CN105400542A - Selective removal of nitrogen compounds in oil products using biimidazole SO3H-functionalized ionic liquid - Google Patents
Selective removal of nitrogen compounds in oil products using biimidazole SO3H-functionalized ionic liquid Download PDFInfo
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- CN105400542A CN105400542A CN201510635337.4A CN201510635337A CN105400542A CN 105400542 A CN105400542 A CN 105400542A CN 201510635337 A CN201510635337 A CN 201510635337A CN 105400542 A CN105400542 A CN 105400542A
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Abstract
The invention relates to a new method for selectively removing basic (quinoline) and non-basic (indole) nitrogen compounds in oil products using double-core acidic ionic liquid. The method is characterized in that the ionic liquid is biimidazole SO3H-functionalized acidic ionic liquid, which can be operated at normal temperature and normal pressure, and after reaction and simple treatment, the recycled ionic liquid is repeatedly usable. Compared with traditional method, the method has the characteristics that: (1) acid treating denitrification according to background technology is not needed, and problems such as equipment corrosion and waste water discharge, and the like are substantially solved; (2) the ionic liquid denitrification method has mild reaction conditions, the operation is easy, and the ionic liquid can be repeatedly used; and (3) compared with other ionic liquids, the ionic liquid can remove basic and non-basic nitrogen compounds in oil products at the same time, the selectivity is high, the denitrification is carried for one time, and the nitrogen content is reduced to below 10mg/L, so that the disadvantage that the original denitrification agent can only remove basic or non-basic nitrogen compounds is overcome.
Description
Technical field
The invention belongs to petrochemical industry, relate to a kind of with two imidazoles SO
3h functionalization acidic ionic liquid body is denitrfying agent, the basic nitrogen compound (quinoline) in oil product and non basic nitrogen compound (indoles) is carried out the novel method of selectively removing.
Background technology
Nitrogen is present in crude oil with the organic compound of different shape, and its content is generally between 0.05%-0.5%.Nitrogen-containing organic compound in oil product can be divided into alkalescence and non-alkaline compound two class according to its alkaline power, and wherein basic nitrogen compound is mainly aliphatic amide, aniline, pyridine, quinoline and its derivates; Non basic nitrogen compound then comprises pyrroles, indoles, carbazole and derivative thereof.Can enter air with the form of NOx after nitride burning in oil product, cause air suspended particulated to pollute, NOx is one of main component of PM2.5.The moisture content of NOx in air is combined, and can form acid rain, has great harm, can cause the generation of a series of disease such as human skin, eye simultaneously to article such as the building be directly exposed under rainwater, equipment, historical relics.In addition, the existence of the NOx environmental problem that photo-chemical smog, ozonosphere also may to be caused thinning etc. more serious.The nearest more than ten years, haze weather and acid rain damaging range have the trend expanded gradually.Secondly: in oil product, the existence of nitride also can impact the character of oil product itself.Nitrogenous compound in oil all has adverse influence to the catalysis processing of oil, the use properties of product and stability in storage etc.Even if contain very micro-nitrogenous compound in oil fuel or lubricating oil, also can form colloid, make oil deterioration, thus make the quality of product and store stability to be deteriorated; To store or in transportation, nitrogenous compound also can etching apparatus at oil product; Producing colloid, is cause oil product in oil secondary processing process darken and produce the major cause of precipitation.Again: in the technological processs such as hydrofining, hydrocracking and catalytic cracking, the existence of the basic nitrogen compound in raw material oil product, can cause noble metal catalyst selectivity and activity decrease, even causes in catalyzer
poison loseslive.There are some researches show, the hydrodesulfurization reaction of quinoline to dibenzothiophene has high inhibition effect, the existence of a small amount of quinoline, also very large to the hydrogenating desulfurization influential effect of dibenzothiophene.In some acid catalyzed reactions, the existence of the basic nitrogen compound in raw material also can increase the consumption of acid, causes cost to increase.Along with day by day increasing the weight of of topsoil, specification is with strict further for environmental regulation, and in fuel, the problem that removes of nitride also receives increasing concern.Although China does not still have nitride minimum content in fuel oil at present
countrystandard, but believe in the near future, the clean fuel oil of zero nitrogen content will become the certainty of historical development.
The conventional removal methods of oil product nitride has hydrodenitrification and Non-hydrogenation technology.Hydrodenitrification is one of current most widely used method, and this kind of method technics comparing is ripe, and has that technique is simple, easy to operate, oil product yield advantages of higher, but facility investment needed for hydrogenation is larger, and operational condition harshness, process cost is higher.And deep hydrogenation can make oil quality be deteriorated, stability declines, and either shallow hydrogenation can make again denitrification percent reduce.The method of Non-hydrogenation technology industrialization has acid treating and solvent extraction to refine, acid treating is more satisfactory to basic nitrogen removal effect, but there is equipment corrosion, the problems such as discharge of wastewater, solvent extraction is refining except removing except nitrogenous compound, can also remove the polycyclic aromatic hydrocarbons in oil product, colloid and contain the compound such as oxygen, sulfur-bearing.But the selectivity of Conventional solvents extraction is generally poor, and while removing nitride, alkene is also removed, and causes oily yield obviously to reduce.Meanwhile, solvent extraction is comparatively large to the consumption of solvent, and thus the method is comparatively applicable to the preliminary denitrogenation to the less demanding oil product of basic nitrogen decreasing ratio or raw material.At present, remove the method for basic nitrogen and non-alkaline for oil product simultaneously, very rare.
Summary of the invention
The present invention proposes a kind of novel method of by employing double-core acidic ion liquid, the alkalescence in oil product and non basic nitrogen compound being carried out to selectively removing.The method adopts all has the double-core ionic liquid of good solubility to make denitrfying agent and solvent to basic nitrogen and non basic nitrogen, oil product is carried out denitrogenation processing, such ionic liquid has good water-soluble, be insoluble to gasoline, diesel oil, by processes such as stirring-extraction-sedimentations, can effectively the basic nitrogen in oil product and non basic nitrogen compound be extracted in ionic liquid; After reaction terminates, ionic liquid is after simple process, reusable.
The object of this invention is to provide and a kind ofly remove simulation oil product neutral and alkali nitrogen and the novel method of non basic nitrogen, a large amount of mineral acid of need consumption, the denitrfying agent that exist in traditional non-power hydracid process for purification can not be reused to overcome, equipment corrosion and the shortcoming such as discharge of wastewater is many.
The present invention is solved the problem by following scheme, utilizes the adjustability of structure of ionic liquid, and by the combination of zwitterion, design and synthesis all has the ionic liquid of removal effect to basic nitrogen and non basic nitrogen, at a certain temperature, carries out denitrification reaction to oil product.After reaction terminates, be separated by oil product by separatory with ionic liquid, ionic liquid is treated or after washed with diethylether process, can continue to reuse as denitrfying agent.
Ionic liquid described in the inventive method has following structural formula:
M=3 or 4
N=3 or 4
Y=HSO
4or H
2pO
4or BF
4or CF
3cOO or CH
3cOO or CH
3sO
3or CF
3sO
3or CH
3c
6h
5sO
3
Present method is realized by following steps:
The preparation of simulation oil product:
Basic nitrogen simulation oil product: be dissolved in the normal heptane of 100mL by analytically pure for 161.43mg quinoline and make solution, the concentration of the nitrogen in solution is 175mg L
-1
Non basic nitrogen simulation oil product: be dissolved in the normal heptane of 100mL by analytically pure for 146.32mg indoles and make solution, the concentration of the nitrogen in solution is 175mg L
-1.
Mixing nitrogen simulation oil product: analytically pure for 161.43mg quinoline and the analytically pure indoles of 146.32mg are dissolved in the normal heptane of 200mL and make solution, the concentration of the nitrogen in solution is 175mg L
-1.
Ionic liquid denitrogenation is tested: in the reaction flask with stopper and magneton, add 1g ionic liquid, add 5-50g and simulate oil product, stirred at ambient temperature 10-40min, leave standstill 30min, upper strata oil product drawn by suction pipe, measures the nitrogen content of oil product before and after denitrogenation with TN-3000 apparatus for nitrogen examination, calculates ionic liquid accordingly to the denitrification percent of oil product.
Present method, compared with traditional method, is characterized in:
(1) without the need to adopting the traditional strong acid in background technology, equipment corrosion and discharge of wastewater problem is significantly improved.
(2) reaction conditions is gentle, and denitrogenation program is simple, to basic nitrogen and the disposable decreasing ratio of non basic nitrogen high.
(3) ionic liquid is reusable, and after reuse 6 times, its denitrification percent, still more than 90%, overcomes denitrfying agent in background technology and can not reuse problem.
specific implementation method
Below in conjunction with embodiment, method of the present invention is described further, but is not limitation of the invention.
Embodiment 1: get 10g quinoline simulation oil product in reaction flask, add 1g double-core ionic liquid, stirring reaction 0.5h at 40 DEG C, after sedimentation 0.5h, get upper strata oil product TN-3000 apparatus for nitrogen examination and survey nitrogen content, denitrification percent is 98.61%.
Embodiment 2-8: experiment condition and step are with embodiment 1, and just change ionic liquid, denitrogenation the results are shown in
table 1.
table 1embodiment 2-8 ionic liquid removes quinoline simulation oil product result
Embodiment 9: get 10g indoles simulation oil product in reaction flask, add 1g double-core ionic liquid
, stirring reaction 0.5h at 40 DEG C, after sedimentation 0.5h, get upper strata oil product TN-3000 apparatus for nitrogen examination and survey nitrogen content, denitrification percent is 99.74%.
Embodiment 10-16: experiment condition and step are with embodiment 9, and just change ionic liquid, denitrogenation the results are shown in
table 2.
table 2embodiment 10-16 ionic liquid removes indoles simulation oil product result
Embodiment 17: get 10g and simulate oil product in reaction flask containing the mixing nitrogen of quinoline and indoles, add 1g double-core ionic liquid, stirring reaction 0.5h at 50 DEG C, after sedimentation 0.5h, get upper strata oil product TN-3000 apparatus for nitrogen examination and survey nitrogen content, denitrification percent is 99.58%.
Embodiment 18: Selective ion mode liquid, experiment condition and step, with embodiment 9, test complete separating oil and ionic liquid, and ionic liquid is not treated, and carry out the experiment of denitrogenation next time, denitrogenation the results are shown in
table 3, ionic liquid reuses 6 times, and denitrification effect, still up to 98.76%, demonstrates good repeat performance.
Table 3 ionic liquid repeats to remove indoles simulation oil product
| Multiplicity | Denitrification percent (%) |
| 1 | 99.07 |
| 2 | 99.06 |
| 3 | 99.05 |
| 4 | 99.03 |
| 5 | 98.99 |
| 6 | 98.76 |
The foregoing is only preferred embodiments more of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1., with a novel method for double-core ionic liquid selectively removing oil product neutral and alkali nitrogen and non basic nitrogen, it is characterized in that adopted ionic liquid is for two imidazoles SO
3h functionalization acidic ionic liquid body, has following structure:
M=3 or 4
N=3 or 4
Y=HSO
4or H
2pO
4or BF
4or CF
3cOO or CH
3cOO or CH
3sO
3or CF
3sO
3or CH
3c
6h
5sO
3
Denitrification process: with in the tool plug reaction flask of magneton, add 1g ionic liquid, 10-50g simulates oil product, stirred at ambient temperature 10-40min, leaves standstill 10min, draws upper strata oil product, the nitrogen content of oil product before and after denitrogenation is measured with TN-3000 apparatus for nitrogen examination, calculate denitrification percent, oil product used is quinoline or indoles simulation oil product, and nitrogen content is 175mg L
-1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106967453A (en) * | 2017-04-26 | 2017-07-21 | 青岛科技大学 | The method for removing oil product neutral and alkali and non basic nitrogen compound |
| 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 |
| CN107586559A (en) * | 2017-11-06 | 2018-01-16 | 李俊霞 | A kind of method of nitride in efficient removal oil product |
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| TW200619370A (en) * | 2004-12-10 | 2006-06-16 | Chinese Petroleum Corp | Removing sulfur or nitrogen containing compound in gasoline and diesel fuel using oxidation and extraction method in ion liquid at room temperature |
| JP2010215737A (en) * | 2009-03-13 | 2010-09-30 | Idemitsu Kosan Co Ltd | Method of purifying hydrocarbon oil by desulfurization or denitrification |
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| CN103305261A (en) * | 2013-06-19 | 2013-09-18 | 青岛科技大学 | Synthesis method of novel ionic liquid and application of novel ionic liquid to oil product denitrification |
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2015
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040045874A1 (en) * | 2002-06-17 | 2004-03-11 | Institut Francais Du Petrole, Rueil Malmaison Cedex, France | Processing for eliminating sulfur-containing compounds and nitrogen-containing compounds from hydrocarbon |
| TW200619370A (en) * | 2004-12-10 | 2006-06-16 | Chinese Petroleum Corp | Removing sulfur or nitrogen containing compound in gasoline and diesel fuel using oxidation and extraction method in ion liquid at room temperature |
| CN101861374A (en) * | 2007-11-14 | 2010-10-13 | 环球油品公司 | Methods of denitrogenating diesel fuel |
| JP2010215737A (en) * | 2009-03-13 | 2010-09-30 | Idemitsu Kosan Co Ltd | Method of purifying hydrocarbon oil by desulfurization or denitrification |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106967453A (en) * | 2017-04-26 | 2017-07-21 | 青岛科技大学 | The method for removing oil product neutral and alkali and non basic nitrogen compound |
| CN106967453B (en) * | 2017-04-26 | 2018-10-12 | 青岛科技大学 | The method for removing oil product neutral and alkali and non basic nitrogen compound |
| 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 |
| CN107586559A (en) * | 2017-11-06 | 2018-01-16 | 李俊霞 | A kind of method of nitride in efficient removal oil product |
| CN107586559B (en) * | 2017-11-06 | 2019-08-16 | 浙江普泽环保科技有限公司 | A kind of method of nitride in efficient removal oil product |
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