JPH0239502B2 - MONOMECHIRUHIDORAJINNOKAISHUHOHO - Google Patents

MONOMECHIRUHIDORAJINNOKAISHUHOHO

Info

Publication number
JPH0239502B2
JPH0239502B2 JP4038882A JP4038882A JPH0239502B2 JP H0239502 B2 JPH0239502 B2 JP H0239502B2 JP 4038882 A JP4038882 A JP 4038882A JP 4038882 A JP4038882 A JP 4038882A JP H0239502 B2 JPH0239502 B2 JP H0239502B2
Authority
JP
Japan
Prior art keywords
hydrazine
monomethylhydrazine
methanol
reaction solution
hydrochloride
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 - Lifetime
Application number
JP4038882A
Other languages
Japanese (ja)
Other versions
JPS58157751A (en
Inventor
Shiro Hojo
Yoichi Hasegawa
Masatoshi Higuchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NIPPON HYDROGENE KOGYO
Original Assignee
NIPPON HYDROGENE KOGYO
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NIPPON HYDROGENE KOGYO filed Critical NIPPON HYDROGENE KOGYO
Priority to JP4038882A priority Critical patent/JPH0239502B2/en
Publication of JPS58157751A publication Critical patent/JPS58157751A/en
Publication of JPH0239502B2 publication Critical patent/JPH0239502B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は新規なモノメチルヒドラジンの製造工
程における反応液からモノメチルヒドラジンを回
収する方法に関する。 モノメチルヒドラジンは、医薬品、農薬等の製
造に極めて有用な化学工業薬品である。 従来、モノメチルヒドラジンの製造方法として
は、アンモニアと次亜塩素酸ソーダとの反応で得
られるクロルアミンにモノメチルアミンを反応さ
せるいわゆる変形ラツシツヒ法、及びヒドラジン
のメチルハライドによるアルキル化法等が知られ
ている。しかし、前者は生成するモノメチルヒド
ラジンの収率が悪く、反応生成液中の濃度が極め
て低いため目的物の取出しに多量のエネルギーを
必要とする。又、後者は、目的のモノメチルヒド
ラジンのほかに、非対称ジメチルヒドラジン、対
称ジメチルヒドラジン、トリメチルヒドラジン等
の副生物を多量に併産するため、目的物の分離精
製工程が繁雑であり、かつ収率も低い。このた
め、従来の方法はいずれも工業的製造法としては
満足すべきものではなかつた。 本発明者らは、さきに、工業的に大量生産され
る安価なメタノールとともに工業的基礎材料であ
るヒドラジンと塩酸とから容易に得られるヒドラ
ジンモノ塩酸塩とを、ヒドラジンジ塩酸塩又は塩
化メチルの存在下に加熱反応させることによつ
て、モノメチルヒドラジンを極めて高い選択率で
容易に得ることができる画期的製造方法、並びに
反応生成物からのモノメチルヒドラジンの回収方
法を発明し、特許出願中である。(特願昭55−
173116)。 その発明方法においては、モノメチルヒドラジ
ンを高選択率で得る場合のヒドラジンモノ塩酸塩
の転化率は30%以下程度であるため、反応生成液
中にはモノメチルヒドラジン塩酸塩のほかに、未
反応のヒドラジンモノ塩酸塩、メタノール、水等
が残存している。この反応液からモノメチルヒド
ラジンを取出すためには、モノメチルヒドラジン
塩酸塩とヒドラジンモノ塩酸塩のメタノールに対
する溶解度が異ることに着目し、反応液からメタ
ノールと水とを蒸留で追出した残部に、新たにメ
タノールを加えてモノメチルヒドラジン塩酸塩を
溶解させ、メタノールに不溶のヒドラジン塩酸塩
を分離し、分離母液に苛性ソーダ等のアルカリを
加えて中和し、遊離したモノメチルヒドラジンを
蒸留で回収する方法が発明方法であつた。 上記の発明方法においては、分離されたヒドラ
ジンモノ塩酸塩はそのまま次の反応に原料として
循環使用できるので極めて好都合である。しか
し、反応液中のメタノールと水とを追い出した後
に、新たにメタノールを加えねばならぬこと、モ
ノメチルヒドラジンを塩酸塩から遊離させるため
に、ヒドラジンモノ塩酸塩分離後の母液にアルカ
リを加えて中和する工程を必要とするため、モノ
メチルヒドラジン塩酸塩および若干溶解している
ヒドラジンモノ塩酸塩から食塩が生成され、これ
を分離除去する操作も必要となるなどの欠点も有
していた。 本発明者らは、これらの欠点を改良し、反応生
成液から更に容易な操作でより経済的にモノメチ
ルヒドラジンを取出す方法について種々研究中
に、反応液中からある程度の水を留去させた後の
残液に水加ヒドラジンを添加して蒸留すればモノ
メチルヒドラジンが定量的に留出することを見出
し、鋭意研究を重ねた結果、本発明を完成するに
至つた。 本発明は、ヒドラジンモノ塩酸塩とメタノール
とを、ヒドラジン塩酸塩又は塩化メチルの存在下
に反応させて得られるモノメチルヒドラジン塩酸
塩を含む反応液に、ヒドラジンを添加して蒸留す
ることを特徴とする、モノメチルヒドラジンの回
収方法である。 本発明において、反応液に添加するヒドラジン
は100%水加ヒドラジンが好適である。添加する
水加ヒドラジンの量は、反応液中に存在する塩酸
のモル数に対し、1.2〜2.0モルの範囲が好適であ
る。蒸留の方法は回分式、連続式のいずれでもよ
いが、反応液の加熱温度は120℃以下が好適であ
る。 本発明の方法によれば、さきのヒドラジンモノ
塩酸塩を結晶として分離除去した後アルカリで中
和して蒸留する方法に比して、工程が簡略であ
り、かつモノメチルヒドラジンの留出後の缶残液
は塩酸を加えて塩酸塩に調整して次の反応に再使
用することができる。又、蒸留の際モノメチルヒ
ドラジンのほかに水加ヒドラジンの一部を回収す
ることもできる。 以下、実施例により本発明方法を説明する。 実施例 1 ヒドラジン塩酸塩の50%水溶液に所定量のメタ
ノールを添加し、ヒドラジン塩酸塩の存在下に反
応して得られた反応液を濃縮して大部分の水を留
出させた後、これに100%水加ヒドラジンを添加
し、回転蒸留塔(ガラス製、内径25mm、高さ100
cm、ジヤケツト付、ジヤケツト内に100℃の水蒸
気を通す)を用いて、100mmHgの減圧下に連続的
に蒸留した。 留出液および缶残の組成を分析し、その結果を
表1に示す。 表1によりモノメチルヒドラジンの回収率は
97.7%である。
The present invention relates to a novel method for recovering monomethylhydrazine from a reaction solution in a monomethylhydrazine manufacturing process. Monomethylhydrazine is an extremely useful industrial chemical for the production of pharmaceuticals, agricultural chemicals, and the like. Conventionally, known methods for producing monomethylhydrazine include the so-called modified Raschzig method, in which monomethylamine is reacted with chloramine obtained by the reaction of ammonia and sodium hypochlorite, and the alkylation method of hydrazine with methyl halide. . However, in the former method, the yield of monomethylhydrazine produced is poor and the concentration in the reaction product solution is extremely low, so a large amount of energy is required to extract the target product. In addition, the latter produces a large amount of by-products such as asymmetric dimethyl hydrazine, symmetric dimethyl hydrazine, and trimethyl hydrazine in addition to the desired monomethyl hydrazine, so the separation and purification process of the desired product is complicated and the yield is low. low. For this reason, none of the conventional methods was satisfactory as an industrial manufacturing method. The present inventors first prepared hydrazine dihydrochloride or methyl chloride from hydrazine monohydrochloride, which is easily obtained from hydrazine and hydrochloric acid, which are industrial basic materials, as well as inexpensive methanol, which is industrially mass-produced. We have invented an innovative production method that allows monomethylhydrazine to be easily obtained with extremely high selectivity by carrying out a heated reaction in the presence of a chemical reaction, and a method for recovering monomethylhydrazine from the reaction product, and are currently applying for a patent. be. (Special application 1982-
