JP2003342242A - Method for producing alkyl nitrite - Google Patents
Method for producing alkyl nitriteInfo
- Publication number
- JP2003342242A JP2003342242A JP2003071283A JP2003071283A JP2003342242A JP 2003342242 A JP2003342242 A JP 2003342242A JP 2003071283 A JP2003071283 A JP 2003071283A JP 2003071283 A JP2003071283 A JP 2003071283A JP 2003342242 A JP2003342242 A JP 2003342242A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl nitrite
- nitric acid
- producing
- nitric oxide
- alkanol
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、硝酸から亜硝酸ア
ルキルを効率よく製造する方法に関する。亜硝酸アルキ
ルは、各種酸化プロセス（シュウ酸ジアルキル、炭酸ジ
アルキル等の製造）において有用な化合物である。TECHNICAL FIELD The present invention relates to a method for efficiently producing alkyl nitrite from nitric acid. Alkyl nitrite is a useful compound in various oxidation processes (production of dialkyl oxalate, dialkyl carbonate, etc.).
【０００２】[0002]
【従来の技術】亜硝酸アルキルを製造する方法として、
一酸化窒素と酸素とアルカノールを反応させる方法が知
られている（特許文献１、特許文献２）。しかしなが
ら、この方法は、相当量の硝酸が副生して窒素成分のロ
スを来たすという点で満足できるものではなく、この副
生硝酸を有効に再利用できる方法が要望されていた。As a method for producing alkyl nitrite,
A method of reacting nitric oxide, oxygen, and an alkanol is known (Patent Documents 1 and 2). However, this method is not satisfactory in that a considerable amount of nitric acid is by-produced to cause loss of the nitrogen component, and a method capable of effectively reusing this by-produced nitric acid has been demanded.
【０００３】一酸化炭素と亜硝酸メチルから炭酸ジメチ
ルを連続的に製造する方法においても、生成した一酸化
窒素を酸素及びメタノールと反応させて亜硝酸メチルに
再生する方法が知られていて、その際、硝酸を窒素源と
してガスに同伴させて補給することが開示されているが
（特許文献３）、この方法は硝酸の熱分解によって二酸
化窒素などを発生させることを目的とするもので、分解
反応が効率的ではなく適用温度範囲も限られるものであ
った。この場合、硝酸と一酸化窒素とメタノールの接触
も起り得るが、一酸化窒素と酸素とメタノールから亜硝
酸メチルを生成させる系では、酸素の供給によりガス中
の酸素及び二酸化窒素の濃度が高くなるため、硝酸と一
酸化窒素とメタノールから亜硝酸メチルを効率よく生成
させるのは非常に困難であることが、本発明者の研究の
過程で判明した。Also in the method for continuously producing dimethyl carbonate from carbon monoxide and methyl nitrite, there is known a method of reacting the generated nitric oxide with oxygen and methanol to regenerate methyl nitrite. At this time, it is disclosed that nitric acid is supplied as a nitrogen source along with the gas (Patent Document 3), but this method is intended to generate nitrogen dioxide and the like by thermal decomposition of nitric acid. The reaction was not efficient and the application temperature range was limited. In this case, contact between nitric acid, nitric oxide, and methanol may occur, but in a system that produces methyl nitrite from nitric oxide, oxygen, and methanol, the oxygen supply increases the concentrations of oxygen and nitrogen dioxide in the gas. Therefore, it was found in the course of research by the present inventors that it is very difficult to efficiently generate methyl nitrite from nitric acid, nitric oxide, and methanol.
