JPS63156744A - Recovery of acetic acid - Google Patents
Recovery of acetic acidInfo
- Publication number
- JPS63156744A JPS63156744A JP30378386A JP30378386A JPS63156744A JP S63156744 A JPS63156744 A JP S63156744A JP 30378386 A JP30378386 A JP 30378386A JP 30378386 A JP30378386 A JP 30378386A JP S63156744 A JPS63156744 A JP S63156744A
- Authority
- JP
- Japan
- Prior art keywords
- acetic acid
- liquid
- methyl acetate
- column
- extraction
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 238000011084 recovery Methods 0.000 title description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 43
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 25
- 238000004821 distillation Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000012452 mother liquor Substances 0.000 claims abstract description 18
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- 230000018044 dehydration Effects 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 12
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 8
- 238000000638 solvent extraction Methods 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000002002 slurry Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 bromine compound Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Landscapes
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Extraction Or Liquid Replacement (AREA)
- 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〉
本発明はテレフタル酸製造過程において溶媒として用い
る酢酸の回収方法に関し、特に水中に含まれ損失する酢
酸を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 acetic acid used as a solvent in the process of producing terephthalic acid, and particularly to a method for recovering acetic acid contained in water and lost.
〈従来の技術〉
パラキシレンを触媒の存在下、酢酸溶媒中で分子状酸素
含有ガスにより液相酸化してテレフタル酸を製造する方
法によって得られるスラリー状の酸化反応生成物からテ
レフタル酸を分離した反応母液から酢酸を回収するに当
たり１例えば、該反応母液を蒸留して、溶媒−水混合液
を得、続いて該混合液を溶媒脱水蒸留塔に導入して溶媒
を回収することは公知である（特開昭５１−６３３６９
号公報）。<Prior art> Terephthalic acid was separated from a slurry-like oxidation reaction product obtained by a method of producing terephthalic acid by liquid-phase oxidation of paraxylene with a molecular oxygen-containing gas in an acetic acid solvent in the presence of a catalyst. In recovering acetic acid from a reaction mother liquor, for example, it is known that the reaction mother liquor is distilled to obtain a solvent-water mixture, and then the mixture is introduced into a solvent dehydration distillation column to recover the solvent. (Unexamined Japanese Patent Publication No. 51-63369
Publication No.).
〈発明が解決しようとする問題点〉 しかしながら、この方法は溶媒である酢酸が。<Problem that the invention seeks to solve> However, this method uses acetic acid as a solvent.
その中に含まれる水分を蒸留除去する工程で損失すると
いう問題があり、その為溶媒の原単位が高くなるという
欠点がある。There is a problem in that the water contained therein is lost in the process of distilling and removing it, resulting in a disadvantage that the unit consumption of the solvent becomes high.
〈問題点を解決するための手段および作用〉そこで１本
発明者らは上記実情に鑑がみ、酢酸から水分を除去する
脱水蒸留塔の留出水に微量含まれる酢酸を回収する方法
について鋭意研究した結果、パラキシレンの酸化反応の
際、溶媒である酢酸から副生ずる酢酸メチルを用いて液
−液抽出することにより有効に回収できることを見出し
。<Means and effects for solving the problems> 1. In view of the above-mentioned circumstances, the present inventors have worked diligently on a method for recovering acetic acid contained in trace amounts in distilled water from a dehydration distillation column that removes water from acetic acid. As a result of research, it was discovered that para-xylene can be effectively recovered by liquid-liquid extraction using methyl acetate, which is a by-product from the solvent acetic acid, during the oxidation reaction.
本発明を完成させた。The present invention has been completed.
すなわち１本発明はパラキシレンを酢酸溶媒中、触媒の
存在下分子状酸素含有ガスで液相酸化してテレフタル酸
を製造する方法によって得られるスラリー状の酸化反応
生成物からテレフタル酸を分離した反応母液から酢酸を
回収するに当たり。Specifically, the present invention is a reaction in which terephthalic acid is separated from a slurry-like oxidation reaction product obtained by a method for producing terephthalic acid by liquid-phase oxidation of paraxylene with a molecular oxygen-containing gas in an acetic acid solvent in the presence of a catalyst. In recovering acetic acid from mother liquor.
該反応母液を脱水蒸留塔に導入して、塔下部から酢酸を
回収し、塔上部から水を主体とし、酢酸−酢酸メチルを
含む混合液を留出せしめた後、該混合液中に微量含まれ
る酢酸を、液相酸化反応で副生した回収酢酸メチルを主
体とする抽出溶媒を用いて液−液抽出することにより回
収することを特徴とする酢酸の回収方法である。The reaction mother liquor is introduced into a dehydration distillation column, acetic acid is recovered from the bottom of the column, and a mixture mainly composed of water and containing acetic acid and methyl acetate is distilled from the top of the column. This is a method for recovering acetic acid, which is characterized in that acetic acid is recovered by liquid-liquid extraction using an extraction solvent mainly composed of recovered methyl acetate produced as a by-product in a liquid phase oxidation reaction.
以下９本発明の詳細な説明する。Hereinafter, nine aspects of the present invention will be described in detail.
本発明で用いられるテレフタル酸の製造方法としては、
パラキシレンを酢酸溶媒中、触媒の存在下２分子状酸素
含有ガスで、液相酸化してテレフタル酸を製造する方法
であればどの様な方法でもよい。The method for producing terephthalic acid used in the present invention is as follows:
Any method may be used as long as it produces terephthalic acid by liquid phase oxidation of paraxylene in an acetic acid solvent with a bimolecular oxygen-containing gas in the presence of a catalyst.
触媒としては１重金属化合物単独系が通常用いられる。As the catalyst, a single heavy metal compound is usually used.
反応促進剤は使用しても、しなくてもよく使用する場合
は公知のアセトアルデヒド、メチルエチルケトン、パラ
アルデヒド、または臭素化合物などが選ばれる。重金属
触媒としては１通常、コバルト化合物、さらに必要に応
じて、バナジウム化合物、クロム化合物、マンガン化合
物、鉄化合物、ニッケル化合物が用いられる。触媒の使
用量は重金属触媒が７通常、酢酸に対して０．０１〜１
．０重量％であり１反応促進剤を使用する場合には反応
促進剤の使用量は重金属に対して１〜１０重量倍である
。反応温度は１通常、１２０〜２７５℃である。分子状
酸素含有ガスとしては９純酸素や工業排ガスも使用可能
であるが、工業的には通常の空気が用いられる。反応系
中の酸素分圧、全反応圧力が１〜５０気圧の範囲で、排
ガス中の酸素濃度が１〜８％の範囲になるように操作す
るのが好ましい。反応方式としては回分式。A reaction accelerator may or may not be used. When used, a known acetaldehyde, methyl ethyl ketone, paraaldehyde, or a bromine compound is selected. As the heavy metal catalyst, a cobalt compound is usually used, and if necessary, a vanadium compound, a chromium compound, a manganese compound, an iron compound, or a nickel compound is used. The amount of catalyst used is usually 7% of heavy metal catalyst, 0.01 to 1% per acetic acid.
．． When the amount is 0% by weight and one reaction accelerator is used, the amount of reaction accelerator used is 1 to 10 times the weight of the heavy metal. The reaction temperature is usually 120 to 275°C. Although 9-pure oxygen or industrial exhaust gas can be used as the molecular oxygen-containing gas, ordinary air is used industrially. It is preferable to operate so that the oxygen partial pressure in the reaction system and the total reaction pressure are in the range of 1 to 50 atm, and the oxygen concentration in the exhaust gas is in the range of 1 to 8%. The reaction method is batchwise.
半連続式、連続式のいずれも採用できるが、連続式が好
ましく用いられる。Although either a semi-continuous type or a continuous type can be employed, a continuous type is preferably used.
かくして酸化反応を行った結果１本発明における酸化反
応混合物の反応母液中には反応で副生した酢酸メチルが
含まれている。従来、テレフタル酸を分離した反応母液
は１次いで蒸留分離して水分を除去した後、溶媒として
再使用している。この場合９反応母液中の＃酸メチルは
水分と共に留出し、廃棄されていた。本発明では、この
微量の酢酸を含む水−酢酸メチルを蒸留して酢酸メチル
の少くとも一部、好ましくはほぼ全量を回収し。As a result of carrying out the oxidation reaction in this manner, 1. The reaction mother liquor of the oxidation reaction mixture in the present invention contains methyl acetate which was a by-product of the reaction. Conventionally, the reaction mother liquor from which terephthalic acid has been separated is first separated by distillation to remove water, and then reused as a solvent. In this case, the methyl acid #9 in the mother liquor of reaction 9 was distilled out together with water and discarded. In the present invention, at least a portion, preferably substantially the entire amount, of methyl acetate is recovered by distilling the water-methyl acetate containing a trace amount of acetic acid.
これを前記酢酸を微量含む水の抽出溶媒に使用するもの
である。This is used as an extraction solvent for the water containing a trace amount of acetic acid.
以下２図面を参照しつつ本発明を説明する。The present invention will be described below with reference to two drawings.
第１図は本発明の一実施態様のフローを示す図である。FIG. 1 is a diagram showing the flow of one embodiment of the present invention.
酸化反応で得られるスラリー状の酸化反応生成物からテ
レフタル酸を分離した反応母液（１）を先ず、塔頂９０
〜１１０’Ｃ，塔底１１０〜１３０℃の脱水蒸留塔（２
）で蒸留することにより、塔下部から酢酸（３）を回収
し、塔上部から水を主体とする混合液（４）を留出せし
める。この混合液（４）中には微量の酢酸および酢酸メ
チルが含まれているが、微量であるため１通常は分液せ
ずに単相になっている。尚１反応母液（１）については
、常圧下１例えば１２０〜１５０℃で蒸留して酢酸−ホ
ー酢酸メチル混合蒸気を蒸発させ、脱水蒸留塔に供給す
る方法でもよい。次いで、混合液（４）を常法により、
液−液抽出基（５）の上部に導入し、抽出塔下部に後述
する方法にて回収した酢酸メチルを主体とする抽出溶媒
（６）を供給し、相互に向流接触させることにより、塔
上部より酢酸を含有する酢酸メチル（７ンを得る。この
ようにして得た酢酸メチル（７）を１例えば、塔頂５０
〜６５℃、塔底９０〜１１０°Ｃの蒸留塔（８）で蒸留
することにより、酢酸（９）を分離取得し１例えば、脱
水蒸留塔（２）て得られた酢酸（３）と共に回収する。The reaction mother liquor (1) from which terephthalic acid was separated from the slurry-like oxidation reaction product obtained in the oxidation reaction was first collected at the top 90 of the column.
~110'C, bottom 110~130°C dehydration distillation column (2
), acetic acid (3) is recovered from the lower part of the column, and a mixed liquid (4) mainly consisting of water is distilled from the upper part of the column. This mixed solution (4) contains a trace amount of acetic acid and methyl acetate, but since it is a trace amount, it is usually a single phase without being separated. Note that the reaction mother liquor (1) may be distilled under normal pressure at, for example, 120 to 150° C. to evaporate the acetic acid-methyl foracetate mixed vapor and then supplied to the dehydration distillation column. Next, the mixed solution (4) was prepared using a conventional method.
The column is introduced into the upper part of the liquid-liquid extraction group (5), and an extraction solvent (6) mainly composed of methyl acetate recovered by the method described later is supplied to the lower part of the extraction column, and the column is brought into countercurrent contact with the column. Methyl acetate (7) containing acetic acid is obtained from the upper part.
By distilling in a distillation column (8) at ~65°C and a bottom of 90-110°C, acetic acid (9) is separated and collected. do.
蒸留分離した酢酸メチル（１０）は１通常、全量ないし
ほぼ全量抽出溶媒として活用する。一方、抽出塔底部か
ら得られる水（１１）の中には溶解度に相当する酢酸メ
チルを含有する為、この混合物を蒸留塔（１２）で前記
同様、蒸留することにより、塔頂より酢酸メチル（１３
）を回収することができる。このようにして得た酢酸メ
チルは前記同様１通常、全量ないしほぼ全量抽出溶媒と
して活用できるが１本発明の場合、酢酸メチルが次々と
副生される為、敢えて全量回収する必要はない。また２
本発明を実施する場合、酢酸メチルの沸点が低い為、低
温廃熱の回収が容易であり、第２図に示すように、抽出
塔上部から得られる酢酸を含有する酢酸メチル（７）を
熱交換器（１５）を介して脱水蒸留塔（２）の底部液（
３）の熱を有効に回収すると、工業的に更に有利である
。また、酢酸メチルについては、液相酸化反応において
発生するガスの中にも酢酸メチルが含まれているので、
この酢酸メチルを酢酸と接触させ、ガス中に含まれる副
生酢酸メチルのほぼ全量を酢酸に吸収させて回収し、蒸
留塔で蒸留分離の後、抽出溶媒として活用することや、
液相酸化反応において発生するガスを凝縮器によって得
れる凝縮液に含まれる酢酸メチルを蒸留塔で蒸留分離の
後、抽出溶媒として活用することも可能である。Methyl acetate (10) separated by distillation is generally used in all or almost all amount as an extraction solvent. On the other hand, since the water (11) obtained from the bottom of the extraction column contains methyl acetate corresponding to the solubility, by distilling this mixture in the distillation column (12) in the same manner as above, methyl acetate ( 13
) can be recovered. As described above, all or almost all of the methyl acetate thus obtained can normally be used as an extraction solvent, but in the case of the present invention, since methyl acetate is successively produced as a by-product, it is not necessary to recover the entire amount. Also 2
When carrying out the present invention, since the boiling point of methyl acetate is low, it is easy to recover low-temperature waste heat, and as shown in Figure 2, methyl acetate (7) containing acetic acid obtained from the upper part of the extraction column is heated. The bottom liquid (
It is industrially more advantageous if the heat of 3) is effectively recovered. Regarding methyl acetate, the gas generated in the liquid phase oxidation reaction also contains methyl acetate.
This methyl acetate is brought into contact with acetic acid, and almost all of the by-product methyl acetate contained in the gas is absorbed and recovered by the acetic acid, and after distillation separation in a distillation column, it is used as an extraction solvent.
It is also possible to use the gas generated in the liquid phase oxidation reaction as an extraction solvent after distilling and separating methyl acetate contained in a condensate obtained by a condenser using a distillation column.
〈実施例〉 以下実施例により本発明を具体的に説明する。<Example> The present invention will be specifically explained below using Examples.
実施例１
パラキシレンを酢酸溶媒中、触媒として酢酸コバルトを
１反応促進剤としてパラアルデヒドを用い、温度１２０
℃、圧力２０ Ｋ ｇ ／ ｃ ｍ Ｇの条件下で液相
空気酸化して粗テレフタル酸を得た。Example 1 Para-xylene in an acetic acid solvent, cobalt acetate as a catalyst, para-aldehyde as a reaction promoter, temperature 120
℃ and a pressure of 20 K g/cm G to obtain crude terephthalic acid.
得られたテレフタル酸混合スラリーをＯＫｇ／ｃｍＧに
減圧し、混合物スラリーの蒸発潜熱により１２０℃から
１０５℃に冷却せしめた。冷却後の混合物スラリーは遠
心分Ｍ機により母液と分離しテレフタル酸結晶を得た。The resulting terephthalic acid mixed slurry was reduced in pressure to OKg/cmG, and cooled from 120°C to 105°C by the latent heat of vaporization of the mixed slurry. After cooling, the mixture slurry was separated from the mother liquor using a centrifugal separator to obtain terephthalic acid crystals.
次に分離母液を塔頂１００℃、塔底１２０°Ｃの脱水蒸
留塔に導入し。Next, the separated mother liquor was introduced into a dehydration distillation column with a temperature of 100°C at the top and 120°C at the bottom.
塔下部から酢酸を回収すると共に塔上部から水を主体と
する混合液（酢酸１．４％および酢酸メチル−０７７％
を含む）を得た。Acetic acid is recovered from the lower part of the tower, and a mixed liquid mainly composed of water (1.4% acetic acid and 77% methyl acetate) is collected from the upper part of the tower.
) obtained.
以下１図面を参照しつつ本実施例を説明する。This embodiment will be described below with reference to one drawing.
第３図に従って、抽出、溶媒回収からなる操作を行った
。According to FIG. 3, operations consisting of extraction and solvent recovery were performed.
先ず、上記混合液（４）を（１６）を経由し。First, the mixture (4) is passed through (16).
塔径７００ｍｍφ、充填高さ６ｍの蒸留塔（１２）に導
入し、塔頂から酢酸メチル（１３）を回収する。回収し
た酢酸メチル（１３）は、受そう（１７）に受入れ貯留
させ、該酢酸メチルを抽出塔（５）に充満させた。抽出
塔は塔径１０００ｍｍφ、充填高さが４ｍである。次に
、抽出塔の（５）の下から５０°Ｃに設定した酢酸メチ
ル（６）を７．５ｍ／Ｈ，上部に脱水蒸留塔から留出し
た酢酸および酢酸メチルを含む水を主体とする混合液（
４）を５０°Ｃに設定して、５ｍ／Ｈ供給した。抽出塔
（５）の最下部からは溶解度に相当する酢酸メチルを含
有した水（１１）（以下、抽残相）を得、抽出塔の最上
部からは酢酸を抽出した酢酸メチル（７）（以下、抽出
相）を得た。その両液をそれぞれ（１２）および、塔径
１０００ｍｍφ。The mixture is introduced into a distillation column (12) having a column diameter of 700 mmφ and a packing height of 6 m, and methyl acetate (13) is recovered from the top of the column. The recovered methyl acetate (13) was received and stored in the receiving tank (17), and the extraction column (5) was filled with the methyl acetate. The extraction column has a column diameter of 1000 mmφ and a filling height of 4 m. Next, from the bottom of the extraction column (5), methyl acetate (6) was heated to 50°C at 7.5 m/H, and at the top, water containing mainly acetic acid and methyl acetate distilled from the dehydration distillation column was added. Mixture(
4) was set at 50°C and supplied at 5m/H. Water (11) (hereinafter referred to as raffinate phase) containing methyl acetate corresponding to the solubility is obtained from the bottom of the extraction column (5), and methyl acetate (7) (from which acetic acid has been extracted) is obtained from the top of the extraction column (5). Hereinafter, an extraction phase) was obtained. (12) and a column with a diameter of 1000 mmφ.
充填高さ６ｍの蒸留塔（８）に供給し、酢酸メチル（１
０）、（１３）を精製回収した。水を主体とする混合液
（４）を供給して１２時間後、蒸留塔（１２）の底部液
（１４）に含まれる酢酸濃度を測定したところ０．１７
％であった。また、抽出相と抽残相との分離界面も良好
であり、運転操作上に問題はなかった。Methyl acetate (1
0) and (13) were purified and recovered. 12 hours after supplying the mixed liquid (4) mainly consisting of water, the acetic acid concentration contained in the bottom liquid (14) of the distillation column (12) was measured to be 0.17.
%Met. Moreover, the separation interface between the extraction phase and the raffinate phase was also good, and there were no problems in operation.
〈発明の効果〉
本発明によれば、脱水蒸留塔の留出水に微量含まれる酢
酸までも回収する事ができる。この結果、留出水と共に
廃棄されていた酢酸の損失が著しく低下する。しかも２
反応母液中の副生酢酸メチルを回収し抽出溶媒として活
用するので、系が複雑になることもなく２回収再使用が
容易であり。<Effects of the Invention> According to the present invention, even trace amounts of acetic acid contained in the distilled water of the dehydration distillation column can be recovered. As a result, the loss of acetic acid, which would have been discarded together with distilled water, is significantly reduced. And 2
Since the by-product methyl acetate in the reaction mother liquor is recovered and used as an extraction solvent, the system can be easily recovered and reused twice without complicating the system.
工業的メリットは大きい。その為、酢酸原単位が低くな
り、極めて経済的で工業的に有利な方法を提供できた。The industrial benefits are great. Therefore, the basic unit of acetic acid was reduced, and an extremely economical and industrially advantageous method could be provided.
第１図および第２図は本発明の一実施態様を示すフロー
であり、また、第３図は本実施例で使用したフローであ
り１図中の数字および文字は次のことを示す。
２：脱水蒸留塔、５：抽出塔、８．１２：酢酸メチル回
収塔、１５：熱交換器、１７：酢酸メチル受そう。
特許出願大東し株式会社
手 続 補 正 書
１．事件の表示
昭和６１年特許願第 ３０３７８３ 号２、発明の
名称
酢酸の回収方法
自発
５、補正だより増加する発明の数 ０
６、補正の対象
明細書の特許請求の範囲および発明の詳細な（１）
特許請求の範囲を別紙のとおり補正する。
（２） 明細書第３ページ下から第３〜２行目および
第５ページ第９〜１０行目
「反応で副生した」を
「反応で酢酸から副生した」と補正する。
−２、
特許請求の範囲
（１）パラキシレンを酢酸溶媒中、触媒の存在下分子状
酸素含有ガスで液相酸化してテレフタル酸を製造する方
法によって得られるスラリー状の酸化反応生成物からテ
レフタル酸を分離した反応母液から酢酸を回収するにあ
たり、該反応母液を脱水蒸留塔に導入して、塔下部から
酢酸を回収し、塔上部から水を主体とし、酢酸−酢酸メ
チルを含む混合液を留出せしめた後、該混合液中に微量
歯まれる酢酸を、液相酸化反応で酢酸から副生した回収
酢酸メチルを主体とする抽出溶媒を用いて液−液抽出す
ることにより回収することを特徴とする酢酸の回収方法
。
（２）酢酸メチルを主体とする抽出溶媒が液相酸化反応
において発生するガスに含まれる酢酸メチルのほぼ全量
を回収したものを含有する特許請求の範囲第１項記載の
酢酸の回収方法。1 and 2 are flows showing one embodiment of the present invention, and FIG. 3 is a flow used in this embodiment. Numbers and letters in FIG. 1 indicate the following. 2: Dehydration distillation column, 5: Extraction column, 8.12: Methyl acetate recovery column, 15: Heat exchanger, 17: Receiving methyl acetate. Patent Application Daito Co., Ltd. Procedures Amendment 1. Indication of the case: Patent Application No. 303783 of 1985 2, Name of the invention: Method for recovering acetic acid spontaneously 5, Number of inventions increasing due to amendment 0 6, Claims of the specification to be amended and details of the invention ( 1)
The scope of claims is amended as shown in the attached sheet. (2) In lines 3 and 2 from the bottom of page 3 of the specification and lines 9 and 10 of page 5, "by-produced in the reaction" is corrected to "by-produced from acetic acid in the reaction." -2. Claims (1) Terephthalic acid is produced from a slurry-like oxidation reaction product obtained by a method for producing terephthalic acid by liquid-phase oxidation of paraxylene with a molecular oxygen-containing gas in an acetic acid solvent in the presence of a catalyst. To recover acetic acid from the reaction mother liquor from which the acid has been separated, the reaction mother liquor is introduced into a dehydration distillation column, acetic acid is recovered from the lower part of the column, and a mixed liquid mainly composed of water and containing acetic acid and methyl acetate is collected from the upper part of the column. After distillation, a small amount of acetic acid present in the mixed liquid is recovered by liquid-liquid extraction using an extraction solvent mainly composed of recovered methyl acetate, which is a by-product from acetic acid in a liquid phase oxidation reaction. A method for recovering acetic acid, characterized by: (2) The method for recovering acetic acid according to claim 1, wherein the extraction solvent mainly containing methyl acetate contains a solvent obtained by recovering almost the entire amount of methyl acetate contained in the gas generated in the liquid phase oxidation reaction.
Claims (2)
酸素含有ガスで液相酸化してテレフタル酸を製造する方
法によって得られるスラリー状の酸化反応生成物からテ
レフタル酸を分離した反応母液から酢酸を回収するに当
たり、該反応母液を脱水蒸留塔に導入して、塔下部から
酢酸を回収し、塔上部から水を主体とし、酢酸−酢酸メ
チルを含む混合液を留出せしめた後、該混合液中に微量
含まれる酢酸を、液相酸化反応で副生した回収酢酸メチ
ルを主体とする抽出溶媒を用いて液−液抽出することに
より回収することを特徴とする酢酸の回収方法。(1) Terephthalic acid is separated from the reaction mother liquor from the slurry-like oxidation reaction product obtained by a method of producing terephthalic acid by liquid-phase oxidation of paraxylene with a molecular oxygen-containing gas in the presence of a catalyst in an acetic acid solvent. To recover acetic acid, the reaction mother liquor is introduced into a dehydration distillation column, acetic acid is recovered from the bottom of the column, and a mixed liquid mainly composed of water and containing acetic acid and methyl acetate is distilled from the top of the column. A method for recovering acetic acid, which comprises recovering a trace amount of acetic acid contained in a liquid mixture by liquid-liquid extraction using an extraction solvent mainly composed of recovered methyl acetate produced as a by-product in a liquid phase oxidation reaction.
において発生するガスに含まれる酢酸メチルのほぼ全量
を回収したものを含有する特許請求の範囲第１項記載の
酢酸の回収方法。(2) The method for recovering acetic acid according to claim 1, wherein the extraction solvent mainly containing methyl acetate contains a solvent obtained by recovering almost the entire amount of methyl acetate contained in the gas generated in the liquid phase oxidation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30378386A JPS63156744A (en) | 1986-12-22 | 1986-12-22 | Recovery of acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30378386A JPS63156744A (en) | 1986-12-22 | 1986-12-22 | Recovery of acetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63156744A true JPS63156744A (en) | 1988-06-29 |
| JPH041734B2 JPH041734B2 (en) | 1992-01-14 |
Family
ID=17925233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30378386A Granted JPS63156744A (en) | 1986-12-22 | 1986-12-22 | Recovery of acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63156744A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0635474A1 (en) * | 1993-07-12 | 1995-01-25 | Glitsch, Inc. | Method and apparatus for recovering acetic acid from aqueous streams |
| WO2006109999A1 (en) * | 2005-04-14 | 2006-10-19 | Amtpacific Co., Ltd. | Recovering method of acetic acid from effluent of terephthalic acid production process |
| JP2012158614A (en) * | 2003-10-02 | 2012-08-23 | Mitsubishi Gas Chemical Co Inc | Process for producing high-purity terephthalic acid |
| CN103012102A (en) * | 2011-09-27 | 2013-04-03 | 中国石油化工股份有限公司 | Method of recovering acetic acid and water in production of aromatic carboxylic acid |
| CN104874196A (en) * | 2015-03-26 | 2015-09-02 | 南京师范大学 | Method for processing sodium and ammonium acetate-diazonium organic compound-methanol-water mixed solution |
| CN105001073A (en) * | 2015-07-02 | 2015-10-28 | 中国石油天然气集团公司 | PTA production method with low energy consumption, low material consumption andlow refuse discharge |
| JP2018062512A (en) * | 2016-10-12 | 2018-04-19 | 三菱ケミカル株式会社 | Method and apparatus for producing aqueous organic carboxylic acid solution |
-
1986
- 1986-12-22 JP JP30378386A patent/JPS63156744A/en active Granted
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0635474A1 (en) * | 1993-07-12 | 1995-01-25 | Glitsch, Inc. | Method and apparatus for recovering acetic acid from aqueous streams |
| JPH0753443A (en) * | 1993-07-12 | 1995-02-28 | Glitsch Inc | Process and apparatus for recovering acetic acid from water-soluble stream |
| KR100356427B1 (en) * | 1993-07-12 | 2003-04-11 | 글리치인코포레이티드 | Method and apparatus for recovering acetic acid from aqueous streams |
| JP2012158614A (en) * | 2003-10-02 | 2012-08-23 | Mitsubishi Gas Chemical Co Inc | Process for producing high-purity terephthalic acid |
| JP5047501B2 (en) * | 2003-10-02 | 2012-10-10 | 三菱瓦斯化学株式会社 | Method for producing high purity terephthalic acid |
| WO2006109999A1 (en) * | 2005-04-14 | 2006-10-19 | Amtpacific Co., Ltd. | Recovering method of acetic acid from effluent of terephthalic acid production process |
| CN103012102A (en) * | 2011-09-27 | 2013-04-03 | 中国石油化工股份有限公司 | Method of recovering acetic acid and water in production of aromatic carboxylic acid |
| CN104874196A (en) * | 2015-03-26 | 2015-09-02 | 南京师范大学 | Method for processing sodium and ammonium acetate-diazonium organic compound-methanol-water mixed solution |
| CN104874196B (en) * | 2015-03-26 | 2016-09-14 | 南京师范大学 | A kind of method processing sodium and ammonium acetate salt-diazonium Organic substance-methanol-water mixed solution |
| CN105001073A (en) * | 2015-07-02 | 2015-10-28 | 中国石油天然气集团公司 | PTA production method with low energy consumption, low material consumption andlow refuse discharge |
| JP2018062512A (en) * | 2016-10-12 | 2018-04-19 | 三菱ケミカル株式会社 | Method and apparatus for producing aqueous organic carboxylic acid solution |
| JP2021138772A (en) * | 2016-10-12 | 2021-09-16 | 三菱ケミカル株式会社 | Production method and apparatus of aqueous solution of organic carboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH041734B2 (en) | 1992-01-14 |
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