JPH08229306A - Production of useful material using pseudo moving layer type chromatographic separation operation - Google Patents

Abstract

PURPOSE: To efficiently produce useful materials with a small number of stages. by successively effecting chemical reaction within a system where sepn. operation is executed in pseudo moving layer type chromatographic sepn. operation to separate and recover the components (materials) desired to be separated out of soln. contg. plural components. CONSTITUTION: A pseudo moving layer apparatus consists of column groups endlessly connected with plural pieces of columns 1 to 8 in series and strongly acidic cation exchange resin are packed as packing materials into all these columns. The respective columns are set at the state satisfying the conditions of chemical reaction. The apparatus is provided with pipings including one piece from a supply port for eluate to an extract withdrawing port, three pieces from this withdrawing port to a raw material liquid supply port, three pieces from this raw material liquid supply port to a raffinate withdrawing port and one piece from this raffinate withdrawing port to an eluate supply port. The material having weak affinity is moved in a liquid flow direction and the material having strong affinity is moved in a direction of intermittent layer movement, by which the materials varying in the affinity are separated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method of performing a simulated moving bed chromatographic separation operation for separating and recovering a separation target component (substance) from a solution containing a plurality of components. By efficiently performing a useful substance in a small number of steps.

[0002]

[Prior art]

BACKGROUND OF THE INVENTION Generally, when a useful substance is produced by a chemical reaction, the reaction step and the separation step are usually performed separately.

For example, a substance produced by a reversible reaction, for example, an ester is produced by an esterification reaction of an alcohol and an acid in the presence of an acid catalyst, and then a raw material and a product are mixed to obtain a high-purity ester. A separation step such as distillation is carried out in the next stage of the esterification reaction for separation and, in the case of a plurality of products, for separating the products from each other. This is because the reaction rate of esterification, which is a reversible reaction, does not rise above the equilibrium value, and therefore a separation step such as distillation is indispensable for high purification.

Further, when the useful substance to be obtained in the sequential reaction in which the raw material A is converted to B and then C is produced from the material B is the intermediate product, the substance B is Since it is an intermediate product of the sequential reaction, it is not always easy to recover the substance B at a high rate by separating the sequentiality of the reaction that produces the substance B from the substance A and the reaction that produces the substance B from the substance B. is not. In particular, when a series of sequential reactions occur in a reactor that is not separated, it is difficult to separate the first and second sequential reactions. [Prior Art] Based on the background art as described above, for example, by extracting a reaction product out of the system according to the principle of a reversible reaction, the reaction is promoted toward the production target substance to efficiently produce the target substance. Given that, some suggestions have been made. For example, reactive distillation in which a reversible reaction is withdrawn to the outside of the system to advance the reversible reaction in the direction of producing the product, and the reaction and separation are performed in one step in order to combine the two steps in one distillation apparatus. The so-called method has been put to practical use (Mitsuho Hirata: “Latest Distillation Engineering”, p.207,
Nikkan Kogyo Shimbun, 1971).

The production process of methyl acrylate is an example of this reactive distillation. Acrylic acid and sulfuric acid as a catalyst are supplied to the upper part of the reactive distillation column, and methanol is continuously supplied to the lower part of the column to obtain methanol and an objective compound. In this process, methyl acrylate is distilled from the top of the tower, and water and sulfuric acid as a catalyst are discharged from the bottom of the tower.

Further, a reaction in which a chromatographic separation apparatus is used and a catalyst column for performing the reaction is separately provided in a part of the system of the apparatus so that the separation and the reaction are alternately performed in the zone. There is also a proposal for a reactor equipped with a section (Japanese Patent Publication No. 62-18202). The isomerization reaction of glucose and fructose in the isomerized sugar is an example of this.

[0007]

However, the above-mentioned reactive distillation method has a problem that the applicable reaction system is extremely limited because it is necessary that the boiling points of the respective substances are different in an appropriate relationship. . In other words, as a result of the separation method and means being defined by physical parameters such as boiling point, it cannot be applied to substances that cannot be separated under such conditions, for example, thermally unstable substances such as physiologically active substances. .

Further, in the above-mentioned reaction apparatus in which a reaction section is provided in the apparatus for chromatographic separation, substantially, the liquid is allowed to continuously flow between the separation tower and the reaction tower outside the system for performing the chromatographic separation. It is equivalent to an apparatus and is the same as a conventional two-step type apparatus using a reaction apparatus and a chromatographic separation apparatus in that separation and reaction are performed separately. Rather, a separate column for separation and reaction is provided to carry out the reaction. It is necessary to perform a complicated operation in which the liquid to be performed is separated from the separation system, passed through the reaction column, and then returned to the separation system again, which complicates the configuration and control of the apparatus.

