CN109134407B - Preparation method of aviation kerosene precursor - Google Patents
Preparation method of aviation kerosene precursor Download PDFInfo
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- CN109134407B CN109134407B CN201811155471.4A CN201811155471A CN109134407B CN 109134407 B CN109134407 B CN 109134407B CN 201811155471 A CN201811155471 A CN 201811155471A CN 109134407 B CN109134407 B CN 109134407B
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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Abstract
The invention relates to a preparation method of an aviation kerosene precursor, which comprises the steps of mixing furfural, 2-methylfuran and a solid Lewis acid catalyst, placing the mixture in a closed reactor, and carrying out catalytic reaction to prepare a C15 furan trimer; the catalytic reaction conditions are as follows: the reaction temperature is 100 ℃ and 150 ℃, no solvent is added, and the reaction time is 7-16 hours. The molar ratio of the furfural to the 2-methylfuran is 1: (2-3), the mass ratio of the furfural to the catalyst is (5-20):1, and the invention adopts a solid Lewis acid catalyst condensation reaction with metal Zr as a core metal element. The catalyst has the advantages of high activity, good stability, repeated utilization, high yield of reaction products, high selectivity and the like. Meanwhile, the Lewis acid type catalyst does not generate acid protons, so that the corrosion of the catalyst to equipment at high temperature is avoided, the treatment after reaction is convenient, and the catalyst is environment-friendly.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of an aviation kerosene precursor.
Background
Today, renewable energy is of great interest due to the lack of petroleum fuels. Currently, biodiesel and bioethanol from natural renewable biomass resources have been widely used as liquid fuels, but there are still some limitations when they are used as transportation fuels. These fuels require grain as raw material, are costly and have a land battle with human beings. Meanwhile, biodiesel has low oxidation stability and poor flowability at low temperature, and bioethanol has low combustion heat value and can only be used as an additive of gasoline. These limitations have prompted the need for the development of new fuels. As is known, aviation kerosene is a special liquid fuel, is specially used for the flight requirements of spacecrafts, and is a strategic material of the country. The composition mainly comprises paraffin hydrocarbon and aromatic hydrocarbon with carbon number between 8-16. At present, aviation kerosene is mainly refined from petrochemical resources. Due to the non-regenerability of the traditional petrochemical resources, the development of a new technology for preparing aviation kerosene from renewable resources is imperative.
Lignocellulose is a renewable resource in the nature, and has large resource quantity and wide distribution. It can be converted by processing to obtain various types of platform molecules such as furfural, furfuryl alcohol, 5-hydroxymethyl furfural and the like. The platform molecules can be further upgraded to synthesize different liquid fuel molecules and high value-added chemicals. However, these platform molecules typically contain only 5-6 carbon atoms, well below the minimum carbon number requirement for jet fuel. Therefore, it is necessary to obtain a high carbon number fuel precursor by forming an intermolecular C — C bond, thereby satisfying the C8-16 molecular precursor requirement in jet fuel. In 2005, Dumesic and Huber et al [ Science, 308 (2005) 1446-. Since then, new condensation reactions have been reported for the condensation reaction of biomass-based platform molecules, thereby constructing new precursor molecules for jet fuel. For example, pinacol coupling [ Dalton Transactions, 46 (2017) 6177-6182], ketonization [ ChemSusChem, 6 (2013) 141-151 ], olefin condensation [ chem. Rev, 106 (2006) 4044-4098 ], hydroxyalkylation/alkylation (HAA) [ Energy environ. Sci, 5 (2012) 6328-6344 ] were studied to construct new C-C bond production diesel precursors.
Among these methods, HAA reaction has been attracting attention in recent years, and a typical example of this reaction is condensation of 2-methylfuran (2-MF) and a carbonyl group-containing compound to form a furan-type trimer precursor, which is further hydrogenated/dehydrated to give the corresponding branched alkane. Investigations have found that the relevant reactions for synthesizing fuel precursors are usually catalyzed by bronsted acids (liquid protic acids and solid protic acids) to obtain the desired product. However, the use of liquid protonic acid catalyst (such as sulfuric acid) still has more defects, such as high environmental pollution, strong corrosion to equipment and complicated post-treatment [ Catal. Today, 234 (2014) 91-99 ]. The residual acid in the product is liable to poison the catalyst in the subsequent high-temperature hydrodeoxygenation step. Recently, researchers at the institute of chemical and physical research in the department of Chinese academy of sciences reported that the fuel precursor molecules of various aviation kerosene are prepared by catalyzing the condensation coupling reaction of furan molecules and various molecules by using lignosulfonate-based acidic resin as a catalyst, and a better reaction effect is obtained [ Green Chem, 18 (2016) 1218-. However, it is not easy to find that the solid protonic acid catalyst can solve the problem of recovering the liquid protonic acid catalyst, but part of the catalyst still has the problems of poor thermal stability, easy loss of acid sites, obvious reduction of catalyst activity in recycling and the like. Therefore, in view of the existing problems, the development of a catalyst having high activity, low corrosiveness and being capable of repeated multiple use is a problem to be solved in preparing an aviation kerosene precursor by HAA reaction of 2-methylfuran and furfural. In connection with the related studies, various chinese patent applications (CN 103087748A, CN105985216A and CN 108130112A) have been applied to HAA condensation reactions of macroconjugates, all of which use proton type solid acids to catalyze the related HAA condensation reactions, and thus the above-mentioned technical problems still remain.
It has been found through investigations that catalysts having Lewis acidity (Lewis) are capable of catalyzing HAA-type reactions such as Friedel-crafts alkylation in organic synthetic chemistry. Based on the method, the solid Lewis acid catalyst is developed to catalyze the condensation reaction of furfural and 2-methylfuran to prepare the C15 furan type tripolymer molecule, so that the problems caused by the protonic acid catalyst can be avoided, and the method meets the requirement of green chemistry and environmental friendliness. Meanwhile, related researches on preparation of the C15 furan type trimer aviation kerosene precursor by the condensation reaction of furfural and 2-methylfuran catalyzed by the solid Lewis acid catalyst are not reported, and the method has very important significance for developing more efficient Lewis acid catalysts to catalyze renewable biomass molecules to synthesize aviation kerosene in the future.
Disclosure of Invention
The invention aims to provide a preparation method of an aviation kerosene precursor so as to obtain a C15 furan trimer diesel precursor with high yield.
The technical scheme of the invention comprises the following specific steps:
furfural, 2-methylfuran and a solid Lewis acid catalyst are uniformly mixed and then added into a closed reactor for catalytic condensation reaction to prepare an aviation kerosene precursor C15 furan trimer.
The conditions of the condensation reaction are as follows: the reaction temperature is 100-150 ℃, the stirring speed is 500-800rpm, the solvent-free reaction is carried out, and the reaction time is 7-16 hours.
The molar ratio of the furfural to the 2-methylfuran is 1: (2-3), and the mass ratio of the furfural to the solid Lewis acid catalyst is (5-20): 1.
The solid Lewis acid catalyst is prepared by adopting a sol-gel method.
The preparation method of the solid Lewis acid catalyst comprises the following steps:
(1) weighing 2g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) in 75mL of hydrochloric acid with the concentration of 1.6mol/L, and stirring for 3h at 40 ℃ to obtain a mixed solution;
(2) 4.25g tetraethyl orthosilicate (TEOS) as silicon source and a certain mass of ZrOCl2•8H2Adding O as a zirconium source into the mixed solution to enable the Si/Zr molar ratio to be (10-25): 1, and continuously stirring for 24 hours at 40 ℃ to obtain a suspension;
(3) transferring the obtained suspension into a reaction kettle, placing the reaction kettle in an oven, and placing for 24 hours at 100 ℃;
(4) taking the reaction kettle out of the oven, cooling to room temperature, filtering, and washing with deionized water for three times to obtain a catalyst precursor;
(5) and drying the catalyst precursor obtained after filtering and cleaning in an oven at 100 ℃, fully grinding the dried catalyst precursor, and calcining at 550 ℃ for 6 hours to obtain the Zr/SBA-15 catalyst.
In the above method for producing a solid Lewis acid catalyst, the best effect is obtained when the Si/Zr ratio is controlled to 20: 1.
The invention has the advantages that: the Zr/SBA-15 catalyst with Lewis acidity prepared by adopting a sol-gel method can be used for catalyzing HAA reaction, so that side reactions (such as furan ring opening) which are easily generated in the traditional proton acid catalysis reaction are avoided. The catalyst does not generate acidic protons in the reaction and has extremely low corrosivity. The catalyst can be reused, the product yield is high, and the byproducts are few. In addition, the invention reports that the HAA reaction of furfural and 2-methylfuran is catalyzed by using a solid Lewis acid catalyst for the first time, so that the reaction selectivity is high, the post-treatment is convenient, and the industrial application prospect is good.
Drawings
FIG. 1 is a schematic diagram of the synthesis of C15 furan trimer according to the present invention.
FIG. 2 is a nuclear magnetic spectrum H spectrum representation of the product obtained in example 1 of the present invention.
FIG. 3 is a C-spectrum NMR chart of the product obtained in example 1 of the present invention.
FIG. 4 is a Py-IR characterization of the product obtained in example 1 of the present invention.
FIG. 5 shows NH of the product obtained in example 1 of the present invention3-a TPD profile.
FIG. 6 is a wide angle XRD characterization of a series of Zr/SBA-15 of the present invention.
FIG. 7 is a small angle XRD representation of a series of Zr/SBA-15 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
As shown in figure 1, furfural and 2-methylfuran can be subjected to condensation reaction under the catalysis of a solid Lewis acid catalyst to generate C15 furan trimer.
The solid Lewis acid catalysts used in the present invention include Zr/SBA-15, Fe/SBA-15, W/SBA-15 and Sn/SBA-15.
The preparation method of the solid Lewis acid catalyst Zr/SBA-15 comprises the following steps:
(1) weighing 2g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) in 75mL of hydrochloric acid with the concentration of 1.6mol/L, and stirring for 3h at 40 ℃ to obtain a mixed solution;
(2) 4.25g tetraethyl orthosilicate (TEOS) as silicon source and a certain mass of ZrOCl2•8H2Adding O as a zirconium source into the mixed solution to enable the Si/Zr molar ratio to be (10-25): 1, and continuously stirring for 24 hours at 40 ℃ to obtain a suspension;
(3) transferring the obtained suspension into a reaction kettle, placing the reaction kettle in an oven, and placing for 24 hours at 100 ℃;
(4) taking the reaction kettle out of the oven, cooling to room temperature, filtering, and washing with deionized water for three times to obtain a catalyst precursor;
(5) and drying the catalyst precursor obtained after filtering and cleaning in an oven at 100 ℃, fully grinding the dried catalyst precursor, and calcining at 550 ℃ for 6 hours to obtain the Zr/SBA-15 catalyst.
The preparation method of the solid Lewis acid catalyst Fe/SBA-15 comprises the following steps:
(1) weighing 2g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) in 75mL of hydrochloric acid with the concentration of 1.6mol/L, and stirring for 3h at 40 ℃ to obtain a mixed solution;
(2) 4.25g tetraethyl orthosilicate (TEOS) as silicon source and a certain mass of FeCl3Adding the iron source into the mixed solution to ensure that the Si/Fe molar ratio is (10-25): 1, and continuously stirring for 24 hours at 40 ℃ to obtain a suspension;
(3) transferring the obtained suspension into a reaction kettle, placing the reaction kettle in an oven, and placing for 24 hours at 100 ℃;
(4) taking the reaction kettle out of the oven, cooling to room temperature, filtering, and washing with deionized water for three times to obtain a catalyst precursor;
(5) and drying the catalyst precursor obtained after filtering and cleaning in an oven at 100 ℃, fully grinding the dried catalyst precursor, and calcining at 550 ℃ for 6 hours to obtain the Fe/SBA-15 catalyst.
The preparation method of the solid Lewis acid catalyst W/SBA-15 comprises the following steps:
(1) weighing 2g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) in 75mL of hydrochloric acid with the concentration of 1.6mol/L, and stirring for 3h at 40 ℃ to obtain a mixed solution;
(2) 4.25g tetraethyl orthosilicate (TEOS) as silicon source and a certain mass of H2WO4Adding the tungsten source into the mixed solution to enable the Si/W molar ratio to be (10-25): 1, and continuously stirring for 24 hours at 40 ℃ to obtain a suspension;
(3) transferring the obtained suspension into a reaction kettle, placing the reaction kettle in an oven, and placing for 24 hours at 100 ℃;
(4) taking the reaction kettle out of the oven, cooling to room temperature, filtering, and washing with deionized water for three times to obtain a catalyst precursor;
(5) and drying the catalyst precursor obtained after filtering and cleaning in an oven at 100 ℃, fully grinding the dried catalyst precursor, and calcining at 550 ℃ for 6 hours to obtain the W/SBA-15 catalyst.
The preparation method of the solid Lewis acid catalyst Sn/SBA-15 comprises the following steps:
(1) weighing 2g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) in 75mL of hydrochloric acid with the concentration of 1.6mol/L, and stirring for 3h at 40 ℃ to obtain a mixed solution;
(2) 4.25g tetraethyl orthosilicate (TEOS) as silicon source and a certain mass of SnCl4Adding the tin source into the mixed solution to enable the Si/Sn molar ratio to be (10-25): 1, and continuously stirring for 24 hours at 40 ℃ to obtain a suspension;
(3) transferring the obtained suspension into a reaction kettle, placing the reaction kettle in an oven, and placing for 24 hours at 100 ℃;
(4) taking the reaction kettle out of the oven, cooling to room temperature, filtering, and washing with deionized water for three times to obtain a catalyst precursor;
(5) and drying the catalyst precursor obtained after filtering and cleaning in an oven at 100 ℃, fully grinding the dried catalyst precursor, and calcining at 550 ℃ for 6 hours to obtain the Sn/SBA-15 catalyst.
The above catalyst can be represented by the general formula M/SBA-15(x), wherein M represents the supported metal species and x in parentheses represents the molar ratio of silicon to metal in the catalyst.
As shown in FIG. 4, it can be seen from the pyridine infrared chart that for Zr/SBA-15(20), the oscillations at 1450 and 1600cm-1 are caused by Lewis acids, while the minor peak at 1540cm-1 is designated as Bronsted acidity. The peak at 1490cm-1 is attributable to mixed Bronsted and Lewis acidity. Based on the area of these peaks, Lewis acidity is the predominant acidic species for the Zr/SBA-15(20) catalyst.
As shown in FIG. 5, all prepared Zr/SBA-15 with different Si/Zr ratios showed significant desorption peaks around 50-150 ℃ which can be attributed to weak acid sites in these catalysts. Broad and low peak signals around 200-450 ℃ were also observed, indicating that a small number of moderately acidic sites were also present in the catalyst, but much lower than the weakly acidic sites.
FIG. 6 is a wide angle XRD characterization of a series of Zr/SBA-15 showing that all catalysts exhibit similar diffraction peaks with broad peaks around 20-30, which is attributable to the amorphous structure of the silica material. In addition, no crystalline Zr oxide diffraction peak was observed, indicating the uniformity of Zr sites in the catalyst.
FIG. 7 is a series of small angle XRD profiles of Zr/SBA-15, in which it can be seen that the Si/Zr ratio of 15-25 exhibits a distinct diffraction peak around 0.9 deg., which can be attributed to the (100) diffraction peak of the 2D hexagonal p6mm structure. Weaker peaks near 1.6 ° and 1.8 ° are assigned to the (110) and (200) diffraction peaks, respectively. When the Si/Zr ratio is 10, the intensity of the (110) and (200) diffraction peaks becomes very weak, probably because the ordered skeleton structure of mesoporous SBA-15 is destroyed by excessive Zr loading.
Furfural, 2-methylfuran and a solid Lewis acid catalyst are uniformly mixed and then added into a closed reactor for catalytic condensation reaction to prepare an aviation kerosene precursor C15 furan trimer.
The conditions of the condensation reaction are as follows: the reaction temperature is 100-150 ℃, the stirring speed is 500-800rpm, the solvent-free reaction is carried out, and the reaction time is 7-16 hours.
The molar ratio of the furfural to the 2-methylfuran is 1: (2-3), and the mass ratio of the furfural to the solid Lewis acid catalyst is (5-20): 1.
A series of solid Lewis acid catalysts prepared below were used to catalyze the condensation reaction of furfural and 2-methylfuran.
Examples 1-7 are presented to illustrate the catalytic effect of a range of solid lewis acid catalysts.
Example 1:
60 mg of Zr/SBA-15(20) (Si/Zr ratio: 20, based on the content of zirconium in furfural: 0.45 mol%), 2.05g of 2-methylfuran, and 0.96 g of furfural (furfural/2-methylfuran: 10: 25) were put into a pressure-resistant tube, and N was added thereto2The reaction product is confirmed to be 5,5' - (furan-2-yl methylene) bis (2-methylfuran) (diesel oil precursor) by nuclear magnetic analysis at 140 ℃ for 15h at a stirring speed of 800rpm under a protective atmosphere. Quantitative analysis by gas chromatography using naphthalene as an internal standard gave a yield of 93.9% of diesel precursor. Zirconium content being zirconium
Example 2:
essentially the same as in example 1, except that: the Si/Zr ratio is 10: Zr/SBA-15(10) of 1 replaces Zr/SBA-15(20) in the example 1, and the detection result shows that the yield of the diesel precursor obtained in the example of the invention is 79.8%.
Example 3:
essentially the same as in example 1, except that: the Si/Zr ratio is 15: Zr/SBA-15(15) of 1 replaces Zr/SBA-15(20) in the example 1, and the detection result shows that the yield of the diesel precursor obtained in the example of the invention is 89.4%.
Example 4:
essentially the same as in example 1, except that: the Si/Zr ratio is 25: Zr/SBA-15(25) of 1 replaces Zr/SBA-15(20) in example 1, and the detection result shows that the yield of the diesel precursor obtained in the example of the invention is 86.6%.
Example 5:
essentially the same as in example 1, except that: as a result of using Fe/SBA-15(20) having an iron metal content of 0.45 mol% instead of Zr/SBA-15(20) in example 1, the yield of the diesel precursor obtained in the example of the present invention was 5.6%.
Example 6:
essentially the same as in example 1, except that: as a result of using Sn/SBA-15(20) having a tin metal content of 0.45 mol% in place of Zr/SBA-15(20) in example 1, the yield of the diesel precursor obtained in the example of the present invention was found to be 17%.
Example 7:
essentially the same as in example 1, except that: as a result of using W/SBA-15(20) having a tungsten metal content of 0.45 mol% instead of Zr/SBA-15(20) in example 1, the yield of the diesel precursor obtained in the example of the present invention was found to be 86.5%.
Examples 8-18 demonstrate the catalytic effect of catalysts of different metal contents.
Example 8:
essentially the same as in example 1, except that: the Si/Zr ratio is 10: 1. zr content 0.226 mol% Zr/SBA-15(10) instead of the Si/Zr ratio in example 1 being 20: 1. the Zr content is 0.45 mol percent of Zr/SBA-15(20), and the detection result shows that the yield of the diesel precursor obtained in the embodiment of the invention is 68.7 percent.
Example 9:
essentially the same as in example 1, except that: the Si/Zr ratio is 15: 1. zr content 0.226 mol% Zr/SBA-15(15) instead of the Si/Zr ratio in example 1 being 20: 1. the Zr content is 0.45 mol percent of Zr/SBA-15(20), and the detection result shows that the yield of the diesel precursor obtained in the embodiment of the invention is 71.4 percent.
Example 10:
essentially the same as in example 1, except that: as a result of examination, when Zr/SBA-15(20) having a Zr content of 0.226 mol% was used in place of Zr/SBA-15(20) having a Zr content of 0.45 mol% in example 1, the yield of the diesel precursor obtained in the example of the present invention was 86.9%.
Example 11:
essentially the same as in example 1, except that: the Si/Zr ratio is 25: 1. zr content 0.226 mol% Zr/SBA-15(25) instead of the Si/Zr ratio in example 1 being 20: 1. the Zr content is 0.45 mol percent of Zr/SBA-15(20), and the detection result shows that the yield of the diesel precursor obtained in the embodiment of the invention is 65.5 percent.
Example 12:
essentially the same as in example 1, except that: the Si/Zr ratio is 10: 1 Zr/SBA-15(10) instead of the Si/Zr ratio in example 1 was 20:1 Zr/SBA-15(20), the detection result shows that the yield of the diesel precursor obtained in the embodiment of the invention is 79.8%.
Example 13:
essentially the same as in example 1, except that: the Si/Zr ratio is 15: Zr/SBA-15(15) of 1 replaces Zr/SBA-15(20) in the example 1, and the detection result shows that the yield of the diesel precursor obtained in the example of the invention is 88.4%.
Example 14:
essentially the same as in example 1, except that: the Si/Zr ratio is 25: Zr/SBA-15(25) of 1 replaces Zr/SBA-15(20) in example 1, and the detection result shows that the yield of the diesel precursor obtained in the example of the invention is 88.6%.
Example 15:
essentially the same as in example 1, except that: the Si/Zr ratio is 10: 1. zr content 0.53 mol% Zr/SBA-15(10) instead of the Si/Zr ratio in example 1 being 20: 1. the Zr content is 0.45 mol percent of Zr/SBA-15(20), and the detection result shows that the yield of the diesel precursor obtained in the embodiment of the invention is 79.3 percent.
Example 16:
essentially the same as in example 1, except that: the Si/Zr ratio is 15: 1. zr content 0.53 mol% Zr/SBA-15(15) instead of the Si/Zr ratio in example 1 being 20: 1. the Zr content is 0.45 mol percent of Zr/SBA-15(20), and the detection result shows that the yield of the diesel precursor obtained in the embodiment of the invention is 84.8 percent.
Example 17:
essentially the same as in example 1, except that: the Si/Zr ratio is 20: 1. zr content 0.53 mol% Zr/SBA-15(20) instead of the Si/Zr ratio in example 1 being 20: 1. the Zr content is 0.45 mol percent of Zr/SBA-15(20), and the detection result shows that the yield of the diesel precursor obtained by the embodiment of the invention is 88.4 percent.
Example 18:
essentially the same as in example 1, except that: the Si/Zr ratio is 25: 1. zr content 0.53 mol% Zr/SBA-15(25) instead of the Si/Zr ratio in example 1 being 20: 1. the Zr content is 0.45 mol percent of Zr/SBA-15(20), and the detection result shows that the yield of the diesel precursor obtained in the embodiment of the invention is 86.5 percent.
Examples 19-21 show the reaction at different temperatures.
Example 19:
essentially the same as in example 1, except that: the yield of the diesel precursor obtained in the inventive example was 69.6%, as measured by replacing 140 ℃ in example 1 with 100 ℃.
Example 20:
essentially the same as in example 1, except that: the yield of the diesel precursor obtained in the inventive example was 84.5%, as measured by replacing 140 ℃ in example 1 with 120 ℃.
Example 21:
essentially the same as in example 1, except that: the yield of the diesel precursor obtained in the inventive example was 89.5%, as measured by replacing 140 ℃ in example 1 with 150 ℃.
Examples 22-25 show the reaction at different reaction times.
Example 22:
essentially the same as in example 1, except that: when 7h was used instead of 15h in example 1, the yield of diesel precursor obtained in the inventive example was 79.2%, as determined.
Example 23:
essentially the same as in example 1, except that: when 10h was used instead of 15h in example 1, the yield of diesel precursor obtained in the inventive example was 89.3%, as determined.
Example 24:
essentially the same as in example 1, except that: when 14h was used instead of 15h in example 1, the yield of diesel precursor obtained in the inventive example was 90.6%, as measured.
Example 25:
essentially the same as in example 1, except that: the yield of the diesel precursor obtained in the inventive example was 87.4%, as measured by replacing 15h in example 1 with 16 h.
Examples 26-30 show the reaction at different furfural/2-methylfuran ratios.
Example 26:
essentially the same as in example 1, except that: the ratio of furfural to 2-methylfuran is 10: 20, that is, the amount of 2-methylfuran was 1.64g instead of 2.05g in example 1, and it was found that the yield of the diesel precursor obtained in the example of the present invention was 76.1%.
Example 27:
essentially the same as in example 1, except that: the ratio of furfural to 2-methylfuran is 10: 22, that is, the amount of 2-methylfuran was 1.8 g instead of 2.05g in example 1, it was found that the yield of the diesel precursor obtained in the example of the present invention was 78.3%.
Example 28:
essentially the same as in example 1, except that: the ratio of furfural to 2-methylfuran is 10: 24, that is, the amount of 2-methylfuran was 1.97g instead of 2.05g in example 1, it was found that the yield of diesel precursor obtained in the example of the present invention was 87.4%.
Example 29:
essentially the same as in example 1, except that: the ratio of furfural to 2-methylfuran is 10: 28, that is, the amount of 2-methylfuran was 2.3g instead of 2.05g in example 1, it was found that the yield of diesel precursor obtained in the example of the present invention was 94.7%.
Example 30:
essentially the same as in example 1, except that: the ratio of furfural to 2-methylfuran is 10: 30, that is, the amount of 2-methylfuran was 2.46g instead of 2.05g in example 1, it was found that the yield of diesel precursor obtained in the example of the present invention was 94.1%.
The above description is not intended to be restrictive, and those skilled in the art will recognize that the invention can be practiced without departing from the spirit and scope of the appended claims.
Claims (6)
1. The preparation method of the aviation kerosene precursor is characterized by comprising the following steps:
uniformly mixing furfural, 2-methylfuran and a solid Lewis acid catalyst, and adding the mixture into a closed reactor to perform catalytic condensation reaction to prepare aviation kerosene precursor C15 furan trimer;
the solid Lewis acid catalyst is selected from one of Zr/SBA-15, Fe/SBA-15, Sn/SBA-15 and W/SBA-15.
2. The method for preparing an aviation kerosene precursor as defined in claim 1, wherein the reaction temperature is 100 ℃ and 150 ℃ and the reaction time is 7-16 hours.
3. The process for preparing an aviation kerosene precursor as claimed in claim 1, wherein no solvent is required in the reaction system.
4. The process for the preparation of an aviation kerosene precursor of claim 1 wherein said molar ratio of furfural to 2-methylfuran is 1: (2-3), and the mass ratio of the furfural to the solid Lewis acid catalyst (5-20) is 1.
5. The method of making an aviation kerosene precursor as defined in claim 1, wherein said method of making a solid lewis acid catalyst Zr/SBA-15 comprises the steps of:
(1) weighing 2g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in 75mL of hydrochloric acid with the concentration of 1.6mol/L, and stirring for 3 hours at 40 ℃ to obtain a mixed solution;
(2) 4.25g of tetraethyl orthosilicate is used as a silicon source and ZrOCl with certain mass2•8H2O is added into the mixed solution as a zirconium sourceStirring at 40 deg.C for 24 hr to obtain suspension, wherein the Si/Zr molar ratio is (10-25): 1;
(3) transferring the obtained suspension into a reaction kettle, placing the reaction kettle in an oven, and placing for 24 hours at 100 ℃;
(4) taking the reaction kettle out of the oven, cooling to room temperature, filtering, and washing with deionized water for three times to obtain a catalyst precursor;
(5) and drying the catalyst precursor obtained after filtering and cleaning in an oven at 100 ℃, fully grinding the dried catalyst precursor, and calcining at 550 ℃ for 6 hours to obtain the Zr/SBA-15 catalyst.
6. A process for the preparation of an aviation kerosene precursor as defined in claim 5, wherein the Si/Zr ratio is made 20: 1.
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