CN102443433B - Method for producing low-sulfur gasoline - Google Patents
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- CN102443433B CN102443433B CN201010508141.6A CN201010508141A CN102443433B CN 102443433 B CN102443433 B CN 102443433B CN 201010508141 A CN201010508141 A CN 201010508141A CN 102443433 B CN102443433 B CN 102443433B
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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 reducing in gasoline, the method for producing low-sulphur oil.
Background technology
Along with the increasingly stringent of environmental regulation, countries in the world have proposed stricter restriction to the composition of motor spirit as sulphur content, vapour pressure, benzene content, aromatic hydrocarbons total content, olefin(e) centent, wherein particularly harsh to the restriction of the sulphur content in gasoline.At present, in gasoline product, 90%～99% sulphur is from catalytically cracked gasoline, and therefore, reducing sulfur content of catalytic cracking gasoline is the key point that reduces finished product content of sulfur in gasoline.
China's catalytically cracked gasoline is main blend component in 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, wherein the octane value of normal paraffin is low, and the longer octane value of carbochain is lower; The octane value of isoparaffin is higher, and collateralization degree is higher, it is higher to arrange compacter octane value; Alkene, aromatic hydrocarbons are high-octane number components, the highest with the octane value of aromatic hydrocarbons.China's catalytically cracked gasoline presents the feature of high olefin, low arene content, and the volume content of alkene is conventionally in 40～50% left and right, and the volume content of aromatic hydrocarbons is less than 20%.Alkene becomes the important component in China's catalytically cracked gasoline octane value source, thereby the variation of olefin(e) centent is very large on the impact 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 significantly to reduce.
CN 1478866A discloses a kind of method of gasoline desulfur.Gasoline stocks is cut into light gasoline fraction, heavy naphtha by the method; Heavy naphtha contacts with Hydrobon catalyst together with hydrogen, carries out selective hydrodesulfurization reaction, and reaction effluent is after high-pressure separator is isolated gas phase, and remaining liquid phase contacts with hydrogenating desulfurization alcohol catalyst after mixing with new hydrogen again.The method energy production sulphur content is lower than 200 μ g/g, and mercaptan sulfur is lower than the gasoline of 10 μ g/g, and hydro-sweetening process causes that the loss of octane value is very little, but can not meet the gasoline of production sulphur content lower than 50 μ g/g.
CN101089130A discloses a kind of method of producing low-sulphur oil.The method comprises that gasoline stocks carries out selective hydrodesulfurization reaction under catalyst for selectively hydrodesulfurizing exists, reaction product contacts with hydrogenating desulfurization alcohol catalyst, after reaction, obtain low-sulphur oil product, 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 metal oxide is 11.0～31.0wt%.The method can be processed the full distillation gasoline of poor quality of high-sulfur, high alkene content, and flow process is simple, easy to operate, and not only total sulfur content is lower than 50 μ g/g for gained gasoline products, 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 hydrodesulfurization reaction process, H in reactant flow
2s content constantly increases, and can make alkene and hydrogen sulfide reaction in gasoline generate new mercaptan sulfur, and these mercaptan are also mainly C
5above macromole mercaptan.
US6416658B1 proposes a kind of naphtha desulfurization method, petroleum naphtha is carried out to hydrogenating desulfurization simultaneously and is separated into light boiling range petroleum naphtha and heavy boiling range petroleum naphtha, by making light boiling range petroleum naphtha further contact with hydrogen with reflux type, remove the regeneration mercaptan that hydrodesulfurization process generates subsequently in hydrogenating desulfurization fixed bed.
Although adopt countercurrent hydrogenation desulfurization can avoid new mercaptan to generate, because the olefin(e) centent in gasoline is higher, in hydro-sweetening process, still have part olefin saturated, cause product loss of octane number.
