Shikimic acid production method, shikimic acid production apparatus

Abstract

A stable supply of shikimic acid can be achieved. [Solution] The shikimic acid production method of the present invention includes an oil reduction step of reducing the oil content from a raw material consisting of a plant material, an extraction step of extracting a shikimic acid extract containing shikimic acid from the raw material after the oil reduction step, a first removal step of removing amino acids and cations from the shikimic acid extract, and an adsorption step of adsorbing the shikimic acid contained in the shikimic acid extract onto the anion exchange resin by contacting the shikimic acid extract with an anion exchange resin after the first removal step, an elution step of eluting the shikimic acid adsorbed onto the anion exchange resin to obtain a shikimic acid product liquid containing the shikimic acid, and a drying step of drying the shikimic acid product liquid.

Description

[Technical field]

[0001] The present invention relates to a method and an apparatus for producing shikimic acid, for example, from raw materials made of plant materials. [Background technology]

[0002] Shikimic acid is an organic compound produced by plants and fungi, and is used as a raw material in organic synthesis, for example as a raw material for the synthesis of pharmaceuticals. In recent years, the physiological activity of shikimic acid has also attracted attention, and it is expected to be used as a raw material for cosmetics, as its melanin production inhibitory effect (skin whitening effect) has been revealed.

[0003] At present, the main source of shikimic acid is extracts from the fruit (star anise) of the Illicium verum plant; however, Illicium verum is not only used as a synthetic raw material for pharmaceuticals and cosmetics, but is also in high demand as a raw material for spices, fragrances, and herbal medicines. In addition, harvest yields are greatly affected by the climate, meaning that supply is unstable. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2019 / 039553 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in consideration of the above-mentioned problems, and has an object to provide a novel method and apparatus for producing shikimic acid that can realize a stable supply of shikimic acid. [Means for solving the problem]

[0006] The present invention is characterized in that it is a shikimic acid production method and apparatus that carry out an oil reduction process for reducing the oil content from a raw material made of a plant material, an extraction process for extracting a shikimic acid extract containing shikimic acid from the raw material after the oil reduction process, a first removal process for removing amino acids and cations from the shikimic acid extract, an adsorption process for adsorbing the shikimic acid contained in the shikimic acid extract onto an anion exchange resin by contacting the shikimic acid extract with an anion exchange resin after the first removal process, an elution process for eluting the shikimic acid adsorbed onto the anion exchange resin to obtain a shikimic acid product liquid containing the shikimic acid, and a drying process for drying the shikimic acid product liquid. Effect of the Invention

[0007] The present invention provides a novel method and apparatus for producing shikimic acid that can realize a stable supply of shikimic acid. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a schematic diagram of a manufacturing apparatus according to one embodiment of the present invention. [Diagram 2] FIG. 1 is a flow diagram of a method for producing shikimic acid in one embodiment of the present invention. [Diagram 3] FIG. 4 is a flow chart showing the contents of an oil content reduction process in one embodiment of the present invention. [Figure 4] FIG. 2 is a flow diagram of a recycling method according to one embodiment of the present invention. [Diagram 5] Graph showing the shikimic acid content of each plant material. [Figure 6] Graph showing the shikimic acid content of each part of a plant material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an embodiment of the present invention; FIG. 2 is a schematic diagram showing an embodiment of the present invention;

[0010] The raw material used in the shikimic acid production method and shikimic acid production apparatus of the present invention is a plant material containing shikimic acid. Shikimic acid is a compound and an ionic compound having a carboxy group. As the plant material containing shikimic acid, plant materials of the family Pinaceae such as Ryukyu pine, Kuromatsu, and Todomatsu, and plant materials of the genus Calophyllum in the family Calophyllum can be used. As the plant material of the genus Calophyllum, Calophyllum santa maria, etc. can be used. Shikimic acid is a compound and an ionic compound having a carboxy group.

[0011] Fig. 1 is a schematic diagram of a manufacturing apparatus (shikimic acid manufacturing apparatus) 1 according to one embodiment of the present invention. As shown in Fig. 1, the shikimic acid manufacturing apparatus 1 includes a grinder 10, an oil content reducing section 11, an extraction section 12, a first cation exchange section 13, an anion exchange section 14, an elution section 15, a second cation exchange section 16, a synthesis adsorption section 17, a toxic substance adsorption section 18, a spray dryer 19, a column washing section 20, and a recycle section 21.

[0012] The crusher 10 is not particularly limited as long as it is a machine or device capable of crushing plant material containing shikimic acid, and any known device can be used. For example, the crusher 10 can be a crusher that utilizes compression force, shear force, impact force, friction force, or the like.

[0013] The oil reduction unit 11 is provided to reduce the oil content of the raw material. The oil reduction unit 11 can be configured according to the type of oil (volatile oil, non-volatile vegetable oil, etc.) contained in the raw material. For example, the oil reduction unit 11 can be configured with a steam distillation device, a solvent extraction device, and a seed separation device. The steam distillation device can de-oil plant materials containing a large amount of volatile oil. The solvent extraction device can de-oil plant materials containing a large amount of non-volatile vegetable oil. The seed separation device separates seeds from plant materials containing oil mainly only in the seeds. This allows the oil content of the raw material to be reduced by using parts other than the seeds as the raw material. Each of the steam distillation device, the solvent extraction device, and the seed separation device can be a known device.

[0014] The extraction unit 12 is provided to extract an extract containing shikimic acid (shikimic acid extract) from the raw material after the oil content has been reduced in the oil content reduction unit 11. The extraction unit 12 has a container (tank) for storing the raw material, a water adding device for adding water to the raw material, a solvent supplying device for supplying a solvent, and the like, as necessary.

[0015] The first cation exchange section 13 and the second cation exchange section 16 are provided to exchange cations in the shikimic acid extract or the shikimic acid product liquid described later with other cations. The first cation exchange section 13 and the second cation exchange section 16 have a cation exchange resin. The cation exchange resin is a resin having a crosslinked polymer as a resin matrix and having a cation exchange group. Examples of the cation exchange resin include resins having acid groups such as carboxyl groups (-COOH) and sulfo groups (-SO3H) on the side chains of the polymer chain. For example, each of the first cation exchange section 13 and the second cation exchange section 16 can be configured in the form of a column-type structure (cation exchange resin tower). The cation exchange resin tower has a resin storage section provided in a flow path, and the resin storage section is filled with a cation exchange resin. The cation exchange resin tower (first cation exchange resin tower) in the first cation exchange section 13 and the cation exchange resin tower (second cation exchange resin tower) in the second cation exchange section 16 are constructed separately.

[0016] The anion exchange section 14 is provided to adsorb shikimic acid contained in the shikimic acid extract after the cation exchange treatment in the first cation exchange section 13. For example, the anion exchange section 14 has an anion exchange resin. The anion exchange resin is a resin having a crosslinked polymer as a resin matrix and having an anion exchange group. For example, an anion exchange resin having a styrene resin as a matrix and having a quaternary ammonium group or an amino group as an anion exchange group can be mentioned. For example, the anion exchange section 14 is configured in the form of a column-type structure (anion exchange resin tower). The anion exchange resin tower has a resin storage section provided in a flow path, and the resin storage section is filled with anion exchange resin.

[0017] The elution section 15 is provided to elute the shikimic acid adsorbed on the anion exchange resin of the anion exchange section 14 to obtain a product liquid containing shikimic acid (shikimic acid product liquid). For example, hydrochloric acid can be used to elute shikimic acid, so the elution section 15 has a hydrochloric acid supply device that supplies hydrochloric acid. The shikimic acid product liquid after treatment in the elution section 15 is subjected to cation exchange treatment in the second cation exchange section 16.

[0018] The synthetic adsorption section 17 has a synthetic adsorbent and is provided to remove aromatic carboxylic acids from the shikimic acid production liquid after the cation exchange treatment in the second cation exchange section 16. A hydrophobic synthetic adsorbent can be used as the synthetic adsorbent. For example, the synthetic adsorption section 17 can be configured in the form of a column-type structure (synthetic adsorbent packed tower). The synthetic adsorbent packed tower has an adsorbent storage section provided in the flow path, and the adsorbent storage section is filled with a synthetic adsorbent.

[0019] The toxic substance adsorption section 18 has a toxic substance adsorbent and is provided to remove toxic substances such as anisatin or neoanisatin from the shikimic acid production solution. An ODS (octadecylsilane) compound can be used as the toxic substance adsorbent. For example, the toxic substance adsorption section 18 can be configured in the form of a column-type structure (a tower packed with a toxic substance adsorbent). The toxic substance adsorbent-packed tower has an adsorbent storage section provided in the flow path, and the adsorbent storage section is packed with a toxic substance adsorbent.

[0020] The spray dryer 19 is provided to obtain powdered shikimic acid by volatilizing the moisture of the shikimic acid production solution. For example, the spray dryer 19 has a function of discharging hot air, and the shikimic acid production solution is dried by the hot air to obtain powdered shikimic acid.

[0021] The column washing section 20 is provided for washing the inside of each resin tower or packed tower with pure water. The column washing section 20 has a pure water supply device for supplying pure water, and supplies a predetermined amount of pure water to the inside of each resin tower or packed tower to wash the inside of each resin tower or packed tower.

[0022] The recycle section 21 is provided to recover and reuse the treated water (washed water) after washing each column (anion exchange resin tower, second cation exchange resin tower, synthetic adsorbent packed tower, toxic substance adsorbent packed tower) after the anion exchange resin tower. Since the washed water may contain shikimic acid remaining in each column, the recycle section 21 is configured to generate a recycled liquid (corresponding to a shikimic acid extract) containing shikimic acid from the recovered washed water and return the recycled liquid to the first removal step (step S4). Specifically, the recycle section 21 has a recycle column configured in a column-type structure filled with anion exchange resin. In the recycle section 21, the shikimic acid contained in the washed water is adsorbed to the anion exchange resin packed in the recycle column, and the shikimic acid adsorbed to the anion exchange resin is eluted with hydrochloric acid or the like to obtain a recycled liquid.

[0023] The above-mentioned configuration of the shikimic acid production apparatus 1 is merely an example, and does not need to be limited thereto. For example, the shikimic acid production apparatus 1 may have a configuration (waste liquid treatment unit) for treating waste liquid generated when the anion exchange unit 14 adsorbs shikimic acid. In addition, the configuration of the shikimic acid production apparatus 1 described above may be separated into a plurality of devices to form a shikimic acid production system composed of a plurality of devices.

[0024] The method for producing shikimic acid of the present invention will be described below. Fig. 2 is a flow diagram of the method for producing shikimic acid in one embodiment of the present invention. Fig. 3 is a flow diagram showing the details of the oil content reduction treatment in one embodiment of the present invention.

[0025] As shown in Fig. 2, the shikimic acid production method of the present invention is composed of a grinding step (step S1), an oil content reduction step (step S2), a shikimic acid extraction step (step S3), a first removal step (step S4), an adsorption step (step S5), an elution step (step S6), a second removal step (step S7), an aromatic carboxylic acid removal step (step S8), a toxic substance removal step (step S9), and a drying step (step S10). Each step will be described below.

[0026] In the pulverization step (step S1), the plant material containing shikimic acid is pulverized to a predetermined size by a pulverizer 10. Here, in the pulverization step (step S1), the plant material is pulverized (roughly pulverized) so that the particle size after pulverization is about 2 to 5 mm. The plant material pulverized in the pulverization step (step S1) (pulverized material) is used as a raw material for shikimic acid.

[0027] In the oil content reduction step (step S2), the oil content of the raw material is reduced according to the type of raw material (the type of oil contained in the raw material). As shown in FIG. 3, in the oil content reduction step (step S2), if the raw plant material contains seeds, it is determined whether or not to separate the seeds (step S11). In step S11, if the raw plant material is a plant material of the genus Calophylla and is a fruit containing seeds, it is desirable to separate the seeds, and if the plant material is a Calophylla plant material but only a part (such as pericarp, leaves, or branches) that does not contain seeds, there is no need to separate the seeds. Even if the raw plant material is a fruit containing Calophylla seeds, whether or not to separate the seeds may be determined according to necessity, taking into account the manufacturing equipment, manufacturing costs, etc.

[0028] If the seeds are to be separated (step S11: YES), a seed separation step (step S12) is carried out, and the process proceeds to step S13, which will be described later. In the seed separation step (step S12), a rotary or sliding seed separation device is used to separate the fruit into the seed portion and the non-seed portion (pericarp). Here, after the seed separation step (step S12), the seeds can be discarded and only the non-seed portion can be used as the raw material, or both the seeds and the non-seed portion can be used as the raw material. When the seed separation step (step S12) is completed, the process proceeds to step S13.

[0029] In step S13, it is determined whether the raw material contains a large amount of volatile oil. If the raw material contains a large amount of volatile oil (step S13: YES), a de-oiling process by steam distillation is carried out using a steam distillation device (step S14), and the oil reduction process (step S2) is terminated. For example, when a plant material of the Pinaceae family is used as the raw material, the raw material contains a large amount of volatile oil, so de-oiling is carried out by steam distillation.

[0030] If the raw material does not contain a large amount of volatile oil (step S13: NO), it is determined whether the raw material contains a large amount of vegetable oil (non-volatile vegetable oil) (step S15). If the raw material contains a large amount of non-volatile vegetable oil (step S15: YES), a de-oiling process using an organic solvent is performed using a solvent extraction device (step S16), and a de-solventization process (step S17) is performed to remove the organic solvent and leave only the raw material, and the oil reduction process (step S2) is terminated. For example, when seeds of a plant material of the genus Calophylla are used as the raw material, the raw material contains a large amount of non-volatile vegetable oil, so de-oiling is performed using an organic solvent. The same applies when not only seeds but also the entire fruit including seeds is used as the raw material, or when various parts including seeds of a plant material of the genus Calophylla are mixed.

[0031] Also, if the raw material does not contain a large amount of non-volatile vegetable oil (step S15: NO), i.e., if the raw material contains neither volatile oil nor non-volatile vegetable oil, the oil reduction step (step S2) is terminated. For example, if the seeds are discarded after the seed separation step (step S12) and only the parts other than the seeds are used as the raw material, the raw material will not contain volatile oil or non-volatile vegetable oil. In other words, the seed separation step (step S12) can also be considered a type of oil reduction step (oil reduction means).

[0032] In the shikimic acid extraction step (step S3), the extraction unit 12 extracts a shikimic acid extract, which is a liquid containing shikimic acid, from the raw material whose oil content has been reduced in the oil content reduction step (step S2). For example, the shikimic acid extract is extracted from the raw material by a hot water reflux extraction method. Specifically, the raw material is put into a reaction vessel together with a predetermined amount of water, and the mixture of the raw material and water in the reaction vessel is heated at 60°C to 98°C while performing reflux cooling. After the extraction reaction is completed, the mixture of the raw material and water is filtered to obtain the shikimic acid extract.

[0033] In the first removal step (step S4), the shikimic acid extract is brought into contact with the cation exchange resin of the first cation exchange unit 13. As a result, the amino acids contained in the shikimic acid extract are adsorbed onto the cation exchange resin, and the cations contained in the shikimic acid extract are converted into hydrogen ions (H + ) is substituted. Thus, amino acids and cations can be removed from the shikimic acid extract.

[0034] In the adsorption step (step S5), after the first removal step (step S4), the shikimic acid extract from which amino acids and cations have been removed in the first removal step is brought into contact with the anion exchange resin of the anion exchange unit 14, so that the shikimic acid contained in the shikimic acid extract is adsorbed onto the anion exchange resin. In addition, by treating the shikimic acid extract with the anion exchange resin, all nonionic compounds can be removed from the shikimic acid extract, as well as all water-insoluble substances (such as fine particles).

[0035] In the elution step (step S6), the shikimic acid adsorbed to the anion exchange resin of the anion exchange unit 14 is eluted by the elution unit 15 to obtain a shikimic acid product liquid containing shikimic acid. For example, in the elution step (step S6), hydrochloric acid is used to elute shikimic acid from the anion exchange unit 14. At this time, in order to efficiently elute shikimic acid from the anion exchange resin, the concentration of hydrochloric acid may be 1 mol / L (1 N).

[0036] In the second removal step (step S7), after the elution step (step S6), the shikimic acid production solution obtained in the elution step (step S6) is brought into contact with the cation exchange resin of the second cation exchange section 16. The action and effect of the second removal step (step S7) is similar to that of the first removal step (step S4), and amino acids and cations can be removed from the shikimic acid production solution. In the first removal step (step S4), most of the amino acids and cations are removed from the shikimic acid extract solution that is the basis of the shikimic acid production solution, but the first removal step (step S4) alone may result in amino acids and cations remaining in the shikimic acid extract solution. The second removal step (step S7) allows complete or almost complete removal of amino acids and cations from the shikimic acid production solution.

[0037] In the aromatic carboxylic acids removal step (step S8), the shikimic acid production solution is brought into contact with a synthetic adsorbent in the synthetic adsorption section 17 to remove aromatic carboxylic acids contained in the shikimic acid production solution.

[0038] In the toxic substance removal step (step S9), the shikimic acid-producing solution is brought into contact with a toxic substance adsorbent in the toxic substance adsorption section 18 to remove toxic substances such as anisatin or neoanisatin contained in the shikimic acid-producing solution.

[0039] As described above, a shikimic acid purified liquid in which impurities have been removed from the shikimic acid production liquid can be obtained by going through the second removal step (step S7), the aromatic carboxylic acids removal step (step S8), and / or the toxic substance removal step (step S9). The second removal step (step S7), the aromatic carboxylic acids removal step (step S8), and the toxic substance removal step (step S9) can be collectively referred to as a purification step.

[0040] In the drying step (step S10), the shikimic acid-containing shikimic acid-producing solution or the shikimic acid-purified solution is dried with hot air by a spray dryer 19 to obtain powdered shikimic acid. That is, according to the shikimic acid production method of the present invention, powdered shikimic acid can be obtained (produced) from a plant material containing shikimic acid by going through the above steps.

[0041] The order of the above-mentioned steps is an example, and is not limited thereto, and the order of the steps can be changed. For example, when the seed separation step (step S12) is performed, the crushing step (step S1) can be performed after the oil reduction step (step S2). In addition, the order of the second removal step (step S7), the aromatic carboxylic acid removal step (step S8), and the toxic substance removal step (step S9) can be changed as appropriate.

[0042] The present disclosure will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. [Example 1] 10 kg of mesocarp of Calophyllum indicum was prepared as a raw material. The raw material was roughly crushed using a crushing device. The particle size of the crushed material was about 2 mm. Since only the mesocarp of Calophyllum indicum was used, the oil content reduction process was omitted. Then, 10 L of shikimic acid extract was obtained by hot water reflux extraction. 10 L of the shikimic acid extract was passed through a column packed with a cation exchange resin (Amberlite (registered trademark) IR120B (trade name), manufactured by Organo Corporation) for 2 hours, and then 10 L of the shikimic acid extract was passed through a column packed with an anion exchange resin (Amberlite (registered trademark) IRA400 (trade name), manufactured by Organo Corporation) for 2 hours. This allowed shikimic acid and amino acids to be adsorbed onto the anion exchange resin. Then, 1N hydrochloric acid was used to elute the shikimic acid adsorbed onto the anion exchange resin. This process took about 2 hours. The shikimic acid product solution thus obtained was passed through a column packed with a cation exchange resin (Amberlite (registered trademark) IR120B (trade name), manufactured by Organo Corporation) for about 2 hours. Thereafter, the shikimic acid product solution was passed through a column packed with a hydrophobic synthetic adsorbent (Diaion (registered trademark) HP20 (trade name), manufactured by Mitsubishi Chemical Corporation) and a column packed with an ODS-based compound, in that order. Through these steps, 12 L of shikimic acid product solution (purified shikimic acid solution) was obtained. Then, the water content of the shikimic acid product solution was volatilized using a spray dryer. As a result, 1 kg of shikimic acid was obtained.

[0043] In the shikimic acid production method of the present invention, a first removal step (step S4) of removing amino acids and cations from the shikimic acid extract, an adsorption step (step S5) of adsorbing shikimic acid contained in the shikimic acid extract to an anion exchange resin after the first removal step (step S4), an elution step (step S6) of eluting the shikimic acid adsorbed to the anion exchange resin to obtain a shikimic acid product solution containing the shikimic acid, and a drying step (step S10) of drying the shikimic acid product solution are performed. In this way, since amino acids and cations are removed from the shikimic acid extract before the adsorption step (step S5), the amount of washing water for column washing after the adsorption step (step S5) can be reduced. Specifically, when the same amount of raw material is treated, the amount of shikimic acid product solution after the elution step (step S6) is 1 / 10 to 1 / 20 compared to the conventional method. That is, a shikimic acid product solution with a high concentration of shikimic acid (high-concentration shikimic acid product solution) can be obtained. Therefore, it is possible to efficiently produce shikimic acid and realize a stable supply of shikimic acid. In addition, in the conventional method, the concentration of shikimic acid in the shikimic acid production solution was low, so a step of concentrating the shikimic acid production solution (concentration step) was required, but in the method of the present invention, the concentration step is not required, and shikimic acid can be produced very efficiently.

[0044] Furthermore, according to the present invention, after the elution step (step S6), a second removal step (step S7) is carried out to remove amino acids and cations from the shikimic acid production solution. This allows complete or almost complete removal of amino acids and cations from the shikimic acid production solution and the dried shikimic acid.

[0045] Furthermore, according to the present invention, after the elution step (step S6), a toxic substance removal step (step S9) is carried out to remove toxic substances from the shikimic acid production solution. Therefore, the toxic substances can be removed from the shikimic acid production solution and the dried shikimic acid.

[0046] Furthermore, according to the present invention, when the plant material is a plant material of the genus Calophyllum, the oil content reduction step (step S2) can be a seed separation step (step S12) in which the fruit is separated into seeds and parts other than the seeds, and the parts other than the seeds are used as the raw material. In this case, the de-oiling step by steam distillation (step S14) and the de-oiling step by organic solvent (step S16) can be omitted, making large-scale equipment unnecessary and allowing efficient production of shikimic acid.

[0047] In addition, in the present invention, the washing treatment water can be recycled in parallel with the above-mentioned method for producing shikimic acid. Figure 4 is a flow diagram of a method for recycling the washing treatment water in one embodiment of the present invention.

[0048] As shown in Fig. 4, the method for recycling cleaning water of the present invention comprises a cleaning water supplying step (step S21), a cleaning water recovering step (step S22), an elution step (step S23), and a recycled liquid supplying step (step S24). Each step will be described below.

[0049] In the washing water supplying step (step S21), a predetermined amount of pure water is supplied to the inside of each resin tower or packed tower by the column washing unit 20 (pure water supplying device) to wash the inside of each resin tower or packed tower.

[0050] In the cleaning treatment water recovery process (step S22), the recycle section 21 recovers the treated water (cleaning treatment water) after cleaning each column after the anion exchange resin tower (after the anion exchange resin tower, the second cation exchange resin tower, the synthetic adsorbent packed tower, and the toxic substance adsorbent packed tower), and adsorbs the shikimic acid contained in the cleaning treatment water onto the anion exchange resin in the recycle section 21.

[0051] In the elution step (step S23), the shikimic acid adsorbed on the anion exchange resin of the recycle section 21 is eluted with hydrochloric acid or the like to obtain a recycled liquid. At this time, the concentration of the hydrochloric acid may be, for example, 1 mol / L (1N).

[0052] In the recycled liquid supply step (step S24), the recycled liquid obtained in the elution step (step S23) is supplied to the first cation exchange section 13. That is, the recycled liquid obtained in the elution step (step S23) is returned to the cation exchange treatment.

[0053] According to the present invention, by carrying out the method for recycling the washing treatment water, the shikimic acid contained in the washing treatment water is returned to the middle of the shikimic acid production method, so that the shikimic acid contained in the raw material can be utilized without leakage. In other words, the ratio of the amount of shikimic acid actually obtained to the amount of raw material input can be increased, the amount of shikimic acid produced can be increased, and a stable supply of shikimic acid can be realized.

[0054] In this invention, the oil reduction step corresponds to the oil reduction step (step S2), and similarly thereafter, the extraction step corresponds to the shikimic acid extraction step (step S3), the first removal step corresponds to the first removal step (step S4), the adsorption step corresponds to the adsorption step (step S5), the elution step corresponds to the elution step (step S6), the drying step corresponds to the drying step (step S10), the second removal step corresponds to the second removal step (step S7), the third removal step corresponds to the toxic substance removal step (step S9), the seed separation step corresponds to the seed separation step (step S12), and the oil reduction unit corresponds to the oil reduction unit 11. The extraction section corresponds to the extraction section 12, the first cation exchange resin corresponds to the first cation exchange resin of the first cation exchange section 13, the anion exchange resin corresponds to the anion exchange resin of the anion exchange section 14, the elution section corresponds to the elution section 15, the spray dryer corresponds to the spray dryer 19, the second cation exchange resin corresponds to the second cation exchange resin of the second cation exchange section 16, the toxic substance adsorbent corresponds to the toxic substance adsorbent of the toxic substance adsorption section 18, and the shikimic acid manufacturing apparatus corresponds to the shikimic acid manufacturing apparatus 1, but this invention is not limited to this embodiment and can be various other embodiments. In addition, the specific configurations etc. listed in the above-mentioned embodiment are only examples and can be appropriately changed according to the actual product.

[0055] The present invention can also be provided as a shikimic acid production apparatus for realizing the shikimic acid production method, as well as a shikimic acid production method. Furthermore, the present invention can also be provided as a novel shikimic acid extraction method. For example, the invention of claim 1 can be a shikimic acid extraction method for extracting shikimic acid from a raw material consisting of a plant material of the genus Calophyllum. The invention of claim 2 can be a shikimic acid extraction method according to claim 1, in which the raw material is a pericarp, leaf or branch of a plant material of the genus Calophyllum. The invention of claim 3 can be a shikimic acid extraction method according to claim 1 or 2, in which the raw material is a plant material in a blue or green state before discoloration. The invention of claim 4 can be a shikimic acid extraction method according to claim 1, 2 or 3, in which the raw material is a pericarp within 90 days from fruiting. The invention of claim 5 can be a shikimic acid extraction method according to any one of claims 1 to 4, in which the raw material is a pericarp 30 days or more from fruiting. The invention of claim 6 can be a method for extracting shikimic acid according to any one of claims 1 to 5, in which the raw material is the mesocarp of the plant material.

[0056] Figure 5 is a graph showing the shikimic acid content of each plant material. Figure 6 is a graph showing the shikimic acid content of each part of the plant material. As shown in Figure 5, shikimic acid was particularly highly accumulated in the peel of Calophyllum indicum with 172.1 mg / gDW, which is higher than the shikimic acid content of about 120 mg / gDW in the fruit of Illicium verum, which is used as the main source of shikimic acid. Ryukyu pine also contains shikimic acid with 17.5 mg / gDW, and compared to the 9.9 mg / gDW (leaves) of Japanese black pine, Calophyllum indicum contains a very large amount of shikimic acid. As shown in Figure 6, in addition to the peel of Calophyllum indicum, high levels of shikimic acid were also accumulated in the leaves (80.1 mg / gDW) and branches (23.4 mg / gDW). The shikimic acid content of Calophyllum indus leaves exceeded the 37.9 mg / gDW (leaf) content of Calophyllum santa maria, which is considered a promising alternative source of shikimic acid. Furthermore, while the fruits of Illicium verum can only be harvested once a year, Calophyllum verum blooms in all four seasons, bearing fruit two or three times a year, and is an evergreen tree whose branches and leaves can be used, making it possible to obtain raw materials throughout the year. As described above, Calophyllum verum is a promising source of shikimic acid, as it is a stable source of shikimic acid.

[0057] Therefore, by extracting shikimic acid from a raw material made of a plant material of the genus Calophyllum, a stable supply of shikimic acid can be realized. In addition, by using the pericarp, leaves or branches of the plant material of the genus Calophyllum, which are parts where shikimic acid is highly accumulated, as the raw material, shikimic acid can be efficiently produced. In addition, since the pericarp, leaves or branches of the plant material of the genus Calophyllum have a very low oil content, there is also the advantage that the oil content reduction step can be omitted. Furthermore, by using the pericarp of the plant material of the genus Calophyllum, which are parts where shikimic acid is particularly highly accumulated, as the raw material, shikimic acid can be produced more efficiently. In particular, it is preferable to use the mesocarp of the plant material of the genus Calophyllum. In addition, when the pericarp, leaves or branches of the plant material of the genus Calophyllum are used as the raw material, it is preferable to use those in a blue or green state before discoloration. The pericarp of the plant material of the genus Calophyllum has a lower shikimic acid content when it is more than 90 days after fruiting than when it is less than 90 days after fruiting. Therefore, when the pericarp of the plant material of the genus Calophyllum is used as a raw material, it is preferable to use the pericarp within 90 days after fruiting. Furthermore, the pericarp of the plant material of the genus Calophyllum has a higher shikimic acid content when it is more than 30 days after fruiting than when it is less than 30 days after fruiting, and the shikimic acid content is further increased when it is more than 60 days after fruiting than when it is less than 60 days after fruiting. Therefore, when the pericarp of the plant material of the genus Calophyllum is used as a raw material, it is preferable to use the pericarp that is more than 30 days after fruiting, and more preferably the pericarp that is more than 60 days after fruiting. Furthermore, when the leaves of the plant material of the genus Calophyllum are used as a raw material, the leaves may be unshed, and it is preferable to use undiscolored blue or green leaves. [Industrial Applicability]

[0058] The present invention can be used in the industry of producing shikimic acid. [Explanation of symbols]

[0059] 1...Shikimic acid production equipment 10...Crusher 11...Oil reduction section 12...Extraction part 13…First cation exchange section 14…Anion exchange section 15…Elution section 16…Second cation exchange section 17…Synthetic adsorption part 18...Toxic substance adsorption part 19…Spray dryer 20…Column washing section 21…Recycling Department

Claims

1. A selection process for selecting a fruit of Calophyllum commune of the genus Calophyllum commune that has been in fruition for 30 days or more and not later than 90 days as a plant material; A seed separation step of separating the fruit into seeds and skin and using the skin as a raw material; After the seed separation step, an extraction step of extracting a shikimic acid extract containing shikimic acid from the raw material; a first removal step of removing amino acids and cations from the shikimic acid extract; After the first removal step, an adsorption step of contacting the shikimic acid extract with an anion exchange resin to adsorb the shikimic acid contained in the shikimic acid extract onto the anion exchange resin; an elution step of eluting the shikimic acid adsorbed on the anion exchange resin to obtain a shikimic acid product solution containing the shikimic acid; A drying step of drying the shikimic acid-producing solution is carried out. Shikimic acid production method.

2. After the elution step, a second removal step is carried out to remove amino acids and cations from the shikimic acid-producing solution. The method for producing shikimic acid according to claim 1.

3. A recycling liquid generating process for recovering the cleaning treatment water generated in the process after the adsorption process and generating a recycling liquid containing shikimic acid from the cleaning treatment water; A recycling step is carried out in which the recycled liquid is returned to the first removal step as the shikimic acid extract. The method for producing shikimic acid according to claim 2.

4. A seed separation unit that separates a fruit of the genus Calophyllum that is 30 days or more and less than 90 days after fruiting into seeds and pericarp, and uses the pericarp as a raw material; An extraction unit that extracts a shikimic acid extract containing shikimic acid from the raw material; a first cation exchange resin for removing amino acids and cations from the shikimic acid extract; an anion exchange resin for adsorbing the shikimic acid extract from which amino acids and cations have been removed by the first cation exchange resin; an elution section for eluting the shikimic acid adsorbed on the anion exchange resin to obtain a shikimic acid product solution containing the shikimic acid; A spray dryer for drying the shikimic acid production liquid; A second cation exchange resin for removing amino acids and cations from the shikimic acid-producing solution; a column washing section for washing the anion exchange resin, the elution section, or the second cation exchange resin with pure water; a recycle section for recovering the washing treatment water produced in the column washing section, generating a recycled liquid containing shikimic acid from the washing treatment water, and returning the recycled liquid to the anion exchange resin as the shikimic acid extract. Shikimic acid production equipment.

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