CN107304375A - A kind of catalytic diesel oil conversion process catalyst grade matches somebody with somebody process - Google Patents

A kind of catalytic diesel oil conversion process catalyst grade matches somebody with somebody process Download PDF

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Publication number
CN107304375A
CN107304375A CN201610252798.8A CN201610252798A CN107304375A CN 107304375 A CN107304375 A CN 107304375A CN 201610252798 A CN201610252798 A CN 201610252798A CN 107304375 A CN107304375 A CN 107304375A
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China
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molecular sieve
acid
reaction
catalyst
accordance
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CN107304375B (en
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柳伟
杜艳泽
秦波
高杭
张晓萍
董立廷
贝耀明
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Abstract

Match somebody with somebody process, including herein below the invention discloses a kind of catalytic diesel oil conversion process catalyst grade：（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, the hydrocracking catalyst bed haptoreaction with grading loading in cracker；Two hydrocracking catalyst beds wherein in hydrocracking reactor, upper bed layer uses the hydrocracking catalyst using Mo Co as active metal component, and lower floor uses the hydrocracking catalyst that Mo Ni or W Ni are active metal component；（3）Step（2）Obtain hydrocracking reaction effluent and obtain naphtha component and diesel component through separating and being fractionated.The inventive method, there is provided device liquid receipts, reduces the hydrogenation saturation of the gasoline component of generation on the premise of catalytic diesel oil conversion ratio is met, and improves gasoline component octane number.

Description

A kind of catalytic diesel oil conversion process catalyst grade matches somebody with somebody process
Technical field
The present invention relates to a kind of hydrocarbon hdyrotreating method, specifically a kind of catalytic diesel oil conversion process catalyst grade With process.
Background technology
Since the new century, with the increasingly enhancing of people's environmental consciousness, the increasingly strict of national environmental protection regulation and The fast development of national economy, countries in the world are all being continuously increased to the demand for cleaning automotive fuel.Catalytic cracking（FCC）Technology It is one of 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 domestic increasingly heavy for processing crude quality Change, the raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, many enterprises are in order to reach improvement quality of gasoline in addition Or the purpose of propylene enhancing, to catalytic cracking unit transform or improve the operating severity of catalytic cracking unit, led The product of catalytic cracking is caused, the quality of particularly catalytic diesel oil more deteriorates.
To improve the utilization rate of petroleum resources, the total quality level of petrol and diesel oil fuel is improved, realizes that product blending is optimal Change and the maximized target of value of the product, meet the country to clean fuel increasing need, high aromatics diesel hydro-conversion The novel technique that is hydrocracked of production high added value naphtha component and low-sulfur cleaning diesel fuel has before application well Scape.Domestic and international researcher has also carried out substantial amounts of research work.It is external to be catalyzed using hydrocracking process technology Cracking light cycle oil is converted into the relevant report of ultra-low-sulphur diesel and high octane value gasoline blending component.Such as：Nineteen ninety-five NPRA Meeting, David A.Pappal et al. are described by Mobil, Akzo Nobel/Nippon Ketjen and M.W.Kellogg companies A kind of single-stage hydrocracking technology of exploitation；NPRA meetings in 2005, Vasant P. Thakkar et al. describe UOP The LCO UnicrackingTM technologies of company's exploitation.It is reported that both the above technology can be by the catalytic cycle oil group of low value Divide and be converted into high octane gasoline component and fine-quality diesel oil blending component.The yield and octane number of the gasoline component of technology production It is a good and bad important indicator of the technology, therefore, how the hydrogenation of gasoline component is reduced on the premise of high conversion is ensured Saturation is the key of the technology.
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 is contacted after first passing around pretreatment with Cracking catalyst, production cleaning diesel oil and high-new alkane value gasoline.But It is, the hydrogenation saturation for the reduction gasoline component that this method can not be selective, 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 up of beta-molecular sieve and boehmite, vib and group VIII active metal component is added using conventional method, but Catalyst is same stronger to gasoline component saturability, is unfavorable for catalytic diesel oil hydro-conversion production high-knock rating gasoline process.
The content of the invention
Problem present in high-knock rating gasoline technology is converted into for poor quality catalytic cracking diesel, the invention provides one Plant catalytic diesel oil conversion process catalyst grade and match somebody with somebody process, preferably on the premise of catalytic diesel oil conversion ratio is met, to carry Received for device liquid, reduce the hydrogenation saturation of the gasoline component of generation, improve gasoline component octane number.
The catalytic diesel oil conversion process catalyst grade of the present invention matches somebody with somebody process, including herein below：
（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, is hydrocracked with grading loading in cracker Beds haptoreaction；
（3）Step（2）Obtain hydrocracking reaction effluent and obtain naphtha component and diesel component through separating 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 the inventive method, the Hydrobon catalyst and hydrocracking catalyst of selection can use commercially available prod, It can be prepared according to this area Conventional wisdom.Hydrobon catalyst used in the present invention can use conventional hydrocracking pretreatment Catalyst, typically using group vib and/or group VIII metal as active component, using aluminum oxide or silicon-containing alumina as carrier.The Group vib metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.On the basis of the weight of catalyst, the Group vib tenor is calculated as 8wt%~28wt% with oxide, and group VIII tenor is calculated as 2wt%~15wt% with oxide.
Described hydrocracking catalyst, wherein upper bed layer catalyst are using Mo-Co as active metal component, with containing modified Y The aluminum oxide and/or amorphous silica-alumina of molecular sieve are carrier, with catalyst weight, MoO3 10%~18%, CoO 2%~10%, Modified Y molecular sieve 40%~90%, preferably 50%~80%, surplus is aluminum oxide and/or amorphous silica-alumina；Lower bed layer catalyst with Mo-Ni or W-Ni is active metal component, and aluminum oxide and/or amorphous silica-alumina containing modified Y molecular sieve and modified beta molecular sieve are Carrier, with catalyst weight, MoO3 Or WO315%~30%, NiO 2%~15%, modified Y molecular sieve 5%~50%, preferably 10% ~30%, beta-molecular sieve 5%~50%, preferably 10%~30%, surplus is aluminum oxide and/or amorphous silica-alumina.
The modified Y molecular sieve and modified beta molecular sieve that the present invention is used can be conventional method modified molecular screens, modified Y points Son sieve property is as follows：SiO2/Al2O3Mol ratio 8 ~ 50, preferably 10 ~ 30；The m of specific surface area 500~9002/ g, preferably 600~800 m2/g；0.30~0.60ml/g of pore volume, preferably 0.35~0.50ml/g of pore volume；Relative crystallinity 80%~130%, preferably 90%~ 110%, cell parameter 2.432~2.460, preferably 2.435~2.450；Meleic acid 0.4~1.5mmol/g of amount, preferably 0.5 ~ 1.3 mmol/g；Modified beta molecular sieve property is as follows：400 ~ 800m of specific surface area2/ g, preferably 500 ~ 700m2/g；0.2 ~ 0.60ml/ of pore volume G, preferably 0.3 ~ 0.5ml/g；Infrared 0.1 ~ 0.6mmol/g of acid content, preferably 0.2 ~ 0.5mmol/g； SiO2/Al2O3Mol ratio 30 ~ 100, preferably 40 ~ 80.
Wherein, upper bed layer catalyst is as follows using the preferred modification process of modified Y molecular sieve：（1）Close in conventional manner Into Y molecular sieve be that former powder carries out Ammonium Salt Ionic exchange in ammonium salt aqueous solution；（2）To step（1）In after obtained ammonium exchanges Y molecular sieve carry out either shallow dealuminzation or dealumination complement silicon；（3）To step（2）Y molecular sieve after processing is handled with aluminum salt solution, Dry；（4）By liquid or gaseous unsaturated olefin and step（3）The Y molecular sieve of acquisition is fully contacted, then in oxygen-containing atmosphere Middle progress carbon deposit reaction；（5）By step（4）The carbon deposit Y molecular sieve quick high-temp calcination process of preparation；（6）By step（5）Obtain Molecular sieve carry out deep sealumination modified processing；（7）Step（6）The Y molecular sieve of acquisition carries out processing of making charcoal, obtained after filtering, drying To the Y molecular sieve of pretreatment；
Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：Using NaY zeolite as raw material, wherein SiO in NaY molecular sieve2/ Al2O3Mol ratio is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Wherein ammonium salt is ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate Or the one or more in ammonium oxalate, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0 ~ 3.0 mol/L, 60 ~ 120 DEG C, exchanged at preferably 60 ~ 90 DEG C, swap time is 1 ~ 3 hour, exchange times are 1 ~ 4 time, the NaY boilings after finally being exchanged Stone Na2O content is less than 3.0%.
