JP3013093B2 - Polyolefin production method - Google Patents
Polyolefin production methodInfo
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- JP3013093B2 JP3013093B2 JP2200009A JP20000990A JP3013093B2 JP 3013093 B2 JP3013093 B2 JP 3013093B2 JP 2200009 A JP2200009 A JP 2200009A JP 20000990 A JP20000990 A JP 20000990A JP 3013093 B2 JP3013093 B2 JP 3013093B2
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- reactor
- gas
- reaction
- catalyst
- oxygen
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、ポリオレフィンの製造において安定した運
動を行なうための方法に関し、詳しくは、気相流動床反
応器によるポリオレフィンの製造において、反応開始時
に起こりやすい溶融樹脂の発生を抑制し、反応装置の運
転を円滑に行なう方法に関するものである。Description: FIELD OF THE INVENTION The present invention relates to a method for performing a stable exercise in the production of polyolefin, and more particularly, to the production of polyolefin by a gas-phase fluidized-bed reactor, The present invention relates to a method for suppressing the occurrence of a molten resin which is likely to occur and smoothly operating a reactor.
［従来の技術］ ポリオレフィンの気相流動床による重合プロセスにお
いては、流動床反応器にあらかじめ種ポリマーと呼ばれ
る樹脂の粉末を充填して流動を開始し、原料混合ガス、
触媒および助触媒としてのアルキルアルミニウム化合物
を連続的に供給すると共に、ガス中の不純物（酸素、水
分等）を除去しながら重合反応を行ない、所定の滞留時
間の間に成長した重合体粒子を抜き出す。上記の種ポリ
マーを使用しないと、供給した触媒が分散し難いため、
粒状樹脂が生成せず、したがって流動床も形成されない
ので、流動床系の重合反応器においては、運転開始時に
必ず種ポリマーが使用されてきた。[Prior Art] In a polymerization process of a polyolefin using a gas-phase fluidized bed, a fluidized-bed reactor is charged with a resin powder called a seed polymer in advance, and fluidization is started.
While continuously supplying an alkylaluminum compound as a catalyst and a cocatalyst, a polymerization reaction is carried out while removing impurities (oxygen, moisture, etc.) in a gas, and polymer particles grown during a predetermined residence time are extracted. . If the above seed polymer is not used, the supplied catalyst is difficult to disperse,
Since no granular resin is formed and thus no fluidized bed is formed, a seed polymer has always been used in a fluidized bed polymerization reactor at the start of operation.
気相流動床によるポリオレフィンの製造において最も
重要な点は、投入された触媒が反応器内できる限り均一
に分散され、かつ流動化ガスが反応器内に均一に分散さ
れて、これらにより反応熱が充分に除去されることであ
る。すなわち、反応器内において触媒濃度が局部的に著
しく高くなったり、ガスが充分に分散せずに冷却効果が
不完全となった場合には、溶融樹脂が生成し、これが塊
状となって流動化を妨げ、温度分布が一層不均一になっ
てさらに溶融樹脂が生成し、この悪循環が繰り返され
て、ついには樹脂を容器内から抜き出すことが不可能と
なり、反応を停止せざるをえなくなる。The most important point in the production of polyolefin by a gas-phase fluidized bed is that the charged catalyst is dispersed as uniformly as possible in the reactor, and the fluidizing gas is evenly dispersed in the reactor, thereby reducing the heat of reaction. Is to be sufficiently removed. In other words, when the catalyst concentration in the reactor becomes extremely high locally or the gas is not sufficiently dispersed and the cooling effect becomes incomplete, a molten resin is formed, which becomes a mass and becomes fluidized. And the temperature distribution becomes more non-uniform, and further molten resin is generated. This vicious cycle is repeated, so that it becomes impossible to remove the resin from the container, and the reaction must be stopped.
以上の問題点の内、後者の流動化ガスの均一な分散に
ついては、樹脂の粒径および粒径分布、かさ密度などと
流動化ガス速度との関係を検討し、かつ容器の構造を配
慮することなどによって比較的容易に解決することがで
きる。しかし、前者の触媒の分散に関しては、触媒およ
び樹脂の粉末の運動により発生する静電気のため、容器
壁へ触媒の微粉末が付着して触媒濃度が増大する結果、
均一な分散状態を実現することがきわめて困難であっ
た。多くの場合、反応開始後約半日間にこの現象が著し
く現われ、壁面のみ温度が上昇してそこで樹脂の溶融が
発生する。Among the above problems, regarding the latter uniform dispersion of the fluidizing gas, consider the relationship between the fluidizing gas velocity and the particle size and particle size distribution of the resin, the bulk density, etc., and consider the structure of the container. It can be relatively easily solved by the above. However, regarding the former catalyst dispersion, due to static electricity generated by the movement of the catalyst and resin powder, the catalyst fine powder adheres to the container wall and the catalyst concentration increases,
It was extremely difficult to achieve a uniform dispersion. In many cases, this phenomenon becomes remarkable about half a day after the reaction starts, and the temperature of only the wall surface rises, and melting of the resin occurs there.
