CN107974292B

CN107974292B - A kind of vapour oil treatment process

Info

Publication number: CN107974292B
Application number: CN201610922006.3A
Authority: CN
Inventors: 许友好; 罗一斌; 王新; 欧阳颖; 达志坚; 舒兴田; 汪燮卿
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2016-10-21
Filing date: 2016-10-21
Publication date: 2019-10-25
Anticipated expiration: 2036-10-21
Also published as: CN107974292A

Abstract

The present invention relates to a kind of vapour oil treatment process, which includes: that gasoline stocks are sent into fluidizing reactor to contact with mixed catalyst and carry out desulfurization and aromatization under hydro condition, obtains desulfurization and aromatization products；Gained desulfurization and aromatization products are cut, light gasoline fraction and heavy naphtha are obtained；Gained light gasoline fraction is subjected to etherification process, obtains etherificate oil；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；By weight and on the basis of the weight of the alkene aromatized catalyst, passivation content is 0.1-5.0 weight % in the alkene aromatized catalyst；The passivation includes selected from least one of carbon, sulphur and nitrogen element.Method provided by the invention can reduce sulphur and olefin(e) centent in gasoline, and can improve the octane number of gasoline simultaneously and keep high yield of gasoline.

Description

A kind of vapour oil treatment process

Technical field

The present invention relates to a kind of vapour oil treatment process.

Background technique

Atmosphere pollution caused by motor vehicle exhaust emission is got worse.As people are to the pay attention to day by day of environmental protection, China The paces of vehicle fuel quality upgrading are accelerated, standard GB/T 17930-2013 requires sulfur content in gasoline to be not more than 10 μ g/ G, volume fraction of olefins are not more than 24%.

Catalytically cracked gasoline is the chief component of China's motor petrol, and 75% or so is accounted in gasoline pool, and it is special Point is alkene with higher and sulfur content.The deep desulfuration of gasoline is realized using hydrogen addition technology and is reduced in catalytically cracked gasoline Olefin(e) centent it is not difficult, but since alkene is antiknock component, being greatly reduced for content will lead to octane number Heavy losses, to influence the automobile-used performance of gasoline and the economic benefit of oil plant, therefore in the deep desulfuration for realizing gasoline Octane number is kept to become the hot spot of China's clean gasoline production simultaneously.

Currently, the deep desulfuration of gasoline is mainly the method for using hydrodesulfurization or adsorbing desulfurization.

Selective hydrodesulfurization is one of the major way of current removing thiophene-type sulfide, but the reactions such as alkene saturation are same Sample largely occurs, and causes loss of octane number larger.In addition, the deep hydrogenation method for restoring octane number is similarly approved by people, It is that second reactor is set to promote cracking hydrocarbon, the isomery of low octane rating while carrying out deep desulfuration and alkene is saturated Change and alkylated reaction, to achieve the purpose that restore octane number.Chinese patent CN101845322A has invented a kind of reduction vapour The method of sulphur and olefin(e) centent in oil, raw material catalytic cracking gasoline first pass through pre-hydrogenator removing alkadienes, subsequently into Fractionating column cutting is fractionated into light, heavy petrol, and light petrol carries out facing hydrogen absorption desulfurization, and heavy petrol enters selective hydrogenation reactor and adds Hydrogen desulfurization, reaction effluent enter back into hydro-upgrading reactor and carry out hydro-upgrading, reduce olefin(e) centent, the heavy petrol after modification It reconciles to obtain the clean gasoline for meeting standard requirements with light petrol absorption desulfurization product.Absorbing desulfurization catalyst is in gasoline Although sulfide has good removal effect, absorption desulfurization carries out under conditions of facing hydrogen, can be saturated catalytically cracked gasoline In alkene, especially light petrol carries out absorption desulfurization, and the olefin component octane number in light petrol is higher, will cause the pungent of gasoline Alkane value is largely lost.

Absorption method removes the sulfur-containing compound in fuel oil, is to carry out facing hydrogen reaction absorption to light oil using adsorbent, raw Sulphur is removed at metal sulfide or using sulfide polarity, hydrogen consumption is lower, and desulfuration efficiency is high, can produce sulfur content in 10 μ g/g Following gasoline.Although absorbing process realizes the deep desulfuration of gasoline under the conditions of low hydrogen consumes, gasoline product octane number is still omited There is loss.Especially when handling olefin(e) centent height and the high gasoline stocks of sulfur content, still cause octane number loss compared with Greatly.

For most of catalytic cracking units, for propylene enhancing and butylene yield and the octane number for improving gasoline, It is effective method using containing the catalyst or auxiliary agent with MFI structure molecular sieve.United States Patent (USP) USP3758403 is disclosed The method that ZSM-5 molecular sieve is added in catalytic cracking catalyst can be improved the octane number of gasoline and increase C3~C4 alkene Yield.But as it is known by one skilled in the art, propylene enhancing and butylene yield are to sacrifice gasoline production as cost.

