ULTRASONIC OXIDATIVE DESULFURIZATION METHOD FOR GASOLINE OR DIESEL
20240425766 · 2024-12-26
Inventors
Cpc classification
C10G27/12
CHEMISTRY; METALLURGY
C10G2300/104
CHEMISTRY; METALLURGY
International classification
Abstract
The present application refers to an ultrasonic oxidative desulfurization method for gasoline or diesel, comprising: Step 1, mixing an oxidant solution with an organic acid catalyst solution to obtain a mixture solution, wherein the oxidant reacts with the organic acid catalyst to obtain a peroxy acid; Step 2, mixing the mixture solution with gasoline or diesel and heating to 50 to 70 C., and performing an ultrasonic oxidative reaction under ultrasonic waves at 15 to 25 kHz to obtain a pre-prepared oil; wherein a mass flow ratio of the oxidant solution, the organic acid catalyst solution and the gasoline or diesel is (0.03-0.08):(0.01-0.03):1; Step 3, performing a phase separation process to the pre-prepared oil; and Step 4, recycling the organic acid catalyst and performing a countercurrent extraction for the gasoline or diesel to obtain a desulfurized gasoline or diesel.
Claims
1. An ultrasonic oxidative desulfurization method for gasoline or diesel, comprising: Step 1, mixing an oxidant solution with an organic acid catalyst solution to obtain a mixture solution, wherein an oxidant of the oxidant solution reacts with an organic acid catalyst of the organic acid catalyst solution to obtain a peroxy acid; Step 2, mixing the mixture solution with the gasoline or the diesel and heating to 50 to 70 C., and performing an ultrasonic oxidative reaction under ultrasonic waves at 15 to 25 kHz to obtain a pre-prepared oil; wherein a mass flow ratio of the oxidant solution, the organic acid catalyst solution and the gasoline or diesel is (0.03-0.08):(0.01-0.03):1; Step 3, performing a phase separation process to the pre-prepared oil, wherein an upper layer is gasoline or diesel containing sulfone and sulfoxide, and a lower layer is an aqueous phase containing the organic acid catalyst; and Step 4, recycling the organic acid catalyst and performing a countercurrent extraction for the gasoline or the diesel to obtain a desulfurized gasoline or a desulfurized diesel.
2. The ultrasonic oxidative desulfurization method for gasoline or diesel according to claim 1, wherein a method for recycling the organic acid catalyst comprises: drying and dehydrating the aqueous phase containing the organic acid catalyst by a desiccant to obtain a dehydrated organic acid catalyst, and formulating the dehydrated organic acid catalyst into a solution and conveying the solution into the mixture solution in Step 1.
3. The ultrasonic oxidative desulfurization method for gasoline or diesel according to claim 2, wherein the desiccant is passed through a saturated steam at 170 to 190 C. and 0.5 to 2 MPa, and the desiccant is heated to 150 to 170 C. for the drying and dehydrating, and a dehydrated desiccant is conveyed into the aqueous phase containing the organic acid catalyst.
4. The ultrasonic oxidative desulfurization method for gasoline or diesel according to claim 1, further comprising a post-treatment step for the desulfurized gasoline or the desulfurized diesel: performing a desolvent treatment for the desulfurized gasoline or the desulfurized diesel at a condition of 90 to 110 C. and 0.5 to 1.5 kPa, to obtain a desolvated and desulfurized gasoline or a desolvated and desulfurized diesel.
5. The ultrasonic oxidative desulfurization method for gasoline or diesel according to claim 1, further comprising a step of recycling an extractant from a sulfone-containing waste solvent generated from the countercurrent extraction.
6. The ultrasonic oxidative desulfurization method for gasoline or diesel according to claim 5, wherein the recycling an extractant comprises the following steps: dehydrating the sulfone-containing waste solvent at 110 to 130 C. and 8 to 12 kPaA to obtain circulating water and a dehydrated sulfone-containing waste solvent; recycling solvent from the dehydrated sulfone-containing waste solvent at 90 to 120 C. and 1 to 5 kPaA to obtain circulating solvent; and mixing the circulating water with the circulating solvent to obtain the extractant, wherein the extractant is conveyed into a step of the countercurrent extraction for the gasoline or the diesel.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0042]
DETAILED DESCRIPTION
[0043] The present application is further described in detail below in combination with
[0044] An embodiment of the present application discloses an ultrasonic oxidative desulfurization system for gasoline or diesel. Referring to
[0045] The pipeline mixer 1 is in communication with the inlet of the ultrasonic reactor 3 by pipelines, and pipelines between the pipeline mixer 1 and the ultrasonic reactor 3 is provided with a gasoline or diesel feed pump 2.
