CN107974289B - A kind of processing method and system of gasoline - Google Patents
A kind of processing method and system of gasoline Download PDFInfo
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- CN107974289B CN107974289B CN201610921940.3A CN201610921940A CN107974289B CN 107974289 B CN107974289 B CN 107974289B CN 201610921940 A CN201610921940 A CN 201610921940A CN 107974289 B CN107974289 B CN 107974289B
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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
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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
-
- 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
Abstract
The present invention relates to a kind of processing method and system of gasoline, which includes: to cut gasoline stocks, obtains light gasoline fraction, middle gasoline fraction and heavy naphtha；Gained light gasoline fraction is subjected to etherification process, obtains etherificate oil；Gasoline fraction in gained and heavy naphtha are sent into fluidizing reactor and is contacted with mixed catalyst and carries out desulfurization and aromatization under hydro condition, obtains sulfur-free gasoline fraction；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；According to the flow direction of reaction mass in the fluidizing reactor, the middle gasoline fraction feed entrance point is located at the downstream of the heavy naphtha feed entrance point.Method and system provided by the invention can reduce sulphur and olefin(e) centent in gasoline, and can improve the octane number of gasoline simultaneously and keep high yield of gasoline.
Description
Technical field
The present invention relates to a kind of processing method and system of gasoline.
Background technique
Atmosphere pollution caused by motor vehicle exhaust emission is got worse.As people are to the pay attention to day by day of environmental protection, China
The paces of vehicle fuel quality upgrading are accelerated, standard GB/T 17930-2013 requires sulfur content in gasoline to be not more than 10 μ g/
G, volume fraction of olefins are not more than 24%.
Catalytically cracked gasoline is the chief component of China's motor petrol, and 75% or so is accounted in gasoline pool, and it is special
Point is alkene with higher and sulfur content.The deep desulfuration of gasoline is realized using hydrogen addition technology and is reduced in catalytically cracked gasoline
Olefin(e) centent it is not difficult, but since alkene is antiknock component, being greatly reduced for content will lead to octane number
Heavy losses, to influence the automobile-used performance of gasoline and the economic benefit of oil plant, therefore in the deep desulfuration for realizing gasoline
Octane number is kept to become the hot spot of China's clean gasoline production simultaneously.
Currently, the deep desulfuration of gasoline is mainly the method for using hydrodesulfurization or adsorbing desulfurization.
Selective hydrodesulfurization is one of the major way of current removing thiophene-type sulfide, but the reactions such as alkene saturation are same
Sample largely occurs, and causes loss of octane number larger.In addition, the deep hydrogenation method for restoring octane number is similarly approved by people,
It is that second reactor is set to promote cracking hydrocarbon, the isomery of low octane rating while carrying out deep desulfuration and alkene is saturated
Change and alkylated reaction, to achieve the purpose that restore octane number.Chinese patent CN101845322A discloses a kind of reduction vapour
The method of sulphur and olefin(e) centent in oil, raw material catalytic cracking gasoline first pass through pre-hydrogenator removing alkadienes, subsequently into
Fractionating column cutting is fractionated into light, heavy petrol, and light petrol carries out facing hydrogen absorption desulfurization, and heavy petrol enters selective hydrogenation reactor and adds
Hydrogen desulfurization, reaction effluent enter back into hydro-upgrading reactor and carry out hydro-upgrading, reduce olefin(e) centent, the heavy petrol after modification
It reconciles to obtain the clean gasoline for meeting standard requirements with light petrol absorption desulfurization product.Absorbing desulfurization catalyst is in gasoline
Although sulfide has good removal effect, absorption desulfurization carries out under conditions of facing hydrogen, can be saturated catalytically cracked gasoline
In alkene, especially light petrol carries out absorption desulfurization, and the olefin component octane number in light petrol is higher, will cause the pungent of gasoline
Alkane value is largely lost.
Absorption method removes the sulfur-containing compound in fuel oil, is to carry out facing hydrogen reaction absorption to light oil using adsorbent, raw
Sulphur is removed at metal sulfide or using sulfide polarity, hydrogen consumption is lower, and desulfuration efficiency is high, can produce sulfur content in 10 μ g/g
Following gasoline.Although absorbing process realizes the deep desulfuration of gasoline under the conditions of low hydrogen consumes, gasoline product octane number is still omited
There is loss.Especially when handling olefin(e) centent height and the high gasoline stocks of sulfur content, still cause octane number loss compared with
Greatly.
For most of catalytic cracking units, for propylene enhancing and butylene yield and the octane number for improving gasoline,
It is effective method using containing the catalyst or auxiliary agent with MFI structure molecular sieve.United States Patent (USP) USP3758403 is invented
The method that ZSM-5 molecular sieve is added in catalytic cracking catalyst can be improved the octane number of gasoline and increase C3~C4 alkene
Yield.But as it is known by one skilled in the art, propylene enhancing and butylene yield are to sacrifice gasoline production as cost.
Aromatizing low-carbon paraffin is the effective ways for improving low-carbon alkanes utility value.People are to high silica alumina ratio molecular sieve
A large amount of research is carried out for the aromatization process of catalyst, especially using ZSM-5, ZSM-11, ZSM-21 molecular sieve as catalyst
Process carried out a large amount of research, and using the zeolite with MFI structure be used to produce from coking or pyrolysis gasoline low
The aromatisation of carbon hydro carbons.
Summary of the invention
The object of the present invention is to provide a kind of processing method and system of gasoline, method and system provided by the invention can
The sulphur and olefin(e) centent in gasoline are reduced, and the octane number of gasoline can be improved simultaneously and keep high yield of gasoline.
To achieve the goals above, the present invention provides a kind of vapour oil treatment process, which includes: by gasoline original
Material is cut, and light gasoline fraction, middle gasoline fraction and heavy naphtha are obtained；Gained light gasoline fraction is carried out at etherificate
Reason obtains etherificate oil；Gasoline fraction in gained and heavy naphtha are sent into fluidizing reactor and contacted with mixed catalyst
And desulfurization and aromatization are carried out under hydro condition, obtain sulfur-free gasoline fraction；Wherein, the mixed catalyst includes inhaling
Attached desulphurization catalyst and alkene aromatized catalyst；According to the flow direction of reaction mass in the fluidizing reactor, the middle vapour
Oil distillate feed entrance point is located at the downstream of the heavy naphtha feed entrance point.
Preferably, the method also includes: by gained etherificate oil and sulfur-free gasoline fraction mix, obtain gasoline products.
Preferably, by weight and on the basis of the weight of the alkene aromatized catalyst, the alkene aromatisation is urged
Passivation content is 0.1-5.0 weight % in agent；The passivation includes selected from least one of carbon, sulphur and nitrogen element.
Preferably, the preparation step of the alkene aromatized catalyst includes: by fresh aromatized catalyst in pre-reaction
It is contacted in device with carbon containing and/or sulphur and/or nitrogen compound and carries out green coke；Or aromatized catalyst will be regenerated in pre-reaction
It is contacted in device with carbon containing and/or sulphur and/or nitrogen compound and carries out green coke；Or aromatized catalyst to be generated is carried out endless
Full coke burning regeneration.
Preferably, the pre-reactor is the reactor outside the fluidizing reactor or is positioned at the fluidised form
Change the pre lift zone in reactor.
Preferably, the preparation step of the alkene aromatized catalyst includes: that fresh aromatized catalyst is carried out aging
Processing；Wherein, it is 500-800 DEG C that the condition of the aging process, which includes: temperature, and the time is 1-360 hours, and aging atmosphere is water
Vapor atmosphere.
Preferably, the micro-activity of the alkene aromatized catalyst is 20-55, and the micro-activity uses RIPP 92-
The mat activity test method of 90 catalytic cracking industry equilibrium catalysts is measured.
Preferably, volume fraction of olefins is greater than 20 body % in the gasoline stocks.
Preferably, in the gasoline stocks sulfur content more than 10 μ g/g.
Preferably, the gasoline stocks are selected from catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, thermal cracking vapour
At least one of oil and direct steaming gasoline.
Preferably, the cut point of the light gasoline fraction and middle gasoline fraction be 50-80 DEG C, the middle gasoline fraction with again
The cutting temperature of gasoline fraction is 80-130 DEG C.
Preferably, the step of etherification process includes: to contact the light gasoline fraction with alcohols, makes the light petrol
With alcohols etherification reaction occurs for the alkene in fraction under the action of catalyst for etherification, obtains the etherificate oil；Wherein, the ether
The temperature for changing reaction is 20-200 DEG C, pressure 0.1-5MPa, and weight (hourly) space velocity (WHSV) is 0.1-20 hours-1, the alcohols and light petrol
The molar ratio of fraction is 1:(0.1-100), the catalyst for etherification includes at least one in resin, molecular sieve and heteropoly acid
Kind.
Preferably, the fluidizing reactor is riser reactor and/or dense-phase fluidized bed reactor.
Preferably, the absorbing desulfurization catalyst contains silica, aluminium oxide, zinc oxide and desulphurizing activated metal, institute
Stating desulphurizing activated metal is selected from least one of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium.
Preferably, on the basis of the dry weight of the absorbing desulfurization catalyst and in terms of oxide weight, the absorption
Zinc oxide described in desulphurization catalyst accounts for 10-90 weight %, and silica accounts for 5-85 weight %, and aluminium oxide accounts for 5-30 weight %；
On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, taken off described in the absorbing desulfurization catalyst
The content of sulphur active metal is 5-30 weight %.
Preferably, it is counted by butt and on the basis of the total weight of the alkene aromatized catalyst, the alkene aromatisation
Catalyst contains the molecular sieve of 10-30 weight %, the aromatization activity metal oxide of 0-20 weight % and 50-90 weight %'s
Carrier；Wherein, the molecular sieve includes Y molecular sieve and/or MFI structure molecular sieve, and the aromatization activity metal is selected from the
The metallic element of Group IVB, the metallic element of Group VB, the metallic element of group VIB, the metallic element of group VIII, group ib
Metallic element, group iib metallic element and at least one of the metallic element of group III A, the carrier includes oxidation
Silicon and/or aluminium oxide.
Preferably, the MFI structure molecular sieve is selected from least one of ZSM-5, ZSM-8 and ZSM-11, the virtue
Structure active metal is selected from least one of Fe, Zn and Ga.
Preferably, by weight, the alkene aromatized catalyst accounts for the ratio of the mixed catalyst as 1-30 weight
Measure %.
Preferably, it is 350-500 DEG C that the condition of the desulfurization and aromatization, which includes: reaction temperature, and weight (hourly) space velocity (WHSV) is
2-50 hours-1, reaction pressure 0.5-3.0MPa, the sum of hydrogen volume and the middle gasoline fraction and heavy naphtha volume
Ratio is 1-500.
Preferably, the method also includes: the etherification process is carried out after the light gasoline fraction is pre-processed again,
Wherein, the pretreatment is selected from least one of caustic extraction processing, mercaptan conversion processing and selective hydrogenation processing.
The present invention also provides a kind of processing system of gasoline, the system include gasoline stocks fractionating column, fluidizing reactor,
High-pressure separator, pretreatment unit, ether-based device, etherification product fractionating column and mixer；The gasoline stocks fractionating column setting
There are gasoline stocks entrance, light gasoline fraction outlet, the outlet of middle gasoline fraction and heavy naphtha outlet, the fluidizing reactor
Lower part be provided with hydrogen inlet, enterprising material mouth and the lower feed inlet below the enterprising material mouth, the fluidization reaction
Desulfurization and aromatization products outlet are provided at the top of device, the etherification product fractionating column is provided with etherification product entrance, tail gas
Outlet and etherificate oil export；The upper feeding of middle the gasoline fraction outlet and the fluidizing reactor of the gasoline stocks fractionating column
Mouth is in fluid communication, the lower feed inlet fluid of the heavy naphtha outlet and the fluidizing reactor of the gasoline stocks fractionating column
Connection, the desulfurization of the fluidizing reactor and aromatization products outlet entering by the high-pressure separator and the mixer
Mouth is in fluid communication；The light gasoline fraction outlet of the gasoline stocks fractionating column passes sequentially through the pretreatment unit and ether-based device
It is in fluid communication with the etherification product entrance of the etherification product fractionating column, the etherificate oil export of the etherification product fractionating column and institute
The entrance for stating mixer is in fluid communication.
The present invention has following technical effect that compared with prior art
1, method and system of the invention carries out the gasoline stocks of the high alkene of high-sulfur to be cut into light gasoline fraction, middle gasoline
Fraction and heavy naphtha, by middle gasoline fraction and heavy naphtha and absorbing desulfurization catalyst and alkene aromatized catalyst into
Alkene in gasoline can be carried out cracking and aromatisation while reducing content of sulfur in gasoline by row desulfurization and aromatization,
Produce C5Following hydro carbons simultaneously cuts and carries out etherification reaction in light gasoline fraction, to both reduce the content of alkene in gasoline,
It also improves the octane number of gasoline and keeps the high income of gasoline stocks, it being capable of direct producing country V even VI label gasoline of state.
