Method of production of the alkali-resistant and thermal-resistant polyols

FIELD: chemical industry; method of production of the alkali-resistant and thermal-resistant polyols.

SUBSTANCE: the invention is pertaining to the improved method of production of the alkali- resistant and thermal-resistant polyols representing the sugar-alcohol syrups. The method provides for the following stages: hydrogenation of the hydrolysate of the corresponding polysaccharide with formation of the hydrogenated sugar-alcohol syrup, the alkaline and thermal treatment of the hydrogenated syrup for production of the stabilized sugar-alcohol syrup, refining of the stabilized sugar-alcohol syrup by its gating through, at least, one ion-exchange resin, in which the stabilized sugar-alcohol syrup is refined by means of its double gating through the cationic- anionic ion-exchange configuration (CACA) including, at least, the first weak-acid cationic ion-exchange resin and the second strongly-base, medium-base or weak-base anion-exchanging resin. The method allows to have the alkali-resistant and thermal-resistant polyols not having the shortcomings of the polyols of the previous level of the engineering.

EFFECT: the invention ensures production of the alkali-resistant and thermal-resistant polyols not having the shortcomings of the polyols of the previous level of the engineering.

18 cl, 3 ex, 1 dwg

 

The technical field

The invention relates to a method for producing stable to alkali and heat-resistant polyols, in which the sugar alcohols are treated with reagents in order to obtain a stabilized sugar alcohol syrup with reagents and stable alcoholic syrup was subjected to purification by skipping stable sugar-alcoholic syrup through at least one ion exchange resin.

Under the polyol refers to a sugar alcohol syrups, namely the hydrogenation products of hydrolyzates of polysaccharides, which include, but are not limited to the number, the hydrolysates obtained from starch, Xylenol, arabinoxylans, cellulose and other plant polysaccharides. Typical starch hydrolysates are, for example, dextrose, glucose syrups with a high dextrose equivalent (DE), high maltose syrups, standard glucose syrups and maltodextrins, including maltodextrins with low dextrose equivalent (DE).

Prior art

Resistance to alkalis and thermal stability of the sugar alcohols are significant factors in a number of industrial and food applications, as shown in the publications of JP 63/079844 and EP 0711743. Resistance to alkali and heat resistance in these documents reach the processing of sugar alcohols re what gentami thus, in order to remove color-forming components.

In JP 63/079844 sugar alcohol syrups treated at pH 9.5 to 13 and high temperatures in a period of time ranging from 30 min to 2 hours.

In EP 0711743 stabilization is carried out using the stages of fermentation, acidification or caramelization.

Stable so the sugar syrup then directed to the purification stage, receiving the result, this final product.

In JP 63/079844 mentioned cleaning stage includes processing the treated syrup ion exchange resins. When this syrup, pre-cooled to 50°first passed through a strongly acidic cationic resin and then, as mentioned above, through poorly - or srednesrocnye resin at ratio of 1:2. The temperature at which applied these resins, the above patent document was not provided.

In example 1 of EP 0711743 stable syrup cleanse using a strongly acidic cation resin and strong base anion resin. There is also no mention about any temperature at which the used ion-exchange resin.

In EP 1095925 is considered an improved method of purification of sugar alcohol syrups, which were subjected to alkaline and thermostabilization processing. In this way the cleaning is done by at least one transmission from abilityone sugar alcohol syrup through a strongly acidic cationic resin at a temperature below 50° Since, in the preferred case when the temperature is below 40°and in the most preferred case from 20 to 30°C.

In EP 1095925 informed about the importance of working temperatures of the resin to the desired degree of recovery of sugars after cleaning. This obviously implies that the working temperature is below 30°To cause possession of the products excellent heat resistance and resistance to alkali, which is required in many applications. The importance of temperature is greater, the higher the content of the syrup is capable of hydrolysis alcohol, such as maltitol, maltitol and hydrogenated oligosaccharides.

In the US 5254174 discuss the importance of working temperature, strong acid cation resin for hydrolysis of the treated substrate. In order to prevent hydrolysis of the oligosaccharides are encouraged to apply in the processing of oligosaccharides strongly acidic cationic resin at temperatures ranging from 25 to 35°C.

In the US 4329183 discusses how the reaction of the inversion of sucrose is prevented by regulating the temperature of a strongly acidic cation resin in the range from 25 to 30°C.

The use of strongly acidic cation resins when cleaning stabilized sugar alcohol syrup, however, has the disadvantage that, when you need products with low content of reducing Sugars is necessary to work at temperatures from 20 to 30° C. For cooling syrups to these relatively low temperatures require the use of additional cooling equipment, and additional energy. Due to these low temperatures, the viscosity is relatively concentrated syrups increases, resulting processing is complicated even more (if there is pressure in the resin). This is especially true in the case of syrups obtained by hydrogenation, and among other hydrolysates of starch, mainly consisting of di-, tri - and higher oligosaccharides (e.g., syrups middle and high content of maltose, maltodextrins). Another disadvantage of strongly acidic resins is that their regeneration requires a large excess of acid.

In EP 0262711 for cleaning light juice beet sugar is discussed using a combination of weak acid cationic and non-core environments anionic resins.

Disclosure of the invention

It should be noted that the purpose of the above method is the partial demineralization of bright juice beet sugar (as described in the example). However, from the above examples it is clear that the removal of cations and discoloration are not fully exploited.

The aim of the invention is to provide a method of preparing stable to alkali and heat-resistant polyols do not have is their above described disadvantages.

This goal is achieved by providing a method of preparing stable to alkali and heat-resistant polyols, in which:

the hydrolysate of the corresponding polysaccharide hydronaut with the formation of the sugar alcohol syrup;

- carry out alkaline and heat treatment of the hydrogenated syrup in order to obtain stable sugar syrup;

- stable sugar-alcoholic syrup was subjected to purification by passing a stabilized sugar alcohol syrup through at least one ion-exchange resin,

and in which stable sugar-alcoholic syrup cleanse using a double pass through the cation-anion ion-exchange configuration (KAKA), including at least the first weak acid cationic ion exchange resin and the second strongly, moderately or weakly basic anion exchange resin.

In one of the preferred methods according to the invention, the process temperature is from 20 to 60°C.

In one of the preferred methods according to the invention in the configuration KAKA uses a system of "carousel", which includes at least 3 pairs of columns, where each pair of columns consists of a column filled with a cationic ion exchange resin, and the column filled with anion ion exchange resins. At least two pairs of columns are used for cleaning hundred is alizirovannoj sugar alcohol syrup while the third pair of columns subjected to regeneration.

The advantage of this system is that the refining stabilized sugar alcohol syrup can be made in a continuous way.

In one specific preferred methods according to the invention mentioned cationic ion exchange resin in the column consists of two layers, with the layer ion-exchange resin at the outlet of the column consists of a strongly acidic ion-exchange resin.

In a more specific method according to the invention called a strongly acidic ion-exchange resin is from 0.5 to 50% by volume of cation exchange resin in the column.

In another more specific method according to the invention mentioned layer of strongly acidic ion-exchange resin is from 5 to 25% of the volume of the cationic resin in the column.

In one of the preferred methods according to the invention, the process temperature is from 30 to 50°C.

In one specific preferred methods according to the invention, the process temperature is from 35 to 45°C.

In one of the specific methods according to the invention the processing of sugar alcohols in order to obtain a stabilized sugar alcohol syrup at the first stage includes, as mentioned previously, the hydrogenation of the corresponding hydrolyzate of the polysaccharide with the formation of the hydrogenated sugar alcohol syrup followed by alkali and heat treatment of the hydrogenated syrup, getting mentioned stable sugar-alcoholic syrup.

In one of the more specific methods according to the invention the reaction of hydrogenation is interrupted, when the residual content of reducing sugars (calculated on dry weight) falls below 0.2%.

In the most specific way according to the invention the reaction of hydrogenation is interrupted, when the residual content of reducing sugars (calculated on dry weight) falls below 0.1%.

In one of the preferred methods according to the invention, the conductivity of refined sugar alcohol syrups is less than 1% of the initial conductivity.

In one of the preferred methods according to the invention, the conductivity of refined sugar alcohol syrups is less than 0.5% of the initial conductivity.

In the method according to the invention mainly use sugar alcohols, which have a certain method Bertrand total content of reducing sugars after hydrolysis ranges from 3.5 to 98%.

