JPS6141559B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating a mixture of glucose and fructose into a glucose solution and a fructose solution using a fixed bed filled with a strongly acidic cation exchange resin of alkaline earth metal type. The purpose of this method is to obtain high-purity glucose and fructose solutions at high yields. Conventionally, as a method for separating glucose and fructose from a mixed sugar solution of glucose and fructose, there has been a method of separating glucose and fructose by column chromatography using a calcium-type cation exchange resin (U.S. Patent No. 3044904, Japanese Patent Publication No. 45-24807). ), a method for separating fructose and glucose from sutucarose or invert sugar containing sutucallose (Japanese Patent Publication No. 46-5782, Japanese Patent Publication No. 101140/1972), a method for separating fructose and glucose from isomerized sugar using a simulated moving bed (JP-A-53-26336, JP-A-53-
No. 88335) have been proposed. However, these methods have various difficulties and are not satisfactory when applied industrially. For example, the method of U.S. Patent No. 3,044,904 describes a principle method for separating fructose from a mixture of fructose and glucose, but there are difficulties in industrial application; US Patent No.
Although this method is an improvement on the method of No. 3044904, it is not possible to obtain relatively high yield and high purity glucose and fructose solutions. In addition, the method disclosed in Japanese Patent Publication No. 46-5782 leaves a part of the cation exchange resin in the H form and passes the raw sugar solution through it, converting sucrose in the sugar solution and adsorbing impure salts. The method of implementation is
In order to increase the separation efficiency between fructose and glucose, a very long column is required, and this method is not necessarily advantageous from an industrial perspective. Furthermore, although JP-A-51-101140 is an improvement on the method of the above-mentioned patent, the number of columns is very large and the operation is complicated and impractical for industrial application. Furthermore, JP-A-53-
No. 26336 and JP-A-53-88335 differ in that the former uses zeolite as an adsorbent and the latter uses a cation exchange resin, but a pseudo moving bed is used as the separation method. Therefore, the number of columns is very large, the operation is complicated, and there are many problems when it is applied industrially. When applied as an industrial device, using a fixed bed has the advantage of being easier to operate and more reliable than a simulated moving bed. As mentioned above, the method of this issue has the drawback that it is not possible to obtain highly purified glucose and fructose solutions in high yields. In other words, the method disclosed in Japanese Patent Publication No. 45-24807 uses a fixed bed filled with an alkaline earth metal-type strongly acidic cation exchange resin to convert a stock solution containing glucose and fructose (hereinafter simply referred to as the stock solution) into glucose. Separation into liquid and fructose liquid is carried out by passing the stock solution and water through the fixed bed in that order, and dividing the effluent into each using a so-called chromatographic separation method. Follow the steps below. That is, when the stock solution and water are passed through the fixed bed in this order, glucose and fructose are chromatographically separated, and the effluent is divided to some extent into glucose part G and fructose part F as shown in FIG. Then, as shown in Figure 2, this effluent was separated into seven types: dilute liquid A, glucose liquid B, glucose rich liquid C, fructose rich liquid D, fructose liquid E, dilute fructose liquid, and dilute liquid G. , thin liquids A and G are received in a thin liquid tank and taken out of the system, glucose liquid B and fructose liquid H are respectively received in a receiving tank and taken out of the system as products, and further glucose rich liquid C, fructose rich liquid D, The diluted fructose solution is received in three recycling tanks, and then the glucose-rich solution is continuously recycled.
