CN114797880A - Composite metal oxide catalyst and preparation method and application thereof - Google Patents

Composite metal oxide catalyst and preparation method and application thereof Download PDF

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CN114797880A
CN114797880A CN202210714145.2A CN202210714145A CN114797880A CN 114797880 A CN114797880 A CN 114797880A CN 202210714145 A CN202210714145 A CN 202210714145A CN 114797880 A CN114797880 A CN 114797880A
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water
metal oxide
component
soluble
salt
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黄龙
邵恒
朱春梅
刘伟
高乐
褚海斌
陈醒
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Beijing Fleming Technology Co ltd
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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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • 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
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Abstract

The invention provides a composite metal oxide catalyst and a preparation method and application thereof, and relates to the technical field of catalysts. The composite metal oxide catalyst provided by the invention comprises a component A2 (layered metal oxide, alkaline earth metal and aluminum with the molar ratio of 1-6: 1, wherein the alkaline earth metal is one or more of Mg, Ca and Ba), a component A1 (Ni and/or Co, 40-50 wt%) and a component A3 (La and/or Ce, 0.1-1 wt%) which are loaded on the surface of the component A2. In the composite metal oxide catalyst provided by the invention, the component A1 and the component A3 have strong interaction with the layered metal oxide, the specific surface area of the layered metal oxide is large, the dispersion degree of the component A1 and the component A3 on the surface of the component A2 is high, the catalytic activity and the catalytic stability for the selective hydrogenation reaction of the cyano compounds are high, the conversion rate of raw materials is high, the selectivity of products is high, and the service life of the catalyst is long.

Description

Composite metal oxide catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a composite metal oxide catalyst and a preparation method and application thereof.
Background
Amines are very important organic compounds and are important versatile intermediates for the preparation of multipurpose natural products, pharmaceuticals, pesticides, dyes, pigments, polymers. Primary amines are among all the amines the most valuable intermediates, since they can be functionalized directly. The primary amine is a product of complete hydrogenation of nitrile, and in the hydrogenation reaction of nitrile compounds, a highly active intermediate imine is easily produced, and this easily undergoes a condensation reaction with an intermediate product and a target product to produce various secondary amines, tertiary amines and other high-boiling-point polymers, and the boiling points of these by-products are very different, so that the separation of a large amount of primary amines in industry is often difficult.
The selectivity of the catalyst to the reaction product is greatly affected, and metals such as nickel, cobalt, lead, ruthenium, copper, platinum and rhodium can be used to catalyze nitrile compounds to selectively produce amine compounds, wherein the metals such as nickel, cobalt and ruthenium are mainly used to hydrogenate nitriles to primary amines, while copper, platinum and rhodium are used to reduce nitriles to secondary amines in most cases. For example, Chinese patent CN103539676 discloses a 40% Ni-5% Mo/Al alloy 2 O 3 A supported catalyst at 80 deg.C,8MPa H 2 The reaction is carried out under the condition, the isophthalonitrile is completely converted, and the yield of the 1, 3-dimethylamino benzene reaches 98.02 percent. However, Al 2 O 3 And the diatomite carrier has certain acidity, which can promote condensation side reaction, the by-product is attached to the surface of the catalyst to reduce or inactivate the activity of the catalyst, and the stability of the catalyst is poor.
Disclosure of Invention
In view of the above, the present invention provides a composite metal oxide catalyst, and a preparation method and an application thereof, and the composite metal oxide catalyst provided by the present invention has high catalytic activity and stability for hydrogenation catalysis of cyano-containing amine-based substances, and has a high recycling rate.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a composite metal oxide catalyst, which comprises a component A2, a component A1 and a component A3, wherein the component A1 and the component A3 are loaded on the surface of the component A2;
the component A1 comprises one or two of Ni and Co;
the component A2 is a layered metal oxide, wherein the metals in the layered metal oxide comprise alkaline earth metals and aluminum; the alkaline earth metal comprises one or more of Mg, Ca and Ba; the molar ratio of the alkaline earth metal to the aluminum is (1-6): 1;
the component A3 is one or two of La and Ce;
in the composite metal oxide catalyst, the content of the component A1 is 40-50 wt%, and the content of the component A3 is 0.1-1 wt%.
The invention provides a preparation method of the composite metal oxide catalyst, which comprises the following steps:
mixing water-soluble transition metal salt, water-soluble alkaline earth metal salt, water-soluble aluminum salt, water-soluble rare earth metal salt, alkaline precipitator, pore-expanding agent and water, and performing coprecipitation to obtain a precursor; the water-soluble transition metal salt comprises one or two of water-soluble nickel salt and water-soluble cobalt salt; the water-soluble rare earth metal salt comprises one or two of water-soluble lanthanum salt and water-soluble cerium salt;
and roasting the precursor and then reducing to obtain the composite metal oxide catalyst.
Preferably, the pore-expanding agent comprises one or more of citric acid, carboxymethyl cellulose and oxalic acid;
the pore-expanding agent accounts for 1-5% of the mass of the transition metal in the water-soluble transition metal salt.
Preferably, the alkaline precipitant comprises one or more of ammonia water, alkali metal hydroxide and alkali metal salt;
the pH value of the mixed solution is 9-11.
Preferably, the temperature of the coprecipitation is 100-160 ℃, and the time is 4-8 h.
Preferably, the roasting temperature is 400-700 ℃, and the roasting time is 1-5 h.
Preferably, the reduction is hydrogen reduction, the temperature of the hydrogen reduction is 400-700 ℃, and the time is 2-8 hours.
The invention provides the application of the composite metal oxide catalyst in the technical scheme or the composite metal oxide catalyst obtained by the preparation method in the technical scheme in the selective hydrogenation reaction of cyano compounds.
Preferably, the cyano compound comprises one or more of acetonitrile, adiponitrile, benzonitrile, 1, 2-cyanobenzene and isophthalonitrile.
Preferably, the composite metal oxide catalyst is subjected to reduction activation before use; the reduction activation is hydrogen reduction, the temperature of the hydrogen reduction is 400-700 ℃, and the time is 2-8 hours;
the temperature of the selective hydrogenation reaction is 40-120 ℃, and the gauge pressure of hydrogen is 3-30 Mpa.
The invention provides a composite metal oxide catalyst, which comprises a component A2, a component A1 and a component A3, wherein the component A1 and the component A3 are loaded on the surface of the component A2; the component A1 comprises one or two of Ni and Co; the component A2 is a layered metal oxide, wherein the metals in the layered metal oxide comprise alkaline earth metals and aluminum; the alkaline earth metal comprises one or more of Mg, Ca and Ba; the molar ratio of the alkaline earth metal to the aluminum is (1-6): 1; the component A3 is one or two of La and Ce; in the composite metal oxide catalyst, the content of the component A1 is 40-50 wt%, and the content of the component A3 is 0.1-1 wt%. In the composite metal oxide catalyst provided by the invention, Ni and Co are main active components, the active components are high in content, rare earth metal is an auxiliary agent, the layered metal oxide is used as a carrier and plays a role of the active components, strong interaction exists among the component A1, the component A3 and the component A2, the specific surface area of the component A2 is large, and the dispersity of one or two of Ni and Co and the rare earth metal on the surface of the layered metal oxide is high, so that the catalyst has the characteristics of high catalytic activity and catalytic stability for the selective hydrogenation reaction of a cyano compound, high conversion rate of raw materials, high selectivity of a product and long service life of the catalyst, and has a good application prospect in the aspect of catalyzing the selective hydrogenation reaction of the cyano compound.
The invention provides a preparation method of the composite metal oxide catalyst, which comprises the following steps: mixing water-soluble transition metal salt, water-soluble alkaline earth metal salt, water-soluble aluminum salt, water-soluble rare earth metal salt, alkaline precipitator, pore-expanding agent and water, and performing coprecipitation to obtain a precursor; the water-soluble transition metal salt comprises one or two of water-soluble nickel salt and water-soluble cobalt salt; the water-soluble rare earth metal salt comprises one or two of water-soluble lanthanum salt and water-soluble cerium salt; and roasting the precursor to obtain the composite metal oxide catalyst. The composite metal oxide catalyst can be prepared by one-pot coprecipitation and roasting, and has the advantages of simple preparation process, simple operation, low cost and environmental friendliness.
Drawings
FIG. 1 is an XRD pattern of a composite metal oxide catalyst and an activation catalyst prepared in example 4, wherein a is a precursor, b is a calcined product, and c is a composite metal oxide catalyst;
FIG. 2 is a graph of the cyclic catalytic stability results for the activated catalyst prepared in example 4;
FIG. 3 is a graph comparing gas chromatography data of 1, 3-dimethylaminophenyl product and high polymer obtained during the 1 st to 15 th catalytic cycles (i.e., data 1 to data 15) of the activated catalyst prepared in example 4 during the testing of the stability of the cyclic catalysis;
FIG. 4 is a comparative close-up of gas chromatographic data for the product 1, 3-dimethylaminophenyl of FIG. 3;
FIG. 5 is a comparative enlarged view of the gas chromatographic data of the byproduct polymer in FIG. 3;
FIG. 6 is a mass spectrum fragment of GC-MS of trimer in by-product during the catalytic application of the activated catalyst prepared in example 3 of application example 4.
Detailed Description
The invention provides a composite metal oxide catalyst, which comprises a component A2, a component A1 and a component A3, wherein the component A1 and the component A3 are loaded on the surface of the component A2.
In the present invention, the component a2 is a layered metal oxide in which the metals include alkaline earth metals and aluminum; the alkaline earth metal comprises one or more of Mg, Ca and Ba; the molar ratio of the alkaline earth metal to the aluminum is (1-6): 1, preferably (2-5): 1, more preferably (3 to 4): 1.
in the present invention, the component a1 includes one or both of Ni and Co.
In the invention, the component A3 is one or two of La and Ce.
In the invention, the content of the component A1 in the composite metal oxide catalyst is 40-50 wt%, preferably 40-48 wt%, and more preferably 40-45 wt%; the content of the component A3 is 0.1-1 wt%, preferably 0.2-0.8 wt%, and more preferably 0.4-0.6 wt%; the content of the component A2 is preferably 49-59.9 wt%, more preferably 51.2-59.8 wt%, and further preferably 54.4-59.6 wt%.
The invention provides a preparation method of the composite metal oxide catalyst, which comprises the following steps:
mixing water-soluble transition metal salt, water-soluble alkaline earth metal salt, water-soluble aluminum salt, water-soluble rare earth metal salt, alkaline precipitator, pore-expanding agent and water, and performing coprecipitation to obtain a precursor; the water-soluble transition metal salt comprises one or two of water-soluble nickel salt and water-soluble cobalt salt;
and roasting the precursor to obtain the composite metal oxide catalyst.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The method mixes water-soluble transition metal salt, water-soluble alkaline earth metal salt, water-soluble aluminum salt, water-soluble rare earth metal salt, alkaline precipitator, pore-expanding agent and water, and coprecipitates to obtain the precursor.
In the invention, the water-soluble transition metal salt comprises one or two of water-soluble nickel salt and water-soluble cobalt salt, preferably comprises one or more of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt acetate, cobalt sulfate and cobalt chloride.
In the invention, the water-soluble alkaline earth metal salt comprises one or more of water-soluble magnesium salt, water-soluble calcium salt and water-soluble barium salt, and preferably comprises one or more of magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium chloride, calcium nitrate, calcium acetate, calcium chloride, barium nitrate, barium acetate and barium chloride.
In the present invention, the water-soluble aluminum salt preferably includes one or more of aluminum nitrate, aluminum acetate, aluminum sulfate and aluminum chloride.
In the invention, the water-soluble rare earth metal salt comprises one or two of water-soluble lanthanum salt and water-soluble cerium salt, and preferably comprises one or more of lanthanum chloride, lanthanum nitrate, cerium chloride and cerium nitrate.
The mass ratio of the water-soluble transition metal salt, the water-soluble alkaline earth metal salt, the water-soluble aluminum salt and the water-soluble rare earth metal salt is not particularly limited, and the composite metal oxide catalyst with the component A1 content of 40-50 wt%, the component A3 content of 0.1-1 wt% and the component A2 content of 49-59.9 wt% can be obtained.
In the invention, the alkaline precipitant preferably comprises one or more of ammonia water, alkali metal hydroxide and alkali metal salt, wherein the alkali metal hydroxide is preferably one or two of KOH and NaOH; the alkali metal salt preferably comprises NaHCO 3 、KHCO 3 、Na 2 CO 3 And K 2 CO 3 One or more of (a); the concentration of the ammonia water is preferably 10-20 wt%, and more preferably 12-18 wt%; the alkali metal hydroxide is preferably used in the form of a solid or aqueous alkali metal hydroxide solution, the alkali metal salt is preferably used in the form of a solid or aqueous alkali metal salt solution; the concentrations of the alkali metal hydroxide aqueous solution and the alkali metal salt aqueous solution are independently preferably 0.1 to 1.0mol/L, and more preferably 0.2 to 0.8 mol/L.
The mixing is not particularly limited, and the raw materials can be uniformly mixed, specifically, stirred and mixed. In a specific embodiment of the present invention, the mixing is preferably performed by dissolving a water-soluble transition metal salt, a water-soluble alkaline earth metal salt, a water-soluble aluminum salt, and a water-soluble rare earth metal salt in water, mixing the obtained inorganic salt solution with an alkaline reagent, and mixing the obtained inorganic saline-alkaline solution with a pore-expanding agent. The amount of water used in the present invention is not particularly limited, and the water-soluble transition metal salt, the water-soluble alkaline earth metal salt, the water-soluble aluminum salt and the water-soluble rare earth metal salt may be dissolved. The amount of the alkaline precipitant is not particularly limited, and the pH of the inorganic saline-alkaline solution may be adjusted to 9 to 11, and the pH of the mixed solution is more preferably 9.5 to 10.5, and even more preferably 10.
In the invention, the pore-expanding agent preferably comprises one or more of citric acid, carboxymethyl cellulose and oxalic acid, and the mass of the pore-expanding agent is preferably 1-5%, more preferably 2-4% and even more preferably 3% of the mass of the transition metal in the water-soluble transition metal salt.
In the invention, the temperature of the coprecipitation is preferably 100-160 ℃, more preferably 110-150 ℃, and further preferably 120-140 ℃, and the time of the coprecipitation is preferably 4-8 h, more preferably 5-7 h, and further preferably 6 h.
After the coprecipitation is completed, the invention preferably further comprises washing, drying and crushing the coprecipitate in sequence to obtain a precursor. The washing is not particularly limited, and the washing may be carried out until the product is neutral. In the invention, the drying temperature is preferably 70-120 ℃, and more preferably 80-100 ℃; in the present invention, the drying time is not particularly limited, and the drying time may be set to a constant weight. The crushing is not particularly limited, and the particle size of the composite metal oxide catalyst is 10 to 100 meshes.
After the precursor is obtained, the precursor is roasted and reduced to obtain the composite metal oxide catalyst. In the invention, the roasting temperature is preferably 400-700 ℃, more preferably 450-650 ℃, and further preferably 500-600 ℃; the roasting time is preferably 1-5 hours, more preferably 2-4 hours, and further preferably 2-3 hours. In the invention, the reduction is preferably hydrogen reduction, and the temperature of the hydrogen reduction is preferably 400-700 ℃, more preferably 450-650 ℃, and further preferably 500-600 ℃; the time for the reduction activation is preferably 2-8 h, more preferably 3-7 h, and further preferably 4-6 h.
After the reduction is completed, the present invention preferably further comprises cooling the resulting reduced product to room temperature to obtain a composite metal oxide catalyst. The cooling method of the present invention is not particularly limited, and may be any cooling method known to those skilled in the art, specifically, natural cooling.
The invention provides the application of the composite metal oxide catalyst in the technical scheme or the composite metal oxide catalyst obtained by the preparation method in the technical scheme in the selective hydrogenation reaction of cyano compounds.
In the invention, the cyano compound preferably comprises one or more of acetonitrile, adiponitrile, benzonitrile, 1, 2-cyanobenzene and isophthalonitrile, and more preferably comprises adiponitrile, benzonitrile or isophthalonitrile; and the acetonitrile, adiponitrile, benzonitrile, 1, 2-cyanobenzene and isophthalonitrile are subjected to selective hydrogenation reaction to respectively obtain ethylamine, hexamethylenediamine, benzylamine and 1, 3-dimethylamino benzene.
In the present invention, the method of application preferably comprises the steps of: mixing a cyano compound, a composite metal oxide catalyst and an organic solvent, and carrying out selective hydrogenation reaction to obtain an amine compound; the composite metal oxide catalyst is the composite metal oxide catalyst in the technical scheme or the composite metal oxide catalyst obtained by the preparation method in the technical scheme.
In the invention, the composite metal oxide catalyst is preferably subjected to reduction activation before use, the reduction activation is preferably hydrogen reduction, and the temperature of the hydrogen reduction is preferably 400-700 ℃, more preferably 450-650 ℃, and further preferably 500-600 ℃; the time for hydrogen reduction is preferably 2-8 h, more preferably 3-7 h, and further preferably 4-6 h.
In the present invention, the mass ratio of the cyano compound to the composite metal oxide catalyst is preferably 1: (0.1 to 0.5), more preferably 1: (0.1 to 0.4), and more preferably 1: (0.2-0.3).
In the invention, the organic solvent preferably comprises one or more of methanol, toluene, ethanol and N-methylpyrrolidone, and the dosage of the organic solvent is not particularly limited, so that the selective hydrogenation reaction can be smoothly carried out.
In the invention, the pressure (gauge pressure) of hydrogen in the selective hydrogenation reaction process is preferably 3-30 MPa, more preferably 5-25 MPa, and further preferably 10-20 MPa; the temperature of the selective hydrogenation reaction is preferably 40-120 ℃, more preferably 50-100 ℃, and further preferably 60-80 ℃; the time of the selective hydrogenation reaction is preferably 1-14 h, more preferably 2-12 h, and further preferably 3-10 h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
69.85g of Co (NO) 3 ) 2 ·6H 2 O、46.15g Mg(NO 3 ) 2 ·6H 2 O、22.51g Al(NO 3 ) 3 ·9H 2 O and 0.78g La (NO) 3 ) 2 ·6H 2 Dissolving O in pure water to obtain an inorganic salt solution, adding 17wt% ammonia water into the inorganic salt solution to adjust the pH value to 10.0, then adding 0.8g of oxalic acid, coprecipitating at 100 ℃ for 6 hours, washing the obtained precipitate to be neutral, and drying at 85 ℃ to constant weight to obtain a precursor; and roasting the precursor for 2 hours at 500 ℃ in an air atmosphere, reducing the precursor for 3 hours at 400 ℃ in flowing hydrogen, and naturally cooling the precursor to room temperature to obtain the composite metal oxide catalyst (recorded as B1).
Example 2
69.79g of Ni (NO) 3 ) 2 ·6H 2 O、47.04g Ba(NO 3 ) 2 ，22.51g Al(NO 3 ) 3 ·9H 2 O and 0.78g La (NO) 3 ) 2 ·6H 2 Dissolving O in pure water to obtain an inorganic salt solution, adding 17wt% ammonia water into the inorganic salt solution to adjust the pH value to 11.0, then adding 3.2g of citric acid, coprecipitating at the temperature of 130 ℃ for 4h, washing the obtained precipitate to be neutral, and drying at the temperature of 90 ℃ to constant weight to obtain a precursor; and roasting the precursor for 2 hours at 450 ℃ in an air atmosphere, reducing the precursor for 4 hours at 500 ℃ in flowing hydrogen, and naturally cooling the precursor to room temperature to obtain the composite metal oxide catalyst (recorded as B2).
Example 3
69.79g of Ni (NO) 3 ) 2 ·6H 2 O、7.84g Ba(NO 3 ) 2 ，38.46g Mg(NO 3 ) 2 ·6H 2 O、22.51g Al(NO 3 ) 3 ·9H 2 O and 0.78g La (NO) 3 ) 2 ·6H 2 Dissolving O in pure water to obtain an inorganic salt solution, adding a KOH solution with the concentration of 0.35mol/L into the inorganic salt solution to adjust the pH value to 10.5, then adding 1.2g of carboxymethyl cellulose, coprecipitating at the temperature of 140 ℃ for 3 hours, washing an obtained precipitation product to be neutral, and drying at the temperature of 95 ℃ to constant weight to obtain a precursor; and roasting the precursor for 3.5h at 550 ℃ in an air atmosphere, reducing the precursor for 5h at 450 ℃ in flowing hydrogen, and naturally cooling to room temperature to obtain the composite metal oxide catalyst (recorded as B3).
Example 4
69.79g of Ni (NO) 3 ) 2 ·6H 2 O、46.15g Mg(NO 3 ) 2 ·6H 2 O、22.51g Al(NO 3 ) 3 ·9H 2 O and 0.78g La (NO) 3 ) 2 ·6H 2 Dissolving O … in pure water to obtain inorganic salt solution, and adding Na with concentration of 0.30mol/L 2 CO 3 And NaHCO 3 Adjusting the pH value of the mixed solution to 9.5, then adding 2.0g of carboxymethyl cellulose, coprecipitating at 120 ℃ for 6 hours to obtain a precipitate, washing the precipitate with water to neutrality, and drying at 100 ℃ to constant weight to obtain a precursor; and roasting the precursor for 4 hours at 450 ℃ in an air atmosphere, reducing the precursor for 2 hours at 550 ℃ in flowing hydrogen, and naturally cooling the precursor to room temperature to obtain the composite metal oxide catalyst (recorded as B4).
Fig. 1 is an XRD spectrum of the catalyst prepared in example 4, wherein a is a precursor, b is a calcined product, and c is a composite metal oxide catalyst. As can be seen from fig. 1, the preparation method provided by the present invention successfully prepares a catalyst precursor with a hydrotalcite structure, and the precursor is calcined to be converted into a composite metal oxide catalyst.
Comparative example 1
69.79g of Ni (NO) 3 ) 2 ·6H 2 O、46.15g Mg(NO 3 ) 2 ·6H 2 O、22.51g Al(NO 3 ) 3 ·9H 2 O and 0.78g Ce (NO) 3 ) 3 ·6H 2 Dissolving O in pure water to obtain an inorganic salt solution, adding a NaOH solution with the concentration of 0.30mol/L into the inorganic salt solution to adjust the pH value to 9.5, coprecipitating for 5 hours at the temperature of 110 ℃, washing an obtained precipitation product to be neutral, and drying to constant weight at the temperature of 90 ℃ to obtain a precursor; and roasting the precursor for 2h at 500 ℃ in an air atmosphere, reducing the precursor for 2h at 500 ℃ in flowing hydrogen, and naturally cooling the precursor to room temperature to obtain the composite metal oxide catalyst (marked as C1).
Comparative example 2
69.79g of Ni (NO) 3 ) 2 ·6H 2 O、46.15g Mg(NO 3 ) 2 ·6H 2 O、22.51g Al(NO 3 ) 3 ·9H 2 Dissolving O in pure water to obtain inorganic salt solution, and adding Na with the concentration of 0.20mol/L into the inorganic salt solution 2 CO 3 Adjusting the pH value of the solution to 9.0, adding 1.6g of citric acid, coprecipitating at 110 ℃ for 5h, washing the obtained precipitate with water to neutrality, and drying at 100 ℃ to constant weight to obtain a precursor; and roasting the precursor for 2h at 450 ℃ in an air atmosphere, reducing the precursor for 2h at 450 ℃ in flowing hydrogen, and naturally cooling the precursor to room temperature to obtain the composite metal oxide catalyst (marked as C2).
Comparative example 3
A composite metal oxide catalyst and an activated catalyst were prepared according to the preparation method of example 4, differing from example 4 only in Ni (NO) 3 ) 2 ·6H 2 The mass of O was 12.39g, and an activated catalyst (designated as C3) was obtained
Comparative example 4
46.15g Mg (NO) 3 ) 2 ·6H 2 O and 22.51g Al (NO) 3 ) 3 ·9H 2 Dissolving O in pure water to obtain an inorganic salt solution, adding ammonia water with the concentration of 15wt% into the inorganic salt solution to adjust the pH value to 9.5, then adding 1.6g of citric acid, coprecipitating at the temperature of 110 ℃ for 5 hours to obtain a precipitate, washing the precipitate with water to be neutral, and drying at the temperature of 100 ℃ to constant weight to obtain the magnesium-aluminum hydrotalcite; placing the magnesium aluminum hydrotalcite in Ni (NO) 3 ) 2 Aqueous solution (containing 69.79g of Ni (NO) 3 ) 2 ·6H 2 O), soaking for 36h at room temperature, taking out, and drying at 90 ℃ to constant weight to obtain a precursor; and roasting the precursor for 2 hours at 450 ℃ in an air atmosphere, reducing the precursor for 5 hours at 450 ℃ in flowing hydrogen, and naturally cooling the precursor to room temperature to obtain the composite metal oxide catalyst (marked as C4).
Application example 1
Before use, the composite metal oxide catalysts prepared in examples 1 to 4 and comparative examples 1 to 3 are respectively subjected to reduction activation according to respective reduction conditions, and the obtained activated catalyst and a commercial raney nickel catalyst (marked as D1, purchased from liening zhongli catalyst science and technology ltd) are used as catalysts for catalyzing the reaction of selective hydrogenation of adiponitrile to prepare hexamethylene diamine, and the specific steps are as follows:
adding adiponitrile and a catalyst into a high-pressure reaction kettle, introducing hydrogen (7 MPa), and carrying out selective hydrogenation reaction for 4 hours at the temperature of 80 ℃ to obtain a crude product of the hexamethylene diamine (hexamethylene diamine and a byproduct, namely cyclohexylimine), wherein the mass of the catalyst is 3% of that of the adiponitrile, and the catalytic results of the activated catalyst are shown in Table 1:
TABLE 1 catalysis results of composite metal oxide catalysts prepared in examples 1-4 and comparative examples 1-3
Figure 397837DEST_PATH_IMAGE001
As can be seen from Table 1, the composite metal oxide catalyst prepared by the invention is used for catalyzing the reaction of preparing hexanediamine by selective hydrogenation of adiponitrile after reduction and activation, the conversion rate of the adiponitrile conversion rate is more than 99.87%, the selectivity of the hexanediamine is more than 93.22%, and the selectivity of a byproduct, namely cycloheximide, is less than 5.07%.
Comparative application example 1
A commercial Raney nickel catalyst (marked as D1 and purchased from Liaoning Zhongli catalyst science and technology Co., Ltd.) is used for catalyzing the reaction of selectively hydrogenating adiponitrile to prepare hexamethylene diamine, and the specific steps are as follows:
adding adiponitrile and an activation catalyst into a high-pressure reaction kettle, introducing hydrogen (7 MPa), and carrying out selective hydrogenation reaction for 5h at the temperature of 80 ℃ to obtain a crude product of the hexamethylene diamine (hexamethylene diamine and a byproduct, namely cyclohexylimine), wherein the mass of the activation catalyst is 3% of that of the adiponitrile, and the catalyst is used for 2 times. Primary catalytic effect: the conversion of adiponitrile was 95.94% and the selectivity to hexamethylene diamine was 76.73%. Catalytic effect for the 2 nd time: the conversion of adiponitrile was 92.95% and the selectivity to hexamethylenediamine was 58.94%.
Application example 2
The catalyst B4 prepared in the example 4 is subjected to reduction activation by adopting the reduction conditions of the example 4, and the obtained activated catalyst is used for catalyzing the reaction of preparing 1, 3-dimethylamino benzene by selectively hydrogenating isophthalonitrile, and the specific steps are as follows:
adding isophthalonitrile, an N-methylpyrrolidone solvent and an activation catalyst into a high-pressure reaction kettle, introducing hydrogen (7 MPa), and selectively hydrogenating for 4 hours at the temperature of 65 ℃ to obtain a1, 3-dimethylamino benzene crude product (1, 3-dimethylamino benzene and a byproduct high polymer), wherein the mass ratio of the isophthalonitrile to the N-methylpyrrolidone solvent is 1:9, and the mass of the activation catalyst is 3% of that of the isophthalonitrile. The catalyst is recycled for 21 times, and the catalyst after each catalytic reaction is reduced and activated according to the reduction conditions of the example 4, and then the next catalytic reaction is carried out. The initial catalytic reaction of the catalyst is recorded as recycling and used for 0 time, the 2 nd catalytic reaction is recorded as recycling and used for 1 time, the 3 rd catalytic reaction is recorded as recycling and used for 2 times, and the rest is done in the same way. The cycle stability catalysis results of the catalyst are shown in fig. 2-fig. 5 and table 2, wherein fig. 2 is a cycle catalysis stability result diagram of the activated catalyst, fig. 3 is a gas chromatography data comparison diagram of the product 1, 3-dimethylaminobenzene and the high polymer in the cycle catalysis stability test process of the activated catalyst, wherein the product 1, 3-dimethylaminobenzene is recycled for 1-15 times (namely, data 1-data 15), fig. 4 is a gas chromatography data comparison partial enlarged view of the product 1, 3-dimethylaminobenzene in fig. 3, and fig. 5 is a gas chromatography data comparison partial enlarged view of the high polymer as the byproduct in fig. 3.
Table 2 cycle stability catalytic results for the composite metal oxide catalyst prepared in example 4
Figure 393475DEST_PATH_IMAGE002
As can be seen from fig. 2 to 5 and table 2, after the composite metal oxide catalyst prepared by the present invention is recycled for 20 times, the performance of the catalyst is not significantly reduced, and high conversion rate and selectivity are still maintained, which indicates that the catalyst prepared by the present invention has strong stability, high activity and long catalytic life.
Application example 3
The composite metal oxide catalyst prepared in the example 2 is subjected to reduction activation according to the reduction conditions of the example 2, and the obtained activated catalyst is used for catalyzing the reaction of preparing the benzylamine by selectively hydrogenating benzonitrile, and the specific steps are as follows:
adding benzonitrile and an activating catalyst into a high-pressure reaction kettle, introducing hydrogen (5 MPa), and carrying out selective hydrogenation reaction for 4.5h at 70 ℃ to obtain a crude product of benzylamine (benzylamine and a byproduct dibenzylamine), wherein the mass of the activating catalyst is 3% of that of the benzonitrile, and the catalytic result of the activating catalyst is as follows: the conversion of benzonitrile was 99.83%, the selectivity to benzylamine was 91.22%, and the selectivity to by-product (dibenzylamine) was 7.96%.
Comparative application example 2
A commercial Raney nickel catalyst (marked as D1, purchased from Liaoning Zhongli catalyst science and technology Co., Ltd.) is used for catalyzing the reaction of preparing the benzylamine by selectively hydrogenating benzonitrile, and the specific steps are as follows:
adding cyanobenzene and an activating catalyst into a high-pressure reaction kettle, introducing hydrogen (5 MPa), and carrying out selective hydrogenation reaction for 5 hours at 70 ℃ to obtain a crude benzylamine product (benzylamine and a byproduct dibenzylamine), wherein the mass of the activating catalyst is 3% of that of the cyanobenzene, and the catalyst is utilized for 3 times. Primary reaction catalytic effect: the conversion rate of benzonitrile was 99.91%, and the selectivity to benzylamine was 86.73%. The 1 st recycling of catalytic effect: the conversion of benzonitrile was 98.94% and the selectivity to benzylamine was 74.67%. The 2 nd circulation utilizes the catalytic effect: the conversion of benzonitrile was 93.61%, and the selectivity to benzylamine was only 14.72%.
Application example 4
The composite metal oxide catalysts prepared in example 1 and comparative example 4 are subjected to reduction activation according to the reduction conditions of example 4, and the obtained activated catalyst is used for catalyzing the reaction of preparing 1, 3-dimethylamino benzene by selectively hydrogenating isophthalonitrile, and the specific steps are as follows:
adding isophthalonitrile, an N-methylpyrrolidone solvent and an activation catalyst into a high-pressure reaction kettle, introducing hydrogen (6 MPa), and carrying out selective hydrogenation reaction for 4h at 90 ℃ to obtain a1, 3-dimethylamino benzene crude product (1, 3-dimethylamino benzene and a byproduct high polymer), wherein the mass ratio of the isophthalonitrile to the N-methylpyrrolidone solvent is 1:9, and the mass of the activation catalyst is 3% of that of the isophthalonitrile.
Catalytic result of catalyst B1: the conversion of isophthalonitrile was 99.62%, the selectivity for 1, 3-dimethylaminophenyl was 91.22%, and the selectivity for the by-product polymer was 9.82%.
Catalytic result of catalyst C4: the conversion of isophthalonitrile was 98.11%, the selectivity for 1, 3-dimethylaminophenyl was 46.06%, and the selectivity for the by-product polymer was 7.43%.
Fig. 6 is a mass spectrum fragment diagram of GC-MS of trimer in the by-product obtained from the catalytic reaction of catalyst B1, and it can be known from fig. 6 that, in the hydrogenation reaction of isophthalonitrile catalyzed by catalyst B1, a trimer by-product exists in the by-product, the molecular weight is 374, and the structural formula is shown in formula I:
Figure 124671DEST_PATH_IMAGE003
formula I.
Comparative application example 3
A commercial Raney nickel catalyst (marked as D1, purchased from Liaoning Zhongli catalyst science and technology Co., Ltd.) is used for catalyzing the reaction of preparing 1, 3-dimethylamino benzene by selectively hydrogenating isophthalonitrile, and the specific steps are as follows:
adding isophthalonitrile, an N-methylpyrrolidone solvent and an activation catalyst into a high-pressure reaction kettle, introducing hydrogen (6 MPa), and carrying out selective hydrogenation reaction for 4h at 90 ℃ to obtain a1, 3-dimethylamino benzene crude product (1, 3-dimethylamino benzene and a byproduct high polymer), wherein the mass ratio of the isophthalonitrile to the N-methylpyrrolidone solvent is 1:9, the mass of the activation catalyst is 3% of that of the isophthalonitrile, and the catalyst is utilized for 3 times. Primary reaction catalytic effect: the conversion of isophthalonitrile was 99.94% and the selectivity of 1, 3-dimethylaminophenyl was 84.23%. The high polymer selectivity was 9.63%. The 1 st cycle utilizes the catalytic effect: the conversion of isophthalonitrile was 99.95%, the selectivity for 1, 3-dimethylaminophenyl was 79.85%, and the selectivity for high polymer was 11.35%. The 2 nd circulation utilizes the catalytic effect: the conversion of isophthalonitrile was 95.61%, the selectivity for 1, 3-dimethylaminophenyl was 16.79%, and the selectivity for high polymer was 18.60%.
Application example 5
The composite metal oxide catalyst prepared in example 3 is subjected to reduction activation according to the reduction conditions of example 3, and the obtained activated catalyst is used for catalyzing the reaction of preparing 1, 3-dimethylamino benzene by selectively hydrogenating isophthalonitrile, and the specific steps are as follows:
adding isophthalonitrile, an N-methylpyrrolidone solvent and an activation catalyst into a high-pressure reaction kettle, introducing hydrogen (5 MPa), and carrying out selective hydrogenation reaction for 4.5h at the temperature of 80 ℃ to obtain a1, 3-dimethylamino benzene crude product (1, 3-dimethylamino benzene and a byproduct high polymer), wherein the mass ratio of the isophthalonitrile to the N-methylpyrrolidone solvent is 1:9, and the mass of the activation catalyst is 3% of that of the isophthalonitrile. Catalytic results for activated catalyst B5: the conversion of isophthalonitrile was 100%, the selectivity for 1, 3-dimethylaminophenyl was 92.76%, and the selectivity for the by-product polymer was 5.48%.
Application example 6
The composite metal oxide catalyst prepared in example 1 is subjected to reduction activation according to the reduction conditions of example 1, and the obtained activated catalyst is used for catalyzing the reaction of preparing 1, 3-dimethylamino benzene by selectively hydrogenating isophthalonitrile, and the specific steps are as follows:
adding isophthalonitrile, an N-methylpyrrolidone solvent and an activation catalyst into a high-pressure reaction kettle, introducing hydrogen (7 MPa), and carrying out selective hydrogenation reaction for 4h at 65 ℃ to obtain a1, 3-dimethylamino benzene crude product (1, 3-dimethylamino benzene and a byproduct high polymer), wherein the mass ratio of the isophthalonitrile to the N-methylpyrrolidone solvent is 1:9, the mass of the activation catalyst is 3% of that of the isophthalonitrile, and the catalysis result of the activation catalyst is as follows: the conversion of isophthalonitrile was 100%, the selectivity for 1, 3-dimethylaminophenyl was 96.75%, and the by-product polymer was 2.47%.
Application example 7
The composite metal oxide catalyst prepared in the example 2 is subjected to reduction activation according to the reduction conditions of the example 2, and the obtained activated catalyst is used for catalyzing the reaction of preparing 1, 3-dimethylamino benzene by selectively hydrogenating isophthalonitrile, and the specific steps are as follows:
in fixed bed continuous reaction kettleWherein the mass ratio of the isophthalonitrile to the methanol solvent is 1:6, the reaction pressure is 8MPa, the reaction temperature is 100 ℃, and the airspeed of the reaction liquid is 2.0 h -1 Space velocity of hydrogen gas is 500 h -1 The loading of the activated catalyst was 50 ml. Catalytic results of the activated catalyst: the conversion of isophthalonitrile was 100%, the selectivity for 1, 3-dimethylaminophenyl was 95.82%, and the by-product polymer was 2.63%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A composite metal oxide catalyst, characterized by comprising a component a2 and a component a1 and a component A3 supported on the surface of the component a 2;
the component A1 comprises one or two of Ni and Co;
the component A2 is a layered metal oxide, and the metals in the layered metal oxide comprise alkaline earth metals and aluminum; the alkaline earth metal comprises one or more of Mg, Ca and Ba; the molar ratio of the alkaline earth metal to the aluminum is (1-6): 1;
the component A3 is one or two of La and Ce;
in the composite metal oxide catalyst, the content of the component A1 is 40-50 wt%, and the content of the component A3 is 0.1-1 wt%.
2. The method for producing a composite metal oxide catalyst according to claim 1, comprising the steps of:
mixing water-soluble transition metal salt, water-soluble alkaline earth metal salt, water-soluble aluminum salt, water-soluble rare earth metal salt, alkaline precipitator, pore-expanding agent and water, and performing coprecipitation to obtain a precursor; the water-soluble transition metal salt comprises one or two of water-soluble nickel salt and water-soluble cobalt salt; the water-soluble rare earth metal salt comprises one or two of water-soluble lanthanum salt and water-soluble cerium salt;
and roasting the precursor and then reducing to obtain the composite metal oxide catalyst.
3. The method according to claim 2, wherein the pore-expanding agent comprises one or more of citric acid, carboxymethyl cellulose and oxalic acid;
the pore-expanding agent accounts for 1-5% of the mass of the transition metal in the water-soluble transition metal salt.
4. The method according to claim 2, wherein the alkaline precipitant comprises one or more of ammonia water, alkali metal hydroxide and alkali metal salt.
5. The preparation method according to claim 2, 3 or 4, characterized in that the temperature of the coprecipitation is 100 to 160 ℃ and the time is 4 to 8 hours.
6. The preparation method according to claim 2, wherein the roasting temperature is 400-700 ℃ and the roasting time is 1-5 h.
7. The preparation method according to claim 2, wherein the reduction is hydrogen reduction, and the temperature of the hydrogen reduction is 400-700 ℃ for 2-8 h.
8. Use of the composite metal oxide catalyst according to claim 1 or the composite metal oxide catalyst obtained by the preparation method according to any one of claims 2 to 7 in a selective hydrogenation reaction of a cyano compound.
9. The use according to claim 8, wherein the cyano compound comprises one or more of acetonitrile, adiponitrile, benzonitrile, 1, 2-cyanobenzene and isophthalonitrile.
10. Use according to claim 8, wherein the complex metal oxide catalyst is reductively activated prior to use; the reduction activation is hydrogen reduction, the temperature of the hydrogen reduction is 400-700 ℃, and the time is 2-8 hours;
the temperature of the selective hydrogenation reaction is 40-120 ℃, and the gauge pressure of hydrogen is 3-30 Mpa.
CN202210714145.2A 2022-06-23 2022-06-23 Composite metal oxide catalyst and preparation method and application thereof Pending CN114797880A (en)

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