JPS626533B2 - - Google Patents
Info
- Publication number
- JPS626533B2 JPS626533B2 JP54044955A JP4495579A JPS626533B2 JP S626533 B2 JPS626533 B2 JP S626533B2 JP 54044955 A JP54044955 A JP 54044955A JP 4495579 A JP4495579 A JP 4495579A JP S626533 B2 JPS626533 B2 JP S626533B2
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- cobalt
- polyhydric alcohol
- methanol
- acid ester
- 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
Links
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 35
- 229930195729 fatty acid Natural products 0.000 claims description 35
- 239000000194 fatty acid Substances 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 229910017052 cobalt Inorganic materials 0.000 claims description 26
- 239000010941 cobalt Substances 0.000 claims description 26
- -1 fatty acid ester Chemical class 0.000 claims description 20
- 150000005846 sugar alcohols Polymers 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 2
- FDPHDGUADUFPHZ-UHFFFAOYSA-L cobalt(2+);heptanoate Chemical compound [Co+2].CCCCCCC([O-])=O.CCCCCCC([O-])=O FDPHDGUADUFPHZ-UHFFFAOYSA-L 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- UQJDVLPHTXQTRP-UHFFFAOYSA-N 2,2-bis(heptanoyloxymethyl)butyl heptanoate Chemical compound CCCCCCC(=O)OCC(CC)(COC(=O)CCCCCC)COC(=O)CCCCCC UQJDVLPHTXQTRP-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- NCGQPNAQUYGWMI-UHFFFAOYSA-N [3-heptanoyloxy-2,2-bis(heptanoyloxymethyl)propyl] heptanoate Chemical compound CCCCCCC(=O)OCC(COC(=O)CCCCCC)(COC(=O)CCCCCC)COC(=O)CCCCCC NCGQPNAQUYGWMI-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 229940094933 n-dodecane Drugs 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は多価アルコールの脂肪酸エステルおよ
び脂肪酸コバルトを含む混合液から脂肪酸コバル
トを分離する方法に関するものであり、特に本発
明はコバルトカルボニル錯体を触媒とするヒドロ
エステル化反応におけるコバルトの回収方法とし
て工業的に有利に適用される。Detailed Description of the Invention The present invention relates to a method for separating fatty acid cobalt from a mixed liquid containing a fatty acid ester of a polyhydric alcohol and a fatty acid cobalt. In particular, the present invention relates to a hydroesterification reaction using a cobalt carbonyl complex as a catalyst. It is advantageously applied industrially as a method for recovering cobalt.
コバルトカルボニル錯体を触媒とする多価アル
コール、オレフインおよび一酸化炭素のヒドロエ
ステル化反応による多価アルコールの脂肪酸エス
テルの製造法においては、反応生成液からパラフ
インまたはオレフインを用いて多価アルコールの
脂肪酸エステルを抽出することによりコバルトカ
ルボニル錯体を分離する方法が提案されている
（特公昭53−31128、特公昭53−37327）。この方法
の利点は、コバルトを活性種の形態で回収できる
ためにそのまま反応系に循環して使用し得るとこ
ろにあるが、コバルトカルボニル錯体がパラフイ
ンまたはオレフインにある程度溶解することによ
る回収ロスと回収触媒の失活による触媒活性の低
下のために、新触媒の追加と回収触媒の活性化処
理を行なつて収率を一定に維持する必要がある。 In the method for producing fatty acid esters of polyhydric alcohols by the hydroesterification reaction of polyhydric alcohols, olefins and carbon monoxide using a cobalt carbonyl complex as a catalyst, fatty acid esters of polyhydric alcohols are produced using paraffin or olefin from the reaction product liquid. A method has been proposed to separate cobalt carbonyl complexes by extracting them (Japanese Patent Publications No. 53-31128 and No. 53-37327). The advantage of this method is that cobalt can be recovered in the form of active species, so it can be recycled to the reaction system and used as is, but there is a recovery loss due to the cobalt carbonyl complex dissolving to some extent in paraffin or olefin, and recovery catalyst Since the catalyst activity decreases due to the deactivation of the catalyst, it is necessary to maintain the yield constant by adding new catalyst and activating the recovered catalyst.
一般に、前述したヒドロエステル化反応による
多価アルコールの脂肪酸エステルの製造法におい
て得られる反応生成液には、多価アルコールの脂
肪酸エステル、未反応オレフイン、コバルトカル
ボニル錯体、コバルトカルボニル錯体に対して過
剰量のピリジン類塩基配位子、および副反応によ
り生成する原料オレフインよりも炭素原子数が１
個多い脂肪酸が含まれている。この反応生成液を
蒸留して未反応オレフインおよびピリジン類塩基
を留去すれば、コバルトカルボニル錯体はその不
安定性のゆえにすみやかに分解して、共存する遊
離の脂肪酸に捉えられて脂肪酸コバルトに転化
し、多価アルコールの脂肪酸エステルおよび脂肪
酸コバルトを含む混合液が得られる。本発明にお
いては、主として上記のような混合液が対象とな
るが、勿論他の方法で得られる多価アルコールの
脂肪酸エステルおよび脂肪酸コバルトを含む混合
液も対象とすることができる。 In general, the reaction product liquid obtained in the method for producing fatty acid esters of polyhydric alcohols by the hydroesterification reaction described above contains an excess amount of fatty acid esters of polyhydric alcohols, unreacted olefins, cobalt carbonyl complexes, and cobalt carbonyl complexes. The number of carbon atoms is 1 compared to the pyridine base ligand and the raw material olefin produced by the side reaction.
Contains a lot of fatty acids. When this reaction product solution is distilled to remove unreacted olefins and pyridine bases, the cobalt carbonyl complex is quickly decomposed due to its instability and is captured by coexisting free fatty acids and converted into fatty acid cobalt. , a liquid mixture containing fatty acid ester of polyhydric alcohol and fatty acid cobalt is obtained. In the present invention, the above-mentioned mixed liquids are mainly targeted, but, of course, mixed liquids containing fatty acid esters of polyhydric alcohols and fatty acid cobalt obtained by other methods can also be targeted.
本発明において、多価アルコールの脂肪酸エス
テルとはグリセリン、エチレングリコール、トリ
メチロールプロパン、ペンタエリスリトール等の
多価アルコールの炭素原子数５〜11の脂肪酸との
モノエステルまたはポリエステルであつて、通常
はコバルトカルボニル錯体およびピリジン類塩基
の存在下に前記多価アルコールを炭素原子数４〜
10のオレフインおよび一酸化炭素と反応させるこ
とにより得られる。また、脂肪酸コバルトとは炭
素原子数５〜11の脂肪酸のコバルト塩であり、通
常は前記多価アルコールの脂肪酸エステルの酸成
分と同一構造を有する脂肪酸のコバルト塩であ
る。勿論、前記混合液中には若干のピリジン類塩
基あるいは遊離の脂肪酸が含まれていてもよい。 In the present invention, fatty acid esters of polyhydric alcohols are monoesters or polyesters of polyhydric alcohols such as glycerin, ethylene glycol, trimethylolpropane, and pentaerythritol with fatty acids having 5 to 11 carbon atoms, and are usually cobalt. The polyhydric alcohol has 4 to 4 carbon atoms in the presence of a carbonyl complex and a pyridine base.
Obtained by reacting with 10 olefin and carbon monoxide. Moreover, fatty acid cobalt is a cobalt salt of a fatty acid having 5 to 11 carbon atoms, and usually is a cobalt salt of a fatty acid having the same structure as the acid component of the fatty acid ester of the polyhydric alcohol. Of course, the mixed liquid may contain some pyridine base or free fatty acid.
本発明は、前述した多価アルコールの脂肪酸エ
ステルおよび脂肪酸コバルトを含む混合液に、炭
素原子数６〜20のパラフイン、メタノールおよび
場合により水を添加して多価アルコールの脂肪酸
エステルを含む相と脂肪酸コバルトを含む相との
二相に分離することにより達成される。炭素数６
〜20のパラフインの添加量は混合液中のエステル
に対して0.2〜10重量倍、好ましくは１〜５重量
倍であり、メタノールの添加量はパラフインに対
して0.1〜10重量倍、好ましくは0.5〜３重量倍で
あり、水の添加量はメタノールに対して０〜５重
量倍、好ましくは0.05〜１重量倍であり、添加時
または添加後に、液−液の接触を良好にするため
に、５分間〜２時間撹拌することが望ましい。本
発明においては、温度、圧力、雰囲気などの条件
は支配的因子ではなく、通常は常温、常圧で大気
中においてさえ本発明を実施することができる。 The present invention produces a phase containing a fatty acid ester of a polyhydric alcohol and a fatty acid by adding paraffin having 6 to 20 carbon atoms, methanol, and optionally water to the liquid mixture containing the fatty acid ester of a polyhydric alcohol and fatty acid cobalt. This is achieved by separating into two phases: a cobalt-containing phase and a cobalt-containing phase. Carbon number 6
The amount of paraffin added is 0.2 to 10 times, preferably 1 to 5 times the weight of the ester in the mixed solution, and the amount of methanol added is 0.1 to 10 times the weight of paraffin, preferably 0.5 times. ~3 times by weight, and the amount of water added is 0 to 5 times, preferably 0.05 to 1 times by weight, relative to methanol, in order to improve liquid-liquid contact during or after addition. It is desirable to stir for 5 minutes to 2 hours. In the present invention, conditions such as temperature, pressure, atmosphere, etc. are not dominant factors, and the present invention can be practiced even in the atmosphere at normal temperature and pressure.
多価アルコールの脂肪酸エステルは上層に分離
するパラフイン相に含有され、たとえば蒸留等の
操作により精製することができる。一方、脂肪酸
コバルトは下層に分離するメタノール相に含有さ
れ、溶媒を留去することにより取得することがで
きるが、通常は、そのまま、あるいは適当に濃縮
したのち、ヒドロエステル化反応の触媒原料とし
て使用される。 The fatty acid ester of polyhydric alcohol is contained in the paraffin phase that separates into the upper layer, and can be purified, for example, by distillation or other operations. On the other hand, fatty acid cobalt is contained in the methanol phase that separates into the lower layer, and can be obtained by distilling off the solvent, but it is usually used as a catalyst raw material for the hydroesterification reaction, either as it is or after being appropriately concentrated. be done.
次に本発明を実施例により更に具体的に説明す
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。 Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例 １
ヘプタン酸コバルト7.10重量％を含有するトリ
メチロールプロパントリヘプタノエート1.96ｇに
ｎ−ドデカン7.39ｇ、メタノール7.57ｇおよび水
0.40ｇを添加し、30分間撹拌したのち30分間静置
し、二相に分離させた。各相を分取してそれぞれ
トリメチロールプロパントリヘプタノエートおよ
びヘプタン酸コバルトについて定量した結果、ト
リメチロールプロパントリヘプタノエートは上層
にその85％が分配し、ヘプタン酸コバルトは下層
にその100％が分配していた。Example 1 1.96 g of trimethylolpropane triheptanoate containing 7.10% by weight of cobalt heptanoate, 7.39 g of n-dodecane, 7.57 g of methanol and water
0.40 g was added, stirred for 30 minutes, and then allowed to stand for 30 minutes to separate into two phases. As a result of separating each phase and quantifying trimethylolpropane triheptanoate and cobalt heptanoate, 85% of trimethylolpropane triheptanoate was distributed in the upper layer, and 100% of cobalt heptanoate was distributed in the lower layer. was distributing it.
実施例 ２
ヘプタン酸コバルト7.25重量％を含有するトリ
メチロールプロパントリヘプタノエート1.88ｇに
ｎ−ヘキサン6.25ｇ、メタノール7.55ｇおよび水
0.40ｇを添加し、実施例１と同様の操作を行なつ
たところ、トリメチロールプロパントリヘプタノ
エートはその77％が上層に分配し、ヘプタン酸コ
バルトはその91％が下層に分配していた。Example 2 1.88 g of trimethylolpropane triheptanoate containing 7.25% by weight of cobalt heptanoate, 6.25 g of n-hexane, 7.55 g of methanol and water
When 0.40 g was added and the same operation as in Example 1 was performed, 77% of trimethylolpropane triheptanoate was distributed in the upper layer, and 91% of cobalt heptanoate was distributed in the lower layer. .
実施例 ３
ヘプタン酸コバルト6.73重量％を含有するペン
タエリスリトールテトラヘプタノエート2.04ｇに
ｎ−ドデカン4.48ｇ、メタノール4.53ｇおよび水
0.24ｇを添加し、実施例１と同様の操作を行なつ
たところ、ペンタエリスリトールテトラヘプタノ
エートはその94％が上層に分配し、ヘプタン酸コ
バルトはその99％が下層に分配していた。Example 3 2.04 g of pentaerythritol tetraheptanoate containing 6.73% by weight of cobalt heptanoate, 4.48 g of n-dodecane, 4.53 g of methanol and water
When 0.24 g was added and the same operation as in Example 1 was performed, 94% of pentaerythritol tetraheptanoate was distributed in the upper layer, and 99% of cobalt heptanoate was distributed in the lower layer.
実施例 ４
ヘプタン酸コバルト6.43重量％を含有するトリ
メチロールプロパントリヘプタノエート1.98ｇに
ｎ−ドデカン7.36ｇおよびメタノール7.87ｇを添
加し、実施例１と同様の操作を行なつたところ、
トリメチロールプロパントリヘプタノエートはそ
の69％が上層に分配し、ヘプタン酸コバルトはそ
の99％が下層に分配していた。Example 4 7.36 g of n-dodecane and 7.87 g of methanol were added to 1.98 g of trimethylolpropane triheptanoate containing 6.43% by weight of cobalt heptanoate, and the same operation as in Example 1 was performed.
69% of trimethylolpropane triheptanoate was distributed in the upper layer, and 99% of cobalt heptanoate was distributed in the lower layer.
実施例 ５
ヘプタン酸コバルト6.57重量％を含有するペン
タエリスリトールテトラヘプタノエート2.0ｇに
ｎ−ドデカン7.36ｇおよびメタノール7.76ｇを添
加し、実施例１と同様の操作を行なつた。その結
果、ペンタエリスリトールテトラヘプタノエート
はその76％が上層に分配し、ヘプタン酸コバルト
はその97％が下層に分配していた。Example 5 The same operation as in Example 1 was carried out by adding 7.36 g of n-dodecane and 7.76 g of methanol to 2.0 g of pentaerythritol tetraheptanoate containing 6.57% by weight of cobalt heptanoate. As a result, 76% of pentaerythritol tetraheptanoate was distributed in the upper layer, and 97% of cobalt heptanoate was distributed in the lower layer.
Claims (1)
酸コバルトを含む混合液に炭素原子数６〜20のパ
ラフインおよびメタノールを添加して多価アルコ
ールの脂肪酸エステルを含む相と脂肪酸コバルト
を含む相との二相に分離することを特徴とする脂
肪酸コバルトの分離方法。 ２ 多価アルコールの脂肪酸エステルおよび脂肪
酸コバルトを含む混合液に炭素原子数６〜20のパ
ラフイン、メタノールおよび水を添加して多価ア
ルコールの脂肪酸エステルを含む相と脂肪酸コバ
ルトを含む相の二相に分離することを特徴とする
脂肪酸コバルトの分離方法。[Scope of Claims] 1. A phase containing a fatty acid ester of a polyhydric alcohol and a phase containing a cobalt fatty acid are obtained by adding paraffin having 6 to 20 carbon atoms and methanol to a mixed liquid containing a fatty acid ester of a polyhydric alcohol and a cobalt fatty acid. A method for separating cobalt fatty acid into two phases. 2 Paraffin having 6 to 20 carbon atoms, methanol, and water are added to a mixed solution containing a fatty acid ester of a polyhydric alcohol and a cobalt fatty acid to form two phases: a phase containing a fatty acid ester of a polyhydric alcohol and a phase containing fatty acid cobalt. A method for separating fatty acid cobalt, characterized by separating it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4495579A JPS55139335A (en) | 1979-04-13 | 1979-04-13 | Separation of cobalt salt of fatty acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4495579A JPS55139335A (en) | 1979-04-13 | 1979-04-13 | Separation of cobalt salt of fatty acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55139335A JPS55139335A (en) | 1980-10-31 |
| JPS626533B2 true JPS626533B2 (en) | 1987-02-12 |
Family
ID=12705900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4495579A Granted JPS55139335A (en) | 1979-04-13 | 1979-04-13 | Separation of cobalt salt of fatty acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55139335A (en) |
-
1979
- 1979-04-13 JP JP4495579A patent/JPS55139335A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55139335A (en) | 1980-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4041057A (en) | Hydroesterification process | |
| US3530168A (en) | Preparation of esters | |
| CA2446638A1 (en) | Process for preparing carboxylic acids and derivatives thereof | |
| CA1113491A (en) | Manufacture of butanedicarboxylic acid esters | |
| EP0922691B1 (en) | Hydroformylation process | |
| US4258203A (en) | Preparation of butanedicarboxylic acid esters | |
| DE4419898C2 (en) | Process for the preparation of an aldehyde | |
| US4169956A (en) | Manufacture of butanedicarboxylic acid esters | |
| US4256909A (en) | Preparation of dimethyl butanedicarboxylates | |
| US4894474A (en) | Preparation of alkyl pentenoates | |
| US2997494A (en) | Method of preparing vinyl esters of carboxylic acids | |
| JPS626533B2 (en) | ||
| US4310686A (en) | Preparation of butanedicarboxylic esters | |
| JP2680069B2 (en) | Process for producing tricyclodecanecarboxylic acid ester | |
| US3974194A (en) | Method of separating cobalt catalyst from a liquid polyol ester product | |
| US2953611A (en) | Method and addition compounds for separating olefines from mixtures | |
| JPS626532B2 (en) | ||
| CA2075622A1 (en) | Azeotropic assisted transvinylation technology | |
| JPH0729978B2 (en) | Process for producing α-phenylpropionic acid derivative | |
| JPS626531B2 (en) | ||
| JPH0380144B2 (en) | ||
| JP3238894B2 (en) | Method for producing methyl methacrylate | |
| JPS6228773B2 (en) | ||
| JPH02104558A (en) | Production of alkyl pentenate | |
| US4578367A (en) | Methods for reprocessing cobalt catalysts used in hydrocarboxylation |