CN112023932B - Nanometer bimetallic catalyst and preparation method and application thereof - Google Patents
Nanometer bimetallic catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000003225 biodiesel Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 239000003921 oil Substances 0.000 abstract description 19
- 235000019198 oils Nutrition 0.000 abstract description 11
- 235000012424 soybean oil Nutrition 0.000 abstract description 8
- 239000003549 soybean oil Substances 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 229930182555 Penicillin Natural products 0.000 description 6
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010813 internal standard method Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000011943 nanocatalyst Substances 0.000 description 6
- 229940049954 penicillin Drugs 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000004677 hydrates Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
-
- 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
Abstract
The invention discloses a nano bimetallic catalyst and a preparation method and application thereof, wherein the nano bimetallic catalyst comprises CaO and CuO, the mass ratio of CaO to CuO precursors is 1:1-5:1, and the preparation method of the nano bimetallic catalyst and the application thereof in preparing biodiesel by transesterification are provided. The CuO is used for effectively cooperating with CaO to promote transesterification; the method comprises the steps of carrying out transesterification reaction of soybean oil on CaO/CuO catalysts with different doping ratios, wherein under the conditions that the alcohol-to-oil ratio is 13:1, the catalyst dosage is 5% (based on oil weight), the reaction temperature is 72 ℃ and the reaction time is 90min, ca in CaO and CuO precursors is as follows 2+ And Cu 2+ The mass ratio is 4:1, the mass yield of the biodiesel is the highest and is 79%.
Description
Technical Field
The invention relates to a bimetallic catalyst and a preparation method and application thereof, in particular to a nano bimetallic catalyst and a preparation method and application thereof.
Background
The biodiesel is fatty acid alkyl ester (namely biodiesel) prepared by using animal and vegetable oil, waste restaurant oil, engineering microalgae and the like as raw oil and short-chain alcohol (methanol and ethanol) through an ester exchange process under the action of a catalyst, and can replace petrochemical diesel. Biodiesel is a typical green energy source, has excellent environmental protection performance, safety performance, renewable performance and the like, and has the main advantages that: has continuous renewable performance, good environmental protection performance and good substitution performance. The development of biodiesel industry has great significance for opening up energy paths, protecting environment, saving resources and further implementing sustainable development strategy.
In the biodiesel transesterification industry, a key issue is the choice of catalyst, which is typically a basic catalyst in industrial production, including both homogeneous (liquid) and heterogeneous (solid) catalysts. Common homogeneous basic catalysts include sodium hydroxide, potassium hydroxide and their alkoxides. The catalyst is used for preparing biodiesel, and has the advantages of high reaction speed, small alcohol consumption, low cost and the like. However, the raw oil contains a small amount of water and free fatty acid, the free fatty acid and alkali can be subjected to saponification reaction in the reaction process, so that the product contains more fatty soap, the product is difficult to separate, the yield of biodiesel is reduced, and meanwhile, the separation process of the homogeneous catalyst after the reaction is finished is complex, so that the catalyst recycling rate is low. Therefore, highly efficient, easily separable solid basic catalysts are becoming a growing point of research.
The solid alkaline catalyst has the advantages of wide raw materials, environmental protection, reusability, high catalytic activity and the like, and among a plurality of solid alkaline catalysts, such as CaO, niO, znO, la 2 O 3 And the like, caO has stronger alkalinity and shows higher catalytic activity. And CaO has low price, rich raw materials and strong alkalinity, and has small solubility in methanol, so the method has considerable application prospect in preparing biodiesel by utilizing transesterification reaction. CaO is highly alkaline, but CaO absorbs water and CO very easily in air 2 Resulting in reduced catalyst activity and glycerol by-product is also prone to deactivation of its active site. Next, in the reaction system, ca 2+ Is easy to leach, and reduces the activity of the catalyst.
Disclosure of Invention
The invention aims to: the first aim of the invention is to provide a nano bimetallic catalyst with strong alkalinity, high activity, easy separation and lower cost, the second aim of the invention is to provide a preparation method of the nano bimetallic catalyst, and the third aim of the invention is to provide the application of the nano bimetallic catalyst in preparing biodiesel through transesterification.
The technical scheme is as follows: the nano bimetallic catalyst comprises CaO and CuO, wherein the mass ratio of CaO to CuO precursors is 1:1-5:1.
The preparation method of the nano bimetallic catalyst comprises the following steps:
(1) Ca (OH) 2 And dissolving methacrylic acid solution in water, stirring, and filtering to obtain Ca (MAA) 2 ·H 2 O precursorSolution, ca (MAA) 2 ·H 2 The O precursor solution is transparent and colorless;
(2) CuCO is added to 3 ·Cu(OH) 2 Reacting methacrylic acid solution with dichloromethane at 19-21deg.C, evaporating until the liquid disappears, and drying to obtain solid Cu (MAA) 2 A polymer;
(3) Ca (MAA) 2 ·H 2 Mixing the O precursor solution with absolute ethanol, and 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 And Cu (MAA) 2 Mixing with absolute ethanol, stirring, evaporating until the liquid disappears, and drying to obtain Ca (MAA) 2 And Cu (MAA) 2 A mixture of complexes;
(4) Ca (MAA) 2 And Cu (MAA) 2 Calcining the complex to 649-651 ℃, and preserving heat to obtain the nano bimetallic CaO/CuO catalyst.
In step (1), ca (OH) 2 And methacrylic acid in a molar ratio of 1:2 to 2.5.
Further, in the step (1), the stirring speed is 350-400 r/min.
In step (2), cuCO 3 ·Cu(OH) 2 And methacrylic acid in a molar ratio of 29.5:117.9-118. In the step (2), the stirring rotating speed is 350-400 r/min.
In step (3), the evaporation is rotary evaporation. In the step (3), the drying is vacuum drying.
In the step (4), the temperature rising rate of calcination is 0.95-1.05 ℃/min. In step (4), after the catalyst is prepared, the catalyst is added with Ca (OH) 2 Sealing and preserving in the presence of CaO and silica gel to prevent the catalyst from mixing with water and CO 2 Is deactivated by contact with (a) a metal.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The transition metal Cu can activate O-H bond of methanol to accelerate CH 3 O - Is generated; meanwhile, the CuO has an empty valence layer d orbit and can interact with the lone pair electrons of the ester oxygen atoms of the triglyceride to promote the reactionThe substances are adsorbed on the catalyst, so that the transesterification reaction is effectively promoted by the cooperation of CaO;
(2) The method comprises the steps of carrying out transesterification reaction of soybean oil on CaO/CuO catalysts with different doping ratios, wherein under the conditions that the alcohol-to-oil ratio is 13:1, the catalyst dosage is 5% (based on oil weight), the reaction temperature is 72 ℃ and the reaction time is 90min, ca in CaO/CuO precursors is as follows 2+ And Cu 2+ The mass ratio is 4:1, the mass yield of the biodiesel is the highest and is 79%.
Drawings
FIG. 1 is an XRD pattern of a CaO/CuO catalyst sample of the present invention;
FIGS. 2 (a) - (e) are SEM images of CaO/CuO catalyst samples at 1000x, 2000x, 5000x, 10000x, 15000x in order.
Detailed Description
The technical scheme of the invention is further described below by referring to examples.
Example 1
The preparation method of the nano bimetallic catalyst of the embodiment comprises the following steps:
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 subjected to rotary evaporation on a rotary evaporator until the liquid disappeared, and then dried in a vacuum oven for 12 hours to obtain solid Cu (MAA) 2 A polymer.
③Ca(MAA) 2 And Cu (MAA) 2 Preparation of the 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 And Cu (MAA) 2 Mixing with 50mL of absolute ethanol at a mass ratio of 1:1, stirring at room temperature for 1 hr (380 r/min), rotary evaporating on rotary evaporator until the liquid disappears, and drying in vacuum oven for 12 hr to obtain Ca (MAA) 2 /Cu(MAA) 2 A complex.
(4) Preparation of CaO/CuO catalyst
Ca (MAA) obtained in (3) was used as the catalyst 2 /Cu(MAA) 2 The complex is put into a tube furnace for thermal process, calcined to 650 ℃ (heating rate 1 ℃/min) at room temperature, and kept at 650 ℃ for 10min, thus obtaining the CaO/CuO catalyst. The catalyst was stored in a desiccation dish in a sealed condition for use in Ca (OH) 2 In the presence of CaO and silica gel, prevents the catalyst from mixing with water and CO 2 Is a contact of (a) with a substrate.
The prepared CaO/CuO 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 (reaction temperature: 72 ℃, stirring rate: 400 r/min), the biodiesel is obtained, and the yield of the biodiesel is 67% by using a gas chromatography internal standard method.
Example 2
(1) The preparation method of the nano bimetallic catalyst of the embodiment comprises the following steps: ca (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 subjected to rotary evaporation on a rotary evaporator until the liquid disappeared, and then dried in a vacuum oven for 12 hours to obtain solid Cu (MAA) 2 A polymer.
③Ca(MAA) 2 And Cu (MAA) 2 Preparation of the 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 And Cu (MAA) 2 Mixing with 50mL of absolute ethanol at a mass ratio of 2:1, stirring at room temperature for 1 hr (380 r/min), rotary evaporating on rotary evaporator until the liquid disappears, and drying in vacuum oven for 12 hr to obtain Ca (MAA) 2 /Cu(MAA) 2 A complex.
(4) Preparation of CaO/CuO catalyst
Ca (MAA) obtained in (3) was used as the catalyst 2 /Cu(MAA) 2 The complex is put into a tube furnace for thermal process, calcined to 650 ℃ (heating rate 1 ℃/min) at room temperature, and kept at 650 ℃ for 10min, thus obtaining the CaO/CuO catalyst. The catalyst was stored in a desiccation dish in a sealed condition for use in Ca (OH) 2 In the presence of CaO and silica gel, prevents the catalyst from mixing with water and CO 2 Is a contact of (a) with a substrate.
The prepared CaO/CuO 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 (reaction temperature: 72 ℃, stirring rate: 400 r/min), the biodiesel is obtained, and the yield of the biodiesel is 72% by using a gas chromatography internal standard method.
Example 3
The preparation method of the nano bimetallic catalyst of the embodiment comprises the following steps:
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 subjected to rotary evaporation on a rotary evaporator until the liquid disappeared, and then dried in a vacuum oven for 12 hours to obtain solid Cu (MAA) 2 A polymer.
③Ca(MAA) 2 And Cu (MAA) 2 Preparation of the 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 And Cu (MAA) 2 Mixing with 50mL of absolute ethanol at a mass ratio of 3:1, stirring at room temperature for 1 hr (380 r/min), rotary evaporating on rotary evaporator until the liquid disappears, and drying in vacuum oven for 12 hr to obtain Ca (MAA) 2 /Cu(MAA) 2 A complex.
(4) Preparation of CaO/CuO catalyst
Ca (MAA) obtained in (3) was used as the catalyst 2 /Cu(MAA) 2 The complex is put into a tube furnace for thermal process, calcined to 650 ℃ (heating rate 1 ℃/min) at room temperature, and kept at 650 ℃ for 10min, thus obtaining the CaO/CuO catalyst.The catalyst was stored in a desiccation dish in a sealed condition for use in Ca (OH) 2 In the presence of CaO and silica gel, prevents the catalyst from mixing with water and CO 2 Is a contact of (a) with a substrate.
The prepared CaO/CuO 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 (reaction temperature: 72 ℃, stirring rate: 400 r/min), the biodiesel is obtained, and the yield of the biodiesel is 73% by using a gas chromatography internal standard method.
Example 4
The preparation method of the nano bimetallic catalyst of the embodiment comprises the following steps:
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 subjected to rotary evaporation on a rotary evaporator until the liquid disappeared, and then dried in a vacuum oven for 12 hours to obtain solid Cu (MAA) 2 A polymer.
③Ca(MAA) 2 And Cu (MAA) 2 Preparation of the 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 And Cu (MAA) 2 Mixing with 50mL of absolute ethanol at a mass ratio of 4:1, stirring at room temperature for 1 hr (380 r/min), rotary evaporating on rotary evaporator until the liquid disappears, and drying in vacuum oven for 12 hr to obtain Ca (MAA) 2 /Cu(MAA) 2 A complex.
(4) Preparation of CaO/CuO catalyst
Ca (MAA) obtained in (3) was used as the catalyst 2 /Cu(MAA) 2 The complex is put into a tube furnace for thermal process, calcined to 650 ℃ (heating rate 1 ℃/min) at room temperature, and kept at 650 ℃ for 10min, thus obtaining the CaO/CuO catalyst. The catalyst was stored in a desiccation dish in a sealed condition for use in Ca (OH) 2 In the presence of CaO and silica gel, prevents the catalyst from mixing with water and CO 2 Is a contact of (a) with a substrate.
The prepared CaO/CuO 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 (reaction temperature: 72 ℃, stirring rate: 400 r/min), the biodiesel is obtained, and the yield of the biodiesel is 79% by using a gas chromatography internal standard method.
Example 5
The preparation method of the nano bimetallic catalyst of the embodiment comprises the following steps:
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 pear-shaped bottles and run on a rotary evaporatorRotary evaporation until the liquid disappeared, then placing it in a vacuum drying oven to dry for 12h to obtain solid Cu (MAA) 2 A polymer.
③Ca(MAA) 2 And Cu (MAA) 2 Preparation of the 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 And Cu (MAA) 2 Mixing with 50mL of absolute ethanol at a mass ratio of 5:1, stirring at room temperature for 1 hr (380 r/min), rotary evaporating on rotary evaporator until the liquid disappears, and drying in vacuum oven for 12 hr to obtain Ca (MAA) 2 /Cu(MAA) 2 A complex.
(4) Preparation of CaO/CuO catalyst
Ca (MAA) obtained in (3) was used as the catalyst 2 /Cu(MAA) 2 The complex is put into a tube furnace for thermal process, calcined to 650 ℃ (heating rate 1 ℃/min) at room temperature, and kept at 650 ℃ for 10min, thus obtaining the CaO/CuO catalyst. The catalyst was stored in a desiccation dish in a sealed condition for use in Ca (OH) 2 In the presence of CaO and silica gel, prevents the catalyst from mixing with water and CO 2 Is a contact of (a) with a substrate.
The prepared CaO/CuO 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 (reaction temperature: 72 ℃, stirring rate: 400 r/min), the biodiesel is obtained, and the yield of the biodiesel is 78% as determined by using a gas chromatography internal standard method.
XRD analysis was performed on CaO/CuO nanocatalysts prepared in examples 1 to 5, and the results are shown in FIG. 1. Diffraction peaks representing CaO (JCPDS Cards No.77-2376 #) appear at 2θ=32.72°,43.75 °, and CuO (JCPDS C) appears at 2θ=35.5 °,38.6 °,48.8 °,58.4 °,61.6 °Ards No.45-0937 #). The ratio of CaO to CuO in the CaO/CuO nano catalyst is from 1:1 to 5:1, and along with the reduction of the CuO, the diffraction peak corresponding to the CuO is obviously reduced, and the diffraction peak corresponding to the CaO is gradually enhanced. At the same time, a distinct diffraction peak also appears at 2θ= 30.09 °,43.75 °, which corresponds to CaCO 3 Diffraction peaks of (JCPDS Cards No.47-1743 #) indicate that CaCO is generated by the CaO/CuO catalyst in the storage process when the CaO/CuO catalyst contacts air 3 . As can be seen from FIG. 1, caCO decreases with decreasing CuO 3 The corresponding diffraction peak is gradually enhanced, thereby showing that the CuO has a certain protection effect on the CaO and can effectively prevent the CaO from being mixed with CO in the air 2 And (3) contact.
SEM analysis of CaO/CuO (1:1) nanocatalyst prepared in example 1 was performed and the results are shown in FIGS. 2 (a) - (e). As can be seen from FIGS. 2 (a) - (e), the CaO/CuO nano-catalyst obtained by high-temperature calcination has a rich pore structure, which is beneficial to improving the rate of transesterification and shortening the reaction time.
EDX scanning is carried out on the prepared CaO/CuO nano catalyst, the analysis of catalyst elements is shown in table 1, and the result shows that Ca element and Cu element are uniformly mixed.
TABLE 1 analysis of CaO/CuO (1:1) nanocatalyst elements
Comparative example 1
The CaO catalyst prepared in the prior art 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 (reaction temperature: 72 ℃, stirring rate: 400 r/min), the biodiesel is obtained, and the yield of the biodiesel is 73% by using a gas chromatography internal standard method.
Claims (9)
1. A nano bimetallic catalyst, characterized in that: the catalyst comprises CaO and CuO, wherein the mass ratio of the CaO precursor to the CuO precursor is 1:1-5:1, and the catalyst has a porous structure; the preparation method of the catalyst comprises the following steps:
(1) Ca (OH) 2 And dissolving methacrylic acid solution in water, stirring, and filtering to obtain Ca (MAA) 2 ·H 2 O precursor solution, ca (MAA) 2 ·H 2 The O precursor solution is transparent and colorless;
(2) CuCO is added to 3 ·Cu(OH) 2 Reacting methacrylic acid solution with dichloromethane at 19-21deg.C, evaporating until the liquid disappears, and drying to obtain solid Cu (MAA) 2 A polymer;
(3) The Ca (MAA) 2 ·H 2 Mixing the O precursor solution with absolute ethanol, and 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 And Cu (MAA) 2 Mixing with absolute ethanol, stirring, evaporating until the liquid disappears, and drying to obtain Ca (MAA) 2 And Cu (MAA) 2 A mixture of complexes;
(4) The Ca (MAA) 2 And Cu (MAA) 2 Calcining the complex to 649-651 ℃, and preserving heat to obtain the nano bimetallic CaO/CuO catalyst.
2. The nano-bimetallic catalyst of claim 1, wherein: in step (1), the Ca (OH) 2 And the molar ratio of methacrylic acid is 1:2-2.5.
3. The method for preparing the nano bimetallic catalyst according to claim 1, wherein: in step (2), the CuCO 3 ·Cu(OH) 2 And methacrylic acid in a molar ratio of 29.5:117.9-118.
4. The nano-bimetallic catalyst of claim 1, wherein: in the step (2), the stirring speed is 350-400 r/min.
5. The nano-bimetallic catalyst of claim 1, wherein: in step (3), the evaporation is rotary evaporation.
6. The nano-bimetallic catalyst of claim 1, wherein: in the step (3), the drying is vacuum drying.
7. The nano-bimetallic catalyst of claim 1, wherein: in the step (4), the temperature rising rate of the calcination is 0.95-1.05 ℃/min.
8. The nano-bimetallic catalyst of claim 1, wherein: in step (4), after the catalyst is prepared, the catalyst is added with Ca (OH) 2 Sealing and preserving in the presence of CaO and silica gel.
9. Use of the nano-bimetallic catalyst of claim 1 in transesterification to prepare biodiesel.
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