JPH06107611A - Production of betaine - Google Patents

Abstract

PURPOSE:To efficiently produce high-purity betaine from a waste liquor of the Stephen process or a chromatographic waste liquor at a lower cost than that of a conventional method without using a chemical such as a regenerating agent. CONSTITUTION:A waste liquor of the Stephen process or a chromatographic waste liquor is used as a raw material solution and a salt type strong acidic cation exchange resin is used as a separating agent to fractionate the resultant effluent fraction. Thereby, a high-purity betaine fraction is obtained and crystallized by a boiling method. The hydrous crystal of the betaine is produced by regulating the boiling temperature to <=90 deg.C and the anhydrous crystal is produced by carrying out the whole process ranging from the boiling to the separation at >=100 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering and producing betaine from beet sugar industrial waste with high purity.

[0002]

BACKGROUND OF THE INVENTION Betaine is a useful substance that has been conventionally used as a feed additive and has also been developed as a seasoning and a flavor improver. Betaine is a basic nitrogen-containing compound that is widely present in the animal and plant kingdoms, and is particularly abundant in sugar beet root and other plants of the family Chenopodiaceae and aquatic animals such as octopus and squid. Further, it is known that it is a chemically stable substance and is not decomposed even in a high alkali treatment with coal or the like during the production of beet sugar and a heat treatment such as concentration and crystallization, and is transferred into molasses.

Conventionally, in order to recover betaine industrially,
A method of recovering from molasses that is classified as a by-product of the beet sugar industry by a chromatographic separation method, and chemically recovering from so-called Steffen waste liquid that is classified as a waste of sugar beet industry after recovering further sucrose from the molasses The method was mainly adopted. Furthermore, in addition, other cases reported as examples of recovery of betaine include an example obtained from a recycled waste liquid of a resin used in the ion-exchange desalting method, which is classified as a sugar beet sugar industrial waste, and a chemical treatment using sugar beet fermentation residue as a raw material. There has been an example in which betaine was obtained by removing the metal salt by means of or by using adsorption on an ion exchange resin.

FIG. 1 shows a flow chart of the production of betaine by the conventional chemical method and ion exchange desalination method. As shown in FIG. 1, the chemical method is to treat the Steffen waste liquor with sulfuric acid, divide it into a precipitate and a solution, and further purify the solution to obtain betaine. The ion-exchange desalting method is a method in which the ion-exchange resin obtained by subjecting molasses to an ion-exchange desalting treatment is eluted with ammonia, and the recycled waste liquid is purified to obtain betaine.

[0005]

However, in the above-mentioned method which has been conventionally performed, hydrochloric acid, sulfuric acid, an organic solvent,
Since a chemical such as ammonia is used, the refining cost is high. Moreover, betaine of high purity could not be efficiently obtained from these methods.

Furthermore, recently, sucrose has been recovered from waste molasses, which is a by-product of the beet sugar industry, by using an ion exchange resin as a separating agent. It is classified as industrial waste.)
No case has been reported in which high-purity betaine was recovered from E.coli. Therefore, in order to solve the above-mentioned problems, the present invention does not use a chemical such as a regenerant from the Steffuffen waste liquid or the chromatographic waste liquid, at a lower cost than the conventional method, efficiently, and with high purity. It is an object to provide a method for producing betaine.

[0007]

In order to solve the above-mentioned problems, the present invention provides a waste liquid (a so-called chromatographic waste liquid) produced when sucrose is recovered from beet molasses using a salt type strongly acidic cation exchange resin as a separating agent. ) Is used as the raw material liquid, or the waste liquid generated when sucrose is recovered from the beet sugar concentrate by the Steffen method (so-called Steffen waste liquid) is used as the raw material liquid, and this raw material liquid is separated into salt-type strongly acidic cation exchange resin This is a method for producing betaine by separating it using the agent and collecting betaine.

The composition of the chromatographic waste liquid or the Steffen waste liquid used in the present invention is as follows, for example.

