JPH0515788A - Recovery of liquid phase oxidizing catalyst of para-xylene - Google Patents
Recovery of liquid phase oxidizing catalyst of para-xyleneInfo
- Publication number
- JPH0515788A JPH0515788A JP3172795A JP17279591A JPH0515788A JP H0515788 A JPH0515788 A JP H0515788A JP 3172795 A JP3172795 A JP 3172795A JP 17279591 A JP17279591 A JP 17279591A JP H0515788 A JPH0515788 A JP H0515788A
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- carbonate
- acetic acid
- catalyst
- manganese
- 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
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はパラキシレンの酸化用金
属触媒の回収方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering a metal catalyst for paraxylene oxidation.
【０００２】[0002]
【従来の技術】パラキシレンを酢酸溶媒中、コバルト、
マンガン及び臭素化合物より成る触媒の存在下、分子状
酸素により液相酸化してテレフタル酸を製造する方法は
ＳＤ法としてよく知られている。この方法で生成したテ
レフタル酸を分離した後の反応母液中には、酢酸溶媒の
ほか、触媒の金属成分が含有されているので、これらを
回収して再使用することが望ましい。2. Description of the Related Art Para-xylene is added to cobalt,
The method for producing terephthalic acid by liquid-phase oxidation with molecular oxygen in the presence of a catalyst composed of manganese and bromine compounds is well known as the SD method. Since the reaction mother liquor after separating the terephthalic acid produced by this method contains the acetic acid solvent and the metal component of the catalyst, it is desirable to recover and reuse them.
【０００３】従来、酢酸溶媒は、反応母液をたき上げて
回収し、次いで、蒸留して水分を除去して再使用してい
る。一方、触媒の金属成分は、前記たき上げにて得られ
た残留物と水を混合し、金属成分を水に溶解させ水溶液
とし、これに炭酸ソーダを加えて炭酸塩として沈殿させ
て回収している。Conventionally, the acetic acid solvent is reused after raising the reaction mother liquor to recover it and then distilling it to remove water. On the other hand, the metal component of the catalyst is obtained by mixing the residue obtained by the above-mentioned pumping with water and dissolving the metal component in water to form an aqueous solution, and adding sodium carbonate to this to precipitate it as a carbonate to recover it. There is.
【０００４】この炭酸塩として金属触媒を回収する方法
としては、炭酸ソーダを上記水溶液のpHが６．５〜７．
５の範囲に加えた時点で少なくとも２０分間の熟成処理
の後、更に、pHが８．５以上になるまで炭酸ソーダを添
加する方法が知られている（特公昭５６−２５１９
５）。As a method for recovering the metal catalyst as the carbonate, sodium carbonate is used as the aqueous solution having a pH of 6.5 to 7.
After aging treatment for at least 20 minutes when added to the range of 5, the method of adding sodium carbonate until the pH becomes 8.5 or more is known (Japanese Patent Publication No. 56-2519).
5).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
方法においては、沈殿物の熟成に時間を要し、連続的回
収処理に不向きであった。また、沈殿物を処理槽から取
り出した後、沈殿物を濾過、洗浄を行う必要があり多大
な労力を要していた。However, in the above method, it takes a long time to ripen the precipitate, which is not suitable for the continuous recovery process. Further, it is necessary to filter and wash the precipitate after taking out the precipitate from the processing tank, which requires a great deal of labor.
【０００６】[0006]
【課題を解決するための手段】本発明者等は上記実情に
鑑み、簡易な工程で効率的に触媒の金属成分を回収する
方法につき種々検討した結果、連続式沈殿濃縮装置を用
いた特定の方法において、触媒の金属成分が連続的に効
率よく回収されることを見い出し、本発明に到達した。In view of the above situation, the inventors of the present invention have made various studies on a method for efficiently recovering a metal component of a catalyst with a simple process, and as a result, have found that a specific method using a continuous precipitation concentrator is used. In the method, they found that the metal component of the catalyst was continuously and efficiently recovered, and arrived at the present invention.
【０００７】すなわち、本発明は、パラキシレンを、酢
酸溶媒中、酢酸コバルト、酢酸マンガン及び臭素化合物
から成る触媒の存在下、分子状酸素により液相酸化して
テレフタル酸を製造する方法において、 酸化反応混
合物からテレフタル酸と酢酸溶媒を除去した後の酢酸コ
バルト、酢酸マンガンを含む残留物に水を加えて水溶液
とし、 該水溶液にそのpHが８．５以上になるまで炭
酸アルカリを添加して、コバルト及びマンガンの炭酸塩
を含むスラリーとし、 該スラリーを連続式沈殿濃縮
装置で処理して、コバルト及びマンガンの炭酸塩を沈殿
させ、 連続式沈殿濃縮装置の底部よりコバルト及び
マンガンの炭酸塩を含む濃縮スラリーとして取り出し、
該濃縮スラリーを、酢酸と反応させて得られる酢酸
コバルト及び酢酸マンガンを含む溶液を前記触媒の金属
成分として再使用すること、を特徴とするパラキシレン
の液相酸化触媒の回収方法、に存する。That is, the present invention provides a method for producing terephthalic acid by liquid-phase oxidation of paraxylene with molecular oxygen in the presence of a catalyst consisting of cobalt acetate, manganese acetate and a bromine compound in an acetic acid solvent. Water is added to the residue containing cobalt acetate and manganese acetate after removing the terephthalic acid and acetic acid solvent from the reaction mixture to make an aqueous solution, and alkali carbonate is added to the aqueous solution until the pH thereof becomes 8.5 or more, A slurry containing carbonates of cobalt and manganese is treated with a continuous precipitation concentrator to precipitate the carbonates of cobalt and manganese, and the carbonates of cobalt and manganese are contained from the bottom of the continuous precipitation concentrator. Take out as a concentrated slurry,
And a solution containing cobalt acetate and manganese acetate obtained by reacting the concentrated slurry with acetic acid is reused as a metal component of the catalyst.
【０００８】以下、本発明を詳細に説明する。本発明で
対象となるテレフタル酸の製造法は、パラキシレンを酢
酸溶媒中、酢酸コバルト、酢酸マンガン及び臭素化合物
から成る触媒の存在下、分子状酸素により液相酸化する
方法である。使用される臭素化合物としては臭化水素、
臭化ナトリウム等が挙げられる。触媒の添加量として
は、酢酸コバルト、酢酸マンガンは、溶媒に対する各々
の金属として、通常１００〜１０００ppm 、また、臭素
化合物は、溶媒に対する臭素として、通常３００〜３０
００ppm である。The present invention will be described in detail below. The method for producing terephthalic acid, which is the subject of the present invention, is a method in which para-xylene is subjected to liquid-phase oxidation with molecular oxygen in the presence of a catalyst composed of cobalt acetate, manganese acetate and a bromine compound in an acetic acid solvent. Hydrogen bromide as the bromine compound used,
Examples thereof include sodium bromide. As the amount of the catalyst added, cobalt acetate and manganese acetate are usually 100 to 1000 ppm as each metal with respect to the solvent, and the bromine compound is usually 300 to 30 as bromine with respect to the solvent.
It is 00 ppm.
【０００９】溶媒である酢酸は、パラキシレン１重量部
に対し、通常１〜１０重量部用いられる。また、酢酸中
には約３０重量％までの水分を含んでいてよい。反応条
件としては通常、１５０〜２３０℃の温度、２〜１００
気圧の圧力で行い、分子状酸素含有ガスとしては、通
常、空気が使用される。酸化反応によって生成したテレ
フタル酸は、酸化反応混合物から、通常、晶析、遠心分
離等により分離される。Acetic acid as a solvent is usually used in an amount of 1 to 10 parts by weight per 1 part by weight of paraxylene. Also, acetic acid may contain up to about 30% by weight of water. The reaction conditions are usually 150 to 230 ° C., 2 to 100.
The pressure is atmospheric pressure, and air is usually used as the molecular oxygen-containing gas. The terephthalic acid produced by the oxidation reaction is usually separated from the oxidation reaction mixture by crystallization, centrifugation or the like.
【００１０】反応母液の主成分は酢酸であるので、反応
母液の一部はそのまま反応系に戻して再使用することが
できるが、通常、大部分又は全量についてたき上げ処理
を行い、酢酸溶媒、水分を蒸発分離する。たき上げられ
た含水酢酸は蒸留塔にて水分をある程度除去した後に再
使用される。一方、たき上げ後の残留物は、通常、残留
物に対して１〜１０重量倍の水を加えて、残留物中の触
媒の金属成分を溶解させ水溶液とする。この際、該残留
物に含まれていた微量のテレフタル酸やその他反応副生
物が固形分として析出する場合は、これを分離しておく
方が好ましい。得られた水溶液（以下「原液」という）
は、触媒成分として酢酸コバルト、酢酸マンガンを含有
するほかに、残存酢酸及び酸性副生物を含み、通常、pH
が２以下の強酸性液である。また、原液中の金属濃度
は、通常０．０５〜３重量％である。Since the main component of the reaction mother liquor is acetic acid, a part of the reaction mother liquor can be returned as it is to the reaction system and reused. However, usually, most or all of the reaction mother liquor is subjected to a lifting treatment to remove acetic acid solvent, Water is separated by evaporation. The hydrous acetic acid thus pumped up is reused after removing some water in the distillation column. On the other hand, the residue after the lifting is usually made into an aqueous solution by adding 1 to 10 times by weight of water to the residue to dissolve the metal component of the catalyst in the residue. At this time, when a small amount of terephthalic acid or other reaction by-products contained in the residue is precipitated as a solid content, it is preferable to separate it. Obtained aqueous solution (hereinafter referred to as "stock solution")
In addition to containing cobalt acetate and manganese acetate as catalyst components, it also contains residual acetic acid and acidic byproducts.
Is a strongly acidic liquid of 2 or less. The metal concentration in the stock solution is usually 0.05 to 3% by weight.
【００１１】次に、原液に、炭酸アルカリを添加し、pH
を８．５以上、好ましくは８．７〜９．５に調整し、以
下のようにコバルト及びマンガンの炭酸塩を生成させる
（「ＡｃＯ」はアセチル基を示す。以下、この反応を炭
酸化と称することがある。）。炭酸アルカリとしては、
炭酸リチウム、炭酸ナトリウム、炭酸カリウム等がある
が、炭酸ナトリウムが一般的である。
Ｃｏ（ＡｃＯ）2 ＋Ｎａ2 ＣＯ3 →ＣｏＣＯ3 ↓
Ｍｎ（ＡｃＯ）2 ＋Ｎａ2 ＣＯ3 →ＭｎＣＯ3 ↓
炭酸化反応において、pHが８．５に満たない場合は、炭
酸塩が沈殿物として、析出及び沈降する速度が低下する
ので好ましくない。また、pHが１０以上では、沈殿物の
析出、沈降はほぼ一定であるが、沈殿物の水洗処理量が
多くなるので経済的ではない。従来の回分式沈殿槽を用
いる方法では、沈殿後の、良好な濾過分離を行うため
に、水溶液のpHを２段階制御し、かつ、一定の熟成時間
を必要としていたが、本発明の方法では、一度にpHを
８．５以上にして、すみやかに沈殿物を得ることができ
る。Next, add alkali carbonate to the undiluted solution to adjust the pH.
Is adjusted to 8.5 or more, preferably 8.7 to 9.5, and carbonates of cobalt and manganese are produced as follows (“AcO” represents an acetyl group. Hereinafter, this reaction is referred to as carbonation. Sometimes referred to.). As an alkali carbonate,
There are lithium carbonate, sodium carbonate, potassium carbonate and the like, but sodium carbonate is common. Co (AcO) 2 + Na 2 CO 3 → CoCO 3 ↓ Mn (AcO) 2 + Na 2 CO 3 → MnCO 3 ↓ In the carbonation reaction, when the pH is less than 8.5, carbonate precipitates as a precipitate. And the rate of sedimentation is reduced, which is not preferable. When the pH is 10 or more, precipitation and sedimentation of the precipitate are almost constant, but the amount of the precipitate washed with water increases, which is not economical. In the conventional method using a batch type precipitation tank, the pH of the aqueous solution was controlled in two steps and a certain aging time was required in order to perform good filtration separation after precipitation, but in the method of the present invention, The pH can be adjusted to 8.5 or more at a time, and the precipitate can be immediately obtained.
【００１２】添加する炭酸アルカリは、粉末のまま加え
てもよいが、通常２〜３０重量％、好ましくは５〜２０
重量％の水溶液が使用される。また、該炭酸アルカリ水
溶液及び原液の温度は、通常１０〜６０℃、好ましくは
３０〜４０℃である。原液に炭酸アルカリを添加する段
階としては、原液を後述の連続式濃縮沈殿装置（以下
「濃縮装置」と略すことがある）に導入する前で添加、
混合してもよいし、また、水溶液と炭酸アルカリを別々
に供給し、濃縮装置中で混合することも可能である。し
かしながら、一般的には、前者の方法が好ましい。すな
わち、濃縮装置の前に設けた混合槽において、原液と炭
酸アルカリを十分に混合して炭酸化反応を完了し、コバ
ルト及びマンガンの炭酸塩を含むスラリーとしてから、
該スラリーを濃縮装置で処理する方法が好ましい。The alkali carbonate to be added may be added as a powder, but it is usually 2 to 30% by weight, preferably 5 to 20%.
A weight% aqueous solution is used. The temperature of the alkaline carbonate aqueous solution and the stock solution is usually 10 to 60 ° C, preferably 30 to 40 ° C. The step of adding the alkali carbonate to the stock solution is to add the stock solution before introducing the stock solution into a continuous concentration-precipitation device (hereinafter, may be abbreviated as “concentrator”) described below,
They may be mixed, or the aqueous solution and the alkali carbonate may be separately supplied and mixed in a concentrator. However, in general, the former method is preferred. That is, in a mixing tank provided in front of the concentrating device, the stock solution and alkali carbonate are sufficiently mixed to complete the carbonation reaction, and after forming a slurry containing carbonates of cobalt and manganese,
A method of treating the slurry with a concentrator is preferred.
【００１３】本発明における濃縮装置、すなわち、連続
式沈殿濃縮装置とは、通常、シックナー、クラリファイ
ヤー、沈殿槽、濃縮槽等の多くの名称で呼ばれるもので
あり、液体中の固体粒子群を連続的に重力沈降させて分
離するという処理を行うことができるものであれば形式
について特に限定はない。以下、濃縮装置として最も広
く用いられている中心軸駆動型シックナーを図面により
例示して、本発明の濃縮装置での処理について説明す
る。The concentrating device in the present invention, that is, a continuous precipitation concentrating device is usually called by many names such as thickener, clarifier, settling tank, concentrating tank, etc. The form is not particularly limited as long as it can be subjected to a process of gravitationally settling and separating. Hereinafter, the processing in the concentrating device of the present invention will be described by exemplifying the central axis drive type thickener most widely used as the concentrating device with reference to the drawings.
【００１４】図１は本発明を実施することができる濃縮
装置の縦断面の略図であり、１は供給口、２は越流口、
３は回転軸、４は撹拌羽根、５はブレード、６は排出口
である。例えば、炭酸塩を含むスラリーを供給口１より
供給すると、水溶液は撹拌羽根４でゆっくりと撹拌され
つつ、周辺に向って流れていく。スラリー中の炭酸塩
は、徐々に沈降分離し、また、上澄液は越流口２に流れ
込む。更に、沈殿物は、中央の回転軸３に取り付けられ
たブレード５によって中央に集められ、通常、沈殿した
炭酸塩を５〜５０重量％、好ましくは１０〜３０重量％
含有する濃縮スラリーとして、排出口６より連続的に取
り出す。FIG. 1 is a schematic vertical cross-sectional view of a concentrating device in which the present invention can be carried out. 1 is a supply port, 2 is an overflow port,
3 is a rotating shaft, 4 is a stirring blade, 5 is a blade, and 6 is an outlet. For example, when a slurry containing carbonate is supplied from the supply port 1, the aqueous solution flows toward the periphery while being slowly stirred by the stirring blade 4. The carbonate in the slurry gradually sediments and separates, and the supernatant liquid flows into the overflow port 2. Further, the precipitate is centrally collected by a blade 5 attached to the central rotating shaft 3, and usually 5 to 50% by weight, preferably 10 to 30% by weight of precipitated carbonate is contained.
The concentrated slurry contained is continuously taken out from the outlet 6.
【００１５】取り出された濃縮スラリーは、通常、該ス
ラリーの１０倍量以上、好ましくは１００倍量以上の酢
酸を加えて再溶解し、酢酸化反応により、以下のように
酢酸コバルトと酢酸マンガンを生成させて、触媒の金属
成分の溶液として再使用される。
ＣｏＣＯ3 ＋２ＡｃＯＨ→Ｃｏ（ＡｃＯ）2
ＭｎＣＯ3 ＋２ＡｃＯＨ→Ｍｎ（ＡｃＯ）2
また、より安定した性能を有する触媒成分を回収するた
めには、好ましくは、前述の濃縮装置より取りだした濃
縮スラリーを、上記の酢酸処理を行う前に、水で懸洗し
ておくとよい。水懸洗の方法としては、濃縮スラリーを
取り出し、懸洗槽にて行えばよい。また、濃縮装置よ
り、濃縮スラリーを取り出すことなく、濃縮装置の排出
口付近より洗浄水を供給し、炭酸塩の粒子群が全体一団
となって均一に沈降するように向流洗浄する方法も採用
される。この場合の上昇流の洗浄水の速度は、通常、炭
酸塩の自由沈降速度の０．０５〜０．５倍になるように
する。The concentrated slurry thus taken out is usually redissolved by adding 10 times or more, preferably 100 times or more, of acetic acid, and cobalt acetate and manganese acetate are added as follows by an acetic acid reaction. It is produced and reused as a solution of the metal component of the catalyst. CoCO 3 + 2AcOH → Co (AcO) 2 MnCO 3 + 2AcOH → Mn (AcO) 2 In order to recover a catalyst component having more stable performance, it is preferable that the concentrated slurry taken out from the above-mentioned concentrating device is Before carrying out the acetic acid treatment, it is recommended to wash with water. As a method of suspending washing with water, the concentrated slurry may be taken out and carried out in a suspending washing tank. Also, without removing the concentrated slurry from the concentrating device, the washing water is supplied from the vicinity of the outlet of the concentrating device, and the countercurrent washing is performed so that the carbonate particle groups as a whole settle uniformly. To be done. In this case, the velocity of the ascending wash water is usually 0.05 to 0.5 times the free sedimentation velocity of the carbonate.
【００１６】[0016]
【実施例】次に、本発明を実施例により更に詳細に説明
するが、本発明はその要旨を越えない限り以下の実施例
に限定されるものではない。
実施例１
溶媒に対してＣｏ原子として３００ppm の酢酸コバル
ト、Ｍｎ原子として２００ppm の酢酸マンガン及びＢｒ
原子として１０００ppm の臭化水素酸を含有する含水酢
酸（含水量：２０重量％）を溶媒とし、溶媒／パラキシ
レン重量比３で反応温度２１０℃、圧力２５kg／cm2 、
滞留時間１２０分でチタン製反応容器にてパラキシレン
を空気により連続的に酸化した。EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Example 1 To a solvent, 300 ppm of cobalt acetate as Co atom, 200 ppm of manganese acetate as Mn atom and Br were used.
Using water-containing acetic acid (water content: 20% by weight) containing 1000 ppm of hydrobromic acid as a solvent at a solvent / paraxylene weight ratio of 3 at a reaction temperature of 210 ° C. and a pressure of 25 kg / cm 2 ,
Paraxylene was continuously oxidized with air in a titanium reaction vessel with a residence time of 120 minutes.
【００１７】次いで、酸化反応混合物よりテレフタル酸
粒子を遠心分離した反応母液を蒸発器に導入し溶媒をた
き上げた。蒸発器底部より得られるタール状残留物１重
量部を約２重量部の水と混合し撹拌処理をしたのち、水
スラリー中の固形分を濾過し触媒水溶液２．５重量部を
得た。このようにして得た原液（Ｃｏ：０．４９％、Ｍ
ｎ：０．３２％、酢酸：２．４７％含有）１．５ｍ3 ／
hrと、炭酸ナトリウムの１５重量％水溶液３．０ｍ3 ／
hrを混合槽（体積３０ｍ3 ）に供給し、両液を撹拌混合
して、pH８．７〜９．０に維持し、炭酸塩を含むスラリ
ーを得た。Then, the reaction mother liquor obtained by centrifuging the terephthalic acid particles from the oxidation reaction mixture was introduced into the evaporator to lift the solvent. 1 part by weight of the tar-like residue obtained from the bottom of the evaporator was mixed with about 2 parts by weight of water and stirred, and then the solid content in the water slurry was filtered to obtain 2.5 parts by weight of an aqueous catalyst solution. The stock solution thus obtained (Co: 0.49%, M
n: 0.32%, acetic acid: 2.47% included) 1.5 m 3 /
hr and sodium carbonate 15 wt% aqueous solution 3.0 m 3 /
hr was supplied to a mixing tank (volume: 30 m 3 ), and both solutions were stirred and mixed to maintain pH at 8.7 to 9.0 to obtain a carbonate-containing slurry.
【００１８】該スラリーを４．５ｍ3 ／hrで連続式沈殿
濃縮装置（体積３０ｍ3 ）に供給し、一方、濃縮装置の
底部より洗浄水３．０ｍ3 ／hrを供給した。この結果、
濃縮装置の上部より４．３ｍ3 ／hrでオーバーフローす
る上澄液中のコバルト及びマンガンの濃度は共に１０pp
m 以下であった。また、濃縮装置の底部より取出ポンプ
により取り出される濃縮スラリー中の炭酸塩の濃度は１
４．３重量％であった。更に、該濃縮スラリーに対し、
２倍モル量の含水酢酸（含水率５％）を加えて再作用す
る金属触媒の原液を得た。該原液を使用した触媒を用い
てパラキシレンの液相酸化反応の連続運転を１ケ月続け
たが、テレフタル酸の収率は一定であった。The slurry was supplied at a rate of 4.5 m 3 / hr to a continuous precipitation concentrator (volume: 30 m 3 ), while washing water of 3.0 m 3 / hr was supplied from the bottom of the concentrator. As a result,
Concentrations of cobalt and manganese in the supernatant liquid overflowing from the top of the concentrator at 4.3 m 3 / hr were both 10 pp
It was less than m. The concentration of carbonate in the concentrated slurry taken out from the bottom of the concentrator by the take-out pump is 1
It was 4.3% by weight. Furthermore, for the concentrated slurry,
A two-fold molar amount of hydrous acetic acid (water content: 5%) was added to obtain a stock solution of a metal catalyst that would react again. The liquid phase oxidation reaction of paraxylene was continuously operated for one month using a catalyst using the stock solution, but the yield of terephthalic acid was constant.
【００１９】[0019]
【発明の効果】本発明によれば、パラキシレンの液相酸
化反応において触媒として用いられる酢酸コバルト及び
酢酸マンガンを、高回収率で、かつ、連続的に回収、再
使用することができる。すなわち、連続式沈殿濃縮装置
を用いることにより、反応残液中の触媒金属成分をすみ
やかに炭酸塩の沈殿物とし、濾過分離の操作なしに連続
的に酢酸コバルト及び酢酸マンガンとして回収すること
ができる。EFFECTS OF THE INVENTION According to the present invention, cobalt acetate and manganese acetate used as catalysts in the liquid phase oxidation reaction of paraxylene can be continuously recovered and reused at a high recovery rate. That is, by using a continuous precipitation concentrator, the catalytic metal component in the reaction residual liquid can be promptly converted to a carbonate precipitate, and can be continuously recovered as cobalt acetate and manganese acetate without an operation of filtration and separation. .
【図１】本発明を実施することができる連続式濃縮沈殿
装置の縦断面の略図である。FIG. 1 is a schematic diagram of a vertical cross-section of a continuous concentrating and precipitating apparatus in which the present invention can be implemented.
１ 供給口 ２ 越流口 ３ 回転軸 ４ 撹拌羽根 ５ ブレード ６ 排出口 1 supply port 2 Overflow outlet 3 rotation axes 4 stirring blades 5 blades 6 outlets
Claims (3)
ルト、酢酸マンガン及び臭素化合物から成る触媒の存在
下、分子状酸素により液相酸化してテレフタル酸を製造
する方法において、 酸化反応混合物からテレフタル酸と酢酸溶媒を除去
した後の酢酸コバルト、酢酸マンガンを含む残留物に水
を加えて水溶液とし、 該水溶液にそのpHが８．５以上になるまで炭酸アル
カリを添加して、コバルト及びマンガンの炭酸塩を含む
スラリーとし、 該スラリーを連続式沈殿濃縮装置で処理して、コバ
ルト及びマンガンの炭酸塩を沈殿させ、 該連続式沈殿濃縮装置の底部より、コバルト及びマ
ンガンの炭酸塩を含む濃縮スラリーとして取り出し、 該濃縮スラリーを、酢酸と反応させて得られる酢酸
コバルト及び酢酸マンガンを含む溶液を前記触媒の金属
成分として再使用すること、を特徴とするパラキシレン
の液相酸化触媒の回収方法。1. A method for producing terephthalic acid by liquid phase oxidation of paraxylene with molecular oxygen in the presence of a catalyst comprising cobalt acetate, manganese acetate and a bromine compound in an acetic acid solvent, wherein terephthalic acid is obtained from an oxidation reaction mixture. Water is added to the residue containing cobalt acetate and manganese acetate after removing the acid and acetic acid solvent to form an aqueous solution, and alkali carbonate is added to the aqueous solution until the pH of the solution becomes 8.5 or more. A carbonate-containing slurry, which is treated with a continuous precipitation concentrator to precipitate cobalt and manganese carbonate, and a concentrated slurry containing cobalt and manganese carbonate from the bottom of the continuous precipitation concentrator. And a solution containing cobalt acetate and manganese acetate obtained by reacting the concentrated slurry with acetic acid is used as the catalyst gold. Reuse that method for recovering the liquid phase oxidation catalyst of paraxylene, wherein as component.
重量％である請求項１の方法。2. The carbonate concentration in the concentrated slurry is 5 to 50.
The method of claim 1 which is weight percent.
供給し、炭酸塩の向流洗浄を行う請求項１の方法。3. The method according to claim 1, wherein washing water is supplied from the bottom of the continuous precipitation concentrator to carry out countercurrent washing of carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3172795A JP2557578B2 (en) | 1991-07-12 | 1991-07-12 | Method for recovering liquid phase oxidation catalyst for paraxylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3172795A JP2557578B2 (en) | 1991-07-12 | 1991-07-12 | Method for recovering liquid phase oxidation catalyst for paraxylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0515788A true JPH0515788A (en) | 1993-01-26 |
| JP2557578B2 JP2557578B2 (en) | 1996-11-27 |
Family
ID=15948506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3172795A Expired - Lifetime JP2557578B2 (en) | 1991-07-12 | 1991-07-12 | Method for recovering liquid phase oxidation catalyst for paraxylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2557578B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004359691A (en) * | 2003-06-05 | 2004-12-24 | Eastman Chem Co | Extraction process for removal of impurity from aqueous mixture |
| KR100695793B1 (en) * | 2005-04-08 | 2007-03-16 | 미쓰이 가가쿠 가부시키가이샤 | Method for recovery of oxidation catalyst |
| US7326808B2 (en) | 2006-03-01 | 2008-02-05 | Eastman Chemical Company | Polycarboxylic acid production system employing cooled mother liquor from oxidative digestion as feed to impurity purge system |
| US7326807B2 (en) | 2006-03-01 | 2008-02-05 | Eastman Chemical Company | Polycarboxylic acid production system with enhanced heating for oxidative digestion |
| US7420082B2 (en) | 2006-03-01 | 2008-09-02 | Eastman Chemical Company | Polycarboxylic acid production system employing hot liquor removal downstream of oxidative digestion |
| US7501537B2 (en) | 2006-03-01 | 2009-03-10 | Eastman Chemical Company | Polycarboxylic acid production system employing oxidative digestion with reduced or eliminated upstream liquor exchange |
| WO2010008055A1 (en) | 2008-07-17 | 2010-01-21 | 三菱化学株式会社 | Method and apparatus for treating wastewater |
| US7829037B2 (en) | 2006-03-01 | 2010-11-09 | Eastman Chemical Company | Oxidation system with sidedraw secondary reactor |
| JP2013039561A (en) * | 2011-08-17 | 2013-02-28 | Korea Inst Of Geoscience & Mineral Resources (Kigam) | Method for producing cma liquid catalyst from spent cmb catalyst |
| CN103861650A (en) * | 2012-12-17 | 2014-06-18 | 兴忠行股份有限公司 | Method for recovering cobalt manganese catalyst from terephthalic acid reaction mother solution |
| CN107586973A (en) * | 2017-07-18 | 2018-01-16 | 百川化工(如皋)有限公司 | A kind of method of Call Provision manganese in waste material from cobalt-manganese catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5625195A (en) * | 1979-08-08 | 1981-03-10 | Otsuka Pharmaceut Co Ltd | 2-dialkylaminoquinazoline derivative |
-
1991
- 1991-07-12 JP JP3172795A patent/JP2557578B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5625195A (en) * | 1979-08-08 | 1981-03-10 | Otsuka Pharmaceut Co Ltd | 2-dialkylaminoquinazoline derivative |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004359691A (en) * | 2003-06-05 | 2004-12-24 | Eastman Chem Co | Extraction process for removal of impurity from aqueous mixture |
| KR100695793B1 (en) * | 2005-04-08 | 2007-03-16 | 미쓰이 가가쿠 가부시키가이샤 | Method for recovery of oxidation catalyst |
| EP2574606A1 (en) | 2006-03-01 | 2013-04-03 | Grupo Petrotemex, S.A. De C.V. | Polycarboxylic acid production system employing cooled mother liquor from oxidative digestion as feed to impurity purge system |
| US7326807B2 (en) | 2006-03-01 | 2008-02-05 | Eastman Chemical Company | Polycarboxylic acid production system with enhanced heating for oxidative digestion |
| US7420082B2 (en) | 2006-03-01 | 2008-09-02 | Eastman Chemical Company | Polycarboxylic acid production system employing hot liquor removal downstream of oxidative digestion |
| US7501537B2 (en) | 2006-03-01 | 2009-03-10 | Eastman Chemical Company | Polycarboxylic acid production system employing oxidative digestion with reduced or eliminated upstream liquor exchange |
| US7829037B2 (en) | 2006-03-01 | 2010-11-09 | Eastman Chemical Company | Oxidation system with sidedraw secondary reactor |
| US7326808B2 (en) | 2006-03-01 | 2008-02-05 | Eastman Chemical Company | Polycarboxylic acid production system employing cooled mother liquor from oxidative digestion as feed to impurity purge system |
| WO2010008055A1 (en) | 2008-07-17 | 2010-01-21 | 三菱化学株式会社 | Method and apparatus for treating wastewater |
| EP3034472A1 (en) | 2008-07-17 | 2016-06-22 | Mitsubishi Chemical Corporation | Treatment method and treatment apparatus of wastewater |
| JP2013039561A (en) * | 2011-08-17 | 2013-02-28 | Korea Inst Of Geoscience & Mineral Resources (Kigam) | Method for producing cma liquid catalyst from spent cmb catalyst |
| CN103861650A (en) * | 2012-12-17 | 2014-06-18 | 兴忠行股份有限公司 | Method for recovering cobalt manganese catalyst from terephthalic acid reaction mother solution |
| CN107586973A (en) * | 2017-07-18 | 2018-01-16 | 百川化工(如皋)有限公司 | A kind of method of Call Provision manganese in waste material from cobalt-manganese catalyst |
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| Publication number | Publication date |
|---|---|
| JP2557578B2 (en) | 1996-11-27 |
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