JPH05339195A - Production of carboxylic acid - Google Patents

Production of carboxylic acid

Info

Publication number
JPH05339195A
JPH05339195A JP4145240A JP14524092A JPH05339195A JP H05339195 A JPH05339195 A JP H05339195A JP 4145240 A JP4145240 A JP 4145240A JP 14524092 A JP14524092 A JP 14524092A JP H05339195 A JPH05339195 A JP H05339195A
Authority
JP
Japan
Prior art keywords
carboxylic acid
acid
carbon dioxide
gas
contg
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
JP4145240A
Other languages
Japanese (ja)
Inventor
Norihiko Fujita
矩彦 藤田
Chihiro Matsuura
千尋 松浦
Daisuke Hiroishi
大介 広石
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.)
NISHIYAMA KK
Nishiyama Corp
Original Assignee
NISHIYAMA KK
Nishiyama Corp
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 NISHIYAMA KK, Nishiyama Corp filed Critical NISHIYAMA KK
Priority to JP4145240A priority Critical patent/JPH05339195A/en
Publication of JPH05339195A publication Critical patent/JPH05339195A/en
Pending legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PURPOSE:To efficiently obtain a carboxylic acid such as formic acid or acetic acid using inexpensive raw materials by bringing a carbon dioxide-contg. gas into contact with water in the presence of iron ion followed by irradiating the system with electromagnetic waves such as gamma-rays, electron beams or ultraviolet light. CONSTITUTION:A Pyrex ampul is packed with an iron ion(e.g. in the form of ferrous sulfate)-contg. aqueous solution and the resultant space is fed with a gas (e.g. carbon dioxide-contg. nitrogen gas) to replace the air therein followed by heat sealing. Thence, the resulting heat-sealed ampul is irradiated with electromagnetic waves such as gamma-rays from Co-60, electron beams or ultraviolet light for a specified time followed by unsealing to isolate the reaction product from the liquor in the ampul, thus affording the objective carboxylic acid such as formic acid, acetic acid, oxalic acid or succinic acid using inexpensive raw materials. It is preferable that the concentration of the iron ion be 1nmol to 5mol per l of water and the dose of the electromagnetic waves 0.01-1.000KGy.

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、カルボン酸の製造方法
に関するものである。詳しく述べると、二酸化炭素より
カルボン酸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 a carboxylic acid. More specifically, it relates to a method for producing a carboxylic acid from carbon dioxide.

【０００２】[0002]

【従来の技術】従来、ギ酸は、加圧下で水酸化ナトリウ
ムに一酸化炭素を加熱反応させ、ギ酸ナトリウムを製造
し、これを希酸で分解して所望のギ酸を得るという方法
で製造している（化学大辞典第２巻第７０４頁）。しか
しながら、このような方法では、一酸化炭素を得るため
に多量のコークスを得る必要があるばかりでなく、水酸
化ナトリウムや希酸を必要とし、さらに、それぞれの廃
液の処理の問題があった。2. Description of the Related Art Conventionally, formic acid is produced by a method in which sodium hydroxide is heated and reacted with carbon monoxide under pressure to produce sodium formate, which is decomposed with a dilute acid to obtain a desired formic acid. (Dictionary of Chemistry, Volume 2, Page 704). However, in such a method, not only a large amount of coke needs to be obtained in order to obtain carbon monoxide, but also sodium hydroxide and a dilute acid are required, and further there is a problem of treatment of each waste liquid.

【０００３】また、酢酸は、エチレンをワッカー法等に
より液相酸化し、得られるアセトアルデヒドを酢酸マン
ガンおよび酢酸セリウムを触媒として酸化することによ
り製造している（化学大辞典第３巻第８１１頁）。しか
しながら、このような方法では、アセトアルデヒドを得
るために高価なエチレンを出発原料とするだけでなく、
廃液の処理に問題があった。Acetic acid is produced by liquid-phase oxidation of ethylene by the Wacker method or the like, and the resulting acetaldehyde is oxidized with manganese acetate and cerium acetate as catalysts (Chemical Encyclopedia, Vol. 3, page 811). .. However, such a method not only uses expensive ethylene as a starting material to obtain acetaldehyde, but also
There was a problem in the treatment of the waste liquid.

【０００４】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 human activities 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.

【０００５】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、実現には相応の努力と覚悟が要求さ
れ、また深海底投棄には莫大な運転費用を要するという
問題がある。However, since afforestation requires a vast amount of land and a long period of time, there is a problem that a considerable effort and preparation are required to realize it, and a huge operating cost is required for dumping in the deep sea.

【０００６】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 emitted from industries such as the chemical industry and the steel industry, but satisfactory results have not yet been obtained.

【０００７】[0007]

【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、カルボン酸の新規な製造方法を提供することに
ある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a novel method for producing a carboxylic acid.

【０００８】本発明の他の目的は、炭酸ガスと水との反
応により高い付加価値を有するカルボン酸を製造する方
法を提供することにある。Another object of the present invention is to provide a method for producing a carboxylic acid having a high added value by reacting carbon dioxide gas with water.

