巴西专利BR112014014883B1 method for the recovery of polycarboxylic acid from an aqueous mixture

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专利摘要:
POLYCARBOXYLIC ACID EXTRACTION. The present invention relates to a method for recovering polycarboxylic acid from an aqueous mixture comprising the steps of: providing an aqueous mixture comprising polycarboxylic acid and at least 5% by weight of dissolved halide salt, based on total weight of water and material dissolved in the aqueous mixture, extract the polycarboxylic acid from the aqueous mixture in a first organic liquid comprising an organic solvent selected from the group consisting of ketones and ethers, thus obtaining an organic solution of the polycarboxylic acid and a aqueous residual liquid comprising the halide salt, and extracting the polycarboxylic acid from the organic solution of carboxylic acid in an aqueous liquid, thereby obtaining an aqueous solution of polycarboxylic acid and a second organic liquid. The method according to the invention allows a combined concentration and purification step for polycarboxylic acid feed solutions.
公开号:BR112014014883B1
申请号:R112014014883-0
申请日:2012-12-21
公开日:2021-02-02
发明作者:André Banier De Haan；Jan Van Kriek；Tanja Dekic Zivkovic
申请人:Purac Biochem B.V；
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专利说明:

[001] The present invention relates to a method for the preparation of a carboxylic acid solution using extraction.
[002] Isolating carboxylic acids from an aqueous mixture containing impurities, such as salts, can be difficult. Carboxylic acids can be manufactured by fermenting a carbon source, such as carbohydrates or glycerol, by microorganisms. In such a process a fermentation of a carbohydrate source is generally fermented by means of a microorganism in order to form a carboxylic acid. The liquid in which the carbohydrate source is fermented is called the fermentation broth or fermentation medium. The formation of carboxylic acid during fermentation will result in a decrease in the pH of the fermentation broth. Since such a decrease in pH can damage the metabolic process of the microorganism, it is a common practice to add a neutralizing agent, that is, a base, in the fermentation medium in order to neutralize the pH. As a result, the carboxylic acid produced in the fermentation medium is typically present in the form of a carboxylate salt. Although there are microorganisms that are to some extent resistant to acidic environments, such that fermentation can be conducted at a low pH (for example, at a pH of 3), even in such processes at least part of the carboxylic acid is obtained in the form of a carboxylate salt.
[003] To recover the carboxylic acid from the fermentation broth, after fermentation, downstream processing is necessary. In such processing, the carboxylate salt in the fermentation broth has to be converted to carboxylic acid. In addition, carboxylic acid (or carboxylate, if not yet converted) needs to be isolated from the fermentation broth. Since a fermentation broth comprises several compounds, including significant amounts of biomass (such as microorganisms) and salt (from the neutralizing agent), the recovery and isolation of carboxylic acid can be quite complex, usually requiring several processing steps and leading to waste material, especially salt residues.
[004] For polycarboxylic acids, specific problems occur. Polyacids generally have a low solubility in water. On the one hand, this means that the main polyacid body can be removed from water relatively easily, using methods such as precipitation or crystallization. On the other hand, which results in the formation of dilute acid solutions from which, for economic reasons and for HSE reasons, it is still desired to remove the polyacid. Although it is possible to remove the last fractions also by crystallization or precipitation, this operation involves multiple phases, which requires expensive operating conditions and apparatus. There is therefore a need for a method for removing polycarboxylic acids from aqueous solutions, which combines efficient removal with relatively low-cost operation.
[005] WO95 / 03268 describes a process for the recovery of an organic acid, including mono-, di- and tricarboxylic acids comprised of 3 to 8 carbon atoms from a fermentation broth by clarifying the broth to remove at least minus a substantial portion of the impurities in it, producing a clarified diet; acidulate the clarified feed by adding an amount of mineral acid effective to lower the pH of the feed from about 1.0 to about 4.5, producing an acidic feed that is substantially saturated with respect to at least one electrolyte selected from the group consisting of MHS04, M2S04, M3P04, M2HP04, MH2P04, and MN03, where M is selected from the group consisting of Na, NH4, and K; extract the acidulated feed with an extraction mixture, which includes (a) water, (b) a mineral acid, in an amount effective to maintain the pH of the feed between about 1.0 and about 4.5, and (c ) an oxygenated solvent that has limited miscibility with water. The extraction produces a solvent extract and a first refined one. The solvent extract is subjected back to extraction with an aqueous liquid, thus producing an aqueous extract rich in organic acid and a refined solvent depleted in organic acid.
[006] A problem with the extraction sequence followed by return to extraction is the formation of diluted materials. Generally, when a compound is extracted from water using an organic liquid, and then extracted from the organic liquid using water, the concentration of the compound in the aqueous liquid product is less than in the aqueous starting liquid. This is, of course, a disadvantage, because it generates diluted liquids that require greater concentration. This is of particular importance when the starting liquid no longer has a relatively low acid concentration, as in the case of relatively insoluble polyacids. There is, therefore, a need in the art for an extraction / return process for the extraction of polycarboxylic acids, which allows the isolation of a polycarboxylic acid from a salt solution, even when the polyacid concentration is relatively low, without the formation of more dilute acid solutions. The present invention provides such a process.
[007] The present invention is directed to a method for recovering polycarboxylic acid from an aqueous mixture comprising the steps of - providing an aqueous mixture comprising polycarboxylic acid, and at least 5% by weight of salt of dissolved halide, based on the total weight of the water and material dissolved in the aqueous mixture, - extracting the polycarboxylic acid from the aqueous mixture into a first organic liquid comprising an organic solvent selected from the group consisting of ketones and ethers, obtaining thus, an organic solution of polycarboxylic acid and an aqueous residue liquid comprising the halide salt, and - extracting the organic polycarboxylic acid from the organic solution of carboxylic acid in an aqueous liquid, thus obtaining an aqueous solution of polycarboxylic acid and a second organic liquid.
[008] It should be noted that CN101979368 describes extraction of acid from a solution containing a salt. The extractor is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, ethylene glycol, diethyl ether, methyl acetate or ethyl acetate.
[009] JP8 - 337552 describes the conversion of an acid-to-acid salt, followed by extraction that takes place with an oxygenated saturated heterocyclic solvent.
[0010] None of the references describes a return process for extraction. Therefore, these references are not relevant.
[0011] It was found that the process according to the invention, which is characterized by the use of a specific carboxylic acid, that is, a polycarboxylic acid, in combination with a specific salt, that is, a halide salt, in a specific amount, that is, in an amount of at least 5% by weight of dissolved halide salt, leads to a process in which the concentration of carboxylic acid in the aqueous solution obtained after extraction and return to extraction is higher than that of aqueous mixture before extraction. This concentration effect is advantageous, for example, when the aqueous solution of carboxylic acid obtained after returning to the extraction is to be concentrated, in which case the energy costs are saved by having to evaporate less water to obtain a certain concentration of acid carboxylic. In addition, the product obtained in the process according to the invention has a high degree of purity. Other advantages of the present invention will become apparent from the additional report.
