JPH0635418B2 - Purification method of acetic acid - Google Patents
Purification method of acetic acidInfo
- Publication number
- JPH0635418B2 JPH0635418B2 JP59176729A JP17672984A JPH0635418B2 JP H0635418 B2 JPH0635418 B2 JP H0635418B2 JP 59176729 A JP59176729 A JP 59176729A JP 17672984 A JP17672984 A JP 17672984A JP H0635418 B2 JPH0635418 B2 JP H0635418B2
- Authority
- JP
- Japan
- Prior art keywords
- acetic acid
- acid
- product
- potassium permanganate
- peracetic acid
- 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 - Lifetime
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明は過酢酸を用いて酢酸を精製する方法即ち、過マ
ンガン酸カリウム試験保持時間の短かい酢酸に過酢酸を
添加し、50℃から120℃の範囲で温度で1〜20時
間加熱処理した後、蒸留することを特徴とする酢酸の精
製方法に関するものである。酢酸の工業的な製造法とし
ては、アセトアルデヒドの酸化による法、石油ナフサあ
るいはブタン、プロパン等の直接酸化による法、オレフ
ィン類と過酢酸あるいは不飽和アルコール類と過酢酸
(これらの場合の過酢酸は酸素導入剤として作用する)
からエポキサイドを合成する際に副成する酢酸を精製し
て得る法、メタノールと一酸化炭素から直接合成する法
などがあるが一般にこれらの合成酢酸中には種々の不純
物が混入しているため、この酢酸を精製することは、か
なりやっかいである。DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for purifying acetic acid using peracetic acid, that is, by adding peracetic acid to acetic acid having a short potassium permanganate test retention time at a temperature in the range of 50 ° C. to 120 ° C. The present invention relates to a method for purifying acetic acid, which comprises performing a heat treatment for 1 to 20 hours and then distilling it. As an industrial production method of acetic acid, a method by oxidation of acetaldehyde, a method by direct oxidation of petroleum naphtha or butane, propane, etc., olefins and peracetic acid or unsaturated alcohols and peracetic acid (peracetic acid in these cases is Acts as an oxygen introducing agent)
There is a method of purifying by-product acetic acid when epoxide is synthesized from, a method of directly synthesizing from methanol and carbon monoxide, etc. However, since various impurities are generally mixed in these synthetic acetic acid, Purifying this acetic acid is rather cumbersome.
特に還元性物質が製品酢酸中に極微量含まれていても製
品酢酸としての価値が失なわれる。従来酢酸中の還元性
物質含有量をあらわす尺度として酢酸の製品分析規格の
中に過マンガン酸カリウム試験法があり、この場合の変
色保持時間は一般向酢酸製品規格としては5分以上であ
るが、用途によっては過マンガン酸カリウム保持時間が
60分以上が要求される。In particular, the value of the acetic acid product is lost even if a reducing substance is contained in the acetic acid product in an extremely small amount. Conventionally, as a measure of the content of reducing substances in acetic acid, the acetic acid product analysis standard includes the potassium permanganate test method, and the discoloration retention time in this case is 5 minutes or more as a general acetic acid product standard. Depending on the application, a holding time of potassium permanganate of 60 minutes or more is required.
以前、本出願人はすぐれた酢酸の精製方法(特公昭48
−30615)を提案したが、これは過酢酸を添加しな
がら蒸留することにより、過マンガン酸カリウム試験保
持時間の長い酢酸を得る方法であった。しかし、この方
法でも、ある種の副成酢酸に対しては全く効果が得られ
なかった。Previously, the applicant of the present invention was found to have an excellent purification method for acetic acid (Japanese Patent Publication No.
-30615) was proposed, which was a method of obtaining acetic acid having a long retention time in the potassium permanganate test by distilling while adding peracetic acid. However, even this method was not effective at all with respect to some by-product acetic acid.
そこで本発明者らが鋭意検討を重ねた結果、上記方法で
は精製される酢酸と過酢酸との接触が蒸留塔内でのみし
か行なわれない(接触時間が短い)ためである事実を解
明し、本発明に至った。Therefore, as a result of intensive studies by the present inventors, the fact that the above-mentioned method makes contact between purified acetic acid and peracetic acid only in the distillation column (short contact time) has been clarified. The present invention has been completed.
本発明の方法に従えば、前処理として蒸留塔に仕込む前
に原料となる酢酸に対し少量の過酢酸を加え、一定温度
で一定時間保持した後、蒸留精製したところ、従来の方
法では改良しえず、過マンガン酸カリウム保持時間の短
かかった酢酸についても、この試験に充分合格し得る純
良酢酸を得ることが可能になった。According to the method of the present invention, a small amount of peracetic acid was added to acetic acid as a raw material before charging to a distillation column as a pretreatment, and the mixture was maintained at a constant temperature for a predetermined time and then purified by distillation. First of all, it has become possible to obtain pure good acetic acid that can sufficiently pass this test even with acetic acid having a short retention time of potassium permanganate.
本発明に用いる過酢酸は酢酸や酢酸エチル等の溶媒で稀
釈され、20〜40%の溶液として用いられる。過酢酸
の添加量は精製される酢酸に対して0.1重量%〜5重量
%の範囲から選ばれるが、過酢酸の添加量については精
製しようとするそれぞれの酢酸の品質に応じて適量添加
してやることが有利である。The peracetic acid used in the present invention is diluted with a solvent such as acetic acid or ethyl acetate and used as a 20 to 40% solution. The addition amount of peracetic acid is selected from the range of 0.1% to 5% by weight with respect to the acetic acid to be purified, but the addition amount of peracetic acid should be an appropriate amount according to the quality of each acetic acid to be purified. Is advantageous.
本発明における加熱処理では温度は50〜120℃の範囲で
あり、時間は温度との関数で選ばれる。例えば、50℃
なら20時間程度、120℃では1時間程度である。従
って、これ等処理条件(過酢酸の添加量及び加熱温度、
時間等)は精製される酢酸中の還元性物質の含有量によ
って影響されるので、適宜実験から決定されるべきであ
る。In the heat treatment of the present invention, the temperature is in the range of 50 to 120 ° C, and the time is selected as a function of the temperature. For example, 50 ℃
If so, it takes about 20 hours, and at 120 ° C, it takes about 1 hour. Therefore, these processing conditions (amount of peracetic acid added and heating temperature,
Since the time) is influenced by the content of the reducing substance in the acetic acid to be purified, it should be appropriately determined from experiments.
蒸留では通常の蒸留精製法が採用される。先ず第1精製
蒸留し、塔頂より酢酸中の微量低沸点成分及び過酢酸溶
媒を留出させる。更にこの釜出液を第2精製蒸留し、塔
頂より製品として過マンガン酸カリウム試験保持時間の
長い純良酢酸を得る。In distillation, a usual distillation purification method is adopted. First, the first purification distillation is performed, and a trace amount of a low boiling point component in acetic acid and a peracetic acid solvent are distilled from the top of the column. Further, this kettle liquor is subjected to the second purification distillation to obtain pure good acetic acid having a long potassium manganate test retention time as a product from the top of the column.
なお、添加された過酢酸は加熱処理及び蒸留中に熱分解
し、製品と同じ酢酸に変えるので、余分な分離精製を必
要としない。Since the added peracetic acid is thermally decomposed during the heat treatment and distillation and converted into the same acetic acid as the product, no extra separation and purification is required.
以下に、本発明の効果を明らかにした実施例及び比較例
を示す。Examples and comparative examples that clarify the effects of the present invention will be shown below.
実施例1. ε−カプロラクトン合成における副成酢酸を撹拌器、凝
縮器を備えた5の加熱可能な容器に3000g仕込
み、酢酸エチル、酢酸で30%に稀釈された過酢酸を9
g(過酢酸純量)添加する。内部温度を120℃に昇温
し、更に1時間同温度で撹拌する。Example 1. 3000 g of acetic acid by-produced in the synthesis of ε-caprolactone was charged into a heatable container 5 equipped with a stirrer and a condenser, and 9% of peracetic acid diluted to 30% with ethyl acetate and acetic acid was charged.
g (net amount of peracetic acid) is added. The internal temperature is raised to 120 ° C., and the mixture is further stirred for 1 hour at the same temperature.
次に、上記液を常圧にて連続蒸留する。まず第1精製塔
(内径50φ、60段の棚段塔)では、塔底から50段
目に100g/Hの速度で先の過酢酸処理液を連続的に
仕込み、還流比を30として塔頂から酢酸エチル6.3%
を含有する酢酸を10g/Hで留出させる。Next, the above liquid is continuously distilled at atmospheric pressure. First, in the first purification tower (inner diameter 50φ, 60 tray tray tower), the above-mentioned peracetic acid treatment liquid was continuously charged at a rate of 100 g / H at the 50th tray from the bottom of the tower, and the reflux ratio was set to 30 at the top of the tower. From ethyl acetate 6.3%
The acetic acid containing is distilled off at 10 g / H.
更に塔底から90g/Hで酢酸を連続的に抜き取り、第
2精製塔に供給した。第2精製塔(内径50φ、40段
の棚段塔)では塔底から20段目に第1精製塔の缶抜きと
り液を90g/Hの速度で仕込み、還流比を2として塔
頂より85g/Hで製品酢酸を留出させた。このようにし
て得られた製品酢酸の過マンガン酸カリウム試験の結果
は150分であった。Furthermore, acetic acid was continuously withdrawn from the bottom of the column at 90 g / H and supplied to the second purification column. In the second purification tower (inner diameter 50φ, 40 tray tray tower), the can extractor from the first purification tower was charged at the 20th tray from the bottom of the tower at a rate of 90 g / H, and the reflux ratio was 2, and 85 g from the top of the tower. The product acetic acid was distilled off at / H. The product acetic acid thus obtained was tested for potassium permanganate in a result of 150 minutes.
比較例1. 実施例1の副成酢酸を過酢酸添加による加熱処理しなか
った以外は連続蒸留に関して実施例1と同様に実施し
た。得られた製品酢酸の過マンガン酸カリウム試験の結
果はゼロ分であった。Comparative Example 1. The continuous distillation was performed in the same manner as in Example 1 except that the by-product acetic acid of Example 1 was not heat-treated by adding peracetic acid. The result of the potassium permanganate test of the resulting product acetic acid was zero minutes.
実施例2. 実施例1の過酢酸添加後の加熱を50℃にて20時間と
した以外は実施例1と同様の方法で行った。得られた製
品酢酸の過マンガン酸カリウム試験の結果は65分であ
った。Example 2. The same procedure as in Example 1 was carried out except that the heating after the addition of peracetic acid in Example 1 was carried out at 50 ° C. for 20 hours. The result of potassium permanganate test on the resulting product acetic acid was 65 minutes.
実施例3. 実施例1のε−カプロラクトン合成の副成酢酸のかわり
にC12・C14のα−オレフィンオキサイド合成に於ける副
成酢酸を用いた以外は実施例1と同様の方法で行った。
得られた製品酢酸の過マンガン酸カリウム試験の結果は
70分であった。Example 3. The same procedure as in Example 1 was carried out except that the by-product acetic acid in the synthesis of C 12 · C 14 α-olefin oxide was used in place of the by-product acetic acid in the synthesis of ε-caprolactone of Example 1.
The resulting product, acetic acid, had a potassium permanganate test result of 70 minutes.
比較例2. 実施例3の副成酢酸を過酢酸添加による加熱処理しなか
った以外は連続蒸留に関して実施例3と同様に実施し
た。得られた製品酢酸の過マンガン酸カリウム試験の結
果はゼロ分であった。Comparative example 2. The continuous distillation was performed in the same manner as in Example 3 except that the by-product acetic acid of Example 3 was not heat-treated by adding peracetic acid. The result of the potassium permanganate test of the resulting product acetic acid was zero minutes.
実施例4. 実施例1のε−カプロラクトン合成の副成酢酸のかわり
に、グリセリン合成に於ける副成酢酸を用いた以外は実
施例1と同様の方法で行なった。得られた製品酢酸の過
マンガン酸カリウム試験の結果は200分であった。Example 4. The same procedure as in Example 1 was carried out except that the byproduct acetic acid in the synthesis of glycerin was used in place of the byproduct acetic acid in the synthesis of ε-caprolactone in Example 1. The result of the potassium permanganate test on the resulting product acetic acid was 200 minutes.
比較例3. 実施例4の副成酢酸を過酢酸添加による加熱処理しなか
った以外は連続蒸留に関して実施例4と同様に実施し
た。得られた製品酢酸の過マンガン酸カリウム試験の結
果は95分であった。Comparative Example 3. The continuous distillation was performed in the same manner as in Example 4 except that the byproduct acetic acid of Example 4 was not heat-treated by adding peracetic acid. The result of potassium permanganate test on the resulting product acetic acid was 95 minutes.
Claims (1)
い酢酸に過酢酸を添加し、50℃から120℃の範囲の温
度で1〜20時間加熱処理した後、蒸溜することを特徴と
する酢酸の精製方法1. An acetic acid characterized in that peracetic acid is added to acetic acid having a short holding time for potassium permanganate test, the mixture is heated at a temperature in the range of 50 ° C. to 120 ° C. for 1 to 20 hours, and then distilled. Purification method
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59176729A JPH0635418B2 (en) | 1984-08-27 | 1984-08-27 | Purification method of acetic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59176729A JPH0635418B2 (en) | 1984-08-27 | 1984-08-27 | Purification method of acetic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6156151A JPS6156151A (en) | 1986-03-20 |
JPH0635418B2 true JPH0635418B2 (en) | 1994-05-11 |
Family
ID=16018760
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59176729A Expired - Lifetime JPH0635418B2 (en) | 1984-08-27 | 1984-08-27 | Purification method of acetic acid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0635418B2 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9100216D0 (en) * | 1991-01-05 | 1991-02-20 | Bp Chem Int Ltd | Process |
JP3220234B2 (en) * | 1992-07-07 | 2001-10-22 | ダイセル化学工業株式会社 | Purification of acetic anhydride or a mixture of acetic anhydride and acetic acid with ozone |
US5783731A (en) * | 1995-09-11 | 1998-07-21 | Hoechst Celanese Corporation | Removal of carbonyl impurities from a carbonylation process stream |
IN192600B (en) * | 1996-10-18 | 2004-05-08 | Hoechst Celanese Corp | |
US6339171B1 (en) | 1996-10-18 | 2002-01-15 | Celanese International Corporation | Removal or reduction of permanganate reducing compounds and alkyl iodides from a carbonylation process stream |
US7208625B1 (en) * | 2006-08-04 | 2007-04-24 | Lyondell Chemical Technology, L.P. | Removing permanganate-reducing impurities from acetic acid |
CA2976310A1 (en) | 2015-02-25 | 2016-09-01 | Sabic Global Technologies B.V. | Process for removing impurities from acetic acid |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4830615A (en) * | 1971-08-24 | 1973-04-23 |
-
1984
- 1984-08-27 JP JP59176729A patent/JPH0635418B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4830615A (en) * | 1971-08-24 | 1973-04-23 |
Also Published As
Publication number | Publication date |
---|---|
JPS6156151A (en) | 1986-03-20 |
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Legal Events
Date | Code | Title | Description |
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EXPY | Cancellation because of completion of term |