CN101376842B - Method for reducing sulfur content in gasoline - Google Patents
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- CN101376842B CN101376842B CN2007101211955A CN200710121195A CN101376842B CN 101376842 B CN101376842 B CN 101376842B CN 2007101211955 A CN2007101211955 A CN 2007101211955A CN 200710121195 A CN200710121195 A CN 200710121195A CN 101376842 B CN101376842 B CN 101376842B
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Abstract
The invention discloses a method for reducing the sulfur content in gasoline which includes of cutting fraction oil containing sulfur gasoline into a light fraction and a heavy fraction; a hydrogenation refining method is adopted to desulfurize the heavy fraction gasoline; the method including the following steps is adopted to desulfurize the light fraction gasoline: a) in an extraction unit which takes an ion liquid as an extraction agent and under the extraction condition of the ion liquid, the light fraction gasoline is contacted with the ion liquid, then the light fraction gasoline with reduced sulfur content and the ion liquid rich in sulphocompounds are obtained through separation; b) in an extraction unit which takes water as an extraction agent, the ion liquid of the sulphocompounds obtained in step a is contacted with the water, then the sulphocompounds and the mixture of water and ion liquid are obtained through separation; c) the mixture of the water and the ion liquid are obtained through the separation step b of a distilling method and then a regenerated ion liquid is obtained; d) the heavy fraction gasoline desulfurized through the hydrogenation refining method is mixed with the light fraction gasoline the sulfur content of which is reduced, thus obtaining product oil.
Description
Technical field
The present invention relates to a kind of gasoline modifying method, particularly relate to a kind of through reducing sulfur in gasoline content carries out upgrading to gasoline method.
Background technology
Catalytically cracked gasoline is the important composition source of gasoline product because octane value is higher.But because this olefin content in gasoline and sulphur content are higher relatively, generally be respectively 15-45% and 500-5000ppm, be difficult to satisfy the requirement of gasoline products standard.For example, in Europe II motor spirit technical requirements 1 regulation that can reference: sulphur content is not more than that 500ppm, olefin(e) centent are not more than 30%, aromaticity content is not more than 40% (wherein the benzene content in the aromatic hydrocarbons is not more than 2.5%); Europe III motor spirit technical requirements 2 regulations: sulphur content is not more than 150ppm, aromaticity content is not more than at 35% o'clock, and olefin(e) centent is not more than 25%.Therefore, this type gasoline all need be made with extra care the rear and can be used as product oil or the use of product oil blend component.
In the prior art, can adopt several different methods to reduce the sulphur content in the gasoline fraction oil.
Hydrogenation is a kind of very effective desulfurization technology.But during hydrogenation in the gasoline alkene cause octane value to descend inevitably simultaneously by saturated.In order to solve in the gasoline behind the low molecular weight olefins hydrogenation by the saturated problem that causes gasoline octane rating to descend significantly, a lot of patented technologies adopt the process for selective hydrogenation that full distillation gasoline is cut in advance lighting end gasoline and last running gasoline.Wherein, lighting end gasoline can adopt the alkali wash desulfurization, and last running gasoline is through the hydrogenation reaction desulfurization.Because the lighting end gasoline of enrichment alkene is hydrogenation not, has avoided loss of octane number.And last running gasoline reduces because of the octane value that hydrogenation causes, then can adopt the method for octane value recovering that it is compensated.For example, this type of different technology is all disclosed in US 5411658, US 5391288, CN 1465668A, CN1521241A and CN146566A.Yet; Alkali wash can only remove in the lighting end gasoline straight catenate sulfide such as mercaptan, thioether; And can't remove the cyclic thiophene sulfocompounds; Its product with hydrogenation after the last running gasoline sulphur content still higher (greater than 150ppm) of mixing the gasoline products that the back obtains, can not obtain satisfying motor spirit standard or the lower gasoline products of sulphur content of Europe III.
Alkylation is a kind of non-hydrogenating desulfurization technology.Under catalyst action, thiophenes in the gasoline and olefine reaction generate the alkylated substituted thiazoline fen.CN1552705A has proposed with the ionic liquid-catalyzed method that makes octene-1 and thiophene-type sulfide alkylation reduce sulphur content of chlorine aluminic acid type; Reaction such as octene-1 and thiophene back carbon number increases; The elevation of boiling point, thus gasoline fraction broken away from, reached the desulfurization purpose of gasoline fraction.The weak point of this method is that alkylate is wanted could separate with gasoline fraction after the redistillation; And when adopting distillating method to separate; A large amount of gasoline products is an overhead product; A spot of reorganization by sulfocompound such as mercaptan, thioether and thiophene and the generation of alkene generation alkylated reaction is divided into bottoms, and energy consumption is high.In addition, the reaction of olefine in low carbon number self is difficult to avoid, thereby brings loss of octane number.And having the report to show, the RON of chlorine aluminic acid type ionic liquid catalyzed alkylation desulfurization instance and alkene lose bigger, are respectively 2.1 octane value units and 5.02 weight % (referring to Huang Weixia; Li Yunlong, Wang Xieqing, the application of ionic liquid in the catalytically cracked gasoline desulfurization; The chemical industry progress; 23 the 3rd phases of volume, 2004,297～299 pages).
Extraction process is another kind of non-hydrogenating desulfurization technology.For example, the GT-DeSulf method has been improved the aromatic hydrocarbons extraction technique (referring to Joseph Gentry, Tofik Khanmamedov, Randi WrightWytcherley from two aspects; Profitable desulfurization; HYDROCARBON ENGINEER; 2002, No.2).This method with extraction technique and hydrogen addition technology combination, is divided into lighting end and last running to sour gasoline earlier on the one hand, and extracting and hydrogenation have improved extraction solvent (Techtiv on the other hand respectively
TM-DS), and in extracting aromatic hydrocarbons, extracting thiophenes more up hill and dale, but part mercaptan and thioether can remain in and take out in the excess.The advantage of this method is: the treatment capacity of hydrogenation unit has been reduced in (1), and during (2) extraction lighting end gasoline, the alkene more than 90% can be stayed and take out in the excess, directly as gasoline product, has avoided hydrogenation to cause loss of octane number.Shortcoming is: (1) is taken out excess and is also wanted alkali cleaning to remove thioether and mercaptan etc., just can obtain super low-sulfur oil; (2) aromatic hydrocarbons and thiophene-based are drawn out of together, have caused the loss of taking out high-octane rating aromatic component in the excess.
