CN108949229A - 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: gasoline after full distillation gasoline raw material and refining agent haptoreaction are refined, and gasoline after purification is subjected to cutting fractionation and obtains light gasoline fraction and heavy naphtha；Light gasoline fraction is contacted into progress level-one etherification reaction with alcohol and obtains level-one etherificate product；Level-one etherificate product is fractionated to the tower top azeotropic mixture and tower bottom level-one etherification product of the lighter hydrocarbons to be pure and mild based on C5；And part tower top azeotropic mixture is subjected to washing and olefin skeletal isomerization and handles to obtain isomerization product；Remaining tower top azeotropic mixture is contacted into progress second level etherification reaction with isomerization product and obtains second level etherificate product, and product progress washing process will be etherified through second level and obtain second level etherification product；It collects heavy naphtha, tower bottom level-one etherification product and second level etherification product and obtains clean gasoline.This method can reduce the internal circulating load of energy consumption and alcohol while reducing the olefin(e) centent in 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, with while reducing the olefin(e) centent and sulfur content in gasoline, the internal circulating load of alcohol, reduces the energy of system in reduction system Consumption.

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 and tower bottom level-one etherification product that product fractionation is the pure and mild lighter hydrocarbons based on C5；And it will The part tower top azeotropic mixture successively carries out washing and olefin skeletal isomerization processing, obtains isomerization product；(3) in second level ether Change under reaction condition, second level etherification reaction is carried out after remaining described tower top azeotropic mixture is mixed with the isomerization product, is obtained It is etherified product to second level, and product will be etherified through second level and carry out washing process, obtains second level etherification product；(4) institute is collected Heavy naphtha, the tower bottom level-one etherification product and the second level etherification product are stated, clean gasoline (product) is obtained.

According to another aspect of the present invention, a kind of system for producing clean gasoline is provided, which includes: that purification is anti- Answer device, gasoline Cutting Tap, level-one methyltertiarvbutyl ether reactor, etherificate fractionating column, second level methyltertiarvbutyl ether reactor, one-stage water wash tower, second level washing Tower, isomerization reactor and clean gasoline collecting tank, wherein the feed inlet of the gasoline Cutting Tap and the finishing reactor Discharge port be connected, light gasoline fraction outlet be connected with the feed inlet of the level-one methyltertiarvbutyl ether reactor, heavy naphtha export and The clean gasoline collecting tank is connected；The wherein discharge port of the feed inlet of the etherificate fractionating column and the level-one methyltertiarvbutyl ether reactor Be connected, tower top azeotropic mixture outlet be connected respectively with the feed inlet of the feed inlet of the second level methyltertiarvbutyl ether reactor and second level water scrubber, The outlet of tower bottom level-one etherification product is connected with the clean gasoline collecting tank；The wherein feed inlet of the isomerization reactor and institute The tower top discharge port for stating second level water scrubber is connected, discharge port is connected with the feed inlet of the second level methyltertiarvbutyl ether reactor；It is wherein described The feed inlet of one-stage water wash tower is connected with the discharge port of the second level methyltertiarvbutyl ether reactor, and tower top discharge port and the clean gasoline are received Collect tank to be connected.

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

(1) portion by being etherified to level-one in the tower top azeotropic mixture for the pure and mild lighter hydrocarbons based on C5 that product is fractionated Divide and carry out olefin skeletal isomerization processing, the linear alkene for wherein not having etherification activity is transformed into the uncle with etherification activity Isomerization product is then mixed with remaining tower top azeotropic mixture and directly carries out second level etherification reaction by carbon olefin, without adding In the case where secondary alcohol, secondary application is carried out to the alcohol in tower top azeotropic mixture, thus greatly improving the total amount that can be etherified alkene, While reducing olefin(e) centent in gasoline, reduces the internal circulating load of alcohol, reduces the recycling load and energy consumption of alcohol；

(2) by the way that isomerization product wholly or largely is introduced two with the tower top azeotropic mixture without isomerization processing In grade etherification reaction, it can reduce the operating load of level-one etherification reaction and fractional distillation process, reduce the energy consumption of fractional distillation process；

(3) by being added isomerization product and the tower top azeotropic mixture without isomerization processing simultaneously to second level etherification reaction In, advantageously reduce the alfin ratio of second level etherification reaction, be not only advantageous to avoid because alfin ratio it is excessively high caused by alcohol side reaction, And the consumption of the alcohol in tower top azeotropic mixture is also advantageously improved, it reduces the internal circulating load of alcohol, reduce the recycling load and energy of alcohol Consumption.

