CN102199442A - Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant - Google Patents
Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant Download PDFInfo
- Publication number
- CN102199442A CN102199442A CN2011100962597A CN201110096259A CN102199442A CN 102199442 A CN102199442 A CN 102199442A CN 2011100962597 A CN2011100962597 A CN 2011100962597A CN 201110096259 A CN201110096259 A CN 201110096259A CN 102199442 A CN102199442 A CN 102199442A
- Authority
- CN
- China
- Prior art keywords
- oil product
- extractant
- oil
- agent
- amine proton
- 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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention relates to a method for applying an amine proton-type ionic liquid extractant in desulfurization of an oil product and recovering the extractant. The method comprises the following steps of: adding the amine proton-type ionic liquid extractant and a fuel oil to a treatment container according to a certain ratio, and carrying out reaction under stirring at the temperature of 20-65 DEG C and a stirring speed of 300-1200 rpm for 15-60 minutes; standing for demixing after reaction to separate an oil product layer and an extractant layer, wherein the oil product is desulfurized oil and detection shows that the sulfide content decreases by 13-77%; and distilling the extractant layer, and intercepting an extractant fraction to recover the extractant, wherein the recovered extractant can be used for desulfurization without effect lowering. A 56-58 DEG C fraction is intercepted when DMCEAP (N,N-dimethyl(cyanoethyl)ammonium propionate) is distilled to recover and a 82-84 DEG C fraction is intercepted when DMHEEAP (N,N-dimethyl-N-(2-hydroxyethoxyethyl)ammonium propionate) is recovered; the recovery rate is 70-95%; and the method is environmentally-friendly, and is a high-efficiency pollution-free desulfurization method; and simultaneously the extractant can be recycled, so as to greatly lower desulfurization cost.
Description
Technical field
The invention belongs to fuel oil and carry out the technical field of impurity separation method, relate to solvent extraction technology with chemical process.The present invention also belongs to fuel oil purified technical field, relates to the method that is used for desulfurization with the proton type ionic liquid.Specifically be with there being substituent organic acid ammonium salt to remove method assorted, condensed ring sulfide.
Background technology
In recent years, the atmosphere polluting problem that vehicle exhaust causes is serious day by day, the harm maximum of sulfide wherein, various countries are to the increasingly stringent that requires of sulphur content in the fuel oil, most countries has all proposed to solve from the source measure of automobile exhaust pollution, promptly adopt new technology and new technology,, realize cleaning of fuel oil to reduce the sulphur content in the fuel oil.At present, sulfur method commonly used is hydrogenating desulfurization (HDS) in the industry
[1-2]This method can effectively be eliminated fatty sulphur and non-fatty sulphur in the oil product, and dibenzothiophene condensed ring organic sulfides such as (DBT) is difficult to realize removing because of sterically hindered influence.For realizing the deep desulfuration target, indexs such as reactor pressure that classical hydrotreatment is used and treatment time just must improve, and it is extremely urgent therefore to carry out the deep desulfurization of fuel oil technical study.Non-hydrogenating desulfurization technology has become the focus of research, as biocatalytic desulfurization
[3], adsorption desulfurize
[4]And abstraction desulfurization
[5]Deng.Abstraction desulfurization is a kind ofly to have the technology that the principle of different solubilities is carried out desulfurization according to organic sulfide in the solvent and hydrocarbon polymer, can carry out under low-temp low-pressure even normal temperature and pressure.Yet extraction agent at present commonly used be organic solvent substantially, and volatility greatly, strong toxicity, environmental pollution be serious.Therefore, carry out green, safety, the research of novel extraction agent efficiently is significant.
Reference:
1.Alonso，L.；Arce，A.；Francisco，M.；Rodriguez，O.；Soto，A.，Gasolinedesulfurization?using?extraction?with[C-8mim][BF4]ionic?liquid.Aiche?J?2007，53(12)，3108-3115.
