CN115125030A - Polyethylene glycol porous ionic liquid and preparation method and application thereof - Google Patents
Polyethylene glycol porous ionic liquid and preparation method and application thereof Download PDFInfo
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- CN115125030A CN115125030A CN202210962730.4A CN202210962730A CN115125030A CN 115125030 A CN115125030 A CN 115125030A CN 202210962730 A CN202210962730 A CN 202210962730A CN 115125030 A CN115125030 A CN 115125030A
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- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
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Abstract
The invention relates to the technical field of porous ionic liquid. The invention provides a polyethylene glycol porous ionic liquid and a preparation method and application thereof, wherein chlorinated polyethylene glycol is mixed with imidazole sodium to obtain imidazole functionalized polyethylene glycol; mixing imidazole functionalized polyethylene glycol with 3-chloropropyltrimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid; mixing the ethanol solution of the porous nano silicon spheres with imidazole functionalized polyethylene glycol ionic liquid, and then reacting to obtain the polyethylene glycol porous ionic liquid. The polyethylene glycol porous ionic liquid obtained by the invention is stable liquid at room temperature, has good thermal stability below 200 ℃, and the structure of the porous nano silicon spheres stably exists in the polyethylene glycol porous ionic liquid; after the catalyst is applied to an adsorption extraction desulfurization process, the desulfurization rate can reach 92.2 percent; has better reusability, and the desulfurization rate is reduced from 92.2 percent to 87.4 percent after 3 times of reutilization.
Description
Technical Field
The invention relates to the technical field of porous ionic liquid, in particular to polyethylene glycol porous ionic liquid and a preparation method and application thereof.
Background
Since the 21 st century, the production and holding of fuel-powered vehicles has increased dramatically, resulting in a dramatic increase in the consumption of vehicle fuel and an increase in the emission of exhaust gases from vehicles which are inconvenient to use industrial desulfurization processes. Under the large environment that the global fuel consumption is continuously increased, the sulfide in the fuel oil brings serious influence to the environment, and the phenomena of acid rain, haze and the like which seriously harm the health safety of people and the environmental safety are not optimistic, so that the fuel oil desulfurization is very necessary. The main methods for desulfurizing fuel oil include Hydrodesulfurization (HDS) and non-hydrodesulfurization (NHDS). Non-hydrodesulfurization (NHDS) is a desulfurization technique proposed for some disadvantages of the prior art hydrodesulfurization, and mainly includes Oxidative Desulfurization (ODS), Biological Desulfurization (BDS), Adsorptive Desulfurization (ADS), and Extractive Desulfurization (EDS).
The adsorption desulfurization method has a good removal effect on thiophene sulfur-containing compounds, is simple in operation, low in cost and relatively few in by-products harmful to the environment, but the adsorbent has the problems that active components are easy to lose, a catalyst is easy to poison or inactivate and the like, and is suitable for being used in small-sized oil refineries in industry. The Extraction Desulfurization (EDS) mechanism is that the solubility difference between the oil product and the extractant is formed by utilizing the polarity difference between the sulfide and the oil product to separate, and finally the dissolution of the sulfide in the two phases of the oil product and the extractant is balanced, so that the purpose of removing the sulfide is realized. Because the extraction desulfurization has low requirements on operation conditions, can be carried out under the conditions of normal temperature, normal pressure and even low temperature and low pressure, has little influence on the properties of substances in fuel oil, and can be recycled, the extraction desulfurization technology becomes a popular research project at present, but the efficiency of the extraction desulfurization is low, and the development of the extraction desulfurization technology in the desulfurization field is influenced.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a polyethylene glycol porous ionic liquid and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of polyethylene glycol porous ionic liquid, which comprises the following steps:
(1) mixing chlorinated polyethylene glycol and imidazole sodium to obtain imidazole functionalized polyethylene glycol;
(2) mixing imidazole functionalized polyethylene glycol with 3-chloropropyltrimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid;
(3) mixing the ethanol solution of the porous nano silicon spheres with imidazole functionalized polyethylene glycol ionic liquid, and then reacting to obtain the polyethylene glycol porous ionic liquid.
Preferably, the mole ratio of the chlorinated polyethylene glycol to the imidazole sodium in the step (1) is 1: 1.8-2.2; the molecular weight of the chlorinated polyethylene glycol is 400-800.
Preferably, the mixing temperature in the step (1) is 75-85 ℃, the mixing stirring time is 10-14 h, and the stirring speed is 900-1100 r/min.
Preferably, the molar ratio of the imidazole functionalized polyethylene glycol to the 3-chloropropyltrimethoxysilane in the step (2) is 0.4-0.6: 1.
preferably, the mixing temperature in the step (2) is 75-85 ℃, the mixing time is 10-14 h, and the mixing speed is 900-1100 r/min.
Preferably, the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid in the step (3) is 2-6: 94-98.
Preferably, the mass volume ratio of the porous nano silicon spheres to the ethanol in the step (3) is 0.14-0.60 g: 20 mL.
Preferably, the reaction temperature in the step (3) is 75-85 ℃, the reaction stirring time is 8-12 h, and the stirring speed is 900-1100 r/min.
The invention also provides the polyethylene glycol porous ionic liquid prepared by the preparation method.
The invention also provides application of the polyethylene glycol porous ionic liquid in an adsorption extraction desulfurization process.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of polyethylene glycol porous ionic liquid, which comprises the steps of mixing chlorinated polyethylene glycol and imidazole sodium to obtain imidazole functionalized polyethylene glycol; mixing imidazole functionalized polyethylene glycol with 3-chloropropyltrimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid; mixing the ethanol solution of the porous nano silicon spheres with imidazole functionalized polyethylene glycol ionic liquid, and then reacting to obtain the polyethylene glycol porous ionic liquid. The preparation method provided by the invention has simple and convenient working procedures, the obtained polyethylene glycol porous ionic liquid is stable liquid at room temperature, has good thermal stability below 200 ℃, and the structure of the porous nano silicon spheres stably exists in the polyethylene glycol porous ionic liquid.
(2) The invention provides a polyethylene glycol porous ionic liquid, which is applied to desulfurization, and comprises the hydrogen bonding effect between hydroxyl on the surface of a silicon ball and thiophene, the electrostatic effect between a carbon chain group in polyethylene glycol and thiophene, and the strong aromaticity of imidazole cations in the polyethylene glycol porous ionic liquid, so that after the polyethylene glycol porous ionic liquid is contacted with Thiophene (TP), due to the strong polarity of the imidazole cations, the thiophene discrete pi bonds are induced to generate polarization, and the polarized pi bonds and the porous imidazole functionalized silicon-based polyethylene glycol porous ionic liquid generate pi-pi complexing effect, thereby obviously improving the desulfurization effect.
(3) After the polyethylene glycol porous ionic liquid provided by the invention is applied to an adsorption extraction desulfurization process, the desulfurization rate can reach 92.2%; has better reusability, and the desulfurization rate is reduced from 92.2 percent to 87.4 percent after 3 times of reutilization.
Drawings
FIG. 1 shows that the molecular weight of polyethylene glycol is 800, and the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid is 2: an FT-IR spectrum of the 98 polyethylene glycol porous ionic liquid;
FIG. 2 shows that the molecular weight of polyethylene glycol is 800, and the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid is 2: 98, 2(a) is a TEM analysis image under a magnification of 1: 100000, 2(b) is a TEM analysis image under a magnification of 1: 50000, 2(c) is a TEM analysis image under a magnification of 1: 20000, 2(e) is an EDS energy spectrum of nitrogen element of the polyethylene glycol porous ionic liquid under a magnification of 1: 50000, 2(f) is an EDS energy spectrum of oxygen element of the polyethylene glycol porous ionic liquid under a magnification of 1: 50000, and 2(g) is an EDS energy spectrum of silicon element of the polyethylene glycol porous ionic liquid under a magnification of 1: 50000;
FIG. 3 shows that the molecular weight of polyethylene glycol is 800, and the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid is 2: TG and DTG profiles of 98 polyethylene glycol porous ionic liquids;
FIG. 4 shows that the molecular weight of polyethylene glycol is 800, and the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid is 2: 98N of polyethylene glycol porous ionic liquid 2 An adsorption capacity graph;
FIG. 5 is a graph of desulfurization performance of Thiophene (TP) by polyethylene glycol porous ionic liquids obtained from polyethylene glycols of different molecular weights;
FIG. 6 is a diagram of desulfurization performance of a polyethylene glycol porous ionic liquid to Thiophene (TP) obtained by mixing porous nano-silicon spheres and imidazole functionalized polyethylene glycol ionic liquid at different mass ratios;
FIG. 7 is a graph of desulfurization performance of Thiophene (TP) by polyethylene glycol porous ionic liquid at different reaction temperatures;
FIG. 8 is a graph of desulfurization performance of different amounts of polyethylene glycol porous ionic liquids on Thiophene (TP);
FIG. 9 is a graph of desulfurization performance of polyethylene glycol porous ionic liquid on different simulated oils;
FIG. 10 is a FT-IR analysis characterization chart of the porous ionic liquid of polyethylene glycol prepared in example 2 before and after desulfurization;
FIG. 11 is a chart of the reusability study of the porous ionic liquid of polyethylene glycol prepared in example 2.
Detailed Description
The invention provides a preparation method of polyethylene glycol porous ionic liquid, which comprises the following steps:
(1) mixing chlorinated polyethylene glycol and imidazole sodium to obtain imidazole functionalized polyethylene glycol;
(2) mixing imidazole functionalized polyethylene glycol with 3-chloropropyltrimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid;
(3) mixing the ethanol solution of the porous nano silicon spheres with imidazole functionalized polyethylene glycol ionic liquid, and then reacting to obtain the polyethylene glycol porous ionic liquid.
In the invention, the chlorinated polyethylene glycol in the step (1) can be purchased or prepared, and the invention provides a preparation method of the chlorinated polyethylene glycol, which comprises the following steps:
mixing polyethylene glycol, thionyl chloride and pyridine to obtain chlorinated polyethylene glycol.
In the invention, the molar ratio of the polyethylene glycol, the thionyl chloride and the pyridine is preferably 5-7: 5-7: 0.5 to 1.5, and more preferably 5.5 to 6.5: 5.5-6.5: 0.8 to 1.2, more preferably 6: 6: 1.
in the invention, the mixing is carried out in an oil bath, and the mixing temperature is preferably 35-45 ℃, more preferably 38-42 ℃, and more preferably 40 ℃; the mixing and stirring time is preferably 2-4 h, more preferably 2.5-3.5 h, and even more preferably 3 h; the rotation speed is preferably 900-1100 r/min, more preferably 950-1050 r/min, and even more preferably 1000 r/min.
