CN106929099A - A kind of method of inferior patrol hydro-upgrading - Google Patents
A kind of method of inferior patrol hydro-upgrading Download PDFInfo
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- CN106929099A CN106929099A CN201511025449.4A CN201511025449A CN106929099A CN 106929099 A CN106929099 A CN 106929099A CN 201511025449 A CN201511025449 A CN 201511025449A CN 106929099 A CN106929099 A CN 106929099A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of method of inferior patrol hydro-upgrading, including into pre-hydrogenator reaction after (1) catalytic gasoline mixes with hydrogen；(2) reacted into the first hydrodesulphurisatioreactors reactors after pre- hydrogenation products mix with hydrogen；(3) step (2) product enters in fractionating column, cuts into light, heavy gasoline components；(4) from fractionator overhead light petrol component out as reformulated gasoline blend component, hydro-upgrading reactor reaction is entered from after bottom of towe heavy gasoline components out and hydrogen mixing；(5) product of step (4) reacts into the second hydrodesulphurisatioreactors reactors；(6) after the cooling of step (5) product, gas-liquid separation is carried out into product separator, product separator top hydrogen out is recycled, and bottom liquid phases product enters stabilizer and removes sulfurous gas, and reformulated gasoline product is mixed to obtain with light petrol.The method of the present invention reduces the loss of octane number in gasoline hydrogenation modification while alkene and sulfur content is greatly reduced.
Description
Technical field
The present invention relates to a kind of hydrogenation modification method of catalytically cracked gasoline inferior, for reducing catalytic gasoline
In sulphur and olefin(e) centent, reduce loss of octane number.
Background technology
China's haze weather occurs frequently in recent years, and the urban air-quality in the whole nation 70% is not up to standard, car tail
Gas pollutant emission is one of important sources of big and medium-sized cities haze, and quality of gasoline upgrading turns into reduction automobile
The important measures of exhaust pollutant discharge.More than 70% component is catalytic cracking vapour in China's motor petrol
Oil, the characteristics of it has sulphur and olefin(e) centent high, therefore the key of quality of gasoline upgrading is to reduce catalysis vapour
Sulphur and olefin(e) centent in oil；But alkene is the significant contributor of octane number, using conventional hydrogenation
Desulfurating and reducing olefinic hydrocarbon technology will significantly lose the octane number of gasoline.How catalytic gasoline both desulfurization, drop alkene are realized
Hydrocarbon, keeps the multiple target of octane number again, upgrades as China quality of gasoline in the urgent need to address great
Technical barrier.
Catalyzed gasoline hydrogenation desulfurization technology is mainly divided to two major classes both at home and abroad at present.One class is that selective hydrogenation takes off
Sulphur technology：By the improvement to technique and catalyst, suppress the alkene saturated activity of catalyst, in hydrogenation
Avoid alkene by excessive saturation while desulfurization, reduce the loss of octane number of hydrodesulfurization；It is another kind of
Technology is catalytic gasoline modification technology：Hydrodesulfurization uses conventional hydrogenation catalyst, then by isomery
The reaction such as change, aromatisation is processed hydrodesulfurization gasoline, improves the octane number of gasoline to make up hydrogenation
Loss of octane number in sweetening process.
ZL200410020932.9 discloses a kind of hydrogenation modification method of inferior patrol.The method is one
Plant the process of full cut catalyzed gasoline hydrogenation desulfurization Olefin decrease.Exist in hydrogen and temperature gradually rises
Under conditions of, contacted with three kinds of catalyst, form three reaction zones.First reaction zone temperature is relatively low, makes
With Hydrobon catalyst, the diolefin in main removing gasoline；Second, third reaction zone temperature is high,
Second reaction zone uses gasoline reforming catalyst, carries out including aromatisation, isomerization and benzene alkylation reaction
Modification reaction, improve gasoline octane number, improve product quality；3rd reaction zone is added using selectivity
Hydrogen desulphurization catalyst, removes organic sulfur compound in oil to greatest extent.The method is fed using full cut, pungent
The loss of alkane value is larger.
ZL200410060574.4 discloses a kind of inferior patrol hydrogenation modifying process.Its technical process
It is：Feed gasoline is cut into light fraction and heavy distillat, wherein heavy distillat elder generation and hydrogen at 60~90 DEG C
Mixing, then with Hydrobon catalyst haptoreaction, reacted effluent again with aromatization modification be catalyzed
Agent contact carries out aromatization modification reaction, obtains high-octane rating low-sulphur oil cut；Heavy petrol after modification
Cut is mixed with light fraction or through the pretreated light fraction of removal of mercaptans again, obtains final product product gasoline.This
Patent needs that, using the method for alkali refining removal of mercaptans, the discharge of the disagreeableness alkaline residue of environment can be caused.
ZL200910080111.7 discloses a kind of adding for the ultra-deep desulfurization-recovery octane number of inferior patrol
Hydrogen method for modifying：By distillation gasoline inferior complete be cut into gently, heavy distillat, light petrol is taken off two with selectivity
Alkene catalyst and desulfurization-hydro carbons highly branched chain hydroisomerization catalyst contact；Heavy petrol is set to be reacted in first paragraph
Area contacts with catalyst for selectively hydrodesulfurizing, then in second segment reaction zone and supplement desulfurization-hydro carbons list
Branched chain isomer/aromatization catalyst contact；Light, the mixing of heavy distillat gasoline after by treatment, obtain cleaning vapour
Oil product.Light petrol after this patent is only fractionated to inferior patrol carries out de- diene treatment, and heavy petrol evaporates
Contain compared with homodiene hydrocarbon in point, the quick coking of catalyst for selectively hydrodesulfurizing, influence operation week can be caused
Phase.
ZL 201110035512.8 discloses a kind of method of inferior gasoline upgrading.The method is first to complete
Distillation gasoline carries out the de- diene treatment of selectivity, then its be cut into gently, in, weigh three components, light vapour
Directly as clean gasoline blend component, middle gasoline component is introduced into hydro-upgrading reactor and carries out aromatization oil
Change, isomerization etc. are reacted, and are then mixed into hydrodesulphurisatioreactors reactors with heavy petrol.The method of the present invention
Sulphur, olefin(e) centent in gasoline can be greatly reduced, reduces the octane number brought in upgrading processes and damages
Lose, but the bad gasoline higher for treatment thiophene content, loss of octane number during V gasoline of producing country
It is larger；Because directly being cut to gasoline after pre- hydrogenation using the patented method, to ensure light petrol sulphur
Content meets the mediation of state V and requires, need to control very low light petrol ratio (less than 25m%), as far as possible will
Thiophene is switched in heavy petrol, causes heavy petrol ratio, olefin(e) centent to rise；Due to hydro-upgrading unit drop
After middle gasoline mixes with heavy petrol after alkene limited extent, therefore modification, its sulfur content, olefin(e) centent are equal
It is higher, deep hydrodesulfurizationof need to be carried out during V gasoline of producing country, cause loss of octane number big.
US 5413698 discloses the process that a kind of two-stage method produces low sulfur clean gasoline, first will
FCC gasoline cutting fractionation, heavy petrol first passes through hydrodesulfurization, hydro-upgrading is then carried out again and recovers pungent
Alkane value, the heavy petrol hydro-upgrading product for obtaining reconciles with light petrol product again.Although the technology can give birth to
Product meets the clean gasoline of the sulphur index request of Europe IV, while can recover hydrodesulfurization by hydro-upgrading causing
Loss of octane number, but the difficult clean gasoline for meeting production Europe V sulphur index requests.
The content of the invention
It is existing to overcome it is a primary object of the present invention to provide a kind of method of inferior patrol hydro-upgrading
In technology during gasoline upgrading octane number reduction it is more, reformulated gasoline alkene and sulfur content it is higher lack
Fall into.
The object of the present invention is achieved like this, a kind of method of inferior patrol hydro-upgrading, the method bag
Include following steps：
(1) enter pre-hydrogenator after catalytic gasoline mixes with hydrogen, exist in catalyst for pre-hydrogenation
Under reacted, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 100~260 DEG C of reaction temperature,
2.0~8.0h of volume space velocity-1, 10~200v/v of hydrogen to oil volume ratio；
(2) the first hydrodesulphurisatioreactors reactors are entered after pre- hydrogenation products mix with hydrogen, in mild hydrogenation
Reacted in the presence of desulphurization catalyst, reaction condition is：1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature
200~300 DEG C, 3.0~8.0h of volume space velocity-1, 200~400v/v of hydrogen to oil volume ratio；
(3) step (2) product enters in fractionating column, in 0.5~1.0Mpa of tower top pressure, enters material temperature
90~130 DEG C of degree, 70~110 DEG C of tower top temperature cuts into light, weight at 190~230 DEG C of column bottom temperature
Gasoline component；
(4) from fractionator overhead light petrol component out directly as reformulated gasoline blend component, from
Enter hydro-upgrading reactor after fractionation column bottom heavy gasoline components out and hydrogen mixing, change in hydrogenation
Reacted in the presence of matter catalyst, reaction condition is：1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature
320~450 DEG C, 1.0~3.0h of volume space velocity-1, 250~500v/v of hydrogen to oil volume ratio；
(5) product of step (4) enters the second hydrodesulphurisatioreactors reactors, is urged in selective hydrodesulfurization
Reacted in the presence of agent, reaction condition is：1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature 220~
350 DEG C, 2.0~5.0h of volume space velocity-1, 250~500v/v of hydrogen to oil volume ratio；And
(6) after the cooling of step (5) product, gas-liquid separation is carried out into product separator, product is separated
Device top hydrogen out is recycled after being processed through desulphurization of recycle hydrogen tower into circulating hydrogen compressor, product
Separator bottom liquid-phase product enters stabilizer, in 0.7~1.2Mpa of tower top pressure, feeding temperature
140~200 DEG C, 120~180 DEG C of tower top temperature is removed under the conditions of 180~240 DEG C of column bottom temperature and contained
Sulphur gas, reformulated gasoline product is mixed to get with light petrol.
The method of inferior patrol hydro-upgrading of the present invention, wherein, the catalyst for pre-hydrogenation carrier
The preferably mixture of aluminum oxide, silica or both, active component is preferably in the VIth B, the VIIIth race
One or more, based on catalyst weight 100%, active component oxide content is preferably 10~
30%, balance of carrier.
The method of inferior patrol hydro-upgrading of the present invention, wherein, the catalyst for pre-hydrogenation compares table
Area is preferably 100~300m2/ g, pore volume is preferably 0.2~0.6ml/g.
The method of inferior patrol hydro-upgrading of the present invention, wherein, the mild hydrogenation desulfurization catalyst
Agent carrier is preferably the mixture of aluminum oxide and hydrogen type molecular sieve, and active component is preferably the VIth B, the VIIIth
One or more in race, the molecular sieve is preferably in HZSM-5, HMCM-22, H β and HY
One or more, the molecular sieve preferably accounts for the 10~60% of catalyst weight, active component oxidation
Thing preferably accounts for the 5~15% of catalyst weight.
The method of inferior patrol hydro-upgrading of the present invention, wherein, the mild hydrogenation desulfurization catalyst
Agent specific surface area is preferably 200~400m2/ g, pore volume is preferably 0.4~0.8ml/g.
The method of inferior patrol hydro-upgrading of the present invention, wherein, the catalyst for hydro-upgrading is carried
Body is preferably the compound of aluminum oxide and molecular sieve, and active component is preferably in the VIth B, the VIIIth race
Plant or several, the molecular sieve is preferably the one kind or several in ZSM-5, Beta, SAPO molecular sieve
Kind, in terms of catalyst weight 100%, the molecular sieve content is preferably 60~90%, the activearm
Sub-oxide content is preferably 1~10%.
The method of inferior patrol hydro-upgrading of the present invention, wherein, the catalyst for hydro-upgrading ratio
Surface area is preferably 200~500m2/ g, pore volume is preferably 0.2~0.5ml/g.
The method of inferior patrol hydro-upgrading of the present invention, wherein, the selective hydrodesulfurization is urged
Agent is preferably with Al2O3、SiO2、TiO2And ZrO2In one or more be carrier, with P2O5、
K2One or more in O and MgO are auxiliary agent, and active component is preferably in VI B races, VIII race
Plant or several, based on catalyst weight 100%, active component oxide preferably accounts for 6~20%, auxiliary agent
It is preferred that accounting for 1~15%, balance of carrier；The catalyst for selectively hydrodesulfurizing specific surface area is preferably
170~270m2/ g, pore volume is preferably 0.3~0.6ml/g.
The method of inferior patrol hydro-upgrading of the present invention, wherein, the catalytic gasoline splits for catalysis
Change gasoline, sulfur content is preferably lower than or equal to 1000mg/kg, and olefin(e) centent is preferably lower than or equal to 45
V%.
Beneficial effects of the present invention：
1st, using the pre- hydrogenation technique of full distillation gasoline, the diene content in gasoline is reduced, and significantly drop
Mercaptans content in low light petrol, instead of alkali refining removal of mercaptans operation, it is to avoid the disagreeableness alkali of environment
The discharge of slag, diene content is reduced in heavy petrol, significantly extends the fortune of Hydrobon catalyst
Line period；
2nd, mild hydrogenation sulfur removal technology is carried out again after employing the pre- hydrogenation technique of full cut, is then carried out again
Weight component cuts flow, realizes the slight desulfurization of full distillation gasoline, while most of thiophene is removed, because
This can improve light petrol cutting relative to the flow that weight component cutting is directly carried out after full cut in advance hydrogenation
Ratio, reduces heavy petrol alkene and sulfur content, reduces the octane number damage that heavy petrol hydrodesulfurization is caused
Lose, be specially adapted to process thiophene content bad gasoline high；
3rd, using the flow of " desulfurization of heavy petrol first hydro-upgrading back end hydrogenation ", relative to " heavy petrol elder generation
The flow of hydrodesulfurization back end hydrogenation modification ", the olefin(e) centent of heavy petrol hydro-upgrading unit feed is high, energy
Enough ensure gasoline aromatization rate high, reduce loss of octane number；Due to catalyst for hydro-upgrading with plus
Hydrogen desulfurizing function, therefore heavy petrol experienced first slight desulfurization, then deep desulfuration relay sweetening process,
It is equally beneficial for reducing loss of octane number.
Brief description of the drawings
Fig. 1 is the flow chart of hydro-upgrading method for ungraded gasoline of the present invention.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is with technical solution of the present invention as preceding
Put and implemented, give detailed implementation method and process, but protection scope of the present invention is not limited to
Following embodiments, the experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part.
The method of inferior patrol hydro-upgrading of the invention is：Catalytic gasoline and hydrogen are mixed into pre- hydrogenation
Reactor removes alkadienes；Pre- hydrogenation products are carried out after mixing with hydrogen into the first hydrodesulphurisatioreactors reactors
Mild hydrogenation desulphurization reaction, desulfurization product enter back into fractionating column by gasoline be cut into gently, two groups of heavy petrol
Point；From the next light petrol of fractionating column ejection directly as clean gasoline blend component, go out from fractionation column base
The heavy petrol for coming be introduced into hydro-upgrading reactor carry out mild hydrogenation desulfurization and isomery aromatization,
Heavy petrol hydrogenation products enter back into the second hydrodesulphurisatioreactors reactors and carry out deep hydrodesulfurizationof reaction；From second
After hydrodesulphurisatioreactors reactors material cooling out, gas-liquid separation is carried out into product separator；From gas-liquid
Separator hydrogen out is used through desulfurization process Posterior circle, liquid-phase product enter stabilizer removing lighter hydrocarbons and
Final reformulated gasoline product is mixed to get after hydrogen sulfide with light petrol.
Technological process of the invention can also be expressed as：Enter pre-add hydrogen after gasoline stocks and hydrogen are mixed
Reactor, 1.0~3.0Mpa of hydrogen dividing potential drop, 100~260 DEG C of reaction temperature, volume space velocity 2.0~
8.0h-1, contacted with catalyst for pre-hydrogenation under the conditions of 10~200v/v of hydrogen to oil volume ratio be hydrogenated with it is anti-
Should, it is into monoolefine and anti-by diene thioetherification by the diene selective saturation of easy green coke in catalytic gasoline
Low boiling mercaptan in light petrol should be transferred in heavy petrol.Pre- hydrogenation products enter the after mixing with hydrogen
One hydrodesulphurisatioreactors reactors, in 1.0~3.0Mpa of hydrogen dividing potential drop, 200~300 DEG C of reaction temperature, volume
3.0~8.0h of air speed-1, under 200~400v/v of hydrogen to oil volume ratio with mild hydrogenation hydrodesulfurization catalyst
Mild hydrogenation desulphurization reaction is carried out, hydrogenation of total effluent desulfurization product enters fractionating column after cooling, in tower top
0.5~1.0Mpa of pressure, 90~130 DEG C of feeding temperature, 70~110 DEG C of tower top temperature, column bottom temperature
Under the conditions of 190~230 DEG C by gasoline be divided into gently, heavy gasoline components.From the light petrol that fractionating column ejection comes
Component is modification light petrol, and hydrogenation is introduced into after mixing with hydrogen from fractionation column base heavy petrol out
Reforming reactor, in 1.0~3.0Mpa of hydrogen dividing potential drop, 320~450 DEG C of reaction temperature, volume space velocity
1.0~3.0h-1, contacted with catalyst for hydro-upgrading under the conditions of 250~500v/v of hydrogen to oil volume ratio, occur
Hydrodesulfurization, aromatisation and isomerization reaction, while with the reaction such as a small amount of alkene saturation.Hydro-upgrading
Product enters back into the second hydrodesulphurisatioreactors reactors, in 1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature
220~350 DEG C, 2.0~5.0h of volume space velocity-1, under the conditions of 250~500v/v of hydrogen to oil volume ratio with choosing
The contact of selecting property Hydrobon catalyst carries out deep hydrodesulfurizationof reaction, after the cooling of hydrodesulfurization product, enters
Entering product separator separation carries out gas-liquid separation.From gas-liquid separator hydrogen out by after desulfurization process
Recycle, liquid-phase product enters product stabilizer, in 0.7~1.2Mpa of tower top pressure, feeding temperature
140~200 DEG C, 120~180 DEG C of tower top temperature, remove gasoline under the conditions of 180~240 DEG C of column bottom temperature
The lighter hydrocarbons and hydrogen sulfide of middle dissolving, are finally mixed to get reformulated gasoline product with light petrol.
Wherein, under the above-mentioned reaction condition of the first hydrodesulphurisatioreactors reactors, in the full cut of catalytic gasoline
30~50% sulfur-containing compounds will be hydrogenated removing, while the removal efficiency of thiophene is more than 60%, alkene is satisfied
10% is less than with rate；The light petrol component come from fractionating column ejection can be directly entered products pot as clear
Clean gasoline blend component, it is also possible to through Etherification of Light FCC Gasoline cell processing, remakes after lifting light petrol octane number
It is clean gasoline blend component；Initially entered from Fractionator Bottom heavy gasoline components out and hydrogen mixing plus
Hydrogen reforming reactor, contacts with catalyst for hydro-upgrading, carry out mild hydrogenation desulfurization and olefin isomerization virtue
Structureization is reacted, by heavy gasoline components sulfur content hydrogenation and removing 20~50%；Go out from hydro-upgrading reactor
The heavy petrol hydrogenation products for coming enter back into the second hydrodesulphurisatioreactors reactors, with catalyst for selectively hydrodesulfurizing
Contact, by sulfur content hydrogenation and removing to less than 50mg/kg (gasoline standard of state IV) or less than 10
Mg/kg (state V and above gasoline standard).
The present invention is applied to the hydro-upgrading of catalytically cracked gasoline inferior, and gasoline upgrading technique of the invention is adopted
Pre-processed with full distillation gasoline and mild hydrogenation desulfurization, be then separated into catalytic gasoline by fractionating column
Gently, two components are weighed, heavy petrol is using first hydro-upgrading and then the technological process of hydrodesulfurization.
When the inventive method production sulfur content is less than IV gasoline blend component of 50mg/kg states, organon is pungent
The loss of alkane value is less than 1.0 units；When production sulfur content is less than V gasoline blend component of 15mg/kg states,
Research octane number (RON) loss is less than 2.0 units；The yield of blend gasoline product is all higher than 99.0w%.
Each catalyst used in following comparative example, embodiment is identical, and specific preparation process is exemplified below：
(1) catalyst for pre-hydrogenation：Industrial alumina powder 100g is taken, 50g water is added, mediated, extruded
Shaping, 120 DEG C of drying, 500 DEG C are calcined 4 hours, then are calcined 4 hours at 900 DEG C, obtain catalyst
Carrier.By stirring and dissolving in 14g ammonium molybdates addition 45g water, 75g nickel nitrates, 12g lemons are added
Acid, stirring and dissolving is made catalyst activity metal impregnation liquid.Catalyst carrier is added into above-mentioned maceration extract
In, taken out after being impregnated 3 hours under normal temperature, it is aged 12 hours, then 120 DEG C of drying, 500 DEG C of roastings
4 hours, finished catalyst A (referring to ZL201210367401.1, being not limited to the method) is obtained.
(2) mild hydrogenation desulphurization catalyst：Take industrial boehmite powder 84g, HY molecular sieve
42g, plus sesbania powder 4g, nitric acid 3.5g, water 120g, kneading, extrusion molding, 120 DEG C of drying,
500 DEG C are calcined 4 hours, obtain catalyst carrier.Stirred during 14g ammonium molybdates are added into 55g water, plus
Enter 6g phosphoric acid, 11g cobalt nitrates, stirring and dissolving is made catalyst activity metal impregnation liquid.Using upper
Metallic solution impregnated catalyst support is stated, is aged 6 hours, then 120 DEG C of drying, 500 DEG C of roastings 4
Hour, finished catalyst B (being not limited to the method) is obtained.
(3) catalyst for hydro-upgrading：HZSM-5 molecular sieves 150g, alumina powder 40g are taken, plus
150ml concentration for 3g/100ml dilute nitric acid solution, mediate, extrusion molding, 120 DEG C drying,
500 DEG C are calcined 4 hours, obtain catalyst carrier.Take above-mentioned carrier 100g be put into 200ml molybdenums, nickel,
In the solution of lanthanum, solution concentration is MoO310g/100ml、NiO 3.5g/100ml、La2O3
1.6g/100ml, impregnates 2 hours under normal temperature, by 120 DEG C of drying of catalyst, 500 DEG C of roastings after separation of solid and liquid
Burn 4 hours, finished catalyst C is obtained and (referring to ZL200410074059.1, is not limited to the party
Method).
(4) catalyst for selectively hydrodesulfurizing：Take ZrO obtained in 50g2-Al2O3Powder, adds
10g kaliophilites, 1.25g sesbania powders, 30ml water, kneading, extrusion molding, 120 DEG C of drying, 550 DEG C
Roasting 4 hours, obtains catalyst carrier.Weigh 13g cobalt nitrates, 15g ammonium molybdates EDTA, dilute
Ammoniacal liquor complexing dissolving, adds 10g ammonium dihydrogen phosphates, 15g magnesium nitrates, and stirring and dissolving is made catalysis
Agent active metal maceration extract.Using above-mentioned metallic solution impregnated catalyst support, 4 hours are aged, then
120 DEG C of drying, 450 DEG C are calcined 4 hours, be obtained finished catalyst D (referring to
ZL201010252648.X, is not limited to the method).
Comparative example 1
With a kind of catalytically cracked gasoline as raw material, its property is shown in Table the catalytic gasoline 1 listed by 1.Catalysis vapour
It is oily first in hydrogen dividing potential drop 2.2Mpa, 110 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:1
Under the conditions of pre-processed using A catalyst, subsequently into fractionating column cut into gently, heavy petrol two
Component, fractionation column pressure on top surface 0.74Mpa, 121 DEG C of feeding temperature, 81 DEG C of tower top temperature, bottom of towe temperature
206 DEG C of degree, heavy naphtha accounts for the 65% of raw material.Heavy petrol is mixed into hydro-upgrading with hydrogen first
Reactor is in hydrogen dividing potential drop 2.0MPa, 370 DEG C of reaction temperature, volume space velocity 1.22h-1, hydrogen to oil volume ratio
250:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulphurisatioreactors reactors
In hydrogen dividing potential drop 1.8MPa, 255 DEG C of reaction temperature, volume space velocity 2.44h-1, hydrogen to oil volume ratio 250:1
Under the conditions of carry out hydrodesulfurization using D catalyst, carry out gas-liquid into product separator after product cooling
Separate, product separator top hydrogen out compresses after recycle hydrogen sulphur tower desulfurization process into recycle hydrogen
Machine is recycled, and product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.84Mpa,
154 DEG C of feeding temperature, 143 DEG C of tower top temperature removes sulfurous gas under the conditions of 213 DEG C of column bottom temperature,
Clean gasoline product is mixed to get with light petrol component.Process conditions and generation oil nature are shown in Table 2.From table
2 can be seen that product sulfur content for 41mg/kg, desulfurization degree 89.3%, and olefin(e) centent is under 41.0%
26.0% is dropped to, octane number (RON) loses 1.2 units.
Comparative example 2
The feedstock oil that comparative example 2 is used is identical with comparative example 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 120 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, subsequently into fractionating column cut into gently, two components of heavy petrol, fractionation column
Pressure on top surface 0.75Mpa, 116 DEG C of feeding temperature, 72 DEG C of tower top temperature, 202 DEG C of column bottom temperature, weight vapour
Oil distillate accounts for the 80% of raw material.Heavy petrol is mixed into hydro-upgrading reactor in hydrogen point with hydrogen first
Pressure 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:1 reaction bar
Hydro-upgrading is carried out using C catalyst under part, subsequently into hydrodesulphurisatioreactors reactors in hydrogen dividing potential drop
1.8MPa, 275 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:Used under the conditions of 1
D catalyst carries out hydrodesulfurization, and gas-liquid separation, product point are carried out into product separator after product cooling
From device top, hydrogen out is recycled after recycle hydrogen sulphur tower desulfurization process into circulating hydrogen compressor,
Product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.89Mpa, feeding temperature
151 DEG C, 141 DEG C of tower top temperature removes sulfurous gas, with light petrol under the conditions of 211 DEG C of column bottom temperature
Component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.Can from table 2
Go out, product sulfur content be 11mg/kg, desulfurization degree 97.1%, olefin(e) centent drops to from 41v%
22.3v%, octane number (RON) loses 2.2 units.
Comparative example 3
The feedstock oil that comparative example 3 is used is identical with comparative example 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 120 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, then enters hydrogenation of total effluent desulfurization reactor after mixing with hydrogen, in hydrogen dividing potential drop
2.2MPa, 240 DEG C of reaction temperature, volume space velocity 5.0h-1, hydrogen to oil volume ratio 300:1 reaction condition
Lower use B catalyst carries out hydrodesulfurization, subsequently into fractionating column cut into gently, two groups of heavy petrol
Point, fractionation column pressure on top surface 0.70Mpa, 117 DEG C of feeding temperature, 74 DEG C of tower top temperature, column bottom temperature
200 DEG C, heavy naphtha accounts for the 70% of raw material.It is anti-that heavy petrol is mixed into hydrodesulfurization with hydrogen first
Device is answered in hydrogen dividing potential drop 1.8MPa, 255 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio
300:Hydrodesulfurization is carried out using D catalyst under the conditions of 1, subsequently into hydro-upgrading reactor in hydrogen point
Pressure 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:1 reaction bar
Hydro-upgrading is carried out using C catalyst under part, gas-liquid point is carried out into product separator after product cooling
From product separator top hydrogen out enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process
Recycle, product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.89Mpa, enters
154 DEG C of material temperature degree, 144 DEG C of tower top temperature removes sulfurous gas under the conditions of 213 DEG C of column bottom temperature, with
Light petrol component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.From table 2
As can be seen that product sulfur content is 10mg/kg, desulfurization degree 97.4%, olefin(e) centent declines from 41v%
To 24.2v%, octane number (RON) 1.7 units of loss.
Embodiment 1
The feedstock oil that embodiment 1 is used is identical with comparative example 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 110 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, then enters the first hydrodesulphurisatioreactors reactors after mixing with hydrogen, in hydrogen dividing potential drop
2.2MPa, 230 DEG C of reaction temperature, volume space velocity 5.0h-1, hydrogen to oil volume ratio 250:1 reaction condition
Lower use B catalyst carries out hydrodesulfurization, and two groups of weight gasoline are cut into subsequently into fractionating column
Point, fractionation column pressure on top surface 0.74Mpa, 120 DEG C of feeding temperature, 83 DEG C of tower top temperature, column bottom temperature
207 DEG C, heavy naphtha accounts for the 60% of raw material.It is anti-that heavy petrol is mixed into hydro-upgrading with hydrogen first
Device is answered in hydrogen dividing potential drop 2.0MPa, 370 DEG C of reaction temperature, volume space velocity 1.22h-1, hydrogen to oil volume ratio
250:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulphurisatioreactors reactors
In hydrogen dividing potential drop 1.8MPa, 240 DEG C of reaction temperature, volume space velocity 2.44h-1, hydrogen to oil volume ratio 250:1
Under the conditions of carry out hydrodesulfurization using D catalyst, carry out gas-liquid into product separator after product cooling
Separate, product separator top hydrogen out compresses after recycle hydrogen sulphur tower desulfurization process into recycle hydrogen
Machine is recycled, and product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.86Mpa,
157 DEG C of feeding temperature, 145 DEG C of tower top temperature removes sulfurous gas under the conditions of 217 DEG C of column bottom temperature,
Clean gasoline product is mixed to get with light petrol component.Process conditions and generation oil nature are shown in Table 2.From table
2 can be seen that product sulfur content for 40mg/kg, desulfurization degree 89.5%, and olefin(e) centent is under 41v%
27.5v% is dropped to, octane number (RON) loses 0.5 unit.
Embodiment 2
The feedstock oil that embodiment 2 is used is identical with comparative example 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 120 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, then enters the first hydrodesulphurisatioreactors reactors after mixing with hydrogen, in hydrogen dividing potential drop
2.2MPa, 240 DEG C of reaction temperature, volume space velocity 5.0h-1, hydrogen to oil volume ratio 300:1 reaction condition
Lower use B catalyst carries out hydrodesulfurization, and two groups of weight gasoline are cut into subsequently into fractionating column
Point, fractionation column pressure on top surface 0.71Mpa, 117 DEG C of feeding temperature, 74 DEG C of tower top temperature, column bottom temperature
201 DEG C, heavy naphtha accounts for the 70% of raw material.It is anti-that heavy petrol is mixed into hydro-upgrading with hydrogen first
Device is answered in hydrogen dividing potential drop 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio
300:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulphurisatioreactors reactors
In hydrogen dividing potential drop 1.8MPa, 260 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:1
Hydrodesulfurization is carried out using D catalyst under part, gas-liquid point is carried out into product separator after product cooling
From product separator top hydrogen out enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process
Recycle, product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.87Mpa, enters
152 DEG C of material temperature degree, 142 DEG C of tower top temperature removes sulfurous gas under the conditions of 211 DEG C of column bottom temperature, with
Light petrol component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.From table 2
As can be seen that product sulfur content is 10mg/kg, desulfurization degree 97.4%, olefin(e) centent declines from 41v%
To 25.5v%, octane number (RON) 1.2 units of loss.
Embodiment 3
The feedstock oil that embodiment 3 is used is shown in Table the catalytic gasoline 2 listed by 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 120 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, then enters the first hydrodesulphurisatioreactors reactors after mixing with hydrogen, in hydrogen dividing potential drop
2.2MPa, 250 DEG C of reaction temperature, volume space velocity 5.0h-1, hydrogen to oil volume ratio 300:1 reaction condition
Lower use B catalyst carries out hydrodesulfurization, and two groups of weight gasoline are cut into subsequently into fractionating column
Point, fractionation column pressure on top surface 0.72Mpa, 115 DEG C of feeding temperature, 74 DEG C of tower top temperature, column bottom temperature
205 DEG C, heavy naphtha accounts for the 65% of raw material.It is anti-that heavy petrol is mixed into hydro-upgrading with hydrogen first
Device is answered in hydrogen dividing potential drop 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio
300:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulphurisatioreactors reactors
In hydrogen dividing potential drop 1.8MPa, 270 DEG C of reaction temperature, volume space velocity 2.5h-1, hydrogen to oil volume ratio 300:1
Hydrodesulfurization is carried out using D catalyst under part, gas-liquid point is carried out into product separator after product cooling
From product separator top hydrogen out enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process
Recycle, product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.88Mpa, enters
150 DEG C of material temperature degree, 140 DEG C of tower top temperature removes sulfurous gas under the conditions of 208 DEG C of column bottom temperature, with
Light petrol component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.From table 2
As can be seen that product sulfur content is 10mg/kg, desulfurization degree 98.6%, olefin(e) centent declines from 40v%
To 24v%, octane number (RON) 1.4 units of loss.
Table 1
Table 2
Comparative result when comparative example 1 is IV gasoline products of producing country with embodiment 1, comparative example 2 and reality
Comparative result when applying example 2 for V gasoline products of producing country.Differ primarily in that embodiments of the invention
1st, (the first hydrodesulfurization is anti-for the processing unit containing " desulfurization of full cut mild hydrogenation " of embodiment 2
Answer device), and comparative example 1, comparative example 2 do not have.Be can be seen that by the result of table 2 and contained for treatment sulphur
Amount 382mg/kg, the catalytic gasoline of alkene 41.0v%, under the desulfurization degree of IV scheme of state 89.5%, implement
Example 1 loses 0.7 unit less compared with the octane number of comparative example 1；It is real under the desulfurization degree of V scheme of state 97.4%
Apply example 2 and lose 1.0 units less compared with the octane number of comparative example 2；
Comparative result when comparative example 3 is V gasoline products of producing country with embodiment 2.Differ primarily in that
The flow of the use of embodiments of the invention 2 " desulfurization of heavy petrol first hydro-upgrading back end hydrogenation ", and comparative example
3 flows for using " heavy petrol elder generation hydrodesulfurization back end hydrogenation is modified ".Be can be seen that by the result of table 2
Under the identical desulfurization degree of V scheme of state 97.4%, embodiment 2 loses 0.5 list less compared with the octane number of comparative example 3
Position；Additionally, being urged using the another kind of the inventive method treatment sulfur content 695mg/kg, alkene 40v%
Change gasoline, under 98.6% desulfurization degree, alkene reduction 16v%, octane number only loses 1.4 units.
Beneficial effects of the present invention：
1st, using the pre- hydrogenation technique of full distillation gasoline, the diene content in gasoline is reduced, and significantly drop
Mercaptans content in low light petrol, instead of alkali refining removal of mercaptans operation, it is to avoid the disagreeableness alkali of environment
The discharge of slag, diene content is reduced in heavy petrol, significantly extends the fortune of Hydrobon catalyst
Line period；
2nd, mild hydrogenation sulfur removal technology is carried out again after employing the pre- hydrogenation technique of full cut, is then carried out again
Weight component cuts flow, realizes the slight desulfurization of full distillation gasoline, while most of thiophene is removed, because
This can improve light petrol cutting relative to the flow that weight component cutting is directly carried out after full cut in advance hydrogenation
Ratio, reduces heavy petrol alkene and sulfur content, reduces the octane number damage that heavy petrol hydrodesulfurization is caused
Lose, be specially adapted to process thiophene content bad gasoline high；
3rd, using the flow of " desulfurization of heavy petrol first hydro-upgrading back end hydrogenation ", relative to " heavy petrol elder generation
The flow of hydrodesulfurization back end hydrogenation modification ", the olefin(e) centent of heavy petrol reforming unit charging is high, Neng Goubao
Card gasoline aromatization rate high, reduces loss of octane number；Because catalyst for hydro-upgrading is de- with hydrogenation
Sulfur functional, therefore heavy petrol experienced first slight desulfurization, then deep desulfuration relay sweetening process, equally
Advantageously reduce loss of octane number.
Certainly, the present invention can also have other various embodiments, without departing substantially from spiritual and its essence of the invention
In the case of, those of ordinary skill in the art can make various corresponding changes and deformation according to the present invention,
But these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (9)
1. a kind of method of inferior patrol hydro-upgrading, it is characterised in that the method includes following step
Suddenly：
(1) enter pre-hydrogenator after catalytic gasoline mixes with hydrogen, exist in catalyst for pre-hydrogenation
Under reacted, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 100~260 DEG C of reaction temperature,
2.0~8.0h of volume space velocity-1, 10~200v/v of hydrogen to oil volume ratio；
(2) the first hydrodesulphurisatioreactors reactors are entered after pre- hydrogenation products mix with hydrogen, in mild hydrogenation
Reacted in the presence of desulphurization catalyst, reaction condition is：1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature
200~300 DEG C, 3.0~8.0h of volume space velocity-1, 200~400v/v of hydrogen to oil volume ratio；
(3) step (2) product enters in fractionating column, in 0.5~1.0Mpa of tower top pressure, enters material temperature
90~130 DEG C of degree, 70~110 DEG C of tower top temperature cuts into light, weight at 190~230 DEG C of column bottom temperature
Gasoline component；
(4) from fractionator overhead light petrol component out directly as reformulated gasoline blend component, from
Enter hydro-upgrading reactor after fractionation column bottom heavy gasoline components out and hydrogen mixing, change in hydrogenation
Reacted in the presence of matter catalyst, reaction condition is：1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature
320~450 DEG C, 1.0~3.0h of volume space velocity-1, 250~500v/v of hydrogen to oil volume ratio；
(5) product of step (4) enters the second hydrodesulphurisatioreactors reactors, is urged in selective hydrodesulfurization
Reacted in the presence of agent, reaction condition is：1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature 220~
350 DEG C, 2.0~5.0h of volume space velocity-1, 250~500v/v of hydrogen to oil volume ratio；And
(6) after the cooling of step (5) product, gas-liquid separation is carried out into product separator, product is separated
Device top hydrogen out is recycled after being processed through desulphurization of recycle hydrogen tower into circulating hydrogen compressor, product
Separator bottom liquid-phase product enters stabilizer, in 0.7~1.2Mpa of tower top pressure, feeding temperature
140~200 DEG C, 120~180 DEG C of tower top temperature is removed under the conditions of 180~240 DEG C of column bottom temperature and contained
Sulphur gas, reformulated gasoline product is mixed to get with light petrol.
2. the method for inferior patrol hydro-upgrading according to claim 1, it is characterised in that institute
It is the mixture of aluminum oxide, silica or both to state catalyst for pre-hydrogenation carrier, and active component is the VIth
One or more in B, the VIIIth race, based on catalyst weight 100%, active component oxide content
It is 10~30%, balance of carrier.
3. the method for inferior patrol hydro-upgrading according to claim 1, it is characterised in that institute
Catalyst for pre-hydrogenation specific surface area is stated for 100~300m2/ g, pore volume is 0.2~0.6ml/g.
4. the method for inferior patrol hydro-upgrading according to claim 1, it is characterised in that institute
It is the mixture of aluminum oxide and hydrogen type molecular sieve to state mild hydrogenation desulfurization catalyst agent carrier, and active component is the
One or more in VI B, the VIIIth race, the molecular sieve be HZSM-5, HMCM-22, H β and
One or more in HY, the molecular sieve accounts for the 10~60% of catalyst weight, active component oxidation
Thing accounts for the 5~15% of catalyst weight.
5. the method for inferior patrol hydro-upgrading according to claim 1, it is characterised in that institute
Mild hydrogenation desulphurization catalyst specific surface area is stated for 200~400m2/ g, pore volume is 0.4~0.8ml/g.
6. the method for inferior patrol hydro-upgrading according to claim 1, it is characterised in that institute
It is the compound of aluminum oxide and molecular sieve to state catalyst for hydro-upgrading carrier, and active component is the VIth B, the
One or more in VIII race, the molecular sieve is the one kind in ZSM-5, Beta, SAPO molecular sieve
Or it is several, in terms of catalyst weight 100%, the molecular sieve content is 60~90%, the activearm
Sub-oxide content is 1~10%.
7. the method for inferior patrol hydro-upgrading according to claim 1, it is characterised in that institute
Catalyst for hydro-upgrading specific surface area is stated for 200~500m2/ g, pore volume is 0.2~0.5ml/g.
8. the method for inferior patrol hydro-upgrading according to claim 1, it is characterised in that institute
Catalyst for selectively hydrodesulfurizing is stated with Al2O3、SiO2、TiO2And ZrO2In one or more for carry
Body, with P2O5、K2One or more in O and MgO are auxiliary agent, and active component is VI B races, VIII
One or more in race, based on catalyst weight 100%, active component oxide accounts for 6~20%,
Auxiliary agent accounts for 1~15%, balance of carrier；The catalyst for selectively hydrodesulfurizing specific surface area is
170~270m2/ g, pore volume is 0.3~0.6ml/g.
9. the method for inferior patrol hydro-upgrading according to claim 1, it is characterised in that institute
Catalytic gasoline is stated for catalytically cracked gasoline, sulfur content is less than or equal to 1000mg/kg, olefin(e) centent is small
In or equal to 45v%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109722308A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A method of producing low-sulfur, low-alkene gasoline |
| WO2020052145A1 (en) * | 2018-09-11 | 2020-03-19 | 福州大学 | Method for upgrading fcc gasoline |
| CN116144398A (en) * | 2021-11-19 | 2023-05-23 | 中国石油天然气股份有限公司 | Method and system for producing low sulfur low olefin motor gasoline blending component |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313576C (en) * | 2003-09-15 | 2007-05-02 | 中国石油化工股份有限公司 | Process for hydrogenating treatment of foulty gasoline |
| CN1313575C (en) * | 2003-09-15 | 2007-05-02 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN103468310B (en) * | 2012-06-07 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of production method of low-sulphur oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109722308A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A method of producing low-sulfur, low-alkene gasoline |
| CN109722308B (en) * | 2017-10-31 | 2021-03-12 | 中国石油化工股份有限公司 | Method for producing low-sulfur low-olefin gasoline |
| WO2020052145A1 (en) * | 2018-09-11 | 2020-03-19 | 福州大学 | Method for upgrading fcc gasoline |
| CN109652123A (en) * | 2018-12-29 | 2019-04-19 | 中海油天津化工研究设计院有限公司 | A kind of method of coker gasoline liquid phase circulation hydrogenation dialkene removal |
| CN116144398A (en) * | 2021-11-19 | 2023-05-23 | 中国石油天然气股份有限公司 | Method and system for producing low sulfur low olefin motor gasoline blending component |
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