CN115627180B - Boron nitride-based porous ionic liquid and preparation method and application thereof - Google Patents
Boron nitride-based porous ionic liquid and preparation method and application thereof Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 130
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 239000000295 fuel oil Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 21
- 230000023556 desulfurization Effects 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 239000011343 solid material Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000011344 liquid material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 34
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 18
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 10
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- NICUQYHIOMMFGV-UHFFFAOYSA-N 4-Methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C(C)=CC=C2 NICUQYHIOMMFGV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000005496 phosphonium group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- BAWOGMCLIXEBFZ-UHFFFAOYSA-N BPCl Chemical compound BPCl BAWOGMCLIXEBFZ-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 and at the same time Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Ceramic Products (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a boron nitride-based porous ionic liquid and a preparation method and application thereof, wherein boron nitride with abundant micropore structures is used as a guest frame, the size of the ionic liquid is larger than the pore size of the boron nitride, micropore channels of the boron nitride cannot be filled, the structure of the ionic liquid is regulated and controlled through hydrogen bonding between the boron nitride and the ionic liquid, and the boron nitride-based porous ionic liquid with remarkable stability is synthesized. The porous ionic liquid obtained by the method is green and safe, is simple to operate, and can be produced in a large scale. The boron nitride-based porous ionic liquid has the properties of liquid and solid materials, can reduce the dosage of the ionic liquid while improving the material performance, and has good application prospect in the aspect of deep desulfurization of fuel oil.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a boron nitride-based porous ionic liquid and a preparation method and application thereof.
Background
The combustion of sulfides in the fuel oil can generate a large amount of harmful gases and soot particles, which are harmful to human health and destroy ecological environment. Therefore, the cleaning of fuel has become a significant research topic. The hydrodesulfurization technology is mainly adopted in industry, and has the defects of high energy consumption, high investment cost, severe reaction conditions, difficult removal of square-fragrance organic sulfide and the like. Finding an excellent desulfurization process has become an indispensable research topic. The Extraction Desulfurization (EDS) has the advantages of low energy consumption, simple operation, mild reaction conditions, no need of an extra reaction bed and the like, so that the extraction desulfurization technology is paid attention to by researchers. However, in the process of extraction desulfurization, designing and using efficient extractant is one of the key links.
Ionic liquids are of great interest as a class of green solvents due to their good solubility, extremely low vapor pressure, stable physical and chemical properties, and the like. The application of the metal-based ionic liquid rich in the Lewis acid center in the aspect of removing sulfur compounds is larger and larger, wherein the pyridine-type iron-based ionic liquid and organic sulfide (DBT) can extract sulfide in fuel oil from an oil phase to an extraction phase through hydrogen bonding, lewis acid alkali action and pi-pi complexation, so that clean utilization of the fuel oil is realized, but the traditional ionic liquid still has the problem of low single desulfurization rate, so that the pyridine-type iron-based ionic liquid is difficult to be used for industrial production.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides a boron nitride-based porous ionic liquid material with high dispersibility, remarkable stability and high performance, which is prepared by adjusting the ionic liquid structure through boron nitride micropores.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a boron nitride-based porous ionic liquid consists of microporous boron nitride and ionic liquid, wherein the size of the ionic liquid is larger than that of the micropores of the boron nitride, and the ionic liquid and the boron nitride form an interaction, so that the porous ionic liquid with a rich pore structure is formed.
Preferably, the ionic liquid is selected from any one of imidazole ionic liquid, pyridine ionic liquid, quaternary phosphonium ionic liquid or quaternary ammonium ionic liquid.
The Boron Nitride (BN) is a structural carrier with potential application due to a special layer structure and large specific surface area, is relatively convenient to produce and relatively low in price, and can be designed into a microporous solid material (m-BN) with a rich pore structure by using a surfactant as a template agent to modulate the structure of the BN. The pyridine type plasma liquid with obvious stability and larger molecular size (the ionic liquid can not fill the micropores of the boron nitride, so that the porous structure can exist permanently) has unique anions and cations so as to have aromaticity and rich Lewis acid centers, and the boron nitride-based porous ionic liquid material with high dispersibility, obvious stability and high performance can be obtained by means of anchoring m-BN in the pyridine type plasma liquid.
Further, the microporous boron nitride has a micropore size of not more than 1nm, preferably in the pore size range of 0.5 to 1nm.
Further, the mass of the microporous boron nitride accounts for 1-20% of the total mass of the porous ionic liquid.
Further, the invention also provides a preparation method of the boron nitride-based porous ionic liquid, which comprises the following steps:
(1) Adding a surfactant into the methanol aqueous solution, stirring uniformly, adding boric acid, and stirring uniformly;
(2) Adding melamine into the solution in the step (1), and stirring for reaction to obtain white precipitate;
(3) Separating the white precipitate in the step (2), and calcining in an inert atmosphere to obtain microporous boron nitride;
(4) And (3) mixing the microporous boron nitride prepared in the step (3) with the ionic liquid, stirring for full dispersion, and then carrying out vacuum drying to obtain the microporous boron nitride.
Preferably, in the step (2), the molar ratio of boric acid to melamine is 1: 4-1: 8.
Preferably, in step (3), the calcining conditions are: the gas flow rate is 60-100 ml/min, and the temperature is kept at 700-900 ℃ for 2-5 h, preferably 3h at a heating rate of 2-10 ℃/min (preferably 5 ℃/min).
Preferably, in the step (4), the dispersion is carried out in a magnetic stirring mode and is provided with condensation reflux, the magnetic stirring rotating speed is 400-800 rpm/min, the condensation reflux temperature is 60-100 ℃, and the time is 5-10 h; the temperature of vacuum drying is 60-100 ℃ and the drying time is 4-10 h.
Furthermore, the invention also discloses application of the boron nitride-based porous ionic liquid in removing sulfides in fuel oil.
Furthermore, the invention also claims the application of the boron nitride based porous ionic liquid in absorbing sulfur dioxide and carbon dioxide gas.
The beneficial effects are that:
(1) According to the invention, boron nitride with abundant micropore structures is used as a guest frame, the size of the ionic liquid is larger than the pore size of the boron nitride, micropore channels of the boron nitride cannot be filled, the structure of the ionic liquid is regulated and controlled through hydrogen bonding between the boron nitride and the ionic liquid, and the boron nitride-based porous ionic liquid with remarkable stability is synthesized. The porous ionic liquid obtained by the method is green and safe, is simple to operate, and can be produced in a large scale.
(2) The boron nitride-based porous ionic liquid disclosed by the invention is taken as a novel ionic liquid, has the properties of liquid and solid materials, can reduce the dosage of the ionic liquid while improving the material performance, has a good application prospect in the aspect of deep desulfurization of fuel oil, has obvious stability and oil immiscibility, can avoid potential pollution to the environment, and realizes the recycling of raw materials. The method not only realizes the optimal utilization of the traditional ionic liquid and widens the design thought of the extractant, but also prepares a porous ionic liquid material, can reduce the sulfur content in the diesel oil from hundreds of ppm to several ppm, and provides a new thought for ultra-deep desulfurization of the diesel oil and gas absorbing materials.
Drawings
The foregoing and other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
Fig. 1 is a molecular size simulation diagram of an N 2 adsorption-desorption isotherm and pore size distribution of microporous boron nitride prepared by the invention.
FIG. 2 is an x-ray diffraction pattern of a boron nitride based porous ionic liquid prepared according to the present invention.
FIG. 3 shows desulfurization efficiencies of extractants having different boron nitride contents.
FIG. 4 is a graph showing desulfurization efficiency of boron nitride based porous ionic liquids at different temperatures.
FIG. 5 is a graph of desulfurization efficiency of boron nitride based porous ionic liquids for various sulfur-containing substrates.
FIG. 6 is a graph showing the performance of a boron nitride-based porous ionic liquid in multiple stepwise extractions of sulfur-containing compounds in fuel oil.
Fig. 7 is a graph of the absorption properties of boron nitride based porous ionic liquids for sulfur dioxide gas.
Fig. 8 is a graph of carbon dioxide gas absorption performance of a boron nitride based porous ionic liquid.
Detailed Description
The invention will be better understood from the following examples.
In the invention, the boron nitride with the micropore structure is specifically synthesized according to the following steps:
(1) The volume ratio of methanol to deionized water is 1:1, firstly adding 25mL of methanol into an equal volume of deionized water to prepare 50mL of methanol aqueous solution, adding 1.0g of surfactant (Pluronic P 123:5800g mol-1) into the methanol aqueous solution, magnetically stirring and dispersing for 30 minutes at 50 ℃, adding 0.6184g of boric acid into the solution, continuously dispersing and stirring for 15 minutes, and obtaining the aqueous solution with the molar ratio of boric acid to melamine of 1: and 8, 10.0896g of melamine is taken in the solution, and the reaction is continued with stirring for 24 hours. Obtaining white solid powder.
(2) And (3) placing the solid powder obtained in the step (1) in a quartz ark, and calcining at a high temperature in an inert nitrogen atmosphere to obtain the microporous boron nitride material.
In the step (1), the surfactant, boric acid and melamine are purchased from the market.
In the step (2), the atmosphere is nitrogen. The gas flow rate is 60-100 ml/min, the heating rate of the high-temperature calcination is 5 ℃/min, the high-temperature calcination temperature is 700 ℃, and the holding time is 3h.
The surface of the microporous boron nitride material prepared by the invention contains a large number of nitrogen-containing functional groups, and is a solid material with abundant pore structures.
The boron nitride-based porous ionic liquid is prepared by the following steps:
(1) Adding boron nitride into ionic liquid (selected from any one of imidazole ionic liquid, pyridine ionic liquid, quaternary phosphonium ionic liquid or quaternary ammonium ionic liquid) with the size larger than the micropore size of boron nitride according to the mass ratio of 1% -20%, dispersing in an IKA magnetic heating stirrer for 5-10 h at 60-100 ℃ under the condition of condensation reflux, and rotating at 400-800 rpm/min.
(2) Transferring the sample obtained in the step (1) into a vacuum drying oven, wherein the temperature is 60-100 ℃, and the drying time is 4-10 h, so that the boron nitride-based porous ionic liquid is obtained.
The pyridine-type and imidazole-type ionic liquids were synthesized according to references W.Zhu, P.Wu, L.Yang, Y.Chang, Y.Chao, H.Li, Y.Jiang, W.Jiang and S.Xun, chem.Eng.J 229 (2013) 250-256.
The adsorption and desorption isotherm and the pore size distribution diagram (fig. 1a and 1 b) of the microporous boron nitride N 2 prepared above, and the molecular size simulation diagram (fig. 1 b) of the ionic liquid are shown in fig. 1. It can be seen that the prepared microporous boron nitride has abundant porous structure, the pore size distribution of the boron nitride is mainly 0.5-1nm, and the molecular size of the pyridine type ionic liquid [ BPy ] [ FeCl 4 ] isThe boron nitride-based porous ionic liquid retains a rich porous structure.
The x-ray diffraction patterns of the prepared boron nitride-based porous ionic liquid are shown in fig. 2, diffraction peaks at 12.4 degrees and 21.4 degrees are characteristic diffraction peaks of pyridine-type ionic liquid [ BPy ] [ FeCl 4 ], wherein the offset occurs because the interlayer spacing is reduced due to the interaction of boron nitride and pyridine-type ionic liquid, and the characteristic peak of boron nitride is strong and weak because the content of boron nitride is low.
The following are the types of fuels used in the examples:
The model oil is prepared by dissolving sulfur-containing compounds such as Dibenzothiophene (DBT), 4, 6-dimethyldibenzothiophene (4, 6-DMDBT), 4-methyldibenzothiophene (4-MDBT) and Benzothiophene (BT) in n-octane, and adding n-tetradecane as internal standard substance.
Adding an oil product and the boron nitride-based porous ionic liquid into a double-neck sleeve bottle according to a certain proportion, magnetically stirring and reacting at a set temperature, separating the reacted boron nitride-based porous ionic liquid from the oil product by a simple pouring method, detecting the content of sulfide in the oil product by adopting a gas chromatograph (GC-FID) in the reaction process, and calculating the desulfurization rate:
Example 1
0.0202G of prepared microporous boron nitride is added into 2.0g of pyridine-based ionic liquid [ BPy ] [ FeCl 4 ], the rotating speed is set to be 500rpm, the mixture is magnetically stirred for 10 hours at 100 ℃, and then a sample is placed in an oven at 80 ℃ to be dried for 4 hours, so that the boron nitride-based microporous ionic liquid 1% -m-BN-PIL is obtained.
Example 2
Adding 0.0619g of prepared microporous boron nitride into 2.0g of pyridine-type ionic liquid [ BPy ] [ FeCl 4 ], setting the rotating speed to be 500rpm, magnetically stirring for 10 hours at 100 ℃, and then drying a sample in an oven at 80 ℃ for 4 hours to obtain the 3% -m-BN-PIL of the boron nitride-based porous ionic liquid.
Example 3
Adding 0.1505g of prepared microporous boron nitride into 2.0g of pyridine-type ionic liquid [ BPy ] [ FeCl 4 ], setting the rotating speed to be 500rpm, magnetically stirring for 10 hours at 100 ℃, and then drying a sample in an oven at 80 ℃ for 4 hours to obtain the boron nitride-based porous ionic liquid 7% -m-BN-PIL.
Example 4
0.3529G of prepared microporous boron nitride is added into 2.0g of pyridine-based ionic liquid [ BPy ] [ FeCl 4 ], the rotating speed is set to be 500rpm, the mixture is magnetically stirred for 10 hours at 100 ℃, and then a sample is placed in an oven at 80 ℃ to be dried for 4 hours, so that the boron nitride-based microporous ionic liquid 15% -m-BN-PIL is obtained.
Example 5
Adding 0.5000g of prepared microporous boron nitride into 2.0g of pyridine-type ionic liquid [ BPy ] [ FeCl 4 ], setting the rotating speed to be 500rpm, magnetically stirring for 10 hours at 100 ℃, and then drying a sample in an oven at 80 ℃ for 4 hours to obtain the boron nitride-based porous ionic liquid 20% -m-BN-PIL serving as an extractant.
Example 6
Adding 0.1505g of prepared microporous boron nitride into 2.0g of imidazole-based ionic liquid [ C 6BIM2][FeCl4]2 ], setting the rotating speed to be 500rpm, magnetically stirring for 10 hours at 60 ℃, and then drying a sample in an oven at 80 ℃ for 4 hours to obtain the boron nitride-based microporous ionic liquid 7% -m-BN-PIL serving as an extractant.
Example 7
2.5G of DBT model oil and 0.5050g of boron nitride-based porous ionic liquid 1% -m-BN-PIL obtained in example 1 are added into a double-neck sleeve bottle, magnetic stirring reaction is carried out in a water bath with the temperature of 40 ℃, tap water is adopted for condensation reflux, the upper layer of clear suspension liquid is taken every 10 minutes in the reaction process and injected into GC-FID to detect the content of residual sulfide in the model oil, and the desulfurization rate after experimental balance is calculated. According to the above scheme, 2.5gDBT model oil was added to each of the other two-necked flask, 0.5155g of 3% -m-BN-PIL obtained in example 2, 0.5376g of 7% -m-BN-PIL obtained in example 3, 0.5882g of 15% -m-BN-PIL obtained in example 4, 0.625g of 20% -m-BN-PIL obtained in example 5, and 0.5g of pyridine type ionic liquid [ BPy ] [ FeCl 4 ] were added, and the desulfurization rates after experimental equilibrium were calculated, respectively, and the results are shown in FIG. 3. It can be seen that: the extraction performance of the boron nitride-based porous ionic liquid is positively correlated with the anchoring amount of microporous boron nitride, when the optimal boron nitride anchoring amount is 20%, the desulfurization rate of the boron nitride-based porous ionic liquid can reach 59.2%, and compared with the traditional pyridine-type ionic liquid [ BPy ] [ FeCl 4 ], the boron nitride-based porous ionic liquid obtained after the boron nitride anchoring can improve the removal performance of sulfides in fuel oil.
Example 8
2.5G of DBT model oil is added into a double-neck sleeve bottle, 0.625g of boron nitride-based porous ionic liquid 20% -m-BN-PIL obtained in example 5 is added into the oil, magnetic stirring reaction is carried out in water baths with different temperatures (30 ℃,40 ℃,50 ℃ and 60 ℃), tap water is adopted for condensation reflux, the upper clear suspension is taken every 10 minutes in the reaction process and injected into GC-FID to detect the content of residual sulfide in the model oil, and the desulfurization rate after experimental balance is calculated, so that the result is shown in figure 4. The boron nitride-based porous ionic liquid is sensitive to temperature, and the higher temperature is unfavorable for removing sulfides in the fuel oil by the boron nitride-based porous ionic liquid, and the desulfurization rate can reach 59.2% at the optimum temperature of about 40 ℃.
Example 9
2.5G of DBT model oil was added to a double neck flask, and 0.625g of the boron nitride based porous ionic liquid 20% -m-BN-PIL obtained in example 5 was added to the oil. According to the scheme, 2.5g of DBT model oil is added into another double-neck sleeve bottle, 0.5g of pyridine type ionic liquid is added into the oil, magnetic stirring reaction is carried out in a constant-temperature water bath at 40 ℃, tap water is adopted for condensation reflux, upper clear suspension is respectively taken every 10 minutes in the reaction process and injected into GC-FID to detect the content of sulfide in the model oil, and the desulfurization rate after experimental balance is respectively calculated.
2.5G of 4,6-DMDBT model oil was added to a double neck flask, and 0.625g of the boron nitride based porous ionic liquid described in example 5 was added to the oil. According to the scheme, 2.5g of 4,6-DMDBT model oil is added into another double-neck sleeve bottle, 0.5g of pyridine type ionic liquid is added into the oil, magnetic stirring reaction is carried out in a constant-temperature water bath at 40 ℃, tap water is adopted for condensation reflux, the upper clear suspension is respectively taken every 10 minutes in the reaction process, the content of sulfide in the model oil is detected by injecting the upper clear suspension into GC-FID, and the desulfurization rate after experimental balance is respectively calculated.
2.5G of 4-MDBT model oil was added to the double-necked flask, and 0.625g of the boron nitride-based porous ionic liquid described in example 5 was added to the oil. According to the scheme, 2.5g of 4-DMDBT model oil is added into another double-neck sleeve bottle, 0.5g of pyridine type ionic liquid is added into the oil, magnetic stirring reaction is carried out in a constant-temperature water bath at 40 ℃, tap water is adopted for condensation reflux, the upper layer of clear suspension liquid is respectively taken every 10 minutes in the reaction process and injected into GC-FID to detect the content of sulfide in the model oil, and the desulfurization rate after experimental balance is respectively calculated.
As shown in fig. 5, it can be seen that compared with the conventional ionic liquid, the boron nitride-based porous ionic liquid has higher removal efficiency improvement on different sulfur-containing substrates.
Example 10
2.5G of DBT model oil and 0.625g of the boron nitride-based porous ionic liquid 20% -m-BN-PIL obtained in the example 5 are added into a double-neck sleeve bottle, magnetic stirring reaction is carried out in a water bath with the temperature of 40 ℃, tap water is adopted for condensation reflux, after the reaction reaches equilibrium, the upper oil is poured, the upper oil is fully separated from the extractant, then 0.625g of the boron nitride-based porous ionic liquid described in the example 5 is added into the oil, and the operation is repeated. According to the above scheme, 2.5g of DBT model oil was added to the other double-necked flask, then 0.5g of pyridine type ionic liquid [ BPy ] [ FeCl 4 ] was added to the oil, and at the same time, tap water was used for condensation reflux, the upper clear suspension was injected into GC-FID to detect the content of residual sulfide in the model oil, and the above operation was repeated 4 times, and the result is shown in FIG. 6. It can be seen that after the extractant is used for 4 times, the boron nitride-based porous ionic liquid can reduce the sulfur-containing compound in the fuel to below 8ppm, and the boron nitride-based porous ionic liquid can achieve the purpose of deep desulfurization relative to the traditional pyridyl ionic liquid.
Example 11
The preparation method comprises the steps of respectively taking 0.1475g of the boron nitride-based porous ionic liquid and the traditional imidazole-based ionic liquid [ C 6BIM2][FeCl4]2 ] in the embodiment 6, respectively placing the boron nitride-based porous ionic liquid and the traditional imidazole-based ionic liquid in a stainless steel absorption kettle, adding a magnet, covering a sealing cover, closing a steel bottle air valve at the water bath temperature of 40 ℃, starting a vacuum pump to vacuumize a system, enabling the pressure in an absorption device to reach 4kPa and enable the indication number to be unchanged, closing the vacuum pump, opening a steel bottle valve and an air inlet valve of the buffer kettle, introducing a certain amount of sulfur dioxide gas into the buffer kettle, closing the steel bottle, opening the air inlet valve of the absorption bottle, introducing the sulfur dioxide gas into the absorption bottle at the speed of 4mL/min, stirring, absorbing and keeping the stirring speed of 500rpm, recording the temperature and the pressure on a display at the moment, continuously adding the sulfur dioxide gas into the absorption kettle device when the pressure is unchanged within 10 minutes, repeating the operation steps, and obtaining another set of data, and calculating the absorption amount of the sulfur dioxide by the extractant under the 0-102KPa according to the absorption amount of the extractant under each pressure point, and the sulfur dioxide absorption effect of 7% -m-PIL and the imidazole-based ionic liquid [ C 6BIM2][FeCl4]2 -based on the sulfur dioxide under the pressure of 0-102 KPa. As shown in fig. 7, it can be seen that the introduction of microporous boron nitride effectively improves the absorption of sulfur dioxide by imidazole-based ionic liquids, which illustrates that the boron nitride-based porous ionic liquid described in example 6 is a type of ionic liquid with a rich pore structure.
Example 12
Respectively taking 0.1032g of the boron nitride-based porous ionic liquid and the traditional pyridine-based ionic liquid [ BPy ] [ FeCl 4 ] in the embodiment 5, namely, carbon dioxide absorbent, respectively placing the carbon dioxide absorbent and the boron nitride-based porous ionic liquid in a stainless steel absorption kettle, adding a magnet, covering a sealing cover, closing a steel bottle air valve at the water bath temperature of 40 ℃, starting a vacuum pump to vacuumize the system, enabling the pressure in the absorption kettle device to reach 4kPa and the indication number to be unchanged, closing the vacuum pump, opening the steel bottle valve and a buffer kettle air inlet valve, closing the steel bottle after a certain amount of carbon dioxide gas is introduced into the buffer kettle, opening the absorption bottle air inlet valve to introduce carbon dioxide gas into the absorption bottle at the speed of 4mL/min, stirring, absorbing and keeping the stirring speed of 500rpm, recording the temperature and the pressure on a data display when the pressure is unchanged within 10 minutes, continuously introducing CO 2 gas into the device, repeating the above operation steps, and obtaining another group of data, and calculating the absorption amount of the extractant under the carbon dioxide air pressure of 0-100KPa according to the absorption amount of the extractant at each pressure point, wherein the boron nitride-based porous ionic liquid 20% -37 m and the pyridine-based carbon dioxide-based ionic liquid [ BPCl ] is 35. As shown in fig. 8, it can be seen that the introduction of microporous boron nitride effectively improves the absorption of carbon dioxide by pyridine-type ionic liquids, and the boron nitride-based porous ionic liquid described in example 5 is a type of ionic liquid with a rich pore structure.
The invention provides a boron nitride-based porous ionic liquid, a preparation method and an application thought and method thereof, and particularly the method and the method for realizing the technical scheme are a plurality of methods, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by one of ordinary skill in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (4)
1. The application of the boron nitride-based porous ionic liquid in removing sulfides in fuel oil is characterized in that the boron nitride-based porous ionic liquid consists of microporous boron nitride and ionic liquid, the size of the ionic liquid is larger than that of the micropores of the boron nitride, and the ionic liquid and the boron nitride form an interaction, so that the boron nitride-based porous ionic liquid with a rich pore channel structure is formed;
The ionic liquid is pyridine-type ionic liquid [ BPy ] [ FeCl 4 ];
The micropore size of the micropore boron nitride is not more than 1nm;
The mass of the microporous boron nitride accounts for 1-20% of the total mass of the boron nitride-based porous ionic liquid;
The boron nitride-based porous ionic liquid is prepared by the following steps:
(1) Adding a surfactant into the methanol aqueous solution, stirring uniformly, adding boric acid, and stirring uniformly;
(2) Adding melamine into the solution in the step (1), and stirring for reaction to obtain white precipitate;
(3) Separating the white precipitate in the step (2), and calcining in an inert atmosphere to obtain microporous boron nitride;
(4) And (3) mixing the microporous boron nitride prepared in the step (3) with the ionic liquid, stirring for full dispersion, and then carrying out vacuum drying to obtain the microporous boron nitride.
2. The use according to claim 1, characterized in that in step (2) the molar ratio of boric acid to melamine is 1: 4-1: 8.
3. The use according to claim 1, wherein in step (3), the calcination conditions are: the gas flow rate is 60-100 ml/min, and the temperature is kept at 700-900 ℃ for 2-5h at the heating rate of 2-10 ℃/min.
4. The use according to claim 1, wherein in step (4), the dispersing is performed by magnetic stirring, and the magnetic stirring is performed at a speed of 400-800 rpm/min for 5-10 hours at a temperature of 60-100 ℃; the temperature of vacuum drying is 60-100 ℃, and the drying time is 4-10 h.
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