JPH0440353B2 - - Google Patents
Info
- Publication number
- JPH0440353B2 JPH0440353B2 JP30858786A JP30858786A JPH0440353B2 JP H0440353 B2 JPH0440353 B2 JP H0440353B2 JP 30858786 A JP30858786 A JP 30858786A JP 30858786 A JP30858786 A JP 30858786A JP H0440353 B2 JPH0440353 B2 JP H0440353B2
- Authority
- JP
- Japan
- Prior art keywords
- trioxane
- formaldehyde
- triethylamine
- column
- aqueous solution
- 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
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 88
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 81
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 51
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000004821 distillation Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- -1 boron trifluoride compound Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 3
- 229930182556 Polyacetal Natural products 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SFXNZFATUMWBHR-UHFFFAOYSA-N 2-morpholin-4-yl-2-pyridin-3-ylacetonitrile Chemical compound C=1C=CN=CC=1C(C#N)N1CCOCC1 SFXNZFATUMWBHR-UHFFFAOYSA-N 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000003940 butylamines Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はトリオキサンの回収方法に関し、さら
に詳しくは、特に三フツ化ホウ素化合物触媒を用
いて、トリオキサンとエチレンオキシドとの共重
合体を製造する際に、得られるトリオキサン、ト
リエチルアミン、及びホルムアルデヒドを含む水
溶液より、トリオキサンを回収すると同時に、ホ
ルムアルデヒドを有効に回収する方法に関するも
のである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for recovering trioxane, and more particularly, to a method for recovering trioxane, particularly when producing a copolymer of trioxane and ethylene oxide using a boron trifluoride compound catalyst. The present invention also relates to a method for effectively recovering trioxane and formaldehyde from an aqueous solution containing trioxane, triethylamine, and formaldehyde.
トリオキサンをエチレンオキシドと酸性触媒の
存在下に共重合させると、ポリオキシメチレンコ
ポリマーが得られる。この重合物は、ポリアセタ
ール樹脂と呼ばれ、工業的に非常に有用な樹脂で
ある。この共重合反応において、反応の停止を行
なうために、反応終了点において塩基を加え、酸
性触媒を中和することが通常行なわれている。こ
の塩基としては、通常、ｎ―ブチルアミン、トリ
エチルアミン、トリブチルアミンが用いられ、ベ
ンゼンのような有機溶媒中で中和処理される。
（特公昭43−16159、同48−11357号公報）
しかしながら、これらの脂肪族アミンを使用し
て重合触媒を中和後、重合体を洗浄ろ過して得ら
れたろ液中の溶媒／アミン／未反応モノマー（ト
リオキサン）を効率良く回収分離する方法は知ら
れていない。ただ、ｎ―ブチルアミン／ベンゼ
ン／トリオキサンの３成分を蒸留回収する方法は
知られているが（特公昭48−11357号公報）、ｎ―
ブチルアミンのような第一級脂肪族アミンは、ト
リオキサンの分解より生じたホルムアルデヒドと
縮合反応物を作るために回収工程が複雑になる。
Copolymerization of trioxane with ethylene oxide in the presence of an acidic catalyst results in a polyoxymethylene copolymer. This polymer is called polyacetal resin, and is an industrially very useful resin. In this copolymerization reaction, in order to stop the reaction, a base is usually added at the end of the reaction to neutralize the acidic catalyst. As this base, n-butylamine, triethylamine, or tributylamine is usually used, and the base is neutralized in an organic solvent such as benzene.
(Japanese Patent Publication Nos. 43-16159 and 48-11357) However, after neutralizing the polymerization catalyst using these aliphatic amines, the solvent/amine/non-solvent in the filtrate obtained by washing and filtering the polymer. There is no known method for efficiently collecting and separating the reaction monomer (trioxane). However, although a method for distilling and recovering the three components n-butylamine/benzene/trioxane is known (Japanese Patent Publication No. 11357/1983),
Primary aliphatic amines such as butylamine form a condensation reaction product with formaldehyde generated from the decomposition of trioxane, which complicates the recovery process.
