Process for the preparation of a catalyst and use thereof

Abstract

The application discloses a preparation method of a catalyst and application of the catalyst, and at least comprises the following steps: impregnating a carrier precursor in a mixture containing an active component precursor, an additive precursor and a surfactant, drying and calcining to obtain the catalyst; the carrier precursor is at least one of alumina, magnesia and zirconia; the active component precursor is cobalt nitrate; the additive precursor is lanthanum nitrate; and the surfactant is L-arginine. The catalyst prepared by the application has higher acetonitrile selectivity and better stability and other advantages compared with a sample without adding L-arginine.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of a catalyst and application thereof, and belongs to the technical field of chemical catalyst preparation. BACKGROUND

[0002] Acetonitrile is a quite widely used organic chemical raw material, which is used as an extraction agent for extracting butadiene and isoprene from olefins and paraffins in petroleum chemical industry, and is widely used as a synthetic raw material for fine chemicals such as organic synthesis, medicines, pesticides, surfactants, dyes and the like, and a mobile phase solvent for thin layer chromatography, paper chromatography, spectroscopy, polarography and high performance liquid chromatography (HPLC), and is used as a DNA synthesis purification solvent, an organic EL material synthesis solvent, an electronic component such as a chip cleaning solvent and the like. These uses have high requirements on the purity (≥99.9%) of acetonitrile. Acetonitrile with a purity ≥99.9% is quite popular in the market and is widely used, and its consumption proportion is more than 66%.

[0003] At present, acetonitrile is mainly recovered from a crude by-product in a propylene ammoxidation process for producing acrylonitrile, but only 20-30 kg of acetonitrile with low purity can be obtained from 1 ton of acrylonitrile, and it is difficult to obtain acetonitrile with a purity ≥99.9%. Ethanol ammoniation and dehydrogenation for producing acetonitrile is a beneficial supplement to the source of acetonitrile. Compared with other methods for obtaining acetonitrile, the ethanol ammoniation and dehydrogenation process is simple, has low energy consumption, high atom utilization rate, high acetonitrile selectivity, few side reactions, low investment and low operation cost, and can realize industrialization.

[0004] The existing acetonitrile dehydrogenation and ammoniation process for producing acetonitrile has the problems or defects of low ethanol conversion rate and acetonitrile selectivity, and poor catalyst stability. SUMMARY

[0005] The application aims to develop a CoLa / Al catalyst with high selectivity and stability for ethanol dehydrogenation and ammoniation for producing acetonitrile, which is the first report of the catalyst for ethanol dehydrogenation and ammoniation for producing acetonitrile.

[0006] The catalysts for the production of acetonitrile from ethanol amination dehydrogenation are divided into two categories: dehydrogenation / hydrogenation catalysts and dehydration catalysts. The dehydrogenation / hydrogenation catalysts mainly use Ni, Cu, Fe, Cr, Co, Rh, Zr, Pb and Ag as the main active components, among which the most widely used is nickel. It is usually necessary to add a second and a third component as a catalyst promoter, such as Cu, Co, Na, Mg and Ca and rare earth elements. These catalysts exhibit good catalytic activity under suitable reaction conditions, and the introduction of the catalyst promoter can also improve the product distribution. Al2O3, SiO2 and HZSM-5 are often used as dehydration condensation catalysts because their surfaces have certain acidity. Among them, Al2O3 is an excellent catalyst for alcohol dehydration and is also a carrier that is widely used in industrial metal carrier catalysts.

[0007] According to an aspect of the present application, a preparation method of a catalyst is provided, the preparation method comprising at least the following steps:

[0008] impregnating a carrier precursor in a mixture containing an active component precursor, an additive precursor and a surfactant, drying and calcining to obtain the catalyst;

[0009] The carrier precursor is selected from at least one of alumina, magnesia and zirconia.

[0010] The active component precursor is cobalt nitrate; the additive precursor is lanthanum nitrate; and the surfactant is L-arginine.

