JPS6028404A - Production of transition metal catalyst supported by carrier - Google Patents
Production of transition metal catalyst supported by carrierInfo
- Publication number
- JPS6028404A JPS6028404A JP58135101A JP13510183A JPS6028404A JP S6028404 A JPS6028404 A JP S6028404A JP 58135101 A JP58135101 A JP 58135101A JP 13510183 A JP13510183 A JP 13510183A JP S6028404 A JPS6028404 A JP S6028404A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- liquid hydrocarbon
- metal compound
- hydrocarbon compound
- compound
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は担体付遷移金属触媒の効率的な製造法に関する
。詳しくは、担体に液状の遷移金属化合物を接触して、
担体付遷移金属触媒を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an efficient method for producing a supported transition metal catalyst. Specifically, by contacting a carrier with a liquid transition metal compound,
The present invention relates to a method for producing a supported transition metal catalyst.
遷移金属化合物を種々の担体に担持した触媒は醸化反応
、重合反応等に用いられ、中でもハロゲン化マグネシウ
ムを含有する担体に遷移金属化合物を担持した触媒は、
有機金属化合物、中でも有機アルミニウム化合物と組み
合せることによって触媒当シ高収率でオレフィンを重合
してポリオレフィンを与えることが時分３９−１２１０
５号公報で提案されて以来数多くの改良触媒が提案され
ている。Catalysts in which transition metal compounds are supported on various carriers are used in fermentation reactions, polymerization reactions, etc. Among them, catalysts in which transition metal compounds are supported on carriers containing magnesium halide are used in fermentation reactions, polymerization reactions, etc.
By combining with organometallic compounds, especially organoaluminum compounds, it is possible to polymerize olefins with catalysts in high yields to give polyolefins.
Since the catalyst was proposed in Publication No. 5, many improved catalysts have been proposed.
改良触媒の中でも、担体を液状の遷移金属化合物でスラ
リー状態で接触することによって得られる担体付遷移金
属触媒の性能が優れている。しかしながら該方法では、
担持した後担持されていない遊離の遷移金属化合物を除
去しないと触媒の性能が劣ることから通常は炭化水素化
合物で担体遷移金属触媒を繰シ返し洗浄することが行わ
れる。Among the improved catalysts, supported transition metal catalysts, which are obtained by contacting a carrier with a liquid transition metal compound in a slurry state, have excellent performance. However, in this method,
Since the performance of the catalyst deteriorates unless the unsupported free transition metal compound is removed after being supported, the supported transition metal catalyst is usually washed repeatedly with a hydrocarbon compound.
従って洗浄に用いた大量の炭化水素化合物の回収再利用
を行う必要がちシ、分解、洗浄、蒸留に要する設備及び
その処理に要するエネルギーはぼう犬であシ、簡略化す
ることが望まれる。Therefore, it is necessary to recover and reuse a large amount of hydrocarbon compounds used for cleaning, and it is desirable to simplify the equipment and energy required for decomposition, cleaning, and distillation.
本発明者らは上記課題について種々の検討を行った結果
、特定の方法を行うことによって、液状炭化水素化合物
の回収が極めて簡略化されることを見い出し本発明を完
成した。As a result of various studies regarding the above-mentioned problem, the inventors of the present invention have found that recovery of liquid hydrocarbon compounds can be extremely simplified by carrying out a specific method, and have completed the present invention.
本発明の目的は、簡略化された担体付遷移金属触媒の製
造法を提供することにある。An object of the present invention is to provide a simplified method for producing a supported transition metal catalyst.
本発明は、担体に液状の遷移金属化合物をスラリー状態
で接触し、次いで担持されていない遊離の遷移金属化合
物を液状炭化水素化合物で繰シ返し洗浄して担持遷移金
属触媒を得る方法に於て洗浄用液状炭化水素化合物とし
て洗浄前の遷移金属化合物含有液状炭化水素化合物に比
較して、遷移金属化合物を少ない比率でしか含有しない
回収液状炭化水素化合物を用いることを特徴とする担体
付遷移金属触媒の製造法に関する。The present invention provides a method for obtaining a supported transition metal catalyst by contacting a carrier with a liquid transition metal compound in a slurry state, and then repeatedly washing unsupported free transition metal compounds with a liquid hydrocarbon compound. A supported transition metal catalyst characterized in that a recovered liquid hydrocarbon compound containing a transition metal compound in a smaller proportion than the liquid hydrocarbon compound containing a transition metal compound before cleaning is used as a cleaning liquid hydrocarbon compound. Concerning the manufacturing method.
本発明の方法が適用可能な担体付遷移金属触媒の製造法
については格別の制限はないが、比較的濃い濃度の遷移
金属化合物溶液を用いる必要のちるオレフィン重合用触
媒の製造に適用する効果が犬である。Although there are no particular restrictions on the method for producing supported transition metal catalysts to which the method of the present invention can be applied, it is effective when applied to the production of catalysts for olefin polymerization, which requires the use of relatively concentrated transition metal compound solutions. It's a dog.
オレフィン重合用の担体付遷移金属触媒の製造法として
は多くの方法が知られておシ先の持分３９−１２１０５
号、特開５０−１２６５９０、特開５２−１０４５９３
、特開５４−４１９８５、特開５６−８１１、特開５６
−６７３１１、特開５６−１１９０８号の公報で開示さ
れた触媒の製造法などが具体的事例として挙げられる。Many methods are known for producing supported transition metal catalysts for olefin polymerization.
No., JP 50-126590, JP 52-104593
, JP 54-41985, JP 56-811, JP 56
Specific examples include methods for producing catalysts disclosed in JP-A-67311 and JP-A-56-11908.
即ちその製造法の中に担体を液状の遷移金属化合物と接
触することによって担持し、次いで液状炭化水素化合物
で洗浄する工程があるものであれば適用可能である。That is, any manufacturing method is applicable as long as it includes a step of supporting the carrier by contacting it with a liquid transition metal compound and then washing it with a liquid hydrocarbon compound.
本憚明に於て、担体としては種々の無機化合物が挙げら
れるが中でもＭｔＣｔ２ 、ＭＬ？Ｂｒ２などのノ・ロ
ゲン化マグネシウム及びそれらとＡｔ２０３、ＳｉＯ２
、ｋｔｃＬ３ などの混合、さらに好ましくは、Ｃ−０
結合、Ｃ−Ｎ結合、Ｃ−Ｐ結合を含有する有機化合物を
含有する上記化合物が挙げられる。In this discussion, various inorganic compounds can be used as the carrier, among which MtCt2, ML? Magnesium chloride such as Br2 and them together with At203, SiO2
, ktcL3, etc., more preferably C-0
The above compounds include organic compounds containing a bond, a C--N bond, and a C--P bond.
本発明に於て、液状の遷移金属化合物としては、ＴｉＣ
４、Ｊｃｚ３ などのそれ自身液状であるもの及び／又
はそれらと液状炭化水素化合物との混合物又は、ＴｉＣ
ｌ２、ｖＣｔ３などのそれ自身は固体であるが適当な錯
化物例えばエーテル等で液状炭化水素に可溶化したもの
の液状炭化水素溶液などが挙げられる。In the present invention, the liquid transition metal compound is TiC
4. Those which are liquid themselves such as Jcz3 and/or mixtures thereof with liquid hydrocarbon compounds, or TiC
Examples include liquid hydrocarbon solutions of l2, vCt3, etc., which are solids themselves, but are solubilized in liquid hydrocarbons with suitable complexes such as ether.
本発明に於て液状の炭化水素化合物としては脂肪族、脂
環族、芳香族炭化水素及び／又は、それらの１部の水素
がハロゲン原子で置換されたハロゲン化炭化水素が挙げ
られ具体的にはヘキサン、ベンジン、テカン、シクロヘ
キサンベンゼン、トルエン、キシレン、エチルベンゼン
、クメン等がそれぞれ単独で或は混合物で、又、石油ベ
ンジン、灯油、軽油などの蒸留留分など、又、塩化メチ
ン／、塩化エチレン、Ａ化エチレン、クロロベンゼン、
ブロモベンゼンなどが好ましく用いられる。In the present invention, liquid hydrocarbon compounds include aliphatic, alicyclic, aromatic hydrocarbons, and/or halogenated hydrocarbons in which a portion of hydrogen atoms thereof have been replaced with halogen atoms. Hexane, benzine, tecane, cyclohexane benzene, toluene, xylene, ethylbenzene, cumene, etc., each singly or in a mixture, petroleum benzine, kerosene, light oil, etc. distilled fractions, etc., and methine chloride/ethylene chloride , A-ethylene, chlorobenzene,
Bromobenzene and the like are preferably used.
本発明に於て洗浄前の遷移金属化合物含有液状炭化水素
化合物に比較して遷移金属化合物を少ない比率でしか含
有しない回収液状炭化水素化合物を用いて洗浄すること
の具体化の方法としては、例えば遷移金属触媒を担持し
た固体部を１０回洗浄して、担体的遷移金属触媒を得る
操作を繰シ返し行う時、例えば洗浄溶媒をＡｉｊ （担
体付遷移金属触媒のｉ回目の合成でｊ回目の洗浄を表わ
す）とした時、Ａ１２をＡ２Ｂのために用いＡ１３をＡ
２２のために又Ａ２２はＡ３１のために用いるというよ
うに段階的に繰シ上げて用いていくという方法ももちろ
ん可能であるがそのためには回収液用のタンクが多量に
必要でありしかも、洗浄回数が多くなり余シ好ましくな
い。好ましい形態としては例えば１〜３回は処理（例え
ば中和水洗）蒸留回収にまわし４〜６回は次の触媒製造
の際の１〜３回に用い、又、７〜９回は遷移金属化合物
を含有しない炭化水素化合物を用い回収液は４〜６回の
洗浄に用いその回収液はさらに１〜３回の洗浄に用いる
といった方法で行うことである。上記の例れば洗浄用炭
化水素化合物が処理蒸留することなく３回使用できるこ
とになシ回収精製が１／３で良いこととなる。In the present invention, as a method for implementing cleaning using a recovered liquid hydrocarbon compound containing a transition metal compound in a smaller proportion than the transition metal compound-containing liquid hydrocarbon compound before cleaning, for example, When the solid part supporting the transition metal catalyst is washed 10 times to obtain a supported transition metal catalyst, for example, the washing solvent is Aij (in the i-th synthesis of the supported transition metal catalyst, the j-th ), A12 is used for A2B and A13 is used for A2B.
Of course, it is also possible to gradually increase the number of uses, such as using A22 for A31, and A22 for A31. This is not desirable as the number of times increases. As a preferable form, for example, 1 to 3 times are used for treatment (for example, neutralization and washing with water) and distilled recovery, 4 to 6 times are used for 1 to 3 times in the next catalyst production, and 7 to 9 times are used for the transition metal compound. The method is to use a hydrocarbon compound that does not contain . In the above example, the cleaning hydrocarbon compound can be used three times without being subjected to process distillation, which means that the amount of recovery and purification can be reduced to 1/3.
本発明の方法を用いることによシ担体付遷移金属触媒が
効率的に製造することが可能にな９工業的価値が犬であ
る。以下に実施例を挙げ本発明をさらに具体的に説明す
る。By using the method of the present invention, it is possible to efficiently produce a supported transition metal catalyst, which has great industrial value. EXAMPLES The present invention will be explained in more detail with reference to Examples below.