また、有機溶媒を用いることは、可燃性の関係
上、取り扱いの制約も大きく、工業的に好ましく
ない。 Furthermore, the use of organic solvents is industrially undesirable because of its flammability, which imposes great restrictions on handling.
本発明者らは、上記の問題点を考慮して、重合
後の酸性触媒の中和剤として低沸点のアミンを、
また、媒体として水を用いる方法について検討し
た結果、トリエチルアミン／水を含む系で、重合
触媒を中和することが望ましいことがわかつた。
しかしながら、トリエチルアミンは沸点89℃の液
体であること、また重合物から分離したトリオキ
サンは、水と70：30で91℃の共沸混合物を作るこ
とが知られている。従つて、沸点89℃のトリエチ
ルアミンと沸点91℃のトリオキサンと水との共沸
混合物を分離するには、沸点差がわずか２℃であ
り、非常に困難である。そこでこれを解決するた
め本発明者らは、トリエチルアミン、トリオキサ
ン、水より成る系よりトリエチルアミンとトリオ
キサンを蒸留分離する方法を以前提案した。（特
願昭56−62406号公報及び特願昭57−50408号公
報）
〔発明が解決しようとする問題点〕
しかしながら、重合物を分離したトリオキサン
水溶液中にはトリオキサンの分解生成物であるホ
ルムアルデヒドを相当含有しているので、これら
のトリエチルアミンとトリオキサンの分離方法に
おいてはホルムアルデヒドを焼却あるいは排水と
して処理することになり工業的に好ましくない場
合がある。そこでホルムアルデヒドを回収し再利
用することが強く望まれる。 In consideration of the above problems, the present inventors used a low boiling point amine as a neutralizing agent for the acidic catalyst after polymerization.
Furthermore, as a result of examining methods using water as a medium, it was found that it is desirable to neutralize the polymerization catalyst with a system containing triethylamine/water.
However, it is known that triethylamine is a liquid with a boiling point of 89°C, and that trioxane separated from the polymer forms an azeotrope with water at a ratio of 70:30 at 91°C. Therefore, it is extremely difficult to separate an azeotropic mixture of triethylamine, which has a boiling point of 89°C, trioxane, which has a boiling point of 91°C, and water, since the difference in boiling points is only 2°C. In order to solve this problem, the present inventors previously proposed a method for separating triethylamine and trioxane by distillation from a system consisting of triethylamine, trioxane, and water. (Japanese Patent Application No. 56-62406 and 57-50408) [Problems to be solved by the invention] However, formaldehyde, which is a decomposition product of trioxane, is contained in the trioxane aqueous solution from which the polymer is separated. Since the triethylamine and trioxane contain a considerable amount of formaldehyde, formaldehyde must be incinerated or treated as wastewater in these methods of separating triethylamine and trioxane, which may not be industrially preferable. Therefore, it is strongly desired to recover and reuse formaldehyde.
本発明者らは、このような事情のもとで、前記
発明の改良について鋭意検討した結果、第２の蒸
留塔における濃縮部よりホルムアルデヒドを含む
水溶液を抜き出すことで、第二塔へ供給された全
てのホルムアルデヒドを回収し、その上回収した
ホルムアルデヒド水溶液中にはトリエチルアミン
が殆んど含まれていないことを見い出し、この知
見に基づいて本発明の完成に至つた。
Under these circumstances, the present inventors conducted intensive studies on improving the invention, and found that by extracting an aqueous solution containing formaldehyde from the concentrating section in the second distillation column, the aqueous solution containing formaldehyde was supplied to the second column. All of the formaldehyde was recovered, and the inventors discovered that the recovered aqueous formaldehyde solution contained almost no triethylamine, and based on this finding, the present invention was completed.
