CN106675637A

CN106675637A - Method for producing high aromatic gasoline

Info

Publication number: CN106675637A
Application number: CN201510761500.1A
Authority: CN
Inventors: 方向晨; 刘建锟; 柳伟; 杨涛; 郭蓉; 蒋立敬; 曾榕辉; 黄新露
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2015-11-11
Filing date: 2015-11-11
Publication date: 2017-05-17
Anticipated expiration: 2035-11-11
Also published as: CN106675637B

Abstract

The invention discloses a method for producing high aromatic gasoline. The method comprises the following steps: arranging two reaction areas in a reactor, including a fluidized bed reaction area and at least one micro-expanded bed reaction area; arranging the micro-expanded bed reaction area on the lower part in the reactor, arranging the fluidized bed reaction area on the upper part in the reactor and separating the micro-expanded bed reaction area from the fluidized bed reaction area through a distributing plate; mixing raw oil with hydrogen, causing the mixture to enter into the micro-expanded bed reaction area from the bottom of the reactor and contact with a catalyst bed layer of a micro-expanded bed and performing hydrofining reaction; upward flowing and contacting with a catalyst in the fluidized bed reaction area for hydrocracking reaction; discharging the generated oil from the top of the reactor; and acquiring the high aromatic gasoline after completing the processes of fractionation, absorption and stabilization. According to the method disclosed by the invention, the micro-expanded bed is combined with the fluidized bed, the reactor is simple in structure and high in space utilization, the process operation is stable and the flexibility is high.

Description

A kind of method for producing high aromatic-hydrocarbon gasoline

Technical field

The present invention relates to a kind of method for producing high aromatic-hydrocarbon gasoline.

Background technology

Catalytic cracking（FCC）Technology is one of main technological means of heavy oil lighting, is all occupied an important position in the oil refining enterprise of countries in the world.Current China's catalytic cracking unit year, total working ability alreadyd exceed 1.7 hundred million tons, and catalytic diesel oil annual production has reached 35,000,000 tons.In China's petrol and diesel oil product is constituted, catalytically cracked gasoline accounts for 80% of product gasoline or so, and catalytic diesel oil accounts for 30% of diesel product or so.In recent years, on the one hand as crude quality is deteriorated, the raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, the operating severity for causing catalytic cracking unit is improved, the reduction of catalytic diesel oil quality；On the other hand, it is to reduce content of olefin in gasoline producing more propylene simultaneously, many catalytic units select MIP, MIP-CGP or FDFCC technology, but these technologies make the further in poor quality of catalytic diesel oil quality while producing more propylene and effectively reduction gasoline olefin.

Although the property of different enterprises' catalytic diesel oils difference, all has common feature, i.e. density big（>0.94g/cm³）, Cetane number it is low（<20）It is high with arene content（>75%）, catalytic diesel oil become restriction efficiently, low consumption realize the main bottleneck that diesel quality is upgraded.Therefore, the processing route for finding an efficient, low consumption and economy for catalytic diesel oil quality upgrading as early as possible, is the technical problem of current urgent need to resolve.

In order to reduce the density of catalytic diesel oil, improve Cetane number, the de- virtue technology of hydrofinishing deep desulfuration, maximum are emerged successively and improves diesel cetane-number MCI technologies, poor ignition quality fuel Mhug Technology（MHUG）The refining technology such as catalytic diesel oil technology is mixed with high-pressure hydrocracking, these technologies commercial Application, and catalytic diesel oil density is can obviously reduce, improve Cetane number.Although after refined or modification, sulfur content can be greatly lowered catalytic diesel oil, and Cetane lndex can be improved, and Cetane number is still less than 21.5；Extremely under harsh conditions, Cetane number is also slightly larger than 21.5, and Cetane number and density still have relatively large distance from the index of derv fuel；As can be seen here, it is also economically very irrational even simply producing ordinary diesel oil with high density, low-cetane catalytic diesel oil under current petrol and diesel oil pricing system.

CN200810228348.0 discloses a kind of method for hydrogen cracking for producing high-knock rating gasoline.Feedstock oil carries out removing impurities qualitative response after mixing with hydrogen into first reactor；Reaction effluent carries out hydrocracking reaction into second reactor；It is hydrocracked using suitable catalyst, and operates under certain nitrogen content.The method has the features such as can processing raw material more inferior, catalyst runs cycle length and good hydrocracked product quality, for various high arene content diesel oil distillates as raw material, producing the hydrocracking process process of high-knock rating gasoline.But there are problems that catalyst inactivation is fast, poor to adaptability to raw material, temperature rise cannot be solved.

CN200910162161.X discloses a kind of method for producing high-knock rating gasoline by poor ignition quality fuel, diesel raw material oil-hydrogen mixture successively with the Hydrobon catalyst and the hydrocracking catalyst haptoreaction of second reaction zone of the first reaction zone, control the aromatic hydrocarbons saturation depth of the first reaction zone, i.e. with diesel raw material oil phase ratio, the saturation factor of bicyclic and bicyclic above aromatic hydrocarbons is more than 50% in the reaction effluent of the first described reaction zone, and on the basis of the liquid component of the reaction effluent of the first reaction zone, its mononuclear aromatics content increases to more than 40 mass %.The method adopts one-pass technological process, and moderate control reaction depth can be by the poor-quality diesel-oil by cut fraction of high arene content production low-sulfur, high-knock rating gasoline, while the cleaning diesel oil blending component of low-sulfur can also be produced.But the method two reaction zones catalyst can not be inactivated synchronously, i.e. the catalyst inactivation of two reaction zones can not be matched well with the aromatic hydrocarbons saturation factor for designing, also cannot solve temperature rise it is big the problems such as.

CN02109674.0 discloses a kind of Cascade boiling bed residual oil method of hydrotreating and equipment, and residual hydrogenation reaction is carried out using various functions catalyst combination in one more than two sections of tandem fluidized bed reactor, can effectively improve bottoms conversion and product quality.Tandem fluidized bed reactor has multiple conversion zones with the addition of independent catalyst and outlet, per section of three phase separation part for being provided with the feed distributing plate with float valve structure and being made up of air guide, baffle component, gas-liquid division board and demister, material can effectively carry out three-phase fluidization reaction and three phase separation in reactor, and can carry out catalyst and replace online.Although can realize using two or more type catalyst in the reactor, but need to use baroque inner member, increased equipment investment, be unfavorable for the stable operation of fluidized bed reactor, in reactor space availability ratio reduce, and cannot solve temperature rise it is big the problems such as.

CN200910012497.8 discloses a kind of method of boiling-bed catalyst, and at least two catalyst are used in fluidized bed reactor, and under ebullated bed operating condition, the particle size along reaction mass flowing direction catalyst is sequentially reduced.The present invention overcomes prior art needs using multiple fluidized bed reactors or the complicated inner member of setting could realize the scheme of different catalysts in fluidized bed reactor.The inventive method flow process is simple, structure of reactor simple, space reactor utilization rate is high, and technological operation is steady, flexibility is high, can be used for various boiling bed hydrogenation processing procedures.But this invention is suitable for the process that course of reaction is suitable for ebullated bed system, and course of reaction is difficult to precise controlling, and cannot solve temperature rise it is big the problems such as.

The content of the invention

For the deficiencies in the prior art, the present invention provides a kind of method for producing high aromatic-hydrocarbon gasoline, the inventive method is in the form of slight expanded-bed is combined with ebullated bed, structure of reactor is simple, space availability ratio is high, technological operation is steady, flexibility is high, the production process of high aromatic-hydrocarbon gasoline is capable of achieving in same reactor, while the inventive method effectively can be allocated to temperature rise, solves the problems, such as that conventional reactor cannot realize that reaction temperature rising is big.

The method of the production high aromatic-hydrocarbon gasoline of the present invention, including following content：Two reaction zones, including an ebullating bed reactor area, and at least one slight expanded-bed reaction zone are set in reactor；Slight expanded-bed reaction zone is arranged on bottom in reactor, and ebullating bed reactor area is arranged on reactor internal upper part, and slight expanded-bed reaction zone can be separated with ebullating bed reactor area by distribution grid；Ebullating bed reactor area volume accounts for the 20% ~ 80% of reactor volume, preferably 30% ~ 70%, and remaining part is slight expanded-bed reaction zone；Catalyst inventory is the 10% ~ 80% of reaction zone volume, preferably 50% ~ 60% in ebullating bed reactor area；

Microdilatancy reaction zone is entered after feedstock oil and hydrogen mixing from reactor bottom, contact with slight expanded-bed beds, carry out hydrofining reaction, then proceed to flow up contact with the catalyst in ebullating bed reactor area and carry out hydrocracking reaction, generate oil to discharge from reactor head, through fractionation, Vapor recovery unit process the gasoline of the higher high arene content of liquid yield can be obtained.

In the inventive method, described microdilatancy reaction zone can be single microdilatancy reaction zone, it is also possible to the tandem compound of multiple microdilatancy reaction zones, can also be that multi-catalyst system level is matched somebody with somebody in independent microdilatancy reaction zone.

In the inventive method, described feedstock oil can be the oil product rich in high aromatic hydrocarbons inferior such as catalytic diesel oil inferior, coker gas oil, and the unconventional oil product such as various coal tar, wood tar, cracked oil, ethylene bottom oil etc., can also be the above-mentioned raw materials mixture of two or more, the arene content of feedstock oil is more than 40%.

In the inventive method, the feedstock oil is contacted with the Hydrobon catalyst of microdilatancy reaction zone, carries out hydrofinishing desulfurization, denitrogenation, polycyclic aromatic hydrocarbon appropriateness saturation and part ring-opening reaction, and most of impurity is removed；Hydrobon catalyst is typically chosen that activity is low, resistance to dirt holds that dirty performance is strong, slow down pressure drop and increase that function is strong, the catalyst that pore volume is big, surface area is big and particle size is big, it is ensured that the alkane and mononuclear aromatics in feedstock oil does not occur supersaturation.

In the inventive method, microdilatancy reaction zone can be so that by the way of either shallow Hydrobon catalyst and deep hydrofinishing catalyst grading loading, the either shallow Hydrobon catalyst of microdilatancy reaction zone and the volume loadings of deep hydrofinishing catalyst be 1:9～9:1, preferably 3:7～7:3.Ratio that can be to pass through online displacement apparatus adjustment catalyst according to the change of raw material in operation process and product.

Either shallow Hydrobon catalyst generally comprises hydrogenation active metals and carrier, hydrogenation active metals are selected generally from one or more in group vib and VIII, usually one or more in W, Mo, Ni and Co, active metallic content in terms of oxide weight generally 0.1% ~ 15% in catalyst.Carrier is generally inorganic refractory oxide, such as aluminum oxide, amorphous silicon aluminium, silica, titanium oxide.The pore volume 0.1-1.5ml/g of catalyst, preferred 0.3-0.6ml/g, specific surface area 100-500m²/ g, preferred 260-320m²/g.Hydrobon catalyst can be prepared according to prior art; FBN series Bird's Nest hydrogenation protecting agent, FZC-10 series, FZC-100 series that the GSK series and ICR122 series and Fushun Petrochemical Research Institute that the KF series and KG series, CHEVRON companies that the business Hydrobon catalyst that can also be used, such as Uop Inc. are developed is developed is developed.

The carrier that deep hydrofinishing catalyst is used is inorganic refractory oxide, such as aluminum oxide, amorphous silicon aluminium, silica, titanium oxide.Business Hydrobon catalyst mainly has：HC-K, HC-T, HC-P that Uop Inc. develops, and Fushun Petrochemical Research Institute develop 3936,3996, FF-16, FF-26, FF-36 etc..Common auxiliary agent, such as one or more in K, P, Mg, Zr and Ca can be contained in catalyst.

The reaction condition that the hydrofinishing of described slight expanded-bed reaction zone is general is：Entrance 0.1 ~ 30MPa of hydrogen dividing potential drop, preferably 7 ~ 10MPa, 0.1 ~ 10h of volume space velocity^-1, preferably 0.5 ~ 1.5 h^-1, reaction temperature is 200 ~ 500 DEG C, preferably 300 ~ 350 DEG C.

In the inventive method, described microdilatancy reaction zone can also be by the way of multiple catalysts mixed packing, i.e., either shallow is hydrogenated with the granular size of deep hydrogenation catalyst, aperture, bed voidage can be consistent, it is also possible to selected according to actual needs.

In the inventive method, described microdilatancy reaction zone can also be by the way of multiple catalysts level be matched somebody with somebody.Using classification filling the granular size of bed catalyst from down to up, aperture, bed voidage can also be made ascending, activity suitable matching from low to high；Wherein granular size, aperture and bed voidage can be selected according to actual needs.

It is preferred that the Hydrobon catalyst increased using 2 ~ 10 kinds of activity along liquid phase material flow direction, is the easy to operate Hydrobon catalyst that 2 ~ 3 kinds of activity can be used to increase.Hydrobon catalyst activity is typically obtained by the content of hydrogenation active metals in adjustment catalyst, and adjacent catalyst bed hydrogenation active metals content preferably differs 3% ~ 15% with oxide percentages difference 1% ~ 50%.It is preferred that the filling order along the dynamic direction beds voidage of liquid phase stream from small to large, the voidage difference of adjacent catalyst bed is 0.05 ~ 0.35, preferably 0.1 ~ 0.2.

In the inventive method, described ebullating bed reactor area filling hydrocracking catalyst, hydrocracking catalyst is typically chosen active higher, the selective strong catalysis material that particularly chain rupture ability is relatively strong, sour amount is moderate, is high aromatic-hydrocarbon gasoline by raw material orientation cracking.Simultaneously using ebullated bed system inner height back-mixing the characteristics of, unconverted oil carries out further cracking, improves the yield of aromatic type gasoline.

The general reaction condition in described ebullating bed reactor area is：Entrance 0.1 ~ 30MPa of hydrogen dividing potential drop, preferably 7 ~ 10MPa, 0.1 ~ 10h of volume space velocity^-1, preferably 0.5 ~ 1.5 h^-1, reaction temperature is 200 ~ 500 DEG C, preferably 300 ~ 350 DEG C.

Described hydrocracking catalyst, generally comprise carrier and active metal, group VIII and/or vib metals element of the described active metal in the periodic table of elements, group VIII active metal can be Ni and/or Co, vib active metal can be W and/or Mo, group VIII active metallic content is 3% ~ 15%, and vib active metallic content is 10% ~ 40%, in terms of metal oxide；Described carrier

Typically with aluminum oxide, unformed silicon and molecular sieve etc. as carrier, the molecular sieve content in carrier is generally 5wt%～60wt%.Hydrocracking catalyst can be prepared using prior art, business hydrocracking catalyst, the ICR126 that ZHC-01, ZHC-02, ZHC-04, FC-14, FC-24, FC-28, CHEVRON company that such as Fushun Petrochemical Research Institute develops develops can also be used.

