JP3777681B2 - Method for stabilizing methylthiopropionaldehyde - Google Patents
Method for stabilizing methylthiopropionaldehyde Download PDFInfo
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- JP3777681B2 JP3777681B2 JP31245396A JP31245396A JP3777681B2 JP 3777681 B2 JP3777681 B2 JP 3777681B2 JP 31245396 A JP31245396 A JP 31245396A JP 31245396 A JP31245396 A JP 31245396A JP 3777681 B2 JP3777681 B2 JP 3777681B2
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- JP
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- Prior art keywords
- mtpa
- methylthiopropionaldehyde
- stabilizing
- present
- hydroxide
- 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 - Fee Related
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ＣＨ3 ＳＣＨ2 ＣＨ2 ＣＨＯで表されるメチルチオプロピオンアルデヒド（以下、ＭＴＰＡと称する）の安定化方法に関する。さらに詳しくはＭＴＰＡを含む系の貯蔵、または蒸留精製時の安定化方法に関するものである。
【０００２】
【従来の技術】
メチルチオプロピオンアルデヒド（ＭＴＰＡ）は、メチオニンの原料として重要な化合物であり、通常メチルメルカプタンとアクロレインをアミン触媒存在下に反応させた後、未反応原料および触媒を蒸留で除去することにより製造している。しかしＭＴＰＡは分子内にホルミル基と硫黄原子を有し非常に不安定なため蒸留精製時に分解したり、長期間にわたる貯蔵時或いは運搬時に劣化を起こすことが知られている。
それ故、ＭＴＰＡの貯蔵時の劣化防止を目的として安定化剤を添加する方法がいくつか提案されている。
【０００３】
例えば、（１）ＭＴＰＡにピリジン、ピコリン、Ｎ，Ｎ−ジアルキルアニリン等のアミン類を添加する方法（特公昭４７−３２９６３号公報、特開昭４９−１１６０１７号公報等）、（２）フェノール化合物とアミン化合物を組み合わせて添加する方法（特公平３−７２０５８号公報）、（３）水酸化マグネシウム、水酸化カルシウム等の添加物とｐＨを２〜６に調整することでＭＴＰＡを安定化する方法（特公平３−７７１８９号公報）、（４）プロトトロピック剤と脱酸素剤を組み合わせて添加する方法（特表平６−５０６００１号公報）等が知られている。他方、特表平６−５０６００１号公報には、高温時には金属材料の存在により、ＭＴＰＡ劣化が速まることが記載されている。
【０００４】
【発明が解決しようとする課題】
しかしながら、このような安定化方法は、金属製の容器中でＭＴＰＡを夏期の高温状態で長期間貯蔵する場合には、その効果が小さく、ＭＴＰＡの劣化が深刻になることもあり、再度精製する必要が生じるなど、工業的に必ずしも満足できるものではない。それ故、ガラスライニングやポリ内装の容器を使用することも考えられるが、容器費用が高価になるとの欠点を有する。また、ＭＴＰＡは蒸留精製時にも熱的に劣化分解しその回収率が低下するが、これに関しても有効な手段は見出せていない。
【０００５】
かかる事情下に鑑み本発明者らは、ＭＴＰＡに対し、貯蔵時の安定性や蒸留精製時に於いても劣化防止効果の高い安定化剤を見出すべく鋭意検討した結果、本発明方法を完成するに至った。
【０００６】
【課題を解決するための手段】
すなわち本発明方法は、安定化剤として酸化水酸化鉄を添加存在せしめることを特徴とするメチルチオプロピオンアルデヒドの安定化方法を提供するにある。
さらに本発明方法は、メチルチオプロピオンアルデヒドの蒸留精製時に安定化剤として酸化水酸化鉄をメチルチオプロピオンアルデヒド中に存在せしめることを特徴とするメチルチオプロピオンアルデヒドの安定化方法を提供するものである。
【０００７】
