KR20170036231A - Purifying method of dodecanedioic acid - Google Patents
Purifying method of dodecanedioic acid Download PDFInfo
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- KR20170036231A KR20170036231A KR1020150135136A KR20150135136A KR20170036231A KR 20170036231 A KR20170036231 A KR 20170036231A KR 1020150135136 A KR1020150135136 A KR 1020150135136A KR 20150135136 A KR20150135136 A KR 20150135136A KR 20170036231 A KR20170036231 A KR 20170036231A
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- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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Abstract
The present invention relates to a method for purifying a dodecanedioic acid which can induce crystal growth while increasing the number of microcrystals, thereby increasing the crystal size and obtaining high purity dodecanedioic acid at a high yield.
Description
The present invention relates to a method for purifying dodecanedioic acid. More specifically, the present invention relates to a method for purifying dodecanedioic acid, which can induce crystal growth while increasing the number of microcrystals, thereby increasing the crystal size and obtaining high purity dodecanedioic acid at a high yield .
Dodecanedioic acid (DDDA), a raw material of nylon, is a relatively inexpensive chemical substance very important to the chemical industry. It is used in various industrial applications such as polymer plasticizers, epoxy curing agents, adhesives and powder coatings, .
However, the reaction for synthesizing dodecanedioic acid proceeds mostly in a solution phase, and various methods for separating and purifying the finally prepared dodecanedioic acid from a reaction solution containing impurities have been studied.
Conventionally known methods for the separation and purification of dodecanedioic acid can be roughly summarized in two ways. One method is to remove excess organic solvent and purified water at high temperature to remove impurities, and the other is to melt in a solvent and recrystallize to room temperature.
However, the method of purifying dodecanedioic acid by using an excessive amount of organic solvent has a limitation that harmful gas is generated in a process of filtering with a high temperature organic solvent, and a method of dissolving in a solvent and recrystallizing is complicated in dissolution process, The crystallized dodecanedioic acid has a small size and the yield is reduced in the filtering process.
In addition, in the case of the previously known dodecanedioic acid separation purification, since it is a dodecanedioic acid separation purification obtained through chemical synthesis from a petrochemical raw material, it is sensitive to price fluctuation and increases burden on environmental pollution, Alternative methods of producing renewable, sustainable and environmentally friendly dodecanedioic acid and its derivatives are being sought.
To this end, research has been conducted on a technique for producing dodecanedioic acid by a biological process using a strain. However, the dodecanedioic acid produced by the biological process also has a problem that the size of the dodecanedioic acid crystallized in the separation and purification process through recrystallization is small, so that it is difficult to overcome the limit of the yield reduction in the filtering process.
Therefore, it is necessary to study a technique for securing a high purity and high yield in the process of separating and purifying dodecanedioic acid produced by a biological process through recrystallization.
The present invention is to provide a dodecanedioic acid purification method capable of obtaining high purity dodecanedioic acid at a high yield by increasing the crystal size by inducing crystal growth while inhibiting the generation of a large number of microcrystals .
In the present specification, there is provided a process for producing a dodecanedioic acid solution, comprising the steps of: cooling to a temperature below the saturation temperature above supersaturation, while maintaining the concentration of the dodecanedioic acid solution below the saturation concentration and above the supersaturation concentration; To a concentration lower than the saturation concentration and the supersaturation concentration, and repeating the step for two or more times. The micrododecane dioxanic acid crystals having a maximum diameter of less than 2 mu m contained in the cooled dodecanedioic acid solution Is less than 1% by weight based on the total weight of the dodecanedioic acid.
Hereinafter, a method for purifying dodecanedioic acid according to a specific embodiment of the present invention will be described in detail.
According to an embodiment of the invention, there is provided a process for producing a dodecanedioic acid solution, comprising the steps of: cooling to a temperature below the saturation temperature above the supersaturation temperature while maintaining the concentration of the dodecanedioic acid solution below the saturation concentration and above the supersaturation concentration; And a solvent is added to the solution to dilute the solution to a concentration lower than the saturation concentration and the supersaturation concentration, and the step of repeating the step is repeated two or more times, and the fine dodecane having the maximum diameter of less than 2 탆 contained in the cooled dodecanedioic acid solution A process for the purification of dodecanedioic acid in which the cadedioic acid crystal is less than 1% by weight can be provided.
The present inventors have found that by using the above-mentioned specific dodecanedioic acid purification method, the temperature and concentration of the dodecanedioic acid solution are maintained in a certain region, specifically in the metastable region, And the purity thereof is increased. The present inventors have confirmed through experiments that the present invention has been completed.
Particularly, while the dodecanedioic acid solution is cooled and diluted repeatedly, the dodecanedioic acid solution undergoes a crystallization reaction in the metastable region, so that a large number of fine new crystals are prevented from being produced, It is possible to maximize the growth of the generated crystals and to increase the yield of crystals during the crystal separation process through filtering.
Thus, in the prior art using a single-step recrystallization method in which a dodecanedioic acid solution is rapidly cooled, a plurality of fine new crystals that occur outside the metastable region and occur in the supersaturated region are minimized, It is possible to maximize the size of the dodecanedioic acid crystals and to increase the efficiency in the filtering process.
Specifically, the dodecanedioic acid purification process may include cooling to a temperature below the supersaturation temperature saturation temperature while maintaining the concentration of the dodecanedioic acid solution that is below the saturation concentration and above the supersaturation concentration.
In the present specification, an unsaturated state means a state in which the substance is not dissolved to such an extent that the substance can be dissolved in a solvent and is additionally soluble, and a saturated state means a state in which a substance is dissolved so as to be dissolved in a solvent and is no longer dissolved it means.
In the present specification, the metastable state refers to a state in which a solute is contained in an amount larger than an amount that can be dissolved in a solvent, and does not spontaneously form new crystal nuclei, .
The supersaturated state is another kind of a state in which a solute is contained in an amount larger than an amount capable of dissolving in a solvent. Unlike the metastable state, it may mean an unstable state in which a new crystal nucleus is spontaneously formed.
That is, both the metastable state and the supersaturated state correspond to a state in which a solute is contained in an amount larger than an amount that can be dissolved in a solvent, but they can be distinguished from each other depending on whether or not they voluntarily produce new crystal nuclei.
4, the solubility curve of FIG. 4 is prepared by adding 5 g of dodecanedioic acid and 50 ml of acetone to a crystallizer (500 cc), stirring the mixture at 55 ° C. and 250 rpm for 30 minutes, The saturation temperature (the solubility temperature) at which crystals are formed while the temperature is lowered at a rate of 1 캜 / min while the stirring speed is lowered to 10 rpm in the unsaturated solution in which all of the liquor is dissolved in acetone is measured while varying the concentration of the unsaturated solution Can be obtained.
In the supersaturation curve of FIG. 4, when crystals are formed when the dodecanedioic acid solution reaches the saturation temperature, the cooling rate is reduced to 0.5 ° C / min to measure the growth of crystals, and the temperature at which the microcrystals are rapidly formed is determined The supersaturation temperature can be obtained by measuring while varying the concentration.
In FIG. 4, the region between the supersaturation curve and the solubility curve can be referred to as a metastable region B. A region on the supersaturation curve and a region having a higher or lower temperature than the supersaturation curve can be referred to as a supersaturation region (A) The point on the solubility curve may be a saturated state, and the region having a lower concentration or higher temperature than the solubility curve may be referred to as an unsaturated region (C).
The temperature and the concentration in the respective regions, for example, the unsaturated region, the saturated region, the metastable region, and the supersaturated region are respectively referred to as unsaturated temperature, unsaturated concentration, saturated temperature, saturated concentration, metastable temperature, metastable concentration, Temperature, supersaturated concentration.
Cooling the dodecanedioic acid solution to a temperature below the supersaturation temperature saturation temperature while maintaining the concentration of the dodecanedioic acid solution below the saturation concentration or above the supersaturation concentration, The crystal can be moved to the metastable region and crystal growth can proceed without adding any additional crystal nuclei, using the dodecanedioic acid crystal formed first when the dodecanedioic acid solution is saturated, as a crystal nucleus.
