FI115380B - Viscous liquid compositions of xylitol and a process for their preparation - Google Patents

Abstract

Uncrystallisable or slowly crystallisable viscous liquid xylitol compositions containing 51-80 % xylitol, 0.1-44 % D-arabitol, and 5-48.9 % oligomers or polymers incapable of reducing glucose, these percentages being determined on the basis of the dry compositions. A method for preparing said compositions is also provided. The compositions may be used in cosmetics, pharmaceuticals and confectionery.

Description

115380

Xylitol viscous liquid compositions and process for their preparation

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The present invention relates to viscous liquid compositions of xylitol, as well as to a process for their preparation.

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More specifically, it relates to novel xylitol liquid compositions which are viscous and difficult to crystallize, containing D-arabitol and non-reducing glucose oligomers or polymers. The invention also relates to a process for obtaining compositions which are viscous and difficult to crystallize.

Thick or viscous syrups obtained by hydrolysis followed by hydrogenation of starch, and in particular sorbitol syrup, are widely used in sucrose syrups. as substitutes for gypsum in numerous food or pharmaceutical applications.

• · »·! 20 Although sorbitol is not as sweet as sugar, it does have the advantage over sugar i> · ''. it does not cause tooth decay. Promotes low viscosity of sorbitol- * »<·» *; Effects due to its low molecular weight may in fact be i. ·: ·. with a higher concentration of syrups which in this case are just as viscous and non-crystallizing as sucrose syrups.

:. ·. 25

Due to the inherent wetting properties of polyols, the most soluble t [t. polyols have found use in the cosmetic field. High solubility of sorbitol, ** ·. and its high water retention capacity has led to a very high use of sorbitol syrups as fillers, for example in toothpastes.

! 30 2 115380

Xylitol, which is another polyol, has the advantage that it is practically as sweet as sucrose and, moreover, like sorbitol, it does not cause tooth decay.

However, its low molecular weight, which is even lower than sorbitol, and its low solubility, which at a temperature below 30 ° C is lower than that of sorbitol and sucrose, causes it not to only form sufficiently thick, non-crystalline syrups that could substitute sucrose or sorbitol syrups for food or pharmaceutical applications or, alternatively, sorbitol or glycerol syrups for cosmetic applications.

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However, high viscous liquid compositions of xylitol are described, for example, in European Patent Application No. 431,995. They are viscous and non-crystallizable but contain no more than 50% xylitol, the remainder of the composition being essentially hydrogenated starch hydrolyzate having a high titanium content of mal-15.

Other concentrated liquid formulations of xylitol containing 50 to 90% xylitol, 10 to 50% other polyols and having retarded crystallization are also described in International Patent Application WO92 / 06943. By slow crystallization-20, it is meant that xylitol crystallizes slowly and hard and forms'. microcrystals that are hardly palpable or detectable by concentration; in liquid compositions containing them. These concentrated liquids:. the compositions are truly non-crystallizing only at 20 ° C if they have a xylitol content of less than 70% and a solids content of less than 70%. Under these particular circumstances, these compositions are not particularly; ': Viscose. Furthermore, it is not surprising that xylitol does not crystallize therein, since last,,; this does not appear to be below its solubility limit in this case.

. ·. In these compositions, which contain more xylitol or are more concentrated,. . the slow crystallization of xylitol is caused by other low molecular weight »* · '. The presence of polyols such as sorbitol, maltitol, mannitol and glycerol. It may also be reinforced by other polyols present in the mother liquors of 3,115,380 derived from the crystallization of xylitol obtained by hydrogenation of hydrolysates of wood or corn cob. These polyols present in the mother liquors also have a low molecular weight. They are especially L-arabitol and galactitol. They are always present in concentrated xylitol liquid compositions when these mother liquors 5 are used as a source of xylitol instead of solutions formed by dissolving pure crystalline xylitol and adding sorbitol, mannitol, maltitol, glycerol.

The methods used to prepare these concentrated xylitol liquid compositions are always such that they are added to crude xylitol solutions, such as crystallization mother liquors or mother liquors obtained by recrystallization of crystallized xylitol, low molecular weight polyols such as , mannitol, maltitol or hydrogenated starch hydrolyzate with high maltitol content.

