JP5052234B2 - Method for producing succinic acid - Google Patents
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- JP5052234B2 JP5052234B2 JP2007185680A JP2007185680A JP5052234B2 JP 5052234 B2 JP5052234 B2 JP 5052234B2 JP 2007185680 A JP2007185680 A JP 2007185680A JP 2007185680 A JP2007185680 A JP 2007185680A JP 5052234 B2 JP5052234 B2 JP 5052234B2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims description 422
- 239000001384 succinic acid Substances 0.000 title claims description 196
- 238000004519 manufacturing process Methods 0.000 title claims description 43
- 239000013078 crystal Substances 0.000 claims description 136
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 126
- 239000007788 liquid Substances 0.000 claims description 96
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 62
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 44
- 229910052783 alkali metal Inorganic materials 0.000 claims description 36
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 34
- 238000000926 separation method Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- -1 alkali metal salt Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000011084 recovery Methods 0.000 claims description 13
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 244000005700 microbiome Species 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims 2
- 235000011044 succinic acid Nutrition 0.000 description 169
- 229960005137 succinic acid Drugs 0.000 description 169
- 239000000706 filtrate Substances 0.000 description 50
- 238000002425 crystallisation Methods 0.000 description 49
- 230000008025 crystallization Effects 0.000 description 49
- 239000000243 solution Substances 0.000 description 44
- 238000003756 stirring Methods 0.000 description 30
- 239000011550 stock solution Substances 0.000 description 28
- 238000012545 processing Methods 0.000 description 25
- 230000015556 catabolic process Effects 0.000 description 23
- 239000012535 impurity Substances 0.000 description 18
- 238000001953 recrystallisation Methods 0.000 description 17
- 238000000967 suction filtration Methods 0.000 description 12
- 238000000746 purification Methods 0.000 description 11
- 230000005496 eutectics Effects 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000000909 electrodialysis Methods 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- 238000010956 selective crystallization Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 235000020083 shōchū Nutrition 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はコハク酸の製造方法に関する。さらに詳しくは、コハク酸アルカリ金属塩を含有する液に硫酸を添加し、アルカリ金属硫酸塩とコハク酸とを分別晶析する方法を用いることにより高純度に精製された、ポリマー、食品、医薬品、その他化学品の合成原料として有用なコハク酸の製造方法に関する。 The present invention relates to a method for producing succinic acid. More specifically, polymers, foods, pharmaceuticals, purified to a high purity by using a method of adding sulfuric acid to a liquid containing an alkali metal succinate and fractional crystallization of the alkali metal sulfate and succinic acid, The present invention also relates to a method for producing succinic acid useful as a raw material for synthesis of chemical products.
コハク酸は、ポリマー、食品、医薬品、その他化学品の合成原料として広く用いられており、特にポリマー原料としてコハク酸を用いる場合、ポリマーの重合度維持や着色防止などのために、高純度のコハク酸が要求される。コハク酸の高純度化は精製段数を重ねれば可能ではあるが、工業的生産を経済的に行うためには、分離精製工程の簡略化が必要となる。 Succinic acid is widely used as a raw material for the synthesis of polymers, foods, pharmaceuticals, and other chemicals. Especially when succinic acid is used as a polymer raw material, high-purity succinic acid is used to maintain the degree of polymerization of the polymer and prevent coloring. Acid is required. Although it is possible to increase the purity of succinic acid by repeating the number of purification stages, it is necessary to simplify the separation and purification process in order to economically perform industrial production.
一般に、発酵法によるコハク酸の製造において、ｐＨを制御せずに発酵を行うと、反応の進行に伴って生産されたコハク酸が反応系内に蓄積する。これにより、反応液のｐＨが低下して菌体のコハク酸生産反応の適正領域から逸脱し、その結果、コハク酸の生産速度が大きく低下する。そのため、通常、アルカリを添加することによりｐＨを制御して生産速度を維持する。したがって、コハク酸アルカリ金属塩は、発酵法によるコハク酸の製造における反応液に多く見られる形態である。 In general, in the production of succinic acid by a fermentation method, when fermentation is performed without controlling the pH, succinic acid produced as the reaction proceeds accumulates in the reaction system. As a result, the pH of the reaction solution is lowered to deviate from the appropriate range for the succinic acid production reaction of the cells, and as a result, the production rate of succinic acid is greatly reduced. Therefore, the pH is usually controlled by adding an alkali to maintain the production rate. Therefore, alkali metal succinate is a form often found in a reaction solution in the production of succinic acid by a fermentation method.
コハク酸アルカリ金属塩を含む反応液から高純度のコハク酸を製造する方法として、水分解電気透析によりコハク酸塩の不飽和水溶液を遊離コハク酸の過飽和水溶液に変換し、該過飽和コハク酸水溶液から結晶化させる方法が知られている（特許文献１参照）。 As a method for producing high-purity succinic acid from a reaction solution containing an alkali metal succinate, an unsaturated aqueous solution of succinate is converted into a supersaturated aqueous solution of free succinic acid by hydrolytic electrodialysis, and the supersaturated succinic acid aqueous solution is used. A method of crystallization is known (see Patent Document 1).
しかしながら、特許文献１の方法では、コハク酸を分離精製する際に、過飽和水溶液を得るための水分解電気透析処理前に、通常の電気透析等の工程を実施する必要があることから、処理工程数が多いという問題点を有している。また、この電気透析を用いる方法で工業生産を実施する場合、電気透析膜の洗浄のための薬液の使用や膜の劣化による交換など、装置購入の初期投資だけでなく、稼働後のランニングコストが高くなるという問題も有している。 However, in the method of Patent Document 1, when separating and purifying succinic acid, a process such as normal electrodialysis needs to be performed before water-splitting electrodialysis for obtaining a supersaturated aqueous solution. There is a problem that the number is large. In addition, when industrial production is carried out by this method using electrodialysis, not only the initial investment for equipment purchase, such as the use of chemicals for washing electrodialysis membranes and replacement due to membrane deterioration, but also the running cost after operation is reduced. It also has the problem of becoming expensive.
また、別の方法としては、Ｃａ（ＯＨ）2を添加してコハク酸Ｃａにし、これを結晶と
して回収した後、硫酸を添加することによりＣａを石膏として結晶化させ、コハク酸は溶解液として回収し、さらに冷却して晶析する方法も知られている（特許文献２参照）。しかしながら、特許文献２の方法では、処理工程数が多く、コハク酸Ｃａの回収時にアルカリ廃液が発生するという問題点を有している。
As another method, Ca (OH) 2 is added to form succinic acid Ca, and this is recovered as crystals. Then, sulfuric acid is added to crystallize Ca as gypsum, and succinic acid is used as a solution. A method of recovering and further cooling and crystallizing is also known (see Patent Document 2). However, the method of Patent Document 2 has a problem that the number of treatment steps is large, and an alkaline waste liquid is generated during the recovery of Ca succinate.
さらに、別の方法としては、酸性下で硫酸アンモニウムを添加し、塩析によりコハク酸を回収した後、メタノール抽出して残存硫酸アンモニウムを除去し、溶媒を回収して晶析する方法が知られている（特許文献３）。しかしながら、特許文献３の方法では、水およびメタノールの２つの液相系で処理を行うため、処理工数が増えるとともに、有機溶媒対応の設備も必要になるという問題点を有している。 Furthermore, as another method, after adding ammonium sulfate under acidic conditions and recovering succinic acid by salting out, methanol extraction is performed to remove residual ammonium sulfate, and solvent is recovered and crystallized. (Patent Document 3). However, the method of Patent Document 3 has a problem in that the treatment is performed in two liquid phases of water and methanol, so that the number of treatment steps is increased and equipment for organic solvents is also required.
以上のことから、処理工数が少なく、汎用的な設備でランニングコストが安く、シンプルな分離精製工程から成り立つ、効率的な製造方法を確立することが望まれていた。
本発明の課題は、コハク酸アルカリ金属塩から、シンプルな分離精製方法により、高度に精製されたコハク酸を効率的に得ることができる製造方法を提供することにある。 An object of the present invention is to provide a production method capable of efficiently obtaining highly purified succinic acid from an alkali metal succinate by a simple separation and purification method.
本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、コハク酸アルカリ金属塩含有液に硫酸を添加し、アルカリ金属硫酸塩とコハク酸とが共存する状態において、アルカリ金属硫酸塩とコハク酸とを分別して晶析することにより、コハク酸アルカリ金属塩含有液から高純度のコハク酸を簡便で効率的に分離精製できることを見出し、本発明を完成するに至った。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, by adding sulfuric acid to the succinic acid alkali metal salt-containing liquid and separating the alkali metal sulfate and succinic acid in a state where the alkali metal sulfate and succinic acid coexist, the succinic acid alkali is obtained. It has been found that high-purity succinic acid can be easily and efficiently separated and purified from a metal salt-containing liquid, and the present invention has been completed.
すなわち、本発明は、コハク酸アルカリ金属塩含有液に硫酸を添加して、アルカリ金属硫酸塩とコハク酸とが共存する状態とした上で、初めにアルカリ金属硫酸塩結晶を選択的に析出させて除去し、続いてコハク酸結晶を選択的に析出させて回収する二段階の晶析を行うことを特徴とするコハク酸の製造方法である。 That is, in the present invention, sulfuric acid is added to a succinic acid alkali metal salt-containing liquid so that the alkali metal sulfate and succinic acid coexist, and then the alkali metal sulfate crystals are first selectively precipitated. The succinic acid production method is characterized in that succinic acid crystals are selectively removed and subsequently succinic acid crystals are selectively precipitated and recovered to perform two-stage crystallization.
さらに、本発明は、例えば、以下の事項からなる。
［１］ コハク酸のアルカリ金属塩を含有する液に硫酸を添加する工程（１）と、アルカリ金属硫酸塩結晶を析出させて前記液より除去する工程（２）と、コハク酸結晶を析出させて回収する工程（３）とを含むことを特徴とするコハク酸の製造方法。
Furthermore, this invention consists of the following matters, for example.
[1] A step (1) of adding sulfuric acid to a liquid containing an alkali metal salt of succinic acid, a step (2) of precipitating an alkali metal sulfate crystal and removing it from the liquid, and precipitating a succinic acid crystal And a step (3) of recovering the succinic acid.
