CN105400542B - 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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- CN105400542B CN105400542B CN201510635337.4A CN201510635337A CN105400542B CN 105400542 B CN105400542 B CN 105400542B CN 201510635337 A CN201510635337 A CN 201510635337A CN 105400542 B CN105400542 B CN 105400542B
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- ionic liquid
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- denitrification
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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, is related to one kind with double imidazoles SO3H functionalization acidic ionic liquids body is denitrogenation
Agent, by the basic nitrogen compound in oil product（Quinoline）With non basic nitrogen compound（Indoles）Carry out the new method of selectively removing.
Background technology
Nitrogen is present in crude oil with the organic compound of different shape, and its content is typically between 0.05 %-0.5 %.Oil
Nitrogen-containing organic compound in product can be divided into alkalescence and the class of non-alkaline compound two, wherein basic nitrogen compound according to its alkaline power
Predominantly fatty amine, aniline, pyridine, quinoline and its derivates；Non basic nitrogen compound then comprising pyrroles, indoles, carbazole and its is spread out
It is biological.Air can be entered in the form of NOx after nitride burning in oil product, cause air suspended particulated to pollute, NOx
It is one of main component of PM2.5.NOx is combined with the moisture content in air, can form acid rain, to being directly exposed to rainwater under
Building, equipment, historical relic and other items have greatly harm, while a series of generation of diseases such as human skin, eye can be caused.Separately
Outward, the presence of NOx also can result in the more serious environmental problems such as photochemical fog, ozone layer be thinning.Nearest more than ten years, mist
Haze weather and acid rain damaging range have the trend for gradually expanding.Secondly：Property of the presence of nitride to oil product itself in oil product
Will also result in impact.Nitrogen-containing compound in oil is catalyzed processing, the performance of product and stability in storage to oil
Deng there is detrimental effect.Even contain very micro nitrogen-containing compound in fuel oil or lubricating oil, it is also possible to form colloid,
Oil deterioration is made, so that the quality of product and storage stability are deteriorated；In oil product storage or transportation, nitrogen-containing compound
Can also etching apparatus；Colloid is produced, is the main original for causing oil product in oil secondary processing process to darken and producing precipitation
Cause.Again：In hydrofinishing, it is hydrocracked with the technical process such as catalytic cracking, the basic nitrogen compound in raw material oil product is deposited
, noble metal catalyst selectivity and activity decrease can be caused, or even cause catalyst poisoning to inactivate.There are some researches show, quinoline
There is high inhibition to act on the hydrodesulfurization reaction of dibenzothiophenes, the presence of a small amount of quinoline takes off to the hydrogenation of dibenzothiophenes
Sulphur influential effect is also very big.In some acid catalyzed reactions, the presence of the basic nitrogen compound in raw material can also increase acid
Consume, cause cost to increase.With increasingly increasing for atmosphere pollution, environmental regulation specification further and strict, nitride in fuel
Removing problem also receive more and more attention.Although China is at present to nitride minimum content in fuel oil still without country's mark
Standard, but believe in the near future, the clean fuel oil of zero nitrogen content will become the certainty of historical development.
Oil product nitride routine removal methods have hydrodenitrogeneration and Non-hydrogenation technology.Hydrodenitrogeneration is most widely used at present
One of method, this kind of method technics comparing is ripe, and has the advantages that process is simple, easy to operate, oil product high income, but adds
Equipment investment needed for hydrogen is than larger, and operating condition is harsh, and operating cost is higher.And deep hydrogenation becomes can oil quality
Difference, stability declines, and either shallow hydrogenation reduces denitrification percent again.The method of Non-hydrogenation technology industrialization has acid treating and molten
Agent extracting and refining, acid treating is more satisfactory to basic nitrogen removal effect, but there is equipment corrosion, the problems such as discharge of wastewater, solvent
Extracting and refining in addition to it can remove nitrogen-containing compound, can also remove the polycyclic aromatic hydrocarbon in oil product, colloid and it is oxygen-containing, contain
The compounds such as sulphur.But the selectivity of Conventional solvents extraction is typically poor, and while nitride is removed, alkene is also removed, and leads
Oil yield is caused substantially to reduce.At the same time, solvent extraction is larger to the consumption of solvent, thus the method is relatively adapted to basic nitrogen
The preliminary denitrogenation of the less demanding oil product of removal efficiency or raw material.It is presently used for the side that oil product removes basic nitrogen and non-alkaline simultaneously
Method is very rare.
The content of the invention
The present invention propose it is a kind of by using double-core acidic ion liquid in oil product alkalescence and non basic nitrogen compound
Carry out the new method of selectively removing.The method is using the double-core ionic liquid for having good solubility to basic nitrogen and non basic nitrogen
Body makees denitrifier and solvent, and oil product is carried out into denitrogenation processing, and such ionic liquid has good water solubility, insoluble in gasoline,
Diesel oil, by processes such as stirring-extraction-sedimentations, you can effectively extract the basic nitrogen in oil product and non basic nitrogen compound
Into ionic liquid；After reaction terminates, ionic liquid is reusable Jing after simple process.
It is an object of the invention to provide the new method of a kind of removing simulation oil product neutral and alkali nitrogen and non basic nitrogen, to overcome biography
Need to consume present in the non-hydrogenation acid treating method of system a large amount of inorganic acids, denitrifier can not reuse, equipment corrosion and waste water
The shortcomings of discharging many.
The present invention is solved the above problems by below scheme, using the adjustability of structure of ionic liquid, by zwitterion
Combination, design synthesis has the ionic liquid of removal effect to basic nitrogen and non basic nitrogen, at a certain temperature, oil product entered
Row denitrification reaction.After reaction terminates, oil product is separated with ionic liquid by point liquid, ionic liquid is without process or Jing second
After ether carrying out washing treatment, denitrifier reuse is may continue as.
Ionic liquid described in the inventive method has following structural formula：
M=3 or 4
N=3 or 4
Y= HSO4Or H2PO4Or BF4Or CF3COO or CH3COO or CH3SO3Or CF3SO3Or CH3C6H5SO3
This method is realized by following steps：
The preparation of simulation oil product：
Basic nitrogen simulates oil product：The analytically pure quinoline of 161.43mg is dissolved in the normal heptane of 100 mL and makes solution,
The concentration of the nitrogen in solution is 175 mg L-1
Non basic nitrogen simulates oil product：The analytically pure indoles of 146.32mg is dissolved in the normal heptane of 100mL and makes solution,
The concentration of the nitrogen in solution is 175mg L-1。
Mixing nitrogen simulation oil product：The analytically pure quinoline of 161.43mg and the analytically pure indoles of 146.32mg are dissolved in
Solution is made in the normal heptane of 200mL, the concentration of the nitrogen in solution is 175mg L-1。
Ionic liquid denitrogenation is tested：In the reaction bulb with stopper and magneton, 1 g ionic liquids are added, add 5-50
G simulates oil product, and 10-40 min are stirred under room temperature, stands 30 min, and suction pipe draws upper strata oil product, is surveyed with TN-3000 apparatuss for nitrogen examination
Determine the nitrogen content of oil product before and after denitrogenation, denitrification percent of the ionic liquid to oil product is calculated accordingly.
This method is characterized in compared with conventional method：
（1）The traditional strong acid in background technology need not be adopted, equipment corrosion and discharge of wastewater problem is significantly improved.
（2）Reaction condition is gentle, and denitrogenation program is simple, high to basic nitrogen and the disposable removal efficiency of non basic nitrogen.
（3）Ionic liquid is reusable, after reuse 6 times, its denitrification percent still more than 90%, in overcoming background technology
Denitrifier can not reuse problem.
Specific implementation method
The method of the present invention is described further with reference to embodiment, but is not limitation of the invention.
Embodiment 1：Take 10 g quinoline and simulate oil product in reaction bulb, add 1 g double-core ionic liquids, the h of stirring reaction 0.5 at 40 DEG C, after 0.5 h of sedimentation,
Take upper strata oil product TN-3000 apparatuss for nitrogen examination and survey nitrogen content, denitrification percent is 98.61 %.
Embodiment 2-8：Experiment condition, with embodiment 1, simply changes ionic liquid with step, and denitrogenation the results are shown in Table 1.
The embodiment 2-8 ionic liquid of table 1 removing quinoline simulation oil product result
Embodiment 9：Take 10 g indoles and simulate oil product in reaction bulb, add 1 g double-core ionic liquids, the h of stirring reaction 0.5 at 40 DEG C, sedimentation
After 0.5 h, take upper strata oil product TN-3000 apparatuss for nitrogen examination and survey nitrogen content, denitrification percent is 99.74 %.
Embodiment 10-16：Experiment condition, with embodiment 9, simply changes ionic liquid with step, and denitrogenation the results are shown in Table 2.
The embodiment 10-16 ionic liquid of table 2 removing indoles simulation oil product result.
Embodiment 17：Take mixing nitrogen of 10 g containing quinoline and indoles and simulate oil product in reaction bulb, add 1 g double-cores from
Sub- liquid, the h of stirring reaction 0.5 at 50 DEG C,
After settling 0.5 h, take upper strata oil product TN-3000 apparatuss for nitrogen examination and survey nitrogen content, denitrification percent is 99.58 %.
Embodiment 18：Select ionic liquid
, with step with embodiment 9, experiment finishes separating oil and ionic liquid to experiment condition, and ionic liquid is carried out next without process
Secondary denitrogenation experiment, denitrogenation the results are shown in Table 3, and ionic liquid is reused 6 times, and denitrification effect is still up to 98.76%, show good
Repeat performance.
The ionic liquid of table 3 repeats removing indoles simulation oil product
| Number of repetition | Denitrification percent（%） |
| 1 | 99.07 |
| 2 | 99.06 |
| 3 | 99.05 |
| 4 | 99.03 |
| 5 | 98.99 |
| 6 | 98.76 |
The foregoing is only some preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent
Change and modification, the covering scope of the present invention all should be belonged to.
Claims (1)
1. a kind of new method with double-core ionic liquid selectively removing oil product neutral and alkali nitrogen and non basic nitrogen, it is characterised in that institute
The ionic liquid for adopting is double imidazoles SO3H functionalization acidic ionic liquid bodies, with following structure：
M=3 or 4
N=3 or 4
Y=HSO4Or H2PO4Or BF4Or CF3COO or CH3COO or CH3SO3Or CF3SO3Or CH3C6H5SO3
Denitrification process：In the tool plug reaction bulb with magneton, 1g ionic liquids, 10-50g simulation oil products is added to stir under room temperature
10-40min is mixed, 30min is stood, upper strata oil product is drawn, with TN-3000 apparatuss for nitrogen examination the nitrogen content of oil product before and after denitrogenation is determined,
Denitrification percent is calculated, oil product used is quinoline or indoles simulation oil product, and nitrogen content is 175mgL-1。
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| 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 |
| 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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| FR2840916B1 (en) * | 2002-06-17 | 2004-08-20 | Inst Francais Du Petrole | PROCESS FOR REMOVAL OF SULFUR AND NITROGEN COMPOUNDS FROM HYDROCARBON CUT |
| 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 |
| US7749377B2 (en) * | 2007-11-14 | 2010-07-06 | Uop Llc | 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 |
| CN103146415B (en) * | 2013-03-07 | 2015-03-11 | 青岛科技大学 | Novel method for removing indole in oil product through ionic liquid |
| CN103305261B (en) * | 2013-06-19 | 2016-01-27 | 青岛科技大学 | The synthesis of one class novel ion liquid and the application in oil denitrification thereof |
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