CN115739176A - Preparation method of vacancy polyacid-based ionic liquid supported catalyst, product and application of product - Google Patents
Preparation method of vacancy polyacid-based ionic liquid supported catalyst, product and application of product Download PDFInfo
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Abstract
The invention discloses a preparation method of a vacancy polyacid based ionic liquid supported catalyst, a product and application thereof. The method has simple operation process, adopts heterogeneous catalyst, is easy to recover, and has better oxidation removal effect on thiophene sulfides in oil products. In particular, for dibenzothiophene, a small amount of hydrogen peroxide (H) is used 2 O 2 30 wt%) as an oxidizing agent, can realize high-efficiency and rapid desulfurization under mild conditions. The catalyst has the characteristics of high catalytic efficiency, stable structure, good circulation stability and the like.
Description
Technical Field
The invention belongs to the field of material preparation and catalytic reaction, and particularly relates to a preparation method of a vacancy polyacid-based ionic liquid supported catalyst, a product and application thereof.
Background
With the continuous development of the modern construction of society, the problems of serious air pollution, acid rain and the like caused by the improper discharge of sulfur oxides (SOx) and sulfate particles generated by the combustion of a large amount of sulfur-containing fuel cause great harm to the health of human beings.
Therefore, improving fuel quality, producing clean fuel, and reducing sulfur content emissions are one of the global concerns. At present, the domestic and foreign desulfurization process mainly comprises methods such as Hydrodesulfurization (HDS), oxidation Desulfurization (ODS), extraction Desulfurization (EDS), adsorption Desulfurization (ADS) and the like. Wherein the conventional Hydrodesulfurization (HDS) technology is limited by the need to consume a large amount of hydrogen, the severe reaction conditions and the large equipment investment, and is difficult to remove thiophene sulfides in fuels, so that it is not suitable for the current ultra-low fuel desulfurization target. Oxidative Desulfurization (ODS) is favored as a simple, efficient and most promising desulfurization technique because of its mild reaction conditions and no need to consume expensive hydrogen during the reaction.
Polyoxometallates (POMs), as a class of metal oxide clusters, have enormous application potential in catalysis due to their abundant structure and excellent redox properties. Meanwhile, the POMs can show unique acidic, multifunctional and 'pseudo liquid phase' behaviors under mild conditions, and the acidity and redox performance of the POMs can be adjusted in a wide range by changing chemical components of the POMs, so that the POMs can be used as solid acid catalysts and electron transfer catalysts for researching catalytic oxidation desulfurization properties, and for example, patent CN 113083368A proposes a metal organic framework supported heteropoly acid oxidation desulfurization catalyst.
However, the problems of low specific surface area and high solubility in organic solvents have limited the further use of polyoxometallates in oxidative desulfurization reactions.
Therefore, the development of a heterogeneous catalyst which can effectively improve the specific surface area and chemical stability of the catalyst under the premise of ensuring the oxidation activity of the absent polyacid is of great significance.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of the vacancy polyacid-based ionic liquid supported catalyst.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a vacancy polyacid-based ionic liquid supported catalyst comprises the following steps,
preparation of deficient polyoxometallate Na 9 [A-PW 9 O 34 ]·7H 2 O；
Obtaining polyacid-based ionic liquid POMs-IL by adopting ion exchange;
obtaining the vacancy polyacid-based ionic liquid supported catalyst POMs-IL/SiO by an impregnation method 2 。
As a preferred scheme of the preparation method of the vacancy polyacid-based ionic liquid supported catalyst, the vacancy polyacid-based ionic liquid supported catalyst comprises the following steps: the deficient polyoxometallate Na 9 [A-PW 9 O 34 ]·7H 2 O, the preparation method comprises the following steps,
dissolving sodium tungstate in water, and stirring until the solid is completely dissolved;
then dropwise adding phosphoric acid, adjusting the pH value to 8.9-9.0, dropwise adding glacial acetic acid while stirring to generate a large amount of white precipitate, finally measuring the pH value of the solution to be 7.5 +/-0.3, stirring the solution for 1h, performing suction filtration to obtain the precipitate, and drying to obtain Na 9 [A-PW 9 O 34 ]·7H 2 O。
As a preferable scheme of the preparation method of the vacancy polyacid-based ionic liquid supported catalyst, the vacancy polyacid-based ionic liquid supported catalyst comprises the following steps: the molar ratio of the sodium tungstate to the phosphoric acid is 6.
As a preferred scheme of the preparation method of the vacancy polyacid-based ionic liquid supported catalyst, the vacancy polyacid-based ionic liquid supported catalyst comprises the following steps: the preparation method of the polyacid-based ionic liquid POMs-IL comprises the following steps,
the absent polyacid Na 9 [A-PW 9 O 34 ]·7H 2 Dissolving O in deionized water to form a solution A;
dissolving 1-hexadecyl-3-methylimidazole chloride serving as an ionic liquid in deionized water to form a solution B;
and dropwise adding the solution B into the solution A to form a precipitate, continuously stirring for 1h, carrying out suction filtration to obtain the precipitate, and drying at the temperature of between 60 and 100 ℃ for 6 to 24h to obtain the POMs-IL precursor.
As a preferable scheme of the preparation method of the vacancy polyacid-based ionic liquid supported catalyst, the vacancy polyacid-based ionic liquid supported catalyst comprises the following steps: the mol ratio of the vacancy polyacid to the ionic liquid is 1.
As a preferred scheme of the preparation method of the vacancy polyacid-based ionic liquid supported catalyst, the vacancy polyacid-based ionic liquid supported catalyst comprises the following steps: the vacancy polyacid-based ionic liquid supported catalyst POMs-IL/SiO 2 A process for the preparation thereof, comprising,
dissolving POMs-IL in acetonitrile, adding silicon dioxide, and stirring uniformly;
transferring the mixture into a hydrothermal reaction kettle, reacting for 12-48 h at 60-100 ℃, cooling, stirring and drying at 50 ℃ to obtain the vacancy polyacid-based ionic liquid supported catalyst.
As a preferred scheme of the preparation method of the vacancy polyacid-based ionic liquid supported catalyst, the vacancy polyacid-based ionic liquid supported catalyst comprises the following steps: the solid-to-liquid ratio of POMs-IL, silicon dioxide and acetonitrile is 0.5g:1.5g:60mL.
As a preferred scheme of the preparation method of the vacancy polyacid-based ionic liquid supported catalyst, the vacancy polyacid-based ionic liquid supported catalyst comprises the following steps: the hydrothermal reaction temperature is 80 ℃, and the reaction time is 24 hours; the silicon dioxide is nano silicon dioxide, and the particle size of the silicon dioxide is 7-40 nm.
The invention further aims to overcome the defects in the prior art and provide a product prepared by the preparation method of the vacancy polyacid-based ionic liquid supported catalyst.
The invention also aims to overcome the defects in the prior art and provide the application of the product prepared by the preparation method of the vacancy polyacid-based ionic liquid supported catalyst in oxidative desulfurization of fuel oil.
The invention has the beneficial effects that:
the prepared default polyacid based ionic liquid supported catalyst has high activity and stability, can be recycled, is harmless to human bodies and environment, and is an environment-friendly material; compared with the traditional catalyst, the catalyst prepared by the invention can completely remove thiophene sulfides which are difficult to remove in fuel oil in a short time; meanwhile, the preparation method adopted by the invention has mild conditions, no pollution and simple operation, and meets the requirement of environmental protection.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a schematic diagram of the formation process of the ionic liquid supported catalyst with the deficient polyacid group prepared by the invention.
FIG. 2 is an infrared spectrum of the vacancy polyacid based ionic liquid supported catalyst prepared by the invention.
FIG. 3 is a PXRD diagram of a deficient polyacid based ionic liquid supported catalyst prepared in accordance with the present invention.
FIG. 4 is SEM photograph of the ionic liquid supported catalyst with deficient polyacid group prepared in the invention, and A is the Na deficient polyacid 9 [A-PW 9 O 34 ]·7H 2 Photograph of O, B is that of the ionic liquid with the polyacid group at the absent positionPanels C and D are panels of supported catalysts.
FIG. 5 is a diagram illustrating the performance of oxidative desulfurization of the catalyst supported on the ionic liquid with vacancy and multiple acid groups.
FIG. 6 is a diagram showing the effect of the lack-position polyacid group ionic liquid supported catalyst prepared by the present invention on the wide applicability of different sulfides.
FIG. 7 is a test chart of the cycle performance of the ionic liquid supported catalyst with the defect multi-acid groups prepared by the invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and it will be appreciated by those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention and that the present invention is not limited by the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Sodium tungstate, phosphoric acid and glacial acetic acid are all from the alatin pharmaceutical industry, 1-hexadecyl-3-methylimidazolium chloride is from Shanghai source leaf Biotech Co., ltd, nano-silicon dioxide is from the alatin pharmaceutical industry, CAS No. 112945-52-5, particle size: 7-40nm, specific surface area (BET): 100m 2 (ii) in terms of/g. Other raw materials are all common commercial products.
Example 1
The embodiment provides a preparation method of a vacancy polyacid-based ionic liquid supported catalyst, which comprises the following specific steps:
(1) Preparation of deficient polymetallicOxometallate Na 9 [A-PW 9 O 34 ]·7H 2 O：
Dissolving 120g of sodium tungstate in 150mL of water, stirring until the solid is completely dissolved, then dropwise adding 4.0mL of 0.06mol (85%) phosphoric acid, and adjusting the pH to 9.0;
adding 22.4mL (0.4 mol) of glacial acetic acid dropwise under stirring to generate a large amount of white precipitate, finally measuring the pH of the solution to be 7.5 +/-0.3, stirring the solution for 1h, performing suction filtration to obtain the precipitate, and drying to obtain Na 9 [A-PW 9 O 34 ]·7H 2 O。
(2) Obtaining POMs-IL by adopting an ion exchange method:
2.564g of the deficient polyacid Na 9 [A-PW 9 O 34 ]·7H 2 Dissolving O in 100ml of deionized water to form a solution A;
dissolving 3.087g of ionic liquid 1-hexadecyl-3-methylimidazolium chloride in 100ml of deionized water to form a solution B;
dropwise adding the solution B into the solution A to form a white precipitate, wherein the molar ratio of the vacancy polyacid to the ionic liquid is 1;
stirring for 1h, filtering out precipitate, washing for multiple times until no Cl is detected in the filtrate - And carrying out suction filtration to obtain a precipitate, and drying in a blast drying oven at 80 ℃ for 12h to obtain the POMs-IL.
(3) The POMs-IL/SiO are obtained by the dipping method 2 ：
Dissolving 0.5g of POMs-IL in 60mL of acetonitrile, adding 1.0g of nano silicon dioxide, stirring the mixture for 30min at 50 ℃, transferring the mixed solution to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and placing the hydrothermal reaction kettle into a forced air drying oven to react for 24h at 80 ℃;
cooling, stirring and drying at 50 deg.C to obtain the vacancy polyacid-based ionic liquid supported catalyst POMs-IL/SiO 2 (1:2)。
The preparation process of the vacancy polyacid-based ionic liquid supported catalyst material is shown in figure 1.
Example 2
The embodiment provides a preparation method of a vacancy polyacid based ionic liquid supported catalyst, which comprises the following specific steps:
(1) Preparation of deficient polyoxometallate Na 9 [A-PW 9 O 34 ]·7H 2 O is specifically the same as in step (1) in example 1.
(2) POMs-IL were obtained by ion exchange, specifically the same as in step (2) in example 1.
(3) The POMs-IL/SiO are obtained by the dipping method 2 ：
Dissolving 0.5g of POMs-IL in 60mL of acetonitrile, adding 1.5g of nano silicon dioxide, stirring the mixture for 30min at 50 ℃, transferring the mixed solution to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and placing the hydrothermal reaction kettle into a forced air drying oven to react for 24h at 80 ℃;
cooling, stirring and drying at 50 deg.C to obtain the default polyacid-based ionic liquid supported catalyst POMs-IL/SiO 2 (1:3)。
Example 3
The embodiment provides a preparation method of a vacancy polyacid based ionic liquid supported catalyst, which comprises the following specific steps:
(1) Preparation of deficient polyoxometallate Na 9 [A-PW 9 O 34 ]·7H 2 O is specifically the same as in step (1) in example 1.
(2) POMs-IL were obtained by ion exchange in the same manner as in step (2) in example 1.
