JP2716481B2 - Glycine production method - Google Patents
Glycine production methodInfo
- Publication number
- JP2716481B2 JP2716481B2 JP63260654A JP26065488A JP2716481B2 JP 2716481 B2 JP2716481 B2 JP 2716481B2 JP 63260654 A JP63260654 A JP 63260654A JP 26065488 A JP26065488 A JP 26065488A JP 2716481 B2 JP2716481 B2 JP 2716481B2
- Authority
- JP
- Japan
- Prior art keywords
- glycine
- glycolonitrile
- diketopiperazine
- reaction
- 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 - Fee Related
Links
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims description 44
- 239000004471 Glycine Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 claims description 21
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 21
- FYWDUQCSMYWUHV-UHFFFAOYSA-N 3-chloro-5-hydroxypentan-2-one Chemical compound CC(=O)C(Cl)CCO FYWDUQCSMYWUHV-UHFFFAOYSA-N 0.000 claims description 17
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 6
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 4
- 229940091173 hydantoin Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- YMAWOPBAYDPSLA-UHFFFAOYSA-N glycylglycine Chemical compound [NH3+]CC(=O)NCC([O-])=O YMAWOPBAYDPSLA-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NFODSNOCEFVBRY-UHFFFAOYSA-N 2-(carbamoylamino)acetamide Chemical compound NC(=O)CNC(N)=O NFODSNOCEFVBRY-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 108010008488 Glycylglycine Proteins 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 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
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002332 glycine derivatives Chemical class 0.000 description 1
- XKUKSGPZAADMRA-UHFFFAOYSA-N glycyl-glycyl-glycine Natural products NCC(=O)NCC(=O)NCC(O)=O XKUKSGPZAADMRA-UHFFFAOYSA-N 0.000 description 1
- 108010067216 glycyl-glycyl-glycine Proteins 0.000 description 1
- 229940043257 glycylglycine Drugs 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical class OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- Y02P20/141—Feedstock
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はグリシンの製造法に関する。特に、グリコロ
ニトリルとアンモニアおよび炭酸ガスを反応させてグリ
シンを製造する方法に関する。The present invention relates to a method for producing glycine. In particular, it relates to a method for producing glycine by reacting glycolonitrile with ammonia and carbon dioxide.
グリシンは加工食品の食品添加剤や農薬、医薬の原料
として広く使用されている有用な化合物である。Glycine is a useful compound widely used as a food additive for processed foods, a raw material for agricultural chemicals and pharmaceuticals.
従来、グリシンの製造方法としては、主としてモノク
ロル酢酸のアミノ化法、ストレッカー法、ヒダントイン
法等が知られている。モノクロル酢酸法は毒物であるシ
アン化水素を使用しないという長所があるが、２級およ
び３級アミン同族体が副生し、グリシン収率が低い。ま
た、ストレッカー法は反応時に副生するイミノジ酢酸塩
や加水分解後の中和塩の分離が必要である。シアン化水
素とホルムアルデヒドを原料とし、ヒダントインを経由
し、その加水分解によりグリシンを製造する方法は公知
である。たとえば、シア化水素とアルデヒドとアンモニ
アおよび二酸化炭素を水溶媒中で100℃以上で加熱する
方法（USP3,536,726）。また、たとえば水媒体中シアン
化水素とホルムアルデヒドおよび炭酸アンモニウムを加
熱する方法（特開昭49−127915）。また、たとえばグリ
コロニトリル、アンモニアおよび炭酸ガスを加熱しアン
モニアと炭酸ガスを除去した後、アルキルアミンあるい
はアルキルアンモニウムハドロオキシドで処理する方法
（特開昭53−28115）。また、たとえばグリコロニトリ
ル、アンモニアおよび炭酸ガスを加熱しアンモニアと炭
酸ガスを除去した後、鉱酸で処理して加水分解する方法
（特開昭53−28116）。また、たとえばグリコロニトリ
ル、アモニアおよび炭酸ガスを加熱し、アルカリ金属あ
るいはアルカリ土類金属の水酸化物、炭酸塩および重炭
酸塩等のアルカリ性物質で処理する方法（特開昭53−31
6161）等である。Conventionally, as a method for producing glycine, an amination method of monochloroacetic acid, a Strecker method, a hydantoin method and the like have been known. The monochloroacetic acid method has the advantage of not using the toxic hydrogen cyanide, but has secondary tertiary and homologous tertiary amines as by-products, resulting in low glycine yield. In the Strecker method, it is necessary to separate iminodiacetic acid salt by-produced during the reaction and neutralized salt after hydrolysis. A method for producing glycine by using hydrogen cyanide and formaldehyde as raw materials and hydrolyzing the same via hydantoin is known. For example, a method of heating hydrogen cyanide, aldehyde, ammonia and carbon dioxide in an aqueous solvent at 100 ° C. or higher (US Pat. No. 3,536,726). Also, for example, a method of heating hydrogen cyanide, formaldehyde and ammonium carbonate in an aqueous medium (JP-A-49-127915). Also, for example, a method of heating glycolonitrile, ammonia and carbon dioxide gas to remove the ammonia and carbon dioxide gas, and then treating with an alkylamine or an alkylammonium hydroxide (Japanese Patent Application Laid-Open No. 53-28115). Also, for example, a method of heating glycolonitrile, ammonia and carbon dioxide gas to remove ammonia and carbon dioxide gas, and then treating with a mineral acid to hydrolyze (JP-A-53-28116). Further, for example, a method in which glycolonitrile, amonia and carbon dioxide gas are heated and treated with an alkaline substance such as an alkali metal or alkaline earth metal hydroxide, carbonate and bicarbonate (Japanese Patent Laid-Open No. 53-31)
6161).
しかしながら、これらの方法はいずれも副生生物が多
く、グリシンの選択性が必ずしも充分とはいえない。ま
た、アルカリ性の塩あるいは金属で加水分解する方法で
はグリシの選択性は向上するが、仕込んだグリコロニト
リルに対して等モル以上のアルカリを必要とするだけで
なく、グリシン塩を加水分解する必要がある。また、生
成した塩とグリシンとの分離工程が煩雑となりグリシン
製造の経済性を大きく損なう。However, all of these methods have many by-products and the selectivity of glycine is not always sufficient. In addition, the method of hydrolyzing with an alkaline salt or metal improves the selectivity of glyci, but not only requires an equimolar amount or more of alkali than the charged glycolonitrile, but also requires hydrolysis of glycine salt. There is. In addition, the step of separating glycine from the produced salt is complicated, and the economics of glycine production is greatly impaired.
本発明者らはグリシンの選択率を向上させるために鋭
意検討を行い、副生量のヒダントイン酸あるいは2,5−
ジケトピペラジンを反応器へ供給することにより正味の
ヒダントイン酸あるいは2,5−ジケトピペラジンの副生
量が減少し、その結果グリシンの選択率が大幅に向上す
ることを見い出し本発明に至った。すなわち、本発明は
グリコロニトリル、炭酸ガスおよびアンモニアを水の存
在下、100〜200℃に加熱してグリシを製造するにあた
り、ヒダントイン酸および／または2,5−ジケトピペラ
ジンを反応器へ供給することを特徴とするグリシンの製
造方法である。The present inventors have conducted intensive studies in order to improve the selectivity of glycine, and found that by-produced amounts of hydantoic acid or 2,5-
It was found that by supplying diketopiperazine to the reactor, the amount of by-products of net hydantoic acid or 2,5-diketopiperazine was reduced, and as a result, the selectivity of glycine was significantly improved, leading to the present invention. . That is, the present invention supplies hydantoic acid and / or 2,5-diketopiperazine to a reactor for producing glyci by heating glycolonitrile, carbon dioxide gas and ammonia to 100 to 200 ° C. in the presence of water. A method for producing glycine.
本発明の方法は水溶媒中で行われる。 The method of the present invention is performed in an aqueous solvent.
本発明の方法で使用されるグリコロニトリルは純粋な
ものは当然であるが、硫酸やリン酸等の安定剤を含有し
ていても使用することができる。また、反応条件下でグ
リコロニトリルを生成し得る化合物も使用することがで
きる。このような化合物の例としてはシアン化水素とホ
ルムアルデヒドの混合物、あるいはシアン化ナトリウム
とパラホルムアルデヒドの混合物等が挙げられる。グリ
コロニトリルの使用量は使用する水に対し、１〜50wt％
の範囲である。The glycolonitrile used in the method of the present invention is naturally pure, but can be used even if it contains a stabilizer such as sulfuric acid or phosphoric acid. Further, compounds capable of forming glycolonitrile under the reaction conditions can also be used. Examples of such compounds include a mixture of hydrogen cyanide and formaldehyde, a mixture of sodium cyanide and paraformaldehyde, and the like. The amount of glycolonitrile used is 1 to 50 wt% based on the water used.
Range.
本発明の方法で使用する炭酸ガスおよびアンモニアは
これらをそのまま使用してもよいが、反応条件下でこれ
らの化合物を生成する化合物、たとえば、炭酸アンモニ
ウムや重炭酸アンモニウムを使用してもよい。また、こ
れらを混合して使用しても好ましい結果が得られる。As the carbon dioxide gas and ammonia used in the method of the present invention, these may be used as they are, or a compound which produces these compounds under the reaction conditions, for example, ammonium carbonate or ammonium bicarbonate may be used. Further, even when these are mixed and used, preferable results are obtained.
アンモニアの使用量はグリコロニトリルに対し、当モ
ル以上、好ましくは１〜50モル倍である。また、炭酸ガ
スの使用量はグリコロニトリルに対し当モル以上、好ま
しくは１〜50モル倍である。The amount of ammonia to be used is at least equimolar, preferably 1 to 50 times the molar amount of glycolonitrile. The amount of carbon dioxide used is at least equimolar to glycolonitrile, preferably 1 to 50 times.
本発明の方法で供給するヒダントイン酸および2,5−
ジケトピペラジンの供給量はこれらを供給しないで同一
条件下で反応を行った場合に副生する量が好ましい。さ
らに好ましくは、この副生量を目安に試行的にこれらの
供給量を変えて反応を行い、ヒダントイン酸あるいは2,
5−ジケトピペラジンの正味の副生量が０となる量を供
給することが好ましい。ヒダントイン酸および2,5−ジ
ケトピペラジンの副生量は仕込みのグリコロニトリル濃
度の影響を受け、グリコロニトリル濃度が高いほどそれ
らの副生量は多くなる。通常、水溶媒中、グリコロニト
リル、アンモニアおよび炭酸ガスを100〜200℃で加熱し
た場合、ヒダントイン酸および2,5−ジケトピペラジン
の副生量はそれぞれ仕込みのグリコロニトリルの１〜10
モル％、0.1〜10モル％である。したがって、本発明の
方法で供給するヒダントイン酸および2,5−ジケトピペ
ラジンの供給量としてはそれぞれグリコロニトリルの１
〜10モル％、0.1〜10モル％程度で良い。Hydantoic acid provided by the method of the present invention and 2,5-
The amount of diketopiperazine to be supplied is preferably an amount produced as a by-product when the reaction is carried out under the same conditions without supplying these. More preferably, the reaction is carried out by changing these supply amounts on a trial basis using the amount of by-products as a guide, and hydantoic acid or 2,2
It is preferable to supply an amount by which the net by-product amount of 5-diketopiperazine becomes zero. The by-products of hydantoic acid and 2,5-diketopiperazine are affected by the glycolonitrile concentration in the feed, and the higher the glycolonitrile concentration, the greater the by-products. Usually, in a water solvent, when glycolonitrile, ammonia and carbon dioxide gas are heated at 100 to 200 ° C., the amount of by-produced hydantoic acid and 2,5-diketopiperazine is 1 to 10 of the charged glycolonitrile, respectively.
Mol%, 0.1 to 10 mol%. Accordingly, the supply amounts of hydantoic acid and 2,5-diketopiperazine supplied by the method of the present invention are each one of glycolonitrile.
It may be about 10 mol%, about 0.1 to 10 mol%.
本発明の方法で供給するヒダントイン酸あるいは2,5
−ジケトピペラジンは反応器へあらかじめ供給しておい
てもよく、また、連続的に供給しても好ましい結果が得
られる。この場合、グリシン精製系より分離してヒダン
トイン酸及び2,5−ジケトピペラジン濃度を高めた成分
を回収循環する事ができる。Hydantoic acid or 2,5 supplied by the method of the present invention
-Diketopiperazine may be supplied to the reactor in advance, or a continuous result may provide favorable results. In this case, the components separated from the glycine purification system and having an increased concentration of hydantoic acid and 2,5-diketopiperazine can be recovered and circulated.
反応圧力は特に制限はないが反応中に発生するアンモ
ニア、炭酸ガスあるいは溶媒の蒸気等を適宜抜き出して
も反応させることができる。The reaction pressure is not particularly limited, but the reaction can be carried out by appropriately extracting ammonia, carbon dioxide gas or solvent vapor generated during the reaction.
本発明の方法で使用される反応温度は低い方がグリシ
ンの収率は向上するが反応速度が遅くなる。従って、反
応温度は100〜200℃が好ましい。The lower the reaction temperature used in the method of the present invention, the higher the glycine yield but the lower the reaction rate. Therefore, the reaction temperature is preferably from 100 to 200 ° C.
本発明の方法は回分式でも、また、半流通式、あるい
は、流通式でも行うことができる。The method of the present invention can be carried out batchwise, semi-flowwise or flow-through.
本発明の方法を実施例および比較例により詳細に説明
する。The method of the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１ チタンライニングした100mlオートクレーブにグリコ
ロニトリル2.9g（51.0mmol）、炭酸アンモニウム49.0g
（600mmol、純度85％）、水45.5g、ヒダントイン酸0.34
g（2.87mmol）および2,5−ジケトピペラジン0.03g（0.2
3mol）を入れ150℃まで１時間で加熱した。この時の反
応圧力は43気圧であった。４時間反応後反応液を室温ま
で冷却し、液体クロマトグラフで分析した結果、ヒダン
トイン酸アミド0.10mmol、ヒダントイン酸3.06mmol、2,
5−ジケトピペラジン0.24mmol、ヒダントイン0.06mmo
l、グリシルグリシン1.54mmol、トリグリシン0.02mmol
およびグリシン43.57mmolであった。この回収生成物か
ら供給したヒダントイン酸および2,5−ジケトピペラジ
ンを除いたグリシンのグリコロニトリル基準の選択率は
92.5％であった。Example 1 In a titanium-lined 100 ml autoclave, 2.9 g (51.0 mmol) of glycolonitrile and 49.0 g of ammonium carbonate
(600 mmol, purity 85%), water 45.5 g, hydantoic acid 0.34
g (2.87 mmol) and 2,5-diketopiperazine 0.03 g (0.2
3 mol) and heated to 150 ° C. for 1 hour. The reaction pressure at this time was 43 atm. After reacting for 4 hours, the reaction solution was cooled to room temperature and analyzed by liquid chromatography. As a result, 0.10 mmol of hydantoic acid amide, 3.06 mmol of hydantoic acid, 2,
0.24 mmol of 5-diketopiperazine, 0.06 mmol of hydantoin
l, glycylglycine 1.54mmol, triglycine 0.02mmol
And glycine was 43.57 mmol. The selectivity based on glycolonitrile of glycine excluding hydantoic acid and 2,5-diketopiperazine supplied from the recovered product is as follows.
92.5%.
比較例１ オートクレーブへヒダントイン酸および2,5−ジケト
ピペラジンを供給しないこと以外は実施例１と同じ方法
で反応を行った。この結果を実施例１と共に第１表に示
す。Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that hydantoic acid and 2,5-diketopiperazine were not supplied to the autoclave. The results are shown in Table 1 together with Example 1.
実施例２〜３ グリコロニトリルの濃度、炭酸アンモニウムの量、反
応温度を第１表のように変え、他は実施例１と同様の方
法で反応を行った。結果を第１表に示す。Examples 2-3 The reaction was carried out in the same manner as in Example 1 except that the concentration of glycolonitrile, the amount of ammonium carbonate and the reaction temperature were changed as shown in Table 1. The results are shown in Table 1.
比較例２〜３ グリコロニトリルの濃度、炭酸アンモニウムの量、反
応温度を第１表のように変え、オートクレーブへヒダン
トイン酸および2,5−ジケトピペラジンを供給しないこ
と以外は実施例２〜３と同じ方法で反応を行った。この
結果を第１表に示す。Comparative Examples 2-3 Examples 2-3 were performed except that the concentration of glycolonitrile, the amount of ammonium carbonate, and the reaction temperature were changed as shown in Table 1 and no hydantoic acid and 2,5-diketopiperazine were supplied to the autoclave. The reaction was performed in the same manner as described above. Table 1 shows the results.
〔発明の効果〕 本発明の方法、すなわち、ヒダントイン酸および2,5
−ジケトピペラジンを供給して反応を行った結果、グリ
シンの選択率は６〜９％向上し、実施例１及び２ではグ
リシンの選択率として90％以上が得られた。このよう
に、本発明の方法はヒダントイン経由のグリシン製造を
工業的に有利な方法にまで向上させることができる。 [Effect of the Invention] The method of the present invention, namely, hydantoic acid and 2,5
As a result of carrying out the reaction by supplying diketopiperazine, the selectivity of glycine was improved by 6 to 9%, and in Examples 1 and 2, a selectivity of glycine of 90% or more was obtained. Thus, the method of the present invention can improve the production of glycine via hydantoin to an industrially advantageous method.
Claims (1)
ニアを水の存在下、100〜200℃に加熱してグリシンを製
造するにあたり、ヒダントイン酸および／または2,5−
ジケトピペラジンを反応器へ供給することを特徴とする
グリシンの製造方法。1. A method for producing glycine by heating glycolonitrile, carbon dioxide and ammonia to 100 to 200 ° C. in the presence of water, wherein hydantoic acid and / or 2,5-
A method for producing glycine, comprising supplying diketopiperazine to a reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63260654A JP2716481B2 (en) | 1988-10-18 | 1988-10-18 | Glycine production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63260654A JP2716481B2 (en) | 1988-10-18 | 1988-10-18 | Glycine production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02108653A JPH02108653A (en) | 1990-04-20 |
| JP2716481B2 true JP2716481B2 (en) | 1998-02-18 |
Family
ID=17350922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63260654A Expired - Fee Related JP2716481B2 (en) | 1988-10-18 | 1988-10-18 | Glycine production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2716481B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0456838B1 (en) * | 1989-12-06 | 1995-11-02 | MITSUI TOATSU CHEMICALS, Inc. | Process for producing glycine |
-
1988
- 1988-10-18 JP JP63260654A patent/JP2716481B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02108653A (en) | 1990-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4499706B2 (en) | Method for producing methionine and its salt | |
| US9745258B1 (en) | Cyclic process for producing taurine | |
| US9815778B1 (en) | Cyclic process for producing taurine | |
| EP2186796B1 (en) | Process for producing methionine | |
| US20070055078A1 (en) | Process for producing methionine | |
| US5258550A (en) | Process for preparing glycine | |
| US3536726A (en) | Preparation of alpha-amino-carboxylic acids | |
| JP2716481B2 (en) | Glycine production method | |
| US4518801A (en) | Process for the hydrolysis of 5-(β-methylmercaptoethyl)-hydantoin | |
| EP0459803B1 (en) | Method for purifying glycine | |
| JP2716467B2 (en) | Glycine production method | |
| KR950001631B1 (en) | How to prepare glycine | |
| JPS5829296B2 (en) | Method for producing monomethylhydrazine | |
| JP2764346B2 (en) | Glycine production method | |
| WO1998003467A1 (en) | Process for making aqueous betaine solutions | |
| JPH02306946A (en) | Method for preventing discoloration of glycine | |
| US4014928A (en) | Process for purifying α-amino acids | |
| JPS62267253A (en) | Production of alpha-amino acid | |
| KR100562176B1 (en) | Method for preparing D, L-methionine or salts thereof | |
| JPH03193748A (en) | Production of glycine | |
| JPH03232847A (en) | Production of glycine | |
| EP0151651B1 (en) | Process for the preparation of a starting material for the production of phenylalanine | |
| EP0018177B1 (en) | Process for producing alpha-halogeno-beta-alanines or the mineral acid salts thereof | |
| JPH0687803A (en) | Glycine production method | |
| JPH0768222B2 (en) | Method for producing 4-methyl-5-[(2-aminoethyl) -thiomethyl-imidazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |