DE1935330A1 - Prepn of maltitol sweetening agent - Google Patents

Abstract

production of 4-(alpha-D-gluco-pyranosyl)-D-sorbitol (maltitol) by converting starch to maltose using at least one alpha-1,6-gluco-sidase and beta-amylase and reducing the maltose formed with H2 at high pressure. Maltitol has no calorific value and may be used as a sweetening agent for foodstuffs and drinks. The process can be carried out on a technical scale giving high yields of high purity which results in very economical production.

Description

Process for the production of maltitol The invention relates to a process for the production of maltitol, ie 4- (α-D-glucopyranoxyl) -D-sorbitol, a product of the formula obtained by high pressure hydrogenation reduction from maltose Maltose and from it maltitol have hitherto been obtained in such a way that (1) starch is liquefied, preferably with the aid of α-amylase, with heating; (2) the solution obtained was saccharified by means of malt amylase, ie a mixture of α- and β-amylase, to give maltose with a purity of at most 50 to 63%; (3) separated the dextrins from the degradation product containing larger amounts of protein and borderline dextrins by alcoholic fractionation; (4) the dextrin-free maltose of silver 60% purity was brought to about 90% purity by repeated recrystallization; and (5) the purified maltose was reduced to maltitol by high pressure hydrogenation.

This procedure causes great cleaning difficulties and is also uneconomical for the reason that it is only low at high manufacturing costs Yields.

Paper chromatographic measurements show that after step (2) Saccharified solutions contain around 50% maltose, 30% dextrins and 20% oligosaccharides. In the saccharification process, the so-called oC-1,6-glucoside bonds are retained. Limit dextrins obtained so that a complete amylolysis of the starch according to the previously known Procedure is not feasible. For this reason, the hydrogenation becomes less purified Saccharification solutions according to stage (5) only reduced the maltose contained therein, while the ot and ß-limit dextrins remain. On the other hand, if you clean them saccharified solutions in a cumbersome and costly manner after stage (3) and (4), 100 kg of starch or 102 kg of saccharified starch products only become 3 kg of a 95% strength maltose were obtained. A technically applicable procedure is here thus not before.

The previously used to saccharify the liquefied starch in stage (2) applied ß-amylase is only for the selective decomposition of the α-1, 4-glycoside bonds, which are the most important bonds of the linear chains of the starch molecules and can only consist entirely of linear-chain -1,4-glucoside bonds break down the starch molecules. The branched molecular chain of amylopectin in starch is - as far as its side chains are formed by α-1,4-glucoside bonds - in itself also decomposable, however, the α-1, 6-glucoside bonds inhibit this degradation, from which the side chains are formed, the saccharification of the starch molecules by means of ß-amylase and stop the saccharification reaction leaving behind the Frontier dextrins.

The object on which the invention is based is the elimination the disadvantages described by developing a technically applicable and economical feasible process for the production of high-purity maltitol in high yield by breaking down liquefied starch with certain, selective acting Amylases to maltose and reduction of the purified in a particularly expedient manner Maltose by a high-pressure hydrogenation known per se.

The inventive method is characterized in that one (α) a starch slurry by heating at a temperature between 70 and 180, preferably 120 to 180 ° C completely gelatinized and dissolves, (b) in the a temperature between 45 and 60 ° C cooled starch solution an α-1,6-glucosidase Stir in uniformly and allow to act, (c) ß-Amglase into the reaction mixture stirred in and allowed to act until the end of the ß-amylolysis and (d) the obtained Maltose after purification in the presence of a hydrogenation catalyst at liner Tempe'ratur between 800 and 150 ° C and a pressure between 20 and 100 kg / cm² to the maltitol hydrogenated.

