CN108949226A - Produce the method and system of clean gasoline - Google Patents

Abstract

The invention discloses a kind of method and system for producing clean gasoline.This method comprises: being fractionated being cut after full distillation gasoline raw material and refining agent haptoreaction as light gasoline fraction and heavy naphtha；Light gasoline fraction is contacted with alcohol and carries out level-one etherification reaction, obtains level-one etherificate product；Level-one etherificate product is fractionated and is etherified Fractionator Bottom fraction for tower top azeotropic mixture and level-one；Tower top azeotropic mixture is mixed with isomerization product and carries out second level etherification reaction, obtain second level etherificate product, second level etherificate product is subjected to washing process and obtains second level etherification product, and at least partly second level etherification product is fractionated and is etherified Fractionator Bottom fraction for overhead and second level；Second overhead is subjected to olefin skeletal isomerization processing, obtains isomerization product, and isomerization product is back in second level etherification reaction.This method can reduce the content of alkene in clean gasoline produced and improve the octane number of gasoline.

Description

Produce the method and system of clean gasoline

Technical field

The present invention relates to clean gasoline production fields, and in particular to a method of produce clean gasoline and a kind of life The system for producing clean gasoline.

Background technique

Recently as the increasingly strict of legislations of environmental protection, countries in the world and area are to the olefin(e) centent and sulphur in gasoline The limitation of content is increasingly stringent, and market is continuously increased the demand of high-grade gasoline also with the development of automobile market；In order to It is adapted to environmental protection and the market demand, China has also put into effect the state that more strict requirements are made to the olefin(e) centent in gasoline Six standards, the first stage requires olefin(e) centent to be no more than 18vol% in six standard of state, and second stage requires olefin(e) centent to be no more than 15vol%.However, at present China be more than 70% gasoline from catalytic cracking process, and the catalytic cracking that this technique produces Olefin(e) centent is generally higher (usually in 40%-50vol%) in gasoline, is not content with aforementioned claim.

In order to produce the low alkene gasoline of low-sulfur, traditional gasoline processing technology is as shown in Figure 1, comprising the following steps: (1) by vapour Oil carries out cutting fractionation and obtains light gasoline fraction and heavy naphtha；(2) light gasoline fraction is subjected to desulfurization, de- basic nitrogen and taken off After alkadienes (purification) processing, further progress etherification process obtains etherified benzine；(3) after collecting etherified benzine and desulfurization Heavy naphtha obtain clean gasoline.However, as countries in the world and area are to the olefin(e) centent and sulfur content in gasoline Limitation is increasingly stringent, and this method is not able to satisfy production requirement gradually.

A kind of Etherification of Light FCC Gasoline technique and the modifying catalytically cracked gasoline containing the technique are disclosed in CN101270301A Method, and specifically disclosing the alkadienes and mercaptan sulfur in the chosen property hydrogenation and removing gasoline of catalytic gasoline, adding will be complete after hydrogen Distillation gasoline be cut into it is light, weigh two components, a large amount of Tertiary olefin has been concentrated in light petrol, warp and methanol are in catalyst for etherification Under effect, it is etherified through second level into ether compound.It is from a certain piece of column plate extraction C4-C6 among etherificate fractionating column in that patent The azeotropic mixture of component and methanol, which is sent to second methyltertiarvbutyl ether reactor, further to react.But tert amyl methyl ether(TAME) (TAME) is also C6 group The one kind divided is easy to enter in methyltertiarvbutyl ether reactor with charging, the equilibrium conversion of C5 active olefin in reactor is caused to drop It is low.

A kind of olefin-containing Etherification of Light FCC Gasoline method is disclosed in CN1654602A, specifically providing one kind can contract significantly Short processes process, to reduce production equipment and bring the olefin-containing Etherification of Light FCC Gasoline method operated conveniently, this method is not used Noble metal catalyst, thus solve noble metal and be easy to be lost the technological deficiency with sulfur poisoning.The technical solution of the invention is as follows: First segment will remove alkadienes by using difunctional non-precious metal catalyst and removing basic nitrogen is combined into one section of progress selectivity Hydrogenation reaction, second segment are that heterogeneous activity alkene and methanol carry out etherification reaction of hydro-refining, generate etherified gasoline.But technique Second stage reactor carries out etherification reaction of hydro-refining and has the following disadvantages: in the case where facing hydrogen state easily by some olefin in catalytic light gasoline Saturation, this not only increases hydrogen consumption, and also reduces the amount of etherification product and the octane number of catalytic gasoline, simultaneously because Using secondary plus hydrogen, has more hydrogen and be dissolved in etherified gasoline product, need to add stabilizer for hydrogen gas therein It proposes, which again increases the investments of device.

Summary of the invention

It is of the existing technology the purpose of the invention is to overcome the problems, such as, provide a kind of method for producing clean gasoline and System while to reduce the olefin(e) centent and sulfur content in clean gasoline, improves the content of etherate in clean gasoline.

To achieve the goals above, according to an aspect of the invention, there is provided a kind of method for producing clean gasoline, is somebody's turn to do Method includes: (1) under the conditions of facing hydrogen refining reaction, by full distillation gasoline raw material and refining agent haptoreaction, after obtaining purification Gasoline, and gasoline after the purification is subjected to cutting fractionation, obtain light gasoline fraction and heavy naphtha；(2) it is etherified in level-one Under reaction condition, the light gasoline fraction is contacted with alcohol and carries out level-one etherification reaction, obtains level-one etherificate product；It will be described Level-one is etherified the tower top azeotropic mixture that product fractionation is the pure and mild lighter hydrocarbons based on C5 and level-one is etherified Fractionator Bottom fraction；(3) Under the conditions of second level etherification reaction, the tower top azeotropic mixture is mixed with isomerization product and carries out second level etherification reaction, obtains two Second level etherificate product is carried out washing process and obtains second level etherification product by grade etherificate product, and will at least partly institute It states the fractionation of second level etherification product and is etherified Fractionator Bottom fraction for based on the C5 component and not overhead of ether-containing and second level； Second overhead is subjected to olefin skeletal isomerization processing, obtains the isomerization product, and by the isomerization Product reflux is into second level etherification reaction；(4) heavy naphtha is collected, the level-one is etherified Fractionator Bottom fraction, residue The second level etherification product and the second level be etherified Fractionator Bottom fraction, obtain clean gasoline (product).

Meanwhile according to another aspect of the present invention, a kind of system for producing clean gasoline is provided, which includes: Finishing reactor, gasoline Cutting Tap, level-one methyltertiarvbutyl ether reactor, level-one are etherified fractionating column, second level methyltertiarvbutyl ether reactor, water scrubber, two Grade etherificate fractionating column, isomerization reactor and clean gasoline collecting tank, wherein the feed inlet of the gasoline Cutting Tap with it is described The discharge port of finishing reactor is connected, light gasoline fraction outlet is connected with the feed inlet of the level-one methyltertiarvbutyl ether reactor, heavy petrol Fraction outlets are connected with the clean gasoline collecting tank；Wherein the feed inlet of the level-one etherificate fractionating column and the level-one are etherified The discharge port of reactor is connected, the feed inlet of the outlet of tower top azeotropic mixture and the second level methyltertiarvbutyl ether reactor, tower bottom distillate outlet with The clean gasoline collecting tank is connected；Wherein the feed inlet of the water scrubber is connected with the discharge port of second level methyltertiarvbutyl ether reactor, goes out Material mouth is connected with the feed inlet of second level etherificate fractionating column and the clean gasoline collecting tank respectively；The wherein second level The overhead outlet of etherificate fractionating column is connected with the feed inlet of the isomerization reactor, tower bottom distillate exports and described clear Clean gasoline collecting tank is connected；The wherein feed inlet phase of the discharge port of the isomerization reactor and the second level methyltertiarvbutyl ether reactor Even.

A kind of method and system for producing clean gasoline of the present invention, can be realized following beneficial effect.

(1) by the way that the overhead for being etherified based on the C5 component and not ether-containing that fractionation obtain through second level is carried out alkene The linear alkene for wherein not having etherification activity is transformed into the Tertiary olefin with etherification activity by hydrocarbon skeletal isomerizations processing； Meanwhile obtained all or part of isomerization product reflux is mixed into hair with the tower top azeotropic mixture for being etherified fractionation acquisition through level-one Raw second level etherification reaction, to carry out secondary use to the alcohol in tower top azeotropic mixture in the case where being not necessarily to add secondary alcohol, thus The total amount that can be etherified alkene is being greatly improved, while reducing olefin(e) centent in gasoline, the internal circulating load of alcohol is being reduced, reduces returning for alcohol Receive load and energy consumption；

(2) it is improved, is flowed back using the Tertiary olefin relative amount in isomerization product with etherification activity Into second level etherification reaction with the tower top azeotropic mixture haptoreaction of level-one etherificate fractionation, can be used in adjusting in second level etherification reaction Alfin ratio, and then avoid because alfin ratio it is excessively high caused by alcohol side reaction, and reduce by-product diformazan in second level etherification product The content of ether；

(3) method of present invention production clean gasoline, the technique handled by using second level etherification process combination isomerization Process, can obtain sulfur content lower than 10 μ g/g and olefin(e) centent is greatly reduced and (meets state's six first stage gasoline standard) Clean gasoline.

Detailed description of the invention

Fig. 1 is the process flow (adding hydrogen-etherificate) of traditional mode of production clean gasoline according to prior art；

Fig. 2 is the structural schematic diagram that the system of clean gasoline is produced in specific embodiment according to the present invention.

Description of symbols

1 is full distillation gasoline raw material, 2 be hydrogen, 3 be finishing reactor, 4 be refining reaction product, 5 be lightness-removing column (tank), 6 be hydrogen and part C4 and following components, 7 be gasoline after purification, 8 be gasoline Cutting Tap, 9 be light gasoline fraction, 10 be Heavy naphtha, 11 be fresh alcohol, 12 be the mixture of light gasoline fraction and alcohol, 13 be level-one methyltertiarvbutyl ether reactor, 14 be level-one Etherificate product, 15 be level-one etherificate fractionating column, 16 be the tower top azeotropic mixture of the pure and mild lighter hydrocarbons based on C5,17 be level-one be etherified Fractionator Bottom fraction, 18 be second level methyltertiarvbutyl ether reactor, 19 be the second etherificate product, 20 be water scrubber, 21 be second level etherificate produce Object, 22 rich alcohol water, 23 be alcohol recovery tower, 24 be recycle alcohol, 25 desalted waters, 26 and 27 be second level etherification product, 28 be second level ether Changing fractionating column, 29 as based on the C5 component and not overhead of ether-containing, 30 is that second level is etherified Fractionator Bottom fraction, 31 is Heat exchanger, 32 be heating furnace, 33 be isomerization reactor, 34 be isomerization product.

Specific embodiment

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

Countries in the world and the area status increasingly stringent to the limitation of olefin(e) centent and sulfur content in gasoline are faced, this The inventor of invention has conducted extensive research the method for producing clean gasoline, and proposes by etherificate product Remaining C5 component, which carries out isomerization processing, can be etherified alkene total amount to improve, and play the technology of the effect of etherification of olefine to greatest extent Scheme；And it is based on this technical solution, in order to optimize the etherificate effect of clean gasoline, inventor has advanced optimized cleaning vapour The production procedure of oil, and propose the method and system of present invention production clean gasoline.

According to an aspect of the present invention, the method for the production clean gasoline includes: that (1) is facing hydrogen refining reaction condition Under, by full distillation gasoline raw material and refining agent haptoreaction, gasoline after being refined, and gasoline after the purification is cut Fractionation, obtains light gasoline fraction and heavy naphtha；(2) under the conditions of level-one etherification reaction, by the light gasoline fraction and alcohol Contact carries out level-one etherification reaction, obtains level-one etherificate product；Level-one etherificate product is fractionated and is with C5 to be pure and mild The tower top azeotropic mixture and level-one of main lighter hydrocarbons are etherified Fractionator Bottom fraction；(3) under the conditions of second level etherification reaction, by the tower top Azeotropic mixture is mixed with isomerization product carries out second level etherification reaction, obtains second level etherificate product, the second level is etherified and is generated Object carries out washing process and obtains second level etherification product, and by the part second level etherification product fractionation for based on C5 component and The overhead of ether-containing and second level are not etherified Fractionator Bottom fraction；Second overhead is subjected to olefin skeletal isomery Change processing, obtains the isomerization product, and the isomerization product is back in second level etherification reaction；(4) described in collecting Heavy naphtha, level-one etherificate Fractionator Bottom fraction, the remaining second level etherification product and second level etherificate fractionation Tower bottom distillate obtains clean gasoline.

According to the method for the present invention, it can not required for carrying out the amount of second level etherification product of fractionation processing, it can be with It is reasonably selected according to the regurgitant volume of the ratio of active olefin pure and mild in second level etherification reaction and isomerization product, however It is recommended that in this step, second level etherification product is not carried out fractionation processing all, to avoid in the overhead not The substance that etherification reaction occurs flows back repeatedly, influences to be etherified effect.

In the case of with the method for the invention it is preferred to, it is anti-that the isomerization product can all participate in the second level etherificate It answers, it can also be with second level etherification reaction described in subparticipation；When second level etherification reaction described in the isomerization product subparticipation, Remaining part point, which returns, participates in the level-one etherification reaction.In order to improve the utilization rate of alcohol in second level etherification reaction, meet etherification of olefine It is required that under preferable case, in the second level etherification reaction, in the mixture of the tower top azeotropic mixture and the isomerization product The molar ratio of alcohol and active olefin is (1.2-2.5): 1；It, can be according to two for the above method provided by the present invention The molar ratio demand of alcohol and active olefin reasonably adjusts the fractionation amount of second level etherification product in grade etherification reaction and isomerization produces The reflux type and regurgitant volume of object.Furthermore in order to further decrease the content of by-product dimethyl ether in second level etherification product, preferably In the case of, in the second level etherification reaction, alcohol and activity in the mixture of the tower top azeotropic mixture and the isomerization product The molar ratio of alkene is (1.4-2.0): 1.Wherein the molar ratio of pure and mild active olefin can be analyzed by online or offline inspection The method of active olefin total amount is calculated and is monitored in light petrol, and wherein active olefin total amount can be obtained by gas chromatography analysis It takes (similarly hereinafter).

According to the method for the present invention, wherein the full distillation gasoline raw material refers to that boiling range range falls into 30 DEG C of -250 DEG C of ranges Petroleum hydrocarbon-fraction, can selected from rich in alkene coker gasoline, pyrolysis gasoline and catalytically cracked gasoline etc..Generally, institute Stating full distillation gasoline is the mixture that carbon molecules number is C4-C12 the hydrocarbon component, including alkene, alkane, cycloalkane and aromatic hydrocarbons, wherein Component with etherification activity is mainly the Tertiary olefin of C4-C7.Because the content of active olefin is significant with the increase of carbon number It reduces, carbon atom number various active olefin contents in 7 or more component are seldom in gasoline, and with the increase of carbon number, living The etherificate equilibrium conversion and reaction rate of property alkene substantially reduce, therefore the raw material of etherification in gasoline mainly considers C4-C7 Component, wherein based on C5 and C6 Tertiary olefin.

In the case of with the method for the invention it is preferred to, C4 component is less than 2% in the full distillation gasoline raw material, total C5 alkene Hydrocarbon is not less than 8%.The C5 alkene being wherein present in full distillation gasoline raw material shares six kinds of isomers, wherein 2- methyl- The Tertiary olefin of 1- butylene and 2- methyl-2-butene with etherification activity, and 1- amylene, suitable (anti-) -2- amylene and 3- methyl - 1- butylene does not have etherification activity.The olefin isomerization that etherification activity will not had by being exactly based in the present invention is lived at etherificate Property 2-methyl-1-butene alkene and 2- methyl-2-butene, thus improve can be etherified alkene total amount, play etherification of olefine to greatest extent Effect.

It according to the method for the present invention, can be without spy for the refining agent employed in hydrogen subtractive process that faces of (1) It is different to require, it is referred to the conventional selection of this field；However, in order to realize and meanwhile desulfurization, dialkene removal, de- basic nitrogen it is multiple Effect, under preferable case, the refining agent is on the basis of its total weight, zinc oxide, 5wt%- containing 10wt%-80wt% The alumina binder of 40wt%, the laminated clay column of 0wt%-40wt%, 0.1wt%-16wt% group VIII metal, with And the molecular sieve component of 0.1wt%-5wt%.The more preferable refining agent contains 15wt%- on the basis of its total weight The zinc oxide of 60wt%, the alumina binder of 3wt%-35wt%, 5wt%-40wt% laminated clay column, 5wt%-16wt% Group VIII metal and 0.5wt%-5wt% molecular sieve component.

It is preferred that the metal selected from group VIII is Ni and/or Co in the refining agent.

It is preferred that molecular sieve component is the combination of one or more of ZSM and SAPO Series Molecules sieve in the refining agent； More preferably it is selected from ZSM-35, ZSM-22, ZSM-11, ZSM-5, SAPO-5, SAPO-11, SAPO-20, SAPO-31 and SAPO- One or more of 34 combination；Particularly preferably selected from one of ZSM-35, SAPO-11, SAPO-31 and SAPO-34 Or several combination.

It is preferred that laminated clay column is selected from rectorite, Yun Mengshi, bentonite, montmorillonite and smectite in the refining agent One or more of combination.

It is preferred that the precursor of the alumina binder is after roasting with γ-Al in the refining agent₂O₃Form deposit In substance, more preferably (intend thin water selected from hydrated alumina, Aluminum sol, boehmite (boehmite), false boehmite Aluminium stone), the combination of hibbsite, one or more of amorphous hydroted alumina.

According to the method for the present invention, wherein preparation method for refining agent, there is no particular/special requirements, are referred to ability The conventional scheme in domain, under preferable case, the refining agent can be prepared by the following method: (1) being glued optional layer column Soil and binder precursor object and acid solution are made into slurries, then carry out aging process；(2) by the slurries and oxygen after aging process Change zinc and molecular sieve mixing, obtains carrier mixture and it is formed, is dried, roasts carrier is made；(3) draw into carrier Enter metallic compound, then it is dried and roasting obtains oxidation state refining agent；(4) hydrogen reducing is used, is made described Refining agent.

According to the method for the present invention, full distillation gasoline raw material and refining agent haptoreaction can in finishing reactor into Row, wherein finishing reactor can be selected from any one of fixed bed, moving bed or fluidized bed form.It is described under preferable case It is 320 DEG C -460 DEG C, preferably 340 DEG C -440 DEG C, such as 340 DEG C, 350 DEG C, 360 that face hydrogen refining reaction condition, which include: temperature, DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 400 DEG C, 410 DEG C, 420 DEG C, 430 DEG C, any two institute in 440 DEG C and these point values Any number in the range of composition；Pressure is 0.5MPa-4.0MPa, preferably 1.0MPa-3.5MPa, such as 1.0MPa, 1.2MPa, 1.5MPa, 1.8MPa, 2.0MPa, 2.2MPa, 2.5MPa, 2.8MPa, 3.0MPa, 3.2MPa, 3.5MPa and these Any number in range that any two in point value are constituted；Volume space velocity is 2h^-1-20h^-1, preferably 4h^-1-10h^-1, Such as 4h^-1、5h^-1、6h^-1、7h^-1、8h^-1、9h^-1、10h^-1And appointing in the range that is constituted of any two in these point values Meaning numerical value；Hydrogen to oil volume ratio is 0.1-0.8, preferably 0.2-0.5, such as in 0.2,0.3,0.4,0.5 and these ratios Any ratio in the range that any two are constituted.

According to the method for the present invention, anti-by selecting refining agent appropriate and facing hydrogen purification under the introduction of above content It answers condition to carry out refinement treatment to full distillation gasoline raw material, the various sulfide in gasoline, including mercaptan sulfur and thiophene can be removed Pheno sulphur, so that the cutting of subsequent light gasoline fraction is no longer limited by sulfur content index；Simultaneously under hydro condition, in gasoline two Olefine selective saturation, can satisfy Con trolling index requirement of the light gasoline fraction to 200 μ g/g of diene content <；And pass through Activated alumina and molecular sieve component are introduced in refining agent, the basic nitrogen compound in gasoline can be made with stronger absorption With so that 2 μ g/g of gasoline neutral and alkali nitride < after purification.To sum up, by using the above-mentioned refinement treatment step of the present invention As raw material of etherification, the sulphur, basic nitrogen, alkadienes equal size for influencing catalyst life are substantially reduced for treated gasoline stocks, Be conducive to improve the service life of subsequent etherificate and isomerization catalyst, the removing of alkadienes is also beneficial to reduce in product gasoline Gum level.

According to the method for the present invention, for gasoline after purification is carried out cutting fractionation in (1) the step of, can be in vapour It is carried out in oily Cutting Tap (tower internals can be filler, sieve plate, float valve tray or combinations thereof), wherein being evaporated eventually for light gasoline fraction Point can not have particular/special requirement, usually the mixture of C4-C7 component in full distillation gasoline be fractionated as light gasoline fraction, at this Whole C5 component and part or all of C6 component are generally included in light gasoline fraction.Thus under preferable case, the light petrol 60 DEG C -100 DEG C of the fraction end point of distillation.

According to the method for the present invention, can there is no particular/special requirement for level-one etherification reaction in (2), be referred to this The common process method and Conventional process parameters in field, however, comprehensively considering the bearing capacity of equipment, energy consumption and gasoline products In olefin(e) centent, under preferable case, the molar ratio of alcohol and active olefin is (1.1-1.6) in the level-one etherification reaction: 1, Such as in the range that is constituted of any two in 1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1 and these ratios Any ratio；It is preferred that the alcohol is methanol or ethyl alcohol, more preferable methanol.

In the case of with the method for the invention it is preferred to, the choosing of the catalyst for etherification employed in the level-one etherification reaction From one or more of the catalyst and modified molecular sieve catalyst of routine or modified resin, heteropoly acid or carried heteropoly acid. The routine or modified resin that wherein can be used include but is not limited to large porous strong acid type, cation exchange resin, halogen modified tree One of rouge, perfluorosulfonic acid type resin and several；The heteropolyacid catalyst that can be used includes but is not limited to that Dawson type is miscellaneous One of polyacid and Keggin-type heteropoly acid and several；The catalyst for the carried heteropoly acid that can be used includes but is not limited to silicon One of glue support type, activated carbon supported type and resin-carried type and several, the modified molecular sieve catalyst packet that can be used Include but be not limited to one of ZSM-5, ZSM-35 and HY type, HM type and beta molecular sieve and several.

According to the method for the present invention, the reactor for carrying out level-one etherification reaction can be fixed bed, expanded bed, in mixed phase bed One or more of combinations.Under preferable case, the level-one etherification reaction condition includes: that temperature is 30 DEG C -120 DEG C, preferably It is that any two in 40 DEG C -90 DEG C, such as 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C and these point values are constituted Any number in range；Pressure is 0.1-2.0MPa, preferably 0.2-1.0MPa, for example, 0.2MPa, 0.3MPa, 0.4MPa, The range that any two in 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa and these point values are constituted In any number；Volume space velocity is 0.1-5.0h^-1, preferably 0.5-3.0h^-1, such as 0.5h^-1、1h^-1、1.5h^-1、2h^-1、 2.5h^-1、3h^-1And any number in the range that is constituted of any two in these point values.

According to the method for the present invention, in (2) by level-one etherificate product fractionation it the step of, is referred to The conventional separate mode of this field, can etherificate fractionating column (inner member can be filler, sieve plate, float valve tray or its group Close) in carry out.The purpose of the step is the tower top azeotropic mixture and ethers chemical combination that will include whole pure and mild lighter hydrocarbons based on C5 Object is separated, so that etherificate fractionator overhead is substantially free of ether compound, tower bottom is substantially free of pure and mild C5 alkene, i.e., will The level-one etherificate product fractionation is that the tower top azeotropic mixture of the pure and mild lighter hydrocarbons based on C5 and level-one are etherified Fractionator Bottom fraction. In addition, the influence in order to avoid TAME to the equilibrium conversion of C5 active olefin, under preferable case, the overhead extraction it is pure and mild with TAME is not contained in the tower top azeotropic mixture of lighter hydrocarbons based on C5.Technique about the step of by level-one etherificate product fractionation Condition is referred to foregoing purpose and is reasonably adjusted, such as: the pressure for being etherified fractionating column is 0.2-0.5MPa, and column bottom temperature is 100-150 DEG C, tower top temperature is 40-80 DEG C.

According to the method for the present invention, the purpose for secondary etherification reaction being carried out in (3) is to make full use of the tower top The isomerization product of remaining alcohol in azeotropic mixture and reflux, to optimize the etherificate effect of clean gasoline.For secondary etherification reaction Process focuses on, and needs to control alcohol and active olefin in the mixture of the tower top azeotropic mixture and the isomerization product Molar ratio makes it preferably (1.4-2.5): 1；Moreover, in order to further decrease by-product dimethyl ether in second level etherification product Content, under preferable case, in the second level etherification reaction, in the azeotropic mixture with alcohol in the mixture of the isomerization product Molar ratio with active olefin is (1.4-2.0): 1, such as 1.4:1,1.5:1,1.6:1,1.7:1,1.8:1,1.9:1,2.0:1 And any ratio in the range that is constituted of any two in these ratios.

According to the method for the present invention, secondary etherification reaction is carried out in another methyltertiarvbutyl ether reactor, wherein for etherificate The selection of reactor, the selection of catalyst for etherification and the selection of secondary etherification reaction condition can be with an etherification reactions It is identical or different, and it is specifically chosen the specific descriptions for being referred to front during about an etherification reaction.

According to the method for the present invention, the purpose for second level etherificate product being carried out washing process in (3) is removing Second level is etherified the alcohol in product, and to reduce the energy consumption of subsequent fractionation step, the step can (tower internals be can be in water scrubber Filler, sieve plate, float valve tray or combinations thereof) in carry out, can be by the way that the second level be etherified product and water counter current contacting, benefit It is etherified the remaining alcohol in the dissolubility difference elimination reaction product of product and alcohol in water in second level with alcohol, obtains second level etherificate Product and rich alcohol water, under preferable case, the condition of the water-washing step are as follows: temperature is 10 DEG C -50 DEG C, pressure 0.1MPa- 1.0MPa, it is 1:0.2-2.0 that second level, which is etherified product and the volume ratio of water,.Wherein used water be softened water, demineralized water or Deionized water.

According to the method for the present invention, the second level etherification product is fractionated as based on C5 component and not in (3) The overhead and second level of ether-containing are etherified the step of Fractionator Bottom fraction, are referred to the conventional separate mode of this field, It can be carried out in another etherificate fractionating column (inner member can be filler, sieve plate, float valve tray or combinations thereof).The step Purpose be by based on C5 component overhead and with second level etherification reaction production ether compound separate so that It is etherified in fractionator overhead distillate and is free of ether compound, and be substantially free of C5 component in tower bottom distillate, i.e., by described two Grade etherification product fractionation is etherified Fractionator Bottom fraction for based on the C5 component and not overhead of ether-containing and second level.About The process conditions of the step of by second level etherification product fractionation are referred to foregoing purpose and reasonably adjust, such as: etherificate The pressure of fractionating column is 0.2-0.5MPa, and column bottom temperature is 100-150 DEG C, and tower top temperature is 40-80 DEG C.

It according to the method for the present invention, is by C5 for the purpose for carrying out olefin skeletal isomerization processing step in (3) Linear alkene in alkene without etherification activity is transformed into the Tertiary olefin with etherification activity.In actual operation, described Olefin skeletal isomerization processing step includes: under the conditions of isomerization reaction, by the washing product and alkene of the overhead Hydrocarbon skeletal isomerizations catalyst haptoreaction, obtains isomerization product.

According to the method for the present invention, can there is no particular/special requirement for the selection of the olefin skeletal isomerization catalyst, It can choose and the linear alkene in C5 alkene without etherification activity is arbitrarily enabled to be transformed into the tertiary carbon with etherification activity The olefin skeletal isomerization catalyst of alkene.Under preferable case, the olefin skeletal isomerization catalyst include host agent, auxiliary agent and Modified compound, and the weight ratio of three is 1:(0.05-0.15): (0.01-0.2), includes molecular sieve and oxygen in the host agent Change al binder, and the weight ratio of the molecular sieve and alumina binder is 1:(0.01-1.0), the auxiliary agent is rare earth Oxide, the modified compound are selected from hydroxyl organic compound.

Under preferable case, the molecular sieve described in the olefin skeletal isomerization catalyst is selected from ZSM and SAPO series point It is one or more of in son sieve, more preferably it is selected from ZSM-5, ZSM-11, ZSM-22, ZSM-35, SAPO-5, SAPO-11, SAPO- 20, the combination of one or more of SAPO-31 and SAPO-34；Particularly preferably in ZSM-22, ZSM-35 and SAPO-11 One or more of combinations, the preferably described molecular sieve is Hydrogen or ammonia type molecular sieve.

Under preferable case, the precursor of the binder is after roasting with γ-Al₂O₃Form there are substances, more preferably Selected from hydrated alumina, Aluminum sol, boehmite (boehmite), false boehmite (boehmite), three hydration oxygen Change the combination of one or more of aluminium, amorphous hydroted alumina.

Under preferable case, the rare earth oxide is the combination selected from one or more of lanthanum, cerium, praseodymium oxide.

Under preferable case, the hydroxyl organic compound is selected from cell alcohol or phenol, polyalcohol or sugar and aforementioned raw material Any combination, the preferably described hydroxyl organic compound are selected from phenols or the polyalcohol of C2-C7, and wherein phenols includes but is not limited to The polyalcohol of the combination of one or more of phenol, benzenediol, benzenetriol, naphthols, cresols and amino phenols, C2-C7 include but It is not limited to the combination of one or more of ethylene glycol, butanediol, glycerine, pentaerythrite, xylitol and sorbierite.

According to the present invention, the olefin skeletal isomerization catalyst can obtain by the following method: (1) prepare carrier: Molecular sieve, alumina binder precursor, rare earth precursor are mixed to get carrier pulp in acid condition, then by institute State carrier paste drying, roasting forms carrier；(2) organic solution of hydroxyl organic compound is prepared, and by aforementioned preparation Carrier impregnation is in the organic solution of the hydroxyl organic compound, and then low pressure is dried to obtain the olefin skeletal isomerization and urges Agent.

The rare earth precursor that can wherein use for the compound that is able to produce rare earth oxide under the roasting condition, such as For acetate, carbonate, nitrate, sulfate, rhodanate, oxalates, hydroxide and oxide selected from rare earth element One or more of.

The temperature for being wherein dried and roasting to carrier paste can not have particular/special requirement, realize corresponding function. Such as it is -150 DEG C of room temperature that the condition of the drying, which includes: temperature, preferably 90-150 DEG C, more preferably 100-130 DEG C；Time is 0.5 hour or more, preferably 1-10 hours；The condition of roasting include: temperature be 400-700 DEG C, preferably 450-650 DEG C, when Between be 0.5 hour or more, preferably 1-10 hours.

It wherein can be according to used hydroxyl organic compound for preparing the organic solution of hydroxyl organic compound Solubility selected, such as can include but is not limited in the fatty alcohol of water, the alkane of C6-C8 or aromatic hydrocarbons, C2-C4 one Kind or several combinations.

In the case of with the method for the invention it is preferred to, the isomerization reaction condition includes: that temperature is 200 DEG C -450 DEG C, preferably 280 DEG C -420 DEG C, such as 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 400 DEG C, 410 DEG C, it is any in the range that is constituted of any two in 420 DEG C and these point values Numerical value；Pressure is 0.01MPa-1.0MPa, preferably 0.05MPa-0.5MPa, for example, 0.05MPa, 0.1MPa, 0.15MPa, Any two institute in 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa and these point values Any number in the range of composition；Volume space velocity 0.1h^-1-6h^-1, preferably 0.2h^-1-4h^-1, such as 0.2h^-1、0.5h^-1、1h^-1、 1.5h^-1、2h^-1、2.5h^-1、3h^-1、3.5h^-1、4h^-1And the arbitrary number in the range that is constituted of any two in these point values Value.

According to the method for the present invention, in order to be adapted to the reaction temperature of olefin skeletal isomerization processing, under preferable case, It further include that pre-add is carried out to the overhead before the overhead is carried out olefin skeletal isomerization processing step The step of heat；In addition, converting to optimize the heat of entire process flow, under preferable case, isomerization product pair can also be used The overhead exchanges heat.

According to the method for the present invention, it in order to improve olefin conversion and prevent the side reactions such as alkene oligomerization, is etherified in level-one The alcohol being added in reaction process is excessive, it is therefore necessary to which excessive alcohol is recycled and recycled.For this purpose, being mentioned in the present invention And method involved in the step of washing process is carried out to second level etherificate product, can generate rich alcohol water in the step, and in order to It realizes the recycling to alcohol and recycles, in the method according to the invention further include: the distillation processing rich alcohol water is to recycle Alcohol and water, and optionally by recycled alcohol reflux into level-one etherification reaction, the water recycled is optionally back to washing step In rapid.

According to the method for the present invention, wherein the step of distillation handles rich alcohol water can (tower internals can be in alcohol recovery tower Filler, sieve plate, float valve tray or combinations thereof) in carry out, can using distillation method realize water and alcohol separation, alcohol recycle The alcohol of the overhead extraction of tower recycles, and returns at the top of water scrubber after the water of the tower bottom extraction of alcohol recovery tower is exchanged heat, cooled down Recycling.Wherein distillation condition can be reasonably selected according to selected alcohol.

According to the method for the present invention, wherein pressure is gauge pressure.

According to the second aspect of the invention, a kind of system for producing clean gasoline is provided, as shown in Fig. 2, the system It include: finishing reactor 3, gasoline Cutting Tap 8, level-one methyltertiarvbutyl ether reactor 13, level-one etherificate fractionating column 15, second level methyltertiarvbutyl ether reactor 18, water scrubber 20, second level etherificate fractionating column 28, isomerization reactor 33 and clean gasoline collecting tank, wherein the gasoline is cut The feed inlet for cutting tower 8 is connected with the discharge port of the finishing reactor 3, light gasoline fraction outlet and the level-one methyltertiarvbutyl ether reactor 13 feed inlet is connected, heavy naphtha outlet is connected with the clean gasoline collecting tank；Wherein the level-one is etherified fractionating column 15 feed inlet is connected with the discharge port of the level-one methyltertiarvbutyl ether reactor 13, tower top azeotropic mixture exports and the second level etherification reaction The feed inlet of device 18, tower bottom distillate outlet are connected with the clean gasoline collecting tank；Wherein the feed inlet of the water scrubber 20 with The discharge port of second level methyltertiarvbutyl ether reactor 18 is connected, discharge port is etherified feed inlet, the Yi Jisuo of fractionating column 28 with the second level respectively Clean gasoline collecting tank is stated to be connected；The wherein overhead outlet of the second level etherificate fractionating column 28 and the isomerization reaction The feed inlet of device 33 is connected, tower bottom distillate outlet is connected with the clean gasoline collecting tank；The wherein isomerization reactor 33 Discharge port be connected with the feed inlet of the second level methyltertiarvbutyl ether reactor 18.

The system of this production clean gasoline provided by the present invention, equipment is simple, flexible operation, can be suitable for this hair The method of bright proposed production clean gasoline, to reduce gasoline products in relatively low energy consumption and alcohol yield Olefin(e) centent and sulfur content, improve the octane number of gasoline products.

The system according to the present invention, in order to increase system formulation flexibility, under preferable case, the isomerization reactor 33 The also selective feed inlet with level-one methyltertiarvbutyl ether reactor 13 of discharge port be connected.Under this configuration, operator can root According to actual needs, the isomerization product generated by the isomerization reactor 33 is all delivered to second level methyltertiarvbutyl ether reactor 18 In, or be partially delivered in second level methyltertiarvbutyl ether reactor 18, rest part is delivered in level-one methyltertiarvbutyl ether reactor 13, and then is being guaranteed In the case that isomerization product can fully enter subsequent processing operations, level-one methyltertiarvbutyl ether reactor 13 and second level etherification reaction are adjusted The molar ratio of alcohol and active olefin in device 18.

The system according to the present invention, in order to realize the recycling to alcohol excessive in level-one methyltertiarvbutyl ether reactor and recycle, It in the system further include alcohol recovery tower 23 under preferable case, the tower bottom richness alcohol water out and the alcohol of the water scrubber 20 The feed inlet of recovery tower 23 is connected, the feed inlet of the recycling alcohol outlet of the alcohol recovery tower 23 and the level-one methyltertiarvbutyl ether reactor 13 It is connected.

The system according to the present invention, in order to be adapted to the reaction temperature of olefin skeletal isomerization processing, under preferable case, Heating furnace 32 is additionally provided between the second level etherificate fractionating column 28 and the isomerization reactor 33.Meanwhile being to optimize this The heat of system is converted, and under preferable case, is etherified between fractionating column 28 and the heating furnace 32 in the second level and is additionally provided with heat exchanger 31, the heat exchanger 31 respectively with the flow path and connection that are connected between second level etherificate fractionating column 28 and the heating furnace 32 Flow path between the isomerization reactor 33 and the second level methyltertiarvbutyl ether reactor 18 is connected.

The system according to the present invention, wherein for used finishing reactor 3, gasoline Cutting Tap 8, level-one etherification reaction Device 13, level-one etherificate fractionating column 15, second level methyltertiarvbutyl ether reactor 18, water scrubber 20, alcohol recovery tower 23, second level etherificate fractionating column 28, The selection of heat exchanger 31, heating furnace 32, isomerization reactor 33 and clean gasoline collecting tank can not have particular/special requirement, As long as can be realized respective requirement, and meet the requirement of the method for production clean gasoline according to the present invention.

It will be further illustrated below by embodiment and comparative example clear to the system of present invention production clean gasoline and production The method of clean gasoline is described in detail.

Full distillation gasoline raw material employed in following examples and comparative examples is limited from Sinopec share The boiling range range of the catalytic cracking unit production of Yanshan Mountain branch company of company is 30 DEG C of -220 DEG C of gasoline fractions, and component and attribute are such as Shown in table 1.

Table 1

Component	Content	Component	Content
				N-alkane, wt%	4.4	Isoparaffin, wt%	34.0
Total olefin, wt%	26.9	C4, wt%	1.4
				C5 alkene, wt%	12.3	Aromatic hydrocarbons, wt%	29.0
Cycloalkane, wt%	5.4	Basic nitrogen, ppm	14.3
				Alkadienes, wt%	0.4	Sulfur content, ppm	804
Density, kg/m3	731.8	RON	83.5

Refining agent employed in following examples and comparative examples is described as follows:

Take 1.81 kilograms of boehmite (Shandong Aluminum Plant produces, and contains 1.32 kilograms of butt) and 2.45 kilograms of montmorillonite (Shandong catalyst branch contains 1.66 kilograms of butt) mixes under stiring, is then added 8.9 kilograms of deionized water and is uniformly mixed Afterwards, hydrochloric acid (chemistry is pure, and Beijing Chemical Plant produces) stirring acidification that 290 milliliters of 30wt% are added is warming up to 80 DEG C always after 1 hour Change 2 hours.6.25 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%) and 0.38 are added after temperature reduction Kilogram ZSM-35 (Shandong catalyst branch) is simultaneously stirred 1 hour and is obtained carrier pulp.The carrier pulp uses The spray dryer of NiroBowenNozzleTowerTM model is spray-dried, and spray drying pressure is 8.5 to 9.5MPa, 500 DEG C of inlet temperature is hereinafter, outlet temperature is about 150 DEG C.The microballoon obtained by spray drying is first 1 hour dry at 180 DEG C, Then it is roasted at 650 DEG C and obtains within 1 hour purification agent carrier, by 3.4 kilograms of purification agent carrier, 3.68 kilogram of six hydration nitre Sour nickel (Beijing chemical reagents corporation, purity be greater than 98.5%), 0.6 kilogram of deionized water solution dipping, obtained mixture warp After crossing 180 DEG C of dryings 4 hours, roasting 1 hour at 650 DEG C of air atmosphere can be prepared by refining agent precursor.Refining agent precursor is 425 DEG C hydrogen atmosphere in reductase 12 hour refining agent can be obtained.

The chemical composition of the refining agent are as follows: zinc oxide content 53.3wt%, alumina bound agent content are 11.3wt%, Montmorillonite content is 14.1wt%, and SAPO-31 content is 3.3wt%, nickel content 18.0wt%.

Olefin skeletal isomerization catalyst employed in following examples and comparative examples is described as follows:

By 107.9 grams of commercially available Hydrogen ZSM-35 molecular sieves and 16.4 grams of hydrated aluminas (German Condea Products, Butt is 74 weight %) mixing, add 0.7 gram of concentrated nitric acid, 18.0 grams of lanthanum nitrates (Chinese medicines group is analyzed pure) and 107.7 grams of water to exist 1.1 millimeters of Φ of cylindrical bar is extruded on double screw banded extruder, wet bar roasts 2 hours after 120 DEG C are 4 hours dry in 550 DEG C, Obtain that molecular sieve content in carrier after molding is 84wt%, lanthanum oxide content 6wt%, alumina host content are 10wt%.

20.0 grams of carriers are weighed in large beaker, are soaked with 19.4 milliliters of n-heptane solution containing 1.4 grams of o-cresols in room temperature It stain 0.5 hour, then, obtains catalyst within dry 2 hours under the conditions of pressure 0.01MPa when 90 DEG C dry, is weighed as 21.3 grams.

The chemical composition of the olefin skeletal isomerization catalyst are as follows: molecular sieve content 79wt%, lanthanum oxide content 5.6wt%, alumina host content 9.4wt%, o-cresol 6.1wt%.

Embodiment 1

The system for producing clean gasoline: there is structure as shown in Figure 2.

The method for producing clean gasoline: the catalyst for etherification that wherein etherification procedure uses is is commercially available from Dandong jewel special type tree The macropore sulfonic acid cation exchange resin of rouge Co., Ltd, trade names are II S of D005-,；Specific process flow is as follows:

It is delivered in finishing reactor 3 (fixed bed reactors) after aforementioned full distillation gasoline 1 is mixed with hydrogen 2, in temperature Degree is 390 DEG C, pressure 2.5MPa, volume space velocity 4.0h^-1, hydrogen hydrocarbon volume ratio is 0.3 to face under the conditions of hydrogen refining reaction, with Refining agent haptoreaction obtains refining reaction product 4；Refining reaction product 4 removes hydrogen therein and portion through lightness-removing column (tank) 5 After dividing C4 following components 6, into gasoline Cutting Tap 8, (inner member is float valve tray, light gasoline fraction to gasoline 7 after obtained purification The end point of distillation be 75 DEG C), cutting fractionation obtain light petrol component 9 (wherein sulphur, basic nitrogen, diene content are as shown in A in table 2) and Heavy gasoline components 10；Light gasoline fraction 9 is merged to the light petrol formed to evaporate with recycle alcohol 24 and fresh alcohol 11 as raw material of etherification Point and the mixture 12 (alcohol is methanol, and the molar ratio of methanol and active olefin is 1.5:1) of alcohol be delivered to level-one methyltertiarvbutyl ether reactor In 13 (fixed bed reactors), at -80 DEG C of temperature 45 C, reaction pressure 0.6MPa, volume space velocity 2.0h^-1Level-one etherificate it is anti- It is contacted under the conditions of answering with catalyst for etherification and carries out level-one etherification reaction, generated level-one and be etherified product 14；Level-one is etherified and is generated Object 14 is delivered in level-one etherificate fractionating column 15 (inner member is float valve tray), and being etherified fractionation pressure tower in level-one is 0.2MPa, Tower top temperature is 55 DEG C, and column bottom temperature carries out the fractionation that level-one is etherified product under conditions of being 120 DEG C, pure and mild with C5 to obtain Based on lighter hydrocarbons tower top azeotropic mixture 16 (wherein be free of TAME) and level-one etherificate Fractionator Bottom fraction 17 (do not contain wherein C5 alkene and alcohol)；The tower top azeotropic mixture 16 of the pure and mild lighter hydrocarbons based on C5 is delivered to second level methyltertiarvbutyl ether reactor 18, and (fixed bed is anti- Answer device) in mixed with the isomerization product 34 of reflux after (in mixed material the molar ratio of methanol and active olefin be 1.5: 1), at -80 DEG C of temperature 60 C, reaction pressure 0.6MPa, volume space velocity 2.0h^-1Second level etherification reaction under the conditions of urged with etherificate Agent contact carries out second level etherification reaction, generates second level and is etherified product 19；Second level etherificate product 19 is delivered to water scrubber In 20 (inner member is structured packing), by with desalted water temperature be 40 DEG C, pressure 0.8MPa, second level be etherified product with The volume ratio of desalted water is counter current contacting under conditions of 1:0.6, obtains second level etherification product 21 in tower top, obtains rich alcohol in tower bottom Water 22；The part 60wt% 27 in second level etherification product 21 is delivered to second level etherificate fractionating column 28, is etherified fractionating column pressure in second level Power is 0.3MPa, and tower top temperature is 55 DEG C, and column bottom temperature carries out the fractionation of second level etherification product under conditions of being 120 DEG C, to obtain It is able to based on C5 component and the not overhead 29 of ether-containing and second level etherificate Fractionator Bottom fraction 30；Will based on C5 component, And the overhead 29 of ether-containing is not delivered in isomerization reactor 33 after being heated to 360 DEG C in heating furnace 32, is being reacted Pressure is 0.2MPa, volume space velocity 2h^-1Isomerization reaction under the conditions of with olefin skeletal isomerization catalyst haptoreaction, obtain Isomerization product 34 is delivered in heat exchanger 31 and based on C5 component and not the tower top of ether-containing does not distillate by isomerization product 34 Object 29 is back in second level methyltertiarvbutyl ether reactor 18 after being exchanged heat, while the rich alcohol water 22 that 20 tower bottom of water scrubber produces being delivered to Separation is distilled in alcohol recovery tower 23, is obtained recycle alcohol 24 in tower top, is obtained desalted water 25 in tower bottom, by 24 washability of recycle alcohol It is back to level-one methyltertiarvbutyl ether reactor 13, desalted water is shunted to the return water scrubber 20 of washability；It collects and divides in gasoline Cutting Tap 8 From obtained heavy naphtha 10, level-one etherificate Fractionator Bottom fraction 17, remaining second level etherification product part 26 and second level ether Change Fractionator Bottom fraction 30, obtains clean gasoline, be denoted as S1, product property is as shown in table 3.

Embodiment 2

The system for producing clean gasoline: the structure referring to shown in Fig. 2, difference are that 33 a part of isomerization product is delivered to two In grade methyltertiarvbutyl ether reactor 18, a part is back in level-one methyltertiarvbutyl ether reactor 13.

The method for producing clean gasoline: referring to embodiment 1, difference is, catalyst for etherification used is a kind of containing Y type point The catalyst of son sieve, method for preparing catalyst bibliography CN 105080589A；60-80 DEG C of etherification reaction temperature；In addition, In second level methyltertiarvbutyl ether reactor, the regurgitant volume of isomerization product 34 is controlled, so that the mixture of tower top azeotropic mixture and isomerization product The molar ratio of middle alcohol and active olefin is adjusted to 1.6:1, and extra isomerization product is returned in level-one methyltertiarvbutyl ether reactor 13. The clean gasoline reconciled is denoted as S2, and product property is as shown in table 3.

Comparative example 1

The system for producing clean gasoline: there is structure as shown in Figure 1.The method for producing clean gasoline: by full distillation gasoline Feedstock transportation to fractionating column carries out fraction cutting (end point of distillation of light petrol is 75 DEG C), and overhead extraction light gasoline fraction, tower bottom is adopted Heavy naphtha out；Light gasoline fraction is first passed through into lye (NaOH solution that concentration is 14wt%) extracting and removes mercaptan therein Then sulphur removes the impurity such as basic nitrogen and metal ion therein by washing (desalted water), finally by selective hydrogenation (temperature The RLF- that degree is 120 DEG C, pressure 1.5MPa, hydrogen-oil ratio 200, dialkene removal catalyst are Research Institute of Petro-Chemical Engineering's production 10w) remove light gasoline fraction (wherein sulphur, basic nitrogen, diene content such as B institute in table 2 after alkadienes therein is refined Show)；Then by the mixture of light gasoline fraction and alcohol after purification, (alcohol is methanol, and the molar ratio of methanol and active olefin is It 1.4:1) is delivered in level-one methyltertiarvbutyl ether reactor (fixed bed reactors), at -75 DEG C of temperature 50 C, reaction pressure 0.6MPa, body Product air speed is 2.0h^-1Level-one etherification reaction under the conditions of contacted with catalyst for etherification (with embodiment 1) carry out level-one etherification reaction, It generates level-one and is etherified product；Level-one generated etherificate product is delivered to etherificate fractionating column (inner member is float valve tray) It is 0.3MPa in etherificate fractionation pressure tower, tower top temperature is 65 DEG C, and column bottom temperature carries out level-one etherificate life under conditions of being 130 DEG C At the separation of object, tower bottom separation obtains level-one etherificate Fractionator Bottom fraction (wherein without C5 alkene and alcohol), and tower top separation obtains The azeotropic mixture (being wherein free of TAME) of the pure and mild lighter hydrocarbons based on C5；The azeotropic mixture of the pure and mild lighter hydrocarbons based on C5 is delivered to two In grade methyltertiarvbutyl ether reactor (fixed bed reactors, the molar ratio of methanol and active olefin is 2.3:1 in azeotropic mixture), in temperature 60 DEG C -75 DEG C, reaction pressure 0.6MPa, volume space velocity 2.0h^-1Second level etherification reaction under the conditions of with catalyst for etherification (with implement Example 1) contact progress second level etherification reaction, it generates second level and is etherified product, generated second level etherificate product is washed into (water Condition is washed referring to embodiment 1) after obtain second level etherification product, while being 290 DEG C in reaction temperature by heavy naphtha, pressure is 1.9MPa, hydrogen-oil ratio 400, volume space velocity 4h^-1Under conditions of carry out selective hydrodesulfurization (catalyst be petrochemical industry section Learn the RSDS-22 of research institute's production), obtain desulfurization heavy naphtha；Gather level-one etherificate Fractionator Bottom fraction, second level etherificate produces Object and desulfurization heavy naphtha, obtain clean gasoline, are denoted as D1, and product property is as shown in table 3.

Comparative example 2

The system for producing clean gasoline: referring to structure as shown in Figure 2, difference is that isomerization product 34 is all back to one In grade methyltertiarvbutyl ether reactor 13.

The method for producing clean gasoline: referring to embodiment 1, difference is, isomerization product 34 is all back to level-one In methyltertiarvbutyl ether reactor 13, the only tower top azeotropic mixture 16 of the lighter hydrocarbons to pure and mild based on C5 in second level methyltertiarvbutyl ether reactor 18 at this time (molar ratio of methanol and active olefin is 2.7:1) carries out etherification process.Obtained clean gasoline is denoted as D2, and product property is such as Shown in table 3.

The product property test of clean gasoline prepared by embodiment 1-2 and comparative example 1-2 is as follows:

(1) it sulfur content: is surveyed using total sulfur content in petrochemical industry standard SH/T 0253-1992 oils Determine method (coulometry) measurement, and by respective data record in table 3；

(2) basic n content: petrochemical industry standard SH/T 0162-92 (2006) oil product neutral and alkali nitrogen is used Measuring method measurement；

(3) composition (diene content, etherate content and olefin(e) centent) of product gasoline is measured using gas chromatography, And by respective data record in table 3；

(4) GB/T 5487-1995 is respectively adopted and measures the preceding research octane number (RON) with blend gasoline after reaction of reaction (RON), and by respective data record in table 3；

(5) energy consumption of alcohol recovery tower is calculated using the method that flowsheeting calculates.

Table 2.

Property	A	B
			Sulfur content, ppm	7	7
Basic n content, ppm	< 2	< 2
			C5 total olefin, wt%	39	41
Diene content, ppm	< 10	100

Table 3.

	S1	S2	D1	D2
					Sulfur content, ppm	6	6	35	7
Etherate content, wt%	12.5	12.9	10.2	13.1
					Olefin(e) centent, wt%	16.7	16.3	19.1	16.2
△RON	0.7	0.8	0.2	0.8
					The energy consumption of alcohol recovery tower, kgEO/t light petrol	8	10	10	15
Diformazan ether content, ppm in second level etherification product	150	230	500	800

Note:

1, the sulfur content in full distillation gasoline raw material is 804ppm, RON 83.5；

2, △ RON indicates the value added of the product gasoline RON compared with full distillation gasoline raw material；

3, the energy consumption of alcohol recovery tower is calculated for the total treating capacity of light petrol and is obtained, and unit is kgEO/t light petrol.

It can be seen from data in table 2 compared with light petrol refining methd employed in comparative example 1, the present invention is in phase To under simplified processing step, in the case where keeping C5 total olefin content substantially, so that influencing the sulphur of catalyst life, alkalinity Nitrogen, alkadienes equal size are substantially reduced.

It can be seen from data in table 3 compared with the method used by the comparative example 1, clean gasoline produced according to the invention The Examples 1 and 2 of method keeping substantially, or even on the basis of reducing energy consumption, considerably reduce second level ether generated Change the content of the dimethyl ether (by-product) in product, and reduce the olefin(e) centent in clean gasoline produced, improves institute Etherate content and octane number in the clean gasoline of production.

It can be seen from data in table 3 compared with the method used by the comparative example 2, clean gasoline produced according to the invention The Examples 1 and 2 of method significantly reduce the energy consumption of alcohol recovery tower in the case where being etherified the substantially comparable situation of effect, and it is significant The content for reducing the dimethyl ether (by-product) in second level etherification product generated.

The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (17)

1. a kind of method for producing clean gasoline, which is characterized in that the described method includes:

(1) under the conditions of facing hydrogen refining reaction, by full distillation gasoline raw material and refining agent haptoreaction, gasoline after being refined, And gasoline after the purification is subjected to cutting fractionation, obtain light gasoline fraction and heavy naphtha；

(2) under the conditions of level-one etherification reaction, the light gasoline fraction is contacted with alcohol and carries out level-one etherification reaction, obtains level-one It is etherified product；Level-one etherificate product is fractionated to the tower top azeotropic mixture and level-one etherificate of the lighter hydrocarbons to be pure and mild based on C5 Fractionator Bottom fraction；

(3) under the conditions of second level etherification reaction, the tower top azeotropic mixture is mixed with isomerization product and carries out second level etherification reaction, Second level etherificate product is obtained, second level etherificate product is subjected to washing process and obtains second level etherification product, and by part Second level etherification product fractionation is etherified Fractionator Bottom for based on C5 component and the not overhead of ether-containing and second level and evaporates Point；Second overhead is subjected to olefin skeletal isomerization processing, obtains the isomerization product, and by the isomery Change product reflux into second level etherification reaction；

(4) heavy naphtha, level-one etherificate Fractionator Bottom fraction, the remaining second level etherification product and institute are collected Second level etherificate Fractionator Bottom fraction is stated, clean gasoline is obtained.

2. the isomerization product all participates in the second level etherification reactions according to the method described in claim 1, wherein, or Second level etherification reaction described in person's subparticipation, rest part, which returns, participates in the level-one etherification reaction.

3. according to the method described in claim 1, wherein, in the second level etherification reaction, the tower top azeotropic mixture with it is described The molar ratio of alcohol and active olefin is (1.2-2.5): 1, preferably (1.4-2.0): 1 in the mixture of isomerization product.

4. the method according to claim 1, wherein the refining agent is contained on the basis of its total weight Have the zinc oxide of 15wt%-60wt%, the alumina binder of 3wt%-35wt%, 5wt%-40wt% laminated clay column, The molecular sieve component of the metal and 0.5wt%-5wt% selected from group VIII of 5wt%-16wt%；The wherein Section VIII The metal of race is preferably Ni and/or Co；

Preferably, molecular sieve component is the combination of one or more of ZSM and SAPO Series Molecules sieve in the refining agent, more excellent It is selected as the combination selected from one or more of ZSM-35, SAPO-11, SAPO-31 and SAPO-34.

5. the method according to claim 1, wherein the hydrogen refining reaction condition of facing includes: temperature It is 320 DEG C -460 DEG C, preferably 340 DEG C -440 DEG C, pressure 0.5MPa-4.0MPa, preferably 1.0MPa-3.5MPa, volume Air speed is 2h^-1-20h^-1, preferably 4h^-1-10h^-1, hydrogen to oil volume ratio 0.1-0.8, preferably 0.2-0.5.

6. the method according to claim 1, wherein 60 DEG C -100 of the light gasoline fraction end point of distillation ℃。

7. the method according to claim 1, wherein alcohol and active alkene in the level-one etherification reaction The molar ratio of hydrocarbon is (1.1-1.6): 1, the preferably described alcohol is methanol or ethyl alcohol, more preferable methanol.

8. the method according to claim 1, wherein the level-one etherification reaction and the second level ether It is identical or different to change catalyst for etherification employed in reaction, is separately selected from cation exchange resin, heteropoly acid or negative One or more of catalyst and modified molecular sieve catalyst of carrying heteropolyacid.

9. the method according to claim 1, wherein the level-one etherification reaction condition and described two Grade etherification reaction condition is identical or different, and the two separately includes: that temperature is 30 DEG C -120 DEG C, preferably 40 DEG C -90 DEG C, Pressure is 0.1MPa-2.0MPa, preferably 0.2MPa-1.0MPa, volume space velocity 0.1h^-1-5.0h^-1, preferably 0.5h^-1- 3.0h^-1。

10. the method according to claim 1, wherein the olefin skeletal isomerization processing step packet It includes: under the conditions of isomerization reaction, the washing product of the overhead being contacted instead with olefin skeletal isomerization catalyst It answers, obtains isomerization product；

Wherein the olefin skeletal isomerization catalyst includes host agent, auxiliary agent and modified compound, and the weight ratio of three is 1: (0.05-0.15): (0.01-0.2) includes molecular sieve and alumina binder and the molecular sieve and oxidation in the host agent The weight ratio of al binder is 1:(0.01-1.0), the auxiliary agent is rare earth oxide, and the modified compound, which is selected from, to be contained Hydroxyl organic compound；

It is preferred that molecular sieve is one or more of ZSM and SAPO Series Molecules sieve group in the olefin skeletal isomerization catalyst It closes, more preferably the combination selected from one or more of ZSM-22, ZSM-35 and SAPO-11；

It is preferred that the rare earth oxide be selected from lanthanum, cerium, praseodymium one or more of oxide combination；

It is preferred that the hydroxyl organic compound is selected from the polyalcohol of phenols or C2-C7, wherein phenols include but is not limited to phenol, The polyalcohol of the combination of one or more of benzenediol, benzenetriol, naphthols, cresols and amino phenols, C2-C7 includes but is not limited to The combination of one or more of ethylene glycol, butanediol, glycerine, pentaerythrite, xylitol and sorbierite.

11. the method according to claim 1, wherein the isomerization reaction condition includes: temperature Degree is 200 DEG C -450 DEG C, is preferably 280 DEG C -420 DEG C, is preferably pressure 0.01MPa-1.0MPa, 0.05MPa-0.5MPa, Volume space velocity is 0.1h^-1-6h^-1, preferably 0.2h^-1-4h^-1。

12. the method according to claim 1, wherein the method also includes (3) washings by described in The rich alcohol water that step obtains carries out distillation processing to recycle alcohol and water, and optionally by recycled alcohol reflux to level-one etherification reaction In, and optionally the water recycled is back in the water-washing step of (3).

13. a kind of system for producing clean gasoline, which is characterized in that the system comprises: finishing reactor (3), gasoline cutting Tower (8), level-one methyltertiarvbutyl ether reactor (13), level-one are etherified fractionating column (15), second level methyltertiarvbutyl ether reactor (18), water scrubber (20), two Grade etherificate fractionating column (28), isomerization reactor (33) and clean gasoline collecting tank,

Wherein the feed inlet of the gasoline Cutting Tap (8) is connected with the discharge port of the finishing reactor (3), light gasoline fraction goes out Mouth is connected with the feed inlet of the level-one methyltertiarvbutyl ether reactor (13), heavy naphtha exports and the clean gasoline collecting tank phase Even；

Wherein the feed inlet of level-one etherificate fractionating column (15) be connected with the discharge port of the level-one methyltertiarvbutyl ether reactor (13), tower Push up feed inlet, tower bottom distillate outlet and the clean gasoline collecting tank of azeotropic mixture outlet and the second level methyltertiarvbutyl ether reactor (18) It is connected；

Wherein the feed inlet of the water scrubber (20) be connected with the discharge port of second level methyltertiarvbutyl ether reactor (18), discharge port respectively with institute The feed inlet and the clean gasoline collecting tank for stating second level etherificate fractionating column (28) are connected；

The wherein feed inlet of the overhead outlet of second level etherificate fractionating column (28) and the isomerization reactor (33) It is connected, tower bottom distillate outlet is connected with the clean gasoline collecting tank；

Wherein the discharge port of the isomerization reactor (33) is connected with the feed inlet of the second level methyltertiarvbutyl ether reactor (18).

14. system according to claim 13, wherein the discharge port of the isomerization reactor (33) it is also selective with The feed inlet of level-one methyltertiarvbutyl ether reactor (13) is connected.

15. system according to claim 13, wherein further include alcohol recovery tower (23), the water scrubber in the system (20) tower bottom richness alcohol water out is connected with the feed inlet of the alcohol recovery tower (23), the recycling alcohol outlet of the alcohol recovery tower (23) It is connected with the feed inlet of the level-one methyltertiarvbutyl ether reactor (13).

16. system according to claim 13, wherein in second level etherificate fractionating column (28) and the isomerization reaction Heating furnace (32) are additionally provided between device (33).

17. system according to claim 16, wherein in second level etherificate fractionating column (28) and the heating furnace (32) Between be additionally provided with heat exchanger (31), the heat exchanger (31) respectively be connected to second level etherificate fractionating column (28) and described add It flow path between hot stove (32) and is connected between the isomerization reactor (33) and the second level methyltertiarvbutyl ether reactor (18) Flow path is connected.