(4) 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 following components, 7 be gasoline after purification, 8 be gasoline Cutting Tap, 9 be light gasoline fraction, 10 attach most importance to Gasoline fraction, 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 ether Change product, 15 be etherified fractionating column, 16 be the tower top azeotropic mixture of the pure and mild lighter hydrocarbons based on C5,17-19 as tower bottom level-one ether Change product, 20 be second level methyltertiarvbutyl ether reactor, 21 be second level be etherified product, 22 be one-stage water wash tower, 23 be second level etherification product, 24 be rich alcohol water, 25 be alcohol recovery tower, 26 be recycle alcohol, 27-29 be desalted water, 30 be second level water scrubber, 31 be dealcoholysis lighter hydrocarbons, 32 it is rich alcohol water, 33 be heat exchanger, 34 be heating furnace, 35 be isomerization reactor, 36 is 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 being etherified product to level-one In remaining C5 component carry out isomerization and handle to improve to be etherified alkene total amount, play the effect of etherification of olefine to greatest extent Technical solution either will however, inventor has found during the isomerized products to C5 component carry out etherification process again The isomerized products of C5 component are back in level-one methyltertiarvbutyl ether reactor, are still introduced into second level methyltertiarvbutyl ether reactor and are etherified Processing can all increase the load of the energy consumption of technique, the internal circulating load of alcohol and alcohol recycling.It is of the invention in order to improve such case Inventor further provides the method and its corresponding system of a kind of new 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 tower bottom level-one etherification product of main lighter hydrocarbons；And the part tower top azeotropic mixture is successively carried out to washing and alkene Hydrocarbon skeletal isomerizations processing, obtains isomerization product；(3) under the conditions of second level etherification reaction, by remaining tower top azeotropic Object carries out second level etherification reaction after mixing with the isomerization product, obtains second level etherificate product, and second level is etherified and is generated Object carries out washing process, obtains second level etherification product；(4) collect the heavy naphtha, the tower bottom level-one etherification product and The second level etherification product, obtains the clean gasoline.

According to the method for the present invention, comprehensively consider the olefin(e) centent in the bearing capacity, energy consumption and gasoline products of equipment, The isomerization product can all participate in the second level etherification reaction, can also with second level etherification reaction described in 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 (1.4-2.5): 1；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 mixture of the tower top azeotropic mixture and the isomerization product The molar ratio of alcohol and active olefin is (1.4-2.0): 1.Wherein the molar ratio of pure and mild active olefin can be by online or offline The method for testing and analyzing active olefin total amount in light petrol calculates and monitoring, and wherein active olefin total amount can pass through gas-chromatography Method analysis obtains (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% the gold selected from group VIII The molecular sieve component of category and 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, and usually the mixture of C4-C7 component in full distillation gasoline raw material is fractionated as light gasoline fraction, Whole C5 component and part or all of C6 component are generally included in the light gasoline fraction.It is described light thus under preferable case 60 DEG C -100 DEG C of the gasoline 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 level-one methyltertiarvbutyl ether reactor can be one of fixed bed, expanded bed, mixed phase bed Or several combination.Under preferable case, the level-one etherification reaction condition include: temperature be 30 DEG C -120 DEG C, preferably 40 DEG C - In the range that any two in 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；Pressure is 0.1-2.0MPa, preferably 0.2-1.0MPa, for example, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, Appointing in the range that any two in 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa and these point values are constituted Meaning numerical value；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 be by the tower top azeotropic mixture of whole pure and mild lighter hydrocarbons based on C5 and ether compound into Row separation, so that etherificate fractionator overhead is substantially free of ether compound, tower bottom is substantially free of alcohol and is substantially free of C5 alkene Level-one etherificate product is fractionated the tower top azeotropic mixture of the lighter hydrocarbons to be pure and mild based on C5 and tower bottom level-one etherificate produces by hydrocarbon Object.In addition, the influence in order to avoid TAME to the equilibrium conversion of C5 active olefin, under preferable case, the overhead extraction alcohol With in the tower top azeotropic mixture of the lighter hydrocarbons based on C5 do not contain TAME.About the step of by level-one etherificate product fractionation Process conditions are referred to foregoing purpose and are reasonably adjusted, such as: the pressure for being etherified fractionating column is 0.2-0.5MPa, tower bottom temperature Degree is 100-150 DEG C, and tower top temperature is 40-80 DEG C.

According to the method for the present invention, in (2) by the purpose that part tower top azeotropic mixture is washed be removing this Alcohol in the tower top azeotropic mixture of part, the step can (tower internals can be filler, sieve plate, float valve tray or its group in water scrubber Close) in carry out, poor solubility of the alcohol in hydrocarbon and water can be utilized by by this part tower top azeotropic mixture and water counter current contacting It is different, the remaining alcohol in this part tower top azeotropic mixture is removed using the method for extraction.Specific way is by water from water scrubber top Be added, the tower top azeotropic mixture containing pure and mild lighter hydrocarbons from water scrubber lower part enter, after washing process, dealcoholysis lighter hydrocarbons from washing tower top Extraction, rich alcohol water are produced from tower bottom.Under preferable case, the condition of the water-washing step are as follows: temperature is 10 DEG C -50 DEG C, pressure For 0.1MPa-1.0MPa, the volume ratio 1:0.2-2.0 of tower top azeotropic mixture and water.Wherein preferably used water is softened water, removes Salt water or deionized water.

It according to the method for the present invention, is by C5 for the purpose for carrying out olefin skeletal isomerization processing step in (2) 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 dealcoholysis product of the tower top azeotropic mixture (dealcoholysis lighter hydrocarbons) and olefin skeletal isomerization 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), the host agent include molecular sieve and alumina binder, and the molecular sieve With the weight ratio 1:(0.01-1.0 of the alumina binder), the auxiliary agent is rare earth oxide, the modified compound choosing Self-contained 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 being carried out in advance to washing dealcoholysis product (dealcoholysis lighter hydrocarbons) between washing process step and olefin skeletal isomerization processing step The step of heating；In addition, converting to optimize the heat of entire process flow, under preferable case, isomerization product pair can be used Washing dealcoholysis product exchanges heat.

According to the method for the present invention, the purpose for secondary etherification reaction being carried out in (3) is by remaining tower top Azeotropic mixture carries out second level etherification reaction after mixing with the isomerization product, to reduce the olefin(e) centent in gasoline products.For The process of secondary etherification reaction focuses on, and makes full use of the remaining alcohol in the tower top azeotropic mixture, needs to control the tower The molar ratio for pushing up alcohol and active olefin in the mixture of azeotropic mixture and the isomerization product makes it preferably (1.4-2.5): 1； Moreover, under preferable case, being etherified in the second level to further decrease the content of by-product dimethyl ether in second level etherification product In reaction, the molar ratio of alcohol and active olefin is (1.4- in the mixture of the tower top azeotropic mixture and the isomerization product 2.0): any two in 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 these ratios Any ratio in the range constituted.

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.

It according to the method for the present invention, is de- by the purpose for carrying out washing process through second level etherificate product in (3) Except the alcohol in second level etherificate product, can another water scrubber (tower internals can be filler, sieve plate, float valve tray or A combination thereof) in carry out, dissolution of the alcohol in hydrocarbon and water can be utilized by the way that the second level is etherified product and water counter current contacting The remaining alcohol in difference elimination reaction product is spent, obtains second level etherification product and rich alcohol water, under preferable case, the washing step Rapid condition are as follows: temperature is 10 DEG C -50 DEG C, pressure 0.1MPa-1.0MPa, and it is 1 that second level, which is etherified product and the volume ratio of water: 0.2-2.0.Wherein used water is softened water, demineralized water or deionized water.

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 twice, be to be washed to part tower top azeotropic mixture and second level etherificate product respectively Step can generate rich alcohol water in the two steps, and in order to realize the recycling to alcohol and recycle, according to the present invention Method in further include: the distillation processing rich alcohol water is to recycle alcohol and water, and optionally by recycled alcohol reflux to level-one ether Change in reaction, optionally the water recycled is back in water-washing step.

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, alcohol recovery tower tower bottom produce desalted water exchanged heat, cool down after return to water scrubber Top 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 Include: finishing reactor 3, gasoline Cutting Tap 8, level-one methyltertiarvbutyl ether reactor 13, etherificate fractionating column 15, second level methyltertiarvbutyl ether reactor 20, One-stage water wash tower 22, second level water scrubber 30, isomerization reactor 35 and clean gasoline collecting tank, wherein the gasoline is cut The feed inlet of tower 8 is connected with the discharge port of the finishing reactor 3, light gasoline fraction exports and the level-one methyltertiarvbutyl ether reactor 13 Feed inlet be connected, heavy naphtha outlet be connected with the clean gasoline collecting tank；Wherein it is described etherificate fractionating column 15 into Material mouth is connected with the discharge port of the level-one methyltertiarvbutyl ether reactor 13, the outlet of tower top azeotropic mixture respectively with the second level methyltertiarvbutyl ether reactor 20 feed inlet and the feed inlet of second level water scrubber 30 are connected, tower bottom level-one etherification product exports and the clean gasoline collecting tank It is connected；Wherein the feed inlet of the isomerization reactor 35 be connected with the tower top discharge port of the second level water scrubber 30, discharge port It is connected with the feed inlet of the second level methyltertiarvbutyl ether reactor 20；Wherein the feed inlet of the one-stage water wash tower 22 and the second level are etherified The discharge port of reactor 20 is connected, and tower top discharge port is connected with the clean gasoline collecting tank.

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 35 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 35 is all delivered to second level methyltertiarvbutyl ether reactor 20 In, or be partially delivered in second level methyltertiarvbutyl ether reactor 20, rest part is delivered to level-one methyltertiarvbutyl ether reactor 13, and then different in guarantee In the case that structure product can fully enter subsequent processing operations, level-one methyltertiarvbutyl ether reactor 13 and second level methyltertiarvbutyl ether reactor are adjusted The molar ratio of alcohol and active olefin in 20.

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 25 under preferable case, the tower bottom of first water scrubber 22 and the second water scrubber 30 Rich alcohol water out is connected with the feed inlet of the alcohol recovery tower 25 respectively, the recycling alcohol outlet of the alcohol recovery tower 25 and described one The feed inlet of grade methyltertiarvbutyl ether reactor 13 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 34 is additionally provided between the second level water scrubber 30 and the isomerization reactor 35.Meanwhile in order to optimize the system Heat is converted, and under preferable case, heat exchanger 33 is additionally provided between the second level water scrubber 30 and the heating furnace 34, described to change Hot device 33 respectively with the flow path being connected between the second level water scrubber 30 and the heating furnace 34 and be connected to the isomerization Flow path between reactor 35 and the second level methyltertiarvbutyl ether reactor 20 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, etherificate fractionating column 15, second level methyltertiarvbutyl ether reactor 20, one-stage water wash tower 22, alcohol recovery tower 25, second level water scrubber 30, heat exchange The selection of device 33, heating furnace 34, isomerization reactor 35 and clean gasoline collecting tank can not have particular/special requirement, as long as It 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 product) 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 (fluidized-bed reactor) after aforementioned full distillation gasoline raw material 1 is mixed with hydrogen 2, It is 429 DEG C, pressure 2.6MPa, volume space velocity 6.5h in temperature^-1, hydrogen hydrocarbon volume ratio is 0.28 to face hydrogen refining reaction condition Under, refining reaction product 4 is obtained with refining agent haptoreaction；Refining reaction product 4 removes hydrogen therein through lightness-removing column (tank) 5 After part C4 following components 6, into gasoline Cutting Tap 8, (inner member is float valve tray, light petrol to gasoline 7 after obtained purification The fraction end point of distillation is 75 DEG C), cutting fractionation obtains light petrol component 9 (wherein sulphur, basic nitrogen, diene content such as A institute in table 2 Show) and heavy gasoline components 10；Light gasoline fraction 9 is merged as raw material of etherification with recycle alcohol 26 and fresh alcohol 11 to the light vapour formed It is anti-that the mixture 12 (alcohol is methanol, and the molar ratio of methanol and active olefin is 1.4:1) of oil distillate and alcohol is delivered to level-one etherificate It answers in device 13 (fixed bed reactors), at -75 DEG C of temperature 50 C, reaction pressure 0.6MPa, volume space velocity 2.0h^-1Level-one ether Change to contact under reaction condition with catalyst for etherification and carry out level-one etherification reaction, generates level-one and be etherified product 14；Level-one is etherified Product 14 is delivered in etherificate fractionating column 15 (inner member is float valve tray), is 0.3MPa, tower top in etherificate fractionation pressure tower Temperature is 65 DEG C, and column bottom temperature carries out the separation that level-one is etherified product under conditions of being 130 DEG C, and tower bottom separation obtains tower bottom one Grade etherification product 17 (wherein without containing C5 alkene and alcohol), tower top separation obtain the tower top azeotropic mixture of the pure and mild lighter hydrocarbons based on C5 16 (being wherein free of TAME)；The tower top azeotropic mixture 16 of the pure and mild lighter hydrocarbons based on C5 is shunted, part of tower top azeotropic Object 19 enter second level water scrubber 30 (inner member is structured packing), by with desalted water temperature be 40 DEG C, pressure 0.8MPa, The volume ratio of tower top azeotropic mixture and desalted water is counter current contacting under conditions of 1:0.4, dealcoholysis lighter hydrocarbons 31 is obtained in tower top, in tower bottom Obtain rich alcohol water；Dealcoholysis lighter hydrocarbons 31 are heated to be delivered in isomerization reactor 35 after 380 DEG C in heating furnace 34, are being reacted Pressure is 0.3MPa, volume space velocity 2h^-1Isomerization reaction under the conditions of with olefin skeletal isomerization catalyst haptoreaction, obtain Isomerization product 36 is delivered to after being exchanged heat in heat exchanger 33 with dealcoholysis lighter hydrocarbons 31 by isomerization product 36, with remaining institute It states tower top azeotropic mixture 18 and is delivered to second level methyltertiarvbutyl ether reactor 20 (fixed bed reactors, methanol and work in mixed material together Property alkene molar ratio be 1.8:1) in, at -75 DEG C of temperature 60 C, reaction pressure 0.6MPa, volume space velocity 2.0h^-1Second level It is contacted under the conditions of etherification reaction with catalyst for etherification and carries out second level etherification reaction, generated second level and be etherified product 21；By second level ether Change product 21 be delivered in one-stage water wash tower 22 (inner member is structured packing), by with desalted water temperature be 40 DEG C, pressure Power is 0.8MPa, and it is counter current contacting under conditions of 1:0.6 that second level, which is etherified product and the volume ratio of desalted water, obtains two in tower top Grade etherification product 23 obtains rich alcohol water in tower bottom；The rich alcohol water that one-stage water wash tower 22 and 30 tower bottom of second level water scrubber are produced is defeated It send into alcohol recovery tower 25 distillation to separate, obtains recycle alcohol 26 in tower top, obtain desalted water 27 in tower bottom, recycle alcohol 26 is optional Property be back to level-one methyltertiarvbutyl ether reactor 13, desalted water is shunted, a part of desalted water 28 returns to one-stage water wash tower 22, another portion Desalted water 29 is divided to be back to second level water scrubber 30；It collects heavy naphtha 10 isolated in gasoline Cutting Tap 8, be etherified The tower bottom level-one etherification product 17 that 13 bottom of fractionating column obtains and the second level etherification product 23 obtained in 22 tower top of one-stage water wash tower, Clean gasoline is obtained, S1 is denoted as, 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 36 part of isomerization product is delivered to second level In methyltertiarvbutyl ether reactor 20, rest 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；Etherification reaction temperature is 60-80 DEG C；In addition, In second level methyltertiarvbutyl ether reactor, by rubbing for the tower top azeotropic mixture and alcohol in the mixture of the isomerization product and active olefin You return to level-one methyltertiarvbutyl ether reactor than being adjusted to 1.5:1, and by extra isomerization product.The clean gasoline note reconciled For S2, 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: full distillation gasoline is delivered to fractionating column progress fraction cutting, and (end of light petrol evaporates Point is 75 DEG C), overhead extraction light gasoline fraction, tower bottom produces heavy naphtha；Light gasoline fraction is first passed through lye, and (concentration is The NaOH solution of 14wt%) extracting removes mercaptan sulfur therein, then by washing (desalted water) remove basic nitrogen therein and The impurity such as metal ion, finally by selective hydrogenation, (temperature is 120 DEG C, pressure 1.5MPa, hydrogen-oil ratio 200, dialkene removal are urged Agent is the RLF-10w of Research Institute of Petro-Chemical Engineering's production) remove the light gasoline fraction after alkadienes therein is refined (wherein sulphur, basic nitrogen, diene content are as shown in B in table 2)；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 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, volume space velocity 2.0h^-1Level-one etherification reaction under the conditions of with etherificate be catalyzed Agent (with embodiment 1) contact carries out level-one etherification reaction, generates level-one and is etherified product；Level-one generated is etherified product It is 0.3MPa that etherificate fractionating column (inner member is float valve tray), which is delivered to, in etherificate fractionation pressure tower, and tower top temperature is 65 DEG C, tower Bottom temperature carries out the separation that level-one is etherified product under conditions of being 130 DEG C, tower bottom separation obtains tower bottom level-one etherification product (its In without C5 alkene and alcohol), tower top separation obtains the tower top azeotropic mixture (being wherein free of TAME) of the pure and mild lighter hydrocarbons based on C5；It will The tower top azeotropic mixture of the pure and mild lighter hydrocarbons based on C5 is delivered to second level methyltertiarvbutyl ether reactor (fixed bed reactors, in tower top azeotropic mixture The molar ratio of methanol and active olefin is 2.3:1) in, at -75 DEG C of temperature 60 C, reaction pressure 0.6MPa, volume space velocity is 2.0h^-1Second level etherification reaction under the conditions of contacted with catalyst for etherification (with embodiment 1) carry out second level etherification reaction, generate second level It is etherified product, generated second level etherificate product is washed after (washing conditions are referring to embodiment 1) and obtains second level etherificate Product, while being 290 DEG C, pressure 1.9MPa in reaction temperature by heavy naphtha, hydrogen-oil ratio 400, volume space velocity 4h^-1 Under conditions of carry out selective hydrodesulfurization (catalyst be Research Institute of Petro-Chemical Engineering production RSDS-22), obtain desulfurization Heavy naphtha；Gather tower bottom level-one etherification product, second level etherification product and desulfurization heavy naphtha, obtain clean gasoline, remembers For D1, 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 36 is all back to one In grade methyltertiarvbutyl ether reactor 13；

The method for producing clean gasoline: referring to embodiment 1, difference is, by the pure and mild lighter hydrocarbons based on C5 produced Tower top azeotropic mixture in 40wt% enter second level methyltertiarvbutyl ether reactor (molar ratio of methanol and active olefin be in tower top azeotropic mixture 2.3:1), while by 60wt% in the tower top azeotropic mixture of the pure and mild lighter hydrocarbons based on C5 produced second level water scrubber is sequentially entered Isomerization product is obtained with isomerization reactor, and isomerization product is all back to level-one methyltertiarvbutyl ether reactor (wherein methanol Molar ratio with active olefin is 1.4:1).Obtained clean gasoline is denoted as D2, and product property is 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 etherificate fractionator and alcohol recovery tower is calculated using the method that flowsheeting calculates.

Table 2.

Property	A	B
			Sulfur content, ppm	3	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	7	6	35	6
Etherate content, wt%	11.7	12.6	10.2	12.7
					Olefin(e) centent, wt%	17.9	17.2	19.1	17.0
△RON	0.4	0.8	0.2	0.9
					It is etherified fractionator energy consumption, kgEO/t light petrol	12	14	12	18
The energy consumption of alcohol recovery tower, kgEO/t light petrol	9	11	10	15
					Diformazan ether content, ppm in second level etherification product	120	80	500	520

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 etherificate fractionator and the energy consumption of alcohol recovery tower are to calculate to obtain for the total treating capacity of light petrol, 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 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 Method Examples 1 and 2 in the case where being etherified the substantially comparable situation of effect, significantly reduce energy consumption, and significantly reduce The content of 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 tower bottom level-one of the lighter hydrocarbons to be pure and mild based on C5 Etherification product；And the part tower top azeotropic mixture is successively carried out to washing and olefin skeletal isomerization processing, obtain isomerization production Object；

(3) it under the conditions of second level etherification reaction, is carried out after remaining described tower top azeotropic mixture is mixed with the isomerization product Second level etherification reaction obtains second level etherificate product, and will be etherified product through second level and carry out washing process, obtains second level etherificate Product；

(4) heavy naphtha, the tower bottom level-one etherification product and the second level etherification product are collected, cleaning vapour is obtained Oil.

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 (1.4-2.5): 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%；Wherein selected from described the The metal of VIII group 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 dealcoholysis product of the tower top azeotropic mixture being connect with olefin skeletal isomerization catalyst Touching reaction, 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), the host agent include molecular sieve and alumina binder and the molecular sieve and the oxygen The weight ratio for changing al binder is 1:(0.01-1), the auxiliary agent is rare earth oxide, and the modified compound is selected from 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. according to the method described in claim 10, wherein, the isomerization reaction condition includes: that temperature is 200 DEG C -450 DEG C, preferably 280 DEG C -420 DEG C, be 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 (2) and institutes by described in It states the rich alcohol water that (3) water-washing step obtains and carries out distillation processing to recycle alcohol and water, and extremely optionally by the alcohol reflux recycled In level-one etherification reaction, and optionally the water recycled is back in the water-washing step of (2) and/or (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), etherificate fractionating column (15), second level methyltertiarvbutyl ether reactor (20), one-stage water wash tower (22), two Grade water scrubber (30), isomerization reactor (35) 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 it is described etherificate fractionating column (15) feed inlet be connected with the discharge port of the level-one methyltertiarvbutyl ether reactor (13), tower top it is total Boiling object outlet be connected respectively with the feed inlet of the feed inlet of the second level methyltertiarvbutyl ether reactor (20) and second level water scrubber (30), tower bottom The outlet of level-one etherification product is connected with the clean gasoline collecting tank；

Wherein the feed inlet of the isomerization reactor (35) is connected with the tower top discharge port of the second level water scrubber (30), discharges Mouth is connected with the feed inlet of the second level methyltertiarvbutyl ether reactor (20)；

Wherein the feed inlet of the one-stage water wash tower (22) is connected with the discharge port of the second level methyltertiarvbutyl ether reactor (20), tower top goes out Material mouth is connected with the clean gasoline collecting tank.

14. system according to claim 13, wherein the discharge port of the isomerization reactor (35) 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 in the system alcohol recovery tower (25), first water The tower bottom richness alcohol water out for washing tower (22) and the second water scrubber (30) is connected with the feed inlet of the alcohol recovery tower (25) respectively, institute The recycling alcohol outlet for stating alcohol recovery tower (25) is connected with the feed inlet of the level-one methyltertiarvbutyl ether reactor (13).

16. system according to claim 15, wherein in the second level water scrubber (30) and the isomerization reactor (35) heating furnace (34) are additionally provided between.

17. system according to claim 16, wherein between the second level water scrubber (30) and the heating furnace (34) Be additionally provided with heat exchanger (33), the heat exchanger (33) respectively be connected to the second level water scrubber (30) and the heating furnace (34) Between flow path and the flow path that is connected between the isomerization reactor (35) and the second level methyltertiarvbutyl ether reactor (20) be connected.