2.Bosmann，A.；Datsevich，L.；Jess，A.；Lauter，A.；Schmitz，C.；Wasserscheid，P.，Deep?desulfurization?of?diesel?fuel?by?extraction?with?ionic?liquids.Chem?Commun2001，(23)，2494-2495.
3.Sipma，J.；Henstra，A.M.；Parshina，S.N.；Lens，P.N.L.；Lettinga，G.；Stams，A.J.M.，Microbial?CO?conversions?with?applications?in?synthesis?gas?purification?andbio-desulfurization.Crit?Rev?Biotechnol?2006，26(1)，41-65.
4.Jayaraman，A.；Yang，F.H.；Yang，R.T.， Effects?of?nitrogen?compounds?andpolyaromatic?hydrocarbons?on?desulfurization?of?liquid?fuels?by?ad
5.Pereiro，A.B.；Rodriguez，A.，An?Ionic?Liquid?Proposed?as?Solvent?in?AromaticHydrocarbon?Separation?by?Liquid?Extraction.Aiche?J?2010，56(2)，381-386.
Summary of the invention
The object of the present invention is to provide a kind of extracting process, can high-level efficiency remove sulfocompound in the oil product-particularly those assorted, condensed ring sulphur compounds, and can reclaim extraction agent easily.
Ionic liquid has that better chemical stability, steam are forced down, designability and advantage such as can be recycled, and is considered to substitute " green solvent " of volatile organic solvent.Amine proton type ionic liquid not only has general ionic liquid excellent physical chemistry, also has unique advantages such as high-level efficiency, low cost, low-viscosity, easily recovery, environmental friendliness.Discover that amine proton type ionic liquid has good extraction ability to the sulfide in the oil product.
Using the proton type ionic liquid two prerequisites to be arranged during sulfocompound in as extraction agent extraction oil product: need extraction agent that very little solubleness is arranged in oil product, the compound with sulfur-bearing has very large avidity simultaneously.The extraction agent that the present invention selects is an amine proton type ionic liquid, and its amine positively charged ion contains one or more in alkyl, cyano group, hydroxyl, the alkoxyl group, and negatively charged ion is inorganic or organic neutrality or acidic anionic, as CH
3COO
-, HSO
4 -, BF
4 -, PF
6 -, NTf
2 -(two fluoroform sulfimide ion), wherein best kind such as N, N-dimethyl (nitrile ethyl) propionic acid ammonium (being designated hereinafter simply as DMCEAP) and N, N-dimethyl-N-(2-(2-hydroxyl-oxethyl)) propionic acid ammonium (hereinafter to be referred as DMHEEAP).
The mass ratio of extraction agent amine proton type ionic liquid and oil product is 1/10～2/1 during processing; The content of sulphur is 200～1600ppm in the oil product.
The step of handling is: in proportion ion liquid abstraction agent of extraction agent amine proton type and oil fuel are added in the processing vessel, at 20～65 ℃ of following stirring reaction 15～60min, mixing speed is 300～1200rpm.Standing demix after reaction is finished is told oil product layer and extraction agent layer.Oil product is sweet oil, and sulfide content descends 13～77% after testing.The extraction agent layer distills, and intercepting extraction agent cut to be reclaiming extraction agent, and the extraction agent of recovery can the reuse desulfurization, and effect does not reduce.As distill the cut of 56-58 ℃ of intercepting when reclaiming DMCEAP, and the cut of 82-84 ℃ of intercepting when reclaiming DMHEEAP.The rate of recovery 70～95%.Warp
1HNMR and
13The test of CNMR, the result shows that the ionic liquid structure does not change.Show that through desulfurization test once more effect of extracting does not change.
Described oil product is the work in-process in crude oil, fuel oil or the crude oil refining process.
The present invention is an extraction agent with one or more the amine proton type ionic liquid that contains in the positively charged ion in alkyl, cyano group, hydroxyl, the alkoxyl group, develops a kind of new technology of DBT in the oil product being carried out abstraction desulfurization.The amine proton type ion liquid abstraction agent that this process adopted has advantages such as solvability is good, operational condition is gentle, steam forces down, structure can design.And, be a kind of efficient, green sulfur method to not pollution of environment.Simultaneously extraction agent can recycling use, makes desulphurization cost be reduced significantly.
Below the invention will be further described with embodiment.
Embodiment
Embodiment 1
Under the room temperature condition, 1g DMCEAP is joined in the simulation oil product of 1g sulfur-bearing (dibenzothiophene) 1600ppm, magnetic agitation 20min, rotating speed 500rpm leaves standstill, layering, detects through gas chromatograph, and the sulphur content in the oil product is reduced to 592ppm.After reaction was finished, the liquid static layering was separated ionic liquid layer, carries out underpressure distillation, collects 56～58 ℃ of cuts, warp
1H NMR and
13The test of C NMR, the result shows that the ionic liquid structure does not change.The ionic liquid that distills is reused under the same conditions, and the sulphur content in the oil product drops to 642ppm.
Embodiment 2
Under the room temperature condition, 1g DMHEEAP is joined in the simulation oil product of 1g sulfur-bearing (dibenzothiophene) 1600ppm, magnetic agitation 20min, rotating speed 500rpm leaves standstill, layering, detects through gas chromatograph, and the sulphur content in the oil product is reduced to 592ppm.After reaction was finished, the liquid static layering was separated ionic liquid layer, carries out underpressure distillation, collects 56～58 ℃ of cuts, warp
1H NMR and
13The test of C NMR, the result shows that the ionic liquid structure does not change.The ionic liquid that distills is reused under the same conditions, and the sulphur content in the oil product drops to 693ppm.
Embodiment 3
Under the room temperature condition, 2g DMCEAP is joined in the simulation oil product of 1g sulfur-bearing (dibenzothiophene) 1600ppm, magnetic agitation 20min, rotating speed 500rpm leaves standstill, layering, detects through gas chromatograph, and the sulphur content in the oil product is reduced to 375ppm.After reaction was finished, the liquid static layering was separated ionic liquid layer, carries out underpressure distillation, collects 56～58 ℃ of cuts, warp
1H NMR and
13The test of C NMR, the result shows that the ionic liquid structure does not change, ionic liquid can reuse.
Embodiment 4
Under the room temperature condition, 2g DMHEEAP is joined in the simulation oil product of 1g sulfur-bearing (dibenzothiophene) 1600ppm, magnetic agitation 20min, rotating speed 500rpm leaves standstill, layering, detects through gas chromatograph, and the sulphur content in the oil product is reduced to 385ppm.After reaction was finished, the liquid static layering was separated ionic liquid layer, carries out underpressure distillation, collects 56～58 ℃ of cuts, warp
1H NMR and
13The test of C NMR, the result shows that the ionic liquid structure does not change, ionic liquid can reuse.
Claims (4)
1. the agent of amine proton type ion liquid abstraction is used for oil product desulfurization method, it is characterized in that step is:
(1) in proportion ion liquid abstraction agent of amine proton type and oil product are added in the processing vessel, at 20～65 ℃ of following stirring reaction 15～60min, mixing speed is 300～1200rpm;
(2) standing demix after reaction is finished is told oil product layer and extraction agent layer, and oil product is sweet oil, and sulfide content descends 13～77% after testing;
The agent of described amine proton type ion liquid abstraction, its amine positively charged ion contains one or more in alkyl, cyano group, hydroxyl, the alkoxyl group, and negatively charged ion is inorganic or organic neutrality or acidic anionic, as CH
3COO
-, HSO
4 -, BF
4 -, PF
6 -, NTf
2 -Oil product is the work in-process in crude oil, fuel oil or the crude oil refining process; The mass ratio of extraction agent amine proton type ionic liquid and oil product is 1/10～2/1; The content of sulphur is 200～1600ppm in the oil product.
