change in the chemical scale composition from first to last bodies,
there is a difference in the physical structure; scales in the last bodies are always,
more cOl,llpact and more difficult to attack by chemicals and usually the most
difficult to remove mechanically. This difference in physical structure is caused
by the higher sulphate content, but there also exists the fact that the scales in
first evaporator bodies have a higher percentage of phosphates 'and organic matter,
giving a certain porosity and mechanical softness. It is, possible to designate in a,
scheme such as in Fig. I the general tendency in the' composition of scales for the
first to the last effects in' an evaporator set.
It is important in studying incrustation problems that a detailed knowledge
be collected ,as to the general composition of scales. A semi-quantitative analysis
permits of the classification of scales. It has been proposed to classify scales
according to the chief constituents as shown in Table 1.

TABLE I
SPEOIFIC CLASSES OFSOALE IN RAW-SUGAR MILLS

Type Chief constituent I Composition

Phosphate scale
Sulphate scale
Silicic acid scale
Sesquioxide scale
Organic acid scale
Phosphate of lime and More than 25 per cent. P 20;
magnesium
SUlphate of calcium' More than 25 per cent. SO.
Silicic 'acid usually combined "More than 30 per cortt.. SiO.
with sesquioxides
Fe.0 3 and A1.0 3 usually More than 15 per cent. F.O",
combined with Si0 3 and
phosphates
+
A1.03
The only organic acids More than 10 per cent. oxalic
actually determined and and aconitic acid
analysed in scales are
oxalic acid and aconitic
acid

This is a useful system because it enables one to discuss in an objective way,

the cleaning and behavionr of evaporator scales and to compare the experience of
one mill with that of another.
The results of the analysis of a large number of scales .areshown in .Table 2.

TABLE 2
COMPOSITION OF SOALES IN EVAPORATORS OF RAW-SUGAR MILLS
(Summary' of 550 analyses of incrustations for ,Java mills 1927,1940)

Low Medium. High

CaO .. <10 10-30 > 30
MgO .. < 3 3- 8 > 8
Fe.0 3 • < 3 3-10 >10
A1.0 3 < 1 1~ 2 > 3
SO. '< 5 5-25 > 25
p.O. . . . . .. I .. < 5 5~25 > 25
SiO... .. < 5 5-30 > 30
Organic acids (oxalic and aconitic acid) < 2 2-15 > 15
Percentage of analysed samples .. 10 80 10

A method for rapid analyses of scales making it possible to estimate the overall composition.
after some experience, is as follows :~
 Pieter Hom:;; 531

CO.
1\
19. scale 10 ml. RN0 3 5g'. scale in 150 1111. Erlenmeyer 25 ml, ReI I : I
boil I boil

\ I I
filter add 0.5 ml. RNO" boil extract filtrate with ether,
and filter evaporate, test for oxalic
I . acid
to filtrate add
ammo Mo. reagent
J
I I
I
yellow precipitate
insoluble filtrate
i
P a0 5 BiO a. silicates
plus organic matter I I
treat 5ml. neutralize' 5 ml,
witih- BaCIa with ammonia, add
for sulphate an excess of acetic
acid, boil
I
I
I I
filtrate with
Precipitate
Sesquioxides excess ammo
Fe.0 3 AI a0 3 oxalate
I
I I
boil filtrate with excess Precipitate
ammo and ammo 'phosphate CaO
precipitate Mg ammo phos-
phate MgO

However, in addition to the composition it is much more important to collect

figures as to the amount of scale that is formed per unit oftime or per unit of weight
of evaporated water. This is important, not only from a practical point of view,
but also for future studies of the prevention of scale formation. In this respect
more quantitative data on the rate of scaling have to be collected.

THEORIES OF SCALE FORMATION

The cause of the formation of a hard incrustation on an evaporating surface
1S usually explained by the fact that the precipitating incrustant becomes super-
saturated and adheres to the surface. iAn explanation as to why a solid in super-
saturation attaches itself to the surface and does not remain as a suspended solid
in the solution is that at a higher temperature the constituent has a so-called nega-
tive temperature solubility coefficient. This accounts for the fact that calcium
sulphate adheres more strongly to a heating surface than e.g. calcium phosphate.
This theory, however, is not sufficient to explain all the phenomena.
In the first place the scaling constituents with the exception of calcium sulphate
and perhaps calcium phosphate, arenot in true solution in sugar juices. Silicic
acid, iron oxide and different oompounds of calcium are present in a complex
form. The mechanism of precipitation may not be explained in terms of solubility
figures. The second explanation is that on an evaporating surface a vapour bubble
is formed. This means that locally a solution is evaporating at such a rate that
one may speak ora drying-out of the solution, and there remain on the surface all
.thoseeolids which are irreversibly soluble in the juice.
 L ~_.~.-ZT'

532 Manufacturing Section

Precipitation in slfgar juices would cau~l;l incrustation specifically for the

insoluble non-sugars, whereby the adherence to the surface is given by the rate of
evaporation. This is counteracted by a number of mechanical factors such as
the speed of circulation, the dissolving power' of the juice to be concentrated,
mechanical factors such as suspended matter in the solution to be evaporated,
etc. However, even this does not constitute ott satisfactory theoretical explanation
of scale formation. There are different methods of diminishing 'scaleformation
by the addition of phosphates and protective organic colloids, generally speaking
by vegetable mucilages, which sometimes have a tendency to decrease the rate
of scaling.
The two theories given above, however, do not give any explanation for .what,
may be valuable in the so-called electrical water treatment methods. What is the
function of organic colloids? It has been observed many times that small changes
in the average composition of juice cause tremendous differences in the rate of
scaling. Young immature cane has a tendency to deposit a scale rich in silicic
acid. It has been observed that over-ripe cane has the tendency to promote heavy
scaling, especially as regards the formation of sulphate scales in the last bodies.
Among the vegetable mucilages recommended for scale prevention, which
have shown their value in the treatment of boiler feedwater, must be mentioned
alginates, lignins and cactus-juice extracts. A number of other mucilages such
as starches, glues and pectinates are practically without effect,
These phenomena involve the chemical affinity between, the organic colloid
and the scaling actions, but the reactions cannot be explained by the rules of
stoichiometry. There are known examples of similar reactions in which small
quantities of organic colloids change either the rate of growth of crystals, e.g., of
calcium sulphate, or prevent the coagulation and mutual adherence of colloidal
precipitates,e.g., the incrustant on the evaporating surface. Analogies can be
found in the effect of some of the protective colloids in the prevention of the growth
of large crystals in the manufacture of ice cream and in electro: plating with colloids
added. The organic colloid may act as a kind of stabilizer, so that in the concen-
tration process some of the inorganic non-sugars that would otherwise be pre-
cipitated are held in colloidal solution by the protective action of some kind of
inorganic colloid..
The effect of added phosphates is simpler to explain sin~e there are two
anions in solution, sulphate and phosphate. The precipitated calcium phosphate
has less tendency to adhere to an evaporating surface than calcium sulphate.
A satisfactory theory as to the effect of electrical treatments has not yet'
been provided. The electrical treatment" if it works, may perhaps have some effect
upon inorganic non-sugars present in a colloidal form in sugar juice such as silicic
acid and sesquioxides, but no effect upon dissolved non-sugars, such as calcium,
sulphate. That 'an electrical treatment of juices will have an after-effect upon
(a) the rate of precipitation, and (b) the growth of crystallized incrustations, is
not selfevident. It may be that the stability of a colloidal system is changed and
that the form in which it is precipitated on concentration is thus influenced.
 Pieter Honig 533

However, this matter must receive further careful study before anything definite
may be said about it.

COMPOSITION OF SCALES AS INFLUENCED BY THE COMPOSITION

OF THE JUICE
It has been found that the rate of scaling and decomposition of deposited
scale are related in a complex way to the composition ofthe juice-to be concentrated.
.It should be noted that the suspended matter in juice has no direct effect
upon the scaling. It. is the author's experience that if limed, mixed juice without
settling be passed through' the evaporator the rate of scaling is reduced. When
preheated, limed raw juice was concentrated without settling in apre-evaporator,
acting as a flash-tank and giving complete removal of included air and at the same
,time improving the 'steam economy, scaling in the pre-evaporator was insignificant.
In the same way it has been observed that there is no direct relation between
the clarity of the clarified juice and the scaling of evaporators .. Only the dissolved
non-sugars or those that are present in a colloidal state can enter into the formation
of scale.
The' following rules may be stated as to the composition of scales:
1. If the sulphate content of clarified juice exceeds 800 mg. S04 per litre,
atypical sulphate scale in the third and fourth body of the evaporator is usually
found.
2. If the phosphate content of the juice is high and the pH of the clarified
juice is over 8, or below 6.5, a typical phosphate scale is formed in the first two
bodies of the evaporator set.
3. The lime and magnesium contents of the clarified juice are of the greatest
significance in relation to the rate of deposition and also the composition of scale.
If the total hardness of the clarified juice exceeds 700 mg. CaO per litre it is .found,
that the scales are high in calcium in the last three bodies of the evaporator and
that a substantial percentage of magnesia is found in the first body ofthe evaporator.
4. If the effet supply juice is a mixture of clarified juice, coming from the
clarifiers, ,and filtrate, together with sweet juices from the press station, there is.
great risk of the formation of scales high in silicic acid in the last bodies of the
evaporator and high in sesquioxides in the first bodies of the evaporator. The
available data give the impression that it is specifically the difference in the pH
values.of these two juices wihch gives an after-effect in the evaporators, resulting
in the precipitation of these non-sugars, where this precipitation in statu nascendi
is the cause of this typical scaling.
Further it has been found that the sweet water from a press station is one of
the undesirable components of mixed clarified juice, usually" ell-using an' excep-
"
tionally high degree of scaling, especially scales high in sesquioxides and silicic
acid. This degree of scaling cannot be correlated with the concentrations of these
non-sugars; it is caused more by their physical-chemical nature. Clarified juices
have been made either acid by sulphur dioxide or. slightly alkaline by the addition
of milk of lime to settlings before filtration, as a corrective meth0fl to prevent either
 534 M amifacturing Section

-discolouration in the evaporator process or to prevent the formation of acid con-

densate that can sometimes be observed in factories where acid juices are concen-
trated, or to improve the rate of filtration. This practice is always responsible for
an increase in the rate of scaling. Once again a precipitation reaction must occur
on concentration and' heating- after mixing and the precipitate of organic non-
sugar is deposited on a heating surface. .
It is possible to give an indication as to. what might be expected as to com-
position of scales with the standard procedure for evaporating cane juices. The
I concentrations of scaling non-sugars in clarified juice lie between the limits shown
in Table 3.
TABLE 3
NON-SUGAR CONCENTRATION IN CLARIFIED JUICE IN MG. PER LITRE

Low Medium High

CaO MgO ·. .. < 300 400-500 > 600
MgO ·. ·. < 100 100.,..-200 >200
Fe.O. ·. ·. -e 20 30- 40 > 45
Al.O. · . < 5 5-'--,20 >25
SiG. <150 200-250 >300
P.O. ... < 30 40-70 > 100
SO. < 300 300-4PO >600

It has been found that the scale composition more or less follows the trend
shown in Fig. 1. This composition is not influenced by the turbidity. If a clarified
juice is high in phosphate this isusually not caused by an incomplete precipitation
of inorganic phosphate, but is caused by the presence of organic phosphorus com-
pounds, particularly phosphatides and protein-phosphates.
The concentrations of phosphates in mixed juice and clarified juice are shown
in Table 4. If the phosphate concentrations exceed these figures a rather high
percentage of phosphate is found in the scales of all effetsof the evaporator set.
TABLE 4

Mixed juice Clarified juice

Total P 20 6 in mg. /litre 300-550 30-100

Protein phosphate determined according to Javillier-
Colin... .. 30- 60 5- 15
Lipoid phosphate 20- 50 10- 30
Phytin phosphate .. absent absent
Inorganic phosphate 250-450 15-60

The indications are that the following pr~ctical suggestions would be of USe in
preventing the formation of different scales:
(i) Every effort shortld be made to reduce the calcium and magnesium contents
inclarified juiceto-a minimum. For this, regular control of the hardness of clarified
juices is necessary. 'A direct soap titration method of determining calcium and
magnesium may be used.
(ii) 'Extreme fluctuations in pH, particularly in the clarified juice have .to
be avoided. This .involves a proper technique of Inning, heating and settling and
the avoidance of mixing clarified juices of different pH values before concentration.
 Pieter Honig 535

(iii) A high proportion of sulphate in soales is unavoida~le if no sulphur is

applied in the purification of mixed juice having a high sulphate content. This is
influenced by the soil upon which the cane has been grown.
(iv) In the scales which have an exceptionally high content of 8 1° 2 and R 20 a,
the only way to reduce the scaling is by the introduction of extra phosphate in
the clarification process. This reacts specifically to remove silicic acid and ses-
quioxides., It isa question of economy whether such a method can be recommended.
At present methods are being developed to diminish the rate of scaling by
the addition of small amounts of phosphate, in the form of neutral phosphates, to
the clarified juice. These form a suspended precipitate during the concentration
processes and also have an absorptive action upon some of the scaling non-sugars.
There is also an indication that certain protective colloids, which will be discussed
later, have an effect upon scaling due to sulphate arid calcium phosphate, especially
sulphate scaling. Scales are formed but of a different physical structure which
can be more readily removed by the standard cleaning operations ..

THE QUANTITY OF INCRUSTATING SCALE COMPONENTS AND THE

RELATION TO THE INSOLUBLE INORGANIC NON-SUGARS PRESENT '
IN JUICES·
When the quantities of insoluble inorganic non-sugars present in clarified
cane juice are normal the amount of scale formed in each evaporator body per
litre of evaporated clarified juice may be classified as follows:-
~ . .
low 1-2 mg.
average 2-'-4 n;rg.
\

hi~ 4 ~g.

For a quadruple effect the total amount of scale will be four times as great.
The scaling is not distributed evenly over all bodies. The heaviest, scaling
occurs in the first and last effects.
The amounts of suspended matter in clarified' juice and evaporation syrup
have been studied in Java. It was found that in the normal factory processes
considerable quantities of non-sugars were precipitated in the concentration
process. These non-sugars were chiefly inorganic, the organic consisting chiefly
of pentosans, small amounts of organic matter of a proteinie nature, and certain
amounts of lipoids. The latter are usually designated in the literature as waxes
or as waxy matter, but they have a much more complex nature than might be
expected from this single word. They consist of phosphatides, sterols, fatty acids
and esters of higher fatty acids and alcohols related to true cane waxes. It was
found that the higher the proportion of organic matter in the suspended solids
removed by centrifuging, the 10IYer the rate of scaling.
It was found that .the amount of suspended solids in syrup, calculated pOl'
litre of clarified juice was 0.1-1g.; on, syrup this reJ:.l~flsents O.5-5g. per litro.
536 Manufacturing Section

The organic matter in these .solids varied from 10-60 per cent. on insolu ble. *
It consisted chiefly of phosphate and sulphate of calcium, sesquioxides and smaller
amounts of silicic acid. Theinsoluble organic non-sugars per cent. total organic
non-sugar solids showed the following ranges : -
a. protein as calculated from N content 15-25
b. pentosans (pectins) 5-20
c. waxy matter, soluble inorganic solvents 5---'--20
d. gums 3-10
If the amount of scale that is formed in the different bodies be compared
with the amount of inorganic scaling non.sugars present in the juice,and the
amount of scaling non-sugars found as suspended non-sugar in syrups, the follow-
ing conclusions may be derived: Of the total amount. of scale-forming non-sugars
present in clarified juice onlya small percentage deposits on the evaporating sur-
faces. The main difference in composition between the scale and the suspended
solids is that the suspended solids are high in organic non-sugars. It has been found
that the rate of scaling is higher if the percentage of organic non-sugars in suspended
solids is low. A percentage of, determinable organic non-sugars (dry solids minus
ash) less than 15 is regarded as low. A high percentage exceeds 40. A high percen-
tage of organic non-sugars correlates with a low rate of scaling.
These facts lead to the conclusion that the degree of scaling may be expressed
in terms of the amounts of scaling non-sugar adhering to the evaporator surface
in mg. per litre of evaporated water as follows:
low .. <18 mg. per litre
medium 1~-20
" " "
high >20
" " "
Per square meter evaporating surface the rate of scaling per hour can be
classified as follows :
low .. <150 mg. per litre
medium 150-400 " " "
high >400
" " "
In evaporators a scale weighing less thar; 0.1 kg. per m. 2 is regarded as thin
scale, a medium scale weighs O.I~.5 kg. and a heavy scale more than 1 kg. per
m 2 • Scaling is considered extremely heavy if after 250 hours operation more than
1 kg. scale per m. 2 is formed.

* The complex nature of the organic non-sugars makes it very difficult to give the composition
with exact. chemical compounds. A classification of the non-sugars is based upon:
(a) nitrogen content X 61- == protein non-sugar,
(b) extractable with chloroform = wafCY matter,
(0) with acidified alcohol washed 'solids extracted with cold water.
To the flltrnte added alcohol 95%. The precipitate filtered. The ash free precipitate
is called "gums."
(d) The washed solids distilled with 12.5 per cent. HOI. The distillate precipitated with
phloroglucin = pentosans, and calculated as pectins according to the table of Koenig.
 Pieter Honig 537

THE EFFECT OF SCALING ON THE HEAT TRANSFER; THE EXPRES-

SION AND EVALUATION OF'THE SPEED OF SCALING
The main significance of scaling in the sugar factory is the effect in reducing
the coefficient of heat transfer, so making it necessary to clean the 'evaporators
periodically in order to restore the original heat transfer and maintain their,
capacity. It is astonishing that-the sugar industry has not yet been able to evolve
convenient methods for the rapid determination of the coefficient of heat transfer
in evaporators; At present practical values for the average rate of evaporation

to condenser
Il'"

evaporator bodY ....~..........~~piping fo~ removal

of Qncondehsable gases.

T1

V~notch water meter

type of a recording
condensate meter BS sight glass ..
the rotR-meter.
Condensate

Figure 2.-Tl=temperature of the used vapour.

T2= condensate.
T3= juice.

in kg. per m. 2 are used. These figures usually lie between 20 and 30 kg. perm.f,
depending upon the type of evaporator and the difference between the pressure
of the steam used in the first body and the vacuum applied in the last effect. The
performance does not depend only upon the overall heat transfer but is also related
to the way the evaporator bodies are constructed, the removal of non-condensible
gases and condensates and the juice level in the evaporators..It is possible to
 .~--y­

-------
538 Manufacturing Section

reduce the personal judgment of evaporator work by simple devices for measuring
the amount of condensate. The so-called V-notch water meter is the best known
device* (See Fig. 2).
The performance of evaporators is also affected by entrainment. Among the
most important factors affecting this is the difference in the temperatures of the
juice in the last and second last bodies of an evaporator set, as entrainment is
caused mainly by the self-evaporation of the juice entering the last body. .This
can take place in a more or less explosive way with fountain effects, and may be
the cause of considerable losses. This difference in temperature increases with the

2
J..
Q)
1/U = a + bT
lI-t
CI.)
t:1
«1 50
~
+'

~400
(I)
.£:

n
10
p

5 10 15

T = ,days of operation..
Figure 3.-The change of the overall heat transfer of an evaporato/body with time of oporabion.

decrease in the heat transfer in the last body and for this reason the rate of scaling
is an important factor in causing unknown mechanical losses in sugar mills. The
only way to come to a good understanding of the significance of scaling is to
determine the actual value of the overall heat transfer. This may be done simply by
measuring with recording instruments the amount of condensate formed in' the
last body in a given period, and 'noting the temperatures of the steam, juice and
condensate.

* For V-notch water meters refer to :

L. A. Tromp: Machinery and. Equipment of the Cane Sugar IFactory, p. ,42;1, 1946.
Norman Rodger', London; Oliver Lyle: The efficient ues of Fuel, H.M. Stationery
Office, London, p. 2-4, 1944. ' '
 Pieter Honig 539
\

Overall heattransfer =cal./m. 2 evaporating surface/hour JOC.

Heat content of condensed steam in cal. per kg. =606.5 +0.305 (T l ~ T 2) .
Overall heat transfer =
kg. of condensate x heat content per kg.
----:---.----'------.------,--'---~---------

evapvsurfaoe in m. 2 x time in hours (T1-T s)

-Deterrninations have shown that the decrease in heat transfer with scaling
is the greatest in the last body of an evaporator set. The decrease is much less

4
t<)
0
..-
X 3
(\J

~
~
2

,5
T= days of operation:
Figure 4.~The graphic method of determining the change in overall heat Lransfer with the time
of operation.

in the second and third effects but sometimes with juices that have
. . . ~. ,
not been properly
. .

clarified, is higher again in the first body, The change ofthe heat transfer is shown
diagramatically in Fig. 3.
For a comparison it is convenient to express the reciprocal of the square
of the heat transfer as a function of the time of operation. ?,his is represented
usually by a straight-line, as shown in Fig. 4.
By this method it becomes possible to collect data for comparing the rate of
scaling in relation t~the system of operating evaporators; the composition and
pre-treatment of juices to be concentrated; and the influence of special chemicals
 ------
,~/

540 Manufacturing Section

added to juic~s and acting as scale inhibitors or other methods-for, instance,

electrical methods-that influence scaling. In this way one is able to come to an
objective judgment of the practical and economic value of proposed ways and
means.to prevent scale formation.
One of the first observations on the cleaning operation is that it is most
important to olean the tubeswell.enough 'for the overall heat transfer to be re-
stored to approximately the original value. It is known that this does not always
happen in actual practice, as the time for complete cleaning may not be available
or the scales maybe very difficult to remove. It is generally accepted that the
peferred method of cleaning involves treatment with chemicals and if possible
a mechanical cleaning has to be avoided. Besides being expensive, due to the rather
extensive manual manipulation, all existing methods of mechanical cleaning damage
the evaporator tubes and so reduce the life of the evaporator. It is the duty of the
chief of fabrication, in on-o por at.ion with his colleague the mill engineer, to take
care 'of this cleaning operation. Personal inspection is necessary after cleaning
to ensure that the evaporators are in good working condition .before they are re-
started, but even this in many cases may not be sl{fficient. The standard accepted
.in actual practice depends largely on the system in use-factories that close down
every week-end usually have a system whereby a weekly cleaning is given to the
evapor,ator. The only requirement is that during the week's operation the overall
heat transfer does not fall below a certain limit, so that still after six days of
operation sufficient concentration can be obtained.
Papers have been and are being published regularly on evaporators and
specificallyon scaling, and a number of methods have been proposed for the cleaning
or prevention of scaling. In all this literature agoo~l, technical study of the most
important factor, namely, the heat transfer and the way in which it is affected
by the factors discussed, is lacking. This pointis stressed because no real progress
can be made until studies of this phenomena are undertaken in at least 20 or 30
mills working under different conditions and 'with juices of varied composition.
It could easily be 'done if the proper equipment were installed for measuring
temperature and the amount of condensate, and observations made over a sufficient
peri~. '
It is of course..a well-known fact that the overall heat transfer is not the only
factor that gives a full picture of what actually happens in scaling. The composition
of the scale is important-sulphate scales for instance, are hard and difficult to
remove, but they are not the worst type of scale in affecting the overall heat
transfer. Much mote serious in this respect are the porous scales consisting of
sesquioxides, while between these extreme types are the phosphate scales. These
latter scales may be removed by a periodic cleaning, much more easily than the
stLlphate scales.

MECHANICAI"AND CHEMICAL'METHODS OF SCALE REMOVAL

The remQval of sca'les,is an operation that has to be 'done in aU sugar factories.
On' th6'one !1;J.aiIJd there'is theext.!l'eme method. of removal
by mechanical means
onily.For this purpose a liiumber of suitable tools has ,been, develctped, among
 Pieter Honig 541

which bherotar y drill or scmper, driven by an electric motor 0,1' compressed air,
is becoming popular in the larger mills. On the other hand there is the extensive
use of the chemical methods. Of bhe materials that have been used or proposed
only a few have remained in use, the most important being caustic soda or soda
ash. The chemical effects of a tratement with soda can be expressed in the simplest
way by the following equations:
CaS0 4 + Na 2C0 3 -~-> CaCOg .+ :Na 2S0 4
CaSiOg .+ 2NaOH - - - > Na 28i0 3 + Ca(OHh
ca} . Cal
Mg HP0 4 + NaOH -> MgfNaP04 +H20
It is not so much the dissolving action of the chemical as such that is important,
but rather the softening of the scale so that after boiling with a soda solution it
(Jan be removed by a spray of water. In cases where boiling with soda is not
sufficient it may be followed by' boiling from one to six hours with acid, usually
hydrochloric at .5 to one per cent. The effect of an acid treatment may be shown
by the following table :

Mg g 42 ~j
Cag }(PO) Ca °
Mg lfHP 4 + Ca C12
( + HCl --->
Ca IN PO I
Mg f a 4 J
Ca
Mg fl H P0 4 + NaCl
Ca:COg +Hq - - - - - - > CaC1 2 + CO2
The acid acts in several ways; It neutralizes the soda ash not removed from
the evaporator body and scales by the washing with water. It has a dissolving
action upon some of the constituents, specifically the carbonates, and it gives a
transforination of the phosphates. V61:y small amounts of sulphate are dissolved,
an effect that also can be obtained 'by boiling only with water. All these actions'
together change the porosity and the 'hardness of the scales so that they become
easier to remove. The attachment between the scale and tube surface is lessened
so that in most cases washing with water only will remove remaining scales.
, The acid has a disadvantage because of its effect upon the iron 'of the bottom
plate of the evaporator.
The results of an acid boiling are given in Table 5.
TABLE 5
"
-- ,
I I
I i
I

No. of g. solids total added calcu- j acid II acid

I acid total total
evapor- I
per 1. • solids I pure lated . before after used acid' acid
ator spent in spent acid cone: boil boil in used in used
body acid acids per of acid- pel' cent. pel' cent, Cleaning cleaning in kg.
solution in kg. body kg. percent. process process
pel' cent. per cent.

I 3.2 20.8 20 0.35 0.21 0.08 0.13 0.27 17.5

II 2.8 18.2 20 0,35 0.21 0.16 0.05 0.19 12.4
III 7.4 48.1 40 0.69 0.42 0.31 0.11 0.38 24.7
IV 22.0 143. ' 40 0.69 0.37 0.26 0.11 O.4il 28.0
I
The data in this table have been collected by Mr. F. de Miguel, Central Palma of the Compania
Azuearore, Alta Gracia, [;hba. .
542 Manufacturing Section

The chemical compositions of the dried solids present in the spent acids are '
given in Table 6.
_ 'l'ABLE 6

First body jsecond body I Third body IFourth body

----
Organic and volatile matter . 50.8 55.7' 56.5 [' 71.0
CaO 10.9 3.6 10.8 11.3
MgO trace trace t.race Ii trace
Fe.O.
CnO
23.6
positive
I 15.7
trace
15.0 2.1
negative I negative
Cl 21.9 30.8 27.2 I 13.3
SiO, 2.6 2.2 9.2, 3.8
P,O.
SO.
10.6
trace
I 1.9
trace
5.1
trace
\1 2.1
traoe
. Total solids in spent acid kg. 20.8 18.2 48.1 143.
Total Fe 2 0 3kg. 4.95 2.85 7.2 3.0
1
Calculated as Fe in kg. i
Fe
(Factor = 0.7) 3.41 2.0 5.0 2.1.
Fe 20 3

Besides the' use of caustic soda or soda ash alone a number of claims have been'
made to the effect that improved cleaning is obtained when they are used in com-
bination with each other or with other chemicals. It has been found, that with the
usual scales in raw sugar mills half the caustic soda can be replaced by soda ash
with a corresponding saving in cost. It has been found also that the higher the
concentration of the soda solution, the better the cleaning effect. There are practical
reasons limiting this concentration, the most important factor being the cost of
the material.

IIi addition the handling of concentrated soda solutions becomes risky and
unpleasant for the labourers because it is practically impossible to avoid coming
into contact with the solution. This can partly be overcome by using a-system of
piping und.pumps of suitable materials to fill the evaporator. The cost factor can
be overcome by- using the soda solution several times. It can also be partly re-
vivified by adding a certain amount of milk of lime to the spent soda solution in-
special tanks. This practice has been in use in a number of factories, but satis-
factory results can only be obtained if this caustisizing is done at a high temperature-
preferably over 90°C. It is desirable; too, that the tank be equipped with a stirrer
and that after settling the precipitate formed be removed by a bottom valve. By
the addition- of extra soda, the soda solution can be restored to its original strength..

It should be pointed out that a large number of variations occur in the way
soda is used and little attention is paid to the process in many, sugar factories.
The cleaning liquors are usually found in a hidden corner outside the main building
of the sugar 'factory. In the author's opinion the fact that the preparation and care-
of these materials are not usually under the careful supervision of the mill technolo-
gist results partly from the belief that they do not form an -essential part oftiul
factory report and of the control of the sugar mill. The following figures may.serve
as a g,?ide to the quantitie:;;involved and as to the cpsts that,' are connected with:
 Pieter Honig 543

this cleaning operation: A ,high consumption of caustic soda per 1,000 tons of
cane i~ 100 kg. and higher, while a low value is 20 kg. ~~ high consumption of
hydrochloric acid per 1;000 tons of cane is 10 1. HCl of 20 Be perl,OOOtons of
cane while a low value is 3 1.
It has been proposed several' times to use with the caustic soda a certain
.amount of -sodium or ammonium fluoride, especially the latter,or ammonium or
sodium chloride. The practical value of these additions is very controversial.
Fluorides are still used in a number of factories. Their effect when used with soda
liquor in concentrations in excess of 0.01 per cent. may be explained 011 the basis
of solubility considerations:- .
Calcium } . calCiUm}.
" . phosphate
Magnesmm
+ fluoride ->. .
n:agnesmm
fluoride + phosphate
That is there is an ion exchange process for the lower concentrations.
Because sugar mills are usually located a great distance from heavy chemical
industries, acid is one of the more expensive chemicals. For this reason it has been
proposed to replacehydrochloi'ic acid with sodium bisulphate or by sulphamic
.acid. The prices of these acids delivered at a sugar mill taken at an equi-molecular
basis are lower than that for the hydrochloric. A disadvantage of sulphuric acid
is the danger in handling it in a sugar mill where labourers are probably not ex-
perienced in handling dangerous chemicals. Technical bisulphate of soda has been
used many times in cleaning operations in sugar mills, but usually after a period
it has been replaced by hydrochloric acid, which has a higher dissolving effect.
. 'The use of sulphamic acid is still developmental. One of the advantages, that is
.claimed but. not proved by factory data is that the dissolving effect is greater
than that of acid sulphates as the sulphamates are of a greater solnbility than
the corresponding sulphates.'.
To counteract the dissolving action of acids upon the evaporators, it has been
eustomary in many countries to add so-called inhibitors to the hydrochloric acid.
A large group of chemicals-c-amido acids and sometimes special materials' of the
-quinoidine tYPl?-reduces the dissolving action of the 'acid on steel to avery con-
siderable extent without influencing the solvent action upon the scaling com
ponents. There is no published information on the value of these inhibitors.
The dissolving, action should. be expressed as the amount of iron dissolved
'per' m. 2 per 24 hours of treatment; it can be obtained only by determining the
amount of iron 'present in the spent acid after each treatment. The figures in
"Table 7 were taken from the results of' a number of experiments on cast iron
vessels.
TABLE 7

Six hours boiling with HCl, kg.

~-----i8000;'::OdY1\Till:",:o"'1 Fm,;,:,'O"Y
First body

0.36
per m ·2 dissolved .
, ·R,eduction in thickness m m. 0.041 I 0.024 0.062 I. 0.025
----------------'---~)~,----'------~----'_:.._--'---'~-~
 544 Manufacturing Section

This means that with 100 acid boilings the thickness of the bottom of the
evaporators may be reduced from -li-} in. assuming a
homogeneous tcorrosion.
It is up to technologists in the modern sugar mill to collect more data on this
phenomena.
The approximate prices of chemicals used' in cleaning sugar mill evaporators
is given in Table 8. .
TABLE 8
--~----~--_ --_.
Caustic soda, 76 per cent. NazO per.Ib. 3-4 cents
Soda ash, 58 per cent. NazO 1-2
Sodium bisulphate (nitre cake) 1.5-3
Hydrochloric acid 18 Be . ·2-2.5
Sulphamic acid (HO-SOz-NH z) 15
Ammonium fluoride 16
Sodium fluoride 13-14

* All prices are the Chemical Market Prices, U.S.A., May, 1950, technical qualities, standard
packing, off factory U.S.A.

NEW METHODS IN SCALE PREVENTION

The most. important factor in reducing scaling to a minimum is the proper
clarification of the juices to be concentrated. This means, primarily, that the con-
centration of the scaling non-sugar components has to be at a minimum, and
secondly, that factors causing the precipitation of the incrustating non-sugars
present in 'a colloidal state must be avoided. These factors include the constancy
of temperature,the regularity of the pH and variations in the composition of the
juices to be evaporated being as small as possible. It is a well-known fact that if
a sugar factory has to mill canes of widely varying compositions-young and over- .
mature cane, cane harvested a short time previously and that harvested several
days before crushing-the clarification is upset and the rate of scaling varies.
A number of methods to reduce scaling have been proposed in recent years.
Most of these method~ find their origin in the treatment of boiler feed water and
it has' been thought possible without further fundamental studies to introduce
these methods ill the treatment of cane juices. It has to be understood that in
many cases even the reactions occuring in the treatment of water are not yet
fully explained; whether it is possible to introduce these methods for such a
complex chemical-physical system as cane juice, is problematical. Many of these
methods have been applied to a considerable extent, but many also have been
discarded. '
The methods for reducing or preventing the scale formation may be sub-
divided into mechanical, chemical and physical methods.
MECHANICAL MEANS

The oldest method for scale prevention involved the introduction of wires,
, bars, etc., into evaporator tubes in the hope that part of the scale would adhere
to them thus reducing the scaling of the evaporator surfaces. In the literature
before 1900 there are many instances where this method has been tried with favour-
able results, but there is practically no sugar factory in the world where this method
is still in, use.
 Pieter Honig 545

The second development in this field was the addition of inert. material or
clarifying agents to the t.hin juice. After passing ,t.hrough the evaporators .they
were removed from one of the intermediate juices or syrup by filtration before
being sent. to bhe panfloor. This method has found a limited applicat.ion,t.hough
not. with the intention of reducing scaling, but. more as a result. of a shortage of
filter capacity, It may give satisfactory results. It. is possible, for instance, to
pass bhe unsettled, heated, limed mixed juices through the first. body ofan evapor-
ator set. Similar methods involve t.he addition of-powdered vegetable carbons
to the thin juice and its removal by filtration from t.hesyrup ; kieselguhr has
been used in the same way. This has been done as an experiment. in Java where
t.he syrups were filtered with kieselguhr in combination wit.h the sulphitatiori
process for white sugar manufacture. All these methods have certain effects upon
scaling, but. not. to such an extent that all scaling could be prevented, Sometimes
a change in t.he composition of the scale was observed. For instance, with the use
of kieselguhr the scaling by lime salts is diminished but.' bhat by silicic acid is
increased. At the present moment. it. cannot. be said bhaf any of these mechanical
met hods represents a solution for the scaling problem in t he raw sugar mills.
CHEMICAL METHODS

One method to prevent. the forma.tion of calcium sulphate scale in boilers

makes use.of phosphates which causet.he negative temperature Go-efficient. of the
solubility of calcium sulphate 't.o be tr-ansformed into a positive co-efficient. of
the corresponding phosphate compounds. This treatment combined with the use
of organic colloids, such as alginat.es, lignins and tannic acid compounds, vegetable
mucilages or various other preparations, has given very satisfactory results. In
analogy with the boiler-feed water treatment, proposals have been made to the
sugar industry to use the same or modified chemicals for scale prevention in factory
evaporators. At .the present moment this technique is not a part of the rationalized
procedure in sugar mills, but is more or less directed and guided by manufacturers
of such chemicals. The most import.ant manufacturers of anit-scale chemicals
are given in Appendix 1.
Most of the anti-scale chemicals available consist of a mixture of phosphates,
mono- and di-sodium phosphate and tet.ra-sodium-pyro-phosphate (Na 4PZ0 7) ,
soda and an organic mucilage, classified as a protective colloid. The ratio of pro-
tective colloid to the inorganic phosphates may reach as high as 1 to 10, but it
is usually lower. The quantities that. have to be used according to the recommen-
dations given to sugar mills vary from 0.02,0.01 kg. per ton of cane. It can be
said that a high application of these commercial products, requires a quantity
of 5-10 mg. P Z0 5 per litre and 0.5,2 mg. of organic colloid per litre but in relation
to the amount of scaling' non-sugars present these quantities are insufficient to
explain the scale inhibiting effect, if it exists. *
The facts that have been pr~sented in the technical literature concerning the
practical value of these anti-scale chemicals are insufficient to allow of a definite
conolusion. It may be that some are of practical value, but the manner in which ,
* A manufacturer of alginates recommends the use of 10 mg. of sodium alginate pel' litre
of juice to be evaporated.
546 Pathology Section

the action of these chemicals is explained and presented by many of the manu-
facturers is often a misjudgment of the chemical knowledge of the average sugar
technologist. It is understandable from the manufacturer's point of view that the
composition of these chemicals be kept a secret, partly because the chemicals are
available on the open market. It must be possible for the various experimental
stations to develop better ntethods .and better recipes, ~f as mentioned above, the
results with boiler-feed water treatment can be transferred to the treatment of
cane juices. This fact has not .been proven and requires further study before we
know anything definite about it.
I

SYSTEM A

,
n~ I ID -ll>

SYSTEMB insul~ted
e Le.c t.r-cde ,

Figme 5.-Schematic representation of elect.rical.isystems for water treatrnent.

Dimensions: D=2.5-20 em., L=30-80 om.i surfa.oe insulated electrode 0.02-0.2m."
Duration of electrical treatment: 0.05-3 sec.
Capacity: D=l" 2 m" per hr. 2" 5, 3" 10, 6' 30,8" 160.
Electrical current: Current ~0.001~1000amp.
VoltageE=L5 v. D.C., 110 V., 220 V. A.C. single phase.
Frequency f=D.C., 50, 60 and high.
Energy w=O.Ol-lOOO watts.
 \ \ I

Pieter .Honig 547

PHYSICAL METHODS

At the present moment several methods involving the use of electric current
have been introduced with a certain amount of technical reticence and mystery
for the treatment of water and canejuices. Direct or alternating current maybe
used and according to the prospectuses it causes a change in the physical charac-
teristics ofincrustating substances, so that they are prtJcipitated as fine. sludges and
do not crystallize, with the result- that this represents the final solution fora very
bothersome problem in our sugar mills. The best known systems ,y~ have at the
present moment are given in Appendix II.
In each of the first three methods a current is passed -through the water or
juice to be treated between two insulated ~lectrodes. The first two use single-
phase alternating current of a. standard voltage, while the third system uses a
direct current of a low voltage from one or two dry-cell batteries. The form of
this system is given in Fig. 5 together with some particulars of the conditions to
be applied according to the prospectuses from the manufaoturers and information
. found in the literature.
The Solavite process uses a number of cells, containing "active" hydrogen
absorbed on carbon. Electrical current is not used in this system. The hydrogen
works, according to the promotors, 9n the scaling components, making them
incapable of forming scale. According to the explanation given this electrical
current has an effect which at the present moment nobody has peen able to ex-
plain. But it is .understood that there may be .a· change in the hydration and the
electrical charge of the ions or colloidal impurities in such a way that upon heating
and concentration they are no longer able to form a hard scale, hut are precipitated
. asa. suspended sludge which does not hinder the heat transfer and can be easily
removed. One must give the benefit of the doubt to these new systems, hut one
is sometimes worried and displeased by the tendentious way facts relating to them
are presented.
The information presented to sugar technologists is insufficient for one to be
convinced that these instruments give the results the promotors are trying to
make one believe. The description of performance and the testimonies from users
are given in such profusion and in such a way, that they are seldom of aesistance
to the technologists trying to develop the manufacture of sugar along rational lines.

THE NECESSITY FOR FURTHER STUDIES

The necessity for further studies is evident because a number of new methods
for scale prevention h~ve been introduced to us in recent years. It is estimated
that at the present moment at least one million tons of cane sugar are manu-
faotured each year, in factories using anti-scale chemicals either continuously or
intermittently. The results obtained are very controversial and well conducted
research is required to find the solution to thequestions arising from the proposals
and the proper methods of applying these new procedures. Physical methods of
preventing scaling are used in factories producing about half a .rnillion tons of
sugar annually. The remark regarding the value of the chemical methods may also'
be applied to these methods. I
548 M anufacturing Section

The scaling of evaporators still forms' one of the bottlenecks in modern sugar
manufacture and a satisfactory. method to prevent scaling has not yet been found.
In the first place attention has to be given to the ordinary manufacturing processes,
liming, settling, filtering, and the way the juices are handled and mixed before
they are sent to the evaporators; in the second place it may be possible to develop
physical or chemical methods to diminish the scaling. But if real progress has to
be made in this field we must have a better understanding of ·the role of phosphates
added to thil'l. juice, of the function of different types of protective colloids in
scaling and precipitation, and where physical methods are proposed, we must
know the relationship between the type of current, its periodicity, voltage, current'
density or amp. per 1000 Iitres of juice treated. These measurements on the
'effect of scaling should always be done in strict conjunction with the determination
of the overall heat transfer in evaporators. More data are required as' to the
changes in the overall heat transfer in evaporators under practical conditions.
It is also very important that research studies be made to determine the amounts
of scaling non-sugars present in thin juice, and the amounts that are precipitated
in the different bodies, whether adhering tothe evaporating surfaces or suspended
in the concentrated juice. It is important to know more about-the effect of certain'
organic non-sugars upon the rate of scaling because there are indications that
with certain organic colloids present in the mill juices the rate of scaling is de-
o \

creased.
The many chemical reactions taking place in an evaporator in the sugar
factory have not received very much attention. For practical sugar manufacture
optimum results can only be obtained if all factors are kept as constant as possible.
The chemical reactions in evaporators are manifold, and the conditions con-'
stantly changing owing to factors bearing an unknown relationship to juice com-
position and the physical conditions existing during the evaporation process. It
requires a greater attention on the part of the research technologists, who must
devote their energy,knowl~,dge and experience to solve these most fascinating
problems in the cane sugar industry.'

APPENDIX I
D. W. Haering & Co" Inc., P.O. Box 6037, San Antonio, Texas; tetra-phospho-glucoeate. '
Wright Chemical Corp., 627, W. Lake Street, Chicago, Ill.; tetrafcsforg and Wrikorg C.
E. F. Drew & Oo., Inc., 15 East 26th Street, New York 10, N.Y.; APA-M and EO.
American Kat Corp., 331 Madison Avenue, New York 17, N.Y.; Kat.
Feedwaters Inc., 140 Cedar Street, New York 6, N.Y.; Tangite SE.
Alginate Industries, 4 Moorgate, London, E.C.2;, Sodium alginate SS/LH.
Kelco Company, <\1 Nassau Street, New, York 5, N.Y.; Keltex-aodium alginate,

APPENDIX II
Name of System Manufacturer Address
C.E.P.I. S;A. Epuro Avenue de France, Antwerp,'
Belgium. '
Superstat SuperstanLtd. Portsoken House 155, Minories,
London, E.C.3., England.
Hydrotron .Heller Laboratories Inc. 196 Morgan Street, Jersey City 2,
RJ., U.S.A. '
Solavite Sola Catalytic Co. 2013 Elm Street, Dallas, Texas;
U.S.A.
 G. C. Dymond 549

DISCUSSION
The Chairman endorsed the author's remarks that data published on, the scale-inhibiting
substances should be substantiated by tests.
Mr. Selman commented that scaling problem was not as acute in Queensland as over-
seas. Regarding evaporator sets, he said that steady rates of evaporation' could be attained
providing there were no changes in air or in cane. Once the noxious gases were eliminated the
condensate rate remained steady. This also applied to heaters. ' , '
Mr. Grant ,said that scale was very severe in South Afric.,a but the addition of phosphate
to the juice had considerably reduced the amount. Most of the scale-preventing materials as
well as the " Superstat " had been used with little success. ,
Mr. Hebert said that in Hawaii 'these chemicals had been used in different factories with
varying success. With ,the silica scales, manual Iabour was the only means of removal. Mr.
Elliott supported Mr. Hebert, in that no means had been devised to prevent scale. Mr. Hebert
mentioned that at the end of the week decreased heat transfer resulted in syrup of low brix
being produced. The capacity of evaporator sets was usually increased 50'~per cent. above
requirements to combat this and it was suggested that two final vessels be installed so that
one at a time could be taken off for cleaning.
Dr. Douwes Dekker discussed the scale problem in relation to the brix of the syrup. In
South Africa, if a low brix (50-55) be maintained at the beginning of the week, scale deposits
were low and the brix couldbe maintained. However, if the syrup were boiled to 65 brix early
in the week, scale would reduce the brix to 45 towards the close of the week.
Mr. Knox asked Dr. Honig if he had observed that the scale in thefirst pot was black and
that in the last pot was white. It seemed that the former scale was formed at low brix and high
temperature while the latter occurred under conditions of high brix and low temperature. He
wondered if the set could be run in reverse to induce precipitation of the scale-forming non-sugars.
However, Dr.-Honig said that this pI'ocess increased the colour formation very much. .The black
scale in the first vessel was caused by coagulation of impurities while the white scale in the last
'vessel was due to concentration of soluble impurities. Mr. Knox had found j.hat., in distillery
work, a scale was deposited on the tubes of. boilers at low temperatures while a sludge was
produced at high temperatures.
Gundu Rao mentioned two regions inTndia, one where a cloanout, of effets was necessary
each week, and another where the effets were cleaned every three weeks. This was due apparently
to a difference in phosphate content of the juice which 'was 80 mg. per litre in the former area
and 300 mg. per litre in the latter. The same varieties of cane grown in each area showed a
similar difference which could be attributed to the soil characteristics.
A request for information on the influence of phosphate on thesesquioxides in scale came
from-Mr. Whalley. He said that 1!J.e scales at Kalamia contained a good dealof alumina, 60 per
cent. in the first vessel and 40 per cent. in the last. HG also wished to know the solubility relation-
ships of iron, aluminium and phosphates with pH.
Mr. Agarwal supporting Dr. Douwes .Dekker said that he maintained thebrix of syrup at
about 55 subsequent to cleaning and evaporators would .thcn run satisfactorily for three weeks.
If liquor cooled off in the last vessel 'due to poor cane supply, scaling was bad; consequently,
the liquor was diluted prior to a hold up and this scaling was avoided.
Replying to Dr. Douwes Dekker, Dr. Honig said that the purpose of an evaporator set was
to produce a syrup of at least 65 brix. In .Queensland, the operator had Iittle trouble due to low
scale forma£ionin the fifth pot. To Mr..Whalley he replied that he could supply data showing
the effects of pH on the solubility of metallic non-sugars in juice, He mentioned the difficulty
of removing clay from juice which subsequently formed scale in the evaporator. Dr. Honig also
pointed out that overliming was to be avoided, as a heavy scale always res~llted.