In the invention, after the reaction is finished, the mixed liquid is poured into a separating funnel, ether is added, shaking and oscillation are carried out, standing and layering are carried out, and the lower layer is chlorinated polyethylene glycol.
In the invention, the molar volume ratio of the polyethylene glycol to the diethyl ether is preferably 5-7 mol: 1-3L, more preferably 5.5-6.5 mol: 1.5 to 2.5L, more preferably 6 mol: 2L.
In the invention, the preparation process of the chlorinated polyethylene glycol is as follows:
in the invention, the imidazole sodium in the step (1) can be obtained by purchase or preparation, and the invention provides a preparation method of the imidazole sodium, which comprises the following steps:
and (3) reacting sodium ethoxide and imidazole in ethanol to obtain the imidazole sodium.
In the invention, the molar volume ratio of sodium ethoxide, ethanol and imidazole is preferably 0.8-1.2 mol: 1.8-2.2L: 0.8 to 1.2mol, more preferably 0.9 to 1.1 mol: 1.9-2.1L: 0.9 to 1.1mol, more preferably 1 mol: 2L: 1 mol.
In the invention, the reaction is carried out in an oil bath, and the temperature of the reaction is preferably 65-75 ℃, more preferably 68-72 ℃, and more preferably 70 ℃; the stirring time of the reaction is preferably 8-12 h, more preferably 9-11 h, and even more preferably 10 h; the rotation speed is preferably 900-1100 r/min, more preferably 950-1050 r/min, and even more preferably 1000 r/min.
In the present invention, the molar ratio of the chlorinated polyethylene glycol to the sodium imidazolide in the step (1) is preferably 1: 1.8 to 2.2, and more preferably 1: 1.9 to 2.1, more preferably 1: 2; the molecular weight of the chlorinated polyethylene glycol is preferably 400-800, more preferably 500-700, and even more preferably 600.
In the invention, the mixing temperature in the step (1) is preferably 75-85 ℃, more preferably 78-82 ℃, and more preferably 80 ℃; the mixing time is preferably 10-14 h, more preferably 11-13 h, and even more preferably 12 h; the stirring speed is preferably 900 to 1100r/min, more preferably 950 to 1050r/min, and still more preferably 1000 r/min.
In the invention, after the reaction in the step (1) is finished, the mixed liquid is placed in acetone, sodium chloride is precipitated, and the supernatant is taken and subjected to reduced pressure rotary evaporation to remove the acetone, so that the imidazole functionalized polyethylene glycol is obtained.
In the invention, the temperature of the reduced pressure rotary evaporation is preferably 25-35 ℃, more preferably 28-32 ℃, and more preferably 30 ℃.
In the present invention, the reaction process of step (1) is as follows:
in the invention, the molar ratio of the imidazole functionalized polyethylene glycol to the 3-chloropropyltrimethoxysilane in the step (2) is preferably 0.4-0.6: 1, more preferably 0.45 to 0.55: 1, more preferably 0.5: 1.
in the invention, the mixing temperature in the step (2) is preferably 75-85 ℃, more preferably 78-82 ℃, and even more preferably 80 ℃; the mixing time is preferably 10-14 h, more preferably 11-13 h, and even more preferably 12 h; the stirring speed is preferably 900-1100 r/min, more preferably 950-1050 r/min, and even more preferably 1000 r/min.
In the present invention, the reaction process of step (2) is as follows:
in the invention, the porous nano silicon spheres are prepared in the step (3), and the invention provides a preparation method of the porous nano silicon spheres, which comprises the following steps:
and (3) reacting a mixture of hexadecyl trimethyl ammonium bromide and tetraethyl silicate in an ethanol water solution to obtain the porous nano silicon spheres.
In the invention, before the mixture is added into the ethanol water solution, the ethanol water solution is preferably subjected to ultrasonic treatment, wherein the ultrasonic treatment time is preferably 10-30 min, more preferably 15-25 min, and more preferably 20 min; the frequency of the ultrasonic wave is preferably 35-45 kHz, more preferably 38-42 kHz, and even more preferably 40 kHz.
In the invention, the mole ratio of hexadecyl trimethyl ammonium bromide to tetraethyl silicate in the mixture is preferably 0.8-1.2: 0.8 to 1.2, more preferably 0.9 to 1.1: 0.9 to 1.1, more preferably 1: 1; the volume ratio of water to ethanol in the ethanol water solution is preferably 0.4-0.8: 1, more preferably 0.5 to 0.7: 1, more preferably 0.6: 1.
in the invention, the mass volume ratio of the mixture to the ethanol water solution is preferably 0.4-0.6 g: 40 to 60mL, more preferably 0.45 to 0.55 g: 45-55 mL, more preferably 0.5 g: 50 mL.
In the invention, the reaction is carried out in a water bath, and the reaction temperature is preferably 25-35 ℃, more preferably 28-32 ℃, and more preferably 30 ℃; the reaction time is preferably 4-8 h, more preferably 5-7 h, and even more preferably 6 h; in the reaction process, the stirring speed is preferably 900-1100 r/min, more preferably 950-1050 r/min, and even more preferably 1000 r/min.
In the invention, after the water bath is finished, the obtained sample is centrifugally washed to remove unreacted organic matters and ammonia; the centrifugally washed solution is preferably ethanol; the number of times of the centrifugal washing is preferably 2 to 4 times, and more preferably 3 times.
