Process for recovering 3-hydroxypropionic acid and slurry composition comprising 3-hydroxypropionic acid

Abstract

The present invention relates to a process for recovering 3-hydroxypropionic acid and a slurry composition comprising a precipitate produced in the process for recovering 3-hydroxypropionic acid and 3-hydroxypropionic acid, the process for recovering 3-hydroxypropionic acid comprising: forming 3-hydroxypropionate salt crystals in a concentrated solution comprising 3-hydroxypropionic acid in the presence of an alkali metal salt; producing a solution comprising 3-hydroxypropionate salt crystals separated from the concentrated solution; agitating an acid and the solution comprising 3-hydroxypropionate salt crystals to form a precipitate; and subjecting the precipitate to a first washing.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application claims Korean Patent Application No. 10-2021-0166976, Korean Patent Application No. 10-2021-0167303, Korean Patent Application No. 10-2021-0166978, and Korean Patent Application No. 10-2021, filed on November 29, 2021. The interests of Korean Patent Application No. 1-0167409, No. 10-2022-0159392, No. 10-2022-0159394, and No. 10-2022-0159395, filed on November 24, 2022, the disclosures of which are incorporated herein by reference in their entirety.

[0003] This invention relates to a process for recovering 3-hydroxypropionic acid and a slurry composition containing 3-hydroxypropionic acid. Background Technology

[0004] 3-Hydroxypropionic acid (3HP) is a platform compound that can be converted into various chemicals such as acrylic acid, methyl acrylate, and acrylamide. Since being identified by the U.S. Department of Energy (DOE) as one of the 12 high-value-added biochemicals in 2004, it has been actively studied in academia and industry.

[0005] The production of 3-hydroxypropionic acid is mainly carried out through two methods: chemical and biological. However, in the case of chemical methods, it has been pointed out that the initial materials are expensive and that the process is not environmentally friendly because toxic substances are generated during the production process. Therefore, environmentally friendly biological methods have attracted attention.

[0006] When organic acids are produced through microbial fermentation, other byproducts are generated in addition to organic acids such as 3-hydroxypropionic acid during the fermentation process. Therefore, a process for extracting and separating organic acids from the fermentation broth is needed. Methods for extracting and separating organic acids from microbial fermentation broth include electrodialysis, reverse osmosis membrane extraction, and solution-organic solvent reaction extraction containing organic acids. In particular, the reverse extraction method using sodium hydroxide (NaOH) is widely used due to its high yield. However, in these methods, since the product is in the form of an organic acid salt, a drawback is that a process is still needed to convert it into an organic acid, and the purity is low.

[0007] Unlike other organic acids produced through fermentation, 3-hydroxypropionic acid exhibits high hydrophilicity and high solubility and reactivity with water. This makes it difficult to apply conventional organic acid separation and purification processes such as precipitation and extraction.

[0008] Reactive extraction methods utilize highly reactive diluents, such as amines or alcohols, that extract organic acids. This allows for selective extraction of organic acids and offers relatively high extraction efficiency. Therefore, reactive extraction methods are often attempted, even when isolating and purifying 3HP. As an example, a method using trioctylamine (TOA) as the amine has been proposed, but it suffers from low extraction efficiency for 3HP and requires large amounts of organic solvent. Furthermore, when using tridecaneamine as the amine, the extraction efficiency of 3HP is higher than that of TOA, but the problem is that emulsification occurs during the extraction process, preventing the separation of the organic and aqueous phases.

[0009] Therefore, there is a need to develop a process for recovering 3-hydroxypropionic acid from feedstock solutions containing 3-hydroxypropionic acid, such as microbial fermentation broth, with high purity and high yield. Summary of the Invention

[0010] Technical issues

[0011] The object of the present invention is to provide a process for recovering 3-hydroxypropionic acid, wherein the washing liquid used to wash the precipitate formed by the reaction of 3-hydroxypropionate crystals with acid is reused in the process, thereby recovering 3-hydroxypropionic acid with high purity and high yield, and to provide a slurry composition comprising the precipitate formed in the above process and 3-hydroxypropionic acid.

[0012] Technical solution

[0013] This article provides a process for recovering 3-hydroxypropionic acid, comprising: forming 3-hydroxypropionate crystals in a concentrate containing 3-hydroxypropionic acid in the presence of an alkali metal salt; preparing a solution containing the 3-hydroxypropionate crystals separated from the concentrate; stirring the acid and the solution containing the 3-hydroxypropionate crystals to form a precipitate; and performing a first washing on the precipitate.

[0014] This article also provides a slurry composition comprising a precipitate represented by the following structural formula 4 and 3-hydroxypropionic acid.

[0015] [Structure 4]

[0016] Cations (Anions)·pH2O

[0017] in,

[0018] The cation is Na. + Mg 2+ or Ca2+ ,

[0019] The anion is SO42-. 2- PO4 3- or CO3 2- ,

[0020] p is the number of water molecules in the hydrate, which is an integer greater than or equal to 1.

[0021] The process for recovering 3-hydroxypropionic acid and the slurry composition containing 3-hydroxypropionic acid according to embodiments of the present invention will now be described in more detail.

[0022] It should be understood that unless the steps included in the preparation method described herein are specified as sequential or consecutive or otherwise stated, one step and another included in the preparation method should not be construed as being limited to the order described herein. Therefore, it should be understood that the order of steps included in the preparation method can be changed to the extent understood by those skilled in the art, and in such cases, incidental changes that are obvious to those skilled in the art fall within the scope of the invention.

[0023] In this invention, alkali metals include both alkali metals and alkaline earth metals.

[0024] According to one embodiment of the present invention, a process for recovering 3-hydroxypropionic acid is provided, comprising: forming 3-hydroxypropionate crystals in a concentrate containing 3-hydroxypropionic acid in the presence of an alkali metal salt; preparing a solution containing the 3-hydroxypropionate crystals separated from the concentrate; stirring the acid and the solution containing the 3-hydroxypropionate crystals to form a precipitate; and performing a first washing on the precipitate.

[0025] Furthermore, the process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention may further include: reusing the first washing solution used for the first washing of the precipitate.

[0026] The inventors have discovered through experiments that when 3-hydroxypropionic acid is concentrated in the presence of an alkali metal salt to form 3-hydroxypropionate crystals, stirring the solution containing the 3-hydroxypropionate crystals and acid, separating and washing the resulting precipitate, and reusing the washing solution during the process can prevent the loss of 3-hydroxypropionic acid during the process and enable the recovery of 3-hydroxypropionic acid with high concentration and high recovery rate, thereby completing the present invention.

[0027] When a solution containing 3-hydroxypropionate crystals reacts with an acid, a precipitate can form. For example, when the 3-hydroxypropionate is Ca(3HP)2 and sulfuric acid is used as the acid, a reaction as described in reaction scheme 1 below can be carried out to produce a slurry composition containing a precipitate (CaSO4·2H2O) and 3-hydroxypropionic acid. Furthermore, the precipitate can be filtered from this slurry composition to recover the 3-hydroxypropionic acid (3HP) contained in the filtrate.

[0028] [Reaction Scheme 1]

[0029] Ca(3HP)2+H2SO4+2H2O->CaSO4·2H2O+2(3HP)

[0030] Meanwhile, precipitates such as CaSO4·2H2O have good water-absorbing properties, resulting in a large amount of 3-hydroxypropionic acid being retained in the precipitate along with water, and also causing the loss of 3-hydroxypropionic acid. To reduce the loss of 3-hydroxypropionic acid, the precipitate can be washed with a large amount of water; however, in this case, the problem is that the concentration of 3-hydroxypropionic acid in the final product solution is very low.

[0031] However, in a process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention, the washing liquid used to wash the precipitate is reused during the process of recovering 3-hydroxypropionic acid. This can prevent the loss of 3-hydroxypropionic acid and also prevent the concentration of 3-hydroxypropionic acid in the final product solution from decreasing, so that 3-hydroxypropionic acid can be recovered at high concentration and high recovery rate.

[0032] The reuse of washing solution refers to the reuse of the washing solution used to wash precipitates during the recovery process of 3-hydroxypropionic acid. For example, in the process of recovering 3-hydroxypropionic acid, the washing solution can be reused as a liquid material in steps that require liquid materials, and reuse can include not only the reuse of the washing solution before the precipitate formation step, but also the reuse of the washing solution after the precipitate formation step.

[0033] For example, when the washing solution is reused before the precipitate formation step, it can be reused as a solvent in the step of preparing a solution containing 3-hydroxypropionate crystals, and it can be reused in the fermentation broth in the step of fermenting a bacterial strain capable of producing 3-hydroxypropionic acid to produce a 3-hydroxypropionic acid fermentation broth. Furthermore, when the washing solution is reused after the precipitate formation step, it is mixed with a filtrate in which the precipitate has been filtered to prepare a mixture, and 3-hydroxypropionic acid (3HP) can be recovered from the mixture.

[0034] In a process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention, after the formation of 3-hydroxypropionate crystals, the 3-hydroxypropionate crystals are separated from the concentrate, and a solution containing the 3-hydroxypropionate crystals separated from the concentrate can be prepared.

[0035] As described above, since 3-hydroxypropionate crystals are produced during the fermentation process, the concentrate from which the fermentation broth has been concentrated may contain a large number of impurities such as bacterial strains, carbon sources, and alkali metal salts, in addition to the 3-hydroxypropionate crystals. However, in a process for recovering 3-hydroxypropionic acid according to an embodiment of the present invention, impurities can be removed by solid-liquid separation and recovery of 3-hydroxypropionate crystals from the concentrate, and no impurities are present even in a solution prepared by dissolving the separated 3-hydroxypropionate crystals in a solvent such as distilled water.