【０００９】[0009]

【課題を解決するための手段】これらの諸目的は、鉄イ
オンの存在下に、二酸化炭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カルボン酸
の製造方法により達成される。These objects are achieved by a method for producing a carboxylic acid, which comprises contacting a gas containing carbon dioxide with water and irradiating an electromagnetic wave in the presence of iron ions. To be achieved.

【００１０】[0010]

【作用】本発明によるカルボン酸の製造方法は、通常、
水中に水溶性鉄化合物を溶解させ、このようにして得ら
れる水溶液とを二酸化炭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 a carboxylic acid according to the present invention is usually
It is carried out by dissolving a water-soluble iron compound in water, bringing the aqueous solution thus obtained into contact with a gas containing carbon dioxide, and irradiating an electromagnetic wave.

【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
するコンプレックスがある。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. that form ferrous or ferric ions, or a complex 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】水溶液と二酸化炭素含有ガスとの接触は、
反応溶液中の空間に該二酸化炭素含有ガスを充填して
も、あるいは該水溶液を攪拌しても、あるいは該水溶液
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 aqueous solution and the carbon dioxide-containing gas is
The space in the reaction solution may be filled with the carbon dioxide-containing gas, the aqueous solution may be stirred, or the carbon dioxide-containing gas may be blown into the aqueous solution. Further, the reaction may be a batch system or a continuous system. Furthermore, it may be under normal pressure or under pressure.

【００１３】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
１〜１，０００ＫＧｙ、好ましくは、１〜１００ＫＧｙ
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 preferred. The irradiation amount of the electromagnetic wave is 0.0
1 to 1,000 KGy, preferably 1 to 100 KGy
Is.

【００１４】このような方法で得られるカルボン酸は、
主としてギ酸、酢酸、シュウ酸、コハク酸等であるが、
その他にアセトアルデヒド等のアルデヒド類や炭化水素
類、また窒素が存在する場合には、アミン類等も同時に
得られる。The carboxylic acid obtained by such a method is
Mainly formic acid, acetic acid, oxalic acid, succinic acid, etc.,
In addition, aldehydes such as acetaldehyde and hydrocarbons, and amines when nitrogen is present are also obtained.

【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の濃度で硫酸第一鉄を含有する２０ｍｌの水溶液
を容量８０ｍｌのパイレックスアンプルに充填したの
ち、その空間にＣＯ2 −Ｎ2 混合ガス（ＣＯ2 ／Ｎ2 ＝
３０ｍｌ／３０ｍｌ）を供給して空気を置換するととも
に溶封した。この溶封アンプルにコバルト６０のガンマ
線を４ＫＧｙ／ｈｒの線量率で照射した。照射は室温で
実施した。所定時間の照射終了後、開封し、溶液中に含
有する全カルボン酸を"Y.Kasai,T.Tanimura,Z.Tamura,"
Spectrophotometric Determinationof Carboxylic Acid
by the Formation of Hydroxamic Acids with Dicyclo
hexylcarbodiimide",Anal.Chem. 47 (1),34(1975)の方
法にしたがって分析した。この方法では、溶液中の全カ
ルボン酸が高感度で測定される。照射時間が２時間、４
時間および８時間におけるカルボン酸の濃度は、それぞ
れ３３０μＭ、２２０μＭおよび６８μＭであった。Example 1 A Pyrex ampoule having a volume of 80 ml was filled with 20 ml of an aqueous solution containing ferrous sulfate at a concentration of 2 mM, and then CO 2 -N 2 mixed gas (CO 2 / N 2 =) was filled in the space.
(30 ml / 30 ml) was supplied to replace the air and sealed. This sealed ampoule was irradiated with gamma rays of cobalt 60 at a dose rate of 4 KGy / hr. Irradiation was performed at room temperature. After irradiation for a predetermined period of time, the package was opened and the total carboxylic acid contained in the solution was "Y. Kasai, T. Tanimura, Z. Tamura,"
Spectrophotometric Determination of Carboxylic Acid
by the Formation of Hydroxamic Acids with Dicyclo
Hexylcarbodiimide ", Anal . Chem . 47 (1 ), 34 (1975). This method was used to measure all carboxylic acids in solution with high sensitivity.
The concentrations of carboxylic acid at hours and 8 hours were 330 μM, 220 μM and 68 μM, respectively.

【００１７】実施例２ 実施例１において、硫酸第一鉄の濃度を０．２ｍＭとす
る以外は同様な方法を行なったところ、８時間の照射に
より生成したカルボン酸の濃度は１５μＭであった。Example 2 The same method as in Example 1 was carried out except that the concentration of ferrous sulfate was 0.2 mM. As a result, the concentration of carboxylic acid produced by irradiation for 8 hours was 15 μM.

【００１８】実施例３ 実施例１と同様の方法において、ＣＯ2 −Ｎ2 混合ガス
の代りにＣＯ2 −Ｎ2 −Ｈ2 混合ガス（ＣＯ2 ／Ｎ2 ／
Ｈ2 ＝２０ｍｌ：２０ｍｌ：２０ｍｌ）を用いた。照射
時間が２時間、４時間、８時間および１６時間における
カルボン酸の濃度は、それぞれ３０７μＭ、２７７μ
Ｍ、１５９μＭおよび９７μＭであった。Example 3 In the same manner as in Example 1, instead of the CO 2 --N 2 mixed gas, a CO 2 --N 2 --H 2 mixed gas (CO 2 / N 2 /
H 2 = 20 ml: 20 ml: 20 ml) was used. The carboxylic acid concentrations at the irradiation times of 2, 4, 8 and 16 hours were 307 μM and 277 μM, respectively.
M, 159 μM and 97 μM.

【００１９】実施例４ 実施例１において、硫酸第一鉄の濃度を０．２ｍＭとす
る以外は、同様の方法を行なったところ、１６時間の照
射により生成したカルボン酸の濃度は１３μＭであっ
た。Example 4 The same method as in Example 1 was repeated except that the concentration of ferrous sulfate was 0.2 mM. The concentration of carboxylic acid produced by irradiation for 16 hours was 13 μM. ..

【００２０】実施例５ 実施例１において、ガンマ線線量率を１．０ＫＧｙ／ｈ
ｒとする以外は、同様の方法を行なったところ、２時間
および４時間の照射により生成したカルボン酸の濃度
は、それぞれ３４５μＭおよび３００μＭであった。Example 5 In Example 1, the gamma ray dose rate was set to 1.0 KGy / h.
When the same method was carried out except that r was used, the concentrations of the carboxylic acid produced by irradiation for 2 hours and 4 hours were 345 μM and 300 μM, respectively.

【００２１】実施例６ 実施例１において、ガンマ線線量率を０．４ＫＧｙ／ｈ
ｒとする以外は同様の方法を行なったところ、２時間、
４時間および８時間の照射により生成したカルボン酸の
濃度は、それぞれ２９０μＭ、２９７μＭおよび２６８
μＭであった。 実施例７ 実施例１において、ガラスアンプルの空間に充填するガ
スをＣＯ2 （６０ｍｌ）とする以外は、同様の方法を行
なったところ、２時間および４時間の照射により生ずる
カルボン酸の濃度は、それぞれ６６９μＭおよび７２３
μＭであった。Example 6 In Example 1, the gamma ray dose rate was 0.4 KGy / h.
When the same method was performed except that r was set,
The concentrations of carboxylic acid produced by irradiation for 4 hours and 8 hours were 290 μM, 297 μM and 268, respectively.
μM. Example 7 The same method as in Example 1 was repeated except that the gas filling the space of the glass ampoule was CO 2 (60 ml), and the concentration of carboxylic acid produced by irradiation for 2 hours and 4 hours was 669 μM and 723, respectively
μM.

【００２２】実施例８ 実施例１において、ガラスアンプルの空間に充填するガ
スをＣＯ2 （６０ｍｌ）およびガンマ線の照射線量率
０．４ＫＧｙ／ｈｒとする以外は同様の方法を行なった
ところ、２時間および４時間の照射により生ずるカルボ
ン酸の濃度は、それぞれ７７３μＭおよび７０５μＭで
あった。Example 8 The same method as in Example 1 was repeated except that the gas filling the space of the glass ampoule was CO 2 (60 ml) and the irradiation dose rate of gamma rays was 0.4 KGy / hr. And the concentration of carboxylic acid produced by irradiation for 4 hours was 773 μM and 705 μM, respectively.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 Ｄ 7419−4Ｈ ３００ Ｃ０７Ｃ 27/04 27/08 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location // C07B 61/00 D 7419-4H 300 C07C 27/04 27/08

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 鉄イオンの存在下に、二酸化炭素を含有
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
徴とするカルボン酸の製造方法。1. A method for producing a carboxylic acid, which comprises contacting a gas containing carbon dioxide with water in the presence of iron ions and irradiating an electromagnetic wave. 【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に記載のカルボン酸の製造方法。2. The method for producing a carboxylic acid according to claim 1, wherein the electromagnetic wave is gamma ray, electron beam or ultraviolet ray.
JP4145240A 1992-06-05 1992-06-05 Production of carboxylic acid Pending JPH05339195A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4145240A JPH05339195A (en) 1992-06-05 1992-06-05 Production of carboxylic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4145240A JPH05339195A (en) 1992-06-05 1992-06-05 Production of carboxylic acid

Publications (1)

Publication Number Publication Date
JPH05339195A true JPH05339195A (en) 1993-12-21

Family

ID=15380571

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4145240A Pending JPH05339195A (en) 1992-06-05 1992-06-05 Production of carboxylic acid

Country Status (1)

Country Link
JP (1) JPH05339195A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010099626A (en) * 2008-10-27 2010-05-06 Mitsui Eng & Shipbuild Co Ltd Apparatus and method for reducing and fixing carbon dioxide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010099626A (en) * 2008-10-27 2010-05-06 Mitsui Eng & Shipbuild Co Ltd Apparatus and method for reducing and fixing carbon dioxide

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