【発明の実施の形態】
以下、本発明方法について具体的に説明する。
本発明に於いて用いられるＭＴＰＡは、特に制限されるものではなく、メチルメルカプタンとアクロレインより反応された粗生成物、該粗生成物より低沸分を蒸留除去しただけの粗精製品、さらには精留により高純度に精製された生成物等が挙げられ、これらに酸化水酸化鉄を添加・存在せしめればよい。
【０００８】
またＭＴＰＡの蒸留或いは精留時に該ＭＴＰＡ中に酸化水酸化鉄を添加、存在せしめた後、これら蒸留或いは精留等の操作を行う。これら操作は操作に際しＭＴＰＡ中に酸化水酸化鉄が存在していればよく、操作条件は公知の方法で実施すればよい。一般に、ＭＴＰＡまたはＭＴＰＡを含む系の蒸留は約５０〜約１５０℃、約１０〜約５０ｍｍＨｇの条件で行われる。
【０００９】
酸化水酸化鉄はＭＴＰＡに対して約１０〜約５０００ｐｐｍ、好ましくは約１００〜約１０００ｐｐｍ添加される。この際、前記安定剤添加量がこの範囲以下の場合には効果が十分ではなく、また、この範囲以上である場合には十分な安定効果は得られるものの経済的ではない。安定剤の添加方法は、特に限定されないが、例えば塊状や粉状の酸化水酸化鉄を直接添加しても良いし、あるいは適当な溶媒の溶液として添加しても良い。
【００１０】
尚、本発明方法の実施に際してはＭＴＰＡ中に安定剤として酸化水酸化鉄を存在せしめるのみで目的とする所望とするＭＴＰＡの劣化防止効果を発揮するが、必要に応じて当該分野で公知の安定化方法や安定化剤の使用等を併用することは勿論可能である。
【００１１】
【発明の効果】
以上詳述した本発明方法によれば、ＭＴＰＡ中に少量の酸化水酸化鉄を添加するのみで、ＭＴＰＡを高温で長期間貯蔵した場合や、貯蔵容器として金属性容器を使用した場合、更には蒸留精製を行う場合にも、効果的にＭＴＰＡの劣化を防止し得るもので、その工業的価値は頗る大である。
【００１２】
【実施例】
以下、本発明方法を実施例によって、より具体的に説明するが、本発明方法はこれら実施例の記載により限定されるものではない。
【００１３】
実施例１
精製したＭＴＰＡ（純度９８．１％）を内容積２０ｍｌの蓋付き試験管に１０ｇ入れ、さらに表１の試験液の欄に記載の如くステンレス片（ＳＵＳ−３０４Ｌ）や安定剤を添加し密栓してサンプルを作製した。このサンプルを１００℃の恒温槽に入れ、２４時間経過後にサンプリングし純度変化をガスクロマトグラフにより分析した。その結果を表１に示す。
【００１４】
【表１】
実施例２
精製したＭＴＰＡ（純度９８．１％）を内容積２０ｍｌの蓋付き試験管に１０ｇ入れ、さらに表２の試験液の欄に記載の如く鉄片や安定剤を添加し密栓してサンプルを作製した。このサンプルを１００℃の恒温槽に入れ、２４時間経過後にサンプリングし、純度変化をガスクロマトグラフにより分析した。その結果を表２に示す。
【００１６】
【表２】
実施例３
精製したＭＴＰＡ（純度９８．１％）を内容積２０ｍｌの蓋付き試験管に１０ｇ入れ、さらに表３の試験液の欄に記載の如くステンレス片（ＳＵＳ−３０４Ｌ）や安定剤を添加し密栓してサンプルを作製した。このサンプルを５０℃の恒温槽に入れ、経時的にサンプリングし純度変化をガスクロマトグラフによる分析で追跡した。その結果を表３に示す。
【００１８】
【表３】
実施例４
精製したＭＴＰＡ（純度９８．１％）２８０ｇを５００ｍｌガラス製フラスコに入れ、さらに表４の試験液の欄に記載の如くステンレス片（ＳＵＳ−３０４Ｌ）や安定剤を添加した。これにガラス製蒸留塔（３０ｍｍφ×４７０ｍｍＨ、マクマホン充填）を接続し、圧力２０ｔｏｒｒ、釜温１２０℃、還流比２０で蒸留を行った。実験終了後に留出液と釜液をガスクロマトグラフで分析し、ＭＴＰＡ量を計算し、仕込み時とのバランスを算出した。その結果を表４に示す。
【００２０】
【表４】
BACKGROUND OF THE INVENTION
The present invention relates to a method for stabilizing methylthiopropionaldehyde (hereinafter referred to as MTPA) represented by CH 3 SCH 2 CH 2 CHO. More specifically, the present invention relates to a method for stabilizing a system containing MTPA or during distillation purification.
[0002]
[Prior art]
Methylthiopropionaldehyde (MTPA) is an important compound as a raw material for methionine, and is usually produced by reacting methyl mercaptan and acrolein in the presence of an amine catalyst, and then removing unreacted raw material and catalyst by distillation. . However, it is known that MTPA has a formyl group and a sulfur atom in the molecule and is very unstable, so that it decomposes during distillation purification or deteriorates during long-term storage or transportation.
Therefore, several methods of adding a stabilizer for the purpose of preventing deterioration during storage of MTPA have been proposed.
[0003]
For example, (1) a method of adding amines such as pyridine, picoline, N, N-dialkylaniline to MTPA (Japanese Patent Publication No. 47-32963, Japanese Patent Laid-Open No. 49-1116017, etc.), (2) phenolic compound (3) Method of stabilizing MTPA by adjusting pH to 2-6 with additives such as magnesium hydroxide and calcium hydroxide (Japanese Patent Publication No. 3-77189), (4) a method of adding a prototropic agent and an oxygen scavenger in combination (Japanese Patent Publication No. 6-506001), and the like are known. On the other hand, JP-A-6-506001 describes that MTPA deterioration is accelerated due to the presence of a metal material at high temperatures.
[0004]
[Problems to be solved by the invention]
However, such a stabilization method is less effective when MTPA is stored in a metal container at a high temperature in summer for a long period of time, and MTPA degradation may become serious. It is not always satisfactory industrially, such as the need arises. Therefore, it is conceivable to use a container with a glass lining or a poly interior, but it has a disadvantage that the container cost becomes expensive. MTPA is also thermally degraded and decomposed during distillation purification and its recovery rate is lowered, but no effective means has been found in this regard.
[0005]
In view of such circumstances, the present inventors have intensively studied on MTPA to find a stabilizer having a high effect of preventing deterioration even during storage and distillation purification. As a result, the present inventors have completed the method of the present invention. It came.
[0006]
[Means for Solving the Problems]
That is, the method of the present invention provides a method for stabilizing methylthiopropionaldehyde, characterized by adding iron oxide hydroxide as a stabilizer.
Furthermore, the method of the present invention provides a method for stabilizing methylthiopropionaldehyde, wherein iron hydroxide hydroxide is present in methylthiopropionaldehyde as a stabilizer during distillation purification of methylthiopropionaldehyde.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the method of the present invention will be specifically described.
The MTPA used in the present invention is not particularly limited, and is a crude product obtained by reacting methyl mercaptan and acrolein, a crude product obtained by distilling off a low boiling point from the crude product, and Examples include products purified to high purity by rectification, and iron oxide hydroxide may be added to these products.
[0008]
Further, after MTPA is distilled or rectified, iron hydroxide hydroxide is added to the MTPA, and after that, operations such as distillation or rectification are performed. These operations may be performed as long as iron oxide hydroxide is present in the MTPA, and the operation conditions may be implemented by a known method. In general, distillation of MTPA or a system containing MTPA is conducted at about 50 to about 150 ° C. and about 10 to about 50 mmHg.
[0009]
The iron oxide hydroxide is added in an amount of about 10 to about 5000 ppm, preferably about 100 to about 1000 ppm, based on MTPA. At this time, when the added amount of the stabilizer is below this range, the effect is not sufficient, and when it is above this range, a sufficient stabilizing effect is obtained, but it is not economical. The method for adding the stabilizer is not particularly limited. For example, massive or powdered iron oxide hydroxide may be added directly, or may be added as a solution in an appropriate solvent.
[0010]
In carrying out the method of the present invention, the desired MTPA deterioration prevention effect is exhibited only by allowing iron oxide hydroxide to be present as a stabilizer in MTPA. Of course, it is possible to use a combination of a method for stabilizing and the use of a stabilizer.
[0011]
【The invention's effect】
According to the method of the present invention described in detail above, when only a small amount of iron oxide hydroxide is added to MTPA, MTPA is stored at a high temperature for a long period of time, or when a metallic container is used as a storage container, Even when distillation purification is performed, the MTPA can be effectively prevented from deteriorating, and its industrial value is very large.
[0012]
【Example】
Hereinafter, the method of the present invention will be described more specifically with reference to examples. However, the method of the present invention is not limited to the description of these examples.
[0013]
Example 1
Put 10 g of purified MTPA (purity 98.1%) into a test tube with a cap of 20 ml and add stainless steel strip (SUS-304L) and stabilizer as shown in the column of test solution in Table 1 and seal tightly. A sample was prepared. This sample was placed in a thermostatic bath at 100 ° C., sampled after 24 hours, and analyzed for purity change by gas chromatography. The results are shown in Table 1.
[0014]
[Table 1]
Example 2
10 g of purified MTPA (purity 98.1%) was put into a test tube with a cap of 20 ml and a sample was prepared by adding iron pieces and stabilizers as described in the column of test solution in Table 2 and sealing. This sample was placed in a thermostat at 100 ° C., sampled after 24 hours, and analyzed for purity change by gas chromatography. The results are shown in Table 2.
[0016]
[Table 2]
Example 3
Put 10 g of purified MTPA (purity 98.1%) into a test tube with a cap of 20 ml and add stainless steel strip (SUS-304L) and stabilizer as shown in the column of test solution in Table 3 and seal tightly. A sample was prepared. This sample was placed in a thermostat at 50 ° C., sampled over time, and the change in purity was followed by analysis using a gas chromatograph. The results are shown in Table 3.
[0018]
[Table 3]
Example 4
280 g of purified MTPA (purity 98.1%) was placed in a 500 ml glass flask, and stainless steel pieces (SUS-304L) and stabilizers were added as described in the column of test solution in Table 4. A glass distillation column (30 mmφ × 470 mmH, packed in McMahon) was connected thereto, and distillation was performed at a pressure of 20 torr, a kettle temperature of 120 ° C., and a reflux ratio of 20. After completion of the experiment, the distillate and the kettle liquid were analyzed with a gas chromatograph, the amount of MTPA was calculated, and the balance with the charge was calculated. The results are shown in Table 4.
[0020]
[Table 4]
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31245396A JP3777681B2 (en) | 1996-11-22 | 1996-11-22 | Method for stabilizing methylthiopropionaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31245396A JP3777681B2 (en) | 1996-11-22 | 1996-11-22 | Method for stabilizing methylthiopropionaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10152467A JPH10152467A (en) | 1998-06-09 |
| JP3777681B2 true JP3777681B2 (en) | 2006-05-24 |
Family
ID=18029385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31245396A Expired - Fee Related JP3777681B2 (en) | 1996-11-22 | 1996-11-22 | Method for stabilizing methylthiopropionaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3777681B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3205643A1 (en) * | 2016-02-15 | 2017-08-16 | Evonik Degussa GmbH | Method for the preparation of 3-methylthiopropionaldehyde |
| CN107903197B (en) * | 2017-12-22 | 2018-12-14 | 蓝星安迪苏南京有限公司 | The stabilizer for preparing and storing for 3- methylthiopropionaldehyde |
| EP3656760A1 (en) | 2018-11-21 | 2020-05-27 | Evonik Operations GmbH | Storage stable form of 3-methylthiopropionaldehyde |
-
1996
- 1996-11-22 JP JP31245396A patent/JP3777681B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH10152467A (en) | 1998-06-09 |
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