KR101988374B1 - Method of preparation of ethylamine or acetonitrile by reductive amination of ethanol - Google Patents

Abstract

More particularly, the present invention relates to a catalyst capable of efficiently producing ethylamine or acetonitrile at a normal pressure or lower by reacting ethanol with ammonia, and more particularly, to a catalyst for the production of ethylamine Or acetonitrile, a method for producing the same, and a process for producing ethylamine using the same.

Description

[0001] The present invention relates to a process for preparing ethylamine or acetonitrile by reductive amination of ethanol on a Ni / Al2O3 catalyst,

The present invention relates to the production of ethylamine or acetonitrile, and more particularly to the production of ethylamine or acetonitrile using Ni / Al ₂ O ₃ A method of producing ethylamine which can efficiently produce ethylamine under normal pressure by reacting ethanol with ammonia in the presence of hydrogen on a catalyst, and a method of producing ethylamine by reacting Ni / Al ₂ O ₃ The present invention relates to a method for producing acetonitrile, which can efficiently produce acetonitrile at normal pressure or below by reacting ethanol with ammonia on a catalyst.

Ethylamines are important intermediates and raw materials in a variety of fields such as chemicals, pharmaceuticals, agriculture, rubber, and solvents. It is also widely used in various fields as an intermediary of production of refined chemical products and mainly used for herbicides, pharmaceuticals, fibers, insecticides, antibiotics, synthesis of corrosion inhibitors, and synthesis of epoxy hardeners.

Ethylamine synthesis methods include amination using ethanol or acetaldehyde, hydrogenation of acetonitrile, and hydroamineation of olefins. The amination reaction of ethanol has been studied for a long time due to its high synthesis efficiency, and it has received constant interest as an environmentally friendly reaction. In addition, it can be synthesized under relatively mild reaction conditions as compared with other reactions requiring high temperature and high pressure, so that ethylamine can be produced at low production cost.

The amination reaction of ethanol proceeds through the following successive steps. The carbonyl compound formed through the ethanol oxidation reaction acts as an initiator of the reaction, and the resulting carbonyl compound undergoes a condensation process to react with the reactant ammonia to form an intermediate imine. Then, monoethylamine (MEA) is formed through the hydrogenation reaction, and diethylamine (DEA) and triethylamine (TEA) are formed through the continuous reaction.

The catalysts used for the reductive amination of ethanol mainly use precious metal catalysts such as Pt, Pd and Rh which are used for hydrogenation and dehydrogenation reactions. However, since precious metal catalysts can not be continuously used, catalyst researches have been conducted to replace them. Catalysts such as alkali metals or transition metal complexes, particularly transition metal catalysts such as Ni, Co and Fe, exhibit catalytic activities similar to those of noble metal catalysts, and are readily available as alternative catalysts.

As a prior art related to the catalyst for the production of ethylamine, U.S. Patent No. 4255357 (Publication date: 1981.03.10.) Describes the production of ethyl amines from ethanol using alumina or a catalyst prepared by impregnating a diatomaceous earth support with nickel or cobalt Is described. The patent literature mentions that a catalytically active substance such as cobalt, nickel or the like is supported on a support material selected from among alumina or diatomaceous earth supports and cobalt among the active materials used is said to be more useful for the amination process .

However, Fischer et al. (A. Fischer, et al) proposed a process for the amination of 1,3-propanediol based on cobalt catalysts (J. Catal. 183, (1999) 373) The amination reaction of 1,3-propanediol using cobalt-iron and cobalt-lanthanum catalyst is carried out under the conditions of a reaction temperature of 195 ° C. and a high pressure of 135 bar, the yield of the desired diamine product is only 35% And the low yield of the product under the condition of economical efficiency was an undesirable catalytic reaction process.

Japanese Laid-Open Patent Application No. 2015-501804 (Laid-open date: 2015.01.19) describes a method for producing ethylamine from ethanol using a heterogeneous catalyst containing copper, nickel or cobalt. In this document, catalysts in which 34 wt% of cobalt is supported on Al ₂ O ₃ have an ethylamine selectivity of greater than 90% under reaction conditions of 185 - 188 ° C and 66 bar pressure. This catalyst has a dangerous disadvantage because it reacts under high pressure conditions.

On the other hand, acetonitrile (ACN), also known as methyl cyanide, is contained in small quantities in the coal wastewater of coal and coal. Such acetonitrile is important as a raw material for the organic synthesis industry, and is used for the synthesis of acetophenone, ethylamine, vitamin B and the like, and is also used as a solvent for acrylonitrile-based fibers and as a solvent for refining petroleum hydrocarbons.

The production method of acetonitrile is prepared by amination using ethanol or acetylene, and the amination reaction of ethanol is an eco-friendly reaction as described above, and the reaction is relatively mild under the reaction conditions requiring high temperature and high pressure It is possible to produce acetonitrile at a low production cost.

As a conventional technique related to a catalyst for producing acetonitrile, Y Hu et al. Disclosed a method for producing acetonitrile through a reductive amination reaction of ethanol using a Cu / γ-Al ₂ O ₃ catalyst (Reac Kinet Mech Cat (2012) 106: 127-139). The reaction must be carried out at a high temperature, and there is a problem that a large amount of ammonia is required to be used compared to ethanol.

In addition, catalysts using Co, Ni and the like have been developed, but there have been problems in that they are carried out under high temperature and high pressure reaction conditions, and that the conversion of ethanol or the selectivity of acetonitrile is inferior.

Therefore, there is a continuing need for research and development of a new catalyst capable of producing ethylamine or acetonitrile using the reductive amination reaction of ethanol.

U.S. Patent No. 4255357 (Published on January 3, 1981) Japanese Laid-Open Patent Publication No. 2015-501804 (published on 2015.01.19)

The main object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide a Ni / Al ₂ O ₃ The present invention provides a method for producing ethylamine or acetonitrile by reducing amination of ethanol which can maintain a high catalytic activity under normal pressure for a long period of time using a catalyst and has a high yield for the desired ethylamine or acetonitrile have.

According to an aspect of the present invention, there is provided a method of manufacturing a metal-supported catalyst, comprising the steps of: (a) (b) activating the catalyst of step (a) in contact with hydrogen; (c) mixing the predetermined amount of ethanol and ammonia in the presence of hydrogen in step (b) to form an amination reaction mixture, wherein the partial pressure of hydrogen in step (c) is 4 times Or less of the total amount of the ethylamine.

