CN113754875A - Polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and preparation method thereof - Google Patents

Polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and preparation method thereof Download PDF

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CN113754875A
CN113754875A CN202111173963.8A CN202111173963A CN113754875A CN 113754875 A CN113754875 A CN 113754875A CN 202111173963 A CN202111173963 A CN 202111173963A CN 113754875 A CN113754875 A CN 113754875A
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ionic liquid
gasoline
heteropoly acid
polyether type
temperature
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张连正
李方方
徐冬梅
高军
马艺心
赵萍萍
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Shandong University of Science and Technology
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine groups
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    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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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
    • C10G21/12—Organic compounds only
    • C10G21/22—Compounds containing sulfur, selenium, or tellurium
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Abstract

The invention discloses a polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and a preparation method thereof. Firstly, reacting cationic liquid with ethylene oxide under inert atmosphere to generate an intermediate I, and then reacting the intermediate I with 1, 3-propane sultone according to the ratio of 1:1 to generate an intermediate II, and finally slowly dropwise adding a heteropoly acid aqueous solution into the intermediate IIAnd reacting for 10-12h at 80-85 ℃ to obtain the polyether type heteropoly acid temperature-controlled ionic liquid. By introduction of
Figure DDA0003292363130000011
The acidity of the ionic liquid is regulated by the acid group and the heteropoly acid, the melting point of the ionic liquid is reduced by introducing polyether groups with different polymerization degrees, the ionic liquid with stable property is obtained, and the purposes of high-temperature homogeneous reaction and low-temperature two-phase separation are realized by regulating the solubility response of the polyether type ionic liquid in gasoline and diesel.

Description

Polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and preparation method thereof
Technical Field
The invention belongs to the field of oil product denitrification, and particularly relates to polyether type heteropoly acid temperature-controlled ionic liquid for removing basic nitrides of gasoline and diesel oil and a preparation method thereof.
Background
Efficient separation of high value-added compounds from complex systems is one of the important research directions in chemical engineering, where great challenges arise from the separation of complex systems. The organic nitride is one of high value-added components of complex systems, and has an extremely important position in the production life of people. In industry, organic nitrogen compounds are also mainly derived from petroleum and coal-based products, wherein basic nitrogen compounds include pyridine, aniline, quinoline, and the like, and derivatives thereof. In addition, there are also trace amounts of organic nitrides in fuel oils such as gasoline and diesel, which can be converted into NO causing atmospheric pollution or serious harm to the environment and human health such as acid rain, photochemical smog and the like during the combustion process of the oilsx. Removal is more difficult than sulfide and the presence of nitrides can seriously affect catalytic hydrogenation removal (HDS) of sulfides. However, the pollution of the atmosphere caused by various waste gases generated by the combustion of the waste gases is increasingly serious while creating a great deal of economic value. Due to the increasing strictness of environmental requirements, it is necessary to remove the nitrogen compounds from the fuel oil as much as possible.
At present, denitrification methods are mainly divided into hydrodenitrogenation and non-hydrodenitrogenation, and the non-hydrodenitrogenation methods mainly include adsorption denitrification, solvent refining denitrification, complex denitrification, oxidation denitrification and the like at present.
Kim et al [ Ultra-deep depletion and condensation of diesel fuel by selective adsorption over the same solvents: A study on adsorption selectivity and mechanism [ J ]. Catalysis Today,2006,111(1-2):74-83 ] compared several adsorbents, activated carbon and activated alumina for adsorption removal of nitrogen and sulfur from model diesel compounds and examined their adsorption capacity and selectivity. But the adsorption denitrification operation process is relatively complex, the automation degree is low, and the yield of refined oil is low; the adsorbent needs to be regenerated, otherwise, the dosage of the adsorbent is large.
Compared with the traditional separation means, the liquid-liquid extraction process based on the functional ionic liquid is an environment-friendly and efficient separation means in recent years, the structures of ILs can be designed, the molecular recognition capability is relatively strong, and multiple action modes such as hydrogen bonds, static electricity, pi-pi bonds, van der Waals force and the like are provided, so that the liquid-liquid extraction process based on the functional ionic liquid has wide research and application in multiple fields such as organic synthesis, catalysis, electrochemistry, extraction separation, biomass conversion and the like. Zhou et al [ Removal of nitrogen compounds from fungal oils using animal-based ionic liquids [ J].Liquid Fuels Technology,2017,35(1):45-50.]Several imidazole ionic liquids with different anionic characteristics were studied and their denitrification performance on model oils containing indole or quinoline was determined. The experimental results show that [ C ]4mim]HSO4The model oil has good denitrification performance, and the denitrification efficiency of the model oil reaches about 99 percent. In addition, after the ionic liquid is circulated for 5 times, the removal rate of quinoline and indole can reach 98.4% and 96.3%, respectively.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides polyether type heteropoly acid temperature-controlled ionic liquid for removing alkaline nitrides in gasoline and diesel oil and a preparation method thereof, wherein the ionic liquid is temperature-controlled ionic liquid which has double acidic sites with adjustable acidity, phase states and solubility in gasoline and diesel oil and responds to temperature change, and can be used for removing trace alkaline nitrides in gasoline and diesel oil by temperature-controlled phase separation.
In order to achieve the purpose, the invention adopts the technical scheme that:
a polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil is composed of a polyether group with temperature response capability, a cation framework with a strong acid functional group and heteropoly acid anions, and the structural formula of the temperature control ionic liquid is as follows:
Figure BDA0003292363110000021
wherein the cation X+Is one of imidazole cation, pyridine cation and tetramethylguanidine cation, and the structures of the imidazole, the pyridine and the tetramethylguanidine are respectively as follows:
Figure BDA0003292363110000022
n represents-CH2CH2The number of O-is 11-85;
the heteropoly acid anion Y-Is phosphotungstate, silicotungstic acid or phosphomolybdate.
The polyether type heteropoly acid temperature-controlled ionic liquid can remove alkaline nitride with high efficiency and high selectivity, thereby removing trace alkaline nitride in gasoline and diesel oil to an extremely low degree.
The invention is provided by introduction
Figure BDA0003292363110000023
The acidic group and the heteropoly acid provide the functional ionic liquid with adjustable acidity, and high removal efficiency and selectivity can be realized; the melting point of the ionic liquid is reduced by introducing polyether groups with different polymerization degrees, and the solubility response of the polyether type ionic liquid in gasoline and diesel oil is regulated and controlled. At room temperature, the ionic liquid and single-component, double-component or multi-component solvent (gasoline and diesel oil) are not mutually soluble, when the Critical Solution Temperature (CST) is reached, the solvent and the ionic liquid are in a completely mutually soluble state to form a homogeneous solution, and the polyether type heteropoly acid temperature control ionic liquid can be in more sufficient contact with alkaline nitride in gasoline for reaction. Compared with the traditional two-phase extraction process, the mechanical stirring is not needed,and can achieve higher alkaline nitride removal effect under the condition of less using amount of polyether type heteropoly acid temperature control ionic liquid, and simplify the operation process.
Specifically, the polyether type heteropoly acid temperature control ionic liquid used for removing basic nitrides of gasoline and diesel oil comprises the following specific steps:
adding polyether type heteropoly acid temperature control ionic liquid into the gasoline and diesel oil to be treated, and stirring in a sealing way, wherein the polyether type heteropoly acid temperature control ionic liquid and the gasoline and diesel oil are not mutually soluble at room temperature; reacting at 40-80 deg.C until the critical solution temperature is reached, wherein the system is completely dissolved; and cooling to room temperature after the reaction is finished, standing for layering, wherein the upper liquid phase is the gasoline and diesel phase subjected to denitrification, and the lower liquid phase is the temperature control ionic liquid phase. The purposes of high-temperature homogeneous reaction and low-temperature two-phase separation are realized by regulating and controlling the temperature. The temperature control ionic liquid phase after phase separation can be separated for recycling.
Specifically, the mass ratio of the polyether type heteropoly acid temperature control ionic liquid to gasoline and diesel oil is 1: 10-50 ℃, the temperature is 40-80 ℃, and the reaction time is 10-40 min.
Specifically, the total mass fraction of the basic nitrides in the gasoline and diesel oil is less than 1%. The basic nitride is pyridine and quinoline, wherein the mass ratio of the pyridine to the quinoline is 1: 1.
Further, the ionic liquid after phase separation is added into new gasoline and diesel oil again for the same operation, and the ionic liquid is recycled for more than 5 times.
The preparation method of the polyether type heteropoly acid temperature-control ionic liquid for removing the basic nitride of the gasoline and diesel oil specifically comprises the following steps:
(1) adding a cationic liquid into a high-pressure reaction kettle containing a solvent A, adding ethylene oxide, sealing the kettle, replacing with nitrogen or inert gas for 3-5 times, stirring and reacting at 30 ℃ for 2 hours under a certain pressure of nitrogen or inert atmosphere, heating to 70-75 ℃ for 6-10 hours, and removing the solvent A to obtain an intermediate I, wherein the cationic liquid is N-methylimidazole, pyridine or 1,1,3, 3-tetramethylguanidine;
(2) dissolving 1, 3-propane sultone in a solvent B, dropwise adding an intermediate I into the obtained solution, sealing the kettle, replacing with inert gas for 3-5 times, reacting at 50-60 ℃ for 5-6h under an inert atmosphere with certain pressure, and removing the solvent B to obtain an intermediate II, wherein the molar ratio of the intermediate I to the 1, 3-propane sultone is 1: 1;
(3) slowly dropwise adding a heteropoly acid aqueous solution into the intermediate II, and reacting at 80-85 ℃ for 10-12h to obtain polyether type heteropoly acid temperature control ionic liquid; the heteropoly acids include, but are not limited to, phosphotungstic acid (H)3O40PW12·xH2O), silicotungstic acid (H)4[Si(W3O10)4]·xH2O), phosphomolybdic acid (H)3[P(Mo3O10)4]) Any one of them.
The solvent A in the step (1) is one of ethanol, methanol and N, N-dimethylformamide.
And (3) the solvent B in the step (2) is one of ethyl acetate and toluene.
The total removal efficiency of the polyether type heteropoly acid temperature-controlled ionic liquid to the basic nitride can reach 95.5-99.1%. The polyether type heteropoly acid ionic liquid can be recycled for 5-10 times.
The invention uses polyether chains with different polymerization degrees of temperature control structural units and
Figure BDA0003292363110000031
acidic group (-SO)3H, sulfonic group) is introduced into the cation of the ionic liquid together, and the acidic ionic liquid with the temperature control effect is prepared.
Compared with the traditional method, the method of the invention has the following beneficial effects: (1) by introduction of
Figure BDA0003292363110000032
The acidity of the ionic liquid is regulated and controlled by the acidic groups and the heteropoly acid, and the melting point of the ionic liquid is reduced by introducing polyether groups with different polymerization degrees, so that the ionic liquid with stable properties is obtained; (2) the purposes of high-temperature homogeneous reaction and low-temperature two-phase separation are realized by regulating and controlling the solubility response of the polyether type ionic liquid in gasoline and diesel oil; (3) not only realizes the high-efficiency removal of alkaline nitride in homogeneous reaction under the condition of using a small amount of ionic liquid, but also realizes the easy separation and return of the denitrifierRecycling and recycling properties, reducing the loss of the ionic liquid in the recycling process and providing a new idea for the denitrification of gasoline and diesel.
Drawings
FIG. 1 is an IR spectrum of intermediate I referred to in example 1.
FIG. 2 is an infrared spectrum of 1, 3-propane sultone and intermediate II in example 1.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to limit the scope of the present invention, but are intended to cover modifications within the scope of the present invention.
Example 1
(1) Synthesis of polyether type heteropoly acid temperature control ionic liquid
Adding 0.1mol of 1,1,3, 3-tetramethylguanidine (cationic liquid) and 20mL of ethanol into an autoclave, placing the autoclave in a refrigerator for freezing for 12h, weighing 35mL of ethylene oxide, adding the ethylene oxide into the autoclave, sealing the autoclave, and replacing the air in the autoclave with nitrogen gas at the pressure of 3.5MPa for 3 times. Stirring in water bath at 30 deg.C for 2 hr, heating to 70 deg.C, reacting for 6-10 hr, cooling, releasing pressure, and opening the kettle. The reaction solution was distilled under reduced pressure in a round-neck flask to remove absolute ethanol to a constant weight to obtain an intermediate I, and the average degree of polymerization n was calculated according to the product weight gain method (see table 1). Adding 0.1mol of 1, 3-propane sultone into a high-pressure reaction kettle, adding 30mL of ethyl acetate to completely dissolve the 1, dropwise adding the intermediate I into a water bath at 30 ℃ according to a molar ratio of 1:1, sealing the kettle, and heating to 50 ℃ for reaction for 5 hours. After the reaction is finished, transferring the obtained reaction mixture into a single-neck flask, and removing the solvent ethyl acetate by reduced pressure distillation to obtain an intermediate II. And (3) putting 0.1mol of the intermediate II into a single-neck flask, slowly dropwise adding 20mL of aqueous solution dissolved with 0.1mol of phosphotungstic acid by using a constant-pressure dropping funnel, and stirring and reacting the mixture at 80 ℃ for 10-12h after the dropwise adding is finished. And (4) after the reaction is finished, reducing the pressure and dehydrating to constant weight, and drying to obtain the target product polyether type heteropoly acid ionic liquid (III).
Figure BDA0003292363110000041
FIG. 1 is an infrared spectrum of intermediate I, which is shown at 3400cm-1Absorption of stretching vibration in the position of-OH, 2970cm-1，2872cm-11658cm for saturated C-H stretching vibration absorption-1Is the telescopic vibration absorption of C ═ N, 1109cm-1There is C-O-C asymmetric telescopic vibration absorption at 942cm-1The point is the symmetrical telescopic vibration absorption of C-O-C. Can be attributed to the stretching vibration of C-O-C after polymerization of the ethyleneoxy units in the cationic structure of the intermediate I.
FIG. 2 is an IR spectrum of 1, 3-propane sultone and intermediate II, which is seen at 1247cm-1Telescopic vibration of 1041cm with S ═ O-1The stretching vibration of S-O can be attributed to the stretching vibration of S ═ O and S-O in the sulfonic acid group grafted on the basis of the intermediate I by the intermediate II.
TABLE 1
Cationic liquid Volume of ethylene oxide Average degree of polymerization of ethylene oxide group
Example 1 1,1,3, 3-tetramethylguanidine 15 23
Example 2 N-methylimidazole 8 11
Example 3 N-methylimidazole 25 49
Example 4 Pyridine compound 30 66
Example 5 Pyridine compound 50 85
Example 6 1,1,3, 3-tetramethylguanidine 20 37
Example 7 1,1,3, 3-tetramethylguanidine 40 76
(2) Removal of alkaline nitride from gasoline and diesel oil simulation oil
Preparing simulated oil: 32g of p-xylene and 1.86g of basic nitride (the mass ratio of pyridine to quinoline is 1:1) are accurately weighed and dissolved in 160g of normal hexane to prepare the gasoline and diesel simulated oil with the mass fraction of 0.96%.
Removing alkaline nitride:
a) adding 1g of the polyether type heteropoly acid ionic liquid (n ═ 23) prepared in the step (1) into a reaction bottle with magnetic stirring, then adding 50g of gasoline-diesel simulated oil (1:50), sealing, heating in a water bath, carrying out magnetic stirring, and reacting for 10min at 40 ℃. Standing at room temperature for layering, wherein the upper liquid phase is a denitrified gasoline and diesel simulated oil phase, the lower layer is a temperature-controlled ionic liquid phase, and the upper simulated oil phase is collected. Quantitative analysis is carried out by gas chromatography, the content of alkaline nitride before and after extraction is measured, and the total removal efficiency of the nitride is measured to be 95.9 percent, wherein the removal efficiency of the pyridine reaches 96.2 percent.
b) And (3) adding a back-extraction agent anhydrous ether into the temperature-controlled ionic liquid phase, stirring, standing until complete layering is achieved, separating an upper anhydrous ether phase and a lower regenerated polyether type heteropoly acid temperature-controlled ionic liquid, returning to the step a for repeated use, wherein the repeated use times and the effect are shown in the following table 2.
TABLE 2
Figure BDA0003292363110000051
Figure BDA0003292363110000061
Note: the 2 nd regeneration, i.e. the 1 st regeneration.
Example 2:
(1) synthesis of polyether type heteropoly acid temperature control ionic liquid
As shown in Table 1, this example is the same as example 1 except that the cationic liquid and the ethylene oxide are added by volume. The specific reaction process is as follows:
Figure BDA0003292363110000062
(2) removal of alkaline nitride from gasoline and diesel oil simulation oil
a) 1g of ionic liquid denitrifier (n: 11) was added to a reaction flask equipped with magnetic stirring, then 40g of the gasoline-diesel simulated oil (1:40) prepared in example 1 was added thereto, and the mixture was sealed, heated in a water bath and magnetically stirred, and reacted at 50 ℃ for 10 min. Standing at room temperature for layering, wherein the upper liquid phase is a denitrified gasoline and diesel simulated oil phase, the lower layer is a temperature-controlled ionic liquid phase, and the upper simulated oil phase is collected. Quantitative analysis is carried out by gas chromatography, the content of alkaline nitride before and after extraction is measured, the total removal efficiency of the nitride is 95.5 percent, wherein the removal efficiency of the pyridine reaches 96.1 percent.
b) The polyether type heteropoly acid temperature-controlled ionic liquid is regenerated by the stripping agent as in example 1 and is reused, and the repeated use times and the effect are shown in the following table 3.
TABLE 3
Figure BDA0003292363110000063
Figure BDA0003292363110000071
Note: the 2 nd regeneration, i.e. the 1 st regeneration.
Example 3:
(1) synthesis of polyether type heteropoly acid temperature control ionic liquid
As shown in Table 1, this example is the same as example 1 except that the cationic liquid and the ethylene oxide are added by volume.
(2) Removal of alkaline nitride from gasoline and diesel oil simulation oil
a) 1g of ionic liquid denitrifier (n: 49) was added to a reaction flask equipped with magnetic stirring, 30g of the gasoline-diesel simulated oil (1:30) prepared in example 1 was then added thereto, the mixture was sealed, heated in a water bath and magnetically stirred, and the mixture was reacted at 50 ℃ for 20 min. Standing at room temperature for layering, wherein the upper liquid phase is a denitrified gasoline and diesel simulated oil phase, the lower layer is a temperature-controlled ionic liquid phase, and the upper simulated oil phase is collected. Quantitative analysis is carried out by gas chromatography, the content of alkaline nitride before and after extraction is measured, and the total removal efficiency of the nitride is 96.3 percent, wherein the removal efficiency of the pyridine reaches 96.9 percent.
b) The polyether type heteropoly acid temperature-controlled ionic liquid is regenerated by the stripping agent as in example 1 and is reused, and the repeated use times and the effect are shown in the following table 4.
TABLE 4
Number of times of use Total nitride removal efficiency (%) Removal efficiency of pyridine (%)
1 st time 96.3 96.9
2 nd time 96.2 96.6
3 rd time 95.9 96.2
4 th time 95.5 95.8
5 th time 95.2 95.2
6 th time 94.8 95.1
7 th time 94.5 94.7
Note: the 2 nd regeneration, i.e. the 1 st regeneration.
Example 4:
(1) synthesis of polyether type heteropoly acid temperature control ionic liquid
As shown in Table 1, this example is the same as example 1 except that the cationic liquid and the ethylene oxide are added by volume. The specific reaction process is as follows:
Figure BDA0003292363110000081
(2) removal of alkaline nitride from gasoline and diesel oil simulation oil
a) 1g of ionic liquid denitrifying agent (n-68) is added, then 25g of the gasoline and diesel simulated oil (1:25) prepared in example 1 is added, sealed, heated in a water bath and magnetically stirred, and reacted at 60 ℃ for 30 min. Standing at room temperature for layering, wherein the upper liquid phase is a denitrified gasoline and diesel simulated oil phase, the lower layer is a temperature-controlled ionic liquid phase, and the upper simulated oil phase is collected. Quantitative analysis is carried out by gas chromatography, the content of basic nitride before and after extraction is measured, and the total removal efficiency of pyridine and quinoline is 97.2 percent, wherein the removal efficiency of pyridine reaches 98.3 percent.
b) The polyether type heteropoly acid temperature-controlled ionic liquid is regenerated by the stripping agent as in example 1 and is reused, and the repeated use times and the effect are shown in the following table 5.
TABLE 5
Number of times of use Total nitride removal efficiency (%) Removal efficiency of pyridine (%)
1 st time 97.2 98.3
2 nd time 97.1 98.0
3 rd time 96.7 97.7
4 th time 96.4 97.3
5 th time 96.3 96.8
6 th time 95.8 96.2
7 th time 95.3 95.7
8 th time 95.1 95.6
Note: the 2 nd regeneration, i.e. the 1 st regeneration.
Example 5:
(1) synthesis of polyether type heteropoly acid temperature control ionic liquid
As shown in Table 1, this example is the same as example 1 except that the cationic liquid and the ethylene oxide are added by volume.
(2) Removal of alkaline nitride from gasoline and diesel oil simulation oil
a) 1g of ionic liquid denitrifier (n: 85) was added to a reaction flask equipped with magnetic stirring, 20g of the gasoline-diesel simulated oil (1:20) prepared in example 1 was then added thereto, the mixture was sealed, heated in a water bath and magnetically stirred, and the mixture was reacted at 70 ℃ for 30 min. Standing at room temperature for layering, wherein the upper liquid phase is a denitrified gasoline and diesel simulated oil phase, the lower layer is a temperature-controlled ionic liquid phase, and the upper simulated oil phase is collected. Quantitative analysis is carried out by gas chromatography, the content of basic nitride before and after extraction is measured, and the total removal efficiency of pyridine and quinoline is 99.1 percent, wherein the removal efficiency of pyridine reaches 98.5 percent.
b) The polyether type heteropoly acid temperature-controlled ionic liquid is regenerated by the stripping agent as in example 1 and is reused, and the repeated use times and the effect are shown in the following table 6.
TABLE 6
Number of times of use Total nitride removal efficiency (%) Removal efficiency of pyridine (%)
1 st time 99.1 98.5
2 nd time 99.0 98.3
3 rd time 98.7 97.9
4 th time 98.8 97.7
5 th time 98.4 97.3
6 th time 98.1 96.8
7 th time 97.9 96.6
8 th time 97.8 96.3
9 th time 97.2 96.1
Note: the 2 nd regeneration, i.e. the 1 st regeneration.
Example 6:
(1) synthesis of polyether type heteropoly acid temperature control ionic liquid
As shown in Table 1, this example was the same as example 1 except that the ethylene oxide was added in the same amount by volume.
(2) Removal of alkaline nitride from gasoline and diesel oil simulation oil
a) 1g of polyether type heteropoly acid temperature-controlled ionic liquid denitrifying agent (n is 37) is added, 15g of the prepared gasoline and diesel oil simulation oil (1:15) in the example 1 is added, the mixture is sealed, heated in a water bath and magnetically stirred, and the mixture reacts for 40min at 70 ℃. Standing at room temperature for layering, wherein the upper liquid phase is a denitrified gasoline and diesel simulated oil phase, the lower layer is a temperature-controlled ionic liquid phase, and the upper simulated oil phase is collected. Quantitative analysis is carried out by gas chromatography, the content of basic nitride before and after extraction is measured, and the total removal efficiency of pyridine and quinoline is 97.3 percent, wherein the removal efficiency of pyridine reaches 97.6 percent.
b) The polyether type heteropoly acid temperature-controlled ionic liquid is regenerated by the stripping agent as in example 1 and is reused, and the repeated use times and the effect are shown in the following table 7.
TABLE 7
Number of times of use Total nitride removal efficiency (%) Removal efficiency of pyridine (%)
1 st time 97.3 97.6
2 nd time 97.1 97.4
3 rd time 96.8 97.1
4 th time 96.5 96.8
5 th time 96.4 96.5
6 th time 96.1 96.3
7 th time 95.9 96.2
8 th time 95.7 95.9
9 th time 95.3 95.6
Note: the 2 nd regeneration, i.e. the 1 st regeneration.
Example 7:
(1) synthesis of polyether type heteropoly acid temperature control ionic liquid
As shown in Table 1, this example was the same as example 1 except that the ethylene oxide was added in the same amount by volume.
(2) Removal of alkaline nitride from gasoline and diesel oil simulation oil
a) 1g of polyether type heteropoly acid temperature-controlled ionic liquid denitrifying agent (n is 76) is added into a reaction bottle with magnetic stirring, 10g of gasoline and diesel oil simulated oil (1:10) prepared in example 1 is added, sealing is carried out, water bath heating is carried out, magnetic stirring is carried out, and reaction is carried out for 40min at 80 ℃. Standing at room temperature for layering, wherein the upper liquid phase is a denitrified gasoline and diesel simulated oil phase, the lower layer is a temperature-controlled ionic liquid phase, and the upper simulated oil phase is collected. Quantitative analysis is carried out by using gas chromatography, the content of basic nitride before and after extraction is measured, and the total removal efficiency of pyridine and quinoline is measured to be 98.5 percent, wherein the removal efficiency of pyridine reaches 98.7 percent.
b) The polyether type heteropoly acid temperature-controlled ionic liquid is regenerated by the stripping agent as in example 1 and is reused, and the repeated use times and the effect are shown in the following table 8.
TABLE 8
Number of times of use Total nitride removal efficiency (%) Removal efficiency of pyridine (%)
1 st time 98.5 98.9
2 nd time 98.3 98.7
3 rd time 98.2 98.1
4 th time 97.9 98.0
5 th time 97.5 97.9
6 th time 97.4 97.7
7 th time 97.1 97.4
8 th time 96.7 97.1
9 th time 96.2 96.6
10 th time 96.1 96.4
Note: the 2 nd regeneration, i.e. the 1 st regeneration.

Claims (6)

1. The polyether type heteropoly acid temperature-controlled ionic liquid for removing basic nitrides of gasoline and diesel oil is characterized in that the temperature-controlled ionic liquid consists of a polyether group with temperature response capability, a cation framework with a strong acid functional group and heteropoly acid anions, and the structural formula of the temperature-controlled ionic liquid is as follows:
Figure FDA0003292363100000011
wherein the cation X+Is one of imidazole cation, pyridine cation and tetramethylguanidine cation;
n represents-CH2CH2The number of O-is 11-85;
the heteropoly acid anion Y-Is phosphotungstate, silicotungstic acid or phosphomolybdate.
2. The polyether type heteropoly acid temperature-controlled ionic liquid for removing basic nitrides of gasoline and diesel oil as claimed in claim 1, which is characterized in that the specific steps of the polyether type heteropoly acid temperature-controlled ionic liquid for removing the basic nitrides of gasoline and diesel oil are as follows:
adding polyether type heteropoly acid temperature control ionic liquid into the gasoline and diesel oil to be treated, and stirring in a sealing way, wherein the polyether type heteropoly acid temperature control ionic liquid and the gasoline and diesel oil are not mutually soluble at room temperature; reacting at 40-80 deg.C until the critical solution temperature is reached, wherein the system is completely dissolved; and cooling to room temperature after the reaction is finished, standing for layering, wherein the upper liquid phase is the gasoline and diesel phase subjected to denitrification, and the lower liquid phase is the temperature control ionic liquid phase.
3. The polyether type heteropoly acid temperature-controlled ionic liquid for removing basic nitrides of gasoline and diesel oil as claimed in claim 2, wherein the mass ratio of the polyether type heteropoly acid temperature-controlled ionic liquid to gasoline and diesel oil is 1: 10-50, and the reaction time is 10-40 min.
4. The polyether type heteropoly acid temperature-controlled ionic liquid for removing basic nitrides of gasoline and diesel oil as claimed in claim 2, wherein the total mass fraction of the basic nitrides in the gasoline and diesel oil is less than 1%, the basic nitrides are pyridine and quinoline, and the mass ratio of the pyridine to the quinoline is 1: 1.
5. The preparation method of the polyether type heteropoly acid temperature-controlled ionic liquid for removing the basic nitrides of gasoline and diesel oil, which is disclosed by claim 1, is characterized by comprising the following steps of:
(1) adding a cationic liquid into a high-pressure reaction kettle containing a solvent A, adding ethylene oxide, sealing the kettle, replacing with nitrogen or inert gas, stirring and reacting at 30 ℃ for 2h under a nitrogen or inert atmosphere with a certain pressure, heating to 70-75 ℃ for reacting for 6-10h, and removing the solvent A to obtain an intermediate I, wherein the cationic liquid is N-methylimidazole, pyridine or 1,1,3, 3-tetramethylguanidine;
(2) dissolving 1, 3-propane sultone in a solvent B, dropwise adding an intermediate I into the obtained solution, sealing the kettle, replacing with inert gas for 3-5 times, reacting at 50-60 ℃ for 5-6h under an inert atmosphere with certain pressure, and removing the solvent B to obtain an intermediate II, wherein the molar ratio of the intermediate I to the 1, 3-propane sultone is 1: 1;
(3) slowly dropwise adding a heteropoly acid aqueous solution into the intermediate II, and reacting at 80-85 ℃ for 10-12h to obtain polyether type heteropoly acid temperature control ionic liquid; the heteropoly acid is any one of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
6. The preparation method of the polyether type heteropoly acid temperature-controlled ionic liquid for removing basic nitrides of gasoline and diesel oil as claimed in claim 5, wherein the solvent A is one of ethanol, methanol and N, N-dimethylformamide, and the solvent B is one of ethyl acetate and toluene.
CN202111173963.8A 2021-10-08 2021-10-08 Polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and preparation method thereof Pending CN113754875A (en)

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CN101861374A (en) * 2007-11-14 2010-10-13 环球油品公司 Methods of denitrogenating diesel fuel
CN102442951A (en) * 2010-10-12 2012-05-09 上海欣年石化助剂有限公司 Preparation method of functionalized polyacid-type sulfonic ionic liquid
CN102757323A (en) * 2011-04-26 2012-10-31 中国科学院兰州化学物理研究所 Method for preparing alkoxy ether compounds
CN103333114A (en) * 2013-07-18 2013-10-02 青岛科技大学 Imidazole ionic liquid with dual functions of oxidation and temperature control and synthetic method of ionic liquid
CN105038841A (en) * 2015-07-05 2015-11-11 青岛科技大学 Method for catalyzing fuel oil oxidation desulphurization by polyether type oxovanadium heteropolyacid ionic liquid
CN107267191A (en) * 2017-05-31 2017-10-20 宁波大学 With the method for nitride in imidazole type dication liquid removal diesel oil
CN107699274A (en) * 2017-11-06 2018-02-16 李俊霞 A kind of method of nitride in removing oil product
CN109331873A (en) * 2018-11-19 2019-02-15 万华化学集团股份有限公司 A method of Diacetone Acrylamide is prepared using temperature control inversion of phases heteropoly acid ionic-liquid catalyst

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101861374A (en) * 2007-11-14 2010-10-13 环球油品公司 Methods of denitrogenating diesel fuel
CN102442951A (en) * 2010-10-12 2012-05-09 上海欣年石化助剂有限公司 Preparation method of functionalized polyacid-type sulfonic ionic liquid
CN102757323A (en) * 2011-04-26 2012-10-31 中国科学院兰州化学物理研究所 Method for preparing alkoxy ether compounds
CN103333114A (en) * 2013-07-18 2013-10-02 青岛科技大学 Imidazole ionic liquid with dual functions of oxidation and temperature control and synthetic method of ionic liquid
CN105038841A (en) * 2015-07-05 2015-11-11 青岛科技大学 Method for catalyzing fuel oil oxidation desulphurization by polyether type oxovanadium heteropolyacid ionic liquid
CN107267191A (en) * 2017-05-31 2017-10-20 宁波大学 With the method for nitride in imidazole type dication liquid removal diesel oil
CN107699274A (en) * 2017-11-06 2018-02-16 李俊霞 A kind of method of nitride in removing oil product
CN109331873A (en) * 2018-11-19 2019-02-15 万华化学集团股份有限公司 A method of Diacetone Acrylamide is prepared using temperature control inversion of phases heteropoly acid ionic-liquid catalyst

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