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CN116554036A - Method for preparing hexamethylenediamine by taking 6-aminocapronitrile as raw material - Google Patents

Method for preparing hexamethylenediamine by taking 6-aminocapronitrile as raw material Download PDF

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CN116554036A
CN116554036A CN202310502301.3A CN202310502301A CN116554036A CN 116554036 A CN116554036 A CN 116554036A CN 202310502301 A CN202310502301 A CN 202310502301A CN 116554036 A CN116554036 A CN 116554036A
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aminocapronitrile
catalyst
nickel
hexamethylenediamine
cobalt
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陈曼柏
李珊
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a method for preparing hexamethylenediamine by taking 6-aminocapronitrile as a raw material, wherein the hexamethylenediamine is prepared by the reaction of 6-aminocapronitrile and hydrogen in the presence of a diluent by taking a supported nickel-cobalt alloy as a catalyst. According to the method for preparing hexamethylenediamine, disclosed by the invention, the reaction temperature of 6-aminocapronitrile can be reduced by using the supported nickel-cobalt alloy catalyst and ammonia as diluents, hexamethylenediamine is prepared by hydrogenation under low pressure, the selectivity of hexamethylenediamine is improved, and the amount of byproducts DCH, HMI, BHT is reduced; can improve the activity of the catalyst, reduce the dosage of the catalyst, and only needs half of the dosage of the Raney nickel catalyst.

Description

Method for preparing hexamethylenediamine by taking 6-aminocapronitrile as raw material
Technical Field
The invention belongs to the technical field of organic chemical industry, relates to a method for preparing hexamethylenediamine by taking 6-aminocapronitrile as a raw material, and particularly relates to a method for preparing hexamethylenediamine by hydrogenating 6-aminocapronitrile.
Background
The hexamethylenediamine (1, 6-hexamethylenediamine) has wide application, is mainly used for manufacturing nylon 66, and nylon 66 is the earliest polyamide which realizes industrialization, and is the most important two polyamide substance classes in parallel with nylon 6, so that people are paid attention to and researched. Besides being used for the production of nylon 66, the hexamethylenediamine can also be used for producing nylon 610, nylon 612 and other products, and has a great deal of application in the aspects of polyimine carboxylate foam plastics, polyurethane foam plastics, paint, epoxy resin curing agents, organic crosslinking agents, pesticides, iron ore, copper ore flotation agents and the like, so that the hexamethylenediamine is an important organic chemical raw material.
At present, the large-scale industrialized hexamethylenediamine synthesis method is an adiponitrile hydrogenation method, the adiponitrile production process mainly comprises a butadiene direct hydrocyanation method and an acrylonitrile electrolytic dimerization method, and the technologies are mainly mastered by international oligopolists and become neck technology developed by the domestic nylon industry. Chinese patent CN1251087a discloses a process for the continuous hydrogenation of adiponitrile using a kettle reactor, using a sponge cobalt catalyst in a reaction medium that is substantially alkali free, to catalyze the hydrogenation of adiponitrile at relatively low temperatures and pressures. The method can not entrain catalyst in the process of extracting the reaction liquid, and is easy to cause pipeline blockage. Therefore, the current large-scale industrialized adiponitrile hydrogenation process for preparing hexamethylenediamine mainly adopts a fluidized bed reactor, but the catalyst concentration in the reactor is high and the collision is intense, so that the catalyst is easy to break and pulverize, and the stable operation of the device is influenced. In addition, the process for preparing hexamethylenediamine by hydrogenation of adiponitrile inevitably generates diaminocyclohexane, the melting boiling point of the impurity is close to that of hexamethylenediamine, and the impurity is difficult to separate and is a key impurity affecting the quality of nylon 66 products.
6-aminocapronitrile is an important chemical intermediate, can be used for producing 1, 6-hexamethylenediamine by complete hydrogenation, and caprolactam and ammonia produce a key intermediate 6-aminocapronitrile under the action of a catalyst, and the high-purity 6-aminocapronitrile is obtained by separation and hydrogenation reaction, so that the required hexamethylenediamine product is obtained.