Step（2）The either shallow dealuminzation or dealumination complement silicon process can be hydro-thermal process, acid treatment or ammonium fluosilicate process In one or more：Wherein, step is worked as（2）During for hydrothermal treatment process, treatment temperature be 400 ~ 600 DEG C, pressure be 0.01 ~ 0.5MPa, processing time is 1.0 ~ 4.0 hours；Work as step（2）During for acid treatment process, acid used is sulfuric acid, hydrochloric acid, nitre One or more in acid, citric acid, oxalic acid and acetic acid, acid solutions are with H+0.1 ~ 0.7mol/L is calculated as, acid solution is with dividing The mixed proportion of son sieve is according to the solid mass ratio 3 of liquid:1~30:1,30 ~ 80 DEG C for the treatment of temperature, processing time is 0.5 ~ 3h；Work as step （2）During for ammonium fluosilicate dealumination complement silicon process, its method adds water for Y molecular sieve is made into the water sample mixing of the solid mass ratio 3 ~ 6 of liquid, so Afterwards, it is that 0.3 ~ 1.2mol/L ammonium fluosilicates aqueous solution is handled 0.5 ~ 2 hour in 50 ~ 80 DEG C to add concentration.
Step（3）Aluminium salt used in described aluminium salt processing procedure be one kind in aluminium chloride, aluminum sulfate or aluminum nitrate or A variety of, aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and processing time is 0.5 ~ 3 hour.Step（3）Middle aluminium The drying means of Y molecular sieve after salt treatment is 100 ~ 400 DEG C of 0.5 ~ 4h of heating, removes the moisture in molecular sieve.
Step（4）Described unsaturated olefin is alkene, the alkadienes of the positive structure that carbon number is 2 ~ 10 or isomery；Wherein Described alkene is fully contacted with molecular sieve refers to that unsaturated hydrocarbons is diffused into inside molecular sieve, if from liquid unsaturated hydrocarbons, Then molecular sieve answers thorough impregnation in liquefied olefines.
Step（4）Described oxygen-containing atmosphere is air, the mixture or oxygen of oxygen and nitrogen and the mixing of inert gas One kind in thing, 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 of degree, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 50 hour, preferably 2 ~ 40 hours.
Step（5）Described quick high-temp calcination process process is：The Y molecular sieve of carbon deposit is directly added into and is warming up in advance 400 ~ 600 DEG C of Muffle kiln roasting 5 ~ 300 minutes, preferably 5 ~ 60 minutes.
Step（6）Described in deep sealumination modified processing procedure can be acid treatment or ammonium fluosilicate processing, when for acid treatment Can be the one or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid and acetic acid using acid, acid concentration is with H during process+ It is calculated as 0.2 ~ 2mol/L；Acid solution and step（5）The mixed proportion of gained molecular sieve is generally according to the solid mass ratio 3 of liquid:1~30:1； 60 ~ 120 DEG C for the treatment of temperature, processing time is 0.5 ~ 3h；Work as step（6）During for ammonium fluosilicate processing procedure, its method is will step Suddenly（4）Obtained Y molecular sieve, which adds water, is made into the water sample mixing of the solid mass ratio 3 ~ 6 of liquid, and then, addition concentration is 0.8 ~ 2mol/L fluorine silicon Sour aqueous ammonium is handled 1 ~ 4 hour in 70 ~ 100 DEG C.
