CN101260314A - Oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent - Google Patents
Oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent Download PDFInfo
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- CN101260314A CN101260314A CNA2008101057232A CN200810105723A CN101260314A CN 101260314 A CN101260314 A CN 101260314A CN A2008101057232 A CNA2008101057232 A CN A2008101057232A CN 200810105723 A CN200810105723 A CN 200810105723A CN 101260314 A CN101260314 A CN 101260314A
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Abstract
The invention relates to a new method of desulfurization for oil products and solvent recovery, comprising the following steps of: oxidizing sulfide in the oil products by organic or inorganic peroxide, then compositing imidazole ionic liquid and alcohols or alcamines and alcohols derivate or alcamines derivate according to a definite proportion, which are used as desulfurizer, and extracting and removing the oxide of organic sulfur or inorganic sulfur in the oil products. At the same time, the added ironic liquid has the advantages of designable structure and polarity, so the new method can improve the desulfurization degree above 98 percent, after desulphurizinig heavy oil with higher boiling point, performing the solvent recovery by back-extracting alcohols, alcamines, ethers, nitriles with lower boiling point and the derivates of alcohols, alcamines, ethers and nitriles, while light oil with lower boiling point can perform the solvent recovery by means of reduced pressure distillation.
Description
Technical field:
The present invention relates under the catalyzed oxidation condition sulfide in the oil product is carried out oxidation, be compounded to form the abstraction desulfurization agent with ionic liquid and organic solvent again the sulfide in the oil product is extracted, reclaim extraction agent then and carry out reusable a kind of desulfurizing oil novel method.
Background technology:
Along with crude resources is exhausted day by day, market competition violent day by day, the refining ratio of mixing of high-sulfur crude oil rises year by year, and the sulphur content of FCC stock oil also increases thereupon, causes the sulphur content of follow-up processed oil also to improve constantly, so the desulphurization problem of oil product is urgent day by day.Therefore, carry out the research that low cost, high efficiency method reduce sulfur content in oil products, become the task of top priority of China's oil refining industry.
As green solvent, unique character such as ionic liquid has that polarity is strong, solvability good, low-steam pressure, structure can design, have broad application prospects in fields such as extracting and separating, catalyzed reactions, especially replacing traditional catalyzer, the easy volatile solvent, aspects such as reduction VOC pollution have remarkable advantages.Caused people's attention as sweetening agent with the sulfocompound that removes in the oil product with ionic liquid.
But existing at present research mainly concentrates on independent employing ionic liquid carries out the abstraction desulfurization experiment, as studies show that glyoxaline ion liquid is to thiophene, DBT, main sulfurous organic compound has preferably solvability (as application (patent) number: among the CN200610066595 and apply for (patent) number CN200410037677 and application (patent) number CN03137916) and patent (publication number) CN101063046 and patent (publication number) CN101153225 in the oil fuel such as DMDBT.Desulfuration efficiency is low, the ionic liquid consumption is big, viscosity is high, thereby oil product intermediate ion liquid residue content height influences oil quality, the high deficiency of desulphurization cost but these class methods exist, and is difficult to be well used in industry.And traditional oxidation sweetening adopts alcohols or alcamines organic solvent as extraction agent mostly, and the ubiquity desulfuration efficiency is low, and organic solvent is easy to volatilization and causes deficiencies such as secondary pollution, sweetening agent loss are big.
Based on above present Research, the double solvents that the present invention forms with green solvent-ionic liquid and traditional extraction agent is to get the abstraction desulfurization agent after the oxidation to have lot of advantages.Glyoxaline ion liquid is more stable, and experiment shows thiophene, DBT, and main sulfurous organic compound has solvability preferably in the oil fuel such as mercaptan.And alcohols that is added or alcamines organic solvent contain-the OH base, show slightly alkalescence, itself are exactly good desulfurization extraction agent.Find after deliberation, after adding a certain amount of alcohols, alcamines or their derivative solvent in the ionic liquid, can improve ion liquid relevant performance greatly.In addition, in the solvent recuperation part, adopted strip at low temperatures principle, compare with traditional distillating method, both saved energy, can not change the performance of solvent again because of pyrogenic distillation, can reach fine reusable effect.More than research all shows, the ionic liquid that adds organic solvent has very big potentiality to be exploited and industrial prospect aspect oxidation sweetening of oil product.
Summary of the invention
The present invention relates to carboxyalkyl organism compound or carboxyalkyl ionic liquid is catalyzer, with superoxide (as H
2O
2Or peroxy acid etc.) for oxygenant oil product is carried out oxidation, carry out a kind of oxidation-extraction desulfurization novel method that the compound composite desulfurizing agent that forms extracts oil product by a certain percentage by in glyoxaline ion liquid and alcohols, alcamines and alcohols or the alcamines derivative one or more.Oil product involved in the present invention comprises the work in-process oil in crude oil, oil fuel, light hydrocarbon, heavy oil and the crude oil refining process.
The ionic liquid that uses among the present invention is made up of imidazoles positively charged ion and a kind of negatively charged ion, and organic solvent is by alcohols, alcamines, alcohols or alcamines derivative.A kind of by in the alkyl imidazole of different side chain carbon numbers of imidazoles positively charged ion wherein, negatively charged ion can be neutral or alkaline ion.Organic solvent is insoluble to a kind of in alcohols, alcamines, alcohols or the alcamines derivative of oil fuel by being dissolved in ionic liquid, as: glycol ether, triglycol, polyoxyethylene glycol-200 and polyoxyethylene glycol-400 and furfuryl alcohol, tetramethylolmethane, thanomin, trolamine etc., but be not limited to above-mentioned solvent.More than ion liquid structural formula can be exemplified below:
[emim] [PF
6]: 1-ethyl-3-Methylimidazole fluorophosphate
[bmim] [BF
4]: 1-butyl-3-Methylimidazole fluoroborate
[bmim] [PF
6]: 1-butyl-3-Methylimidazole fluorophosphate
[dmim] [PF
6]: 1-decyl-3-Methylimidazole fluorophosphate
In a certain amount of above-mentioned organic solvent, make both form new mixed extractant pure, the above-mentioned ion liquid dissolving of exsiccant.Join in proportion in a certain amount of sour product, at a certain temperature, add proper amount of oxidant and catalyzer and carry out desulfurization; The concentration range of ionic liquid in double solvents is 0.1%-99.9%.At pressure 0.1atm～50atm, temperature is at 273K～353K, and the reaction times is carried out the experiment that removes of sulfurous organic compound or inorganics to the oil product of sulfur-bearing in the 0.2-10h scope.The clear layering of meeting after the liquid of desulfurization system leaves standstill, after the separation with the extraction agent layer under certain temperature and pressure, the alcohols, alcamines, ethers, nitrile and their derivative that add a certain amount of lower boiling (boiling point is less than 150 ℃) are stripped, the sweetening agent that obtains is reusable, renewable recycling after the strippant underpressure distillation.
Embodiment:
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
With 3ml[Bmim] [PF
6] mix with the 2ml poly(oxyethylene glycol) 400, join in the analog gasoline of 10ml sulfur-bearing (thiophene) 1500ppm, under normal pressure stirs, when being warming up to 60 ℃, add the H of 2ml
2O
2With the acetate of 1ml, behind the magnetic agitation 3h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be dropped to 22ppm.After finishing using, isolate gasoline, solvent layer by underpressure distillation, is reclaimed solvent and can reuse.
Embodiment 2
With 3ml[Dmim] [PF
6] mix with the 2ml poly(oxyethylene glycol) 400, join in the analog gasoline of 10ml sulfur-bearing (thiophene) 1500ppm, under normal pressure stirs, when being warming up to 60 ℃, add the H of 2ml
2O
2With the acetate of 1ml, behind the magnetic agitation 3h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be dropped to 10ppm.After finishing using, isolate gasoline, solvent layer by underpressure distillation, is reclaimed solvent and can reuse.
Embodiment 3
With 4ml[Dmim] [PF
6] mix with the 1ml poly(oxyethylene glycol) 400, join in the analog gasoline of 10ml sulfur-bearing (thiophene) 1500ppm, under normal pressure stirs, when being warming up to 60 ℃, add the H of 1ml
2O
2With the acetate of 0.5ml, behind the magnetic agitation 3h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be dropped to 6ppm.After finishing using, isolate gasoline, solvent layer by underpressure distillation, is reclaimed solvent and can reuse.
Embodiment 4
With 4ml[Dmim] [PF
6] mix with the 1ml poly(oxyethylene glycol) 400, join in the straight-run diesel oil of 10ml sulphur content 700ppm, under normal pressure stirs, when being warming up to 60 ℃, add the H of 1ml
2O
2With the acetate of 0.5ml, behind the magnetic agitation 3h, leave standstill, layering, detect with KY3000 sulphur apparatus for nitrogen examination, the sulphur content in the oil product can be dropped to 25ppm.After finishing using, isolate oil product, after normal temperature and pressure was down with acetonitrile back extraction 30min, static layering was isolated sweetening agent can reuse with solvent layer, and acetonitrile vacuum-treat under 50 ℃ of conditions can be reused.
Embodiment 5
With 4ml[Dmim] [PF
6] mix with the 1ml thanomin, join in the straight-run spirit of 10ml sulphur content 260ppm, under normal pressure stirs, when being warming up to 60 ℃, add the H of 1ml
2O
2With the acetate of 0.5ml, behind the magnetic agitation 3h, leave standstill, layering, detect with KY3000 sulphur apparatus for nitrogen examination, the sulphur content in the oil product can be dropped to 8ppm.After finishing using, isolate oil product, solvent layer by underpressure distillation, is reclaimed solvent and can reuse.
Claims (10)
1. oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent, it is characterized in that choosing with in alkyl imidazo ion liquid and alcohols or alcamines and alcohol derivatives or the alcamines derivative one or more compound by a certain percentage as sweetening agent, in the presence of oxygenant and catalyzer, utilize the principle of oxidation-extraction to carry out desulfurization, solvent after the more lower boiling light oil desulfurization utilizes the method for underpressure distillation to reclaim, and the solvent after the mink cell focus desulfurization of higher can be with the recovery of stripping of lower boiling reverse-extraction agent.
2. a kind of oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent according to claim 1 is characterized in that the positively charged ion of the glyoxaline ion liquid that adopts is the ion that contains the alkyl imidazole of different side chain carbon numbers or contain glyoxaline structure.
3. a kind of oil oxidation-extraction desulfurization technique according to claim 1 based on ionic liquid composite solvent, it is characterized in that the oil product that this oxidation-extraction desulfurization technique removes comprises crude oil, oil fuel, the work in-process oil in light hydrocarbon, heavy oil and the crude oil refining process.
4. a kind of oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent according to claim 1, the temperature that it is characterized in that desulfurization is at 273K～473K.
5. a kind of oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent according to claim 1, the pressure range that it is characterized in that this sweetening process is preferably in 1～10atm at 0.1～50atm.
6. a kind of oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent according to claim 1 is characterized in that the concentration of ionic liquid in double solvents is 0.1%～99.9%.
7. a kind of oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent according to claim 1 is characterized in that agent-oil ratio in this desulfurization technology is between 1: 20～10: 1.
8. a kind of oil oxidation-extraction desulfurization method based on ionic liquid composite solvent according to claim 1 is characterized in that desulfurization time is controlled between 0.2h～10h.
9. a kind of oil oxidation-extraction desulfurization method based on ionic liquid composite solvent according to claim 1 is characterized in that the reverse-extraction agent that solvent recuperation adopts is alcohols, alcamines, ethers, nitrile or their derivative of lower boiling (boiling point is less than 150 ℃).
