CN113145153A - Hydrophobic bimetallic nano-catalyst and preparation method and application thereof - Google Patents

Hydrophobic bimetallic nano-catalyst and preparation method and application thereof Download PDF

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CN113145153A
CN113145153A CN202110175241.XA CN202110175241A CN113145153A CN 113145153 A CN113145153 A CN 113145153A CN 202110175241 A CN202110175241 A CN 202110175241A CN 113145153 A CN113145153 A CN 113145153A
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catalyst
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cao
cuo
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CN113145153B (en
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朱宗渊
刘岩冰
黄旭
卢青青
石清宇
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Jiangsu University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The invention discloses a hydrophobic bimetallic nano-catalyst and a preparation method and application thereof, wherein the active components of the catalyst are CaO, CuO and BN, the mass ratio of the CaO, CuO and BN precursors is 4:1: 0.4-0.6, the preparation method of the catalyst is provided, and the catalyst is applied to the production of biodiesel through transesterification of soybean oil, so that the yield of the biodiesel is improved.

Description

Hydrophobic bimetallic nano-catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solid alkaline catalysts, and particularly relates to a preparation method of a hydrophobic bimetallic nano-catalyst and application of the hydrophobic bimetallic nano-catalyst in biodiesel transesterification.
Background
While the fossil energy is promoted to be clean, efficient and economical, development and utilization of new energy and renewable energy need to be actively invested. The biodiesel is an important component of clean renewable energy, has physical and chemical properties similar to those of fossil diesel, and has the advantages of high flash point, high cetane number, low viscosity and biodegradability. The most widely used and mature process in the preparation method of biodiesel is an ester exchange method, which means that raw oil and low-carbon chain alcohol generate fatty acid alkyl ester (i.e. biodiesel) and byproduct glycerol under the action of a catalyst. The key problems of the biodiesel industry are the selection of catalysts, and the common use of homogeneous acid/base catalysts in transesterification reactions, but the problems of difficult separation, low catalyst recycling and the like exist in homogeneous catalysts. Therefore, the biodiesel produced industrially at present usually adopts a solid catalyst, and compared with an acid catalyst, the alkaline catalyst has the unique advantages of strong catalytic activity, easy separation from products and the like. Therefore, the search for highly efficient, environmentally friendly and easily separable solid basic catalysts is becoming a focus of research.
The solid alkaline catalyst used as the ester exchange reaction catalyst for producing the biodiesel has the advantages that: the catalyst has high activity and can be repeatedly used; ② the raw materials have wide sources and low price, such as limestone, calcium hydroxide and the like; thirdly, the method is environment-friendly and produces less alkaline waste liquid. In the common solid alkaline catalyst, CaO has the advantages of rich raw materials, simple preparation process, low solubility in methanol and the like, so the application of CaO in the production of biodiesel by using ester exchange reaction has better prospect. However, CaO has a common disadvantage of being very hygroscopic in air and CO2Leading to the reduction of the activity of the catalyst, and the inactivation of the active sites of the byproduct glycerol is also easy to cause; secondly, in the reaction system, Ca2+Easy leaching and reduced catalyst activity. Compared with other catalysts, the conversion rate of the existing CaO/CuO bimetallic nano-catalyst is lower, and the catalyst is easy to react with water, so that the active sites of the catalyst are reduced.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the present invention is to provide a hydrophobic bimetallic nano-catalyst for improving transesterification reaction rate, the second purpose of the present invention is to provide a preparation method of the hydrophobic bimetallic nano-catalyst, and the third purpose of the present invention is to provide an application of the hydrophobic bimetallic nano-catalyst in the production of biodiesel.
The technical scheme is as follows: according to the hydrophobic bimetallic nano-catalyst, active components of the catalyst are CaO, CuO and BN, and the mass ratio of the CaO, CuO and BN precursor is 4:1: 0.4-0.6.
