JPH0369561B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention deals with solanesol, which is carried out using a purification tower.
Concerning a method for purifying crystalline substances such as decaprenol, coenzyme Q ₁₀ , etc. Conventionally, a method for purifying crystalline substances using a purification tower involves forming a crystalline layer on the inner wall of the tower, then heating the outer wall of the tower to sweat this crystalline layer, removing impurities, and then dissolving it by heating. method is known.
However, this method has the drawback that a sufficient purification effect cannot be obtained because the crystal layer often peels off from the inner wall of the column. The present inventor has completed the present invention as a result of various studies on methods for solving the above-mentioned drawbacks of conventional purification methods and obtaining purified products with high purity and recovery rate. The present invention is a method for crystallizing and refining a crystalline substance using a purification tower consisting of an outer cylinder and a perforated inner cylinder spaced apart from the outer cylinder. In general, a crystalline substance purification device is equipped with a distributor 1 at the top and a single storage tank 3 or a plurality of storage tanks 3 with branch piping, which is detachably attached to the bottom 2a.
A purification tower 2 equipped with a purification tower 2, a circulation device 4 that re-supplies purified liquid stored in a storage tank 3 to a distributor 1 with a pump 4a, and a heat medium tank 5b equipped with a temperature control unit 5a, which connects a pump 5c. A heat medium circulation device 5 that causes the heat medium supplied to flow down the purification tower outer wall 2b and recovers it in a heat medium tank 5b.
and a constant temperature bath 6 having a temperature control unit 6a and containing the storage tank 3 filled with liquid. In the purification method of the present invention, a method similar to the purification process using this purification device is adopted, but it differs greatly from the conventional method in that the purification column 2 equipped with the perforated inner cylinder 7 is used as described above. There is. The perforated inner cylinder 7 is made of steel or other metals, glass, ceramics, polycarbonate or other synthetic resins, and is made of, for example, wire mesh or punched metal. The distance between the purification tube 2, that is, the outer tube 2 and the perforated inner tube 7 is about 2 to 15 mm, especially 5 mm.
~10 mm is preferred. If this distance is too short, the film of the crystalline material flowing down the inner wall 2c of the outer cylinder will be biased, and a homogeneous crystal layer cannot be formed, resulting in poor purification effect. On the other hand, if this distance is too long, the weight of the crystal layer will be unbalanced,
This is not preferable because the layer will peel off. Perforated inner cylinder 7
The opening size of the pores is about 0.14~0.8mm, especially 0.21~
0.42 is preferred. If the viscosity of the crystalline substance-containing liquid flowing down the outer cylinder inner wall 2c is relatively low, a small size is preferable. Crystalline substances can be used directly or by dissolving them in ethanol or other suitable solvent.
supply to. Next, this crystalline substance-containing liquid flows down the outer cylinder inner wall 2c in the form of a thin film. On the other hand, when refining a crystalline substance with a melting point of about 40°C by adding a solvent, the heating medium stored in the heating medium tank 5b is initially
After adjusting the temperature to about 0.degree. C., it is allowed to flow down along the outer wall 2b of the outer cylinder, and then the starting temperature is lowered to 10 to 40.degree. C., completing preparations for crystallization. After that, about 60~
Cool to 0-20°C over 150 minutes. The crystalline substance-containing liquid flowing down the inner wall 2c of the outer cylinder gradually grows a crystal layer as the temperature of the heat medium decreases, until the heat medium reaches zero.
Stop the downstream circulation when the temperature reaches ~20°C. After the heating medium flows down for about 10-15 minutes at this temperature, the temperature of about 0.1
It is heated to about 10-40°C at a heating rate of 0.8°C/min to 0.8°C/min, and kept at the same temperature for about 30-120 minutes to cause the crystal layer to sweat. After the sweating operation is completed, the storage tank 3 is replaced with a new one, and the temperature of the heat medium is rapidly raised to 40° C. or higher to melt and flow down the crystal layer, and the crystal layer is stored in the storage tank 3. The obtained molten crystals are concentrated to obtain a purified product. According to the purification method of the present invention, the inner wall 2c of the purification column 2
Crystals can be obtained with high purity and recovery rate without the crystal layer peeling off. EXAMPLES Next, the present invention will be described with reference to Examples to further specifically illustrate the present invention. Example 1 A fractional crystallization purification tower (outer cylinder and internal cylinder) was constructed by attaching a perforated stainless steel inner cylinder 7 with an opening of 0.25 mm, a diameter of 26 mm, and a length of 900 mm to a glass outer cylinder 2 with a diameter of 44 mm and a length of 900 mm. The following crystallization purification was carried out using a purification apparatus with a distance between cylinders (9 mm). 250.6 g of solanesol with a purity of 88.2% by weight was dissolved in 751.8 ml of ethanol and continuously supplied to the distributor 1 at the top of the purification column at a flow rate of 400 ml/min. The supplied solution flowed down the outer cylinder inner wall 2c in the form of a thin film, was stored in the storage tank 3, and was continuously circulated and supplied to the distributor 1. Separately, a heating medium whose starting temperature was adjusted to 20° C. was flowed down on the outer wall 2b of the outer cylinder under program control. Cool this heat medium to 0℃ over 120 minutes,
A crystal layer of the solanesol solution was grown on the inner wall 2c of the outer cylinder, and circulation of the solution was stopped. Next, change the heat medium to 0
After flowing down for 20 minutes at a temperature of .degree. C., it was heated to 16.degree. C. at a heating rate of 0.178.degree. C./min and kept at this temperature for 50 minutes to cause the crystal layer to sweat. Thereafter, the storage tank 3 was replaced with a new one, and the temperature of the heat medium was rapidly raised to 40°C to cause the crystal layer to melt and flow down. The molten crystals were taken out from storage tank 3 and concentrated to obtain 166.4 g of purified solanesol (purity 93.0%, recovery rate 70.0%). Example 2 The operation of Example 1 was repeated four times after the recovery step, and a test for improving the purity of purified solanesol was conducted. The results are shown in Table 1.