[0009]

[Table 1]

The ion exchange resin used in the present invention has a low divinylbenzene content, for example, 6%.
It is preferable that the content is about the same, that is, that the degree of drafting is low,
For example, resins such as Diaion UBK530K (trade name) and Dowex 99 (trade name) are preferably used, and the average particle diameter thereof is preferably 320 to 360 μm.
Moreover, it is preferable to use a sodium salt as a salt to be bound with this.

Next, a method for producing betaine of the present invention using a salt type strong acid cation exchange resin will be described. For example, chromatographic waste liquid is Diaion UBK530K, average particle size 3
A case of treatment with 60 micron, Na type will be explained. A stainless steel column with an inner diameter of 180 mm and a height of 1000 mm with a heat insulation jacket is prepared by using the above-mentioned DIAION UBK.
24l of 530K-Na type is filled and the temperature is adjusted to 80 ° C.
Chromatography waste liquid (Brix 57.6, sucrose 1) that had been pretreated from the top of this column with a filter and heated to 80 ° C.
0.9% (per solid content), betaine 10.1% (per solid content) 1.2l (5% of resin amount (V / V)) was supplied, and SV (space velocity: outflow amount 1 / resin) Amount l / 1 hour)
At 0.55, the resin is made to flow down, and then distilled water at 80 ° C. is supplied at the same SV. The first effluent, 6.6 l, was discarded, and 0.8 l was sequentially collected as one fraction.
The results shown in Table 2 were obtained. Regarding the analysis method of sucrose and betaine, the liquid chromatography method was used for sucrose and the Rynekke salt method was used for betaine. The indications in Table 2 are based on anhydrous basis.

[0012]

[Table 2]

As shown in Table 2, due to the molecular sieving effect of the resin, betaine flows out after the disaccharide sucrose and other non-sugar components, and the betaine purity of each fraction differs. Therefore, by arbitrarily selecting the recovery fraction, that is, by changing the cut point, it is possible to obtain a recovery liquid with high betaine purity. The recovered solution is concentrated and crystal growth is performed by the infusion method to easily collect betaine monohydrate crystals. Also, anhydrous betaine crystals can be obtained by performing decoction at high temperature.

In the above example, one condition was explained, but the concentration range of each waste liquid supplied to the resin column may be Brix 10 to 60, and the supply amount is 2.5 to 7.5 with respect to the resin. % (V / V), liquid flow rate SV
Is not significantly different in the range of 0.25 to 0.75. As described above, the present invention uses a chromatographic waste liquid and a Steffen waste liquid as a separating agent of a salt type strongly acidic cation exchange resin, recovers the resulting effluent in an appropriate range, and concentrates and sucrose the same. High-purity betaine can be easily produced as monohydrate crystals or anhydrous crystals. In particular, in the present invention, it is possible to manufacture without using any chemicals that cause environmental problems, and the industrial value is extremely large.

That is, when making hydrous crystals, the decoction temperature is set to 9
When the anhydrous crystal is prepared at 0 ° C. or lower, all the steps from the decoction to the separation are maintained at 100 ° C. or higher while the crystal is grown and separated, and the crystal is not washed.

[0016]

Example 1 A stainless steel column having a diameter of 180 mm and a height of 1000 mm with a heat insulating jacket was filled with 24 liters of an average particle size of 330 μm of Dowex 99 regenerated into Na type, and warm water was circulated at 80 ° C. in the jacket to keep it warm While passing 80 ° C warm water from the top of the column, keep the resin tank at 80 ° C.
To adjust the temperature. When the effluent reaches 80 ° C, the hot water supply is stopped. Next, chromatographic waste liquid (Brix 49.2,
Sucrose 17.25% on BX, betaine 17.10% on
BX) 1.2 l is filtered, heated to 80 ° C. and SV 0.5
5. Flow down the ion exchange resin column at 5 and continue at 80 ° C.
Of distilled water is supplied at the same SV.

