JP4005151B2 - How to wash crude inden - Google Patents
How to wash crude inden Download PDFInfo
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- JP4005151B2 JP4005151B2 JP29119694A JP29119694A JP4005151B2 JP 4005151 B2 JP4005151 B2 JP 4005151B2 JP 29119694 A JP29119694 A JP 29119694A JP 29119694 A JP29119694 A JP 29119694A JP 4005151 B2 JP4005151 B2 JP 4005151B2
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- Prior art keywords
- washing
- indene
- water
- inden
- droplet diameter
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Description
【０００１】
【産業上の利用分野】
本発明はコ−ルタ−ル蒸留工程において得られる留分から、高純度のインデンを製造する方法に関する。詳しくは、高純度のインデンを製造する場合の分離精製工程の一つである洗浄工程に関するものである。
【０００２】
【従来の技術】
コ−ルタ−ル系軽質油を原料として高純度で高品質のインデンを得る場合、一連の工程の中で、精製工程の一つとして酸水溶液及び／またはアルカリ水溶液による薬洗工程は不可欠であり、薬洗工程を行なうことにより保存安定性や重合モノマ−として使用する場合の反応阻害性などに著しく効果があることが一般的に知られている。
【０００３】
また、薬洗後、インデン層中に溶存又は微粒として懸濁した溶剤、及びそれとともに含有され除去されるべき酸性及び／または塩基性の微量不純物が再びインデン中に逆抽出するのを防ぐため、水洗処理も上記薬洗工程に伴い不可欠な工程の一つである。さらに、水洗を行なうことにより、インデン層中の（無機）酸又は塩基がその後の蒸留や脱水工程の蒸留塔の配管、トレ−やリボイラ−に蓄積するのを防ぎ、腐食や閉塞を防止する。なお、水洗方法に関しては、特別な方法等は考えられておらず、薬洗工程の後、一般的な公知の方法により行なわれている。
【０００４】
【発明が解決しようとする課題】
しかしながら、公知の方法により水洗を行なうと、インデンを含む留分の比重が１に極めて近いため、水とインデンの全体もしくは一部がエマルジョン化してしまい、その分離のため、長時間の静置又は大型の分離槽が必要となる。さらには長時間静置したり大型の分離槽を用いても分離しない場合、インデン収率の低下をきたす。
【０００５】
本発明は上記問題点を解決し、効率良く水洗を行なう方法を提供することをその目的とする。
【０００６】
【課題を解決するための手段及び作用】
上記課題を解決すべく、鋭意研究を行なった結果、スタティクミキサ−を用いて液滴径を制御し、さらには水洗処理温度を調整することにより、水洗に伴うエマルジョンの発生を抑えられ、分離も良いことを見出し、本発明を完成するに至った。
【０００７】
すなわち、本発明は粗インデンを水洗するに際し、液滴径０．５〜１．８ｍｍで水洗することを特徴とする。
【０００８】
さらに、水洗時の温度が５０〜９５℃であることを特徴とする。
本発明において、粗インデンとは、コ−ルタ−ル蒸留からタ−ル酸等の不純物をある程度除去したインデンを含む残油である。残油中に占めるインデンの割合は特に限定しない。３０〜４０％の低濃度でも９０％以上の高濃度でも本発明の方法は適用される。なお、このコ−ルタ−ル留分からタ−ル酸を除去し、インデンを所定濃度まで濃縮する工程は公知の方法により行なわれる。
【０００９】
水洗は例えばスタティックミキサ−（ラインミキサ−とも言う）にて行なう。この時の液滴径は一般式（１）によって求められ、スタティックミキサ−の内径、総流量によって決まる。
Ｄ＝（１０００Ｆ／９ｄ2 π）-1.088×３７．５×（ｄ／１０）0.456
Ｄ：平均液滴径（ｍｍ）
ｄ：スタティックミキサ−内径（ｍｍ）
Ｆ：２液合計流量（ｌ／Ｈ）
・・・・・・・（１）
スタティックミキサ−により制御される液滴径としては、最小液滴径としては、０．５ｍｍ、好ましくは０．７ｍｍ、より好ましくは０．９ｍｍであり、これ以上細かすぎると静置分離に時間を有し、うまくいかない。また、最大液滴径としては１．８ｍｍ、好ましくは１．５ｍｍ、より好ましくは１．２ｍｍであり、これ以上大きすぎると混合が不十分で目的とする洗浄効果が得られない。
【００１０】
本発明の水洗に用いる装置としては、液滴径の大きさを制御し、液滴に非常に狭い分布を持たせることのできる装置であり、例えば、スタティックミキサ−である。
【００１１】
水洗時の温度は５０〜９５℃、望ましくは７０〜８０℃である。温度が低いとインデンと水の比重差が小さく、分離が困難となるため、また温度が高いとインデンが蒸発し、系外へ逃げてしまい、歩留りが低下するため、好ましくない。
【００１２】
さらに、水洗は１段でも効果はあるが、２段階で行う方が好ましく、更に１段目はインデン：水の流量比を２：１に、２段目は１：１にて行なうと良好である。
【００１３】
【実施例】
次に本発明の実施例を説明する。
原料にコ−ルタ−ル蒸留により、沸点範囲が１７０〜２１０℃のタ−ル酸留分をサイドカット油として抜き出し、この留分からタ−ル酸を除去したインデンを９０〜９５％含む残油を使用し、これに酸水溶液として硫酸を加え、酸洗浄し、分離槽にて酸水溶液を分離した。次いでアルカリ水溶液として苛性ソ−ダを加えアルカリ洗浄し分離槽にて分離した。次いで下記の条件で水洗を行なった。
【００１４】
酸及びアルカリ洗浄後のインデン含有残油をスタティックミキサ−にて２段階洗浄を行なった。１段目のインデン：水の流量比は２：１、２段目のインデン：水の流量比は１：１で行なった。この時の液滴径、水洗温度、スタティックミキサ−を通過する時間（接触時間）および結果を表１に示す。
【００１５】
【表１】
表１より、２段目洗浄時のＰＨは全て８と安定しており、洗浄効果は良く、インデンの歩留りも高かった。またエマルジョンの発生は最も高いもので５％と、ほとんど認められなかった。
【００１７】
（参考例）
液滴径、水洗温度を変えた以外は実施例と同じ条件で水洗を行なった。液滴径、水洗温度、接触時間および結果を表２に示す。
【００１８】
【表２】
表２より液滴径０．３５ｍｍ、１．０ｍｍの場合、実施例と比較し、歩留りは低く、エマルジョン発生率も高かった。液滴径２．０ｍｍの場合、液滴径が大きい分、油水分離が良く、実施例と比較し、歩留りの低下はなかったものの、２段目洗浄時のＰＨは１１と実施例のＰＨ８に比べ高く、洗浄効果は悪かった。
【００２０】
【発明の効果】
本発明によれば、
１）エマルジョンの発生が防止でき、インデンの回収歩留りが向上する。
２）静置分離に長時間要したり、分解のため静置分離槽を大型化する必要もなく、効率よく水洗処理が行なえる。
３）さらに水洗処理に伴う排水量が最小限に抑えられ、廃水処理費用の削減が図れる。[0001]
[Industrial application fields]
The present invention relates to a method for producing high-purity indene from a fraction obtained in a coal distillation process. Specifically, the present invention relates to a washing process which is one of the separation and purification processes when producing high-purity indene.
[0002]
[Prior art]
In the case of obtaining high-purity and high-quality indene using cold tar light oil as a raw material, a chemical washing step with an aqueous acid solution and / or an alkaline aqueous solution is indispensable as one of the purification steps in the series of steps It is generally known that the chemical washing step is remarkably effective in storage stability and reaction inhibition when used as a polymerization monomer.
[0003]
In addition, to prevent the solvent dissolved in the indene layer or suspended as fine particles after the chemical washing, and the acidic and / or basic trace impurities to be removed together with it from being back-extracted into the indene again, Washing with water is one of the indispensable processes along with the chemical washing process. Further, by washing with water, the (inorganic) acid or base in the indene layer is prevented from accumulating in the distillation column piping, tray or reboiler in the subsequent distillation or dehydration process, and corrosion and blockage are prevented. In addition, regarding the water washing method, the special method etc. are not considered, but after the chemical washing process, it is performed by the general well-known method.
[0004]
[Problems to be solved by the invention]
However, when washing with water by a known method, the specific gravity of the fraction containing indene is very close to 1, so that the whole or a part of water and indene is emulsified, and for the separation, A large separation tank is required. Furthermore, if it is not allowed to stand for a long time or using a large separation tank, the indene yield is lowered.
[0005]
The object of the present invention is to solve the above-mentioned problems and to provide a method for efficiently washing with water.
[0006]
[Means and Actions for Solving the Problems]
As a result of diligent research to solve the above problems, by controlling the droplet size using a static mixer and further adjusting the washing temperature, it is possible to suppress the generation of emulsion due to washing and separation. As a result, the present invention has been completed.
[0007]
That is, the present invention is characterized in that when the crude indene is washed with water, it is washed with a droplet diameter of 0.5 to 1.8 mm.
[0008]
Furthermore, the temperature at the time of water washing is 50-95 degreeC, It is characterized by the above-mentioned.
