JP3369639B2 - Purification method of 1,3-butylene glycol - Google Patents
Purification method of 1,3-butylene glycolInfo
- Publication number
- JP3369639B2 JP3369639B2 JP15385693A JP15385693A JP3369639B2 JP 3369639 B2 JP3369639 B2 JP 3369639B2 JP 15385693 A JP15385693 A JP 15385693A JP 15385693 A JP15385693 A JP 15385693A JP 3369639 B2 JP3369639 B2 JP 3369639B2
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- butylene glycol
- column
- distilled
- tower
- liquid obtained
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は1,3-ブチレングリコ−ル
の精製法に関する。さらに詳しくは臭気の無い極めて高
品質の1,3-ブチレングリコ−ルの製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for purifying 1,3-butylene glycol. More specifically, it relates to a method for producing odorless and extremely high quality 1,3-butylene glycol.
【０００２】1,3-ブチレングリコ−ルは沸点 208℃の粘
調な無色透明、無臭の液体で、すぐれた溶解性を有して
おり、化学的安定性にすぐれた誘導体を生成する。従っ
て、その用途は各種の合成樹脂、界面活性剤の原料とし
て、又そのすぐれた吸湿特性、低揮発性、低毒性を利用
して化粧品及湿剤、高沸点溶剤、不凍液の素材としても
利用されている。1,3-Butylene glycol is a viscous, colorless, transparent and odorless liquid having a boiling point of 208 ° C., has excellent solubility, and forms a derivative having excellent chemical stability. Therefore, its application is used as a raw material for various synthetic resins and surfactants, and also as a raw material for cosmetics and humectants, high boiling point solvents, and antifreeze liquids due to its excellent hygroscopicity, low volatility and low toxicity. ing.
【０００３】特に近年、化粧品業界では無毒、無刺激の
1,3-ブチレングリコ−ルが保湿剤として優れた性質を有
するため、その需要を大きく伸ばしている。Particularly in recent years, non-toxic and non-irritating in the cosmetics industry.
Since 1,3-butylene glycol has excellent properties as a moisturizing agent, its demand is greatly expanding.
【０００４】[0004]
【従来の技術】しかし、1,3-ブチレングリコ−ルに残存
する臭気のため使用範囲が限定され、特に無臭のいわゆ
る化粧品グレ−ドの1,3-ブチレングリコ−ルの品質アッ
プおよび収率アップが強く望まれていた。2. Description of the Related Art However, the use range of 1,3-butylene glycol is limited due to the residual odor, and the quality and yield of so-called cosmetic grade 1,3-butylene glycol are particularly odorless. Up was strongly desired.
【０００５】アセトアルド−ルの接触還元による1,3-ブ
チレングリコ−ルの精製に於ては反応装置からでてきた
該反応混合物から1,3-ブチレングリコ−ルを製品として
得るに当り、アルコ−ル類を除去した後、水分を除去し
更に塩、高沸点物の除去を行い、しかる後に低沸点物を
除去し、該蒸留塔の底部より1,3-ブチレングリコ−ルを
缶出製品として得ていた（特開昭６３−１５６７３８号
公報）。In the purification of 1,3-butylene glycol by catalytic reduction of acetoaldol, in obtaining 1,3-butylene glycol as a product from the reaction mixture discharged from the reactor, alcohol -After removing the polyols, water is further removed to remove salts and high-boiling substances, and then low-boiling substances are removed, and 1,3-butylene glycol is removed from the bottom of the distillation column. (Japanese Patent Laid-Open No. 63-156738).
【０００６】この精製工程に於いて従来脱水蒸留を行う
場合、塔頂より留出する液を一部塔頂に還流する方法が
採られてきた。In the conventional dehydration distillation in this purification step, a method has been adopted in which a liquid distilled from the top of the column is partially refluxed to the top of the column.
【０００７】このような方法であると臭気成分の除去が
不十分であるため、引き続く製品化工程において1,3-ブ
チレングリコ−ル無臭品の収率向上が計れず問題となっ
ていた。また、臭気を有する1,3-ブチレングリコ−ル
（例えば、一般に市販されている純度98％以上）から無
臭の1,3-ブチレングリコ−ル（例えば、純度99.7％〜9
9.97％）を蒸留精製によって得るに当たって1,3-ブチレ
ングリコ−ル中に含まれる極微量の臭い成分の除去は、
水を添加することにより促進されることが開示されてい
る（特公平３−80139号公報）。[0007] With such a method, the removal of odorous components is insufficient, so that the yield of 1,3-butylene glycol odorless product cannot be improved in the subsequent production steps, which has been a problem. In addition, odorous 1,3-butylene glycol (for example, commercially available purity of 98% or more) to odorless 1,3-butylene glycol (for example, purity 99.7% to 9%).
9.97%) is obtained by distillation purification, the removal of the trace amount of odorous components contained in 1,3-butylene glycol is
It is disclosed that it is promoted by adding water (Japanese Patent Publication No. 3-80139).
【０００８】[0008]
【発明が解決しようとする課題】上記の方法では高い品
質の、すなわち、無臭の1,3-ブチレングリコ−ルを得る
ことはできるが、無臭の1,3-ブチレングリコ−ルの収率
は５０〜６０％程度である。このことを勘案し、1,3-ブ
チレングリコ−ルの着臭と蒸留操作における損失の問題
を解決すべく鋭意検討した結果、以下に述べる本発明を
完成させた。According to the above-mentioned method, it is possible to obtain high-quality, that is, odorless 1,3-butylene glycol, but the yield of odorless 1,3-butylene glycol is high. It is about 50 to 60%. Taking this into consideration, as a result of intensive studies to solve the problems of odor of 1,3-butylene glycol and loss in the distillation operation, the present invention described below was completed.
【０００９】[0009]
【発明の構成】すなわち、本発明は「アセトアルド−ル
の液相水素還元法によって得られた反応混合物から、1,
3-ブチレングリコ−ルを蒸留精製するプロセスに於て、
脱水蒸留を行う際、塔頂部に新たに水を添加することを
特徴とする1,3-ブチレングリコ−ルの精製方法」であ
る。That is, the present invention relates to "a reaction mixture obtained by a liquid phase hydrogen reduction method of acetoaldole, 1,
In the process of distilling and purifying 3-butylene glycol,
The method for purifying 1,3-butylene glycol is characterized in that water is newly added to the top of the column when performing dehydration distillation. "
【００１０】本発明のポイントは「脱水蒸留を行う際、
脱水蒸留塔の塔頂部に新たに水を添加する」ことにあ
る。以下に本発明の1,3-ブチレングリコ−ルの精製方法
を具体的に説明する。The point of the present invention is that "at the time of performing dehydration distillation,
New water is added to the top of the dehydration distillation column. " The method for purifying 1,3-butylene glycol of the present invention will be specifically described below.
【００１１】なお、アセトアルド−ルの液相水素還元法
によって1,3-ブチレングリコ−ルを製造する際にはかな
りの量のエタノ−ルとブタノ−ルが必ず副生する。When producing 1,3-butylene glycol by the liquid phase hydrogen reduction method of acetoaldole, a considerable amount of ethanol and butanol are always by-produced.
【００１２】したがって、工業的に1,3-ブチレングリコ
−ルを製造する場合にはエタノ−ルとブタノ−ルを回収
する必要がある。Therefore, in the case of industrially producing 1,3-butylene glycol, it is necessary to recover ethanol and butanol.
【００１３】したがって、本発明で述べる「脱水蒸留」
というのは通常、副生したエタノ−ルとブタノ−ルを回
収除去した後に行われる。Therefore, the "dehydration distillation" described in the present invention
This is usually done after recovering and removing by-produced ethanol and butanol.
【００１４】図−１は本発明の方法を実施するための１
実施態様を示した装置のフロ−シ−トであり、１−１が
脱水塔、１−２が脱塩塔（薄膜蒸発器）、１−３が脱高
沸塔、１−４が製品塔である。FIG. 1 shows a method for carrying out the method of the present invention.
1 is a dewatering tower, 1-2 is a desalting tower (thin film evaporator), 1-3 is a deboiling tower, 1-4 is a product tower. Is.
【００１５】反応粗液からアルコ−ル類を回収除去され
た、水を含んだ粗1,3-ブチレングリコ−ルは、脱水塔１
−１にはいる。The crude 1,3-butylene glycol containing water from which alcohols have been recovered and removed from the crude reaction liquid is used in the dehydration tower 1.
Enter -1.
【００１６】以下に述べる蒸留塔は、多孔板塔、泡鐘塔
などでもよいが、好ましくはスルザ−・パッキング、メ
ラパック（共に住友重機械の商品名）等を充填した低圧
損失の充填塔がより適当である。これは1,3-ブチレング
リコ−ルが200 ℃以上では熱分解され臭気に対して悪影
響を及ぼす為（特開昭６３−１５６７３８号公報）、蒸
留温度をできるだけ低くする為である。The distillation column described below may be a perforated plate column, a bubble column, or the like, but a low pressure loss packed column packed with Sulzer packing, Melapak (both are trade names of Sumitomo Heavy Industries), etc. is more preferable. Appropriate. This is because 1,3-butylene glycol is thermally decomposed at 200 ° C. or higher and adversely affects odor (Japanese Patent Laid-Open No. 63-156738), so that the distillation temperature is made as low as possible.
【００１７】また1,3-ブチレングリコ−ルにかかる熱履
歴（滞留時間）が長い場合も、同様に影響がでる。従っ
て、採用されるリボイラ−はプロセス側流体の滞留時間
の短い、例えば自然流下型薄膜蒸発器、強制撹拌型薄膜
蒸発器等の薄膜蒸発器が適当である。Also, when the thermal history (residence time) applied to 1,3-butylene glycol is long, the same effect is exerted. Therefore, as the reboiler to be adopted, a thin film evaporator having a short residence time of the process side fluid, for example, a natural flow-down type thin film evaporator or a forced stirring type thin film evaporator is suitable.
【００１８】ここで蒸留塔塔頂部より新たに水を添加す
る。水は普通水でもよいが、高度の精製処理を行うた
め、純水（イオン交換水）、蒸留水がより望ましい。Here, water is newly added from the top of the distillation column. The water may be ordinary water, but pure water (ion-exchanged water) or distilled water is more preferable because it performs a high-level purification treatment.
【００１９】アルコ−ル類を除去された、粗1,3-ブチレ
ングリコ−ルは、脱水塔の中央部に供給する必要があ
る。供給位置が高すぎると溜出液中の1,3-ブチレングリ
コ−ルの濃度が高くなり、逆に低すぎると缶出液中の水
分濃度が高くなるので、好ましくない。塩、高沸物を含
んだ1,3-ブチレングリコ−ルは、蒸留塔下部から排出さ
れ脱塩塔１−２に送られる。Crude 1,3-butylene glycol from which alcohols have been removed must be fed to the central part of the dehydration column. If the feed position is too high, the concentration of 1,3-butylene glycol in the distillate will be high, and if it is too low, the water concentration in the bottom liquid will be high, which is not preferable. 1,3-Butylene glycol containing salts and high boiling substances is discharged from the lower part of the distillation column and sent to the desalting column 1-2.
