Phosphomolybdenum blue reaction type extraction agent and preparation method and application thereof

Abstract

The invention relates to the technical field of extraction, in particular to a phosphomolybdenum blue reactive extractant and a preparation method and application thereof. The preparation method of the phosphomolybdenum blue reaction type extraction agent comprises the following steps: mixing phosphomolybdic acid and a reducing agent, and reacting at 50-150 DEG C; the reducing agent comprises ethylene glycol and / or polyethylene glycol. The phosphomolybdenum blue reaction type extractant has the advantages that the preparation method is simple, the atom utilization rate is high, the extractant is environmentally friendly, the desulfurization rate is high when the extractant is used for diesel extraction-oxidation coupling ultra-deep desulfurization, the reaction system is simple, the reaction condition is mild, oil phase separation is convenient after reaction, and the oxidation product sulfone can be recycled.

Description

Technical Field

[0001] The invention relates to the field of extraction technology, in particular to a phosphomolybdenum blue reactive extractant and a preparation method and application thereof. Background Art

[0002] In recent years, with the proposal of the "dual carbon" strategic goal, diesel utilization has gradually transformed and upgraded to be cleaner, more refined and more valuable. However, the presence of sulfides can lead to equipment corrosion, metal catalyst poisoning, reduced production efficiency, increased energy consumption and carbon emissions. In addition, the combustion of high-sulfur diesel will emit a large amount of sulfur oxides (SO x ), leading to a series of environmental problems such as haze and acid rain, which seriously endanger the ecological environment and human health. Therefore, efficient removal of sulfur compounds in diesel and clean utilization of diesel are of great significance to the sustainable development of human society. The commonly used hydrodesulfurization technology in industry requires more stringent reaction conditions when removing aromatic sulfides from diesel, resulting in high energy consumption, high hydrogen consumption and high carbon emissions, and its products are toxic and harmful H 2 S gas, which hinders the clean, refined and high-value utilization of diesel. Extraction-oxidation coupled desulfurization has the advantages of both extraction desulfurization and oxidation desulfurization, and is a typical non-hydrogenation desulfurization technology. Its principle is to first extract sulfides to the reactive extractant phase, and then catalytically oxidize the sulfides to the corresponding sulfone substances through the oxidant to increase the polarity, avoid oil oxidation, and separate and recover high value-added products. Therefore, the development of reactive extractants with both extraction and catalytic properties is the focus of current research.

[0003] Polyoxometalates (POMs) are nanoscale metal-oxygen cluster compounds formed by high oxidation states of pre-transition metal ions (such as V, Mo, W, etc.) and oxygen. Kiggen-type heteropolyacids (1:12A series) are the most typical representatives of polyacid structures, and are also the most synthesized, most thoroughly studied, and most promising class of heteropoly compounds. Among them, phosphomolybdic acid (HPMo) is mainly used as an oxidation-reduction catalyst, but phosphomolybdic acid has extremely strong hydrophilicity and its direct catalytic performance is limited, so it needs to be modified and designed. Oxidized phosphomolybdic acid molecules will be reduced to reduced phosphomolybdic acid after gaining one or more electrons. Due to the dd transition of the metal center and the intramolecular charge transfer, it presents a characteristic blue color, so the reduced phosphomolybdic acid is also called "phosphomolybdic blue". The higher oxidizing property of the central metal ion gives phosphomolybdic acid the ability to accommodate additional electrons and maintain the original structure unchanged. The additional electrons introduced during the reduction process can not only be localized on a certain metal center, but also be delocalized between the reduced metal center and the oxidized metal ion connected to it due to the influence of temperature. The reduction process will change the electron density on the surface oxygen of phosphomolybdic acid, which will have an important impact on its coordination ability, which makes phosphomolybdic blue present different physical and chemical properties from oxidized phosphomolybdic acid. There are four main methods for the synthesis of phosphomolybdic blue: constant potential electrolysis, chemical reduction, direct synthesis and hydrothermal synthesis. At present, research on the synthesis of solid phosphomolybdenum blue catalysts by the above methods has been reported, but there are fewer reports on liquid phosphomolybdenum blue with both extraction and catalytic oxidation properties.

[0004] Therefore, how to modify phosphomolybdic acid and reduce it to a liquid phosphomolybdic blue reactive extractant is the focus and difficulty of the research. Summary of the invention

[0005] In order to solve the above problems in the prior art, the present invention provides a phosphomolybdenum blue reactive extractant and a preparation method and application thereof.