樹脂の粉末が流動することにより静電気を帯びる事実
は日常よく経験されるところであり、たとえば、樹脂粉
をパイプで輸送する際に、その粉末がパイプの内面に薄
く付着することなどが知られている。流動床によるポリ
オレフィンの製造においてもこれらの事実は従来から経
験されており、その対策として米国特許4,855,370号に
おいては反応器内に水分を含有したガスを供給し、特開
昭56−4608号においては液状炭化水素を共存させる方法
を開示しており、さらに米国特許4,532,311号ではクロ
ム含有化合物の添加を、また、特開平１−230607号では
アルコール、ケトンなどをそれぞれ反応器内に添加する
方法を開示している。しかしこれらはいずれも重合反応
中に特定物質を反応器内に供給する方法であるため、実
施に当たり特別の装置を設置する必要があり、かつ運転
操作も複雑にならざるを得ない。したがって、より簡便
な方法で有効に上記の欠点を排除する手段が強く求めら
れていた。The fact that resin powder is charged with static electricity by flowing is a commonly-experienced phenomenon.For example, when resin powder is transported by pipe, it is known that the powder adheres thinly to the inner surface of the pipe. . These facts have been experienced in the production of polyolefins by fluidized beds, and as a countermeasure, U.S. Pat.No. 4,855,370 supplies a gas containing water into the reactor, and JP-A-56-4608 discloses It discloses a method for coexisting liquid hydrocarbons, further discloses adding a chromium-containing compound in U.S. Pat.No. 4,532,311, and discloses a method of adding an alcohol, a ketone, etc., in a reactor, respectively, in JP-A-1-230607. are doing. However, each of these methods is a method of supplying a specific substance into the reactor during the polymerization reaction, so that it is necessary to install a special device for implementation, and the operation operation must be complicated. Therefore, there has been a strong demand for a means for effectively eliminating the above-mentioned disadvantages by a simpler method.
［発明が解決しようとする課題］ 本発明は、気相流動床による重合反応において上記の
欠点を排除し、反応系に特に新たな設備を設けることな
く、きわめて容易な手段で静電気の発生に基づく溶融樹
脂の生成を防止してポリオレフィン粒子を製造する方法
を提供することを目的とする。[Problems to be Solved by the Invention] The present invention eliminates the above-mentioned drawbacks in a polymerization reaction using a gas-phase fluidized bed, and is based on the generation of static electricity by a very easy means without providing a new facility in the reaction system. It is an object of the present invention to provide a method for producing polyolefin particles while preventing generation of a molten resin.
［課題を解決するための手段］ 本発明者らは、上記の目的に沿って鋭意検討した結
果、あらかじめ反応器に酸素を含有する粒子を充填して
流動床反応を開始することにより、溶融樹脂の生成を防
ぐことができることを見出して本発明に到達した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies along the above-mentioned object, and as a result, by filling a reactor with oxygen-containing particles in advance to start a fluidized bed reaction, The present inventors have found that the formation of the compound can be prevented and arrived at the present invention.
すなわち本発明は、気相流動床によるα−オレフィン
の重合反応において、分子状の酸素を含有し、かつ流動
床を形成し得る粒子を、あらかじめ反応器内に充填して
反応を開始することを特徴とするポリオレフィンの製造
法を提供するものである。That is, in the present invention, in the polymerization reaction of an α-olefin by a gas-phase fluidized bed, particles containing molecular oxygen and capable of forming a fluidized bed are charged into a reactor in advance to start the reaction. It is intended to provide a method for producing a characteristic polyolefin.
以下に本発明の内容を詳述する。 Hereinafter, the content of the present invention will be described in detail.
本発明で使用する気相流動床とは、実質的に気−固系
で運転される流動床系をすべて包含し、攪拌機を有する
場合または有しない場合のいずれであってもよい。The gas-phase fluidized bed used in the present invention encompasses substantially all fluidized-bed systems operated in a gas-solid system, and may or may not have a stirrer.
本発明で用いるα−オレフィンとしては、通常炭素数
２〜８のもの、たとえば、エチレン、プロピレン、１−
ブテン、１−ヘキセン、４−メチル−１−ペンテン、１
−オクテンなどのα−オレフィンが挙げられる。これら
は単独でまたは２種以上の混合物として用いられる。The α-olefin used in the present invention generally has 2 to 8 carbon atoms, for example, ethylene, propylene, 1-
Butene, 1-hexene, 4-methyl-1-pentene, 1
Α-olefins such as octene. These are used alone or as a mixture of two or more.
使用する重合触媒としては、チタンおよび／またはバ
ナジウム化合物を含有するチーグラー触媒またはクロム
化合物を含有するフィリップス触媒など公知のものが挙
げられる。Examples of the polymerization catalyst used include known catalysts such as a Ziegler catalyst containing a titanium and / or vanadium compound and a Phillips catalyst containing a chromium compound.
一般に上記の触媒に対して、水、酸素などは還元作用
を抑制する有害な不純物であり、アルキルアルミニウム
などの助触媒でこれらを除去した後に反応を開始する必
要があるとされてきた。しかしながら本発明者らによれ
ば、分子状の酸素を含有する粒子をあらかじめ反応器内
に充填した後に反応を開始することにより、重合反応を
大きく低下させることなく、反応開始後の静電気の発生
による塊状の溶融樹脂の生成を著しく抑制することがで
きる事実が判明した。この事実は従来実施されている種
ポリマーの使用においては経験されていなかったところ
である。In general, it has been considered that water, oxygen, and the like are harmful impurities that suppress the reducing action with respect to the above-mentioned catalyst, and it is necessary to start the reaction after removing these with a promoter such as alkyl aluminum. However, according to the present inventors, by starting the reaction after previously filling particles containing molecular oxygen into the reactor, without significantly reducing the polymerization reaction, the generation of static electricity after the start of the reaction It has been found that the formation of a massive molten resin can be significantly suppressed. This fact has not been experienced in the use of seed polymers conventionally practiced.
上記のあらかじめ反応器内に充填して使用する分子状
の酸素を含有する粒子は、流動床を形成し得るものであ
ればいかなる種類のものでも使用することができるが、
流動化の条件および製品の品質への影響などを考慮すれ
ば、粒状樹脂、特に製品ポリオレフィンに類似した成分
からなる粒状樹脂に分子状酸素を含有させたものが好ま
しい。この目的で使用するポリオレフィン粒子の性状と
しては、平均粒径500〜2,000μｍで微粉が少なく、か
つ、かさ密度0.25〜0.5g/cm3のものが好ましい。The above-mentioned particles containing molecular oxygen to be filled in the reactor in advance can be of any type as long as they can form a fluidized bed.
Considering the conditions of fluidization and the effect on the quality of the product, it is preferable to use a granular resin, especially a granular resin comprising a component similar to the product polyolefin, containing molecular oxygen. As the properties of the polyolefin particles used for this purpose, those having an average particle diameter of 500 to 2,000 μm, a small amount of fine powder, and a bulk density of 0.25 to 0.5 g / cm 3 are preferable.
上記粒子が含有すべき酸素の量は必ずしも厳密に制限
されるものではなく、粒子を分子状の酸素と室温で充分
に接触させることにより容易に目的を達することができ
る。この粒子がポリオレフィン粒子である場合には、1k
gのポリオレフィン粒子に対して0.02〜0.2kgの酸素を、
所要時間１時間以上で通気接触させることが好ましい。The amount of oxygen to be contained in the particles is not necessarily strictly limited, and the object can be easily achieved by bringing the particles into sufficient contact with molecular oxygen at room temperature. If the particles are polyolefin particles, 1k
0.02 to 0.2 kg of oxygen per g of polyolefin particles,
It is preferable that the contact is made with aeration for at least one hour.
粒子に含有された分子状の酸素は、粒子全体にわたり
均一に分布していることが好ましい。このため酸素を含
有させるには、粒子の貯蔵容器に分子状の酸素を含む不
活性ガスを流入させたり、あるいは攪拌機付き混合機ま
たはスクリューミキサー内で粒子を酸素含有不活性ガス
で処理する方法などが用いられる。また、これらの方法
を併用してもよい。Preferably, the molecular oxygen contained in the particles is uniformly distributed throughout the particles. Therefore, in order to contain oxygen, a method of flowing an inert gas containing molecular oxygen into a particle storage container, or a method of treating particles with an oxygen-containing inert gas in a mixer with a stirrer or a screw mixer, etc. Is used. Further, these methods may be used in combination.
分子状の酸素を含有する不活性ガスとしては、乾燥し
た空気が実用上最も好ましい。As the inert gas containing molecular oxygen, dry air is most practically preferable.
含酸素粒子を反応器へ充填する方法としては、気体輸
送が一般に用いられ、また、充填量は重合反応に必要な
流動床高さを保つ量とする。As a method for filling the oxygen-containing particles into the reactor, gas transport is generally used, and the filling amount is an amount that maintains the height of the fluidized bed required for the polymerization reaction.
［発明の効果］ 本発明に従い、分子状の酸素を含有する粒子を反応開
始時に用いて、気相流動床によるポリオレフィン粒子の
製造を行なったところ、反応器内の温度は局部的に高温
を示すことなく、運転停止後の反応器内には溶融樹脂の
生成が認められず、含酸素粒子を用いない場合に比べて
著しく円滑な運転が可能となった。[Effects of the Invention] According to the present invention, when polyolefin particles are produced by a gas-phase fluidized bed using particles containing molecular oxygen at the start of the reaction, the temperature in the reactor shows a locally high temperature. No production of molten resin was observed in the reactor after the operation was stopped, and the operation was significantly smoother than when no oxygen-containing particles were used.
［実施例および比較例］ 実施例１ 気相流動床反応により、直鎖低密度エチレン・１−ブ
テン共重合体を製造するに際し、まず反応系内にエチレ
ン40モル％、水素８モル％、１−ブテン17モル％および
窒素35モル％からなる原料ガスを循環させ、加熱しなが
ら反応系内の水分量が1ppm以下になるまで乾燥した。次
に種ポリマーとしてあらかじめ製造してあったエチレン
・１−ブテン共重合体の粒状樹脂（平均粒径1,000μ
ｍ）の貯蔵サイロの下部から乾燥空気を空搭速度0.75cm
/secで送入し、これを24時間継続して分子状の酸素を含
有させた。この間に送入された酸素の量は0.13kg−酸素
/kg−種ポリマーであった。[Examples and Comparative Examples] Example 1 In producing a linear low-density ethylene / 1-butene copolymer by a gas phase fluidized bed reaction, first, 40 mol% of ethylene, 8 mol% of hydrogen, -A raw material gas consisting of 17 mol% of butene and 35 mol% of nitrogen was circulated and dried while heating until the water content in the reaction system became 1 ppm or less. Next, a granular resin of an ethylene / 1-butene copolymer (average particle diameter 1,000 μm) previously produced as a seed polymer
m) Dry air from the lower part of the storage silo with an airborne speed of 0.75cm
/ sec and continued for 24 hours to contain molecular oxygen. The amount of oxygen sent during this time is 0.13 kg-oxygen
/ kg-seed polymer.
上記種ポリマーを窒素気流により反応器に充填し、上
記ガスにより流動化させて反応を開始した。触媒はシリ
カ−塩化マグネシウム−四塩化チタン系の固体触媒成分
をジエチルアルミニウムクロリドにより活性化したもの
である。助触媒としてトリエチルアルミニウムを用い
た。The reactor was charged with the seed polymer in a nitrogen stream and fluidized with the gas to start the reaction. The catalyst is obtained by activating a solid catalyst component based on silica-magnesium chloride-titanium tetrachloride with diethylaluminum chloride. Triethylaluminum was used as a promoter.
触媒の供給を開始した後、重合反応は順調に開始し、
密度0.920g/cm3、メルトフローレート0.9g/10minのエチ
レン・１−ブテン共重合体が得られた。反応器内の温度
に場所による偏りは見られず、また15日間運転を継続し
た後停止して反応器内部の点検を行なったところ、溶融
樹脂によるシートの生成は観察されなかった。After starting the supply of the catalyst, the polymerization reaction started smoothly,
An ethylene / 1-butene copolymer having a density of 0.920 g / cm 3 and a melt flow rate of 0.9 g / 10 min was obtained. The temperature in the reactor did not show any deviation depending on the location, and after the operation was continued for 15 days, the operation was stopped and the inside of the reactor was inspected. As a result, no sheet was formed by the molten resin.
比較例１ 実施例１で使用した流動床反応器を用い、同例と同様
にして直鎖低密度エチレン・１−ブテン共重合体を製造
するに当り、種ポリマーにあらかじめ分子状の酸素を含
有させないで使用した。すなわち、反応系内を実施例１
と同じ原料ガスを用いて乾燥した後、実施例１と同じエ
チレン・１−ブテン共重合体からなる種ポリマー粒状樹
脂に空気に送入を行なわないで貯蔵サイロから窒素気流
により反応器内に充填し、原料ガスにより流動化させて
反応を開始した。触媒および助触媒は実施例１で使用し
たものと同様である。Comparative Example 1 Using the fluidized-bed reactor used in Example 1 to produce a linear low-density ethylene / 1-butene copolymer in the same manner as in Example 1, the seed polymer contained molecular oxygen in advance. Used without letting. That is, Example 1 was used in the reaction system.
After drying using the same raw material gas as in Example 1, the seed polymer granular resin comprising the same ethylene / 1-butene copolymer as in Example 1 was charged into the reactor by a nitrogen stream from a storage silo without feeding into the air. Then, the reaction was started by fluidizing with the raw material gas. The catalyst and cocatalyst are the same as those used in Example 1.
触媒の供給を開始して３時間経過した頃から、ガス分
散板上30cmの高さの反応器壁温度計が流動床平均温度よ
り１〜２℃高い値を示し始めた。さらに触媒供給開始後
５時間目頃からは前記の温度が10℃高くなり、かつガス
分散板上70cmの高さの反応器壁温度も２〜３℃高い温度
を示すに至った。この後、重合生成物中にシート状の溶
融ポリエチレンが現われはじめ、12時間後には重合物抜
き出し口が閉塞したため反応を停止した。About three hours after the start of the catalyst supply, a reactor wall thermometer 30 cm above the gas dispersion plate began to show a value of 1-2 ° C. higher than the fluidized bed average temperature. From about 5 hours after the start of the supply of the catalyst, the temperature increased by 10 ° C., and the temperature of the reactor wall 70 cm above the gas dispersion plate also increased by 2 to 3 ° C. Thereafter, sheet-like molten polyethylene began to appear in the polymerization product, and after 12 hours, the reaction was stopped because the polymer outlet was blocked.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 幹一 神奈川県川崎市中原区宮内438 (72)発明者 佐野 裕彦 東京都葛飾区高砂８―24―１ (56)参考文献 特開 昭61−123606（ＪＰ，Ａ) 特開 平２−135205（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 2/00 - 2/34 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Michiichi Watanabe 438 Miyauchi, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture (72) Inventor Hirohiko Sano 8-24-1 Takasago, Katsushika-ku, Tokyo (56) References JP-A 61-61 123606 (JP, A) JP-A-2-135205 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08F 2/00-2/34
Claims (1)
応において、粒子重量1kgに対し乾燥空気の酸素0.02〜
0.2kgを１時間以上通気接触することにより分子状の酸
素を含有させた、流動床を形成し得るポリオレフィン粒
子を、あらかじめ反応器内に充填して反応を開始するこ
とを特徴とするポリオレフィンの製造法。In a polymerization reaction of an α-olefin in a gas-phase fluidized bed, oxygen of dry air is 0.02 to 1 kg per particle weight.
The production of a polyolefin, characterized in that polyolefin particles containing a molecular oxygen by bringing into contact with 0.2 kg of air for at least 1 hour and forming a fluidized bed are charged into a reactor in advance and the reaction is started. Law.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2200009A JP3013093B2 (en) | 1990-07-27 | 1990-07-27 | Polyolefin production method |
| AU82257/91A AU643057B2 (en) | 1990-07-27 | 1991-07-26 | Process for producing polyolefin |
| DE69119390T DE69119390T2 (en) | 1990-07-27 | 1991-07-26 | METHOD FOR PRODUCING POLYOLEFINES |
| CA002066770A CA2066770C (en) | 1990-07-27 | 1991-07-26 | Process for producing polyolefin |
| PCT/JP1991/001010 WO1992002563A1 (en) | 1990-07-27 | 1991-07-26 | Process for producing polyolefin |
| US07/844,590 US5385991A (en) | 1990-07-27 | 1991-07-26 | Method for producing polyolefin |
| KR1019920700612A KR0172613B1 (en) | 1990-07-27 | 1991-07-26 | Process for producing polyolefin |
| EP91913120A EP0494316B1 (en) | 1990-07-27 | 1991-07-26 | Process for producing polyolefin |
| US08/328,083 US5525687A (en) | 1990-07-27 | 1994-10-24 | Method for producing polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2200009A JP3013093B2 (en) | 1990-07-27 | 1990-07-27 | Polyolefin production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0485308A JPH0485308A (en) | 1992-03-18 |
| JP3013093B2 true JP3013093B2 (en) | 2000-02-28 |
Family
ID=16417278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2200009A Expired - Fee Related JP3013093B2 (en) | 1990-07-27 | 1990-07-27 | Polyolefin production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3013093B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6743463B2 (en) | 2016-04-12 | 2020-08-19 | 住友化学株式会社 | Method for producing polyolefin |
-
1990
- 1990-07-27 JP JP2200009A patent/JP3013093B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0485308A (en) | 1992-03-18 |
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