JPH089558B2 - Method for producing allyl chloride - Google Patents
Method for producing allyl chlorideInfo
- Publication number
- JPH089558B2 JPH089558B2 JP2413781A JP41378190A JPH089558B2 JP H089558 B2 JPH089558 B2 JP H089558B2 JP 2413781 A JP2413781 A JP 2413781A JP 41378190 A JP41378190 A JP 41378190A JP H089558 B2 JPH089558 B2 JP H089558B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- allyl chloride
- dichloropropane
- activated carbon
- 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.)
- Expired - Fee Related
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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アリルクロライドの製
造方法に関する。さらに詳しくは、１，２−ジクロルプ
ロパンから、接触分解による脱塩化水素反応により、ア
リルクロライドを製造する方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing allyl chloride. More specifically, it relates to a method for producing allyl chloride from 1,2-dichloropropane by a dehydrochlorination reaction by catalytic decomposition.
【０００２】[0002]
【従来の技術】１，２−ジクロルプロパンは、プロピレ
ンをクロルヒドリン化し、プロピレンオキサイド中間体
を製造する際に副生する。また、プロピレンの高温塩素
化によりアリルクロライドを製造する際にも副生する。
この副生物である１，２−ジクロルプロパンの有効利用
として、脱塩化水素反応によりアリルクロライドを製造
することが知られている。該アリルクロライドは、エピ
クロルヒドリン、アリルアルコール、ジアリルフタレー
トなどの工業薬品、樹脂の原料として有用である。2. Description of the Related Art 1,2-Dichloropropane is a by-product when propylene is converted into chlorohydrin to produce a propylene oxide intermediate. It is also produced as a by-product in the production of allyl chloride by high temperature chlorination of propylene.
As an effective use of this by-product, 1,2-dichloropropane, it is known to produce allyl chloride by a dehydrochlorination reaction. The allyl chloride is useful as a raw material for resins such as epichlorohydrin, allyl alcohol, diallyl phthalate and other industrial chemicals.
【０００３】従来、１，２−ジクロルプロパンの脱塩化
水素反応は熱分解および接触分解による方法が知られて
いる。即ち、熱分解反応は、５００〜７００℃の高温下
に短時間で脱塩化水素反応が行なわれる。また、接触分
解反応は、塩化カルシウム、シリカアルミナ、活性炭な
どの触媒を用いて、２００〜５００℃の低温下に脱塩化
水素反応が行なわれる。Conventionally, the dehydrochlorination reaction of 1,2-dichloropropane is known to be a method of thermal decomposition or catalytic decomposition. That is, in the thermal decomposition reaction, a dehydrochlorination reaction is carried out in a short time at a high temperature of 500 to 700 ° C. In the catalytic cracking reaction, a dehydrochlorination reaction is carried out at a low temperature of 200 to 500 ° C. using a catalyst such as calcium chloride, silica alumina, activated carbon or the like.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、熱分解
反応では炭素質が生成するため、収率の低下および反応
管の閉塞などの問題があり、長期間にわたって安定的に
製造することが困難であった。また、接触分解反応でも
上記触媒の活性が時間の経過と伴して急速に劣化してい
く問題があり、長期間にわたって安定的に製造すること
ができなかった。However, since carbonaceous matter is produced in the thermal decomposition reaction, there are problems such as a decrease in yield and clogging of the reaction tube, and it is difficult to stably manufacture for a long period of time. It was Further, even in the catalytic cracking reaction, there is a problem that the activity of the above-mentioned catalyst deteriorates rapidly with the passage of time, and it has not been possible to stably produce the catalyst over a long period of time.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意研究を重ねてきた。その結果、上記
接触分解による脱塩化水素反応において、活性炭を触媒
として用い、水蒸気の存在下で、１，２−ジクロルプロ
パンを脱塩化水素することにより、長期間、安定してア
リルクロライドを製造することができることを見い出し
本発明を完成するに至った。[Means for Solving the Problems] The present inventors have conducted extensive studies to solve the above problems. As a result, in the dehydrochlorination reaction by catalytic cracking, 1,2-dichloropropane is dehydrochlorinated in the presence of water vapor using activated carbon as a catalyst to stably produce allyl chloride for a long period of time. As a result, they have found that they can be accomplished and completed the present invention.
【０００６】即ち、本発明は、活性炭と水蒸気の共存下
において、１，２−ジクロルプロパンを加熱することを
特徴とするアリルクロライドの製造方法である。That is, the present invention is a method for producing allyl chloride, which comprises heating 1,2-dichloropropane in the presence of activated carbon and steam.
【０００７】本発明において用いられる活性炭は、炭素
質原料、賦活方法、細孔径分布、細孔容積、比表面積等
には特に限定されず、公知のものを制限なく使用するこ
とができる。アリルクロライドの空時収量を考えると、
細孔容積が０．３ｃｍ3 ／ｇ以上で比表面積が３００ｍ
2 ／ｇ以上の活性炭が好ましい。また、その形状につい
ても特に限定されるものではないが、取扱いの容易さな
どから、通常は破砕品や球状、円筒状などの成型品が好
適である。The activated carbon used in the present invention is not particularly limited in carbonaceous raw material, activation method, pore size distribution, pore volume, specific surface area and the like, and known ones can be used without limitation. Considering the space-time yield of allyl chloride,
Pore volume of 0.3 cm 3 / g or more and specific surface area of 300 m
Activated carbon of 2 / g or more is preferable. Further, the shape thereof is not particularly limited, but a crushed product or a molded product such as a spherical shape or a cylindrical shape is usually preferable because of easy handling.
【０００８】本発明において反応の形式は、特に制限さ
れるものではなく回分式又は連続式のいずれでも良い
が、工業的には連続式で行うのが好ましい。活性炭と共
存させる水蒸気の量は、１，２−ジクロルプロパンの転
化率すなわち、例えば本発明を連続式で行う場合におい
ては空間速度ＳＶ（１，２−ジクロルプロパン供給量／
活性炭充填量）や反応温度により変化する。通常の連続
式の反応条件下（ＳＶ＝１００〜５０００００ｈｒ-1、
１００〜５００℃）では、供給する１，２−ジクロルプ
ロパンに対して１０ｍｏｌ％以上であれば良い。しか
し、過剰の水蒸気を使用するのは、エネルギー的に不利
であるので、通常は、１０〜２００ｍｏｌ％の範囲内で
行なうのが好ましい。本発明の反応温度は、好ましくは
１００〜５００℃の範囲であり、さらに好ましくは２０
０〜５００℃の範囲である。また、圧力は好ましくは
０．５〜１０気圧の範囲であり、さらに好ましくは０．
５〜５気圧の範囲である。尚、活性炭の使用方法は固定
床式あるいは流動床式のいずれでも良い。In the present invention, the reaction system is not particularly limited and may be either a batch system or a continuous system, but it is industrially preferably carried out in a continuous system. The amount of water vapor to be coexisted with the activated carbon is the conversion rate of 1,2-dichloropropane, that is, space velocity SV (1,2-dichloropropane supply amount /
It varies depending on the activated carbon filling amount) and the reaction temperature. Under normal continuous reaction conditions (SV = 100 to 500,000 hr −1 ,
At 100 to 500 ° C.), it may be 10 mol% or more with respect to 1,2-dichloropropane supplied. However, it is energetically unfavorable to use an excessive amount of steam, so that it is usually preferable to carry out in the range of 10 to 200 mol%. The reaction temperature of the present invention is preferably in the range of 100 to 500 ° C, more preferably 20.
It is in the range of 0 to 500 ° C. The pressure is preferably in the range of 0.5 to 10 atm, more preferably 0.
It is in the range of 5 to 5 atmospheres. The activated carbon may be used in either a fixed bed type or a fluidized bed type.
【０００９】[0009]
【効果】本発明の方法によれば、水蒸気を存在させない
でアリルクロライドを製造した場合の様に、１，２−ジ
クロルプロパンの転化率が時間の経過と伴に急速に低下
することがなく、反応初期の転化率が長期にわたり維持
される。このことにより、本発明において、前記活性炭
と供に存在させた水蒸気は、該活性炭の触媒活性の劣化
を抑制しているものと考えられる。[Effect] According to the method of the present invention, the conversion of 1,2-dichloropropane does not decrease rapidly with the passage of time as in the case of producing allyl chloride in the absence of water vapor. The conversion rate at the initial stage of the reaction is maintained for a long time. From this, in the present invention, it is considered that the steam present together with the activated carbon suppresses the deterioration of the catalytic activity of the activated carbon.
【００１０】以上の説明より理解されるように、本発明
によれば、１，２−ジクロルプロパンよりアリルクロラ
イドを１００〜５００℃の低温で、かつ初期活性を長期
間維持した状態で製造できる。また、前記副生物である
１，２−ジクロルプロパンを有効に利用することが可能
である。As can be understood from the above description, according to the present invention, allyl chloride can be produced from 1,2-dichloropropane at a low temperature of 100 to 500 ° C. and in the state where the initial activity is maintained for a long period of time. . Further, it is possible to effectively use the by-product 1,2-dichloropropane.
【００１１】[0011]
【実施例】以下、本発明を更に具体的に説明するため実
施例を挙げるが、本発明はこれらの実施例に限定される
ものではない。EXAMPLES Examples will be given below to describe the present invention more specifically, but the present invention is not limited to these examples.
