JPH01261360A - Production of perchloromethyl mercatpan - Google Patents
Production of perchloromethyl mercatpanInfo
- Publication number
- JPH01261360A JPH01261360A JP8926988A JP8926988A JPH01261360A JP H01261360 A JPH01261360 A JP H01261360A JP 8926988 A JP8926988 A JP 8926988A JP 8926988 A JP8926988 A JP 8926988A JP H01261360 A JPH01261360 A JP H01261360A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- acidic aqueous
- carbon disulfide
- perchloromethyl
- present
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 perchloromethyl Chemical group 0.000 title 1
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 13
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 36
- RYFZYYUIAZYQLC-UHFFFAOYSA-N perchloromethyl mercaptan Chemical compound ClSC(Cl)(Cl)Cl RYFZYYUIAZYQLC-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はパークロロメチルメルカプタンの製造法に関す
る。パークロロメチルメルカプタンは、医薬、農薬の合
成原料として重要な化合物であるチオホスゲンの原料と
して用いられる。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing perchloromethyl mercaptan. Perchloromethyl mercaptan is used as a raw material for thiophosgene, which is an important compound as a raw material for the synthesis of pharmaceuticals and agricultural chemicals.
〈従来技術〉
パークロロメチルメルカプタンの酸性水溶液中での製造
法としては、４０％硫酸水溶液中で製造する方法（米国
特許第３９９３６９３号明細書）、並びに無機酸性水溶
液中、連続で製造し、除熱を有機相と水相を分離後水相
のみ冷却し循環する方法（特開昭４７−１０４６８号公
報）が公知である。<Prior art> As methods for producing perchloromethyl mercaptan in an acidic aqueous solution, there is a method of producing it in a 40% sulfuric acid aqueous solution (US Pat. No. 3,993,693), and a method of producing perchloromethyl mercaptan continuously in an inorganic acidic aqueous solution and removing it. A method is known in which heat is separated into an organic phase and an aqueous phase, and then only the aqueous phase is cooled and circulated (JP-A-47-10468).
〈従来技術の問題点〉
従来技術の酸性水溶液中での製造法は、回分法、連続法
ともに収率が低い。また、従来法の回分法は、除熱律速
のため小規模の製造には適しているが工業的ではない。<Problems with the prior art> The conventional production method in an acidic aqueous solution has a low yield in both the batch method and the continuous method. In addition, the conventional batch method is suitable for small-scale production because of heat removal rate control, but is not industrially suitable.
一方、連続法においては、工業的規模での適用が可能で
あるがパークロロメチルメルカプタン収率、選択率の低
下、二硫化炭素の転化率の低下等の問題を有している。On the other hand, the continuous method can be applied on an industrial scale, but has problems such as a decrease in the perchloromethyl mercaptan yield and selectivity, and a decrease in the conversion rate of carbon disulfide.
〈発明が解決しようとする手段〉
本発明者は、パークロロメチルメルカプタンの ′工
業的かつ、高収率な製造法について鋭意検討したところ
、塩素化反応を短時間で行うことにより収率が向上する
ことを見出した。また、反応方法としでは、外部熱交換
器を備えた外部循環冷却式反応装置においてのみ本発明
が可能であることを見出し発明を完成させるに至った。<Means to be Solved by the Invention> The present inventor has intensively studied an industrial and high-yield production method for perchloromethyl mercaptan, and has found that the yield can be improved by carrying out the chlorination reaction in a short time. I found out what to do. Furthermore, regarding the reaction method, the present inventors discovered that the present invention was possible only in an external circulation cooling type reactor equipped with an external heat exchanger, and thus completed the present invention.
即ち、本発明は、二硫化炭素を酸性水溶液中、塩素によ
り塩素化しパークロロメチルメルカプタンを製造するに
あたり、外部熱交換器を備えた反応装置を用い、二硫化
炭素の酸性水溶液を循環冷却しながら、二硫化炭素に対
して塩素を１．０ｋｇ／Ｈ−ｋｇ以上で供給することに
よりパークロロメチルメルカプタンを高収率で製造でき
、る方法を提供するものである。That is, the present invention uses a reaction apparatus equipped with an external heat exchanger to chlorinate carbon disulfide with chlorine in an acidic aqueous solution to produce perchloromethyl mercaptan, while circulating and cooling the acidic aqueous solution of carbon disulfide. The present invention provides a method in which perchloromethyl mercaptan can be produced in high yield by supplying chlorine at a rate of 1.0 kg/H-kg or more to carbon disulfide.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に用いる反応装置としては、撹拌機を備えた反応
器に、二硫化炭素に対して、除熱能力４００１ｃ ｃ
ａ １ ／ Ｈ−ｋｇ以上の外部循環冷却器および循環
ポンプより構成される。The reactor used in the present invention is a reactor equipped with a stirrer and has a heat removal capacity of 4001cc for carbon disulfide.
Consists of an external circulation cooler and circulation pump of a 1/H-kg or more.
該外部循環冷却器の冷却能力としては、４００ｋｃａｌ
／Ｈ−ｋｇ以下では、本反応は発熱量が大であるため、
除熱不充分で反応温度の上昇が起り、本発明を適用でき
ない。また、１００００ｋｃａ１／Ｈ−ｋｇ以上の除熱
能力を有する外部循環冷却器は装置サイズが大となるた
め、工業的ではない。The cooling capacity of the external circulation cooler is 400 kcal.
/H-kg or less, this reaction has a large calorific value, so
The present invention cannot be applied because the reaction temperature increases due to insufficient heat removal. Further, an external circulation cooler having a heat removal capacity of 10,000 kcal/H-kg or more is not industrially suitable because the device size is large.
このため、好ましくは、４００〜１００００ ｋ ｃａ
ｌ／！（・−の除熱能力を有する外部循環冷却器である
。For this reason, preferably 400 to 10,000 kca
l/! (It is an external circulation cooler with a heat removal capacity of -.
外部循環冷却装置のサイズおよび循環ポンプの能力は、
■的とする除熱量により決定される。The size of the external circulation cooling device and the capacity of the circulation pump are
■Determined by the target amount of heat removal.
反応器については、冷却用ジャケットを有しても良いが
、大きな効果は望めない。The reactor may have a cooling jacket, but no great effect can be expected.
反応温度としては、０〜３０℃の範囲が好ましく、０℃
以下では凍結等の問題が発生する可能性があるため好ま
しくない。また、３０℃以上では原料の二硫化炭素の飛
散が発生し収率の低下が起こる。The reaction temperature is preferably in the range of 0 to 30°C, and 0°C
The following is not preferable because problems such as freezing may occur. Moreover, at temperatures above 30° C., carbon disulfide, which is a raw material, scatters and the yield decreases.
酸性水溶液としては、硫酸、塩酸水溶液であればどちら
でも良く、また、混合して用いても同等支障はない。濃
度としては、硫酸を使用した場合は２０ｗｔ％以上の濃
度が必要であり、塩酸を使用した場合は１０ｗｔ％以上
必要である。混合して使用する場合においては混合濃度
が２５ｗｔ％以上であれば良い。As the acidic aqueous solution, either sulfuric acid or hydrochloric acid aqueous solution may be used, and there is no problem even if they are used as a mixture. As for the concentration, when sulfuric acid is used, the concentration is required to be 20 wt% or more, and when hydrochloric acid is used, the concentration is required to be 10 wt% or more. When used as a mixture, it is sufficient that the concentration of the mixture is 25 wt% or more.
酸性水溶液と二硫化炭素の重量比は１００：３〜１００
： ２５の範囲である。１００：３以下では除熱効率
は良いが生産効率が悪く、１００：２５以上では除熱効
率が悪いために本発明の適用が困難となる。The weight ratio of acidic aqueous solution and carbon disulfide is 100:3 to 100
: The range is 25. If it is less than 100:3, the heat removal efficiency is good but the production efficiency is poor, and if it is more than 100:25, the heat removal efficiency is poor, making it difficult to apply the present invention.
塩素供給量としては、二硫化炭素に対して、４゜５〜５
．５倍モル量の範囲である。４．５倍モル瓜以下ではパ
ークロロメチルメルカプタン収率の低下、二硫化炭素添
加率の低下が起こ、り好ましくない。また、５゜５倍モ
ル量以上では、生成したパークロロメチルメルカプタン
の分解が促進され、パークロロメチルメルカプタン収率
、選択率の低下が起こり好ましくない。The amount of chlorine supplied is 4°5 to 5% relative to carbon disulfide.
．． The range is 5 times the molar amount. If it is less than 4.5 times the molar amount, the yield of perchloromethyl mercaptan will decrease and the carbon disulfide addition rate will decrease, which is not preferable. On the other hand, if the molar amount is 5.5 times or more, the decomposition of the produced perchloromethyl mercaptan will be accelerated, resulting in a decrease in perchloromethyl mercaptan yield and selectivity, which is undesirable.
塩素供給速度としては、二硫化炭素に対して、１．０ｋ
ｇ／Ｈ−ｋｇ以上であれば良いが、５．０ｋｇ／Ｈ−ｋ
ｇ以上では、大規模の除熱装置が必要となり、工業的で
はなく、また、１．０ｋｇ／Ｈ−ｋｇ以下では収率の低
下が発生し好ましくない。The chlorine supply rate is 1.0k for carbon disulfide.
g/H-kg or more is fine, but 5.0kg/H-k
If the amount is more than 1.0 kg/H-kg, a large-scale heat removal device is required, which is not suitable for industrial use, and if it is less than 1.0 kg/H-kg, the yield will decrease, which is not preferable.
