KR20230080344A - Process of recovering 3-hydroxypropionic acid and hydrates of alkali metal salts - Google Patents

Abstract

The present invention relates to a process for recovering 3-hydroxypropionic acid and hydrates of alkali metal salts, comprising the following steps: forming and separating crystals of 3-hydroxypropionate from a concentrate containing 3-hydroxypropionic acid in the presence of an alkali metal salt; and adding acid to an aqueous solution containing the separated crystals of 3-hydroxypropionate to form and separate hydrates of an alkali metal salt and 3-hydroxypropionic acid.

Description

Recovery process of alkali metal salt hydrate and 3-hydroxypropionic acid {PROCESS OF RECOVERING 3-HYDROXYPROPIONIC ACID AND HYDRATES OF ALKALI METAL SALTS

The present invention relates to a process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.

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 selected as a Top 12 value-added bio-chemical by the US Department of Energy (DOE) in 2004, it has been actively researched in academia and industry.

The production of 3-hydroxypropionic acid is largely done by two methods, chemical and biological, but in the case of the chemical method, it is pointed out that it is not environmentally friendly due to the high cost of the initial material and the generation of toxic substances during the production process. , Eco-friendly bioprocesses are in the limelight.

Unlike other organic acids produced through a fermentation process, 3-hydroxypropionic acid exhibits high hydrophilicity and high water solubility and reactivity. Accordingly, it is difficult to apply conventional organic acid separation and purification processes such as precipitation or extraction.

The reactive extraction method is a method of extracting an organic acid using an active diluent such as an amine or an alcohol having good reactivity with the organic acid, and selective extraction of the organic acid is possible and the extraction efficiency is relatively high. Accordingly, an attempt has been made to apply the reaction extraction method even when separating and purifying 3HP. As an example, a method using trioctylamine (TOA) as the amine has been proposed, but there are problems in that the extraction efficiency of 3HP is low and a large amount of organic solvent is required. In addition, when tridecylamine is used as an amine, although the extraction efficiency of 3HP is higher than that of TOA, there is a problem in that an emulsion phenomenon in which an organic phase and an aqueous phase are not separated during extraction occurs.

Accordingly, it is necessary to develop a method for recovering high-purity 3-hydroxypropionic acid with high efficiency.

The present invention is to provide a method for recovering a hydrate of an alkali metal salt that can be recycled together with high purity 3-hydroxypropionic acid with high efficiency.

In the present specification, forming and isolating crystals of 3-hydroxypropionic acid in a concentrate containing 3-hydroxypropionic acid in the presence of an alkali metal salt; Forming an aqueous solution containing crystals of the 3-hydroxypropionate; and forming and separating an alkali metal salt hydrate and 3-hydroxypropionic acid by adding an acid to the aqueous solution containing the 3-hydroxypropionic acid crystals; A process for recovering a hydrate of an alkali metal salt and 3-hydroxypropionic acid is provided.

Hereinafter, a recovery process of an alkali metal salt hydrate and 3-hydroxypropionic acid according to a specific embodiment of the present invention will be described in more detail.

Unless it is specified that the steps constituting the manufacturing method described in this specification are sequential or continuous, or there is another special order, one step and the other steps constituting one manufacturing method are limited to the order described in the specification. not interpreted Therefore, the order of the constituent steps of the manufacturing method may be changed within the range easily understood by those skilled in the art, and in this case, the accompanying changes obvious to those skilled in the art are included in the scope of the present invention.

In the present specification, the alkali metal is meant to include both alkali metals and alkaline earth metals.

According to one embodiment of the invention, forming and separating crystals of 3-hydroxypropionic acid from a concentrate containing 3-hydroxypropionic acid in the presence of an alkali metal salt; Forming an aqueous solution containing crystals of the 3-hydroxypropionate; And adding an acid to the aqueous solution containing the crystals of 3-hydroxypropionic acid to form an alkali metal salt hydrate and 3-hydroxypropionic acid, and recovering the alkali metal salt hydrate and 3-hydroxypropionic acid, comprising the step of separating them. process can be provided.

The inventors of the present invention concentrating 3-hydroxypropionic acid in the presence of an alkali metal salt to form crystals of 3-hydroxypropionic acid can recover high-purity 3-hydroxypropionic acid with a high recovery rate, and the 3-hydroxypropionic acid It was confirmed through experiments that when an acid is added to an aqueous solution containing crystals of hydroxypropionic acid, it is possible to efficiently recover not only high-purity hydroxypropionic acid but also hydrates of alkali metal salts that can be recycled for various purposes, thereby completing the invention.

The crystals of the 3-hydroxypropionic acid salt may include a calcium salt of 3-hydroxypropionic acid, and a precipitate may be formed when an acid is added to the 3-hydroxypropionic acid salt. For example, when 3-hydroxypropionic acid salt is Ca(3HP) ₂ and sulfuric acid is used as an acid, a slurry composition containing a precipitate and 3-hydroxypropionic acid may be produced according to Reaction Formula 1 below. In addition, by filtering the precipitate from this slurry composition, 3-hydroxypropionic acid contained in the filtrate may be recovered.

[Scheme 1]

Ca(3HP) ₂ + H ₂ SO ₄ + 2H ₂ O -> CaSO ₄ 2H ₂ O + 2(3HP)

However, since precipitates such as CaSO ₄ ·2H ₂ O have a property of absorbing water well, such precipitates having a high water content can greatly reduce the fluidity of the slurry composition. For this reason, not only is it difficult to transfer the slurry composition, but it is also difficult to filter the precipitate from the slurry composition, and a large amount of 3-hydroxypropionic acid remains in the precipitate, resulting in a low recovery rate of 3-hydroxypropionic acid.

In contrast, in the recovery process according to the embodiment, the precipitate formed by adding an acid to an aqueous solution containing crystals of 3-hydroxypropionic acid formed from a concentrate containing 3-hydroxypropionic acid in the presence of an alkali metal salt. Since the particle size is large and the water content is remarkably low, the fluidity of the slurry composition including the same may be increased. Accordingly, filtration of the precipitate from the slurry composition becomes easy, and 3-hydroxypropionic acid can be recovered with a high recovery rate, and hydrates of alkali metal salts such as CaSO ₄ 2H ₂ O formed in the above process are also highly efficient. can be separated and recovered.

On the other hand, at the time of adding an acid to the aqueous solution containing the crystals of 3-hydroxypropionate, the temperature of the aqueous solution containing the crystals of 3-hydroxypropionate may be 0 ° C. or more and 90 ° C. or less, more specifically, 0 ° C. 15 ℃ or more, 30 ℃ or more, 35 ℃ or more, 40 ℃ or more, 45 ℃ or more, 50 ℃ or more, 55 ℃ or more, 90 ℃ or less, 80 ℃ or less, 75 ℃ or less, 70 ℃ or less, 65 ℃ may be below.

The particle size and moisture content of the precipitate may be affected by the temperature conditions of the process of adding the acid. For example, in the process of adding the acid, when the temperature of the aqueous solution is 25 ° C. or higher, the particle diameter (D ₅₀ standard) of the precipitate may be 30 μm or higher, and when the temperature of the aqueous solution is 60 ° C. or higher, the particle size of the precipitate ( D ₅₀ standard) may be 120 μm or more. That is, when acid is added to the crystals of 3-hydroxypropionate under the above-described temperature conditions, the precipitate may have a large particle size and a low moisture content.

In the step of adding the acid, a precipitate represented by Structural Formula 3 may be formed.

[Structural Formula 3]

Cation (Anion)·pH ₂ O

In Structural Formula 3, Cation is the cation of the alkali metal salt, the Anion is the anion of the acid, and p is the number of water molecules in the hydrate, which is an integer greater than or equal to 1.

The cation may be, for example, Na ⁺ , Mg ²⁺ or Ca ²⁺ , but in the case of Mg ²⁺ or Ca ²⁺ , crystals of 3-hydroxypropionate may be more effectively formed. In addition, the anion may be SO ₄ ^2- , PO ₄ ^3- or CO ₃ ^2- , but is not limited thereto.

In addition, the particle size of the precipitate may be 0.5 μm or more, 1.0 μm or more, 1.5 μm or more, 500.0 μm or less, 400.0 μm or less, 300.0 μm or less, 200.0 μm or less, 100 μm or less, 80 μm or less, 50 μm or less, 30 μm or less ㎛ or less, 20 μm or less, 8.0 μm or less, 7.0 μm or less, 6.0 μm or less, or 5.0 μm or less. Since the precipitate satisfies the above-mentioned particle size, the water content of the precipitate may be lowered, and thus, the flowability of the slurry containing the precipitate may be increased, and thus the filtration of the precipitate from the slurry may be facilitated. The particle size of the precipitate may be measured by scanning electron microscopy (SEM).

The precipitate may represent various particle shapes of prismatic, spherical, plate-shaped, and needle-shaped particles. At this time, the particle size of the precipitate is measured based on the longest straight-line distance among the straight-line distances between crystal planes included in the precipitate.

In addition, the moisture content of the precipitate may be 200% or less, 150% or less, 130% or less, 110% or less, 100% or less, 80% or less, 70% or less, 1% or more, 10% or more, or 30% or more. . If the moisture content of the precipitate is too high, the flowability of the slurry containing the precipitate is lowered, making it difficult to proceed with the process, and it is difficult to separate the precipitate from the slurry, making it difficult to recover 3-hydroxypropionic acid in high yield.

On the other hand, the aqueous solution containing the crystals of 3-hydroxypropionate should contain crystals of 3-hydroxypropionate in an aqueous solution containing crystals of 3-hydroxypropionate to ensure reaction efficiency due to acid addition, and also increase the relative content compared to other by-products. Therefore, the purity and efficiency of recovery of 3-hydroxypropionic acid can be further increased.

For example, the aqueous solution containing the crystals of 3-hydroxypropionate may contain 100 g/L or more of the crystals of 3-hydroxypropionate, and more specifically, the aqueous solution containing the crystals of 3-hydroxypropionate Crystals of 3-hydroxypropionate 100 g/L or more, 150 g/L or more, 200 g/L or more, 300 g/L or more, or 1,000 g/L or less, 900 g/L or less, 800 g/L or less, 700 g/L or less, and may include 650 g/L or less.

When acid is added to the aqueous solution containing the crystals of 3-hydroxypropionate, the concentration and addition amount of the acid can be determined in consideration of the amount of crystals of 3-hydroxypropionate in the aqueous solution,

For example, 0.1 M to 10 M acid may be added in an amount of 10% or 500% of the volume of the aqueous solution containing the crystals of 3-hydroxypropionate, or 100% by weight of the crystals of 3-hydroxypropionate. The acid added may be 20% by weight or more, 30% by weight or more, and 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less may be used.

When the amount of the added acid is too small, the conversion rate from crystals of 3-hydroxypropionic acid salt to 3-hydroxypropionic acid may be low, so the amount of 3-hydroxypropionic acid recovered may be small, and the amount of the acid added may be too small. In many cases, the concentration of unreacted cations and anions remaining in the finally obtained aqueous solution of 3-hydroxypropionic acid is too high, making it difficult to proceed with subsequent processes such as polylactic acid (PLA) manufacturing process or bio-acrylic acid (Bio-AA) manufacturing process. can affect

In the recovery step, the acid may be phosphoric acid, and the hydrate of the alkali metal salt may be phosphate. That is, in the recovery process, phosphoric acid may be added to the aqueous solution containing the 3-hydroxypropionic acid crystals to form and separate phosphate and 3-hydroxypropionic acid.

The inventors of the present invention confirmed through experiments that when phosphoric acid is added to an aqueous solution containing the crystals of 3-hydroxypropionic acid, not only high-purity hydroxypropionic acid but also phosphate that can be recycled for various purposes can be efficiently recovered, and the invention has been completed. The phosphate may be an inorganic phosphate or an organic phosphate, and the organic phosphate may be recovered and recycled through an organic solvent.

When phosphoric acid is added to 3-hydroxypropionate, a precipitate may be formed. For example, when 3-hydroxypropionate is Ca(3HP) ₂ and inorganic phosphoric acid is used as the acid, a precipitate is formed as shown in Scheme 5 below. And 3-hydroxypropionic acid may be produced, but is not limited thereto. On the other hand, when organic phosphoric acid is used as an acid, a slurry composition containing a precipitate and 3-hydroxypropionic acid may be produced in Scheme 6 below, but is not limited thereto. In addition, by filtering the precipitate from this slurry composition, 3-hydroxypropionic acid contained in the filtrate may be recovered.

[Scheme 5]

Ca(3HP) ₂ + H ₃ POn -> CaHPOn + 2(3HP)

In Scheme 5 above,

Said n is an integer of 2-5.

[Scheme 6]

3Ca(3HP) ₂ + 2[RO _z -H ₃ PO _m ] -> Ca ₃ [RO _z -(PO _m )] ₂ + 6(3HP)

In Scheme 6 above,

R may be an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a phenyl group,

z is 0 or 1;

m is an integer from 2 to 5;

In addition, the phosphate contained in the precipitate produced through Scheme 5 may be CaHPOn, and the precipitate may include a phosphate of Structural Formula 3 or a hydrate of phosphate, but is not limited thereto.

[Structural Formula 3]

Ca _x H _y (POn) _z mH ₂ O

x and z are each independently an integer from 1 to 10,

y is an integer from 0 to 10;

n is an integer from 2 to 5;

m is an integer from 0 to 5;

When phosphoric acid is added to the aqueous solution containing the 3-hydroxypropionate crystals, the concentration and addition amount of the acid may be determined in consideration of the amount of 3-hydroxypropionate crystals in the aqueous solution.

For example, phosphoric acid may be added in an equivalent amount of 0.8 to 2.0 times the equivalent of 3-hydroxypropionic acid in an aqueous solution containing crystals of 3-hydroxypropionate, and 0.1M to 10M phosphoric acid may be added to the 3-hydroxypropionic acid equivalent. It may be added in an amount of 10% or 500% of the volume of the aqueous solution containing crystals of hydroxypropionate, or phosphoric acid may be 20% by weight or more, 30% by weight or more with respect to 100% by weight of crystals of 3-hydroxypropionate, , 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less can be used.

When the amount of added phosphoric acid is too small, the conversion rate of 3-hydroxypropionic acid to 3-hydroxypropionic acid in crystals of 3-hydroxypropionic acid salt may be low, so the amount of 3-hydroxypropionic acid recovered may be small, and the amount of phosphoric acid added may be too small. In many cases, the concentration of unreacted cations and anions remaining in the finally obtained 3-hydroxypropionic acid aqueous solution is too high to produce acrylic acid (AA), poly 3-hydroxypropionic acid (P(3HP)), and PLH (Poly Lactate Hydracrylate) process or bio-acrylic acid (Bio-AA) manufacturing process, etc. On the other hand, since phosphoric acid can be used as a catalyst for the conversion reaction of acrylic acid (AA), when a trace amount of phosphoric acid remains, the manufacturing process of acrylic acid or the like can advantageously proceed with phosphoric acid as a catalyst.

The recovery process according to the embodiment is to separate the crystals of 3-hydroxypropionate from the concentrate after the step of forming the crystals of 3-hydroxypropionate, and to prepare an aqueous solution of the crystals of 3-hydroxypropionate. Further steps may be included.

As described above, as the crystals of 3-hydroxypropionate are produced in the fermentation process, the concentrate obtained by concentrating the fermentation broth may contain a large amount of impurities such as strains, carbon sources, and alkali metal salts in addition to the crystals of 3-hydroxypropionate. . However, in the process of recovering 3-hydroxypropionic acid according to the embodiment, the impurities can be removed by recovering crystals of 3-hydroxypropionic acid salt from the concentrated liquid by solid-liquid separation, and the separated 3-hydroxypropionic acid A solution prepared by dissolving salt crystals in a solvent such as distilled water may not contain the aforementioned impurities.

Therefore, when ammonia is added to the concentrate without separating the crystals of 3-hydroxypropionate from the concentrate, it is difficult to finally recover high-concentration and high-purity 3-hydroxypropionic acid because the concentrate contains a large amount of impurities. can

For example, crystals of 3-hydroxypropionate may be separated from the concentrate using a filter flask and a vacuum pump, and the separated crystals of 3-hydroxypropionate may be dissolved in a solvent such as distilled water to obtain 3-hydroxypropionate. Aqueous solutions of crystals of propionate can be prepared.

The solution containing crystals of 3-hydroxypropionate may contain crystals of 3-hydroxypropionate at a concentration of 100 g/L or more, 150 g/L or more, or 200 g/L or more, and 800 g/L or less, 750 It may be included at a concentration of less than g/L and less than 700 g/L. If the concentration of the crystals of 3-hydroxypropionate contained in the crystal-containing solution of 3-hydroxypropionate is too low, the concentration of the finally recovered 3-hydroxypropionic acid may be low, and the crystals of 3-hydroxypropionate If the concentration of is too high, 3-hydroxypropionic acid may be precipitated, or the solid concentration after precipitation may be too high, and the recovery rate may be reduced due to a decrease in fluidity.

Thereafter, an acid may be added to the aqueous solution of the crystals of 3-hydroxypropionate to form a slurry composition containing a precipitate and 3-hydroxypropionic acid, and the aqueous solution of the crystals of 3-hydroxypropionate before the addition of the acid is specified By stirring in the temperature range and maintaining this temperature condition until the time of acid addition, the above precipitate may be formed. The precipitate formed in this specific temperature range may have a large particle diameter and a low moisture content.

also, The recovery process according to the embodiment may further include filtering the precipitate and washing the filtered precipitate after the step of adding the acid.

The precipitate can be filtered from the slurry composition using a filter flask and a vacuum pump, etc., and hydrates of alkali metal salts can be recovered from the precipitate, and the filtered precipitate can be washed to remove 3-hydroxypropionic acid contained in the precipitate. Additional recovery is possible.

Therefore, the 3-hydroxypropionic acid may be included in the filtrate obtained by filtering the precipitate. In addition, 3-hydroxypropionic acid may be included in the washing solution for washing the precipitate. However, since the washing liquid may contain other impurities in 3-hydroxypropionic acid, 3-hydroxypropionic acid may be recovered from the filtrate obtained by filtering the washing liquid.

Components such as hydrates of alkali metal salts contained in the precipitate can be confirmed through known methods such as X-ray glare spectrometry (XRF), and also X-ray diffraction analyzer (Bruker AXS D4-Endeavor XRD) The type and crystal form of the substance can be confirmed by doing so. In addition, the moisture content of the hydrate of the alkali metal salt can be checked with a moisture meter, and impurities other than the hydrate of the alkali metal salt can be determined by nuclear magnetic resonance spectroscopy (NMR), high performance liquid chromatography (HPLC), or X-ray glare spectrometry (XRF). ) The component can be confirmed through a known method such as.

As described above, the hydrate of an alkali metal salt obtained in the process of recovering 3-hydroxypropionic acid derived from an environmentally friendly bio process is naturally radioactive, unlike the by-product obtained in the process of recovering 3-hydroxypropionic acid obtained from a known chemical fixation process. Mineral-derived by-products such as nuclides (radium (226Ra), thorium (232Th), potassium (40K)) may not exist or may have high whiteness.

For example, in the process of recovering 3-hydroxypropionic acid derived from an eco-friendly bioprocess, dihydrate, hemihydrate, and anhydrite are included at least 90% of the total content, especially CaSO4 that does not contain natural radionuclides. Hydrates of alkali metal salts can be recovered.

In one embodiment, the 3-hydroxypropionic acid recovery rate of the 3-hydroxypropionic acid recovery process provided by the present invention is 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, such as, 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%, 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 is not limited thereto. The recovery rate may be calculated based on weight.

The step of forming and separating an alkali metal salt hydrate and 3-hydroxypropionic acid by adding an acid to the aqueous solution containing the 3-hydroxypropionic acid crystals includes the addition of an acid containing the alkali metal salt hydrate and 3-hydroxypropionic acid. The method may include separating the hydrate of the alkali metal salt from the solution and electrodialysis the acid-added solution from which the hydrate of the alkali metal salt is separated.

In particular, the recovered 3-hydroxypropionic acid may contain various impurities and some of the 3-hydroxypropionic acid may remain in the form of a salt. The hydrate of the alkali metal salt is first separated and the remaining filtrate is electrodialyzed to remove impurities. The content can be greatly reduced and the purity of 3-hydroxypropionic acid among the finally recovered components can be greatly increased.

The electrodialysis may use a constant voltage method or a constant current method, and electricity may be applied to the electrodialysis device to purify impurities such as other ions in the acid addition solution in which the hydrate of the alkali metal salt is separated, and also 3-hydroxy 3-hydroxypropionic acid of high purity can be recovered by converting components present as propionic acid salts into 3-hydroxypropionic acid.

Conventionally, the fermented liquid was directly put into an electrodialysis device to remove impurities, but there was a problem in that the cation dissociated from 3-hydroxypropionate clogged the membrane or caused fouling, reducing the efficiency of the recovery process.

However, in the recovery process of one embodiment, after first forming crystals of 3-hydroxypropionate, acid is added to separate hydrates of alkali metal salts and 3-hydroxypropionic acid, and then 3-hydroxypropionic acid is separated by electrodialysis. Due to the recovery of propionic acid, problems such as the above-described fouling phenomenon can be prevented, and high-purity 3-hydroxypropionic acid can be recovered with high efficiency.

The electrodialysis amount is not particularly limited during the electrodialysis, but may be selected from, for example, 5 to 50 Flux, or 10 to 30 Flux.

The electrodialysis may use a conventionally known electrodialysis device, an electrodialysis method, or an electrodialysis system. For example, an electrodialysis system may include an electrodialysis tank having two opposing electrodes and a cation-selective membrane and/or anion-selective membrane positioned between the electrodes; a supply tank for supplying a reactant to the electrodialysis tank; a desalination tank for recovering a desalination product formed while the reactant supplied to the electrodialysis tank passes through the electrodialysis tank; A concentration tank for recovering cations, anions, or salts formed while the reactant supplied to the electrodialysis tank passes through the electrodialysis tank; may be provided.

Electrodialysis of the acid-added solution from which the hydrate of the alkali metal salt is separated; In the desalination tank for recovering the desalination product formed by electrodialysis of the acid-added solution from which the hydrate of the alkali metal salt is separated, the conductivity is 50% compared to the initial value. or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less.

When the electrodialysis time or the amount of electrodialysis increases, the rate at which some impurities are removed may increase, but the recovery target 3-hydroxypropionic acid may move to the concentration tank, and the overall process time may increase significantly.

The initial electrical conductivity of the desalination tank is not particularly limited, but is 5 mS/cm or more and 200 mS/cm or less, 10 mS/cm or more and 180 mS/cm or less, 20 mS/cm or more and 150 mS/cm or less, or 30 mS/cm or more. It may be 130 mS/cm or less. If the initial electrical conductivity of the desalination tank is too low, it may be difficult to separate the ionic material to be separated, and if it is too high, desalination takes a long time and the degree of contamination of the separation membrane may increase.

A cation exchange resin column is used in the process of recovering 3-hydroxypropionic acid formed after the process of adding an acid to the aqueous solution containing the crystals of 3-hydroxypropionic acid to form a hydrate of an alkali metal salt and 3-hydroxypropionic acid. may be

Specifically, the step of forming and separating the hydrate of the alkali metal salt and 3-hydroxypropionic acid by adding an acid to the aqueous solution containing the crystals of 3-hydroxypropionic acid salt, the solution containing the formed 3-hydroxypropionic acid contacting a cation exchange resin column; and recovering 3-hydroxypropionic acid from the solution contacting the cation exchange resin column.

The cation exchange resin column serves to convert 3-hydroxypropionic acid present in a solution containing 3-hydroxypropionic acid into 3-hydroxypropionic acid, and thus, higher-purity 3-hydroxypropionic acid with higher efficiency. can be separated and recovered.