【００１２】実施例１ 細孔容積が０．８ｃｍ3 ／ｇで比表面積が９８０ｍ2 ／
ｇの粒状活性炭（植物系原料）５ｇをガラス製反応管
（φ＝２０ｍｍ）に入れ、窒素ガスを流通させながら、
５００℃で５時間加熱した。その後、反応温度まで降温
し、反応に供した。反応は、固定床常圧流通装置を使用
し、１，２−ジクロルプロパンはマイクロ定量ポンプに
より０．５ｍｌ／分の速度で気化器に送られ、ガス化し
て反応管内へ導入し、水蒸気はマイクロ定量ポンプを使
って、水を気化器に送りガス化させた後、反応管内へ導
入した。水蒸気の導入量は、１，２−ジクロルプロパン
に対して２０〜１００ｍｏｌ％の範囲で、また、反応温
度は、２００〜４５０℃の範囲で変えた。反応は、４８
時間連続して行ない、サンプリングは反応開始後の０〜
１時間、５〜６時間および４７〜４８時間の各１時間の
計３回行なった。サンプリングは、ドライアイス−メタ
ノールで冷却して補集した後、分液ロートで油層を分離
し行なった。生成物の分析は、ＰＥＧ・２０Ｍキャピラ
リーカラムを具ええＦＩＤ型ガスクロマトグラフにより
行なった。１，２−ジクロルプロパンの転化率およびア
リルクロライドの選択率は次式により算出した。 未反応ＰＤＣ重量 転化率（％）＝（１−───────────）×１００ ＰＤＣ供給重量 （ただし、ＰＤＣは１，２−ジクロルプロパンを表わす。） アリルクロライド重量 選択率（％）＝────────────── ×１００ 生 成 物 重 量 結果は、表１にまとめて示した。Example 1 Pore volume 0.8 cm 3 / g and specific surface area 980 m 2 /
5 g of granular activated carbon (plant-based raw material) was placed in a glass reaction tube (φ = 20 mm) and nitrogen gas was passed through the reaction tube,
Heated at 500 ° C. for 5 hours. Then, the temperature was lowered to the reaction temperature and the reaction was performed. For the reaction, a fixed bed atmospheric pressure distribution device was used, and 1,2-dichloropropane was sent to a vaporizer at a rate of 0.5 ml / min by a micro metering pump, gasified and introduced into a reaction tube, and steam was generated. Using a micro metering pump, water was sent to a vaporizer for gasification and then introduced into the reaction tube. The amount of steam introduced was changed in the range of 20 to 100 mol% with respect to 1,2-dichloropropane, and the reaction temperature was changed in the range of 200 to 450 ° C. The reaction is 48
It is carried out continuously for a time, and sampling is 0 to 0 after the start of the reaction.
One hour, 5 to 6 hours, and 47 to 48 hours, 1 hour each, a total of 3 times. Sampling was performed by cooling with dry ice-methanol to collect it, and then separating the oil layer with a separating funnel. The analysis of the product was carried out by a FID gas chromatograph equipped with a PEG-20M capillary column. The conversion of 1,2-dichloropropane and the selectivity of allyl chloride were calculated by the following formulas. Unreacted PDC weight Conversion rate (%) = (1 ------------)-100 PDC supply weight (however, PDC represents 1,2-dichloropropane) Allyl chloride weight selection Rate (%) = ────────────── × 100 Product weight The results are summarized in Table 1.
【００１３】[0013]
【表１】 [Table 1]
【００１４】比較例１ 実施例１における水蒸気の供給をしないで、反応を行な
った。反応操作は、実施例１と同様にして行なった。結
果は、表２に示した。Comparative Example 1 The reaction was carried out without supplying steam in Example 1. The reaction operation was performed in the same manner as in Example 1. The results are shown in Table 2.
【００１５】[0015]
【表２】 [Table 2]
【００１６】実施例２ 実施例１の活性炭（植物系）を、細孔容積が０．６ｃｍ
3 ／ｇで比表面積が８５０ｍ2 ／ｇの破砕活性炭（石炭
系原料）に変え、その他の操作は、実施例１と全く同様
にして反応を行なった。結果を表３に示した。Example 2 The activated carbon of Example 1 (plant type) was used, and the pore volume was 0.6 cm.
A crushed activated carbon (coal-based raw material) having a specific surface area of 3 / g and a specific surface area of 850 m 2 / g was used, and the reaction was performed in the same manner as in Example 1 except for the other operations. The results are shown in Table 3.
【００１７】[0017]
【表３】 [Table 3]
Claims (1)
２−ジクロルプロパンを加熱することを特徴とするアリ
ルクロライドの製造方法。1. In the coexistence of activated carbon and steam, 1,
A method for producing allyl chloride, which comprises heating 2-dichloropropane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2413781A JPH089558B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing allyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2413781A JPH089558B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing allyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04224530A JPH04224530A (en) | 1992-08-13 |
| JPH089558B2 true JPH089558B2 (en) | 1996-01-31 |
Family
ID=18522351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2413781A Expired - Fee Related JPH089558B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing allyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH089558B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299151B (en) * | 2018-02-09 | 2020-03-10 | 浙江大学 | Method for preparing 2-methylallyl chloride from 1, 2-dichlorotert-butyl alkane |
-
1990
- 1990-12-25 JP JP2413781A patent/JPH089558B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04224530A (en) | 1992-08-13 |
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