[Table] Example 3 Using the purification apparatus used in Example 1, decaprenol was crystallized and purified in the following manner. 250.6 g of decaprenol with a purity of 68.9% was dissolved in 751.8 ml of ethanol, and the solution was continuously supplied to the distributor 1 at the top of the purification column at a flow rate of 400 ml/min.
The supplied solution flowed down the inner wall 2c of the outer cylinder in the form of a thin film, was stored in the storage tank 3, and was continuously supplied in circulation to the distributor 1. Separately, a heating medium whose starting temperature was adjusted to 30° C. by program control was allowed to flow down onto the outer wall 2b of the outer cylinder. The heating medium was cooled down to 10° C. over 120 minutes to grow a crystal layer of the decaprenol solution on the inner wall 2c of the outer cylinder, and the circulation of the solution was stopped. Next, heat medium 10℃
After flowing down for 20 minutes at a temperature of , the crystal layer was heated to 23°C at a heating rate of 0.178°C/min and held at this temperature for 50 minutes to cause the crystal layer to sweat. Thereafter, the storage tank 3 was replaced with a new one, and the temperature of the heat medium was rapidly raised to 50°C to cause the crystal layer to melt and flow down. The molten crystals were taken out from storage tank 3 and concentrated to obtain 126.6 g of purified decaprenol (purity 90.8%, recovery rate 66.6%). Example 4 Using the purification apparatus used in Example 1, coenzyme Q ₁₀ was purified as follows. 250.6g of Coenzyme Q ₁₀ with a purity of 81.8% in ethanol
The solution was dissolved in 751.8 ml and continuously supplied to the distributor 1 at the top of the purification column at a flow rate of 400 ml/min. The supplied solution flowed down the outer cylinder inner wall 2c in the form of a thin film, was stored in the storage tank 3, and was continuously circulated and supplied to the distributor 1. Separately, a heating medium whose starting temperature was adjusted to 40°C was flowed down on the outer wall 2b of the outer cylinder under program control. This heating medium was cooled down to 15℃ over 120 minutes,
A crystal layer of the coenzyme Q ₁₀ solution was grown on the inner wall 2c of the outer cylinder, and circulation of the solution was stopped. Next, heat the heat medium to 15℃
After flowing down for 20 minutes at a temperature of , the crystal layer was heated to 28°C at a heating rate of 0.178°C/min and held at this temperature for 50 minutes to cause the crystal layer to sweat. Thereafter, the storage tank 3 was replaced with a new one, and the temperature of the heat medium was rapidly raised to 55°C to cause the crystal layer to melt and flow down. The molten crystals were taken out from storage tank 3 and concentrated to obtain 166.4 g of purified coenzyme Q ₁₀ (purity 94.9%, recovery rate 77.0%). Example 5 Solanesol crystals were produced in the same manner as in Example 1, except that instead of the perforated inner cylinder 7 made of stainless steel mesh with an opening of 0.25 mm, the perforated inner cylinder 7 made of stainless steel punch metal with an opening of 0.42 mm was used. Purification was performed to obtain 164.6 g of purified product (purity 93.1%, recovery rate 69.3%). Example 6 Crystallization and purification of solanesol was carried out in the same manner as in Example 2, except that stainless steel mesh perforated inner tubes 7 with mesh openings of 0.149 mm, 0.210 mm, and 0.420 mm were used instead of 0.25 mm. Summer. The result of the fourth iteration of the same operation as in Example 2 is
Shown in the table.

