JP2010180171A - Method for producing acrylic acid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply producing high-purity acrylic acid having no discoloration from a 3-hydroxypropionic acid fermented solution produced by a biochemical method using resources of biologic origin, especially glycerin obtained from oils and fats and/or a saccharide derived from a biomass, as a raw material. <P>SOLUTION: The method for producing acrylic acid includes a step for extracting 3-hydroxypropionic acid from a 3-hydroxypropionic acid-containing fermented solution with an organic solvent having low affinity for water and performing a dehydration reaction in a specific temperature range. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing acrylic acid using a 3-hydroxypropionic acid composition produced by a biochemical method using glycerin and / or biomass-derived sugar obtained from biological resources, particularly oils and fats, as a raw material. About.

  Acrylic acid is widely used industrially, such as various acrylates, acrylates, and polyacrylates, and is particularly known as a raw material monomer for water-absorbing resins. As a method for producing acrylic acid, a production method by two-stage oxidation of propylene and a production method by hydrolysis of acrylonitrile with sulfuric acid are known. On the other hand, recently, from the viewpoint of global warming prevention and environmental protection, attention has been focused on the use of recyclable biological resources as a carbon source as a substitute for conventional fossil raw materials.

  For example, fatty acid methyl esters obtained by transesterification of fats and oils, so-called biodiesel fuel (BDF), have already been put into practical use by being partially mixed with light oil. This BDF is obtained by reacting fats and oils, which are triglycerides of fatty acids, with methanol to form methyl esters of fatty acids, and glycerin is obtained as a by-product. The glycerin produced as a by-product has become an excessive supply source, and development of an effective utilization method is underway. As an example of the effective utilization method of this glycerol, the manufacturing method of acrylic acid via acrolein by the dehydration reaction of glycerol is mentioned (refer patent document 1, 2).

Also disclosed is a method for producing acrylic acid by dehydrating 3-hydroxypropionic acid obtained by fermenting 3-hydroxypropionic acid using glycerin as a carbon source (see Patent Documents 3 and 4). Yes. (See Patent Documents 5 and 6)
As a method for producing 3-hydroxypropionic acid, a production method using a sugar such as glucose derived from biomass as a raw material has been disclosed (see Patent Document 7), and a method for producing acrylic acid from a sugar derived from biomass has been widely studied. ing.

  A method of producing acrylic acid by dehydration from 3-hydroxypropionic acid or a salt thereof obtained by fermentation using glycerin or sugar from the above-mentioned biological resources as a carbon source is a method of producing 3-hydroxypropion in the presence of an organic reagent. It is disclosed that after the acid ammonium salt is heated to decompose into 3-hydroxypropionic acid, acrylic acid is further generated by dehydration, but there is a by-product organic acid and it is immiscible as an organic reagent. Since heat treatment was performed at a high temperature using the organic amine, there was a problem in quality and there was room for improvement.

JP 2005-213225 A International Publication WO2006 / 114506 International Publication WO2001 / 16346 JP 2007-82476 A JP-T-2004-532855 International Publication WO2003-8295 JP-T-2004-514431

  In the method for producing acrylic acid, a 3-hydroxypropionic acid-containing fermentation broth (hereinafter referred to as 3HPA composition) which is a 3-hydroxypropionic acid composition produced by a biochemical method (hereinafter also referred to as 3HPA composition) In addition to 3-hydroxypropionic acid (hereinafter sometimes referred to as 3HPA), organic acids such as lactic acid, acetic acid, and butyric acid produced as metabolites are mixed in. These had problems with the productivity and purity of acrylic acid when the dehydration reaction was performed using organic amine extracted from 3HPA fermentation broth containing by-products. That is, since the 3HPA fermentation solution is a dilute aqueous solution, it is preferable to remove water in order to increase the reaction rate of the dehydration reaction and increase the productivity, but a method such as distillation causes a problem such as high cost. In addition, it was difficult to separate the organic acid, and there was a quality problem that it was mixed in the product as an impurity. Furthermore, due to the heat treatment of organic amine extracts at high temperatures, quality problems generally attributed to thermally unstable amines, specifically coloring the product during storage A problem has been found that occurs.

  Therefore, the present invention provides a high-purity acrylic that is not colored from a 3-hydroxypropionic acid fermentation broth produced by a biochemical method using glycerin and / or biomass-derived sugars obtained from biological resources, particularly oils and fats, as raw materials. It aims at providing the manufacturing method of an acid.