According to an embodiment of the present invention, the metal-supported catalyst may be Ni / Al ₂ O ₃ .

According to an embodiment of the present invention, the Ni / Al ₂ O ₃ may be prepared by mixing (d-1) a nickel precursor aqueous solution with a support compound and stirring the mixture; (d-2) drying the mixture of step (d-1); And (d-3) firing the dried mixture in the step (d-2).

According to one embodiment of the present invention, the support compound may be at least one selected from the group consisting of alumina, silica, alumina-silica, and zirconia.

Also, according to one embodiment of the present invention, the nickel precursor may be nickel chloride, nickel acetate, nickel nitrate and mixtures thereof

Also, according to an embodiment of the present invention, the stirring in the step (d-1) may be performed at room temperature.

Also, according to an embodiment of the present invention, the drying in step (d-2) may be performed at 50 to 120 ° C.

Also, according to an embodiment of the present invention, the firing in the step (d-3) may be performed at 400 to 600 ° C under an air flow at a heating rate of 1 to 3 ° C min ^-1 .

Also, according to an embodiment of the present invention, the reaction of step (c) may be carried out at a pressure lower than the atmospheric pressure.

Also, according to an embodiment of the present invention, the Ni loading amount of the Ni / Al ₂ O ₃ may be 5 to 25 wt%, and preferably the nickel content may be 10 wt%, based on the total weight of the catalyst.

Also, according to an embodiment of the present invention, the partial pressure ratio of ammonia / ethanol in the amination reaction may be 0.5 to 5.

According to an embodiment of the present invention, the partial pressure ratio of hydrogen / ethanol in the amination reaction may be 4 to 20.

According to an embodiment of the present invention, the space velocity in the amination reaction may be 0.1 to 2.0 h ^-1 and the temperature may be 150 to 250 ° C.

According to another embodiment of the present invention, there is also provided a process for preparing a metal supported catalyst, comprising the steps of: (i) preparing a metal supported catalyst; (ii) activating the catalyst of step (i) in contact with hydrogen; (iii) mixing a predetermined proportion of ethanol and ammonia in the step (ii) to form an amination reaction mixture, wherein the partial pressure of ammonia in step (iii) is 1 to 7 times the partial pressure of ethanol The present invention provides a method for producing acetonitrile by reductive amination reaction of ethanol.

According to another embodiment of the present invention, the metal supported catalyst is the same as described above, and the reaction of step (iii) may be carried out at normal pressure or below.

According to another embodiment of the present invention, the space velocity and temperature in the amination reaction may be the same as described above.

The method of producing ethylamine or acetonitrile by reductive amination of ethanol according to the method of the present invention shows excellent selectivity to ethylamine and acetonitrile even under normal pressure unlike the conventional method, The low inactivation results in a high ethanol conversion rate and a high selectivity of ethylamine and acetonitrile over a long period of time.

The Ni / Al ₂ O ₃ catalyst according to the present invention is characterized in that the selectivity of ethylamine and acetonitrile can be controlled according to the reaction conditions. Therefore, the production of ethylamine or acetonitrile It has an easy effect.

1 is a graph showing the conversion of ethanol and the selectivity of ethylamine of the catalysts of Examples 1 to 5 according to the present invention.
2 is a graph showing the distribution between conversion and selectivity of each product under the same reaction conditions of Examples 1 to 5 according to the present invention.
FIG. 3 is a graph showing the experimental results of amination reaction activity according to the space velocity of Example 2. FIG.
4 is a graph showing the amination activity of the catalyst of Example 2 according to the present invention in accordance with changes in partial pressure of ammonia.
5 is a graph showing the experimental results of the amination reaction activity according to the hydrogen partial pressure change of the catalyst of Example 2 according to the present invention.
FIG. 6 is a graph showing the experimental results of amination reaction activity according to the temperature condition change of Example 2 according to the present invention. FIG.
7 is a graph showing the amination activity of the catalyst of Example 2 according to the present invention in the presence of ammonia or hydrogen.
8 is a graph showing the stability test results of the catalyst of Example 2 according to the present invention over time.
FIG. 9 is a graph showing the amination reaction activity test results according to the ammonia partial pressure change of the catalyst of Example 2 according to another embodiment of the present invention. FIG.
FIG. 10 is a graph showing the amination activity of the catalyst of Example 2 according to another embodiment of the present invention when the ratio of ammonia / ethanol is 2/1, (B) shows the conversion of ethanol and the selectivity of products according to temperature conditions.
FIG. 11 is a graph showing the amination reaction activity test result according to the change of temperature condition when the ratio of ammonia / ethanol of the catalyst of Example 2 according to another embodiment of the present invention is 3/1. FIG. 11 (a) (B) shows the conversion of ethanol and the selectivity of products according to temperature conditions.
12 is a graph showing the amination activity of the catalyst of Example 2 according to another embodiment of the present invention, wherein (a) shows the conversion rate of ethanol according to the space velocity, (b) Shows the conversion of ethanol and the selectivity of products according to the space velocity.
13 is a graph showing the stability test results of the catalyst of Example 2 according to another embodiment of the present invention over time.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings attached hereto. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

According to one aspect of the present invention, there is provided a process for preparing a metal supported catalyst, comprising: (a) preparing a metal supported catalyst; (b) activating the catalyst of step (a) in contact with hydrogen; And (c) mixing a predetermined proportion of ethanol and ammonia in the presence of hydrogen in step (b) to form an amination reaction mixture, wherein the partial pressure of hydrogen in step (c) And more preferably about 4 times or more. The present invention also relates to a method for producing ethylamine by reductive amination of ethanol.

Wherein the metal-supported catalyst is Ni / Al ₂ O ₃ , and the Ni / Al ₂ O ₃ is produced by: (d-1) mixing an aqueous nickel precursor solution with a support compound and stirring; (d-2) drying the mixture of step (d-1); And (d-3) firing the dried mixture in the step (d-2).

The support compound is not particularly limited and may be specifically at least one selected from the group consisting of alumina (Al ₂ O ₃ ), silica (SiO ₂ ), alumina-silica and zirconia (ZrO ₂ ) It can be Al ₂ O ₃ having a high specific surface area.

The Al ₂ O ₃ is a metal oxide having a specific surface area of about 150 to 300 m ² / g, and is made of an oxide by calcining the alumina gel at about 400 to 1000 ° C. The Al ₂ O ₃ is porous and has high thermal stability, high purity, and has the advantage of having a specific physical property by controlling the synthesis conditions. When the specific surface area of the support compound is 150 to 300 m < ² > / g, nickel can be supported at an appropriate ratio, which is preferable.

The nickel precursor is not particularly limited, but the nickel precursor may be at least one selected from nickel chloride, nickel acetate, nickel nitrate, and mixtures thereof. As described later, it is preferable that nickel is supported so as to be 5 to 25% by weight based on the total weight of the catalyst. Therefore, it is preferable to mix nickel precursors in an appropriate ratio in an aqueous solution.

Also, the stirring in the step (d-1) may be carried out at room temperature and is preferably carried out for about 30 minutes to 2 hours.

The drying in step (d-2) may be performed after removing moisture, and may be performed at 50 to 120 ° C.

The calcination in the step (d-3) may be carried out at a temperature rising rate of 1 to 3 ° C min ^{-1 and at} a temperature of 400 to 600 ° C for 1 to 3 hours under an air flow. When the calcination temperature is higher than 600 ° C, the catalyst particles lose their thermal stability, resulting in aggregation and a reduction in the specific surface area of the catalyst. When the calcination temperature is lower than 400 ° C, nickel ions are converted into NiO oxides There is a problem that the activity drops because it does not exist.

The Ni loading amount of the Ni / Al ₂ O ₃ catalyst is preferably such that the nickel content is 5 to 25% by weight based on the total weight of the catalyst. When the content of nickel is less than 5% by weight based on the total weight of the nickel catalyst, the content of nickel is too small and the particle size is small and the degree of dispersion is increased. However, By weight based on the total weight of the catalyst, the nickel component is not uniformly dispersed in the support. More preferably, the nickel content is preferably 10% by weight based on the total weight of the catalyst.

Also, as described above, when the nickel content is 10% by weight based on the total weight of the catalyst, the highest ethanol conversion and the selectivity of ethylamine can be exhibited.

Meanwhile, in the method of producing ethylamine by the reductive amination of ethanol, the partial pressure ratio of ammonia / ethanol in the amination reaction is 0.5 to 5, the partial pressure ratio of hydrogen / ethanol is 6 to 20, The speed may be from 0.1 to 2.0 h < -1 > and the temperature may be from 150 to 250 < 0 > C.

When the production process is proceeded under the above conditions, the conversion of ethanol increases, the secondary and tertiary amines are increased by continuous reaction, and the selectivity of ethylamine can be kept constant.

Also, as the partial pressure of hydrogen increases, the conversion of ethanol and the selectivity of ethylamine are increased. The selectivity of ethylamine increases rapidly with the partial pressure of hydrogen at four times higher than the partial pressure of ethanol in the partial pressure of hydrogen At higher pressures, the variation of ethylamine selectivity decreases.

The hydrogen also serves to reduce the catalyst, and the specific conditions for reduction depend on the particular catalyst composition being activated. The activation may include alloy formation, a suitable phase orientation of the metal, and an oxidation level of the metal.

Also, the reaction of step (c) may be performed at a pressure lower than the atmospheric pressure, unlike the conventional high-pressure reaction.

The production of ethylamine is preferably carried out in a fixed-bed packed reactor for continuous reaction.

The method of producing ethylamine by reductive amination of ethanol according to the present invention shows excellent selectivity to ethylamine even under atmospheric pressure unlike the prior art, and the inactivation of the catalyst is low with the reaction time, The high ethanol conversion and high ethylamine selectivity can be maintained.

According to another embodiment of the present invention, there is provided a process for producing a metal-supported catalyst, comprising the steps of: (i) preparing a metal-supported catalyst; (ii) activating the catalyst of step (i) in contact with hydrogen; (iii) mixing a predetermined proportion of ethanol and ammonia in the step (ii) to form an amination reaction mixture, wherein the partial pressure of ammonia in step (iii) is 1 to 7 times the partial pressure of ethanol The present invention provides a method for producing acetonitrile by reductive amination of ethanol.

In the process for producing acetonitrile by the reductive amination of ethanol according to the present invention, the reaction of step (iii) can be carried out under the existing high-pressure reaction and pressure below the leg pressure.

Further, the metal supported catalyst production process, the type and the nickel loading of the support compound type, nickel precursor as a Ni / Al ₂ O _3, the Ni / Al ₂ O ₃ are the same as those described in the production method of the ethylamine. Here, when the nickel content is 10% by weight with respect to the total weight of the catalyst, the highest ethanol conversion ratio and selectivity of acetonitrile can be shown.

When forming the amination reaction mixture in the step (iii), the partial pressure ratio of ammonia / ethanol is preferably 1 to 7, more preferably 1.5 to 5.

Also, in the method for producing acetonitrile by reductive amination of ethanol, the space velocity in the amination reaction may be 0.1 to 2.0 h ^-1 and the temperature may be 180 to 280 ° C.

The preparation of the acetonitrile is preferably carried out in a fixed-bed packed reactor for continuous reaction.

The method of producing acetonitrile by reductive amination of ethanol according to the present invention shows excellent selectivity to acetonitrile even under atmospheric pressure unlike the prior art, and the inactivation of the catalyst is low with the reaction time, The high ethanol conversion and high selectivity of acetonitrile can be maintained.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, it should be understood that the following examples are intended to illustrate the present invention and not to limit the present invention.

[Example]

The examples show the preparation of the nickel-supported catalyst according to the present invention.

≪ Example 1 >

1.335 g of nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ .6H ₂ O) as a nickel precursor was dissolved in 5 ml of distilled water, and this aqueous solution was carried on 5 g of a γ-Al ₂ O ₃ support. And the mixture was stirred at room temperature for 1 hour. The prepared solution was thoroughly dried at 100 ° C. for 12 hours after removing moisture at 70 ° C. and 50 rpm using a rotary evaporator (Eylar N1000). Next, the dried material was fired at 500 ° C for 2 hours while flowing air at a heating rate of 2 ° C min ^-1 to prepare NiO / Al ₂ O ₃ having a nickel content of 5% by weight.

≪ Example 2 >

2.819 g of nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ .6H ₂ O) as a nickel precursor was dissolved in 5 ml of distilled water, and this aqueous solution was carried on 5 g of an Al ₂ O ₃ support. Stir for 1 hour. The prepared solution was thoroughly dried at 100 ° C. for 12 hours after removing moisture at 70 ° C. and 50 rpm using a rotary evaporator (Eylar N1000). Next, the dried material was fired at 500 ° C for 2 hours while flowing air at a heating rate of 2 ° C min ^-1 to prepare NiO / Al ₂ O ₃ having a nickel content of 10% by weight.

≪ Example 3 >

4.451 g of nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ .6H ₂ O) as a nickel precursor was dissolved in 5 ml of distilled water, and this aqueous solution was carried on 5 g of Al ₂ O ₃ support. Stir for 1 hour. The prepared solution was thoroughly dried at 100 ° C. for 12 hours after removing moisture at 70 ° C. and 50 rpm using a rotary evaporator (Eylar N1000). Next, the dried material was fired at 500 ° C. for 2 hours while flowing air at a rate of 2 ° C. min ^-1 to prepare NiO / Al ₂ O ₃ having a nickel content of 15% by weight.

<Example 4>

After 6.320 g of nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ .6H ₂ O) as a nickel precursor was dissolved in 5 ml of distilled water, this aqueous solution was supported on 5 g of Al ₂ O ₃ support, Stir for 1 hour. The prepared solution was thoroughly dried at 100 ° C. for 12 hours after removing moisture at 70 ° C. and 50 rpm using a rotary evaporator (Eylar N1000). Next, the dried material was fired at 500 ° C. for 2 hours while flowing air at a rate of 2 ° C. min ^-1 to prepare NiO / Al ₂ O ₃ having a nickel content of 20 wt%.

&Lt; Example 5 >

8.427 g of nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ .6H ₂ O) as a nickel precursor was dissolved in 5 ml of distilled water, and this aqueous solution was carried on 5 g of Al ₂ O ₃ support. Stir for 1 hour. The prepared solution was thoroughly dried at 100 ° C. for 12 hours after removing moisture at 70 ° C. and 50 rpm using a rotary evaporator (Eylar N1000). Next, the dried material was fired at 500 ° C. for 2 hours while flowing air at a rate of 2 ° C. min ^-1 to prepare NiO / Al ₂ O ₃ having a nickel content of 25 wt%.

[Experimental Example] Preparation of ethylamine from the reductive amination reaction of ethanol

In order to confirm the effect of the present invention, a reductive amination reaction of ethanol was carried out under the following conditions. The catalyst of the above example was charged in a U-shaped quartz fixed bed reactor and the reaction temperature was controlled by using an external heater. At this time, the reaction time was controlled by adjusting the space time (WHSV) of the reactant and gas flowing into the reactor and the partial pressure of ethanol, ammonia, and hydrogen. The product was analyzed using a gas chromatography (Gas Chromatograph, Chrompack, CP 9001) equipped with a CP-Volamine capillary column (60 x 0.32 mm) and a Flame Ionization Detector (FID). N ₂ was used as a carrier gas. The temperature of the oven was maintained at 60 ° C. for the initial 9 minutes, then increased to 200 ° C. at 20 ° C./min and maintained for 5 minutes.

Here, the conversion of ethanol, the selectivity of product and the time of space (WHSV) were calculated by the following equations: F _EtOH and F _i are the molar flow rates of ethanol and products (ethylene, ethylamine, acetonitrile) _EtOH and C _i denotes the number of carbon atoms of the molecular weight and the product of each of ethanol.

[Equation 1]: Conversion rate of ethanol

(2): selectivity of product

[Equation 3] Spatial time (WHSV)

<Experimental Example 1> Amination activity of catalyst according to nickel content

The catalysts prepared according to Examples 1 to 5 were packed in a fixed-bed reactor operated continuously to convert to the active state. The atmosphere in contact with the catalyst inside the reactor was maintained at 600 ° C for 3 hours with hydrogen, then cooled to 190 ° C and maintained.

Thereafter, the total flow rate was set to 50 cm at a molar ratio of 0.2 g of the activated catalyst, a reaction temperature of 190 ° C, a WHSV of 0.9 h ^-1 and EtOH / NH ₃ / H ₂ / N ₂ = 1/3/6/23.8 ³ min &lt; ^{-1 &} gt ;. Here, the partial pressure of ethanol was fixed to 3 kPa, nitrogen was used as a diluent for controlling the partial pressure of other reactants, and the above conditions were maintained for 13 hours.

Using the catalysts of Examples 1, 2, 3, 4 and 5 activated, the amination reaction activity of ethanol according to the nickel content of the catalyst was measured under the reaction conditions shown in Table 1 below. 1 and Fig.

Hereinafter, monoethylamine is referred to as MEA, diethylamine as DEA, triethylamine as TEA, and acetonitrile as ACN.

division catalyst reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) Hydrogen
(kPa) Space velocity
(h ^-1 ) Average
Conversion Rate
(%) EA selectivity (%) Selectivity (%) MEA DEA TEA ACN C ₂ H ₄ Experimental Example
1-1 Example 1 190 3 9 18 0.9 45.1 85.5 42.6 36.7 6.2 14.6 0 Experimental Example
1-2 Example 2 190 3 9 18 0.9 76.5 90.1 36.6 44 9.5 7.2 1.4 Experimental Example
1-3 Example 3 190 3 9 18 0.9 65.3 87.0 38 40.6 8.4 10.6 1.8 Experimental Example
1-4 Example 4 190 3 9 18 0.9 63.6 88.8 39 40.8 9 9.3 1.8 Experimental Example
1-5 Example 5 190 3 9 18 0.9 59.5 89.5 40 41.1 8.4 8.5 1.9

As shown in Table 1 and FIG. 1, the catalyst of Example 2 exhibited the highest ethanol conversion rate at 76.5% under the same reaction conditions except for the content of nickel, and the highest ethanol conversion was obtained in Example 3, Example 4, Example 5, and Example 1, respectively.

In addition, the selectivity of the products was not significantly different according to the Ni content of each catalyst, and the catalysts of Examples 1 to 5 showed a selectivity of 90% or more with respect to ethylamine. The above results are closely related to the metal surface area and the metal dispersion of the catalyst, and the higher the metal dispersion and the metal surface area, the better the catalyst performance.

Also, as shown in FIG. 2, the selectivity of DEA and TEA increased and the selectivity of MEA and ACN decreased with increasing conversion of ethanol under the same reaction conditions regardless of Ni content. This result means that the reductive amination reaction of ethanol proceeds to a continuous stage, and the path of the reductive amination reaction of ethanol is as shown in the following reaction formula 1.

Reaction 1. Reaction path of ethanol to ethylamine

As shown in Reaction Scheme 1, the first step in the reductive amination of ethanol is to dehydrogenate ethanol to acetaldehyde, and then the hydrogenated acetaldehyde reacts with ammonia to form an imine as an amination intermediate. The formed imine is converted to MEA through a hydrogenation reaction, and DEA and TEA are formed by a continuous reaction between ethylamine and ethanol.

Experimental Example 2 Amination Reaction Activity by Spatial Velocity Change

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

The conditions of the catalyst of Example 2, which was changed to the active state, were set as in Experimental Example 1, except for the space velocity, and the reductive amination reaction of the catalyst according to the space velocity Experiments were conducted. The reaction products were analyzed using gas chromatography, and the results are shown in Table 2 and FIG.

division reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) Hydrogen
(kPa) 1 / WHSV (h) Average
Conversion Rate
(%) EA selectivity (%) Selectivity (%) MEA DEA TEA ACN C ₂ H ₂ Experimental Example
2-1 190 3 9 18 0.55 81.1 88.2 33.9 43.8 10.5 10.2 1.5 Experimental Example
2-2 190 3 9 18 0.90 76.5 90.1 36.6 44 9.5 7.2 1.4 Experimental Example
2-3 190 3 9 18 1.23 69.5 88.2 38.5 42.2 7.5 10.4 1.4 Experimental Example
2-4 190 3 9 18 1.64 54.7 85.6 40.6 38.5 6.5 13.4 1.7 Experimental Example
2-5 190 3 9 18 2.38 38.6 82.5 41.2 35.5 5.8 16.1 1.3

As shown in FIG. 3 and Table 2, the conversion rate of ethanol decreased from 81.1% to 38.6% as the space velocity increased, and the selectivity of ethylamine was 80% And the selectivity of MEA was increased and the selectivity of DEA and TEA were decreased as the space velocity was increased. In addition, the selectivity of ACN increased and the selectivity of ethylene was negligible in the range of all space velocities.

From the above results, it can be concluded that the increase of the space velocity from the production distribution of ethylamine according to the space velocity decreases the contact time between the reactant and the catalyst, and the continuous reaction does not proceed.

<Experimental Example 3> Amination reaction activity according to partial pressure of ammonia

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

Except that the partial pressure of ammonia was changed to the same value as in Experimental Example 1. The reductive amination reaction of the catalyst according to partial pressure of ammonia was carried out under the reaction conditions shown in Table 3 below, was subjected to the experiment, at this time, the ammonia was investigated in a molar ratio of 1/6 EtOH / H _2. The reaction products were analyzed using gas chromatography, and the results are shown in Table 3 and FIG.

division reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) Hydrogen
(kPa) Space velocity
(h ^-1 ) Average
Conversion Rate
(%) EA selectivity (%) Selectivity (%) MEA DEA TEA ACN C ₂ H ₂ Experimental Example
3-1 190 3 1.5 18 0.9 71.2 85.9 10.6 45.1 30.2 7.4 2.6 Experimental Example
3-2 190 3 3.0 18 0.9 77.0 92.2 19 51 22.2 5.5 2 Experimental Example
3-3 190 3 6.0 18 0.9 76.5 88.4 31.3 45.5 11.6 7.2 1.7 Experimental Example
3-4 190 3 9.0 18 0.9 73.9 90.1 36.6 44 9.5 8.4 1.4

As shown in Table 3 and FIG. 4, the conversion rate of ethanol was decreased with the increase of the ammonia ratio in the catalyst prepared in Example 2, and the highest conversion rate of 77% was obtained when the partial pressure of ammonia was 3 kPa . In addition, as the partial pressure of ammonia increased, the amount of ammonia on the active site was occupied, which resulted in a slight decrease in the conversion of ethanol because of the lack of active sites.

On the other hand, in the selectivity, as the partial pressure of ammonia increased, the selectivity of MEA increased and the generation of side reaction ACN predominated, and the selectivity of DEA and TEA decreased. It is considered that the higher the concentration of ammonia, the more favorable the formation of MEA, and the more the ammonia interferes with the adsorption of ethanol on the catalyst surface, thereby hindering the formation of DEA and TEA.

Considering the conversion of ethanol, it was found that the ammonia partial pressure of 3 kPa was the optimal concentration for the reductive amination of ethanol.

<Experimental Example 4> Reductive amination reaction activity of the catalyst according to the partial pressure of hydrogen

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

Except that the partial pressure of hydrogen was removed using the catalyst of Example 2 which was changed to the active state. The reductive amination reaction of the catalyst according to the hydrogen partial pressure was performed under the reaction conditions shown in Table 4 below was subjected to the experiment, at this time, the hydrogen was investigated in a molar ratio of 1/3 EtOH / NH _3. The reaction products were analyzed using gas chromatography, and the results are shown in Table 4 and FIG.

division reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) Hydrogen
(kPa) Space velocity
(h ^-1 ) Average
Conversion Rate
(%) EA selectivity (%) Selectivity (%) MEA DEA TEA ACN C ₂ H ₂ Experimental Example
4-1 190 3 3.0 0 0.9 70.2 6.4 3.3 3 0.1 93.5 0.1 Experimental Example
4-2 190 3 3.0 6.0 0.9 75.2 52.2 13.6 28.7 9.9 46.1 1.4 Experimental Example 4-3 190 3 3.0 12.0 0.9 76.6 70.3 16.1 39.1 15.1 27.7 1.9 Experimental Example
4-4 190 3 3.0 18.0 0.9 77.9 87.4 18 48.3 21.1 10.4 1.9 Experimental Example
4-5 190 3 3.0 24.0 0.9 84.5 87.3 17.9 47.8 21.6 10.1 2.5

As shown in Table 4 and FIG. 5, the catalyst prepared in Example 2 tended to increase the conversion of ethanol from 70.2% to 84.5% as the partial pressure of hydrogen increased.

In the absence of hydrogen, the selectivity of ACN was found to be over 95%, and as the partial pressure of hydrogen increased, the selectivity of ethylamine increased sharply.

<Experimental Example 5> Reductive amination reaction activity of the catalyst according to the temperature change

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

The remainder of the conditions were the same as those of Experimental Example 1 except for the temperature except for the temperature of the catalyst of Example 2 which was converted into the active state. The reductive amination activity of the catalyst Respectively. The reaction products were analyzed using gas chromatography, and the results are shown in Table 5 and FIG.

division reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) Hydrogen
(kPa) Space velocity
(h ^-1 ) Average
Conversion Rate
(%) EA selectivity (%) Selectivity (%) MEA DEA TEA ACN C ₂ H ₂ Experimental Example
5-1 170 3 9.0 18 0.9 49.6 99.6 14.6 56.1 28.9 0 0.1 Experimental Example
5-2 180 3 9.0 18 0.9 57.1 99.5 17.1 56 26.4 0.5 0 Experimental Example 5-3 190 3 9.0 18 0.9 68.9 89.3 15 49.2 25.1 8.8 1.4 Experimental Example
5-4 200 3 9.0 18 0.9 74.4 85.6 13.9 46.8 24.9 12.4 2 Experimental Example
5-5 210 3 9.0 18 0.9 87.8 61.6 10.4 33.8 17.4 18.6 4.6

As shown in Table 5 and FIG. 6, the catalyst prepared in Example 2 tended to increase the conversion of ethanol to 87.8% at a reaction temperature of 210 ° C. as the reaction temperature increased. On the other hand, the selectivity to ethylamine decreased and the selectivity to ACN and ethylene increased.

Experimental Example 6 Reductive Amination Reaction Activity of Catalyst with and without Ammonia and Hydrogen

According to Experimental Example 3 and Experimental Example 4, the partial pressures of ammonia and hydrogen showed significant influence on ethanol conversion and ethylamine selectivity. In order to better understand the effect of the reactants on the reductive amination of ethanol, the on / off experiments of ammonia or hydrogen of the catalyst of Example 2 were performed.

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

Except that the partial pressures of hydrogen and ammonia were the same as those of Experimental Example 1 except for partial pressures of hydrogen and ammonia. The catalysts according to partial pressures of hydrogen and ammonia under the reaction conditions of Table 6 A reductive amination reaction activity experiment was conducted where the molar ratio of the other reactants was controlled using a nitrogen diluent when no ammonia or hydrogen was present in the reactant stream. The reaction products were analyzed using gas chromatography, and the results are shown in Table 6 and FIG.

division Experimental Example 6 NH ₃ / H ₂
Partial pressure (kPa) NH ₃ / H ₂ = 3/6 Average conversion rate (%) 76.6 Selectivity
(%) MEA 14.9 DEA 49.2 TEA 28.1 ACN 6.3 C ₂ H ₄ 1.5 NH ₃ / H ₂ = 0/6 Average conversion rate (%) 14.7 Selectivity
(%) MEA 0 DEA 0 TEA 0 ACN 0 C ₂ H ₄ 71.1 NH ₃ / H ₂ = 3/6 Average conversion rate (%) 70.4 Selectivity
(%) MEA 15.0 DEA 46.8 TEA 20.2 ACN 7.9 C ₂ H ₄ 2.2 NH ₃ / H ₂ = 3/0 Average conversion rate (%) 70.5 Selectivity
(%) MEA 2.8 DEA 3.7 TEA 0 ACN 86.4 C ₂ H ₄ 0.9 NH ₃ / H ₂ = 3/6 Average conversion rate (%) 67.1 Selectivity
(%) MEA 17.7 DEA 50.6 TEA 22.8 ACN 9.1 C ₂ H ₄ 2.8

As shown in Table 6 and Figure 7, when ammonia is removed from the reactant stream, the conversion of ethanol is reduced to about 15%, and since the nitrogen-containing compound can not be formed, the dehydration / dehydrogenation products include C ₂ H ₄ , C ₂ H ₆ and acetaldehyde are produced.

Conversion of the ammonia-depleted reactant stream back to standard reaction conditions will restore the conversion and selectivity levels of ethanol to near initial levels. Here, the removal of hydrogen shows no significant change in the ethanol conversion, but ACN is mainly produced and only a small amount of ethylamine is produced.

The increase in the selectivity of ACN is believed to be due to the dehydrogenation of the intermediate imines formed in the amination reaction of ethanol, and this result confirms that the presence of hydrogen is an important parameter controlling the production of ethanol to ethylamine have.

In addition, when the hydrogen is removed from the reactant stream to the standard reaction condition, the conversion and selectivity of ethanol are restored to almost the initial level, and the ethanol conversion and product selectivity are greatly influenced by the reactant composition Respectively.

&Lt; Experimental Example 7 > Measurement of stability of catalyst over time during reductive amination reaction

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

Using the catalyst of Example 2 which was converted into the active state, the reaction was carried out under the same conditions as in Experimental Example 1 at a molar ratio of EtOH / NH ₃ / H ₂ / N ₂ = 1/1/6 / 25.8 The stability of the reductive amination reaction was tested. The reaction products were analyzed using gas chromatography, and the results are shown in Table 7 and FIG.

division Conversion Rate (%) Ethylamine selectivity (%) 0.3 h 90 h 0.08 h 90 h Experimental Example 7 81.9 68.2 MEA DEA TEA MEA DEA TEA 19.1 40.9 20.3 17.0 43.7 21.8

As shown in Table 7 and FIG. 8, the ethanol conversion of the catalyst prepared in Example 2 gradually decreased from 81% to 69% until 5 hours, and then remained stable. In addition, ethylamine selectivity was maintained at 80% or more for a reaction time of 90 hours, and the selectivity of each ethylamine was kept almost constant at MEA / DEA / TEA = 22/43/17.

Accordingly, it was confirmed that the Ni / Al ₂ O ₃ catalyst according to the present invention has high thermo-mechanical stability during the reductive amination reaction of ethanol to produce ethylamine.

[Experimental Example] Preparation of acetonitrile from the reductive amination reaction of ethanol

In order to confirm the effect of the present invention, a reductive amination reaction of ethanol was carried out under the following conditions. The catalyst of the above example was charged in a U-shaped quartz fixed bed reactor and the reaction temperature was controlled by using an external heater. At this time, the reaction was carried out by adjusting the space time (WHSV) of the reactant and gas introduced into the reactor, and the partial pressure of ethanol and ammonia. The product was analyzed using a gas chromatography (Gas Chromatograph, Chrompack, CP 9001) equipped with a CP-Volamine capillary column (60 x 0.32 mm) and a Flame Ionization Detector (FID). N ₂ was used as a carrier gas. The temperature of the oven was maintained at 60 ° C. for the initial 9 minutes, then increased to 200 ° C. at 20 ° C./min and maintained for 5 minutes.

<Experimental Example 8> Amination reaction activity according to partial pressure of ammonia

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

Thereafter, the activated catalyst was set to 0.2 g, the reaction temperature was 190 ° C., the WHSV was 0.9 h ^-1 , the partial pressure of ethanol was fixed at 3 kPa, and the total flow rate was set at 50 cm ³ min ^-1 . Here, nitrogen was used as a diluent for controlling the partial pressures of other reactants, and the above conditions were maintained for 13 hours.

The reductive amination reaction activity of the catalyst according to the partial pressure of ammonia was tested under the reaction conditions shown in Table 3 below. The results are shown in Tables 8 and 9 below.

Hereinafter, acetonitrile is described as ACN, monoethylamine as MEA, and diethylamine as DEA.

division reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) Space velocity
(h ^-1 ) Average
Conversion Rate
(%) Deactivation rate
(%) Selectivity (%) ACN MEA DEA C ₂ H ₄ Experimental Example
8-1 190 3 3 0.9 55.6 14.5 88.0 6.2 5.6 0.2 Experimental Example
8-2 190 3 6 0.9 55.8 -0.2 89.9 6.7 2.5 0.8 Experimental Example
8-3 190 3 9 0.9 45.6 -13.6 93.5 5.2 - 1.0 Experimental Example
8-4 190 3 15 0.9 37.6 -14.6 92.4 5.2 - 1.4 Experimental Example
8-5 190 3 21 0.9 37.1 -17.8 93.4 5.0 - 1.6

As shown in Table 8 and FIG. 9, the catalyst prepared in Example 2 exhibited the highest ethanol conversion when the partial pressure of ammonia was 6, and the highest ACN selectivity of 93.5% at 9 kPa .

Considering the conversion of ethanol, it was found that the partial pressure of ammonia of 6 kPa was the optimal concentration for the reductive amination reaction of ethanol.

Experimental Example 9 Reductive Amination Reaction Activity of Catalyst (NH ₃ / EtOH = 2/1)

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

Using the catalyst of Example 2, which was converted into the activated state, the remaining conditions except for the temperature were set as in Experimental Example 8, and the partial pressure of ammonia was set to 6 kPa. The reductive amination reaction activity of the catalyst according to the temperature change was performed under the reaction conditions shown in Table 9 below. The reaction products were analyzed using gas chromatography, and the results are shown in Table 9 and FIG. 10 below.

division reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) Space velocity
(h ^-1 ) Average
Conversion Rate
(%) Deactivation rate
(%) Selectivity (%) ACN MEA DEA C ₂ H ₄ Experimental Example
9-1 180 3 6 0.9 24.1 -2.1 89.9 9.3 - 0.5 Experimental Example
9-2 190 3 6 0.9 55.8 -0.2 89.9 6.7 2.5 0.8 Experimental Example
9-3 200 3 6 0.9 68.1 3.0 90.2 5.0 2.2 1.5 Experimental Example
9-4 210 3 6 0.9 82.6 0.2 93.6 3.2 1.2 1.8 Experimental Example
9-5 220 3 6 0.9 88.0 6.2 96.9 2.0 0.0 1.9

As shown in Table 9 and FIG. 10, as the reaction temperature increased, the catalyst prepared in Example 2 exhibited the highest conversion rate of ethanol at a reaction temperature of 220 ° C, which was 88.0%, and the selectivity to ACN The highest value was 96.9% at 220 ℃.

Considering the conversion of ethanol, it was found that 220 캜 is the optimal temperature for the reductive amination of ethanol at 6 kPa partial pressure of ammonia.

<Experimental Example 10> Reductive amination reaction activity (NH ₃ / EtOH = 3/1)

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

Using the catalyst of Example 2 which was converted into the active state, the remaining conditions except for the temperature were set as in Experimental Example 8, and the partial pressure of ammonia was set to 9 kPa. The reductive amination reaction activity of the catalyst according to the temperature change was performed under the reaction conditions shown in Table 9 below. The reaction products were analyzed using gas chromatography, and the results are shown in Table 10 and Fig.

division reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) Space velocity
(h ^-1 ) Average
Conversion Rate
(%) Deactivation rate
(%) Selectivity (%) ACN MEA DEA C ₂ H ₄ Experimental Example
10-1 190 3 9 0.9 45.9 -3.6 93.8 5.2 - 1.0 Experimental Example
10-2 200 3 9 0.9 53.4 0.9 95.0 4.6 - 0.9 Experimental Example
10-3 210 3 9 0.9 75.3 1.9 94.2 5.4 - 1.0 Experimental Example
10-4 220 3 9 0.9 89.0 2.5 96.2 3.4 - 1.7 Experimental Example
10-5 230 3 9 0.9 92.8 0.4 95.8 2.9 - 2.1 Experimental Example
10-6 240 3 9 0.9 92.4 4.6 97.0 2.0 - 2.0

As shown in Table 10 and FIG. 11, as the reaction temperature increased, the catalyst prepared in Example 2 exhibited the highest conversion ratio of ethanol at a reaction temperature of 230 ° C., which was 92.8%, and the selectivity to ACN Was 97.0% at 240 ° C and 95.8% at 230 ° C.

Considering the conversion of ethanol, it was found that 230 ℃ was the optimal temperature for the reductive amination of ethanol at 9 kPa partial pressure. The ethanol conversion and the ACN selectivity at 9 kPa partial pressure of ammonia were 6 kPa ammonia partial pressure And the selectivity of ACN was better than that of ethanol.

<Experimental Example 11> Amination reaction activity according to spatial velocity change

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

The total flow rate was then set to 50 cm ³ min ^-1 at a molar ratio of 0.2 g of the activated catalyst, a reaction temperature of 230 ° C. and EtOH / NH ₃ / N ₂ = 1/3 / 29.8 under standard reaction conditions, Respectively. Here, the partial pressure of ethanol was fixed to 3 kPa, nitrogen was used as a diluent for controlling the partial pressure of other reactants, and the above conditions were maintained for 13 hours.

division reaction
Temperature
(° C) ethanol
(kPa) Ammo
Nia
(kPa) 1 / WHSV (h) Average
Conversion Rate
(%) Deactivation rate
(%) Selectivity (%) ACN MEA DEA C ₂ H ₄ Experimental Example
11-1 230 3 9 1.1 82.6 0.2 93.6 3.2 1.2 1.8 Experimental Example
11-2 230 3 9 0.91 73.1 0.3 91.7 4.3 2.1 1.7 Experimental Example
11-3 230 3 9 0.55 50.4 3.6 96.0 2.6 - 1.2 Experimental Example
11-4 230 3 9 0.39 34.0 -0.9 96.3 2.6 - 0.9 Experimental Example
11-5 230 3 9 0.3 29.4 -1.4 96.9 1.7 - 1.0 Experimental Example
11-6 230 3 9 0.27 25.2 9.0 97.2 1.7 - 0.8

As shown in Table 11 and FIG. 12, the conversion rate of ethanol from the catalyst prepared in Example 2 decreased from 82.6% to 25.2% as the space velocity increased, and the selectivity of ACN was 91.7% To 97.2%, respectively. Also, the selectivity of MEA, DEA and C ₂ H ₄ decreased with increasing space velocity.

Considering the conversion of ethanol, it was found that the space velocity was the optimum space velocity when 0.90 h ^-1 .

&Lt; Experimental Example 12 > Experiments on the stability of catalysts over time of reductive amination reaction

The catalyst prepared according to Example 2 was activated in the same manner as in Experimental Example 1 above.

Using the catalyst of Example 2 which was converted into the active state, the same conditions as those of Experimental Example 11 were set, and the space velocity was set to 0.90 h ^-1 , and then the stability test of the reductive amination reaction of ethanol with time was carried out Respectively. The reaction products were analyzed using gas chromatography, and the results are shown in Table 12 and FIG.

division Conversion Rate (%) Selectivity (%) 0.3 h 100 h 0.08 h 90 h Experimental Example 12 91.5 78.2 ACN MEA C ₂ H ₄ ACN MEA C ₂ H ₄ 95.9 2.7 2.4 97.6 2.0 1.4

As shown in Table 12 and FIG. 13, the ethanol conversion of the catalyst prepared in Example 2 gradually decreased from 91.5% to 78.2% by 100 hours. Also, the ACN selectivity was maintained above 95% during the reaction time of 100 hours.

Accordingly, it has been confirmed that the Ni / Al ₂ O ₃ catalyst according to another embodiment of the present invention has high thermo-mechanical stability during the reductive amination of ethanol to produce acetonitrile.

The Ni / Al ₂ O ₃ catalyst according to the present invention is characterized in that the selectivity of ethylamine and acetonitrile can be controlled according to the reaction conditions. Therefore, the production of ethylamine or acetonitrile .

Claims (19)

A process for the production of ethylamine by reductive amination of ethanol,
(a) preparing a Ni / Al ₂ O ₃ catalyst;
(b) activating the catalyst of step (a) in contact with hydrogen;
(c) mixing a predetermined proportion of ethanol and ammonia with the hydrogen-activated catalyst of step (b) in the presence of hydrogen to form an amination reaction mixture,
Wherein the partial pressure ratio of hydrogen / ethanol in step (c) is 6 to 20, and the partial pressure ratio of ammonia / ethanol is 0.5 to 5. The method according to claim 1, delete The method according to claim 1,
The preparation of the Ni / Al ₂ O ₃ catalyst
(d-1) mixing the nickel precursor aqueous solution with alumina and stirring the mixture;
(d-2) drying the mixture of step (d-1); And
(d-3) calcining the dried mixture of step (d-2). delete The method of claim 3,
Wherein the nickel precursor is one selected from the group consisting of nickel chloride, nickel acetate, nickel nitrate, and mixtures thereof. The method of claim 3,
Wherein the calcination in the step (d-3) is carried out at a temperature rising rate of 1 to 3 占 폚 min ^{-1 at} a temperature of 400 to 600 占 폚 under an air flow. The method according to claim 1,
Wherein the reaction of step (c) is carried out at atmospheric pressure or lower. The method according to claim 1,
Wherein the amount of nickel supported is in the range of 5 to 25% by weight of nickel relative to the total weight of the catalyst. delete The method according to claim 1,
Wherein the space velocity in the amination reaction is 0.1 to 2.0 h &lt; ^-1 &gt;, and the temperature is 150 to 250 &lt; ⁰ &gt; C. A method for producing acetonitrile by reductive amination of ethanol,
(i) preparing a Ni / Al ₂ O ₃ catalyst;
(ii) activating the catalyst of step (i) in contact with hydrogen;
(iii) mixing a predetermined proportion of ethanol and ammonia with the hydrogen-activated catalyst of step (ii) to form an amination reaction mixture,
Wherein the partial pressure ratio of ammonia to ethanol in the step (iii) is 1.5 to 5. The method according to claim 1, wherein the ammonia / delete 12. The method of claim 11,
The preparation of the Ni / Al ₂ O ₃ catalyst
(d-1) mixing the nickel precursor aqueous solution with alumina and stirring the mixture;
(d-2) drying the mixture of step (d-1); And
(d-3) calcining the dried mixture of step (d-2). The method of producing acetonitrile by reductive amination of ethanol. delete 14. The method of claim 13,
Wherein the nickel precursor is one selected from the group consisting of nickel chloride, nickel acetate, nickel nitrate, and mixtures thereof. 14. The method of claim 13,
Wherein the calcination in the step (d-3) is carried out at a temperature rising rate of 1 to 3 占 폚 min ^{-1 at} a temperature of 400 to 600 占 폚 under an air flow. 12. The method of claim 11,
Wherein the reaction of step (iii) is carried out at atmospheric pressure or less. 12. The method of claim 11,
Wherein the amount of nickel supported is in the range of 5 to 25% by weight of nickel relative to the total weight of the catalyst. 12. The method of claim 11,
Wherein the space velocity in the amination reaction is 0.1 to 2.0 h &lt; ^-1 &gt;, and the temperature is 180 to 280 &lt; 0 &gt; C.

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