The preparation method of the hydrophobic bimetallic nano-catalyst comprises the following steps:
(1) reacting Ca (OH)2Dissolving the powder and methacrylic acid solution in deionized water, stirring, and filtering to obtain transparent colorless Ca (MAA)2·H2O precursor solution;
(2) mixing CuCO3·Cu(OH)2Reacting the powder, a methacrylic acid solution and dichloromethane at the temperature of 19-21 ℃, evaporating the solution until the liquid disappears after the reaction is finished, and then drying to obtain solid Cu (MAA)2A polymer;
(3) ball milling hexagonal boron nitride to obtain BN powder, and mixing Ca (MAA)2·H2Mixing the O precursor solution in anhydrous ethanol, standing to form white viscous Ca (MAA)2The complex is washed with absolute ethyl alcohol and filtered to collect Ca (MAA)2Complex of Ca (MAA)2Complex, Cu (MAA)2Mixing the polymer and BN powder in absolute ethyl alcohol, stirring, carrying out rotary evaporation on the obtained solution until the liquid disappears, and then drying to obtain a CaO/CuO/BN precursor;
(4) and calcining the CaO/CuO/BN precursor to 645-655 ℃, and preserving the temperature to obtain the hydrophobic bimetallic nano-catalyst.
Further, in the step (1), Ca (OH)2And methacrylic acid at a molar ratio of 1:2 to 2.01.
In step (2), CuCO3·Cu(OH)2And methacrylic acid in a molar ratio of 29.5:117.9 to 118. The evaporation is rotary evaporation.
In the step (3), the ball milling is carried out in a ball mill under the conditions that the ball-material ratio is 40-41 and the ball milling rotating speed is 500-501 rpm.
In the step (4), the temperature rise rate of the calcination is 0.9-1.1 ℃/min. In Ca (OH)2And in the presence of CaO and silica gel, the prepared hydrophobic bimetallic nano-catalyst is hermetically stored in a drying dish for later use.
The invention relates to application of a hydrophobic bimetallic nano-catalyst in preparation of biodiesel.
In the early stage, Ca in CaO/CuO catalyst is aimed at2+And Cu2+The catalysts with different proportions are subjected to transesterification reaction, and the influence of different proportions on the yield of the biodiesel is discussed. On the basis, the CaO/CuO catalyst with the best mixture ratio is selected, and BN with different proportions is added, so that the influence of the BN on the performance of the CaO/CuO catalyst is researched. CaO is formed by Ca (OH)2Powder, methacrylic acid (MAA) solution and ethanol, CuO from CuCO3·Cu(OH)2The preparation method comprises the steps of preparing powder, methacrylic acid (MAA) solution and dichloromethane, preparing BN from h-BN (hexagonal boron nitride), mixing the powder, the MAA solution and the dichloromethane in a certain ratio to obtain a CaO/CuO/BN precursor, putting the CaO/CuO/BN precursor into a tubular furnace for a thermal process, and calcining to obtain the hydrophobic bimetallic CaO/CuO/BN nano catalyst.
A hydrophobic double-metal CaO/CuO/BN nano catalyst is designed and constructed based on the strong basicity of CaO, and the adsorption of grease macromolecules on the surface of the catalyst and the desorption of glycerin byproducts on the surface of the catalyst are enhanced by utilizing the super-stability and the hydrophobic property of BN, so that the yield of biodiesel is improved.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: on the basis of the previous research, the invention designs and synthesizes the hydrophobic bimetallic nano-catalyst for the transesterification reaction to produce the biodiesel, and the expected effects are as follows: the CaO/CuO/BN nano-catalyst designed based on CaO has higher catalytic activity, accelerates the reaction rate and shortens the reaction time; secondly, the catalyst of the invention can effectively improve the yield of the soybean oil biodiesel.
Drawings
FIG. 1 is an XRD characterization analysis of a CaO/CuO/BN catalyst;
FIGS. 2(a) to (b) are SEM characteristic analysis views of a CaO/CuO/BN catalyst, FIG. 2(a) is an SEM view (10 μm) of the CaO/CuO/BN catalyst, and FIG. 2(b) is an SEM view (1 μm) of the CaO/CuO/BN catalyst;
FIGS. 3(a) - (g) are EDS layered images of CaO/CuO/BN catalyst;
FIGS. 4(a) to (b) are graphs showing the hydrophobicity of a CaO/CuO/BN catalyst, FIG. 4(a) is a graph showing the contact angle analysis of a CaO/CuO/BN (5:1:0.5) catalyst, and FIG. 4(b) is a graph showing the contact angle analysis of a CaO/CuO/BN (5:1:0.25) catalyst.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
①Ca(MAA)2Preparation of hydrates
Ca(OH)2The powder (7.4g,0.1mol) and methacrylic acid (MAA) solution (17.2g,0.2mol) were dissolved in 200mL deionized water and stirred continuously at room temperature for 0.5h (380 r/min). Carrying out suction filtration by using a circulating water vacuum pump to obtain Ca2+And MAA-Ca (MAA)2·H2And the O precursor solution is transparent and colorless.
②Cu(MAA)2Preparation of polymers
CuCO3·Cu(OH)2The powder (6.51g,29.5mmol), MAA solution (10.15g,117.9mmol) and 80mL of dichloromethane were reacted at 20 ℃ and a stirring rate of 380r/min for 48 h. After the reaction, the solution was poured into a pear-shaped flask, rotary-evaporated on a rotary evaporator until the liquid disappeared, and then it was dried in a vacuum oven for 12 hours (45 ℃ C.) to obtain solid Cu (MAA)2A polymer.
Preparation of BN precursor
Hexagonal boron nitride (h-BN) powder (4g) was ground in a planetary ball mill at a ball to feed ratio of 40 at 500rpm for 8 hours to obtain fine powder particles for use.
④Ca(MAA)2/Cu(MAA)2Preparation of/BN complexes
Mixing 10mL Ca (MAA)2·H2Mixing the O precursor solution in 200mL absolute ethanol, standing for 20min to form uniform white viscous Ca (MAA)2The complex is washed with absolute ethyl alcohol and filtered to collect Ca (MAA)2The complex was compounded and weighed. With Ca (MAA)2Based on the mass of the complex, Ca (MAA)2、Cu(MAA)2Mixing with boron nitride powder at a mass ratio of 4:1:0.5 in 80mL of anhydrous ethanol, and continuously stirring at room temperature for 0.5h (380r/min) to obtain productRotary evaporation was performed on a rotary evaporator until the liquid disappeared, which was then placed in a vacuum oven to dry for 12h (45 ℃ C.) to obtain Ca (MAA)2/Cu(MAA)2Mixtures of/BN complexes.
Preparation of CaO/CuO/BN nano catalyst
The Ca (MAA) obtained in the fourthly2/Cu(MAA)2the/BN complex is put into a tube furnace to be subjected to a thermal process, is calcined to 650 ℃ (the heating rate is 1 ℃/min) at room temperature, and is kept for 15min at 650 ℃, so that the CaO/CuO/BN catalyst is obtained. The catalyst is stored in a sealed dry dish for later use, and is protected from water and CO in the presence of KOH, commercial CaO and silica gel2Is deactivated.
The prepared CaO/CuO/BN nano catalyst is used in transesterification of soybean oil (8.72g), the reaction is carried out in a penicillin bottle, the alcohol-oil ratio is 13:1, the catalyst loading is 5 percent (based on the weight of the oil), the catalyst is placed into a constant-temperature heating magnetic stirrer to react for 90min (the reaction temperature is 72 ℃, and the stirring speed is 400r/min) to obtain the biodiesel, the conversion rate of the soybean oil is 89.72 percent by using a gas chromatography internal standard method, the yield of the biodiesel is 86.85 percent, and the yield is higher than that of the biodiesel produced by catalyzing the soybean oil with the existing CaO/CuO (4:1) catalyst (79 percent).
Example 2
①Ca(MAA)2Preparation of hydrates
Ca(OH)2The powder (7.4g,0.1mol) and methacrylic acid (MAA) solution (17.2g,0.2mol) were dissolved in 200mL deionized water and stirred continuously at room temperature for 0.5h (380 r/min). Carrying out suction filtration by using a circulating water vacuum pump to obtain Ca2+Ca of MAA (MAA)2·H2And the O precursor solution is transparent and colorless.
②Cu(MAA)2Preparation of polymers
CuCO3·Cu(OH)2The powder (6.51g,29.5mmol), MAA solution (10.15g,117.9mmol) and 80mL of dichloromethane were reacted at 20 ℃ and a stirring rate of 380r/min for 48 h. After the reaction, the solution was poured into a pear-shaped flask, rotary-evaporated on a rotary evaporator until the liquid disappeared, and then placed in a vacuum drying ovenDrying for 12h (45 ℃ C.) to give solid Cu (MAA)2A polymer.
Preparation of BN precursor
Hexagonal boron nitride (h-BN) powder (4g) was ground in a planetary ball mill at a ball to feed ratio of 40 at 500rpm for 8 hours to obtain fine powder particles for use.
④Ca(MAA)2/Cu(MAA)2Preparation of/BN complexes
Mixing 10mL Ca (MAA)2·H2Mixing the O precursor solution in 200mL absolute ethanol, standing for 20min to form uniform white viscous Ca (MAA)2The complex is washed with absolute ethyl alcohol and filtered to collect Ca (MAA)2The complex was compounded and weighed. With Ca (MAA)2Based on the mass of the complex, Ca (MAA)2、Cu(MAA)2And boron nitride powder in an amount of 4:1:0.2 by mass in 80mL of anhydrous ethanol, stirring at room temperature for 0.5h (380r/min) continuously, subjecting the obtained product to rotary evaporation on a rotary evaporator until the liquid disappears, and drying in a vacuum oven for 12h (45 ℃ C.) to obtain Ca (MAA)2/Cu(MAA)2Mixtures of/BN complexes.
Preparation of CaO/CuO/BN nano catalyst
The Ca (MAA) obtained in the fourthly2/Cu(MAA)2the/BN complex is put into a tube furnace to be subjected to a thermal process, is calcined to 650 ℃ (the heating rate is 1 ℃/min) at room temperature, and is kept for 15min at 650 ℃, so that the CaO/CuO/BN catalyst is obtained. The catalyst is stored in a sealed dry dish for later use, and is protected from water and CO in the presence of KOH, commercial CaO and silica gel2Is deactivated.
The prepared CaO/CuO/BN nano catalyst is used in transesterification of soybean oil (8.72g), the reaction is carried out in a penicillin bottle, the alcohol-oil ratio is 13:1, the catalyst loading is 5 percent (based on the weight of the oil), the catalyst is placed into a constant-temperature heating magnetic stirrer to react for 90min, (the reaction temperature is 72 ℃, the stirring speed is 400r/min), biodiesel is obtained, the conversion rate of the soybean oil is 89.24 percent and the yield of the biodiesel is 81.62 percent by using a gas chromatography internal standard method
Example 3
①Ca(MAA)2Preparation of hydrates
Ca(OH)2The powder (7.4g,0.1mol) and methacrylic acid (MAA) solution (17.2g,0.2mol) were dissolved in 200mL deionized water and stirred continuously at room temperature for 0.5h (380 r/min). Carrying out suction filtration by using a circulating water vacuum pump to obtain Ca2+Ca of MAA (MAA)2·H2And the O precursor solution is transparent and colorless.
②Cu(MAA)2Preparation of polymers
CuCO3·Cu(OH)2The powder (6.51g,29.5mmol), MAA solution (10.15g,117.9mmol) and 80mL of dichloromethane were reacted at 20 ℃ and a stirring rate of 380r/min for 48 h. After the reaction, the solution was poured into a pear-shaped flask, rotary-evaporated on a rotary evaporator until the liquid disappeared, and then it was dried in a vacuum oven for 12 hours (45 ℃ C.) to obtain solid Cu (MAA)2A polymer.
Preparation of BN precursor
Hexagonal boron nitride (h-BN) powder (4g) was ground in a planetary ball mill at a ball to feed ratio of 40 at 500rpm for 8 hours to obtain fine powder particles for use.
④Ca(MAA)2/Cu(MAA)2Preparation of/BN complexes
Mixing 10mL Ca (MAA)2·H2Mixing the O precursor solution in 200mL absolute ethanol, standing for 20min to form uniform white viscous Ca (MAA)2The complex is washed with absolute ethyl alcohol and filtered to collect Ca (MAA)2The complex was compounded and weighed. With Ca (MAA)2Based on the mass of the complex, Ca (MAA)2、Cu(MAA)2And boron nitride powder in an amount of 5:1:0.5 by mass in 80mL of anhydrous ethanol, continuously stirring at room temperature for 0.5h (380r/min), subjecting the obtained product to rotary evaporation on a rotary evaporator until the liquid disappears, and then drying in a vacuum oven (temperature) for 12h (45 ℃ C.) to obtain Ca (MAA)2/Cu(MAA)2Homogeneous mixtures of/BN complexes.
Preparation of CaO/CuO/BN nano catalyst
The Ca (MAA) obtained in the fourthly2/Cu(MAA)2the/BN complex is put into a tube furnace to be subjected to a thermal process, is calcined to 650 ℃ (the heating rate is 1 ℃/min) at room temperature, and is kept for 15min at 650 ℃, so that the CaO/CuO/BN catalyst is obtained. The catalyst is stored in a sealed dry dish for later use, and is protected from water and CO in the presence of KOH, commercial CaO and silica gel2Is deactivated.
The prepared CaO/CuO/BN nano-catalyst is used in transesterification of soybean oil (8.72g), the reaction is carried out in a penicillin bottle, the alcohol-oil ratio is 13:1, the catalyst loading capacity is 5 percent (based on the weight of the oil), the catalyst is placed into a constant-temperature heating magnetic stirrer to react for 90min, the biodiesel is obtained, the conversion rate of the soybean oil is 91.45 percent by using a gas chromatography internal standard method, and the yield of the biodiesel is 84.57 percent. Compared with the existing CaO/CuO (5:1) catalyst, the yield (78%) of the biodiesel produced by catalyzing the soybean oil is higher.
Structural characterization 1
XRD characterization analysis was performed on the prepared CaO/CuO/BN catalyst, and as shown in FIG. 1, the catalyst precursor component ratios were CaO/CuO/BN 5:1:0.5 and CaO/CuO/BN 5:1:0.25, respectively, and distinct CaO, CuO and BN diffraction peaks appeared in the XRD pattern. Specifically, diffraction peaks representing CaO (JCPD No.77-2376) are present at 2 θ ═ 32.22 °, 37.37 ° and 53.89 °, and assigned to the (111), (200) and (220) crystal planes of CaO, respectively. Diffraction peaks representing CuO (JCPD No.45-0937) appear at 2 θ ═ 35.49 °, 38.73 °, 48.72 °, 61.53 °, 66.24 ° and 68.08 °, and are respectively assigned to the (002), (111), (-202), (-113), (-311), and (-220) crystal planes of CuO. Diffraction peaks representing BN (JCPD No.73-2095) appear at 2 θ ═ 26.74 ° and 41.63 °, and are assigned to the (002) and (100) crystal planes of BN, respectively. At the same time, the catalyst has certain CaCO3And Ca3B2O6Presence, CaCO appears at 29.40 ° 2 θ3Diffraction peaks ascribed to CaCO3The (104) crystal plane of (a), Ca appears at 30.67 ° and 48.02 ° 2 θ3B2O6Diffraction peaks, respectively assigned to Ca3B2O6The (113) and (223) crystal planes of (A) indicate that the catalyst is being prepared or treatedA trace amount of CaO and CO in the air2React to form CaCO3And CaO can form Ca with BN and oxygen in the air3B2O6. Comparing with XRD pattern, under the condition of a certain proportion of CaO and CuO, the addition amount of BN is increased, so that CaCO can be effectively inhibited3While at the same time, a large amount of Ca is produced3B2O6Therefore, it is necessary to appropriately control the influence of the addition amount of BN on the catalyst.
Structural characterization 2
SEM analysis was performed on the CaO/CuO/BN catalyst at a ratio of 5:1:0.5 as shown in FIGS. 2(a) - (b). In FIG. 2(a), Ca (MAA) can be seen2The elongated fibers of (a) are destroyed at high temperature, and it can be seen in fig. 2(b) that the catalysts exhibit a certain sheet-like structure due to the addition of BN, and that there are large gaps between the catalysts, facilitating the transfer of grease macromolecules within their channels.
Structural characterization 3
EDS layered image analysis was performed on CaO/CuO/BN catalyst at a ratio of 5:1:0.5 as shown in FIGS. 3(a) - (g). From the layered images, Ca, O, Cu, B and N are uniformly dispersed, indicating that three different catalyst precursors, Ca (MAA), can be prepared by rotary evaporation2、Cu(MAA)2And BN were well mixed.
Structural characterization 4
The CaO/CuO/BN catalysts were analyzed for hydrophobicity by contact angle tests for catalysts with different amounts of BN added, as shown in FIGS. 4(a) - (b). Under the same conditions, it can be seen that when the CaO/CuO/BN catalyst at the ratio of 5:1:0.5 contacts water, larger water drops exist on the surface, and when the CaO/CuO/BN catalyst at the ratio of 5:1:0.25 exists on the surface, smaller water drops exist, which shows that the addition of BN can make the catalyst have certain hydrophobicity. In the CaO/CuO/BN catalyst, the addition amount of BN is smaller than that of CaO and CuO, so that the retention time of water on the surface of the catalyst is shorter and the water is finally absorbed.

Claims (9)

1. A hydrophobic bimetallic nanocatalyst, characterized by: the active components of the catalyst are CaO, CuO and BN, and the mass ratio of the CaO, the CuO and the BN precursor is 4:1: 0.4-0.6.
2. A method for preparing the hydrophobic bimetallic nanocatalyst of claim 1, comprising the steps of:
(1) reacting Ca (OH)2Dissolving the powder and methacrylic acid solution in deionized water, stirring, and filtering to obtain transparent colorless Ca (MAA)2·H2O precursor solution;
(2) mixing CuCO3·Cu(OH)2Reacting the powder, a methacrylic acid solution and dichloromethane at the temperature of 19-21 ℃, evaporating the solution after the reaction is finished until the liquid disappears, and then drying to obtain solid Cu (MAA)2A polymer;
(3) ball milling hexagonal boron nitride to obtain BN powder, and mixing Ca (MAA)2·H2Mixing the O precursor solution in anhydrous ethanol, standing to form white viscous Ca (MAA)2The complex is washed with absolute ethyl alcohol and filtered to collect Ca (MAA)2Complex of Ca (MAA)2Complex, Cu (MAA)2Mixing the polymer and BN powder in absolute ethyl alcohol, stirring, evaporating the obtained solution until the liquid disappears, and then drying to obtain a CaO/CuO/BN precursor;
(4) and calcining the CaO/CuO/BN precursor to 645-655 ℃, and preserving the temperature to obtain the hydrophobic bimetallic nano-catalyst.
3. The method of preparing a hydrophobic bimetallic nanocatalyst of claim 2, wherein: in the step (1), the Ca (OH)2And methacrylic acid at a molar ratio of 1:2 to 2.01.
4. The method of preparing a hydrophobic bimetallic nanocatalyst of claim 2, wherein: in the step (2), the CuCO is3·Cu(OH)2And methacrylic acid in a molar ratio of 29.5:117.9 to 118.
5. The method of preparing a hydrophobic bimetallic nanocatalyst of claim 2, wherein: in the steps (2) and (3), the evaporation is rotary evaporation.
6. The method of preparing a hydrophobic bimetallic nanocatalyst of claim 2, wherein: in the step (3), the ball milling conditions are that the ball-material ratio is 40-41 and the ball milling rotating speed is 500-501 rpm.
7. The method of preparing a hydrophobic bimetallic nanocatalyst of claim 2, wherein: in the step (4), the temperature rise rate of the calcination is 0.9-1.1 ℃/min.
8. The method of preparing a hydrophobic bimetallic nanocatalyst of claim 2, wherein: in step (4), in Ca (OH)2And in the presence of CaO and silica gel, the prepared hydrophobic bimetallic nano-catalyst is hermetically stored in a drying dish for later use.
9. Use of the hydrophobic bimetallic nanocatalyst of claim 1 in the production of biodiesel.
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