JP7476499B2 - Method for producing shikimic acid or its derivatives - Google Patents

Description

The present invention relates to a method for producing shikimic acid or a derivative thereof.

Cyclic compounds such as aromatic carboxylic acid compounds are used, for example, as raw materials for resins such as engineering plastics and pharmaceuticals, as well as for fragrances and cosmetics, or as raw materials for these.

Such cyclic compounds are traditionally produced using fossil resources such as petroleum, natural gas, and coal as raw materials. In recent years, however, there have been attempts to use biomass resources as raw materials due to concerns over global warming caused by the depletion of fossil resources and the increase in carbon dioxide concentrations.

For example, Patent Document 1 discloses a method of producing methane from biomass by microbial fermentation, producing benzene from the methane by a catalytic reaction, and then producing a benzene derivative from the benzene. The benzene derivative produced in this way is used as a raw material for aromatic polymers, making it possible to realize polymers that are not dependent on fossil resources.

JP 2004-123666 A

However, the conventional methods are still not efficient enough in producing benzene derivatives. Specifically, because benzene derivatives (such as phthalic acid) are produced from biomass via methane and benzene, there is a problem that the amount of benzene derivatives synthesized is small compared to the effort and energy input.

There is also a demand for increasing the purity of the benzene derivatives produced. Patent Document 1 discloses purifying benzene using a method such as distillation, which can increase the purity of the benzene derivatives, but this consumes a lot of energy.

An object of the present invention is to provide a method for producing solid, highly pure shikimic acid or a derivative thereof in high yield.

These objects can be achieved by the present invention described below in (1) to (7) .
(1) a raw material liquid preparation step of preparing a raw material liquid containing shikimic acid or a derivative thereof from biomass;
a drying step of adding a desiccant to the raw liquid and then vacuum-drying the raw liquid under reduced pressure to concentrate the raw liquid;
An extraction step of adding an extraction solvent to the raw material liquid to extract shikimic acid or a derivative thereof to obtain an extract;
a precipitation step of obtaining the solute of the extract as a solid;
a step of performing a re-dissolving process after the precipitation step, in which the solute is dissolved in a good solvent to obtain a solution;
subjecting the solution to an activated carbon treatment;
a step of subjecting the solution that has been treated with activated carbon to a reprecipitation treatment by adding a poor solvent and recovering a precipitate as a solid;
having
The drying step and the extraction step are carried out simultaneously by adding the desiccant and the extraction solvent to the raw material liquid;
A method for producing shikimic acid or a derivative thereof, characterized in that the recovered solid is in powder form and has an ISO whiteness of 70% or more as measured in accordance with the ISO whiteness test method specified in JIS P 8148:2001.
(2) the drying step includes a process of adding the desiccant to a concentrated liquid obtained by concentrating the raw material liquid, and further concentrating the concentrated liquid;
The method for producing shikimic acid or a derivative thereof according to (1) above , wherein the amount of the desiccant added is 1 to 300 g per 100 g of the concentrated solution .
(3) A raw material liquid preparation step of preparing a raw material liquid containing shikimic acid or a derivative thereof from biomass;
a drying step of vacuum drying the raw material liquid to obtain a dried product;
a redissolving step of dissolving the dried product in a good solvent to obtain a solution;
an adsorption step of subjecting the solution to an activated carbon treatment;
an extraction step of liquid-liquid extracting shikimic acid or a derivative thereof from the solution treated with the activated carbon using an extraction solvent to obtain an extract;
a precipitation step of recovering the solute from the extract as a solid;
having
A method for producing shikimic acid or a derivative thereof, characterized in that the recovered solid is in powder form and has an ISO whiteness of 70% or more as measured in accordance with the ISO whiteness test method specified in JIS P 8148:2001.
(4) a step of performing a re-dissolving process after the precipitation step, in which the solute is dissolved in a good solvent to obtain a solution;
subjecting the solution to an activated carbon treatment;
a step of subjecting the solution that has been treated with activated carbon to a reprecipitation treatment by adding a poor solvent and recovering a precipitate as a solid;
The method for producing shikimic acid or a derivative thereof according to (3) above,

(5) The method for producing shikimic acid or a derivative thereof according to (3) or (4) above, wherein the dried product has a liquid phase content of 30% by mass or less.

(6) The method for producing shikimic acid or a derivative thereof according to any one of (1) to (5) above, further comprising an acidification step of adding an acid to the raw liquid, which is performed prior to the drying step.

(7) A method for producing shikimic acid or a derivative thereof according to any one of (1) to (6) above, wherein the precipitation step is a step of evaporating the solvent contained in the extract.

According to the present invention, it is possible to produce solid, highly pure shikimic acid or a derivative thereof in high yield.

FIG. 1 is a process diagram illustrating a first embodiment of a method for producing a cyclic compound or a derivative thereof of the present invention. FIG. 2 is a process diagram illustrating a second embodiment of the method for producing a cyclic compound or a derivative thereof of the present invention.

The method for producing the cyclic compound or its derivative of the present invention will be described in detail below based on the preferred embodiment shown in the attached drawings.

<Method for producing cyclic compound or derivative thereof>
First Embodiment
First, a first embodiment of the method for producing a cyclic compound or a derivative thereof of the present invention will be described.

Figure 1 is a process diagram illustrating a first embodiment of the method for producing a cyclic compound or a derivative thereof of the present invention.

The method for producing a cyclic compound or a derivative thereof according to this embodiment (hereinafter, abbreviated as "method for producing a cyclic compound") includes a raw liquid preparation step S01 for preparing a raw liquid from biomass, an acidification step S02 for adding an acid to the raw liquid, a drying step S03 for drying the raw liquid containing the cyclic compound or a derivative thereof to obtain a dried product, an extraction step S04 for extracting the cyclic compound or a derivative thereof from the dried product using a solvent to obtain an extract, and a precipitation step S05 for recovering the solute of the extract as a solid. According to this method for producing a cyclic compound, a solid, high-purity cyclic compound or a derivative thereof can be produced with a high yield.

Each step will be explained below. In the following explanation, cyclic compounds or their derivatives will be abbreviated to "cyclic compounds."

(Raw material liquid preparation step S01)
A raw material liquid is prepared from biomass by the method described in JP 2011-229544 A.

(Acidification step S02)
Next, an acid is added to the obtained raw material liquid as required. This allows a solid with high crystallinity to be obtained when the solid is recovered in the step described below. Therefore, a solid with high purity of the cyclic compound can be recovered in high yield.

The pH of the raw liquid after the addition of acid is not particularly limited, but is preferably about 1.0 to 6.5, and more preferably about 1.5 to 5.0. This makes it possible to recover high purity solids at a high yield while minimizing deterioration of the equipment, etc., when recovering solids in the process described below. In other words, it is possible to achieve both suppression of deterioration of the equipment, etc., and high purity and high yield of the recovered solids.

Examples of acids that can be added include formic acid, acetic acid, hydrochloric acid, propionic acid, butyric acid, and valeric acid. These acids are easily removed by evaporation in the drying process described below. For this reason, they are useful as acids to be added to acidify the raw material liquid.

(Drying step S03)
Next, the raw liquid is dried to obtain a dry product.

Methods for drying the raw liquid include, for example, boiling drying, spray drying, heat transfer drying, infrared drying, hot air drying, and vacuum drying. In addition, a combination of multiple drying methods including these may be used. Below, four representative drying methods will be explained in order.

- Boiling and drying method -
In the boiling and drying method, a raw liquid placed in a container is heated using a heating device such as a hot plate. When the container is heated by thermal conduction, the solvent in the raw liquid evaporates. This causes the solute to precipitate as a solid. As the solvent evaporates, the solid dries, and a dried product is obtained.

The heating temperature should be set to a temperature equal to or higher than the temperature at which the solvent evaporates, and although this varies depending on the type of solvent, it is preferable that the temperature is, for example, about 70 to 200°C, and more preferably about 80 to 150°C. This allows the solvent to evaporate efficiently while suppressing denaturation, decomposition, coloration, etc. of the cyclic compound.

The heating time is set appropriately depending on the degree of solvent evaporation, but as an example, it is preferably about 10 minutes to 10 hours, and more preferably about 30 minutes to 6 hours.

To suppress oxidation that occurs during heating, heating may be performed under a non-oxidizing gas or while spraying a non-oxidizing gas, if necessary.

This boiling and drying method has the advantage that it is possible to use simple equipment, making it easier to reduce manufacturing costs.

The obtained dried material may be crushed or pulverized as necessary. This increases the specific surface area of the dried material, thereby improving the extraction efficiency of the cyclic compounds in the extraction process described below.

- Spray drying method -
The spray drying method is a method in which, for example, a raw liquid is atomized using a nozzle in a drying chamber and then exposed to hot air (spray drying). As a result, the solvent in the raw liquid evaporates and the precipitated solute is formed into particles. This results in a dried product that is easy to handle.

In addition, because the raw liquid is atomized prior to drying, the specific surface area of the raw liquid is increased. This allows for uniform heating in a short period of time, minimizing denaturation and decomposition of solutes. In addition, such dried material provides high extraction efficiency for cyclic compounds in the extraction process described below.

Furthermore, since heat is conducted to the raw material liquid via the hot air, there is little unevenness in the temperature rise, which has the advantage that it is easy to achieve a uniform drying state.
Another advantage is that the efficiency of raising the temperature of the raw material liquid is high, and energy efficiency is high.

The dried material obtained by the spray drying method has a relatively uniform particle size. This makes it possible to omit or simplify the subsequent classification process, and to obtain a dried material that is highly fluid and easy to handle while keeping production costs down.

The average particle size of the particulate dried product produced is not particularly limited, but is preferably about 5 to 300 μm, and more preferably about 10 to 200 μm. This allows for a dried product to be obtained that is highly efficient in the process described below and is easy to handle in terms of flowability, etc.

The inlet temperature of the hot air is set appropriately depending on the boiling point of the solvent, but is preferably about 30 to 200°C, and more preferably about 40 to 150°C, for example.

In addition, since the spray drying method allows drying in a closed space, it is possible to dry the material under an inert gas such as nitrogen or argon, if necessary. This makes it possible to suppress oxidation of the dried material.

-Heat transfer drying method-
The heat transfer drying method (indirect heating drying method) is a method in which the raw material liquid is indirectly heated, for example, via a heat transfer surface, whereby the solvent in the raw material liquid in contact with the heat transfer surface evaporates, resulting in a dried product.

Examples of heat transfer surfaces include metal bodies in the shape of a disk, drum, cylinder, etc. In the heat transfer drying method, when the raw liquid is sprayed onto these heat transfer surfaces, it dries in a short time, and a dried material is obtained on the heat transfer surface. This dried material is scraped off with a scraper and collected as lumps or granules.

In addition, the raw liquid is thinned prior to drying, which increases the specific surface area of the raw liquid. This allows the temperature to be raised uniformly in a short period of time, minimizing denaturation and decomposition of the solute.

The temperature of the heat transfer surface is set appropriately depending on the boiling point of the solvent, but is preferably about 70 to 200°C, and more preferably about 80 to 150°C. This allows the solvent to evaporate efficiently while suppressing denaturation, decomposition, and coloring of the cyclic compound.

The heat transfer surface may also be placed under reduced pressure. This increases the efficiency of solvent evaporation and prevents oxidation and burning of the cyclic compound.

The heating time is set appropriately depending on the degree of solvent evaporation, but as an example, it is preferably about 10 minutes to 10 hours, and more preferably about 30 minutes to 6 hours.

The obtained dried material may be crushed or pulverized as necessary. This increases the specific surface area of the dried material, thereby improving the extraction efficiency of the cyclic compounds in the extraction process described below.

- Vacuum drying method -
The vacuum drying method is a method in which the raw liquid is placed in a sealed container and the pressure in the container is reduced to increase the solvent partial pressure difference between the raw liquid and the inside of the container, thereby promoting drying. This allows the raw liquid to be dried reliably in a short time, and a dried product to be obtained. In addition, low molecular weight impurity components can be efficiently removed, so the purity and whiteness of the finally obtained cyclic compound can be increased.

In addition, in the vacuum drying method, oxidation and combustion are unlikely to occur because the process is carried out under reduced pressure. This prevents the cyclic compounds from being denatured by oxidation or discolored due to burning. As a result, the purity and whiteness of the final cyclic compounds can be improved.

In addition, in the vacuum drying method, the raw liquid may be heated as necessary. In this case, the heating temperature is set appropriately according to the boiling point of the solvent, but as an example, it is preferably about 30 to 200°C, and more preferably about 40 to 150°C.

The heating time is set appropriately depending on the degree of solvent evaporation, but for example, it is preferably about 10 minutes to 24 hours, and more preferably about 30 minutes to 6 hours.

The pressure inside the sealed container during vacuum drying is not particularly limited as long as it is less than atmospheric pressure, but as an example, it is preferably 100 Pa or less, and more preferably 20 Pa or less. This allows for particularly efficient drying, and can minimize denaturation of cyclic compounds due to heating. In addition, denaturation and coloration due to oxidation can also be minimized.

The obtained dried material may be crushed or pulverized as necessary. This increases the specific surface area of the dried material, thereby improving the extraction efficiency of the cyclic compounds in the extraction process described below.

Although four drying methods have been described above, this process is not limited to a process that removes a large amount of liquid phase like the various drying methods described above, and may be a process in which some of the liquid phase remains. In other words, it may be a process that obtains an incompletely dried product.

The liquid phase content in the dried material is preferably 30% by mass or less, and more preferably 1% to 20% by mass. This reduces the time and energy required for drying, allowing for efficient processing.

In addition, if it is possible to reduce the liquid phase content to within the above range, a concentration method such as distillation, adsorption, extraction, membrane separation, dialysis, or reverse osmosis may be used in place of or in combination with the drying method described above. Concentration methods are easy to use in terms of technical difficulty and efficiency because they do not aim for complete drying. This makes it possible to obtain a dried product at a lower cost and in a shorter time.

When the liquid phase content is reduced to the above range by the concentration method, there is a risk that the concentration efficiency will gradually decrease as the concentration proceeds. In consideration of this problem, when using the concentration method, a process of repeatedly reducing pressure and returning to normal pressure during concentration may be performed as necessary. This causes the air bubbles to contract and expand, promoting the rise and bursting of the contained air bubbles, thereby making it possible to efficiently eliminate the air bubbles. As a result, the decrease in concentration efficiency can be suppressed.

The pressure in the decompression operation is not particularly limited, but is preferably about 0.1 to 100 kPa, and more preferably about 1 to 80 kPa. This allows the contained air bubbles to rise and burst efficiently, and promotes concentration while sufficiently suppressing a decrease in concentration efficiency.

The ratio of the time for the depressurization operation to the time for the normal pressure return operation is adjusted appropriately depending on the degree of bubble generation and the concentration speed, but as an example, it is preferable for it to be about 1:10 to 10:1. This allows for efficient removal of bubbles.

The time for the decompression operation is not particularly limited, but is preferably about 1 to 10 seconds, for example. This allows air bubbles to be removed efficiently.

(Extraction step S04)
Next, the cyclic compound is subjected to solid-liquid extraction from the dried product using a solvent to obtain an extract.

The solid-liquid extraction process is a process in which the cyclic compounds contained in the dried product are selectively extracted by utilizing their solubility in a solvent. In other words, it is a process in which a solvent that dissolves the cyclic compounds is used to obtain a solution of the cyclic compounds as an extract. This allows the cyclic compounds to be selectively transferred to the solvent side, while the impurities remain in the dried product. As a result, a highly pure cyclic compound is produced.

Examples of solvents include water, methanol, ethanol, isopropanol, acetone, acetonitrile, hexane, chloroform, and tetrahydrofuran.

The temperature of the solid-liquid extraction process is not particularly limited, but is preferably about 5 to 80°C, and more preferably about 10 to 50°C. This allows the solubility of the solvent to be optimized, making it possible to achieve both the purity of the extracted cyclic compounds and the extraction rate (extraction capacity).

That is, if the temperature is below the lower limit, the extraction rate may decrease. On the other hand, if the temperature exceeds the upper limit, impurities may also migrate more easily, and the purity of the cyclic compound may decrease.

The time for the solid-liquid extraction process is appropriately set depending on the temperature, but is, for example, about 30 minutes to 10 hours.
The extraction rate can be increased by heating under pressure.

The amount of solvent is not particularly limited, but is preferably about 3 to 200 g per 1 g of dried material, and more preferably about 10 to 50 g. This optimizes the amount of solvent. That is, if the amount of solvent is below the lower limit, the dissolution of the extract may become saturated and not all of the extract may be extracted. On the other hand, if the amount of solvent is above the upper limit, excess solvent may be produced and may be wasted. Also, the amount of impurities extracted may increase, and the purity of the cyclic compound may decrease.

When a concentration method is used in the drying process, the drying process and the extraction process may be carried out simultaneously. Specifically, a desiccant such as silica gel and a solvent for solid-liquid extraction may be added to the raw liquid or a liquid concentrate that has been concentrated to a certain extent. This allows the solid-liquid extraction process to be carried out simultaneously while the concentration is proceeding.

The amount of desiccant added is set appropriately depending on the amount of liquid phase and is not particularly limited, but it is preferable to add about 1 to 300 g per 100 g of concentrated liquid.

(Deposition step S05)
Next, the solute of the extract containing the cyclic compound is precipitated as a solid. This precipitation treatment may be any treatment that removes the extract.

Specifically, the precipitation step is preferably a step of evaporating the solvent contained in the extract (concentration to dryness). This type of treatment allows a solid to be easily precipitated from the extract containing the cyclic compound by a simple operation such as heating or reducing pressure. In other words, separation and drying of the solute dissolved in the extract can be performed simultaneously, enabling highly efficient treatment.

Examples of such evaporation processes include heating, decompression, and gas spraying, and a combination of several of these methods may be used.

Of these, the method of heating the extract to volatilize it is preferably used. The heating temperature is not particularly limited as long as it is a temperature at which the extract can be volatilized and is below the melting point of the cyclic compound, but is preferably about 50 to 300°C, and more preferably about 80 to 250°C. This makes it possible to efficiently remove the extract while suppressing deterioration of the cyclic compound.

Furthermore, a solid may be precipitated by a method other than the process of evaporating the solvent.
As such a method, for example, a crystallization process is mentioned, in which the solubility of the cyclic compound dissolved in the extract is reduced to selectively precipitate the cyclic compound. The crystallization process refines the cyclic compound, so that it becomes possible to precipitate a cyclic compound with a higher purity.

The crystallization process may be any process that causes a specific solute to precipitate as a solid in the raw liquid.

Specific examples include a process in which the temperature of the raw liquid is changed to utilize the temperature dependency of solubility for crystallization, a process in which the solvent is evaporated from the raw liquid by heating or reducing pressure, etc., a process in which a solvent in which the solute has low solubility is added to utilize the solvent-type dependency of solubility for crystallization, and a process in which the pH of the raw solution is changed to utilize the pH responsiveness of solubility for crystallization, and the like. One or a combination of these processes can be used.

For example, when using a crystallization process that utilizes pH responsiveness, the solubility of cyclic compounds in water generally decreases at low pH. Therefore, by lowering the pH in the crystallization process to, for example, about 1 to 4, the solubility can be reduced and the cyclic compounds can be precipitated.

The temperature at this time is not particularly limited, but is preferably about 15 to 80°C, and more preferably about 20 to 60°C. This allows both the crystallization process capacity and yield to be achieved.

The crystallization process may be a batch process or a continuous process.
For the crystallization operation, a known stirring tank is used.

In order to promote crystallization, seed crystals containing the solid components to be precipitated may be added as necessary. This promotes crystallization with the seed crystals acting as nuclei, thereby increasing the crystallization efficiency and facilitating high purity.
After the crystallization treatment, the solids in the extract may be separated by a solid-liquid separation treatment.

Examples of solid-liquid separation treatments include filtration, sedimentation, dehydration under reduced pressure, and dehydration under pressure, among which filtration is particularly preferred from the viewpoints of ease of operation and accuracy of separation. Specifically, a centrifugal filter can be used.
The solid-liquid separation operation may be a batch operation or a continuous operation.

Thereafter, if necessary, washing is carried out with a poor solvent, and then drying is carried out, whereby a solid cyclic compound can be recovered.
Prior to the above crystallization procedure, a concentration treatment may be carried out.

(Other processes)
The recovered solid cyclic compound may also be subjected to other additional processing steps.

Other treatments include, for example, redissolution treatment, activated carbon treatment, reprecipitation treatment, etc.

-Remelting process-
The re-dissolving process is a process in which the recovered cyclic compound is dissolved in a good solvent, thereby preparing a solution of the cyclic compound.
Examples of good solvents include water, methanol, hexane, and chloroform.

- Activated carbon treatment -
Next, the prepared solution is treated with activated carbon. As a result, the polymer components in the solution are adsorbed by the activated carbon and removed. Note that, although other adsorption media may be used instead of activated carbon, activated carbon is preferably used.

Add activated charcoal to the solution and stir. Activated charcoal can also be used to decolorize the solutes in the solution.

The temperature for the activated carbon treatment is preferably about 30 to 150°C. The time for the activated carbon treatment is not particularly limited, but is preferably about 10 minutes to 10 hours.

The amount of activated carbon added per 100 g of solution is not particularly limited, but is preferably 0.01 to 3 g, and more preferably 0.1 to 1 g. This prevents the solute from being adsorbed by the activated carbon, while still providing sufficient decolorization.

The activated carbon treatment may be performed as necessary, and may be omitted. The order of the activated carbon treatment is not limited to that of the present embodiment, and may be performed, for example, before the drying step or between the extraction step and the precipitation step.
After the treatment, the activated carbon is removed by solid-liquid separation such as filtration.

-Reprecipitation treatment-
The reprecipitation process is a process in which a poor solvent for the cyclic compound is added to the prepared solution to obtain a precipitate of the cyclic compound. That is, a poor solvent is added to the solution to reduce the solubility of the cyclic compound, causing it to precipitate as a solid. This allows the cyclic compound to be selectively precipitated, thereby achieving high purity.

The precipitated solid is separated by solid-liquid separation and then dried to recover the solid cyclic compound.

The poor solvent is not particularly limited as long as it is miscible with water and has a lower solubility for shikimic acid than water, but examples of the poor solvent include ethanol, acetonitrile, acetone, isopropanol, and ethyl acetate.

Second Embodiment
Next, a second embodiment of the method for producing a cyclic compound or a derivative thereof of the present invention will be described.

Figure 2 is a process diagram for explaining a second embodiment of the method for producing a cyclic compound or a derivative thereof of the present invention. Note that among the symbols used in Figure 2, the steps with the same symbols as those in Figure 1 indicate that they are the same as the steps explained in the first embodiment.

The second embodiment will be described below, but in the following explanation, the differences from the first embodiment will be mainly described, and explanations of similar points will be omitted.

The method for producing a cyclic compound or a derivative thereof according to this embodiment includes a raw liquid preparation step S01 for preparing a raw liquid from biomass, an acidification step S02 for adding an acid to the raw liquid, a drying step S03 for drying the raw liquid containing the cyclic compound or a derivative thereof to obtain a dried product, a redissolution step S06 for redissolving the dried product to obtain a solution, an adsorption step S07 for subjecting the solution to an adsorption treatment to obtain a treated liquid, an extraction step S08 for extracting the cyclic compound or a derivative thereof from the treated liquid to obtain an extract, and a precipitation step S05 for recovering the solute of the extract as a solid. According to this method for producing a cyclic compound, a solid, high-purity cyclic compound or a derivative thereof can be produced with a high yield.

Each step will be explained below. In the following explanation, cyclic compounds or their derivatives will be abbreviated to "cyclic compounds."

(Raw material liquid preparation step S01)
First, a liquid source is prepared in the same manner as in the first embodiment.

(Acidification step S02)
Next, as necessary, an acid is added to the obtained raw material liquid in the same manner as in the first embodiment.

(Drying step S03)
Next, in the same manner as in the first embodiment, the raw material liquid is dried to obtain a dried product.

(Redissolving step S06)
Next, if necessary, the dried product is dissolved in a good solvent to prepare a solution of the cyclic compound.
Examples of good solvents include water, methanol, hexane, and chloroform.

(Adsorption step S07)
Next, the prepared solution is subjected to an adsorption treatment such as an activated carbon treatment. This activated carbon treatment is the same as the activated carbon treatment according to the first embodiment. As a result, the polymer components in the solution are adsorbed by the activated carbon and removed. Note that, although other adsorption media may be used instead of activated carbon, activated carbon is preferably used.

This step may be performed as necessary, and may be omitted. The order of this step is not limited to that in this embodiment, and may be performed, for example, before the drying step, between the extraction step and the precipitation step, or both.

After the treatment, the activated carbon is removed by solid-liquid separation such as filtration. This results in a solution of the cyclic compound from which at least some of the impurities have been removed.

(Extraction step S04)
Next, the solution, i.e., the dried product obtained in the drying step S03, is subjected to a re-dissolution process and an adsorption process using an organic solvent, and the liquid resulting from dissolving the dried product is subjected to a liquid-liquid extraction process of the cyclic compound to obtain an extract.

Liquid-liquid extraction is a process that selectively extracts cyclic compounds by utilizing the difference in solubility in an organic solvent between cyclic compounds and impurities such as inorganic salts contained in a solution. In other words, it is a process that uses an organic solvent that dissolves cyclic compounds to obtain a solution of the cyclic compounds as an extract. This allows the cyclic compounds to be selectively transferred to the organic solvent, while impurities such as inorganic salts can be left in the solvent that was originally contained in the solution. As a result, a highly pure cyclic compound is produced.

Examples of organic solvents include n-butanol, isobutanol, iso-n-pentanol, isopentyl alcohol, n-hexanol, 2-hexanol, chloroform, hexane, diethyl ether, dichloromethane, and carbon tetrachloride.