173116). In the method of the invention, when monomethylhydrazine is obtained with high selectivity, the conversion rate of hydrazine monohydrochloride is about 30% or less, so in addition to monomethylhydrazine hydrochloride, unreacted hydrazine is contained in the reaction product solution. Monohydrochloride, methanol, water, etc. remain. In order to extract monomethylhydrazine from this reaction solution, we focused on the difference in the solubility of monomethylhydrazine hydrochloride and hydrazine monohydrochloride in methanol. A method was invented in which methanol was added to dissolve monomethylhydrazine hydrochloride, hydrazine hydrochloride insoluble in methanol was separated, the separated mother liquor was neutralized by adding an alkali such as caustic soda, and the liberated monomethylhydrazine was recovered by distillation. It was a method. The method of the invention described above is extremely convenient because the separated hydrazine monohydrochloride can be recycled as it is as a raw material for the next reaction. However, after expelling methanol and water from the reaction solution, new methanol must be added, and in order to liberate monomethylhydrazine from the hydrochloride, an alkali is added to the mother liquor after the separation of hydrazine monohydrochloride. Since it requires a step of mixing, common salt is produced from monomethylhydrazine hydrochloride and slightly dissolved hydrazine monohydrochloride, and it also has the disadvantage that it also requires an operation to separate and remove it. The present inventors, while conducting various research on methods for improving these drawbacks and more economically extracting monomethylhydrazine from the reaction product solution through easier operations, discovered that after distilling off a certain amount of water from the reaction solution, They discovered that monomethylhydrazine could be quantitatively distilled out by adding hydrazine hydrate to the residual liquid and distilling the mixture, and as a result of extensive research, they completed the present invention. The present invention is characterized in that hydrazine is added to a reaction solution containing monomethylhydrazine hydrochloride obtained by reacting hydrazine monohydrochloride and methanol in the presence of hydrazine hydrochloride or methyl chloride, and then distilled. , a method for recovering monomethylhydrazine. In the present invention, hydrazine added to the reaction solution is preferably 100% hydrated hydrazine. The amount of hydrazine hydrate to be added is preferably in the range of 1.2 to 2.0 moles relative to the number of moles of hydrochloric acid present in the reaction solution. The distillation method may be either a batch method or a continuous method, but the heating temperature of the reaction solution is preferably 120° C. or lower. According to the method of the present invention, the process is simpler than the previous method in which hydrazine monohydrochloride is separated and removed as crystals, neutralized with alkali, and then distilled, and the process is simpler, and The residual solution can be adjusted to a hydrochloride salt by adding hydrochloric acid and reused in the next reaction. Furthermore, in addition to monomethylhydrazine, a portion of hydrated hydrazine can also be recovered during distillation. The method of the present invention will be explained below with reference to Examples. Example 1 A predetermined amount of methanol was added to a 50% aqueous solution of hydrazine hydrochloride, and the resulting reaction solution was concentrated to distill off most of the water. Add 100% hydrazine hydrate to
Continuous distillation was carried out under a reduced pressure of 100 mmHg using a vacuum cleaner (with a jacket and passing steam at 100°C through the jacket). The compositions of the distillate and bottoms were analyzed and the results are shown in Table 1. According to Table 1, the recovery rate of monomethylhydrazine is
It is 97.7%.

