JPS6327456A - Production of acetin - Google Patents
Production of acetinInfo
- Publication number
- JPS6327456A JPS6327456A JP17133186A JP17133186A JPS6327456A JP S6327456 A JPS6327456 A JP S6327456A JP 17133186 A JP17133186 A JP 17133186A JP 17133186 A JP17133186 A JP 17133186A JP S6327456 A JPS6327456 A JP S6327456A
- Authority
- JP
- Japan
- Prior art keywords
- acetic acid
- reaction
- water
- acetin
- glycerin
- 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
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 107
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 9
- 230000021736 acetylation Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 235000011187 glycerol Nutrition 0.000 claims description 17
- 239000012345 acetylating agent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 4
- 230000000397 acetylating effect Effects 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 229960000583 acetic acid Drugs 0.000 abstract 8
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000012362 glacial acetic acid Substances 0.000 abstract 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 38
- 235000013773 glyceryl triacetate Nutrition 0.000 description 19
- 239000001087 glyceryl triacetate Substances 0.000 description 19
- 229960002622 triacetin Drugs 0.000 description 19
- 239000004348 Glyceryl diacetate Substances 0.000 description 14
- 235000019443 glyceryl diacetate Nutrition 0.000 description 14
- 239000007788 liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000052 vinegar Substances 0.000 description 8
- 235000021419 vinegar Nutrition 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 238000000998 batch distillation Methods 0.000 description 2
- 238000001944 continuous distillation Methods 0.000 description 2
- -1 diacetate Chemical compound 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- XYAUIVRRMJYYHR-UHFFFAOYSA-N acetic acid;propane-1,2,3-triol Chemical compound CC(O)=O.OCC(O)CO XYAUIVRRMJYYHR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)゛
グリセリンの酢酸エステルつまりアセチンにはモノアセ
テート、ジアセテート、トリアセテートの3種類あり溶
剤!可塑剤、香料固定剤、湿潤剤等工業的に大へん有用
な物質である。[Detailed description of the invention] (Industrial application field) ゛Acetate ester of glycerin, or acetin, has three types of solvents: monoacetate, diacetate, and triacetate! It is a very useful substance industrially as a plasticizer, perfume fixative, wetting agent, etc.
(従来技術)
このアセチン類はグリセリンをアセチル化して工業的に
製造されている。例えばドイツ特許134.867には
、グリセリンと酢酸を硫酸触媒で反応させアセチン類の
混合物を得る方法がしるされている。一般に有機酸とア
ルコールとのエステル化反応は下式で示される。(Prior Art) These acetins are industrially produced by acetylating glycerin. For example, German Patent No. 134.867 describes a method of reacting glycerin and acetic acid with a sulfuric acid catalyst to obtain a mixture of acetins. Generally, the esterification reaction between an organic acid and an alcohol is shown by the following formula.
R−COOH+R’ −OH→
R−COOR’ 十820
(式中R,R’ は任意のアルキル基、アリール基等を
示す)
この反応には通常酸触媒を用いる。例えば硫酸塩酸 リ
ン酸等の鉱酸の他、芳香族スルホン酸(p−トルエンス
ルホン酸 ベンゼンスルホン酸)または三フッ化ホウ素
−ジエチルエーテル錯体等のルイス酸及び陽イオン交換
樹脂(市販芯ダイヤイオン PK216、アンバーライ
トIP−120B等)などが適宜、任意に選択され使用
される。R-COOH+R'-OH→R-COOR' For example, in addition to mineral acids such as sulfuric acid and phosphoric acid, Lewis acids such as aromatic sulfonic acids (p-toluenesulfonic acid and benzenesulfonic acid) or boron trifluoride-diethyl ether complex, and cation exchange resins (commercially available core Diamond PK216) , Amberlite IP-120B, etc.) are arbitrarily selected and used.