Water is passed in this order through the stock solution, fructose-rich solution, diluted fructose solution, and the effluent is again taken out into each tank as shown in Figure 2, and this process is repeated to obtain a glucose solution and a fructose solution. . However, in this method, as shown in FIG. 2, the adsorption zones of glucose and fructose in the effluent are quite close to each other, making it impossible to obtain highly purified glucose and fructose solutions in high yield. The present invention solves the above-mentioned drawbacks of the conventional separation method using a fixed bed packed with strongly acidic cation exchange resins of alkaline earth metal type, and enables highly purified glucose and fructose solutions to be produced in high yields. It is characterized by the fact that a mixed stock solution of glucose and fructose is passed in a downward or upward flow through a fixed bed filled with an alkaline earth metal-type strongly acidic cation exchange resin to obtain a glucose solution and a fructose solution. In separating the liquid, a specified amount of the stock solution and a specified amount of water are passed in the order of the stock solution and the water, and the effluent is circulated through the packed bed for at least two cycles or more in the order in which it flows through the packed bed. A preliminary step is performed to amplify the distance between the formed glucose adsorption zone and fructose adsorption zone, and after the circulation of the preceding step, the dilute glucose solution, glucose solution, glucose/fructose mixture, fructose solution, and dilute fructose solution are chromatographed in this order from the outlet. Of the effluent that flows out with a specific concentration distribution, a specified amount of the glucose solution and a specified amount of the fructose solution are taken out of the system in spots, while the other liquids are circulated again in the order in which they flow out. is injected into the glucose/fructose mixture in the circulating fluid where the fructose content ratio is slightly lower than the fructose content ratio of the undiluted solution, and a specified amount of water is injected into the diluted fructose solution in the circulating fluid. Afterwards, a steady process is performed in which the solution is injected spot-wise and circulated so that the total volume of the stock solution and water to be injected is equal to the total volume of the glucose solution and fructose solution taken out of the system, and the steady process is repeated thereafter. The present invention relates to a method for separating glucose and fructose, which is characterized by sequentially taking out a glucose solution and a fructose solution. Hereinafter, an example of an embodiment of the present invention will be described in detail using the drawings. FIG. 1 is an explanatory diagram showing the flow of a glucose and fructose separation device, in which one end of an inlet pipe 3 is connected to the upper end of an adsorption tower 2 filled with an alkaline earth metal type strongly acidic cation exchange resin 1. and pump the other end
communicate with. Further, one end of the outflow pipe 5 is connected to the lower end of the adsorption tower 2, and the other end is connected to the outflow branch pipes 5a, 5b, 5c,
5d, 5e, and 5f, respectively. A glucose thin material tank 6, a glucose liquid tank 7, a glucose rich liquid tank 8, a fructose rich liquid tank 9, a fructose liquid tank 10, and a fructose thin material tank 11 are installed, each having a weir 22 inside,
The effluent from the outflow branch pipe 5a is sent to the glucose thin material tank 6.
The effluent from the outflow branch pipe 5b flows into the glucose liquid tank 7, the effluent from the outflow branch pipe 5c flows into the glucose rich liquid layer 8, and the effluent from the outflow branch pipe 5d flows into the fructose rich liquid tank 9. The structure is such that the effluent from the branch pipe 5e flows into the fructose liquid tank 10, and the effluent from the outflow branch pipe 5f flows into the fructose thin product tank 11, respectively. On the other hand, one end of the suction pipe 12a is connected to the lower part of the glucose thin liquid tank 6, one end of the suction pipe 12b is connected to the lower part of the glucose liquid tank 7, one end of the suction pipe 12c is connected to the lower part of the glucose rich liquid tank 8, and one end of the suction pipe 12c is connected to the lower part of the glucose rich liquid tank 9.
One end of the suction pipe 12d is connected to the bottom of the fructose solution tank 10, one end of the suction pipe 12e is connected to the bottom of the fructose liquid tank 10, and one end of the suction pipe 12f is connected to the bottom of the fructose thin product tank 11, and the other ends of all the suction pipes are connected. It is connected to a suction main pipe 13, and the suction main pipe 13 communicates with the pump 4. Further, a stock solution tank 14 and a water tank 15 are installed, and one end of the introduction pipe 16a is connected to the bottom of the stock solution tank 14, and one end of the introduction pipe 16b is connected to the bottom of the water tank 15, and the other end of these introduction pipes is connected. Connected to pumps 17 and 18, respectively. Also pumps 17, 18
One end of the discharge pipes 19a, 19b is connected to each of the two ends, and the other end is connected to the middle of the inflow pipe 3. Note that a glucose liquid extraction pipe 20 is branched and attached to the suction pipe 12b, and a fructose liquid extraction pipe 21 is branched and attached to the suction pipe 12e. When separating a glucose solution and a fructose solution from a stock solution using the glucose and fructose separation device configured as described above, in the present invention, first, a specified amount of the stock solution and a specified amount of water are passed through the stock solution and then the water. Then, a preliminary step is performed in which the effluent is circulated again through the packed bed in the order in which it flows out for at least two cycles or more. That is, a specified amount of the stock solution is poured into the stock solution tank 14 from the top of the adsorption tower 2, in which some water layer is formed above the packed bed of the strongly acidic cation exchange resin 1.
Then, when the predetermined amount of the stock solution has finished flowing in, a predetermined amount of water is continuously caused to flow in from the water tank 15 using the pump 18. On the other hand, the effluent is discharged from the lower part of the adsorption tower 2 simultaneously with the inflow of the stock solution and water. As shown in FIG. 2, the effluent liquid is separated into a glucose part G and a fructose part F to some extent as a glucose liquid and a fructose liquid and then flows out.
Using 5b, 5c, 5d, 5e, and 5f, the liquids flowing out are, in order, glucose thin tank 6, glucose liquid tank 7, glucose rich liquid tank 8, fructose rich liquid tank 9,
It is received in a fructose liquid tank 10 and a fructose thin product tank 11. After the liquid of each portion is received in each tank in this way, the liquid of each of these portions is then allowed to flow back into the adsorption tower 2 in the order in which it was discharged and circulated. That is, the pump 4 is used to first cause the liquid in the glucose thin tank 6 to flow from the upper part of the adsorption tower 2 through the suction pipe 12a, and then the liquid in the glucose liquid tank 7, the glucose rich liquid tank 8, the fructose rich liquid tank 9, and the fructose The liquids in the liquid tank 10 and the fructose thin layer 11 are passed through the suction pipes 12a, 12b, 12c, 12d, 12e, 12 in the order in which they flow out.
F, respectively, and the effluent is introduced from the upper part of the adsorption tower 2 one after another, and the effluent is returned to the glucose thin tank 6, the glucose liquid tank 7, the glucose rich liquid tank 8, the fructose rich liquid tank 9, the fructose liquid tank 10, It is received in each tank of the fructose thin product tank 11. When the above circulation is carried out, the concentration distribution of the effluent of the second cycle shown in Figure 3 and the concentration distribution of the effluent of the third cycle shown in Figure 4 each time the cycle is repeated. As shown, the concentration curves of glucose part G and fructose part F gradually diverge. This indicates that the distance between the glucose adsorption zone and the fructose adsorption zone formed while moving in the packed bed was gradually increased. In the present invention, the distance between the glucose adsorption zone and the fructose adsorption zone can be amplified by performing the preceding step of circulating the effluent as described above, so that a relatively high purity glucose solution can be obtained in the subsequent regular step. It is possible to obtain fructose solution with high yield. For example, when obtaining a glucose solution and a fructose solution from the effluent in the third cycle after circulation, the glucose solution and the fructose solution are sequentially taken out by performing the routine steps described below. In the third cycle, as shown in Figure 4, a portion of the glucose liquid that first flows out goes to the glucose thin liquid tank 6, and a portion of the next relatively high-purity glucose liquid goes to the glucose liquid tank. 7, the next portion of the glucose-rich mixture is transferred to the glucose-rich liquid tank 8,
The next portion of the fructose-rich liquid mixture is sent to the fructose-rich liquid tank 9, the next relatively high-purity fructose liquid portion is sent to the fructose liquid tank 10, and the final portion of the fructose thin liquid to be drained is fed to the fructose-rich liquid tank 9. Since the thin liquid tank 11 is used to separate a portion of the relatively high-purity glucose liquid in the glucose liquid tank 7 using the glucose liquid take-out pipe 20, the fructose liquid take-out pipe 21
A portion of the relatively high purity fructose solution in the fructose solution tank 10 is taken out of the system. On the other hand, the effluents from the other tanks are again circulated in the order of their outflow using the pump 4, and at this time, a specified amount of stock solution and a specified amount of water are injected spot-wise into the portions described below. That is, in the circulation in the steady process, the effluent from the glucose thin liquid tank 6 and the effluent from the glucose rich liquid tank 8 are made to flow into the adsorption tower 2 in this order using the pump 4.
Next, a specified amount of the stock solution is pumped from the stock solution tank 14 to the pump 17.
influx using. After a specified amount of the stock solution is injected, the effluent in the fructose rich liquid tank 9 and the effluent in the fructose thin liquid tank 11 are made to flow in this order, and then a specified amount of water is injected from the water tank 15 using the pump 18. On the other hand, the effluent flowing out from the adsorption tower 2 is divided into 6, 7, 8, 6, 7, 8, and 7 parts, respectively, as shown in Fig. 4.
It is received in each tank 9, 10, and 11 in order. From then on,
Glucose and fructose solutions are sequentially extracted through a regular process in which the extraction of glucose and fructose solutions and the injection of the stock solution and water are repeated in the same way. In the present invention, by first carrying out the preceding steps as described above and then sequentially repeating the steady steps, it is possible to sequentially extract relatively highly purified glucose and fructose solutions at relatively high yields. In this case, it is necessary that the glucose outflow curve and the fructose outflow curve be not disturbed during the circulation in the preceding process, and the glucose and fructose outflow curve formed in the steady process, for example, as shown in Fig. 4, must not be disturbed. It is necessary that the concentration distribution be reproduced in sequence thereafter. In the present invention, this is achieved by three technical means as explained below. First, when the effluent from the adsorption tower 2 is circulated through the preceding process and the regular process, the effluent flows into the adsorption tower 2 in the order in which it is discharged. Regarding circulation, in order to re-inflow the effluent into the adsorption tower 2 in the order in which it flows out, as many small tanks as possible are provided, and the effluent is received in order in these large number of tanks.When the reception is completed, the effluent is then transferred to each tank in the order in which it was received. It is possible to flow the effluent into the adsorption tower, but this method requires too many tanks and must be changed frequently, making it unsuitable for industrial equipment. Therefore, in the present invention, each tank 6, 7, 8,
This is achieved by providing a large number of weirs 22 at 9, 10, and 11. For example, to explain the glucose thin substance tank 6, if four weirs 22 with the other end open alternately are provided at intervals in the tank 6, the inside of the tank will be A, B, C, D, E from top to bottom. It can be divided into 5 chambers, and the liquid flows in from the top,
Since the liquid stays in chambers E, D, C, B, and A in the order in which it flows in, by taking out the liquid from the lower part of the tank, it becomes possible to drain it in the order in which it entered. Therefore, by providing four of these weirs 22, one tank has the separation capacity of five tanks. In Figure 1, there are six tanks, but if each tank is provided with four weirs, the same effect as dividing into 30 tanks can actually be obtained. Note that the same effect can be obtained by constructing each tank in the form of a serpentine tube having a relatively large diameter as shown in FIGS. 5 and 6, for example. As explained above, when the effluent from the adsorption tower 2 is circulated through the preceding process and the steady process by using the tank shapes as shown in Figures 1, 5, and 6, the effluent can be They can flow into the adsorption tower in the order of outflow. Second, the injection point of the stock solution in the steady process is to be at a portion of the glucose/fructose mixture in the circulating fluid where the fructose content ratio is slightly lower than the fructose content ratio of the stock solution. The glucose/fructose mixing part in the circulating fluid corresponds to the GL part when explained in Fig. 4, but in order to set the injection point of the stock solution to a part slightly lower than the fructose content ratio of the stock solution, it is shown in Fig. 4. If the ratio of glucose concentration G' and fructose concentration F' in the solid line part is equal to the ratio of glucose concentration and fructose concentration of the stock solution, for example, the part slightly before the solid line part, that is, the part indicated by dotted line m, is placed in the glucose rich liquid tank. 8 and the intake switching point to the fructose rich liquid tank 9. Third, the total amount of stock solution and water injected in the steady-state process must match the total amount of glucose liquid and fructose liquid taken out of the system. Only by making full use of the three technical means described above will it be possible to obtain highly purified glucose and fructose solutions in high yields. To explain the circulation in the preceding step of the present invention, as the circulation continues, the concentration curves of both sugars change as shown in Figures 2, 3, and 4, and the glucose part G and the fructose part F change. and become separated, but at the same time, the concentration of both sugars in the effluent also decreases. Therefore, if the number of cycles is too high, the sugar concentration will drop too much, which is not preferable, and the number of cycles should usually be about 3 to 5. Next, the inflow amounts of the stock solution and water during the preceding process and the water balance during the steady process in the present invention will be explained. First, the inflow amount of stock solution in the preceding process is 0.2 to 0.7
/-resin (ion exchange resin),
Within this range, the more the stock solution is allowed to flow in, the higher the concentration of both sugar solutions obtained in the regular process can be. However, if the amount of resin exceeds 0.7/-, the separation efficiency will decrease, which is not preferable. Next, the inflow amount of water is roughly proportional to the inflow amount of the stock solution, and is 0.2 ~
A ratio of 0.8/-resin is good; if more than this flows in, both sugars will be diluted more than necessary, which is not preferable. The water balance during the steady process is 0.05 to 0.15/% of the glucose dilute solution in Figure 4.
-Resin, preferably around 0.1/-resin, is received into the glucose thin tank 6, and the partial reflow of the glucose solution is 0.2 to 0.3/-resin, preferably 0.25/-
- A portion of the glucose-rich mixture is received as 0.15 to 0.4/- resin, preferably around 0.3/- resin, into the glucose-rich liquid tank 8, and a portion of the fructose-rich mixture is 0.1-0.3/-resin, preferably 0.2/-
- A part of the fructose liquid is received in the fructose liquid tank 9 as before and after resin, and a portion of the fructose liquid is received as 0.1 to 0.2/- resin, preferably 0.15/- to the fructose liquid tank 10 as around 0.15/-, and a part of the fructose thin liquid is 0.05 to 0.2/-. 0.15/−
It is preferable to receive the resin, preferably around 0.1/- resin, into the fructose thin material tank 11, respectively. The amount of stock solution to be injected is 0.1 to 0.3/- resin, preferably around 0.15/- resin, and the amount of water to be injected is 0.15 to 0.3/- resin, preferably around 0.2/- resin. Although six tanks are used in FIG. 1, if the concentration of the glucose solution or fructose solution to be taken out of the system does not need to be so high, the glucose thin material tank 6 or the fructose thin material tank 11 can be omitted. It is. However, 4 of the glucose liquid tank 7, glucose rich liquid tank 8, fructose rich liquid tank 9, and fructose liquid tank 10
Tanks are essential. The strongly acidic cation exchange resin used in the present invention is preferably porous, and the finer the particle size, the better from the standpoint of separation. However, if it is too fine, it will cause a large pressure loss in industrial equipment, causing an inability to pass liquid or one-sided flow, so a mesh of 40 to 200 mesh (in a wet state) is usually used. In the present invention, this strongly acidic cation exchange resin is used in the form of an alkaline earth metal adsorbed thereon, and is usually regenerated with calcium chloride and used in the calcium form. In addition, the raw sugar solution is generally an isomerized sugar solution obtained by isomerizing glucose, and the concentration of the sugar solution is 35 to 60%. Although the separation performance is better when the liquid is passed at room temperature, a temperature of 60°C to 80°C is preferable from the viewpoint of pressure loss during liquid passing and prevention of microbial contamination. The fructose liquid fraction separated according to the present invention becomes a product, while the glucose liquid fraction is returned to the isomerization process. Examples of the present invention will be described below. Example 850 ml of strongly acidic cation exchange resin XT-1022E (manufactured by Tokyo Organic Chemical Industry Co., Ltd.) with a particle size of 50 to 70 mesh was packed into a column with a diameter of 21 mm and a height of 2110 mm.
A 1N calcium chloride solution 3/- was passed through the resin to completely regenerate it into calcium form. Next, 255 ml of a sugar solution with an undiluted concentration of 45%, a glucose content ratio of 58%, and a fructose content ratio of 42% was added to this resin at temperature.