〈発明の効果〉
本発明によると、工業的規模でのパークロロメチルメル
カプタンの高収率製造が可能となった。<Effects of the Invention> According to the present invention, perchloromethyl mercaptan can be produced in high yield on an industrial scale.
〈実施例〉
以下、実施例により本発明を具体的に説明するが本発明
はこれら実施例のみに限定されるものではない。<Examples> The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
撹拌機、外部循環冷却装置を備えた、１０（１のグラス
ライニング反応装置に二硫化炭素７．４３ｋｇ、水３０
ｋｇ、塩酸３．２ｋｇを仕込み、次いで撹拌、外部循環
冷却しながら塩素を二硫化炭素に対して、１．０ｋｇ／
Ｈ−ｋｇで４．９時間、３６゜２ｋｇ（ｔ％給した。反
応温度は９〜１２℃で行い、外部循環冷却装置の冷却媒
体温度は４℃であった。Example 1 7.43 kg of carbon disulfide, 30 kg of water in a 10 (1) glass-lined reactor equipped with a stirrer and an external circulation cooling device.
3.2 kg of hydrochloric acid, and then stirred and cooled by external circulation while adding chlorine to carbon disulfide at a rate of 1.0 kg/
36°2 kg (t%) was fed for 4.9 hours at H-kg. The reaction temperature was 9 to 12°C, and the cooling medium temperature of the external circulation cooling device was 4°C.
外部循環冷却装置の除熱能力は温度差５℃の場合８００
ｋｃａｌ／Ｈ・℃の能力の装置を用いた。The heat removal capacity of the external circulation cooling system is 800 when the temperature difference is 5°C.
An apparatus with a capacity of kcal/H·°C was used.
また、反応器ジャケットの除熱能力は温度差５℃の場合
、７０ｋｃａｌ／Ｈ・℃の能力であった。Further, the heat removal capacity of the reactor jacket was 70 kcal/H·°C when the temperature difference was 5°C.
反応終了後直ちに分液しガスクロマトグラフィーにより
パークロロメチルメルカプタンの分析を行った。結果を
表１に示した。Immediately after the reaction was completed, the liquid was separated and perchloromethyl mercaptan was analyzed by gas chromatography. The results are shown in Table 1.
実施例２〜５
実施例１と同じ装置で、表１に示した条件下、反応を行
った。結果を表１に示した。Examples 2 to 5 Reactions were carried out using the same apparatus as in Example 1 under the conditions shown in Table 1. The results are shown in Table 1.
比較例１〜３
実施例１で使用した１００ｇの反応器で表２に示した条
件で、外部循環冷却を行わずに反応器ジャケットのみに
よる冷却で、温度が３０℃以上にならないように反応を
行った。結果を表２に示した。Comparative Examples 1 to 3 The reaction was carried out in the 100 g reactor used in Example 1 under the conditions shown in Table 2, with cooling only by the reactor jacket without external circulation cooling, so that the temperature did not exceed 30 °C. went. The results are shown in Table 2.
Claims (1)
ロロメチルメルカプタンを製造するにあたり、外部熱交
換器を備えた反応装置を用い、二硫化炭素の酸性水溶液
を循環冷却しながら、二硫化炭素に対して塩素を１．０
ｋｇ／Ｈ・ｋｇ以上で供給することを特徴とするパーク
ロロメチルメルカプタンの製造法。In producing perchloromethyl mercaptan by chlorinating carbon disulfide with chlorine in an acidic aqueous solution, a reaction apparatus equipped with an external heat exchanger is used to circulate and cool the acidic aqueous solution of carbon disulfide. and chlorine to 1.0
A method for producing perchloromethyl mercaptan, characterized in that it is supplied in a quantity of kg/H·kg or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8926988A JP2504113B2 (en) | 1988-04-13 | 1988-04-13 | Process for producing perchloromethyl mercaptan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8926988A JP2504113B2 (en) | 1988-04-13 | 1988-04-13 | Process for producing perchloromethyl mercaptan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01261360A true JPH01261360A (en) | 1989-10-18 |
| JP2504113B2 JP2504113B2 (en) | 1996-06-05 |
Family
ID=13966033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8926988A Expired - Fee Related JP2504113B2 (en) | 1988-04-13 | 1988-04-13 | Process for producing perchloromethyl mercaptan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2504113B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233718A (en) * | 2020-03-19 | 2020-06-05 | 宁夏格瑞精细化工有限公司 | Method for continuously synthesizing perchloromethylmercaptan |
-
1988
- 1988-04-13 JP JP8926988A patent/JP2504113B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233718A (en) * | 2020-03-19 | 2020-06-05 | 宁夏格瑞精细化工有限公司 | Method for continuously synthesizing perchloromethylmercaptan |
| CN111233718B (en) * | 2020-03-19 | 2022-03-11 | 宁夏格瑞精细化工有限公司 | Method for continuously synthesizing perchloromethylmercaptan |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2504113B2 (en) | 1996-06-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |