CN115125030B - 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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- CN115125030B CN115125030B CN202210962730.4A CN202210962730A CN115125030B CN 115125030 B CN115125030 B CN 115125030B CN 202210962730 A CN202210962730 A CN 202210962730A CN 115125030 B CN115125030 B CN 115125030B
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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
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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, a preparation method and application thereof, wherein chlorinated polyethylene glycol and imidazole sodium are mixed to obtain imidazole functionalized polyethylene glycol; mixing imidazole functionalized polyethylene glycol with 3-chloropropyl trimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid; and mixing the ethanol solution of the porous nano silicon spheres with the 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 method is applied to the adsorption extraction desulfurization process, the desulfurization rate can reach 92.2 percent; has better reusability, and the desulfurization rate is reduced from 92.2% to 87.4% after 3 times of repeated use.
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 yield and holding capacity of fuel automobiles have been rapidly increased, resulting in rapid increase of fuel consumption for automobiles, and increase of the emission of automobile exhaust gas inconvenient to use the industrial desulfurization method. In a large environment with continuously increased global fuel consumption, sulfide in fuel oil has serious influence on the environment, and the formed acid rain, haze and other phenomena seriously endangering the health and safety of people and environmental safety are optimistic, so that the fuel oil desulfurization is very necessary. The main methods of fuel desulfurization are two major classes, hydrodesulfurization (HDS) and non-hydrodesulfurization (NHDS). Non-hydrodesulfurization (NHDS) is a desulfurization technology proposed for some drawbacks of the current stage hydrodesulfurization technology, mainly including Oxidative Desulfurization (ODS), biological Desulfurization (BDS), adsorption Desulfurization (ADS), and Extractive Desulfurization (EDS).
The adsorption desulfurization method has better removal effect on thiophene sulfur compounds, the operation of adsorption desulfurization is simpler, the cost is lower, byproducts harmful to the environment are relatively fewer, but the adsorbent has the problems of easy loss of active components, easy poisoning or inactivation of catalysts and the like, is suitable for small-sized oil refineries in industry, and is characterized by the properties of the adsorbent, including activity, capacity, selectivity, service life and regeneration, and the adsorbent which is used more at present comprises molecular sieves, active carbon, metal oxides and the like. The mechanism of Extraction Desulfurization (EDS) is to separate the oil product and the extractant by utilizing the difference of the polarity of the sulfide and the oil product to form the difference of the solubility of the oil product and the extractant, so that the dissolution of the sulfide in two phases of the oil product and the extractant is balanced finally, and the purpose of removing the sulfide is realized. Because the extraction desulfurization has lower requirements on the operation conditions, can be performed at normal temperature, normal pressure, 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 generally lower, 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 with sodium imidazole to obtain imidazole functionalized polyethylene glycol;
(2) Mixing imidazole functionalized polyethylene glycol with 3-chloropropyl trimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid;
(3) And mixing the ethanol solution of the porous nano silicon spheres with the imidazole functionalized polyethylene glycol ionic liquid, and then reacting to obtain the polyethylene glycol porous ionic liquid.
Preferably, the molar ratio of the chloropolyethylene glycol to the imidazole sodium in the step (1) is 1:1.8 to 2.2; the molecular weight of the chloro-polyethylene glycol is 400-800.
Preferably, the temperature of the mixing in the step (1) is 75-85 ℃, the stirring time of the mixing is 10-14 h, and the stirring rotating speed is 900-1100 r/min.
Preferably, the molar ratio of the imidazole functionalized polyethylene glycol to the 3-chloropropyl trimethoxysilane in the step (2) is 0.4 to 0.6:1.
preferably, the temperature of the mixing in the step (2) is 75-85 ℃, the stirring time of the mixing is 10-14 h, and the stirring speed is 900-1100 r/min.
Preferably, in the step (3), the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid is 2-6: 94-98.
Preferably, in the step (3), the mass volume ratio of the porous nano silicon spheres to the ethanol is 0.14 g-0.60 g:20mL.
Preferably, the temperature of the reaction in the step (3) is 75-85 ℃, the stirring time of the reaction is 8-12 h, and the stirring speed is 900-1100 r/min.
The invention also provides the polyethylene glycol porous ionic liquid obtained by the preparation method.
The invention also provides application of the polyethylene glycol porous ionic liquid in an adsorption extraction desulfurization process.
