CN107974294B

CN107974294B - A kind of vapour oil treatment process

Info

Publication number: CN107974294B
Application number: CN201610921807.8A
Authority: CN
Inventors: 许友好; 毛俊义; 王新; 袁清; 于敬川; 聂红; 李大东
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: CN107974294A

Abstract

The present invention relates to a kind of vapour oil treatment process, which includes: to cut gasoline stocks, obtains light gasoline fraction and heavy naphtha；Gained light gasoline fraction is subjected to etherification process, obtains etherificate oil；Gained heavy naphtha is sent into fluidizing reactor and is contacted with mixed catalyst and carries out desulfurization and aromatization under hydro condition, obtains heavy petrol product；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；The preparation step of the alkene aromatized catalyst includes: that fresh aromatized catalyst is carried out aging process.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 is cut, and light gasoline fraction and heavy naphtha are obtained；Gained light gasoline fraction is subjected to etherification process, is etherified Oil；Will gained heavy naphtha be sent into fluidizing reactor in contact with mixed catalyst and under hydro condition progress desulfurization and Aromatization obtains heavy petrol product；Wherein, the mixed catalyst includes that absorbing desulfurization catalyst and alkene aromatisation are urged Agent；The preparation step of the alkene aromatized catalyst includes: that fresh aromatized catalyst is carried out aging process.

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

Preferably, it is 500-800 DEG C that the condition of the aging process, which includes: temperature, and the time is 1-360 hours, aging gas Atmosphere includes steam atmosphere.

Preferably, the micro-activity of the alkene aromatized catalyst is 20-55, and the micro-activity uses RIPP 92- The mat activity test method of 90 catalytic cracking industry equilibrium catalysts is measured.

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

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

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

Preferably, the cut point of the light gasoline fraction and 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 heavy naphtha 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, the gasoline stocks of the high alkene of high-sulfur are carried out being cut into light gasoline fraction and heavy naphtha by method of the invention Afterwards, heavy naphtha and absorbing desulfurization catalyst and alkene aromatized catalyst are subjected to desulfurization and aromatization, reduced While content of sulfur in gasoline, the alkene in gasoline can be subjected to aromatisation, to both reduce the content of alkene in gasoline, also It improves the octane number of gasoline and keeps the high income of gasoline stocks, it being capable of direct producing country V even VI label gasoline of state.

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

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

4, alkene aromatized catalyst of the invention passes through aging process, 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 fractionating column, 3 heavy naphtha

4 hydrogen, 5 fluidizing reactor, 6 desulfurization and aromatization products

7 high-pressure separator, 8 tail gas, 9 heavy petrol product

10 light gasoline fraction, 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: to cut gasoline stocks, obtains light Gasoline fraction and heavy naphtha；Gained light gasoline fraction is subjected to etherification process, obtains etherificate oil；By gained heavy naphtha It is sent into fluidizing reactor and is contacted with mixed catalyst and carry out desulfurization and aromatization under hydro condition, obtain weight vapour Oil product；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；The alkene aromatisation The preparation step of catalyst includes: that fresh aromatized catalyst is carried out aging process.

According to the present invention, for direct producing country V even VI label gasoline of state.The method can also include: by gained Etherificate oil and the mixing of heavy petrol product, 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 and heavy naphtha volume ratio ( The status of criterion (STP) 0 DEG C of (273K), 1.01 × 10⁵Under Pa) it is 1-500, preferably 50-200.

According to the present invention, absorbing desulfurization catalyst is well-known to those skilled in the art, 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 aging process.Aging process refers to deposits in vapor Fresh aromatized catalyst is subjected to high-temperature process under the conditions, to reduce its activity.The condition of the aging process can be with Include: temperature be 500-800 DEG C, the time be 1-360 hours, aging atmosphere is steam atmosphere, preferably 100% vapor gas Atmosphere.

A kind of specific embodiment of aging process, by fresh aromatized catalyst and vapor or steam-laden aging Media contact, under certain thermal and hydric environment (temperature be 500 DEG C -800 DEG C) after aging -360 hours 1 hour, obtained aging Aromatized catalyst.Further, the aging process refers to fresh aromatized catalyst in 800 DEG C and 100% vapor Aging certain time is under condition (referring to RIPP 92-90) to reduce activity, if ageing time is 4h or 17h.Further, newly The ageing method of fresh aromatized catalyst is implemented: fresh aromatized catalyst is packed into the preferably close phase of reactor Fluidized bed is contacted with vapor or steam-laden aging medium, under certain thermal and hydric environment (temperature is 500 DEG C -800 DEG C) After aging -360 hours 1 hour, aging aromatized catalyst is obtained.Further, the aging medium include air, dry gas, The gas or other gases such as nitrogen after gas or air and burning oil firing after regenerated flue gas, air and dry combustion gas.Institute The weight ratio for stating the vapor and aging medium in steam-laden aging medium is 0.2-0.9, preferably 0.40-0.60.Institute Stating regenerated flue gas can come from regenerating unit of the invention, can be from other regenerating units.

According to the 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, the item of methanol and light gasoline fraction molar ratio 1-2 Etherification reaction occurs under part, etherification product is sent into rectifying column separation, obtains etherificate oil in tower bottom, unreacted lighter hydrocarbons and methanol follow Ring utilizes.Etherification procedure reaction temperature preferably is 55-60 DEG C of inlet temperature, and outlet temperature is preferably less than 90 DEG C, air speed 1-2h^-1, the molar ratio of methanol and light gasoline fraction active olefin (isomeric olefine, such as iso-amylene) 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.

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

As shown in Figure 1, the gasoline stocks 1 of high alkene high-sulfur, which are introduced into fractionating column 2, carries out cutting fractionation, it is fractionated as light vapour The cut point of oil distillate 10 and heavy naphtha 3, light gasoline fraction and heavy naphtha is about 65~70 DEG C.Light gasoline fraction into Enter pretreatment unit 11 after the pretreatment such as removal of mercaptans, obtains light petrol 12 before being etherified, be mixed into ether-based device with methanol 13 14 reactions, etherification product 15 are fractionated the fractionation of tower 16 and obtain etherificate oil 18 and containing methanol-fueled exhaust 17.Heavy naphtha 3 and hydrogen 4 After mixing enter fluidizing reactor 5, contact with absorbing desulfurization catalyst and alkene aromatized catalyst carry out adsorb desulfurization and Aromatization, desulfurization and aromatization products 6 enter high-pressure separator 7, obtain heavy petrol product 9 and tail gas 8.Heavy petrol product 9 mix in mixer 19 with the etherificate oil 18 after etherification process, obtain clean gasoline with high octane product 20.

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

Embodiment I-II

The full fraction of gasoline stocks used in embodiment I and embodiment II is stable gasoline A and B, and property is listed in table 1.

Stable gasoline A and B are distilled in fractionating column respectively, are cut into light fraction and heavy distillat, controls light fraction The end point of distillation is 65-70 DEG C (being carried out according to ASTM D86 standard).Wherein, the light gasoline fraction that stable gasoline A distills is denoted as LCN-A, heavy naphtha are denoted as HCN-A, and the light gasoline fraction that stable gasoline B distills is denoted as LCN-B, heavy naphtha note Property for HCN-B, stable gasoline A and the B light gasoline fraction and heavy naphtha distilled is listed in table 2.Light gasoline fraction Desulfurization, dialkene removal pretreatment are carried out under hydro condition through finishing reactor, makes sulfur content and alkadienes in light gasoline fraction Content is down to 10ppm hereinafter, being then mixed into methyltertiarvbutyl ether reactor with methanol carries out etherification reaction, and etherification reaction condition is anti- 55-80 DEG C of temperature is answered, air speed 1.2h^-1, methanol and light gasoline fraction active olefin (isomeric olefine) molar ratio 1.2, reaction obtains Etherificate after oil gas enter etherificate fractionating column separation, top gaseous phase is to include residual carbon five and methanol containing methanol-fueled exhaust, tower bottom Etherificate oil is obtained, the tower top temperature for being etherified fractionating column is 60-80 DEG C, and column bottom temperature is 110-140 DEG C.Corresponding etherificate oil is denoted as LCN-A-M and LCN-B-M, property are equally listed in table 2.

Absorbing desulfurization catalyst used in following example and comparative example is by Sinopec Group Catalyst branch production, 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 3.

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 RIPP 134-90 measure, remaining composition measuring method phase Seemingly.

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 1A

The fresh aromatized catalyst that the trade mark is OTAZ-C-3 is packed into dense-phase fluidized bed reactor, in aging temperature 780 DEG C, continuous ageing 8 hours under 100% water vapor conditions, obtain the OTAZ-C-3 catalyst of aging, micro-activity 35.

The heavy naphtha for HCN-A will be numbered in small-sized continuous fluidized bed reactor and including absorbing desulfurization catalyst The mixed catalyst of FCAS and the aromatized catalyst OTAZ-C-3 of above-mentioned aging (OTAZ-C-3 account for total catalyst weight 7%) Contact 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 heavy naphtha is 6 hours^-1, the volume ratio of hydrogen and heavy naphtha is 75.It is obtained by reactor head Desulfurization and aromatization products are cooled and separated to obtain tail gas and heavy petrol product (is denoted as HCN-A heavy petrol product, similarly hereinafter, property It is shown in Table 4).The regeneration temperature of mixed catalyst is 550 DEG C, is recycled in the mixed catalyst Returning reactor after regeneration.

Embodiment 1B

It is essentially identical with embodiment 1A operation, the difference is that, aromatized catalyst includes the fresh aromatisation of mixing Catalyst and aging aromatized catalyst, the two weight ratio are 5:95.HCN-B heavy petrol product characteristics are listed in table 4.

Comparative example 1

It is essentially identical with the operation of embodiment 1, the difference is that being replaced using the aromatized catalyst without aging same Etc. weight aging aromatized catalyst, HCN-A heavy petrol product characteristics are listed in table 4.

Comparative example 2

It is essentially identical with the operation of embodiment 1, the difference is that all being inhaled using absorbing desulfurization catalyst FCAS Attached desulphurization reaction, HCN-A heavy petrol product characteristics are listed in table 4.

It can be seen from Table 4 that embodiment 1A is suitable with the desulfuration efficiency of comparative example 1 and comparative example 2, and embodiment 1A Anti-knock index 1.8 units of loss fewer than comparative example 2,1.3 units of loss fewer than comparative example 1.

Embodiment 2A

It is essentially identical with the operation of embodiment 1, it is numbered at for the heavy naphtha of HCN-B the difference is that using Reason, operating condition are as follows: reaction temperature is 400 DEG C, reactor pressure 1.8MPa, and the weight (hourly) space velocity (WHSV) of gasoline stocks is 8 hours^-1, The volume ratio of hydrogen and gasoline stocks is 60.HCN-B heavy petrol product characteristics are listed in table 5.

Embodiment 2B

It is essentially identical with embodiment 2A operation, the difference is that, aromatized catalyst includes the fresh aromatisation of mixing Catalyst and aging aromatized catalyst, the two weight ratio are 5:95.HCN-B heavy petrol product characteristics are listed in table 5.

Comparative example 3

It is essentially identical with the operation of embodiment 2, the difference is that being replaced using the aromatized catalyst without aging same Etc. weight aging aromatized catalyst, HCN-B heavy petrol product characteristics are listed in table 5.

Comparative example 4

It is essentially identical with the operation of embodiment 2, the difference is that all being inhaled using absorbing desulfurization catalyst FCAS Attached desulphurization reaction, HCN-B heavy petrol product characteristics are listed in table 5.

It can be seen from Table 5 that embodiment 2A is suitable with the desulfuration efficiency of comparative example 3 and comparative example 4, and embodiment 2A Anti-knock index 1.6 units of loss fewer than comparative example 4,1.3 units of loss fewer than comparative example 3.

Embodiment 3

Heavy petrol product and etherificate oil LCN-A-M that embodiment 1A is obtained are mixed to get clean gasoline with high octane to produce Product, property are listed in table 6.

Comparative example 5

Heavy petrol product and etherificate oil LCN-A-M that comparative example 2 obtains are mixed to get gasoline products, property is listed in table 6.

It can be seen from Table 6 that embodiment 3 is suitable with the sulfur content of comparative example 5, and the anti-knock index of embodiment 3 compares Ratio 5 increases about 4 units.

Embodiment 4

Heavy petrol product and etherificate oil LCN-B-M that embodiment 2 obtains are mixed to get clean gasoline with high octane product, Property is listed in table 6.

Comparative example 6

Heavy petrol product and etherificate oil LCN-B-M that comparative example 4 obtains are mixed to get gasoline products, property is listed in table 6.

It can be seen from Table 6 that embodiment 4 is suitable with the sulfur content of comparative example 6, and the anti-knock index of embodiment 4 compares Ratio 6 increases about 2 units.

Table 1

Table 2

Table 3

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 4

Table 5

Table 6

Claims

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

Gasoline stocks are cut, light gasoline fraction and heavy naphtha are obtained；

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

Gained heavy naphtha is sent into fluidizing reactor and is contacted with mixed catalyst and carries out desulfurization under hydro condition And aromatization, obtain heavy petrol product；

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

The preparation step of the alkene aromatized catalyst includes: that fresh aromatized catalyst is carried out aging process；The alkene The micro-activity of hydrocarbon aromatizing catalyst is 20-55, and the micro-activity is urged using RIPP 92-90 catalytic cracking industry balance The mat activity test method of agent is measured.

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

3. the condition of the aging process includes: that temperature is 500-800 DEG C according to the method described in claim 1, wherein, when Between be 1-360 hours, aging atmosphere includes steam atmosphere.

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

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

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

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

8. 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.

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

10. 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.

11. according to the method described in claim 10, 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 %.

12. 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.

13. according to the method for claim 12, 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.

14. 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 %.

15. 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 heavy naphtha volume ratio are 1- 500。

16. according to the method described in claim 1, the method also includes: after the light gasoline fraction is pre-processed again Carry out the etherification process, wherein the pretreatment is at caustic extraction processing, mercaptan conversion processing and selective hydrogenation At least one of reason.