CN105733672A - Ultra low sulfur gasoline combination production method - Google Patents
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Abstract
The invention discloses an ultra low sulfur gasoline combination production method including the steps of: mixing and pre-heating full-range fluid catalytic cracking (FCC) gasoline and hydrogen, performing pre-hydrogenation, removing part of dialkene from the FCC gasoline raw material, and performing a heavy process on part of a light sulfide; introducing a reacted discharging object into a fractionating tower, fractionating the reacted discharging object into light gasoline and heavy gasoline at the temperature of 65-100 DEG C, and controlling a light gasoline sulfur content within 20-50mug/g; mixing the heavy gasoline flowed from the fractionating tower with the hydrogen, entering a hydrogenation modified reactor for aromatization/isomerization and improving the octane number, introducing reacted discharging object into a hydrodesulfurization reactor for selective hydrodesulfurization, and controlling a heavy gasoline sulfur content within 40-70mug/g; and carrying out gas-liquid separation on the hydrodesulfurized heavy gasoline, mixing the heavy gasoline with the light gasoline after hydrogen sulfide in the heavy gasoline is removed through gas stripping, entering a fixed bed hydrogen adsorption desulphurization reactor, mixing with the hydrogen for the fixed bed hydrogen adsorption desulphurization reaction, controlling the sulfur content in mixed gasoline within 10mug/g, and realizing ultra deep desulphurization on the premise of no loss of the octane number.
Description
Technical field
The present invention relates to the processing method of a kind of catalytically cracked gasoline, particularly a kind of combined technical method producing super-low sulfur clean gasoline with catalytically cracked gasoline.
Background technology
State's V gasoline standard (sulfur content is not higher than 10 μ g/g) will perform in China in 1 day January in 2018, the desulfurization of catalytic cracking (FCC) gasoline is the key of China's gasoline cleaning, and FCC gasoline ultra-deep desulfurization (sulfur content is not higher than the 10 μ g/g) technology of exploitation advanced person has become the difficult problem that petroleum refining industry of China faces.
At present, the technology path of hydrodesulfurization is mainly walked in whole world FCC gasoline desulfurization.The feature that China's FCC gasoline sulfur content is high, olefin(e) centent is high, major part refinery achieves state's IV quality of gasoline upgrading by the technology path of hydrodesulfurization, but when hydrodesulfurization technology (such as Prime-G+ technology, CDHydro/CDHDS technology, OCT-M technology, RSDS technique etc.) produces the super low-sulfur oil meeting state's V standard, the greater loss of octane number can be caused, it is difficult to meet the cost-effectiveness requirement of refinery while deep desulfuration.
Zhao Leping et al. (petroleum refining and chemical industry, 2012,43 (8): 13.) a kind of catalytically cracked gasoline ultra-deep desulfurization technique is described, adopting full fraction FCC gasoline to enter fractionating column fractional distillation is light gasoline and heavy petrol, sulfur content is down to 10 below μ g/g by light gasoline after alkali-free sweetening and absorption fractionating column, sulfur content is down to 10 below μ g/g by hydrodesulfurization by heavy petrol, finally light, the heavy petrol after desulfurization is mixed to get the super low-sulfur oil that sulfur content is not more than 10 μ g/g.This technique belongs to the type of skill of FCC gasoline selective hydrodesulfurization, although the production of super low-sulfur oil can be realized, but loss of octane number is relatively big, more than 2 units, it is impossible to avoid the FCC gasoline selective hydrodesulfurization technology shortcoming that loss of octane number is bigger under high desulfurization rate.
China Patent Publication No. CN102010751A, describe the efficient combination production method of a kind of ultra-low sulfur and high-octane number gasoline, full fraction FCC gasoline raw material is adopted to carry out low temperature orientation sulfur transfer reaction under hydro condition, then oil product cuts fractional distillation is weight gasoline fraction, counterweight distillation gasoline carries out selective hydrodesulfurization and supplementary desulfurization-hydro carbons isomery/aromatization processes, by the heavy distillat gasoline mixing after light fraction gasoline and process, obtain the gasoline products of ultra-low sulfur and high-octane number.Isomery aromatization is mainly with the alkene in heavy petrol for converting object, isomery aromatization process is carried out again after first carrying out hydrodesulfurization due to this technique heavy petrol, in heavy petrol deep desulfurization process by saturated a large amount of alkene, greatly reduce the olefin(e) centent entered in isomery aromatization reactor gasoline, be unfavorable for giving full play to isomery aromatisation function.
China Patent Publication No. CN102899083A, describe a kind of full fraction FCC gasoline ultra-deep desulfurization combined method, first complete for FCC distillation gasoline is removed in dialkene removal reactor alkadienes, then removing the sulfur of 40-60% in selective hydrodesulfurization reactor, the sulfur in FCC gasoline is down to 10 below μ g/g through absorption desulfurization reactor by the FCC gasoline after gas-liquid separation and air stripping.This technique can realize the production of super low-sulfur oil, and the ADSORPTION IN A FIXED BED desulfurization technology adopted is in ultra-deep desulfurization process loss of octane number relatively low (0.7-0.8 unit), but carry out hydrotreatment owing to full fraction FCC gasoline is directly entered selective hydrodesulfurization reactor by this technique, FCC gasoline sulfur content is down to 76 μ g/g by 165.6 μ g/g, when desulfurization degree 54%, octane number (RON) loss reaches 0.6 unit, realizing ultra-deep desulfurization RON and lose 1.3-1.4 unit, loss of octane number is bigger.
Summary of the invention
It is an object of the invention to, it is provided that the combination production method of a kind of super low-sulfur oil so that it is while ultra-deep desulfurization, keep octane number preferably.
For achieving the above object, the present invention provides the combination production method of a kind of super low-sulfur oil, comprises the following steps:
1) catalytic gasoline of whole fraction is mixed with hydrogen, enter pre-hydrogenator after preheating and be hydrogenated with in advance, the part alkadienes in elimination catalytically cracked gasoline raw material, and by part lightweight sulfide heaviness；
2) by step 1) reaction effluent introducing fractionating column, at 65-100 DEG C, fractional distillation is light gasoline and heavy petrol, and light gasoline sulfur content controls at 20-50 μ g/g；
3) by step 2) heavy petrol that goes out of fractionation column underflow and hydrogen is mixed into hydro-upgrading reactor and carries out aromatisation and isomerization upgrading reacts, and improves octane number；
4) by step 3) reaction effluent enter hydrodesulphurisatioreactors reactors carry out selective hydrodesulfurization, remove wherein part organic sulfur compound, heavy petrol sulfur content controlled at 40-70 μ g/g；
5) by step 4) heavy petrol after hydrodesulfurization carries out gas-liquid separation, and air stripping remove after hydrogen sulfide therein with step 2) fractionator overhead light gasoline out is mixed into fixing bed and faces hydrogen adsorption desulfurization reactor, mix with hydrogen and be fixed bed and face hydrogen adsorption desulphurization reaction, remove wherein part thiophene sulphur, mercaptan sulfur, thioether sulfur, blend gasoline sulfur content is controlled within 10 μ g/g.
Wherein, in step 1) in, described pre-hydrotreating reaction condition is: hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 1.0～10.0h-1, reaction temperature 80～250 DEG C, hydrogen to oil volume ratio 1～100v/v, catalyst is catalyst for pre-hydrogenation.Pre-hydrotreating reaction condition is preferably: hydrogen dividing potential drop 2.0～3.0MPa, volume space velocity 2.0～4.0h-1, reaction temperature 80～200 DEG C, hydrogen to oil volume ratio 4～10v/v.
Wherein, described catalyst for pre-hydrogenation is: with resistant to elevated temperatures inorganic oxide for carrier, with a kind of in VI B race element (or its compound) and VIII race's element (or its compound) or the catalyst for pre-hydrogenation being combined as active component.
Wherein, described catalyst for pre-hydrogenation is: with Al2O3、SiO2、MgO、TiO2Monomer or complex are carrier, by vehicle weight 100%, the VI B race element (or its compound) of 4～10% and the one in VIII race's element (or its compound) of 6～15% or its combination as active component (such as Co, Mo, the monomer of Ni, W or complex).
Wherein, in step 2) in, light gasoline sulfur content controls at 20-50 μ g/g, and the extraction ratio of light gasoline controls at 35-55wt%.
Wherein, in step 2) in, the diene value of heavy petrol is less than 1.0gI/100g.
In step 2) in, the operating condition of fractionating column is determined by sulfur distribution situation and boiling range in FCC gasoline raw material, such as can adopt fractionation column pressure on top surface 0.7-0.75MPa, column bottom temperature 190-230 DEG C, tower top temperature 65-100 DEG C, much more as far as possible light gasoline is extracted out, to reduce the loss of octane number of heavy petrol hydrodesulfurization under ensureing the premise that light gasoline sulfur content is not more than 50 μ g/g, mercaptan sulfur is not more than 10 μ g/g.Through step 2), step 1) reaction effluent fractional distillation is light, heavy petrol, wherein light gasoline sulfur content controls at 20-50 μ g/g, the extraction ratio of light gasoline controls to be preferred at 35-55wt%, to reduce the loss of octane number of heavy petrol hydrodesulfurization, the diene value of heavy petrol is less than 1.0gI/100g, to meet the long-term operation needs of device.
Wherein, in step 3) in, the reaction condition of hydro-upgrading is hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 0.8～8.0h-1, reaction temperature 100～500 DEG C, hydrogen to oil volume ratio 100～800v/v, catalyst is catalyst for hydro-upgrading.The reaction condition of hydro-upgrading is preferably: hydrogen dividing potential drop 1.5～2.5MPa, volume space velocity 0.8～1.8h-1, reaction temperature 320～440 DEG C, hydrogen to oil volume ratio 200～400v/v.
Wherein, described catalyst for hydro-upgrading is: according to catalyst weight absolutely meter, metal oxide content 1-10%, molecular sieve content is 10-90%, and surplus is binding agent；Metal is one or more in Co, Mo, Ni, W；Molecular sieve is one or more (particularly HZSM-5 and/or HSAPO-11) in HZSM-5, HZSM-22, HZSM-23, HSAPO-11；The specific surface area of catalyst for hydro-upgrading is 200-800m2/ g, pore volume 0.10-0.55ml/g.
Wherein, in step 4) in, the reaction condition of selective hydrodesulfurization is hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 1.0～8.0h-1, reaction temperature 100～400 DEG C, hydrogen to oil volume ratio 100～800v/v, catalyst is catalyst for selectively hydrodesulfurizing.The reaction condition of selective hydrodesulfurization is preferably: hydrogen dividing potential drop 1.5～2.5MPa, volume space velocity 1.8～3.3h-1, reaction temperature 200～320 DEG C, hydrogen to oil volume ratio 200～400v/v.
Wherein, described catalyst for selectively hydrodesulfurizing is: with resistant to elevated temperatures inorganic oxide for carrier, with a kind of in VI B race element (or its compound) and VIII race's element (or its compound) or its be combined as the catalyst for selectively hydrodesulfurizing of active component.
Wherein, described catalyst for selectively hydrodesulfurizing is: with Al2O3、SiO2、MgO、TiO2Monomer or complex are carrier, by vehicle weight 100%, one in the VI B race element (or its compound) of 10～20% and 3～10% VIII race's element (or its compound) or its combination as active component (such as Co, Mo, Ni, the monomer of W or complex), and add 1～3% auxiliary agent P.
Wherein, in step 4) in, the heavy petrol sulfur content after hydrodesulphurisatioreactors reactors processes controls at 40-70 μ g/g, and the desulfurization degree of hydrodesulphurisatioreactors reactors controls at 70-85%.
Wherein, in step 5) in, fixing bed faces hydrogen adsorption desulphurization reaction condition and is: hydrogen dividing potential drop 0.2～6.0MPa, volume space velocity 1.0～8.0h-1, reaction temperature 100～500 DEG C, hydrogen to oil volume ratio 10～100v/v, catalyst is adsorption desulfurizing agent.Fixing bed faces the reaction condition of hydrogen adsorption desulfurization and is preferably: hydrogen dividing potential drop 0.5～3.0MPa, volume space velocity 1.0～3.0h-1, reaction temperature 300～420 DEG C, hydrogen to oil volume ratio 10～100v/v.
Wherein, described adsorption desulfurizing agent is with one or more in nano-ZnO, CuO, CaO, MgO for carrier, and by vehicle weight 100%, metal component is one or more in Ni, Co, Mo of 1～20%.
Wherein, in step 5) in, the content of sulfur in gasoline facing the process of hydrogen adsorption desulfurization reactor through fixing bed controls at 5-10 μ g/g, can realize with minimum loss of octane number manufacturing country V super low-sulfur oil.
Wherein, in step 5) in, the content of sulfur in gasoline facing the process of hydrogen adsorption desulfurization reactor through fixing bed controls at 1-10 μ g/g, to meet the sulfur content index of state's V gasoline；
Wherein, in step 5) in, the fixing bed of configuration at least two faces hydrogen adsorption desulfurization reactor, uses a wherein reactor to be fixed bed and faces hydrogen adsorption desulphurization reaction；When the gasoline product sulfur content in the reactor in using is more than 10 μ g/g (represent adsorption desulfurizing agent saturated), another reactor that starts to put into operation reacts, the reactor entrance regeneration stage that switching is lower；Reactor under switching regenerates qualified rear preparation and produces next time.So " reaction-regeneration-reaction " process realizes the long period of process for adsorption desulfuration unit, continuous prodution, the cycle of operation of separate unit absorption desulfurization reactor at least 6 months.
Wherein, it is nitrogen oxygen atmosphere that fixing bed faces the medium of hydrogen adsorption desulfurization reactor regeneration, oxygen volume content 1～30%, regeneration gas volume space velocity 100～1000h-1, regeneration temperature 300～600 DEG C, 20-100 hour recovery time, in regeneration gas sulfur content lower than 10 μ g/g time represent regeneration qualified.
The present invention existing FCC gasoline hydro-upgrading, sulfur removal technology basis on, hydrodesulfurization technology is coupled with ADSORPTION IN A FIXED BED desulfurization technology, both the advantage that absorption sweetening process loss of octane number is little had been played, evade again the shortcoming that the ADSORPTION IN A FIXED BED desulfurization reactor cycle of operation caused owing to adsorption desulfurizing agent sulfur capacity is little is short, in the maintenance being simultaneously achieved octane number of ultra-deep desulfurization.
Specifically, compared with being used alone FCC gasoline hydro-upgrading, desulfurization technology, the inventive method has the advantage that
(1) octane number does not lose: the combination technique route manufacturing country V gasoline of the present invention, and compared with individually adopting FCC gasoline hydro-upgrading, desulfurization technology, octane number (RON) loses 0.8 unit less；Hydrodesulphurisatioreactors reactors temperature reduces about 30 DEG C, can be greatly prolonged its service cycle.
(2) higher yield of gasoline: the combination technique route manufacturing country V gasoline of the present invention, liquid is received in more than 98%, it is ensured that higher liquid is received.
(3) by FCC gasoline pre-hydrotreating, the part alkadienes in gasoline can be removed, make hydro-upgrading, desulfurization reactor have longer cycle of operation；After the lightweight sulfide heaviness in FCC gasoline, it is ensured that cutting out more enough low-sulfur light gasoline fractions and major part alkene is retained wherein, the olefin(e) centent reduced in heavy petrol guarantees that it loses octane number less in hydrodesulfurization.
(4) fixing bed is faced hydrogen adsorption desulfurization unit arrange 2 reactors one open one standby use and can in-situ regeneration, greatly ensure that the seriality of absorption desulfurization unit operation, solve the problem that cycle of operation that the low Sulfur capacity of adsorption desulfurizing agent causes is short.
(5) product sulfur content is down to 50 μ about g/g by FCC gasoline hydro-upgrading, desulfurization technology, and octane number improves 0.5 unit, and product sulfur is down to 10 μ about g/g, about 0.8 unit of loss of octane number, uneconomical；It is high that the fixing bed of FCC gasoline faces hydrogen adsorption desulfurization technology desulfurization degree, loss of octane number is little, but sorbent suspension sulfur capacity limits, it is used alone reactor cycle of operation shorter, does not also have at present and be used alone fixing bed and face hydrogen adsorption desulfurization technology and carry out the serialization industrial report commerical test of short-term (only have report).The present invention gives full play to the feature of two technology, allow hydro-upgrading, desulfurization technology that product sulfur is down to 50 μ about g/g under the premise that octane number increases, so the content of sulfur in gasoline that fixing for entrance bed faces hydrogen adsorption desulfurization reactor is substantially reduced, while giving full play to its little feature of desulfurization loss of octane number, substantially prolongs the cycle of operation of every absorption desulfurization reactor, then ensure that the loss of octane number that combination technique can be only small produces super low-sulfur oil.The two technical unit is used in combination, and can realize part coupling in heat-exchange network design and hydrogen gas system design etc..
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Accompanying drawing explanation
Fig. 1 is the combination production method device flow chart of super low-sulfur oil of the present invention；
Wherein, accompanying drawing labelling:
The full distillation gasoline of 1:FCC
2: new hydrogen
3: pre-hydrogenator
4: fractionating column
5: light gasoline
6: heavy petrol
7: dry gas
8: hydro-upgrading reactor
9,16: high score tank
10: stripping tower
11,19: recycle hydrogen
12: sour gas
13: weight blend gasoline
14,15: absorption desulfurization reactor
17: Mixer pot
18: gasoline product
20: hydrodesulphurisatioreactors reactors
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in detail, and what listed illustrative embodiments was only used as to illustrate, it is not intended as the restriction of the present invention.
Refer to Fig. 1, it is the combination production method device flow chart of super low-sulfur oil of the present invention.For keeping octane number while ultra-deep desulfurization preferably, the present invention provides the combination production method of a kind of super low-sulfur oil, comprises the following steps:
1) catalytic gasoline of whole fraction is mixed with hydrogen, enter pre-hydrogenator after preheating and be hydrogenated with in advance, the part alkadienes in elimination catalytically cracked gasoline raw material, and by part lightweight sulfide heaviness；
2) by step 1) reaction effluent introducing fractionating column, at 65-100 DEG C, fractional distillation is light gasoline and heavy petrol, and light gasoline sulfur content controls at 20-50 μ g/g；
3) by step 2) heavy petrol that goes out of fractionation column underflow and hydrogen is mixed into hydro-upgrading reactor and carries out aromatisation and isomerization upgrading reacts, and improves octane number；
4) by step 3) reaction effluent enter hydrodesulphurisatioreactors reactors carry out selective hydrodesulfurization, remove wherein part organic sulfur compound, heavy petrol sulfur content controlled at 40-70 μ g/g；
5) by step 4) heavy petrol after hydrodesulfurization carries out gas-liquid separation, and air stripping remove after hydrogen sulfide therein with step 2) fractionator overhead light gasoline out is mixed into fixing bed and faces hydrogen adsorption desulfurization reactor, mix with hydrogen and be fixed bed and face hydrogen adsorption desulphurization reaction, remove wherein part thiophene sulphur, mercaptan sulfur, thioether sulfur, blend gasoline sulfur content is controlled within 10 μ g/g.
In conjunction with Fig. 1, the method for the present invention specifically can adopt below scheme:
nullAfter the full distillation gasoline of FCC 1 mixes with new hydrogen 2，Enter pre-hydrogenator 3 after preheating to be hydrogenated with in advance，Then pre-hydrogenator 3 bottom discharge is introduced fractionating column 4，Fractional distillation is light gasoline 5 and heavy petrol 6，Tower top dry gas 7 sends into fuel gas pipe network，The heavy petrol that fractionation column underflow goes out mixes with hydrogen，Enter hydro-upgrading reactor 8 after preheating and carry out aromatisation and the reaction of isomerization upgrading，Enter hydrodesulphurisatioreactors reactors 20 after reaction effluent heat exchange and carry out hydrodesulfurization reaction，High score tank 9 is entered after reaction effluent heat exchange，Tank deck recycle hydrogen 11 is sent into hydro-upgrading reactor 8 after removing hydrogen sulfide and is recycled，Deliver to stripping tower 10 after tank bottoms heavy gasoline components heat exchange and remove hydrogen sulfide and lighter hydrocarbons，Tower top sour gas 12 sends into sour gas pipe network，The heavy petrol that stripping tower underflow goes out mixes with new hydrogen 2 and recycle hydrogen 19 after being mixed into blend gasoline 13 heat exchange with light gasoline 5，Absorption desulfurization reactor 14 or 15 (two reactor switchings use) is entered after preheating，High score tank 16 is delivered to after reaction effluent heat exchange，Tank deck recycle hydrogen 19 is delivered to absorption desulfurization reactor 14 and is recycled，Tank bottoms gasoline products delivers to blending tank 17，Produce super low-sulfur oil product 18.
Wherein, in step 1) in, described pre-hydrotreating reaction condition is: hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 1.0～10.0h-1, reaction temperature 80～250 DEG C, hydrogen to oil volume ratio 1～100v/v, catalyst is catalyst for pre-hydrogenation.Pre-hydrotreating reaction condition is preferably: hydrogen dividing potential drop 2.0～3.0MPa, volume space velocity 2.0～4.0h-1, reaction temperature 80～200 DEG C, hydrogen to oil volume ratio 4～10v/v.
Wherein, described catalyst for pre-hydrogenation is: with resistant to elevated temperatures inorganic oxide for carrier, with a kind of in VI B race element (or its compound) and VIII race's element (or its compound) or the catalyst for pre-hydrogenation being combined as active component.
Wherein, described catalyst for pre-hydrogenation is: with Al2O3、SiO2、MgO、TiO2Monomer or complex are carrier, by vehicle weight 100%, the VI B race element (or its compound) of 4～10% and the one in VIII race's element (or its compound) of 6～15% or its combination as active component (such as Co, Mo, the monomer of Ni, W or complex).
Wherein, in step 2) in, light gasoline sulfur content controls at 20-50 μ g/g, and the extraction ratio of light gasoline controls at 35-55wt%.
Wherein, in step 2) in, the diene value of heavy petrol is less than 1.0gI/100g.
In step 2) in, the operating condition of fractionating column is determined by sulfur distribution situation and boiling range in FCC gasoline raw material, such as can adopt fractionation column pressure on top surface 0.7-0.75MPa, column bottom temperature 190-230 DEG C, tower top temperature 65-100 DEG C, much more as far as possible light gasoline is extracted out, to reduce the loss of octane number of heavy petrol hydrodesulfurization under ensureing the premise that light gasoline sulfur content is not more than 50 μ g/g, mercaptan sulfur is not more than 10 μ g/g.Through step 2), step 1) reaction effluent fractional distillation is light, heavy petrol, wherein light gasoline sulfur content controls at 20-50 μ g/g, the extraction ratio of light gasoline controls to be preferred at 35-55wt%, to reduce the loss of octane number of heavy petrol hydrodesulfurization, the diene value of heavy petrol is less than 1.0gI/100g, to meet the long-term operation needs of device.
Wherein, in step 3) in, the reaction condition of hydro-upgrading is hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 0.8～8.0h-1, reaction temperature 100～500 DEG C, hydrogen to oil volume ratio 100～800v/v, catalyst is catalyst for hydro-upgrading.The reaction condition of hydro-upgrading is preferably: hydrogen dividing potential drop 1.5～2.5MPa, volume space velocity 0.8～1.8h-1, reaction temperature 320～440 DEG C, hydrogen to oil volume ratio 200～400v/v.
Wherein, described catalyst for hydro-upgrading is: according to catalyst weight absolutely meter, metal oxide content 1-10%, molecular sieve content is 10-90%, and surplus is binding agent；Metal is one or more in Co, Mo, Ni, W；Molecular sieve is one or more (particularly HZSM-5 and/or HSAPO-11) in HZSM-5, HZSM-22, HZSM-23, HSAPO-11；The specific surface area of catalyst is 200-800m2/ g, pore volume 0.10-0.55ml/g.
Wherein, in step 4) in, the reaction condition of selective hydrodesulfurization is hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 1.0～8.0h-1, reaction temperature 100～400 DEG C, hydrogen to oil volume ratio 100～800v/v, catalyst is catalyst for selectively hydrodesulfurizing.The reaction condition of selective hydrodesulfurization is preferably: hydrogen dividing potential drop 1.5～2.5MPa, volume space velocity 1.8～3.3h-1, reaction temperature 200～320 DEG C, hydrogen to oil volume ratio 200～400v/v.
Wherein, described catalyst for selectively hydrodesulfurizing is: with resistant to elevated temperatures inorganic oxide for carrier, with a kind of in VI B race element (or its compound) and VIII race's element (or its compound) or its be combined as the catalyst for selectively hydrodesulfurizing of active component.
Wherein, described catalyst for selectively hydrodesulfurizing is: with Al2O3、SiO2、MgO、TiO2Monomer or complex are carrier, by vehicle weight 100%, one in the VI B race element (or its compound) of 10～20% and 3～10% VIII race's element (or its compound) or its combination as active component (such as Co, Mo, Ni, the monomer of W or complex), and add 1～3% auxiliary agent P.
Wherein, in step 4) in, the heavy petrol sulfur content after hydrodesulphurisatioreactors reactors processes controls at 40-70 μ g/g, and the desulfurization degree of hydrodesulphurisatioreactors reactors controls at 70-85%.
Wherein, in step 5) in, fixing bed faces hydrogen adsorption desulphurization reaction condition and is: hydrogen dividing potential drop 0.2～6.0MPa, volume space velocity 1.0～8.0h-1, reaction temperature 100～500 DEG C, hydrogen to oil volume ratio 10～100v/v, catalyst is adsorption desulfurizing agent.Fixing bed faces the reaction condition of hydrogen adsorption desulfurization and is preferably: hydrogen dividing potential drop 0.5～3.0MPa, volume space velocity 1.0～3.0h-1, reaction temperature 300～420 DEG C, hydrogen to oil volume ratio 10～100v/v.
Wherein, described adsorption desulfurizing agent is with one or more in nano-ZnO, CuO, CaO, MgO for carrier, and by vehicle weight 100%, metal component is one or more in Ni, Co, Mo of 1～20%.
Wherein, in step 5) in, the content of sulfur in gasoline facing the process of hydrogen adsorption desulfurization reactor through fixing bed controls at 5-10 μ g/g, can realize with minimum loss of octane number manufacturing country V super low-sulfur oil.
Wherein, in step 5) in, the content of sulfur in gasoline facing the process of hydrogen adsorption desulfurization reactor through fixing bed controls at 1-10 μ g/g, to meet the sulfur content index of state's V gasoline；
Wherein, in step 5) in, the fixing bed of configuration at least two faces hydrogen adsorption desulfurization reactor, uses a wherein reactor to be fixed bed and faces hydrogen adsorption desulphurization reaction；When the gasoline product sulfur content in the reactor in using is more than 10 μ g/g (represent adsorption desulfurizing agent saturated), another reactor that starts to put into operation reacts, the reactor entrance regeneration stage that switching is lower；Reactor under switching regenerates qualified rear preparation and produces next time.So " reaction-regeneration-reaction " process realizes the long period of process for adsorption desulfuration unit, continuous prodution, the cycle of operation of separate unit absorption desulfurization reactor at least 6 months.
Wherein, it is nitrogen oxygen atmosphere that fixing bed faces the medium of hydrogen adsorption desulfurization reactor regeneration, oxygen volume content 1～30%, regeneration gas volume space velocity 100～1000h-1, regeneration temperature 300～600 DEG C, 20-100 hour recovery time, in regeneration gas sulfur content lower than 10 μ g/g time represent regeneration qualified.
Embodiment a
The present embodiment provides the combination production method of a kind of super low-sulfur oil, comprises the following steps:
1) catalytic gasoline of whole fraction is mixed with hydrogen, enter pre-hydrogenator after preheating and be hydrogenated with in advance, the part alkadienes in elimination catalytically cracked gasoline raw material, and by part lightweight sulfide heaviness；Described pre-hydrotreating reaction condition is: hydrogen dividing potential drop 1.0MPa, volume space velocity 1.0h-1, reaction temperature 80 DEG C, hydrogen to oil volume ratio 1v/v, catalyst is catalyst for pre-hydrogenation；Described catalyst for pre-hydrogenation is: with Al2O3Monomer is carrier, by vehicle weight 100%, the VI B race element of 4% and VIII race's element of 6% as active component；
2) by step 1) reaction effluent introducing fractionating column, fractionation column pressure on top surface 0.7MPa, column bottom temperature 190 DEG C, tower top temperature 65 DEG C, fractional distillation is light gasoline and heavy petrol, and light gasoline sulfur content controls at 20 μ g/g；The extraction ratio of light gasoline controls at 35wt%；The diene value of heavy petrol is less than 1.0gI/100g；
3) by step 2) heavy petrol that goes out of fractionation column underflow is mixed into hydrogen that hydro-upgrading reactor carries out aromatisation, isomerization upgrading reacts, and improves octane number；The reaction condition of hydro-upgrading is hydrogen dividing potential drop 1.0MPa, volume space velocity 0.8h-1, reaction temperature 100 DEG C, hydrogen to oil volume ratio 100v/v；Catalyst is catalyst for hydro-upgrading；Described catalyst for hydro-upgrading is: according to catalyst weight absolutely meter, Co oxide content 1%, HZSM-5 molecular sieve content is 10%, and surplus is binding agent；The specific surface area of catalyst is 200m2/ g, pore volume 0.10ml/g；
4) by step 3) reaction effluent enter hydrodesulphurisatioreactors reactors carry out selective hydrodesulfurization, remove wherein part organic sulfur compound, heavy petrol sulfur content controlled at 40 μ g/g, the desulfurization degree of hydrodesulphurisatioreactors reactors controls 70%；The reaction condition of selective hydrodesulfurization is hydrogen dividing potential drop 1.0MPa, volume space velocity 1.0h-1, reaction temperature 100 DEG C, hydrogen to oil volume ratio 100v/v；Catalyst is catalyst for selectively hydrodesulfurizing；Described catalyst for selectively hydrodesulfurizing is: with Al2O3Monomer is carrier, and by vehicle weight 100%, the VI B race element of 10% and 3% VIII race's element are as active component, and add 1% auxiliary agent P；
5) by step 4) heavy petrol after hydrodesulfurization carries out gas-liquid separation, and air stripping remove after hydrogen sulfide therein with step 2) fractionator overhead light gasoline out is mixed into fixing bed and faces hydrogen adsorption desulfurization reactor, mix with hydrogen and be fixed bed and face hydrogen adsorption desulphurization reaction, remove wherein part thiophene sulphur, mercaptan sulfur, thioether sulfur, blend gasoline sulfur content is controlled within 1 μ g/g；Fixing bed faces hydrogen adsorption desulphurization reaction condition: hydrogen dividing potential drop 0.2MPa, volume space velocity 1.0h-1, reaction temperature 100 DEG C, hydrogen to oil volume ratio 10v/v, catalyst is adsorption desulfurizing agent；Described adsorption desulfurizing agent is with nano-ZnO for carrier, and by vehicle weight 100%, metal component is the Ni of 1%；
Wherein, in step 5) in, the fixing bed of configuration at least two faces hydrogen adsorption desulfurization reactor, uses a wherein reactor to be fixed bed and faces hydrogen adsorption desulphurization reaction；When the gasoline product sulfur content in the reactor in using is more than 10 μ g/g (represent adsorption desulfurizing agent saturated), another reactor that starts to put into operation reacts, the reactor entrance regeneration stage that switching is lower；Reactor under switching regenerates qualified rear preparation and produces next time.So " reaction-regeneration-reaction " process realizes the long period of process for adsorption desulfuration unit, continuous prodution, the cycle of operation of separate unit absorption desulfurization reactor at least 6 months；
Wherein, it is nitrogen oxygen atmosphere that fixing bed faces the medium of hydrogen adsorption desulfurization reactor regeneration, oxygen volume content 1%, regeneration gas volume space velocity 100h-1, regeneration temperature 300 DEG C, 20 hours recovery times, in regeneration gas sulfur content lower than 10 μ g/g time represent regeneration qualified.
Embodiment b
The present embodiment provides the combination production method of a kind of super low-sulfur oil, comprises the following steps:
1) catalytic gasoline of whole fraction is mixed with hydrogen, enter pre-hydrogenator after preheating and be hydrogenated with in advance, the part alkadienes in elimination catalytically cracked gasoline raw material, and by part lightweight sulfide heaviness；Described pre-hydrotreating reaction condition is: hydrogen dividing potential drop 6.0MPa, volume space velocity 10.0h-1, reaction temperature 250 DEG C, hydrogen to oil volume ratio 100v/v, catalyst is catalyst for pre-hydrogenation；Described catalyst for pre-hydrogenation is: with Al2O3Monomer is carrier, by vehicle weight 100%, the VI B race element of 10% and VIII race's element of 15% as active component；
2) by step 1) reaction effluent introducing fractionating column, fractionation column pressure on top surface 0.75MPa, column bottom temperature 230 DEG C, tower top temperature 100 DEG C, fractional distillation is light gasoline and heavy petrol, and light gasoline sulfur content controls at 50 μ g/g；The extraction ratio of light gasoline controls at 55wt%；The diene value of heavy petrol is less than 1.0gI/100g；
3) by step 2) heavy petrol that goes out of fractionation column underflow is mixed into hydrogen that hydro-upgrading reactor carries out aromatisation, isomerization upgrading reacts, and improves octane number；The reaction condition of hydro-upgrading is hydrogen dividing potential drop 6.0MPa, volume space velocity 8.0h-1, reaction temperature 500 DEG C, hydrogen to oil volume ratio 800v/v；Catalyst is catalyst for hydro-upgrading；Described catalyst for hydro-upgrading is: according to catalyst weight absolutely meter, Co oxide content 10%, HZSM-5 molecular sieve content is 90%, and surplus is binding agent；The specific surface area of catalyst is 800m2/ g, pore volume 0.55ml/g；
4) by step 3) reaction effluent enter hydrodesulphurisatioreactors reactors carry out selective hydrodesulfurization, remove wherein part organic sulfur compound, heavy petrol sulfur content controlled at 70 μ g/g, the desulfurization degree of hydrodesulphurisatioreactors reactors controls 85%；The reaction condition of selective hydrodesulfurization is hydrogen dividing potential drop 6.0MPa, volume space velocity 8.0h-1, reaction temperature 400 DEG C, hydrogen to oil volume ratio 800v/v；Catalyst is catalyst for selectively hydrodesulfurizing；Described catalyst for selectively hydrodesulfurizing is: with Al2O3Monomer is carrier, and by vehicle weight 100%, the VI B race element of 20% and 10% VIII race's element are as active component, and add 3% auxiliary agent P.
5) by step 4) heavy petrol after hydrodesulfurization carries out gas-liquid separation, and air stripping remove after hydrogen sulfide therein with step 2) fractionator overhead light gasoline out is mixed into fixing bed and faces hydrogen adsorption desulfurization reactor, mix with hydrogen and be fixed bed and face hydrogen adsorption desulphurization reaction, remove wherein part thiophene sulphur, mercaptan sulfur, thioether sulfur, blend gasoline sulfur content is controlled within 10 μ g/g；Fixing bed faces hydrogen adsorption desulphurization reaction condition: hydrogen dividing potential drop 6.0MPa, volume space velocity 8.0h-1, reaction temperature 500 DEG C, hydrogen to oil volume ratio 100v/v, catalyst is adsorption desulfurizing agent；Described adsorption desulfurizing agent is with nano-ZnO for carrier, and by vehicle weight 100%, metal component is the Ni of 20%；
Wherein, in step 5) in, the fixing bed of configuration at least two faces hydrogen adsorption desulfurization reactor, uses a wherein reactor to be fixed bed and faces hydrogen adsorption desulphurization reaction；When the gasoline product sulfur content in the reactor in using is more than 10 μ g/g (represent adsorption desulfurizing agent saturated), another reactor that starts to put into operation reacts, the reactor entrance regeneration stage that switching is lower；Reactor under switching regenerates qualified rear preparation and produces next time.So " reaction-regeneration-reaction " process realizes the long period of process for adsorption desulfuration unit, continuous prodution, the cycle of operation of separate unit absorption desulfurization reactor at least 6 months；
Wherein, it is nitrogen oxygen atmosphere that fixing bed faces the medium of hydrogen adsorption desulfurization reactor regeneration, oxygen volume content 30%, regeneration gas volume space velocity 1000h-1, regeneration temperature 600 DEG C, 100 hours recovery times, in regeneration gas sulfur content lower than 10 μ g/g time represent regeneration qualified.
Embodiment c
The present embodiment provides the combination production method of a kind of super low-sulfur oil, comprises the following steps:
1) catalytic gasoline of whole fraction is mixed with hydrogen, enter pre-hydrogenator after preheating and be hydrogenated with in advance, the part alkadienes in elimination catalytically cracked gasoline raw material, and by part lightweight sulfide heaviness；Described pre-hydrotreating reaction condition is: hydrogen dividing potential drop 2.0MPa, volume space velocity 2.0h-1, reaction temperature 80 DEG C, hydrogen to oil volume ratio 4v/v, catalyst is catalyst for pre-hydrogenation；Described catalyst for pre-hydrogenation is: with Al2O3Monomer is carrier, by vehicle weight 100%, the VI B race element of 4% and VIII race's element of 6% as active component；
2) by step 1) reaction effluent introducing fractionating column, fractionation column pressure on top surface 0.7MPa, column bottom temperature 190 DEG C, tower top temperature 65 DEG C, fractional distillation is light gasoline and heavy petrol, and light gasoline sulfur content controls at 20 μ g/g；The extraction ratio of light gasoline controls at 35wt%；The diene value of heavy petrol is less than 1.0gI/100g；
3) by step 2) heavy petrol that goes out of fractionation column underflow is mixed into hydrogen that hydro-upgrading reactor carries out aromatisation, isomerization upgrading reacts, and improves octane number；The reaction condition of hydro-upgrading is hydrogen dividing potential drop 1.5MPa, volume space velocity 0.8h-1, reaction temperature 320 DEG C, hydrogen to oil volume ratio 200v/v；Catalyst is catalyst for hydro-upgrading；Described catalyst for hydro-upgrading is: according to catalyst weight absolutely meter, Co oxide content 1%, HZSM-5 molecular sieve content is 10%, and surplus is binding agent；The specific surface area of catalyst is 200m2/ g, pore volume 0.10ml/g；
4) by step 3) reaction effluent enter hydrodesulphurisatioreactors reactors carry out selective hydrodesulfurization, remove wherein part organic sulfur compound, heavy petrol sulfur content controlled at 40 μ g/g, the desulfurization degree of hydrodesulphurisatioreactors reactors controls 70%；The reaction condition of selective hydrodesulfurization is hydrogen dividing potential drop 1.5MPa, volume space velocity 1.8h-1, reaction temperature 200 DEG C, hydrogen to oil volume ratio 200v/v；Catalyst is catalyst for selectively hydrodesulfurizing；Described catalyst for selectively hydrodesulfurizing is: with Al2O3Monomer is carrier, and by vehicle weight 100%, the VI B race element of 10% and 3% VIII race's element are as active component, and add 1% auxiliary agent P；
5) by step 4) heavy petrol after hydrodesulfurization carries out gas-liquid separation, and air stripping remove after hydrogen sulfide therein with step 2) fractionator overhead light gasoline out is mixed into fixing bed and faces hydrogen adsorption desulfurization reactor, mix with hydrogen and be fixed bed and face hydrogen adsorption desulphurization reaction, remove wherein part thiophene sulphur, mercaptan sulfur, thioether sulfur, blend gasoline sulfur content is controlled within 5 μ g/g；Fixing bed faces hydrogen adsorption desulphurization reaction condition: hydrogen dividing potential drop 0.5MPa, volume space velocity 1.0h-1, reaction temperature 300 DEG C, hydrogen to oil volume ratio 10v/v, catalyst is adsorption desulfurizing agent；Described adsorption desulfurizing agent is with nano-ZnO for carrier, and by vehicle weight 100%, metal component is the Ni of 1%；
Wherein, in step 5) in, the fixing bed of configuration at least two faces hydrogen adsorption desulfurization reactor, uses a wherein reactor to be fixed bed and faces hydrogen adsorption desulphurization reaction；When the gasoline product sulfur content in the reactor in using is more than 10 μ g/g (represent adsorption desulfurizing agent saturated), another reactor that starts to put into operation reacts, the reactor entrance regeneration stage that switching is lower；Reactor under switching regenerates qualified rear preparation and produces next time.So " reaction-regeneration-reaction " process realizes the long period of process for adsorption desulfuration unit, continuous prodution, the cycle of operation of separate unit absorption desulfurization reactor at least 6 months；
Wherein, it is nitrogen oxygen atmosphere that fixing bed faces the medium of hydrogen adsorption desulfurization reactor regeneration, oxygen volume content 1%, regeneration gas volume space velocity 100h-1, regeneration temperature 300 DEG C, 20 hours recovery times, in regeneration gas sulfur content lower than 10 μ g/g time represent regeneration qualified.
Embodiment d
The present embodiment provides the combination production method of a kind of super low-sulfur oil, comprises the following steps:
1) catalytic gasoline of whole fraction is mixed with hydrogen, enter pre-hydrogenator after preheating and be hydrogenated with in advance, the part alkadienes in elimination catalytically cracked gasoline raw material, and by part lightweight sulfide heaviness；Described pre-hydrotreating reaction condition is: hydrogen dividing potential drop 3.0MPa, volume space velocity 4.0h-1, reaction temperature 200 DEG C, hydrogen to oil volume ratio 10v/v, catalyst is catalyst for pre-hydrogenation；Described catalyst for pre-hydrogenation is: with Al2O3Monomer is carrier, by vehicle weight 100%, the VI B race element of 10% and VIII race's element of 15% as active component；
2) by step 1) reaction effluent introducing fractionating column, fractionation column pressure on top surface 0.75MPa, column bottom temperature 230 DEG C, tower top temperature 100 DEG C, fractional distillation is light gasoline and heavy petrol, and light gasoline sulfur content controls at 50 μ g/g；The extraction ratio of light gasoline controls at 55wt%；The diene value of heavy petrol is less than 1.0gI/100g；
3) by step 2) heavy petrol that goes out of fractionation column underflow is mixed into hydrogen that hydro-upgrading reactor carries out aromatisation, isomerization upgrading reacts, and improves octane number；The reaction condition of hydro-upgrading is hydrogen dividing potential drop 2.5MPa, volume space velocity 1.8h-1, reaction temperature 440 DEG C, hydrogen to oil volume ratio 400v/v；Catalyst is catalyst for hydro-upgrading；Described catalyst for hydro-upgrading is: according to catalyst weight absolutely meter, Co oxide content 10%, HZSM-5 molecular sieve content is 90%, and surplus is binding agent；The specific surface area of catalyst is 800m2/ g, pore volume 0.55ml/g；
4) by step 3) reaction effluent enter hydrodesulphurisatioreactors reactors carry out selective hydrodesulfurization, remove wherein part organic sulfur compound, heavy petrol sulfur content controlled at 70 μ g/g, the desulfurization degree of hydrodesulphurisatioreactors reactors controls 85%；The reaction condition of selective hydrodesulfurization is hydrogen dividing potential drop 2.5MPa, volume space velocity 3.3h-1, reaction temperature 320 DEG C, hydrogen to oil volume ratio 400v/v；Catalyst is catalyst for selectively hydrodesulfurizing；Described catalyst for selectively hydrodesulfurizing is: with Al2O3Monomer is carrier, and by vehicle weight 100%, the VI B race element of 20% and 10% VIII race's element are as active component, and add 3% auxiliary agent P.
5) by step 4) heavy petrol after hydrodesulfurization carries out gas-liquid separation, and air stripping remove after hydrogen sulfide therein with step 2) fractionator overhead light gasoline out is mixed into fixing bed and faces hydrogen adsorption desulfurization reactor, mix with hydrogen and be fixed bed and face hydrogen adsorption desulphurization reaction, remove wherein part thiophene sulphur, mercaptan sulfur, thioether sulfur, blend gasoline sulfur content is controlled within 10 μ g/g；Fixing bed faces hydrogen adsorption desulphurization reaction condition: hydrogen dividing potential drop 3.0MPa, volume space velocity 3.0h-1, reaction temperature 420 DEG C, hydrogen to oil volume ratio 100v/v, catalyst is adsorption desulfurizing agent；Described adsorption desulfurizing agent is with nano-ZnO for carrier, and by vehicle weight 100%, metal component is the Ni of 20%；
Wherein, in step 5) in, the fixing bed of configuration at least two faces hydrogen adsorption desulfurization reactor, uses a wherein reactor to be fixed bed and faces hydrogen adsorption desulphurization reaction；When the gasoline product sulfur content in the reactor in using is more than 10 μ g/g (represent adsorption desulfurizing agent saturated), another reactor that starts to put into operation reacts, the reactor entrance regeneration stage that switching is lower；Reactor under switching regenerates qualified rear preparation and produces next time.So " reaction-regeneration-reaction " process realizes the long period of process for adsorption desulfuration unit, continuous prodution, the cycle of operation of separate unit absorption desulfurization reactor at least 6 months；
Wherein, it is nitrogen oxygen atmosphere that fixing bed faces the medium of hydrogen adsorption desulfurization reactor regeneration, oxygen volume content 30%, regeneration gas volume space velocity 1000h-1, regeneration temperature 600 DEG C, 100 hours recovery times, in regeneration gas sulfur content lower than 10 μ g/g time represent regeneration qualified.
The present invention existing FCC gasoline hydro-upgrading, sulfur removal technology basis on, hydrodesulfurization technology is coupled with ADSORPTION IN A FIXED BED desulfurization technology, both the advantage that absorption sweetening process loss of octane number is little had been played, evade again the shortcoming that the ADSORPTION IN A FIXED BED desulfurization reactor cycle of operation caused owing to adsorption desulfurizing agent sulfur capacity is little is short, in the maintenance being simultaneously achieved octane number of ultra-deep desulfurization.
Specifically, compared with being used alone FCC gasoline hydro-upgrading, desulfurization technology, the inventive method has the advantage that
(1) octane number does not lose: the combination technique route manufacturing country V gasoline of the present invention, and compared with individually adopting FCC gasoline hydro-upgrading, desulfurization technology, octane number (RON) loses 0.8 unit less；Hydrodesulphurisatioreactors reactors temperature reduces about 30 DEG C, can be greatly prolonged its service cycle.
(2) higher yield of gasoline: the combination technique route manufacturing country V gasoline of the present invention, liquid is received in more than 98%, it is ensured that higher liquid is received.
(3) by FCC gasoline pre-hydrotreating, the part alkadienes in gasoline can be removed, make hydro-upgrading, desulfurization reactor have longer cycle of operation；After the lightweight sulfide heaviness in FCC gasoline, it is ensured that cutting out more enough low-sulfur light gasoline fractions and major part alkene is retained wherein, the olefin(e) centent reduced in heavy petrol guarantees that it loses octane number less in hydrodesulfurization.
(4) fixing bed is faced hydrogen adsorption desulfurization unit arrange 2 reactors one open one standby use and can in-situ regeneration, greatly ensure that the seriality of absorption desulfurization unit operation, solve the problem that cycle of operation that the low Sulfur capacity of adsorption desulfurizing agent causes is short.
(5) product sulfur content is down to 50 μ about g/g by FCC gasoline hydro-upgrading, desulfurization technology, and octane number improves 0.5 unit, and product sulfur is down to 10 μ about g/g, about 0.8 unit of loss of octane number, uneconomical；It is high that the fixing bed of FCC gasoline faces hydrogen adsorption desulfurization technology desulfurization degree, loss of octane number is little, but sorbent suspension sulfur capacity limits, it is used alone reactor cycle of operation shorter, does not also have at present and be used alone fixing bed and face hydrogen adsorption desulfurization technology and carry out the serialization industrial report commerical test of short-term (only have report).The present invention gives full play to the feature of two technology, allow hydro-upgrading, desulfurization technology that product sulfur is down to 50 μ about g/g under the premise that octane number increases, so the content of sulfur in gasoline that fixing for entrance bed faces hydrogen adsorption desulfurization reactor is substantially reduced, while giving full play to its little feature of desulfurization loss of octane number, substantially prolongs the cycle of operation of every absorption desulfurization reactor, then ensure that the loss of octane number that combination technique can be only small produces super low-sulfur oil.The two technical unit is used in combination, and can realize part coupling in heat-exchange network design and hydrogen gas system design etc..
Below by the embodiment under different technology conditions and experimental data thereof, the invention will be further described, to clearly show that its technique effect.
The raw material used in the present invention is full fraction FCC gasoline, full fraction FCC gasoline adopts two kinds of cutting schemes to cut after pre-hydrogenation, weight gasoline proportionality respectively 45%:55% and the 30%:70% of cutting scheme 1 and 2 correspondence, after cutting fractional distillation, weight gasoline property is in Table 1, and each reactor process condition is in Table 2.
Weight gasoline property under table 1FCC gasoline and different cutting scheme
The process conditions of each reactor under the different embodiment of table 2
Embodiment 1
Full fraction FCC gasoline enters pre-hydrogenator elimination part alkadienes and by after lightweight sulfide heaviness, enter fractionating column and carry out cutting fractional distillation according to cutting scheme 1, weight gasoline cutting ratio 45%:55%, heavy petrol carries out hydro-upgrading, selective hydrodesulfurization and its sulfur content is down to 60 μ g/g, heavy petrol after hydrodesulfurization is mixed into ADSORPTION IN A FIXED BED desulfurization reactor after gas-liquid separation, air stripping with light gasoline, further deep desulfuration, Fig. 1 is shown in technological process.Wherein, catalyst for pre-hydrogenation used by pre-hydrogenator is industrial agent；Hydro-upgrading agent used by heavy petrol hydro-upgrading reactor is industrial agent；Selective hydrodesulfurization agent used by heavy petrol hydrodesulphurisatioreactors reactors is industrial agent；Heavy petrol after desulfurization enters fixing bed and faces hydrogen adsorption desulfurization reactor after mixing with light gasoline, adsorption desulfurizing agent used is industrial agent, and reaction result is in Table 3.
Table 3 data show, after the hydrogenated upgrading of heavy petrol, selective hydrodesulfurization, sulfur content is reduced to 60.0 μ g/g by 387.0 original μ g/g, and after the heavy petrol after hydro-upgrading, desulfurization mixes with light gasoline, full fraction FCC gasoline RON increases by 0.5 unit；Heavy petrol after hydro-upgrading, desulfurization is mixed into fixing bed after gas-liquid separation, air stripping go out hydrogen sulfide and faces hydrogen adsorption desulfurization reactor with light gasoline, carry out ultra-deep desulfurization, sulfur content is down to 4.6 μ g/g by 51.1 μ g/g, meet the sulfur content requirement of state V standard, octane number (RON) does not lose, and total liquid yield is 98.2%.
Table 3 embodiment 1 data
Embodiment 2
Raw materials used, catalyst, cutting scheme, each reactor process condition are identical with embodiment 1, institute is the difference is that cancelling ADSORPTION IN A FIXED BED desulfurization reactor, the operation temperature of hydrodesulphurisatioreactors reactors relatively embodiment 1 is high about 30 DEG C, after the hydrogenated upgrading of heavy petrol, selective hydrodesulfurization, sulfur content is down to 8 μ g/g, directly it is in harmonious proportion with light gasoline, after light gasoline product is in harmonious proportion with heavy petrol product, sulfur content is 22.2 μ g/g, it is only capable of meeting the sulfur content requirement of state IV standard, loss of octane number 0.5 unit, total liquid yield 98.4%, concrete reaction result is in Table 4.
Table 4 embodiment 2 data
Embodiment 3
Raw materials used, catalyst, cutting scheme, each reactor process condition are identical with embodiment 1, and institute is the difference is that cancelling hydro-upgrading reactor.After heavy petrol chosen property hydrodesulfurization, sulfur content is reduced to 60.0 μ g/g by 387.0 original μ g/g, and after the heavy petrol after hydrodesulfurization mixes with light gasoline, full fraction FCC gasoline RON loses 0.5 unit；Heavy petrol after hydrodesulfurization is mixed into fixing bed after gas-liquid separation, air stripping go out hydrogen sulfide and faces hydrogen adsorption desulfurization reactor with light gasoline, carry out ultra-deep desulfurization, sulfur content is down to 4.6 μ g/g by 51.1 μ g/g, meet the sulfur content requirement of state V standard, octane number (RON) reduces by 1.1 units, and total liquid yield is 99.86%.
Table 5 embodiment 3 data
Embodiment 4
Raw materials used, catalyst and reaction process condition and embodiment 2 are identical, and institute carries out cutting fractional distillation the difference is that fractionating column according to cutting scheme 2, and weight gasoline cutting ratio 30%:70%, concrete reaction result is in Table 6.
Table 6 data show, after the hydrogenated upgrading of heavy petrol, selective hydrodesulfurization, sulfur content is down to 9.2 μ g/g, directly it is in harmonious proportion with light gasoline, after light gasoline product is in harmonious proportion with heavy petrol product, product sulfur content is 8.9 μ g/g, meet the sulfur content requirement of state's V gasoline standard, but octane number (RON) loses 0.8 unit, total liquid yield 98.4%.
Table 6 embodiment 4 data
Certainly; the present invention also can have other various embodiments; when without departing substantially from present invention spirit and essence thereof, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but these change accordingly and deform the protection domain that all should belong to the claims in the present invention.
Claims (18)
1. the combination production method of a super low-sulfur oil, it is characterised in that comprise the following steps:
1) catalytic gasoline of whole fraction is mixed with hydrogen, enter pre-hydrogenator after preheating and be hydrogenated with in advance, the part alkadienes in elimination catalytically cracked gasoline raw material, and by part lightweight sulfide heaviness；
2) by step 1) reaction effluent introducing fractionating column, at 65-100 DEG C, fractional distillation is light gasoline and heavy petrol, and light gasoline sulfur content controls at 20-50 μ g/g；
3) by step 2) heavy petrol that goes out of fractionation column underflow and hydrogen is mixed into hydro-upgrading reactor and carries out aromatisation and isomerization upgrading reacts, and improves octane number；
4) by step 3) reaction effluent enter hydrodesulphurisatioreactors reactors carry out selective hydrodesulfurization, remove wherein part organic sulfur compound, heavy petrol sulfur content controlled at 40-70 μ g/g；
5) by step 4) heavy petrol after hydrodesulfurization carries out gas-liquid separation, and air stripping remove after hydrogen sulfide therein with step 2) fractionator overhead light gasoline out is mixed into fixing bed and faces hydrogen adsorption desulfurization reactor, mix with hydrogen and be fixed bed and face hydrogen adsorption desulphurization reaction, remove wherein part thiophene sulphur, mercaptan sulfur, thioether sulfur, blend gasoline sulfur content is controlled within 10 μ g/g.
2. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 1) in, described pre-hydrotreating reaction condition is: hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 1.0～10.0h-1, reaction temperature 80～250 DEG C, hydrogen to oil volume ratio 1～100v/v, catalyst is catalyst for pre-hydrogenation.
3. the combination production method of super low-sulfur oil according to claim 2, it is characterized in that, described catalyst for pre-hydrogenation is: with resistant to elevated temperatures inorganic oxide for carrier, with a kind of in VI B race element and VIII race's element or the catalyst for pre-hydrogenation being combined as active component.
4. the combination production method of super low-sulfur oil according to claim 2, it is characterised in that described catalyst for pre-hydrogenation is: with Al2O3、SiO2、MgO、TiO2Monomer or complex are carrier, by vehicle weight 100%, the VI B race element of 4～10% and the one in VIII race's element of 6～15% or its combination as active component.
5. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 2) in, the extraction ratio of light gasoline controls at 35-55wt%.
6. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 2) in, the diene value of heavy petrol is less than 1.0gI/100g.
7. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 3) in, the reaction condition of hydro-upgrading is hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 0.8～8.0h-1, reaction temperature 100～500 DEG C, hydrogen to oil volume ratio 100～800v/v, catalyst is catalyst for hydro-upgrading.
8. the combination production method of super low-sulfur oil according to claim 7, it is characterised in that described catalyst for hydro-upgrading is: according to catalyst weight absolutely meter, metal oxide content 1-10%, molecular sieve content is 10-90%, and surplus is binding agent；Metal is one or more in Co, Mo, Ni, W；Molecular sieve is one or more in HZSM-5, HZSM-22, HZSM-23, HSAPO-11；The specific surface area of catalyst for hydro-upgrading is 200-800m2/ g, pore volume 0.10-0.55ml/g.
9. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 4) in, the reaction condition of selective hydrodesulfurization is hydrogen dividing potential drop 1.0～6.0MPa, volume space velocity 1.0～8.0h-1, reaction temperature 100～400 DEG C, hydrogen to oil volume ratio 100～800v/v, catalyst is catalyst for selectively hydrodesulfurizing.
10. the combination production method of super low-sulfur oil according to claim 9, it is characterized in that, described catalyst for selectively hydrodesulfurizing is: with resistant to elevated temperatures inorganic oxide for carrier, with a kind of in VI B race element and VIII race's element or its be combined as the catalyst for selectively hydrodesulfurizing of active component.
11. the combination production method of super low-sulfur oil according to claim 9, it is characterised in that described catalyst for selectively hydrodesulfurizing is: with Al2O3、SiO2、MgO、TiO2Monomer or complex are carrier, and by vehicle weight 100%, one in the VI B race element of 10～20% and 3～10% VIII race's element or its combination are as active component, and add 1～3% auxiliary agent P.
12. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 4) in, the desulfurization degree of hydrodesulphurisatioreactors reactors controls at 70-85%.
13. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 5) in, fixing bed faces hydrogen adsorption desulphurization reaction condition and is: hydrogen dividing potential drop 0.2～6.0MPa, volume space velocity 1.0～8.0h-1, reaction temperature 100～500 DEG C, hydrogen to oil volume ratio 10～100v/v, catalyst is adsorption desulfurizing agent.
14. the combination production method of super low-sulfur oil according to claim 13, it is characterized in that, described adsorption desulfurizing agent is with one or more in nano-ZnO, CuO, CaO, MgO for carrier, and by vehicle weight 100%, metal component is one or more in Ni, Co, Mo of 1～20%.
15. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 5) in, the content of sulfur in gasoline facing the process of hydrogen adsorption desulfurization reactor through fixing bed controls at 5-10 μ g/g.
16. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 5) in, the content of sulfur in gasoline facing the process of hydrogen adsorption desulfurization reactor through fixing bed controls at 1-10 μ g/g.
17. the combination production method of super low-sulfur oil according to claim 1, it is characterised in that in step 5) in, the fixing bed of configuration at least two faces hydrogen adsorption desulfurization reactor, uses a wherein reactor to be fixed bed and faces hydrogen adsorption desulphurization reaction；When the gasoline product sulfur content in the reactor in using is more than 10 μ g/g, another reactor that starts to put into operation reacts, the reactor entrance regeneration stage that switching is lower；Reactor under switching regenerates qualified rear preparation and produces next time.
18. the combination production method of super low-sulfur oil according to claim 17, it is characterised in that it is nitrogen oxygen atmosphere that fixing bed faces the medium of hydrogen adsorption desulfurization reactor regeneration, oxygen volume content 1～30%, regeneration gas volume space velocity 100～1000h-1, regeneration temperature 300～600 DEG C, 20-100 hour recovery time, in regeneration gas sulfur content lower than 10 μ g/g time regenerate qualified.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106381168A (en) * | 2016-11-16 | 2017-02-08 | 郝智敏 | Catalytic gasoline desulfurization method capable of satisfying maximum light gasoline etherification olefin reduction demands |
| CN106590736A (en) * | 2016-12-07 | 2017-04-26 | 陕西延长石油（集团）有限责任公司 | Full-range FCC gasoline combined desulfurization process and device |
| CN108219841A (en) * | 2018-03-26 | 2018-06-29 | 福州大学 | A kind of method for cleaning of catalytic gasoline of whole fraction |
| CN109370638A (en) * | 2018-11-13 | 2019-02-22 | 陈开龙 | The desulfurizing method by adsorption of FCC gasoline |
| WO2020052145A1 (en) * | 2018-09-11 | 2020-03-19 | 福州大学 | Method for upgrading fcc gasoline |
| CN112812864A (en) * | 2021-02-10 | 2021-05-18 | 于向真 | S-Zorb process octane number auxiliary agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
| CN101368111A (en) * | 2007-08-16 | 2009-02-18 | 中国石油天然气集团公司 | Hydrogenation modification method for catalytically cracked gasoline |
| CN101845322A (en) * | 2010-05-12 | 2010-09-29 | 中国石油天然气股份有限公司 | Production method for lowering contents of sulfur and alkene in gasoline |
| CN102634368A (en) * | 2011-02-10 | 2012-08-15 | 中国石油天然气股份有限公司 | Method for inferior gasoline modification |
| CN102634371A (en) * | 2011-02-10 | 2012-08-15 | 中国石油天然气股份有限公司 | Method for gasoline modification |
| CN102634370A (en) * | 2011-02-10 | 2012-08-15 | 中国石油天然气股份有限公司 | Method for gasoline hydrogenation modification |
| US20130240405A1 (en) * | 2010-11-19 | 2013-09-19 | Indian Oil Corporation Limited | Process for deep desulfurization of cracked gasoline with minimum octane loss |
-
2014
- 2014-12-11 CN CN201410764677.2A patent/CN105733672A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368111A (en) * | 2007-08-16 | 2009-02-18 | 中国石油天然气集团公司 | Hydrogenation modification method for catalytically cracked gasoline |
| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
| CN101845322A (en) * | 2010-05-12 | 2010-09-29 | 中国石油天然气股份有限公司 | Production method for lowering contents of sulfur and alkene in gasoline |
| US20130240405A1 (en) * | 2010-11-19 | 2013-09-19 | Indian Oil Corporation Limited | Process for deep desulfurization of cracked gasoline with minimum octane loss |
| CN102634368A (en) * | 2011-02-10 | 2012-08-15 | 中国石油天然气股份有限公司 | Method for inferior gasoline modification |
| CN102634371A (en) * | 2011-02-10 | 2012-08-15 | 中国石油天然气股份有限公司 | Method for gasoline modification |
| CN102634370A (en) * | 2011-02-10 | 2012-08-15 | 中国石油天然气股份有限公司 | Method for gasoline hydrogenation modification |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106381168A (en) * | 2016-11-16 | 2017-02-08 | 郝智敏 | Catalytic gasoline desulfurization method capable of satisfying maximum light gasoline etherification olefin reduction demands |
| CN106381168B (en) * | 2016-11-16 | 2018-06-15 | 郝智敏 | A kind of catalytic gasoline sulfur method for meeting maximum Etherification of Light FCC Gasoline Olefin decrease demand |
| CN106590736A (en) * | 2016-12-07 | 2017-04-26 | 陕西延长石油（集团）有限责任公司 | Full-range FCC gasoline combined desulfurization process and device |
| CN106590736B (en) * | 2016-12-07 | 2019-05-07 | 陕西延长石油（集团）有限责任公司 | A kind of full fraction FCC gasoline combination sulfur removal technology and equipment |
| CN108219841A (en) * | 2018-03-26 | 2018-06-29 | 福州大学 | A kind of method for cleaning of catalytic gasoline of whole fraction |
| CN108219841B (en) * | 2018-03-26 | 2019-11-05 | 福州大学 | A kind of method for cleaning of catalytic gasoline of whole fraction |
| WO2020052145A1 (en) * | 2018-09-11 | 2020-03-19 | 福州大学 | Method for upgrading fcc gasoline |
| CN109370638A (en) * | 2018-11-13 | 2019-02-22 | 陈开龙 | The desulfurizing method by adsorption of FCC gasoline |
| CN109370638B (en) * | 2018-11-13 | 2020-12-04 | 博兴兴业精细化工产业发展有限公司 | Adsorption desulfurization method of FCC gasoline |
| CN112812864A (en) * | 2021-02-10 | 2021-05-18 | 于向真 | S-Zorb process octane number auxiliary agent and preparation method thereof |
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