2, desulfurization of the invention and aromatization are carried out in a fluidizing reactor using two kinds of catalyst, are both mentioned
High reaction efficiency, also reduces cost of investment, without increasing or changing reactor.
3, method of the invention can also reduce the light component in gasoline, reduce gasoline vapour pressure.
4, light gasoline fraction is carried out etherification process by the present invention, can either reduce wherein alkene, additionally it is possible to produce higher octane
The etherificate oil of value, improves the octane number of gasoline products.
5, the present invention by gasoline stocks be cut into it is light, in, heavy naphtha, gasoline fraction is handled from molecular level, no
Only flexible operation, also help reduction alkene adds hydrogen saturation.
6, desulfurization of the invention and aromatization are carried out in a fluidizing reactor using two kinds of catalyst, can be with
Gasoline step-by-step processing method (desulfurization after aromatisation or gasoline elder generation aromatisation after the desulfurization of gasoline elder generation) is avoided to need individually to increase aromatization
Change reactor and subsystem, can also need to change existing absorption desulfurization to avoid gasoline desulfurization and aromatisation coupled catalyst and urge
The preparation process flow and catalyst abrasion intensity of agent and aromatized catalyst, both improve reaction efficiency, also reduce
Cost of investment.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is a kind of flow diagram of specific embodiment of the method for the present invention, also includes that present system is a kind of specific
The structural schematic diagram of embodiment.
Description of symbols
Gasoline fraction in 1 gasoline stocks, 2 gasoline stocks fractionating column 3
4 heavy naphtha, 5 hydrogen, 6 fluidizing reactor
Lower 9 desulfurization of feed inlet of 7 enterprising material mouths 8 and aromatization products
10 high-pressure separator, 11 tail gas, 12 sulfur-free gasoline fraction
13 light gasoline fraction, 14 pretreatment unit 15 is etherified preceding light petrol
16 ether-based device, 17 methanol, 18 etherification product
19 etherification product fractionating column, 20 tail gas 21 is etherified oil
22 mixer, 23 gasoline products
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
RIPP test method is for details, reference can be made to " petrochemical analysis method " in the present invention, and Yang Cui is surely equal to be compiled, nineteen ninety version.
The present invention provides a kind of vapour oil treatment process, which includes: to cut gasoline stocks, obtains light
Gasoline fraction, middle gasoline fraction and heavy naphtha；Gained light gasoline fraction is subjected to etherification process, obtains etherificate oil；By institute
Gasoline fraction and heavy naphtha, which are sent into, in obtaining contacts with mixed catalyst in fluidizing reactor and carries out under hydro condition
Desulfurization and aromatization obtain sulfur-free gasoline fraction；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene
Aromatized catalyst；According to the flow direction of reaction mass in the fluidizing reactor, the middle gasoline fraction feed entrance point is located at
The downstream of the heavy naphtha feed entrance point.The feed entrance point refers to what fluidizing reactor was arranged from bottom to top
Material inlet.
According to the present invention, for direct producing country V even VI label gasoline of state.The method can also include: by gained
Etherificate oil and the mixing of sulfur-free gasoline fraction, obtain gasoline products.
According to the present invention, desulfurization and aromatization refer to gasoline stocks under hydro condition in absorbing desulfurization catalyst and
Desulfurization is carried out under the collective effect of alkene aromatized catalyst and converts alkene to the process of aromatic hydrocarbons, it is during which anti-with cracking
It answers, condition may include: that reaction temperature is 350-500 DEG C, and preferably 380-420 DEG C, weight (hourly) space velocity (WHSV) is 2-50 hours-1, excellent
It is selected as 5-20 hours-1, reaction pressure 0.5-3.0MPa, preferably 1.5-2.5MPa, hydrogen volume and the middle gasoline fraction
Ratio with the sum of heavy naphtha volume is (in the status of criterion (STP) 0 DEG C of (273K), 1.01 × 105Under Pa) it is 1-500, it is excellent
It is selected as 50-200.
According to the present invention, absorbing desulfurization catalyst is well-known to those skilled in the art, can contain silica, oxygen
Change aluminium, zinc oxide and desulphurizing activated metal, the desulphurizing activated metal can for selected from cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver,
At least one of tin and vanadium.
A kind of specific embodiment, on the basis of the dry weight of the absorbing desulfurization catalyst and with oxide weight
Meter, zinc oxide described in the absorbing desulfurization catalyst account for 10-90 weight %, and silica accounts for 5-85 weight %, and aluminium oxide accounts for
5-30 weight %；On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, the absorption desulfurization is urged
The content of desulphurizing activated metal described in agent is 5-30 weight %.
According to the present invention, the absorbing desulfurization catalyst can also contain 1-10 weight % class coke mass.Industrial practice
Show that the carbon content on absorbing desulfurization catalyst has shadow to desulfuration efficiency and the octane number loss of absorbing desulfurization catalyst
It rings, with increasing for absorbing desulfurization catalyst carbon content, absorbing desulfurization catalyst desulfuration efficiency gradually declines, octane number damage
Mistake reduces therewith.Similarly, the sulfur content that absorbing desulfurization catalyst keeps certain is very important.Practice have shown that suction to be generated
It is 9 weight %-10 weight % that attached desulphurization catalyst, which carries sulfur content, and regenerative adsorption desulphurization catalyst carries 5 weight %-6 weight % of sulfur content,
The sulphur difference of absorbing desulfurization catalyst to be generated and regenerative adsorption desulphurization catalyst is that 4 weight % or so are the most suitable.To reduce gasoline
Loss of octane number will have been generally acknowledged that reasonable " small sulphur poor, big cycle volume " operation adjustment for the behaviour of " partial circulating amount, big sulphur are poor "
Make, reduce regenerative adsorption desulphurization catalyst sulfur content, improve absorbing desulfurization catalyst sulfur content to be generated, reduces octane number damage
It loses, two kinds of operation essence have been to maintain the higher load sulfur content that the absorbing desulfurization catalyst of reaction is participated in reactor, reduce and inhale
The activity of attached desulphurization catalyst, reduces loss of octane number.
