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
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. 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.

1.1. Ionic form of the resin

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
Cation exchange resin in the calcium form Cation exchange resin in the sodium form Cation exchange resin in the potassium and/or sodium form

Kind of separation
Fructose/dextrose Mannose/dextrose Sorbitol/mannitol Glucose/galactose

Dextrose/higher saccharides Maltose/higher saccharides 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. 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

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.

AVH Association 7th Symposium Reims, March 2000

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. CONTINUOUS CHROMATOGRAPHIC SEPARATION SYSTEMS 2.1. Typical requirements of industrial scale chromatographic separation using ion exchange resins as separation medium
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.

1.2.Main characteristics of resin influencing the quality of the separation

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. The higher the exchange capacity, the more the retention of compounds able to complex with calcium is increased.
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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.

Association AVH 7e Symposium Reims, mars 2000

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. 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.
Table 2: Continuous SMB principles.
Zone definition
water A B Z1 Z2 B A Z3 B A +B A Z4 A or = B

Table 3: Rules for adapting hydraulical conditions in the different zones. BV per zone Product A B BV1 > BVA > BVB BV2 < BVA > BVB BV3 < BVA > BVB BV4 < BVA < BVB

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. 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. 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 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
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A extract Zone 1 Zone 2

B raffinate Zone 3 Zone 4

A B

desorption desorption elution

adsorption desorption

adsorption desorption

adsorption adsorption safety zone

separation

A is the slow compound B is the fast compound

NB: as example for the glucose/fructose separation A = fructose 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. The following rules (table 3) will govern the technical design of such a system.

AVH Association 7th Symposium Reims, March 2000

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. 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.

Table 4: SMB typical performance from glucose fructose separation. Productivity: 1 500 g Dry Substance/l resin.day. Feed Composition % DS Recoveries % of inlet % DS fraction Fructose Glucose Dpn Fructose Glucose Dpn 60 42 53 5 Extract 92.2 6.6 1.2 93.1 5.2 10.2 26.9 Raffinate 5.0 87.2 7.8 6.9 94.8 89.8 27.2

Table 5: Dextrose enrichment from high dextrose content syrups. Productivity: 1 400 g Dry Substance/l resin. day. Feed Composition % DS Dextrose DP2 DP3 Dpn Total Recoveries % of inlet Dextrose DP2 DP3 Dpn % DS fraction 93.0 4.2 0.7 2.1 100.0 Extract 99.3 0.4 0.0 0.3 100.0 90.0 8.0 2.0 10.0 42.2 Raffinate 59.1 24.6 4.3 12.0 100.0 10.0 92.0 98.0 90.0 4.3

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). 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. 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. 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.
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2.3. Typical separation performances

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).

3. INDUSTRIAL PLANTS
This technology is largely used industrially for the pharmaceutical and biotechnological industries, where plant sizes are quite small ( 100 L

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.

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. 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.

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.

3.3. 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.

3.2. Column engineering

The design of the separation column is clearly very important in such a process.
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4. APPLICATION OF THE CONCEPT OF CONTINUOUS ION EXCHANGE PROCESS

Ion exchange is largely used industrially. The ion exclusion process can be a preliminary refining

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

CONCLUSION
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.

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