CN106929099B - 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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- 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
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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
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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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
- 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
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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
- C10G2300/20—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)
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Abstract
It is reacted into pre-hydrogenator after being mixed with hydrogen the invention discloses a kind of method of inferior patrol hydro-upgrading, including (1) catalytic gasoline；(2) it is reacted into the first hydrodesulphurisatioreactors reactors after pre- hydrogenation products are mixed with hydrogen；(3) step (2) product enters in fractionating column, cuts into light, heavy gasoline components；(4) the light petrol component being ejected from fractionation column is as reformulated gasoline blend component, into hydro-upgrading reactor reaction after the heavy gasoline components come out from bottom of tower and hydrogen mixing；(5) product of step (4) is reacted into the second hydrodesulphurisatioreactors reactors；(6) after the cooling of step (5) product, gas-liquid separation is carried out into product separator, the hydrogen come out at the top of product separator recycles, and bottom liquid phases product enters stabilizer removing 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 in catalytic gasoline sulphur and
Olefin(e) centent reduces 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, automobile exhaust pollution object row
Put be big and medium-sized cities haze one of important sources, quality of gasoline upgrading, which becomes, reduces important arranging for automobile exhaust pollution object discharge
It applies.70% or more component is catalytically cracked gasoline in China's motor petrol, has the characteristics that sulphur and olefin(e) centent are high, therefore vapour
The key of oil quality upgrading is the sulphur and olefin(e) centent reduced in catalytic gasoline；But alkene is the main contributions of octane number
Person will substantially lose the octane number of gasoline using conventional hydrodesulfurization Olefin decrease technology.How to realize catalytic gasoline both desulfurization,
Olefin decrease, and the multiple target of octane number is kept, become China's quality of gasoline and upgrades significant technology issues in the urgent need to address.
Catalyzed gasoline hydrogenation desulfurization technology mainly divides two major classes both at home and abroad at present.One kind is selective hydrodesulfurization technology：
By the improvement to technique and catalyst, inhibits the alkene saturated activity of catalyst, alkene quilt is avoided while hydrodesulfurization
Excessive saturation, reduces the loss of octane number of hydrodesulfurization；Another kind of technology is catalytic gasoline modification technology：Hydrodesulfurization makes
With conventional hydrogenation catalyst, then hydrodesulfurization gasoline is handled by the reaction such as isomerization, aromatisation, improves gasoline
Octane number is to make up the loss of octane number in hydrodesulfurization.
ZL200410020932.9 discloses a kind of hydrogenation modification method of inferior patrol.This method is that a kind of full fraction is urged
Change the process of gasoline hydrodesulfurizationmethod Olefin decrease.Under conditions of hydrogen exists and temperature gradually rises, with three kinds of catalyst
Contact forms three reaction zones.First reaction zone temperature is relatively low, using Hydrobon catalyst, main pair removed in gasoline
Alkene；Second, third reaction zone temperature is high, and second reaction zone uses gasoline reforming catalyst, carries out including aromatisation, isomerization
Modification with benzene alkylation reaction is reacted, and the octane number of gasoline is improved, and improves product quality；Third reaction zone is added using selectivity
Hydrogen desulphurization catalyst, organic sulfur compound during removing is oily to greatest extent.This method is fed using full fraction, and loss of octane number is larger.
ZL200410060574.4 discloses a kind of inferior patrol hydrogenation modifying process.Its technical process is：By raw material vapour
Oil is cut into light fraction and heavy distillat at 60~90 DEG C, and wherein heavy distillat is first mixed with hydrogen, then is connect with Hydrobon catalyst
Reaction is touched, the effluent after reaction is contacted with aromatization modification catalyst again carries out aromatization modification reaction, obtains high-octane rating
Low-sulphur oil fraction；Heavy naphtha after modification is mixed with light fraction or through the pretreated light fraction of removal of mercaptans again,
Up to product gasoline.This patent needs the method using alkali refining removal of mercaptans, can cause the discharge of the disagreeableness alkaline residue of environment.
ZL200910080111.7 discloses a kind of hydro-upgrading side of the ultra-deep desulfurization of inferior patrol-recovery octane number
Method：Full distillation gasoline inferior is cut into light, heavy distillat, keeps light petrol and the de- diene catalyst of selectivity and desulfurization-hydro carbons more
Branch hydroisomerization catalyst contacts；Heavy petrol is set to be contacted with catalyst for selectively hydrodesulfurizing in first segment reaction zone, then
It is contacted with supplement desulfurization-hydro carbons list branched chain isomer/aromatization catalyst in second segment reaction zone；Treated by general gently, heavy distillat vapour
Oil mixing, obtains clean gasoline product.This patent only carries out de- diene to the light petrol after inferior patrol fractionation and handles, and weight vapour
Containing compared with homodiene hydrocarbon in oil distillate, the quick coking of catalyst for selectively hydrodesulfurizing can be caused, influence the cycle of operation.