［２］ 前記工程（１）において添加される硫酸量が、前記液中に含まれるアルカリ金属と同当量数であることを特徴とする［１］に記載のコハク酸の製造方法。
［３］ 前記工程（２）におけるアルカリ金属硫酸塩結晶の除去が、前記工程（１）において硫酸添加した液を濃縮および加熱してアルカリ金属硫酸塩結晶を析出させ、かつ、コハク酸が溶解した状態で、固液分離することにより行われることを特徴とする［１］に記載のコハク酸の製造方法。
[2] The method for producing succinic acid according to [1], wherein the amount of sulfuric acid added in the step (1) is the same equivalent number as the alkali metal contained in the liquid.
[3] Removal of the alkali metal sulfate crystals in the step (2) is performed by concentrating and heating the liquid added with sulfuric acid in the step (1) to precipitate the alkali metal sulfate crystals, and the succinic acid is dissolved. The method for producing succinic acid according to [1], which is carried out by solid-liquid separation in a state.
［４］ 前記硫酸添加した反応液を濃縮および加熱した後の液中のアルカリ金属硫酸塩濃度が２０ｇ/１００ｇ-水以上であり、かつ、コハク酸の濃度が６０ｇ/１００ｇ-水以下であり、前記加熱温度が５０℃以上であることを特徴とする［３］に記載のコハク酸の製造方法。 [4] The concentration of the alkali metal sulfate in the solution after concentration and heating of the reaction solution added with sulfuric acid is 20 g / 100 g-water or more, and the concentration of succinic acid is 60 g / 100 g-water or less, The method for producing succinic acid according to [3], wherein the heating temperature is 50 ° C or higher.
［５］ 前記工程（３）におけるコハク酸結晶の回収が、前記アルカリ金属硫酸塩結晶を除去した液を冷却してコハク酸を晶析させ、かつ、前記工程（２）において除去されずに液中に残存するアルカリ金属硫酸塩が溶解した状態で、固液分離することによって行われることを特徴とする［１］〜［４］のいずれかに記載のコハク酸の製造方法。 [5] Recovery of the succinic acid crystals in the step (3) is performed by cooling the liquid from which the alkali metal sulfate crystals have been removed to crystallize the succinic acid, and without being removed in the step (2). The method for producing succinic acid according to any one of [1] to [4], which is performed by solid-liquid separation in a state in which the alkali metal sulfate remaining therein is dissolved.
［６］ 前記アルカリ金属硫酸塩結晶を除去した液の冷却温度が５０℃以下であることを特徴とする［５］に記載のコハク酸の製造方法。
［７］ 前記回収されたコハク酸結晶を、前記アルカリ金属硫酸塩結晶を除去した液の冷却温度より低い温度の水で洗浄する工程をさらに含むことを特徴とする［５］または［６］に記載のコハク酸の製造方法。
[6] The method for producing succinic acid according to [5], wherein the cooling temperature of the liquid from which the alkali metal sulfate crystals have been removed is 50 ° C. or lower.
[7] The method according to [5] or [6], further including a step of washing the recovered succinic acid crystal with water having a temperature lower than a cooling temperature of the liquid from which the alkali metal sulfate crystal has been removed. The manufacturing method of succinic acid of description.
［８］ 前記回収されたコハク酸結晶を水で再溶解し、得られた溶液を冷却することによりコハク酸を再晶析させて回収する工程をさらに含むことを特徴とする［５］または［６］に記載のコハク酸の製造方法。 [8] The method further comprises the step of re-dissolving the recovered succinic acid crystals with water and recrystallizing and recovering the succinic acid by cooling the obtained solution [5] or [ [6] The method for producing succinic acid according to [6].
［９］ 前記コハク酸結晶を水で再溶解した後であって、コハク酸を再晶析させて回収する前に、コハク酸結晶を再溶解した液を活性炭で処理する工程をさらに含むことを特徴とする［８］に記載のコハク酸の精製造方法。 [9] The method further includes a step of treating the liquid in which the succinic acid crystals are redissolved with activated carbon after redissolving the succinic acid crystals with water and before recrystallizing and recovering the succinic acid. The method for producing succinic acid according to [8], which is characterized in that it is characterized.
［１０］ 前記コハク酸結晶回収後の残液を、前記工程（２）における濃縮および加熱する前の液に加えて再処理することを特徴とする［３］に記載のコハク酸の製造方法。
［１１］ 前記回収されたコハク酸結晶を水洗し、回収された洗浄水を、前記工程（２）における濃縮および加熱する前の液に加えて再処理することを特徴とする［３］に記載のコハク酸の製造方法。
[10] The method for producing succinic acid according to [3], wherein the residual liquid after the succinic acid crystal recovery is added to the liquid before concentration and heating in the step (2) and reprocessed.
[11] The method according to [3], wherein the recovered succinic acid crystals are washed with water, and the recovered washing water is added to the liquid before being concentrated and heated in the step (2) and reprocessed. A method for producing succinic acid.
［１２］ 前記コハク酸アルカリ金属塩を含有する液が、微生物による培養液であることを特徴とする［１］に記載のコハク酸の製造方法。
［１３］ 前記コハク酸アルカリ金属塩を含有する液の溶媒が水であることを特徴とする［１］に記載のコハク酸の製造方法。
[12] The method for producing succinic acid according to [1], wherein the liquid containing the alkali metal succinate is a culture liquid using microorganisms.
[13] The method for producing succinic acid according to [1], wherein the solvent of the liquid containing the alkali metal succinate is water.
本発明の製造方法を用いれば、高純度のコハク酸を効率的に製造することができる。 By using the production method of the present invention, highly pure succinic acid can be produced efficiently.
以下、本発明に係るコハク酸の製造方法について、詳細に説明する。なお、図１は、本発明のコハク酸の製造工程を示すフローチャートである。
＜コハク酸のアルカリ金属塩を含有する液の準備＞
本発明では、コハク酸のアルカリ金属塩を含有する液を原料に用いる。この液はコハク酸のアルカリ金属塩を含むものであれば特に限定されず、塩の種類もアルカリ金属であれば特に制限されないが、有機溶剤を含有しない水を溶媒とするものが好ましい。
Hereinafter, the method for producing succinic acid according to the present invention will be described in detail. In addition, FIG. 1 is a flowchart which shows the manufacturing process of the succinic acid of this invention.
<Preparation of liquid containing alkali metal salt of succinic acid>
In the present invention, a liquid containing an alkali metal salt of succinic acid is used as a raw material. This solution is not particularly limited as long as it contains an alkali metal salt of succinic acid, and is not particularly limited as long as the type of the salt is an alkali metal, but a solution containing water containing no organic solvent as a solvent is preferable.
コハク酸のアルカリ金属塩を含有する液としては、例えば、微生物によって発酵生産されたコハク酸のアルカリ金属塩の反応液を挙げることができる。微生物を用いたコハク酸アルカリ金属塩の反応液は、例えば、コハク酸生産能を有する微生物を、炭素源や窒素源等を含有した培地液中で、ｐＨ調整剤として水酸化アルカリ金属水溶液を添加しながら行う培養によって得ることができる。この反応液中には、発酵の副生成物として酢酸や乳酸等の他の有機酸およびその金属塩が少量含有されていてもよい。 Examples of the liquid containing an alkali metal salt of succinic acid include a reaction liquid of an alkali metal salt of succinic acid fermented and produced by a microorganism. For the reaction solution of succinic acid alkali metal salt using microorganisms, for example, a microorganism having succinic acid-producing ability is added to an aqueous solution of alkali metal hydroxide as a pH adjuster in a medium solution containing a carbon source, a nitrogen source, etc. It can obtain by culture | cultivation performed. This reaction solution may contain a small amount of other organic acids such as acetic acid and lactic acid and metal salts thereof as fermentation by-products.
本発明では、コハク酸のアルカリ金属塩を含有する液に硫酸を添加することにより、アルカリ金属硫酸塩とコハク酸とが共存する状態とした上で、初めにアルカリ金属硫酸塩結晶を選択的に析出させて除去し、続いてコハク酸結晶を選択的に析出させて回収する二段階の晶析を行うことにより、コハク酸のアルカリ金属塩を遊離型コハク酸に酸転化することができる。さらに、酸転化したコハク酸を水で再溶解し、これを冷却して結晶を再晶析させて回収することにより、高純度のコハク酸を得ることができる。 In the present invention, by adding sulfuric acid to the liquid containing the alkali metal salt of succinic acid, the alkali metal sulfate and succinic acid coexist in a coexisting state. The alkali metal salt of succinic acid can be acid-converted to free succinic acid by carrying out two-stage crystallization in which the succinic acid crystals are selectively precipitated and recovered by precipitation. Furthermore, high-purity succinic acid can be obtained by re-dissolving the acid-converted succinic acid with water, cooling it, recrystallizing and recovering the crystals.
＜硫酸添加＞
コハク酸アルカリ金属塩含有液への硫酸の添加は、液中のアルカリ金属の対イオンとして硫酸イオンを供給してアルカリ金属硫酸塩とし、次工程のアルカリ金属硫酸塩の晶析（以下「高温晶析」ともいう。）において、それを最大限結晶化して除去することが目的である。しかしながら、アルカリ金属に対して硫酸を添加することは、不純物として硫酸根を残すことになり、高純度のコハク酸取得の障害の原因となる。このため、反応液に添加する硫酸量は、反応液に含有するアルカリ金属と同当量数であることが望ましい。
<Addition of sulfuric acid>
Addition of sulfuric acid to the succinic acid alkali metal salt-containing liquid is performed by supplying sulfate ions as counter ions of the alkali metal in the liquid to obtain alkali metal sulfate, and crystallization of the alkali metal sulfate in the next step (hereinafter referred to as “high-temperature crystallization”). The purpose is to crystallize and remove it as much as possible. However, the addition of sulfuric acid to the alkali metal leaves a sulfate radical as an impurity, causing an obstacle to obtaining high-purity succinic acid. For this reason, it is desirable that the amount of sulfuric acid added to the reaction solution is the same number as the alkali metal contained in the reaction solution.