According to the present invention, alkene aromatized catalyst is to refer to hydrocarbon conversions such as alkene in gasoline stocks be aromatic hydrocarbons
Catalyst, generally comprise molecular sieve, preferably include molecular sieve, carrier and metal, for example, in terms of butt and with alkene virtue
On the basis of the total weight of structure catalyst, the alkene aromatized catalyst can the molecular sieve containing 10-30 weight %, 0-20
The aromatization activity metal oxide of weight % and the carrier of 50-90 weight %；Wherein, the molecular sieve may include Y molecule
Sieve and/or MFI structure molecular sieve, preferably five-membered ring high-silica zeolite, high-silica zeolite can be Hydrogen, be also possible to
By rare earth and/or P Modification, silica alumina ratio is preferably greater than 100, more preferably greater than 150.The MFI structure molecular sieve is can
Selected from least one of ZSM-5, ZSM-8 and ZSM-11.The aromatization activity metal can play partial desulfurization or hydrocarbon
Class transformation function, such as can be first for metallic element, the metal of group VIB of metallic element, Group VB selected from group ivb
Element, the metallic element of group VIII, the metallic element of group ib, the metallic element of group iib and group III A metallic element
At least one of, the wherein metallic element of group ivb preferred Zr or/and Ti；The preferred V of the metallic element of Group VB；Group VIB
Metallic element preferred Mo or/and W；One or more of the metallic element of group VIII preferred Fe, Co, Ni element；
The preferred Cu of the metallic element of group ib；The preferred Zn of the metallic element of group iib；The preferred Ga of the metallic element of group III A.It is described
Aromatization activity metal is preferably selected from least one of Fe, Zn and Ga, and content is preferably 0.5-5 weight %.The carrier
Preferably include silica and/or aluminium oxide.The partial size of the alkene aromatized catalyst is generally 20-120 microns, with absorption
Desulphurization catalyst partial size is suitable.Absorbing desulfurization catalyst and alkene aromatized catalyst are separately formed (such as spraying by the present invention
It is dry) after be used in mixed way.
A kind of specific embodiment, the MFI structure molecular sieve, preparation process may include ammonia exchange, P Modification,
In particular metal component modification and calcination process step are by the obtained sodium form with MFI structure of conventional crystallization point
Son sieve is according to molecular sieve: ammonia salt: H2O=1:(0.1-1): the weight ratio of (5-10) is in room temperature to exchanging 0.3-1 hours at 100 DEG C
After filter, introduce phosphorus-containing compound and containing selected from one of Fe, Co, Ni, Zn, Mn, Ga and Sn or a variety of compounds pair
Molecular sieve is modified, and is roasted 0.5-8 hours at 400-800 DEG C later, wherein the described treatment process roasted is also possible to
It is carried out under steam atmosphere.Further, MFI structure molecular sieve provided by the present invention, during the preparation process to molecular sieve
Being modified can be is carried out by the way of dipping or ion exchange.Further, the phosphorus-containing compound can be choosing
From or mixtures thereof one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate.Further, the Fe, Co, Ni, Zn,
Mn, Ga and Sn compound can be selected from their water soluble salt, the water soluble salt can for selected from sulfate, nitrate,
One of chlorate.Further, MFI structure molecular sieve provided by the present invention, contains phosphorus and metal component, acid site
In conjunction with the dehydrogenation close centre of metal, and the presence of phosphorus simultaneously not only can be improved the structural stability of molecular sieve but also make gold
The ability of dehydrogenation sulfurization of category.
The method that the present invention introduces metal active constituent on molecular sieve or carrier can use existing various gold-supporteds
Belong to the method for oxide, such as method of dipping, i.e., using one or more of metal salt solution impregnated zeolites or carrier；Or it is heavy
The method in shallow lake, i.e., using on one or more of metal salt solutions or its oxide, hydroxide deposition to molecular sieve or carrier；Or
Person's soild oxide and/or its precursor-metal salt or its hydroxide and molecular sieve or carrier mechanical mixture, grinding or not
The method of grinding；Or colloidal sol facture, gelling process and hydro-thermal method etc..The metal salt is mainly the sulfate of metal, nitre
Hydrochlorate, acetate, halide and metal ammonium salt, metal sodium salt etc..Preferred method present invention introduces metal active constituent is heavy
The method of the method or dipping in shallow lake.
Present inventors discovered unexpectedly that the micro-activity of alkene aromatized catalyst effect in 20-55 is more excellent,
The micro-activity is measured using the mat activity test method of RIPP 92-90 catalytic cracking industry equilibrium catalyst.However
From manufacturer's production or the not yet used fresh aromatized catalyst of homemade qualification, activity is active generally 60 or more
Higher, cracking performance is stronger, and therefore, fresh aromatized catalyst is handled, and to reduce acid amount, increases acid strength, has
Conducive to the generation for reducing hydrogen transfer reaction.
A kind of embodiment, the alkene aromatized catalyst pass through Passivation Treatment, and the alkene aromatisation through transpassivation is urged
Passivation content can be 0.1-5.0 weight %, preferably 0.3-2.0 weight %, further preferably 0.3-1 weight in agent
Measure %；The passivation may include selected from least one of carbon, sulphur and nitrogen element.The step of Passivation Treatment, can wrap
It includes: fresh aromatized catalyst being contacted in pre-reactor with carbon containing and/or sulphur and/or nitrogen compound and carries out green coke；
Or regeneration aromatized catalyst is contacted in pre-reactor with carbon containing and/or sulphur and/or nitrogen compound and carries out green coke；
Or aromatized catalyst to be generated is subjected to incomplete singeing regeneration.The aromatized catalyst to be generated refers to react in fluidization
By using the catalyst for having loaded certain coke, activity reduces, is not enough to continue to react in device.Aromatisation to be generated is urged
Agent, which carries out incomplete singeing regeneration, reduces loaded coke content, can obtain more suitable activity.The regeneration
Aromatized catalyst is generally 450-690 DEG C through regeneration gained, regeneration temperature completely by aromatized catalyst to be generated, regeneration gas
Generally oxygen-containing gas is returned in fluidizing reactor by regenerated catalyst circulation and is recycled.Regenerate aromatized catalyst
Coke content needs as fresh aromatized catalyst in pre-reactor generally in 0.1 weight % hereinafter, hyperactivity
Middle carry out green coke.
The green coke of the fresh aromatized catalyst and regeneration aromatized catalyst can be reacted being located at the fluidization
It carries out, can also be carried out in the pre lift zone being located in the fluidizing reactor, used in green coke in reactor outside device
Carbon containing and/or sulphur and/or nitrogen compound can be gasoline, hydrogen sulfide or carbon disulfide etc., and gasoline both can be the gasoline
Raw material, or the gasoline stocks outside fluidizing reactor, such as catalytically cracked gasoline, steam cracking gasoline or other
The gasoline of olefin-containing.
A kind of embodiment, the alkene aromatized catalyst pass through aging process.Aging process refers to deposits in vapor
Fresh aromatized catalyst is subjected to high-temperature process under the conditions, to reduce its activity.The condition of the aging process can be with
Include: temperature be 500-800 DEG C, the time be 1-360 hours, aging atmosphere is steam atmosphere, preferably 100% vapor gas
Atmosphere.
A kind of specific embodiment of aging process, by fresh aromatized catalyst and vapor or steam-laden aging
Media contact, under certain thermal and hydric environment (temperature be 500 DEG C -800 DEG C) after aging -360 hours 1 hour, obtained aging
Aromatized catalyst.Further, the aging process refers to fresh aromatized catalyst in 800 DEG C and 100% vapor
Aging certain time is under condition (referring to RIPP 92-90) to reduce activity, if ageing time is 4h or 17h.Further, newly
The ageing method of fresh aromatized catalyst is implemented: fresh aromatized catalyst is packed into the preferably close phase of reactor
Fluidized bed is contacted with vapor or steam-laden aging medium, under certain thermal and hydric environment (temperature is 500 DEG C -800 DEG C)
After aging -360 hours 1 hour, aging aromatized catalyst is obtained.Further, the aging medium include air, dry gas,
The gas or other gases such as nitrogen after gas or air and burning oil firing after regenerated flue gas, air and dry combustion gas.Institute
The weight ratio for stating the vapor and aging medium in steam-laden aging medium is 0.2-0.9, preferably 0.40-0.60.Institute
Stating regenerated flue gas can come from regenerating unit of the invention, can be from other regenerating units.
According to the difference of alkene in gasoline and sulfur content, absorbing desulfurization catalyst and alkene aromatisation in fluidizing reactor
The ratio of catalyst can be different, for example, by weight, the alkene aromatized catalyst accounts for the ratio of the mixed catalyst
For 1-30 weight %, preferably 3-15 weight %.
According to the present invention, gasoline stocks are well-known to those skilled in the art, can be selected from catalytically cracked gasoline, urge
Change at least one of drippolene, coker gasoline, pressure gasoline and direct steaming gasoline.The gasoline that the present invention is handled is preferably height
Alkene and high sulfur oil, volume fraction of olefins are generally higher than 20 body %, preferably greater than 30 body %, more preferably greater than 40 body %,
Further preferably greater than 50 body %, sulfur content is generally more than 10 μ g/g, preferably greater than 50 μ g/g, more preferably greater than 100 μ g/g,
Further preferably greater than 500 μ g/g are still more preferably greater than 1000 μ g/g, the organic sulfur compound in gasoline be generally mercaptan,
Thioether, thiophene, alkylthrophene, benzothiophene and methyl benzothiophene etc..
According to the present invention, the cut point of the light gasoline fraction and middle gasoline fraction can be 50-80 DEG C, the middle gasoline
The cutting temperature of fraction and heavy naphtha can be 80-130 DEG C.Desulfurization and the cutting of aromatization products are generally in fractionating column
It is carried out from low to high according to boiling range, for example, the operating condition of the fractionating column of gasoline cutting are as follows: tower top temperature is 60-80 DEG C, tower bottom
Temperature is 120-160 DEG C, operating pressure 0.05-0.3MPa.
According to the present invention, etherification process refers to C in light gasoline fraction5Low-carbon hydro carbons below (such as iso-amylene and ring
Amylene) and alcohols progress etherification reaction, to generate high-octane etherificate oil, for example, the step of etherification process can wrap
Include: the light gasoline fraction contacted with alcohols, make the alkene in the light gasoline fraction under the action of catalyst for etherification with
Etherification reaction occurs for alcohols, obtains the etherificate oil；Wherein, the temperature of the etherification reaction can be 20-200 DEG C, and pressure can
Think 0.1-5MPa, weight (hourly) space velocity (WHSV) can be 0.1-20 hours-1, the molar ratio of the alcohols and light gasoline fraction can be 1:
(0.1-100), the catalyst for etherification may include selected from least one of resin, molecular sieve and heteropoly acid, the hydro carbons
It can be for selected from least one of methanol, ethyl alcohol and propyl alcohol.
Strong acid cation exchange resin catalyst is loaded on one section of etherificate by a kind of specific embodiment of etherification process
And/or in two sections of etherificate fixed bed reactors, etherificate will be passed through by pretreated light gasoline fractions such as desulfurization and dialkene removals
It is 50-90 DEG C in reaction temperature in reactor, liquid hourly space velocity (LHSV) 1.0-3.0h-1, methanol and light gasoline fraction active olefin (isomery
Alkene, such as iso-amylene) etherification reaction occurs under conditions of molar ratio 1-2, etherification product is sent into rectifying column separation, is obtained in tower bottom
To etherificate oil, unreacted lighter hydrocarbons and methanol loop are utilized.Etherification procedure reaction temperature preferably is inlet temperature 55-60
DEG C, for outlet temperature less than 90 DEG C, air speed is preferably 1-2h-1, the molar ratio of methanol and light gasoline fraction is preferably 1.2-1.4.Its
In, it is suitable for using mixed phase bed reactor that one section of etherificate olefin(e) centent is higher, and two sections of etherificate olefin(e) centents are lower, is suitable for using exhausted
Thermosetting fixed bed reactor.In addition, isomerization unit also can be applied to during Etherification of Light FCC Gasoline.Etherification of Light FCC Gasoline has reduction
Content of olefin in gasoline improves octane number, reduces vapour pressure and improve added value and strengthen many advantages, such as reconciling benefit, etherificate
Oil can be used as octane number blend component carry out using, can also be mixed with heavy naphtha as full distillation gasoline produce
Product.
According to the present invention, fluidizing reactor is well-known to those skilled in the art, for example, can for selected from fluidized bed,
It is riser, downstriker pipeline reactor, the compound reactor being made of riser with fluidized bed, defeated by riser and downstriker
Line sending constitute compound reactor, be made of two or more risers compound reactor, by two or two with
On the fluidized bed compound reactor constituted, the compound reactor that is made of two or more downstriker pipelines, it is excellent
It is selected as riser reactor and/or fluidized-bed reactor, above-mentioned every kind of reactor is segmented into two or more reactions
Area.The fluidized-bed reactor can be for selected from fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying
One or more of bed and dense-phase fluidized bed；The riser reactor can for selected from equal diameter riser, etc. linear speeds mention
One or more of riser and various variable diameters risers.Preferably, it is anti-to be selected from dense-phase fluidized for the fluidizing reactor
Answer device.It should be noted that the fluidizing reactor is at least provided with two feed inlets, including at least one heavy naphtha
Feed inlet and at least one gasoline fraction feed inlet, and the feed inlet of each heavy naphtha is respectively positioned on each middle gasoline
The upstream of fraction feed inlet.Be arranged such can by the higher heavy naphtha of sulfur content preferentially with desulphurizing activated higher absorption
Hydrodesulfurization catalyst improves absorption desulfuration efficiency to realize from molecular level processes gasoline fraction.
According to the present invention, light gasoline fraction need to generally be pre-processed before carrying out etherification reaction, to remove sulfide
With the impurity such as alkadienes, to extend the service life of catalyst for etherification.Therefore, the method for the invention can also include: will be described light
Gasoline fraction carries out the etherification process after being pre-processed again, wherein the pretreatment can for selected from caustic extraction processing,
At least one of mercaptan conversion processing and selective hydrogenation processing.Caustic extraction processing uses lye by the sulphur of light gasoline fraction
Alcohol extracting is removed into lye；Mercaptan conversion processing converts other sulfide for small molecule mercaptan and removes, and can use
The modes such as conventional alkali-free sweetening technique and pre-add hydrogen carry out, and used catalyst and co-catalyst all can be commonly used in the art
Catalyst.Selective hydrogenation processing be it is well-known to those skilled in the art, for removing alkadienes in gasoline, and can be by 3-
Methyl-1-isomerization of butene is 2-methyl-1-butene alkene.
The present invention also provides a kind of processing system of gasoline, which includes gasoline stocks fractionating column 2, fluidizing reactor
6, high-pressure separator 10, pretreatment unit 14, ether-based device 16, etherification product fractionating column 19 and mixer 22；The gasoline is former
Material fractionating column 2 is provided with gasoline stocks entrance, light gasoline fraction outlet, the outlet of middle gasoline fraction and heavy naphtha outlet, institute
The lower part for stating fluidizing reactor 6 is provided with hydrogen inlet, enterprising material mouth and the lower feed inlet below the enterprising material mouth,
The top of the fluidizing reactor 6 is provided with desulfurization and aromatization products outlet, and the etherification product fractionating column 19 is provided with
Etherification product entrance, offgas outlet and etherificate oil export；The outlet of middle gasoline fraction and the stream of the gasoline stocks fractionating column 2
The enterprising material mouth of state reactor 6 is in fluid communication, heavy naphtha outlet and the fluidization of the gasoline stocks fractionating column 2
The lower feed inlet of reactor 6 is in fluid communication, and the desulfurization of the fluidizing reactor 6 and aromatization products outlet pass through the high pressure
The entrance of separator 10 and the mixer 22 is in fluid communication；The light gasoline fraction outlet of the gasoline stocks fractionating column 2 is successively
It is in fluid communication by the etherification product entrance of the pretreatment unit 14 and ether-based device 16 and the etherification product fractionating column 19,
The etherificate oil export of the etherification product fractionating column 19 and the entrance of the mixer 22 are in fluid communication.The fluidizing reactor
6 hydrogen inlet can be same entrance with enterprising material mouth, can also be same entrance, preferably enterprising material mouth with lower feed inlet
It is hydrogen inlet with lower feed inlet.
The present invention is further illustrated below in conjunction with attached drawing, but the present invention is not therefore subject to any restriction.
As shown in Figure 1, high alkene and high-sulfur gasoline stocks 1, which are first passed through gasoline stocks fractionating column 2, carries out cutting fractionation, point
It evaporates for light gasoline fraction 13, middle gasoline fraction 3 and heavy naphtha 4, wherein the cut point of light, middle gasoline fraction is 50~80
DEG C, in, the cut point of heavy naphtha be 80~130 DEG C；After middle gasoline fraction 3 and heavy naphtha 4 are respectively mixed with hydrogen 5
Respectively enter fluidizing reactor 6 enterprising material mouth 7 and lower feed inlet 8, with absorbing desulfurization catalyst and alkene Aromatizatian catalytic
Agent contact carries out absorption desulfurization and aromatization, and desulfurization and aromatization products 9 enter high-pressure separator 10, obtain sulfur-free gasoline
Fraction 12 and tail gas 11.Light gasoline fraction 13 enters light vapour before pretreatment unit 14 obtains being etherified after the pretreatment such as removal of mercaptans
Oil 15, is then mixed into Etherification of Light FCC Gasoline device 16 with methanol 17 and is reacted, etherification product 18 is fractionated tower 19 and is fractionated
To etherificate oil 21 and the tail gas 20 containing methanol.The etherificate oil 21 after sulfur-free gasoline fraction 12 and etherification process after adsorbing desulfurization
Clean gasoline with high octane product 23 is mixed to get in mixer 22.
The following examples will be further described the present invention, but not thereby limiting the invention.
The full fraction of gasoline stocks used in embodiment and comparative example is stable gasoline A, and property is listed in table 1.
Absorbing desulfurization catalyst used in embodiment and comparative example is catalyzed by Sinopec Group
The production of agent branch company, goods number FCAS, used aromatized catalyst are that catalyst is made in laboratory by oneself, and the trade mark is
OTAZ-C-3, absorbing desulfurization catalyst and aromatized catalyst property are listed in table 2.
Wherein, the preparation method of aromatized catalyst OTAZ-C-3 is: by 50g (NH4)2SO4It is dissolved in 1000g water, to institute
It obtains and 100g (butt) crystallization product ZSM-5 molecular sieve (production of Chang Ling catalyst plant, non-amine method synthesis) is added in solution, at 95 DEG C
After exchanging 1h, filter cake is filtered to obtain；By 8.6g (NH4)2HPO4It is dissolved in 60g water, is mixed with dipping and dries with filter cake；It adds
6.0gGa(NO3)3·9H2O is dissolved in 120g water, is mixed with dipping and is dried with above-mentioned sample；Gained sample is in 580 DEG C of calcination process 3
Hour, obtain molecular sieve product；Gained molecular sieve product is added in 500 grams of (butt) sial colloids, it is spray-dried to be made
Microspherical catalyst.