In addition, in this extraction process, instead of the liquid-liquid extraction process described above, a solid-liquid extraction process similar to that of the first embodiment may be performed. In that case, a second drying process may be performed to solidify the solution obtained in the adsorption process S07. The second drying process may be performed in the same manner as the drying process according to the first embodiment.

(Deposition step S05)
Next, in the same manner as in the first embodiment, the solute of the extract containing the cyclic compound is precipitated, and if necessary, washed and dried, whereby the solid cyclic compound can be recovered.

Thereafter, other steps similar to those in the first embodiment may be performed as necessary.

<Cyclic Compound or Derivative>
Next, embodiments of the cyclic compound or a derivative thereof of the present invention will be described.

The cyclic compound or its derivative according to this embodiment is, for example, a compound represented by the following formula (1).

［式（１）中、環Ａは、飽和環、部分飽和環もしくは芳香環の５員環、飽和環、部分飽和環もしくは芳香環の６員環、または、５員環もしくは６員環を含む縮合環であり、Ｘは単結合または１つ以上の炭素数を含む結合であり、Ｙは水素原子またはアルキル基、Ｒ^２～Ｒ^６（環Ａが５員環の場合はＲ^２～Ｒ^５）は、独立して、水素原子、水酸基、アミノ基、アルコキシ基、カルボキシル基またはカルボニル基である。］

[In formula (1), ring A is a five-membered saturated ring, partially saturated ring, or aromatic ring, a six-membered saturated ring, partially saturated ring, or aromatic ring, or a fused ring containing a five-membered ring or a six-membered ring, X is a single bond or a bond containing one or more carbon atoms, Y is a hydrogen atom or an alkyl group, and R ² to R ⁶ (R ² to R ⁵ when ring A is a five-membered ring) are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group.]

The derivative of a cyclic compound is any one of the compounds represented by the above formula (1), compounds derived from the compounds represented by the above formula (1), and salts of the compounds represented by the above formula (1), or a mixture of two or more of these.

Compounds derived from the compound represented by formula (1) above include esters, acid anhydrides, amides, acid halides, etc. of the compound represented by formula (1). Examples of esters include methyl esters, ethyl esters, propyl esters, and butyl esters.

Examples of salts of the compound represented by the above formula (1) include sodium salts, potassium salts, ammonium salts, etc.

In addition, such cyclic compounds are preferably derived from biomass and are in powder form. This makes it possible to obtain chemical products or chemical product raw materials that have a low environmental impact and are easy to handle.

In addition, such cyclic compounds preferably have an ISO whiteness of 70% or more, more preferably 80% or more, measured according to the ISO whiteness test method specified in JIS P 8148:2001. Such cyclic compounds are chemical products or chemical raw materials with few impurities even if derived from biomass. In particular, when producing light-colored chemical products, it is necessary to prevent the color of the raw materials from transferring to the chemical product. In such cases, by using cyclic compounds with an ISO whiteness within the above range, color defects are less likely to occur and high-quality chemical products can be obtained.

The ISO whiteness is measured using a spectrophotometer (e.g., PF7000R manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS P 8148:2001 "Method of measurement of ISO whiteness (diffuse blue light reflectance)".

Here, the compound represented by formula (1) will be further explained.
Examples of the saturated ring, partially saturated ring, or aromatic 5-membered ring include a furan structure, a thiophene structure, a pyrrole structure, a pyrrolidine structure, a tetrahydrofuran structure, a 2,3-dihydrofuran structure, a pyrazole structure, an imidazole structure, an oxazole structure, an isoxazole structure, a thiazole structure, and an isothiazole structure.

Examples of the six-membered saturated ring include hydrocarbon-based saturated rings such as a cyclohexane structure, nitrogen-containing saturated rings such as a piperidine structure, piperazine structure, triazinane structure, tetraazinane structure, pentazinane structure, and quinuclidine structure, oxygen-containing saturated rings such as a tetrahydropyran structure and a morpholine structure, and sulfur-containing saturated rings such as a tetrahydrothiopyran structure.

Examples of the six-membered partially saturated ring include hydrocarbon partially saturated rings such as a cyclohexene structure or a cyclohexadiene structure, nitrogen-containing partially saturated rings such as a piperidine structure, oxygen-containing partially saturated rings such as a pyran structure, and sulfur-containing partially saturated rings such as a thiazine structure.

Examples of the six-membered aromatic ring include hydrocarbon aromatic rings such as a benzene structure, and nitrogen-containing aromatic rings (nitrogen-containing unsaturated rings) such as a pyridine structure, pyridazine structure, pyrimidine structure, pyrazine structure, triazine structure, tetrazine structure, and pentazine structure.

Examples of fused rings include a fused ring of a 6-membered ring and a 5-membered ring, and a fused ring of two 6-membered rings. Of these, examples of fused rings of a 6-membered ring and a 5-membered ring include indole-based structures such as indole, indolenine, indoline, isoindole, isoindolenine, isoindoline, isodolizine, purine, and indolizidine. Examples of fused rings of two 6-membered rings include quinoline-based structures such as quinoline, isoquinoline, quinolizidine, quinoxaline, cinnoline, quinazoline, phthalazine, naphthyridine, and pteridine.

X is a single bond or a bond containing one or more carbon atoms.
When X is a single bond, the oxygen atom is directly bonded to a ring-constituting atom of ring A.

On the other hand, examples of bonds containing one or more carbon atoms include hydrocarbon groups having 1 to 4 carbon atoms, ether bonds, ester bonds, amide bonds, carbonyl groups, vinylidene groups, etc., and these may be used alone or in combination of two or more.

Of these, the hydrocarbon group having 1 to 4 carbon atoms may be either linear or branched, and may be either saturated or unsaturated. The hydrogen atom of the hydrocarbon group may be substituted with a substituent such as an alkyl group having 1 to 2 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, or a halogen atom.

In addition to the bonds described above, X may contain any atom or atomic group. For example, X may be an atomic group that contains a carbonyl group and a bond containing one or more carbon atoms.

Y is a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 4.

When ring A is a 6-membered ring, R ² to R ⁶ are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group, and when ring A is a 5-membered ring, R ² to R ⁵ are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group.

When ring A is a 6-membered ring and any of R ² to R ⁶ is a carbonyl group, or when ring A is a 5-membered ring and any of R ² to R ⁵ is a carbonyl group, the ring-constituting atom of ring A is a carbon atom and there is a double bond between the carbon atom and an oxygen atom, which is referred to as a carbonyl group.

