CN107974288B

CN107974288B - A kind of vapour oil treatment process

Info

Publication number: CN107974288B
Application number: CN201610921938.6A
Authority: CN
Inventors: 王新; 欧阳颖; 许友好; 于敬川
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: CN107974288A

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；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 discloses 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 invented 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, stating 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 %；The passivation includes selected from least one of carbon, sulphur and nitrogen element；In terms of butt and with On the basis of the total weight of the alkene aromatized catalyst, the alkene aromatized catalyst includes the natural of 15-60 weight % Phosphorous and carried metal the MFI structure of minerals, the inorganic oxide binder of 10-30 weight % and 20-80 weight % point Son sieve.

Preferably, the method also includes: by gained etherificate oil and heavy petrol product 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, 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, the n (SiO of the molecular sieve₂)/n(Al₂O₃) it is greater than 100；With P₂O₅It counts and with the dry weight of molecular sieve On the basis of, the phosphorus content of the molecular sieve is 0.1-5 weight %；In terms of the oxide of carried metal and with the dry basis of molecular sieve On the basis of amount, the carried metal content of the molecular sieve is 0.5-5 weight %；The Al distribution parameter D (Al) of the molecular sieve is full Foot: 0.6≤D (Al)≤0.85, wherein D (Al)=Al (S)/Al (C), Al (S) indicate point using the measurement of TEM-EDS method The inside H in crystal face edge of son sieve crystal grain indicates to use apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) The outside H of geometric center of crystal face described in the zeolite crystal of TEM-EDS method measurement is arbitrarily greater than 100 square nanometers areas apart from interior The aluminium content in domain, wherein the H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The molecular sieve Carried metal distribution parameter D (M) meets: 2≤D (M)≤10, wherein D (M)=M (S)/M (C), M (S) indicate to use TEM-EDS The inside H in crystal face edge of the zeolite crystal of method measurement contains apart from interior any carried metal greater than 100 square nanometers regions Amount, M (C) indicate the outside H of geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method apart from interior arbitrarily large Carried metal content in 100 square nanometers regions；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 40-80 The ratio of body %, the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers are greater than 90 body %；The molecular sieve it is strong The ratio that sour amount accounts for total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 15-80.

Preferably, the carried metal is zinc and/or gallium, and the natural mineral matter includes being selected from kaolin, more water kaolinites At least one of soil, montmorillonite, diatomite, convex-concave stick stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite, institute Stating inorganic oxide binder includes at least one in silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina Kind.

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 yield 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 makes alkene aromatized catalyst containing passivation by Passivation Treatment Activity it is 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；By weight and with institute On the basis of the weight for stating alkene aromatized catalyst, passivation content is 0.1-5.0 weight in the alkene aromatized catalyst Measure %, preferably 0.3-2.0 weight %, further preferably 0.3-1 weight %；The passivation includes being selected from carbon, sulphur and nitrogen At least one of element；It is counted by butt and on the basis of the total weight of the alkene aromatized catalyst, the alkene aromatization Changing catalyst includes the natural mineral matter of 15-60 weight %, the inorganic oxide binder of 10-30 weight % and 20-80 weight Measure the MFI structure molecular sieve of the phosphorous and carried metal of %；Preferably include natural mineral matter, the 12-28 weight of 20-55 weight % Measure the MFI structure molecular sieve of the inorganic oxide binder of % and the phosphorous and carried metal of 35-70 weight %.

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, the n (SiO of molecular sieve described in the alkene aromatized catalyst₂)/n(Al₂O₃) it is greater than 100；With P₂O₅Count and with On the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-5 weight %；In terms of the oxide of carried metal simultaneously On the basis of the dry weight of molecular sieve, the carried metal content of the molecular sieve is 0.5-5 weight %；The Al of the molecular sieve Distribution parameter D (Al) meets: 0.6≤D (Al)≤0.85, wherein D (Al)=Al (S)/Al (C), Al (S) indicate to use TEM- The inside H in crystal face edge of the zeolite crystal of EDS method measurement apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) indicates that the outside H of geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method is arbitrarily greater than apart from interior The aluminium content in 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center distance 10%；The carried metal distribution parameter D (M) of the molecular sieve meets: 2≤D (M)≤10, wherein D (M)=M (S)/M (C), M (S) it indicates arbitrarily to receive greater than 100 squares using the inside H in crystal face edge of the zeolite crystal of TEM-EDS method measurement apart from interior The carried metal content in rice region, M (C) are indicated in the geometry of crystal face described in the zeolite crystal using the measurement of TEM-EDS method The outside H of the heart is apart from interior any carried metal content for being greater than 100 square nanometers regions；The total hole mesopore volume Zhan of the molecular sieve The ratio of volume is 40-80 body %, and the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers is greater than 90 Body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 15-80. Preferably, the n (SiO of the molecular sieve₂)/n(Al₂O₃) it is greater than 120；With P₂O₅Count and on the basis of the dry weight of molecular sieve, The phosphorus content of the molecular sieve is 0.2-4 weight %；It is counted using the oxide of carried metal and using the dry weight of molecular sieve as base Standard, the carried metal content of the molecular sieve are 0.5-3 weight %；The Al distribution parameter D (Al) of the molecular sieve meets: 0.65 ≤D(Al)≤0.8；The carried metal distribution parameter D (M) of the molecular sieve meets: 3≤D (M)≤6；The mesoporous of the molecular sieve The ratio that volume accounts for total pore volume is 50-70 body %, the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers Example is greater than 92 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 65-75%, the ratio between B acid acid amount and L acid acid amount For 20-50.

According to the present invention, the carried metal refers to the metal loaded on molecular sieve by mode of loading, does not include aluminium And the alkali metal such as sodium, potassium, it can be zinc and/or gallium, also may include other metals, the present invention is simultaneously not limited.

It according to the present invention, is this field skill using the aluminium content and carried metal content of TEM-EDS method measurement molecular sieve Known to art personnel, wherein the geometric center be also it is well-known to those skilled in the art, can be calculated according to formula It arrives, the present invention repeats no more, and the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line, for example, conventional six sides In the point of intersection of three opposed apexes lines, the crystal face is the geometric center of the hexagon crystal face of piece shape ZSM-5 molecular sieve One face of regular crystal grain, the direction inwardly or outwardly refer both to the direction inwardly or outwardly on the crystal face.

According to the present invention, the mesopore volume of the molecular sieve accounts for the ratio of total pore volume using N2 adsorption BET specific surface area Method measures, and the mesopore volume is that aperture is greater than 2 nanometers of pore volumes less than 100 nanometers；The strong acid of the molecular sieve Acid amount accounts for the ratio of total acid content using NH₃- TPD method measures, and the acid site of the strong acid is NH₃Desorption temperature is greater than 300 Acid site corresponding to DEG C；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.

According to the present invention, natural mineral matter refers under the comprehensive function of the various substances of the earth's crust and (claims geologic process) formation Natural simple substance or compound, and distinctive chemical component and relatively-stationary chemical component with chemical formula expression, such as can To include selected from kaolin, halloysite, montmorillonite, diatomite, convex-concave stick stone, sepiolite, galapectite, hydrotalcite, swelling At least one of soil and rectorite, inorganic oxide binder, which refers to, to be played the role of bonding the inorganic of each component in the catalyst Oxide, such as may include selected from least one of silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina.

A kind of specific embodiment of the preparation method of alkene aromatized catalyst of the present invention: by alkene aromatisation Catalyst prepare raw material and water is mixed with beating and is spray-dried；Wherein, the dry of raw material is prepared by weight and with described It is described to prepare the inorganic oxide that raw material includes the natural mineral matter of 15-60 weight %, 10-30 weight % on the basis of base weight amount The MFI structure molecular sieve of the phosphorous and carried metal of the presoma and 20-80 weight % of binder.

According to the present invention, the preparation step of the MFI structure molecular sieve of the phosphorous and carried metal may include: a, will be brilliant After MFI structure molecular sieve pulp obtained by changing is filtered and washed, washing molecular sieve is obtained；Wherein, in terms of sodium oxide molybdena and with water It washes on the basis of total dry weight of molecular sieve, the sodium content of the washing molecular sieve is less than 3 weight %；B, by gained in step a Washing molecular sieve carries out desiliconization processing in aqueous slkali, and after being filtered and washed, obtains desiliconization molecular sieve；C, by step b Middle gained desiliconization molecular sieve carries out ammonium exchange processing, obtains ammonium exchange molecular sieve；Wherein, molecule is exchanged in terms of sodium oxide molybdena and with ammonium On the basis of total dry weight of sieve, the sodium content of the ammonium exchange molecular sieve is less than 0.2 weight %；D, by gained ammonium in step c Exchange molecular sieve carries out dealumination treatment in the Compound-acid dealuminzation agent solution being made of fluosilicic acid, organic acid and inorganic acid, goes forward side by side After row filtering and washing, dealuminzation molecular sieve is obtained；E, dealuminzation molecular sieve obtained in step d is subjected to P Modification processing and load After the load processing of metal, modified molecular screen is obtained；F, gained modified molecular screen in step e is subjected to hydrothermal calcine processing, obtained To described phosphorous and carried metal MFI structure molecular sieve.

According to the present invention, MFI structure molecular sieve pulp obtained by crystallization is well-known to those skilled in the art, and the present invention is not It repeats again, wherein MFI structure molecular sieve is also well-known to those skilled in the art, be can be obtained by no amine crystallization, can also be with It is the molecular sieve prepared by template agent method, wherein being not required to roast without the resulting molecular sieve of amine crystallization, by point of template agent method preparation Son sieve roasts in air after need to drying, and the silica alumina ratio of ZSM-5 molecular sieve is generally less than 100.

According to the present invention, it is well-known to those skilled in the art for being handled using aqueous slkali progress desiliconization, described in step b Aqueous slkali can be for selected from sodium hydroxide solution and/or potassium hydroxide solution, preferably sodium hydroxide solution, the desiliconization processing Condition may include: the weight ratio of alkali in molecular sieve and aqueous slkali with dry basis be 1:(0.1-1), preferably 1: (0.15-0.4)；The temperature of desiliconization processing is room temperature to 100 DEG C, preferably 50-85 DEG C, and the time is -8 hours 15 minutes, preferably It is -4 hours 30 minutes.

According to the present invention, ammonium exchange processing is well-known to those skilled in the art, for example, can will be at alkali in step c Desiliconization molecular sieve after reason is according to molecular sieve: ammonium salt: H₂O=1:(0.1-1): the weight ratio of (5-10) is in room temperature at 100 DEG C Exchange is filtered after 0.5-2 hours, makes the Na on zeolite₂O content % heavy less than 0.2.The ammonium salt can be common inorganic Ammonium salt, for example, selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate.

According to the present invention, organic acid described in step d and inorganic acid are well known to the skilled person, for example, institute Stating organic acid can be for selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably grass Acid；Inorganic acid can be for selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid.

According to the present invention, dealumination treatment described in step d is well-known to those skilled in the art, but is not reported nothing Machine acid, organic acid and fluosilicic acid are used for dealumination treatment together.The dealumination treatment can be primary or be performed in multiple times, can first by Organic acid exchanges molecular sieve mixing with the ammonium, then fluosilicic acid and inorganic acid are exchanged to molecular sieve mixing with the ammonium Think and first organic acid is added in ammonium exchange molecular sieve, then cocurrent is added at a slow speed by fluosilicic acid and inorganic acid, or fluorine is first added Silicic acid adds inorganic acid, and preferably cocurrent is added at a slow speed for fluosilicic acid and inorganic acid.The condition of the dealumination treatment can be with are as follows: with The molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.02-0.5): (0.05-0.5): (0.05-0.5), preferably 1:(0.05-0.3): (0.1-0.3): (0.1-0.3)；Treatment temperature is 25-100 DEG C, handles the time It is 0.5-6 hours.

According to the present invention, P Modification processing and the load of carried metal processing are well-known to those skilled in the art, steps P Modification processing may include: by least one in phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate described in rapid e Kind phosphorus-containing compound carries out dipping and/or ion exchange to molecular sieve；The load processing of carried metal described in step e can wrap It includes: will be dissolved in deionized water containing the soluble-salt selected from least one of zinc and gallium carried metal, adjust pH with ammonium hydroxide Value is precipitated out carried metal in the form of hydroxide, is then uniformly mixed gained sediment with molecular sieve.