The present invention has been made in order to solve the above-mentioned problems of the prior art, and except for the conventional method of reaction distillation, which is applicable only to a limited substance, the two methods of reaction and separation are used. It is an object of the present invention to provide a method for producing a useful substance, which enables production of a chemical substance which requires two or more steps and high-purity separation and recovery in one step with one apparatus.

Another object of the present invention is to reduce the number of steps in the production of useful substances without requiring complicated operations as described above, and in a reversible reaction, proceed the reaction beyond the equilibrium reaction rate. It is also an object of the present invention to provide a method for producing a useful substance capable of facilitating the production of an intermediate substance in a sequential reaction.

[0011]

In order to achieve the above-mentioned various objects, the present inventor uses a liquid in a system in which a plurality of columns having a packing layer formed therein are connected in an endless circulation type. The operation of flowing in one direction and the positions of the inlet of the raw material liquid and the eluent and the outlet of the predetermined component connected to this system are intermittently moved in the above one direction by switching the valve, and the filler layer is applied to the inlet and outlet. Is moved in the direction opposite to the liquid flow direction by an intermittent layer movement operation to move a substance having a weak affinity to the packing material in the column in the liquid flow direction, and a substance having a strong affinity. In the direction of the intermittent layer movement described above, and a method using a simulated moving bed type chromatographic separation operation in which substances having different affinities are continuously separated. When the reaction conditions are satisfied, the substance is reacted and produced. While supplying a liquid containing a component generated as the raw material liquid, the plurality of columns, the filler layer is substantially homogeneous in all columns, and the inside of the entire column satisfies the conditions of the chemical reaction. A method for producing a useful substance using a simulated moving bed chromatographic separation operation, which is characterized in that

In the above, the term "affinity" refers to a phenomenon that a slow speed appears when a component contained in a liquid to be treated is eluted with an eluent in a chromatographic separation operation between a packing material and each component. It was thought that it originated from the fact that there was a difference in some matching affinity, and this acting force (affinity) was called the above-mentioned affinity. However, in general simulated moving bed chromatography separation, "adsorption" and "sorption" were performed. It is not particularly distinguished from the content expressed as ". For example, when the affinity is different, for example, a 1,4-dioxane solution of an ester and water is supplied to a filler layer of a strong acid cation exchange resin, and a chromatographic separation operation of eluting with 1,4-dioxane is performed to obtain water. Elutes later than the ester. This is because there is a stronger affinity between the cation exchange resin and water than between the ester as in the case where the ion exchange resin is used as a desiccant. Further, when the two components in the aqueous solution are separated using the packing material for gel chromatography, one is faster and the other elutes later with the relationship between the size of the pores inside the packing material and the molecular weight of the two components in the aqueous solution. This is because a stronger affinity acts between the other component and the ion exchange resin.

As a simulated moving bed type chromatographic separation apparatus used for carrying out such a method, for example, a simulated moving bed apparatus described in Example 1 below, Japanese Patent Application Laid-Open No. 62- The device described in Japanese Patent No. 91205, the device described in Japanese Patent Application Laid-Open No. 4-227804, and the like can be mentioned as particularly preferable examples. However, the supply position of the eluent or the raw material liquid and the extraction position of the extraction liquid are intermittent at predetermined time intervals. If you want to move in the liquid flow direction,
The method of the present invention can be applied and carried out without particular limitation using an apparatus based on a known simulated moving bed chromatographic separation apparatus.

In carrying out the method of the present invention, particularly preferably, the packed tower group from the first section withdrawal position to the raw material liquid supply position downstream and / or the second section downstream from the raw material liquid supply position. It is preferable that the reaction and the chromatographic separation proceed simultaneously with the packed tower group up to the extraction position. Specifically, the operating conditions may be determined so as to maintain the reaction speed at which the reaction ends in the above two packed tower groups and the moving speed at which the product can sufficiently move to the outlet. By doing so, only the reaction product or only the reaction product and one of the raw materials flow out from the outlet, and the subsequent separation step can be significantly simplified.

The present invention is also particularly effective in carrying out a reversible reaction. Examples of the reversible reaction include ester synthesis reaction and ester exchange reaction by ion exchange resin, and toluene disproportionation reaction by zeolite or silica-alumina. It is preferable to supply a liquid containing components that generate two or more different substances as the raw material liquid.

In the present invention, a liquid containing a component which produces a substance to be separated as an intermediate product or a final product by an irreversible reaction of at least two stages is supplied as the above-mentioned raw material liquid to carry out a sequential reaction. For example, the production of ethylene glycol by the hydration reaction of ethylene oxide using an ion exchange resin can be mentioned.

In the above description, "to satisfy the condition of the chemical reaction" means that the condition of the reaction is obtained by using, for example, a filler having a separating ability and a catalytic ability for the reaction as a filler. If the reaction does not require a catalyst and the raw material is supplied to the simulated moving bed type apparatus and the reaction proceeds under conditions such as temperature at the same time, the reaction of the raw material liquid is caused by using a water jacket or the like. There is no particular limitation as long as it satisfies the temperature conditions required for the above.

The former filler is preferably mixed particles of a separating agent and a catalyst or particles having both separating ability and catalytic ability. Preferred examples are ion exchange resins, zeolites,
Examples thereof include silica alumina. Further, as a filler when the reaction proceeds at a temperature without the need for a catalyst, an adsorbent having only the ability to separate silica gel, styrene-divinylbenzene copolymer, acrylic acid polymer and the like can be used.

In the apparatus used for carrying out the method of the present invention, it is necessary that the packing material is packed "homogeneously" in all columns, so that the reaction and separation can be carried out in one step. It can be realized only by the operation of chromatographic separation.

[0020]

EXAMPLES The present invention will be described in detail below based on examples, but it goes without saying that the present invention is not limited to these examples.

Example 1 Regarding the reaction of producing n-butyl methacrylate and water from methacrylic acid and n-butanol, the reaction / separation using a simulated moving bed was examined. N-butyl methacrylate is used as a fiber treatment agent, a paper coating agent, a paint internal plasticizer, and the like.

The device of FIG. 1 is used as the simulated moving bed device. This device consists of a group of 8 columns (towers) 1 to 8 each having an inner diameter of 1 cm and a length of 30 cm, which are connected in an endless series. Amber, which is a strongly acidic cation exchange resin, is used as a packing material for all columns. List 15 (Product name:
H type) is filled in 23.6 ml each.

The column configuration in this Example 1 is one from the eluent supply port to the extract outlet, three from the extract outlet to the raw material liquid inlet, and from the raw material liquid to the raffinate outlet. 3 from the raffinate extraction port to the eluent supply port.

The adsorption equilibrium, the overall mass transfer capacity coefficient and the reaction rate equation were determined by preliminary experiments, and numerical simulations were performed under the following operating conditions.

Reaction temperature 85 ° C. Flow path switching cycle 60 minutes Raw material concentration Methacrylic acid 5.69 mol / l n-butanol 5.69 mol / l Solvent used 1,4-dioxane Eluent 1,4-dioxane Supply flow rate and withdrawal flow rate Raw material 0.15 ml / min Eluent 3.60 ml / min Extract solution (water extraction category) 3.38 ml / min Raffinate solution (ester extraction category) 0.37 ml / min Effluent solution (eluent 0.20 ml / min The liquid composition of each outlet liquid when almost in a steady state was as shown in Table 1 below. The concentration distribution in the layer immediately before switching the flow path was as shown in FIG. Due to the insufficient reaction rate, unreacted acid and alcohol were extracted together with the ester, and unreacted alcohol was extracted together with the water, but the formed ester and water were separated well and the reverse reaction occurred near the two outlets. It was shown that the reaction was suppressed.

[0026]

[Table 1]

Example 2 An esterification reaction was carried out to produce β-phenylethyl acetate (ester) and water from β-phenylethyl alcohol (alcohol) and acetic acid (acid). Β-Phenylethyl acetate is used as a fragrance for hair sprays and fragrances.

The simulated moving bed apparatus of FIG. 1 was used. This equipment consists of 8 columns (towers) with an inner diameter of 1 cm and a length of 30 cm.
~ 8 is composed of a group of columns connected in an endless series,
23.6 ml of Amberlyst 15 (trade name, H type) which is a strongly acidic cation exchange resin as a packing material in all columns
Are filled one by one. The flow path was switched by controlling the opening and closing of the solenoid valve with a sequencer. Thick lines in the figure exemplify the flow paths within a certain switching cycle. The flow of the liquid was an upward flow, and in order to omit the circulation pump, the circulation flow was once taken out of the system as an effluent before the place where the eluent was supplied and was supplied together with a new eluent by the eluent supply pump. All towers were kept at a constant temperature as water jacketed columns.