ZL 201110035512.8 discloses a kind of method of inferior gasoline upgrading.This method is first to full distillation gasoline
Carry out the de- diene processing of selectivity, then its be cut into it is light, in, weigh three components, light petrol reconciles directly as clean gasoline
Component, middle gasoline component are introduced into hydro-upgrading reactor and carry out the reactions such as aromatisation, isomerization, be then mixed into heavy petrol
Enter hydrodesulphurisatioreactors reactors.Sulphur, olefin(e) centent in gasoline can be greatly reduced in the method for the present invention, reduce upgrading processes
In the loss of octane number that brings, but for handling the higher bad gasoline of thiophene content, octane number when V gasoline of producing country
It loses larger；Because directly being cut to gasoline after pre-add hydrogen using the patented method, to ensure that light petrol sulfur content meets
State V, which reconciles, to be required, and need to control very low light petrol ratio (being less than 25m%), thiophene is switched in heavy petrol as possible, leads to weight
Gasoline proportionality, olefin(e) centent rise；Due to hydro-upgrading unit Olefin decrease limited extent, middle gasoline and heavy petrol after modification
After mixing, sulfur content, olefin(e) centent are higher, and when V gasoline of producing country need to carry out deep hydrodesulfurizationof, and octane number is caused to damage
It loses big.
US 5413698 discloses a kind of process of two-stage method production low sulfur clean gasoline, first cuts FCC gasoline
Fractionation is cut, heavy petrol first passes through hydrodesulfurization, then carries out hydro-upgrading again and restores octane number, obtained heavy petrol hydro-upgrading
Product reconciles with light petrol product again.Although the technology can produce the clean gasoline for meeting IV sulphur index request of Europe, lead to simultaneously
Loss of octane number caused by hydrodesulfurization, but the difficult clean gasoline for meeting production Europe V sulphur index requests can be restored by crossing hydro-upgrading.
Invention content
The main purpose of the present invention is to provide a kind of methods of inferior patrol hydro-upgrading, to overcome vapour in the prior art
Octane number reduces more, reformulated gasoline alkene and the higher defect of sulfur content in oily upgrading processes.
The object of the present invention is achieved like this, and a kind of method of inferior patrol hydro-upgrading, this method includes following step
Suddenly：
(1) enter pre-hydrogenator after catalytic gasoline is mixed with hydrogen, reacted in the presence of catalyst for pre-hydrogenation,
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, hydrogen oil volume
Than 10~200v/v；
(2) enter the first hydrodesulphurisatioreactors reactors after pre- hydrogenation products are mixed with hydrogen, in mild hydrogenation desulphurization catalyst
In the presence of reacted, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 200~300 DEG C of reaction temperature, volume space velocity 3.0~
8.0h-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, 90~130 DEG C of feeding temperature, tower
70~110 DEG C of temperature is pushed up, light, heavy gasoline components are cut at 190~230 DEG C of column bottom temperature；
(4) the light petrol component being ejected from fractionation column is directly as reformulated gasoline blend component, from fractionation column bottom
Heavy gasoline components and hydrogen out enter hydro-upgrading reactor after mixing, and are carried out in the presence of catalyst for hydro-upgrading anti-
It answers, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 320~450 DEG C of reaction temperature, 1.0~3.0h of volume space velocity-1, hydrogen oil body
250~500v/v of product ratio；
(5) product of step (4) enter the second hydrodesulphurisatioreactors reactors, in the presence of catalyst for selectively hydrodesulfurizing into
Row reaction, reaction condition are：1.0~3.0Mpa of hydrogen partial pressure, 220~350 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, hydrogen
Oil volume is than 250~500v/v；And
(6) after the cooling of step (5) product, gas-liquid separation is carried out into product separator, is come out at the top of product separator
Hydrogen enters circulating hydrogen compressor after the processing of desulphurization of recycle hydrogen tower and recycles, and product separator bottom liquid phases product enters steady
Tower is determined, in 0.7~1.2Mpa of tower top pressure, 140~200 DEG C of feeding temperature, 120~180 DEG C of tower top temperature, column bottom temperature 180
Sulfurous gas is removed under the conditions of~240 DEG C, 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 is preferably oxygen
Change the mixture of aluminium, silica or both, active component is preferably one or more of the VIth B, the VIIIth race, by catalyst weight
100% meter of amount, active component oxide content is preferably 10~30%, and surplus is carrier.
The method of inferior patrol hydro-upgrading of the present invention, wherein the catalyst for pre-hydrogenation specific surface area is preferred
For 100~300m2/ g, it is preferably 0.2~0.6ml/g that hole, which holds,.
The method of inferior patrol hydro-upgrading of the present invention, wherein the mild hydrogenation desulfurization catalyst agent carrier is excellent
It is selected as the mixture of aluminium oxide and hydrogen type molecular sieve, active component is preferably one or more of the VIth B, the VIIIth race, described
Molecular sieve is preferably one or more of HZSM-5, HMCM-22, H β and HY, and the molecular sieve preferably accounts for catalyst weight
10~60%, active component oxide preferably accounts for the 5~15% of catalyst weight.
The method of inferior patrol hydro-upgrading of the present invention, wherein the mild hydrogenation desulphurization catalyst specific surface
Product is preferably 200~400m2/ g, it is preferably 0.4~0.8ml/g that hole, which holds,.
The method of inferior patrol hydro-upgrading of the present invention, wherein the catalyst for hydro-upgrading carrier is preferably
The compound of aluminium oxide and molecular sieve, active component are preferably one or more of the VIth B, the VIIIth race, and the molecular sieve is excellent
It is selected as one or more of ZSM-5, Beta, SAPO molecular sieve, in terms of catalyst weight 100%, the molecular sieve content is excellent
60~90% are selected as, the active component oxide content is preferably 1~10%.
The method of inferior patrol hydro-upgrading of the present invention, wherein the catalyst for hydro-upgrading specific surface area is excellent
It is selected as 200~500m2/ g, it is preferably 0.2~0.5ml/g that hole, which holds,.
The method of inferior patrol hydro-upgrading of the present invention, wherein the catalyst for selectively hydrodesulfurizing is preferred
With Al2O3、SiO2、TiO2And ZrO2One or more of be carrier, with P2O5、K2One or more of O and MgO are auxiliary agent,
Active component is preferably one or more of VI B races, VIII race, and based on catalyst weight 100%, active component oxide is preferred
6~20% are accounted for, auxiliary agent preferably accounts for 1~15%, and surplus is carrier；The catalyst for selectively hydrodesulfurizing specific surface area is preferably
170~270m2/ g, it is preferably 0.3~0.6ml/g that hole, which holds,.
The method of inferior patrol hydro-upgrading of the present invention, wherein the catalytic gasoline is catalytically cracked gasoline, sulphur
Content is preferably lower than or equal to 1000mg/kg, and olefin(e) centent is preferably lower than or equal to 45v%.
Beneficial effects of the present invention：
1, using the pre- hydrogenation technique of full distillation gasoline, the diene content in gasoline is reduced, and be greatly reduced in light petrol
Mercaptans content avoid the discharge of the disagreeableness alkaline residue of environment instead of alkali refining removal of mercaptans process, alkadienes in heavy petrol
Content is reduced, and substantially extends the cycle of operation of Hydrobon catalyst；
2, mild hydrogenation sulfur removal technology is carried out again after using the pre- hydrogenation technique of full fraction, then carries out weight group cutting again
Flow is cut, realizes the slight desulfurization of full distillation gasoline, while most of thiophene being removed, therefore relative to straight after full fraction pre-add hydrogen
The flow for tapping into the cutting of row weight component can be improved light petrol cutting ratio, reduce heavy petrol alkene and sulfur content, reduces weight vapour
Loss of octane number caused by oily hydrodesulfurization is specially adapted to the high bad gasoline of processing thiophene content；
3, using the flow of " the hydro-upgrading back end hydrogenation desulfurization of heavy petrol elder generation ", relative to " after the hydrodesulfurization of heavy petrol elder generation plus
The olefin(e) centent of the flow of hydrogen modification ", heavy petrol hydro-upgrading unit feed is high, can ensure the high aromatization rate of gasoline, subtract
Few loss of octane number；Since catalyst for hydro-upgrading is with hydrodesulfurization function, heavy petrol experienced first slight desulfurization,
The relay sweetening process of deep desulfuration again is equally beneficial for reducing loss of octane number.
Description of the drawings
Fig. 1 is the flow chart of hydro-upgrading method for ungraded gasoline of the present invention.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The method of inferior patrol hydro-upgrading of the present invention is：It is de- that catalytic gasoline and hydrogen are mixed into pre-hydrogenator
Except alkadienes；Pre- hydrogenation products enter the first hydrodesulphurisatioreactors reactors after being mixed with hydrogen and carry out mild hydrogenation desulphurization reaction, take off
Sulphur product enters back into fractionating column and gasoline is cut into light, two components of heavy petrol；The light petrol being ejected from fractionating column is directly made
For clean gasoline blend component, it is de- that the heavy petrol come out from fractionation column base is introduced into hydro-upgrading reactor progress mild hydrogenation
Sulphur and isomery aromatization, heavy petrol hydrogenation products enter back into the second hydrodesulphurisatioreactors reactors, and to carry out deep hydrodesulfurizationof anti-
It answers；After the material cooling that the second hydrodesulphurisatioreactors reactors come out, gas-liquid separation is carried out into product separator；From gas-liquid separation
Device come out hydrogen recycled after desulfurization process, liquid-phase product enter stabilizer removing lighter hydrocarbons and hydrogen sulfide after with light petrol
It is mixed to get final reformulated gasoline product.