上述したように微生物による発酵液には、通常、コハク酸の他に副生成物として他の有
機酸が共存する。したがって、反応で添加される水酸化アルカリ金属は、コハク酸だけでなく他の有機酸の中和のためにも添加される。このように、液に含有するコハク酸当量数とアルカリ金属当量数とは必ずしも一致しない。つまり、正確に硫酸添加量を求めるにはコハク酸当量数よりアルカリ金属当量数を用いることが望ましい。
As described above, in addition to succinic acid, other organic acids usually coexist in the fermentation broth by microorganisms as a by-product. Therefore, the alkali metal hydroxide added in the reaction is added not only for succinic acid but also for neutralization of other organic acids. Thus, the number of succinic acid equivalents and the number of alkali metal equivalents contained in the liquid do not necessarily match. That is, it is desirable to use the alkali metal equivalent number rather than the succinic acid equivalent number in order to accurately obtain the amount of sulfuric acid added.
＜高温晶析＞
硫酸添加した液を、アルカリ金属硫酸塩濃度が液における飽和溶解度以上、かつ、コハク酸濃度が液における飽和溶解度以下になるように濃縮および加熱して、アルカリ金属硫酸塩結晶が選択的に析出する状態となるようにする。濃縮・加熱後のアルカリ金属硫酸塩濃度、コハク酸濃度および温度は、前記条件を満たし、かつ、アルカリ金属硫酸塩結晶の選択的結晶化に支障をきたさなければ、特に限定されない。
<High temperature crystallization>
The sulfuric acid-added liquid is concentrated and heated so that the alkali metal sulfate concentration is equal to or higher than the saturated solubility in the liquid and the succinic acid concentration is equal to or lower than the saturated solubility in the liquid to selectively precipitate alkali metal sulfate crystals. To be in a state. The concentration of alkali metal sulfate, concentration of succinic acid and temperature after concentration and heating are not particularly limited as long as the above conditions are satisfied and selective crystallization of alkali metal sulfate crystals is not hindered.
コハク酸とアルカリ金属塩とが共存した系において、コハク酸の溶解度は温度上昇とともに高くなる一方、アルカリ金属塩の溶解度は温度上昇とともに下がるか、あるいはほぼ一定の傾向にある。したがって、コハク酸を選択的に晶析させて回収する次の工程（以下「低温晶析」ともいう。）でコハク酸の回収量をより上げ、かつ、不純物となるアルカリ金属塩の含有量をより下げるためには、濃縮・加熱後の温度は、コハク酸が熱分解しない範囲で高いことが好ましく、通常５０℃以上、より好ましくは７０〜８０℃である。 In a system in which succinic acid and an alkali metal salt coexist, the solubility of succinic acid increases with increasing temperature, while the solubility of alkali metal salt decreases with increasing temperature, or tends to be almost constant. Therefore, in the next step of selectively crystallizing and recovering succinic acid (hereinafter also referred to as “low-temperature crystallization”), the recovered amount of succinic acid is further increased, and the content of alkali metal salt as an impurity is increased. In order to lower the temperature, the temperature after concentration and heating is preferably high as long as succinic acid is not thermally decomposed, and is usually 50 ° C. or higher, more preferably 70 to 80 ° C.
また、濃縮・加熱後のアルカリ金属硫酸塩およびコハク酸の濃度は、例えば、加熱温度を５０℃以上とする場合は、液中のアルカリ金属硫酸塩濃度が２０ｇ/１００ｇ-水以上、かつ、コハク酸の濃度が６０ｇ/１００ｇ-水以下の範囲であることが好ましく、アルカリ金属硫酸塩濃度が６０〜８０ｇ/１００ｇ-水、かつ、コハク酸の濃度が３０〜５０ｇ/１
００ｇ-水の範囲であることがより好ましい。
The concentration of alkali metal sulfate and succinic acid after concentration / heating is, for example, when the heating temperature is 50 ° C. or higher, and the alkali metal sulfate concentration in the liquid is 20 g / 100 g-water or higher and The acid concentration is preferably in the range of 60 g / 100 g-water or less, the alkali metal sulfate concentration is 60-80 g / 100 g-water, and the succinic acid concentration is 30-50 g / 1.
A range of 00 g-water is more preferable.
上記数値範囲を外れた場合、例えば、コハク酸濃度が上記範囲よりも高いと、アルカリ金属硫酸塩と一緒にコハク酸も析出しコハク酸のロスにつながる。また、コハク酸濃度が上記範囲よりも低いと、次工程である低温晶析工程でのコハク酸結晶の回収率が低下する傾向にある。一方、アルカリ金属硫酸塩濃度が上記範囲よりも高いと、結晶量が多くなり固液分離効率が低下する傾向にある。また、アルカリ金属硫酸塩濃度が上記範囲よりも低いと、結晶量が少なくなり、全体に対するアルカリ金属硫酸塩の結晶比率が低下し、除去効率が落ちる傾向にある。 For example, if the succinic acid concentration is higher than the above range, succinic acid is precipitated together with the alkali metal sulfate, leading to loss of succinic acid. On the other hand, when the succinic acid concentration is lower than the above range, the recovery rate of succinic acid crystals in the low-temperature crystallization step, which is the next step, tends to decrease. On the other hand, when the alkali metal sulfate concentration is higher than the above range, the amount of crystals increases and the solid-liquid separation efficiency tends to decrease. On the other hand, when the alkali metal sulfate concentration is lower than the above range, the amount of crystals decreases, the crystal ratio of the alkali metal sulfate to the whole decreases, and the removal efficiency tends to decrease.
析出したアルカリ金属硫酸塩結晶の固液分離方法としては、固液分離中の系内の温度を濃縮・加熱時と等しい温度以上に維持し、分離処理時にコハク酸の結晶を析出させることなくアルカリ金属塩のみ析出させた状態を保持できる機能を持ち合わせた遠心分離、遠心濾過、フィルタープレス、膜濾過などの方法を採用することができる。 As a solid-liquid separation method for the precipitated alkali metal sulfate crystals, the temperature in the system during the solid-liquid separation is maintained at a temperature equal to or higher than that during concentration and heating, and the alkali metal sulfate crystals are precipitated without precipitating succinic acid crystals during the separation process. Methods such as centrifugal separation, centrifugal filtration, filter press, membrane filtration, etc., having the function of maintaining the state in which only the metal salt is deposited can be employed.
＜低温晶析＞
上記アルカリ金属硫酸塩結晶を除去した液を冷却し、コハク酸結晶が選択的に析出する状態となるようにする。
<Low temperature crystallization>
The liquid from which the alkali metal sulfate crystals have been removed is cooled so that succinic acid crystals are selectively precipitated.
冷却した液には、結晶化していないコハク酸と、前工程で結晶化されずに残存したアルカリ金属硫酸塩とが溶解している。このため、アルカリ金属硫酸塩をより確実に溶解した状態にするために、冷却と一緒に水希釈してアルカリ金属硫酸塩濃度を下げてもよい。 In the cooled liquid, succinic acid that has not been crystallized and the alkali metal sulfate remaining without being crystallized in the previous step are dissolved. For this reason, in order to make an alkali metal sulfate dissolved more reliably, it may be diluted with water together with cooling to lower the alkali metal sulfate concentration.
冷却の温度は、コハク酸を選択的に結晶化させるのに支障をきたさなければ、特に限定されないが、高温晶析の温度より低い５０℃以下が好ましく、３５〜４０℃がより好ましい。 The cooling temperature is not particularly limited as long as it does not hinder the selective crystallization of succinic acid, but is preferably 50 ° C. or lower, more preferably 35 to 40 ° C., lower than the temperature of high temperature crystallization.
アルカリ金属硫酸塩としては、ボウショウ（硫酸ナトリウム）や硫酸カリウムが挙げられるが、ボウショウ（硫酸ナトリウム）が特に好ましい。ボウショウの水に対する飽和溶解度は、結晶水型から無水塩型への転移温度以上で概ね一定である。これに対して、コハク酸の水に対する飽和溶解度は、温度が高くなるにつれて増加する。そのため、両者の飽和溶解度曲線は図２に示すように交差する。この交差温度より高い温度領域でボウショウを選択的に析出させることが可能であり、この交差温度より低い温度領域でコハク酸を選択的に析出させることが可能である。なお、両者の飽和溶解度差の大きい温度で選択的に晶析することが好ましい。また、図２に示したようにボウショウ（硫酸ナトリウム）の場合、結晶水型から無水塩型への転移温度（３２．４℃）以下では、飽和溶解度が低下して析出しやすくなる。そのため、低温晶析は３５℃以上で行うことが好ましい。 Examples of the alkali metal sulfate include bow show (sodium sulfate) and potassium sulfate, but bow show (sodium sulfate) is particularly preferable. The saturation solubility of water of bouchein is generally constant above the transition temperature from the crystal water type to the anhydrous salt type. In contrast, the saturation solubility of succinic acid in water increases with increasing temperature. Therefore, the saturation solubility curves of both intersect as shown in FIG. It is possible to selectively deposit bowsho in a temperature range higher than the crossing temperature, and it is possible to selectively precipitate succinic acid in a temperature range lower than the crossing temperature. In addition, it is preferable to selectively crystallize at a temperature having a large difference in saturation solubility between the two. Further, as shown in FIG. 2, in the case of bousho (sodium sulfate), at a transition temperature (32.4 ° C.) or lower from the crystal water type to the anhydrous salt type, the saturation solubility is lowered and the precipitation tends to occur. Therefore, it is preferable to perform low temperature crystallization at 35 ° C. or higher.
結晶回収は、コハク酸が結晶化析出した液（以下「結晶液」ともいう。）を固液分離し、結晶に付着している不純物をリンスにより除去して行なわれる。
固液分離の方法としては、遠心分離、遠心濾過、フィルタープレス濾過、膜濾過などの方法を採用することができる。コハク酸の回収効率、付着不純物の除去効率などを考慮すると、濾布型固液分離が有利であり、特にフィルタープレスおよび／または遠心濾過を採用することが好ましい。また、結晶回収率維持の観点から、結晶液は冷却時の温度で維持されることが好ましい。
Crystal recovery is performed by solid-liquid separation of a liquid in which succinic acid is crystallized and precipitated (hereinafter also referred to as “crystal liquid”) and removing impurities adhering to the crystal by rinsing.
