CN102443433A - Method for producing low-sulfur gasoline - Google Patents
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Abstract
The invention relates to a method for producing low-sulfur gasoline, which comprises the following steps that: firstly, gasoline raw materials are fractionated into light and heavy gasoline fractions, the light gasoline fractions are subjected to alkali washing for removing sulfur and alcohol, the heavy gasoline fractions are subjected to catalytic hydrogenation for removing sulfur-containing compounds, the heavy gasoline fractions after the hydrogenation desulfuration are introduced into a counter flow reactor from the middle part, hydrogenation sulfur and alcohol removal catalysts are filled in positions under a material inlet of the counter flow reactor, hydrogen-rich gas is introduced from the bottom of the reactor, a part of heavy gasoline fractions are vaporized into gas phase ingredients and liquid phase ingredients, the liquid phase ingredients flow from top to bottom and are in count flow contact with hydrogen gas on the catalysts for carrying out hydrogenation sulfur and alcohol removal reaction, the liquid phase ingredients after the sulfur and alcohol removal flow out from the bottom of the reactor, the gas phase ingredients and other gas are discharged out from the top of the reactor, the gas phase ingredients after the condensation are mixed with the liquid phase ingredients discharged from the bottom of the tower and the light gasoline fractions subjected to the alkali washing for removing sulfur and alcohol to obtain gasoline products. When the method provided by the invention is adopted, the gasoline product with the sulfur and alcohol sulfur content lower than 3mug/g can be producted, and simultaneously, the total sulfur content of the gasoline product is reduced.
Description
Technical field
The present invention relates to a kind of method of gasoline hydrodesulfurizationmethod.More particularly, be a kind of sulphur content and regeneration mercaptan sulfur content, the method for producing low-sulphur oil that reduces in the gasoline.
Background technology
Along with the increasingly stringent of environmental regulation, countries in the world have proposed more strict restriction to the composition of motor spirit such as sulphur content, vapour pressure, benzene content, aromatic hydrocarbons total content, olefin(e) centent, and are wherein particularly harsh to the restriction of the sulphur content in the gasoline.At present, 90%～99% sulphur is from catalytically cracked gasoline in the gasoline product, and therefore, reducing sulfur content of catalytic cracking gasoline is the key point that reduces the finished product content of sulfur in gasoline.
China's catalytically cracked gasoline is a main blend component in the gasoline mediation pond, and massfraction accounts for more than 80%.Catalytically cracked gasoline can be divided into normal paraffin (n-P), isoparaffin (i-P), naphthenic hydrocarbon (N), alkene (O) and five components of aromatic hydrocarbons (A) from forming, and wherein the octane value of normal paraffin is low, and the long more octane value of carbochain is low more; The octane value of isoparaffin is higher, and the collateralization degree is high more, it is high more to arrange compact more octane value; Alkene, aromatic hydrocarbons are high-octane number components, and is the highest with the octane value of aromatic hydrocarbons.China's catalytically cracked gasoline presents the characteristic of high olefin, low arene content, and about 40～50%, the volume content of aromatic hydrocarbons is less than 20% usually for the volume content of alkene.Alkene becomes the important component in China catalytically cracked gasoline octane value source, thereby the variation of olefin(e) centent is very big to the influence of catalytically cracked gasoline octane value.In traditional catalytic gasoline hydrogenation sweetening process, it is low-octane alkane that alkene is easy to hydrogenation saturated, causes gasoline octane rating to reduce significantly.
CN 1478866A discloses a kind of method of gasoline desulfur.This method is cut into light gasoline fraction, heavy naphtha with gasoline stocks; Heavy naphtha contacts with Hydrobon catalyst with hydrogen together, carries out selective hydrodesulfurization reaction, after reaction effluent is isolated gas phase through HP separator, contacts with the hydrogenating desulfurization alcohol catalyst after remaining liquid phase and the new hydrogen mixing again.This method can the production sulphur content be lower than 200 μ g/g, and mercaptan sulfur is lower than the gasoline of 10 μ g/g, and the hydro-sweetening process causes that the loss of octane value is very little, but can not satisfy the gasoline that the production sulphur content is lower than 50 μ g/g.
CN101089130A discloses a kind of method of producing low-sulphur oil.This method comprises that gasoline stocks carries out the selective hydrodesulfurization reaction in the presence of catalyst for selectively hydrodesulfurizing; Reaction product contacts with the hydrogenating desulfurization alcohol catalyst; Obtain the low-sulphur oil product after the reaction; The content of described hydrogenating desulfurization alcohol catalyst mesolite is 50.0～90.0wt%, and the total content of transition metal oxide and lanthanide rare MOX is 11.0～31.0wt%.This method can be handled the inferior full distillation gasoline of high-sulfur, high alkene content, and flow process is simple, and is easy to operate, and gained gasoline products not only total sulfur content is lower than 50 μ g/g, and mercaptan sulfur content is lower than 10 μ g/g, and its product loss of octane number is lower than 2 units.
But in the hydrodesulfurization reaction process, H in the reactant flow
2S content constantly increases, and can make alkene and hydrogen sulfide reaction in the gasoline generate new mercaptan sulfur, and these mercaptan mainly also are C
5Above macromole mercaptan.
US6416658B1 proposes a kind of naphtha desulfurization method; Petroleum naphtha is carried out hydrogenating desulfurization simultaneously and separates into the light boiling range petroleum naphtha and the heavy boiling range petroleum naphtha; Through in the hydrogenating desulfurization fixed bed, making the light boiling range petroleum naphtha, remove the regeneration mercaptan that hydrodesulfurization process generates subsequently further with reflux type and contacted with hydrogen.
Though adopt the countercurrent hydrogenation desulfurization can avoid new mercaptan to generate, because olefin content in gasoline is higher, it is saturated still to have part alkene in the hydro-sweetening process, causes the product loss of octane number.
CN 1916118A discloses a kind of method of gasoline hydrogenation modifying.This method is cut into light gasoline fraction and heavy naphtha with gasoline stocks, and light gasoline fraction removes mercaptan wherein through alkali cleaning refining desulfurization alcohol; The heavy gasoline cut contacts with catalyst for hydro-upgrading together with hydrogen and carries out hydrogenating desulfurization and hydro-upgrading reaction; Resultant of reaction is through cooling; Isolated liquid gets into stabilizer tower, stablizes light gasoline fraction behind bottom stream and the mercaptan removal and mixes and obtain gasoline products.Present method can produce that sulphur content is lower than 150 μ g/g in the gasoline products, and the volume content of alkene satisfies the premium of European III emission requirement index less than 18%.
CN 1809624A discloses the method for a kind of while fractionation and the full boiling range naphtha stream materials flow of hydrogenation.This method adopts catalytic distillation technology that full boiling range naphtha stream is carried out hydrogenating desulfurization processing and fractionation simultaneously.Light boiling range petroleum naphtha after the fractionation is hydrogenation reaction in the adverse current fixed bed further; To remove recombinant mercaptans; Be characterized in before the hydro-sweetening light boiling range petroleum naphtha being carried out fractionation; Remove the lighting end that does not contain mercaptan, cause the alkene of this part cut saturated because of hydrogenation reaction, but hydrogenation of total effluent desulfurization meeting significantly increases the alkene loss in the gasoline lighting end with minimizing.
Can find out from above patent documentation; For domestic high olefin catalytically cracked gasoline; Generally adopt the gasoline refining technology of first fractionation back end hydrogenation; Promptly earlier with catalytically cracked gasoline cut into gently, last running, be rich in alkene and mercaptan sulfur in the lighting end, concentrated most sulfide and part alkene in the last running.Then, utilize alkali cleaning extracting mode to remove gasoline lighting end mercaptan wherein, handle removing the sulfide in the last running through hydrogenating desulfurization, when can guarantee the product desulfurization, gasoline products alkene is saturated minimum, and loss of octane number is minimum.
In the time of the desulfurization of catalytically cracked gasoline heavy fractioning hydrogenation, alkene in the reactant flow and H
2S is prone to reaction and generates mercaptan, and these mercaptan again hydrodesulfurization reaction can take place, and generate corresponding hydrocarbon and H
2S.Because air speed is high, temperature of reaction is lower, has the part mercaptan compound not carry out hydrodesulfurization reaction as yet and has promptly left beds, causes and contains a spot of mercaptan sulfur in the product, is called regeneration mercaptan.Last running product sulphur content is low more behind the hydrogenation, and regeneration mercaptan proportion is big more, last running product sulphur content 50 μ g/g behind the hydrogenation, and regeneration mercaptan accounts for the product total sulfur more than 50%, during last running product sulphur content 10 μ g/g, almost all is the regeneration mercaptan sulfur behind the hydrogenation.Therefore in order to produce low-sulfur and super low-sulfur oil, must remove the regeneration mercaptan in the gasoline last running behind the hydrogenation.
Mercaptan behind the hydrogenation in the gasoline last running mainly is macromole mercaptan; Stable in properties; Traditional oxidation extraction desulfurization alcohol method can't be removed these macromole mercaptan, reduces mercaptan sulfur content and can only mercaptan be converted into disulphide, but the product total sulfur does not reduce.
Summary of the invention
The technical problem that the present invention will solve is on the basis of existing technology, provides a kind of under the non-hydro state, removes sulfur in gasoline alcohol sulphur, reduces the method for gasoline total sulfur content simultaneously.
A kind of method of producing low-sulphur oil may further comprise the steps:
A kind of method of producing low-sulphur oil comprises that with the gasoline stocks fractionation be light gasoline fraction and heavy naphtha; Light gasoline fraction removes mercaptan wherein; Heavy naphtha removes sulfocompound through shortening; Heavy naphtha after the hydrogenating desulfurization is introduced counter-current reactor from the middle part; Below the counter-current reactor opening for feed is conversion zone, filling hydrogenating desulfurization alcohol catalyst, and hydrogen-rich gas is introduced by the counter-current reactor bottom; Heavy naphtha partly is vaporizated into gaseous component and liquid phase component; Liquid phase component from top to bottom flows, and on catalyzer, carries out the hydro-sweetening reaction with the hydrogen counter current contact, and the liquid phase component behind the mercaptan removal flows out from reactor bottom; Gaseous component, unreacted hydrogen and hydrogen sulfide are discharged by the counter-current reactor top; Gaseous component mixes with the light gasoline fraction of the liquid phase component of discharging at the bottom of the tower, caustic wash desulfuration alcohol through condensation and after removing hydrogen sulfide and obtains gasoline products.
In the method provided by the invention, described counter current contact reactor drum is the reactor drum of gas-liquid two-phase reverse flowing reactive on catalyzer.The counter current contact reactor drum operational condition be: the conversion zone temperature is 140～300 ℃, preferred 190～250 ℃, and pressure is 0.2～4MPa, is preferably 0.5～2MPa that air speed is 2.0～10.0h
-1, preferred 2.0～4.0h
-1, hydrogen to oil volume ratio is 1～60Nm
3/ m
3, preferred 1～50Nm
3/ m
3
The beneficial effect of method provided by the invention is:
With the full cut fractionation of gasoline is light gasoline fraction and heavy naphtha, and heavy naphtha carries out hydrogenating desulfurization, and the heavy naphtha after the hydrogenating desulfurization contains more regeneration mercaptan, and said regeneration mercaptan boiling point is higher than 120 ℃.And the light constituent of heavy naphtha mainly is higher C6 of olefin(e) centent and C7 cut.Heavy naphtha part vaporization in counter-current reactor, wherein contain than the gaseous component of polyene hydrocarbon not with reactor drum in the hydrogenating desulfurization alcohol catalyst contact the hydrogen loss that adds that can avoid alkene.Reaction removes mercaptan to liquid phase component with hydrogen-rich gas on mercaptan-eliminating catalyst.Because the stripping effect of hydrogen is reacted the hydrogen sulfide that produces and in time shifted out reaction zone, prevent the generation once more of mercaptan simultaneously, can more fully remove mercaptan wherein.The sulphur content and the mercaptan sulfur content of the gasoline products that method provided by the invention is produced all satisfy IV class content of sulfur in gasoline standard in world's fuel oil standard, even can satisfy Euro V emissions, and loss of octane number is low.As visible gasoline products sulphur content of producing is lower than 50 μ g/g among the embodiment 1,2, mercaptan sulfur is lower than 3 μ g/g.
Description of drawings
Accompanying drawing is the schematic flow sheet of method provided by the invention.
Embodiment
The method of production low-sulphur oil provided by the invention is such practical implementation:
Gasoline stocks is cut into light gasoline fraction, heavy naphtha under 60～70 ℃, the yield of light gasoline fraction and heavy naphtha is respectively 30%～60% and 40%～70% of gasoline stocks massfraction; Light gasoline fraction removes mercaptan wherein.Heavy naphtha and hydrogen-rich gas are introduced in the reactor drum together; Carry out selective hydrodesulfurization reaction contacting with Hydrobon catalyst; Heavy naphtha process HP separator separation after the hydrogenating desulfurization obtains the heavy naphtha after hydrogen-rich gas and the hydrogenating desulfurization, and described hydrogen-rich gas is through removing H
2S recycles after handling.
Described light gasoline fraction removes the method for mercaptan can select caustic wash desulfuration alcohol or Merox catalytic oxidation desulfurization alcohol technology in the prior art for use; Wherein Merox catalytic oxidation desulfurization alcohol can be 30～60 ℃ in temperature; Under the non-pressurized condition; The light gasoline fraction of alcohol to be desulfurization is realized through sulfonated phthalocyanine cobalt volume space velocity is 2～6h during the liquid of raw material
-1
Described heavy naphtha hydrodesulfurization reaction condition is: temperature of reaction is 250～400 ℃, preferred 210～260 ℃; Pressure is 0.2～6MPa, preferred 0.4～2.5MPa; Volume space velocity is 2～15h during feeding liquid
-1, preferred 4～10h
-1Hydrogen-oil ratio is 100～1000Nm
3/ m
3
Described Hydrobon catalyst is VIB or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.
In the method provided by the invention; Heavy naphtha after the described hydrogenating desulfurization is introduced the counter current contact reactor drum from the middle part; Described counter current contact reactor drum is meant the catalytic reactor drum of gas-liquid two-phase adverse current on catalyzer in the reactor drum; Heavy naphtha part in the counter current contact reactor drum is vaporizated into gas-liquid two-phase, and the hydro-sweetening catalyst loading is in heavy naphtha opening for feed bottom, and hydrogen-rich gas is introduced from reactor bottom.Heavy naphtha is vaporized isolated liquid phase component from top to bottom through conversion zone, and mercaptan on the hydrogenating desulfurization alcohol catalyst in the liquid phase component and the reaction of hydrogen counter current contact generate hydrocarbon component and H
2S.Liquid phase component behind the mercaptan removal flows out from reactor bottom.Operational condition in the described counter-current reactor is: the conversion zone temperature is 140～300 ℃, preferred 190～250 ℃, and pressure is 0.2～4MPa, is preferably 0.5～2MPa that air speed is 2.0～10.0h
-1, preferred 2.0～4.0h
-1, hydrogen to oil volume ratio is 1～60Nm
3/ m
3, preferred 1～50Nm
3/ m
3
In the method provided by the invention, heavy naphtha vaporize isolated gaseous component, unreacted hydrogen and hydrogen sulfide of part in the counter current contact reactor drum discharged by reactor head.Described counter current contact reactor drum top preferably is provided with fractionation zone, is beneficial to the separation of weight component.Described fractionation zone filling filler or column plate, theoretical plate number is at the 2-7 piece.The heavy naphtha opening for feed is in fractionation zone bottom or bottom.Gaseous component is discharged by reactor head after the whole caterpillar of the overhead product after condensation and the gas-liquid separation; Also can a part draw return device as backflow, another part is as the reactor head discharging.Preferred scheme be a part with the reactor head overhead product as backflow, reflux ratio is 0.1～1.Reactor head distillates the gasoline fraction final boiling point and is not higher than 120 ℃.
In the method provided by the invention, preferably introduce the stripping medium, with the stripping of hydrogen sulfide in the enhanced reactor at the counter current contact reactor bottom.Described stripping medium is selected from non-hydrogen rare gas element and/or lighter hydrocarbons, like nitrogen, carbonic acid gas, ethane etc.
In the method provided by the invention, mix obtaining gasoline products behind the heavy petrol gaseous component depriving hydrogen sulphide that the heavy petrol liquid phase component behind the mercaptan removal that discharge above-mentioned counter-current reactor bottom, counter current contact reactor head are discharged with petroleum naphtha after alkali cleaning is refining.
In the method provided by the invention, all be provided with stripping tower or stabilizer tower in the prior art in the gasoline hydrogenation technology in order to remove lighter hydrocarbons and hydrogen sulfide such as the methane in the gasoline, ethane behind the hydrogenation.Method provided by the invention is in the practical implementation process; Can use conventional existing stabilizer tower of gasoline hydrogenation device or stripping tower, filling hydrogenating desulfurization alcohol catalyst under the heavy naphtha opening for feed, opening for feed top filling filler; Can simplify technical process, save facility investment.
In the method provided by the invention, described Hydrobon catalyst is VIB and/or the VIII family non-precious metal catalyst that loads on aluminum oxide and/or the silica-alumina supports, and preferred catalyzer is for containing molybdenum and/or tungsten, nickel and/or cobalt; In oxide compound and with the catalyzer total mass is benchmark, and the massfraction of said molybdenum and/or tungsten is 3%～25%, the massfraction of nickel and/or cobalt is 1%～10%.
In the method provided by the invention, described gasoline stocks is for being the petroleum hydrocarbon cut of final boiling point ≯ 230 ℃ for boiling range.Being preferably boiling range is 30～230 ℃, contains the petroleum hydrocarbon fraction of 5wt% alkene at least.Be selected from catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, pyrolysis gasoline and the pressure gasoline one or more mixture.
In the method provided by the invention, the heavy naphtha Hydrobon catalyst can be identical with the hydrogenating desulfurization alcohol catalyst, also can be different, and hydro-sweetening reaction severity is compared the hydrodesulfurization reaction severity and will be relaxed.
Method provided by the invention is light, heavy naphtha with the full cut fractionation of gasoline, and heavy naphtha carries out hydrogenating desulfurization earlier, can avoid the lighting end gasoline hydrodesulfurizationmethod to cause the product loss of octane number.Heavy naphtha after the hydrogenating desulfurization is introduced the counter current contact reactor drum again, the regeneration mercaptan that hydrogenation and removing wherein generates in hydrodesulfurization process.Contained regeneration mercaptan boiling point is higher than 120 ℃ in the heavy naphtha; Heavy naphtha is introduced in the counter-current reactor part be vaporizated into gaseous component and liquid phase component; Gaseous component is higher C6 of olefin(e) centent and C7 cut; By discharging on reactor drum top, not with reactor drum in the hydrogenating desulfurization alcohol catalyst contact the hydrogen loss that adds that can avoid alkene; The following loading catalyst of reactor feed mouth, the liquid phase component that contains the mercaptan of regenerating removes mercaptan with hydrogen reaction on mercaptan-eliminating catalyst.Because hydrogen and the effect of stripping medium stripping are reacted the hydrogen sulfide that produces and can in time be shifted out reaction zone, prevent the generation once more of mercaptan in addition, can more fully remove mercaptan wherein.
Below in conjunction with accompanying drawing method provided by the present invention is further explained.But therefore do not limit the present invention.
Accompanying drawing is the schematic flow sheet of the method for production low-sulphur oil provided by the invention.Gasoline stocks gets into separation column 2 through pipeline 1 and is cut into light gasoline fraction and heavy naphtha; Wherein light gasoline fraction is distillated through pipeline 3 dereaction devices 18 alkali cleaning refining desulfurization alcohol by cat head; Heavy naphtha by tower at the bottom of discharging get into pumps 5 through pipeline 4; Heavy naphtha after boosting gets into process furnace 8 with after hydrogen from pipeline 17 mixes through pipeline 7, and the material after the preheating gets in the hydrogenators 10 through pipeline 9; Contact with Hydrobon catalyst, sulfocompound in the heavy naphtha and hydrogen generate hydrocarbon and H
2S; Heavy naphtha behind the reaction desulfuration gets into HP separator 12 through pipeline 11; The hydrogen-rich gas that contains hydrogen sulfide that comes out from HP separator 12 tops removes hydrogen sulfide after pipeline 14 gets into compressor 15; Hydrogen-rich gas after the compression through pipeline 16 or with from the additional fresh hydrogen of pipeline 6 through pipeline 17, mix dereaction with heavy naphtha.
Heavy naphtha after the hydrogenating desulfurization of coming out from HP separator 12 bottoms gets into catalysis stripping towers 19 middle parts through pipeline 13; In tower, flow contact reacts from the hydrogen that tower bottom gets in stripping section hydrogenating desulfurization alcohol catalyst superinverse downwards with from pipeline 20; Regeneration mercaptan and hydrogen reaction in the heavy naphtha remove, and generate H
2S.Liquid flows out from pipeline 21 at the bottom of the tower; The heavy petrol heavy constituent of a part after pipeline 23 obtains mercaptan removal, another part gets into reboiler 25 vaporizations through pipeline 24, returns in the tower through pipeline 26; A part of light constituent of heavy petrol distillates from top of tower; Get into condensing surface 27 through pipeline 22 and carry out condensation, get into gas-liquid separator 29 through pipeline 28 again, the hydrogen-rich gas that comes out from gas-liquid separator 29 tops is drawn through pipeline 30 and is reclaimed; A liquid product part of coming out from gas-liquid separator 29 bottoms refluxes the heavy petrol light constituent of another part after pipeline 32 caterpillars obtain separating through pipeline 31.Petroleum naphtha after refining take off behind the H2S with mercaptan removal after the heavy petrol heavy constituent through pipeline 24 with separate after the heavy petrol light constituent be mixed into full distillation gasoline product through pipeline 33 and see off through pipeline 34.
Following embodiment will further explain method provided by the invention, but therefore not limit the present invention.
Catalyzer used in embodiment and the Comparative Examples is produced by Sinopec catalyzer Chang Ling branch office, and trade names are RSS-1A, and it mainly consists of, and in total catalyst weight, contains the NiO of 4.5wt%, the WO of 14.5wt%
3Al with surplus
2O
3
Comparative Examples 1
Gasoline stocks is a catalytically cracked gasoline, earlier gasoline stocks is cut, and obtains heavy naphtha and light gasoline fraction, and the character of catalytically cracked gasoline raw material, heavy naphtha and light gasoline fraction is as shown in table 1.Heavy naphtha is introduced hydrogenator after hydrogenating desulfurization, obtains sulphur content 90 μ g/g, the heavy petrol product of mercaptans content 25 μ g/g.With after through Merox catalytic oxidation desulfurization alcohol technology, catalyzer is the RDM-02 catalyzer, to produce by Sinopec catalyzer Chang Ling branch office, the sulfonated phthalocyanine cobalt contents is greater than 1%.Reaction conditions: 40 ℃ of temperature, normal pressure, volume space velocity 4h during liquid
-1Heavy petrol, air sweetening heavy petrol character are seen table 2 behind the hydrogenation, can find out from table 2, and mercaptan is less than 10 μ g/g in the heavy naphtha behind air sweetening, and total sulfur and octane value do not become basically.Behind the air sweetening behind heavy naphtha and the caustic wash desulfuration alcohol light gasoline fraction mix and obtain gasoline products, character is seen table 3.Can find out the gasoline products mercaptans content less than 10 μ g/g from table 3, sulphur content satisfies Europe III emission standard less than 150 μ g/g, and product RON loss of octane number is less than 1.1.
Embodiment 1
Gasoline fractionation, heavy fractioning hydrogenation sweetening process are identical with Comparative Examples 1.Different is that heavy naphtha is introduced in the stripping tower after the hydrogenating desulfurization.Described stripping tower diameter is 32mm, highly is 4m, and charging is above highly to be 1m, the hole random packing of filling Φ 3mm rolling metal.The mercaptan-eliminating catalyst of filling below opening for feed RSS-1A is 140g altogether, and the stripping tower working pressure is 1.3MPa, and the beds medial temperature is 220 ℃; Inlet amount is 700g/h, and the feed hydrogen oil ratio is 25, and the bottom product part is returned stripping tower after the reboiler heating; The part discharging, load 500g/h.The cat head discharging is the non-condensable gas discharging after condensation, liquid-phase product partial reflux, part discharging, reflux ratio 0.5.The cat head liquid-phase product removes H wherein through further stripping
2Behind the S with mercaptan removal after gasoline last running product mix and obtain heavy naphtha behind the mercaptan removal, its character is seen table 2.Mix to obtain gasoline products with gasoline lighting end behind the caustic wash desulfuration alcohol, gasoline products character is seen table 3.
Can find out from table 2, compare with Comparative Examples through present embodiment that the mercaptans content of gasoline last running product drops to less than 3 μ g/g from 9 μ g/g, sulphur content is fallen by 90 μ g/g and is dropped to 60 μ g/g, and the product loss of octane number increases by 0.1.Mercaptans content is less than 3 μ g/g in the mixed gasoline products, and sulphur content drops to 41 μ g/g, and the product sulphur content satisfies Europe IV emission standard, and the Comparative Examples product can only satisfy Europe III emission standard.Compare with Comparative Examples through present embodiment gained gasoline products, upgrade to and satisfy Europe IV emission standard by satisfying Europe III emission standard, and product RON loss of octane number only increases by 0.1.
Comparative Examples 2
The gasoline fractionation process is identical with Comparative Examples 1, and the heavy naphtha after the cutting is through deep hydrodesulfurizationof, and product property is seen table 4, product sulphur content 28 μ g/g wherein, and mercaptans content 19 μ g/g, mercaptans content accounts for 67.8% of total sulfur.Heavy naphtha behind the hydrogenation is without air sweetening; Carry out the hydro-sweetening reaction but further in fixed bed, contact with hydrogen, catalyzer RSS-1A, the pressure of hydro-sweetening reaction is 1.6MPa, and temperature is 230 ℃; Hydrogen-oil ratio is 150, and the feed volume air speed is 5h
-1Obtain heavy naphtha behind the hydro-sweetening, character is as shown in table 2.Through hydro-sweetening, product mercaptan is less than 8 μ g/g, and total sulfur is reduced to 20 μ g/g, but product research method octane value (RON) reduces 4.5.Light gasoline fraction behind heavy naphtha behind the mercaptan removal and the caustic wash desulfuration alcohol mixes and obtains gasoline products, and character is seen table 5.Can find out the product mercaptans content less than 10 μ g/g from table 5, sulphur content satisfies Europe IV emission standard less than 50 μ g/g, and product octane value RON loses less than 2.5.
Embodiment 2
Gasoline fractionation, heavy naphtha hydrodesulfurization process are identical with embodiment 1.Heavy naphtha after the hydrogenating desulfurization is introduced hydro-sweetening in the stripping tower, and used stripping tower and catalyst loading are identical with embodiment 1.Different is that the stripping tower working pressure is 0.9MPa, and the following beds medial temperature of charging is 200 ℃, and inlet amount is 700g/h, and the feed hydrogen oil ratio is 10, and discharging is 400g/h at the bottom of the cat head.The cat head discharging is the non-condensable gas discharging after condensation, liquid-phase product partial reflux, part discharging, reflux ratio 0.2.The cat head discharging removes H wherein through further stripping
2Behind the S with mercaptan removal after the heavy naphtha product mix the heavy naphtha that obtains behind the mercaptan removal, its character is seen table 4.Mix to obtain gasoline products with light gasoline fraction behind the caustic wash desulfuration alcohol, character is seen table 5.
Can find out that from table 3 through this enforcement, compare with Comparative Examples, the mercaptans content of gasoline last running product drops to 3 μ g/g from 8 μ g/g, the product sulphur content drops to 10 μ g/g from 20 μ g/g, and product RON loss of octane number is less than Comparative Examples 0.3.Mixed full cut product mercaptans content is less than 3 μ g/g, sulphur content 6.7 μ g/g, and the product sulphur content satisfies the gasoline products of Euro V emissions.Compare with Comparative Examples through present embodiment gained gasoline products, upgrade to and satisfy Euro V emissions by satisfying Europe IV emission standard, and product octane value RON loss is lower than Comparative Examples 0.2.
Table 1
Table 2
Table 3
| Product property | Comparative Examples 1 | Embodiment 1 |
| Density (20 ℃), g/cm 3 | 0.7216 | 0.7212 |
| Sulphur content, μ g/g | 60 | 41 |
| Mercaptans |
6 | ＜3 |
| Volume fraction of olefins, % | 31.8 | 31.8 |
| RON | 91.3 | 91.2 |
| The RON loss | 1.1 | 1.2 |
Table 4
| Product property | Gasoline last running behind the hydrogenation | Comparative Examples 2 | Embodiment 2 |
| Density (20 ℃), g/cm 3 | 0.7694 | 0.7694 | 0.7692 |
| Sulphur, μ g/ |
28 | 20 | 10 |
| Mercaptans content, μ g/ |
19 | 8 | ＜3 |
| Volume fraction of olefins, % | 22 | 20 | 21.5 |
| RON | 86.9 | 86.6 | 86.8 |
| The RON loss | 4.2 | 4.5 | 4.3 |
Table 5
| Gasoline products character | Comparative Examples 2 | Embodiment 2 |
| Density (20 ℃), g/cm 3 | 0.7216 | 0.7212 |
| Sulphur content, μ g/ |
13 | 6.7 |
| Mercaptans content | 5 | ＜3 |
| Volume fraction of olefins, % | 26.7 | 28.1 |
| RON | 89.9 | 90.1 |
| The RON loss | 2.5 | 2.3 |
Claims (11)
1. a method of producing low-sulphur oil comprises that with the gasoline stocks fractionation be light gasoline fraction and heavy naphtha; Light gasoline fraction removes mercaptan wherein; Heavy naphtha removes sulfocompound through shortening; It is characterized in that the heavy naphtha after the hydrogenating desulfurization is introduced counter-current reactor from the middle part; Below the counter-current reactor opening for feed is conversion zone, filling hydrogenating desulfurization alcohol catalyst, and hydrogen-rich gas is introduced by the counter-current reactor bottom; Heavy naphtha partly is vaporizated into gaseous component and liquid phase component; Liquid phase component from top to bottom flows, and on catalyzer, carries out the hydro-sweetening reaction with the hydrogen counter current contact, and the liquid phase component behind the mercaptan removal flows out from reactor bottom; Gaseous component, unreacted hydrogen and hydrogen sulfide are discharged by the counter-current reactor top; Gaseous component mixes with the light gasoline fraction of the liquid phase component of discharging at the bottom of the tower, caustic wash desulfuration alcohol through condensation and after removing hydrogen sulfide and obtains gasoline products.
2. according to the method for claim 1, it is characterized in that described counter current contact reactor feed mouth loads or do not load distillation filler or fractionating tray with top.
3. according to the method for claim 1 or 2, it is characterized in that described counter current contact reactor bottom also introduces the stripping medium, the stripping medium is selected from non-hydrogen rare gas element and/or lighter hydrocarbons.
4. according to the method for claim 1, it is characterized in that the operational condition in the described counter-current reactor is: pressure is 0.2～4MPa, and the conversion zone temperature is 140～300 ℃, and air speed is 2.0～10.0h
-1, hydrogen to oil volume ratio is 1～60Nm
3/ m
3
5. according to the method for claim 2, it is characterized in that the operational condition in the described counter-current reactor is: pressure is 0.5～2.0MPa, and the conversion zone temperature is 190～250 ℃, and air speed is 2.0～4.0h
-1, hydrogen to oil volume ratio is 1～50Nm
3/ m
3
6. according to the method for claim 1, it is characterized in that described counter-current reactor top distillates the gasoline fraction final boiling point and is not more than 120 ℃.
7. according to the method for claim 1, it is characterized in that described gasoline stocks fractionation is light gasoline fraction and heavy naphtha, cut point is 60～90 ℃.
8. according to the method for claim 1, it is characterized in that described hydrodesulfurization reaction condition is: temperature of reaction is 250～400 ℃, and pressure is 0.2～6MPa, and volume space velocity is 2～15h during feeding liquid
-1,, hydrogen-oil ratio is 100～1000Nm
3/ m
3
9. according to the method for claim 1, it is characterized in that described hydrogenating desulfurization alcohol catalyst is VIB or the VIII family non-precious metal catalyst that loads on aluminum oxide and/or the silica-alumina supports.
10. according to the method for claim 9; It is characterized in that described hydrogenating desulfurization alcohol catalyst contains molybdenum and/or tungsten, nickel and/or cobalt; In oxide compound and with the catalyzer total mass is benchmark, and the massfraction of said molybdenum and/or tungsten is 3%～25%, the massfraction of nickel and/or cobalt is 1%～10%.
11., it is characterized in that described gasoline stocks is that boiling range is 30 ℃～230 ℃, contains the petroleum hydrocarbon fraction of 5wt% alkene at least according to the method for claim 1.
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| CN103468310A (en) * | 2012-06-07 | 2013-12-25 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
| CN108018075A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method of gasoline desulfurization and the device of gasoline desulfurization |
| CN111393248A (en) * | 2019-07-15 | 2020-07-10 | 中国石化工程建设有限公司 | Device and method for oil gas desulfurization and light hydrocarbon recovery |
| CN112662427A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Gasoline fraction desulfurization method, method for producing low-sulfur gasoline and reaction system |
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| CN103468309A (en) * | 2012-06-07 | 2013-12-25 | 中国石油化工股份有限公司 | Low sulfur gasoline production method |
| CN103468310A (en) * | 2012-06-07 | 2013-12-25 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
| CN103468309B (en) * | 2012-06-07 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method of producing low-sulphur oil |
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| CN108018075B (en) * | 2016-10-31 | 2020-04-28 | 中国石油化工股份有限公司 | Gasoline desulfurization method and gasoline desulfurization device |
| CN111393248A (en) * | 2019-07-15 | 2020-07-10 | 中国石化工程建设有限公司 | Device and method for oil gas desulfurization and light hydrocarbon recovery |
| CN111393248B (en) * | 2019-07-15 | 2023-05-26 | 中国石化工程建设有限公司 | Device and method for desulfurizing oil gas and recovering light hydrocarbon |
| CN112662427A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Gasoline fraction desulfurization method, method for producing low-sulfur gasoline and reaction system |
| CN112662427B (en) * | 2019-10-15 | 2022-12-13 | 中国石油化工股份有限公司 | Gasoline fraction desulfurization method, method for producing low-sulfur gasoline and reaction system |
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