[Table] Example 7 In Example 2, the diameter of the perforated inner cylinder 7 was 38 mm and 20 mm (distance between the outer cylinder and the perforated inner cylinder) instead of 26 mm (distance between the outer cylinder and the perforated inner cylinder). Crystallization and purification of solanesol was carried out in the same manner except that stainless steel mesh perforated inner cylinders 7 with distances between the inner cylinders of 3.0 mm and 12.0 mm, respectively, were used. Table 3 shows the results of the fourth repeated operation similar to Example 2.

[Table] Comparative Example 1 Crystallization and purification of solanesol was carried out in the same manner as in Example 1, except that a conventional fractional crystallization purification tower from which the perforated stainless steel mesh inner cylinder 7 was removed was used. As a result, after letting the heat medium flow down for 20 minutes at 0℃, we tried to heat it up to 16℃ at a temperature increase rate of 0.178℃/min, but at 14℃ the crystal layer suddenly peeled off from the inner wall 2c of the outer cylinder. Crystal layer sweating could not be achieved. The exfoliated crystals were taken out and concentrated to obtain 122.5 g of purified solanesol (purity 89.2%, recovery rate 49.4%). Comparative example 2 Aperture 0.125mm instead of 0.25mm
Crystallization and purification of solanesol was carried out in the same manner as in Example 2, except that the perforated inner tube 7 made of 0.840 mm stainless steel mesh was used. Table 4 shows the results of the fourth repeated operation similar to Example 2.

[Table] Comparative Example 3 The diameter of the perforated inner cylinder 7 was 42 mm and 10 mm (distance between the outer cylinder and the perforated inner cylinder) instead of 26 mm (distance between the outer cylinder and the perforated inner cylinder). Crystallization and purification of solanesol was carried out in the same manner as in Example 2, except that the perforated inner cylinder 7 made of stainless steel mesh with openings of 1.0 mm and 17.0 mm, respectively, was used. Example 2
Table 5 shows the results of the fourth iteration of the same procedure.

【table】 [Brief explanation of drawings]

FIG. 1 is a flow sheet of a conventional crystalline substance purification apparatus, and FIG. 2 is a longitudinal cross-sectional side view of a purification column used in the method of the present invention. 1...Distributor, 2...Refining tower (outer cylinder),
2a...same bottom, 2b...same outer wall, 2c...same inner wall, 2
d... Jacket, 3... Storage tank, 4... Purified liquid circulation device, 5... Heat medium circulation device, 7... Perforated inner cylinder.

Claims (1)

[Claims] 1 A crystalline material-containing liquid is allowed to flow down the inner wall of the outer cylinder of a purification tower consisting of an outer cylinder and an inner cylinder arranged with a space therebetween to grow a crystal layer, and then the outer cylinder A method for purifying a crystalline substance, which is characterized by flowing a heating medium down an outer wall and heating it to cause the crystalline layer to sweat, and then rapidly increasing the temperature to melt and flow down the crystalline layer. 2. The method for purifying a crystalline substance according to claim 1, wherein the distance between the outer cylinder and the perforated inner cylinder is about 2 to 15 mm. 3 The opening size of the hole in the perforated inner cylinder is 0.14 to 0.8
2. The method for purifying a crystalline substance according to claim 1, wherein the crystalline substance is 1 mm.