According to the invention in the liquefaction stage (b) during or before α-1,6-glucosidase added to the saccharification process has a specific Effect on the splitting of the α-1,6-glucoside bonds of the side chains of amylopectin and thereby converts the amylopectin into molecules of the amylose type, the exclusively linear chain Contain 1,4-glucoside bonds. The 4-1,6-glueosidase used builds the inhibitory α-1, 6-glucoside bonds selectively and thereby enables an uninterrupted, complete Action of ß-amylase. In this way the action of the ß-amylase is facilitated.

The following experiments show that by using α-1, 6-glucosidase in the saccharification stage progress achieved: in experiment (A), which corresponds to the known method is a 10% slurry of sweet potato starch liquefied by means of α-amylase up to the dextrose equivalent (D.E.) of 2.7%, whereupon 25 units of ß-amylase per g of starch are added and the mixture at 55 ° C im Saccharified over the course of 16 hours. In experiment (B), on the other hand, saccharification is used by adding 25 units of ß-amylase and 10 units of α-1,6-glucosidase carried out per g of starch. From the results according to the following list it can be seen that in case (B) the saccharification solution contains significantly more maltose contains (90.4%) than in case (A) (69.6%): experiment maltose glucose malt triose dextrin A 69.6% 1.1% 3.5% 25.7% B 90.4 0.4 1.3 7.9 The ones used according to the invention α-1,6-glucosidases can be obtained from yeast and plant substances, for example by growing the strains of Aerobaster aerogenes, and are called Isoamylase or R-enzyme, however, for practical use they have a very low value Potency.

The Bender et al. 1961 extracted pullulanase (Biochem. Z. 334, 1961, 79) shows a somewhat higher effectiveness and was used for the determination used to build up starches, but only in the form of very dilute solutions with 1% or less strength. Useful technical applications for these enzymes have been made not suggested.

The inventors of the present process, however, found more extensive Collection of culture samples and soil bacteria from very different locations repeated separation of different types of bacteria from the highly effective enzymes from the strains of the genera Escherichia, Pseudomonas, Lactobacillus, Mierococcus, Nocardia et al.

Of the bacteria selected by separation methods, those became from the genera Pseudomonas and Lactobacillus for the present process as found particularly suitable. The enzymes obtained differentiate EicE somewhat from one another with regard to the type of nutrient medium and enzymatic properties. After review the usability of the enzymes either on their own or in a mixture with one another it was found that the combined use of Pr @@ ulanass.

the enzyme obtained from a strain of the Pseudomonas genus in particular gives good results.

In accordance with the invention are commonly available starches, including Grain, potato, sweet potato and bleached corn starch, applicable. The liquefaction of the starch can optionally be achieved by: (1) Heating the aqueous Starch slurries at 100 to 18,000, (2) using added α-amylase with heating to 70 to 9500, (3) by heating to over 100 ° C of up to one pH 3 to 5 acidified slurry.

As in the subsequent amylolysis of the dissolved starch by means of ß-amylase only the molecules consisting of an even number of glucose units to the maltose is broken down from two glucose units, while maltotriose and glucose are broken down remain unchanged, and since thus, the smaller the molecules of the dissolved starch, which are subjected to amylolysis, the lower the maltose content the completely amylolysed starch is -is in the liquefaction or thermal dissolution of starch, it is advisable to use the lowest possible D.E. to be observed.

On the other hand, the reactions proceed by means of ß-amylase and α-1, 6-glucosidase useful as amylolysis and dilution proceed the starch solution - i.e.

the amylose of the starch should at least be canceled at the time when the saccharification can start.

In this sense, the D.E. the strength at the time of the dissolution not higher than 5, preferably about 1 to 2. When the starch slurry by heating to be liquefied in the absence of a liquefying enzyme, that must be done continuously heated with agitation at or below 180 ° C e und'die treatment time such be dimensioned that a D.E. from about 1 to 2 is reached.

For the same reason, a liquefying enzyme should be used the starch is continuously liquefied at a temperature between 85 and 95 ° C, taking into account the ineffectiveness of the enzyme from heat and the duration of the treatment with regard to the D.E. is limited to several minutes su. When liquefying the degree of dissociation tends to increase greatly with an acid; in this case can liquefied by heating at a pil in the range between about 4 to about 3.5 will.

The starch solution obtained by one of the methods given above has a very high viscosity. Solutions with one for economical production per se particularly advantageous concentration between 20 and 30% but become gel-like after your cooling, and the subsequent downgrading (retrogradation) of the amylose molecules prevents the saccharification enzyme from acting. Even one Solution that is not downgraded is not supposed to be using a starch concentration of 30% or more can be used, since the action of the ß-amylase inhibitory seems to be the breeding ground. Accordingly is a solution with a starch concentration particularly suitable for the following treatments in the range of 10 to 20%.

As mentioned, liquefied starch is easily downgraded. It is therefore necessary to apply them quickly at as high a temperature as possible treat before the viscosity by the amylolysis, which is caused by the addition of the ß-amylase and α-1,6-glucosidase is caused, is decreased. Therefore, a gelatinized Starch solution immediately and continuously cooled by means of a vacuum cooler and Immediately follow the enzyme addition. For this purpose it is useful to have a Protion of ß-amylase or a relatively strong heat-resistant enzyme, obtained from a strain of the genus Lactobacillus (e.g. L.gayomii, ATCC 8290, or L.

plantarum-ATCC 8008) at a relatively high temperature of about 60 ° C, and after the viscosity has dropped, add the rest of the enzyme. For practical Carrying out the starch saccharification it is important to do the primary pre-conversion Addiction on the properties of the applied enzymes - in a period from 20 to 60 Minutes to perform so that enzymes of different types can mix, then cool the solution to 45 to 500a and after adding land mix the remaining Enzymes transfer the mixture into the saccharification vessel as in this stage the If the viscosity of the solution is still high, the secondary pre-saccharification takes about 1 up to 4 hours.

Since then the saccharification runs in considerable dimensions and the viscosity drops, is a pouring together of a very high viscosity solution with oxygen in a large amount of a less viscous solution. Demsu sequence Downgrading is avoided and the solution passes through the cooler in the pre-saccharification vessel kept at a suitable temperature. The mixing of the enzymes and the saccharification will now proceed in an adequate manner and the viscosity of the solution will decrease, though a. Downgrading is avoided. The solution is then pumped into the saccharification vessel for saccharification in batch operation. Since the saccharification takes 2 to 3 days, the solution is kept at a suitable temperature between 45 and 50 ° C and the pH adjusted with the enzymes between 4.5 and 6.0. In this way, the Saccharification to be terminated.

The solution obtained is a converted syrup with a Maltose content from 92 to 94% and a content of glucose, maltotriose etc. of about 5 *. The solution is then filtered and cleaned with ease; after the usual post-treatment a colorless clear sugar solution is obtained. From 100 kg of dehydrated starch Usually 103 kg of pure maltose obtained up to 95%.

In some pills, a small amount of residual high molecular weight makes it difficult Dextrins filtering and purifying.

This is due to an effort to limit starch liquefaction to an extremely low level to a correspondingly increased maltose content to get. In this case, filtering can be done by adding a small amount α-Amylase facilitates the saccharification for the purpose of decomposing the dextrin will.

The pure maltose obtained is reduced by hydrogenation in an autoclave to pure maltitol in the following way: Gains by dissolving maltose in water a 40 to 60% solution to which 8 to 10% by weight Raney nickel are added. Hydrogen is then injected into the solution under a pressure of 20 to 100 kg / cm2 where the temperature is increased from then on up to 100 to 120 ° C.

The pH is often lowered in these cases and the reaction slows down and the yield of maltitol is noticeable about 90% with education of about 8% sorbitol. To improve the yield is therefore used during the hydrogenation the pH be ..

correct. Nevertheless, this means that the yield is only slightly up to increased to 93%. However, calcium carbonate is used as a mild neutralizing agent Added to the starting maltose in an amount of 0.06 to 0.3%, the sorbitol yield increases 1.6% - a sign that the maltose conversion is coming to an end - and the maltitol yield to more than 96%. The result is both in terms of purity and yield satisfactory. 103.5 kg of maltitol are obtained from 100 kg of starch or 103 kg of maltose with a purity of about 95%.

The determination of those which are suitable for use as a sweetener Properties of maltitol are based on the following findings: I. The sweetness.

A group test of the sweet Gesohaok was carried out by 30 people von Naltit showed that this substance tastes completely mild. The taste goes away quickly and does not give a dull aftertaste. Maltitol is sweeter than glucose, however less sweet than cane sugar; the sweetness is about 75% of that of cane sugar.

(A) Distinctive distinction.

This is determined by a paired preferential determination on the following basis: 1). Equation: where x²-single group result α1-number of correct answers α2-number of wrong answers N - α1 + α2 2). Table for x² (degree of freedom 1): Degree of identification 20% 10% 5% 1% 0.1% x² 1,642 2,706 3,841 6,635 10,827 3). If one took into account the distinctive distinction in the degree of labeling at 5 or 1%, the result was: x²> 6.635 - 1% yes 6.63>x²> 3.84 - 5% yes x²> 3.84 no.

(B) Examiner results.

1). Candy tests of D-glucose, D-fructose, sacchardis and maltitol were each repeated at least five times for each candy test. As can be seen from the following list, the sweeteners to be compared can be classified in terms of their sweetness as follows: D-fructose>sucrose>maltitol> D-glucose. Concentrated sugar compared to maltitol tration % D-fructose D-glucose sucrose 70 42.78 6.02 28.46 35 17.86 3.13, 15.86, 20 28.14 1.59 12.57 10 20.16 0.083 8.37 2). In the comparative sweetness test of maltitol and sucrose, a 35% maltitol solution was compared with sucrose solutions of different concentrations according to the following table to exclude the viscosity factor: % Sucrose x² 5 January 21 10 January 21 15 January 21 18 17.28 20 8.63 25 3.67 30 2.83 The results show that the 35% maltitol solution is as sweet as a 25% sucrose solution.

II, The non-crystallization.

Maltitol is 100% abundantly soluble in water. Even a highly concentrated one Solution of 80% maltitol does not form crystals, but remains in the form of a viscous liquid. In addition, maltitol is used to prevent the crystallization of others Sugar applicable; for example a mixture of sucrose or crystallizes Dextrose with maltitol does not.

III. The calorie-free nutritional value.

Experiments showed that - while maltose easily by different Enzymes is cut off - maltitol remains almost unaffected: its loss is only few percent. This degree of degradation was determined with the help of the following enzymes: (A) a cane sugar amylase obtained from a stalk of the Rhyzopus rescue, (B) a from the pig pancreas extracted enzymes and (C) one by salting out a self-dissolving Enzymes obtained from oat extract solution.

Details of the pre-search are given below.

1). Enzymes and their activity; (A) Cane sugar amylase from Rhizopus: (1) MAr 8 U / ml (SD: 120 U / ml) (2) MA: 0.8 U / ml (SD: 12 U / ml) (B) Extraction enzyme from pig pancreas: NA: 0.17 U / ml (C) salting-out enzyme from self-dissolving yeast extract solution: MA: 0.07 U / ml.

2). Temperature and composition of the active solutions for the enzymes: (A) Temp. -40 ° C 1% maltitol or maltose solution 5 ml buffer solution (0.1 mol acetic acid, pH 5.0) 4 ml enzyme solution 1 ml (B) Temp. -40 ° C 1% maltitol or maltose solution 5 ml Buffer solution (0.1 mol phosphoric acid, pH 7.5) 4 ml enzyme solution 1 ml (C) temp. -35 ° C 1% maltitol or maltose solution 5 ml buffer solution (0.1 mol acetic acid, pH 6.5) 4 ml enzyme solution 1 ml 3). Determination of the degree of degradation: the reducing force each active solution in the unit of time was expressed in glucose values according to the Lehmann-Shawl method determined and the values obtained were as those of the direct saccharification in the Unit of time viewed.

