JPH06179640A - Production of methylamines - Google Patents

Abstract

PURPOSE:To obtain mono-and dimethylamines by reacting methanol with ammonia using mordenite treated with an alcoholic solution containing a tetraalkoxysilane dissolved therein in a liquid layer and suppressing the formation of trimethylamine. CONSTITUTION:Methanol is made to react with ammonia to suppress the formation of trimethylamine and produce mono- and dimethylamines. In the process, a catalyst prepared by treating mordenite with an alcoholic solution containing a silicon alkoxide, especially a tetraalkoxysilane dissolved in methanol, ethanol, isopropyl alcohol, etc., is used as a catalyst. The methylamines are compounds useful as a raw material for producing various organic synthetic intermediates. The mono- and dimethylamines are obtained in a large amount according to this method. Since the amount of trimethylamine formed as a by-product is small, a step for recycling the trimethylamine to the reactional system and disproportionating the trimethylamine can be omitted. Thereby, the process for producing the methylamines can be simplified to reduce the amount of utilities used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing amines, and more particularly to a method for producing a larger amount of mono- and dimethylamine than trimethylamine in producing methylamines from methanol and ammonia. The methylamines obtained by the method of the present invention are useful compounds as raw materials for producing solvents and raw materials for producing various organic synthetic intermediates.

[0002]

2. Description of the Related Art Methylamines, that is, monomethylamine, dimethylamine and trimethylamine are produced by a method of reacting methanol or a mixture of methanol and dimethyl ether with ammonia, a method of catalytic reduction of hydrocyanic acid and the like. Thus, these methylamines are mono,
It is produced as a mixture of di and trimethylamine, and has a corresponding use. On the other hand, the demand for these methylamines is biased toward dimethylamine or monomethylamine, and the demand for trimethylamine is small at present. Methylamines obtained by the reaction of methanol and ammonia using ordinary amorphous silica alumina as a catalyst are
Since trimethylamine is the main product, there is a problem that the amount of dimethylamine, which is in high demand, is small. In order to overcome these difficulties, when dehydrated crystalline aluminosilicate (zeolite) having a pore size of 5 to 10 angstrom is used as a catalyst for the reaction between alcohol having 1 to 18 carbon atoms and ammonia, mono and diamine are It is disclosed that it is produced preferentially over triamine. Further, natural zeolite and synthetic zeolite are shown as types of zeolite suitable for the above-mentioned reaction. As natural zeolite, faujas stone, analsite,
Clinoptile light, ferrierite, chabazite,
Gmelinite, levinite, erionite and mordenite are disclosed as suitable. As the synthetic zeolite, X-type, Y-type, A-type and the like are disclosed to be suitable (USP., 3,384,667; 19).
68 years).

A method in which methanol and ammonia are mixed at a specific ratio and reacted in the presence of a catalyst such as mordenite to obtain a large amount of monomethylamine (Japanese Patent Laid-Open No. 56-1).
13747) and a crystalline aluminosilicate selected from Na mordenite to disproportionate monomethylamine to obtain dimethylamine with high selectivity (JP-A-56-46).
846) method is also disclosed. USP. , 3,
A method of using a naturally occurring mineral for mordenite used in the same manner as 384,667 (JP-A-57-16944).
4), a method of using mordenite ion-exchanged with lanthanum ions as a catalyst (JP-A-58-49340), and a method of using mordenite having an ion exchange amount of an alkali metal within a specific range (JP-A-59). -21005
0), a method using steam-treated mordenite as a catalyst (JP-A-59-227841), a method using a low binder content A-type zeolite as a catalyst (JP-A-58-69846) or Rho-type (ZK- 5) A method of using zeolite as a catalyst is also disclosed.

When the zeolite type catalyst is used by the above method, the amount of trimethylamine produced can be suppressed. Furthermore, in order to make the amount of trimethylamine produced zero or substantially zero, the pores of mordenite are formed into silicon tetrachloride. There is also known a method of using a catalyst modified by the CVD treatment of JP-A No. 03-262540; J. Ca.
tal. 131, 482 (1991)). A method in which a compound obtained by precipitating and modifying a compound of silicon, aluminum, phosphorus or boron on chabazite, erionite, ZK-5 and Rho type zeolite is used as a catalyst.
-254256; USP. , 4,683,334) to reduce the amount of trimethylamine produced. Also,
There is also known a method of reacting alcohol and ammonia with a non-zeolitic molecular sieve SAPO as a catalyst to give an alkylamine (Japanese Patent Laid-Open No. 02-734).

[0005]

As described above, by using various conventionally disclosed zeolite-based catalysts in the reaction of methanol and ammonia, the production amount of trimethylamine, which is in low demand, can be suppressed to a low level. It is now possible to increase the amount of dimethylamine, which contains a lot of substances. However, even if these zeolite compounds are used as catalysts, the production ratio of trimethylamine is usually 2
It can be reduced to 0% and at most about 10%. If the amount of trimethylamine produced can be reduced to about 3 to 5%, it is not necessary to recycle trimethylamine, which is in low demand, to the reaction system to disproportionate, and the manufacturing process can be simplified to reduce utility such as steam.

As a method for reducing the amount of trimethylamine produced to several percent, CVD (c
chemical vapor position)
Discloses a method of using the deposited material as a catalyst (Japanese Patent Application Laid-Open No. 03-262540; USP.,
5,137,854). However, although this method can be easily carried out in the laboratory, it is difficult to industrially produce a large amount of catalyst. The object of the present invention is to
A method for producing methylamine which does not have the above-mentioned problems, that is, the amount of dimethylamine and monomethylamine obtained is increased, and the amount of trimethylamine produced is kept low at 3 to 5%, more preferably 1 to 2%. It is to provide an industrial production method of amine.

[0007]

Means for Solving the Problems The present inventor has conducted various studies on a method for industrially producing methylamine which suppresses the amount of trimethylamine produced to a very low level and obtains a large amount of dimethylamine. As a result, if mordenite treated in a liquid layer using an alcohol solution in which alkoxysilanes are dissolved is used as a catalyst used when reacting methanol and ammonia, the production amount of trimethylamine is reduced to 5% or less. They have found that they can be retained, and have completed the present invention. That is, the present invention is a method for producing methylamines, which comprises reacting mordenite with methanol in the presence of a catalyst treated with an alcohol solution of tetraalkoxyorthosilicate in producing methylamines by reacting methanol with ammonia. is there.

Conventional mordenite, which has been frequently used in the reaction for producing methylamines from methanol and ammonia, is a crystalline aluminosilicate represented by Na ₈ (Al ₈ Si ₄₀ O ₉₆ ) / 24H ₂ O ( ATLAS
OF ZEOLITE STRUCTURE TYPE
S, W. M. Meier and D.M. H. Olso
n, 1987, Butterworths). _{Further, Me1 / n (AlSi 5 O} 12) · 3H 2 O If (Me represents an n-valent alkali or alkaline earth atom or hydrogen) are labeled with (JP 57-16944
4; JP-A-59-21050, etc.). In either case, normal or synthetic mordenite (Norton Zeolon, UCC LZM
-8, CM of La Grande Paroisse-
180 or the like), the Si / Al ratio is 5, and the (silica / alumina) ratio (SiO ₂ / Al ₂ O ₃ ) is 10
However, those having a (silica / alumina) ratio of more than 11 are not known except for special synthetic products.

However, the mordenite used in the method of the present invention has a (silica / alumina) ratio of 10 or more. If the (silica / alumina) ratio is around 10, ordinary synthetic or natural mordenite is used. Those having a (silica / alumina) ratio of 11 or more can be obtained by subjecting ordinary mordenite to a conventional method such as acid treatment, or (10 + n) Na ₂ O (sodium silicate solution and aluminum chloride solution). 3 + n) Al ₂ O ₃ (87-
n) SiO ₂ (where n is 0 to 4) is prepared by preparing a gel-like slurry and subjecting this to hydrothermal synthesis at 130 ° to 250 ° C. for 10 hours to several days (Am. Minera).
l. 65, 1012 (1972)). When the hydrogen ion type mordenite used is usually used, a high catalytic activity is often obtained.

Since synthetic or natural mordenite is obtained as Na ion type, it is converted into hydrogen ion type by thermal decomposition after ion exchange with ammonium ion. Alternatively, Na-type mordenite is converted to a hydrogen ion type by treating with 1 to 3 normal mineral acid. Na in mordenite
A content of 0.2 wt% or less shows high catalytic activity. However, if the Na content is 3 wt% or less, practical activity can be obtained. The content of K is preferably 5 wt% or less in terms of catalytic activity. The silicon compound used in the treatment of mordenite is silicon alkoxide Si (OR).
₄ , R represents a lower alkyl group such as methyl, ethyl or isopropyl. Particularly, tetramethyl orthosilicate, tetraethyl orthosilicate and the like are frequently used in the method of the present invention. These silicon alkoxides can be easily obtained as industrial raw materials and can be easily produced by reacting silicon tetrachloride with alcohols such as methanol or ethanol.

The treatment of mordenite is carried out in a liquid layer, but it is essential to use an alcoholic solvent as a solvent for dissolving alkoxide of silicon. When a solvent other than alcohol is used as the solvent, the amount of trimethylamine produced cannot be kept sufficiently low. For example, in the specification of JP-A No. 61-254256, a silicon compound, for example, chabazite treated with tetraethyl orthosilicate, is used as a catalyst for the purpose of suppressing the production of trimethylamine in the reaction between methanol and ammonia.
I use erionite. The above-mentioned specification discloses the use of a non-polar organic solvent such as toluene, benzene or hexane as a preferable solvent for dissolving the silicon compound. On the contrary, in the method of the present invention, when benzene, toluene or the like is used as the solvent for the silicon compound, the amount of trimethylamine produced is only about 8 to 10%, and the amount of trimethylamine produced is 5% or less. It cannot be reduced. In the method of the present invention, the alcohol used as the solvent is often a lower alcohol such as methanol, ethanol or isopropyl alcohol. In addition, compounds such as methyl cellosolve and ethyl cellosolve may be used as a solvent. Further, if the solvent used has a large amount of water, the silicon alkoxide is hydrolyzed and wasted, so it is preferable that the amount of water in the solvent is as small as possible. It is also preferable that the mordenite used for the treatment of the silicon compound is in a sufficiently dry state, and the water content in the mordenite needs to be kept at 4 wt% or less. The silicon alkoxide is used by dissolving it in the alcohol solvent described above, and the amount of dissolution is 0.1 to 50.
The range of wt%, especially 1 to 30 wt% is often used. Mordenite is suspended in the aforementioned alcohol solution of silicon alkoxide to deposit and fix the silicon compound on the mordenite. The amount of silicon alkoxide used for the mordenite to be treated is 3 to the weight of the mordenite.
The range of 50%, especially 5 to 30% is often used.

The temperature at which the treatment is carried out is from room temperature to the boiling point of the alcohol solution, and the range of 20 ° to 90 ° C. is often used. When the treatment is carried out under pressure, the treatment temperature can be further increased. The time required for the treatment mainly varies depending on the treatment temperature, but it is 8 hours to 100 near room temperature.
At 60 ° to 90 ° C., the range of 1 to 20 hours is often used. The mordenite after the treatment is separated from the treatment solution by a conventional method such as filtration or centrifugation and heated under an atmosphere of an inert gas such as nitrogen, or heated under reduced pressure to adhere or adsorb the organic solvent or the like. Remove. Then, heat treatment is performed at 400 ° to 600 ° C. in an air or oxygen atmosphere to obtain a catalyst.

