CN111054441A - Preparation method and application of silicotungstic acid shell-coated and core-embedded zeolite imidazole framework - Google Patents
Preparation method and application of silicotungstic acid shell-coated and core-embedded zeolite imidazole framework Download PDFInfo
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 111
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 44
- 239000010457 zeolite Substances 0.000 title claims abstract description 44
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 10
- JFRHWQBNJASIQN-UHFFFAOYSA-N CO.CC1=C(N=CN1)C Chemical compound CO.CC1=C(N=CN1)C JFRHWQBNJASIQN-UHFFFAOYSA-N 0.000 claims abstract description 8
- NVLDSCWHEUSPCV-UHFFFAOYSA-N [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NVLDSCWHEUSPCV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000000536 complexating effect Effects 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 62
- 239000003225 biodiesel Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 12
- 239000004519 grease Substances 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 5
- 241000195493 Cryptophyta Species 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 150000007517 lewis acids Chemical class 0.000 abstract description 7
- 239000002879 Lewis base Substances 0.000 abstract description 6
- 150000007527 lewis bases Chemical class 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 15
- 125000004430 oxygen atom Chemical group O* 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 8
- 230000000269 nucleophilic effect Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000011964 heteropoly acid Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000005935 nucleophilic addition reaction Methods 0.000 description 4
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 4
- 125000005457 triglyceride group Chemical group 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- 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
- C11C3/10—Ester interchange
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The invention relates to a biomass energy utilization technology, and aims to provide a preparation method and application of a silicotungstic acid shell-coated and core-embedded zeolite imidazole framework. The method comprises the following steps: dissolving silicotungstic acid in a cobalt nitrate methanol solution, adding the solution into a dimethyl imidazole methanol solution, continuously stirring at room temperature, and performing centrifugal treatment after full complexing reaction; filtering, cleaning and drying the solid product to obtain a silicotungstic acid nucleus embedded zeolite imidazole framework; adding the mixture into a silicotungstic acid aqueous solution, carrying out ultrasonic treatment, continuously stirring at room temperature, fully reacting, and carrying out centrifugal treatment; and filtering, washing and drying the solid product to obtain the product. The zeolite imidazole framework of the invention can maintain the structural integrity of uniform pore diameter in the high-temperature and high-pressure reaction process, and simultaneously provides active catalytic sites of Lewis acid and Lewis base. The catalyst realizes the uniform distribution of silicotungstic acid in higher loading capacity, has good stability when being recycled, has high conversion efficiency after being regenerated, and has long recycling service life.
Description
Technical Field
The invention relates to a biomass energy utilization technology, in particular to a preparation method and application of a silicotungstic acid shell-coated and core-embedded zeolite imidazole framework.
Background
The microalgae has the unique advantages of high oil content, high growth rate and the like, and is regarded as an important choice of biodiesel raw materials. The traditional method for preparing biodiesel by converting microalgae grease usually uses a homogeneous catalyst, and although higher conversion efficiency is obtained, the problems of equipment corrosion, environmental pollution and the like caused by difficult recovery of an acid-base catalyst are difficult to solve, and the continuous and healthy development of the industry is restrained. The problem can be solved by the biodiesel prepared by transforming the biological grease with the heterogeneous catalyst developed in recent years, and the method becomes a research hotspot of the catalyst at home and abroad. The heteropoly acid is an excellent strong protonic acid heterogeneous catalyst, but the specific surface area of particles is small, so that the reaction activity of the heteropoly acid cannot be fully exerted; and is easily dissolved in polar organic solvent to form a homogeneous system, which makes the catalyst difficult to recover and causes the corrosion of equipment. When a solid acid catalyst is prepared by supporting a heteropoly acid on a carrier having a large specific surface area, it is an effective method for solving the above problems. The zeolitic imidazole framework has a uniform pore structure and excellent chemical stability, maintains structural integrity even in polar solvents, and is an excellent porous support that provides both lewis acid and lewis base active catalytic sites. Therefore, the heteropolyacid is loaded on the zeolite imidazole framework to prepare the acid-base bifunctional catalyst, which is the technical key for realizing the efficient recycling of the catalyst for preparing the biodiesel by converting the algae oil.
Malkar et al supported phosphotungstic acid inside a zeolite imidazole framework ZIF-8 centered on zinc atoms to prepare a catalyst for esterification reaction of benzoic anhydride and cinnamyl alcohol, but the catalyst structure has limited phosphotungstic acid loading (less than 18%) to result in a catalytic efficiency of only 60%, and in order to improve the catalytic efficiency, more phosphotungstic acid needs to be loaded but the zeolite imidazole framework is collapsed. Jeon et al supported phosphotungstic acid on the surface of zeolite imidazole framework ZIF-8 particles centered on zinc atoms to prepare the catalyst for the transesterification of soybean oil, but the phosphotungstic acid is agglomerated at the periphery of the zeolite imidazole framework to cause the reduction of the specific surface area of the catalyst (only 457 m)2/g), although a higher phosphotungstic acid loading (50%) was achieved, the catalytic efficiency of the transesterification was not significantly improved (only 73%).
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method and application of a silicotungstic acid shell-coated and core-embedded zeolite imidazole framework.
In order to solve the technical problem, the solution of the invention is as follows:
provides a preparation method of a silicotungstic acid shell-coated and core-embedded zeolite imidazole framework, which comprises the following steps:
(1) respectively dissolving 0.72-7.2 g of cobalt nitrate hexahydrate and 1.63-16.3 g of dimethyl imidazole in 50-500 mL of methanol to prepare a cobalt nitrate methanol solution and a dimethyl imidazole methanol solution; dissolving 0.1-1 g of silicotungstic acid in a cobalt nitrate methanol solution, and adding the solution into a dimethyl imidazole methanol solution at the adding speed of 50 mL/min; continuously stirring for 12h at room temperature, and centrifuging after full complexing reaction; filtering out the solid product, washing for 3 times by using deionized water, and then drying to obtain a silicotungstic acid nucleus embedded zeolite imidazole framework;
(2) dissolving 0.2-2 g of silicotungstic acid in 10-50 mL of deionized water to prepare a silicotungstic acid aqueous solution; adding 0.3-3 g of silicotungstic acid nucleus embedded zeolite imidazole framework into a silicotungstic acid aqueous solution; after ultrasonic treatment is carried out for 30min, stirring is carried out continuously for 24h at room temperature, and centrifugal treatment is carried out after full reaction; and filtering out the solid product, washing the solid product for 3 times by using deionized water, and then drying the solid product to obtain the silicotungstic acid shell-coated and core-embedded zeolite imidazole framework.
In the invention, the stirring in the steps (1) and (2) is performed by using a magnetic stirrer at a rotating speed of 100-500 rpm.
In the invention, the drying treatment in the steps (1) and (2) is drying in an oven at 60-100 ℃ for 6-10 h.
The invention further provides an application method of the silicotungstic acid shell-coated and core-embedded zeolite imidazole skeleton prepared by the method in catalyzing algae oil to prepare biodiesel, which comprises the following steps:
mixing the catalyst coated by silicotungstic acid shell and embedded by core with microalgae grease according to the mass ratio of 1: 25, and placing the mixture in a polytetrafluoroethylene sealed reaction kettle; then adding methanol according to the molar ratio of the alcohol to the oil of 10: 1, and reacting for 2 hours at the constant temperature of 200 ℃ to obtain a fatty acid methyl ester product, namely the biodiesel.
In the invention, the main component of the prepared biodiesel comprises fatty acid methyl ester with the carbon chain length of C14-C22.
Description of the inventive principles:
in the process of catalyzing the algae oil to prepare the biodiesel, carbonyl of fatty acid components in the algae oil is combined with free protons provided by silicotungstic acid to form active carbocation, then the carbocation and methanol are subjected to nucleophilic addition reaction to obtain a tetrahedral intermediate, and the tetrahedral intermediate is subjected to reactionElimination reaction loss of H2O and H+And generating a fatty acid methyl ester product, namely the biodiesel. On the other hand, triglyceride components in the microalgae oil are combined with cobalt atoms (Lewis acid) in a zeolite imidazole framework, and two oxygen atoms of carbonyl groups in the triglyceride form resonance under the action of electron delocalization to generate electrophilic carbon atoms; meanwhile, nitrogen atoms (Lewis base) in the zeolite imidazole framework are coordinated with methanol molecules to induce proton shift in methanol hydroxyl groups to generate nucleophilic oxygen atoms, and the nucleophilic oxygen atoms attack electrophilic carbon atoms of triglyceride carbonyl groups to generate ester exchange reaction, so that a fatty acid methyl ester product, namely the biodiesel is obtained.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares the heterogeneous catalyst by coating the silicotungstic acid shell and embedding the core into the zeolite imidazole framework, avoids the problems of equipment corrosion, environmental pollution and the like caused by difficult recovery of the homogeneous acid-base catalyst, and provides a green and efficient new method for preparing the biodiesel by converting the microalgae grease.
2. The zeolite imidazole framework can keep the structural integrity of uniform pore diameter in the high-temperature and high-pressure reaction process and simultaneously provides active catalytic sites of Lewis acid and Lewis base; the association of silicotungstic acid with the zeolitic imidazole framework via N-O bonds avoids dissolution in polar solvents, providing sufficient protonic acid sites for catalytic reactions.
3. Compared with the phosphotungstic acid loaded on a zeolite imidazole framework centered on zinc atoms reported in the prior literature, the silicotungstic acid shell-coated and core-embedded zeolite imidazole framework catalyst developed by the invention realizes the uniform distribution of silicotungstic acid at higher loading, and the specific surface area is still as high as 1101 mm when the silicotungstic acid loading is 50 percent2And/g, so that the catalytic transesterification efficiency of the microalgae grease is as high as 98%.
4. The catalyst has good stability when being recycled, the conversion efficiency of the fresh catalyst can reach 96% after the catalyst is regenerated, and the recycling service life of the catalyst can reach more than or equal to 2000 hours.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. The examples may provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the invention in any way.
Example 1
0.72g of cobalt nitrate hexahydrate and 1.63g of dimethylimidazole were taken and dissolved in 50mL of methanol, respectively. 0.1g of silicotungstic acid is dissolved in a cobalt nitrate methanol solution, slowly added into a dimethyl imidazole methanol solution (the adding speed is 50mL/min), and continuously stirred at the rotating speed of 100rpm for 12 hours at room temperature. And after full complexing reaction, centrifuging, filtering out the solid, washing the solid for 3 times by using deionized water, and drying the solid in an oven at the temperature of 60 ℃ for 6 hours to obtain the silicotungstic acid nucleus embedded zeolite imidazole framework.
Dissolving 0.2g of silicotungstic acid in 10mL of deionized water, adding 0.3g of the obtained silicotungstic acid nucleus embedded zeolite imidazole skeleton into a silicotungstic acid aqueous solution, carrying out ultrasonic treatment for 30min, and continuously stirring at the rotating speed of 100rpm for 24h at room temperature. After full reaction, centrifuging, filtering out solid, washing with deionized water for 3 times, and drying in an oven at 60 deg.C for 6h to obtain silicotungstic acid shell-coated and core-embedded zeolite imidazole skeleton (at this time, the specific surface area of 50% of silicotungstic acid load is up to 1101m2/g)。
Taking 0.4g of the silicotungstic acid shell-coated and core-embedded zeolite imidazole skeleton obtained as a catalyst, mixing the catalyst with 10g of microalgae, putting the mixture into a polytetrafluoroethylene sealed reaction kettle, adding 5mL of methanol (the molar ratio of alcohol to oil is 10: 1), and reacting for 2 hours at a constant temperature of 200 ℃. Carbonyl of fatty acid components in the microalgae grease is combined with free protons provided by silicotungstic acid to form active carbonium ions, then the carbonium ions and methanol undergo nucleophilic addition reaction to obtain tetrahedral intermediates, and the tetrahedral intermediates lose H through elimination reaction2O and H+And generating a fatty acid methyl ester product, namely the biodiesel. On the other hand, triglyceride components in the microalgae oil are combined with cobalt atoms (Lewis acid) in a zeolite imidazole framework, and two oxygen atoms of carbonyl groups in the triglyceride form resonance under the action of electron delocalization to generate electrophilic carbon atoms; with nitrogen atoms in the zeolitic imidazole framework (Lewis)Alkali) is coordinated with methanol molecules to induce proton shift in methanol hydroxyl to generate nucleophilic oxygen atoms, and the nucleophilic oxygen atoms attack electrophilic carbon atoms of triglyceride carbonyl to generate ester exchange reaction, so as to obtain fatty acid methyl ester product, namely biodiesel. The catalyst ensures that the efficiency of the microalgae grease catalyzed transesterification is up to 98 percent, the catalyst can be recycled after regeneration to reach 96 percent of the conversion efficiency of the fresh catalyst, and the recycling service life of the catalyst is more than or equal to 2000 hours.
Example 2
7.2g of cobalt nitrate hexahydrate and 16.3g of dimethylimidazole were dissolved in 500mL of methanol, respectively. 1g of silicotungstic acid is dissolved in a cobalt nitrate methanol solution, slowly added into a dimethyl imidazole methanol solution (the adding speed is 50mL/min), and continuously stirred at the rotating speed of 500rpm for 12 hours at room temperature. And after full complexing reaction, centrifuging, filtering out the solid, washing the solid for 3 times by using deionized water, and drying the solid in an oven at 100 ℃ for 10 hours to obtain the silicotungstic acid nucleus embedded zeolite imidazole framework.
Dissolving 2g of silicotungstic acid in 50mL of deionized water, adding 3g of the obtained silicotungstic acid nucleus embedded type zeolite imidazole skeleton into a silicotungstic acid aqueous solution, carrying out ultrasonic treatment for 30min, and continuously stirring at the rotating speed of 500rpm for 24h at room temperature. After full reaction, centrifuging, filtering out solid, washing with deionized water for 3 times, and drying in an oven at 100 deg.C for 10 hr to obtain silicotungstic acid shell-coated and core-embedded zeolite imidazole skeleton (at this time, the specific surface area of 50% of silicotungstic acid load is up to 1101m2/g)。
Taking 4g of the silicotungstic acid shell-coated and core-embedded zeolite imidazole skeleton obtained as a catalyst, mixing the catalyst with 100g of microalgae oil, placing the mixture into a polytetrafluoroethylene sealed reaction kettle, adding 50mL of methanol (the molar ratio of alcohol to oil is 10: 1), and reacting at a constant temperature of 200 ℃ for 2 hours. Carbonyl of fatty acid components in the microalgae grease is combined with free protons provided by silicotungstic acid to form active carbonium ions, then the carbonium ions and methanol undergo nucleophilic addition reaction to obtain tetrahedral intermediates, and the tetrahedral intermediates lose H through elimination reaction2O and H+And generating a fatty acid methyl ester product, namely the biodiesel. On the other hand, triglyceride components in microalgal oil and fat are bonded to cobalt atoms (Lewis acid) in the zeolitic imidazole skeletonUnder the action of electron delocalization, two oxygen atoms of carbonyl groups in triglyceride form resonance to generate an electrophilic carbon atom; meanwhile, nitrogen atoms (Lewis base) in the zeolite imidazole framework are coordinated with methanol molecules to induce proton shift in methanol hydroxyl groups to generate nucleophilic oxygen atoms, and the nucleophilic oxygen atoms attack electrophilic carbon atoms of triglyceride carbonyl groups to generate ester exchange reaction, so that a fatty acid methyl ester product, namely the biodiesel is obtained. The catalyst ensures that the efficiency of the microalgae grease catalyzed transesterification is up to 98 percent, the catalyst can be recycled after regeneration to reach 96 percent of the conversion efficiency of the fresh catalyst, and the recycling service life of the catalyst is more than or equal to 2000 hours.
Example 3
3.6g of cobalt nitrate hexahydrate and 8.1g of dimethylimidazole were dissolved in 250mL of methanol, respectively. 0.5g of silicotungstic acid is dissolved in a cobalt nitrate methanol solution, and then slowly added into a dimethyl imidazole methanol solution (the adding speed is 50mL/min), and the mixture is continuously stirred at the rotating speed of 300rpm for 12 hours at room temperature. And after full complexing reaction, centrifuging, filtering out the solid, washing the solid for 3 times by using deionized water, and drying the solid in an oven at the temperature of 80 ℃ for 8 hours to obtain the silicotungstic acid nucleus embedded zeolite imidazole framework.
Dissolving 1g of silicotungstic acid in 25mL of deionized water, adding 1.5g of the obtained silicotungstic acid nucleus embedded type zeolite imidazole skeleton into a silicotungstic acid aqueous solution, carrying out ultrasonic treatment for 30min, and continuously stirring at the rotating speed of 300rpm for 24h at room temperature. After full reaction, centrifuging, filtering out solid, washing with deionized water for 3 times, and drying in an oven at 80 deg.C for 8h to obtain silicotungstic acid shell-coated and core-embedded zeolite imidazole skeleton (at this time, the specific surface area of 50% of silicotungstic acid load is up to 1101m2/g)。
Taking 2g of the silicotungstic acid shell-coated and core-embedded zeolite imidazole skeleton obtained as a catalyst, mixing the catalyst with 50g of microalgae oil, placing the mixture into a polytetrafluoroethylene sealed reaction kettle, adding 25mL of methanol (the molar ratio of alcohol to oil is 10: 1), and reacting for 2 hours at a constant temperature of 200 ℃. Carbonyl of fatty acid components in the microalgae grease is combined with free protons provided by silicotungstic acid to form active carbonium ions, then the carbonium ions and methanol undergo nucleophilic addition reaction to obtain tetrahedral intermediates, and the tetrahedral intermediates lose H through elimination reaction2O and H+And generating a fatty acid methyl ester product, namely the biodiesel. On the other hand, triglyceride components in the microalgae oil are combined with cobalt atoms (Lewis acid) in a zeolite imidazole framework, and two oxygen atoms of carbonyl groups in the triglyceride form resonance under the action of electron delocalization to generate electrophilic carbon atoms; meanwhile, nitrogen atoms (Lewis base) in the zeolite imidazole framework are coordinated with methanol molecules to induce proton shift in methanol hydroxyl groups to generate nucleophilic oxygen atoms, and the nucleophilic oxygen atoms attack electrophilic carbon atoms of triglyceride carbonyl groups to generate ester exchange reaction, so that a fatty acid methyl ester product, namely the biodiesel is obtained. The catalyst ensures that the efficiency of the microalgae grease catalyzed transesterification is up to 98 percent, the catalyst can be recycled after regeneration to reach 96 percent of the conversion efficiency of the fresh catalyst, and the recycling service life of the catalyst is more than or equal to 2000 hours.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. A preparation method of a silicotungstic acid shell-coated and core-embedded zeolite imidazole framework is characterized by comprising the following steps:
(1) respectively dissolving 0.72-7.2 g of cobalt nitrate hexahydrate and 1.63-16.3 g of dimethyl imidazole in 50-500 mL of methanol to prepare a cobalt nitrate methanol solution and a dimethyl imidazole methanol solution; dissolving 0.1-1 g of silicotungstic acid in a cobalt nitrate methanol solution, and adding the solution into a dimethyl imidazole methanol solution at the adding speed of 50 mL/min; continuously stirring for 12h at room temperature, and centrifuging after full complexing reaction; filtering out the solid product, washing for 3 times by using deionized water, and then drying to obtain a silicotungstic acid nucleus embedded zeolite imidazole framework;
(2) dissolving 0.2-2 g of silicotungstic acid in 10-50 mL of deionized water to prepare a silicotungstic acid aqueous solution; adding 0.3-3 g of silicotungstic acid nucleus embedded zeolite imidazole framework into a silicotungstic acid aqueous solution; after ultrasonic treatment is carried out for 30min, stirring is carried out continuously for 24h at room temperature, and centrifugal treatment is carried out after full reaction; and filtering out the solid product, washing the solid product for 3 times by using deionized water, and then drying the solid product to obtain the silicotungstic acid shell-coated and core-embedded zeolite imidazole framework.
2. The method according to claim 1, wherein the stirring in steps (1) and (2) is performed by using a magnetic stirrer at a rotation speed of 100-500 rpm.
3. The method according to claim 1, wherein the drying treatment in steps (1) and (2) is drying in an oven at 60-100 ℃ for 6-10 h.
4. The application method of the silicotungstic acid shell-coated and core-embedded zeolite imidazole skeleton prepared by the method of claim 1 in catalyzing algae oil to prepare biodiesel is characterized by comprising the following steps:
mixing the catalyst coated by silicotungstic acid shell and embedded by core with microalgae grease according to the mass ratio of 1: 25, and placing the mixture in a polytetrafluoroethylene sealed reaction kettle; then adding methanol according to the molar ratio of the alcohol to the oil of 10: 1, and reacting for 2 hours at the constant temperature of 200 ℃ to obtain a fatty acid methyl ester product, namely the biodiesel.
5. The method of claim 4, wherein the biodiesel fuel comprises fatty acid methyl ester with carbon chain length of C14-C22.
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