The technological process of the present invention can also be expressed as：Enter pre-hydrogenator after gasoline stocks and hydrogen are mixed,
In 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/ of hydrogen to oil volume ratio
It is contacted with catalyst for pre-hydrogenation under the conditions of v and carries out hydrogenation reaction, the diene selective of easy green coke in catalytic gasoline is saturated into list
Alkene, and low boiling point mercaptan in light petrol is transferred in heavy petrol by diene thioetherification reaction.Pre- hydrogenation products and hydrogen
Enter the first hydrodesulphurisatioreactors reactors after mixing, in 1.0~3.0Mpa of hydrogen partial pressure, 200~300 DEG C of reaction temperature, volume space velocity
3.0~8.0h-1, with mild hydrogenation hydrodesulfurization catalyst to carry out mild hydrogenation desulfurization under 200~400v/v of hydrogen to oil volume ratio anti-
It answers, hydrogenation of total effluent desulfurization product enters fractionating column after cooling, in 0.5~1.0Mpa of tower top pressure, feeding temperature 90~130
DEG C, gasoline is divided into light, heavy gasoline components under the conditions of 70~110 DEG C of tower top temperature, 190~230 DEG C of column bottom temperature.From fractionation
The light petrol component that tower top comes out is to modify light petrol, and the heavy petrol come out from fractionation column base is introduced into after being mixed with hydrogen
Hydro-upgrading reactor, in 1.0~3.0Mpa of hydrogen partial pressure, 320~450 DEG C of reaction temperature, 1.0~3.0h of volume space velocity-1, hydrogen oil
It is contacted with catalyst for hydro-upgrading under the conditions of 250~500v/v of volume ratio, hydrodesulfurization, aromatisation and isomerization reaction occurs,
Simultaneously with reactions such as a small amount of alkene saturations.Hydro-upgrading reaction product enters back into the second hydrodesulphurisatioreactors reactors, in hydrogen partial pressure
1.0~3.0Mpa, 220~350 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, under the conditions of 250~500v/v of hydrogen to oil volume ratio
It is contacted with catalyst for selectively hydrodesulfurizing and carries out deep hydrodesulfurizationof reaction, after the cooling of hydrodesulfurization product, into product point
It is detached from device and carries out gas-liquid separation.From gas-liquid separator come out hydrogen recycled after desulfurization process, liquid-phase product into
Enter product stabilizer, in 0.7~1.2Mpa of tower top pressure, 140~200 DEG C of feeding temperature, 120~180 DEG C of tower top temperature, bottom of tower
The lighter hydrocarbons and hydrogen sulfide dissolved in gasoline are removed under the conditions of 180~240 DEG C of temperature, are finally mixed to get reformulated gasoline with light petrol
Product.
Wherein, under the above-mentioned reaction condition of the first hydrodesulphurisatioreactors reactors, 30~50% contain in the full fraction of catalytic gasoline
Sulphur compound will be hydrogenated removing, while the removal efficiency of thiophene is more than 60%, and alkene saturation factor is less than 10%；It is ejected from fractionating column
The light petrol component come can be directly entered products pot as clean gasoline blend component, can also be through Etherification of Light FCC Gasoline unit at
Reason is re-used as clean gasoline blend component after promoting light petrol octane number；The heavy gasoline components and hydrogen come out from Fractionator Bottom
Mixing initially enters hydro-upgrading reactor, is contacted 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%；The heavy petrol come out from hydro-upgrading reactor adds hydrogen
Product enters back into the second hydrodesulphurisatioreactors reactors, is contacted with catalyst for selectively hydrodesulfurizing, by sulfur content hydrogenation and removing to small
In 50mg/kg (IV gasoline standard of state) or it is less than 10mg/kg (state V and the above gasoline standard).
The present invention is suitable for the hydro-upgrading of catalytically cracked gasoline inferior, and gasoline upgrading technique of the invention uses full fraction
Gasoline pre-processes and mild hydrogenation desulfurization, then by fractionating column by catalytic gasoline be separated into it is light, weigh two components, heavy petrol is adopted
With first hydro-upgrading and then the technological process of hydrodesulfurization.
When the method for the present invention produces sulfur content less than IV gasoline blend component of 50mg/kg states, research octane number (RON) loss is small
In 1.0 units；When producing sulfur content less than V gasoline blend component of 15mg/kg states, research octane number (RON) loss is less than 2.0
Unit；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, is mediated, extrusion molding, 120 DEG C of drying,
500 DEG C roast 4 hours, then are roasted 4 hours at 900 DEG C, obtain catalyst carrier.It is molten by being stirred in 14g ammonium molybdates addition 45g water
Solution, adds 75g nickel nitrates, 12g citric acids, catalyst activity metal impregnation liquid is made in stirring and dissolving.By catalyst carrier plus
Entering in above-mentioned maceration extract, taken out after being impregnated 3 hours under room temperature, is aged 12 hours, then 120 DEG C of drying, 500 DEG C roast 4 hours,
Finished catalyst A (referring to ZL201210367401.1, being not limited to this method) is made.
(2) mild hydrogenation desulphurization catalyst：Industrial boehmite powder 84g, HY molecular sieve 42g is taken, sesbania powder 4g, nitre are added
Sour 3.5g, water 120g are mediated, extrusion molding, and 120 DEG C of drying, 500 DEG C roast 4 hours, obtain catalyst carrier.By 14g molybdic acids
Ammonium is added in 55g water and stirs, and 6g phosphoric acid, 11g cobalt nitrates is added, and catalyst activity metal impregnation liquid is made in stirring and dissolving.Using
Above-mentioned metallic solution impregnated catalyst support is aged 6 hours, and then 120 DEG C of drying, 500 DEG C roast 4 hours, and catalyst is made
Finished product B (is not limited to this method).
(3) catalyst for hydro-upgrading：HZSM-5 molecular sieves 150g, alumina powder 40g are taken, a concentration of 3g/ of 150ml are added
The dilute nitric acid solution of 100ml is mediated, extrusion molding, and 120 DEG C of drying, 500 DEG C roast 4 hours, obtain catalyst carrier.It takes
It states carrier 100g to be put into the solution of 200ml molybdenums, nickel, lanthanum, solution concentration MoO310g/100ml、NiO 3.5g/100ml、
La2O31.6g/100ml impregnates 2 hours under room temperature, and by 120 DEG C of drying of catalyst after separation of solid and liquid, 500 DEG C roast 4 hours, system
Obtain finished catalyst C (referring to ZL200410074059.1, being not limited to this method).
(4) catalyst for selectively hydrodesulfurizing：Take ZrO made from 50g2-Al2O310g kaliophilites, 1.25g is added in powder
Sesbania powder, 30ml water are mediated, extrusion molding, and 120 DEG C of drying, 550 DEG C roast 4 hours, obtain catalyst carrier.Weigh 13g nitre
Sour cobalt, 15g ammonium molybdates EDTA, weak aqua ammonia complexing dissolving, add 10g ammonium dihydrogen phosphates, 15g magnesium nitrates, stirring and dissolving, system
At catalyst activity metal impregnation liquid.Using above-mentioned metallic solution impregnated catalyst support, it is aged 4 hours, then 120 DEG C of bakings
Dry, 450 DEG C roast 4 hours, and finished catalyst D (referring to ZL201010252648.X, being not limited to this method) is made.
Comparative example 1
Using a kind of catalytically cracked gasoline as raw material, property is shown in Table the catalytic gasoline 1 listed by 1.Catalytic gasoline is first in hydrogen point
Press 2.2Mpa, 110 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:Located in advance using A catalyst under the conditions of 1
Reason cuts into light, two components of heavy petrol subsequently into fractionating column, fractionation column pressure on top surface 0.74Mpa, 121 DEG C of feeding temperature,
81 DEG C of tower top temperature, 206 DEG C of column bottom temperature, heavy naphtha accounts for the 65% of raw material.Heavy petrol is mixed into hydrogen first to be added
Hydrogen reforming reactor is in hydrogen partial pressure 2.0MPa, 370 DEG C of reaction temperature, volume space velocity 1.22h-1, hydrogen to oil volume ratio 250:1 reaction
Under the conditions of using C catalyst carry out hydro-upgrading, subsequently into hydrodesulphurisatioreactors reactors in hydrogen partial pressure 1.8MPa, reaction temperature
255 DEG C, volume space velocity 2.44h-1, hydrogen to oil volume ratio 250:Hydrodesulfurization is carried out using D catalyst under the conditions of 1, after product cooling
Gas-liquid separation is carried out into product separator, the hydrogen come out at the top of product separator enters after recycle hydrogen sulphur tower desulfurization process
Circulating hydrogen compressor recycles, and product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.84Mpa, charging
154 DEG C of temperature, 143 DEG C of tower top temperature remove sulfurous gas under the conditions of 213 DEG C of column bottom temperature, are mixed to get with light petrol component
Clean gasoline product.Process conditions and generation oil nature are shown in Table 2.From table 2 it can be seen that product sulfur content is 41mg/kg, desulfurization
Rate 89.3%, olefin(e) centent drop to 26.0% from 41.0%, and octane number (RON) loses 1.2 units.
Comparative example 2
The feedstock oil that comparative example 2 uses is identical as comparative example 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction temperature 120
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, is cut subsequently into fractionating column
At light, 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, column bottom temperature
202 DEG C, heavy naphtha accounts for the 80% of raw material.Heavy petrol is mixed into hydro-upgrading reactor in hydrogen partial pressure with hydrogen first
2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:It is carried out using C catalyst under 1 reaction condition
Hydro-upgrading, subsequently into hydrodesulphurisatioreactors reactors in hydrogen partial pressure 1.8MPa, 275 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen
Oil volume is than 300:Hydrodesulfurization is carried out using D catalyst under the conditions of 1, entering product separator after product cooling carries out gas-liquid point
From the hydrogen at the top of product separator out enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process and recycles, production
Product separator bottom liquid-phase product enters stabilizer, in tower top pressure 0.89Mpa, 151 DEG C of feeding temperature, and 141 DEG C of tower top temperature,
Sulfurous gas is removed under the conditions of 211 DEG C of column bottom temperature, clean gasoline product is mixed to get with light petrol component.Process conditions and life
It is shown in Table 2 at oil nature.From table 2 it can be seen that product sulfur content is 11mg/kg, desulfurization degree 97.1%, olefin(e) centent is from 41v%
Drop to 22.3v%, octane number (RON) loses 2.2 units.
Comparative example 3
The feedstock oil that comparative example 3 uses is identical as comparative example 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction temperature 120
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, then is entered after being mixed with hydrogen
Hydrogenation of total effluent desulfurization reactor, in hydrogen partial pressure 2.2MPa, 240 DEG C of reaction temperature, volume space velocity 5.0h-1, hydrogen to oil volume ratio
300:Hydrodesulfurization is carried out using B catalyst under 1 reaction condition, light, two groups of heavy petrol are cut into subsequently into fractionating column
Point, fractionation column pressure on top surface 0.70Mpa, 117 DEG C of feeding temperature, 74 DEG C of tower top temperature, 200 DEG C of column bottom temperature, heavy naphtha
Account for the 70% of raw material.Heavy petrol is mixed into hydrodesulphurisatioreactors reactors in hydrogen partial pressure 1.8MPa, reaction temperature 255 with hydrogen first
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:Hydrodesulfurization is carried out using D catalyst under the conditions of 1, is changed subsequently into hydrogen is added
Qualitative response device is in hydrogen partial pressure 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:1 reaction condition
It is lower that C catalyst is used to carry out hydro-upgrading, product separator is entered after product cooling and carries out gas-liquid separation, product separator top
Hydrogen out enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process and recycles, the production of product separator bottom liquid phases
Product enter stabilizer, in tower top pressure 0.89Mpa, 154 DEG C of feeding temperature, 144 DEG C of tower top temperature, 213 DEG C of conditions of column bottom temperature
Lower removing sulfurous gas is mixed to get clean gasoline product with light petrol component.Process conditions and generation oil nature are shown in Table 2.From
Table 2 is as can be seen that product sulfur content is 10mg/kg, and desulfurization degree 97.4%, olefin(e) centent drops to 24.2v% from 41v%, pungent
Alkane value (RON) loses 1.7 units.
Embodiment 1
The feedstock oil that embodiment 1 uses is identical as comparative example 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction temperature 110
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, then is entered after being mixed with hydrogen
First hydrodesulphurisatioreactors reactors, in hydrogen partial pressure 2.2MPa, 230 DEG C of reaction temperature, volume space velocity 5.0h-1, hydrogen to oil volume ratio 250:1
Reaction condition under using B catalyst carry out hydrodesulfurization, cut into two components of weight gasoline subsequently into fractionating column, be fractionated
Column overhead pressure 0.74Mpa, 120 DEG C of feeding temperature, 83 DEG C of tower top temperature, 207 DEG C of column bottom temperature, heavy naphtha accounts for raw material
60%.Heavy petrol is mixed into hydro-upgrading reactor in hydrogen partial pressure 2.0MPa, 370 DEG C of reaction temperature, volume with hydrogen first
Air speed 1.22h-1, hydrogen to oil volume ratio 250:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, it is de- subsequently into hydrogen is added
Reaction of Salmon-Saxl device is in hydrogen partial pressure 1.8MPa, 240 DEG C of reaction temperature, volume space velocity 2.44h-1, hydrogen to oil volume ratio 250:It is used under the conditions of 1
The progress hydrodesulfurization of D catalyst enters product separator and carries out gas-liquid separation, come out at the top of product separator after product cooling
Hydrogen enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process and recycles, 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 under the conditions of 217 DEG C of column bottom temperature
Sulfurous gas is mixed to get clean gasoline product with light petrol component.Process conditions and generation oil nature are shown in Table 2.It can be with from table 2
Find out, product sulfur content is 40mg/kg, and desulfurization degree 89.5%, olefin(e) centent drops to 27.5v%, octane number from 41v%
(RON) 0.5 unit is lost.
Embodiment 2
The feedstock oil that embodiment 2 uses is identical as comparative example 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction temperature 120
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, then is entered after being mixed with hydrogen
First hydrodesulphurisatioreactors reactors, in hydrogen partial pressure 2.2MPa, 240 DEG C of reaction temperature, volume space velocity 5.0h-1, hydrogen to oil volume ratio 300:1
Reaction condition under using B catalyst carry out hydrodesulfurization, cut into two components of weight gasoline subsequently into fractionating column, be fractionated
Column overhead pressure 0.71Mpa, 117 DEG C of feeding temperature, 74 DEG C of tower top temperature, 201 DEG C of column bottom temperature, heavy naphtha accounts for raw material
70%.Heavy petrol is mixed into hydro-upgrading reactor in hydrogen partial pressure 2.0MPa, 380 DEG C of reaction temperature, volume with hydrogen first
Air speed 1.5h-1, hydrogen to oil volume ratio 300:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulfurization
Reactor is in hydrogen partial pressure 1.8MPa, 260 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:It is urged using D under the conditions of 1
Agent carries out hydrodesulfurization, and product separator is entered after product cooling and carries out gas-liquid separation, the hydrogen of product separator top out
Gas enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process and recycles, and product separator bottom liquid phases product enters steady
Determine tower, in tower top pressure 0.87Mpa, 152 DEG C of feeding temperature, 142 DEG C of tower top temperature removes under the conditions of 211 DEG C of column bottom temperature and contains
Sulphur gas is mixed to get clean gasoline product with light petrol component.Process conditions and generation oil nature are shown in Table 2.It can from table 2
Go out, product sulfur content is 10mg/kg, and desulfurization degree 97.4%, olefin(e) centent drops to 25.5v%, octane number (RON) from 41v%
Lose 1.2 units.
Embodiment 3
The feedstock oil that embodiment 3 uses is shown in Table the catalytic gasoline 2 listed by 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction
120 DEG C of temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, then mixed with hydrogen
Enter the first hydrodesulphurisatioreactors reactors after conjunction, in hydrogen partial pressure 2.2MPa, 250 DEG C of reaction temperature, volume space velocity 5.0h-1, hydrogen oil body
Product ratio 300:Hydrodesulfurization is carried out using B catalyst under 1 reaction condition, two, weight gasoline is cut into subsequently into fractionating column
Component, fractionation column pressure on top surface 0.72Mpa, 115 DEG C of feeding temperature, 74 DEG C of tower top temperature, 205 DEG C of column bottom temperature, heavy petrol evaporates
Divide and accounts for the 65% of raw material.Heavy petrol is mixed into hydro-upgrading reactor in hydrogen partial pressure 2.0MPa, reaction temperature with hydrogen first
380 DEG C, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:Under 1 reaction condition using C catalyst carry out hydro-upgrading, then into
Enter hydrodesulphurisatioreactors reactors in hydrogen partial pressure 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, entering product separator after product cooling carries out gas-liquid separation, product separator top
The hydrogen that portion comes out enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process and recycles, product separator bottom liquid phases
Product enters stabilizer, in tower top pressure 0.88Mpa, 150 DEG C of feeding temperature, 140 DEG C of tower top temperature, 208 DEG C of items of column bottom temperature
Sulfurous gas is removed under part, 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 it can be seen that product sulfur content is 10mg/kg, desulfurization degree 98.6%, olefin(e) centent drops to 24v% from 40v%, pungent
Alkane value (RON) loses 1.4 units.
Table 1
Table 2
Comparative result when comparative example 1 and embodiment 1 are IV gasoline products of producing country, comparative example 2 are production with embodiment 2
Comparative result when V gasoline products of state.The main distinction is the embodiment of the present invention 1, embodiment 2 containing " full fraction is slight
The processing unit (the first hydrodesulphurisatioreactors reactors) of hydrodesulfurization ", and comparative example 1, comparative example 2 do not have.It can be seen by 2 result of table
Go out, for the catalytic gasoline of processing sulfur content 382mg/kg, alkene 41.0v%, under IV scheme of state, 89.5% desulfurization degree, implements
Example 1 loses 0.7 unit less compared with 1 octane number of comparative example；Under V scheme of state, 97.4% desulfurization degree, embodiment 2 is pungent compared with comparative example 2
Alkane value loses 1.0 units less；
Comparative result when comparative example 3 and embodiment 2 are V gasoline products of producing country.The main distinction is the reality of the present invention
Flow of the example 2 using " the hydro-upgrading back end hydrogenation desulfurization of heavy petrol elder generation " is applied, and comparative example 3 is using " after the hydrodesulfurization of heavy petrol elder generation
The flow of hydro-upgrading ".It can be seen from 2 result of table under V scheme of state, 97.4% identical desulfurization degree, embodiment 2 relatively compares
3 octane number of example loses 0.5 unit less；In addition, using the method for the present invention processing sulfur content 695mg/kg, alkene 40v% it is another
A kind of catalytic gasoline, under 98.6% desulfurization degree, alkene reduces 16v%, and octane number only loses 1.4 units.
Beneficial effects of the present invention：
1, using the pre- hydrogenation technique of full distillation gasoline, the diene content in gasoline is reduced, and be greatly reduced in light petrol
Mercaptans content avoid the discharge of the disagreeableness alkaline residue of environment instead of alkali refining removal of mercaptans process, alkadienes in heavy petrol
Content is reduced, and substantially extends the cycle of operation of Hydrobon catalyst；
2, mild hydrogenation sulfur removal technology is carried out again after using the pre- hydrogenation technique of full fraction, then carries out weight group cutting again
Flow is cut, realizes the slight desulfurization of full distillation gasoline, while most of thiophene being removed, therefore relative to straight after full fraction pre-add hydrogen
The flow for tapping into the cutting of row weight component can be improved light petrol cutting ratio, reduce heavy petrol alkene and sulfur content, reduces weight vapour
Loss of octane number caused by oily hydrodesulfurization is specially adapted to the high bad gasoline of processing thiophene content；
3, using the flow of " the hydro-upgrading back end hydrogenation desulfurization of heavy petrol elder generation ", relative to " after the hydrodesulfurization of heavy petrol elder generation plus
The olefin(e) centent of the flow of hydrogen modification ", the charging of heavy petrol reforming unit is high, can ensure the high aromatization rate of gasoline, reduces pungent
Alkane value is lost；Since catalyst for hydro-upgrading is with hydrodesulfurization function, heavy petrol experienced first slight desulfurization, then deep
The relay sweetening process for spending desulfurization is equally beneficial for reducing loss of octane number.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
1. a kind of method of inferior patrol hydro-upgrading, which is characterized in that this approach includes the following steps：