Β-Phenylethyl acetate (ester) was produced under the following operating conditions.

Reaction temperature 85 ° C. Channel switching cycle 45 minutes Raw material concentration Acetic acid 5.69 mol / l β-phenylethyl alcohol 5.69 mol / l Solvent was 1,4-dioxane Eluent 1,4-dioxane Each supply flow rate and withdrawal flow rate Raw material 0.55 ml / min Eluent 4.49 ml / min Extract solution (water extraction category) 4.38 ml / min Raffinate solution (ester extraction category) 0.66 ml / min Effluent solution (elution) (Liquid immediately before the liquid was supplied) 0.34 ml / min After 450 minutes, it became almost a steady state, and the composition of each outlet liquid was as shown in Table 2 below. The concentration distribution in the layer immediately before the switching of the flow paths was as shown in FIG. The raw materials, acid and alcohol, stayed in the vicinity of the raw material supply port, indicating that the ester formation reaction was carried out in the packed tower groups on both sides of the raw material supply port.

[0031]

[Table 2]

The overall reaction rate at this time is (5.69 × 0.55-0.06 × 0.66) / (5.
69 × 0.55) × 100 = 98.7%. The ester purity is 4.76 / (0.06 + 0.05 + 4.76 + 0.0).
4) × 100 = 96.9 mol%.

Comparative Example Acetic acid, β-phenylethyl alcohol and 1,4-dioxane solution were placed in a side-arm Erlenmeyer flask, to which a catalyst strong acidic cation exchange resin Amberlyst 15 (trade name, H type) was added, Batch reaction was performed under the following conditions.

Amount of catalyst Amberlyst 15 10.34 g Amount of raw material added Acetic acid 12.01 g (0.200 mol) β-phenylethyl alcohol 24.43 g (0.200 mol) Amount of solvent (1,4-dioxane) 66.97 g Raw material liquid The volume of (mixture of acid, alcohol and solvent) is 1
00 ml.

At a reaction temperature of 85 ° C. for 340 minutes, almost equilibrium was reached, and the composition of the reaction solution at that time was as follows.

Acetic acid 0.74 mol / l β-phenylethyl alcohol 0.74 mol / l β-phenylethyl acetate 1.26 mol / l water 1.26 mol / l Reversible reaction rate 1.26 / 2.00 × 100 = 63.0%.

[0037]

EFFECTS OF THE INVENTION According to the method of the present invention, it is possible to carry out production of a chemical substance, which requires two or more steps of reaction and separation, and high-purity separation and recovery in one step with one apparatus. Moreover, since such an apparatus can be operated in substantially the same manner as the operation of the conventional simulated moving bed type chromatographic separation, it has a complicated configuration and operation like an apparatus in which a conventional reaction tower is provided in a chromatographic separation system. It is possible to obtain the effect that the number of steps can be reduced without requiring the above.

Further, according to the method of the present invention, there is an effect that the reaction and the separation can proceed at the same time, and in the reversible reaction, the reaction can proceed more than the equilibrium reaction rate.

In the reversible reaction, the target substance produced in the reaction can be immediately separated from the mixed solution to improve the reaction efficiency, and the side effect can be reduced. In addition, it is possible to reduce the number of steps such as separating unreacted raw material and returning it to the original raw material, and to reduce the amount to be returned.

When the intermediate product B is the target substance in the sequential reaction of A → B → C, retention of B in the system is not desirable, but according to the method of the present invention, B is produced and B is removed from the system at the same time. This is advantageous for continuous production of B.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a simulated moving bed apparatus assumed in a numerical simulation of a first embodiment and an operation state of a simulated moving bed apparatus of a second embodiment.

FIG. 2 is a diagram showing a concentration distribution in a layer in a steady state in the numerical simulation of Example 1.

FIG. 3 is a diagram showing a concentration distribution in a bed when the simulated moving bed apparatus according to the second embodiment is in a steady state during operation.