[0011] Optionally, the mass of the surfactant is 1.0-3.0wt% of the mass of the carrier precursor, and the mass of the surfactant is based on the mass of L-arginine.

[0012] Optionally, the upper limit of the mass of the surfactant is independently selected from 3.0wt%, 2.8wt%, 2.5wt%, 2.0wt% and 1.5wt%, and the lower limit is independently selected from 1.0wt%, 1.2wt%, 1.5wt% and 2.0wt%.

[0013] Optionally, the mass of the additive precursor is 0.1-1.0wt% of the mass of the carrier precursor, and the mass of the additive precursor is based on the mass of lanthanum in lanthanum nitrate.

[0014] Optionally, the upper limit of the mass of the additive precursor is independently selected from 1.0wt%, 0.9wt%, 0.8wt%, 0.7wt%, 0.6wt% and 0.5wt%, and the lower limit is independently selected from 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt% and 0.6wt%.

[0015] Optionally, the mass of the active component precursor is 5-30wt% of the mass of the support precursor, the mass of the active component precursor being the mass of cobalt element in the cobalt nitrate.

[0016] Optionally, the upper limit of the mass of the active component precursor is independently selected from 30wt%, 25wt%, 20wt%, 15wt%, 10wt%, and the lower limit is independently selected from 5wt%, 10wt%, 15wt%, 20wt%, 25wt% of the mass of the support precursor.

[0017] Optionally, the impregnation is vacuum isovolumetric impregnation; the time of the impregnation is 2-5h.

[0018] Optionally, the vacuum degree of the vacuum isovolumetric impregnation is 1-10Pa.

[0019] Optionally, the time of the impregnation is selected from any value or range value between any two points of 2h, 3h, 4h, 5h.

[0020] Optionally, the temperature of the drying is 110-130℃; the time of the drying is 6-12h.

[0021] Optionally, the temperature of the drying is selected from any value or range value between any two points of 110℃, 115℃, 120℃, 125℃, 130℃.

[0022] Optionally, the time of the drying I is selected from any value or range value between any two points of 6h, 7h, 8h, 9h, 10h, 11h, 12h.

[0023] Optionally, the temperature of the calcination is 500-700℃; the atmosphere of the calcination is air atmosphere; the time of the calcination is 2-4h.

[0024] Optionally, the temperature of the calcination is selected from any value or range value between any two points of 500℃, 550℃, 600℃, 650℃, 700℃.

[0025] Optionally, the time of the calcination is selected from any value or range value between any two points of 2h, 2.5h, 3h, 3.5h, 4h.

[0026] According to another aspect of the present application, a catalyst is provided, which is prepared by the above-mentioned preparation method.

[0027] According to still another aspect of the present application, a method for preparing acetonitrile by dehydrogenation and ammoniation of ethanol is provided, which at least comprises the following steps:

[0028] The raw material containing ethanol and ammonia gas is mixed, contacted with the catalyst, and reacted to obtain a product containing acetonitrile;

[0029] The catalyst is selected from the catalyst prepared by the preparation method described above or at least one of the above catalysts.

[0030] Optionally, the molar ratio of ammonia gas to ethanol is 8-2:1.

[0031] The mass space velocity of ethanol is 0.1-1.0h -1 ;

[0032] The pressure of the reaction is 0.1-0.2MPa.

[0033] The temperature of the reaction is 400-470℃.

[0034] Optionally, the mass space velocity of ethanol is selected from any value in 0.1h -1 , 0.2h -1 , 0.3h -1 , 0.4h -1 , 0.5h -1 , 0.6h -1 , 0.7h -1 , 0.8h -1 , 0.9h -1 , 1.0h -1 or a range value between any two of the above.

[0035] Optionally, the pressure of the reaction is selected from any value in 0.1MPa, 0.15MPa, 0.2MPa or a range value between any two of the above.

