Association AVH 7e Symposium Reims, mars 2000

Technology of
chromatographic separation
in glucose syrup processes
Dominique PAILLAT, Michel COTILLON and Marc-Andr THOLEYRE
Applexion S.A., 78681 Epne, France

INTRODUCTION

1.1. Ionic form of the resin

Chromatographic separation is a widely used

unit operation in sugar or sugar derivatives production. Over the last two decades there has
been remarkable progress toward the understanding of the phenomenon of chromatographic
separation, which has expanded the applications
field of this technology and induced major
improvements in process control and column
design.

Classically, separation of sugars is done with

resins in the calcium form, while the separation
sugar/non-sugar is achieved with resin in the
potassium form. The table 1 shows typical commercial separation media for sugar solutions:

Table 1: Separation support type according to the kind of

separation.
Separation
support

First, this presentation summarises the essential

criteria to optimise in the design of a chromatographic separator, then describes performances
of latest innovation related to continuous systems applied to glucose industry (polyols, glucose syrups).
The concept of continuous chromatographic
separation can easily be adapted and transferred
to continuous ion exchange systems providing
possible economic interests.

Kind of
separation

Cation exchange
resin in the
calcium form

Fructose/dextrose
Mannose/dextrose

Sorbitol/mannitol
Glucose/galactose

Cation exchange
resin in the
sodium form

Dextrose/higher saccharides
Maltose/higher saccharides

Cation exchange
resin in the
potassium and/or
sodium form

Sucrose/fructose and dextrose

Sucrose from molasses

Resins in the calcium form produce simultaneously two kinds of separation:

first it acts as a molecular sieve: large size
molecules not being able to enter the resin
beads are more or less excluded due to their
size.

1. RESIN AS SEPARATION
SUPPORT
The typical separation media used for large scale
chromatographic systems in aqueous form
applied on saccharides are sulfonated cross linked styrenic divynilbenzene cation exchange
resins in salt form, but can also be anionic resins
in salt form.

second action is a separation related to stability

difference of sugar-calcium complex: only polyols and certain sugars (fructose, galactose) are
capable of forming such complex. The other
components (sucrose, glucose) do not form com62

AVH Association 7th Symposium Reims, March 2000

2. CONTINUOUS
CHROMATOGRAPHIC
SEPARATION SYSTEMS

plex with the resin, thus explaining the separation.

Resins in the potassium form act with the principle of ion exclusion, based on electromagnetic
phenomenon and as a molecular sieve.

2.1. Typical requirements of

industrial scale chromatographic
separation using ion exchange
resins as separation medium

1.2.Main characteristics of resin

influencing the quality of the
separation

Sugar solutions are feeding the separator at

constant and high dry substance level between
50 and 70% DS, at high temperature between
60 and 80 C and free of any suspended solids.
Best compromise shall be found to optimize operating pressure of the whole system.
For the separation of sugars, demineralized feedstocks are used to avoid any replacement of the
counter ion in the resin by cation in the feedstock, which would lower the separation performance.
Furthermore, oxidizing substances in the feedstock must be eliminated, as they affect the stability of ion exchange resin.
Usually both feedstocks and eluent (water) are
degassed prior to entering the separator to avoid
resin oxydation (which affects the resin life
time), and to avoid degassing inside the resin
vessels, which would create channelling.
The kind and quality of dissolved ions in the
eluent must be perfectly controlled.
The same requirements as for the feedstock need
to be respected.
Usually, eluent is demineralized water or
condensate, coming from the concentration of
fractions out of the separator.
Assuming that quality requirement of both feed
and eluent are respected, resin regeneration is
not necessary.
Nevertheless, normal operating conditions of the
separation creates resin fines, which may affect
pressure drop and fluid distribution (channelling). Then external backwash of resin bed to
remove such resin fines is becoming necessary.

Major physical properties of the separation

media are particule size, particle and pore size
distribution, and ability to withstand osmotic
shocks.
1.2.1. Generally, a spherical shape and a smaller
and uniform particle size distribution give better
separation performance.
Particle size and distribution are of main interest
for the kinetics of the separation. The smaller the
beads, the bigger the exchange surface per volume unit, the better the separation performance.
Size distribution and bead size determine the
hydraulic pressure drops of the system.
The smaller the beads, the higher the pressure
drop, and the higher the operating cost.
Therefore, an economically optimum particle
size exists in each case.
Almost all applications use ion exchange resins
with a particle diameter between 0.2 and
0.4 mm.
1.2.2. Resins typically suffer from high mechanical stress resulting from high hydraulic pressure
drops and repeated swelling and shrinkage
cycles. Therefore, the ability to withstand osmotic shocks must be high. The mechanical property is related to cross linkage, or divynilbenzene
(DVB) rate (typically between 4 and 8%):
lower DVB rate exhibits a greater tendency to
swell and shrink
higher DVB rate provides greater physical durability, gives smaller microscope size, higher total
exchange capacity and lower humidity rate.