Aromatizing low-carbon paraffin is the effective ways for improving low-carbon alkanes utility value.People are to high silica alumina ratio molecular sieve A large amount of research is carried out for the aromatization process of catalyst, especially using ZSM-5, ZSM-11, ZSM-21 molecular sieve as catalyst Process carried out a large amount of research, and using the zeolite with MFI structure be used to produce from coking or pyrolysis gasoline low The aromatisation of carbon hydro carbons.

Summary of the invention

The object of the present invention is to provide a kind of vapour oil treatment process, method provided by the invention be can reduce in gasoline Sulphur and olefin(e) centent, and the octane number of gasoline can be improved simultaneously and keep high yield of gasoline.

To achieve the goals above, the present invention provides a kind of vapour oil treatment process, which includes: by gasoline original Material, which is sent into fluidizing reactor, to be contacted with mixed catalyst and carries out desulfurization and aromatization under hydro condition, is taken off Sulphur and aromatization products；Gained desulfurization and aromatization products are cut, light gasoline fraction and heavy naphtha are obtained；By institute It obtains light gasoline fraction and carries out etherification process, obtain etherificate oil；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene Hydrocarbon aromatizing catalyst；By weight and on the basis of the weight of the alkene aromatized catalyst, the alkene aromatisation is urged Passivation content is 0.1-5.0 weight % in agent；The passivation includes selected from least one of carbon, sulphur and nitrogen element.

Preferably, the method also includes: by gained etherificate oil and heavy naphtha mix, obtain gasoline products.

Preferably, the alkene aromatized catalyst passes through Passivation Treatment, and the step of Passivation Treatment includes: will be fresh Aromatized catalyst contacts with carbon containing and/or sulphur and/or nitrogen compound in pre-reactor and carries out green coke；Or it will regeneration Aromatized catalyst contacts with carbon containing and/or sulphur and/or nitrogen compound in pre-reactor and carries out green coke；Or it will be to be generated Aromatized catalyst carries out incomplete singeing regeneration.

Preferably, the pre-reactor is the reactor outside the fluidizing reactor or is positioned at the fluidised form Change the pre lift zone in reactor.

Preferably, volume fraction of olefins is greater than 20 body % in the gasoline stocks.

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

Preferably, the gasoline stocks are selected from catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, thermal cracking vapour At least one of oil and direct steaming gasoline.

Preferably, the cut point of the light gasoline fraction and heavy naphtha is 60-80 DEG C.

Preferably, the step of etherification process includes: to contact the light gasoline fraction with alcohols, makes the light petrol With alcohols etherification reaction occurs for the alkene in fraction under the action of catalyst for etherification, obtains the etherificate oil；Wherein, the ether The temperature for changing reaction is 20-200 DEG C, pressure 0.1-5MPa, and weight (hourly) space velocity (WHSV) is 0.1-20 hours^-1, the alcohols and light petrol The molar ratio of fraction is 1:(0.1-100), the catalyst for etherification includes at least one in resin, molecular sieve and heteropoly acid Kind.

Preferably, the fluidizing reactor is riser reactor and/or dense-phase fluidized bed reactor.

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

Preferably, on the basis of the dry weight of the absorbing desulfurization catalyst and in terms of oxide weight, the absorption Zinc oxide described in desulphurization catalyst accounts for 10-90 weight %, and silica accounts for 5-85 weight %, and aluminium oxide accounts for 5-30 weight %； On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, taken off described in the absorbing desulfurization catalyst The content of sulphur active metal is 5-30 weight %.

Preferably, it is counted by butt and on the basis of the total weight of the alkene aromatized catalyst, the alkene aromatisation Catalyst contains the molecular sieve of 10-30 weight %, the aromatization activity metal oxide of 0-20 weight % and 50-90 weight %'s Carrier；Wherein, the molecular sieve includes Y molecular sieve and/or MFI structure molecular sieve, and the aromatization activity metal is selected from the The metallic element of Group IVB, the metallic element of Group VB, the metallic element of group VIB, the metallic element of group VIII, group ib Metallic element, group iib metallic element and at least one of the metallic element of group III A, the carrier includes oxidation Silicon and/or aluminium oxide.

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

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

Preferably, it is 350-500 DEG C that the condition of the desulfurization and aromatization, which includes: reaction temperature, and weight (hourly) space velocity (WHSV) is 2-50 hours^-1, reaction pressure 0.5-3.0MPa, hydrogen and gasoline stocks volume ratio are 1-500.

Preferably, the method also includes: the etherification process is carried out after the light gasoline fraction is pre-processed again, Wherein, the pretreatment is selected from least one of caustic extraction processing, mercaptan conversion processing and selective hydrogenation processing.

The present invention has following technical effect that compared with prior art

1, method of the invention is by the gasoline stocks of the high alkene of high-sulfur and absorbing desulfurization catalyst and alkene Aromatizatian catalytic Agent carries out desulfurization and aromatization, and while reducing content of sulfur in gasoline, the alkene in gasoline can be carried out to cracking and virtue Structure produces C₅Following hydro carbons and cut etherification reaction is carried out in light gasoline fraction, to both reduce alkene in gasoline Content also improves the octane number of gasoline and keeps the high income of gasoline stocks, being capable of direct producing country V even VI label of state Gasoline.

2, desulfurization of the invention and aromatization are carried out in a fluidizing reactor using two kinds of catalyst, are both mentioned High reaction efficiency, also reduces cost of investment, without increasing or changing reactor.

3, method of the invention can also reduce the light component in gasoline, reduce gasoline vapour pressure.

4, alkene aromatized catalyst of the invention passes through Passivation Treatment, keeps the activity of alkene aromatized catalyst moderate, Be conducive to the progress of aromatisation.

5, light gasoline fraction is carried out etherification process by the present invention, can either reduce wherein alkene, additionally it is possible to produce higher octane The etherificate oil of value, improves the octane number of gasoline products.

6, desulfurization of the invention and aromatization are carried out in a fluidizing reactor using two kinds of catalyst, can be with Gasoline step-by-step processing method (desulfurization after aromatisation or gasoline elder generation aromatisation after the desulfurization of gasoline elder generation) is avoided to need individually to increase aromatization Change reactor and subsystem, can also need to change existing absorption desulfurization to avoid gasoline desulfurization and aromatisation coupled catalyst and urge The preparation process flow and catalyst abrasion intensity of agent and aromatized catalyst, both improve reaction efficiency, also reduce Cost of investment.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:

Fig. 1 is a kind of flow diagram of specific embodiment of the method for the present invention.

Description of symbols

1 gasoline stocks, 2 hydrogen, 3 fluidizing reactor

6 tail gas of 4 desulfurization and 5 high-pressure separator of aromatization products

Complete 8 fractionating column of fraction, 9 light gasoline fraction of 7 gasoline

10 heavy naphtha, 11 pretreatment unit 12 is etherified preceding light petrol

13 methanol, 14 ether-based device, 15 etherification product

16 fractionating columns 17 are etherified oil containing methanol-fueled exhaust 18

19 mixer, 20 gasoline products

Specific embodiment

Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

RIPP test method is for details, reference can be made to " petrochemical analysis method " in the present invention, and Yang Cui is surely equal to be compiled, nineteen ninety version.

The present invention provides a kind of vapour oil treatment process, which includes: that gasoline stocks are sent into fluidization reaction It is contacted in device with mixed catalyst and carries out desulfurization and aromatization under hydro condition, obtain desulfurization and aromatization products； Gained desulfurization and aromatization products are cut, light gasoline fraction and heavy naphtha are obtained；By gained light gasoline fraction into Row etherification process obtains etherificate oil；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene Aromatizatian catalytic Agent；By weight and on the basis of the weight of the alkene aromatized catalyst, passivation in the alkene aromatized catalyst Content is 0.1-5.0 weight %, preferably 0.3-2.0 weight %, further preferably 0.3-1 weight %；The passivation packet It includes selected from least one of carbon, sulphur and nitrogen element.

According to the present invention, for direct producing country V even VI label gasoline of state.The method can also include: by gained Etherificate oil and heavy naphtha mixing, obtain gasoline products.

According to the present invention, desulfurization and aromatization refer to gasoline stocks under hydro condition in absorbing desulfurization catalyst and Desulfurization is carried out under the collective effect of alkene aromatized catalyst and converts alkene to the process of aromatic hydrocarbons, it is during which anti-with cracking It answers, condition may include: that reaction temperature is 350-500 DEG C, and preferably 380-420 DEG C, weight (hourly) space velocity (WHSV) is 2-50 hours^-1, excellent It is selected as 5-20 hours^-1, reaction pressure 0.5-3.0MPa, preferably 1.5-2.5MPa, hydrogen (marking with gasoline stocks volume ratio Quasi- situation (STP) 0 DEG C of (273K), 1.01 × 10⁵Under Pa) it is 1-500, preferably 50-200.

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

A kind of specific embodiment, on the basis of the dry weight of the absorbing desulfurization catalyst and with oxide weight Meter, zinc oxide described in the absorbing desulfurization catalyst account for 10-90 weight %, and silica accounts for 5-85 weight %, and aluminium oxide accounts for 5-30 weight %；On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, the absorption desulfurization is urged The content of desulphurizing activated metal described in agent is 5-30 weight %.

According to the present invention, the absorbing desulfurization catalyst can also contain 1-10 weight % class coke mass.Industrial practice Show that the carbon content on absorbing desulfurization catalyst has shadow to desulfuration efficiency and the octane number loss of absorbing desulfurization catalyst It rings, with increasing for absorbing desulfurization catalyst carbon content, absorbing desulfurization catalyst desulfuration efficiency gradually declines, octane number damage Mistake reduces therewith.Similarly, the sulfur content that absorbing desulfurization catalyst keeps certain is very important.Practice have shown that suction to be generated It is 9 weight %-10 weight % that attached desulphurization catalyst, which carries sulfur content, and regenerative adsorption desulphurization catalyst carries 5 weight %-6 weight % of sulfur content, The sulphur difference of absorbing desulfurization catalyst to be generated and regenerative adsorption desulphurization catalyst is that 4 weight % or so are the most suitable.To reduce gasoline Loss of octane number will have been generally acknowledged that reasonable " small sulphur poor, big cycle volume " operation adjustment for the behaviour of " partial circulating amount, big sulphur are poor " Make, reduce regenerative adsorption desulphurization catalyst sulfur content, improve absorbing desulfurization catalyst sulfur content to be generated, reduces octane number damage It loses, two kinds of operation essence have been to maintain the higher load sulfur content that the absorbing desulfurization catalyst of reaction is participated in reactor, reduce and inhale The activity of attached desulphurization catalyst, reduces loss of octane number.

