Crystalline mixture solid composition and process for...

Sugar – starch – and carbohydrates – Products – Sugars only

Reexamination Certificate

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C127S029000, C127S058000, C127S060000, C127S061000, C536S001110, C536S123130, C536S124000, C536S127000

Reexamination Certificate

active

06746541

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a crystalline mixture solid composition which comprises
&agr;-D-glucopyranosyl-1,1-mannitol and
&agr;-D-glucopyranosyl-1,6-sorbitol and may further comprise
&agr;-D-glucopyranosyl-1,1-sorbitol in a certain case and to a process for the preparation thereof.
PRIOR ART
Hydrogenated palatinose (hydrogenated isomaltulose) has been known as one of low-calorie sweeteners which do not cause a carious tooth. The hydrogenated palatinose is a mixture of two sugar alcohols, that is, an almost equimolar mixture of &agr;-D-glucopyranosyl-1,1-mannitol (to be abbreviated as GPM hereinafter) and its isomer &agr;-D-glucopyranosyl-1,6-sorbitol (to be abbreviated as GPS-6 hereinafter), which can be obtained by forming palatinose (isomaltulose) from cane sugar by means of a transferase and then hydrogenating the palatinose.
The hydrogenated palatinose is known as an extremely useful sweetener which exhibits an excellent sweet taste like cane sugar, has low hygroscopicity, heat resistance, acid resistance, alkali resistance, excellent processability such as tablettability and granulability, and physiological properties such as low calorie, noncariogenic properties and insulin non-irritating properties.
As the method of crystallizing the hydrogenated palatinose, H. Schiweck's report (Alimenta. 19,5-16, 1980) discloses a vacuum crystalizar process. However, this process is very complicated and repeats the steps of evaporation, aging and centrifugation, thereby consuming a huge amount of energy and boosting product costs.
JP-A 60-181094 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”) discloses a process for crystallizing an aqueous solution of hydrogenated palatinose having a solid content of about 80% in a vacuum crystallization apparatus. However, since this process requires a special apparatus such as a vacuum crystallization apparatus and employs a batch system, it is not practical due to its low production efficiency.
JP-A 62-148496 discloses a process for crystallizing hydrogenated palatinose in accordance with a kneading method using seed crystals. This process is used to crystallize mainly a GPM component out of hydrogenated palatinose components. That is, the water content of the hydrogenated palatinose is adjusted to a range of more than 5% and 20% or less, the liquid temperature is maintained at a range of 50 to 90° C. according to the content of water, seed crystals are added and mixed, and the mixed product is solidified by cooling the temperature at around room temperature, dried and ground to obtain crystallized hydrogenated palatinose powders. However, this process has a problem with processing (such as grindability) as the kneaded product obtained by this process has high stickiness and also a problem with distribution (such as caking and the propagation of microorganisms) as cooling and drying take long time.
It is also known that when a transferase is caused to act on cane sugar, trehalulose (&agr;-D-glucopyranosyl-1,1-fructose) is formed in addition to isomaltulose. Generally speaking, when hydrogenated palatinose is produced, after only palatinose is obtained by crystallization separation, the residual mixture containing trehalulose is discarded or disposed at a low cost. It is known that trehalulose is converted into GPM and &agr;-D-glucopyranosyl-1,1-sorbitol (to be abbreviated as GPS-1) by hydrogenation. That is, when a transferase is caused to act on cane sugar as a raw material and the obtained mixture is hydrogenated, a mixture of GPM, GPS-6 and GPS-1 can be obtained. To obtain such a mixture, a process is known as disclosed in JP-A 7-51079. This process comprises the first step of carrying out the conversion reaction of cane sugar, the second step of removing unreacted cane sugar and the third step of carrying out a hydrogenation reaction in the presence of a catalyst. As for solidification, the above publication discloses a fine particulate product obtained by vaporizing water for solidification and grinding. However, the product is an amorphous and glass-like solid, has high hygroscopicity, and is difficult to handle and easily worn by abrasion during circulation.
SUMMARY OF THE INVENTION
In object of the present invention to provide a crystalline mixture solid composition which has almost no hygroscopicity, is easy to handle and dissolve, and hardly worn by abrasion, comprises GPM, GPS-6 and GPS-1.
It is another object of the present invention to provide a composition which comprises GPM and GPS-6 and may further comprise GPS-1 in a certain case and has a specific surface area of 0.07 to 0.1 m
2
/g.
It is still another object of the present invention to provide a power-saving and labor-saving process for producing the above composition of the present invention in an extremely short period of time with a small-scale apparatus.
Other objects and advantages of the present invention will become apparent from the following description.
According to the present invention, firstly, the above objects and advantages of the present invention are attained by a crystalline mixture solid composition which comprises 20 to 75 wt % of &agr;-D-glucopyranosyl-1,1-mannitol, 23 to 70 wt % of &agr;-D-glucopyranosyl-1,6-sorbitol and 2 to 25 wt % of &agr;-D-glucopyranosyl-1,1-sorbitol (above weight percentages are based on the total weight of
&agr;-D-glucopyranosyl-1,1-mannitol,
&agr;-D-glucopyranosyl-1,6-sorbitol and
&agr;-D-glucopyranosyl-1,1-sorbitol).
According to the present invention, secondly, the above objects and advantages of the present invention are attained by a composition which comprises 20 to 75 wt % of
&agr;-D-glucopyranosyl-1,1-mannitol, 23 to 70 wt % of
&agr;-D-glucopyranosyl-1,6-sorbitol and 2 to 25 wt % of
&agr;-D-glucopyranosyl-1,1-sorbitol and has a specific surface area of 0.07 to 0.1 m
2
/g.
According to the present invention, thirdly, the above objects and advantages of the present invention are attained by a composition which comprises 30 to 75 wt % of
&agr;-D-glucopyranosyl-1,1-mannitol and 25 to 70 wt % of
&agr;-D-glucopyranosyl-1,6-sorbitol and has a specific surface area of 0.07 to 0.1 m
2
/g.
Further, according to the present invention, fourthly, the above objects and advantages of the present invention are attained by a process for producing the above composition of the present invention, the process comprising the steps of:
(1) continuously supplying a raw material, which is obtained by optionally removing trehalulose from a mixture of isomaltulose and trehalulose produced from cane sugar through an isomerization reaction according to circumstances and hydrogenation into a kneader having a thin and long cooling zone together with seed crystals; and
(2) discharging the reaction product from an outlet continuously.
The present invention is described in detail hereinbelow.
A description is first given of the process of the present invention.
In the process of the present invention, the crystalline mixture solid composition of the present invention is produced from a raw material obtained by hydrogenating a mixture containing isomaltulose and trehalulose produced from cane sugar through an isomerization reaction. Before hydrogenation, trehalulose may be removed. The crystalline mixture solid composition of the present invention is produced by injecting the raw material into the kneader having a thin and long cooling zone together with seed crystals.
As for the preferred ratio of isomaltulose and trehalulose before hydrogenation, the amount of isomaltulose is 5 to 100% and that of trehalulose is 0 to 95%.
The crystalline mixture solid composition of the present invention can be produced by hydrogenating a mixture containing isomaltulose and trehalulose which is produced from cane sugar through an isomerization reaction or a mixture from which trehalulose has been removed without separating impurities. After hydrogenation, if necessary crystallization or the like is carried out as required to change the ratio of the three components.
The transferase used in the

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