CN114713224A

CN114713224A - Catalyst for preparing ethylamine by catalyzing ethanol amination and preparation method and application thereof

Info

Publication number: CN114713224A
Application number: CN202210341517.1A
Authority: CN
Inventors: 王帅; 袁孟宇; 顾国顶
Original assignee: Xiamen University
Current assignee: Xiamen University
Priority date: 2022-04-02
Filing date: 2022-04-02
Publication date: 2022-07-08
Anticipated expiration: 2042-04-02
Also published as: CN114713224B

Abstract

The invention discloses a catalyst for catalyzing ethanol amination to prepare ethylamine and a preparation method and application thereof. The catalyst takes metal Cu as an active component, and contains a metal auxiliary agent M and a carrier Z, a chemical general formula can be expressed as Cu-M/Z, the weight ratio of Cu in the catalyst composition is 5-40 wt.%, the weight ratio of M is 0.1-10 wt.%, and the balance is the carrier. The catalyst can be prepared by an impregnation method. The catalyst can be used for preparing ethylReaction of amine: the raw material gas is composed of C₂H₅OH、NH₃、H₂And N₂Composition is carried out; the reaction temperature is 140-250 ℃, the total gas flow rate is 20-200 ml/min, wherein C₂H₅The partial pressure of OH is 1-10 kPa, NH₃The partial pressure of (A) is 5 to 50kPa, H₂The partial pressure of (A) is 15 to 80kPa, N₂The partial pressure of (A) is 10-80 kPa, and the total reaction pressure is normal pressure. The method for preparing ethylamine provided by the invention utilizes the large-particle-size metal Cu nanoparticle catalyst to improve the selectivity of ethanol amination reaction so as to stably generate diethylamine, and has obvious advantages compared with the existing method.

Description

Catalyst for preparing ethylamine by catalyzing ethanol amination and preparation method and application thereof

Technical Field

The invention belongs to the technical field of catalysis, and particularly relates to a catalyst for catalyzing ethanol amination to prepare ethylamine, and a preparation method and application thereof.

Background

The organic amine is an amino group (-NH) formed by substituting hydrogen atoms on ammonia by organic groups₂-NHR and-NR₂) A class of organic compounds featuring functional groups belongs to the derivatives of ammonia. The organic amine can be simply divided into aliphatic amine and aromatic amine, and the application of the ethyl amine compound in the lower aliphatic amine is very wide. The ethylamine mainly comprises monoethylamine, diethylamine and triethylamine, wherein the diethylamine is mainly used for manufacturing medicines, pesticides, dyes, rubber vulcanization accelerators, textile auxiliaries, metal preservatives, emulsifiers, polymerization inhibitors and the like, and can also be used as a refining solvent of wax, an activator in the polymerization of conjugated diene emulsion and an antifreeze agent for preparing engines. The ethylamine has large market demand at present and has wide application prospect.

Ethylamines are produced industrially mainly by ethanol amination reaction catalyzed by metal catalysts such as metallic nickel and the like. Ethanol amination is a typical tandem reaction. Specifically, ethanol will first be dehydrogenated over a metal catalyst to acetaldehyde; then acetaldehyde reacts with ammonia gas to generate an imine intermediate, and the imine intermediate is hydrogenated to generate monoethylamine; through the same reaction path, monoethylamine can be used as an amine source to perform further amination reaction with ethanol to obtain diethylamine and triethylamine. However, the product ethylamine has a stronger nucleophilicity than ammonia during the reaction, and is more susceptible to amination with ethanol, which results in difficulty in controlling the selectivity of a single ethylamine in ethanol amination. For example, chinese patent document CN101455963A discloses a catalyst for preparing ethylamine and a production method thereof, wherein the active components of the catalyst are mainly cobalt, nickel and iron, and the selectivities for obtaining monoethylamine, diethylamine and triethylamine at 98% ethanol conversion are 22.6%, 58.5% and 18.1%, respectively (reaction temperature 160 ℃). Chinese patent document CN101569862A discloses an alumina supported cobalt based catalyst (cobalt content 15% -35%) for preparing ethylamine, which has selectivity of 17.4%, 49.9% and 32.5% for monoethylamine, diethylamine and triethylamine at 170 ℃ and 98.3% conversion respectively. Recently, Jeong et al reported that the selectivity of ethylamine was controlled by using a supported metal Ni catalyst prepared by modifying rare earth oxide, and the highest selectivity of diethylamine obtained at 40% conversion of ethanol was about 48% (reaction temperature 200 ℃ C.), while the selectivity of triethylamine in the product was about 10% (Ye-Seul Jeong, Yeast Wo, mount-June Park, et al.

In addition, in addition to the formation of the ethyl amine product, side reactions such as acetaldehyde aldol condensation and deep dehydrogenation of an imine intermediate to form acetonitrile are also easy to occur in the ethanol amination reaction, and the complexity of the ethanol amination reaction system is further increased. Currently, the major bottleneck in the ethanol amination reaction is how to obtain high selectivity to a single ethylamine product, especially diethylamine, at high ethanol conversion. The method is very important for effectively reducing the separation and purification cost and energy consumption in the industrial production process. Therefore, the development of a high-efficiency heterogeneous catalyst for realizing selective catalytic amination conversion of ethanol to prepare a single ethylamine has very important value.

Disclosure of Invention

The invention aims to provide a catalyst for catalyzing ethanol amination to prepare ethylamine, a preparation method and application thereof, and the solution of the invention is as follows:

a catalyst for catalyzing ethanol amination to prepare ethylamine is characterized in that: the catalyst takes metal Cu as an active component, and contains a metal auxiliary agent M and a carrier Z, wherein the chemical general formula can be expressed as Cu-M/Z, the metal auxiliary agent M is one or a combination of more of Li, Na, K, Pt, La, Pr or Re, and the carrier Z is Nb₂O₅、Al₂O₃、ZnO、MgO、SiO₂、ZrO₂、CeO₂Or TiO₂The catalyst composition comprises 5-40 wt.% of Cu, 0.1-10 wt.% of M and the balance of a carrier.

A preparation method of a catalyst for preparing ethylamine by catalyzing ethanol amination comprises the following specific steps:

1) loading of Cu: dissolving active metal Cu precursor salt in a solvent, adding a carrier Z, stirring and dipping to prepare dipping liquid containing Cu/Z;

2) loading of the metal additive M: adding an auxiliary agent precursor salt into the Cu/Z impregnation liquid prepared in the step 1), and continuously stirring and impregnating to prepare an impregnation liquid containing Cu-M/Z;

3) heating and evaporating the Cu-M/Z impregnation liquid prepared in the step 2) to dryness, and roasting the obtained solid to prepare the catalyst for preparing the ethylamine by catalyzing ethanol amination.

Preferably, the active metal Cu precursor salt in the step 1) is formed by combining one or more of copper nitrate, copper sulfate, copper chloride, copper acetate or copper acetylacetonate.

Preferably, the solvent in step 1) is one or a combination of water, anhydrous ethanol and acetone.

Preferably, the dipping time is 4-24 h.

Preferably, the assistant precursor salt in step 2) is formed by combining one or more of potassium nitrate, potassium chloride, sodium nitrate, sodium chloride, lanthanum nitrate, lanthanum chloride, praseodymium nitrate, praseodymium chloride, lithium nitrate, lithium chloride, platinum nitrate, perrhenic acid, rhenium nitrate, platinum chloride or rhenium chloride.

Preferably, the heating and drying temperature in the step 3) is 70-150 ℃, and the heating and drying time is 2-24 h; the roasting atmosphere is air, the roasting temperature is 300-800 ℃, and the roasting time is 2-10 h.

The application of the catalyst for catalyzing ethanol amination to prepare ethylamine is characterized by comprising the following specific steps: granulating a catalyst Cu-M/Z, pretreating, and introducing raw gas to perform a reaction for preparing ethylamine; wherein the raw material gas consists of C₂H₅OH、NH₃、H₂And N₂The composition is that the reaction temperature is 140-250 ℃, the total gas flow rate is 20-200 ml/min, and C₂H₅The partial pressure of OH is 10-80 kPa, NH₃The partial pressure of (A) is 10-80 kPa, H₂The partial pressure of (A) is 10-80 kPa, N₂The partial pressure of (A) is 10 to 80kPa, and the total reaction pressure is normal pressure (100 kPa).

Preferably, the pretreatment temperature is 150-550 ℃, and the pretreatment atmosphere is H₂And N₂The pretreatment time is 1-3 h.

Preferably, the grain size of the catalyst Cu-M/Z is 40-60 meshes.

The mechanism of the method for preparing ethylamine provided by the invention is as follows:

the key to the selective formation of diethylamine in the ethanol amination reaction is that the metal catalyst needs to have good adsorption capacity to monoethylamine and acetaldehyde intermediate species simultaneously so as to promote the formation of diethylamine and inhibit the further conversion of diethylamine into triethylamine. The adsorption capacity of the metal catalyst has close relation with the types, particle sizes and the like of metal active sites; the extensive screening of the metal catalysts showed that: the supported metal Cu catalyst with the metal Cu particle size of more than 10nm has better monoethylamine and acetaldehyde adsorption capacity, and can show higher diethylamine selectivity when being used for ethanol amination reaction.

Compared with the existing catalyst for catalyzing ethanol amination to prepare ethylamine, the catalyst has the following advantages:

1) the catalyst for preparing ethylamine by catalyzing ethanol amination provided by the invention takes non-noble metal Cu as active metal, and the catalyst has the advantages of simple preparation method, simple and easily obtained raw materials, and effectively reduced production cost for preparing the ethylamine catalyst.

2) The preparation method of the catalyst provided by the invention realizes effective regulation and control of product selectivity by preparing the Cu nanoparticle catalyst with larger particle size. The preparation method of the catalyst provided by the invention can prepare the Cu nanoparticle catalyst with larger particle size, and the prepared catalyst is applied to the catalysis of ethanolamine reaction to realize effective regulation and control of product selectivity, specifically, the catalyst provided by the invention can effectively inhibit the conversion of diethylamine to triethylamine so as to improve the selectivity of diethylamine, and as a result, the selectivity of diethylamine can reach 73% when the conversion rate of ethanol exceeds 60%.

3) The method for preparing the ethylamine provided by the invention realizes that the selectivity of the diethylamine is effectively improved under the conditions of lower temperature and lower pressure and higher ethanol conversion rate, thereby further reducing the production cost of the diethylamine and being beneficial to large-scale commercial application and popularization.

Drawings

FIG. 1 is an X-ray diffraction (XRD) pattern of a Cu-supported catalyst of different metal oxide carriers according to the present invention;

FIG. 2 shows Cu/Al loadings in the invention₂O₃Catalyst X-ray diffraction (XRD) pattern;

FIG. 3 shows 20 wt.% Cu/γ -Al for the catalyst in example 8 of the present invention₂O₃Transmission Electron Microscope (TEM) images of (a).

Detailed Description

The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that the particular materials, reaction times and temperatures, process parameters, etc. listed in the examples are exemplary only and are intended to be exemplary of suitable ranges, and that insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be within the scope of the invention. The examples, where specific techniques or conditions are not indicated, are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by manufacturers, and are all conventional products which can be purchased in the market.

Example 1

The preparation steps of the catalyst for preparing the ethylamine by ethanol amination are as follows:

1) loading of Cu: dissolving 1.25g of copper acetate in 40mL of ethanol, ultrasonically dissolving for 5min at room temperature, and then continuing stirring for 30 min; however, the device is not suitable for use in a kitchenAfter this 2.0g of SiO were added₂The carrier is continuously stirred and dipped for 6 hours to prepare the Cu/SiO-containing carrier₂The impregnation liquid of (4);

2) loading of the metal additive M: the metal additive is not used in the embodiment;

3) the Cu/SiO-containing material prepared in the step 1)₂The impregnation liquid is subjected to rotary evaporation at the temperature of 60 ℃ for 1 hour, then is continuously dried at the temperature of 110 ℃ for 6 hours, the obtained solid is fully ground and then is calcined at the temperature of 450 ℃ in an air atmosphere for 4 hours, and the catalyst for preparing ethylamine by catalyzing ethanol amination can be prepared, and the obtained catalyst is recorded as 20 wt.% Cu/SiO₂. The XRD characterization of the catalyst is shown in fig. 1, and the characteristic peaks of metallic Cu can be clearly seen from fig. 1: 2 θ is diffraction peaks at 43.3 °, 50.4 ° and 74.1 ° for the Cu (111), (200) and (220) crystal planes, respectively.

The steps for preparing ethylamine by ethanol amination are as follows: the prepared catalyst Cu/SiO₂Granulating to 40-60 meshes, and placing 0.6g of catalyst in 50% H₂/N₂Pretreating the mixed gas at 250 ℃ for 2h, and then putting the pretreated mixed gas into a catalyst evaluation device to carry out ethanol amination: the feed gas is according to C₂H₅OH：NH₃：H₂A partial pressure ratio of 1:5:8, wherein C₂H₅OH gas partial pressure of 3kPa, NH₃Gas partial pressure of 15kPa, H₂Gas partial pressure of 24kPa, N₂The gas partial pressure is 58kPa, the reaction temperature is 180 ℃, the total gas flow rate is 60mL/min, and the total reaction pressure is normal pressure (100 kPa); the reaction results are shown in Table 1.

Example 2

The catalyst for the amination of ethanol to produce ethylamine was prepared similarly to example 1, except that the carrier was changed to γ -Al in step 1)₂O₃The same conditions were followed to produce a catalyst of 20 wt.% Cu/γ -Al₂O₃The XRD characterization of the catalyst is shown in fig. 1.

Conditions for the amination of ethanol to produce ethylamine referring to example 1, the reaction results are shown in table 1.

Example 3

The preparation of the catalyst for the amination of ethanol to produce ethylamine is similar to that of example 1, except thatChanging the support to Nb in step 1)₂O₅The same conditions were followed to produce a catalyst of 20 wt.% Cu/Nb₂O₅The XRD characterization of the catalyst is shown in fig. 1.

The conditions for the amination of ethanol to produce ethylamine are as in example 1 and the results are shown in Table 1.

Example 4

The catalyst for the amination of ethanol to make ethylamine was prepared similarly to example 1, except that the support was changed to MgO in step 1), and the remaining conditions were the same, to make 20 wt.% Cu/MgO catalyst whose XRD characterization is shown in fig. 1.

TABLE 1 Effect of Metal oxide Supports on the Ethanolamine Performance of Metal Cu catalysts

(reaction conditions: 180 ℃, 100kPa, 60mL/min, Cu loading 20 wt.%, gas partial pressure ratio)

C₂H₅OH:NH₃:H₂Not less than 1:5:8,0.6g catalyst)

As can be seen from Table 1, the metal oxide support has a significant effect on the conversion of ethanol and the selectivity of the product, when the metal oxide support is γ -Al₂O₃In this case, the selectivity of diethylamine can be as high as 71%.

As can be seen from fig. 1, the Cu-based catalyst prepared by this method has distinct metal characteristic peaks (2 θ ═ 43.3 °, 50.4 ° and 74.1 °) on different oxide supports, which indicates that the metal Cu on the catalyst has a larger particle size, and thus has a higher selectivity to diethylamine.

Example 5

For ethanol aminationPreparation of a catalyst for producing ethylamine was similar to example 1 except that the amount of copper acetate used in step 1) was changed to 0.31g, the ultrasonic dissolution time was adjusted to 10min, and the carrier was changed to γ -Al₂O₃The same conditions were followed to produce a catalyst of 5 wt.% Cu/γ -Al₂O₃The XRD characterization of the catalyst is shown in figure 2, and the characteristic peak of the metal Cu can be obviously seen from figure 2,

the conditions for the amination of ethanol to produce ethylamine are as in example 1 and the reaction results are shown in Table 2.

Example 6

The preparation of a catalyst for ethanol amination to ethylamine was similar to that of example 5, except that the amount of copper acetate used in step 1) was changed to 0.62g, the ultrasonic dissolution time was adjusted to 10min, and the carrier was changed to γ -Al₂O₃The same conditions were followed to produce a catalyst of 10 wt.% Cu/γ -Al₂O₃The XRD characterization of the catalyst is shown in fig. 2.

Example 7

The preparation of the catalyst for ethanol amination to produce ethylamine was similar to that of example 1, except that the amount of copper acetate used in step 1) was changed to 0.93g, the ultrasonic dissolution time was adjusted to 10min, and the carrier was changed to γ -Al₂O₃The same conditions were followed to produce a catalyst of 15 wt.% Cu/γ -Al₂O₃The XRD characterization of the catalyst is shown in fig. 2.

Example 8

The preparation of the catalyst for ethanol amination to ethylamine was similar to that of example 1, except that the amount of copper acetate used in step 1) was changed to 1.25g, the ultrasonic dissolution time was adjusted to 10min, and the carrier was changed to γ -Al₂O₃The same conditions were followed to produce a catalyst of 20 wt.% Cu/γ -Al₂O₃The XRD characterization of the catalyst is shown in fig. 2. The TEM characterization of the catalyst is shown in figure 3.

Example 9

The preparation of the catalyst for ethanol amination to produce ethylamine was similar to that of example 1, except that the amount of copper acetate used in step 1) was changed to 1.55g, the ultrasonic dissolution time was adjusted to 10min, and the carrier was changed to γ -Al₂O₃The same conditions were followed to produce 25 wt.% Cu/γ -Al catalyst₂O₃The XRD characterization of the catalyst is shown in fig. 2.

TABLE 2 metallic Cu loading vs. Cu/gamma-Al₂O₃Effect of catalyst Ethanolamine Performance

(reaction conditions: 180 ℃, 100kPa, 60mL/min, gas partial pressure ratio C₂H₅OH:NH₃:H₂＝

1:5:8,0.6g catalyst)

As can be seen from table 2, the loading of the active metal Cu has a significant effect on the conversion of ethanol and the selectivity of the product, and when the loading of the metal Cu is 20 wt.%, the selectivity of diethylamine can be as high as 71%.

As can be seen from fig. 2: with the increase of the metal loading capacity of the Cu-based catalyst prepared by the method provided by the invention, the metal characteristic peak of Cu is gradually enhanced, namely the particle size of metal Cu is increased; meanwhile, the conversion rate of the ethanol and the selectivity of the diethylamine in the product are improved. This indicates that the particle size of metallic Cu on the catalyst has a significant effect on the conversion of ethanol and the selectivity of the product. In addition, the catalyst shown in FIG. 3 is 20 wt.% Cu/Al₂O₃The TEM results of (a) show: the Cu on the prepared catalyst had a larger particle size (about 70nm), which is consistent with the results calculated from the XRD data.

Example 10

The catalyst used for the amination of ethanol to produce ethylamine was prepared as in example 8.

The conditions for amination of ethanol to produce ethylamine were similar to example 1, except that: the pre-reduction temperature of the catalyst is 300 ℃, the reduction time is 2h, and the rest conditions are the same as example 1. The reaction results are shown in Table 3.

Example 11

The conditions for amination of ethanol to produce ethylamine were similar to example 1, except that: the pre-reduction temperature of the catalyst is 350 ℃, the reduction time is 2h, and the rest conditions are the same as example 1. The reaction results are shown in Table 3.

TABLE 3 Pre-reduction temperature vs. 20 wt.% Cu/Al₂O₃Effect of catalyst Ethanolamine Performance

1:5:8,0.6g Cu/Al₂O₃)

As can be seen from Table 3, the pre-reduction temperature has a significant effect on the conversion of ethanol and the selectivity of the product, and the selectivity of diethylamine can reach up to 71% when the reduction temperature is 250 ℃.

Example 12

1) loading of Cu: dissolving 1.25g of copper acetate in 40mL of ethanol, ultrasonically dissolving for 5min at room temperature, and then continuing stirring for 30 min; then 2g of gamma-Al are added₂O₃The carrier is continuously stirred and dipped for 6 hours to prepare the Cu/gamma-Al-containing carrier₂O₃The impregnation liquid of (4);

2) loading of the metal additive M: Cu/gamma-Al contained in the product obtained in the step 2)₂O₃0.032g of potassium nitrate is added into the impregnation liquid to be continuously stirred and impregnated for 6 hours to obtain the Cu-K/gamma-Al-containing material₂O₃The impregnation liquid of (4);

3) the Cu-K/gamma-Al-containing material prepared in the step 2)₂O₃The impregnation liquid is subjected to rotary evaporation at the temperature of 60 ℃ for 1 hour, then is continuously dried at the temperature of 110 ℃ for 6 hours, the obtained solid is fully ground and then is calcined at the temperature of 450 ℃ in an air atmosphere for 4 hours, and the catalyst for preparing ethylamine by catalyzing ethanol amination can be prepared, and the obtained catalyst is marked as 20 wt.% Cu to 0.1 wt.% K/gamma-Al₂O₃. The XRD characterization of the catalyst is shown in fig. 1.

The conditions for the amination of ethanol to produce ethylamine are as in example 1 and the results are shown in Table 4.

Example 13

The catalyst for ethanol amination to ethylamine was prepared similarly to example 12, except that in step 2) the potassium nitrate was changed to lanthanum nitrate in an amount of 0.042g, and the other conditions were the same, to give a catalyst of 20 wt.% Cu to 0.1 wt.% La/γ -Al₂O₃。

Example 14

The catalyst for ethanol amination to produce ethylamine was prepared similarly to example 12, except that in step 2) the potassium nitrate was changed to praseodymium nitrate in an amount of 0.028g, and the other conditions were the same, to produce a catalyst of 20 wt.% Cu to 0.1 wt.% Pr/γ -Al₂O₃。

Example 15

The catalyst for ethanol amination to ethylamine was prepared similarly to example 12, except that in step 2) potassium nitrate was changed to sodium nitrate in an amount of 0.025g, and the same conditions were used to produce a catalyst of 20 wt.% Cu to 0.1 wt.% Na/γ -Al₂O₃。

TABLE 4 adjuvant vs. 20 wt.% Cu/Al₂O₃Catalyst ethanol aminationEffect of Performance

1:5:8,0.6g Cu/Al₂O₃)

As can be seen from Table 4, the addition of the auxiliary agent has an effect of promoting the conversion rate of ethanol and the selectivity of the product, and when the potassium auxiliary agent is added, the selectivity of diethylamine can reach 73%.

Claims

1. A catalyst for catalyzing ethanol amination to prepare ethylamine is characterized in that: the catalyst takes metal Cu as an active component, and contains a metal auxiliary agent M and a carrier Z, wherein the chemical general formula can be expressed as Cu-M/Z, the metal auxiliary agent M is one or a combination of more of Li, Na, K, Pt, La, Pr or Re, and the carrier Z is Nb₂O₅、Al₂O₃、ZnO、MgO、SiO₂、ZrO₂、CeO₂Or TiO₂The catalyst composition comprises 5-40 wt.% of Cu, 0.1-10 wt.% of M and the balance of a carrier.

2. The preparation method of the catalyst for catalyzing ethanol amination to prepare ethylamine as claim 1, which is characterized by comprising the following specific steps:

3. The method for preparing catalyst for preparing ethylamine by catalytic ethanol amination as claimed in claim 2, wherein the active metal Cu precursor salt in the step 1) is one or more of cupric nitrate, cupric sulfate, cupric chloride, cupric acetate or cupric acetylacetonate.

4. The method for preparing catalyst for preparing ethylamine by catalyzing ethanol amination as claimed in claim 2, wherein the solvent in the step 1) is one or more of water, absolute ethyl alcohol and acetone.

5. The method for preparing the catalyst for preparing the ethylamine by catalyzing ethanol amination as claimed in claim 2, wherein the dipping time is 4-24 h.

6. The method for preparing catalyst for preparing ethylamine by catalyzing amination of ethanol according to claim 2, wherein the auxiliary agent precursor salt in the step 2) is one or more of potassium nitrate, potassium chloride, sodium nitrate, sodium chloride, lanthanum nitrate, lanthanum chloride, praseodymium nitrate, praseodymium chloride, lithium nitrate, lithium chloride, platinum nitrate, perrhenic acid, rhenium nitrate, platinum chloride or rhenium chloride.

7. The method for preparing the catalyst for preparing the ethylamine by catalyzing the amination of the ethanol according to claim 2, wherein the heating and evaporating temperature in the step 3) is 70-150 ℃, and the heating and evaporating time is 2-24 h; the roasting atmosphere is air, the roasting temperature is 300-800 ℃, and the roasting time is 2-10 h.

8. The use of the catalyst of claim 1 for the catalytic amination of ethanol to produce ethylamine, comprising the steps of: granulating a catalyst Cu-M/Z, pretreating, and introducing raw gas to perform a reaction for preparing ethylamine; wherein the raw material gas is composed of C₂H₅OH、NH₃、H₂And N₂The reaction temperature is 140-250 ℃, the total gas flow rate is 20-200 ml/min, and the reaction temperature is C₂H₅The partial pressure of OH is 10-80 kPa, NH₃The partial pressure of (A) is 10-80 kPa, H₂The partial pressure of (A) is 10 to 80kPa, N₂The partial pressure of (A) is 10 to 80kPa, and the total reaction pressure is normal pressure (100 kPa).

9. The application of the catalyst for preparing ethylamine by catalyzing ethanol amination as claimed in claim 8, wherein the pretreatment temperature is 150-550 ℃, and the pretreatment atmosphere is H₂And N₂The pretreatment time is 1-3 h.

10. The use of a catalyst for the catalytic amination of ethanol to produce ethylamine as claimed in claim 8, wherein the catalyst Cu-M/Z has a particle size of 40 to 60 mesh.