  The method for producing acrylic acid according to the present invention uses 3-hydroxypropionic acid fermentation liquor and / or a dehydration reaction composition of the fermentation liquor and an organic solvent having low water affinity, so that there is no coloration and organic by-products. It is characterized in that high-purity acrylic acid with little acid, that is, lactic acid, acetic acid, butyric acid, etc. is simple and can be obtained at low cost.

  The inventors of the present invention have studied various methods for producing acrylic acid from 3HPA produced by a biochemical method. After extracting 3HPA and the like using an organic solvent with low water affinity, the inventors heated at a specific temperature. It was found that by performing dehydration treatment, the obtained acrylic acid not only has a small amount of impurities but also has a high purity, and the above-mentioned problem that coloring does not occur can be solved brilliantly.

That is, the present invention
(1) A method for producing acrylic acid using a composition containing 3-hydroxypropionic acid obtained by fermentation of biological resources,
(A-1) An extract composition obtained by extracting at least 3-hydroxypropionic acid, which is brought into contact with a fermentation broth containing 3-hydroxypropionic acid and an organic solvent having low water affinity, exceeds 190 ° C. A step of producing an acrylic acid composition by heating at a low temperature and / or (a-2) a fermentation broth containing 3-hydroxypropionic acid and an organic solvent having low water affinity The organic solvent composition obtained by heating at a temperature not exceeding 190 ° C. to perform a dehydration reaction, and producing an acrylic acid composition,
(B) A method for producing acrylic acid, comprising a step of purifying acrylic acid from the 3-hydroxypropionic acid composition obtained by the steps a-1 and / or a-2.

  (2) Preferably, it is a method for producing acrylic acid using a fermentation broth containing 3-hydroxypropionic acid obtained by fermentation of sugar.

  (3) Preferably, it is a method for producing acrylic acid using a fermentation broth containing 3-hydroxypropionic acid obtained by fermentation using glycerin produced by hydrolysis and / or transesterification of fats and oils as a carbon source.

  (4) The method for producing acrylic acid, wherein the organic solvent having low water affinity is an organic solvent having 6 or more carbon atoms and one or more nitrogen atoms and / or oxygen atoms.

  (5) Acrylic acid that may remove inorganic cations in the fermentation broth by ion exchange before bringing the fermentation broth containing 3-hydroxypropionic acid into contact with the organic solvent having low water affinity. It is a manufacturing method.

  (6) A step of removing ammonia contained in the fermentation broth by heating using an organic solvent having 6 or more carbon atoms and 1 or more nitrogen atoms as the organic solvent having low water affinity. It is the manufacturing method of acrylic acid which you may have.

  (7) The organic solvent having low water affinity obtained in the step of purifying the acrylic acid is a method for producing acrylic acid that may be recovered and used again.

  According to the present invention, it is simple and inexpensive, and it is possible to obtain high-purity acrylic acid with few organic acids such as lactic acid, acetic acid, and butyric acid, which are by-products, and further, colorless acrylic acid.

Process diagram-1 for recovering acrylic acid from culture solution Process for recovering acrylic acid from culture medium Figure-2

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

  First, details of the case of using the step (a-1) (see FIGS. 1 and 2) will be described below.

  The present invention is a method for producing high-purity acrylic acid using 3-hydroxypropionic acid contained in a fermentation broth as a raw material.

  Fermentation liquids containing 3-hydroxypropionic acid and its salts can be obtained from various sources, and methods for obtaining 3-hydroxypropionic acid and its salts include enzymatic processes and fermentation processes. The fermentation reaction for producing this acid is not particularly limited, and typically fermented in the presence of a microorganism, for example, a microorganism described in International Publication WO2001 / 16346 or JP-A-2007-82476. Can be produced.

  As sugars used for fermentation, hexoses such as glucose, lactose, galactose and fructose, pentoses such as xylose, and sugars obtained by hydrolysis of starch and the like can be used.

  Biomass-derived glycerin used for fermentation is obtained by transesterifying fatty acid triglycerides, which are fats and oils of animals and plants, with alcohols such as methyl alcohol to separate the ester phase and the glycerin phase. When fatty acids and glycerides are included as impurities, they are purified by distillation, but in the present invention, impurities may be included as long as they do not affect fermentation.

  As the base used for neutralizing the fermentation broth, ammonia and hydroxides of alkali metals and alkaline earth metals can be used. However, ammonia is preferably used because it is weakly basic and easily undergoes salt exchange. It is.

  The 3HPA fermentation liquid obtained by fermentation may contain lactic acid, acetic acid, butyric acid and the like as by-products in addition to 3HPA.

  Next, the solid content is removed from the fermentation broth containing 3HPA and its salt, and the solution portion of the fermentation broth (sometimes referred to as the fermentation broth supernatant) is recovered. The solid-liquid separation method can be more easily recovered by a known method such as centrifugation or membrane filtration.

  Since the fermentation broth supernatant contains sugar and glycerin that are carbon sources for fermentation, 3HPA that is a product, organic acids that are by-products, etc., an organic solvent is added as an extractant and extracted to extract 3HPA. to recover. Since organic acids and the like are easily dissolved in the extractant, they are contained in the 3HPA extract. In general, the extractant must be used in an amount sufficient to extract the desired portion of dissolved 3-hydroxypropionic acid from the aqueous solution. This can be readily determined by experiment and the required amount of extractant can be reduced by using known multi-stage countercurrent liquid-liquid extraction methods.

  Useful extractants used in the present invention are organic amines that are immiscible with water. Preferably, the organic amine has 6 or more carbon atoms and is liquid at room temperature, preferably has a boiling point higher than 150 ° C. (measured at a pressure of 1 atm), more preferably has a boiling point of 250 ° C. Higher than (measured at a pressure of 1 atm) is better.

  As the organic amine used in the present invention, primary, secondary, tertiary and quaternary amine salts can be used. The nitrogen atom of the amine may be substituted with alkyl, aryl, and aralkyl groups. These groups may also be linear or branched, and may be substituted or unsubstituted. The groups may be the same or different from one another. Alkyl groups are preferred, especially higher alkyl groups (eg at least 8 carbon atoms).

  In the present invention, as shown in FIG. 1, the 3HPA fermentation liquid and the organic solvent are mixed, then the organic phase and the aqueous phase are separated, and then heated to perform a dehydration reaction and distillation. As shown, a suspension in which 3HPA fermentation liquid and an organic solvent are mixed can be prepared, the aqueous phase present in excess can be distilled first, and then the remaining organic phase can be heated to perform a dehydration reaction and distillation. . At this stage, organic acids that are by-produced and mixed with the organic solvent during fermentation are removed. High-purity acrylic acid can be obtained by further distillation-purifying a distillation distillate containing low-boiling substances such as water and acetic acid and acrylic acid purified by the dehydration reaction. The embodiment shown in FIG. 1 is preferably used because the utility phase can be reduced because the aqueous phase is phase-separated and water distillation is not required.

  In the method of the present invention, acrylic acid can be provided by heating 3HPA extracted from the fermentation broth supernatant with an extractant and performing dehydration distillation. 3-Hydroxypropionic acid can be converted to acrylic acid by heating the extractant containing 3HPA at a temperature below 190 ° C. and evaporating the water produced by the dehydration reaction. The heating temperature should be 100 ° C. or higher, but if the temperature is low, the dehydration time becomes long and the productivity is lowered, and if the temperature is too high, the amines as the extractant become unstable, causing problems such as coloring in the product. Therefore, it is preferably 130 ° C. to 180 ° C.

  In the step of dehydration reaction and distillation of the present invention, it is preferable to heat the organic amine at a low temperature and in a short time, so that distillation under reduced pressure is one of the preferred modes. The pressure may be set so that dehydration distillation proceeds within the heating temperature range, and is not particularly limited.

  The dehydration reaction of the present invention is preferably a dehydration reaction in the presence of a dehydration catalyst to evaporate generated water. Examples of the dehydration catalyst include an acid catalyst such as a mineral acid, a base catalyst such as a metal hydroxide, and a calcium phosphate salt. Neutral catalysts such as calcium lactate, aluminum oxide, silicon dioxide and zeolite can be used. As described above, acrylic acid is distilled in this step, and high-boiling substances such as lactic acid and organic amine as an extractant can be separated.

  The low boiling point material containing acrylic acid obtained in the step (a-1) can be further purified by distillation to obtain acrylic acid. In addition, water, acetic acid and a small amount of butyric acid having a boiling point lower than that of acrylic acid are also separated in this step, and high-purity acrylic acid is obtained.

  Next, the case where the step (a-2) is used will be described in detail below.

  3HPA is converted to acrylic acid by adding ethers and ketones having 3 to 7 carbon atoms to the supernatant of the fermentation broth and heating. Since most of the produced acrylic acid is contained on the organic layer side, acrylic acid can be obtained by a known purification method such as distillation of the organic layer taken out by layer separation. The purity of the obtained acrylic acid can be further increased by performing known distillation or crystallization.

