JPS58201801A - Removal of reaction heat of polymerization - Google Patents

Abstract

PURPOSE:To remove reaction heat from a high viscous solution uniformly without adhesion of a high polymer, by taking out partially a reaction solution having a viscosity of <= a specific value in a polymerizer to the outside, recycling it through a multi-tubular heat exchanger with a built-in static mixer to the polymerizer. CONSTITUTION:A monomer, a solvent and a catalyst are fed from the feed lines 1, 2, and 3 respectively to the polymerizer 4, and polymerization is carried out. A reaction solution having <=500 poise viscosity in the polymerizer 4 is at least partially taken out through the line 9 to the outside, fed through the branched line 7 to the multi-tubular heat exchanger 5 consisting of the pipe 11 with the built-in static mixer 12 by the circulating pump 6, subjected to heat exchange with the cooling water 8, cooled, and recycled through the line 10 to the polymerizer 4, so that the polymerization is carried out while the reaction heat in the polymerizer 4 is removed.

Description

【発明の詳細な説明】 本発明は、重合反応槽の除熱方法に関し、さらに詳しく
は重合反応槽内の高粘度反応液の反応熱を除去する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing heat from a polymerization reaction tank, and more particularly to a method for removing reaction heat from a high viscosity reaction liquid in a polymerization reaction tank.

一般に重合反応においては、反応熱を除去しなければな
らない。特に重合反応が高粘度液中で行なわれる場合に
は、溶液の熱容量が大きいので除熱方法が大きな問題と
なる。Generally, in polymerization reactions, reaction heat must be removed. Particularly when the polymerization reaction is carried out in a highly viscous liquid, the heat removal method becomes a big problem because the heat capacity of the solution is large.

従来、例えばポリブタジェン、ポリイソプレン等の溶液
重合においては、重合反応槽内に除熱用コイルが設置さ
れていて、冷媒としてアンモニアを用いて重合反応の除
熱が行なわれていた。しかしながら、この方法では、冷
却水を用いる場合よりもはるかに大きい電力を要し、経
済的な負担が大になるという欠点があり、また冷媒とし
てアンモニアを用いているため、被冷却液との温度差が
大きく、このため冷却が不均一になったり、またコイル
に重合物が付着固化し、伝熱効率が低下したり、または
清掃が困難になるという欠点があった。Conventionally, in solution polymerization of polybutadiene, polyisoprene, etc., a heat removal coil has been installed in the polymerization reaction tank, and ammonia has been used as a refrigerant to remove heat from the polymerization reaction. However, this method has the drawback that it requires much more power than when using cooling water, which imposes a heavy economic burden.Also, since ammonia is used as a refrigerant, the temperature of the liquid to be cooled is The difference is large, and as a result, there are disadvantages in that cooling becomes uneven, polymers adhere to and solidify on the coil, reducing heat transfer efficiency, and making cleaning difficult.

本発明の目的は、上記従来技術の欠点を解消し、高粘度
液であっても水冷却により効率よく除熱することができ
る重合反応槽の除熱方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for removing heat from a polymerization reaction tank, which eliminates the drawbacks of the prior art described above and can efficiently remove heat by water cooling even from a highly viscous liquid.

本発明の除熱方法は、重合反応槽内の反応液の粘度が５
００ボイズ以下である反応液の少くとも一部を外部に取
り出し、スタティックはキサ−を内蔵する多管式熱交換
器を通して前記反応槽に再循環させることを特徴とする
。In the heat removal method of the present invention, the viscosity of the reaction liquid in the polymerization reaction tank is 5.
The present invention is characterized in that at least a part of the reaction liquid having a 0.00 void or less is taken out to the outside and recirculated to the reaction tank through a multi-tubular heat exchanger having a built-in static heater.

本発明における重合とは、合成ゴムまたは合成樹脂の乳
化重合、溶液重合、懸濁重合、バルク重合等であり、好
ましくは溶液重合であり、例えば、スチレン−ブタジェ
ン乳化重合、スチレン−ブタジェン溶液重合、ポリブタ
ジェン溶液重合、ポリイソプレン溶液重合等があげられ
る。Polymerization in the present invention includes emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, etc. of synthetic rubber or synthetic resin, preferably solution polymerization, such as styrene-butadiene emulsion polymerization, styrene-butadiene solution polymerization, Examples include polybutadiene solution polymerization and polyisoprene solution polymerization.

