THE PEOPLE

BEHIND SUGAR

Presents a Technical Paper to BSST 11/10/2012

Decolourisation Techniques used in Sugar Refining

What is Refined Sugar?

THE PEOPLE BEHIND SUGAR

Early Sugar Refining in London

Bone Char Treatment

Taylor Filters

The Wash Floor

What is Refined Sugar?

Typical Refined Sugar Colours
EEC Grade I 20 IU colour

Bottlers Grade 35 IU colour

EEC Grade II 45 IU colour
EEC Grade III 60 IU colour
White Sugar

<100 IU colour (typical)

What is Refined Sugar?

Other Typical Refined Sugar Requirements

Filtered (as a dissolved solution)

Suspended solids less than 2ppm
Pol 99.9 minimum
Ash 0.015% maximum
Invert 0.020% maximum

Other The full list of requirements for refined sugar may vary from one
grade of sugar to another and these are often on a sliding scale as in the
case of EEC Sugars. However, the important parameters listed above
along with sugar colours are typical specifications for refined sugars.
Sugars such as bottlers grade may be subject to individual purchasers
specifications, and the likes of the international Cola beverage companies
have their own world standards for acceptable sugars for their drinks
formulations.

What is Refining?

A series of steps for removing

impurities and Colour

Affination

Melting

Clarification

Phosphotation or
Carbonatation

Filtration

Pressure Filtration or
Deep Bed Filtration

Decolorisation

Ion Exchange Resin ,

Powdered Activated
Carbon or Granular
Activated Carbon

Primary Decolourisation

Phosphatation
Carbonatation

Evaporation

Crystallisation

Drying

Conditioning

Bagging and
packing

3 , 4 or 5 boiling or
backboiling

Secondary Decolourisation
Ion Exchange Resin
Powder Activated Carbon
Granular Activated Carbon

Types of Colorants in Raw Sugar

Types of Colorants in Raw Sugar

Indicator Value = Colour pH9 / Colour pH4

Origin of Colorants in Raw Sugar

Colour Profile in Raw Sugar

45.0
40.0
35.0
30.0

25.0
20.0
15.0

10.0

A
E

5.0
0.0
0.0

5.0

High

10.0

15.0

20.0

25.0

Molecular Weight

30.0

35.0

40.0

Low

Colours after Affination

Process

45.0

Percent Removed

C
A

40.0

Affination

56%

43%

34%

35.0

30.0

B
25.0

20.0

15.0

D
10.0

5.0

0.0
0.0

5.0

High

10.0

15.0

20.0

25.0

Molecular Weight

30.0

35.0

40.0

Low

34%

34%

Colours after Carbonatation

Process

45.0

Percent Removed

C
A

56%

43%

34%

34%

34%

Carbonatation 80%

50%

50%

50%

20%

40.0

Affination
35.0

30.0

B
25.0

20.0

15.0

D
10.0

5.0

0.0
0.0

5.0

High

10.0

15.0

20.0

25.0

Molecular Weight

30.0

35.0

40.0

Low

Colours after Ion Exchange Resin

Process

45.0

Percent Removed

C
A

Affination

56%

43%

34%

34%

34%

Carbonatation

80%

50%

50%

50%

20%

0%

92%

67%

93%

50%

40.0

35.0

Acrylic

30.0

B
25.0

20.0

15.0

D
10.0

5.0

0.0
0.0

5.0

High

10.0

15.0

20.0

25.0

Molecular Weight

30.0

35.0

40.0

Low

Colours after Carbon

Process

45.0

Percent Removed

C
A

Affination

56%

43%

34%

34%

34%

Carbonatation

80%

50%

50%

50%

20%

Acrylic

0%

92%

67%

93%

50%

Carbon

33%

40%

50%

72%

50%

40.0

35.0

30.0

B
25.0

20.0

15.0

D
10.0

5.0

0.0
0.0

5.0

High

10.0

15.0

20.0

25.0

Molecular Weight

30.0

35.0

40.0

Low

Decolourisation Systems Comparison

20.00

18.00

16.00

14.00

12.00

10.00

8.00

6.00

4.00

2.00

0.00

10

15

20

25

Resin/Granular Carbon

30 5

35 10

40 15

20

Bone Char

25

Processing Choices

COLOUR
REMOVAL
ACROSS
PROCESS

50%

50%

50-80%

90%

IER
CARBONATATION
CRYSTALLISATION

RAW
SUGAR

GAC

AFFINATION

&
CENTRIFUGAL
SEPARATION

PHOSPHATATION

PAC

REFINED
SUGAR

Removal Chart

How do they Work?

Affination

Raw
Sugar
Bin

Syrup

Overflow to
Recovery
Steam

Weigher

44oC
Wash
Water

To Melter

Syrup

How do they Work?

Affination

A large proportion of the Raw Sugar Colour is on the

surface syrup layer and the rest is included in the Crystal
It is easy in Affination to OVERWASH and dissolve
crystal rather than just remove surface syrup
Only two Variables that can be controlled by the Affination Process:
Magma Temperature
Wash Water Addition

How do they Work?

Affination

Magma Too Hot Too Much Crystal will be dissolved

Magma Too Cold Impurity not removed from Surface of Crystal
Magma Temperature Just Right All Surface Impurity Removed and
No Crystal Dissolved
Around 44C is correct Magma Temperature
Magma Temperature needs to be measured not Green Syrup
Temperature

How do they Work?

Affination

Syrup is a closed circuit with just an overflow to Recovery

The only way Impurity or Crystal can be dissolved is by the
addition of Water at the Centrifuge
Typically aim for 72 brix and 84-88 purity to give 7% of Raw
Sugar going into Green Syrup

How do they Work?

Carbonatation

How do they Work?

Carbonatation
CAPTURE of impurities so that they can be
filtered out of the syrup
REMOVAL of impurities by filtration

Note: In carbonatation the CaCO3 that is

formed is the filter aid
A SIMPLE SERIES OF REACTIONS:

CaO + H2O
Ca(OH)2 + CO2
Ca 2+ + imps
Ca(OH)2 + CO2 + Imps

Ca(OH)2
CaCO3
Ca(imps) 2+
CaCO3(Imps)

How do they Work?

Carbonatation

Liquor is a
concentrated solution

There is barely enough

water to dissolve the
sucrose so not much
is left over to dissolve

anything else

Some impurities are

already out of solution

(turbidity) or close to
precipitation

Adding lime into the syrup does three things:

o Raises the pH
o Changes the ionic strength of the solution
o Changes the ionic environment of the impurities
The local environment of any dissolved species is significantly disturbed.
Many species are no longer soluble (or as soluble as they were)
Bubbling CO2 into the mixture causes precipitation of CaCO3 to occur
These crystallites provide nucleation sites for the co-precipitation of some of the
impurities
Many of the high Mw species are acids at the higher pHs seen in carb they form
anions which can then complex with Ca 2+

How do they Work?

Carbonatation
Filterability vs % Lime
4.50E-07
4.00E-07
3.50E-07
3.00E-07
2.50E-07
2.00E-07
1.50E-07
1.00E-07
5.00E-08
0.00E+00

Final colour

Quality
Amount added
Method of addition

Lime

Final colour vs % LIme

950
900
850
800
750
700
650
600

0.4
0.4

0.5

0.6

0.7

0.8

0.9

1.1

0.5

1.2

0.7

0.8

Colour (RL)

F (Powd Lime)

CO2
Gassing rate
Bubble size
Kinetics of absorption

Large bubbles

Small bubbles

Slower kinetics
Poor mixing
Less crystallites but larger

0.9

% Lime

Amount of lime (% CaO on brix)

F (Rock Lime)

0.6

Faster kinetics
Propensity to form Foam
Lots of crystallites

Colour (PL)

1.1

1.2

How do they Work?

Carbonatation
Mixing
Rate determining step is the transfer of
Ca(OH)2 to the surface of the gas bubbles

Phase boundary
layer

Transfer of CO2 through the phase boundary

layer can become rate limiting
CO2 concentration and pressure of the gas can
influence the CO2 absorption efficiency

CO2
GAS

pH
We are titrating a basic solution with an acidic
gas.
Our reactor is continuous so every stage of
the titration is represented within the vessel

Ca 2+
LIMED SYRUP

How do they Work?

Carbonatation

How do they Work?

Phosphatation

How do they Work?

Phosphatation

3Ca(OH)2 + 2 H3 PO4 = Ca3(PO)4 + H20

There are two steps in the process: Floc Formation and Floc Separation.
Mechanism;

Precipitate formation: Phosphoric acid and Lime reacts to produce a

large amount of calcium phosphate crystals.
Those crystals adsorb in their surface the colloids in suspension
producing a primary floc.
A cationic decolorant (high molecular cationic polymer) can be used to
capture negative charged colorants
Flocculant (high molecular anionic polymer) is added to coagulate
primary flocs into bigger secondary flocs.

How do they Work?

Phosphatation
Liquor
Heating
Chemical
Addition

Ph
FC

Flocculant

FC

Lime
Acid

Decol.
Air

FC

Reaction
Primary
Floc
Formation
Aeration
FC

Flocculant
Addition
TC

Secondary
Floc
Formation

Steam

Raw Liquor

Scums

Clarified
Liquor

How do they Work?

Phosphatation
The more air in the system the better the
performance of the clarifier.
Cavitation:
A disc at the end of a hollow shaft rotates in the liquor
producing microscopic air bubbles.

