JPH072819A - Purification of glycidol - Google Patents
Purification of glycidolInfo
- Publication number
- JPH072819A JPH072819A JP14751393A JP14751393A JPH072819A JP H072819 A JPH072819 A JP H072819A JP 14751393 A JP14751393 A JP 14751393A JP 14751393 A JP14751393 A JP 14751393A JP H072819 A JPH072819 A JP H072819A
- Authority
- JP
- Japan
- Prior art keywords
- glycidol
- side cut
- boiling point
- cut line
- tower
- 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
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- Epoxy Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、グリシド−ルの精製方
法に関するものである。グリシド−ルは、グリシジルエ
ーテル、グリシジルエステル、グリセリンエーテル、グ
リセリンエステル、アミノプロパンジオール等、医薬
品、塗料、半導体用UV硬化剤の中間体の原料として有
用な物質である。FIELD OF THE INVENTION The present invention relates to a method for purifying glycidyl. Glycidole is a substance useful as a raw material for intermediates of glycidyl ether, glycidyl ester, glycerin ether, glycerin ester, aminopropanediol, etc. for pharmaceuticals, paints, and UV curing agents for semiconductors.
【0002】[0002]
【従来の技術】従来、アリルアルコ−ルおよび過酸化水
素を反応させて得られるグリシドールの精製は以下のよ
うに行なわれていた。すなわち、未反応のアリルアルコ
ール、水の一部およびアクロレイン等の反応によって副
生した低沸物質を除き、さらに、触媒および、副生する
グリセリンおよびグリセリンアリルエーテル等の高沸点
成分を除く。次いで、通常の、塔頂において適当な還流
比をとる蒸留が行われ、サイドカットにより製品グリシ
ドールが得られる。2. Description of the Related Art Conventionally, purification of glycidol obtained by reacting allyl alcohol with hydrogen peroxide has been carried out as follows. That is, unreacted allyl alcohol, a part of water and low boiling substances by-produced by the reaction such as acrolein are removed, and further catalysts and high-boiling components such as glycerin and glycerin allyl ether produced as by-products are removed. Then, ordinary distillation is carried out at the top of the column with an appropriate reflux ratio, and the product glycidol is obtained by side-cutting.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、公知の
製造プロセス(例えば特公昭60−55512号公報)
に基づいてグリシドールの製造を行ったところ、製品中
へのアクリル酸やグリシドアルデヒド、さらには、グリ
セリンやグリシドグリセリンエーテルなどの混入率が高
く、グリシドールの熱安定性は良好であるとは言えなか
った。However, a known manufacturing process (for example, Japanese Patent Publication No. 60-55512).
When glycidol was produced based on, glycidol and glycidaldehyde in the product, and further, the mixing ratio of glycerin and glycidglycerin ether is high, and it can be said that the thermal stability of glycidol is good. There wasn't.
【0004】すなわち、前述の実験で得られたグリシド
ールは純度99.3%程度であり、このグリシドールを
25℃付近の温度で貯蔵した場合、グリシドール含有量
の低下は月当り約2%であった。That is, the glycidol obtained in the above experiment had a purity of about 99.3%, and when this glycidol was stored at a temperature near 25 ° C., the decrease in the glycidol content was about 2% per month. .
【0005】[0005]
【発明の目的】本発明の目的は、高純度かつ熱安定性の
優れたグリシドール、さらには、品質の優れたグリシド
ール誘導体を与えることが可能なグリシドールを得るた
めの精製方法を提供することにある。OBJECT OF THE INVENTION It is an object of the present invention to provide a purification method for obtaining glycidol, which is highly pure and has excellent thermal stability, and further, a glycidol derivative having excellent quality. .
【0006】[0006]
【課題を解決するための手段】本発明は、鋭意検討を重
ねた結果、前述の問題点を解決すべくなされたものであ
り、高純度かつ熱安定性の優れたグリシドールを得るこ
とのできるグリシドールの精製方法を見出だしたことに
基づいている。As a result of intensive studies, the present invention has been made to solve the above-mentioned problems, and it is possible to obtain glycidol having high purity and excellent thermal stability. It is based on the finding of the purification method of.
【0007】すなわち、本発明は、「触媒の存在下、ア
リルアルコ−ルおよび過酸化水素を反応させて得られる
グリシドールを含む反応粗液より脱低沸、脱高沸処理し
た粗グリシドールをサイドカットラインを有する蒸留塔
において精製する際、該サイドカットラインに少なくと
も理論段2段を有するサイドカット塔を設置することを
特徴とするグリシドールの精製方法」である。That is, the present invention is directed to "a crude glycidol which has been subjected to a low boiling point and a high boiling point-treated crude glycidol from a reaction crude liquid containing glycidol obtained by reacting allyl alcohol and hydrogen peroxide in the presence of a catalyst. The method for purifying glycidol is characterized in that a side-cut column having at least two theoretical plates is installed in the side-cut line when purifying in a distillation column having ".
【0008】通常グリシドールの製造は、反応工程、脱
低沸工程、脱高沸工程、製品化工程の順で行われるが、
ここでそれ以前の工程とは反応工程、脱低沸工程、脱高
沸工程の1つまたは複数を指す。このプロセスにおい
て、製品中のアクリル酸やグリシドアルデヒド、さらに
は、グリセリンやグリシドグリセリンエーテルなどの混
入率を下げるため製品塔の段数を増やすと圧力損失が大
きくなる。Glycidol is usually produced in the order of reaction step, low boiling point removal step, high boiling point removal step, and commercialization step.
Here, the step before that refers to one or more of a reaction step, a deboiling step and a deboiling step. In this process, when the number of stages of the product column is increased in order to reduce the mixing ratio of acrylic acid and glycidaldehyde in the product, and further, glycerin and glycidglycerin ether, the pressure loss increases.
【0009】すなわち、塔底の温度が高くなり、グリシ
ドールの高沸点物への変化が促進され、好ましくない。That is, the temperature at the bottom of the column becomes high and the conversion of glycidol to a high boiling point substance is promoted, which is not preferable.
【0010】また、製品塔の段数増と低圧力損失を満た
すことのできる規則充填物塔を用いれば、目的は達成で
きるが、規則充填物は高価であり経済的に見て好ましく
ない。 本発明のポイントは、製品中のアクリル酸やグ
リシドアルデヒド、さらには、グリセリンやグリシドグ
リセリンエーテルなどの混入率を下げるため、サイドカ
ットラインを有する蒸留塔の該サイドカットラインに少
なくとも理論段2段を有するサイドカット塔を設置した
ことにある。The object can be achieved by using an ordered packing column capable of satisfying an increase in the number of stages of the product tower and a low pressure loss, but the ordered packing is expensive and economically unfavorable. The point of the present invention is to reduce the mixing ratio of acrylic acid, glycidaldehyde, and further glycerin, glycidglycerin ether, etc. in the product, so that at least theoretical plate 2 is provided in the side cut line of the distillation column having the side cut line. It is the installation of a side-cut tower with steps.
【0011】理論段2段未満ではグリシドール純度が9
9.7%に到達しない。Below 2 theoretical plates, the purity of glycidol is 9
Does not reach 9.7%.
【0012】また、理論段の上限に制限はないが、設備
経済性、圧力損失の観点から5段程度で充分である。な
お、理論段1段は通常、実段2〜3に相当する。The upper limit of the theoretical plate is not limited, but from the viewpoint of facility economy and pressure loss, about 5 plates is sufficient. It should be noted that the theoretical stage 1 usually corresponds to the actual stage 2 to 3.
【0013】粗グリシドールを製品化塔へフィードする
位置はサイドカットライン抜き出し位置より上部で、か
つ、製品化塔の全段数の下から45%〜75%程度にする必
要がある。The position for feeding the crude glycidol to the productization tower must be above the side cut line withdrawal position and about 45% to 75% from the bottom of the total number of stages of the productization tower.
【0014】また、サイドカットラインからの抜き出し
液は通常、サイドカット塔の全段数の下から0%〜20%
程度にする必要がある。位置がサイドカット塔の下部か
ら20%以上では低沸物の混入量が多くなり、好ましくな
い。Further, the liquid extracted from the side cut line is usually 0% to 20% from the bottom of the total number of side cut towers.
Need to be about. If the position is 20% or more from the lower part of the side-cut column, the amount of low-boiling substances will increase, which is not preferable.
【0015】本発明における具体的なプロセスの1例を
ブロック図で示した添付の図1に基づいて説明する。こ
こでは製品化工程を示している。An example of a specific process according to the present invention will be described with reference to the attached FIG. 1 which is a block diagram. Here, the commercialization process is shown.
【0016】図1において、1−1から6−6は各機器
を結ぶ導管、9/9は薄膜式蒸発器である。In FIG. 1, 1-1 to 6-6 are conduits connecting the respective devices, and 9/9 is a thin film type evaporator.
【0017】7/7は製品化工程における蒸留塔、8/
8が本発明のポイントであるサイドカットラインに設置
したサイドカット塔、10−10、11−11は熱交換
器である。製品化工程の蒸留塔7/7における還流比は
2〜3程度にすることが好ましい。この還流比が3以上
ではエネルギ−の損失が多くなるので、好ましくない。
逆に、2以下にすると低沸物の混入量が多くなり、好
ましくない。7/7 is a distillation column in the production process, 8 /
8 is a side cut tower installed on the side cut line which is the point of the present invention, 10-10 and 11-11 are heat exchangers. The reflux ratio in the distillation column 7/7 in the commercialization process is preferably about 2-3. If the reflux ratio is 3 or more, energy loss increases, which is not preferable.
On the other hand, when it is 2 or less, the amount of low-boiling substances mixed in increases, which is not preferable.
【0018】脱触媒処理された液1−1は7−7の製品
化塔へフィードされ、グリシドールおよび微量の高沸成
分を含む気化物は3−3を通り、サイドカット塔8/8
にフィードされる。製品グリシドールは11−11の熱
交換器を経て5−5より得られる。サイドカット塔8/
8における還流比は0.5〜0.8程度にすることが好まし
い。この還流比が0.8以上ではエネルギ−効率が悪いの
で好ましくない。逆に、0.5以下にすると製品中のハイ
ボイラ−量が多くなり、好ましくない。The decatalyzed liquid 1-1 is fed to the productization tower 7-7, the vaporized product containing glycidol and a trace amount of high boiling components passes through 3-3, and the side cut tower 8/8.
Will be fed to. The product glycidol is obtained from 5-5 via a 11-11 heat exchanger. Side cut tower 8 /
The reflux ratio in 8 is preferably about 0.5 to 0.8. If the reflux ratio is 0.8 or more, the energy efficiency is poor, which is not preferable. On the contrary, if it is less than 0.5, the amount of high boiler in the product increases, which is not preferable.
【0019】微量の低沸成分は水とともに10−10の
熱交換器を経て2−2より系外へ抜かれる。製品化塔の
缶出液は6−6を通って系外へ抜かれる。A small amount of low boiling point component is withdrawn from the system from 2-2 through a heat exchanger of 10-10 together with water. The bottoms of the productization tower is discharged from the system through 6-6.
【0020】サイドカット塔8/8の缶出液は4−4を
通って7−7の製品化塔へ戻される。 各機器を結ぶ導
管1−1から6−6を流れる物質の組成は概略以下の通
りである。(重量%) 1−1:グリシドール 50〜65% 水 30〜45% 低沸点成分 0.2〜 0.6% 高沸点成分 0.3〜 0.7% 2−2:グリシド−ル 1〜7% 水 92〜98% その他 0.5〜1.5% 3−3:グリシド−ル 98.5〜99.3% 高沸点成分 95〜98% 4−4:グリシド−ル 95〜98% 高沸点成分 2〜5% 5−5:グリシド−ル 99.6〜99.8% 高沸点成分 0.2〜0.4% 6−6:グリシド−ル 50〜80% 高沸点成分 20〜50%ここで低沸点成分とはア
リルアルコール、グリシドアルデヒドなどを示す。The bottom liquid of the side cut tower 8/8 is returned to the product production tower of 7-7 through 4-4. The composition of the substance flowing through the conduits 1-1 to 6-6 connecting the respective devices is roughly as follows. (Wt%) 1-1: Glycidol 50 to 65% Water 30 to 45% Low boiling point component 0.2 to 0.6% High boiling point component 0.3 to 0.7% 2-2: Glycidyl 1 to 7% Water 92 to 98% Other 0.5 -1.5% 3-3: Glycidole 98.5-99.3% High-boiling point component 95-98% 4-4: Glycidol 95-98% High-boiling point component 2-5% 5-5: Glycidol 99.6-99.8% High boiling point component 0.2 to 0.4% 6-6: Glycidole 50 to 80% High boiling point component 20 to 50% Here, the low boiling point component means allyl alcohol, glycidaldehyde and the like.
