JPH01108972A - Reactor for liquid-liquid different phases - Google Patents

Abstract

PURPOSE:To improve efficiency of reaction, by providing partition plates of a structure in which a light liquid phase and heavy liquid phase are moved at suitable speeds in the reactor and carrying out continuous series multistage reaction in one vessel of the reactor. CONSTITUTION:For example, the interior of a vessel 1 is divided into two or more compartments 3, 4 and 5 with partition plates 27 and 27 having many holes and the interiors of the respective compartments 3, 4 and 5 are divided into the interior and exterior with intermediate walls 8 to provide stirrers in the interiors in a reaction vessel for carrying out reaction in a light liquid phase and heavy liquid phase, such as hydrolysis of oils and fats with lipase, synthesis of oils and fats and various esterification reactions. An introduction port 27 for the heavy liquid phase and an overflow port 29 for the light liquid phase are provided in the upper part of the compartment 5 in the topmost layer. An introduction port 9 for the light liquid phase and outlet 30 for the heavy liquid phase are provided under the compartment 3 in the lowermost layer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is a liquid-liquid heterophase reaction system in which a continuous multiple-throttle reaction is carried out while stirring and mixing these different phases, and at the same time as the reaction, these different phases are reacted simultaneously in the same reactor. This invention relates to a reaction device that continuously separates and efficiently obtains products.

[Conventional technology and its problems]

Most of the chemical reactions in the chemical industry are heterophasic (gas-
There are many reactions that are useful in the liquid-liquid heterophase reaction, which is one of these reactions.

For example, hydrolysis of fats and oils by lipase, modification of fats and oils,
These include the synthesis of fats and oils, the synthesis of various esters, the various peptide synthesis reactions seen in the synthesis of the artificial sweetener aspartame using protease, and the nitration, sulfonation, and alkylation reactions of organic compounds. It will be done. In these heterophasic reactions, in order to increase the reaction efficiency, the reaction is usually carried out as a fine emulsion, and after reaching a predetermined reaction rate, the reaction is stopped and then separated into each phase to separate the products. This is a batch operation for collection. It is also possible to carry out a continuous reaction by continuously supplying the raw materials, but in this case, in addition to the reactor, a step for separating the emulsion is required.

In this way, in a reaction in a liquid-liquid heterophasic dispersion system that does not dissolve in each other, it is necessary to separate the reaction system into each phase again after the reaction, and this method generally includes static separation, centrifugation, Alternatively, methods such as separation using a membrane can be mentioned, but if these separation steps are combined after the reaction,
The system becomes complicated and the cost burden becomes large, which poses problems in industrialization.

The present inventors have already discovered that liquids used in enzymatic or microbial reactions
We have proposed a continuous reaction method that can simultaneously separate products while maintaining a high reaction rate in liquid heterophase reactions (Japanese Patent Application No. 122994/1982). However, most chemical reactions and biochemical reactions are reactions in which the reaction rate decreases as the reaction rate increases, and the reaction rate can be expressed as a decreasing function of the reaction rate. In such reactions, a tubular reactor is more efficient than a complete mixing reactor, especially when continuous reactions are carried out while maintaining a high reaction rate. In other words, in Japanese Patent Application No. 122994/1982, in order to maintain a high reaction rate, a long residence time is required because the reaction rate is slow, and a large reaction volume is required to ensure a high production rate. Become.

In addition, even in the case of a complete mixing reactor, the disadvantages of a tubular reactor can be overcome to a large extent by connecting several reactors in series to form a multi-stage reactor, but this requires a large number of glue actors, making the system complex. Not suitable for practical use.

[Means for solving problems]

In order to solve the above problems, the inventors of the present invention filed a patent application filed in 1983.
The reaction method can be carried out efficiently without losing the characteristics of the reaction method according to No. 122994, that is, the separation of two phases is carried out at the same time as well as the reaction, and also taking into account the characteristics due to the difference in the reactor type as mentioned above. As a result of extensive research aimed at developing a reactor that would allow the light liquid phase and heavy liquid phase to move up and down at appropriate speeds, it was found that We have developed an efficient reactor that can carry out serial multi-stage reactions continuously.

That is, the present invention is divided into two or more compartments at the top and bottom by a partition plate having holes, and each compartment is provided with an inner wall that partitions the inside and outside, and a stirrer is attached to the inner chamber. The top compartment has a heavy liquid phase inlet and a light liquid phase overflow port at the top, and the bottom compartment has a light liquid phase inlet below the stirrer. The present invention provides a liquid-liquid heterophase reactor having two liquid phases that are mutually insoluble or poorly soluble and have different specific gravities, in which a heavy liquid phase outlet is provided in the lowermost compartment.

The present invention is a reactor in which a light liquid phase and a heavy liquid phase are separated into two layers, an upper and a lower layer. By mixing the light liquid phase and heavy liquid phase as reaction raw materials in the vicinity,
or in a reactor in which the reaction raw materials present in the light liquid phase and/or the heavy liquid phase can be converted into products and the products present in the light liquid phase and/or the heavy liquid phase in the immiscible portion can be taken out. To provide an apparatus capable of carrying out a continuous multi-stage reaction in which a light liquid phase and a heavy liquid phase are divided into multiple stages in a reactor by a partition plate having a structure in which a light liquid phase and a heavy liquid phase can each be moved up and down at appropriate speeds.

Therefore, according to the present invention, a more compact reactor can be realized in a two-phase heterophasic reaction, and an extremely excellent reaction method can be established in which separation of two phases can be carried out simultaneously with the reaction.

The present invention will be explained in more detail based on drawings showing preferred embodiments of the present invention, taking as an example a liquid-liquid two-phase reaction in which an aqueous solution is used as a heavy liquid phase and a non-aqueous solution phase with a specific gravity smaller than water is used as a light liquid phase. do. As a reaction example, A+B-+C+D (A,
B is a reaction raw material, and C and D are products. Now assume that A and C are water-soluble, and B and D are water-insoluble. The liquid-liquid two-phase system reaction represented by ) will be explained using FIG. FIG. 1 shows an example of a reactor having the features of the present invention. From the bottom of the reactor 1, 2 is an aqueous phase, and 3, 4.5 are reaction parts, which are divided into three compartments by a partition plate 27 having holes. The greater the number of compartments, the better the efficiency, but the equipment becomes more complex and expensive. Therefore, 2 to 10 pieces is preferable. In order to form a non-aqueous solution phase and an aqueous phase into a fine emulsion in each part separated by a partition plate and perform an efficient reaction, the two phases are mixed here by a helical screw type stirring blade 25 having a draft tube 8. .

6 is a non-aqueous solution (light liquid) phase. As shown in FIG. 1, there are baffle plates 10 and 22 at the top and bottom of the reactor, respectively.
Providing this is preferable because it prevents complete mixing of the liquids at the top and bottom of the reactor and forms a portion where the non-aqueous solution phase and the aqueous phase are separated.

Reaction raw material A (aqueous phase) and reaction raw material B (non-aqueous phase) are pumped into this reactor at a constant ratio from a reaction raw material (aqueous phase) storage tank 16 and a reaction raw material (non-aqueous solution phase) storage tank 17, respectively, by a pump 19. 18, water (heavy liquid phase) inlet 28 and non-aqueous solution (light liquid phase) inlet 9 are charged. Water and the non-aqueous solution may be charged either in parallel flow or in countercurrent flow, but it is usually preferable to charge them in countercurrent flow.

The partition plate that separates the inside of the reactor should be one that minimizes the mixing of liquids in the upper and lower parts of the partition plate, and that has a movement speed that is commensurate with the supply rate when non-aqueous solution and water are continuously supplied. used. That is, it is most preferable that the liquid phases of the non-aqueous solution and water move up and down by the same amount as the supply speed. The shape and material of the partition plate are not particularly limited as long as they meet the above conditions, such as perforated plate trays, bubble bell trays, bubble trays, etc. used in tray columns for distillation, extraction, etc. Types of materials used include stainless steel, glass, ceramics, and synthetic polymers.

The uppermost compartment is provided with an overflow port 29 for a non-aqueous solution (light liquid phase), and the lowermost compartment is provided with an outlet 30 for water (heavy liquid phase). , take out C.

By using the method of the present invention, products can be separated at the same time as the reaction, so it is possible to perform not only batch operations but also continuous or semi-continuous reactions in which reaction raw materials are supplied while continuously extracting products. It is. In addition, by dividing the inside of the reactor into multiple stages with partition plates and preventing complete mixing of the liquids, efficient reactions can be carried out, making it possible to shorten reaction time, downsize the reactor, and increase product concentration. Become.

When using the draft tube 8 and stirring blade 25 as shown in Fig. 1 as the inner wall, the diameter of the draft tube is not particularly limited and may be determined depending on the desired reaction, but it is not limited to 50% of the diameter of the reaction tank. A diameter of ~90% is preferably used.

In addition, the rotational speed of the stirring blade is such that the lower layer in the reactor is well rolled up and mixing occurs near the interface between the non-aqueous phase and the aqueous phase. The setting may be made so that a part that does not mix remains.