CN 1916118A discloses a kind of method of gasoline hydrogenation modifying.Gasoline stocks is cut into light gasoline fraction and heavy naphtha by the method, and light gasoline fraction removes mercaptan wherein through alkali cleaning refining desulfurization alcohol; Heavy gasoline cut contacts with catalyst for hydro-upgrading together and carries out hydrogenating desulfurization and hydro-upgrading reaction with hydrogen, resultant of reaction is through cooling, isolated liquid enters stabilizer tower, and the light gasoline fraction of stablizing after bottom stream and mercaptan removal is mixed to get gasoline products.Present method can produce that in gasoline products, sulphur content is lower than 150 μ g/g, and the volume content of alkene is less than 18%, meets the premium of European III emission requirement index.
CN 1809624A discloses a kind of method of while fractionation and the full boiling range naphtha stream material stream of hydrogenation.The method adopts catalytic distillation technology to carry out hydrogenating desulfurization processing and fractionation to full boiling range naphtha stream simultaneously.Light boiling range petroleum naphtha after fractionation is hydrogenation reaction in adverse current fixed bed further, to remove recombinant mercaptans, be characterized in, before hydro-sweetening, light boiling range petroleum naphtha is carried out to fractionation, remove the not lighting end containing mercaptan, to reduce the olefin saturated that causes this part cut because of hydrogenation reaction, but hydrogenation of total effluent desulfurization meeting significantly increases the alkene loss in gasoline lighting end.
Can find out from above patent documentation, for domestic high olefin catalytically cracked gasoline, generally adopt the gasoline refining technique of first fractionation back end hydrogenation, first catalytically cracked gasoline is cut into gently, last running, in lighting end, be rich in alkene and mercaptan sulfur, in last running, concentrated most sulfide and part alkene.Then, utilize alkali cleaning extracting mode to remove gasoline lighting end mercaptan wherein, remove the sulfide in last running by hydrogenating desulfurization processing, when can ensureing product desulfurization, gasoline products olefin saturated is minimum, loss of octane number minimum.
When the desulfurization of catalytically cracked gasoline heavy fractioning hydrogenation, the alkene in reactant flow and H
2s easily reacts generation mercaptan, and hydrodesulfurization reaction can occur again these mercaptan, generates corresponding hydrocarbon and H
2s.Because air speed is high, temperature of reaction is lower, has part mercaptan compound not yet to carry out hydrodesulfurization reaction and has left beds, causes in product and contains a small amount of mercaptan sulfur, is called regeneration mercaptan.After hydrogenation, last running product sulphur content is lower, and regeneration mercaptan proportion is larger, last running product sulphur content 50 μ g/g after hydrogenation, and regeneration mercaptan accounts for product total sulfur more than 50%, after hydrogenation, when last running product sulphur content 10 μ g/g, is all almost regeneration mercaptan sulfur.Therefore in order to produce low-sulfur and super low-sulfur oil, must remove the regeneration mercaptan in gasoline last running after hydrogenation.
Mercaptan after hydrogenation in gasoline last running is mainly macromole mercaptan, stable in properties, traditional oxidation extraction desulfurization alcohol method cannot be removed these macromole mercaptan, reduces mercaptan sulfur content and mercaptan can only be converted into disulphide, but product total sulfur does not reduce.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, provides a kind of and remove mercaptan from gasoline sulphur under non-hydrogen state, reduces the method for gasoline total sulfur content simultaneously.
A method of producing low-sulphur oil, comprises the following steps:
Produce a method for low-sulphur oil, comprise that by 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 hydrogenating desulfurization is introduced to counter-current reactor from middle part, counter-current reactor opening for feed is conversion zone below, filling hydrogenating desulfurization alcohol catalyst, hydrogen-rich gas is introduced by counter-current reactor bottom, heavy naphtha part is vaporizated into gaseous component and liquid phase component, liquid phase component from top to bottom flows, and carries out hydro-sweetening react on catalyzer with hydrogen counter current contact, and the liquid phase component after mercaptan removal flows out from reactor bottom; Gaseous component, unreacted hydrogen and hydrogen sulfide are discharged by counter-current reactor top; Gaseous component is mixed to get gasoline products through condensation and after removing hydrogen sulfide with the liquid phase component of discharging at the bottom of tower, the light gasoline fraction of caustic wash desulfuration alcohol.
In method provided by the invention, described counter current contact reactor is the reactor of gas-liquid two-phase reverse flowing reactive on catalyzer.Counter current contact reactor operational condition be: conversion zone temperature is 140～300 DEG C, preferably 190～250 DEG C, and pressure is 0.2～4MPa, is preferably 0.5～2MPa, and 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:
Be light gasoline fraction and heavy naphtha by full gasoline cut fractionation, heavy naphtha carries out hydrogenating desulfurization, and the heavy naphtha after hydrogenating desulfurization contains more regeneration mercaptan, and described regeneration mercaptan boiling point is higher than 120 DEG C.And the light constituent of heavy naphtha is mainly C6 and C7 cut that olefin(e) centent is higher.Heavy naphtha is part vaporization in counter-current reactor, wherein contains compared with the gaseous component of polyene hydrocarbon and does not contact with hydrogenating desulfurization alcohol catalyst in reactor the hydrogen loss that adds that can avoid alkene.On mercaptan-eliminating catalyst, reaction removes mercaptan to liquid phase component with hydrogen-rich gas.Due to the stripping effect of hydrogen, the hydrogen sulfide that reaction produces shifts out reaction zone in time, prevents the generation again of mercaptan, can more fully remove mercaptan wherein simultaneously.Sulphur content and the mercaptan sulfur content of the gasoline products that method provided by the invention is produced all meet IV class content of sulfur in gasoline standard in world's fuel oil specification, even can meet Euro V emissions, and loss of octane number are low.As visible gasoline products sulphur content of producing in embodiment 1,2 lower than 50 μ g/g, mercaptan sulfur lower than 3 μ g/g.
Brief description of the 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 so concrete enforcement:
Gasoline stocks is cut at 60～70 DEG C to light gasoline fraction, heavy naphtha, 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 is introduced in reactor together with hydrogen-rich gas, carry out selective hydrodesulfurization reaction contacting with Hydrobon catalyst, heavy naphtha after hydrogenating desulfurization separates through high-pressure separator the heavy naphtha obtaining after hydrogen-rich gas and hydrogenating desulfurization, and described hydrogen-rich gas is through removing H
2s recycles after processing.
Described light gasoline fraction removes the method for mercaptan can select caustic wash desulfuration alcohol or Merox catalytic oxidation desulfurization alcohol technique in prior art, wherein Merox catalytic oxidation desulfurization alcohol can be 30～60 DEG C in temperature, under the condition of normal pressure, the light gasoline fraction of alcohol to be desulfurization is realized by sulfonated phthalocyanine cobalt, and when the liquid of raw material, volume space velocity is 2～6h
-1.
Described heavy naphtha hydrodesulfurization reaction condition is: temperature of reaction is 250～400 DEG C, preferably 210～260 DEG C; Pressure is 0.2～6MPa, preferred 0.4～2.5MPa; When feeding liquid, volume space velocity is 2～15h
-1, preferred 4～10h
-1; Hydrogen-oil ratio is 100～1000Nm
3/ m
3.
Described Hydrobon catalyst is VIB or the VIII family non-precious metal catalyst loading in unformed aluminum oxide or silica-alumina supports.
In method provided by the invention, heavy naphtha after described hydrogenating desulfurization is introduced counter current contact reactor from middle part, described counter current contact reactor refers to the catalytic reactor of gas-liquid two-phase adverse current on catalyzer in reactor, heavy naphtha part in counter current contact reactor is vaporizated into gas-liquid two-phase, 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 by conversion zone, and the mercaptan on hydrogenating desulfurization alcohol catalyst in liquid phase component reacts with hydrogen counter current contact and generates hydrocarbon component and H
2s.Liquid phase component after mercaptan removal flows out from reactor bottom.Operational condition in described counter-current reactor is: conversion zone temperature is 140～300 DEG C, preferably 190～250 DEG C, and pressure is 0.2～4MPa, is preferably 0.5～2MPa, and 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 method provided by the invention, heavy naphtha vaporize isolated gaseous component, unreacted hydrogen and hydrogen sulfide of part in counter current contact reactor discharged by reactor head.Described counter current contact reactor top preferably arranges fractionation zone, is beneficial to the separation of weight component.Described fractionation zone filling filler or column plate, theoretical plate number is at 2-7 piece.Heavy naphtha opening for feed is in bottom, fractionation zone or bottom.Gaseous component discharged by reactor head after all caterpillars of overhead product after condensation and gas-liquid separation; Also can a part draw return device as backflow, another part is as reactor head discharging.Preferred scheme is using a part for reactor head overhead product as backflow, and reflux ratio is 0.1～1.Reactor head distillates gasoline fraction final boiling point not higher than 120 DEG C.
