JPS6115863B2 - - Google Patents
Info
- Publication number
- JPS6115863B2 JPS6115863B2 JP4426778A JP4426778A JPS6115863B2 JP S6115863 B2 JPS6115863 B2 JP S6115863B2 JP 4426778 A JP4426778 A JP 4426778A JP 4426778 A JP4426778 A JP 4426778A JP S6115863 B2 JPS6115863 B2 JP S6115863B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- ester
- lactic acid
- lactate
- 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.)
- Expired
Links
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 34
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 19
- 239000004310 lactic acid Substances 0.000 claims description 17
- 235000014655 lactic acid Nutrition 0.000 claims description 17
- 229940107700 pyruvic acid Drugs 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052714 tellurium Inorganic materials 0.000 claims description 8
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 13
- -1 alkali metal salt Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000003903 lactic acid esters Chemical class 0.000 description 5
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 4
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 4
- 229940076788 pyruvate Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 3
- 239000004251 Ammonium lactate Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229940059265 ammonium lactate Drugs 0.000 description 3
- 235000019286 ammonium lactate Nutrition 0.000 description 3
- VRYNVZJQBANJOF-UHFFFAOYSA-N azane;2-oxopropanoic acid Chemical compound [NH4+].CC(=O)C([O-])=O VRYNVZJQBANJOF-UHFFFAOYSA-N 0.000 description 3
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000001540 sodium lactate Substances 0.000 description 3
- 235000011088 sodium lactate Nutrition 0.000 description 3
- 229940005581 sodium lactate Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000004201 L-cysteine Substances 0.000 description 2
- 235000013878 L-cysteine Nutrition 0.000 description 2
- 102000003855 L-lactate dehydrogenase Human genes 0.000 description 2
- 108700023483 L-lactate dehydrogenases Proteins 0.000 description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- QLDHWVVRQCGZLE-UHFFFAOYSA-N acetyl cyanide Chemical compound CC(=O)C#N QLDHWVVRQCGZLE-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- RZOBLYBZQXQGFY-UHFFFAOYSA-N ammonium lactate Chemical class [NH4+].CC(O)C([O-])=O RZOBLYBZQXQGFY-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229940001447 lactate Drugs 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DAEPDZWVDSPTHF-UHFFFAOYSA-M sodium pyruvate Chemical compound [Na+].CC(=O)C([O-])=O DAEPDZWVDSPTHF-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 102000020018 Cystathionine gamma-Lyase Human genes 0.000 description 1
- 108010045283 Cystathionine gamma-lyase Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DXISOTXRTSGIEG-UHFFFAOYSA-N O(Cl)Cl.[In] Chemical compound O(Cl)Cl.[In] DXISOTXRTSGIEG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 102100040653 Tryptophan 2,3-dioxygenase Human genes 0.000 description 1
- 101710136122 Tryptophan 2,3-dioxygenase Proteins 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- HWXBTNAVRSUOJR-UHFFFAOYSA-N alpha-hydroxyglutaric acid Natural products OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 description 1
- 229940009533 alpha-ketoglutaric acid Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- HLKMEIITONDPGG-UHFFFAOYSA-L barium(2+);2-hydroxypropanoate Chemical compound [Ba+2].CC(O)C([O-])=O.CC(O)C([O-])=O HLKMEIITONDPGG-UHFFFAOYSA-L 0.000 description 1
- HDDQRHGTFKLBCI-UHFFFAOYSA-L barium(2+);2-oxopropanoate Chemical compound [Ba+2].CC(=O)C([O-])=O.CC(=O)C([O-])=O HDDQRHGTFKLBCI-UHFFFAOYSA-L 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- UZWMCCLZMHPPKW-UHFFFAOYSA-L calcium;2-oxopropanoate Chemical compound [Ca+2].CC(=O)C([O-])=O.CC(=O)C([O-])=O UZWMCCLZMHPPKW-UHFFFAOYSA-L 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QIESBVQBFFBEJV-UHFFFAOYSA-N chloro hypochlorite;tin Chemical compound [Sn].ClOCl QIESBVQBFFBEJV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OVGXLJDWSLQDRT-UHFFFAOYSA-L magnesium lactate Chemical compound [Mg+2].CC(O)C([O-])=O.CC(O)C([O-])=O OVGXLJDWSLQDRT-UHFFFAOYSA-L 0.000 description 1
- 239000000626 magnesium lactate Substances 0.000 description 1
- 235000015229 magnesium lactate Nutrition 0.000 description 1
- 229960004658 magnesium lactate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 1
- 239000001521 potassium lactate Substances 0.000 description 1
- 235000011085 potassium lactate Nutrition 0.000 description 1
- 229960001304 potassium lactate Drugs 0.000 description 1
- 229940054269 sodium pyruvate Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明はピルビン酸およびそのエステルの製造
方法、より詳細には、乳酸およびそのエステルを
含酸素ガスと反応させてピルビン酸およびそのエ
ステルを製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing pyruvic acid and its ester, and more particularly to a method for producing pyruvic acid and its ester by reacting lactic acid and its ester with an oxygen-containing gas.
ピルビン酸は生体内物質代謝経路での重要な中
間体であり、各種の生理活性物質を合成する有用
な合成原料である。また、インドールとピルビン
酸およびアンモニアを原料として、これにトリプ
トフアナーゼを作用させ、酵素法により、Ｌ−ト
リプトフアンを製造する方法における重要な原料
となる。このほかにも、硫化水素、アンモニアお
よびピルビン酸にシステインデスルフヒドラーゼ
の作用で、Ｌ−システインを合成する主要原料と
しても重要であり、同様にフエノール、アンモニ
アおよびピルビン酸にチロシナーゼの作用でＬ−
チロシンを合成する際の主要原料でもある。 Pyruvate is an important intermediate in the metabolic pathway of living organisms, and is a useful synthetic raw material for synthesizing various physiologically active substances. In addition, it is an important raw material in a method for producing L-tryptophan by an enzymatic method by using indole, pyruvic acid, and ammonia as raw materials and allowing tryptophanase to act on the raw materials. In addition, it is also important as a main raw material for synthesizing L-cysteine through the action of cysteine desulfhydrase on hydrogen sulfide, ammonia, and pyruvate, and similarly, it is an important raw material for synthesizing L-cysteine through the action of tyrosinase on phenol, ammonia, and pyruvate. −
It is also the main raw material for synthesizing tyrosine.
従来、ピルビン酸は、シアン化ソーダと塩化ア
セチルを反応させてシアン化アセチルを合成し、
これを加水分解する方法、または、酒石酸を硫酸
水素カリウムと反応させることにより製造されて
いる。しかしながら、シアン化アセチルを経由す
る方法は、収率が低く、副生成物が多量に生成
し、分離精製も困難である。また酒石酸を原料と
する方法は、原料が高価であつて、収率も悪い。 Conventionally, pyruvic acid was synthesized by reacting sodium cyanide and acetyl chloride to acetyl cyanide.
It is produced by hydrolyzing this or by reacting tartaric acid with potassium hydrogen sulfate. However, the method using acetyl cyanide has a low yield, produces a large amount of by-products, and is difficult to separate and purify. In addition, the method using tartaric acid as a raw material requires an expensive raw material and has a poor yield.
一方、アセトアルデヒドと、青酸のような安価
で工業的に大量に得られる原料から、容易に得ら
れる乳酸を原料とするピルビン酸の製法は、工業
的にみて有望な製造プロセスとなり得るポテンシ
アルを持つている。従来、乳酸からピルビン酸を
製造する既知の方法には(1)乳酸脱水素酵素または
乳酸脱水素酵素を持つ微生物、バクテリアなどの
作用で乳酸を脱水素する方法、(2)過マンガン酸カ
リなどの酸化剤を用い試薬酸化により乳酸を酸化
脱水素する方法、および(3)乳酸を気相で高温下脱
水素する方法、などが知られている。しかしなが
ら、前記１の方法は副生物としてα−ケト−グル
タル酸が副生し、これの分離が困難なこと、およ
び大量の高BOD廃水が出ることなどの欠点があ
る。２の方法は、収率も高々50％で、酸化剤の過
マンガン酸カリが高価であるなどの欠点がある。
３の方法は収率、とくに選択率が低いうえに、触
媒の寿命も短いという欠点がある。 On the other hand, the production method of pyruvic acid using lactic acid, which is easily obtained from raw materials such as acetaldehyde and hydrocyanic acid, which are inexpensive and can be obtained in large quantities industrially, has the potential to become a promising production process from an industrial perspective. There is. Conventionally, known methods for producing pyruvic acid from lactic acid include (1) dehydrogenation of lactic acid by the action of lactate dehydrogenase or microorganisms or bacteria that have lactate dehydrogenase, (2) potassium permanganate, etc. A method of oxidatively dehydrogenating lactic acid by reagent oxidation using an oxidizing agent, and (3) a method of dehydrogenating lactic acid in a gas phase at high temperature are known. However, method 1 has drawbacks such as the production of α-keto-glutaric acid as a by-product, which is difficult to separate, and a large amount of high-BOD wastewater produced. Method 2 has disadvantages, such as the yield being only 50% at most, and the oxidizing agent, potassium permanganate, being expensive.
Method 3 has the drawbacks of low yield, particularly low selectivity, and short catalyst life.
本発明の目的とするところは、従来法のような
欠点のない、乳酸およびそのエステルの酸化脱水
素によるピルビン酸およびそのエステルの新規な
製造法を提供することにある。 An object of the present invention is to provide a new method for producing pyruvic acid and its esters by oxidative dehydrogenation of lactic acid and its esters, which does not have the disadvantages of conventional methods.
本発明者は、乳酸の酸化脱水素方法、とくに、
酸化脱水素に用いる触媒に関して種々研究た結
果、白金または／およびパラジウムに鉛、錫、テ
ルルおよびイソジウムから成る群から選ばれた一
種以上の元素またはその元素の化合物を含有する
触媒の存在下に乳酸およびそのエステルを含酸素
ガスと反応させると効率よくピルビン酸およびそ
のエステルを与えることを見出して、本発明を完
成するに至つた。 The present inventor provides a method for oxidative dehydrogenation of lactic acid, in particular,
As a result of various studies on catalysts used for oxidative dehydrogenation, lactic acid The present inventors have discovered that pyruvic acid and its ester can be efficiently produced by reacting the ester thereof with an oxygen-containing gas, thereby completing the present invention.
乳酸またはそのエステルを酸化脱水素してピル
ビン酸またはそのエステルを製造するには、白金
または／およびパラジウムのような貴金属のみを
含有する触媒を用いる場合には、ピルビン酸また
はそのエステルは、実質的に生成しない。ところ
が、これらの貴金属とともに、鉛、錫、テルルお
よびイソジウムから成る群から選ばれた１種以上
の元素またはその元素の化合物を含有する触媒を
用いた場合には、意外なことに、乳酸またはその
エステルから、かつて考えられなかつたほどの効
率と収率でピルビン酸またはそのエステルが生成
する。 When a catalyst containing only noble metals such as platinum and/or palladium is used to produce pyruvic acid or its ester by oxidative dehydrogenation of lactic acid or its ester, pyruvic acid or its ester is substantially is not generated. However, when a catalyst containing one or more elements selected from the group consisting of lead, tin, tellurium, and isodium or a compound of such elements is used together with these precious metals, it is surprising that lactic acid or its Pyruvate or its esters are produced from esters with unprecedented efficiency and yields.
すなわち、本発明の方法は、乳酸またはそのエ
ステルを白金または／およびパラジウムに鉛、
錫、テルルおよびイソジウムから成る群から選ば
れた一種以上の元素またはその元素の化合物を含
有する触媒の存在下に含酸素ガスで酸化して、ピ
ルビン酸またはそのエステルを製造する方法であ
る。 That is, in the method of the present invention, lactic acid or its ester is added to platinum or/and palladium with lead,
This is a method for producing pyruvic acid or its ester by oxidizing it with an oxygen-containing gas in the presence of a catalyst containing one or more elements selected from the group consisting of tin, tellurium, and isodium or a compound of the element.
本発明の方法の出発物質は、遊離酸状態の乳
酸、乳酸のアルカリ金属塩、あるいは乳酸エステ
ルのいずれの形態であつても良い。 The starting material for the method of the present invention may be in the form of lactic acid in the free acid state, an alkali metal salt of lactic acid, or a lactic acid ester.
乳酸塩としては乳酸ナトリウム、乳酸カリウム
等の乳酸アルカリ金属塩、乳酸カルシウム、乳酸
マグネシウム等の乳酸アルカリ土類金属塩、また
は乳酸アンモニウム塩があげられる。 Examples of the lactate include alkali metal lactate salts such as sodium lactate and potassium lactate, alkaline earth metal salts of lactate such as calcium lactate and magnesium lactate, and ammonium lactate salts.
本発明の方法は、通常、液相において反応を実
施するが、気相で反応させることもできる。液相
反応を行なう場合には、通常、溶媒を用いる。原
料が遊離の酸、アルカリ金属塩、アルカリ土類金
属塩またはアンモニウム塩の場合には水溶媒を用
いるのが有利である。原料がエステルの場合には
ジオキサン、アセトン、などの乳酸エステルを溶
かす有機溶媒を溶媒に用いる。 In the method of the present invention, the reaction is usually carried out in the liquid phase, but the reaction can also be carried out in the gas phase. When carrying out a liquid phase reaction, a solvent is usually used. If the raw materials are free acids, alkali metal salts, alkaline earth metal salts or ammonium salts, it is advantageous to use an aqueous solvent. When the raw material is an ester, an organic solvent that dissolves the lactic acid ester, such as dioxane or acetone, is used as the solvent.
反応を実施する際の乳酸（遊離酸、アルカリ金
属塩、アルカリ土類金属塩、アンモニウム塩また
はエステルなど）の溶媒中の濃度は、２〜30wt
％、通常は５〜20wt％の範囲が適当である。 The concentration of lactic acid (free acid, alkali metal salt, alkaline earth metal salt, ammonium salt or ester, etc.) in the solvent when carrying out the reaction is between 2 and 30 wt.
%, usually in the range of 5 to 20 wt%.
本発明の方法で用いられる触媒は、白金また
は／およびパラジウムに、鉛、錫、テルルおよび
イソジウムから成る群から選ばれた一種以上の元
素またはその元素の化合物を含むものであつて、
通常は、適当な担体上に担持して反応に供する。
担体としては、活性炭、アルミナ、マグネシアな
どが用いられるが、液相反応の場合には、活性
炭、気相反応の場合には活性炭またはアルミナな
どが多用される。 The catalyst used in the method of the present invention contains platinum or/and palladium and one or more elements selected from the group consisting of lead, tin, tellurium and isodium, or a compound of the element,
Usually, it is supported on a suitable carrier and subjected to the reaction.
Activated carbon, alumina, magnesia, etc. are used as the carrier, and in the case of a liquid phase reaction, activated carbon is often used, and in the case of a gas phase reaction, activated carbon or alumina is often used.
触媒成分の担体上への担持量は、貴金属が0.5
〜10wt％、好ましくは１〜5wt％の範囲であり、
鉛、錫、テルルおよびインジウムから成る群から
選ばれた１種以上の元素または化合物が0.1〜
20wt％、好ましくは１〜10wt％の範囲である。
担持触媒の調製法は、たとえば、塩化白金酸の水
溶液および酢酸鉛の混合水溶液を活性炭に浸漬さ
せ、乾燥、水洗後、水中に懸濁させ、ホルマリ
ン、ヒドラジンまたは水素で還元するなどの方法
で調製する。また市販されている前記貴金属を含
有する担持触媒に鉛、錫、テルルおよびインジウ
ムから成る群から選ばれた元素の水溶性化合物を
浸漬する方法によつても製造できる。水溶性の前
記卑金属元素の化合物としては、硝酸塩、オキシ
塩化錫、オキシ塩化テルルまたはオキシ塩化イン
ジウムなどが多用される。 The amount of catalyst components supported on the carrier is 0.5% for precious metals.
~10wt%, preferably 1-5wt%,
One or more elements or compounds selected from the group consisting of lead, tin, tellurium, and indium in an amount of 0.1 to
20wt%, preferably in the range of 1 to 10wt%.
The supported catalyst can be prepared by, for example, immersing activated carbon in a mixed aqueous solution of chloroplatinic acid and lead acetate, drying, washing with water, suspending in water, and reducing with formalin, hydrazine, or hydrogen. do. It can also be produced by a method in which a water-soluble compound of an element selected from the group consisting of lead, tin, tellurium, and indium is immersed in a commercially available supported catalyst containing the noble metal. As the water-soluble compound of the base metal element, nitrate, tin oxychloride, tellurium oxychloride, indium oxychloride, etc. are often used.
触媒の使用量は、とくに制限はないが、反応液
１に対し、５〜100ｇの範囲が多用される。触
媒は、反応後別して長期間にわたり、繰返し使
用することができる。 The amount of catalyst used is not particularly limited, but is often in the range of 5 to 100 g per 1 reaction solution. The catalyst can be used repeatedly for a long period of time after the reaction.
本発明の方法で用いられる酸化剤は、含酸素ガ
スであつて、酸素、空気、または、酸素もしくは
空気を窒素のような不活性気体で希釈したものを
用いる。 The oxidizing agent used in the method of the present invention is an oxygen-containing gas such as oxygen, air, or oxygen or air diluted with an inert gas such as nitrogen.
本発明の方法を実施する反応温度は液相反応の
場合、室温〜100℃、好ましくは、35〜60℃の範
囲であつて、反応圧力は、常圧が多用される。反
応に要する時間は、触媒の使用量および反応温度
により定まるが、通常は、バツチ式の反応の場
合、0.5〜５時間の範囲である。 In the case of a liquid phase reaction, the reaction temperature at which the method of the present invention is carried out is in the range of room temperature to 100°C, preferably 35 to 60°C, and the reaction pressure is often atmospheric pressure. The time required for the reaction is determined by the amount of catalyst used and the reaction temperature, but is usually in the range of 0.5 to 5 hours in the case of a batch reaction.
気相反応を行なう際の原料物質は、乳酸エステ
ルが好ましい。乳酸エステルとしては、乳酸メチ
ルが多用される。反応温度は、100〜250℃、とく
に、150〜200℃の範囲が好ましい、乳酸エステル
をスチームあるいは窒素などの不活性気体と混合
し、これに空気を添加して反応させる。接触時間
は0.1秒〜10秒の範囲が好ましい。 The raw material used in the gas phase reaction is preferably lactic acid ester. As the lactic acid ester, methyl lactate is often used. The reaction temperature is preferably in the range of 100 to 250°C, particularly 150 to 200°C. Lactic acid ester is mixed with steam or an inert gas such as nitrogen, and air is added to the mixture for reaction. The contact time is preferably in the range of 0.1 seconds to 10 seconds.
以下、実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
内容１のステンレススチール円筒にバツフル
板、タービン翼型撹拌器、空気吹込管を付けたも
のを反応器として用いた。Example 1 A stainless steel cylinder as described in Content 1 equipped with a baffle plate, a turbine blade type stirrer, and an air blowing pipe was used as a reactor.
乳酸ソーダ11.2ｇを150ｇの水に溶かした水溶
液、および3wt％白金、5wt％の硝酸鉛を担持し
た活性炭粉末2.5ｇを上記反応器に仕込み、45℃
に保ち空気を150ml/minで吹込み600回転／分で
回転しながら反応させた。 An aqueous solution of 11.2 g of sodium lactate dissolved in 150 g of water and 2.5 g of activated carbon powder supporting 3 wt% platinum and 5 wt% lead nitrate were charged into the above reactor and heated at 45°C.
The reaction was carried out while blowing air at 150 ml/min and rotating at 600 rpm.
高速液体クロマトグラフの分析により反応開始
後、２時間で乳酸ソーダは実質的に消失したのが
認められたので反応操作を停止し、反応液から触
媒を別した。反応液は無色清澄であり、着色は
全く認められなかつた。高速液体クロマトグラフ
イーで分析した結果ピルビン酸ソーダ10ｇ（収率
90.9％）が生成していた。反応液を濃縮し、イオ
ン交換して遊離の酸としてオルトフエニレンジア
ミンとの縮合物を生成させ、そのNMRスペクト
ルから、得られた化合物がピルビン酸であること
を確認した。 High performance liquid chromatography analysis showed that sodium lactate had substantially disappeared 2 hours after the start of the reaction, so the reaction operation was stopped and the catalyst was separated from the reaction solution. The reaction solution was clear and colorless, with no coloration observed at all. As a result of analysis by high performance liquid chromatography, 10 g of sodium pyruvate (yield
90.9%) were generated. The reaction solution was concentrated and ion-exchanged to produce a condensate with orthophenylenediamine as a free acid, and its NMR spectrum confirmed that the resulting compound was pyruvic acid.
実施例 ２
実施例１と同じ装置と反応条件で、活性炭担持
5wt％白金、5wt％酸化錫触媒2.0ｇを用い、遊離
の乳酸9.0ｇを出発物質として反応させた。反応
時間３時間で、遊離のピルビン酸が、7.6ｇ（収
率86.4％）生成した。Example 2 Activated carbon supported using the same equipment and reaction conditions as Example 1
A reaction was carried out using 2.0 g of a 5 wt% platinum and 5 wt% tin oxide catalyst and 9.0 g of free lactic acid as a starting material. In a reaction time of 3 hours, 7.6 g (86.4% yield) of free pyruvic acid was produced.
実施例 ３
実施例１と同じ装置と反応条件で、乳酸メチル
エステル10.4ｇをジオキサン150ｇに溶解し、5wt
％パラジウム、2wt％酸化テルル、2wt％酸化イ
ンジウム活性炭触媒を用いて反応させた。反応時
間５時間でピルビン酸メチル9.2ｇが得られた。Example 3 Using the same equipment and reaction conditions as Example 1, 10.4 g of lactic acid methyl ester was dissolved in 150 g of dioxane, and 5 wt.
% palladium, 2 wt% tellurium oxide, and 2 wt% indium oxide activated carbon catalyst. After a reaction time of 5 hours, 9.2 g of methyl pyruvate was obtained.
実施例 ４
1wt％白金、2wt％酸化鉛を担持したアルミナ
粒状触媒をガラス管に充填し、乳酸メチルエステ
ルの蒸気、スチーム、空気を１：３：１の割合で
175℃に加熱してある触媒床を接触時間3.5秒で通
過させた。反応管通過液をガスクロマトグラフイ
ーにより分析したところ、乳酸メチルの転化率40
％、ピルビン酸メチルへの選択率80％であつた。Example 4 A glass tube was filled with an alumina granular catalyst supporting 1wt% platinum and 2wt% lead oxide, and lactate methyl ester vapor, steam, and air were added at a ratio of 1:3:1.
A contact time of 3.5 seconds was passed through the catalyst bed which had been heated to 175°C. Analysis of the liquid passing through the reaction tube by gas chromatography revealed that the conversion rate of methyl lactate was 40.
%, and the selectivity to methyl pyruvate was 80%.
比較例 １
底面に１μステンレススチール焼結金属板を備
えた内径108mmφ、高さ185mmの気泡塔に７重量％
の乳酸アンモニウム塩水溶液6000ｇおよび２重量
％の白金を担持させた活性炭粉末67.2ｇを仕込
み、PH7.0、50℃に保ちながら底面から空気を
2000/hrで吹き込み反応させた。Comparative Example 1 7% by weight in a bubble column with an inner diameter of 108 mmφ and a height of 185 mm with a 1μ stainless steel sintered metal plate on the bottom.
6,000 g of an aqueous solution of ammonium lactate and 67.2 g of activated carbon powder supporting 2% by weight of platinum were charged, and air was blown from the bottom while maintaining the pH at 7.0 and 50°C.
The reaction was carried out by blowing at 2000/hr.
反応開始後２時間で乳酸アンモニウム塩が消失
したことを高速液体クロマトグラフイー分析で確
認し、反応を停止した。触媒を濾別した無色の反
応液を高速液体クロマトグラフイーで分析したと
ころピルビン酸アンモニウム塩84ｇ（収率20％）
が得られた。 It was confirmed by high performance liquid chromatography analysis that the ammonium lactate salt had disappeared 2 hours after the start of the reaction, and the reaction was stopped. Analysis of the colorless reaction solution after filtering off the catalyst using high performance liquid chromatography revealed 84 g of ammonium pyruvate (yield 20%).
was gotten.
比較例 ２
空気吹き込み管およびバツフル板を備えた内容
１のステンレススチール円筒の撹拌槽に0.2重
量％の乳酸バリウム塩水溶液250ｇおよび10重量
％のパラジウムを担持させた活性炭粉末0.8ｇを
仕込み、PH4.0および70℃に保ちながら空気を
16.5/minで吹き込みつつタービン翼型撹拌器
で750回転／分で撹拌し反応させた。反応１時間
でピルビン酸バリウム塩ガ0.1ｇ（収率20％）が
得られた。Comparative Example 2 250 g of a 0.2% by weight barium lactate salt aqueous solution and 0.8g of activated carbon powder supporting 10% by weight of palladium were charged into the stainless steel cylindrical stirring tank of Content 1 equipped with an air blowing pipe and a buffer plate, and the pH was 4. Air while keeping at 0 and 70℃
The reaction was carried out by stirring at 750 rpm with a turbine blade type stirrer while blowing at 16.5 rpm. After 1 hour of reaction, 0.1 g (yield 20%) of barium pyruvate salt was obtained.
実施例 ５
内径38mmφ、高さ300mmのガラス製円筒の反応
槽に0.2重量％の乳酸カルシウム塩水溶液150ｇお
よび２重量％の白金と１重量％の炭酸鉛とを担持
させた活性炭粉末0.84ｇを仕込み、PH6.0および
90℃に保ちながら20mmφガラスポールフイルタよ
り空気を1.5/minで吹き込み反応させた。Example 5 150 g of a 0.2 wt% calcium lactate salt aqueous solution and 0.84 g of activated carbon powder supporting 2 wt% platinum and 1 wt% lead carbonate were placed in a glass cylindrical reaction tank with an inner diameter of 38 mmφ and a height of 300 mm. , PH6.0 and
While maintaining the temperature at 90°C, air was blown at 1.5/min through a 20 mmφ glass pole filter to cause a reaction.
反応30分でピルビン酸カルシウム塩0.2ｇ（収
率68％）を得た。 0.2 g (yield 68%) of calcium pyruvate salt was obtained in 30 minutes of reaction.
実施例 ６
ステンレススチール製１オートクレーブに10
重量％の乳酸アンモニウム溶液500ｇを入れた。
溶媒にはＮ・Ｎ−ジメチルホルムアミドが50：50
の比率のものを用いた。ついで、10重量％のパラ
ジウムに１重量％の錫を担持させた活性炭粉末
8.0ｇを加え、3.0−10Kg/cm2の加圧下、70℃、PH
7.0でタービン翼型反応機を300回転／分で撹拌し
ながらかきまぜて反応させた。Example 6 1 stainless steel autoclave 10
500 g of a wt% ammonium lactate solution was added.
The solvent is 50:50 N/N-dimethylformamide.
A ratio of Next, activated carbon powder containing 1% by weight of tin supported on 10% by weight of palladium was added.
Add 8.0g, under pressure of 3.0-10Kg/ cm2 , 70℃, PH
7.0, a turbine blade type reactor was stirred at 300 revolutions/min to carry out the reaction.
反応２時間でピルビン酸アンモニウム24.5ｇ
（収率51％）を得た。 24.5g of ammonium pyruvate in 2 hours of reaction
(yield 51%).
実施例 ７
５重量％白金および１重量％の鉛を担持させた
活性炭よりなる固定床中、８重量％乳酸アンモニ
ウム水溶液300ｇを80℃、PH7.0で空気を1.2/mi
ｎで吹き込み反応を行つた。Example 7 In a fixed bed made of activated carbon carrying 5% by weight of platinum and 1% by weight of lead, 300 g of an 8% by weight ammonium lactate aqueous solution was heated at 80°C, pH 7.0, and air was blown at 1.2/mi.
The blowing reaction was carried out at n.
反応１時間でピルビン酸アンモニウム14.1ｇ
（収率52％）を得た。 14.1g of ammonium pyruvate in 1 hour of reaction
(yield 52%).
Claims (1)
してピルビン酸およびそのエステルを製造する方
法において、白金または／およびパラジウムに、
鉛、錫、テルルおよびインジウムから成る群から
選ばれた１種以上の元素またはその元素の化合物
を含有する触媒の存在下に反応させることを特徴
するピルビン酸およびそのエステルの製造方法。1 In a method for producing pyruvic acid and its ester by oxidizing lactic acid and its ester with an oxygen-containing gas, platinum or/and palladium is
1. A method for producing pyruvic acid and its ester, which comprises reacting in the presence of a catalyst containing one or more elements selected from the group consisting of lead, tin, tellurium and indium or a compound of the element.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4426778A JPS54138514A (en) | 1978-04-17 | 1978-04-17 | Preparation of pyruvic acid |
| US06/028,695 US4242525A (en) | 1978-04-17 | 1979-04-10 | Process for producing salts of pyruvic acid |
| CH339579A CH641140A5 (en) | 1978-04-17 | 1979-04-10 | METHOD FOR PRODUCING A SALT OF PYRUVINIC ACIDS. |
| CA325,454A CA1101882A (en) | 1978-04-17 | 1979-04-12 | Process for producing salts of pyruvic acid |
| GB7912999A GB2018773B (en) | 1978-04-17 | 1979-04-12 | Process for producing salts of pyruvic acid |
| IT21888/79A IT1120113B (en) | 1978-04-17 | 1979-04-13 | PROCESS TO PRODUCE SALTS OF PYRUVIC ACID |
| DE2915395A DE2915395C2 (en) | 1978-04-17 | 1979-04-14 | Process for the preparation of a salt of pyruvic acid |
| FR7909654A FR2423472A1 (en) | 1978-04-17 | 1979-04-17 | PROCESS FOR PREPARING SALTS OF PYRUVIC ACID |
| NLAANVRAGE7902985,A NL184516C (en) | 1978-04-17 | 1979-04-17 | PROCESS FOR THE PREPARATION OF SALTS OF PYROVINIC ACID. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4426778A JPS54138514A (en) | 1978-04-17 | 1978-04-17 | Preparation of pyruvic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54138514A JPS54138514A (en) | 1979-10-27 |
| JPS6115863B2 true JPS6115863B2 (en) | 1986-04-26 |
Family
ID=12686729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4426778A Granted JPS54138514A (en) | 1978-04-17 | 1978-04-17 | Preparation of pyruvic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54138514A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60174377U (en) * | 1984-04-26 | 1985-11-19 | シャープ株式会社 | video phone |
| JPH0640961B2 (en) * | 1986-05-15 | 1994-06-01 | 花王株式会社 | Oxidation reaction catalyst composition |
| JPH01265055A (en) * | 1988-04-14 | 1989-10-23 | Mitsubishi Petrochem Co Ltd | Production of sodium alpha-ketobutyrate |
-
1978
- 1978-04-17 JP JP4426778A patent/JPS54138514A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54138514A (en) | 1979-10-27 |
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