JPS605574B2 - How to produce methyl chloride and ammonia - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing methyl chloride and ammonia from ammonium chloride and methanol.

A method for producing chlorinated hydrocarbons from ammonium chloride and alcohols through a catalytic reaction is described in U.S. Patent No. 27553.
No. 10, No. 2755311 and No. 2755316
There is a description in the issue.

These patents state that alumina etc. are used as a catalyst and that amines and ethers are obtained as by-products in addition to chlorinated hydrocarbons and ammonia as reaction products, but the amounts etc. are not clearly stated. Not listed.
However, according to the research of the present inventor, when ammonium chloride and methanol are reacted by the method described in the above invention, a large amount of methylamines is produced as a by-product, making it impossible to selectively obtain methyl chloride. do not have. Particularly under conditions where there is a large amount of unreacted methanol, the amount of dimethyl ether produced is extremely large, and these methods cannot be said to be economically or industrially advantageous production methods. As a result of intensive studies on a method for selectively producing methyl chloride and ammonia from methanol and ammonium chloride, the inventor found that when activated carbon is used as a catalyst, not only methyl chloride but also ammonia can be produced with extremely high selectivity. He found that dimethyl ether can be obtained in high yield and that the formation of dimethyl ether can be suppressed to an almost negligible level even under conditions where there is a large amount of unreacted methanol. Furthermore, they found that methyl chloride and ammonia could be obtained in even better yields by supporting certain metal elements on activated carbon, and completed the present invention.

That is, the present invention uses ammonium chloride and methanol,
A catalytic reaction is carried out in the gas phase in the presence of a catalyst in which activated carbon is loaded with one or more metal elements selected from alkali metals, alkali metals, zinc, zirconium, copper, aluminum, iron group elements, and palladium. This is a method for producing methyl chloride and ammonia.

The ammonium chloride used as a raw material in the present invention can be used in solid form, or in the form of an aqueous solution or slurry by mixing with water and sublimating it inside or outside the reactor.

There are no particular restrictions on the ammonium chloride used at this time, and a wide variety of ammonium chlorides can be used, including those obtained from natural sources, those obtained by the ammonia-soda method, double decomposition of ammonium sulfate and salt, and the like. Moreover, in these ammonium chloride or ammonium chloride aqueous solution, methylamines, their hydrochlorides, or tetramethylammonium chloride,
Even if hydrogen chloride or the like is mixed in, these contaminants are effectively utilized in the catalytic reaction, so they can be used without any particular problem. As the activated carbon catalyst used in the present invention, activated carbon manufactured from any raw material such as blue coal, bone, charcoal, lignite, peat, pecan shell, saran coal, petroleum residue, etc. can be used. , any shape may be used as long as there is no particular problem.

There is no particular limit to the amount of metal elements added to activated carbon, but it is generally 0.5 to 4 parts per 100 parts of activated carbon, especially 2 parts.
It is preferable to add in a range of 30 parts to 30 parts.

If it is less than 0.5 part, no substantial effect can be obtained, and if it is more than 4 parts, there is no problem, but there is no particular effect.

Further, these metals can be added in various forms such as hydrochloride, sulfate, molybdate, aluminate, hydroxide, and oxide. The raw material gas and the catalyst may be brought into contact with each other by any suitable method such as a fixed bed method or a fluidized bed method.

The feed ratio of raw material ammonium chloride and methanol can be selected arbitrarily, but when only ammonium chloride is used as a chlorine source, the molar ratio of ammonium chloride to methanol is 0.1 to 5.0, preferably 0.3 to 1. Use in the range of .5.

molar ratio of ammonium chloride to methanol is 5.0
When the size becomes larger, the amount of unreacted ammonium chloride increases, and a large amount of energy is required to recover and recycle it. In addition, when the molar ratio is less than 0.1, the amount of unreacted methanol increases, and decomposition reactions are likely to occur.
This is not preferable because the selectivity of methyl chloride decreases. In carrying out the present invention, the reaction temperature ranges from 250 to 600 qo, preferably from 280 to 45,000 qo. At temperatures below 25,000, a substantial reaction rate cannot be obtained, and the ammonium chloride concentration in the raw material gas decreases because the vapor pressure of ammonium chloride is low.

Moreover, at a temperature of 600 qo or more, decomposition reactions increase and the methyl chloride selectivity decreases. The reaction pressure is not particularly limited and may be normal pressure, increased pressure, or reduced pressure, but it is usually convenient to operate at normal pressure or slightly increased pressure.

The feed space velocity (SV) of the reactants to the reactor can vary over a fairly wide range, but is usually in the range from 100 to 3000 hrl, preferably from 200 to 2000 hrl.

The reaction product of the present invention can be easily combined with the reaction products methyl chloride, ammonia, unreacted methanol, and "unreacted ammonium chloride" by a commonly known method such as a dry collection method or a hot water quench method. Can be separated.

Unreacted ammonium chloride can be recycled and used again as a reaction raw material. The unreacted ammonium chloride, separated methyl chloride, ammonia and unreacted methanol can be easily separated by known methods, and the unreacted methanol can be used again as a reaction raw material. According to the present invention, when activated carbon alone is used as a catalyst, the reaction may be inhibited if a large amount of water coexists in the reaction system. This method is extremely convenient as an industrial method because it is possible to obtain ammonia and ammonia, and the product can be easily collected and separated using simple methods such as water absorption.

Example 1 40% of a catalyst (sodium aluminate content: 1%) prepared by adding activated carbon (DSW-18 to 12 mesh manufactured by Daiichi Carbon Industry Co., Ltd.) to a 5M% alumic acid aqueous solution and evaporating it to dryness.
A mixed gas of methanol and ammonium chloride was charged into a reactor on the 22nd side of the inner wall heated in an electric furnace.
The molar ratio of ammonium chloride to methanol was 0.9, and the SV650hr-IL reaction temperature was 35500.
The reaction was carried out in a fixed bed method.

The high-temperature reaction product gas is introduced into a cylindrical glass air-cooled collector equipped with a filter, and gradually reduced to about 120q0.
After collecting the entire amount of unreacted ammonium chloride as a solid, the remaining reaction gas is introduced into an absorption tube containing water, where it is separated into soluble components, mainly consisting of ammonia and methanol, and unreacted components, mainly consisting of methyl chloride. It was separated into components and analyzed by gas chromatography. As a result, the methanol conversion rate was 71.0% and the ammonium chloride conversion rate was 65.0%.
0%, methyl chloride yield 59.8% (based on supplied methanol), 64.3% (based on supplied ammonium chloride), ammonia yield 63.7% (based on supplied ammonium chloride), methylamine neck yield 2.4 % (based on supplied methanol), 1
．． 3% (based on supplied ammonium chloride) was obtained, and only trace amounts of hydrocarbons such as dimethyl ether and methane were detected.

Comparative Example 1 The same method as in Example 1 was used except that activated carbon containing no sodium aluminate was used as a catalyst.

As a result, methanol conversion rate was 49.1%, ammonium chloride conversion rate was 43.0%, methyl chloride yield was 39.2% (based on supplied methanol), 42.1% (based on supplied ammonium chloride), and ammonia yield was 42. 1% (based on ammonium chloride feed).

Only trace amounts of hydrocarbons such as methylamines, dimethyl ether, and methane were detected. Examples 2-10
and Comparative Examples 2 to 5 Using the catalyst shown in Table 1, under the reaction conditions shown in Table 1,
The reaction was carried out using the same method as in Example 1.

The results are shown in Table 1. ship candle M debt fart X 2 Chigo turnip day Bitterness; Hair× IH's Rn 2 days ．． Up.

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a Koshu Examples 11 to 20 and Comparative Examples 6 to 9 Except that methanol and ammonium chloride were supplied with water in the proportions shown in Table 2, and the catalysts shown in Table 2 were used.
The reaction was carried out in the same manner as in Example 1.

The results are shown in Table 2. ship ship cicada product Z earth death d poison Library building During ~ cicada oat Horiren n charge 5 It's hard.

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Claims (1)

[Claims] 1 Ammonium chloride and methanol are aerated in the presence of a catalyst in which activated carbon supports one or more metal elements selected from alkali metals, alkaline earth metals, zinc, zirconium, copper, aluminum, iron group elements, and palladium. A method for producing methyl chloride and ammonia characterized by catalytic reaction in a phase.