In method provided by the invention, preferably introduce stripping medium at counter current contact reactor bottom, with the stripping of hydrogen sulfide in enhanced reactor.Described stripping medium is selected from non-hydrogen rare gas element and/or lighter hydrocarbons, as nitrogen, carbonic acid gas, ethane etc.
In method provided by the invention, the petroleum naphtha after refining with alkali cleaning after the heavy petrol liquid phase component after the mercaptan removal that discharge above-mentioned counter-current reactor bottom, the heavy petrol gaseous component depriving hydrogen sulphide that counter current contact reactor head is discharged is mixed to get gasoline products.
In method provided by the invention, in prior art, in gasoline hydrogenation technique, be all provided with stripping tower or stabilizer tower in order to remove the lighter hydrocarbons such as methane, ethane and the hydrogen sulfide in gasoline after hydrogenation.Method provided by the invention is in specific implementation process, can use the conventional existing stabilizer tower of gasoline hydrogenation device or stripping tower, under heavy naphtha opening for feed, load hydrogenating desulfurization alcohol catalyst, opening for feed top filling filler, can simplification of flowsheet, save facility investment.
In method provided by the invention, described Hydrobon catalyst is VIB and/or the VIII family non-precious metal catalyst loading in aluminum oxide and/or silica-alumina supports, and preferred catalyzer is for containing molybdenum and/or tungsten, nickel and/or cobalt; In oxide compound and taking catalyzer total mass as benchmark, the massfraction of described molybdenum and/or tungsten is 3%～25%, the massfraction of nickel and/or cobalt is 1%～10%.
In method provided by the invention, described gasoline stocks for boiling range be the petroleum hydrocarbon cut of final boiling point ≯ 230 DEG C.Being preferably boiling range is 30～230 DEG C, at least contains the petroleum hydrocarbon fraction of 5wt% alkene.Be selected from catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, pyrolysis gasoline and pressure gasoline the mixture of one or more.
In method provided by the invention, heavy naphtha Hydrobon catalyst and hydrogenating desulfurization alcohol catalyst can be identical, also can be different, and hydro-sweetening reaction severity is compared hydrodesulfurization reaction severity and will be relaxed.
Method provided by the invention is light, heavy naphtha by full gasoline cut fractionation, and heavy naphtha first carries out hydrogenating desulfurization, can avoid lighting end gasoline hydrodesulfurizationmethod to cause product loss of octane number.Heavy naphtha after hydrogenating desulfurization is introduced counter current contact reactor again, the regeneration mercaptan that hydrogenation and removing wherein generates in hydrodesulfurization process.In heavy naphtha, contained regeneration mercaptan boiling point is higher than 120 DEG C, heavy naphtha is introduced to part in counter-current reactor and be vaporizated into gaseous component and liquid phase component, gaseous component is C6 and the C7 cut that olefin(e) centent is higher, discharged by reactor top, do not contact with hydrogenating desulfurization alcohol catalyst in reactor 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.Due to hydrogen and the effect of stripping medium stripping, the hydrogen sulfide that reaction produces can shift out reaction zone in time, prevents the generation again of mercaptan, can more fully remove mercaptan wherein in addition.
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed.But not thereby limiting the invention.
Accompanying drawing is the schematic flow sheet of the method for production low-sulphur oil provided by the invention.Gasoline stocks enters 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 device 18 alkali cleaning refining desulfurization alcohol by tower top, heavy naphtha by tower at the bottom of discharging enter pump 5 through pipeline 4, after heavy naphtha after boosting mixes with from the hydrogen of pipeline 17, enter process furnace 8 through pipeline 7, material after preheating enters in hydrogenator 10 through pipeline 9, contact with Hydrobon catalyst, the sulfocompound in heavy naphtha and hydrogen generate hydrocarbon and H
2s, heavy naphtha after reaction desulfuration enters high-pressure separator 12 through pipeline 11, from removing hydrogen sulfide, the high-pressure separator 12 tops hydrogen-rich gas that contains hydrogen sulfide out enters compressor 15 through pipeline 14, hydrogen-rich gas after compression through pipeline 16 or with together with supplementary fresh hydrogen from pipeline 6 through pipeline 17, mix dereaction with heavy naphtha.
Heavy naphtha from the hydrogenating desulfurization out of high-pressure separator 12 bottoms enters catalysis stripping tower 19 middle parts through pipeline 13, in tower, flow contact reacts with the hydrogen entering from tower bottom from pipeline 20 in stripping section hydrogenating desulfurization alcohol catalyst superinverse downwards, regeneration mercaptan and hydrogen reaction in heavy naphtha remove, and generate H
2s.At the bottom of tower, liquid flows out from pipeline 21, a part obtains the heavy petrol heavy constituent after mercaptan removal through pipeline 23, another part enters reboiler 25 through pipeline 24 and vaporizes, return in tower through pipeline 26, a part of light constituent of heavy petrol distillates from top of tower, enter condenser 27 through pipeline 22 and carry out condensation, enter gas-liquid separator 29 through pipeline 28 again, draw and reclaim through pipeline 30 from gas-liquid separator 29 tops hydrogen-rich gas out, reflux through pipeline 31 from a gas-liquid separator 29 bottoms liquid product part out, the heavy petrol light constituent of another part after pipeline 32 caterpillars obtain separation.After the de-H2S of petroleum naphtha after refining, through pipeline 24, the heavy petrol light constituent after separating is mixed into full distillation gasoline product through pipeline 33 and sends through pipeline 34 with heavy petrol heavy constituent after mercaptan removal.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Catalyzer used in embodiment and comparative example is produced by Sinopec catalyzer Chang Ling branch office, and trade names are RSS-1A, and its chief component is, in total catalyst weight, and the NiO that contains 4.5wt%, the WO of 14.5wt%
3al with surplus
2o
3.
Comparative example 1
Gasoline stocks is catalytically cracked gasoline, first 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 through Merox catalytic oxidation desulfurization alcohol technique, catalyzer is RDM-02 catalyzer, by Sinopec catalyzer Chang Ling, branch office produces, sulfonated phthalocyanine cobalt contents is greater than 1%.Reaction conditions: 40 DEG C of temperature, normal pressure, volume space velocity 4h when liquid
-1.After hydrogenation, heavy petrol, air sweetening heavy petrol character are in table 2, and as can be seen from Table 2, in the heavy naphtha after air sweetening, mercaptan is less than 10 μ g/g, and total sulfur and octane value do not become substantially.After air sweetening, after heavy naphtha and caustic wash desulfuration alcohol, light gasoline fraction is mixed to get gasoline products, and character is in table 3.Gasoline products mercaptans content is less than 10 μ g/g as can be seen from Table 3, and sulphur content is less than 150 μ g/g, meets Europe III emission standard, 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 example 1.Different is that after hydrogenating desulfurization, heavy naphtha is introduced in stripping tower.Described stripping tower diameter is 32mm, is highly 4m, and charging is highly 1m above, the hole random packing of filling Φ 3mm rolling metal.Opening for feed loads mercaptan-eliminating catalyst RSS-1A 140g altogether below, and stripping tower working pressure is 1.3MPa, and beds medial temperature is 220 DEG C, inlet amount is 700g/h, and feed hydrogen oil ratio is 25, and bottom product part is returned to stripping tower after reboiler heating, part discharging, load 500g/h.Tower top discharging is non-condensable gas discharge after condensation, liquid-phase product partial reflux, part discharging, reflux ratio 0.5.Tower top liquid-phase product removes H wherein through further stripping
2after S with mercaptan removal after gasoline last running Product mix obtain heavy naphtha after mercaptan removal, its character is in table 2.Be mixed to get gasoline products with the gasoline lighting end after caustic wash desulfuration alcohol, gasoline products character is in table 3.
As can be seen from Table 2, by the present embodiment, compared with comparative example, the mercaptans content of gasoline last running product drops to and is less than 3 μ g/g from 9 μ g/g, and sulphur content is fallen by 90 μ g/g and dropped to 60 μ g/g, and product loss of octane number increases by 0.1.In mixed gasoline products, mercaptans content is less than 3 μ g/g, and sulphur content drops to 41 μ g/g, and product sulphur content meets Europe IV emission standard, and comparative example product can only meet Europe III emission standard., upgrade to and meet Europe IV emission standard by meeting Europe III emission standard, and product RON loss of octane number only increases by 0.1 compared with comparative example by the present embodiment gained gasoline products.
Comparative example 2
Gasoline fractionation process is identical with comparative example 1, and the heavy naphtha after cutting is through deep hydrodesulfurizationof, and product property is in table 4, wherein product sulphur content 28 μ g/g, and mercaptans content 19 μ g/g, mercaptans content accounts for 67.8% of total sulfur.Heavy naphtha after hydrogenation is without air sweetening, but further in fixed bed, contact and carry out hydro-sweetening reaction with hydrogen, catalyzer RSS-1A, the pressure of hydro-sweetening reaction is 1.6MPa, temperature is 230 DEG C, hydrogen-oil ratio is 150, and feed volume air speed is 5h
-1.Obtain heavy naphtha after hydro-sweetening, character is as shown in table 2.By hydro-sweetening, product mercaptan is less than 8 μ g/g, and total sulfur is down to 20 μ g/g, but product research method octane value (RON) reduces 4.5.Light gasoline fraction after heavy naphtha after mercaptan removal and caustic wash desulfuration alcohol is mixed to get gasoline products, and character is in table 5.Product mercaptans content is less than 10 μ g/g as can be seen from Table 5, and sulphur content is less than 50 μ g/g, meets Europe IV emission standard, and product octane value RON loss is less than 2.5.
Embodiment 2
Gasoline fractionation, heavy naphtha hydrodesulfurization process are identical with embodiment 1.Heavy naphtha after hydrogenating desulfurization is introduced hydro-sweetening in stripping tower, and stripping tower used and catalyst loading are identical with embodiment 1.Different is that stripping tower working pressure is 0.9MPa, and the following beds medial temperature of charging is 200 DEG C, and inlet amount is 700g/h, and feed hydrogen oil ratio is 10, and at the bottom of tower top, discharging is 400g/h.Tower top discharging is non-condensable gas discharge after condensation, liquid-phase product partial reflux, part discharging, reflux ratio 0.2.Tower top discharging removes H wherein through further stripping
2after S with mercaptan removal after heavy naphtha Product mix obtain the heavy naphtha after mercaptan removal, its character is in table 4.Be mixed to get gasoline products with the light gasoline fraction after caustic wash desulfuration alcohol, character is in table 5.
As can be seen from Table 3, by this enforcement, compared with comparative example, the mercaptans content of gasoline last running product drops to 3 μ g/g from 8 μ g/g, and 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 example 0.3.Mixed full cut product mercaptans content is less than 3 μ g/g, sulphur content 6.7 μ g/g, and product sulphur content meets the gasoline products of Euro V emissions., upgrade to and meet Euro V emissions by meeting Europe IV emission standard, and product octane value RON loses lower than comparative example 0.2 compared with comparative example by the present embodiment gained gasoline products.
Table 1
Table 2
Table 3
| Product property | Comparative example 1 | Embodiment 1 |
| Density (20 DEG C), g/cm 3 | 0.7216 | 0.7212 |
| Sulphur content, μ g/g | 60 | 41 |
| Mercaptans content | 6 | ＜3 |
| Volume fraction of olefins, % | 31.8 | 31.8 |
| RON | 91.3 | 91.2 |
| RON loss | 1.1 | 1.2 |
Table 4
| Product property | Gasoline last running after hydrogenation | Comparative example 2 | Embodiment 2 |
| Density (20 DEG C), g/cm 3 | 0.7694 | 0.7694 | 0.7692 |
| Sulphur, μ g/g | 28 | 20 | 10 |
| Mercaptans content, μ g/g | 19 | 8 | ＜3 |
| Volume fraction of olefins, % | 22 | 20 | 21.5 |
| RON | 86.9 | 86.6 | 86.8 |
| RON loss | 4.2 | 4.5 | 4.3 |
Table 5
| Gasoline products character | Comparative example 2 | Embodiment 2 |
| Density (20 DEG C), g/cm 3 | 0.7216 | 0.7212 |
| Sulphur content, μ g/g | 13 | 6.7 |
| Mercaptans content | 5 | ＜3 |
| Volume fraction of olefins, % | 26.7 | 28.1 |
| RON | 89.9 | 90.1 |
| RON loss | 2.5 | 2.3 |
Claims (11)
1. produce a method for low-sulphur oil, comprise that by 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 hydrogenating desulfurization to introduce counter-current reactor from middle part, counter-current reactor opening for feed is conversion zone below, filling hydrogenating desulfurization alcohol catalyst, hydrogen-rich gas is introduced by counter-current reactor bottom, heavy naphtha part is vaporizated into gaseous component and liquid phase component, liquid phase component from top to bottom flows, and carries out hydro-sweetening react on catalyzer with hydrogen counter current contact, and the liquid phase component after mercaptan removal flows out from reactor bottom; Gaseous component, unreacted hydrogen and hydrogen sulfide are discharged by counter-current reactor top; Gaseous component is mixed to get gasoline products through condensation and after removing hydrogen sulfide with the liquid phase component of discharging at the bottom of tower, the light gasoline fraction of mercaptan removal.
2. according to the method for claim 1, it is characterized in that the above part filling of described counter-current reactor opening for feed or do not load distillation filler or fractionating tray.
3. according to the method for claim 1 or 2, it is characterized in that also introducing stripping medium bottom described counter-current reactor, 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 described counter-current reactor is: pressure is 0.2～4MPa, and conversion zone temperature is 140～300 DEG C, 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 described counter-current reactor is: pressure is 0.5～2.0MPa, and conversion zone temperature is 190～250 DEG C, 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 gasoline fraction final boiling point and is not more than 120 DEG C.
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 DEG C.
8. according to the method for claim 1, it is characterized in that described hydrodesulfurization reaction condition is: temperature of reaction is 250～400 DEG C, and pressure is 0.2～6MPa, and when feeding liquid, volume space velocity is 2～15h
-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 loading in aluminum oxide and/or 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 taking catalyzer total mass as benchmark, the massfraction of described molybdenum and/or tungsten is 3%～25%, the massfraction of nickel and/or cobalt is 1%～10%.
11. according to the method for claim 1, it is characterized in that described gasoline stocks is that boiling range is 30 DEG C～230 DEG C, at least contains the petroleum hydrocarbon fraction of 5wt% alkene.
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| 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 |
| 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 |
| 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 |
| 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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| EP0832958A1 (en) * | 1996-09-24 | 1998-04-01 | Institut Francais Du Petrole | Process and apparatus for the production of low sulphur catalytically cracked gasolines |
| CN1465668A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline |
| CN101787307A (en) * | 2009-01-22 | 2010-07-28 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0832958A1 (en) * | 1996-09-24 | 1998-04-01 | Institut Francais Du Petrole | Process and apparatus for the production of low sulphur catalytically cracked gasolines |
| CN1465668A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline |
| CN101787307A (en) * | 2009-01-22 | 2010-07-28 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
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