Step（7）Described treatment conditions of making charcoal are：It is calcined 2 ~ 4 hours, is remained on removing molecular sieve at 400 ~ 600 DEG C Carbon deposit.
In the inventive method, the process conditions of described hydrofining reaction are：Reaction temperature is 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 during liquid-1, preferably 0.5~3.0h-1；Hydrogen to oil volume ratio is 100~2000, preferably 500~1500.
In the inventive method, the process conditions of described hydrocracking reaction are：Reaction temperature is 340~440 DEG C, preferably 360~430 DEG C；Reaction pressure is 4.0~15.0 MPa, preferably 6.0~12.0 MPa；Volume space velocity is 0.2~6.0h during liquid-1, preferably 0.5~3.0h-1；Hydrogen to oil volume ratio is 100~2000, preferably 500~1500.
In the inventive method, the property of the catalytic cracking diesel oil is generally：Density is 0.88~0.99g/cm3, it is done 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 is 500~2000ppm.
Compared with prior art, the advantage of catalytic cracking diesel oil method for transformation of the invention is：Catalytic diesel oil hydrogenation turns Change technology production gasoline component composition is mainly mononuclear aromatics, monocyclic naphthenes and alkane.Its paraffin and monocyclic cycloalkanes Hydrocarbon especially linear paraffins are low octane rating component.The main saturation including mononuclear aromatics in the source of monocyclic naphthenes and bicyclic The ring-opening reaction of cycloalkane；The source of alkane can be then chain-breaking reaction or the polycyclic aromatic hydrocarbon open loop of original alkyl-substituted aromatic hydrocarbon Chain rupture is produced again.From the point of view of reaction angle, to realize high gasoline yield, the open loop chain rupture of the cycloalkanes aromatic hydrocarbons of hydrogenation saturation generation and Original alkyl-substituted aromatic hydrocarbon chain rupture is difficult to avoid in raw material, then may be used but if certain isomerization can be carried out to branched paraffin To improve the octane number of this portion of paraffins.For monocyclic naphthenes reduction, then need while cracking rate is ensured, reduction is single The saturation of PAH.Therefore, the selectivity for improving cracking and hydrogenation saturated reaction is to improve the key of gasoline component octane number.Work There are following characteristics in the cracker on industry device：Cracking zone top reaction temperature is general between 360 ~ 380, such temperature Degree is conducive to playing the hydrogenation saturability of catalyst, therefore, and cracking agent too high hydrogenation activity in top will promote aromatic hydrocarbons saturation Reaction, is unfavorable for improving gasoline component octane number.And bottom bed reaction temperature typically can reach 400 DEG C, such temperature makes Obtain aromatic hydrocarbons saturated reaction to be limited by thermodynamical equilibrium, be unfavorable for carrying out hydrogenation saturated reaction, meanwhile, the too high reaction temperature of lower floor Also so that cracking excessively, increases gasoline component second pyrolysis, gasoline component yield is reduced, a large amount of gas components are produced.Therefore, It is hydrocracked with the selective angle of aromatic hydrocarbons saturation to consider from raising, the present invention loads low hydrogenation activity/height on cracking zone top Cracking activity catalyst, so that upper bed layer catalyst hydrogenation ability is weaker, even in the technique bar for being relatively adapted to aromatic hydrocarbons saturation Under part also will not supersaturation, meanwhile, the higher cracking activity of upper bed layer, which is also increased, urges bavin conversion ratio to generate more gasoline Component, in addition, top cracking agent is prepared using molecular sieve using specific process has active and anti-nitrogen concurrently, is also more applicable for top High nitride reaction environment, meets high resistance to nitrogen ability and the reaction requirement of high reaction activity；And cracking pars infrasegmentalis can then be loaded High hydrogenation activity/low cracking activity catalyst, due to the reaction temperature that lower floor is too high, even if using the cracking agent of high hydrogenation activity It also is difficult to play aromatic hydrocarbons saturability, and high hydrogenation activity is then conducive to C+The terminating reaction of ion, splits with reference to lower floor is weaker Change activity, reduce gasoline component secondary cracking, improve gasoline yield.In addition, with the addition of β points in reactor lower part cracking agent Son sieve is also beneficial to improve catalyst isomerism ability, so as to further lift gasoline products octane number.
