A bimetallic catalyst, a preparation method thereof, and its application in alcoholamine alkylation reaction

Abstract

The present invention discloses a bimetallic catalyst, a preparation method thereof, and its application in the alkylation reaction of alcoholamines, relating to the technical field of metal catalysts. The bimetallic catalyst comprises a carrier and an active component supported on the carrier; the active component comprises Ni and Cu; and the loading amounts of Ni and Cu are 8-15% and 3-7% of the weight of the carrier, respectively, in weight percentage. The present invention utilizes a method combining femtosecond laser technology with gradient pressure cryogenic freezing technology to modify and activate alumina, effectively increasing its specific surface area and optimizing its pore structure. Furthermore, by loading appropriate amounts of Ni and Cu active components onto the carrier to form a bimetallic catalyst, the selectivity and yield of the target product, tert-butylaminoethoxyethanol, in the alkylation reaction of alcoholamines using diethylene glycol and tert-butylamine as raw materials are significantly improved, showing broad application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of metal catalysts, in particular to a bimetallic catalyst, a preparation method thereof and application thereof in an alcoholamine alkylation reaction. Background Art

[0002] The alkylation of alcoholamines, a key reaction in organic synthesis, involves the nucleophilic substitution of alcohols with nitrogen-containing compounds (such as amines) under the catalysis of a catalyst, introducing a carbon atom onto the nitrogen atom to form a C-N bond. This reaction, due to its unique chemical transformation and wide applicability, has demonstrated significant application value in various industrial fields, including petrochemicals, fine chemicals, and pharmaceuticals, becoming an important method for synthesizing organic compounds with specific functions and structures.

[0003] The alcoholamine alkylation reaction to produce tert-butylaminoethoxyethanol using diethylene glycol and tert-butylamine as raw materials is a typical example. The resulting tert-butylaminoethoxyethanol is a compound with a wide range of applications. In the selective desulfurization of refinery gas and natural gas, tert-butylaminoethoxyethanol, due to its unique chemical properties, can effectively and selectively remove organic sulfur, improving gas purity. Furthermore, this compound is used as a pharmaceutical intermediate in the synthesis of compounds with specific pharmacological activities, providing an important chemical foundation for new drug development and possessing a wide range of applications.

[0004] However, despite the enormous potential of tert-butylaminoethoxyethanol, the current state of the amine alkylation reaction, which uses diethylene glycol and tert-butylamine as raw materials to prepare this compound, faces several challenges. Although a variety of catalysts and methods have been used for this reaction, the selectivity and yield of the target product, tert-butylaminoethoxyethanol, remain suboptimal. This limits the compound's production efficiency and industrial application prospects. Furthermore, in the field of catalyst research, the properties of the support, which serves as the catalyst's skeleton and support, play a crucial role in its catalytic performance. Unfortunately, in order to improve the selectivity and yield of tert-butylaminoethoxyethanol, existing technologies often focus on improving the catalyst's active components, while research on the catalyst support is relatively weak. Summary of the Invention

[0005] To solve the above problems, the present invention provides a bimetallic catalyst, a preparation method thereof, and application thereof in an alcoholamine alkylation reaction.

[0006] In a first aspect, the present invention provides a bimetallic catalyst comprising a carrier and an active component supported on the carrier;

[0007] The active components include Ni and Cu;

[0008] In terms of weight percentage, the loading amounts of Ni and Cu are 8-15% and 3-7% of the weight of the support, respectively;

[0009] The preparation method of the carrier includes the following steps:

[0010] Step (1): obtaining aluminum oxide;

[0011] Step (2): performing femtosecond laser activation treatment on the aluminum oxide to obtain a first aluminum oxide;

[0012] Step (3): freezing the first aluminum oxide in a gradient pressure low temperature environment to obtain a second aluminum oxide;

[0013] Step (4): The second alumina is subjected to a cyclic treatment in sequence according to the femtosecond laser activation treatment in step (2) and the freezing treatment in step (2) to obtain the carrier.

