EP0797686A1 - Method and apparatus for making a pure simple sugar solution by hydrolysing at least one compound sugar in the presence of a selective adsorbent - Google Patents

Method and apparatus for making a pure simple sugar solution by hydrolysing at least one compound sugar in the presence of a selective adsorbent

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Publication number
EP0797686A1
EP0797686A1 EP95941780A EP95941780A EP0797686A1 EP 0797686 A1 EP0797686 A1 EP 0797686A1 EP 95941780 A EP95941780 A EP 95941780A EP 95941780 A EP95941780 A EP 95941780A EP 0797686 A1 EP0797686 A1 EP 0797686A1
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EP
European Patent Office
Prior art keywords
compound
hydrolysis
microporous
adsorbent
solution
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EP95941780A
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German (de)
French (fr)
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EP0797686B1 (en
Inventor
Germain-Robert Durand
Pierre Faugeras
Françoise LAPORTE
Claude Moreau
Marie-Claude Neau
Gabriel Roux
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EPISUCRES SA
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Agrichimie
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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
    • C13K3/00—Invert sugar; Separation of glucose or fructose from invert sugar
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/06—Glucose; Glucose-containing syrups obtained by saccharification of starch or raw materials containing starch

Definitions

  • the invention relates to a method and an installation for manufacturing a liquid solution of simple sugars (oses) from a liquid solution comprising at least one compound sugar (oside), and in particular a holoside (polysaccharide or oligosaccharide) such as sucrose, inulin, starch ...
  • a holoside polysaccharide or oligosaccharide
  • FR-A-1526 029 describes a process for bleaching juice, syrups, molasses and even sugar drains making it possible to transform all or part of the sucrose comprising a bleaching step by ion exchange resins, with partial hydrolysis or total, a purification and bleaching step using ion exchange resins and a concentration step.
  • the starting materials being very loaded with cations and anions, the resins are quickly saturated, so that this process cannot find practical applications in industry.
  • this process is in several stages, and requires a low entry concentration (20 to 30 brix).
  • the invention aims to overcome these drawbacks by proposing a method and an installation for manufacturing a solution of simple sugars under profitable conditions on an industrial scale.
  • the subject of the invention is therefore a process and an installation which make it possible to obtain, by hydrolysis, simple sugars in solution with a yield, a reaction rate and a purity sufficiently high to envisage their industrial production at a reasonable cost price. and with limited industrial investment.
  • the invention aims to propose a method which can be implemented in installations of small or medium size and capacity.
  • the invention further aims to propose such a method and such an installation compatible with the ecological constraints of respect for the environment, in particular without producing effluents.
  • the invention thus aims to propose a method and an installation for manufacturing simple sugars in a single step, continuously and without solvent for extraction by hydrolysis of a solution of sugar (s) compound (s).
  • the invention also aims to propose a method and an installation for manufacturing a pure solution, in particular colorless, of simple sugars by hydrolysis.
  • the invention aims to propose a process for manufacturing, in a single step and continuously, an aqueous solution of simple sugars of agrifood quality, in particular colorless and more particularly comprising less than 1% of hydrolysis residues other than simple sugars.
  • the invention also aims to propose a method for manufacturing a solution of simple sugars by hydrolysis of a solution of sugar (s) compound (s) having a conversion rate greater than 95% obtained with a reaction time (or residence time) of less than 4 hours.
  • the invention also aims to propose a method and an installation for the manufacture of an aqueous solution of simple sugars by hydrolysis at a temperature above 50 ° C. - in particular of the order of 85 ° C. - of a sugar solution ( s) highly concentrated compound (s) - in particular whose proportion by weight of dry matter is greater than 60% -.
  • the invention more particularly aims to propose a process and an installation for the industrial manufacture of a pure and colorless solution of dares, - in particular of glucose and fructose - by hydrolysis of a solution of polysaccharide (s) and / or d oligosaccharide (s) - in particular starch or sucrose -.
  • the invention relates to a process for manufacturing a solution of simple sugars from a liquid solution comprising at least one compound sugar, by hydrolysis in the presence of a heterogeneous catalysis system (i.e. - say one or more solid catalysts), characterized in that the hydrolysis reaction medium is brought into contact with at least one microporous solid adsorbent compound chosen to be compatible with the hydrolysis and catalysis conditions and for selectively adsorb residues or by-products other than simple sugars under the reaction conditions of hydrolysis.
  • the adsorbent component (s) is (are) chosen so as not to adsorb the starting sugar (s) compound (s).
  • a microporous solid adsorbent compound which can be used in a process according to the invention is a mineral compound of natural or synthetic origin formed by three-dimensional sequences of tetrahedrons T04 with T representing at least two different elements of the periodic classification such as Si, Al, B , Fe, Ga, Ge etc .. In this sequence, the oxygen atoms of the TO4 tetrahedra are in common with the neighboring tetrahedra.
  • a solid microporous adsorbent compound is D a solid with pores generally smaller than about 10 -9 m.
  • an absorbent microporous solid compound is distinguished from macroporous solids (whose pores have dimensions generally greater than 10 ° m) such as resins, and mesoporous solids (whose pores have dimensions generally between 2.10 'm and 10 ° m).
  • the catalysis system and the microporous solid adsorbent compound (s) are chosen so that:
  • the hydrolysis reaction is carried out with a conversion greater than 99% of the sugar (s) compound (s) and with a selectivity in simple sugars greater than 80%, - the compound (s) adsorbent (s) microporous solid (s) is (are) able to adsorb the whole quantity of residues or by-products during the reaction time.
  • microporous solid adsorbent compound (s) which captures the by-products, it is possible to carry out the reaction at high temperature with a high conversion rate and a high initial concentration.
  • in sugar in particular greater than 65 brix, for example of the order of 68 brix. It also follows that the solution obtained is a syrup of high purity in simple sugars, and in particular is colorless.
  • a tectosilicate or a clay in protonic form is used as heterogeneous acid catalyst of the hydrolysis reaction.
  • a catalyst makes it possible to obtain a conversion of the compound sugar greater than 99% in a time less than 2 hours, with an optimal selectivity for simple sugars greater than 80%.
  • Tectosilicates are microporous compounds characterized by a structure comprising: - a three-dimensional framework formed by the sequence of tetrahedrons TO4, Si04, T representing an element of classification such as Al, B, Ga, Ge, ... and,
  • a zeolite (aluminosilicate) in protonic form such as a faujasite Y in form H of Si / Ai ratio between 2 and 100, especially between 10 and 10, is used as the acid catalyst. and 20, advantageously of the order of 15.
  • the heterogeneous catalysis system and the operating conditions are chosen so as to avoid, on the one hand, the formation of products other than simple sugars and, on the other hand, the degradation of these simple sugars, and in particular to minimize or even avoid the formation of HMF (in the case in particular of hexoses, fructose, or polyfructans and dyes).
  • the heterogeneous catalyst can itself have a role of selective adsorbent. However, the catalyst is chosen so that it does not absorb sugars, and in particular, simple sugars.
  • the invention relates in particular to a method of manufacturing a solution comprising at least one hexose from a solution comprising at least one holoside (such as sucrose) hydrolysable into at least one hexose (such as fructose and glucose ).
  • a holoside such as sucrose
  • hexose such as fructose and glucose
  • a microporous solid adsorbent compound a molecular sieve is used, the porosity of which (pore and channel size) is defined to selectively adsorb by-products other than simple sugars and sugar (ies). ) starting compound (s), and in particular for adsorbing the molecules of colored by-products and / or the molecules of HMF.
  • solid microporous adsorbent compound a tectosilicate or a clay, in particular an adsorbent zeolite, or alumina.
  • a microporous solid adsorbent compound which simultaneously acts as catalyst or catalyst support for hydrolysis.
  • the reaction medium is brought into contact with an adsorbent zeolite in particular in protonic form, or in partially calcined ammonium form, which acts both as a heterogeneous acid catalyst, and molecular sieve adsorbing unwanted products such as dyes and HMF.
  • This first variant has the advantage of providing a process in which a solution of simple sugars is obtained in a short time with a single solid compound to be managed.
  • At least one microporous solid adsorbent compound distinct from the heterogeneous catalyst is used.
  • a zeolite in protonic form is used as heterogeneous acid catalyst, and an adsorbent zeolite forming a molecular sieve is used, as a microporous solid adsorbent compound, the acidity of which is low but nevertheless compatible with acid catalysis.
  • This second variant offers the advantage of allowing a separate control of the catalysis of the hydrolysis, and of the adsorption of the dyes or of HMF or other undesirable by-products.
  • the hydrolysis reaction is carried out in a multicontact reactor - in particular a pulsed reaction / extraction column - continuously.
  • At least one microporous solid adsorbent compound preferably preformed, is circulated, in particular in extruded form, circulating against the flow of the reaction medium.
  • the solid microporous adsorbent compound can be regenerated by continuous in particular by calcination after its passage in the reactor, then recycled at the inlet of the reactor.
  • a heterogeneous powder catalyst is used and this catalyst is circulated in a co-current dispersion of the reaction medium in the reactor.
  • the heterogeneous catalyst and the compound (s) adsorbent (s) solid (s) microporous are mixed and this mixture of solids is circulated against the flow of the reaction medium.
  • the proportion by weight of the dry matter in sugar ( ⁇ ) compound (s) can be greater than 60% (syrup of more than 60 brix) - in particular of the order of 65% to 70% (syrup of 65 brix to 70 brix) -.
  • the heterogeneous catalyst is used in an amount of 1% to 20% - in particular of the order of 7.5% - by weight of the dry matter of the starting solution.
  • the microporous solid adsorbent compound is used in an amount of 2% to 40% - in particular of the order of 15% - by weight of the dry matter of the starting solution.
  • a weight of adsorbent compound (when this microporous solid adsorbent compound is distinct from the heterogeneous catalyst) is used which is greater than the weight of the heterogeneous catalyst, in particular of the order of twice the weight of the heterogeneous catalyst.
  • one or more solid microporous adsorbent compounds can be used simultaneously, each of them having defined selective adsorption properties for adsorbing a by-product or a family of by-products. It is possible, for example, to use a microporous solid adsorbent compound capable of adsorbing HMF, and another microporous solid adsorbent compound capable of adsorbing dyes and / or polymers.
  • the ability of a molecular sieve to selectively adsorb a particular product depends on its structure in space, the size of the pores, cages and channels it contains and the physico-chemical affinities. It is known in practice to define, manufacture or choose a solid microporous absorbent compound (molecular sieve) according to the products to be adsorbed selectively.
  • one or more heterogeneous catalysts can be used simultaneously producing distinct effects.
  • the reaction is carried out at a temperature between 60 ° C and 150 ° C - in particular of the order of 80 ° C to 85 ° C -, and catalysts and compound (s) are used microporous solid adsorbent (s) compatible with this temperature.
  • catalysts and compound (s) are used microporous solid adsorbent (s) compatible with this temperature.
  • the tectosilicates resist this temperature range perfectly.
  • the residence time of the reaction medium in the reactor is less than 2 hours and is in particular between 0.5 hour and 1 hour.
  • the starting solution comprises at least one oside chosen from the group formed by inulin (polysaccharide), starch (polysaccharide), sucrose (oligosaccharide), maltose (oligosaccharide), cellobiose ( oligosaccharide) or lactose (oligosaccharide).
  • inulin polysaccharide
  • starch polysaccharide
  • sucrose oligosaccharide
  • maltose oligosaccharide
  • cellobiose oligosaccharide
  • lactose oligosaccharide
  • the invention relates in particular to a process for the manufacture of a colorless solution of dares from starch or / of sucrose in a liquid medium by hydrolysis in the presence of an acidic heterogeneous catalyst.
  • the starting solution (and therefore the reaction medium and the final solution) is an aqueous solution.
  • the invention also relates to an installation for implementing a method according to the invention.
  • An installation according to the invention is characterized in that it comprises at least one reactor and means for bringing a reaction medium for hydrolysis of a liquid solution comprising at least one compound sugar, into contact with a heterogeneous catalysis system hydrolysis and at least one solid microporous absorbent compound.
  • the installation is characterized in that it comprises at least one pulsed column, and means for simultaneously circulating continuously in the pulsed column the liquid hydrolysis reaction medium, the heterogeneous catalysis system of hydrolysis and the microporous solid absorbent compound (s).
  • the installation is characterized in that it comprises means for circulating the absorbent compound (s) solid (s) microporous against the current of the liquid hydrolysis reaction medium.
  • the pulsed column acts not only as a separator, but also and above all as a continuous multicontact reactor.
  • the hydrolysis reaction and the continuous selective extraction of unwanted by-products and impurities (dyes, etc.) are thus carried out simultaneously in the pulsed column, in a single step.
  • the starting sugar solution can be highly concentrated, the reaction time is reduced and the use of toxic or polluting solvents and the discharge of polluting effluents are avoided.
  • the invention also relates to a method and an installation for manufacturing a solution of simple sugars comprising in combination all or part of the characteristics mentioned above or below.
  • FIG. 1 is a diagram illustrating an installation for implementing a method according to a first variant of the invention
  • FIG. 2 is a diagram illustrating an installation for implementing a method according to a second variant of the invention
  • - Figure 3 is a diagram illustrating an installation for implementing a method according to a third variant of the invention.
  • the installation for implementing the manufacturing method according to the invention essentially consists of a pulsed column 1 at the lower part 2 of which a concentrated solution of compound sugar, in particular starch or sucrose.
  • the reaction products namely the solution of simple sugar (s), in particular glucose and fructose, are extracted at the upper part 3 of the pulsed column 1.
  • a heterogeneous catalyst in the form of powder is mixed in a mixer 4 in the solution of compound sugar before introducing it into column 1.
  • This heterogeneous catalyst is an acid catalyst, for example a Y (H) zeolite in powder form.
  • This catalyst dispersed in the compound sugar solution which circulates from bottom to top in column 1 is extracted with the liquid phase in which it is dispersed at the top 3.
  • a filter 5 makes it possible to separate the catalyst from the aqueous solution of sugars simple at the outlet of column 1.
  • the catalyst recovered on filter 5 is recycled to the mixer 4 either directly if it is still active, or after a regeneration step, for example by passing through a calcination oven 6 or any other suitable regeneration device depending on the nature of the catalyst.
  • one or more solid microporous adsorbent compound (s) which circulates (s) by gravity from top to bottom in column 1 are continuously introduced into the upper part 3 of column 1. which is recovered at the lower part 2.
  • the adsorbent compound is for example an extruded zeolite Y (H) shaped (in granules, sticks, cylinders, beads, etc.) forming an adsorbent molecular sieve.
  • the solid microporous adsorbent compound must be compatible with the acid catalyst used for hydrolysis. In particular, it must not neutralize the acidity of the catalyst.
  • the pieces of microporous solid adsorbent compound recovered in the lower part 2 are transported by a device forming a hydraulic elevator to a screen 7 making it possible to isolate the granules and / or cylinders which are then introduced into a calcination oven 8 in which the solid microporous adsorbent compound is regenerated, the products trapped in the pores of this compound being burnt.
  • the microporous solid adsorbent compound can be recycled and reintroduced into the upper part 2 of column 1 continuously.
  • the pulsed columns are known vertical multi-contact devices in which pulsations can be maintained (see for example the document "Pulsed Perforated-Plate Colu ns", DH Logsdail, MJ Slaten, Handbook of Solvent Extraction, Teh C.Lo Malcol HI Baird, Cari Hanson, Krieger Publishing Company, Malabar, Florida, 1991, 11-2, p 335-372, incorporated by reference in the present description).
  • the packing (baskets and crowns, or discs and crowns) as well as the amplitude and frequency of the pulsations are determined to obtain continuous circulation from bottom to top of the reaction medium and the continuous circulation of the solid catalyst (s) and the microporous solid absorbent compound (s).
  • the temperature inside the pulsed column can be maintained at the reaction temperature, in particular between 80 ° and 85 ° C.
  • the weight proportions of the starting solution of sugar (s) compound (s), of catalyst, are adjusted. acid and microporous solid adsorbent compound (s) as indicated above by adjusting the flow rates of the various components and the circulation speed in the pulsed column 1 so that the desired conversion of the sugar (s) (s) compound (s) is obtained at the upper outlet 3 of the pulsed column 1. Thanks to the invention, a total conversion of the compound sugar can be obtained despite a residence time of the reaction medium in the pulsed column 1 which is weak, especially less than two hours.
  • FIG. 2 differs from that of FIG. 1 only in the fact that the heterogeneous acid catalyst is no longer introduced co-current with the starting solution of sugar (s) compound (s), but circulates against -current with the microporous solid adsorbent compound (s).
  • the acid catalyst is then not in powder form, but in the form of granules and / or balls and / or cylinders in order to be able to circulate by gravity through the pulsed column 1 from the upper part 3 to the lower part 2.
  • the heterogeneous acid catalyst is recovered with the microporous solid adsorbent compound in the lower part 2 of the column 1 and transported by hydraulic lift to the sieve 7 which is in this case a double sieve making it possible to separate the balls and / or granules and / or cylinders of acid catalyst of the granules and / or cylinders of microporous solid adsorbent compound.
  • the particle size of the acid catalyst will be different from that of the microporous solid adsorbent compound.
  • the acid catalyst is either directly reintroduced into the upper part 3 of column 1 if it is still active, or regenerated, by example through a calcination oven 6 or other regeneration device, before recycling to the upper part 3.
  • the solid microporous adsorbent compound follows the same circuit as that described with reference to FIG. 1. It should be noted that the acid catalyst heterogeneous can also serve as selective adsorbent of one of one or more residue (s) or byproduct (s) of reaction.
  • the concentrated solution of compound sugar (s) is directly introduced into the lower part 2 and circulates from bottom to top in the pulsed column 1. In the upper part 3, the solution of simple sugars is recovered directly. In this variant, it should be noted that the operations in FIG.
  • FIG. 3 illustrates a variant similar to FIG. 1 in which the microporous solid adsorbent compound and the acid catalyst are formed from one and the same microporous solid adsorbent in proton form.
  • the variant of FIG. 3 differs from that of FIG. 1 only in that the mixer 4, the filter 5 and the regeneration step 6 are omitted. In this variant, a single solid compound circulates in the pulsed column 1.
  • a sucrose syrup comprising 300 g of sucrose, 167.5 g of water and 22.5 g of zeolite Y in proton form, the Si / Al ratio of which is 15, in powder form.
  • sucrose is mixed with the remaining four fifths of the water and with the wet zeolite.
  • This syrup is introduced into a stirred mixer, heated to 82 ° C. The syrup is kept for 25 minutes in this mixer, then the solution is suddenly cooled to 25 ° C.
  • the solution obtained is a glucose and fructose syrup with a conversion rate 95% sucrose.
  • the solution is clear, transparent, but colored yellow.
  • a liquid chromatographic analysis under pressure of HPLC type makes it possible to note the presence of 600 ppm of HMF. This presence is explained by the use of too small a quantity of zeolite whose adsorption power is too low.
  • the syrup is prepared in an identical manner to Example 1 and this syrup is kept in the mixer at 82 ° C. for a period of 40 minutes.
  • the final solution is a solution of glucose and fructose, the sucrose conversion rate being 100%.
  • HPLC chromatographic analysis reveals the presence of 1200 ppm of HMF in the solution.
  • the glucose and fructose solution is clear, transparent, but colored yellow.
  • a sucrose syrup is prepared in an identical manner to Examples 1 and 2 with the 22.5 g of zeolite Y in the proton powder form of Example 1. Then 45 g of adsorbent zeolite Y in partially calcined ammonium (NH4) form, extruded, shaped into cylinders and whose Si / Ai ratio is 15. This zeolite has a binder and is therefore less acidic and less active than the previous one.
  • NH4 partially calcined ammonium
  • this adsorbent zeolite is placed in a sucrose syrup formed from 300 g of sucrose and 167.5 g of water. It can be seen that with the 45 g of the adsorbent zeolite and in the absence of an acidic pulverulent zeolite, the conversion rate of the sucrose into simple sugars is only 60% after a residence time of one hour. Consequently, the adsorbent zeolite plays a weak role of catalyst in the reaction.
  • sucrose syrup is prepared as in Example 3 with 22.5 g of powdery zeolite and 45 g of adsorbent zeolite. Wait 40 minutes instead of the 25 minutes of Example 3, then cool abruptly to 25 ° C. It is found that the syrup obtained from fructose and glucose is perfectly clear, transparent, colorless, stable over several months. The sucrose conversion rate is 100%. HPLC chromatography reveals the presence of 100 to 120 ppm of HMF. The adsorbent zeolite is beige-brown in color.
  • An aqueous starch syrup is prepared comprising 500 g / l of starch, and more than 20 g / l of zeolite Y in protonic form, the Si / Al ratio of which is 15 (Faujasite) as indicated in Example 1.
  • the reaction temperature is 150 ° C and the reaction time is 60 minutes.
  • the final solution is a solution of simple sugars, (the rate of conversion into simple sugars is 100%) of which more than 85% glucose and less than 15% maltose.
  • Maltose is a diholoside composed of two units of D glucose. It is therefore a precursor of glucose which can be recycled in. the hydrolysis starting solution.
  • the invention is also applicable to the hydrolysis of other sugars composed of simple sugars.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
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Abstract

PCT No. PCT/FR95/01615 Sec. 371 Date Jul. 10, 1997 Sec. 102(e) Date Jul. 10, 1997 PCT Filed Dec. 6, 1995 PCT Pub. No. WO96/17962 PCT Pub. Date Jun. 13, 1996A method and an apparatus for making a simple sugar solution from a liquid solution including at least one compound sugar by performing hydrolysis in the presence of a heterogeneous catalyst. The method comprises contacting the hydrolysis reaction medium with at least one microporous solid adsorbent compound selected for compatibility with the hydrolysis and . catalysis conditions and for selectively adsorbing by-products other than simple sugars under the hydrolysis reaction conditions. A pure, colourless, food-grade simple sugar solution is achieved.

Description

PROCEDE ET INSTALLATION DE FABRICATION D'UNE SOLUTION PURE PROCESS AND PLANT FOR MANUFACTURING A PURE SOLUTION
DE SUCRES SIMPLES PAR HYDROLYSE D'AU MOINS UN SUCRE COMPOSESINGLE SUGARS BY HYDROLYSIS OF AT LEAST ONE COMPOUND SUGAR
EN PRESENCE D'UN ADSORBANT SELECTIFIN THE PRESENCE OF A SELECTIVE ADSORBENT
L'invention concerne un procédé et une installation de fabrication d'une solution liquide de sucres simples (oses) à partir d'une solution liquide comprenant au moins un sucre composé (oside), et notamment un holoside (polysaccharide ou oligosaccharide) tel que le saccharose, l'inuline, l'amidon...The invention relates to a method and an installation for manufacturing a liquid solution of simple sugars (oses) from a liquid solution comprising at least one compound sugar (oside), and in particular a holoside (polysaccharide or oligosaccharide) such as sucrose, inulin, starch ...
La réaction d'hydrolyse des sucres composés en milieu liquide, généralement aqueux, en présence d'un catalyseur acide, est connue. Cette réaction, parfois appelée "réaction d'inversion des sucres", permet d'obtenir normalement un "sucre inverti", c'est-à-dire un mélange de sucres simples, et notamment des hexoses. En particulier, si l'on part d'une solution de saccharose, on obtient un sucre inverti formé d'un mélange de fructose et de glucose.The hydrolysis reaction of compound sugars in liquid medium, generally aqueous, in the presence of an acid catalyst, is known. This reaction, sometimes called "sugar inversion reaction", normally makes it possible to obtain an "invert sugar", that is to say a mixture of simple sugars, and in particular hexoses. In particular, if one starts from a sucrose solution, one obtains an invert sugar formed from a mixture of fructose and glucose.
La publication "Les sucres invertis", BUSSIERE et al., IAA Juillet/Août 1990 pages 645 à 649 décrit déjà la réaction d'hydrolyse en présence de résines échangeuses d'ions à titre de catalyseur acide hétérogène. Pour éviter la formation de colorants, on considère jusqu'à maintenant qu'il est préférable d'opérer à basse température (de l'ordre de 30 à 35° C). En particulier, il convient, dans le cas des hexoses, d'éviter la formation de 1 ' hydroxy éthylfurfural (HMF) et de ses dérivés ou produits intermédiaires (polymères, hu ines, acide lévulinique ou for ique... ) . Or, les réactions engendrant la formation du HMF et de ses dérivés sont aussi catalysées en milieu acide et favorisées par une température élevée, notamment supérieure à 50° C. En outre, l'utilisation d'une résine échangeuse d'ions à titre de catalyseur acide interdit les hautes températures. II est à noter à cet égard que si l'on souhaite obtenir effectivement un mélange de sucres simples, il convient de s'assurer que la réaction s'arrête au stade de l'hydrolyse, sans aller jusqu'à la dégradation des sucres et à la formation de produits dérivés tels que les polyols, polymères, acides, HMF...The publication "Les sugres invertis", BUSSIERE et al., IAA July / August 1990 pages 645 to 649 already describes the hydrolysis reaction in the presence of ion exchange resins as heterogeneous acid catalyst. To avoid the formation of dyes, it is considered until now that it is preferable to operate at low temperature (of the order of 30 to 35 ° C). In particular, in the case of hexoses, it is advisable to avoid the formation of hydroxyethylfurfural (HMF) and of its derivatives or intermediate products (polymers, oils, levulinic or formal acid, etc.). However, the reactions causing the formation of HMF and its derivatives are also catalyzed in an acid medium and favored by a high temperature, in particular above 50 ° C. In addition, the use of an ion exchange resin as acid catalyst prohibits high temperatures. It should be noted in this regard that if it is wished to obtain a mixture of simple sugars, it is necessary to ensure that the reaction stops at the hydrolysis stage, without going as far as degradation. sugars and the formation of derivative products such as polyols, polymers, acids, HMF ...
On préfère donc jusqu'à maintenant limiter le taux de conversion du sucre composé pour éviter la formation des sous-produits indésirables. Ainsi, les réactions d'hydrolyse connues ne permettent pas d'obtenir, à des conditions économiquement rentables, des solutions pures de sucres simples intégralement convertis, c'est-à- dire sans sucre composé ni produits dérivés. De plus, aux basses températures utilisées jusqu'à maintenant avec les résines échangeuses d'ions, la conversion du sucre composé est faible et la réaction nécessite un temps considérable, classiquement de l'ordre de 12 heures à 48 heures. En outre, les sucres composés ont, à ces températures, une forte viscosité. Il n'est pas possible en pratique d'utiliser une solution de départ fortement concentrée en sucre composé, et une étape de concentration doit être prévue après l'hydrolyse. Egalement, l'utilisation des résines échangeuses d'ions engendre, du point de vue industriel, de nombreux inconvénients (formation d'effluents, difficultés de régénération, coût de production élevé).Up to now, it is therefore preferred to limit the conversion rate of the compound sugar to avoid the formation of undesirable by-products. Thus, the known hydrolysis reactions do not make it possible to obtain, at economically profitable conditions, pure solutions of simple sugars which are fully converted, that is to say without compound sugar or derived products. In addition, at the low temperatures used until now with ion exchange resins, the conversion of the compound sugar is low and the reaction requires considerable time, conventionally of the order of 12 hours to 48 hours. In addition, the compound sugars have a high viscosity at these temperatures. It is not possible in practice to use a starting solution highly concentrated in compound sugar, and a concentration step must be provided after the hydrolysis. Also, the use of ion exchange resins generates, from the industrial point of view, many drawbacks (formation of effluents, regeneration difficulties, high production cost).
Ainsi, FR-A-1526 029 décrit un procédé de décoloration de jus, sirops, mélasses et même égouts de sucreries permettant de transformer en totalité ou en partie le saccharose comprenant une étape de décoloration par résines échangeuses d'ions, avec hydrolyse partielle ou totale, une étape de purification et décoloration par résines échangeuses d'ions et une étape de concentration. Les produits de départ étant très chargés en cations et anions, les résines sont rapidement saturées, de sorte que ce procédé ne peut pas trouver d'applications pratiques dans l'industrie. En outre, ce procédé est en plusieurs étapes, et nécessite une concentration d'entrée faible (20 à 30 brix) .Thus, FR-A-1526 029 describes a process for bleaching juice, syrups, molasses and even sugar drains making it possible to transform all or part of the sucrose comprising a bleaching step by ion exchange resins, with partial hydrolysis or total, a purification and bleaching step using ion exchange resins and a concentration step. The starting materials being very loaded with cations and anions, the resins are quickly saturated, so that this process cannot find practical applications in industry. In addition, this process is in several stages, and requires a low entry concentration (20 to 30 brix).
Pour toutes ces raisons, les procédés connus tels que celui décrit dans la publication sus-citée, ont connu un développement industriel limité et ne permettent pas de produire des sucres invertis à faible coût.For all these reasons, the known methods such as that described in the abovementioned publication, have experienced limited industrial development and do not allow the production of invert sugars at low cost.
L'invention vise à pallier ces inconvénients en proposant un procédé et une installation de fabrication d'une solution de sucres simples dans des conditions rentables à l'échelle industrielle.The invention aims to overcome these drawbacks by proposing a method and an installation for manufacturing a solution of simple sugars under profitable conditions on an industrial scale.
L'invention a ainsi pour objet un procédé et une installation qui permettent d'obtenir, par hydrolyse, des sucres simples en solution avec un rendement, une vitesse de réaction et une pureté suffisamment élevés pour envisager leur production industrielle à un prix de revient raisonnable et moyennant des investissements industriels limités. En particulier, l'invention vise à proposer un procédé pouvant être mis en oeuvre dans des installations de taille et capacité faibles ou moyennes .The subject of the invention is therefore a process and an installation which make it possible to obtain, by hydrolysis, simple sugars in solution with a yield, a reaction rate and a purity sufficiently high to envisage their industrial production at a reasonable cost price. and with limited industrial investment. In particular, the invention aims to propose a method which can be implemented in installations of small or medium size and capacity.
L'invention vise en outre à proposer un tel procédé et une telle installation compatibles avec les contraintes écologiques de respect de l'environnement, notamment sans production d'effluents.The invention further aims to propose such a method and such an installation compatible with the ecological constraints of respect for the environment, in particular without producing effluents.
L'invention vise ainsi à proposer un procédé et une installation de fabrication de sucres simples en une seule étape, en continu et sans solvant d'extraction par hydrolyse d'une solution de sucre(s) composé(s ) .The invention thus aims to propose a method and an installation for manufacturing simple sugars in a single step, continuously and without solvent for extraction by hydrolysis of a solution of sugar (s) compound (s).
L'invention vise aussi à proposer un procédé et une installation de fabrication d'une solution pure, notamment incolore, de sucres simples par hydrolyse. En particulier, l'invention vise à proposer un procédé de fabrication, en une seule étape et en continu d'une solution aqueuse de sucres simples de qualité agro¬ alimentaire, notamment incolore et plus particulièrement comprenant moins de 1 % de résidus d'hydrolyse autres que des sucres simples.The invention also aims to propose a method and an installation for manufacturing a pure solution, in particular colorless, of simple sugars by hydrolysis. In particular, the invention aims to propose a process for manufacturing, in a single step and continuously, an aqueous solution of simple sugars of agrifood quality, in particular colorless and more particularly comprising less than 1% of hydrolysis residues other than simple sugars.
L'invention vise aussi à proposer un procédé de fabrication d'une solution de sucres simples par hydrolyse d'une solution de sucre(s) composé(s) ayant un taux de conversion supérieur à 95 % obtenu avec une durée de réaction (ou un temps de séjour) inférieure à 4 heures.The invention also aims to propose a method for manufacturing a solution of simple sugars by hydrolysis of a solution of sugar (s) compound (s) having a conversion rate greater than 95% obtained with a reaction time (or residence time) of less than 4 hours.
L'invention vise aussi à proposer un procédé et une installation de fabrication d'une solution aqueuse de sucres simples par hydrolyse à une température supérieure à 50° C -notamment de l'ordre de 85° C- d'une solution de sucre(s) composé(s) fortement concentrée - notamment dont la proportion pondérale de matière sèche est supérieure à 60 %-. L'invention vise plus particulièrement à proposer un procédé et une installation de fabrication industrielle d'une solution pure et incolore d'osés, - notamment de glucose et de fructose- par hydrolyse d'une solution de polysaccharide(s) et/ou d ' oligosaccharide(s) - notamment d'amidon ou de saccharose-.The invention also aims to propose a method and an installation for the manufacture of an aqueous solution of simple sugars by hydrolysis at a temperature above 50 ° C. - in particular of the order of 85 ° C. - of a sugar solution ( s) highly concentrated compound (s) - in particular whose proportion by weight of dry matter is greater than 60% -. The invention more particularly aims to propose a process and an installation for the industrial manufacture of a pure and colorless solution of dares, - in particular of glucose and fructose - by hydrolysis of a solution of polysaccharide (s) and / or d oligosaccharide (s) - in particular starch or sucrose -.
Pour ce faire, l'invention concerne un procédé de fabrication d'une solution de sucres simples à partir d'une solution liquide comprenant au moins un sucre composé, par hydrolyse en présence d'un système de catalyse hétérogène (c'est-à-dire d'un ou plusieurs catalyseurs solides), caractérisé en ce qu'on met le milieu réactionnel d'hydrolyse au contact d'au moins un composé adsorbant solide microporeux choisi pour être compatible avec les conditions d'hydrolyse et de catalyse et pour adsorber sélectivement les résidus ou sous-produits autres que les sucres simples dans les conditions réactionnelles de l'hydrolyse. Selon l'invention, le (les) composant(s) adsorbant(s) est (sont) choisi(s) pour ne pas adsorber le (les) sucre(s) composé(s) de départ. Un composé adsorbant solide microporeux utilisable dans un procédé selon l'invention est un composé minéral d'origine naturelle ou synthétique formé par des enchaînements tridimensionnels de tétraèdres T04 avec T représentant au moins deux éléments différents de la classification périodique tels que Si, Al, B, Fe, Ga, Ge etc.. Dans cet enchaînement, les atomes d'oxygène des tétraèdres TO4 sont en commun avec les tétraèdres voisins.To do this, the invention relates to a process for manufacturing a solution of simple sugars from a liquid solution comprising at least one compound sugar, by hydrolysis in the presence of a heterogeneous catalysis system (i.e. - say one or more solid catalysts), characterized in that the hydrolysis reaction medium is brought into contact with at least one microporous solid adsorbent compound chosen to be compatible with the hydrolysis and catalysis conditions and for selectively adsorb residues or by-products other than simple sugars under the reaction conditions of hydrolysis. According to the invention, the adsorbent component (s) is (are) chosen so as not to adsorb the starting sugar (s) compound (s). A microporous solid adsorbent compound which can be used in a process according to the invention is a mineral compound of natural or synthetic origin formed by three-dimensional sequences of tetrahedrons T04 with T representing at least two different elements of the periodic classification such as Si, Al, B , Fe, Ga, Ge etc .. In this sequence, the oxygen atoms of the TO4 tetrahedra are in common with the neighboring tetrahedra.
Un composé adsorbant solide microporeux est D un solide présentant des pores de dimensions généralement inférieures à environ 10-9 m. A ce titre, il est à noter qu'un composé absorbant solide microporeux se distingue des solides macroporeux (dont les pores ont des dimensions généralement supérieures a 10 ° m) tels que les résines, et des solides mésoporeux (dont les pores ont des dimensions généralement comprises entre 2.10 ' m et 10 ° m).A solid microporous adsorbent compound is D a solid with pores generally smaller than about 10 -9 m. As such, it should be noted that an absorbent microporous solid compound is distinguished from macroporous solids (whose pores have dimensions generally greater than 10 ° m) such as resins, and mesoporous solids (whose pores have dimensions generally between 2.10 'm and 10 ° m).
Selon l'invention, on choisit le système de catalyse et le(les) composé(s) adsorbant(s) solide(s) microporeux de telle sorte que :According to the invention, the catalysis system and the microporous solid adsorbent compound (s) are chosen so that:
- la réaction d'hydrolyse s'effectue avec une conversion supérieure à 99 % du(des) sucre(s) composé(s) et avec une sélectivité en sucres simples supérieure à 80 %, - le(les) composé(s) adsorbant(s) solide(s) microporeux est(sont) apte(s) à adsorber toute la quantité de résidus ou sous-produits pendant la durée de la réaction.- the hydrolysis reaction is carried out with a conversion greater than 99% of the sugar (s) compound (s) and with a selectivity in simple sugars greater than 80%, - the compound (s) adsorbent (s) microporous solid (s) is (are) able to adsorb the whole quantity of residues or by-products during the reaction time.
Grâce au(x) composé(s) adsorbant(s) solide(s) microporeux qui capte(nt) les sous-produits, il est possible d'effectuer la réaction à haute température avec un taux de conversion important et une forte concentration initiale en sucre, notamment supérieurs à 65 brix, par exemple de l'ordre de 68 brix. Il en résulte aussi que la solution obtenue est un sirop d'une grande pureté en sucres simples, et notamment est incolore.Thanks to the microporous solid adsorbent compound (s) which captures the by-products, it is possible to carry out the reaction at high temperature with a high conversion rate and a high initial concentration. in sugar, in particular greater than 65 brix, for example of the order of 68 brix. It also follows that the solution obtained is a syrup of high purity in simple sugars, and in particular is colorless.
Il en résulte aussi que le temps de séjour est bref et que l'installation de mise en oeuvre est peu volumineuse et simple. Selon une autre caractéristique de l'invention, on utilise un tectosilicate ou une argile sous forme protonique à titre de catalyseur hétérogène acide de la réaction d'hydrolyse. On constate en effet, qu'un tel catalyseur permet d'obtenir une conversion du sucre composé supérieure à 99 % en un temps inférieur à 2 h, avec une sélectivité optimale en sucres simples supérieure à 80 %.It also results therefrom that the residence time is short and that the installation for installation is not bulky and simple. According to another characteristic of the invention, a tectosilicate or a clay in protonic form is used as heterogeneous acid catalyst of the hydrolysis reaction. In fact, it is found that such a catalyst makes it possible to obtain a conversion of the compound sugar greater than 99% in a time less than 2 hours, with an optimal selectivity for simple sugars greater than 80%.
Les tectosilicates sont des composés microporeux caractérisés par une structure comportant : - une charpente tridimensionnelle formée par l'enchaînement de tétraèdres TO4, SiÛ4, T représentant un élément de classification tel que Al, B, Ga, Ge, ... et,Tectosilicates are microporous compounds characterized by a structure comprising: - a three-dimensional framework formed by the sequence of tetrahedrons TO4, Si04, T representing an element of classification such as Al, B, Ga, Ge, ... and,
- un réseau monodimensionnel, bidimensionnel, ou tridimensionnel de canaux et cavités de dimensions moléculaires contenant des cations de compensation éventuels, de l'eau ou d'autres molécules ou sels.- a one-dimensional, two-dimensional, or three-dimensional network of molecular-size channels and cavities containing possible compensation cations, water or other molecules or salts.
En particulier, et selon l'invention, on utilise, à titre de catalyseur acide, une zéolithe (aluminosilicate) sous forme protonique, telle qu'une faujasite Y sous forme H de rapport Si/Ai compris entre 2 et 100, notamment entre 10 et 20, avantageusement de 1 ' ordre de 15. On choisit le système de catalyse hétérogène et les conditions opératoires (concentrations, température... ) de façon à éviter, d'une part, la formation d'autres produits que les sucres simples et, d'autre part, la dégradation de ces sucres simples, et notamment pour minimiser, voire éviter la formation du HMF (dans le cas notamment des hexoses, du fructose, ou des polyfructanes et de colorants). Le catalyseur hétérogène peut lui-même avoir un rôle d' adsorbant sélectif. Néanmoins, on choisit le catalyseur de telle sorte qu'il n'adsorbe pas les sucres, et notamment, les sucres simples.In particular, and according to the invention, a zeolite (aluminosilicate) in protonic form, such as a faujasite Y in form H of Si / Ai ratio between 2 and 100, especially between 10 and 10, is used as the acid catalyst. and 20, advantageously of the order of 15. The heterogeneous catalysis system and the operating conditions (concentrations, temperature, etc.) are chosen so as to avoid, on the one hand, the formation of products other than simple sugars and, on the other hand, the degradation of these simple sugars, and in particular to minimize or even avoid the formation of HMF (in the case in particular of hexoses, fructose, or polyfructans and dyes). The heterogeneous catalyst can itself have a role of selective adsorbent. However, the catalyst is chosen so that it does not absorb sugars, and in particular, simple sugars.
L'invention concerne en particulier un procédé de fabrication d'une solution comprenant au moins un hexose à partir d'une solution comprenant au moins un holoside (tel que le saccharose) hydrolysable en au moins un hexose (tel que le fructose et le glucose). Selon l'invention, on utilise à titre de composé adsorbant solide microporeux un tamis moléculaire dont la porosité (dimension des pores et des canaux) est définie pour adsorber sélectivement les sous-produits autres que les sucres simples et le (les) sucre(s) composé(s) de départ, et notamment pour adsorber les molécules de sous-produits colorés et/ou les molécules de HMF.The invention relates in particular to a method of manufacturing a solution comprising at least one hexose from a solution comprising at least one holoside (such as sucrose) hydrolysable into at least one hexose (such as fructose and glucose ). According to the invention, as a microporous solid adsorbent compound, a molecular sieve is used, the porosity of which (pore and channel size) is defined to selectively adsorb by-products other than simple sugars and sugar (ies). ) starting compound (s), and in particular for adsorbing the molecules of colored by-products and / or the molecules of HMF.
Selon l'invention, on utilise, à titre de composé adsorbant solide microporeux, un tectosilicate ou une argile, notamment une zéolithe adsorbante, ou de 1 ' alumine .According to the invention, use is made, as solid microporous adsorbent compound, a tectosilicate or a clay, in particular an adsorbent zeolite, or alumina.
Dans une première variante, avantageusement, et selon l'invention, on utilise un composé adsorbant solide microporeux faisant simultanément office de catalyseur ou de support de catalyseur pour l'hydrolyse. En particulier, dans cette variante, et selon l'invention, on met le milieu réactionnel au contact d'une zéolithe adsorbante notamment sous forme protonique, ou sous forme ammonium partiellement calcinée, qui fait office à la fois de catalyseur acide hétérogène, et de tamis moléculaire adsorbant les produits indésirables tels que les colorants et le HMF. Cette première variante présente 1 ' avantage de procurer un procédé dans lequel on obtient une solution de sucres simples en peu de temps avec un seul composé solide à gérer.In a first variant, advantageously, and according to the invention, a microporous solid adsorbent compound is used which simultaneously acts as catalyst or catalyst support for hydrolysis. In particular, in this variant, and according to the invention, the reaction medium is brought into contact with an adsorbent zeolite in particular in protonic form, or in partially calcined ammonium form, which acts both as a heterogeneous acid catalyst, and molecular sieve adsorbing unwanted products such as dyes and HMF. This first variant has the advantage of providing a process in which a solution of simple sugars is obtained in a short time with a single solid compound to be managed.
Dans une deuxième variante, avantageusement et selon l'invention, on utilise au moins un composé adsorbant solide microporeux distinct du catalyseur hétérogène. Par exemple, on utilise une zéolithe sous forme protonique à titre de catalyseur hétérogène acide, et on utilise, à titre de composé adsorbant solide microporeux, une zéolithe adsorbante formant tamis moléculaire dont l'acidité est faible mais néanmoins compatible avec la catalyse acide. Cette deuxième variante offre l'avantage de permettre un contrôle distinct de la catalyse de l'hydrolyse, et de 1 ' adsorption des colorants ou du HMF ou autres sous-produits indésirables. Selon une autre caractéristique de l'invention, on effectue la réaction d'hydrolyse dans un réacteur multicontact -notamment une colonne puisée de réaction/extraction- en continu.In a second variant, advantageously and according to the invention, at least one microporous solid adsorbent compound distinct from the heterogeneous catalyst is used. For example, a zeolite in protonic form is used as heterogeneous acid catalyst, and an adsorbent zeolite forming a molecular sieve is used, as a microporous solid adsorbent compound, the acidity of which is low but nevertheless compatible with acid catalysis. This second variant offers the advantage of allowing a separate control of the catalysis of the hydrolysis, and of the adsorption of the dyes or of HMF or other undesirable by-products. According to another characteristic of the invention, the hydrolysis reaction is carried out in a multicontact reactor - in particular a pulsed reaction / extraction column - continuously.
Selon l'invention, on fait circuler au moins un composé adsorbant solide microporeux, de préférence préformé, notamment sous forme extrudée, circulant à contre-courant du milieu réactionnel. Le composé adsorbant solide microporeux peut être régénéré en continu notamment par calcination après son passage dans le réacteur, puis recyclé à l'entrée du réacteur. En outre, avantageusement et selon l'invention, on utilise un catalyseur hétérogène en poudre et on fait circuler ce catalyseur en dispersion à co-courant du milieu réactionnel dans le réacteur.According to the invention, at least one microporous solid adsorbent compound, preferably preformed, is circulated, in particular in extruded form, circulating against the flow of the reaction medium. The solid microporous adsorbent compound can be regenerated by continuous in particular by calcination after its passage in the reactor, then recycled at the inlet of the reactor. In addition, advantageously and according to the invention, a heterogeneous powder catalyst is used and this catalyst is circulated in a co-current dispersion of the reaction medium in the reactor.
En variante, avantageusement et selon l'invention, on mélange le catalyseur hétérogène et le (les) composé(s) adsorbant(s) solide(s) microporeux et on fait circuler ce mélange de solides à contre-courant du milieu réactionnel.As a variant, advantageously and according to the invention, the heterogeneous catalyst and the compound (s) adsorbent (s) solid (s) microporous are mixed and this mixture of solids is circulated against the flow of the reaction medium.
Selon l'invention, on utilise une solution de départ fortement concentrée en sucre(s) composé(s). Selon l'invention, la proportion pondérale de la matière sèche en sucre(ε) composé(s) peut être supérieure à 60 % (sirop de plus de 60 brix) -notamment de l'ordre de 65 % à 70 % (sirop de 65 brix à 70 brix)-.According to the invention, a starting solution highly concentrated in sugar (s) compound (s) is used. According to the invention, the proportion by weight of the dry matter in sugar (ε) compound (s) can be greater than 60% (syrup of more than 60 brix) - in particular of the order of 65% to 70% (syrup of 65 brix to 70 brix) -.
Selon l'invention, on utilise le catalyseur hétérogène à raison de 1 % à 20 % -notamment de l'ordre de 7, 5 %- en poids de la matière sèche de la solution de départ. Avantageusement, on utilise le composé adsorbant solide microporeux à raison de 2 % à 40 % -notamment de l'ordre de 15 %- en poids de la matière sèche de la solution de départ. Ainsi, selon l'invention, on utilise un poids de composé adsorbant (lorsque ce composé adsorbant solide microporeux est distinct du catalyseur hétérogène) supérieur au poids du catalyseur hétérogène, -notamment de l'ordre du double du poids du catalyseur hétérogène-.According to the invention, the heterogeneous catalyst is used in an amount of 1% to 20% - in particular of the order of 7.5% - by weight of the dry matter of the starting solution. Advantageously, the microporous solid adsorbent compound is used in an amount of 2% to 40% - in particular of the order of 15% - by weight of the dry matter of the starting solution. Thus, according to the invention, a weight of adsorbent compound (when this microporous solid adsorbent compound is distinct from the heterogeneous catalyst) is used which is greater than the weight of the heterogeneous catalyst, in particular of the order of twice the weight of the heterogeneous catalyst.
Il est à noter que l'on peut utiliser un ou plusieurs composés adsorbants solides microporeux simultanément, chacun d'entre eux ayant des propriétés d'adsorption sélective définies pour adsorber un sous- produit ou une famille de sous-produits. On peut par exemple utiliser un composé adsorbant solide microporeux apte à adsorber le HMF, et un autre composé adsorbant solide microporeux apte à adsorber des colorants et/ou des polymères. L'aptitude d'un tamis moléculaire à -adsorber sélectivement tel ou tel produit dépend de sa structure dans l'espace, de la dimension des pores, cages et canaux qu'il renferme et des affinités physico-chimiques. On sait en pratique définir, fabriquer ou choisir un composé absorbant solide microporeux (tamis moléculaire) en fonction des produits à adsorber sélectivement.It should be noted that one or more solid microporous adsorbent compounds can be used simultaneously, each of them having defined selective adsorption properties for adsorbing a by-product or a family of by-products. It is possible, for example, to use a microporous solid adsorbent compound capable of adsorbing HMF, and another microporous solid adsorbent compound capable of adsorbing dyes and / or polymers. The ability of a molecular sieve to selectively adsorb a particular product depends on its structure in space, the size of the pores, cages and channels it contains and the physico-chemical affinities. It is known in practice to define, manufacture or choose a solid microporous absorbent compound (molecular sieve) according to the products to be adsorbed selectively.
Egalement, on peut utiliser un ou plusieurs catalyseurs hétérogènes simultanément produisant des effets distincts. En particulier, on peut utiliser des catalyseurs qui présentent des vitesses d'épuisement distinctes, et/ou des catalyseurs favorisant des réactions subséquentes de l'hydrolyse, par exemple 1 ' isomérisation du glucose en fructose...Also, one or more heterogeneous catalysts can be used simultaneously producing distinct effects. In particular, it is possible to use catalysts which have distinct depletion rates, and / or catalysts promoting subsequent reactions of hydrolysis, for example the isomerization of glucose into fructose ...
Selon l'invention, on effectue la réaction à une température comprise entre 60° C et 150° C -notamment de l'ordre de 80° C à 85° C-, et on utilise des catalyseur(s ) et composé(s) adsorbant(s) solides microporeux compatibles avec cette température. Il est à noter en particulier que les tectosilicates résistent parfaitement à cette gamme de température. En pratique, on constate que l'on peut obtenir, dans un procédé selon l'invention une conversion totale du (des) sucre(s) composé(s) en sucres simples en moins de deux heures. Ainsi, selon l'invention, le temps de séjour du milieu réactionnel dans le réacteur est inférieur à 2 heures et est notamment compris entre 0,5 heure et 1 heure .According to the invention, the reaction is carried out at a temperature between 60 ° C and 150 ° C - in particular of the order of 80 ° C to 85 ° C -, and catalysts and compound (s) are used microporous solid adsorbent (s) compatible with this temperature. It should be noted in particular that the tectosilicates resist this temperature range perfectly. In practice, it can be seen that, in a process according to the invention, it is possible to obtain a total conversion of the sugar (s) compound (s) into simple sugars in less than two hours. Thus, according to the invention, the residence time of the reaction medium in the reactor is less than 2 hours and is in particular between 0.5 hour and 1 hour.
Selon l'invention, la solution de départ comporte au moins un oside choisi dans le groupe formé de l'inuline (polysaccharide) , de l'amidon (polysaccharide) , du saccharose (oligosaccharide) , du maltose (oligosaccharide) , du cellobiose (oligosaccharide) ou du lactose (oligosaccharide).According to the invention, the starting solution comprises at least one oside chosen from the group formed by inulin (polysaccharide), starch (polysaccharide), sucrose (oligosaccharide), maltose (oligosaccharide), cellobiose ( oligosaccharide) or lactose (oligosaccharide).
L'invention concerne en particulier un procédé de fabrication d'une solution incolore d'osés à partir d'amidon ou/de saccharose en milieu liquide par hydrolyse en présence d'un catalyseur hétérogène acide.The invention relates in particular to a process for the manufacture of a colorless solution of dares from starch or / of sucrose in a liquid medium by hydrolysis in the presence of an acidic heterogeneous catalyst.
Selon l'invention et avantageusement, la solution de départ (et donc le milieu réactionnel et la solution finale) est une solution aqueuse.According to the invention and advantageously, the starting solution (and therefore the reaction medium and the final solution) is an aqueous solution.
L'invention concerne aussi une installation de mise en oeuvre d'un procédé selon l'invention. Une installation selon l'invention est caractérisée en ce qu'elle comporte au moins un réacteur et des moyens pour mettre un milieu réactionnel d'hydrolyse d'une solution liquide comprenant au moins un sucre composé, au contact d'un système de catalyse hétérogène d'hydrolyse et d'au moins un composé absorbant solide microporeux. Selon l'invention, l'installation est caractérisée en ce qu'elle comporte au moins une colonne puisée, et des moyens pour faire circuler simultanément en continu dans la colonne puisée le milieu réactionnel liquide d'hydrolyse, le système de catalyse hétérogène d'hydrolyse et le (les) composé(s) absorbant(s) solide (s) microporeux.The invention also relates to an installation for implementing a method according to the invention. An installation according to the invention is characterized in that it comprises at least one reactor and means for bringing a reaction medium for hydrolysis of a liquid solution comprising at least one compound sugar, into contact with a heterogeneous catalysis system hydrolysis and at least one solid microporous absorbent compound. According to the invention, the installation is characterized in that it comprises at least one pulsed column, and means for simultaneously circulating continuously in the pulsed column the liquid hydrolysis reaction medium, the heterogeneous catalysis system of hydrolysis and the microporous solid absorbent compound (s).
Avantageusement et selon l'invention, l'installation est caractérisée en ce qu'elle comporte des moyens pour faire circuler le (les) composés absorbant(s) solide(s) microporeux à contre-courant du milieu réactionnel liquide d'hydrolyse.Advantageously and according to the invention, the installation is characterized in that it comprises means for circulating the absorbent compound (s) solid (s) microporous against the current of the liquid hydrolysis reaction medium.
Il est à noter que dans un procédé et une installation selon l'invention, la colonne puisée fait office non pas uniquement de séparateur, mais également et surtout de réacteur multicontact continu. On réalise ainsi simultanément dans la colonne puisée, en une seule étape, la réaction d'hydrolyse et l'extraction sélective en continu des sous-produits et impuretés indésirables (colorants, ... ). En outre, grâce à l'invention , la solution sucrée de départ peut être fortement concentrée, la durée de réaction est réduite et on évite l'emploi de solvants toxiques ou polluants et le rejet d'effluents polluants .It should be noted that in a method and an installation according to the invention, the pulsed column acts not only as a separator, but also and above all as a continuous multicontact reactor. The hydrolysis reaction and the continuous selective extraction of unwanted by-products and impurities (dyes, etc.) are thus carried out simultaneously in the pulsed column, in a single step. In addition, thanks to the invention, the starting sugar solution can be highly concentrated, the reaction time is reduced and the use of toxic or polluting solvents and the discharge of polluting effluents are avoided.
Il est à noter à cet égard que les caractéristiques combinées de l'invention permettent l'obtention de ce résultat par le fait qu'il est possible d'opérer avec des sirops concentrés (Brix supérieur à 65) à haute température, avec une faible durée de réaction, les conditions réactionnelles déplaçant l'équilibre fortement.It should be noted in this regard that the combined characteristics of the invention allow this result to be obtained by the fact that it is possible to operate with concentrated syrups (Brix greater than 65) at high temperature, with a low reaction time, reaction conditions shifting the balance strongly.
L'invention concerne aussi un procédé et une installation de fabrication d'une solution de sucres simples comprenant en combinaison tout ou partie des caractéristiques mentionnées ci-dessus ou ci-après.The invention also relates to a method and an installation for manufacturing a solution of simple sugars comprising in combination all or part of the characteristics mentioned above or below.
D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description suivante se référant aux figures annexées dans lesquelles :Other characteristics and advantages of the invention will appear on reading the following description referring to the appended figures in which:
- la figure 1 est un schéma illustrant une installation de mise en oeuvre d'un procédé selon une première variante de l'invention,FIG. 1 is a diagram illustrating an installation for implementing a method according to a first variant of the invention,
- la figure 2 est un schéma illustrant une installation de mise en oeuvre d'un procédé selon une deuxième variante de l'invention, - la figure 3 est un schéma illustrant une installation de mise en oeuvre d'un procédé selon une troisième variante de l'invention.- Figure 2 is a diagram illustrating an installation for implementing a method according to a second variant of the invention, - Figure 3 is a diagram illustrating an installation for implementing a method according to a third variant of the invention.
Sur la figure 1, l'installation de mise en oeuvre du procédé de fabrication selon l'invention se compose essentiellement d'une colonne puisée 1 à la partie inférieure 2 de laquelle on introduit une solution concentrée de sucre composé, notamment d'amidon ou de saccharose. On extrait à la partie supérieure 3 de la colonne puisée 1 des produits de réaction, à savoir la solution de sucre(s) simple(s), notamment de glucose et de fructose .In FIG. 1, the installation for implementing the manufacturing method according to the invention essentially consists of a pulsed column 1 at the lower part 2 of which a concentrated solution of compound sugar, in particular starch or sucrose. The reaction products, namely the solution of simple sugar (s), in particular glucose and fructose, are extracted at the upper part 3 of the pulsed column 1.
Pour réaliser l'hydrolyse dans cette colonne puisée, on mélange dans un mélangeur 4, un catalyseur hétérogène sous forme de poudre dans la solution de sucre composé avant de l'introduire dans la colonne 1. Ce catalyseur hétérogène est un catalyseur acide, par exemple une zéolithe Y(H) sous forme pulvérulente. Ce catalyseur dispersé dans la solution de sucre composé qui circule de bas en haut dans la colonne 1 est extrait avec la phase liquide dans laquelle il est dispersé à la partie supérieure 3. Un filtre 5 permet de séparer le catalyseur de la solution aqueuse de sucres simples à la sortie de la colonne 1. Le catalyseur récupéré sur le filtre 5 est recyclé dans le mélangeur 4 soit directement s'il est encore actif, soit après une étape de régénération par exemple par passage dans un four de calcination 6 ou tout autre dispositif de régénération approprié selon la nature du catalyseur.To carry out the hydrolysis in this pulsed column, a heterogeneous catalyst in the form of powder is mixed in a mixer 4 in the solution of compound sugar before introducing it into column 1. This heterogeneous catalyst is an acid catalyst, for example a Y (H) zeolite in powder form. This catalyst dispersed in the compound sugar solution which circulates from bottom to top in column 1 is extracted with the liquid phase in which it is dispersed at the top 3. A filter 5 makes it possible to separate the catalyst from the aqueous solution of sugars simple at the outlet of column 1. The catalyst recovered on filter 5 is recycled to the mixer 4 either directly if it is still active, or after a regeneration step, for example by passing through a calcination oven 6 or any other suitable regeneration device depending on the nature of the catalyst.
En outre, on introduit en continu, à la partie supérieure 3 de la colonne 1 , un ou plusieurs composé(s) adsorbant(s) solide(s) microporeux qui circule(nt) par gravité de haut en bas dans la colonne 1 et que l'on récupère à la partie inférieure 2. Le composé adsorbant est par exemple une zéolithe Y(H) extrudée mise en forme (en granulés, bâtonnets, cylindres, billes, ... ) formant tamis moléculaire adsorbant. Le composé adsorbant solide microporeux doit être compatible avec le catalyseur acide utilisé pour l'hydrolyse. En particulier, il ne doit pas neutraliser l'acidité du catalyseur. Les morceaux de composé adsorbant solide microporeux récupérés en partie inférieure 2, sont transportés par un dispositif formant ascenseur hydraulique jusqu'à un tamis 7 permettant d'isoler les granulés et/ou cylindres qui sont ensuite introduits dans un four de calcination 8 dans lequel le composé adsorbant solide microporeux est régénéré, les produits piégés dans les pores de ce composé étant brûlés. A la sortie du four 8, le composé adsorbant solide microporeux peut être recyclé et réintroduit à la partie supérieure 2 de la colonne 1 en continu.In addition, one or more solid microporous adsorbent compound (s) which circulates (s) by gravity from top to bottom in column 1 are continuously introduced into the upper part 3 of column 1. which is recovered at the lower part 2. The adsorbent compound is for example an extruded zeolite Y (H) shaped (in granules, sticks, cylinders, beads, etc.) forming an adsorbent molecular sieve. The solid microporous adsorbent compound must be compatible with the acid catalyst used for hydrolysis. In particular, it must not neutralize the acidity of the catalyst. The pieces of microporous solid adsorbent compound recovered in the lower part 2 are transported by a device forming a hydraulic elevator to a screen 7 making it possible to isolate the granules and / or cylinders which are then introduced into a calcination oven 8 in which the solid microporous adsorbent compound is regenerated, the products trapped in the pores of this compound being burnt. On leaving the oven 8, the microporous solid adsorbent compound can be recycled and reintroduced into the upper part 2 of column 1 continuously.
Les colonnes puisées sont des dispositifs connus multicontacts verticaux dans lesquels on peut entretenir des pulsations (cf par exemple le document "Pulsed Perforated-Plate Colu ns", D.H. Logsdail, M.J. Slaten, Handbook of Solvent Extraction, Teh C.Lo Malcol H.I. Baird, Cari Hanson, Krieger Publishing Company, Malabar, Florida, 1991, 11-2, p 335-372, incorporé par référence à la présente description). Le garnissage (paniers et couronnes, ou disques et couronnes) ainsi que l'amplitude et la fréquence des pulsations sont déterminés pour obtenir la circulation continue de bas en haut du milieu réactionnel et la circulation continue du (des) catalyseur(s) solides (s) et du (des) composé(s) absorbant(s) solide(s) microporeux.The pulsed columns are known vertical multi-contact devices in which pulsations can be maintained (see for example the document "Pulsed Perforated-Plate Colu ns", DH Logsdail, MJ Slaten, Handbook of Solvent Extraction, Teh C.Lo Malcol HI Baird, Cari Hanson, Krieger Publishing Company, Malabar, Florida, 1991, 11-2, p 335-372, incorporated by reference in the present description). The packing (baskets and crowns, or discs and crowns) as well as the amplitude and frequency of the pulsations are determined to obtain continuous circulation from bottom to top of the reaction medium and the continuous circulation of the solid catalyst (s) and the microporous solid absorbent compound (s).
Il est à noter qu'une telle installation est excessivement simple dans son principe et sa mise en oeuvre. La température à l'intérieur de la colonne puisée peut être maintenue à la température de réaction, notamment entre 80° et 85° C. On ajuste les proportions pondérales de la solution de départ de sucre(s) composé(s), de catalyseur acide et de composé(s) adsorbant(s) solide(s) microporeux comme indiqué ci-dessus en réglant les débits des différents composants et la vitesse de circulation dans la colonne 1 puisée de telle sorte que la conversion souhaitée du (des) sucre(s) composé(s) soit obtenue à la sortie 3 supérieure de la colonne puisée 1. Grâce à l'invention, une conversion totale du sucre composé peut être obtenue malgré un temps de séjour du milieu réactionnel dans la colonne puisée 1 qui est faible, notamment inférieur à deux heures.It should be noted that such an installation is excessively simple in principle and in its implementation. The temperature inside the pulsed column can be maintained at the reaction temperature, in particular between 80 ° and 85 ° C. The weight proportions of the starting solution of sugar (s) compound (s), of catalyst, are adjusted. acid and microporous solid adsorbent compound (s) as indicated above by adjusting the flow rates of the various components and the circulation speed in the pulsed column 1 so that the desired conversion of the sugar (s) (s) compound (s) is obtained at the upper outlet 3 of the pulsed column 1. Thanks to the invention, a total conversion of the compound sugar can be obtained despite a residence time of the reaction medium in the pulsed column 1 which is weak, especially less than two hours.
La variante de la figure 2 diffère de celle de la figure 1 uniquement dans le fait que le catalyseur acide hétérogène n'est plus introduit à co-courant avec la solution de départ de sucre(s) composé(s), mais circule à contre-courant avec le(les) composé(s) adsorbant(s) solide(s) microporeux. Le catalyseur acide se présente alors non pas sous forme pulvérulente, mais sous forme de granulés et/ou de billes et/ou de cylindres pour pouvoir circuler par gravité à travers la colonne puisée 1 de la partie supérieure 3 à la partie inférieure 2. Le catalyseur acide hétérogène est récupéré avec le composé adsorbant solide microporeux à la partie inférieure 2 de la colonne 1 et transporté par ascenseur hydraulique vers le tamis 7 qui est dans ce cas un tamis double permettant de séparer les billes et/ou granulés et/ou cylindres de catalyseur acide des granulés et/ou cylindres de composé adsorbant solide microporeux. Pour ce faire, la granulométrie du catalyseur acide sera différente de celle du composé adsorbant solide microporeux. A la sortie du tamis 7, le catalyseur acide est soit directement réintroduit à la partie supérieure 3 de la colonne 1 s'il est encore actif, soit régénéré, par exemple à travers un four de calcination 6 ou autre dispositif de régénération, avant son recyclage à la partie supérieure 3. Le composé adsorbant solide microporeux suit le même circuit que celui décrit en référence à la figure 1. Il est à noter que le catalyseur acide hétérogène peut aussi faire office d1adsorbant sélectif d'un ou plusieurs résidu(s) ou sous-produit(s) de réaction. La solution concentrée de sucre(s) composé(s) est directement introduite à la partie inférieure 2 et circule de bas en haut dans la colonne puisée 1. A la partie supérieure 3, on récupère la solution de sucres simples directement. Dans cette variante, il est à noter que les opérations de la figure 1 de mélange dans le mélangeur 4 et de filtration dans le filtre 5 sont supprimées. La figure 3 illustre une variante similaire à la figure 1 dans laquelle le composé adsorbant solide microporeux et le catalyseur acide sont formés d'un seul et même solide microporeux adsorbant sous forme protonique. On peut par exemple utiliser une zéolithe adsorbante Y sous forme protonique extrudee. La variante de la figure 3 se distingue de celle de la figure 1 uniquement par le fait que le mélangeur 4, le filtre 5 et l'étape de régénération 6 sont supprimés. Dans cette variante, un seul composé solide circule dans la colonne puisée 1. EXEMPLE 1 :The variant of FIG. 2 differs from that of FIG. 1 only in the fact that the heterogeneous acid catalyst is no longer introduced co-current with the starting solution of sugar (s) compound (s), but circulates against -current with the microporous solid adsorbent compound (s). The acid catalyst is then not in powder form, but in the form of granules and / or balls and / or cylinders in order to be able to circulate by gravity through the pulsed column 1 from the upper part 3 to the lower part 2. The heterogeneous acid catalyst is recovered with the microporous solid adsorbent compound in the lower part 2 of the column 1 and transported by hydraulic lift to the sieve 7 which is in this case a double sieve making it possible to separate the balls and / or granules and / or cylinders of acid catalyst of the granules and / or cylinders of microporous solid adsorbent compound. To do this, the particle size of the acid catalyst will be different from that of the microporous solid adsorbent compound. At the outlet of the sieve 7, the acid catalyst is either directly reintroduced into the upper part 3 of column 1 if it is still active, or regenerated, by example through a calcination oven 6 or other regeneration device, before recycling to the upper part 3. The solid microporous adsorbent compound follows the same circuit as that described with reference to FIG. 1. It should be noted that the acid catalyst heterogeneous can also serve as selective adsorbent of one of one or more residue (s) or byproduct (s) of reaction. The concentrated solution of compound sugar (s) is directly introduced into the lower part 2 and circulates from bottom to top in the pulsed column 1. In the upper part 3, the solution of simple sugars is recovered directly. In this variant, it should be noted that the operations in FIG. 1 of mixing in the mixer 4 and of filtration in the filter 5 are eliminated. FIG. 3 illustrates a variant similar to FIG. 1 in which the microporous solid adsorbent compound and the acid catalyst are formed from one and the same microporous solid adsorbent in proton form. One can for example use an adsorbent zeolite Y in extruded proton form. The variant of FIG. 3 differs from that of FIG. 1 only in that the mixer 4, the filter 5 and the regeneration step 6 are omitted. In this variant, a single solid compound circulates in the pulsed column 1. EXAMPLE 1:
On prépare un sirop de saccharose comprenant 300 g de saccharose, 167,5 g d'eau et 22,5 g de zéolithe Y sous forme protonique dont le rapport Si/Ai est de 15, sous forme pulvérulente. Pour préparer ce sirop, on mouille un cinquième de l'eau avec la poudre de zéolithe, puis on mélange le saccharose avec les quatre cinquièmes restants de l'eau et avec la zéolithe mouillée.A sucrose syrup is prepared comprising 300 g of sucrose, 167.5 g of water and 22.5 g of zeolite Y in proton form, the Si / Al ratio of which is 15, in powder form. To prepare this syrup, one fifth of the water is wetted with the zeolite powder, then the sucrose is mixed with the remaining four fifths of the water and with the wet zeolite.
On introduit ce sirop dans un mélangeur agité, chauffé à 82° C. On maintient le sirop 25 minutes dans ce mélangeur, puis on refroidit brutalement la solution à 25° C.This syrup is introduced into a stirred mixer, heated to 82 ° C. The syrup is kept for 25 minutes in this mixer, then the solution is suddenly cooled to 25 ° C.
On constate que la solution obtenue est un sirop de glucose et de fructose avec un taux de conversion du saccharose de 95 %. La solution est limpide, transparente, mais colorée jaune.It is found that the solution obtained is a glucose and fructose syrup with a conversion rate 95% sucrose. The solution is clear, transparent, but colored yellow.
Une analyse chromatographique liquide sous pression de type HPLC permet de constater la présence 600 ppm de HMF. Cette présence s'explique par l'utilisation d'une quantité trop faible de zéolithe dont le pouvoir d'adsorption est trop faible.A liquid chromatographic analysis under pressure of HPLC type makes it possible to note the presence of 600 ppm of HMF. This presence is explained by the use of too small a quantity of zeolite whose adsorption power is too low.
EXEMPLE 2 :EXAMPLE 2:
On prépare le sirop de façon identique à l'exemple 1 et l'on maintient ce sirop dans le mélangeur à 82° C pendant une durée de 40 minutes.The syrup is prepared in an identical manner to Example 1 and this syrup is kept in the mixer at 82 ° C. for a period of 40 minutes.
On constate que la solution finale est une solution de glucose et de fructose, le taux de conversion du saccharose étant de 100 % . L'analyse chromatographique HPLC révèle la présence de 1 200 ppm de HMF dans la solution. La solution de glucose et de fructose est limpide, transparente, mais colorée jaune.It is found that the final solution is a solution of glucose and fructose, the sucrose conversion rate being 100%. HPLC chromatographic analysis reveals the presence of 1200 ppm of HMF in the solution. The glucose and fructose solution is clear, transparent, but colored yellow.
EXEMPLE 3 :EXAMPLE 3:
On prépare un sirop de saccharose de façon identique aux exemples 1 et 2 avec les 22,5 g de la zéolithe Y sous forme protonique en poudre de l'exemple 1. On ajoute ensuite dans le mélangeur chauffé à 82° C, 45 g de zéolithe adsorbante Y sous forme ammonium (NH4) partiellement calcinée, extrudee, mise en forme de cylindres et dont le rapport Si/Ai est 15. Cette zéolithe comporte un liant et est donc moins acide et moins active que la précédente.A sucrose syrup is prepared in an identical manner to Examples 1 and 2 with the 22.5 g of zeolite Y in the proton powder form of Example 1. Then 45 g of adsorbent zeolite Y in partially calcined ammonium (NH4) form, extruded, shaped into cylinders and whose Si / Ai ratio is 15. This zeolite has a binder and is therefore less acidic and less active than the previous one.
Après 25 minutes de séjour dans le mélangeur, on refroidit brutalement à 25° C et on analyse la solution finale. On constate que le taux de conversion est de 95 %. La solution finale est un sirop de glucose et de fructose parfaitement limpide, transparent, incolore et qui reste stable pendant plusieurs mois. La chromatographie liquide HPLC révèle la présence de 60 ppm de HMF, correspondant à une pureté alimentaire. On constate par contre que la zéolithe adsorbante extrudee est colorée beige-brun.After 25 minutes of stay in the mixer, the mixture is suddenly cooled to 25 ° C. and the final solution is analyzed. It can be seen that the conversion rate is 95%. The final solution is a perfectly clear, transparent, colorless glucose and fructose syrup that remains stable for several months. HPLC liquid chromatography reveals the presence of 60 ppm of HMF, corresponding to food purity. On the other hand, it is found that the extruded adsorbent zeolite is beige-brown in color.
Simultanément à cette manipulation, on étudie l'activité de la zéolithe adsorbante à titre de catalyseur de l'hydrolyse par une manipulation séparée. Pour ce faire, on place cette zéolithe adsorbante dans un sirop de saccharose formé de 300 g de saccharose et de 167,5 g d'eau. On constate qu'avec les 45 g de la zéolithe adsorbante et en l'absence de zéolithe pulvérulente acide, le taux de conversion du saccharose en sucres simples n'est que de 60 % après un temps de séjour d'une heure. En conséquence, la zéolithe adsorbante joue un faible rôle de catalyseur dans la réaction.Simultaneously with this manipulation, we studies the activity of the adsorbent zeolite as a catalyst for hydrolysis by separate manipulation. To do this, this adsorbent zeolite is placed in a sucrose syrup formed from 300 g of sucrose and 167.5 g of water. It can be seen that with the 45 g of the adsorbent zeolite and in the absence of an acidic pulverulent zeolite, the conversion rate of the sucrose into simple sugars is only 60% after a residence time of one hour. Consequently, the adsorbent zeolite plays a weak role of catalyst in the reaction.
EXEMPLE 4 :EXAMPLE 4:
On prépare le même sirop de saccharose que dans l'exemple 3 avec 22,5 g de zéolithe pulvérulente et 45 g de zéolithe adsorbante. On attend 40 minutes au lieu des 25 minutes de l'exemple 3, puis on refroidit brutalement à 25° C. On constate que le sirop obtenu de fructose et glucose est parfaitement limpide, transparent, incolore, stable sur plusieurs mois. Le taux de conversion du saccharose est de 100 % . La chromatographie HPLC révèle la présence de 100 à 120 ppm de HMF. La zéolithe adsorbante est colorée beige-brun.The same sucrose syrup is prepared as in Example 3 with 22.5 g of powdery zeolite and 45 g of adsorbent zeolite. Wait 40 minutes instead of the 25 minutes of Example 3, then cool abruptly to 25 ° C. It is found that the syrup obtained from fructose and glucose is perfectly clear, transparent, colorless, stable over several months. The sucrose conversion rate is 100%. HPLC chromatography reveals the presence of 100 to 120 ppm of HMF. The adsorbent zeolite is beige-brown in color.
Les exemples 3 et 4 démontrent qu'avec un temps de séjour compris entre 25 minutes et 40 minutes, on obtient, dans un réacteur discontinu, un conversion du saccharose de 95 à 100 % en glucose et fructose avec une pureté alimentaire. Les réactions des exemples ci-dessus peuvent être effectuées en continu dans les installations représentées aux figures avec des temps de séjour encore plus faibles. EXEMPLE 5 :Examples 3 and 4 demonstrate that with a residence time of between 25 minutes and 40 minutes, a conversion of the sucrose from 95 to 100% into glucose and fructose with food purity is obtained in a batch reactor. The reactions of the above examples can be carried out continuously in the installations shown in the figures with even shorter residence times. EXAMPLE 5:
On prépare un sirop acqueux d'amidon comprenant 500 g/1 d'amidon, et plus de 20 g/1 de zéolithe Y sous forme protonique dont le rapport Si/Ai est de 15 (Faujasite) comme indiqué dans l'exemple 1. La température de réaction est de 150 ° c et le temps de réaction est de 60 minutes.An aqueous starch syrup is prepared comprising 500 g / l of starch, and more than 20 g / l of zeolite Y in protonic form, the Si / Al ratio of which is 15 (Faujasite) as indicated in Example 1. The reaction temperature is 150 ° C and the reaction time is 60 minutes.
On constate que la solution finale est une solution de sucres simples, (le taux de conversion en sucres simples est de 100 %) dont plus de 85 % de glucose et moins de 15% de maltose. Le maltose est un diholoside composé de deux unités de D glucose. C'est donc un précurseur du glucose qui peut être recyclé dans . la solution de départ d'hydrolyse.It can be seen that the final solution is a solution of simple sugars, (the rate of conversion into simple sugars is 100%) of which more than 85% glucose and less than 15% maltose. Maltose is a diholoside composed of two units of D glucose. It is therefore a precursor of glucose which can be recycled in. the hydrolysis starting solution.
L'invention est aussi applicable à l'hydrolyse d'autre sucres composés en sucres simples. The invention is also applicable to the hydrolysis of other sugars composed of simple sugars.

Claims

REVENDICATIONS
1/ - Procédé de fabrication d'une solution de sucres simples à partir d'une solution liquide comprenant au moins un sucre composé, par hydrolyse en présence d'un système de catalyse hétérogène, caractérisé en ce qu'on met le milieu réactionnel d'hydrolyse au contact d'au moins un composé adsorbant solide microporeux choisi pour être compatible avec les conditions d'hydrolyse et de catalyse et pour adsorber sélectivement les résidus ou sous-produits autres que les sucres simples dans les conditions réactionnelles de l'hydrolyse.1 / - Process for manufacturing a solution of simple sugars from a liquid solution comprising at least one compound sugar, by hydrolysis in the presence of a heterogeneous catalysis system, characterized in that the reaction medium is put into action. hydrolysis in contact with at least one microporous solid adsorbent compound chosen to be compatible with the hydrolysis and catalysis conditions and to selectively adsorb residues or by-products other than simple sugars under the reaction conditions of hydrolysis.
2/ - Procédé selon la revendication 1 de fabrication d'une solution comprenant au moins un hexose à partir d'une solution comprenant au moins un holoside hydrolysable en au moins un hexose, caractérisé en ce qu'on utilise, à titre de composé adsorbant solide microporeux, un tamis moléculaire apte à adsorber les molécules d'hydroxyméthylfurfural et/ou de sous-produits colorés. 3/ - Procédé selon l'une des revendications2 / - Method according to claim 1 for manufacturing a solution comprising at least one hexose from a solution comprising at least one hydrolyzable holoside into at least one hexose, characterized in that one uses, as adsorbent compound microporous solid, a molecular sieve capable of adsorbing molecules of hydroxymethylfurfural and / or colored by-products. 3 / - Method according to one of claims
1 et 2, caractérisé en ce qu'on choisit le système de catalyse et le(s) composé(s) adsorbant(s) solide(s) microporeux (s) de telle sorte que :1 and 2, characterized in that the catalysis system and the microporous solid adsorbent compound (s) are chosen so that:
- la réaction d'hydrolyse s'effectue avec une conversion supérieure à 99 % du(des) sucre(s) composé(s) et avec une sélectivité en sucres simples supérieure à 80 %,the hydrolysis reaction is carried out with a conversion greater than 99% of the sugar (s) compound (s) and with a selectivity for simple sugars greater than 80%,
- le(s) composé(s) adsorbant(s) solide(s) microporeux est(sont) apte(s) à adsorber toute la quantité de résidus ou sous-produits pendant la durée de la réaction.- the microporous solid adsorbent compound (s) is (are) capable of adsorbing the entire quantity of residues or by-products during the duration of the reaction.
4/ - Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on utilise un tectosilicate ou une argile à titre composé adsorbant solide microporeux. 5/ - Procédé selon la revendication 4, caractérisé en ce qu'on utilise une zéolithe adsorbante à titre de composé adsorbant solide microporeux. 6/ - Procédé selon la revendication 5, caractérisé en ce que la zéolithe adsorbante est sous forme ammonium. 1 - Procédé selon l'une des revendications4 / - Method according to one of claims 1 to 3, characterized in that a tectosilicate or a clay is used as microporous solid adsorbent compound. 5 / - Process according to claim 4, characterized in that an adsorbent zeolite is used as a solid microporous adsorbent compound. 6 / - Process according to claim 5, characterized in that the adsorbent zeolite is in ammonium form. 1 - Method according to one of claims
1 à 6, caractérisé en ce qu'on utilise un catalyseur faisant aussi office de composé adsorbant solide microporeux.1 to 6, characterized in that a catalyst is used which also acts as a microporous solid adsorbent compound.
8/ - Procédé selon l'une des revendications 1 à 6, caractérisé en ce qu'on utilise un composé adsorbant solide microporeux distinct du catalyseur hétérogène.8 / - Method according to one of claims 1 to 6, characterized in that one uses a microporous solid adsorbent compound distinct from the heterogeneous catalyst.