CN111995526 a discloses a method for synthesizing hexamethylenediamine by 6-aminocapronitrile through fixed bed hydrogenation, 6-aminocapronitrile and hydrogen are subjected to hydrogenation reaction in a fixed bed reactor under the action of a catalyst to prepare hexamethylenediamine, the reaction temperature is 150 ℃, the reaction pressure is 5MPa, the reaction temperature is higher, the reaction pressure is higher, the catalyst usage amount is larger, and the selectivity of hexamethylenediamine is lower.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for preparing hexamethylenediamine by taking 6-aminocapronitrile as a raw material, which can reduce the reaction temperature and the reaction pressure of 6-aminocapronitrile, prepare hexamethylenediamine by hydrogenation at low temperature and low pressure, reduce the use amount of a catalyst and improve the selectivity of hexamethylenediamine.
The technical scheme for realizing the purpose of the invention comprises the following steps:
a method for preparing hexamethylenediamine by taking 6-aminocapronitrile as a raw material, taking a supported nickel-cobalt alloy catalyst as a catalyst, and reacting the 6-aminocapronitrile with hydrogen in the presence of a diluent.
The active components of the supported nickel-cobalt alloy catalyst comprise active elements such as nickel and cobalt.
The mass content of the nickel in the catalyst is 1.0-10%, preferably 3-5%;
the mass content of the cobalt in the catalyst is 0.1-2%, preferably 0.5-1.5%;
wherein the mass of nickel is measured by the mass of nickel element, and the mass of cobalt is measured by the mass of cobalt element.
The diluent comprises alcohols, such as any one or a combination of at least two of ethanol, methanol, tertiary butanol, isopropanol, n-propanol, isobutanol and n-butanol; also comprises ammonia substances such as any one or at least two of ammonia, methylamine, ethylamine, propylamine, ethylenediamine, hexamethylenediamine and hexamethylenetetramine; ammonia substances such as ammonia, hexamethylenediamine are preferred. When ammonia is used as the diluent, the molar ratio of ammonia to 6-aminocapronitrile is 1 to 10, preferably 3 to 5 to 1.
The molar ratio of the hydrogen to the 6-aminocapronitrile is (2-100): 1.
The reaction temperature is 30-120 ℃, preferably 60-90 ℃, and the reaction pressure is 0.1-4.0 MPa, preferably 1.5-2.5 MPa.
The mass ratio of the catalyst to the 6-aminocapronitrile is (0.05-0.5): 1.
The reaction time is 5-500 seconds.
The carrier of the nickel-cobalt alloy catalyst is spherical silicon dioxide containing mesopores;
the aperture of the carrier is 2-50 nm;
the specific surface area of the carrier is 200-450 m 2 /g；
The pore volume of the carrier is 0.5-1.5 ml/g;
the bulk density of the carrier is 0.3-1.0 g/ml.
The nickel-cobalt alloy is dispersed on the carrier in a nano-form, and the particle size of the active component is 0.5-5.0 nm.
The preparation method of the supported nickel-cobalt alloy catalyst is not limited, and the preparation method can be the following scheme and comprises the following steps:
a1 A mixed solution containing a nickel precursor and a cobalt precursor is obtained, and a carrier is immersed in the mixed solution to obtain a catalyst precursor; or alternatively
a2 Respectively obtaining a solution containing a nickel precursor and a solution containing a cobalt precursor, immersing a carrier in the solution containing the cobalt precursor for treatment, drying, and immersing the obtained solid in the solution containing the nickel precursor to obtain a catalyst precursor;
b) And (3) carrying out reduction treatment on the catalyst precursor obtained in a 1) or a 2) to obtain the nickel-cobalt alloy catalyst.
In particular, in the present application, the means for obtaining the catalyst precursor includes both co-impregnation and stepwise impregnation methods. In the co-impregnation method, a mixed solution containing both the nickel precursor and the cobalt precursor is first prepared, and then the support is impregnated in the mixed solution. In the step impregnation method, the support is first impregnated with a solution containing a cobalt precursor to obtain a semi-dry solid, and then the semi-dry solid is impregnated with a solution containing a nickel precursor.
The nickel precursor comprises a nickel ammine complex including an inorganic ammine complex, preferably at least one of nickel hexammine nitrate, nickel hexammine chloride.
The cobalt precursor comprises a cobalt ammonia complex, preferably an inorganic ammonia complex. The cobalt ammine complex is at least one selected from cobalt hexaammine nitrate and cobalt hexaammine trichloride.
The nickel ammonia complex is obtained by reacting and mixing a solution containing a nickel source with ammonia water.