【0021】ここで高沸点成分とはグリセリン、グリセ
リンアリルエ−テル、グリセリン多量体などを示す。Here, the high boiling point component means glycerin, glycerin allyl ether, glycerin multimer and the like.
【0022】この発明によるグリシド−ルの純度および
熱安定性向上に対する効果を、以下の実施例によりさら
に詳しく説明する。The effect of the present invention on improving the purity and thermal stability of glycidyl will be described in more detail with reference to the following examples.
【0023】[0023]
【実施例1】反応後、脱低沸処理、脱高沸処理した液6
75.9Kg/時間(グリシド−ル濃度59.6重量
%)を図1の1−1よりサイドカットライン3−3に理
論段2段(実段5段)を有するサイドカット塔8−8を
設置した製品化塔7−7へフィ−ドした。[Example 1] Liquid 6 that had been subjected to a low boiling point removal process and a high boiling point removal process after the reaction
75.9 kg / hour (glycidyl concentration 59.6% by weight) was used in 1-1 of FIG. 1 to the side cut line 3-3 in the side cut column 8-8 having two theoretical plates (five actual plates). It was fed to the installed commercialization tower 7-7.
【0024】その結果5−5より350.2g/時間
(グリシド−ル濃度99.7重量%)で製品グリシド−
ルが得られた。As a result, the product glycidin was obtained from 5-5 at 350.2 g / hour (glycidyl concentration 99.7% by weight).
I got Le.
【0025】一貫収率は75.5%であった。The consistent yield was 75.5%.
【0026】このグリシドールを25℃で貯蔵した場
合、グリシドール含有量の低下は月当り約1.3%であ
った。When this glycidol was stored at 25 ° C., the reduction in glycidol content was about 1.3% per month.
【0027】[0027]
【比較例1】サイドカットライン3−3に理論段1.2段
(実段3段)を有するサイドカット塔8−8を設置した
製品化塔7−7へフィ−ドした以外は実施例1と同様の
条件で運転した。その結果5−5より351.0g/時
間(グリシド−ル濃度99.5重量%)で製品グリシド
−ルが得られた。[Comparative Example 1] As Example 1 except that the side cut line 3-3 was fed to a commercialization tower 7-7 in which a side cut tower 8-8 having 1.2 theoretical plates (3 actual plates) was installed. It operated under similar conditions. As a result, the product glycidyl was obtained from 5-5 at a rate of 351.0 g / hour (glycidyl concentration 99.5% by weight).
【0028】このグリシドールを25℃で貯蔵した場
合、グリシドール含有量の低下は月当り約1.7%であ
った。When this glycidol was stored at 25 ° C., the reduction in glycidol content was about 1.7% per month.
【0029】[0029]
【比較例2】製品化工程は図1よりサイドカット塔を取
り除き、製品化塔よりのサイドカットで製品を得る装置
により実験を行った。それ以前の工程は実施例1と同様
にして行った。すなわち、反応後、脱低沸処理、脱高沸
処理した液675.9Kg/時間(グリシド−ル濃度5
9.6重量%)%)を製品化塔へフィ−ドした。[Comparative Example 2] In the commercialization process, an experiment was conducted by an apparatus for removing the sidecut tower from FIG. 1 and obtaining a product by sidecutting from the commercialization tower. The steps before that were performed in the same manner as in Example 1. That is, after the reaction, the solution subjected to the deboiling treatment and the deboiling treatment 675.9 Kg / hour (glycidyl concentration 5
9.6% by weight) was fed to the commercialization tower.
【0030】その結果353.2Kg/時間(グリシド
−ル濃度99.3重量%)で製品グリシド−ルが得られ
た。As a result, the product glycidyl was obtained at 353.2 Kg / hour (glycidyl concentration 99.3% by weight).
【0031】一貫収率は75.8%であった。このグリ
シドールを25℃で貯蔵した場合、グリシドール含有量
の低下は月当り約2%であった。The consistent yield was 75.8%. When this glycidol was stored at 25 ° C, the reduction in glycidol content was about 2% per month.
【0032】[0032]
【発明の効果】触媒の存在化、アリルアルコ−ルおよび
過酸化水素を反応させて得られるグリシドールを含む反
応粗液より脱低沸、脱高沸処理した粗グリシドールをサ
イドカットラインを有する蒸留塔において精製する際、
該サイドカットラインに少なくとも理論段2段を有する
サイドカット塔を設置することにより高純度かつ熱安定
性に優れた品質のよいグリシド−ルを製造することが可
能になった。(以下余白)INDUSTRIAL APPLICABILITY In a distillation column having a side cut line, crude glycidol that has been subjected to a low boiling point and a high boiling point treatment from a reaction crude liquid containing glycidol obtained by reacting a catalyst with allyl alcohol and hydrogen peroxide is used. When purifying
By installing a side-cut column having at least two theoretical plates in the side-cut line, it became possible to produce high-quality glycidol having high purity and excellent thermal stability. (Below margin)
【図1】図1は本発明の方法を実施する具体的なプロセ
スの1実施態様を示したブロック図である。FIG. 1 is a block diagram showing one embodiment of a specific process for carrying out the method of the present invention.
1−1〜6−6:各機器を結ぶ導管 7/7:製品化工程における蒸留塔 8/8:サイドカットラインに設置したサイドカット塔 9/9:薄膜式蒸発器 10−10:熱交換器 11−11:熱交換器 1-1 to 6-6: Conduit connecting each equipment 7/7: Distillation tower in commercialization process 8/8: Side cut tower installed on side cut line 9/9: Thin film evaporator 10-10: Heat exchange Vessel 11-11: Heat exchanger
Claims (1)
過酸化水素を反応させて得られるグリシドールを含む反
応粗液より脱低沸、脱高沸処理した粗グリシドールをサ
イドカットラインを有する蒸留塔において精製する際、
該サイドカットラインに少なくとも理論段2段を有する
サイドカット塔を設置することを特徴とするグリシドー
ルの精製方法。1. A distillation column having a side cut line, wherein crude glycidol which has been subjected to low boiling point and high boiling point removal from a reaction crude liquid containing glycidol obtained by reacting allyl alcohol and hydrogen peroxide in the presence of a catalyst is used. When purifying
A method for purifying glycidol, characterized in that a side-cut column having at least two theoretical plates is installed in the side-cut line.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14751393A JP3247770B2 (en) | 1993-06-18 | 1993-06-18 | Method for purifying glycidol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14751393A JP3247770B2 (en) | 1993-06-18 | 1993-06-18 | Method for purifying glycidol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH072819A true JPH072819A (en) | 1995-01-06 |
JP3247770B2 JP3247770B2 (en) | 2002-01-21 |
Family
ID=15432046
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14751393A Expired - Fee Related JP3247770B2 (en) | 1993-06-18 | 1993-06-18 | Method for purifying glycidol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3247770B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001031600A (en) * | 1999-07-14 | 2001-02-06 | Nippon Shokubai Co Ltd | Production of highly pure monoethylene glycol |
US6783853B2 (en) | 2001-09-28 | 2004-08-31 | Invista North America S.A.R.L. | Hetero-composite yarn, fabrics thereof and methods of making |
-
1993
- 1993-06-18 JP JP14751393A patent/JP3247770B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001031600A (en) * | 1999-07-14 | 2001-02-06 | Nippon Shokubai Co Ltd | Production of highly pure monoethylene glycol |
US6783853B2 (en) | 2001-09-28 | 2004-08-31 | Invista North America S.A.R.L. | Hetero-composite yarn, fabrics thereof and methods of making |
Also Published As
Publication number | Publication date |
---|---|
JP3247770B2 (en) | 2002-01-21 |
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