本発明における重合反応槽内の反応液の粘度は５００ボ
イズ以下が適当である。粘度が５００ボイズをこえると
、反応液の循環が困難と九る。本発明の効果が充分発揮
できる反応液の好ましい粘度は１０〜２００ボイズであ
る。In the present invention, the viscosity of the reaction liquid in the polymerization reaction tank is suitably 500 voids or less. When the viscosity exceeds 500 voids, it is difficult to circulate the reaction solution. The preferred viscosity of the reaction liquid is 10 to 200 voids to fully exhibit the effects of the present invention.

本発明において使用される多管式熱交換器のチューブの
長さは好ましくは１〜１．５ｍであり、チューブ内を流
れる反応液の速度は好ましくは１ｃＩ！Ｌ／ｓ〜３０ｃ
ｙｎ／ｇ、さらに好ましくは３ｃＷＬ／、ｓ′〜２０園
／Ｓである。The tube length of the shell-and-tube heat exchanger used in the present invention is preferably 1 to 1.5 m, and the velocity of the reaction liquid flowing inside the tube is preferably 1 cI! L/s~30c
yn/g, more preferably 3 cWL/, s' to 20 WL/S.

本発明において、循環する反応液の一部の量は反応器に
ついてのエンタルピー収支から決定される。In the present invention, the amount of a portion of the circulating reaction liquid is determined from the enthalpy balance for the reactor.

以下、本発明を図面によりさらに詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to the drawings.

第１図は、本発明の一実施例を示す重合反応槽の除熱方
法の系統図である。図において、重合反応槽４には、単
量体溶剤および触媒の各供給ライン１．２および３が設
けられ、またその上部には反応溶液の抜出しライン９が
設けられている。反応溶液の一部は分岐ライン７を経て
循環ポンプ６により外部熱交換器５に供給され、ここで
冷却水８と熱交換され、冷却された後、ライン１０から
重合反応槽４にＯＩｉ環される。熱交換器５は多管式の
熱変換器であるが、第２図に示すように、管１１内にス
タチックミキサ１２が取付けられている。FIG. 1 is a system diagram of a method for removing heat from a polymerization reaction tank, showing one embodiment of the present invention. In the figure, a polymerization reaction tank 4 is provided with monomer solvent and catalyst supply lines 1.2 and 3, and a reaction solution withdrawal line 9 is provided above the supply lines 1.2 and 3, respectively. A part of the reaction solution is supplied via a branch line 7 to an external heat exchanger 5 by a circulation pump 6, where it is heat exchanged with cooling water 8, cooled, and then OIi-circulated from a line 10 to a polymerization reaction tank 4. Ru. The heat exchanger 5 is a multi-tubular heat converter, and as shown in FIG. 2, a static mixer 12 is installed inside the tube 11.

管内に重合反応液が流通し、管外を冷却水が流れる。ス
タチックミキサ１２は、よく知られるように、らせん形
の充填子１３が液の流通方向に方向を変えて順次設けら
れているもので、液が流通して充填子の先端に衝突し、
異なる方向に分割を繰返すことにより、液を半径方向に
効率よく攪拌するものである。熱交換器５に供給する反
応液の量は、スタチックミキサの圧力操作によりポンプ
６の消費電力が過大になり、水冷による利益が損なわれ
ないように決定すべきである。A polymerization reaction liquid flows inside the tube, and cooling water flows outside the tube. As is well known, the static mixer 12 is one in which spiral-shaped fillers 13 are sequentially provided in different directions in the flow direction of the liquid, and as the liquid flows, it collides with the tips of the fillers.
By repeating division in different directions, the liquid is efficiently stirred in the radial direction. The amount of reaction liquid supplied to the heat exchanger 5 should be determined so that the power consumption of the pump 6 becomes excessive due to the pressure operation of the static mixer and the benefits of water cooling are not impaired.

ポリブタジェンの溶液重合に本発明を適した実施例によ
れば、第１図の装置系統において伝熱面積５０ｎ／の熱
交換器５を２基直列に用いた場合、熱交換器５人口の溶
液（粘度１００ボイズ）の流速１０ＣｒＩＬ／、１′、
温度６０℃に対して熱交換器５出口の溶液の流速は１０
　ｒｘ／　ｚ　、温度は４０℃であった、 上記のようにスタテックミキサを内蔵する熱交換器は、
冷却媒体との温度差が小さくても、攪拌効果が大きいの
で、伝熱速度が高く、熱容量の大きい高粘度液であって
も水冷却により充分除熱することができる。本実施例と
従来のアンモニアを使用した除熱方法とをエネルギー的
に比較すると、本実施例は従来法よりも９０％のエネル
ギー消費数の減少がみられた。According to an embodiment in which the present invention is suitable for solution polymerization of polybutadiene, when two heat exchangers 5 having a heat transfer area of 50 n/are used in series in the apparatus system shown in FIG. Flow rate 10CrIL/, 1',
For a temperature of 60°C, the flow rate of the solution at the outlet of heat exchanger 5 is 10
rx/z and the temperature was 40°C. As mentioned above, the heat exchanger with a built-in static mixer is
Even if the temperature difference with the cooling medium is small, the stirring effect is large, so even a highly viscous liquid with a high heat transfer rate and large heat capacity can be sufficiently removed by water cooling. Comparing this example with a conventional heat removal method using ammonia in terms of energy, it was found that this example reduced energy consumption by 90% compared to the conventional method.

以下、本発明の効果を列挙すれば以下のとおりである。The effects of the present invention are listed below.

（１）冷却水によって除熱を行なうことができ、このた
め従来のようにアンモニア等の冷媒を必要とせず、′唯
１消費量を著しく低減することができる。(1) Heat can be removed by cooling water, so there is no need for a refrigerant such as ammonia as in the past, and the consumption can be significantly reduced.

（２）冷却水による除熱は、アンモニア等の冷媒で行な
う場合と比較して、冷媒と溶液の温度差が小さいので、
熱交換器の管壁に接する溶液の温度はそれほど低下せず
、このため重合物の品質を高めることができる。(2) When heat is removed using cooling water, the temperature difference between the refrigerant and the solution is smaller than when using a refrigerant such as ammonia.
The temperature of the solution in contact with the tube wall of the heat exchanger does not drop significantly, which makes it possible to improve the quality of the polymer.

（３）冷却水による除熱は、アンモニア等の冷Ｈで行な
う場合と比較して、大型の設備を必要とせず、またスタ
チックミキサの使用により、伝熱効率が向上するので熱
交換器を小型化することができる。(3) Heat removal using cooling water does not require large equipment compared to using cold H such as ammonia, and the use of a static mixer improves heat transfer efficiency, making the heat exchanger smaller. can be converted into

【図面の簡単な説明】[Brief explanation of drawings]

