CN108624357A

CN108624357A - A kind of catalytic diesel oil conversion process

Info

Publication number: CN108624357A
Application number: CN201710182289.7A
Authority: CN
Inventors: 柳伟; 方向晨; 杜艳泽; 王凤来; 秦波; 高杭; 张晓萍
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2017-03-24
Filing date: 2017-03-24
Publication date: 2018-10-09
Anticipated expiration: 2037-03-24
Also published as: CN108624357B

Abstract

The invention discloses a kind of catalytic diesel oil conversion process, including the following contents：（1）The mixed material of catalytic cracking diesel oil and hydrogen is introduced into hydrogenation reactor and carries out hydrofining reaction；（2）Hydrofining reaction effluent is directly entered cracker, with hydrocracking catalyst bed haptoreaction in cracker；Two hydrocracking catalyst beds above and below grading loading wherein in hydrocracking reactor；Upper bed layer catalyst is using W Ni and/or Mo Ni as active metal component, using modified Y molecular sieve and alkali metal and/or alkali-earth metal modified aluminium oxide as carrier；For lower bed layer catalyst using Mo Co as active metal component, modified Y molecular sieve and carbon deposit aluminium oxide are carrier；（3）Step（2）It obtains hydrocracking reaction effluent and obtains naphtha component and diesel component through detaching and being fractionated.For present invention process under the premise of better meeting catalytic diesel oil conversion ratio, reduce the gasoline component of generation adds hydrogen saturation, improves gasoline component octane number.

Description

A kind of catalytic diesel oil conversion process

Technical field

The invention belongs to hydrotreating techniques fields, relate in particular to a kind of catalytic diesel oil hydroconversion process.

Background technology

Since the new century, with being increasingly enhanced of people's environmental consciousness, national environmental protection regulation increasingly stringent and The fast development of national economy, demand of the countries in the world to cleaning automotive fuel are all being continuously increased.Catalytic cracking（FCC）Technology It is one of the main technique means of heavy oil lighting, important status is all occupied in the oil refining enterprise of countries in the world.I State's catalytic cracking unit annual working ability alreadys exceed 100,000,000 tons at present, is only second to the U.S..In petrol and diesel oil product composition, catalysis is split Change gasoline and account for 80% or so, catalytic diesel oil accounts for 30% or so.In recent years, with the increasingly heaviness of domestic processed crude quality, The raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, in addition many enterprises improve quality of gasoline or increasing to reach The purpose for producing propylene has carried out catalytic cracking unit the operating severity for being transformed or improving catalytic cracking unit, has caused to be catalyzed The product of cracking, especially catalytic diesel oil quality more deteriorate.

To improve the utilization rate of petroleum resources, the total quality level of vapour, diesel fuel is improved, realizes that product blending is optimal Change and the maximized target of value of the product, satisfaction are domestic to clean fuel increasing need, high aromatics diesel hydro-conversion The hydrocracking process technology for producing high added value naphtha component and low-sulfur cleaning diesel fuel has good application prospect. Domestic and international researcher has also carried out a large amount of research work.Foreign countries are existing to use hydrocracking process technology by catalytic cracking Light cycle oil is converted into the relevant report of ultra-low-sulphur diesel and high octane value gasoline blending component.

US2010116712 discloses a kind of catalytic diesel oil hydrogenating conversion process, and this method is using common process method and splits Change catalyst, feedstock oil contacts after first passing around pretreatment with Cracking catalyst, production cleaning diesel oil and high-new alkane value gasoline.But It is that the reduction gasoline component that this method can not be selective adds hydrogen saturation, and therefore, gasoline products loss of octane number is larger.

EP20110834653 discloses a kind of preparation method of polycyclic aromatic hydrocarbon hydrogenation conversion catalyst, the catalyst carrier It is made of beta-molecular sieve and boehmite, using conventional method addition group VIB and group VIII active metal component, but Catalyst is equally stronger to gasoline component saturability, is unfavorable for catalytic diesel oil hydro-conversion production high-knock rating gasoline process.

Invention content

In view of the deficiencies of the prior art, the present invention provides a kind of catalytic diesel oil conversion process, turn meeting catalytic diesel oil Under the premise of rate, reduce the gasoline component of generation adds hydrogen saturation, improves gasoline component octane number.

The catalytic diesel oil conversion process of the present invention, including the following contents：

（1）The mixed material of catalytic cracking diesel oil and hydrogen is introduced into hydrogenation reactor and carries out hydrofining reaction；

（2）Hydrofining reaction effluent is directly entered cracker, with hydrocracking catalyst bed in cracker Haptoreaction；The upper and lower two hydrocracking catalyst beds of grading loading, upper and lower two beds wherein in hydrocracking reactor The mass ratio 1 of hydrocracking catalyst：5~5：1, preferably 1：2~2：1；Upper bed layer catalyst is with W-Ni and/or Mo-Ni Active metal component, using the aluminium oxide of modified Y molecular sieve and carrying alkali metal or alkaline-earth metal as carrier, with catalyst weight Meter, WO₃And/or MoO₃8%~18%, NiO2%~10%, modified Y molecular sieve 40%~90%, preferably 50%~80%, alkali metal and/ Or alkali-metal-oxide content is 0.2% ~ 5%, preferably 1% ~ 3%, surplus is aluminium oxide；Lower bed layer catalyst is to live with Mo-Co Property metal component, modified Y molecular sieve and carbon deposit aluminium oxide are carrier, with catalyst weight, MoO₃8wt%~18wt%, CoO are 2wt%~10wt%, Y molecular sieve content are 5% ~ 50%, preferably 10% ~ 40%, and alumina content is 10% ~ 50%, preferably 20% ~ 40%, Carbon content 0.2% ~ 12%, preferably 2% ~ 5%；The alkali and alkaline earth metal ions are selected from one or more of Na, K, Mg and Ca, excellent Select Na and/or Mg；

（3）Step（2）It obtains hydrocracking reaction effluent and obtains naphtha component and diesel component through detaching and being fractionated, wherein Naphtha component directly goes out device as high-knock rating gasoline blend component, and diesel component can directly go out device blended diesel, Cracker is recycled into further to react.