In the invention, after centrifugal washing, a sample is dried, wherein the drying temperature is preferably 65-75 ℃, more preferably 68-72 ℃, and more preferably 70 ℃; the drying time is preferably 22-26 h, more preferably 23-25 h, and even more preferably 24 h.
In the invention, after drying, calcining the sample, wherein the calcining is carried out in a muffle furnace, and the heating rate of the calcining is preferably 1-3 ℃/min, more preferably 1.5-2.5 ℃/min, and more preferably 2 ℃/min; the target temperature of the calcination is preferably 530-570 ℃, more preferably 540-560 ℃, and more preferably 550 ℃; and (3) performing heat preservation after the target temperature is reached, wherein the heat preservation time is preferably 4-8 h, more preferably 5-7 h, and even more preferably 6 h. And calcining the sample to obtain the porous nano silicon spheres.
In the invention, the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid in the step (3) is preferably 2-6: 94-98, more preferably 3-5: 95-97, more preferably 4: 96.
in the invention, the mass-to-volume ratio of the porous nano silicon spheres to the ethanol in the step (3) is preferably 0.14g to 0.60 g: 20mL, more preferably 0.22g to 0.52 g: 20mL, more preferably 0.30g to 0.44 g: 20 mL.
In the invention, in the step (3), ultrasonic treatment is carried out after the porous nano silicon spheres are dispersed in ethanol, wherein the ultrasonic treatment time is preferably 20-40 min, more preferably 25-35 min, and more preferably 30 min; the frequency of the ultrasonic wave is preferably 35 to 45kHz, more preferably 38 to 42kHz, and even more preferably 40 kHz.
In the invention, the reaction temperature in the step (3) is preferably 75-85 ℃, more preferably 78-82 ℃, and more preferably 80 ℃; the stirring time of the reaction is preferably 8-12 h, more preferably 9-11 h, and even more preferably 10 h; the stirring speed is preferably 900 to 1100r/min, more preferably 950 to 1050r/min, and still more preferably 1000 r/min.
In the invention, after the reaction in the step (3) is finished, the excessive ethanol is removed by rotary evaporation, and the polyethylene glycol porous ionic liquid is obtained.
In the invention, the rotary evaporation temperature is preferably 45-55 ℃, more preferably 48-52 ℃, and more preferably 50 ℃.
The invention also provides the polyethylene glycol porous ionic liquid prepared by the preparation method.
The invention also provides application of the polyethylene glycol porous ionic liquid in an adsorption extraction desulfurization process.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 0.06mol of polyethylene glycol with the average molecular mass of 800, 0.06mol of thionyl chloride and 0.01mol of pyridine into a 200mL round-bottom flask, performing oil bath at 40 ℃, magnetically stirring at the rotating speed of 1000r/min for 3 hours, pouring into a separating funnel, adding 20mL of diethyl ether, shaking, oscillating, standing for layering, wherein the lower layer is chlorinated polyethylene glycol;
dissolving 0.01mol of sodium ethoxide in 20mL of ethanol, adding the solution into a 100mL round-bottom flask, stirring the solution until the solution is uniform, adding 0.01mol of imidazole, performing oil bath at 70 ℃, and performing magnetic stirring at the rotating speed of 1000r/min for 10 hours to obtain imidazole sodium;
adding 0.002mol of imidazole sodium and 0.001mol of chlorinated polyethylene glycol into a 100mL round bottom flask, carrying out oil bath at 80 ℃, stirring at the rotating speed of 1000r/min for 12h, precipitating the reacted sodium chloride in acetone, taking supernate, and carrying out reduced pressure rotary evaporation at 30 ℃ to remove acetone to obtain imidazole functionalized polyethylene glycol (namely ImPEG);
adding 0.005mol of imidazole functionalized polyethylene glycol and 0.01mol of 3-chloropropyltrimethoxysilane into a 50mL round bottom flask, carrying out oil bath at 80 ℃, and stirring at the rotating speed of 1000r/min for 12h to obtain imidazole functionalized polyethylene glycol ionic liquid;
50mL of an aqueous ethanol solution (water to ethanol volume ratio of 0.6: 1) was added to a 100mL beaker, sonicated at 40kHz for 20min, and then 0.5g of a mixture of cetyltrimethylammonium bromide and tetraethyl silicate was added, wherein the molar ratio of cetyltrimethylammonium bromide to tetraethyl silicate was 1: 1, magnetically stirring for 6 hours in a water bath at the temperature of 30 ℃ at the rotating speed of 1000r/min, centrifuging, taking out, centrifugally washing for 3 times by using ethanol to remove unreacted organic matters and ammonia, centrifugally washing, drying in a 70 ℃ oven for 24 hours, putting a dried sample in a muffle furnace, heating at the speed of 2 ℃/min, and calcining for 6 hours at the constant temperature after the temperature reaches 550 ℃ to obtain porous nano silicon spheres;
dispersing 0.20g of porous nano silicon spheres in 20mL of ethanol, performing ultrasonic treatment at the frequency of 40kHz for 30min, adding the porous nano silicon spheres into 9.80g of imidazole functionalized polyethylene glycol ionic liquid, performing oil bath at 80 ℃, performing magnetic stirring at the rotating speed of 1000r/min for 10h, and performing rotary evaporation at 50 ℃ to remove excessive ethanol, thereby obtaining the polyethylene glycol porous ionic liquid (namely PS-ImPEG) with the porous nano silicon spheres loading of 2%.
The polyethylene glycol porous ionic liquid obtained in the example, imidazole functionalized polyethylene glycol and porous nano silicon spheres were subjected to a Tencor 27 Fourier transform infrared spectrometer (Bruker instruments Co., Ltd., Germany)FT-IR analysis with 4cm resolution -1 The scanning range is 4000-450cm -1 . The experimental results show that the FT-IR spectrogram is shown in FIG. 1, and can be seen from the graph, 2876cm -1 The peak of (A) is a symmetric stretching vibration peak of C-H, 1248cm -1 The peak of (A) is an asymmetric stretching vibration absorption peak of-C-O-C-, 1180cm -1 The skeleton vibration of imidazole ring shows that the polyethylene glycol porous ionic liquid contains a large amount of external crown imidazole functionalized polyethylene glycol, and imidazole cation endows the porous liquid with fluidity; the porous nano silicon spheres are 1090cm -1 Is antisymmetric stretching vibration peak of Si-O-Si, 801cm -1 And 464cm -1 And an obvious symmetric stretching vibration peak of Si-O is shown, which indicates that the structure of the porous nano silicon spheres stably exists in the polyethylene glycol porous ionic liquid.
The polyethylene glycol porous ionic liquid obtained in the embodiment is characterized by adopting a German Zeiss SIGMA type scanning electron microscope, the voltage is set to be 10.0kv, and the magnification is respectively 1: 100000, 1: 50000 and 1: 20000; and (3) carrying out amplification observation on the test position by adopting an accelerating voltage of 20kv, carrying out element qualitative and semi-quantitative analysis on the sample by using an X-ray energy spectrum analyzer, and deriving pictures representing different elements. The experimental results show that the TEM and EDS analyses are shown in FIG. 2, wherein FIG. 2(a) is a TEM analysis picture at a magnification of 1: 100000, FIG. 2(b) is a TEM analysis picture at a magnification of 1: 50000, FIG. 2(c) is a TEM analysis picture at a magnification of 1: 20000, and FIGS. 2(e), (f) and (g) are EDS energy spectra of nitrogen, oxygen and silicon elements of the polyethylene glycol porous ionic liquid at a magnification of 1: 50000 respectively. According to TEM analysis images, clear porous nano silicon spheres can be observed in transmission electron microscope images with different magnifications, which shows that a silicon dioxide framework is firm and cannot collapse in the process of silicon oxidation on the surface of the silicon dioxide framework, and single nano particles are combined together to form a large aggregate due to strong interaction between imidazole functionalized polyethylene glycol and a silane coupling agent, which shows that the structure of the silicon spheres is kept unchanged in a liquid state. And the EDS energy spectrum chart shows that nitrogen, oxygen and silicon elements are uniformly distributed in the polyethylene glycol porous ionic liquid, which indicates that the imidazole functionalized polyethylene glycol is stored in the polyethylene glycol porous ionic liquid except for the corona. Therefore, the structure of the porous nano silicon spheres is well preserved in the polyethylene glycol porous ionic liquid.
The thermal performance of the polyethylene glycol porous ionic liquid obtained in the example was analyzed by a STA449F3 thermogravimetric analyzer (Chiari, Germany), and the polyethylene glycol porous ionic liquid was subjected to N 2 Under the protection of (2), the temperature is increased from room temperature to 800 ℃, and the temperature increase rate is 10 ℃/min. The experimental result shows that the curves of TG and DTG are shown in figure 3, and it can be observed from the figure that the weight loss of 4% in the temperature range of 30-100 ℃ on the TG curve is caused by released moisture, which indicates that the polyethylene glycol porous ionic liquid has good thermal stability below 200 ℃; the weight loss of 62% at 100-400 ℃ may be the gradual decomposition of the organic part in PS-PEG; the weight loss of 16% at 400-700 ℃ on the TG curve is probably the gradual decomposition of the porous nano-silicon spheres PS in the PS-PEG, and the mass loss reaches the balance at about 500 ℃, which is consistent with the data of DTG.
The polyethylene glycol porous ionic liquid (namely PS-ImPEG) and the polyethylene glycol (namely ImPEG) obtained in the embodiment are subjected to N treatment by adopting TRISTARII3020 full-automatic specific surface area and pore analyzer (American Mike instruments Co., Ltd.) 2 Characterization of the amount of adsorption of (1), N obtained 2 The adsorption capacity is shown in figure 4, and it can be seen that polyethylene glycol has no adsorption capacity, which indicates that there are no permanent cavity pores in the liquid, while polyethylene glycol porous ionic liquid has obvious N 2 The adsorption capacity is that the pore structure of the porous nano silicon spheres is reserved in the polyethylene glycol porous ionic liquid.
According to the preparation method of the embodiment, polyethylene glycol porous ionic liquids with polyethylene glycol molecular weights of 400 and 600 are respectively prepared, the prepared polyethylene glycol porous ionic liquids are applied to Thiophene (TP) simulation oil desulfurization, the dosage of the polyethylene glycol porous ionic liquids during desulfurization is 2mL, the dosage of the simulation oil is 10mL, the oil bath temperature is 50 ℃, sulfur content of the polyethylene glycol porous ionic liquids obtained by using polyethylene glycols with different molecular weights is measured by a TSN-2000 type sulfur-nitrogen determinator, and the analysis conditions for measuring the sulfur content are as follows: the FPD detector temperature was 280 ℃, the injection port temperature was 250 ℃, and the hold was 180 s. The experimental result shows that the desulfurization performance of the polyethylene glycol porous ionic liquid obtained from polyethylene glycol with different molecular weights to Thiophene (TP) is shown in fig. 5, and it can be seen from the figure that when the desulfurization time is 30min, the desulfurization rates of the polyethylene glycol with the molecular weights of 400 and 600 are higher than that of the polyethylene glycol with the molecular weight of 800, and after 60min, the desulfurization rates of the three polyethylene glycol porous ionic liquids are almost the same, and along with the prolonging of time, the desulfurization rate increase speed of the polyethylene glycol porous ionic liquid with the molecular weight of 800 is obviously higher than that of the other two polyethylene glycol porous ionic liquids, which is probably because the larger the average molecular weight of the polyethylene glycol is, the stronger the electrostatic effect is, and the desulfurization rate is enhanced therewith. When the desulfurization time is 150min, the desulfurization rate of the polyethylene glycol porous ionic liquid with the polyethylene glycol molecular weight of 800 reaches an equilibrium value, and the highest desulfurization rate is 90.2%.
According to the preparation method of the embodiment, the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid is controlled to be 0: 100. 4: 96 and 6: 94, obtaining polyethylene glycol porous ionic liquid with the loading amounts of the porous nano silicon spheres being 0%, 4% and 6%, applying the prepared polyethylene glycol porous ionic liquid to Thiophene (TP) simulation oil desulfurization, wherein the dosage of the polyethylene glycol porous ionic liquid during desulfurization is 2mL, the dosage of the simulation oil is 10mL, the oil bath temperature is 50 ℃, and measuring the sulfur content of the polyethylene glycol porous ionic liquid obtained by the porous nano silicon spheres and the imidazole functionalized polyethylene glycol ionic liquid under different mass ratios. The experimental result shows that the desulfurization performance of the polyethylene glycol porous ionic liquid to Thiophene (TP) obtained by the porous nano silicon spheres and the imidazole functionalized polyethylene glycol ionic liquid under different mass ratios is shown in fig. 6, and it can be seen from the figure that after 30min, the desulfurization rate of the porous nano silicon spheres with the loading of 2% is the lowest and is only 27.1%, and the desulfurization rate is rapidly increased along with the increase of time, when the desulfurization is performed for 90min, the desulfurization rate is obviously higher than that of the polyethylene glycol porous ionic liquid with the loading of 4% and 6% of the porous nano silicon spheres, which is probably because the mass of the silicon spheres is too large, agglomeration occurs in the porous imidazole functionalized silicon-based polyethylene glycol porous ionic liquid, so that accumulation is generated, and after 150min, the desulfurization rate of the polyethylene glycol porous ionic liquid with the loading of 2% of the porous nano silicon spheres reaches the highest and is 90.2%.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to Thiophene (TP) simulation oil desulfurization, the dosage of the polyethylene glycol porous ionic liquid is 2mL during desulfurization, the dosage of the simulation oil is 10mL, the oil bath temperatures are set to be 40 ℃, 50 ℃ and 60 ℃, and the sulfur content of the polyethylene glycol porous ionic liquid at different reaction temperatures is measured. Experimental results show that the desulfurization performance of the polyethylene glycol porous ionic liquid on Thiophene (TP) at different reaction temperatures is shown in figure 7, and it can be seen from the figure that after 30min, the desulfurization rates are not greatly different, the desulfurization rate at 60 ℃ is slightly higher than 40 ℃ and 50 ℃ and is 32.1%, but the desulfurization rates are obviously and rapidly increased along with the increase of desulfurization time, and after 60min, the desulfurization effect at 50 ℃ is remarkably increased and is always increased and is higher than 60 ℃ and 40 ℃, which means that when the temperature is higher, the electrostatic effect is weakened therewith. After 150min, the desulfurization rate reached equilibrium, which was 90.2%.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to Thiophene (TP) simulation oil desulfurization, the dosage of the polyethylene glycol porous ionic liquid is controlled to be 2mL, 4mL and 6mL respectively during desulfurization, the dosage of the simulation oil is 10mL, the oil bath temperature is 50 ℃, and the sulfur content of the polyethylene glycol porous ionic liquid under different dosages is measured. The experimental result shows that the desulfurization performance of the polyethylene glycol porous ionic liquid on Thiophene (TP) under different dosages is as shown in fig. 8, and it can be seen from the figure that after 30min of desulfurization, the desulfurization effects of dosages of 2, 4 and 6mL are not obviously different, the desulfurization rate of 4mL after 60min is slightly higher than that of 2mL and 6mL, the desulfurization rate is also obviously improved along with the prolonging of time, after 90min, the desulfurization rates of 2mL and 6mL are the same, 4mL is the highest, 30min is performed, the desulfurization rates of 2mL and 4mL are slowly increased, the same value is achieved, and after 150min, the desulfurization rate of 4mL is higher than that of 2 mL. The TP in the simulated oil is saturated in the porous imidazole functionalized silicon-based polyethylene glycol porous ionic liquid, and the desulfurization rate is up to 92.2%.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to desulfurization of Thiophene (TP) simulation oil, the dosage of the polyethylene glycol porous ionic liquid is 4mL respectively during desulfurization, the dosage of the simulation oil is 10mL, the oil bath temperature is 50 ℃, the simulation oil is Benzothiophene (BT), Thiophene (TP) and Dibenzothiophene (DBT) respectively, and the sulfur content of the polyethylene glycol porous ionic liquid to different types of simulation oil is measured. The experimental result shows that the desulfurization performance of the polyethylene glycol porous ionic liquid on different simulated oils is shown in fig. 9, and it can be seen from the graph that after 150min, BT (94.4%) > TP (92.2%) > DBT (75.1%). This is probably due to the difference in electron cloud density of sulfur atoms of different sulfides, benzothiophene (5.716) > thiophene (5.696), which has a large electron cloud density and a large hydrogen bonding force with nano silicon spheres. And because the volume of dibenzothiophene is larger, the adsorption effect of nano silicon spheres on the dibenzothiophene is smaller than that of benzothiophene and thiophene.
Example 2
Adding 0.06mol of polyethylene glycol with the average molecular mass of 800, 0.06mol of thionyl chloride and 0.01mol of pyridine into a 200mL round bottom flask, performing oil bath at 42 ℃, magnetically stirring at the rotating speed of 900r/min for 2.8h, pouring into a separating funnel, adding 20mL of diethyl ether, shaking, oscillating, standing for layering, wherein the lower layer is chlorinated polyethylene glycol;
dissolving 0.01mol of sodium ethoxide in 20mL of ethanol, adding the solution into a 100mL round-bottom flask, stirring the solution until the solution is uniform, adding 0.01mol of imidazole, performing oil bath at 68 ℃, and performing magnetic stirring at the rotating speed of 900r/min for 10.5 hours to obtain imidazole sodium;
adding 0.002mol of imidazole sodium and 0.001mol of chlorinated polyethylene glycol into a 100mL round-bottom flask, carrying out oil bath at 82 ℃, stirring at the rotating speed of 900r/min for 11h, precipitating the reacted sodium chloride in acetone, taking supernatant, and carrying out reduced pressure rotary evaporation at 32 ℃ to remove acetone to obtain imidazole functionalized polyethylene glycol;
adding 0.005mol of imidazole functionalized polyethylene glycol and 0.01mol of 3-chloropropyltrimethoxysilane into a 50mL round-bottom flask, carrying out oil bath at 82 ℃, and stirring at the rotating speed of 900r/min for 11h to obtain imidazole functionalized polyethylene glycol ionic liquid;
45mL of an aqueous ethanol solution (water to ethanol volume ratio of 0.5: 1) was added to a 100mL beaker and sonicated at 35kHz for 30min, followed by 0.48g of a mixture of cetyltrimethylammonium bromide and tetraethyl silicate, wherein the molar ratio of cetyltrimethylammonium bromide to tetraethyl silicate was 1: 1.1, magnetically stirring for 7 hours in a water bath at the temperature of 35 ℃ at the rotating speed of 900r/min, centrifuging, taking out, centrifugally washing for 4 times by using ethanol to remove unreacted organic matters and ammonia, centrifugally washing, drying in a 65 ℃ oven for 26 hours, putting a dried sample in a muffle furnace, heating at the speed of 1.5 ℃/min to reach 530 ℃, and calcining at constant temperature for 7 hours to obtain porous nano silicon spheres;
dispersing 0.20g of porous nano silicon spheres in 20mL of ethanol, carrying out ultrasonic treatment at the frequency of 45kHz for 30min, adding into 9.80g of imidazole functionalized polyethylene glycol ionic liquid, carrying out oil bath at 82 ℃, carrying out magnetic stirring at the rotating speed of 900r/min for 9h, and carrying out rotary evaporation at 45 ℃ to remove excessive ethanol, thus obtaining the polyethylene glycol porous ionic liquid with the porous nano silicon spheres loading of 2%.
The polyethylene glycol porous ionic liquid prepared by the embodiment is applied to TP desulfurization under the optimal condition, and FT-IR analysis and characterization are carried out on the polyethylene glycol porous ionic liquid before and after desulfurization; and (3) taking out the porous ionic liquid (bottom layer) after the reaction is finished, drying the polyethylene glycol porous ionic liquid at 70 ℃ to evaporate the residual simulation oil because the polyethylene glycol porous ionic liquid is insoluble in the simulation oil, then adding 10ml of fresh simulation oil to perform the next reaction, re-extracting for 5 times, and researching the influence of the recycling times on the desulfurization rate of the polyethylene glycol porous ionic liquid. The experimental results show that the FT-IR analysis chart is shown in FIG. 10, and the recycling study chart is shown in FIG. 11. As can be seen from FIG. 11, the polyethylene glycol porous ionic liquid has better reusability, and when the polyethylene glycol porous ionic liquid is reused for 3 times, the desulfurization degree is only slightly reduced, and is reduced from 92.2% to 87.4%, and is only reduced by 4.8%. After the 4 th time of recycling, the desulfurization rate is obviously reduced to 50.2%, and after the 5 th time of recycling, the desulfurization rate is reduced to 44.2%.
Example 3
Adding 0.06mol of polyethylene glycol with the average molecular mass of 700, 0.06mol of thionyl chloride and 0.01mol of pyridine into a 200mL round-bottom flask, performing oil bath at 38 ℃, magnetically stirring at the rotating speed of 1100r/min for 3.2h, pouring into a separating funnel, adding 20mL of diethyl ether, shaking, oscillating, standing for layering, wherein the lower layer is chlorinated polyethylene glycol;
dissolving 0.01mol of sodium ethoxide in 20mL of ethanol, adding the solution into a 100mL round-bottom flask, stirring the solution until the solution is uniform, adding 0.01mol of imidazole, performing oil bath at 72 ℃, and performing magnetic stirring at the rotating speed of 1100r/min for 9.5 hours to obtain imidazole sodium;
adding 0.002mol of imidazole sodium and 0.001mol of chlorinated polyethylene glycol into a 100mL round-bottom flask, carrying out oil bath at 78 ℃, stirring at the rotating speed of 1100r/min for 13h, precipitating the reacted sodium chloride in acetone, taking supernatant, and carrying out reduced pressure rotary evaporation at 28 ℃ to remove acetone to obtain imidazole functionalized polyethylene glycol;
adding 0.005mol of imidazole functionalized polyethylene glycol and 0.01mol of 3-chloropropyltrimethoxysilane into a 50mL round bottom flask, carrying out oil bath at 78 ℃, and stirring at the rotating speed of 1100r/min for 13h to obtain imidazole functionalized polyethylene glycol ionic liquid;
55mL of an aqueous ethanol solution (water to ethanol volume ratio of 0.7: 1) was added to a 100mL beaker, sonicated at 45kHz for 15min, and then 0.52g of a mixture of cetyltrimethylammonium bromide and tetraethyl silicate was added, wherein the molar ratio of cetyltrimethylammonium bromide to tetraethyl silicate was 1: 0.9, magnetically stirring for 5 hours in a water bath at the temperature of 25 ℃ at the rotating speed of 1100r/min, centrifuging, taking out, centrifugally washing for 2 times by using ethanol to remove unreacted organic matters and ammonia, centrifugally washing, drying in a 75 ℃ oven for 22 hours, putting a dried sample in a muffle furnace, heating at the speed of 2.5 ℃/min, and calcining at constant temperature for 5 hours after the temperature reaches 560 ℃ to obtain porous nano silicon spheres;
dispersing 0.30g of porous nano silicon spheres in 20mL of ethanol, carrying out ultrasonic treatment at the frequency of 35kHz for 30min, adding into 9.70g of imidazole functionalized polyethylene glycol ionic liquid, carrying out oil bath at 78 ℃, carrying out magnetic stirring at the rotating speed of 1100r/min for 11h, and carrying out rotary evaporation at the temperature of 50 ℃ to remove redundant ethanol, thus obtaining the polyethylene glycol porous ionic liquid with the porous nano silicon spheres loading of 3%.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to TP desulfurization by adopting the method consistent with the embodiment 2, and as a result, after the polyethylene glycol porous ionic liquid is repeatedly used for 3 times, the desulfurization rate is reduced from 92.0% to 86.9%, the desulfurization rate is reduced by 5.1%, and the reusability is better.
According to the embodiment, the polyethylene glycol porous ionic liquid is stable at room temperature, has good thermal stability below 200 ℃, and has a structure of porous nano silicon spheres stably existing in the polyethylene glycol porous ionic liquid; after the catalyst is applied to an adsorption extraction desulfurization process, the desulfurization rate can reach 92.2 percent; has better reusability, and the desulfurization rate is reduced from 92.2 percent to 87.4 percent after 3 times of reutilization.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the polyethylene glycol porous ionic liquid is characterized by comprising the following steps:
(1) mixing chlorinated polyethylene glycol and imidazole sodium to obtain imidazole functionalized polyethylene glycol;
(2) mixing imidazole functionalized polyethylene glycol with 3-chloropropyltrimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid;
(3) mixing the ethanol solution of the porous nano silicon spheres with imidazole functionalized polyethylene glycol ionic liquid, and then reacting to obtain the polyethylene glycol porous ionic liquid.
2. The method according to claim 1, wherein the molar ratio of the chlorinated polyethylene glycol to the imidazole sodium in step (1) is 1: 1.8-2.2; the molecular weight of the chlorinated polyethylene glycol is 400-800.
3. The preparation method according to claim 2, wherein the mixing temperature in the step (1) is 75-85 ℃, the mixing time is 10-14 h, and the mixing speed is 900-1100 r/min.
4. The preparation method of claim 1, wherein the molar ratio of the imidazole-functionalized polyethylene glycol to the 3-chloropropyltrimethoxysilane in the step (2) is 0.4-0.6: 1.
5. the preparation method according to claim 1, wherein the mixing temperature in the step (2) is 75-85 ℃, the mixing time is 10-14 h, and the mixing speed is 900-1100 r/min.
6. The preparation method according to claim 1, wherein the mass ratio of the porous nano silicon spheres to the imidazole-functionalized polyethylene glycol ionic liquid in the step (3) is 2-6: 94-98.
7. The preparation method according to claim 1, wherein the mass-to-volume ratio of the porous nano silicon spheres to the ethanol in the step (3) is 0.14g to 0.60 g: 20 mL.
8. The preparation method according to claim 7, wherein the reaction temperature in the step (3) is 75-85 ℃, the reaction stirring time is 8-12 h, and the stirring rotation speed is 900-1100 r/min.
9. The polyethylene glycol porous ionic liquid obtained by the preparation method of any one of claims 1 to 8.
10. Use of the polyethylene glycol porous ionic liquid of claim 9 in an adsorptive extraction desulfurization process.
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