At 60℃, the liquid is passed in a downward flow at SV0.4, and then water is
340ml of water was passed through. Next, the effluent that flows out
The resin was collected in fractions of 0.05/- resin, and the liquid was sequentially passed from the top of the column in the order in which they were collected, and three cycles were repeated. Figure 7 shows the state of separation of glucose and fructose in the effluent of the third cycle. That is, each fraction is a dilute glucose solution, a glucose solution, a glucose-rich mixed solution, a fructose-rich mixed solution,
Divided into fructose solution and diluted fructose solution. The boundary between the glucose-rich mixed liquid and the fructose-rich mixed liquid was set at a point where the fructose content ratio was slightly lower than the fructose content ratio of the undiluted solution, that is, 39%. Next, 212.5ml of glucose solution (glucose
49.8g, fructose 5.4g) and fraction number No. 31~
170ml of 4-fraction fructose solution of 35 (fructose 32.8
g, glucose 3.1 g) is taken out of the system, and instead 170 ml of stock solution (glucose 53.2 g, fructose 38.6 g) is removed from the system.
g) and 212.5 ml of water were injected and the circulation continued again. That is, injections are performed in the order of dilute glucose solution, glucose rich mixture, undiluted solution, fructose rich mixture, dilute fructose solution, and water.
The glucose solution and fructose solution were separated by withdrawing and injecting the sugar solution every cycle. Table 1 shows the average sugar composition of the glucose solution and fructose solution taken out of the system. 【table】

[Brief explanation of the drawing]

The drawings all show an example of the embodiment of the present invention, and FIG. 1 is an explanatory diagram showing the flow of the method for separating glucose and fructose, and FIG. 2, FIG. 3, and FIG.
Each figure shows the concentration distribution of glucose and fructose in the effluent; the vertical axis represents the concentration of both sugars, and the horizontal axis represents the amount of effluent. Figure 3 shows the 4th cycle of the second cycle of circulation.
The figure is a graph of the concentration distribution in the third cycle of circulation. Figures 5 and 6 are explanatory diagrams showing other embodiments of the receiving tank used in the present invention, and Figure 7 shows the concentration distribution of glucose and fructose in the effluent of the third cycle of circulation in the example. It is a graph, where the vertical axis represents the concentration of both sugars, and the horizontal axis represents each fraction number.
It represents. 1... Strongly acidic cation exchange resin, 2... Adsorption tower, 3... Inflow pipe, 4... Pump, 5... Outflow pipe, 6... Glucose thin material tank, 7... Glucose liquid tank, 8... Glucose rich liquid tank, 9... Fructose rich liquid tank, 10... Fructose liquid tank, 11... Fructose thin liquid tank, 12... Inhalation tube, 13... Inhalation main tube, 14...
...Standard solution tank, 15...Water tank, 16...Introduction pipe, 1
7, 18...pump, 19...discharge pipe, 20...
Glucose liquid extraction pipe, 21...Fructose liquid extraction pipe, 22...Weir.

Claims (1)

[Claims] 1 When a mixed stock solution of glucose and fructose is passed in a downward or upward flow through a fixed bed filled with an alkaline earth metal type strongly acidic cation exchange resin to separate it into a glucose solution and a fructose solution, a specified amount is A glucose adsorption zone and fructose adsorption are formed while moving in the packed bed by passing the stock solution and a specified amount of water in the order of stock solution and water, and circulating the effluent through the packed bed in the order of flow for at least two or more cycles. A preceding process is performed to amplify the distance between the bands, and after the circulation of the preceding process, dilute glucose solution, glucose solution,
Of the effluent that flows out with a chromatographic concentration distribution in the order of glucose/fructose mixture, fructose solution, and diluted fructose solution, a specified amount of glucose solution and a specified amount of fructose solution are taken out of the system in spots, while the other The solution is circulated again in the order of flow, but at this time, a specified amount of the stock solution is injected spot-wise into the glucose/fructose mixed liquid part of the circulating fluid, where the fructose content ratio is slightly lower than the fructose content ratio of the stock solution. , a specified amount of water is injected in spots after the dilute fructose solution in the circulating fluid flows, and the total volume of the stock solution and water to be injected is made equal to the total volume of the glucose solution and fructose solution taken out of the system. 1. A method for separating glucose and fructose, which comprises performing a steady step of circulating the glucose and then repeatedly performing the steady step to sequentially take out a glucose solution and a fructose solution.