In the method according to the invention preferably use sugar alcohols, which have a certain method Bertrand total content of reducing sugars after hydrolysis is in the range from 40 to 95%./p>

Most preferably, in the method according to the invention are used sugar alcohols, which have a certain method Bertrand total content of reducing sugars after hydrolysis is in the range from 50 to 92%.

In one of the preferred methods according to the invention called sugar alcohols obtained by hydrogenation of maltose syrups with concentrations ranging from medium to high.

Further characteristics and features of the present invention are explained on the basis of the carried out example with reference to the accompanying drawing. It should be borne in mind that the specific aspects of this example are described as one of the preferred examples, the components of the scope of the claims above General description of the invention, and in any case can not be interpreted as limiting the scope of the invention as such and scope of the following claims.

The attached drawing is a schematic of the system carousel according to the invention.

The first stage in the method according to the invention involves the hydrogenation of the hydrolyzate of the corresponding polysaccharide (also called sugar alcohol), followed by alkali and heat treatment of the hydrogenated sugar alcohol syrup order to obtain a stabilized sugar alcohol syrup and, finally, cleaning or refining stabilized sugar alcohol syrup, then get resistant to alkali and heat-resistant sugar-alcoholic syrup.

The method according to the invention is advantageous for the sugar alcohol syrups with a total content of reducing sugars after hydrolysis, determined by the method of Bertrand, varying in the range from 3.5 to 98%. Further it was also found that this method also gives very good results when processing sugar alcohol syrups with a total content of reducing sugars after hydrolysis, determined by the method of Bertrand, varying in the range from 40 to 95%, preferably from 50 to 92%. Typical sugar alcohol syrups, like mentioned above, is produced by hydrogenation of maltose syrups with a concentration of maltose from medium to high.

The hydrogenation is carried out using conventional, known in the art methods. The hydrogenation is interrupted, when the residual content of reducing sugars (calculated on dry weight) falls below 0.2%, preferably below 0.1%.

After that, hydrogenated sugar-alcoholic syrup is subjected to alkali and heat treated in order to obtain a stabilized sugar alcohol syrup, and sugar stable-alcoholic syrup during this process becomes.

At the next stage, this hundred is alizirovannaya sugar-alcoholic syrup cleanse or rafinuyut order to remove the present non-ferrous components. Cleaning stage consists of a dual pass (KAKA) through cation-anion (CA) ion-exchange configuration. In this process, the use of weak acid cation resin and strongly, moderately or weakly basic anionic resin at a temperature in the range from 20 to 60°or in a more preferred method, the temperature varies from 30 to 50°or, in an even more preferred method from 35 to 45°C.

Thus, it is extremely important that after processing KAKA syrups would be almost completely demineralizer and colorless. In addition, these syrups should be substantially colorless when they are more alkaline and heat treatment.

In one of the preferred methods used configuration KAKA in the "carousel", as shown in the drawing. A similar system consists of 3 pairs of columns (or sets), where each pair of columns consists of a column filled with a cationic resin, and the column filled with anion resin. Two pairs of columns are used for cleaning the treated syrup (KAKA), while the third pair of columns used for regeneration. Then refined syrup is passed through a second group of columns AC and collect. Thus, when the first pair of speakers is exhausted, the power switch on the second pair of columns, and then refined soroptomist after the third group of columns CA. At the same time the first group of resins desalinate and regenerate.

In one embodiment of the method according to the invention the cationic resin in the column consists of two layers, with the layer of resin at the entrance to the column consists of a strongly acidic ion-exchange resin. This layer is from 0.5 to 50% by volume of the cationic resin is preferably from 5 to 25%.

After processing, the conductivity of refined sugar alcohol syrups is less than 1%, mostly less than 0.5% of the initial conductivity.

Sugar alcohol syrups obtained using the method according to the invention are most suitable for cooking foods with alkaline pH or products containing an alkaline component, or products that handle or receive by means of heat treatment.

Hereinafter the invention is explained using several examples, which, however, in no case should not be interpreted as limiting the scope of the invention as such and scope of the invention, formulated in the accompanying claims.

Example 1:

Highly concentrated maltose syrup hydronaut in accordance with standard methods up until the residual content of reducing sugars will not be less than 0.2% (by dry weight).

Then hydrogenated syrup (about 50% (based on dry weight), having the th the following composition, subjected to alkali and heat treatment, in which the pH of the syrup was adjusted to 11 and then heated for 2 hours at 100°C.

The syrup is as follows (% dry weight):

Sorbitol6,5
Maltitol62,5
Maltotriose18,5
Polyols with a higher degree of polymerization12,4

After alkaline treatment hydrogenated syrup is cooled to a temperature in the range from 35 to 40°and purified with ion exchangers. The system consists of three pairs of columns. Each pair consists of a column filled with a cationic resin, and the column filled with anion resin. Used cationic resin is a weak acid cation resin (Lewatit S8528), and the anionic resin is a strong base resin (Lewatit OS 1074). Glass columns filled with resin, have a double wall with an inner diameter of 25 mm, the Volume of the resin is 100 ml Lewatit S8528 and 100 ml of Lewatit OS 1074. The column is heated to 35°and apply the volumetric rate of 200 ml/h

The power of the first pair of columns stop after processing in the said first pair of columns 31000 ml syrup (stage 1). After that the power switch on the second pair of columns, which before use is stayed as a "finishing" of the pair.

Next connect the third pair of columns as "finishing" pair", while the first pair is freshened and regenerated (stage 2). The power of the second pair of columns also stop after 31000 ml and switch the power to the third pair of columns (stage 3). Thus, the work continues in the configuration of the carousel, where there is always regenerated one pair of columns, the following refinement system KAKA, which continues to operate. Refined syrup is collected at the outlet of the second pair of columns configuration KAKA.

The value of extinction unrefined substrate before KAKA-equal treatment of 2.45 (1-cm cuvette 420 nm).

After completing the processing in the first stage refined so the syrup is subjected to testing for resistance to alkali and thermal stability.

This test, called the S-test, described in detail in EP 711743. The increased stability of the sugar alcohol is reflected by the low values of extinction, defined using this S-test (predominantly <0,1).

Said value of extinction (S-value) sugar alcohol syrup after refining was determined for syrups, collected on the first, second and third stages, as shown in the drawing.

KAKA-processingS-value :
Stage 1 0,055
Stage 20,052
Stage 30,051

Comparative example 1:

The syrup maltitol example 1 is subjected to ion exchange purification using the following combinations of resins:

(A) strong acid - srednednevnoe (Dowex 15 CM Purolite A8478)

(B) strong acid - strong base (Dowex 15 CM and Lewatit).

Then conduct purification step at two different temperatures: 23 and 35°C.

The following table S-values thus treated syrups are compared with the S-values of the products obtained by the process according to the invention.

Example 1(A) 23°(A) 35°(In) 23°(In)35°
S-value : 0,0510,0890,0950,0750,085

It can be concluded that the results obtained using KAKA-processing according to the invention, in all cases better than the same quantities obtained by known methods.

Example 2:

The syrup maltitol used in example 1 was subjected to ion exchange treatment with the use described in example 1 system KAKA "carousel", where the cationic resin in the column consists of a compound word is, in which 90 ml of weak acid cation resin (TMAS NR) is located on top of a layer of 10 ml of a strongly acidic cationic resin (Dowex CM15). Anionic resin is srednednevnoe resin (Purolite A847S).

Used in example 1, the syrup maltitol rafinuyut through equal amounts of cationic and anionic resins at 35°C. Refined syrup has an S value equal to 0.63.

Separate experiments on the purification of sugar syrup with a double bandwidth KAKA and using a single pass of the SPACECRAFT.

Raw=Merital after heating .Fr. passing through the ion-exchange resin
25.09.20012 V 19/9/01KAKAFrom=HP 336 62 ml
pH=10,5A=O ml
cond.=295 μS/cmKA (link A.Fr.)C=15 CM 100 ml
EXT. NaOH=25 ml/kgA=A847S 100 ml
needs. NaOH=10,1flow rate of 200 ml/hour
ml/kg35°
Brix=50,5

KAKA
Vol. layersPHCOND.
21,480,4
23,06,80,3
24,66,90,3
26,26,80,3
27,86,90,3
29.46,90,3
31,07,10,3
32.67,10,4
34,27,30,4
35.87,70,4
37,47,80,6
39,080,7
40,68,41,2
42,28.93
43,89,37,6
to 45.49,514,9
47,09,823,1

mix-sample3900 ml

AHS
abs 420 nm 0.2103% RS/bx 0,041

CA
Vol. layerspHCOND.
23,87,70,5
25,67,50,3
27,47,50,3
29,27,50,3
31,07,50,4
32,87,60,4
34,67,40,3
36,37,30,3
38,17,50,3
39,97,40,3
41,77,10,3
43,57,10,3
45,37,20,3
47,17,20,3
48,970,3
50,66,950,3
52,46,80,3
54,26,90,7
56,06,70,8
57,86,92,2
to 59.67,67,2
61,48,116,9
63,1 8,325,2
64,98,333,7

mix-sample5600 ml

AHS abs
420 nm 0,3294% RS/bx 0,049

1. The method of obtaining resistant to alkali and heat-resistant polyols, which represents a sugar alcohol syrups, which includes the following stages:

hydrogenation of the corresponding hydrolyzate of the polysaccharide with the formation of hydrogenated chernosvitova syrup;

alkaline and heat treatment of the hydrogenated syrup in order to obtain a stabilized sugar alcohol syrup;

cleaning stabilized sugar alcohol syrup by passing a stabilized sugar alcohol syrup through at least one ion-exchange resin,

characterized in that a stable sugar-alcoholic syrup cleanse using a double pass through the cation-anion ion-exchange configuration (KAKA), including at least the first weak acid cationic ion exchange resin and the second strongly, moderately or weakly basic anion exchange resin.

2. The method according to claim 1, characterized in that the stage of cleaning the stable Saha is but-alcoholic syrup by passing it through an ion-exchange resin is carried out at a temperature in the range from 20 to 60° C.

3. The method according to claim 1 or 2, characterized in that in the configuration KAKA uses a system of "carousel", which includes at least 3 pairs of columns, where each pair of columns consists of a column filled with a cationic ion exchange resin, and the column filled with anion ion exchange resin, and at least two pairs of columns are used for cleaning stabilized sugar alcohol syrup, while at least the third pair of columns is used for regeneration.

4. The method according to claim 3, characterized in that the cationic ion exchange resin in the column consists of two layers, with the layer ion-exchange resin at the outlet of the column consists of a strongly acidic ion-exchange resin.

5. The method according to claim 4, characterized in that the layer of strongly acidic ion-exchange resin is from 0.5 to 50% by volume of cation exchange resin in the column.

6. The method according to claim 5, characterized in that the layer of strongly acidic ion-exchange resin is from 5 to 25% by volume of cation exchange resin in the column.

7. The method according to any of claim 2, 4-6, characterized in that the purification stage stabilized sugar alcohol syrup is carried out at a temperature in the range from 30 to 50°C.

8. The method according to claim 3, characterized in that the purification stage stabilized sugar alcohol syrup is carried out at a temperature within the range of the x from 30 to 50° C.

9. The method according to any of claim 2, 4-6, characterized in that the purification stage stabilized sugar alcohol syrup is carried out at a temperature in the range from 35 to 45°C.

10. The method according to claim 3, characterized in that the purification stage stabilized sugar alcohol syrup is carried out at a temperature in the range from 35 to 45°C.

11. The method according to claim 1, characterized in that the hydrogenation reaction is interrupted when the residual content of reducing sugars (calculated on dry weight) falls below 0.2%.

12. The method according to claim 1, characterized in that the hydrogenation reaction is interrupted when the residual content of reducing sugars (calculated on dry weight) falls below 0.1%.

13. The method according to claim 1, characterized in that the conductivity of refined sugar alcohol syrups is less than 1% of the initial conductivity.

14. The method according to claim 1, characterized in that the conductivity of refined sugar alcohol syrups is less than 0.5% of the initial conductivity.

15. The method according to claim 1, characterized in that use sugar alcohols, which have a certain method Bertrand total content of reducing sugars after hydrolysis ranges from 3.5 to 98%.

16. The method according to claim 1, characterized in that use sugar alcohols, which have a certain method Bertrand common with what the actual content of reducing sugars after hydrolysis is from 40 to 95%.

17. The method according to claim 1, characterized in that use sugar alcohols, which have a certain method Bertrand total content of reducing sugars after hydrolysis ranges from 50 to 92%.

18. The method according to any of PP-17, characterized in that the sugar alcohols obtained by hydrogenation of highly concentrated maltose syrups.



 

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