8 l of the first effluent is discarded and 0.8 l
Fraction, No. Collect 3 fractions 11-13. The same treatment as this was repeated 8 times to obtain a recovered solution having a betaine purity of 88.30%. The recovered liquid was concentrated to Brix 60 to obtain a mother liquor, and crystal growth was performed by a sucrose method using a rotary evaporator. Keep the water bath temperature at 90 ° C and the vacuum degree in the flask to 120
Crystal growth was performed at Torr and a liquid temperature of 80 ° C. to obtain 1217 g of a crystal slurry of betaine monohydrate. Centrifuge this at 3000 rpm, and
After 9 g of water was sprayed, it was allowed to stand and dry for 5 hours at 105 ° C. in a thermostat to obtain 518 g of betaine having a purity of 98.0% and a water content of 1.5%. Photographs before and after drying the hydrous betaine are shown in FIG. 2, FIG. 2 (a) before being dried, and FIG. 2 (b) after being dried. The dried crystals become milky white due to the loss of water from the inside, and the surface has no gloss.
The purity of the obtained betaine was quantified by a rapid colorimetric method of precipitation with a lineecke salt, using the commercially available reagent betaine as a reference. The recovery rate of this crude crystal was 50.5% with respect to betaine in the supplied chromatographic waste liquid on an anhydrous basis.

[0018]

Example 2 The same column containing the resin used in Example 1 was adjusted to 80 ° C. as in Example 1, and Steffen waste liquid (Brix 54.8, betaine 15.
1.2% of 2% (per solid content) was filtered and heated to 80 ° C., and the resin tank was allowed to flow down with SV 0.55, followed by 80
C. hot water at the same SV was supplied and the first effluent 8 l was discarded, no. Collect 3 fractions 12-14. The same scan was repeated 8 times to obtain a recovered solution having a betaine purity of 89.7%.

This recovered liquid was used as in Example 1 for Brix 6
Concentrate to 0 to give mother liquor, and heat oil bath at high temperature of 130 ℃
Keep the vacuum inside the flask at 300 Torr and the liquid temperature at 1
When crystal growth was performed at 10 ° C., 1036 g of anhydrous betaine crystal slurry was obtained. 3000 rpm
Centrifuge without water sprinkling in a thermostat
The mixture was allowed to stand and dry at 2 ° C. for 2 hours to obtain 325 g of anhydrous betaine crystals having a purity of 99.0% and a water content of 0.27%. Photographs of anhydrous betaine before and after drying are shown in FIG. 3, where FIG. 3 (a) is before drying and FIG. 3 (b) is after drying. The water content of the anhydrous crystal is only dried, and it remains transparent and does not lose its luster even after drying.

The recovery rate of this anhydrous betaine was 32.0% with respect to betaine in the supplied Steffen waste liquid.

[0021]

According to the present invention, the following effects are exhibited. (1) High-purity betaine can be produced without using any chemicals that cause environmental problems. (2) High-purity betaine can be easily produced as monohydrate crystals or anhydrous crystals.

[Brief description of drawings]

FIG. 1 shows a flow chart of the production of betaine by a conventional chemical method and an ion exchange desalination method.

2A and 2B show states before and after drying of hydrous betaine, FIG. 2A being before drying and FIG. 2B being after drying.

3A and 3B show states before and after drying of anhydrous betaine, where FIG. 3A is before drying and FIG. 3B is after drying.

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[Procedure amendment]

[Submission date] September 30, 1993

[Procedure Amendment 2]

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Claims (2)

[Claims] 1. A waste liquid generated when sucrose is recovered from a sugar beet molasses using a salt-type strong acid cation exchange resin as a separating agent is used as a raw material liquid, and the raw material liquid is used as a separating agent. A method for producing betaine, characterized in that the betaine is collected and separated to collect betaine. 2. A waste liquid generated when sucrose is collected from beet sugar-to-sugar by the Steffen method is used as a raw material liquid, and the raw material liquid is fractionated by using a salt type strong acid cation exchange resin as a separating agent to recover betaine. A method for producing betaine characterized by the above.