すなわち本発明は、トリオキサン、トリエチル
アミン及びホルムアルデヒドを含む水溶液より、
トリオキサンを蒸留回収するにあたり、第一塔の
蒸留塔に、トリオキサン、トリエチルアミン及び
ホルムアルデヒドを含む水溶液を供給し、塔頂よ
りトリエチルアミン、トリオキサン及び水を留出
させ、塔底よりトリオキサン及びホルムアルデヒ
ドを含む水溶液を抜き出して、第２の蒸留塔に供
給し、その塔頂よりトリオキサンを回収すると共
に、該蒸留塔の濃縮部よりホルムアルデヒドを含
む水溶液を抜き出すことを特徴とするトリオキサ
ンを回収する方法を提供するものである。 That is, the present invention provides an aqueous solution containing trioxane, triethylamine, and formaldehyde.
To recover trioxane by distillation, an aqueous solution containing trioxane, triethylamine and formaldehyde is supplied to the first distillation column, triethylamine, trioxane and water are distilled out from the top of the column, and an aqueous solution containing trioxane and formaldehyde is distilled from the bottom of the column. To provide a method for recovering trioxane, which comprises extracting it, supplying it to a second distillation column, recovering trioxane from the top of the column, and extracting an aqueous solution containing formaldehyde from a concentrating section of the distillation column. be.
本発明において用いられるトリオキサン、トリ
エチルアミン及びホルムアルデヒドを含む水溶液
は、通常触媒として三フツ化ホウ素化合物を用い
て、トリオキサンとエチレンオキシドとの共重合
体を製造する際の重合反応の停止処理によつて得
られる。すなわち、この共重合反応において反応
の停止を行なうために、反応の終期にトリエチル
アミンを含む水溶液に重合物をろ過することによ
つて得られる。 The aqueous solution containing trioxane, triethylamine, and formaldehyde used in the present invention is usually obtained by using a boron trifluoride compound as a catalyst to terminate the polymerization reaction when producing a copolymer of trioxane and ethylene oxide. . That is, in order to stop the reaction in this copolymerization reaction, it can be obtained by filtering the polymer into an aqueous solution containing triethylamine at the final stage of the reaction.
水溶液中のトリオキサンの濃度は0.1〜10重量
％、トリエチルアミンの濃度は0.01〜0.5重量％、
ホルムアルデヒドの濃度は１〜３重量％の範囲が
望ましい。 The concentration of trioxane in the aqueous solution is 0.1-10% by weight, the concentration of triethylamine is 0.01-0.5% by weight,
The concentration of formaldehyde is preferably in the range of 1 to 3% by weight.
また本発明で用いる第１及び第２の蒸留塔とし
ては、例えば充填塔、シーブトレイ塔、泡鐘段塔
などが挙げられる。 Examples of the first and second distillation columns used in the present invention include a packed column, a sieve tray column, and a bubble column column.
次に、本発明における実施態様の１例を添付図
面によつて説明すると、図中符号，はそれぞ
れ第１及び第２蒸留塔、は蒸留塔の還流タン
クである。まずトリオキサン、トリエチルアミン
及びホルムアルデヒドを含む水溶液を、第１の蒸
留塔に供給段１を通して供給し、90℃に保たれ
た塔頂２よりトリエチルアミン、水及びトリオキ
サンから成る留出物を取り出す。この留出物は中
和工程へ戻される。他方、100℃に保たれた塔底
３よりトリオキサン、ホルムアルデヒドを含む水
溶液を取り出し、この塔底物を第２の蒸留塔に
供給して、91℃に保たれた塔頂４よりトリオキサ
ン及び水を含む組成物を、塔底９より水を取り出
す。また、非水溶性有機溶媒を５より還流タンク
へ供給して６より上層成分のトリオキサンを含
む有機溶媒相を取り出し、下相成分の水相は７を
通して第２蒸留塔に戻す。６より取り出された
トリオキサンを含む有機溶媒相は、別の蒸留塔へ
供給してトリオキサンを回収する。さらに第２の
蒸留塔の濃縮部８よりホルムアルデヒドを含む
水溶液を取り出しホルムアルデヒドを回収し、ポ
リアセタールの原料として再利用する。 Next, an example of an embodiment of the present invention will be described with reference to the accompanying drawings. In the drawings, reference numerals indicate first and second distillation columns, respectively, and reference numerals indicate a reflux tank of the distillation column. First, an aqueous solution containing trioxane, triethylamine, and formaldehyde is fed to the first distillation column through the feed stage 1, and a distillate consisting of triethylamine, water, and trioxane is taken out from the top 2 of the column, which is maintained at 90°C. This distillate is returned to the neutralization step. On the other hand, an aqueous solution containing trioxane and formaldehyde is taken out from the column bottom 3 kept at 100°C, this column bottom is fed to a second distillation column, and trioxane and water are extracted from the column top 4 kept at 91°C. The water containing the composition is taken out from the bottom 9 of the tower. Further, a water-insoluble organic solvent is supplied to a reflux tank through 5, an organic solvent phase containing trioxane as an upper layer component is taken out through 6, and an aqueous phase as a lower phase component is returned to the second distillation column through 7. The organic solvent phase containing trioxane taken out from step 6 is supplied to another distillation column to recover trioxane. Further, an aqueous solution containing formaldehyde is taken out from the concentration section 8 of the second distillation column, and the formaldehyde is recovered and reused as a raw material for polyacetal.
本発明によれば、触媒として三フツ化ホウ素化
合物を用いて、トリオキサンとエチレンオキシド
との共重合体を製造する際に得られるトリオキサ
ン、トリエチルアミン及びホルムアルデヒドを含
む水溶液により、トリオキサンを回収すると同時
にホルムアルデヒドを有効に回収することが出
来、また回収されたホルムアルデヒド水溶液中に
は、トリエチルアミン及びフツ素成分が殆んど混
入されておらず再利用が可能である。 According to the present invention, an aqueous solution containing trioxane, triethylamine, and formaldehyde obtained when producing a copolymer of trioxane and ethylene oxide using a boron trifluoride compound as a catalyst is used to recover trioxane and at the same time effectively remove formaldehyde. Furthermore, the recovered formaldehyde aqueous solution contains almost no triethylamine and fluorine components and can be reused.
（実施例）
トリオキサンとエチレンオキシド（トリオキサ
ンに対して２重量％）とを三フツ化ホウ素ジブチ
ルエーテラートを触媒として共重合させ、反応の
終期に0.2％トリエチルアミンを含む水溶液で重
合体を洗浄する。得られたろ液は、トリオキサン
を４％、ホルムアルデヒドを２％含む。(Example) Trioxane and ethylene oxide (2% by weight based on trioxane) are copolymerized using boron trifluoride dibutyl etherate as a catalyst, and at the end of the reaction, the polymer is washed with an aqueous solution containing 0.2% triethylamine. The resulting filtrate contains 4% trioxane and 2% formaldehyde.
この水溶液を図面に示す如く3〓デイクソンパツ
キングを充填した塔高2.4ｍの充填塔に、供給段
１を通して毎時１Kg供給する。塔頂２を90℃に保
ち、トリエチルアミン、水、トリオキサンよりな
る留出物（トリエチルアミン20％、トリオキサン
57％、水23％）を毎時10ｇ取り出す。一方、塔底
温度100℃にて塔底３よりトリオキサン3.5％及び
ホルムアルデヒド1.8％含む水溶液を毎時990ｇ取
り出す。得られた塔底物を、同じく3〓デイクソン
パツキングを充填した塔高2.4ｍの充填塔に供給
し、91℃の塔頂４よりトリオキサン50％、水50％
を含む組成物を毎時62ｇ取り出し、塔底９より水
を毎時775ｇ取り出す。一方ベンゼンを還流タン
ク（）へ供給口５より毎時150ｇ供給してトリ
オキサンを含む上層成分を取出口６より毎時181
ｇ取り出し、下層成分は抜出口７を通して毎時35
ｇ蒸留塔（）へ戻す。さらに蒸留塔（）の濃
縮部８よりホルムアルデヒド10％を含む水溶液を
毎時180ｇ取り出す。なお、濃縮部８より取り出
したホルムアルデヒド水溶液中にはフツ素が
0.5ppm以下、トリエチルアミンがＮ分として
0.5ppm含有されていた。 As shown in the drawing, 1 kg of this aqueous solution is supplied per hour through the feed stage 1 to a packed tower having a tower height of 2.4 m packed with 3〓 Dickson packing. The top 2 of the column was maintained at 90°C, and a distillate consisting of triethylamine, water, and trioxane (triethylamine 20%, trioxane
57%, water 23%) at a rate of 10g per hour. On the other hand, 990 g of an aqueous solution containing 3.5% trioxane and 1.8% formaldehyde is taken out from the bottom 3 of the tower every hour at a bottom temperature of 100°C. The obtained column bottom material was supplied to a packed column with a column height of 2.4 m also packed with 3〓 Dickson packing, and 50% trioxane and 50% water were added from the column top 4 at 91°C.
