JP2860055B2 - Method for removing hydrophobic organic solvent from aqueous solution after reaction for production of trioxane - Google Patents
Method for removing hydrophobic organic solvent from aqueous solution after reaction for production of trioxaneInfo
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- JP2860055B2 JP2860055B2 JP15998694A JP15998694A JP2860055B2 JP 2860055 B2 JP2860055 B2 JP 2860055B2 JP 15998694 A JP15998694 A JP 15998694A JP 15998694 A JP15998694 A JP 15998694A JP 2860055 B2 JP2860055 B2 JP 2860055B2
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- Prior art keywords
- aqueous solution
- organic solvent
- hydrophobic organic
- reaction
- separation
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、ホルムアルデヒド水溶
液の加熱により得られるトリオキサンの分離に際し、ト
リオキサンを含む疎水性有機溶剤溶液を原料として蒸留
塔に供給し、塔頂部より疎水性有機溶剤を留出させ、塔
底よりトリオキサンを取り出す、トリオキサンの連続蒸
留分離方法に於て、副生する、ホルムアルデヒド・メタ
ノ−ルと疎水性有機溶剤とを含む塔頂からの「反応後水
溶液（以後、”反応後水溶液”という）」を別の分離塔
に導き、該分離塔一塔で効率良く、”反応後水溶液”か
ら、疎水性有機溶剤を除去する方法を提供する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for separating trioxane obtained by heating an aqueous formaldehyde solution by supplying a hydrophobic organic solvent solution containing trioxane as a raw material to a distillation column and distilling the hydrophobic organic solvent from the top of the column. Then, trioxane is removed from the bottom of the column. In the continuous distillation and separation method of trioxane, an aqueous solution after the reaction (hereinafter, referred to as “the reaction after the reaction”) from the top of the column containing formaldehyde methanol and a hydrophobic organic solvent by-produced. The present invention provides a method for efficiently removing a hydrophobic organic solvent from an "aqueous solution after a reaction" by introducing the aqueous solution (hereinafter referred to as ")" to another separation tower and efficiently using one of the separation towers.
【０００２】[0002]
【従来の技術】ホルムアルデヒド水溶液の加熱により得
られるトリオキサンの分離方法としては、抽出蒸留法
（特公昭４０−８５４５号公報、特公昭４２−８４０４
１号公報、特公昭６４−１０５１３号公報、特公平５−
２１６０１号公報）が用いられている。これらは抽出溶
剤として、例えばベンゼン・クロルベンゼン・ジクロロ
メタンなどの疎水性有機溶剤を用いている。2. Description of the Related Art Extraction distillation (JP-B-40-8545, JP-B-42-8404) is known as a method for separating trioxane obtained by heating an aqueous formaldehyde solution.
No. 1, Japanese Patent Publication No. Sho 64-10513,
No. 21601). These use a hydrophobic organic solvent such as benzene / chlorobenzene / dichloromethane as an extraction solvent.
【０００３】トリオキサンを含む疎水性有機溶剤を原料
として、抽出蒸留法でトリオキサンと疎水性有機溶剤を
分離した時に副生する、ホルムアルデヒド・メタノ−ル
・メチラ−ル・ギ酸メチル及び疎水性有機溶剤とを含む
塔頂の反応後水溶液から、疎水性有機溶剤を除去する方
法について、有効な技術の確立は知られていない。[0003] Using a hydrophobic organic solvent containing trioxane as a raw material, formaldehyde, methanol, methylal, methyl formate and a hydrophobic organic solvent are by-produced when trioxane and a hydrophobic organic solvent are separated by extractive distillation. No effective technique has been established for the method of removing the hydrophobic organic solvent from the aqueous solution after the reaction at the top of the column.
【０００４】[0004]
【発明が解決しようとする課題】ホルムアルデヒド水溶
液の加熱により得られるトリオキサンの製造に際し、塔
頂部のホルムアルデヒド・メタノ−ルと、疎水性有機溶
剤とを含む反応後水溶液より、疎水性有機溶剤を除去す
る為には、一般的には蒸留塔を用いて精留する方法が行
われる。しかし、この様な方法では、該水溶液に含まれ
るホルムアルデヒド・メタノ−ルなどの、疎水性有機溶
剤を分離する事は極めて困難である。In the production of trioxane obtained by heating an aqueous formaldehyde solution, the hydrophobic organic solvent is removed from the aqueous solution after the reaction containing the formaldehyde methanol at the top of the tower and a hydrophobic organic solvent. For this purpose, a rectification method using a distillation column is generally used. However, in such a method, it is extremely difficult to separate a hydrophobic organic solvent such as formaldehyde / methanol contained in the aqueous solution.
【０００５】即ち、それは、各成分の沸点が約−１９〜
１００℃と広範囲である為であって、例えば、ホルムア
ルデヒド（沸点−１９．３℃／７６０ｍｍＨｇ）、メタ
ノ−ル（沸点６４．５℃／７６０ｍｍＨｇ）、水は、沸
点１００℃／７６０ｍｍＨｇである。もし、疎水性有機
溶剤としてベンゼンを用いるとすれば、ベンゼンは、沸
点８０．１℃／７６０ｍｍＨｇである。That is, the boiling point of each component is about -19 to
The range is as wide as 100 ° C., for example, formaldehyde (boiling point: 19.3 ° C./760 mmHg), methanol (boiling point: 64.5 ° C./760 mmHg), and water have a boiling point of 100 ° C./760 mmHg. If benzene is used as the hydrophobic organic solvent, benzene has a boiling point of 80.1 ° C./760 mmHg.
【０００６】従って、これらの混合水溶液から、ベンゼ
ンを分離する為には、相当高い段数の蒸留塔を要し、若
しくは、二塔の蒸留塔を要し、時として、脱気工程・分
離層の工程も要する。更に蒸留塔の運転には、多大な電
力・蒸気を要する他、温度・圧力制御などの為、複雑な
操作を伴い、工業生産を考えると、経済的に不満足なと
ころがある。そこで、一塔による簡易な除去方法の確立
が強く望まれた。Therefore, in order to separate benzene from these mixed aqueous solutions, a considerably high number of distillation columns or two distillation columns are required, and sometimes a degassing step / separation layer is required. A process is also required. Furthermore, the operation of the distillation column requires a large amount of electric power and steam, and requires complicated operations for controlling temperature and pressure, and is economically unsatisfactory when considering industrial production. Therefore, establishment of a simple removal method using one tower was strongly desired.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の問
題点を考慮し、鋭意検討した結果、分離塔の炊き上げを
抑え、不活性ガス導入を着想、更には反応後水溶液フィ
−ドを塔底から塔頂へ変更する事により、分離塔の塔底
より抜き出す水溶液中の、疎水性有機溶剤の濃度が著し
く低減する事を見い出した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies in consideration of the above-mentioned problems, and as a result, have found the idea of suppressing the cooking of the separation tower, introducing an inert gas, and furthermore, considering the aqueous solution after the reaction. It was found that the concentration of the hydrophobic organic solvent in the aqueous solution withdrawn from the bottom of the separation column was significantly reduced by changing the column from the bottom to the top.
【０００８】即ち、本発明は、ホルムアルデヒド・メタ
ノ−ルと、疎水性有機溶剤とを含む反応後水溶液より、
疎水性有機溶剤を除去するにあたり、分離塔々頂付近か
ら該水溶液を供給し、分離塔々底付近から不活性ガスを
供給し、該水溶液中の疎水性有機溶剤を除去する事を特
徴とする、「未反応物及び副生物含有反応後水溶液」か
ら疎水性有機溶剤の除去を効率的に行うことに関するも
のである。[0008] That is, the present invention provides an aqueous solution comprising formaldehyde methanol and a hydrophobic organic solvent.
In removing the hydrophobic organic solvent, the aqueous solution is supplied from around the top of the separation tower, an inert gas is supplied from around the bottom of the separation tower, and the hydrophobic organic solvent in the aqueous solution is removed. , "Effective removal of a hydrophobic organic solvent from an aqueous solution containing unreacted substances and by-products".
【０００９】本発明において処理される反応後水溶液
は、ホルムアルデヒド０．１〜３０重量％、メタノ−ル
０．１〜３０重量％及び疎水性有機溶剤０．００１〜５
重量％を含む。更には、ホルムアルデヒド０．１〜３０
重量％、メタノ−ル０．１〜３０重量％、メチラ−ル
０．１〜３０重量％、ギ酸メチル０．１〜３０重量％と
疎水性有機溶剤０．００１〜５重量％とを含む反応後水
溶液に於て有効である。The post-reaction aqueous solution to be treated in the present invention comprises formaldehyde 0.1 to 30% by weight, methanol 0.1 to 30% by weight and a hydrophobic organic solvent 0.001 to 5%.
% By weight. Furthermore, formaldehyde 0.1 to 30
% By weight, 0.1 to 30% by weight of methanol, 0.1 to 30% by weight of methylal, 0.1 to 30% by weight of methyl formate and 0.001 to 5% by weight of a hydrophobic organic solvent Effective in post-aqueous solutions.
【００１０】分離塔に供給する該水溶液及び塔内温度は
１０〜１００℃、好ましくは２５〜７５℃、更に好まし
くは３５〜４５℃、塔内圧力は１００〜３０００ヘクト
パスカル、好ましくは５００〜１５００ヘクトパスカ
ル、更に好ましくは９００〜１１００ヘクトパスカル、
又、分離塔に供給する水溶液の量（Ｋｇ／時間）をＬと
し、不活性ガスの量（ＮＭ3 ／時間）をＧとすると、Ｌ
／Ｇ＝１０〜１００、好ましくは３０〜７０の範囲が望
ましい。The aqueous solution to be supplied to the separation column and the temperature in the column are 10 to 100 ° C., preferably 25 to 75 ° C., more preferably 35 to 45 ° C., and the pressure in the column is 100 to 3000 hPa, preferably 500 to 1500 hPa. , More preferably 900-1100 hPa,
When the amount (Kg / hour) of the aqueous solution supplied to the separation tower is L and the amount (NM 3 / hour) of the inert gas is G, L
/ G = 10 to 100, preferably 30 to 70.
【００１１】本発明の疎水性有機溶剤は、沸点２５〜１
５０℃／７６０ｍｍＨｇ、水に対する溶解度０．００１
〜３ｇ／１００ｇ（２０℃）である。例えば、ベンゼン
・クロロベンゼン・ジクロロメタン・トルエン・クロロ
ホルムが良いが、特に好ましい溶剤はベンゼンである。
反応後水溶液中の疎水性有機溶剤の除去は、分離塔塔頂
付近に供給する該水溶液の温度及び塔内温度を高くする
か、または分離塔塔底付近からの不活性ガスの供給量を
上げれば除去効果は向上するが、同時にホルムアルデヒ
ド・メタノ−ルの損失も大きくなり経済的でない。The hydrophobic organic solvent of the present invention has a boiling point of 25 to 1
50 ° C./760 mmHg, solubility in water 0.001
３3 g / 100 g (20 ° C.). For example, benzene / chlorobenzene / dichloromethane / toluene / chloroform is preferable, but a particularly preferred solvent is benzene.
After the reaction, the hydrophobic organic solvent in the aqueous solution can be removed by increasing the temperature of the aqueous solution supplied near the top of the separation tower and the temperature inside the column, or increasing the supply amount of the inert gas from near the bottom of the separation tower. If the removal effect is improved, the loss of formaldehyde / methanol increases at the same time, which is not economical.
【００１２】尚、分離塔に供給する不活性ガスは比熱が
小さい事から、塔内温度に与える影響は小さく、加熱・
冷却などの必要はない。又、本発明で用いる分離塔とし
ては、例えば充填塔、シ−ブトレイ塔、泡鐘塔などがあ
げられる。次に本発明における実施態様の１例を添付図
面によって説明すると、図１中符号Ｉは充填塔である。Since the inert gas supplied to the separation column has a small specific heat, the influence on the temperature inside the column is small, and
There is no need for cooling. Examples of the separation tower used in the present invention include a packed tower, a sieve tray tower, and a bubble bell tower. Next, an example of an embodiment of the present invention will be described with reference to the accompanying drawings. In FIG.
【００１３】先ず、ホルムアルデヒド・メタノ−ル・メ
チラ−ル・ギ酸メチルと、ベンゼンとを含む反応後水溶
液を充填塔Ｉに原料供給ライン１を通して供給し、２か
ら窒素ガスを供給し、塔頂３よりベンゼンを含む窒素ガ
スを排出する。この排出ガスは除害設備へ送る。又、塔
底４を通してホルムアルデヒド・メタノ−ル・メチラ−
ル・ギ酸メチルを含む脱有機溶剤後の水溶液を取り出
す。First, after the reaction, an aqueous solution containing formaldehyde, methanol, methylal, methyl formate and benzene is supplied to the packed column I through the raw material supply line 1, nitrogen gas is supplied from 2, and the top 3 Discharge nitrogen gas containing more benzene. This exhaust gas is sent to abatement equipment. Also, formaldehyde, methanol, methyla
The aqueous solution after the organic solvent containing methyl ruformate is taken out.
