JPH0730131B2 - Method of removing heat of polymerization - Google Patents
Method of removing heat of polymerizationInfo
- Publication number
- JPH0730131B2 JPH0730131B2 JP1865985A JP1865985A JPH0730131B2 JP H0730131 B2 JPH0730131 B2 JP H0730131B2 JP 1865985 A JP1865985 A JP 1865985A JP 1865985 A JP1865985 A JP 1865985A JP H0730131 B2 JPH0730131 B2 JP H0730131B2
- Authority
- JP
- Japan
- Prior art keywords
- cooling
- polymerization
- liquid
- heat
- condensed
- 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
Links
- 238000006116 polymerization reaction Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 14
- 238000001816 cooling Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 20
- 239000007791 liquid phase Substances 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000498 cooling water Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は重合熱の除去方法に関する。詳しくは、液相の
存在下にエチレン、塩化ビニル、プロピレン、ブテン−
１、ヘキセン−１、ヘプテン−１、オクテン−１の単
独、或は相互の共重合反応を行うに際し、液相の１部を
気化、冷却凝縮させることにより重合熱を除去する方法
に関する。TECHNICAL FIELD The present invention relates to a method for removing heat of polymerization. Specifically, in the presence of a liquid phase, ethylene, vinyl chloride, propylene, butene-
The present invention relates to a method for removing a heat of polymerization by vaporizing, cooling and condensing a part of a liquid phase when a copolymerization reaction of 1, hexene-1, heptene-1, and octene-1 or mutual mutual reaction is carried out.
従来の技術 重合反応を工業的規模で実施するに際しては、重合反応
熱を効率よく除去することは重要な問題であり、特に大
型の反応機では、重合反応を液相の存在下に行い、液相
の１部を蒸発させ、その蒸気を冷却凝縮し、凝縮液は重
合反応機にもどす、いわゆる還流冷却機を用いる方法は
良く知られている。例えば西ドイツ国特許公開公報第23
05211号など多くの例が知られている。又、このような
還流冷却器を用いる際に問題となる冷却器伝熱面への重
合体の付着による伝熱効率の低下に対しては、液滴を噴
霧することが知られている（例えば特開昭48-88186号、
特開昭51-84887号、特開昭52-96687号など） 発明が解決しようとする問題点 しかしながら単に液滴を噴霧するだけでは、特に冷却凝
縮部への蒸気の導入ラインと、冷却凝縮した液の反応機
へのもどりラインが別に設けられた装置では伝熱効率の
低下防止に不充分であり、長期間の連続運転に耐えない
という問題があった。2. Description of the Related Art Efficient removal of the heat of polymerization reaction is an important issue when carrying out the polymerization reaction on an industrial scale.Especially for large reactors, the polymerization reaction is performed in the presence of a liquid phase. It is well known to use a so-called reflux condenser in which a part of the phase is evaporated, the vapor is cooled and condensed and the condensate is returned to the polymerization reactor. For example, West German Patent Publication No. 23
Many examples are known, such as 05211. Further, it is known to spray droplets to reduce the heat transfer efficiency due to the adhesion of the polymer to the heat transfer surface of the cooler, which is a problem when using such a reflux cooler (for example, a special method). Kaisho 48-88186,
Problems to be Solved by the Invention However, by merely spraying liquid droplets, especially when the vapor is introduced into the cooling / condensing section and the cooling / condensing is performed. An apparatus provided with a separate return line for the liquid to the reactor is insufficient to prevent reduction in heat transfer efficiency and has a problem that it cannot withstand continuous operation for a long period of time.
問題点を解決するための手段 本発明者らは上記問題を解決した長期間の連続重合にも
耐える重合熱の除去方法について鋭意検討し本発明を完
成した。Means for Solving the Problems The present inventors completed the present invention by earnestly investigating a method for removing the heat of polymerization that can withstand long-term continuous polymerization, which solves the above problems.
即ち本発明は、エチレン、塩化ビニル、プロピレン、ブ
テン−１、ヘキセン−１、ヘプテン−１、オクテン−１
の単独、或は相互の共重合反応を液相の存在下に行うに
際し、該液相の一部を気化させ、気化した蒸気を冷却凝
縮して重合熱を除去する方法において、該気化した蒸気
の冷却凝縮部までの流路の少なくとも一部を冷却し、し
かも該冷却部及び／又は上方に冷却凝縮部で冷却凝縮さ
れるものと同一のもの、反応機に導入される追加の単量
体、液状媒体、及び冷却凝縮部で冷却凝縮した液から選
ばれた実質的に不揮発分を含有しない液を噴霧すること
を特徴とする重合熱の除去方法である。That is, the present invention includes ethylene, vinyl chloride, propylene, butene-1, hexene-1, heptene-1, octene-1.
In the method of carrying out the homopolymerization reaction of each of them in the presence of a liquid phase, a part of the liquid phase is vaporized, and the vaporized vapor is cooled and condensed to remove the heat of polymerization. Of at least a part of the flow path to the cooling / condensing section, and the same as that which is cooled and condensed in the cooling section and / or in the cooling / condensing section, and the additional monomer introduced into the reactor. The method for removing the heat of polymerization is characterized in that a liquid containing substantially no non-volatile component selected from the liquid medium and the liquid condensed by cooling in the cooling condenser is sprayed.
本発明において、重合に用いる単量体は、エチレン、塩
化ビニル、プロピレン、ブテン−１、ヘキセン−１、ヘ
プテン−１、オクテン−１でありそれらの単独或は相互
の共重合反応の際の重合熱の除去に適用される。In the present invention, the monomers used for the polymerization are ethylene, vinyl chloride, propylene, butene-1, hexene-1, heptene-1, and octene-1, which are polymerized during the copolymerization reaction of them alone or with each other. Applied for heat removal.
液相を構成する成分としては、従って上記単量体の他
に、重合に際して反応を阻害しない反応条件下に液状で
ある化合物が併用可能であり、プロパン、ブタン、ペン
タン、ヘキサン、ヘプタン、オクタンなどの炭化水素化
合物、場合によっては水も使用可能である。As the component constituting the liquid phase, therefore, in addition to the above-mentioned monomer, a compound that is liquid under the reaction conditions that do not inhibit the reaction during polymerization can be used in combination, such as propane, butane, pentane, hexane, heptane, octane, etc. It is also possible to use the hydrocarbon compounds of, and optionally water.
本発明においては反応条件としては特に限定はないが、
液相の気化及び該気化した蒸気が比較的高い温度で冷却
凝縮し、効率的に重合熱が除去できる条件、即ち、冷却
凝縮部に導入される冷却水の温度が常温に近い温度で良
い重合温度及び圧力下に運転されるのが好ましい。In the present invention, the reaction conditions are not particularly limited,
Liquid phase vaporization and the vaporized vapor is cooled and condensed at a relatively high temperature to efficiently remove the heat of polymerization, that is, the temperature of the cooling water introduced into the cooling condenser is good when the temperature is close to room temperature. It is preferably operated under temperature and pressure.
本発明において噴霧される実質的に不揮発分を含有しな
い液としては冷却凝縮部で冷却凝縮されるものと同一の
もの或は反応機に導入される追加の単量体、或は液状媒
体、又は、冷却凝縮部で冷却凝縮した液が使用できる。In the present invention, the substantially non-volatile content liquid to be sprayed is the same as that which is cooled and condensed in the cooling / condensing section, or an additional monomer introduced into the reactor, or a liquid medium, or The liquid cooled and condensed in the cooling condenser section can be used.
本発明の態様について以下に図面を用いて説明する。第
１図に反応機まわりの概要を示す。１は反応槽、２は冷
却凝縮部、３はブロワー、４は本発明の態様を示すに重
要な部分であり第２図に拡大して示す。５は反応槽で気
化した蒸気の冷却凝縮部への流路、６は該流路を冷却す
るための冷却水の入りのライン、７は出のライン、14は
冷却用ジャケット、８は噴霧用液の導入ライン、９は噴
霧ノズル、10は冷却凝縮部への冷却水導入ライン、11は
導出ライン、12は冷却凝縮部で凝縮した液の反応槽への
もどりライン、13は非凝縮ガスのもどりラインである。Aspects of the present invention will be described below with reference to the drawings. Figure 1 shows the outline of the reactor and its surroundings. Reference numeral 1 is a reaction tank, 2 is a cooling / condensing section, 3 is a blower, and 4 is an important part for showing an embodiment of the present invention, which is enlarged and shown in FIG. 5 is a flow path to the cooling / condensing part of vaporized vapor in the reaction tank, 6 is a line for entering cooling water for cooling the flow path, 7 is an output line, 14 is a cooling jacket, 8 is for spraying Liquid introduction line, 9 is a spray nozzle, 10 is a cooling water introduction line to the cooling condenser, 11 is a discharge line, 12 is a return line for the liquid condensed in the cooling condenser to the reaction tank, and 13 is a non-condensed gas. It is a return line.
本発明において反応槽１で気化した蒸気は流路４を通っ
て冷却凝縮部に送られる。冷却凝縮部の構造は特に制限
はないが通常は多管式の熱交換器と同様の構造とするの
が好ましい。該部で冷却凝縮した液はライン12より反応
槽にもどる。又図面に示すように非凝縮ガスはブロワー
などで強制的に反応槽にもどすのが好ましい。In the present invention, the vaporized vapor in the reaction tank 1 is sent to the cooling condensing section through the flow path 4. The structure of the cooling / condensing part is not particularly limited, but it is usually preferable to have a structure similar to that of a multi-tube heat exchanger. The liquid cooled and condensed in the section returns to the reaction tank through the line 12. Further, as shown in the drawing, it is preferable to forcibly return the non-condensed gas to the reaction tank by using a blower or the like.
作用および効果 本発明の方法を実施することにより長時間にわたって運
転を続けても冷却凝縮部の冷却能力が低下することなく
重合熱を除去することが可能となり工業的に極めて価値
がある。Actions and Effects By carrying out the method of the present invention, it is possible to remove the heat of polymerization without lowering the cooling capacity of the cooling condenser section even if the operation is continued for a long time, which is of great industrial value.
本発明の方法が優れている理由の１つには蒸気の１部が
流路５の壁面で凝縮し同伴した重合体、触媒などととも
に壁面に付着し、それに液を噴霧することで洗い流して
しまうため、重合体とか触媒などが２の冷却凝縮部にま
で同伴されることがないため冷却凝縮部の伝熱効率の低
下により重合熱が除去できなくなるなどの問題が生じな
いものと思われる。One of the reasons why the method of the present invention is excellent is that a part of the vapor is condensed on the wall surface of the flow path 5 and adheres to the wall surface together with the entrained polymer, catalyst, etc., and is washed away by spraying the liquid on it. Therefore, it is considered that no polymer or catalyst is entrained in the second cooling / condensing section, and the heat of polymerization in the cooling / condensing section is reduced, so that the heat of polymerization cannot be removed.
実施例 以下に実施例を挙げ本発明をさらに説明する。Examples The present invention will be further described below with reference to Examples.
内容積40m3の重合槽を用い液状プロピレンを液状媒体と
する塊状重合法で三塩化チタンとジエチルアルミニウム
クロライドからなる触媒を用いて連続重合を行った。重
合槽は冷却可能なジャケットで覆れており（最大除熱量
600Mcal/H）ほぼ一定の冷却水を導入することで一定の
熱量を除去し、第１図に示す還流冷却器で残りの重合熱
を除去する方法で毎時2.4T/Hでポリプロピレンを重合し
た。（三塩化チタン触媒1.2kg/H） この時毎時約1200Mcalの発熱はジャケットで約300Mca
l、多管式の熱交換器である冷却凝縮部で約900Mcalが除
去されている。Continuous polymerization was carried out by a bulk polymerization method using liquid propylene as a liquid medium in a polymerization tank having an internal volume of 40 m 3 using a catalyst composed of titanium trichloride and diethylaluminum chloride. The polymerization tank is covered with a jacket that can be cooled (maximum heat removal amount).
(600 Mcal / H) A constant amount of heat was removed by introducing almost constant cooling water, and polypropylene was polymerized at 2.4 T / H per hour by the method of removing the remaining heat of polymerization by the reflux condenser shown in FIG. (Titanium trichloride catalyst 1.2kg / H) At this time, heat generation of about 1200Mcal per hour is about 300Mca in the jacket.
l, About 900Mcal is removed in the cooling and condensing part which is a multi-tube heat exchanger.
実施例では、第２図の14（５は8Bの配管であり、約2mが
10Bの配管でおおわれている。）は約4000kg/Hで20℃の
水を流し、しかも14の上方20cmのところより液状プロピ
レンが700kg/Hでスプレーされた。この条件で３ケ月運
転したのち熱交換器を解体したところほとんど固形分の
付着は見られなかった。14に冷却水を通すことなく単に
液状プロピレンをスプレーしながら運転したところ３ケ
月の運転で熱交換器の約1/5の管にポリプロピレンが付
着していた。一方14に単に冷却水を通すことだけで運転
したところ約２ケ月の運転で冷却凝縮部での除熱が困難
になり運転を中止して解体したところ多管式熱交の約1/
3の管にポリプロピレンが付着ししかも約1/5の管はほぼ
閉塞していた。In the embodiment, 14 (5 in FIG. 2 is an 8B pipe, about 2 m
It is covered with 10B piping. ) Flowed water at about 4000 kg / H at 20 ° C, and liquid propylene was sprayed at 700 kg / H from 20 cm above 14. After operating for 3 months under these conditions, the heat exchanger was disassembled, and almost no solid content was found. When it was operated by simply spraying liquid propylene without passing cooling water through it, polypropylene adhered to about 1/5 of the tubes in the heat exchanger after 3 months of operation. On the other hand, when it was operated by simply passing cooling water through 14, it was difficult to remove heat in the cooling condensing part after about 2 months of operation, and the operation was discontinued and dismantled.
Polypropylene was attached to the tube of 3 and about 1/5 of the tube was almost blocked.
第１図は本発明の方法を適用した反応機を示す図面であ
り第２図はその詳細である。FIG. 1 is a drawing showing a reactor to which the method of the present invention is applied, and FIG. 2 is its details.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｆ 2/04 ＭＡＷ 14/00 ＭＫＡ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C08F 2/04 MAW 14/00 MKA
Claims (1)
ン−１、ヘキセン−１、ヘプテン−１、オクテン−１の
単独、或は相互の共重合反応を液相の存在下に行うに際
し、該液相の一部を気化させ、気化した蒸気を冷却凝縮
して重合熱を除去する方法において、該気化した蒸気の
冷却凝縮部までの流路の少なくとも一部を冷却し、しか
も該冷却部及び／又は上方に冷却凝縮部で冷却凝縮され
るものと同一のもの、反応機に導入される追加の単量
体、液状媒体、及び冷却凝縮部で冷却凝縮した液から選
ばれた実質的に不揮発分を含有しない液を噴霧すること
を特徴とする重合熱の除去方法。1. A liquid phase of ethylene, vinyl chloride, propylene, butene-1, hexene-1, heptene-1, octene-1, or a mutual copolymerization reaction in the presence of a liquid phase. In a method of vaporizing a portion of the vaporized vapor and cooling and condensing the vaporized vapor to remove the heat of polymerization, cooling at least a portion of the flow path to the cooling condenser of the vaporized vapor, and further cooling the cooling portion and / or The same as the one that is cooled and condensed in the cooling condenser section, the additional monomer that is introduced into the reactor, the liquid medium, and the substantially non-volatile content selected from the liquid that is cooled and condensed in the cooling condenser section. A method for removing the heat of polymerization, which comprises spraying a liquid not containing it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1865985A JPH0730131B2 (en) | 1985-02-04 | 1985-02-04 | Method of removing heat of polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1865985A JPH0730131B2 (en) | 1985-02-04 | 1985-02-04 | Method of removing heat of polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61179206A JPS61179206A (en) | 1986-08-11 |
| JPH0730131B2 true JPH0730131B2 (en) | 1995-04-05 |
Family
ID=11977740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1865985A Expired - Lifetime JPH0730131B2 (en) | 1985-02-04 | 1985-02-04 | Method of removing heat of polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730131B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2533726Y2 (en) * | 1990-07-23 | 1997-04-23 | 船井電機株式会社 | Recording and playback equipment |
-
1985
- 1985-02-04 JP JP1865985A patent/JPH0730131B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61179206A (en) | 1986-08-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |