CN108659883A

CN108659883A - The method and system of gasoline desulfurization and aromatisation

Info

Publication number: CN108659883A
Application number: CN201710194199.XA
Authority: CN
Inventors: 许友好; 王新; 徐莉; 于敬川; 汪燮卿
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-03-28
Filing date: 2017-03-28
Publication date: 2018-10-16
Anticipated expiration: 2037-03-28
Also published as: CN108659883B

Abstract

The present invention relates to the method and system of a kind of gasoline desulfurization and aromatisation, this method includes：Gasoline stocks are subjected to the first cutting, obtain the first light gasoline fraction and the first heavy naphtha；The first heavy naphtha of gained is sent into first set fluidizing reactor and is contacted with mixed catalyst and carries out desulfurization and aromatization in the case where facing hydrogen state, obtains desulfurization and aromatization products；The first light gasoline fraction of gained is sent into second set of fluidizing reactor and carries out desulphurization reaction with absorbing desulfurization catalyst, obtains desulfurization product；Gained desulfurization and aromatization products are subjected to the second cutting, obtain the second light gasoline fraction and the second heavy naphtha；The second light gasoline fraction of gained and the desulfurization product are subjected to etherification process together, obtain etherificate oil.Method and system provided by the invention can reduce sulphur and olefin(e) centent in gasoline, and can reduce the loss of octane number of gasoline simultaneously and keep high yield of gasoline.

Description

The method and system of gasoline desulfurization and aromatisation

Technical field

The present invention relates to the methods and system of a kind of gasoline desulfurization and aromatisation.

Background technology

Atmosphere pollution getting worse caused by motor vehicle exhaust emission.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 that have higher alkene 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 using hydrodesulfurization or the method for adsorbing desulfurization.Selective hydrodesulfurization It is one of the major way of current removing thiophene-type sulfide, but the reactions such as alkene saturation equally largely occur, and cause octane number It loses larger.In addition, the deep hydrogenation method for restoring octane number is similarly approved by people, it is to carry out deep desulfuration and alkene While saturation, setting second reactor is to promote cracking hydrocarbon, isomerization and the alkylated reaction of low octane rating, to reach Restore the purpose of octane number.Absorption method removes the sulfur-containing compound in fuel oil, be light oil is carried out facing hydrogen using adsorbent it is anti- It should adsorb, generate metal sulfide or remove sulphur using sulfide polarity, hydrogen consumption is relatively low, and desulfuration efficiency is high, can produce sulphur and contain Amount is in the 10 following gasoline of μ g/g.Although absorbing process realizes the deep desulfuration of gasoline under the conditions of low hydrogen consumes, gasoline product is pungent Alkane value is still slightly lost.Especially when handling olefin(e) centent height and the high gasoline stocks of sulfur content, still cause gasoline pungent The loss of alkane value is larger.

Chinese patent CN101845322A discloses a kind of method reducing sulfur in gasoline and olefin(e) centent, and catalytic material is split Change gasoline and first pass through pre-hydrogenator removing alkadienes, light, heavy petrol is fractionated into subsequently into fractionating column cutting, light petrol into Row faces hydrogen absorption desulfurization, and heavy petrol enters selective hydrogenation reactor hydrodesulfurization, and it is anti-that reaction effluent enters back into hydro-upgrading It answers device to carry out hydro-upgrading, reduces olefin(e) centent, the heavy petrol after modification reconciles with light petrol absorption desulfurization product to be met The clean gasoline that standard requires.

The method that Chinese patent CN1766057A discloses production low sulfur, low olefin gasoline, is by full boiling range cracked naphtha At least two fractions are separated into, polyunsaturated compounds are selectively hydrogenated, then by light gasoline fraction etherificate, heavy naphtha Hydrodesulfurization or chemisorption carry out removal of sulphur, finally merge two kinds of fractions and obtain low sulfur, low olefin gasoline.The present invention will be handled Low sulfur, low olefin gasoline is obtained, but gasoline product octane number is expected to reduce to a certain degree.

Chinese patent CN103657709A discloses a kind of reaction absorption desulfurization-aromatization technique and its catalyst, The catalyst not only has reaction absorption desulfurizing function in hydrorefining catalyst cracking gasoline feedstock, but also being capable of Coupling Adsorption Desulphurization reaction and aromatization, reaching deep desulfuration, octane number is not substantially reduced simultaneously, catalyst main component For Ni/ZnO-ZSM-5.Foregoing invention is each provided with a kind of good distillate modifying process and catalyst.

For most of catalytic cracking units, for propylene enhancing and butylene yield and the octane number for improving gasoline, Using containing with MFI structure molecular sieve catalyst or auxiliary agent be effective method.United States Patent (USP) USP3758403 is invented The method that ZSM-5 molecular sieve is added in catalytic cracking catalyst can improve 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. In addition, aromatizing low-carbon paraffin is the effective ways for improving low-carbon alkanes utility value.People to being with high silica alumina ratio molecular sieve The aromatization process of catalyst has carried out a large amount of research, especially using ZSM-5, ZSM-11, ZSM-21 molecular sieve as catalyst Process has carried out a large amount of research, and the low-carbon for being used to produce from coking or pyrolysis gasoline using the zeolite with MFI structure The aromatisation of hydro carbons.

As it is known by one skilled in the art, conventional catalytic cracking main fractionating tower tower top is generally using one section of condensation, it is cold Temperature is 40 DEG C or so afterwards, and condensate liquid (catalytic gasoline) part returns to main fractionating tower tower top, another part conduct as reflux Raw gasoline is sent to absorbing-stabilizing system.

Since technique is when reducing sulfur content of catalytic cracking gasoline for gasoline absorbing desulfurization (abbreviation S Zorb), octane number Lose less, while plant energy consumption is relatively low.Therefore, domestic many oil plants select S Zorb technologies to handle catalytic cracking vapour Oil builds more set S Zorb devices, the in this way space there is optimization catalytically cracked gasoline processing technological flow.

Invention content

The object of the present invention is to provide the method and system of a kind of gasoline desulfurization and aromatisation, methods provided by the invention Sulphur and olefin(e) centent in gasoline can be reduced with system, and the loss of octane number of gasoline can be reduced simultaneously and keep high gasoline Yield.

To achieve the goals above, the present invention provides a kind of method of gasoline desulfurization and aromatisation, and this method includes：By vapour Oily raw material carries out the first cutting, obtains the first light gasoline fraction and the first heavy naphtha；The first heavy naphtha of gained is sent Enter and contacted with mixed catalyst in first set fluidizing reactor and carry out desulfurization and aromatization in the case where facing hydrogen state, obtains Desulfurization and aromatization products；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；By institute It obtains the first light gasoline fraction second set of fluidizing reactor of feeding and desulphurization reaction is contacted and carried out with absorbing desulfurization catalyst, obtain Desulfurization product；Gained desulfurization and aromatization products are subjected to the second cutting, the second light gasoline fraction is obtained and the second heavy petrol evaporates Point；The second light gasoline fraction of gained and the desulfurization product are subjected to etherification process together, obtain etherificate oil.

Optionally, this method further includes：The second heavy naphtha of gained is mixed with etherificate oil, obtains gasoline products.

Optionally, the alkene aromatized catalyst includes selected from fresh aromatized catalyst, passivation aromatized catalyst At least one of with aging aromatized catalyst；Wherein, in the passivation aromatized catalyst, passivation content is 0.1- 5.0 weight %, the passivation include selected from least one of carbon, sulphur and nitrogen element.

Optionally, volume fraction of olefins is more than 10 body % in the gasoline stocks.

Optionally, in the gasoline stocks sulfur content more than 10 μ g/g.

Optionally, 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.

Optionally, the gasoline stocks are catalytically cracked gasoline, and described the step of being cut gasoline stocks includes：It will The tower top oil gas for carrying out the main destilling tower of catalytic cracking carries out two sections of condensations, and first segment is condensed gained gasoline product as described the Second segment is condensed gained gasoline product as first light gasoline fraction by one heavy naphtha.

Optionally, the cut point of first light gasoline fraction and the first heavy naphtha be 60-100 DEG C, described second The cut point of light gasoline fraction and the second heavy naphtha is 60-100 DEG C.

Optionally, the first set fluidizing reactor and second set of fluidizing reactor are each independently selected from fluidisation Bed, riser, downstriker pipeline reactor, the compound reactor being made of riser and fluid bed, by riser and downlink Formula pipeline constitute compound reactor, be made of two or more risers compound reactor, by two or two A above fluid bed compound reactor constituted and the recombination reaction being made of two or more downstriker pipelines At least one of device, preferably equal diameter riser, variable diameters riser, one kind in dense-phase fluidized bed reactor or several Kind, first set fluidizing reactor belongs to gasoline absorbing desulfurization and aromatisation device, and second set of fluidizing reactor belongs to vapour Oily adsorpting desulfurization device.

Optionally, the absorbing desulfurization catalyst contains silica, aluminium oxide, zinc oxide and desulphurizing activated metal, institute It is selected from least one of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium to state desulphurizing activated metal.

Optionally, 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 %.

Optionally, 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 0.1-20 weight % and 50-89 weight % Carrier；Wherein, the molecular sieve includes Y molecular sieve and/or MFI structure molecular sieve, the aromatization activity metal be selected from The metallic element of group ivb, the metallic element of Group VB, the metallic element of group VIB, the metallic element of group VIII, I B At least one of the metallic element of the metallic element of race, the metallic element of group iib and group III A, the carrier include oxygen SiClx and/or aluminium oxide.

Optionally, the MFI structure molecular sieve is selected from least one of ZSM-5, ZSM-8 and ZSM-11, the aromatization Change active metal and is selected from least one of Fe, Zn and Ga.

Optionally, by weight, the alkene aromatized catalyst accounts for the ratio of the mixed catalyst as 1-30 weights Measure %.

Optionally, the condition of the desulfurization and aromatization and the desulphurization reaction includes each independently：Reaction temperature Degree is 350-500 DEG C, and weight (hourly) space velocity (WHSV) is 2-50 hours^-1, reaction pressure 0.5-3.5MPa.

Optionally, the step of etherification process includes：By second light gasoline fraction and the desulfurization product and alcohol Class contacts, and the alkene in second light gasoline fraction and the desulfurization product is made to be sent out with alcohols under the action of catalyst for etherification Raw etherification reaction obtains the etherificate oil；Wherein, the temperature of the etherification reaction is 20-200 DEG C, pressure 0.1-5MPa, weight When air speed be 0.1-20 hours^-1, the sum of the molal quantity of the alcohols and molal quantity of the second light gasoline fraction and desulfurization product Ratio is 1：(0.1-100), the catalyst for etherification include selected from least one of resin, molecular sieve and heteropoly acid.

The present invention also provides a kind of system of gasoline desulfurization and aromatisation, which includes：Gasoline stocks cutter unit, A set of fluidizing reactor, first set high-pressure separator, second set of fluidizing reactor, second set of high-pressure separator, destilling tower, Methyltertiarvbutyl ether reactor, etherification product fractionating column and mixer；The gasoline stocks cutter unit is provided with gasoline stocks entrance, first Light gasoline fraction exports and the outlet of the first heavy naphtha, the first set fluidizing reactor are provided with feed inlet and reaction oil Gas exports, and the first set high-pressure separator is provided with feed inlet, gas vent and desulfurization and aromatization products outlet, institute It states second set of fluidizing reactor and is provided with feed inlet and reaction oil gas outlet, second set of high-pressure separator is provided with charging Mouth, gas vent and desulfurization product outlet, the destilling tower are provided with feed inlet, the outlet of the second light gasoline fraction and the second heavy vapour Oil distillate exports；The methyltertiarvbutyl ether reactor is provided with feed inlet and reacting product outlet, and the etherification product fractionating column is provided with Feed inlet, gas-phase product outlet and etherificate oil export；The mixer is provided with inlet port and outlet port；The gasoline stocks are cut The outlet of the first heavy naphtha and the feed inlet of the first set fluidizing reactor for cutting unit are in fluid communication, the first set The reaction oil gas outlet of fluidizing reactor and the feed inlet of the first set high-pressure separator are in fluid communication, and the first set is high Press the feed inlet fluid communication of the desulfurization and aromatization products outlet and the destilling tower of separator, the second weight of the destilling tower Gasoline fraction is exported to be in fluid communication with the feed inlet of the mixer, the second light gasoline fraction outlet of the destilling tower with it is described The feed inlet of methyltertiarvbutyl ether reactor is in fluid communication, the first light gasoline fraction outlet and described second of the gasoline stocks cutter unit The feed inlet for covering fluidizing reactor is in fluid communication, the reaction oil gas outlet and described second of second set of fluidizing reactor The feed inlet for covering high-pressure separator is in fluid communication, desulfurization product outlet and the etherification reaction of second set of high-pressure separator The feed inlet of device is in fluid communication, the feed inlet stream of the reacting product outlet of the methyltertiarvbutyl ether reactor and the etherification product fractionating column Body is connected to, and the etherificate oil export of the etherification product fractionating column is in fluid communication with the feed inlet of the mixer.

Optionally, the gasoline stocks cutter unit may be provided at the top of catalytic cracking main fractionating tower, using condensed in two stages Flow is equipped with first segment condenser, the first knockout drum, second segment condenser and the second knockout drum；The catalysis is split Change main fractionating tower and be provided with feed inlet and tower top oil gas vent, first knockout drum is provided with feed inlet, product liquid Outlet and gas phase product exit, second knockout drum are provided with feed inlet, liquid product outlet and rich gas outlet；It is described The charging that the tower top oil gas vent of catalytic cracking main fractionating tower passes through the first segment condenser and first knockout drum Mouth is in fluid communication, and the gas-phase product outlet of first knockout drum passes through second segment condenser and second gas-liquid separation The feed inlet of tank is in fluid communication, and the liquid product outlet of first knockout drum is the of the gasoline stocks cutter unit One heavy naphtha exports, and the liquid product outlet of second knockout drum is the first of the gasoline stocks cutter unit Light gasoline fraction exports.

The present invention has the following technical effects compared with prior art：

1, method of the invention need not increase or gasoline stocks can be divided into the first light petrol using destilling tower Then two kinds of gasoline fractions are handled in two sets of fluidizing reactors, can be distinguished by fraction and the second heavy naphtha respectively Using reaction condition that is harsh or mitigating, while reducing gasoline component sulfur content, additionally it is possible to keep the octane number of gasoline with In high yield.

2, the first heavy naphtha and absorbing desulfurization catalyst and aromatized catalyst are carried out desulfurization and aromatization by the present invention Change reaction, it is ensured that octane number does not reduce, while being carried out in a fluidizing reactor using two kinds of catalyst, both improves 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, the second light gasoline fraction is carried out etherification process by the present invention, not only eliminates light gasoline fraction pretreatment unit, Moreover, wherein alkene can either be reduced, additionally it is possible to produce high-octane etherificate oil, improve the octane number of gasoline products.

5, alkene aromatized catalyst of the invention passes through aging and/or Passivation Treatment, makes alkene aromatized catalyst Activity is moderate, is conducive to the progress of aromatisation.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Description of the drawings

Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, 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 includes a kind of flow diagram of specific implementation mode of the method for the present invention, also includes a kind of tool of present system The structural schematic diagram of body embodiment.

Fig. 2 includes the flow diagram of the method for the present invention another kind specific implementation mode, also includes that present system is another The structural schematic diagram of kind specific implementation mode.

Reference sign

1 catalytic cracking main fractionating tower, 2 first segment condenser, 3 first knockout drum

45 second knockout drum of second segment condenser, 6 first set fluidizing reactor

78 second sets of first set high-pressure separator, 9 second sets of fluidizing reactor high-pressure separators

10 destilling tower, 11 methyltertiarvbutyl ether reactor, 12 etherification product fractionating column

13 mixer, 14 pipeline, 15 pipeline

16 pipeline, 17 pipeline, 18 pipeline

19 pipeline, 20 pipeline, 21 pipeline

22 pipeline, 23 pipeline, 24 pipeline

25 pipeline, 26 pipeline, 27 pipeline

28 pipeline, 29 pipeline, 30 pipeline

31 pipeline, 32 pipeline, 33 pipeline

34 pipeline, 35 pipeline, 36 pipeline

37 pipeline, 100 gasoline stocks cutter unit

Specific implementation mode

The specific implementation mode of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched The specific implementation mode stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

In the present invention RIPP test methods for details, reference can be made to《Petrochemical analysis method》, Yang Cui is surely equal to be compiled, nineteen ninety version.

The present invention provides a kind of method of gasoline desulfurization and aromatisation, and this method includes：Gasoline stocks progress first is cut It cuts, obtains the first light gasoline fraction and the first heavy naphtha；It is anti-that the first heavy naphtha of gained is sent into first set fluidization It answers and is contacted with mixed catalyst in device and carry out desulfurization and aromatization in the case where facing hydrogen state, obtain desulfurization and aromatisation production Object；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；The first light petrol of gained is evaporated It is distributed into second set of fluidizing reactor and desulphurization reaction is contacted and carried out with absorbing desulfurization catalyst, obtain desulfurization product；By institute It obtains desulfurization and aromatization products carries out the second cutting, obtain the second light gasoline fraction and the second heavy naphtha；By gained second Light gasoline fraction and the desulfurization product carry out etherification process together, obtain etherificate oil.

According to the present invention, in order to which direct producing country V even VI label gasoline of state, this method can also include：By gained Two heavy naphthas are mixed with etherificate oil, obtain gasoline products.

According to the present invention, desulfurization and aromatization refer to that the first heavy naphtha is urged in the case where facing hydrogen state in absorption desulfurization Desulfurization is carried out under agent and the collective effect of alkene aromatized catalyst and converts alkene to the process of aromatic hydrocarbons, is during which accompanied by Cracking reaction；Desulphurization reaction refers to that the first light gasoline fraction is taken off under the action of under facing hydrogen state in absorbing desulfurization catalyst The process of sulphur.The condition of the desulfurization and aromatization and the desulphurization reaction may include each independently：Reaction temperature It is 350-500 DEG C, preferably 380-420 DEG C, weight (hourly) space velocity (WHSV) is 2-50 hours^-1, preferably 5-20 hours^-1, reaction pressure is 0.5-3.5MPa, preferably 1.5-2.5MPa；Hydrogen and the first heavy naphtha volume ratio are (in 0 DEG C of the status of criterion (STP) (273K)、1.01×10⁵Under Pa) it is 1-500, preferably 50-200, alternatively, hydrogen and the first light gasoline fraction volume ratio ( The status of criterion (STP) 0 DEG C of (273K), 1.01 × 10⁵Under Pa) it is 1-500, preferably 50-200.

According to the present invention, absorbing desulfurization catalyst is well-known to those skilled in the art, for example, the absorption desulfurization is urged Agent can contain silica, aluminium oxide, zinc oxide and desulphurizing activated metal, the desulphurizing activated metal can be selected from At least one of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium.

A kind of specific implementation mode, 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, 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 the alkene virtue On the basis of the total weight of structure catalyst, the alkene aromatized catalyst can the molecular sieve containing 10-30 weight %, 0.1- The carrier of the aromatization activity metal oxide and 50-89 weight % of 20 weight %；Wherein, the molecular sieve may include Y points Son sieve and/or MFI structure molecular sieve, preferably five-membered ring high-silica zeolite, the high-silica zeolite can be Hydrogens, can also It is 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 can Think selected from least one of ZSM-5, ZSM-8 and ZSM-11.The aromatization activity metal can play partial desulfurization or Hydrocarbon conversion function, such as can be that metallic element, metallic element, the metal of group VIB of Group VB selected from group ivb are first The metallic element of element, the metallic element of group VIII, the metallic element of group ib, the metallic element of group iib and group III A At least one of；The metallic element preferred Zr or/and Ti of wherein group ivb, the preferred V of metallic element of Group VB, group VIB Metallic element preferred Mo or/and W, one or more of metallic element preferred Fe, Co, Ni of group VIII element, The preferred Cu of metallic element of group ib, the preferred Zn of metallic element of group iib, the preferred Ga of metallic element of group III A, into one Step ground, the aromatization activity metal are preferably selected from least one of Fe, Zn and Ga, and content is preferably 0.5-5 weight %. The carrier preferably includes silica and/or aluminium oxide.It is micro- that the grain size of the alkene aromatized catalyst is generally 20-120 Rice is suitable with absorbing desulfurization catalyst grain size.Absorbing desulfurization catalyst and alkene aromatized catalyst are separately formed by the present invention It is used in mixed way after (such as spray drying).

A kind of specific implementation mode, 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, be introduced into phosphorus-containing compound and one or more in Fe, Co, Ni, Zn, Mn, Ga and Sn change molecular sieve Property, it is roasted 0.5-8 hours at 400-800 DEG C later, wherein the described processing procedure roasted can also be in steam atmosphere Lower progress.Further, MFI structure molecular sieve provided by the present invention, being modified to molecular sieve in preparation process can be with It is to be carried out by the way of dipping or ion exchange.Further, the phosphorus-containing compound can be selected from phosphoric acid, phosphoric acid hydrogen Or mixtures thereof one of ammonium, ammonium dihydrogen phosphate or ammonium phosphate.Further, Fe, Co, Ni, Zn, Mn, Ga and Sn chemical combination Object can be selected from their water soluble salt, and the water soluble salt can be one in sulfate, nitrate, chlorate Kind.Further, MFI structure molecular sieve provided by the present invention, containing phosphorus and metal component, the dehydrogenation in acid site and metal Close centre combines, and the presence of phosphorus simultaneously can not only improve the structural stability of molecular sieve but also make the ability of dehydrogenation of metal Sulfurization.

The method that the present invention introduces metal active constituent on molecular sieve or carrier, may be used existing various gold-supporteds Belong to the method for oxide, such as method of dipping, that is, uses one or more of metal salt solution impregnated zeolites or carrier；Or it is heavy The method in shallow lake uses 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 in shallow lake or the method for dipping.

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, and preferred ratio is obtained according to many experiments of inventor, for example, by weight, The ratio that the alkene aromatized catalyst accounts for the mixed catalyst is 1-30 weight %, preferably 3-15 weight %.