(3) The POMs-IL/SiO are obtained by the dipping method 2 ：
Dissolving 0.5g of POMs-IL in 60mL of acetonitrile, adding 2.0g of nano silicon dioxide, stirring the mixture for 30min at 50 ℃, transferring the mixed solution to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and placing the hydrothermal reaction kettle into a forced air drying oven to react for 24h at 80 ℃;
cooling, stirring and drying at 50 deg.C to obtain the default polyacid-based ionic liquid supported catalyst POMs-IL/SiO 2 (1:4)。
The infrared characteristic peaks of polyoxometallate, ionic liquid and silica are evident from figure 2, indicating successful preparation of the supported catalyst.
From FIG. 3, it is apparent that the X-ray diffraction peak of silica is weak, and the characteristic peaks belonging to polyoxometallate and ionic liquid are weak due to the influence of the amorphous peak of silica.
From FIG. 4, it is evident that the morphology change process during the catalyst preparation process and the morphology of the loaded catalyst, it can be seen that the vacancy polyacid PW 9 From the original regular crystal shape to the surface waxy layer structure with good lipophilicity of the polyacid-based ionic liquid, and finally to the small-particle supported catalyst with high specific surface area.
Example 4
The oxidation desulfurization performance test of the supported catalyst prepared in the embodiment 1 to 3 specifically comprises the following steps:
1. configuration of simulated oil
0.290g of Dibenzothiophene (DBT) and 0.315g of tetradecane were added to 100mL of n-octane, sonicated for 30min, and configured to 500ppm of a simulated sulfur-containing fuel.
0.216g of Benzothiophene (BT) and 0.315g of tetradecane were added to 100mL of n-octane, sonicated for 30min, and configured to 500ppm of a simulated sulfur-containing fuel.
0.341g of 4,6-dimethyldibenzothiophene (4.6-DMDBT) and 0.315g of tetradecane are added to 100mL of n-octane, and the mixture is subjected to ultrasonic treatment for 30min to prepare 500ppm of simulated sulfur-containing fuel.
2. Oxidation desulfurization experiment of fuel oil
A. 0.01g of the vacancy-deficient polyacid-based ionic liquid supported catalyst prepared in examples 1 to 3 and 32. Mu.L of 30wt% 2 O 2 Adding into 25mL round bottom flask containing 5mL DBT simulated oil, stirring, and reacting at 50 deg.C for 5-30min.
After the reaction was complete, the oil phase was filtered off. And extracting with acetonitrile, separating the upper oil phase, analyzing the sulfur content in the simulated oil by using gas chromatography, and calculating the desulfurization rate.
The desulfurization rate is calculated by the formula:
after many experiments, it was found that 0.01g of the vacancy polyacid-based ionic liquid supported catalyst (POMs-IL/SiO 2 (1, 3)) prepared in example 2 as shown in FIG. 5 was consumed in H% at 30wt of 24. Mu.L 2 O 2 The catalyst is an oxidant, the oxidative desulfurization effect of the reaction at 50 ℃ for 10min is the best, and 100% desulfurization can be realized.
The catalyst POMs-IL/SiO2 (1.
B. 0.01g of the catalyst POMs-IL/SiO prepared in example 2 were each weighed out 2 (1 2 O 2 Adding into 25mL round bottom flask containing 5mL 4.6-DMDBT simulation oil, stirring, and reacting at 50 deg.C for 5-30min. After the reaction was complete, the oil phase was filtered off. And extracting with acetonitrile, separating the upper oil phase, analyzing the sulfur content in the simulated oil by using a gas chromatography, and calculating the desulfurization rate.
C. 0.01g of the catalyst POMs-IL/SiO prepared in example 2 were each weighed out 2 30wt% H2O2 (1. After the reaction was complete, the oil phase was filtered off. And extracting with acetonitrile, separating the upper oil phase, analyzing the sulfur content in the simulated oil by using a gas chromatography, and calculating the desulfurization rate.
Catalyst POMs-IL/SiO prepared as in example 2 2 (1. The result is shown in fig. 6, and the result shows that the vacancy polyacid-based ionic liquid supported catalyst has a good removal effect on the thiophene sulfides, and the thiophene sulfides can be substantially removed in a short time.
Example 5
And (3) testing the cycle performance of the vacancy polyacid-based ionic liquid supported catalyst.
On the basis of the test of oxidative desulfurization performance, the catalyst POMs-IL/SiO prepared in example 2 2 (1.