[0036] Optionally, the temperature of the reaction is selected from any value in 400℃, 430℃, 450℃, 460℃, 470℃ or a range value between any two of the above.

[0037] The beneficial effects that can be produced by the present application include:

[0038] The cobalt and lanthanum in the CoLa / Al catalyst prepared by the present application are uniformly distributed in the catalyst, and are not easy to agglomerate during the reaction, thereby affecting the diffusion of reactants and products in the catalyst and the reaction performance of the catalyst, etc.

[0039] The catalyst prepared by the present application can be applied to the process of ethanol dehydrogenation and ammoniation to prepare acetonitrile, and compared with the conventional CoLa / Al catalyst without adding L-arginine, the catalyst has higher acetonitrile selectivity and better stability, etc. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1TEM and HRTEM images of the 20Co / Al2O3 catalyst of the present application (A: TEM image of the 20Co / Al2O3 catalyst; B: HRTEM image of the 20Co / Al2O3 catalyst).

[0041] Figure 2 TEM and HRTEM images of the 20Co0.125La / Al2O3 catalyst of the present application (C: TEM image of the 20Co0.125La / Al2O3 catalyst; D: HRTEM image of the 20Co0.125La / Al2O3 catalyst).

[0042] Figure 3 TEM and HRTEM images of the 20Co0.25La / Al2O3 catalyst of the present application (E: TEM image of the 20Co0.25La / Al2O3 catalyst; F: HRTEM image of the 20Co0.25La / Al2O3 catalyst).

[0043] Figure 4 TEM and HRTEM images of the 20Co0.5La / Al2O3 catalyst of the present application (G: TEM image of the 20Co0.5La / Al2O3 catalyst; H: HRTEM image of the 20Co0.5La / Al2O3 catalyst). DETAILED DESCRIPTION

[0044] The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.

[0045] In the examples of the present application, the raw materials were purchased through commercial channels unless otherwise specified.

[0046] In the examples of the present application, Agilent 7890A GC analysis was used, with an FID detector and hydrogen as the carrier gas.

[0047] In the examples of the present application, the catalyst activity evaluation indicators, i.e., ethanol conversion rate, ammonia conversion rate and acetonitrile selectivity, were all calculated based on mass:

[0048] Calculation of main reactant conversion rate and acetonitrile selectivity:

[0049] Ethanol conversion rate:

[0050]

[0051] Ammonia conversion rate:

[0052]

[0053] Acetonitrile selectivity:

[0054]

[0055] In the above formula, m represents mass.

[0056] Comparative Example 1

[0057] Co(NO3)2-6H2O 9.86 g, L-arginine 0.120 g were dissolved in 5.5 g of water, 7.975 g of alumina was put in a closed container, the impregnation solution was sucked into the carrier by vacuum isometric impregnation, vacuumed to 10 Pa, then impregnated at 25°C for 3 hours, oven dried at 120°C for 6 hours, and calcined at 700°C for 3 hours to prepare a catalyst Cat-A, in which the content of Co was 20 wt%.

[0058] Comparative Example 2

[0059] Co(NO3)2-6H2O 9.86 g, L-arginine 0.120 g were dissolved in 5.5 g of water, 7.975 g of alumina was put in a closed container, the impregnation solution was sucked into the carrier by vacuum isometric impregnation, vacuumed to 10 Pa, then impregnated at 25°C for 3 hours, oven dried at 120°C for 6 hours, and calcined at 700°C for 3 hours to prepare a catalyst Cat-A, in which the content of Co was 20 wt%.

[0060] Comparative Example 3

[0061] Co(NO3)2-6H2O 9.86 g, L-arginine 0.120 g were dissolved in 5.5 g of water, 7.975 g of alumina was put in a closed container, the impregnation solution was sucked into the carrier by vacuum isometric impregnation, vacuumed to 10 Pa, then impregnated at 25°C for 3 hours, oven dried at 120°C for 6 hours, and calcined at 700°C for 3 hours to prepare a catalyst Cat-A, in which the content of Co was 20 wt%.

[0062] Example 1

[0063] Co(NO3)2-6H2O 9.86 g, L-arginine 0.120 g were dissolved in 5.5 g of water, 7.975 g of alumina was put in a closed container, the impregnation solution was sucked into the carrier by vacuum isometric impregnation, vacuumed to 10 Pa, then impregnated at 25°C for 3 hours, oven dried at 120°C for 6 hours, and calcined at 700°C for 3 hours to prepare a catalyst Cat-A, in which the content of Co was 20 wt%.

[0064] Example 2

[0065] Co(NO3)2.6H2O, 0.032 g La(NO3)2.6H2O, 0.08 g L-arginine were dissolved in 5.5 g water, 7.975 g alumina was put in a closed container, the impregnation solution was absorbed into the carrier by vacuum isometric impregnation method, vacuumed to 10 Pa, then impregnated at 25 °C for 2 h, oven dried at 130 °C for 8 h, and calcined at 500 °C for 4 h to prepare the catalyst Cat-E. The contents of Co and La in the catalyst Cat-E were 5 wt% and 0.1 wt%, respectively.

[0066] Example 3

[0067] Co(NO3)2.6H2O, 0.316 g La(NO3)2.6H2O, 0.240 g L-arginine were dissolved in 5.5 g water, 7.975 g alumina was put in a closed container, the impregnation solution was absorbed into the carrier by vacuum isometric impregnation method, vacuumed to 10 Pa, then impregnated at 25 °C for 5 h, oven dried at 110 °C for 12 h, and calcined at 600 °C for 2 h to prepare the catalyst Cat-F. The contents of Co and La in the catalyst Cat-F were 30 wt% and 1.0 wt%, respectively.

[0068] Example 4

[0069] Co(NO3)2.6H2O, 0.158 g La(NO3)2.6H2O, 0.160 g L-arginine were dissolved in 5.5 g water, 7.975 g alumina was put in a closed container, the impregnation solution was absorbed into the carrier by vacuum isometric impregnation method, vacuumed to 10 Pa, then impregnated at 25 °C for 4 h, oven dried at 110 °C for 12 h, and calcined at 550 °C for 4 h to prepare the catalyst Cat-G. The contents of Co and La in the catalyst Cat-G were 15 wt% and 0.5 wt%, respectively.

[0070] Example 5

[0071] The catalysts prepared in Comparative Examples 1 and 2 were evaluated for the performance of the reaction of dehydrogenation ammoniation of ethanol to acetonitrile on a fixed bed reactor. The reactor had a diameter of 14 mm, and the catalyst loading was 4 g. The temperature was raised to 430 °C at a heating rate of 3 °C / min under the condition of ammonia, and ethanol was introduced. The reaction time was 3 h. The reaction conditions were as follows: the temperature was 430 °C, the pressure was 0.1 MPa, the mass space velocity of ethanol was 0.5 h-1, and the molar ratio of ammonia to ethanol was 6:1. The products were analyzed by Agilent 7890A GC FID detector with hydrogen as the carrier gas. The specific evaluation results are shown in Table 1. -1

[0072] Example 6

[0073] ​The performance of the catalyst prepared in Comparative Example 3 for the dehydrogenation and amination of ethanol to acetonitrile was evaluated in a fixed-bed reactor. The reactor diameter was 14 mm, the catalyst loading was 4 g, and the temperature was increased to 430 °C at a rate of 3 °C / min under ammonia conditions. Ethanol was then introduced, and the reaction time was 3 h. The reaction conditions were: temperature 430 °C, pressure 0.1 MPa, and ethanol mass hourly space velocity (HHSV) 0.5 h⁻¹. -1 The molar ratio of ammonia to ethanol was 6:1. The products were analyzed using an Agilent 7890A GC FID detector with hydrogen as the carrier gas. The specific evaluation results are shown in Table 1.

[0074] Example 7

[0075] The performance of the catalyst prepared in Comparative Example 3 for the dehydrogenation and amination of ethanol to acetonitrile was evaluated in a fixed-bed reactor. The reactor diameter was 14 mm, the catalyst loading was 4 g, and the temperature was increased to 430 °C at a rate of 3 °C / min under ammonia atmosphere. Ethanol was then introduced, and the reaction time was 98 h. The reaction conditions were: temperature 430 °C, pressure 0.1 MPa, and ethanol mass hourly space velocity (HHSV) 0.5 h⁻¹. -1 The molar ratio of ammonia to ethanol was 6:1. The products were analyzed using an Agilent 7890A GC FID detector with hydrogen as the carrier gas. The specific evaluation results are shown in Table 1.

[0076] Example 8

[0077] The performance of the catalyst prepared in Example 1 for the dehydrogenation and amination of ethanol to acetonitrile was evaluated in a fixed-bed reactor. The reactor diameter was 14 mm, the catalyst loading was 4 g, and the temperature was increased to 430 °C at a rate of 3 °C / min under ammonia conditions. Ethanol was then introduced, and the reaction time was 3 h. The reaction conditions were: temperature 430 °C, pressure 0.1 MPa, and ethanol mass hourly space velocity (HHSV) 0.5 h⁻¹. -1 The molar ratio of ammonia to ethanol was 6:1. The products were analyzed using an Agilent 7890A GC FID detector with hydrogen as the carrier gas. The specific evaluation results are shown in Table 1.

[0078] Example 9

[0079] The performance of the catalyst prepared in Example 1 for the dehydrogenation and amination of ethanol to acetonitrile was evaluated in a fixed-bed reactor. The reactor diameter was 14 mm, the catalyst loading was 4 g, and the temperature was increased to 430 °C at a rate of 3 °C / min under ammonia conditions. Ethanol was then introduced, and the reaction time was 98 h. The reaction conditions were: temperature 430 °C, pressure 0.1 MPa, and ethanol mass hourly space velocity (HHSV) 0.5 h⁻¹. -1 The molar ratio of ammonia to ethanol was 6:1. The products were analyzed using an Agilent 7890A GC FID detector with hydrogen as the carrier gas. The specific evaluation results are shown in Table 1.

[0080] Example 10

[0081] The catalyst prepared in Example 2 was evaluated for the performance of the reaction of ethanol dehydrogenative ammoniation to prepare acetonitrile on a fixed bed reactor. The reactor had a diameter of 14 mm, and the catalyst loading was 4 g. The temperature was raised to 430℃ at a rate of 3℃ / min under the condition of ammonia, ethanol was introduced, and the reaction time was 26 h. The reaction conditions were: the temperature was 430℃, the pressure was 0.2 MPa, the mass space velocity of ethanol was 0.1 h -1 , and the molar ratio of ammonia to ethanol was 2:1. The product was analyzed by Agilent 7890A GC FID detector with hydrogen as the carrier gas, and the specific evaluation results are shown in Table 1.

[0082] Example 11

[0083] The catalyst prepared in Example 3 was evaluated for the performance of the reaction of ethanol dehydrogenative ammoniation to prepare acetonitrile on a fixed bed reactor. The reactor had a diameter of 14 mm, and the catalyst loading was 4 g. The temperature was raised to 470℃ at a rate of 3℃ / min under the condition of ammonia, ethanol was introduced, and the reaction time was 4 h. The reaction conditions were: the temperature was 470℃, the pressure was 0.1 MPa, the mass space velocity of ethanol was 1.0 h -1 , and the molar ratio of ammonia to ethanol was 8:1. The product was analyzed by Agilent 7890A GC FID detector with hydrogen as the carrier gas, and the specific evaluation results are shown in Table 1.

[0084] Example 12

[0085] The catalyst prepared in Example 4 was evaluated for the performance of the reaction of ethanol dehydrogenative ammoniation to prepare acetonitrile on a fixed bed reactor. The reactor had a diameter of 14 mm, and the catalyst loading was 4 g. The temperature was raised to 400℃ at a rate of 3℃ / min under the condition of ammonia, ethanol was introduced, and the reaction time was 20 h. The reaction conditions were: the temperature was 400℃, the pressure was 0.1 MPa, the mass space velocity of ethanol was 0.3 h -1 , and the molar ratio of ammonia to ethanol was 4:1. The product was analyzed by Agilent 7890A GC FID detector with hydrogen as the carrier gas, and the specific evaluation results are shown in Table 1.

[0086] Table 1 Reaction performance of catalysts in the reaction of ethanol dehydrogenative ammoniation to prepare acetonitrile

[0087] Catalyst number Cat-A Cat-B Cat-C Cat-C Cat-D Cat-D Cat-E Cat-F Cat-G Reaction pressure (Mpa) 0.10 0.10 0.10 0.10 0.10 0.10 0.20 0.10 0.10 Ethanol weight hourly space velocity (h -1 )]]> 0.5 0.5 0.5 0.5 0.5 0.5 0.1 1.0 0.3 Reaction temperature (°C) 430 430 430 430 430 430 430 470 400 Ammonia alcohol molar ratio 6:1 6:1 6:1 6:1 6:1 6:1 2:1 8.0 4.0 Reaction time (h) 3 3 3 98 3 98 26 4 20 Ethanol conversion (%) 99.02 99.12 99.42 96.72 99.99 99.95 99.78 99.65 99.50 Acetonitrile selectivity (%) 78.60 79.20 82.10 77.66 84.40 84.20 84.13 84.74 85.13

[0088] The experimental results of Table 1 show that the addition of L-arginine alone has little effect on the reaction performance over Co / Al2O3(Cat-A vs Cat-B), while the addition of lanthanum can promote the reaction performance over Co / Al2O3(Cat-A vs Cat-C). Compared with the Co / Al2O3 catalyst without L-arginine (Cat-C), the Co / Al2O3 catalyst with L-arginine (Cat-D) has higher selectivity for acetonitrile and better stability. The reaction performance of Cat-E, Cat-F and Cat-G prepared under the reaction conditions investigated is excellent.

[0089] Table 2 Structural properties of Co / Al2O3 catalysts with different La contents

[0090] S BET a (m 2 / g)]]> V b (cm 3 / g)]]> 20Co / Al203 80 0.548 20Co0.125La / Al203 95 0.537 20Co0.25La / Al203 97 0.533 20Co0.50La / Al203 91 0.512

[0091] In Table 2, a refers to the specific surface area; b refers to the cumulative desorption pore volume. The experimental results of Table 2 show that the porous structure and specific surface area of the La-modified Co / Al2O3 samples were characterized by N2 physical adsorption. It can be seen that the La-modified catalysts have a larger specific surface area and a smaller pore volume compared with the 20Co / Al2O3 catalyst, which may be due to the better dispersion of the catalyst surface microcrystals. It can be seen that the addition of La in the Co / Al2O3 catalyst can increase the specific surface area of the catalyst and thus improve the reaction performance.

[0092] Figure 1 TEM and HRTEM characterization of Co / Al2O3 catalysts (A is the TEM image of 20Co / Al2O3 catalyst; B is the HRTEM image of 20Co / Al2O3 catalyst). It can be seen that there are large Co3O4 or CoAl2O4 particles in the 20Co / Al2O3 catalyst, and high-resolution transmission electron microscopy analysis identifies the particles as Co3O4 or CoAl2O4, corresponding to the (2 2 0) crystal plane of Co3O4 or CoAl2O4.

[0093] Figure 2TEM and HRTEM characterization of 20Co0.125La / Al2O3 catalyst (C is TEM image of 20Co0.125La / Al2O3 catalyst; D is HRTEM image of 20Co0.125La / Al2O3 catalyst). It can be seen that the Co3O4 or CoAl2O4 particles in the catalyst after La addition look smaller than those in 20Co / Al2O3, which can indicate that the dispersion of the active component in the catalyst is better after La addition. Meanwhile, high-resolution transmission electron microscopy analysis identifies the particles as Co3O4 or CoAl2O4, which is consistent with 20Co / Al2O3 catalyst, corresponding to the (2 2 0) crystal plane of Co3O4 or CoAl2O4.

[0094] Figure 3 TEM and HRTEM characterization of 20Co0.25La / Al2O3 catalyst (E is TEM image of 20Co0.25La / Al2O3 catalyst; F is HRTEM image of 20Co0.25La / Al2O3 catalyst). It can be seen that the Co3O4 or CoAl2O4 particles in the catalyst after La addition look smaller than those in 20Co / Al2O3, and the Co3O4 or CoAl2O4 particles are smallest and the active component is best dispersed when the La addition amount is 0.25 in the four catalysts. High-resolution transmission electron microscopy analysis identifies the particles as Co3O4 or CoAl2O4, corresponding to the (2 2 0) crystal plane of Co3O4 or CoAl2O4.

[0095] Figure 4 TEM and HRTEM characterization of 20Co0.5La / Al2O3 catalyst (G is TEM image of 20Co0.5La / Al2O3 catalyst; H is HRTEM image of 20Co0.5La / Al2O3 catalyst). It can be seen that the Co3O4 or CoAl2O4 particles in the catalyst after La addition look smaller than those in 20Co / Al2O3, and the active component is well dispersed. High-resolution transmission electron microscopy analysis identifies the particles as Co3O4 or CoAl2O4, corresponding to the (1 1 1) crystal plane of Co3O4 or CoAl2O4.

[0096] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the preferred embodiments are disclosed as above, they are not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the disclosed technical content without departing from the scope of the technical solution of the present application, which are equivalent to equivalent embodiments, and are within the scope of the technical solution.

Claims

1. A process for the preparation of acetonitrile by ethanol dehydrogenative amination, characterized in that, The method comprises the following steps: The raw material containing ethanol and ammonia gas is mixed, contacted with a catalyst, reacted to obtain a product containing acetonitrile; The preparation method of the catalyst comprises the following steps: The carrier precursor is impregnated in a mixture containing an active component precursor, an additive precursor and a surfactant, dried and calcined to obtain the catalyst; The carrier precursor is at least one of alumina, magnesia and zirconia; The active component precursor is cobalt nitrate, the additive precursor is lanthanum nitrate, and the surfactant is L-arginine; The calcination temperature is 500-700 DEG C; The calcination atmosphere is air atmosphere; The calcination time is 2-4h.

2. The method of claim 1, wherein, The mass of the surfactant is 1.0-3.0wt% of the mass of the carrier precursor, and the mass of the surfactant is the mass of L-arginine.

3. The method of claim 1, wherein, The mass of the additive precursor is 0.1-1.0wt% of the mass of the carrier precursor, and the mass of the additive precursor is the mass of lanthanum in lanthanum nitrate.

4. The method of claim 1, wherein, The mass of the active component precursor is 5-30wt% of the mass of the carrier precursor, and the mass of the active component precursor is the mass of cobalt in cobalt nitrate.

5. The method of claim 1, wherein, The impregnation is vacuum isometric impregnation, and the impregnation time is 2-5h.

6. The method of claim 5, wherein, The vacuum degree of the vacuum isometric impregnation is 1-10Pa.

7. The method of claim 1, wherein, The drying temperature is 110-130 DEG C; The drying time is 6-12h.

8. The method of claim 1, wherein, The molar ratio of ammonia gas to ethanol is 2-8:1; The mass space velocity of the ethanol is 0.1-1.0 h -1 ; The reaction pressure is 0.1-0.2 MPa; The reaction temperature is 400-470 DEG C.

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