【００１４】充填塔Ｉに反応後水溶液を供給するに際し
ては、充填塔内に於ける該水溶液の片流れを防止する
為、充填塔内の該水溶液吹き出し口付近に分散板を設置
する。若しくは、該水溶液を均一に吹き出させる為の構
造を有する吹き出しノズルを用いる事が好ましい。又、
充填塔への充填物は、規則充填物、不規則充填物、どち
らでも良い。When supplying the aqueous solution after the reaction to the packed tower I, a dispersion plate is installed near the outlet of the aqueous solution in the packed tower in order to prevent one-sided flow of the aqueous solution in the packed tower. Alternatively, it is preferable to use a blowing nozzle having a structure for uniformly blowing the aqueous solution. or,
The packing into the packed tower may be either a structured packing or an irregular packing.
【００１５】[0015]
【実施例】以下、本発明の内容を実施例で示すが、これ
は本発明の範囲を限定するものではない。EXAMPLES The contents of the present invention will be described below by way of examples, which do not limit the scope of the present invention.
【００１６】[0016]
【実施例１】ホルムアルデヒド・メタノ−ル・メチラ−
ル・ギ酸メチルと、ベンゼンとを含む反応後水溶液は、
ホルムアルデヒド７．８重量％、メタノ−ル７．６重量
％、メチラ−ル７．６重量％、ギ酸メチル６．９重量
％、ベンゼン０．３重量％である。EXAMPLE 1 Formaldehyde / Methanol / Methyla
The aqueous solution after the reaction containing methyl ruformate and benzene,
7.8% by weight of formaldehyde, 7.6% by weight of methanol, 7.6% by weight of methylal, 6.9% by weight of methyl formate and 0.3% by weight of benzene.
【００１７】該水溶液を３２℃に保温し、図１に示す如
く、６φディクソンパッキングを充填した塔高２．０ｍ
の分離塔に、１から毎時１６．１Ｋｇ供給する。分離塔
下部２から毎時０．２８ＮＭ3 の窒素ガスを供給する。
この塔底液の分析値を表１に示した。The aqueous solution was kept at a temperature of 32 ° C., and as shown in FIG.
Is fed from 1 to 16.1 kg per hour. A nitrogen gas of 0.28 NM 3 / h is supplied from the lower part 2 of the separation tower.
The analytical values of the bottom liquid are shown in Table 1.
【００１８】[0018]
【比較例１】実施例１で使用した充填塔、及び反応後水
溶液を用い、塔底温度を９３．５℃に保ちながら、窒素
ガスの供給を断った状態で充填塔１から該水溶液を毎時
１６．１Ｋｇ供給し、環流比１０で蒸留を行った。この
塔底液の分析値を表１に示した。[Comparative Example 1] packed column used in Example 1, and an aqueous solution using a post-reaction, while maintaining the bottom temperature to 93.5 ° C., per hour the aqueous solution from the packed tower 1 while refused the supply of nitrogen gas 16.1 kg was supplied and distillation was performed at a reflux ratio of 10. The analytical values of the bottom liquid are shown in Table 1.
【００１９】[0019]
【実施例２】ホルムアルデヒド７．７重量％、メタノ−
ル１１．５重量％、メチラ−ル６．１重量％、ギ酸メチ
ル２．１重量％、ベンゼン０．３重量％を含む反応後水
溶液を４１℃に保温し、実施例１と同じ分離塔を用い、
分離塔に１から毎時１６．２Ｋｇ供給する。分離塔下部
から毎時０．２８ＮＭ3 の窒素ガスを供給する。この結
果、塔底より取り出された水溶液の分析値を表２に示し
た。Example 2 7.7% by weight of formaldehyde, methano-
After the reaction, containing 11.5% by weight of toluene, 6.1% by weight of methylal, 2.1% by weight of methyl formate, and 0.3% by weight of benzene, the aqueous solution was kept at 41 ° C., and the same separation column as in Example 1 was used. There use,
1 per hour 16.2Kg supplied to the minute Hanareto. A nitrogen gas of 0.28 NM 3 / h is supplied from the lower part of the separation tower. As a result, the analytical values of the aqueous solution taken out from the bottom of the column are shown in Table 2.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【発明の効果】トリオキサン製造における塔頂の副生物
等含有する反応後水溶液より有効成分を損失する事な
く、疎水性有機溶剤０．３％を１ＰＰＭ以下に除去出来
る。According to the present invention, 0.3% of the hydrophobic organic solvent can be removed to 1 PPM or less without losing the effective component from the aqueous solution containing by-products at the top of the column in the production of trioxane.
【図１】本発明の分離塔の模式図。FIG. 1 is a schematic view of a separation tower of the present invention.
１．反応後水溶液を、ライン１を通して供給する。 ２．窒素ガスを、ライン２を通して供給する。 ３．塔頂３よりベンゼンを含む窒素ガスを排出する。 ４．塔底４を通してホルムアルデヒド・メタノール・メ
チラール・ギ酸メチルを含む水溶液を取り出す。 ５．充填塔Ｉ。1. After the reaction, the aqueous solution is supplied through line 1. 2. Nitrogen gas is supplied through line 2. 3. Nitrogen gas containing benzene is discharged from the top 3. 4. An aqueous solution containing formaldehyde, methanol, methylal and methyl formate is taken out through the bottom 4. 5. Packing tower I.
Claims (5)
有機溶剤とを含むトリオキサン製造の反応後水溶液よ
り、疎水性有機溶剤を除去するに当り、分離塔々頂部付
近から該水溶液を供給し、分離塔々底付近から不活性ガ
スを供給することを特徴とする該水溶液中の疎水性有機
溶剤を除去する方法。1. To remove a hydrophobic organic solvent from an aqueous solution after the production of trioxane containing formaldehyde methanol and a hydrophobic organic solvent, the aqueous solution is supplied from the vicinity of the top of each of the separation columns. A method for removing a hydrophobic organic solvent in an aqueous solution, comprising supplying an inert gas from near each bottom.
０℃、分離塔内圧力が、１００〜３０００ヘクトパスカ
ルである請求項１記載の方法。2. The temperature of the aqueous solution in the separation tower is from 10 to 10.
2. The method according to claim 1, wherein the pressure in the separation column is 0 ° C. and the pressure in the separation column is 100 to 3000 hPa.
℃、分離塔内圧力が、５００〜１５００ヘクトパスカル
である請求項１記載の方法。3. The temperature of the aqueous solution in the separation column is from 25 to 75.
The method according to claim 1, wherein the temperature in the separation column is from 500 to 1500 hPa.
の量（Ｋｇ／時間）をＬとし、分離塔々底付近から供給
する不活性ガスの量（ＮＭ3 ／時間）をＧととすると、
Ｌ／Ｇ＝３０〜７０である請求項１記載の方法。4. An amount (Kg / hour) of the aqueous solution supplied from the vicinity of the top of the separation tower is L, and an amount (NM 3 / hour) of the inert gas supplied from the vicinity of the bottom of the separation tower is G. ,
The method according to claim 1, wherein L / G = 30-70.
ンである請求項１記載の方法。5. The method according to claim 1, wherein the hydrophobic organic solvent in the aqueous solution is benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15998694A JP2860055B2 (en) | 1994-07-12 | 1994-07-12 | Method for removing hydrophobic organic solvent from aqueous solution after reaction for production of trioxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15998694A JP2860055B2 (en) | 1994-07-12 | 1994-07-12 | Method for removing hydrophobic organic solvent from aqueous solution after reaction for production of trioxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0827145A JPH0827145A (en) | 1996-01-30 |
| JP2860055B2 true JP2860055B2 (en) | 1999-02-24 |
Family
ID=15705505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15998694A Expired - Lifetime JP2860055B2 (en) | 1994-07-12 | 1994-07-12 | Method for removing hydrophobic organic solvent from aqueous solution after reaction for production of trioxane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2860055B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288580B (en) * | 2013-06-17 | 2017-08-29 | 天津渤化永利化工股份有限公司 | Benzene, methanol, the method for formaldehyde in a kind of recovery metaformaldehyde device waste gas |
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1994
- 1994-07-12 JP JP15998694A patent/JP2860055B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0827145A (en) | 1996-01-30 |
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