Reasons for the Destruction of Sugar

During the Processing of Sugarcane

Gillian Eggleston

Southern Regional Research Center-USDA-ARS

New Orleans, Louisiana
U.S.A.
 Presentation Outline

1. Why sugar losses are such a problem

2. Review the mechanisms of sugar

destruction and color formation in the
factory

3. Examples of industrial losses of sugars

and some solutions to reduce them
Why Sugar Losses are Such
A Problem
Why Sugar Losses are Such a Problem

• Loss of sucrose yields in raw sugar

• Loss of alcohol yields
• LOSS OF PROFITS ($$$$ OR REALES)
• Color formation
• More unwanted molasses formed
Mechanisms of Sugar Destruction
and Color Formation in the
Factory
Factory Flow Chart to Evaporation (Brazil)
pH=3.8-4.5
65 oC Rt= 1 min Juice
Sulphitation
100%
62-65 oC
Pre-Heater
Filtrate
pH=5.2-5.5 ~65.5 oC
MJ
~35-42 oC Liming
Tank
~65.0 oC 2-8 min
Heater
Flash Tank 105-112oC pH=6.7-7.3
101 oC pH=6.4-7.0
Clarifier Evaporator
Station Syrup
Rt=1 min Rt=90-120 min 96 oC
Rt=30 min pH=5.7-6.3
“Acid” (up to pH 8.3) Thermal Degradation or Inversion of
Sucrose in Aqueous Solution
C H2OH
O Sucrose
OH
OH
OH O
HOCH 2 protonation of glycosidic oxygen
O
HO
CH2OH
Non-Specific OH

Degradation 2,6-anhydrofructose*
ent
gem
rr an
CH2OH
rea
HOCH2 OH
O HO CH2 O
HO
+ H2O O
HO
OH
OH
OH + CH2OH CH2OH
OH OH OH

Glucose* Fructose Carbocation (Fru+) Fructose*

Fru+ Sucrose-OH
OH

HOCH2 CH2OH HO CH2 O O-SUC

O
O OH
HO
HO O
CH2OH
O
OH
OH
Difructosedianhydrides* 1-Kestose* (GF2)
 “Acid” Thermal Degradation of Sucrose

H2O
SUCROSE GLUCOSE + FRUCTOSE
Up to pH 8.3

Factory Conditions That Affect the Acid Degradation of Sucrose:

Occurs more in dilute solutions, e.g. juices,

where more water is available (low Brix)
The more acidic the conditions the greater the
rate of degradation
The higher the temperature the greater the rate
The higher the retention time the more
degradation occurs
 Percentage of Sucrose Acid Degraded in One Hour

pH
Temp Brix
5.0 5.5 6.0 6.5 7.0
60oC 10 0.050 0.016 0.005 0.0016 0.0005

60 0.025 0.008 0.003 0.0008 0.0003

70 0.019 0.006 0.002 0.0006 0.0002

80 0.012 0.004 0.001 0.0004 0.0001

90oC 10 1.26 0.40 0.13 0.040 0.013

60 0.069 0.22 0.069 0.022 0.007

70 0.51 0.16 0.051 0.016 0.005

80 0.32 0.10 0.032 0.010 0.003

Parker, Cane Sugar Handbook

 “Acid” Degradation of Sucrose

Effect of Salts in Industrial Solutions

Salts are known to catalyze (speed up) the degradation of sucrose

Mechanism For example, M = Ca, Mg or Al and Z = charge

M(H2O)nZ+ M(H2O)(n-1)(OH) (Z-1)+ + H+

Interaction of water molecule with a cation (M) of Z+ charge

Then
These extra H+ ions (protons) increase the protonation of the glycosidic linkage of
the sucrose molecule and therefore degradation into glucose and fructose
C H2OH
O
CH2OH
OH OH
O HOCH2
OH O

CH 2
OH O
OH
OH
OH
+ HO
CH2OH
O
HO OH OH
CH2OH
H+
OH
Sucrose Glucose Fructose
Effect of Various Salts on the Sucrose Acid Degradation
at 100 oC and 65 Brix Sucrose

1.5
1.4
[alpha]589nm

1.3 Magnesium chloride

MgCl2
1.2 Sodium Chloride NaCl
1.1 Calcium chloride CaCl2
Magnesium acetate
1 Mg(OAc)2
0.9
0.8
0 1 2 3 4 5
Reaction time (hours)

Eggleston et al, (1996). J. Carbohydr. Chem.

 “Acid” Degradation of Sucrose

Effect of Invert Sugars

Invert sugars can catalyze the acid degradtion of sucrose

Mechanism
Acid conditions
Glucose + Fructose Acids + color
(H+) compounds

Then

C H2OH
O
CH2OH
OH HOCH2 OH
OH O O

CH 2
OH O
OH
OH
OH
+ HO
CH2OH
O
HO OH OH
CH2OH
H+
OH
Sucrose Glucose Fructose
 Effect of Adding Invert Sugar (Fructose) on
Sucrose Acid Degradation
15 Brix Sucrose, pH 6.0, 80 oC

0.8
% sucrose loss

0.6
0% Fructose
0.4 1.5% Fructose

0.2 3% Fructose

0.0
0 2 4 6

Reaction time (hours)

Andrews et al, 2000. SPRI Proc.

“Acid” Thermal Degradation or Inversion of Sucrose

CHEMISTRY REVIEW
In dilute solution (juices) the acid degradation of
sucrose (inversion) produces a simple mixture of
glucose and fructose
In concentrated solution (syrups) the product
profile is far more complex and many of the
products are optically active
Salts and invert sugars (glucose and fructose)
can increase the acid degradation of sucrose

BRIX WATER:SUCROSE RATIO

10 171:1
60 12:1
 Degradation of
Glucose and Fructose
and
Formation of Color
 Degradation of Glucose and Fructose and
Formation of Color

Alkaline
Acid Conditions
Conditions
Mild Severe
pH 5-6; up to 60oC pH 3-4; 60-100oC >pH 7
Enolization,
mostly isomerization,
ionize and
enolization,
mutorotate Condensation and
isomerization,
polymerization

slow slow very fast

low color low color very high color

Some Reported Products of Fructose Acid Degradation in Water at
Elevated Temperatures (~100oC)
Isomerization Dehydration Fragmentation Condensation
Products Products Products Products
glucose 5-hydroxymethyl-2- formic acid “humin” or high
furaldehyde (HMF) molecular weight
colored compounds
5-methyl-2-furaldehyde levulinic acid
α-angelica lactone dihydoxyacetone
2-(2-hydroxyacetyl)furan glyceraldehyde*

Isomaltol 2-furaldehyde
4-hydroxy-2,3,5- pyruvaldehyde
hexanetrione
4-hydroxy2(OHmethyl) lactic acid*
-5-methyl-3(2H)-furanone
acetic acid
2-(2-hydroxy Acetol
acetyl)furan formate
2,3-btanedione
Note: Compounds in yellow are major products (generally >1% absolute yield)
 Degradation of Glucose and Fructose
and Formation of Color
Alkaline
Acid Conditions
Conditions
Mild Severe
pH 5-6; up to 60oC pH 3-4; 60-100oC >pH 7
Enolization,
mostly
ionize and isomerization,
enolization,
mutorotate condensation,
isomerization,
polymerization

slow slow very fast

very high color +

low color + acids low color + acids
acids
 Alkaline Degradation of Glucose and Fructose
Isomerization
Lobry de Bruyn-Alberda van Ekenstein Rearrangement
Mannose Enediol
O OH
HO OH
HO HO
OH OH
via an enediol intermediate OH
OH
OH OH

O OH
OH O
HO HO
OH OH
OH OH
OH OH
Glucose Fructose
 Alkaline Degradation of Glucose and Fructose

Glucose and Fructose

Enediol Anion

C3 Acids Carboxylic Acids

Color Compounds
Effect of Constant Reactiion pH on Color Formation after 8 Hours
of Sucrose Degradation (65Brix; 100oC)

5000
Autotitrator used
ICU color at 420nm

4000
Alkaline degradation
of invert sugars
3000
Acid degradation
2000 of sucrose and invert sugars

1000

0
3 4 5 6 7 8 9 10 11

pH

Eggleston and Vercellotti, 2000. J. Carbohdyr. Chem

Degradation of Glucose and Fructose and Formation of Color
Glucose and fructose also can form color by reacting
with amino-acids: Maillard Browning Reactions

Invert Sugar + Amino-acid

Early Maillard Reaction

Amadori Rearrangement

Advanced Maillard Reaction

Fission Dehydration Strecker Degradation

Melanoidin Color Polymers (brown pigments)

Can occur at all pHs in a sugarcane factory, but occurs particularly under alkaline
conditions
Occurs mostly in boiling
Examples of Industrial Losses of
Sugars
 Measurement of Minimum Sucrose Losses at the Factory
((%Glu) out - (%Glu)in )
Brix Brix
% Sucrose loss = X MWSuc X 100
(%Suc)in X MWGlu
Shaffler et al, 1986
Brix

((%Glu) out - (%Glu)in )

Chloride Chloride
% Sucrose loss = X MWSuc X 100
(%Suc)in X MWGlu
Chloride

Gas Chromatography
or Ion chromatgraphy

Note on Measurement of Sucrose Losses at the Factory or Refinery

Flow rates are changing all the time so large amounts of samples are
required, and only trends are given.
 Across Robert-Type Evaporators
at a
Louisiana, U.S.A. Raw Sugar Factory
 Cora Texas Factory, Louisiana
Configuration of Robert’s-type Evaporators
Pre 1
111oC 2 11 21 31 T1

121oC 104oC 93oC 69oC

CJ Pre 2 12 22 32 T2
111oC 104oC 93oC
1 111oC 4 5 6
3 13 23 33 T3
121oC

Vacuum
Note: T2 triple evaporators only studied
Target temperatures shown
pans
Effect of Target FES pH on Calculated % Sucrose Losses
Only conservative (minimum) estimates

Target pH % Sucrose Losses

FES CJ Early Mid Late Season
Av.
5.6 ~6.1-6.3 0.810 0.307 0.855 0.657
5.9 ~6.7 0.690 0.276 0.669 0.545
6.3 ~7.1 0.531 0.235 0.590 0.452
6.7 ~7.4 0.370 0.075 0.370 0.272
High sucrose losses in early Increases in late season
season are attributable to are because of resistant
the lowest cane quality, scale build-up in later
and high invert which can evaporators and
catalyze sucrose degradation lowered cane quality

Higher target pHs needed in early season. This will have to be a

compromise as increased lime addition will counteractively increase
some scaling)
The Best Way to Reduce Sucrose Losses is to Have:

1. Optimum Target pHs

2. Strong pH Control
Sucrose Losses Across Clarification
Systems Under Extreme Conditions
 Florida, U.S.A. Factory
Factory Flow Rate: ~ 26,000 short tons cane/day

Juice Clarifier

• hot lime clarification

• Dorr 444clarifier temperature ~104 oC
• composite factory samples (six) taken every 10min in and out
of the clarifier, taking 3h retention time (estimation) into account

Syrup Clarifier
• syrup phosphatation clarification
• clarifier temperature 82-85 oC
• composite factory samples (six) taken every 10min in and out
of the syrup clarifier, taking a 1h retention time (estimation)
into account
Average Chemical Parameter Measurements Across Juice and Syrup Clarifiers

Chemical Average ∆
Parameter In Out In to Out
Juice Clarifier Av. Turbidity (ICU)
pH (room 9.38 8.46 - 0.92 In out
temp) 23978 5072
Brix (%) 12.93 12.87 - 0.05
78.8% turbidity
Sucrose (%) 11.91 11.99 + 0.08 removal
Glucose (%) 0.123 0.129 + 0.006
Fructose (%) 0.138 0.135 - 0.003
Chloride (%) 0.074 0.076 + 0.002
Av. Turbidity (ICU)
Syrup Clarifier
In out
pH (room 7.31 6.84 - 0.47 4181 1144
temp)
Brix (%) 66.95 64.37 - 2.58 72.6% turbidity
removal
Sucrose (%) 12.72 13.08 + 0.36
Glucose (%) 0.169 0.216 + 0.047
Fructose (%) 0.172 0.212 + 0.040
Chloride (%) 0.352 0.341 - 0.011
 % Sucrose Losses
Across Juice Clarifier
Composite Juice # Gluc%Sucrose on Gluc%Sucrose on
Brix Basis Chloride Basis
1 0.0 0.0
2 0.0 0.0
3 0.0 0.0
4 0.0061 0.0
5 0.47 0.417
6 0.58 0.345

Across Syrup Clarifier

Composite Syrup # Gluc%Sucrose on Brix Gluc%Sucrose on
Basis Chloride Basis
1 0.54 0.70
2 0.64 0.85
3 0.54 0.64
4 1.01 1.26
5 0.53 0.77
6 0.50 0.57
 Color Changes Across Juice Clarifier

18
Color at 420nm (ICU) 16
Too high pH conditions (over
Thousands 14
Color in liming) cause alkaline
12 degradation of invert sugars
Color out
10 and color formation
8
6
1 2 3 4 5 6
Juice Number

Color Changes Across Syrup Clarifier

18
Color at 420nm (ICU)

16
14 Low pH conditions
Thousands

Color in mimimize color formation

12
Color out but increase sucrose loss
10
8
6
1 2 3 4 5 6
Syrup Number
Thank You For Listening!