US20040045874A1 discloses a kind of use butyl methyl imidazoles bis trifluoromethyl sulphonamide and the butyl methyl pyridine bis trifluoromethyl sulphonamide plasma liquid method for butanethiol (sulphur content 1000ppm) in the main extraction agent extraction gasoline, and the volume ratio of ionic liquid and analog gasoline is 0.25.Do not add when helping extraction agent, the butanethiol decreasing ratio has only 4.9～7.7%, add butanethiol 10 times (equivalence ratios) help extraction agent trifluoromethanesulfonic acid or trimethylammonium oxygen drone tetrafluoride boron after, butanethiol can basically all remove (mercaptan sulfur＜10ppm).Its open defect is the ion liquid abstraction agent and helps the extraction agent price too expensive.
US7001504B2 discloses a kind of method with thiophene-type sulfide in ethyl-methyl imidazoles fluoroform sulphonate, ethyl-methyl imidazoles aluminum tetrachloride, butyl methyl imidazoles aluminum tetrachloride and the butyl methyl imidazoles hexafluorophosphate plasma liquid extraction gasoline; The thiophene-based decreasing ratio can reach 85%; If initial oxidation becomes sulfone or sulfoxide to extract again, the thionaphthene decreasing ratio can reach 98%.But ion liquid cationic components all adopts di-alkyl-imidazole.Because the production technique of di-alkyl-imidazole is complicated, price is obviously higher.
The existing employing in the ion liquid extracting process; Except like positively charged ion be many alkyl imidazole ionic liquids on the high side, the regeneration of ionic liquid adopts usually that evaporation, reduction vaporization, hydrogen or rare gas element gas are carried, the methods such as sulfocompound in the organic solvent reextraction ionic liquid realize.For method with this type of the sulfocompound regeneration of ionic liquid in the organic solvent reextraction ionic liquid; Because in the removal process again of organic solvent; A large amount of organic solvents separates with a spot of extractum with the form of overhead product usually, and energy consumption problems such as volatilization high and organic solvent are restricted the industrial application of these class methods.
Summary of the invention
The technical problem that the present invention will solve is the defective that exists in the existing gasoline desulfating method, and a kind of method of more efficiently reduction sulfur in gasoline content newly is provided.
The present invention provides a kind of method that reduces sulfur in gasoline content, comprise with the sour gasoline distillate be cut into light, weigh two cuts; Last running gasoline is adopted the hydrofinishing process desulfurization; With gently heating up in a steamer the method desulfurization that gasoline divides employing to comprise the steps: be the extraction cells of extraction agent with the ionic liquid a); Under the ion liquid abstraction condition; Lighting end gasoline is contacted with ionic liquid, obtain lighting end gasoline that sulphur content reduced and the ionic liquid that is enriched with sulfocompound through separating; B) be the extraction cells of extraction agent with water, the ionic liquid of the enrichment sulfocompound that step a) is obtained contacts with water, obtains sulfocompound and water and ion liquid mixture through separating; C) water and the ion liquid mixture that employing distillating method separating step b) obtain obtain the regenerated ionic liquid; D) the lighting end gasoline that will be have partly or entirely reduced through the last running gasoline of hydrofinishing process desulfurization and part or all of sulphur content mixes and obtains product oil.
Compare with existing method, advantage of the present invention mainly shows the following aspects:
1. the present invention regenerates to ionic liquid as extraction agent with water, no matter is operational condition, still all realizations more easily such as recycling of the sulfocompound of regeneration back by-product.The ionic liquid that uses in the inventive method, water and entrainer etc. all can be recycled, and do not discharge basically or discharge seldom, and the ionic liquid steam forces down, and be non-volatile basically, favourable to environmental protection.
2. with traditional alkali wash desulfurization ratio, the inventive method desulfuration efficiency is high, realizes the deep desulfuration of lighting end gasoline more easily.For example adopt the inventive method that lighting end gasoline is carried out desulfurization, can sulphur content be taken off to 10ppm; And adopt traditional alkali cleaning method that same lighting end gasoline is carried out desulfurization, because can not remove thiophene-based, sulphur content is still more than 80ppm.
3. the present invention pays attention to selecting ionic liquid or the ionic liquid combination low to hydrocarbon solubility, and the alkene loss of said extraction process is little, and is favourable to the anti-knock index that keeps gasoline products to greatest extent.For example, the result who provides from embodiment sees, adopts the inventive method to carry out gasoline desulfur, and wherein, lighting end gasoline anti-knock index, last running gasoline anti-knock index and mixed full distillation gasoline anti-knock index loss all are not more than 1.0 octane value units.
Description of drawings
Fig. 1 provides a kind of schematic flow sheet of method for the present invention.
According to the method described in the present invention, said the sour gasoline distillate is cut into light, as to weigh two cuts method and operational condition is usual method in this area and condition.Preferred cutting temperature is 60-120 ℃, further is preferably 70-100 ℃.It is the 30-70 weight % of sour gasoline distillate total amount that said cutting preferably makes the amount of lighting end gasoline, further is preferably 30-60 weight %.
Embodiment
According to the method described in the present invention, said ionic liquid be selected from any water-soluble, through one or more in the reproducible ionic liquid after distillation and the water sepn.They can be commercially available commodity or adopt any one existing method to prepare.Wherein preferred anionic is one or more in fluoroboric acid root, inferior sulfate radical or the sulfuric acid mono alkyl ester ionic ionic liquid.Further be preferably fluoroboric acid root, inferior sulfate radical or sulfuric acid mono alkyl ester negatively charged ion and nitrogen-containing organic compound positively charged ion, for example, be selected from the ionic liquid of monoalkyl imidazoline, di-alkyl-imidazole, quaternary ammonium alkyl cation composition one or more.