On the other hand, the cation exchange resin may be a polymer including a functional group capable of ion exchange in the matrix, wherein the functional group capable of ion exchange introduced into the matrix is -COOH, -SOOH, -POOH, such as hydrogen cation (H ⁺ ) exchange. It may be in acid form.

In addition, polystyrene, an acrylic polymer, etc. may be used as the matrix of the cation exchange resin, and various matrixes such as homopolymer, co-polymer, block-polymer, and random copolymer may be used.

The particles of the cation exchange resin may have a spherical or irregular shape, and the particle size distribution range of the cation exchange resin may be 0.3 mm to 1.2 mm.

The exchange efficiency of the cation exchange resin may be 1.2 eq to 2.0 eq, or 1.6 eq to 1.9 eq in consideration of the stability of the cation exchange resin and the degree of ion desorption in the cation exchange resin.

In addition, the cation exchange resin may be used alone or in combination of two or more types, and since the exchange efficiency differs depending on the type of resin used, the resin may be selected considering the size, shape, exchanger, etc. of the particle.

Meanwhile, the resin volume of the cation exchange resin column may be 10 BV or more, 11 BV or more, or 12 BV or more. The resin volume (BED VOLUME; BV) means the volume occupied by the filler in the column. If the resin volume content of the cation exchange resin column is too low, exchange efficiency decreases during ion exchange, and if the resin volume content is too high, ion exchange time increases, which may be uneconomical.

Meanwhile, in the recovery process according to the embodiment, crystals of 3-hydroxypropionic acid salt may be formed in the concentrate containing 3-hydroxypropionic acid in the presence of an alkali metal salt before the acid addition process.

The concentrate containing 3-hydroxypropionic acid may contain 3-hydroxypropionic acid at a concentration of 300 g/L or more, 350 g/L or more, 400 g/L or more, 450 g/L or more, or 500 g/L or more. It may contain 3-hydroxypropionic acid at a concentration of 900 g/L or less, 850 g/L or less, or 800 g/L or less. Whether or not crystals of 3-hydroxypropionic acid are formed appears to be influenced by the presence of an alkali metal salt and the concentration of 3-hydroxypropionic acid in the concentrate.

In addition, when the concentration of the crystals of 3-hydroxypropionic acid in the concentrate is higher than the water solubility of the crystals of 3-hydroxypropionic acid, the crystals of 3-hydroxypropionic acid can be more easily produced. .

For example, since the water solubility of Ca(3HP) ₂ , which is the crystal of 3-hydroxypropionic acid, is 450 g/L at room temperature, the concentration of 3-hydroxypropionic acid in the concentrate is 450 g/L. If it exceeds, the formation of Ca(3HP) ₂ crystals may be promoted. In addition, since the water solubility of Mg(3HP) ₂ , which is a crystal of 3-hydroxypropionic acid, is 250 g/L at room temperature, the concentration of 3-hydroxypropionic acid in the concentrate exceeds 250 g/L. In this case, the production of Mg(3HP) ₂ crystals can be promoted.

While containing the alkali metal salt, from the concentrate satisfying the above concentration It is possible to form crystals of 3-hydroxypropionate, and the alkali metal salt may be selected without limitation from the purpose range for forming crystals of 3-hydroxypropionate. For example, the alkali metal salt is Na ⁺ , Mg ²⁺ And Ca ²⁺ may include one or more cations selected from the group consisting of, but when using Mg ²⁺ or Ca ²⁺ cations, or salts thereof, crystals of 3-hydroxypropionate may be more effectively formed. . For example, the alkali metal salt may be Ca(OH) ₂ , Mg(OH) ₂ , or a mixture thereof.

The alkali metal salt is added and remains in the process of producing the 3-hydroxypropionic acid fermentation broth, or added during the process of forming crystals of 3-hydroxypropionic acid in the concentrate containing 300 g/L or more of 3-hydroxypropionic acid. It can be. In addition, the concentration of the alkali metal salt may be 10% to 100%, or 30% to 90% of the concentration of 3-hydroxypropionic acid, for example, 10 to 900 g/L, 50 to 800 g/L, or 100 to 900 g/L. It may be present in the concentrate at a concentration of 700 g/L or 200 to 600 g/L.

In addition, the step of forming crystals of 3-hydroxypropionic acid salt from the concentrate containing 3-hydroxypropionic acid may further include a step of contacting the concentrate of 3-hydroxypropionic acid with a non-solvent. When contacting with a non-solvent, crystals of the 3-hydroxypropionate may be more easily formed. When the concentrated solution of 3-hydroxypropionic acid formed in the presence of the alkali metal salt is brought into contact with a non-solvent, the rate of crystal formation is controlled compared to the crystals produced at a faster rate by over-concentration, so that crystals of pure 3-hydroxypropionic acid salt are formed and then crystallized size can be increased. In the case of the crystal of 3-hydroxypropionate, it contains a very low content of impurities inside the crystal and has excellent filterability due to the even crystal formation, so it is easy to purify and has excellent shape stability and heat stability in the crystal state. , It is possible to efficiently mass-produce 3-hydroxypropionic acid with high purity.

For example, when a non-solvent is brought into contact with a concentrated solution of 3-hydroxypropionic acid formed in the presence of an alkali metal salt, an alkali metal salt of 3-hydroxypropionic acid is generated, and the concentration of the alkali metal salt of 3-hydroxypropionic acid increases. Microcrystals are formed and solid-liquid phase separation occurs. Then, as crystallization progresses, the alkali metal salt of 3-hydroxypropionic acid grows into solid crystals (crystals of 3-hydroxypropionic acid salt), glycerol, Crystals of 3-hydroxypropionate produced while being separated from liquid impurities such as 1,3-propanediol contain impurities at a very low content. At this time, the non-solvent serves to promote the crystallization of the alkali metal salt of 3-hydroxypropionic acid, so that the solid-liquid separation ability is increased and crystals of 3-hydroxypropionic acid salt having higher purity can be produced.

The volume ratio between the concentrate of 3-hydroxypropionic acid and the non-solvent may be determined in consideration of the concentration of 3-hydroxypropionic acid or the volume of the concentrate and the non-solvent, for example, the concentrate and the non-solvent may be 1:0.5 to 1: 20, or from 1:0.5 to 1:10, or from 1:0.8 to 1:8, or from 1:1 to 1:5.

If the volume of the non-solvent is too small compared to the concentrated solution, the concentration at which crystals are formed is high, so the rate of crystal formation is increased, so that pure crystal particles cannot be slowly formed and irregular crystal particles can be quickly formed, solid-liquid It may be difficult to separate liquid impurities and alkali metal salts of 3-hydroxypropionic acid to be purified due to low resolution. In addition, if the volume of the non-solvent is too large compared to the concentrated solution, the crystals formed may be melted and released in some cases due to the solubility of the non-solvent, and the time in the crystal filtration process after crystal formation increases, leading to an increase in the amount of waste liquid may not be economical.

The non-solvent may include an alcohol-based non-solvent, a ketone-based non-solvent, a nitrile-based non-solvent, or a mixture of two or more thereof, and more specifically, one or more alcohol-based non-solvents may be used.

The ketone-based non-solvent is one selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isoamyl ketone, isophorone and di-(isobutyl) ketone may contain more than The alcohol-based non-solvent is methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, benzyl alcohol, cyclohexanol, diacetone alcohol, ethylene glycol monoethyl ether, diethylene It may include at least one selected from the group consisting of glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-methoxyethanol and 1-decanol. The nitrile non-solvent is acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile , Difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, may include one or more selected from the group consisting of 4-fluorophenylacetonitrile.

Forming crystals of 3-hydroxypropionate by contacting the concentrate with the non-solvent is 0 ° C or more, 15 ° C or more, 30 ° C or more, 35 ° C or more, 40 ° C or more, 45 ° C or more, 50 ° C or more, 55 ° C or higher, and may be performed at a temperature of 100 °C or less, 90 °C or less, 80 °C or less, 75 °C or less, 70 °C or less, 65 °C or less, or 0 °C to 100 °C.

At this time, the concentration may be adjusted to the above temperature range by adding a non-solvent at the above-described temperature to the concentrate or by heating or cooling in a state in which the concentrate and the non-solvent are mixed.

The crystal of 3-hydroxypropionate may have the form of Structural Formula 1 or Structural Formula 2 below. That is, the crystal of 3-hydroxypropionate may include 3-hydroxypropionate in the form of Structural Formula 1 or Structural Formula 2 below.

In Structural Formulas 1 and 2 below, Cation represents a cation, 3HP represents 3-hydroxypropionic acid that binds to a cation, and n represents an integer of 1 or more as the number of 3HP that binds to a cation. (3HP) The number of water molecules bonded to n, which is an integer greater than or equal to 1. The cation may be, for example, Na ⁺ , Mg ²⁺ or Ca ²⁺ , but in the case of Mg ²⁺ or Ca ²⁺ , crystals of 3-hydroxypropionate may be more effectively formed.

[Structural Formula 1]

Cation(3HP) _n

[Structural Formula 2]

Cation(3HP) _n mH ₂ O

In addition, the step of forming crystals of 3-hydroxypropionate may further include stirring the concentrate.

The stirring step is 0 to 70 degrees Celsius, 0 to 60 degrees Celsius, 0 to 50 degrees Celsius, 0 to 40 degrees Celsius, 0 to 35 degrees Celsius, 0 to 30 degrees Celsius, 10 to 70 degrees Celsius, 10 to 10 degrees Celsius 60 degrees Celsius, 10 to 50 degrees Celsius, 10 to 40 degrees Celsius, 10 to 35 degrees Celsius, 10 to 30 degrees Celsius, 15 to 70 degrees Celsius, 15 to 60 degrees Celsius, 15 to 50 degrees Celsius, 15 to 40 degrees Celsius ( For example, room temperature) and / or 100 to 2000 rpm, 100 to 1500 rpm, 100 to 1000 rpm, 100 to 500 rpm, 100 to 400 rpm, or 200 to 400 rpm (eg, about 300 rpm) conditions.

The crystal of 3-hydroxypropionate may have a particle size distribution D ₅₀ of 20 μm or more, 25 μm or more, 30 μm or more, or 35 μm or more, and 300 μm or less, 250 μm or less, 200 μm or less, 150 μm, or 90 μm. Or less, it may be 85 μm or less, 80 μm or less, or 75 μm or less.

In addition, the particle size distribution D ₁₀ of the crystals of 3-hydroxypropionate may be 5 μm or more and 40 μm or less, 8 μm or more and 35 μm or less, and 10 μm or more and 30 μm or less, and the particles of the 3-hydroxypropionate crystals The size distribution D ₉₀ may be 50 μm or more and 200 μm or less, 60 μm or more and 190 μm or less, 65 μm or more and 180 μm or less, and 70 μm or more and 175 μm or less.

The particle size distributions D ₅₀ , D ₁₀ , and D ₉₀ mean particle diameters corresponding to 50%, 10%, and 90% of the cumulative volume, respectively, in the particle size distribution curve of the particles, and the D ₅₀ , D ₁₀ , and D ₉₀ can be measured using, for example, a laser diffraction method. The laser diffraction method is generally capable of measuring particle diameters of several millimeters in the submicron region, and can obtain results with high reproducibility and high resolution.

If the particle size distributions D ₅₀ , D ₁₀ , and D ₉₀ of the crystals of 3-hydroxypropionate are too large, impurities to be removed during crystallization may be included in the crystals, resulting in reduced purification efficiency. this can be lowered

Meanwhile, (D ₉₀ -D ₁₀ )/D ₅₀ of the crystal of 3-hydroxypropionate may be 1.00 or more and 3.00 or less, 1.20 or more and 2.80 or less, 1.40 or more and 2.60 or less, or 1.60 or more and 2.40 or less.

In addition, the crystals of 3-hydroxypropionate may have a volume average particle diameter of 30 μm or more and 100 μm or less, 35 μm or more and 95 μm or less, and 40 μm or more and 90 μm or less, and have a number average particle diameter of 1 μm or more and 30 μm or less, 3 ㎛ or more and 25 μm or less, 5 μm or more and 20 μm or less, and the volume average particle diameter may 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.

If the volume average particle diameter, number average particle diameter, and volume average particle diameter of the crystal of 3-hydroxypropionate are too large, impurities to be removed during crystallization may be included in the crystal, resulting in poor purification efficiency. this can be lowered

In addition, the aspect ratio (LW Ratio; Length to width ratio) and average aspect ratio in the particle size distribution (D ₁₀ , D ₅₀ , D ₉₀ ) of the crystals of 3-hydroxypropionate are 0.50 or more and 3.00 or less, 0.70 or more and 2.80 or less, respectively. , may be greater than or equal to 1.00 and less than or equal to 2.50. If the aspect ratio of the crystals of 3-hydroxypropionate is too large, problems of flowability and clogging may occur during transfer of the crystals, and if the aspect ratio is too small, liquid permeability may be reduced during filtration of the crystals.

The water content contained in the crystal of the 3-hydroxypropionate can be measured by the Karl Fischer method, and the water content contained in the crystal of the 3-hydroxypropionate is 200 ppm or more and 5000 ppm or less. , 250 ppm or more and 4800 ppm or less, 300 ppm or more and 4600 ppm or less, and 350 ppm or more and 4400 ppm or less.

At this time, the water contained in the crystals of the 3-hydroxypropionate means attached water contained between the crystals, not crystal water (for example, Ca(3HP) ₂ ·2H ₂ O). In addition, if the water content contained in the crystals of 3-hydroxypropionate is excessively high, it may be recovered in the form of a slurry rather than a crystalline solid, or impurities may be contained within the water, which may cause a problem in improving or decreasing the purity.

In the recovery process according to the embodiment, as described below, 3-hydroxypropionic acid is produced through a process such as fermenting a strain having 3-hydroxypropionic acid-producing ability, and the crystal of 3-hydroxypropionic acid salt is It may contain radioactive carbon isotopes ( ¹⁴ C).

A radioactive carbon isotope ( ¹⁴ C) is approximately 1 in 10 ¹² carbon atoms in the Earth's atmosphere, has a half-life of about 5700 years, and the carbon stock is composed of cosmic rays and ordinary nitrogen ( ¹⁴ N). It can be abundant in the upper atmosphere due to nuclear reactions that On the other hand, in fossil fuels, radiocarbon isotopes decay long ago and ^{the 14} C ratio may be practically zero. When bio-derived raw materials are used as raw materials for 3-hydroxypropionic acid or fossil fuels are used together with them, the content of radioactive carbon isotopes (pMC; percent modern carbon) contained in 3-hydroxypropionic acid according to the ASTM D6866-21 standard and bio-carbon content can be measured.

As the measurement method, for example, carbon atoms included in the target compound may be converted into graphite or carbon dioxide gas and measured using a mass spectrometer or liquid scintillation spectroscopy. At this time, an accelerator for separating ¹⁴ C ions from ¹² C ions together with the mass spectrometer may be used to separate two isotopes, and the content and content ratio may be measured with a mass spectrometer.

The crystal of 3-hydroxypropionate may have a radiocarbon isotope content of 20 pMC (percent modern carbon) or more, 50 pMC or more, 90 pMC or more, or 100 pMC or more, measured according to the ASTM D6866-21 standard, and The content may be 20% by weight or more, 50% by weight or more, 80% by weight, 90% by weight or 95% by weight.

The radiocarbon isotope ratio (pMC) means the ratio of the radiocarbon isotope ( ¹⁴ C ) contained in the crystal of the 3-hydroxypropionate to the radiocarbon isotope ( ¹⁴ C ) of the modern standard reference material, Since the 1950s nuclear test program is still in effect and not extinguished, it may be greater than 100%.

In addition, the bio-carbon content refers to the bio-carbon content with respect to the total carbon content included in the crystal of the 3-hydroxypropionate, and the larger the value, the more eco-friendly the compound may be.

On the other hand, if the radiocarbon isotope content (pMC) and biocarbon content of the crystal of 3-hydroxypropionate are too low, eco-friendliness is reduced, and it may not be regarded as a bio-derived material.

The crystalline state of the crystal of the 3-hydroxypropionate can be confirmed through a peak in an X-ray diffraction (XRD) graph.

For example, when the crystal of 3-hydroxypropionate is analyzed by X-ray diffraction (XRD), a 2θ value may appear between crystal lattice peaks in the range of 8 to 22°.

For example, when the concentrate contains magnesium hydroxide (Mg(OH) ₂ ) and the crystal of 3-hydroxypropionate formed is Mg(3HP) ₂ , X-ray diffraction for Mg(3HP) ₂ ( Upon XRD) analysis, a peak between the crystal lattice due to the bond between 3-hydroxypropionic acid and magnesium may appear in a 2θ value range of 8 to 15°. These peaks show different results from the X-ray diffraction (XRD) analysis results for magnesium hydroxide (Mg(OH) ₂ ) or magnesium sulfate (Mg(SO ₄ )), and the 2θ value as a result of the X-ray diffraction (XRD) analysis When a specific peak appears in the range of 8 to 15°, it can be confirmed that a crystal of Mg(3HP) ₂ is formed.

Specifically, upon X-ray diffraction (XRD) analysis of Mg(3HP) ₂ , 3 or more, 4 or more, or 5 or more peaks may appear in the range of 2θ values from 8 to 15 °, for example, Peaks may appear in the ranges of 2θ values 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 °.

In addition, when calcium hydroxide (Ca(OH) ₂ ) is included in the concentrate and the crystal of 3-hydroxypropionate formed is Ca(3HP) ₂ , X-ray diffraction (XRD) analysis of Ca(3HP) ₂ At this time, a peak between 3-hydroxypropionic acid and the crystal lattice due to calcium bonding may appear in the range of 2θ value of 10 to 22 °. These peaks show different results from the X-ray diffraction (XRD) analysis results for calcium hydroxide (Ca(OH) ₂ ) or calcium sulfate (Ca(SO ₄ )), and the 2θ value as a result of the X-ray diffraction (XRD) analysis When a specific peak appears in the range of 10 to 22°, it can be confirmed that a crystal of Ca(3HP) ₂ is formed.

Specifically, during X-ray diffraction (XRD) analysis of Ca(3HP) ₂ , 3 or more, 5 or more, 7 or more, or 9 or more peaks may appear in the range of 2θ values of 10 to 22 °, For example, the 2θ value is 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°, 21.5 to 22 .0 Each peak may appear in the range of °.

On the other hand, the angle of incidence (θ) means the angle formed by the crystal plane and the X-ray when the X-ray is irradiated to a specific crystal plane, and the peak is 2 of the incident angle of the X-ray at which the horizontal axis (x axis) in the x-y plane is incident. As the double (2θ) value of the angle of incidence of the incident X-ray, which is the horizontal axis (x-axis) on the graph where the vertical axis (y-axis) in the x-y plane is the diffraction intensity, increases in the positive direction, The first derivative (slope of the tangent line, dy/dx) of twice the incident angle (2θ) of X-rays, the horizontal axis (x-axis), for the diffraction intensity, the vertical axis (y-axis), changes from a positive value to a negative value , means the point where the first derivative (slope of the tangent line, dy/dx) is zero.

In addition, the crystal of 3-hydroxypropionate has an X-ray diffraction (XRD) analysis of spacing (d value) between atoms in the crystal of 1.00 Å or more and 15.00 Å or less, 1.50 Å or more and 13.00 Å or less, 2.00 Å or more 11.00 It may be Å or less, 2.50 Å or more and 10.00 Å or less.

For example, when the crystal of 3-hydroxypropionate is Mg(3HP) ₂ , the spacing (d value) between atoms in the crystal of the peak appearing in the range of 2θ value from 8 to 15 ° is 1.00 Å or more. It may be 15.00 Å or less, 2.00 Å or more and 13.00 Å or less, 4.00 Å or more and 11.00 Å or less, 5.50 Å or more and 10.00 Å or less.

In addition, when the crystal of 3-hydroxypropionate is Ca(3HP) ₂ , the spacing (d value) between atoms in the crystal of the peak appearing in the range of 2θ value from 10 to 22 ° is 1.00 Å or more and 15.00 Å. Or less, 2.00 Å or more and 13.00 Å or less, 3.00 Å or more and 10.00 Å or less, 3.40 Å or more and 9.00 Å or less, 4.00 Å or more and 8.50 Å or less.

In addition, the crystal of 3-hydroxypropionate may have a glass transition temperature of -55 °C or more and -30 °C or less, a melting point of 30 °C or more and 170 °C or less, and a crystallization temperature of 25 °C or more and 170 °C or less.

The glass transition temperature, melting point, and crystallization temperature of the crystal of 3-hydroxypropionate may be measured by differential scanning calorimetry (DSC), and the temperature increase rate at the time of measurement may be 1 to 20 °C/min. In addition, the crystal of 3-hydroxypropionate may have a glass transition temperature of -55 °C or more -30 °C or less, -50 °C or more -35 °C or less, -45 °C or more -40 °C or less. In addition, the melting point of the crystal of 3-hydroxypropionate may be 30 ℃ or more and 170 ℃ or less, 31 ℃ or more and 160 ℃ or less, 32 ℃ or more and 150 ℃ or less. In addition, the crystallization temperature of the crystal of 3-hydroxypropionate may be 25 ℃ or more and 170 ℃ or less, 27 ℃ or more and 160 ℃ or less, 30 ℃ or more and 150 ℃ or less. In addition, the crystallization stability period of the crystal of the 3-hydroxypropionate may be -40 ℃ to 150 ℃.

The purity of 3-hydroxypropionate contained in the crystals of 3-hydroxypropionate may be calculated as a percentage (%) of the mass of the compound having the structural formulas of Formula 1 and/or Formula 2 relative to the mass of the total recovered crystals. can For example, the purity of 3-hydroxypropionate contained in the crystal of 3-hydroxypropionate is 70% or more, 80% or more, 90% or more, 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.

The recovery process according to one embodiment, prior to the step of forming crystals of 3-hydroxypropionic acid, fermenting a strain having 3-hydroxypropionic acid-producing ability to produce a 3-hydroxypropionic acid fermentation broth and the Concentrating the fermentation broth to form a concentrate containing 300 g/L or more of the 3-hydroxypropionic acid may be included.

The strain having the ability to produce 3-hydroxypropionic acid may contain at least one selected from the group consisting of glycerol dehydratase and aldehyde dehydrogenase, or a gene encoding the two proteins there is.

In one example, the 3-hydroxypropionic acid producing strain may further include a gene (gdrAB) encoding glycerol dehydratase reactivator (GdrAB). In one example, the strain producing 3-hydroxypropionic acid may be a strain capable of biosynthesizing additional vitamin B12.

The glycerol dehydratase may be encoded by dhaB (GenBank accession no. U30903.1) gene, but is not limited thereto. The dhaB gene may be an enzyme derived from Klebsiella pneumonia, but is not limited thereto. The gene encoding the glycerol dehydratase may include a gene encoding dhaB1, dhaB2 and/or dhaB3. The glycerol dehydratase protein _and the gene encoding it are genes and/or It may contain variations in the amino acid sequence.

The gene (aldH) encoding the aldehyde dehydrogenase (ALDH) is, for example, aldH (GenBank Accession no. U00096.3; EaldH) derived from Escherichia coli or E. coli K12 MG1655 cell line. gene, the puuC gene derived from K. pneumoniae, and/or the KGSADH gene derived from Azospirillum brasilense, but is not limited thereto. The aldehyde dehydrogenase protein and the gene encoding it may include mutations in the gene and/or amino acid sequence within the range of maintaining an activity for producing 3-hydroxypropionic acid from 3-hydroxypropanal.

The medium for producing the fermentation broth may be selected without limitation from a range of purposes for producing 3-hydroxypropionic acid. In one example, the medium may contain glycerol as a carbon source. In another example, the medium may be waste glycerol (crude glycerol) and/or pretreated waste glycerol, but is not limited thereto. In one example, the medium for production may further include vitamin B12.

In the step of fermenting the strain having the ability to produce 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 is 1 to 200 g/L , 10 to 150 g/L, 30 to 130 g/L or 40 to 100 g/L.

In addition, the fermentation may be neutral fermentation, for example, pH may be maintained in the 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 thereto. The pH range can be appropriately adjusted as needed. The alkali metal salt may be added for the neutral fermentation. The alkali metal salt may include Mg ²⁺ , Ca ² or a mixture thereof. In addition, the alkali metal salt may be Ca(OH) ₂ or Mg(OH) ₂ , but is not limited thereto.

The recovery process according to the embodiment may include, after producing the 3-hydroxypropionic acid fermentation broth, removing (separating) cells from the fermentation broth; Purifying and/or decolorizing the fermentation broth and/or the fermentation broth from which cells are removed; and/or filtering the fermentation broth and/or the fermentation broth from which cells are removed.

Removal (separation) of the cells may be performed by selecting a method known in the art without limitation within the range of cell (strain) removal purposes. In one example, the separation of the cells may be performed by centrifugation.

The step of purifying and/or decolorizing the fermentation broth and/or the fermentation broth from which cells are removed may be performed by selecting a method known in the art without limitation within the range of the purpose of purification of the fermentation broth. It may be performed by removing the activated carbon after mixing with the fermentation broth, but is not limited thereto.

The step of filtering the fermentation broth and/or the fermentation broth from which cells are removed limits methods known in the art in the scope of the purpose of removal of solid impurities, removal of proteins and/or materials with hydrophobic functional groups, and/or decoloration. It may be performed by selecting without, for example, filter filtration, and / or activated carbon filtration method may be performed, but is not limited thereto.

In the recovery process according to the embodiment, after the step of fermenting the strain having the ability to produce 3-hydroxypropionic acid to produce a 3-hydroxypropionic acid fermentation broth, the fermentation broth is concentrated to obtain a concentrate containing the 3-hydroxypropionic acid. It may include the step of forming.

Concentration of the fermentation broth may be performed by evaporation of the fermentation broth (eg, a liquid component of the fermentation broth).

The concentration may be performed by any means commonly available for evaporating the liquid component of the fermentation broth, for example, rotary evaporation, evaporation concentration, vacuum concentration, vacuum concentration, etc., but is not limited thereto. .

In one example, the concentration of 3-hydroxypropionic acid in the fermentation broth after concentration is 2 to 50 times, 2 to 40 times, 2 to 30 times, 2 to 20 times, 2 to 10 times, 5 to 50 times, compared to before concentration. It may be increased by 5 to 40 times, 5 to 30 times, 5 to 20 times, or 5 to 10 times.

In addition, the recovery process according to the embodiment may further include forming a hydroxide of the alkali metal by reacting the hydrate of the alkali metal salt with ammonia water.

The present inventors confirmed through experiments that the hydrate of the alkali metal salt and ammonia water can be reacted to recover the hydroxide of the alkali metal that can be recycled for various purposes with a high recovery rate, and completed the invention.

A hydroxide of an alkali metal may be formed by reacting an anhydride formed by drying a hydrate of an alkali metal salt such as CaSO ₄ ·2H ₂ O with aqueous ammonia. For example, the anhydride may be calcium sulfate (CaSO ₄ ), and the calcium sulfate and ammonia water react as shown in Reaction Formula 2 below to form hydroxides of alkali metals such as Ca(OH) ₂ and ammonium sulfate.

[Scheme 2]

CaSO ₄ + 2NH ₃ H ₂ O -> Ca(OH) ₂ + (NH ₄ ) ₂ SO ₄

Alkali metal hydroxides such as Ca(OH) ₂ are reused as alkali metal salts in the step of forming crystals of 3-hydroxypropionic acid salts, or reused as neutralizers in the process of fermenting strains capable of producing 3-hydroxypropionic acid. Neutral fermentation can take place.

In addition, since the ammonium sulfate can be recycled as sulfuric acid fertilizer through processes such as concentration and drying, the recovery process according to the embodiment is eco-friendly because waste generation is reduced, and economical due to reuse of the alkali metal hydroxide and the like. In-process construction is possible.

In addition, the recovery process may further include drying the separated hydrate of the alkali metal salt after separating the hydrate of the alkali metal salt formed in the step of adding the acid, and drying the hydrate of the alkali metal salt to anhydrous Anhydrides of alkali metal salts such as gypsum can be recovered.

Therefore, the ammonia water may be reacted with the hydrate of the alkali metal salt or reacted with the dried anhydride of the alkali metal salt.

The reaction of the hydrate or anhydride of the alkali metal salt and the ammonia water is not limited thereto, but may be achieved by adding ammonia water to a solution containing the hydrate or anhydride of the alkali metal salt, or adding the hydrate or anhydride of the alkali metal salt to the ammonia water. It can be done by

An ammonium salt may be additionally formed in addition to the hydroxide of the alkali metal by the reaction of the alkali metal salt hydrate or anhydride with the ammonia. For example, the ammonium salt may be ammonium sulfate ((NH ₄ ) ₂ SO ₄ ).

In addition, the ammonium sulfate can be recycled as a fertilizer, etc., and can be specifically used as a sulfite fertilizer after a process of concentrating and/or drying the formed ammonium sulfate.

In the process of forming the hydroxide of the alkali metal, the equivalent of ammonia relative to the total equivalent of the hydrate or anhydride of the alkali metal salt can be used in an amount of 1 time or more and 50 times or less, 5 times or more and 40 times or less, 10 times or more and 30 times or less. . When the amount of ammonia used is too small, the content of the alkali metal hydroxide that can be reused may be reduced by reducing the amount of alkali metal hydroxide from the hydrate or anhydride of the alkali metal salt.

In addition, the recovery process according to the embodiment may further include forming a hydroxide of an alkali metal by introducing the hydrate of the alkali metal salt into a solution containing hydroxide ions (OH-).

The present inventors confirmed through experiments that the hydrate of the alkali metal salt, which can be recycled for various purposes, can be recovered with a high recovery rate by injecting the hydrate of the alkali metal salt into a solution containing hydroxide ions (OH ^- ), and completed the invention.

A hydroxide of an alkali metal may be formed by adding a solution containing hydroxide ion (OH ^- ) to an anhydride formed by drying a hydrate of an alkali metal salt such as CaSO ₄ ·2H ₂ O. For example, the anhydride may be calcium sulfate (CaSO ₄ ), and the solution containing hydroxide ions (OH ^- ) may be a solution containing sodium hydroxide, and the calcium sulfate and sodium hydroxide react as shown in Reaction Formula 3 below. As a result, hydroxides of alkali metals such as Ca(OH) ₂ may be formed.

[Scheme 3]

CaSO ₄ + NaOH -> Ca(OH) ₂ + Na ₂ SO ₄

Alkali metal hydroxides such as Ca(OH) ₂ are reused as alkali metal salts in the step of forming crystals of 3-hydroxypropionic acid salts, or reused as neutralizers in the process of fermenting strains capable of producing 3-hydroxypropionic acid. Neutral fermentation can take place.

In addition, the recovery process may further include drying the separated hydrate of the alkali metal salt after separating the hydrate of the alkali metal salt formed in the step of adding the acid, and drying the hydrate of the alkali metal salt to anhydrous Anhydrides of alkali metal salts such as gypsum can be recovered.

Therefore, a hydrate of the alkali metal salt or an anhydride of the alkali metal salt may be added to the solution containing the hydroxide ion (OH ^- ).

In addition, the hydroxide ion (OH ^- ) containing solution is not particularly limited as long as it is a solution containing hydroxide ion (OH ^- ), but, for example, the hydroxide ion (OH ^- ) containing solution is sodium hydroxide (NaOH), potassium hydroxide ( KOH), barium hydroxide (Ba(OH) ₂ ), lithium hydroxide (LiOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), calcium hydroxide (Ca(OH) ₂ ) and strontium hydroxide (Sr(OH) ₂ ). It may include one or more selected from the group consisting of

In the process of forming the hydroxide of the alkali metal, the equivalent of hydroxide ion relative to the total equivalent of the hydrate or anhydride of the alkali metal salt may be used in an amount of 1 time or more and 20 times or less, 2 times or more and 15 times or less, 3 times or more and 10 times or less. there is. When the equivalent of the used hydroxide ion is too small, the content of the alkali metal hydroxide that can be reused may be reduced because the alkali metal hydroxide is reduced from the hydrate or anhydride of the alkali metal salt.

The recovery rate of the alkali metal hydroxide is 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, such as 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%, 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 is not limited thereto. The recovery rate may be calculated based on weight.

The hydroxide of the alkali metal may be reused as the alkali metal salt in the step of forming and separating crystals of 3-hydroxypropionic acid from the concentrate containing the 3-hydroxypropionic acid.

In addition, the hydroxide of the alkali metal may be reused during the fermentation to achieve neutral fermentation.

In addition, the recovery process according to the embodiment may further include forming a carbonate of an alkali metal by reacting a hydrate of the alkali metal salt with a carbonate.

The inventors of the present invention confirmed through experiments that carbonates of alkali metals that can be recycled for various uses can be recovered with a high recovery rate by reacting the hydrates of the alkali metal salts with the carbonates, and completed the invention.

An alkali metal carbonate may be formed by reacting an anhydride formed by drying a hydrate of an alkali metal salt such as CaSO ₄ ·2H ₂ O with a carbonate. For example, the anhydride may be calcium sulfate (CaSO ₄ ), and the carbonate may be ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), which are carbonates of alkali metals such as CaCO ₃ in the reaction shown in Scheme 4 below. Ammonium persulfate may be formed.

[Scheme 4]

CaSO ₄ + (NH ₄ ) ₂ CO ₃ -> CaCO ₃ + (NH ₄ ) ₂ SO ₄

The alkali metal carbonate, such as CaCO ₃ , is reused as an alkali metal salt in the step of forming crystals of 3-hydroxypropionate, or reused as a neutralizing agent in the process of fermenting strains capable of producing 3-hydroxypropionic acid, resulting in neutral fermentation. It can be done.

In addition, since the ammonium sulfate can be recycled as sulfuric acid fertilizer through processes such as concentration and drying, the recovery process according to the embodiment is eco-friendly because waste generation is reduced, and economical due to reuse of the alkali metal carbonate and the like. In-process construction is possible.

In addition, the recovery process may further include drying the separated hydrate of the alkali metal salt after separating the hydrate of the alkali metal salt formed in the step of adding the acid, and drying the hydrate of the alkali metal salt to anhydrous Anhydrides of alkali metal salts such as gypsum can be recovered.

Accordingly, the carbonate may be reacted with the hydrate of the alkali metal salt or reacted with the dried anhydride of the alkali metal salt.

The reaction between the hydrate or anhydride of the alkali metal salt and the carbonate is not limited thereto, but may be achieved by introducing the carbonate into a solution containing the hydrate or anhydride of the alkali metal salt, or the hydrate of the alkali metal salt into a solution containing the carbonate. Alternatively, anhydride may be added.

In addition, the carbonate is not particularly limited as long as it is a compound containing a carbonate ion (CO ₃ ^2- ), but may be, for example, ammonium carbonate ((NH ₄ ) ₂ CO ₃ ).

An ammonium salt may be additionally formed in addition to the carbonate of the alkali metal by the reaction of the alkali metal salt hydrate or anhydride with the ammonium carbonate. For example, the ammonium salt may be ammonium sulfate ((NH ₄ ) ₂ SO ₄ ).

In addition, the ammonium sulfate can be recycled as a fertilizer, etc., and can be specifically used as a sulfite fertilizer after a process of concentrating and/or drying the formed ammonium sulfate.

In the process of forming the carbonate of the alkali metal, the equivalent of the carbonate relative to the total equivalent of the hydrate or anhydride of the alkali metal salt may be used in an amount of 1 time or more and 20 times or less, 2 times or more and 15 times or less, 5 times or more and 10 times or less. . When the content of the carbonate used is too small, the content of the alkali metal carbonate that can be reused may be reduced because the alkali metal carbonate is converted from a hydrate or anhydride of the alkali metal salt to an alkali metal carbonate.

In addition, the recovery rate of the alkali metal carbonate is 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, such as 40 to 99.9%, 50 to 99.9%, or 60 to 99.9%. %, 70 to 99.9%, 80 to 99.9%, 90 to 99.9%, 40 to 99%, 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 is not limited thereto. The recovery rate may be calculated based on weight.

The alkali metal carbonate may be reused as the alkali metal salt in the step of forming and separating crystals of 3-hydroxypropionic acid from the concentrate containing the 3-hydroxypropionic acid.

In addition, the carbonate of the alkali metal may be reused during the fermentation to achieve neutral fermentation.

According to another embodiment of the present invention, a slurry composition containing 3-hydroxypropionic acid including a precipitate represented by Structural Formula 4 and 3-hydroxypropionic acid may be provided.

[Structural Formula 4]

Cation (Anion)·pH ₂ O

In Structural Formula 4, Cation is a cation of the alkali metal salt, for example, it may be Na ⁺ , Mg ²⁺ or Ca ²⁺ , but in the case of Mg ²⁺ or Ca ²⁺ the crystal of 3-hydroxypropionate is more effectively can be formed

In addition, the anion is an anion of the acid, and may be, for example, SO ₄ ^2- , PO ₄ ^3- , or CO ₃ ^2- , but is not limited thereto. Said p is the number of water molecules in a hydrate, and is an integer greater than or equal to 1.

The slurry composition may be formed in the recovery process according to the embodiment, and is separated from the concentrate at a temperature of, for example, 0 ° C. to 90 ° C., 15 ° C. to 90 ° C., or 30 ° C. to 90 ° C. It may be formed in the step of adding acid to crystals of 3-hydroxypropionate.

The particle diameter of the precipitate may be 0.5 μm or more, 1.0 μm or more, 1.5 μm or more, 500.0 μm or less, 400.0 μm or less, 300.0 μm or less, 200.0 μm or less, 100 μm or less, 80 μm or less, 50 μm or less, 30 ㎛ or less, 20 μm or less, 8.0 μm or less, 7.0 μm or less, 6.0 μm or less, or 5.0 μm or less. Since the precipitate satisfies the above-mentioned particle size, the water content of the precipitate may be lowered, and thus, the flowability of the slurry containing the precipitate may be increased, and thus the filtration of the precipitate from the slurry may be facilitated. The particle size of the precipitate may be measured by scanning electron microscopy (SEM).

The precipitate may represent various particle shapes of prismatic, spherical, plate-shaped, and needle-shaped particles. At this time, the particle size of the precipitate is measured based on the longest straight-line distance among the straight-line distances between crystal planes included in the precipitate.

In addition, the water content of the precipitate may be 150% or less, 130% or less, 110% or less, 100% or less, 80% or less, 70% or less, 1% or more, 10% or more, or 30% or more. If the moisture content of the precipitate is too high, the flowability of the slurry containing the precipitate is lowered, making it difficult to proceed with the process, and it is difficult to separate the precipitate from the slurry, making it difficult to recover 3-hydroxypropionic acid in high yield.

According to the present invention, it is possible to provide a method for efficiently separating and recovering 3-hydroxypropionic acid derived from an eco-friendly bioprocess in a high-purity state and also efficiently recovering hydrates of alkali metal salts that can be recycled for various purposes. can

Figure 1 shows the results of X-ray diffraction analysis of the precipitate formed in Example 1.
Figure 2 shows the results of X-ray diffraction analysis of the precipitate formed in Example 2.
3 is a graph showing the amount of change in electrical conductivity over time in the electrodialysis process of Example 4.
Figure 4 shows the results of X-ray diffraction analysis of solid A in Example 6.
5 shows the results of standard X-ray diffraction analysis of calcium hydroxide.
6 shows the results of X-ray diffraction analysis of solid A in Example 7.
7 shows the results of X-ray diffraction analysis of solid B in Example 7.
8 shows the results of X-ray diffraction analysis of solid A in Example 8.
9 shows the results of standard X-ray diffraction analysis of calcium carbonate.
10 shows the results of X-ray diffraction analysis of solid B in Example 8.
11 is a graph overlapping X-ray diffraction analysis results of solid A, calcium carbonate and solid B in Example 8.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are only for illustrating the content of the present invention, and the scope of the present invention is not limited by the following examples.

Preparation Example 1: Preparation of strain for producing 3-hydroxypropionic acid

A recombinant vector containing genes encoding glycerol dehydratase and aldehyde dehydrogenase known to produce 3-hydroxypropionic acid (3HP) using glycerol as a substrate manufactured. The prepared recombinant vector was introduced into E.coli strain W3110 to prepare a strain producing 3-hydroxypropionic acid.

More specifically, a plasmid pCDF containing a gene encoding glycerol dehydratase (dhaB), a gene encoding aldehyde dehydrogenase (aldH) and a gene encoding glycerol dehydratase reactivase (gdrAB) 3-Hydroxypropionic Acid Production strains were made. The process of preparing the 3-hydroxypropionic acid-producing strain of Preparation Example 1 and the vectors, primers, and enzymes used were carried out with reference to Example 1 of Korean Patent Publication No. 10-2020-0051375 (incorporated herein by reference) did

Preparation Example 2: Ca (3HP) ₂ crystal manufacturing

The strain for producing 3-hydroxypropionic acid prepared in Preparation Example 1 was fermented and cultured at 35° C. in a 5 L fermentor using unrefined glycerol as a carbon source to produce 3-hydroxypropionic acid. In order to prevent a decrease in pH due to the production of 3-hydroxypropionic acid, calcium hydroxide (Ca(OH) ₂ ), an alkali metal salt, was added to maintain a neutral pH during fermentation.

After fermentation culture, cells were removed by centrifugation (4000 rpm, 10 minutes, 4 ° C.), and the primary fermentation broth was purified (primary purification) using activated carbon. Specifically, activated carbon was added to the fermentation broth from which cells were removed by centrifugation, mixed well, and then centrifuged again to separate the activated carbon. Thereafter, the fermentation broth from which the activated carbon was separated was filtered with a vacuum pump through a 0.7 um filter paper to purify the fermentation broth of 3-hydroxypropionic acid.

The concentration of 3-hydroxypropionic acid of the fermentation broth after the primary purification is 50 to 100 g/L, and the fermentation broth is concentrated to a concentration of 600 g/L using a rotary evaporator (50 ° C, 50 mbar) to obtain a concentrate After preparing, ethanol twice the volume of the concentrate was added and stirred (300 rpm) at room temperature to produce Ca(3HP) ₂ crystals. At this time, the concentration of the alkali metal salt in the concentrate was 493.3 g/L (Ca(OH) ₂ standard). The resulting crystals were washed three times with ethanol (EtOH) and dried in an oven at 50° C. to finally recover the crystals.

Example 1

An aqueous solution containing 600 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and stirred for 10 minutes at a temperature of 25 °C and 350 rpm.

37 ml of 5M sulfuric acid solution was added to 77 ml of the aqueous solution at a uniform rate for 5 minutes and further stirred for 30 minutes to form a slurry containing CaSO ₄ precipitate and 3-hydroxypropionic acid.

In order to separate the CaSO ₄ precipitate, filtration was performed using a filtration flask and a vacuum pump. Then, after obtaining the filtrate (A) before washing in the filtration flask, the filtered CaSO ₄ precipitate was washed with 30 ml of distilled water and then filtered to obtain a filtrate (B) after washing. Thereafter, the CaSO ₄ precipitate was dried in an oven at 60° C. for 20 hours to finally obtain a dried CaSO ₄ precipitate. In addition, filtrates (A) and (B) containing 3-hydroxypropionic acid were obtained.

Example 2

An aqueous solution containing 150 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and the temperature was raised to 60° C. while stirring at 350 rpm.

250 mL of a 2.72 M sulfuric acid solution was added to 1 L of the aqueous solution at a uniform rate for 60 minutes and further stirred for 30 minutes to form a slurry containing CaSO ₄ precipitate and 3-hydroxypropionic acid, and the temperature dropped to room temperature. It was stirred until

In order to separate the CaSO ₄ precipitate, filtration was performed using a filtration flask and a vacuum pump. Then, after obtaining the filtrate (A) before washing in the filtration flask, the filtered CaSO ₄ precipitate was washed with 100 ml of distilled water and then filtered to obtain a filtrate (B) after washing. Thereafter, the CaSO ₄ precipitate was dried in an oven at 60° C. for 20 hours to finally obtain a dried CaSO ₄ precipitate. In addition, filtrates (A) and (B) containing 3-hydroxypropionic acid were obtained.

Example 3

A cation exchange resin column was prepared by filling the ion exchange column with 12 BV of cation exchange resin and then washing with water. At this time, TRILITE®CMP28LH from SAMYANG CORPORATION was used as a cation exchange resin.

The entire filtrate containing 3-hydroxypropionic acid obtained in Example 2 was introduced into the cation exchange resin column at a flow rate (SV) of 2.4, and then distilled water was introduced into the cation exchange resin column at a flow rate (SV) of 7.2 or less. Thus, an aqueous solution of 3-hydroxypropionic acid having a pH of 2.5 or less was obtained.

Example 4

An aqueous solution containing 300 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and stirred for 10 minutes at 60 °C and 350 rpm.

A 5M sulfuric acid solution was added to the aqueous solution at a uniform rate for 5 minutes so that the equivalents of 3-hydroxypropionic acid and sulfuric acid were 1:1, and further stirred for 30 minutes to obtain CaSO ₄ precipitate and 3-hydroxypropionic acid. A slurry was formed.

In order to separate the CaSO ₄ precipitate, filtration was performed using a filtration flask and a vacuum pump. Then, after obtaining the filtrate (A) before washing in the filtration flask, the filtered CaSO ₄ precipitate was washed with 30 ml of distilled water and then filtered to obtain a filtrate (B) after washing. Thereafter, the CaSO ₄ precipitate was dried in an oven at 40° C. for 20 hours to finally obtain a dried CaSO ₄ precipitate.

The obtained filtrate (B) was subjected to electrodialysis using an electrodialysis device manufactured by InnoMeditech. Specifically, the electrodialysis tank of the electrodialysis device used InnoMeditech's L3 membrane as a cation and anion separation membrane, and proceeded for 40 minutes in a constant voltage method of 20 cells (20V, 1V per cell). At this time, 3-hydroxypropionic acid was recovered by performing electrodialysis until the electrical conductivity of the desalination tank was lowered to 10% compared to the initial conductivity of the desalination tank of 100%.

Example 5

An aqueous solution containing 300 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and the temperature was raised to 60° C. while stirring at 350 rpm.

A 5M sulfuric acid solution was added to the aqueous solution at a uniform rate for 5 minutes so that the equivalents of 3-hydroxypropionic acid and sulfuric acid were 1:1.2, and further stirred for 30 minutes to obtain CaSO ₄ precipitate and 3-hydroxypropionic acid. A slurry was formed.

In order to separate the CaSO ₄ precipitate, filtration was performed using a filtration flask and a vacuum pump. Then, after obtaining the filtrate (A) before washing in the filtration flask, the filtered CaSO ₄ precipitate was washed with 30 ml of distilled water and then filtered to obtain a filtrate (B) after washing. Thereafter, the CaSO ₄ precipitate was dried in an oven at 40° C. for 20 hours to finally obtain a dried CaSO ₄ precipitate.

The obtained filtrate (B) was subjected to electrodialysis using an electrodialysis device manufactured by InnoMeditech. Specifically, the electrodialysis tank of the electrodialysis device used InnoMeditech's L3 membrane as a cation and anion separation membrane, and proceeded for 40 minutes in a constant voltage method of 20 cells (20V, 1V per cell). At this time, as shown in FIG. 1, electrodialysis was performed until the electrical conductivity of the desalination tank decreased to 10% compared to the initial conductivity of the desalination tank of 100%, and 3-hydroxypropionic acid was recovered.

Example 6

An aqueous solution containing 600 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and stirred for 10 minutes at a temperature of 25 °C and 350 rpm.

37 ml of 5 M sulfuric acid solution was added to 77 ml of the aqueous solution at a uniform rate for 5 minutes and further stirred for 30 minutes to form a slurry containing CaSO ₄ precipitate and 3-hydroxypropionic acid. In order to separate the CaSO ₄ precipitate, filtration was performed using a filtration flask and a vacuum pump.

The separated CaSO ₄ precipitate was dried in an oven at 80 ° C for 20 hours to recover solid A, anhydrite (CaSO ₄ ), and 2.72 g of anhydrite (CaSO ₄ ) was added to 400 mL of 1 M aqueous ammonia solution (compared to anhydrite) 20 equivalents), and stirred at 200 rpm using a magnetic stirring bar while maintaining the temperature at 30 °C. After a reaction time of 4 hours, the precipitate was filtered using a filter flask and a vacuum pump to obtain Solid B containing a small amount of water. Thereafter, the solid B was dried to recover the dried solid B.

Example 7

An aqueous solution containing 600 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and stirred for 10 minutes at a temperature of 25 °C and 350 rpm.

37 ml of 5 M sulfuric acid solution was added to 77 ml of the aqueous solution at a uniform rate for 5 minutes and further stirred for 30 minutes to form a slurry containing CaSO ₄ precipitate and 3-hydroxypropionic acid. In order to separate the CaSO ₄ precipitate, filtration was performed using a filtration flask and a vacuum pump.

The separated CaSO ₄ precipitate was dried in an oven at 80 °C for 20 hours to recover solid A, anhydrite (CaSO ₄ ), and 5.44 g of anhydrite (CaSO ₄ ) was added to 200 mL of 1 M sodium hydroxide (NaOH) aqueous solution. (5 equivalents compared to anhydrite), and stirred at 200 rpm using a magnetic stirring bar while maintaining the temperature at 30 °C. After a reaction time of 4 hours, the precipitate was filtered using a filter flask and a vacuum pump to obtain Solid B containing a small amount of water. Thereafter, the solid B was dried to recover 2.38 g of the dried solid B.

Example 8

An aqueous solution containing 600 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and stirred for 10 minutes at a temperature of 25 °C and 350 rpm.

37 ml of 5 M sulfuric acid solution was added to 77 ml of the aqueous solution at a uniform rate for 5 minutes and further stirred for 30 minutes to form a slurry containing CaSO ₄ precipitate and 3-hydroxypropionic acid. In order to separate the CaSO ₄ precipitate, filtration was performed using a filtration flask and a vacuum pump.

The separated CaSO ₄ precipitate was dried in an oven at 80 °C for 20 hours to recover solid A, anhydrite (CaSO ₄ ), and 4.08 g of anhydrite (CaSO ₄ ) was mixed with 0.2 M ammonium carbonate ((NH ₄ ) ₂ After adding CO ₃ ) to 750 mL of an aqueous solution (5 equivalents compared to anhydrite), the mixture was stirred at 200 rpm using a magnetic stirring bar while maintaining the temperature at 30 °C. After a reaction time of 4 hours, the precipitate was filtered using a filter flask and a vacuum pump to obtain Solid B containing a small amount of water. Thereafter, the solid B was dried to recover 2.67 g of the dried solid B.

Example 9

An aqueous solution containing 250 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and stirred for 10 minutes at 60 °C and 200 rpm.

A 5 M phosphoric acid solution was added to the aqueous solution at a uniform rate for 5 minutes so that the equivalents of 3-hydroxypropionic acid and phosphoric acid were 1:1, and further stirred for 30 minutes to obtain a calcium phosphate precipitate and 3-hydroxypropionic acid. A slurry containing

In order to separate the calcium phosphate precipitate, filtration was performed using a filtration flask and a vacuum pump. Then, after obtaining the filtrate (A) before washing in the filtration flask, the filtered calcium phosphate precipitate was washed with 30 ml of distilled water and then filtered to obtain a filtrate (B) after washing. Thereafter, the calcium phosphate precipitate was dried in an oven at 80° C. for 20 hours to finally obtain a dried calcium phosphate precipitate.

A cation exchange resin column was prepared by filling a cation exchange resin with 12 BV in a resin tower for ion exchange (Junchoja Co., Ltd., JCL-GF-F110) and then washing with water. At this time, TRILITE®CMP28LH from SAMYANG CORPORATION was used as a cation exchange resin.

The entire obtained filtrate (B) was introduced into the cation exchange resin column at a flow rate (SV) of 2.4 m³h ^-1 , and then distilled water was introduced into the cation exchange resin column at a flow rate (SV) of 7.2 m³h ^-1 or less, pH A 2.5 or less 3-hydroxypropionic acid aqueous solution was obtained.

Example 10

An aqueous solution containing 250 g/L of Ca(3HP) ₂ crystals recovered in Preparation Example 2 was prepared, and stirred for 10 minutes at a temperature of 25 °C and 200 rpm.

A 5 M phosphoric acid solution was added to the aqueous solution at a uniform rate for 5 minutes so that the equivalents of 3-hydroxypropionic acid and phosphoric acid were 1:1, and further stirred for 30 minutes to obtain a calcium phosphate precipitate and 3-hydroxypropionic acid. A slurry containing

In order to separate the calcium phosphate precipitate, filtration was performed using a filtration flask and a vacuum pump. Then, after obtaining the filtrate (A) before washing in the filtration flask, the filtered calcium phosphate precipitate was washed with 30 ml of distilled water and then filtered to obtain a filtrate (B) after washing. Thereafter, the calcium phosphate precipitate was dried in an oven at 80° C. for 20 hours to finally obtain a dried calcium phosphate precipitate.

A cation exchange resin column was prepared by filling a cation exchange resin with 12 BV in a resin tower for ion exchange (Junchoja Co., Ltd., JCL-GF-F110) and then washing with water. At this time, TRILITE®CMP28LH from SAMYANG CORPORATION was used as a cation exchange resin.

The entire obtained filtrate (B) was introduced into the cation exchange resin column at a flow rate (SV) of 2.4 m³h ^-1 , and then distilled water was introduced into the cation exchange resin column at a flow rate (SV) of 7.2 m³h ^-1 or less, pH A 2.5 or less 3-hydroxypropionic acid aqueous solution was obtained.

Comparative Example 1

A 5M sulfuric acid solution was added to the 3-hydroxypropionic acid fermentation broth (concentration of about 100 g/L), which was first purified in Preparation Example 2, so that the equivalents of 3-hydroxypropionic acid and sulfuric acid were 1:1, and uniformly mixed for 5 minutes. The mixture was added at high speed and further stirred for 30 minutes to form a slurry containing CaSO ₄ precipitate and 3-hydroxypropionic acid.

In order to separate the CaSO ₄ precipitate, filtration was performed using a filtration flask and a vacuum pump. Then, after obtaining the filtrate (A) before washing in the filtration flask, the filtered CaSO ₄ precipitate was washed with 30 ml of distilled water and filtered to obtain the filtrate (B) after washing and concentrated (about 30% by weight). ). The concentrated filtrate was passed through a cation exchange resin (Samyang, TRILITE® CMP28LH) to remove residual ionic impurities, and a solution containing 3-hydroxypropionic acid having a concentration of 300 g/L was recovered.

Thereafter, the CaSO ₄ precipitate was dried in an oven at 40° C. for 20 hours to finally obtain a dried CaSO ₄ precipitate.

<Test Example>

1. Calcium (Ca) element removal rate evaluation

In Examples 1 to 5, 9, 10 and Comparative Example 1, when the crystals of 3-hydroxypropionate (Ca(3HP) ₂ crystals) were converted to 3-hydroxypropionic acid, CaSO ₄ precipitates (or calcium phosphate precipitates) The content of the calcium (Ca) element removed due to generation was measured through ion chromatography (Ion Chromatography) analysis.

Specifically, the content of calcium (Ca) element contained in the 32.0 wt% Ca (3HP) ₂ aqueous solution (X _ref ) and the content of calcium (Ca) element contained in the filtrate (B) after washing (X _filtration ) After analyzing each, the calcium (Ca) element removal rate was calculated through the following general formula 1, and the results are shown in Table 1 below.

[Formula 1]

Calcium (Ca) element removal rate (%) = (X _ref - X _filtration )/X _ref * 100

2. Measurement of recovery of 3-hydroxypropionic acid

The recovery rate of 3-hydroxypropionic acid obtained in Examples 1 to 5, 9, and 10 and Comparative Example 1 was measured and calculated using high-performance liquid chromatography (HPLC).

Specifically, the absolute amount (X) of 3-hydroxypropionic acid in the aqueous solution containing Ca(3HP) ₂ crystals and the absolute amount (Y) of 3-hydroxypropionic acid in the filtrate were measured, and 3 - Hydroxypropionic acid recovery was calculated.

[Formula 2]

Recovery of 3-hydroxypropionic acid (%) = ( Y / X ) * 100

3. Determination of impurity content

Impurities contained in the final recovered solutions in Examples 1 to 5, 9, and 10 and Comparative Example 1 were measured by nuclear magnetic resonance spectroscopy (NMR) and high performance liquid chromatography (HPLC). On the other hand, if the impurity content was not measured, it was marked as '-'.

(1) High-Performance Liquid Chromatography (HPLC)

The ratio of impurities (glycerol, acetate and 1,3-propanediol) and 3-hydroxypropionic acid (3HP) was measured using HPLC.

For HPLC, 0.5 mM sulfuric acid (H ₂ SO ₄ ) was flowed at a flow rate of 0.4 mL/min using an Aminex HPX-87H ion exclusion column (7.8 * 300 mm, 9 ㎛), and the temperature of the column was 35 ℃, The injection volume was 5 μL and the UV detector was 210 nm.

(2) ¹ H-NMR

The content ratio of impurities (glycerol, acetate, and 1,3-propanediol) and 3-hydroxypropionic acid (3HP) was analyzed using ¹ H-NMR.

Before purification, 100 μL of alkali metal 3-hydroxypropionic acid and purified 3-hydroxypropionic acid were dissolved in 500 μL of NMR solvent D2O for sampling, and 11.5 μL of water-removed mimethylformamide (DMF) was added. One solution was transferred to an NMR tube and a sample for ¹ H-NMR measurement was prepared.

¹ H-NMR spectrum (AVANCE III HD FT-NMR spectrometer (500 MHz for 1H), manufactured by Bruker) was measured using the measurement sample.

Calcium (Ca) element removal rate (%) Recovery of 3-hydroxypropionic acid (%) Impurity content (ppm) glycerol acetate 1,3-propanediol Example 1 99.0 69.68 - - - Example 2 98.0 99.50 - - - Example 3 99.0 99.10 - - - Example 4 99.0 99.80 detection limit detection limit detection limit Example 5 99.9 95.20 detection limit detection limit detection limit Example 9 90.0 92.00 detection limit 110 detection limit Example 10 90.0 91.00 detection limit 120 detection limit Comparative Example 1 95.0 90.00 2451 455 120

Referring to Table 1, it was confirmed that in Examples 1 to 5, 9, and 10, 3-hydroxypropionic acid was recovered at about 69.68% or more while elemental calcium was removed by 90% or more. In addition, it was confirmed that no impurities were detected in Examples 4 and 5 in which 3-hydroxypropionic acid was purified through electrodialysis.

Through this, in the case of the 3-hydroxypropionic acid recovery process of the above example, it was confirmed that high-purity 3-hydroxypropionic acid can be efficiently produced by effectively separating cations from 3-hydroxypropionic acid salt.

4. Sediment composition analysis

When crystals of 3-hydroxypropionic acid salt (Ca(3HP) ₂ crystals) are converted to 3-hydroxypropionic acid, a precipitate including CaSO ₄ appears to be formed. proceeded using

Specifically, key element chemical analyzes were performed on a ThermoARL Advant'X Sequential XRF equipped with Uniquant standardless software and loss on ignition (LOI) normalization (moisture content included in normalization), loss on ignition (LOI). on ignition) value was measured by the loss in an electric furnace maintained at 975 ° C, and the crystal moisture was measured by the difference in loss in drying oven at 250 ° C.