In the present invention, crude indene is a residual oil containing indene from which impurities such as taric acid have been removed to some extent from cold distillation. The proportion of indene in the residual oil is not particularly limited. The method of the present invention can be applied at a low concentration of 30 to 40% or a high concentration of 90% or more. The step of removing taric acid from this coal cut and concentrating indene to a predetermined concentration is carried out by a known method.
[0009]
Washing with water is performed by, for example, a static mixer (also referred to as a line mixer). The droplet diameter at this time is determined by the general formula (1) and is determined by the inner diameter of the static mixer and the total flow rate.
D = (1000F / 9d 2 π) −1.088 × 37.5 × (d / 10) 0.456
D: Average droplet diameter (mm)
d: Static mixer—inner diameter (mm)
F: Total flow rate of two liquids (l / H)
・ ・ ・ ・ ・ ・ ・ (1)
As the droplet diameter controlled by the static mixer, the minimum droplet diameter is 0.5 mm, preferably 0.7 mm, more preferably 0.9 mm. I have and it doesn't work. The maximum droplet diameter is 1.8 mm, preferably 1.5 mm, and more preferably 1.2 mm. If it is too large, mixing is insufficient and the intended cleaning effect cannot be obtained.
[0010]
The apparatus used for the water washing of the present invention is an apparatus capable of controlling the size of the droplet diameter and giving the droplet a very narrow distribution, for example, a static mixer.
[0011]
The temperature at the time of washing with water is 50 to 95 ° C, desirably 70 to 80 ° C. If the temperature is low, the difference in specific gravity between indene and water is small and separation is difficult, and if the temperature is high, indene evaporates and escapes from the system, resulting in a decrease in yield.
[0012]
Further, although washing with water is effective even with one stage, it is preferable to carry out with two stages, and it is better to carry out the inden: water flow ratio at 2: 1 in the first stage and 1: 1 at the second stage. is there.
[0013]
【Example】
Next, examples of the present invention will be described.
A tar oil fraction having a boiling point range of 170 to 210 ° C. is extracted as a side cut oil by a coal distillation, and a residual oil containing 90 to 95% of indene from which the tar acid has been removed. The sulfuric acid was added to this as an acid aqueous solution, the acid wash was carried out, and the acid aqueous solution was isolate | separated in the separation tank. Next, caustic soda was added as an alkaline aqueous solution, washed with alkali, and separated in a separation tank. Next, washing with water was performed under the following conditions.
[0014]
The indene-containing residual oil after acid and alkali washing was washed in two stages with a static mixer. The first-stage inden: water flow ratio was 2: 1, and the second-stage inden: water flow ratio was 1: 1. Table 1 shows the droplet diameter, the washing temperature, the time for passing through the static mixer (contact time), and the results.
[0015]
[Table 1]
According to Table 1, the PH at the second stage cleaning was all stable at 8, the cleaning effect was good, and the yield of inden was high. In addition, the generation of emulsion was the highest at 5% and was hardly recognized.
[0017]
(Reference example)
Washing was performed under the same conditions as in the Examples except that the droplet diameter and the washing temperature were changed. The droplet diameter, washing temperature, contact time and results are shown in Table 2.
[0018]
[Table 2]
From Table 2, in the case of droplet diameters of 0.35 mm and 1.0 mm, the yield was low and the emulsion generation rate was high compared to the Examples. In the case of a droplet diameter of 2.0 mm, the oil-water separation is good due to the large droplet diameter, and although the yield is not reduced compared to the example, the PH at the second-stage cleaning is 11 and PH8 of the example The cleaning effect was poor.
[0020]
【The invention's effect】
According to the present invention,
1) Emulsion can be prevented and indene recovery yield is improved.
2) It does not require a long time for stationary separation, and it is not necessary to increase the size of the stationary separation tank for decomposition, so that it can be efficiently washed with water.
3) Furthermore, the amount of wastewater associated with the water washing treatment can be minimized, and wastewater treatment costs can be reduced.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29119694A JP4005151B2 (en) | 1994-11-25 | 1994-11-25 | How to wash crude inden |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29119694A JP4005151B2 (en) | 1994-11-25 | 1994-11-25 | How to wash crude inden |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08143869A JPH08143869A (en) | 1996-06-04 |
| JP4005151B2 true JP4005151B2 (en) | 2007-11-07 |
Family
ID=17765707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29119694A Expired - Lifetime JP4005151B2 (en) | 1994-11-25 | 1994-11-25 | How to wash crude inden |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4005151B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007005731A (en) * | 2005-06-27 | 2007-01-11 | Jsr Corp | Liquid for immersion exposure and method for refining thereof |
| JP5895639B2 (en) * | 2012-03-21 | 2016-03-30 | 三菱化学株式会社 | Method for producing (meth) acrylic acid ester |
-
1994
- 1994-11-25 JP JP29119694A patent/JP4005151B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08143869A (en) | 1996-06-04 |
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