Subhash Chandra

Lime
 Lime is clarifying agents are used in the chemical
treatment of sugar cane juice for the manufacturing of
plantation white consumption sugar.

 Lime used for clarification should be fresh, good purity

and reactivity and free from grits and stones.
 Wherever process of juice clarification is followed, lime is
the main clarification agent. Lime is usually added to the
juice as Milk of lime, a white milky liquid containing
slaked lime in suspension and in solution.
 In some part of world, however the clarification agent is
partly hydrated lime which is added to the juice a fine dry
powder.
Sr. PARAMETER LIMIT(%)

1. CaO content >90

2. Acid insoluble silica <1.5

3. Iron as Fe2O3 <2.5

4. Magnesium, as MgO <2.0

5. Aluminium as Al2O3 <1.0

6. Dead Burnt Lime <1.0

7. Sulphates(SO4)-- Absent
 Lime first neutralizes the free organic acids present in
cane juice, forming calcium organic salt.
 Lime reacts with phosphoric acid present in cane juice
and forms tri-calcium phosphate of formula Ca3(PO4)2
 Lime combines with nitrogenous impurities and partly
precipitated.
 Lime reacts with cane juice and removes coloring matters
like chlorophyll and anthocyanin.
 Lime reacts with cane juice and SO2 to form precipitate of
calcium sulphite CaSO3.
 When lime is added some of it undergoes reaction and
some remains in solution in the form of soluble CaO.
 Lime is the oldest and cheapest chemical being used in
sugar manufacture, as a juice Clarificant. The quantities
consumed depend on the process adopted for
clarification such as—
(i) for defecation consumption is 0.08 to 0.1% cane.
(ii) for sulphitation 0.12 to 0.15% cane.
(in) for carbonation 1.5 to 2% cane.
In Indian factories lime ie. calcium oxide CaO is used in
the form of lumps or powder but in Louisiana hydrated
lime i.e Ca(OH)2 in powder form or pulverised quick lime
has replaced the lumps completely. Lime is obtained from
high grade limestone by burning it in kilns. Many Indian
sulphitation plants prefer producing lime in kilns,
installed at the factory site procuring limestone and coal,
for their process use.
Lime stone i.e. calcium carbonate when heated is
decomposed with the formation of calcium oxide and carbon
dioxide.
CaCO3 CaO + CO2
100 56 + 44
Thus pure calcium carbonate on dissociation will yield 56%,
CaO. The reaction is endothermic heat absorbed being 42.5
K Cal. per mole. The optimum temperature range is 1100°C to
1300°C, though the dissociation commences at 600°C.
Burning at temperatures exceeding 1350°C for longer periods
results in production of dead burnt lime'. Higher SiO2 or
MgO content in limestone can cause formation of 'dead-
burnt' lime even at 1200°C. Properly burnt lime is highly
porous, light in weight and slakes quickly to form Calcium
hydroxide i.e. Ca(OH)2 on account of the easy penetration of
water molecules in the atomic interspaces
Lime i.e. CaO is highly hygroscopic and forms calcium hydroxide
on reacting with water.
CaO + H2O Ca (OH)2 + 15.2 KCal
The reaction is exothermic and heat is evolved during reaction.

SULPHUR
Sulphur is an important chemical used in plantation white sugar
manufacture for generating SO2in the clarification house.
Elemental sulphur occurs mostly in U.S.A., Italy and Japan,
though in sulphide form it is found in copper, iron and other
mineral deposits. The atomic weight of sulphur is 32.06 while its
melting point is 113°-115°C At 444.7°C which is the boiling point of
sulphur at ordinary pressure sublimation occurs. For use in sugar
manufacture sulphur must be of very high purity (above 99%).,
the maximum permissible levels of impurities being—
(i) Moisture-1%,
(ii) ash 0.1%,
(iit) bituminous matter -0.1%,
(iv) arsenic 0-05%.
Sulphur has an atomic weight of 32.06 and melts at 113°C. It
vapourises at 444°C when heated out of contact with air.
On account of its self sustained burning characteristic a
mass of pure sulphur once ignited burns completely in air.

In fact in one simple practical test a small quantity of

sulphur to be used in factory is ignited in a silica dish and if
the entire mass is burnt out in air the quality of sulphur is
considered satisfactory. Presence of impurities is indicated
by formation of a dark layer on the surface which hinders
combustion by restricting supply of oxygen (i.e. air).
Sulphur dioxide — Combustion of sulphur in a current of air generates
sulphur dioxide SO2.
When sulphur is heated in air it first melts and at about 363°C burns with blue flame
producing S02 and traces of SO3.
S + O2 SO2 + 2217 kcal/kg
Sulphur dioxide is a colourless gas 2.264 times heavier than air and possess an
obnoxious
smell. It is a poisonous gas. It can be liquified under pressure the liquid boiling at -10°C.
Molecular weight of SO2 is 64.06. In the presence of moisture SO2 is oxidised to SO3
during the process of combustion of sulphur.
Sulphur dioxide is highly soluble in water, 45 volumes being soluble in one volume of
water. However, a saturated solution of sulphur dioxide in water when boiled expels S02
completely.
It combines with water to form sulphurous acid.
H2O + SO2 H2 SO3
If the SO2 contains traces of S03 some sulphuric acid is formed
H2O + SO3 H2SO4
The sulphurous acid is dibasic and forms both normal and acid salts.
H2 SO3 H+ + HSO-3 Hydrosulphiteion
H2SO3 2H+ + SO3- Sulphite ion
Sulphur dioxide bleaches juice by acting on the coloring matter.
Sulphurous acid is a strong bleaching agent. It bleaches the coloring
matter originally present in the cane juice. It prevents or slows down the
color formation in later stages of the processing. It reduces the ferric salts
which are highly colored compounds formed by the action of iron of the
equipment with polyphenols into colorless ferrous compounds. Sulphur
dioxide gas decreases the viscosity of the juices. The lower the viscosity of
juice, the easier is crystallization.
Advantage of sulphitation - The advantages of sulphitation are
presented as follows (Hugot, 1986):
 The mud settles more rapidly and hence improved capacity of clarifiers
The mixture of sugar crystals and molasses
 (massecuites) before centrifuging
are less viscous and boil faster.

 Better crystallization in consequence.

 There is a marked improvement in the color of the sugar, there appears
to be a significantly reduced transfer of color from the mother liquor
into the crystal.
 There is a slight gain in the capacity of centrifugals.
Better elimination of phosphates and waxes leading to better refining
 quality and filterability of the sugar produced
Action of SO2 on juice clarification
SO2 neutralizes the excess quantity of lime added and
precipitates calcium sulphite.
Ca (OH)2 + H2SO3 CaSO3 + H2O
If more SO2 gas is passed and the juice is made slightly acidic, part
of calcium sulphite is converted into soluble calcium bisulphite,
which is undesired.
CaSO 3+ H2SO3 Ca (HSO3)2
Further addition of lime increases the pH and precipitation of
calcium sulphate starts again. The precipitation is complete when all
the acidity is neutralized by lime.
2H2 SO3 + 2Ca (OH)2 CaSO3 + 4H2 O
If highly acidic juice containing the soluble calcium bisulphate in
solution is boiled, it again decomposes into precipitated calcium
sulphate and sulphure dioxide.
2Ca (HSO3) 2 CaSO3 + SO2
 Disadvantages of Sulphitation

Kulkarni (2010) reported the demerits of sulphitation

process that the use of the sulfur burner is difficult as it
causes the toxic SO2 to be released into the atmosphere,
leading to serious environmental pollution.

It can also create health problems for the workers handling

the sulfur burners. The low color sugar and good luster
obtained from syrup sulphitation is a temporary one. The
color can increase from 60 IU to 100 IU or even 120 IU
within 6 to 10 months (Kulkarni, 2010).
 Reducing Sugars
Sucrose is fairly stable at high pH, but undergoes
decomposition when subjected to low pH. Sucrose is
hydrolysed at low pH into reducing sugars following the
reaction.

This reaction is catalysed by hydrogen ions and the rate of

hydrolysis is higher, higher the temperature and lower the
pH. Thus pH below 7.0 is to be avoided in all the treatments
of juice in clarification to prevent inversion since the above
reaction is irreversible.
The juices normally contain 0.5 to 1% reducing sugars which
play vital role in determining the exhaustion potential of
molasses in the final phase of crystallisation. Reducing sugars
also have to be kept intact to obtain maximum crystallisation
of sucrose in final boiling. Reducing sugars are more reactive
than the sucrose/ and unlike the latter are unstable at high pH.
High temperature accelerates this decomposition. Out of these
two hexoses,fructose is more sensitive to alkaline conditions
and is decomposed more rapidly than glucose. When reducing
sugars are reacted upon by alkali, fructose is destroyed first
while more fructose is formed from glucose in accordance with
Lobry De Bruyn Van Ekenstein transformation, whereby
equilibrium of glucose and fructose is maintained in alkaline
medium.
The decomposition of reducing sugars in alkaline condition
results in formation of lactic, gluconic, saccharanic and oxalic
and other organic acids which combine with lime to form
calcium salts. While salts like calcium oxalate and calcium
lactate are stable some other organic acid salts decompose into
acids under influence of heat. Under mild alkaline condition
slightly coloured acids like lactic acid are formed. At higher
At higher temperatures, the acids formed, combine with
lime to form coloured compounds. Thus the decomposition
of reducing sugars has to be avoided for following reasons—
(i) Organic acids are formed which increase calcium content
of juices,
(ii) The salts of organic acids increase scaling of evaporator,
(iii) Dark coloured compounds are formed which increase
colour content of juice,
(iv) Exhaustibility of molasses is adversely affected.

The conditions under which sucrose remains stable are

contrary to those for reducing sugars and therefore as far as
possible pH close to 7.0 should be maintained and the time
of contact at high or low pH should be minimal. Particularly
at high temperatures minimum time of reaction is essential
when pH deviates from 7.0 either way
Phosphate—As stated earlier phosphate precipitation
after reaction with lime is the main reaction responsible for juice
clarification. The reactions between lime and phosphates take time for
reaching equilibrium and are rendered more complex in nature in juice
due to the presence of organic acids, proteins and inorganic compounds.
Lime reacts with soluble phosphates as follows

Main reaction of clarification –

3Ca(OH)2 + 2H3PO4 Ca3(PO4)2 +6H2O
The tricalcium phosphate is transformed into insoluble hydroxyapatite
with drop in pH of juice. Formation of hydroxyapatite is accelerated by
high temperature and optimum conditions for formation of phosphate
precipitate are a. pH of 7.5-8 and b. heating to 100°C.
 100°C.Cane juice contains phosphates both in ionic
and nonionic form in varying amounts from 50-200
mgms per litre and the optimum level of P2O5 of 300
ppm.

 The purifying effect is to be caused by the absorptive

power of calcium phosphate and it has been observed
that calcium phosphate clarification is most effective
in eliminating colloids and finely dispersed matter
 Phosphoric Acid
Phosphoric acid and phosphates are used in the sugar
industry for various purposes, which mainly can be
classified under two headings:
 The clarification of sucrose solutions
 The conditioning of (feed) water

 The purifying effect is to be caused by the absorptive

power of calcium phosphate and it has been observed
that calcium phosphate clarification is most effective in
eliminating colloids and finely dispersed matter.
 Since the filtering properties of a calcium phosphate
precipitate are, however, unsatisfactory, low pressure
(bag) filters or flotation process is preferred to filter
presses
Sr. PARAMETER LIMIT
No.

1. PHYSICAL APPEARANCE COLORLESS

VISCOUS LIQUID
2. PURITY AS H3PO4 85.0

3. P2O5 CONTENT,MIN 61.5

4. IRON(PPM) MAX. 3000

5. SULPHATE AS(SO4)% 1.25

6. SPECIFIC GRAVITY AT25°C 1.7

The advantages from adding phosphate are:
 Clearer juice
 Greater colloid elimination
 Fewer lime salts in clarified juice
 More rapid settling
 Faster mud filtration
 Better colour of sugar
SUGGESTION
Always use food grade phosphoric acid for process industry.
Fertilizer grade phosphoric acid contains sulphate. Hence if
phosphoric acid gives white, thick precipitate with barium
chloride solution it should be rejected. If turbidity is
observed the sample should be analyzed for its phosphate
and sulphate content before use in the process.
 Color Precipitant
This is relatively new process aid, color precipitant are does
not reduce the conc. of color forming constituents such as
amino acid & polyphenols . As the ppt. formed by color
coagulant has to be removed, it should be added either
before lime addition or flocculent addition .
Color coagulant is characterizing by a strong basic centre
coupled with a long chain hydrocarbon or some times a
polymer chain.
Optimum dose has to be determined in the lab by
determining color of sugar solutions.
For Untreated syrup - Dose 100-150 ppm
For Untreated Melt - Dose 250-300 ppm
 Mill Sanitation Chemical

Target of MSC is to increase sucrose recovery, reducing

dextran formation, fructose degradation products, organic
acids as well as bad odour during the manufacture of sugar,
by control over various micro-organism like leuconostoc
mesenteroids and leuconostoc dextranicam.

Generally MSC used in three forms-

1. Di-thiocarbamate (Na/K dimethyl di thio carbamate)
2. Quaternary ammonium compound (Benzalkonium
chloride)
3. Halogen based (Sodium hypo chlorite, chlorine di oxide)
 Specification
Sr.No Chemical Requirement
1. Di-thio carbamate i. Yellow appearance
ii. pH value 9-10,
iii. Active content 35-40

2. Quaternary i. Colorless liquid

Ammonium ii. pH 8-9
Compound iii. Active content 30-35

3. Halogen based i. Colorless liquid

ii. pH value 10-11
iii. Cl content 15-20
Optimum dose of Mill Sanitation Chemical is
depend upon the RS and dextran content in
primary juice. Tentative optimum doses of MSC per
ton of crush cane is follows-
Sr.No. CHEMICAL NAME ACTIVE DOSE ppm
CONTENT(%) ON CANE

1. Di-thio carbamate 35-40 12-15

2. QAC 50 4-5

3. Halogen Based 25 10-15

1 . Increase in sugar recovery by reducing loss of
sucrose to 0.10-0.20 kg/ton of cane as against
loss of sucrose 0.2-1 kg/ton of cane if MSC
are not used.

2. Reduction in formation of dextran on mills

leading to less dextran content in
intermediated sugar product.

3. Reduction in color forming precursors such

as fructose degradation product.
 FLOCCULANT

These are special synthetic flocculating agents. Now

generally called polymer flocculants .

 The polyelectrolyte are mostly

ployacrylamides,anionic and of high molecular weight.
 Action of these polyelectrolyte is to produce the
secondary flocculation.
 FORMULA
CH2=CH--C—ONa
CH2=CH--C--NH2
O O
Acryl amide Sodium acryl ate

CH2 CH CH2 CH
CONH2 COONa
X Y

POLYACRYLAMIDE CHAIN
Bridging Theory Of Flocculation -
Flocculant act as a chain, the chain molecules form
interparticle bridges and bind the particles together.
Effect Of Molecular Weight-
 All polymer flocculants are of high molecular weight.
 Rate of settling is a function of molecular weight, i.e. settling
rate increased with increasing molecular weight.
 Molecular weights below 106 act only as stabilizers and are not
large enough for bridging.
 Molecular weights should be on the order of 107 for good
clarification.
Benefits-
 A good flocculent benefits are:
 It improves flocculation
 Increases settling rate
 Reduces mud volume
 Decrease Pol in cake
 Most important, increases the clarity of the clarified juice and
melt.
Viscosity Reducers-
Target of viscosity reducers is to increase fluidity of mother
liquor by lowering viscosity of massecuite, reducing surface
tension leading to improvement in boiling house
efficiency,crystallisation, centrifugation & exhaustion of
molasses.
Benefits-
 Reduce time for C-Boiling.
 Better purging, less washing.
 Reduce ash content on sugar.
 Better molasses exhaustibility in quality & quantity.
 Higher sucrose recovery.
Chemical Nature -

These are surface active chemicals. These compound are

generally organic compounds with high molecular weight.

Optimum Dose -
Optimum Dose has to be determined by carrying out
efficiency test in the laboratory.