The mass percentage concentration of nickel and cobalt in the mixed solution is 0.5-2.0wt%; wherein the content of nickel in the mixed solution is calculated by the content of nickel element; the content of cobalt in the mixed solution is calculated as the content of cobalt element.
The nickel source is soluble nickel salt, the soluble nickel salt is selected from at least one of inorganic acid salts of nickel, and the soluble nickel salt is selected from at least one of nickel nitrate and nickel chloride.
The cobalt ammonia complex is obtained by mixing a solution containing a cobalt source with ammonia water, wherein the cobalt source is soluble cobalt salt, the soluble cobalt salt is selected from at least one of cobalt inorganic acid salts, and the soluble cobalt salt is selected from at least one of cobalt nitrate and cobalt chloride.
Specifically, a solution containing a nickel source is mixed with ammonia water under heating to react, thereby obtaining a solution containing a nickel ammine complex.
Specifically, a solution containing a cobalt source is mixed with ammonia water under heating to obtain a solution containing a cobalt ammine complex.
The mass concentration of the ammonia water is 25-28 wt%, and the pH value of the ammonia water used for mixing the nickel ammonia complex solution and the cobalt ammonia complex solution is 10-12.
The a 2) is as follows: mixing the obtained solution containing the cobalt ammine complex with ammonia water, immersing a carrier therein, mixing, stirring, filtering, washing and drying to obtain a solid;
mixing the obtained solution containing nickel ammonia complex with ammonia water, adding the obtained solid into the mixture, mixing and stirring the mixture, filtering the mixture, and washing the mixture to obtain the catalyst precursor.
The drying condition is 100-200 ℃ for not less than 2 hours.
The carrier in the step a 1) and the step a 2) is prepared by adopting the following method: 1) Mixing raw materials containing silicon dioxide powder, silica sol, acid, dispersing agent and organic amine to obtain mixed slurry; 2) And (2) forming the mixed slurry obtained in the step (1) in a high Wen Youzhu by a jet generator, and then aging and roasting to obtain the micron spherical silica, namely the carrier. The raw materials in the step 1) further comprise an additive, wherein the additive is at least one selected from wollastonite, kaolin, silicon carbide fiber, glass fiber and talcum powder.
In the step 1), the mass percentage of the silicon dioxide powder in the mixed slurry is 10-30%, the mass percentage of the silica sol in the mixed slurry is 60-80%, and the addition amount of the dispersing agent is SiO in the mixed slurry 2 0.1 to 5 percent of the mass, wherein the addition amount of the additive is SiO in the mixed slurry 2 0.1 to 5 percent of the mass. SiO in the mixed slurry 2 The molar ratio of the catalyst to the organic amine is 1:0.05-0.2. The molar ratio of the acid to the organic amine is 1:1-3.
In step 1), the particle size of the silicon dioxide powder is 0.1-2 mu m; siO in the silica sol 2 The mass fraction of the silica sol is 20-40%, and SiO in the silica sol is 2 The particle size of (2) is 2-50 nm. The acid is at least one selected from organic acid and inorganic acid. The organic acid comprises at least one of salicylic acid, acetic acid, oxalic acid and citric acid. The inorganic acid comprises at least one of hydrochloric acid, nitric acid and phosphoric acid. The dispersing agent is at least one selected from methanol, ethanol, isopropanol, amine acetate, ammonium citrate, polyethylene glycol and polymaleic acid. The organic amine is at least one selected from ethylenediamine, ethanolamine, triethylenediamine, diethylenetriamine and hexamethylenetetramine.
In the step 2), the oil in the oil column is at least one selected from vacuum pump oil, transformer oil, paraffin oil, solvent oil, vegetable oil and mineral oil containing C10-C13 mixed straight-chain alkane; the temperature of the oil column is 80-150 ℃. The aperture of the nozzle of the jet flow generator is 0.1-1.0 mm; the jet velocity is 1-20 m/s.
In the step 2), the aging time is 3-24 hours. The roasting temperature is 500-700 ℃ and the roasting time is 10-24 h.
In the step b), the reducing atmosphere is selected from hydrogen or a mixed gas of hydrogen and an inactive gas. The inactive gas is selected from at least one of inert gases. The inert gas is at least one selected from nitrogen and argon. The reducing atmosphere is a mixed atmosphere of hydrogen and nitrogen, and the volume percentage of the hydrogen in the mixed gas is 10-30%. The reduction treatment conditions are as follows: the reduction temperature is 250-800 ℃ and the reduction time is 0.5-3.0 h.
The invention has the characteristics and effects that:
1. according to the method for preparing hexamethylenediamine, disclosed by the invention, the reaction temperature and the reaction pressure of 6-aminocapronitrile can be reduced by adopting a supported nickel-cobalt alloy catalyst and using ammonia as a diluent, and hexamethylenediamine is prepared by hydrogenation at low temperature and low pressure, so that the selectivity of hexamethylenediamine can be improved, and the amounts of byproducts DCH (cyclohexanediamine), HMI (cyclohexylimine) and BHT (dihexanetriamine) can be reduced.
2. The supported nickel-cobalt alloy catalyst can improve the activity of the catalyst, reduce the dosage of the catalyst, and only needs half or less of the dosage of the Raney nickel catalyst.
Description of the embodiments
The invention will be further illustrated by the following examples, but the invention is not limited to these examples. Unless otherwise indicated, the starting materials and reagents in the examples of the invention were all purchased commercially.
Nickel-cobalt alloy supported catalyst for preparing hexamethylenediamine by hydrogenating 6-aminocapronitrile, mesoporous silica is used as carrier, and NixCo is used for catalyst composition 1 -x/SiO 2 The catalyst is prepared by adopting an impregnation method, and is prepared by washing, drying and reducing, active components of metal nickel and cobalt are loaded, wherein the nickel content in the catalyst is 1.0-10% by weight, and the cobalt content is 0.1-2% by weight.
The carrier is formed mesoporous silica, the shape of the carrier is spherical, and the pore diameter of the catalyst particles is 2-50 nm.
The specific surface area of the carrier is 100-350 m 2 /g, wellThe volume is 0.5-1.5 ml/g, and the bulk density is 0.6-1.0 g/ml.
The method comprises the steps of preparing acidic nickel and cobalt solutions into ammonia complex precursors, impregnating the precursor solutions of the two metals on a silicon oxide carrier together or step by step, washing, drying, reducing and the like, wherein the used atmosphere is hydrogen balanced by inert gases such as nitrogen or argon.
The nickel source used for preparing the nickel catalyst is nickel nitrate or nickel chloride, the cobalt source is cobalt nitrate, cobalt chloride or cobalt chloride, and the concentration of the nickel source and the cobalt source is generally 100-5000 ppm.
The prepared nickel-cobalt catalyst is highly dispersed on a silicon oxide carrier in a nano-form, and the nano-particle size of the nickel-cobalt alloy is 1.0-5.0 nm.
6-aminocapronitrile is hydrogenated to prepare hexamethylenediamine under the conditions of the reaction temperature of 60-90 ℃ and the reaction pressure of 1.5-2.5 MPaG.
Example 1
Preparation of supported nickel-cobalt alloy catalyst
a) Weighing SiO with average particle size of 2 μm 2 21g of powder, 15ml of concentrated hydrochloric acid and SiO 2 126g (wherein SiO) of 30% by weight of alkaline silica sol 2 The average particle size of (2) is 25 nm) and 10ml of methanol are fully mixed, 15g of hexamethylenetetramine is added, and fully dissolved, thus obtaining mixed slurry;
b) And d, selecting a nozzle with the aperture of 0.25mm, mounting the nozzle to a jet generator, injecting the mixed slurry obtained in the step a into 25# transformer oil with the temperature of 95 ℃ at the speed of 5m/s for molding, standing and aging for 4 hours, separating molded pellets from the oil, and vacuum drying at the temperature of 80 ℃ for 12 hours. Washing the obtained product to be neutral, drying at 140 ℃ for 10 hours, and roasting at 550 ℃ for 12 hours to obtain micron spherical silicon oxide particles, namely a carrier;
c) 4.0485g of NiCl was weighed out 2 ·6H 2 O (nickel content 24.70%) is dissolved in 10ml deionized water to prepare a solution, and the solution is heated to micro-boiling condition and then added to NiCl 2 1mL of 25% ammonia water is added dropwise into the solution until precipitation is completely dissolved again, and then 1mL of 36.5% hydrochloric acid and 1mL of pure H are added dropwise 2 O 2 Until the precipitate is completely dissolved, obtaining transparent solution of nickel hexammoniate trichloride, and fixing the volume to 50.00ml, thus obtaining solution containing nickel ammine complex;
d) Weigh 2.024g CoCl 2 ·6H 2 O (cobalt content 24.7%) was dissolved in 10ml deionized water to prepare a solution, which was heated to slightly boiling, and then cooled to CoCl 2 1mL of 25% ammonia water was added dropwise to the solution to complete precipitation, followed by 1mL of 36.5% hydrochloric acid and 1mL of pure H 2 O 2 Until the precipitate is completely dissolved, obtaining a red transparent cobalt hexammoniate trichloride solution, and fixing the volume to 50.00ml to obtain a cobalt ammine complex-containing solution;
e) Transferring 5700 mu L of the solution containing the cobalt ammonia complex to 144.3mL of ammonia water solution with pH of 12, adding 6.0g of the spherical silicon oxide particles prepared in the step b, mixing, fully stirring at 60 ℃ for 3.0 hours, filtering the mixed solution, washing with deionized water, and drying at 120 ℃ for 2 hours to obtain a solid;
f) Transferring 14250 mu L of solution containing nickel-ammonia complex to 135.7mL of ammonia water solution with pH of 12, adding the dried solid prepared in the step e, mixing, fully stirring at 60 ℃ for 3.0 hours, filtering, washing with deionized water, and drying at 120 ℃ for 2 hours to obtain a catalyst precursor;
g) Placing the catalyst precursor in a tube furnace, at H 2 And N 2 Mixed gas (H) 2 Reducing for 0.5h at 400 ℃ in the atmosphere with the volume percentage of 10% in the mixed gas to obtain a nickel-cobalt alloy catalyst, and marking the nickel-cobalt alloy catalyst as sample No. 1;
h) In sample 1# the mass percent of nickel in the sample was 4.6wt% and the mass percent of cobalt in the sample was 0.95wt%. Sample 1# nickel-cobalt alloy is dispersed on a silicon oxide carrier in a nano-form, and the particle size of the nickel-cobalt alloy ranges from 0.75 nm to 3.52nm, and the average particle size is 2.18nm.
Example 2
a) Weighing SiO with average particle size of 2 μm 2 21g of powder, 5ml of concentrated nitric acid and SiO 2 126g (wherein SiO) of 30% by weight of alkaline silica sol 2 25nm average particle size) and ethanol 10ml, and addingAdding 2g (300 meshes) of wollastonite and 15g of hexamethylenetetramine, and fully dissolving to obtain mixed slurry;
b) A nozzle with the aperture of 0.25mm is selected and mounted on a jet generator, the mixed slurry obtained in the step a is injected into 25# transformer oil with the temperature of 90 ℃ at the speed of 5m/s for molding, the mixture is kept stand and aged for 4 hours, molded pellets are separated from the oil, and the mixture is dried in vacuum at the temperature of 60 ℃ for 24 hours. Washing the obtained product to be neutral, drying at 140 ℃ for 10 hours, and roasting at 550 ℃ for 12 hours to obtain micron spherical silicon oxide particles, namely a carrier;
c) 4.9529g Ni (NO) 3 ) 2 (nickel content: 20.19%) was dissolved in 10ml of deionized water to prepare a solution, and was heated to slight boiling, and then was added to Ni (NO) 3 ) 2 1mL of 28% ammonia water is added dropwise into the solution until precipitation is completely dissolved again, and then 1mL of 68% concentrated nitric acid and 1mL of pure H are added dropwise 2 O 2 Until the precipitate is completely dissolved, obtaining transparent nickel hexammoniate nitrate solution, and fixing the volume to 50.00ml, thus obtaining solution containing nickel ammine complex;