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The use of mother liquors obtained from the hydrogenation and crystallization of hydrolysates of wood or corn cob is much more economically advantageous in the preparation of concentrated liquid compositions of xylitol. This is in fact; allows disposal of the by-product, but its use is limited * »| 20 in food, pharmaceutical and cosmetic applications because of the L-arabitol which '' '. is present in these hydrolysates, is not a natural polyol and because of galactitol; , which is also here, is known to cause cataracts.

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Compositions having a higher viscosity or a concentrated liquid composition of xylitol :. '. 25 non-crystallising or retarded crystallization and not »I»; ''; being L-arabitol and galactitol, so far only use has been possible; of pure crystalline xylitol. These compositions are therefore expensive to produce, because the crystalline xylitol which must be used for their production is itself expensive: the product. In addition, sorbitol, mannitol, maltitol, glycerol and hydrogenated starch hydrolysates with high maltitol content are also expensive products. In addition, these products do not provide the desired viscosity values.

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What is now needed are viscous compositions or concentrated liquid formulations of xylitol which are non-crystallizable or have retarded crystallization that are not hazardous to health and are advantageous to obtain.

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Such compositions have useful uses in the manufacture of toothpaste fillers, cosmetic or pharmaceutical products, and in the manufacture of various confectionery products.

From European Patent No. 421,882, which is to the applicant, it is known to obtain xylitol silicas with 80 to 90% xylitol content, the remainder being essentially D-arabitol, a natural D-series pentitol of sugars. These syrups, which are not very viscous and are particularly well suited for crystallization of xylitol, are obtained by microbiological conversion of glucose to D-arabitol, microbiological oxidation of ΟΙ5 arabol to D-xylulose, enzymatic isomerization of D-xylulose and then D-xylose. by catalytic hydrogenation of a mixture of xylulose and D-xylose to xylitol and D-arabitol. These xylitol syrups, which do not contain L-arabitol or galactitol but only D-i-arabitol as an additional polyol, allow easy extraction of pure xylitol crystals in three yields.

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• «:. ·. In this case, the concentration of D-arabitol reaches up to 50% or orally: 1. in the mother liquors, which time clearly indicates that D-arabitol is not an anti-crystallization agent of xylitol.

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It is therefore due to the Applicant that he has found that combinations of non-reducing high molecular weight glucose oligomers or polymers of D-arabitol. · ·. which are present in these syrups make it possible to prevent crystallization of xylitol. j. its in it. This finding is all the more surprising since the combination is not dependent on the presence of essential amounts of so-called xylitol crystallization agents, such as sorbitol, maltitol, mannitol, glycerol, L-arabitol, or galactitol. all are anti-crystallization agents of low molecular weight mole.

In addition, the presence of non-reducing high molecular weight oligomers or polymers of glucose in these xylitol syrups makes it possible to obtain a certain amount of thickness, even diluted, in these syrups, which is useful in numerous applications.

Non-reducing high molecular weight glucose oligomers or polymers are understood to include: maltotriitol, maltotetraitol and their higher homologues obtained by incomplete hydrolysis of starch followed by hydrogenation of these hydrolysates, as well as the isomers of these compounds.

The viscous liquid xylitol compositions of the invention are therefore known for the fact that they contain: - 51% to 80% xylitol t - 0.1% to 44% D-arabitol. 5% to 48.9% of non-reducing glucose oligomers or polymers.

20 ..: Preferably they include: <· •; - 53% to 75% xylitol: '; ': - 2% -35% D-arabitol - 8% - 45% non-reducing glucose oligomers or polymers.

25 •.,. * Even cheaper, they include: *: '! - 55% - 75% xylitol: -: - 4% - 30% D-arabitol: *: - 10% - 41% non-reducing glucose oligomers or polymers.

·: ··: 30 6 115380

The Applicant Company has further found that the crystallization or solubility limit of pure xylitol in water as a function of temperature can be estimated by the formula: y = 83.2x + 9130 83-x 5 where x is the temperature of xylitol solution in degrees Celsius and y is xylitol solubility limit in grams of xylitol per 100 g of water.

The data calculated from this equation corresponds very well to the measured values of the solubility of xylitol in water as a function of temperature, as can be seen, for example, in si-10 in Vol. 368, " techniques collection, Coordinator JL Multon, Tec and Doc, Lavoisier APRIA, 1992.

Thus, temperatures of 10 °, 20 °, 30 °, 40 °, 50 ° and 60 ° C are related to the measured solubilities of xylitol in 138, 168, 217, 292, 400 and 614 g / 100 cm 3 of water. It happens that the above equation allows the following values to be calculated from the same temperatures: 136.5, 171, 219, 290.402 and 614, thus showing excellent correspondence between theoretical and experimental values in the temperature range 0-70 ° C.

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• · · · '20 The hyperbola representing this equation distinguishes, in the region where it is relevant, the level • ·: to the area below the curve where xylitol is in an unsaturated state and therefore cannot crystallize and to the supersaturated region above the curve and • » t ';;. * where xylitol should normally crystallize.

• * ·. . However, the Applicant has found, after numerous experiments, that the simultaneous presence of xylitol, D-arabitol and non-reducing glucose oligomers or polymers in xylitol solutions also • unexplainedly increases the solubility or crystallization of xylitol. clearly slows down. Therefore, the compositions according to the invention of the invention allow to obtain retarded crystallization properties of xylitol in the range of 1.1 to 1.2 and non-crystallized compositions of supersaturated values in the range of 1.0 to 1.1. At such values, the xylitol concentration limits of the inventive compositions are obtained by multiplying the indexers of the above equation by values of 1.1 or 1.2.

It follows that the preferred liquid compositions of xylitol, which have retarded crystallization properties or do not crystallize at a given temperature, are characterized in that their water content is adjusted so that their xylitol content, expressed in grams of xylitol per 100 g of water, is 83.2x + 9130 and 100x + 11000 10 83 - x 83 - x (x is the temperature of the compositions in degrees Celsius).

Other more preferred concentrated xylitol liquid compositions which do not crystallize at given temperatures are characterized in that their water content is adjusted so that their xylitol content is within the values defined by the following equations: 83.2x + 9130 and 91.5x + 10050 83 - x 83 - x (x is the temperature of the compositions in degrees Celsius).

»· • · t # 20 When it is desired that the xylitol liquid compositions of the invention •«

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.:. have retarded crystallization properties at about 20 ° C, their water content *. ,,. I must be adjusted so that their xylitol content, expressed in grams of xylitol per 100 g of water, is between 188 g and 206 g.

When I want these same compositions not to crystallize at about 20::; ° C, their water content must be adjusted so that their xylitol content, expressed as: - grams of xylitol per 100 g of water is in the range of 171 g to 188 g.

• · «* t: 1 * *; The process for preparing the liquid xylitol liquid compositions of the invention consists in mixing non-reducing glucose oligomers or polymers with xylitol syrups obtained in accordance with European Patent Application No. 8115380421.882. These preferably have a high molecular weight and are preferably derived from hydrogenated dextrins or maltodextrins.

Another method which permits the preparation of the liquid xylitol liquid compositions of the invention is the use of xylose syrups or xylose powders obtained by the fermentation process described in European Patent No. 421,882, with the addition of reducing oligomers or polymers derived from starch hydrolyzates which are low in glucose and maltose, and preferably do not contain these two sugars in the olefin, and finally the mixture is subjected to hydrogenation under conditions known to those skilled in the art. In this case, the amounts of reducing oligomers and polymers that are added are selected such that the liquid compositions obtained contain at least 51% xylitol. It should be noted that the liquid composition obtained using this process is in this case 15 according to the invention because it necessarily contains D-arabitol because the fermentation xylose used contains more or less D-xylulose.

A third method for preparing the liquid xylitol liquid compositions of the invention is to carry out the steps already described in European Patent No. 421,882 of European Patent ..., 20 to microbiologically and chemically convert glucose, but to perform all or part of the fermentation. or enzymatic conversion in the presence of oligomers or polymers of glucose.

The oligomers or polymers of glucose refer to: maltotriose, maltotetrasose and their higher homologues obtained from the imperfect starch. hydrolysis, as well as isomers of these compounds having branched molecules.

Surprisingly, the applicant company found that in the presence of these glucose-reducing oligomers Ii * V * 30 or polymers, the microbiological conversion of the glu- '' 'cosine to D-arabitol and then D-arabitol was not impaired at all. conversion to D-xylulose, that these same oligomers or polymers remained unchanged during these microbiological conversions and did not significantly impair the enzymatic isomerization of D-xylulose to D-xylose. Catalytic hydrogenation of the resulting syrup containing these glucose oligomers and in this case leads to a syrup containing xylitol (derived from D-xylose reduction and half of D-xylulose reduction), D-arabitol (half of which is obtained from D-xylulose reduction) and non-reducing oligomers or polymers of glucose (obtained from their reducing equivalents).

This third method for preparing the liquid compositions of xylitol according to the invention is therefore such that microbiological conversions of glucose to D-arabitol and then to D-xylulose, enzymatic isomerization of D-xylulose to a mixture of D-xulose and D-xylulose and then catalytic hydrolysis of and is characterized in that microbiological conversions, isomerization and hydrogenation occur in the presence of glucose oligomers and / or polymers.

This method is even more advantageous because it is possible in this case to use a single raw material which is really advantageous and which may consist of '1 · ·' mother liquors, for example crystallization of dextrose, containing '···' about 4 to 7%. oligomers or polymers of glucose remaining from enzymatic saccharifications.

• t s »1 M« \ · !. Another raw material that can be used in the process of the invention may be crude starch hydrolyzate derived from acidic liquefaction and its; After 25 by enzymatic saccharization. Such a hydrolyzate is less »1 1 *« t ·, ·, expensive to produce than a double enzymatic hydrolyzate which has a • (high glucose content. In addition, acidic liquefaction, which is used instead of enzymatic ... liquefaction, produces reversible products and branched molecules, * · which avoid subsequent enzymatic saccharification and thus remain in the form of '' '30 high molecular weight oligomers or polymers which prevent crystallization of xylitol and provide viscosity to the compositions.

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To carry out the process of the invention, when the crude starch hydrolyzate obtained from acidic liquefaction is used as the raw material, this liquefaction is generally carried out by heating to about 130-150 ° C 5 starch milk at a concentration of 25-45% in the presence of sufficient hydrochloric acid 5 - 2.0.

This liquefaction is preferably carried out until the DE (dextrose equivalent) is 30 to 50.

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Enzymatic saccharification is then performed on this crude hydrolyzate obtained by the acidic pathway, amyloglucosidase. This saccharization is usually carried out at a temperature of 50-60 ° C for 20-200 hours at pH 5.0-6.0 and a dry matter content of 20-40% using 4000-500000 international units of enzymatic activity per kg of dry matter. agent. Whatever amyloglucosidase may be used, however, the use of fungal myoglucosidase is preferred. Preferably, saccharization is carried out to the end, that is, until a glucose content of 75% to 90% is obtained. The glucose in these syrups • ·); The oligomer or polymer content in this case is generally 5-20%.

• · • · 20

Another raw material that is preferred is the enzymatic hydro-dextrin of dextrin. lysate. In the context of the present invention, the term "dextrins" is understood to mean products obtained by heating a starch which has been adjusted to a low moisture value, usually in the presence of acidic or alkaline catalysts. This star j. ·. The "dry foaming" of 25 lys, most often in the presence of acid, produces both starch and

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. ' * ·. depolymerization of the iris and condensation of the starch fragments thus obtained; it results in the production of highly branched and high molecular weight molecules which are no longer completely hydrolyzable by amyloglu-

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t; t cosidases.

v; 3o 115380 π

When dextrins are used as raw materials in the process of the invention, it is preferable to use dextrins obtained from dry starch roasting in the presence of an acid catalyst such as hydrochloric acid. For example, the acid is sprayed onto the starch and the resulting mixture is pre-dried at 80 to 130 ° C until an aqueous content of 5% or less is obtained. The mixture is then roasted at a temperature of about 140-250 ° C for 30 minutes to about 6 hours to obtain a dextrin with a DE value of about 0.5 to 10 at the end of the reaction. It is possible to use any type of starch, especially corn, wheat, , rice, potato or cassava starch.

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Traditionally, dextrins are classified into two categories: white dextrins, which do not differ greatly in appearance from the raw material used, and yellow dextrins, which are produced under more severe conditions and whose color intensity is related to the natural degree of structural modification. The four reaction types that occur during dextrinization are, at low temperature, hydrolysis of substantially alpha 1-4 bonds and then, at higher temperatures, condensation, transglycosylation, and finally, internal dehydration reactions.

The preferred method of the present invention utilizes white dextrins which are substantially free of internal glucose anhydrides. In addition, the enzymatic hydrolysis of the more converted dextrins. , it would no longer allow the high glucose contents claimed to be>> <

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'I !. 'To provide a xylitol level greater than 51%.

• * ·; . Dextrins, such as those marketed by the applicant company under the trademarks TACKIDEX®, ··· '135, 140, 145, 150, are particularly recommended and may be used as raw materials for the xylitol concentrates of the invention. liquid compositions.,. for others.

In order to carry out the process of the invention, when the dextrins are used as raw materials, they are dissolved in water with a dry matter content of about 20-45%, preferably 12-53,580, so that glucose undergoes at least one saccharification. carisease enzyme such as amyloglucosidase.

Preferably, and although not necessary when only slightly converted dextrin is used, this enzymatic action of amyloglucosidase is preferably preceded by the action of heat-resistant alpha-amylase.

The enzymatic action of amyloglucosidase and, optionally, the action of alpha-amylase on dextrin allows for the generation of a fraction consisting essentially of glucose and one substantially composed of polymers of glucose. These polymer molecules do not undergo the following microbiological and enzymatic steps, but they become non-reducing glucose polymers during the final catalytic hydrogenation. These highly viscosity improving polymers also play a role as crystallization inhibitors for xylitol in the compositions of the invention.

Regardless of which raw material is selected for carrying out the process of the invention, the mother liquors from crystallization of dextrose, crude acid enzyme starch: lyshydrolyzate or saccharified dextrin, are usually diluted ** to 20 g / l and 2 to 4 g / L of organic yeast in the form of corn grain or yeast extract and supplemented with 1 to 3 g / L of KH 2 PO 4 and 1 to 2 g / L of MgSO 4 - 7H 2 O.

The culture medium thus obtained is introduced into a fermentation vessel, then sterilized and inoculated with about 10% of a 24 hour culture of the Pichia microorganism.

t · »'* Pichia ohmeri strain # ATCC 20.209 generally gives good results.

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4 * *

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'·; The fermentation is continued by aeration at a temperature of about 30 ° C for 80-100 v: 30 hours at a pH of about 4.5, preferably maintained with ammonium hydroxide 1 »l *» 13 115380 until substantially all glucose has been converted to D-arabitol.

The entire interior of the fermentation vessel is then sterilized to kill the yeast and then inoculated again, this time with a preculture of Acetobacter suboxydans.

The fermentation is then continued with aeration at 20 to 40 ° C for about 24 to 48 hours at pH 4.0 to 6.0. Thereafter, virtually all D-arabitol is oxidized to D-xylulose. The broth thus obtained is conventionally released from the microorganisms by centrifugation or filtration, then purified in a conventional manner by decolorization treatments, which may be carried out on growth mastic or by demineralization treatments with cationic or anionic resins. It is then generally concentrated to a dry solids content of 40%, which is the optimum value for the subsequent enzyme isomerization reaction.

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It is possible to use for this step, the enzymatic isomerization of xylulose to xylose, a commercial glucose isomerase of the type used for the preparation of very fructose corn syrups, for example, known under the trademark SPEZYME® and marketed in FINLAND; '20 SUGAR or that obtainable under French Patent No. 2,353,562, which is the applicant.

• ·> »I

• ·

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] ''. 'Preferably, the isomerization is carried out at a temperature of 40 to 80 ° C and a pH of preferably 6.0 to 8.5, usually in the presence of an enzyme protecting agent such as sodium. 25 bisulfite and magnesium salt.

In general, isomerization is continued until about 20-75% of D-xylulose> -:> f. is converted to D-xylose. The highest values of isomerization lead to compositions containing little D-arabitol, while lower values of isomerization yielded compositions containing much more D-arabitol. The D-xylose-rich syrup obtained from this enzymatic isomerization, which in this case generally contains 5 to 35% of glucose oligomers or polymers, 25 to 75% of xylulose and 20 to 70% of xylose, is then purified by demineralization and then subjected to catalytic hydrogenation in the presence of Raney nickel or in the presence of catalysts or ruthenium.

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Preferably, the hydrogenation step is carried out in the presence of Raney Nickel Catalyst at a hydrogen pressure of 40 to 70 bar at a temperature of 100 to 150 ° C and a concentration of 20 to 60%.

The hydrogenation is continued until the reducing sugar content of the hydrogenated syrup is less than 2%, preferably less than 1%, and more preferably less than 0.5%.

The hydrogenated syrup thus obtained is filtered to remove the catalyst, then de-mineralized and preferably concentrated to give the compositions of the invention.

EXAMPLE 1: Use of Hydroles a) Conversion of glucose to D-arabitol • · * I · *; To a fermentation vessel with a working capacity of 10 ms is added: ', - 8000 liters of hydrol, corresponding to the mother liquors in dextrose monohydrate. . > crystalline, diluted to give a solution containing 170 g / l of dry substance

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- 16 kg of yeast extract:. 25 - 8kg KH2PO4 - 8 kg MgSO4-7H2O * ·. * · ·, Hydrol's carbohydrate analysis had the following spectrum: * * · _. Glucose 86.1% '. Maltose 9.5% »* * · ·

Maltotriosis (DP3) 2.0% 15 115380

Maltotetraose (DP4) 0.5% DP5 0.3% DP6 0.4% DP7 0.5% DP8 - 20 0.4% DP> 20 nd. about 0.3%

After sterilization of the culture medium and after cooling to 30 ° C, 800 liters of a culture of Pichia Ohmer No. ATCC 20,209, as described in French Patent No. 2,009,331, which was 24 hours old, was inoculated into a fermentation vessel.

Aeration was continued throughout the conversion of glucose from glucose to D-arabitol, i.e., at a flow rate of 130 Nm / hour for 90 hours and the pH was maintained at 4.5 by the addition of ammonium hydroxide.

After this first fermentation, the carbohydrate analysis of the broth was as follows:. . D-arabitol 78.8% - Maltose 14.5% DP3 3.2% DP4 0.8% ':: DP5 0.5% DP6 0.5% ν': DP7 0.8% DP8 - 20 0.5 % • DP> 20 0.4% b) Conversion of D-arabitol to D-xylulose

Mill! 15

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The entire contents of the fermentation vessel were heated for 20 minutes at 120 '*' 'and then, after cooling to 30 ° C, were inoculated with 600 liters

Pre-culture of Acetobacter suboxydans. After 24 hours of fermentation with aeration of 16,113,580 l / v / min, the fermentation was stopped, bacteria and yeast residues were filtered off and decolorization was performed on activated charcoal and demineralized with strong cationic and weak anion-ion exchange resins and then strong cation-strong anionic acid.

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The carbohydrate analysis of the obtained syrup was as follows:

Xylulose 20.0%

Xylose 57.0%

Maltose 15.7% DP> 3 7.3% c) Isomerization of D-xylulose to D-xylose 10 This syrup was concentrated to a dry solids content of 40%, then rinsed through a SPEZYME® trademark glucose isomerase column immobilized at 65 ° C. The pH was adjusted to 7.7 with sodium carbonate and after addition of 0.4 g / l sodium bisulfite and 1 g / l magnesium chloride. This syrup was flushed at a flow rate of 2 volumes syrup per column space at 15 hours per hour.

This isomerization reaction yielded xylol of the following composition: 1 ·: Syrup: · · · · · · · · · · · · · · · · · · ·

Xylose 57.0%

Maltose 15.7% f DP> 3 7.3%, 20 It is therefore observed that the oligomers and polymers of maltose and glucose remained unchanged during all these steps and did not inhibit

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'' microbiological and enzymatic conversion of glucose to D-xylose.

* 1 · 115380 n d) Hydrogenation This xylose-rich syrup was demineralized in a resin mixed bed, then hydrogenated under hydrogen pressure in the presence of 50 bar Raney nickel and at 120 ° C. After 5 hours of hydrogenation, this syrup had a reducing sugar content of less than 0.1%.

This syrup was demineralized and then concentrated to various solids contents. Its dry carbohydrate composition in this case was as follows:

Xylitol 67.0%

Arabitol 10.0%

Milk 16.0%

Glucose Non-Reducing Oligo- and 7.0% Polysaccharides with DP> 3 EXAMPLE 2: Use of Acid / Enzyme Starch Hydrolyzate Starch milk having a dry matter content of 36% was supplemented with 4 g / L technical hydrochloric acid.

15 * .. * It was pumped into a converter annular space consisting of three concentric tubes, the largest and smallest of which were steam-heated to 150 ° C.

The residence time in the converter was adjusted so that the DE value of the glucose syrup was 37.

After cooling to 55 ° C and adjusting to pH 5.0. . per kg of starch was added 0.8% w / w DEXTROZYME® [Trademark Aminoglucosidase from NOVO].

* The saccharification was allowed to proceed for 80 hours, after which the hydrolyzate was obtained, which after purification was as follows: '' 'Glucose 88.3% * Maltose 3.8% 18 115380 DP3 2.0% DP4 1.0% DP5 1.0% DP6 0.8% DP7 0.7% DP8 - 20 2.3% DP> 20 0.1% This hydrolyzate was diluted to a solids content of 170 g / L and was used in all procedures, which are described in Example 1.

5 At the end of all these operations, a xylitol syrup was obtained having the following composition:

Xylitol 70.3% D-arabitol 10.1%

Maltitol 6.3% DP3> 3 13.3% of which DP3 3.4% DP4 1.7% DP5 1.5% dpö 1.4% DP7 1.4% • 7 ···: 'DP8-20 3, 6% DP> 20 0.2%>: EXAMPLE 3: Dextrin Conversion The white dextrin marketed by the applicant as TACKIDEX® 135 was dissolved in hot water with a dry matter content of 30%. The pH of this solution was adjusted to 5.5 and this dextrin solution was thermostated to 55 ° C.

* * »0.8% w / w DEXTROZYME® Trademark Amyloglucosidase • 15 NOVO companies were then added per kg of dextrin.

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The saccharification was allowed to continue for 75 hours, at the end of which the hydrolyzate was obtained having the following carbohydrate spectrum:

Glucose 87.7% DP2 2.2% DP3 0.4% DP4 2.9% DP5 1.7% DP6 - 20 4.0% DP> 20 1.1% 5 This hydrolyzate was diluted to a dry matter content of 170 g / l and was used in all the procedures described in Example 1.

However, enzymatic isomerization was carried out at a flow rate of four volumes of syrup per column volume and per hour to give a syrup having the following composition:

Xylulose 41.8%

Xylose 31.8% DP2 3.7% DP> 20 17.0% •: · ·: After all these procedures, a xylitol syrup was obtained having the following: 23.8% DP2 3.7%. "·! DP3 0.7% DP4 4.9% • 7 DP5 2.9%: / DP6-20 6.7% DP> 20 1.8% where DP> 3 17.0% 15 20 1 1 5380 EXAMPLE 4: Preparation Using Mixtures

The xylitol syrup, which is not particularly viscous and is easily crystallizable, was obtained by fermentation of pure dextrose according to European Patent No. 421,882 and following the procedures described in Example 1, and having the following composition:

Xylitol 87% D-arabitol 12%

The other 1% was mixed with hydrogenated dextrin TACKIDEX® 135 to give the following compositions a and b: 10 Composition a: Xylitol 54.4% D-arabitol 7.5% DP> 3 37.5%

Composition b: Xylitol 79.0% D-arabitol 10.9% 15 DP> 3 9.0% * ·; These formulations were concentrated to various dry solids contents.

: · · I EXAMPLE 5: Comparison 20 v Pure xylitol solutions (c), xylitol solutions with 70% xylitol content and 30% (d) maltitol content and solutions with 70% xylitol content and D-arabito- ,:; additional content 30% (e), prepared. All these solutions were concentrated to various dry solids. * Content.

EXAMPLE 6: Stability of Compositions of the Invention

The liquid xylitol compositions of all Examples 1-5 were concentrated to give a xylitol content of 185 g xylitol per 100 g water, i.e.: - for the compositions of Example 1, a total solids concentration of 73.4% by weight, - for was Example 2, 72.5%, - for Example 3, 76.9%, - for Example 4, composition a, 77.3%, 10 - for Example 4, composition b, 70.1%, 64.9% for solution c in Example 5, 72.5% for compositions d and e in example 5.

Each of these compositions yielded a xylitol content of 185 g xylitol per 100 g water.

At 20 ° C, after six weeks, only compositions c, d and e of Example 5 had crystallized.

· · 20 At 30 ° C, at the end of the same time, no composition crystallized.

* »» * *: At 16 ° C, even after six weeks, all the compositions of Examples 1-2-3 Ii and the compositions of Example 4 a and b contained only small barely detectable microcrystals when compared to the compositions of Example 5. , d; : 25 and e with formation of large xylitol crystals.

rt »· [,; The same liquid compositions of Examples 1-5 were concentrated to give xylitol containers of 310 g xylitol per 100 g water, i.e.: In the compositions of Examples 1, the total solids content was 82.3% by weight. 30 per weight, - in Example 2, 81.5%, 22 115380 - in Example 3, 84.8%, - in the composition of Example 4, 1.85%, - in the composition of Example 4, b, 79.7%, - in the solution c of Example 5, 75.6%, Compositions d and e of Example 5, 81.6%.

In all these compositions, the xylitol content reached 310 g xylitol per 100 g water.

At 40 ° C, after 6 weeks, only compositions c, d and d of Example 5 had crystallized.

At 41 ° C, after the same time, no composition crystallized.

At 37 ° C, even after six weeks, all compositions of Examples 1-2-3 and compositions a and b of Example 4 contained little microcrystalline, whereas in compositions 5, c, d and e of Example 5 there was formation of xylitol crystals.

• 1 * * I · · f · · '·

> · I

. . These examples show that when the xylitol content, expressed in grams per * * · · · · · 100 grams of water in the compositions of the invention is within the range defined by: * * · «83.2x + 9130 and 91.5x 10050 83 - x 83 -x; ·. Where x is the temperature in degrees, in this case, these compositions remain non k · ·> I I ·, · · ·. for crystallization, although xylitol is present in supersaturation.

• · «| t * * * ,,. Similarly, when the xylitol content of the compositions of the invention is within the range defined by the equations:; 30 91.5x + 10050 and 100x 11000 83 -x 83-x 23 115380

In this case, they have retarded crystallization properties.

EXAMPLE 7: Viscosity of Compositions of the Invention The necessary times for a flow of 50 ml of the compositions of the invention were compared to the flow rate of prior art syrups. These flow times are directly proportional to the viscosities of the syrups or compositions. In other words, the longer these times are, the higher the viscosities.

For this purpose, all compositions of Examples 1-5 were adjusted to a solids content of 70% by weight, which is the value where xylitol is below its solubility limit (except for composition 5 of Example 5). 50 ml of each composition is then placed in a 1 cm diameter burette. Flow times were measured using a timer.

15

The following values were obtained at 23 ° C: - Example 1 composition: 811 seconds - Example 2 composition: 798 seconds !!, - Example 3 composition: 823 seconds 20 - Example 4 composition a: 1709 seconds <1 * t «« ·. ,.,: - Example 4 composition b: 529 seconds • · - Example 5 composition c: 346 seconds * * · i ► t ·:: '; - Example 5 composition d: 710 seconds - Example 5 composition e: 340 seconds; (; 25 - pure water for 48 seconds I «(• I · t •; · · * These measurements show that the liquid compositions of the invention are viscous and thicker than prior art syrups.

»♦ * * t ·» *: «« »

Claims (9)

1. Viscous liquid formulations of xylitol, characterized in that they contain: - 51 - 80% xylitol, - 0.1 - 44% D-arabitol, - 5 - 48.9% non-reducing oligomers or polymers of glucose, wherein these percentages are expressed on the basis of the dry weight of the compositions. 2. Viscous liquid compositions of xylitol according to claim 1, which have delayed crystallization properties or which are non-crystallizable at given temperatures, characterized in that their xylitol contents, expressed in grams of xylitol per 100 g of water, are between the values defined by equation 83: , 2x + 9130 and 100x + 11000 83. x 83 - x where x is the temperature in degrees centigrade of the compositions. 3. Viscous liquid formulations of xylitol according to claim 1, which are non-crystallizable at given temperatures, characterized in that their xylitol contents, expressed in grams of xylitol per 100 g of water, are between the values defined by the equations: «83.2 x + 9130 and 91.5x + 10050; 83 -x 83 -x where x is the temperature in degrees centigrade of the compositions. Viscous liquid formulations of xylitol according to claims 1 and 2, which have delayed crystallization properties at 20 ° C, characterized in that their xylitol contents, expressed in grams of xylitol per 100 g of water, are between 188 g and 206. g. 5. Viscous liquid compositions of xylitol according to claims 1 and 3, which are non-crystallizable at 20 ° C, characterized in that their xylitol contents, expressed in grams of xylitol per 100 g of water, are between 171 g and 188 g. A process for preparing concentrated liquid compositions of xylitol according to claims 1 to 5, in which microbiological conversion of glucose to D-arabitol and then D-xylulose, enzymatic isomerization of D-xylolose to a mixture of D-xylose and D xylose and then catalytic hydrogenation of this mixture, characterized in that the microbiological conversions, isomerization and hydrogenation occur in the presence of reducing oligomers and / polymers of glucose. Process according to claim 6, characterized in that the reducing oligomers and / or glucose phase polymers use solutions from the crystallization of dextrose. » Process according to claim 6, characterized in that the reducing oligomers and polymers of glucose are obtained by using starch hydrolysates obtained by acidic liquid formation and after the enzymatic saccharification. 9. A process according to claim 6, characterized in that the reducing oligomers and polymers of glucose are attached using dextrose as an enzymatic saccharification.