A filler 7 may also be used as shown in FIG.

In this case, the form of the filler is not particularly limited, and fillers such as Raschig rings, Lessing rings, Berl saddles, Interlocks saddles, and Paul rings, which are commonly used as fillers, or cylindrical nets are used. You may. The material is not particularly limited either, and metal, porcelain, plastic, etc. can be used.

By using a filler, the contact efficiency between the aqueous phase and the non-aqueous solution phase is increased, and in systems using catalysts or biocatalysts such as enzymes and microorganisms, the contact efficiency between the catalyst and the reaction raw materials is increased, increasing the efficiency. reactions can be made. However, if these conditions are satisfied even without using a filler, there is no need to use a filler.

When using this reactor to carry out reactions using ordinary chemical catalysts or biocatalysts such as enzymes or microorganisms, the catalysts used for these reactions are efficiently retained in the reactor, but the aqueous phase or It may dissolve slightly in the aqueous solution phase.

Therefore, in consideration of the efficient use of these catalysts or the influence on product quality, it is preferable to concentrate and recover these catalysts.

In the present invention, the term "catalyst" refers to all catalysts including not only ordinary chemical catalysts but also biocatalysts such as enzymes and microorganisms.

Static separation, centrifugation,
Methods such as membrane separation may be used, but it is preferable to use an ultrafiltration membrane for continuous separation. The ultrafiltration membrane to be used is not particularly limited in terms of material and shape, as long as it does not allow the catalyst used in the reaction to pass through. Cellulose acetate membranes and polyacrylonitrile membranes can be used to recover what is dissolved in the aqueous phase. Hydrophilic materials such as , polysulfone membranes, polyamide membranes, etc. are preferably used, and hydrophobic materials such as polypropylene membranes, polyethylene membranes, Teflon membranes, etc. are preferably used to recover dissolved materials in the non-aqueous solution phase. can be preferably used. Furthermore, membranes made of inorganic materials such as porous glass and porous ceramics can be preferably used for membrane separation of either the aqueous phase or the non-aqueous phase. Furthermore, any shape can be used, such as a flat membrane, a tube, a spiral, and a hollow fiber. The molecular weight cutoff of the ultrafiltration membrane varies depending on the catalyst used in the reaction, and it is sufficient as long as it has a pore size that can prevent the permeation of these catalysts.Although it is not particularly limited, it is generally about 3,000 to 50,000. preferable. The aqueous phase or non-aqueous phase not containing the catalyst may be continuously extracted by ultrafiltration, and the concentrated catalyst solution may be continuously or semi-continuously returned to the reaction system.

Note that if most of the catalyst is retained within the reactor and dissolution in the aqueous phase or non-aqueous phase can be ignored, there is no need to separate these catalysts by ultrafiltration. It is also possible to fill the insoluble carrier with a catalyst that has been immobilized in advance by various methods, and in this case as well, the catalyst recovery step by ultrafiltration is not necessary. Alternatively, it is also possible to omit the ultrafiltration step and add fresh catalyst corresponding to the amount of catalyst dissolved in the aqueous phase or non-aqueous phase.

If such a method is used, the catalysts can be retained in the reactor and efficiently recovered and reused without any special pretreatment. The catalyst can be retained in the packing material by adsorption without any special pretreatment, or it can be filled with a catalyst that has been insolubilized by various methods (supported catalyst, immobilized biocatalyst, etc.), or alternatively, There are methods such as using it in a free state without using a filler, but which method to use may be appropriately selected depending on the characteristics of the catalyst, reaction conditions, etc.

The characteristics of the present invention are that the reaction is carried out by mixing the upper and lower layers in the reactor near the interface, and the reaction is carried out while leaving unmixed parts in the upper and lower parts of the reactor, and the reaction is carried out at the same time. In a reactor where the light and heavy liquid phases can be taken out independently, complete mixing of the liquids in the reactor is prevented, and the light and heavy liquid phases move at the same speed as their respective feed rates. By providing a partition plate with a structure that allows efficient reactions, that is, continuous series multi-stage reactions can be performed in a single reactor. Therefore, the reaction raw materials can be added continuously and the product can be obtained at the same time. Furthermore, since the reaction can be carried out continuously, the concentration of each product in the reactor can be maintained constant.

