CN113145153B - Hydrophobic bimetallic nano-catalyst and preparation method and application thereof - Google Patents
Hydrophobic bimetallic nano-catalyst and preparation method and application thereof Download PDFInfo
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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
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- 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
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- 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
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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 CaO, cuO and BN precursors is 4:1:0.4-0.6, the preparation method of the catalyst is provided, and the application of the catalyst in biodiesel production by transesterification of soybean oil is provided, so that the yield of biodiesel is improved.
Description
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
The development and the utilization of new energy and renewable energy are required to be actively put into practice while the clean and efficient energy conservation and utilization of fossil energy are promoted. The biodiesel is clean and renewable in energy and important components, has physicochemical properties similar to those of fossil diesel, and has the advantages of high flash point, high cetane number, low viscosity and biodegradability. The most applied and most mature process in the biodiesel preparation method is the transesterification method, which means that the raw oil and the low carbon chain alcohol generate fatty acid alkyl ester (namely biodiesel) and by-product glycerin under the action of a catalyst. The key problem of the biodiesel industry is the selection of the catalyst, the homogeneous acid/base catalyst is usually used in the transesterification reaction, but the homogeneous catalyst is difficult to separate, and the catalyst is low in recycling. Therefore, the biodiesel produced industrially at present usually adopts a solid catalyst, and compared with an acidic catalyst and an alkaline catalyst, the biodiesel has the unique advantages of strong catalytic activity, easiness in product separation and the like. Thus, searching for a solid basic catalyst that is efficient, environmentally friendly and easily separable is becoming a focus of research.
The solid alkaline catalyst has several advantages in producing biodiesel as a transesterification catalyst: (1) the catalyst has high activity and can be reused; (2) wide raw material source and low priceCheap, such as limestone, calcium hydroxide, etc.; (3) 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, small solubility in methanol and the like, so that the CaO has a good prospect in the production of biodiesel by utilizing transesterification. However, caO has a common disadvantage of being very prone to absorb water and CO in the air 2 Resulting in reduced catalyst activity and by-product glycerol also tends to deactivate its active site; next, in the reaction system, ca 2+ Is easy to leach, and reduces the activity of the catalyst. Compared with other catalysts, the existing CaO/CuO bimetallic nano-catalyst has lower conversion rate, and the catalyst is easy to react with water, so that the active site of the catalyst is reduced.
Disclosure of Invention
The invention aims to: the first object of the invention is to provide a hydrophobic bimetallic nano-catalyst for improving transesterification reaction rate, the second object of the invention is to provide a preparation method of the hydrophobic bimetallic nano-catalyst, and the third object of the invention is to provide an application of the hydrophobic bimetallic nano-catalyst in biodiesel production.
The technical scheme is as follows: the active components of the hydrophobic bimetallic nano catalyst are CaO, cuO and BN, and the mass ratio of CaO, cuO and BN precursors is 4:1:0.4-0.6.
The preparation method of the hydrophobic bimetallic nano catalyst comprises the following steps:
(1) Ca (OH) 2 Dissolving the powder and methacrylic acid solution in deionized water, stirring, and filtering to obtain transparent colorless Ca (MAA) 2 ·H 2 An O precursor solution;
(2) CuCO is added to 3 ·Cu(OH) 2 Reacting the powder, methacrylic acid solution and methylene dichloride 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) 2 A polymer;
(3) Milling hexagonal boron nitride to obtain BN powder, and mixing Ca (MAA) 2 ·H 2 Mixing the O precursor solution with the non-aqueous solutionIn water ethanol, the mixture is stood to form white viscous Ca (MAA) 2 The complex was washed with absolute ethanol and filtered to collect Ca (MAA) 2 Complexes, ca (MAA) 2 Complex, cu (MAA) 2 Mixing a polymer and BN powder in absolute ethyl alcohol, stirring, performing rotary evaporation on the obtained solution until the liquid disappears, and then drying to obtain a CaO/CuO/BN precursor;
(4) Calcining the CaO/CuO/BN precursor to 645-655 ℃, and preserving heat to obtain the hydrophobic bimetallic nano-catalyst.
Further, in the step (1), ca (OH) 2 And methacrylic acid in a molar ratio of 1:2 to 2.01.
In step (2), cuCO 3 ·Cu(OH) 2 And methacrylic acid in a molar ratio of 29.5:117.9-118. Evaporation is rotary evaporation.
In the step (3), 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 rising rate of calcination is 0.9-1.1 ℃/min. In Ca (OH) 2 And sealing and storing the prepared hydrophobic bimetallic nano-catalyst in a drying dish for standby in the presence of CaO and silica gel.
The invention relates to application of a hydrophobic bimetallic nano catalyst in preparation of biodiesel.
Earlier, for Ca in CaO/CuO catalysts 2+ And Cu 2+ The transesterification reaction is carried out by catalysts with different proportions, and the influence of the different proportions on the biodiesel yield is discussed. Based on the method, caO/CuO catalysts with the best proportion are selected, BN with different proportions is added, and therefore the influence of BN on the performance of the CaO/CuO catalysts is explored. CaO is composed of Ca (OH) 2 Powder and methacrylic acid (MAA) solution and ethanol, cuO is prepared from CuCO 3 ·Cu(OH) 2 Powder, methacrylic acid (MAA) solution and methylene dichloride, BN is prepared from h-BN (hexagonal boron nitride), the powder, the methacrylic acid (MAA) solution and the methylene dichloride are mixed according to a certain proportion to obtain CaO/CuO/BN precursor, and the CaO/CuO/BN precursor is placed into a tube furnace for thermal process and calcined to obtain the hydrophobic bimetallic CaO/CuO/BN nano-catalyst.
The hydrophobic bimetallic CaO/CuO/BN nano-catalyst is constructed based on the strong alkaline design of CaO, and the super stability and the hydrophobic property of BN are utilized to enhance the adsorption of grease macromolecules on the catalyst surface and the desorption of glycerin byproducts on the catalyst surface, so that the yield of biodiesel is improved.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: on the basis of the prior research, the invention designs and synthesizes the hydrophobic bimetallic nano catalyst for producing biodiesel by transesterification, and the expected effect is as follows: (1) the CaO/CuO/BN nano catalyst designed based on CaO has higher catalytic activity, accelerates the reaction rate and shortens the reaction time; (2) the catalyst of the invention can effectively improve the yield of the soybean oil biodiesel.
Drawings
FIG. 1 is an XRD characterization analysis chart of a CaO/CuO/BN catalyst;
FIGS. 2 (a) - (b) are SEM characterization analysis graphs of CaO/CuO/BN catalysts, FIG. 2 (a) is an SEM graph (10 μm) of CaO/CuO/BN catalysts, and FIG. 2 (b) is an SEM graph (1 μm) of CaO/CuO/BN catalysts;
FIGS. 3 (a) - (g) are EDS layered images of CaO/CuO/BN catalysts;
FIGS. 4 (a) - (b) are graphs of hydrophobicity analysis of CaO/CuO/BN catalysts, FIG. 4 (a) is graph of CaO/CuO/BN (5:1:0.5) catalyst contact angle analysis, and FIG. 4 (b) is graph of CaO/CuO/BN (5:1:0.25) catalyst contact angle analysis.
Detailed Description
The technical scheme of the invention is further described below by referring to examples.
Example 1
①Ca(MAA) 2 Preparation of hydrates
Ca(OH) 2 The powder (7.4 g,0.1 mol) and methacrylic acid (MAA) solution (17.2 g,0.2 mol) were dissolved in 200mL deionized water and stirred continuously at room temperature for 0.5 hours (380 r/min). Filtering with circulating water vacuum pump to obtain Ca 2+ And MAA - Ca (MAA) 2 ·H 2 The O precursor solution is transparent and colorless.
②Cu(MAA) 2 Preparation of the Polymer
CuCO 3 ·Cu(OH) 2 The powder (6.51 g,29.5 mmol), MAA solution (10.15 g,117.9 mmol) and 80mL of dichloromethane were reacted at 20℃with stirring at 380r/min for 48h. After the reaction, the solution was poured into a pear-shaped bottle, and rotary evaporation was performed on a rotary evaporator until the liquid disappeared, which was then dried in a vacuum oven for 12h (45 ℃) to give solid Cu (MAA) 2 A polymer.
(3) Preparation of BN precursor
Hexagonal boron nitride (h-BN) powder (4 g) was ground in a planetary ball mill at a ball-to-material ratio of 40, a rotation speed of 500rpm, and a time of 8 hours to obtain fine powder particles for use.
④Ca(MAA) 2 /Cu(MAA) 2 Preparation of the BN Complex
10mL of Ca (MAA) 2 ·H 2 Mixing the O precursor solution with 200mL absolute ethanol, and standing for 20min to form uniform white viscous Ca (MAA) 2 The complex was washed with absolute ethanol and filtered to collect Ca (MAA) 2 The complex was then weighed. With Ca (MAA) 2 The mass of the complex is taken as a reference, ca (MAA) 2 、Cu(MAA) 2 And boron nitride powder were mixed in a mass ratio of 4:1:0.5 in 80mL of absolute ethanol, stirred continuously at room temperature for 0.5h (380 r/min), and the obtained product was subjected to rotary evaporation on a rotary evaporator until the liquid disappeared, and then was dried in a vacuum oven for 12h (45 ℃ C.) to obtain Ca (MAA) 2 /Cu(MAA) 2 Mixture of BN complexes.
(5) Preparation of CaO/CuO/BN nano-catalyst
Ca (MAA) obtained in (4) was added to the solution 2 /Cu(MAA) 2 the/BN complex is put into a tube furnace for heat treatment, calcined to 650 ℃ at room temperature (heating rate of 1 ℃/min), and kept at 650 ℃ for 15min, thus obtaining the CaO/CuO/BN catalyst. The catalyst is stored in a drying dish for standby in a sealing way, and the catalyst is prevented from being mixed with water and CO in the presence of KOH, commercial CaO and silica gel 2 Is deactivated by contact with (a) a metal.
The prepared CaO/CuO/BN nano catalyst is used for transesterification of soybean oil (8.72 g), the reaction is carried out in a penicillin bottle, the alcohol-oil ratio is 13:1, the catalyst loading amount is 5% (based on oil weight), the mixture is placed in a constant-temperature heating magnetic stirrer for reaction for 90min (reaction temperature: 72 ℃ C., stirring rate: 400 r/min) to obtain biodiesel, the conversion rate of the soybean oil is 89.72% by using a gas chromatography internal standard method, the biodiesel yield is 86.85%, and compared with the biodiesel yield (79%) produced by catalyzing the soybean oil by using the existing CaO/CuO (4:1) catalyst.
Example 2
①Ca(MAA) 2 Preparation of hydrates
Ca(OH) 2 The powder (7.4 g,0.1 mol) and methacrylic acid (MAA) solution (17.2 g,0.2 mol) were dissolved in 200mL deionized water and stirred continuously at room temperature for 0.5 hours (380 r/min). Filtering with circulating water vacuum pump to obtain Ca 2+ And Ca of MAA- (MAA) 2 ·H 2 The O precursor solution is transparent and colorless.
②Cu(MAA) 2 Preparation of the Polymer
CuCO 3 ·Cu(OH) 2 The powder (6.51 g,29.5 mmol), MAA solution (10.15 g,117.9 mmol) and 80mL of dichloromethane were reacted at 20℃with stirring at 380r/min for 48h. After the reaction, the solution was poured into a pear-shaped bottle, and rotary evaporation was performed on a rotary evaporator until the liquid disappeared, which was then dried in a vacuum oven for 12h (45 ℃) to give solid Cu (MAA) 2 A polymer.
(3) Preparation of BN precursor
Hexagonal boron nitride (h-BN) powder (4 g) was ground in a planetary ball mill at a ball-to-material ratio of 40, a rotation speed of 500rpm, and a time of 8 hours to obtain fine powder particles for use.
④Ca(MAA) 2 /Cu(MAA) 2 Preparation of the BN Complex
10mL of Ca (MAA) 2 ·H 2 Mixing the O precursor solution with 200mL absolute ethanol, and standing for 20min to form uniform white viscous Ca (MAA) 2 The complex was washed with absolute ethanol and filtered to collect Ca (MAA) 2 The complex was then weighed. With Ca (MAA) 2 The mass of the complex is taken as a reference, ca (MAA) 2 、Cu(MAA) 2 And boron nitride powder in a mass ratio of 4:1:0.2 in 80mL of the powderIn aqueous ethanol, stirring was continued at room temperature for 0.5h (380 r/min), and the resulting product was subjected to rotary evaporation on a rotary evaporator until the liquid disappeared, and then it was dried in a vacuum oven for 12h (45 ℃ C.) to give Ca (MAA) 2 /Cu(MAA) 2 Mixture of BN complexes.
(5) Preparation of CaO/CuO/BN nano-catalyst
Ca (MAA) obtained in (4) was added to the solution 2 /Cu(MAA) 2 the/BN complex is put into a tube furnace for heat treatment, calcined to 650 ℃ at room temperature (heating rate of 1 ℃/min), and kept at 650 ℃ for 15min, thus obtaining the CaO/CuO/BN catalyst. The catalyst is stored in a drying dish for standby in a sealing way, and the catalyst is prevented from being mixed with water and CO in the presence of KOH, commercial CaO and silica gel 2 Is deactivated by contact with (a) a metal.
The prepared CaO/CuO/BN nano catalyst is used in transesterification of soybean oil (8.72 g), the reaction is carried out in a penicillin bottle, the alcohol-oil ratio is 13:1, the catalyst loading amount is 5 percent (based on oil weight), the catalyst is placed in a constant temperature heating magnetic stirrer for reaction for 90min, (the reaction temperature is 72 ℃, the stirring rate is 400 r/min), the biodiesel is obtained, the conversion rate of the soybean oil is 89.24 percent by using a gas chromatography internal standard method, and the biodiesel yield is 81.62 percent
Example 3
①Ca(MAA) 2 Preparation of hydrates
Ca(OH) 2 The powder (7.4 g,0.1 mol) and methacrylic acid (MAA) solution (17.2 g,0.2 mol) were dissolved in 200mL deionized water and stirred continuously at room temperature for 0.5 hours (380 r/min). Filtering with circulating water vacuum pump to obtain Ca 2+ And Ca of MAA- (MAA) 2 ·H 2 The O precursor solution is transparent and colorless.
②Cu(MAA) 2 Preparation of the Polymer
CuCO 3 ·Cu(OH) 2 The powder (6.51 g,29.5 mmol), MAA solution (10.15 g,117.9 mmol) and 80mL of dichloromethane were reacted at 20℃with stirring at 380r/min for 48h. After the reaction, the solution was poured into a pear-shaped bottle, subjected to rotary evaporation on a rotary evaporator until the liquid disappeared, and then dried in a vacuum oven for 12 hours (45 ℃ C.) to obtain solid Cu (MAA) 2 A polymer.
(3) Preparation of BN precursor
Hexagonal boron nitride (h-BN) powder (4 g) was ground in a planetary ball mill at a ball-to-material ratio of 40, a rotation speed of 500rpm, and a time of 8 hours to obtain fine powder particles for use.
④Ca(MAA) 2 /Cu(MAA) 2 Preparation of the BN Complex
10mL of Ca (MAA) 2 ·H 2 Mixing the O precursor solution with 200mL absolute ethanol, and standing for 20min to form uniform white viscous Ca (MAA) 2 The complex was washed with absolute ethanol and filtered to collect Ca (MAA) 2 The complex was then weighed. With Ca (MAA) 2 The mass of the complex is taken as a reference, ca (MAA) 2 、Cu(MAA) 2 And boron nitride powder were mixed in a mass ratio of 5:1:0.5 in 80mL of absolute ethanol, stirred continuously at room temperature for 0.5h (380 r/min), and the obtained product was subjected to rotary evaporation on a rotary evaporator until the liquid disappeared, and then dried in a vacuum oven (temperature) for 12h (45 ℃ C.) to obtain Ca (MAA) 2 /Cu(MAA) 2 A homogeneous mixture of BN complexes.
(5) Preparation of CaO/CuO/BN nano-catalyst
Ca (MAA) obtained in (4) was added to the solution 2 /Cu(MAA) 2 the/BN complex is put into a tube furnace for heat treatment, calcined to 650 ℃ at room temperature (heating rate of 1 ℃/min), and kept at 650 ℃ for 15min, thus obtaining the CaO/CuO/BN catalyst. The catalyst is stored in a drying dish for standby in a sealing way, and the catalyst is prevented from being mixed with water and CO in the presence of KOH, commercial CaO and silica gel 2 Is deactivated by contact with (a) a metal.
The prepared CaO/CuO/BN nano catalyst is used for transesterification of soybean oil (8.72 g), the reaction is carried out in a penicillin bottle, the alcohol-oil ratio is 13:1, the catalyst loading amount is 5% (based on oil weight), the catalyst is placed in a constant temperature heating magnetic stirrer for reaction for 90min (the reaction temperature is 72 ℃, the stirring rate is 400 r/min), the biodiesel is obtained, the conversion rate of the soybean oil is 91.45% by using a gas chromatography internal standard method, and the yield of the biodiesel is 84.57%. Compared with the existing CaO/CuO (5:1) catalyst, the method has higher yield (78%) of biodiesel produced by catalyzing soybean oil.
Structural characterization 1
XRD characterization analysis is carried out on the prepared CaO/CuO/BN catalyst, as shown in figure 1, the component proportions of the catalyst precursor are CaO/CuO/BN=5:1:0.5 and CaO/CuO/BN=5:1:0.25, and obvious diffraction peaks of CaO, cuO and BN appear in an XRD pattern. Specifically, diffraction peaks representing CaO (JCPD No. 77-2376) appear at 2θ=32.22°, 37.37 ° and 53.89 °, respectively attributed to the (111), (200) and (220) crystal planes of CaO. Diffraction peaks representing CuO (JCPD No. 45-0937) are present at 2θ=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 2θ=26.74° and 41.63 °, respectively attributed to the (002) and (100) crystal planes of BN. At the same time, the catalyst contains a certain amount of CaCO 3 And Ca 3 B 2 O 6 There is a CaCO present at 2θ=29.40° 3 Diffraction peaks, ascribed to CaCO 3 (104) crystal plane of (2 theta = 30.67 ° and 48.02 ° Ca is present 3 B 2 O 6 Diffraction peaks respectively attributed to Ca 3 B 2 O 6 The (113) and (223) planes of (C) indicate that trace amounts of CaO and CO in the air during catalyst preparation or handling 2 Generating CaCO by reaction 3 And CaO reacts with BN and oxygen in the air to form Ca 3 B 2 O 6 . Compared with XRD patterns, under the condition of a certain ratio of CaO to CuO, the increase of the addition amount of BN can effectively inhibit CaCO 3 But at the same time, more Ca is generated 3 B 2 O 6 Therefore, it is necessary to reasonably control the influence of the addition amount of BN on the catalyst.
Structural characterization 2
SEM analysis was performed on CaO/CuO/BN catalysts at a 5:1:0.5 ratio, as shown in FIGS. 2 (a) - (b). Ca (MAA) can be seen in FIG. 2 (a) 2 The long fiber-like structure of (a) is destroyed at high temperature, and it can be seen in FIG. 2 (b) that the catalyst exhibits a certain lamellar structure due to the addition of BN, and the catalyst has a large gap therebetween, facilitating the use of the lipid macromolecules thereinAnd (3) transferring in the channel.
Structural characterization 3
EDS layered image analysis was performed on CaO/CuO/BN catalysts at a 5:1:0.5 ratio as shown in FIGS. 3 (a) - (g). From the layered image, ca element, O element, cu element, B element and N element were uniformly dispersed, demonstrating that three different catalyst precursors Ca (MAA) can be prepared by rotary evaporation 2 、Cu(MAA) 2 And BN.
Structural characterization 4
The catalysts of different BN additions were subjected to contact angle tests and analyzed for the hydrophobicity of CaO/CuO/BN catalysts as shown in fig. 4 (a) - (b). Under the same conditions, it can be seen that when the CaO/CuO/BN catalyst in the ratio of 5:1:0.5 contacts water, larger water drops exist on the surface, and smaller water drops exist on the surface of the catalyst in the ratio of 5:1:0.25, which indicates that the catalyst has certain hydrophobicity due to the addition of BN. In the CaO/CuO/BN catalyst, the addition amount of BN is smaller than that of CaO and CuO, so that the water stays on the surface of the catalyst for a shorter time and is finally absorbed.
Claims (7)
1. A hydrophobic bimetallic nanocatalyst for the production of biodiesel, characterized in that: the active components of the catalyst are CaO, cuO and BN, and the mass ratio of the CaO, cuO and BN precursors is 4:1:0.4-0.6;
the preparation of the hydrophobic bimetallic nano-catalyst comprises the following steps:
(1) Ca (OH) 2 Dissolving the powder and methacrylic acid solution in deionized water, stirring, and filtering to obtain transparent colorless Ca (MAA) 2 ·H 2 An O precursor solution;
(2) CuCO is added to 3 ·Cu(OH) 2 Reacting the powder, methacrylic acid solution and dichloromethane at the temperature of 19-21 ℃, evaporating the solution after the reaction until the liquid disappears, and then drying to obtain solid Cu (MAA) 2 A polymer;
(3) Milling hexagonal boron nitride to obtain BN powder, and mixing Ca (MAA) 2 ·H 2 Mixing the O precursor solution with absolute ethanolIn (2), standing to form white viscous Ca (MAA) 2 The complex was washed with absolute ethanol and filtered to collect Ca (MAA) 2 Complexes, ca (MAA) 2 Complex, cu (MAA) 2 Mixing a 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 heat to obtain the hydrophobic bimetallic nano-catalyst.
2. The hydrophobic bimetallic nanocatalyst for biodiesel production according to claim 1, characterized in that: in step (1), the Ca (OH) 2 And methacrylic acid in a molar ratio of 1:2 to 2.01.
3. The hydrophobic bimetallic nanocatalyst for biodiesel production according to claim 1, characterized in that: in step (2), the CuCO 3 ·Cu(OH) 2 And methacrylic acid in a molar ratio of 29.5:117.9-118.
4. The hydrophobic bimetallic nanocatalyst for biodiesel production according to claim 1, characterized in that: in the steps (2) and (3), the evaporation is rotary evaporation.
5. The hydrophobic bimetallic nanocatalyst for biodiesel production according to claim 1, characterized in that: in the step (3), the ball milling condition is that the ball-material ratio is 40-41 and the ball milling rotating speed is 500-501 rpm.
6. The hydrophobic bimetallic nanocatalyst for biodiesel production according to claim 1, characterized in that: in the step (4), the temperature rising rate of the calcination is 0.9-1.1 ℃/min.
7. Hydrophobic bimetallic nanocatalyst for biodiesel production according to claim 1, characterized in thatThe method is characterized in that: in step (4), ca (OH) 2 And sealing and storing the prepared hydrophobic bimetallic nano-catalyst in a drying dish for standby in the presence of CaO and silica gel.
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