As a method for solid-liquid separation, methods such as centrifugation, centrifugal filtration, filter press filtration, membrane filtration and the like can be employed. Considering the recovery efficiency of succinic acid, the removal efficiency of adhering impurities, filter cloth type solid-liquid separation is advantageous, and it is particularly preferable to employ a filter press and / or centrifugal filtration. Further, from the viewpoint of maintaining the crystal recovery rate, the crystal solution is preferably maintained at the temperature during cooling.
また、結晶液の結晶を固液分離により濾過面に回収した状態で、濾過面に水または後述の再晶析で回収される固液分離後の濾液を洗浄液として供給することにより、結晶に付着した不純物を洗い流すこともできる。洗浄液は、結晶回収率維持の観点から、結晶液の温度以下に冷却されていることが好ましい。また、洗浄液のコハク酸濃度は、洗浄液へのコハク酸溶解ロスを抑制するためその温度における飽和溶解度に近い濃度であることが好ましい。たとえば、洗浄液として水を用いる場合には、水温を低くして飽和溶解度を下げることが好ましい。供給する液量は、濾液中の不純物の種類や量、所望の精製度、回収率などに応じて適宜調整することができる。 In addition, while the crystals of the crystal liquid are collected on the filtration surface by solid-liquid separation, water or the filtrate after solid-liquid separation collected by recrystallization described later is supplied to the filtration surface as a washing liquid, thereby adhering to the crystals. It is also possible to wash away impurities. The cleaning liquid is preferably cooled below the temperature of the crystal liquid from the viewpoint of maintaining the crystal recovery rate. Further, the succinic acid concentration of the cleaning liquid is preferably close to the saturation solubility at that temperature in order to suppress succinic acid dissolution loss in the cleaning liquid. For example, when water is used as the cleaning liquid, it is preferable to lower the saturation solubility by lowering the water temperature. The amount of liquid to be supplied can be appropriately adjusted according to the type and amount of impurities in the filtrate, the desired degree of purification, the recovery rate, and the like.
＜結晶溶解・活性炭処理・再晶析＞
コハク酸結晶回収の固液分離において、結晶に付着している不純物の濃度をさらに低減させたい場合は、回収したコハク酸結晶を、水または温水で溶解し、必要に応じて活性炭処理した後、冷却して再結晶化し、再度固液分離を行うことにより、付着している不純物を除去することができる。
<Crystal dissolution / activated carbon treatment / recrystallization>
In the solid-liquid separation of succinic acid crystal recovery, if you want to further reduce the concentration of impurities adhering to the crystal, the recovered succinic acid crystal is dissolved in water or warm water and treated with activated carbon as necessary, By recrystallizing by cooling and solid-liquid separation again, the adhering impurities can be removed.
この場合、溶解後のコハク酸濃度および冷却温度は、冷却時の結晶化に支障をきたさなければ特に限定されない。また、固液分離時の処理は、結晶の回収のみで行ってもよいし、必要に応じて水の供給による洗浄を加えて行ってもよい。また、再結晶化および再固液分離の操作回数は一回に限定されるものでもない。 In this case, the succinic acid concentration after dissolution and the cooling temperature are not particularly limited as long as they do not hinder crystallization during cooling. In addition, the treatment at the time of solid-liquid separation may be performed only by collecting crystals, or may be performed by adding water as needed. Further, the number of operations for recrystallization and re-solid-liquid separation is not limited to one.
＜乾燥＞
回収されたコハク酸結晶は、水分の乾燥を行い乾燥品にすることもできる。この場合の乾燥方法は、コハク酸が変質せず、不純物が混入しない範囲において実施されるものであれば、特に限定されない。
<Dry>
The recovered succinic acid crystals can be dried by drying the water. The drying method in this case is not particularly limited as long as it is carried out within a range in which succinic acid is not altered and impurities are not mixed.
なお、低温晶析および再晶析によるコハク酸結晶回収後の残液を、濃縮・加熱する前の液に戻して再処理をすることもできる。再処理を行う場合は、系内の不純物が蓄積していくため、分離精製効率を考え、適宜、低温晶析の濾液を再処理せず、系外に除去することが望ましい。 In addition, the residual liquid after recovery of succinic acid crystals by low-temperature crystallization and recrystallization can be returned to the liquid before being concentrated and heated for reprocessing. When reprocessing is performed, impurities in the system accumulate, so that separation and purification efficiency is considered and it is desirable to remove the low temperature crystallization filtrate from the system without reprocessing as appropriate.
以上のように、本発明のコハク酸の製造方法は、コハク酸アルカリ金属塩の含有液に硫
酸を添加し、アルカリ金属硫酸塩とコハク酸とが共存する状態において、アルカリ金属硫酸塩とコハク酸とを分別して晶析する方法であって、処理工程数が少なく晶析手法だけのシンプルな精製方法である。本発明の製造方法により、高純度のコハク酸結晶を、晶析操作を行う汎用設備により効率的に得ることを可能とした。
As described above, in the method for producing succinic acid of the present invention, the sulfuric acid is added to the liquid containing the succinic acid alkali metal salt, and the alkali metal sulfate and succinic acid are mixed in the state where the alkali metal sulfate and succinic acid coexist. This is a simple purification method with a small number of processing steps and only a crystallization technique. The production method of the present invention makes it possible to efficiently obtain a high-purity succinic acid crystal using general-purpose equipment for performing a crystallization operation.
［実施例］
以下、実施例に基づいて本発明をより具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。なお、以下の実施例等では、各工程で成分分析した際にサンプリングロスが若干生じているが、このサンプリングロスについては考慮せずに収量等を記載している。
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by these Examples. In the following examples and the like, a sampling loss occurs slightly when the components are analyzed in each step, but the yield and the like are described without considering this sampling loss.
＜モデル液での共晶点測定＞
コハク酸１４４ｇおよびボウショウ１０８ｇを、水１８０ｇが入った５００ｍＬ共栓つき三角フラスコに加えて過飽和共存スラリー液を調製した。スラリー液をウォーターバス中でスターラー撹拌することにより、３５℃、４５℃、６０℃および８０℃の各液温に調整し、各温度到達後２時間以上撹拌した後に、上清のコハク酸およびボウショウの濃度を分析した。その結果、コハク酸の濃度は、３５℃で４．６ｇ／１００ｇ-水、４５℃で７
．８ｇ／１００ｇ-水、６０℃で２０．０ｇ／１００ｇ-水、８０℃で５５．３ｇ／１００ｇ-水となった。また、ボウショウの濃度は、３５℃で４６．４ｇ／１００ｇ-水、４５℃で４２．０ｇ／１００ｇ-水、６０℃で３６．９ｇ／１００ｇ-水、８０℃で２８．８ｇ／１００ｇ-水となった。これらの溶解度曲線は図２（共存系参照）、共晶線は図３に示す
通りになった。なお、「ｇ／１００ｇ-水」とは、１００ｇの水に溶解している溶質重量
ｇによって示した濃度単位である。
<Measurement of eutectic point in model solution>
A supersaturated coexisting slurry solution was prepared by adding 144 g of succinic acid and 108 g of boushou to a 500 mL conical flask with a stopper containing 180 g of water. The slurry solution was stirred in a water bath with a stirrer to adjust the solution temperature to 35 ° C., 45 ° C., 60 ° C. and 80 ° C., and after stirring for 2 hours or more after reaching each temperature, succinic acid and bow The concentration of was analyzed. As a result, the concentration of succinic acid was 4.6 g / 100 g-water at 35 ° C. and 7 at 45 ° C.
. 8 g / 100 g-water, 20.0 g / 100 g-water at 60 ° C., and 55.3 g / 100 g-water at 80 ° C. In addition, the concentration of bouchein was 46.4 g / 100 g-water at 35 ° C., 42.0 g / 100 g-water at 45 ° C., 36.9 g / 100 g-water at 60 ° C., and 28.8 g / 100 g-water at 80 ° C. It became. These solubility curves are as shown in FIG. 2 (see coexisting system), and the eutectic lines are as shown in FIG. “G / 100 g-water” is a concentration unit represented by the solute weight g dissolved in 100 g of water.
図２より、コハク酸とボウショウの２成分モデル系では、低温になるとコハク酸溶解度が低下してボウショウ溶解度が上昇し、高温になるとコハク酸溶解度が上昇してボウショウ溶解度が低下する傾向が得られ、高温域でボウショウを選択的に析出させること、あるいは、低温域でコハク酸を選択的に析出させることが可能であることが確認された。 As shown in FIG. 2, in the two-component model system of succinic acid and boushou, the solubility of succinic acid decreases and the solubility of succinic acid increases at low temperatures, and the solubility of succinic acid increases and the solubility of succinic acid decreases at high temperatures. It has been confirmed that it is possible to selectively deposit bowsho in a high temperature range or to selectively precipitate succinic acid in a low temperature range.
また、共晶線は図３に示すように若干左に傾いている傾向であることがわかった。この共晶線から左下の領域の組成を有するコハク酸とボウショウの共存液において、その共存液を濃縮して両者の含有比が一定の濃度推移線が共晶線と交差する場合、交差する共晶点の温度以上に共存液温度を選定して濃縮すると、ボウショウを選択的に結晶化する状態が得られること、さらには析出したボウショウを除去した後、冷却するとコハク酸を選択的に結晶化する状態が得られることが確認された。 Further, it was found that the eutectic line tends to be slightly inclined to the left as shown in FIG. In the coexisting solution of succinic acid and bowshaw having a composition in the lower left region from this eutectic line, if the coexisting solution is concentrated and the concentration transition line with a constant content ratio of both crosses the eutectic line, Selecting and concentrating the coexisting liquid temperature above the temperature of the crystal point gives a state of selective crystallization of bousho, and further, after removing the precipitated bousho and cooling, succinic acid is selectively crystallized. It was confirmed that the state to do was obtained.