2.2. Description of various FAST

systems: SMB, multistage SMB,
SSMB, New Sequential
Under the generic term FAST (Finnsugar
Applexion Separation Technology), we regroup
the various chromatographic processes developed by Applexion and Finnsugar, now commercialized through Applexion.

The higher the exchange capacity, the more the

retention of compounds able to complex with
calcium is increased.
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Association AVH 7e Symposium Reims, mars 2000

Table 3: Rules for adapting hydraulical conditions in the different zones.

The FAST chromatographic systems for

sugars/sweeteners production are suitable for
recovering two or more products. The choice of
one of these technologies is technically driven.

BV per zone

2.2.1. SMB (Simulated Moving Bed)

This system originated in the 1960s with
Broughton et al. who developed it for the oil
industry as an improvement of batch systems. It
is a continuous chromatographic separation system where the sequential rotation of the resin
zones simulates the movement of the resin,
counter-current of the fluid circulation loop.
In the mid 80s, this technology was applied in
cane and beet molasses separation.
Almost all HFCS producers are familiar with
such a process for fructose enrichment application, which is used to get a final 55% fructose
syrup after remix.
SMB, defined as a system with a continuous
supply of feed material, is typically devoted to
dichotomous separation and optimal for binary
mixed solutions.
For memory, the separation is composed of four
zones defined in table 2.

A
+B
A

Z1

Z2

A
Z3

A
extract
Zone 1

A
Z4

or =
B

Zone 3

Zone 4

desorption

adsorption

adsorption

adsorption

desorption

desorption

desorption

adsorption

elution
A is the slow compound
B is the fast compound

separation

safety zone

NB: as example for the

glucose/fructose separation
A = fructose

BV3

BV4

< BVA

< BVA

< BVA

> BVB

> BVB

> BVB

< BVB

2.2.3. SSMB (Sequential Simulated Moving Bed)

SSMB is, as its name suggests, a derivative development from the SMB conventional system.
That means, the same design principle governs
both technologies:
8 (or more) identical cells
loop circulation
injection/extraction possible at the inlet/outlet
of each separation cell
Particularity of such development consists in:
discontinuous feed and extraction of fractions
subdivision of each SMB step in 3 or 4 substeps

B
raffinate
Zone 2

BV2

> BVA

2.2.2. Multistage SMB process (patented)

This recent development includes a two-stage
process. It is a combination of two Separations of
any type, one after the other to improve recovery and purity of overlapping components, like
sucrose and betaine in beet molasses desugarization.
In order to limit the scale of the 2nd system, an
intermediate evaporator is needed.

Zone definition

A B

BV1

the separation productivity will be a function

of specific BV difference between components
to be separated. The greater the difference, the
higher the load of the system can be.
the eluent amount increases when the load of
the system increases. The greater the difference in specific BV, the higher the required
eluent amount.
the dry substance level of the feedstock will be
as high as possible to limit the dispersion
during injection (optimum at 60 Brix for glucose/fructose separation).
the number of separation cells influences the
separation performances.
Theoretically, the more the vessels, the better
the purity of fractions.
Optimum seems to be 8 to 12 separation vessels.

Table 2: Continuous SMB principles.

water

Product

B = glucose

Each zone is defined by a bed volume (BV),

result of flow in the zone and sequence time.
This BV is adjusted according to specific elution
BV of compounds to be separated.

Therefore, linear velocity in the system can be

optimized in each zone, fractions are extracted
under optimal conditions, thus having positive
effects on pressure drops and fraction purity.
This technology required a more sophisticated

The following rules (table 3) will govern the

technical design of such a system.
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AVH Association 7th Symposium Reims, March 2000

Table 4: SMB typical performance from glucose fructose

separation. Productivity: 1 500 g Dry Substance/l resin.day.

monitoring control system, but has to be considered when high purities of fractions need to be
achieved.
2.2.4. New Sequential multiprofile process (patented)
Under the FAST, a new milestone in the development of large scale chromatography technology (patented) was developed for multiple compounds separation (more than 2 compounds).
This system is an elution technique, discontinuous, where separation is achieved on the total
length of the separator. Feedstock is injected at a
fixed point of the separator and extract fractions
are collected at the end of the separator.
That means the separator length and feed volume need to be adjusted and adapted to the difference of affinity of compounds to be separated
with the resin.
This process has two or more profiles of dissolved material (or dry solids profiles = DS-profiles)
moving in the entire resin bed (all columns in
the circulation loop), in contrast to only one
profile in conventional SMB systems, both continuous and sequential.
This enables a much more efficient use of the
resin, resulting in higher capacity at a given product recovery, purity and resin volume. Or alternatively, higher product purity and recovery is
achieved, at the same resin capacity as with the
conventional techniques.

Feed

Extract

Raffinate

Composition

Fructose

42

92.2

5.0

% DS

Glucose

53

6.6

87.2

Dpn

1.2

7.8

Recoveries

Fructose

93.1

6.9

% of inlet

Glucose

5.2

94.8

10.2

89.8

26.9

27.2

Dpn
% DS fraction

60

Table 5: Dextrose enrichment from high dextrose content

syrups. Productivity: 1 400 g Dry Substance/l resin. day.
Feed

Extract

Raffinate

Composition

Dextrose

93.0

99.3

59.1

% DS

DP2

4.2

0.4

24.6

DP3

0.7

0.0

4.3

Dpn

2.1

0.3

12.0

Total

100.0

100.0

100.0

Recoveries

Dextrose

90.0

10.0

% of inlet

DP2

8.0

92.0

DP3

2.0

98.0

Dpn

10.0

90.0

42.2

4.3

% DS fraction

of resin). It is also used in the sugar industry for

sugar separation or purification of low purity
solutions where the bed size involved is much
larger ( 100 m3 of resin).

This process can also be described as a 2-profile process, to differentiate from the
1-profile conventional chromatographic separation processes (pulse test). Actually the New
Sequential process can have even more than
two DS-profiles; in ion exclusion processes, e.g.
molasses separation, two profiles are preferred.

Plant capacity and resin productivity for a given

application, determine the total resin bed to be
installed. In some cases, due to mechanical
construction limitation, and especially column
diameter, more than one separator is required.
This is for instance the case of molasses desugarization plants where 100 m3 of resin are required.

2.3. Typical separation

performances

For high capacity units (e.g. in the case of

molasses desugarization) an Applexion continuous ion exclusion plant includes 2 identical
lines. Each line consists of 4 identical towers
(2 columns per tower) in which the resin bed
volume per column is 40 m3.

The most classical application of chromatography in glucose industry is the glucose fructose
separation for HFCS production (table 4).
A new development appears with the production of very high glucose content products, more
than 99% (table 5).

Typically, depending on the process, the separator will include 4 to 12 identical columns.
For lay out consideration, the columns or compartments can be stacked on top of each other
(towers) in order to reduce floor space requirement.

3. INDUSTRIAL PLANTS
This technology is largely used industrially for
the pharmaceutical and biotechnological industries, where plant sizes are quite small ( 100 L
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Association AVH 7e Symposium Reims, mars 2000

For industrial units design, Applexion R & D

department conducts pilot level experiments,
that allow scale up to any size of industrial plant.

Resin packing preventing of back mixing of

separated products and minimizing of dilution of
fractions, as well as flow distribution and fraction collections, are probably the most important
design parameters.
During a normal cycle, the resin will alternately
swell and shrink according to the osmotic pressure of the different liquid phases. The larger
resin bed volume is generally under water, while
the smallest one is generally when the sugar
fraction or the salts fraction is passing
through. It should be noted that the resin bed
volume also depends on working temperature.
Overfilling of the columns creates high pressure
drops or high pressure in the system, which can
be dangerous as far as the mechanical resistance
of the vessels is concerned.
The beads will with time tend to reach a perfect
arrangement giving the smallest void volume
between them. This is why it is necessary to top
off to adjust resin bed volume and minimize void
volume on top of the resin bed.
Special equipment is then required to perfectly
control this operation without any risk of damaging the vessels.

3.1. Feed and eluent quality

requirements
First of all, the products coming into the separator must be absolutely free of any suspended
solids. If not, the resin will act as a perfect filter,
and suspended solids will accumulate on top of
the bed giving high pressure drop and poor distribution. This is why it is sometimes necessary
to install main filters but most of the time, safety filters or stop filters to protect the whole plant.
In some cases, it is also necessary to adjust the
chemical properties of the incoming products to
improve separation performances or avoid any
post precipitation in the resin itself due to pH
changes when compounds are separated.
pH also needs to be adjusted in the separator to
prevent in some cases product hydrolysis.
Above all, the separation medium shall remain
under its initial ionic form which has been selected for optimum separation.
Considering ion exclusion, most of the raw products to be treated generally contain a lot of
cations such as Ca++, Mg++, Na+, K+.
In this case, it is necessary to remove the divalent cations prior to separation to maintain the
resin in equilibrium with the monovalent
cations entering the system and the remaining
divalent cations.

3.3. Distribution and collection

networks
As said, design of distribution and collection networks is also very important when high productivity and high purities are required, and this is
especially the case when large vessels are
concerned.
The networks need to be mechanically resistant,
easy to remove for maintenance and cleaning
aspects, but do need for process reasons to be
designed to provide symmetrical distribution of
fluids on the separator media to avoid channelling, turbulence, back mixing and ensure the full
utilization of the total installed resin bed and a
plug flow distribution.
For that purpose, depending on vessel diameter,
it is sometimes necessary to divide the network
into multiple identical sections, each one devoted to distribute on the corresponding surface
area.

The decalcification process can be a chemical

precipitation or better, globally integrated in the
process in front.
We have taken this advantage in the beet sugar
industry eliminating the Ca++ with ion exchange
resin prior concentration giving some benefits in
evaporation cost, but also using ion exchange
resins to eliminate Ca++ and adjust pH for further enzymatic reaction for instance.
A good plant design will have the possibility of
transfering the resin from the vessels, using special pumps and fixed pipes, to an external tank
where both periodical backwash and special
resin conditioning or defouling can be performed in case of any accidental pollution.

3.2. Column engineering

4. APPLICATION OF THE
CONCEPT OF CONTINUOUS ION
EXCHANGE PROCESS

The design of the separation column is clearly

very important in such a process.

Ion exchange is largely used industrially. The ion

exclusion process can be a preliminary refining
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AVH Association 7th Symposium Reims, March 2000

step followed by ion exchange as a polishing

step. Such a process will allow significant savings
in chemicals as well as effluent treatment costs.
Ion exchange can be operated batchwise or
according to a continuous mode.
In principle, for the batchwise process, one
column is in production while another one is in
regeneration or waiting. In the continuous
process, one column will be in production while
many others will be in regeneration.

(resin replacement) or for special resin defouling

steps, irrespective of the repetitive standard
sequences included in the normal cycle, without
stopping the plant.
The special defouling procedure can take place
in the column itself or, just like for an SMB
plant, in an external tank designed for that purpose.

This way of working generally permits, compared to batch process:

a better utilization of the resin capacity and
therefore a smaller total installed resin bed.
a better usage of chemicals and water and therefore less effluents and water going with the
product during the sweetening on and off
phases.
continuous flows on both production and
regeneration streams.

Chromatographic separation can find multiple

fields of application in sugar refining.
Many factors influence the design and performance of such a process, which needs to be optimized individually. Clearly, the largest operation
cost resides in the concentration of the fractions,
usually achieved by evaporation, or in combination with reverse osmosis. Water removal has a
major effect on design, investment and operation costs. If it is a bottleneck for production
capacity, compromise has to be reached in order
to optimize the economics of the process.
Applexion is sharing experience and research
resources with Finnsugar to provide every sugar
producer with their best expertise. We propose
our pilot facilities for any development and optimization on an individual case by case basis.

CONCLUSION

In order to fully take advantage of the continuous ion exchange or adsorption process, it is
however absolutely necessary to fully respect
the optimum process working conditions such as
contact time with the resin, and linear velocity
through the bed and this for pressure drop, as
well as resin life considerations. The number of
columns both in production and regeneration is
decided accordingly.

REFERENCES
1. Yoritomi et Al., US Patent, Method for the
chromatographic separation of soluble components in feed solution, May 12, 1981.

Applexion is offering continuous ion exchange

plants based on the SMB concept, developed for
separation and ion exclusion. In such plants, the
columns are static and are arranged in towers.
All sequences from the batch process are included and can be performed in the same way.
Just like the SMB process, only the inlet and
outlet valves corresponding to the necessary
incoming and outgoing fluids are changed from
one step to the next.

2. Katashi Shioba, Starch hydrolysis product,

1992 pp 555 572
3. Franois Rousset, New developments in
chromatographic
separation
of
beet
molasses, British Sugar Eurotechlink 97,
June 1997.
4. Marc-Andr Theoleyre, Use of mathematical
model with a view to optimizing SMB plant,
American Chemical Society, New Orleans,
1997.

In principle, it is possible to affect the different

columns into specific zones, each according to its
process parameters.
The automation system easily allows to adjust
the number of columns in parallel or in series in
order to improve or optimize process conditions
without any mechanical modification. All flows
as well as step time are controlled according to
desired production rate.

5. Stanislas Baudouin, Applexion internal

report, January 1999.
6. Goran Hyki, Hannu Paananen, Michel
Cotillon, Gary Cornelius, Presentation of the
FAST separation technology, ASSBT, 13th
February 1999.

The fixed bed arrangement also permits the bypass of one column for maintenance purposes
67