Ingredients (wt%) SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO SO ₃ LOI crystal moisture Example 1 0.53 0.68 0.42 31.19 - 52.83 13.44 12.38 Example 2 - 0.50 0.35 30.12 - 49.13 18.77 17.8

Then, the type and crystal form of the material were measured for the obtained precipitate using an X-ray diffraction analyzer (Bruker AXS D4-Endeavor XRD). Specifically, the applied voltage was 40 kV and the applied current was 40 mA, and the measured range of 2theta was 10° to 90°, and was measured by scanning at 0.05° intervals.

wt% gypsum minerals complete
gypsum half number
gypsum myriad
gypsum subtotal calcite dolomite illite chlorite microcline subtotal Example 1 1.56 42.57 51.69 95.82 0.16 0.78 0.41 0.27 2.56 4.18 Example 2 72.04 23.65 2.12 97.81 - 0.22 1.04 - 0.83 2.09

Referring to Tables 2 and 3, the precipitate obtained in the examples contained dihydrate gypsum, hemihydrate gypsum, and anhydrite at 95.82% or more of the total content, and hardly contained minerals such as calcite and dolomite. , SiO ₂ and the like were also confirmed to contain almost no impurities.

5. Crystal phase analysis of the precipitate

In Examples 6 to 8, the type and crystal form of the materials were measured for solids A and B using an X-ray diffraction analyzer (Bruker AXS D4-Endeavor XRD). Specifically, the applied voltage was 40 kV and the applied current was 40 mA, Cu-Kα radiation (wavelength λ = 1.54184 Å) was irradiated, and the range of 2theta measured was 10 ° to 90 °, scanned at 0.05 ° intervals was measured.

Diffraction angles (2θ±0.2°) where main peaks appear in the XRD analysis results of solids A and B of Example 6, and diffraction angles where main peaks appear in the standard XRD analysis results of calcium hydroxide (Ca(OH) ₂ ) (2θ±0.2°) is shown in Table 4 below.

Diffraction angles (2θ±0.2°) where main peaks appear in the XRD analysis results of solids A and B of Example 7, and diffraction angles where main peaks appear in the standard XRD analysis results of calcium hydroxide (Ca(OH) ₂ ) (2θ±0.2°) is shown in Table 5 below.

Diffraction angles (2θ±0.2°) at which the main peaks appear in the XRD analysis results of solids A and B of Example 8 and diffraction angles (2θ±0.2°) at which the main peaks appear in the standard XRD analysis results of calcium carbonate are shown in Table 6 below.

Meanwhile, FIG. 4 shows the XRD analysis results of solid A (CaSO ₄ ) of Example 6, and FIG. 5 shows the standard XRD analysis results of calcium hydroxide (Ca(OH) ₂ ). In addition, FIG. 6 shows the XRD analysis results of Solid A (CaSO ₄ ) of Example 7, and FIG. 7 shows the XRD analysis results of Solid B of Example 7. In addition, Figure 8 shows the XRD analysis results of solid A (CaSO ₄ ) of Example 8, Figure 9 shows the standard (standard) XRD analysis results of calcium carbonate (CaCO ₃ ), Figure 10 is Example 8 It shows the XRD analysis results of solid B of, and FIG. 11 is a graph overlapping the analysis results of solid A (CaSO ₄ ), calcium carbonate and solid B of Example 8.

Diffraction angle at which the main peak appears (2θ±0.2°) Solid A (CaSO ₄ ) 23, 25.4, 28.6, 31.4, 32, 36.4, 38.8, 40.9, 41.4, 43.4, 45.6, 46.9, 48.8, 49.2, 52.4, 55.8, 57.9, 59.2 standard calcium hydroxide 18, 28.8, 34, 47.2, 51, 54.4, 56.2, 59.5 solid B 18, 28.8, 34, 47.2, 51, 54.4, 56.2, 59.5

Diffraction angle at which the main peak appears (2θ±0.2°) Solid A (CaSO ₄ ) 23, 25.4, 28.6, 31.4, 32, 36.4, 38.8, 40.9, 41.4, 43.4, 45.6, 46.9, 48.8, 49.2, 52.4, 55.8, 57.9, 59.2 standard calcium hydroxide 18, 28.8, 34, 47.2, 51, 54.4, 56.2, 59.5 solid B 18, 28.8, 34, 47.2, 51, 54.4, 56.2, 59.5

Referring to Tables 4 and 5, the XRD patterns of Solid B of Examples 6 and 7 are the same as the standard XRD patterns of calcium hydroxide, and in particular, the XRD patterns of Solid A were not observed in the XRD patterns of Solid B, so anhydrous gypsum ( It was confirmed that the reaction between CaSO ₄ ) and ammonia water (or sodium hydroxide) was 100% conversion, so that anhydrous gypsum (CaSO ₄ ) did not remain and calcium hydroxide was produced.

Diffraction angle at which the main peak appears (2θ±0.2°) Solid A (CaSO ₄ ) 23, 25.4, 28.6, 31.4, 32, 36.4, 38.8, 40.9, 41.4, 43.4, 45.6, 46.9, 48.8, 49.2, 52.4, 55.8, 57.9, 59.2 standard calcium carbonate 23, 29.2, 31.2, 36, 39.4, 43.2, 47.4, 48.5, 57.5 solid B 23, 29.2, 31.2, 36, 39.4, 43, 47, 47.4, 48.5, 56.4, 57.2

Referring to Table 6, the XRD pattern of solid B of Example 8 is the same as the standard XRD pattern of calcium carbonate, and in particular, the XRD pattern of solid A was not observed in the XRD pattern of solid B, so that anhydrous gypsum (CaSO ₄ ) It was confirmed that the reaction of ammonium carbonate ((NH ₄ ) ₂ CO ₃ ) was performed at a conversion rate of 100%, so that anhydrous gypsum (CaSO ₄ ) did not remain and calcium carbonate was produced.

6. alkali Recovery rate of metal hydroxide

The recoveries of the alkali metal hydroxide (solid B) of Examples 6 and 7 and the metal carbonate (solid B) of Example 8 were measured by high performance liquid chromatography (HPLC), and the results are shown in Table 7 below. Specifically, the content (Y) of the alkali metal salt contained in the concentrate and the content (X) of the finally recovered alkali metal hydroxide/carbonate (solid B) were measured, and substituted into the following general formula 3, respectively, to determine the alkali metal The recovery of hydroxide was calculated.

[Formula 3]

Recovery of alkali metal hydroxide/carbonate (%) = X/Y * 100

Recovery of alkali metal hydroxide/carbonate (%) Example 6 85 Example 7 80 Example 8 89

According to Table 7, 80% or more of the alkali metal salt used in the process of 3-hydroxypropionic acid fermentation or crystal formation of 3-hydroxypropionate is finally recovered in the form of alkali metal hydroxide (or alkali metal carbonate). confirmed that it was.

Claims (21)

Forming and separating crystals of 3-hydroxypropionic acid from a concentrated solution containing 3-hydroxypropionic acid in the presence of an alkali metal salt;
Forming an aqueous solution containing crystals of the 3-hydroxypropionate; and
Forming and separating a hydrate of an alkali metal salt and 3-hydroxypropionic acid by adding an acid to an aqueous solution containing the crystals of the 3-hydroxypropionic acid salt;
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 1,
The aqueous solution containing the crystals of 3-hydroxypropionate contains at least 100 g / L of crystals of 3-hydroxypropionate, the recovery process of hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 1,
Forming and separating a hydrate of an alkali metal salt and 3-hydroxypropionic acid by adding acid to an aqueous solution containing the crystals of 3-hydroxypropionic acid salt,
Separating the hydrate of the alkali metal salt from the hydrate of the alkali metal salt and the acid addition solution containing 3-hydroxypropionic acid; and
Electrodialysis of the acid addition solution from which the hydrate of the alkali metal salt is separated;
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 3,
electrodialysis of the acid-added solution from which the hydrate of the alkali metal salt was separated;
Performed until the conductivity in the desalination tank for recovering the desalination product formed by electrodialysis of the acid addition solution from which the hydrate of the alkali metal salt is separated is lowered to 50% or less compared to the initial value,
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 1,
Forming a hydroxide of an alkali metal by reacting the hydrate of the alkali metal salt with ammonia water; further comprising,
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 1,
Injecting the hydrate of the alkali metal salt into a solution containing hydroxide ions (OH ^- ) to form an alkali metal hydroxide; further comprising,
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 5 or 6,
The hydroxide of the alkali metal is reused as the alkali metal salt in the step of forming and separating crystals of 3-hydroxypropionic acid from the concentrate containing the 3-hydroxypropionic acid,
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 5 or 6,
Fermenting a strain having 3-hydroxypropionic acid producing ability to produce a 3-hydroxypropionic acid fermentation broth; and
Concentrating the fermentation broth to form a concentrate containing the 3-hydroxypropionic acid; further comprising,
The hydroxide of the alkali metal is reused during the fermentation to achieve neutral fermentation,
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 1,
Forming a carbonate of an alkali metal by reacting the hydrate of the alkali metal salt with the carbonate; further comprising,
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 1,
The acid is phosphoric acid,
The hydrate of the alkali metal salt is a phosphate,
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 1,
Forming and separating a hydrate of an alkali metal salt and 3-hydroxypropionic acid by adding acid to an aqueous solution containing the crystals of 3-hydroxypropionic acid salt,
contacting the formed solution containing 3-hydroxypropionic acid with a cation exchange resin column; and
Recovering 3-hydroxypropionic acid from the solution in contact with the cation exchange resin column;
A process for recovering hydrates of alkali metal salts and 3-hydroxypropionic acid.
According to claim 1,
At the time of adding an acid to the aqueous solution containing the crystals of 3-hydroxypropionate, the temperature of the aqueous solution containing the crystals of 3-hydroxypropionate is 0 ° C. or more and 90 ° C. or less. Recovery process of propionic acid.
According to claim 1,
When an acid is added to the aqueous solution containing the crystals of 3-hydroxypropionate, a precipitate having a particle size of 0.5 μm or more and 500.0 μm or less is formed, a hydrate of an alkali metal salt and 3-hydroxypropionic acid Recovery process.
According to claim 13,
The water content of the precipitate is 200% or less, the recovery process of the hydrate of the alkali metal salt and 3-hydroxypropionic acid.
According to claim 1,
The concentrate is a recovery process of a hydrate of an alkali metal salt and 3-hydroxypropionic acid containing 300 g / L or more of the 3-hydroxypropionic acid.
According to claim 1,
The concentrate contains 350 g / L or more and 900 g / L or less of the 3-hydroxypropionic acid, a hydrate of an alkali metal salt and a recovery process of 3-hydroxypropionic acid.
According to claim 1,
The aqueous solution containing the crystals of 3-hydroxypropionic acid salt contains the crystals of 3-hydroxypropionic acid salt at a concentration of 100 g/L or more and 800 g/L or less, recovery of hydrates of alkali metal salts and 3-hydroxypropionic acid process.
According to claim 1,
The alkali metal salt is Ca(OH) ₂ , Mg(OH) ₂ or a mixture thereof, a hydrate of an alkali metal salt and a recovery process of 3-hydroxypropionic acid.
According to claim 1,
The 3-hydroxypropionic acid crystals contain a calcium salt of 3-hydroxypropionic acid, a hydrate of an alkali metal salt and a recovery process of 3-hydroxypropionic acid.
According to claim 1,
The crystal of 3-hydroxypropionic acid salt has a particle size distribution of D ₅₀ of 20 μm or more and 300 μm or less, and (D ₉₀ -D ₁₀ ) / D ₅₀ of 1.00 or more and 3.00 or less, an alkali metal salt hydrate and 3-hydroxypropionic acid. recovery process.
According to claim 1,
The crystal of 3-hydroxypropionate is a hydrate of an alkali metal salt having a radiocarbon isotope content of 20 pMC (percent modern carbon) or more and a bio-carbon content of 20% by weight or more, measured according to ASTM D6866-21 standard, and 3- Recovery process of hydroxypropionic acid.

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