＜反応液の硫酸添加と共晶点測定＞
有機酸、カチオン、アニオンおよび糖のＨＰＬＣ分析により求めた表１に示す組成を有し、発酵生産によるコハク酸Ｎａを含有する除菌した反応液（Ａ）、（Ｂ）、（Ｃ）各１．０Ｌをそれぞれビーカーに分取した。次いで、各反応液に含まれるアルカリ金属濃度と同当量になるように、反応液（Ａ）には１１１ｇの硫酸を、反応液（Ｂ）には８４ｇの硫酸を、反応液（Ｃ）には５０ｇの硫酸を、それぞれスターラーで撹拌しながら添加した。この液を、それぞれロータリーエバポレータで５倍濃縮して過飽和状態にした後、スラリー液を３００ｍＬ共栓付き三角フラスコに全量投入した。次いで、これらをウォーターバス中でスターラー撹拌することにより、３５℃、４５℃、６０℃および８０℃の各液温に調整し、各温度到達後２時間以上撹拌した後に、それぞれの上清のコハク酸およびボウショウの濃度を測定し、溶解度曲線（図４）および共晶線（図５）を確認した。
<Addition of sulfuric acid to reaction solution and eutectic point measurement>
Each of the sterilized reaction liquids (A), (B), and (C) having the composition shown in Table 1 obtained by HPLC analysis of organic acids, cations, anions, and sugars and containing sodium succinate by fermentation production. 0.0 L was dispensed into each beaker. Next, 111 g of sulfuric acid is added to the reaction solution (A), 84 g of sulfuric acid is added to the reaction solution (B), and 84 g of sulfuric acid is added to the reaction solution (C) so as to be equivalent to the alkali metal concentration contained in each reaction solution. 50 g of sulfuric acid was added with stirring with a stirrer. Each of these liquids was concentrated 5 times with a rotary evaporator to be in a supersaturated state, and then the entire amount of the slurry liquid was put into a 300 mL conical stoppered Erlenmeyer flask. Then, these were stirred with a stirrer in a water bath to adjust the liquid temperature to 35 ° C., 45 ° C., 60 ° C. and 80 ° C., and stirred for 2 hours or more after reaching each temperature. The concentration of acid and bowshade was measured and the solubility curve (FIG. 4) and eutectic line (FIG. 5) were confirmed.
反応液の溶解度曲線および共晶線は、モデル液と同様であり、上記のような分別晶析が可能であることが確認された。
〔実施例１〕
＜反応液（Ａ）の分離精製＞
（硫酸添加）
表１に示した組成を有する反応液（Ａ）２０８０ｇ（２．０Ｌ）を撹拌しながら、反応液（Ａ）中に含まれるアルカリ金属と同当量数の濃硫酸２２３ｇを添加し、処理原液を調製した。表２に示すように、処理原液は、反応液量が２３０３ｇ（２．２Ｌ）、コハク酸含有量が２３１ｇ（１３．７ｇ/１００ｇ-水）、ボウショウ含有量が３２３ｇ（１９．２ｇ/１００ｇ-水）となった。
The solubility curve and eutectic line of the reaction solution were the same as the model solution, and it was confirmed that fractional crystallization as described above was possible.
[Example 1]
<Separation and purification of reaction solution (A)>
(Addition of sulfuric acid)
While stirring 2080 g (2.0 L) of the reaction solution (A) having the composition shown in Table 1, 223 g of concentrated sulfuric acid having the same number as the alkali metal contained in the reaction solution (A) was added, Prepared. As shown in Table 2, the processing stock solution has a reaction solution amount of 2303 g (2.2 L), a succinic acid content of 231 g (13.7 g / 100 g-water), and a bowel content of 323 g (19.2 g / 100 g-). Water).
（高温晶析）
続いて、処理原液をロータリーエバポレータで１０８２ｇまで濃縮し、コハク酸濃度を４６ｇ／１００ｇ-水、ボウショウ濃度を６５ｇ／１００ｇ-水とし、共栓つき三角フラスコに全量移した。三角フラスコに栓をした密閉状態にして、８０℃のウォーターバス中でスターラー撹拌をしながら昇温した。濃縮液を温度８０℃の状態で２時間撹拌した後、事前に８０℃に加熱した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。
(High temperature crystallization)
Subsequently, the processing stock solution was concentrated to 1082 g by a rotary evaporator, the succinic acid concentration was 46 g / 100 g-water, the bow concentration was 65 g / 100 g-water, and the whole amount was transferred to an Erlenmeyer flask with a stopper. The flask was sealed in a conical flask, and the temperature was raised while stirring with a stirrer in an 80 ° C. water bath. The concentrated solution was stirred at a temperature of 80 ° C. for 2 hours, and then subjected to solid filtration by suction filtration using a Nutsche having an inner diameter of 110 mm and a 5B filter paper heated to 80 ° C. in advance.
回収した濾液は７９８ｇであり、その内訳は、コハク酸２１５ｇ、ボウショウ７７ｇ、水分４８３ｇ、その他２２ｇであった。また、回収した結晶重量は２８４ｇであり、その内訳はボウショウ２４５ｇ、コハク酸１６ｇ、水分１７ｇ、その他成分５ｇであった。高温晶析により処理原液中のコハク酸は濾液中に９３％回収され、処理原液中のボウショウは結晶として７６％除去された。 The recovered filtrate was 798 g, and the breakdown was 215 g of succinic acid, 77 g of bowel, 483 g of water, and 22 g of others. The recovered crystal weight was 284 g, and the breakdown was 245 g of bousho, 16 g of succinic acid, 17 g of water, and 5 g of other components. By crystallization at high temperature, 93% of succinic acid in the processing stock solution was recovered in the filtrate, and 76% of the bowel in the processing stock solution was removed as crystals.
（低温晶析）
高温晶析で回収した濾液７９８ｇを、共栓付き三角フラスコに全量移し、三角フラスコに栓をした密閉状態にして、３５℃のウォーターバス中でスターラー撹拌をしながら降温した。濃縮液を温度３５℃の状態で２時間撹拌した後、事前に３５℃に保温した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。さらに、ヌッチェ上に結晶を全量回収した後、３５℃の水２１５ｇをヌッチェ上の結晶に供給して結晶の洗浄を行った。
(Low temperature crystallization)
A total amount of 798 g of the filtrate recovered by high-temperature crystallization was transferred to an Erlenmeyer flask with a stopper, sealed in a stoppered Erlenmeyer flask, and the temperature was lowered while stirring with a stirrer in a 35 ° C. water bath. The concentrated liquid was stirred at a temperature of 35 ° C. for 2 hours, and then solid-liquid separation was performed by suction filtration using a Nutsche having an inner diameter of 110 mm and a filter paper of 5B, which had been kept at 35 ° C. in advance. Furthermore, after all the crystals were collected on Nutsche, 215 g of water at 35 ° C. was supplied to the crystals on Nutsche to wash the crystals.
回収した結晶重量は１７６ｇであり、その内訳はコハク酸１６４ｇ、ボウショウ０ｇ、水分１０ｇ、その他成分２ｇであった。また、回収した濾液は水洗浄分も含めて合計８３７ｇであり、その内訳は、コハク酸５１ｇ、ボウショウ７７ｇ、水分６８８ｇ、その他２０ｇであった。処理原液中のコハク酸含有量を１００％とすると、低温晶析により、結晶中にコハク酸は７１％回収され、ボウショウは濾液中に２４％含有し除去された。また、回収したコハク酸結晶は完全にＮａを除去することができ、さらにコハク酸以外の有機酸等の他の不純物も９７％除去できた。 The recovered crystal weight was 176 g, and the breakdown was 164 g of succinic acid, 0 g of bowel, 10 g of water, and 2 g of other components. Further, the collected filtrate was 837 g in total including the amount of water washed, and the breakdown was 51 g of succinic acid, 77 g of bowel, 688 g of water, and 20 g of others. Assuming that the succinic acid content in the processing stock solution was 100%, 71% of succinic acid was recovered in the crystal by low temperature crystallization, and 24% of bowel was contained in the filtrate and removed. The recovered succinic acid crystals were able to completely remove Na, and 97% of other impurities such as organic acids other than succinic acid could be removed.
（再晶析）
低温晶析で回収した結晶に含有するその他成分を除去するため、低温晶析で回収した結晶１７６ｇを、共栓付き三角フラスコ中の水６５０ｇにスターラー撹拌しながら添加した。次いで、三角フラスコに栓をした密閉状態にして、６５℃のウォーターバス中でスターラー撹拌をしながら昇温した。６５℃加温およびスターラー撹拌は継続し、結晶の完全溶解を確認したところで、５℃までウォーターバス中でスターラー撹拌をしながら冷却した。濾液を温度５℃の状態で２時間撹拌した後、事前に５℃に保冷した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。さらに、ヌッチェ上に結晶を全量回収した後、５℃の水１６０ｇをヌッチェ上の結晶に供給して結晶の洗浄を行った。
(Recrystallization)
In order to remove other components contained in the crystals recovered by the low temperature crystallization, 176 g of the crystals recovered by the low temperature crystallization were added to 650 g of water in the conical flask with a stopper while stirring with a stirrer. Next, the conical flask was sealed and the temperature was raised while stirring with a stirrer in a 65 ° C. water bath. Heating at 65 ° C. and stirring with a stirrer were continued, and when complete dissolution of crystals was confirmed, the mixture was cooled to 5 ° C. while stirring with a stirrer in a water bath. The filtrate was stirred at a temperature of 5 ° C. for 2 hours, and then solid-liquid separation was performed by suction filtration using a Nutsche having an inner diameter of 110 mm and 5B filter paper that had been previously cooled to 5 ° C. Further, after all the crystals were collected on Nutsche, 160 g of water at 5 ° C. was supplied to the crystals on Nutsche to wash the crystals.
回収した結晶重量は１５２ｇであり、その内訳はコハク酸１４０ｇ、ボウショウ０ｇ、水分１２ｇ、その他成分０ｇであった。また、回収した濾液は水洗浄分も含めて合計８３４ｇであり、その内訳は、コハク酸２４ｇ、ボウショウ０ｇ、水分８０８ｇ、その他２ｇであった。処理原液中のコハク酸含有量を１００％とすると、再晶析により、結晶としてコハク酸は６１％回収された。また、回収したコハク酸結晶は完全に不純物を除去できた。低温晶析および再晶析で回収した濾液を次回以降の処理にリサイクルする場合、本実施例におけるリサイクルできないコハク酸のロスは１６ｇ、処理原液中の含有量に対して７％となった。 The recovered crystal weight was 152 g, and the breakdown was 140 g of succinic acid, 0 g of bowel, 12 g of water, and 0 g of other components. The collected filtrate was 834 g in total, including the water wash, and the breakdown was 24 g of succinic acid, 0 g of bowel, 808 g of water, and 2 g of others. Assuming that the succinic acid content in the processing stock solution is 100%, 61% of succinic acid was recovered as crystals by recrystallization. Moreover, the recovered succinic acid crystals could completely remove impurities. When the filtrate collected by low-temperature crystallization and recrystallization was recycled to the subsequent treatment, the loss of succinic acid that could not be recycled in this example was 16 g, which was 7% of the content in the treatment stock solution.
〔実施例２〕
＜反応液（Ｂ）の分離精製＞
（硫酸添加）
表１に示した組成を有する反応液（Ｂ）２０６０ｇ（２．０Ｌ）を撹拌しながら、反応液中に含まれるアルカリ金属と同当量数の濃硫酸１６８ｇを添加し、処理原液を調製した。表２に示すように、得られた処理原液は、反応液量が２２２８ｇ（２．１Ｌ）、コハク酸含有量が１６１ｇ（９．３ｇ/１００ｇ-水）、ボウショウ含有量が２４４ｇ（１４．０ｇ/１００ｇ-水）となった。
[Example 2]
<Separation and purification of reaction solution (B)>
(Addition of sulfuric acid)
While stirring 2060 g (2.0 L) of the reaction solution (B) having the composition shown in Table 1, 168 g of concentrated sulfuric acid having the same number as the alkali metal contained in the reaction solution was added to prepare a processing stock solution. As shown in Table 2, the obtained processing stock solution has a reaction solution amount of 2228 g (2.1 L), a succinic acid content of 161 g (9.3 g / 100 g-water), and a bowel content of 244 g (14.0 g). / 100 g-water).
（高温晶析）
続いて、処理原液をロータリーエバポレータで７９５ｇまで濃縮し、コハク酸濃度を４６ｇ／１００ｇ-水、ボウショウ濃度を６９ｇ／１００ｇ-水とし、共栓つき三角フラスコに全量移した。三角フラスコに栓をした密閉状態にして、８０℃のウォーターバス中でスターラー撹拌をしながら昇温した。濃縮液を温度８０℃の状態で２時間撹拌した後、事前に８０℃に加熱した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。
(High temperature crystallization)
Subsequently, the processing stock solution was concentrated to 795 g with a rotary evaporator, the succinic acid concentration was 46 g / 100 g-water, the bow concentration was 69 g / 100 g-water, and the whole amount was transferred to an Erlenmeyer flask with a stopper. The flask was sealed in a conical flask, and the temperature was raised while stirring with a stirrer in an 80 ° C. water bath. The concentrated solution was stirred at a temperature of 80 ° C. for 2 hours, and then subjected to solid filtration by suction filtration using a Nutsche having an inner diameter of 110 mm and a 5B filter paper heated to 80 ° C. in advance.
回収した濾液は５７７ｇであり、その内訳は、コハク酸１５２ｇ、ボウショウ５８ｇ、水分３３８ｇ、その他２９ｇであった。また、回収した結晶重量は２１８ｇであり、その内訳はボウショウ１８５ｇ、コハク酸１０ｇ、水分１７ｇ、その他成分６ｇであった。高温晶析により処理原液中のコハク酸は濾液に９４％回収され、ボウショウは結晶に７６％含有され除去された。 The collected filtrate was 577 g, and the breakdown was 152 g of succinic acid, 58 g of bowel, 338 g of water, and 29 g of others. The recovered crystal weight was 218 g, and the breakdown was 185 g boushou, 10 g succinic acid, 17 g water, and 6 g other components. As a result of high-temperature crystallization, 94% of succinic acid in the processing stock solution was recovered in the filtrate, and 76% of bowel was contained in the crystals and removed.
（低温晶析）
高温晶析で回収した濾液５７７ｇを、共栓付き三角フラスコに全量移し、三角フラスコに栓をした密閉状態にして、３５℃のウォーターバス中でスターラー撹拌をしながら降温した。濃縮液を温度３５℃の状態で２時間撹拌した後、事前に３５℃に保温した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。さらに、ヌッチェ上に結晶を全量回収した後、３５℃の水１５２ｇをヌッチェ上の結晶に供給して結晶の洗浄を行った。
(Low temperature crystallization)
The total amount of 577 g of the filtrate collected by high temperature crystallization was transferred to a conical stoppered Erlenmeyer flask, sealed in a stoppered Erlenmeyer flask, and the temperature was lowered while stirring with a stirrer in a 35 ° C water bath. The concentrated liquid was stirred at a temperature of 35 ° C. for 2 hours, and then solid-liquid separation was performed by suction filtration using a Nutsche having an inner diameter of 110 mm and a filter paper of 5B, which had been kept at 35 ° C. in advance. Further, after all the crystals were collected on Nutsche, 152 g of water at 35 ° C. was supplied to the crystals on Nutsche to wash the crystals.
回収した結晶重量は１２５ｇであり、その内訳はコハク酸１１３ｇ、ボウショウ０ｇ、水分１０ｇ、その他成分２ｇであった。また、回収した濾液は水洗浄分も含めて合計６０４ｇであり、その内訳は、コハク酸３９ｇ、ボウショウ５８ｇ、水分４８０ｇ、その他２７ｇであった。処理原液中のコハク酸含有量を１００％とすると、低温晶析により、結晶中にコハク酸は７０％回収され、ボウショウは濾液中に２４％含有され除去された。また、回収したコハク酸結晶は完全にＮａを除去することができ、さらに他の不純物も９７％除去できた。 The recovered crystal weight was 125 g, and the breakdown was 113 g of succinic acid, 0 g of bowel, 10 g of water, and 2 g of other components. The collected filtrate was 604 g in total, including the water wash, and the breakdown was 39 g of succinic acid, 58 g of bowel, 480 g of water, and 27 g of others. Assuming that the succinic acid content in the processing stock solution was 100%, 70% of succinic acid was recovered in the crystals by low temperature crystallization, and 24% of bowel was contained in the filtrate and removed. Further, the recovered succinic acid crystal was able to completely remove Na, and 97% of other impurities could be removed.
（再晶析）
低温晶析で回収した結晶に含有するその他成分を除去するため、低温晶析で回収した結
晶１２５ｇを、共栓付き三角フラスコ中の水４５０ｇにスターラー撹拌しながら添加した。三角フラスコに栓をした密閉状態にして、６５℃のウォーターバス中でスターラー撹拌をしながら昇温した。
(Recrystallization)
In order to remove other components contained in the crystals recovered by the low temperature crystallization, 125 g of the crystals recovered by the low temperature crystallization were added to 450 g of water in the conical flask with a stopper while stirring with a stirrer. The flask was sealed in a conical flask, and the temperature was raised while stirring with a stirrer in a water bath at 65 ° C.
６５℃加温およびスターラー撹拌は継続し、結晶の完全溶解を確認したところで、活性炭ＢＡ−５０（味の素ファインテクノ製）をコハク酸重量に対して３％の３．４ｇ添加した。活性炭添加後１時間、６５℃加温および撹拌を継続して処理した後、事前に６５℃に保温した内径１１０ｍｍのヌッチェおよび５Ｃの濾紙を用いて吸引濾過して濾液を回収した。回収した濾液は５５０ｇで、濾液中のコハク酸は１０９ｇであった。 Heating at 65 ° C. and stirring with a stirrer were continued, and when complete dissolution of the crystals was confirmed, activated carbon BA-50 (manufactured by Ajinomoto Fine-Techno) was added in an amount of 3.4 g of 3% based on the weight of succinic acid. One hour after the addition of the activated carbon, the mixture was continuously heated and stirred at 65 ° C., and then suction filtered using a Nutsche having an inner diameter of 110 mm and 5C filter paper previously kept at 65 ° C., and the filtrate was collected. The collected filtrate was 550 g, and succinic acid in the filtrate was 109 g.
回収した濾液は、共栓付き三角フラスコに全量移し、三角フラスコに栓をした密閉状態にして５℃のウォーターバス中でスターラー撹拌をしながら冷却した。濾液を温度５℃の状態で２時間撹拌した後、事前に５℃に保冷した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。さらに、ヌッチェ上に結晶を全量回収した後、５℃の水１１０ｇをヌッチェ上の結晶に供給して結晶の洗浄を行った。 The entire amount of the collected filtrate was transferred to a conical stoppered Erlenmeyer flask, cooled in a water bath at 5 ° C. while stirring with a stirrer in a sealed state where the Erlenmeyer flask was stoppered. The filtrate was stirred at a temperature of 5 ° C. for 2 hours, and then solid-liquid separation was performed by suction filtration using a Nutsche having an inner diameter of 110 mm and 5B filter paper that had been previously cooled to 5 ° C. Furthermore, after all the crystals were collected on Nutsche, 110 g of water at 5 ° C. was supplied to the crystals on Nutsche to wash the crystals.
回収した結晶重量は９７ｇであり、その内訳はコハク酸９０ｇ、ボウショウ０ｇ、水分７ｇ、その他成分０ｇであった。また、回収した濾液は水洗浄分も含めて合計５６３ｇであり、その内訳は、コハク酸１９ｇ、ボウショウ０ｇ、水分５４３ｇ、その他１ｇであった。処理原液中のコハク酸含有量を１００％とすると、再晶析により、結晶中にコハク酸は５６％回収された。また、回収したコハク酸結晶は完全に不純物を除去できた。低温晶析および再晶析で回収した濾液を次回以降の処理にリサイクルする場合、本実施例におけるリサイクルできないコハク酸のロスは１４ｇ、処理原液の含有量に対して９％となった。 The recovered crystal weight was 97 g, and the breakdown was 90 g of succinic acid, 0 g of bowel, 7 g of water, and 0 g of other components. The collected filtrate was 563 g in total, including the water wash, and the breakdown was 19 g of succinic acid, 0 g of bowel, 543 g of moisture, and 1 g of others. When the succinic acid content in the processing stock solution was 100%, 56% of succinic acid was recovered in the crystals by recrystallization. Moreover, the recovered succinic acid crystals could completely remove impurities. When the filtrate collected by low-temperature crystallization and recrystallization was recycled for the subsequent treatment, the loss of succinic acid that could not be recycled in this example was 14 g, which was 9% based on the content of the treatment stock solution.