According to the present invention, the hydrothermal calcine processing of molecular sieve is well-known to those skilled in the art, water described in step f Thermal bake-out treatment conditions can be with are as follows: the atmosphere of calcination process is steam atmosphere；Maturing temperature is 400-800 DEG C, calcining time It is 0.5-8 hours.

Heretofore described washing be it is well-known to those skilled in the art, mode can be with are as follows: by 5-10 times 30-60 DEG C Water molecular sieve after filtering is eluted.

According to the present invention, the presoma of the inorganic oxide binder refers to for generating in catalytic cracking catalyst The catalytic cracking catalyst of inorganic oxide binder prepares raw material, such as may include selected from silica solution, Aluminum sol, peptization At least one of boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.

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, 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, be closed with removing vulcanization The impurity such as object and alkadienes, to extend the service life of catalyst for etherification.The method can also include: by the light gasoline fraction into The etherification process is carried out again after row pretreatment, wherein the pretreatment can be at caustic extraction processing, mercaptan conversion At least one of reason and selective hydrogenation processing.Caustic extraction processing is extracted the mercaptan of light gasoline fraction to alkali using lye It is removed in liquid；Mercaptan conversion processing converts other sulfide for small molecule mercaptan and removes, can be using conventional alkali-free The modes such as deodorizing technology, pre-add hydrogen carry out, the catalyst that used catalyst and co-catalyst all can be commonly used in the art.Selection Property hydrotreating be it is well-known to those skilled in the art, for removing alkadienes in gasoline, and can be by 3-methyl-1-butene It is isomerized to 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 are first sent 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.

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

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

Phosphorus content of the invention is measured using GB/T 30905-2014 standard method, and the content of carried metal uses GB/T 30905-2014 standard method is measured, and sodium content is measured using GB/T 30905-2014 standard method.

The research method of TEM-EDS measuring method of the invention referring to solid catalyst, petrochemical industry, 29 (3), 2000: 227。

The measuring method of total specific surface area, mesoporous pore volume, total pore volume, 2-20 nanometers of mesoporous pore volume of the invention It is as follows:

The AS-3 produced using Quantachrome instrument company, the measurement of AS-6 static state n2 absorption apparatus.

Instrument parameter: being placed in sample processing system for sample, is evacuated to 1.33 × 10 at 300 DEG C^-2Pa, heat-insulation pressure keeping 4h purifies sample.At -196 DEG C of liquid nitrogen temperature, test purification sample is not pressing P/P on year-on-year basis₀Under the conditions of to the adsorbance of nitrogen And desorption rate, obtain N₂Adsorption-desorption isothermal curve.Then total specific surface area is calculated using two parameter BET formula, micropore compares table Area and middle pore specific surface area take than pressing P/P₀=0.98 adsorbance below is the total pore volume of sample, utilizes BJH formula meter The pore-size distribution of hollow sections is calculated, and mesoporous pore volume (2-100 nanometers) and 2-20 nanometers of mesoporous hole are calculated using integration method Volume.

The measuring method of B acid acid amount and L acid acid amount of the invention is as follows:

The FTS3000 type Fourier infrared spectrograph produced using BIO-RAD company, the U.S..

Test condition: tabletted be placed in the pond in situ of infrared spectrometer of sample is sealed, is vacuumized at 350 DEG C To 10^-3Pa keeps 1h, the gas molecule of sample surfaces is desorbed clean, is cooled to room temperature.Pressure is imported into pond in situ is The pyridine steam of 2.67Pa is warming up to 200 DEG C, is evacuated to 10 again after balancing 30min^-3Pa keeps 30min, is cooled to room Temperature, in 1400-1700cm^-1Scanning, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions in wave-number range.Again by infrared suction Sample in receives pond moves to heat-treatment zone, is warming up to 350 DEG C, is evacuated to 10^-3Pa keeps 30min, is cooled to room temperature, records The infrared spectrum of 350 DEG C of pyridine adsorptions.Instrument automatic integration obtains B acid acid amount and L acid acid amount.

The measuring method of total acid content and strong acid acid amount of the invention is as follows:

Using II 2920 temperature programmed desorption instrument of Merck & Co., Inc, U.S. Autochem.

