JPS62138505A - Multi-chamber continuous polymerization method - Google Patents
Multi-chamber continuous polymerization methodInfo
- Publication number
- JPS62138505A JPS62138505A JP27669585A JP27669585A JPS62138505A JP S62138505 A JPS62138505 A JP S62138505A JP 27669585 A JP27669585 A JP 27669585A JP 27669585 A JP27669585 A JP 27669585A JP S62138505 A JPS62138505 A JP S62138505A
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- valve
- polymerization
- valves
- circulation line
- 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.)
- Pending
Links
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はα−オレフィン自身を媒体とする塊状重合法に
関する。詳しくは、スラリー循環ラインを設けた反応槽
を2漕以上連結した重合機を用いたα−オレフィンの連
続重合方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a bulk polymerization method using α-olefin itself as a medium. Specifically, the present invention relates to a method for continuous polymerization of α-olefins using a polymerization machine in which two or more reaction vessels each having a slurry circulation line are connected.
α−オレフィンヲ重合するに際し、α−オレフィン自身
を液状媒体とする塊状重合法で重合することは、古くか
ら知られている。又多くの銘柄のポリマーを得るため、
或は重合熱の除去が大型の反応機では困難であることか
ら、2槽以上の重合漕を連結した反応機を用いて重合反
応を行うことも知られている。しかしながら塊状重合法
でα−オレフィンを重合する場合には反応1背の圧力は
温度で定まってしまう上に得られるポリプロピレンの分
子mを制御するために水素を導入ししかもより後の四の
重合槽での゛水素の量を増大させる場合には重合温間を
後段で下げないとスラリーを#夜することが困難である
。従って例えば特開昭53−25585ではより後の重
合槽で重合温度を低下させることが示されている。又ス
ラリーポンプを用いてスラリーポンプする方法もよく知
られている。It has been known for a long time that α-olefins are polymerized by bulk polymerization using the α-olefin itself as a liquid medium. In addition, in order to obtain many brands of polymer,
Alternatively, since it is difficult to remove the polymerization heat in a large reactor, it is also known to carry out the polymerization reaction using a reactor in which two or more polymerization tanks are connected. However, when polymerizing α-olefins using the bulk polymerization method, the pressure at the back of reaction 1 is determined by the temperature, and hydrogen is introduced in order to control the molecule m of the polypropylene obtained. When increasing the amount of hydrogen in the step, it is difficult to make the slurry overnight unless the polymerization temperature is lowered in the latter stage. Therefore, for example, JP-A-53-25585 discloses lowering the polymerization temperature in a later polymerization tank. A method of pumping slurry using a slurry pump is also well known.
しかしながら温度差で圧力差を作り移液する方法は後の
漕では重合温度が下がるため、解媒活性が低下しさらに
は除熱が困難になるという問題があり、重合温度につい
ての自由度もない。又後者の方法では重合温度音大きく
下げる必要はないものの大きな逆圧ではスラIJ −,
7ンプの負荷が増大し場合によっては閉基してしまう問
題がある。さらに移液量が昇圧された圧力と次の反応槽
の圧力差によるという点は変らないためスラリーの移液
i1を制御するためスラリーの循環ライ/l−設は弁の
開閉動作によってスラリーを移液する方法が考えられる
が、弁特に高圧用のそれは長時間開閉動作ヲ様り返すと
漏れを生ずる場合が多く危険な上に取り替えに用する費
用も犬である。However, the method of creating a pressure difference using a temperature difference and transferring the liquid has the problem that the polymerization temperature decreases in the later tanks, which reduces desolvation activity and makes it difficult to remove heat, and there is no flexibility in determining the polymerization temperature. . In addition, in the latter method, although it is not necessary to lower the polymerization temperature significantly, a large reverse pressure will cause the slurry IJ -,
There is a problem that the load on the 7 pump increases and, in some cases, it may close. Furthermore, since the amount of liquid transferred depends on the difference between the increased pressure and the pressure in the next reaction tank, in order to control the slurry transfer i1, the slurry circulation line/l-equipment transfers the slurry by opening and closing the valve. One option is to drain the valve, but valves, especially those for high pressure, often leak if they are opened and closed for long periods of time, which is not only dangerous, but also expensive to replace.
〔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する方法について鋭意検討
した結果特定の方法で上記問題が解決できることを見い
出し本発明を完成した。即ち本発明はスラリーの循環ラ
インを設けた反応槽を241“フ以上循猿ラインより取
り出した移液ラインにより連結した重合嵌を用いてα−
オレフィン自身を媒体とする塊状重合法でα−オレフィ
/ヲ連続的に重合する方法において循環ラインの反応槽
へのもどり部及び移液ラインに弁開度可変の弁を設け、
重合反応の開始から各端の重合条件が所望の条件となる
までは、スラリーの移液量と弁の開閉操作で制御し、6
槽の重合条件が所望の条件となってから後は弁の弁じ4
度でスラリーの移液量を制御することを特徴とする多1
′3連続重合方法である。[Means for Solving the Problems] As a result of intensive study on methods for solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a specific method, and have completed the present invention. That is, the present invention uses a polymer fitting to connect a reaction tank equipped with a slurry circulation line with a liquid transfer line taken out from a circulation line of 241" or more.
In a method of continuously polymerizing α-olefin / olefin by bulk polymerization using olefin itself as a medium, a valve with a variable opening degree is provided in the return section of the circulation line to the reaction tank and in the liquid transfer line,
From the start of the polymerization reaction until the polymerization conditions at each end reach the desired conditions, the amount of slurry transferred and the opening/closing of valves are controlled.
After the polymerization conditions in the tank reach the desired conditions, turn the valve valve 4.
A multi-function device characterized by controlling the amount of slurry transferred at a
'3 continuous polymerization method.
本発明においてα−オレフィンとはプロピレン、ブテン
−1、ヘキセン−1及びそれらの混合′吻又はエチレン
との混合物を示す。In the present invention, the α-olefin refers to propylene, butene-1, hexene-1, and mixtures thereof or mixtures thereof with ethylene.
本発明において上記α−オレフィンを重合するに際して
使用する触媒としては公知のものが使用でき特に限定は
なく、遷移金属化合物と有機金属化合物からなる触媒系
が用いられ、具体的にはチタンのハロダン化物或はそれ
をハロゲン化マグネシウム、シリカ、アルミナなどの担
体に担持したものが、遷移金属化合物として用いられ有
機アルミニウム、有機マグネシウムなどの有機金属化合
物として好ましく用いられる。In the present invention, any known catalyst can be used to polymerize the α-olefin, and there are no particular limitations. A catalyst system consisting of a transition metal compound and an organometallic compound is used, and specifically, a titanium halide is used. Alternatively, those supported on a carrier such as magnesium halide, silica, or alumina are used as transition metal compounds, and are preferably used as organometallic compounds such as organoaluminum and organomagnesium.
本発明の、態様を図面を用いて詳述する。Embodiments of the present invention will be explained in detail using the drawings.
反応!1,2.3を連結した3漕からなる重合機ヲ用い
てα−オレフィンが塊状重合法で重合される。反応槽3
からのスラリーは、ff3−4t%Iてスラリーの後処
理工程に送られる。各1は液面計1−1.2−1.3−
1によって液面高さが検知され、その信号によって制御
器1−5.2−5゜3−5によって1−3.1−4.2
−3.2−4゜3−3.3−4の6弁が操作され液面が
一定となるように制御される。reaction! An α-olefin is polymerized by a bulk polymerization method using a polymerization machine consisting of three tanks in which units 1, 2, and 3 are connected. Reaction tank 3
The slurry from ff3-4t%I is sent to a slurry post-treatment step. Each 1 is a liquid level gauge 1-1.2-1.3-
The liquid level height is detected by the controller 1-5.2-5°3-5 according to the signal.
-3.2-4° 3-3.3-4 six valves are operated to control the liquid level to be constant.
本発明に一しいて重要なのは6槽が所望の条件で安定す
るまでのみ6弁は開閉することで液面が制御さn、安定
した条件になった後は6弁の弁開度によってit;II
alされることである。この目的のためには升の形状
としてはV&−ル弁などのスラリーを特定の弁開度で定
↑よ的に移液することが可能なものが好ましいものとし
て挙げられ、又必要に応じ弁座にα−オレフィン或いは
不活性溶媒をフラツシングすること、或いは特定の時間
間隔で短時間液面の制御を6弁の開閉で行いスラリーの
つまり防止を行うことも可能である。What is most important to the present invention is that the liquid level is controlled by opening and closing the six valves only until the six tanks are stabilized under the desired conditions, and after the conditions are stable, it is controlled by the valve opening of the six valves; II
It is to be treated. For this purpose, it is preferable that the shape of the box be one that allows the slurry to be transferred steadily up and down at a specific valve opening, such as a V&R valve, and a valve that can be opened as needed. It is also possible to prevent clogging of the slurry by flushing α-olefin or an inert solvent at the slurry, or by controlling the liquid level for short periods at specific time intervals by opening and closing six valves.
6弁の開閉による液面の制御は次のようにして行われる
、例として反応槽1について述べる。反応槽1から抜き
出されたスラリーはポンプ1−2で昇圧し、弁1−4が
閉の時は弁1−3が開となり反応槽1に循環してもどり
、弁1−4が開の時は弁1−3が閉となりスラリーは反
応槽2に移液される。弁1−3が開の時と弁1−4が開
の時の時間比を定めることで反応槽1から反応槽2への
スラリーの概略の移液量が定まる(詳細には反応槽1側
と反応槽2側の圧損差が加わる)。弁1−4が開の際は
弁1−3は閉となっているため逆流のおそれはまったく
なく、スラリーポンプ1−2で昇圧したスラリーが反応
槽2に移液されるため、少しの逆圧が生じても移液可能
である。弁の開閉を小きざみに行えば反応槽1に対して
反応槽2の差圧が大きくても多量のスラリーが一度に移
妓されることがなく、重合開始の際或いは条件変更の際
各種の圧力が変動しても良好に液面を制御できる。各・
iUが所望の条件に安定した後には弁の弁開度によって
スラリーの移’f’J、 Mが制御される。この際それ
ぞれの弁の弁開度(特により閉側)に制限値を設け、そ
の制限値以上に弁開度を変えないようにしておくのが好
ましい、なぜなら、スラIJ −中の固形粒子以下の弁
一度ではスラリーがろ過され開広してしまうからである
。従って弁開度を1bす限値ヲ毬えて変見る必要の生じ
た時には、自動的に弁の開閉によるa]lI aに切り
侠わるように制御、+Il器1−5.2−5.3−5t
−設定しておくのが好ましい。なお破線は制−系の連結
状態を示す。Control of the liquid level by opening and closing the six valves is performed as follows.Reaction tank 1 will be described as an example. The slurry extracted from the reaction tank 1 is pressurized by the pump 1-2, and when the valve 1-4 is closed, the valve 1-3 is opened and is circulated back to the reaction tank 1. At this time, valve 1-3 is closed and the slurry is transferred to reaction tank 2. By determining the time ratio between when valve 1-3 is open and when valve 1-4 is open, the approximate amount of slurry transferred from reaction tank 1 to reaction tank 2 is determined (in detail, the amount of slurry transferred from reaction tank 1 to reaction tank 2 is determined) and the pressure drop difference on the reaction tank 2 side is added). When valve 1-4 is open, valve 1-3 is closed, so there is no risk of backflow.Since the slurry pressurized by slurry pump 1-2 is transferred to reaction tank 2, there is no risk of backflow. Liquid transfer is possible even under pressure. By opening and closing the valve in small steps, even if the differential pressure between reaction tank 1 and reaction tank 2 is large, a large amount of slurry will not be transferred at once, and various changes will be made when starting polymerization or changing conditions. The liquid level can be well controlled even if the pressure fluctuates. each·
After iU has stabilized to a desired condition, the slurry movement 'f'J, M is controlled by the valve opening degree of the valve. At this time, it is preferable to set a limit value for the valve opening degree of each valve (especially on the closer side) and to prevent the valve opening degree from changing beyond that limit value, because the solid particles in the slug IJ- This is because if the valve is opened only once, the slurry will be filtered and spread out. Therefore, when it becomes necessary to change the valve opening degree beyond the limit value of 1b, the valve opening is automatically controlled to switch to a]lI a by opening and closing the valve, +Il device 1-5.2-5.3 -5t
- It is preferable to set this in advance. Note that the broken line indicates the connection state of the control system.
升のml閉及び弁の弁開度の1fJll +卸の一例を
以下に述べる。An example of ml closing of the square and opening of the valve 1fJll + wholesale will be described below.
升の開閉により制御器する場合は液面計によシ液面を検
知し予め設定された液面と比較し、液面が設定値より制
い場合にはスラリーのモドリの弁1−3の開の時間を一
定時間短くする。1−3の弁が一定の回数間となった後
にも液面が前回の測定レベルより高い場合には弁1−4
の開の時+i’] v。When controlling by opening and closing the tank, the liquid level is detected by a liquid level gauge and compared with the preset liquid level, and if the liquid level is lower than the set value, the slurry control valve 1-3 is activated. Shorten the opening time by a certain amount of time. If the liquid level is higher than the previous measurement level even after the valve 1-3 has been activated a certain number of times, the valve 1-4
+i'] v.
一定時間長くする。次いで同(>Jeに一定の回数の後
前回の測定レベルと比較し、低くなっていればさらに設
定値と比較して、升の開の時間′fti史する方法が挙
げられる。Extend for a certain amount of time. Next, after a certain number of times, the level is compared with the previous measurement level, and if it is lower, it is further compared with a set value, and the opening time 'fti of the cell is recorded.
各端の条件がほぼ安定した後の制御区v法としては筐ず
6弁の弁開度に上限、下限を設定する(上限については
必ずしも必要ではない)。次いで各弁を各種の圧力、ポ
ンプの吐出圧力、ポンプの吐出址によって予め設定され
た升一度にする。次いで各種の液面を検知し、設定値と
比較し設定値より高い場合にはスラリーの移0.側の升
の5部開度を一定値だけ大きくする。一定時間抜同様に
tL面の(・寅知された高さを設定値と比較し、より液
面が旨くなっていればスラリーの戻り11111の弁の
弁開度を一定値だけ小さくする同様に一定時間ごとに設
定された液面と検知された液面全比較しその値により弁
開度を操作することが行われる。After the conditions at each end are approximately stabilized, the control section v method sets upper and lower limits for the valve openings of the six valves (upper limits are not necessarily required). Then, each valve is adjusted to a predetermined volume according to various pressures, pump discharge pressures, and pump discharge ends. Next, various liquid levels are detected and compared with the set value, and if the level is higher than the set value, the slurry transfer is 0. Increase the opening degree of the 5th part of the side square by a certain value. In the same way as for a certain period of time, compare the known height of the tL surface with the set value, and if the liquid level is better, reduce the valve opening of the slurry return valve 11111 by a certain value. The set liquid level is compared with the detected liquid level at regular intervals, and the valve opening degree is controlled based on the value.
本発明の方法を実施することにより弁への過度の負荷を
さけることが可能となるため長時間の運転を安定に行う
ことが可能となる。By carrying out the method of the present invention, it becomes possible to avoid excessive load on the valve, so that stable operation for a long period of time becomes possible.
上記本発明の制御法全ポリプロピレンの塊状重合法のプ
ラントに適用したところ、3000時間の運転を連続的
に行ってもまったく問題が生じなかった、この時各種の
条件を大幅に変える操作(重合スタートも含め)を5回
実施したが、弁からのひnれはまったく見られなかった
。一方弁の開閉動作による移散(6弁が2.5分/1回
で開閉を繰り返している)を行なったところ約1100
時間で一つの升で漏れを生じたので運転を中断した。When the control method of the present invention was applied to a plant for bulk polymerization of all-polypropylene, no problems occurred even after 3,000 hours of continuous operation. 5 times, but no fins were observed from the valve. When dispersion was performed by opening and closing one-way valves (6 valves were opened and closed repeatedly at a rate of 2.5 minutes/1 time), approximately 1100
At one time, one tank leaked, so operation was suspended.
本発明の方法を実施することによって、極めて安定した
運転を弁の破損などのトラブルなく長時間行うことが可
能となり工業的に極めて価値がある。By carrying out the method of the present invention, it is possible to carry out extremely stable operation for a long period of time without troubles such as damage to valves, which is extremely valuable industrially.
第1図は本発明の方法全実施するためのプラントノフロ
ーの1部を示すフロー図で6る。
1.2.3・・・重合槽、1−2.2−2.3−2・・
・スラリーポンプ、1−1,2−1,3−1・・・液面
計、1−311−412−312−413−3゜3−4
・・・弁、1−5.2−5.3−5・・・制御器。FIG. 1 is a flow diagram showing a part of the plant flow for carrying out the entire method of the present invention. 1.2.3...Polymerization tank, 1-2.2-2.3-2...
・Slurry pump, 1-1, 2-1, 3-1...Liquid level gauge, 1-311-412-312-413-3゜3-4
...Valve, 1-5.2-5.3-5...Controller.
Claims (2)
、循環ラインより取り出した移液ラインにより連結した
重合機を用いてα−オレフィン自身を媒体とする塊状重
合法でα−オレフィンを連続的に重合する方法において
、循環ラインの反応槽へのもどり部及び移液ラインに弁
開度可変の弁を設け、重合反応の開始から各槽の重合条
件が所望の条件となるまでは、スラリーの移液量を弁の
開閉操作で制御し、各槽の重合条件が所望の条件となっ
てから後は弁の弁開度でスラリーの移液量を制御するこ
とを特徴とする多槽連続重合方法。(1) α-olefin is continuously produced using a bulk polymerization method using α-olefin itself as a medium, using two or more reaction vessels equipped with a slurry circulation line and a polymerization machine connected by a liquid transfer line taken out from the circulation line. In the method of polymerizing the slurry continuously, valves with variable opening degrees are installed in the return section of the circulation line to the reaction tank and in the liquid transfer line, and the slurry is The slurry transfer amount is controlled by opening and closing the valves, and after the polymerization conditions in each tank reach the desired conditions, the slurry transfer amount is controlled by the valve opening degree. Polymerization method.
量を用いる特許請求の範囲第1項記載の方法。(2) The method according to claim 1, in which the amount of slurry in each tank is used as the control value for the amount of slurry transferred.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27669585A JPS62138505A (en) | 1985-12-11 | 1985-12-11 | Multi-chamber continuous polymerization method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27669585A JPS62138505A (en) | 1985-12-11 | 1985-12-11 | Multi-chamber continuous polymerization method |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS62138505A true JPS62138505A (en) | 1987-06-22 |
Family
ID=17573035
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27669585A Pending JPS62138505A (en) | 1985-12-11 | 1985-12-11 | Multi-chamber continuous polymerization method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62138505A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008190739A (en) * | 2007-02-01 | 2008-08-21 | Sumitomo Heavy Ind Ltd | Cooling device and semiconductor inspection device |
-
1985
- 1985-12-11 JP JP27669585A patent/JPS62138505A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008190739A (en) * | 2007-02-01 | 2008-08-21 | Sumitomo Heavy Ind Ltd | Cooling device and semiconductor inspection device |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0886655B1 (en) | A process and an apparatus for polymerization of olefin monomers | |
EP1962996B1 (en) | Gas-phase process and apparatus for the polymerization of olefins | |
EP1660223A1 (en) | Olefin polymerization process with optimized product discharge | |
RU2009133299A (en) | DEVICE FOR LIQUID PHASE POLYMERIZATION OF OLEFINS | |
US9840567B2 (en) | Olefin polymerization process with continuous transfer | |
KR20200116091A (en) | Remote pressure sensing for polymer reactor control | |
JPS62138505A (en) | Multi-chamber continuous polymerization method | |
EP2004323B1 (en) | Flushing in a multiple loop reactor | |
KR101465918B1 (en) | Process for supplying catalyst to a polymerization reactor | |
CN1138049A (en) | Process for polymerising olefin in gas phase | |
EP2598543B1 (en) | Pressure control of the catalyst mixing vessel | |
JPS6172007A (en) | Continuous polymerization | |
EP2607385B1 (en) | Loop reactor providing an advanced production split control | |
EA009423B1 (en) | Polyolefin production using high olefin concentration | |
US20140073748A1 (en) | Method for improving ethylene polymerization reactions | |
US20150361199A1 (en) | Olefin Polymerization Process With Continuous Discharging | |
CA2250264C (en) | A process and an apparatus for polymerization of olefin monomers | |
JPS5879533A (en) | Supplying method for catalyst | |
KR20230051053A (en) | Methode for cleaning the reactor | |
RU2574700C1 (en) | Circulating reactor with improved monitoring of flow division | |
JPS5940841B2 (en) | Polymerization method of α-olefin | |
JPH07118342A (en) | Vapor phase polymerization of olefin |