Background technology
Along with the enhancing of mankind's environmental consciousness, in vehicle exhaust, objectionable impurities more and more causes the attention of people to the pollution of atmospheric environment, and the composition of countries in the world to motor spirit proposes increasingly strict requirement, especially sulphur content.European Union came into effect Europe IV automobile exhaust emission standard in 2005, require that content of sulfur in gasoline is less than 50ug/g, come into effect Euro V emissions on September 1st, 2009, require that content of sulfur in gasoline is less than 10ug/g, also plan to carry out more strict Europe VI standard at about 2014; China will implement state III gasoline standard (GB17930-2006) the end of the year 2009, require that sulphur content is not more than 150ug/g; Plan to implement integrally state four gasoline standard in 1 day January in 2014, require that sulphur content is not more than 50ug/g; Rise on January 1st, 2018 and implement integrally state five gasoline standard, require that sulphur content is not more than 10ug/g.The continuous upgrading of gasoline quality standard, makes the gasoline production technology of oil refining enterprise be faced with more and more stern challenge.
In current domestic gasoline product, the sulphur of more than 90% carrys out catalytic cracking (FCC) gasoline, and therefore the reduction of sulfur content of catalytic cracking gasoline is the key point reducing finished product content of sulfur in gasoline.
The sulphur content reducing catalytically cracked gasoline can adopt catalytically cracked material weighted BMO spaces (front-end hydrogenation), catalytic gasoline hydrogenation desulfurization (back end hydrogenation) two kinds of modes usually.Wherein, catalytically cracked material pre-treatment significantly can reduce the sulphur content of catalytically cracked gasoline, but needs to operate under temperature and pressure all very exacting terms, simultaneously because unit capacity is large, cause hydrogen to consume also larger, these all will improve investment or the running cost of device.However, due to the heaviness of world's crude oil, increasing catalytic cracking unit starts to process the inferior raw material containing normal, vacuum residuum etc., and therefore catalytically cracked material hydrogenation unit amount is also increasing year by year.Meanwhile, along with the innovation of catalytic cracking technology, the application gradually of catalytic cracking desulfurization auxiliary, the sulfur content of catalytic cracking gasoline of China's Some Enterprises can reach below 500ug/g, or even below 150ug/g.But if the sulphur content of catalytically cracked gasoline will be reduced further, make it to be less than 50ug/g(and meet Europe IV emission standard to the restriction of content of sulfur in gasoline), even be less than 10ug/g(and meet the restriction of Euro V emissions to content of sulfur in gasoline), then must increase substantially the operating severity of catalytically cracked material hydrogenation unit, very uneconomical economically.
Compare front-end hydrogenation, catalytic gasoline hydrogenation desulfurization is all lower than catalytically cracked material weighted BMO spaces in plant investment, production cost and hydrogen consumption, and its different desulfurization depth can meet the requirement of different size sulphur content.If but it is saturated in a large number and make loss of octane number very large to adopt traditional hydrofinishing process can make to have in catalytically cracked gasoline high-octane olefin component.Therefore, develop that a kind of to invest low, that loss of octane number is little low-sulphur oil production technology extremely urgent.
In light fractions of FCC naphtha, olefin(e) centent is high, and in last running, olefin(e) centent is lower, so can adopt the method that cut cuts, catalytically cracked gasoline is cut into lighting end and last running; Traditional hydrogenating desulfurization technology is taked in last running, and lighting end adopts non-hydrodesulfurization.Document shows that catalytically cracked gasoline medium sulphide content is mainly divided into the large class of thio-alcohol, thioether class, thiophene-based 3: thiophene-based content is the highest, accounts for about 70% of sulfide; Next is thio-alcohol, accounts for sulfide about 16% ~ 20%; Thioether class content is relatively less compared with other two classes.In thiophene-type sulfide in gasoline, thiotolene content is higher, accounts for about 40%, is secondly that thiophene accounts for about 15%.Known from the boiling point of sulfide: gasoline light constituent, thio-alcohol mainly concentrates on less than 80 DEG C, and thiophene is present in the cut of 80 DEG C ~ 90 DEG C, within the scope of 100 DEG C ~ 120 DEG C, sulphur content is the highest, accounting for about 20% of total sulfur content, should major part be thiotolene and a small amount of tetramethylene sulfide etc.Adopt non-hydrodesulfurization when taking off the sulfide in gasoline lighting end, cut point that is light, last running is higher, and in last running, olefin(e) centent is fewer, then the olefin loss that causes of hydrogenation is less; When cut point is 80 DEG C, lighting end is mainly mercaptan; When cut point is 90 DEG C, in lighting end, thiophene content is higher, now must remove thiophene and just can make sulphur content ≯ 10ug/g in lighting end.Therefore the crucial thiophene being to remove in lighting end of non-hydrogenating desulfurization.
Embodiment
It is as follows that the present invention reduces content of sulfur in gasoline method flow: gasoline stocks enters separation column 2 through pipeline 1 and cuts into gently, heavy naphtha, wherein heavy naphtha is after pipeline 4 mixes with the sour distillate oil from pipeline 19, pump 6 is entered through pipeline 5, heavy naphtha after boosting is after pipeline 7 mixes with the hydrogen from pipeline 27, process furnace 9 is entered through pipeline 8, material after heating enters reactor 11 through pipeline 10 and contacts with Hydrobon catalyst, hydrogenated oil enters high-pressure separator 21 through pipeline 12, from separator 21 top, hydrogen-rich gas out enters compressor 24 through pipeline 23, hydrogen-rich gas after compression is through pipeline 25 inlet pipe line 27 together with the supplementary live gas from pipeline 26, mix with the heavy distillate from pipeline 7.Bottom separator 21, hydrogenated heavy gasoline cut out mixes stabilizer tower through pipeline 22 with the alkali cleaning-extraction-washing light gasoline fraction from pipeline 29.
Lighting end gasoline enters alkali cleaning treating tower 13 through pipeline 3, gasoline after caustic wash desulfuration alcohol enters extraction tower 15 through pipeline 14, bottom extraction tower 15, extraction phase out enters revivifier 18 through pipeline 17, the extraction agent separated bottom revivifier 18 enters extraction tower 15 top through pipeline 20, oily through pipeline 19 and the heavy distillate mixing back end hydrogenation process from pipeline 4 from the sour distillate of revivifier 18 recovered overhead.From extraction tower 15 top, desulfurization benzoline out enters washing device 28 through pipeline 16, lighting end after washing mixes with the heavy distillate from pipeline 22 through pipeline 29, mixed gasoline enters stabilizer tower 31 through pipeline 30, and separation obtains lighter hydrocarbons and gasoline products is drawn through pipeline 32,33 respectively.
The following examples will be further described method provided by the invention, but not limit the scope of the invention.
Embodiment 1
With FCC gasoline A for raw material, first raw material is cut, cut point is 95 DEG C, and heavy naphtha accounts for the per-cent 52% of raw material, and the character of the full cut of gasoline (FCCN), light gasoline fraction (LCN), heavy naphtha (HCN) is as shown in table 1.The advanced alkaline cleaner mercaptan removal of light gasoline fraction, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and after alkali cleaning, the mercaptan sulfur content in light gasoline fraction is reduced to 15.3ug/g; Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, obtains alkali cleaning-extraction light gasoline fraction and extraction phase; Extraction agent is n-formylmorpholine, and agent-oil ratio is 2:1, and extraction progression is 4 grades, and extraction temperature is 55 DEG C, removes the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Extraction phase enters reboiler, and regeneration temperature is 110 DEG C, and the extraction agent of regeneration recycles, and the sour gasoline steamed mixes laggard hydrogenation unit with heavy naphtha; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is water, the extraction agent in removing alkali cleaning-extraction gasoline fraction; Heavy naphtha hydrotreatment obtains hydrogenated heavy gasoline cut.
After gasoline adopts the technology of the present invention process, alkali cleaning-extraction-washing light gasoline fraction (LCN '), hydrogenated heavy gasoline cut (HCN '), gasoline products (FCCN ') character are as shown in table 1-2.
Table 1-1 gasoline stocks and cut character thereof
Table 1-2 gasoline stocks character after present invention process process
Contrast table 1-1 and table 1-2 can find out, gasoline stocks is after present invention process process, in light gasoline fraction, sulphur content is down to 20.1ug/g from 220ug/g, and namely abstraction desulfurization technique of the present invention possesses higher sweetening power, and light gasoline fraction sulphur content can be made to reach below 50ug/g; In heavy naphtha, sulphur content is down to 8.1ug/g from 1430ug/g; Content of sulfur in gasoline is down to 13.9ug/g from 849ug/g, shows to adopt this technique, production sulphur content can meet the gasoline of state IV standard lower than 50ug/g, sulphur content.
Embodiment 2
With FCC gasoline B for raw material, the advanced alkaline cleaner mercaptan removal of light gasoline fraction, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and the mercaptan sulfur content in gasoline is reduced to 22.5ug/g; Cut by gasoline after alkali cleaning, cut point is 100 DEG C, gets lighting end gasoline and investigates extraction agent sweetening effectiveness.Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, obtains alkali cleaning-extraction gasoline fraction and extraction phase; Extraction agent is tetramethylene sulfone, and agent-oil ratio is 3:1, and extraction progression is 4 grades, and extraction temperature is 45 DEG C, removes the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is ethanol, and the extraction agent in removing treated gasoline cut, obtains alkali cleaning-extraction-washing light gasoline fraction.Result is as follows: raw material lighting end sulphur content 342.6ug/g, and after alkali cleaning extracting and washing, sulphur content is reduced to 21.1ug/g, shows to adopt this technique, production sulphur content can meet the gasoline of state IV standard lower than 50ug/g, sulphur content.
Embodiment 3
The gasoline produced with the catalytic cracking after wax tailings hydrotreatment is for raw material, and cutting gasoline stocks, cut point is 92 DEG C, gets lighting end gasoline and investigates extraction agent sweetening effectiveness.The advanced alkaline cleaner mercaptan removal of light gasoline fraction, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and after alkali cleaning, the mercaptan sulfur content in light gasoline fraction is reduced to 4.2ug/g; Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, obtains alkali cleaning-extraction light gasoline fraction and extraction phase, and extraction agent is n-formylmorpholine, agent-oil ratio is 2:1, extraction progression is 4 grades, and extraction temperature is 38 DEG C, removes the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is methane amide, and the extraction agent in removing treated gasoline cut, obtains alkali cleaning-extraction-washing light gasoline fraction.Result is as follows: raw material lighting end sulphur content 19.0ug/g, after alkali cleaning extracting and washing, sulphur content is reduced to 8.3ug/g.Show that the gasoline that this invented technology is produced the catalytic cracking after wax oil hydrogenation process is effective equally.The gasoline produced with the catalytic cracking after wax oil hydrogenation process is for raw material, and light gasoline fraction sulphur content is lower, but does not reach the requirement of state V normal benzene sulphur content.Adopt this technique, production sulphur content can meet the gasoline of state V standard lower than 10ug/g, sulphur content.
Embodiment 4
With FCC gasoline C for raw material first cuts raw material, cut point is 89 DEG C, gets lighting end gasoline and investigates extraction agent sweetening effectiveness.Concrete grammar is as follows:
1. the preparation of gasoline
In light gasoline fraction, add thiophene, investigate extraction agent to the sweetening effectiveness of different sulphur content gasoline.
Add 1000ug/g in lighting end gasoline, be designated as sample 1;
Add 500ug/g in lighting end gasoline, be designated as sample 2;
Do not add thiophene in lighting end gasoline, be designated as sample 3;
2. get above-mentioned gasoline and investigate extraction agent sweetening effectiveness.The advanced alkaline cleaner mercaptan removal of light gasoline fraction, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and after alkali cleaning, the mercaptan sulfur content in light gasoline fraction is reduced to 18.3ug/g; Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, obtains alkali cleaning-extraction light gasoline fraction and extraction phase, and extraction agent is tetramethylene sulfone, agent-oil ratio is 3:1, extraction progression is 4 grades, and extraction temperature is 25 DEG C, removes the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is ethylene glycol, the extraction agent in removing alkali cleaning-extraction gasoline fraction.The results are shown in Table 4-1
Sulphur content after each lighting end gasoline desulfur of table 4-1
Table 4-1 shows, the abstraction desulfurization technique in present invention process has higher sweetening power, and de-thiophenic sulfur ability is remarkable.
Embodiment 5
Take analog gasoline as raw material, the mercaptan removal of high spot reviews extraction, de-thiophene effect.
1. the configuration of analog gasoline
Thiophene content in the analog gasoline prepared in experiment is about 500ug/g, and the content of mercaptan is about 190ug/g, and total sulfur is 241.57ug/g.Analog gasoline composition is in Table 5-1
Table 5-1 analog gasoline composition
2. the advanced alkaline cleaner mercaptan removal of analog gasoline, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and after alkali cleaning, the mercaptan sulfur content in light gasoline fraction is reduced to 115.2ug/g; Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, obtains alkali cleaning-extraction light gasoline fraction and extraction phase, and extraction agent is tetramethylene sulfone, agent-oil ratio is 3:1, extraction progression is 4 grades, and extraction temperature is 60 DEG C, removes the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is glycerol, the extraction agent in removing gasoline fraction.
2. after alkali cleaning extracting and washing, result is as follows, and sulfur removal rate reaches 92%, and after desulfurization, analog gasoline sulphur content is 19.32ug/g.As can be seen here, the abstraction desulfurization technique in present invention process has higher sweetening power, the Major Sulfides in light gasoline fraction: thiophenic sulfur and mercaptan sulfur, has good removal effect, makes the sulphur content in cut reach the ≯ standard of 50ug/g.
Embodiment 6
With FCC gasoline D for raw material, get the light gasoline fraction of boiling point 80 DEG C ~ 100 DEG C, investigate extraction agent sweetening effectiveness in present invention process.
The advanced alkaline cleaner mercaptan removal of light gasoline fraction, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and after alkali cleaning, the mercaptan sulfur content in light gasoline fraction is reduced to 24.6ug/g; Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, and extraction agent is n-formylmorpholine, and agent-oil ratio is 2:1, and extraction progression is 4 grades, and extraction temperature is 30 DEG C, obtains alkali cleaning-extraction light gasoline fraction and extraction phase; Remove the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is methyl alcohol, and the extraction agent in removing treated gasoline cut, obtains alkali cleaning-extraction-washing light gasoline fraction.
Result is as follows: raw material lighting end sulphur content 133.0ug/g, after extracting and washing, sulphur content is reduced to 19.3ug/g, show to adopt this technique, the light gasoline fraction sulphur content of 80 DEG C ~ 100 DEG C can be made lower than 50ug/g, the sulfur content in gasoline standard reaching state IV standard.
Embodiment 7
With FCC gasoline E for raw material cuts, cut point is 95 DEG C, gets lighting end gasoline, investigates regenerating extracting agent sweetening effectiveness.
Extraction agent is fresh dose of nitrogen dimethylformamide (DMF); The advanced alkaline cleaner mercaptan removal of light gasoline fraction, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and after alkali cleaning, the mercaptan sulfur content in light gasoline fraction is reduced to 16.3ug/g; Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, and extraction agent is nitrogen dimethylformamide (DMF), and agent-oil ratio is 2:1, and extraction progression is 2 grades, and extraction temperature is 30 DEG C, obtains alkali cleaning-extraction light gasoline fraction and extraction phase; Remove the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is water, and the extraction agent in removing treated gasoline cut, obtains alkali cleaning-extraction-washing light gasoline fraction.
Reclaim extraction agent in 1, under the condition of 95 DEG C, act on 6h, the extraction agent of recovery carries out abstraction desulfurization experiment.The advanced alkaline cleaner mercaptan removal of light gasoline fraction, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and after alkali cleaning, the mercaptan sulfur content in light gasoline fraction is reduced to 16.3ug/g; Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, and extraction agent is the nitrogen dimethylformamide (DMF) reclaimed, and agent-oil ratio is 2:1, and extraction progression is 2 grades, and extraction temperature is 30 DEG C, obtains alkali cleaning-extraction light gasoline fraction and extraction phase; Remove the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is water, and the extraction agent in removing treated gasoline cut, obtains alkali cleaning-extraction-washing light gasoline fraction.
Result is as follows: the desulfurization degree of fresh extraction agent is 67.2%, and the desulfurization degree of the extraction agent recycled is 65.8%.Experimental result shows that extraction agent has and recycles performance preferably.
Embodiment 8
With FCC gasoline F for raw material, cut raw material, cutting temperature is 120 DEG C, gets light gasoline fraction, investigates extraction agent sweetening effectiveness in present invention process.
The advanced alkaline cleaner mercaptan removal of light gasoline fraction, alkali cleaning is conventional alkali cleaning (aqueous sodium hydroxide solution of 10% concentration), and after alkali cleaning, the mercaptan sulfur content in light gasoline fraction is reduced to 20.3ug/g; Alkali cleaning light gasoline fraction enters abstraction desulfurization unit, and extraction agent is the n-formylmorpholine reclaimed, and agent-oil ratio is 2:1, and extraction progression is 4 grades, and extraction temperature is 30 DEG C, obtains alkali cleaning-extraction light gasoline fraction and extraction phase; Remove the thiophene in lighting end gasoline, mercaptan, thioether, disulfides sulfide; Alkali cleaning-extraction light gasoline fraction enters washing device, and washing composition is methane amide, and the extraction agent in removing treated gasoline cut, obtains alkali cleaning-extraction-washing light gasoline fraction.
Raw material lighting end sulphur content 244.0ug/g, after alkali cleaning extracting and washing, sulphur content is reduced to 49.0ug/g, and as can be seen here, the abstraction desulfurization technique in present invention process has higher sweetening power, and sulphur content in light gasoline fraction can be made to reach ≯ the standard of 50u g/g.