In more preferred embodiment; Said ionic liquid is elected the ionic liquid of fluoroboric acid root, inferior sulfate radical or sulfuric acid mono alkyl ester negatively charged ion and monoalkyl imidazoline cation composition as; Or the ion liquid mixture of the ionic liquid of fluoroboric acid root, inferior sulfate radical or sulfuric acid mono alkyl ester negatively charged ion and monoalkyl imidazoline cation composition and fluoroboric acid root, inferior sulfate radical or sulfuric acid mono alkyl ester negatively charged ion and di-alkyl-imidazole cation composition; By percentage to the quality and with said mixed ionic liquid is benchmark, and positively charged ion is that the ion liquid content of di-alkyl-imidazole preferably is not more than 50% in the said mixture.
According to the method described in the present invention, the sour gasoline distillate contacts [or the ionic liquid of enrichment sulfocompound contacts with water in the step b)] in the wherein said step a) with ionic liquid, can adopt the extracting operation method of any known to realize.For example, can adopt under agitation with ionic liquid and sour gasoline distillate (or with water and the ionic liquid that is enriched with sulfocompound) blended extracting process in extractor; Or the method that in the extraction tower device, the sour gasoline distillate ionic liquid of sulfocompound (or be enriched with) and extraction agent ionic liquid (or water) is flowed and contact in opposite directions.Said extraction plant can be any extraction plant well known in the art.For example, a kind of extraction plant of forming by a plurality of stirring tanks that provides in " Elementary Chemical Engineering " (department of chemistry of Peking University writes group and compiles, 202 pages of " Elementary Chemical Engineering " (second editions), Higher Education Publishing House, 1983) etc.
According to the method described in the present invention, the extraction conditions of said step a), adopting with the ionic liquid is the usual operational condition of extraction agent.For example, in US7001504B2, conditions such as the agent-oil ratio of extraction agent in the ion liquid abstraction and sour gasoline distillate, extraction temperature are described.Here quote as a reference.
In preferred embodiment, the extraction of said step a) preferably makes the sulphur content of the lighting end gasoline products gasoline after the final extraction be not more than 50ppm, further preferably is not more than 10ppm.Said is that the preferred temperature of extraction conditions of the extraction cells of extraction agent is a room temperature-200 ℃ with the ionic liquid; The volume ratio of said ionic liquid and lighting end gasoline is 0.01-1; Further preferred temperature is 50-100 ℃, and the volume ratio of ionic liquid and lighting end gasoline is 0.1-0.5.
According to the method described in the present invention; The contact conditions of said step b) preferably includes: temperature is a room temperature to 90 ℃; Further be preferably room temperature to 50 ℃, the ion liquid volume ratio of described water and enrichment sulfocompound is 0.1-10, further is preferably 0.5-2.5.
According to the method described in the present invention; In the fractionation by distillation operation of said step c); Water separates with ionic liquid as overhead product, and wherein said distillating method can be that any one is this area conventional process, for example; Can adopt the method for air distillation to separate, also can adopt the method for underpressure distillation to separate.Be preferably underpressure distillation.
In further preferred embodiment; Said distillation also is included in water and the ion liquid mixture and introduces entrainer; Said entrainer is selected from one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, normal hexane, hexanaphthene, the benzene; Preferred one or more in Virahol, isopropylcarbinol, hexanaphthene and benzene, it is 0.1-10 that the introducing amount of said entrainer makes the volume ratio of said entrainer and said water and ion liquid compound, is preferably 0.1-1.
In " Elementary Chemical Engineering " relevant for the detailed description of component distillation device, method; For example; (department of chemistry of Peking University writes group and compiles in comprising the device of being made up of two azeotropy rectification columns, to carry out " azeotropic distillation " method; 188 pages of " Elementary Chemical Engineering " (second editions), Higher Education Publishing House, 1983); Or adopt falling film evaporator to carry out distillatory method (referring to " the industry standard QB/T 1163-91 of the People's Republic of China falling film evaporator ").Here quote as a reference in the lump.Through reducing distillation temperature, favourable to ion liquid recovery at water and ion liquid mixture introducing azeotrope.
According to the method described in the present invention, the water that obtains through fractionation by distillation or the mixed solution of water and entrainer can partly or entirely recycle.
According to the method described in the present invention; It is conventionally known to one of skill in the art that catalyzer and concrete operations and condition are used in said employing hydrofinishing process counterweight distillation gasoline desulfurization; For example, can carry out the desulfurization operations of last running gasoline with reference to EP940464 or the disclosed process for selective hydrogenation of CN 1465668A.In the present invention, preferred hydrofining reaction desulfurization condition comprises: hydrogen partial pressure is the 1.0-4.0 MPa, and temperature of reaction is 200-380 ℃, and liquid hourly space velocity is 3.0-5.0 hour
-1, hydrogen to oil volume ratio is 200-600Nm
3/ m
3Said Hydrobon catalyst can be VIB or the VIII family non-precious metal catalyst that loads on aluminum oxide or the silica-alumina supports.Last running gasoline contacts with Hydrobon catalyst with hydrogen together, and hydrogenating desulfurization, denitrogenation, saturation of olefins are separated the gasoline fraction after obtaining making with extra care at last, and hydrogen-rich gas recycles.
The step that after the heavy fractioning hydrogenation desulfurization, also can comprise according to the method described in the present invention, an octane value recovering.According to technology well known in the art; When needs counterweight distillation gasoline carries out deep desulfuration; Contained alkene is simultaneously by saturated in the distillate; The octane value of oil product obviously reduces behind the hydrogenation with making, and the step of octane value recovering is that the generation oil after the hydrogenating desulfurization is contacted with octane value recovering catalyst under the octane value recovering reaction conditions, the step that low octane rating component is wherein transformed.CN1465666A discloses a kind of method of deep desulfurization olefin hydrocarbon reduction of gasoline, wherein octane value recovering catalyst system therefor, operational condition etc. is described, and quotes as a reference here.
