Fused-ring alkane fuel and photocatalytic preparation process thereof

Abstract

A process for preparing a fused-ring alkane fuel, wherein the fused-ring alkane fuel has the following structure: ##STR00001##
wherein n is 1 or 2; R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are H or CH.sub.3 or CH.sub.2CH.sub.3;
the fused-ring alkane fuel has a density of greater than 0.870 g/cm.sup.3, a freezing point of not higher than 50 C., and a net mass heat value of not less than 42.0 MJ/kg; the process for preparing a fused-ring alkane fuel, wherein the process includes steps of: (1) in a presence of ultraviolet light and a photocatalyst, a Diels-Alder cycloaddition reaction between a substituted or unsubstituted cyclic enone and a substituted or unsubstituted furan molecule occurs to produce a fuel precursor molecule: ##STR00002##
(2) the fuel precursor molecule obtained in the step (1) is subjected to hydrodeoxygenation to produce the fused-ring alkane fuel. ##STR00003##

Claims

1. A process for preparing a fused-ring alkane fuel, wherein the fused-ring alkane fuel has the following structure: ##STR00008## wherein n is 1 or 2; R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are H or CH.sub.3 or CH.sub.2CH.sub.3; the fused-ring alkane fuel has a density of greater than 0.870 g/cm.sup.3, a freezing point of not higher than 50 C., and a net mass heat value of not less than 42.0 MJ/kg; and the process for preparing a fused-ring alkane fuel, wherein the process comprises steps of: (1) in a presence of ultraviolet light and a photocatalyst, a Diels-Alder cycloaddition reaction between a substituted or unsubstituted cyclic enone and a substituted or unsubstituted furan molecule occurs to produce a fuel precursor molecule: ##STR00009## (2) the fuel precursor molecule obtained in the step (1) is subjected to hydrodeoxygenation to produce the fused-ring alkane fuel. ##STR00010##

2. The process according to claim 1, wherein the photocatalyst in the step (1) is one or more selected from the group consisting of ZnO/HZSM-5, ZnO/Na-ZSM, ZnO/H, ZnO/HY, ZnO/LaY, Ti-MCM-41, TiO.sub.2/Al.sub.2O.sub.3, TiO.sub.2/SiO.sub.2, TiO.sub.2/MK-10, TiO.sub.2/SBA-15, P25, ZnO/C.sub.3N.sub.4, TiO.sub.2/C.sub.3N.sub.4, ZnO/WO.sub.3, TiO.sub.2/WO.sub.3, C.sub.3N.sub.4, WO.sub.3, and WO.sub.2.72, wherein the photocatalyst is added in an amount of 1% to 20% by weight of reactants; a reaction temperature ranges from 40 C. and 30 C., and a reaction time ranges from 9 h to 24 h.

3. The process according to claim 1, wherein the substituted or unsubstituted cyclic enone in the step (1) is one or more selected from the group consisting of cyclopentenone, 3-methyl-2-cyclopentenone, 4-methyl-2-cyclopentenone, 5-methyl-2-cyclopentenone, 4,4-dimethyl-2-cyclopentenone, 3,4-dimethyl-2-cyclopentenone, 3,5-dimethyl-2-cyclopentenone, 4,5-dimethyl-2-cyclopentenone, 3,4,4-trimethyl-2-cyclopentenone, 3,4,5-trimethyl-2-cyclopentenone, 3 -ethyl-2-cyclopentenone, 4-ethyl-2-cyclopentenone, 5-ethyl-2-cyclopentenone, 4,4-diethyl-2-cyclopentenone, 3,4-diethyl-2-cyclopentenone, 3,5-diethyl-2-cyclopentenone, 4,5-diethyl-2-cyclopentenone, 3,4,4-triethyl-2-cyclopentenone, 3,4,5-triethyl-2-cyclopentenone, cyclohexenone, 2-methyl-2-cyclohexenone, 3-methyl-2-cyclohexenone, 4-methyl-2-cyclohexenone, 5-methyl-2-cyclohexenone, 6-methyl-2-cyclohexenone, 2,3-dimethyl-2-cyclohexenone, 2,4-dimethyl-2-cyclohexenone, 2,5-dimethyl-2-cyclohexenone, 2,6-dimethyl-2-cyclohexenone, 3,4-dimethyl-2-cyclohexenone, 3,5-dimethyl-2-cyclohexenone, 3,6-dimethyl-2-cyclohexenone, 4,5-dimethyl-2-cyclohexenone, 4,6-dimethyl-2-cyclohexenone, 5,6-dimethyl-2-cyclohexenone, 2-ethyl-2-cyclohexenone, 3-ethyl-2-cyclohexenone, 4-ethyl-2-cyclohexenone, 5-ethyl-2-cyclohexenone, 6-ethyl-2-cyclohexenone, 2,3-diethyl-2-cyclohexenone, 2,4-diethyl-2-cyclohexenone, 2,5-diethyl-2-cyclohexenone, 2,6-diethyl-2-cyclohexenone, 3,4-diethyl-2-cyclohexenone, 3,5-diethyl-2-cyclohexenone, 3,6-diethyl-2-cyclohexenone, 4,5-diethyl-2-cyclohexenone, 4,6-diethyl-2-cyclohexenone, 5,6-diethyl-2-cyclohexenone, 2,3,4-trimethyl-2-cyclohexenone, 2,3,5-trimethyl-2-cyclohexenone, 2,3,6-trimethyl-2-cyclohexenone, 3,4,5-trimethyl-2-cyclohexenone, 3,4,6-trimethyl-2-cyclohexenone, 4,5,6-trimethyl-2-cyclohexenone, and 4,5,6-trimethyl-2-cyclohexenone; the substituted or unsubstituted furan is one or more selected from the group consisting of furan, 2-methylfuran, 3-methylfuran, 2,3-dimethylfuran, 2,4-dimethylfuran, 2,5-dimethylfuran, 2-ethylfuran, 3-ethylfuran, 2,3-diethylfuran, 2,4-diethylfuran and 2,5-diethylfuran; wherein the substituted or unsubstituted cyclic enone is not higher than 40 wt % based on a total mass of the substituted or unsubstituted cyclic enone and the substituted or unsubstituted furan.

4. The process according to claim 1, wherein the fuel precursor molecule in the step (2) is hydrodeoxygenated under the following conditions: in a presence of a hydrodeoxygenation catalyst, a reaction temperature of 200 C. to 280 C., a hydrogen gas pressure of 4 MPa to 8 MPa, and a reaction time of 24 h to 48 h.

5. The process according to claim 4, wherein the hydrodeoxygenation catalyst is one or more of copper, nickel, platinum, gold or palladium loaded on one or more of supporters Al.sub.2O.sub.3, SiO.sub.2, HZSM-5, MCM-41, H, SBA-15 or HY; the hydrodeoxygenation catalyst is added in an amount of 1% to 40% by weight of the fuel precursor molecule.

6. The process according to claim 1, wherein the ultraviolet light in the step (1) is a light having a wavelength between 300 nm and 360 nm.

7. The process according to claim 1, wherein the photocatalyst in the step (1) increases a selectivity to a target product of the Diels-Alder cycloaddition reaction between the substituted or unsubstituted cyclic enone and the substituted or unsubstituted furan molecule.

8. The process according to claim 2, wherein the ultraviolet light in the step (1) is a light having a wavelength between 300 nm and 360 nm.

9. The process according to claim 2, wherein the photocatalyst in the step (1) increases a selectivity to a target product of the Diels-Alder cycloaddition reaction between the substituted or unsubstituted cyclic enone and the substituted or unsubstituted furan molecule.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The invention is further illustrated by combining the following examples, and the examples are only illustrative but not limited. Table 1 shows the synthesis reaction of the fuel precursor molecules in Examples 1-30.

(2) TABLE-US-00001 TABLE 1 Fuel Precursor molecule Synthesis Reactions Catalyst Yield of Raw amount fuel Serial Raw materials material (in reactant)/ Reaction Reaction precursor No. (mass ratio) mass/g Catalyst wt % temperature/ C. time/h molecules/% Example 1 30% 20 None 10 10 24 30 cyclopentenone 70% furan Example 2 30% 20 ZnO/HZSM-5 10 10 24 90 cyclopentenone 70% furan Example 3 30% of4,4- 20 ZnO/HZSM-5 5 30 24 80 dimethyl-2- cyclopentenone 70% furan Example 4 20% of 3,4,5- 20 ZnO/HZSM-5 20 30 24 89 trimethyl-2- cyclopentenone 80% furan Example 5 40% 20 ZnO/HY 1 40 20 66 cyclohexenone 60% furan Example 6 30% 2-methyl-2- 20 ZnO/HY 10 10 24 83 cyclohexenone 70% furan Example 7 20% 3,5- 20 ZnO/LaY 10 10 24 82 dimethyl-2- cyclohexenone 80% furan Example 8 10% 2,3,5 - 20 ZnO/LaY 10 25 24 78 trimethyl-2- cyclohexenone 90% furan Example 9 20% of 3-ethyl-2- 20 Ti-MCM-41 10 30 24 86 cyclopentenone 80% furan Example 10 30% of 3-ethyl-2- 20 Ti-MCM-41 20 0 24 88 cyclohexenone 70% 2- methylfuran Example 11 30% of 3-ethyl-2- 20 Ti-MCM-41 10 0 24 82 cyclohexenone 70% 2- methylfuran Example 12 20% 3-Ethyl-2- 20 Ti-MCM-41 20 0 24 90 cyclohexenone 80% 2- methylfuran Example 13 30% 20 TiO.sub.2/SiO.sub.2 10 10 10 85 cyclopentenone 70% 2- methylfuran Example 14 40% of 3-methyl- 20 TiO.sub.2/SiO.sub.2 10 10 9 80 2-cyclopentenone 60% 2- methylfuran Example 15 30% of 4,4- 20 TiO.sub.2/MK-10 10 0 9 86 dimethyl-2- cyclopentenone 70% 2- methylfuran Example 16 30% of 3,4,5- 20 TiO.sub.2/MK-10 10 0 12 90 trimethyl-2- cyclopentenone 70% 2- methylfuran Example 17 20% 20 ZnO/HY 5 15 9 93 cyclohexenone 80% 2,3- dimethylfuran Example 18 30% 3-methyl-2- 20 ZnO/HY 5 15 9 89 cyclohexenone 70% 2,3- dimethylfuran Example 19 30% 3,5- 20 TiO.sub.2/SBA-15 5 0 9 83 dimethyl-2- cyclohexenone 70% 2,4- dimethylfuran Example 20 20% 2,3,5- 20 TiO.sub.2/SBA-15 5 0 12 92 trimethyl-2- cyclohexenone 80% 2-ethylfuran Example 21 40% of 3-ethyl-2- 20 TiO.sub.2/Al.sub.2O.sub.3 5 20 9 84 cyclopentenone 60% 2,3- diethylfuran Example 22 10% 3-ethyl-2- 20 P25 5 20 9 92 cyclohexenone 90% 2,4- diethylfuran Example 23 40% 20 P25 10 40 24 82 cyclohexenone 60% 2,5- diethylfuran Example 24 40% 20 ZnO/Hbeta 10 40 24 85 cyclohexenone 60% 2,5- dimethylfuran Example 25 40% 20 ZnO/Hbeta 10 40 24 88 cyclopentenone 60% 2,5- dimethylfuran Example 26 40% 20 ZnO/Hbeta 10 10 24 90 cyclopentenone 60% 2,5- dimethylfuran Example 27 40% 20 ZnO/C.sub.3N.sub.4 10 10 24 91 cyclopentenone 60% 2,5- dimethylfuran Example 28 40% 20 TiO.sub.2/C.sub.3N.sub.4 10 10 24 85 cyclopentenone 60% 2,5- dimethylfuran Example 29 40% 20 ZnO/WO.sub.3 10 10 24 83 cyclopentenone 60% 2,5- dimethylfuran Example 30 40% 20 TiO.sub.2/WO.sub.3 10 10 24 81 cyclopentenone 60% 2,5- dimethylfuran

(3) The specific reaction steps are exemplified by Example 1 in Table 1: in a 25 mL single-port jacketed glass reactor, 6 g of cyclopentenone and 14 g of furan were added and bubbled with nitrogen gas for 0.5 h whiling being stirring, and then the reactor was sealed; a circulation with 10 C. water started and the reaction mixture was irradiated by a high-pressure mercury lamp for 24 h; the obtained fuel precursor molecules were analyzed by using gas chromatography-mass spectrometry, and the result shows that the yield of the target product, [2+4] cycloaddition fuel precursor molecule A, was 30%, and the others were the by-products of the [2+2] product B of the photochemical reaction of the cyclopentenone per se and the [2+2] product C of the photochemical reaction between the cyclopentenone and the furan; the reaction was described in the following scheme:

(4) ##STR00007##

(5) Example 2 was conducted by adding 2 g of a photocatalyst ZnO/HZSM-5 on the basis of Example 1, and the other reaction conditions were the same as those in Example 1. The results show that the yield of the fuel precursor molecules A was 90%. Clearly, adding the photocatalyst can significantly increase the selectivity to the target product of the Diels-Alder reaction. The reaction conditions and yields of Examples 3-30 were shown in Table 1. As seen from Table 1, the selectivity to the target product, the [2+4] cycloaddition fuel precursor molecules, of the photocatalytic Diels-Alder reaction was greatly improved.

(6) Table 2 shows the reaction conditions and results of Examples 31 to 52 in which the fuel precursor molecules of Examples 1-30 in Table 1 were hydrodeoxygenated to produce the fused-ring alkane fuels (the fuel precursor molecules obtained in Examples 1 and 2 have the same structure; the fuel precursor molecules obtained in Examples 10, 11, and 12 have the same structure; the fuel precursor molecules obtained in Examples 25, 26, 27, 28, 29 and 30 have the same structure).

(7) TABLE-US-00002 TABLE 2 Hydrodeoxygenation Reaction of Fuel Precursor Molecules Reactant (fuel precursor Hydrogen Reaction Reaction Serial No. molecules 20 g) Catalyst (mass) pressure/MPa temperature/ C. time/h Example Example 1 5 g Pd/HY 6 200 24 31 Example Example 3 5 g Pd/H 6 200 24 32 Example Example 4 5 g Pd/HZSM-5 6 200 24 33 Example Example 5 5 g Pt/HZSM-5 6 200 48 34 Example Example 6 5 g Pt/HY 6 200 48 35 Example Example 7 5 g Pt/HY 6 200 48 36 Example Example 8 8 g Ni/HZSM-5 8 250 48 37 Example Example 9 8 g Ni/HY 8 250 48 38 Example Example 10 8 g Ni/H 8 250 48 39 Example Example 13 8 g Cu/HZSM-5 8 280 48 40 Example Example 14 8 g Cu/HY 8 280 48 41 Example Example 15 8 g Cu/H 8 280 48 42 Example Example 16 5 g Au/HZSM-5 4 200 48 43 Example Example 17 5 g Au/HY 4 200 48 44 Example Example 18 5 g Au/H 4 200 24 45 Example Example 19 5 g Pd/SBA-15 6 200 24 46 Example Example 20 5 g Pt/SBA-15 6 200 24 47 Example Example 21 5 g Au/SBA-15 6 200 24 48 Example Example 22 8 g Ni/SiO.sub.2 8 200 48 49 Example Example 23 5 g Pd/HY 6 200 24 50 Example Example 24 5 g Pd/HZSM-5 6 200 24 51 Example Example 25 8 g Ni/HZSM-5 8 250 24 52

(8) The hydrodeoxygenation reaction of the fuel precursor molecules is exemplified by Example 35 of Table 2, and the specific steps are described as follows: a 100 mL autoclave were charged with 20 g of the fuel precursor molecules obtained in Example 6 and 5 g of a catalyst Pd/HZSM-5, sealed, replaced with N.sub.2 for three times, and then charged with 6 MPa of H.sub.2, and the mixture was raised to temperature 200 C. with stirring and reacted for 24 h; the reaction solution was analyzed by using gas chromatography-mass spectrometry, to qualitatively determine the product and calculate the reaction yield; the fuel precursor molecules were fully converted, and the target product of fused ring alkaline fuel molecules has the yield of 91%; the reaction conditions and product yields of the other examples are shown in Table 2.

(9) The fused-ring alkane fuel obtained in Example 35 was measured to have a density of 0.896 g/cm.sup.3, a freezing point of less than 70 C., and a mass heat value of 42.4 MJ/kg. The measurement results of the fused-ring alkane fuels obtained in the other examples are shown in Table 3.

(10) TABLE-US-00003 TABLE 3 Properties of Fused-ring alkane Fuels Obtained in Examples 31-52 Freezing Mass heat value Serial No. Density (g/cm.sup.3) point ( C.) (MJ/kg) Example 31 0.883 52 42.1 Example 32 0.879 60 42.3 Example 33 0.875 60 42.5 Example 34 0.906 57 42.3 Example 35 0.896 <70 42.4 Example 36 0.892 <70 42.5 Example 37 0.890 <70 42.7 Example 38 0.887 <70 42.8 Example 39 0.886 <70 43.1 Example 40 0.880 63 42.3 Example 41 0.876 70 42.4 Example 42 0.876 68 42.4 Example 43 0.872 <70 43.2 Example 44 0.884 68 42.5 Example 45 0.880 <70 42.9 Example 46 0.881 <70 43.0 Example 47 0.876 <70 42.9 Example 48 0.874 <70 43.4 Example 49 0.872 <70 43.5 Example 50 0.872 <70 43.1 Example 51 0.885 60 42.4 Example 52 0.875 <70 42.5

(11) From the above results, it can be seen that a substituted or unsubstituted furan and a substituted or unsubstituted cycloenones may prepare the fused-ring alkane fuels in a high selectivity and a high yield through a heterogeneous photocatalytic Diels-Alder cycloaddition reaction and then through a hydrodeoxygenation reaction. The resultant fused-ring alkane fuels have excellent performances of high density, high heat value, low freezing point, and high thermal stability.