【００２０】蒸留塔塔頂部より新たに添加する水の量は
供給される粗液の量に対して１〜２００重量部、好まし
くは、５〜５０重量部である。新たに添加する水の量は
粗液中に含まれる不純物の量により少なすぎると効果が
不充分であるが、多すぎてもリボイラ−の熱負荷が増加
するので好ましくない。The amount of water newly added from the top of the distillation column is 1 to 200 parts by weight, preferably 5 to 50 parts by weight, based on the amount of the crude liquid supplied. If the amount of water newly added is too small due to the amount of impurities contained in the crude liquid, the effect is insufficient, but if it is too large, the heat load of the reboiler increases, which is not preferable.
【００２１】脱水塔における還流比がゼロの場合、水を
新たに添加する位置は蒸留塔塔頂部である。脱水塔にお
ける還流比がゼロでない場合、水を新たに添加する位置
は蒸留塔中央部側である。When the reflux ratio in the dehydration tower is zero, the position at which water is newly added is the top of the distillation tower. When the reflux ratio in the dehydration tower is not zero, the position where water is newly added is on the side of the distillation tower center.
【００２２】新たに添加する水の温度は常温で特に問題
はないこの時、蒸留塔塔頂部の圧力は１００Ｔｏｒｒ以
下、望ましくは２０〜６０Ｔｏｒｒの減圧下で行われ
る。２０Ｔｏｒｒ以下であると、コンデンサ−の冷凍負
荷が増加するため望ましくない。The temperature of the newly added water is normal temperature, and there is no particular problem. At this time, the pressure at the top of the distillation column is 100 Torr or less, preferably 20 to 60 Torr. If it is 20 Torr or less, the refrigerating load of the condenser increases, which is not desirable.
【００２３】上記のような減圧下で行われると蒸留塔内
の温度は塔頂部で２０〜４０℃、塔底部で１２０〜１４
０℃に保持される。When the distillation is performed under reduced pressure as described above, the temperature in the distillation column is 20 to 40 ° C. at the top of the column and 120 to 14 at the bottom of the column.
Hold at 0 ° C.
【００２４】このように、新たに添加する水に同伴され
て除去される物質は主にアルド−ル水素還元時に生成し
たブタノ−ル、２−エチルブタノ−ル、２，４−ジメチ
ルジオキサンなどであり、結果として1,3-ブチレングリ
コ−ルの純度が向上し、かつ、収率が向上する。すなわ
ち、臭気成分が除去された高品質の1,3-ブチレングリコ
−ルが効率よく得られる。Thus, the substances removed by being entrained in the newly added water are mainly butanol, 2-ethylbutanol, and 2,4-dimethyldioxane, which are produced during the reduction of aldol with hydrogen. As a result, the purity of 1,3-butylene glycol is improved and the yield is improved. That is, high-quality 1,3-butylene glycol free of odorous components can be efficiently obtained.
【００２５】[0025]
【実施例】図-1に示されるフロ−シ−トに従って本発明
の方法を実施例に基づいて説明する。原料としてアセト
アルド−ル 100部、水素を 6.5部反応器に仕込んだ。EXAMPLES The method of the present invention will be described based on examples according to the flow chart shown in FIG. As a raw material, 100 parts of acetaldol and 6.5 parts of hydrogen were charged into the reactor.
【００２６】反応器の温度を 125〜135 ℃、圧力 150 K
g/cm2に保持した。The temperature of the reactor is 125 to 135 ° C. and the pressure is 150 K.
It was kept at g / cm 2 .
【００２７】触媒としてラネ−ニッケルを 3.5部加え
た。3.5 parts of Raney-nickel was added as a catalyst.
【００２８】反応器から取り出された反応粗液は触媒を
分離されたのち、苛性ソ−ダで中和された。その後、ア
ルコ−ル類を除去された粗1,3-ブチレングリコ−ルは図
-1に示す脱水塔 1-1に仕込まれた。The reaction crude liquid taken out from the reactor was separated from the catalyst and then neutralized with caustic soda. After that, the crude 1,3-butylene glycol from which alcohols have been removed is
It was placed in the dehydration tower 1-1 shown in -1.
【００２９】脱水塔では仕込み液量100 部に対して塔頂
より純水 15 部を加え、圧力50torrで蒸留塔底部より水
分 0.5重量％以下の粗1,3-ブチレングリコ−ルを得た。In the dehydration column, 15 parts of pure water was added to the charged liquid amount of 100 parts from the top of the column, and crude 1,3-butylene glycol having a water content of 0.5% by weight or less was obtained from the bottom of the distillation column at a pressure of 50 torr.
【００３０】脱水された粗1,3-ブチレングリコ−ルは次
に、脱塩塔 1-2に仕込まれた。ここでは仕込液量100 部
に対して蒸発残分として、塩、高沸物および1,3-ブチレ
ングリコ−ルの一部が底部より 5部、排出された。塔頂
からは1,3-ブチレングリコ−ル及び低沸物と高沸物の一
部が 95 部留出された。The dehydrated crude 1,3-butylene glycol was then charged to the desalting tower 1-2. Here, 5 parts of salt, high boiling point and 1,3-butylene glycol were partially discharged from the bottom as evaporation residue for 100 parts of the charged liquid. From the top of the column, 95 parts of 1,3-butylene glycol and a part of low boiling material and high boiling material were distilled.
【００３１】脱塩塔 1-2より留出された1,3-ブチレング
リコ−ル及び低沸物及び高沸物の一部は、脱高沸塔 1-3
に仕込まれ、塔底より高沸物と1,3-ブチレングリコ−ル
の一部が排出される。塔頂より1,3-ブチレングリコ−ル
及び低沸物が留出され製品塔1-4に仕込まれた。A part of 1,3-butylene glycol and low boiling materials and high boiling materials distilled from the desalting tower 1-2 is removed from the high boiling tower 1-3.
The high-boiling substance and part of 1,3-butylene glycol are discharged from the bottom of the column. From the top of the column, 1,3-butylene glycol and low-boiling substances were distilled out and charged into the product column 1-4.
【００３２】製品塔 1-4においては、塔頂から低沸物及
び1,3-ブチレングリコ−ルの一部が留出される。塔底か
らは製品1,3-ブチレングリコ−ルが取り出された。In the product tower 1-4, low boiling substances and part of 1,3-butylene glycol are distilled from the top of the tower. The product 1,3-butylene glycol was removed from the bottom of the column.
【００３３】実施例における、脱高沸塔、製品塔でのそ
れぞれの仕込液量に対する塔底での高沸物等の抜き取り
及び塔頂からの低沸物等の抜き取りのカット率は脱水塔
に水を添加する以前と比べて以下のようになった。In the examples, the cut rates for withdrawing high boiling substances and the like from the bottom and withdrawing low boiling substances and the like from the top of the column for the respective amounts of the charged liquids in the deboiling tower and product tower are different from those in the dehydrating tower. Compared to before adding water, the results are as follows.
【００３４】
脱高沸塔 製品塔
カット率 カット率
水添加前 17 ％ 11 ％
後 11 ％ 7 ％
また、製品1,3-ブチレングリコ−ルの臭気は、蒸留条件
が厳しくなったにもかかわらず以下の様に水添加前と同
じ品質のものが得られた。De-high boiling tower Product tower Cut rate Cut rate Before water addition 17% 11% After water 11% 7% Further, the odor of the product 1,3-butylene glycol is not the same even though the distillation conditions become severe. The same quality as before water addition was obtained as follows.
【００３５】
臭気評点とは、評価試料としてほとんど無臭の1,3-ブチ
レングリコ−ルを 5とし、僅かに臭気の感じられるもの
を 10 としその相対評価で点数をつける。[0035] The odor score is 1,3-butylene glycol, which is almost odorless as an evaluation sample, and 10 is a substance with a slight odor.
【００３６】評価試料は水と 1:1で混合し、共栓広口試
薬瓶に入れ、密栓し室温にて静置した後、大気中にてす
みやかに臭いをかぎ、比較する方法によって行った。The evaluation sample was mixed with water in a ratio of 1: 1 and placed in a common-ended wide-mouthed reagent bottle, and the container was sealed, allowed to stand at room temperature, and immediately smelled in the air, and the comparison was performed.
【００３７】[0037]
【発明の効果】そこで脱水塔において、塔頂よりの留出
液を還流する代わりに塔頂部に新たに、水を添加したと
ころ、臭気成分が水に同伴して除去されるため、後に続
く脱高沸塔、製品塔においてその高沸物及び低沸物を除
去するためのカット液量を低減でき、また極めて臭気の
少ない優れた1,3-ブチレングリコ−ルを製造することが
できた。In the dehydration tower, therefore, when water is newly added to the top of the tower instead of refluxing the distillate from the top, the odorous components are removed along with the water, and the subsequent removal of It was possible to reduce the amount of the cut liquid for removing the high-boiling substances and the low-boiling substances in the high-boiling tower and the product tower, and to produce excellent 1,3-butylene glycol with extremely low odor.
【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.
【符号の説明】 なし[Explanation of symbols] None
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 31/00 C07C 29/00 ─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) C07C 31/00 C07C 29/00
Claims (4)
って得られた反応粗液から触媒を分離し、中和し、アル
コール類を除去して得られた粗１，３−ブチレングリコ
ールを、 （ｉ）脱水蒸留塔の塔頂または塔頂に近い中央部側に新
たに水を添加しながら脱水蒸留し、 （ii）上記（ｉ）で得られた塔底液を脱塩塔により蒸留
し、 （iii）上記（ii）で得られた塔頂液を脱高沸塔により
蒸留し、 （iv）上記（iii）で得られた塔頂液を脱低沸塔により
蒸留し、 脱低沸塔底部から１，３−ブチレングリコールを回収す
ることを特徴とする精製１，３−ブチレングリコールの
製造方法。1. A crude 1,3-butylene glycol obtained by separating a catalyst from a reaction crude liquid obtained by a liquid phase hydrogen reduction method of acetoaldol, neutralizing it, and removing alcohols, ) Dehydration distillation is performed while newly adding water to the top of the dehydration distillation column or the central portion near the top of the column, (ii) the bottom liquid obtained in (i) above is distilled by a desalting column, iii) The top liquid obtained in (ii) above is distilled by a deboiling tower, (iv) The top liquid obtained in (iii) is distilled by a deboiling tower, and the bottom of the deboiling tower is removed. A method for producing purified 1,3-butylene glycol, which comprises recovering 1,3-butylene glycol from
まれる不純物が、ブタノール、２−エチルブタノール、
２，４−ジメチルジオキサンの少なくとも一種であり、
（ｉ）脱水蒸留で上記不純物を除去することを特徴とす
る請求項１に記載の精製１，３−ブチレングリコールの
製造方法。2. Impurities contained in the crude 1,3-butylene glycol include butanol, 2-ethylbutanol,
At least one of 2,4-dimethyldioxane,
(I) The method for producing purified 1,3-butylene glycol according to claim 1, wherein the impurities are removed by dehydration distillation.
脱水蒸留塔により行われ、（ii）上記（ｉ）で得られた
塔底液を、薄膜蒸発器を有する脱塩塔により蒸留するこ
とを特徴とする請求項１又は２に記載の精製１，３−ブ
チレングリコールの製造方法。3. (i) dehydration distillation is carried out by a dehydration distillation column having a reboiler, and (ii) the bottom liquid obtained in (i) above is distilled by a desalting column having a thin film evaporator. The method for producing the purified 1,3-butylene glycol according to claim 1 or 2.
記評価方法による臭気が５であることを特徴とする請求
項１〜３のいずれかに記載の精製１，３−ブチレングリ
コールの製造方法。 評価方法：試料の精製1,3-ブチレングリコールを水と
１：１で混合し、共栓広口試薬瓶に入れ、密栓し、室温
にて静置した後、大気中にてすみやかに臭いをかぎ、評
価基準試料（評価基準試料としてほとんど無臭の１，３
−ブチレングリコールを５とし、僅かに臭気の感じられ
るものを１０とする）と比較し、その相対評価で点数を
つける。4. The method for producing purified 1,3-butylene glycol according to claim 1, wherein the odor of purified 1,3-butylene glycol is 5 according to the following evaluation method. Evaluation method: Sample purification 1,3-butylene glycol was mixed with water at a ratio of 1: 1 and placed in a ground-stop wide-mouthed reagent bottle, which was then sealed and allowed to stand at room temperature, then immediately smelled in the air. , Evaluation standard sample (almost odorless 1,3 as an evaluation standard sample
-Butylene glycol is set to 5 and those having a slight odor are set to 10), and a score is given by the relative evaluation.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15385693A JP3369639B2 (en) | 1993-06-24 | 1993-06-24 | Purification method of 1,3-butylene glycol |
| EP97104946A EP0787709B1 (en) | 1993-03-24 | 1993-11-19 | An improved process for the preparation of 1,3-betylene glycol |
| DE69328043T DE69328043T2 (en) | 1993-03-24 | 1993-11-19 | Improved process for the production of 1,3-butylene glycol |
| DE69331565T DE69331565D1 (en) | 1993-03-24 | 1993-11-19 | An improved process for the production of 1,3-butylene glycol |
| EP98113585A EP0884297B1 (en) | 1993-03-24 | 1993-11-19 | An improved process for the preparation of 1,3-butylene glycol |
| EP93402815A EP0616992B2 (en) | 1993-03-24 | 1993-11-19 | Process for the preparation of 1,3-butylene glycol |
| DE69320454T DE69320454T3 (en) | 1993-03-24 | 1993-11-19 | Process for the preparation of 1,3-butylene glycol |
| TW082110290A TW295577B (en) | 1992-06-12 | 1993-12-06 | |
| US08/163,308 US5345004A (en) | 1993-03-24 | 1993-12-08 | Process for the preparation of 1,3-butylene glycol |
| KR1019930027356A KR100276161B1 (en) | 1993-03-24 | 1993-12-11 | Process for the preparation of 1,3-butylene glycol |
| US08/264,733 US5583270A (en) | 1993-03-24 | 1994-06-23 | Process for the preparation of 1,3-butylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15385693A JP3369639B2 (en) | 1993-06-24 | 1993-06-24 | Purification method of 1,3-butylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710789A JPH0710789A (en) | 1995-01-13 |
| JP3369639B2 true JP3369639B2 (en) | 2003-01-20 |
Family
ID=15571607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15385693A Expired - Fee Related JP3369639B2 (en) | 1992-06-12 | 1993-06-24 | Purification method of 1,3-butylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3369639B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3369707B2 (en) * | 1994-03-17 | 2003-01-20 | ダイセル化学工業株式会社 | Purification method of 1,3-butylene glycol |
| KR100595399B1 (en) * | 1998-08-07 | 2006-07-03 | 다이셀 가가꾸 고교 가부시끼가이샤 | 1,3-butylene glycol of high purity and method for producing the same |
| JP4530461B2 (en) * | 2000-02-04 | 2010-08-25 | ダイセル化学工業株式会社 | Method for purifying 1,3-butylene glycol |
| WO2006118111A1 (en) * | 2005-04-28 | 2006-11-09 | Adeka Corporation | Alkanediol composition, process for producing the same and cosmetic |
| JP7380161B2 (en) * | 2019-12-09 | 2023-11-15 | 株式会社レゾナック | Method for producing paraaldol |
| JP7380181B2 (en) * | 2019-12-20 | 2023-11-15 | 株式会社レゾナック | Method for producing paraaldol |
-
1993
- 1993-06-24 JP JP15385693A patent/JP3369639B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0710789A (en) | 1995-01-13 |
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