[0046] The gasoline or diesel heater 21 is connected to the pipelines between the ultrasonic reactor 3 and the gasoline or diesel feed pump 2, and the gasoline or diesel heater 21 is configured to heat the mixture of gasoline or diesel and peroxy acid to 50 to 70 C. to obtain pre-prepared oil.
[0047] The phase separation tank 4 is configured to perform phase separation treatment for the pre-prepared oil, and the phase separation tank 4 is provided with an inlet, a light-phase outlet, and a heavy-phase outlet. The inlet of the phase separation tank 4 is in communication with the outlet of the ultrasonic reactor 3 by pipelines. The heavy-phase outlet of the phase separation tank 4 is in communication with an inlet of a catalyst dehydrator 41 by pipelines, the catalyst dehydrator is filled with a desiccant, and the desiccant in this embodiment of the present application is anhydrous magnesium sulfate in 80 to 100 mesh. An outlet of the catalyst dehydrator 41 is in communication with a catalyst circulation pump 121 by pipelines, and an outlet of the catalyst circulation pump 121 is in communication with an inlet of the catalyst pump 12 by pipelines.
[0048] The extraction tower 5 is provided with a first outlet and a second inlet located at the top of the extraction tower 5, and a second outlet and a first inlet located at the bottom of the extraction tower 5. The light-phase outlet of the phase separation tank 4 is in communication with the first inlet of the extraction tower 5 by pipelines. The first outlet of the extraction tower 5 is in communication with a desolvation tower 6 by pipelines, and the desolvation tower 6 is configured to remove solvent from the desulfurized gasoline or diesel.
[0049] The desulfurization system further includes a recovery unit 7 for recycling the extractant. The recovery unit includes a waste solvent tank 71, a solvent dehydration tower 72 and a solvent recovery tower 73. The waste solvent tank 71 is in communication with the second outlet of the extraction tower 5 by pipelines. The solvent dehydration tower 72 is provided with an first inlet, a first steam outlet and an first outlet, and the solvent recovery tower 73 is also provided with an second inlet, a second steam outlet and an second outlet. The first inlet of the solvent dehydration tower 72 is in communication with the waste solvent tank 71 by pipelines, the second inlet of the solvent recovery tower 73 is in communication with the first outlet of the solvent dehydration tower 72 by pipelines, and the first steam outlet of the solvent dehydration tower 72 and the second steam outlet of the solvent recovery tower 73 are both in communication with the second inlet of the extraction tower 5 by pipelines.
[0050] The bottom of the solvent recovery tower 73 is in communication with an extraction oil desolvation tower 9 by pipelines. The extraction oil is usually recovered at the bottom of the solvent recovery tower 73, and the extraction oil is conveyed to the extraction oil desolvation tower 9, so as to extract and remove the residual solvent in the extraction oil. After removing the solvent, the extraction oil can be recovered as a by-product, to enhance the efficiency of industrial production.
[0051] The solvent recovery tower 73 is in communication with a tail gas combustion system 8 by pipelines, the solvent gas in the vacuum system will be dissolved in water, the small amount of non-condensable gas in the gasoline or diesel is not easy to be dissolved in water, and the non-condensable gas contains methane and other harmful gases or flammable and explosive gases. The above gases are treated by the tail gas combustion system 8 before emission, so as to ensure the safety of production and reduce the pollution to the environment.
1. EXAMPLE
[0052] Examples 1 to 7 relate to ultrasonic oxidative desulfurization for diesel.
Example 1
[0053] The ultrasonic oxidative desulfurization method for diesel in this Example is as follows.
[0054] The hydrogen peroxide solution (with a mass fraction of 30%) was conveyed to the pipeline mixer 1 through the oxidant pump, at the same time, the formic acid catalyst solution (with a mass fraction of 85%) was conveyed to the pipeline mixer 1 through the catalyst pump, and the diesel was conveyed to the pipeline of the desulfurization system through the gasoline or diesel feed pump 2. In particular, the flow rate of the diesel was 60 kg/h, the flow rate of the hydrogen peroxide solution was 1.8 kg/h, and the flow rate of the formic acid catalyst solution was 0.6 kg/h.
[0055] The hydrogen peroxide solution and the formic acid catalyst solution reacted to generate peroxy acid, the peroxy acid and the diesel were mixed and then heated to 55 C. by the gasoline or diesel heater 21, and then the peroxy acid and the diesel were conveyed to the ultrasonic reactor 3. The ultrasonic frequency in the ultrasonic reactor 3 was 20 kHz. The peroxy acid and the diesel were ultrasonic oxidized to produce the pre-prepared oil and the aqueous phase containing the organic acid catalyst.
[0056] The pre-prepared oil and the aqueous phase containing the organic acid catalyst were conveyed to the phase separation tank 4 for phase separation treatment. The aqueous phase containing the organic acid catalyst was conveyed to the catalyst dehydrator 41 to be dried and dehydrated by anhydrous magnesium sulfate in 100 mesh, and the dehydrated organic acid catalyst was conveyed to the feed pipeline of the catalyst by the catalyst circulation pump 121, so as to achieve the recycling.
[0057] The magnesium sulfate saturated with water was placed in saturated steam at 180 C. and 1 MPa, and the magnesium sulfate was heated to 160 C. for being dried and dehydrated to obtain anhydrous magnesium sulfate, and the anhydrous magnesium sulfate was re-conveyed to the aqueous phase containing the organic acid catalyst, so as to achieve the recycling of the anhydrous magnesium sulfate.
[0058] The extractant was a NMP aqueous solution, and the extractant entered into the extraction tower 5 through the second inlet at the top of the extraction tower 5, and the diesel containing sulfone and sulfoxide entered into the extraction tower 5 through the first inlet at the bottom of the extraction tower 5 to perform the countercurrent extraction to the diesel containing sulfone and sulfoxide, so as to obtain desulfurized diesel. The desulfurized diesel was then conveyed to the desolvation tower 6 with a temperature of 100 C. and a pressure of 1 kPaA for desolvation to obtain the desolvated desulfurized diesel.
[0059] The sulfone-containing waste solvent which was conveyed out of the second outlet of the extraction tower 5 was conveyed to the waste solvent tank 71, and then conveyed to the solvent dehydration tower 72 for being dehydrated so as to obtain the circulating water. The solvent dehydration tower 72 had a temperature of 120 C. and a pressure of 10 kPaA. The dehydrated sulfone-containing waste solvent was conveyed to the solvent recovery tower 73 to obtain the circulating solvent. The solvent recovery tower 73 had a temperature of 110 C. and a pressure of 3 kPaA. The circulating water and the circulating solvent were mixed to from the extractant, then the extractant was conveyed to the solvent recovery tower 73 and heat exchanged to 70 C. with the solvent steam, and then the extractant was re-conveyed to the extraction tower 5, so as to achieve the recycling of the extractant.
[0060] The non-condensable gas generated in the solvent recovery tower 73 was conveyed to the tail gas combustion system 8 for the tail gas treatment; and the extraction oil recovered from the bottom of the solvent recovery tower 73 was conveyed to the extraction oil desolvation tower 9 having a temperature of 130 C. and a pressure of 1 kPaA, so as to obtain the extraction oil as a by-product.
Example 2
[0061] The ultrasonic oxidative desulfurization method for diesel of this example differs from Example 1 in that the flow rate of the hydrogen peroxide solution was 3 kg/h and the flow rate of the formic acid catalyst solution was 1.2 kg/h.
Example 3
[0062] The ultrasonic oxidative desulfurization method for diesel of this example differs from Example 1 in that the flow rate of the hydrogen peroxide solution was 4.8 kg/h and the flow rate of the formic acid catalyst solution was 1.8 kg/h.
Example 4
[0063] The ultrasonic oxidative desulfurization method for diesel of this example differs form Example 2 in that the temperature was 110 C. and the pressure was 8 kPaA in the solvent dehydration tower 72.
Example 5
[0064] The ultrasonic oxidative desulfurization method for diesel of this example differs form Example 2 in that the temperature was 130 C. and the pressure was 12 kPaA in the solvent dehydration tower 72.
Example 6
[0065] The ultrasonic oxidative desulfurization method for diesel of this example differs from Example 2 in that the temperature was 90 C. and the pressure was 1 kPaA in the solvent recovery tower 73.
Example 7
[0066] The ultrasonic oxidative desulfurization method for diesel of this example differs from Example 2 in that the temperature was 120 C. and the pressure was 5 kPaA in the solvent recovery tower 73.
[0067] Example 8 to 14 relate to ultrasonic oxidative desulfurization for gasoline.
Example 8
[0068] The ultrasonic oxidative desulfurization method for gasoline in this Example is as follows.
[0069] The hydrogen peroxide solution (with a mass fraction of 30%) was conveyed to the pipeline mixer 1 through the oxidant pump, at the same time, the formic acid catalyst solution (with a mass fraction of 85%) was conveyed to the pipeline mixer 1 through the catalyst pump, and the gasoline was conveyed to the pipeline of the desulfurization system through the gasoline or diesel feed pump 2. In particular, the flow rate of the gasoline was 60 kg/h, the flow rate of the hydrogen peroxide solution was 1.8 kg/h, and the flow rate of the formic acid catalyst solution was 0.6 kg/h.
[0070] The hydrogen peroxide solution and the formic acid catalyst solution reacted to generate peroxy acid, the peroxy acid and the gasoline were mixed and then heated to 55 C. by the gasoline or diesel heater 21, and then the peroxy acid and the gasoline were conveyed to the ultrasonic reactor 3. The ultrasonic frequency in the ultrasonic reactor 3 was 20 kHz. The peroxy acid and the gasoline were ultrasonic oxidized to produce the pre-prepared oil and the aqueous phase containing the organic acid catalyst.
[0071] The pre-prepared oil and the aqueous phase containing the organic acid catalyst were conveyed to the phase separation tank 4 for phase separation treatment. The aqueous phase containing the organic acid catalyst was conveyed to the catalyst dehydrator 41 to be dried and dehydrated by anhydrous magnesium sulfate in 100 mesh, and the dehydrated organic acid catalyst was conveyed to the feed pipeline of the catalyst by the catalyst circulation pump 121, so as to achieve the recycling.
[0072] The magnesium sulfate saturated with water was placed in saturated steam at 180 C. and 1 MPa, and the magnesium sulfate was heated to 160 C. for being dried and dehydrated to obtain anhydrous magnesium sulfate, and the anhydrous magnesium sulfate was re-conveyed to the aqueous phase containing the organic acid catalyst, so as to achieve the recycling of the anhydrous magnesium sulfate.
[0073] The extractant was a NMP aqueous solution, and the extractant entered into the extraction tower 5 through the second inlet at the top of the extraction tower 5, and the gasoline containing sulfone and sulfoxide entered into the extraction tower 5 through the first inlet at the bottom of the extraction tower 5 to perform the countercurrent extraction to the gasoline containing sulfone and sulfoxide, so as to obtain desulfurized gasoline. The desulfurized gasoline was then conveyed to the desolvation tower 6 with a temperature of 100 C. and a pressure of 1 kPaA for desolvation to obtain the desolvated desulfurized gasoline.
[0074] The sulfone-containing waste solvent which was conveyed out of the second outlet of the extraction tower 5 was conveyed to the waste solvent tank 71, and then conveyed to the solvent dehydration tower 72 for being dehydrated so as to obtain the circulating water. The solvent dehydration tower 72 had a temperature of 120 C. and a pressure of 10 kPaA. The dehydrated sulfone-containing waste solvent was conveyed to the solvent recovery tower 73 to obtain the circulating solvent. The solvent recovery tower 73 had a temperature of 110 C. and a pressure of 3 kPaA. The circulating water and the circulating solvent were mixed to from the extractant, then the extractant was conveyed to the solvent recovery tower 73 and heat exchanged to 70 C. with the solvent steam, and then the extractant was re-conveyed to the extraction tower 5, so as to achieve the recycling of the extractant.
Example 9
[0075] The ultrasonic oxidative desulfurization method for gasoline of this example differs from Example 8 in that the flow rate of the hydrogen peroxide solution was 3 kg/h and the flow rate of the formic acid catalyst solution was 1.2 kg/h.
Example 10
[0076] The ultrasonic oxidative desulfurization method for gasoline of this example differs from Example 8 in that the flow rate of the hydrogen peroxide solution was 4.8 kg/h and the flow rate of the formic acid catalyst solution was 1.8 kg/h.
Example 11
[0077] The ultrasonic oxidative desulfurization method for gasoline of this example differs form Example 9 in that the temperature was 110 C. and the pressure was 8 kPaA in the solvent dehydration tower 72.
Example 12
[0078] The ultrasonic oxidative desulfurization method for gasoline of this example differs form Example 9 in that the temperature was 130 C. and the pressure was 12 kPaA in the solvent dehydration tower 72.
Example 13
[0079] The ultrasonic oxidative desulfurization method for gasoline of this example differs from Example 9 in that the temperature was 90 C. and the pressure was 1 kPaA in the solvent recovery tower 73.
Example 14
[0080] The ultrasonic oxidative desulfurization method for gasoline of this example differs from Example 9 in that the temperature was 120 C. and the pressure was 5 kPaA in the solvent recovery tower 73.
2. PERFORMANCE TESTING
[0081] (1) The desolvated desulfurized diesel prepared in accordance with the preparation method in Examples 1 to 7 and the desolvated desulfurized gasoline prepared in accordance with the preparation method in Examples 8 to 14 were tested in accordance with the GB/T11140-2008 Standard test method for sulfur in petroleum products by wavelength dispersive X-ray fluorescence spectrometry, and the sulfur content of the desolvated desulfurized diesel and the desolvated desulfurized gasoline were tested respectively, and the sulfur content was measured in ppm (parts per million). [0082] (2) Equal amounts of aqueous phase containing the organic acid catalyst were collected at the heavy-phase outlet of the phase separation tanks of the desolvated desulfurized diesel in Examples 1 to 7 and the desolvated desulfurized gasoline in Examples 8 to 14 respectively, and then the content of the peroxy acid in the aqueous phase containing the organic acid catalyst was determined by the iodometry.
[0083] The results of the above performance tests are shown in Table 1 and Table 2.
TABLE-US-00001 TABLE 1 The results of the performance test of the desolvated desulfurized diesel in Examples 1 to 7 The sulfur content of the The content of peroxy acid in desolvated desulfurized aqueous phase containing the Test items diesel (ppm) organic acid catalyst (%) Example 1 12 0.29 Example 2 6 0.83 Example 3 6 2.30 Example 4 8 0.85 Example 5 7 0.84 Example 6 9 0.82 Example 7 8 0.9
TABLE-US-00002 TABLE 2 The results of the performance test of the desolvated desulfurized gasoline in Examples 8 to 14 The sulfur content of the The content of peroxy acid in desolvated desulfurized aqueous phase containing the Test items gasoline (ppm) organic acid catalyst (%) Example 8 11 0.32 Example 9 5 0.76 Example 10 5 2.55 Example 11 7 0.82 Example 12 7 0.79 Example 13 9 0.82 Example 14 8 0.84
3. ANALYSIS AND SUMMARY OF RESULTS
[0084] Combining Examples 1 to 14 with Table 1 and Table 2, it can be seen that the sulfur content of the desolvated desulfurized diesel prepared in Example 1 and the desolvated desulfurized gasoline prepared in Example 8 were 12 ppm and 11 ppm, respectively, the sulfur content of the desolvated desulfurized diesel prepared in Examples 2 and 3 were 6 ppm and 6 ppm, respectively, and the sulfur content of the desolvated desulfurized gasoline prepared in Example 9 and Example 10 were 5 ppm and 5 ppm, respectively. And it can be known from the above that the sulfur content of the desolvated desulfurized diesel obtained in Example 2 and Example 3 was much lower than that of Example 1, and the sulfur content of the desolvated desulfurized gasoline obtained in Example 9 and Example 10 was much lower than that of Example 8.
[0085] The contents of peroxy acid in the aqueous phase containing the organic acid catalyst in the process of preparing the desolvated desulfurized diesel in Examples 3 and the desolvated desulfurized gasoline in Example 10 were 2.3% and 2.55%, respectively, and the contents of peroxy acid in the aqueous phase containing the organic acid catalyst in the process of preparing the desolvated desulfurized diesel in Example 2 and the desolvated desulfurized gasoline in Example 9 were 0.83% and 0.76%, respectively.
[0086] It can be known from the above that the content of peroxy acid generated in the process of preparing the desolvated desulfurized diesel in Example 3 was higher than that of Example 2, and the content of peroxy acid generated in the process of preparing the desolvated desulfurized gasoline in Example 10 was higher than that of Example 9. Therefore, although Examples 2 to 3 and Examples 9 to 10 all reduced the sulfur content in the desolvated desulfurized diesel and the desolvated desulfurized gasoline, a greater amount of peroxy acid remained in both Examples 3 and Example 10, that is to say, the wasted oxidant is more, and difficulty of recycling the organic acid catalyst in both Example 3 and Example 10 was increased.
[0087] In summary, the mass flow ratios of the oxidant solution, the organic acid catalyst solution and the gasoline or diesel in Example 2 and Example 9 can enhance the effect of oxidative desulfurization of the gasoline or diesel, while reducing the degree of waste of the oxidant and the difficulty of recycling the organic acid catalyst.
[0088] The temperature parameters and pressure parameters in the solvent dehydration tower and the temperature parameters and pressure parameters in the solvent recovery tower in Examples 4 to 7 were different from those in Example 2, and the temperature parameters and pressure parameters in the solvent dehydration tower and the temperature parameters and pressure parameters in the solvent recovery tower in Examples 11 to 14 were different from those in Example 9. It can be known from Table 1, the sulfur contents in the desolvated desulfurized diesel and the desolvated desulfurized gasoline prepared in Examples 4 to 7 were all higher than that of Example 2, and the sulfur contents in the desolvated desulfurized diesel and the desolvated desulfurized gasoline prepared in Examples 11 to 14 were all higher than that of Example 9. Therefore, the desulfurization effect on the gasoline or diesel in Examples 4 to 7 was worse than that of Example 2, and the desulfurization effect on the gasoline or diesel in Examples 11 to 14 was worse than that of Example 9.
[0089] It can be known from the above that, in Example 2 and Example 9, the temperature parameters were both 120 C. and the pressure parameters were both 10 kPaA in the solvent dehydration tower, and the temperature parameters were both 110 C. and the pressure parameters were both 3 kPaA in the solvent dehydration tower. The above parameters can make the extractant in the sulfone-containing waste solvent be more efficiently recycled back to the extraction tower, so as to make the content of the extractant be sufficient in the extractor tower, and to extract and separate the sulfone in the gasoline or diesel conveyed to the extraction tower more sufficiently and thoroughly, which enhances the desulfurization effect of the gasoline or diesel.
[0090] The above are the preferred embodiments of the present application, which are not intended to limit the protection scope of the present application. Therefore, all equivalent changes made according to the structure, shape and principle of the present application should be covered within the protection scope of the present application.
LISTING OF REFERENCE SIGNS
[0091] 1. pipeline mixer; [0092] 11. oxidant pump; [0093] 12. catalyst pump; [0094] 121. catalyst circulation pump; [0095] 2. gasoline or diesel feed pump; [0096] 21. gasoline or diesel heater; [0097] 3. ultrasonic reactor; [0098] 4. phase separation tank; [0099] 41. catalyst dehydrator; [0100] 5. extraction tower; [0101] 6. desolvation tower; [0102] 7. recovery unit; [0103] 71. waste solvent tank; [0104] 72. solvent dehydration tower; [0105] 73. solvent recovery tower; [0106] 8. tail gas combustion system; [0107] 9. extraction oil desolvation tower.