According to of the present invention preferred embodiment a kind of, the method for reduction sulfur in gasoline content provided by the invention can realize through flow process shown in Figure 1.As shown in Figure 1; The sour gasoline distillate through 16 introduce knockout towers 4 cut into light, weigh two cuts, said cutting temperature is 60-120 ℃, is preferably 70-100 ℃; It is the 30-70 weight % of gasoline total amount that said cutting makes the amount of lighting end gasoline, is preferably 30-60 weight %; Lighting end gasoline is that the extraction cells 1 of extraction agent contacts under the ion liquid abstraction condition with the ionic liquid that warp 13 is introduced with the ionic liquid through 6 introducings; Said contact makes the sulphur content of the lighting end gasoline products gasoline after the final extraction be not more than 50ppm; Further preferably be not more than 10ppm; Afterwards, obtain the lighting end gasoline that sulphur content reduced and draw through separating through 14; The ionic liquid that is enriched with sulfocompound is that the extraction cells 2 of extraction agent contacts with the water that warp 12 is introduced with water through 7 introducings; The ion liquid abstraction that is enriched with in the ionic liquid of sulfocompound is gone into water; Afterwards, draw through 11 through separating the sulfocompound that obtains; The mixture of ionic liquid and water is gone into to distill unit 3 through 8 and is removed the water in the ionic liquid through distillation; The all or part of warp 10 that separates the regeneration of ionic liquid that obtains is circulated back to extraction cells 1, and water is drawn through 9; Heavy distillate is introduced unifining desulphurization reaction unit 5 through 18 and is carried out desulfurization; Hydrogen is wherein introduced hydrodesulfurization reaction unit 5 through 17; Generation after unifining desulfurization oil through 15 draw after, obtain 19 recovery of product oil warp with mixing through the 14 lighting end gasoline of drawing.
According to the described flow process of Fig. 1, wherein by 11 sulfocompounds of drawing, can mix the back with the last running gasoline of cutting and get into hydrodesulfurization reaction unit 5 and carry out upgrading, also can reclaim separately.Sulfocompound after reclaiming separately can adopt the further processing and utilization of any one prior art, for example reclaims sulfide with methods such as oxidations.The water that warp 9 is drawn can partly or entirely recycle.
According to the method described in the present invention, wherein said sour gasoline distillate can be one or more in full cut catalytic cracking (FCC) gasoline, catalytic pyrolysis (DCC) gasoline, coker gasoline, steam cracking gasoline, the pressure gasoline.
Following embodiment will do further explanation to the present invention.
Embodiment 1-7 explanation is applicable to ionic liquid of the present invention and result of use thereof.
In 200 ml containers, packing into, (make by oneself, the preparation method sees John D.Holbrey etc., J.Chem.Soc. to 15 milliliters of Methylimidazole borofluoride ion liquid; Dalton Trans., 1999,2133-2139) with 100 milliliters of analog gasoline [sulphur contents: 200ppm; 100 ml n-hexanes (M=86.18, b.p.=68 ℃, d=0.66g/ml) with 34.6mg thiophene (M=84.14; B.p.=84 ℃, d=1.07)], 50 ℃ are stirred 5min down; Leave standstill 5min after stopping to stir; Pipette upper strata desulfurization analog gasoline (taking out excess) and measure sulphur content, and { thiophene decreasing ratio %=[thiophene content in (thiophene content in thiophene content in the analog gasoline-extraction back analog gasoline)/analog gasoline] * 100}, the result lists in table 1 to calculate the thiophene decreasing ratio.Sulphur content adopts coulometry to measure (coulomb measuring method: SH/T0253-92, down together).
Pipette lower floor's ionic liquid to the 200ml container, add 75mL water, at room temperature stir 5min; Make ionic liquid soluble in water fully, leave standstill 5min, pipette the sulfide of extracting out on the upper strata and the oil of carrying under one's arms after; In ionic liquid aqueous solution, add entrainer normal hexane 5mL; Distillation lower floor ionic liquid aqueous solution under 70 ℃/0.05mmHg condition, steam the azeotrope of water and organic solvent after, obtain the 15ml regeneration of ionic liquid.Explanation is through not loss of regeneration of ionic liquid.
In 200 ml containers, pack into 15 milliliters of regeneration of ionic liquid that obtain by embodiment 1 and 100 milliliters of analog gasolines identical with embodiment 1.All the other steps are identical with embodiment 1.The sulphur content of the desulfurization analog gasoline (taking out excess) that obtains after the extraction is listed in table 1.
15 milliliters of regeneration of ionic liquid and the 100 milliliters of once desulfurization analog gasolines that obtain by embodiment 2 of in 200 ml containers, packing into.Repeat embodiment 1 same steps as 4 times.The sulphur content of the desulfurization analog gasoline (taking out excess) that obtains after the extraction is listed in table 1.
In 200 ml containers, pack into 15 milliliters of 1-methyl-3-NSC 158165 tetrafluoride boron (SolventInnovation company, Germany) ionic liquid and 100 milliliters of analog gasolines identical with embodiment 1.All the other steps are identical with embodiment 1.The sulphur content of the desulfurization analog gasoline (taking out excess) that obtains after the extraction is listed in table 1
Adopt with embodiment 1 same procedure and carry out ionic liquid regeneration; Just the add-on of water is 150mL; Water temperature is 50 ℃, adds entrainer Virahol 5mL behind the separation sulfide, distillation lower floor ionic liquid aqueous solution under 90 ℃/0.1mmHg condition; After steaming the azeotrope of water and organic solvent, obtain regeneration of ionic liquid 15mL.
In 200 ml containers, pack into 15 milliliters of triethylamine vitriol (self-control, the preparation method sees father-in-law Jianyang etc., Green Chemistry, 2006,8,96-99).Ionic liquid and 100 milliliters of analog gasolines identical with embodiment 1.All the other steps are identical with embodiment 1.The sulphur content of the desulfurization analog gasoline (taking out excess) that obtains after the extraction is listed in table 1
Adopt with embodiment 1 same procedure and carry out ionic liquid regeneration, just the add-on of water is 150mL, and water temperature is 50 ℃, distillation lower floor ionic liquid aqueous solution under 120 ℃ of condition of normal pressure, steam water after, obtain regeneration of ionic liquid 15mL.
