JPS6324983B2 - - Google Patents
Info
- Publication number
- JPS6324983B2 JPS6324983B2 JP206185A JP206185A JPS6324983B2 JP S6324983 B2 JPS6324983 B2 JP S6324983B2 JP 206185 A JP206185 A JP 206185A JP 206185 A JP206185 A JP 206185A JP S6324983 B2 JPS6324983 B2 JP S6324983B2
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- malate
- caustic soda
- disodium
- hydrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 239000002002 slurry Substances 0.000 claims description 41
- WPUMTJGUQUYPIV-UHFFFAOYSA-L sodium malate Chemical compound [Na+].[Na+].[O-]C(=O)C(O)CC([O-])=O WPUMTJGUQUYPIV-UHFFFAOYSA-L 0.000 claims description 24
- 235000019265 sodium DL-malate Nutrition 0.000 claims description 23
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 16
- DOJOZCIMYABYPO-UHFFFAOYSA-M sodium;3,4-dihydroxy-4-oxobutanoate Chemical compound [Na+].OC(=O)C(O)CC([O-])=O DOJOZCIMYABYPO-UHFFFAOYSA-M 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000001630 malic acid Substances 0.000 description 4
- 235000011090 malic acid Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- CBVOCNWSAAUNIY-UHFFFAOYSA-N 2-hydroxybutanedioic acid;sodium Chemical compound [Na].[Na].OC(=O)C(O)CC(O)=O CBVOCNWSAAUNIY-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- BWAUQTFFVCLSOS-UHFFFAOYSA-N sodiosodium hydrate Chemical compound O.[Na].[Na] BWAUQTFFVCLSOS-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明の目的はdl−リンゴ酸ジナトリウム低水
和物をdl−リンゴ酸から直接工業的に有利に製造
する方法を提供するにある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The object of the present invention is to provide an industrially advantageous method for directly producing dl-malic acid disodium low hydrate from dl-malic acid.
dl−リンゴ酸ジナトリウムは食品添加物であ
り、食品加工用その他に使用され、需要は増大の
傾向にある。 dl-Disodium malate is a food additive used for food processing and other purposes, and demand is on the rise.
従来、リンゴ酸ジナトリウム水和物の製造方法
は種々提案されているが、その何れもがリンゴ酸
ジナトリウム水溶液からリンゴ酸ジナトリウム水
和物の結晶として採取する方法であつた。リンゴ
酸ジナトリウムは水に対する溶解度が大きく、リ
ンゴ酸ジナトリウムを溶液から結晶として採取す
るには加熱濃縮は勿論のこと、取扱い工程数も多
く繁雑である。
Conventionally, various methods for producing disodium malate hydrate have been proposed, but all of them involve collecting disodium malate hydrate as crystals from an aqueous disodium malate solution. Disodium malate has a high solubility in water, and collecting disodium malate as crystals from a solution requires not only heating and concentration but also many handling steps and is complicated.
そこで、本発明者は先にdl−リンゴ酸ジナトリ
ウムを水溶液とせずにdl−リンゴ酸にソーダ灰又
は重炭酸ソーダ等の炭酸塩を混合し苛性ソーダ水
溶液を加えて反応を行ない、中和度を80〜90％と
してスラリー状のリンゴ酸ジナトリウムとした
後、更に苛性ソーダ水溶液を加えてPHを調整しdl
−リンゴ酸ジナトリウムのスラリーを経て直接粉
末化する製造方法を提案した（特願昭59−20838
号）。しかし更に能率的な製造方法が望まれた。 Therefore, the present inventor did not first make dl-malic acid disodium into an aqueous solution, but instead mixed dl-malic acid with a carbonate such as soda ash or sodium bicarbonate, added a caustic soda aqueous solution, and conducted the reaction to achieve a degree of neutralization of 80 to 80. After making a slurry of disodium malate to 90%, add an aqueous solution of caustic soda to adjust the pH.
- Proposed a manufacturing method of directly powdering disodium malate through slurry (Patent application No. 59-20838)
issue). However, a more efficient manufacturing method was desired.