Claims (6)

[Claims] 1. An operation of flowing a liquid in one direction in a system in which a plurality of towers each having a filler layer formed therein are connected in an endless circulation type,
The positions of the raw material liquid, the eluent inlet, and the predetermined component outlet connected to this system are intermittently moved in the above-mentioned one direction by switching the valve so that the filler layer does not appear to be in the liquid flow direction with respect to the inlet / outlet. By the operation of intermittent layer movement of moving in the opposite direction, a substance having a weak affinity to the packing material in the column is moved in the liquid flow direction, and a substance having a strong affinity is moved to the intermittent layer. Is a method using a simulated moving bed chromatographic separation operation in which substances with different affinities are continuously separated by moving in the direction of, and the substance to be separated is not substantially contained but the chemical reaction conditions are satisfied. By supplying a liquid containing a component that produces the substance as a reaction product as the raw material liquid, the plurality of columns make the packing layer substantially homogeneous in all columns, and A condition that satisfies the reaction conditions A method for producing a useful substance using a simulated moving bed type chromatographic separation operation, which comprises: 2. An operation of flowing a liquid in one direction in a system in which a plurality of towers each having a filler layer formed therein are connected in an endless circulation type,
The positions of the raw material liquid, the eluent inlet, and the predetermined component outlet connected to this system are intermittently moved in the above-mentioned one direction by switching the valve so that the filler layer does not appear to be in the liquid flow direction with respect to the inlet / outlet. By the operation of intermittent layer movement of moving in the opposite direction, a substance having a weak affinity to the packing material in the column is moved in the liquid flow direction, and a substance having a strong affinity is moved to the intermittent layer. Is a method using a simulated moving bed chromatographic separation operation in which substances with different affinities are continuously separated by moving in the direction of, and substances that do not substantially contain the substance to be separated but have different affinities due to the reversible reaction. Is supplied as the raw material liquid, and the plurality of columns make the filler layer substantially homogeneous in all columns, and the inside of all the columns satisfies the conditions for the reversible reaction. Characterized by the state And a method for producing a useful substance using a simulated moving bed chromatographic separation operation. 3. An operation of flowing a liquid in one direction in a system in which a plurality of towers having a filler layer formed therein are connected in an endless circulation type,
The positions of the raw material liquid, the eluent inlet, and the predetermined component outlet connected to this system are intermittently moved in the above-mentioned one direction by switching the valve so that the filler layer does not appear to be in the liquid flow direction with respect to the inlet / outlet. By the operation of intermittent layer movement of moving in the opposite direction, a substance having a weak affinity to the packing material in the column is moved in the liquid flow direction, and a substance having a strong affinity is moved to the intermittent layer. Is a method using a simulated moving bed chromatographic separation operation in which substances having different affinities are continuously separated by moving the substances to be separated into intermediate products or final products by at least two or more irreversible reactions. A liquid containing a component generated as a product is supplied as the raw material liquid, and the plurality of towers make the filler layer substantially homogeneous in all towers, and the inside of all the towers satisfies the above-mentioned chemical reaction conditions. Ready to go A method for producing a useful substance using a simulated moving bed chromatographic separation operation, which is characterized in that 4. A plurality of filler-filled towers are connected by a connecting pipe or a connecting pipe having a shutoff valve to flow the liquid in one direction to an endless circulation type system, and to supply the eluent to any of the columns. , Withdrawing the separated first partitioned liquid in the reaction liquid from the column downstream of the eluent supply position, and continuously or intermittently supplying the reaction raw material liquid to the column downstream of the extraction position of the first partitioned liquid. The separated second separated liquid in the reaction liquid is withdrawn from the tower downstream of the supply position of the reaction raw material liquid, the supply position of these eluents, the withdrawal position of the first divided liquid, the reaction raw material liquid While performing the operation of simulated moving bed type chromatographic separation in which each position of the supply position and the withdrawal position of the second divided liquid is synchronously intermittently moved to the downstream side of the liquid flow, the reaction raw material liquid is simultaneously added to the reaction raw material liquid in the system. A method of causing a chemical reaction of contained components, The reaction raw material liquid is a liquid that does not substantially contain the substance to be separated, but contains a component that produces the substance as a reaction product when the conditions of the chemical reaction are satisfied. A method for producing a useful substance for simultaneously performing a chemical reaction and a simulated moving bed chromatographic separation, characterized in that the packing is in a state where all the columns are substantially homogeneous and the conditions of the chemical reaction are satisfied. . 5. The tower according to claim 4, wherein the reaction raw material liquid is supplied at a position downstream of the position where the first divided liquid is withdrawn,
And / or a method for producing a useful substance, characterized in that a liquid-phase chemical reaction is carried out in a column up to a withdrawal position of a second divided liquid downstream of a supply position of a reaction raw material liquid. 6. The method according to any one of claims 1 to 5,
The method for producing a useful substance, wherein the packing material in the column in which the packing material layer is formed has a function of catalyzing a chemical reaction of components contained in the raw material liquid supplied into the system.