In following embodiment and comparative example, Na in catalyst2O、NiO、ZnO、Ga2O3、Al2O3、SiO2Content X
Ray fluorescence measures, wherein Al2O3、SiO2Content referring specifically to RIPP134-90 measure, remaining composition measuring method phase
Seemingly.
GB/T5487-1995 and GB/T is respectively adopted in the octane number RON and MON of gasoline in the embodiment of the present invention and comparative example
503-1995 standard method is measured, anti-knock index=(MON+RON)/2, gasoline PONA using simulation distillation and it is gasoline detailed
Hydrocarbon analyzes (ASTM D2887 and ASTM D6733-01 (2011) test method is respectively adopted to be tested), and content of sulfur in gasoline is adopted
It is measured with SH/T0689-2000.
Embodiment 1
Stable gasoline A is distilled in fractionating column, be cut into it is light, in, heavy naphtha, control light gasoline fraction is whole
It evaporates a little for 60~70 DEG C (being carried out according to ASTM D86 standard), the middle gasoline fraction end point of distillation is 80~130 DEG C.Wherein, stablize vapour
The light gasoline fraction that oily A distills is denoted as LCN-A, and middle gasoline fraction is denoted as MCN-A, and heavy naphtha is denoted as HCN-A, property
It is shown in Table 3.Light gasoline fraction carries out desulfurization, dialkene removal pretreatment through finishing reactor under hydro condition, makes light gasoline fraction
Middle sulfur content and diene content be down to 10ppm hereinafter, be then mixed into methanol methyltertiarvbutyl ether reactor carry out etherification reaction,
Etherification reaction condition are as follows: 55-80 DEG C of reaction temperature, air speed 1.2h-1, methanol rubs with light gasoline fraction active olefin (isomeric olefine)
Your ratio 1.2, oil gas enters etherificate fractionating column and separates after the etherificate reacted, top gaseous phase be include residual carbon five and methanol
Containing methanol-fueled exhaust, tower bottom obtains etherificate oil, and the tower top temperature for being etherified fractionating column is 60-80 DEG C, and column bottom temperature is 110-140 DEG C.
Etherificate oil is denoted as LCN-A-M, and property is shown in Table 3.
The fresh aromatized catalyst that the trade mark is OTAZ-C-3 is packed into dense-phase fluidized bed reactor, in aging temperature 780
DEG C, continuous ageing 8 hours under 100% water vapor conditions, obtain the OTAZ-C-3 catalyst of aging, micro-activity 45.
The heavy naphtha that the middle gasoline fraction and number that number is MCN-A are HCN-A respectively enters fluidizing reactor
Enterprising material mouth and lower feed inlet, in small-sized continuous fluidized bed reactor with include sulfur absorbent catalyst FCAS and aging
The mixed catalyst contact of aromatized catalyst OTAZ-C-3 (OTAZ-C-3 account for total catalyst weight 7%), wherein MCN-A exists
The residence time of residence time ratio HCN-A in reactor is short, carries out absorption desulfurization and aromatization.Operating condition are as follows: anti-
Answering temperature is 400 DEG C, reactor pressure 2.1MPa, and total weight (hourly) space velocity (WHSV) of middle gasoline fraction and heavy naphtha is 6 hours-1,
The ratio of the sum of hydrogen volume and the middle gasoline fraction and heavy naphtha volume is 75.The desulfurization obtained by reactor head
It is cooled and separated to obtain tail gas and sulfur-free gasoline fraction with aromatization products.The regeneration temperature of mixed catalyst is 550 DEG C, then
It is recycled in mixed catalyst Returning reactor after life.Sulfur-free gasoline fraction property is shown in Table 3, sulfur-free gasoline fraction and etherificate
After oily LCN-A-M mixing, gasoline products are obtained, main character is listed in table 4.
Comparative example 1
It is essentially identical with the operation of comparative example 1, the difference is that all being inhaled using absorbing desulfurization catalyst FCAS
Attached desulphurization reaction obtains gasoline products, main character is listed in table 4 after sulfur-free gasoline fraction is mixed with etherificate oil LCN-A-M.
It can be seen from Table 4 that embodiment 1 is suitable with the desulfuration efficiency of comparative example 1, and the organon octane of embodiment 1
Value increases about 4.5 units than comparative example 1.
Table 1
Table 2
| Catalyst | FCAS | OTAZ-C-3 |
| Chemical composition, weight % | ||
| Aluminium oxide | 13 | 50.3 |
| Sodium oxide molybdena | / | 0.06 |
| Nickel oxide | 21 | / |
| Zinc oxide | 52 | / |
| Gallium oxide | / | 1.5 |
| Silica | 14 | 48.14 |
| Apparent density, kg/m3 | 1010 | 800 |
| Pore volume, mL/g | / | 0.27 |
| Specific surface area, m2/g | / | 218 |
| Abrasion index, again when %-1 | / | 1.5 |
| Screening composition, weight % | ||
| 0~40 micron | 14.5 | 13.9 |
| 40~80 microns | 51.9 | 49.5 |
| > 80 microns | 33.6 | 36.6 |
| Micro-activity | / | 80 |
Table 3
Table 4
Claims (20)
1. a kind of vapour oil treatment process, the processing method include:
Gasoline stocks are cut, light gasoline fraction, middle gasoline fraction and heavy naphtha are obtained；
Gained light gasoline fraction is subjected to etherification process, obtains etherificate oil；
Gasoline fraction in gained and heavy naphtha are sent into fluidizing reactor and is contacted with mixed catalyst and is facing hydrogen item
Desulfurization and aromatization are carried out under part, obtain sulfur-free gasoline fraction；Wherein, the mixed catalyst includes absorption desulfurization catalyst
Agent and alkene aromatized catalyst；The micro-activity of the alkene aromatized catalyst is 20-55, and the micro-activity uses
The mat activity test method of RIPP 92-90 catalytic cracking industry equilibrium catalyst is measured；
According to the flow direction of reaction mass in the fluidizing reactor, the middle gasoline fraction feed entrance point is located at the heavy petrol
The downstream of fraction feed entrance point.
2. according to the method described in claim 1, the method also includes: by gained etherificate oil and sulfur-free gasoline fraction mix,
Obtain gasoline products.
3. according to the method described in claim 1, wherein, by weight and using the weight of the alkene aromatized catalyst as base
Standard, passivation content is 0.1-5.0 weight % in the alkene aromatized catalyst；The passivation includes being selected from carbon, sulphur and nitrogen
At least one of element.
4. method according to claim 1 or 3, wherein the preparation step of the alkene aromatized catalyst includes:
Fresh aromatized catalyst is contacted in pre-reactor with carbon containing and/or sulphur and/or nitrogen compound and carries out green coke；
Or
Regeneration aromatized catalyst is contacted in pre-reactor with carbon containing and/or sulphur and/or nitrogen compound and carries out green coke；
Or
Aromatized catalyst to be generated is subjected to incomplete singeing regeneration.
5. according to the method described in claim 4, wherein, the pre-reactor is the reaction outside the fluidizing reactor
Device is the pre lift zone in the fluidizing reactor.
6. according to the method described in claim 1, wherein, the preparation step of the alkene aromatized catalyst includes: will be fresh
Aromatized catalyst carries out aging process；Wherein, it is 500-800 DEG C that the condition of the aging process, which includes: temperature, time 1-
360 hours, aging atmosphere was steam atmosphere.
7. according to the method described in claim 1, wherein, volume fraction of olefins is greater than 20 volume % in the gasoline stocks.
8. according to the method described in claim 1, wherein, sulfur content is more than 10 μ g/g in the gasoline stocks.
9. according to the method described in claim 1, wherein, the gasoline stocks are selected from catalytically cracked gasoline, catalytic pyrolysis vapour
At least one of oil, coker gasoline, pressure gasoline and direct steaming gasoline.
10. according to the method described in claim 1, wherein, the cut point of the light gasoline fraction and middle gasoline fraction is 50-80
DEG C, the cutting temperature of the middle gasoline fraction and heavy naphtha is 80-130 DEG C.
11. according to the method described in claim 1, wherein, the step of etherification process include: by the light gasoline fraction with
Alcohols contact, makes the alkene in the light gasoline fraction that etherification reaction occur with alcohols under the action of catalyst for etherification, obtains
The etherificate oil；Wherein, the temperature of the etherification reaction is 20-200 DEG C, pressure 0.1-5MPa, weight (hourly) space velocity (WHSV) 0.1-20
Hour-1, the molar ratio of the alcohols and light gasoline fraction is 1:(0.1-100), the catalyst for etherification include selected from resin, point
At least one of son sieve and heteropoly acid.
12. according to the method described in claim 1, wherein, the fluidizing reactor is riser reactor and/or dense-phase flow
Fluidized bed reactor.
13. according to the method described in claim 1, wherein, the absorbing desulfurization catalyst contains silica, aluminium oxide, oxygen
Change zinc and desulphurizing activated metal, the desulphurizing activated metal be in cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium extremely
Few one kind.
14. according to the method for claim 13, wherein on the basis of the dry weight of the absorbing desulfurization catalyst and with
Oxide weight meter, zinc oxide described in the absorbing desulfurization catalyst account for 10-90 weight %, and silica accounts for 5-85 weight %,
Aluminium oxide accounts for 5-30 weight %；On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, the absorption
The content of desulphurizing activated metal described in desulphurization catalyst is 5-30 weight %.
15. according to the method described in claim 1, wherein, in terms of butt and with the total weight of the alkene aromatized catalyst
On the basis of, the alkene aromatized catalyst contains the aromatization activity metal oxygen of the molecular sieve of 10-30 weight %, 0-20 weight %
The carrier of compound and 50-90 weight %；Wherein, the molecular sieve includes Y molecular sieve and/or MFI structure molecular sieve, the aromatization
Changing active metal is metallic element, the metallic element of Group VB, the metallic element of group VIB, group VIII selected from group ivb
Metallic element, the metallic element of group ib, the metallic element of group iib and group III A metallic element at least one
Kind, the carrier includes silica and/or aluminium oxide.
16. according to the method for claim 15, wherein the MFI structure molecular sieve is selected from ZSM-5, ZSM-8 and ZSM-
At least one of 11, the aromatization activity metal is selected from least one of Fe, Zn and Ga.
17. according to the method described in claim 1, wherein, by weight, the alkene aromatized catalyst accounts for the mixing and urges
The ratio of agent is 1-30 weight %.
18. according to the method described in claim 1, wherein, the condition of the desulfurization and aromatization includes: that reaction temperature is
350-500 DEG C, weight (hourly) space velocity (WHSV) is 2-50 hours-1, reaction pressure 0.5-3.0MPa, hydrogen volume and the middle gasoline fraction and
The ratio of the sum of heavy naphtha volume is 1-500.
19. according to the method described in claim 1, the method also includes: after the light gasoline fraction is pre-processed again
Carry out the etherification process, wherein the pretreatment is at caustic extraction processing, mercaptan conversion processing and selective hydrogenation
At least one of reason.
20. a kind of processing system of gasoline, which includes gasoline stocks fractionating column (2), fluidizing reactor (6), high pressure point
From device (10), pretreatment unit (14), ether-based device (16), etherification product fractionating column (19) and mixer (22)；
The gasoline stocks fractionating column (2) be provided with gasoline stocks entrance, light gasoline fraction outlet, middle gasoline fraction outlet and again
Gasoline fraction outlet, the lower part of the fluidizing reactor (6) are provided with hydrogen inlet, enterprising material mouth and are located at the upper feeding
The lower feed inlet of mouthful lower section, desulfurization and aromatization products outlet, the etherificate are provided at the top of the fluidizing reactor (6)
Product fractionation tower (19) is provided with etherification product entrance, offgas outlet and etherificate oil export；
The enterprising material mouth fluid of middle the gasoline fraction outlet and the fluidizing reactor (6) of the gasoline stocks fractionating column (2)
Connection, the lower feed inlet fluid of the heavy naphtha outlet and the fluidizing reactor (6) of the gasoline stocks fractionating column (2)
Connection, the desulfurization of the fluidizing reactor (6) and aromatization products outlet pass through the high-pressure separator (10) and described mixed
The entrance of clutch (22) is in fluid communication；
The light gasoline fraction outlet of the gasoline stocks fractionating column (2) passes sequentially through the pretreatment unit (14) and ether-based device
(16) it is in fluid communication with the etherification product entrance of the etherification product fractionating column (19), the ether of the etherification product fractionating column (19)
Carburetion outlet and the entrance of the mixer (22) are in fluid communication.
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| CN104673377A (en) * | 2015-02-04 | 2015-06-03 | 中国石油大学(北京) | Quality improvement method of catalytic cracking gasoline |
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| CN101270301A (en) * | 2007-03-23 | 2008-09-24 | 中国石油天然气股份有限公司 | Light gasoline etherification technique and catalytically cracked gasoline modification method containing the technique |
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