Embodiment
Below by embodiment, the present invention is further described, but is not so limited the present invention.It is described in the inventive method Body phase silica alumina ratio measured using chemical analysis.Top layer silica alumina ratio uses transmission electron microscope X-ray electronic spectroscopy Measure.
Embodiment 1
The preparation method of molecular sieve 1 and physico-chemical property：
（1）The former powder 200g of NaY molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 1.5mol/L with concentration is according to liquid-solid ratio 4:1 Mixing, 80 DEG C exchange 2 hours, repeat this process 2 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.5%；
（2）To step（1）560 DEG C of obtained Y molecular sieve, 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, 75 DEG C is then heated to, in stirring During add 0.6mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours.
（4）First by step（3）The dry 3h of 120 DEG C of gained molecular sieve, then, takes hexadiene soaking step（3）Point of gained Son sieve 2 hours, then, is heated 4 hours in air atmosphere at 150 DEG C；
（5）Step（4）Molecular sieve after processing, which is directly placed into, to be previously heated in 450 DEG C of Muffle furnace, is calcined 10 minutes；
（6）Step（5）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, and it is 0.8mol/L's to add concentration Ammonium fluosilicate solution 100ml, 95 DEG C are handled 2 hours；
（7）Through step（6）After Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, 550 DEG C of roastings 2 hours, acquisition Molecular sieve 1 used in embodiment.The transmission electron microscope EDAX results of gained molecular sieve 1 determine its outer surface to 80nm thickness, surface Layer silica alumina ratio is 42, and molecular sieve body phase silica alumina ratio is 11.5.XRD analysis result shows that its lattice constant is 2.441, relative crystallization Degree 96%.Pore volume 0.36ml/g, specific surface area 740m2/ g, it is 0.90mmol/g that infrared analysis result, which determines Y-1 meleic acids amount,.
Embodiment 2
The modification process of molecular sieve 2：
（1）The former powder 200g of NaY molecular sieve for taking laboratory to prepare, the ammonium nitrate for being 0.6mol/L with concentration is according to liquid-solid ratio 3:1 Mixing, 80 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）530 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1Mpa；
（3）Step（2）Sieve is according to liquid-solid ratio 8:1 and 0.5mol/L oxalic acid solution（Concentration is with H+Meter）400ml is mixed, Ran Housheng Temperature is to 50 DEG C, isothermal reaction 2 hours；
（4）Step（3）Gained molecular sieve is according to liquid-solid ratio 5:1 mixes with distilled water stirring, 80 DEG C is then heated to, in stirring During add 0.5mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours.
（5）Step（4）The dry 9h of 100 DEG C of gained molecular sieve；
（6）Take hexadiene soaking step（5）The molecular sieve of gained 3 hours, then, 150 DEG C are heated 25 hours in air atmosphere；
（7）Step（6）Molecular sieve after processing, which is directly placed into, to be previously heated in 400 DEG C of Muffle furnace, is calcined 35 minutes；
（8）Step（7）The molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with distilled water, then, and addition concentration is 1.0 mol/L Ammonium fluosilicate solution 100ml, 75 DEG C are handled 2 hours；
（9）Through step（8）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours after 550 DEG C are calcined 2 hours, are obtained Molecular sieve 2.
The transmission electron microscope EDAX results of molecular sieve 2 determine its outer surface to 140nm thickness, and superficial layer silica alumina ratio is 50, Molecular sieve body phase silica alumina ratio is 20.XRD analysis result shows that its lattice constant is 2.434, relative crystallinity 97%.Pore volume 0.38 Ml/g, specific surface area 680m2/ g, it is 0.66mmol/g that infrared analysis result, which determines meleic acid amount,.
Embodiment 3
The preparation method of molecular sieve 3 and physico-chemical property：
Y molecular sieve uses conventional method modification, that is, takes NaY molecular sieve ammonium first to exchange to Na2O content 2.0%, then, with 0.10mol/L ammonium fluosilicate solutions are according to liquid-solid ratio 10:1 mixing is warming up to after 80 DEG C, isothermal reaction 2h, ammonium fluosilicate processing Afterwards, sample hydro-thermal process 2h at a temperature of 0.1MPa, 540 DEG C after filtering, washing obtains molecular sieve 3.The silica alumina ratio of molecular sieve 3 is 15.0.XRD analysis result shows that its lattice constant is 2.442, relative crystallinity 92%.Pore volume 0.36ml/g, infrared analysis result It is 0.93mmol/g to determine meleic acid amount.
Embodiment 4
The preparation method of molecular sieve 4 and physico-chemical property：
Using conventional method modification, i.e. beta-molecular sieve, conventionally ammonium is exchanged to sodium oxide content and is less than beta-molecular sieve After 1.0%, first, the hydro-thermal process 2h under 1.0Mpa, 580 DEG C of operating conditions, then the dust technology with 0.5mol/L is solid according to liquid Mass ratio 10:90 DEG C of isothermal reaction 2h, gained molecular sieve SiO after 1 mixing2/Al2O3Mol ratio is 60, specific surface area 550m2/ G, pore volume 0.34ml/g, it is 0.30mmol/g that infrared analysis result, which determines meleic acid amount,.
Embodiment 5
The preparation method of catalyst 1 and physico-chemical property：
（1）Take the 70g of molecular sieve 1 to prepare macroporous aluminium oxide with 30g conventional methods to mix, add 4g/100ml dust technologies in mixing Mixing is rolled to extrudable shape in device, and extruded moulding obtains carrier T-1 on banded extruder；
（2）T-1 is taken to be impregnated in Mo-Co active metal maceration extracts, impregnated sample obtains catalyst after drying, roasting, numbers For C-1.Catalyst pore volume 0.40ml/g, specific surface area 430m2/ g, MoO315wt%, CoO 5wt%；
Embodiment 6
The preparation method of catalyst 2 and physico-chemical property：
（1）Take the 20g of molecular sieve 3, the 10g of molecular sieve 4 to prepare macroporous aluminium oxide with 70g conventional methods and mix, add 4g/100ml Dust technology is mixed in a mixer to roll to extrudable shape, and extruded moulding obtains carrier T-2 on banded extruder；
（2）T-2 is taken to be impregnated in W-Ni active metal maceration extracts, impregnated sample obtains catalyst after drying, roasting, numbers For C-2.Catalyst pore volume 0.41ml/g, specific surface area 280m2/ g, WO320wt%, NiO 6wt%；
Embodiment 7
The preparation method of catalyst 3 and physico-chemical property：
（1）Take the 70g of molecular sieve 3 to prepare macroporous aluminium oxide with 30g conventional methods to mix, add 4g/100ml dust technologies in mixing Mixing is rolled to extrudable shape in device, and extruded moulding obtains carrier T-3 on banded extruder；
（2）T-3 is taken to be impregnated in Mo-Co active metal maceration extracts, impregnated sample obtains catalyst after drying, roasting, numbers For C-3.Catalyst pore volume 0.39ml/g, specific surface area 420m2/ g, MoO315wt%, CoO 5wt%；
Embodiment 8
The preparation method of catalyst 4 and physico-chemical property：
（1）Take the 30g of molecular sieve 3 to prepare macroporous aluminium oxide with 70g conventional methods to mix, add 4g/100ml dust technologies in mixing Mixing is rolled to extrudable shape in device, and extruded moulding obtains carrier T-4 on banded extruder；
（2）T-4 is taken to be impregnated in W-Ni active metal maceration extracts, impregnated sample obtains catalyst after drying, roasting, numbers For C-4.Catalyst pore volume 0.42ml/g, specific surface area 300m2/ g, WO320wt%, NiO 6wt%；
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 and once produces gasoline and hydrogenated diesel oil, an anti-filling by flow Regular refiner catalyst, two instead load different preparation method and different gradation mode catalyst systems, catalyst for refining reason respectively Change property, raw material oil nature and evaluation result and be listed in table 1 ~ 4.
The anti-catalyst for refining physicochemical property of table 1 one
The raw material oil nature of table 2
The type of feed and operating condition of the anticatalyst of table 3 two.
The product of table 4 is distributed and property contrast.

Claims (14)

1. a kind of catalytic diesel oil conversion process catalyst grade matches somebody with somebody process, including herein below：（1）Catalytic cracking diesel oil and hydrogen The mixed material of gas is introduced into hydrogenation reactor and carries out hydrofining reaction；（2）Hydrofining reaction effluent, which is directly entered, to be split Change the hydrocracking catalyst bed haptoreaction of grading loading in reactor, with cracker；Wherein hydrocracking reaction Two hydrocracking catalyst beds in device, wherein upper bed layer catalyst are using Mo-Co as active metal component, with containing modified Y points The aluminum oxide and/or amorphous silica-alumina of son sieve are carrier, with catalyst weight, MoO310%~18%, CoO 2%~10%, changes Property Y molecular sieve 40%~90%, surplus be aluminum oxide and/or amorphous silica-alumina；Lower bed layer catalyst is using Mo-Ni or W-Ni as activity Metal component, aluminum oxide and/or amorphous silica-alumina containing modified Y molecular sieve and modified beta molecular sieve are carrier, with catalyst weight Meter, MoO3Or WO3 15%~30%, NiO 2%~15%, modified Y molecular sieve 5%~50%, beta-molecular sieve 5%~50%, surplus is oxidation Aluminium and/or amorphous silica-alumina；Two bed hydrocracking catalyst mass ratioes are 1 up and down：5~5：1；（3）Step（2）Added Hydrogen cracking reaction effluent obtains naphtha component and diesel component through separating and being fractionated.
2. in accordance with the method for claim 1, it is characterised in that：Described modified Y molecular sieve property is as follows：SiO2/Al2O3 Mol ratio 8 ~ 50,500~900m of specific surface area2/ g, 0.30~0.60ml/g of pore volume, relative crystallinity 80%~130%, structure cell ginseng Number 2.432~2.460,0.4~1.5mmol/g of meleic acid amount；Modified beta molecular sieve property is as follows：400 ~ 800m of specific surface area2/ G, pore volume 0.2 ~ 0.60ml/g, infrared 0.1 ~ 0.6mmol/g of acid content, SiO2/Al2O3Mol ratio 30 ~ 100.
3. in accordance with the method for claim 1, it is characterised in that：Upper bed layer catalyst uses modified Y molecular sieve modification Process is as follows：（1）The Y molecular sieve synthesized in conventional manner is that former powder carries out Ammonium Salt Ionic exchange in ammonium salt aqueous solution；（2）It is right Step（1）In obtained ammonium exchange after Y molecular sieve carry out either shallow dealuminzation or dealumination complement silicon；（3）To step（2）Y after processing Molecular sieve is handled with aluminum salt solution, is dried；（4）By liquid or gaseous unsaturated olefin and step（3）The Y molecular sieve of acquisition fills Tap is touched, and carbon deposit reaction is then carried out in oxygen-containing atmosphere；（5）By step（4）The carbon deposit Y molecular sieve quick high-temp roasting of preparation Processing；（6）By step（5）Obtained molecular sieve carries out deep sealumination modified processing；（7）Step（6）The Y molecular sieve of acquisition through filtering, After drying, processing of making charcoal is carried out, modified Y molecular sieve is obtained.
4. in accordance with the method for claim 3, it is characterised in that：Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：With NaY zeolite is raw material, wherein SiO in NaY molecular sieve2/Al2O3Mol ratio is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%, ammonium Saline solution 0.3 ~ 6.0mol/L of concentration, at 60 ~ 120 DEG C, swap time is 1 ~ 3 hour, and exchange times are 1 ~ 4 time, are finally obtained NaY zeolite Na after must exchanging2O content is less than 3.0%.
5. in accordance with the method for claim 3, it is characterised in that：Step（2）The either shallow dealuminzation or dealumination complement silicon process are One or more during hydro-thermal process, acid treatment or ammonium fluosilicate.
6. in accordance with the method for claim 5, it is characterised in that：Work as step（2）During for hydrothermal treatment process, treatment temperature is 400 ~ 600 DEG C, pressure is 0.01 ~ 0.5MPa, and processing time is 1.0 ~ 4.0 hours；Work as step（2）During for acid treatment process, institute It is the one or more in sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid and acetic acid with acid, acid solutions are with H+It is calculated as 0.1 ~ The mixed proportion of 0.7mol/L, acid solution and molecular sieve is according to the solid mass ratio 3 of liquid:1~30:1,30 ~ 80 DEG C for the treatment of temperature, processing Time is 0.5 ~ 3h；Work as step（2）During for ammonium fluosilicate dealumination complement silicon process, its method adds water for Y molecular sieve and is made into liquid stereoplasm Water sample mixing of the amount than 3 ~ 6, then, it is that 0.3 ~ 1.2mol/L ammonium fluosilicates aqueous solution handles 0.5 ~ 2 in 50 ~ 80 DEG C to add concentration Hour.
7. in accordance with the method for claim 3, it is characterised in that：Step（3）Aluminium salt used in described aluminium salt processing procedure It is the one or more in aluminium chloride, aluminum sulfate or aluminum nitrate, aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, processing time is 0.5 ~ 3 hour.
8. in accordance with the method for claim 3, it is characterised in that：Step（3）Described drying condition is：At 100 ~ 400 DEG C Dry 0.5 ~ 4h.
9. in accordance with the method for claim 3, it is characterised in that：Step（4）Described unsaturated olefin is that charcoal atomicity is 2 ~ 10 positive structure or alkene, the alkadienes of isomery.
10. in accordance with the method for claim 3, it is characterised in that：Step（4）Described oxygen-containing atmosphere be air, oxygen with One kind in the mixture or oxygen of nitrogen and the mixture of inert gas, the volume fraction of oxygen in the gas phase be 10% ~ 100%；Carbon deposit reaction condition is：50 ~ 500 DEG C of reaction temperature, the reaction time is 1 ~ 50 hour.
11. in accordance with the method for claim 3, it is characterised in that：Step（5）Described quick high-temp calcination process process For：The Y molecular sieve of carbon deposit is directly added into and is warming up to 400 ~ 600 DEG C of Muffle kiln roasting 5 ~ 300 minutes in advance.
12. in accordance with the method for claim 3, it is characterised in that：Step（6）Described in deep sealumination modified processing procedure be acid Processing or ammonium fluosilicate processing；Work as step（6）During for acid treatment process, the acid used is sulfuric acid, hydrochloric acid, nitric acid, citric acid, grass One or more in acid, acetic acid, acid solutions are with H+It is calculated as 0.2 ~ 2mol/L, the mixed proportion of acid solution and molecular sieve is pressed According to the solid mass ratio 3 of liquid:1~30:1,60 ~ 120 DEG C for the treatment of temperature, processing time is 0.5 ~ 3h；Work as step（6）At ammonium fluosilicate During reason process, method is the water sample mixing that Y molecular sieve adds water and is made into the solid mass ratio 3 ~ 6 of liquid, then, add concentration be 0.8 ~ The 2mol/L ammonium fluosilicates aqueous solution is handled 1 ~ 4 hour in 70 ~ 100 DEG C.
13. in accordance with the method for claim 3, it is characterised in that：Step（7）Described treatment conditions of making charcoal are：400~600 It is calcined 2 ~ 4 hours at DEG C, the carbon deposit remained on removing molecular sieve.
14. in accordance with the method for claim 3, it is characterised in that：The process conditions of described hydrofining reaction are：Reaction Temperature is 320~440 DEG C, and reaction pressure is 4.0~15.0MPa, and volume space velocity is 0.2~6.0h during liquid-1, hydrogen to oil volume ratio is 100~2000；The process conditions of described hydrocracking reaction are：Reaction temperature be 340~440 DEG C, reaction pressure be 4.0~ 15.0 MPa, volume space velocity is 0.2~6.0h during liquid-1, hydrogen to oil volume ratio is 100~2000.
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