JPS61200933A - Production of alkyl chloride - Google Patents
Production of alkyl chlorideInfo
- Publication number
- JPS61200933A JPS61200933A JP60040023A JP4002385A JPS61200933A JP S61200933 A JPS61200933 A JP S61200933A JP 60040023 A JP60040023 A JP 60040023A JP 4002385 A JP4002385 A JP 4002385A JP S61200933 A JPS61200933 A JP S61200933A
- Authority
- JP
- Japan
- Prior art keywords
- chloride
- alcohol
- zinc chloride
- alkyl
- hydrochloric acid
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、塩化亜鉛を再生することなくアルキルアルコ
ールと塩化水素とから、連続的に塩化アルキルを製造す
る方法である。すなわち、本発明は塩化アルキルを工業
的に有利に製造しうる方法である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is a method for continuously producing alkyl chloride from alkyl alcohol and hydrogen chloride without regenerating zinc chloride. That is, the present invention is an industrially advantageous method for producing alkyl chloride.
従来、アルキルアルコールよシ塩化アルキルを製造する
主な方法は、（１）塩化亜鉛を含むアルコールと塩酸と
の混合液を常圧で加熱する。または、（２）アルコール
と塩化チオニルとを・反応も；せ／ることによるもので
ある。Conventionally, the main methods for producing alkyl alcohols and alkyl chlorides are (1) heating a mixture of alcohol and hydrochloric acid containing zinc chloride at normal pressure; Alternatively, (2) the alcohol and thionyl chloride are reacted.
しかし、（１）の方法では塩化亜鉛をアルコールに対し
て当モル以上使用し表ければならず、さらに１度使用し
た塩化亜鉛を再使用する時には２５０℃以上に強熱しな
ければならない。従って、工業的に・・この・方法を用
いるには、塩化亜鉛を多量用いるので操作が煩雑となり
、しかも、塩化亜鉛の再生を高温で実施するので装置の
材質上困難がある。また、これを再使用せずに排水に流
すには塩化亜鉛の毒性が高いため、問題がある。また、
（２）の方法では塩化チオニルが高価であるばかりでな
く、副生物として亜硫酸ガスが生じ、この処理が必要で
ある。However, in method (1), zinc chloride must be used in an amount equivalent to or more than the mole of alcohol, and furthermore, when zinc chloride that has been used once is to be reused, it must be ignited to 250° C. or higher. Therefore, if this method is used industrially, the operation is complicated because a large amount of zinc chloride is used, and furthermore, the regeneration of zinc chloride is carried out at high temperature, which is difficult due to the material of the equipment. Additionally, zinc chloride is highly toxic, which poses a problem if it is flushed down the drain without being reused. Also,
In method (2), not only is thionyl chloride expensive, but also sulfur dioxide gas is produced as a by-product, which requires treatment.
従って、この方法では、工業的に高価になるばかシでな
く操作が煩雑となシ好ましくない。Therefore, this method is not desirable because it is industrially expensive and the operation is complicated.
そこで、本発明者らは鋭意検討を重ね、その結果、本発
明を完成した。Therefore, the inventors of the present invention conducted extensive studies, and as a result, completed the present invention.
即ち、本発明は液相触媒反応で、アルキルアルコールと
塩化水素とから塩化アルキルを合成するに°際し、反応
温度に維持した塩化亜鉛を含む塩酸溶液に、アルキルア
ルコールと塩化水素（無水）、トを連続的に導入、接触
させ、生成する塩化アルキルを直ちに気相で系外へ溜め
させることを特徴とする塩化アルキルの製造方法である
。That is, in the present invention, when synthesizing alkyl chloride from alkyl alcohol and hydrogen chloride using a liquid phase catalytic reaction, alkyl alcohol, hydrogen chloride (anhydrous), This is a method for producing alkyl chloride, which is characterized in that the alkyl chloride is continuously introduced and brought into contact with each other, and the produced alkyl chloride is immediately stored outside the system in a gas phase.
本発明において、原料として用いられるアルキルアルコ
ールは炭素数３乃至５の直鎖状又は分枝状のものである
。具体的にはｎ−プロピルアルコール、１ｓｏ−７’ロ
ピルアルコール、ｎ−ブチルアルコール、ｓｅｅ −７
”ｆルアルコール等カ挙ケラレる。In the present invention, the alkyl alcohol used as a raw material is a linear or branched alkyl alcohol having 3 to 5 carbon atoms. Specifically, n-propyl alcohol, 1so-7'lopyl alcohol, n-butyl alcohol, see-7
``There is a lot of vignetting, including alcohol.
アルキルアルコールの導入方法は連続式が採用される。A continuous method is adopted as the method of introducing the alkyl alcohol.
その供給速度は反応温度、装置能力等忙従う反応速度及
び溜め速度（生成物）によって塩化アルキルが系内に滞
留しない様に、実験上から適宜、決めるべきである。通
常、溜め 塩化アルキルの当モルが選らばれる。The feed rate should be appropriately determined experimentally, depending on the reaction temperature, equipment capacity, etc., and the accumulation rate (product) so that the alkyl chloride does not remain in the system. Usually, the equimolar amount of the reservoir alkyl chloride is chosen.
他の原料、塩化水素（無水）の供給量はアルキルアルコ
ールの１〜２モル倍、好マシくハ１．１〜１．５モル倍
の範囲である。The amount of other raw materials, hydrogen chloride (anhydrous), to be supplied is in the range of 1 to 2 moles, preferably 1.1 to 1.5 moles, of the alkyl alcohol.
触媒として用いられる塩化亜鉛は塩酸溶液（完溶）の形
態で使用される。塩化亜鉛を含む塩酸溶液は通常、塩化
亜鉛と塩酸（飽和）水溶液とを当モルずつ混合せしめて
、調製される。Zinc chloride used as a catalyst is used in the form of a hydrochloric acid solution (completely dissolved). A hydrochloric acid solution containing zinc chloride is usually prepared by mixing equimolar amounts of zinc chloride and a (saturated) aqueous solution of hydrochloric acid.
このとき、該組成は大略、塩化水素１４．８１、水３０
．０％、塩化亜鉛５５．２１である。さらに、母液であ
る塩化亜鉛を含む塩酸溶液には、定常運転を速かに実現
させるべく、前以って、塩化亜鉛に対して、原料、アル
キルアルコールの当モルが投入される。At this time, the composition is approximately 14.81% hydrogen chloride and 30% water.
．． 0%, zinc chloride 55.21. Further, in order to quickly realize steady operation, the same mole of the raw material, alkyl alcohol, relative to zinc chloride is added to the mother liquor, a hydrochloric acid solution containing zinc chloride, in advance.
予め、仕込まれる触媒含有母液の量は通常、原料アルキ
ルアルコールの供給速度（１時間娼り）に対し、その塩
化亜鉛の当モル以上が選ばれる。The amount of the catalyst-containing mother liquor charged in advance is usually selected to be equal to or more than the equivalent mole of zinc chloride relative to the feed rate (1 hour fermentation) of the raw material alkyl alcohol.
又、塩化亜鉛の触媒寿命はアルキルアルコールの総仕込
量で、塩化亜鉛に対し、１２モル倍以上使用可能であシ
、反応最終の母液はそのま＼、次回の反応へ再使用され
る。Furthermore, the catalyst life of zinc chloride is that the total amount of alkyl alcohol charged can be used in an amount of 12 moles or more compared to zinc chloride, and the mother liquor at the end of the reaction can be reused as is for the next reaction.
反応温度は９０〜１４０℃の範囲から選ばれるが、通常
、塩化アルキルの蒸溜温度に応じて、母液の沸騰温度に
設定するのが適当である。The reaction temperature is selected from the range of 90 to 140°C, but it is usually appropriate to set it to the boiling temperature of the mother liquor depending on the distillation temperature of the alkyl chloride.
反応装置としては、例えば、工業上、一般に広く使用さ
れる槽式が採用でき、これに簡単な分溜能力を持つ分離
塔を付帯することで足りる。後者はは原料、アルキルア
ルコールと生成物塩化アルキルを両者の沸点差で分離で
きる機能を有するもの、例えば、ｆＩｉ、ｉ型還流器が
代用できる。このとき、該冷却器の頂部温度は通常、塩
化アルキルの沸騰±２℃で管理することで、系外への原
料ロスを最小限にとどめうる。As the reaction apparatus, for example, a tank type which is generally widely used in industry can be adopted, and it is sufficient to attach a separation column having a simple fractionation capacity to this. For the latter, a device capable of separating the raw material, alkyl alcohol, and the product, alkyl chloride, based on the difference in their boiling points, such as an fIi or type I reflux device, can be used instead. At this time, the temperature at the top of the cooler is usually controlled at ±2° C. of the boiling point of the alkyl chloride, thereby minimizing the loss of raw materials to the outside of the system.
