EP0203844B1 - Process and apparatus for the preparation of crystalline anhydrous fructose - Google Patents

Process and apparatus for the preparation of crystalline anhydrous fructose Download PDF

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Publication number
EP0203844B1
EP0203844B1 EP86401006A EP86401006A EP0203844B1 EP 0203844 B1 EP0203844 B1 EP 0203844B1 EP 86401006 A EP86401006 A EP 86401006A EP 86401006 A EP86401006 A EP 86401006A EP 0203844 B1 EP0203844 B1 EP 0203844B1
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crystallization
fructose
zone
crystals
mass
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German (de)
French (fr)
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EP0203844A1 (en
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Patrick Haon
Patrick Lemay
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Roquette Freres SA
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Roquette Freres SA
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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K11/00—Fructose

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  • the subject of the invention is a method and an installation for producing anhydrous crystallized fructose.
  • the known methods provide for the dissolution of a syrup rich in fructose in an alcohol or in water and slow cooling with simultaneous seeding and the crystallization operation requires the use of several mixers of the horizontal type.
  • French Patent No. 2,128,835 describes a process for obtaining large fructose crystals in an aqueous medium and continuously.
  • this method has the disadvantage of requiring, for its continuous implementation, sophisticated and very delicate apparatus.
  • Patent No. 1,596,220 describes a continuous process for crystallizing a solution of fructose diluted in methanol, the crystallization being partially carried out in a vertical mixer. This process, in addition to the fact that it is only applicable to dilute solutions of fructose, requires an additional device for the preparation of the crystal primer.
  • Patent application FA-A 2 217 421 describes four processes for crystallizing fructose, only one of which, moreover, presents as the least advantageous, proceeds by cooling alone.
  • the invention also relates to other arrangements which are preferably used at the same time and which will be more explicitly discussed below.
  • Fructose syrups obtained, for example, from a starch hydrolyzate which is isomerized and then enriched by chromatography, having a dry matter content of approximately 75 to 95%, are used as the raw material. by weight, the fructose entering for at least 90% and, preferably, for a proportion greater than 93% by weight, in the composition of the syrup on dry materials; said syrup also generally contains 0.1 to 4% of a mixture of di-, tri- and polysaccharides, the complement to 100 consisting essentially of glucose.
  • the fructose syrup in question contains from 6 to 30% of water or of a water-alcohol mixture, the alcohol part being able to be ethanol, methanol, isopropanol or a mixture of these alcohols.
  • This concentrated syrup is conveyed to a vertical or inclined crystallization zone, which it travels continuously from top to bottom from a point located near its upper end and inside which it is subjected, in the presence of fructose crystals playing the role of germs of crystallization, to a kneading and to a temperature gradient generally decreasing from top to bottom.
  • the temperature of the syrup is brought or maintained, at the time of its introduction into the crystallization zone, at a value chosen in the range from 40 to 80 ° C, preferably from 45 to 65 ° C and, in practice, from 48 to 55 ° C.
  • the temperature gradient established inside the crystallization zone within the mass subjected to crystallization corresponds to a decrease of 0.2 to 2 ° C, preferably from 0.4 to 1.5 ° C and again more preferably from 0.5 to 1 ° C. per hour and is such that at the exit from said zone, at a point situated in the vicinity of the lower end thereof, the mass subjected to crystallization which includes the syrup, the crystals initially present, the enlarged crystals and those possibly formed by the crystallization phenomenon, is brought to a temperature within a range of 5 to 40 ° C, preferably from 15 to 40 ° C and more preferably still from 15 to 30 ° C.
  • the recycled fraction is subjected to a treatment capable of fragmenting the crystals contained in this fraction in order to increase the number of germs and to break possible aggregates of crystals; this treatment can be carried out using a grinder.
  • the means generally represented in 7 comprise a device 10 for fragmenting the crystals contained in the recycled fraction; this device 10 can be constituted by a grinder.
  • the cooling fluid is water and that the average temperature difference at a given point of the enclosure between this water and the mass subjected to crystallization, is of the order of 5 at 15 ° C.
  • the mass rich in crystals extracted at the lower end of the enclosure is at a temperature in the region of 15 ° C, the temperature gradient generally decreasing from top to bottom therefore corresponding to approximately 0.5 ° C per hour.
  • the fructose content of the mother liquors recovered after separation of the anhydrous fructose crystals is 85.6% on dry matter, the complement to 100 being constituted by mono-, di-, tri- and polysaccharides which have not crystallized .
  • the crystals collected after turbination and washing have excellent physical and chemical properties.
  • Example 1 The apparatus and the operating conditions of Example 1 are used.
  • Example 1 The apparatus and the operating conditions of Example 1 are used.
  • the installation is always supplied at a rate of 0.75 m3 per hour but with a fructose syrup of a composition differing from that used in the previous example only in that it contains 15% water and not alcohol.
  • the syrup temperature at the entrance to the enclosure is around 52 ° C.
  • the mass rich in crystals extracted at the lower end of the enclosure is at a temperature in the region of 20 ° C, the temperature gradient having a value of 0.5 ° C per hour.
  • the crystallization yield, after washing the crystals, is 40%.
  • the invention allows the continuous and regular crystallization of an anhydrous fructose of high chemical purity and having a homogeneous particle size distribution.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)
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Abstract

1. Method for the production of anhydrous crystalline fructose characterized by the fact - that the mass subject to crystallization traverses from top to bottom, continuously and with malaxation, a crystallization zone of vertical or inclined direction in which there is established a temperature gradient decreasing globally downwards possibly modulated, - that the crystallization zone is supplied in the vicinity of its upper end, on the one hand, with fructose syrup having a richness in fructose higher than 90% and preferably higher than 93%, and a proportion of dry matter higher than 70% and preferably comprised between 75 and 95% by weight and, on the other hand, with mass subject to crystallization which is taken up and recycled from an intermediate level of the crystallization zone, spaced from its ends by at least one sixth of the total length of said zone, the amount of mass subject to crystallization and recycled representing by volume from 40 to 110% of the amount of fructose syrup introduced into the zone, and - that there is extracted, continuously, in the vicinity of the lower end of the crystallization zone, a product highly enriched in anhydrous fructose crystals from which said crystals are recovered.

Description

L'invention a pour objet un procédé et une installation de production de fructose cristallisé anhydre.The subject of the invention is a method and an installation for producing anhydrous crystallized fructose.

Il est connu de préparer le fructose cristallisé anhydre par refroidissement de sirops riches en fructose en présence de cristaux de fructose qui jouent le rôle de germes de cristallisation.It is known to prepare anhydrous crystallized fructose by cooling syrups rich in fructose in the presence of fructose crystals which act as seeds of crystallization.

Les procédés connus prévoient la dissolution d'un sirop riche en fructose dans un alcool ou dans l'eau et un refroidissement lent avec un ensemencement simultané et l'opération de cristallisation nécessite la mise en oeuvre de plusieurs malaxeurs du type horizontal.The known methods provide for the dissolution of a syrup rich in fructose in an alcohol or in water and slow cooling with simultaneous seeding and the crystallization operation requires the use of several mixers of the horizontal type.

Ces procédés connus présentent notamment l'inconvénient de nécessiter au moins deux malaxeurs dont un joue le rôle de pied; de plus, dans le cas de la cristallisation en milieu aqueux, les cristaux obtenus sont de faible taille et difficiles à purifier dans des conditions économiques.These known methods have the particular disadvantage of requiring at least two mixers, one of which acts as a foot; moreover, in the case of crystallization in an aqueous medium, the crystals obtained are of small size and difficult to purify under economic conditions.

Les derniers développements de ces procédés sont reflétés notamment pour la cristallisation en milieu aqueux par le brevet français N° 2.128.835 déposé le 10 mars 1972 par la Société SUOMEN SO-KERI OSAKEYHTIO et pour la cristallisation en milieu alcoolique par le brevet français N° 1.596.220 déposé par la Société BOEHRINGER MANNHEIM le 20 décembre 1980.The latest developments in these processes are reflected in particular for crystallization in an aqueous medium by French patent No. 2,128,835 filed on March 10, 1972 by the Company SUOMEN SO-KERI OSAKEYHTIO and for crystallization in alcoholic medium by French patent No. 1,596,220 filed by BOEHRINGER MANNHEIM on December 20, 1980.

Le brevet français N° 2 128 835 décrit un procédé permettant d'obtenir en milieu aqueux et en continu de gros cristaux de fructose. Ce procédé présente cependant l'inconvénient de nécessiter, pour sa mise en oeuvre continue, un appareillage sophistiqué et très délicat.French Patent No. 2,128,835 describes a process for obtaining large fructose crystals in an aqueous medium and continuously. However, this method has the disadvantage of requiring, for its continuous implementation, sophisticated and very delicate apparatus.

Le brevet N° 1 596 220 présente un procédé continu de cristallisation d'une solution de fructose diluée dans le méthanol, la cristallisation étant partiellement réalisée dans un malaxeur vertical. Ce procédé, outre le fait qu'il n'est applicable qu'a des solutions diluées de fructose, nécessite un dispositif supplémentaire pour la préparation de l'amorce cristalline.Patent No. 1,596,220 describes a continuous process for crystallizing a solution of fructose diluted in methanol, the crystallization being partially carried out in a vertical mixer. This process, in addition to the fact that it is only applicable to dilute solutions of fructose, requires an additional device for the preparation of the crystal primer.

La demande de brevet FA-A 2 217 421 décrit quatre procédés de cristallisation du fructose dont un seul d'ailleurs présente comme le moins avantageux, procède par refroidissement seul.Patent application FA-A 2 217 421 describes four processes for crystallizing fructose, only one of which, moreover, presents as the least advantageous, proceeds by cooling alone.

Ces procédés ne donnent pas entièrement satisfaction tant du point de vue de la productivité par unité de volume de l'appareillage que de celui du bilan énergétique.These methods are not entirely satisfactory both from the point of view of the productivity per unit volume of the apparatus and that of the energy balance.

On connaît également par la demande de brevet EP-A 0 147 269 un procédé de cristallisation comportant un recyclage relatif au dextrose monohy- drate.Also known from patent application EP-A 0 147 269 is a crystallization process comprising recycling relating to dextrose monohydrate.

Pour faire face aux contraintes notamment économiques toujours plus sévères, la Société Demanderesse a cherché à mettre au point un procédé et une installation du genre en question qui répondent mieux que ceux qui existent déjà aux divers desiderata de la pratique, en particulier précisément du point de vue de la productivité de l'opération de cristallisation par unité de volume de l'appareillage utilisé et du bilan énergétique.To cope with ever more severe economic constraints in particular, the Applicant Company has sought to develop a process and installation of the kind in question which respond better than those which already exist to the various wishes of the practice, in particular precisely from the point of view of the productivity of the crystallization operation per unit volume of the apparatus used and of the energy balance.

Et elle a trouvé que ce but pouvait être atteint grâce à un procédé caractérisé par le fait:

  • - que la masse soumise à la cristallisation parcourt de haut en bas, en continu et sous malaxage une zone de cristallisation de direction verticale ou inclinée, dans laquelle est établi un gradient de température globalement décroissant vers le bas éventuellement modulé, 4
  • - que l'on alimente la zone de cristallisation au voisinage de son extrémité supérieure, d'une part, en sirop de fructose ayant une richesse en fructose supérieure à 90% et de préférence supérieure à 93% et un taux de matières sèches supérieur à 70% et de préférence de 75% à 95% en poids et, d'autre part, en masse soumise à la cristallisation qui est prélevée et recyclée à partir d'un niveau intermédiaire de la zone de cristallisation, distant de ses extrémités d'au moins 1/6, de préférence d'au moins 1/5 et encore plus préférentiellement d'au moins 1/4 de la longueur totale de ladite zone, la quantité de masse soumise à la cristallisation et recyclée représentant en volume de 40 à 110% et plus préférentiellement encore de 80 à 100% de la quantité de sirop de fructose introduite dans la zone, et
  • - que l'on extrait, en continu, au voisinage de l'extrémité inférieure de la zone de cristallisation, un produit fortement enrichi en cristaux de fructose anhydre à partir duquel on récupère lesdits cristaux.
And she found that this goal could be achieved through a process characterized by the fact:
  • - that the mass subjected to crystallization traverses from top to bottom, continuously and under kneading a crystallization zone of vertical or inclined direction, in which a globally decreasing downward temperature gradient is established, possibly modulated, 4
  • - that the crystallization zone near its upper end is supplied, on the one hand, with fructose syrup having a richness in fructose greater than 90% and preferably greater than 93% and a dry matter content greater than 70% and preferably from 75% to 95% by weight and, on the other hand, by mass subjected to crystallization which is removed and recycled from an intermediate level of the crystallization zone, distant from its ends at least 1/6, preferably at least 1/5 and even more preferably at least 1/4 of the total length of the said zone, the quantity of mass subjected to crystallization and recycled representing by volume from 40 to 110% and more preferably still from 80 to 100% of the amount of fructose syrup introduced into the area, and
  • - that is extracted, continuously, near the lower end of the crystallization zone, a product highly enriched in anhydrous fructose crystals from which said crystals are recovered.

Pour mettre en oeuvre le susdit procédé, on a recours, conformément à l'invention, à une installation comprenant essentiellement une enceinte de cristallisation d'axe vertical ou incliné et équipée

  • - d'un système d'alimentation en sirop de fructose au voisinage de son extrémité supérieure,
  • -d'un système de malaxage et d'un système de régulation de température propres à établir à l'intérieur de l'enceinte et au sein de la masse soumise à la cristallisation contenue dans l'enceinte, un gradient de température globalement décroissant de haut en bas, et
  • - d'un système d'extraction continue au voisinage de son extrémité inférieure, d'un produit fortement enrichi en cristaux de fructose anhydre qui est acheminé par des moyens appropriés vers un système propre à récupérer les cristaux à partir de ce produit,
  • - de moyens propres à prélever à un niveau intermédiaire de l'enceinte, distant des extrémités de celle-ci d'au moins 1/6, de préférence 1/5 et plus préférentiellement encore 1/4 de la longueur totale, une quantité de masse soumise à la cristallisation qui correspond, en volume, de 40 à 110% et plus préférentiellement encore de 80 à 100% de la quantité de sirop de fructose introduit au voisinage de l'extrémité supérieure de l'enceinte, lesdits moyens propres à prélever la masse soumise à la cristallisation étant de plus propres à la recycler dans l'enceinte à un niveau de préférence voisin de l'extrémité supérieure de celle-ci.
To implement the above process, use is made, in accordance with the invention, of an installation essentially comprising a crystallization chamber with a vertical or inclined axis and equipped
  • - a fructose syrup supply system near its upper end,
  • -a kneading system and a temperature regulation system capable of establishing, inside the enclosure and within the mass subjected to crystallization contained in the enclosure, a temperature gradient generally decreasing by up and down, and
  • - a continuous extraction system near its lower end, a product highly enriched in anhydrous fructose crystals which is conveyed by appropriate means to a system capable of recovering the crystals from this product,
  • - means suitable for taking at an intermediate level of the enclosure, distant from the ends thereof at least 1/6, preferably 1/5 and more preferably still 1/4 of the total length, an amount of mass subjected to crystallization which corresponds, by volume, from 40 to 110% and more preferably still from 80 to 100% of the amount of fructose syrup introduced in the vicinity of the upper end of the enclosure, said means suitable for withdrawing the mass subjected to crystallization being more suitable for recycling it in the enclosure at a level preferably close to the upper end thereof.

L'invention vise également d'autres dispositions qui s'utilisent de préférence en même temps et dont il sera plus explicitement question ci-après.The invention also relates to other arrangements which are preferably used at the same time and which will be more explicitly discussed below.

Et elle pourra, de toute façon, être bien comprise à l'aide du complément de description qui suit et du dessin annexé qui sont relatifs à des modes de réalisation avantageux. La figure unique du dessin montre schématiquement une installation conforme à l'invention.And it can, in any case, be well understood with the aid of the additional description which follows and of the appended drawing which relate to advantageous embodiments. The single figure of the drawing schematically shows an installation according to the invention.

Se proposant, par conséquent, de produire du fructose cristallisé anhydre conformément à l'invention, on s'y prend comme suit ou de façon équivalente.Proposing, therefore, to produce anhydrous crystallized fructose in accordance with the invention, this is done as follows or in an equivalent manner.

On utilise comme matière première des sirops de fructose obtenus, par example, à partir d'un hydro- lysat d'amidon que l'on a isomérisé puis enrichi par chromatographie, présentant une teneur en matières sèches d'environ 75 à 95% en poids, le fructose entrant pour au moins 90% et, de préférence, pour une proportion supérieure à 93% en poids, dans la constitution sur matières sèches du sirop; ledit sirop contient par ailleurs généralement de 0,1 à 4% d'un mélange de di-, tri- et polysaccharides, le complément à 100 étant essentiellement constitué par du glucose.Fructose syrups obtained, for example, from a starch hydrolyzate which is isomerized and then enriched by chromatography, having a dry matter content of approximately 75 to 95%, are used as the raw material. by weight, the fructose entering for at least 90% and, preferably, for a proportion greater than 93% by weight, in the composition of the syrup on dry materials; said syrup also generally contains 0.1 to 4% of a mixture of di-, tri- and polysaccharides, the complement to 100 consisting essentially of glucose.

Suivant un mode de réalisation particulier de l'invention, le sirop de fructose en question, d'une richesse supérieure à 90%, contient de 6 à 30% d'eau ou d'un mélange eau-alcool, la partie alcool pouvant être de l'éthanol, du méthanol, de l'iso- propanol ou un mélange de ces alcools.According to a particular embodiment of the invention, the fructose syrup in question, with a richness greater than 90%, contains from 6 to 30% of water or of a water-alcohol mixture, the alcohol part being able to be ethanol, methanol, isopropanol or a mixture of these alcohols.

Ce sirop concentré est acheminé vers une zone de cristallisation verticale ou inclinée, qu'il parcourt en continu de haut en bas à partir d'un point situé au voisinage de son extrémité supérieure et à l'intérieur de laquelle il est soumis, en présence de cristaux de fructose jouant le rôle de germes de cristallisation, à un malaxage et à un gradient de température globalement décroissant de haut en bas.This concentrated syrup is conveyed to a vertical or inclined crystallization zone, which it travels continuously from top to bottom from a point located near its upper end and inside which it is subjected, in the presence of fructose crystals playing the role of germs of crystallization, to a kneading and to a temperature gradient generally decreasing from top to bottom.

La température du sirop est amenée ou maintenue, au moment de son introduction dans la zone de cristallisation, à une valeur choisie dans l'intervalle de 40 à 80°C, de préférence de 45 à 65°C et, dans la pratique, de 48 à 55°C.The temperature of the syrup is brought or maintained, at the time of its introduction into the crystallization zone, at a value chosen in the range from 40 to 80 ° C, preferably from 45 to 65 ° C and, in practice, from 48 to 55 ° C.

Le gradient de température établi à l'intérieur de la zone de cristallisation au sein de la masse soumise à la cristallisation correspond à une diminution de 0,2 à 2°C, de préférence de 0,4 à 1,5°C et encore plus préférentiellement de 0,5 à 1°C par heure et est tel qu'à la sortie de ladite zone, à un point situé au voisinage de l'extrémité inférieure de celle-ci, la masse soumise à cristallisation qui comprend le sirop, les cristaux initialement présents, les cristaux grossis et ceux éventuellement formés par le phénomène de cristallisation, se trouve amenée à une température située à l'intérieur d'un intervalle de 5 à 40°C, de préférence de 15 à 40°C et plus préférentiellement encore de 15 à 30°C.The temperature gradient established inside the crystallization zone within the mass subjected to crystallization corresponds to a decrease of 0.2 to 2 ° C, preferably from 0.4 to 1.5 ° C and again more preferably from 0.5 to 1 ° C. per hour and is such that at the exit from said zone, at a point situated in the vicinity of the lower end thereof, the mass subjected to crystallization which includes the syrup, the crystals initially present, the enlarged crystals and those possibly formed by the crystallization phenomenon, is brought to a temperature within a range of 5 to 40 ° C, preferably from 15 to 40 ° C and more preferably still from 15 to 30 ° C.

Au fur et à mesure que la masse soumise à la cristallisation se rapproche de l'extrémité inférieure de la zone de cristallisation, sa richesse en cristaux de fructose anhydre augmente, ladite masse formant à la sortie de la zone une "masse riche en cristaux".As the mass subjected to crystallization approaches the lower end of the crystallization zone, its richness in anhydrous fructose crystals increases, said mass forming at the exit of the zone a "mass rich in crystals" .

L'obtention, au voisinage de l'extrémité inférieure de la zone de cristallisation d'une masse riche en cristaux qui puisse être extraite en continu sans dérèglement des paramètres du processus de cristallisation, dérèglement qui se répercuterait au niveau de l'étape suivante de séparation de la phase liquide et des cristaux et qui pourrait nécessiter des arrêts intermittents de l'installation, en d'autres termes la mise à la disposition de l'utilisateur d'un procédé permettant d'arriver à une productivité par unité de volume de l'appareillage utilisé supérieure à celle des installations conformes à l'art antérieur, est rendu possible, conformément à l'invention, grâce au prélèvement, à un niveau intermédiaire de la zone de cristallisation, distant des extrémités de celle-ci d'au moins un sixième de sa longueur totale, d'une fraction de la masse soumise à cristallisation qui est recyclée et réintroduite dans la zone de cristallisation à un niveau voisin de son extrémité supérieure.Obtaining, in the vicinity of the lower end of the crystallization zone, a mass rich in crystals which can be continuously extracted without disruption of the parameters of the crystallization process, disruption which would be reflected in the next step of separation of the liquid phase and the crystals and which could necessitate intermittent shutdowns of the installation, in other words the provision to the user of a process making it possible to arrive at a productivity per unit volume of the apparatus used is greater than that of the installations in accordance with the prior art, is made possible, in accordance with the invention, by virtue of the sampling, at an intermediate level of the crystallization zone, distant from the ends thereof minus one sixth of its total length, of a fraction of the mass subjected to crystallization which is recycled and reintroduced into the crystallization zone at a level close to its upper end.

La fraction prélevée et recyclée représente, en volume, de 40 à 110% et plus préférentiellement encore de 80 à 100% du volume de sirop de fructose alimentant la zone de cristallisation.The fraction removed and recycled represents, by volume, from 40 to 110% and more preferably still from 80 to 100% of the volume of fructose syrup supplying the crystallization zone.

Suivant un mode de réalisation préférentiel, la fraction recyclée est soumise à un traitement propre à fragmenter les cristaux contenus dans cette fraction afin d'augmenter le nombre de germes et de casser d'éventuels agrégats de cristaux; ce traitement peut être effectué à l'aide d'un broyeur.According to a preferred embodiment, the recycled fraction is subjected to a treatment capable of fragmenting the crystals contained in this fraction in order to increase the number of germs and to break possible aggregates of crystals; this treatment can be carried out using a grinder.

Le débit d'alimentation en sirop de fructose est choisi de façon telle que le temps de séjour moyen, d'une fraction donnée de la masse soumise à cristallisation à l'intérieur de la zone de cristallisation soit de 30 à 120 heures, de préférence de 50 à 90 heures et plus préférentiellement encore de 60 à 75 heures; la valeur adoptée dépend des capacités d'échange thermique des moyens comportés par la zone et à l'aide desquels est établi, à l'intérieur de ladite zone au sein de la masse soumise à la cristallisation, le gradient de température décroissant.The rate of supply of fructose syrup is chosen such that the average residence time of a given fraction of the mass subjected to crystallization inside the crystallization zone is from 30 to 120 hours, preferably from 50 to 90 hours and more preferably still from 60 to 75 hours; the value adopted depends on the heat exchange capacities of the means comprised by the zone and with the help of which is established, inside said zone within the mass subjected to crystallization, the decreasing temperature gradient.

Le niveau intermédiaire auquel est réalisé le prélèvement de la fraction soumise à cristallisation qui est destinée au recyclage, est de préférence distant des extrémités de la zone de cristallisation d'au moins 1/6 et, dans la pratique, de l'ordre d'au moins 1/5 et plus préférentiellement de 1/4 de la longueur totale de ladite zone.The intermediate level at which the withdrawal of the fraction subjected to crystallization which is intended for recycling is carried out, is preferably distant from the ends of the crystallization zone by at least 1/6 and, in practice, of the order of at least 1/5 and more preferably 1/4 of the total length of said area.

La viscosité de la masse soumise à cristallisation augmente au fur et à mesure que croît la proportion de cristaux de fructose anhydre, c'est-à-dire dans le sens descendant. L'installation est donc, de préférence, équipée de moyens de refoulement ou d'aspiration propres à assurer le cheminement de la masse à l'intérieur de la zone.The viscosity of the mass subjected to crystallization increases as the proportion of anhydrous fructose crystals increases, that is to say in the downward direction. The installation is therefore preferably equipped with discharge or suction means capable of ensuring the movement of the mass inside the zone.

Par ailleurs, les moyens de malaxage et d'homogénéisation comportés par l'installation doivent être agencés de telle sorte que les zones mortes soient évitées et que l'échange thermique entre la masse soumise à cristallisation et les moyens de refroidissement soit le plus efficace possible.Furthermore, the kneading and homogenization means provided by the installation must be arranged in such a way that dead zones are avoided and that the heat exchange between the mass subjected to crystallization and the cooling means is as efficient as possible. .

Le produit extrait de la zone de cristallisation et qui constitue, comme déjà indiqué, une masse riche en cristaux, comprend des cristaux de fructose anhydre d'un spectre granulométrique caractérisé par une faible proportion de fins et de gros cristaux et donc par une forte proportion de cristaux de taille intermédiaire, ce spectre ne variant pas dans le temps, ce grâce à quoi l'étape de traitement suivante, qui consiste à séparer ces cristaux de la phase liquide dans laquelle ils baignent, ne connaît pas de perturbation.The product extracted from the crystallization zone and which constitutes, as already indicated, a mass rich in crystals, comprises anhydrous fructose crystals of a particle size spectrum characterized by a small proportion of fine and large crystals and therefore by a high proportion crystals of intermediate size, this spectrum does not vary over time, whereby the following treatment step, which consists in separating these crystals from the liquid phase in which they are immersed, does not experience any disturbance.

Cette séparation comprend un turbinage et éventuellement un lavage grâce auxquels on récupère la majeure partie de la phase liquide; celle-ci forme des eaux-mères dont la concentration en fructose est inférieure à celle du sirop de fructose de départ - cette concentration atteint généralement de 75 à 92% - et dans lesquels on retrouve la presque totalité des mono-, di-, tri- et polysaccharides contenus dans le sirop de fructose de départ.This separation comprises a turbination and possibly a washing by which the major part of the liquid phase is recovered; this forms mother liquors whose fructose concentration is lower than that of the starting fructose syrup - this concentration generally reaches 75 to 92% - and in which we find almost all of the mono-, di-, tri- and polysaccharides contained in the starting fructose syrup.

Les eaux-mères recueillies peuvent être partiellement recyclées.The mother liquors collected can be partially recycled.

Ceci étant, pour mettre en oeuvre le procédé conforme à l'invention, on peut avoir recours à une enceinte unique 1 ayant la forme d'un cylindre de révolution d'axe XY.However, to implement the method according to the invention, recourse may be had to a single enclosure 1 having the shape of a cylinder of revolution of axis XY.

L'axe XY est disposé avantageusement suivant la verticale mais peut également être incliné. L'enceinte est équipée

  • - d'un système d'alimentation en sirop de fructose au niveau de l'extrémité supérieure de l'enceinte et représenté schématiquement par une canalisation 2,
  • - d'un système de malaxage et de régulation de la température dont il va être question et
  • - d'un système d'extraction en continu au niveau de l'extrémité inférieure de l'enceinte et schématiquement représenté par une canalisation 3, ce système étant propre à récupérer la masse cristalline obtenue à la sortie de la zone de cristallisation.
  • Le système de malaxage et de régulation de la température dont il est question ci-dessus peut avantageusement comporter
  • - un ensemble de bras de malaxage 4 portés à intervalles réguliers par un arbre rotatif 5 dont l'axe est confondu avec l'axe XY de l'enceinte,
  • - des nappes de refroidissement 6 disposées en alternance avec les bras malaxeurs 4 et portées par la paroi de l'enceinte 1, ces nappes de refroidissement étant parcourues par un fluide de refroidissement.
  • Conformément à l'invention, l'enceinte comporte en outre des moyens globalement représentés en 7 et propres
  • - à prélever à un niveau intermédiaire 8 de l'enceinte, distant des extrémités de l'enceinte d'au moins 1/6, de préférence 1/5 et encore plus préférentiellement 1/4 de la longueur totale de l'enceinte, une fraction de la masse M soumise à cristallisation et parcourant l'enceinte de haut en bas et
  • - à recycler cette fraction à un niveau 9 situé de préférence au voisinage de l'extrémité supérieure de l'enceinte.
The XY axis is advantageously arranged vertically but can also be tilted. The enclosure is equipped
  • a system for supplying fructose syrup at the upper end of the enclosure and represented diagrammatically by a pipe 2,
  • - a mixing and temperature regulation system which will be discussed and
  • - a continuous extraction system at the lower end of the enclosure and schematically represented by a pipe 3, this system being suitable for recovering the crystalline mass obtained at the outlet of the crystallization zone.
  • The mixing and temperature regulation system mentioned above can advantageously include
  • a set of mixing arms 4 carried at regular intervals by a rotary shaft 5 whose axis coincides with the axis XY of the enclosure,
  • - Cooling layers 6 arranged alternately with the mixer arms 4 and carried by the wall of the enclosure 1, these cooling layers being traversed by a cooling fluid.
  • According to the invention, the enclosure further comprises means generally represented in 7 and specific
  • - to be taken at an intermediate level 8 of the enclosure, distant from the ends of the enclosure at least 1/6, preferably 1/5 and even more preferably 1/4 of the total length of the enclosure, a fraction of the mass M subjected to crystallization and traversing the enclosure from top to bottom and
  • - To recycle this fraction at a level 9 preferably located near the upper end of the enclosure.

La capacité d'échange thermique, le système de régulation de température, la vitesse de rotation des moyens de malaxage et la vitesse avec laquelle la masse soumise à cristallisation parcourt l'enceinte, c'est-à-dire la durée moyenne de séjour d'une fraction donnée de cette masse à l'intérieur de l'enceinte, sont choisies de façon telle que s'établisse, au sein de l'ensemble de la masse soumise à cristallisation, le gradient de température prévu conformément à l'invention.The heat exchange capacity, the temperature regulation system, the speed of rotation of the kneading means and the speed with which the mass subjected to crystallization traverses the enclosure, that is to say the average residence time d 'a given fraction of this mass inside the enclosure, are chosen so that the temperature gradient provided for in accordance with the invention is established within the whole of the mass subjected to crystallization.

De préférence, les moyens globalement représentés en 7 comportent un dispositif 10 de fragmentation des cristaux contenus dans la fraction recyclée; ce dispositif 10 peut être constitué par un broyeur.Preferably, the means generally represented in 7 comprise a device 10 for fragmenting the crystals contained in the recycled fraction; this device 10 can be constituted by a grinder.

On signale que, dans la pratique, le fluide de refroidissement est de l'eau et que l'écart moyen de température en un point donné de l'enceinte entre cette eau et la masse soumise à cristallisation, est de l'ordre de 5 à 15°C.It is pointed out that, in practice, the cooling fluid is water and that the average temperature difference at a given point of the enclosure between this water and the mass subjected to crystallization, is of the order of 5 at 15 ° C.

EXEMPLE 1EXAMPLE 1

a) On a recours à une installation conforme à l'invention comportant une enceinte cylindrique unique d'un volume utile de 50 m3 et équipée d'un broyeur.a) Use is made of an installation in accordance with the invention comprising a single cylindrical enclosure with a useful volume of 50 m 3 and equipped with a grinder.

On introduit dans cette enceinte, avec un débit de 0,75 m3 par heure, un sirop de fructose ayant une teneur en matières sèches sucrées de 90% et comprenant 94% en poids sur matière sèche de fructose, les 6% restants étant constitués par 3% de glucose et par 3% de di-, tri- et polysaccharides.Is introduced into this enclosure, with a flow rate of 0.75 m 3 per hour, a fructose syrup having a sweet dry matter content of 90% and comprising 94% by weight on fructose dry matter, the remaining 6% being constituted by 3% of glucose and by 3% of di-, tri- and polysaccharides.

Ce sirop contient 10% d'un mélange de 49% d'eau et de 51 % d'alcool; ce sirop a une densité de 1,45.This syrup contains 10% of a mixture of 49% water and 51% alcohol; this syrup has a density of 1.45.

La température du sirop à l'entrée de l'enceinte est d'environ 50°C.The syrup temperature at the entrance to the enclosure is approximately 50 ° C.

Simultanément on recycle, avec un débit de 0,7 m3 par heure, une fraction de la masse en cours de cristallisation prélevée à un niveau sensiblement médian de l'enceinte et passée sur le broyeur.Simultaneously, a fraction of the mass during crystallization taken from a substantially median level of the enclosure and passed over the mill is recycled, with a flow rate of 0.7 m3 per hour.

La durée de passage moyen à l'intérieur de l'enceinte d'une fraction donnée de la masse soumise à la cristallisation est d'environ 66 heures.The average passage time inside the enclosure of a given fraction of the mass subjected to crystallization is approximately 66 hours.

La masse riche en cristaux extraite au niveau de l'extrémité inférieure de l'enceinte se trouve à une température voisine de 15°C, le gradient de température globalement décroissant de haut en bas correspondant donc à environ 0,5°C par heure.The mass rich in crystals extracted at the lower end of the enclosure is at a temperature in the region of 15 ° C, the temperature gradient generally decreasing from top to bottom therefore corresponding to approximately 0.5 ° C per hour.

La teneur en fructose des eaux-mères récupérées après séparation des cristaux de fructose anhydre est de 85,6% sur matières sèches, le complément à 100 étant constitué par les mono-, di-, tri- et polysaccharides qui n'ont pas cristallisé.The fructose content of the mother liquors recovered after separation of the anhydrous fructose crystals is 85.6% on dry matter, the complement to 100 being constituted by mono-, di-, tri- and polysaccharides which have not crystallized .

Le rendement de cristallisation qui est donné par la formule:

Figure imgb0001
dans laquelle

  • - A, qui représente la richesse en fructose sur matières sèches du sirop d'alimentation, est égale à 94% et
  • - H, qui représente la richesse des eaux-mères avant lavage des cristaux, est égale à 85,6%, s'établit à 58,3%.
The crystallization yield which is given by the formula:
Figure imgb0001
 in which
  • - A, which represents the richness in fructose on dry matter of the feed syrup, is equal to 94% and
  • - H, which represents the richness of the mother liquors before washing the crystals, is equal to 85.6%, stands at 58.3%.

On produit par jour 13 tonnes de fructose anhydre pur, ce qui correspond à une productivité de 0,260 tonne par jour et par m3 de l'enceinte.13 tonnes of pure anhydrous fructose are produced per day, which corresponds to a productivity of 0.260 tonnes per day and per m 3 of the enclosure.

Ce résultat est nettement supérieur à celui qui l'on obtient lors de la cristallisation du même sirop de fructose dans un réacteur horizontal dont la productivité s'établit à 0,2 tonne par m3 de l'enceinte et par jour.This result is significantly higher than that obtained during the crystallization of the same fructose syrup in a horizontal reactor whose productivity is 0.2 tonnes per m 3 of the enclosure and per day.

De plus, il ne se produit aucune perturbation nécessitant l'arrêt de l'installation qui fonctionne en continu.In addition, there is no disturbance that necessitates the shutdown of the continuously operating installation.

Les cristaux recueillis après turbinage et lavage présentent d'excellentes propriétés physiques et chimiques.The crystals collected after turbination and washing have excellent physical and chemical properties.

Ces cristaux sont d'une pureté de 99,8%, leur indice d'écoulement est bon et leur répartition granulométrique est la suivante:

  • - cristaux de taille supérieure à 1250 lim: 5%
  • - cristaux de taille comprise entre 1250 et 500 µm: 45%
  • - cristaux de taille comprise entre 500 et 200 .m: 45%
  • - cristaux de taille inférieure 200 wm: 5%.
These crystals are 99.8% pure, their in the flow dice is good and their particle size distribution is as follows:
  • - crystals larger than 1250 l im: 5%
  • - crystals of size between 1250 and 500 µm: 45%
  • - crystals of size between 500 and 200 .m: 45%
  • - crystals of smaller size 200 wm: 5%.

b) On utilise l'appareillage et les conditions opératoires de l'example 1.b) The apparatus and the operating conditions of Example 1 are used.

Toutefois, à un moment donné, après avoir atteint l'équilibre du système, on prélève la fraction recyclée non plus à un niveau intermédiaire mais à un point de l'enceinte situé dans le dernier sixième de la hauteur totale.However, at a given moment, after reaching the equilibrium of the system, the recycled fraction is no longer taken at an intermediate level but at a point in the enclosure located in the last sixth of the total height.

On assiste alors rapidement à une évolution des paramètres de la cristallisation qui se manifeste au bout de quelques jours par une mauvaise séparation au niveau des turbines et qui finit par nécessiter l'arrêt de l'installation et l'évacuation de la masse qu'elle contient avant redémarrage dans les conditions conformes à l'invention.We then quickly witness an evolution of the crystallization parameters which manifests itself after a few days by poor separation at the level of the turbines and which ends up necessitating the stopping of the installation and the evacuation of the mass which it contains before restarting under the conditions according to the invention.

EXEMPLE 2EXAMPLE 2

a) On utilise l'appareillage et les conditions opératoires de l'exemple 1.a) The apparatus and the operating conditions of Example 1 are used.

L'installation est toujours alimentée à raison de 0,75 m3 par heure mais avec un sirop de fructose d'une composition ne différant de celle utilisée dans l'exemple précédent que par le fait qu'elle contient 15% d'eau et pas d'alcool.The installation is always supplied at a rate of 0.75 m3 per hour but with a fructose syrup of a composition differing from that used in the previous example only in that it contains 15% water and not alcohol.

La température de sirop à l'entrée de l'enceinte est d'environ 52°C.The syrup temperature at the entrance to the enclosure is around 52 ° C.

Simultanément on recycle, avec un débit de 0,6 m3 par heure, une fraction de la masse en cours de cristallisation prélevée à un niveau sensiblement médian de l'enceinte. Cette masse est soumise au broyage de façon à casser d'éventuels agrégats de cristaux.Simultaneously, a fraction of the mass during crystallization taken from a substantially median level of the enclosure is recycled, with a flow rate of 0.6 m3 per hour. This mass is subjected to grinding so as to break possible aggregates of crystals.

La masse riche en cristaux extraite au niveau de l'extrémité inférieure de l'enceinte se trouve à une température voisine de 20°C, le gradient de température ayant une valeur de 0,5°C par heure.The mass rich in crystals extracted at the lower end of the enclosure is at a temperature in the region of 20 ° C, the temperature gradient having a value of 0.5 ° C per hour.

La teneur en fructose des eaux-mères récupérées après séparation et lavage des cristaux de fructose anhydre est de 90% sur matières sèches, le complément à 100 étant constitué par des mono-, di-, tri- et polysaccharides qui n'ont pas cristallisé.The fructose content of the mother liquors recovered after separation and washing of the anhydrous fructose crystals is 90% on dry materials, the complement to 100 consisting of mono-, di-, tri- and polysaccharides which have not crystallized .

Le rendement de la cristallisation, après le lavage des cristaux, est de 40%.The crystallization yield, after washing the crystals, is 40%.

Dans ces conditions, on produit par jour 8,6 tonnes de fructose anhydre pur, ce qui correspond à une productivité de 0,172 tonne par jour et par m3 de l'enceinte.Under these conditions, 8.6 tonnes of pure anhydrous fructose are produced per day, which corresponds to a productivity of 0.172 tonnes per day per m3 of the enclosure.

On constate à nouveau une grande régularité au niveau du fonctionnement de l'installation et une grande facilité au niveau du turbinage des cristaux.Again, there is great regularity in the operation of the installation and great ease in the turbination of the crystals.

Ces cristaux sont d'une pureté de 99,9%, leur indice d'écoulement est bon et leur répartition granulométrique est la suivante:These crystals are 99.9% pure, their flow index is good and their particle size distribution is as follows:

  • - cristaux de taille supérieure à 1250 lim: 4%- crystals larger than 1250 l im: 4%
  • - cristaux de taille comprise entre 1250 et 500 )lm: 47%- crystals of size between 1250 and 500) lm: 47%
  • - cristaux de taille comprise entre 500 et 200 µm: 46%- crystals of size between 500 and 200 µm: 46%
  • - cristaux de taille inférieure à 200 um: 3%.- crystals of size less than 200 μm : 3%.

b) Comme dans l'exemple précédent, après avoir atteint l'équilibre de fonctionnement, on prélève la fraction recyclée à un point de l'enceinte situé dans le dernier sixième de la hauteur totale.b) As in the previous example, after having reached operating equilibrium, the recycled fraction is taken from a point in the enclosure located in the last sixth of the total height.

On assiste à nouveau à une évolution des paramètres de la cristallisation et il est nécessaire d'arrêter, pour les mêmes raisons et après quelques jours, l'installation.There is again a change in the crystallization parameters and it is necessary to stop, for the same reasons and after a few days, the installation.

Outre une amélioration-de la productivité par m3 de réacteur, l'invention permet la cristallisation continue et régulière d'un fructose anhydre d'une pureté chimique élevée et présentant une répartition granulométrique homogène.In addition to an improvement in productivity per m 3 of reactor, the invention allows the continuous and regular crystallization of an anhydrous fructose of high chemical purity and having a homogeneous particle size distribution.

Claims (8)

1. Method for the production of anhydrous crystalline fructose characterized by the fact
- that the mass subject to crystallization traverses from top to bottom, continuously and with malaxation, a crystallization zone of vertical or inclined direction in which there is established a temperature gradient decreasing globally downwards possibly modulated,
- that the crystallization zone is supplied in the vicinity of its upper end, on the one hand, with fructose syrup having a richness in fructose higher than 90% and preferably higher than 93%, and a proportion of dry matter higher than 70% and preferably comprised between 75 and 95% by weight and, on the other hand, with mass subject to crystallization which is taken up and recycled from an intermediate level of the crystallization zone, spaced from its ends by at least one sixth of the total length of said zone, the amount of mass subject to crystallization and recycled representing by volume from 40 to 110% of the amount of fructose syrup introduced into the zone, and
- that there is extracted, continuously, in the vicinity of the lower end of the crystallization zone, a product highly enriched in anhydrous fructose crystals from which said crystals are recovered.
2. Method according to claim 1, characterized by the fact that the fraction of mass subjected to crystallization which is taken up and recycled represents by volume from 80 to 100% of the volume of fructose syrup supplying the crystallization zone.
3. Method according to one of claims 1 and 2, characterized by the fact that the intermediate level at which is taken up the fraction subjected to crystallization, which fraction is intended for recycling, is preferably spaced from the ends of the crystallization zone by at least one fifth of the total length of the latter and, in practice, of at least one fourth of the total length of said zone.
4. Method according to one of claims 1 to 3, characterized by the fact
- that the temperature of the syrup, at the moment of its introduction into the crystallization zone, is brought to or maintained, at a value selected in the range from 40 to 80°C, preferably from 45 to 65°C and, in practice, from 48 to 55°C,
- that the temperature gradient established inside the crystallization zone within the mass subject to crystallization corresponds to a reduction from 0.2 to 2°C, preferably from 0.4 to 1.5°C and still more preferably from 0.5 to 1°C per hour, and
- that at the outlet of said zone, at a point situated in the vicinity of the lower end of the latter, the mass subjected to crystallization which comprises the syrup, the crystals initially present and those formed by the crystallization phenomenon, is brought to a temperature situated within a range from 5 to 40°C, preferably from 15 to 40°C and still more preferably from 15 to 30°C.
5. Method according to one of claims 1 to 4, characterized by the fact that the average dwell time of a given fraction of the mass subject to crystallization inside the crystallization zone is from 30 to 120 hours, preferably from 50 to 90 hours and still more preferably from 60 to 75 hours.
6. Method according to one of claims 1 to 5, characterized by the fact that the fructose syrup serving as raw material has a content of dry matter from about 75 to 95%, fructose entering for at least 90% and, preferably, for a proportion higher than 93% by weight, into the constitution on dry matter of the syrup.
7. Method according to one of claims 1 to 6, characterized by the fact that the fructose syrup serving as raw material contains from 6 to 30% of water or a water-ethanol, water-methanol or water-isopropanol mixture, and/or a mixture of these alcohols.
8. Installation for the production of crystallization fructose characterized by the fact that it comprises essentially a crystallization vessel of vertical or inclined axis and equipped
- with a system of supply of fructose syrup in the vicinity of its upper end,
- with a system of malaxation and a system of temperature regulation adapted to establish inside the vessel and within the mass subjected to crystallization contained in the vessel, an overall temperature gradient decreasing from top to bottom,
- with a continuous extraction system in the vicinity of its lower end, for a product highly enriched in anhydrous fructose crystals which is led by suitable means to a system adapted to recover the crystals from this product, and
- with means adapted to take up at an intermediate level of the vessel, spaced from the ends of the latter by at least 1/6, preferably 1/5 and still more preferably 1/4 of its total length, an amount of mass subject to crystallization which corresponds, in volume, to 40 to 110% and, preferably, to 80 to 100% of the amount of fructose syrup introduced in the vicinity of the upper end of the vessel, said means adapted to take up the mass subject to crystallization being also adapted to recycle it into the vessel, preferably at a level close to the upper end of the latter.
EP86401006A 1985-05-15 1986-05-12 Process and apparatus for the preparation of crystalline anhydrous fructose Expired EP0203844B1 (en)

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AT86401006T ATE42343T1 (en) 1985-05-15 1986-05-12 PROCESS AND APPARATUS FOR THE PREPARATION OF ANHYDROUS CRYSTALLINE FRUCTOSE.

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FR8507430A FR2582016B1 (en) 1985-05-15 1985-05-15 PROCESS AND PLANT FOR THE PRODUCTION OF ANHYDROUS CRYSTALLIZED FRUCTOSE
FR8507430 1985-05-15

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DE4041317B4 (en) * 1990-01-18 2005-09-08 Xyrofin Oy Process for crystallizing crystal water-free fructose from its aqueous solutions
US5549757A (en) * 1994-06-10 1996-08-27 Ingredient Technology Corporation Process for recrystallizing sugar and product thereof
FR2796310B1 (en) * 1999-07-01 2001-10-19 Rhodia Chimie Sa MULTIFUNCTIONAL SYNTHESIS AND CRYSTALLIZATION PROCESS AND REACTOR
BR0103406A (en) * 2001-08-15 2004-05-04 Getec Guanabara Quimica Ind S Process of producing high purity crystalline fructose using low fructose syrup originating from sucrose and product obtained

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US3513023A (en) * 1966-04-29 1970-05-19 Boehringer Mannheim Gmbh Process for the production of crystalline fructose
CH483272A (en) * 1967-05-02 1969-12-31 Belge Atel Reunies Baking device for continuous crystallization
US3607392A (en) * 1967-12-21 1971-09-21 Boehringer Mannheim Gmbh Process and apparatus for the recovery of crystalline fructose from methanolic solution
FR1597729A (en) * 1968-12-06 1970-06-29
JPS502017B1 (en) * 1969-06-27 1975-01-23
JPS5239901B2 (en) * 1973-02-12 1977-10-07
JPS5012245A (en) * 1973-06-04 1975-02-07
US3981739A (en) * 1974-08-30 1976-09-21 Amstar Corporation Continuous crystallization
US4059460A (en) * 1975-11-07 1977-11-22 A. E. Staley Manufacturing Company Solid anhydrous dextrose
GB2053019B (en) * 1979-07-06 1983-10-26 Zurita H G Heat exchangers for crystallization of crystallizable suspension whilst in motion
FR2555201B1 (en) * 1983-11-17 1986-10-31 Roquette Freres PROCESS AND PLANT FOR PRODUCING CRYSTALLIZED MONOHYDRATE DEXTROSE
JPS60118200A (en) * 1983-11-29 1985-06-25 加藤化学株式会社 Continuous crystallizing method and apparatus of anhydrous crystalline fructose

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ATE42343T1 (en) 1989-05-15
FR2582016A1 (en) 1986-11-21
FI862025A (en) 1986-11-16
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US5015297A (en) 1991-05-14
JPS61268695A (en) 1986-11-28
DE3662915D1 (en) 1989-05-24
FI84082C (en) 1991-10-10
FR2582016B1 (en) 1987-09-18
FI84082B (en) 1991-06-28

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