JP4165053B2 - How to remove deposits in the reactor - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、反応槽内の付着物の除去方法に関するものである。更に詳しくは、本発明は、オレフィン重合用固体触媒の固体成分を合成する反応に用いた反応槽内のバッフル及び攪拌機軸に付着した付着物を除去する方法であって、反応槽の開放や、高圧水によるジェット洗浄をせずに、短時間で経済的に除去することができるという優れた特徴を有する反応槽内の付着物の除去方法に関するものである。
【０００２】
【従来の技術】
オレフィン重合用固体触媒の固体成分の合成反応での攪拌機の回転数は、固体成分の粒径を制御する因子となっている。固体成分の合成反応時、攪拌の混合効果を向上する目的で、還元槽にバッフルが備えられるが、反応槽内の液面レベル付近から上部のバッフル部、攪拌機軸には攪拌による飛沫などにより、飛散した固体成分が付着し、徐々に大きく成長する。
【０００３】
バッフルに固体成分が付着し成長した場合、還元槽の混合状態が付着していない場合と違ってくるため、制御したい固体成分の粒径に収斂しない現象がおこる。また、攪拌機軸に固体成分が付着し成長した場合は、攪拌機回転時のバランスが崩れ、軸固定部を破壊する等機械トラブルを引き起こす原因となる。
【０００４】
付着物した固体成分の除去のために、反応槽を開放し、高圧水によるジェット洗浄等による物理的な力で付着物を壊しながら、除去するのが一般的な方法であった。この方法は、反応槽の開放のための準備として、反応槽内を窒素等不活性ガスで置換を行なったり、高圧水によるジェット洗浄後の廃水処理も行わなければならず、経済的負担も大きい。
【０００５】
【発明が解決しようとする課題】
かかる状況の下、本発明が解決しようとする課題は、オレフィン重合用固体触媒の固体成分を合成する反応に用いた反応槽内のバッフル及び攪拌機軸に付着した付着物を除去する方法であって、反応槽の開放や、高圧水によるジェット洗浄をせずに、短時間で経済的に除去することができるという優れた特徴を有する反応槽内の付着物の除去方法を提供することである。
【０００６】
【課題を解決するための手段】
本発明者等は、上記課題に鑑み鋭意検討した結果、特定の極性溶剤を使用することにより上記課題が解決できることを見出し、本発明を完成するに至った。
すなわち、本発明は、オレフィン重合用固体触媒の固体成分を合成する反応に用いた反応槽内のバッフル及び攪拌機軸に付着した付着物を除去する方法であって、一般式Ｒ1ＯＨ（Ｒ1は炭素数１〜８のアルキル基を表す。）で表されるアルコール、一般式Ｒ2ＣＯＲ3（Ｒ2及びＲ3は炭素数１〜４のアルキル基を表す。）で表されるケトン及びアセチルアセトンからなる群から選ばれる少なくとも一種である極性化合物を含む溶剤中に付着物を溶解して除去する反応槽内の付着物の除去方法に係るものである。
【０００７】
【発明の実施の形態】
オレフィン重合用固体触媒の固体成分としては、チタン原子、マグネシウム原子、ハロゲン原子及び電子供与性化合物を含有し、かつ該固体触媒の平均粒径が３〜６０μｍのものを例示することができる。一般にオレフィン重合用固体触媒は、例えばＳｉ−Ｏを有する有機系ケイ素化合物及びエステル化合物の存在下、一般式Ｔｉ（ＯＲ1）aＸ4-a（Ｒ1は炭素数が１〜２０の炭化水素基、Ｘはハロゲン原子、ａは、０＜ａ＜＝４の数字を表す。）で表されるチタン化合物を有機マグネシウム化合物で還元して得られる固体成分に、エーテル化合物と四塩化チタン混合物、もしくはエーテル化合物と四塩化チタンとエステル化合物の混合物で処理することで得られる３価のチタン化合物含有固体触媒があげられる。
【０００８】
オレフィン重合用固体触媒の固体成分の合成反応では、適当な溶剤に溶解もしくは希釈したチタン化合物、有機ケイ素化合物及びエステル化合物を投入した反応槽に、攪拌しながら有機マグネシウム化合物を添加する方法、あるいは、逆に、適当な溶剤に溶解もしくは希釈した有機マグネシウム化合物の溶液を投入した反応槽に、攪拌しながらチタン化合物、有機ケイ素化合物及びエステル化合物の混合物を添加する方法がある。溶剤としては、ヘキサン、ヘプタン、オクタン、デカン用の脂肪族炭化水素、ジエチルエーテル、ジブチルエーテル、ジイソアミルエーテル、テトラヒドロフラン等エーテル化合物があげられる。