[0036] For example, 3-hydroxypropionate crystals can be separated from a concentrate using a filter flask, a vacuum pump, etc., and the separated 3-hydroxypropionate crystals can be dissolved in a solvent such as distilled water to produce a solution containing 3-hydroxypropionate crystals.

[0037] The solution containing 3-hydroxypropionate crystals can contain 3-hydroxypropionate crystals at concentrations of 100 g / L or higher, 150 g / L or higher, or 200 g / L or higher, and can also contain 3-hydroxypropionate crystals at concentrations of 800 g / L or lower, 750 g / L or lower, or 700 g / L or lower. If the concentration of 3-hydroxypropionate crystals in the solution is too low, the final recovered concentration of 3-hydroxypropionic acid will be lower; if the concentration of 3-hydroxypropionate crystals is too high, the recovery rate of 3-hydroxypropionic acid will be lower.

[0038] In the process of recovering 3-hydroxypropionic acid, after preparing a solution containing 3-hydroxypropionate crystals, the acid and the solution containing 3-hydroxypropionate crystals can be stirred to prepare a slurry containing precipitate and 3-hydroxypropionic acid.

[0039] The steps of stirring the acid and the solution containing 3-hydroxypropionate crystals are not limited to this, but may further include: adding the acid to the solution containing 3-hydroxypropionate crystals at a temperature above 30°C and below 90°C before stirring the acid and the solution containing 3-hydroxypropionate crystals to form a precipitate.

[0040] Because the acid is added to the 3-hydroxypropionate crystals at a temperature above 30°C and below 90°C, the resulting precipitate has a large particle size and a significantly low moisture content, thereby increasing the flowability of the slurry composition containing the precipitate. This facilitates the filtration of the precipitate from the slurry composition and allows for the recovery of 3-hydroxypropionic acid with a high recovery rate.

[0041] Meanwhile, the temperature at which the acid is added to the 3-hydroxypropionate crystal can be above 30°C, above 35°C, above 40°C, above 45°C, above 50°C, or above 55°C, and can also be below 90°C, below 80°C, below 75°C, below 70°C, or below 65°C.

[0042] The size and moisture content of the precipitate appear to be affected by the temperature conditions of the acid addition step. When acid is added to 3-hydroxypropionate crystals under the aforementioned temperature conditions, the precipitate can have a large particle size and low moisture content.

[0043] Furthermore, prior to the step of stirring the acid and the solution containing 3-hydroxypropionate crystals to form a precipitate, the process may further include adding the acid and the solution containing 3-hydroxypropionate crystals into the reactor continuously or in two or more separate steps.

[0044] Because the acid and the solution containing 3-hydroxypropionate crystals are added to the reactor continuously or in two or more separate steps, the resulting precipitate has a particle size of up to 10.0 μm or larger, and its moisture content can be significantly low. This promotes the filtration of the precipitate from the slurry composition, and as the fluidity of the slurry composition increases, the filtration is further accelerated, allowing for the recovery of 3-hydroxypropionic acid with a high recovery rate. Furthermore, the large particle size of the precipitate (up to 10.0 μm) not only significantly promotes filtration but also reduces dust generated when the separated precipitate is recycled to other industrial sectors such as cement production, which can be highly advantageous in processing.

[0045] As the concentration of reactants contained in the reactor remains low, larger precipitate particle sizes can be formed. To maintain a low concentration of reactants in the reactor, the acid and the solution containing 3-hydroxypropionate crystals can be added to the reactor continuously, or in two or more separate steps.

[0046] When acid and / or 3-hydroxypropionate crystals are continuously added to the reactor, they can be added at a rate of 0.01 g / min or more, 0.05 g / min or more, or 0.10 g / min or more, and at a rate of 5.00 g / min or less, 3.00 g / min or less, 1.00 g / min or less, or 0.50 g / min or less. Furthermore, when acid or 3-hydroxypropionate crystals are continuously added to the reactor, they can be added continuously for 10 minutes or more, 20 minutes or more, 30 minutes or more, or 50 minutes or more, and can be added continuously for 10 hours or less, 5 hours or less, or 2 hours or less. Because acid and / or 3-hydroxypropionate crystals are continuously added to the reactor at the above rates and times, precipitates with a particle size of 10.0 μm or more can be formed.

[0047] For example, in the process of recovering 3-hydroxypropionic acid, a solution containing 3-hydroxypropionate crystals can be continuously added to the reactor at a rate of 0.01 g / min or more and 5.00 g / min or less for a period of 10 minutes or more and 10 hours or less.

[0048] Furthermore, the acid and / or 3-hydroxypropionate crystals can be added to the reactor in two, three, four, or five separate increments, or in fewer than 20, 15, 13, or 10 increments. In this case, the amounts of reactants added at each stage can be controlled to be the same or different, and the same amount of reactants can be added to each stage to ensure a uniform reaction.

[0049] Furthermore, when the acid and / or 3-hydroxypropionate crystals are added in two or more batches, they can be added at intervals of 1 minute or more, 3 minutes or more, or 5 minutes or more, and at intervals of less than 30 minutes, 25 minutes or less, 20 minutes or less, or 15 minutes or less. By adding the acid and / or the solution containing 3-hydroxypropionate crystals to the reactor in batches at the above stages and intervals, large precipitates with a particle size of 10.0 μm or more can be formed.

[0050] For example, in the process of recovering 3-hydroxypropionic acid, the acid can be added to the reactor in three or more but less than 20 portions, and the acid can be added to the reactor in batches at intervals of more than 1 minute but less than 30 minutes.

[0051] The temperature inside the reactor can be above 20°C, above 30°C, above 35°C, above 40°C, above 45°C, above 50°C, or above 55°C, and can also be below 90°C, below 80°C, below 75°C, below 70°C, or below 65°C. The temperature inside the reactor meeting the above ranges allows for a large particle size and low moisture content in the formed precipitate.

[0052] Meanwhile, relative to the total content of 100% by weight of 3-hydroxypropionate crystals, the total content of acid added to the reactor can be more than 20% by weight or more than 30% by weight, and can be less than 80% by weight, less than 70% by weight, less than 60% by weight, or less than 50% by weight. When the content of added acid is too small, the conversion rate from 3-hydroxypropionate crystals to 3-hydroxypropionic acid is low, and therefore the content of recovered 3-hydroxypropionic acid will be small. When the content of added acid is too large, the concentration of unreacted cations and anions remaining in the final aqueous solution of 3-hydroxypropionic acid becomes too high, which will adversely affect the progress of subsequent processes such as the preparation process of polylactic acid (PLA) and the preparation process of bio-acrylic acid (Bio-AA).

[0053] The acid may be, for example, selected from sulfuric acid, hydrochloric acid, phosphoric acid, carbonic acid, and nitric acid.

[0054] In a process for recovering 3-hydroxypropionic acid according to one embodiment of the invention, after stirring an acid and a solution containing 3-hydroxypropionate crystals to form a slurry containing a precipitate and 3-hydroxypropionic acid, the precipitate is filtered from the slurry, and the 3-hydroxypropionic acid contained in the filtrate can be recovered. For example, the filtration can be performed using a filter flask and a vacuum pump.

[0055] Meanwhile, the precipitate can be represented by the following structural formula 3.

[0056] [Structure 3]

[0057] Cations (Anions)·pH2O

[0058] In structural formula 3, the cation is an alkali metal salt cation, the anion is an acid anion, and p is the number of water molecules in the hydrate, which is an integer greater than or equal to 1.

[0059] The cation may be, for example, Na. + Mg 2+ or Ca 2+ However, when it is Mg 2+ or Ca 2+ At this time, precipitates can be formed more effectively. Furthermore, the anion can be SO42-. 2- PO4 3- or CO3 2-However, it is not limited to this.

[0060] Furthermore, the particle size of the precipitate can be 1.0 μm or larger, 1.5 μm or larger, 10.0 μm or larger, 13.0 μm or larger, or 15.0 μm or larger, and can be less than 300.0 μm, less than 250.0 μm, less than 200.0 μm, less than 150.0 μm, less than 100.0 μm, less than 50.0 μm, less than 30.0 μm, less than 20.0 μm, less than 8.0 μm, less than 7.0 μm, less than 6.0 μm, less than 5.0 μm, or less than 2.0 μm. The precipitate meeting these particle size requirements allows for a reduction in its moisture content, which increases the fluidity of the slurry containing the precipitate and facilitates its filtration from the slurry. For example, the particle size of the precipitate can be 10.0 μm or larger, in which case filtration separation from the slurry becomes very easy, and dust generated during recycling to other industrial sectors such as cement production is reduced, which can be very advantageous in processing.

[0061] Precipitates can exhibit various particle shapes, such as angular, spherical, plate-like, and needle-like. Furthermore, the particle size of the precipitates is measured using scanning electron microscopy (SEM). Here, the particle size is measured based on the linear distance between the crystal planes that has the longest linear distance among the crystal planes contained within the precipitate.

[0062] Furthermore, the moisture content of the precipitate can be below 150%, 130%, 110%, 100%, 80%, or 70%, and can be above 1%, 10%, or 30%. If the moisture content of the precipitate is too high, the fluidity of the slurry containing the precipitate decreases, making the process difficult and making it difficult to separate the precipitate from the slurry, thus making it difficult to recover 3-hydroxypropionic acid in a high yield.

[0063] The moisture content of the precipitate can be calculated by substituting the weight of the precipitate before drying and the weight of the precipitate after drying into Equation 1 below.

[0064] [Equation 1]

[0065] Moisture content (wt%) = (Weight of precipitate before drying - Weight of precipitate after drying) / (Weight of precipitate after drying) * 100

[0066] In a process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention, the precipitate separated from the slurry can be first washed, and the first washing solution used can be reused.