The 15 milliliters of 1-methyl-3-NSC 158165 ethylsulfuric acid ester salt of in 200 ml containers, packing into (is made by oneself; The preparation method sees Simone Himmler etc., Green Chemistry, 2006; 8,887-894) ionic liquid and 100 milliliters of analog gasolines identical with embodiment 1.All the other steps are identical with embodiment 1.The sulphur content of the desulfurization analog gasoline (taking out excess) that obtains after the extraction is listed in table 1.
Adopt with embodiment 1 same procedure and carry out ionic liquid regeneration; Just the add-on of water is 100mL; Water temperature is a room temperature, adds entrainer Virahol 15mL behind the separation sulfide, distillation lower floor ionic liquid aqueous solution under 90 ℃/0.1mmHg condition; After steaming the azeotrope of water and organic solvent, obtain regeneration of ionic liquid 15mL.
The 15 milliliters of 1-methyl-3-NSC 158165 octyl group sulfuric acid of in 200 ml containers, packing into (is made by oneself; The preparation method sees Simone Himmler etc., Green Chemistry, 2006; 8,887-894) ionic liquid and 100 milliliters of analog gasolines identical with embodiment 1.All the other steps are identical with embodiment 1.The sulphur content of the desulfurization analog gasoline (taking out excess) that obtains after the extraction is listed in table 1.
Adopt with embodiment 1 same procedure and carry out ionic liquid regeneration; Just the add-on of water is 30mL; Water temperature is 50 ℃, adds entrainer isopropylcarbinol 15mL behind the separation sulfide, distillation lower floor ionic liquid aqueous solution under 90 ℃/0.1mmHg condition; After steaming the azeotrope of water and organic solvent, obtain regeneration of ionic liquid 15mL.
Table 1
| Embodiment | Extraction times | Sulphur content/ppm | Thiophene decreasing ratio/% |
| 1 | 1 | 98 | 51.0 |
| 2 | 1 | 99 | 50.0 |
| 3 | 4 | 7 | 96.5 |
| 4 | 1 | 163 | 18.5 |
| 5 | 1 | 170 | 15.0 |
| 6 | 1 | 143 | 28.5 |
| 7 | 1 | 111 | 44.5 |
The presentation of results that table 1 provides, negatively charged ion are that fluoroboric acid root, inferior sulfate radical or sulfuric acid mono alkyl ester ionic ionic liquid all have good renewable performance, all can be used as extraction agent and are used for the present invention.In addition, the ion of being made up of monoalkyl imidazoline has and better takes off the thiophene effect.
The 10 milliliters of Methylimidazole borofluoride ion liquid of in 200 ml containers, packing into (are made by oneself; The preparation method is with embodiment 1), 100 milliliters of analog gasolines, wherein contain 50 ml n-hexanes (33g, d=0.66g/ml), 20 milliliters of 1-hexene (13.4g; D=0.67g/ml), 20 milliliters of 4-methyl-1-pentene (13.2g; D=0.66g/ml) and 10 milliliters of benzene (8.8g d=0.88g/ml), also has 36 microlitre thiophene (d=1.07g/ml; The about 214ppm of sulphur content) and 8 microlitre 2-thiotolenes (d=1.014g/ml, the about 39ppm of sulphur content).Extraction temperature is 35 ℃, and all the other steps are identical with embodiment 1.Represent ion liquid selectivity (method of calculation of the method for calculation of olefin removal rate and arene engaging scraping rate and thiophene decreasing ratio are identical) with the thiophene decreasing ratio and the ratio of the summation of olefin removal rate and arene engaging scraping rate, the result lists in the table 2.Alkene after the desulfurization in the analog gasoline and aromaticity content employing chromatography determination (method: SH/T 0714-2002, down together).
10 milliliters of 1-butyl-4-methylimidazole borofluoride ion liquid (the Solvent Innovation company of in 200 ml containers, packing into; Germany) analog gasoline identical with 100 milliliters of compositions and embodiment 9, extraction conditions is also identical with embodiment 9 with thiophene, alkene and arene content determination method.Extraction results is listed in the table 2.
The 8 milliliters of Methylimidazole borofluoride ion liquid of in 200 ml containers, packing into (are made by oneself; The preparation method is with embodiment 1) analog gasoline identical with 2 milliliters of 1-methyl-3-NSC 158165 octyl group sulfuric acid ionic liquid (preparation method is with embodiment 7) and 100 milliliters of compositions and embodiment 9, extraction conditions is also identical with embodiment 9 with thiophene, alkene and arene content determination method.Extraction results is listed in the table 2.
Table 2
| Embodiment | Thiophene decreasing ratio/% | 2-thiotolene decreasing ratio/% | Olefin removal rate/% | Arene engaging scraping rate/% | Thiophene removes |
| 8 | 32.5 | 23.9 | 0.1 | 5.5 | 5.8 |
| 9 | 23.0 | 33.3 | 17.5 | 36.5 | 0.4 |
| 10 | 28.5 | 26.5 | 5.0 | 9.0 | 2.0 |
The result that table 2 provides can further specify, and the ion liquid desulfuration selectivity of monoalkyl imidazoline class is apparently higher than di-alkyl-imidazole class ionic liquid.When monoalkyl imidazoline class ionic liquid is adopted in this explanation as the extraction agent desulfurization, can reduce the loss of alkene and aromatic hydrocarbons, favourable to reducing the gasoline octane rating loss.But relatively different ionic liquid is not difficult to find out that to 2-thiotolene decreasing ratio the 2-thiotolene decreasing ratio of many alkyl imidazole ionic liquids is apparently higher than monoalkyl imidazoline class ionic liquid.Therefore, monoalkyl imidazoline class ionic liquid shows different selectivity with many alkyl imidazole ionic liquids to dissimilar thiophene sulfocompounds.Adopt two kinds of dissimilar ionic liquid mixture, can take into account decreasing ratio and the selectivity of ionic liquid different sulfur-bearing sulfide.The alkylthrophene class is many in the heavy gasoline fraction, and therefore, along with the raising of cutting temperature, the weightening finish of lighting end gasoline is introduced di-alkyl-imidazole class ionic liquid at monoalkyl imidazoline class ionic liquid, and is favourable to carrying the doctor positive decreasing ratio.
Present embodiment explanation the present invention provides the effect of method.
This instance carries out desulfurization according to flow process shown in Figure 1 to the sour gasoline distillate.
Full distillation gasoline raw material is cut into lighting end gasoline and last running gasoline, and cutting temperature is 85 ℃, and wherein, light gasoline fraction accounts for 39.9 (weight) % of raw material.Lighting end, last running and full distillation gasoline raw material properties are seen table 3, table 4 and table 5 respectively.
Lighting end is abstraction desulfurization in the ion liquid abstraction unit; The extraction cells working order is carried out in 5 extraction sections being made up of 5 extractors and 5 slurry tanks; Ionic liquid is the (self-control of Methylimidazole fluoroborate; The preparation method is with embodiment 1), the extraction agent in each extractor and the volume ratio of petroleum naphtha are 0.1, except that first extractor adds fresh ionic liquid as the extraction agent; All the other four sections are all adopted last extraction section regenerated ionic liquid as extraction agent; Extraction temperature is 50 ℃, and the desulfurization petroleum naphtha (raffinate) that reclaims from slurry tank top gets into next extractor and continues desulfurization from the bottom, and sulfide that reclaims from the slurry tank bottom and ion liquid mixture (extraction liquid) order are introduced the water extraction cells and carried out ionic liquid regeneration with the distillation unit.The regenerated ionic liquid returns extractor and reuses.Wherein, water extraction cells operational condition: the volume ratio of water and sulfocompound and ionic liquid mixture is 3.0, and temperature is a room temperature; Distillation procedure unit operation condition: ZN series vacuum decompressioning and concentrating tank (by concentration tank, first condensing surface, vapour liquid separator, second condensing surface, water cooler, formed by liquid bath and depressurized system; Wenzhou shellfish promise machinery ltd); Distillation temperature is 70 ℃; In mixture, add entrainer benzene during distillation, water and entrainer benzene volume ratio be 2.0.The character of the petroleum naphtha product after lighting end gasoline and the extraction, olefin(e) centent form and anti-knock index is listed in table 3.
Last running gasoline 5 carries out desulfurization in the unifining unit.Hydrobon catalyst is RSDS-1 (a Chang Ling oil-refining chemical head factory catalyst plant product).Hydrogenating desulfurization refining reaction condition: hydrogen partial pressure is 2.2 MPas, and temperature of reaction is 300 ℃, and liquid hourly space velocity is 4.0 hours
-1, hydrogen to oil volume ratio is 400.The character of heavy petrol product, olefin(e) centent and anti-knock index are listed in table 4 after last running gasoline and the hydrogenating desulfurization.
With the lighting end gasoline of above-mentioned sulphur content reduction and the last running gasoline concoction of sulphur content reduction, obtain the gasoline products that sulphur content reduces, its olefin(e) centent and anti-knock index are as shown in table 5.With the raw oil contrast, the sulphur content of blended gasoline has reduced by 96.5%, reaches 49ppm, and anti-knock index only reduces by 0.5 unit.
Comparative Examples 1
Press the sulfur-bearing lighting end gasoline A and the sulfonation phthalein mountain valley with clumps of trees and bamboo cobalt alkali lye contact desulfuriation alcohol (referring to 20～22 pages of " Jiangsu Petrochemical Engineering College journal " the 13rd the 4th phases of volume) of embodiment 11 said condition cuttings; The sulphur content of the desulfurization lighting end gasoline that obtains is seen table 3, and the sulfide decreasing ratio is 48.1%.Total sulfur content is 82.4ppm, and is more much higher than the total sulfur content 7.8ppm that presses behind embodiment 11 abstraction desulfurizations.Sulphur content behind the last running gasoline hydrogenation is 76ppm (table 4), and after being in harmonious proportion with the lighting end gasoline of caustic wash desulfuration, the sulphur content of gasoline product is 79ppm.
Table 3
| Project | Before the lighting end extraction (6) | Lighting end extraction back (14) | After the alkali cleaning (Comparative Examples 1) |
| 20 ℃ of density, g/cm 3 | 0.671 | 0.674 | 0.673 |
| Total sulfur content, ppm | 171.4 | 7.8 | 82.4 |
| Mercaptan and thioether content, ppm | 94.5 | 0 | 5.7 |
| Olefin(e) centent, body % | 57.5 | 57.2 | ? |
| Over point, ℃ | 32 | ? | ? |
| 50% distillates a little, ℃ | 46 | ? | ? |
| Final boiling point, ℃ | 83 | ? | ? |
| Anti-knock index | 90.0 | 89.5 | 89.8 |
| The anti-knock index loss | ? | 0.5 | 0.2 |
Table 4
| Project | Before the heavy fractioning hydrogenation (18) | Behind the heavy fractioning hydrogenation (15) |
| 20 ℃ of density, g/cm 3 | 0.789 | 0.785 |
| Sulphur content, ppm | 1020 | 76 |
| Mercaptan and thioether content, ppm | 103 | 30 |
| Olefin(e) centent, body % | 36.2 | 28.8 |
| Over point, ℃ | 88 | 86 |
| 50% distillates a little, ℃ | 145 | 142 |
| Final boiling point, ℃ | 198 | 202 |
| Anti-knock index | 87.2 | 86.5 |
| The anti-knock index loss | ? | 0.7 |
Table 5
| Project | Full feedstock (16) | Mediation product (19) |
| 20 ℃ of density, g/cm 3 | 0.743 | 0.740 |
| Sulphur content, ppm | 680 | 49 |
| Mercaptan and thioether content, ppm | 100 | 0 |
| Olefin(e) centent, body % | 51.3 | 46.8 |
| Over point, ℃ | 40 | 38 |
| ?50％，℃ | 92 | 92 |
| Final boiling point, ℃ | 195 | 196 |
| Anti-knock index | 88.7 | 88.2 |
| The anti-knock index loss | ? | 0.5 |
Embodiment 12
Present embodiment explanation the present invention provides the effect of method.