【０００９】
本発明においては、一般式Ｒ1ＯＨ（Ｒ1は炭素数１〜８のアルキル基を表す。）で表されるアルコール、一般式Ｒ2ＣＯＲ3（Ｒ2及びＲ3は炭素数１〜４のアルキル基を表す。）で表されるケトン及びアセチルアセトンからなる群から選ばれる少なくとも一種である極性化合物を含む溶剤中に付着物を溶解して除去する。
【００１０】
一般式Ｒ1ＯＨ（Ｒ1は炭素数１〜８のアルキル基を表す。）で表されるアルコールとしては、メタノール、エタノール、n−プロパノール、iso−プロパノール、ｎ−ブタノール、２−ブタノール、ｔｅｒｔ−ブタノール、１−ペンタノール、２−ペンタノール、３−ペンタノール、iso−アミルアルコール、tert−アミルアルコール、１−ヘキサノール、sec−ヘキサノール、シクロへキサノール、２−エチルヘキサノール、１−オクタノール、２−オクタノールで等をあげることができ、汎用性、取り扱い性の容易さの観点から、ｎ−ブタノールが好ましい。
【００１１】
一般式Ｒ2ＣＯＲ3で表されるケトンとしては、アセトン、メチルエチルケトン、ジエチルケトン、ジイソプロピルケトン、メチル−イソブチルケトン、ジイソブチルケトン等をあげることができる。
【００１２】
溶剤は上記の極性化合物と不活性炭化水素の混合液であることができる。不活性炭化水素としては、トルエン、キシレン、ケロシン、ブタン、ペンタン、ヘキサン、ヘプタン等をあげることができる。極性化合物／不活性炭化水素の混合比率は、容量で１／１５〜１／６０であることが好ましい。該比が過小であると 付着物の溶解が不十分となり、付着物除去が達成されない場合があり、一方該比が過大であると 除去作業終了後、極性化合物の反応槽からの置換のために多くの時間と多量の洗浄用溶媒を使用し、経済上不利となる場合がある。
【００１３】
付着物の溶解を行う具体的な方法の例としては、次の方法をあげることができる。
▲１▼バッフル、攪拌機軸に付着物が付着している反応槽に、バッフル、攪拌機軸の付着物の両者が浸る量の不活性炭化水素を、反応槽に備えられている内部観察窓で確認しながら、積算流量計を介して供給する。攪拌機は起動していても、していなくともよい。
▲２▼続いて、供給された不活性炭化水素の量を分母とし、１／３０〜１／６０の割合の量の極性化合物を積算流量計を介して、反応槽に供給し、混合液とする。
▲３▼不活性炭化水素、極性物質の反応槽への供給終了後、攪拌機が起動していない場合は、起動する。攪拌機の回転数は、反応槽内で混合液が流動していることが内部観察窓から確認できる程度の回転数でよい。反応槽の圧力は、反応槽の設計耐圧以下となるよう混合液の温度を調整する。
【００１４】
溶解時の溶剤の温度は、室温〜２００℃であることが好ましい。該温度が低すぎると付着物の溶解に要する時間が長くなる場合がある。一方該温度が高すぎると反応槽内圧力が高くなり、圧力調整のため脱ガス量が多くなるため、反応槽の混合液量の減少し、付着物が混合液に浸らなくなる場合がある。
【００１５】
【実施例】
以下、実施例によって本発明を具体的に説明するが、本発明の範囲は実施例のみに限定されるものではない。
ここであげるオレフィン重合用固体触媒の固体成分の合成反応では、水分及び酸素の存在しない不活性溶媒、不活性ガス中での反応を行うことが、必須のものである。
【００１６】
実施例１
［固体成分の還元反応］
特開平１０−２１２３１２号公報に記載の実施例１の内容に準じてオレフィン重合用固体触媒の固体成分の還元反応を反応槽でおこなった。還元反応はバッチ方式で行った。
内径１．２ｍで、容積が約３ｍ3のジャケット付反応槽を露点−７０℃の窒素で充分に置換と乾燥を行った後、脱水したヘキサン１１６０リットルとテトラブトキシチタン３６ｋｇとフタル酸ジイソブチル１４ｋｇとテトラエトキシシラン３４９ｋｇを投入し、攪拌機の回転数１３０ｒｐｍで攪拌し均一溶液とした。つぎに、ｎ−ブチルマグネシウムクロライドのジーｎ―ブチルエーテル溶液８５２リットルを反応槽の温度を８℃に保ち、５時間かけて徐々に投入した。
投入終了後８℃で1時間攪拌した後、２０℃でさらに1時間攪拌した。
かかる合成反応を反応槽で、１０数バッチ行ったところ、反応槽のバッフルと攪拌機軸の液面付近又は、それらの上部に直径で約２０ｃｍ大の付着物が形成されていることが、反応槽に備えられている内部確認用の窓から確認された。
［付着物の除去］
固体成分の付着物が付着した反応槽にヘキサン２５００リットルを加え、室温で、１６０ｒｐｍの回転数で、３時間 攪拌を継続した。続いて、このヘキサンを反応槽から抜き出し、反応槽に備えられている内部確認用の窓から反応槽内部を確認したところ、付着物は攪拌によって崩れることもなく洗浄する前と特に変化はなかった。
次に固体成分の付着物が付着した反応槽にヘキサン２５００リットルとｎ−ブタノール１００リットルを加え、室温で、１６０ｒｐｍの回転数で、約３時間 攪拌を継続した。続いて、この混合液を反応槽から抜き出し、反応槽に備えられている内部確認用の窓から反応槽内部を確認したところ、付着物は全くなくなっていた。
反応槽の使用を再開するにあたっては、ｎ−ブタノールがオレフィン重合用固体触媒の重合活性を低下させる被毒物となることから、これを完全に除くために、露点−７０℃の乾燥窒素を反応槽に毎分約１〜２ｍ3で約２〜３時間通気させた。
以上、反応槽へｎ−ブタノールの投入から反応槽の乾燥窒素の通気による乾燥終了までに要した時間は約７時間であった。
【００１７】
比較例１
付着物した固体成分の除去のために、反応槽を開放し、高圧水によるジェット洗浄による物理的な力で付着物を壊しながら除去した例について説明する。
▲１▼オレフィン重合用固体触媒の固体成分の合成反応を行う反応槽の開放する場合、反応槽内部が炭化水素溶媒やハロゲン化合物が残留しているので、窒素ガスを反応槽に通気させ、これらを槽内部から完全に除去した。
▲２▼続いて、反応槽内に空気を通気させ、反応槽内の窒素を空気と置換を行った。
▲３▼続いて、反応槽のマンホール部を開放し、高圧水によるジェット洗浄を行い、付着物の除去を行う。▲４▼高圧水によるジェット洗浄終了後、反応槽のマンホール部を閉じ、反応槽内部の水分を完全に除去するため、露点が−７０℃近辺の乾燥窒素を通気させた。水分の除去完了は、通気させている乾燥窒素の排気窒素の露点が−６５℃以下とした。
以上の▲１▼〜▲４▼までの一連の作業には、約６０時間を要した。
【００１８】
【発明の効果】
以上説明したとおり、本発明により、オレフィン重合用固体触媒の固体成分を合成する反応に用いた反応槽内のバッフル及び攪拌機軸に付着した付着物を除去する方法であって、反応槽の開放や、高圧水によるジェット洗浄をせずに、短時間で経済的に除去することができるという優れた特徴を有する反応槽内の付着物の除去方法を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for removing deposits in a reaction tank. More specifically, the present invention is a method for removing deposits adhering to the baffle and stirrer shaft in the reaction vessel used in the reaction for synthesizing the solid component of the solid catalyst for olefin polymerization, and opening the reaction vessel, The present invention relates to a method for removing deposits in a reaction tank having an excellent feature that it can be removed economically in a short time without jet cleaning with high-pressure water.
