CN113713857A - Polyoxometallate oxidation desulfurization catalyst and preparation method and application thereof - Google Patents

Polyoxometallate oxidation desulfurization catalyst and preparation method and application thereof Download PDF

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CN113713857A
CN113713857A CN202110981338.XA CN202110981338A CN113713857A CN 113713857 A CN113713857 A CN 113713857A CN 202110981338 A CN202110981338 A CN 202110981338A CN 113713857 A CN113713857 A CN 113713857A
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polyoxometallate
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sulfur
desulfurization catalyst
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CN113713857B (en
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吴华东
汪剑
郭嘉
张林锋
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Wuhan Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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Abstract

The invention relates to a polyoxometallate oxidation desulfurization catalyst, a preparation method and application thereof. The polyoxometallate oxidation desulfurization catalyst is 1-methyl-3-propanesulfonic acid imidazole phosphomolybdic tungstate, and has the following structural formula:
Figure DDA0003229134240000011
the invention prepares the oxidative desulfurization catalyst by combining organic cations and polyoxometallate anions, takes ionic liquid as a solvent and an extracting agent, and takes hydrogen peroxide as an oxidant, and carries out oxidative removal on sulfur-containing compounds in oil products; the desulfurization efficiency is high, thiophene and benzothiophene sulfides which are difficult to remove in the fuel oil can be effectively reduced, the dosage of the catalyst is greatly reduced, the catalyst is insoluble in the extractant, and the cyclic utilization rate is high; oxygen gasThe consumption of the catalyst is low, the industrial application cost is reduced, and the catalyst has good application value in the aspect of catalytic oxidation desulfurization of fuel oil.

Description

Polyoxometallate oxidation desulfurization catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of oil oxidation desulfurization, in particular to a polyoxometallate oxidation desulfurization catalyst and a preparation method and application thereof.
Background
Since the 21 st century, automobiles bring great convenience to human beings, but the burning of sulfur-containing gasoline causes the appearance of haze weather, and the public health is seriously harmed. The requirement of countries in the world on the sulfur content in gasoline is increasingly strict, and since 1 month in 2019, China comprehensively supplies national VIA standard gasoline (the sulfur content is less than 10ppm), the gasoline will develop to be sulfur-free in the future. At present, high-sulfur catalytic cracking (FCC) gasoline in gasoline pools in China accounts for about 70%, sulfides in the FCC gasoline mainly exist in the form of benzothiophene and thiophene and account for more than 80% of the total content of the sulfides, and serious challenges are brought to deep desulfurization of gasoline. At present, the domestic and foreign desulfurization methods mainly comprise hydrodesulfurization and non-hydrodesulfurization processes. Hydrodesulfurization (HDS) is the main desulfurization method adopted in the world at present, and becomes the most widely applied desulfurization technology at present due to the characteristics of high treatment efficiency and strong desulfurization capability. However, the technology has large investment scale and high energy consumption, and in the process of hydrodesulfurization, a large amount of olefin in gasoline is subjected to hydrogenation saturation, so that octane number (RON) is lost and a large amount of hydrogen source is consumed. Among the non-hydrodesulfurization, Oxidative Desulfurization (ODS) is most promising among these methods because of its high efficiency and mild reaction conditions.
Polyoxometallate (POMs) is a compound with definite composition, easily regulated structure and excellent characteristics of acidity, oxidation-reduction property and the like. The polyoxometallate serving as an ultra-strong solid acid catalyst not only has a unique hexagonal cage structure, but also has unique acidity, multifunctionality and pseudo-liquid phase behavior. Different elements in the polyoxometallate can show the difference between acidity and oxidation-reduction property, so that the catalytic performance of the polyoxometallate is controllable, and the design of a catalyst is facilitated.
The industrial application of polyoxometallate catalysts in oxidative desulfurization remains challenging. At present, how to design and synthesize a novel polyoxometallate catalyst, regulate and control the structural composition of the novel polyoxometallate catalyst to improve the catalytic performance and improve the cycle performance of the catalyst is a hotspot of research. As a homogeneous catalyst, reactants and the catalyst are dissolved in a liquid phase, and polyoxometallate shows high activity, but the separation and recovery difficulty of the polyoxometallate directly influences the catalytic efficiency and the cycle performance.
Disclosure of Invention
In view of the above, it is necessary to provide a polyoxometallate oxidative desulfurization catalyst, and a preparation method and an application thereof, so as to solve the technical problems of difficult separation and recovery and poor cycle performance of the polyoxometallate catalyst in the prior art.
The first aspect of the invention provides a polyoxometallate oxidative desulfurization catalyst, which is 1-methyl-3-propanesulfonic acid imidazole phosphomolybdenum tungstate, and has the following structural formula:
Figure BDA0003229134220000021
the second aspect of the present invention provides a preparation method of a polyoxometallate oxidation desulfurization catalyst, which comprises the following steps:
mixing 1-methyl-3-propanesulfonic acid imidazole salt and phosphomolybdotungstic acid H3PMo6W6O40Mixing and reacting to obtain the 1-methyl-3-propanesulfonic acid imidazole phosphomolybdic tungstate.
The third aspect of the invention provides an application of a polyoxometallate oxidation desulfurization catalyst, wherein the polyoxometallate oxidation desulfurization catalyst is applied to removing sulfur-containing compounds in oil products.
The fourth aspect of the invention provides a method for removing sulfur-containing compounds in oil products, which comprises the following steps:
and (3) mixing and reacting the sulfur-containing oil product, the oxidant, the extractant and the polyoxometallate oxidation desulfurization catalyst, standing and layering after the reaction is finished, and obtaining an upper layer solution, namely the desulfurized oil product.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares the oxidative desulfurization catalyst by combining organic cations and polyoxometallate anions, takes ionic liquid as a solvent and an extracting agent, and takes hydrogen peroxide as an oxidant, and carries out oxidative removal on sulfur-containing compounds in oil products; the desulfurization efficiency is high, thiophene and benzothiophene sulfides which are difficult to remove in the fuel oil can be effectively reduced, the dosage of the catalyst is greatly reduced, the catalyst is insoluble in the extractant, and the cyclic utilization rate is high; the consumption of the oxidant is less, the industrial application cost is reduced, and the method has good application value in the aspect of catalytic oxidation and desulfurization of fuel oil.
Drawings
FIG. 1 is a test X-ray diffraction pattern of 1-methyl-3-propanesulfonic acid imidazole phosphomolybdenum tungstate according to the present invention at a test angle 2 θ in the range of 5 ° to 50 °;
FIG. 2 is an infrared spectrum of 1-methyl-3-propanesulfonic acid imidazole phosphomolybdenum tungstate of the present invention;
FIG. 3 is a thermogravimetric-differential thermogram of 1-methyl-3-propanesulfonic acid imidazole phosphomolybdenum tungstate of the present invention;
FIG. 4 is an XPS analysis spectrum of 1-methyl-3-propanesulfonic acid imidazole phosphomolybdenum tungstate of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In a first aspect of the present invention, there is provided a polyoxometallate oxidative desulfurization catalyst which is 1-methyl-3-propanesulfonic acid imidazole phosphomolybdotungstate (i.e., [ MIMPs ]]3PMo6W6O40) It has the following structural formula:
Figure BDA0003229134220000041
the second aspect of the present invention provides a preparation method of a polyoxometallate oxidation desulfurization catalyst, which comprises the following steps:
mixing 1-methyl-3-propanesulfonic acid imidazole salt and phosphomolybdic tungstic acid (H)3PMo6W6O40) Mixing and reacting to obtain the 1-methyl-3-propanesulfonic acid imidazoleAzolyphosphomolybdotungstate ([ MIMPs)]3PMo6W6O40)。
In the present invention, the imidazole salt of 1-methyl-3-propanesulfonic acid is obtained by mixing and reacting methylimidazole with 1, 3-propanesultone.
Further, the molar ratio of the methyl imidazole to the 1, 3-propane sultone is 1: 1.
Further, the mixing reaction process of the methyl imidazole and the 1, 3-propane sultone is carried out in toluene, and the dosage ratio of the methyl imidazole to the toluene is 1 g: (8-12) mL.
Further, in the process of mixing and reacting the methyl imidazole and the 1, 3-propane sultone, the reaction temperature is 70-90 ℃, and preferably 80 ℃; the reaction time is 1-3 hours, preferably 2 hours.
Further, after the process of the mixed reaction of the methyl imidazole and the 1, 3-propane sultone is finished, the method further comprises the following steps: washing and drying the reaction product by ethyl acetate to obtain the 1-methyl-3-propanesulfonic acid imidazole salt.
In the invention, the phosphomolybdic tungstic acid is obtained by mixing and reacting disodium hydrogen phosphate, sodium molybdate and sodium tungstate.