[0067] When the 3-hydroxypropionic acid contained in the filtrate is further recovered after filtering the washing liquid without reusing the washing liquid, the filtered washing liquid is still included in the final product solution, which leads to the problem that the concentration of 3-hydroxypropionic acid in the final product solution is very low.

[0068] However, in a process for recovering 3-hydroxypropionic acid according to an embodiment of the present invention, since the washing liquid is reused during the recovery process, the concentration of 3-hydroxypropionic acid can be prevented from decreasing, and the 3-hydroxypropionic acid contained in the washing liquid is recycled during the process, thereby preventing the loss of 3-hydroxypropionic acid and allowing 3-hydroxypropionic acid to be recovered with a high recovery rate.

[0069] Furthermore, in a process for recovering 3-hydroxypropionic acid according to an embodiment of the present invention, after a first washing of the precipitate, a second washing is performed on the precipitate after the first washing, and the second washing solution used can be reused.

[0070] Meanwhile, the washing water used to wash the precipitate is not limited to this, and can be at least one selected from distilled water, a hydroxyl-containing solution, or an amino-containing solution. Distilled water is preferred to reduce the formation of byproducts. The distilled water can be distilled water, double-distilled water, or triple-distilled water. The hydroxyl-containing solution can be an alcohol, ethanol, methanol, or isopropanol. The amino-containing solution can be ammonia, dimethylamine, trimethylamine, or aniline.

[0071] The volume ratio of the first washing solution to the second washing solution used for washing the precipitate can be 1:1.5 to 1:10.0, 1:2 to 1:7, or 1:3 to 1:5.

[0072] The separated precipitate may include 3-hydroxypropionic acid, 3-hydroxypropionate, 3-hydroxypropionate crystals, and other impurities. In the first washing of the precipitate, 3-hydroxypropionic acid and 3-hydroxypropionate, which have high solubility, can be initially included in the first washing solution and recovered.

[0073] Therefore, in order to recover 3-hydroxypropionic acid and 3-hydroxypropionate at a high concentration, the first washing solution can be used in a smaller volume than the second washing solution. That is, since the first washing solution and the second washing solution are used in a volume ratio of 1:1.5 to 1:10.0, the first washing solution containing a high concentration of 3-hydroxypropionic acid and 3-hydroxypropionate can be recovered through the first washing step.

[0074] Subsequently, in the second washing step, residual 3-hydroxypropionic acid and 3-hydroxypropionate, as well as other impurities contained in the precipitate from the first washing, can be removed. Furthermore, to recover high-purity precipitate, a second washing solution can be used in a larger volume than the first washing solution.

[0075] The step of reusing the first washing solution and / or the second washing solution is not limited thereto. For example, in the step of preparing a solution containing 3-hydroxypropionate crystals, at least one washing solution selected from the first washing solution and the second washing solution can be reused as a solvent.

[0076] As described above, a solution containing 3-hydroxypropionate crystals can be prepared by dissolving the 3-hydroxypropionate crystals separated from the concentrate in a solvent such as distilled water, and the first and / or second washing solutions can be reused as solvents for dissolving the 3-hydroxypropionate crystals.

[0077] Furthermore, since the first washing solution contains a high concentration of 3-hydroxypropionic acid and 3-hydroxypropionate, it can be reused as a solvent for dissolving 3-hydroxypropionate crystals. Therefore, the loss of 3-hydroxypropionic acid generated during the recovery process can be prevented, and the recovery rate of 3-hydroxypropionic acid can be improved.

[0078] Furthermore, the process for recovering 3-hydroxypropionic acid will be described in detail below, but prior to the step of forming 3-hydroxypropionate crystals, the process may further include: fermenting a bacterial strain capable of producing 3-hydroxypropionic acid to produce a 3-hydroxypropionic acid fermentation broth, and concentrating the fermentation broth to form a concentrate containing 3-hydroxypropionic acid.

[0079] Furthermore, in the step of producing 3-hydroxypropionic acid fermentation broth, at least one washing liquid selected from the first washing liquid and the second washing liquid can be reused.

[0080] Since the second washing solution also contains 3-hydroxypropionic acid and 3-hydroxypropionate, it can be reused in the step of producing 3-hydroxypropionic acid fermentation broth.

[0081] Since a filtration step is performed after the fermentation broth production step, the second washing liquid containing impurities can be reused in the fermentation broth production step, and the first washing liquid containing a high concentration of 3-hydroxypropionic acid and 3-hydroxypropionate can be reused in the step of preparing a solution containing 3-hydroxypropionate crystals.

[0082] Meanwhile, since the first and second washing solutions may contain impurities other than 3-hydroxypropionic acid, the washing solutions can be further filtered and then reused in the recycling process.

[0083] In addition, at least one washing liquid selected from the first washing liquid and the second washing liquid is mixed with the filtrate in which the precipitate has been filtered to prepare a mixture, from which 3-hydroxypropionic acid can be recovered.

[0084] When filtering (solid-liquid separation) a slurry composition, it is separated into a precipitate and a filtrate. The filtrate contains 3-hydroxypropionic acid, which can then be recovered. Simultaneously, as described above, the first and / or second washing solutions also contain 3-hydroxypropionic acid remaining on the surface of the precipitate, such that the first and / or second washing solutions are mixed with the filtrate. When recovering 3-hydroxypropionic acid from the mixture, the recovery rate of 3-hydroxypropionic acid can be improved.

[0085] In a process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention, the recovery rate of 3-hydroxypropionic acid can be 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 40% to 99.9%, 50% to 99.9%, 60% to 99.9%, 70% to 99.9%, 80% to 99.9%, 90% to 99.9%, 40% to 99.9%, 9 ... 9%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, 90% to 99%, 40% to 97%, 50% to 97%, 60% to 97%, 70% to 97%, 80% to 97%, 90% to 97%, 40% to 95%, 50% to 95%, 60% to 95%, 70% to 95%, 80% to 95%, or 90% to 95%, but not limited to these. Recovery rates can be calculated based on weight.

[0086] In a process for recovering 3-hydroxypropionic acid according to one embodiment of the invention, the water removed by processes such as concentration and evaporation can be reused during the washing process. Water removed by processes such as concentration and evaporation is typically discarded as wastewater. However, in the process for recovering 3-hydroxypropionic acid, the water removed by processes such as concentration and evaporation can be reused during the washing process, thereby reducing the amount of wastewater generated.

[0087] For example, the step of concentrating the fermentation broth to form a concentrate containing 3-hydroxypropionic acid is carried out by evaporating the fermentation broth, and the water removed by evaporation can be liquefied and reused in at least one wash selected from the first wash and the second wash.

[0088] Furthermore, the process for recovering 3-hydroxypropionic acid may further include: drying the precipitate from the first wash and the precipitate from the second wash. Thus, the water removed by drying can be liquefied and reused in at least one wash selected from the first and second washes.

[0089] Furthermore, after stirring the acid and a solution containing 3-hydroxypropionate crystals to form a slurry containing precipitate and 3-hydroxypropionic acid, the filtrate after filtering the slurry can be purified by methods such as ion exchange. The purified solution containing 3-hydroxypropionic acid can be concentrated to prepare a concentrated 3-hydroxypropionic acid solution.

[0090] At this point, concentration is achieved through evaporation, and the water removed by evaporation can be liquefied and reused in at least one wash selected from the first wash and the second wash.

[0091] Meanwhile, in a process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention, 3-hydroxypropionic acid crystals can be formed from the concentrate containing 3-hydroxypropionic acid in the presence of an alkali metal salt before preparing a solution containing 3-hydroxypropionate crystals separated from the concentrate.

[0092] Concentrates containing 3-hydroxypropionic acid can contain 3-hydroxypropionic acid at concentrations of 300 g / L or higher, 350 g / L or higher, 400 g / L or higher, 450 g / L or higher, or 500 g / L or higher, and can also contain 3-hydroxypropionic acid at concentrations of 900 g / L or lower, 850 g / L or lower, or 800 g / L or lower. Whether 3-hydroxypropionate crystals form appears to be affected by the presence of the alkali metal salt, the concentration of 3-hydroxypropionic acid in the concentrate, etc.

[0093] Furthermore, when the concentration of 3-hydroxypropionic acid crystals in the concentrate is higher than the water solubility of 3-hydroxypropionic acid crystals, 3-hydroxypropionic acid crystals can be formed more easily. For example, the water solubility of Ca(3HP)₂ as 3-hydroxypropionic acid crystals at room temperature is 450 g / L; therefore, when the concentration of 3-hydroxypropionic acid in the concentrate exceeds 450 g / L, the formation of Ca(3HP)₂ crystals can be promoted. Similarly, the water solubility of Mg(3HP)₂ as 3-hydroxypropionic acid crystals at room temperature is 250 g / L; therefore, when the concentration of 3-hydroxypropionic acid in the concentrate exceeds 250 g / L, the formation of Mg(3HP)₂ crystals can be promoted.

[0094] Even when alkali metal salts are present, 3-hydroxypropionate crystals can be formed from a concentrated solution meeting the above concentrations. There are no limitations on the selection of alkali metal salts within the range intended for forming 3-hydroxypropionate crystals. For example, the alkali metal salt may include those selected from Na. + Mg 2+ and Ca 2+ One or more cations in Mg, but when using Mg 2+ or Ca 2+ When the cation of its salt or a cation is present, 3-hydroxypropionate crystals can be formed more efficiently. For example, the alkali metal salt can be Ca(OH)₂, Mg(OH)₂, or a mixture thereof.

[0095] Alkali metal salts are added and remain in the process of producing 3-hydroxypropionic acid fermentation broth, or they can be added in a process where 3-hydroxypropionic acid concentrate containing 300 g / L or more of 3-hydroxypropionic acid forms 3-hydroxypropionate crystals. Furthermore, the concentration of the alkali metal salt can be 10% to 100% or 30% to 90% of the 3-hydroxypropionic acid concentration, and for example, it can be present in the concentrate at concentrations of 10 g / L to 900 g / L, 50 g / L to 800 g / L, 100 g / L to 700 g / L, or 200 g / L to 600 g / L.

[0096] Furthermore, the step of forming 3-hydroxypropionate crystals in a concentrate containing 3-hydroxypropionic acid can further include contacting the concentrate with a non-solvent. When the concentrate is contacted with a non-solvent, 3-hydroxypropionate crystals are formed more readily. Compared to crystals formed at a high rate due to excessive concentration, when the concentrate of 3-hydroxypropionic acid is contacted with a non-solvent in the presence of an alkali metal salt, pure 3-hydroxypropionate crystals can be formed by controlling the crystal formation rate, thereby increasing the crystal size. These 3-hydroxypropionate crystals contain very little impurity within the crystal and exhibit excellent filterability due to uniform crystal formation. Therefore, they are not only easy to purify, but also possess excellent shape stability and thermal stability in the crystalline state, enabling the efficient large-scale production of high-purity 3-hydroxypropionic acid.

[0097] For example, when a non-solvent is contacted with a concentrated solution of 3-hydroxypropionic acid in the presence of an alkali metal salt, an alkali metal salt of 3-hydroxypropionic acid is produced. As the concentration of the alkali metal salt increases, fine crystals form, and solid-liquid phase separation occurs. Subsequently, as crystallization proceeds, the alkali metal salt of 3-hydroxypropionic acid grows into solid crystals (3-hydroxypropionate crystals), and the resulting 3-hydroxypropionate crystals contain very low levels of impurities, while being separated from liquid impurities such as glycerol and 1,3-propanediol. In this case, the non-solvent is used to promote the crystallization of the alkali metal salt of 3-hydroxypropionic acid, thereby increasing the solid-liquid separation capability and producing 3-hydroxypropionate crystals with higher purity.

[0098] The volume ratio between the concentrate and the non-solvent of 3-hydroxypropionic acid can be determined by taking into account the concentration of 3-hydroxypropionic acid or the volume of the concentrate and the non-solvent. For example, the concentrate and non-solvent can be used at a volume ratio of 1:0.5 to 1:20, or 1:0.5 to 1:10, or 1:0.8 to 1:8, or 1:1 to 1:5.

[0099] If the volume of the non-solvent is too small compared to the concentrate, the concentration of crystals formed is high, and the crystal formation rate increases, making it impossible to slowly form pure crystal particles; instead, irregular crystal particles form rapidly. Furthermore, the solid-liquid separation capability is low, making it difficult to separate liquid impurities from the alkali metal salt of 3-hydroxypropionic acid to be purified. Conversely, if the volume of the non-solvent is too large compared to the concentrate, the formed crystals may dissolve in some cases due to the solubility of the non-solvent, increasing the time spent in the crystal filtration process after crystal formation and increasing the amount of waste liquid, which is uneconomical.

[0100] Non-solvents may include alcohol non-solvents, ketone non-solvents, nitrile non-solvents, or mixtures of two or more thereof, and more specifically, at least one alcohol non-solvent may be used.

[0101] Ketone nonsolvents may include one or more selected from acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isopentyl ketone, isophorone, and di(isobutyl) ketone. Alcohol nonsolvents may include one or more selected from methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, benzyl alcohol, cyclohexanol, diacetone alcohol, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-methoxyethanol, and 1-decyl alcohol. Nitrile nonsolvents may include one or more selected from acetonitrile, propionitrile, butyronitrile, valerate, octanoic acid, heptanitrile, cyclopentanoic acid, cyclohexanenitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile.

[0102] The step of contacting the concentrate with a non-solvent to form 3-hydroxypropionate crystals can be carried out at temperatures above 0°C, above 15°C, above 30°C, above 35°C, above 40°C, above 45°C, above 50°C, or above 55°C, and can also be carried out at temperatures below 100°C, below 90°C, below 80°C, below 75°C, below 70°C, below 65°C, or between 0°C and 100°C.

[0103] At this point, the temperature can be adjusted to the above range by adding a non-solvent to the concentrate at the above temperature, or by heating or cooling the concentrate and non-solvent mixture.

[0104] 3-Hydroxypropionate crystals can be in the form shown in Structural Formula 1 or Structural Formula 2 below. That is, 3-hydroxypropionate crystals can include 3-hydroxypropionate in the form shown in Structural Formula 1 or Structural Formula 2.

[0105] In structural formulas 1 and 2, "cation" refers to a cation, "3HP" refers to 3-hydroxypropionic acid bound to the cation, and "n" is the number of "3HP" molecules bound to the cation and is an integer greater than or equal to 1. In structural formula 2, "m" is the number of water molecules bound to the cation (3HP)n in the hydrate, and "m" is an integer greater than or equal to 1. The cation can be, for example, Na+, Mg... 2+ or Ca 2+ However, in Mg 2+ or Ca 2+ Under certain conditions, 3-hydroxypropionate crystals can be formed more effectively.

[0106] [Structure 1]

[0107] Cation (3HP) n

[0108] [Structure 2]

[0109] Cation (3HP) n ·mH2O

[0110] Furthermore, the step of forming 3-hydroxypropionate crystals may further include stirring the concentrate.

[0111] The stirring process can be carried out at the following temperatures: 0°C to 70°C, 0°C to 60°C, 0°C to 50°C, 0°C to 40°C, 0°C to 35°C, 0°C to 30°C, 10°C to 70°C, 10°C to 60°C, 10°C to 50°C, 10°C to 40°C, 10°C to 35°C, 10°C to 30°C, 15°C to 70°C, 15°C to 60°C, 15°C to 50°C, 15°C to 40°C, 15°C to 35°C. Performed at temperatures of 15°C to 30°C, 20°C to 70°C, 20°C to 60°C, 20°C to 50°C, 20°C to 40°C, 20°C to 35°C, or 20°C to 30°C (e.g., room temperature), and / or at 100 rpm to 2000 rpm, 100 rpm to 1500 rpm, 100 rpm to 1000 rpm, 100 rpm to 500 rpm, 100 rpm to 400 rpm, or 200 rpm to 400 rpm (e.g., approximately 300 rpm).

[0112] Particle size distribution D of 3-hydroxypropionate crystals 50 It can be 20μm or larger and 90μm or smaller, 25μm or larger and 85μm or smaller, 30μm or larger and 80μm or smaller, or 35μm or larger and 75μm or smaller.

[0113] In addition, the particle size distribution D of 3-hydroxypropionate crystals 10 The particle size distribution D of 3-hydroxypropionate crystals can be greater than 5 μm and less than 40 μm, greater than 8 μm and less than 35 μm, or greater than 10 μm and less than 30 μm. 90 It can be 50μm or larger and 200μm or smaller, 60μm or larger and 190μm or smaller, 65μm or larger and 180μm or smaller, or 70μm or larger and 175μm or smaller.

[0114] Particle size distribution D 50 D 10 and D 90 This refers to the particle size at which the cumulative volume of the particles reaches 50%, 10%, and 90% respectively in the particle size distribution curve, where D... 50 D 10 and D 90 Methods such as laser diffraction can be used for measurement. Laser diffraction methods can typically measure particle sizes from submicron to several millimeters and can yield results with high reproducibility and high resolution.

[0115] If the particle size distribution D of 3-hydroxypropionate crystals 50 D 10 and D 90 If the particle size is too large, the crystals will contain impurities that must be removed during the crystallization process, leading to reduced purification efficiency. If the particle size distribution is too small, the liquid permeability will be reduced during crystal filtration.

[0116] Meanwhile, the (D) of 3-hydroxypropionate crystals 90 -D 10 ) / D 50 It can be 1.00 or higher and 3.00 or lower, 1.20 or higher and 2.80 or lower, 1.40 or higher and 2.60 or lower, or 1.60 or higher and 2.40 or lower.

[0117] In addition, the volume average particle size of 3-hydroxypropionate crystals can be 30 μm or more and 100 μm or less, 35 μm or more and 95 μm or less, or 40 μm or more and 90 μm or less; the number average particle size can be 1 μm or more and 30 μm or less, 3 μm or more and 25 μm or less, or 5 μm or more and 20 μm or less; and the volume average particle size can be 10 μm or more and 70 μm or less, 15 μm or more and 60 μm or less, or 20 μm or more and 55 μm or less.

[0118] If the volume-average particle size, number-average particle size, and volume-average particle size of 3-hydroxypropionate crystals are too large, the crystals will contain impurities that must be removed during crystallization, leading to reduced purification efficiency. If they are too small, the liquid permeability will be reduced during crystal filtration.

[0119] In addition, the particle size distribution (D) of 3-hydroxypropionate crystals 10 D 50 D 90 The aspect ratio (LW) and average LW ratio in the crystals are ≥0.50 and ≤3.00, ≥0.70 and ≤2.80, and ≥1.00 and ≤2.50. If the LW ratio of the 3-hydroxypropionate crystals is too large, flowability and clogging problems will occur during crystal transfer; if the LW ratio is too small, liquid permeability will be reduced during crystal filtration.

[0120] The water content of 3-hydroxypropionate crystals can be measured by the Karl Fischer method. The water content of 3-hydroxypropionate crystals can be above 200 ppm and below 5000 ppm, above 250 ppm and below 4800 ppm, above 300 ppm and below 4600 ppm, or above 350 ppm and below 4400 ppm.

[0121] At this point, the water contained in the 3-hydroxypropionate crystals refers to the adhering water contained between the crystals, not the crystal water (e.g., Ca(3HP)2·2H2O). Furthermore, if the water content in the 3-hydroxypropionate crystals is too high, it will be recycled as a slurry rather than a crystalline solid, or it will contain impurities in the water, which will cause problems with reduced purity improvement.

[0122] In a process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention, since 3-hydroxypropionic acid is prepared by fermentation of bacterial strains capable of producing 3-hydroxypropionic acid using a process such as described below, the 3-hydroxypropionate crystals may contain radioactive carbon isotopes ( 14 C).

[0123] Radiocarbon isotopes ( 14 C) Every 10 in the Earth's atmosphere 12 A carbon atom contains approximately 1 atom and has a half-life of approximately 5700 years, and this is due to cosmic rays and normal nitrogen ( 14 Nuclear reactions involving nitrogen (N) can enrich carbon reserves in the upper atmosphere. Meanwhile, in fossil fuels, isotopes have long been broken down, making... 14The C ratio may be essentially zero. When using bio-derived feedstocks as 3-hydroxypropionic acid feedstocks, or when using them in conjunction with fossil fuels, the content of radioactive carbon isotopes (pMC; modern carbon percentage) and bio-carbon in 3-hydroxypropionic acid can be measured according to ASTM D6866-21.

[0124] After the carbon atoms in the compound to be measured are prepared into graphite or carbon dioxide gas form, the content can be measured, for example, by mass spectrometry, or according to liquid scintillation analysis. At this point, methods for analyzing carbon atoms from... 12 Separation from C ions 14 The two radioactive isotopes are separated by an accelerator and a mass spectrometer for C ions, and the content and content ratio can be measured by the mass spectrometer.

[0125] 3-hydroxypropionate crystals, as measured according to ASTM D6866-21, have a radiocarbon isotope content of 20 pMC (modern carbon percentage) or more, 50 pMC or more, 90 pMC or more, or 100 pMC or more, and a biocarbon content of 20 wt% or more, 50 wt% or more, 80 wt% or more, 90 wt% or more, or 95 wt% or more.

[0126] Radiocarbon isotope ratio (pMC) refers to the radiocarbon isotope content (PMC) in a 3-hydroxypropionate crystal. 14 C) and the radiocarbon isotopes of the current standard reference material ( 14 The proportion of C) and it can be greater than 100% because the nuclear testing procedures of the 1950s are still valid and have not been extinguished.

[0127] Furthermore, biocarbon content refers to the amount of biocarbon contained relative to the total carbon content within the 3-hydroxypropionate crystals. A higher value generally corresponds to an environmentally friendly compound.

[0128] At the same time, if the radioactive carbon isotope content (pMC) and biocarbon content of 3-hydroxypropionate crystals are too low, their environmental friendliness is reduced, and they cannot be regarded as bio-derived materials.

[0129] The crystallization state of 3-hydroxypropionate crystals can be confirmed by peaks in X-ray diffraction (XRD) patterns.

[0130] For example, during X-ray diffraction (XRD) analysis, 3-hydroxypropionate crystals can exhibit peaks between lattice values ​​in the range of 8° to 22°.

[0131] For example, when the concentrate contains magnesium hydroxide (Mg(OH)₂) and the formed 3-hydroxypropionate crystals are Mg(3HP)₂, during X-ray diffraction (XRD) analysis of Mg(3HP)₂, lattice peaks caused by the bonding between 3-hydroxypropionic acid and magnesium appear in the 2θ value range of 8° to 15°. This peak shows a different result from the XRD analysis results of magnesium hydroxide (Mg(OH)₂) or magnesium sulfate (Mg(SO₄)). As a result of XRD analysis, it can be determined that Mg(3HP)₂ crystals are formed when a specific peak appears in the 2θ value range of 8° to 15°.

[0132] Specifically, during the X-ray diffraction (XRD) analysis of Mg(3HP)2, more than three, four, or five peaks can appear in the 2θ value range of 8° to 15°, and for example, peaks can appear in the 2θ value ranges of 8.2° to 9.3°, 9.5° to 11.0°, 11.2° to 12.7°, 12.9° to 13.3°, and 13.5° to 14.8°, respectively.

[0133] Furthermore, when the concentrate contains calcium hydroxide (Ca(OH)2) and the 3-hydroxypropionate crystals formed therefrom are Ca(3HP)2, during X-ray diffraction (XRD) analysis of Ca(3HP)2, lattice peaks caused by the bonding between 3-hydroxypropionic acid and calcium appear in the 2θ value range of 10° to 22°. This peak shows a different result from the XRD analysis results of calcium hydroxide (Ca(OH)2) or calcium sulfate (Ca(SO4)). As a result of the XRD analysis, it can be determined that Ca(3HP)2 crystals are formed when a specific peak appears in the 2θ value range of 10° to 22°.

[0134] Specifically, during the X-ray diffraction (XRD) analysis of Ca(3HP)2, more than 3, 5, 7, or 9 peaks can appear in the 2θ value range of 10° to 22°, and for example, peaks can appear in the 2θ value ranges of 10.0° to 11.0°, 11.1° to 11.6°, 11.6° to 12.5°, 12.7° to 13.6°, 13.8° to 16.0°, 17.0° to 18.0°, 19.0° to 19.8°, 20.2° to 21.2°, or 21.5° to 22.0°, respectively.

[0135] Meanwhile, the incident angle (θ) refers to the point on the graph of the diffraction intensity where the horizontal axis (x-axis) in the xy plane is twice the incident angle of the incident X-ray (2θ) and the vertical axis (y-axis) in the xy plane is zero, where the first differential value (the slope of the tangent, dy / dx) is zero. As the value of twice the incident angle of the incident X-ray (2θ) as the horizontal axis (x-axis) increases in the positive direction, twice the incident angle of the X-ray (2θ) as the horizontal axis (x-axis) changes from a positive value to a negative value relative to the first differential value (the slope of the tangent, dy / dx) of the diffraction intensity as the vertical axis (y-axis).

[0136] Furthermore, X-ray diffraction (XRD) analysis revealed that 3-hydroxypropionate crystals can exhibit certain interatomic relationships within the crystal. The above and the following, The above and the following, The above and the following, The above and The following distances (d values).

[0137] For example, when the 3-hydroxypropionate crystal is Mg(3HP)₂, the interatomic distance (d value) in the crystal with peaks appearing in the 2θ value range of 8° to 15° can be... The above and the following, The above and the following, The above and the following, The above and the following.

[0138] Furthermore, when the 3-hydroxypropionate crystal is Ca(3HP)₂, the interatomic distance (d value) in the crystal with peaks appearing in the 2θ value range of 10° to 22° can be... The above and the following, The above and the following, The above and the following, The above and The following, or The above and the following.

[0139] In addition, 3-hydroxypropionate crystals can have a glass transition temperature above -55°C and below -30°C, a melting point above 30°C and below 170°C, and a crystallization temperature above 25°C and below 170°C.

[0140] The glass transition temperature, melting point, and crystallization temperature of 3-hydroxypropionate crystals can be measured by differential scanning calorimetry (DSC), wherein the heating rate during the measurement process can be from 1 °C / min to 20 °C / min. Furthermore, 3-hydroxypropionate crystals can have glass transition temperatures above -55 °C and below -30 °C, above -50 °C and below -35 °C, or above -45 °C and below -40 °C. Furthermore, the melting point of 3-hydroxypropionate crystals can be above 30 °C and below 170 °C, above 31 °C and below 160 °C, or above 32 °C and below 150 °C. Furthermore, the crystallization temperature of 3-hydroxypropionate crystals can be above 25 °C and below 170 °C, above 27 °C and below 160 °C, or above 30 °C and below 150 °C. Furthermore, the crystallization stability range of 3-hydroxypropionate crystals can be from -40 °C to 150 °C.

[0141] The purity of 3-hydroxypropionate contained in 3-hydroxypropionate crystals can be calculated as a percentage (%) of the mass of the compound having structural formula 1 and / or structural formula 2 relative to the mass of the total recovered crystals. For example, the purity of 3-hydroxypropionate contained in 3-hydroxypropionate crystals can be more than 70%, more than 80%, more than 90%, 70% to 99.9%, 80% to 99.9%, 90% to 99.9%, 70% to 99%, 80% to 99%, or 90% to 99%, but is not limited thereto.

[0142] As described above, the process for recovering 3-hydroxypropionic acid may include: fermenting a bacterial strain capable of producing 3-hydroxypropionic acid to produce a 3-hydroxypropionic acid fermentation broth, and concentrating the fermentation broth to form a concentrate containing more than 300 g / L of 3-hydroxypropionic acid before the step of forming 3-hydroxypropionate crystals.

[0143] The bacterial strain capable of producing 3-hydroxypropionic acid may include genes encoding at least one or both proteins selected from glycerol dehydrase and aldehyde dehydrogenase.

[0144] In one instance, the 3-hydroxypropionic acid-producing strain may further include a gene (gdrAB) encoding a glycerol dehydratase activator (GdrAB). In another instance, the 3-hydroxypropionic acid-producing strain may further be a bacterial strain capable of biosynthesizing vitamin B12.

[0145] The glycerol dehydratase may be encoded by the dhaB gene (GenBank accession number U30903.1), but is not limited thereto. The dhaB gene may be an enzyme from Klebsiella pneumoniae, but is not limited thereto. Genes encoding glycerol dehydratase may include genes encoding dhaB1, dhaB2, and / or dhaB3. The glycerol dehydratase protein and the gene encoding it may include mutations in the gene and / or amino acid sequence, said mutations being within the range that maintain the enzymatic activity of breaking down glycerol into 3-hydroxypropanal (3-HPA) and water (H2O).

[0146] The gene (aldH) encoding aldehyde dehydrogenase (ALDH) can be, for example, the aldH gene (GenBank accession number U00096.3; EaldH) from *Escherichia coli* or the *E. coli* K12 MG1655 cell line, the puuC gene from *Klebsiella pneumoniae*, and / or the KGSADH gene from *Azospirillum brasilense*, but is not limited thereto. The aldehyde dehydrogenase protein and the gene encoding it can include mutations in the gene and / or amino acid sequence, said mutations being within the range that maintain the activity of producing 3-hydroxypropionic acid from 3-hydroxypropanal.

[0147] The culture medium used to generate the fermentation broth can be selected without limitation from the scope of its use in the production of 3-hydroxypropionic acid. In one example, the culture medium may contain glycerol as a carbon source. In another example, the culture medium may be crude glycerol and / or pretreated crude glycerol, but is not limited thereto. In one example, the generating culture medium may further include vitamin B12.

[0148] In the step of fermenting a bacterial strain capable of producing 3-hydroxypropionic acid to produce a 3-hydroxypropionic acid fermentation broth, the concentration of 3-hydroxypropionic acid contained in the 3-hydroxypropionic acid fermentation broth may be from 1 g / L to 200 g / L, from 10 g / L to 150 g / L, from 30 g / L to 130 g / L, or from 40 g / L to 100 g / L.

[0149] Furthermore, fermentation can be neutral, for example, maintained within a pH range of 6 to 8, 6.5 to 8, 6 to 7.5, or 6.5 to 7.5 during fermentation, but is not limited to this. The pH range can be adjusted appropriately as needed. Alkali metal salts can be added for neutral fermentation. Alkali metal salts may include Mg. 2+ Ca 2+ Or mixtures thereof. In addition, alkali metal salts can be Ca(OH)2 or Mg(OH)2, but are not limited to these.

[0150] A process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention may further include: removing (separating) cells from the fermentation broth; purifying and / or decolorizing the fermentation broth and / or the cell-free fermentation broth; and / or filtering the fermentation broth and / or the cell-free fermentation broth after the step of producing 3-hydroxypropionic acid fermentation broth.

[0151] Within the scope of the desired cell (strain) removal, cell removal (isolation) can be performed by any method known in the art without limitation. In one instance, cell isolation can be performed by centrifugation.

[0152] Within the scope of the purpose of purifying the fermentation broth, the steps of purifying and / or decolorizing the fermentation broth and / or the fermentation broth that has already had cells removed can be carried out by selecting methods known in the art, without limitation. For example, the steps can be carried out by mixing activated carbon with the fermentation broth and then removing the activated carbon, but are not limited thereto.

[0153] Within the scope of removing solid impurities, removing proteins and / or materials with hydrophobic functional groups, and / or decolorizing, the steps of filtering fermentation broth and / or fermentation broth with cells removed can be performed by any method known in the art, without limitation. For example, the steps can be performed by filter filtration and / or activated carbon filtration, but are not limited thereto.

[0154] A process for recovering 3-hydroxypropionic acid according to one embodiment of the present invention may include: after a step of fermenting a bacterial strain capable of producing 3-hydroxypropionic acid to produce a 3-hydroxypropionic acid fermentation broth, concentrating the fermentation broth to form a concentrate containing 3-hydroxypropionic acid.

[0155] The fermentation broth can be concentrated by evaporating the fermentation broth (e.g., the liquid component of the fermentation broth).

[0156] Concentration can be carried out by any method commonly used for evaporating the liquid components of the fermentation broth. For example, concentration can be achieved through rotary evaporation, evaporative concentration, vacuum concentration, reduced pressure concentration, etc., but is not limited to these methods.

[0157] In one instance, the concentration of 3-hydroxypropionic acid in the fermentation broth after concentration can increase by 2 to 50 times, 2 to 40 times, 2 to 30 times, 2 to 20 times, 2 to 10 times, 5 to 50 times, 5 to 40 times, 5 to 30 times, 5 to 20 times, or 5 to 10 times compared to before concentration.

[0158] According to another embodiment of the present invention, a slurry composition comprising 3-hydroxypropionic acid is provided, the slurry composition comprising a precipitate represented by the following structural formula 4 and 3-hydroxypropionic acid.

[0159] [Structure 4]

[0160] Cations (Anions)·pH2O

[0161] In structural formula 4, the cation is an alkali metal salt cation; for example, it can be Na. + Mg 2+ or Ca 2+ However, when it is Mg 2+ or Ca 2+ At this time, 3-hydroxypropionate crystals can be formed more effectively.

[0162] Furthermore, the anion is an acid anion, and may be, for example, SO42-. 2- PO4 3- or CO3 2- However, it is not limited to this. p is the number of water molecules in the hydrate, which is an integer greater than or equal to 1.

[0163] The slurry composition can be formed in a process for recovering 3-hydroxypropionic acid according to one embodiment of the invention, and for example, it can be formed in the step of adding acid to 3-hydroxypropionate crystals separated from the concentrate at a temperature of, for example, above 30°C and below 90°C.

[0164] The particle size of the precipitate can be 1.0 μm or larger, 1.5 μm or larger, 10.0 μm or larger, 13.0 μm or larger, or 15.0 μm or larger, and can be less than 300.0 μm, less than 250.0 μm, less than 200.0 μm, less than 150.0 μm, less than 100.0 μm, less than 50.0 μm, less than 30.0 μm, less than 20.0 μm, less than 8.0 μm, less than 7.0 μm, less than 6.0 μm, less than 5.0 μm, or less than 2.0 μm. The precipitate meeting these particle size requirements allows for a reduction in its moisture content, which increases the flowability of the slurry containing the precipitate and facilitates its filtration from the slurry. For example, the particle size of the precipitate can be 10.0 μm or larger, in which case filtration separation from the slurry becomes very easy, and dust generated during recycling to other industrial sectors such as cement production is reduced, which can be very advantageous in processing.

[0165] Precipitates can exhibit various particle shapes, such as angular, spherical, plate-like, and needle-like. Furthermore, the particle size of the precipitate can be measured using scanning electron microscopy (SEM). In this case, the particle size can be measured based on the longest linear distance between the crystal planes contained within the precipitate.

[0166] Furthermore, the moisture content of the precipitate can be below 150%, below 130%, below 110%, below 100%, below 80%, or below 70%, and above 1%, above 10%, or above 30%. If the moisture content of the precipitate is too high, the fluidity of the slurry containing the precipitate decreases, making the process difficult and making it difficult to separate the precipitate from the slurry, thus making it difficult to recover 3-hydroxypropionic acid in a high yield.

[0167] Beneficial effects

[0168] The process for recovering 3-hydroxypropionic acid provided by this invention can easily separate fermentation byproducts and / or additives through the crystallization of 3-hydroxypropionate, thereby recovering high-purity 3-hydroxypropionate. The recovered 3-hydroxypropionate crystals are reacted with acid, and the precipitate is separated from the prepared slurry, thus recovering 3-hydroxypropionic acid with high purity and high yield. Simultaneously, the wash water used to wash the precipitate can be reused in the process, thereby recovering 3-hydroxypropionic acid with high concentration, high purity, and high yield. Attached Figure Description

[0169] Figure 1 This is a scanning electron microscope (SEM) image of the precipitate formed in Example 3.

[0170] Figure 2 This is a scanning electron microscope (SEM) image of the precipitate formed in Comparative Example 3.

[0171] Figure 3 This is a scanning electron microscope (SEM) image of the precipitate formed in Example 4.

[0172] Figure 4 This is a scanning electron microscope (SEM) image of the precipitate formed in Example 5. Detailed Implementation

[0173] The invention will be described in more detail below with reference to embodiments. However, the following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0174] Preparation Example 1: Preparation of bacterial strains for the production of 3-hydroxypropionic acid

[0175] A recombinant vector was prepared, and genes encoding glycerol dehydratase and aldehyde dehydrogenase were introduced into the vector. Glycerol dehydratase and aldehyde dehydrogenase are known to use glycerol as a substrate to produce 3-hydroxypropionic acid (3HP). The prepared recombinant vector was introduced into Escherichia coli strain W3110 to prepare a 3-hydroxypropionic acid-producing strain.

[0176] More specifically, the BtuR gene encoding adenosine transferase was cloned into a plasmid pCDF containing genes encoding glycerol dehydratase (dhaB), aldehyde dehydrogenase (aldH), and glycerol dehydratase reactivator (gdrAB). The obtained pCDF_J23101_dhaB_gdrAB_J23100_aldH_btuR vector was introduced into strain W3110 (KCCM 40219) using an electroporation apparatus (Bio-Rad, Gene Pulser Xcell) to prepare a 3-hydroxypropionic acid-producing strain. The preparation process of the 3-hydroxypropionic acid-producing strain in Preparation Example 1, as well as the vectors, primers, and enzymes used, were performed according to Example 1 of Korean Unexamined Patent Publication No. 10-2020-0051375, which is incorporated herein by reference.

[0177] Preparation Example 2: Preparation of Ca(3HP)2 crystals

[0178] At 35°C, in a 5L fermenter, using unpurified glycerol as a carbon source, the 3-hydroxypropionic acid-producing strain prepared in Example 1 was fermented and cultured to produce 3-hydroxypropionic acid. To prevent the pH from decreasing due to the production of 3-hydroxypropionic acid, calcium hydroxide (Ca(OH)2), as an alkali metal salt, was added to maintain the pH at neutral during fermentation.

[0179] Following fermentation, cells were removed by centrifugation (4000 rpm, 10 min, 4 °C), and the primary fermentation broth was purified using activated charcoal (primary purification). Specifically, activated charcoal was added to the fermentation broth from which bacterial cells had been removed by centrifugation, the mixture was thoroughly mixed, and then centrifuged again to separate the activated charcoal. The fermentation broth containing the activated charcoal was then filtered through 0.7 μm filter paper using a vacuum pump to purify the 3-hydroxypropionic acid fermentation broth.

[0180] After primary purification, the concentration of 3-hydroxypropionic acid in the fermentation broth was between 50 g / L and 100 g / L. The broth was concentrated to 600 g / L using a rotary evaporator (50°C, 50 mbar) to prepare a concentrate. Ethanol was added at twice the volume of the concentrate, and the mixture was stirred at room temperature (300 rpm) to produce Ca(3HP)₂ crystals. At this point, the concentration of the alkali metal salt in the concentrate was 493.3 g / L (based on Ca(OH)₂). The resulting crystals were washed three times with ethanol (EtOH) and dried in an oven at 50°C for final crystal recovery.

[0181] Comparative Example 1

[0182] 5.0 g of Ca(3HP)₂ crystals recovered in Preparation Example 2 were added to 13.5 ml of distilled water to prepare an aqueous solution of Ca(3HP)₂, which was stirred at 60 °C and 350 rpm for 10 minutes. 2.5 g of 95% sulfuric acid solution was added to the Ca(3HP)₂ aqueous solution at a uniform rate over 5 minutes to achieve a sulfur (S) to calcium (Ca) molar ratio of 0.9, and the mixture was further stirred for 30 minutes to form a slurry containing CaSO₄ precipitate and 3-hydroxypropionic acid.

[0183] The CaSO4 precipitate was separated by filtration using a filter flask and a vacuum pump. The filtrate (B) before washing was then obtained in the filter flask. The filtered CaSO4 precipitate was then washed with 20 ml of distilled water, and filtered again to obtain the washed filtrate (C). The filtrate was then washed with 40 ml of distilled water and filtered again to obtain a second washing solution (D). The CaSO4 precipitate was then dried in an oven at 40°C for 20 hours to obtain the final dried CaSO4 precipitate.

[0184] Example 1

[0185] Except that in the preparation of the Ca(3HP)2 aqueous solution, the first washing solution (C) of Comparative Example 1 was reused instead of 13.5 ml of distilled water, the filtrate (G), the first washing solution (H), the second washing solution (I), and the dried CaSO4 precipitate were obtained in the same manner as in Comparative Example 1.

[0186] <Experimental Example>

[0187] Measurement of the concentration of 1,3-hydroxypropionic acid

[0188] The concentration of 3-hydroxypropionic acid was measured using high performance liquid chromatography (HPLC) for the pre-wash filtrate (B, G), first washing solution (C, H), and second washing solution (D, I) obtained in Example 1 and Comparative Example 1, and the results are shown in Table 1 below.

[0189] Measurement of the recovery rate of 2,3-hydroxypropionic acid

[0190] The recoveries of 3-hydroxypropionic acid obtained in Example 1 and Comparative Example 1 were measured and calculated using high performance liquid chromatography (HPLC), and the results are shown in Table 1 below.

[0191] Specifically, the absolute amount (Y) of 3-hydroxypropionic acid in Ca(3HP)2 aqueous solution was measured by high performance liquid chromatography (HPLC). 参照 The content of 3-hydroxypropionic acid in the pre-wash filtrate (B or G) (Y) 过滤 The content of 3-hydroxypropionic acid in the first washing solution (C or H) (Y)洗涤1 The content of 3-hydroxypropionic acid contained in the second washing solution (D or I) (Y) 洗涤2 Substitute these values ​​into Equations 2 through 4 below to calculate the recovery rate of 3-hydroxypropionic acid.

[0192] [Equation 2]

[0193] Recovery rate (%) of 3-hydroxypropionic acid in the pre-wash filtrate (B or G) = Y 过滤 / Y 参照 *100

[0194] [Equation 3]

[0195] Recovery rate (%) of 3-hydroxypropionic acid in the first washing solution (C or H) = Y 洗涤1 / Y 参照 *100

[0196] [Equation 4]

[0197] Recovery rate (%) of 3-hydroxypropionic acid in the second washing solution (D or I) = Y 洗涤2 / Y 参照 *100

[0198] Furthermore, it is assumed that the 3-hydroxypropionic acid recovered from the unwashed pre-filtrate and the first and second washing solutions is retained in the CaSO4 precipitate, which is shown in Table 1 below as the recovery rate of 3-hydroxypropionic acid contained in the CaSO4 precipitate.

[0199] [Table 1]

[0200]

[0201] Referring to Table 1, it can be confirmed that since Example 1 reused the first washing solution (C) of Comparative Example 1 to prepare the Ca(3HP)2 aqueous solution, both Example 1 and Comparative Example 1 used the same amount of Ca(3HP)2 crystals. However, compared to Comparative Example 1, Example 1 exhibited a significantly higher concentration of 3-hydroxypropionic acid in all filtrates and washing solutions. This can be expected because 3-hydroxypropionic acid was not lost during the process but was recycled within the process.

[0202] Example 2

[0203] 6.12 g of Ca(3HP)2 crystals recovered in Preparation Example 2 were added to 13 ml of distilled water to prepare a 32.0 wt% Ca(3HP)2 aqueous solution, which was stirred at 60 °C and 350 rpm for 10 minutes.

[0204] 2.5 g of 95% sulfuric acid solution was added to an aqueous solution of Ca(3HP)2 at a uniform rate over 5 minutes to achieve a sulfur (S) to calcium (Ca) molar ratio of 0.85, and the mixture was further stirred for 30 minutes to form a slurry containing CaSO4 precipitate and 3-hydroxypropionic acid.

[0205] Filtration was performed using a filter flask and a vacuum pump to separate the CaSO4 precipitate. The unwashed filtrate (A) was then obtained in the filter flask, and the filtered CaSO4 precipitate was washed with 30 ml of distilled water, followed by filtration to obtain the washed filtrate (B). The CaSO4 precipitate was then dried in an oven at 40°C for 20 hours to finally obtain the dried CaSO4 precipitate. Furthermore, filtrates (A) and (B) containing 3-hydroxypropionic acid were obtained.

[0206] Example 3

[0207] The process for recovering 3-hydroxypropionic acid was carried out in the same manner as in Example 2, except that the filtered CaSO4 precipitate was washed with 250 ml of distilled water instead of 30 ml of distilled water.

[0208] Comparative Example 2

[0209] The process for recovering 3-hydroxypropionic acid was carried out in the same manner as in Example 2, except that the Ca(3HP)2 aqueous solution was stirred at 25°C instead of at 60°C.

[0210] Comparative Example 3

[0211] The process for recovering 3-hydroxypropionic acid was carried out in the same manner as in Example 3, except that the Ca(3HP)2 aqueous solution was stirred at 25°C instead of at 60°C.

[0212] <Experimental Example>

[0213] 1. Evaluation of calcium (Ca) removal rate

[0214] When the 3-hydroxypropionate crystals (Ca(3HP)2 crystals) in Example 3 and Comparative Example 3 were converted into 3-hydroxypropionic acid, CaSO4 precipitate was generated. Therefore, the content of removed calcium (Ca) element was measured by inductively coupled plasma analysis.

[0215] Specifically, the calcium (Ca) content (X) in a 32.0 wt% Ca(3HP)2 aqueous solution was analyzed. 参照 ) and the content of calcium (Ca) element contained in the filtrate (B) after washing (X) 过滤The removal rate of calcium (Ca) was calculated according to Equation 5 below, and the results are shown in Table 2 below.

[0216] [Equation 5]

[0217] Calcium (Ca) removal rate (%) = (X) 参照 -X 过滤 ) / X 参照 *100

[0218] 2. Measurement of precipitate particle size

[0219] The particle size of the CaSO4 precipitates formed in Example 3 and Comparative Example 3 was confirmed by scanning electron microscopy analysis, and the results are shown in Table 2 below.

[0220] At this point, the particle size of the CaSO4 precipitate is measured based on the straight-line distance between the crystal planes with the longest straight-line distance among the crystal planes contained in the precipitate.

[0221] on the other hand, Figure 1 These are scanning electron microscope (SEM) images of the precipitate formed in Example 3. Figure 2 This is a scanning electron microscope (SEM) image of the precipitate formed in Comparative Example 3.

[0222] 3. Measurement of moisture content in precipitates

[0223] The weights of the CaSO4 precipitates formed in Example 3 and Comparative Example 3 before and after drying were substituted into Equation 6 below to calculate the moisture content of the precipitates, and the results are shown in Table 2 below.

[0224] [Equation 6]

[0225] Moisture content (wt%) = (Weight of precipitate before drying - Weight of precipitate after drying) / (Weight of precipitate after drying) * 100

[0226] 4. Measurement of the recovery rate of 4,3-hydroxypropionic acid

[0227] The recoveries of 3-hydroxypropionic acid obtained in Example 2 and Comparative Example 2 were measured by high performance liquid chromatography (HPLC), and the results are shown in Table 3 below.

[0228] Specifically, the content of 3-hydroxypropionic acid in a 32.0 wt% Ca(3HP)2 aqueous solution was measured by high performance liquid chromatography (HPLC). 参照 The content of 3-hydroxypropionic acid in the pre-wash filtrate (A) (Y) 过滤1 The content of 3-hydroxypropionic acid in the washing filtrate (B) and the content of 3-hydroxypropionic acid (Y) 过滤2Substitute these values ​​into Equations 7 and 8 below to calculate the recovery rate of 3-hydroxypropionic acid in the pre-wash filtrate (A) and post-wash filtrate (B).

[0229] [Equation 7]

[0230] Recovery rate (%) of 3-hydroxypropionic acid in the pre-wash filtrate (A) = Y 过滤1 / Y 参照 *100

[0231] [Equation 8]

[0232] Recovery rate (%) of 3-hydroxypropionic acid in the filtrate (B) after washing = Y 过滤2 / Y 参照 *100

[0233] [Table 2]

[0234] Example 3 73.1 1.5-4.5 68.0 Comparative Example 3 76.8 0.2-2.0 175.0

[0235] [Table 3]

[0236]

[0237] Referring to Tables 2 and 3, it can be confirmed that the CaSO4 precipitate formed in Example 3, where sulfuric acid was added at 60°C, has a larger particle size and a significantly lower moisture content compared to the CaSO4 precipitate formed in Comparative Example 3, where sulfuric acid was added at 25°C. Furthermore, it can be confirmed that Example 2, where sulfuric acid was added at 60°C, has a significantly higher recovery rate of 3-hydroxypropionic acid compared to Comparative Example 2, where sulfuric acid was added at 25°C.

[0238] Example 4

[0239] 5.8 g of Ca(3HP)2 crystals recovered in Preparation Example 2 were added to 9.2 ml of distilled water and stirred for 1 hour to prepare an aqueous solution of Ca(3HP)2 (concentration of 630 g / L).

[0240] Add 10.9 ml of distilled water to a new flask and heat to 60°C using a heating mantle. Then, add 24 mg of sulfuric acid in 10 portions (24 mg each) at 6-minute intervals to the flask containing distilled water. Simultaneously, add a Ca(3HP)₂ aqueous solution to the flask containing distilled water at a rate of 0.25 g / min over 1 hour, and then stir. The resulting mixture is then stirred for another 30 minutes to form a slurry containing CaSO₄ precipitate and 3-hydroxypropionic acid.

[0241] Then, the CaSO4 precipitate and filtrate were separated using a filter flask and a vacuum pump.

[0242] Example 5

[0243] 5.8 g of Ca(3HP)2 crystals recovered in Preparation Example 2 were added to 9.2 ml of distilled water and stirred for 1 hour to prepare an aqueous solution of Ca(3HP)2.

[0244] Add 25.7 ml of distilled water to a new flask and heat to 60°C using a heating mantle. Then, divide 240 mg of sulfuric acid into 48 mg portions, adding them to the flask containing distilled water in five separate additions at 12-minute intervals. Simultaneously, add a Ca(3HP)₂ aqueous solution to the flask containing distilled water at a rate of 0.25 g / min over 1 hour, and then stir. The mixture is then further stirred for 30 minutes to form a slurry containing CaSO₄ precipitate and 3-hydroxypropionic acid.

[0245] Then, the CaSO4 precipitate and filtrate were separated using a filter flask and a vacuum pump.

[0246] <Experimental Example>

[0247] 1. Measurement of precipitate particle size

[0248] The particle size of the CaSO4 precipitates recovered in Examples 4 and 5 was confirmed by scanning electron microscopy analysis, and the results are shown in Table 4 below. In this case, the particle size of the CaSO4 precipitates was measured based on the straight-line distance between the crystal planes containing the longest straight-line distance among the crystal planes in the precipitate. On the other hand, Figure 3 The image shows a scanning electron microscope (SEM) image of the precipitate formed in Example 4. Figure 4 This is a scanning electron microscope (SEM) image of the precipitate formed in Example 5.

[0249] Measurement of the recovery rate of 2,3-hydroxypropionic acid

[0250] The recovery rates of 3-hydroxypropionic acid in Examples 4 and 5 were measured by high performance liquid chromatography (HPLC), and the results are shown in Table 4 below.

[0251] Specifically, before adding the product to the flask, the content (X) of 3-hydroxypropionic acid in the Ca(3HP)2 aqueous solution and the content (Y) of 3-hydroxypropionic acid in the filtrate were analyzed by HPLC, and then substituted into Equation 9 below to calculate the recovery rate of 3-hydroxypropionic acid.

[0252] [Equation 9]

[0253] Recovery rate of 3-hydroxypropionic acid (%) = Y / X * 100

[0254] 3. Evaluation of slurry fluidity

[0255] The flowability of the slurries formed in Examples 4 and 5 was evaluated according to the following criteria, and the results are shown in Table 4 below.

[0256] <Judgment Criteria>

[0257] High: When the slurry inside the flask is poured and removed without washing solvent, the volume of slurry remaining inside the flask is less than 10%.

[0258] Low: When the slurry inside the flask is poured out and removed without washing solvent, the volume of slurry remaining inside the flask is greater than 10%.

[0259] 4. Evaluation of slurry filtration rate

[0260] The filtration rate of the slurries formed in Examples 4 and 5 was evaluated according to the following criteria, and the results are shown in Table 4 below.

[0261] <Judgment Criteria>

[0262] Rapid: The injection flow rate of the filtrate obtained in the filtration flask is above 50 ml / min.

[0263] Slow: The injection rate of the filtrate obtained in the filtration flask is less than 50 ml / min.

[0264] [Table 4]

[0265]

[0266] Referring to Table 4, it can be confirmed that in the cases where Ca(3HP)2 aqueous solution is added continuously and sulfuric acid is added separately, the CaSO4 precipitate formed in Examples 4 and 5 has a large particle size, high precipitate flowability, fast precipitate filtration speed, and a 3-hydroxypropionic acid recovery rate of over 74.5%.

Claims

1. A process for recovering 3-hydroxypropionic acid, comprising: 3-hydroxypropionic acid crystals are formed in a concentrated solution containing 3-hydroxypropionic acid in the presence of calcium hydroxide, magnesium hydroxide or mixtures thereof as alkali metal salts. Prepare a solution comprising 3-hydroxypropionate crystals separated from the concentrate; The acid and the solution containing 3-hydroxypropionate crystals are stirred to form a precipitate; and The precipitate was subjected to a first wash. The process further includes adding acid to the solution containing 3-hydroxypropionate crystals at a temperature above 35°C and below 90°C before stirring the acid and the solution containing 3-hydroxypropionate crystals to form a precipitate.

2. The process for recovering 3-hydroxypropionic acid according to claim 1, This further includes reusing the first washing solution used for the first washing of the precipitate.

3. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, Before stirring the acid and the solution containing 3-hydroxypropionate crystals to form a precipitate, The process further includes adding the acid and the solution containing 3-hydroxypropionate crystals to the reactor continuously or in two or more separate steps.

4. The process for recovering 3-hydroxypropionic acid according to claim 3, wherein, The solution containing 3-hydroxypropionate crystals is continuously added to the reactor.

5. The process for recovering 3-hydroxypropionic acid according to claim 3, wherein, The acid is added to the reactor in three to twenty portions.

6. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, The acid content is 20% or more and 80% or less relative to 100% by weight of the 3-hydroxypropionate crystals.

7. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, After the precipitate is first washed... The process further includes performing a second wash on the precipitate after the first wash and reusing the second wash solution.

8. The process for recovering 3-hydroxypropionic acid according to claim 7, wherein, In preparing a solution containing 3-hydroxypropionate crystals separated from the concentrate, at least one washing solution selected from the first washing solution and the second washing solution is reused as a solvent.

9. The process for recovering 3-hydroxypropionic acid according to claim 7, wherein, At least one washing liquid selected from the first washing liquid and the second washing liquid is mixed with a filtrate in which the precipitate has been filtered to prepare a mixture, and the 3-hydroxypropionic acid is recovered from the mixture.

10. The process for recovering 3-hydroxypropionic acid according to claim 7, further comprising: Fermentation of bacterial strains capable of producing 3-hydroxypropionic acid to produce 3-hydroxypropionic acid fermentation broth; and The fermentation broth was concentrated to form the concentrate containing 3-hydroxypropionic acid. In the process of fermenting a bacterial strain capable of producing 3-hydroxypropionic acid to produce a 3-hydroxypropionic acid fermentation broth, at least one washing solution selected from the first washing solution and the second washing solution is reused.

11. The process for recovering 3-hydroxypropionic acid according to claim 10, wherein, The concentrated fermentation broth is prepared by evaporating the fermentation broth to form a concentrate containing 3-hydroxypropionic acid. The water removed by evaporation is liquefied and reused in at least one wash selected from the first wash and the second wash.

12. The process for recovering 3-hydroxypropionic acid according to claim 7, This further includes the precipitate after drying and washing. in, The moisture removed by the drying process is liquefied and reused in at least one wash selected from the first wash and the second wash.

13. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, The precipitate is represented by the following structural formula 3: [Structure 3] Cations (Anions) · pH2O in, The cation is Ca. 2+ or Mg 2+ , The anion is the anion of the acid. p is the number of water molecules in the hydrate, which is an integer greater than or equal to 1.

14. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, The particle size of the precipitate is greater than 1.0 μm.

15. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, The moisture content of the precipitate is below 150%.

16. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, The 3-hydroxypropionate crystal is represented by either structural formula 1 or structural formula 2 below: [Structure 1] Cation (3HP) n [Structure 2] Cation (3HP) n ·mH2O in, The cation is Ca. 2+ or Mg 2+ , The 3HP is 3-hydroxypropionic acid bound to the cation. The number of 3HP molecules that bind to the cation is an integer greater than or equal to 1. The m is the number of water molecules in the hydrate, which is an integer greater than or equal to 1.

17. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, The particle size distribution D of the 3-hydroxypropionate crystals 50 It is above 20 μm and below 90 μm, (D 90 -D 10 ) / D 50 It is between 1.00 and 3.

00.

18. The process for recovering 3-hydroxypropionic acid according to claim 1, wherein, The recovery rate of 3-hydroxypropionic acid is over 40%.

19. A slurry composition comprising a precipitate represented by the following structural formula 4 and 3-hydroxypropionic acid, [Structure 4] Cations (Anions) · pH2O in, The cation is Mg 2+ or Ca 2+ , The anion is SO42-. 2- PO4 3- or CO3 2- , p is the number of water molecules in the hydrate, which is an integer greater than or equal to 1. The particle size of the precipitate is greater than 10.0 μm.

20. The slurry composition according to claim 19, wherein: The moisture content of the precipitate is below 150%.

Images