第１図は、本発明における重合反応装置の除熱方法の系
統図、第２図は、本発明に用いる伝熱管内のスタチック
ミキサを示す切欠部分斜視図である。 ４・・・重合反応槽、６・・・循環ポンプ、５・・・熱
交換器、７・・・重合反応ライン、８・・・冷却水ライ
ン、１２・・・スタチックミキサ。 代理人　弁理士　　川　北　武　長 第１図 第２図 手続補正書く方式） ％式％ １、事件の表示 昭和５７年　特　許　願第１４６９１号２、発明の名称
　重合反応熱の除熱方法３、補正をする者 事件との関係　特許出願人 ４、代理人〒１０３ 住　所　東京都中央区日本橋茅場町−丁目１１番８号（
紅菌ビルディング）電話０３　（６３９）　５５９２番
氏　名（７６５８）弁理士　川　　北　　武　　長５、
補正命令の日付　昭和５８年６月８日（発送日　昭和５
８年６月２８日） ６、補正の対象　明細書の発明の名称の欄。 （１） ７、補正の内容 （１）明細書第１頁第３行目の「重合反応槽の除熱方法
」を「重合反応熱の除熱方法」に改める。 以上 （２） 手続補正書く自発） 昭和５８年　６月３０日 特許庁長官　若　杉　和　夫　殿 １、事件の表示 昭和５７年　特　許願第１４６９１号 ２、発明の名称　重合反応熱の除熱方法３、補正をする
者 事件との関係　特許出願人 ４、代理人〒１０３ 住　所　東京都中央区日本橋茅場町−丁目１１番８号（
紅菌ビルディング）電話０３　（６３９）５５９２番氏
　名（７６５８）弁理士　川　　北　　武　　長５、補
正命令の日付　自発 ６、１！正の対象　明細書の特許請求の範囲の欄および
明細書の詳細な説明の欄。 （１） ７、補正の内容 （１）明細書の特許請求の範囲の欄を別紙のように改め
る。 （２）明細書第１頁第１１行目の「反応槽」を「反応熱
」に改める。 （３）明細書第２頁第１２行目の「反応槽」を「反応熱
ｊに改める。 以上 （２、 特許請求の範囲 重合反応槽内の反応液の粘度が５００ボイズ以下である
反応液の少なくとも一部を外部に取り出し、スタティッ
クミキサーを内蔵する多管式熱交換器を通して前記反応
槽に再循環させることを特徴とする重合反応塾の除熱方
法。 （３） ｌFIG. 1 is a system diagram of a heat removal method for a polymerization reaction apparatus according to the present invention, and FIG. 2 is a cutaway partial perspective view showing a static mixer in a heat exchanger tube used in the present invention. 4... Polymerization reaction tank, 6... Circulation pump, 5... Heat exchanger, 7... Polymerization reaction line, 8... Cooling water line, 12... Static mixer. Agent: Takenaga Kawakita (Figure 1, Figure 2, procedural amendment writing method) % formula % 1. Indication of the case 1982 Patent Application No. 14691 2. Title of the invention Method for removing heat of polymerization reaction 3. Relationship with the case of the person making the amendment Patent applicant 4, agent 103 Address 11-8 Nihonbashi Kayaba-cho, Chuo-ku, Tokyo (
Hong Kong Building) Telephone 03 (639) 5592 Number Name (7658) Patent Attorney Takeshi Kawakita Cho 5,
Date of amendment order: June 8, 1982 (Shipping date: 1978)
(June 28, 2008) 6. Subject of amendment: column for the title of the invention in the description. (1) 7. Contents of the amendment (1) "Method for removing heat from polymerization reaction tank" in the third line of page 1 of the specification shall be changed to "Method for removing heat of polymerization reaction." Above (2) Voluntary amendment to the procedure) June 30, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case, 1982 Patent Application No. 146912, Title of the invention: Method for removing heat of polymerization reaction 3 , Relationship with the case of the person making the amendment Patent applicant 4, agent 103 Address 11-8 Nihombashi Kayaba-cho, Chuo-ku, Tokyo (
Hong Kong Building) Telephone: 03 (639) 5592 Name (7658) Patent Attorney Takeshi Kawakita 5, Date of Amendment Order Voluntary 6, 1! Positive subject matter: Claims section of the specification and Detailed Description section of the specification. (1) 7. Contents of the amendment (1) The claims section of the specification will be amended as shown in the attached sheet. (2) "Reaction tank" on page 1, line 11 of the specification is changed to "heat of reaction." (3) "Reaction tank" in the 12th line of page 2 of the specification is changed to "reaction heat j. A heat removal method for a polymerization reaction school, characterized in that at least a portion of the heat is taken out to the outside and recirculated to the reaction tank through a multi-tubular heat exchanger incorporating a static mixer. (3) l

Claims (1)

【特許請求の範囲】[Claims] 重合反応槽内の反応液の粘度が５００ボイズ以下である
反応液の少なくとも一部を外部に取り出し、スタティッ
クミキサーを内蔵する多管式熱交換器を通して前記反応
槽に再循環させることを特徴とする重合反応槽の除熱方
法。At least a part of the reaction liquid in the polymerization reaction tank having a viscosity of 500 voids or less is taken out to the outside and recirculated to the reaction tank through a multi-tubular heat exchanger incorporating a static mixer. A method for removing heat from a polymerization reaction tank.