【０００４】また、特許文献１では、亜硝酸アルキル再
生用反応塔の塔底液（硝酸を含有する）を抜き出して該
反応塔に冷却・循環しながら亜硝酸アルキルを製造する
方法が開示されていて、その際、硝酸と一酸化窒素とア
ルカノールの接触も起っているが、前記と同様に、酸素
の供給によりガス中の酸素及び二酸化窒素の濃度が高く
なっているため、硝酸と一酸化窒素とメタノールから亜
硝酸メチルを効率よく生成させることは非常に困難であ
ることが、同様に本発明者の研究の過程で判明した。Further, Patent Document 1 discloses a method for producing an alkyl nitrite by extracting a bottom liquid (containing nitric acid) of a reaction tower for regeneration of an alkyl nitrite and cooling and circulating it in the reaction tower. At that time, nitric acid, nitric oxide and alkanol also come into contact with each other, but similarly to the above, since the concentration of oxygen and nitrogen dioxide in the gas is increased by the supply of oxygen, nitric acid and nitric oxide are increased. Efficient production of methyl nitrite from nitrogen and methanol proved to be very difficult, as well as in the course of research by the present inventors.
【０００５】一方、二酸化窒素を生成させる方法とし
て、下記反応式（１）のように硝酸と一酸化窒素を反応
させる方法が知られているが（非特許文献１）、この方
法では最初に下記反応（２）が起る。On the other hand, as a method of producing nitrogen dioxide, a method of reacting nitric acid with nitric oxide as shown by the following reaction formula (1) is known (Non-patent document 1). Reaction (2) occurs.
【０００６】 ＮＯ ＋ ２ＨＮＯ３ → ３ＮＯ２ ＋ Ｈ２Ｏ （１） ＮＯ ＋ ＨＮＯ３ → ＮＯ２ ＋ ＨＮＯ２ （２）NO + 2HNO 3 → 3NO 2 + H 2 O (1) NO + HNO 3 → NO 2 + HNO 2 (2)
【０００７】しかし、反応（２）は平衡反応でその平衡
が原系に大きく偏っているため、二酸化窒素及び亜硝酸
を高濃度で生成させることが困難である。更に、平衡を
生成系にずらそうとしても、二酸化窒素の水への溶解度
が比較的大きく、しかも水溶液中では二酸化窒素と硝酸
が平衡関係にあることから、二酸化窒素が高濃度になる
ほど或いは圧力が高くなるほど硝酸が生成し、結果とし
て二酸化窒素及び亜硝酸を高濃度で生成させることが困
難になるという問題がある。このように、この方法は、
硝酸から二酸化窒素及び亜硝酸を生成させる方法として
工業的に好適なものではないことが、本発明者の研究の
過程でわかった。However, since the reaction (2) is an equilibrium reaction and the equilibrium is largely biased toward the original system, it is difficult to produce nitrogen dioxide and nitrous acid at high concentrations. Furthermore, even if an attempt is made to shift the equilibrium to the production system, the solubility of nitrogen dioxide in water is relatively large, and since nitrogen dioxide and nitric acid are in equilibrium in an aqueous solution, the higher the concentration of nitrogen dioxide or the pressure is There is a problem that the higher it is, the more nitric acid is produced, and as a result, it is difficult to produce nitrogen dioxide and nitrous acid at high concentrations. Thus, this method
It was found in the course of research by the present inventors that it is not industrially suitable as a method for producing nitrogen dioxide and nitrous acid from nitric acid.
【０００８】また、一酸化窒素の製法として、濃硝酸
を、ビスマス、銅、鉛、水銀などの金属、又は、酸化鉄
（II）、三酸化二砒素で還元する方法も知られているが
（非特許文献２）、この方法は量論反応を利用するもの
で、上記金属や酸化物を大量に必要とすることから、工
業的な方法としては好ましくなかった。A known method for producing nitric oxide is to reduce concentrated nitric acid with a metal such as bismuth, copper, lead or mercury, or iron (II) oxide or diarsenic trioxide ( Non-Patent Document 2), this method utilizes a stoichiometric reaction and requires a large amount of the above-mentioned metals and oxides, which is not preferable as an industrial method.
【０００９】[0009]
【特許文献１】特開平１１−１８９５７０号公報[Patent Document 1] JP-A-11-189570
【特許文献２】特開平６−２９８７０６号公報[Patent Document 2] JP-A-6-298706
【特許文献３】特開平６−２５１０４号公報[Patent Document 3] JP-A-6-25104
【非特許文献１】ＣＨＥＭＩＳＴＲＹ ＬＥＴＴＥＲ
Ｓ，１０２９（１９７６）[Non-Patent Document 1] CHEMISTRY LETTER
S, 1029 (1976)
【非特許文献２】化学大辞典１縮刷版第３２刷，６６５
頁[Non-Patent Document 2] Chemistry Dictionary 1 Reduced Edition 32nd edition, 665
page
【００１０】[0010]
【発明が解決しようとする課題】本発明は、硝酸（例え
ば、一酸化窒素と酸素とアルカノールを出発物質とする
亜硝酸アルキルの製造方法における副生硝酸など）から
亜硝酸アルキルを効率よく製造できる、工業的に好適な
亜硝酸アルキルの製造方法を提供することを課題とす
る。According to the present invention, alkyl nitrite can be efficiently produced from nitric acid (for example, by-produced nitric acid in the method for producing alkyl nitrite starting from nitric oxide, oxygen and alkanol). An object of the present invention is to provide an industrially suitable method for producing alkyl nitrite.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、前記の課
題を解決すべく鋭意検討した結果、非特許文献１の方法
において、アルコールを共存させることにより（２）式
で生成する亜硝酸を速やかに亜硝酸アルキルに変換し、
全体として硝酸と一酸化窒素の反応を極めて円滑に進め
られることを見出して、本発明を完成するに至った。即
ち、本発明は、硝酸及びアルカノールを含有する水溶液
を一酸化窒素ガスと接触させて亜硝酸アルキルを生成さ
せることを特徴とする亜硝酸アルキルの製造方法にあ
る。更に、本発明は、前記一酸化窒素ガスが、一酸化窒
素ガス中に分子状酸素が存在することにより生成する窒
素酸化物を実質的に含有しない、前記の亜硝酸アルキル
の製造方法にもある。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that in the method of Non-Patent Document 1, nitrous acid produced by the formula (2) by coexisting alcohol Is quickly converted to alkyl nitrite,
As a whole, they have found that the reaction between nitric acid and nitric oxide can proceed extremely smoothly, and have completed the present invention. That is, the present invention is a method for producing alkyl nitrite, which comprises contacting an aqueous solution containing nitric acid and an alkanol with nitric oxide gas to produce alkyl nitrite. Furthermore, the present invention also resides in the method for producing an alkyl nitrite, wherein the nitric oxide gas is substantially free of nitrogen oxides produced by the presence of molecular oxygen in the nitric oxide gas. .
【００１２】本発明の好ましい態様としては、（１）前
記一酸化窒素ガスが一酸化窒素ガス中に分子状酸素が存
在することにより生成する窒素酸化物を実質的に含有し
ていない、前記の亜硝酸アルキルの製造方法、（２）前
記一酸化窒素が、二酸化窒素、三酸化二窒素、四酸化二
窒素、及び、分子状酸素を実質的に含有していない、前
記の亜硝酸アルキルの製造方法、（３）前記水溶液が６
０重量％以下の濃度で硝酸を含有する前記の亜硝酸アル
キルの製造方法、（４）前記水溶液が５〜７０重量％の
濃度でアルカノールを含有する前記の亜硝酸アルキルの
製造方法などがある。In a preferred embodiment of the present invention, (1) the nitric oxide gas is substantially free of nitrogen oxides produced by the presence of molecular oxygen in the nitric oxide gas. Method for producing alkyl nitrite, (2) Production of alkyl nitrite, wherein the nitric oxide is substantially free of nitrogen dioxide, dinitrogen trioxide, dinitrogen tetraoxide, and molecular oxygen Method, (3) The aqueous solution is 6
There are a method for producing the above alkyl nitrite containing nitric acid at a concentration of 0% by weight or less, and (4) a method for producing the above alkyl nitrite in which the aqueous solution contains an alkanol at a concentration of 5 to 70% by weight.
【００１３】[0013]
【発明の実施の形態】本発明で用いる硝酸及びアルカノ
ールを含有する水溶液において、硝酸濃度は特に制限さ
れるものではなく、高濃度でも低濃度でもよいが、工業
的な効率を考慮すれば、該水溶液は６０重量％以下（特
に１〜６０重量％）、更には２０重量％以下（特に１〜
２０重量％）の濃度で硝酸を含有していることが好まし
い。BEST MODE FOR CARRYING OUT THE INVENTION In the aqueous solution containing nitric acid and alkanol used in the present invention, the nitric acid concentration is not particularly limited and may be a high concentration or a low concentration. The aqueous solution is 60% by weight or less (especially 1 to 60% by weight), and further 20% by weight or less (especially 1 to
It is preferable to contain nitric acid at a concentration of 20% by weight).
【００１４】本発明で用いるアルカノールとしては、炭
素数１〜３のアルカノール（メタノール、エタノール、
ｎ−プロパノール、ｉ−プロパノール）が好ましく挙げ
られるが、中でもメタノールが特に好ましい。アルカノ
ールは前記水溶液に含有（均一に溶解又は混合）されて
おり、前記水溶液は５〜７０重量％の濃度でアルカノー
ルを含有していることが好ましい。The alkanol used in the present invention is an alkanol having 1 to 3 carbon atoms (methanol, ethanol,
(n-propanol and i-propanol) are preferred, and methanol is particularly preferred. The alkanol is contained (uniformly dissolved or mixed) in the aqueous solution, and the aqueous solution preferably contains the alkanol at a concentration of 5 to 70% by weight.
【００１５】このような硝酸及びアルカノールを含有す
る水溶液としては、例えば、前記の一酸化窒素と酸素と
アルカノールを反応させる亜硝酸アルキルの製造方法
（特許文献１、特許文献２など）において生じる硝酸及
びアルカノールを含有する水溶液が挙げられる。この水
溶液においては、硝酸の濃度は２０重量％以下、更には
１〜２０重量％、特に２〜１５重量％程度であることが
好ましく、アルカノールの濃度は１５〜６０重量％、更
には２０〜５５重量％であることが好ましい。Examples of the aqueous solution containing nitric acid and alkanol include nitric acid produced in the method for producing alkyl nitrite by reacting nitric oxide, oxygen and alkanol (Patent Document 1, Patent Document 2, etc.). An aqueous solution containing an alkanol may be mentioned. In this aqueous solution, the concentration of nitric acid is preferably 20% by weight or less, more preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, and the concentration of alkanol is 15 to 60% by weight, further 20 to 55% by weight. It is preferably in the weight%.
【００１６】本発明で用いる一酸化窒素ガスは純ガスで
あってもよいが、通常は窒素等の不活性ガスで希釈され
た混合ガスとして反応系に供給される。この場合、混合
ガスは、一酸化窒素を４容量％以上含有していることが
好ましく、反応の進行を妨げないガス成分（一酸化炭
素、二酸化炭素、アルコール蒸気等）を更に含んでいて
も差し支えない。また、一酸化窒素ガスは、亜硝酸アル
キルを効率よく生成させるために、一酸化窒素ガス中に
分子状酸素が存在することにより生成する窒素酸化物を
実質的に含有していないことが好ましい。例えば、二酸
化窒素、三酸化二窒素、四酸化二窒素、及び、分子状酸
素を実質的に含有していないことが好ましい。なお、一
酸化窒素は、硝酸１モルに対して１〜５０モル、更には
１．５〜２０モル、特に２〜１０モルの割合で用いるこ
とが好ましい。The nitric oxide gas used in the present invention may be a pure gas, but it is usually supplied to the reaction system as a mixed gas diluted with an inert gas such as nitrogen. In this case, the mixed gas preferably contains 4% by volume or more of nitric oxide, and may further contain gas components (carbon monoxide, carbon dioxide, alcohol vapor, etc.) that do not hinder the progress of the reaction. Absent. Further, it is preferable that the nitric oxide gas does not substantially contain a nitrogen oxide generated by the presence of molecular oxygen in the nitric oxide gas, in order to efficiently generate the alkyl nitrite. For example, it is preferably substantially free of nitrogen dioxide, dinitrogen trioxide, dinitrogen tetraoxide, and molecular oxygen. In addition, nitric oxide is preferably used in a ratio of 1 to 50 mol, further 1.5 to 20 mol, and particularly 2 to 10 mol per 1 mol of nitric acid.
