CN109908962B - Jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material, preparation method and application - Google Patents
Jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material, preparation method and application Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 111
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 106
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- 240000008866 Ziziphus nummularia Species 0.000 title 1
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- 241001247821 Ziziphus Species 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000696 magnetic material Substances 0.000 claims abstract description 15
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- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 6
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- 239000012047 saturated solution Substances 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 16
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- COPKIGDNCXOKOL-UHFFFAOYSA-N C1(C=CC=C1)C(=O)[Mo] Chemical compound C1(C=CC=C1)C(=O)[Mo] COPKIGDNCXOKOL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material, a preparation method and application. The preparation steps are as follows: firstly, respectively adopting a substitution reaction to prepare heteropoly acid ionic liquid, adopting a solvothermal method to prepare an aminated magnetic composite material, and then adopting an ultrasonic loading method to prepare the heteropoly acid ionic liquid loaded aminated magnetic composite material. The product obtained by the method is powdery, brown, uniform in particle size distribution, and stable in property, and has a jujube cake-shaped structure. The defect that the magnetic material is easy to agglomerate is overcome, and the obtained material has good dispersibility, high magnetic property, easily obtained raw materials and high yield; the catalyst has magnetism and catalytic activity, can be effectively used for the desulfurization of petroleum samples, and can be separated, recycled and reused.
Description
Technical Field
The invention relates to a jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material, a preparation method and an application technology thereof, in particular to a preparation method of heteropoly acid ionic liquid and aminated magnetic composite material, a preparation method of jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material, and the purposes of catalyzing a petroleum sample to desulfurize by using the jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material as a catalyst and hydrogen peroxide as an oxidant, realizing deep desulfurization of petrochemical industry and the like.
Background
With the progress and development of science and technology, petroleum plays an important role in promoting the industrialization process. However, sulfur in the form of hydrogen sulfide, thiophene, disulfide, etc. in petroleum not only affects the quality of the oil, but also Sulfur Oxides (SO) generated by combustion thereofx) But also poses great threats to the ecological environment and human health. Therefore, how to efficiently and deeply desulfurize to obtain petroleum with ultra-low sulfur content becomes a hot point of research in the field of current petrochemical industry.
Currently common means of deep desulfurization include hydrodesulfurization and non-hydrodesulfurization. The traditional hydrodesulfurization means has the defects of difficult removal of thiophene substances, over high cost, harsh conditions, time consumption, high energy consumption and the like. For example, Ye et al (Journal of Hazardous Materials,2019,366: 432-. And the non-hydrogenation desulfurization is more and more favored by researchers due to low energy consumption and environmental protection. Non-hydrodesulfurization techniques include, for example, adsorptive desulfurization (e.g., Zheng et al (Journal of Hazardous Materials,2019,362:424-2O3Modified Ag-CeOx/TiO2-SiO2The composite material can effectively adsorb 4, 6-dimethyl dibenzothiophene in a simulated oil sample, thereby realizing adsorption desulfurization and extraction desulfurization (such as: juliano et al (Applied Catalysis B: Environmental,2018,230:177-183) with cyclopentadienyl carbonyl molybdenum complex CpMo (CO)3R is a catalyst, hydrogen peroxide is an oxidant, and oxidative desulfurization and biological desulfurization (such as: cano et al (Journal of Cleaner Production,2018,181:663-674) desulfurization using anaerobic biotechnology and oxidative desulfurization (e.g.: pouladi et al (J Journal of Cleaner Production,2019,209:965-977) optimize the experimental conditions for oxidative desulfurization by the response surface method), and the like. Wherein the oxidative desulfurization is carried out by an oxidant, such as hydrogen peroxide (H)2O2) And oxidizing the organic sulfide into corresponding sulfone or sulfoxide, improving the solubility of the organic sulfide in a polar solvent, and separating the organic sulfide from petroleum by means of extraction, distillation and the like, thereby achieving the purpose of deep desulfurization.
In recent years, ionic liquids have been referred to as "green solvents" due to their presenceGood thermal stability and chemical stability, and is widely applied to catalytic oxidation desulfurization. The ionic liquid is introduced into the heteropoly acid with redox activity, so that the heteropoly acid ionic liquid with double oxidation active centers can be formed, and excellent catalytic activity is shown. (SiW) having high catalytic activity was synthesized by a sol-gel method such as Xun (Chemical Engineering Journal,2016,288:608-617)12O40-IL) heteropolyacid ionic liquid catalyst, which catalyst is at 60 ℃, the ratio of the amount of oxidant to the amount of sulphur species: when n (O/S) ═ 4, the desulfurization rate reaches 99.9%, which shows that the heteropoly acid ionic liquid has good desulfurization activity. However, the heteropolyacid ionic liquid also has the disadvantages of low recovery rate and the like, so that the selection of a proper immobilization method is particularly important. A common carrier is SiO2、Al2O3、Fe3O4Etc. of Fe3O4Has stronger magnetism, can realize the quick separation of the catalyst and the oil sample, and is gradually one of hot carriers. If the heteropoly acid ionic liquid and the magnetic material can be combined to obtain the heteropoly acid ionic liquid loaded magnetic composite material, the advantages of high selectivity, good dispersibility, repeated utilization and the like of the heteropoly acid ionic liquid loaded magnetic composite material can be expected to be realized, and the heteropoly acid ionic liquid loaded magnetic composite material has important and positive significance in the aspects of catalyst regeneration and recycling, oil product quality improvement and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the amido magnetic composite material loaded by the heteropoly acid ionic liquid with the jujube cake type structure, which has high selectivity and good dispersibility and can be repeatedly utilized.
In order to solve the technical problems, the invention adopts the technical scheme that: a jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material is prepared from heteropoly acid ionic liquid and aminated magnetic composite material through loading heteropoly acid ionic liquid on aminated nano magnetic material by ultrasonic immersion method, and finally obtaining heteropoly acid ionic liquid loaded amino nano magnetic composite material.
The preparation method of the jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material comprises the following steps: the amino-nanometer magnetic composite material loaded with the heteropoly acid ionic liquid is finally obtained by preparing the heteropoly acid ionic liquid through substitution reaction, preparing the aminated magnetic composite material through a solvothermal method and loading the heteropoly acid ionic liquid on the aminated nanometer magnetic material through an ultrasonic impregnation method.
The preparation of the heteropoly acid ionic liquid comprises the following specific steps: slowly dripping halogenated hydrocarbon into N-methylimidazole or pyridine during magnetic stirring, heating and refluxing, and continuously refluxing and stirring until complete reaction; cooling after the reaction is finished, extracting excessive reaction raw materials with ethyl acetate for multiple times, and removing residual ethyl acetate by reduced pressure distillation to obtain ionic liquid; and further slowly dropwise adding a phosphotungstic acid aqueous solution under stirring, continuously refluxing after dropwise adding is finished, carrying out reduced pressure distillation after the reaction is finished, removing excessive water and byproducts in the reaction solution, and drying to obtain the heteropoly acid ionic liquid.
The halogenated hydrocarbon is one of C4-C12 chlorinated or brominated hydrocarbon;
the mass ratio of the N-methylimidazole or pyridine to the halogenated hydrocarbon is 0.5: 1-1: 5, preferably 1: 1-1: 2; the reflux stirring reaction temperature of the N-methylimidazole or pyridine and the halogenated hydrocarbon is 60-150 ℃, the reaction time is 2-24 hours, the preferable reaction temperature is 80-100 ℃, and the reaction time is 6-10 hours; the phosphotungstic acid aqueous solution is a saturated solution; the mass ratio of the ionic liquid to the phosphotungstic acid is 2: 1-8: 1, and the preferred mass ratio of the ionic liquid to the phosphotungstic acid is 3: 1-5: 1; after the dripping is finished, continuously refluxing for 2-12h, preferably for 6-10 h; the drying temperature is 60-120 ℃ and the time is 2-24 h, and the preferable drying temperature is 80-100 ℃ and the time is 6-10 h.
According to the invention, the N-methylimidazole or pyridyl ionic liquid is selected, and the structure and properties of the material, such as solubility, polarity and the like, can be regulated and controlled by adjusting the type of the substituent group, so that different degradation catalysts can be selected for different types of sulfur-containing oil products.
The preparation method of the aminated magnetic composite material specifically comprises the following steps: dissolving ferric iron and acetate in ethylene glycol; the mass ratio of the ferric iron to the acetate is 1: 1-1: 10, the mass concentration of the ferric iron in the ethylene glycol is 20-400 g/L, and the mass concentration of the acetate in the ethylene glycol is 40-600 g/L; stirring for 5-30 min at room temperature; then adding 5-80mL of organic polyamine, and stirring until a stable orange solution is formed; transferring the reaction solution into a reaction kettle, and reacting for 2-24 h at 100-240 ℃; and (4) cooling, performing magnetic separation and washing until the pH value is 7, and performing vacuum drying to obtain the aminated magnetic composite material.
The ferric iron is one of ferric trichloride and ferric sulfate.
The acetate is one of sodium acetate or ammonium acetate.
The mass concentration of the ferric iron in the ethylene glycol is preferably 40-120 g/L.
The mass concentration of the acetate in the ethylene glycol is preferably 60-180 g/L.
The organic polyamine is one of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylpentamine.
The amount of the organic polyamine is preferably 20 to 60 mL.
The reaction temperature in the reaction kettle is preferably 150-200 ℃, and the reaction time is preferably 10-20 h.
The preparation method of the heteropolyacid ionic liquid loaded aminated composite material specifically comprises the following steps: respectively ultrasonically dispersing the aminated magnetic composite material into an aqueous solution to ensure that the mass concentration of the aminated magnetic composite material is preferably 5-100 g/L, dissolving the prepared heteropoly acid ionic liquid into acetone to ensure that the mass concentration of the prepared heteropoly acid ionic liquid is preferably 20-500 g/L, slowly dropwise adding the prepared heteropoly acid ionic liquid into the aminated magnetic composite material, and ultrasonically dispersing the aminated magnetic composite material into the aqueous solution to ensure that the mass ratio of the aminated magnetic composite material to the heteropoly acid ionic liquid is 1: 1-1: 10; continuing to perform ultrasonic treatment for 5-30 min after the dropwise addition is finished; and after the reaction is finished, vacuum drying for 2-24 hours at 30-100 ℃ to obtain the heteropolyacid ionic liquid loaded amination composite material.
The mass concentration of the aminated magnetic composite material in water is preferably 10-40 g/L.
The mass concentration of the heteropoly acid ionic liquid in acetone is preferably 50-150 g/L.
The mass ratio of the aminated magnetic composite material to the heteropoly acid ionic liquid is preferably 1: 4-1: 6.
The invention also provides application of the heteropolyacid ionic liquid loaded aminated composite material as a catalyst and hydrogen peroxide as an oxidant in catalyzing desulfurization of a petroleum sample.
According to the invention, the application of the heteropolyacid ionic liquid supported aminated composite material is preferably used for catalyzing desulfurization of petroleum samples.
The specific catalytic desulfurization method of the invention is as follows:
under the condition of room temperature oscillation, adding 0.2-5 g of the heteropolyacid ionic liquid-loaded aminated magnetic composite material in the amount of each liter of simulated oil sample into the jujube cake type structure heteropolyacid ionic liquid-loaded aminated magnetic composite material, uniformly dispersing the heteropolyacid ionic liquid-loaded aminated magnetic composite material by ultrasonic treatment, and quickly adding H2O20.04-10 mL of solution (30 wt%), and after ultrasonic treatment for a certain time (2-20min), separating the catalyst and the simulated oil sample under the action of an external magnetic field, and extracting 5mL of acetonitrile. Under the condition of 305-; the desulfurization rate can be more than 85%.
The invention has the advantages and beneficial effects that:
1. according to the preparation method, the substitution reaction is firstly adopted to prepare the heteropoly acid ionic liquid, the solvothermal method is adopted to prepare the aminated magnetic composite material, the ultrasonic loading method is then adopted to prepare the heteropoly acid ionic liquid loaded aminated magnetic composite material, and the preparation technology is characterized in that the magnetic composite material with a special jujube cake type structure can be obtained, so that the problem that the magnetic material is easy to agglomerate is effectively solved. Experiments prove that: the method has the advantages of simple operation steps and low cost, the obtained composite material has uniform particle size distribution, stable property, quick reaction, easily obtained raw materials and high yield, can be effectively used as a catalyst for the desulfurization of petroleum samples, realizes the dual functions of catalysis and magnetism of the material, and is favorable for the separation and recovery of the catalyst.
2. The heteropolyacid ionic liquid loaded aminated magnetic composite material with the special date cake type structure, which has dual functions of catalysis and magnetism, has the advantages of low price of adopted raw materials, easy obtainment and purification and high catalytic activity for desulfurization of petroleum samples; the invention has the advantages of simple preparation method, low cost, cheap and easily obtained materials, environmental protection and high added value of resources.
3. The invention adopts a direct one-step method to synthesize amino-modified ferroferric oxide instead of a conventional silicon dioxide-modified ferroferric oxide magnetic core, and the method has the advantages that: (1) the magnetic core content is high, so that the magnetic separation effect is good; (2) the ferroferric oxide surface is subjected to amino functional modification, so that the ferroferric oxide surface is further favorably and firmly combined with heteropoly acid ionic liquid, the stability of the material is improved, the dispersibility of the material is improved, the specific surface area of the material is improved, and a special jujube cake type structure is formed; in addition, the chemical synthesis method can be carried out in a homogeneous system, the reaction is uniform and easy to control, and the particle size of the obtained material is uniform.
4. The date cake structure can be observed by an electron microscope, and is particularly shown in figure 4; the advantages of this particular configuration are: (1) a large amount of heteropoly acid ionic liquid is densely embedded on the surface of the aminated magnetic material, which shows that the heteropoly acid ionic liquid loaded by the dipping method is more easily dispersed on the surface of the aminated magnetic material and is not easy to agglomerate; (2) the jujube cake type structure can improve the stability of the material, improve the dispersibility of the material, improve the specific surface area of the material and is beneficial to the occurrence of catalytic desulfurization reaction.
5. The method has the advantages of mild reaction conditions, cheap raw materials, convenient operation and low cost, and the catalytic oxidation desulfurization process is used, so that the desulfurization can be more thoroughly carried out, and the problems of secondary pollution and the like do not exist; the material obtained by the invention integrates amino functionalized magnetic core, ionic liquid and heteropoly acid, and is an important guarantee for high catalytic desulfurization activity.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material.
Fig. 2 is an infrared spectrum (FTIR) of the jujube cake-structured heteropoly acid ionic liquid loaded aminated magnetic composite according to the embodiment of the present invention.
FIG. 3 is an X-ray diffraction pattern (XRD) of the jujube cake-structured heteropoly acid ionic liquid loaded aminated magnetic composite material obtained in the example of the present invention.
Fig. 4 is transmission electron microscope (TEM a) and (SEM b) photographs of the obtained date cake type structure heteropoly acid ionic liquid supported aminated magnetic composite material according to the example of the present invention.
FIG. 5 shows X-ray spectra (XPS) (a-f) of the resulting jujube cake-structured heteropoly acid ionic liquid-supported aminated magnetic composite material according to the example of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments, so that the objects and effects of the present invention will be more apparent, but the present invention is not limited to the following embodiments. The preparation process flow chart of the invention is shown in figure 1, and the specific steps refer to each embodiment.
Example 1
0.1mol of N-methylimidazole is taken to be heated in a water bath and stirred by magnetic force, and 0.1mol of N-butyl bromide is slowly dropped when the temperature reaches 80 ℃. After the dropwise addition, the temperature is controlled at 85 ℃ and the mixture is stirred until the mixture completely reacts to obtain golden yellow, transparent and sticky liquid. And after the reaction is finished, cooling to 50 ℃, extracting excessive reaction raw materials by ethyl acetate for multiple times, and removing residual ethyl acetate by reduced pressure distillation to obtain the bromo-N-methylimidazole ionic liquid.
The obtained bromo-N-methylimidazole ionic liquid further reacts with phosphotungstic acid to obtain heteropoly acid ionic liquid: weighing 12mmol of bromo-N-methylimidazole ionic liquid, weighing 3mmol of phosphotungstic acid to be completely dissolved in deionized water, slowly dropwise adding a phosphotungstic acid solution while stirring, and gradually generating white precipitates. After the addition was complete, the mixture was refluxed at 60 ℃ for 8 h. And (3) after the reaction is finished, carrying out reduced pressure distillation to remove excessive water and HBr in the reaction solution, and drying at 80 ℃ for 12h to obtain the heteropoly acid ionic liquid.
Obtaining aminated Fe by solvothermal method3O4: separately weighing 4g FeCl3·6H2O and 12g of anhydrous sodium acetate are dissolved in 120mL of ethyl acetateIn glycol, stir at room temperature for 10 min. Then 40mL of ethylenediamine was added and stirred until a stable orange solution was formed. Transferring the reaction solution into a reaction kettle, reacting for 8h at 180 ℃, cooling, collecting black products by using a magnet, washing for a plurality of times by using deionized water and absolute ethyl alcohol until the pH value is 7, and drying for 12h in vacuum at 80 ℃ to obtain the aminated Fe3O4。
Finally, the heteropolyacid ionic liquid is loaded with the amino magnetic composite material by an ultrasonic impregnation method: 0.1g of aminated Fe was taken3O410mL of deionized water was added and dispersed uniformly by sonication. Dissolving 0.5g of heteropoly acid ionic liquid in 10mL of acetone, and slowly dropwise adding aminated Fe in ultrasonic3O4In the method, heteropoly acid ionic liquid and aminated Fe3O4The amino groups on the surface act sufficiently to be fully loaded. And continuing to perform ultrasonic treatment for 10min after the dropwise addition is finished. And after the ultrasonic treatment is finished, vacuum drying is carried out for 12 hours at the temperature of 80 ℃, excessive acetone is removed, and the heteropoly acid ionic liquid loaded amino magnetic composite material is finally obtained.
The ionic liquid-supported aminated magnetic composite material with the date cake type structure heteropoly acid in the embodiment takes bromo-N-methylimidazole ionic liquid as a raw material, and the specific synthesis path is as follows:
the operation steps of examples 2 to 6 are the same as those of example 1, and the raw material substances, raw material formula and preparation condition parameters are shown in Table 1.
TABLE 1 raw material Components and preparation parameters of examples 1 to 6 of the present invention
The jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material prepared by the embodiment of the invention is characterized by means of infrared spectrograms (FTIR), X-ray diffraction patterns (XRD), Transmission Electron Microscope (TEM) photos, Scanning Electron Microscope (SEM) photos, X-ray energy spectrums (XPS) and the like, and is used as a catalyst for simulating catalytic oxidation desulfurization of oil samples.
Fig. 2 to 5 are an infrared spectrum (FTIR), an X-ray diffraction pattern (XRD), a Transmission Electron Microscope (TEM) photograph, a Scanning Electron Microscope (SEM) photograph and an X-ray energy spectrum (XPS), respectively, of the jujube cake-structured heteropoly acid ionic liquid-supported aminated magnetic composite material obtained in example 1 according to the present invention.
As can be seen from FIG. 2(a), 1640cm-1Is a characteristic absorption peak of N-H, 582cm-1Is Fe3O4Characteristic absorption peak of Fe-O bond of (2). FIG. 2(b) has 4 characteristic absorption peaks for a typical Keggin-type heteropolyanion, respectively assigned to the central tetrahedron (P-O): 1080cm-1、(W＝O)：978cm-1，891cm-1And 802cm-1Each corresponds to WO6Bridging (W-O) between co-angle octahedrons in octahedral structurec-W) and (W-O)b—W)。1570cm-1The skeleton C of imidazole ring is the stretching vibration peak of N, 1470cm-1And 1380cm-1Is C-H bending vibration peak on side chain methyl, 1160cm-1Is the C-H bending vibration peak on the imidazole ring. Fig. 2(c), namely: the heteropolyacid ionic liquid loaded amino magnetic composite material reserves Keggin structure of heteropolyacid and main characteristic peaks of ionic liquid and aminated magnetic core.
As can be seen from FIG. 3, the characteristic diffraction peaks (JCPDS 70-0705) of heteropoly acid appear at the 2 theta angles of 6.82 degrees, 8.62 degrees, 9.62 degrees and 10.60 degrees, which are respectively assigned to the crystal faces of (010), (200), (002) and (102), and are consistent with Keggin type heteropolyanions in FI-IR characterization. The characteristic diffraction peaks of the aminated magnetic core at 2 theta angles of 30.35 degrees, 36.41 degrees, 40.97 degrees, 57.20 degrees and 59.45 degrees are basically consistent with the standard spectrum (JCPDS 76-0957) of an orthorhombic crystal structure and are respectively assigned to crystal faces (220), (311), (422), (511) and (446). There were many new diffraction peaks between 15 and 35 degrees, presumably due to the influence of ionic liquids.
TEM and SEM images of the sample from fig. 4. As can be seen from fig. 4(a), the heteropolyacid ionic liquid loaded amino magnetic composite material obtained by loading by the impregnation method has a more regular spherical structure, and the average particle size is about 50-100 nm; and the heteropoly acid ionic liquid can be well dispersed in the gaps of the aminated magnetic material. As is apparent from fig. 4(b), a large amount of heteropoly acid ionic liquid is densely embedded on the surface of the aminated magnetic material, which indicates that the heteropoly acid ionic liquid loaded by the immersion method is more easily dispersed on the surface of the aminated magnetic material to form a "date cake type structure" and is not easy to agglomerate.
From the XPS spectrum of the sample in FIG. 5, the catalyst is composed of six elements of Fe, O, N, P, W and C (from FIG. 5(a)), wherein two characteristic peaks of 710.99 eV and 401.62eV are respectively assigned to Fe of Fe2P3O4And imidazole ring of N1s, indicating successful binding of the heteropolyacid ionic liquid to the aminated magnetic material. Fig. 5(b) shows that C1S shows a broad overlapping signal, and the peak separation process is performed to separate the signal into four characteristic peaks, the binding energies of which are 284.67, 285.39, 286.72 and 289.20eV, respectively, indicating the presence of C-C, C-O, C-S and C-N bonds. W4f As shown in FIG. 5(c), there appears a distinct dual characteristic peak with binding energies of 36.23 and 38.37eV, respectively, corresponding to W4f7/2(-WN) and W4f5/2(—WO3) Spin orbit, indicating W as W6+Exist in the form of (1). Compared with W4f of pure heteropoly acid, W4f7/2The binding energy of (a) is shifted from 34eV to 36.23eV and from 37eV to 38.37eV, which is probably because the W ═ O bond is converted into a weaker W-O-Fe bond after the heteropoly acid ionic liquid is bound to the aminated magnetic material. The binding energy of N1s in FIG. 5(d) is shifted from 399eV to 401.62eV, which illustrates that the heteropolyacid ionic liquid coordinates with the amino groups on the surface of the aminated magnetic material. In FIG. 5(e), Fe2p shows two characteristic peaks corresponding to binding energies 710.99 and 723.54eV, respectively, and Fe-O-C is presumed to be formed. FIG. 5(f) shows a broad peak, and three characteristic peaks, corresponding to binding energies of 529.90 (Fe-O), 531.24 (-OH) and 533.69eV (C-O), were observed after the peak separation treatment. The results show that the heteropoly acid ionic liquid is successfully loaded on the aminated magnetic material, and the Keggin structure of the heteropoly acid ionic liquid is still maintained. By calculating the peak planeAs can be seen, the mass percentages of Fe, W and N are respectively 2.90%, 18.55% and 2.94%.
The following is an example of the catalytic oxidative desulfurization application of example 1 to a simulated oil sample.
Application example 1:
the ionic liquid-supported aminated magnetic composite material with the date cake type structure heteropoly acid obtained in the example 1 is applied to catalytic oxidation desulfurization of simulated oil samples. Preparing a series of simulated oil samples with the concentration (100-2000mg/g) by taking dibenzothiophene as a sulfur source and n-octane as a simulated oil sample, taking 50mL of the simulated oil sample, respectively adding a heteropoly acid ionic liquid loaded amino magnetic composite material with a certain mass (0.005-0.025g), uniformly dispersing the heteropoly acid ionic liquid loaded amino magnetic composite material by ultrasonic treatment, and rapidly adding H2O2And (3) the solution (30 wt%) (4.00-12.00 mu L), and after ultrasonic treatment for a certain time (2-20min) under the condition of 305-345K, separating the catalyst and the simulated oil sample under the action of an external magnetic field, and extracting 5mL of acetonitrile. The residual concentration of dibenzothiophene in n-octane was analyzed by a PERSEE G5 gas chromatograph (equipped with a KB-5 capillary column 30 m. times.0.32 mm. times.0.50 μm) and a flame ionization detector (under the analysis conditions of 190 ℃ for column temperature, 220 ℃ for detector temperature, 220 ℃ for inlet temperature, and 1 μ L for sample introduction). The desulfurization rate X was calculated according to the formula (1), and an isothermal adsorption curve was plotted:
in the formula: x-simulated oil sample desulfurization rate;
C0simulation of the sulphur content in the oil sample before desulfurization, mg/g
CtSimulation of the sulphur content of the oil sample after desulfurization, mg/g
The ultrasonic time and H are investigated by a single factor method2O2The influence of the dosage, the reaction temperature, the catalyst dosage and the like on the catalytic oxidation desulfurization performance of the obtained material obtains the optimal catalytic degradation conditions, namely: 0.025g of catalyst to catalyze and oxidize 50mL of simulated oil sample with the concentration of 500mg/g, and n (O) at 323K: n (S) is 8:1, and when the ultrasonic time is 10min, the catalytic degradation rate reaches 88.13%; catalytic reduction after 5 times of catalyst reuseThe dissolution rate is reduced by only 2.51%, which shows that the material has good catalytic desulfurization performance and reusability.
Application example 2:
the heteropolyacid ionic liquid supported aminated magnetic composite material obtained in the example 3 is applied to catalytic oxidation desulfurization of a simulated oil sample. The procedure was as in application example 1. The ultrasonic time and H are optimized by a response surface method2O2The influence of the dosage, the reaction temperature, the catalyst dosage and the like on the catalytic oxidation desulfurization performance of the obtained material obtains the optimal catalytic degradation conditions, namely: 0.02g of catalyst is used for catalytic oxidation of 50mL of simulated oil sample with the concentration of 500mg/g, and n (O) is measured at 323K: n (S) is 4:1, and the catalytic degradation rate reaches 95.22% when the ultrasonic time is 5 min; the catalytic degradation rate of the catalyst is only reduced by 1.82 percent after the catalyst is repeatedly used for 5 times, which shows that the material has good catalytic desulfurization performance and reusability, and is a catalyst with excellent performance.
Experiments prove that the heteropolyacid ionic liquid loaded aminated magnetic composite material comprises the following components in percentage by weight: the method has simple operation steps and low cost, and the obtained heteropolyacid ionic liquid loaded aminated magnetic composite material has a jujube cake type structure; the magnetic separation is realized under an external magnetic field; the catalyst has excellent catalytic desulfurization effect on catalytic oxidation desulfurization of a simulated oil sample, and is a potential high-quality catalyst.
Claims (8)
1. A preparation method of a jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material is characterized by comprising the following steps: the method comprises the following steps: preparing heteropoly acid ionic liquid by adopting a substitution reaction; the preparation method of the aminated magnetic composite material by adopting a solvothermal method comprises the following specific steps: dissolving ferric iron and acetate in ethylene glycol; the mass ratio of the ferric iron to the acetate is 1: 1-1: 10, the mass concentration of the ferric iron in the ethylene glycol is 20-400 g/L, and the mass concentration of the acetate in the ethylene glycol is 40-600 g/L; stirring for 5-30 min at room temperature; then adding 5-80mL of organic polyamine, and stirring until a stable orange solution is formed; transferring the reaction solution into a reaction kettle, and reacting for 2-24 h at 100-240 ℃; cooling, performing magnetic separation, washing until the pH value is 7, and performing vacuum drying to obtain the aminated magnetic composite material; and then loading the heteropoly acid ionic liquid on the aminated nano magnetic material by an ultrasonic impregnation method, and finally obtaining the heteropoly acid ionic liquid loaded amino nano magnetic composite material.
2. The preparation method of the jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material according to claim 1, characterized in that: the preparation method of the heteropoly acid ionic liquid comprises the following specific steps: slowly dripping halogenated hydrocarbon into N-methylimidazole or pyridine during magnetic stirring, heating and refluxing, and continuously refluxing and stirring until complete reaction; cooling after the reaction is finished, extracting excessive reaction raw materials with ethyl acetate for multiple times, and removing residual ethyl acetate by reduced pressure distillation to obtain ionic liquid; and further slowly dropwise adding a phosphotungstic acid aqueous solution under stirring, continuously refluxing after dropwise adding is finished, carrying out reduced pressure distillation after the reaction is finished, removing excessive water and byproducts in the reaction solution, and drying to obtain the heteropoly acid ionic liquid.
3. The preparation method of the jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material according to claim 2, characterized in that: the halogenated hydrocarbon is one of C4-C12 chlorinated or brominated hydrocarbon; the mass ratio of the N-methylimidazole or pyridine to the halogenated hydrocarbon is 0.5: 1-1: 5; the reflux stirring reaction temperature of the N-methylimidazole or pyridine and the halogenated hydrocarbon is 60-150 ℃, and the reaction time is 2-24 hours; the phosphotungstic acid aqueous solution is a saturated solution; the mass ratio of the ionic liquid to the phosphotungstic acid is 2: 1-8: 1; after the dropwise addition is finished, continuously refluxing for 2-12 h; the drying temperature is 60-120 ℃, and the drying time is 2-24 h.
4. The preparation method of the jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material according to claim 3, characterized in that: the mass ratio of the N-methylimidazole or pyridine to the halogenated hydrocarbon is 1: 1-1: 2; the reflux stirring reaction temperature of the N-methylimidazole or pyridine and the halogenated hydrocarbon is 80-100 ℃, and the reaction time is 6-10 h; the mass ratio of the ionic liquid to the phosphotungstic acid is 3: 1-5: 1; after the dropwise addition is finished, continuously refluxing for 6-10 h; the drying temperature is 80-100 ℃, and the drying time is 6-10 h.
5. The preparation method of the jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material according to claim 1, characterized in that: the ferric iron is one of ferric trichloride and ferric sulfate, and the acetate is one of sodium acetate or ammonium acetate; the mass concentration of the ferric iron in the ethylene glycol is 40-120 g/L, the mass concentration of acetate in the ethylene glycol is 60-180 g/L, the organic polyamine is one of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylpentamine, and the dosage of the organic polyamine is 20-60 mL; the reaction temperature in the reaction kettle is 150-200 ℃, and the reaction time is 10-20 h.
6. The preparation method of the jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material according to claim 1, characterized in that: the preparation method of the heteropolyacid ionic liquid loaded aminated composite material specifically comprises the following steps: respectively ultrasonically dispersing an aminated magnetic composite material into an aqueous solution to enable the mass concentration of the aminated magnetic composite material to be 5-100 g/L, dissolving the prepared heteropoly acid ionic liquid into acetone to enable the mass concentration of the heteropoly acid ionic liquid to be 20-500 g/L, slowly dropwise adding the heteropoly acid ionic liquid into the aminated magnetic composite material to be ultrasonically dispersed into the aqueous solution to enable the mass ratio of the aminated magnetic composite material to the heteropoly acid ionic liquid to be 1: 1-1: 10; continuing to perform ultrasonic treatment for 5-30 min after the dropwise addition is finished; and after the reaction is finished, vacuum drying for 2-24 hours at 30-100 ℃ to obtain the heteropolyacid ionic liquid loaded amination composite material.
7. The preparation method of the jujube cake type structure heteropoly acid ionic liquid loaded aminated magnetic composite material according to claim 1, characterized in that: the mass concentration of the aminated magnetic composite material in water is 10-40 g/L, the mass concentration of the heteropoly acid ionic liquid in acetone is 50-150 g/L, and the mass ratio of the aminated magnetic composite material to the heteropoly acid ionic liquid is 1: 4-1: 6.
8. The application of the ionic liquid-supported aminated magnetic composite material of the heteropoly acid with the jujube cake type structure in catalyzing desulfurization of a petroleum sample is characterized in that the ionic liquid-supported aminated magnetic composite material of the heteropoly acid with the jujube cake type structure is prepared by the method of claim 1, and the specific catalytic desulfurization method comprises the following steps: under the condition of room temperature oscillation, adding 0.2-5 g of heteropolyacid ionic liquid-loaded aminated magnetic composite material in a jujube cake type structure in each liter of simulated oil sample, performing ultrasonic treatment to uniformly disperse the heteropolyacid ionic liquid-loaded aminated magnetic composite material, and quickly adding H2O20.04-10 mL of solution, separating the catalyst and a simulated oil sample under the action of an external magnetic field after carrying out ultrasonic treatment for a certain time, and extracting 5mL of acetonitrile; under the condition of 305-; the desulfurization rate can be more than 85%.
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