JP2560391B2 - Fluorene production method - Google Patents
Fluorene production methodInfo
- Publication number
- JP2560391B2 JP2560391B2 JP63039620A JP3962088A JP2560391B2 JP 2560391 B2 JP2560391 B2 JP 2560391B2 JP 63039620 A JP63039620 A JP 63039620A JP 3962088 A JP3962088 A JP 3962088A JP 2560391 B2 JP2560391 B2 JP 2560391B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorene
- fraction
- crystallization
- coal tar
- weight
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Working-Up Tar And Pitch (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、フルオレンの製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing fluorene.
［従来の技術とその問題点］ 従来、コールタールからフルオレンを製造すること
は、文献上は見られるが実用上はほとんど行われていな
かった。更に、フルオレンを高純度の状態で高い収率で
かつ簡単な工程で容易に得る方法は、全くなかった。[Prior Art and its Problems] Conventionally, production of fluorene from coal tar has been seen in the literature but practically not performed. Furthermore, there has been no method for obtaining fluorene in a highly pure state with a high yield and by simple steps.
本発明は、かかる点に鑑みてなされたものであり、高
純度のフルオレンを高い収率で、しかも、極めて簡単な
工程で容易に得ることができるフルオレンの製造方法を
提供するものである。The present invention has been made in view of the above points, and provides a method for producing fluorene, which enables high-purity fluorene to be obtained at a high yield and in an extremely simple process.
［問題点を解決するための手段］ 本発明は、コールタールまたはコールタールの一部に
水添処理を施す工程と、水添処理された該コールタール
を蒸留して水添留出油を得る工程と、該水添留出油の23
0〜350℃留分に蒸留を施してフルオレン＞20WT％、アセ
ナフテン＜25WT％、ジベンゾフラン＜6WT％、アセナフ
テンWT％／ジベンゾフランWT％≠1.1のフルオレン留分
を得る工程と、該フルオレン留分に晶析を施して固相分
を得る工程と、該固相分に所定の溶剤を添加して晶析に
よりフルオレンを得る工程とを具備することを特徴とす
るフルオレンの製造方法である。[Means for Solving the Problems] The present invention provides a step of subjecting coal tar or a part of coal tar to hydrogenation, and distilling the hydrogenated coal tar to obtain a hydrogenated distillate. Process and 23 of the hydrogenated distillate
A step of subjecting a 0-350 ° C. fraction to distillation to obtain a fluorene fraction of fluorene> 20 WT%, acenaphthene <25 WT%, dibenzofuran <6 WT%, acenaphthene WT% / dibenzofuran WT% ≠ 1.1, and crystallization of the fluorene fraction A method for producing fluorene, comprising: a step of performing a precipitation to obtain a solid phase content; and a step of adding a predetermined solvent to the solid phase content to obtain fluorene by crystallization.
ここで、コールタールに施す水添処理の水素化深度
は、600〜3000SCF/BL（Standard Cubic Feet/Barrel）
に設定するのが好ましい。水素化深度が、600SCF/BLに
満たない場合は、本発明にて使用する水添留出油として
適したものが得られない。また、3000SCF/BLを越える
と、フルオレンの水素化が急激に進みフルオレンの量が
激減する。水添処理に際しては、Ni−Mo、Co−Mo、Ni−
Co−Moの何れかのような通常重質油の水添時に使用する
触媒を使用するのが好ましい。Here, the hydrogenation depth of the hydrogenation treatment applied to coal tar is 600 to 3000SCF / BL (Standard Cubic Feet / Barrel).
It is preferable to set to. If the hydrogenation depth is less than 600 SCF / BL, no suitable hydrogenated distillate used in the present invention can be obtained. Moreover, when it exceeds 3000 SCF / BL, the hydrogenation of fluorene rapidly progresses and the amount of fluorene decreases sharply. During hydrogenation, Ni-Mo, Co-Mo, Ni-
It is preferred to use the catalysts normally used during hydrogenation of heavy oils such as Co-Mo.
また、コールタールとしては、予め蒸留された軟ピッ
チ留分（280℃以上の留分のもの）を使用しても良い。Further, as the coal tar, a soft-pitch fraction (distillate having a temperature of 280 ° C. or higher) that has been distilled in advance may be used.
また、水添留出油に施す蒸留は、複数回として製造す
るフルオレンの純度を高めるのが好ましい。Further, it is preferable that the distillation applied to the hydrogenated distillate oil is performed a plurality of times to enhance the purity of fluorene produced.
また、固相分に添加する溶剤としては、溶解度パラメ
ータ７〜14.5の炭化水素系溶剤を用いるのが好ましい。
具体的には、エタノール、ｎ−ヘキサン、シクロヘキサ
ン等を挙げることができる。Further, it is preferable to use a hydrocarbon solvent having a solubility parameter of 7 to 14.5 as the solvent added to the solid phase.
Specifically, ethanol, n-hexane, cyclohexane, etc. can be mentioned.
また、固相分の晶析処理は、必要に応じて１段階以上
のものとしても良い。晶析処理時の温度は、室温〜80℃
の範囲で適宜設定するのが好ましい。Moreover, the crystallization treatment of the solid phase may be carried out in one or more steps, if necessary. The temperature during crystallization is room temperature to 80 ° C.
It is preferable to set appropriately within the range.
［作用］ 本発明にかかるフルオレンの製造方法によれば、水添
処理を施したコールタールから得られる水添留出油の23
0〜350℃留分に、更に蒸留を施してフルオレン留分を得
てこれに晶析を施してフルオレンを得るので、高純度の
フルオレンを高い収率で、しかも、極めて簡単な工程で
容易に得ることができる。[Operation] According to the method for producing fluorene according to the present invention, 23 of hydrogenated distillate obtained from hydrogenated coal tar is used.
The 0-350 ° C fraction is further distilled to obtain a fluorene fraction, and crystallization is performed to obtain fluorene. Therefore, high-purity fluorene can be obtained in a high yield and with an extremely simple process. Obtainable.
［実施例］ 以下、本発明の実施例について図面を参照して説明す
る。[Embodiment] An embodiment of the present invention will be described below with reference to the drawings.
第１図に示す如く、まず、コールタール11を蒸留12し
て得た280℃留分に水添化深度約1250SCF/BLの水添処理
を施して水添油13を得る。この水添油13に１次蒸留14を
施し230〜350℃留分15を得る。この230〜350℃留分15に
２次蒸留16を施してフルオレン留分17を得る。このフル
オレン留分17の主な組成は、フルオレン42.9重量％、ジ
ベンゾフラン5.6重量％、オクタヒドロアントラセン
（以下、OHA記す）6.9重量％、メチルジベンゾフラン−
１（以下、M.D−１と記す）5.7重量％、メチルジベンゾ
フラン−３（以下、M.D−３と記す）4.8重量％であっ
た。この固相分に22℃の晶析温度で第１段晶析18を施し
た。第１段晶析18後の主な組成は、フルオレン83.4重量
％％、ジベンゾフラン4.0重量％、OHA1.3重量％、M.D−
12.1重量％、M.D−31.2重量％であった。次いで、第１
段晶析後に溶媒としてエタノールを使用し、室温で第２
段晶析19を施した。第２段晶析19後の主な組成は、フル
オレン95.4重量％、ジベンゾフラン2.0重量％、OHA0.3
重量％、M.D−30.1重量％であった。As shown in FIG. 1, first, a 280 ° C. fraction obtained by distilling 12 coal tar 11 is subjected to a hydrogenation treatment at a hydrogenation depth of about 1250 SCF / BL to obtain hydrogenated oil 13. This hydrogenated oil 13 is subjected to primary distillation 14 to obtain a fraction 15 at 230 to 350 ° C. The 230-350 ° C. fraction 15 is subjected to secondary distillation 16 to obtain a fluorene fraction 17. The main composition of this fluorene fraction 17 is 42.9% by weight of fluorene, 5.6% by weight of dibenzofuran, 6.9% by weight of octahydroanthracene (hereinafter referred to as OHA), methyldibenzofuran-
1 (hereinafter referred to as MD-1) was 5.7% by weight and methyldibenzofuran-3 (hereinafter referred to as MD-3) was 4.8% by weight. This solid phase was subjected to first stage crystallization 18 at a crystallization temperature of 22 ° C. The main composition after the first stage crystallization 18 was fluorene 83.4% by weight, dibenzofuran 4.0% by weight, OHA 1.3% by weight, MD-
It was 12.1% by weight and MD-31.2% by weight. Then the first
After step crystallization, ethanol was used as the solvent and the second
Stage crystallization 19 was performed. After the second stage crystallization 19, the main composition was 95.4% by weight of fluorene, 2.0% by weight of dibenzofuran, 0.3% of OHA.
% By weight, MD-30.1% by weight.
なお、１次蒸留14では40−15段の蒸留塔を使用し、２
次蒸留16では10−60段の蒸留塔を使用した。これらの蒸
留塔の内容は、それぞれ下記の通りであった。In the primary distillation 14, a 40-15-stage distillation column is used.
In the next distillation 16, a 10-60 stage distillation column was used. The contents of these distillation columns were as follows.
蒸留塔の内容 （１）１次蒸留塔（40−15段） 塔径［mm］ :100 充填高さ［mm］:1600 充填物 ：下部−マクマホン6mm/上部−ヘリパッ
クNo.4 理論段数 :15 還流比 :5（３秒−開/15秒−閉） 仕込み量［Kg］：約40（塔内ホールドアップ 約1.9 ［Kg］） （２）２次蒸留塔（10−60段） 塔径［mm］ :40 充填高さ［mm］:2100 充填物 ：ヘリパックNo.2 理論段数 :60 還流比 :5（３秒−開/15秒−閉） 仕込み量［Kg］：約10（塔内ホールドアップ 約0.4 ［Kg］） このように実施例によれば、純度95.4％のフルオレン
を軟ピッチから蒸留及び晶析操作により極めて容易に製
造することができた。Contents of distillation column (1) Primary distillation column (40-15 stages) Tower diameter [mm]: 100 Packing height [mm]: 1600 Packing material: Lower-McMahon 6mm / Upper-Helipack No.4 Theoretical plate number: 15 Reflux ratio: 5 (3 sec-open / 15 sec-close) Charge [Kg]: Approximately 40 (holdup in the column is approximately 1.9 [Kg]) (2) Secondary distillation column (10-60 plates) Column diameter [ mm]: 40 Packing height [mm]: 2100 Packing: Helipack No. 2 Number of theoretical plates: 60 Reflux ratio: 5 (3 seconds-open / 15 seconds-closed) Charge amount [Kg]: Approx. 10 (holding in tower) Thus, according to the examples, fluorene having a purity of 95.4% could be extremely easily produced from soft pitch by distillation and crystallization operations.
［発明の効果］ 以上説明した如く、本発明にかかるフルオレンの製造
方法によれば、高純度のフルオレンを高い収率で、しか
も、極めて簡単な工程で容易に得ることができるもので
ある。[Effects of the Invention] As described above, according to the method for producing fluorene of the present invention, highly pure fluorene can be easily obtained with a high yield and in an extremely simple process.
第１図は、本発明の実施例を示す説明図である。 11……コールタール、12……蒸留、13……水添油、14…
…１次蒸留、15……230〜350℃留分、16……２次蒸留、
17……フルオレン留分、18……第１段晶析、19……第２
段晶析、20……フルオレン。FIG. 1 is an explanatory diagram showing an embodiment of the present invention. 11 ... coal tar, 12 ... distillation, 13 ... hydrogenated oil, 14 ...
... primary distillation, 15 ... 230-350 ° C fraction, 16 ... secondary distillation,
17 …… Fluorene fraction, 18 …… 1st stage crystallization, 19 …… 2nd
Stage crystallization, 20 ... Fluorene.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岩間 卓郎 東京都千代田区丸の内１丁目１番２号 日本鋼管株式会社内 (72)発明者 谷口 博昭 東京都千代田区丸の内１丁目１番２号 アドケムコ株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takuro Iwama 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nippon Steel Tube Co., Ltd. (72) Hiroaki Taniguchi 1-2-1 Marunouchi, Chiyoda-ku, Tokyo Adchemco Co., Ltd. In the company
Claims (2)
水添処理を施す工程と、水添処理された該コールタール
を蒸留して水添留出油を得る工程と、該水添留出油の23
0〜350℃留分に蒸留を施してフルオレン＞20WT％、アセ
ナフテン＜25WT％、ジベンゾフラン＜6WT％、アセナフ
テンWT％／ジベンゾフランWT％≠1.1のフルオレン留分
を得る工程と、該フルオレン留分に晶析を施して固相分
を得る工程と、該固相分に所定の溶剤を添加して晶析に
よりフルオレンを得る工程とを具備することを特徴とす
るフルオレンの製造方法。A step of subjecting the coal tar or a part of the coal tar to hydrogenation; a step of distilling the hydrogenated coal tar to obtain a hydrogenated distillate; Of 23
A step of subjecting a 0-350 ° C. fraction to distillation to obtain a fluorene fraction of fluorene> 20 WT%, acenaphthene <25 WT%, dibenzofuran <6 WT%, acenaphthene WT% / dibenzofuran WT% ≠ 1.1, and crystallization of the fluorene fraction A method for producing fluorene, comprising: a step of performing a precipitation to obtain a solid phase component; and a step of adding a predetermined solvent to the solid phase component to obtain fluorene by crystallization.
段階以上のものである特許請求の範囲第１項記載のフル
オレンの製造方法。2. The crystallization treatment by adding a solvent to the solid phase is carried out in one step.
The method for producing fluorene according to claim 1, which is a step or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63039620A JP2560391B2 (en) | 1988-02-24 | 1988-02-24 | Fluorene production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63039620A JP2560391B2 (en) | 1988-02-24 | 1988-02-24 | Fluorene production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01216945A JPH01216945A (en) | 1989-08-30 |
| JP2560391B2 true JP2560391B2 (en) | 1996-12-04 |
Family
ID=12558153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63039620A Expired - Lifetime JP2560391B2 (en) | 1988-02-24 | 1988-02-24 | Fluorene production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2560391B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012114144A1 (en) * | 2011-02-25 | 2012-08-30 | Litwin | Method for obtaining fluorene by crystallization from the melt |
-
1988
- 1988-02-24 JP JP63039620A patent/JP2560391B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01216945A (en) | 1989-08-30 |
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