[0012] Not wishing to be limited by theory, it is believed that one or more of the following effects can occur in the extraction process according to the invention.
[0013] It may be that the presence of the halide salt in the aqueous mixture increases the extraction of the carboxylic acid from the aqueous mixture within the first organic liquid. This will contribute to the concentration effect described above.
[0014] Secondly, it may be that the halide salt dissolved decreases the solubility of the organic solvent in water. In particular, at higher concentrations of dissolved halide salt, less solvent based on ketone (such as, for example, MIBK) can dissolve in the aqueous mixture. This effect can be strongest at high temperatures, in particular in the temperature range of 20 ° to 100 ° C. Therefore, forward and / or return extraction are preferably conducted at a temperature of at least 25 ° C, from preferably at least 30 ° C, more preferably at least 40 ° C. This effect is considered to be valid for ketones and ethers in general. The lower solubility of the organic liquid in water will result in streams with a higher purity and less solvent losses, both in the forward and return extraction and can, therefore, lead to a more efficient process. In contrast, the solubility of water in alcohol and the solubility of alcohol in water increase when the temperature is increased in the temperature range of 25 ° C and 100 ° C.
[0015] Thirdly, the solubility of water in the organic solvent during extraction can also be reduced by the presence of the dissolved halide salt.
[0016] Fourthly, it was found that the dissolved halide salt can suppress the formation of the emulsion, thus increasing the separation phase between aqueous and organic liquids. This is particularly advantageous when the aqueous mixture comprises traces of biomass. Biomass from a fermentation process typically comprises compounds that can act as surfactants. Therefore, when an aqueous mixture comprising the biomass is brought into contact with an organic solvent, an emulsion will typically be formed. This emulsion formation is undesirable, as it can hinder the process of phase extraction and separation.
[0017] Other preferred embodiments of the present invention will be described below.
[0018] Figure 1 shows a schematic representation of an embodiment of the present invention. In Figure 1, (1) represents the aqueous starting mixture, which, where it is supplied to an extraction reactor (2), where it is brought into contact with an organic liquid (3). A stream (4), which comprises the carboxylic acid in which the organic liquid is removed from the extraction reactor (2). Aqueous liquid residue (5) is also removed from the extraction reactor (2). A stream (4) comprising the carboxylic acid in the organic liquid is supplied to the re-extraction reactor (6), where it is brought into contact with the aqueous liquid supplied through the line (7). The aqueous solution of the carboxylic acid in the product is removed via the tubing (8). The organic liquid is removed through the pipe (9), and recycled to the extraction reactor (2) through the line (3), optionally after intermediate purification steps (not shown).
[0019] The term "extraction" as used herein refers to liquid-liquid extraction, also known as solvent extraction. Solvent extraction is an extraction method based on the difference in solubility of a compound in two different liquids, that is, in the present case, the solubility of the carboxylic acid in water (present in the aqueous mixture and the aqueous liquid) in relation to the solubility of carboxylic acid in the organic solvent (present in the organic liquid). Forward extraction is the process in which the compound to be extracted is extracted from the aqueous mixture in the organic liquid. Re-extraction is the process in which the compound to be extracted is extracted from the organic liquid in an aqueous liquid.
[0020] The term "solubility" as used herein refers to the maximum amount of weight of a compound that can be dissolved in a certain amount of an aqueous mixture at a certain temperature.
[0021] Forward extraction and re-extraction as used in the method of the present invention are based on the difference in solubility of the carboxylic acid in water and the organic solvent at different temperatures. The solubility of a compound in one solvent in relation to another solvent can be expressed in terms of the distribution ratio (DR). This ratio gives an indication of how a compound will be distributed throughout the aqueous phase (for example, the aqueous mixture ) and the organic phase (for example, the organic liquid) in a two-phase equilibrium system. The distribution ratio can be defined as the relationship between the concentration of carboxylic acid dissolved in the organic phase ([carboxylic acid] organic) in relation to the concentration of carboxylic acid dissolved in water ([carboxylic acid] water), provided that the two phases are in equilibrium with each other: DR = [carboxylic acid] organic / [carboxylic acid] water (1)
[0022] From formula (1) it can be concluded that the higher the distribution ratio, the more carboxylic acid will dissolve in the organic phase.
[0023] The distribution ratio depends on many variables, including temperature and the specific composition of the organic and aqueous phase. For example, the concentration of the halide salt dissolved in the aqueous mixture and the type of solvent used will influence the distribution ratio.
[0024] During forward extraction, carboxylic acid should preferably dissolve better in the organic solvent than in the water. Therefore, the distribution ratio in the forward extraction should be as high as possible. In particular, a high distribution ratio during forward extraction is desirable that any carboxylic acid still present in the waste liquid will directly lead to a decrease in the total yield of carboxylic acid, when this waste liquid cannot be reworked and / or recycled back into the process again, or used for other purposes and must be disposed of. In case the distribution ratio during the forward extraction is high, relatively little carboxylic acid will be lost since most of the carboxylic acid will have been dissolved in the organic liquid. It is preferred that the DR in forward extraction, also indicated as DFE, is at least 0.1, more in particular at least 0.4, even more in particular at least 0.8.
[0025] During re-extraction, the opposite is true. Carboxylic acid should preferably dissolve better in the aqueous phase than in the organic liquid. It is preferred for DR on re-extraction, also indicated as also indicated as DBE to be at most 0.5, more in particular at most 0.3, even more particularly at most 0.1.
[0026] If the forward extraction distribution ratio is greater than the distribution ratio for reextraction, this will contribute to a concentration effect, in which the aqueous solution of carboxylic acid obtained after reextraction has a higher concentration of carboxylic acid than the aqueous mixture used as the starting material in the forward extraction. It is preferable that the ratio between DFE and DBE is at least at least 1.1, more preferably at least 2. The ratio between DFE and DBE will generally not be more than 10.
The method of the invention comprises the step of providing an aqueous mixture comprising the polycarboxylic acid and dissolved halide salt. The aqueous mixture is the mixture to be extracted with the organic liquid.
[0028] The aqueous mixture is preferably an aqueous solution, since the extraction can be more easily carried out when no solid material is present. Such a solution can be referred to as an aqueous feed solution. However, the presence of solid matter in the aqueous mixture is possible, to some extent, depending on the equipment used, as will be evident to the person skilled in the art. Thus, the aqueous mixture can also be a suspension. Examples of solid matter that may be present in said suspension are carboxylic acid, in solid form, undissolved halide salt and insoluble impurities.
[0029] The aqueous mixture comprises polycarboxylic acid, in this specification, often abbreviated to carboxylic acid. In one embodiment, polycarboxylic acid is a di- or tricarboxylic acid comprising at least 2, but not more than 6 carbon atoms (C2 - 6 carboxylic acid). In one embodiment, polycarboxylic acid is selected from the group consisting of succinic acid, citric acid, fumaric acid, itaconic acid, adipic acid, maleic acid, 2,5-furandicarboxylic acid, mandelic acid, malic acid, and tartaric acid. Preferably, the polycarboxylic acid is selected from the group consisting of succinic acid, citric acid, fumaric acid, itaconic acid, adipic acid, and 2,5-furandicarboxylic acid. Polycarboxylic acid can, in particular, be selected from succinic acid, fumaric acid, itaconic acid, and 2,5-furandicarboxylic acid.
[0030] The content of carboxylic acid present in the aqueous mixture is preferably as high as possible. In general, the content of carboxylic acid is limited by the solubility of the acid in the aqueous mixture. The aqueous mixture can comprise the carboxylic acid in solid form, but preferably, the solids content is as low as possible in the form of solids can create more difficult extraction and phase separation. It is within the scope of the specialist to determine the type of commercially available extraction equipment capable of handling solids. Therefore, the content of carboxylic acid in the aqueous mixture may be higher, but it is preferably equal to or less than the solubility of the carboxylic acid in the aqueous mixture. Preferably, more than 99% by weight of the carboxylic acid present in the aqueous mixture is in dissolved form. In one embodiment, the amount of acid is at least 50% of the maximum amount of acid that can be dissolved in the aqueous mixture containing the salt under extraction conditions, in particular at least 70%.
[0031] In one embodiment, the aqueous mixture has a pH of 2 or less, typically a pH of less than 1, for example a pH of 0 to 1. It is preferred for the pH to be relatively low, to ensure that the carboxylic acid it is present in the mixture in the form of acid, allowing extraction.
[0032] The aqueous mixture can also comprise impurities, in particular impurities originating from a fermentation process. Such impurities can be soluble or insoluble in the aqueous mixture. Examples of dissolved impurities are sugars, proteins and salts. Insoluble biomass (eg microorganisms) and insoluble salts are examples of insoluble impurities. These impurities can all typically be present in a fermentation broth. More details on how to obtain the aqueous mixture are provided below.
[0033] The aqueous mixture comprises at least. 5% by weight of dissolved halide salt. Dissolved halide salt as used herein refers to the halide salt in its dissolved state, that is, in the form of solvated ions, in water. The dissolved halide salt can originate from an acidulation reaction in which a polycarboxylate salt is reacted with a halogen acid. The dissolved halide salt can also originate from adding halide salt to an aqueous mixture to increase the concentration of dissolved halide salt. Combinations are, of course, also possible.
[0034] As for the amount of dissolved salt, the following is commented. The effects described above are more pronounced when large amounts of dissolved halide salt are present in the aqueous mixture. For this reason, the use of relatively high concentrations of salt may be preferred. On the other hand, the presence of large amounts of salts can decrease the solubility of the acid in the mixture to a value that is so low that no significant extraction can be carried out. In general, a salt concentration of more than 30% by weight is therefore not desirable. Depending on the amount and nature of the acid, and the nature of the salt, it may be preferred for the amount of salt to be at least 8% by weight, or at least 10% by weight. Again, depending on the amount and nature of the acid, and the nature of the salt, it may be preferred for the amount of salt to be a maximum of 20% by weight, or a maximum of 15% by weight. It is within the scope of the expert to determine the appropriate salt concentration on a case-by-case basis.
[0035] The cations present in the halide salt are preferably one or more selected from the group consisting of magnesium, calcium, potassium, sodium, nickel, cobalt, iron and aluminum, and ammonium. It is preferred to use one or more cations selected from the group of magnesium, calcium, sodium and potassium. The use of calcium and magnesium is particularly preferred, as these cations show a particularly high concentration effect. The use of magnesium may be especially preferred for this reason. Although cation mixtures can be used, for reasons of processing efficiency, it is preferred that at least 90% of the cation in the halide salt be of a single type, according to the above-mentioned preferences. Preferably, the cation is magnesium, as explained below.
[0036] The halide salt can be a fluoride, chloride, bromide, or iodide. The use of chloride is preferred. This selection applies in combination with the preference for the aforementioned cations. Specific examples of preferred salts are those of MgCl2, CaCl2, NaCl, and KCl. These salts have been found to contribute to the concentration effect of the present invention. The use of calcium and magnesium chloride is considered preferred, as they have a high concentration effect. The use of magnesium chloride may be particularly preferred, as it combines a high concentration effect with suitable possibilities for further processing, as will be discussed later.
[0037] In one embodiment, the halide salt is capable of thermal decomposition in HCl. In this embodiment, the halide is, of course, a chloride. Examples of salts capable of thermal decomposition in HCl are chloride salts selected from the group consisting of beryllium chloride, magnesium chloride, titanium chloride, vanadium chloride, chromium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, aluminum chloride, yttrium chloride and zirconium chloride. Such salts can be recycled using thermal decomposition, as described below. Good results were obtained using FeCl3 and MgCl2.
[0038] The aqueous mixture can be prepared by adding halide salt to an aqueous premix that comprises the carboxylic acid.
However, the aqueous mixture is preferably prepared by acidifying a carboxylate salt with an acid, thereby forming an aqueous mixture comprising the carboxylic acid and a halide salt. The acidulation step is typically conducted by bringing the carboxylate salt into contact with an acidic solution.
However, in some embodiments, it may also be possible to contact the gaseous acid carboxylate salt, for example, in certain cases, when using HCl.
[0041] Appropriate carboxylate salts are generally those that are capable of forming a halide salt when acidified, that is, carboxylate salts of an inorganic cation. Examples of suitable carboxylate salts are magnesium carboxylate, calcium carboxylate, sodium carboxylate and potassium carboxylate. In view of the desirable recycling step using thermal decomposition, and taking into account the effect of the pronounced concentration obtained for this compound, preferably magnesium carboxylate is used.
[0042] The carboxylate salt can be in solid and / or dissolved form. In one embodiment, the carboxylate salt is provided in solid form. In this case, the acidulation step is carried out by placing the carboxylate salt in contact with an acidic solution. The advantage of preparing the aqueous mixture of carboxylate salt in solid form is that the very high concentration of carboxylic acid can thus be obtained, such as a concentration of at least 15% by weight, in particular at least 25% by weight, up to, for example, 50% by weight, or for example 40% by weight. The carboxylate salt can also be in dissolved form, typically as part of an aqueous solution. In this case, the acidulation step can be carried out by placing the carboxylate salt in contact with an acidic solution or an acidic gas. This embodiment can be preferred for the polycarboxylic acids of the present invention.
[0043] The acidulation step can also be conducted by a mixture of carboxylic acid and carboxylate salt. Such a mixture can, for example, be obtained from a low pH fermentation. The mixture can be, for example, an aqueous suspension or solution.
[0044] The acid used in the acidulation step is typically a strong acid, such as hydrochloric acid or sulfuric acid. In view of the necessary presence of at least 5% by weight of a halide salt, the use of hydrochloric acid is preferred. In such a case, an aqueous mixture is obtained comprising carboxylic acid and a chloride salt. Acidulation by HCl can, for example, be accomplished by bringing the carboxylate salt in contact with an aqueous HCl solution or by bringing a solution of carboxylate salt or suspension in contact with HCl gas.
[0045] When acidulation of the carboxylate salt is conducted by contact with an acidic solution, which preferably has an acid concentration as high as possible. This high concentration of acid will result in an aqueous mixture with a high concentration of carboxylic acid, which is desirable. Therefore, the acidic solution comprises at least 5% by weight, more preferably at least 10% by weight and even more preferably, at least 20% by weight of acid, based on the total weight of the acidic solution.
[0046] Acidulation is typically conducted using an excess of acid. The excess is preferably small, such that the aqueous mixture obtained is not highly acidic, which may not be desirable, in view of the processing of such a mixture. For example, the excess acid used may be such that the resulting aqueous mixture has a pH of 2 or less, preferably a pH of 0 to 1.
[0047] In case an acidic gas is used (for example, gaseous HCl), it can be contacted by bringing in contact with a carboxylate solution or suspension. In particular, the HCl gas can be blown through the solution or suspension. In case the HCI gas is used, the HCl can originate from a thermal decomposition step, as described above.
[0048] Preferably, acidulation is conducted at a temperature of 75 ° C or less. At higher temperatures, it becomes uneconomical to adapt the equipment to the adverse conditions of an acidic environment at high temperatures.
[0049] After acidulation, the solid material can be removed from the aqueous mixture, for example by filtration. For example, in the case where the polycarboxylic acid has a low solubility in water, the carboxylic acid that precipitates during the acidification step can be by filtration, with the remaining solution containing dissolved carboxylic acid and the halide salt being subjected to extraction by process according to the invention.
[0050] The aqueous mixture can be concentrated after acidulation before the extraction of a concentration step. The upper limit for the concentration step is, in general, the solubility of the halide salt or polycarboxylic acid, whichever comes first. Adequate concentrations for these compounds have been described elsewhere.
[0051] In one embodiment, a carboxylate salt is used which originates from a fermentation process. Thus, the method of the invention may further comprise a fermentation step, to form the carboxylic acid, which fermentation process comprises the steps of fermenting a carbon source, such as a carbohydrate, by means of a microorganism in a fermentation broth to form the carboxylic acid and neutralize at least part of the carboxylic acid by adding a base, in particular a magnesium or calcium base, thereby obtaining a carboxylate salt.
[0052] The fermentation processes for the production of carboxylic acids are known in the art and do not require further explanation here. It is within the scope of the person skilled in the art to select, using his common knowledge, an appropriate fermentation process, depending on the desired acid to be produced, the carbon source and the microorganism available.
[0053] The product of the fermentation process is a fermentation broth, which is an aqueous liquid comprising a carboxylate salt, biomass, and optionally other components, such as impurities, such as sugars, proteins and salts .
[0054] If so desired, the fermentation broth can be subjected to a biomass removal step, for example, a filtration step, before further processing. This is generally preferred for improving the quality of the product.
[0055] Depending on the carboxylic acid produced, another intermediate step may be the separation of the solid reaction product, for example, magnesium carboxylate, from the fermentation broth, before, after, or simultaneously with the removal of biomass, and optionally subjecting the magnesium carboxylate to a washing step.
[0056] Depending on the carboxylic acid produced, another intermediate step can be submitted to the fermentation broth for a concentration step to increase the concentration of magnesium carboxylate in the composition before acidification. This step can be performed before, after or simultaneously with the removal of biomass.
[0057] Other intermediate steps, for example, purification steps, can be carried out as desired, as will be apparent to the person skilled in the art.
[0058] In general, for polycarboxylic acids a way of carrying out a suitable processing sequence would be as follows: - the formation of a fermentation medium comprising a dissolved polycarboxylate salt, as described above, - optional removal of biomass, as described above, - optional concentration step to increase the concentration of the polycarboxylate salt, - acidification, to convert the polycarboxylate salt into polycarboxylic acid, with accompanying formation of the halide salt, - separation of insoluble polycarboxylic acids at from the mixture to obtain a liquid containing polycarboxylic acid for its level of solubility and halide salt, - optional concentration of the solution to increase the concentration of the halide salt (when necessary, followed by the removal of the additional acid precipitate), or optional addition of halide salt, to ensure the desired halide salt concentration, - extraction, as described above.
[0059] In the method according to the invention, the aqueous mixture discussed above is subjected to an extraction step by contacting it with an organic liquid comprising an organic solvent selected from the group of ketones and ethers, thus obtaining a solution of organic carboxylic acid and an aqueous residue liquid comprising the halide salt. In this forward extraction, the carboxylic acid is separated from the impurities present in the aqueous mixture, dissolving it in a first organic liquid. The impurities will remain in the aqueous mixture.
[0060] Preferably, the organic liquid comprises at least 90% by weight of the organic solvent, preferably at least 95% by weight, more preferably at least 99% by weight. In one embodiment, the organic liquid is the organic solvent. Typically, small amounts of water can be present in the first organic liquid, particularly when the liquid (in part) comprises organic solvent recycled from a recycling step after extraction.
[0061] The organic solvent is selected from the group of ketones and ethers. It was found that these compounds have good properties in the process according to the invention, where they have a good concentration effect. The selection of a suitable organic solvent can contribute to the establishment of a high distribution ratio during forward extraction. In that case, only a relatively small amount of carboxylic acid will be lost in the aqueous residual liquid.
[0062] It is preferred to use ketones, in particular, C5 + ketones, more especially, C5 - C8 ketones in the present invention. C5 + means ketones with at least 5 carbon atoms. Mixtures can also be used. The use of C9 + ketones is less preferred, because these compounds are believed to show a lower concentration effect, and may result in more contaminants present in the final product. The use of methyl isobutyl ketone (MIBK) has been found to be particularly attractive to obtain a good concentration effect. In addition, the use of ketones has been found to be preferred because they are stable under process conditions, as they do not react or decompose substantially, thus giving rise to few contaminants, and allowing for a stable process operation. Ethers can also be used, especially C3 - C6 ethers. It has been found, however, that they are less preferred, in particular because the use of ethers resulted in the loss of more solvent and more contaminants in the final product. Within the ether group, the use of tert-butyl methyl ether (MTBE) and diethyl ether (DEE) may be preferred, but less preferred than the use of ketones.
[0063] The method of the invention does not require the use of extracting agents, such as amines. In fact, the use of extraction agents in which the organic solvent is generally undesirable. An extraction agent is a compound that forms a complex with the compound to be extracted (in this case, the carboxylic acid). However, the formation (during forward extraction) and breaking of the complex would require a relatively large amount of energy, such that the temperature difference between forward extraction and return would have to be greater than necessary. Therefore, the organic liquid preferably comprises none or substantially no extracting agents, in particular, none or substantially no amine extracting agents. Thus, the carboxylic acid in the process of the invention is preferably extracted, in its neutral acid form and not in the form of a salt or a complex.
[0064] The organic liquid is preferably essentially free of amines, ethers and alcohols, which means that these compounds, if present at all, are each present in an amount of less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, calculated with respect to the weight of the organic liquid.
[0065] The ratio of the organic liquid to aqueous mixture used in the forward extraction is determined by the following considerations. On the one hand, if the amount of organic liquid is relatively high, the extraction efficiency, expressed as the percentage of acid in the aqueous mixture that is extracted in the organic liquid, will be high. On the other hand, a large amount of organic liquid will have to be used, and the concentration effect will be reduced. On the other hand, if the amount of organic liquid is relatively low, the effect of the concentration will be improved, but the extraction efficiency will be reduced.
[0066] The Distribution Ratio (DR) defined above can provide guidance in this regard. In one embodiment, the amount of organic liquid used in the forward extraction can be in the range of 0.5 / DR to 1.5 / DR times the amount of aqueous mixture.
[0067] The use of an amount of organic liquid in the range of 0.5 / DR to 0.8 / DR times the amount of aqueous mixture for extraction forward may be desirable for a good concentration effect. However, the yield of the extraction step may, in this case, be less than 99%. The use of an amount of organic liquid in the range of 1.3 / DR to 1.5 / DR times the amount of aqueous extraction mixture forward can result in an extraction yield of more than 99%, but it typically has an effect less pronounced concentration. The use of an amount of organic liquid in the range of 0.8 / DR to 1.3 / DR, and in particular in the range of 1.0 / DR to 1.2 / DR, times the amount of aqueous extraction mixture for forward is more desirable, because both a good concentration effect and an extraction yield of more than 99% can be obtained. The extraction yield, as used herein, refers to the percentage by weight of the carboxylic acid that is extracted in the organic liquid during the forward extraction.
[0068] Forward extraction is typically conducted by contacting the aqueous mixture with the first organic liquid, thus obtaining a solution of organic carboxylic acid and an aqueous residual liquid comprising the halide salt. Preferably, the extraction is a countercurrent extraction, i.e., the aqueous mixture and the organic liquid are contacted with each other using countercurrent currents. In such a configuration, a very efficient extraction of carboxylic acid in which the organic liquid can be obtained, in particular, with regard to yield.
[0069] The extraction is preferably carried out in an extraction column. In case the used organic solvent has a lower density than water (for example, in the case of MIBK), the organic solvent is preferably fed to the bottom of the column, whereas the aqueous mixture is fed to the top of the column.
Therefore, two phases will be formed: a higher phase comprising the organic solvent and a lower phase comprising the aqueous mixture. At the interface of the two phases, any biomass and / or solid material present in the aqueous mixture will accumulate. As described above, biomass does not cause emulsification, due to the presence of salt in the aqueous mixture. By feeding the organic solvent, at the bottom of the column, the organic solvent will move upwards, through the aqueous mixture, thus extracting the carboxylic acid and forming an organic solution of carboxylic acid. At the bottom of the column, an aqueous residual liquid can be obtained, typically in the form of an aqueous saline solution, a solution comprising the halide salt.
[0071] Extraction forward can be conducted at a temperature of 20 to 100 ° C, preferably at a temperature of 30 to 80 ° C, for example, at a temperature of 40 to 60 ° C. In order to reach the desirable temperature for the forward extraction, the aqueous and / or liquid organic mixture can be heated before the forward extraction. As described above, higher temperatures within the range of 20 to 100 ° C are advantageous with respect to a decrease in the solubility of the organic solvent in water. In addition, the distribution ratio may increase with increasing temperatures and / or may lead to a stronger concentration effect. Taking into account the possible corrosive conditions of the aqueous acid mixture, a temperature above 60 ° C can be disadvantageous. However, corrosion can, for example, be prevented by using plastic or glass-lined extraction equipment. The aqueous residual liquid formed in the forward extraction comprises the halide salt. The aqueous residual liquid is typically obtained in the form of an aqueous salt solution, which comprises the halide salt solution. This solution is relatively pure, since insoluble impurities typically remain at the interface of the water / organic interface during extraction.
[0072] To avoid the loss of acid from the system, it is preferred for the concentration of polycarboxylic acid in the residual liquid to be as low as possible. In one embodiment, the concentration of the polycarboxylic acid in the residual liquid is less than 1% by weight, in particular less than 0.5% by weight, more in particular less than 0.1% by weight. It has been found that the extraction using the method according to the invention allows to obtain such very low acid losses. In order to prevent the loss of solvent from the system, and to avoid problems in further processing, in particular when using a thermal decomposition step, it is preferred that the concentration of the solvent in the residual liquid be as low as possible. In one embodiment, the concentration of the solvent in the waste liquid is less than 1% by weight, in particular less than 0.5% by weight, more particularly less than 0.2% by weight, and preferably below 0 , 1% by weight. It was found that the extraction using the method according to the invention allows obtaining such losses of very low content solvents.
[0073] It is preferred that at least 80% of the acid present in the system is in the organic phase after forward extraction, in particular at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at minus 99%. It is preferred that at least 90% of the halide salt present in the system to be present in the aqueous residual liquid after extraction forward, preferably at least 95%, more preferably at least 98%, in particular at least 99%.
[0074] The organic carboxylic acid solution is subsequently subjected to a re-extraction step. Optionally, the organic carboxylic acid solution obtained in the forward extraction is subjected to an intermediate washing step to remove any impurities present in the organic carboxylic acid solution. Such impurities are typically entrained from the aqueous mixture, for example, chloride or metal ions. In such a washing step, the organic solution of carboxylic acid is brought into contact with a washing liquid. Such a step can decrease the amount of impurities, such as chloride and / or metal ions in the final product, that is, the aqueous solution of carboxylic acid. Removing these ions can prevent further corrosion problems. The washing liquid is typically an aqueous liquid. In one embodiment, part of the aqueous carboxylic acid solution formed as a product of re-extraction is used as a washing liquid. In this embodiment, a small part, for example, 0.5 to 5% by weight, in particular 0.5 to 2% by weight, of the total aqueous carboxylic acid solution of the product can be used for washing. The washing liquid can subsequently be recycled back to the aqueous mixture, where it will be subjected to re-extraction again. Care must be taken during washing to not remove excess acid from the organic liquid, as this will negatively affect the concentration of carboxylic acid in the final product. It is within the skill of the person skilled in the art to determine the proper washing conditions.
[0075] The organic solution of carboxylic acid formed in the extraction forward is, optionally after being washed, extracted again with an aqueous liquid, thus obtaining an aqueous solution of carboxylic acid and a second organic liquid. This step can be referred to here as the second extraction or re-extraction. The results of re-extraction in an aqueous solution of carboxylic acid, which has a higher degree of purity and in particular a lower concentration of the salt than the initial aqueous mixture. As explained above, the aqueous carboxylic acid solution of the product of the present invention typically has a higher concentration of carboxylic acid than the aqueous mixture.
[0076] The ratio of aqueous liquid to organic acid solution used for re-extraction is determined by the following considerations. On the one hand, if the amount of aqueous liquid is relatively high, the extraction efficiency, expressed as the percentage of acid in the organic acid solution that is extracted in the aqueous liquid, will be high. On the other hand, a large amount of aqueous liquid will have to be used, and the effect of the concentration will be reduced. On the other hand, if the amount of aqueous liquid is relatively low, the concentration effect will be improved, but the extraction efficiency will be reduced.
[0077] An adequate value for the ratio of aqueous liquid to organic acid solution used in which re-extraction can be derived from the distribution ratio (DR) defined above. In one embodiment, the amount of aqueous liquid used for re-extraction is 0.5 * DR to 1.5 * DR times the amount of the organic solution of carboxylic acid. These reasons can, in particular, be important with regard to the concentration effect of the present method. The use of an amount of aqueous liquid in the range of 0.5 * DR to 0.8 * DR times the amount of organic carboxylic acid solution for re-extraction may be desirable for a good concentration effect. However, the yield of the re-extraction step may in this case be less than 99% yield. The use of an amount of aqueous liquid in the range of 1.3 * DR to 1.5 * DR times the amount of organic carboxylic acid solution for reextraction can result in a reextraction yield of more than 99%, but typically has a less pronounced concentration effect. The use of an amount of aqueous liquid in the range of 0.8 * DR to 1.3 * DR, and in particular in the range of 1.0 * DR to 1.2 * DR times the amount of organic carboxylic acid solution is more desirable, because both a concentration effect and a good re-extraction yield of more than 99% can be obtained. The re-extraction yield, as used herein, refers to the percentage by weight of the carboxylic acid that is extracted into the aqueous liquid during re-extraction. Re-extraction is typically conducted by contacting the organic solution of carboxylic acid with the aqueous liquid, thereby obtaining an aqueous solution of carboxylic acid and a second organic liquid. The aqueous solution of carboxylic acid is the solution of the product. If so desired, the second organic liquid, in whole or in part, can be recycled for extraction forward as the first organic liquid, optionally, after having been subjected to a purification step. Preferably, the extraction is a countercurrent extraction. In such a configuration, a very efficient extraction of carboxylic acid in which the aqueous liquid can be obtained, in particular, with respect to yield.
[0078] The extraction is preferably carried out in an extraction column. In the event that the organic solvent used has a density lower than that of water, the aqueous liquid is preferably fed to the top of the column, while the organic solution of carboxylic acid is fed to the bottom of the column. Therefore, it will form two phases: an upper phase which comprises the organic solvent and a lower phase which comprises the aqueous liquid. When feeding the aqueous liquid in the upper phase of the column, which will pass down through the organic solution of carboxylic acid, thus extracting the carboxylic acid and forming an aqueous solution of carboxylic acid. An aqueous solution of carboxylic acid can then be recovered at the bottom of the column.
[0079] It is noted that in any case to evaporate the organic solvent from the organic solution of carboxylic acid after extraction forward, thereby obtaining the carboxylic acid directly. However, the best results have been obtained when using a re-extraction according to the present invention. Re-extraction resulted in less impurities and a more energy efficient process.
[0080] Re-extraction can be carried out at a temperature of 20 to 100 ° C, preferably at a temperature of 80 ° C or less, more preferably at a temperature of 60 ° C or less. Re-extraction is preferably conducted at a temperature above 0 ° C, preferably at a temperature of at least 10 ° C, due to the energy costs associated with cooling. Temperatures equal to or close to the temperature in the forward extraction are particularly preferred for re-extraction. This can save energy, as less heating and / or cooling is required between the different streams of the extraction process. In this way, in one embodiment, the reextraction is carried out at a temperature that within 10 ° C, for example, within 5 ° C of the temperature at which the forward extraction is carried out. The use of a similar temperature for forward and return extraction is also referred to here as isothermal conditions. Forward extraction and reextraction can be conducted at approximately the same temperature, for example, using the temperature difference between forward extraction and reextraction below 5 ° C.
[0081] In one embodiment, extraction in the organic liquid (extraction forward) is conducted at a lower temperature than extraction with the aqueous liquid (re-extraction). Such an extraction method is also known as a regular temperature balance extraction. The temperature during re-extraction, in this case, is 5 to 45 ° C, for example, 10 to 20 ° C higher than the forward extraction temperature.
[0082] In another embodiment, extraction in the organic liquid (extraction forward) is conducted at a higher temperature than extraction in the aqueous liquid (re-extraction). Such an extraction method can be indicated as a reverse balance extraction temperature. In reverse temperature swing extraction, the re-extraction step can, in this case, be conducted at a temperature that is 10 to 50 ° C or 20 to 30 ° C lower than the temperature at which the forward extraction is accomplished. It was verified that operating the extraction in reverse temperature oscillation mode can lead to an increase in the concentration of the acid in the product.
[0083] In an embodiment of the process according to the invention, the organic solution of carboxylic acid is brought into thermal contact with the second organic liquid using a heat exchanger. This is advantageous when forward and backward extraction are conducted at different temperatures.
[0084] The aqueous solution of carboxylic acid obtained after re-extraction as carried out in accordance with the present invention has a higher concentration of carboxylic acid than the aqueous mixture that was fed for the forward extraction. This is also illustrated in the examples below.
[0085] The extent of the concentration effect of the method of this invention depends on the ratio between the organic liquid and aqueous mixture used in the extraction forward, the ratio of the organic solution of carboxylic acid and aqueous liquid used for re-extraction, the temperature where the extraction steps are conducted, the type of organic liquid used and the amount of dissolved halide salt present in the aqueous mixture. In addition, it is preferred to select the process conditions, in such a way that, in order to obtain a high extraction yield. In this regard, it is preferable that the amount by weight of organic liquid used in the forward extraction is 1.0 / DR to 1.2 / DR times the amount by weight of the aqueous mixture while the amount by weight of the aqueous liquid used on re-extraction it is from 1.0 * DR to 1.2 * DR times the amount by weight of the organic solution of carboxylic acid. It is even more preferred that the amount by weight of organic liquid used in the forward extraction is 1.1 / DR to 1.2 / DR times the amount by weight of the aqueous mixture while the amount by weight of aqueous liquid used in the extraction is 1.1 * DR to 1.2 * DR times the amount by weight of the organic carboxylic acid solution. These weight ratios result in a special effect of good concentration when, additionally combined with a forward extraction temperature of 50 to 60 ° C. The organic liquid used in this case is preferably a ketone, more preferably MIBK. In this case, the re-extraction is preferably carried out at 20 to 60 ° C, more preferably at 50 to 60 ° C.
[0086] Thus, the following combination of parameters can result in a particularly good concentration effect and can at the same time result in a good extraction yield: - a forward extraction temperature of 30 to 60 ° C, in particular 50 to 60 ° C; - a re-extraction temperature of 20 to 60 ° C; - an amount by weight of organic liquid used in the forward extraction that is 1.1 / DR to 1.2 / DR times the amount by weight of the aqueous mixture; - an amount by weight of aqueous liquid used for re-extraction which is 1.1 * DR to 1.2 * DR times the amount by weight of the organic solution of carboxylic acid; - the organic liquid being a ketone, in particular, a C5-C8 ketone group, more particularly methyl isobutyl ketone.
[0087] The total yield of the method of the present invention depends on both the extraction yield on extraction forward and the extraction yield on re-extraction. The yield of forward extraction can be increased by driving the extraction forward with countercurrent currents (see also above). This countercurrent extraction can be carried out in one or more vessels (for example, a mixer or decanter). The yield of the extraction step can be increased by increasing the size and / or the number of the vessel (s). When more than one vessel is used, the vessels are connected in series with each other. In this case, the second or additional vessel further extracts the aqueous liquid obtained after extraction in the previous vessel. Preferably, however, the re-extraction is carried out in a vessel (for example, an extraction column) that is large enough to obtain the desired high yield (typically above 99%). For example, large extraction columns with a height of 10 to 20 meters are known in the art. The expert will be able to adjust the size and / or the number of vessels to obtain a yield of 99% or more.
[0088] The re-extraction yield can be increased in the same way as described above for forward extraction. If more than one vessel is used, the second or additional vessel further extracts the organic liquid obtained after extraction in the previous vessel.
[0089] The method of the invention may further comprise the step of concentrating the aqueous solution of the product's carboxylic acid by evaporation of water. The water evaporated in this step can be recycled through reuse as the aqueous liquid on re-extraction. It is possible that the aqueous carboxylic acid solution of the product will comprise a smaller amount of organic solvent and residue from the extraction step, if it is present, for example, in the order of 0.1 to 3% by weight based on the total amount of the solution aqueous carbohydrate. When an evaporation step is carried out, the organic solvent is also typically evaporated in the concentration step, often increased by a water extraction effect.
[0090] As indicated above, the second organic liquid obtained on re-extraction can be recycled through reuse as the first organic liquid for extraction forward.
[0091] In the case of the halide salt of a chloride salt (for example, MgCl2), the method of the invention preferably comprises the step of subjecting the aqueous residual liquid obtained in the extraction to a thermal decomposition step at temperatures at least 300 ° C, thus forming a metal oxide (for example, MgO) and HCl. In this step, the chloride salt is thermally hydrolyzed under the formation of metal oxide and HCl, in which the compounds can be recycled in other steps in a process for the preparation of carboxylic acid. For example, metal oxide can be used in a fermentation process, for example as a neutralizing agent or as a precursor to it. For this purpose, metal oxide can be brought into contact with water to obtain a suspension of metal hydroxide (for example, Mg (OH) 2). In addition, HCl can be used to acidify magnesium carboxylate obtained in a fermentation process. HCl is typically dissolved in water, during or after thermal decomposition, thereby obtaining a solution of HCl.
[0092] Thus, the thermal decomposition step provides a process in which the waste material is recycled and in which consequently relatively little waste is produced.
[0093] The method of the invention is preferably a continuous process. However, it can also be conducted as a batch process.
[0094] The invention will be further illustrated by the following examples, without being limited to them or so. General Procedure
[0095] The general procedure is created to imitate a continuous extraction process. That is, the volume ratios between the extractor and the medium to be extracted are such that the concentration of the acid in the medium to be extracted is not significantly affected by the extraction.
[0096] A feed solution was prepared comprising the acid and salt in the amounts stipulated in the table. The solutions were stirred overnight.
[0097] 1000 g of this feed solution was mixed with about 100 g of methyl isobutyl ketone as a solvent and stirred at 20 ° C for a minimum of 15 minutes. The mixture was transferred to a separating funnel where the phases were separated. Samples from both phases were taken for analysis. Then, about 100 g of the organic phase was mixed with 10 g of pure water and stirred for a minimum of 15 min at 20 ° C. Subsequently, the entire mixture is transferred back to the separating funnel, the phases are allowed to separate and samples of both phases are taken. The samples were analyzed for acid content. Example 1: Extraction of different types of acids
[0098] Solutions containing magnesium chloride as salt and, respectively, succinic acid, itaconic acid, and fumaric acid. The composition of the feeding solutions is shown in table 1.1. The results are shown in tables 1.2, 1.3 and 1.4. These tables also give the concentration ratio, which is the ratio between the concentration of acid in the product and the concentration of acid in the food.
Table 1.2: Succinic acid
Table 1.3: Itaconic acid
Table 1.4: Fumaric acid
Example 2: effect of the type of salt
[0099] To investigate the effect of the nature of the salt, succinic acid was extracted from solutions containing succinic acid and different types of salts. The composition of the initial solution and the concentration of acid in the products are shown in Table 2.1 below. From the table it can be seen that magnesium chloride has a particularly high concentration ratio.

权利要求:
Claims (32)
[0001]
1. Method for the recovery of polycarboxylic acid from an aqueous mixture, characterized by the fact that it comprises the steps of (a) providing an aqueous mixture comprising polycarboxylic acid and from 5 to 30% by weight of dissolved chloride salt , based on the total weight of the water and material dissolved in the aqueous mixture, (b) extracting the polycarboxylic acid from the aqueous mixture in a first organic liquid comprising at least 90% by weight of an organic solvent selected from the group consisting of in C5-C8 ketones and C3-C6 ethers, thus obtaining a solution of the organic polycarboxylic acid and an aqueous residual liquid comprising the halide salt, and (c) extracting the organic polycarboxylic acid from the polycarboxylic acid solution in a liquid aqueous, thus obtaining an aqueous solution of polycarboxylic acid and a second organic liquid, wherein the polycarboxylic acid is a di- or tri-carboxylic acid thus comprising at least 2, m those no more than 6 carbon atoms; and in which the cations present in the chloride salt are one or more selected from the group consisting of magnesium, calcium, sodium and potassium ions.
[0002]
Method according to claim 1, characterized in that the aqueous mixture comprises from 8 to 20% by weight of dissolved chloride salt.
[0003]
Method according to claim 1 or 2, characterized in that the organic solvent is a C5C8 ketone.
[0004]
Method according to claim 3, characterized in that the organic solvent is methyl isobutyl ketone.
[0005]
Method according to any one of claims 1 to 4, characterized in that the first extraction step (b) is carried out at a temperature of at least 30 ° C.
[0006]
Method according to any one of claims 1 to 5, characterized in that the second extraction step (c) is carried out at a temperature lower than the temperature at which the first extraction is carried out.
[0007]
Method according to claim 6, characterized in that the second extraction step (c) is carried out at a temperature of 10 to 50 ° C lower than the temperature at which the first extraction is carried out.
[0008]
Method according to any one of claims 1 to 6, characterized in that the second extraction step (c) is carried out within 10 ° C of the temperature at which the first extraction (b) is carried out.
[0009]
Method according to any one of claims 1 to 8, characterized in that the polycarboxylic acid is selected from the group among succinic acid, citric acid, fumaric acid, itaconic acid, adipic acid, maleic acid, 2.5- furandicarboxylic, malic acid, and tartaric acid.
[0010]
10. Method according to claim 9, characterized in that the polycarboxylic acid is selected from the group among succinic acid, citric acid, fumaric acid, itaconic acid, adipic acid and 2,5-furandicarboxylic acid.
[0011]
11. Method according to claim 9, characterized by the fact that polycarboxylic acid is selected from the group among succinic acid, fumaric acid, itaconic acid and 2,5-furandicarboxylic acid.
[0012]
Method according to any one of claims 1 to 11, characterized in that the chloride salt is magnesium chloride and / or calcium chloride.
[0013]
Method according to any one of claims 1 to 12, characterized in that the organic solvent is free of extractors, said extractors being compounds that form a complex with the carboxylic acid to be extracted.
[0014]
Method according to any one of claims 1 to 13, characterized in that the organic solvent is free of amine extractors, said amine extractors being compounds that form a complex with the carboxylic acid to be extracted.
[0015]
Method according to any one of claims 1 to 14, characterized in that the aqueous mixture has a pH 2 or less.
[0016]
16. Method according to any one of claims 1 to 15, characterized in that said polycarboxylic acid from step (a) is derived from a fermentation process, said process comprising the steps of: (i) fermentation of a carbon source through a microorganism in a fermentation broth to form polycarboxylic acid; and (ii) neutralizing at least part of the polycarboxylic acid by adding base.
[0017]
17. Method according to claim 16, characterized in that the base of magnesium, calcium, sodium or potassium is used to neutralize at least part of the polycarboxylic acid.
[0018]
Method according to any one of claims 1 to 17, characterized in that the polycarboxylic acid of step (a) is prepared by acidifying a polycarboxylate salt with an acid.
[0019]
19. Method according to any one of claims 1 to 17, characterized in that the method further comprises the steps of: - preparing an aqueous mixture by acidifying a polycarboxylate salt with HCl, thereby obtaining a polycarboxylic acid which is partially in the form of solid and partially dissolved and a dissolved chloride salt, - subject the aqueous mixture to a separation step to separate the solid polycarboxylic acid from the aqueous medium comprising dissolved polycarboxylic acid and dissolved chloride salt, and - subject the aqueous medium comprising dissolved polycarboxylic acid and dissolved chloride salt to an extraction step.
[0020]
20. Method according to any one of claims 1 to 17, characterized in that it still comprises the step of: - preparing an aqueous mixture by acidifying a polycarboxylate salt with HCl, thus obtaining a polycarboxylic acid, which is partially in the solid and partially dissolved form and a dissolved chloride salt; - subjecting an aqueous mixture to a separation step to separate the solid polycarboxylic acid from the aqueous medium comprising dissolved polycarboxylic acid and dissolved chloride salt; and - subjecting the aqueous medium comprising dissolved polycarboxylic acid and dissolved chloride salt to an extraction step, with intermittent concentration or adjustment of the chloride salt concentration.
[0021]
21. Method according to any one of claims 18 to 20, characterized in that said acidification step is carried out in a mixture of polycarboxylic acid and polycarboxylate salt.
[0022]
22. The method of any one of claims 18 to 21, characterized in that said acidification step comprises bringing the polycarboxylate salt in solid form or in aqueous solution in contact with the aqueous HCl solution.
[0023]
23. The method of any one of claims 18 to 21, characterized in that said acidification step comprises placing an aqueous solution of the polycarboxylate salt in contact with the gaseous HCl.
[0024]
24. Method according to any one of claims 1 to 23, characterized in that it further comprises - subjecting the chloride salt solution obtained in step (b) to a thermal decomposition step at a temperature of at least 300 ° C , thus decomposing the chloride salt into a metal oxide and HCl; e - dissolve the HCl formed in the thermal decomposition step in water, thus obtaining an HCl solution; and - optionally, recycling the metal oxide in a fermentation process as a neutralizing agent or a precursor to it.
[0025]
25. Method according to any one of claims 1 to 23, characterized in that the chloride salt is MgCl2.
[0026]
26. Method according to claim 25, characterized by the fact that it further comprises: - subjecting the magnesium chloride solution obtained in step (b) to a thermal decomposition step at a temperature of at least 300 ° C, thus decomposing the chloride salt in a magnesium oxide (MgO) and HCl.
[0027]
27. The method of claim 26, characterized by the fact that MgO is recycled for use in a fermentation process as a neutralizing agent or as a precursor to it.
[0028]
28. Method according to claim 26, characterized by the fact that it still comprises placing the MgO in contact with water, thus obtaining a sludge of magnesium hydroxide (Mg (OH2).
[0029]
29. The method of claim 28, characterized in that said magnesium hydroxide (Mg (OH) 2) sludge is recycled for use in a fermentation process as a neutralizing agent.
[0030]
30. Method according to any of claims 26 to 29, characterized in that the HCl obtained in the thermal decomposition step is used in an acidification step either as an HCl gas or as an aqueous HCl solution, said aqueous solution being obtained by dissolving the HCl formed in the thermal decomposition step in water.
[0031]
31. Method according to any one of claims 26 to 29, characterized in that it further comprises dissolving the HCl formed in the thermal decomposition step in water, thus obtaining the HCl solution.
[0032]
32. The method of any one of claims 26 to 29, characterized in that said HCl obtained in the thermal decomposition step is used in the acidification of a magnesium polycarboxylate salt to form an aqueous mixture comprising the corresponding polycarboxylic acid and magnesium chloride (MgCl2), said HCl being used in acidification either as HCl gas or as an aqueous solution of HCl, said aqueous solution being obtained by dissolving the HCl formed in the thermal decomposition step in water.

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US20150004663A1|2015-01-01|

JP6118338B2|2017-04-19|

KR101650694B1|2016-08-24|

AU2012356848A1|2014-07-31|

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2019-06-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

2019-10-29| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

2020-04-22| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

2020-11-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-02-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

US201161579730P| true| 2011-12-23|2011-12-23|

EP11195691.8|2011-12-23|

US61/579,730|2011-12-23|

EP11195691|2011-12-23|

PCT/EP2012/076735|WO2013093043A1|2011-12-23|2012-12-21|Polycarboxylic acid extraction|

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