[0002]
[Prior art]
The rotation speed of the stirrer in the synthesis reaction of the solid component of the solid catalyst for olefin polymerization is a factor for controlling the particle size of the solid component. For the purpose of improving the mixing effect of stirring during the synthesis reaction of the solid components, the reduction tank is equipped with a baffle, but from the vicinity of the liquid level in the reaction tank to the upper baffle part, the stirrer shaft due to splashing by stirring, etc. The scattered solid components adhere and gradually grow larger.
[0003]
When the solid component adheres to the baffle and grows, the phenomenon does not converge to the particle size of the solid component to be controlled because the mixed state of the reduction tank is different from the case where it does not adhere. In addition, when a solid component adheres to the stirrer shaft and grows, the balance during rotation of the stirrer is lost, which causes mechanical troubles such as breaking the shaft fixing portion.
[0004]
In order to remove the adhered solid component, it was a general method to open the reaction vessel and remove the adhered material while destroying the adhered material with a physical force such as jet washing with high-pressure water. In this method, as a preparation for opening the reaction tank, the inside of the reaction tank must be replaced with an inert gas such as nitrogen, or waste water treatment after jet cleaning with high-pressure water must be performed, resulting in a large economic burden. .
[0005]
[Problems to be solved by the invention]
Under such circumstances, the problem to be solved by the present invention is a method for removing deposits adhering to the baffle and stirrer shaft in the reaction vessel used for the reaction for synthesizing the solid component of the solid catalyst for olefin polymerization. An object of the present invention is to provide a method for removing deposits in a reaction tank having an excellent feature that it can be removed economically in a short time without opening the reaction tank or performing jet cleaning with high-pressure water.
[0006]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by using a specific polar solvent, and have completed the present invention.
That is, the present invention is a method for removing deposits adhering to a baffle and a stirrer shaft in a reaction vessel used for a reaction for synthesizing a solid component of an olefin polymerization solid catalyst, which has the general formula R 1 OH (R 1 Represents an alkyl group having 1 to 8 carbon atoms), a ketone represented by the general formula R 2 COR 3 (R 2 and R 3 represent an alkyl group having 1 to 4 carbon atoms), and The present invention relates to a method for removing deposits in a reaction vessel by dissolving and removing deposits in a solvent containing at least one polar compound selected from the group consisting of acetylacetone.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the solid component of the solid catalyst for olefin polymerization include those containing a titanium atom, a magnesium atom, a halogen atom and an electron donating compound, and having an average particle diameter of 3 to 60 μm. In general, the solid catalyst for olefin polymerization is, for example, a general formula Ti (OR 1 ) a X 4-a (R 1 is a hydrocarbon having 1 to 20 carbon atoms) in the presence of an organic silicon compound having Si—O and an ester compound. A solid component obtained by reducing a titanium compound represented by the group, X is a halogen atom, a is a number of 0 <a <= 4) with an organomagnesium compound, an ether compound and a titanium tetrachloride mixture, Or the trivalent titanium compound containing solid catalyst obtained by processing with the mixture of an ether compound, titanium tetrachloride, and an ester compound is mention | raise | lifted.
[0008]
In the synthesis reaction of the solid component of the solid catalyst for olefin polymerization, a method of adding an organomagnesium compound with stirring to a reaction vessel charged with a titanium compound, an organosilicon compound and an ester compound dissolved or diluted in an appropriate solvent, or Conversely, there is a method in which a mixture of a titanium compound, an organosilicon compound and an ester compound is added to a reaction vessel in which a solution of an organomagnesium compound dissolved or diluted in a suitable solvent is added. Examples of the solvent include hexane, heptane, octane, aliphatic hydrocarbons for decane, ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether, and tetrahydrofuran.
[0009]
In the present invention, an alcohol represented by a general formula R 1 OH (R 1 represents an alkyl group having 1 to 8 carbon atoms), a general formula R 2 COR 3 (R 2 and R 3 are each represented by 1 to 4 carbon atoms). The deposit is dissolved and removed in a solvent containing at least one polar compound selected from the group consisting of ketones and acetylacetone.
[0010]
Examples of the alcohol represented by the general formula R 1 OH (R 1 represents an alkyl group having 1 to 8 carbon atoms) include methanol, ethanol, n-propanol, iso-propanol, n-butanol, 2-butanol, and tert. -Butanol, 1-pentanol, 2-pentanol, 3-pentanol, iso-amyl alcohol, tert-amyl alcohol, 1-hexanol, sec-hexanol, cyclohexanol, 2-ethylhexanol, 1-octanol, 2 N-Butanol is preferable from the viewpoint of versatility and ease of handling.
[0011]
Examples of the ketone represented by the general formula R 2 COR 3, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, methyl - may be mentioned isobutyl ketone, diisobutyl ketone.
[0012]
The solvent can be a mixture of the above polar compound and an inert hydrocarbon. Examples of the inert hydrocarbon include toluene, xylene, kerosene, butane, pentane, hexane, heptane, and the like. The mixing ratio of polar compound / inert hydrocarbon is preferably 1/15 to 1/60 by volume. If the ratio is too small, the deposit may not be sufficiently dissolved, and the removal of the deposit may not be achieved. On the other hand, if the ratio is too large, the polar compound may be replaced from the reaction vessel after the removal operation is completed. Using a lot of time and a large amount of cleaning solvent may be economically disadvantageous.
[0013]
The following method can be mention | raise | lifted as an example of the concrete method of melt | dissolving a deposit | attachment.
(1) Confirm the amount of inert hydrocarbons that can be immersed in both the baffle and the stirrer shaft in the reaction tank with deposits on the baffle and stirrer shaft using the internal observation window provided in the reaction tank. While supplying through an integrating flow meter. The stirrer may or may not be activated.
(2) Subsequently, the amount of the supplied inert hydrocarbon is used as a denominator, and a polar compound having a ratio of 1/30 to 1/60 is supplied to the reaction vessel via an integrating flow meter, To do.
(3) If the stirrer has not been started after the supply of inert hydrocarbons and polar substances to the reaction tank, start them. The rotation speed of the stirrer may be a rotation speed that can confirm from the internal observation window that the mixed liquid is flowing in the reaction vessel. The temperature of the mixed solution is adjusted so that the pressure in the reaction tank is equal to or lower than the design withstand pressure of the reaction tank.
[0014]
The temperature of the solvent at the time of dissolution is preferably room temperature to 200 ° C. If the temperature is too low, it may take a long time to dissolve the deposits. On the other hand, if the temperature is too high, the pressure in the reaction vessel increases, and the amount of degassing increases for pressure adjustment, so that the amount of liquid mixture in the reaction vessel decreases, and the deposit may not be immersed in the liquid mixture.
[0015]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the scope of the present invention is not limited only to an Example.
In the synthesis reaction of the solid component of the solid catalyst for olefin polymerization mentioned here, it is essential to carry out the reaction in an inert solvent or inert gas free from moisture and oxygen.
[0016]
Example 1
[Reduction reaction of solid components]
The reduction reaction of the solid component of the solid catalyst for olefin polymerization was carried out in a reaction vessel in accordance with the contents of Example 1 described in JP-A-10-212312. The reduction reaction was performed in a batch mode.
A jacketed reaction tank having an inner diameter of 1.2 m and a volume of about 3 m 3 was sufficiently replaced and dried with nitrogen having a dew point of −70 ° C., and then dehydrated 1160 liters, tetrabutoxytitanium 36 kg, diisobutyl phthalate 14 kg, 349 kg of tetraethoxysilane was added and stirred at a rotating speed of 130 rpm of a stirrer to obtain a uniform solution. Next, 852 liters of a di-n-butyl ether solution of n-butylmagnesium chloride was gradually added over 5 hours while maintaining the temperature of the reaction vessel at 8 ° C.
After completion of the addition, the mixture was stirred at 8 ° C for 1 hour, and further stirred at 20 ° C for 1 hour.
When 10 or more batches of this synthesis reaction were carried out in the reaction vessel, it was confirmed that deposits approximately 20 cm in diameter were formed near the liquid surface of the baffle and the stirrer shaft of the reaction vessel or on the upper part thereof. It was confirmed from the window for internal confirmation provided in.
[Removal of deposits]
2500 L of hexane was added to the reaction vessel on which the solid component deposits were adhered, and stirring was continued at room temperature for 3 hours at a rotation speed of 160 rpm. Subsequently, when this hexane was extracted from the reaction vessel and the inside of the reaction vessel was confirmed through an internal confirmation window provided in the reaction vessel, the adhering matter was not changed by the stirring and was not particularly changed. .
Next, 2500 liters of hexane and 100 liters of n-butanol were added to the reaction vessel to which the solid component deposits had adhered, and stirring was continued at room temperature at a rotation speed of 160 rpm for about 3 hours. Subsequently, when this mixed solution was extracted from the reaction vessel and the inside of the reaction vessel was confirmed through an internal confirmation window provided in the reaction vessel, no deposits were found.
In resuming the use of the reaction vessel, n-butanol becomes a poison that lowers the polymerization activity of the solid catalyst for olefin polymerization, and in order to completely remove this, dry nitrogen having a dew point of -70 ° C. is used in the reaction vessel. Were aerated at about 1-2 m 3 per minute for about 2-3 hours.
As described above, the time required from the introduction of n-butanol into the reaction vessel to the completion of drying by aeration of dry nitrogen in the reaction vessel was about 7 hours.
[0017]
Comparative Example 1
In order to remove the attached solid component, an example will be described in which the reaction vessel is opened and the deposit is broken while being broken by physical force by jet cleaning with high-pressure water.
(1) When the reaction tank for performing the synthesis reaction of the solid component of the solid catalyst for olefin polymerization is opened, since the hydrocarbon solvent and the halogen compound remain inside the reaction tank, nitrogen gas is passed through the reaction tank. Was completely removed from the tank interior.
(2) Subsequently, air was passed through the reaction vessel, and nitrogen in the reaction vessel was replaced with air.
(3) Subsequently, the manhole part of the reaction tank is opened, and the deposits are removed by jet cleaning with high-pressure water. {Circle around (4)} After completion of jet cleaning with high-pressure water, the manhole portion of the reaction vessel was closed, and dry nitrogen having a dew point of around −70 ° C. was aerated in order to completely remove the water inside the reaction vessel. When the removal of moisture was completed, the dew point of exhaust nitrogen of the dry nitrogen being vented was −65 ° C. or lower.
The series of operations from (1) to (4) above required about 60 hours.
[0018]
【The invention's effect】
As described above, according to the present invention, there is provided a method for removing deposits attached to a baffle and a stirrer shaft in a reaction vessel used for a reaction for synthesizing a solid component of an olefin polymerization solid catalyst. In addition, it was possible to provide a method for removing deposits in a reaction tank having an excellent feature that it can be removed economically in a short time without jet cleaning with high-pressure water.
Claims (7)
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| JP2001326080A JP4165053B2 (en) | 2001-10-24 | 2001-10-24 | How to remove deposits in the reactor |
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| DE602005012386D1 (en) * | 2005-08-10 | 2009-03-05 | Linde Ag | Process for the purification of a reactor |
| JP4830524B2 (en) * | 2006-02-13 | 2011-12-07 | 住友化学株式会社 | Cleaning the rotary valve |
| US8128755B2 (en) | 2010-03-03 | 2012-03-06 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Cleaning solvent and cleaning method for metallic compound |
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