The invention combines the vacancy polyoxometallate and the ionic liquid by an ion exchange method to form polyacid-based ionic liquid, and then loads the polyacid-based ionic liquid on the nano silicon dioxide to successfully prepare the supported catalyst. The method has simple operation process, adopts heterogeneous catalyst, is easy to recover, and has better oxidation removal effect on thiophene sulfides in oil products. In particular, for dibenzothiophene, a small amount of hydrogen peroxide (H) is used 2 O 2 30 wt%) as oxidant, high-efficiency and quick desulfurization can be realized under mild conditions. The catalyst has the characteristics of high catalytic efficiency, stable structure, good circulation stability and the like.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a vacancy polyacid-based ionic liquid supported catalyst is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparation of deficient polyoxometallate Na 9 [A-PW 9 O 34 ]·7H 2 O；
Ion exchange is adopted to obtain polyacid-based ionic liquid POMs-IL;
obtaining the vacancy polyacid-based ionic liquid supported catalyst POMs-IL/SiO by an impregnation method 2 。
2. The vacancy polyacid-based ionic liquid load of claim 1The preparation method of the type catalyst is characterized by comprising the following steps: the deficient polyoxometallate Na 9 [A-PW 9 O 34 ]·7H 2 O, the preparation method comprises the following steps,
dissolving sodium tungstate in water, and stirring until the solid is completely dissolved;
then dropwise adding phosphoric acid, adjusting the pH value to 8.9-9.0, dropwise adding glacial acetic acid while stirring to generate a large amount of white precipitate, finally measuring the pH value of the solution to be 7.5 +/-0.3, stirring the solution for 1h, performing suction filtration to obtain the precipitate, and drying to obtain Na 9 [A-PW 9 O 34 ]·7H 2 O。
3. The preparation method of the vacancy polyacid-deficient ionic liquid supported catalyst as claimed in claim 2, characterized in that: the molar ratio of the sodium tungstate to the phosphoric acid is 6.
4. A process for producing the vacancy polyacid based ionic liquid supported catalyst of any one of claims 1 to 3, wherein: the preparation method of the polyacid-based ionic liquid POMs-IL comprises the following steps,
the absent polyacid Na 9 [A-PW 9 O 34 ]·7H 2 Dissolving O in deionized water to form a solution A;
dissolving ionic liquid 1-hexadecyl-3-methylimidazolium chloride in deionized water to form a solution B;
and dropwise adding the solution B into the solution A to form a precipitate, continuously stirring for 1h, carrying out suction filtration to obtain the precipitate, and drying at the temperature of between 60 and 100 ℃ for 6 to 24h to obtain the POMs-IL precursor.
5. The method for preparing the vacancy polyacid based ionic liquid supported catalyst of claim 4, wherein: the mole ratio of the vacancy polyacid to the ionic liquid is 1.
6. The method for preparing the vacancy polyacid-based ionic liquid supported catalyst as claimed in any one of claims 1 to 3 and 5, wherein: the vacancy polyacid-based ionic liquid supported catalyst POMs-IL/SiO 2 A process for the preparation thereof, comprising,
dissolving POMs-IL in acetonitrile, adding silicon dioxide, and uniformly stirring;
transferring the mixture into a hydrothermal reaction kettle, reacting for 12-48 h at 60-100 ℃, cooling, stirring and drying at 50 ℃ to obtain the vacancy polyacid-based ionic liquid supported catalyst.
7. The preparation method of the vacancy polyacid-deficient ionic liquid supported catalyst as claimed in claim 6, characterized in that: the solid-to-liquid ratio of POMs-IL, silicon dioxide and acetonitrile is 0.5g:1.5g:60mL.
8. The preparation method of the vacancy polyacid-deficient ionic liquid supported catalyst as claimed in claim 7, wherein: the hydrothermal reaction temperature is 80 ℃, and the reaction time is 24 hours; the silicon dioxide is nano silicon dioxide, and the particle size of the silicon dioxide is 7-40 nm.
9. The ionic liquid supported catalyst with the defect multi-acid group prepared by the preparation method of any one of claims 1 to 8.
10. The application of the vacancy polyacid-based ionic liquid supported catalyst in oxidative desulfurization of fuel oil as claimed in claim 9.
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