The beneficial effects of the invention are as follows:
(1) The invention provides a preparation method of polyethylene glycol porous ionic liquid, which comprises the steps of mixing chlorinated polyethylene glycol with sodium imidazole to obtain imidazole functionalized polyethylene glycol; mixing imidazole functionalized polyethylene glycol with 3-chloropropyl trimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid; and mixing the ethanol solution of the porous nano silicon spheres with the 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 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 not only comprises the hydrogen bond effect between hydroxyl groups on the surface of a silicon sphere and thiophene, but also comprises the electrostatic effect between carbon chain groups in polyethylene glycol and thiophene, and because imidazole cations in the polyethylene glycol porous ionic liquid have strong aromaticity, after the polyethylene glycol porous ionic liquid contacts Thiophene (TP), the imidazole cations have strong polarity, the dispersion pi bond of the thiophene is induced to generate polarization effect, and pi bond after polarization and porous imidazole functionalized silicon-based polyethylene glycol porous ionic liquid generate pi-pi complexing effect, so that the desulfurization effect is remarkably improved.
(3) The polyethylene glycol porous ionic liquid provided by the invention can reach a desulfurization rate of 92.2% after being applied to an adsorption extraction desulfurization process; has better reusability, and the desulfurization rate is reduced from 92.2% to 87.4% after 3 times of repeated use.
Drawings
Fig. 1 is a mass ratio of polyethylene glycol molecular weight 800, porous nano silicon spheres to imidazole functionalized polyethylene glycol ionic liquid of 2: FT-IR spectrum of 98 polyethylene glycol porous ionic liquid;
fig. 2 is a mass ratio of polyethylene glycol molecular weight 800, porous nano silicon spheres to imidazole functionalized polyethylene glycol ionic liquid of 2:98, fig. 2 (a) is a TEM analysis chart at a magnification of 1:100000, fig. 2 (b) is a TEM analysis chart at a magnification of 1:50000, fig. 2 (c) is a TEM analysis chart at a magnification of 1:20000, fig. 2 (e) is an EDS spectrum of nitrogen element of the polyethylene glycol porous ionic liquid at a magnification of 1:50000, fig. 2 (f) is an EDS spectrum of oxygen element of the polyethylene glycol porous ionic liquid at a magnification of 1:50000, and fig. 2 (g) is an EDS spectrum of silicon element of the polyethylene glycol porous ionic liquid at a magnification of 1:50000;
fig. 3 is a mass ratio of polyethylene glycol molecular weight 800, porous nano silicon spheres to imidazole functionalized polyethylene glycol ionic liquid of 2: TG and DTG profile of 98 polyethylene glycol porous ionic liquid;
fig. 4 is a mass ratio of polyethylene glycol molecular weight 800, porous nano silicon spheres to imidazole functionalized polyethylene glycol ionic liquid of 2:98 polyethylene glycol porous ionic liquid N 2 An adsorption quantity diagram;
FIG. 5 is a graph showing the desulfurization performance of Thiophene (TP) by polyethylene glycol porous ionic liquids obtained from polyethylene glycols with different molecular weights;
FIG. 6 is a graph showing the desulfurization performance of Thiophene (TP) by polyethylene glycol porous ionic liquid obtained by porous nano-silicon spheres and imidazole functionalized polyethylene glycol ionic liquid under different mass ratios;
FIG. 7 is a graph showing the desulfurization performance of polyethylene glycol porous ionic liquid on Thiophene (TP) at different reaction temperatures;
FIG. 8 is a graph showing the desulfurization performance of Thiophene (TP) with various amounts of polyethylene glycol porous ionic liquid;
FIG. 9 is a graph of desulfurization performance of polyethylene glycol porous ionic liquids for various simulated oils;
FIG. 10 is a characterization chart of FT-IR analysis before and after desulfurization of the polyethylene glycol porous ionic liquid prepared in example 2;
FIG. 11 is a graph of the recycling study of desulfurization of the polyethylene glycol porous ionic liquid 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 with sodium imidazole to obtain imidazole functionalized polyethylene glycol;
(2) Mixing imidazole functionalized polyethylene glycol with 3-chloropropyl trimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid;
(3) And mixing the ethanol solution of the porous nano silicon spheres with the imidazole functionalized polyethylene glycol ionic liquid, and then reacting to obtain the polyethylene glycol porous ionic liquid.
In the invention, the chloropolyethylene glycol in the step (1) can be purchased or prepared, and the invention provides a preparation method of the chloropolyethylene glycol, which comprises the following steps:
mixing polyethylene glycol, sulfoxide chloride and pyridine to obtain chloro polyethylene glycol.
In the present invention, the molar ratio of polyethylene glycol, thionyl chloride and pyridine is preferably 5 to 7:5 to 7:0.5 to 1.5, more preferably 5.5 to 6.5:5.5 to 6.5:0.8 to 1.2, more preferably 6:6:1.
in the present invention, the mixing is performed in an oil bath, and the temperature of the mixing is preferably 35 to 45 ℃, more preferably 38 to 42 ℃, and still more preferably 40 ℃; the stirring time of the mixing is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and still more preferably 3 hours; the rotation speed is preferably 900 to 1100r/min, more preferably 950 to 1050r/min, and still more preferably 1000r/min.
In the invention, after the reaction is finished, the mixed liquid is poured into a separating funnel, diethyl ether is added, shaking oscillation is carried out, standing and layering are carried out, and the lower layer is chloro polyethylene glycol.
In the invention, the mol volume ratio of the polyethylene glycol to the diethyl ether is preferably 5 to 7mol:1 to 3L, more preferably 5.5 to 6.5mol:1.5 to 2.5L, more preferably 6mol:2L.
In the invention, the preparation process of the chloropolyethylene glycol is as follows:
in the invention, the imidazole sodium in the step (1) can be purchased or prepared, and the invention provides a preparation method of the imidazole sodium, which comprises the following steps:
and (3) reacting sodium ethoxide with imidazole in ethanol to obtain the sodium imidazole.
In the invention, the molar volume ratio of the sodium ethoxide to the ethanol to the imidazole is preferably 0.8 to 1.2mol: 1.8-2.2L: 0.8 to 1.2mol, more preferably 0.9 to 1.1mol:1.9 to 2.1L:0.9 to 1.1mol, more preferably 1mol:2L:1mol.
In the present invention, the reaction is carried out in an oil bath, and the temperature of the reaction is preferably 65 to 75 ℃, more preferably 68 to 72 ℃, and still more preferably 70 ℃; the stirring time of the reaction is preferably 8 to 12 hours, more preferably 9 to 11 hours, and still more preferably 10 hours; the rotation speed is preferably 900 to 1100r/min, more preferably 950 to 1050r/min, and still more preferably 1000r/min.
In the present invention, the molar ratio of the chloropolyethylene glycol to the sodium imidazole in the step (1) is preferably 1:1.8 to 2.2, more preferably 1:1.9 to 2.1, more preferably 1:2; the molecular weight of the chloropolyethylene glycol is preferably 400 to 800, more preferably 500 to 700, and still more preferably 600.
In the present invention, the temperature of the mixing in step (1) is preferably 75 to 85 ℃, more preferably 78 to 82 ℃, still more preferably 80 ℃; the stirring time of the mixing is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 12 hours; the stirring speed is preferably 900 to 1100r/min, more preferably 950 to 1050r/min, and still more preferably 1000r/min.
In the invention, after the reaction in the step (1), the mixed liquid is placed in acetone, sodium chloride is precipitated, supernatant fluid is taken, acetone is removed by reduced pressure rotary evaporation, and the imidazole functionalized polyethylene glycol is obtained.
In the present invention, the temperature of the reduced pressure rotary evaporation is preferably 25 to 35 ℃, more preferably 28 to 32 ℃, and still more preferably 30 ℃.
In the present invention, the reaction process of step (1) is as follows:
in the present invention, the molar ratio of the imidazole functionalized polyethylene glycol to the 3-chloropropyl trimethoxysilane in the step (2) is preferably 0.4 to 0.6:1, more preferably 0.45 to 0.55:1, more preferably 0.5:1.
in the present invention, the temperature of the mixing in step (2) is preferably 75 to 85 ℃, more preferably 78 to 82 ℃, still more preferably 80 ℃; the stirring time of the mixing is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 12 hours; the stirring speed is preferably 900 to 1100r/min, more preferably 950 to 1050r/min, and still more preferably 1000r/min.
In the present invention, the reaction process of step (2) is as follows:
in the invention, the porous nano-silicon spheres in the step (3) are prepared, and the invention provides a preparation method of the porous nano-silicon spheres, which comprises the following steps:
and (3) reacting the mixture of cetyl trimethyl ammonium bromide and tetraethyl silicate in an ethanol water solution to obtain the porous nano silicon spheres.
In the present invention, before adding the mixture to the aqueous ethanol solution, the aqueous ethanol solution is preferably subjected to ultrasonic treatment for a period of preferably 10 to 30 minutes, more preferably 15 to 25 minutes, and still more preferably 20 minutes; the frequency of the ultrasonic wave is preferably 35 to 45kHz, more preferably 38 to 42kHz, and even more preferably 40kHz.
In the present invention, the molar ratio of cetyltrimethylammonium bromide to tetraethyl silicate in the mixture is preferably 0.8 to 1.2:0.8 to 1.2, more preferably 0.9 to 1.1:0.9 to 1.1, more preferably 1:1, a step of; 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 0.55g:45 to 55mL, more preferably 0.5g:50mL.
In the present invention, the reaction is carried out in a water bath, and the temperature of the reaction is preferably 25 to 35 ℃, more preferably 28 to 32 ℃, and still more preferably 30 ℃; the reaction time is preferably 4 to 8 hours, more preferably 5 to 7 hours, and still more preferably 6 hours; the stirring speed during the reaction is preferably 900 to 1100r/min, more preferably 950 to 1050r/min, and still more preferably 1000r/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, more preferably 3 times.
In the present invention, the sample is dried after centrifugal washing, and the drying temperature is preferably 65 to 75 ℃, more preferably 68 to 72 ℃, and even more preferably 70 ℃; the drying time is preferably 22 to 26 hours, more preferably 23 to 25 hours, and even more preferably 24 hours.
In the invention, the sample is calcined after drying is finished, the calcination is carried out in a muffle furnace, and the heating rate of the calcination is preferably 1-3 ℃/min, more preferably 1.5-2.5 ℃/min, and even more preferably 2 ℃/min; the target temperature for calcination is preferably 530 to 570 ℃, more preferably 540 to 560 ℃, and even more preferably 550 ℃; the heat is preserved after the target temperature is reached, and the time for heat preservation is preferably 4 to 8 hours, more preferably 5 to 7 hours, and still more preferably 6 hours. And obtaining the porous nano silicon spheres after the sample is calcined.
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 to 98, more preferably 3 to 5:95 to 97, more preferably 4:96.
in the invention, the mass volume ratio of the porous nano silicon spheres to the ethanol in the step (3) is preferably 0.14 g-0.60 g:20mL, more preferably 0.22g to 0.52g:20mL, more preferably 0.30g to 0.44g:20mL.
In the invention, in the step (3), the porous nano silicon spheres are dispersed in ethanol and then subjected to ultrasonic treatment, wherein the ultrasonic treatment time is preferably 20-40 min, more preferably 25-35 min, and even more preferably 30min; the frequency of the ultrasonic wave is preferably 35 to 45kHz, more preferably 38 to 42kHz, and even more preferably 40kHz.
In the present invention, the temperature of the reaction in step (3) is preferably 75 to 85 ℃, more preferably 78 to 82 ℃, still more preferably 80 ℃; the stirring time of the reaction is preferably 8 to 12 hours, more preferably 9 to 11 hours, and still more preferably 10 hours; the stirring speed is preferably 900 to 1100r/min, more preferably 950 to 1050r/min, and still more preferably 1000r/min.
In the invention, after the reaction in the step (3) is finished, the excess ethanol is removed by rotary evaporation, and the polyethylene glycol porous ionic liquid is obtained.
In the present invention, the temperature of the rotary evaporation is preferably 45 to 55 ℃, more preferably 48 to 52 ℃, and still more preferably 50 ℃.
The invention also provides the polyethylene glycol porous ionic liquid obtained 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 weight of 800, 0.06mol of thionyl chloride and 0.01mol of pyridine into a 200mL round bottom flask, magnetically stirring for 3 hours at the speed of 1000r/min at the temperature of 40 ℃ in an oil bath, pouring into a separating funnel, adding 20mL of diethyl ether, shaking, oscillating, standing for layering, wherein the lower layer is chloro polyethylene glycol;
dissolving 0.01mol of sodium ethoxide in 20mL of ethanol, adding the solution into a 100mL round bottom flask, stirring to a uniform system, adding 0.01mol of imidazole, then magnetically stirring the mixture for 10 hours at the temperature of 70 ℃ in an oil bath at the rotating speed of 1000r/min to obtain sodium imidazolate;
adding 0.002mol of sodium imidazole and 0.001mol of chloropolyethylene glycol into a 100mL round bottom flask, stirring for 12 hours at the oil bath 80 ℃ and the rotating speed of 1000r/min, precipitating the reacted sodium chloride in acetone, taking supernatant, and removing acetone by rotary evaporation under reduced pressure at the temperature of 30 ℃ to obtain imidazole functionalized polyethylene glycol (namely ImPEG);
adding 0.005mol of imidazole functionalized polyethylene glycol and 0.01mol of 3-chloropropyl trimethoxysilane into a 50mL round bottom flask, and stirring at the temperature of 80 ℃ in an oil bath at the speed of 1000r/min for 12 hours to obtain imidazole functionalized polyethylene glycol ionic liquid;
50mL of an aqueous ethanol solution (0.6:1 by volume of water and ethanol) was added to a 100mL beaker, sonicated at a frequency of 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 at a rotating speed of 1000r/min in a water bath at 30 ℃, taking out after centrifugation, centrifugally washing for 3 times by using ethanol to remove unreacted organic matters and ammonia, centrifugally washing, putting into a 70 ℃ oven for drying for 24 hours, putting a dried sample into a muffle furnace, heating at a speed of 2 ℃/min, and calcining at a constant temperature for 6 hours after reaching 550 ℃ 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 40kHz for 30min, adding the solution into 9.80g of imidazole functionalized polyethylene glycol ionic liquid, carrying out magnetic stirring at the temperature of 80 ℃ in an oil bath at the rotating speed of 1000r/min for 10h, and carrying out rotary evaporation at the temperature of 50 ℃ to remove redundant ethanol, thereby obtaining the polyethylene glycol porous ionic liquid with the porous nano silicon sphere load of 2% (namely PS-ImPEG).
FT-IR analysis was performed on the polyethylene glycol porous ionic liquid obtained in this example and the imidazole functionalized polyethylene glycol porous nanospheres by using a TENSOR27 Fourier transform infrared spectrometer (Bruce instruments, germany), with a resolution of 4cm -1 Scanning range is 4000-450cm -1 . The experimental result shows that the FT-IR spectrum is shown in FIG. 1, and can be seen from the figure, 2876cm -1 The peak of (C) is C-H symmetrical telescopic vibration peak, 1248cm -1 The peak of (C) is an asymmetric telescopic 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 exocrown imidazole functionalized polyethylene glycol, and imidazole cations endow the porous liquid with fluidity; porous nano silicon sphere is 1090cm -1 Is an antisymmetric telescopic vibration peak of Si-O-Si, 801cm -1 And 464cm -1 The symmetrical telescopic vibration peak of Si-O is obvious, which shows that the structure of the porous nano silicon sphere exists stably 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 scanning electron microscope, the set voltage is 10.0kv, and the amplification factors are respectively 1:100000, 1:50000 and 1:20000; and amplifying and observing the test position by adopting an accelerating voltage of 20kv, performing element qualitative 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 analysis is shown in figure 2, wherein figure 2 (a) is a TEM analysis chart under the magnification of 1:100000, figure 2 (b) is a TEM analysis chart under the magnification of 1:50000, figure 2 (c) is a TEM analysis chart under the magnification of 1:20000, and figures 2 (e), (f) and (g) are EDS energy spectra of nitrogen, oxygen and silicon elements of the polyethylene glycol porous ionic liquid under the magnification of 1:50000 respectively. From the TEM analysis, clear porous nano-silica spheres can be observed in transmission electron microscope images with different magnifications, which indicates that the silica skeleton is firm, and cannot collapse during the oxidation of the surface silicon, and due to the strong interaction between imidazole functionalized polyethylene glycol and silane coupling agent, single nano-particles are combined together to form large aggregates, indicating that the structure of the silica spheres remains unchanged in the liquid state. And the EDS can be used for finding that nitrogen, oxygen and silicon elements are uniformly distributed in the polyethylene glycol porous ionic liquid, so that the imidazole functionalized polyethylene glycol external crown is preserved in the polyethylene glycol porous ionic liquid. Therefore, the structure of the porous nano silicon spheres is well preserved in polyethylene glycol porous ionic liquid.
The polyethylene glycol porous ionic liquid obtained in this example was subjected to thermal performance analysis by using an STA449F3 thermogravimetric analyzer (German relaxation Co.), and the polyethylene glycol porous ionic liquid was subjected to N-phase analysis 2 Under the protection of (2), the temperature is raised from room temperature to 800 ℃, and the temperature raising rate is 10 ℃/min. The experimental results show that the curves of TG and DTG are shown in figure 3, and the weight loss of the curve of TG is 4% in the temperature range of 30-100 ℃ as shown in the figure, and the curve is caused by released water, so that the polyethylene glycol porous ionic liquid has good thermal stability below 200 ℃; a weight loss of 62% at 100-400 ℃, possibly a gradual decomposition of the organic fraction in PS-PEG; the weight loss of the TG curve at 400-700 ℃ is 16%, which is probably the gradual decomposition of the porous nano-silica spheres PS in the PS-PEG, and the mass loss reaches equilibrium at about 500 ℃, which is consistent with the data of the DTG.
Full-automatic specific surface area and pore analyzer (U.S. microphone) using TRISTARII3020The device company) to N the polyethylene glycol porous ionic liquid (namely PS-ImPEG) and polyethylene glycol (namely ImPEG) obtained in the embodiment 2 Adsorption quantity characterization of the obtained N 2 The adsorption capacity is shown in FIG. 4, and it can be seen that polyethylene glycol has no adsorption capacity, which means that there is no permanent cavity hole in the liquid, and polyethylene glycol porous ionic liquid has obvious N 2 The adsorption amount is because the porous 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) simulated oil desulfurization, the dosage of the polyethylene glycol porous ionic liquids is 2mL during desulfurization, the dosage of the simulated oil is 10mL, the oil bath temperature is 50 ℃, the sulfur content of the polyethylene glycol porous ionic liquids obtained by polyethylene glycol with different molecular weights is measured by a TSN-2000 type sulfur nitrogen analyzer, and the specific analysis conditions for sulfur content measurement are as follows: the temperature of the FPD detector is 280 ℃, the temperature of the sample inlet is 250 ℃, and the sample is kept for 180 seconds. Experimental results show that the desulfurization performance of polyethylene glycol porous ionic liquids obtained by polyethylene glycol with different molecular weights on Thiophene (TP) is shown in figure 5, and it can be seen from the figure that when the desulfurization time is 30min, the desulfurization rates of polyethylene glycol molecular weights are 400 and 600 are higher than those of polyethylene glycol porous ionic liquids with molecular weights of 800, and when the desulfurization rate of three polyethylene glycol porous ionic liquids is 60min later, the desulfurization rate increase rate of polyethylene glycol porous ionic liquids with polyethylene glycol molecular weights of 800 is found to be obviously higher than that of the other two polyethylene glycol porous ionic liquids with the time prolonged, which is probably due to the fact that the larger the average molecular weight of polyethylene glycol is, the stronger the electrostatic effect is, and the desulfurization rate is enhanced accordingly. 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 maximum 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 capacity of the porous nano silicon spheres being 0, 4 and 6 percent respectively, applying the prepared polyethylene glycol porous ionic liquid to Thiophene (TP) simulated oil desulfurization, wherein the dosage of the polyethylene glycol porous ionic liquid is 2mL, the dosage of the simulated 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. Experimental results show that the desulfurization performance 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 on Thiophene (TP) is shown in a graph, and as can be seen from the graph, after 30min, the desulfurization rate of the porous nano silicon spheres is the lowest, which is only 27.1%, and the desulfurization rate is also rapidly increased along with the increase of time, when desulfurization is carried out for 90min, the desulfurization rate is obviously greater than that of the polyethylene glycol porous ionic liquid with 4% and 6% of the porous nano silicon spheres, which is probably due to the fact that the mass of the silicon spheres is overlarge, agglomeration occurs in the porous imidazole functionalized silicon polyethylene glycol porous ionic liquid, accumulation is generated, and after 150min, the desulfurization rate of the polyethylene glycol porous ionic liquid with the porous nano silicon spheres with the loading capacity of 2% reaches the highest, which is 90.2%.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to Thiophene (TP) simulated oil desulfurization, the dosage of the polyethylene glycol porous ionic liquid is 2mL during desulfurization, the dosage of the simulated oil is 10mL, the oil bath temperature is 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 polyethylene glycol porous ionic liquid on Thiophene (TP) at different reaction temperatures is shown in a graph in FIG. 7, and after 30min, the desulfurization rates are slightly different, the desulfurization rate at 60 ℃ is slightly higher than 40 ℃ and 50 ℃ and is 32.1%, but the desulfurization rate is obviously and rapidly increased along with the increase of the desulfurization time, after 60min, the desulfurization effect at 50 ℃ is obviously increased and is always increased, and the effects of static electricity are weakened along with the increase of the temperature. After 150min, the desulfurization rate reaches equilibrium, which is 90.2%.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to Thiophene (TP) simulated oil desulfurization, the dosage of the polyethylene glycol porous ionic liquid during desulfurization is controlled to be 2mL, 4mL and 6mL respectively, the dosage of the simulated oil is 10mL, the temperature of an oil bath is 50 ℃, and the sulfur content of the polyethylene glycol porous ionic liquid under different dosages is measured. Experimental results show that the desulfurization performance of polyethylene glycol porous ionic liquid on Thiophene (TP) under different dosages is shown in a graph as shown in the graph, the desulfurization effects of 2,4 and 6mL are not obviously different after 30min of desulfurization, the desulfurization rate of 4mL is slightly higher than 2mL and 6mL after 60min, the desulfurization rate is obviously improved along with the extension of time, the desulfurization rate of 2mL is the same as that of 6mL after 90min, the desulfurization rates of 4mL are the highest, 30min is carried out again, the desulfurization rates of 2mL and 4mL are slowly increased to reach the same value, and the desulfurization rate of 4mL is higher than 2mL after 150 min. This is because TP in the simulated oil has reached saturation in the porous imidazole functionalized silica-based polyethylene glycol porous ionic liquid, and the desulfurization rate is 92.2% at the maximum.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to Thiophene (TP) simulated oil desulfurization, the dosage of the polyethylene glycol porous ionic liquid is 4mL respectively during desulfurization, the dosage of the simulated oil is 10mL, the oil bath temperature is 50 ℃, the simulated oil is respectively Benzothiophene (BT), thiophene (TP) and Dibenzothiophene (DBT), and the sulfur content of the polyethylene glycol porous ionic liquid on different types of simulated oil is determined. Experimental results show that the desulfurization performance of the polyethylene glycol porous ionic liquid on different simulated oils is shown in fig. 9, and from the graph, BT (94.4%) > TP (92.2%) > DBT (75.1%) can be seen after 150 min. This is probably due to the difference in electron cloud density of sulfur atoms of different sulfides, benzothiophene (5.716) > thiophene (5.696), electron cloud density is large, and hydrogen bonding force with the nano-silicon spheres is large. And because the volume of the dibenzothiophene is larger, the adsorption effect of the nano silicon sphere on the dibenzothiophene is smaller, so the nano silicon sphere is lower than that of the benzothiophene and thiophene.
Example 2
Adding 0.06mol of polyethylene glycol with the average molecular weight of 800, 0.06mol of thionyl chloride and 0.01mol of pyridine into a 200mL round bottom flask, magnetically stirring for 2.8 hours at the temperature of 42 ℃ in an oil bath and the rotating speed of 900r/min, pouring into a separating funnel, adding 20mL of diethyl ether, shaking, standing for layering, and obtaining the lower layer of chlorinated polyethylene glycol;
dissolving 0.01mol of sodium ethoxide in 20mL of ethanol, adding the solution into a 100mL round bottom flask, stirring to a uniform system, adding 0.01mol of imidazole, then magnetically stirring the mixture for 10.5 hours at the temperature of 68 ℃ in an oil bath at the rotating speed of 900r/min to obtain sodium imidazolate;
adding 0.002mol of sodium imidazole and 0.001mol of chloropolyethylene glycol into a 100mL round bottom flask, oil-bathing at 82 ℃ and stirring at 900r/min for 11h, precipitating sodium chloride reacted in acetone, taking supernatant, and removing acetone by rotary evaporation under reduced pressure at 32 ℃ to obtain imidazole functionalized polyethylene glycol;
adding 0.005mol of imidazole functionalized polyethylene glycol and 0.01mol of 3-chloropropyl trimethoxysilane into a 50mL round bottom flask, and stirring at the temperature of 82 ℃ in an oil bath at the speed of 900r/min for 11h to obtain imidazole functionalized polyethylene glycol ionic liquid;
45mL of an aqueous ethanol solution (0.5:1 by volume of water and ethanol) was added to a 100mL beaker, sonicated at a frequency of 35kHz for 30min, and then 0.48g of a mixture of cetyltrimethylammonium bromide and tetraethyl silicate was added, wherein the molar ratio of cetyltrimethylammonium bromide to tetraethyl silicate was 1:1.1, magnetically stirring for 7 hours at a rotating speed of 900r/min in a water bath at 35 ℃, taking out after centrifugation, centrifugally washing for 4 times by using ethanol to remove unreacted organic matters and ammonia, putting the centrifugally washed sample into a 65 ℃ oven for drying for 26 hours, putting the dried sample into a muffle furnace, heating at a speed of 1.5 ℃/min, and calcining at a constant temperature for 7 hours after reaching 530 ℃ to obtain the 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 the solution into 9.80g of imidazole functionalized polyethylene glycol ionic liquid, carrying out magnetic stirring at the temperature of 82 ℃ in an oil bath at the rotating speed of 900r/min for 9h, and carrying out rotary evaporation at the temperature of 45 ℃ to remove redundant ethanol, thereby obtaining the polyethylene glycol porous ionic liquid with the porous nano silicon sphere load of 2%.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to TP desulfurization under the optimal condition, and FT-IR analysis characterization is carried out on the polyethylene glycol porous ionic liquid before and after desulfurization; and separating the porous ionic liquid (bottom layer) after the reaction is finished, drying at 70 ℃ to evaporate residual simulated oil because the polyethylene glycol porous ionic liquid is insoluble in the simulated oil, then adding fresh 10ml of the simulated oil to perform the next reaction, re-extracting for 5 times, and researching the influence of the repeated use 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 reusability study chart is shown in FIG. 11. From fig. 11, it can be seen that the polyethylene glycol porous ionic liquid has better recycling property, and when the polyethylene glycol porous ionic liquid is recycled for 3 times, the desulfurization rate is only slightly reduced from 92.2% to 87.4%, and is only reduced by 4.8%. After the 4 th time of repeated use, the desulfurization rate is obviously reduced to 50.2%, and after the 5 th time of repeated use, the desulfurization rate is reduced to 44.2%.
Example 3
Adding 0.06mol of polyethylene glycol with the average molecular weight of 700, 0.06mol of thionyl chloride and 0.01mol of pyridine into a 200mL round bottom flask, magnetically stirring for 3.2 hours at the speed of 1100r/min at the temperature of 38 ℃ in an oil bath, pouring into a separating funnel, adding 20mL of diethyl ether, shaking, standing for layering, and obtaining the lower layer of chlorinated polyethylene glycol;
dissolving 0.01mol of sodium ethoxide in 20mL of ethanol, adding the solution into a 100mL round bottom flask, stirring to a uniform system, adding 0.01mol of imidazole, then carrying out oil bath 72 ℃, and magnetically stirring for 9.5h at a rotating speed of 1100r/min to obtain sodium imidazolate;
adding 0.002mol of sodium imidazole and 0.001mol of chloropolyethylene glycol into a 100mL round bottom flask, stirring for 13h at the speed of 1100r/min at the temperature of 78 ℃ in an oil bath, precipitating out reacted sodium chloride in acetone, taking supernatant, and removing acetone by rotary evaporation under reduced pressure at the temperature of 28 ℃ to obtain imidazole functionalized polyethylene glycol;
adding 0.005mol of imidazole functionalized polyethylene glycol and 0.01mol of 3-chloropropyl trimethoxysilane into a 50mL round bottom flask, and stirring at the temperature of 78 ℃ in an oil bath at the speed of 1100r/min for 13h to obtain imidazole functionalized polyethylene glycol ionic liquid;
55mL of an aqueous ethanol solution (0.7:1 by volume of water and ethanol) was added to a 100mL beaker, sonicated at a frequency of 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 at a rotating speed of 1100r/min in a water bath at 25 ℃, taking out after centrifugation, centrifugally washing for 2 times by using ethanol to remove unreacted organic matters and ammonia, centrifugally washing, drying for 22 hours in a drying oven at 75 ℃, placing a dried sample in a muffle furnace, heating at a speed of 2.5 ℃/min, and calcining at a constant temperature for 5 hours after reaching 560 ℃ to obtain the porous nano-silicon spheres;
dispersing 0.30g of porous nano silicon spheres in 20mL of ethanol, carrying out ultrasonic treatment at 35kHz for 30min, adding the solution into 9.70g of imidazole functionalized polyethylene glycol ionic liquid, carrying out magnetic stirring at the temperature of 78 ℃ in an oil bath at the rotating speed of 1100r/min for 11h, and carrying out rotary evaporation at the temperature of 50 ℃ to remove redundant ethanol, thereby obtaining the polyethylene glycol porous ionic liquid with the loading capacity of the porous nano silicon spheres being 3%.
The polyethylene glycol porous ionic liquid prepared in the embodiment is applied to TP desulfurization by the method consistent with the embodiment 2, and after the polyethylene glycol porous ionic liquid is recycled for 3 times, the desulfurization rate is reduced from 92.0% to 86.9%, and is reduced by 5.1%, so that the polyethylene glycol porous ionic liquid has good recycling property.
From the above examples, the invention provides a polyethylene glycol porous ionic liquid which is stable 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 method is applied to the adsorption extraction desulfurization process, the desulfurization rate can reach 92.2 percent; has better reusability, and the desulfurization rate is reduced from 92.2% to 87.4% after 3 times of repeated use.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the polyethylene glycol porous ionic liquid is characterized by comprising the following steps of:
(1) Mixing chlorinated polyethylene glycol with sodium imidazole to obtain imidazole functionalized polyethylene glycol;
(2) Mixing imidazole functionalized polyethylene glycol with 3-chloropropyl trimethoxysilane to obtain imidazole functionalized polyethylene glycol ionic liquid;
(3) Mixing an 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 molar ratio of the chloropolyethylene glycol to the imidazole sodium in the step (1) is 1:1.8 to 2.2;
in the step (3), the mass ratio of the porous nano silicon spheres to the imidazole functionalized polyethylene glycol ionic liquid is 2-6: 94-98;
the preparation method of the porous nano-silicon spheres in the step (3) comprises the following steps:
and (3) reacting the mixture of cetyl trimethyl ammonium bromide and tetraethyl silicate in an ethanol water solution to obtain the porous nano silicon spheres.
2. The process according to claim 1, wherein the chloropolyethylene glycol in step (1) has a molecular weight of 400 to 800.
3. The method according to claim 2, wherein the temperature of the mixing in the step (1) is 75 to 85 ℃, the stirring time of the mixing is 10 to 14 hours, and the stirring speed is 900 to 1100r/min.
4. The method of claim 1, wherein the molar ratio of imidazole functionalized polyethylene glycol to 3-chloropropyl trimethoxysilane in step (2) is from 0.4 to 0.6:1.
5. the method according to claim 1, wherein the temperature of the mixing in the step (2) is 75 to 85 ℃, the stirring time of the mixing is 10 to 14 hours, and the stirring speed is 900 to 1100r/min.
6. The preparation method of claim 1, wherein the mass-volume ratio of the porous nano-silicon spheres to the ethanol in the step (3) is 0.14 g-0.60 g:20mL.
7. The process according to claim 6, wherein the temperature of the reaction in the step (3) is 75 to 85 ℃, the stirring time of the reaction is 8 to 12 hours, and the stirring speed is 900 to 1100r/min.
8. Polyethylene glycol porous ionic liquid obtained by the preparation method according to any one of claims 1 to 7.
9. The use of the polyethylene glycol porous ionic liquid according to claim 8 in an adsorption extraction desulfurization process.
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