JPS63132859A - Production of pyruvic acid ester - Google Patents
Production of pyruvic acid esterInfo
- Publication number
- JPS63132859A JPS63132859A JP61280248A JP28024886A JPS63132859A JP S63132859 A JPS63132859 A JP S63132859A JP 61280248 A JP61280248 A JP 61280248A JP 28024886 A JP28024886 A JP 28024886A JP S63132859 A JPS63132859 A JP S63132859A
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- catalyst
- reaction
- oxide
- lactic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 pyruvic acid ester Chemical class 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- LCTONWCANYUPML-UHFFFAOYSA-N PYRUVIC-ACID Natural products CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 title abstract description 7
- 229940107700 pyruvic acid Drugs 0.000 title abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003903 lactic acid esters Chemical class 0.000 claims abstract description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 3
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 abstract description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001413 amino acids Chemical class 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 12
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 12
- 229940057867 methyl lactate Drugs 0.000 description 12
- 229940076788 pyruvate Drugs 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010908 decantation Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
することからなるピルビン酸エステルの製造法に関する
。DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for producing a pyruvate ester.
ピルビン酸エステルおよびこれを加水分解することによ
って得られるピルビン酸は、トリプトファン等のアミノ
酸原料として、また各種有機化合物中間体として注目さ
れている有用な物質である。Pyruvate ester and pyruvic acid obtained by hydrolyzing it are useful substances that are attracting attention as raw materials for amino acids such as tryptophan and as intermediates for various organic compounds.
ピルビン酸エステルの製法としては、乳酸エステルを過
マンガン酸カリウムで液相酸化する方法(オーガニ7ク
シンセシス(Org、 5ynthesis )1ユ、
59)が知られているが、工業的製法としては、(1)
バナジウム、モリブデン及びリンの酸化物を触媒とし、
担体としてα−アルミナを用いて、乳酸エステルの気相
酸化脱水素を行なう方法(特公昭56−19854号公
報)、(2)メタバナジン酸アンモニウム、シェラ酸、
水からなる混合物をpka値が3.3〜9.3の範囲に
ある担体に付着焼成した触媒を用い、乳酸エステルの気
相酸化脱水素反応を行なう方法(特公昭57−2433
6号公報)、(3)乳酸エステルを白金やパラジウムな
どの貴金属触媒の存在下に酸素酸化する方法(特開昭5
4−138514号公報)、(4)乳酸エステルをタン
グステンオキシドの存在下に液相において酸素酸化する
方法(特開昭58−62136号公報)などがるる。The method for producing pyruvate ester is a method of liquid phase oxidation of lactic acid ester with potassium permanganate (Org, 5 synthesis) 1 unit,
59) is known, but as an industrial manufacturing method, (1)
Using vanadium, molybdenum and phosphorus oxides as a catalyst,
A method for gas-phase oxidative dehydrogenation of lactic acid ester using α-alumina as a carrier (Japanese Patent Publication No. 19854/1985), (2) ammonium metavanadate, Scheleric acid,
A method of carrying out gas phase oxidative dehydrogenation reaction of lactic acid ester using a catalyst prepared by adhering and calcining a mixture of water to a carrier having a pka value in the range of 3.3 to 9.3 (Japanese Patent Publication No. 57-2433
6), (3) A method of oxidizing lactic acid ester with oxygen in the presence of a precious metal catalyst such as platinum or palladium (Japanese Patent Laid-Open No. 5
4-138514) and (4) a method in which lactic acid ester is oxidized with oxygen in the liquid phase in the presence of tungsten oxide (Japanese Patent Laid-Open No. 58-62136).
しかしながら、(1)(2)の画法は共に気相反応であ
り、工業化の為には設備が大規模になりすぎるといった
欠点がある。(3)の方法は、液相でも気相でもよいと
てれるが、高価な貴金属触媒を必要とする点、有害な重
金属を必要とする点などとも工業的方法とは言い難い。However, the drawing methods (1) and (2) both involve gas phase reactions, and have the disadvantage that the scale of the equipment is too large for industrialization. The method (3) can be carried out in either a liquid phase or a gas phase, but it cannot be called an industrial method as it requires an expensive noble metal catalyst and harmful heavy metals.
又、(4)の方法は液相反応であるが、用いられる触媒
が高価であり、入手が容易で、さらに安価な触媒を用い
た工業的実施に適したピルビン酸エステルの製造法の開
発が求められていた。In addition, method (4) is a liquid phase reaction, but the catalyst used is expensive, and it is difficult to develop a method for producing pyruvic acid ester that is easy to obtain and suitable for industrial implementation using a cheaper catalyst. It was wanted.
本発明者らは乳酸エステルを出発原料とする工業的実施
に適したピルビン酸エステルの製造法を開発すべく検討
を行なった結果、乳酸エステルを安価で、取り扱いが容
易である酸化チタン、酸化ジルコニウムおよび酸化ニオ
ブの少なくとも一種の存在下に液相において酸素酸化す
ると、ピルビン酸エステルが高選択率で生成することを
見出し、本発明を完成するに至った。The present inventors conducted studies to develop a manufacturing method for pyruvate ester suitable for industrial implementation using lactic acid ester as a starting material. The present inventors have discovered that pyruvate ester is produced with high selectivity when oxidized with oxygen in the liquid phase in the presence of at least one of niobium oxide and niobium oxide, and has completed the present invention.
本発明において出発原料として用いられる乳酸エステル
は、たとえば乳酸メチル、乳酸エチル、乳酸n−プロピ
ル、乳酸h−プデルなどを挙げる事ができる。Examples of the lactic acid ester used as a starting material in the present invention include methyl lactate, ethyl lactate, n-propyl lactate, and h-pudel lactate.
本発明の方法に用いられる触媒は、酸化チタン、酸化ジ
ルコニウム、酸化ニオブから成る群から選ばれた一種以
上である。The catalyst used in the method of the present invention is one or more selected from the group consisting of titanium oxide, zirconium oxide, and niobium oxide.
本発明において触媒として使用する酸化チタンは、2,
3.4価チタンの酸化物および過酸化物が知られてrる
が、通常用rられる4価の二酸化チタン(チタニア)が
入手の容易さなどを考慮すると好ましい。二酸化チタン
には構造を異にする3種の変態が知られているが、本発
明に使用する触媒としては、特に限定する必要はない。The titanium oxide used as a catalyst in the present invention is 2,
Although oxides and peroxides of 3.4-valent titanium are known, the commonly used 4-valent titanium dioxide (titania) is preferred in view of its ease of availability. Although three types of modification of titanium dioxide with different structures are known, there is no need to specifically limit the catalyst used in the present invention.
酸化ジルコニウムも通常、二酸化ジルコニウムの形であ
り、このものが入手の容易さなどから好ましい。Zirconium oxide is also usually in the form of zirconium dioxide, which is preferred because of its ease of availability.
チタン及びジルコニウムの他の化合物から出発しても、
反応中酸化物の形になるものは当然本発明の対象となる
。これらは、例えば、チタン、ジルコニウムの酸化物の
水和物、水酸化物、硝酸塩、シュウ酸塩などである。ニ
オブの酸化物、特に酸化ニオブも本方法に用いうるもの
であるが、ピルビン酸エステルへの選択率かや\低く、
また、やや高価であるので、経済性の点から上記チタン
、ジルコニウムからなる触媒の方がより好ましい。Starting from other compounds of titanium and zirconium,
Those that are converted into oxides during the reaction are naturally subject to the present invention. These are, for example, hydrates, hydroxides, nitrates, oxalates of titanium and zirconium oxides. Oxides of niobium, especially niobium oxide, can also be used in this method, but the selectivity to pyruvate ester is rather low;
Furthermore, since they are somewhat expensive, the catalysts made of titanium and zirconium are more preferable from the economic point of view.
触媒量は乳酸エステル1motK対して5f程度でよく
、これ以上多くしてもあまり効果はない。The amount of catalyst may be about 5f per 1 motK of lactic acid ester, and even if it is larger than this, there is not much effect.
反応温度は100〜170℃、好ましくは120〜15
0℃でおり、100℃未溝では反応速度が遅くなり、1
70℃を超えると選択率の低下が著しくなる。反応圧力
は一般に1〜lO気圧といった反応条件が好ましい。The reaction temperature is 100-170°C, preferably 120-15°C.
0℃, and if the temperature is not 100℃, the reaction rate will be slow and 1
When the temperature exceeds 70°C, the selectivity decreases significantly. The reaction pressure is generally preferably 1 to 10 atm.
反応時間は特に限定されるものではないが、後述するよ
うにピルビン酸エステルの反応性が高い為、極力短い事
が好ましく、10時間以下、より好ましくは、5時間以
下で反応を終える事が良い。The reaction time is not particularly limited, but as described later, since the reactivity of pyruvate ester is high, it is preferably as short as possible, and it is good to complete the reaction in 10 hours or less, more preferably 5 hours or less. .
本発明において酸素酸化に使用する含酸素ガスとしては
、酸素ガスまたは酸素と任意の割合の窒素との混合ガス
(たとえば空気)が一般に使用できる。また含酸素ガス
の供給方法としては反応混合物を攪拌し、気相部に流通
させる方法、液中に吹き込む方法、前記加圧系において
は、オートクレーブ中で圧力調節機などを用い、酸素分
圧を常に一定に保つ方法などが考えられる。As the oxygen-containing gas used for oxygen oxidation in the present invention, oxygen gas or a mixed gas (for example, air) of oxygen and nitrogen in any proportion can be generally used. In addition, the oxygen-containing gas can be supplied by stirring the reaction mixture and passing it through the gas phase, or by blowing it into the liquid.In the pressurized system, a pressure regulator or the like is used in an autoclave to adjust the oxygen partial pressure. One possible method is to keep it constant.
本発明において生成するピルビン酸エステルは反応性が
高く、なお100〜170℃という高温での反応となる
為、濃度は極力低い事が好ましい。The pyruvate ester produced in the present invention has high reactivity and the reaction takes place at a high temperature of 100 to 170°C, so it is preferable that the concentration is as low as possible.
濃度としては4モル/L以下が好ましく、高選択率を維
持する為には、転化率を低くおさえるか、もしくは溶媒
を使う必要がある。溶媒としては、エステル系でおり、
なお精製をより簡便にする為にはピルビン酸エステルよ
やも高沸点のものが好ましく、コハク酸ジメチルやコハ
ク酸ジエチルを挙げる事ができる。The concentration is preferably 4 mol/L or less, and in order to maintain high selectivity, it is necessary to keep the conversion rate low or to use a solvent. The solvent is ester-based,
In order to simplify purification, those having a higher boiling point than pyruvate ester are preferable, such as dimethyl succinate and diethyl succinate.
生成物の精製法は反応後、触媒を口過もしくはデカンテ
ーション等により分離し、その後減圧蒸留等の操作によ
り行なう事ができる。なお触媒は繰抄返し使用が可能で
ある為、反応終了後、減圧にする事により生成物である
ピルビン酸エステルを回収する事もできる。The product can be purified by separating the catalyst after the reaction by filtration, decantation, etc., and then performing an operation such as distillation under reduced pressure. Since the catalyst can be used repeatedly, the pyruvic acid ester product can be recovered by reducing the pressure after the reaction is completed.
次に本発明を実施例及び比較例によって更に具体的に説
明する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例1
温度計、還流冷却器、マグネット攪拌子、酸素ガス導入
口、オフガス採取口を備えた100m74つロフラスコ
に、二酸化チタン「和光紬薬■製(アナターゼ型)」2
?、乳酸メチル42 f (0゜403モル)を仕込ん
だ。油浴を130℃に加熱し、反応液中に酸素ガスを1
0 t/ hrsの流速でバブリングさせ、マグネット
攪拌子により攪拌し、反応を開始した。反応開始3時間
後、反応を停止し反応混合物をガスクロマトグラフィー
で分析した。その結果、乳酸メチルの転化率は38.2
%、ピルビン酸メチルへの選択率は93.9%でめった
。Example 1 Titanium dioxide “Wako Tsumugi Yakuhin (anatase type)” 2 was placed in a 100 m 74-hole flask equipped with a thermometer, reflux condenser, magnetic stirrer, oxygen gas inlet, and off-gas sampling port.
? , 42 f (0°403 mol) of methyl lactate were charged. Heat the oil bath to 130°C and add 1 liter of oxygen gas to the reaction solution.
The reaction was started by bubbling at a flow rate of 0 t/hrs and stirring with a magnetic stirrer. Three hours after the start of the reaction, the reaction was stopped and the reaction mixture was analyzed by gas chromatography. As a result, the conversion rate of methyl lactate was 38.2
%, the selectivity to methyl pyruvate was 93.9%.
実施例2
実施例1と同様の実験装置に、二酸化チタン42を仕込
み反応させた他は、実施例1と同様に実験を行った結果
、乳酸メチルの転化率は37.5%、ピルビン酸メチル
への選択率は93.5%であった。Example 2 An experiment was carried out in the same manner as in Example 1, except that titanium dioxide 42 was charged and reacted in the same experimental apparatus as in Example 1. As a result, the conversion rate of methyl lactate was 37.5%, and the conversion rate of methyl pyruvate was 37.5%. The selectivity to was 93.5%.
実施例3
実施例1で得られた反応混合液を冷却、静置後デカンテ
ーションにより、ピルビン酸メチル及び乳酸メチルを回
収し、新たに乳酸メチル42f(0,403モル)を仕
込み、以下実施例1と同様に実験を行った結果、乳酸メ
チルの転化率は37.9%、ピルビン酸メチルへの選択
率は93.8%であった。Example 3 The reaction mixture obtained in Example 1 was cooled, left to stand, and then decanted to recover methyl pyruvate and methyl lactate. Methyl lactate 42f (0,403 mol) was newly charged, and the following examples were carried out. As a result of conducting the same experiment as in 1, the conversion rate of methyl lactate was 37.9%, and the selectivity to methyl pyruvate was 93.8%.
ヌ1旦工
実施例1と同様の実験装置に、酸化ジルコニウム2tを
仕込み反応させた他は実施例1と同様に実験を行った結
果、乳酸メチルの転化率は36.9%、ピルビン酸メチ
ルへの選択率は93.3%であった。An experiment was carried out in the same manner as in Example 1 except that 2 tons of zirconium oxide was charged into the same experimental apparatus as in Example 1 and the reaction was carried out. As a result, the conversion rate of methyl lactate was 36.9%, and the conversion rate of methyl lactate was 36.9%. The selectivity to was 93.3%.
実施例5
実施例1と同様の実験装置に、五酸化ニオブ2tを仕込
み反応させた他は実施例1と同様に実験を行った結果、
乳酸メチルの転化率は38.5%、ピルビン酸メチルへ
の選択率は92.0%であった。Example 5 An experiment was conducted in the same manner as in Example 1, except that 2 tons of niobium pentoxide was charged into the same experimental apparatus as in Example 1 and reacted.
The conversion rate of methyl lactate was 38.5%, and the selectivity to methyl pyruvate was 92.0%.
31!ま
実施例1と同様の実験装置に、二酸化チタン1、Ofと
酸化ジルコニウム1.Ofを仕込み反応させた他は実施
例1と同様に実験を行った結果、乳酸メチルの転化率は
37.6%、ピルビン酸メチルへの選択率は93.8%
であった。31! In the same experimental apparatus as in Example 1, 1.0% of titanium dioxide and 1.0% of zirconium oxide were placed. The experiment was carried out in the same manner as in Example 1 except that Of was charged and the reaction was carried out. As a result, the conversion rate of methyl lactate was 37.6%, and the selectivity to methyl pyruvate was 93.8%.
Met.
比較例1
実施例1と同様の実験装置に、三酸化タングステン2t
を仕込み反応させた他は、実施例1と同様に実験を行っ
た結果、乳酸メチルの転化率は21.7%、ピルビン酸
メチルへの選択率は82.0%であった。Comparative Example 1 2 tons of tungsten trioxide was added to the same experimental equipment as in Example 1.
An experiment was carried out in the same manner as in Example 1, except that the reaction was carried out by charging the reaction mixture. As a result, the conversion rate of methyl lactate was 21.7%, and the selectivity to methyl pyruvate was 82.0%.
比較例2〜8
実施例1と同様の実験装置に、下表に挙げた各触媒を2
f仕込み反応させた他は、実施例1と同様に実験を行っ
た。Comparative Examples 2 to 8 In the same experimental apparatus as in Example 1, two of each catalyst listed in the table below were added.
The experiment was conducted in the same manner as in Example 1, except that f preparation reaction was performed.
(以下余白)(Margin below)
Claims (1)
化ニオブの少くとも一種の存在下、液相において、酸素
酸化することを特徴とするピルビン酸エステルの製造方
法。A method for producing a pyruvate ester, which comprises oxygen-oxidizing a lactic acid ester in a liquid phase in the presence of at least one of titanium oxide, zirconium oxide, and niobium oxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61280248A JPS63132859A (en) | 1986-11-25 | 1986-11-25 | Production of pyruvic acid ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61280248A JPS63132859A (en) | 1986-11-25 | 1986-11-25 | Production of pyruvic acid ester |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63132859A true JPS63132859A (en) | 1988-06-04 |
Family
ID=17622362
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61280248A Pending JPS63132859A (en) | 1986-11-25 | 1986-11-25 | Production of pyruvic acid ester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63132859A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106111173A (en) * | 2016-06-28 | 2016-11-16 | 厦门市净屋环保科技有限公司 | A kind of for being prepared the catalyst of pyruvate by lactate and preparing the method for pyruvate |
-
1986
- 1986-11-25 JP JP61280248A patent/JPS63132859A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106111173A (en) * | 2016-06-28 | 2016-11-16 | 厦门市净屋环保科技有限公司 | A kind of for being prepared the catalyst of pyruvate by lactate and preparing the method for pyruvate |
CN106111173B (en) * | 2016-06-28 | 2017-09-01 | 厦门市净屋环保科技有限公司 | A kind of method for preparing pyruvate |
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