Further, the molar ratio of the disodium hydrogen phosphate to the sodium molybdate to the sodium tungstate is 1:6: 6.
Further, the phosphomolybdic tungstic acid is prepared in water through a process of mixing and reacting disodium hydrogen phosphate, sodium molybdate and sodium tungstate; furthermore, the concentration of the disodium hydrogen phosphate in the reaction system is 0.01-0.1 mol/L.
Further, in the process of the mixing reaction of the disodium hydrogen phosphate, the sodium molybdate and the sodium tungstate, acid is added to adjust the pH value to 1-2, preferably 1.5.
Further, in the process of the mixing reaction of the disodium hydrogen phosphate, the sodium molybdate and the sodium tungstate, the reaction temperature is 80-100 ℃, and preferably 90 ℃; the reaction time is 6-10 hours, preferably 8-9 hours.
Further, the phosphomolybdic tungstic acid is prepared by mixing disodium hydrogen phosphate, sodium molybdate and sodium tungstate for reaction, and specifically comprises the following steps: and (2) uniformly mixing the disodium hydrogen phosphate solution and the sodium molybdate solution, then adding the sodium tungstate solution, dropwise adding concentrated sulfuric acid, adjusting the pH to 1-2, and stirring and reacting at 80-100 ℃ for 6-10 hours.
Further, after the process of the above mixed reaction of disodium hydrogen phosphate, sodium molybdate and sodium tungstate is finished, the method further comprises the following steps: extracting the reaction product with diethyl ether, evaporating and drying to obtain H3PMo6W6O40。
In the present invention, the above imidazole salt of 1-methyl-3-propanesulfonic acid and H3PMo6W6O40Is 3: 1.
In the invention, the mixed reaction process of the 1-methyl-3-propane sulfonic acid imidazolium salt and the phosphomolybdic tungstic acid is carried out in water, and the dosage ratio of the 1-methyl-3-propane sulfonic acid imidazolium salt to the water is 1 g: (60-120) mL.
In the invention, in the process of mixing and reacting the 1-methyl-3-propanesulfonic acid imidazole salt and the phosphomolybdic tungstic acid, the reaction temperature is 15-40 ℃, and preferably 20-30 ℃; the reaction time is 15-30 h, preferably 24 h.
In the invention, after the process of the mixed reaction of the imidazole salt of 1-methyl-3-propane sulfonic acid and the phosphomolybdic tungstic acid is finished, the method further comprises the following steps: the reaction product is decompressed and evaporated, and is dried to obtain polyoxometallate oxidation desulfurization catalyst [ MIMPs]3PMo6W6O40。
The polyoxometallate oxidation desulfurization catalyst has the advantages of cheap and easily-obtained raw materials, simple synthesis and easy industrialization.
The third aspect of the invention provides an application of a polyoxometallate oxidation desulfurization catalyst, wherein the polyoxometallate oxidation desulfurization catalyst is applied to removing sulfur-containing compounds in oil products, and further thiophene sulfur-containing compounds. Further, the compound is at least one of dibenzothiophene, thiophene and 4, 6-dimethyldibenzothiophene.
The fourth aspect of the invention provides a method for removing sulfur-containing compounds in oil products, which comprises the following steps:
and (3) mixing and reacting the sulfur-containing oil product, the oxidant, the extractant and the polyoxometallate oxidation desulfurization catalyst, standing and layering after the reaction is finished, and obtaining an upper layer solution, namely the desulfurized oil product.
In the invention, the oil content of the sulfur-containing oil product is 10-10000 ppm.
In the invention, the oxidant is hydrogen peroxide, and is further hydrogen peroxide with the mass fraction of 25-35%; the extractant is 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim]PF6) 1-octyl-3-methylimidazolium tetrafluoroborate ([ Omim [ ])]BF4) 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim)]BF4) At least one of (1).
In some embodiments of the invention, the sulfur-containing oil is a fuel having a sulfur content of 500 ppm; further, the volume ratio of the oxidant to the sulfur-containing oil product is (0.0028-0.0033): 1, preferably 0.0028: 1; the mass ratio of the sulfur content in the oxidizing agent to the sulfur-containing oil is 2.5: 1, the volume ratio of the extracting agent to the sulfur-containing oil product is 0.1: 1, the dosage ratio of the catalyst to the sulfur-containing oil product is 0.005 g: 1 mL.
In the invention, the reaction process is carried out under the condition of stirring, and the reaction temperature is 40-70 ℃, preferably 50-70 ℃, and more preferably 50-60 ℃; the reaction time is 60 to 180min, preferably 60 to 120min, and further 120 min.
In the invention, after the reactants are stood and layered, the obtained lower layer solution is dried to remove water, and then the sulfur-containing oil product and the oxidant are continuously added to realize the circular desulfurization.
Example 1
The embodiment provides a preparation method of a polyoxometallate oxidation desulfurization catalyst, which comprises the following steps:
(1) adding 0.05mol of methylimidazole and 0.05mol of 1, 3-propane sultone into 40mL of toluene, reacting for 2 hours at 80 ℃, washing the obtained product with ethyl acetate for three times, and drying for 24 hours at 100 ℃ to obtain 1-methyl-3-propane sultone imidazolium salt;
(2) 2.15g of disodium hydrogen phosphate (Na)2HPO4·12H2O, 0.006mol) was dissolved in 12.5mL of deionized water, and 8.71g of sodium molybdate (Na)2MoO4·2H2O, 0.036mol) in 25mL of deionized water, mixing the two solutionsStirring at 90 deg.C for 30 min; followed by mixing 11.88g of sodium tungstate (Na)2WO4·2H2O, 0.036mol) in 50mL of deionized water and added to the above solution, concentrated sulfuric acid was added dropwise, after adjusting the pH to 1.5, the solution was heated to 90 ℃, and then stirred for 8 h; the product obtained is extracted 3 times with diethyl ether and, after evaporation and drying, a yellow powder H is obtained3PMo6W6O40；
(3) 0.621g of imidazole 1-methyl-3-propanesulfonate and 2.34g H3PMo6W6O40Dissolving in 50mL of deionized water, stirring at room temperature for 24h, and evaporating and drying the obtained product under reduced pressure to obtain the polyoxometallate oxidative desulfurization catalyst.
As can be seen from FIG. 1, the crystal structure of the phosphomolybdic tungstic acid in the synthesized 1-methyl-3-propanesulfonic imidazole phosphomolybdic tungstate is not changed, which indicates that the catalyst contains the phosphomolybdic tungstic acid; from FIG. 2, it can be seen that the characteristic peaks of 1-methyl-3-propanesulfonic acid imidazole and phosphomolybdenum tungstate are both found in 1-methyl-3-propanesulfonic acid imidazole phosphomolybdenum tungstate, which indicates that 1-methyl-3-propanesulfonic acid imidazole phosphomolybdenum tungstate is successfully synthesized. As can be seen from figure 3, the weight loss is about 20.1% at 300-580 ℃, and is identical with the mass fraction of 1-methyl-3-propane sulfonic acid imidazole of 20.5%; above 600 ℃ and the remaining amount is 78%, with PMo6W6O40The mass fraction of (A) is 77.8% substantially consistent, indicating that the synthesized substances are [ MIMPs]3PMo6W6O40. As can be seen from FIG. 4, MIMPs and PMo6W6O40Form chemical bonds, further illustrate that the synthesized substances are [ MIMPs]3PMo6W6O40。
Example 2
The sulfur compounds in the fuel oil were removed by using the oxidative desulfurization catalyst prepared in example 1.
Preparing simulated oil:
adding 1g of Dibenzothiophene (DBT) and 0.7g of tetradecane into 500mL of n-octane, and carrying out ultrasonic treatment for 30min to prepare 500ppm of simulated sulfur-containing fuel oil;
dissolving 0.046g of 4, 6-dimethyldibenzothiophene (4,6-DMDBT) and 0.0367mL of tetradecane in 20mL of n-octane, and performing ultrasonic treatment for 30min to prepare 500ppm of simulated sulfur-containing fuel oil;
dissolving 0.0184g of thiophene (BT) and 0.0367mL of tetradecane in 20mL of n-octane, and carrying out ultrasonic treatment for 30min to prepare 500ppm of simulated sulfur-containing fuel.
Group 1: 1mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim [ ])]PF6) Adding into 10mL of simulated oil while stirring, heating to 70 deg.C, holding for 20min, adding 0.05g of catalyst and 28 μ L H2O2And reacting for 120 min.
Group 2: 1mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim [ ])]PF6) Adding into 10mL of simulated oil while stirring, heating to 60 deg.C, holding for 20min, adding 0.05g of catalyst and 28 μ L H2O2And reacting for 120 min.
Group 3: 1mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim [ ])]PF6) Adding into 10mL of simulated oil while stirring, heating to 50 deg.C, holding for 20min, adding 0.05g of catalyst and 28 μ L H2O2And reacting for 120 min.
Group 4: 1mL 1-octyl-3 methylimidazolium hexafluorophosphate ([ Omim [ ]]PF6) Adding into 10mL of simulated oil while stirring, heating to 40 deg.C, holding for 20min, adding 0.05g of catalyst and 28 μ L H2O2And reacting for 120 min.
Group 5: 1mL 1-octyl-3 methylimidazolium hexafluorophosphate ([ Omim [ ]]PF6) Adding into 10mL of simulated oil while stirring, heating to 60 deg.C, holding for 20min, adding 0.05g catalyst and 17 μ L H2O2And reacting for 120 min.
Group 6: 1mL 1-octyl-3 methylimidazolium hexafluorophosphate ([ Omim [ ]]PF6) Adding into 10mL of simulated oil while stirring, heating to 60 deg.C, holding for 20min, adding 0.05g of catalyst and 22 μ L H2O2And reacting for 120 min.
Group 7: 1mL 1-octyl-3 methylimidazolium hexafluorophosphate ([ Omim [ ]]PF6) Adding into 10mL of simulated oil, stirring, heating to 60 deg.C, holding for 20min, and adding0.05g of catalyst and 33. mu. L H2O2And reacting for 120 min.
Group 8: 1mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim [ ])]PF6) Adding into 10mL of simulated oil while stirring, heating to 60 deg.C, holding for 20min, adding 0.05g catalyst and 44 μ L H2O2And reacting for 120 min.
Group 9: 1mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim [ ])]PF6) Adding into 10mL of simulated oil, stirring, heating to 60 deg.C, and reacting for 120 min.
Group 10: 1mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim [ ])]PF6) Adding into 10mL of simulated oil, stirring, heating to 60 deg.C, holding for 20min, and adding 28 μ L H2O2And reacting for 120 min.
Group 11: 0.05g of catalyst was added to 10mL of simulated oil with constant stirring, heated to 60 ℃ and added to 28. mu. L H2O2And reacting for 120 min.
Group 12: 1mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim [ ])]PF6) Adding into 10mL of simulated oil (BT) while stirring, heating to 60 deg.C, holding for 20min, adding 0.05g of catalyst and 28 μ L H2O2And reacting for 120 min.
Group 13: 1mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim [ ])]PF6) Adding into 10mL of simulated oil (4,6-DMDBT) while stirring, heating to 60 deg.C, holding for 20min, adding 0.05g of catalyst and 28 μ L H2O2And reacting for 120 min.
After the reaction is finished, standing for layering, separating the oil product by a simple pouring method, detecting the sulfur content in the oil product by gas chromatography (GC-FID), and calculating the desulfurization rate:
Figure BDA0003229134220000091
TABLE 1
Figure BDA0003229134220000092
Figure BDA0003229134220000101
As can be seen from Table 1, the optimum reaction temperature is 50-70 ℃ selected from application examples 1, 2, 3 and 4, and the amount of the oxidant required for the optimum reaction selected in combination with application examples 2, 5, 6, 7 and 8 is 28 μ L, i.e. the molar ratio of the oxidant to the sulfur content of the fuel oil is 2.5. In combination with application examples 2, 9, 10 and 11, the reaction showed the highest activity in the presence of catalyst, ionic liquid and oxidant. By combining the application examples 12 and 13, the method has higher removal rate on BT, 4,6-DMDBT which is difficult to remove by oxidative desulfurization.
Decanting the upper layer oil, drying the remaining ionic liquid and catalyst to remove H2O2Adding fresh oil containing DBT and H2O2The cycling experiments were carried out under the conditions of group 2 in example 2, with constant stirring and heating to 60 ℃ and the results are shown in Table 2.
TABLE 2
Figure BDA0003229134220000102
Figure BDA0003229134220000111
As can be seen from Table 2, the activity of the polyoxometallate oxidative desulfurization catalyst is not obviously reduced after the polyoxometallate oxidative desulfurization catalyst is circularly regenerated for 33 times, the desulfurization effect is good, the cyclic utilization rate is high, and the regeneration performance is excellent.
Comparative example 1
Compared to group 2 in example 2, the only difference is: the catalyst is H3PMo6W6O40。
Comparative example 2
Compared to group 2 in example 2, the only difference is: the catalyst is 1-methyl-3-propane sulfonic acid imidazole salt.
Comparative example 3
Compared to group 2 in example 2, the only difference is: the catalyst is 1-methyl-3-propanesulfonic imidazole phosphomolybdate ([ MIMPs)]3PMo12O40)。
Comparative example 4
Compared to group 2 in example 2, the only difference is: the catalyst is 1-methyl-3-propanesulfonic acid imidazole phosphotungstate ([ MIMPs)]3PW12O40)。
Comparative example 5
Compared to group 2 in example 2, the only difference is: the catalyst is H3PMo6W6O40And 1-methyl-3-propanesulfonic acid imidazole (molar ratio 1: 3).
TABLE 3
Figure BDA0003229134220000121
As can be seen from Table 3, compared with the catalysts of comparative examples 1-5, the desulfurization catalyst of the present application has high desulfurization efficiency and good cycle performance; meanwhile, as can be seen from comparative example 5, the desulfurization catalyst of the present application is not H3PMo6W6O40And 1-methyl-3-propanesulfonic acid imidazole, but the reaction product.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (10)

1. The polyoxometallate oxidation desulfurization catalyst is characterized by being 1-methyl-3-propanesulfonic acid imidazole phosphomolybdic tungstate, and having the following structural formula:
Figure FDA0003229134210000011
2. a method for preparing the polyoxometallate oxidative desulfurization catalyst as recited in claim 1, comprising the steps of:
mixing 1-methyl-3-propanesulfonic acid imidazole salt and phosphomolybdotungstic acid H3PMo6W6O40And mixing and reacting to obtain the 1-methyl-3-propanesulfonic acid imidazole phosphomolybdenum tungstate.
3. The method for preparing the polyoxometallate oxidative desulfurization catalyst according to claim 2, wherein the 1-methyl-3-propane sulfonic acid imidazolium salt is obtained by mixing and reacting methylimidazole and 1, 3-propane sulfonic acid lactone, and the molar ratio of the methylimidazole to the 1, 3-propane sulfonic acid lactone is 1: 1.
4. The preparation method of the polyoxometallate oxidative desulfurization catalyst as claimed in claim 2, wherein the phosphomolybdic tungstic acid is obtained by mixing and reacting disodium hydrogen phosphate, sodium molybdate and sodium tungstate, and the molar ratio of the disodium hydrogen phosphate to the sodium molybdate to the sodium tungstate is 1:6: 6.
5. The preparation method of the polyoxometallate oxidation desulfurization catalyst according to claim 2, wherein in the process of mixing and reacting the 1-methyl-3-propanesulfonic acid imidazole salt and the phosphomolybdotungstic acid, the reaction temperature is 15-40 ℃, and the reaction time is 15-30 h.
6. The use of the polyoxometallate oxidative desulfurization catalyst as claimed in claim 1, wherein the polyoxometallate oxidative desulfurization catalyst is used for removing sulfur-containing compounds in oil products.
7. The use of the polyoxometallate oxidative desulfurization catalyst of claim 6, wherein the sulfur-containing compound is a thiophene-based sulfur-containing compound.
8. A method for removing sulfur-containing compounds in oil products is characterized by comprising the following steps:
mixing and reacting sulfur-containing oil products, an oxidant, an extractant and the polyoxometallate oxidation desulfurization catalyst of claim 1, standing and layering after the reaction is finished, and obtaining an upper layer solution, namely the desulfurized oil products.
9. The method for removing sulfur-containing compounds from oil products according to claim 8, wherein said oxidant is hydrogen peroxide, and said extractant is 1-octyl-3-methylimidazolium hexafluorophosphate ([ Omim ™)]PF6) 1-octyl-3-methylimidazolium tetrafluoroborate ([ Omim [ ])]BF4) 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim)]BF4) At least one of; the volume ratio of the oxidant to the sulfur-containing oil product is (0.0028-0.0033): 1; the volume ratio of the extracting agent to the sulfur-containing oil product is 0.1: 1, the dosage ratio of the catalyst to the sulfur-containing oil product is 0.005 g: 1 mL; the reaction temperature is 40-70 ℃, and the reaction time is 60-180 min.
10. The method for removing sulfur-containing compounds from oil products according to claim 8, wherein after the reactant is settled and layered, the obtained lower solution is dried to remove water, and then the sulfur-containing oil product and the oxidant are continuously added to realize the cyclic desulfurization.
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