CN107586559B - A kind of method of nitride in efficient removal oil product - Google Patents
A kind of method of nitride in efficient removal oil product Download PDFInfo
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- CN107586559B CN107586559B CN201711080871.9A CN201711080871A CN107586559B CN 107586559 B CN107586559 B CN 107586559B CN 201711080871 A CN201711080871 A CN 201711080871A CN 107586559 B CN107586559 B CN 107586559B
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Abstract
The invention discloses a kind of methods using nitride in more sulfonate ion liquid removal oil products, this method is that more sulfonate ion liquid are added into oil product, the non basic nitrogen compound in oil product is set to carry out protonation removing, the basic nitrogen compound in oil product carries out sulfonated removing.Ionic liquid of the invention removes removal efficiency with higher for the conversion of nitride in oil product, and on the one hand the highly acid of the ionic liquid can generate oligomer conversion removing for single step reaction of going forward side by side is protonated using indoles as the non basic nitrogen compound of representative；On the other hand it can be removed the sulfonated 3- pyridine-sulfonic acid that is converted into is carried out as the basic nitrogen compound of representative using pyridine；Thiophene sulfocompounds in oil product and alkenes compounds can also be promoted to occur to be alkylated and then greatly reduce sulfur-containing compound to interference caused by denitrification process.
Description
Technical field
The invention belongs to technical field of petrochemical industry, are related to a kind of method for removing nitrogen oxides in oil product, especially relate to
A kind of and method using nitride in more sulfonate ion liquid removal oil products.
Background technique
With the rapid development of our country's economy, coal, petroleum, three macrofossil fuel of natural gas consumption be gradually increased,
While creating a large amount of economic values, burn the middle oil product as communications and transportation main fuel the various exhaust gas generated
It pollutes caused by atmosphere and also gets worse.With the increasingly increase of environmental protection pressure, the cleanly production of fuel oil is proposed more
Add strict requirements.
The removing of nitride is a great problem that fuel oil cleanly production faces in oil product, the conventional side for removing nitride
Method has hydrodenitrogeneration and Non-hydrogenation technology.Hydrodenitrogeneration has the advantages such as effect is good, oil yield is high, but its processing cost is high.
It is extraction that Non-hydrogenation technology, which represents technique, but conventional extractant is acid or organic solvent, and there are consumptions greatly, pollution ring
Border, recycles the problems such as difficult difficult at corrosion equipment.Ionic liquid is used as most potential green solvent and catalyst,
Unique performance is shown in all various aspects, ionic liquid is used for fuel oil denitrogenation, can not only realize the greenization of product, and
And it is able to achieve the greenization of process, comply fully with the requirement of " Green Chemistry ".In recent years, using in ionic liquid removing fuel oil
Attention of the technology of nitride by more and more researchers.
Chinese patent 201310241817.3 uses a kind of N, and N- dimethylbenzene amine ionic liquid is as extractant for oil
The removing of nitride in product efficient removal can simulate aniline, pyridine, quinoline and indoles etc. in oil product in a mild condition
Heterocyclic nitride, but its there are oil ratios it is larger, limited to the removal efficiency of nitride in true 93# gasoline etc. lack
It falls into.
Summary of the invention
For current conventional ionic liquid, existing oil ratio is high, at high cost during nitride in removing oil product
The problems such as high, difficult to non basic nitrogen removing in oil product and limited to organonitrogen removal ability in practical oil product, the present invention is public
A kind of method using nitride in more sulfonate ion liquid removal oil products has been opened, nitride in oil product can have been carried out efficient
Conversion removing.
To achieve the above objectives, the technical solution adopted by the present invention are as follows:
The invention discloses a kind of methods of nitride in removing oil product, and more sulfonate ion liquid are added into oil product,
The non basic nitrogen compound in oil product is set to carry out protonation removing, the basic nitrogen compound in oil product carries out sulfonated removing；Wherein institute
State the structural formula of more sulfonate ion liquid are as follows:
。
As a preferred implementation manner, by more sulfonate ion liquid and oil product according to the mass volume ratio of 1g/400mL
20 ~ 30min is stirred in mixing at room temperature, is reacted the non basic nitrogen compound in oil product and is generated oligomer, basic nitrogen compound
It is converted into 3- pyridine-sulfonic acid.Preferably, the non basic nitrogen compound is mainly indoles, and the basic nitrogen compound is main pyridine,
All or part of removing can certainly be carried out, to other non-alkaline/basic nitrogen compound to realize non-alkaline/basic nitrogen in oil product
Compound removes to the greatest extent.
More sulfonate ion liquid are made of being made by the steps as a preferred implementation manner:
1) Isosorbide-5-Nitrae-butane sultones is mixed by the molar ratio of 1:1 with triphenyl phosphorus and is placed in microwave reactor,
In 60 ~ 90 under the power of 400 ~ 600woAfter C reacts 30min ~ 2h, carries out vacuum filtration and carried out after being cleaned with anhydrous propanone true
Sky is dried to obtain substance M；
2) by the concentrated sulfuric acid of substance M and 98wt% by 1:4 molar ratio at room temperature after mixing, be put into microwave
In reactor, 120 under the power of 300wo30min is reacted under the conditions of C, then carries out being filtered by vacuum and being washed with anhydrous propanone
It is dried in vacuo after washing 2 ~ 3 times, obtains more sulfonate ion liquid.
It is verifying of the method for the invention to nitrogenous compound removing situation in oil product below.
1. simulating the configuration of oil product:
A. it accurately weighs 1.153g quinoline and is dissolved in isooctane and dilutes and be settled to 500mL, being configured to nitrogen content is
The simulation oil product of 250mg/L；
B. it accurately weighs 0.706g pyridine and is dissolved in isooctane and dilutes and be settled to 500mL, being configured to nitrogen content is
The simulation oil product of 250mg/L；
C. it accurately weighs 0.577g quinoline and 0.353g pyridine is dissolved in isooctane and dilutes and is settled to 500mL, be configured to
Nitrogen content is the simulation oil product of 250mg/L；
D. a certain amount of 93# gasoline has been purchased from certain petroleum gas station, measuring nitrogen content therein is 145.6mg/L, sulphur
Content is 82.5mg/L.
2. evaluation condition:
In the glass reactor with magnetic agitation, it is proportionally added into simulation oil product and more sulfonate ion liquid,
It is stirred to react 20 ~ 30min at room temperature, draws upper layer oil product after quiescent settling 30min and is analyzed using TNS-3000 type nitrogen element sulphur
Instrument measures wherein nitrogen content and sulfur content.
The present invention compared with the existing technology, has the following advantages and beneficial effects:
1) ionic liquid of the invention is compared with conventional acid ionic liquid with oil ratio in sour density height, denitrification process
It is small, usage amount is few, repeated good, reaction condition is mild and the advantages such as preparation cost is low；
2) ionic liquid prepared by the present invention is applied to oil product compared with conventional ionic liquid or other catalyst
The conversion of middle nitride removes removal efficiency with higher, and on the one hand the highly acid of the ionic liquid can will be using indoles as generation
The non basic nitrogen compound of table protonates single step reaction of going forward side by side and generates oligomer conversion removing；It on the other hand can will be using pyridine as generation
The basic nitrogen compound of table carries out the sulfonated 3- pyridine-sulfonic acid that is converted into and removes；
3) ionic liquid can also promote thiophene sulfocompounds and olefines in oil product in denitrification process
It closes object and occurs to be alkylated and then greatly reduce sulfur-containing compound to interference caused by denitrification process；
4) ionic liquid recycles use aspect, only needs for it to be stripped with anhydrous propanone after denitrification reaction
After taking and washing, then under vacuum conditions dry after it is i.e. reusable.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Embodiment 1
1) preparation of ionic liquid:
A) Isosorbide-5-Nitrae-butane sultones is mixed by the molar ratio of 1:1 with triphenyl phosphorus and is placed in microwave reactor,
In 90 under the power of 600woAfter C reacts 30min, be filtered by vacuum and be dried in vacuo after washing 2 times with anhydrous propanone
To substance M；
B) by the concentrated sulfuric acid of substance M and 98wt% by 1:4 mole at room temperature after mixing, be put into microwave
In reactor, 120 under the power of 300wo30min is reacted under the conditions of C then to carry out being filtered by vacuum and being washed with anhydrous propanone
It is dried in vacuo after 2 ~ 3 times, obtains more sulfonate ion liquid.
1g ionic liquid sample is fitted into the glass reactor with magnetic agitation, 400mL is then added thereto again
The quinoline that nitrogen content is 250mg/L simulates oil product, draws upper layer oil after reaction 20min, quiescent settling 30min is stirred at room temperature
Using the nitrogen content of TNS-3000 type nitrogen element sulphur analysis-e/or determining wherein nitride, the removal efficiency of nitride is product
99.84%。
Embodiment 2
1) preparation of ionic liquid:
A) Isosorbide-5-Nitrae-butane sultones is mixed by the molar ratio of 1:1 with triphenyl phosphorus and is placed in microwave reactor,
In 60 under the power of 400woAfter C reacts 2h, then take progress vacuum after be filtered by vacuum and wash 3 times with anhydrous propanone dry
It is dry to obtain substance M；
B) by the concentrated sulfuric acid of substance M and 98wt% by 1:4 molar ratio at room temperature after mixing, be put into microwave
In reactor, 120 under the power of 300wo30min is reacted under the conditions of C, then carries out being filtered by vacuum and being washed with anhydrous propanone
It is dried in vacuo after washing 2 ~ 3 times, obtains more sulfonate ion liquid.
1g ionic liquid sample is fitted into the glass reactor with magnetic agitation, 400mL is then added thereto again
The pyridine that nitrogen content is 250mg/L simulates oil product, draws upper layer oil after reaction 30min, quiescent settling 30min is stirred at room temperature
Using the nitrogen content of TNS-3000 type nitrogen element sulphur analysis-e/or determining wherein nitride, the removal efficiency of nitride is product
99.63%。
Embodiment 3
1) preparation of ionic liquid
1) Isosorbide-5-Nitrae-butane sultones is mixed by the molar ratio of 1:1 with triphenyl phosphorus and is placed in microwave reactor,
In 75 under the power of 500woAfter C reacts 80h, carries out vacuum filtration and be dried in vacuo to obtain object after being cleaned with anhydrous propanone
Matter M；
2) by the concentrated sulfuric acid of substance M and 98wt% by 1:4 molar ratio at room temperature after mixing, be put into microwave
In reactor, 120 under the power of 300wo30min is reacted under the conditions of C, then carries out being filtered by vacuum and being washed with anhydrous propanone
It is dried in vacuo after washing 2 ~ 3 times, obtains more sulfonate ion liquid.
1g ionic liquid sample is fitted into the glass reactor with magnetic agitation, 400mL is then added thereto again
Nitrogen content is the quinoline of 250mg/L and the simulation oil product of pyridine mixtures, and reaction 25min, quiescent settling is stirred at room temperature
Upper layer oil product is drawn after 30min using the nitrogen content of TNS-3000 type nitrogen element sulphur analysis-e/or determining wherein nitride, nitridation
The removal efficiency of object is 99.72%.
Embodiment 4.
The preparation process of more sulfonate ion liquid is the same as embodiment 1；
1g ionic liquid sample is fitted into the glass reactor with magnetic agitation, 400mL is then added thereto again
Nitrogen content is the 93# gasoline of 134.3mg/L, draws upper layer oil product after reaction 30min, quiescent settling 30min is stirred at room temperature
Using the nitrogen content of TNS-3000 type nitrogen element sulphur analysis-e/or determining wherein nitride, the removal efficiency of nitride is 98.52%.
Embodiment 5.
The preparation process of more sulfonate ion liquid is with embodiment 2:
1g ionic liquid sample is fitted into the glass reactor with magnetic agitation, 400mL is then added thereto again
Nitrogen content is the quinoline of 250mg/L and the simulation oil product of pyridine mixtures, and reaction 30min, quiescent settling is stirred at room temperature
Upper layer oil product is drawn after 30min using the nitrogen content of TNS-3000 type nitrogen element sulphur analysis-e/or determining wherein nitride, then will
It is reused after ionic liquid recycling, measures the content of corresponding nitride respectively:
。
Embodiment 6.
The preparation process of more sulfonate ion liquid is with embodiment 3:
1g ionic liquid sample is fitted into the glass reactor with magnetic agitation, 400mL is then added thereto again
Nitrogen content is 145.6mg/L, and sulfur content is the 93# gasoline of 82.5mg/L, and reaction 60min, quiescent settling is stirred at room temperature
Upper layer oil product is drawn after 30min using the nitrogen content of TNS-3000 type nitrogen element sulphur analysis-e/or determining wherein nitride, then will
It is reused after ionic liquid recycling, measures the content of corresponding nitride respectively:
。
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (3)
1. a kind of method of nitride in removing oil product, it is characterised in that: more sulfonate ion liquid are added into oil product, make oil
Non basic nitrogen compound in product carries out protonation removing, and the basic nitrogen compound in oil product carries out sulfonated removing；It is wherein described more
The structural formula of sulfonate ion liquid are as follows:
；
Specifically, more sulfonate ion liquid are mixed with oil product according to the mass volume ratio of 1g/400mL, at room temperature
20 ~ 30min is stirred, the non basic nitrogen compound in oil product is reacted and generates oligomer, basic nitrogen compound is converted into 3- pyridine-sulfonic acid；
Wherein, more sulfonate ion liquid are made of being made by the steps:
1) Isosorbide-5-Nitrae-butane sultones is mixed by the molar ratio of 1:1 with triphenyl phosphorus and is placed in microwave reactor, 400 ~
In 60 ~ 90 under the power of 600woAfter C reacts 30min ~ 2h, vacuum filtration is carried out and carries out vacuum after being cleaned with anhydrous propanone to do
It is dry to obtain substance M；
2) by the concentrated sulfuric acid of substance M and 98wt% by 1:4 molar ratio at room temperature after mixing, be put into microwave reaction
In device, 120 under the power of 300wo30min is reacted under the conditions of C, then carries out being filtered by vacuum and washs 2 ~ 3 with anhydrous propanone
Vacuum drying, obtains more sulfonate ion liquid after secondary.
2. removing the method for nitride in oil product as described in claim 1, it is characterised in that: the non basic nitrogen compound is Yin
Diindyl.
3. removing the method for nitride in oil product as described in claim 1, it is characterised in that: the basic nitrogen compound is pyridine.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967389A (en) * | 2010-10-27 | 2011-02-09 | 大庆油田有限责任公司 | Denitrifying agent for directly removing basic nitrogen compound from shale oil |
| CN105400542A (en) * | 2015-09-30 | 2016-03-16 | 青岛农业大学 | Selective removal of nitrogen compounds in oil products using biimidazole SO3H-functionalized ionic liquid |
| CN105505450A (en) * | 2015-12-12 | 2016-04-20 | 福建工程学院 | Alkylated gasoline preparation method based on ionic liquid catalyst |
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2017
- 2017-11-06 CN CN201711080871.9A patent/CN107586559B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967389A (en) * | 2010-10-27 | 2011-02-09 | 大庆油田有限责任公司 | Denitrifying agent for directly removing basic nitrogen compound from shale oil |
| CN105400542A (en) * | 2015-09-30 | 2016-03-16 | 青岛农业大学 | Selective removal of nitrogen compounds in oil products using biimidazole SO3H-functionalized ionic liquid |
| CN105505450A (en) * | 2015-12-12 | 2016-04-20 | 福建工程学院 | Alkylated gasoline preparation method based on ionic liquid catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 离子液体非加氢脱氮技术的研究进展;庞海全 等;《化工环保》;20161015;第36卷(第5期);第2.1节 |
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