得られた（反応）生成物は公知の処理手段、例えば、水
洗、アルカリ中和さらには、蒸溜等によって、分離され
容易に精製される。The obtained (reaction) product is easily separated and purified by known treatment means, such as water washing, alkali neutralization, and distillation.
本発明の方法によれば、収率よくしかも従来の方法のよ
うに塩化亜鉛を再生し、又、単純にこの塩酸溶液を排水
に流すことなく、また、高価である塩化チオニルを用い
ることなく簡単に塩化アルキルを連続的に製造すること
ができる。According to the method of the present invention, zinc chloride can be regenerated in a high yield and in a simple manner as in the conventional method, without simply discharging this hydrochloric acid solution into wastewater, and without using expensive thionyl chloride. Alkyl chloride can be produced continuously.
加えて、連続反応であるため、反応缶はバッチ反応のよ
うに大きなものを用いる必要がない。In addition, since it is a continuous reaction, there is no need to use a large reactor as in a batch reaction.
製品、塩化アルキルはカチオン系の界面活性剤の原料又
はカルボン酸、リン酸のエステル化剤等に巾広く用いら
れるものである。The product, alkyl chloride, is widely used as a raw material for cationic surfactants or as an esterification agent for carboxylic acids and phosphoric acids.
以下に、実施例を挙げて、本発明をさらに詳細に説明す
る。EXAMPLES The present invention will be explained in more detail below with reference to Examples.
予め、恒温型還流（冷却）器を付し次５゛・ｏｒｒｏ−
のフラスコに、塩化亜鉛１３６．４ｆ（１，０モル）及
び３３憾塩酸水溶液１１０．６ｔ （１，０モル）さら
に、ｎ−プロピルアルコール６０．１Ｆ（１，０モル）
を投入した。このとき、冷却器の温度は４７±２℃に保
つ。Attach a constant temperature type reflux (cooler) device in advance, and then
In a flask, add 136.4f (1.0 mol) of zinc chloride and 110.6 t (1.0 mol) of aqueous solution of 33% hydrochloric acid, and 60.1F (1.0 mol) of n-propyl alcohol.
was introduced. At this time, the temperature of the cooler is maintained at 47±2°C.
フラスコを１００±３℃に昇温し、反応（缶）液を沸騰
させて連続反応を開始した。先ず、該冷却器の頂部から
塩化プロピルを含む生成物を溜めさせると同時に、両原
料、ｈ−プロピルアルコールを約５時間に６０．１１（
１，０モル）の速度で、且つ（無水）塩化水素を６ ｔ
／ Ｈｒ（０，２７モル／Ｈｒ）で供給した。The temperature of the flask was raised to 100±3° C., and the reaction (can) liquid was boiled to start a continuous reaction. First, the product containing propyl chloride was collected from the top of the cooler, and at the same time, both raw materials, h-propyl alcohol, were heated at 60.11 (60.11%) in about 5 hours.
1,0 mol) and 6 t (anhydrous) hydrogen chloride
/Hr (0.27 mol/Hr).
そして、総仕込ｎ−プロピルアルコールが７２１２ｙ（
１２，０モル）となった時点で反応を停止した。The total n-propyl alcohol used was 7212y (
12.0 mol), the reaction was stopped.
（）（ｃｊ／ｎ −ＰｒｏＨ＝ １．４７ ）運転時間
は６２ Ｈｒであった。反応は終始、円滑に進行し、殊
に、最終のｎ−ＰｒｏＨ／Ｚｒｃ ｌｔ＝ １２ ／
１となったが、触媒、塩化亜鉛の活性低下は見られず、
引続いて長期運転の継続は可能であった。()(cj/n-ProH=1.47) The operating time was 62 Hr. The reaction proceeded smoothly throughout, especially when the final n-ProH/Zrc lt=12/
1, but no decrease in the activity of the catalyst or zinc chloride was observed.
Continued long-term operation was possible.
結果、総溜出（反応）生成物は８２６．７９（組成：
ｉ ５ｏ−Ｐｒｅ １４．０ ％、ｎ−Ｐｒｅ １９３
．０％、ｎ−ＰｒｏＨｌ、０％、Ｈ，０２，０％ ）で
あり、ｎ−プロピルアルコールに対する車通収率は８１
．６１であった。As a result, the total distillation (reaction) product was 826.79 (composition:
i5o-Pre 14.0%, n-Pre 193
．． 0%, n-ProHl, 0%, H, 02,0%), and the vehicle yield rate for n-propyl alcohol is 81
．． It was 61.
又、最終の反応（缶）液組成はＨｃｌ ｅｔｃ １１．
４係、ｎ−ＰｒｏＨｌ ８．２％、Ｈｔ ｏ ４５．４
４、Ｚｒｃｌｔ ２５．０チであった。Also, the final reaction (can) liquid composition is Hcl etc. 11.
Section 4, n-ProHl 8.2%, Hto 45.4
4. Zrclt was 25.0ch.
次いで、得られた（反応）生成物は水洗、アルカリ中和
した後、１０段のオルダーショー装置を用いて、還流比
５〜１０で、（回分式）蒸溜精製した。Next, the obtained (reaction) product was washed with water and neutralized with alkali, and then purified by distillation (batchwise) using a 10-stage Oldershaw apparatus at a reflux ratio of 5 to 10.
結果、製品溜升（温度、４６．５〜４８．０℃）は６０
８、 Ｏｆ （組成： １ｓｏ−Ｐｒｃｌ １．８１、
ｎ−Ｐｒｃ １９８．２係）であシ、精製得率は７３．
５俤であった。As a result, the product volume (temperature, 46.5-48.0℃) was 60
8, Of (composition: 1so-Prcl 1.81,
n-Prc 198.2 section), the purification yield was 73.
It was 5 yen.
備考：）（ｃｌ 塩化水素
ｎ−ＰｒｏＨｎ−プロピルアルコール
１ｓｏ−ｐｒｃｌ 塩化１ｓｏ−プロピルｎ−Ｐｒ
ｃｌ 塩化ｎ−プロピルＨ，Ｏ水
Ｚｎｃｌｔ 塩化亜鉛Notes: ) (cl Hydrogen chloride n-ProHn-propyl alcohol 1so-prcl 1so-propyl chloride n-Pr
cl n-propyl chloride H,O water Znclt zinc chloride
Claims (1)
塩化アルキルを合成するに際し、反応温度に維持した塩
化亜鉛を含む塩酸溶液に、アルキルアルコールと塩化水
素（無水）とを連続的に導入、接触させ、生成する塩化
アルキルを直ちに気相で系外へ溜出させることを特徴と
する塩化アルキルの製造方法When synthesizing alkyl chloride from alkyl alcohol and hydrogen chloride in a liquid-phase catalytic reaction, alkyl alcohol and hydrogen chloride (anhydrous) are continuously introduced and brought into contact with a hydrochloric acid solution containing zinc chloride maintained at the reaction temperature. , a method for producing alkyl chloride, characterized in that the alkyl chloride produced is immediately distilled out of the system in a gas phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60040023A JPS61200933A (en) | 1985-02-28 | 1985-02-28 | Production of alkyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60040023A JPS61200933A (en) | 1985-02-28 | 1985-02-28 | Production of alkyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61200933A true JPS61200933A (en) | 1986-09-05 |
| JPH0557973B2 JPH0557973B2 (en) | 1993-08-25 |
Family
ID=12569303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60040023A Granted JPS61200933A (en) | 1985-02-28 | 1985-02-28 | Production of alkyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61200933A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265399A (en) * | 2013-05-20 | 2013-08-28 | 张家港市振方化工有限公司 | Catalyst-based chlorinated neopentane preparation technology |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57156423A (en) * | 1981-02-26 | 1982-09-27 | Hoechst Ag | Manufacture of gas containing methylchloride |
-
1985
- 1985-02-28 JP JP60040023A patent/JPS61200933A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57156423A (en) * | 1981-02-26 | 1982-09-27 | Hoechst Ag | Manufacture of gas containing methylchloride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265399A (en) * | 2013-05-20 | 2013-08-28 | 张家港市振方化工有限公司 | Catalyst-based chlorinated neopentane preparation technology |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0557973B2 (en) | 1993-08-25 |
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