METHOD FOR PREPARING LIQUID FUEL BY USING y- VALEROLACTONE

Abstract

The present invention provides a method for preparing liquid fuel by using -valerolactone, and steps are as follows: placing a phosphoric acid solution and -valerolactone in a reaction tank for reaction at 220-260 C. for 3-12 hours, cooling to room temperature to obtain a liquid fuel. Using the phosphoric acid solution as a catalyst, -valerolactone can be catalytically converted in one step at a mild temperature (220-260 C.) to produce light and heavy oil products with high calorific value, with a total oil yield up to 33.5 wt %. This technique is simple in process flow and convenience to operate, and has industrial application prospects. Compared with other technologies for preparing high-grade oil products by catalytically converting -valerolactone, using the phosphoric acid solution for catalytic conversion has the obvious advantages that no expensive hydrogen needs to be provided externally, the reaction process is simple, and the temperature is mild.

Claims

1. A method for preparing liquid fuel by using -valerolactone, characterized in that, the method comprises steps as follows: placing a phosphoric acid solution and -valerolactone in a reaction tank for reaction at 220-260 C. for 3-12 hours, cooling to room temperature to obtain a liquid fuel.

2. The method for preparing liquid fuel by using -valerolactone according to claim 1, wherein the phosphoric acid solution has a mass concentration of 100%.

3. The method for preparing liquid fuel by using -valerolactone according to claim 1, wherein a mass ratio of -valerolactone to the phosphoric acid solution is 1:(2-100).

4. The method for preparing liquid fuel by using -valerolactone according to claim 1, wherein placing the phosphoric acid solution and -valerolactone in the reaction tank and heating up to 220-260 C. at 5-10 C./min.

5. A method for preparing liquid fuel by using -valerolactone according to claim 1, wherein the method comprises steps as follows: placing -valerolactone and the phosphoric acid solution in the reaction tank for reaction at 220-260 C. for 3-12 hours, after complete reaction, cooling to room temperature to obtain the liquid fuel; preforming rotary evaporation on the liquid fuel cooled in the step (1) to obtain an oil-water mixture and a phosphoric acid mixture, performing oil-water separation on the oil-water mixture to obtain light oil, and the rotary evaporation is performed at a temperature of 240 C., under a pressure of 0.09 MPa; and performing extraction on the phosphoric acid mixture obtained in the step (2) with dichloromethane, distilling a dichloromethane solution obtained after the extraction by a rotary evaporator to obtain dichloromethane and heavy oil, and the rotary evaporator is operated at a temperature of 60 C., under a pressure of 0.09 MPa.

6. The method for preparing liquid fuel by using -valerolactone according to claim 5, wherein the method comprises a step that at normal pressure, the light oil has a boiling point 245 C., and the heavy oil has a boiling point 245 C.

7. A method for preparing liquid fuel by using -valerolactone according to claim 2, wherein the method comprises steps as follows: placing -valerolactone and the phosphoric acid solution in the reaction tank for reaction at 220-260 C. for 3-12 hours, after complete reaction, cooling to room temperature to obtain the liquid fuel; preforming rotary evaporation on the liquid fuel cooled in the step (1) to obtain an oil-water mixture and a phosphoric acid mixture, performing oil-water separation on the oil-water mixture to obtain light oil, and the rotary evaporation is performed at a temperature of 240 C., under a pressure of 0.09 MPa; and performing extraction on the phosphoric acid mixture obtained in the step (2) with dichloromethane, distilling a dichloromethane solution obtained after the extraction by a rotary evaporator to obtain dichloromethane and heavy oil, and the rotary evaporator is operated at a temperature of 60 C., under a pressure of 0.09 MPa.

8. The method for preparing liquid fuel by using -valerolactone according to claim 7, wherein the method comprises a step that at normal pressure, the light oil has a boiling point 245 C., and the heavy oil has a boiling point 245 C.

9. A method for preparing liquid fuel by using -valerolactone according to claim 3, wherein the method comprises steps as follows: placing -valerolactone and the phosphoric acid solution in the reaction tank for reaction at 220-260 C. for 3-12 hours, after complete reaction, cooling to room temperature to obtain the liquid fuel; preforming rotary evaporation on the liquid fuel cooled in the step (1) to obtain an oil-water mixture and a phosphoric acid mixture, performing oil-water separation on the oil-water mixture to obtain light oil, and the rotary evaporation is performed at a temperature of 240 C., under a pressure of 0.09 MPa; and performing extraction on the phosphoric acid mixture obtained in the step (2) with dichloromethane, distilling a dichloromethane solution obtained after the extraction by a rotary evaporator to obtain dichloromethane and heavy oil, and the rotary evaporator is operated at a temperature of 60 C., under a pressure of 0.09 MPa.

10. The method for preparing liquid fuel by using -valerolactone according to claim 9, wherein the method comprises a step that at normal pressure, the light oil has a boiling point 245 C., and the heavy oil has a boiling point 245 C.

11. A method for preparing liquid fuel by using -valerolactone according to claim 4, wherein the method comprises steps as follows: placing -valerolactone and the phosphoric acid solution in the reaction tank for reaction at 220-260 C. for 3-12 hours, after complete reaction, cooling to room temperature to obtain the liquid fuel; preforming rotary evaporation on the liquid fuel cooled in the step (1) to obtain an oil-water mixture and a phosphoric acid mixture, performing oil-water separation on the oil-water mixture to obtain light oil, and the rotary evaporation is performed at a temperature of 240 C., under a pressure of 0.09 MPa; and performing extraction on the phosphoric acid mixture obtained in the step (2) with dichloromethane, distilling a dichloromethane solution obtained after the extraction by a rotary evaporator to obtain dichloromethane and heavy oil, and the rotary evaporator is operated at a temperature of 60 C., under a pressure of 0.09 MPa.

12. The method for preparing liquid fuel by using -valerolactone according to claim 11, wherein the method comprises a step that at normal pressure, the light oil has a boiling point 245 C., and the heavy oil has a boiling point 245 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG. 1 is a process flow chart for the present invention.

[0022] FIG. 2 is a gas chromatography-mass spectrometry analysis product for light oil in Example 1.

[0023] FIG. 3 is infrared spectra of light oil and heavy oil in Example 1.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Example 1

[0024] The specific steps of the present example using phosphoric acid to convert poly-3-hydroxybutyrate to prepare liquid fuel are as follows (see FIG. 1 for the flow chart):

[0025] (1) 15 g of -valerolactone and 60 mL of a phosphoric acid solution (112.2 g) were taken and placed in a 100 mL para-polyphenyl reaction tank. The temperature was programmed to rise to 240 C. at 5 C./min, and maintained at a constant temperature of 240 C. for 6 hours. After the reaction, it was rapidly cooled to room temperature with cold water. It was found by high-performance liquid chromatography that -valerolactone was completely converted basically, 49% of the oxygen in -valerolactane was removed in form of carbon dioxide, and some oxygen was removed in form of water and carbon monoxide;

[0026] (2) rotary evaporation was performed on the product after the reaction of the step (1) at a condition of 240 C. and 0.09 Mpa to obtain an oil-water mixture and a phosphoric acid mixture, and the oil-water mixture was separated by a separating funnel to obtain light oil with a yield of 24.8 wt %; and

[0027] (3) extraction was perforated on the evaporated phosphoric acid mixture obtained in the step (2) with dichloromethane, and the extracted dichloromethane solution was subjected to rotary distillation under a condition of 60 C. and 0.09 Mpa to recover dichloromethane and to obtain heavy oil with a yield of 8.7%.

[0028] Yields, C, H element distribution and calorific values of the hydrogen oil and heavy oil Obtained in the present example are shown in Table 1.

TABLE-US-00001 TABLE 1 Yields, C, H element distribution and calorific values of light oil and heavy oil Element distribution Calorific value Yield (wt %) C (wt %) H (wt %) (MJ/kg) Light oil 24.8 88.0 8.9 42.4 Heavy oil 8.7 85.7 9.5 41.6 Commercial 80.4 12.3 41.8 oxygenated gasoline

[0029] FIG. 2 is molecular structural formulas of main products identified by gas chromatography-mass spectrometry analysis of the prepared light oil product. As can be seen from FIG. 2, the main products are a low molecular unsaturated benzene ring compounds and cycloalkane compounds.

[0030] These main products shown in FIG. 2 were further verified by infrared spectroscopy analysis of the light oil product in FIG. 3. It can be seen from FIG. 3 that the light oil product contains a CH vibration peak (2800-3100 cm.sup.1) including methyl, methylene and methine, and an aromatic ring functional group (1600 cm .sup.1, 1460 cm.sup.1); and there is no obvious vibration peak at 3200-3670 cm .sup.1, indicating that there are almost no hydroxyl and carboxyl functional groups in the oil product, and -valerolactone is successfully decarboxylated. There is a small vibrational peak at 1780 cm.sup.1, indicating that the oil product contains a small amount of ketone compound, which is consistent with the result of the GCMS analysis in FIG. 2. In addition, the infrared spectrum of the heavy oil is basically similar to that of the light oil, indicating that the main components in the heavy oil also include CH functional groups including methyl, methylene and methine, and aromatic functional groups.

Example 2

[0031] 15 g of -valerolactone and 15 mL of a phosphoric acid solution (28 g) were taken and placed in a 100 mL para-polyphenyl reaction tank. The temperature was programmed to rise to 260 C. and maintained at a constant temperature of 260 C. for 6 hours. After the reaction, it was cooled to room temperature. Light oil was obtained by rotary evaporation, and heavy oil was obtained by extraction using dichloromethane and distillation.

Example 3

[0032] 1 g of -valerolactone and 50 mL of a phosphoric acid solution (93.7 g) were taken and placed in a 100 mL para-polyphenyl reaction tank. The temperature was programmed to rise to 220 C. at 8 C./min and maintained at a constant temperature of 220 C. for 12 hours. After the reaction, it was cooled to room temperature. Light oil was obtained by rotary evaporation, and heavy oil was obtained by extraction using dichloromethane and distillation.

Example 4

[0033] 10 g of -valerolactone and 60 mL of a phosphoric acid solution were taken and placed in a para-polyphenyl reaction tank. The temperature was programmed to rise to 250 C. at 10 C./min and maintained at a constant temperature of 250 C. for 3 hours. After the reaction, it was cooled to room temperature. Light oil was obtained by rotary evaporation, and heavy oil was obtained by extraction using dichloromethane and distillation.

Example 5

[0034] 1 g of -valerolactone and 1.07 mL of a phosphoric acid solution with a mass concentration of 100% (2 g) were placed in a 20 mL para-polyphenyl reaction tank. The temperature was programmed to rise to 260 C. at 10 C./min and was maintained for 5 hours. After the reaction, it was cooled to room temperature. Light oil was obtained by rotary evaporation, and heavy oil was obtained by extraction using dichloromethane and distillation.

Example 6

[0035] 1 g of -valerolactone and 53.4 mL of a phosphoric acid solution with a mass concentration of 100% (100 g) were placed in a para-polyphenyl reaction tank. The temperature was programmed to rise to 230 C. at 5 C./min and was maintained for 8 hours. After the reaction, it was cooled to room temperature. Light oil was obtained by rotary evaporation, and heavy oil was obtained by extraction using dichloromethane and distillation.

Example 7

[0036] 1 g of -valerolactone and 26.7 mL of a phosphoric acid solution with a mass concentration of 100% (50 g) were placed in a para-polyphenyl reaction tank. The temperature was programmed to rise to 260 C. at 10 C./min and maintained for 5 hours. After the reaction, it was cooled to room temperature. Light oil was obtained by rotary evaporation, and heavy oil was obtained by extraction using dichloromethane and distillation.