JP2017115223A - Manufacturing method of l-cysteine mineral acid salt - Google Patents
Manufacturing method of l-cysteine mineral acid salt Download PDFInfo
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- JP2017115223A JP2017115223A JP2015254528A JP2015254528A JP2017115223A JP 2017115223 A JP2017115223 A JP 2017115223A JP 2015254528 A JP2015254528 A JP 2015254528A JP 2015254528 A JP2015254528 A JP 2015254528A JP 2017115223 A JP2017115223 A JP 2017115223A
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- mineral acid
- cysteine
- cystine
- acid salt
- salt
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- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 title claims abstract description 135
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 95
- 239000011707 mineral Substances 0.000 title claims abstract description 95
- 239000002253 acid Substances 0.000 title claims abstract description 90
- 150000003839 salts Chemical class 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000004201 L-cysteine Substances 0.000 claims abstract description 62
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 62
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims abstract description 49
- 229960003067 cystine Drugs 0.000 claims abstract description 49
- 239000004158 L-cystine Substances 0.000 claims abstract description 44
- 235000019393 L-cystine Nutrition 0.000 claims abstract description 44
- 150000003751 zinc Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 238000000746 purification Methods 0.000 abstract description 8
- 235000010755 mineral Nutrition 0.000 description 78
- 229960002433 cysteine Drugs 0.000 description 64
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 13
- 239000011701 zinc Substances 0.000 description 12
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 11
- 239000011592 zinc chloride Substances 0.000 description 11
- 235000005074 zinc chloride Nutrition 0.000 description 11
- 235000018417 cysteine Nutrition 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- VLSOAXRVHARBEQ-UHFFFAOYSA-N [4-fluoro-2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(F)C=C1CO VLSOAXRVHARBEQ-UHFFFAOYSA-N 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- NTTWTSPJXZIBAT-DKWTVANSSA-N (2r)-2-amino-3-sulfanylpropanoic acid;phosphoric acid Chemical compound OP(O)(O)=O.SC[C@H](N)C(O)=O NTTWTSPJXZIBAT-DKWTVANSSA-N 0.000 description 2
- PORCFLIWCKPHRW-DKWTVANSSA-N (2r)-2-amino-3-sulfanylpropanoic acid;sulfuric acid Chemical compound OS(O)(=O)=O.SC[C@H](N)C(O)=O PORCFLIWCKPHRW-DKWTVANSSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
本発明は電解還元によって、Ｌ−シスチンからＬ−システイン鉱酸塩を製造する方法に関する。 The present invention relates to a method for producing L-cysteine mineral acid salt from L-cystine by electrolytic reduction.
Ｌ−システイン鉱酸塩は、医薬品、食品添加物、化粧品等の用途に用いられている。Ｌ−システイン鉱酸塩を製造する方法としては、還元剤を用いて、Ｌ−シスチンを還元させてＬ−システイン鉱酸塩を製造する方法、Ｌ−シスチンの鉱酸水溶液をイオン交換樹脂で処理することでＬ−システイン鉱酸塩を製造する方法、Ｌ−シスチンの鉱酸水溶液に苛性アルカリを添加して中和しＬ−システイン鉱酸塩を製造する方法、Ｌ−シスチンの鉱酸水溶液を陰極液として、電解還元することでＬ−システイン鉱酸塩を製造する方法が挙げられる。 L-cysteine mineral acid salt is used for pharmaceuticals, food additives, cosmetics and the like. As a method for producing L-cysteine mineral acid salt, a method for producing L-cysteine mineral acid salt by reducing L-cystine using a reducing agent, and treating a mineral acid aqueous solution of L-cystine with an ion exchange resin A method for producing an L-cysteine mineral acid salt, a method for producing an L-cysteine mineral acid salt by adding a caustic alkali to an aqueous mineral acid solution for L-cystine, and an aqueous mineral acid solution for L-cystine Examples of the catholyte include a method of producing L-cysteine mineral acid salt by electrolytic reduction.
これらの中でもＬ−シスチンの鉱酸水溶液を陰極液として、電解還元することでＬ−システイン鉱酸塩を製造する方法が、以下の理由で好ましく挙げられる。
Ｌ−シスチンからＬ−システインへの化学反応では、水素化ホウ素ナトリウム等の還元剤が利用されるが、反応後に還元剤を除去する必要がある。
一方、電解還元の場合は、上記のような還元剤を必要とせず、さらに、反応後の精製工程が必要なく、コストを低減することが可能である。
また、電流量の制御は、化学反応の制御（温度、触媒量等）に比べ容易に管理することができ、選択還元が可能であることも利点である。
Among these, a method for producing L-cysteine mineral acid salt by electrolytic reduction using a mineral acid aqueous solution of L-cystine as a catholyte is preferred for the following reasons.
In the chemical reaction from L-cystine to L-cysteine, a reducing agent such as sodium borohydride is used, but it is necessary to remove the reducing agent after the reaction.
On the other hand, in the case of electrolytic reduction, the reducing agent as described above is not required, and further, a purification step after the reaction is not required, and the cost can be reduced.
In addition, the control of the amount of current can be easily managed as compared with the control of the chemical reaction (temperature, amount of catalyst, etc.), and it is advantageous in that selective reduction is possible.
Ｌ−システインの電解還元の反応機構を次に説明する。まず、電解槽にＬ−シスチンの鉱酸水溶液を導入し電流をかけ、電極表面にＬ−シスチンが接触し、電子の受け渡しを行うことで反応が進行する。よって反応初期は電流効率が高いが、反応終了付近では、シスチン濃度が極端に低くなるため、電極表面にシスチンが当たる確率が低くなり、反応の進行が遅くなる。最後は、シスチンよりも水が電気分解され、目的物が得られない状態になる。そのため、電解反応の途中で平衡状態となり、未反応の原料であるＬ−シスチンが残存してしまう問題があった。 Next, the reaction mechanism of the electroreduction of L-cysteine will be described. First, a mineral acid aqueous solution of L-cystine is introduced into an electrolytic cell, an electric current is applied, L-cystine comes into contact with the electrode surface, and the reaction proceeds by transferring electrons. Therefore, although the current efficiency is high at the beginning of the reaction, the cystine concentration becomes extremely low near the end of the reaction, so the probability that the cystine hits the electrode surface becomes low, and the progress of the reaction becomes slow. Finally, water is electrolyzed rather than cystine, and the target product cannot be obtained. For this reason, there has been a problem that L-cystine, which is an unreacted raw material, remains in an equilibrium state during the electrolytic reaction.
例えば、特許文献１には、電解反応によってＬ−シスチンをＬ−システインに還元させてＬ−システイン鉱酸塩を製造する方法が開示されている。なお、Ｌ−システイン鉱酸塩は、医薬品、食品添加物、化粧品用途として用いるためには、高い純度が求められ、具体的には純度９９．８％以上にする必要がある。
該方法では、還元剤を含有させて還元させる方法よりも高い純度は得られるものの、まだ、電解還元のみでは十分な純度が得られるわけではなく、電解還元後に精製工程が必要となっていた。
For example, Patent Document 1 discloses a method for producing L-cysteine mineral acid salt by reducing L-cystine to L-cysteine by electrolytic reaction. In addition, in order to use L-cysteine mineral acid salt as a pharmaceutical, a food additive, and a cosmetics use, high purity is calculated | required, Specifically, it is necessary to make purity 99.8% or more.
In this method, although a higher purity is obtained than in the method of reducing by containing a reducing agent, sufficient purity is not yet obtained only by electrolytic reduction, and a purification step is necessary after electrolytic reduction.
また、特許文献２には、陽イオン交換樹脂を隔膜とし、交互に陰極室と陽極室とを複数設けた密閉型隔膜電解槽の各陰極室内へシステイン鉱酸塩水溶液を連続的に供給循環せしめると共に、各陽極室へは稀鉱酸を連続的に供給循環せしめつつ電解還元する高純度システイン鉱酸塩の製法が開示されている。システイン鉱酸塩水溶液を適度の流速で陰極室に循環せしめ、段階的に電解還元を進めていく方法で、高純度のシステイン鉱酸塩を製造する製法である。
しかしながら、該製法を用いても純度９９．８％のシステイン鉱酸塩を得ることは困難であり、純度９９．８％のシステイン鉱酸塩を得るには精製工程が必要となっていた。
Further, in Patent Document 2, a cation exchange resin is used as a diaphragm, and a cysteine mineral acid aqueous solution is continuously supplied and circulated into each cathode chamber of a sealed diaphragm electrolytic cell in which a plurality of cathode chambers and anode chambers are alternately provided. At the same time, a method for producing a high-purity cysteine mineral salt that is electrolytically reduced while continuously supplying and circulating a rare mineral acid to each anode chamber is disclosed. This is a method for producing high-purity cysteine mineral acid salt by circulating an aqueous cysteine mineral acid salt solution to the cathode chamber at an appropriate flow rate and proceeding electrolytic reduction step by step.
However, it was difficult to obtain a cysteine mineral acid salt having a purity of 99.8% even using this production method, and a purification step was required to obtain a cysteine mineral acid salt having a purity of 99.8%.
上述したように、Ｌ−システイン鉱酸塩の純度を９９．８％以上にする必要があるが、これまでは電解反応後に精製工程を経なければ該純度に達することは不可能であった。煩雑な精製工程を必要とせず、電解反応のみで純度９９．８％以上のＬ−システイン鉱酸塩が得られる製造方法が求められている。 As described above, the purity of the L-cysteine mineral salt needs to be 99.8% or more. However, until now, it has been impossible to reach the purity without a purification step after the electrolytic reaction. There is a need for a production method that does not require a complicated purification step and that can obtain an L-cysteine mineral acid salt having a purity of 99.8% or more only by an electrolytic reaction.
本発明は、精製工程を必要とせず、電解反応のみで純度９９．８％以上のシステイン鉱酸塩を得ることができる、Ｌ−シスチンを還元してＬ−システイン鉱酸塩を製造する方法の提供を課題とする。 The present invention provides a method for producing L-cysteine mineral acid salt by reducing L-cystine, which does not require a purification step and can obtain cysteine mineral acid salt having a purity of 99.8% or more only by electrolytic reaction. Offering is an issue.
本発明者らが鋭意検討した結果、以下の内容の本発明を完成した。 As a result of intensive studies by the present inventors, the present invention having the following contents was completed.
第一の発明は、陽極室と陰極室とをセパレータで分離した電解槽を用い、該陰極室にＬ−シスチンの鉱酸水溶液を導入し電解還元させてＬ−システイン鉱酸塩を製造する方法において、該鉱酸水溶液に亜鉛塩を含有させて反応することを特徴とするＬ−システイン鉱酸塩の製造方法である。 A first invention uses an electrolytic cell in which an anode chamber and a cathode chamber are separated by a separator, and a method for producing an L-cysteine mineral acid salt by introducing a mineral acid aqueous solution of L-cystine into the cathode chamber and electrolytically reducing it. The method for producing an L-cysteine mineral acid salt comprising reacting the aqueous mineral acid solution with a zinc salt.
第二の発明は、鉱酸水溶液中の亜鉛塩の含有量が、０．１〜５．０質量％であることを特徴とする第一の発明に記載のＬ−システイン鉱酸塩の製造方法である。 The second invention is the method for producing an L-cysteine mineral acid salt according to the first invention, wherein the content of the zinc salt in the mineral acid aqueous solution is 0.1 to 5.0% by mass It is.
第三の発明は、鉱酸水溶液が、塩酸水溶液であることを特徴とする第一又は第二の発明に記載のＬ−システイン鉱酸塩の製造方法である。 A third invention is a method for producing an L-cysteine mineral acid salt according to the first or second invention, wherein the mineral acid aqueous solution is a hydrochloric acid aqueous solution.
第四の発明は、陰極室に用いる陰極が、カーボン電極であることを特徴とする第一から第三の発明のいずれか一項に記載のＬ−システイン鉱酸塩の製造方法である。 A fourth invention is the method for producing an L-cysteine mineral acid salt according to any one of the first to third inventions, wherein the cathode used in the cathode chamber is a carbon electrode.
本発明によれば、陽極室と陰極室とをセパレータで分離した電解槽を用い、該陰極室にＬ−シスチンの鉱酸水溶液を導入し電解還元させてＬ−システイン鉱酸塩を製造する方法において、該鉱酸水溶液に亜鉛塩を含有させて反応させることで電流効率が向上し、精製工程を経なくても電解反応のみで、純度が９９．８％以上のＬ−システイン鉱酸塩を得ることができる方法である。 According to the present invention, an electrolytic cell in which an anode chamber and a cathode chamber are separated by a separator is used, and an aqueous L-cystine mineral acid solution is introduced into the cathode chamber and electrolytically reduced to produce an L-cysteine mineral acid salt. In this case, the current efficiency is improved by adding a zinc salt to the mineral acid aqueous solution, and the L-cysteine mineral acid salt having a purity of 99.8% or more is obtained only by an electrolytic reaction without going through a purification step. It is a method that can be obtained.
本発明において、Ｌ−システインとは、アミノ酸の１つで、２−アミノ−３−スルファニルプロピオン酸のことをいう。鉱酸とは無機酸のことであり、例えば、塩酸、硫酸、リン酸、硝酸、ホウ酸等が挙げられる。
Ｌ−システイン鉱酸塩とは、Ｌ−システインと鉱酸との塩のことをいう。本願の製造方法ではＬ−シスチンを原料として用いることで、Ｌ−システイン鉱酸塩を製造することができる。
In the present invention, L-cysteine is one of amino acids and refers to 2-amino-3-sulfanylpropionic acid. The mineral acid is an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and boric acid.
L-cysteine mineral acid salt refers to a salt of L-cysteine and a mineral acid. In the production method of the present application, L-cysteine mineral acid salt can be produced by using L-cystine as a raw material.
本願発明のＬ−システイン鉱酸塩の製造方法について説明する。 The manufacturing method of the L-cysteine mineral acid salt of this invention is demonstrated.
本願発明は、陽極室と陰極室とをセパレータで分離した電解槽を用い、該陰極室にＬ−シスチンの鉱酸水溶液を導入し電解還元させてＬ−システイン鉱酸塩を製造する方法において、該鉱酸水溶液に亜鉛塩を含有させて反応することを特徴とするＬ−システイン鉱酸塩の製造方法である。 The present invention uses an electrolytic cell in which an anode chamber and a cathode chamber are separated by a separator, and a method for producing an L-cysteine mineral acid salt by introducing a mineral acid aqueous solution of L-cystine into the cathode chamber and electrolytically reducing it. A method for producing an L-cysteine mineral acid salt comprising reacting a mineral acid aqueous solution with a zinc salt.
前記陽極室には、鉱酸水溶液を導入し、陽極を浸漬させて使用する。なお、陽極室に用いる無機酸又は有機酸は陰極室に用いる鉱酸水溶液と同一種類である必要はない。
陽極室に導入する鉱酸水溶液の鉱酸の濃度は、一般的に１〜３０％であるのが好ましく挙げられる。
A mineral acid aqueous solution is introduced into the anode chamber, and the anode is immersed for use. Note that the inorganic acid or organic acid used in the anode chamber need not be the same type as the mineral acid aqueous solution used in the cathode chamber.
The concentration of the mineral acid in the aqueous mineral acid solution introduced into the anode chamber is preferably 1 to 30% in general.
前記無機酸としては、塩酸、硫酸、リン酸、ホウ酸等が挙げられる。前記有機酸としては、ギ酸、酢酸、シュウ酸等が挙げられる。 Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, boric acid and the like. Examples of the organic acid include formic acid, acetic acid, and oxalic acid.
陽極の材質としては、酸化イリジウム、金、白金、パラジウム、銀、鉛等が挙げられる。これらの中でも特に酸化イリジウムが、酸素過電圧が低く、耐食性に優れるため好ましく挙げられる。 Examples of the material for the anode include iridium oxide, gold, platinum, palladium, silver, and lead. Among these, iridium oxide is particularly preferable because it has a low oxygen overvoltage and excellent corrosion resistance.
陰極室には、Ｌ−シスチンの鉱酸水溶液を導入し、陰極を浸漬させて使用する。 In the cathode chamber, a mineral acid aqueous solution of L-cystine is introduced and the cathode is immersed for use.
陰極の材料は、亜鉛、錫、カーボン、チタン等が挙げられる。水素過電圧の高いカーボン又はチタンを用いることが好ましく、カーボンを用いることが特に好ましく挙げられる。カーボン材料としては、グラファイト、カーボンペーパー、グラッシーカーボン、ダイヤモンドライクカーボン、等方性炭素等が挙げられる。
カーボン材料を用いたカーボン電極は特に水素過電圧が高いので、水の電気分解が起きづらく、電解還元に電力を効率よく使用することができるため、短時間でＬ−シスチンを還元させてＬ−システインを製造することができる。
Examples of the cathode material include zinc, tin, carbon, and titanium. It is preferable to use carbon or titanium having a high hydrogen overvoltage, and it is particularly preferable to use carbon. Examples of the carbon material include graphite, carbon paper, glassy carbon, diamond-like carbon, and isotropic carbon.
A carbon electrode using a carbon material has a particularly high hydrogen overvoltage, so that water electrolysis is difficult to occur and electric power can be efficiently used for electrolytic reduction. Therefore, L-cystine can be reduced in a short time to produce L-cysteine. Can be manufactured.
Ｌ−シスチンの鉱酸水溶液中に亜鉛塩を含有させて電解還元することで、亜鉛イオンが電子を受けとり、亜鉛金属となり、電極表面に析出する。
Ｚｎ2＋ ＋ ２ｅ− → Ｚｎ
析出した亜鉛金属は電子を放出することで溶解し、そのときの電子がＬ−シスチンをＬ−システインに還元するのに使われる。
Ｚｎ ＋ ＣｙＣｙ ＋ ２Ｈ＋ → Ｚｎ２＋ ＋ ２ＣｙＨ
（式中、ＣｙＣｙはＬ−シスチン、ＣｙＨはＬ−システインを示す。）
このように、亜鉛が電子の受け渡し役（メディエータ）になることで、電流効率が上がり、反応終盤も、Ｌ−シスチンへの反応確率が上がるため、１００％まで反応が進行する。また、反応完了後、不純物の亜鉛は電極表面に析出するため、反応液への混入もなく、後処理が不必要になる。
By carrying out electrolytic reduction by containing a zinc salt in a mineral acid aqueous solution of L-cystine, zinc ions receive electrons, become zinc metal, and deposit on the electrode surface.
Zn 2+ + 2e − → Zn
The deposited zinc metal dissolves by releasing electrons, and the electrons at that time are used to reduce L-cystine to L-cysteine.
Zn + CyCy + 2H + → Zn 2+ + 2CyH
(In the formula, CyCy represents L-cystine and CyH represents L-cysteine.)
Thus, since zinc becomes an electron transfer function (mediator), the current efficiency is increased and the reaction probability at the end of the reaction is increased to L-cystine, so that the reaction proceeds to 100%. In addition, after completion of the reaction, impurity zinc is deposited on the electrode surface, so that it is not mixed into the reaction solution, and post-treatment is unnecessary.
陰極室に用いる鉱酸水溶液における鉱酸の濃度は、１〜３０質量％が好ましく、５〜２０質量％がより好ましく挙げられる。用いるＬ−シスチンの含有量に対し、０．１〜５倍ｍｏｌ含有させることが好ましく挙げられる。
Ｌ−シスチン自体は水への溶解度が低いため、反応効率を上げるため溶解度を上げる必要がある。Ｌ−シスチン鉱酸塩は溶解度が高く反応効率を上げることが出来る。
また、Ｌ−システイン自体は空気酸化して、容易にＬ−シスチンに戻る。Ｌ−システイン鉱酸塩は安定化であるため、鉱酸を加えることで、純度の低下を防ぐことができる。
1-30 mass% is preferable and, as for the density | concentration of the mineral acid in the mineral acid aqueous solution used for a cathode chamber, 5-20 mass% is mentioned more preferably. A preferred content is 0.1-5 times mol with respect to the content of L-cystine used.
Since L-cystine itself has low solubility in water, it is necessary to increase the solubility in order to increase the reaction efficiency. L-cystine mineral salt has high solubility and can increase the reaction efficiency.
In addition, L-cysteine itself is oxidized by air and easily returns to L-cystine. Since L-cysteine mineral acid salt is stabilized, a decrease in purity can be prevented by adding a mineral acid.
Ｌ−シスチンの鉱酸水溶液におけるＬ−シスチンの含有量は、１〜３０質量％が好ましく、５〜２０質量％が特に好ましく挙げられる。
Ｌ−シスチンの濃度を濃くすると結晶が析出し、デットスペースへの結晶析出で未反応が残るなどし、Ｌ−システイン鉱酸塩の純度に悪影響を及ぼす。また、複雑な加温機能を持つ生産設備によりこの結晶析出を防止することは可能であるが、工業的規模の生産においては現実的ではない。そのため、Ｌ−シスチン鉱酸塩及びＬ−システイン鉱酸塩が溶解する濃度範囲として、上記濃度範囲が特に好ましく挙げられる。
ただし、Ｌ−シスチンの鉱酸水溶液におけるＬ−シスチンは完全に鉱酸水溶液に溶解している必要はなく、電解反応中に溶解すればよい。
1-30 mass% is preferable and, as for content of L-cystine in the mineral acid aqueous solution of L-cystine, 5-20 mass% is mentioned especially preferably.
When the concentration of L-cystine is increased, crystals are precipitated and unreacted by crystal precipitation in the dead space, which adversely affects the purity of the L-cysteine mineral acid salt. In addition, although it is possible to prevent this crystal precipitation by using a production facility having a complicated heating function, it is not practical in industrial scale production. Therefore, the above-mentioned concentration range is particularly preferably mentioned as the concentration range in which L-cystine mineral acid salt and L-cysteine mineral acid salt are dissolved.
However, L-cystine in the mineral acid aqueous solution of L-cystine does not need to be completely dissolved in the mineral acid aqueous solution, and may be dissolved during the electrolytic reaction.
該鉱酸水溶液に含有させる亜鉛塩としては、塩化亜鉛、硫酸亜鉛、リン酸亜鉛等が挙げられる。 Examples of the zinc salt contained in the mineral acid aqueous solution include zinc chloride, zinc sulfate, and zinc phosphate.
該鉱酸水溶液における亜鉛塩の含有量は、０．１〜５．０質量％であることが好ましく、０．５〜４．０質量％であることがより好ましく挙げられる。
反応中盤では、亜鉛は電子を運ぶ役割（メディエータ）を担うため、反応効率を上げる目的で、ある程度の添加量は必要になるが、コンタミの原因になるため、多量に加えるのは得策ではない。
亜鉛は、反応終盤の追い切りに必要であるため、本発明は少量でも効果が期待できる。また、最後に電極表面に亜鉛を析出させ、反応溶液から除去する必要があるため、電極面積との兼ね合いで亜鉛塩の添加量を設定する必要がある。
The content of the zinc salt in the aqueous mineral acid solution is preferably 0.1 to 5.0% by mass, and more preferably 0.5 to 4.0% by mass.
In the middle of the reaction, since zinc plays a role of transporting electrons (mediator), a certain amount of addition is necessary for the purpose of increasing the reaction efficiency, but it is not a good idea to add a large amount because it causes contamination.
Since zinc is necessary for the end of the reaction, the present invention can be expected to be effective even in a small amount. Moreover, since it is necessary to finally deposit zinc on the electrode surface and remove it from the reaction solution, it is necessary to set the amount of zinc salt added in consideration of the electrode area.
亜鉛塩を含有させて還元反応を行うことで、電流効率が向上するため、Ｌ−シスチンからＬ−システインへ完全に還元させることが可能であり、その結果、純度９９．８％以上でシステイン鉱酸塩を製造することができる。 Since the current efficiency is improved by carrying out the reduction reaction by containing the zinc salt, it is possible to completely reduce L-cystine to L-cysteine, and as a result, the cysteine ore has a purity of 99.8% or more. Acid salts can be produced.
また、鉛塩、チタン塩、銅塩、スズ塩、クロム塩等の金属塩を用いても、上述したようなメディエータの役割がほぼ機能しないため、電流効率の向上はほとんど見られず、完全にＬ−シスチンをＬ−システインに還元させることができない問題がある。 In addition, even when using metal salts such as lead salts, titanium salts, copper salts, tin salts, chromium salts, the role of the mediator as described above hardly functions, so there is almost no improvement in current efficiency, and it is completely There is a problem that L-cystine cannot be reduced to L-cysteine.
セパレータとしては、ポリ塩化ビニル製やポリテトラフルオロエチレン（ＰＴＦＥ）製隔膜、ショ糖脂肪酸エステル製隔膜、又は陽イオン交換膜を用いることができる。陽イオン交換膜を用いることが好ましく挙げられ、陽イオン交換膜の中でも炭素−フッ素からなる疎水性テフロン（登録商標）骨格とスルホン酸基を持つパーフルオロ側鎖から構成されるパーフルオロカーボン材料である膜（例えば、ナフィオン（登録商標）膜、デュポン社製）が好ましく挙げられる。
セパレータを設けることによって、電解還元したＬ−システインが陽極で酸化により再びＬ−シスチンへ戻ることを防止することができる。
As the separator, a polyvinyl chloride or polytetrafluoroethylene (PTFE) diaphragm, a sucrose fatty acid ester diaphragm, or a cation exchange membrane can be used. It is preferable to use a cation exchange membrane, and among the cation exchange membranes, it is a perfluorocarbon material composed of a hydrophobic Teflon (registered trademark) skeleton composed of carbon-fluorine and a perfluoro side chain having a sulfonic acid group. A membrane (for example, Nafion (registered trademark) membrane, manufactured by DuPont) is preferably mentioned.
By providing the separator, electrolytically reduced L-cysteine can be prevented from returning to L-cystine again by oxidation at the anode.
Ｌ−システイン鉱酸塩としては、Ｌ−システイン塩酸塩、Ｌ−システイン硫酸塩、Ｌ−システインリン酸塩等が挙げられ、本願発明の製造方法によって製造することができる。
陰極室に用いる鉱酸水溶液によって、Ｌ−システイン鉱酸塩が決まり、例えば、塩酸水溶液を用いることで、Ｌ−システイン塩酸塩を得ることができる。
Examples of L-cysteine mineral salts include L-cysteine hydrochloride, L-cysteine sulfate, L-cysteine phosphate, and the like, and can be produced by the production method of the present invention.
The L-cysteine mineral acid salt is determined by the aqueous mineral acid solution used in the cathode chamber. For example, L-cysteine hydrochloride can be obtained by using an aqueous hydrochloric acid solution.
これらのＬ−システイン鉱酸塩の中でもＬ−システイン塩酸塩は、他のＬ−システイン硫酸塩やＬ−システインリン酸塩等よりも融点が高いため、室温で固体であり、取り扱いが容易であるため好ましく挙げられる。 Among these L-cysteine mineral salts, L-cysteine hydrochloride has a higher melting point than other L-cysteine sulfates, L-cysteine phosphates, etc., and is therefore solid at room temperature and easy to handle. Therefore, it is preferable.
次に電解還元方法について説明する。電解還元するときの電流量は、０．１〜２０Ａ／ｄｍ２の電流量で電解反応するのが好ましく、１〜１０Ａ／ｄｍ２で電解反応させるのがより好ましく挙げられる。電流値を上げたほうが反応速度は速くなるが、電流値を上げると電圧が高くなり、副反応の水の電気分解が起こり、反応効率を低下させるため好ましくない。そのため、前記電流量で電解還元することで、効率よくＬ−シスチンからＬ−システインに還元させることができる。 Next, the electrolytic reduction method will be described. Current amount at the time of electrolytic reduction, it is preferable to electrolytic reaction at a current amount of 0.1~20A / dm 2, and the like and more preferably is an electrolytic reaction at 1 to 10 A / dm 2. Increasing the current value increases the reaction rate, but increasing the current value increases the voltage, causing side reaction water electrolysis and reducing the reaction efficiency. Therefore, it is possible to efficiently reduce L-cystine to L-cysteine by electrolytic reduction with the amount of current.
次に電流効率の算出方法について説明する。下記反応式から、Ｌ−シスチン１ｍｏｌが２電子を消費し、Ｌ−システイン２ｍｏｌが生成するため、１電子１ｍｏｌ反応になる。
ＣｙＣｙ ＋ ２Ｈ＋ ＋ ２ｅ− → ２ＣｙＨ
（式中、ＣｙＣｙはＬ−シスチン、ＣｙＨはＬ−システインを示す。）
したがって、電流効率（％）はファラデーの法則に基づいて、以下の計算式により算出することができる。
CyCy + 2H + + 2e − → 2CyH
(In the formula, CyCy represents L-cystine and CyH represents L-cysteine.)
Therefore, the current efficiency (%) can be calculated by the following formula based on Faraday's law.
本発明の製造方法において、陰極室に導入されるＬ−シスチンの鉱酸水溶液及び亜鉛塩以外に他の添加剤を一切含有させる必要はないため、高純度のＬ−システイン鉱酸塩が得られるとともに、不必要な物質の電析もないため、高収率高純度で目的物を容易な操作で得ることができる。 In the production method of the present invention, since it is not necessary to contain any other additive other than the mineral acid aqueous solution and zinc salt of L-cystine introduced into the cathode chamber, a highly pure L-cysteine mineral salt can be obtained. In addition, since there is no electrodeposition of unnecessary substances, the target product can be obtained with high yield and high purity by an easy operation.
Ｌ−システイン鉱酸塩は空気中で安定であり、Ｌ−システインのように空気中で酸化してＬ−シスチンに戻ることはない特徴を有している。 L-cysteine mineral acid salt is stable in the air and has a characteristic that it does not oxidize in the air and returns to L-cystine like L-cysteine.
また必要に応じて、本願発明により得られたＬ−システイン鉱酸塩を、脱酸させてＬ−システインとすることができる。 If necessary, the L-cysteine mineral acid salt obtained by the present invention can be deoxidized to give L-cysteine.
以下に実施例を挙げることによって本発明をさらに詳しく説明する。本発明はこれら実施例に限定されるわけではない。 Hereinafter, the present invention will be described in more detail by giving examples. The present invention is not limited to these examples.
（実施例１）
セパレータとして疎水性テフロン（登録商標）骨格とスルホン酸基を持つナフィオン（登録商標）４２４（デュポン社製）を用いた隔膜電解槽（陽極室及び陰極室の容量が各々１００ｍＬ）で、陽極として酸化イリジウム電極（面積：０．０２５ｄｍ２）、陰極室としてカーボン電極（面積：０．０２５ｄｍ２）を、また陽極液として１０ｗｔ％硫酸５０ｍｌ、陰極液としてＬ−シスチン５ｇ、塩化亜鉛０．１ｇを加えた５．３ｗｔ％塩酸溶液５０ｍｌを用いた。陽極、陰極両方にテフロン（登録商標）製撹拌子を導入し、循環させながら電解を行った。陰極電流密度を５Ａ／ｄｍ２、電解温度を２０℃として電解し、２３時間、３０時間通電した後の陰極液を高速液体クロマトグラフにより分析しＬ−システインの純度を求めた。電流効率（％）は３０時間後のＬ−システインの純度と通電した電気量から算出した。
Example 1
Separation electrolytic cell (capacity of anode chamber and cathode chamber is 100 mL each) using Nafion (registered trademark) 424 (manufactured by DuPont) having hydrophobic Teflon (registered trademark) skeleton and sulfonic acid group as separator, and oxidizing as anode Add an iridium electrode (area: 0.025 dm 2 ), a carbon electrode (area: 0.025 dm 2 ) as the cathode chamber, 50 ml of 10 wt% sulfuric acid as the anolyte, 5 g of L-cystine as the catholyte, and 0.1 g of zinc chloride. In addition, 50 ml of 5.3 wt% hydrochloric acid solution was used. A Teflon (registered trademark) stirrer was introduced into both the anode and cathode, and electrolysis was performed while circulating. Electrolysis was performed at a cathode current density of 5 A / dm 2 and an electrolysis temperature of 20 ° C., and the catholyte after energization for 23 hours and 30 hours was analyzed by high performance liquid chromatography to determine the purity of L-cysteine. The current efficiency (%) was calculated from the purity of L-cysteine after 30 hours and the amount of electricity supplied.
高速液体クロマトグラフの測定条件を以下に示し、検量線を作成して純度（％）を算出した。結果を表１に示す。
使用装置：ＳＨＩＳＥＩＤＯ ＮＡＮＯＳＰＡＣＥ Ｓｌ−１
カラム：ＴＯＳＯＨ ＯＤＳ−１００Ｖ ５μｍ ４．６ｍｍＩＤ ２５センチ
温度：４０℃
溶離液：Ａ) アセトニトリル
Ｂ) ５０ｍＭＮａＨ２ＰＯ４、５ｍＭＫＨ２ＰＯ４（ｐＨ２．２；Ｈ３ＰＯ４ ）
Ａ／Ｂ ＝ ２．５／９７．５ (ｗ／ｗ)
流量：０．４ｍＬ／ｍｉｎ
注入量：１０μＬ
検出波長：２１０ｎｍ
検量線作成は、シスチン及びシステインそれぞれを１００、２００、３００ｐｐｍに調整、高速液体クロマトグラフで測定し、シスチンとシステインのｗｔとＡＲＥＡの検量線を作成した。
The measurement conditions of the high performance liquid chromatograph are shown below, and a calibration curve was created to calculate the purity (%). The results are shown in Table 1.
Equipment used: SHISEIDO NANOSPACE S1-1
Column: TOSOH ODS-100V 5 μm 4.6 mm ID 25 cm Temperature: 40 ° C.
Eluent: A) Acetonitrile B) 50 mM NaH 2 PO 4 , 5 mM KH 2 PO 4 (pH 2.2; H 3 PO 4 )
A / B = 2.5 / 97.5 (w / w)
Flow rate: 0.4 mL / min
Injection volume: 10 μL
Detection wavelength: 210 nm
Calibration curves were prepared by adjusting cystine and cysteine to 100, 200, and 300 ppm, respectively, and measuring them with a high performance liquid chromatograph to prepare calibration curves for cystine and cysteine wt and AREA.
（実施例２）
実施例１に記載の塩化亜鉛の代わりに硫酸亜鉛を０．１ｇ加えた以外は、実施例１と同様に電解し、電流効率及び純度を求め、その結果を表１に示す。
(Example 2)
Electrolysis was performed in the same manner as in Example 1 except that 0.1 g of zinc sulfate was added instead of zinc chloride described in Example 1, and the current efficiency and purity were determined. The results are shown in Table 1.
（実施例３）
実施例１に記載の塩化亜鉛の代わりにリン酸亜鉛を０．１ｇ加えた以外は、実施例１と同様に電解し、電流効率及び純度を求め、その結果を表１に示す。
(Example 3)
Electrolysis was performed in the same manner as in Example 1 except that 0.1 g of zinc phosphate was added instead of zinc chloride described in Example 1, and the current efficiency and purity were determined. The results are shown in Table 1.
（比較例１）
実施例１に記載の塩化亜鉛を加えない点を除き実施例１と同様に電解し、電流効率及び純度を求め、その結果を表１に示す。
(Comparative Example 1)
Electrolysis was carried out in the same manner as in Example 1 except that zinc chloride described in Example 1 was not added, and the current efficiency and purity were determined. The results are shown in Table 1.
（比較例２）
実施例１に記載の塩化亜鉛の代わりに塩化銅を０．１ｇ加えた以外は、実施例１と同様に電解し、電流効率及び純度を求め、その結果を表１に示す。
(Comparative Example 2)
Electrolysis was performed in the same manner as in Example 1 except that 0.1 g of copper chloride was added instead of zinc chloride described in Example 1, and the current efficiency and purity were determined. The results are shown in Table 1.
（比較例３）
実施例１に記載の塩化亜鉛の代わりに硫酸銅を０．１ｇ加えた以外は、実施例１と同様に電解し、電流効率及び純度を求め、その結果を表１に示す。
(Comparative Example 3)
Electrolysis was performed in the same manner as in Example 1 except that 0.1 g of copper sulfate was added instead of zinc chloride described in Example 1, and the current efficiency and purity were determined. The results are shown in Table 1.
（比較例４）
実施例１に記載の塩化亜鉛の代わりに塩化スズを０．１ｇ加えた以外は、実施例１と同様に電解し、電流効率及び純度を求め、その結果を表１に示す。
(Comparative Example 4)
Electrolysis was performed in the same manner as in Example 1 except that 0.1 g of tin chloride was added instead of zinc chloride described in Example 1, and the current efficiency and purity were determined. The results are shown in Table 1.
（比較例５）
実施例１に記載の塩化亜鉛の代わりに塩化チタンを０．１ｇ加えた以外は、実施例１と同様に電解し、電流効率及び純度を求め、その結果を表１に示す。
(Comparative Example 5)
Electrolysis was performed in the same manner as in Example 1 except that 0.1 g of titanium chloride was added instead of zinc chloride described in Example 1, and the current efficiency and purity were determined. The results are shown in Table 1.
（比較例６）
実施例１に記載の塩化亜鉛の代わりに塩化鉛を０．１ｇ加えた以外は、実施例１と同様に電解し、電流効率及び純度を求め、その結果を表１に示す。
(Comparative Example 6)
Electrolysis was performed in the same manner as in Example 1 except that 0.1 g of lead chloride was added instead of zinc chloride described in Example 1, and the current efficiency and purity were determined. The results are shown in Table 1.
実施例１〜６よりも実施例１〜３の方が、電流効率が高く、３０時間後では純度１００％のＬ−システイン鉱酸塩が得られることがわかる。実施の中でも特に実施例１に用いた塩化亜鉛は、他の亜鉛塩よりも解離しやすいため亜鉛イオンになりやすく、メディエータの効果が高いので、短時間で反応が早く進行することが確認できた。
比較例２、３の結果を見ると、水素よりイオン化傾向の低い銅では、金属の析出と溶解を繰り返すことができないため、電子のメディエータの効果が得られず、電流効率、純度の向上は見られない。
比較例４〜６のように、水素よりイオン化傾向が高く、金属が析出と溶解を繰り返すことの出来る金属塩では、若干電子のメディエータの効果が得られるが、亜鉛塩には及ばないものであった。
It can be seen that Examples 1 to 3 have higher current efficiency than Examples 1 to 6, and an L-cysteine mineral acid salt having a purity of 100% can be obtained after 30 hours. In particular, the zinc chloride used in Example 1 was more likely to be dissociated than other zinc salts, so that it was likely to be zinc ions, and the mediator effect was high, so that the reaction proceeded quickly in a short time. .
From the results of Comparative Examples 2 and 3, copper, which has a lower ionization tendency than hydrogen, cannot repeat the deposition and dissolution of the metal, so the effect of the electron mediator cannot be obtained, and the improvement in current efficiency and purity is observed. I can't.
As in Comparative Examples 4 to 6, a metal salt having a higher ionization tendency than hydrogen and capable of repeating the precipitation and dissolution of the metal provides a slight electron mediator effect, but does not reach the zinc salt. It was.
本願発明のＬ−システイン鉱酸塩の製造方法により得られるＬ−システイン鉱酸塩は、純度が９９．８％以上であるので、医薬品、食品添加物、化粧品等の様々な用途で使用することができる。 Since the purity of the L-cysteine mineral acid salt obtained by the method for producing L-cysteine mineral acid salt of the present invention is 99.8% or more, it should be used for various uses such as pharmaceuticals, food additives, cosmetics and the like. Can do.
Claims (4)
該鉱酸水溶液に亜鉛塩を含有させて反応することを特徴とするＬ−システイン鉱酸塩の製造方法。 In the method of producing an L-cysteine mineral acid salt by using an electrolytic cell in which an anode chamber and a cathode chamber are separated by a separator, introducing an aqueous mineral acid solution of L-cystine into the cathode chamber and electrolytically reducing it,
A method for producing an L-cysteine mineral acid salt, comprising reacting the aqueous mineral acid solution with a zinc salt.
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