The dodecanedioic acid solution may have a concentration higher than the saturated concentration and less than the supersaturated concentration. The dodecanedioic acid solution is a saturated solution when it has a saturated concentration and may be a metastable solution when the dodecanedioic acid solution has a concentration lower than the saturation concentration and less than the supersaturated concentration.
More specifically, the dodecanedioic acid solution may have a saturated concentration before the initial cooling proceeds. That is, it can be present as a saturated solution of dodecanedioic acid, and crystal growth can proceed without injecting additional crystal nuclei into the crystal using the dodecanedioic acid crystals formed in a saturated state as a crystal nucleus.
Further, while repeating the step of cooling and diluting the first saturated solution of dodecanedioic acid, the dodecanedioic acid solution may be a saturated solution or a metastable solution.
At a concentration above the supersaturation concentration or below the supersaturation temperature, a plurality of micrododecanedioic acid crystals having a maximum diameter of less than 2 占 퐉 may occur in the dodecanedioic acid solution.
As described above, the saturated solution of dodecanedioic acid is cooled to a temperature below the supersaturation temperature saturation temperature, and since the supersaturated solution is not cooled below the supersaturation temperature, the supersaturated state can not be reached, and thus a fine new crystal is spontaneously generated I can not.
The cooling may proceed at a rate of 0.1 [deg.] C / min to 1 [deg.] C / min. If the cooling rate is excessively increased to more than 1 占 폚 / min, the crystal growth is not sufficiently progressed in the dodecanedioic acid solution. If the cooling rate is excessively decreased to less than 0.1 占 폚 / min, the dodecanedioic acid purification process Can be reduced.
Wherein the step of cooling to a temperature below the supersaturation temperature saturation temperature while maintaining the concentration of the dodecanedioic acid solution below the saturation concentration and above the supersaturation concentration, The temperature of the solution may be higher than the saturation temperature above the supersaturation temperature.
Specifically, for example, a temperature interval obtained by subtracting a temperature below the saturation temperature above the supersaturation temperature from a temperature of the saturated solution of the dodecanedioic acid solution that is lower than the saturation concentration and the supersaturation concentration is 0.1 占 폚 to 28 占 폚, or 1 占 폚 to 25 占 폚, or 3 Deg.] C to 20 [deg.] C, or 5 [deg.] C to 15 [deg.] C.
If the cooling temperature interval is excessively increased beyond 28 ° C, the dodecanedioic acid solution becomes a supersaturated state in which a plurality of new crystal nuclei are spontaneously generated after the above-described metastable state, It may not grow sufficiently and the yield may decrease due to losses in the separation process.
In the cooling step, the dodecanedioic acid solution may be stirred at a rate of 5 to 50 rpm, or 5 to 15 rpm. When the stirring speed is less than 5 rpm, the heat conduction to the inside of the dodecanedioic acid solution is insufficient and the temperature of the solution is not easily controlled. When the stirring speed is more than 50 rpm, the crystallization retrograde reaction occurs due to the stirring speed, Growth can be hindered.
In addition, the dodecanedioic acid purification method may include the step of diluting the solution with a solvent at a concentration lower than the saturation concentration and the supersaturation concentration while maintaining the temperature of the cooled dodecanedioic acid solution.
While the temperature of the cooled dodecanedioic acid solution is maintained, a solvent is added to dilute the solution to a concentration lower than the saturation concentration and the supersaturated concentration. In the step of cooling the solution to the metastable state, The concentration of the dodecanedioic acid solution is lowered and further cooling is carried out to maximize the crystallization of the remaining dodecanedioic acid in the solution to prevent the loss of the dodecanedioic acid and increase the purity while enlarging the size of the crystal .
As described above, the cooled temperature may be a temperature below the supersaturation temperature saturation temperature, i.e., a metastable temperature. In addition, the concentration of the cooled dodecanedioic acid solution may be less than the supersaturation concentration, and may have a metastable concentration exceeding the saturation concentration.
In the step of adding the solvent, examples of the solvent are not limited, and various water-based solvents, organic solvents, and inorganic solvents widely used in the recrystallization reaction can be used without limitation. For example, acetone and the like can be used.
The fine dodecanedioic acid crystals having a maximum diameter of less than 2 mu m contained in the cooled dodecanedioic acid solution may be less than 1 wt%. The fine dodecanedioic acid crystals having a maximum diameter of less than 2 占 퐉 are formed as the dodecanedioic acid solution spontaneously generates a new plurality of crystal nuclei when the solution reaches the supersaturated state out of the quasi-safety region.
That is, in the dodecanedioic acid purification method of this embodiment, the step of cooling and diluting the dodecanedioic acid solution proceeds in a sub-safe zone, and as the growth of new microcrystals is inhibited, The content of micrododecanedioic acid crystals having a maximum diameter of less than 2 占 퐉 and contained in the cadmium oxide solution may be less than 1% by weight. The 1 wt% may mean a content which is insignificant or substantially absent.
In the diluting step, a solvent may be added while maintaining the temperature of the cooled dodecanedioic acid solution to dilute the solution to a concentration lower than the saturation concentration and the supersaturation concentration. To this end, the temperature of the cooled dodecanedioic acid solution The concentration of the cooled dodecanedioic acid solution may be higher than the saturation concentration and the concentration lower than the supersaturated concentration in the step of adding a solvent to dilute the supernatant to a concentration lower than the saturation concentration and the supersaturation concentration.
Cooling the solution to a temperature below the supersaturation temperature saturation temperature while maintaining the concentration of the dodecanedioic acid solution that is lower than the saturation concentration and less than the supersaturation concentration and adding the solvent while maintaining the temperature of the cooled dodecanedioic acid solution The step of diluting to a concentration below the saturation concentration or above the supersaturation concentration may be repeated two or more times.
That is, after one cooling and dilution step, additional cooling and dilution steps may be repeated one or more times. More specifically, for example, one cooling and dilution step may be followed by cooling and dilution with a saturated dodecanedioic acid solution, and the cooling and dilution steps from the second and subsequent steps may be cooling and diluting with the dodecanedioic acid metastable solution, Dilution can proceed.
As described above, while the temperature of the cooled dodecanedioic acid solution is maintained, a solvent is added to dilute the solution to a concentration lower than the saturation concentration and the supersaturated concentration. In the step of cooling, a dodecanedioic acid solution , It is possible to repeat the cooling and dilution steps two or more times, since by adding a solvent to lower the concentration of the dodecanedioic acid solution, a condition has been formed that allows further cooling to proceed. As a result, the dodecanedioic acid remaining in the solution can be crystallized to the maximum to prevent the loss of dodecanedioic acid, and the purity can be increased while increasing the size of the crystal.
Cooling the solution to a temperature below the supersaturation temperature saturation temperature while maintaining the concentration of the dodecanedioic acid solution that is lower than the saturation concentration and not more than the supersaturation concentration and maintaining the temperature of the cooled dodecanedioic acid solution, And the step of diluting the solution to a concentration lower than the saturation concentration and the supersaturation concentration may be carried out simultaneously or sequentially, preferably sequentially.
The dodecanedioic acid solution purified by the dodecanedioic acid purification method may include a dodecanedioic acid crystal having a maximum diameter of 50 m or more. That is, in the dodecanedioic acid purification method of the embodiment, the step of cooling and diluting the dodecanedioic acid solution proceeds in a semi-safe region, and crystal growth is promoted along crystal nuclei generated in a saturated state , And a dodecanedioic acid crystal having a maximum diameter of 50 탆 or more.
Further, the dodecanedioic acid purification method may further include, before the step of cooling to a temperature below the supersaturation temperature saturation temperature while maintaining the concentration of the dodecanedioic acid solution that is lower than the saturation concentration and the supersaturation concentration, To form a dodecanedioic acid saturated solution containing lysic acid.
