CN116550332A - Cobalt-based catalyst and preparation method and application thereof - Google Patents

Cobalt-based catalyst and preparation method and application thereof Download PDF

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CN116550332A
CN116550332A CN202310387841.1A CN202310387841A CN116550332A CN 116550332 A CN116550332 A CN 116550332A CN 202310387841 A CN202310387841 A CN 202310387841A CN 116550332 A CN116550332 A CN 116550332A
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cobalt
mass
catalyst
component precursor
ethanol
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刘盛林
李想
冯超
梅林�
王玉忠
辛文杰
楚卫锋
朱向学
徐龙伢
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The application discloses a method for preparing a Co-based catalyst by hydrogen and application thereof. The preparation method comprises the following steps: immersing an alumina precursor in a mixed solution containing an active component precursor and an auxiliary component precursor, drying, and roasting in a hydrogen atmosphere to obtain the catalyst; the active component precursor is a cobalt-containing compound, and the auxiliary component precursor is lanthanum nitrate. Compared with a sample roasted in an air atmosphere, the catalyst prepared by the invention has the advantages of higher acetonitrile selectivity and the like.

Description

Cobalt-based catalyst and preparation method and application thereof
Technical Field
The application relates to a cobalt-based catalyst and a preparation method and application thereof, and belongs to the technical field of chemical catalyst preparation.
Background
Acetonitrile is an organic chemical raw material with quite wide application, is widely used as an extracting agent for extracting butadiene and isoprene from olefin and alkane in petrochemical industry, is also widely used as a synthetic raw material for organic synthesis, medicines, pesticides, surfactants, dyes and other fine chemicals, and is used as a mobile phase solvent for thin layer chromatography, paper chromatography, spectrum, polarography and High Performance Liquid Chromatography (HPLC), is recently used as a solvent for DNA synthesis and purification, is used as a solvent for organic EL material synthesis, is used as a cleaning solvent for chips, and has high requirements on the purity (more than or equal to 99.9%) of acetonitrile. Acetonitrile with purity more than or equal to 99.9% is popular in the market and has wide application, and the consumption rate of the acetonitrile exceeds 66%.
At present, acetonitrile is mainly recovered as a crude byproduct in the process of producing acrylonitrile by ammoxidation of propylene worldwide, but only 20-30 kg of acetonitrile can be obtained from 1 ton of acrylonitrile, the purity is not high, and particularly, acetonitrile with purity of more than or equal to 99.9% is difficult to reach. The production of acetonitrile by ammonification and dehydrogenation of ethanol is a beneficial supplement to the acetonitrile source. Compared with other acetonitrile obtaining methods, the method for producing acetonitrile by ammonification and dehydrogenation of ethanol has the advantages of simple process, low energy consumption, high atom utilization rate, high acetonitrile selectivity, less side reaction, less investment and low operation cost, and can realize industrialization.
The existing acetonitrile dehydrogenation ammoniation acetonitrile preparation method has the problems of low acetonitrile selectivity and the like.
Disclosure of Invention
The application aims to develop a CoLa/Al catalyst with high acetonitrile selectivity, which is used for preparing acetonitrile by alcohol dehydrogenation and ammonification, and is a report that the catalyst is used for preparing acetonitrile by alcohol dehydrogenation and ammonification for the first time.
According to one aspect of the present application, there is provided a method for preparing a cobalt-based catalyst by hydrogenation, comprising at least the steps of:
immersing an alumina precursor in a mixed solution containing an active component precursor and an auxiliary component precursor, drying, and roasting in a hydrogen atmosphere to obtain the catalyst;
the active component precursor is a cobalt-containing compound, and the auxiliary component precursor is lanthanum nitrate.
Optionally, the mass of the active component precursor is 5-30wt% of the mass of the alumina precursor, and the mass of the active component precursor is calculated by the mass of cobalt element in the cobalt-containing compound;
the mass of the auxiliary component precursor is 0.1-1.0 wt% of that of the alumina precursor, and the mass of the auxiliary component precursor is calculated by the mass of lanthanum element in lanthanum nitrate.
Optionally, the cobalt-containing compound is selected from at least one of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate.
Optionally, the impregnation adopts a vacuum isovolumetric impregnation mode; the soaking time is 2-5 h.
Optionally, the temperature of the drying is 110-130 ℃, and the time of the drying is 6-12 h.
Optionally, the roasting temperature is 500-700 ℃, and the roasting time is 2-4 hours;
the hydrogen atmosphere is selected from H 2 /N 2 Mixture gas, H 2 Mixture gas of He and H 2 Any one of the Ar mixed gases.
Optionally, H in the hydrogen atmosphere 2 The content is 3-50 vol%.
Optionally, H in the hydrogen atmosphere 2 The content of (2) is selected from any value or a range of values between any two values of 3vol%, 5vol%, 10vol%, 15vol%, 20vol%, 25vol%, 30vol%, 35vol%, 40vol%, 50vol%.
Optionally, the flow rate of the hydrogen atmosphere is 10-50 mL/min.
Optionally, the flow rate of the hydrogen atmosphere is any value or a range of values between two values of 10mL/min, 15mL/min, 20mL/min, 25mL/min, 30mL/min, 35mL/min, 40mL/min, 50mL/min.
According to another aspect of the present application, there is provided a cobalt-based catalyst comprising an alumina carrier, and cobalt element and lanthanum element supported on the alumina carrier;
wherein the cobalt element and the lanthanum element are both present in a reduced state.
Optionally, the mass of cobalt element is 5-30wt% of the mass of the alumina carrier;
the mass of lanthanum element is 0.1-1.0wt% of the alumina carrier.
Optionally, the particle size of the cobalt element is 0.1-0.5 nm.
According to yet another aspect of the present application, there is provided a method for preparing acetonitrile by dehydrogenating and ammonifying ethanol, comprising at least the following steps:
the mixed raw materials containing ethanol and ammonia gas are contacted with a catalyst to react, and a product containing acetonitrile is obtained; the catalyst is selected from the catalysts prepared by the preparation method.
Optionally, the molar ratio of ammonia gas to ethanol is 8-2: 1, a step of;
the mass airspeed of the ethanol is 0.1 to 1.0h -1 。
Optionally, the pressure of the reaction is 0.1-0.3 MPa;
the temperature of the reaction is 410-470 ℃.
The beneficial effects that this application can produce include:
cobalt and lanthanum in the prepared CoLa/Al catalyst are uniformly distributed in the catalyst, and are not easy to agglomerate in the reaction process; cobalt is present as reduced cobalt in a state that is greater than cobalt in the oxidized state (cobalt in the air atmosphere calcined sample is present as CoAl 2 O 4 /Co 3 O 4 In the form) is more active; in the roasting process of the hydrogen atmosphere, the sample is decomposed and reduced at the same time, so that small particles of reduced cobalt are kept, and the sample is reduced after air roasting, so that the cobalt particles obtained by reduction are larger. In the reaction of preparing acetonitrile by alcohol dehydrogenation and ammoniation, large-particle cobalt is unfavorable for the diffusion and reaction performance of reactants and products in a catalyst, and the like, so that the selectivity of acetonitrile is low.
The catalyst prepared by the invention can be applied to the process of preparing acetonitrile by alcohol dehydrogenation and ammoniation, and has the advantages of higher acetonitrile selectivity and the like compared with the conventional CoLa/Al catalyst roasted in air atmosphere.
Drawings
FIG. 1 is 20Co0.25La/Al of comparative example 1 of the present application 2 O 3 -TEM and HRTEM images of Air catalysts;
FIG. 2 is 20Co0.25La/Al of comparative example 2 of the present application 2 O 3 -Air-20H 2 /80N 2 TEM and HRTEM plots of the catalyst;
FIG. 3 is 20Co0.25La/Al of example 1 of the present application 2 O 3 -20H 2 /80N 2 TEM and HRTEM plots of the catalyst;
FIG. 4 is 5Co0.1La/Al of example 2 of the present application 2 O 3 -3H 2 /97N 2 TEM and HRTEM plots of the catalyst;
FIG. 5 is a 30Co1La/Al of example 3 of the present application 2 O 3 -50H 2 /35N 2 TEM and HRTEM images of 15Ar catalysts;
FIG. 6 is 15Co0.5La/Al of example 4 of the present application 2 O 3 -15H 2 /70N 2 TEM and HRTEM images of 15He catalyst.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
In the examples of the present application, agilent 7890A GC analysis, FID and TCD detectors, hydrogen and He were used as carrier gases.
In the examples of the present application, catalyst activity evaluation indexes, i.e., ethanol conversion, ammonia conversion and acetonitrile selectivity, were all calculated based on mass:
calculation of the conversion of the main reactants and the selectivity to acetonitrile:
ethanol conversion:
ammonia conversion rate:
acetonitrile selectivity:
in the above formula, m represents mass.
Comparative example 1
9.86g Co (NO) 3 ) 2 ·6H 2 O and 0.079g La (NO) 3 ) 3 ·6H 2 O is dissolved in 5.5g of water, 7.975g of alumina is placed in a closed container, the impregnating solution is sucked into a carrier by adopting a vacuum isovolumetric impregnation method, the vacuum is pumped to 10Pa, then the carrier is impregnated for 3 hours at 25 ℃, the carrier is dried for 6 hours in a baking oven at 120 ℃, 5g of sample is taken and baked for 3 hours at 600 ℃ in an air atmosphere (100 ml/min) to prepare the catalyst Cat-A, wherein the content of Co and La is 20wt% and 0.25wt% respectively.
Comparative example 2
Sample Cat-A prepared in comparative example 1 was weighed 5g in a hydrogen atmosphere (20H 2 /80N 2 100 ml/min) at 600℃for 3 hours to obtain catalyst Cat-B, wherein the Co and La contents were 20wt% and 0.25wt%, respectively.
Example 1
9.86g Co (NO) 3 ) 2 ·6H 2 O and 0.079g La (NO) 3 ) 3 ·6H 2 O was dissolved in 5.5g of water, 7.975g of alumina was placed in a closed vessel, the impregnation solution was sucked into the carrier by a vacuum isovolumetric impregnation method, the vacuum was pulled to 10Pa, then the impregnation was carried out at 25℃for 3 hours, oven-dried at 120℃for 6 hours, and 5g of the sample was taken in a hydrogen atmosphere (20H 2 /80N 2 100 ml/min) at 600℃for 3 hours to obtain catalyst Cat-C, wherein the contents of Co and La were 20wt% and 0.25wt%, respectively.
Example 2
2.11g Co (CH) 3 COO) 2 ·4H 2 O，0.032g La(NO 3 ) 3 ·6H 2 O is dissolved in 5.5g of water, 7.975g of alumina is placed in a closed container, the impregnating solution is sucked into the carrier by adopting a vacuum isovolumetric impregnation method, the vacuum is pumped to 10Pa, then the carrier is impregnated for 2 hours at 25 ℃, and is dried for 8 hours in a baking oven at 130 ℃, 5g of sample is taken and is put in a hydrogen atmosphere (3H 2 /97N 2 50 ml/min) at 500℃for 4 hours to obtain catalyst Cat-D, wherein the Co and La contents were 5wt% and 0.1wt%, respectively.
Example 3
10.00g of Co (NO) 3 ) 2 ·6H 2 O，3.91gCoCl 2 ·6H 2 O，0.316g La(NO 3 ) 3 ·6H 2 O, 0.240. 0.240g L-arginine was dissolved in 5.5g of water, 7.975g of alumina was placed in a closed vessel, the impregnation solution was sucked into the carrier by a vacuum isovolumetric impregnation method, the vacuum was pulled at 10Pa, then impregnation was carried out at 25℃for 5 hours, oven drying was carried out at 110℃for 12 hours, and 5g of the sample was taken in a hydrogen atmosphere (50H 2 /35N 2 150 ml/min/15 Ar) at 600℃for 2 hours to obtain catalyst Cat-E, wherein the Co and La contents were 30wt% and 1.0wt%, respectively.
Example 4
3.70g Co (NO) 3 ) 2 ·6H 2 O，3.57g CoSO 4 ·7H 2 O，0.158g La(NO 3 ) 3 ·6H 2 O, 0.160. 0.160g L-arginine was dissolved in 5.5g of water, 7.975g of alumina was placed in a closed vessel, the impregnating solution was sucked into the carrier by a vacuum isovolumetric impregnation method, the vacuum was pulled up to 10Pa, then the carrier was impregnated for 4 hours at 25℃and dried for 12 hours at 110℃to obtain 5g of a sample under a hydrogen atmosphere (15H 2 /70N 2 250 ml/min/15 He) was calcined at 700℃for 4 hours to obtain catalyst Cat-F having Co and La contents of 15wt% and 0.5wt%, respectively.
In this application, fig. 1 to 6 correspond to comparative examples 1, 2, 3, and 4, respectively;
FIG. 1A is a graph of 20Co0.25La/Al at 200nm 2 O 3 -TEM images of Air catalysts; panel B is 20Co0.25La/Al at 10nm 2 O 3 HRTEM diagram of Air catalyst; by passing throughFIG. 1 shows 20Co0.25La/Al 2 O 3 The Air catalyst has larger Co 3 O 4 Or CoAl 2 O 4 Particles, high resolution transmission electron microscope analysis to identify the particles as Co 3 O 4 Or CoAl 2 O 4 Corresponding to Co 3 O 4 Or CoAl 2 O 4 (2 2 2 0) crystal plane;
FIG. 2C is a graph of 20Co0.25La/Al at 200nm 2 O 3 -Air-20H 2 /80N 2 TEM image of catalyst; FIG. D is 20Co0.25La/Al at 10nm 2 O 3 -Air-20H 2 /80N 2 HRTEM diagram of catalyst; as can be seen from FIG. 2, 20Co0.25La/Al prepared by air calcination-hydrogenation 2 O 3 -Air-20H 2 /80N 2 The catalyst ratio is 20Co0.25La/Al 2 O 3 Co in Air catalyst 3 O 4 Or CoAl 2 O 4 The particles are small, and the high-resolution transmission electron microscope analysis identifies the particles as Co and corresponds to the (1 1 1) crystal face of Co;
FIG. 3E is a graph of 20Co0.25La/Al at 200nm 2 O 3 -20H 2 /80N 2 TEM image of catalyst; f graph is 20Co0.25La/Al at 10nm 2 O 3 -20H 2 /80N 2 HRTEM diagram of catalyst; as can be seen from FIG. 3, 20Co0.25La/Al after hydrogen calcination 2 O 3 -20H 2 /80N 2 The catalyst ratio is 20Co0.25La/Al 2 O 3 The Air catalyst has small particles, which can indicate that the hydrogen atmosphere roasting active component has better dispersity, and the high-resolution transmission electron microscope analysis identifies the particles as Co and corresponds to the (1 1 1) crystal face of Co;
FIG. 4G is a graph of 5Co0.1La/Al at 200nm 2 O 3 -3H 2 /97N 2 TEM image of catalyst; h diagram is 5Co0.1La/Al at 10nm 2 O 3 -3H 2 /97N 2 HRTEM diagram of catalyst; as can be seen from FIG. 4, the high resolution transmission electron microscope analysis shows that the particles are still Co, and 20Co0.25La/Al 2 O 3 -20H 2 /80N 2 The catalyst keeps consistent and corresponds to the (1 1 1) crystal face of Co;
FIG. 5 is a graph I of 30Co1La/Al at 200nm 2 O 3 -50H 2 /35N 2 TEM image of 15Ar catalyst; j graph is 30Co1La/Al at 10nm 2 O 3 -50H 2 /35N 2 HRTEM diagram of/15 Ar catalyst; as can be seen from FIG. 5, the active components are well dispersed, and the high-resolution transmission electron microscope analysis identifies the particles as Co, and the Co corresponds to the (1 1 1) crystal face of Co;
FIG. 6 is a K plot of 15Co0.5La/Al at 200nm 2 O 3 -15H 2 /70N 2 TEM image of 15He catalyst; l diagram 15Co0.5La/Al at 10nm 2 O 3 -15H 2 /70N 2 HRTEM diagram of 15He catalyst; from fig. 6, it can be seen that the active component particles are smallest among the 6 catalysts, and the high-resolution transmission electron microscopy analysis identifies the particles as Co, corresponding to the (2 0 0) crystal plane of Co.
Example 5
The catalysts prepared in comparative examples 1 and 2 were subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 9mm, the catalyst loading amount is 4g, the temperature is raised to 410 ℃ at the heating rate of 3 ℃/min under the nitrogen condition, and ammonia gas and ethanol are introduced. The reaction conditions are as follows: the temperature is 410 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 0.5h -1 The molar ratio of ammonia gas to ethanol is 6:1. the liquid and gas phase products were analyzed using Agilent 7890A GC FID and TCD detectors, respectively, with the carrier gas being hydrogen and nuclear gas, respectively, and the specific evaluation results are shown in table 1.
Example 6
The catalyst prepared in example 1 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 9mm, the catalyst loading amount is 4g, the temperature is raised to 410 ℃ at the heating rate of 3 ℃/min under the nitrogen condition, and ammonia gas and ethanol are introduced. The reaction conditions are as follows: the temperature is 410 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 0.5h -1 The molar ratio of ammonia gas to ethanol is 6:1. the liquid and gas phase products were analyzed using Agilent 7890A GC FID and TCD detectors, respectively, with the carrier gas being hydrogen and nuclear gas, respectively, and the specific evaluation results are shown in table 1.
Example 7
Example on a fixed bed reactorAnd 2, evaluating the reaction performance of the catalyst prepared by the method for preparing acetonitrile by alcohol dehydrogenation and ammonification. The diameter of the reactor is 9mm, the catalyst loading amount is 4g, the temperature is raised to 450 ℃ at the heating rate of 3 ℃/min under the nitrogen condition, and ammonia gas and ethanol are introduced. The reaction conditions are as follows: the temperature is 450 ℃, the pressure is 0.1MPa, and the mass space velocity of the ethanol is 0.5h -1 The molar ratio of ammonia gas to ethanol is 6:1. the liquid and gas phase products were analyzed using Agilent 7890A GC FID and TCD detectors, respectively, with the carrier gas being hydrogen and nuclear gas, respectively, and the specific evaluation results are shown in table 1.
Example 8
The catalyst prepared in example 3 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 9mm, the catalyst loading amount is 4g, the temperature is raised to 430 ℃ at the heating rate of 3 ℃/min under the nitrogen condition, and ammonia gas and ethanol are introduced. The reaction conditions are as follows: the temperature is 430 ℃, the pressure is 0.3MPa, and the ethanol mass airspeed is 0.1h -1 The molar ratio of ammonia gas to ethanol is 2:1. the liquid and gas phase products were analyzed using Agilent 7890A GC FID and TCD detectors, respectively, with the carrier gas being hydrogen and nuclear gas, respectively, and the specific evaluation results are shown in table 1.
Example 9
The catalyst prepared in example 4 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 9mm, the catalyst loading amount is 4g, the temperature is raised to 470 ℃ at the temperature rising rate of 3 ℃/min under the condition of nitrogen, and ammonia gas and ethanol are introduced. The reaction conditions are as follows: the temperature is 470 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 1.0h -1 The molar ratio of ammonia gas to ethanol is 8:1. the liquid and gas phase products were analyzed using Agilent 7890A GC FID and TCD detectors, respectively, with the carrier gas being hydrogen and nuclear gas, respectively, and the specific evaluation results are shown in table 1.
Table 1 reactivity of catalyst for catalyzing alcohol dehydrogenation ammonification to prepare acetonitrile
Catalyst numbering Cat-A Cat-B Cat-C Cat-D Cat-E Cat-F
Reaction pressure (Mpa) 0.10 0.10 0.10 0.10 0.30 0.10
Ethanol mass space velocity (h) -1 ) 0.5 0.5 0.5 0.5 0.1 1.0
Reaction temperature (. Degree. C.) 410 410 410 450 430 470
Molar ratio of ammonia to alcohol 6:1 6:1 6:1 6:1 2:1 8:1
Ethanol conversion (%) 99.88 98.34 99.99 99.99 99.99 99.99
Acetonitrile selectivity (%) 74.85 74.16 83.53 88.47 82.20 85.60
The experimental results in Table 1 show that CoLa/Al is prepared by air atmosphere calcination or by hydrogen atmosphere reduction of samples after air atmosphere calcination 2 O 3 The reaction performance (Cat-A, cat-B) on the catalyst is not greatly changed, and the roasting in the hydrogen atmosphere can promote CoLa/Al 2 O 3 The reaction performance is higher than that of an alumina carrier supported cobalt-lanthanum catalyst (Cat-A) prepared by air atmosphere, the acetonitrile selectivity of the alumina carrier supported cobalt-lanthanum catalyst (Cat-C) prepared by hydrogen atmosphere roasting is higher, and the reaction performance of the prepared Cat-E, cat-F and Cat-G catalysts is under the examined reaction conditionsExcellent.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (10)

1. The preparation method of the cobalt-based catalyst by hydrogen is characterized by at least comprising the following steps:
immersing an alumina precursor in a mixed solution containing an active component precursor and an auxiliary component precursor, drying, and roasting in a hydrogen atmosphere to obtain the catalyst;
the active component precursor is a cobalt-containing compound, and the auxiliary component precursor is lanthanum nitrate.
2. The preparation method according to claim 1, wherein the mass of the active component precursor is 5 to 30wt% of the mass of the alumina precursor, and the mass of the active component precursor is calculated as the mass of cobalt element in the cobalt-containing compound;
the mass of the auxiliary component precursor is 0.1-1.0 wt% of that of the alumina precursor, and the mass of the auxiliary component precursor is calculated by the mass of lanthanum element in lanthanum nitrate.
3. The production method according to claim 1, wherein the cobalt-containing compound is at least one selected from the group consisting of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate.
4. The preparation method according to claim 1, wherein the impregnation adopts a vacuum isovolumetric impregnation mode, and the impregnation time is 2-5 h;
preferably, the temperature of the drying is 110-130 ℃, and the time of the drying is 6-12 h.
5. The method according to claim 1, wherein the baking temperature is 500 to 700 ℃, and the baking time is 2 to 4 hours;
the hydrogen atmosphere is selected from H 2 /N 2 Mixture gas, H 2 Mixture gas of He and H 2 Any one of Ar mixed gas;
preferably, H in the hydrogen atmosphere 2 The content is 3-50 vol%;
preferably, the flow rate of the hydrogen atmosphere is 10-50 mL/min.
6. A cobalt-based catalyst obtained by the production method according to any one of claims 1 to 5, characterized by comprising an alumina carrier and cobalt element and lanthanum element supported on the alumina carrier;
wherein the cobalt element and the lanthanum element are both present in a reduced state.
7. The cobalt-based catalyst according to claim 6, wherein the mass of cobalt element is 5 to 30wt% of the mass of the alumina carrier;
the mass of lanthanum element is 0.1-1.0 wt% of the alumina carrier;
preferably, the particle size of the cobalt element is 0.1-0.5 nm.
8. The method for preparing acetonitrile by dehydrogenating and ammonifying ethanol is characterized by at least comprising the following steps:
the mixed raw materials containing ethanol and ammonia gas are contacted with a catalyst to react, and a product containing acetonitrile is obtained;
the catalyst is selected from the catalysts prepared by the preparation method of any one of claims 1 to 5, or at least one of the catalysis and of claim 6 or 7.
9. The method according to claim 8, wherein the molar ratio of ammonia gas to ethanol is 8-2: 1, a step of;
the mass airspeed of the ethanol is 0.1 to 1.0h -1 。
10. The method according to claim 8, wherein the pressure of the reaction is 0.1 to 0.3MPa;
the temperature of the reaction is 410-470 ℃.
CN202310387841.1A 2023-04-12 2023-04-12 Cobalt-based catalyst and preparation method and application thereof Pending CN116550332A (en)

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