Dissolved air: (Scum Desweetening)

Compressed air is fed into the eye of the aeration
pump impeller. The air blends with the liquor and
dissolves under the pressure. It requires an aeration
chamber or a pressurized tank that provides time for
the air to dissolve. The pressure should be 70 to 100
psig. When the pressure is released the air comes out
of solution in the form of microscopic bubbles.

How do they Work?

Phosphatation

The thickness and consistency of the scums bed is

controlled by:
The weir box setting that regulates the level of
liquor.
The speed of the scums rake that controls the
scums removal.
Self Draining

How do they Work?

Phosphatation

Temperature : 85oC (176oF).

Lower temperatures increases the viscosity of the liquor.
Higher temperatures favours inversion and color formation.
Liquor Concentration: 63 to 65 brix.
Acid dose: 150 to 500 ppm P2O5
Ph on reaction tank: 7.0 to 7.5 Controlled by the addition of lime
Cationic Decolorant: 100 to 300 ppm active ingredient.

Flocculant: Max 10 ppm

How do they Work?

Phosphatation

How do they Work?

Activated Carbon

How do they Work?

Activated Carbon

Macroscopic
Crack / Crevice
Graphitic Crystallite

Graphite
plate

10 millimetres

Coal Particulates

1 millimetre
1000 angstroms

Macroscopic Crack

How do they Work?

Activated Carbon

pH
Non-dissociated form is more strongly adsorbed.
Dissociated form behaves as competitor for adsorption space.

Temperature
As temperature increases, capacity decreases
This may reduce capacity for the most volatile compounds 10-20%.

Particle Volume
Pore size distribution has a dramatic influence on adsorptive performance. Removal of trace
levels of contaminants requires an extensive micropore volume.

Bed Depth
Increasing bed depth means the Mass Transfer Zone is a smaller percentage of the bed.

Flow Rate
Increasing the flow rate does reduce the efficiency.

How do they Work?

Activated Carbon

PAC

GAC

Rely on external surface area

Rely on internal surface area

Cannot normally be reactivated

Can be thermally or chemically re-activated

Requires a precoat filter to be removed

Requires on site regeneration

Varying Quality of feed is accommodated

Varying Quality of feed is NOT accommodated

Low Capex, high opex option

Requires large inventory of GAC

Typical dose 0.05 to 0.5% on Sugar Solids

Typical burn rate 0.5 to 0.8% on Sugar Solids

Contact time 20-30 mins

Contact time 2-5 hrs

Solid effluent

Liquid and Gaseous effluents

How do they Work?

Activated Carbon

USCE - Egypt

How do they Work?

Ion Exchange Resins

How do they Work?

Ion Exchange Resins

Colour

Colour

Cl-

Colour

SUGAR
SYRUP

Cl-

Resin

Resin

+
Cl-

Colour

Colour

SUGAR
SYRUP

Colour

Ion exchange: The colorants exhibit mostly an anionic behavior at

alkaline pH and thereby they can be exchanged against the mobile
chloride ions. However this mechanism is not the only one in color
removal.
Colorant molecular weight
Charge density
Type of charge
Degree of hydrophobicity
pH
Ionic strength of the medium.

How do they Work?

Ion Exchange Resins
Steric effect
Porosity of the decolorizing media is a key parameter.
This illustrates why the decolorization of sugar juices is
carried on at relatively low flow rate.
Hydrophobic effect
Polymeric adsorbents have a polarity. The colorants are
basically hydrophobic (not highly soluble in water) and will
tend to be adsorbed on the hydrophobic part of the
adsorption media.
Van der Waals forces effect
These are attractive forces between chemical groups in
contact. They result from a temporary dipole formation.

Hydrogen bonds
It is an electrostatic attraction that occurs between
molecules in which hydrogen is in a covalent bond with a
highly electronegative element.

How do they Work?

Ion Exchange Resins
Anionic Resins used in sugar have usually a quaternary ammonium functional
group and are in Chloride form.
Styrenic
Has aromatic groups in the structure
Selective for colour but low regeneration
efficiency

Acrylic
Is mostly aliphatic
Less selective but easier
regeneration

Acrylic Macroporous

Styrenic Macroporous

Typical Decolorization

50-60%

65-75%

Regeneration Efficiency

Excellent

Good

10% NaCl

10% NaCl + 0.5% NaOH

Aliphatic

Aromatic

Max Feed Colour IU

2500

800

Colour Loading BVIUs

35000

25000

High

Medium

Regenerant
Matrix

Cost

How do they Work?

Ion Exchange Resins
LARGE EFFLUENT VOLUME
Volume
BV

Flow
(BV/hr)

Temperature
(C)

Material In

Material Out

Sweet off 1

2-4

60-80

Hot Water

Liquor Feed Tank

Sweet off 2

2-4

60-80

Hot Water

Sweetwater Tank

Backwash Lower Bed

1.25

2-4

60-80

Recovered Water

Effluent

Backwash Top Bed

1.25

2-4

60-80

Recovered Water

Effluent

Caustic Regen 1

0.64

1-2

60-80

Reclaimed/Fresh Brine

Reclaim Water Tank

Caustic Regen 2

0.58

1-2

60-80

Reclaimed/Fresh Brine

Effluent

Caustic Regen 3

0.43

1-2

60-80

Reclaimed/Fresh Brine

Effluent

Rinse 1

60-80

Reclaim Water

Effluent

Rinse 2

1.5

60-80

Fresh Water

Effluent

Rinse 3

1.5

60-80

Fresh Water

Reclaim Water Tank

Sweet On 1

0.6

2-4

70-80

Feed Liquor

Reclaim Water Tank

Sweet On 2

2-4

70-80

Feed Liquor

Sweetwater Tank

2-4

70-80

Step

Service

How do they Work?

Ion Exchange Resins

OP TIM UM REM OVAL P ROFILE

14

12

DS
NaCl
Other (COLOUR)

10

0
30
-2

40

50

60

70

80

90

100

110

120

How do they Work?

Brine Recovery
What does Nanofiltration do?
It removes colour from the regeneration effluent (brine) in order to
reuse it.
Why is that important?
To save money: reduce Salt, Caustic and water consumption.
Reduces Chloride to effluent
Key NF figures:
Typical: 75 % decolourisation, 85 % recovery

Concentrate

Feed
Membrane

Permeate

How do they Work?

Brine Recovery

How do they Work?

Brine Recovery
Regeneration Effluent

Colour
-Charged

Na+

Nanofilter

Na+ ClColour
-Charged

Na+

Na+ Cl-

Na+ Cl-

Na+ Cl-

Na+ ClNa+ Cl-

Na+ ClNa+ Cl-

Na+ Cl-

Na+ Cl-

Colour

Na+ -Charged

Feed & Concentrate

mixture
High pressure side

Reclaimed Brine

Nanofilter
Trans Membrane Pressure
(TMP)

Permeate
Low pressure side

How do they Work?

Brine Recovery

How do they Work?

Brine Recovery

How do they Work?

Primary Decolourisation Comparisons
Phosphatation operates at higher Brix (65) compared to Carbonatation, so
less steam used, and less combustible fuel
Carbonatation requires double filtration, phosphatation does not
Phosphatation uses less power than carbonatation
Phosphatation is more flexible than carbonatation, especially on flow
capacities
Carbonatation has a more capital intensive cost
Docolourisations similar percentage
Operational costs similar

How do they Work?

Secondary Decolourisation Comparisons

Some Key Points

Carbon decolourisers are superior in removing impurities & flavenoids

GAC & Bone Char have air emissions
IER has waste water emissions
GAC has traditionally had the lowest operating cost
GAC & PAC do not have de-ashing capabilities
IER and Bone Char do have de-ashing capabilities
Bone char uses 90% more energy than GAC for the same decolourisation
IER has the option of membrane treatment to recover 90% of the salt and
drastically reduce waste emissions

Conclusions
Summary of Decolourisation Process Options

Phosphatation + IER Low Capex & Low Opex

Phosphatation + GAC Low/High Capex & Low Opex
Phosphatation + PAC Low Capex & High Opex
Carbonatation + IER Mid Capex & Low Opex
Carbonatation + GAC High Capex & Low Opex
Carbonatation + PAC High Capex & High Opex

References

Brad Ahlgren, Calgon Carbon Corp. - Carbon 101.ppt

T&L HydraCoRe 70pHT Presentation, Thames Jan 2006.ppt
Robert Albright, Albright Consulting - Architecture and App.ppt
Cane Sugar Refining
with Ion Exchange Resins - Purolite
Colour

Norit - Introduction to the purification of

liquid
sugar with Norit Activated Carbon

1) The chemistry of colour removal: a processing perspective SB Davis Proc

S Afr Sug Technol Ass (2001) 75
2) Separation and identification of sugar colourant (TM Letcher and PG
Whitehead ) Proc S Afr Sug Technol Ass (1996) 70
Comparison of methods
1) A Comparative evaluation of Carbonatation and Phosphatation (AS
Vawda) SIT 940
2) Pros and Cons of various decolorisation processes for production of
refined sugar SIT Savannah May 2010
3) Removal of colour in sugar cane juice clarification by defecation, sulfiation
and carbonation
4) Analysis of Refinery Clarification Processses (TLPT) July 2004

THE PEOPLE
BEHIND SUGAR

Thank You!
To ensure the most efficient and effective
refinery, with maximum output and minimized
energy use and environmental impact, or just to
get the best out of your upgrade and refit, talk
to the people behind sugar.

THE PEOPLE BEHIND SUGAR