10. a kind of oil oxidation-extraction desulfurization method based on ionic liquid composite solvent according to claim 1 is characterized in that service temperature in the reextraction process is at 233K～333K.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101057232A CN101260314A (en) | 2008-05-04 | 2008-05-04 | Oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent |
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| CNA2008101057232A CN101260314A (en) | 2008-05-04 | 2008-05-04 | Oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982525A (en) * | 2010-11-09 | 2011-03-02 | 中国海洋石油总公司 | Method for removing sulfides in gasoline by imidazolium ionic liquid |
| CN102041014A (en) * | 2010-12-30 | 2011-05-04 | 北京低碳清洁能源研究所 | Ionic liquid composite extracting agent for separating asphaltene, preasphaltene and/or heavy oil from coal direct liquefaction residue |
| CN103664481A (en) * | 2013-11-11 | 2014-03-26 | 天津科林泰克科技有限公司 | Method for refining petrobenzene and thiophene by adopting double-partition-wall extraction rectifying tower |
| CN103664480A (en) * | 2013-11-11 | 2014-03-26 | 天津科林泰克科技有限公司 | Method for refining petrobenzene and thiophene by using ionic liquid complex solvent |
| CN104031708A (en) * | 2013-03-06 | 2014-09-10 | 中国石油天然气股份有限公司 | Ionic liquid formula solution for desulfurization of natural gas with high sulfur content |
| CN105694947A (en) * | 2016-03-30 | 2016-06-22 | 青岛科技大学 | Method for removing dibenzothiophene in gasoline by oxidation/extraction |
| CN105733656A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | FCC gasoline oxidation desulfurization method of composite acidic ionic liquid |
| CN110511780A (en) * | 2019-10-08 | 2019-11-29 | 磁悬浮润滑油(苏州)有限公司 | A method of sulfide in improvement desulfurizing agent removing oil product |
| CN112760146A (en) * | 2021-01-13 | 2021-05-07 | 中国石油大学(北京) | Auxiliary agent for improving regeneration performance of liquefied gas sweetening extractant and application thereof |
| CN113322094A (en) * | 2021-05-24 | 2021-08-31 | 江苏大学 | Reactive extraction desulfurization and denitrification and high value-added product recovery process |
-
2008
- 2008-05-04 CN CNA2008101057232A patent/CN101260314A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982525A (en) * | 2010-11-09 | 2011-03-02 | 中国海洋石油总公司 | Method for removing sulfides in gasoline by imidazolium ionic liquid |
| CN102041014A (en) * | 2010-12-30 | 2011-05-04 | 北京低碳清洁能源研究所 | Ionic liquid composite extracting agent for separating asphaltene, preasphaltene and/or heavy oil from coal direct liquefaction residue |
| CN104031708A (en) * | 2013-03-06 | 2014-09-10 | 中国石油天然气股份有限公司 | Ionic liquid formula solution for desulfurization of natural gas with high sulfur content |
| CN103664481A (en) * | 2013-11-11 | 2014-03-26 | 天津科林泰克科技有限公司 | Method for refining petrobenzene and thiophene by adopting double-partition-wall extraction rectifying tower |
| CN103664480A (en) * | 2013-11-11 | 2014-03-26 | 天津科林泰克科技有限公司 | Method for refining petrobenzene and thiophene by using ionic liquid complex solvent |
| CN105733656A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | FCC gasoline oxidation desulfurization method of composite acidic ionic liquid |
| CN105733656B (en) * | 2014-12-11 | 2017-10-17 | 中国石油天然气股份有限公司 | FCC gasoline oxidation desulfurization method of composite acidic ionic liquid |
| CN105694947A (en) * | 2016-03-30 | 2016-06-22 | 青岛科技大学 | Method for removing dibenzothiophene in gasoline by oxidation/extraction |
| CN110511780A (en) * | 2019-10-08 | 2019-11-29 | 磁悬浮润滑油(苏州)有限公司 | A method of sulfide in improvement desulfurizing agent removing oil product |
| CN112760146A (en) * | 2021-01-13 | 2021-05-07 | 中国石油大学(北京) | Auxiliary agent for improving regeneration performance of liquefied gas sweetening extractant and application thereof |
| CN113322094A (en) * | 2021-05-24 | 2021-08-31 | 江苏大学 | Reactive extraction desulfurization and denitrification and high value-added product recovery process |
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Application publication date: 20080910 |