CN107267191A - With the method for nitride in imidazole type dication liquid removal diesel oil - Google Patents
With the method for nitride in imidazole type dication liquid removal diesel oil Download PDFInfo
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- CN107267191A CN107267191A CN201710395683.9A CN201710395683A CN107267191A CN 107267191 A CN107267191 A CN 107267191A CN 201710395683 A CN201710395683 A CN 201710395683A CN 107267191 A CN107267191 A CN 107267191A
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- Prior art keywords
- imidazole type
- diesel oil
- dication
- nitride
- dication liquid
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- 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
- 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
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses the method with nitride in imidazole type dication liquid removal diesel oil, imidazole type dication liquid is obtained by the methylimidazole of 1 benzyl 2 and dioxane bromide and p-methyl benzenesulfonic acid reaction, then with diesel oil and water stirring reaction, obtain denitrogenation diesel oil, this method technique is simple, more preferably, a denitrogenation can remove more than 90% nitride to denitrification effect, and denitrogenation cost is low.
Description
Technical field
The present invention relates to the method for diesel oil denitrogenation, and in particular to nitride in imidazole type dication liquid removal diesel oil
Method.
Background technology
Generally existing contains the compound of nitrogen, such as fatty amines, pyridines, quinolines and aniline in current diesel oil
The alkali compounds such as class and indoles, carbazoles, nitrile and amide-type non-alkaline compound.These contain the chemical combination of nitrogen
Thing maximum harm easily forms nitrogen oxides in automobile engine combustion process（NOx）With some particulate pollutants（PM2.5
And PM10）, it is discharged into air and easily forms the harm such as acid rain, haze, sternness is brought to human being's production, life and health
Test.On the other hand, in oil product these nitrogen-containing compounds contacted with the oxygen in air be oxidized easily, coagulation, not only make
The color and luster of actual oil product is deepened, and also results in the security and stability of oil product and greatly reduce, the quality reduction of oil product.At present
Have in terms of industrial oil denitrification acid-base neutralization salt forming method, physical-chemical absorption method, complexometric extraction partition method, oxidation partition method,
Microbial denitrogenation such as microwave radiation and bacterium etc..Such as publication number CN102373109 patent of invention, disclose and use organic carboxyl acid
The method for neutralizing denitrogenation, although this method technique is simpler, is normally only used for the diesel oil of alkalescence.Publication number CN101861374
Patent of invention, then disclose and mixed with the compound of imidazole sulfates with diesel oil, by cycling extraction technique denitrogenation, this method
Although preferably, design technology is more complicated for denitrification effect, denitrogenation cost is high.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of denitrification effect is more preferable, denitrification process simply uses imidazole type
The method of nitride in dication liquid removal diesel oil.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：With imidazole type dication liquid removal diesel oil
The method of middle nitride, its step is as follows：
A, by 1 benzyl 2 methyl imidazole and dioxane bromide in molar ratio 1:1~2 mixing, is stirred under 70~90 DEG C of temperature conditionss
Mix reaction 8~12 hours, obtain imidazole type bromide；
B, by above-mentioned imidazole type bromide and p-methyl benzenesulfonic acid in molar ratio 1:1, ion-exchange reactions under normal temperature, reaction terminates
Obtain imidazole type dication liquid；
C, by above-mentioned imidazole type dication liquid and water and diesel oil by volume 1:0~2:1~10 mixing, in 25~65 DEG C of temperature
Under the conditions of degree, stirring denitrification reaction 10~30 minutes obtains mixed solution, wherein the nitrogen content of diesel oil used is less than 500ppm；
D, above-mentioned mixed solution stood, until mixed solution is divided into upper and lower two layers of liquid phase, upper phase is separated, obtained
To denitrogenation diesel oil.
Dioxane bromide described in step a is Isosorbide-5-Nitrae-dibromobutane, the imidazole type dication liquid described in step b for it is double-
The toluenesulfonate of [1 benzyl 2 methyl imidazole] butylidene two.
Dioxane bromide described in step a is 1,2- Bromofumes, the imidazole type dication liquid described in step b for it is double-
[1 benzyl 2 methyl imidazole] ethylene toluenesulfonate.
Dioxane bromide described in step a is 1,6- dibromo-hexanes, the imidazole type dication liquid described in step b for it is double-
The toluenesulfonate of [1 benzyl 2 methyl imidazole] hexylidene two.
Step d lower floor's liquid phases at normal temperatures and pressures, are extracted 10 minutes with extractant, carry out vacuum distillation after separation again, obtain
To the imidazole type dication liquid of recovery, described extractant is carbon tetrachloride, ethyl acetate, ether or chloroform；Such miaow
Azoles type dication liquid is reused, and is reduced and is wasted.
Compared with prior art, the advantage of the invention is that a kind of nitrogenized with imidazole type dication liquid removal diesel oil
The method of thing, imidazole type dication is obtained by 1 benzyl 2 methyl imidazole and dioxane bromide and p-methyl benzenesulfonic acid reaction
Liquid, then with diesel oil and water stirring reaction, obtains denitrogenation diesel oil, this method technique is simple, and denitrification effect is more preferable, a denitrogenation
More than 90% nitride can be removed, denitrogenation cost is low.
Embodiment
The present invention is described in further detail with reference to embodiments.
Embodiment 1
Prepare double-[1 benzyl 2 methyl imidazole] ethylene toluenesulfonate：In molar ratio 1:1 by 1- benzyl -2- first
Base imidazoles and 1,2- Bromofume are mixed, and are warming up to 70 DEG C, are stirred vigorously, and reaction obtains imidazole type bromide in 12 hours；Obtain
Imidazole type bromide and p-methyl benzenesulfonic acid equimolar, ion-exchange reactions at normal temperatures, reaction end obtain it is double-[1- benzyls-
2-methylimidazole] ethylene toluenesulfonate.Diesel oil denitrogenation：Double-[1- benzyls are separately added into 25mL round-bottomed flask
Base -2-methylimidazole] ethylene toluenesulfonate 10mL and 10mL simulation diesel oil（Quinoline is dissolved in normal heptane, N：
500ppm）The stirring reaction at a temperature of 25~30 DEG C, reaction stops pouring out the diesel oil phase on upper strata after stirring, standing after 10 minutes,
3~5mL is sampled in digest tube.First cleared up on graphite digestion furnace 3 hours, then use Protein Analyzer（Jinan sea can instrument
Device limited company）Its nitrogen content is measured, is first 96% using denitrification percent.Double-[1 benzyl 2 methyl imidazole] is sub-
The recycling of the toluenesulfonate of ethyl two：Lower floor's liquid phase after layering is taken, ethyl acetate 10mL is added and is extracted, separated
Ethyl acetate, repeats double-[1 benzyl 2 methyl imidazole] the ethylene toluenesulfonate being recycled for five times.Again plus
Enter to simulate diesel oil 10mL, be stirred at room temperature after 10 minutes and stop stirring, the diesel oil phase on upper strata is poured out after standing, sample 3-5mL
In digest tube.Digestion procedure and analysis method ibid, are repeated 5 times according to above-mentioned steps.The denitrification percent for repeating to react five times is equal
For more than 92%.
Embodiment 2
Substantially the same manner as Example 1, different simply 1,2- Bromofumes are substituted by Isosorbide-5-Nitrae-dibromobutane, 1- benzyl -2- first
The mol ratio of base imidazoles and Isosorbide-5-Nitrae-dibromobutane is 1:1.5, reaction temperature be 80 DEG C, the reaction time be 10 hours, then with it is right
Double-p-methyl benzenesulfonic acid of [1 benzyl 2 methyl imidazole] butylidene two is obtained after toluene sulfonic acide equimolar ion-exchange reactions
Salt；The volume ratio of double-toluenesulfonate of [1 benzyl 2 methyl imidazole] butylidene two and simulation diesel oil is 1:5, it is also another to add
The volume ratio of water, double-toluenesulfonate of [1 benzyl 2 methyl imidazole] butylidene two and water is 1:1, in 40~45 DEG C of temperature
The lower stirring reaction of degree, reacts 20 minutes, is first 97% using denitrification percent.Double-[1 benzyl 2 methyl imidazole] Aden reclaimed
The toluenesulfonate of base two recycles denitrification percent to be more than 90%.
Embodiment 3
Substantially the same manner as Example 1, different simply 1,2- Bromofumes are substituted by 1,6- dibromo-hexanes, 1- benzyl -2- first
The mol ratio of base imidazoles and 1,6- dibromo-hexane is 1:2, reaction temperature be 90 DEG C, the reaction time be 8 hours, then with to first
Double-toluenesulfonate of [1 benzyl 2 methyl imidazole] hexylidene two is obtained after base benzene sulfonic acid equimolar ion-exchange reactions；
The volume ratio of double-toluenesulfonate of [1 benzyl 2 methyl imidazole] hexylidene two and simulation diesel oil is 1:10, it is also another to add
The volume ratio of water, double-toluenesulfonate of [1 benzyl 2 methyl imidazole] hexylidene two and water is 1:2, in 60~65 DEG C of temperature
The lower stirring reaction of degree, reacts 30 minutes, is first 93% using denitrification percent.Double-[1 benzyl 2 methyl imidazole] for reclaiming it is sub- oneself
The toluenesulfonate of base two recycles denitrification percent to be more than 90%.
1,2- Bromofumes, Isosorbide-5-Nitrae-dibromobutane and 1,6- dibromo-hexane can also be by other dialkyl group in above-described embodiment
Bromine is substituted, and is obtained different imidazole type dication liquid, is not described one by one herein.
Claims (5)
1. with the method for nitride in imidazole type dication liquid removal diesel oil, it is characterised in that step is as follows：
A, by 1 benzyl 2 methyl imidazole and dioxane bromide in molar ratio 1:1~2 mixing, is stirred under 70~90 DEG C of temperature conditionss
Mix reaction 8~12 hours, obtain imidazole type bromide；
B, by above-mentioned imidazole type bromide and p-methyl benzenesulfonic acid in molar ratio 1:1, ion-exchange reactions under normal temperature, reaction terminates
Obtain imidazole type dication liquid；
C, by above-mentioned imidazole type dication liquid and water and diesel oil by volume 1:0~2:1~10 mixing, in 25~65 DEG C of temperature
Under the conditions of degree, stirring denitrification reaction 10~30 minutes obtains mixed solution, wherein the nitrogen content of diesel oil used is less than 500ppm；
D, above-mentioned mixed solution stood, until mixed solution is divided into upper and lower two layers of liquid phase, upper phase is separated, obtained
To denitrogenation diesel oil.
2. as claimed in claim 1 with the method for nitride in imidazole type dication liquid removal diesel oil, it is characterised in that
Dioxane bromide described in step a is Isosorbide-5-Nitrae-dibromobutane, the imidazole type dication liquid described in step b for it is double-[1- benzyls-
2-methylimidazole] two toluenesulfonate of butylidene.
3. as claimed in claim 1 with the method for nitride in imidazole type dication liquid removal diesel oil, it is characterised in that
Dioxane bromide described in step a is 1,2- Bromofumes, the imidazole type dication liquid described in step b for it is double-[1- benzyls-
2-methylimidazole] ethylene toluenesulfonate.
4. as claimed in claim 1 with the method for nitride in imidazole type dication liquid removal diesel oil, it is characterised in that
Dioxane bromide described in step a is 1,6- dibromo-hexanes, the imidazole type dication liquid described in step b for it is double-[1- benzyls-
2-methylimidazole] two toluenesulfonate of hexylidene.
5. as claimed in claim 1 with the method for nitride in imidazole type dication liquid removal diesel oil, it is characterised in that
Step d lower floor's liquid phase at normal temperatures and pressures, is extracted 10 minutes with extractant, carries out vacuum distillation after separation again, be recycled
Imidazole type dication liquid, described extractant is carbon tetrachloride, ethyl acetate, ether or chloroform.
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| CN201710395683.9A CN107267191A (en) | 2017-05-31 | 2017-05-31 | With the method for nitride in imidazole type dication liquid removal diesel oil |
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Cited By (2)
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| CN107699274A (en) * | 2017-11-06 | 2018-02-16 | 李俊霞 | A kind of method of nitride in removing oil product |
| CN113754875A (en) * | 2021-10-08 | 2021-12-07 | 山东科技大学 | Polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and preparation method thereof |
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| CN107699274A (en) * | 2017-11-06 | 2018-02-16 | 李俊霞 | A kind of method of nitride in removing oil product |
| CN113754875A (en) * | 2021-10-08 | 2021-12-07 | 山东科技大学 | Polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and preparation method thereof |
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