  Examples of the ethers and ketones include methyl tertiary butyl ether, ethyl tertiary butyl ether, and methyl isobutyl ketone. Since the latent heat of evaporation is low and the solvent can be recovered with low energy, methyl tertiary Libutyl-ether is preferably used.

  In the heating, it is preferable to use a catalyst because conversion from 3HPA to acrylic acid is accelerated. As the catalyst, a catalyst containing a hydrated oxide of at least one metal element among Zr, Ti, Hf, Sn, and Nb is preferable.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

  Each component was analyzed by gas chromatography.

Example 1
100 g of a fermentation broth (3-hydroxypropionic acid content: 10%) obtained by the method described in JP-A-2007-82476 was centrifuged at 6000 rpm for 20 minutes, and the culture supernatant was collected. 100 g of tri-n-octylamine was added to the collected culture supernatant and mixed gently with a stir bar for 24 hours at room temperature.

  The organic phase was recovered when the mixture was allowed to stand and separated into two phases. 50 g of aluminum oxide was added to the reaction mixture and heated at 170 ° C. for 1 hour.

  The distillate was collected and cooled to room temperature, and then gradually heated from 100 ° C. to 130 ° C. to remove the distillate. Thereafter, the pressure was reduced and the system was gradually heated to 200 ° C. while maintaining the pressure in the system at 20 kPa, and the distillate was recovered.

  When the distillate was analyzed by GC, it was highly pure acrylic acid, and 3-hydroxypropionic acid, lactic acid, and butyric acid were not detected. In addition, no coloration was observed even when the product was stored for several days.

Example 2
150 g of a fermentation broth (3-hydroxypropionic acid content: 10%) obtained by the method described in JP-A-2007-82476 was centrifuged at 6000 rpm for 20 minutes, and then the culture supernatant was collected. The collected culture supernatant was mixed with 10 g of tri-n-octylamine and 15 g of aluminum oxide, and then gradually heated from 100 ° C. to 110 ° C. to remove the distillate. Thereafter, the temperature was further raised, and the mixture was heated at 180 ° C. for 1 hour.

  The distillate was collected and cooled to room temperature, and then gradually heated from 100 ° C. to 130 ° C. to remove the distillate. Thereafter, the pressure was reduced and the system was gradually heated to 200 ° C. while maintaining the pressure in the system at 20 kPa, and the distillate was recovered.

  When the distillate was analyzed by GC, it was highly pure acrylic acid, and 3-hydroxypropionic acid, lactic acid, and butyric acid were not detected. In addition, no coloration was observed even when the product was stored for several days.

Comparative Example 1
In Example 1, the operation was performed in the same manner except that tri-n-octylamine was not used.

  100 g of a fermentation broth (3-hydroxypropionic acid content: 10%) obtained by the method described in JP-A-2007-82476 was centrifuged at 6000 rpm for 20 minutes, and the culture supernatant was collected. 50g of aluminum oxide was added to this reaction mixture, and it heated at 200 degreeC or more for 5 hours. It took time to distill water, and it was confirmed that the utility cost was higher than that in Example 1.

  The distillate was collected and cooled to room temperature, and then gradually heated from 100 ° C. to 130 ° C. to remove the distillate. Thereafter, the pressure was reduced and the system was gradually heated to 200 ° C. while maintaining the pressure in the system at 20 kPa, and the distillate was recovered.

  When the distillate was analyzed by GC, 3-hydroxypropionic acid was detected in addition to acrylic acid. Trace amounts of lactic acid and butyric acid were also detected. It was confirmed that there were more impurities than acrylic acid obtained in Example 1. No coloration was seen after the product was stored for several days.

Comparative Example 2
In Example 1, the operation was performed in the same manner except that the temperature of the dehydration reaction distillation step was 200 ° C.

  When the product of acrylic acid obtained was stored for several days, coloring was observed.

Claims (1)

A method for producing acrylic acid using a composition containing 3-hydroxypropionic acid obtained by fermentation of biological resources,
(A-1) The extracted composition obtained by extracting at least 3-hydroxypropionic acid from a fermentation broth containing 3-hydroxypropionic acid with an organic solvent having low water affinity at a temperature not exceeding 190 ° C. It was obtained by adding a low water affinity organic solvent to the step of producing an acrylic acid composition by heating and dehydrating and / or (a-2) a fermentation broth containing 3-hydroxypropionic acid. The organic solvent composition is heated at a temperature not exceeding 190 ° C. to perform a dehydration reaction to produce an acrylic acid composition. (B) By the steps a-1 and / or a-2 The manufacturing method of acrylic acid characterized by having the process of refine | purifying acrylic acid from the obtained acrylic acid composition.

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