d) Weigh 2.024g CoCl 2 ·6H 2 O (cobalt content 24.7%) was dissolved in 10ml deionized water to prepare a solution, which was heated to slightly boiling, and then cooled to CoCl 2 1mL of 28% ammonia water was added dropwise to the solution to complete precipitation, followed by 1mL of 36.5% hydrochloric acid and 1mL of pure H 2 O 2 Until the precipitate is completely dissolved, obtaining a red transparent cobalt hexammoniate trichloride solution, and fixing the volume to 50.00ml to obtain a cobalt ammine complex-containing solution;
e) Transferring 2900 mu L of the solution containing the cobalt ammonia complex to 147.1mL of ammonia water solution with pH of 12, adding 6.0g of the spherical silicon oxide particles prepared in the step b, mixing, fully stirring at 60 ℃ for 3.0 hours, filtering the mixed solution, washing with deionized water, and drying at 120 ℃ for 2 hours to obtain a solid;
f) Transferring 9000 mu L of a solution containing nickel-ammonia complex to 141.0mL of ammonia water solution with pH of 12, adding the dried solid prepared in the step e, mixing, fully stirring at 30 ℃ for 2.0 hours, filtering, washing with deionized water, drying at 120 ℃ for 2 hours in an oven, and roasting at 400 ℃ for 2 hours to obtain a catalyst precursor;
g) Placing the catalyst precursor in a tube furnace, at H 2 And N 2 Mixed gas (H) 2 Reducing for 6 hours at 50 ℃ in the atmosphere with the volume percentage of 10% in the mixed gas to obtain a nickel-cobalt alloy catalyst, and marking the nickel-cobalt alloy catalyst as sample No. 2;
in sample 2# the mass percent of nickel in the sample was 3.0wt% and the mass percent of cobalt in the sample was 0.5wt%. Sample 2# nickel-cobalt alloy is dispersed on a silicon oxide carrier in a nano-form, the particle size of the nickel-cobalt alloy ranges from 0.64 nm to 3.25nm, and the average particle size is 1.89nm.
Example 3
Adding 6-aminocapronitrile, ammonia and a catalyst of sample No. 1 into a high-pressure reaction kettle, wherein the mass ratio of the catalyst to the 6-aminocapronitrile is 0.05:1, the molar ratio of the ammonia to the 6-aminocapronitrile is 3:1, and hydrogen is introduced, and the molar ratio of the hydrogen to the 6-aminocapronitrile is 4:1; the reaction temperature is controlled to be 70-80 ℃, the reaction pressure is controlled to be 1.8-2.5 MPa, and the reaction time is controlled to be 30min.
After the reaction, the reaction solution was examined, the conversion of 6-aminocapronitrile was 99.5%, the selectivity of hexamethylenediamine was 97.5%, the by-product cyclohexylimine was 10ppm, cyclohexanediamine was 5ppm, and dihexanetriamine was 10 ppm.
Example 4
Adding 6-aminocapronitrile, ammonia and a catalyst of sample No. 2 into a high-pressure reaction kettle, wherein the mass ratio of the catalyst to the 6-aminocapronitrile is 0.05:1, the molar ratio of the ammonia to the 6-aminocapronitrile is 3:1, and hydrogen is introduced, and the molar ratio of the hydrogen to the 6-aminocapronitrile is 4:1; the reaction temperature is controlled to be 70-80 ℃, the reaction pressure is controlled to be 1.8-2.5 MPa, and the reaction time is controlled to be 30min.
After the reaction, the reaction solution was examined, the conversion of 6-aminocapronitrile was 96.5%, the selectivity of hexamethylenediamine was 98.5%, the by-product cyclohexylimine was 5ppm, cyclohexanediamine was 5ppm, and dihexanetriamine was 10 ppm.
Example 5
a) 4.0485g of NiCl was weighed out 2 ·6H 2 O (nickel content 24.70%) is dissolved in 10ml deionized water to prepare a solution, and the solution is heated to micro-boiling condition and then added to NiCl 2 1mL of 25% ammonia water is added dropwise into the solution until precipitation is completely dissolved again, and then 1mL of ammonia water is added dropwise36.5% hydrochloric acid and 1ml of pure H 2 O 2 Until the precipitate is completely dissolved, obtaining transparent solution of nickel hexammoniate trichloride, and fixing the volume to 50.00ml, thus obtaining solution containing nickel ammine complex;
b) Weigh 2.024g CoCl 2 ·6H 2 O (cobalt content 24.7%) was dissolved in 10ml deionized water to prepare a solution, which was heated to slightly boiling, and then cooled to CoCl 2 1mL of 25% ammonia water was added dropwise to the solution to complete precipitation, followed by 1mL of 36.5% hydrochloric acid and 1mL of pure H 2 O 2 Until the precipitate is completely dissolved, obtaining a red transparent cobalt hexammoniate trichloride solution, and fixing the volume to 50.00ml to obtain a cobalt ammine complex-containing solution;
c) 5700. Mu.L of the solution containing the cobalt ammonia complex was removed to 144.3mL of an aqueous ammonia solution having pH=12, and 6.0g of SiO having an average particle diameter of 2. Mu.m was added 2 Mixing the powder, fully stirring at 60 ℃ for 3.0 hours, filtering the mixed solution, washing with deionized water, and drying at 120 ℃ for 2 hours to obtain a solid;
d) Transferring 14250 mu L of solution containing nickel-ammonia complex to 135.7mL of ammonia water solution with pH of 12, adding the dried solid prepared in the step c, mixing, fully stirring at 60 ℃ for 3.0 hours, filtering, washing with deionized water, and drying at 120 ℃ for 2 hours to obtain a catalyst precursor;
e) Placing the catalyst precursor in a tube furnace, at H 2 And N 2 Mixed gas (H) 2 Reducing for 0.5h at 400 ℃ in the atmosphere with the volume percentage of 10% in the mixed gas to obtain a nickel-cobalt alloy catalyst, and marking the nickel-cobalt alloy catalyst as sample No. 3;
f) In sample 3# the mass percent of nickel in the sample was 4.6wt% and the mass percent of cobalt in the sample was 0.95wt%. Sample 3# nickel-cobalt alloy was dispersed on a silica support, and the particle size of the nickel-cobalt alloy was in the range of 20 to 40nm, with an average particle size of 28nm.
Example 6
Adding 6-aminocapronitrile, ammonia and a catalyst of sample 3# into a high-pressure reaction kettle, wherein the mass ratio of the catalyst to the 6-aminocapronitrile is 0.05:1, the molar ratio of the ammonia to the 6-aminocapronitrile is 3:1, and hydrogen is introduced, and the molar ratio of the hydrogen to the 6-aminocapronitrile is 4:1; the reaction temperature is controlled to be 70-80 ℃, the reaction pressure is controlled to be 1.8-2.5 MPa, and the reaction time is controlled to be 30min.
After the reaction, the reaction solution was examined, the conversion of 6-aminocapronitrile was 85.8%, the selectivity of hexamethylenediamine was 95.5%, the by-product cyclohexylimine was 128ppm, cyclohexanediamine was 20 ppm, and dihexanetriamine was 15 ppm.
Comparative example 1
In a high-pressure reaction kettle, 6-aminocapronitrile, ethanol and nickel catalyst (Anshan Zhongli ZL-N411 type catalyst) are added, the mass ratio of the catalyst to the 6-aminocapronitrile is 0.10:1, and meanwhile, a promoter NaOH is added. The mol ratio of the ethanol to the 6-aminocapronitrile is 3:1, hydrogen is introduced, and the mol ratio of the hydrogen to the 6-aminocapronitrile is 4:1; the reaction temperature is controlled to be 70-80 ℃, the reaction pressure is controlled to be 1.8-2.5 MPa, and the reaction time is controlled to be 30min.
After the reaction, the reaction solution was examined, the conversion of 6-aminocapronitrile was 95.5%, the selectivity of hexamethylenediamine was 85.5%, the byproduct cyclohexylimine was 4500ppm, cyclohexanediamine was 175 ppm, and dihexanetriamine was 18757ppm.
Comparative example 2
Adding 6-aminocapronitrile, ammonia and nickel catalyst (Anshan Zhongli ZL-N411 type catalyst) into a high-pressure reaction kettle, wherein the mass ratio of the catalyst to the 6-aminocapronitrile is 0.10:1, introducing hydrogen into the mixture according to the molar ratio of ammonia to 6-aminocapronitrile of 3:1, wherein the molar ratio of the hydrogen to the 6-aminocapronitrile is 4:1; the reaction temperature is controlled to be 70-80 ℃, the reaction pressure is controlled to be 1.8-2.5 MPa, and the reaction time is controlled to be 30min.
After the reaction, the reaction solution was examined, the conversion of 6-aminocapronitrile was 53.5%, the selectivity of hexamethylenediamine was 90.5%, the by-product cyclohexylimine was 500ppm, cyclohexanediamine was 125 ppm, and dihexanetriamine was 106ppm.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. A method for preparing hexamethylenediamine by taking 6-aminocapronitrile as a raw material, taking a supported nickel-cobalt alloy catalyst as a catalyst, and reacting the 6-aminocapronitrile with hydrogen in the presence of a diluent.
2. The method for preparing hexamethylenediamine by taking 6-aminocapronitrile as a raw material according to claim 1, characterized in that the active components of the supported nickel-cobalt alloy catalyst comprise nickel-cobalt active elements, and the mass content of nickel in the catalyst is 1.0% -10%; the mass content of cobalt in the catalyst is 0.1% -2%.
3. The method for preparing hexamethylenediamine according to claim 1, wherein the diluent is an alcohol or an ammonia substance, preferably an ammonia substance.
4. The method for preparing hexamethylenediamine from 6-aminocapronitrile according to claim 1, characterized in that the molar ratio of hydrogen to 6-aminocapronitrile is (2-100): 1.
5. The method for preparing hexamethylenediamine according to claim 1, wherein the reaction temperature is 30-120 ℃, and the reaction pressure is 0.1-4.0 MPa.
6. The method for preparing hexamethylenediamine by using 6-aminocapronitrile as a raw material according to claim 1, characterized in that the mass ratio of the catalyst to 6-aminocapronitrile is (0.01-0.5): 1.
7. the method for preparing hexamethylenediamine according to claim 1, wherein the reaction time is 5 to 500 seconds.
8. The method for preparing hexamethylenediamine from 6-aminocapronitrile according to claim 1, characterized in that the nickel-cobalt alloy catalyst-supporting carrier is a catalyst containing mesoporesSpherical silica of (2); the aperture of the carrier is 2-50 nm; the specific surface area of the carrier is 200-450 m 2 /g; the pore volume of the carrier is 0.5-1.5 ml/g; the bulk density of the carrier is 0.3-1.0 g/ml.
9. The method for preparing hexamethylenediamine by using 6-aminocapronitrile as a raw material according to claim 1, characterized in that the nickel-cobalt alloy is dispersed on the carrier in a nano-form, and the particle size of the active component is 0.5-5.0 nm.
10. The method for preparing hexamethylenediamine from 6-aminocapronitrile according to claim 3, characterized in that the diluent is ammonia, the molar ratio of ammonia to 6-aminocapronitrile being (1-10): 1.
CN202310502301.3A 2023-05-06 2023-05-06 Method for preparing hexamethylenediamine by taking 6-aminocapronitrile as raw material Pending CN116554036A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR859659A (en) * 1938-08-30 1940-12-24 Du Pont Manufacturing process for aliphatic diamines
FR1040306A (en) * 1950-08-18 1953-10-14 Basf Ag Process for the production of hexamethylenediamine
FR1226216A (en) * 1958-06-11 1960-07-08 California Research Corp Hydrogenation of aromatic nitriles
US20030120115A1 (en) * 2001-10-23 2003-06-26 Andreas Ansmann Supported cobalt catalysts for nitrile hydrogenations
CN112094202A (en) * 2020-09-22 2020-12-18 江苏扬农化工集团有限公司 Method for circularly synthesizing hexamethylene diamine key intermediate
CN112934210A (en) * 2019-12-11 2021-06-11 中国科学院大连化学物理研究所 Isophthalonitrile hydrogenation catalyst, preparation and application thereof
CN114249671A (en) * 2021-11-19 2022-03-29 美瑞新材料股份有限公司 Aliphatic diamine mixture and method for preparing aliphatic diisocyanate based on same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR859659A (en) * 1938-08-30 1940-12-24 Du Pont Manufacturing process for aliphatic diamines
FR1040306A (en) * 1950-08-18 1953-10-14 Basf Ag Process for the production of hexamethylenediamine
FR1226216A (en) * 1958-06-11 1960-07-08 California Research Corp Hydrogenation of aromatic nitriles
US20030120115A1 (en) * 2001-10-23 2003-06-26 Andreas Ansmann Supported cobalt catalysts for nitrile hydrogenations
CN112934210A (en) * 2019-12-11 2021-06-11 中国科学院大连化学物理研究所 Isophthalonitrile hydrogenation catalyst, preparation and application thereof
CN112094202A (en) * 2020-09-22 2020-12-18 江苏扬农化工集团有限公司 Method for circularly synthesizing hexamethylene diamine key intermediate
CN114249671A (en) * 2021-11-19 2022-03-29 美瑞新材料股份有限公司 Aliphatic diamine mixture and method for preparing aliphatic diisocyanate based on same

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