【００１７】硝酸及びアルカノールを含有する水溶液と
一酸化窒素ガスを接触させる（硝酸を一酸化窒素及びア
ルカノールと反応させて亜硝酸アルキルを生成させる）
際の温度は、０〜２００℃、更には２０〜１００℃の範
囲であることが好ましい。また、圧力は、常圧から２０
ＭＰａＧ、更には常圧から３ＭＰａＧ、特に０．２〜１
ＭＰａＧの範囲であることが好ましい。本発明では、こ
のように加圧下でも反応を行うことができる。なお、反
応に用いる硝酸及びアルカノールを含有する水溶液も、
一酸化窒素ガス中に分子状酸素が存在することにより生
成する窒素酸化物を含有していないことが更に好まし
い。Contacting nitric oxide gas with an aqueous solution containing nitric acid and alkanol (reacting nitric acid with nitric oxide and alkanol to form alkyl nitrite)
The temperature at this time is preferably in the range of 0 to 200 ° C, more preferably 20 to 100 ° C. Also, the pressure is from normal pressure to 20
MPaG, further from normal pressure to 3 MPaG, especially 0.2 to 1
It is preferably in the range of MPaG. In the present invention, the reaction can be carried out under pressure as described above. In addition, the aqueous solution containing nitric acid and alkanol used in the reaction,
It is further preferable that the nitrogen oxides produced by the presence of molecular oxygen in the nitric oxide gas are not contained.
【００１８】また、前記反応の際には、８族金属（白金
族金属を除く）又は１Ｂ金属の硝酸塩を触媒として存在
させてもよい。８族金属（白金族金属を除く）の硝酸塩
としては、硝酸第二鉄、硝酸ニッケル、硝酸コバルトが
好ましく挙げられ、１Ｂ金属の硝酸塩としては、硝酸第
二銅が好ましく挙げられる。触媒は、硝酸含有水溶液に
対して、金属換算で２０重量％以下、更には１０重量％
以下、特に０．１〜１０重量％で存在させればよい。In the above reaction, a nitrate of Group 8 metal (excluding platinum group metal) or 1B metal may be present as a catalyst. Preferred nitrates of Group 8 metals (excluding platinum group metals) include ferric nitrate, nickel nitrate, and cobalt nitrate, and preferred nitrates of 1B metal include cupric nitrate. The catalyst is 20% by weight or less, further 10% by weight, in terms of metal, based on the nitric acid-containing aqueous solution.
Hereinafter, it may be present particularly at 0.1 to 10% by weight.
【００１９】前記反応は、液相でバッチ式でも連続式で
も可能である。この反応は、例えば、攪拌槽等の反応器
に硝酸及びアルカノールを含有する水溶液を供給し、液
中に一酸化窒素ガスを流通させながら常圧又は加圧下で
その溶液を攪拌するか、或いは一酸化窒素ガスを圧入し
て加圧下でその溶液を攪拌することにより行われる。こ
のとき、一酸化窒素ガス中に分子状酸素が存在すること
により生成する窒素酸化物は一酸化窒素ガスに実質的に
含まれず、反応系に供給されないことが好ましい。ま
た、該窒素酸化物は、反応器に供給する硝酸及びアルカ
ノールを含有する水溶液にも含まれていないことが更に
好ましい。The above reaction can be carried out in a liquid phase in a batch system or a continuous system. This reaction is carried out, for example, by supplying an aqueous solution containing nitric acid and an alkanol to a reactor such as a stirring tank and stirring the solution under normal pressure or pressure while circulating nitric oxide gas in the solution. It is carried out by injecting nitric oxide gas and stirring the solution under pressure. At this time, it is preferable that the nitrogen oxides produced by the presence of molecular oxygen in the nitric oxide gas are not substantially contained in the nitric oxide gas and are not supplied to the reaction system. Further, it is more preferable that the nitrogen oxide is not contained in the aqueous solution containing nitric acid and alkanol supplied to the reactor.
【００２０】反応器は、この反応を効率よく行うことが
できるものであればよく（複数であってもよい）、攪拌
槽以外に、充填塔やシーブトレイなどの多段塔形式のも
のも使用できるが、反応が気液接触反応になるため、攪
拌槽型反応器を用いる場合は、高攪拌、高ガス分散が可
能な羽根形状及び回転装置などを有する気液接触効率の
高い攪拌装置を用いることが好ましく、多段塔形式の反
応器では気液接触効率の高い充填材を用いることが好ま
しい。生成した亜硝酸アルキルは、前記ガスに同伴させ
て反応系外に導出して（必要に応じて洗浄等により精製
して）、他の反応に利用できる。Any reactor may be used as long as it can carry out this reaction efficiently (a plurality of reactors may be used), and in addition to the stirring tank, a multi-column tower type such as a packed tower or a sieve tray may be used. Since the reaction is a gas-liquid contact reaction, when using a stirred tank reactor, it is necessary to use a stirring device having a high gas-liquid contact efficiency, which has a blade shape and a rotating device capable of high stirring and high gas dispersion. It is preferable to use a packing material having high gas-liquid contact efficiency in a multi-column tower type reactor. The generated alkyl nitrite can be used together with the above gas, taken out of the reaction system (purified by washing or the like if necessary), and used for other reactions.
【００２１】[0021]
【実施例】次に、実施例及び比較例を挙げて本発明を具
体的に説明する。なお、硝酸はイオンクロマトグラフィ
ー及び滴定により、その他はガスクロマトグラフィーに
よりそれぞれ分析した。EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples. The nitric acid was analyzed by ion chromatography and titration, and the others were analyzed by gas chromatography.
【００２２】実施例１
攪拌機（パドル式攪拌羽根４枚付き）、ガス供給ノズ
ル、ガス抜き出しノズル、液抜き出しノズルを備えた１
Ｌ（リットル）容オートクレーブ（ＳＵＳ３１６製）
に、１６．７重量％硝酸水溶液５４０ｇとメタノール２
３０ｇを入れ、窒素でパージした後、窒素で０．４ＭＰ
ａＧまで加圧した。次いで、この圧力を維持するように
ガス抜き出しノズルからガスを抜き出しつつ、攪拌下
（１１００ｒｐｍ）、一酸化窒素と窒素の混合ガス（一
酸化窒素１０容量％）をガス供給ノズルから１６ＮＬ
（ノルマルリットル）／ｈで供給しながら５０℃まで昇
温した。Example 1 1 equipped with a stirrer (with four paddle type stirring blades), a gas supply nozzle, a gas extraction nozzle, and a liquid extraction nozzle
L (liter) autoclave (made by SUS316)
In addition, 540 g of a 16.7 wt% nitric acid aqueous solution and methanol 2
Add 30g, purge with nitrogen, then 0.4MP with nitrogen
Pressurized to aG. Then, while extracting gas from the gas extracting nozzle so as to maintain this pressure, while stirring (1100 rpm), a mixed gas of nitric oxide and nitrogen (10% by volume of nitric oxide) was supplied from the gas supply nozzle to 16 NL.
The temperature was raised to 50 ° C. while supplying (normal liter) / h.
【００２３】５０℃になった時点から１時間後に、ガス
抜き出しノズルから導出されるガス１９．２ＮＬ／ｈを
分析したところ、亜硝酸メチル１１．２容量％、一酸化
窒素２．１容量％、メタノール８．９容量％、水分２．
８容量％、窒素７５．０容量％の組成であった。また、
５０℃になった時点から３時間後に反応液中の硝酸濃度
を測定したところ、９．５重量％であった（硝酸転化速
度：約２ｇ／ｈ）。One hour after the temperature reached 50 ° C., 19.2 NL / h of the gas discharged from the gas extraction nozzle was analyzed and found to be 11.2% by volume of methyl nitrite and 2.1% by volume of nitric oxide. Methanol 8.9% by volume, water content 2.
The composition was 8% by volume and 75.0% by volume of nitrogen. Also,
When the nitric acid concentration in the reaction solution was measured 3 hours after the temperature reached 50 ° C., it was 9.5% by weight (nitric acid conversion rate: about 2 g / h).
【００２４】実施例２〜７
温度、圧力、攪拌などの条件を表１記載のように変えた
ほかは、実施例１と同様に反応を行った。但し、実施例
７では、硝酸水溶液に対して０．２ｍｏｌ／Ｌの濃度で
硝酸第二銅を添加した。結果を表１に示す。Examples 2 to 7 The reaction was carried out in the same manner as in Example 1 except that the conditions such as temperature, pressure and stirring were changed as shown in Table 1. However, in Example 7, cupric nitrate was added at a concentration of 0.2 mol / L to the nitric acid aqueous solution. The results are shown in Table 1.
【００２５】比較例１
硝酸水溶液を１１．７重量％硝酸水溶液７７０ｇに代
え、メタノールを加えなかったほかは、実施例１と同様
に反応を行った。その結果、５０℃になった時点から１
時間後に、ガス抜き出しノズルから導出されるガス１
６．４ＮＬ／ｈを分析したところ、一酸化窒素９．５容
量％、二酸化窒素０．５容量％、水分２．８容量％、窒
素８７．２容量％の組成で、硝酸は殆ど転化していなか
った。Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that the aqueous nitric acid solution was replaced with 770 g of a 11.7% by weight nitric acid aqueous solution and methanol was not added. As a result, 1 from the point when the temperature reached 50 ° C
Gas discharged from the gas extraction nozzle after 1 hour
Analysis of 6.4 NL / h showed that the composition was 9.5% by volume of nitric oxide, 0.5% by volume of nitrogen dioxide, 2.8% by volume of water, and 87.2% by volume of nitrogen, and nitric acid was almost converted. There wasn't.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明により、硝酸から亜硝酸アルキル
を効率よく製造できる工業的に好適な亜硝酸アルキルの
製造方法を提供できる。このため、例えば、一酸化窒素
と酸素とアルカノールを出発物質とする亜硝酸アルキル
の製造方法においては、副生硝酸を再利用して効率よく
亜硝酸アルキルに変換することができ、その結果、窒素
成分のロスを抑えて（即ち、亜硝酸アルキルの生成割合
を高めて）工業的に効率よく亜硝酸アルキルを製造する
ことができるようになる。また、本発明は、低濃度の硝
酸含有水溶液（アルカノールを含む）であっても効率よ
く亜硝酸アルキルを製造できるもので、そのような硝酸
含有水溶液から窒素成分を亜硝酸アルキルとして回収す
る場合に非常に有用である。INDUSTRIAL APPLICABILITY The present invention can provide an industrially suitable method for producing alkyl nitrite, which can efficiently produce alkyl nitrite from nitric acid. Therefore, for example, in a method for producing an alkyl nitrite starting from nitric oxide, oxygen, and an alkanol, the byproduct nitric acid can be reused and efficiently converted into an alkyl nitrite, and as a result, nitrogen It becomes possible to industrially and efficiently produce alkyl nitrite while suppressing the loss of components (that is, increasing the production ratio of alkyl nitrite). Further, the present invention is capable of efficiently producing alkyl nitrite even with a low-concentration nitric acid-containing aqueous solution (including alkanol), and when recovering a nitrogen component from such a nitric acid-containing aqueous solution as alkyl nitrite. Very useful.
フロントページの続き (72)発明者 三井 一昭 山口県宇部市大字小串1978番地の10 宇部 興産株式会社宇部ケミカル工場内 Ｆターム(参考） 4H006 AA02 AC59 BA05 BA34 BE02 BE44 4H039 CA60 CD10 Continued front page (72) Inventor Kazuaki Mitsui 10 Ube at 1978 Kogushi, Ube City, Yamaguchi Prefecture Kosan Co., Ltd.Ube Chemical Factory F-term (reference) 4H006 AA02 AC59 BA05 BA34 BE02 BE44 4H039 CA60 CD10
Claims (6)
を一酸化窒素ガスと接触させて亜硝酸アルキルを生成さ
せることを特徴とする亜硝酸アルキルの製造方法。1. A method for producing alkyl nitrite, which comprises contacting an aqueous solution containing nitric acid and an alkanol with nitric oxide gas to produce alkyl nitrite.
中に分子状酸素が存在することにより生成する窒素酸化
物を実質的に含有していない、請求項１記載の亜硝酸ア
ルキルの製造方法。2. The production of an alkyl nitrite according to claim 1, wherein the nitric oxide gas is substantially free of nitrogen oxides generated by the presence of molecular oxygen in the nitric oxide gas. Method.
酸化二窒素、四酸化二窒素、及び、分子状酸素を実質的
に含有していない、請求項１記載の亜硝酸アルキルの製
造方法。3. The method for producing an alkyl nitrite according to claim 1, wherein the nitric oxide gas is substantially free of nitrogen dioxide, dinitrogen trioxide, dinitrogen tetraoxide, and molecular oxygen. .
酸を含有する、請求項１記載の亜硝酸アルキルの製造方
法。4. The method for producing an alkyl nitrite according to claim 1, wherein the aqueous solution contains nitric acid at a concentration of 60% by weight or less.
ルカノールを含有する、請求項１記載の亜硝酸アルキル
の製造方法。5. The method for producing an alkyl nitrite according to claim 1, wherein the aqueous solution contains an alkanol at a concentration of 5 to 70% by weight.
金属の硝酸塩の存在下で接触させる、請求項１記載の亜
硝酸アルキルの製造方法。6. Group 8 metals (excluding platinum group metals) or 1B
The method for producing an alkyl nitrite according to claim 1, wherein the contact is performed in the presence of a metal nitrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010235461A (en) * | 2009-03-30 | 2010-10-21 | Ube Ind Ltd | Method for producing polycarbonate diol compound |
| WO2018179808A1 (en) * | 2017-03-29 | 2018-10-04 | 宇部興産株式会社 | Method and apparatus for producing alkyl nitrite |
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2003
- 2003-03-17 JP JP2003071283A patent/JP4026521B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010235461A (en) * | 2009-03-30 | 2010-10-21 | Ube Ind Ltd | Method for producing polycarbonate diol compound |
| WO2018179808A1 (en) * | 2017-03-29 | 2018-10-04 | 宇部興産株式会社 | Method and apparatus for producing alkyl nitrite |
| JPWO2018179808A1 (en) * | 2017-03-29 | 2020-02-13 | 宇部興産株式会社 | Method and apparatus for producing alkyl nitrite |
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