JPH0267254A - Production of 1-2c nitrogen-containing compound - Google Patents

Abstract

PURPOSE:To obtain 1-2C nitrogen-containing compound, 1-2C oxygencontaining compound and/or amino acid in high selectivity by reaching methane with ammonia and water under irradiation of light at specific wavelength in a gas phase. CONSTITUTION:Methane is reacted with ammonia and water under irradiation of light rays comprising a line spectrum of 185-254nm (e.g. low-pressure mercury vapor lamp of 50-100W is used as light source) at 70-100 deg.C under 1-5 atm in a gas phase to give the aimed substance. The blending ratio of methane: ammonia:water is (0.06:0.006:1)-(0.06:0.24:1) in molar ratio. Ethylenediamine as 1-2C nitrogen-containing compound is useful as a raw material for producing chelating agent, germicide, surfactant, etc., and monomethylamine is useful as a synthetic intermediate for various kinds of industrial products.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides C0 to C! monomethylamine, ethylenediamine, etc. from methane, ammonia and water. C, -C of nitrogen-containing compounds, methanol, etc. Oxygenates and/or amino acids such as histidine, especially the C1-Ct
The present invention relates to a method for producing a nitrogen-containing compound.

[Conventional technology]

Conventionally, monomethylamine was produced by mixing methanol and ammonia in the presence of an alumina gel solid catalyst at a temperature of 380 to 450°C.
and a pressure of 15 kg/cm". In this conventional method, monomethylamine, dimethylamine and trimethylamine were mixed in a ratio of 4:2.
: 3 (molar ratio), it is difficult to increase the selectivity of monomethylamine. On the other hand, ethylenediamine is prepared by mixing ethylene chloride and aqueous ammonia under pressure.
Although it is produced by reacting at 0 to 180°C, secondary amines and tertiary amines are produced as by-products in this conventional method. As described above, conventional methods for producing monomethylamine and ethylenediamine still have many problems that need to be improved in the future regarding their raw materials and reaction conditions.

On the other hand, various methods have been proposed for producing various useful compounds from methane, ammonia, and/or water.

Science, Volume 117, May 15, 1953, 52
On pages 8-529, glycine, α-alanine,
It is disclosed that amino acids such as β-alanine can be obtained.

Journal of the American Chemical Society ((J, And, Chew, Soc, 77
(1955) 2351), Volume 77, 1977.5
For example, 60
．． 000 volts high frequency pressure spark discharge or 15.0 volts
Direct production of amino acids such as glycine, alanine, sarcosine and organic acids such as formic acid, acetic acid, glycolic acid and lactic acid by reacting a mixture of methane, ammonia, water and hydrogen by silent discharge using a 00 volt transformer. is disclosed.

Life Science Space Research
5science 5pace Research)1
5.95-99 (1977) discloses that hydrogen cyanide, ethane, propane, hydrazine, butane, etc. can be obtained by photolysis of ammonia in the presence of hydrogen, helium and methane.

Journal of the American Chemical Society (J, A+s, Chew, Soc,), 1
May 23, 979, pages 3127-3128, Pt
It is disclosed that amino acids can be obtained by irradiating light using a 2.5 kHz xenon lamp while passing methane through an aqueous NH4Cl solution or an aqueous NH1 solution in the presence of /Ti(h).

Journal Op Photochemistry (Journa)
l of Photochemistry), 13
(1980), pp. 353-356, discloses that methylamine is obtained by photolysis of a mixture of methane and ammonia under irradiation with light of 123.6 na+, the wavelength of a krypton resonance lamp.

JP-A No. 60-224657 discloses that ammonia or a primary or secondary amine is produced by contacting it with a photocatalyst such as ammonium iodide in the liquid phase in the presence of light having an emission spectrum exceeding 160 nm emitted from a high-pressure mercury lamp or the like. A photochemical amine production method has been disclosed in which amines such as monoethylamine and n-propylamine are produced by reacting olefins such as ethylene and propylene with olefins such as ethylene and propylene.

JP-A No. 62-47495 discloses that 4W in the presence of a photocatalyst
Directly converts methane into methanol by electrolysis in a solution containing chloride ions, which is irradiated with light emitted from a low-pressure mercury lamp.
A method for producing chloromethane and dichloromethane is disclosed.

JP-A-62-195339 discloses a method for directly synthesizing methanol by reacting methane and water vapor under irradiation with light emitted from a low-pressure mercury lamp.

JP-A No. 62-249938 discloses that methane and water vapor are reacted under irradiation with light emitted from a 20W low-pressure mercury lamp to produce alcohols such as methanol, organic acids such as acetic acid,
Methods for the direct production of ketones such as acetone and esters such as methyl formate are disclosed.

[Problem to be solved by the invention]

In view of the above-mentioned prior art, the present inventor has conducted various studies on methods of reacting methane, ammonia, and water under light irradiation in order to directly obtain useful chemical substances using methane, and as a result, has developed various useful chemical substances. They discovered that a substance can be obtained and completed the present invention.

The present invention produces C, -C, and nitrogen-containing compounds such as monomethylamine and ethylenediamine by irradiating light with a specific wavelength under specific conditions and causing a gas phase reaction between methane and ammonia in the presence of water. , methanol etc. 01~
02 oxygenates and/or amino acids such as histidine, especially the 01-C! The object of the present invention is to provide a method for producing nitrogen-containing compounds with high selectivity.

[Means to solve the problem]

The present invention allows methane, ammonia and water to be converted into 185n-
and C, -C, nitrogen-containing compounds, 01-02 oxygen-containing compounds and/or amino acids, especially the C3-C2-containing A method for producing a nitrogen compound is provided.

The gas phase reactions of methane, ammonia and water in the present invention are carried out under irradiation with light consisting essentially of a line spectrum of 185 nm and 254 Hm.

The irradiation light of the present invention can include other light rays with wavelengths in the range of 180 Hm to 254 Hm, but if the wavelength is less than 18 On-, the generated nitrogen-containing compounds and oxygen-containing compounds will be photodecomposed. Unpreferably, the wavelength is 25
If it exceeds 4na+, the light energy will be insufficient to decompose water and ammonia, which is not preferable.

According to the ER3 measurement of the chemical reaction of methane-ammonia-water system, CI! The existence of NOg was revealed.

This is produced by a hydrogen abstraction reaction from methylamine. Ethylenediamine is thought to be produced by .CIgNH-rich radical coupling.

Water and ammonia are, for example, 185n in a low-pressure mercury lamp.
It absorbs light of m and decomposes it as follows.

hν ttgo →・OH＋H”
(i) hν NH3→ ・NH, + H'
(2) OH radicals extract hydrogen from methane to generate methyl radicals.

CHa+・OH→・CH3+ HzO(3) Methyl radical combines with NH, to form methylamine.

・CH3+ ・NH, → CH3N Hz
(4) Methylamine generates C1hNH1 by hydrogen abstraction with OH. This radical coupling results in ethylenediamine.

Cl5NB! +・OH→・CHtNIh + HzO(
512・CHJHt -HJCHzCH! NHg
(6) Furthermore, the production of oxygen-containing compounds such as methanol can be considered as follows.

CH4+・OH-CH30H+ H' (71
As a light source of irradiation light in the present invention, for example, 50 to 1
00W low pressure mercury lamp, wavelength 185nn+ and 25
4n- laser light is suitable.

The gas phase reaction temperature in the method of the present invention is 70 to 100°C when the low pressure mercury lamp is used as the light source of the irradiation light.
Preferably it is in the range of 80 to 90°C, and the reaction temperature is 1
If the temperature exceeds 00°C, the wavelength of the light from the low-pressure mercury lamp will shift to a longer wavelength and the optical density at a wavelength of 185n- will decrease, which is undesirable. is unfavorable because the amount of water vapor necessary for the reaction is insufficient.

In the method of the present invention, when a low-pressure mercury lamp is used as the irradiation light source, the reaction pressure is 1 to 5 atm, preferably 1 to 5 atm.
The pressure is in the range of 2 atm, and if the pressure exceeds 5 atm, this is undesirable because problems will arise in the pressure resistance of the material of the low-pressure mercury lamp, and if it is less than 1 atm, it is undesirable because the reaction vessel must be made larger.

The mixing ratio of methane, ammonia and water in the gas phase reaction of methane, ammonia and water in the method of the present invention is usually methane:ammonia:water -0.06 molar ratio.
:0.006:1 to 0.06:0.24:1, and the ammonia amount is in the range of 0.06:0.
If the mixing ratio is lower than 0.006:1, the amount of nitrogen will be insufficient and the object of the present invention will not be achieved, and the amount of ammonia will be less than 0.
．． If it increases more than 061.24:l, most of the irradiated light will be consumed for photodecomposition of ammonia, which is not preferable.

During the gas phase reaction of methane, ammonia and water in the method of the present invention, other gases such as hydrogen, nitrogen, carbon dioxide,
Although there is no problem even if an inert gas is mixed, if a large amount of oxygen is present, a large amount of oxygen-containing compounds will be obtained, which is not preferable when the purpose is to produce nitrogen-containing compounds. However, when oxygen gas is added in a molar ratio of about 1.5 to 4.5% with respect to methane, there is no particular problem as long as the amount of methanol produced or the amount of ethylenediamine produced increases.

The C, -C, nitrogen-containing compound obtained by the method of the present invention has monomethylamine and ethylenediamine as its main components, and a small amount of CH2, which varies depending on the reaction conditions.
N0! , CHsCN-NHzCJ40H.

Ni1 (CJ40H) z, NH (CI3COOH)
z and NHzCHzCN.

The C3-C2 oxygen-containing compound obtained by the method of the present invention contains methanol as a main component, and also contains small amounts of ethanol and formaldehyde.

The amino acids obtained by the method of the present invention vary depending on the reaction conditions, but include histidine and glycine as main components, and small amounts of alanine and glutamic acid.

In addition, small amounts of ethane and hydrogen are obtained according to the process of the invention.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 Using the apparatus shown in Figure 1, methane and
50W low pressure mercury lamp 3 (
The mixture was supplied to a reaction tube 1 (diameter 9ON, length 420 mm) equipped with main wavelengths of 185 nm and 254 nm) and a thermometer 2, and the reaction was carried out at a temperature of 100° C. under light irradiation. Steam and ammonia were supplied through the injection port 12, and methane was supplied through the injection port 13.

The reaction product and unreacted gas were first cooled in a water-cooled condenser 7, and the uncondensed gas was further captured in a pentane slush trap (-130°C) 6. The exhaust gas was returned to the reaction tube 1 again by the circulation pump 10. The pressure in the reaction tube 1 was always maintained at atmospheric pressure by adjusting the water level in the pressure adjustment tank 9. Circulating gas flow rate is IIl/wi
n, and the ratio of the initial number of moles of methane to the number of moles of consumed water vapor, n (CH4) / n (■zO), is 6
X10-", and the reaction was carried out for 5 hours under these conditions. After the reaction was completed, the pentane slush trap was returned to room temperature, and the gas generated at this time was stored in the gas storage tank 4, which had been evacuated in advance by the vacuum system 15. Ta.

The products in the gas phase were analyzed using a gas chromatograph (Shimadzu GC-8A).
, JEOL JGC-1100). Quantification of liquid phase products is carried out using the steam chromatography method (Daii 5SC).
-1) High performance liquid chromatography (Hitachi 655A)
and spectrophotometric method using chromotropic acid (Hitachi 10
0-50 type double beam). The results obtained are shown in Table 1.

Examples 2 to 4 Example 1 except that the raw material gas composition was changed as shown in Table 1
A similar experiment was conducted. The results obtained are shown in Table 1.

Example 5 An experiment similar to Example 1 was conducted except that the amount of ammonia added was increased as shown in Table 2.

The results obtained are shown in Table 2.

Example 6 An experiment similar to Example 4 was conducted except that air was injected from the air injection port 14 as shown in Table 2. The results obtained are shown in Table 2.

Examples 7 and 8 As shown in Table 2, an experiment similar to Example 3 was conducted except that air was injected from the air injection port 14. The results obtained are shown in Table 2.

Example 9 As shown in Table 2, an experiment similar to Example 1 was conducted except that air was injected from the air injection port 14. The results obtained are shown in Table 2.

Example 10 An experiment similar to Example 1 was conducted with the amount of water vapor kept constant at 5 mmol and the molar ratio of ammonia to methane varied. The results obtained for the main products are shown in FIG. As is clear from FIG. 2, the molar ratio of ammonia to methane for obtaining monomethylamine and ethylenediamine as the main components of the C1-C2 nitrogen-containing compound is preferably 0.2-3. Ol is particularly preferably 0.5 to 2.0
It is recognized that it is within the range of .

[Effects of the Invention] According to the present invention, by a method of irradiating light of a specific wavelength from methane, ammonia, and water, CI"' Cz
Nitrogen-containing compounds, 01-C2 oxygen-containing compounds and/or amino acids can be produced.

According to the present invention, by irradiating light of a specific wavelength from methane, ammonia, and water, ethylenediamine, which is useful as a raw material for manufacturing chelating agents, disinfectants, surfactants, etc., and important as an intermediate for various industrial products can be produced. monomethylamine can be produced directly and with high selectivity.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of an apparatus for carrying out the method of the present invention. In FIG. 1, 1...reaction tube; 2...thermometer; 3
...Low pressure mercury lamp; 4...Gas storage tank;5...
Manometer; 6...Pentane slush trap;
7... Water-cooled condenser; 8... Solution storage tank; 9
...Pressure adjustment tank; 10...Circulation pump; 11.
...Flowmeter; 12...Inlet for water vapor and ammonia;
13... Methane inlet; 14... Air inlet; 15
...Vacuum system. FIG. 2 is a graph showing the relationship between the molar ratio of ammonia and methane and the production amount of the main product.

Claims (1)

[Claims] 1. A method for producing a C_1 to C_2 nitrogen-containing compound, which is characterized in that methane, ammonia, and water are subjected to a gas phase reaction under irradiation with light consisting essentially of line spectra of 185 nm and 254 nm. 2. C_1 to C_2 according to claim 1, wherein the C_1 to C_2 nitrogen-containing compounds are monomethylamine and ethylenediamine.
C_2 Method for producing nitrogen-containing compound.