(1) enter pre-hydrogenator after catalytic gasoline is mixed with hydrogen, reacted in the presence of catalyst for pre-hydrogenation, reacted
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, hydrogen to oil volume ratio 10
~200v/v；
(2) enter the first hydrodesulphurisatioreactors reactors after pre- hydrogenation products are mixed with hydrogen, exist in mild hydrogenation desulphurization catalyst
Under reacted, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 200~300 DEG C of reaction temperature, 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, 90~130 DEG C of feeding temperature, tower top temperature
70~110 DEG C are spent, light, heavy gasoline components are cut at 190~230 DEG C of column bottom temperature；
(4) the light petrol component being ejected from fractionation column comes out directly as reformulated gasoline blend component from fractionation column bottom
Heavy gasoline components and hydrogen mixing after enter hydro-upgrading reactor, reacted in the presence of catalyst for hydro-upgrading, instead
The condition is answered to be：1.0~3.0Mpa of hydrogen partial pressure, 320~450 DEG C of reaction temperature, 1.0~3.0h of volume space velocity-1, hydrogen to oil volume ratio
250~500v/v；
(5) product of step (4) enters the second hydrodesulphurisatioreactors reactors, is carried out in the presence of catalyst for selectively hydrodesulfurizing anti-
It answers, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 220~350 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, hydrogen oil body
250~500v/v of product ratio；And
(6) after the cooling of step (5) product, gas-liquid separation, the hydrogen come out at the top of product separator are carried out into product separator
Enter circulating hydrogen compressor after the processing of desulphurization of recycle hydrogen tower to recycle, product separator bottom liquid phases product enters stabilization
Tower, in 0.7~1.2Mpa of tower top pressure, 140~200 DEG C of feeding temperature, 120~180 DEG C of tower top temperature, column bottom temperature 180~
Sulfurous gas is removed under the conditions of 240 DEG C, reformulated gasoline product is mixed to get with light petrol.
2. the method for inferior patrol hydro-upgrading according to claim 1, which is characterized in that the catalyst for pre-hydrogenation carries
Body is the mixture of aluminium oxide, silica or both, and active component is one or more of the VIth B, the VIIIth race, by catalyst
Weight 100% is counted, and active component oxide content is 10~30%, and surplus is carrier.
3. the method for inferior patrol hydro-upgrading according to claim 1, which is characterized in that the catalyst for pre-hydrogenation ratio
Surface area is 100~300m20.2~0.6ml/g of/g, Kong Rongwei.
4. the method for inferior patrol hydro-upgrading according to claim 1, which is characterized in that the mild hydrogenation desulfurization is urged
Agent carrier is the mixture of aluminium oxide and hydrogen type molecular sieve, and active component is one or more of the VIth B, the VIIIth race, institute
It is one or more of HZSM-5, HMCM-22, H β and HY to state molecular sieve, the molecular sieve account for catalyst weight 10~
60%, active component oxide accounts for the 5~15% of catalyst weight.
5. the method for inferior patrol hydro-upgrading according to claim 1, which is characterized in that the mild hydrogenation desulfurization is urged
Agent specific surface area is 200~400m20.4~0.8ml/g of/g, Kong Rongwei.
6. the method for inferior patrol hydro-upgrading according to claim 1, which is characterized in that the catalyst for hydro-upgrading
Carrier is the compound of aluminium oxide and molecular sieve, and active component is one or more of the VIth B, the VIIIth race, the molecular sieve
For one or more of ZSM-5, Beta, SAPO molecular sieve, in terms of catalyst weight 100%, the molecular sieve content is 60
~90%, the active component oxide content is 1~10%.
7. the method for inferior patrol hydro-upgrading according to claim 1, which is characterized in that the catalyst for hydro-upgrading
Specific surface area is 200~500m20.2~0.5ml/g of/g, Kong Rongwei.
8. the method for inferior patrol hydro-upgrading according to claim 1, which is characterized in that the selective hydrodesulfurization
Catalyst is with Al2O3、SiO2、TiO2And ZrO2One or more of be carrier, with P2O5、K2One or more of O and MgO
For auxiliary agent, active component is one or more of VI B races, VIII race, based on catalyst weight 100%, active component oxide
6~20% are accounted for, auxiliary agent accounts for 1~15%, and surplus is carrier；The catalyst for selectively hydrodesulfurizing specific surface area be 170~
270m20.3~0.6ml/g of/g, Kong Rongwei.
9. the method for inferior patrol hydro-upgrading according to claim 1, which is characterized in that the catalytic gasoline is catalysis
Cracking gasoline, sulfur content are less than or equal to 1000mg/kg, and olefin(e) centent is less than or equal to 45v%.
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| CN1597864A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating treatment of foulty gasoline |
| CN1597863A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN103468310A (en) * | 2012-06-07 | 2013-12-25 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
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| CN1597864A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating treatment of foulty gasoline |
| CN1597863A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN103468310A (en) * | 2012-06-07 | 2013-12-25 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
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