実施例１
担体付遷移金属触媒の製造
ａ）内容積６００ｍｔ、直径１２ｍｍ のステンレス製
ボール１．２ｋｉｉ’の入ったポット２個装備した振動
ミルを準備する。窒素雰囲気下、上記ポットにそれぞれ
塩化マグネシウム２０２、テトラエトキシシラン４肌ら
α、α、α−トリクロロトルエン３ｍｌを入れ４０時
間粉砕する。次いで得られた共粉砕物１０？を２００ｍ
ｔの丸底フラスコに入れ１００ｍｔの四塩化チタンと８
０℃で２時間攪拌し次いで静置して８５ｍｔの上澄を除
去し、次いてｎ−へブタン１００ ｍＡを加え攪拌し次
いで静置し１００ｍｔの上澄を除去する操作を９回縁Ｑ
返した。ただし４回〜６回及び７回〜９回の抜き出し液
は、次の洗浄に用いた。Example 1 Production of supported transition metal catalyst a) A vibratory mill equipped with two pots containing 1.2 kii' stainless steel balls with an internal volume of 600 mt and a diameter of 12 mm is prepared. Under a nitrogen atmosphere, 202 ml of magnesium chloride, 4 ml of tetraethoxysilane, and 3 ml of α, α, α-trichlorotoluene were placed in the pot and ground for 40 hours. Then, the obtained co-pulverized product 10? 200m
Put 100 mt of titanium tetrachloride and 8 into a T round bottom flask.
Stir at 0°C for 2 hours, leave to stand and remove 85 m of supernatant, add 100 mA of n-hebutane, stir, leave to stand and remove 100 m of supernatant 9 times.
I returned it. However, the liquids extracted from the 4th to 6th and 7th to 9th times were used for the next cleaning.
ｂ） ａ）の回収洗浄液４〜６回は洗浄の１〜３回に用
い又７〜９回の洗浄液は４〜６回に用い、４〜６回の回
収ｎ−へブタン及び７〜９回の回収用にはフレッシュな
ｎ−へブタンを用いた他はａ）と同様に触媒を合成した
。b) The recovered washing solution 4 to 6 times in a) was used for 1 to 3 times of washing, and the washed solution 7 to 9 times was used for 4 to 6 times, and the recovered n-hebutane was used for 4 to 6 times, and the recovered n-hebutane was used for 7 to 9 times. A catalyst was synthesized in the same manner as in a) except that fresh n-hebutane was used for recovery.
Ｃ） ｂ）の回収洗浄液４〜６回及び７〜９回を用いた
他はｂ）と同様にした。C) The procedure was the same as in b) except that the recovered washing solution in b) was used 4 to 6 times and 7 to 9 times.
実施例２
洗浄溶媒としてトルエンを用いた他は実施例１と同様に
ａ）、ｂ）、ｃ）の触媒を合成した。Example 2 Catalysts a), b), and c) were synthesized in the same manner as in Example 1 except that toluene was used as a washing solvent.
実施例３
内容積５ｔのオートクレーブに実施例１．２テ得た触媒
３０ｍ２％ ジエチルアルミニウムクロライド０．１２
８ｍｔ、ｐ −トルイル酸メチル０−０３ｍｔｓトリエ
チルアルミニウム０ 、０８ ｍｔを５０ｍＡのｎ−へ
ブタン中で混合した触媒と１．５にグのプロピレン１．
８ＮＺの水素を加え７５℃で２時間重合し次いで未反応
のプロピレンを除去した後乾燥して秤量して触媒当シの
取れ高及び極限粘度数（１３５℃テトラリン溶液で測定
、以下ηと略記）、沸騰ｎ−ヘプタン抽出残率（ソック
スレー抽出器を用いて沸騰ｎ−へブタンで６時間抽出し
及びかさ比重を測定した。Example 3 30 m2 of the catalyst obtained in Example 1.2 in an autoclave with an internal volume of 5 tons 0.12% diethylaluminum chloride
8 mt, methyl p-toluate 0-03 mts triethylaluminum 0.08 mt mixed catalyst in n-hebutane at 50 mA and 1.5 g of propylene.
Add 8NZ of hydrogen and polymerize at 75°C for 2 hours, then remove unreacted propylene, dry and weigh to determine catalyst yield and intrinsic viscosity (measured with 135°C tetralin solution, hereinafter abbreviated as η). , boiling n-heptane extraction residue (extracted with boiling n-heptane for 6 hours using a Soxhlet extractor, and measuring the bulk specific gravity.
参考例
各回収へブタン及びトルエン中のＴｉ Ｃｔ４濃度はＴ
ｉ分析結果と洗浄効率の計算結果がほぼ一致しておシ、
１回目の抜き出し液はＴｉＣｔ４を１３ ｖｏ１％、以
下２回目（１，７ｖｏ１％）、３回目（０，２２ｖｏ１
％）４回目（０，０３ｖｏ１％）、５回目（３，７Ｘ
１．０−３ｖｏ１％）、６回目（４，０ＸＩＯ−’ｖｏ
１％）、７回目（６，３ＸＩＯ″” ｖｏ１％）、８回
目（８，ｌＸ１Ｏ−６ｖｏ１％）９回目（１、ＯＸ １
０−６ｖｏ１％）である。Reference example The Ti Ct4 concentration in butane and toluene for each recovery is T
The i-analysis results and the cleaning efficiency calculation results almost match.
The first extraction liquid contained TiCt4 at a concentration of 13 vol.
%) 4th time (0.03vo1%), 5th time (3.7X
1.0-3vo1%), 6th time (4,0XIO-'vo
1%), 7th (6,3XIO″” vo1%), 8th (8,1X1O-6vo1%), 9th (1,OX 1
0-6vol%).
Claims (1)
し、次いで担持されていない遊離の遷移金属化合物を液
状炭化水素化合物で繰勺返し洗浄して担持遷移金属触媒
を得る方法に於て、洗浄用液状炭化水素化合物として洗
浄前の遷移金属化合物含有液状炭化水素化合物に比較し
て、遷移金属化合物を少ない比率でしか含有しない回収
液状炭化水素化合物を用いることを特徴とする担体付遷
移金属触媒の製造法 ２）担体が少なくともハロゲン化マグイシウムを含有す
るものである特許請求の範囲第１項記載の方法[Claims] 1) A supported transition metal catalyst is obtained by contacting a carrier with a liquid transition metal compound in a slurry state, and then repeatedly washing unsupported free transition metal compounds with a liquid hydrocarbon compound. The method is characterized in that a recovered liquid hydrocarbon compound containing a transition metal compound in a smaller proportion than the transition metal compound-containing liquid hydrocarbon compound before cleaning is used as the cleaning liquid hydrocarbon compound. Method for producing a supported transition metal catalyst 2) The method according to claim 1, wherein the support contains at least magisium halide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58135101A JPS6028404A (en) | 1983-07-26 | 1983-07-26 | Production of transition metal catalyst supported by carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58135101A JPS6028404A (en) | 1983-07-26 | 1983-07-26 | Production of transition metal catalyst supported by carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6028404A true JPS6028404A (en) | 1985-02-13 |
| JPH0455204B2 JPH0455204B2 (en) | 1992-09-02 |
Family
ID=15143859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58135101A Granted JPS6028404A (en) | 1983-07-26 | 1983-07-26 | Production of transition metal catalyst supported by carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6028404A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441985A (en) * | 1977-09-09 | 1979-04-03 | Mitsui Petrochem Ind Ltd | Polymerization or copolymerization of olefin |
| JPS56811A (en) * | 1979-06-18 | 1981-01-07 | Mitsui Petrochem Ind Ltd | Preparation of olefin polymer or copolymer |
| JPS5611908A (en) * | 1979-07-11 | 1981-02-05 | Mitsui Petrochem Ind Ltd | Preparation of olefin polymer |
| JPS5667311A (en) * | 1979-11-08 | 1981-06-06 | Mitsui Petrochem Ind Ltd | Production of carrier for olefin polymerization catalyst |
-
1983
- 1983-07-26 JP JP58135101A patent/JPS6028404A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441985A (en) * | 1977-09-09 | 1979-04-03 | Mitsui Petrochem Ind Ltd | Polymerization or copolymerization of olefin |
| JPS56811A (en) * | 1979-06-18 | 1981-01-07 | Mitsui Petrochem Ind Ltd | Preparation of olefin polymer or copolymer |
| JPS5611908A (en) * | 1979-07-11 | 1981-02-05 | Mitsui Petrochem Ind Ltd | Preparation of olefin polymer |
| JPS5667311A (en) * | 1979-11-08 | 1981-06-06 | Mitsui Petrochem Ind Ltd | Production of carrier for olefin polymerization catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0455204B2 (en) | 1992-09-02 |
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