【表】【table】

【表】 実施例 2 実施例1と同様に反応液を濃縮した後、充填塔
つき蒸留器を用いて回分式で蒸留した。 充填塔は内径15mm、高さ600mmで、圧力は200mm
Hgの減圧下に操作し、缶温は100〜120℃で実施
した。分析結果を表2に示す。 表2の結果よりモノメチルヒドラジンの回収率
は95.5%である。留出液はさらに精留すれば純モ
ノメチルヒドラジンが得られる。
[Table] Example 2 After concentrating the reaction solution in the same manner as in Example 1, it was distilled batchwise using a still with a packed column. The packed tower has an inner diameter of 15 mm, a height of 600 mm, and a pressure of 200 mm.
It was operated under reduced pressure of Hg, and the temperature of the reactor was 100 to 120°C. The analysis results are shown in Table 2. From the results in Table 2, the recovery rate of monomethylhydrazine was 95.5%. If the distillate is further rectified, pure monomethylhydrazine can be obtained.

【表】 * 表2の化合物名の欄の記号は表1と同じである。
[Table] * The symbols in the compound name column of Table 2 are the same as in Table 1.

Claims (1)

【特許請求の範囲】[Claims] 1 ヒドラジンモノ塩酸塩とメタノールとを、ヒ
ドラジンジ塩酸塩または塩化メチルの存在下に反
応させて得られるモノメチルヒドラジン塩酸塩を
含む反応液に、ヒドラジンを添加して蒸留するこ
とを特徴とする、モノメチルヒドラジンの回収方
法。
1 Monomethyl hydrazine, which is characterized in that hydrazine is added to a reaction solution containing monomethylhydrazine hydrochloride obtained by reacting hydrazine monohydrochloride and methanol in the presence of hydrazine dihydrochloride or methyl chloride, and then distilled. How to recover hydrazine.
JP4038882A 1982-03-15 1982-03-15 MONOMECHIRUHIDORAJINNOKAISHUHOHO Expired - Lifetime JPH0239502B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4038882A JPH0239502B2 (en) 1982-03-15 1982-03-15 MONOMECHIRUHIDORAJINNOKAISHUHOHO

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4038882A JPH0239502B2 (en) 1982-03-15 1982-03-15 MONOMECHIRUHIDORAJINNOKAISHUHOHO

Publications (2)

Publication Number Publication Date
JPS58157751A JPS58157751A (en) 1983-09-19
JPH0239502B2 true JPH0239502B2 (en) 1990-09-05

Family

ID=12579268

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4038882A Expired - Lifetime JPH0239502B2 (en) 1982-03-15 1982-03-15 MONOMECHIRUHIDORAJINNOKAISHUHOHO

Country Status (1)

Country Link
JP (1) JPH0239502B2 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007046467A1 (en) 2007-09-28 2009-04-02 Saltigo Gmbh Process for the preparation of monomethylhydrazine
CN102516117B (en) * 2011-12-06 2016-01-20 东力(南通)化工有限公司 The technique of producing methyl hydrazine with hydrazine hydrate method
CN105037196B (en) * 2015-08-10 2017-03-29 济南大学 The new method of catalytic synthesis of methyl hydrazine under a kind of normal pressure
CN106543026B (en) * 2016-10-31 2018-01-16 石家庄金派医药化工有限公司 A kind of preparation method of methyl hydrazine
CN109400497A (en) * 2018-12-11 2019-03-01 河北合佳医药科技集团股份有限公司 A kind of process for cleanly preparing of methyl hydrazine

Also Published As

Publication number Publication date
JPS58157751A (en) 1983-09-19

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