〔実施例３〕
＜反応液Ｃの分離精製＞
（硫酸添加）
表１に示した組成を有する反応液（Ｃ）２０４０ｇ（２．０Ｌ）を撹拌しながら、濃硫酸１００ｇを添加し、処理原液を調製した。表２に示すように、処理原液は、反応液量が２１４０ｇ（２．１Ｌ）、コハク酸含有量が７２ｇ（４．０ｇ/１００ｇ-水）、ボウショウ含有量が１４５ｇ（７．９ｇ/１００ｇ-水）となった。
Example 3
<Separation and purification of reaction solution C>
(Addition of sulfuric acid)
While stirring 2040 g (2.0 L) of the reaction solution (C) having the composition shown in Table 1, 100 g of concentrated sulfuric acid was added to prepare a processing stock solution. As shown in Table 2, the processing stock solution had a reaction solution amount of 2140 g (2.1 L), a succinic acid content of 72 g (4.0 g / 100 g-water), and a bowel content of 145 g (7.9 g / 100 g- Water).
（高温晶析）
続いて、処理原液をロータリーエバポレータで４５６ｇまで濃縮し、コハク酸濃度を３６ｇ／１００ｇ-水、ボウショウ濃度を７３ｇ／１００ｇ-水とし、共栓つき三角フラスコに全量移した。三角フラスコに栓をした密閉状態にして、８０℃のウォーターバス中でスターラー撹拌をしながら昇温した。濃縮液を温度８０℃の状態で２時間撹拌した後、事前に８０℃に加熱した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。
(High temperature crystallization)
Subsequently, the treated stock solution was concentrated to 456 g using a rotary evaporator, the succinic acid concentration was 36 g / 100 g-water, the bowel concentration was 73 g / 100 g-water, and the whole amount was transferred to an Erlenmeyer flask with a stopper. The flask was sealed in a conical flask, and the temperature was raised while stirring with a stirrer in an 80 ° C. water bath. The concentrated solution was stirred at a temperature of 80 ° C. for 2 hours, and then subjected to solid filtration by suction filtration using a Nutsche having an inner diameter of 110 mm and a 5B filter paper heated to 80 ° C. in advance.
回収した濾液は３２４ｇであり、その内訳は、コハク酸６６ｇ、ボウショウ３３ｇ、水分１９０ｇ、その他３５ｇであった。また、回収した結晶重量は１３２ｇであり、その内訳はボウショウ１１２ｇ、コハク酸７ｇ、水分１０ｇ、その他成分４ｇであった。高温晶析により処理原液中のコハク酸が濾液中に９１％回収され、ボウショウは結晶として７７％除去された。 The collected filtrate was 324 g, and the breakdown was 66 g of succinic acid, 33 g of bowel, 190 g of water, and 35 g of others. The recovered crystal weight was 132 g, of which 112 g was shochu, 7 g succinic acid, 10 g water, and 4 g other components. 91% of succinic acid in the processing stock solution was recovered in the filtrate by high-temperature crystallization, and 77% of bowel was removed as crystals.
（低温晶析）
高温晶析で回収した濾液３２４ｇを、共栓付き三角フラスコに全量移し、三角フラスコに栓をした密閉状態にして、３５℃のウォーターバス中でスターラー撹拌をしながら降温
した。濃縮液を温度３５℃の状態で２時間撹拌した後、事前に３５℃に保温した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。さらに、ヌッチェ上に結晶を全量回収した後、３５℃の水６６ｇをヌッチェ上の結晶に供給して結晶の洗浄を行った。
(Low temperature crystallization)
A total amount of 324 g of the filtrate recovered by high temperature crystallization was transferred to an Erlenmeyer flask with a stopper, sealed in a stoppered Erlenmeyer flask, and the temperature was lowered while stirring with a stirrer in a 35 ° C. water bath. The concentrated liquid was stirred at a temperature of 35 ° C. for 2 hours, and then solid-liquid separation was performed by suction filtration using a Nutsche having an inner diameter of 110 mm and a filter paper of 5B, which had been kept at 35 ° C. in advance. Further, after all the crystals were collected on Nutsche, 66 g of water at 35 ° C. was supplied to the crystals on Nutsche to wash the crystals.
回収した結晶重量は５９ｇであり、その内訳はコハク酸５１ｇ、ボウショウ０ｇ、水分５ｇ、その他成分３ｇであった。また、回収した濾液は水洗浄分も含めて合計３３１ｇであり、その内訳は、コハク酸１５ｇ、ボウショウ３３ｇ、水分２５１ｇ、その他３２ｇであった。処理原液中のコハク酸含有量を１００％とすると、低温晶析により、結晶中にコハク酸は７０％回収され、ボウショウは濾液中に２３％含有し除去された。また、回収したコハク酸結晶は完全にＮａを除去することができ、さらに他の不純物も９７％除去できた。 The recovered crystal weight was 59 g, and the breakdown was 51 g of succinic acid, 0 g of bowel, 5 g of water, and 3 g of other components. Further, the collected filtrate was 331 g in total including the amount washed with water, and the breakdown was 15 g of succinic acid, 33 g of bowel, 251 g of water, and 32 g of others. Assuming that the succinic acid content in the processing stock solution was 100%, 70% of succinic acid was recovered in the crystal by low temperature crystallization, and 23% of bowel was contained in the filtrate and removed. Further, the recovered succinic acid crystal was able to completely remove Na, and 97% of other impurities could be removed.
（再晶析）
低温晶析で回収した結晶に含有するその他成分を除去するため、低温晶析で回収した結晶５９ｇを、共栓付き三角フラスコ中の水２００ｇにスターラー撹拌しながら添加した。三角フラスコに栓をした密閉状態にして、６５℃のウォーターバス中でスターラー撹拌をしながら昇温した。
(Recrystallization)
In order to remove other components contained in the crystal recovered by the low temperature crystallization, 59 g of the crystal recovered by the low temperature crystallization was added to 200 g of water in the conical flask with a stopper while stirring with a stirrer. The flask was sealed in a conical flask, and the temperature was raised while stirring with a stirrer in a water bath at 65 ° C.
６５℃加温およびスターラー撹拌は継続し、結晶の完全溶解を確認したところで、活性炭ＢＡ−５０（味の素ファインテクノ製）をコハク酸重量に対して５％の２．５ｇ添加した。活性炭添加後１時間、６５℃加温および撹拌を継続して処理した後、事前に６５℃に保温した内径１１０ｍｍのヌッチェおよび５Ｃの濾紙を用いて吸引濾過して濾液を回収した。回収した濾液は２３５ｇで、濾液中のコハク酸は４７ｇであった。 Heating at 65 ° C. and stirring with a stirrer were continued, and when complete dissolution of the crystals was confirmed, activated carbon BA-50 (manufactured by Ajinomoto Fine Techno) was added in an amount of 2.5 g of 5% based on the weight of succinic acid. One hour after the addition of the activated carbon, the mixture was continuously heated and stirred at 65 ° C., and then suction filtered using a Nutsche having an inner diameter of 110 mm and 5C filter paper previously kept at 65 ° C., and the filtrate was collected. The collected filtrate was 235 g, and the succinic acid in the filtrate was 47 g.
回収した濾液は、共栓付き三角フラスコに全量移し、三角フラスコに栓をし密閉した状態にして５℃のウォーターバス中でスターラー撹拌をしながら冷却した。濾液を温度５℃の状態で２時間撹拌した後、事前に５℃に保冷した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。さらに、ヌッチェ上に結晶を全量回収した後、５℃の水５０ｇをヌッチェ上の結晶に供給して結晶の洗浄を行った。 The whole amount of the collected filtrate was transferred to an Erlenmeyer flask with a stopper, and the Erlenmeyer flask was stoppered and sealed, and cooled in a water bath at 5 ° C. while stirring with a stirrer. The filtrate was stirred at a temperature of 5 ° C. for 2 hours, and then solid-liquid separation was performed by suction filtration using a Nutsche having an inner diameter of 110 mm and 5B filter paper that had been previously cooled to 5 ° C. Furthermore, after all the crystals were collected on Nutsche, 50 g of water at 5 ° C. was supplied to the crystals on Nutsche to wash the crystals.
回収した結晶重量は４２ｇであり、その内訳はコハク酸３８ｇ、ボウショウ０ｇ、水分４ｇ、その他成分０ｇであった。また、回収した濾液は水洗浄分も含めて合計２４３ｇであり、その内訳は、コハク酸９ｇ、ボウショウ０ｇ、水分２３３ｇ、その他２ｇであった。処理原液中のコハク酸含有量を１００％とすると、再晶析により、結晶中にコハク酸は５３％回収された。また、回収したコハク酸結晶は完全に不純物を除去できた。低温晶析および再晶析で回収した濾液を次回以降の処理にリサイクルする場合、本実施例におけるリサイクルできないコハク酸のロスは１１ｇ、処理原液の含有量に対して１５％となった。 The recovered crystal weight was 42 g, and the breakdown was 38 g of succinic acid, 0 g of bowel, 4 g of water, and 0 g of other components. Further, the collected filtrate was 243 g in total including the amount washed with water, and the breakdown was 9 g of succinic acid, 0 g of bowel, 233 g of water, and 2 g of others. Assuming that the succinic acid content in the processing stock solution is 100%, 53% of succinic acid was recovered in the crystals by recrystallization. Moreover, the recovered succinic acid crystals could completely remove impurities. When the filtrate collected by low-temperature crystallization and recrystallization was recycled for the subsequent treatment, the loss of succinic acid that could not be recycled in this example was 11 g, and the content of the treatment stock solution was 15%.
〔実施例４〕
＜反応液（Ｂ）の分離精製２回目＞
（硫酸添加）
表１に示した組成を有する反応液（Ｂ）２０６０ｇ（２．０Ｌ）を撹拌しながら、濃硫酸１６８ｇを添加した。この結果、反応液量は２２２８ｇ（２．１Ｌ）、コハク酸含有量は１６１ｇ（９．３ｇ/１００ｇ-水）、ボウショウ含有量は２４４ｇ（１４．０ｇ/１０
０ｇ-水）となった。
Example 4
<Second Separation and Purification of Reaction Solution (B)>
(Addition of sulfuric acid)
While stirring 2060 g (2.0 L) of the reaction solution (B) having the composition shown in Table 1, 168 g of concentrated sulfuric acid was added. As a result, the reaction liquid amount was 2228 g (2.1 L), the succinic acid content was 161 g (9.3 g / 100 g-water), and the bowel content was 244 g (14.0 g / 10).