本発明者は、更に有利な製造方法を探究した結
果リンゴ酸モノナトリウムは第１図曲線１で示さ
れるように曲線２で示されるリンゴ酸ジナトリウ
ムの溶解度に比較して溶解度が小さく、且つ晶出
し易くて水溶液を濃縮すれば、高温度でも容易に
晶出してスラリーと成り、従つて水分の蒸発も速
く濃縮が容易となり、又濃縮されたリンゴ酸モノ
ナトリウムの結晶スラリーに苛性ソーダ水溶液を
加えて中和すれば高温度でも溶解せずにリンゴ酸
ジナトリウムの晶出が起りスラリーとなる事を見
い出した。スラリーから水分の蒸発が起ると更に
晶出が起り、晶出熱を発生するのでスラリー自身
の内部からも加熱される事となり、蒸発速度は加
速され非常に速いものとなる。これらの知見にも
とづきリンゴ酸ジナトリウム低水和物を有利に製
造する方法を完成したものである。
As a result of searching for a more advantageous production method, the present inventor found that monosodium malate has a lower solubility, as shown by curve 1 in Figure 1, than the solubility of disodium malate, shown by curve 2. If you concentrate the aqueous solution because it is easy to extract, it will crystallize easily even at high temperatures to form a slurry, and therefore water will evaporate quickly and concentration will be easy. It was discovered that when neutralized, disodium malate does not dissolve even at high temperatures and crystallizes to form a slurry. When moisture evaporates from the slurry, further crystallization occurs and heat of crystallization is generated, so that the slurry itself is heated from within itself, accelerating the evaporation rate and becoming extremely fast. Based on these findings, a method for advantageously producing disodium malate low hydrate has been completed.
すなわち、本発明はリンゴ酸に苛性ソーダ水溶
液を加えるか、ソーダ灰、重炭酸ソーダ等の炭酸
塩（以下炭酸塩と称す）の一種又は二種を混合
後、水又は苛性ソーダ水溶液を加えて中和反応を
行ない、リンゴ酸モノナトリウムの結晶スラリー
と成し、70〜110℃に加熱濃縮する第一工程と、
第一工程によつて得たスラリーを撹拌しながら70
〜100℃に加熱して水分蒸発を行ないつつ、更に
スラリーが溶解しないよう、又適度の流動性を保
つ様注意して苛性ソーダ水溶液を加えて中和反応
を行なうリンゴ酸ジナトリウムの結晶スラリーと
成し、引続き水分蒸発を行なつて湿つた粉粒体結
晶となす第二工程と、湿つた粉粒体結晶を70〜
130℃に加熱して含水率10％以下の流動性の良い
粉粒体と成す第三工程とから成る、dl−リンゴ酸
ジナトリウム水和物の製造法に関する。 That is, the present invention involves adding an aqueous solution of caustic soda to malic acid, or mixing one or two types of carbonates (hereinafter referred to as carbonates) such as soda ash and sodium bicarbonate, and then adding water or an aqueous solution of caustic soda to perform a neutralization reaction. , a first step of forming a crystal slurry of monosodium malate and heating and concentrating it at 70 to 110°C;
While stirring the slurry obtained in the first step,
While heating to ~100°C to evaporate water, aqueous caustic soda solution is added with care to prevent the slurry from further dissolving and to maintain appropriate fluidity, resulting in a crystalline slurry of disodium malate. Then, the second step is to evaporate water to form wet powder crystals, and the wet powder crystals are heated to 70~70℃.
The present invention relates to a method for producing dl-disodium malate hydrate, which comprises a third step of heating to 130°C to form a powder with good fluidity and a moisture content of 10% or less.
本発明は、第一工程から第三工程までを同一容
器中で実施可能である。このため使用する反応機
はニーダのごとき強力な撹拌機を備えた混合機が
望ましく、温度調整可能なら更に好ましい。次に
本発明を詳細に説明する。 In the present invention, the first step to the third step can be carried out in the same container. For this reason, the reactor used is preferably a mixer equipped with a powerful stirrer such as a kneader, and more preferably if the temperature can be adjusted. Next, the present invention will be explained in detail.