62 g of a composition containing the same were taken out per hour, and 775 g of water was taken out from the bottom 9 of the tower every hour. On the other hand, 150 g of benzene is supplied per hour from the supply port 5 to the reflux tank (), and the upper layer components including trioxane are taken out from the port 6 at 181 g per hour.
g is taken out, and the lower layer components are taken out through the extraction port 7 at 35% per hour.
g Return to the distillation column (). Further, 180 g of an aqueous solution containing 10% formaldehyde is taken out every hour from the concentration section 8 of the distillation column (). Note that fluorine is present in the formaldehyde aqueous solution taken out from the concentration section 8.
0.5ppm or less, triethylamine as N content
It contained 0.5ppm.
取出口８より回収したホルムアルデヒド水溶液
をポリアセタールの原料として再使用したところ
問題はなかつた。 When the formaldehyde aqueous solution recovered from the outlet 8 was reused as a raw material for polyacetal, there were no problems.
図面は、本発明方法を実施するための簡略化し
た図であつて、図中符号は第１蒸留塔、は第
２蒸留塔、は還流タンクである。
The drawing is a simplified diagram for carrying out the method of the present invention, and the reference numerals in the drawing indicate a first distillation column, a second distillation column, and a reflux tank.
Claims (1)
アルデヒドを含む水溶液より、トリオキサンを蒸
留回収するにあたり、第一塔の蒸留塔に、トリオ
キサン、トリエチルアミン及びホルムアルデヒド
を含む水溶液を供給し、塔頂よりトリエチルアミ
ン、トリオキサンおよび水を留出させ、塔底より
トリオキサン及びホルムアルデヒドを含む水溶液
を抜き出して第２の蒸留塔に供給し、その塔頂よ
りトリオキサンを回収すると同時に該蒸留塔の濃
縮部よりホルムアルデヒドを含む水溶液を抜き出
すことを特徴とするトリオキサンを回収する方
法。1. When recovering trioxane by distillation from an aqueous solution containing trioxane, triethylamine, and formaldehyde, an aqueous solution containing trioxane, triethylamine, and formaldehyde is supplied to the first distillation column, and triethylamine, trioxane, and water are distilled out from the top of the column. , an aqueous solution containing trioxane and formaldehyde is extracted from the bottom of the column and supplied to a second distillation column, and at the same time trioxane is recovered from the top of the column, an aqueous solution containing formaldehyde is extracted from the concentration section of the distillation column. How to recover.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30858786A JPS63162686A (en) | 1986-12-26 | 1986-12-26 | Recovery of trioxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30858786A JPS63162686A (en) | 1986-12-26 | 1986-12-26 | Recovery of trioxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63162686A JPS63162686A (en) | 1988-07-06 |
| JPH0440353B2 true JPH0440353B2 (en) | 1992-07-02 |
Family
ID=17982827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30858786A Granted JPS63162686A (en) | 1986-12-26 | 1986-12-26 | Recovery of trioxane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63162686A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3285439B2 (en) * | 1993-03-24 | 2002-05-27 | ダイセル化学工業株式会社 | Method for producing reaction crude liquid and method for producing 1,3-butylene glycol |
-
1986
- 1986-12-26 JP JP30858786A patent/JPS63162686A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63162686A (en) | 1988-07-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |