CN104962312B - Application of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate in removing organic nitrides in diesel oil - Google Patents
Application of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate in removing organic nitrides in diesel oil Download PDFInfo
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- CN104962312B CN104962312B CN201510310413.4A CN201510310413A CN104962312B CN 104962312 B CN104962312 B CN 104962312B CN 201510310413 A CN201510310413 A CN 201510310413A CN 104962312 B CN104962312 B CN 104962312B
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Abstract
The invention discloses 1-butyl-2, 3, 5-trimethylpyrazoleApplication of tetrafluoroborate to removal of organic nitrides in diesel oil. The implementation method comprises the steps of mixing the ionic liquid with the diesel oil, stirring, standing, taking the upper layer of the diesel oil, and measuring the nitrogen content in the diesel oil by using a TN-3000 nitrogen tester, wherein the denitrification efficiency can be calculated by using the following formula:
wherein C is0And C represents the nitrogen concentration in the diesel before and after the treatment, respectively. The influence of the reagent-oil ratio, the reaction time, the temperature, the settling time and the repeated use of the ionic liquid on the denitrification efficiency is explored by a method for controlling a single variable. The ionic liquid is almost insoluble in diesel oil and can be well separated; the ionic liquid is easy to recover and can be repeatedly used; in addition, the ionic liquid can achieve the removal efficiency of organic nitride in diesel oil of more than 95% under the optimal condition, has good removal efficiency after being repeatedly used for more than 5 times, and has wide application prospect in the aspect of removing organic nitride in diesel oil.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and particularly relates to 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate ([ BuMe)3Py]BF4) Application of removing organic nitride from diesel oil.
Background
The diesel oil contains some organic nitrogen compounds, which mainly comprise basic nitrogen such as aniline, pyridine, quinoline and the like, and non-basic nitrogen such as pyrrole, indole, carbazole, amide and the like. The organic nitrogen compounds not only affect the quality of the oil products and deepen the color of the oil products, but also form nitrogen oxides in the combustion process and discharge the nitrogen oxides into the atmosphere to form hazards such as atmospheric pollution, acid rain and the like.
With the increasing environmental problem, in order to protect the environment and improve the quality of oil products, the industrial production must further remove the organic nitrides in the oil products. At present, the methods for industrially removing organic nitrogen compounds in diesel oil comprise hydrofining, clay refining, acid-base refining, complexing refining and the like, but the methods have many defects, such as harsh reaction conditions, expensive equipment, low recovery rate, environmental pollution and the like.
As a new generation of green reagents, ionic liquids have many advantages: stable chemical property, low steam pressure, non-flammability and easy recovery and reuse, and has been widely used in extraction, purification, catalysis, etc. in recent years. The physical and chemical properties of the ionic liquid can be adjusted by changing the types of anions and cations, and the ionic liquid can be combined with organic nitride in diesel oil to form a complex so as to achieve the purpose of removing the organic nitride.
At present, imidazole type and quaternary ammonium salt type ionic liquids have been reported to remove organic nitrogen compounds in oil products, but pyrazole type ionic liquids have not been reported to remove organic nitrogen compounds in diesel oil. The invention uses [ BuMe3Py]BF4For example, the influence of the reagent-oil ratio, the reaction time, the reaction temperature and the settling time on the denitrification efficiency is discussed.
Disclosure of Invention
The invention aims to solve the problems in the prior art, overcome the defects of high cost, harsh reaction conditions, easy environmental pollution and the like of the traditional diesel denitrification, and provide 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate ([ BuMe)3Py]BF4) Application of removing organic nitride from diesel oil.
The compound of the invention has a denitrification efficiency-to-catalyst-to-oil ratio graph shown in figure 1; has a denitrification efficiency versus reaction time graph as shown in FIG. 2; has a denitrification efficiency and reaction temperature relationship chart as shown in figure 3; the denitrification efficiency and the sedimentation time are shown in a graph in figure 4; the denitrification efficiency and the number of reuses were plotted as shown in Table 1.
The invention relates to an instrument model for measuring nitrogen concentration, and parameter data are as follows:
the TN-3000 nitrogen tester measures the nitrogen content in the diesel oil.
The denitrification efficiency can be calculated by the following formula:
wherein C is0And C represents the nitrogen concentration in the diesel before and after the treatment, respectively.
The invention is realized by the following technical scheme:
an application of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate in removing organic nitrides in diesel oil is to mix the 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate and the diesel oil according to the mass ratio of 1: 1-1: 15, stir for 0.5-3 h at the stirring temperature of 20-60 ℃, and carry out sedimentation separation.
Preferably, the mass ratio of the 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate to the diesel oil is 1: 5.
Preferably, the stirring time is 2 h.
Preferably, the stirring temperature is 20 to 40 ℃.
Preferably, the time for the settling separation is 1 h.
Preferably, the removal rate of the 1-butyl-2, 3, 5-trimethyl pyrazole tetrafluoroborate to organic nitrogen compounds in diesel oil is more than 95%.
In the invention, the 1-butyl-2, 3, 5-trimethyl pyrazole tetrafluoroborate has high removal rate to organic nitrogen compounds in diesel oil, and the 1-butyl-2, 3, 5-trimethyl pyrazole tetrafluoroborate can be recycled.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
Example 1: influence of ionic liquid and diesel oil quality (agent-oil ratio) ratio on denitrification efficiency
1g of ionic liquid is taken, 1g of diesel oil, 3g of diesel oil, 5g of diesel oil, 10g of diesel oil and 15g of diesel oil are respectively added, magnetic stirring is carried out for 1h at the temperature of 25 ℃, after sedimentation is carried out for 30min, the upper layer of diesel oil is taken to measure the nitrogen content, and the experimental result is shown in figure 1.
As can be seen from FIG. 1, the denitrification efficiency of the ionic liquid is gradually increased along with the increase of the mass of the ionic liquid and the diesel oil, and is increased from 65.2% at the time of 1: 15 to 93.2% at the time of 1: 1, because the mass ratio of the ionic liquid and the diesel oil is increased, the contact probability of the ionic liquid and the organic nitrides in the diesel oil is increased, and the removal of the organic nitrides in the diesel oil is facilitated.
Example 2: effect of reaction time on Denitrification efficiency
Taking 1g of ionic liquid, adding 5g of diesel oil, reacting for 0.5-3 h at 25 ℃, settling for 30min, taking the upper layer of diesel oil, and measuring the nitrogen content in the upper layer of diesel oil, wherein the experimental result is shown in figure 2.
As can be seen from the graph 2, the reaction time has obvious influence on the denitrification efficiency, the improvement on the denitrification efficiency within 1.5h is obvious, the denitrification efficiency can reach over 90 percent, the denitrification efficiency tends to be stable along with the extension of the reaction time, and the denitrification efficiency of 3.0h is 93.6 percent.
Example 3: influence of temperature on Denitrification efficiency
Taking 1g of ionic liquid, adding 5g of diesel oil, magnetically stirring at 20-60 ℃ for 2h, standing for 30 mm, taking the upper layer of diesel oil to measure the nitrogen content, wherein the experimental result is shown in figure 3.
As can be seen from FIG. 3, the temperature rise at the normal temperature of 20-40 ℃ has no obvious influence on the denitrification efficiency, the denitrification efficiency is kept above 90%, the denitrification efficiency is in a descending trend along with the temperature rise, and the denitrification efficiency is reduced to 70.5% when the temperature reaches 60 ℃, because the removal of organic nitrogen compounds in diesel oil by the ionic liquid is an adsorption process, and the temperature rise is not beneficial to the adsorption of the ionic liquid.
Example 4: influence of settling time on Denitrification Effect
1g of ionic liquid is taken, 5g of diesel oil is added, the mixture is respectively settled for a certain time after being magnetically stirred for 1h at the temperature of 25 ℃, the upper layer oil product is taken to measure the nitrogen content, and the experimental result is shown in figure 4.
As can be seen from FIG. 4, the denitrification efficiency without sedimentation after magnetic stirring for 1 hour is only 53.1%, because the ionic liquid and the diesel oil are not completely separated, when the ionic liquid and the diesel oil are settled for 30min, the denitrification efficiency reaches 89.4%, which indicates that the ionic liquid and the oil phase are basically separated, and the ionic liquid and the oil phase reach a good separation effect after settling for 60min, and the denitrification efficiency is 95.6%.
Example 5: ionic liquid recovery and reuse experiment
After extraction, the ionic liquid and diesel oil are separated by filtration, washed with ether or ethyl acetate for three times, dried in vacuum, and the denitrification efficiency of the ionic liquid with the same mass is measured under the same conditions next time, and the experimental results are shown in table 1.
As can be seen from Table 1, the ionic liquid has good denitrification efficiency after being reused for 5 times.
TABLE 1 reuse number and Denitrification efficiency
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (5)
1. The application of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate to remove organic nitrides in diesel oil is characterized in that 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate and diesel oil are mixed according to the mass ratio of 1: 1-1: 15, stirred for 0.5-3 h at the stirring temperature of 20-40 ℃, and subjected to sedimentation separation.
2. The use of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate for removing organic nitrides in diesel oil according to claim 1, wherein: the mass ratio of the 1-butyl-2, 3, 5-trimethyl pyrazole tetrafluoroborate to the diesel oil is 1: 5.
3. The use of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate as claimed in claim 2 for removing organic nitrides in diesel fuel, wherein: the stirring time was 2 h.
4. The use of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate for removing organic nitrides in diesel oil according to claim 1, wherein: the settling separation time is 1 h.
5. The use of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate for removing organic nitrides in diesel fuel as claimed in claim 4, wherein: the removal rate of 1-butyl-2, 3, 5-trimethyl pyrazole tetrafluoroborate to organic nitrogen compounds in diesel oil is more than 95%.
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