Chapter 4

Clarification

1
 Objectives of juice clarification
The aims of juice clarification are:
 To trap all suspended matter, which can be settled at a satisfactory rate;
 To provide conditions of temperature, pH and ion concentration which will
maximize precipitation of soluble impurities from the juice;
 To produce clarified juice of high quality, with a minimum turbidity, color, and a
low calcium (Ca++) content;
 To produce a settled mud which is amenable to further processing (most commonly
filtration);
 To carry out the above at minimum cost, minimum residence time, minimum loss of
sucrose and minimum formation of color in the juice;
 To obtain a clarified juice pH that will minimize inversion in the subsequent
evaporation operation

2
 Treatment of syrup (saccharate) solution with lime in water is the basic method of
clarification, normally termed defecation.
 Lime has been the universal chemical for neutralization of the acidic juice, and the process
varies in the method and temperature of addition.
 Variations of simple defecation have always the aim of lowering the color and turbidity of the
clarified juice.

These include:
 Sulfitation: This combines treatments with sulphurous acid (from SO2 gas), and treatment
with lime solutions.
• Sulfitation is the practice of adding sulfur dioxide (SO2) to cane juice and syrup for the
purpose of color control.
• Sulfitation may be carried out on cold or warm juice, and, as well, on evaporator syrup
(double Sulfitation).

3
• Sulfur dioxide gas is produced by burning elemental sulfur. The gas is added to the
cane juice during clarification, in the presence of lime, and many of the complex,
little understood reactions that produce color in cane juice are inhibited by the
presence of SO2 gas.
• For example, enzymes responsible for the enzymatic browning reaction are
inhibited. For instance reducing sugars (glucose and fructose) are blocked by sulfur
addition at the aldehyde group and cannot react with amino acids to form browning
polymers in the Maillard reaction.

• Double sulfitation is practiced in many countries, in this process, a second dosage of sulfite
and lime are added to the evaporator syrup at a solids content of 55-65 percent." Double

sulfitation provides a better quality white sugar.

• If sulfitation is done first, because it lowers the pH of the juice, it is important to add the lime
(about 0.20% on juice) in as short a time as possible to prevent sugar loss. The advantages of
using SO2 is a much lower color in the produced sugar.
4
• Risks include increased scaling problems in the evaporators, high sulfite content in the final
product, higher sugar loss due to lower pH, and secondary color formation (color return) on
storage.
• Recently, the use of liquid SO2 has been shown to have advantages over the gas, especially in
a significant reduction in gas consumption (up to 69%) and a better quality of product.

5
 Phosphatation: Small amounts of soluble phosphate may be added to juices to improve
simple defecation.
• In phosphatation, the screened liquor is heated to 60-70°C and mixed with phosphoric acid
(0.005--0.025% P2O5 on solids).
• The mixture is immediately limed to PH 7.0-8.0, aerated with compressed air, and sent to a
clarifier, a tank equipped with heating coils.
• The liquor enters the clarifier at one end and is heated to 88°C while flowing to the outlet at
the opposite end.
• A flocculent precipitate of calcium phosphate forms, reacting with or entrapping colloids,
organic acids, some coloring matter, and suspended particles.
• Air flotation is used to separate the precipitate from the liquor, causing it to rise to the top of
the clarifier as a blanket of scum, which is skimmed off by moving paddles. (This process is
sometimes known as phosflotation) .
• About 25-30 percent of the color is removed in this process.

6
 Carbonatation: Limed juice treatment with carbon dioxide, followed by additional
lime for neutralization is termed ‘carbonatation’.
• It is now rarely used for the clarification of raw juice, but remains a core process for
clarification and decolorization of refinery syrups.

 Another variation, often advocated as a means of lowering the Ca++ content of

clarified juice, and hence of reducing problems with incrustations on evaporator
heating surfaces.
 Industrial juice clarification can combine some or all these treatments. The
implementation of the treatments uses a number of methods for the separation of the
precipitated impurities (sedimentation, flotation and filtration), and hence a quite
wide range of process equipment technologies and designs.

7
Ion - Exchange Processes in the Sugar Industry
 JUICE-SOFTENING PROCESS
 Juice-softening by chromatographic process has been used in the sugar
industry since the early 1980s.
 This process uses resin (ion-exchange resin) to remove the hardness
(limesalts) left in the thin juice after the juice-purification process.
Hardness compounds (e.g., CaCO3, CaC2O4, MgSO4, and CaSO4) are
the dissolved salts of calcium (Ca) and magnesium (Mg) that are not
removed during second carbonation.
 These salts are part of the nonsugars and are not filterable, so they stay
with the juice throughout the process. During evaporation a portion of
these salts precipitate in the evaporators but the larger portion stays in
the juice throughout the process and ends up in molasses.
 Thin juice containing large amounts of hardness, called hard juice, has
some undesirable qualities for sugar processing. When the juice is
heated in the heaters and evaporators, the reactions of hardness
compounds with other ions become more active, so the positive ions
of calcium (Ca) and magnesium (Mg) may bind with negatively
charged ions to form solid compounds.
 The two stations mainly affected by hardness in a negative way in
sugar processing are the following:
 Evaporation: The solid compounds that have more tendency to
precipitate at higher temperatures settle on the tubes causing
scale buildup, and consequently reducing heat transfer
 Crystallization: The solid compounds cause syrups to become
viscous, resulting in low mobility of molecules, slow
crystallization, low sugar recovery, and consequently high
molasses purity
 Following are some major benefits of the juice-softening process:
 Reduces scale formation in evaporators and juice heaters
 Provides a more efficient crystallization and sugar recovery
 Saves on energy and cleaning costs (boil out) of evaporators
 Prepares higher-quality soft thin juice for the rest of the process
 Reduces (or eliminates) the use of antiscalants during evaporation
JUICE-SOFTENING PROCESS

Figure: Thin juice softening

JUICE-SOFTENING BY CHROMATOGRAPHIC PROCESS

 Juice-softening by chromatographic process is a separation technique

based on the exchange of ions by ion-exchange resin (simply resin).
 In this process, the resin in a column selectively attracts some ions and
releases other ions, so the process is an exchange operation, hence the
name ion-exchange chromatography.
 The process is similar to water softening in households, which
involves the exchange of hard-water cations of Ca2+ and Mg2+ for
sodium cations (Na+) from resin to soften water. When resin becomes
nearly exhausted with Ca and Mg ions, it should be regenerated with a
solution containing sodium, such as salt solution (NaCl).
 Ion-exchange resin (resin) is a porous-insoluble polymer in the form
of small (1 to 2 mm diameter) particles
 Resin particles are usually yellowish and can operate at high
temperatures and different pH ranges.
 Because of porosity, resin has a very large surface area, so it can
selectively exchange ions (cations and anions) in a solution for other
ions, hence the name ion-exchange resin.
 The process of exchanging ions for another’s by resin (e.g., in juice
softening by chromatographic process) and separating components of
a compound from each other is called chromatographic process
 Ion-exchange resins are divided into two main groups:
■ Cation-exchange resins (catex), which remove cations from a solution
■ Anion-exchange resins (anex), which remove anions from a solution
 Cation resins contain a functional group (exchangeable group) that
has a negative charge, such as (SO3H)−
 It has the ability to remove cations (postitively-charged ions).
 A functional group is a group of atoms in a molecule that behaves as a
unit and is responsible for its reactions with other substances.
 Examples of functional groups in resins are the sulfonyl (SO3H) and
carboxyl (COOH) groups.
 In the cation resins, the exchangeable ion of the functional group
(e.g., H in SO3H) can be exchanged for a particular cation present in a
solution because of its affinity (capability of absorption) for that ion.
 For example, H can be exchanged for calcium ions (Ca2 ) and
magnesium ions (Mg2 ) in thin juice by passing the juice through a
resin bed (a small or large column filled with resin). When the juice
passes through the resin bed containing the SO3H group, the
following reactions take place:
R-(SO3H)− Ca2 ↔ R-SO3Ca + H
R-(SO3H)− Mg2 ↔ R-SO3Mg + H \
 In a typical thin-juice softening by chromatographic process (see
Figure below), thin juice is fed to large softening columns that are
filled with resin.

Figure. A typical thin-juice softening process

 The softening column is 3 to 5m high and 2 to 3m in diameter. As the
juice passes over the resin, calcium (Ca2+) and magnesium (Mg2+)
ions displace the ions from the resin (usually sodium or hydrogen ions
in thin-juice softening).

Figure. Thin juice softening column

 Based on the chemistry of the juice-softening process, for every Ca
ion that binds with the resin, two Na ions from the resin are released
to the juice. Therefore, the juice that exits the softener is almost free
of Ca ions but contains Na ions in their place.
 The liquid leaving the softener is called the soft juice because Na ions
are much less scale-forming than calcium. Eventually, the resin is
filled with calcium cations. At this time, the resin needs to be
regenerated (reactivated).
 The flow of the feed to the column stops and the resin regeneration
cycle starts. The flow is switched to the next column (called standby
column), which is already regenerated.
 Resin is regenerated by pumping a regenerant, which is a solution
containing Na ions (usually diluted NaCl or NaOH), to the softener
column.
 During regeneration, calcium ions are removed from the resin and
sodium ions occupy their place in the resin. After regeneration, the
resin is ready again for the next softening cycle.
JUICE-SOFTENING SYSTEMS

 There are several juice-softening systems to supply softer juice for

processing.
 The process of juice purification followed by juice softening can
eliminate more than one-third of the non-sucrose content present in
the juice. Therefore, juice softening can be considered part of the
purification station and its efficiency enhancer.
 In the juice-softening process, a cation resin (either strong or weak) is
used to selectively exchange some cations of the juice. An
understanding of the differences in properties between strong-acid-
cation (SAC) resin and weak-acid-cation (WAC) resin is important
because both are used in thin-juice softening.
 The major differences follow:
 SAC resins have a lower exchange capacity than WAC resins.
 SAC resins (in Na form) provide no risk of sucrose inversion, while WAC
resins (in H+ form) may cause some sucrose inversion.
 SAC resins operate at a lower flow rate than WAC resins.
 SAC resins remove all cations, whereas WAC resins remove only cations
equivalent to bicarbonate alkalinity (natural alkalinity).
 SAC resins create some dilution during operation, whereas WAC resins create
more dilution.
 SAC resins expand less during regeneration than WAC resins, which expand
almost twice when they are exhausted.
 SAC resins need a more excessive regenerant over the stoichiometric quantity
(SQ) for regeneration (50 to 150% over SQ ) than WAC resins (about 10% over
SQ ).
Although the advantages are in favor of SAC resins, a softening system
that uses WAC resin is also can be used. Operation of the softening
process generally consists of the following cycles:
1.Service: Heated juice (80 to 90oC) is passed continuously through the
resin bed until the resin is nearly exhausted (saturated with the hardness).
(The higher amount of hardness in the treated juice signifies that the
resin is exhausted.)
2.Backwashing: The resin is backwashed with soft water (factory
condensate) to remove particulates. The backwashing cycle brings the
resin to its original order because, during the service cycle, resin particles
become classified (the largest particles remain at the bottom, while the
smaller ones are distributed on a higher level). A backwash is provided
by applying a uniform flow of water from the bottom of the bed to
fluidize the resin.
3.Regeneration: The resin is regenerated with a regenerant to return the
resin to its original capacity.
4.Rinse: The resin is rinsed with soft water.
5.Service: The regenerated column is again fed with juice.
 The size of the columns depends on the amount of feed to be
processed and its hardness content. Because the regeneration of the
resin beds requires twice as much time, you need double the number
of columns.
 During operation, usually half of the columns are in exchange
position, and the other half undergo regeneration, or stay on standby
for a new use. Typical positions of the columns, based on the design,
are as follows:
 Three-column design: Two in exhausting and one in regenerating
or on standby
 Four-column design: Two or three in exhausting and one or two in
regenerating or on standby
 Five-column design: Three in exhausting and two in regenerating
or on standby
 Nowadays, softening systems are fully automatic and computer
controlled. A flow meter and flow-control valve on each column
regulates the flow through each step of the operation.
 The two different softening methods often used in sugar factories are
 Juice-softening by strong-acid-cation (SAC) resin
 Juice-softening by weak-acid-cation (WAC) resin
JUICE-SOFTENING BY SAC RESIN
In the juice-softening by SAC (strong-acid-cation) resin, the softener
uses resin mainly in sodium form (Na+) to soften the juice. When the
juice containing divalent cations (Ca2+, Mg2+) passes through the resin,
the following reactions take place:
2R−Na+ + Ca2+ ↔ R2−Ca+2 Na+
2R−Na+ + Mg2+ ↔ R2−Mg+2 Na+
Scale-forming cations of the juice (Ca and Mg) are replaced by non-
scale-forming sodium ions from the resin. The efficiency of replacement
determines whether the juice is soft enough to produce soft molasses.
Based on the type of regeneration, thin-juice softening by strong resin
can be divided into three groups:
 Conventional method: Uses Na+ ions in NaCl solution for
regeneration
 Gryllus method: Uses Na+ and K+ ions in low-green syrup for
regeneration
 NRS method: Uses Na+ ions in NaOH solution and soft juice for
regeneration
Conventional Juice Softening

 In conventional juice softening, the softener uses common salt (NaCl)

in a 10% solution to regenerate the resin. Salt is used mainly because
it is inexpensive and plentiful. The process is similar to household
water softening, which uses resin to remove the hardness from the
water.
 Following are disadvantages of the conventional method:
 High water use
 High wastewater
 High sugar loss (Na is more melassigenic than Ca)
 High juice dilution (because after sweeten-off and regeneration,
the resin is rinsed with water)
Gryllus Juice Softening

 In Gryllus juice softening (named after the Hungarian inventor, Eva

Gryllus), ions of Na and K in the low-green (C) syrup are used to
regenerate the resin.
 High sodium and potassium in the syrup make it very efficient to
regenerate the resin after exhaustion with calcium
 The Gryllus method eliminates the main disadvantage of the
conventional method by not producing wastewater.
 Compared with the conventional process, the Gryllus method has the
following advantages:
 No wastewater
 No juice dilution
 Clean evaporators
 Better fuel economy
 No change in the melassigenic properties of the nonsucroses
NRS Juice Softening

 In NRS (new regeneration system) juice softening, Na+ cations in

caustic soda (NaOH) solution and in the soft juice are used to
regenerate the resin.
 This process does not have the disadvantages associated with the
conventional process (NRS does not produce waste effluent) and the
Gryllus process (NRS can soften juice to the extent that soft molasses
can be produced.)
 In NRS softening, soft-thin juice is cooled to 40oC and mixed with

50% caustic. The mixture is then used to regenerate the resin. The

regeneration is operated at a low temperature to produce soluble

calcium saccharate (mono- and di-calcium saccharates are soluble in

water).
 During regeneration, the sodium from the caustic is exchanged for the

calcium ion in the resin. At the same time, sucrose reacts with released

calcium ions to form soluble calcium saccharate.

 Regeneration effluent is pumped to the first-carbonation tank, where

CO2 decomposes the saccharate into sucrose and calcium carbonate

(CaCO3). The second-carbonation juice is filtered and sent to the

softener to produce soft juice.

 A small portion of soft juice is sent back to the softening station to

regenerate the resin, while the main part enters the evaporators.
 The advantages of NRS softening are as follows:
 Produces soft molasses
 No sucrose inversion
 No juice dilution
 No wastewater
 The disadvantage of this process is that additional sugar loss occurs
because of an increase in molasses production.
JUICE-SOFTENING BY WAC RESIN

 The juice-softening by WAC (weak-acid-cation) resin also used in the

sugar industry.
 This technology uses WAC resin, such as Dowex MAC 3, in the
hydrogen (H+) form. Softening occurs according to the following
equation:

2R−H+ + Ca2+ ↔ R2−Ca + 2H+

 When the resin becomes exhausted with calcium, it is regenerated
with a low-concentration acid solution.
 Regenerating the resin with a sulfuric acid solution (H2SO4), instead
of hydrochloric acid (HCl), has two advantages:
 H2SO4 does not corrode stainless steel, while HCl adds chlorides
to the system, which corrodes stainless steel and is more
melassigenic than sulfate.
 H2SO4 produces calcium sulfate, which can be used in the diffuser.
R2−Ca + H2SO4 ↔ 2R−H+ + CaSO4
Because calcium sulfate is insoluble at higher concentration, there is a
risk of calcium sulfate precipitation inside the resin bed during
regeneration. This will result in deposits of calcium sulfate within the
resin structure, which fouls the resin.
Therefore, to avoid precipitate formation and resin fouling, keep the
strength of sulfuric acid low. It is recommended to use H2SO4
concentration in the range of 0.07N (about 0.2% acid).
JUICE-SOFTENING BY TWO-STEP PROCESS

The juice-softening by two-step process was recommended by

Amalgamated Research (the supplier of juice softening by WAC resin). It
is used mainly when the juice contains high hardness. The process
consists of the following two steps:
 Step 1: Pretreatment with soda ash to reduce the amount of
hardness to the 100 to 150mg level
 Step 2: Treatment with the WAC resin to reduce the hardness to
the desired level of about 17mg
Generally, adding soda ash to the juice has the following advantages and
disadvantages:
 Decreases the hardness (advantage)
 Increases juice alkalinity (advantage)
 Completes the lime reaction (advantage)
 Increases Na in the juice, which is partly removed by the resin
(disadvantage)
 Soda ash is highly melassigenic; Na is more melassigenic than all
cations of the juice except potassium; the melassigenic factor of
soda ash is 0.42, which is high (disadvantage)
Exercise

1. Write the chemical exchange reaction in anion exchange resin

2. The two stations highly affected by hardness are
3. Write the chemical regeneration reaction of WAC resin