(発明が解決しようとする問題点)
本反応はエステル化反応と加水分解反応の平衡反応であ
ると考えられエステル化の反応速度を向上させる為に生
成する水を系外に除去する方法も同時に行なわれるのが
常である。しかし酸触媒の使用は製造するエステルによ
っては品質上の問題を生じることもあり、又、酸による
反応装置の腐蝕問題更に、製造プロセスから排出される
廃液中に酸が含まれ中和めるいは回収の工程が必要とな
り品質上、安全上の問題とともに経済性を失わせる要因
のひとつにもなりかねない。しかし酸触媒を使用しない
場合エステル化反応速度は非常に遅く、これまで工業的
製造法としては不敵と考えられていた。(Problem to be solved by the invention) This reaction is considered to be an equilibrium reaction between esterification reaction and hydrolysis reaction, and in order to improve the reaction rate of esterification, there is also a method to remove the water produced from the system at the same time. It is usually done. However, the use of acid catalysts may cause quality problems depending on the ester produced, and there is also the problem of corrosion of the reaction equipment due to the acid.Furthermore, the acid is contained in the waste liquid discharged from the manufacturing process, which can be neutralized or recovered. This requires additional steps, which may cause quality and safety issues as well as a loss of economic efficiency. However, without the use of an acid catalyst, the esterification reaction rate is extremely slow, and so far it has been considered unbeatable as an industrial production method.
本発明者はこれらの問題を解決すべく鋭意検討を重ねつ
いにグリセリンのアセチル化反応において酢酸をアセチ
ル化剤に用いアセチンを製造する際、酸触媒を添加しな
くてもよい方法をついに見出しここに本発明を完成する
に到った。In order to solve these problems, the present inventor has made extensive studies and has finally discovered a method that does not require the addition of an acid catalyst when producing acetin using acetic acid as an acetylating agent in the acetylation reaction of glycerin. The present invention has now been completed.
(発明の構成)
即ち本発明はグリセリンをアセチル化して一般式(1)
%式%(1)
(式中nは2.及び3の整数を示す)
で表わされるアセチンを製造する方法においてアセチル
化剤として酢酸を、グリセリンに対して0.6Xn
から0゜8Xn2モル倍使用し、生成する水を過剰に存
在する酢酸とともに系外に留去することによって無触媒
でアセチル化することを特徴とするアセチンの製造方法
である。つまり生成する水を系外に留去する為に特別な
水のエントレーナー(共沸剤)を使用することなく、積
極的にアセチル化剤である酢酸の上昇蒸気量を増加させ
生成した水の蒸気を同伴留去させることでアセチル化を
完結させる方法であり、それ故グリセリンに対して酢酸
は理論使用量以上の過剰量必要となるが、系外に留去さ
れた酢酸は通常行なわれる酢酸〜水の分離精製工程を経
て回収され得る。グリセリンと酢酸によるエステル化反
応を式(2)に示す。(Structure of the Invention) That is, the present invention provides acetylation in a method of acetylating glycerin to produce acetin represented by the general formula (1) % formula % (1) (wherein n represents an integer of 2. and 3). Acetic acid as agent, 0.6Xn to glycerin
This is a method for producing acetin, which is characterized in that 2 moles of 0°8Xn are used from 0°8Xn, and acetylation is carried out without a catalyst by distilling the produced water out of the system together with an excess of acetic acid. In other words, without using a special water entrainer (azeotropic agent) to distill the generated water out of the system, we actively increase the amount of rising vapor of acetic acid, which is an acetylating agent, to remove the generated water. This method completes the acetylation by entraining and distilling off the vapor, and therefore an excess amount of acetic acid is required compared to the theoretical amount of glycerin used. -Can be recovered through a water separation and purification process. The esterification reaction between glycerin and acetic acid is shown in formula (2).
CH2−0H
CHOH+3C83COOH→
CH2−OH
グリセリン 酢 酸
CH2−00CCH3
CH−000CH(2)
(トリアセチンの場合酢酸の理論使用量は、ジアセチン
を製造する場合にはグリセリンに対して2モル倍、トリ
アセチンの場合には3モル倍である)以下本発明の実施
態様について反応条件を述べより詳しく説明する。原料
グリセリン及び酢酸はその製造法の如何にかがねらず現
在市販されているものでよい。酢酸についてより好まし
くは木酢rti(水分が1%以下のもの)であるグリセ
リンに対する酢酸のモル比は目的とするアセチンがジア
セチンの場合2.4〜3.2モル倍、トリアセチンの場
合5.4〜7.2モル倍である。それぞれの場合につい
て、より少ない酢酸旦では目的とするアセチンにまでア
セチル化されず、酢酸を追加する必要が生じ繁雑である
。文通により多くの酢酸を使用すると、ジアセチンの場
合はトリアセチンにまでアセチル化されてしまうし、ト
リアセチンの場合は回収酢M量が極めて多くなり経済性
を失ってしまいかねない。尚純度の高いトリアセチンを
望むのであれば主成分をトリアセチンとするアセチン混
合物を例えば前述のドイツ特許134.867に記載の
無水酢酸処理法などによって目的は容易に達せられる。CH2-0H CHOH+3C83COOH→ CH2-OH Glycerin Acetic Acid CH2-00CCH3 CH-000CH(2) (In the case of triacetin, the theoretical amount of acetic acid to be used is 2 times the mole of glycerin when producing diacetin, and is 3 times the mole amount).Reaction conditions for embodiments of the present invention will be described below in more detail. The raw material glycerin and acetic acid may be those currently commercially available, regardless of the manufacturing method. For acetic acid, the molar ratio of acetic acid to glycerin, which is wood vinegar rti (water content is 1% or less), is 2.4 to 3.2 times by mole when the target acetin is diacetin, and 5.4 to 5.4 times when the target acetin is triacetin. It is 7.2 times the mole. In each case, if the amount of acetic acid is smaller, the desired acetylation is not achieved, and it becomes necessary to add acetic acid, which is complicated. If a large amount of acetic acid is used for correspondence, diacetin will be acetylated to triacetin, and in the case of triacetin, the amount of recovered vinegar M will be extremely large, leading to loss of economic efficiency. If triacetin with high purity is desired, the objective can be easily achieved by treating an acetin mixture containing triacetin as the main component, for example, with the acetic anhydride method described in the above-mentioned German Patent No. 134.867.
更に過剰量の酢酸は反応開始時に全て反応系に加えるこ
とが反応操作上簡便であるが、分割して反応の進行に伴
なって添加する方法でもよい。Furthermore, although it is convenient for the reaction operation to add the entire excess amount of acetic acid to the reaction system at the beginning of the reaction, it may also be added in portions as the reaction progresses.
反応温度は120〜180’Cの範面て可能であるが好
ましくは150〜160℃でおり、それ以下の温度では
生成したH2Oと迅速に留出させられずエステル化反応
自身も遅くなる。160’Cを超える温度では反応速度
は大きいが得られる製品品質上問題となる場合もある。The reaction temperature can range from 120 to 180°C, but is preferably from 150 to 160°C; if the temperature is lower than that, the produced H2O cannot be distilled off quickly and the esterification reaction itself becomes slow. Although the reaction rate is high at temperatures exceeding 160'C, there may be problems with the quality of the product obtained.
反応圧力は減圧から加圧まで広い圧力範囲で実施可能で
おるが通常の反応装置を使用することを考えると常圧で
行なうのがよい。反応時間は、エステル化をどの程度で
終了させるのかということで設定されるが、仕込モル比
との兼ね合いもある。例えばジアセチンを主成分にする
アセチン混合物を製造する場合、仕込モル比が約3なら
ば反応時間は約10時間程度で充分であり得られるアセ
チン混合物の組成はモノアセチン28% ジアセチン5
7% トリアセチン15%である。これより短い時間で
はモノアセチンの比率が高くトリアセチンの比率は低く
なる。逆に10時間を超えて反応を行なった場合徐々に
トリアセチンの比率が高まっていくが、ジアセチンの比
率はさほど高くならず遂にはトリアセチンの生成量の方
が上まわることになる。反応にともない生成する水は反
応器に付属する蒸留塔の塔頂より酢酸とともに留出する
。この留出液は別に設けた酢酸回収装置によって酢酸と
水を分離し、酢酸は角度反応系へ仕込まれ水は排水とし
て処理される。Although the reaction pressure can be carried out in a wide range of pressures from reduced pressure to increased pressure, it is preferable to carry out the reaction at normal pressure considering the use of a normal reaction apparatus. The reaction time is set depending on how long it takes to complete esterification, but there is also a balance with the charging molar ratio. For example, when producing an acetin mixture containing diacetin as the main component, if the charging molar ratio is about 3, the reaction time is about 10 hours, and the resulting acetin mixture has a composition of 28% monoacetin and 5% diacetin.
7% triacetin 15%. If the time is shorter than this, the ratio of monoacetin will be high and the ratio of triacetin will be low. On the other hand, if the reaction is carried out for more than 10 hours, the proportion of triacetin gradually increases, but the proportion of diacetin does not increase so much, and the amount of triacetin produced eventually exceeds that of triacetin. Water produced during the reaction is distilled out from the top of a distillation column attached to the reactor together with acetic acid. This distillate is separated into acetic acid and water by a separate acetic acid recovery device, the acetic acid is fed into the angular reaction system, and the water is treated as wastewater.
酢酸−水の分離精製工程の使用できない場合には、水の
エントレーナー(例えばベンゼン等)を利用して、塔頂
より留出する、分離下層水を排水に上層のエントレーナ
ーを反応器に付属する蒸留塔の塔頂へ還流液としてサイ
クルすることも当然可能である。この場合でも本発明の
主旨は変わらない。かくして得られた反応粗液は連続お
るいは回分式蒸留塔を用いて過剰の酢酸及び低沸不純物
を留去し、次に精留を行なって製品のアセチンとする。If the acetic acid-water separation and purification process cannot be used, a water entrainer (e.g., benzene, etc.) is used to distill the water from the top of the column, and the separated lower layer water is drained and the upper layer entrainer is attached to the reactor. Of course, it is also possible to cycle the reflux liquid to the top of the distillation column. Even in this case, the gist of the present invention does not change. Excess acetic acid and low-boiling impurities are distilled off from the reaction crude liquid thus obtained using a continuous or batch distillation column, and then rectification is performed to obtain the product acetin.
この精留に用いる装置としては通常の連続あるいは回分
式蒸留塔の他FFEなどの薄膜式蒸発器を用いてもよい
。いずれにせよ、一般に行なわれている蒸留あるいは蒸
発で留出液として容易に製品のアセチンを得ることがで
きる。As an apparatus used for this rectification, a thin film evaporator such as an FFE may be used in addition to a conventional continuous or batch distillation column. In any case, the product acetin can be easily obtained as a distillate through commonly used distillation or evaporation.
以下に本発明を更に詳細に説明する為に実施例をあげる
。Examples will be given below to explain the present invention in more detail.
実施例−1
ジアセチンの製造法
(組成分析はGC分析法によった)
40φ1ONの多孔板塔を備えた51のフラスコにグリ
セリン10309と酢1111813gを仕込み、缶液
温度180’Cで10時間反応させる(対グリセリン約
2.7モル倍)反応の進行に伴って塔頂より水−酢酸の
混合物が留出する。10時間経過後留出液は4999で
あった。その組成は酢138.4% 水63.4%でめ
った。この時の缶液の組成は、酢127.38% モノ
アセチン22.10%ジアセチン31.53% トリア
セチン6.12%でめった。缶液を50’C以下に冷却
したのち、減圧(7QTorr)で過剰量の酢酸を留出
ざぜる。酢鼠留分(Top温度〜60’C)45(1、
酢酸純度89.5% 水10.5%次に再び缶液を80
°C以下に冷却した後減圧下(15Torr)でアセチ
ンの精製を行なう。Example-1 Method for producing diacetin (compositional analysis was by GC analysis method) Glycerin 10309 and vinegar 1111813g were charged into 51 flasks equipped with a 40φ1ON perforated plate column, and reacted for 10 hours at a can temperature of 180'C. (About 2.7 moles of glycerin) As the reaction progresses, a water-acetic acid mixture is distilled from the top of the column. After 10 hours, the distillate had a concentration of 4999. Its composition is 138.4% vinegar and 63.4% water. The composition of the can liquid at this time was 127.38% vinegar, 22.10% monoacetin, 31.53% diacetin, and 6.12% triacetin. After cooling the bottom liquid to below 50'C, excess acetic acid is distilled off under reduced pressure (7 Q Torr). Vinegar distillate (Top temperature ~ 60'C) 45 (1,
Acetic acid purity 89.5% Water 10.5% Next, add the can liquid again to 80%
After cooling to below °C, acetin is purified under reduced pressure (15 Torr).
還流比(R,R) =3
製品留分(丁op温度147〜150″C)15009
組成分析結果は以下の通りであった。Reflux ratio (R, R) = 3 Product fraction (op temperature 147-150″C) 15009
The compositional analysis results were as follows.
モノアセチン22.1% ジアセチン52.8% トリ
アセチン25.1%
実施例−2
トリアセチンの製造法
実施例−1と同様の反応装置を使用しグリセリン552
gと酢酸2160g(対グリセリン6モル倍)を仕込み
、反応を開始した。反応開始後50時間での缶液の分析
は、次の通りでおった。Monoacetin 22.1% Diacetin 52.8% Triacetin 25.1% Example-2 Triacetin production method Using the same reaction apparatus as Example-1, glycerin 552%
g and 2,160 g of acetic acid (6 times the mole of glycerin) were charged to start the reaction. The analysis of the bottom liquid 50 hours after the start of the reaction was as follows.
酢920.85% ジアセチン9.00% トリアセチ
ン70.93%(アセチン比率はモノアセチン0%ジア
セチン10.38% トリアセチン89゜62%)この
反応粗液を50’C以下に冷却後実施例−1と同様にし
て過剰の酢酸を回収し、次いでアセチンを精製した。Vinegar 920.85% Diacetin 9.00% Triacetin 70.93% (acetin ratio: monoacetin 0% diacetin 10.38% triacetin 89°62%) After cooling this reaction crude liquid to below 50'C, Example-1 Excess acetic acid was recovered in the same manner, and then acetin was purified.
得られたアセチンは(Tol)温度145〜147°C
の留分)981(組成ジアセチン8.29% トリアセ
チン91.71%)でおった。The obtained acetin has a (Tol) temperature of 145-147°C
981 (composition: diacetin: 8.29%, triacetin: 91.71%).
実施例−3
実施例−2と同様にして50時間反反応缶温を150’
Cに冷却した。缶液中に存在するジアセチンに対して1
.2モル倍量の無酢量を計算により求め、滴下した。そ
の後3時間150℃で反応を行なったところ缶液中のジ
アセチンは全てトリアセチンに変化した。次に実施例−
1と同様にして過剰の酢酸及び無酢を回収し、次いでト
リアセチンを精製した。Example-3 The reaction vessel temperature was kept at 150' for 50 hours in the same manner as in Example-2.
Cooled to C. 1 for diacetin present in the can liquid.
.. A non-vinegar amount of 2 moles was determined by calculation and added dropwise. Thereafter, the reaction was carried out at 150° C. for 3 hours, and all of the diacetin in the solution was converted to triacetin. Next, an example-
Excess acetic acid and acetic acid were collected in the same manner as in 1, and then triacetin was purified.
Claims (1)
化学式、表等があります▼(1) (式中nは2、及び3の整数を示す) で表わされるアセチンを製造する方法においてアセチル
化剤として酢酸を、グリセリンに対して0、6×n2か
ら0.8×n2モル倍使用し、生成する水を過剰に存在
する酢酸とともに系外に留去することによつて無触媒で
アセチル化することを特徴とするアセチンの製造方法[Claims] i) Glycerin is acetylated to form the general formula (1)▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (1) (In the formula, n indicates an integer of 2 or 3) In the method for producing acetin, acetic acid is used as an acetylating agent, and glycerin is mixed with 0, 6 x n2. A method for producing acetin characterized by using 0.8×n2 moles and performing acetylation without a catalyst by distilling the produced water out of the system together with an excess of acetic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61171331A JP2514001B2 (en) | 1986-07-21 | 1986-07-21 | Method for producing acetin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61171331A JP2514001B2 (en) | 1986-07-21 | 1986-07-21 | Method for producing acetin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6327456A true JPS6327456A (en) | 1988-02-05 |
JP2514001B2 JP2514001B2 (en) | 1996-07-10 |
Family
ID=15921250
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61171331A Expired - Lifetime JP2514001B2 (en) | 1986-07-21 | 1986-07-21 | Method for producing acetin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2514001B2 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56127332A (en) * | 1980-02-08 | 1981-10-06 | Henkel Kgaa | Continuous manufacture of triacetin |
-
1986
- 1986-07-21 JP JP61171331A patent/JP2514001B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56127332A (en) * | 1980-02-08 | 1981-10-06 | Henkel Kgaa | Continuous manufacture of triacetin |
Also Published As
Publication number | Publication date |
---|---|
JP2514001B2 (en) | 1996-07-10 |
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