0 g-water).
（濾液リサイクル）
得られた硫酸添加液に、実施例２の低温晶析工程で回収した濾液６０４ｇおよび再晶析
工程で回収した濾液５６３ｇ加えて混合し、処理原液を調製した。得られた処理原液は、混合液量が３３９５ｇ（３．３Ｌ）、コハク酸含有量が２１９ｇ（７．９ｇ/１００ｇ-水）、ボウショウ含有量が３０２ｇ（１０．９ｇ/１００ｇ-水）となった。
(Filtrate recycling)
To the obtained sulfuric acid addition liquid, 604 g of the filtrate recovered in the low-temperature crystallization step of Example 2 and 563 g of the filtrate recovered in the recrystallization step were added and mixed to prepare a processing stock solution. The obtained processing stock solution has a mixed solution amount of 3395 g (3.3 L), a succinic acid content of 219 g (7.9 g / 100 g-water), and a bowel content of 302 g (10.9 g / 100 g-water). It was.
（高温晶析）
続いて、処理原液をロータリーエバポレータで１０１９ｇまで濃縮し、コハク酸濃度を４９ｇ／１００ｇ-水、ボウショウ濃度を６７ｇ／１００ｇ-水とし、共栓つき三角フラスコに全量移した。三角フラスコに栓をした密閉状態にして、８０℃のウォーターバス中でスターラー撹拌をしながら昇温した。濃縮液を温度８０℃の状態で２時間撹拌を継続した後、事前に８０℃に加熱した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。
(High temperature crystallization)
Subsequently, the processing stock solution was concentrated to 1019 g with a rotary evaporator, the succinic acid concentration was 49 g / 100 g-water, the bow concentration was 67 g / 100 g-water, and the whole amount was transferred to an Erlenmeyer flask with a stopper. The flask was sealed in a conical flask, and the temperature was raised while stirring with a stirrer in an 80 ° C. water bath. The concentrated liquid was continuously stirred for 2 hours at a temperature of 80 ° C., and then subjected to solid filtration by suction filtration using a Nutsche having an inner diameter of 110 mm and 5B filter paper heated to 80 ° C. in advance.
回収した濾液は７４３ｇであり、その内訳は、コハク酸２０２ｇ、ボウショウ７３ｇ、水分４３０ｇ、その他３９ｇであった。また、回収した結晶重量は２７５ｇであり、その内訳はボウショウ２３０ｇ、コハク酸１８ｇ、水分２０ｇ、その他成分８ｇであった。高温晶析により処理原液中のコハク酸は濾液中に９２％回収され、ボウショウは結晶として７６％除去された。 The recovered filtrate was 743 g, and the breakdown was 202 g of succinic acid, 73 g of bowel, 430 g of water, and 39 g of others. The recovered crystal weight was 275 g, and the breakdown was 230 g of bowsho, 18 g of succinic acid, 20 g of water, and 8 g of other components. Due to high temperature crystallization, 92% of succinic acid in the processing stock solution was recovered in the filtrate, and 76% of bowel was removed as crystals.
（低温晶析）
高温晶析で回収した濾液７４３ｇを、共栓付き三角フラスコに全量移し、三角フラスコに栓をした密閉状態にして、３５℃のウォーターバス中でスターラー撹拌をしながら降温した。濃縮液を温度３５℃の状態で２時間撹拌した後、事前に３５℃に保温した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。さらに、ヌッチェ上に結晶を全量回収した後、３５℃の水２０２ｇをヌッチェ上の結晶に供給して結晶の洗浄を行った。
(Low temperature crystallization)
The total amount of 743 g of the filtrate recovered by high temperature crystallization was transferred to an Erlenmeyer flask with a stopper, sealed in a stoppered Erlenmeyer flask, and the temperature was lowered while stirring with a stirrer in a 35 ° C. water bath. The concentrated liquid was stirred at a temperature of 35 ° C. for 2 hours, and then solid-liquid separation was performed by suction filtration using a Nutsche having an inner diameter of 110 mm and a filter paper of 5B, which had been kept at 35 ° C. in advance. Furthermore, after all the crystals were collected on Nutsche, 202 g of water at 35 ° C. was supplied to the crystals on Nutsche to wash the crystals.
回収した結晶重量は１７４ｇであり、その内訳はコハク酸１５６ｇ、ボウショウ０ｇ、水分１４ｇ、その他成分４ｇであった。また、回収した濾液は水洗浄分も含めて合計７７２ｇであり、その内訳は、コハク酸４６ｇ、ボウショウ７３ｇ、水分６１８ｇ、その他３５ｇであった。処理原液中のコハク酸含有量を１００％とすると、この低温晶析により、結晶中にコハク酸は７１％回収され、ボウショウは濾液中に２４％含有し除去された。また、回収したコハク酸結晶は完全にＮａを除去することができ、さらに他の不純物も９６％除去できた。 The recovered crystal weight was 174 g, and the breakdown was 156 g of succinic acid, 0 g of bowel, 14 g of water, and 4 g of other components. Moreover, the collected filtrate was 772 g in total including the amount of water washed, and the breakdown was 46 g of succinic acid, 73 g of bowel, 618 g of water, and 35 g of others. Assuming that the succinic acid content in the processing stock solution is 100%, this low temperature crystallization recovered 71% of succinic acid in the crystals and contained 24% of the bowel in the filtrate. Further, the recovered succinic acid crystal was able to completely remove Na, and 96% of other impurities could be removed.
（再晶析）
低温晶析で回収した結晶に含有するその他成分を除去するため、低温晶析で回収した結晶１７４ｇを、共栓付き三角フラスコ中の水６５０ｇにスターラー撹拌しながら添加した。三角フラスコに栓をした密閉状態にして、６５℃のウォーターバス中でスターラー撹拌をしながら昇温した。
(Recrystallization)
In order to remove other components contained in the crystals recovered by the low temperature crystallization, 174 g of the crystals recovered by the low temperature crystallization were added to 650 g of water in the conical flask with a stopper while stirring with a stirrer. The flask was sealed in a conical flask, and the temperature was raised while stirring with a stirrer in a water bath at 65 ° C.
６５℃加温およびスターラー撹拌は継続し、結晶の完全溶解を確認したところで、活性炭ＢＡ−５０（味の素ファインテクノ製）をコハク酸重量に対して３％の４．７ｇ添加した。活性炭添加後１時間、６５℃加温および撹拌を継続して処理した後、事前に６５℃に保温した内径１１０ｍｍのヌッチェおよび５Ｃの濾紙を用いて吸引濾過して濾液を回収した。回収した濾液は７８５ｇで、濾液中のコハク酸は１５０ｇであった。 Heating at 65 ° C. and stirring with a stirrer were continued, and when complete dissolution of crystals was confirmed, activated carbon BA-50 (manufactured by Ajinomoto Fine-Techno) was added in an amount of 4.7 g of 3% based on the weight of succinic acid. One hour after the addition of the activated carbon, the mixture was continuously heated and stirred at 65 ° C., and then suction filtered using a Nutsche having an inner diameter of 110 mm and 5C filter paper previously kept at 65 ° C., and the filtrate was collected. The collected filtrate was 785 g, and succinic acid in the filtrate was 150 g.
回収した濾液は、共栓付き三角フラスコに全量移し、三角フラスコに栓をした密閉状態にして５℃のウォーターバス中でスターラー撹拌をしながら冷却した。濾液を温度５℃の状態で２時間撹拌した後、事前に５℃に保冷した内径１１０ｍｍのヌッチェおよび５Ｂの濾紙を用いて吸引濾過して固液分離を行った。さらに、ヌッチェ上に結晶を全量回収した
後、５℃の水１５０ｇをヌッチェ上の結晶に供給して結晶の洗浄を行った。
The entire amount of the collected filtrate was transferred to a conical stoppered Erlenmeyer flask, cooled in a water bath at 5 ° C. while stirring with a stirrer in a sealed state where the Erlenmeyer flask was stoppered. The filtrate was stirred at a temperature of 5 ° C. for 2 hours, and then solid-liquid separation was performed by suction filtration using a Nutsche having an inner diameter of 110 mm and 5B filter paper that had been previously cooled to 5 ° C. Furthermore, after all the crystals were recovered on Nutsche, 150 g of water at 5 ° C. was supplied to the crystals on Nutsche to wash the crystals.
回収した結晶重量は１３７ｇであり、その内訳はコハク酸１２５ｇ、ボウショウ０ｇ、水分１２ｇ、その他成分０ｇであった。また、回収した濾液は水洗浄分も含めて合計７９８ｇであり、その内訳は、コハク酸２５ｇ、ボウショウ０ｇ、水分７７１ｇ、その他２ｇであった。処理原液中のコハク酸含有量を１００％とすると、再晶析により、結晶中にコハク酸は５７％回収された。また、回収したコハク酸結晶は完全に不純物を除去できた。低温晶析および再晶析で回収した濾液を次回以降の処理にリサイクルする場合、本実施例におけるリサイクルできないコハク酸のロスは２４ｇ、処理原液の含有量に対して１１％となった。 The recovered crystal weight was 137 g, and the breakdown was 125 g of succinic acid, 0 g of bowel, 12 g of water, and 0 g of other components. Further, the collected filtrate was 798 g in total including the water-washed portion, and the breakdown was 25 g of succinic acid, 0 g of bowel, 771 g of water, and 2 g of others. When the succinic acid content in the processing stock solution was 100%, 57% of succinic acid was recovered in the crystals by recrystallization. Moreover, the recovered succinic acid crystals could completely remove impurities. When the filtrate collected by low-temperature crystallization and recrystallization was recycled for the subsequent treatment, the loss of succinic acid that could not be recycled in this example was 24 g, which was 11% of the content of the treatment stock solution.
Claims (13)
に記載のコハク酸の製造方法。 The solvent of the liquid containing the alkali metal succinate is water.
A method for producing succinic acid according to 1.
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