Specific examples of cyclic compounds include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, mellophanic acid, prenitic acid, pyromellitic acid, phenylacetic acid, hydroxyphenylacetic acid, phenylbutyric acid (phenyllactate), hydroxyphenylbutyric acid, phenylpyruvic acid, hydroxyphenylpyruvic acid, phenyllactic acid, hydroxyphenyllactic acid, anthranilic acid, hydroatropic acid, atropic acid, hydrophenyllactic acid, phenylacetate ... Cinnamic acid (coumaric acid), cinnamic acid, salicylic acid (2-hydroxybenzoic acid), m-salicylic acid (3-hydroxybenzoic acid), p-salicylic acid (4-hydroxybenzoic acid), methoxybenzoic acid, aminobenzoic acid, hydroxybenzoic acid, pyrocatechuic acid (2,3-dihydroxybenzoic acid), β-resorcylic acid (2,4-dihydroxybenzoic acid), gentisic acid (2,5-dihydroxybenzoic acid), γ-resorcylic acid (2,6-dihydroxybenzoic acid), protocatechuic acid (3,4-dihydroxybenzoic acid), α-resorcylic acid (3,5-dihydroxybenzoic acid), trihydroxybenzoic acid, vanillic acid (4-hydroxy-3-methoxybenzoic acid), isovanillic acid (3-hydroxy-4-methoxybenzoic acid), veratric acid, gallic acid, syringic acid, asaronic acid, mandelic acid, vanillylmandelic acid, anisic acid, homoprotocatechuic acid, homovanillic acid, homoisovanillic acid, homoveratric acid, homophthalic acid, homoisophthalic acid, homo These include terephthalic acid, phthalonic acid, isophthalonic acid, terephthalonic acid, atrolactic acid, tropic acid, mellitic acid, phloretic acid, dihydrocaffeic acid, hydroferulic acid, hydroisoferulic acid, umbellic acid, caffeic acid (caffeic acid), ferulic acid, isoferulic acid, sinapic acid, syringic acid, dehydroquinic acid, dehydroshikimic acid, shikimic acid, chorismic acid, L-tryptophan, L-tyrosine, prephenic acid, arogenic acid, and L-phenylalanine.

Other specific examples of cyclic compounds include polyphenols such as flavonoids, lignans, chalcones, stilbenoids, alkaloids, curcuminoids, terpenoids, saponins, various glycosides, and various polyphenol-based aromatic compounds, as well as amino acids and vitamins.

Among these, examples of flavonoids include anthocyanidins such as aurantidin, cyanidin, delphinidin, europinidin, luteolinidin, pelargonidin, malvidin, peonidin, petunidin, and rosinidin, anthocyanins such as procyanidin, flavanones such as naringenin, eriocitrin, pinocembrin, and eriodictyol, flavans such as catechin, flavones such as apigenin, luteolin, baicalein, and chrysin, flavonols such as quercetin and kaempferol, isoflavones, isoflavones, isoflavanes, isoflavandiols, and isoflavonoids such as genistein, as well as neoflavonoids, biflavonoids, aurones, prenylated flavonoids, and O-methylated flavonoids.

Examples of lignans include pinoresinol, lariciresinol, secoisolariciresinol, matairesinol, hydroxymatairesinol, syringaresinol, sesamin, arctigenin, sesaminol, podophyllotoxin, and steganacin.

Further examples of stilbenoids include aglycones such as piceatannol, pinosylvin, pterostilbene, resveratrol, 4'-methoxyresveratrol, pinostilbene, and piciatannol, and oligomers such as α-viniferin, ampelopsin A, ampelopsin E, diptoindonesin C-kawane, diptoindonesin F-dammarbua, ε-viniferin, flexosol A, gnetin H, hemsleyanol D, hopeaphenol, diptoindonesin B, and vaticanol B.

Curcuminoids include, for example, curcumin and shogaol.

Further examples of terpenoids include carotenoids such as lutein, vitamin A, vitamin E, and beta-carotene, as well as steroids such as sitosterol.

Examples of various glycosides include phenolic glycosides such as salicin, β-glucogallin, salicylic acid glucoside, salidroside, gastrodin, poplin, phloridzin, and arbutin, coumarin glycosides such as esculin, flavonoid glycosides such as hesperidin and rutin, and stilbenoid glycosides such as astringin, piceid, and diptoindonesin A.

Furthermore, various polyphenol-based aromatic compounds include, for example, tyrosol, hydroxytyrosol, esculetin, phloretin, rosmarinic acid, salvianic acid A, reticuline, paracoumaryl alcohol, coniferyl alcohol, caffeyl alcohol, etc.

Furthermore, examples of amino acids include phenylalanine and tyrosine.
Furthermore, examples of vitamins include vitamin A, vitamin D, and vitamin E.

Further specific examples of cyclic compounds include aromatic compounds, alicyclic compounds, aliphatic compounds, and heterocyclic compounds.

Among these, examples of aromatic compounds include vanillin, 2-phenylethanol, phenylacetic acid, cinnamic alcohol, isoeugenol, ferulic acid, 4-aminobenzoic acid, anethole, estragole, methyl anthranilate, methyl cinnamate, ethyl cinnamate, phenylacetaldehyde, cinnamic aldehyde, cinnamyl acetate, resorcin, 4-vinylphenol, 4-vinyl-2-methoxyphenol, 3,4-dihydroxystyrene, dopamine, levodopa, hydroquinone, coumarin, 7-hydroxycoumarin, 4-hydroxycoumarin, and xiamenmycin A.

Examples of alicyclic compounds include carveol, perilla alcohol, borneol, methyl jasmonate, 1,8-cineole, L-menthone, valencene, nootkatone, α-pinene, camphene, L-carvone, perilla aldehyde, myrtenal, L-menthyl acetate, and β-ionone.

Furthermore, examples of aliphatic compounds include cis-3-hexenol, cis-3-hexenyl acetate, acetoin, nerol, farnesol, arginine, muconic acid, etc.

Examples of heterocyclic compounds include niacin, niacinamide, maltol, and indole. Among these, an example of indole is 5,6-dihydroxyindole.

On the other hand, examples of derivatives of cyclic compounds include esters, acid anhydrides, amides, acid halides, salts, etc. of the above-mentioned compounds, or all compounds derived from cyclic compounds.

The molecular weight of the cyclic compound or its derivative is not particularly limited, but is preferably 120 to 1,000, and more preferably 130 to 800.

When ring A of the cyclic compound represented by formula (1) is a five-membered saturated or partially saturated ring in which all of the ring-constituting atoms are carbon atoms, it is preferable that one or more of the carbon atoms of ring A to which R ² to R ⁵ and X are bonded are asymmetric carbon atoms. When ring A of the cyclic compound represented by formula (1) is a six-membered saturated or partially saturated ring in which all of the ring-constituting atoms are carbon atoms, it is preferable that one or more of the carbon atoms of ring A to which R ² to R ⁶ and X are bonded are asymmetric carbon atoms.

In such a case, the cyclic compound becomes a stereoisomer. In this case, according to the present embodiment, it is possible to produce a cyclic compound with a high purity of a specific stereoisomer and a low content of other stereoisomers in a high yield. As a result, the complicated process of removing unnecessary stereoisomers is no longer necessary, and the production cost can be reduced.

In addition, in the cyclic compound represented by the above formula (1), when the carbon atom of ring A to which X is bonded is ^C1 , the carbon atom of ring A to which ^R2 is bonded is ^C2 , the carbon atom of ring A to which ^R3 is bonded is ^C3 , the carbon atom of ring A to which ^R4 is bonded is ^C4 , the carbon atom of ring A to which ^R5 is bonded is ^C5 , and the carbon atom of ring A to which ^R6 is bonded is ^C6 , it is preferable that the combination of these carbon atoms being asymmetric carbon atoms is one type selected from the group consisting of the following (a) to (h):

(a) ^C1
(b) ^C2
(c) ^C3
(d) ^C4
(e) ^C1 and ^C4
(f) ^C3 and ^C4
(g) ^C1 , ^C3 and ^C4
(h) ^C3 , ^C4 and ^C5

The following formula (2) is a formula in which the above C ¹ to C ⁶ indications are added to the cyclic compound represented by the above formula (1).

［式（２）中、環Ａは、飽和環、部分飽和環もしくは芳香環の５員環、飽和環、部分飽和環もしくは芳香環の６員環、または、５員環もしくは６員環を含む縮合環であり、Ｘは単結合または１つ以上の炭素数を含む結合であり、Ｙは水素原子またはアルキル基、Ｒ^２～Ｒ^６（環Ａが５員環の場合はＲ^２～Ｒ^５）は、独立して、水素原子、水酸基、アミノ基、アルコキシ基、カルボキシル基またはカルボニル基である。また、Ｃ^１～Ｃ^６は、それぞれ、環Ａの環構成原子としての炭素原子である。］

[In formula (2), ring A is a five-membered saturated ring, partially saturated ring, or aromatic ring, a six-membered saturated ring, partially saturated ring, or aromatic ring, or a fused ring containing a five-membered ring or a six-membered ring; X is a single bond or a bond containing one or more carbon atoms; Y is a hydrogen atom or an alkyl group; R ² to R ⁶ (R ² to R ⁵ when ring A is a five-membered ring) are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group; and C ¹ to C ⁶ are each carbon atoms constituting ring A.]

The cyclic compound and its derivatives are preferably compounds represented by the above formula (2), and more preferably 3-dehydroquinate, 3-dehydroshikimic acid, shikimic acid, chorismic acid, or prephenic acid. These compounds are used in many fields, and their structures are represented by the following formula:

3-dehydroquinate

・3-dehydroshikimic acid

・Shikimic acid

- Chorismic acid

- Prephenic acid

The uses of the above-mentioned cyclic compounds or their derivatives are not particularly limited, but examples of such uses include various chemical products such as fragrance compositions, cosmetic compositions, pharmaceuticals, pesticides, chemicals, materials for electrical and electronic parts, synthetic fibers, resins, and food additives. Cyclic compounds or their derivatives are also used as raw materials for various chemical products. Examples of such raw materials include raw materials for fragrances, cosmetic materials, pharmaceutical materials, pesticide raw materials, chemical raw materials, raw materials for electrical and electronic parts, raw materials for synthetic fibers, raw materials for resins, and raw materials for food additives. Note that raw materials refer to intermediates used in the synthesis of chemical products.

The above describes the method for producing the cyclic compound or its derivative of the present invention based on the embodiments, but the present invention is not limited to these.

For example, the method for producing a cyclic compound or a derivative thereof of the present invention may include any step added to the above embodiment.

Next, specific examples of the present invention will be described.
1. Preparation of cyclic compounds (Example 1)
[1] First, biomass was pretreated to obtain a sugar mixture.

[2] Next, the grown transformant was reacted with a sugar mixture to obtain a culture solution. The culture solution was centrifuged to obtain a supernatant (raw liquid).

[3] Next, acetic acid was added to the obtained raw material liquid.
[4] Next, the obtained raw material liquid was dried by a spray drying method to obtain a particulate dried product. The heating temperature was set to 120° C. at the inlet and 80° C. at the outlet of the hot air. The supply rate of the raw material liquid was set to 0.64 kg/h.

[5] Next, the cyclic compounds were extracted from the dried product using methanol. This resulted in an extract. The temperature of the solid-liquid extraction process was 30°C, the time was 2 hours, and the amount of solvent was 20 g per 1 g of dried product.

[6] Next, the obtained extract was heated and concentrated to evaporate the solvent contained therein. This caused the solid shikimic acid (cyclic compound) to precipitate and be recovered.

[7] Next, the recovered solid shikimic acid was redissolved in pure water. The amount of pure water used for redissolution was 5 g per 1 g of solid shikimic acid.

[8] Next, activated carbon was added to the redissolved solution obtained, and activated carbon treatment was performed. Note that 0.4 g of activated carbon was used per 100 g of the redissolved solution.

[9] Next, ethanol was added as a poor solvent to the redissolved solution that had been treated with activated carbon. This caused solid shikimic acid (a cyclic compound) to precipitate. The precipitate was then separated into solid and liquid by filtration, washed with ethanol, and then dried and collected.

(Examples 2 to 14)
Shikimic acid (cyclic compound) was obtained in the same manner as in Example 1, except that the production conditions were changed as shown in Table 1.

In addition, "concentration and crystallization" in Example 8 of Table 1 refers to a process in which a concentration process and a cooling and crystallization process are sequentially performed to precipitate solid shikimic acid.
The pressure inside the closed container was set to 1 Pa in the vacuum drying method.

(Example 15)
[1] First, biomass was pretreated to obtain a sugar mixture.
[2] Next, the grown transformant was reacted with a sugar mixture to obtain a culture solution, which was then centrifuged to obtain a supernatant (raw liquid).

[3] Next, acetic acid was added to the obtained raw material liquid.
[4] Next, the obtained raw material liquid was dried by a spray drying method to obtain a particulate dried product.

[5] Next, the dried material was redissolved in pure water. The amount of pure water used for redissolution was 5 g per 1 g of dried material.

[6] Next, activated carbon was added to the redissolved solution obtained, and activated carbon treatment was performed. Note that 0.4 g of activated carbon was used per 100 g of the redissolved solution.

[7] Next, the redissolved liquid was subjected to liquid-liquid extraction treatment using 1-butanol as an organic solvent, thereby obtaining a solution containing 1-butanol as a solvent.
[8] Next, the solute was precipitated by concentration to dryness, and the precipitate was collected.

(Examples 16 to 18)
Shikimic acid (cyclic compound) was obtained in the same manner as in Example 15, except that the production conditions were changed as shown in Table 2.

(Example 19)
[1] First, the redissolved solution was treated with activated carbon in the same manner as in Example 15.
[2] Next, the redissolved liquid was spray-dried again to obtain a particulate dried product. The heating temperature was set to 120° C. at the inlet and 80° C. at the outlet of the hot air. The supply rate of the raw material liquid was set to 0.64 kg/h.

[3] Next, the cyclic compounds were extracted from the dried product using methanol. This resulted in an extract. The temperature of the solid-liquid extraction process was 30°C, the time was 2 hours, and the amount of solvent was 20 g per 1 g of dried product.

[4] Next, the obtained extract was heated and concentrated to evaporate the solvent contained therein. This caused the solid shikimic acid (cyclic compound) to precipitate and be recovered.

(Examples 20 to 22)
Shikimic acid (cyclic compound) was obtained in the same manner as in Example 19, except that the production conditions were changed as shown in Table 2.

Comparative Example
[1] First, methane was produced from biomass through microbial fermentation.

[2] Next, methane was used as a raw material and reacted with a catalyst made of zeolite carrying molybdenum and iron to produce benzene, which was then purified by distillation.
[3] Next, shikimic acid was synthesized from benzene.

(Reference example)
A commercially available shikimic acid reagent was prepared.

2. Evaluation of cyclic compounds 2.1 Purity measurement The purity of shikimic acid in the cyclic compounds obtained in each Example and Comparative Example was measured by high performance liquid chromatography (HPLC). The purity was expressed as the ratio of the mass of shikimic acid to the total mass of the recovered solid (unit: mass%).
The measurement conditions are as follows.

<HPLC analysis conditions for shikimic acid>
Column: COSMOSIL 5C18-AR-II (φ4.6 mm × 250 mm) manufactured by Nacalai Tesque Mobile phase: water/methanol/perchloric acid = 4/1/0.0075 (vol/vol/vol) isocratic elution Flow rate: 1 mL/min
Column temperature: 40°C
Detection method: Photodiode array (PDA) detector (210 nm)
The measurement results are shown in Tables 1 and 2.

2.2 Yield Evaluation The yield of shikimic acid was measured for the cyclic compounds obtained in each Example and Comparative Example by high performance liquid chromatography (HPLC) and mass measurement. The yield was calculated by calculating the amount of shikimic acid in the raw liquid by high performance liquid chromatography (HPLC), calculating the recovered amount from the mass of the recovered solid and the purity of shikimic acid, and expressing it as the ratio (unit: %) of the recovered shikimic acid to the amount of shikimic acid in the raw liquid.
The measurement results are shown in Tables 1 and 2.

2.3 Evaluation of Whiteness The ISO whiteness of the cyclic compounds obtained in the Examples and Comparative Examples and the commercially available reagent of the Reference Example was measured using a spectrophotometer.
The measurement results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, in each example, it was possible to recover high purity cyclic compounds in high yields.

In addition, we also produced (recovered) 4-hydroxybenzoic acid, an example of a cyclic compound, instead of shikimic acid, and observed similar trends to the results shown in Tables 1 and 2.

S01 Raw material liquid preparation step S02 Acidification step S03 Drying step S04 Extraction step S05 Precipitation step S06 Re-dissolving step S07 Adsorption step

Claims (7)

A raw material liquid preparation step of preparing a raw material liquid containing shikimic acid or a derivative thereof from biomass;
a drying step of adding a desiccant to the raw liquid and then vacuum-drying the raw liquid under reduced pressure to concentrate the raw liquid;
An extraction step of adding an extraction solvent to the raw material liquid to extract shikimic acid or a derivative thereof to obtain an extract;
a precipitation step of obtaining the solute of the extract as a solid;
a step of performing a re-dissolving process after the precipitation step, in which the solute is dissolved in a good solvent to obtain a solution;
subjecting the solution to an activated carbon treatment;
a step of subjecting the solution that has been treated with activated carbon to a reprecipitation treatment by adding a poor solvent and recovering a precipitate as a solid;
having
The drying step and the extraction step are carried out simultaneously by adding the desiccant and the extraction solvent to the raw material liquid;
A method for producing shikimic acid or a derivative thereof, characterized in that the recovered solid is in powder form and has an ISO whiteness of 70% or more as measured in accordance with the ISO whiteness test method specified in JIS P 8148:2001. The drying step includes a process of adding the desiccant to a concentrated liquid obtained by concentrating the raw material liquid, and further concentrating the concentrated liquid,
2. The method for producing shikimic acid or a derivative thereof according to claim 1, wherein the amount of the desiccant added is 1 to 300 g per 100 g of the concentrated liquid . A raw material liquid preparation step of preparing a raw material liquid containing shikimic acid or a derivative thereof from biomass;
a drying step of vacuum drying the raw material liquid to obtain a dried product;
a redissolving step of dissolving the dried product in a good solvent to obtain a solution;
an adsorption step of subjecting the solution to an activated carbon treatment;
an extraction step of liquid-liquid extracting shikimic acid or a derivative thereof from the solution treated with the activated carbon using an extraction solvent to obtain an extract;
a precipitation step of recovering the solute from the extract as a solid;
having
A method for producing shikimic acid or a derivative thereof, characterized in that the recovered solid is in powder form and has an ISO whiteness of 70% or more as measured in accordance with the ISO whiteness test method specified in JIS P 8148:2001. a step of performing a re-dissolving process after the precipitation step, in which the solute is dissolved in a good solvent to obtain a solution;
subjecting the solution to an activated carbon treatment;
a step of subjecting the solution that has been treated with activated carbon to a reprecipitation treatment by adding a poor solvent and recovering a precipitate as a solid;
The method for producing shikimic acid or a derivative thereof according to claim 3 , comprising the steps of: The method for producing shikimic acid or a derivative thereof according to claim 3 or 4 , wherein the dried product has a liquid phase content of 30 mass% or less. The method for producing shikimic acid or a derivative thereof according to any one of claims 1 to 5 , further comprising an acidification step of adding an acid to the raw liquid, the acidification step being performed before the drying step. The method for producing shikimic acid or a derivative thereof according to claim 1 , wherein the precipitation step is a step of evaporating the solvent contained in the extract.

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