Apart from that, one milliliter of 25% hydrochloric acid was used each Active solution added, the mixtures in the usual way for one hour in the boiling Water hydrolyzes and then the reductin power again in the same way as previously determined. The values obtained were regarded as those of total saccharification. The rate of degradation is calculated according to the equation: direct saccharification value Direct saccharification value in time - in O h 100 (%) Total saccharification value - direct saccharification value in O h 4). Results.

(A) Degradation by the cane sugar amylase (A): Reaction MA: 8 U / lm enzyme solution MA: 0.8 U / ml enzyme solution time h Degree of degradation of Maltitol% maltose% maltitol% maltose% 1/4 - 93.5 - 24.2 1/2 5.1 96.8-48.2 1 5.6 96.8 1.4 58.3 3 6.0 97.6 1.9 91.4 5 6.0 100.0 2.3 99.4 B). Breakdown by the pancreatic enzyme (B): Response time degradation from h maltitol% maltose% 1 - 16.7 2 6.7 27.4 20 8.5 82.1 45 9.05 94.0 120 9.96 98.5 C). Degradation by the yeast enzyme (C): Response time degradation from h maltitol% maltose% 1 0.9 12.8 2 1.7 24.7 3 3.8 32.0 4 5.5 39.8 5 8.5 45.1 7 12.4 67.0 Maltitol has no caloric nutritional value as it is neither digested nor absorbed by the digestive organs of higher animals. This was demonstrated by means of the following experiments on live rabbits: The intestines of the guinea pigs which had not been fed 24 hours before were closed at both ends, whereupon 50 ml of a 20% strength maltitol solution or an equimolecular amount of a sucrose solution were injected. After several hours had elapsed, the amounts of maltitol or sucrose remaining in the intestines were determined. It was found that 90% of the sucrose introduced was lost through absorption and evaporation, while maltitol weighed no loss. The latter proves the inability of the maltitol to be absorbed and digested in the digestive organs. It has also been found that maltitol is not a harmful irritant since the intestinal walls which have been exposed to the action of the maltitol have no irregularities, e.g.

showed no rush of blood.

By the way, recent reports have revealed that xylose and sorbitol, the both were considered calorie-free sweeteners, actually subjugating the metabolism and are therefore not calorie-free like maltitol. Dommach has maltitol as a food ingredient has no energetic nutritional value and can also improve the palatability of food to improve with sweetness and abundance. For these reasons, it is essential for that Preparation of calorie-free beverages and edibles.

(IV). The moisture retention and viscosity.

Maltitol can, thanks to its remarkable ability to be restrained of moisture and thanks to its viscosity as a stabilizer for flavorings, colorings and other additives Serve in food and drink. Its high viscosity (measured in centipoise = Cp) is exemplified below shown on its 7O% solution at different temperatures: ° C 22 274 30 167 40 94.5 5 ° 60, 59 40.3 (V). The heat resistance.

The high stability of the maltitol against heat manifests itself in the fact that that when heated with direct fire it does not discolour underneath and only slightly discolored above 200 ° C. It is the same with cooling not fixed.

As described above, maltitol has reasonable favorable properties and also clearly dietary benefit due to lack of nutritional calorie value maltitol other than food is therefore suitable as an agent for sweetening foods including ko various soft drinks, including carbonated Waters such as cola and cider drinks as well as lactic acid drinks and artificial ones Fruit juices, in particular concentrates therefor. Replacing corn syrup, glucose or cane sugar in common sweet drinks by maltitol means a replacement of the total amount of carbohydrates in the solids content of the drinks a low-calorie substance. This isn't just dated medical and dietary Point of view, but also to improve taste as well as bestow a suitable Viscosity and flower of the drinks are desirable. Thanks to the effect of the addition of maltite the drinks can get their delicious flower adapted to every taste without to leave an unpleasant aftertaste.

Similarly, maltitol gives ill. Application in western and Japanese Sand cakes and sweets sugar-free bakery products with the lowest possible nutritional values. At the same time there is a risk of drying out or crystallization, which occurs more often The use of sugar occurs, remedied by the use of maltitol and thereby its beneficial properties of moisture retention and non-crystallization completely revealed. Cookies and other confectionery products sweetened with maltitol can be used for sugar-free, Serve low-calorie diliter nutrition. In addition, the good heat resistance prevents The maltitol causes excessive discoloration of the confectionery when heated and protects it Maltitol also improves from decomposition and deformation when cooling after baking the economic returns by preventing loss of taste and maintaining it of food quality for a long period of time. When using maltitol as colorless Component for making jellies and the like it can in turn prove its usefulness, for example by preventing undesirable Discoloration and loss of food coloring, by increasing the moisture retentive Properties, by preserving the flavor and by ensuring a long retention period.

Examples.

A). Manufacture of Na'ltose.

I). Apparatus and process scheme.

On the accompanying drawing is an annex on continuous Production of maltose shown schematically.

In the stirred vessel 1, starch and water are continuously supplied adjusted the concentration and pH of the starch slurry formed and the required amount of liquefying enzyme is added, after which the slurry is added pumps into the condenser 2, which is equipped with a multi-blade stirrer, and below it vigorous stirring as long as heated with direct steam at a constant temperature, until it is evenly gelatinized. The gelatinized starch is then made into several Retention tanks 3.3, which are used to maintain a constant temperature are provided with temperature control jackets and temperature regulators, up to the optimum D.E. liquefied.

The liquefied starch is released under normal pressure through a pressure reducing valve let into the cooler 4 and cooled to about 10,000, then immediately into the vacuum cooler 5 injected and cooled here down to a set temperature, whereupon you the solution leads to the first mixer 6 Ubera. The enzyme will proceed to the solution, continuously fed either at the bottom of the vacuum cooler 5 or directly to the mixer 6.

If the total amount of enzyme required is incorporated at once, the solution is pumped from the bottom of the first mixer 6 into the saccharification vessel 8, in which the saccharification is terminated. If, on the other hand, the enzyme is added in two portions the liquid is left in the first mixer for a fixed time 6 and then pumps it continuously from the bottom of this vessel into the second mixer 79 in which the second enzyme part enters at the same time. After a certain dwell time the solution is pumped into the saccharification vessel 8. Thorough mixing and temperature control in the two mixers 6 and 7 is carried out by means of effective stirrers as well as heat exchangers and automatic temperature controllers.

II). Applied enzymes.

1). It serves as a liquefying enzyme α-amylase, 2). as ß-amylase an enzyme extracted from wheat (according to US Patent Application No. 562,528), 3). as α-1,6-glucosidases optionally the following 3 enzymes: (P) pullulanase from Aerobacter aerogenes (Biöchem. Z.

334. 1961, 79), (J) enzyme from Pseudomonas emgloderamosa (according to US patent application No. 73,326; ATOC 21 262) and (L) enzyme from Lactobacillus plantarum (to Japan. Patent Application No. 21,364 (7/1967); ATOC 8008).

The effectiveness of these enzymes was determined in the following way: 1) .α-amylase.

A solution consisting of 1 g of potato starch, 1 ml of a 0.1 M acetic acid buffer solution and 8 ml of water, is poured into several test tubes with an inner diameter of 18 mm and in the same tubes 1 ml of enzyme solution of different concentrations are added filled.

The filled tubes are heated by vigorous swirling in boiling Water, after gelatinizing the starch, leave it to stand in the air for 15 minutes at 65.degree and does it again for the purpose of inactivating the enzyme 10 min in boiling water. After cooling in water at 170 ° C. for 3 minutes, in 1 ml of 0.1% fuchsine solution was added to each tube and the tubes were added twice tilted when opening is blocked. From the solutions evenly colored without turbidity one selects the enzyme solution with the lowest concentration and looks at its Activity as a unit.

2). β-amylase.

A mixture of 5 ml of a 1% solution of soluble starch, 4 ml a 0.1 M acetic acid buffer solution and 1 ml enzyme solution of various concentrations is heated for 30 min at 40 ° C and the produced reducing sugar in maltose values certainly. The effectiveness of that enzyme solution which gives 10 mg of maltose can be seen one as a unit.

3). α-1,6-glucosidase.

A mixture of 1 ml of an enzyme solution is heated for 30 min at 40 ° C, 5 ml of a 1% solution of soluble slimy rice starch and 1 ml of a 0.5 N acetic acid buffer solution (pH 6.0) and pour 1 ml of it into a solution containing 0.5 ml a 0.01 N-iodine-iodopotassium solution and 15 ml of a 0.01 N-sulfuric acid.

The color of the mixture immediately changes to bluish-purple # n. To 15 min the extinction coefficient of the coloration with light of a 620 mμ wavelength measured and the difference between the measured value and the one immediately after the Implementation obtained calculated.

The effectiveness of an enzyme solution is considered to be a difference of 0.01 one as a unit.

III. Starch liquefaction.

In trials 1 to 3, sweet potato starch is used, in trials 4 to 6 grain starch used.

The sweet potato starch is continuously liquefied at 90 ° C Addition of 10 units of α-amylase per g of starch in 1 to 2 minutes to the D.E. from about 1 to 2%; then the temperature is increased for the purpose of enzyme decomposition increased to 120 ° C.

Grain starch is made by heating at 160 to 165 ° C and a pH 6 liquefied without the addition of enzymes. Only example 6 is carried out with the addition of oxalic acid in an amount equivalent to 0.05% of the amount of starch1 and with brief heating at 120 ° C by The D.E. one poses without exception In the range of 0.5 to 2 a.

IV. Saccharification process.

So much for the pre-saccharification with the addition of α-1,6-glucosidase and ß-amylase is carried out in two different stages (experiments 2 to 4), one uses in the first stage a temperature of 70 to 6000 and the heat-resistant one α-1,6-gucosidase (L). To lower the starch viscosity as quickly as possible, the enzyme is continuously introduced into the vacuum cooler 5. As well as. the second Stage of the two-stage pre-saccharification (experiments 2 to 4), as well as the one-stage Pre-saccharification (experiments 1, 5 to 7) is carried out at a temperature of 45 to 509a and a pH 6 with rapid mixing with a powerful stirrer by.

The average duration of treatment for the first stage of pre-saccharification is 20 to 60 minutes - otherwise in the range of 3 to 4 hours. ' With every attempt the liquid is introduced into the main saccharification vessel and de saccharification led to ends in batch operation.

When using the enzyme (J) the temperature is set to 4500: and that pH adjusted to 5.5, - in other cases, however, to 6.0. The duration of the main saccharification is 2 to 3 days.

While the sugar yield is 98% immediately after saccharification, the final yield of crystalline product decreases thanks to the loss of purification to 95%. The maltose content of the test products is in the range from 92 to 95%.

The working conditions and results can be found in detail in Table I below (under “B” there is meant β-amylase) * Table I Example 1 2 3 4 5 6 7 Sweet Potato Starch Grain Sweet Potato Starch content% 30 30 25 25 25 25 10 Condensing Temp ° C 90-92 90-92 90-92 165 165 120 120 Enzyme α-amylase - - Oxalic acid - DE% 1.8 1.5 1.5 0.9 0.8 2 0.5 1. Pre-saccharification step: Enzyme unit ß 50 ß 50 @ Thickness P 50 ß 50 1 40 ß 70 I 30 ß 50 ß 50 F 30 L 40 L 50 pH 6.0 6.0 6.0 6.0 5.5 6.0 Temp. ° C 45-50 70 60 65 45-50 45-50 45-50 2. Pre-saccharification step: Enzyme - F 40 ß 40 I 50 - - - pH - 6.0 6.0 5.5 - - - Temp. ° C - 45-40 45-40 45-40 - - - Exposure time h 48 50 48 40 50 50 Matose content% 93-92 93 93-94 90-93 91-98 90 87 B). Maltose hydrogenation.

Hydrogenation is carried out under the following conditions: 1). The discolored and purified raw material of the composition 96.6% maltose 3.0 malt triose O ,, 4 Dextrose is used in the form of a 40 to 6O% solution.

2). A Raney nickel developed in alkali serves as the catalyst in an amount of 8 to 10% of the starting material.

3). At a temperature between 90 and 10,000 it becomes 2/3 of the hydrogen equivalent absorbed; ' the equilibrium point is reached when the temperature was last increased to 125 ° C of absorption.

4). The hydrogenation pressure is between 20 and 100 kg / cm².

5). Calcium carbonate is used in half of the cases in an amount of 0X3 to 0.05% of the starting material added.

The table below shows the individual conditions and results of the hydrogenation carried out with stirring. Table II without CaCO3 with CaCO3% pH 0.06 0.13 0.25 on- not on represents stilted Initial pH 4.0-6.2 7.0-7.5 7.3 7.4 7.0 pH at end 4.2-3.7 4.3-3.8 4.8 5.7 6.1 not implemented Sugar% - 0.4-1.8 6.2-1.2 0.28 0.28 0.25 Hydrogenation time h 8 - 13 8 - 10 8 8 8 Hydrogenation product contains sorbitol% 7.5 4.6 2.1 1.8 1.6 Maltitol 90.8 93.5 95.9 96.2 96.4 other 1.8 1.9 2.0 2.0 2.0 The Raney nickel is removed from the crude hydrogenation mixture obtained and each product is concentrated, decolorized and purified in the usual way by means of ion exchange.

Claims (7)

Patent to claims 1. Process for the production of maltitol by breaking down 'starch with Amylases and reduction of the purified maltose obtained by high pressure hydrogenation, d a d u r c h e k e k e n n n z e i c h n e t that one (a) a starch slurry completely gelatinized and liquefied by heating at temperatures between 70 and 180 ° C, (b) into the starch solution obtained, cooled to a temperature between 45 and 60 ° C stir in an α-1,6-glucosidase evenly and let it act, (c) into the Stir in the ß-amylase reaction mixture and act until the ß-amylolysis is complete and (d) the maltose obtained after purification in the presence of a catalyst at temperatures between 80 and 150 ° C and a pressure between 20 and 100 kg / cm² hydrogenated to maltitol. 2. The method according to claim 1, characterized in that - that the Liquefaction stage (a) by adjusting the pH to between 3 and 5 and heating at over. 100 ° C without enzyme. 3. The method according to claim 1, characterized in that the Liquefaction stage (a) is carried out with the addition of α-amylase and heating to 95 ° C. 4. The method according to claim 1 to 3, characterized in that one the saccharification stages (b) and (o) by simultaneous rapid stirring in of the Combined α-1,6-glucosidase and β-amylase and heating at 45 to 55 ° C. 5. The method according to claim 1 to 3, characterized in that one carries out the saccharification stages (b) and (c) in reverse order by (b 1) to the starch solution cooled to 45 to 70OQ, stir in the ß-amylase quickly and allowed to act until the viscosity is reduced and (c 1) after adding α-1,6-glucosidase the ß-amylolysis is terminated at 45 to 60 ° C. 6. The method according to claim 1 to 5, characterized in that one in the saccharification stages simultaneously two or more kinds of Applies α-1,6-glucosidase with different behavior. 7. The method according to claim 1 to 6, characterized in that one in the hydrogenation stage (d) one mole of hydrogen binds to each mole of maltose.