In the step of forming a dodecanedioic acid saturated solution containing dodecanedioic acid prepared from the strain, the strain may include Candida tropicalis. The Candida tropicalis is a yeast, and is a representative species of the Candida genus.
Dodecanedioic acid prepared from the above strain means dodecanedioic acid obtained through cell transformation using the strain, and has an advantage of being an environmentally-friendly dodecanedioic acid produced through a biological process.
Examples of the method for preparing dodecanedioic acid from the strain are not limited. For example, the dodecanedioic acid can be prepared by converting whole cells using methyl laurate as a substrate and Candida tropicalis strain .
The methyllaurate substrate is a substance used for growth and proliferation of the strain, and may be absorbed by a strain and used as a bio-constituent carbon. In this process, the methyllaurate substrate may undergo decomposition or conversion to form dodecanedioic acid.
In the method for producing dodecanedioic acid from the strain, the temperature may be 20 to 28 占 폚, or 22 to 27 占 폚, 23 to 26 占 폚 or 25 占 폚, and the pH may be 4 to 6.
In the above dodecanedioic acid purification method, the step of forming a saturated solution of dodecanedioic acid containing dodecanedioic acid prepared from the strain comprises the steps of: separating dodecanedioic acid in a culture medium containing the strain; And dissolving the separated dodecanedioic acid in a solvent and keeping it in a saturated state for 1 to 100 minutes.
The step of separating dodecanedioic acid in the culture medium containing the strain comprises the steps of: adding an acidic solution having a concentration of 5 to 20 N to the culture medium to precipitate dodecanedioic acid crystals; And separating the dodecanedioic acid crystal.
In the step of precipitating dodecanedioic acid crystals by adding an acidic solution at a concentration of 5 to 20 N to the culture solution containing the strain, an acidic solution is added to the culture solution in which dodecanedioic acid is present in a salt form to lower the pH value, It is possible to precipitate dodecanedioic acid.
Examples of the acidic solution include, but are not limited to, a strong acidic solution such as sulfuric acid, nitric acid, hydrochloric acid, and the like, preferably a sulfuric acid solution.
The concentration of the acid solution is 5 to 20 N or 10 to 15 N. When the concentration of the acid solution is less than 5 N, an excessive acid solution is required to meet the conversion molar amount of the salt form dodecanedioic acid, If the concentration of the acid solution exceeds 20 N, impurities due to the strong acid may increase and the yield of dodecanedioic acid may decrease.
In the step of precipitating dodecanedioic acid crystals by adding an acidic solution at a concentration of 5 to 20 N to the culture solution containing the strain, the volume ratio of the acidic solution to the culture medium containing the strain is 0.01 to 0.25 or 0.1 To 0.2.
In the step of separating the dodecanedioic acid crystals, examples of the separation method are not particularly limited, but, for example, filtration or centrifugation may be used.
In addition, the dodecanedioic acid purification method may further include washing and drying steps after separating the dodecanedioic acid crystal. Although the washing method is not limited in any particular way, it is possible to proceed with washing with purified water, and the drying method is not particularly limited. For example, the drying method may be performed at a temperature of 50 to 150 DEG C for 1 to 3 hours Lt; / RTI >
In the step of dissolving the separated dodecanedioic acid in a solvent and maintaining the saturated dodecanedioic acid for 1 to 100 minutes, dissolution of the separated dodecanedioic acid may be carried out at 40 ° C to 60 ° C, or 50 ° C to 55 ° C . If the dissolution temperature is lower than 40 ° C, the dissolution time of dodecanedioic acid may be prolonged and the economical efficiency of the process may decrease. If the dissolution temperature is higher than 60 ° C, the solvent may be volatilized so that the dodecanedioic acid is not completely dissolved, . The dissolution can be carried out in a short time while stirring is being carried out at a speed of 200 to 300 rpm.
Examples of the solvent include, but are not limited to, various water-based solvents, organic solvents, and inorganic solvents widely used in the recrystallization reaction, and acetone, for example, may be used.