[0014] Furthermore, the working condition parameters of the femtosecond laser activation treatment include: femtosecond laser power of 0.8 to 1.7 W, femtosecond laser scanning speed of 400 to 650 mm / s, femtosecond laser scanning spacing of 20 to 30 μm, femtosecond laser wavelength of 1000 to 1100 nm, femtosecond laser pulse frequency of 100 to 200 kHz, femtosecond laser pulse width of 100 to 200 fs, and the number of femtosecond laser scans is 1.

[0015] Furthermore, the freezing step includes the following process:

[0016] The first stage: freezing for 60 to 90 minutes at a pressure of 10 to 15 MPa and a temperature of -40 to -50°C;

[0017] The second stage: freezing for 60 to 90 minutes at a pressure of 5 to 10 MPa and a temperature of -40 to -50°C;

[0018] The third stage: return to room temperature under normal pressure.

[0019] Furthermore, the number of cycles is 3 to 6 times.

[0020] Furthermore, in terms of weight percentage, the loading amounts of Ni and Cu are 10% and 5% of the weight of the carrier, respectively.

[0021] In a second aspect, based on the same inventive concept, the present invention provides a method for preparing the bimetallic catalyst according to any one of the first aspects, the method for preparing the bimetallic catalyst comprising the following steps:

[0022] Obtaining a vector;

[0023] adding the carrier to an impregnation solution containing nickel salt and copper salt, stirring and mixing, and then drying to obtain a first carrier;

[0024] The first carrier is calcined and then heated and reduced in a hydrogen / argon atmosphere to obtain the bimetallic catalyst.

[0025] Furthermore, the nickel salt includes at least one of nickel chloride and its hydrate, nickel acetate and its hydrate, and nickel nitrate and its hydrate; the copper salt includes at least one of copper chloride and its hydrate, copper acetate and its hydrate, and copper nitrate and its hydrate.

[0026] Furthermore, the working condition parameters of the calcination include: temperature of 500-600° C., time of 4-7 hours; the working condition parameters of the heating reduction include: temperature of 550-750° C., time of 2-4 hours.

[0027] In a third aspect, based on the same inventive concept, the present invention provides a bimetallic catalyst as described in any one of the first aspects or a bimetallic catalyst prepared by the preparation method of the bimetallic catalyst as described in any one of the second aspects, and its use in an alkylation reaction of alcoholamines.

[0028] Furthermore, the type of the alcoholamine alkylation reaction includes preparing tert-butylaminoethoxyethanol using diethylene glycol and tert-butylamine as raw materials.

[0029] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art:

[0030] The present invention provides a bimetallic catalyst, its preparation method, and its application in the alkylation of alcoholamines. This method utilizes a combination of femtosecond laser technology and gradient pressure cryogenic freezing to modify and activate alumina, effectively increasing its specific surface area and optimizing its pore structure. Furthermore, by loading appropriate amounts of Ni and Cu active components onto this support to form a bimetallic catalyst, the catalyst significantly improves the selectivity and yield of the target product, tert-butylaminoethoxyethanol, in the alkylation of alcoholamines using diethylene glycol and tert-butylamine as raw materials, demonstrating broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0033] Figure 1 The present invention provides a flow chart of the method for preparing the bimetallic catalyst. DETAILED DESCRIPTION

[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0035] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0036] In a first aspect, the present invention provides a bimetallic catalyst comprising a carrier and an active component supported on the carrier;

[0037] The active components include Ni and Cu;

[0038] In terms of weight percentage, the loading amounts of Ni and Cu are 8-15% and 3-7% of the weight of the support, respectively;

[0039] The preparation method of the carrier includes the following steps:

[0040] Step (1): obtaining aluminum oxide;

[0041] Step (2): performing femtosecond laser activation treatment on the aluminum oxide to obtain a first aluminum oxide;

[0042] Step (3): freezing the first aluminum oxide in a gradient pressure low temperature environment to obtain a second aluminum oxide;

[0043] Step (4): The second alumina is subjected to a cyclic treatment in sequence according to the femtosecond laser activation treatment in step (2) and the freezing treatment in step (2) to obtain the carrier.

[0044] The present invention provides a bimetallic catalyst that utilizes a combination of femtosecond laser technology and gradient pressure cryogenic freezing to modify and activate alumina, effectively increasing its specific surface area and optimizing its pore structure. Furthermore, by loading appropriate amounts of Ni and Cu active components onto the support to form a bimetallic catalyst, the catalyst significantly improved the selectivity and yield of the target product, tert-butylaminoethoxyethanol, in the alkylation of alcoholamines with diethylene glycol and tert-butylamine, demonstrating broad application prospects.

[0045] In some specific embodiments, the alumina in the present invention can be directly obtained by using commercially available products or by preparing the alumina according to the preparation process disclosed in the prior art, for example, by the following method: 100 g of commercial pseudo-diamond stone dry rubber powder (dry basis content 71.5 wt%) is weighed, 2.1 g of sesbania powder and 4.2 g of boric acid are added, and the mixture is mixed evenly to obtain a first mixture; 3.6 g of acetic acid is dissolved in 86 g of deionized water, added to the first mixture, kneaded, and extruded into a clover shape with a diameter of 3.0 mm on a single-screw extruder; and then dried at 100°C for 5 hours, and then calcined at 750°C for 4 hours to obtain alumina.

[0046] In some specific embodiments, the working condition parameters of the femtosecond laser activation treatment include: femtosecond laser power of 0.8~1.7W, femtosecond laser scanning speed of 400~650mm / s, femtosecond laser scanning spacing of 20~30μm, femtosecond laser wavelength of 1000~1100nm, femtosecond laser pulse frequency of 100~200kHz, femtosecond laser pulse width of 100~200fs, and the number of femtosecond laser scans is 1; preferably, the working condition parameters of the femtosecond laser activation treatment include: femtosecond laser power of 1.2W, femtosecond laser scanning speed of 500mm / s, femtosecond laser scanning spacing of 25μm, femtosecond laser wavelength of 1050nm, femtosecond laser pulse frequency of 160kHz, femtosecond laser pulse width of 140fs, and the number of femtosecond laser scans is 1.

[0047] In some specific embodiments, the freezing step comprises the following process:

[0048] The first stage: freezing at a pressure of 10 to 15 MPa and a temperature of -40 to -50°C for 60 to 90 minutes; preferably, freezing at a pressure of 12 MPa and a temperature of -45°C for 70 minutes;

[0049] The second stage: freezing at a pressure of 5 to 10 MPa and a temperature of -40 to -50°C for 60 to 90 minutes; preferably, freezing at a pressure of 8 MPa and a temperature of -45°C for 70 minutes;

[0050] The third stage: return to room temperature under normal pressure.

[0051] In some specific embodiments, the number of cycles is 3 to 6 times.

[0052] In some specific embodiments, the loading amounts of Ni and Cu are 10% and 5% of the weight of the support, respectively, by weight.

[0053] In the second aspect, based on the same inventive concept, the present invention provides a method for preparing the bimetallic catalyst according to any one of the first aspects, such as Figure 1 As shown, the preparation method of the bimetallic catalyst comprises the following steps:

[0054] Obtaining a vector;

[0055] adding the carrier to an impregnation solution containing nickel salt and copper salt, stirring and mixing, and then drying to obtain a first carrier;

[0056] The first carrier is calcined and then heated and reduced in a hydrogen / argon atmosphere to obtain the bimetallic catalyst.

[0057] The preparation method of the bimetallic catalyst provided by the present invention adopts an impregnation-calcination-reduction method, which is simple to operate, does not require additional special equipment, and is suitable for industrial production.

[0058] In some specific embodiments, the nickel salt includes at least one of nickel chloride and its hydrate, nickel acetate and its hydrate, and nickel nitrate and its hydrate; the copper salt includes at least one of copper chloride and its hydrate, copper acetate and its hydrate, and copper nitrate and its hydrate.

[0059] In some specific embodiments, the working condition parameters of the calcination include: temperature of 500-600° C., time of 4-7 hours; the working condition parameters of the heating reduction include: temperature of 550-750° C., time of 2-4 hours.

[0060] In a third aspect, based on the same inventive concept, the present invention provides a bimetallic catalyst as described in any one of the first aspects or a bimetallic catalyst prepared by the preparation method of the bimetallic catalyst as described in any one of the second aspects, and its use in an alkylation reaction of alcoholamines.

[0061] The bimetallic catalyst provided by the present invention can significantly improve the yield and selectivity of the target product and has a wide range of uses.

[0062] In some specific embodiments, the type of alcoholamine alkylation reaction includes preparing tert-butylaminoethoxyethanol using diethylene glycol and tert-butylamine as raw materials.

[0063] It should be noted that the bimetallic catalyst provided in the embodiments of the present invention, its preparation method, and the component raw materials involved in the application in the alkylation reaction of alcoholamines, unless otherwise specified or specified, can be directly commercially available products or homemade using existing public preparation methods; at the same time, the steps and parameters involved, unless otherwise specified or specified, can be carried out according to the preparation process disclosed in the prior art or directly using existing equipment with reference to the instructions for use, and the present invention document will not repeat them one by one.

[0064] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. The experimental methods in the following examples where specific conditions are not specified are generally measured in accordance with national standards. If there are no corresponding national standards, then the methods are carried out in accordance with general international standards, conventional conditions, or the conditions recommended by the manufacturer.

[0065] Example 1

[0066] This example provides a carrier, and the preparation method of the carrier comprises the following steps:

[0067] Step (1): Weigh 100 g of pseudo-boehmite dry rubber powder, add 2.1 g of sesbania powder and 4.2 g of boric acid, and mix well to obtain a first mixture; dissolve 3.6 g of acetic acid in 86 g of deionized water, add the mixture to the first mixture, knead, and extrude into a clover-shaped strip with a diameter of 3.0 mm on a single-screw extruder; then dry at 100° C. for 5 hours, and then calcine at 750° C. for 4 hours to obtain alumina;

[0068] Step (2): The aluminum oxide is subjected to a femtosecond laser activation treatment, wherein the femtosecond laser power is 1.2 W, the femtosecond laser scanning speed is 500 mm / s, the femtosecond laser scanning spacing is 25 μm, the femtosecond laser wavelength is 1050 nm, the femtosecond laser pulse frequency is 160 kHz, the femtosecond laser pulse width is 140 fs, and the number of femtosecond laser scans is 1, to obtain a first aluminum oxide;

[0069] Step (3): freezing the first alumina in a gradient pressure low temperature environment to obtain a second alumina; wherein the freezing treatment comprises the following process: freezing at a pressure of 12 MPa and a temperature of -45°C for 70 minutes, then freezing at a pressure of 8 MPa and a temperature of -45°C for 70 minutes, and finally returning to room temperature at normal pressure;

[0070] Step (4): The second alumina is subjected to a cycle treatment of 5 times in sequence according to the femtosecond laser activation treatment in step (2) and the freezing treatment in step (2) (i.e., the femtosecond laser activation treatment in step (2) and the freezing treatment in step (2) are performed 5 times each) to obtain the carrier.

[0071] Example 2

[0072] This example provides a carrier and a preparation method thereof, which differ from Example 1 only in that: 1) the working condition parameters of the femtosecond laser activation treatment in step (2) are adjusted to: femtosecond laser power of 0.8 W, femtosecond laser scanning speed of 400 mm / s, femtosecond laser scanning spacing of 20 μm, femtosecond laser wavelength of 1000 nm, femtosecond laser pulse frequency of 100 kHz, femtosecond laser pulse width of 100 fs, and the number of femtosecond laser scans is 1; 2) the freezing treatment in step (3) is adjusted to: freezing at a pressure of 10 MPa and a temperature of -50°C for 60 minutes, then freezing at a pressure of 5 MPa and a temperature of -50°C for 60 minutes, and finally returning to room temperature at normal pressure; 3) the number of cycle treatments in step (4) is adjusted to 6 times.

[0073] Example 3

[0074] This example provides a carrier and a preparation method thereof, which differs from Example 1 only in that: 1) the working condition parameters of the femtosecond laser activation treatment in step (2) are adjusted to: femtosecond laser power of 1.7 W, femtosecond laser scanning speed of 650 mm / s, femtosecond laser scanning spacing of 30 μm, femtosecond laser wavelength of 1100 nm, femtosecond laser pulse frequency of 200 kHz, femtosecond laser pulse width of 200 fs, and the number of femtosecond laser scans is 1; 2) the freezing treatment in step (3) is adjusted to: freezing at a pressure of 15 MPa and a temperature of -45°C for 90 minutes, then freezing at a pressure of 10 MPa and a temperature of -45°C for 90 minutes, and finally returning to room temperature at normal pressure; 3) the number of cycle treatments in step (4) is adjusted to 3 times.

[0075] Example 4

[0076] This example provides a bimetallic catalyst, which includes a carrier and an active component loaded on the carrier; the active component includes Ni and Cu; in terms of weight percentage, the loading amounts of Ni and Cu are 10% and 5% of the weight of the carrier, respectively; the carrier is the carrier obtained in Example 1.

[0077] The preparation method of the bimetallic catalyst comprises the following steps:

[0078] 0.426 g of nickel acetate tetrahydrate and 0.157 g of copper acetate monohydrate were weighed and dissolved in 50 mL of deionized water and stirred for 30 min to obtain an impregnation solution containing nickel salt and copper salt;

[0079] 1 g of the carrier obtained in Example 1 was weighed and added to the impregnation solution. The mixture was stirred continuously at room temperature for 2 h, and then heated at 90° C. using a temperature-controlled magnetic stirrer to evaporate excess water. The solid sample was collected and dried in an oven at 100° C. overnight to obtain the first carrier.

[0080] The first carrier was spread flat in a porcelain ark and heated in a muffle furnace at 550 °C for 3 °C min -1 The mixture was calcined at a heating rate of 100 mL / min for 5 h; then placed in a tube furnace with a 10% H2 / Ar atmosphere (gas flow rate of 100 mL / min -1 ) and reduced at 600° C. for 3 h to obtain the bimetallic catalyst.

[0081] Example 5

[0082] This example provides a bimetallic catalyst, which includes a carrier and an active component loaded on the carrier; the active component includes Ni and Cu; in terms of weight percentage, the loading amounts of Ni and Cu are 15% and 7% of the weight of the carrier, respectively; the carrier is the carrier obtained in Example 2.

[0083] The preparation method of the above bimetallic catalyst is the same as that of Example 4.

[0084] Example 6

[0085] This example provides a bimetallic catalyst, which includes a carrier and an active component loaded on the carrier; the active component includes Ni and Cu; in terms of weight percentage, the loading amounts of Ni and Cu are 8% and 3% of the weight of the carrier, respectively; the carrier is the carrier obtained in Example 3.

[0086] The preparation method of the above bimetallic catalyst is the same as that of Example 4.

[0087] Comparative Example 1

[0088] This example provides a carrier and a preparation method thereof, which differs from Example 1 only in that the freezing treatment in step (3) of Example 1 is not performed.

[0089] The preparation method of the above-mentioned carrier comprises the following steps:

[0090] Step (1): Weigh 100 g of pseudo-boehmite dry rubber powder, add 2.1 g of sesbania powder and 4.2 g of boric acid, and mix well to obtain a first mixture; dissolve 3.6 g of acetic acid in 86 g of deionized water, add the mixture to the first mixture, knead, and extrude into a clover-shaped strip with a diameter of 3.0 mm on a single-screw extruder; then dry at 100° C. for 5 hours, and then calcine at 750° C. for 4 hours to obtain alumina;

[0091] Step (2): The alumina is subjected to femtosecond laser activation treatment, the femtosecond laser power is 1.2 W, the femtosecond laser scanning speed is 500 mm / s, the femtosecond laser scanning spacing is 25 μm, the femtosecond laser wavelength is 1050 nm, the femtosecond laser pulse frequency is 160 kHz, the femtosecond laser pulse width is 140 fs, the number of femtosecond laser scans is 1, and the above femtosecond laser activation treatment is repeated 5 times to obtain a carrier.

[0092] Comparative Example 2

[0093] This example provides a carrier and a preparation method thereof, which differs from Example 1 only in that the femtosecond laser activation treatment in step (2) of Example 1 is not performed.

[0094] The preparation method of the above-mentioned carrier comprises the following steps:

[0095] Step (1): Weigh 100 g of pseudo-boehmite dry rubber powder, add 2.1 g of sesbania powder and 4.2 g of boric acid, and mix well to obtain a first mixture; dissolve 3.6 g of acetic acid in 86 g of deionized water, add the mixture to the first mixture, knead, and extrude into a clover-shaped strip with a diameter of 3.0 mm on a single-screw extruder; then dry at 100° C. for 5 hours, and then calcine at 750° C. for 4 hours to obtain alumina;

[0096] Step (2): The alumina is subjected to a freezing treatment in a gradient pressure low-temperature environment, and the above freezing treatment is repeated 5 times to obtain a carrier; wherein the freezing treatment includes the following process: freezing at a pressure of 12 MPa and a temperature of -45°C for 70 minutes, then freezing at a pressure of 8 MPa and a temperature of -45°C for 70 minutes, and finally returning to room temperature at normal pressure.

[0097] Comparative Example 3

[0098] This example provides a carrier and a preparation method thereof. The only difference from Example 1 is that the freezing treatment in step (3) of Example 1 is adjusted to: freezing for 140 minutes at normal pressure and a temperature of -45°C, and finally returning to room temperature at normal pressure.

[0099] Test Example 1

[0100] In this example, the specific surface area and pore size distribution of the carriers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the unmodified alumina (i.e., the alumina obtained in step (1) of Example 1) were measured. The test results are shown in Table 1.

[0101] Table 1

[0102]

[0103]

[0104] As can be seen from Table 1, compared with Comparative Examples 1 to 3 and unmodified alumina, the carrier obtained by the present invention by combining femtosecond laser technology with gradient pressure cryogenic freezing technology has a larger specific surface area and significantly increases the proportion of 20-30 nm pore distribution, effectively increasing its specific surface area and optimizing the pore structure.

[0105] Test Example 2

[0106] This example examines the catalytic performance of the bimetallic catalysts obtained in Examples 4 to 6 for the preparation of tert-butylaminoethoxyethanol using diethylene glycol and tert-butylamine as raw materials.

[0107] Test Method: A bimetallic catalyst (0.026g), diethylene glycol (0.848g), and tert-butylamine (1.752g) were added to a reactor. After sealing, the reactor was purged with H2 three times to remove air. The reactor was then filled with 0.5MPa H2 and stirred at 600rpm using a magnetic stirrer. After reaching the set temperature of 220°C, the temperature was maintained for 7 hours. After the reaction was completed, the reactor was cooled to room temperature, the gas in the reactor was vented, the catalyst was filtered, and the product was collected. Gas phase analysis revealed the selectivity and yield of the target product, tert-butylaminoethoxyethanol, as shown in Table 2.

[0108] Table 2

[0109]

[0110] As shown in Table 2, the bimetallic catalyst provided by the embodiment of the present invention has excellent catalytic performance for preparing tert-butylaminoethoxyethanol from diethylene glycol and tert-butylamine, and the selectivity and yield of the target product can reach up to 90.6% and 85.2%, respectively.

[0111] In summary, the present invention provides a bimetallic catalyst, its preparation method, and its application in the alkylation of alcoholamines. This invention utilizes a method combining femtosecond laser technology with gradient pressure cryogenic freezing to modify and activate alumina, effectively increasing its specific surface area and optimizing its pore structure. Furthermore, by loading appropriate amounts of Ni and Cu active components onto this support to form a bimetallic catalyst, the catalyst significantly improves the selectivity and yield of the target product, tert-butylaminoethoxyethanol, in the alkylation of alcoholamines using diethylene glycol and tert-butylamine as raw materials, demonstrating broad application prospects.

[0112] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in a range format is only for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; therefore, the range description should be considered to have specifically disclosed all possible subranges and single numerical values ​​within the range. For example, the description of a range from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it is intended to include any cited numeral (fractional or integer) within the indicated range.

[0113] The foregoing description is intended only to provide specific embodiments of the present invention, which will enable those skilled in the art to understand and implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not intended to be limited to the embodiments shown herein, but is intended to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A bimetallic catalyst, characterized in that: The bimetallic catalyst includes a carrier and an active component supported on the carrier; The active components include Ni and Cu; In terms of weight percentage, the loading amounts of Ni and Cu are 8-15% and 3-7% of the weight of the support, respectively; The preparation method of the carrier includes the following steps: Step (1): obtaining aluminum oxide; Step (2): performing femtosecond laser activation treatment on the aluminum oxide to obtain a first aluminum oxide; Step (3): freezing the first aluminum oxide in a gradient pressure low temperature environment to obtain a second aluminum oxide; Step (4): subjecting the second alumina to a cyclic treatment in sequence according to the femtosecond laser activation treatment in step (2) and the freezing treatment in step (3) to obtain the carrier; The working condition parameters of the femtosecond laser activation treatment include: femtosecond laser power of 0.8 to 1.7 W, femtosecond laser scanning speed of 400 to 650 mm / s, femtosecond laser scanning spacing of 20 to 30 μm, femtosecond laser wavelength of 1000 to 1100 nm, femtosecond laser pulse frequency of 100 to 200 kHz, femtosecond laser pulse width of 100 to 200 fs, and the number of femtosecond laser scans is 1; The freezing process includes the following steps: The first stage: freezing for 60 to 90 minutes at a pressure of 10 to 15 MPa and a temperature of -40 to -50°C; The second stage: freezing for 60 to 90 minutes at a pressure of 5 to 10 MPa and a temperature of -40 to -50°C; The third stage: return to room temperature under normal pressure.

2. The bimetallic catalyst according to claim 1, characterized in that The number of cycles is 3 to 6 times.

3. The bimetallic catalyst according to claim 1, characterized in that In terms of weight percentage, the loading amounts of Ni and Cu are 10% and 5% of the weight of the support, respectively.

4. A method for preparing a bimetallic catalyst according to any one of claims 1 to 3, characterized in that: The preparation method of the bimetallic catalyst comprises the following steps: Obtaining a vector; adding the carrier to an impregnation solution containing nickel salt and copper salt, stirring and mixing, and then drying to obtain a first carrier; The first carrier is calcined and then heated and reduced in a hydrogen / argon atmosphere to obtain the bimetallic catalyst.

5. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The nickel salt includes at least one of nickel chloride and its hydrate, nickel acetate and its hydrate, and nickel nitrate and its hydrate; the copper salt includes at least one of copper chloride and its hydrate, copper acetate and its hydrate, and copper nitrate and its hydrate.

6. The method for preparing a bimetallic catalyst according to claim 4, characterized in that: The working condition parameters of the calcination include: temperature of 500-600° C. and time of 4-7 hours; the working condition parameters of the heating reduction include: temperature of 550-750° C. and time of 2-4 hours.

7. Use of the bimetallic catalyst according to any one of claims 1 to 3 or the bimetallic catalyst prepared by the preparation method of the bimetallic catalyst according to any one of claims 4 to 6 in the alkylation reaction of alcoholamines.

8. The use according to claim 7, characterized in that The type of the alcoholamine alkylation reaction includes preparing tert-butylaminoethoxyethanol using diethylene glycol and tert-butylamine as raw materials.

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