In present invention process, the Hydrobon catalyst of selection can use commercial product, can also be normal according to this field Knowledge is advised to prepare.Conventional hydrocracking pretreatment catalyst can be used in Hydrobon catalyst used in the present invention, generally with VIB Race and/or group VIII metal are active component, using aluminium oxide or silicon-containing alumina as carrier.Vib metals are generally Mo And/or W, group VIII metal are generally Co and/or Ni.On the basis of the weight of catalyst, vib metals content is to aoxidize Object is calculated as 8wt%~28wt%, and group VIII tenor is calculated as 2wt%~15wt% with oxide.

In present invention process, the preparation method of overlying catalyst, including following content：（a）First use alkali metal and/or Alkaline-earth metal dipping solution impregnates alumina powder, then, dry, roasting；（b）Step（c）Obtained aluminium oxide divides with Y Son sieve, group VIB and Section VIII active metallic compound are uniformly mixed, and dust technology are added, rear extruded moulding, dry, roasting is slurried It burns, obtains catalytic diesel oil reforming catalyst.

Step（a）The alkali and alkaline earth metal ions are selected from one or more of Na, K, Mg and Ca, preferably Na and/or Mg；Step（a）The dipping method is that saturation impregnates, and it is 1.5 that the liquid of dipping process, which consolidates mass ratio,：1~3：1；Described contains alkali Metal and/or the aqueous solution that alkaline-earth metal dipping solution is alkali metal and/or alkali salt；Wherein, the alkali metal and/ Or alkali salt is generally the nitrate of alkali or alkaline earth metal.Alkali metal and/or alkali salt contains in maceration extract Amount is calculated as 2 ~ 15g/100ml by corresponding oxide, and the concentration of alkali metal and/or alkali salt can be according to product in maceration extract It needs to adjust accordingly.Step（a）The drying condition is：It is 1 ~ 5 hour dry at 80 ~ 120 DEG C under air atmosphere；Roast item Part is：It roasts 1 ~ 5 hour at 400 ~ 700 DEG C in air atmosphere.

Step（b）The group VIB active metal is selected from W and/or Mo, and group VIII active metal is selected from Ni, mixing The content of group vib metallic compound accounting based on corresponding oxide is the wt% of 8wt% ~ 18 in object, group VIII metallic compound Content accounting based on corresponding oxide is the wt% of 2 wt% ~ 10.A concentration of 3wt% ~ 30wt% of the dust technology.

Step（b）The drying condition is：It is 1 ~ 5 hour dry at 80 ~ 120 DEG C under air atmosphere；Roasting condition is： It is roasted 1 ~ 5 hour at 400 ~ 700 DEG C under air atmosphere；

The mode of loading of active metal can also use saturation infusion process in the method for the present invention.That is carrying alkali metal and/or alkaline earth The alumina powder of metal with the carrier that is mixed with of Y molecular sieve, then uses the water containing group VIII and group vib salt first Solution carries out saturation dipping to carrier；Wherein group VIB active metal is selected from W and/or Mo, and group VIII active metal is selected from Ni, the content of group vib metallic compound is calculated as 10 ~ 40g/100ml, group VIII metal compound by corresponding oxide in maceration extract The content of object is calculated as 3 ~ 20g/100ml by corresponding oxide, and the concentration of metallic compound can be according to product needs in maceration extract It adjusts accordingly.

In present invention process, prepared by the preferably following method of the upper bed layer catalyst：（I）By modified Y molecular sieve, load alkali The aluminium oxide of metal and/or alkaline-earth metal is uniformly mixed, and dust technology is added, rear extruded moulding is slurried, dry, roasting, which obtains containing, to be changed The silica-alumina supports of property Y molecular sieve；（II）Carrier is contacted with carbon source, carbon deposit reaction is then carried out, obtains carbon deposit carrier；（III） The carbon deposit carrier is roasted in oxygen-containing gas, obtains de- high-area carbon；The carbon content of the de- high-area carbon is the product The 20%~80% of the carbon content of high-area carbon, preferably 30% ~ 70%；Wherein, the oxygen content of the oxygen-containing gas is 0.5v%~8v%； Calcination temperature is 250~390 DEG C, and preferably 300~390 DEG C, roasting time is 3.5~20h, preferably 4 ~ 12h；（IV）It is taken off to described High-area carbon introduces active metal component precursor and drying；（V）By step（IV）Obtained product is heat-treated, the activity Metal component precursor is changed into reactive metal oxides, and retains the charcoal on the decarburization carrier.

The carbon source is selected from various gaseous states or liquid carbonaceous material, can be liquid or gaseous unsaturated olefin, such as Positive structure or isomeric olefine, the alkadienes of C2~C10.In order to improve carbon deposit efficiency, the carbon source can be selected from petroleum ether, benzene, first In benzene, dimethylbenzene, catalytic gasoline, coker gasoline, butadiene, pentadiene, hexadiene, butylene, amylene, heptene and nonene at least It is a kind of.

The condition that the carrier is contacted with carbon source includes：Pressure is 0.1~1 MPa, and the time is 0.1~6 h.When described When carbon source is gaseous state, pressure is 0.1~1MPa, and the time is 0.1~2h；When the carbon source is liquid, 0.1~1MPa of pressure, Time is 0.5~6h.The carrier comes into full contact with the carbon source, generally carries out at normal temperatures, and room temperature is generally 25~40 DEG C.

It is charcoal that the carbon deposit, which reacts the surface conversion that can make the carbon source in the carrier,.Under preferable case, the product Charcoal reaction carries out in the presence of oxygen-containing atmosphere, and carbon deposit reaction temperature is 100~500 DEG C, preferably 180 ~ 300 DEG C；Carbon deposit reacts Time is 20~200 h, preferably 50 ~ 100h.

In carbon deposit reaction, the oxygen content of oxygen-containing atmosphere is 10v~100v%, the oxygen-containing atmosphere be selected from air or The mixture of oxygen and inert gas, preferably air.

The step of method provided by the invention for preparing hydrocracking catalyst（III）In, it is preferable that the calcination temperature It is 300~390 DEG C；The roasting time is 4~20h.

The carbon distribution carrier is put into roaster, warm from room temperature to the roasting with the heating rate of 20~40 DEG C/h Degree, and constant temperature reaches the roasting time under the calcination temperature；The volume ratio of the oxygen-containing gas and the carbon distribution carrier For（500~5000）：1.

For the de- charcoal of realization appropriateness, heating rate, heating final temperature and roasting time when controlling atmosphere when roasting, roasting, tool Body, by the way that the carbon deposit carrier to be placed in low oxygen content atmosphere, specifically to heat up since room temperature in roaster Rate is warming up to calcination temperature, and the calcination temperature is less than general high-temperature roasting, and keeps longer roasting time, i.e., low Prolonged slowly roasting is carried out under calcination temperature.In the present invention, room temperature is 25~40 DEG C.

The active metal component precursor is changed into reactive metal oxides, and retains charcoal on the decarburization carrier Purpose.A kind of preferred embodiment, the heat treatment include：By step（IV）Obtained product is in inert gas and 400 2~10h of roasting is carried out at~700 DEG C, obtains hydrocracking catalyst.Detailed process can be：Described in being carried out in roaster Roasting first introduces inert gas into line replacement into roaster, and inert gas introduces speed control gas/agent（Inert gas and leaching Stain and the de- high-area carbon after drying）Volume ratio be（500~5000）：1, in the atmosphere of inert gas replacement to roaster, oxygen After gas purity is less than 0.1 volume %, with 20~40 DEG C/h heating rates by under roasting furnace temperature elevation to calcination temperature, constant temperature is described The roasting is completed in roasting time.The inert gas used that roasts can be N₂, helium, it is a kind of in neon and argon gas or Several mixed gas.

Above method makes carbon source cover by the way that the carrier contacted with carbon source is first carried out carbon deposit reaction in oxygen-containing atmosphere Acid centre on carrier；Then by the way that carbon distribution carrier to be carried out to low temperature, slowly roasting in the oxygen-containing gas of low oxygen content, Selectively burn off is deposited on the carbon deposit on non-strong acid so that obtained de- high-area carbon has suitable meleic acid distributed architecture. Then, then impregnate active metal obtain hydrocracking catalyst.Inertia high temperature roasting or low temperature for a long time are finally used again Aerobic prolonged roasting is finally retained the hydrocracking catalyst of certain content charcoal.It is provided by the invention to be hydrocracked Catalyst has rational meleic acid intensity distribution, and has the dispersion of suitable active metal component simultaneously, for being catalyzed bavin When the hydrocracking reaction of oil, hydrocracking catalyst can be significantly improved in the reaction effect of start of run, production gasoline production Yield, total liquid yield and the gasoline products octane number of product are significantly improved；And catalyst can keep good during operation Catalytic stability.

In present invention process, the preparation method of lower bed layer catalyst, including following content：（1）By aluminium oxide and liquid or Gaseous unsaturated olefin comes into full contact with, and carbon deposit reaction is then carried out in oxygen-containing atmosphere, obtains carbon deposit aluminium oxide；（2）Carbon deposit Aluminium oxide, modified Y molecular sieve, active metallic compound containing Mo and active metallic compound containing Co are uniformly mixed, and dust technology is added Rear extruded moulding is slurried, dry, roasting obtains catalyst.

Wherein, the unsaturated olefin is the positive structure or isomeric olefine, alkadienes that carbon atom number is 2 ~ 10；It is wherein described Alkene and molecular sieve to come into full contact with refer to that unsaturated olefin diffuses into inside molecular sieve；When use gaseous state unsaturated olefin When, gaseous state unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, 0.1 ~ 2 hour time of contact；When using liquid When state unsaturated hydrocarbons, liquid unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 are small When, molecular sieve answers thorough impregnation in liquefied olefines.The alkene comes into full contact with molecular sieve and generally carries out at normal temperatures, institute The unsaturated hydrocarbons state phase stated is phase under room temperature.

The oxygen-containing atmosphere is one in air, the mixture of oxygen and nitrogen or the mixture of oxygen and inert gas Kind, the volume fraction of oxygen in the gas phase is 10% ~ 100%, preferably air；Carbon deposit reaction condition is：Reaction temperature 50 ~ 500 DEG C, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 200 hour, preferably 10 ~ 100 hours.

In the carbon deposit aluminium oxide, on the basis of carbon deposit alumina weight, carbon content is 0.5wt% ~ 20wt%, preferably The Kong Rong ratios of 2wt ~ 15wt%, carbon deposit aluminium oxide and aluminium oxide before non-carbon deposit are 1:10~1:1.5.

The content of the active metallic compound containing Mo accounting based on corresponding oxide is the wt% of 4wt% ~ 20, is lived containing Co Property metallic compound content based on corresponding oxide accounting be 2 wt% ~ 15wt%.A concentration of 3wt% of the dust technology ~ 30wt%。

The drying condition is：It is 2 ~ 8 hours dry at 90 ~ 150 DEG C；After drying process, the product in aluminium oxide Carbon can roast removing in oxygen-containing atmosphere, can also roast reservation in an inert atmosphere in the catalyst；Roasting condition is： It is roasted 1 ~ 5 hour at 300 ~ 600 DEG C.The inert atmosphere is selected from N₂, helium, one or more of neon or argon gas.Institute The oxygen-containing atmosphere stated is one kind in air, the mixture of oxygen and nitrogen or the mixture of oxygen and inert gas, and oxygen exists Volume fraction in gas phase is 10% ~ 100%, preferably air.

Wherein the mode of loading of Mo-Co active metals can also use saturation infusion process.That is carbon distribution treated aluminium oxide Powder with the carrier that is mixed with of Y molecular sieve, then uses the aqueous solution containing Mo and Co to carry out saturation dipping to carrier first, The concentration of metallic compound can need to adjust accordingly according to product in maceration extract.

The modified Y molecular sieve that the present invention uses can be conventional method modified molecular screen, and modified Y molecular sieve property is as follows： SiO₂/Al₂O₃Molar ratio 8 ~ 50, preferably 10 ~ 30；500~900 m of specific surface area²/ g, preferably 600~800 m²/g；Hole holds 0.30 ~0.60ml/g, preferably hole hold 0.35~0.50ml/g；Relative crystallinity 80%~130%, preferably 90%~110%, cell parameter 2.432~2.460nm, preferably 2.435~2.450；Meleic acid 0.4~1.5mmol/g of amount, preferably 0.5 ~ 1.3 mmol/g；

In present invention process, the process conditions of the hydrofining reaction are：Reaction temperature be 320~440 DEG C, preferably 340 ~420 DEG C；Reaction pressure is 4.0~15.0 MPa, preferably 6.0~12.0 MPa；Volume space velocity is 0.2~6.0h when liquid^-1, excellent Select 0.5~3.0h^-1；Hydrogen to oil volume ratio is 100~2000, preferably 500~1500.

In present invention process, the process conditions of the hydrocracking reaction are：Reaction temperature is 340~440 DEG C, preferably 360~430 DEG C；Reaction pressure is 4.0~15.0MPa, preferably 6.0~12.0MPa；Volume space velocity is 0.2~6.0h when liquid^-1, It is preferred that 0.5~3.0h^-1；Hydrogen to oil volume ratio is 100~2000, preferably 500~1500.

In present invention process, the property of the catalytic cracking diesel oil is generally：Density is 0.88~0.99g/cm³, do Generally 360~400 DEG C of point, arene content is generally 50wt%~95wt%.The sulfur content of catalytic cracking diesel oil is generally 0.2wt%~2wt%, nitrogen content are 500~2000ppm.

Compared with prior art, present invention process advantage is：Catalytic diesel oil hydroconversion reactions process is anti-with cracking The progress answered is gradually reduced along diesel oil distillate accounting in the logistics from top to bottom of cracker bed, gasoline component accounting by It gradually improves, when diesel oil single catalyst system, is meeting bavin in upper reactor bed when catalyst hydrogenation ability is excessively high While oil conversion, lower part bed gasoline component supersaturation causes octane number loss excessive；Work as catalyst hydrogenation activity When insufficient, then catalyst cracking ability is affected, and the ability of catalyst cracking diesel oil declines.For this purpose, rational system should It is Efficient Conversion production gasoline component, the low hydrogenation activity in lower part that the high hydrogenation activity in top and high cracking activity carry out catalytic diesel oil The overcracking and saturation of the gasoline component generated are reduced with low cracking activity, improve gasoline yield and octane number.In addition, catalysis The reaction process process of diesel oil hydrogenation conversion production high-knock rating gasoline is typically denitrogenation after the hydrogenated denitrogenation of catalytic diesel oil raw material Reaction generates oil and carries out hydrocracking reaction generation high octane gasoline component.The hydrocracking catalyst of hydrocracking reaction is logical Often using Y molecular sieve and aluminium oxide as carrier, W-Ni or Mo-Ni are active metal component.For conventional hydrocracking reaction process Hydrocracking catalyst in aluminium oxide both as dispersion Y molecular sieve matrix, decentralized cracking center, meanwhile, on aluminium oxide Better hydrogenation active metals dispersion performance, be also beneficial to cracked product further adds hydrogen saturation, improves cracked product property. But high-knock rating gasoline technology is produced for catalytic diesel oil hydro-conversion, it is desirable that Cracking catalyst has certain hydrogenation capability It terminates carbonium ion, inhibit excessive fragmentation, improve catalyst stability, the hydrogenation active metals loaded on molecular sieve are conducive to carry The matching of height plus hydrogen and acid centre, reduces excessive fragmentation, this partial hydrogenation activity belongs to effective hydrogenation activity, lives on aluminium oxide The property excessively high hydrogenation activity of metal, be easy to cause the saturation of aromatic hydrocarbons in gasoline products, reduces gasoline products octane number, be unfavorable for Gasoline products octane number is improved, this is that catalytic diesel oil hydro-conversion production high-knock rating gasoline technology is undesirable.Conventional Preparation method generally directly prepares aluminium oxide and molecular sieve complex carrier, then passes through impregnation active component, the two On active component synchronized when increasing or decreasing, if improving the hydrogenation activity on molecular sieve, hold mistake on aluminium oxide High hydrogenation activity is easy to cause excessive hydrogenation saturation, if reducing the hydrogenation activity on aluminium oxide, reduces plus hydrogen is saturated, The normal hydrogenation activity of Y molecular sieve can be then influenced, excessive fragmentation is caused.So how active component is in oxygen in equilibrium catalyst Change on aluminium and molecular sieve between hydrogenation capability ability, there is insoluble contradiction, the two is difficult to take into account.

Present invention process is by the way of grading using W-Ni the and/or Mo-Ni metal components of high hydrogenation activity as upper layer The hydrogenation active metals of catalyst, overlying catalyst are equipped with the oxidation that macromolecule sieve content and alkali or alkaline earth metal are modified Aluminium inhibits load active on alumina to a certain degree while not influencing the hydrogenation activity of active metal on Y molecular sieve The hydrogenation activity of metal so that catalyst has moderate hydrogenation activity.Realize that high cracking activity and appropriate hydrogenation activity match；Under Layer catalyst then uses the combination of low molecule sieve content and Mo-Co active metal components, to realize low hydrogenation activity and low cracking Active matching.Meanwhile by carrying out carbon distribution processing, the product of formation to alumina powder in advance in lower catalyst agent preparation process Carbon is filled with cell channels and the surface of aluminium oxide, in this way during subsequently dipping hydrogenation active component, reduces activearm Divide load capacity on alumina, while not influencing the hydrogenation activity of active metal on Y molecular sieve, it is suppressed that be supported on oxygen Change the hydrogenation activity of active metal on aluminium, therefore, lower catalyst agent has better hydrogenation reaction selectivity, can reduce cracking The excessive hydrogenation of the gasoline component of generation on alumina improves gasoline products octane number, improves the effective plus hydrogen of catalyst Ability, while active component is easier to be supported on molecular sieve surface in dipping process, reduces the use of activity component impregnation liquid Amount.

Embodiment

Below by embodiment, the present invention is further described, but is not so limited the present invention.Involved percentage in embodiment Than being mass percent（Except relative crystallinity）, the liquid-solid ratio is that liquid consolidates mass ratio.Embodiment and comparative example use Identical industrial production modified Y molecular sieve and macroporous aluminium oxide are as carrier component, the uniform industrial production model of the two.

Embodiment 1

（1）Configure NaNO₃Aqueous solution, NaNO₃Concentration is with Na₂O is calculated as 8g/100ml；

（2）The NaNO obtained in step 1₃Aqueous solution is according to liquid/solid than 3:1 dipping industrial production macroporous aluminium oxide powder 2h, mistake 120 DEG C of roastings 2h, 550 DEG C of roasting 3h after filter；

（3）Take step（2）Obtained aluminium oxide 40g, industrial production modified Y molecular sieve 80g, MoO₃20g and nickel nitrate 20g is mixed It closes, addition 4g/100ml dust technologies mix in a mixer to roll to extrudable shape, extrusion, molding on banded extruder, dry roasting It burns and obtains catalyst C1.

Embodiment 2

（1）Configure Mg (NO₃)₂Aqueous solution, Mg (NO₃)₂Concentration is calculated as 4g/100ml with MgO；

（2）Mg (the NO that step 1 obtains₃)₂Aqueous solution is according to liquid/solid than 2:1 dipping industrial production macroporous aluminium oxide powder 2h, mistake 110 DEG C of roastings 4h, 500 DEG C of roasting 4h after filter；

（3）Take step（2）Obtained aluminium oxide 30g, industrial production modified Y molecular sieve 90g is mixed, and 4g/100ml dust technologies are added Mixing is rolled to extrudable shape in a mixer, and extruded moulding obtains carrier on banded extruder；

（4）Mo-Ni dipping solutions are configured, by MoO₃, basic nickel carbonate be added in distilled water and prepare inclined Mo-Ni dipping solutions, MoO is adjusted in mixed solution in terms of the oxide of metal salt₃23g/100ml, nickel oxide 8g/100ml；

（5）Take step（4）The Mo-Ni dipping solutions of acquisition, according to liquid-solid ratio 3:1 impregnation steps（3）The catalyst carrier of acquisition 2h, then, 120 DEG C of dry 3h, 500 DEG C of roasting 3h obtain catalyst C2.

Embodiment 3

（1）Configure KNO₃Aqueous solution, KNO₃Concentration is with Na₂O is calculated as 10g/100ml；

（2）The NaNO that step 1 obtains₃Aqueous solution is according to liquid/solid than 2:1 dipping industrial production macroporous aluminium oxide powder 2h, filtering 110 DEG C of roastings 4h, 500 DEG C of roasting 4h afterwards；

（3）Take step（2）Obtained aluminium oxide 50g, industrial production modified Y molecular sieve 100g, metatungstic acid are by 25g and nickel nitrate 20g is mixed, and addition 4g/100ml dust technologies mix in a mixer to roll to extrudable shape, and extrusion, molding, do on banded extruder Dry roasting obtains catalyst C3.

Embodiment 4

（1）Industrial production macroporous aluminium oxide 200g is taken to be positioned in the closed container full of butadiene atmosphere, control pressure 0.3MPa comes into full contact with 20 minutes, then, is heated 70 hours at 180 DEG C in air atmosphere；

（2）Take step（1）Obtained aluminium oxide 80g, Commercial modified Y molecular sieve 50g, MoO₃15g and cobalt nitrate 20g mixing, add Enter 4g/100ml dust technologies mix in a mixer roll to extrudable shape after extruded moulding；

（3）Step（2）After the dry 4h of lower 120 DEG C of sample air atmosphere, it is transferred to 500 DEG C of roasting 3h in nitrogen atmosphere and obtains catalyst C4。

Embodiment 5

（1）Heptene is taken to impregnate industrial production macroporous aluminium oxide 200g 4 hours, then, 160 DEG C of heating 120 are small in air atmosphere When；

（2）Take step（1）Obtained aluminium oxide 100g, Commercial modified Y molecular sieve 60g mixing, is added 4g/100ml dust technologies and exists 120 DEG C of dry 4h obtain 3 carrier of embodiment after mixing rolls extruded moulding in mixer；

（3）Mo-Co dipping solutions are configured, by MoO₃, basic cobaltous carbonate be added in distilled water and prepare inclined Mo-Co dipping solutions, MoO is adjusted in mixed solution in terms of the oxide of metal salt₃30g/100ml、CoO 10g/100ml；

（4）Take step（3）The Mo-Co dipping solutions of acquisition, according to liquid-solid ratio 3:1 impregnation steps（2）The catalyst carrier of acquisition Then 2h after the dry 2h of lower 150 DEG C of air atmosphere, is transferred to 400 DEG C of roasting 4h in helium atmosphere and obtains catalyst C5.

Embodiment 6

With embodiment 2, only by step（3）Calcination atmosphere be changed to air, obtain catalyst C6

Embodiment 7

（1）Heptene is taken to impregnate industrial production macroporous aluminium oxide 200g 2 hours, then, 280 DEG C of heating 80 are small in air atmosphere When；

（2）Take step（1）Obtained aluminium oxide 80g, Commercial modified Y molecular sieve 80g, ammonium metatungstate 22g and cobalt nitrate 20g is mixed It closes, 4g/100ml dust technologies are added mix in a mixer and roll to extrudable shape, extruded moulding after shape；

（3）Step（2）After the dry 4h of lower 120 DEG C of sample air atmosphere, it is transferred to 550 DEG C of roasting 3h in nitrogen atmosphere and obtains catalyst C7。

Embodiment 8

（1）Hexadiene is taken to impregnate industrial production macroporous aluminium oxide 200g 2 hours, then, 360 DEG C of heating 50 in air atmosphere Hour；

（2）Take step（1）Obtained aluminium oxide 100g, modified Y molecular sieve 50g, ammonium metatungstate 30g and cobalt nitrate 60g mixing, adds Enter 4g/100ml dust technologies mix in a mixer roll to extrudable shape after extruded moulding；

（3）Step（2）After the dry 4h of lower 120 DEG C of sample air atmosphere, it is transferred to 450 DEG C of roasting 3h in nitrogen atmosphere and obtains catalyst C8。

Embodiment 9

（3）Take step（2）4g/100ml dust technologies are added mixed in obtained aluminium oxide 40g, industrial production modified Y molecular sieve 80g Mixing is rolled to extrudable shape in clutch, extrusion, molding acquisition carrier on banded extruder；

（4）Take step（1）The carrier of gained is positioned in the closed container full of butadiene atmosphere, and control pressure 0.3MPa is abundant Contact 20 minutes, then, is heated 80 hours in air atmosphere at 200 DEG C；

（5）By step（2）Obtained carbon deposit carrier is positioned in roaster, be passed through into roaster oxygen content be 1% oxygen/ Nitrogen mixed gas is warming up to 380 DEG C, constant temperature calcining 4h with 25 DEG C/h heating rates；

（6）Configure Mo-Ni dipping solutions：Take MoO₃Mo-Ni dipping solutions, gained are configured after being dissolved in water with basic nickel carbonate Active metal is with MoO in dipping solution₃It is respectively 34g/100ml and 11g/100ml with NiO content calculations；

（7）Take step（4）The drying 4 hours of 120 DEG C of sample；

（8）By step（5）Obtained drying sample, which is positioned in roaster, introduces N₂Into line replacement, control gas/agent ratio is gas 2000；

（9）After inert gas replacement to oxygen purity 0.08v%, 550 DEG C are warming up to 40 DEG C/h heating rates, constant temperature handles 6h, Obtain catalyst C9.

Embodiment 10

Configure Mg (NO₃)₂Aqueous solution, Mg (NO₃)₂Concentration is calculated as 4g/100ml with MgO；

（4）Take heptene soaking step（1）Then the carrier of gained 4 hours heats 150 hours for 180 DEG C in air atmosphere；

（5）By step（2）Obtained carbon deposit carrier is positioned in roaster, be passed through into roaster oxygen content be 3% oxygen/ Nitrogen mixed gas is warming up to 350 DEG C, constant temperature calcining 10h with 25 DEG C/h heating rates；

（6）Configure Mo-Ni dipping solutions：Take MoO₃Mo-Ni dipping solutions, gained leaching are configured after being dissolved in water with basic nickel carbonate Active metal is with MoO in stain solution₃It is respectively 30g/100ml and 11g/100ml with NiO content calculations；

（7）Take step（4）The drying 4 hours of 120 DEG C of sample；

（9）After inert gas replacement to oxygen purity 0.08v%, 550 DEG C are warming up to 40 DEG C/h heating rates, constant temperature handles 6h, Obtain catalyst C10.

Comparative example 1：

（1）Take industrial production aluminium oxide 40g, modified Y molecular sieve 80g, MoO₃20g and nickel nitrate 20g mixing, are added 4g/ 100ml dust technologies mix in a mixer to roll to extrudable shape, and extrusion, molding on banded extruder, dry, roasting are catalyzed Agent B1.

Comparative example 2：

（1）Take industrial production macroporous aluminium oxide 80g, Commercial modified Y molecular sieve 50g, MoO₃15g and cobalt nitrate 20g mixing, add Enter 4g/100ml dust technologies mix in a mixer roll to extrudable shape after extruded moulding；（2）Step（1）In sample air After 120 DEG C of dry 4h, it is transferred to 500 DEG C of roasting 3h in air atmosphere and obtains catalyst B2.

1 embodiment catalyst physico-chemical property of table.

Embodiment 9

In order to investigate the reaction effect of catalytic diesel oil hydrogenation conversion catalyst grading loading technology of the present invention, in midget plant On carried out evaluation test, evaluating apparatus is connected using single hop once to be passed through flow and produces gasoline and hydrogenated diesel oil, an anti-filling Regular refiner catalyst, two instead load different preparation methods and different gradation mode catalyst system, catalyst for refining reason respectively Change property, raw material oil nature and evaluation result and is listed in table 2 ~ 5.

2 one anti-catalyst for refining physicochemical property of table

3 raw material oil nature of table

The type of feed and operating condition of 4 two anticatalyst of table.

5 product distribution of table and property comparison.

Claims

1. a kind of catalytic diesel oil conversion process, it is characterised in that including the following contents：（1）The mixing of catalytic cracking diesel oil and hydrogen Material is introduced into hydrogenation reactor and carries out hydrofining reaction；（2）Hydrofining reaction effluent is directly entered cracker, With hydrocracking catalyst bed haptoreaction in cracker；Grading loading two up and down wherein in hydrocracking reactor Hydrocracking catalyst bed, the mass ratio 1 of upper and lower two bed hydrocracking catalysts：5~5：1, preferably 1：2~2：1； Upper bed layer catalyst is using W-Ni and/or Mo-Ni as active metal component, with modified Y molecular sieve and carrying alkali metal or alkaline earth gold The aluminium oxide of category is carrier, with catalyst weight, WO₃And/or MoO₃8%~18%, NiO2%~10%, modified Y molecular sieve 40% ~90%, preferably 50%~80%, alkali metal and/or alkali-metal-oxide content are 0.2% ~ 5%, and surplus is aluminium oxide；Lower bed layer For catalyst using Mo-Co as active metal component, modified Y molecular sieve and carbon deposit aluminium oxide are carrier, with catalyst weight, MoO₃8wt%~18wt%, CoO are 2wt%~10wt%, and Y molecular sieve content is 5% ~ 50%, and alumina content is 10% ~ 50%, and carbon contains Amount 0.2% ~ 12%；（3）Step（2）It obtains hydrocracking reaction effluent and obtains naphtha component and diesel oil group through detaching and being fractionated Point.

2. technique described in accordance with the claim 1, it is characterised in that：The alkali and alkaline earth metal ions are selected from Na, K, Mg and Ca One or more of.

3. technique described in accordance with the claim 1, it is characterised in that：The preparation method of overlying catalyst, including following content：（a）Alkali metal and/or alkaline-earth metal dipping solution is used to impregnate alumina powder first, then, dry, roasting；（b）Step Suddenly（c）Obtained aluminium oxide is uniformly mixed with Y molecular sieve, group VIB and Section VIII active metallic compound, be added dust technology at Extruded moulding after slurry, dry, roasting, obtains catalytic diesel oil reforming catalyst.

4. technique described in accordance with the claim 3, it is characterised in that：Step（a）The alkali and alkaline earth metal ions be selected from Na, K, One or more of Mg and Ca；The dipping method is that saturation impregnates, and it is 1.5 that the liquid of dipping process, which consolidates mass ratio,：1~3： 1；The alkali metal containing and/or alkaline-earth metal dipping solution is the aqueous solution of alkali metal and/or alkali salt；In maceration extract The content of alkali metal and/or alkali salt is calculated as 2 ~ 15g/100ml by corresponding oxide.

5. technique described in accordance with the claim 3, it is characterised in that：Step（a）The drying condition is：80 under air atmosphere ~ It is 1 ~ 5 hour dry at 120 DEG C；Roasting condition is：It roasts 1 ~ 5 hour at 400 ~ 700 DEG C in air atmosphere.

6. technique described in accordance with the claim 3, it is characterised in that：Step（b）The group VIB active metal be selected from W and/ Or Mo, group VIII active metal are selected from Ni, the content of group vib metallic compound accounting based on corresponding oxide is in mixture 8wt% ~ 18wt%, the content of the group VIII metallic compound accounting based on corresponding oxide is 2 wt% ~ 10wt%.

7. technique described in accordance with the claim 1, it is characterised in that：The upper bed layer catalyst is prepared as follows：（I）It will The aluminium oxide of modified Y molecular sieve, carrying alkali metal and/or alkaline-earth metal is uniformly mixed, and dust technology is added, rear extruded moulding is slurried, Dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；（II）Carrier is contacted with carbon source, carbon deposit reaction is then carried out, obtains To carbon deposit carrier；（III）The carbon deposit carrier is roasted in oxygen-containing gas, obtains de- high-area carbon；The de- high-area carbon Carbon content be the carbon deposit carrier carbon content 20%~80%；Wherein, the oxygen content of the oxygen-containing gas be 0.5v%~ 8v%；Calcination temperature is 250~390 DEG C, and roasting time is 3.5~20h；（IV）Active metal group is introduced to the de- high-area carbon Divide precursor and drying；（V）By step（IV）Obtained product is heat-treated, and the active metal component precursor is changed into Reactive metal oxides, and retain the charcoal on the decarburization carrier.

8. technique according to claim 7, it is characterised in that：The carbon source is selected from petroleum ether, benzene,toluene,xylene, urges Change at least one of gasoline, coker gasoline, butadiene, pentadiene, hexadiene, butylene, amylene, heptene and nonene.

9. technique according to claim 7, it is characterised in that：The condition that the carrier is contacted with carbon source includes：Pressure For 0.1~1 MPa, the time is 0.1~6 h.

10. technique according to claim 7, it is characterised in that：The carbon deposit reaction carries out in the presence of oxygen-containing atmosphere, product Charcoal reaction temperature is 100~500 DEG C, and the carbon deposit reaction time is 20~200 h；The oxygen content of oxygen-containing atmosphere be 10v~ 100v%。

11. technique according to claim 7, it is characterised in that：Step（III）In, the calcination temperature is 300~390 DEG C, roasting time is 4~20h.

12. technique according to claim 7, it is characterised in that：The heat treatment includes：By step（IV）Obtained product 2~10h of roasting is carried out at inert gas and 400~700 DEG C, obtains hydrocracking catalyst.

13. technique described in accordance with the claim 1, it is characterised in that：The preparation method of lower bed layer catalyst, including it is following interior Hold：（1）Aluminium oxide and liquid or gaseous unsaturated olefin are come into full contact with, carbon deposit reaction is then carried out in oxygen-containing atmosphere, Obtain carbon deposit aluminium oxide；（2）Carbon deposit aluminium oxide, modified Y molecular sieve, active metallic compound containing Mo and the chemical combination of active metal containing Co Object is uniformly mixed, and dust technology is added, rear extruded moulding is slurried, dry, roasting obtains catalyst.

14. technique according to claim 13, it is characterised in that：The unsaturated olefin is that carbon atom number is 2 ~ 10 Positive structure or isomeric olefine, alkadienes；It refers to that unsaturated olefin diffuses into point that the wherein described alkene comes into full contact with molecular sieve Son sieve is internal；When using gaseous state unsaturated olefin, gaseous state unsaturated olefin is with molecular sieve contact conditions：Pressure 0.1 ~ 1.0MPa, 0.1 ~ 2 hour time of contact；When using liquid unsaturated hydrocarbons, liquid unsaturated olefin and molecular sieve contact conditions For：0.1 ~ 1.0MPa of pressure, 0.5 ~ 4 hour time of contact, molecular sieve answers thorough impregnation in liquefied olefines.

15. technique according to claim 13, it is characterised in that：The oxygen-containing atmosphere is air, oxygen and nitrogen One kind in the mixture of mixture or oxygen and inert gas, the volume fraction of oxygen in the gas phase are 10% ~ 100%；Carbon deposit Reaction condition is：50 ~ 500 DEG C of reaction temperature, reaction time are 1 ~ 200 hour.

16. technique according to claim 13, it is characterised in that：In the carbon deposit aluminium oxide, with carbon deposit aluminium oxide weight On the basis of amount, carbon content is 0.5wt% ~ 20wt%, and the Kong Rong ratios of aluminium oxide are 1 before carbon deposit aluminium oxide and non-carbon deposit:10~1:1.5.

17. technique according to claim 13, it is characterised in that：The content of the active metallic compound containing Mo presses phase It is 4wt% ~ 20wt% to answer oxide meter accounting, the content of the active metallic compound containing the Co accounting based on corresponding oxide be 2 wt% ~ 15wt%。

18. technique according to claim 13, it is characterised in that：The drying condition is：Dry 2 at 90 ~ 150 DEG C ~ 8 hours；After drying process, the carbon distribution in aluminium oxide roasts removing or in an inert atmosphere roasting guarantor in oxygen-containing atmosphere It stays in the catalyst；Roasting condition is：It is roasted 1 ~ 5 hour at 300 ~ 600 DEG C.

19. technique described in accordance with the claim 1, it is characterised in that：Modified Y molecular sieve property is as follows：SiO₂/Al₂O₃Molar ratio 8 ~ 50,500~900m of specific surface area²/ g, hole hold 0.30~0.60ml/g, relative crystallinity 80%~130%, cell parameter 2.432~2.460nm, 0.4~1.5mmol/g of meleic acid amount.

20. technique described in accordance with the claim 1, it is characterised in that：The process conditions of the hydrofining reaction are：Reaction It is 4.0~15.0 MPa that temperature, which is 320~440 DEG C of reaction pressures, and volume space velocity is 0.2~6.0h when liquid^-1, hydrogen to oil volume ratio is 100~2000.

21. technique described in accordance with the claim 1, it is characterised in that：The process conditions of the hydrocracking reaction are：Reaction Temperature is 340~440 DEG C, and reaction pressure is 4.0~15.0 MPa, and volume space velocity is 0.2~6.0h when liquid^-1, hydrogen to oil volume ratio It is 100~2000.

22. technique described in accordance with the claim 1, it is characterised in that：The property of the catalytic cracking diesel oil is：Density is 0.88 ~0.99g/cm³, it is 360~400 DEG C to do, and arene content is 50wt%~95wt%.Sulfur content is 0.2wt%~2wt%, and nitrogen contains Amount is 500~2000ppm.