According to the present invention, the alkene aromatized catalyst may include selected from fresh aromatized catalyst, passivation aromatization Change at least one of catalyst and aging aromatized catalyst.Present inventors discovered unexpectedly that alkene aromatisation is urged The micro-activity of agent effect in 20-55 is more excellent, and the micro-activity is urged using RIPP 92-90 catalytic cracking industry balance The mat activity test method of agent is measured.However from manufacturer production or homemade qualification not yet used fresh virtue Structure catalyst, activity is generally 60 or more, and activity is higher, and cracking performance is stronger, therefore, fresh aromatized catalyst need into Row processing increases acid strength, advantageously reduces the generation of hydrogen transfer reaction to reduce acid amount.

A kind of embodiment, the alkene aromatized catalyst pass through Passivation Treatment, can be with the step of the Passivation Treatment Including：Fresh aromatized catalyst is contacted and given birth to carbon containing and/or sulphur and/or nitrogen compound in pre-reactor It is burnt；Or regeneration aromatized catalyst is contacted and given birth to carbon containing and/or sulphur and/or nitrogen compound in pre-reactor It is burnt；Or aromatized catalyst to be generated is subjected to incomplete singeing regeneration, in the passivation aromatized catalyst, passivation content For 0.1-5.0 weight %, preferably 0.3-2.0 weight %, further preferably 0.3-1 weight %, the passivation can wrap It includes selected from least one of carbon, sulphur and nitrogen element, preferably coke, with or without having sulphur and/or nitrogen.The aromatisation to be generated Catalyst refers in fluidizing reactor by using the catalyst for having loaded certain coke, activity reduces, is not enough to continue It is reacted.Aromatized catalyst to be generated, which is carried out incomplete singeing regeneration, makes loaded coke content reduce, and can obtain More suitable activity.The regeneration aromatized catalyst is by aromatized catalyst to be generated through regeneration gained completely, regeneration temperature Generally 450-690 DEG C, regeneration gas is generally oxygen-containing gas, returns in fluidizing reactor and follows by regenerated catalyst circulation Ring uses.Regenerate aromatized catalyst coke content generally in 0.1 weight % hereinafter, hyperactivity, thus with fresh aromatisation Catalyst equally needs to carry out green coke in pre-reactor, but the activity of fresh aromatized catalyst is higher than institute under normal circumstances Regeneration aromatized catalyst is stated, required amount of coke is less.

The green coke of the fresh aromatized catalyst and regeneration aromatized catalyst can be reacted positioned at the fluidization It carries out, can also be carried out in the pre lift zone 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 include aging aromatized catalyst, aging Aromatizatian catalytic Agent refers to the fresh aromatized catalyst after burin-in process.It will be fresh under the conditions of burin-in process refers to existing for vapor Aromatized catalyst carries out high-temperature process, to reduce its activity.The condition of the burin-in process may include：Temperature is 500- 800 DEG C, the time is 1-360 hours, and aging atmosphere contains vapor, preferably 100% steam atmosphere.

A kind of specific implementation mode of burin-in process, by fresh aromatized catalyst and vapor or steam-laden aging Media contact, under certain thermal and hydric environment after (temperature be 500 DEG C -800 DEG C) aging -360 hours 1 hour, obtained aging Aromatized catalyst.Further, the burin-in process refers to fresh aromatized catalyst in 800 DEG C and 100% vapor Under condition (with reference to RIPP 92-90) aging certain time to reduce activity, as ageing time be 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 Fluid 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, Gas or air after regenerated flue gas, air and dry combustion gas and the gas or other gases such as nitrogen after burning oil firing.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 The regenerating unit that regenerated flue gas can come from the present invention is stated, other regenerating units are can be from.

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 10 body %, preferably greater than 20 body %, more preferably greater than 30 body %, Further preferably greater than 40 body % are further more 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 more than 1000 μ g/g, having in gasoline Machine sulfide is generally mercaptan, thioether, thiophene, alkylthrophene, benzothiophene and methyl benzothiophene etc..

A kind of specific implementation mode, the gasoline stocks are catalytically cracked gasoline, described to cut gasoline stocks Step includes：Future, the tower top oil gas of the main destilling tower of catalytic cracking carried out two sections of condensations, and first segment, which is condensed gained gasoline, to be produced Object condenses gained gasoline product as first light gasoline fraction as first heavy naphtha, using second segment.Specifically Ground, as shown in Fig. 2, two sections of condensers are subsequently arranged in catalytic cracking main fractionating tower 1, by 1 tower top oil gas of catalytic cracking main fractionating tower It is cooled to 60-100 DEG C, preferably 60-80 DEG C, isolated heavy naphtha, uncooled gaseous stream through first segment condenser 2 It is cooled to 40 DEG C or so through second segment condenser 4, isolated light gasoline fraction and rich gas.Heavy naphtha is divided into two strands, and one Stock returns to catalytic cracking main fractionating tower 1 as reflux, and another strand introduces first set fluidizing reactor 6；Above-mentioned light petrol evaporates It separates into second set of fluidizing reactor 8.By adjust 3 cooling temperature of first segment condenser can control the first light gasoline fraction and First heavy naphtha distillates weight ratio, for example, the first light gasoline fraction: the first heavy naphtha=(0.2-2): 1.

According to the present invention, the cut point and the second light vapour of first light gasoline fraction and the first heavy naphtha The cut point of oil distillate and the second heavy naphtha can be each independently 60-100 DEG C, preferably 60-80 DEG C, further excellent It is selected as 65-80 DEG C, the Engler distillation of light gasoline fraction does preferably 60-100 DEG C, further preferably 60-80 DEG C.Desulfurization and The cutting of aromatization products carries out generally in fractionating column according to boiling range from low to high, for example, the behaviour of the fractionating column of gasoline cutting It is as condition：Tower top temperature is 60-80 DEG C, and column bottom temperature is 120-160 DEG C, operating pressure 0.05-0.3MPa.

According to the present invention, fluidizing reactor is well-known to those skilled in the art, for example, can be selected from fluid bed, It is riser, downstriker pipeline reactor, the compound reactor being made of with fluid bed riser, defeated by riser and downstriker Compound reactor that line sending is constituted, the compound reactor being made of two or more risers, by two or two with On the fluid bed compound reactor constituted and the compound reactor being made of two or more downstriker pipelines in At least one, preferably riser reactor and/or fluidized-bed reactor, each above-mentioned reactor be segmented into two or two A above reaction zone.The fluidized-bed reactor can be 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 be to be promoted selected from equal diameter Pipe, etc. one or more of linear speeds riser and various variable diameters risers.Preferably, the fluidizing reactor is selected from close Phase fluidizing reactor, more preferably variable diameters riser reactor.

According to the present invention, etherification process refers to by C in the second light gasoline fraction and desulfurization product₅Low-carbon hydro carbons below (such as iso-amylene and cyclopentene) carries out etherification reaction with alcohols, to generate high-octane etherificate oil, for example, at the etherificate The step of reason may include：Second light gasoline fraction and the desulfurization product are contacted with alcohols, make the described second light vapour Under the action of catalyst for etherification with alcohols etherification reaction occurs for the alkene in oil distillate and the desulfurization product, obtains the ether Carburetion；Wherein, the temperature of the etherification reaction is 20-200 DEG C, pressure 0.1-5MPa, and weight (hourly) space velocity (WHSV) is 0.1-20 hours^-1, The ratio of the sum of the molal quantity of the alcohols and the molal quantity of the second light gasoline fraction and desulfurization product is 1：(0.1-100), institute It includes selected from least one of resin, molecular sieve and heteropoly acid to state catalyst for etherification.

Strong acid cation exchange resin catalyst is loaded on one section of etherificate by a kind of specific implementation mode of etherification process And/or in two sections of etherificate fixed bed reactors, pretreated second light gasoline fractions such as desulfurization and dialkene removal will be passed through It is passed through in methyltertiarvbutyl ether reactor with the desulfurization product, is 50-90 DEG C in reaction temperature, liquid hourly space velocity (LHSV) 1.0-3.0h^-1, methanol and institute State all active olefin (isomeric olefine, such as iso-amylene) molar ratio 1-2 in the second light gasoline fraction and the desulfurization product Under the conditions of occur etherification reaction, etherification product is sent into rectifying column separation, and etherificate oil, unreacted lighter hydrocarbons and methanol are obtained in bottom of tower It recycles.Etherification procedure reaction temperature preferably is 55-60 DEG C of inlet temperature, and outlet temperature is less than 90 DEG C, and air speed is preferred For 1-2h^-1, the molal quantity of methanol and all active olefin molar ratios in second light gasoline fraction and the desulfurization product are excellent It is selected as 1.2-1.4.Wherein, one section etherificate olefin(e) centent it is higher, suitable for use mixed phase bed reactor, two sections etherificate olefin(e) centents compared with It is low, suitable for using insulation fix bed reactor.In addition, isomerization unit can also be applied to the second light gasoline fraction and desulfurization production In object etherification procedure.Second light gasoline fraction and desulfurization product etherificate have reduction content of olefin in gasoline, improve octane number, reduce Many advantages, such as vapour pressure and raising added value and reinforcing reconciliation benefit, etherificate oil can be used as octane number blend component It is used, can also be mixed with the second heavy naphtha as full distillation gasoline product.

As shown in Figure 1, the present invention also provides a kind of system of gasoline desulfurization and aromatisation, which includes：Gasoline stocks Cutter unit 100, first set fluidizing reactor 6,7, second sets of first set high-pressure separator, 8, second sets of fluidizing reactor High-pressure separator 9, destilling tower 10, methyltertiarvbutyl ether reactor 11, etherification product fractionating column 12 and mixer 13；The gasoline stocks cutting Unit 100 is provided with gasoline stocks entrance, the outlet of the first light gasoline fraction and the outlet of the first heavy naphtha, the first set stream State reactor 6 is provided with feed inlet and reaction oil gas outlet, and the first set high-pressure separator 7 is provided with feed inlet, gas Outlet and desulfurization and aromatization products outlet, second set of fluidizing reactor 8 is provided with feed inlet and reaction oil gas goes out Mouthful, second set of high-pressure separator 9 is provided with feed inlet, gas vent and desulfurization product outlet, the destilling tower 10 and is arranged There are feed inlet, the outlet of the second light gasoline fraction and the outlet of the second heavy naphtha；The methyltertiarvbutyl ether reactor 11 is provided with feed inlet And reacting product outlet, the etherification product fractionating column 12 are provided with feed inlet, gas-phase product outlet and etherificate oil export；It is described Mixer 13 is provided with inlet port and outlet port；First heavy naphtha of the gasoline stocks cutter unit 100 exports and institute The feed inlet for stating first set fluidizing reactor 6 is in fluid communication, the outlet of the reaction oil gas of the first set fluidizing reactor 6 with The feed inlet of the first set high-pressure separator 7 is in fluid communication, the desulfurization of the first set high-pressure separator 7 and aromatization products Outlet and the feed inlet of the destilling tower 10 are in fluid communication, and the second heavy naphtha outlet of the destilling tower 10 is mixed with described The feed inlet of device 13 is in fluid communication, the charging of the second light gasoline fraction outlet and the methyltertiarvbutyl ether reactor 11 of the destilling tower 10 Mouth is in fluid communication, and the first light gasoline fraction outlet of the gasoline stocks cutter unit 100 is reacted with second set of fluidization The feed inlet of device 8 is in fluid communication, and the reaction oil gas outlet of second set of fluidizing reactor 8 is detached with second set of high pressure The feed inlet of device 9 is in fluid communication, the desulfurization product outlet of second set high-pressure separator 9 and the methyltertiarvbutyl ether reactor 11 into Material mouth is in fluid communication, the feed inlet fluid of the reacting product outlet of the methyltertiarvbutyl ether reactor 11 and the etherification product fractionating column 12 Connection, the etherificate oil export of the etherification product fractionating column 12 are in fluid communication with the feed inlet of the mixer 13.

Gasoline stocks can be cut and be respectively processed by system provided by the invention, to improve gasoline products Octane number and yield.Wherein gasoline stocks cutter unit 100 can be arranged in catalytic cracking fractionating tower top portion, in order to save fractionation The investment of tower, a kind of specific implementation mode, as shown in Fig. 2, when the gasoline stocks are catalytically cracked gasoline, the gasoline is former Material cutter unit 100 can be arranged in catalytic cracking fractionating tower top portion, using condensed in two stages flow, be equipped with first segment condenser 2, First knockout drum 3, second segment condenser 4 and the second knockout drum 5；The catalytic cracking main fractionating tower 1 be provided with into Material mouth and tower top oil gas vent, first knockout drum 3 are provided with feed inlet, liquid product outlet and gas-phase product and go out Mouthful, second knockout drum 5 is provided with feed inlet, liquid product outlet and rich gas outlet；The main fractionation of catalytic cracking The tower top oil gas vent of tower 1 is in fluid communication by the feed inlet of the first segment condenser 2 and first knockout drum 3, The charging that the gas-phase product outlet of first knockout drum 3 passes through second segment condenser 4 and second knockout drum 5 Mouth is in fluid communication, and the liquid product outlet of first knockout drum 3 is the first weight of the gasoline stocks cutter unit 100 Gasoline fraction exports, and the liquid product outlet of second knockout drum 5 is the first of the gasoline stocks cutter unit 100 Light gasoline fraction exports.The specific implementation mode is only needed two sections of condensers and two knockout drums are additionally arranged and can will be catalyzed Cracking gasoline is split, to save energy consumption caused by gasoline stocks cutting.

A kind of specific implementation mode of the present invention is provided below in conjunction with attached drawing, but it is not thereby limiting the invention.

As shown in Fig. 2, 1 tower top oil gas of catalytic cracking main fractionating tower is cooled to 60-80 through pipeline 14, first segment condenser 2 DEG C or so, condensed stream passes via line 15, which enters in the first knockout drum 3, is separated into the first heavy naphtha, water and gas phase Logistics.Gaseous stream is further cooled to 40-50 DEG C or so through pipeline 19, second segment condenser 4, enters the second gas through pipeline 20 Liquid knockout drum 5 is separated into the first light gasoline fraction and rich gas, and the first light gasoline fraction is drawn through pipeline 21, and rich gas draws through pipeline 22 Go out to gas compressor system.The first heavy naphtha isolated in first knockout drum 3, is divided into two strands, one conduct Reflux via line 17 returns to catalytic cracking main fractionating tower 1, to balance the operation of main catalytic cracking main fractionating tower 1, another stock-traders' know-how Pipeline 16 introduces first set fluidizing reactor 6, is mixed with the hydrogen introduced through pipeline 23, in absorbing desulfurization catalyst and alkene It is reacted under the action of aromatized catalyst, the reaction oil gas of generation introduces first set high-pressure separator 7 through pipeline 24, isolated Desulfurization and aromatization products lead to destilling tower 10, isolated the second light gasoline fraction and the second heavy naphtha through pipeline 25 It is drawn respectively by pipeline 28 and pipeline 27, wherein the cut point of the second light gasoline fraction and the second heavy naphtha is about 60~ 70℃.The first light gasoline fraction isolated in knockout drum 5 introduces second set of fluidizing reactor 8 through pipeline 21, with warp The hydrogen mixing that pipeline 29 introduces, reacts under the action of absorbing desulfurization catalyst, and the reaction oil gas of generation is introduced through pipeline 30 Second set of high-pressure separator 9, isolated desulfurization product are drawn through pipeline 31.The second light gasoline fraction for being drawn by pipeline 28 and The desulfurization product drawn by pipeline 31 converges and is mixed with the methanol introduced through pipeline 33, is reacted into methyltertiarvbutyl ether reactor 11, ether Change product and introduce etherification product fractionating column 12 through pipeline 34, is fractionated into obtain etherificate oil and tail gas, tail gas is drawn through pipeline 36, ether Carburetion, which is drawn through pipeline 35 and converged with the second heavy naphtha, introduces mixer 13, and gasoline products are drawn through pipeline 37.

Difference lies in use gasoline stocks cutter unit 100, such as fractionating column to substitute first segment condenser by Fig. 2 and Fig. 1 2, the first knockout drum 3, second segment condenser 4 and the second knockout drum 5.

The following examples will be further described the present invention, but not thereby limiting the invention.

The crystallinity of the present invention is measured using the standard method of ASTM D5758-2001 (2011) e1.

N (the SiO of the present invention₂)/n(Al₂O₃), i.e., silica alumina ratio is obtained by the content calculation of silica and aluminium oxide, oxidation The content of silicon and aluminium oxide is measured using GB/T 30905-2014 standard methods.

The phosphorus content of the present invention is measured using GB/T 30905-2014 standard methods, and the content of carried metal uses GB/T 30905-2014 standard methods are measured, and sodium content is measured using GB/T 30905-2014 standard methods.

The total specific surface area measurement methods of BET of the present invention are as follows：

The AS-3 produced using Quantachrome instrument companies, AS-6 static state n2 absorption apparatus are measured.

Instrument parameter：Sample is placed in sample processing system, 1.33 × 10 are evacuated at 300 DEG C^-2Pa, heat-insulation pressure keeping 4h purifies sample.At -196 DEG C of liquid nitrogen temperature, test purification sample is not pressing P/P on year-on-year basis₀Under the conditions of to the adsorbance of nitrogen And desorption rate, obtain N₂Then adsorption-desorption isothermal curve utilizes two parameter BET formula to calculate total specific surface area.

The test method of dry weight is in the present invention：Testing molecule sieve or catalyst are placed in Muffle furnace at 600 DEG C Under air atmosphere in carry out roasting 3 hours, obtained product of roasting is cooled to room temperature in closed drying basin, is then claimed Weight.

Absorbing desulfurization catalyst used in following example and comparative example is by Sinopec Group Catalyst branch produces, goods number FCAS, and used fresh aromatized catalyst is that laboratory makes catalyst, board by oneself Number it is OTAZ-C-3, absorbing desulfurization catalyst property is listed in table 3.The preparation method of aromatized catalyst is as follows：

The property of raw materials is as follows：Kaolin (Suzhou China Kaolin Co., Ltd, 75 weight % of solid content) intends thin water Aluminium stone (Shandong Aluminium Industrial Corp, 65 weight % of solid content, first use 31 weight % hydrochloric acid peptizations of concentration when use, the hydrochloric acid with 0.20) molar ratio of boehmite in terms of aluminium oxide is.

By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO₂)/n(Al₂O₃) =27) mother liquor is filtered out, Na is washed to₂O content is less than 3.0 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) It is added in the NaOH solution of 1000g 2.0%, is warming up to 65 DEG C, after reacting 30min, after being quickly cooled to room temperature, filter, washing To filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, after exchanging processing 1h, until Na₂O content is less than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare At the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g is added in stirring, then by 110g hydrochloric acid (mass fraction 10%) and 92g fluosilicic acid (mass fraction 3%) cocurrent is added, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to Filtrate is neutral；By filter cake plus water be beaten solid content be 45 weight % molecular sieve pulps；By 1.2gH₃PO₄(85 weight % of concentration) With 3.3gZn (NO₃)₂·6H₂O is dissolved in 10g water, and ammonium hydroxide is added and adjusts pH=6, is then added in molecular sieve pulp and is mixed Even, drying, the lower 550 DEG C of calcination process 2h of 100% steam atmosphere.Molecular sieve-4 A is obtained, physico-chemical property is listed in table 4.

Boehmite is mixed with kaolin, decationized Y sieve water is used in combination to be configured to the slurry that solid content is 30 weight % Liquid stirs evenly, and slurries pH is adjusted to 2.5 with hydrochloric acid, keeps the pH value, is stirred 1 hour after aging being stood at 50 DEG C 1 hour It forms colloid, prepared molecular sieve-4 A and water is added, form catalyst slurry (solid content is remembered for 35% weight).Continue to stir Microspherical catalyst is made in spray drying afterwards.Then microspherical catalyst is roasted 1 hour at 500 DEG C, obtains the alkene used in the present invention Hydrocarbon aromatizing catalyst, the butt raw material proportioning of alkene aromatized catalyst is 25 weight % kaolin, 25 weight % intend thin water Aluminium stone and 50 weight % molecular sieve-4 As.

Passivation content in passivation aromatized catalyst is measured using RIPP107-90 methods.

In following embodiment and comparative example, NiO, ZnO, Al in catalyst₂O₃、SiO₂Content x-ray fluorescence method It measures, wherein Al₂O₃、SiO₂Content measured referring specifically to RIPP 134-90, remaining composition measuring method is similar.

GB/T 5487-1995 and GB/ is respectively adopted in the octane number RON and MON of gasoline in the embodiment of the present invention and comparative example T 503-1995 standard methods are measured, anti-knock index=(MON+RON)/2, and gasoline PONA is using simulation distillation and gasoline list Body hydrocarbon analyzes (ASTM D2887 and ASTM D6733-01 (2011) test method is respectively adopted to be tested), content of sulfur in gasoline It is measured using SH/T0689-2000.

The experiment of the catalytic cracking unit of the embodiment of the present invention and comparative example is carried out in medium-sized variable diameters riser arrangement , condensed in two stages cooling process may be used in the fractionating column of medium-sized variable diameters riser arrangement, one section of routine can also be used cold Solidifying cooling process.The fluidizing reactor of embodiment and comparative example carries out on small fixed fluidized bed unit.

Embodiment 1

As shown in Fig. 2, 1 tower top of catalytic cracking main fractionating tower uses condensed in two stages cooling process, the operation of first segment condenser 65 DEG C or so of temperature, isolated first heavy naphtha HCN-A-1, uncooled gaseous stream are cooled to through second segment condenser 40 DEG C or so, isolated first light gasoline fraction LCN-A-1.The property of HCN-A-1 and LCN-A-1 is listed in table 2.By the first weight Gasoline fraction HCN-A-1 is sent into first set fluidizing reactor 1 and absorbing desulfurization catalyst FCAS and Fresh olefin aromatisation The mixed catalyst (fresh aromatized catalyst OTAZ-C-3 accounts for the 7% of mixed catalyst total weight) of OTAZ-C-3 contact and Face progress desulfurization and aromatization, reaction condition under hydrogen state and be listed in table 5, is produced by the first heavy petrol that reactor head obtains Object be cooled and separated to obtain tail gas and desulfurization and aromatization products (be denoted as gasoline after HCN-A-1 desulfurization, 5) property is shown in Table, Gasoline after HCN-A-1 desulfurization is sent into destilling tower, 65 DEG C or so of control overhead temperature, tower top obtains the second light petrol Fraction LCN-A-2, bottom of tower obtain the second heavy naphtha HCN-A-2, and property is equally listed in table 2；The first light petrol of gained is evaporated Divide LCN-A-1 to be sent into second set of fluidizing reactor 8 to contact with absorbing desulfurization catalyst FCAS and taken off in the case where facing hydrogen state Reaction of Salmon-Saxl, reaction condition are equally listed in table 5, are cooled and separated to obtain tail gas and be taken off by the desulfurization product that reactor head obtains Sulphur product (is denoted as gasoline after LCN-A-1 desulfurization, 5) property is shown in Table；By the second light gasoline fraction LCN-A-2 and LCN-A-1 desulfurization Gasoline converges and is mixed with methanol afterwards, is reacted into methyltertiarvbutyl ether reactor 11, and etherification reaction condition is 55-80 DEG C of reaction temperature, empty Fast 1.2h^-1, gross activity alkene (isomeric olefine) molar ratio 1.2 in methanol and the second light gasoline fraction and desulfurization product reacts To etherificate after oil gas etherified product fractionation tower 12 fractionation obtain bottom of tower etherificate oil and contain methanol-fueled exhaust with tower top, wherein etherificate production The tower top temperature of object fractionating column is 60-80 DEG C, and column bottom temperature is 110-140 DEG C, and etherificate oil is denoted as LCN-A-M-0, and property is listed in Table 2.Gained the second heavy naphtha HCN-A-2 and LCN-A-M-0 are mixed, the gasoline products as treated gasoline, property are obtained Matter is shown in Table 6.

Embodiment 2

The passivation of aromatized catalyst：HCN-A-1 and LCN-A-1 is mixed, full distillation gasoline CN-A, property row are obtained In table 1.The fresh aromatized catalyst that the trade mark is OTAZ-C-3 is packed into dense-phase fluidized bed reactor, in 410 DEG C of passivation temperature Under the conditions of with the full distillation gasoline CN-A haptoreactions as passivator, continuously inactivating 2 hours, obtain passivation Aromatizatian catalytic Agent, passivation content are 0.5 weight %.

Fresh aromatized catalyst in above-mentioned passivation aromatized catalyst alternative embodiment 1 is subjected to desulfurization and aromatisation Reaction, remaining condition is same as Example 1, obtains gasoline products, and property is shown in Table 6.

Embodiment 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 35.

Fresh aromatized catalyst in above-mentioned aging aromatized catalyst alternative embodiment 1 is subjected to desulfurization and aromatisation Reaction, remaining condition is same as Example 1, obtains gasoline products, and property is shown in Table 6.

Comparative example 1

Catalytic cracking main fractionating tower tower top uses conventional condensation cooling process, 40 DEG C or so of condenser operation temperature, separation Full distillation gasoline CN-A is obtained, property is listed in table 1；Full distillation gasoline CN-A is sent into above-mentioned wherein second set of fluidizing reactor (OTAZ-C-3 accounts for mixed catalytic with the mixed catalyst of absorbing desulfurization catalyst FCAS and alkene aromatized catalyst OTAZ-C-3 The 7% of agent total weight) it contacts and carries out desulfurization and aromatization in the case where facing hydrogen state, reaction condition is listed in table 5, by reactor The product that top obtains is cooled and separated gasoline product after obtaining tail gas and desulfurization and (is denoted as gasoline after CN-A desulfurization, property is shown in Table 5), gasoline product is not fractionated into and is etherified as gasoline products after desulfurization；Gasoline is as gasoline products, property after CN-A desulfurization It is listed in table 6.

Comparative example 2

It is carried out in two steps, the first step is identical as the operation of comparative example 1, and second step is to be sent into gasoline product after CN-A desulfurization Light gasoline fraction LCN-A-S and heavy naphtha HCN-A-S are cut into destilling tower, wherein the control light gasoline fraction end point of distillation For 65-70 DEG C (being carried out according to ASTM D86 standards).By light gasoline fraction LCN-A-S and methanol be mixed into methyltertiarvbutyl ether reactor into Row etherification reaction, etherification reaction condition and operation are same as Example 1, and the corresponding oil that is etherified is denoted as LCN-A-M-S, property row In table 2.

Heavy naphtha HCN-A-S obtained above and etherificate oil LCN-A-M-S is mixed to get gasoline products, property row In table 6.

Comparative example 3

Essentially identical with the operation of embodiment 1, difference replaces the fresh virtues of OTAZ-C-3 using absorbing desulfurization catalyst Structure catalyst, obtains gasoline products, and property is shown in Table 6.

It can be seen from Table 6 that embodiment 1 is suitable with the desulfuration efficiency of comparative example 1 and comparative example 2, but embodiment 1 is ground Study carefully method octane number 2.5 units of loss fewer than comparative example 1,1 unit of loss fewer than comparative example 2 and 3, and embodiment 2-3 is ground The method octane number of studying carefully is better than embodiment 1.

Table 1

Experimental program	Comparative example 1
		Gasoline stocks	CN-A
20 DEG C of density, kg/m³	737.3
		20 DEG C of refractive index	1.4212
Carbon content, % (w)	86.36
		Hydrogen content, % (w)	13.64
Sulfur content, mg/L	421
		Nitrogen content, mg/L	139
Induction period, min	667
		Race forms (FIA methods)
Aromatic hydrocarbons, % (volume fraction)	15.4
		Alkene, % (volume fraction)	54.9
Saturated hydrocarbons, % (volume fraction)	29.7
		Survey RON	90.9
Survey MON	78.9
		Normal pressure boiling range, DEG C
IBP	44
		5%	59
10%	63
		30%	80
50%	106
		70%	139
90%	175
		FBP	204

Table 2

Table 3

Catalyst	FCAS
		Chemical composition, weight %
Aluminium oxide	11
		Nickel oxide	20
Zinc oxide	49
		Silica	20
Apparent density, kg/m³	1130
		Screening composition, weight %
0~40 micron	14.5
		40~80 microns	51.9
>80 microns	33.6

Table 4

Project	Molecular sieve-4 A
		Crystallinity/%	90
n(SiO₂)/n(Al₂O₃)	110
		P₂O₅Content/%	1.5
Metal oxide-loaded content/%	1.6
		S_BET/(m²/g)	440

Table 5

Table 6

Claims

1. a kind of method of gasoline desulfurization and aromatisation, this method include：

Gasoline stocks are subjected to the first cutting, obtain the first light gasoline fraction and the first heavy naphtha；

The first heavy naphtha of gained is sent into first set fluidizing reactor and is contacted with mixed catalyst and is facing hydrogen state Lower progress desulfurization and aromatization, obtain desulfurization and aromatization products；Wherein, the mixed catalyst includes that absorption desulfurization is urged Agent and alkene aromatized catalyst；

The first light gasoline fraction of gained second set of fluidizing reactor of feeding is contacted with absorbing desulfurization catalyst and carries out desulfurization Reaction, obtains desulfurization product；

Gained desulfurization and aromatization products are subjected to the second cutting, obtain the second light gasoline fraction and the second heavy naphtha；

The second light gasoline fraction of gained and the desulfurization product are subjected to etherification process together, obtain etherificate oil.

2. according to the method described in claim 1, this method further includes：The second heavy naphtha of gained is mixed with etherificate oil, Obtain gasoline products.

3. according to the method described in claim 1, wherein, the alkene aromatized catalyst includes being selected from fresh Aromatizatian catalytic Agent, passivation at least one of aromatized catalyst and aging aromatized catalyst；Wherein, the passivation aromatized catalyst In, passivation content is 0.1-5.0 weight %, and the passivation includes selected from least one of carbon, sulphur and nitrogen element.

4. according to the method described in claim 1, wherein, volume fraction of olefins is more than 10 body % in the gasoline stocks.

5. according to the method described in claim 1, wherein, sulfur content is more than 10 μ g/g in the gasoline stocks.

6. 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.

7. according to the method described in claim 1, wherein, the gasoline stocks are catalytically cracked gasoline, described by gasoline stocks The step of being cut include：Future, the tower top oil gas of the main destilling tower of catalytic cracking carried out two sections of condensations, and first segment is condensed Gained gasoline product condenses gained gasoline product as first light petrol as first heavy naphtha, using second segment Fraction.

8. according to the method described in claim 1, wherein, the cut point of first light gasoline fraction and the first heavy naphtha It it is 60-100 DEG C, the cut point of second light gasoline fraction and the second heavy naphtha is 60-100 DEG C.

9. according to the method described in claim 1, wherein, the first set fluidizing reactor and second set of fluidizing reactor It is each independently selected from fluid bed, riser, downstriker pipeline reactor, the recombination reaction being made of riser and fluid bed Device, the compound reactor being made of with downstriker pipeline riser, be made of two or more risers it is compound It reactor, the compound reactor being made of two or more fluid beds and is conveyed by two or more downstrikers At least one of the compound reactor that line is constituted.

10. the method according to claim 1 or 9, wherein the first set fluidizing reactor and second set of fluidization are anti- Device is answered to be each independently one or more of equal diameter riser, variable diameters riser, dense-phase fluidized bed reactor, first Set fluidizing reactor belongs to gasoline absorbing desulfurization and aromatisation device, and second set of fluidizing reactor belongs to gasoline adsorption and take off Sulphur device.

11. 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.

12. according to the method for claim 11, 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 weights % is measured, 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, institute The content for stating desulphurizing activated metal described in absorbing desulfurization catalyst is 5-30 weight %.

13. 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, it is golden that the alkene aromatized catalyst contains the molecular sieve of 10-30 weight %, the aromatization activity of 0.1-20 weight % Belong to the carrier of oxide and 50-89 weight %；Wherein, the molecular sieve includes Y molecular sieve and/or MFI structure molecular sieve, described Aromatization activity metal is metallic element selected from group ivb, the metallic element of Group VB, the metallic element of group VIB, the The metallic element of VIII group, the metallic element of group ib, the metallic element of group iib and group III A metallic element in extremely Few one kind, the carrier includes silica and/or aluminium oxide.

14. according to the method for claim 13, wherein the MFI structure molecular sieve is selected from ZSM-5, ZSM-8 and ZSM-11 At least one of, the aromatization activity metal is selected from least one of Fe, Zn and Ga.

15. 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 %.

16. according to the method described in claim 1, wherein, the condition of the desulfurization and aromatization and the desulphurization reaction Include each independently：Reaction temperature is 350-500 DEG C, and weight (hourly) space velocity (WHSV) is 2-50 hours^-1, reaction pressure 0.5-3.5MPa.

17. according to the method described in claim 1, wherein, the step of etherification process, includes：Second light petrol is evaporated Divide and the desulfurization product is contacted with alcohols, the alkene in second light gasoline fraction and the desulfurization product is made to be urged in etherificate Etherification reaction occurs with alcohols under the action of agent, 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) is 0.1-20 hours^-1, the molal quantity of the alcohols and the second light gasoline fraction and de- The ratio of the sum of the molal quantity of sulphur product is 1：(0.1-100), the catalyst for etherification include selected from resin, molecular sieve and miscellaneous more At least one of acid.

18. a kind of system of gasoline desulfurization and aromatisation, the system include：

Gasoline stocks cutter unit (100), first set fluidizing reactor (6), first set high-pressure separator (7), second set of stream State reactor (8), second set of high-pressure separator (9), destilling tower (10), methyltertiarvbutyl ether reactor (11), etherification product fractionating column (12) and mixer (13)；

The gasoline stocks cutter unit (100) is provided with gasoline stocks entrance, the outlet of the first light gasoline fraction and the first heavy vapour Oil distillate exports, and the first set fluidizing reactor (6) is provided with feed inlet and reaction oil gas outlet, the first set high pressure Separator (7) is provided with feed inlet, gas vent and desulfurization and aromatization products outlet, second set of fluidization reaction Device (8) is provided with feed inlet and reaction oil gas outlet, and second set of high-pressure separator (9) is provided with feed inlet, gas vent It is exported with desulfurization product, the destilling tower (10) is provided with feed inlet, the outlet of the second light gasoline fraction and the second heavy naphtha Outlet；The methyltertiarvbutyl ether reactor (11) is provided with feed inlet and reacting product outlet, etherification product fractionating column (12) setting There are feed inlet, gas-phase product outlet and etherificate oil export；The mixer (13) is provided with inlet port and outlet port；

The outlet of the first heavy naphtha and the first set fluidizing reactor (6) of the gasoline stocks cutter unit (100) Feed inlet be in fluid communication, the outlet of the reaction oil gas of the first set fluidizing reactor (6) is detached with the first set high pressure The feed inlet of device (7) is in fluid communication, and the desulfurization of the first set high-pressure separator (7) and aromatization products export and the distillation The feed inlet of tower (10) is in fluid communication, the second heavy naphtha outlet of the destilling tower (10) and the mixer (13) into Material mouth is in fluid communication, the feed inlet stream of the second light gasoline fraction outlet and the methyltertiarvbutyl ether reactor (11) of the destilling tower (10) Body is connected to, the outlet of the first light gasoline fraction and the second set of fluidizing reactor of the gasoline stocks cutter unit (100) (8) feed inlet is in fluid communication, reaction oil gas outlet and the second set of high pressure point of second set of fluidizing reactor (8) Feed inlet from device (9) is in fluid communication, desulfurization product outlet and the methyltertiarvbutyl ether reactor of second set of high-pressure separator (9) (11) feed inlet is in fluid communication, the reacting product outlet of the methyltertiarvbutyl ether reactor (11) and the etherification product fractionating column (12) Feed inlet be in fluid communication, the feed inlet stream of the etherificate oil export and the mixer (13) of the etherification product fractionating column (12) Body is connected to.

19. the system of gasoline desulfurization and aromatisation according to claim 18, wherein the gasoline stocks cutter unit (100) it may be provided at the top of catalytic cracking main fractionating tower (1), using condensed in two stages flow, be equipped with first segment condenser (2), the One knockout drum (3), second segment condenser (4) and the second knockout drum (5)；

The catalytic cracking main fractionating tower (1) is provided with feed inlet and tower top oil gas vent, and first knockout drum (3) sets It is equipped with feed inlet, liquid product outlet and gas phase product exit, second knockout drum (5) is provided with feed inlet, liquid Product exit and rich gas outlet；

The tower top oil gas vent of the catalytic cracking main fractionating tower (1) passes through the first segment condenser (2) and first gas The feed inlet of liquid knockout drum (3) is in fluid communication, and the gas-phase product outlet of first knockout drum (3) is condensed by second segment Device (4) and the feed inlet of second knockout drum (5) are in fluid communication, the product liquid of first knockout drum (3) Outlet is that the first heavy naphtha of the gasoline stocks cutter unit (100) exports, the liquid of second knockout drum (5) Body product exit is that the first light gasoline fraction of the gasoline stocks cutter unit (100) exports.