The above-described treatment of mordenite with a silicon compound may be carried out not only once but also repeatedly.
Multiple treatments with silicon compounds (eg 2-5 times)
By using the repeated catalyst, the amount of trimethylamine by-produced can be reduced to about 1%. If the starting mordenite is in the form of granules or tablets, it is directly used as a catalyst. When it is in the form of powder, it is extruded or tableted by a conventional method to obtain a catalyst.

The reactants used in the process of the invention are ammonia or a mixture of methanol and dimethyl ether and ammonia. The molar ratio of ammonia to methanol is 0.5 or more, preferably 1 to 10, and the range of 1 to 4 is often used. The amount of reaction gas supplied to the catalyst layer is in the range of 200 to 20000 / h in terms of space velocity SV,
The reaction pressure is 1 to 30 kg / cm ² G.I. Is. When carrying out the reaction, the temperature of the catalyst layer is often 250 to 450 ° C, preferably 250 to 350 ° C.

The reactor used to carry out the process of the present invention is a conventional fixed bed or fluidized bed reactor. Since this reaction is an exothermic reaction of about 14 KCal / mol, when using a fixed bed reactor, it is important to keep the heat of reaction in mind in order to keep the amount of trimethylamine produced at a low level. For this purpose, it is preferable to employ a multitubular reactor. The tube diameter of the multitubular reactor is often in the range of 1 to 3 inches. Methylamines are isolated and obtained by an ordinary separation and purification device from the outlet gas of the reaction device. However, since the amount of trimethylamine produced is 5% or less in the method of the present invention, the separation process of trimethylamine becomes small and trimethylamine is reacted. The whole manufacturing process is simplified by eliminating the need for a system recycling process. The present invention will be described below with reference to Examples and Comparative Examples.

[0016]

【Example】

Example 1 150 g of synthetic mordenite was suspended in 1 liter of an aqueous 0.5 N ammonium nitrate solution, heated on an oil bath and refluxed for 4 hours. The mordenite was separated by filtration, a new 0.5N ammonium nitrate aqueous solution was added, and the same operation was repeated 3 times in total, filtered, washed with water to obtain ammonium type mordenite, and dried and calcined at 600 ° C. to obtain H-mordenite. The Na content in the mordenite was 0.13 wt%. It was stored in a dry sealed container. 60 g of the above H-mordenite was suspended in a solution of 7.5 g of tetraethoxy orthosilicate dissolved in 100 g of ethanol, and the suspension was placed at 60 ° C. for 8 hours.
Heated and shaken for hours. The mordenite was separated by filtration, washed with ethanol, heated in a nitrogen stream and heated at 350 ° C. for 3 hours, and then heated in an air stream to 500 ° C. and heated for 5 hours. This was tablet-molded into tablets each having a size of 3 mm × 3 mm and used as a catalyst. 40 g (64 ml) of the above catalyst was filled in a stainless steel reaction tube having an inner diameter of 1 inch and heated from the outside in a sand fluidized bath. 18 g of methanol / hour and 18.7 g of ammonia / hour were injected into the reaction tube through a vaporizer to make the catalyst layer temperature 310 ° C. and the pressure 19 kg / cm ² G. It was made to react with. After 20 hours from the start of the reaction, the components at the outlet of the reaction tube were collected and analyzed. The conversion of methanol was 90%, the selectivity of monomethylamine was 33.3%, the selectivity of dimethylamine was 63%, and the selectivity of trimethylamine was 3.7%. Met.

Comparative Example 1 60 g of the H-mordenite prepared in Example 1 was suspended in a solution of tetraethoxy orthosilicate 7.5 in 100 g of toluene and the mixture was heated and shaken at 60 ° C. for 8 hours.
The mordenite was filtered off, washed with benzene, heated in a nitrogen stream and heated at 350 ° C. for 3 hours, then in an air stream at 50.
It heated up to 0 degreeC and heated for 5 hours. This is tablet-molded and 3m
Tablets of m × 3 mm were used as a catalyst. 40 g (65 ml) of the above catalyst was filled in a stainless steel reaction tube having an inner diameter of 1 inch, and the synthetic reaction of methylamine from methanol and ammonia was tested under the same reaction conditions as in Example 1. After 20 hours from the start of the reaction, the reaction tube outlet components were collected and analyzed, and the results were as follows: methanol conversion 89%, monomethylamine selectivity 30.1%, dimethylamine selectivity 60.3%, trimethylamine selectivity. It was 9.6%.

Example 2 110 g of natural zeolite (having a mordenite content of about 70%) having a particle size of 2 to 4 mm was put into 1 liter of 2N hydrochloric acid, and 50
Shake for 10 hours at ℃. Zeolite was filtered off, then added to 1 l of fresh 1N hydrochloric acid, and shaken at 50 ° C. for another 10 hours. The zeolite was filtered off, washed with water and dried, and then heated to 500 ° C. to produce H-mordenite. The produced zeolite was almost completely H type, and the Na content was 0.15%. The above H-mordenite 5 was added to 100 g of a methanol solution containing 7 g of tetramethoxy orthosilicate dissolved therein.
0 g was added and shaken at room temperature (20 ° to 25 ° C.) for 60 hours. The H-mordenite was filtered off, washed with methanol, heated in a nitrogen stream and heated at 350 ° C. for 2 hours, and then heated in an air stream to 500 ° C. and heated for 4 hours. The obtained granular zeolite was directly used as a catalyst in the reaction. The catalyst 4 is attached to a stainless steel reaction tube having an inner diameter of 1 inch.
It was filled with 0 g (60 ml) and heated from the outside in a sand fluidized bath. 15 g of methanol / hour, 16 g of ammonia / hour
At a rate of 310 ° C and a pressure of 1
The reaction was carried out at 9 kg / cm ² G. After 30 hours from the start of the reaction, the result of analyzing the components at the outlet of the reaction tube was 90% conversion of
%, Monomethylamine selectivity was 34.4%, dimethylamine selectivity was 62.1%, and trimethylamine selectivity was 3.5%.

Comparative Example 2 7 g of tetramethoxy orthosilicate was added to 100 g of benzene.
50 g of the granular H-type mordenite of Example 2 was added to the solution dissolved in g and shaken at room temperature (20 ° to 25 ° C.) for 60 hours. H-mordenite was filtered off, washed with benzene, heated to 350 ° C. in a nitrogen stream and heated for 3 hours, and then heated to 500 ° C. in an air stream for 4 hours. The obtained granular zeolite was directly used as a catalyst in the reaction. 40 g (61 ml) of the above-mentioned granular catalyst was filled in a stainless steel reaction tube having an inner diameter of 1 inch, and the catalyst layer was heated from the outside in a sand fluidized bath. 15 g of methanol per hour and 16 g of ammonia per hour were injected into the reaction tube through the evaporator at a rate of 3 g.
The reaction was carried out at 10 ° C. and a pressure of 19 kg / cm ² G. Reaction start 30
When the reaction tube outlet component was analyzed after a lapse of time, the conversion of methanol was 90% and the selectivity of monomethylamine was 28.4.
%, The selectivity of dimethylamine was 62.5%, and the selectivity of trimethylamine was 9.1%.

Example 3 200 g of granular mordenite (2 to 3 mm) was gently stirred in 2 l of 0.2 N KCl aqueous solution for 4 hours, washed with water and separated. Then, 4 in 2 l of 1.2 N HCl aqueous solution
The granular mordenite was gently stirred for a while to separate the mordenite by filtration, 2 l of a new 1.2N HCl aqueous solution was added, and the mixture was allowed to stand overnight. This was washed with water, filtered, dried and calcined at 500 ° C. to obtain H-mordenite. The obtained H-mordenite had a Na content of 0.11 wt% and a K content of 2.3 wt%.
50 g of the mordenite was taken, and the mixture was placed in a solution of 9 g of tetraethyl orthosilicate dissolved in 70 g of methanol and shaken at room temperature for 6 hours. The solid is filtered off, and in a nitrogen stream 2
A silylation treatment was carried out by baking at 50 ° C. for 1 hour and at 500 ° C. for 2 hours in an air atmosphere. Further, the above silylation treatment was repeated 4 times in total to prepare a catalyst. 40 g of the obtained catalyst
The same apparatus as in Example 1 was used to test the methylamine synthesis reaction under the same reaction conditions. When the product was quantified 100 hours after the start of the reaction, the conversion of methanol was 91%, the selectivity of monomethylamine was 35.6%, the selectivity of dimethylamine was 63.4%, and the selectivity of trimethylamine was 1.0%. .

[0021]

EFFECTS OF THE INVENTION When methylamines are produced by the reaction of methanol and ammonia, by using mordenite produced by a specific method, which has been treated with an alcohol solution of silicon alkoxide, as a catalyst, The generation rate can be reduced to a low value of 5% or less. This makes it possible to omit the step of recycling and disproportionating trimethylamine to the reaction system, simplifying the methylamine production process, and reducing the amount of use.

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[Procedure amendment]

[Submission date] August 24, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

Means for Solving the Problems The present inventor has conducted various studies on a method for industrially producing methylamine which suppresses the amount of trimethylamine produced to a very low level and obtains a large amount of dimethylamine. As a result, if mordenite treated in a liquid layer using an alcohol solution in which alkoxysilanes are dissolved is used as a catalyst used when reacting methanol and ammonia, the production amount of trimethylamine is reduced to 5% or less. They have found that they can be retained, and have completed the present invention. That is, the present invention is a method for producing methylamines, which comprises reacting mordenite with methanol in the presence of a catalyst treated with an alcohol solution of tetraalkoxysilane to produce methylamines by reacting methanol with ammonia. .

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

Since synthetic or natural mordenite is obtained as Na ion type, it is converted into hydrogen ion type by thermal decomposition after ion exchange with ammonium ion. Alternatively, Na-type mordenite is converted to a hydrogen ion type by treating with 1 to 3 normal mineral acid. Na in mordenite
A content of 0.2 wt% or less shows high catalytic activity. However, if the Na content is 3 wt% or less, practical activity can be obtained. The content of K is preferably 5 wt% or less in terms of catalytic activity. The silicon compound used for the treatment of mordenite is a silicon alkoxide Si (OR) ₄
Wherein R represents a lower alkyl group such as methyl, ethyl or isopropyl. Especially tetramethoxysila
And tetraethoxysilane are often used in the method of the present invention. These silicon alkoxides are easily obtained as industrial raw materials, and can be easily produced by reacting silicon tetrachloride with alcohols such as methanol or ethanol.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

The treatment of mordenite is carried out in a liquid layer, but it is essential to use an alcoholic solvent as the solvent for dissolving the silicon alkoxide . When a solvent other than alcohol is used as the solvent, the amount of trimethylamine produced cannot be kept sufficiently low. For example, the silicon compound to the catalyst is in the specification of JP 61-254256 to use in inhibiting the production of trimethylamine in the reaction of methanol and ammonia purposes, for example, Te
Tiger silane treated chabazite, using erionite, and the like. The above-mentioned specification discloses the use of a non-polar organic solvent such as toluene, benzene or hexane as a preferable solvent for dissolving the silicon compound. On the contrary, in the method of the present invention, when benzene, toluene or the like is used as the solvent for the silicon compound, the amount of trimethylamine produced is only about 8 to 10%, and the amount of trimethylamine produced is 5% or less. It cannot be reduced.
In the method of the present invention, the alcohol used as the solvent is often a lower alcohol such as methanol, ethanol or isopropyl alcohol. In addition, compounds such as methyl cellosolve and ethyl cellosolve may be used as a solvent. Further, if the solvent used has a large amount of water, the silicon alkoxide is hydrolyzed and wasted, so it is preferable that the amount of water in the solvent is as small as possible. Further, it is preferable that the mordenite used for the treatment of the silicon compound is also in a sufficiently dry state, and the water content in the mordenite needs to be maintained at 4 wt% or less. The silicon alkoxide is used by dissolving it in the alcohol solvent described above, and the amount of dissolution is 0.1 to 50.
The range of wt%, especially 1 to 30 wt% is often used. Mordenite is suspended in the aforementioned alcohol solution of silicon alkoxide to deposit and fix the silicon compound on the mordenite. The amount of silicon alkoxide used for the mordenite to be treated is 3 to the weight of the mordenite.
The range of 50%, especially 5 to 30% is often used.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

[0016]

Example 1 150 g of synthetic mordenite was added to 0.5 N ammonium nitrate.
Suspension in 1 liter of aqueous solution, heated on an oil bath and refluxed for 4 hours.
It was The mordenite was filtered out and a new 0.5N ammonium nitrate was added.
Add an aqueous solution of nickel and repeat the same operation a total of 3 times.
Separately, wash with water to make ammonium type mordenite,
After drying, it was baked at 600 ° C. to obtain H-mordenite. Mole
The Na content in the denite was 0.13 wt%. This
It was stored in a dry sealed container.Tetraethoxysilane
A solution of 7.5 g in 100 g of ethanol was added to the above solution.
Suspend 60 g of H-mordenite and heat at 60 ° C for 8 hours
Shaken. After separating the mordenite by filtration and washing with ethanol
Heat in a nitrogen stream and heat at 350 ° C for 3 hours, then air
The temperature was raised to 500 ° C. in an air stream and heated for 5 hours. Hit this
Tablets are formed into 3mm x 3mm tablets and used as a catalyst
It was 40 g (64 ml) of the above catalyst was passed through a 1-inch inner diameter column.
Fill the reaction tube made of stainless steel with a fluidized sand bath from the outside.
Heated. 18 g of methanol per hour, ammonia per hour
18.7 g of pressure was applied to the reaction tube through the vaporizer to make the catalyst layer temperature 3
10 ℃, pressure 19Kg / cm²G. It was made to react with. Reaction start 2
After 0 hours, the reaction tube outlet components were collected and analyzed.
90% conversion of tanol, selectivity of monomethylamine 3
3.3%, dimethylamine selectivity 63%, trimethyl
The selectivity of amine was 3.7%.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

Comparative Example 1 60 g of the H-mordenite prepared in Example 1 was added to tetrae
Toxisilane 7.5 was suspended in a solution prepared by dissolving 100 g of toluene and heated and shaken at 60 ° C. for 8 hours. After removing the mordenite by filtration and washing with benzene, the temperature was raised in a nitrogen stream to 35
The mixture was heated at 0 ° C. for 3 hours, then heated to 500 ° C. in an air stream and heated for 5 hours. This is tablet-molded and 3mm x 3mm
And used as a catalyst. 40 g of the above catalyst
(65 ml) was filled in a stainless steel reaction tube having an inner diameter of 1 inch, and the synthetic reaction of methylamine from methanol and ammonia was tested under the same reaction conditions as in Example 1. After 20 hours from the start of the reaction, the reaction tube outlet components were collected and analyzed. The results were that the conversion of methanol was 89%, the selectivity of monomethylamine was 30.1%, and the selectivity of dimethylamine was 6%.
The selectivity was 0.3% and trimethylamine was 9.6%.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

Example 2 110 g of natural zeolite (having a mordenite content of about 70%) having a particle size of 2 to 4 mm was put into 1 liter of 2N hydrochloric acid, and 50
Shake for 10 hours at ℃. Zeolite was filtered off, then added to 1 l of fresh 1N hydrochloric acid, and shaken at 50 ° C. for another 10 hours. The zeolite was filtered off, washed with water and dried, and then heated to 500 ° C. to produce H-mordenite. The produced zeolite was almost completely H type, and the Na content was 0.15%. 50 g of the above H-mordenite was added to 100 g of a methanol solution in which 7 g of tetramethoxysilane was dissolved and shaken at room temperature (20 ° to 25 ° C.) for 60 hours. H
-The mordenite was separated by filtration, washed with methanol, heated in a nitrogen stream and heated at 350 ° C for 2 hours, and then heated in an air stream to 500 ° C and heated for 4 hours. The obtained granular zeolite was directly used as a catalyst in the reaction. 40 g of the catalyst (60 m) in a stainless steel reaction tube with an inner diameter of 1 inch
l) was filled and heated from the outside in a fluidized sand bath. Methanol (15 g / hr) and ammonia (16 g / hr) were introduced into the reaction tube through the evaporator under pressure and reacted at 310 ° C. and a pressure of 19 kg / cm ² G. After 30 hours from the start of the reaction, the results of analyzing the components at the outlet of the reaction tube showed that the conversion of methanol was 90%, the selectivity of monomethylamine was 34.4%, and the selectivity of dimethylamine was 6%.
The selectivity was 2.1% and the selectivity of trimethylamine was 3.5%.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

Comparative Example 2 50 g of the granular H-type mordenite of Example 2 was added to a solution prepared by dissolving 7 g of tetramethoxysilane in 100 g of benzene and shaken at room temperature (20 ° -25 ° C.) for 60 hours.
H-mordenite was filtered off, washed with benzene, heated to 350 ° C. in a nitrogen stream and heated for 3 hours, and then heated to 500 ° C. in an air stream for 4 hours. The obtained granular zeolite was directly used as a catalyst in the reaction. Inner diameter 1
Inch stainless steel reaction tube with 40 g of the granular catalyst
(61 ml) was charged and the catalyst layer was heated from the outside in a fluidized sand bath. 15 g of methanol / hour and 16 of ammonia / hour
The mixture was pressed into the reaction tube through the evaporator at a rate of g and reacted at 310 ° C. and a pressure of 19 kg / cm ² G. When the reaction tube outlet component was analyzed 30 hours after the start of the reaction, the conversion of methanol was 90
%, Monomethylamine selectivity was 28.4%, dimethylamine selectivity was 62.5%, and trimethylamine selectivity was 9.1%.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

Example 3 200 g of granular mordenite (2 to 3 mm) was gently stirred in 2 l of 0.2 N KCl aqueous solution for 4 hours, washed with water and separated. Then, 4 in 2 l of 1.2 N HCl aqueous solution
The granular mordenite was gently stirred for a while to separate the mordenite by filtration, 2 l of a new 1.2N HCl aqueous solution was added, and the mixture was allowed to stand overnight. This was washed with water, filtered, dried and calcined at 500 ° C. to obtain H-mordenite. The obtained H-mordenite had a Na content of 0.11 wt% and a K content of 2.3 wt%.
Taking 50 g of the mordenite, tetraethoxysilane 9
6g at room temperature in a solution of 70g methanol
I quivered for hours. The solid was filtered off and calcined in a nitrogen stream at 250 ° C. for 1 hour and in an air atmosphere at 500 ° C. for 2 hours to carry out a silylation treatment. Further, the above silylation treatment was repeated 4 times in total to prepare a catalyst. Using 40 g of the obtained catalyst, the methylamine synthesis reaction was tested in the same apparatus as in Example 1 under the same reaction conditions. When the product was quantified 100 hours after the reaction was started, the conversion of methanol was 91%, the selectivity of monomethylamine was 35.6%, the selectivity of dimethylamine was 6%.
The selectivity was 3.4% and the selectivity for trimethylamine was 1.0%.

Claims (1)

[Claims] 1. A method for producing methylamines, which comprises reacting mordenite with methanol in the presence of a catalyst treated with an alcohol solution of tetraalkoxyorthosilicate in producing methylamines.