JPH05229996A - Production of glycine - Google Patents

Production of glycine

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Publication number
JPH05229996A
JPH05229996A JP4033586A JP3358692A JPH05229996A JP H05229996 A JPH05229996 A JP H05229996A JP 4033586 A JP4033586 A JP 4033586A JP 3358692 A JP3358692 A JP 3358692A JP H05229996 A JPH05229996 A JP H05229996A
Authority
JP
Japan
Prior art keywords
iron
carbon dioxide
nitrogen
glycine
tube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP4033586A
Other languages
Japanese (ja)
Inventor
Norihiko Fujita
矩彦 藤田
Chihiro Matsuura
千尋 松浦
Kazuhiro Imai
一洋 今井
Sonoko Utsu
園子 宇津
Hidetake Kakihana
秀武 垣花
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to JP4033586A priority Critical patent/JPH05229996A/en
Publication of JPH05229996A publication Critical patent/JPH05229996A/en
Pending legal-status Critical Current

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PURPOSE:To obtain glycine from an inexpensive raw material in high efficiency without using expensive chemicals by contacting a gas containing carbon dioxide and nitrogen with water in the presence of iron or iron ion and irradiating the system with electromagnetic wave. CONSTITUTION:An aqueous solution containing iron or iron ion (e.g. ferrous sulfate) is filled in a Pyrex glass tube and the space in the tube is charged with a mixed gas containing carbon dioxide gas, nitrogen and hydrogen (CO2/N2/H2 molar ratios are 1/1/1) to substitute air with the mixed gas. The tube is heat-sealed and irradiated with electromagnetic ray such as gamma-ray with cobalt 60 at a dose of 0.4 Mrad/hr. After the irradiation for a prescribed period, the amino acids formed in the solution are recovered to obtain glycine having high added value from inexpensive raw materials such as carbon dioxide gas discharged from chemical industry, iron and steel industry, etc.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、グリシンの製造方法に
関するものである。詳しく述べると、二酸化炭素および
窒素よりグリシンを製造する方法に関するものである。
FIELD OF THE INVENTION The present invention relates to a method for producing glycine. More specifically, it relates to a method for producing glycine from carbon dioxide and nitrogen.

【0002】[0002]

【従来の技術】グリシンは、アミノ酢酸とも称され、最
も簡単なアミノ酸である。従来、グリシンの製造方法と
しては、モノクロル酢酸にアンモニアを反応させる方
法、ホルムアルデヒドとシアン化ナトリウムとのシュト
レッカーアミン合成方法、メチレンアノアセトニトリル
に水酸化バリウム水溶液を作用させる方法等が提案され
ている(化学大辞典3第103頁)。しかしながら、こ
れらの方法は、いずれも高価な化学薬品を出発原料とす
るので高価となる。
Glycine, also called aminoacetic acid, is the simplest amino acid. Conventionally, as a method for producing glycine, a method of reacting monochloroacetic acid with ammonia, a method of synthesizing Strecker amine of formaldehyde and sodium cyanide, a method of reacting methyleneanoacetonitrile with an aqueous barium hydroxide solution, and the like have been proposed ( Chemistry Dictionary 3, page 103). However, these methods are expensive because they use expensive chemicals as starting materials.

【0003】一方、人類の活動に伴なって放出される二
酸化炭素は、グリーンハウス効果によって地球を温暖化
する作用を有している。窒素酸化物やフロンガスもこの
ような作用を有しているが、プロセスの改善や代替物質
の開発によって大気中への蓄積を回避することが可能で
ある。一方、光合成や海洋への溶解といった自然の吸収
プロセスは存在するものの、人口の激増と経済発展に強
く依存する炭酸ガスの増加は、それを上回りつつあり、
大気中の二酸化炭素濃度は、微かづつではあるが高まっ
てきているのが現状である。したがって、それに対する
方策を今から講じ始めなければ、今後数十年で二酸化炭
素濃度は、産業革命以前に比較して2倍に達し、地表の
平均気温も1〜3℃増大するといわれている。海水面の
上昇、異常気象あるいは生態系の変化が懸念されるとと
もに、植林や深海底投棄等の炭酸ガス低減法が幾つか提
案されている。
On the other hand, carbon dioxide released along with the activity of human beings has the effect of warming the earth by the greenhouse effect. Nitrogen oxides and Freon gas also have such effects, but it is possible to avoid their accumulation in the atmosphere by improving the processes and developing alternative substances. On the other hand, although there are natural absorption processes such as photosynthesis and dissolution in the ocean, the increase in carbon dioxide, which is strongly dependent on the rapid population growth and economic development, is surpassing that.
At present, the concentration of carbon dioxide in the atmosphere is increasing, albeit slightly. Therefore, it is said that if no measures are taken to address this, the carbon dioxide concentration will double in the next few decades compared to before the Industrial Revolution, and the average surface temperature will increase by 1 to 3 ° C. There are concerns about rising sea levels, abnormal weather, or changes in the ecosystem, and several carbon dioxide reduction methods such as tree planting and deep-sea dumping have been proposed.

【0004】しかしながら、植林には広大な土地と長時
間とを要するので、ほとんど実現不可能であり、また深
海底投棄には莫大な費用を要するという問題がある。
However, there is a problem in that afforestation requires a vast amount of land and a long period of time, so that it is almost impossible to achieve, and the deep sea dumping requires enormous cost.

【0005】一方、化学工業、鉄鋼業等の産業から排出
される二酸化炭素の処理方法として、種々の方法が提案
されているが、未だ満足すべき結果は得られていない。
On the other hand, various methods have been proposed as a method for treating carbon dioxide discharged from industries such as the chemical industry and the steel industry, but satisfactory results have not yet been obtained.

【0006】[0006]

【発明が解決しようとする課題】したがって、本発明の
目的は、グリシンの新規な製造方法を提供することにあ
る。
Accordingly, it is an object of the present invention to provide a novel method for producing glycine.

【0007】本発明の他の目的は、炭酸ガスと窒素と水
との反応により高い付加価値を有するグリシンを製造す
る方法を提供することにある。
Another object of the present invention is to provide a method for producing glycine having a high added value by reacting carbon dioxide gas, nitrogen and water.

【0008】[0008]

【課題を解決するための手段】これらの諸目的は、鉄ま
たは鉄イオンの存在下に、二酸化炭素および窒素を含有
するガスと水とを接触させて電磁波を照射することを特
徴とするグリシンの製造方法により達成される。
[Means for Solving the Problems] These objects of glycine are characterized in that a gas containing carbon dioxide and nitrogen is brought into contact with water in the presence of iron or iron ions to irradiate electromagnetic waves. This is achieved by the manufacturing method.

【0009】[0009]

【作用】本発明によるグリシンの製造方法は、通常、水
中に鉄の微粉末を懸濁させるかあるいは水溶性鉄化合物
を溶解させ、このようにして得られる懸濁液または水溶
液とを二酸化炭素および窒素を含有するガスとを接触さ
せ、電磁波を照射することにより行われる。
The method for producing glycine according to the present invention is usually carried out by suspending fine iron powder in water or dissolving a water-soluble iron compound, and then subjecting the suspension or aqueous solution thus obtained to carbon dioxide and It is performed by contacting with a gas containing nitrogen and irradiating an electromagnetic wave.

【0010】鉄としては、粒径0.005〜30μm、
好ましくは0.01〜1μmの微粉末があり、水中に懸
濁して使用される。微粉末状鉄の懸濁量は、水に対して
0.01〜10重量%、好ましくは0.05〜3重量%
である。微粉末状鉄の水中への懸濁は、水中に直接添加
してもよいが、必要により界面活性剤を用いてもよい。
Iron has a particle size of 0.005 to 30 μm,
There is preferably 0.01 to 1 μm of fine powder, which is used by suspending in water. The amount of suspension of fine powdery iron is 0.01 to 10% by weight, preferably 0.05 to 3% by weight, with respect to water.
Is. Suspension of finely powdered iron in water may be added directly to water, but a surfactant may be used if necessary.

【0011】水溶性鉄化合物としては、硫酸第一鉄、硝
酸第一鉄、塩化第一鉄、塩化第二鉄、臭化第一鉄、臭化
第二鉄、リン酸鉄、フェリシアン酸鉄、酢酸鉄、プロピ
オン酸鉄、マレイン酸鉄、フマル酸鉄等、第一鉄イオン
または第二鉄イオンを形成するものあるいは両者の共存
するコンピレックスがある。この鉄化合物の濃度は、水
1リットルに対して1nmol〜5モル、好ましくは1
0μmol〜1モルである。
As the water-soluble iron compound, ferrous sulfate, ferrous nitrate, ferrous chloride, ferric chloride, ferrous bromide, ferric bromide, iron phosphate, iron ferricyanate , Iron acetate, iron propionate, iron maleate, iron fumarate, etc., which form ferrous or ferric ions, or Compilex in which both coexist. The concentration of this iron compound is 1 nmol to 5 mol, preferably 1
It is 0 μmol to 1 mol.

【0012】該水懸濁液ないし水溶液と二酸化炭素−窒
素含有ガスとの接触は、反応溶液中の空間に該炭酸ガス
含有ガスを充填しても、あるいは該水懸濁液ないし水溶
液を攪拌しても、あるいは該水懸濁液ないし水溶液中に
該炭酸ガス含有ガスを吹込んでもよい。また、反応は、
回分式でも連続式でもよい。さらに、常圧下でも加圧下
でもよい。
The contact between the water suspension or aqueous solution and the carbon dioxide-nitrogen containing gas may be performed by filling the space in the reaction solution with the carbon dioxide containing gas or by stirring the water suspension or aqueous solution. Alternatively, the carbon dioxide-containing gas may be blown into the aqueous suspension or aqueous solution. Also, the reaction is
It may be a batch system or a continuous system. Furthermore, it may be under normal pressure or under pressure.

【0013】該二酸化炭素−窒素含有ガス中の二酸化炭
素と窒素とのモル比は1:100〜100:1、好まし
くは1:10〜10:1である。また、該ガス中には、
二酸化炭素および窒素の他に、水素、一酸化炭素、酸
素、空気等を含有していてもよい。
The molar ratio of carbon dioxide to nitrogen in the carbon dioxide-nitrogen containing gas is 1: 100 to 100: 1, preferably 1:10 to 10: 1. Also, in the gas,
In addition to carbon dioxide and nitrogen, hydrogen, carbon monoxide, oxygen, air, etc. may be contained.

【0014】本発明で使用される電磁波としては、ガン
マ線、電子線等の放射線や紫外線等の光線があるが、好
ましくはガンマ線である。該電磁波の照射量は、0.0
01〜100Mrad、好ましくは、0.1〜10Mr
adである。
The electromagnetic waves used in the present invention include radiation such as gamma rays and electron rays and light rays such as ultraviolet rays, but gamma rays are preferable. The irradiation amount of the electromagnetic wave is 0.0
01-100 Mrad, preferably 0.1-10 Mr
It is ad.

【0015】[0015]

【実施例】つぎに、実施例を挙げて本発明方法をさらに
詳細に説明する。
EXAMPLES Next, the method of the present invention will be described in more detail with reference to examples.

【0016】実施例1 2mMの硫酸第一鉄を含有する20mlの水溶液を容量
60mlのパイレックスガラス管に充填したのち、その
空間にCO2 −N2 −H2 混合ガス(CO2 /N2 /H
2 (モル比)=1/1/1)を供給して空気を置換する
とともに溶封した。この溶封ガラス管にコバルト60を
用いてガンマ線を0.4Mrad/hrで照射した。所
定時間の照射終了後、溶液中に含有するアミノ酸をAn
al.Chim.Acta,130(1981)377
の方法にしたがって分析したところ、図1の結果が得ら
れた。
Example 1 A Pyrex glass tube having a volume of 60 ml was charged with 20 ml of an aqueous solution containing 2 mM ferrous sulfate, and the space was filled with CO 2 -N 2 -H 2 mixed gas (CO 2 / N 2 / H
2 (molar ratio) = 1/1/1) was supplied to replace the air and sealed. This fusion sealed glass tube was irradiated with gamma rays at 0.4 Mrad / hr using cobalt 60. After irradiation for a predetermined time, the amino acid contained in the solution was
al. Chim. Acta, 130 (1981) 377.
The results shown in FIG. 1 were obtained when analyzed according to the method of 1.

【0017】実施例2 実施例1と同様の方法において、CO2 −N2 −H2
合ガスの代りにCO2 −N2 混合ガス(CO2 /N
2 (モル比)=1:1)を用いた以外は、同様の方法を
行ったところ、図2に示す結果が得られた。
Example 2 In the same manner as in Example 1, instead of the CO 2 —N 2 —H 2 mixed gas, a CO 2 —N 2 mixed gas (CO 2 / N) was used.
When the same method was performed except that 2 (molar ratio) = 1: 1) was used, the results shown in FIG. 2 were obtained.

【0018】実施例3 実施例1と同様の方法において、ガンマ線の代りに紫外
線を照射する以外は、同様の方法を行った。最大波長3
70nmの紫外線は、National 40BA−3
7(40W)により得た。しかしながら、グリシンの収
量は極微量で、24時間の照射を続けても0.14μM
程度の値しか得られなかった。
Example 3 The same method as in Example 1 was carried out except that ultraviolet rays were irradiated instead of gamma rays. Maximum wavelength 3
70 nm UV is National 40BA-3
7 (40 W). However, the yield of glycine is very small, and even if irradiation is continued for 24 hours, 0.14 μM
Only a moderate value was obtained.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の一実施例の電磁波の照射時間とグリシ
ンの濃度との関係を示すグラフである。
FIG. 1 is a graph showing the relationship between the irradiation time of electromagnetic waves and the concentration of glycine in one example of the present invention.

【図2】本発明の一実施例の電磁波の照射時間とグリシ
ンの濃度とpHとの関係を示すグラフである。
FIG. 2 is a graph showing the relationship between the irradiation time of electromagnetic waves, the concentration of glycine, and pH in one example of the present invention.

─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成4年3月18日[Submission date] March 18, 1992

【手続補正1】[Procedure Amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0016[Correction target item name] 0016

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0016】 実施例1 2mMの硫酸第一鉄を含有する20mlの水溶液を容量
60mlのパイレックスガラス管に充填したのち、その
空間にCO2 −N2 −H2 混合ガス(CO2 /N2 /H
2 (モル比)=1/1/1)を供給して空気を置換する
とともに溶封した。この溶封ガラス管にコバルト60を
用いてガンマ線を0.4Mrad/hrで照射した。所
定時間の照射終了後、溶液中に含有するアミノ酸をBi
omed.Chromatog.,Vol.2,99
(1987)377の方法にしたがって分析したとこ
ろ、図1の結果が得られた。
Example 1 A Pyrex glass tube having a volume of 60 ml was charged with 20 ml of an aqueous solution containing 2 mM ferrous sulfate, and the space was filled with CO 2 —N 2 —H 2 mixed gas (CO 2 / N 2 / H
2 (molar ratio) = 1/1/1) was supplied to replace the air and sealed. This fusion sealed glass tube was irradiated with gamma rays at 0.4 Mrad / hr using cobalt 60. After completion of irradiation for a predetermined time, the amino acid contained in the solution was Bi
omed. Chromatog. , Vol. 2,99
(1987) 377, the results shown in FIG. 1 were obtained.

フロントページの続き (72)発明者 垣花 秀武 東京都渋谷区広尾5−1−21Front page continuation (72) Inventor Hidetake Kakihana 5-1-21 Hiroo, Shibuya-ku, Tokyo

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 鉄または鉄イオンの存在下に、二酸化炭
素および窒素を含有するガスと水とを接触させて電磁波
を照射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, which comprises contacting a gas containing carbon dioxide and nitrogen with water in the presence of iron or iron ions to irradiate electromagnetic waves.
【請求項2】 電磁波がガンマ線、電子線または紫外線
である請求項1に記載のグリシンの製造方法。
2. The method for producing glycine according to claim 1, wherein the electromagnetic wave is gamma ray, electron beam or ultraviolet ray.
JP4033586A 1992-02-20 1992-02-20 Production of glycine Pending JPH05229996A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4033586A JPH05229996A (en) 1992-02-20 1992-02-20 Production of glycine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4033586A JPH05229996A (en) 1992-02-20 1992-02-20 Production of glycine

Publications (1)

Publication Number Publication Date
JPH05229996A true JPH05229996A (en) 1993-09-07

Family

ID=12390623

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4033586A Pending JPH05229996A (en) 1992-02-20 1992-02-20 Production of glycine

Country Status (1)

Country Link
JP (1) JPH05229996A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678745A (en) * 2019-01-25 2019-04-26 常宁德邦生物科技有限公司 A kind of refining methd of low titanium ferrous glycine
CN117225336A (en) * 2023-11-13 2023-12-15 东华理工大学南昌校区 Amino acid synthesis equipment and method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678745A (en) * 2019-01-25 2019-04-26 常宁德邦生物科技有限公司 A kind of refining methd of low titanium ferrous glycine
CN109678745B (en) * 2019-01-25 2021-12-10 湖南德邦生物科技有限公司 Refining method of low-titanium ferric glycine
CN117225336A (en) * 2023-11-13 2023-12-15 东华理工大学南昌校区 Amino acid synthesis equipment and method

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