FORTY-FIFTH CONFERENCE

CHEMICAL CLEANING OF EVAPORATORS

BY
P. C. IVIN
Sugar Research Institute, Mackay
ntroduction
There is a current trend in the Queensland sugar industry towards a purely
hemical cleaning treatment of evaporators. Byrne (1977) has reported on the common
rocedure of boiling high concentrations of caustic soda under vacuum.
Honig (1963) has outlined a general approach t o the cleaning of evaporators.
lelection of a suitable cleaning agent will depeng on such factors as the nature and
everity of scaling, cost and corrosive nature of chemicals, the materials of
onstruction of the effets, dangers of use to personnel, ease and speed of the overall
leaning operation, ease of storing reusable solutions and disposal of spent liquors.
Laboratory scale tests allow determination of a number of these factors but are
lot necessarily indicative of what will happen on a large scale. Therefore, pilot scale
vaporators were set up under similar conditions to final vessels at Racecourse and
Lalamia mills in 1976 to allow the formation of typical scale on effet tubes suitable for
hemical cleaning tests.

VAPOUR EXBAUST

W
REMOVABLE L I D

P I L O T EVAPORATOR
( 3 tubes, 1980 m
X 44 mm O . D . )

CONDENSATE

Fig. l-Layout Pilot Evaporator.

 FORTY-FIFTH CONFERENCE

Pilot Plant Evaporators

Fig. 1 shows the general layout of the pilot plants in relation to their parent
vessels.
Three full length stainless steel, type 304, effet tubes were surrounded by a steam
chamber supplied directly from the vapour supply from the previous effet. Syrup was
pumped via a mono pump from a point just under the bottom tube plates to just below
the bottom tube plate in the pilot evaporator. Once a stable syrup level was achieved, a
slight excess head caused the process syrup to return to the main vessel by gravity.
Condensate was collected through a steam trap with flow controlled by a Delasco
5223 peristaltic pump. A fine tube at the top of the steam chamber allowed non-
condensables to be vented into the vacuum above the boiling syrup.
Other valves and pipework served as drain, sampling and cleaning solution access
lines to the vessel.
The Racecourse installation was recently modified to allow input juice to be
supplied from the previous effet.
Performance of the Pilot Evaporators
The initial scaling rates obtained were low at both mills due to a combination of
such factors as unreliable pumping of juice feed from the final vessel to the unit,
inequality of operational conditions obtained for the unit compared with the final
vessel, and variations in the syrup level in the tubes.
Installation of the larger CD42 mono pumps for juice supply and improved
vacuum supply lines produced reliable scaling rates that allowed cleaning tubes to be
carried out every two or three weeks. At Racecourse, relocation of the juice supply line
to deliver from the previous vessel rather than from under the tubeplate of No. 5 vessel
resulted in a greater scaling rate. However, the output syrup Brix dropped from the 68-
72 Brix level of the parent final vessel to 55-60. Future modifications are to be made on
the d a n t to allow automatic control of the output svruD Brix to match that of the
*
vessel when juice is supplied from No. 4 Gessec
TABLE I-Scale analyses, Racecourse Mill pilot evaporator
Date sampled 12.8.76 24.1 0.77 7.1 1.77
Loss on ignition (%) 23.0 43.7 46.2
SiO, (% on ash) 26.6 12.9 5.3
CaO (% on ash) 7.6 48.4 52.1
M g O (% on ash) 0.2 0.2 0.1 5
R,O, (% on ash) - 2.7 4.4
P205 (% on ash) 0.4 - 0.01
SO, (% on ash) trace trace trace

TABLE Il-Scale analyses, Racecourse Mill No. 5 vessel

Date sampled 8.11.76 6.7.77 21.7.77 6.11.77Ta 6.11.77Ba

Loss on ianition (%) 13.9 30.9 19.7 18.5 32.6
SiO, (% & ash) '
CaO (% on ash)
M g O (% on ash)
R,O, (% on ash)
P205 (% o n ash)
SO, (% on ash) 1 2.4 1 6.5 1 3.6 1 trace I trace I
l I I l l I I
aT and B after date indicates sampling from top or bottom sections respectively of tube only.

Tables I and 11 show the composition of scale samples taken from the pilot plant
and parent vessel effet tubes respectively at Racecourse mill. The results indicate large
variations in scale composition with time and from the top to the bottom of the tubes.
Some of the high R203*values are believed to be due to contamination by either the
metal sample brush or from the evaporator tube material itself.
A large change in the nature of the pilot evaporator scales after the 19th August,
1977 coincides with the alteration of juice supply from the parent vessel to that from

"Total sesquioxides e.g. Fe203, AI,O, .

978 FORTY-FIFTH CONFERENCE 323

Vo. 4 vessel outlet. Since the resultant output syrup Brix from the pilot evaporator
lropped from 72 to 60, the change in scale characteristics can be quite expected.
Table I11 shows the scale analyses of samples taken from the Kalamia pilot
xaporator. These indicate similar variability in composition to that exhibited by the
Racecourse scales.
In general, most of the scales are marked by high silica, relatively low calcium and
nagnesium, and, with one exception, low sulphate contents. Paper chromatography
xas used to indicate the presence of significantconcentrations of oxalate and to a lesser
:xtent of aconitate organic salts in a large number of representative scales. Generally
ligher sulphate contents could be expected for final vessel scales. Quite a number of
inalyses carried out on these scales at Sugar Research in the past have indicated high
:alcium sulphate contents of up to 55 per cent on ash (Relf et al., 1959). However,
4nderson (1951) does mention two silica scales with high organic matter and low
alphate content at Pleystowe.
Scales from both the pilot and final vessel at Racecourse were of similar type with
he exception of the period after 19th August, 1977 when the pilot plant output syrup
Brix was non-representative of a final vessel. Therefore, the pilot plants were accepted
is providing typical scaled tubes for the following chemical cleaning tests.
TABLE Ill-Scale analyses, Kalamia Mill pilot evaporator
Date sampled 6.9.77
Loss on ignition (%) 22.0
SiO, (% on ash) 53.3
CaO (% on ash) 12.2
MgO (% on ash) 2.2
, , (% on ash)
RO 16.0
P,O, (% o n ash) 9.2
SO, (% on ash) trace

Pilot Tests on Chemical Cleaning

The general approach used in these tests was to use methods that were relatively
:conomical, of greatest potential and could be carried out in one to two hour periods
iom the boilout of syrup in the effets at weekends. Some proprietary cleaning
naterials were tested but records of their performance are not necessarily conclusive
ince they have not been tested a sufficient number of times with chemical solutions.
fhe effect of lengthy overnight soaks was excluded from the pilot tests although the
)otential of this procedure to improve scale removal is acknowledged.
Tables IV and V show a summary of the chemical solutions tested together with
heir periods of heating. Unless otherwise indicated, all boiling was carried out at
~tmosphericpressure. The percentage scale removal values were based on mass losses
letermined by weighing the entire effet tubes before and after the cleaning procedures.
iny test with scale mass removal greater than 90 per cent appeared to be satisfactory
)n a visual basis. A number of tests were evaluated visually on the percentage of metal
irea exposed after cleaning in those cases where the actual scale mass was too low for
lccurate mass difference determinations.
The results are compatible with the success in the factory of strong concentrations
)f caustic soda solutions with boiling under both atmospheric and vacuum conditions.
Two tests utilising five per cent caustic soda may be misleading in their success since the
cales tested are believed to be more representative of a No. 4 effet vessel in a quin set.
,ewer concentrations of caustic soda solution may be successful with special additives
)ut the combination is expected to be more expensive than caustic soda solutions
done.
The use of a single sulphamic acid treatment with Armohib inhibitor did remove
75 per cent of scale mass but did not take any scaled area back to a clean metal surface.
Zosts for this type of treatment are higher than for the alkali treatments and the
~ossibility of higher corrosion rates even with acid inhibitors makes further
nvestigation along these lines unattractive.
Two stage treatments utilising hot soak periods with low concentrations of caustic
oda solutions after an initial boil with alumina-ferric solution are quite successful.
lowever, the order of the two treatments markedly affects the scale removal efficiency
ind the procedure must begin with the alumina-ferric solution. This type of cleaning
324 FORTY-FIFTH CONFERENCE 1978

has been carried out in a highly successful manner at Plane Creek mill for a number of
seasons and results in substantially clean effet tubes.
Sulphamic acid is a stronger acid and worked well in a two stage treatment.
Regular use of this reagent cannot be justified as long as the present success with the
cheaper alumina-ferric reagent continues.

TABLE IV-Scale removal (%) with single chemical treatments

Note: Concentrations 'ark on a ma&/volume basis.

Scale removal (%)

Chemical treatment
Kalamia
(a) Single caustic treatment
2% Caustic soda 1 h boil
4% Caustic soda 2 h boil
5% Caustic soda I h boil
20% Caustic soda 1 h poor boil
20% Caustic soda 1 h good boil
20% Caustic soda 1 h good boil
20% Caustic soda 1 h good boil
30% Caustic soda 1 h boil -90 kPa vacuum
(b) Caustic and caustic additives
5% Caustic soda + 3% CD 280 I h boil
2% Caustic soda + 0.1 % Busperse 47 1 h boil
10% Caustic soda + 0.1% Busperse 47 I h boil
10% Caustic soda + 0.5% Rapisol I h boil
10% Caustic soda $- 0.5% PDR 201 I h boil
c) Single acid treatment
5% Sulphamic acid + 0.02% Armohib I h boil
L
"Scale formed with low output syrup Brix

LE V-Scale removal (%) with two stage chemicai treatments

Scale removal (%)

Chemical treatment
Racecourse Kalamia
1 ,L% Alumina-ferric 1 h boi1/4&% caustic soda 1 h soak 85OC 99
l,'% Alumina-ferric 1 h boil/4,'% caustic soda 1 h soak 85OC 95
I,'% Alumina-ferric I h boil/4&% caustic soda 1 h soak 85OC 88
1,%' Alumina-ferric I h boil/4&% caustic soda 2 h soak 85OC - 91
1,%' Alumina-ferric 1 h boil/4h% caustic soda 1,1 h soak 85C 95
4,'% Caustic soda 1 h boil/l&% alumina-ferric 1,' h soak 85C - 64
2% Caustic soda 1 h boil/5% Alclean 5032 1 h soak 60C - 100
2% Caustic soda I& h boil/5% Sulphamic acid +
0.02% Armohib ,'h boil 100 98

Corrosion Testing
In 1976 and 1977 pairs of 70:30 brass, mild steel and stainless steel, type 304, test
pieces were installed in the body of the No. 5 effet vessel at Racecourse mill. Here they
were subjected to normal syrup boiling and weekend cleans using a 50-minute boil with
20-25 per cent w/v caustic soda solution at atmospheric pressure followed by a 20-hour
soak period. Corrosion rates were determined by measurement of mass losses in
accordance with the standard method, ASTM 61-72 (Anon, 1972).
The results are shown in Table VI. Although there appears to be some difference in
corrosion rates for stainless steel between the 1976 and 1977 tests, both sets of values
are low.
If a typical crushing season is taken as requiring 20 weekend cleaning treatments
of 21 hours each, then brass, mild steel and stainless steel will corrode at an average rate
of 0.012, 0.029 and 0.0015 mm per crushing season respectively.
The measured corrosion rates were similar to those reported by Uhlig (1955) and
indicate the acceptability of those cleaning procedures using high concentrations of
caustic soda solutions.
These measurements assume that a uniform corrosive attack has taken place and
do not take into account the possibility of stress corrosion or localised pitting.
978 FORTY-FIFTH CONFERENCE 325

tecently, complete effet tubes have been taken from the body of No. 5 vessel at
<acecourse mill for metallurgical analysis. Since this mill has been using concentrated
maustic solutions for more than three years. the results of these tests should be useful in
,onfirming the suitability of these cleaning procedures with stainless steel.
TABLE VI-Corrosion rates of testpieces-Racecourse Mill

/ear I Material
Test exposure
to caustic
Corrosion rate
(mm year-') (mm/season * )
Brass
Mild steel

S.S. 304
Brass
Mild steel

S.S. 304

Corrosion rate for 20 weekends each of 21 hours exposure to caustic

)iscussion
Analyses of scales obtained from the pilot evaporators at Kalamia and
<acecourse have, with one exception, shown very low levels of calcium sulphate
:ompared with most of the analyses of mill scales collected in previous years and this
nay be an important factor in determining the solubility of the scales in caustic soda.
The change in scale composition could be due to a change in cane fertilization
)ractices. Sedl(1971) has reported that luxury uptake of sulphur by cane occurs when
ertilizer sulphate has been applied to the soil. Ammonium sulphate has now been
lisplaced by aqua ammonia, urea and ammonium nitrate and the phosphate fertilizers
,ontain much less sulphate than normal superphosphate.
The industry now has three general approaches to chemical cleaning of effets:
a) A one-hour boil of 20-25 per cent wjv caustic soda solution at atmospheric
pressure;
b) 8-10 per cent w/v caustic soda solution is concentrated to over 25 per cent wjv
concentration under vacuum (Byrne, 1977);
c) A two-stage treatment using a one-hour boil with l + per cent w/v alumina-ferric
solution is followed by an hour and half soak at 85'C with 43 per cent w/v caustic
soda solution.
It is still desirable to consider ways of improving the performance of the first two
.pproaches. Not all scale is removed by these procedures: although performance of the
ffet stations using them does not appear to be greatly affected by this. Again, while
orrosion rates with the higher concentrations of caustic soda solutions appear to be
cceptable, both by observations in the laboratory and in the plant, there could be
.dvantages in finding additives which would allow lower concentrations to be used.
A number of additives affecting such properties as surface wettability are being
~fferedon the market to extend the performance of caustic soda solutions. Claims as to
heir temperature and alkali stability have yet to be substantiated. Even if they do
rove to be stable, they may still be too costly to use. For example, a solution of the
ecommended strength of the Catoleum CD 280 in a five per cent caustic soda solution
5 more expensive than using 20 per cent caustic soda alone. Pilot plant tests will be
arried out on a number of the more economical alternatives in the future.
The third approach has a higher initial capital cost outlay but uses the least
orrosive cleaning reagents, is economical and results in efficient effet scale removal. As
uch it merits careful consideration when planning an approach to a purely chemical
leaning procedure for effet scale removal.
The emphasis in this paper has been on the scales from final effets simply because
hey are usually the hardest to remove. Once a satisfactory treatment has been found
or these vessels, modifications of the procedure can usually handle scales in the other
essels.
 326 FORTY-FIFTH CONFERENCE 197f
Conclusion
Pilot plant evaporators have provided scaled effet tubes suitable for testing
chemical cleaning procedures. These tests confirm the present success in thc
Queensland sugar industry of concentrated caustic soda solutions or a two-stagt
alumina-ferric/caustic soda solution treatment in substantial removal of final vesse
scales.
Some of the apparent ease of scale removal with these treatments may be due to 2
change in the type of scale formed since farming practices now use fertilizers of lowei
sulphate content.
Further investigations are to be carried out into chemical cleaning including tht
use of additives and their effect on the performance of caustic soda solutions. However
the present increased costs of these alternative treatments compared with those now
accepted by the industry will make further developments in this field unlikely.
Acknowledgements
The co-operation of the managements of Racecourse and Kalamia mills it
appreciated. Mr. T. Seldon of Kalamia mill and Messrs. J. Littlemore, R. Garland anc
R. Zemek of Sugar Research Institute gave considerable assistance with plan
operations and scale analyses.
REFERENCES
Anderson, G. A. (1951). Mechanical methods of scale removal, Proc. Qd. Soc. Sugar Cane Technol., 18tl
Conf.. 103-109.
Anon., (1972). 'standard recommended practice for preparing, cleaning and evaluating corrosion tes
specimens, ASTM 61-72,
Byrne, H. J. (1977). Effet cleaning using sodium hydroxide, Proc. Qd. Soc. Sugar Cane Technol., 44th Conf.
- .-.
719.347
-*,
Hodg, P. (1963). Principles of sugar technology, Vol. 111. Elsevier. 1S2-222.
Relf, E. T. and Foster, D. H. (1959). The chemical removal of evaporator scale. Proc. Qd. Soc. Sugar Can1
Technol.. 26th Conf.. 51-56.
Sedl, J. M. (1971). Sulphur nutrition studles with sugar cane. Tech. Comm. No. 2, Bur. Sug. Exp. Stns., Qd
Uhlig, H. H. (1955). Corrosion Handbook. Wiley.