The method of the present invention can be applied to various reactions in a liquid-liquid heterophase system of a light liquid phase and a heavy liquid phase, including the above-mentioned hydrolysis reaction of fats and oils by lipase, synthesis of triglyceride by lipase, transesterification reaction of triglyceride, Alternatively, the synthetic reaction of duputide using a protease, such as the synthesis of the artificial sweetener aspartame (aspartyl phenylalanine methyl ester) from carbobenzyloxy-1-aspartic acid and γ-phenylalanine methyl ester using thermolysin, or alternatively, these biochemical reactions. In addition to these reactions, the present invention can be widely applied to reactions in a liquid-liquid two-phase system such as nitration reactions, sulfonation reactions, and alkylation reactions of organic compounds, but is not limited thereto.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited to these Examples.

Example 1 A case will be described in which the method of the present invention is used to hydrolyze fats and oils with enzymes. In this case, the reactants are oil and water, the enzyme is lipase, and the reaction products are fatty acids and glycerin. The present inventors have already discovered that when hydrolyzing fats and oils using lipase, the product glycerin greatly contributes to the stability of the lipase. According to research conducted by the present inventors, when the glycerin concentration in the aqueous phase in the reaction system is within the range of 10 to 40% by weight, the enzyme is stabilized and hydrolysis of fats and oils preferably proceeds. The method of the present invention makes it easy to keep the concentrations of various components constant in each stage divided by partition plates in the reactor, and is therefore preferably applied to the hydrolysis of fats and oils by lipase. That is, by appropriately adjusting the supply ratio of oil and fat to the aqueous phase, the glycerin concentration in the aqueous phase can be controlled while maintaining a high oil and fat decomposition rate.

FIG. 1 shows an example of a preferred implementation system of the present invention. First, soybean oil was hydrolyzed by lipase using the reaction system shown in FIG. In the hydrolysis of fats and oils by lipase, in FIG. 1, 9 is an oil supply nozzle, 11 is a fatty acid solution storage tank, 14 is a glycerin aqueous solution membrane treatment storage tank, 15 is a glycerin water storage tank, 16 is a water storage tank, 1
7 is an oil storage tank.

In reaction tank 1, 1 kg of decomposed fatty acids (fatty acid content: 85%) obtained by enzymatically decomposing soybean oil, 1 kg of 15 wt% glycerin water, and 2 g of lipase (320,000 units/g) produced from Candida cylindriase was added. The reaction was carried out while maintaining the temperature at 30°C.

The ratio of the diameter of the reaction tank and the diameter of the draft chinive 8 is 10:6.
It is. Further, the stirring blade was a ribbon-type blade 25 as shown in FIG. 1, and stirring was performed at a circumferential speed of about 0.5 m/sec. Soybean oil (fatty acid content: 0%) is continuously supplied to this reaction tank 1 from a nozzle 9 at the bottom of the reaction tank at a flow rate of 50 g/HR by a pump 18 from an oil storage tank 17, and a water storage tank 16
15 wt% glycerin water was charged in advance, and 15 wt% was added at a flow rate of 50 g/HR using the pump 19.
Glycerol water was continuously supplied from the top of the reactor. That is, the oil phase and the aqueous phase were each supplied into the reactor so that the average residence time in the reactor was 20 hours.

By dividing the reaction tank into three stages using partition plates, efficient hydrolysis reaction can be carried out without complete mixing. Further, by providing the baffle plates 10 and 22 at the upper and lower parts of the reaction tank, respectively, the upper side 6 and the lower side 2 can obtain fatty acid containing almost no water or glycerin water containing almost no oil. In this way, fatty acids are continuously extracted by the amount of soybean oil supplied by overflow from the overflow port 29 of the light liquid phase, and glycerin water is continuously extracted from the outlet 30 at the bottom of the reaction tank by the pump 20. 14, the enzyme dissolved in the aqueous phase was concentrated and recovered using an ultrafiltration membrane 13, and the reaction was carried out while adjusting the amount of glycerin water extracted to be 50 g/HR.

In this example, a polyacrylonitrile membrane (molecular weight cut off: 30,000) was used as an ultrafiltration membrane to semi-continuously concentrate the enzyme and return it to the reaction tank.

Using such a reaction apparatus, the reaction was continued while continuously supplying soybean oil and an aqueous glycerin solution and continuously withdrawing a fatty acid solution and an aqueous glycerin solution.

After 20 hours (equal to the average residence time in the reaction tank), the reaction liquid was collected from parts 3, 4, and 5 of reaction tank 1, and the acid value and saponification value of each oil phase were measured. In addition, the glycerin concentration of each aqueous phase was measured. Acid value of 30 parts = 155° Saponification value = Acid value of 198.4 parts =
181, saponification value = 199.5 part acid value = 190
, saponification value=200 was obtained. When the hydrolysis rate was calculated from the following formula, 3. 4. The hydrolysis rates of portion 5 were 78%, 91%, and 95%, respectively.

Furthermore, the glycerin concentrations in the portions 3, 4, and 5 were 24%, 16.4%, and 15.4%, respectively. The decomposition rate of the portion 5 is equal to the decomposition rate of the fatty acid solution obtained in the fatty acid solution storage tank 11, and the glycerin concentration in the aqueous phase of the portion 3 is equal to the glycerin concentration of the aqueous glycerin solution in the aqueous glycerin solution storage tank 15.

Similarly, 40 hours after starting the supply of soybean oil, 60 hours after starting, 80 hours after starting the supply of soybean oil,
After 100 hours, the decomposition rate and glycerin concentration in each part of the reaction tank were measured, and the results were as shown in Table 1.

Table 1 Even after 100 hours of continuous reaction, the enzyme did not deactivate at all, the decomposition rate of soybean oil was 92-95%, and the glycerin concentration in the aqueous phase was maintained at 23-24%. did it.

On the other hand, the water content in the fatty acid solution obtained in the fatty acid solution storage tank 11 was 0.5% or less. In addition, the glycerin water that passed through the ultrafiltration membrane was of good quality. By using this reaction system in this way,
It has been found that it is possible to efficiently recover and reuse enzymes while simultaneously performing reaction and product separation, and maintaining a high decomposition rate.

Comparative Example-1 Here, continuous hydrolysis of soybean oil was carried out using a reaction tank that did not have a partition plate for partitioning the reaction tank into multiple stages as used in Example-1.

In a reaction tank, 1 kg of decomposed fatty acids (85% fatty acid content) obtained by enzymatically decomposing soybean oil, 1 kg of 2ht% glycerin water, and lipase (3
20000 units/g) was added and the reaction tank was heated to 30°C.
The reaction was carried out while maintaining the - The ratio of the diameter of the reaction tank to the diameter of the draft chive is 10:6. Further, stirring was performed using a ribbon-type stirring blade at a circumferential speed of 0.5 m/sec.

Soybean oil was supplied from the lower part of the reaction tank at a flow rate of 50 g/HR, and water was supplied from the upper part at a flow rate of 25 g/HR to carry out a continuous reaction. That is, soybean oil was supplied into the reaction tank so that the average residence time in the reaction tank was 20 hours, and the glycerin concentration in the aqueous phase could be maintained at about 20%.

In this way, the fatty acids produced in the same manner as in Example 1 are continuously extracted by overflow, and after Amagi collects the enzyme dissolved in the aqueous phase using an ultrafiltration membrane, it is continuously extracted from the system. Ta.

The hydrolysis rate and glycerin concentration of soybean oil for each reaction time were measured and the results are shown in Table 2.

Table 2: Even after 100 hours of continuous reaction, no deactivation of the enzyme was observed, but the decomposition rate of soybean oil was 85-86.
%, which is lower than that of Example-1.

Example-2 Using the same equipment as in Example-1, the initially charged soybean oil decomposition solution, 15 wt% glycerin aqueous solution, and enzyme preparation amounts were also the same as in Example-1, and the soybean oil supply amount was the same as in Example-1. 50 g/HR, and the amount of 15 wt% glycerin aqueous solution supplied was changed to 25 g/HR.

That is, the average residence time of the aqueous phase was 40 hours. In this way, continuous hydrolysis of soybean oil was carried out. Table 3 shows the fat and oil decomposition rate and glycerin concentration in each part of the reaction tank for each reaction time.

Table 3 It was found that by adjusting the supply speed of the aqueous phase as described above, high concentration glycerin water could be obtained while maintaining a high decomposition rate.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing one example of the reaction apparatus of the present invention. 14... Product (heavy liquid phase) storage tank for membrane treatment 15... Product (heavy liquid phase) storage tank 16... Reaction raw material (heavy liquid phase) storage tank 17... Reaction raw material (light liquid phase) Storage tanks 18-21... Pump 22... Lower baffle plates 23-24... Valve 25... Stirring blades 26... Stirring motor 27... Reaction tank internal partition plate 28... Heavy liquid Phase inlet 29...product (light liquid phase) overflow port 30...product (heavy liquid phase) outlet

Claims (1)

[Claims] 1 It is partitioned vertically into two or more compartments by a partition plate with holes, and each compartment is provided with an inner wall that partitions the inside and outside, and a stirrer is installed in the inner chamber,
The topmost compartment has a heavy liquid phase inlet and a light liquid phase overflow port above it, and the bottom compartment has a light liquid phase inlet below the stirrer. , a liquid-liquid heterophase reactor having two liquid phases that are mutually insoluble or poorly soluble and have different specific gravities, in which a heavy liquid phase outlet is provided in the lowest compartment.