The shape of hydrocracking catalyst can be the shape such as spherical, elliposoidal, clover, bunge bedstraw herb, four impeller shapes, Raschig ring, butterfly, cellular, and catalyst particle size is 0.1 ~ 10mm.Irregular catalyst particle size refers generally to the Average equivalent diameter of particle（There is identical external surface area with spheric granules）, the pore volume 0.1-0.9 ml/g of catalyst, preferred 0.3-0.5ml/g, specific surface area 100-500m²/ g, preferred 180-260m²/g。

The inventive method preferably adopts following hydrocracking catalyst, with overall catalyst weight gauge, including：Silica-alumina supports 55% ~ 85% containing modified Y molecular sieve, active metal 15% ~ 45%, wherein active metal is in terms of metal oxide；Mass percent of the described modified Y molecular sieve in silica-alumina supports is 15% ~ 90%, preferably 30% ~ 70%, balance of amorphous silica-alumina and/or aluminum oxide；The specific surface area of the catalyst is 200 ~ 400m²/ g, pore volume is 0.2 ~ 0.5ml/g；Group VIII and/or vib metals element of the described active metal in the periodic table of elements, group VIII active metal can be Ni and/or Co, vib active metal can be W and/or Mo, group VIII active metallic content is 3% ~ 15%, vib active metallic content is 10% ~ 40%, in terms of metal oxide；The preparation method of wherein described modified Y molecular sieve, including following content：（1）Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by former powder of NaY zeolite；

（2）To step（1）In the ammonium that obtains exchange after Y molecular sieve carry out hydro-thermal process；（3）To step（2）Y molecular sieve after hydro-thermal process is processed with aluminum salt solution；（4）To step（3）The Y molecular sieve dried process of gained；（5）Step（4）The Y molecular sieve for obtaining impregnates in organic solvent, then rapid draing；（6）By step（5）The Y molecular sieve for obtaining carries out dealumination complement silicon process；（7）Step（6）Y molecular sieve Jing Jing after dealumination complement silicon process is filtered, is dried, roasting, obtains modified Y molecular sieve.

Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：It is raw material in ammonium salt aqueous solution with NaY zeolite, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, exchange times is 1 ~ 4 time, the NaY zeolite after being exchanged, Na₂O content is less than 3.0%；Wherein the SiO2/Al2O3 mol ratios of NaY zeolite raw material are 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Ammonium salt is one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0 ~ 3.0 mol/L.

Step（2）The hydrothermal treatment process is that hydrothermal conditions are in itself vapor or under conditions of being passed through vapor：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and process time is 1.0 ~ 6.0 hours.

Step（3）Aluminium salt used by described aluminium salt processing procedure can be aluminium chloride, aluminum sulfate, aluminum nitrate etc..Aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and process time is 0.5 ~ 3 hour.

Step（4）Described baking temperature is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.

Step（5）One or more of described organic solvent in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene or dimethylbenzene, using supersaturation dipping, dip time is 1 ~ 5h to impregnation method；Baking temperature is 50 ~ 300 DEG C, and higher than the boiling point of organic solvent, drying time is 1 ~ 60 minute, preferably 3 ~ 20 minutes to preferred baking temperature.

Step（6）Described in dealumination complement silicon be processed as method well known to those skilled in the art, can be using conventional ammonium fluosilicate dealumination complement silicon method, i.e., first by step（5）The Y molecular sieve for obtaining adds water and is made into the water sample mixing of liquid-solid ratio 3 ~ 6, then, adds concentration to be that 0.8 ~ 2mol/L ammonium fluosilicates aqueous solution is processed 1 ~ 4 hour in 70 ~ 100 DEG C.Other are such as SiCl₄Gas phase dealumination complement silicon is also suitable.

Step（7）Described calcination process condition is：Roasting 2 ~ 4 hours at 400 ~ 600 DEG C.

The preparation method of described hydrocracking catalyst, including：

First, modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed according to a certain ratio, add dust technology into extruded moulding after slurry, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；Wherein the concentration of dust technology is 3wt% ~ 30wt%；Described drying condition is：It is dried 1 ~ 5 hour at 80 ~ 120 DEG C；Roasting condition is：Roasting 1 ~ 5 hour at 400 ~ 700 DEG C；

2nd, the carrier of step one is impregnated using the maceration extract containing active metal, the carrier drying after dipping, roasting obtain hydrocracking catalyst；Group VIII and/or vib metals element of the wherein described active metal in the periodic table of elements, group VIII active metal can be Ni and/or Co, and vib active metal can be W and/or Mo；The liquid-solid ratio for wherein impregnating is 1.5：1~3：1, carried out by the way of saturation well known in the art dipping, the content of group vib metallic compound is calculated as 20 ~ 60g/100ml by corresponding oxide in maceration extract, the content of group VIII metallic compound is calculated as 3 ~ 20g/100ml by corresponding oxide, and the concentration of metallic compound can be adjusted accordingly according to product needed in maceration extract；Wherein described drying condition is：It is dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting condition is：Roasting 1 ~ 5 hour at 400 ~ 700 DEG C.

In the method for the present invention, the volume loadings of the hydrocracking catalyst in Hydrobon catalyst and ebullated bed in slight expanded-bed are 1:9～9:1, preferably 3:7～7:3.Ratio that can be to pass through online displacement apparatus adjustment catalyst according to the change of raw material in operation process and product.

In the method for the present invention, for voluminous gasoline, can also be by the fuel part for generating or whole cyclic process, circulation ratio can be 0-100%, preferred 30%-70%.

To ensure that differential responses region catalyst inactivation is synchronous controllable and extends the cycle of operation, sampling system and the online exchange system of catalyst are set in each conversion zone, it is ensured that catalyst activity is stable.

The present invention can realize producing high aromatic-hydrocarbon gasoline in a reactor, overcome the scheme that prior art needs to be connected using multistage reactor.The setting of multi-reaction-area, using relax progressively reacted by the way of, condensed-nuclei aromatics condensation carbon deposit in the raw material such as catalytic diesel oil can be avoided under single hop high temperature, so as to have a strong impact on the service life of catalyst.Using the setting of multi-reaction-area, make to process raw material reasonably combined with process conditions and catalyst, give full play to the activity of catalyst, it is ensured that product quality.

The inventive method flow process is simple, structure of reactor simple, space reactor utilization rate is high, and technological operation is steady, flexibility is high, can be used for producing the process of high aromatic-hydrocarbon gasoline.Flexibility is high, can carry out corresponding technique adjustment, production clean gasoline or low-carbon (LC) aromatic hydrocarbons according to product demand.Particularly ebullated bed region, the characteristics of using ebullated bed system inner height back-mixing, unconverted oil carries out further cracking, improves the yield of aromatic type gasoline, without the need for needing the mode that hydrogenation tail oil circulates as conventional hydrocracking technique.

Using the technology of the present invention, 0.92 ~ 0.95g/cm of density is processed³Catalytic diesel oil,<210 DEG C of gasoline fraction yields 30% ~ 50%, octane number（RON）91 ~ 94, sulfur content<10 μ g/g, as the gasoline blend component of state V or can be directly produced the gasoline products of state V；Compared with diesel raw material, modification diesel oil density reduces 0.07g/cm³Left and right, Cetane number（Index）Improve more than 10 units, sulfur content<10μg/g.The present invention also brings considerable economic benefit while enterprise's diesel quality scaling difficulty is preferably alleviated for enterprise.At the same time it can also improving reaction depth, it is to avoid the deficiency such as number of reactors is more, technological process is complicated, catalyst amount is big.

Description of the drawings

Fig. 1 is the schematic diagram of the method for the present invention.

Wherein：1- reactor inlets, 2- distribution grids, 3- microdilatancy reaction zones, 4- ebullating bed reactors area, 5- reactor outlets, 6- catalyst outlets, 7- catalyst adds entrance.

Specific embodiment

Below in conjunction with the drawings and specific embodiments further to being described.

Embodiment 1

Catalytic diesel oil carries out boiling bed hydrogenation process as raw material, and feedstock property is shown in Table 1, and either shallow hydrogenation catalyst A, deep hydrogenation catalyst B and hydrocracking catalyst C are loaded respectively along logistics direction from reactor bottom, the two ratio 1:1:1, the pore volume 0.30ml/g of either shallow hydrogenation catalyst A, specific surface area 200m²/ g, MoO₃The % of 19%, NiO 1.8, voidage 0.36；The pore volume 0.31ml/g of deep hydrogenation catalyst B, specific surface area 240m²/ g, MoO₃25%, NiO 4%, voidage 0.41；The pore volume 0.32ml/g of hydrocracking catalyst C, specific surface area 350m²/ g, MoO₃28%, NiO 8%, voidage 0.46.Process operation condition, temperature：405 DEG C, pressure 15MPa, volume space velocity 1.0h during total liquid^-1, hydrogen to oil volume ratio 750：1, the results are shown in Table 2.

The main character of the catalytic diesel oil of table 1.

Embodiment 2

Catalytic diesel oil carries out boiling bed hydrogenation process as raw material, and feedstock property is shown in Table 1, and either shallow hydrogenation catalyst A, deep hydrogenation catalyst B and hydrocracking catalyst D are loaded respectively along logistics direction from reactor bottom, the two ratio 1:1:1, the pore volume 0.30ml/g of either shallow hydrogenation catalyst A, specific surface area 200m²/ g, MoO₃19%, NiO 1.8%, voidage 0.36；The pore volume 0.31ml/g of deep hydrogenation catalyst B, specific surface area 240m2/g, MoO₃25%, NiO 4%, voidage 0.41；The pore volume 0.35ml/g of hydrocracking catalyst D, specific surface area 360m²/ g, MoO₃31%, NiO 10%, voidage 0.48.Process operation condition, temperature：405 DEG C, pressure 15MPa, volume space velocity 1.0h during total liquid^-1, hydrogen to oil volume ratio 750：1, the results are shown in Table 2.

Embodiment 3

Raw material carries out boiling bed hydrogenation process, reactor fill depth hydrogenation catalyst B and hydrocracking catalyst C, the two ratio 1:1, process operation condition, temperature：405 DEG C, pressure 15MPa, volume space velocity 1.0h during total liquid^-1, hydrogen to oil volume ratio 750：1, the results are shown in Table 2.

Embodiment 4

Raw material carries out boiling bed hydrogenation process, reactor filling hydrocracking catalyst C, process operation condition, temperature：405 DEG C, pressure 15MPa, volume space velocity 1.0h during total liquid^-1, hydrogen to oil volume ratio 750：1, the results are shown in Table 2.

Embodiment 5

Catalytic diesel oil carries out boiling bed hydrogenation process as raw material, and feedstock property is shown in Table 1, and either shallow hydrogenation catalyst A, deep hydrogenation catalyst B and hydrocracking catalyst Cat-1 are loaded respectively along logistics direction from reactor bottom, the two ratio 1:1:1, the pore volume 0.30ml/g of either shallow hydrogenation catalyst A, specific surface area 200m²/ g, MoO₃The % of 19%, NiO 1.8, voidage 0.36；The pore volume 0.31ml/g of deep hydrogenation catalyst B, specific surface area 240m²/ g, MoO₃25%, NiO 4%, voidage 0.41；The pore volume 0.35ml/g of hydrocracking catalyst Cat-1, specific surface area 360m2/g, MoO₃31%, NiO 11%, voidage 0.48.Process operation condition, temperature：405 DEG C, pressure 15MPa, volume space velocity 1.0h during total liquid^-1, hydrogen to oil volume ratio 750：1, the results are shown in Table 2.

The preparation method of wherein described hydrocracking catalyst is as follows：

It is prepared by modified molecular screen：

（1）The NaY molecular sieve original powder 200g of laboratory's preparation is taken, with the ammonium nitrate that concentration is 0.5mol/L according to liquid-solid ratio 3:1 mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange₂O is calculated as 2.5%；

（2）To step（1）530 DEG C of the Y molecular sieve for obtaining, hydro-thermal process 2 hours under 0.1MPa；

（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, then heats to 80 DEG C, and the aluminum sulfate solution 400ml of 0.5mol/L, isothermal reaction 2 hours are added during stirring；

（4）Step（3）150 DEG C of molecular sieve of gained is dried 8h.

（5）Take normal heptane solvent soaking step（4）The molecular sieve of gained 2 hours；

（6）Step（5）Molecular sieve after process was in 130 DEG C of dryings 8 minutes；

（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, adds the ammonium fluosilicate solution 100ml that concentration is 0.8mol/L, and 80 DEG C are processed 2 hours；

（8）Jing steps（7）After Y molecular sieve after ammonium fluosilicate process, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, modified Y molecular sieve is obtained, numbering is Y-1.

It is 45 that Y-1 molecular sieve transmission electron microscope EDAX results determine the silica alumina ratio of its outer surface to 80nm thickness, and the silica alumina ratio of molecular sieve is 11.XRD analysis result shows its lattice constant for 2.440nm, relative crystallinity 98%.Pore volume 0.36ml/g, specific surface area 750m²/ g, it is 0.95mmol/g that infrared analysis result determines Y-1 meleic acids amount.

Hydrocracking catalyst preparation process：

（1）Configuration W-Ni dipping solutions：Configuration 1000ml dipping solutions after ammonium metatungstate 430g and nickel nitrate 440g is dissolved in water are taken, active metal is with WO in gained dipping solution₃36g/100ml and 11g/100ml, solution numbers RY-1 are respectively with NiO cubages；

（2）Take Y-1 60g to mix with 40g macroporous aluminium oxides, add 4g/100ml dust technologies to mix in a mixer and roll to extrudable shape, extruded moulding obtains carrier T-1 on banded extruder；

（3）Taking T-1 60g adds 120ml RY-1 maceration extracts to impregnate 2 hours, then 120 DEG C of dryings 4 hours, 500 DEG C of roastings 3 hours, obtains hydrocracking catalyst, and numbering is Cat-1.

Embodiment 6

Catalytic diesel oil carries out boiling bed hydrogenation process as raw material, and feedstock property is shown in Table 1, and either shallow hydrogenation catalyst A, deep hydrogenation catalyst B and hydrocracking catalyst Cat-2 are loaded respectively along logistics direction from reactor bottom, the two ratio 1:1:1, the pore volume 0.30ml/g of either shallow hydrogenation catalyst A, specific surface area 200m²/ g, MoO₃The % of 19%, NiO 1.8, voidage 0.36；The pore volume 0.31ml/g of deep hydrogenation catalyst B, specific surface area 240m²/ g, MoO₃25%, NiO 4%, voidage 0.41；The pore volume 0.38ml/g of hydrocracking catalyst Cat-2, specific surface area 700m2/g, MoO₃31%, NiO 12%, voidage 0.48.Process operation condition, temperature：405 DEG C, pressure 15MPa, volume space velocity 1.0h during total liquid^-1, hydrogen to oil volume ratio 750：1, the results are shown in Table 2.

The preparation method of wherein hydrocracking catalyst is as follows：

Molecular sieve modified processing procedure：

（1）The NaY molecular sieve original powder of laboratory's preparation is taken, with the ammonium nitrate that concentration is 0.8mol/L according to liquid-solid ratio 3:1 mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange₂O is calculated as 2.0%.

（2）To step（1）560 DEG C of the Y molecular sieve for obtaining, hydro-thermal process 2 hours under 0.1MPa；

（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 6:1 mixes with distilled water stirring, then heats to 90 DEG C, and the aluminum sulfate solution 600ml of 0.8mol/L, isothermal reaction 2 hours are added during stirring；

（4）Step（3）200 DEG C of molecular sieve of gained is dried 4h；

（5）Take toluene solvant soaking step（4）The molecular sieve of gained 3 hours；

（6）Step（5）The drying 30 minutes of 130 DEG C of molecular sieve after process；

（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, adds the ammonium fluosilicate solution 150ml that concentration is 0.9mol/L, and 90 DEG C are processed 2 hours；

（8）Jing steps（7）After Y molecular sieve after ammonium fluosilicate process, 120 DEG C of dryings 2 hours, 550 DEG C of roastings 2 hours, modified Y molecular sieve is obtained, numbering is Y-2.

Hydrocracking catalyst preparation process：

（1）Configuration W-Ni dipping solutions：Configuration 1000ml dipping solutions after ammonium metatungstate 480g and nickel nitrate 480g is dissolved in water are taken, active metal is with WO in gained dipping solution₃40g/100ml and 12g/100ml, solution numbers RY-2 are respectively with NiO cubages；

（2）Take Y-2 30g to mix with 70g macroporous aluminium oxides, add 4g/100ml dust technologies to mix in a mixer and roll to extrudable shape, extruded moulding obtains carrier T-2 on banded extruder；

（3）Taking T-2 60g adds 120ml RY-2 maceration extracts to impregnate 2 hours, then 120 DEG C of dryings 4 hours, 500 DEG C of roastings 3 hours, obtains hydrocracking catalyst, and numbering is Cat-2.

Y-2 molecular sieve transmission electron microscope EDAX results determine its outer surface to 180nm thickness, and the silica alumina ratio of superficial layer is 58, and the silica alumina ratio of molecular sieve body phase is 13.XRD analysis result shows its lattice constant for 2.437nm, relative crystallinity 95%.Pore volume 0.38ml/g, specific surface area 700m²/ g, it is 0.72mmol/g that infrared analysis result determines Y-2 meleic acids amount.

Comparative example 1

By the operating condition of embodiment 1, simply two kinds of catalyst are seated in respectively in two fluidized bed reactors, first reactor loads either shallow hydrogenation catalyst A and deep hydrogenation catalyst B, the two ratio 1 along Flow of Goods and Materials direction:1；Second reactor loads hydrocracking catalyst C, the results are shown in Table 2.The present invention program existing scheme is can be seen that from the data of Tables 1 and 2 to compare, impurity removal percentage is substantially suitable.

The reaction result of table 2.

The octane number result of table 3.

Claims

1. a kind of method for producing high aromatic-hydrocarbon gasoline, it is characterised in that including following content：Two reaction zones, including an ebullating bed reactor area, and at least one slight expanded-bed reaction zone are set in reactor；Slight expanded-bed reaction zone is arranged on bottom in reactor, and ebullating bed reactor area is arranged on reactor internal upper part, and slight expanded-bed reaction zone is separated with ebullating bed reactor area by distribution grid；Ebullating bed reactor area volume accounts for the 20% ~ 80% of reactor volume, and remaining part is slight expanded-bed reaction zone；Catalyst inventory is the 10% ~ 80% of reaction zone volume in ebullating bed reactor area；

Microdilatancy reaction zone is entered after feedstock oil and hydrogen mixing from reactor bottom, contact with slight expanded-bed beds, carry out hydrofining reaction, then proceed to flow up contact with the catalyst in ebullating bed reactor area and carry out hydrocracking reaction, generate oil to discharge from reactor head, through fractionation, Vapor recovery unit process the gasoline of high arene content is obtained.

2. in accordance with the method for claim 1, it is characterised in that：The tandem compound of the single microdilatancy reaction zone of described microdilatancy reaction zone or multiple microdilatancy reaction zones, or individually multi-catalyst system level is matched somebody with somebody in microdilatancy reaction zone.

3. in accordance with the method for claim 1, it is characterised in that：Either shallow Hydrobon catalyst includes hydrogenation active metals and carrier, one or more of hydrogenation active metals in group vib and VIII, for one or more in W, Mo, Ni and Co, active metallic content is calculated as 0.1% ~ 15% with oxide weight in catalyst, carrier is inorganic refractory oxide, one or more in aluminum oxide, amorphous silicon aluminium, silica, titanium oxide；The pore volume 0.1-1.5ml/g of catalyst, specific surface area 100-500m²/g。

4. in accordance with the method for claim 1, it is characterised in that：HC-K, HC-T, HC-P that deep hydrofinishing catalyst is developed selected from Uop Inc., and Fushun Petrochemical Research Institute develop 3936,3996, one or more in FF-16, FF-26, FF-36.

5. in accordance with the method for claim 1, it is characterised in that：The either shallow Hydrobon catalyst of microdilatancy reaction zone and the volume loadings of deep hydrofinishing catalyst are 1:9～9:1.

6. in accordance with the method for claim 1, it is characterised in that：The hydrogenation catalyst that described microdilatancy reaction zone is increased along liquid phase material flow direction using 2 ~ 10 kinds of activity, adjacent catalyst bed hydrogenation active metals content differs 1% ~ 50% with oxide percentages；Along the dynamic direction beds voidage of liquid phase stream filling order from small to large, the voidage difference of adjacent catalyst bed is 0.05 ~ 0.35.

7. in accordance with the method for claim 1, it is characterised in that：The hydrorefined reaction condition of described slight expanded-bed reaction zone is：Entrance 0.1 ~ 30MPa of hydrogen dividing potential drop, 0.1 ~ 10h of volume space velocity^-1, reaction temperature is 200 ~ 500 DEG C.

8. in accordance with the method for claim 1, it is characterised in that：Described hydrocracking catalyst includes carrier and active metal, group VIII and/or vib metals element of the described active metal in the periodic table of elements, group VIII active metal is Ni and/or Co, vib active metal is W and/or Mo, group VIII active metallic content is 3% ~ 15%, vib active metallic content is 10% ~ 40%, in terms of metal oxide；Molecular sieve content in described carrier is generally 5wt%～60wt%.

9. in accordance with the method for claim 1, it is characterised in that：Being shaped as hydrocracking catalyst is spherical, elliposoidal, clover, bunge bedstraw herb, four impeller shapes, Raschig ring, butterfly or cellular, catalyst particle size be 0.1 ~ 10mm；The pore volume 0.1-0.9 ml/g of catalyst, specific surface area 100-500m²/g。

10. in accordance with the method for claim 1, it is characterised in that：Using following hydrocracking catalyst, with overall catalyst weight gauge, including：Silica-alumina supports 55% ~ 85% containing modified Y molecular sieve, active metal 15% ~ 45%, wherein active metal is in terms of metal oxide；Mass percent of the described modified Y molecular sieve in silica-alumina supports is 15% ~ 90%, balance of amorphous silica-alumina and/or aluminum oxide；The specific surface area of the catalyst is 200 ~ 400m²/ g, pore volume is 0.2 ~ 0.5ml/g；Group VIII and/or vib metals element of the described active metal in the periodic table of elements, group VIII active metal is Ni and/or Co, vib active metal is W and/or Mo, group VIII active metallic content is 3% ~ 15%, vib active metallic content is 10% ~ 40%, in terms of metal oxide；The preparation method of wherein described modified Y molecular sieve, including following content：（1）Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by former powder of NaY zeolite；（2）To step（1）In the ammonium that obtains exchange after Y molecular sieve carry out hydro-thermal process；（3）To step（2）Y molecular sieve after hydro-thermal process is processed with aluminum salt solution；（4）To step（3）The Y molecular sieve dried process of gained；（5）Step（4）The Y molecular sieve for obtaining impregnates in organic solvent, then rapid draing；（6）By step（5）The Y molecular sieve for obtaining carries out dealumination complement silicon process；（7）Step（6）Y molecular sieve Jing Jing after dealumination complement silicon process is filtered, is dried, roasting, obtains modified Y molecular sieve.

11. in accordance with the method for claim 11, it is characterised in that：Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：It is raw material in ammonium salt aqueous solution with NaY zeolite, at 60 ~ 120 DEG C, exchanges 1 ~ 3 hour, exchange times is 1 ~ 4 time, the NaY zeolite after being exchanged, Na₂O content is less than 3.0%；The wherein SiO of NaY zeolite raw material₂/Al₂O₃Mol ratio is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Ammonium salt is one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration.

12. in accordance with the method for claim 11, it is characterised in that：Step（2）The hydrothermal treatment process is that hydrothermal conditions are in itself vapor or under conditions of being passed through vapor：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and process time is 1.0 ~ 6.0 hours.

13. in accordance with the method for claim 11, it is characterised in that：Step（3）Aluminium salt used by described aluminium salt processing procedure is aluminium chloride, aluminum sulfate, aluminum nitrate, and aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and process time is 0.5 ~ 3 hour.

14. in accordance with the method for claim 11, it is characterised in that：Step（4）Described baking temperature is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.

15. in accordance with the method for claim 11, it is characterised in that：Step（5）One or more of described organic solvent in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene or dimethylbenzene, using supersaturation dipping, dip time is 1 ~ 5h to impregnation method；Baking temperature is 50 ~ 300 DEG C, and drying time is 1 ~ 60 minute.

16. in accordance with the method for claim 11, it is characterised in that：Step（7）Described calcination process condition is：Roasting 2 ~ 4 hours at 400 ~ 600 DEG C.

17. in accordance with the method for claim 11, it is characterised in that：The preparation method of described hydrocracking catalyst, including：First, modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed according to a certain ratio, add dust technology into extruded moulding after slurry, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；Wherein the concentration of dust technology is 3wt% ~ 30wt%；Described drying condition is：It is dried 1 ~ 5 hour at 80 ~ 120 DEG C；Roasting condition is：Roasting 1 ~ 5 hour at 400 ~ 700 DEG C；2nd, the carrier of step one is impregnated using the maceration extract containing active metal, the carrier drying after dipping, roasting obtain hydrocracking catalyst.

18. in accordance with the method for claim 1, it is characterised in that：The volume loadings of the hydrocracking catalyst in Hydrobon catalyst and ebullated bed in slight expanded-bed are 1：9～9：1.