9/ - Procédé selon la revendication 8 et l'une des revendications 1 à 21 , caractérisé en ce qu'on utilise un poids de composé adsorbant solide microporeux supérieur au poids de catalyseur hétérogène, -notamment de l'ordre du double du poids du catalyseur hétérogène-.9 / - Process according to claim 8 and one of claims 1 to 21, characterized in that a weight of microporous solid adsorbent compound is used which is greater than the weight of heterogeneous catalyst, in particular of the order of twice the weight of heterogeneous catalyst.
10/ - Procédé selon l'une des revendications 1 à 9, caractérisé en ce qu'on choisit le catalyseur hétérogène et les conditions opératoires de façon à minimiser la formation de 1 'hydroxymethylfurfural et/ou de sous-produits colorants.10 / - Method according to one of claims 1 to 9, characterized in that one chooses the heterogeneous catalyst and the operating conditions so as to minimize the formation of one hydroxymethylfurfural and / or coloring by-products.
11/ - Procédé selon l'une des revendications 1 à 10, caractérisé en ce qu'on utilise un tectosilicate ou une argile sous forme protonique à titre de catalyseur hétérogène.11 / - Method according to one of claims 1 to 10, characterized in that a tectosilicate or a clay in protonic form is used as heterogeneous catalyst.
12/ - Procédé selon la revendication 11, caractérisé en ce qu'on utilise, à titre de catalyseur hétérogène, une zéolithe sous forme protonique de rapport Si/Ai compris entre 2 et 100. 13/ - Procédé selon la revendication 11, caractérisé en ce qu'on utilise une faujasite Y sous forme H.12 / - Process according to claim 11, characterized in that, as heterogeneous catalyst, a zeolite in protonic form with an Si / Ai ratio of between 2 and 100 is used. 13 / - Process according to claim 11, characterized in what we use a faujasite Y in form H.
14/ - Procédé selon l'une des revendications 12 et 13, caractérisé en ce qu'on utilise une zéolithe sous forme protonique de rapport Si/Ai compris entre 10 et 20, notamment de l'ordre de 15.14 / - Method according to one of claims 12 and 13, characterized in that a zeolite in proton form with an Si / Ai ratio between 10 and 20, in particular of the order of 15, is used.
15/ - Procédé selon l'une des revendications 1 à 14, caractérisé en ce qu'on réalise l'hydrolyse dans un réacteur multicontact -notamment une colonne puisée (1) de réaction/extraction- en continu, et en ce qu'on fait circuler le (les) composé(s) adsorbant(s) solide(s) microporeux à contre-courant du milieu réactionnel.15 / - Method according to one of claims 1 to 14, characterized in that one realizes hydrolysis in a multicontact reactor - in particular a pulsed reaction / extraction column (1) continuously, and in that the microporous solid adsorbent compound (s) is circulated against -current of the reaction medium.
16/ - Procédé selon la revendication 15, caractérisé en ce qu'en utilise un composé solide préformé notamment sous forme extrudee, circulant à contre-courant, à titre de composé adsorbant solide microporeux. 17/ - Procédé selon l'une des revendications 15 et 16, caractérisé en ce qu'on régénère le composé adsorbant solide microporeux après son passage dans le réacteur (1 ) et en ce qu'on le recycle à l'entrée du réacteur. 18/ - Procédé selon l'une des revendications 15 à 17, caractérisé en ce qu'on utilise un catalyseur hétérogène en poudre et en ce qu'on fait circuler ce catalyseur en dispersion à co-courant du milieu réactionnel . 19/ - Procédé selon la revendication 8 et l'une des revendications 15 à 18, caractérisé en ce qu'on mélange un catalyseur hétérogène et le (les) composé(s) adsorbant(s) solide(s) microporeux, et en ce qu'on fait circuler le mélange à contre-courant du milieu réactionnel. 20/ - Procédé selon l'une des revendications 1 à 19, caractérisé en ce qu'on utilise une solution de départ dont la proportion pondérale de la matière sèche en sucre(s) composé(s) est supérieure à 60 % -notamment de l'ordre de 65 % à 70 %-. 21/ - Procédé selon l'une des revendications 1 à 20, caractérisé en ce qu'on utilise le catalyseur hétérogène à raison de 1 % à 20 % -notamment de l'ordre de 7,5 %- en poids de la matière sèche de la solution de départ. 22/ - Procédé selon l'une des revendications 1 à 21 , caractérisé en ce qu'on utilise le composé adsorbant solide microporeux à raison de 2 % à 40 % -notamment de l'ordre de 15 %- en poids de la matière sèche de la solution de départ.16 / - Process according to claim 15, characterized in that it uses a preformed solid compound in particular in extruded form, flowing against the current, as a microporous solid adsorbent compound. 17 / - Method according to one of claims 15 and 16, characterized in that the microporous solid adsorbent compound is regenerated after its passage through the reactor (1) and in that it is recycled at the inlet of the reactor. 18 / - Method according to one of claims 15 to 17, characterized in that a heterogeneous powder catalyst is used and in that this catalyst is circulated in a co-current dispersion of the reaction medium. 19 / - Process according to claim 8 and one of claims 15 to 18, characterized in that a heterogeneous catalyst and the compound (s) adsorbent (s) solid (s) microporous, and in that that the mixture is circulated against the flow of the reaction medium. 20 / - Method according to one of claims 1 to 19, characterized in that a starting solution is used whose weight proportion of the dry matter in sugar (s) compound (s) is greater than 60% -in particular of from 65% to 70% -. 21 / - Method according to one of claims 1 to 20, characterized in that the heterogeneous catalyst is used at a rate of 1% to 20% - in particular of the order of 7.5% - by weight of the dry matter of the starting solution. 22 / - Method according to one of claims 1 to 21, characterized in that the microporous solid adsorbent compound is used at a rate of 2% to 40% - in particular of the order of 15% - by weight of the dry matter of the starting solution.
23/ - Procédé selon l'une des revendications 1 à 22, caractérisé en ce qu'on effectue la réaction à une température comprise entre 60° C et 150° C - notamment de l'ordre de 80° C à 85° C- et en ce qu'on utilise des catalyseur(s) et composé(s) adsorbant(s) solide(s) microporeux compatible(s) avec cette température.23 / - Method according to one of claims 1 to 22, characterized in that the reaction is carried out at a temperature between 60 ° C and 150 ° C - in particular of the order of 80 ° C to 85 ° C- and in that using catalyst (s) and compound (s) adsorbent (s) solid (s) microporous compatible (s) with this temperature.
24/ - Procédé selon la revendication 14 et l'une des revendications 1 à 23, caractérisé en ce que le temps de séjour du milieu réactionnel dans le réacteur (1) est inférieur à 2 heures -notamment est compris entre 0,5 heure et 1 heure-.24 / - Process according to claim 14 and one of claims 1 to 23, characterized in that the residence time of the reaction medium in the reactor (1) is less than 2 hours - in particular is between 0.5 hour and 1 hour-.
25/ - Procédé selon l'une des revendications 1 à 24 caractérisé en ce que la solution de départ comporte au moins un oside choisi dans le groupe formé de l'inuline, l'amidon, le saccharose, le maltose, le cellobiose ou le lactose.25 / - Method according to one of claims 1 to 24 characterized in that the starting solution comprises at least one oside chosen from the group formed by inulin, starch, sucrose, maltose, cellobiose or lactose.
26/ - Installation pour la mise en oeuvre d'un procédé selon l'une des revendications 1 à 25, caractérisée en ce qu'elle comporte au moins un réacteur (1), et des moyens pour mettre un milieu réactionnel d'hydrolyse d'une solution liquide comprenant au moins un sucre composé au contact d'un système de catalyse hétérogène d'hydrolyse et d'au moins un composé absorbant solide microporeux.26 / - Installation for the implementation of a method according to one of claims 1 to 25, characterized in that it comprises at least one reactor (1), and means for putting a hydrolysis reaction medium d a liquid solution comprising at least one sugar compound in contact with a heterogeneous hydrolysis catalysis system and at least one absorbent solid microporous compound.
27/ - Installation selon la revendication27 / - Installation according to claim
26, caractérisée en ce qu'elle comporte au moins une colonne puisée ( 1 ) et des moyens pour faire circuler simultanément en continu dans la colonne puisée ( 1 ) le milieu réactionnel liquide d'hydrolyse, le système de catalyse hétérogène d'hydrolyse et le (les) composés absorbant(s) solide(s) microporeux.26, characterized in that it comprises at least one pulsed column (1) and means for simultaneously circulating continuously in the pulsed column (1) the liquid hydrolysis reaction medium, the heterogeneous hydrolysis catalysis system and the microporous solid absorbent compound (s).
28/ - Installation selon la revendication28 / - Installation according to claim
27, caractérisée en ce qu'elle comporte des moyens pour faire circuler le (les) composés absorbant(s) solide(s) microporeux à contre-courant du milieu réactionnel liquide d'hydrolyse. 27, characterized in that it comprises means for circulating the microporous solid absorbent compound (s) against the current of the liquid hydrolysis reaction medium.
EP95941780A 1994-12-07 1995-12-06 Method and apparatus for making a pure simple sugar solution by hydrolysing at least one compound sugar in the presence of a selective adsorbent Expired - Lifetime EP0797686B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9414961 1994-12-07
FR9414961A FR2727980A1 (en) 1994-12-07 1994-12-07 PROCESS FOR MANUFACTURING A PURE SOLUTION OF SINGLE SUGARS BY HYDROLYSIS OF AT LEAST ONE COMPOUND SUGAR IN THE PRESENCE OF A SELECTIVE ADSORBANT
PCT/FR1995/001615 WO1996017962A1 (en) 1994-12-07 1995-12-06 Method and apparatus for making a pure simple sugar solution by hydrolysing at least one compound sugar in the presence of a selective adsorbent

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NL1001956C2 (en) * 1995-12-21 1997-06-24 Suiker Unie Process for the preparation of purified inulin.
ITMI20031679A1 (en) * 2003-08-29 2005-02-28 Opocrin Spa PROCESS FOR THE PRODUCTION OF LOW WEIGHT EPARINES
WO2008097878A2 (en) 2007-02-05 2008-08-14 Tate & Lyle Ingredients Americas, Inc. Improved sucrose inversion process
US20210015127A1 (en) * 2017-11-28 2021-01-21 Blue Tree Technologies Ltd. Methods and systems for producing low sugar beverages

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US118523A (en) * 1871-08-29 Improvement in the preparation of fermentable saccharine matters
GB240253A (en) * 1924-07-09 1925-10-01 Karel Urban Improvements in the purification of sugar solutions
US2332758A (en) * 1941-05-28 1943-10-26 American Maize Prod Co Method of making starch conversion products
DE1136676B (en) * 1957-03-21 1962-09-20 Usines De Melle S A Process for the continuous implementation of catalytic reactions in the liquid phase
FR1526029A (en) * 1967-03-09 1968-05-24 Process for obtaining a concentrated syrup, for and colorless of sucrose and invert suere, more particularly from low sugar products
US3963788A (en) * 1974-08-20 1976-06-15 Kruse Walter M Polyhydric alcohol production using ruthenium zeolite catalyst
GB1516435A (en) * 1976-06-08 1978-07-05 Toray Industries Separating fructose from a mixture of sugars
US4746368A (en) * 1986-02-28 1988-05-24 Akzo America Inc. Decolorization of aqueous saccharide solutions and sorbents therefor
FI88933C (en) * 1990-10-15 1993-07-26 Xyrofin Oy Procedure for the production of glucose and fructose by sucrose
FR2697023B1 (en) * 1992-10-16 1994-12-30 Roquette Freres Low-calorie glucose soluble polymer and process for the preparation of this polymer.

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FR2727980A1 (en) 1996-06-14
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