2. be used for oil product desulfurization method according to the described amine proton type of claim 1 ionic liquid, it is characterized in that the agent of described amine proton type ion liquid abstraction is N, N-dimethyl (nitrile ethyl) propionic acid ammonium and N, a kind of in N-dimethyl-N-(2-(2-hydroxyl-oxethyl)) propionic acid ammonium.
3. the agent of amine proton type ion liquid abstraction is used for the recovery method of extraction agent behind the desulfurizing oil, it is characterized in that step (2) reaction finish after standing demix, tell oil product layer and extraction agent layer, its extract layer distills, and intercepting extraction agent cut is to reclaim extraction agent.
4. agent is used for the recovery method of extraction agent behind the desulfurizing oil according to the described amine proton type of claim 3 ion liquid abstraction, it is characterized in that the agent of described amine proton type ion liquid abstraction is N, N-dimethyl (nitrile ethyl) propionic acid ammonium and N, in N-dimethyl-N-(2-(2-hydroxyl-oxethyl)) propionic acid ammonium when a kind of, extract layer distills and reclaims N, intercepts 56-58 ℃ cut during N-dimethyl (nitrile ethyl) propionic acid ammonium; Reclaim N, intercept 82-84 ℃ cut during N-dimethyl-N-(2-(2-hydroxyl-oxethyl)) propionic acid ammonium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110096259 CN102199442B (en) | 2011-04-14 | 2011-04-14 | Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110096259 CN102199442B (en) | 2011-04-14 | 2011-04-14 | Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102199442A true CN102199442A (en) | 2011-09-28 |
| CN102199442B CN102199442B (en) | 2013-11-06 |
Family
ID=44660434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110096259 Active CN102199442B (en) | 2011-04-14 | 2011-04-14 | Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102199442B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560120A (en) * | 2014-11-13 | 2015-04-29 | 青岛科技大学 | Method for extracting removal of sulfides from fuel oil by using polyether type octadecylamine ionic liquid |
| CN105062547A (en) * | 2015-07-15 | 2015-11-18 | 大连大学 | Method for extracting thiophene and benzothiophene simultaneously |
| CN105694945A (en) * | 2016-03-04 | 2016-06-22 | 江苏大学 | Preparation method and application of protic ionic liquid |
| CN108135198A (en) * | 2015-05-27 | 2018-06-08 | 英国贝尔法斯特女王大学 | Chloropropyl alcohol and/or the method for glycidol or its aliphatic ester, the improvement glyceride oil method of refining including this method are removed from glyceride oil |
| CN108607323A (en) * | 2018-05-11 | 2018-10-02 | 东莞理工学院 | A kind of adsorption method of benzothiophene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837332A (en) * | 2005-03-24 | 2006-09-27 | 北京化工大学 | Method for removing sulfide from gasoline and diesel oil through extraction of ion liquid |
| CN1962827A (en) * | 2005-11-11 | 2007-05-16 | 中国科学院过程工程研究所 | Desulfurization regeneration method for sulfur-adsorbent ion liquid |
| CN101153225A (en) * | 2007-09-12 | 2008-04-02 | 中国科学院过程工程研究所 | Oxidization-abstraction desulfurization technology of petroleum product based on ion liquid |
| CN101376842A (en) * | 2007-08-31 | 2009-03-04 | 中国石油化工股份有限公司 | Method for reducing sulfur content in gasoline |
-
2011
- 2011-04-14 CN CN 201110096259 patent/CN102199442B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837332A (en) * | 2005-03-24 | 2006-09-27 | 北京化工大学 | Method for removing sulfide from gasoline and diesel oil through extraction of ion liquid |
| CN1962827A (en) * | 2005-11-11 | 2007-05-16 | 中国科学院过程工程研究所 | Desulfurization regeneration method for sulfur-adsorbent ion liquid |
| CN101376842A (en) * | 2007-08-31 | 2009-03-04 | 中国石油化工股份有限公司 | Method for reducing sulfur content in gasoline |
| CN101153225A (en) * | 2007-09-12 | 2008-04-02 | 中国科学院过程工程研究所 | Oxidization-abstraction desulfurization technology of petroleum product based on ion liquid |
Non-Patent Citations (1)
| Title |
|---|
| 王志国，等: "离子液体在车用燃料油脱硫中的应用", 《化工科技》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560120A (en) * | 2014-11-13 | 2015-04-29 | 青岛科技大学 | Method for extracting removal of sulfides from fuel oil by using polyether type octadecylamine ionic liquid |
| CN108135198A (en) * | 2015-05-27 | 2018-06-08 | 英国贝尔法斯特女王大学 | Chloropropyl alcohol and/or the method for glycidol or its aliphatic ester, the improvement glyceride oil method of refining including this method are removed from glyceride oil |
| CN105062547A (en) * | 2015-07-15 | 2015-11-18 | 大连大学 | Method for extracting thiophene and benzothiophene simultaneously |
| CN105694945A (en) * | 2016-03-04 | 2016-06-22 | 江苏大学 | Preparation method and application of protic ionic liquid |
| CN108607323A (en) * | 2018-05-11 | 2018-10-02 | 东莞理工学院 | A kind of adsorption method of benzothiophene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102199442B (en) | 2013-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102199442B (en) | Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant | |
| AU745496B2 (en) | Removal of naphthenic acids in crude oils and distillates | |
| CN101735882B (en) | Method for regenerating base oil by waste internal-combustion engine oil | |
| CN106753514B (en) | A kind of method of choline eutectic solvent abstraction desulfurization | |
| CN101993750A (en) | Method for refining liquefied petroleum gas | |
| WO2012082203A1 (en) | System and process for capture of h2s from gaseous process streams and process for regeneration of the capture agent | |
| CN105368574A (en) | Deacidifying agent decreasing acid value of liquid organic mixtures and preparation technology | |
| CA2496735A1 (en) | Natural gas treatment process with extraction of the solvent in the acid gas | |
| CN113289458B (en) | Application of amine compound in removing organic sulfide | |
| CN106397252B (en) | Device and method for efficiently recycling DMF (dimethyl formamide) from wastewater | |
| WO2013188367A1 (en) | Process for the treatment of liquefied hydrocarbon gas using 2 -amino -2 (hydroxymethyl) propane - 1, 3 - diol compounds | |
| CN108893137B (en) | Water-based eutectic solvent, preparation method thereof and oil product extraction desulfurization method | |
| CN103361107A (en) | Extraction method of benzothiophene | |
| HRP20110322T1 (en) | Process for the purification of montelukast | |
| US3864245A (en) | Solvent extraction with increased polar hydrocarbon purity | |
| CN102159679A (en) | Method and apparatus for recovering hydrogen in petroleum-based hydrocarbon desulfurization process | |
| CN102408915A (en) | Method for oil product desulfurization through oxidation and extraction | |
| CN105294741A (en) | Method for synthesizing Cu-BTC material by utilizing deep-eutectic solvent as solvent | |
| CN103602346A (en) | Method for desulfurizing oil through oxidation-extraction coupling | |
| CN108018066A (en) | A kind of method of the deep desulfuration containing sulfur feedstock | |
| JP6077650B2 (en) | Process for the treatment of liquefied hydrocarbons using 3- (piperazin-1-yl) propane-1,2-diol compounds | |
| CN101982525A (en) | Method for removing sulfides in gasoline by imidazolium ionic liquid | |
| CN105419859A (en) | Reverse back extraction refining method for petroleum reduced pressure distillation distillate and application thereof | |
| CN102618322A (en) | Method for desulfurizing fuel oil extracted by catalytic oxidation of carboxyl functionalized benzimidazole ionic liquid | |
| CN113318586A (en) | Application of amine compound in improvement of organic sulfur dissolution and absorption removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |