JPH0280320A - Recovering method for transition metal catalyst - Google Patents
Recovering method for transition metal catalystInfo
- Publication number
- JPH0280320A JPH0280320A JP63231334A JP23133488A JPH0280320A JP H0280320 A JPH0280320 A JP H0280320A JP 63231334 A JP63231334 A JP 63231334A JP 23133488 A JP23133488 A JP 23133488A JP H0280320 A JPH0280320 A JP H0280320A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- metal catalyst
- reaction product
- catalyst
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 21
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 150000002366 halogen compounds Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 4
- -1 alkali metal salts Chemical class 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract description 2
- 229940071870 hydroiodic acid Drugs 0.000 abstract description 2
- 229910052741 iridium Inorganic materials 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 150000004678 hydrides Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 238000000605 extraction Methods 0.000 description 26
- 239000010948 rhodium Substances 0.000 description 21
- 229910052703 rhodium Inorganic materials 0.000 description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 17
- 238000011084 recovery Methods 0.000 description 10
- 235000011054 acetic acid Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FEFPDZIYEWFQFK-UHFFFAOYSA-N 2-(4-butylphenyl)propanoic acid Chemical compound CCCCC1=CC=C(C(C)C(O)=O)C=C1 FEFPDZIYEWFQFK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- YPGCWEMNNLXISK-UHFFFAOYSA-N hydratropic acid Chemical class OC(=O)C(C)C1=CC=CC=C1 YPGCWEMNNLXISK-UHFFFAOYSA-N 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- Extraction Or Liquid Replacement (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は遷移金属触媒を用いた化学合成プロセスに於い
て、使用した触媒を反応生成物中から分離回収する方法
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 separating and recovering a used catalyst from a reaction product in a chemical synthesis process using a transition metal catalyst.
〔従来の技術及び発明が解決しようとする課題〕化学合
成プロセスにおいて遷移金属触媒は目的とする反応速度
を目覚ましく向上させることにより、その経済性を高め
ている。特に、いわゆるＣ１化学ではＣｏ、 Ｎｉ、
Ｒｈ、 Ｐｄ、 Ｐｔ等の遷移金属触媒がよく用いられ
る。これらの触媒を用いた化学合成プロセスでは、生成
物中から触媒を分離する必要があり、特にＲｈ、 Ｐｄ
、 Ｐｔ、 Ｉｒ等の高価な触媒を用いる場合には、触
媒を分離、回収する際の回収率がプロセスの経済性に対
して大きな影響を与える。[Prior Art and Problems to be Solved by the Invention] In chemical synthesis processes, transition metal catalysts dramatically improve the desired reaction rate, thereby increasing their economic efficiency. In particular, in so-called C1 chemistry, Co, Ni,
Transition metal catalysts such as Rh, Pd, and Pt are often used. In chemical synthesis processes using these catalysts, it is necessary to separate the catalysts from the products, especially Rh, Pd.
When using expensive catalysts such as , Pt, Ir, etc., the recovery rate when separating and recovering the catalyst has a great influence on the economic efficiency of the process.
従来知られている触媒を分離する方法としては、先ず反
応生成物が比較的低沸点であることを利用して、これを
フランシュすることにより不揮発性触媒と分離する方法
がある。例えば、メタノール法酢酸合成プロセスにおけ
る酢酸とＲｈ触媒の分離にはこのフランシュが用いられ
る。As a conventionally known method for separating a catalyst, there is a method that first takes advantage of the fact that the reaction product has a relatively low boiling point and separates it from a non-volatile catalyst by franching the reaction product. For example, this furanche is used to separate acetic acid and Rh catalyst in the methanol method acetic acid synthesis process.
また、反応生成物と触媒の溶解性の差を利用し、抽出分
離する方法がある。例えば、α−フェニルプロピオン酸
誘導体を含有する反応液に、水又は水と酢酸等の混合物
を抽出溶媒として添加し、反応生成物相と水相に二相分
離させ、水相に触媒として使用したロジウム化合物を抽
出し分離する方法（特開昭６３−１４９３４１、特開昭
６３−１６２６５３）などがある。There is also a method of extraction and separation that takes advantage of the difference in solubility between the reaction product and the catalyst. For example, water or a mixture of water and acetic acid, etc., was added as an extraction solvent to a reaction solution containing an α-phenylpropionic acid derivative, the reaction product phase and the aqueous phase were separated, and the aqueous phase was used as a catalyst. There are methods for extracting and separating rhodium compounds (JP-A-63-149341, JP-A-63-162653).
さらに、触媒の回収率を上げ、プロセスの経済性を高め
るためには、上記のフラッシュ、抽出分離等の方法によ
り回収しきれなかった反応生成物中に残存する触媒を回
収することが必要であり、その手段としては、活性炭等
により吸着し、分離、回収する方法が提案されている（
特開昭６３−１６２０４４）。Furthermore, in order to increase the recovery rate of the catalyst and improve the economic efficiency of the process, it is necessary to recover the catalyst remaining in the reaction products that could not be recovered by the above-mentioned methods such as flashing and extraction separation. As a means of achieving this, a method has been proposed that involves adsorption, separation, and recovery using activated carbon, etc. (
JP-A-63-162044).
しかし、この方法で回収した触媒は再生処理が必要であ
り、特に化学合成プロセスの中に活性炭等により吸着回
収した触媒の再生工程を組み込むことは、プロセスが複
雑になるだけでなく、吸着剤の充填、洗浄、抜取、輸送
という様な複数の固体を取り扱う工程が必要になるから
、プラントの省力化と相反することとなり好ましくない
。However, the catalyst recovered using this method requires regeneration treatment, and in particular, incorporating a regeneration process for the catalyst adsorbed and recovered using activated carbon into the chemical synthesis process not only complicates the process, but also damages the adsorbent. This is undesirable because it requires multiple processes for handling solids, such as filling, washing, sampling, and transportation, which conflicts with the labor saving of the plant.
そこで本発明の目的は、前記したフラッシユ、抽出等に
より触媒の大部分を分離した後に、反応生成物中に微量
残存する遷移金属触媒を効率よく、しかも複雑な触媒再
生操作を要することなく分離、回収し得る方法を提供す
ることである。Therefore, an object of the present invention is to efficiently separate a small amount of transition metal catalyst remaining in the reaction product after separating most of the catalyst by the above-mentioned flashing, extraction, etc., without requiring complicated catalyst regeneration operations. The objective is to provide a method for recovering the waste.
本発明者らは研究を重ねた結果、特定の抽出液を調製す
ることにより、抽出操作のみで反応生成物中からほぼ１
００％近くまで残存する遷移金属触媒を回収することが
出来ることを見出し、本発明に到った。As a result of repeated research, the present inventors have found that by preparing a specific extract solution, almost 100% of the reaction product can be extracted by just the extraction operation.
It has been discovered that it is possible to recover nearly 00% of the remaining transition metal catalyst, and the present invention has been achieved.
即ち本発明は、遷移金属触媒を用いて得られた反応生成
物中に残存する遷移金属触媒を、ハロゲン化合物又はハ
ロゲンを含む水溶液を用いて抽出分離することを特徴と
する遷移金属触媒の回収方法である。That is, the present invention provides a method for recovering a transition metal catalyst, which comprises extracting and separating the transition metal catalyst remaining in a reaction product obtained using a transition metal catalyst using a halogen compound or an aqueous solution containing a halogen. It is.
以下、本発明の方法を更に具体的に説明する。The method of the present invention will be explained in more detail below.
本発明に於いて使用される遷移金属触媒とは、従来一般
に触媒として用いられる遷移金属単体又はその化合物で
あって、Ｆｅ、 Ｃｏ、 Ｎｉ、 Ｃｒ、 Ｃｕ。The transition metal catalyst used in the present invention is a single transition metal or a compound thereof that has been conventionally generally used as a catalyst, such as Fe, Co, Ni, Cr, or Cu.
Ｒｈ、 Ｐｄ、 Ｐｔ、 ｉｒ等の遷移金属を包含す
る。Includes transition metals such as Rh, Pd, Pt, and ir.
次に本発明の抽出液中に含有せしめられるハロゲン化合
物としては、フッ素、塩素、ヨウ素、臭素の水素化合物
、アルカリ金属塩等があり、又ハロゲンとしては、塩素
、ヨウ素が用いられる。特に、抽出条件及び設備的な観
点から塩化水素酸く塩酸）及びヨウ化水素酸が好ましい
。Next, examples of halogen compounds to be contained in the extract of the present invention include hydrogen compounds of fluorine, chlorine, iodine, and bromine, alkali metal salts, and chlorine and iodine are used as the halogens. Particularly preferred are hydrochloric acid (hydrochloric acid) and hydroiodic acid from the viewpoint of extraction conditions and equipment.
抽出液中の濃度としては５重量％から飽和濃度までの範
囲が適当である。また、反応生成物／抽出液の容量比で
９９７１〜２０／８０程度が好ましい結果を与える。The appropriate concentration in the extract is from 5% by weight to saturated concentration. Moreover, a preferable result is obtained when the volume ratio of reaction product/extract liquid is about 9971 to 20/80.
本発明に於いて、抽出液には反応生成物からの遷移金属
触媒の抽出効率を向上するために含酸素有機化合物を添
加することができる。例えば、酢酸、プロピオン酸、安
息香酸等の有機カルボン酸類、アセトン、メチルエチル
ケトン等のケトン類、ジオキサン、ジメチルエーテル等
のエーテル類及びそれらの混合物が好ましく用いられる
。In the present invention, an oxygen-containing organic compound can be added to the extract in order to improve the efficiency of extracting the transition metal catalyst from the reaction product. For example, organic carboxylic acids such as acetic acid, propionic acid and benzoic acid, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and dimethyl ether, and mixtures thereof are preferably used.
水と含酸素有機化合物との最適な混合比は、反応生成物
との相分離が必要なことから、反応溶媒の種類により大
きく異なるが、例えばへキサン反応溶媒系に対しての水
と酢酸の混合比は、水／酢酸の容量比で９８／２〜５０
１５０程度が好ましい。The optimal mixing ratio of water and oxygen-containing organic compound varies greatly depending on the type of reaction solvent, as phase separation from the reaction product is required. The mixing ratio is 98/2 to 50 by volume of water/acetic acid.
About 150 is preferable.
尚、本発明の抽出液を用いる場合の抽出温度は１０〜１
５０℃であるが、室温から１３０℃の範囲が操作的にも
設備的にも好ましい。In addition, when using the extract of the present invention, the extraction temperature is 10 to 1
Although the temperature is 50°C, a range from room temperature to 130°C is preferable in terms of operation and equipment.
本発明を適用する反応生成物とは、前述したように遷移
金属触媒を用いて得られた反応液より、フラッシユ、抽
出等により触媒を分離した後の反応生成物であるが、こ
の反応生成物中に残存する触媒濃度は広範囲であって特
に限定はない。通常、５０００〜５ｐｐｍ程度の範囲で
あるが、抽出効率の面からは５００〜２０ｐｐｍ程度の
反応生成物が好ましい。The reaction product to which the present invention is applied is the reaction product after the catalyst is separated from the reaction solution obtained using the transition metal catalyst by flashing, extraction, etc. as described above. The concentration of catalyst remaining therein can vary widely and is not particularly limited. Usually, the amount of the reaction product is in the range of about 5000 to 5 ppm, but from the viewpoint of extraction efficiency, the reaction product amount is preferably about 500 to 20 ppm.
以下、本発明を実施例について説明するが、本発明はこ
れに限定されるものではない。EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited thereto.
実施例１
ヨウ化ロジウム触媒を用いてヘキサン溶媒中で、２−
（４−インブチルフェニル）エチルアルコールと一酸化
炭素から２−（４−インブチルフェニル）プロピオン酸
を合成した反応液１００ｇ （ロジウム濃度約４０００
ｐｐｍ）に水３０ｇ、酢酸６０ｇを添加して触媒抽出を
行い、２層に分液した。Example 1 In a hexane solvent using a rhodium iodide catalyst, 2-
100g of reaction solution synthesized from (4-butylphenyl)ethyl alcohol and carbon monoxide to 2-(4-butylphenyl)propionic acid (rhodium concentration approx. 4000)
catalytic extraction was performed by adding 30 g of water and 60 g of acetic acid to the mixture (ppm), and the mixture was separated into two layers.
ロジウム触媒は９９％が下層（主に水、酢酸層）に抽出
されたが、上層中にはまだ４ｏｐｐｍ ものロジウム触
媒が残存していた（この１回抽出の模作を行い、分液し
た上層を以下「抽出上層」とする）。この抽出上層６０
ｇに塩酸（３５％）を１蔵滴下し撹拌すると、上層の着
色（ロジウム錯体による着色）は素早く下層に移った。Although 99% of the rhodium catalyst was extracted into the lower layer (mainly water and acetic acid layer), as much as 4 oppm of rhodium catalyst still remained in the upper layer. (hereinafter referred to as the "extraction upper layer"). This extraction upper layer 60
When 1 volume of hydrochloric acid (35%) was added dropwise to g and stirred, the coloring of the upper layer (coloring due to the rhodium complex) quickly transferred to the lower layer.
静置後、分液した上層中のロジウム濃度を分析すると０
、１５ｐｐｍであった。塩酸抽出の回収率は９９．６％
であった。After standing still, the rhodium concentration in the separated upper layer was analyzed and found to be 0.
, 15 ppm. Recovery rate of hydrochloric acid extraction is 99.6%
Met.
実施例２
実施例１と同様に抽出し、約１２０ｐｐｍのロジウム触
媒が残存する抽出上層２９０ ｇ （４００ｍ） に塩
酸（３５％）を２００ｍ１添加し、１時間撹拌を行った
。分液した上層中のロジウム濃度は０．３ｐｐｍｔ’あ
った。塩酸抽出の回収率は９９．１％であった。Example 2 Extraction was carried out in the same manner as in Example 1, and 200 ml of hydrochloric acid (35%) was added to 290 g (400 m) of the upper extraction layer in which about 120 ppm of rhodium catalyst remained, and the mixture was stirred for 1 hour. The rhodium concentration in the separated upper layer was 0.3 ppmt'. The recovery rate of hydrochloric acid extraction was 99.1%.
実施例３
実施例１と同様に抽出し、約１６０ｐｐｍのロジウム触
媒が残存する抽出上層２９０ ｇ （４００ｍｌ）
に塩酸（３５％）を４０ｍ！添加し、１時間撹拌を行っ
た。Example 3 Extracted in the same manner as in Example 1, 290 g (400 ml) of the upper extraction layer in which about 160 ppm of rhodium catalyst remains
40m of hydrochloric acid (35%)! and stirred for 1 hour.
分液した上層中のロジウム濃度は２．５ｐｐｍであった
。塩酸抽出の回収率は９４．６％であった。The rhodium concentration in the separated upper layer was 2.5 ppm. The recovery rate of hydrochloric acid extraction was 94.6%.
実施例４
実施例１と同様に抽出し、約３６０ｐｐｍのロジウム触
媒が残存する抽出上層３００ ｇ （４００ｍｌ） に
塩酸（２１％）を２００ｍｆ添加し、１時間伐拌を行っ
た。分液した上層中のロジウム濃度は１．５ｐｐｍであ
った。塩酸抽出の回収率は９８．６％であった。Example 4 Extraction was carried out in the same manner as in Example 1, and 200 mf of hydrochloric acid (21%) was added to 300 g (400 ml) of the extracted upper layer in which about 360 ppm of rhodium catalyst remained, and the mixture was stirred for 1 hour. The rhodium concentration in the separated upper layer was 1.5 ppm. The recovery rate of hydrochloric acid extraction was 98.6%.
実施例５
実施例１と同様に抽出し、約３２０ｐｐｍのロジウム触
媒が残存する抽出上層３００ ｇ （４００ｍｌ）
に塩酸（１４％）を２００ｍ１添加し、１時間撹拌を行
った。分液した上層中のロジウム濃度は２．９ｐｐｍで
あった。塩酸抽出の回収率は９７．０％であった。Example 5 Extracted in the same manner as in Example 1, 300 g (400 ml) of the upper extraction layer in which about 320 ppm of rhodium catalyst remains
200 ml of hydrochloric acid (14%) was added to the solution and stirred for 1 hour. The rhodium concentration in the separated upper layer was 2.9 ppm. The recovery rate of hydrochloric acid extraction was 97.0%.
実施例６
実施例１と同様に抽出し、約３２０ｐｐｍのロジウム触
媒が残存する抽出上層３００ ｇ （４００ｍｆ）に塩
酸（７％）を２００Ｉｎ！添加し、１時間撹拌を行った
。分液した上層中のロジウム濃度は４．０ｐｐｍであっ
た。塩酸抽出の回収率は９５．９％であった。Example 6 Extraction was carried out in the same manner as in Example 1, and 200 In! of hydrochloric acid (7%) was added to 300 g (400 mf) of the upper extraction layer in which approximately 320 ppm of rhodium catalyst remained. and stirred for 1 hour. The rhodium concentration in the separated upper layer was 4.0 ppm. The recovery rate of hydrochloric acid extraction was 95.9%.
比較例Ｉ
実施例Ｉに示したロジウム触媒が４０ｐｐｍ残存する抽
出上層６０ｇに、水２５ｇ、酢酸５５ｇを加え撹拌、静
置後、分液した。上層中のロジウム濃度を分析すると３
２ｐｐｍであった。２回目の水／酢酸抽出の回収率は２
０％にすぎなかった。Comparative Example I To 60 g of the extracted upper layer in which 40 ppm of the rhodium catalyst shown in Example I remained, 25 g of water and 55 g of acetic acid were added, stirred, allowed to stand, and then separated. Analysis of the rhodium concentration in the upper layer shows 3
It was 2 ppm. The recovery rate for the second water/acetic acid extraction is 2
It was only 0%.
Claims (1)
する遷移金属触媒を、ハロゲン化合物又はハロゲンを含
む水溶液を用いて抽出分離することを特徴とする遷移金
属触媒の回収方法。1. A method for recovering a transition metal catalyst, which comprises extracting and separating the transition metal catalyst remaining in a reaction product obtained using a transition metal catalyst using a halogen compound or an aqueous solution containing a halogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63231334A JPH0280320A (en) | 1988-09-14 | 1988-09-14 | Recovering method for transition metal catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63231334A JPH0280320A (en) | 1988-09-14 | 1988-09-14 | Recovering method for transition metal catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0280320A true JPH0280320A (en) | 1990-03-20 |
Family
ID=16922011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63231334A Pending JPH0280320A (en) | 1988-09-14 | 1988-09-14 | Recovering method for transition metal catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0280320A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5936130A (en) * | 1996-09-11 | 1999-08-10 | Mitsubishi Chemical Corporation | Process for preparing a rhodium complex solution and process for producing an aldehyde |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57501767A (en) * | 1980-11-24 | 1982-10-07 |
-
1988
- 1988-09-14 JP JP63231334A patent/JPH0280320A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57501767A (en) * | 1980-11-24 | 1982-10-07 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5936130A (en) * | 1996-09-11 | 1999-08-10 | Mitsubishi Chemical Corporation | Process for preparing a rhodium complex solution and process for producing an aldehyde |
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