According to the present invention, alkene aromatized catalyst is to refer to hydrocarbon conversions such as alkene in gasoline stocks be aromatic hydrocarbons Catalyst, generally comprise molecular sieve, preferably include molecular sieve, carrier and metal, for example, in terms of butt and with alkene virtue On the basis of the total weight of structure catalyst, the alkene aromatized catalyst can the molecular sieve containing 10-30 weight %, 0-20 The aromatization activity metal oxide of weight % and the carrier of 50-90 weight %；Wherein, the molecular sieve may include Y molecule Sieve and/or MFI structure molecular sieve, preferably five-membered ring high-silica zeolite, high-silica zeolite can be Hydrogen, be also possible to By rare earth and/or P Modification, silica alumina ratio is preferably greater than 100, more preferably greater than 150.The MFI structure molecular sieve can be with For selected from least one of ZSM-5, ZSM-8 and ZSM-11.The aromatization activity metal can play partial desulfurization or hydrocarbon Class transformation function, such as can be first for metallic element, the metal of group VIB of metallic element, Group VB selected from group ivb Element, the metallic element of group VIII, the metallic element of group ib, the metallic element of group iib and group III A metallic element At least one of；The wherein metallic element of group ivb preferred Zr or/and Ti, the preferred V of the metallic element of Group VB, group VIB Metallic element preferred Mo or/and W, one or more of the metallic element of group VIII preferred Fe, Co, Ni element, The preferred Cu of the metallic element of group ib, the preferred Zn of the metallic element of group iib, the preferred Ga of the metallic element of group III A, into one Step ground, the aromatization activity metal are preferably selected from least one of Fe, Zn and Ga, and content is preferably 0.5-5 weight %. The carrier preferably includes silica and/or aluminium oxide.It is micro- that the partial size of the alkene aromatized catalyst is generally 20-120 Rice is suitable with absorbing desulfurization catalyst partial size.Absorbing desulfurization catalyst and alkene aromatized catalyst are separately formed by the present invention It is used in mixed way after (such as spray drying).

A kind of specific embodiment, the MFI structure molecular sieve, preparation process may include ammonia exchange, P Modification, In particular metal component modification and calcination process step are by the obtained sodium form with MFI structure of conventional crystallization point Son sieve is according to molecular sieve: ammonia salt: H₂O=1:(0.1-1): the weight ratio of (5-10) is in room temperature to exchanging 0.3-1 hours at 100 DEG C After filter, introduce phosphorus-containing compound and containing selected from one of Fe, Co, Ni, Zn, Mn, Ga and Sn or a variety of compounds pair Molecular sieve is modified, and is roasted 0.5-8 hours at 400-800 DEG C later, wherein the described treatment process roasted is also possible to It is carried out under steam atmosphere.Further, MFI structure molecular sieve provided by the present invention, during the preparation process to molecular sieve Being modified can be is carried out by the way of dipping or ion exchange.Further, the phosphorus-containing compound can be choosing From or mixtures thereof one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate.Further, the Fe, Co, Ni, Zn, Mn, Ga and Sn compound can be selected from their water soluble salt, the water soluble salt can for selected from sulfate, nitrate, One of chlorate.Further, MFI structure molecular sieve provided by the present invention, contains phosphorus and metal component, acid site In conjunction with the dehydrogenation close centre of metal, and the presence of phosphorus simultaneously not only can be improved the structural stability of molecular sieve but also make gold The ability of dehydrogenation sulfurization of category.

The method that the present invention introduces metal active constituent on molecular sieve or carrier can use existing various gold-supporteds Belong to the method for oxide, such as method of dipping, i.e., using one or more of metal salt solution impregnated zeolites or carrier；Or it is heavy The method in shallow lake, i.e., using on one or more of metal salt solutions or its oxide, hydroxide deposition to molecular sieve or carrier；Or Person's soild oxide and/or its precursor-metal salt or its hydroxide and molecular sieve or carrier mechanical mixture, grinding or not The method of grinding；Or colloidal sol facture, gelling process and hydro-thermal method etc..The metal salt is mainly the sulfate of metal, nitre Hydrochlorate, acetate, halide and metal ammonium salt, metal sodium salt etc..Preferred method present invention introduces metal active constituent is heavy The method of the method or dipping in shallow lake.

According to the difference of alkene in gasoline and sulfur content, absorbing desulfurization catalyst and alkene aromatisation in fluidizing reactor The ratio of catalyst can be different, for example, by weight, the alkene aromatized catalyst accounts for the ratio of the mixed catalyst For 1-30 weight %, preferably 3-15 weight %.

Present inventors discovered unexpectedly that the micro-activity of alkene aromatized catalyst effect in 20-55 is more excellent, The micro-activity is measured using the mat activity test method of RIPP 92-90 catalytic cracking industry equilibrium catalyst.However From manufacturer's production or the not yet used fresh aromatized catalyst of homemade qualification, activity is active generally 60 or more Higher, cracking performance is stronger, and therefore, fresh aromatized catalyst is handled, and to reduce acid amount, increases acid strength, has Conducive to the generation for reducing hydrogen transfer reaction.

A kind of embodiment, the alkene aromatized catalyst pass through Passivation Treatment, can be with the step of the Passivation Treatment It include: that fresh aromatized catalyst is contacted and given birth to carbon containing and/or sulphur and/or nitrogen compound in pre-reactor It is burnt；Or regeneration aromatized catalyst is contacted and given birth to carbon containing and/or sulphur and/or nitrogen compound in pre-reactor It is burnt；Or aromatized catalyst to be generated is subjected to incomplete singeing regeneration.The aromatized catalyst to be generated refers in fluidization By using the catalyst for having loaded certain coke, activity reduces, is not enough to continue to react in reactor.By aromatization to be generated Changing catalyst progress incomplete singeing regeneration reduces loaded coke content, can obtain more suitable activity.It is described Aromatized catalyst is regenerated by aromatized catalyst to be generated through regeneration gained completely, and regeneration temperature is generally 450-690 DEG C, regeneration Gas is generally oxygen-containing gas, returns in fluidizing reactor and is recycled by regenerated catalyst circulation.Regeneration aromatisation is urged Agent coke content needs as fresh aromatized catalyst pre- anti-generally in 0.1 weight % hereinafter, hyperactivity It answers and carries out green coke in device.

The green coke of the fresh aromatized catalyst and regeneration aromatized catalyst can be reacted being located at the fluidization It carries out, can also be carried out in the pre lift zone being located in the fluidizing reactor, used in green coke in reactor outside device Carbon containing and/or sulphur and/or nitrogen compound can be gasoline, hydrogen sulfide or carbon disulfide etc., and gasoline both can be the gasoline Raw material, or the gasoline stocks outside fluidizing reactor, such as catalytically cracked gasoline, steam cracking gasoline or other The gasoline of olefin-containing.

According to the present invention, gasoline stocks are well-known to those skilled in the art, can be selected from catalytically cracked gasoline, urge Change at least one of drippolene, coker gasoline, pressure gasoline and direct steaming gasoline.The gasoline that the present invention is handled is preferably height Alkene and high sulfur oil, volume fraction of olefins are generally higher than 20 body %, preferably greater than 30 body %, more preferably greater than 40 body %, Further preferably greater than 50 body %；Sulfur content is generally more than 10 μ g/g, preferably greater than 50 μ g/g, more preferably greater than 100 μ g/g, Further preferably greater than 500 μ g/g are still more preferably greater than 1000 μ g/g, the organic sulfur compound in gasoline be generally mercaptan, Thioether, thiophene, alkylthrophene, benzothiophene and methyl benzothiophene etc..

According to the present invention, the cut point of the light gasoline fraction and heavy naphtha can be 60-80 DEG C, desulfurization and aromatization The cutting for changing product carries out generally in fractionating column according to boiling range from low to high, for example, the operation item of the fractionating column of gasoline cutting Part are as follows: tower top temperature is 60-80 DEG C, and column bottom temperature is 120-160 DEG C, operating pressure 0.05-0.3MPa.

According to the present invention, etherification process refers to C in light gasoline fraction₅Low-carbon hydro carbons below (such as iso-amylene and ring Amylene) and alcohols progress etherification reaction, to generate high-octane etherificate oil, for example, the step of etherification process can wrap Include: the light gasoline fraction contacted with alcohols, make the alkene in the light gasoline fraction under the action of catalyst for etherification with Etherification reaction occurs for alcohols, obtains the etherificate oil；Wherein, the temperature of the etherification reaction can be 20-200 DEG C, and pressure can Think 0.1-5MPa, weight (hourly) space velocity (WHSV) can be 0.1-20 hours^-1, the molar ratio of the alcohols and light gasoline fraction can be 1: (0.1-100), the catalyst for etherification may include selected from least one of resin, molecular sieve and heteropoly acid, the hydro carbons It can be for selected from least one of methanol, ethyl alcohol and propyl alcohol.

Strong acid cation exchange resin catalyst is loaded on one section of etherificate by a kind of specific embodiment of etherification process And/or in two sections of etherificate fixed bed reactors, etherificate will be passed through by pretreated light gasoline fractions such as desulfurization and dialkene removals It is 50-90 DEG C in reaction temperature in reactor, liquid hourly space velocity (LHSV) 1.0-3.0h^-1, methanol and light gasoline fraction active olefin (isomery Alkene, such as iso-amylene) etherification reaction occurs under conditions of molar ratio 1-2, etherification product is sent into rectifying column separation, is obtained in tower bottom To etherificate oil, unreacted lighter hydrocarbons and methanol loop are utilized.Etherification procedure reaction temperature preferably is inlet temperature 55-60 DEG C, for outlet temperature less than 90 DEG C, air speed is preferably 1-2h^-1, the molar ratio of methanol and light gasoline fraction is preferably 1.2-1.4.Its In, it is suitable for using mixed phase bed reactor that one section of etherificate olefin(e) centent is higher, and two sections of etherificate olefin(e) centents are lower, is suitable for using exhausted Thermosetting fixed bed reactor.In addition, isomerization unit also can be applied to during Etherification of Light FCC Gasoline.Etherification of Light FCC Gasoline has reduction Content of olefin in gasoline improves octane number, reduces vapour pressure and improve added value and strengthen many advantages, such as reconciling benefit, etherificate Oil can be used as octane number blend component carry out using, can also be mixed with heavy naphtha as full distillation gasoline produce Product.

According to the present invention, fluidizing reactor is well-known to those skilled in the art, for example, can for selected from fluidized bed, It is riser, downstriker pipeline reactor, the compound reactor being made of riser with fluidized bed, defeated by riser and downstriker Line sending constitute compound reactor, be made of two or more risers compound reactor, by two or two with On the fluidized bed compound reactor constituted, the compound reactor that is made of two or more downstriker pipelines, it is excellent It is selected as riser reactor and/or fluidized-bed reactor, above-mentioned every kind of reactor is segmented into two or more reactions Area.The fluidized-bed reactor can be for selected from fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying One or more of bed and dense-phase fluidized bed；The riser reactor can for selected from equal diameter riser, etc. linear speeds mention One or more of riser and various variable diameters risers.Preferably, it is anti-to be selected from dense-phase fluidized for the fluidizing reactor Answer device.

According to the present invention, light gasoline fraction need to generally be pre-processed before carrying out etherification reaction, to remove sulfide With the impurity such as alkadienes, to extend the service life of catalyst for etherification.Therefore, the method for the invention can also include: will be described light Gasoline fraction carries out the etherification process after being pre-processed again, wherein the pretreatment can for selected from caustic extraction processing, At least one of mercaptan conversion processing and selective hydrogenation processing.Caustic extraction processing uses lye by the sulphur of light gasoline fraction Alcohol extracting is removed into lye；Mercaptan conversion processing converts other sulfide for small molecule mercaptan and removes, and can use The modes such as conventional alkali-free sweetening technique and pre-add hydrogen carry out, and used catalyst and co-catalyst all can be commonly used in the art Catalyst.Selective hydrogenation processing be it is well-known to those skilled in the art, for removing alkadienes in gasoline, and can be by 3- Methyl-1-isomerization of butene is 2-methyl-1-butene alkene.

There is provided a kind of specific embodiment of the invention with reference to the accompanying drawing, but it is not thereby limiting the invention.

As shown in Figure 1, entering fluidizing reactor 3 after the gasoline stocks 1 of high alkene high-sulfur are mixed with hydrogen 2, with suction Attached desulphurization catalyst and aromatized catalyst contact through transpassivation carry out absorption desulfurization and aromatization, desulfurization after reaction Enter high-pressure separator 5 with aromatization products 4, obtains the full fraction 7 of gasoline and tail gas 6 of low-sulfur.The full fraction 7 of gasoline enters fractionation Tower 8 carries out cutting fractionation, is fractionated as light gasoline fraction 9 and low-sulfur heavy naphtha 10, light gasoline fraction and heavy naphtha Cut point is about 65~70 DEG C.The preprocessed unit 11 of light gasoline fraction carries out the pretreatments such as removal of mercaptans and obtains being etherified preceding light petrol 12, ether-based device 14 then is mixed into methanol 13 and is reacted, and etherification product 15 is fractionated the fractionation of tower 16 and obtains etherificate oil 18 with contain methanol-fueled exhaust 17.Etherificate oil 18 after heavy naphtha 10 and etherification process is mixed to get higher octane in mixer 19 It is worth clean gasoline product 20.

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

The full fraction of gasoline stocks used in embodiment and comparative example is stable gasoline A, and property is listed in table 1.

Absorbing desulfurization catalyst used in embodiment and comparative example is catalyzed by Sinopec Group The production of agent branch company, goods number FCAS, used aromatized catalyst are that catalyst is made in laboratory by oneself, and the trade mark is OTAZ-C-3, absorbing desulfurization catalyst and aromatized catalyst property are listed in table 2.

Wherein, the preparation method of aromatized catalyst OTAZ-C-3 is: by 50g (NH₄)₂SO₄It is dissolved in 1000g water, to institute It obtains and 100g (butt) crystallization product ZSM-5 molecular sieve (production of Chang Ling catalyst plant, non-amine method synthesis) is added in solution, at 95 DEG C After exchanging 1h, filter cake is filtered to obtain；By 8.6g (NH₄)₂HPO₄It is dissolved in 60g water, is mixed with dipping and dries with filter cake；It adds 6.0gGa(NO₃)₃·9H₂O is dissolved in 120g water, is mixed with dipping and is dried with above-mentioned sample；Gained sample is in 580 DEG C of calcination process 3 Hour, obtain molecular sieve product；Gained molecular sieve product is added in 500 grams of (butt) sial colloids, it is spray-dried to be made Microspherical catalyst.

In following embodiment and comparative example, Na in catalyst₂O、NiO、ZnO、Ga₂O₃、Al₂O₃、SiO₂Content X Ray fluorescence measures, wherein Al₂O₃、SiO₂Content referring specifically to RIPP134-90 measure, remaining composition measuring method phase Seemingly.

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

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

Embodiment 1

The fresh aromatized catalyst that the trade mark is OTAZ-C-3 is packed into dense-phase fluidized bed reactor, in passivation temperature 410 With stable gasoline A haptoreaction under the conditions of DEG C, continuously inactivating 2 hours, passivation aromatized catalyst is obtained, passivation content is 0.5 heavy %.

Stable gasoline raw material A is in small-sized continuous fluidized bed reactor and including absorbing desulfurization catalyst FCAS and passivation virtue The mixed catalyst contact of structure catalyst OTAZ-C-3 (OTAZ-C-3 account for total catalyst weight 7%), carries out absorption desulfurization And aromatization.Operating condition are as follows: reaction temperature is 400 DEG C, reactor pressure 2.1MPa, the weight (hourly) space velocity (WHSV) of gasoline stocks It is 6 hours^-1, the volume ratio of hydrogen and gasoline stocks is 75.The desulfurization that obtained by reactor head and aromatization products through cooling, Isolated tail gas and the full fraction of gasoline.The regeneration temperature of mixed catalyst is 550 DEG C, and the mixed catalyst after regeneration returns anti- It answers in device and is recycled.

The full fraction of above-mentioned gasoline is distilled in fractionating column, is cut into light gasoline fraction and low-sulfur heavy naphtha, Controlling the light fraction end point of distillation is 80 DEG C (being carried out according to ASTM D86 standard).Wherein, the light gasoline fraction distilled is denoted as LCN-A, heavy naphtha are denoted as HCN-A, and the property of the light gasoline fraction and heavy naphtha that distill is listed in table 3.Light vapour Oil distillate carries out desulfurization, dialkene removal pretreatment through finishing reactor under hydro condition, make in light gasoline fraction sulfur content and Diene content is down to 10ppm hereinafter, being then mixed into methyltertiarvbutyl ether reactor with methanol carries out etherification reaction, etherification reaction item Part is 55-80 DEG C of reaction temperature, air speed 1.2h^-1, methanol and light gasoline fraction active olefin (isomeric olefine) molar ratio 1.2, instead Oil gas enters etherificate fractionating column separation after the etherificate that should be obtained, and top gaseous phase is the tail containing methanol for including residual carbon five and methanol Gas, tower bottom obtain etherificate oil, and the tower top temperature for being etherified fractionating column is 60-80 DEG C, and column bottom temperature is 110-140 DEG C.Corresponding ether Carburetion is denoted as LCN-A-M, and property is equally listed in table 3.

Heavy naphtha after obtained absorption desulfurization is mixed to get clean gasoline with high octane with etherificate oil LCN-A-M Product, property are listed in table 4.

Comparative example 1

Stable gasoline raw material A is in small-sized continuous fluidized bed reactor and in absorbing desulfurization catalyst FCAS and embodiment 1 Resulting passivation aromatized catalyst OTAZ-C-3 (OTAZ-C-3 account for total catalyst weight 7%) mixed catalyst contact, into Row absorption desulfurization and aromatization.Operating condition are as follows: reaction temperature is 400 DEG C, reactor pressure 2.1MPa, gasoline stocks Weight (hourly) space velocity (WHSV) be 6 hours^-1, the volume ratio of hydrogen and gasoline stocks is 75.The desulfurization and aromatisation obtained by reactor head Product is cooled and separated to obtain gaseous product and the full fraction of gasoline, and the full fraction of gasoline is without cutting and is etherified directly as gasoline Product, property are listed in table 4.The regeneration temperature of mixed catalyst is 550 DEG C, in the mixed catalyst Returning reactor after regeneration It is recycled.

Comparative example 2

It is essentially identical with the operation of comparative example 1, the difference is that all being inhaled using absorbing desulfurization catalyst FCAS Attached desulphurization reaction, the full fraction of gasoline are used as gasoline products without cutting and etherificate, and property is listed in table 4.

It can be seen from Table 4 that embodiment 1 is suitable with the desulfuration efficiency of comparative example 1 and comparative example 2, and embodiment 1 is ground Study carefully method octane number and increase about 2.0 units than comparative example 1, increases about 3.5 units than comparative example 2.

Table 1

Table 2

Catalyst	FCAS	OTAZ-C-3
			Chemical composition, weight %
Aluminium oxide	13	50.3
			Sodium oxide molybdena	/	0.06
Nickel oxide	21	/
			Zinc oxide	52	/
Gallium oxide	/	1.5
			Silica	14	48.14
Apparent density, kg/m³	1010	800
			Pore volume, mL/g	/	0.27
Specific surface area, m²/g	/	218
			Abrasion index, again when %^-1	/	1.5
Screening composition, weight %
			0~40 micron	14.5	13.9
40~80 microns	51.9	49.5
			> 80 microns	33.6	36.6
Micro-activity	/	80

Table 3

Table 4

Claims

1. a kind of vapour oil treatment process, the processing method include:

Gasoline stocks are sent into fluidizing reactor and is contacted with mixed catalyst and carries out desulfurization and aromatization under hydro condition Change reaction, obtains desulfurization and aromatization products；

Gained desulfurization and aromatization products are cut, light gasoline fraction and heavy naphtha are obtained；

Gained light gasoline fraction is subjected to etherification process, obtains etherificate oil；

Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；

By weight and on the basis of the weight of the alkene aromatized catalyst, passivation in the alkene aromatized catalyst Content is 0.1-5.0 weight %；The passivation includes selected from least one of carbon, sulphur and nitrogen element；The alkene aromatisation The micro-activity of catalyst is 20-55, and the micro-activity is micro- using RIPP 92-90 catalytic cracking industry equilibrium catalyst Anti- activity test method is measured.

2. according to the method described in claim 1, wherein, the method also includes: gained etherificate oil and heavy naphtha are mixed It closes, obtains gasoline products.

3. according to the method described in claim 1, wherein, the alkene aromatized catalyst passes through Passivation Treatment, the passivation The step of processing includes:

Fresh aromatized catalyst is contacted in pre-reactor with carbon containing and/or sulphur and/or nitrogen compound and carries out green coke； Or

Regeneration aromatized catalyst is contacted in pre-reactor with carbon containing and/or sulphur and/or nitrogen compound and carries out green coke； Or

Aromatized catalyst to be generated is subjected to incomplete singeing regeneration.

4. according to the method described in claim 3, wherein, the pre-reactor is the reaction outside the fluidizing reactor Device is the pre lift zone in the fluidizing reactor.

5. according to the method described in claim 1, wherein, volume fraction of olefins is greater than 20 volume % in the gasoline stocks.

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

7. according to the method described in claim 1, wherein, the gasoline stocks are selected from catalytically cracked gasoline, catalytic pyrolysis vapour At least one of oil, coker gasoline, pressure gasoline and direct steaming gasoline.

8. according to the method described in claim 1, wherein, the cut point of the light gasoline fraction and heavy naphtha is 60-80 ℃。

9. according to the method described in claim 1, wherein, the step of etherification process include: by the light gasoline fraction with Alcohols contact, makes the alkene in the light gasoline fraction that etherification reaction occur with alcohols under the action of catalyst for etherification, obtains The etherificate oil；Wherein, the temperature of the etherification reaction is 20-200 DEG C, pressure 0.1-5MPa, weight (hourly) space velocity (WHSV) 0.1-20 Hour^-1, the molar ratio of the alcohols and light gasoline fraction is 1:(0.1-100), the catalyst for etherification include selected from resin, point At least one of son sieve and heteropoly acid.

10. according to the method described in claim 1, wherein, the fluidizing reactor is riser reactor and/or dense-phase flow Fluidized bed reactor.

11. according to the method described in claim 1, wherein, the absorbing desulfurization catalyst contains silica, aluminium oxide, oxygen Change zinc and desulphurizing activated metal, the desulphurizing activated metal be in cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium extremely Few one kind.

12. according to the method for claim 11, wherein on the basis of the dry weight of the absorbing desulfurization catalyst and with Oxide weight meter, zinc oxide described in the absorbing desulfurization catalyst account for 10-90 weight %, and silica accounts for 5-85 weight %, Aluminium oxide accounts for 5-30 weight %；On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, the absorption The content of desulphurizing activated metal described in desulphurization catalyst is 5-30 weight %.

13. according to the method described in claim 1, wherein, in terms of butt and with the total weight of the alkene aromatized catalyst On the basis of, the alkene aromatized catalyst contains the aromatization activity metal oxygen of the molecular sieve of 10-30 weight %, 0-20 weight % The carrier of compound and 50-90 weight %；Wherein, the molecular sieve includes Y molecular sieve and/or MFI structure molecular sieve, the aromatization Changing active metal is metallic element, the metallic element of Group VB, the metallic element of group VIB, group VIII selected from group ivb Metallic element, the metallic element of group ib, the metallic element of group iib and group III A metallic element at least one Kind, the carrier includes silica and/or aluminium oxide.

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

15. according to the method described in claim 1, wherein, by weight, the alkene aromatized catalyst accounts for the mixing and urges The ratio of agent is 1-30 weight %.

16. according to the method described in claim 1, wherein, the condition of the desulfurization and aromatization includes: that reaction temperature is 350-500 DEG C, weight (hourly) space velocity (WHSV) is 2-50 hours^-1, reaction pressure 0.5-3.0MPa, hydrogen and gasoline stocks volume ratio are 1- 500。

17. according to the method described in claim 1, wherein, the method also includes: the light gasoline fraction is pre-processed Carry out the etherification process again afterwards, wherein the pretreatment is to add selected from caustic extraction processing, mercaptan conversion processing and selectivity At least one of hydrogen processing.