CN116726932A - Supported nickel-copper catalyst for sterically hindered amine tert-butylaminoethoxy ethanol and preparation method thereof - Google Patents

Supported nickel-copper catalyst for sterically hindered amine tert-butylaminoethoxy ethanol and preparation method thereof Download PDF

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CN116726932A
CN116726932A CN202310675942.9A CN202310675942A CN116726932A CN 116726932 A CN116726932 A CN 116726932A CN 202310675942 A CN202310675942 A CN 202310675942A CN 116726932 A CN116726932 A CN 116726932A
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catalyst
diethylene glycol
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tert
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CN116726932B (en
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徐偲
胡嘉莉
王晓钟
戴立言
陈英奇
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Quzhou Research Institute of Zhejiang University
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Quzhou Research Institute of Zhejiang University
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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
    • B01J23/74—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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/72—Copper
    • 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
    • B01J37/0201—Impregnation
    • 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
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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
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    • Y02P20/584—Recycling of catalysts

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Abstract

The application discloses a supported nickel-copper catalyst for sterically hindered amine tert-butylaminoethoxyethanol and a preparation method thereof. The preparation method comprises the following steps: weighing the metal salts of Ni and Cu according to the load, dissolving the metal salts in deionized water, and stirring to obtain a mixed solution; adding carrier alumina into the mixed solution, stirring, mixing uniformly, heating and evaporating excessive water; and drying, calcining and reducing the generated solid sample to obtain the supported nickel-copper catalyst. The catalyst disclosed by the application is easy to recycle, good in cycle stability, mild in reaction condition for preparing tert-butylamine ethoxyethanol from diethylene glycol, greatly improved in reaction conversion rate and selectivity, and good in industrial prospect.

Description

Supported nickel-copper catalyst for sterically hindered amine tert-butylaminoethoxy ethanol and preparation method thereof
Technical Field
The application relates to the technical field of catalysis, in particular to a supported nickel-copper catalyst for sterically hindered amine tert-butylaminoethoxyethanol and a preparation method thereof.
Background
Tert-butylaminoethoxyethanol (TBEE) is an ammonia-flavored, readily water-soluble, transparent liquid, a secondary aminoether alcohol, having a tertiary butyl group (steric hindrance coefficient 1.74) attached to the amino nitrogen atom in its structure, thus providing the TBEE with severe steric hindrance. The tertiary butyl has strong steric hindrance effect, and can inhibit TBEE and CO 2 The action is generated; but also can obviously increase the alkalinity of the solution and strengthen the TBEE to H 2 The absorption capacity of S, both of which together promote high desulfurization selectivity of TBEE. Moreover, the volatilization loss of the solvent can be effectively reduced due to the higher boiling point of TBEE (117 ℃ C., 10mm Hg). As an efficient natural gas selective desulfurization solvent, the traditional production process of TBEE (taking 2-chloroethoxyethanol and tert-butylamine as raw materials) has serious equipment corrosion and high production cost. In contrast, the industrial route for preparing the ethylene glycol by hydration of the ethylene oxide by reacting the diethylene glycol with the tert-butylamine to obtain the TBEE has the characteristics of cleanness, high efficiency and greenness.
Regarding this route, (1) patent US4487967a uses diethylene glycol and tert-butylamine as starting materials for the first time to prepare TBEE, there are significant problems in the reaction: the loss of active substances is serious, and the utilization rate of active ingredients is not high; (2) Patent CN1922128A studied commercial nickel-based catalysts with different series loadings and homemade Ni/Al 2 O 3 The effect of MCM-41 catalyst in preparing TBEE from diethylene glycol and tert-butylamine shows that the pore size distribution change caused by different carriers has important influence on the activity and selectivity of the catalyst and the yield is lower; (3) Patent CN100572355A adds triethylamine as auxiliary agent to catalyst Ni/Al 2 O 3 In the preparation process of the MCM-42, the MCM-42 is acted on the reaction of diethylene glycol and tert-butylamine, so that the conversion rate (TBEE/TBM molar ratio is 19) of 57.9% is obtained, the preparation process of the catalyst is complex, the production cost is high, and the catalyst is not beneficial to industrialized mass production.
In general, there is little research on this route, and therefore, it is important to develop a catalyst system suitable for the reaction to continue to improve the reaction yield.
Disclosure of Invention
Aiming at the problems of low reaction yield and the like in the diethylene glycol catalytic amination process in the prior art, the application provides a supported nickel-copper catalyst for sterically hindered amine tert-butylaminoethoxyethanol and a preparation method thereof. The catalyst shows higher selectivity to the target product tert-butylamine ethoxyethanol by applying the catalyst to the catalytic amination reaction of diethylene glycol, and the whole reaction process has mild conditions. In addition, the catalyst has the advantages of simple and convenient preparation method, easy recovery in the follow-up process, good cycle stability and good industrialization prospect.
A preparation method of a supported nickel-copper catalyst comprises the following steps:
(1) Weighing the metal salts of Ni and Cu according to the load, dissolving the metal salts in deionized water, and stirring to obtain a mixed solution;
(2) Adding carrier alumina into the mixed solution in the step (1), stirring, mixing uniformly, and heating to evaporate excessive water;
(3) And (3) drying, calcining and reducing the solid sample generated in the step (2) to obtain the supported nickel-copper catalyst.
In the step (1), the metal salt may be at least one of chloride, acetate, acetylacetonate and nitrate, preferably at least one of acetate and nitrate.
In the step (1), the loading amounts of Ni and Cu metal elements are preferably 5-30 wt.% of the mass of the alumina of the carrier, wherein the concentration of Ni salt is 2.13-12.76 g/L, and the concentration of Cu salt is 1.57-9.44 g/L. The Ni loading is more preferably 20wt.% of the alumina mass of the support, the Cu loading is more preferably 5wt.% of the alumina mass of the support, the Ni salt concentration is 8.52g/L, and the Cu salt concentration is 1.57g/L.
In the step (1), the stirring time is preferably 10 to 40 minutes, more preferably 30 minutes.
In the step (2), the stirring time is 1 to 6 hours, more preferably 2 hours. The heating temperature is preferably 70 to 100 ℃, more preferably 90 ℃.
In the step (3), the drying temperature is preferably 70 to 120 ℃, more preferably 100 ℃, and the drying time is preferably 4 to 12 hours, more preferably 12 hours;
in the step (3), the calcination temperature is 300-700 ℃, more preferably 550 ℃, and the time is preferably 3-6 h, more preferably 5h;
in step (3), the reduction is carried out in a tube furnace at 10% H 2 In Ar atmosphere, the gas flow rate is preferably 30-100 mL.min -1 More preferably 50 to 100 mL/min -1 The reduction temperature is 400-700 ℃, more preferably 600 ℃, and the time is preferably 2-5 h, more preferably 3h;
the application also provides the supported nickel-copper catalyst prepared by the preparation method.
The supported nickel-copper catalyst carrier is alumina, and the active components are Ni and Cu.
The application also provides application of the supported nickel-copper catalyst in preparing sterically hindered amine tert-butylamine ethoxyethanol by catalyzing and aminating diethylene glycol.
As a general inventive concept, the present application also provides a method for preparing sterically hindered amine tert-butylaminoethoxyethanol by catalytic amination of diethylene glycol: in a batch reactor with stirring, uniformly mixing the supported nickel-copper catalyst, diethylene glycol and tert-butylamine, sealing and then introducing H 2 Purging for 3 times to remove air in the reaction kettle, and filling H 2 And then setting stirring speed, and carrying out catalytic amination reaction at 180-260 ℃ (preferably 220 ℃) to obtain the target product tert-butylaminoethoxyethanol.
The molar ratio of diethylene glycol to tert-butylamine is 1 (1-6), more preferably 1:3.
The mass of the supported nickel copper catalyst is preferably 0.6 to 1.4wt.%, and more preferably 1.0wt.% of the total mass of diethylene glycol and t-butylamine.
The H is 2 The pressure is preferably 0 to 1.5MPa, more preferably 0.5MPa.
The stirring speed is preferably 400 to 800rpm, and more preferably 500 to 800rpm.
The time for the catalytic amination reaction is 4 to 10 hours, more preferably 7 hours.
Compared with the prior art, the application has the beneficial effects that:
1. the application provides a supported nickel-copper catalyst, which has the advantages of simple preparation method, easily available raw materials, low price and easy recovery.
2. The reaction condition for preparing tert-butylamine ethoxyethanol from diethylene glycol provided by the application is mild, and the reaction conversion rate and selectivity are greatly improved.
3. NiO and CuO in the catalyst precursor are H 2 During the reduction process, niCu alloy is formed, the synergistic effect between Ni and Cu is enhanced, the reduction performance of NiO is improved, and the active center Ni is effective 0 The number of (2) is greatly increased and the catalyst activity is thus improved.
Drawings
FIG. 1 is a comparative X-ray diffraction (XRD) pattern of the supported nickel copper catalyst prepared in example 1, and recovered and reused.
FIG. 2 is a BET plot of the specific surface area of the supported nickel copper catalyst prepared in example 1.
Detailed Description
The application will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer. The raw materials used in the following embodiments are all commercially available. Unless otherwise indicated, room temperature is indicated as 25 ℃.
Example 1
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by dipping, 0.851g of nickel acetate tetrahydrate (Ni loading 20 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred thoroughly for 30min to obtain a homogeneous solution, and then 1g of gamma-Al was weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 550deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 20Ni5Cu/Al 2 O 3 The catalyst (designated S1).
Second, catalytic amination reaction: adding the S1 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step into a reaction kettle, sealing and introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 89.6% by gas phase analysis, the selectivity to TBEE was 84.6% and the yield was 75.8%.
FIG. 1 shows a comparative X-ray diffraction (XRD) pattern of the supported nickel-copper catalyst prepared in example 1 after recovery and reuse. FIG. 2 is a BET plot of the specific surface area of the supported nickel copper catalyst prepared in example 1.
Comparative example 1
In the first step, the preparation of a catalyst: unlike example 1, the above 20Ni5Cu/Al was prepared by coprecipitation method 2 O 3 A catalyst. Weighing 0.425g of nickel acetate tetrahydrate, 0.079g of copper acetate monohydrate and 3.678g of aluminum nitrateNonahydrate, respectively dissolved in deionized water to prepare the water with the concentration of 0.5 mol.L -1 Is a solution of (a) and (b). Then, each solution was added to a three-necked flask in an oil bath at 80℃at a rotation speed of 700rpm, stirred for 10 minutes to mix them sufficiently, then ammonia water (containing 28 wt.%) was added dropwise to the solution, the pH of the suspension was measured to 8 using pH test paper, the dropwise addition was stopped, stirred for 2 hours again, and then crystallized for 2 hours. Cooling to room temperature, filtering, washing with deionized water to neutrality, clamping the filter paper into a surface dish with forceps, drying overnight in a 100deg.C oven, grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling to 550deg.C in a muffle furnace for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 20Ni5Cu/Al 2 O 3 The catalyst (denoted as D1).
Second, catalytic amination reaction: into a reaction vessel, D1 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step were added, and H was introduced after sealing 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 9.2%, the selectivity of TBEE was 71.0% and the yield was 6.5% by gas phase analysis.
Comparative example 2
In the first step, the preparation of a catalyst: unlike example 1, the above 20Ni5Cu/Al was prepared by physical milling 2 O 3 A catalyst. Weighing 0.851g of nickel acetate tetrahydrate, 0.157g of copper acetate monohydrate, 1g of gamma-Al 2 O 3 Grinding with a mortar, mixing, pouring into a surface dish, drying in a 100deg.C oven for 24 hr, spreading the dried sample in a porcelain square boat, and cooling to 550deg.C in a muffle furnace for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow)Speed of 100 mL/min -1 ) Reducing for 3h at 600 ℃ to obtain 20Ni5Cu/Al 2 O 3 Catalyst (denoted as D2).
Second, catalytic amination reaction: into a reaction vessel, D2 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step were added, and H was introduced after sealing 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 35.1% by gas phase analysis, the selectivity to TBEE was 59.4% and the yield was 20.8%.
Example 2
Firstly, preparing a supported nickel-copper catalyst:
the catalyst is prepared by adopting an impregnation method, 0.213g of nickel acetate tetrahydrate (Ni loading 5 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) are weighed and dissolved in 50mL of deionized water, and fully stirred for 30min to obtain a uniform solution, and 1g of gamma-Al is weighed again 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 550deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 5Ni5Cu/Al 2 O 3 The catalyst (denoted S2).
Second, catalytic amination reaction: adding the S2 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step into a reaction kettle, sealing and introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to after the reaction is finishedAnd (3) discharging gas in the kettle at room temperature, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 31.9%, the selectivity of TBEE was 62.4% and the yield was 19.9% by gas phase analysis.
Example 3
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by an immersion method, 0.426g of nickel acetate tetrahydrate (Ni loading 10 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred sufficiently for 30min to obtain a homogeneous solution, and then 1g of gamma-Al was weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 550deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 10Ni5Cu/Al 2 O 3 The catalyst (designated as S3).
Second, catalytic amination reaction: adding the S3 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step into a reaction kettle, sealing and introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 54.0%, the selectivity of TBEE was 56.2% and the yield was 30.3% by gas phase analysis.
Example 4
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by dipping, 0.638g of nickel acetate tetrahydrate (Ni loading 15 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred well for 30min to obtain a catalystTo obtain a homogeneous solution, and weighing 1g of gamma-Al 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 550deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 15Ni5Cu/Al 2 O 3 The catalyst (designated as S4).
Second, catalytic amination reaction: adding the S4 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step into a reaction kettle, sealing and introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 66.7% by gas phase analysis, the selectivity of TBEE was 89.6% and the yield was 59.8%.
Example 5
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by an immersion method, 1.277g of nickel acetate tetrahydrate (Ni loading 30 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred thoroughly for 30min to obtain a homogeneous solution, and then 1g of gamma-Al was weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 550deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3 hours at the temperature of 600 ℃,obtaining 30Ni5Cu/Al 2 O 3 The catalyst (denoted S5).
Second, catalytic amination reaction: into a reaction vessel, the S5 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step were added, and H was introduced after sealing 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 64.1%, the selectivity of TBEE was 82.9% and the yield was 53.2% by gas phase analysis.
Example 6
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by dipping, 0.851g of nickel acetate tetrahydrate (Ni loading 20 wt.%) and 0.628g of copper acetate monohydrate (Cu loading 20 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred thoroughly for 30min to obtain a homogeneous solution, and then 1g of gamma-Al was weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 550deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 20Ni20Cu/Al 2 O 3 The catalyst (designated as S6).
Second, catalytic amination reaction: adding the S6 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step into a reaction kettle, sealing and introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, and filtering the catalystThe product was collected. The conversion of diethylene glycol was 65.6%, the selectivity of TBEE was 86.0% and the yield was 56.3% by gas phase analysis.
Example 7
Firstly, preparing a supported nickel-copper catalyst:
the catalyst is prepared by adopting an impregnation method, 0.851g of nickel acetate tetrahydrate (Ni loading amount is 20 wt.%) and 0.942g of copper acetate monohydrate (Cu loading amount is 30 wt.%) are weighed and dissolved in 50mL of deionized water, and fully stirred for 30min to obtain a uniform solution, and then 1g of gamma-Al is weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 550deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 20Ni30Cu/Al 2 O 3 The catalyst (designated as S7).
Second, catalytic amination reaction: into a reaction vessel, the S7 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step were added, and H was introduced after sealing 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 71.1% by gas phase analysis, the selectivity of TBEE was 63.2% and the yield was 45.0%.
Example 8
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by dipping, 0.851g of nickel acetate tetrahydrate (Ni loading 20 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred thoroughly for 30min to obtain a homogeneous solution, and then 1g of gamma-Al was weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 300deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 20Ni5Cu/Al 2 O 3 The catalyst (designated as S8).
Second, catalytic amination reaction: adding the S8 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step into a reaction kettle, sealing and introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 67.0%, the selectivity of TBEE was 58.5% and the yield was 39.2% by gas phase analysis.
Example 9
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by dipping, 0.851g of nickel acetate tetrahydrate (Ni loading 20 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred thoroughly for 30min to obtain a homogeneous solution, and then 1g of gamma-Al was weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 400deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 20Ni5Cu/Al 2 O 3 The catalyst (denoted S9).
Second, catalytic amination reaction: adding the S9 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step into a reaction kettle, sealing and introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 70.3%, the selectivity of TBEE was 87.4% and the yield was 61.4% by gas phase analysis.
Example 10
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by dipping, 0.851g of nickel acetate tetrahydrate (Ni loading 20 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred thoroughly for 30min to obtain a homogeneous solution, and then 1g of gamma-Al was weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 700deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 600 ℃ to obtain 20Ni5Cu/Al 2 O 3 The catalyst (denoted S10).
Second, catalytic amination reaction: adding the S10 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step into a reaction kettle, sealing and introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. Through the gas-phase analysis of the material,the conversion of diethylene glycol was 65.5%, the selectivity of TBEE was 87.3% and the yield was 57.2%.
Example 11
Firstly, preparing a supported nickel-copper catalyst:
the catalyst was prepared by dipping, 0.851g of nickel acetate tetrahydrate (Ni loading 20 wt.%) and 0.157g of copper acetate monohydrate (Cu loading 5 wt.%) were weighed and dissolved in 50mL of deionized water, and stirred thoroughly for 30min to obtain a homogeneous solution, and then 1g of gamma-Al was weighed 2 O 3 As a carrier, the mixture was added to the solution, stirred continuously at room temperature for 2 hours, and then heated with a magnetic stirrer at 90℃to evaporate excess water. The solid samples were collected and placed in a 100 ℃ oven for drying overnight. Grinding the dried sample with a mortar, spreading in a porcelain square boat, and cooling in a muffle furnace at 550deg.C for 3 min -1 Calcining for 5 hours at the temperature rising rate to obtain the catalyst precursor. Before the reaction, the precursor is put into a tube furnace for 10 percent of H 2 Ar atmosphere (gas flow rate 100mL min) -1 ) Reducing for 3h at 400 ℃ to obtain 20Ni5Cu/Al 2 O 3 The catalyst (denoted S11).
Second, catalytic amination reaction: into a reaction vessel, the S11 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) obtained in the first step were added, and H was introduced after sealing 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 84.5%, the selectivity of TBEE was 58.4% and the yield was 49.3% by gas phase analysis.
Example 12
Into a reaction vessel, S1 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) were added, and after sealing, H was introduced 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.25MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, and discharging the gas in the kettleThe catalyst was filtered and the product was collected. The conversion of diethylene glycol was 50.9%, the selectivity of TBEE was 86.7% and the yield was 44.1% by gas phase analysis.
Example 13
Into a reaction vessel, S1 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) were added, and after sealing, H was introduced 2 Purging 3 times to remove air in the reaction kettle, and then filling 1.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 99.7%, the selectivity of TBEE was 2.7% and the yield was 2.7% by gas phase analysis.
Example 14
Into a reaction vessel, S1 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) were added, and after sealing, H was introduced 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (260 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 87.1% by gas phase analysis, the selectivity to TBEE was 61.4% and the yield was 53.5%.
Example 15
Into a reaction vessel, S1 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) were added, and after sealing, H was introduced 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 4 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 60.3%, the selectivity of TBEE was 91.2% and the yield was 55.0% by gas phase analysis.
Example 16
To the reaction vessel were added S1 catalyst (0.027 g), diethylene glycol (1.830 g,15 mmol), tert-butylamine (1.095 g,15 mmol)) Sealing and then introducing H 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 74.6%, the selectivity of TBEE was 84.6% and the yield was 63.1% by gas phase analysis.
Example 17
Into a reaction vessel, S1 catalyst (0.026 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) were added, and after sealing, H was introduced 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 400rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 68.0%, the selectivity of TBEE was 91.3% and the yield was 62.1% by gas phase analysis.
Example 18
Into a reaction vessel, S1 catalyst (0.016 g), diethylene glycol (0.848 g,8 mmol) and tert-butylamine (1.7512 g,24 mmol) were added, and after sealing, H was introduced 2 Purging 3 times to remove air in the reaction kettle, and then filling 0.5MPa H 2 Setting reaction parameters. The stirring speed of the magnetic stirrer is 600rpm, and the temperature is kept for 7 hours after the set temperature (220 ℃) is reached. Cooling to room temperature after the reaction is finished, discharging gas in the kettle, filtering the catalyst, and collecting the product. The conversion of diethylene glycol was 76.3%, the selectivity of TBEE was 66.3% and the yield was 50.6% by gas phase analysis.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.

Claims (10)

1. The preparation method of the supported nickel-copper catalyst is characterized by comprising the following steps:
(1) Weighing the metal salts of Ni and Cu according to the load, dissolving the metal salts in deionized water, and stirring to obtain a mixed solution;
(2) Adding carrier alumina into the mixed solution in the step (1), stirring, mixing uniformly, and heating to evaporate excessive water;
(3) And (3) drying, calcining and reducing the solid sample generated in the step (2) to obtain the supported nickel-copper catalyst.
2. The method according to claim 1, wherein in the step (1), the metal salt is at least one of chloride, acetate, acetylacetonate and nitrate.
3. The preparation method according to claim 1, wherein in the step (1), the loading amounts of the Ni and Cu metal elements are respectively 20wt.% and 5wt.% of the mass of the alumina of the carrier, wherein the Ni salt concentration is 8.52g/L and the Cu salt concentration is 1.57g/L.
4. The method according to claim 1, wherein in the step (1), the stirring time is 30 minutes.
5. The method according to claim 1, wherein in the step (2), the stirring time is 2 hours and the heating temperature is 90 ℃.
6. The method according to claim 1, wherein in the step (3):
the drying temperature is 100 ℃ and the drying time is 12 hours;
the calcination temperature is 550 ℃ and the calcination time is 5 hours;
the reduction is carried out in a tube furnace at 10% H 2 In Ar atmosphere, the gas flow rate is 30-100 mL.min -1 The reduction temperature was 600℃and the time was 3 hours.
7. The supported nickel-copper catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. The use of the supported nickel copper catalyst according to claim 7 for the catalytic amination of diethylene glycol to prepare the sterically hindered amine tert-butylaminoethoxyethanol.
9. A method for preparing sterically hindered amine tert-butylaminoethoxyethanol by catalytic amination of diethylene glycol is characterized by comprising the following steps: in a batch reactor with stirring, uniformly mixing a supported nickel-copper catalyst, diethylene glycol and tert-butylamine, sealing and then introducing H 2 Purging for 3 times to remove air in the reaction kettle, and filling H 2 Setting stirring speed, and carrying out catalytic amination reaction at 220 ℃ to obtain the target product tert-butylaminoethoxyethanol.
10. The process for the preparation of the sterically hindered amine tert-butylaminoethoxyethanol by catalytic amination of diethylene glycol according to claim 9, wherein: the mol ratio of the diethylene glycol to the tert-butylamine is 1:3; the weight of the supported nickel-copper catalyst is 1.0wt.% of the total weight of diethylene glycol and tert-butylamine; the H is 2 The pressure is 0.5MPa; the stirring speed is 400-800 rpm; the time of the catalytic amination reaction is 7h.
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Publication number Priority date Publication date Assignee Title
CN117138784A (en) * 2023-10-30 2023-12-01 潍坊学院 High-loading high-dispersion Cu-based catalyst and synthesis method and application thereof

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Publication number Priority date Publication date Assignee Title
US20070276162A1 (en) * 2004-02-17 2007-11-29 Andrzej Malek Catalytic Preparation of Severely Sterically Hindered Amino-Ether Alcohols Using a Metal Loaded Catalyst
CN110508287A (en) * 2019-09-02 2019-11-29 吉林大学 Ni-Cu/Al2O3Bimetallic catalyst, preparation method and its preparing the application in tert-butylamine base oxethyl ethyl alcohol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070276162A1 (en) * 2004-02-17 2007-11-29 Andrzej Malek Catalytic Preparation of Severely Sterically Hindered Amino-Ether Alcohols Using a Metal Loaded Catalyst
CN110508287A (en) * 2019-09-02 2019-11-29 吉林大学 Ni-Cu/Al2O3Bimetallic catalyst, preparation method and its preparing the application in tert-butylamine base oxethyl ethyl alcohol

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117138784A (en) * 2023-10-30 2023-12-01 潍坊学院 High-loading high-dispersion Cu-based catalyst and synthesis method and application thereof
CN117138784B (en) * 2023-10-30 2024-02-06 潍坊学院 High-loading high-dispersion Cu-based catalyst and synthesis method and application thereof

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