Test condition: weighing 0.2g sample to be tested and be packed into sample cell, is placed in conductance cell heating furnace, and He gas is carrier gas (50mL/ Min), 600 DEG C are warming up to the rate of 20 DEG C/min, purging 60min drives away the impurity of catalyst surface absorption.Then it is cooled to 100 DEG C, constant temperature 30min switches to NH₃- He gaseous mixture (10.02%NH₃+ 89.98%He) absorption 30min, it is further continued for He gas It is steady to baseline to purge 90min, the ammonia of physical absorption is desorbed.600 DEG C are warming up to 10 DEG C/min heating rate to be taken off It is attached, 30min is kept, desorption terminates.Using TCD detector detection gas change of component, instrument automatic integration obtain total acid content and Strong acid acid amount, the acid site of strong acid are NH₃Desorption temperature be greater than 300 DEG C corresponding to acid site.

The calculation method of D value is as follows: choosing a crystal grain in transmission electron microscope and some crystal face of the crystal grain is formed One polygon, there are 10% distance H of geometric center, edge and geometric center to edge point is (different for the polygon Edge point, H value are different), choose respectively any one piece in the inside H distance in the crystal face edge be greater than 100 square nanometers regions with And any one piece in the outside H distance of crystal face geometric center is greater than 100 square nanometers regions, measures aluminium content, as Al (S1) With Al (C1), and D (Al) 1=Al (S1)/Al (C1) is calculated, choose different crystal grain respectively and measure 5 times, calculating average value is The measuring method of D (Al), D (M) are similar with the measuring method of D (Al).

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

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 property are listed in table 3.The preparation method of aromatized catalyst is as follows:

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

By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO₂)/n(Al₂O₃) =27) mother liquor is filtered out, Na is washed to₂O content is lower than 3.0 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) It is added in the NaOH solution of 1000g 2.0%, is warming up to 65 DEG C, after reacting 30min, after being rapidly cooled to room temperature, filter, washing To filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, after exchange handles 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare At the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g is added in stirring, then by 110g hydrochloric acid (mass fraction 10%) and 92g fluosilicic acid (mass fraction 3%) cocurrent is added, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to Filtrate is neutral；By filter cake plus water be beaten solid content be 45 weight % molecular sieve pulps；By 1.2g H₃PO₄(85 weight % of concentration) With 3.3gZn (NO₃)₂·6H₂O is dissolved in 10g water, and ammonium hydroxide is added and adjusts pH=6, and it is equal that mixing in molecular sieve pulp is then added Even, drying, the lower 550 DEG C of calcination process 2h of 100% steam atmosphere.Molecular sieve-4 A is obtained, physico-chemical property is listed in table 4.

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

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/T5487-1995 and GB/T is respectively adopted in the octane number RON and MON of gasoline in the embodiment of the present invention and comparative example 503-1995 standard method is measured, anti-knock index=(MON+RON)/2, gasoline PONA using simulation distillation and it is gasoline detailed Hydrocarbon analyzes (ASTM D2887 and ASTM D6733-01 (2011) test method is respectively adopted to be tested), and content of sulfur in gasoline is adopted It is measured with 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 weight %.

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 passivation (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 5).The regeneration temperature of mixed catalyst is 550 DEG C, is recycled in the mixed catalyst Returning reactor after regeneration.

Comparative example 1

It is essentially identical with the operation of embodiment 1, the difference is that being replaced using unpassivated aromatized catalyst same Etc. weight passivation aromatized catalyst, HCN-A heavy petrol product characteristics are listed in table 5.

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 5.

It can be seen from Table 5 that embodiment 1 is suitable with the desulfuration efficiency of comparative example 1 and comparative example 2, and embodiment 1 is anti- Quick-fried index 1.8 units of loss fewer than comparative example 2,1.3 units of loss fewer than comparative example 1.

Embodiment 2

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 heavy naphtha is 8 small When^-1, the volume ratio of hydrogen and heavy naphtha is 60.HCN-B heavy petrol product characteristics are listed in table 6.

Comparative example 3

It is essentially identical with the operation of embodiment 2, the difference is that being replaced using unpassivated aromatized catalyst same Etc. weight passivation aromatized catalyst, HCN-B heavy petrol product characteristics are listed in table 6.

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 6.

It can be seen from Table 6 that embodiment 2 is suitable with the desulfuration efficiency of comparative example 3 and comparative example 4, and embodiment 2 is anti- Quick-fried 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 1 obtains are mixed to get clean gasoline with high octane product, Property is listed in table 7.

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 7.

It can be seen from Table 7 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 7.

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 7.

It can be seen from Table 7 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
		Chemical composition, weight %
Aluminium oxide	13
		Sodium oxide molybdena	/
Nickel oxide	21
		Zinc oxide	52
Gallium oxide	/
		Silica	14
Apparent density, kg/m³	1010
		Pore volume, mL/g	/
Specific surface area, m²/g	/
		Abrasion index, when weight %^-1	/
Screening composition, weight %
		0~40 micron	14.5
40~80 microns	51.9
		> 80 microns	33.6
Micro-activity	/

Table 4

Project	Molecular sieve-4 A
		Crystallinity/%	90
n(SiO₂)/n(Al₂O₃)	110
		P₂O₅Content/%	1.5
Metal oxide-loaded content/%	1.6
		S_BET/(m²/g)	440
(V_Mesoporous/V_{Total hole})/%	60
		(V_2nm-20nm/V_Mesoporous)/%	99
(strong acid acid amount/total acid content)/%	70
		The sour amount of B acid/L acid acid amount	35
D (Al distribution)	0.77
		D (M distribution)	3.6

Table 5

Table 6

Table 7

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；

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；

It is counted by butt and on the basis of the total weight of the alkene aromatized catalyst, the alkene aromatized catalyst includes The phosphorous and gold-supported of the natural mineral matter of 15-60 weight %, the inorganic oxide binder of 10-30 weight % and 20-80 weight % The MFI structure molecular sieve of category；The micro-activity of the alkene aromatized catalyst is 20-55, and the micro-activity uses RIPP The mat activity test method of 92-90 catalytic cracking industry equilibrium catalyst 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. 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 body % 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, the n (SiO of the molecular sieve₂)/n(Al₂O₃) it is greater than 100；With P₂O₅ It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-5 weight %；With the oxidation of carried metal Object meter and on the basis of the dry weight of molecular sieve, the carried metal content of the molecular sieve are 0.5-5 weight %；The molecule The Al distribution parameter D(Al of sieve) meet: 0.6≤D(Al)≤0.85, wherein D(Al)=Al(S)/Al(C), and Al(S) it indicates to use The inside H in crystal face edge of the zeolite crystal of TEM-EDS method measurement contains apart from interior any aluminium greater than 100 square nanometers regions Amount, Al(C) indicate the outside H of geometric center of crystal face described in the zeolite crystal measured using TEM-EDS method apart from interior any Greater than the aluminium content in 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center distance 10%；The carried metal distribution parameter D(M of the molecular sieve) meet: 2≤D(M)≤10, wherein D(M)=M(S)/M(C), M(S) It indicates arbitrarily to be greater than 100 square nanometers areas apart from interior using the inside H in crystal face edge of the zeolite crystal of TEM-EDS method measurement The carried metal content in domain, M(C) indicate using TEM-EDS method measurement zeolite crystal described in crystal face geometric center to Outer H is apart from interior any carried metal content for being greater than 100 square nanometers regions；The mesopore volume of the molecular sieve accounts for total pore volume Ratio be 40-80 body %, aperture be 2 nanometers to 20 nanometers the total mesopore volume of mesopore volume Zhan ratio be greater than 90 body %；Institute It is 60-80% that the strong acid acid amount for stating molecular sieve, which accounts for the ratio of total acid content, and the ratio between B acid acid amount and L acid acid amount are 15-80.

14. according to claim 1 or method described in 13, wherein the carried metal is zinc and/or gallium, the natural minerals Matter includes in kaolin, montmorillonite, diatomite, convex-concave stick stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite At least one, the inorganic oxide binder include be selected from silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silicon At least one of aluminium.

15. according to the method for claim 14, wherein the kaolin is halloysite.

16. 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 %.

17. 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。

18. 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.