According to the sour gasoline distillate being carried out desulfurization with embodiment 11 same procedure.Different is:
Full distillation gasoline raw material is cut into lighting end gasoline and last running gasoline, and cutting temperature is 95 ℃, and wherein, light gasoline fraction accounts for 50.0 (weight) % of raw material.Full distillation gasoline raw material properties is seen table 8;
The ion liquid abstraction unit: extraction agent is the compound ion liquid (blending ratio is with embodiment 10) of the fluoroborate of monoalkyl imidazoline and di-alkyl-imidazole, and extraction temperature is 35 ℃;
The water extraction cells: water and enrichment the ion liquid volume ratio of sulphur compound be 3.0, temperature is a room temperature;
The distillation unit: triple effect falling film evaporator (Wenzhou shellfish promise machinery ltd), continous way operation are adopted in distillation.Add the entrainer isopropylcarbinol in the material, the distillation temperature under the reduced pressure is 60 ℃, water and entrainer benzene volume ratio be 2.0.
Lighting end gasoline is listed in table 6 with the character of the lighting end gasoline products of collection front and back.
Character after last running gasoline and the hydrogenating desulfurization, hydrocarbon system form and anti-knock index is listed in table 7.
The lighting end gasoline of above-mentioned sulphur content reduction and the last running gasoline of sulphur content reduction are mixed, obtain the gasoline products that sulphur content reduces, its olefin(e) centent and anti-knock index are as shown in table 8.With the raw oil contrast, the sulphur content of blended gasoline has reduced by 93.1%, reaches 47ppm, and anti-knock index only reduces by 0.8 unit.
Comparative Examples 2
Press the sulfur-bearing lighting end gasoline and the sulfonation phthalein mountain valley with clumps of trees and bamboo cobalt alkali lye contact desulfuriation alcohol (referring to 20～22 pages of " Jiangsu Petrochemical Engineering College journal " the 13rd the 4th phases of volume) of embodiment 14 said condition cuttings; The sulphur content that obtains desulfurization lighting end gasoline is seen table 6, and the sulfide decreasing ratio is 49.9%.Total sulfur content is 92.4ppm, than by high many of the sulphur content 8.1ppm behind embodiment 12 abstraction desulfurizations.Sulphur content behind the last running gasoline hydrogenation is 86ppm (table 7), and being in harmonious proportion the sulphur content of back gasoline product with the lighting end gasoline of caustic wash desulfuration is 89ppm.
Table 6
| Project | Before the lighting end extraction (6) | Lighting end extraction back (14) | After the alkali cleaning (Comparative Examples 1) |
| 20 ℃ of density, g/cm 3 | 0.687 | 0.683 | 0.684 |
| Total sulfur content, ppm | 185.0 | 8.1 | 92.4 |
| Mercaptan and thioether content, ppm | 96.5 | 0 | 7.2 |
| Olefin(e) centent, body % | 53.5 | 51.5 | ? |
| Over point, ℃ | 33 | ? | ? |
| 50% distillates a little, ℃ | 50 | ? | ? |
| Final boiling point, ℃ | 93 | ? | ? |
| Anti-knock index | 88.9 | 88.1 | 88.8 |
| The anti-knock index loss | ? | 0.8 | 0.1 |
Table 7
| Project | Before the heavy fractioning hydrogenation (18) | Behind the heavy fractioning hydrogenation (15) |
| 20 ℃ of density, g/cm 3 | 0.799 | 0.795 |
| Sulphur content, ppm | 1175 | 86 |
| Mercaptan and thioether content, ppm | 108 | 36 |
| Olefin(e) centent, body % | 39.3 | 31.2 |
| Over point, ℃ | 92 | 86 |
| 50% distillates a little, ℃ | 132 | 132 |
| Final boiling point, ℃ | 196 | 202 |
| Anti-knock index | 87.6 | 87.0 |
| The anti-knock index loss | ? | 0.6 |
Table 8
| Project | Full feedstock (16) | Mediation product (19) |
| 20 ℃ of density, g/cm 3 | 0.743 | 0.740 |
| Sulphur content, ppm | 680 | 47 |
| Mercaptan and thioether content, ppm | 100 | 0 |
| Olefin(e) centent, body % | 51.3 | 46.8 |
| Over point, ℃ | 40 | 38 |
| ?50％，℃ | 92 | 95 |
| Final boiling point, ℃ | 195 | 197 |
| Anti-knock index | 88.7 | 87.9 |
| The anti-knock index loss | ? | 0.8 |
Claims (18)
1. method that reduces sulfur in gasoline content, comprise with the sour gasoline distillate be cut into light, weigh two cuts; Last running gasoline is adopted the hydrofinishing process desulfurization; With gently heating up in a steamer the method desulfurization that gasoline divides employing to comprise the steps: be the extraction cells of extraction agent with the ionic liquid a); Under the ion liquid abstraction condition; Lighting end gasoline is contacted with ionic liquid, obtain lighting end gasoline that sulphur content reduced and the ionic liquid that is enriched with sulfocompound through separating; B) be the extraction cells of extraction agent with water, the ionic liquid of the enrichment sulfocompound that step a) is obtained contacts with water, obtains sulfocompound and water and ion liquid mixture through separating; C) water and the ion liquid mixture that employing distillating method separating step b) obtain obtain the regenerated ionic liquid; D) the lighting end gasoline that will be have partly or entirely reduced through the last running gasoline of hydrofinishing process desulfurization and part or all of sulphur content mixes and obtains product oil.
2. according to the said method of claim 1, it is characterized in that said cutting temperature is 60-120 ℃, it is the 30-70 weight % of gasoline total amount that said cutting makes the amount of lighting end gasoline.
3. according to the said method of claim 2, it is characterized in that said cutting temperature is 70-100 ℃, it is the 30-60 weight % of gasoline total amount that said cutting makes the amount of lighting end gasoline.
4. according to the said method of claim 1, it is characterized in that it is in fluoroboric acid root, inferior sulfate radical or the sulfuric acid mono alkyl ester ionic ionic liquid one or more that said ionic liquid is selected from negatively charged ion.
5. according to the said method of claim 4, it is characterized in that said ionic liquid is selected from one or more in the ionic liquid that positively charged ion is nitrogenous organic ion.
6. according to the said method of claim 5, it is characterized in that said nitrogenous organic ion is selected from one or more in monoalkyl imidazoline, di-alkyl-imidazole, the quaternary ammonium alkyl.
7. according to claim 1,4,5 or 6 any said methods, it is characterized in that said ionic liquid is selected from the ionic liquid that positively charged ion is a monoalkyl imidazoline.
8. according to claim 1,4,5 or 6 any said methods; It is characterized in that; Said ionic liquid is that said positively charged ion is the ionic liquid of monoalkyl imidazoline and the ion liquid mixture that positively charged ion is di-alkyl-imidazole; By percentage to the quality and with said mixed ionic liquid is benchmark, and positively charged ion is that the ion liquid content of di-alkyl-imidazole is not more than 50% in the said mixture.
9. according to the said method of claim 1, it is characterized in that the extraction conditions of said step a) comprises: temperature is a room temperature to 200 ℃, and the volume ratio of said ionic liquid and lighting end gasoline is 0-01-1.
10. according to the said method of claim 9, it is characterized in that the extraction conditions of said step a) comprises: temperature is 50-100 ℃, and the volume ratio of said ionic liquid and lighting end gasoline is 0.1-0.5.
11., it is characterized in that the ionic liquid that is enriched with sulfocompound in the said step b) contacts temperature with water be room temperature to 90 ℃ according to the said method of claim 1, the ion liquid volume ratio of described water and enrichment sulfocompound is 0.1-10.
12., it is characterized in that the ionic liquid that is enriched with sulfocompound in the said step b) contacts temperature with water be room temperature to 50 ℃ according to the said method of claim 11, the ion liquid volume ratio of described water and enrichment sulfocompound is 0.5-5.
13., it is characterized in that said distillating method is a vacuum distillation method according to the said method of claim 1.
14. according to claim 1 or 13 said methods; It is characterized in that; Said distillation is included in water and the ionic liquid mixture and introduces entrainer; Said entrainer is selected from one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, hexanaphthene, the benzene, and it is 0.1-10 that the introducing amount of said entrainer makes the volume ratio of said entrainer and said water and ion liquid compound.
15., it is characterized in that said entrainer is selected from one or more in Virahol, isopropylcarbinol, hexanaphthene, the benzene according to the said method of claim 14, the volume ratio of said entrainer and said water and ion liquid compound is 0.1-1.
16., it is characterized in that the extraction of said step a) makes the sulphur content of the finished product gasoline be not more than 50ppm according to the said method of claim 1.
17., it is characterized in that the extraction of said step a) makes the sulphur content of the finished product gasoline be not more than 10ppm according to the said method of claim 16.
18., it is characterized in that said sour gasoline distillate is selected from one or more in catalytic gasoline of whole fraction, catalytic cracking gasoline, coker gasoline, steam cracking gasoline, the pressure gasoline according to the said method of claim 1.
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| CN102533325B (en) * | 2010-12-31 | 2014-05-28 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
| CN102199442B (en) * | 2011-04-14 | 2013-11-06 | 大连大学 | Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant |
| CN103725323A (en) * | 2014-01-21 | 2014-04-16 | 湖北金鹤化工有限公司 | Deodorization-extraction-washing-hydrogenation combined technology for producing low-sulfur gasoline |
| CN103740407B (en) * | 2014-01-21 | 2015-07-01 | 武汉工程大学 | Alkali cleaning-extraction-washing-hydrogenation combined process for producing low-sulfur-content gasoline |
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| CN103740405B (en) * | 2014-01-21 | 2015-07-01 | 长江大学 | Alkali cleaning-extraction-hydrogenation combined process for producing low-sulfur-content gasoline |
| CN103740406A (en) * | 2014-01-21 | 2014-04-23 | 湖北金鹤化工有限公司 | Extraction-hydrogenation combined process for producing low-sulfur-content gasoline |
| CN103756721B (en) * | 2014-01-21 | 2016-03-30 | 武汉工程大学 | A kind of extraction-washing-hydrogenation combination technique producing low-sulphur oil |
| CN103949137B (en) * | 2014-05-14 | 2016-01-13 | 北京国电龙源环保工程有限公司 | A kind of renewable solion being used as flue gas desulfurization |
| CN104762100B (en) * | 2015-03-30 | 2016-03-09 | 浙江大学 | A kind of eutectic solvent extraction removes the method for nitrogenous compound in oil product |
| CN105255515B (en) * | 2015-09-30 | 2017-04-26 | 中国石油大学(北京) | Combination method for producing ultralow sulphur gasoline |
| CN105255516B (en) * | 2015-09-30 | 2017-07-11 | 中国石油大学(北京) | A kind of combined method of gasoline desulfurization |
| CN106221794B (en) * | 2016-07-25 | 2018-03-02 | 中国石油大学(北京) | A kind of selective hydrodesulfurization method |
| CN108003932B (en) * | 2016-10-28 | 2020-04-28 | 中国石油化工股份有限公司 | Method for producing gasoline product |
| CN108018079B (en) * | 2016-10-28 | 2020-04-28 | 中国石油化工股份有限公司 | Method for reducing sulfur content of gasoline |
| CN111019750A (en) * | 2019-12-23 | 2020-04-17 | 宁波中循环保科技有限公司 | Method for removing chlorine in waste engine oil by using strong-alkaline ionic liquid |
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| CN1782024A (en) * | 2004-11-30 | 2006-06-07 | 中国科学院兰州化学物理研究所 | Method for reducing sulfur content in gasoline by ion liquid extraction |
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