CN103146415A - Novel method for removing indole in oil product through ionic liquid - Google Patents
Novel method for removing indole in oil product through ionic liquid Download PDFInfo
- Publication number
- CN103146415A CN103146415A CN2013100850478A CN201310085047A CN103146415A CN 103146415 A CN103146415 A CN 103146415A CN 2013100850478 A CN2013100850478 A CN 2013100850478A CN 201310085047 A CN201310085047 A CN 201310085047A CN 103146415 A CN103146415 A CN 103146415A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- oil product
- novel method
- indoles
- nitrogen removal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 29
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 150000002475 indoles Chemical class 0.000 claims description 17
- 238000004088 simulation Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 229910006069 SO3H Inorganic materials 0.000 abstract 1
- DXGTUUQHTDOFFQ-UHFFFAOYSA-N [N].C1=CC=C2NC=CC2=C1 Chemical compound [N].C1=CC=C2NC=CC2=C1 DXGTUUQHTDOFFQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011831 acidic ionic liquid Substances 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 27
- 238000002474 experimental method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the field of petrochemical engineering, and relates to a novel method for removing non-alkaline nitrogen-indole in an oil product through ionic liquid. The novel method is characterized in that SO3H-containing functionalized acidic ionic liquid is used as a catalyst and a solvent, and the operation can be carried out at lower temperature (20 to 70 DEG C); and after the reaction, the recovered ionic liquid can be reused by being simply treated. Compared with the conventional method, the novel method provided by the invention has following characteristics that (1) the conventional strong acid nitrogen removal and hydrogenation nitrogen removal in the background technology are not needed, so that the problems due to the corrosion of the equipment, the wastewater drainage, and the high price of equipment, can be greatly reduced; (2) the adopted ionic liquid is the water-soluble ionic liquid which can be layered well respect to a simulated oil product after being dissolved by water in a certain proportion, and thus the convenience is provided for the separation after the nitrogen removal treatment; and (3) the implemented liquid nitrogen removal method is mild in condition, the operation is simple and easy to carry out, the ionic liquid can be reused, and the problem in the background technology that the catalyst cannot be recycled can be avoided.
Description
Technical field
The invention belongs to petrochemical industry, relate to a kind of take ionic liquid as catalysts and solvents, with the non basic nitrogen in oil product--the novel method that indoles removes.
Technical background
In oil product, the existence of nitride affects color and the stability of oil product except meeting; Can be with oxynitride NO after burning
XForm enter atmosphere, cause outside serious atmospheric pollution; Also can bring great impact to the reduction of vapour, diesel oil sulphur content.In Oil Production, the organic nitrogen compound of denier just can cause valuable poisoning of catalyst in the technological processs such as catalytic cracking, hydrofining, shortens the work-ing life of catalyzer, thereby increases production cost, reduces output.According to statistics, in crude oil, nitrogen content reduces 90%, and the output of gasoline can improve 20%.Studies show that, one of nitride that exists in oil product---indoles is to hydrodesulfurization reaction inhibited (Xiang Chune etc., chemistry of fuel journal, 2008,36 (6): 684-690), have a strong impact on the quality of oil product.
Indoles is as the non basic nitrogen compound of a quasi-representative, and content is higher in oil product, and conventional removal methods has hydrodenitrification and non-hydrodenitrification.Hydrodenitrification is one of present most widely used method, this kind method technique comparative maturity, and have that technique is simple, easy to operate, oil product yield advantages of higher, but the required facility investment of hydrogenation is larger, and operational condition is harsh, and process cost is higher.And deep hydrogenation can make the oil quality variation, and stability descends, and shallow degree hydrogenation can make again denitrification percent reduce.At present, the focus of research is non-hydrodenitrification method.There are some researches show, but the equal effective elimination basic nitrogen compounds (CN101861374A) such as mineral acid, heteropolyacid, ion exchange resin, acidic ion liquid, but to the present rare bibliographical information of removing of non basic nitrogen compound.Only have in patent CN102390311A mentioned, its method be will be synthetic luxuriant iron class ionic liquid be used for removing the indoles of simulation oil product, be 150mgkg for nitrogen content
-1Oil product, its best denitrification percent is 89%.Although this patent adopts ionic liquid as denitrfying agent, such ionic liquid synthesizes more complicated, and denitrification effect remains further to be improved, and ionic liquid reuse poor effect, is difficult to apply.
Summary of the invention
The present invention proposes a kind of novel method by adopting ionic liquid that the indoles in oil product is removed.The method employing has certain deliquescent ionic liquid to indoles and makes catalysts and solvents, oil product is carried out denitrogenation processing, such ionic liquid has good water-soluble, be insoluble to gasoline, diesel oil, can effectively the indoles in oil product be extracted in the aqueous solution of ionic liquid after water-soluble, be convenient to separating of nitride and oil product; On the other hand, ionic liquid is after solvent wash is processed, and is reusable.
The purpose of this invention is to provide a kind of novel method of indoles in the simulation oil product that removes, a large amount of mineral acids of need consumption, the catalyzer that exist in traditional non-hydrogenation acid treating method can not be reused to overcome, equipment corrosion and the shortcoming such as discharge of wastewater is many.
The present invention is by these problems of following solution, and it is catalysts and solvents that employing has certain deliquescent ionic liquid to indoles, at a certain temperature, oil product is carried out denitrification reaction.After reaction finishes, by separatory, oil product is separated with ionic liquid, ionic liquid through the ether washing and revolve steam dewater after, can continue to use as catalysts and solvents.
The described ionic liquid of the inventive method has following structural formula: be SO
3The H functionalization
The acid type ionic liquid.
X-(CH
2)nSO
3H-Y n＝3，4
Present method realizes by following steps:
The preparation of simulation oil product: the normal heptane that the analytically pure indoles of 125.42mg (1.07mmo1) is dissolved in 100g--toluene is made solution in (mass ratio=80/20), and the concentration of the nitrogen in solution is 150mgkg
-1
Ionic liquid denitrogenation experiment: in a reaction flask with stopper and stirrer, add the 10mmol ionic liquid, with deionized water dilution (m
From: m
Water=2: 1), add 10g simulation oil product, stir 2-6h under 20-70 ℃, standing, suction pipe is drawn the upper strata oil product, measures the nitrogen content of oil product before and after denitrogenation with the TN-3000 apparatus for nitrogen examination, calculates accordingly ionic liquid to the denitrification percent of indoles.
Present method is compared with traditional method, is characterized in:
(1) need not to adopt traditional strong acid in background technology, significantly improved equipment corrosion and discharge of wastewater problem.
(2) owing to having adopted a kind of acidity ionic liquid soluble in water as reaction medium, water-soluble after, can well be used for oil product and separate, reaction conditions is simple.
(3) ionic liquid is reusable, and after reuse 6 times, its denitrification percent is still more than 90%, has overcome in background technology catalyzer and can not reuse problem, has reduced production cost.
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 and contain indoles simulation oil product (N%=150ppm) in reaction flask, add successively 10mmol (C
2H
5)
3N (CH
2)
3SO
3HHSO
4, the 1.6g deionized water, at 40 ℃ of lower stirring reaction 2h, react complete after, after reaction solution sedimentation 24h, get the upper strata oil product and survey nitrogen content, denitrification percent is 98.70%.
Embodiment 2: experiment condition and step just change ionic liquid into (C with embodiment 1
2H
5)
3N (CH
2)
3SO
3HCF
3SO
3, denitrification percent is 98.68%.
Embodiment 3: experiment condition and step just change ionic liquid into (C with embodiment 1
2H
5)
3N (CH
2)
3SO
3HCH
3SO
3, denitrification percent is 96.17%.
Embodiment 4: experiment condition and step just change ionic liquid into (C with embodiment 1
2H
5)
3N (CH
2)
3SO
3HBF
4, denitrification percent is 95.26%.
Embodiment 5-7: experiment condition and step just change respectively ionic liquid into (C with embodiment 1
2H
5)
3N (CH
2)
4SO
3HCF
3SO
3,
Acquired results sees Table 1.
The reaction result of table 1 embodiment 5-8
Embodiment 8-13: experiment condition and step just change ionic liquid into embodiment 1 ionic liquid that reclaims in embodiment 1, carry out repeating the reuse experiment for six times, and reuse the results are shown in Table 2.
The repetition reuse result of table 2 ionic liquid
Comparative example 1: experiment condition and step are with embodiment 1, just with (C
2H
5)
3N (CH
2)
3SO
3HHSO
4Change (C into
2H
5)
3NHSO
4, simulation oil denitrification rate is only 40.90%.
Claims (3)
1. a novel method that removes indoles non basic nitrogen in oil product with ionic liquid, is characterized in that adding the 10mmol ionic liquid in a reaction flask with stopper and stirrer, with deionized water dilution (m
From: m
Water=2: 1), add the 10g oil product, stir 2-6h under 20-70 ℃, standing, suction pipe is drawn the upper strata oil product, measures the nitrogen content of oil product before and after denitrogenation with the TN-3000 apparatus for nitrogen examination, calculates accordingly ionic liquid to the denitrification percent of indoles.
2. a kind of ionic liquid claimed in claim 1 removes the novel method of indoles non basic nitrogen in oil product, and the ionic liquid that it is characterized in that adopting is for containing SO
3The H functionalization
Acidic ion liquid has following structure: X-(CH
2) nSO
3H-Y,
N=3 or 4 wherein;
3. a kind of ionic liquid according to claim 1 removes the novel method of indoles non basic nitrogen in oil product, it is characterized in that oil product used is indoles simulation oil product, and N content is 150mgkg
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310085047.8A CN103146415B (en) | 2013-03-07 | 2013-03-07 | Novel method for removing indole in oil product through ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310085047.8A CN103146415B (en) | 2013-03-07 | 2013-03-07 | Novel method for removing indole in oil product through ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103146415A true CN103146415A (en) | 2013-06-12 |
| CN103146415B CN103146415B (en) | 2015-03-11 |
Family
ID=48544743
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310085047.8A Expired - Fee Related CN103146415B (en) | 2013-03-07 | 2013-03-07 | Novel method for removing indole in oil product through ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103146415B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105219423A (en) * | 2015-11-09 | 2016-01-06 | 扬州大学 | A kind of ionic liquid is used for the method for oil fuel denitrogenation |
| 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 |
| CN105400541A (en) * | 2015-09-30 | 2016-03-16 | 青岛农业大学 | Selective removal of basic nitrogen compounds in oil products using carboxyl-functionalized acid ionic liquid |
| CN110563629A (en) * | 2019-09-27 | 2019-12-13 | 河北科技大学 | Method for extracting indole from wash oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861374A (en) * | 2007-11-14 | 2010-10-13 | 环球油品公司 | Methods of denitrogenating diesel fuel |
-
2013
- 2013-03-07 CN CN201310085047.8A patent/CN103146415B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861374A (en) * | 2007-11-14 | 2010-10-13 | 环球油品公司 | Methods of denitrogenating diesel fuel |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105400541A (en) * | 2015-09-30 | 2016-03-16 | 青岛农业大学 | Selective removal of basic nitrogen compounds in oil products using carboxyl-functionalized acid ionic liquid |
| CN105400541B (en) * | 2015-09-30 | 2017-05-10 | 青岛农业大学 | Selective removal of basic nitrogen compounds in oil products using carboxyl-functionalized acid ionic liquid |
| CN105219423A (en) * | 2015-11-09 | 2016-01-06 | 扬州大学 | A kind of ionic liquid is used for the method for oil fuel denitrogenation |
| CN110563629A (en) * | 2019-09-27 | 2019-12-13 | 河北科技大学 | Method for extracting indole from wash oil |
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| Publication number | Publication date |
|---|---|
| CN103146415B (en) | 2015-03-11 |
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Granted publication date: 20150311 Termination date: 20180307 |