The step of maintaining the saturated state may be carried out for 1 to 100 minutes, or 5 to 30 minutes, whereby crystals of dodecanedioic acid can be sufficiently formed in a saturated state. For example, a solution containing dodecanedioic acid prepared from the strain can be prepared as a solution in a saturated state at the time of its initial manufacture, After that, it can be kept saturated by cooling.
Thus, by keeping the solution containing the dodecanedioic acid prepared from the strain in a saturated state, dodecanedioic acid crystals can be produced in the solution containing the dodecanedioic acid prepared from the strain, Crystals can grow without the introduction of crystal nuclei from the outside, while the dodecanedioic acid crystals act as nuclei for crystal growth in the cooling and diluting processes described later.
The dodecanedioic acid purification method may further include separating dodecanedioic acid from the dodecanedioic acid solution.
As described above, in the step of cooling the dodecanedioic acid solution and diluting it by adding a solvent, a dodecanedioic acid crystal having a maximum diameter of 50 m or more can be formed in the dodecanedioic acid solution, In the step of separating dodecanedioic acid from the dodecanedioic acid solution, the dodecanedioic acid crystal can be separated from the dodecanedioic acid solution.
Examples of the separation method are not limited, but filtration or centrifugal separation methods can be used, for example. In the case of the above filtration method, the dodecanedioic acid crystals in the form of plate-like particles can be separated from the dodecanedioic acid solution using, for example, a filter paper. In the case of the centrifugal separation method, the dodecanedioic acid crystals in the form of plate-like particles can be separated from the dodecanedioic acid solution by using, for example, a centrifuge.
As described above, in the dodecanedioic acid purification method of this embodiment, since the dodecanedioic acid crystal has a diameter of 50 μm or more, efficient separation without loss can be achieved even if the separation method is used, and a high yield can be ensured can do.
The step of separating dodecanedioic acid from the dodecanedioic acid solution may further include a drying step. For example, the drying method may be performed at a temperature of 50 to 100 ° C for 1 to 3 hours Drying can proceed for a period of time.
The purified dodecanedioic acid may have a purity of 90% or more, or 95% or more, or 98% or more. In addition, the purified dodecanedioic acid may have a yield of 65% or more, or 70% or more.
According to the present invention, there is provided a dodecanedioic acid purification method capable of obtaining a high purity dodecanedioic acid at a high yield by increasing crystal size by inducing crystal growth while inhibiting the generation of a plurality of microcrystals .
1 shows an SEM image of DDDA prepared in Example 1. Fig.
2 is a SEM image of the DDDA prepared in Comparative Example 1;
3 shows an SEM image of DDDA prepared in Comparative Example 2. Fig.
4 shows the solubility curve and supersaturation curve of DDDA prepared in Example 1. Fig.
The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
Preparation Example 1: Preparation of dodecanedioic acid (DDDA)
Candida tropicalis strain was used in a 2L volume in a 5L fermenter. The culture medium was composed of Methyl laurate (50 g / L), NH 4 Cl (2.5 g / L) and KH 2 PO 4 (7 g / L) And the crude DDDA culture was prepared.
400 mL of the Crude DDDA culture was placed in a 1 L beaker and 48 mL of 12 N sulfuric acid was added while stirring with a magnetic bar to precipitate crude DDDA.
Crude DDDA was precipitated and a small amount of the remaining culture liquid was filtered out and washed first with 400 ml of regenerated water. At this time, the filtrate obtained after the second washing was used as the regenerated water. After the first washing, the solid was washed with 400 ml of purified water and dried at 95 ° C for 2 hours to obtain 40 g of crude DDDA.
Analysis of the components of the crude DDDA using Py-GC / MS (Agilent G1942N, Ultra Alloy-5) revealed that a majority of monocarboxylic acids or dicarboxylic acids having 8 to 18 carbon atoms occupied the impurities other than DDDA .
≪ Example 1: Purification method of dodecanedioic acid (DDDA) >
5 g of the crude DDDA of Preparation Example 1 and 50 ml of acetone were added to the crystallizer (500 cc), and the crude DDDA solution in an unsaturated state was prepared by stirring the mixture at 55 ° C for 30 minutes at 250 rpm. The temperature was adjusted to 40 And then kept at 40 DEG C for 10 minutes to produce DDDA crystals.
Thereafter, while stirring at 10 rpm, the crystal growth reaction was carried out by adjusting the temperature and the concentration step by step as follows.
I) After the temperature was cooled to 29 DEG C at a rate of 0.5 DEG C / min, 20 mL of acetone was added to dilute the DDDA solution.
Ii) After the temperature was cooled to 18 캜 at a rate of 0.5 캜 / min, 20 ml of acetone was added to dilute the DDDA solution.
Iii) After the temperature was cooled to 7 ° C at a rate of 0.5 ° C / min, 20 ml of acetone was added to dilute the DDDA solution.
Iv) The temperature was cooled to 0 占 폚 at a rate of 0.5 占 폚 / min.
After the crystal growth reaction was completed, DDDA crystals were recovered by filtration and dried at 95 DEG C for 2 hours.
Comparative Examples 1 and 2: Method for purifying dodecanedioic acid (DDDA)
Comparative Example 1
5 g of the crude DDDA of Preparation Example 1 and 50 ml of acetone were added to the crystallizer (500 cc), and the crude DDDA solution in an unsaturated state was prepared by stirring the mixture at 55 ° C for 30 minutes at 250 rpm. The temperature was adjusted to 40 And then kept at 40 DEG C for 10 minutes to produce DDDA crystals.
Thereafter, while stirring at 10 rpm, the temperature was cooled to 0 deg. C at a rate of 0.5 deg. C / min, only DDDA crystals were collected through filtration, and dried at 95 deg. C for 2 hours.
Comparative Example 2
5 g of the crude DDDA of Preparation Example 1 and 50 ml of acetone were added to the crystallizer (500 cc), and the crude DDDA solution in an unsaturated state was prepared by stirring the mixture at 55 ° C for 30 minutes at 250 rpm. The temperature was adjusted to 40 And then kept at 40 DEG C for 10 minutes to produce DDDA crystals.
Thereafter, while stirring at 10 rpm, the crystal growth reaction was carried out by adjusting the temperature and the concentration step by step as follows.
I) After the temperature was cooled to 29 DEG C at a rate of 0.5 DEG C / min, 20 mL of acetone was added to dilute the DDDA solution.
Ii) The temperature was cooled to 0 ° C at a rate of 0.5 ° C / min.
After the crystal growth reaction was completed, only the DDDA crystals were collected through filtration and dried at 95 ° C for 2 hours.
≪ Experimental Example: Physical properties of DDDA obtained in Examples and Comparative Examples >
The physical properties of the DDDA obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2, respectively.
Experimental Example 1: DDDA purity analysis
GC (Agilent 7890, HP-5 30 m X 0.32 mm X 0.25 m) was used for the DDDA prepared in Example 1 and Comparative Examples 1 and 2 (also, crude DDDA prepared in Reference Example 1) The purity was analyzed and the results are shown in Table 1 below.
Experimental Example 2: Analysis of DDDA Size
The diameters of DDDA prepared in Example 1 and Comparative Examples 1 and 2 were analyzed by SEM (TOPCON SM-701), and the results are shown in Table 1 and FIGS.
As shown in Table 1 and FIG. 1, the DDDA purified by the DDDA purification method of Example 1 had higher purity and yield than Comparative Examples 1 and 2, and the maximum diameter of crystals increased to 50 占 퐉 or more .
On the other hand, in the case of Comparative Example 1, the maximum diameter of the DDDA crystal was less than 2 탆, and in Comparative Example 2, it was 2 탆 to 35 탆, which was lower than that of Example 1,
Particularly, in the case of Example 1, it can be confirmed that the number of crystals in the plate phase itself is smaller than that in Comparative Examples 1 and 2. [ That is, in the case of Comparative Examples 1 and 2, a large number of microcrystals of less than 2 탆 were produced, whereas in Example 1, only 50 탆 of macrocrystals were selectively grown while suppressing the generation of microcrystals.
Thus, in the case of using the purification method of Example 1 in which crystallization proceeds in the metastable region between the supersaturation curve and the saturation curve while repeating the cooling and concentration control steps two or more times after the crystal formation, 1, and 2, respectively.
Claims (16)
Wherein the cooled dodecanedioic acid solution contains less than 1% by weight of fine dodecanedioic acid crystals having a maximum diameter of less than 2 占 퐉.
At a concentration above the supersaturation concentration or below the supersaturation temperature,
Wherein a plurality of fine dodecanedioic acid crystals having a maximum diameter of less than 2 占 퐉 are produced in the dodecanedioic acid solution.
In the step of cooling to a temperature below the saturation temperature above supersaturation while maintaining the concentration of the dodecanedioic acid solution below the saturation concentration or above the supersaturation concentration,
Wherein the temperature of the dodecanedioic acid solution below the saturation concentration or above the supersaturation concentration is higher than the saturation temperature above the supersaturation temperature.
In the step of adding a solvent to dilute the solution to a concentration lower than the saturation concentration and the supersaturation concentration while maintaining the temperature of the cooled dodecanedioic acid solution,
Wherein the concentration of the cooled dodecanedioic acid solution is higher than the concentration above the saturation concentration and below the supersaturation concentration.
Wherein the cooling proceeds at a rate of 0.1 占 폚 / min to 1 占 폚 / min.
Wherein the dodecanedioic acid solution is stirred at a rate of 5 rpm to 50 rpm.
Wherein the purified dodecanedioic acid comprises a dodecanedioic acid crystal having a maximum diameter of at least 50 mu m.
Wherein the dodecanedioic acid solution has a saturation concentration before the first cooling step.
Prior to the step of cooling to a temperature below the saturation temperature above the supersaturation temperature while maintaining the concentration of the dodecanedioic acid solution below the saturation concentration or above the supersaturation concentration,
A method for purifying dodecanedioic acid, comprising the step of forming a dodecanedioic acid saturated solution containing dodecanedioic acid prepared from a strain.
The step of forming a saturated solution of dodecanedioic acid containing dodecanedioic acid, which is prepared from the strain,
Isolating dodecanedioic acid in a culture medium containing the strain; And
Dissolving the separated dodecanedioic acid in a solvent and maintaining the saturated dodecanedioic acid for 1 to 100 minutes.
The step of separating the dodecanedioic acid in the culture medium containing the strain comprises:
Precipitating dodecanedioic acid crystals by adding an acidic solution having a concentration of 5 to 20N to the culture solution containing the strain; And
And separating the dodecanedioic acid crystal.
In the step of precipitating dodecanedioic acid crystals by adding an acidic solution having a concentration of 5 to 20 N to the culture solution containing the strain,
Wherein the volume ratio of the acidic solution to the culture medium containing the strain is 0.01 to 0.25.
Wherein the dissolution of the separated dodecanedioic acid proceeds at 40 ° C to 60 ° C.
The above-mentioned dodecanedioic acid purification method comprises:
Further comprising the step of separating dodecanedioic acid from the dodecanedioic acid solution.
Wherein the purified dodecanedioic acid has a purity of at least 90%.
Wherein the purified dodecanedioic acid has a yield of at least 65%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848388A (en) * | 2019-04-29 | 2020-10-30 | 中国科学院微生物研究所 | Crystals of dodecanedioic acid and preparation method thereof |
| CN114436820A (en) * | 2022-01-20 | 2022-05-06 | 浙江工业大学 | Preparation method and application of dodecanedioic acid seed crystal |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848388A (en) * | 2019-04-29 | 2020-10-30 | 中国科学院微生物研究所 | Crystals of dodecanedioic acid and preparation method thereof |
| CN114436820A (en) * | 2022-01-20 | 2022-05-06 | 浙江工业大学 | Preparation method and application of dodecanedioic acid seed crystal |
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