[0006] Based on this, the present invention has the following technical solutions: In a first aspect, the present invention provides a method for preparing a phosphomolybdic blue reactive extractant, comprising: mixing phosphomolybdic acid and a reducing agent, and reacting at 50-150° C.; the reducing agent comprises ethylene glycol and / or polyethylene glycol.

[0007] In the present invention, the reaction temperature of the above reaction can be any value among 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, and 150°C, or a numerical range with any two of the above values ​​as endpoints.

[0008] Preferably, the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(100-5000).

[0009] Preferably, the degree of polymerization of the polyethylene glycol is any value in the range of 2 to 600; more preferably, the degree of polymerization of the polyethylene glycol is any value in the range of 2 to 100, for example, it can be any value in the range of 2, 3, 4, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, or a numerical range with any two of the above values ​​as endpoints.

[0010] Preferably, the reducing agent is ethylene glycol, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(3000-5000); Or, the reducing agent is diethylene glycol, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(500-5000); Or, the reducing agent is triethylene glycol, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(100-4000); preferably, the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(100-3000); Or, the reducing agent is tetraethylene glycol, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(500-4000); preferably, the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(500-3000); Alternatively, the reducing agent is polyethylene glycol with a degree of polymerization of 200-600, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(500-1000).

[0011] Preferably, the preparation method of the phosphomolybdic acid reactive extractant comprises: mixing phosphomolybdic acid and a reducing agent in a molar ratio of 1:(100-5000), reacting at 80-150°C and a rotation speed of 100-2000 rpm, and cooling to room temperature after the reaction; the reducing agent is ethylene glycol and / or polyethylene glycol.

[0012] In a second aspect, the present invention provides a phosphomolybdenum blue reactive extractant, which is prepared by the preparation method.

[0013] In a third aspect, the present invention provides the use of the phosphomolybdenum blue reactive extractant in diesel desulfurization and co-production of sulfone products.

[0014] Preferably, the use of the phosphomolybdenum blue reactive extractant in diesel desulfurization and co-production of sulfone products comprises: mixing diesel, the phosphomolybdenum blue reactive extractant and an oxidant, controlling the oxygen-sulfur molar ratio to (2-30):1, performing an extraction-oxidation coupled ultra-deep desulfurization reaction, and performing phase separation after the reaction is completed.

[0015] Preferably, the volume ratio of the diesel fuel to the phosphomolybdenum blue reactive extractant is (1-10): (1-20).

[0016] Preferably, the reaction temperature is 30-80°C. The reaction temperature can be any value among 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or a numerical range with any two of the above values ​​as endpoints.

[0017] Preferably, the reaction time is 0.5 to 5 h.

[0018] Preferably, the stirring rate of the reaction is 100-2000 rpm.

[0019] Preferably, the oxidant comprises one or more of hydrogen peroxide, tert-butyl hydroperoxide and ozone.

[0020] Based on the above technical solution, the beneficial effects of the present invention are: 1. In the present invention, the raw materials phosphomolybdic acid and ethylene glycol with different polymerization degrees are commercial grade reagents, and the phosphomolybdic blue reactive extractant can be obtained by heating and stirring. The synthesis method is simple and does not require further purification.

[0021] 2. In the present invention, the prepared phosphomolybdenum blue reactive extractant has high catalytic activity, can efficiently convert sulfides in diesel in a short time and can co-produce sulfone products.

[0022] 3. In the present invention, the reaction process of the preparation method is simple to operate, does not require high temperature and high pressure, and is safer. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0024] Figure 1 This is a diagram showing the removal effect of 4,6-DMDBT in diesel by HPMo in Comparative Example 1, EG in Comparative Example 2 and HPMo:EG in different molar ratios in Example 1 provided by the present invention.

[0025] Figure 2 This is a diagram showing the removal effect of 4,6-DMDBT in diesel by HPMo in Comparative Example 1, DEG in Comparative Example 2 and HPMo:DEG in different molar ratios in Example 2 provided by the present invention.

[0026] Figure 3 This is a diagram showing the removal effect of 4,6-DMDBT in diesel by HPMo in Comparative Example 1, TEG in Comparative Example 2 and HPMo:TEG in different molar ratios in Example 3 provided by the present invention.

[0027] Figure 4 This is a diagram showing the removal effect of 4,6-DMDBT in diesel by HPMo in Comparative Example 1, TtEG in Comparative Example 2 and HPMo:TtEG in different molar ratios in Example 4 provided by the present invention.

[0028] Figure 5 This is a diagram showing the removal effect of 4,6-DMDBT in diesel by HPMo in Comparative Example 1, PEG in Comparative Example 2 and HPMo:PEG in different molar ratios in Example 5 provided by the present invention.

[0029] Figure 6 This is a graph showing the effect of the synthesis temperature of the phosphomolybdenum blue extractant on the removal effect of 4,6-DMDBT in diesel in Examples 1 to 3, Example 5 and Comparative Examples 3 to 6 provided by the present invention.

[0030] Figure 7 This is a diagram showing the effect of different oxygen-sulfur ratios on the removal of 4,6-DMDBT from HPMo-3000TEG in Example 17 provided by the present invention.

[0031] Figure 8 This is a diagram showing the effect of different reaction temperatures on the removal of 4,6-DMDBT from HPMo-3000TEG in Example 18 provided by the present invention.

[0032] Figure 9 This is a diagram showing the removal effects of three different sulfides, DBT, 4-MDBT and 4,6-DMDBT, in diesel by HPMo-5000EG, HPMo-2000DEG and HPMo-500PEG in Example 19 provided by the present invention.

[0033] Figure 10 This is a diagram showing the removal effect of three different sulfides, DBT, 4-MDBT and 4,6-DMDBT, in diesel by HPMo-3000TEG in Example 20 provided by the present invention.

[0034] Figure 11 This is a diagram showing the removal effect of HPMo on 4,6-DMDBT in Comparative Example 1.

[0035] Figure 12 This is a diagram showing the extraction and extraction-oxidation coupled removal effects of ethylene glycol with different polymerization degrees on 4,6-DMDBT in diesel in Comparative Example 2 provided by the present invention.

[0036] Figure 13 The UV-visible spectra of TEG in Comparative Example 2, HPMo+3000TEG in Comparative Example 5, and HPMo-TEG phosphomolybdenum blue with different molar ratios in Example 3 provided by the present invention. HPMo-TEG phosphomolybdenum blue has a new intervalence charge transfer band near 800 nm, which belongs to the characteristic absorption band of phosphomolybdenum blue.

[0037] Figure 14 This is a Fourier transform infrared spectrum of HPMo-3000TEG before and after the desulfurization reaction in Example 3 provided by the present invention.

[0038] Figure 15 This is a Fourier transform infrared spectrum of the high value-added sulfone products recovered after the desulfurization reaction of HPMo-3000TEG in Example 11.

[0039] Figure 16 The mass spectrum of the high value-added sulfone product recovered after the desulfurization reaction of HPMo-3000TEG in Example 11 is shown in Figure 16 . DETAILED DESCRIPTION

[0040] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the drawings of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] Unless otherwise specified, the various raw materials used in the examples and comparative examples are commercially available conventional raw materials, and the technical means used are conventional means well known to those skilled in the art.

[0042] The types of diesel used in the following examples: Model diesel is prepared by dissolving dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) or 4,6-dimethyldibenzothiophene (4,6-DMDBT) in dodecane to prepare three model oils with a sulfur content of 500 ppm.

[0043] The total sulfur and total nitrogen element analyzer (multi EA 5100) is used to detect the sulfide content in the oil and calculate the desulfurization rate: .

[0044] Example 1 This embodiment provides a phosphomolybdenum blue reactive extractant, and the preparation method thereof comprises: Different masses of phosphomolybdic acid (0.7301 g, 0.3651 g, 0.1825 g, 0.1216 g, 0.0913 g and 0.0730 g) and 12.4140 g of ethylene glycol in molar ratio were put into a 50 mL glass bottle, which was placed in an oil bath and heated to 100 °C. After stirring at 800 rpm for 3 h, the glass bottle was removed from the oil bath and cooled to room temperature to obtain the desired phosphomolybdenum blue reactive extractants, which were named HPMo-500EG, HPMo-1000EG, HPMo-2000EG, HPMo-3000EG, HPMo-4000EG and HPMo-5000EG, respectively.

[0045] Example 2 This embodiment provides a phosphomolybdenum blue reactive extractant, and the preparation method thereof comprises: Different masses of phosphomolybdic acid (0.7301 g, 0.3651 g, 0.1825 g, 0.1216 g, 0.0913 g and 0.0730 g) and 21.2220 g of diethylene glycol in molar ratio were put into a 50 mL glass bottle, which was placed in an oil bath and heated to 100 °C. After stirring at 800 rpm for 3 h, the glass bottle was removed from the oil bath and cooled to room temperature to obtain the desired phosphomolybdenum blue reactive extractants, which were named HPMo-500DEG, HPMo-1000DEG, HPMo-2000DEG, HPMo-3000DEG, HPMo-4000DEG and HPMo-5000DEG, respectively.

[0046] Example 3 This embodiment provides a phosphomolybdenum blue reactive extractant, and the preparation method thereof comprises: Different masses of phosphomolybdic acid (3.6505 g, 0.7301 g, 0.3651 g, 0.1825 g, 0.1216 g, 0.0913 g and 0.0730 g) and 30.0340 g of triethylene glycol in molar ratio were put into a 50 mL glass bottle, which was placed in an oil bath and heated to 100 °C. After stirring at 800 rpm for 3 h, the glass bottle was removed from the oil bath and cooled to room temperature to obtain the desired phosphomolybdenum blue reactive extractants, which were named HPMo-100TEG, HPMo-500TEG, HPMo-1000TEG, HPMo-2000TEG, HPMo-3000TEG, HPMo-4000TEG and HPMo-5000TEG, respectively.

[0047] Example 4 This embodiment provides a phosphomolybdenum blue reactive extractant, and the preparation method thereof comprises: Different masses of phosphomolybdic acid (0.7301 g, 0.3651 g, 0.1825 g, 0.1216 g, 0.0913 g and 0.0730 g) and 38.846 g of tetraethylene glycol in molar ratio were put into a 50 mL glass bottle, which was placed in an oil bath and heated to 100 °C. After stirring at 800 rpm for 3 h, the glass bottle was removed from the oil bath and cooled to room temperature to obtain the desired phosphomolybdenum blue reactive extractants, which were named HPMo-500TtEG, HPMo-1000TtEG, HPMo-2000TtEG, HPMo-3000TtEG, HPMo-4000TtEG and HPMo-5000TtEG, respectively.

[0048] Example 5 This embodiment provides a phosphomolybdenum blue reactive extractant, and the preparation method thereof comprises: Different masses of phosphomolybdic acid (0.7301 g, 0.3651 g, 0.1825 g, 0.1216 g, 0.0913 g and 0.0730 g) and 40.0000 g of polyethylene glycol 200 were put into a 50 mL glass bottle in a molar ratio, which was placed in an oil bath and heated to 100 °C. After stirring at 800 rpm for 3 h, the glass bottle was removed from the oil bath and cooled to room temperature to obtain the desired phosphomolybdenum blue reactive extractants, which were named HPMo-500PEG, HPMo-1000PEG, HPMo-2000PEG, HPMo-3000PEG, HPMo-4000PEG and HPMo-5000PEG, respectively.

[0049] Example 6 This embodiment provides a phosphomolybdenum blue reactive extractant, named HPMo-500PEG400, and its preparation method is the same as that of Example 5, except that PEG is replaced by PEG400.

[0050] Example 7 This embodiment provides a phosphomolybdenum blue reactive extractant, named HPMo-100PEG600, and its preparation method is the same as that of Example 5, except that PEG is replaced by PEG600.

[0051] Example 8 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL (ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol 200) into the reaction bottle, stir well (800 rpm) and heat to 60 °C, then add hydrogen peroxide (H2O2) at an oxygen-sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, wait for it to separate from the oil, take the upper oil phase and use the total sulfur and total nitrogen element analyzer to detect the content of sulfide in the oil, and calculate the desulfurization rate. The results are as follows: Figure 1 shown.

[0052] Example 9 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of a synthetic reactive extractant (HPMo-500EG, HPMo-1000EG, HPMo-2000EG, HPMo-3000EG, HPMo-4000EG or HPMo-5000EG) and add them to a reaction bottle. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H2O2) at an oxygen:sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, after the reactive extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by a total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 2 shown.

[0053] Example 10 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of a synthetic reactive extractant (HPMo-500DEG, HPMo-1000DEG, HPMo-2000DEG, HPMo-3000DEG, HPMo-4000DEG or HPMo-5000DEG) and add them to the reaction bottle. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H2O2) at an oxygen:sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, after the reactive extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by a total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 3 shown.

[0054] Embodiment 11 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of a synthetic reactive extractant (HPMo-100TEG, HPMo-500TEG, HPMo-1000TEG, HPMo-2000TEG, HPMo-3000TEG, HPMo-4000TEG or HPMo-5000TEG) and add them to a reaction bottle, stir well (800 rpm) and heat to 60 °C, then add hydrogen peroxide (H2O2) at an oxygen:sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, after the reactive extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by a total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 4 shown.

[0055] Example 12 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of a synthetic reactive extractant (HPMo-500TtEG, HPMo-1000TtEG, HPMo-2000TtEG, HPMo-3000TtEG, HPMo-4000TtEG or HPMo-5000TtEG) and add them to a reaction bottle. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H2O2) at an oxygen:sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, after the reactive extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by a total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 5 shown.

[0056] Example 13 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of a model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of a synthesized reactive extractant (HPMo-500PEG, HPMo-1000PEG, HPMo-2000PEG, HPMo-3000PEG, HPMo-4000PEG, or HPMo-5000PEG) and add them to a reaction flask. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H 2 O 2 , 30 wt%) according to an oxygen-sulfur ratio of 4. React for 2 h. After the reactive extractant and the oil phase are separated, take the upper oil phase and detect the sulfide content in the oil by a total sulfur and total nitrogen elemental analyzer, and calculate the desulfurization rate. The results are as Figure 6 shown.

[0057] Example 14 This example provides the application of a phosphomolybdenum blue reactive extractant in the extraction-oxidation coupling ultra-deep desulfurization of diesel and the recovery of high-value sulfone products, including: Take 5 mL of a model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of a synthesized reactive extractant (HPMo-500PEG400) and add them to a reaction flask. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H 2 O 2 , 30 wt%) according to an oxygen-sulfur ratio of 4. React for 2 h. After the reactive extractant and the oil phase are separated, take the upper oil phase and detect the sulfide content in the oil by a total sulfur and total nitrogen elemental analyzer, and calculate the desulfurization rate to be 78.73%.

[0058] Example 15 This example provides the application of a phosphomolybdenum blue reactive extractant in the extraction-oxidation coupling ultra-deep desulfurization of diesel and the recovery of high-value sulfone products, including: Take 5 mL of a model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of a synthesized reactive extractant (HPMo-100PEG600) and add them to a reaction flask. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H 2 O 2 , 30 wt%) according to an oxygen-sulfur ratio of 4. React for 2 h. After the reactive extractant and the oil phase are separated, take the upper oil phase and detect the sulfide content in the oil by a total sulfur and total nitrogen elemental analyzer, and calculate the desulfurization rate to be 66.21%.

[0059] Example 16 This example provides the application of a phosphomolybdenum blue reactive extractant in the extraction-oxidation coupling ultra-deep desulfurization of diesel and the recovery of high-value sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of reactive extractant (HPMo+5000EG, HPMo+2000DEG, HPMo+3000TEG or HPMo+500PEG) synthesized at room temperature (30°C) and add them into the reaction bottle. Stir well (800 rpm) and heat to 60°C. Add hydrogen peroxide (H2O2) at an oxygen-sulfur ratio of 4. 2 O 2 , 30wt%), react for 2 h, after the reactive extractant and the oil product are separated, take the upper oil phase and use the total sulfur and total nitrogen element analyzer to detect the content of sulfide in the oil, and calculate the desulfurization rate. The results are as follows: Figure 7 shown.

[0060] Embodiment 17 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of HPMo-3000TEG synthesized in Example 3 were added to a reaction bottle, stirred thoroughly (800 rpm) and heated to 60 °C. Hydrogen peroxide (H2O2) was added at an oxygen-sulfur ratio of (2, 3, and 4). 2 O 2 , 30 wt%), react for a certain time (10 min, 20 min, 30 min, 60 min, 90 min and 120 min), after the reaction type extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by the total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 7 shown.

[0061] Embodiment 18 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of HPMo-3000TEG synthesized in Example 3 were added to a reaction bottle, stirred thoroughly (800 rpm) and heated to (40°C, 50°C, 60°C and 70°C), and hydrogen peroxide (H2O2) was added at an oxygen-sulfur ratio of 4. 2 O 2, 30 wt%), react for a certain time (10 min, 20 min, 30 min, 45 min, 60 min, 90 min and 120 min), after the reaction type extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by the total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 8 shown.

[0062] Embodiment 19 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: 5 mL of model oil with a sulfide (dibenzothiophene, 4-methyldibenzothiophene or 4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of the synthetic reactive extractant (HPMo-5000EG in Example 3, HPMo-2000DEG in Example 2 and HPMo-500PEG in Example 5) were added to the reaction bottle, stirred thoroughly (800 rpm) and heated to 60°C, and hydrogen peroxide (H2O2) was added at an oxygen-sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, after the reactive extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by a total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 9 shown.

[0063] Embodiment 20 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (dibenzothiophene, 4-methyldibenzothiophene or 4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of the synthetic reactive extractant HPMo-3000TEG and add them into the reaction bottle. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H2O2) at an oxygen-sulfur ratio of 4. 2 O 2 , 30 wt%), react for a certain time (10min, 20 min, 30 min, 60 min, 90 min and 120 min), after the reaction type extractant and the oil product are separated, the upper oil phase is taken and the content of sulfide in the oil is detected by total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 10 shown.

[0064] The present invention has found that the use of other oxidants defined in the present invention at the oxygen-sulfur ratio defined in the present invention has an effect comparable to that of hydrogen peroxide.

[0065] Comparative Example 1 This comparative example provides the application of phosphomolybdic acid in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and different masses of phosphomolybdic acid (0.1337 g, 0.0669 g, 0.0334 g, 0.0227 g, 0.0167 g or 0.0134 g) were added to the reaction bottle, stirred thoroughly (800 rpm) and heated to 60 °C. Hydrogen peroxide (H2O2) was added at an oxygen-sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, after the reactive extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by a total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated. The results are as follows Figure 11 shown.

[0066] Comparative Example 2 This embodiment provides the use of a phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL (ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol 200) and add them to the reaction bottle. Stir thoroughly (800 rpm) and heat to 60 ° C. React for 2 h. After it and the oil are separated, take the upper oil phase and use the total sulfur and total nitrogen element analyzer to detect the sulfide content in the oil. Calculate the desulfurization rate. The results are as follows: Figure 12 shown.

[0067] Comparative Example 3 This comparative example provides a phosphomolybdenum blue reactive extractant, named HPMo+5000EG, and its preparation method is different from that of Example 1 only in that the heating temperature is changed to 30°C.

[0068] Comparative Example 4 This comparative example provides a phosphomolybdenum blue reactive extractant, named HPMo+2000DEG, and its preparation method is different from that of Example 2 only in that the heating temperature is changed to 30°C.

[0069] Comparative Example 5 This comparative example provides a phosphomolybdenum blue reactive extractant, named HPMo+3000TEG, and its preparation method is different from that of Example 3 only in that the heating temperature is changed to 30°C.

[0070] Comparative Example 6 This comparative example provides a phosphomolybdenum blue reactive extractant, named HPMo+500PEG, and its preparation method is different from that of Example 5 only in that the heating temperature is changed to 30°C.

[0071] Comparative Example 7 This comparative example provides a phosphomolybdenum blue reactive extractant, named HPMo-3000EtOH, and its preparation method is different from that of Example 5 only in that ethylene glycol is replaced by an equal amount of ethanol and the heating temperature is changed to 80°C.

[0072] This comparative example further provides the use of the above-mentioned phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of synthetic reactive extractant (HPMo-3000EtOH) and add them to the reaction bottle. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H2O2) at an oxygen-sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, after the reactive extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by a total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated to be 46.70%.

[0073] Comparative Example 8 This comparative example provides a phosphomolybdenum blue reactive extractant, named HPMo-3000BT, and its preparation method is different from that of Example 5 only in that ethylene glycol is replaced by an equal amount of 1,2,4-butanetriol.

[0074] This comparative example further provides the use of the above-mentioned phosphomolybdenum blue reactive extractant in ultra-deep desulfurization of diesel oil by extraction-oxidation coupling and recovery of high value-added sulfone products, including: Take 5 mL of model oil with a sulfide (4,6-dimethyldibenzothiophene) content of 500 ppm and 5 mL of a synthetic reactive extractant (HPMo-3000BT) and add them to the reaction bottle. Stir well (800 rpm) and heat to 60 °C. Add hydrogen peroxide (H2O2) at an oxygen-sulfur ratio of 4. 2 O 2 , 30 wt%)), react for 2 h, after the reactive extractant and the oil product are separated, the upper oil phase is taken and the sulfide content in the oil is detected by a total sulfur and total nitrogen element analyzer, and the desulfurization rate is calculated to be 19.28%.

[0075] The UV-visible spectra of TEG in Comparative Example 2, HPMo+3000TEG in Comparative Example 5 and HPMo-TEG phosphomolybdenum blue with different molar ratios in Example 3 are shown in Figure 13 HPMo-TEG phosphomolybdenum blue has a new intervalence charge transfer band around 800 nm, which is attributed to the characteristic absorption band of phosphomolybdenum blue.

[0076] The Fourier transform infrared spectra of HPMo-3000TEG before and after the desulfurization reaction in Example 3 are shown in Figure 14 The absorption peak of HPMo-3000TEG did not change significantly before and after the desulfurization reaction, indicating that its structure was not destroyed and had good stability.

[0077] The Fourier transform infrared spectrum of the high value-added sulfone products recovered after the desulfurization reaction of HPMo-3000TEG in Example 11 is shown in Figure 15 , at 1252 cm -1 and 1280 cm -1 4,6-DMDBTO was observed 2 The characteristic peak of S=O.

[0078] The mass spectrum of the high value-added sulfone products recovered after the desulfurization reaction of HPMo-3000TEG in Example 11 is shown in Figure 16 ,4,6-DMDBTO 2 of M / Z = 244.1.

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a phosphomolybdenum blue reactive extractant, characterized in that: include: The phosphomolybdic acid and the reducing agent are mixed and reacted at 50-150° C.; the reducing agent comprises ethylene glycol and / or polyethylene glycol.

2. The method for preparing the phosphomolybdenum blue reactive extractant according to claim 1, characterized in that: The molar ratio of the phosphomolybdic acid to the reducing agent is 1:(100-5000).

3. The method for preparing the phosphomolybdenum blue reactive extractant according to claim 1 or 2, characterized in that: The degree of polymerization of the polyethylene glycol is any value between 2 and 600; preferably, the degree of polymerization of the polyethylene glycol is any value between 2 and 100.

4. The method for preparing the phosphomolybdenum blue reactive extractant according to any one of claims 1 to 3, characterized in that: The reducing agent is ethylene glycol, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1: (3000-5000); Or, the reducing agent is diethylene glycol, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(500-5000); Or, the reducing agent is triethylene glycol, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(100-4000); preferably, the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(100-3000); Or, the reducing agent is tetraethylene glycol, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(500-4000); preferably, the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(500-3000); Alternatively, the reducing agent is polyethylene glycol with a degree of polymerization of 200-600, and the molar ratio of the phosphomolybdic acid to the reducing agent is 1:(500-1000).

5. A phosphomolybdenum blue reactive extractant, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 4.

6. Use of the phosphomolybdenum blue reactive extractant according to claim 5 in diesel desulfurization and co-production of sulfone products.

7. The use of the phosphomolybdenum blue reactive extractant according to claim 6 in diesel desulfurization and co-production of sulfone products, characterized in that: include: Diesel, the phosphomolybdenum blue reactive extractant and an oxidant are mixed, the oxygen-sulfur molar ratio is controlled to be (2-30):1, and an extraction-oxidation coupled ultra-deep desulfurization reaction is carried out, and phase separation is carried out after the reaction is completed.

8. The use of the phosphomolybdenum blue reactive extractant according to claim 7 in diesel desulfurization and co-production of sulfone products, characterized in that: The volume ratio of the diesel fuel to the phosphomolybdenum blue reactive extractant is (1-10): (1-20).

9. The use of the phosphomolybdenum blue reactive extractant according to claim 7 in diesel desulfurization and co-production of sulfone products, characterized in that: The reaction temperature is 30~80℃.

10. The use of the phosphomolybdenum blue reactive extractant according to claim 7 in diesel desulfurization and co-production of sulfone products, characterized in that: The oxidant includes one or more of hydrogen peroxide, tert-butyl hydroperoxide and ozone.

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