本発明の第一工程ではリンゴ酸に苛性ソーダ水
溶液を加えるか、炭酸塩の一種又は二種を混合
後、水又は苛性ソーダ水溶液を加えて中和反応を
行ない、リンゴ酸モノナトリウムと成す。炭酸塩
を使用する時は炭酸ガスの発生があるので注意し
ながら反応を行なう。炭酸塩と苛性ソーダを併用
する場合の使用割合及び苛性ソーダ水溶液の濃度
には特に制限はないが、反応後のリンゴ酸モノナ
トリウム濃度が60〜80％に成る様に調整して反応
を行なう。濃度が60％以下では濃縮に時間を要
し、又80％以上では反応が均一に行なわれないな
ど好ましくない。反応にあたつて炭酸塩の使用割
合が多い場合には中和による反応熱の発生が少な
いので、反応を円滑に行なうため加熱が望ましい
が、苛性ソーダが多い場合には発熱量が多いので
加熱は特に要しない。加熱はこれらの使用割合に
より必要に応じて適宜行なえば良い。第一工程で
の中和は正確にリンゴ酸モノナトリウム
（Na／C4H6O5モル比＝1.0）とする必要はなく、中和
度をPH４前後（望ましくは3.8〜4.3）のリンゴ酸
モノナトリウムの晶出範囲とすれば良い。リンゴ
酸モノナトリウムは溶解度が小さく、且つ結晶化
が起り易いため、反応後の溶液には容易にリンゴ
酸モノナトリウムが晶出しスラリーとなる。 In the first step of the present invention, a caustic soda aqueous solution is added to malic acid, or one or two carbonates are mixed, and then water or a caustic soda aqueous solution is added to carry out a neutralization reaction to form monosodium malate. When using carbonates, be careful as carbon dioxide gas is generated. When carbonate and caustic soda are used in combination, there are no particular restrictions on the proportions used and the concentration of the aqueous caustic soda solution, but the reaction is carried out while adjusting the concentration of monosodium malate to be 60 to 80% after the reaction. If the concentration is less than 60%, it will take time to concentrate, and if it is more than 80%, the reaction will not be carried out uniformly, which is undesirable. When a large proportion of carbonate is used in the reaction, less reaction heat is generated due to neutralization, so heating is preferable to ensure a smooth reaction. However, when a large amount of caustic soda is used, heating is not recommended as the amount of heat generated is large. Not particularly necessary. Heating may be carried out as necessary depending on the proportions of these materials used. Neutralization in the first step does not need to be done exactly with monosodium malate (Na/C 4 H 6 O 5 molar ratio = 1.0), but with malic acid at a pH of around 4 (preferably 3.8 to 4.3). It may be within the crystallization range of monosodium. Since monosodium malate has low solubility and crystallization is likely to occur, monosodium malate easily crystallizes in the solution after the reaction to form a slurry.
本発明では第一工程でのスラリーの加熱を70〜
110℃で行なう。リンゴ酸モノナトリウムの溶解
度は第１図曲線１と曲線２との対比からわかるよ
うに小さく、晶出し易い性質のため高温に加熱し
てもスラリーが溶解する事はない。スラリーから
の水分蒸発は非常に速く、更に高温に加熱される
事により、蒸発速度は加速され、容易に蒸発濃縮
される。温度が70℃以下では蒸発が遅く、又110
℃以上ではリンゴ酸モノナトリウムを変質するお
それがあるので好ましくない。 In the present invention, the heating of the slurry in the first step is
Perform at 110℃. The solubility of monosodium malate is small, as seen from the comparison between curves 1 and 2 in Figure 1, and because it tends to crystallize, the slurry does not dissolve even when heated to high temperatures. Water evaporates from the slurry very quickly, and by heating it to a higher temperature, the evaporation rate is accelerated and the slurry is easily evaporated and concentrated. Evaporation is slow when the temperature is below 70℃, and
If the temperature is higher than 0.degree. C., monosodium malate may be denatured, so it is not preferable.
第一工程で濃縮されたスラリーは第二工程にお
いて撹拌しながら70〜100℃に加熱し苛性ソーダ
水溶液をスラリーが溶解しない様に注意して加え
蒸発と中和反応を行ないスラリーのPHを８前後の
リンゴ酸ジナトリウムとする。第二工程で加える
苛性ソーダ水溶液濃度は30％以上を使用する。30
％以下では反応後のスラリー濃度が薄くなり濃縮
に時間を要するので望ましくない。 The slurry concentrated in the first step is heated to 70 to 100℃ while stirring in the second step, and an aqueous solution of caustic soda is added with care so that the slurry does not dissolve. Evaporation and neutralization reactions are carried out to bring the pH of the slurry to around 8. Disodium malate. The concentration of the caustic soda aqueous solution added in the second step is 30% or more. 30
% or less is not desirable because the slurry concentration after reaction becomes thin and it takes time to concentrate.
リンゴ酸ジナトリウムは溶解度が大きく、水溶
液を加熱濃縮しても溶液は粘度を増すばかりで晶
出は起らない。このため75〜85％に濃縮後溶液の
温度を60℃以下に冷却して、リンゴ酸ジナトリウ
ム水和物結晶を晶出する方法の提案が行なわれて
いる（特公昭53−41129号）。本発明では70〜100
℃でリンゴ酸ジナトリウム水和物の晶出を行な
う。第一工程で濃縮されたリンゴ酸モノナトリウ
ムの結晶スラリーに苛性ソーダ水溶液を加えて中
和反応を行ない、中和度がリンゴ酸ジナトリウム
の晶出範囲に達すると、70℃以上の高温にもかか
わらずリンゴ酸ジナトリウム水和物の晶出が容易
に起る。リンゴ酸のモノナトリウムは無水塩であ
るのに対して、本発明の第二工程で晶出するジナ
トリウムは水和物であるために、ジナトリウムの
水和物が晶出し始めると、スラリー中の水分が減
少する。又晶出熱を発生するのでスラリーからの
水分蒸発も速く、濃縮は更に容易に行なわれる。
第二工程での加熱が70℃以下では水分の蒸発が遅
く、又100℃以上では溶解度が大きくなつてスラ
リーが溶解するので本発明では採用しない。 Disodium malate has a high solubility, and even if an aqueous solution is heated and concentrated, the solution will only increase in viscosity and no crystallization will occur. For this reason, a method has been proposed in which disodium malate hydrate crystals are crystallized by concentrating the solution to 75-85% and then cooling the solution to 60° C. or lower (Japanese Patent Publication No. 41129/1983). In the present invention, 70 to 100
Crystallization of disodium malate hydrate is carried out at ℃. Aqueous caustic soda solution is added to the crystal slurry of monosodium malate concentrated in the first step to perform a neutralization reaction, and when the degree of neutralization reaches the crystallization range of disodium malate, the crystalline slurry is heated to 70°C or higher. Crystallization of disodium malate hydrate occurs easily. While monosodium malic acid is an anhydrous salt, the disodium crystallized in the second step of the present invention is a hydrate, so when the hydrate of disodium begins to crystallize, it water content decreases. Furthermore, since heat of crystallization is generated, water evaporates from the slurry quickly, and concentration can be carried out more easily.
If the heating in the second step is 70°C or lower, the evaporation of water will be slow, and if the heating is 100°C or higher, the solubility will increase and the slurry will dissolve, so this is not adopted in the present invention.
本発明では反応物の濃度をスラリー状態で行
う。リンゴ酸ジナトリウムの濃厚溶液は100℃以
下では蒸発が遅く、沸騰させるには120〜130℃に
も加熱を要し、高温度溶液からは晶出は起らな
い。このため前記特公昭53−41129号の提案の様
に60℃以下に冷却しなければならない等困難な点
が多い。従つて本発明では、リンゴ酸モノナトリ
ウムのスラリーを高温に加熱濃縮後、更に水和し
て高温度領域からリンゴ酸のモノナトリウム結晶
をジナトリウム水和物結晶スラリーに変える事が
極めて重要な意味を有する。 In the present invention, the concentration of reactants is determined in a slurry state. Concentrated solutions of disodium malate evaporate slowly at temperatures below 100°C and require heating to 120-130°C to boil, and crystallization does not occur from high-temperature solutions. For this reason, there are many difficulties, such as the need to cool the product to 60° C. or lower, as proposed in Japanese Patent Publication No. 53-41129. Therefore, in the present invention, it is extremely important to heat and concentrate the slurry of monosodium malate to a high temperature and then further hydrate it to convert the monosodium malate crystals into a disodium hydrate crystal slurry from the high temperature range. has.
本発明では70〜100℃に加熱しながらリンゴ酸
ジナトリウムの晶出を行ないスラリーとするため
に水分の蒸発は非常に速い特徴がある。更に加熱
を続けて蒸発し湿つた粉粒体と成つたなら、引続
き温度を70〜130℃に加熱して、含水率10％以下
の流動性の良い粉粒体リンゴ酸ジナトリウム水和
物と成す。第２図はリンゴ酸ジナトリウム水和物
の乾燥温度と含水率の関係を示す。乾燥温度が50
℃以下では含水率約23％で３水和物（計算値
23.29％）、70〜110℃では約９％で１水和物（計
算値9.18％）に相当し、130℃以上で無水塩とな
る。 In the present invention, disodium malate is crystallized while heating to 70 to 100°C to form a slurry, so water evaporates very quickly. If the heating continues and it evaporates into a wet powder, continue to heat the temperature to 70-130℃ to form disodium malate hydrate, a powder with moisture content of 10% or less and good fluidity. I will do it. FIG. 2 shows the relationship between drying temperature and water content of disodium malate hydrate. Drying temperature is 50
Below ℃, the moisture content is approximately 23% and the trihydrate (calculated value)
23.29%), at 70 to 110°C, it is approximately 9%, corresponding to a monohydrate (calculated value 9.18%), and at 130°C or higher, it becomes an anhydrous salt.
次に実施例により本発明を具体的に説明する。
尚、含水率はカールフイツシヤー法により測定し
た。 Next, the present invention will be specifically explained with reference to Examples.
Incidentally, the water content was measured by the Karl Fischer method.
実施例 １
dl−リンゴ酸1500ｇ（11.2モル）をニーダに仕
込み、撹拌しながら48％の苛性ソーダ水溶液933
ｇを注意しながら加えると、激しく水蒸気を発生
しながら反応し、ただちに晶出が起り、スラリー
と成つた。Example 1 1500 g (11.2 moles) of dl-malic acid was charged into a kneader, and 48% caustic soda aqueous solution 933 was added while stirring.
When g was added carefully, the reaction occurred while generating intense water vapor, and crystallization immediately occurred to form a slurry.
生成したスラリーのPHは4.0でリンゴ酸モノナ
トリウムであつた。続いてニーダのジヤケツトに
スチームを通して加熱すると、すみやかに蒸発し
てスラリーは濃縮され、かたさを増して来た。こ
の間のスラリーの温度は100〜105℃であつた。次
に加熱温度を下げて90℃とし、蒸発を続けながら
スラリーが溶解しないように注意して、48％苛性
ソーダ水溶液を加え、PHを7.7に調整し中和反応
を終了した。スラリーは更に加熱を続け、30分後
に湿つた粉粒体になつたので、加熱をスチームに
切換え120℃とした結果30分後に流動性の良い粉
末状dl−リンゴ酸ジナトリウム2075ｇを得た。含
水率は4.2％であつた。 The resulting slurry had a pH of 4.0 and was monosodium malate. Next, when steam was passed through the kneader jacket and heated, the slurry quickly evaporated and became concentrated and hardened. The temperature of the slurry during this time was 100-105°C. Next, the heating temperature was lowered to 90°C, and while continuing evaporation, a 48% aqueous solution of caustic soda was added, taking care not to dissolve the slurry, and the pH was adjusted to 7.7 to complete the neutralization reaction. The slurry continued to be heated, and after 30 minutes it became a wet powder, so the heating was switched to steam and the temperature was raised to 120°C. After 30 minutes, 2075 g of dl-disodium malate powder with good fluidity was obtained. The moisture content was 4.2%.
実施例 ２
dl−リンゴ酸1500ｇ（11.2モル）をソーダ灰
300ｇ（2.8モル）をニーダに仕込み、撹拌混合し
48％の苛性ソーダ水溶液591ｇを注意して加える
と、炭酸ガスを発生しながら反応し、すみやかに
晶出が起つてスラリーとなつた。この時の中和度
はPH4.2（Na／C4H6O5モル比＝1.14）でスラリーはリ
ンゴ酸モノナトリウムであつた。続いてニーダー
のジヤケツトにスチームを通して加熱すると15分
後にはスラリーがかたさを増して来た。この間の
温度は100〜108℃であつた。次に加熱温度を85℃
に下げて48％苛性ソーダ水溶液をスラリーが溶解
しないように注意して加えPHを7.8に調整し中和
反応を終了した。スラリーは更に加熱を続けて水
分を蒸発させ30分後に湿つた粉粒体と成つたの
で、そのまま加熱を続け2180ｇの流動性の良い粉
末状dl−リンゴ酸ジナトリウムを得た。含水率は
8.9％であつた。Example 2 1500 g (11.2 mol) of dl-malic acid was added to soda ash.
Pour 300g (2.8mol) into a kneader and stir to mix.
When 591 g of a 48% aqueous solution of caustic soda was carefully added, the reaction occurred while generating carbon dioxide gas, and crystallization immediately occurred to form a slurry. The degree of neutralization at this time was PH4.2 (Na/C 4 H 6 O 5 molar ratio = 1.14), and the slurry was monosodium malate. Next, steam was passed through the jacket of the kneader to heat it, and after 15 minutes the slurry became hard. The temperature during this period was 100-108°C. Next, increase the heating temperature to 85℃
The pH was adjusted to 7.8 by adding a 48% aqueous solution of caustic soda, taking care not to dissolve the slurry, to complete the neutralization reaction. The slurry was further heated to evaporate water and turned into wet powder after 30 minutes, so heating was continued to obtain 2180 g of powdered disodium dl-malate with good fluidity. The moisture content is
It was 8.9%.
以上説明するとうり本発明にあつてはdl−リン
ゴ酸を水の存在下ナトリウムの炭酸塩や苛性ソー
ダで中和してdl−リンゴ酸ジナトリウムの低水和
物を製造するに当つて、一旦dl−リンゴ酸モノナ
トリウムのスラリー状態となしてから70〜100℃
の温度下で苛性ソーダ溶液で中和してdl−リンゴ
酸ジナトリウム水和物となすから従来法に比し操
業が容易であり、水分の蒸発が容易であり、操業
時間の短縮をはかることができる。
As explained above, in the present invention, when producing a low hydrate of dl-disodium malate by neutralizing dl-malic acid with sodium carbonate or caustic soda in the presence of water, once dl-malic acid is neutralized with sodium carbonate or caustic soda in the presence of water, −70 to 100℃ after forming monosodium malate into a slurry state
It is easier to operate than conventional methods because it is neutralized with a caustic soda solution at a temperature of can.
第１図は、dl−リンゴ酸モノナトリウムとdl−
リンゴ酸ジナトリウムの溶解度曲線、第２図は、
dl−リンゴ酸ジナトリウム水和物の乾燥温度と含
水率の関係を示す。
Figure 1 shows dl-monosodium malate and dl-
The solubility curve of disodium malate, Figure 2, is
The relationship between the drying temperature and water content of dl-disodium malate hydrate is shown.
Claims (1)
イソーダに炭酸ソーダ又は重曹を併用して中和反
応を行ない濃縮されたdl−リンゴ酸モノナトリウ
ムのスラリーとなす第１工程と第１工程によつて
得た反応生成物スラリーに70〜100℃で苛性ソー
ダ水溶液を加え中和反応と水分蒸発を行ないdl−
リンゴ酸ジナトリウム水和物の湿つた粉粒体結晶
となす第２工程と第２工程によつて得た湿つた粉
粒体結晶を70〜130℃に加熱して含水率10％以下
の流動性のよい粉粒体となす第３工程との結合を
特徴とするdl−リンゴ酸ジナトリウム水和物の製
造方法。1. Obtained by the first step and the first step in which dl-malic acid is neutralized using caustic soda alone or in combination with caustic soda and sodium carbonate or baking soda to form a concentrated slurry of monosodium dl-malate. Add a caustic soda aqueous solution to the reaction product slurry at 70 to 100℃ to perform a neutralization reaction and water evaporation.
The second step of forming wet powder crystals of disodium malate hydrate and the wet powder crystals obtained in the second step are heated to 70 to 130°C to form a fluid with a moisture content of 10% or less. 1. A method for producing dl-disodium malate hydrate, which is characterized by combining a powder with good properties and a third step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP206185A JPS61161239A (en) | 1985-01-11 | 1985-01-11 | Production of hydrated disodium dl-malate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP206185A JPS61161239A (en) | 1985-01-11 | 1985-01-11 | Production of hydrated disodium dl-malate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61161239A JPS61161239A (en) | 1986-07-21 |
| JPS6324983B2 true JPS6324983B2 (en) | 1988-05-23 |
Family
ID=11518824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP206185A Granted JPS61161239A (en) | 1985-01-11 | 1985-01-11 | Production of hydrated disodium dl-malate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61161239A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5314919A (en) * | 1987-08-28 | 1994-05-24 | The Procter & Gamble Company | Calcium supplements |
| CN103910621B (en) * | 2013-12-30 | 2015-09-09 | 西安万隆制药股份有限公司 | A kind of L MALIC ACID compound |
| CN104592008B (en) * | 2015-01-04 | 2016-06-15 | 安徽雪郎生物科技股份有限公司 | A kind of preparation method of DL-malic acid hydrogen sodium |
-
1985
- 1985-01-11 JP JP206185A patent/JPS61161239A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61161239A (en) | 1986-07-21 |
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