CN107345156A - A kind of method being hydrocracked - Google Patents

A kind of method being hydrocracked Download PDF

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Publication number
CN107345156A
CN107345156A CN201610289578.2A CN201610289578A CN107345156A CN 107345156 A CN107345156 A CN 107345156A CN 201610289578 A CN201610289578 A CN 201610289578A CN 107345156 A CN107345156 A CN 107345156A
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content
pore volume
modified zeolite
molecular sieve
accordance
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CN107345156B (en
Inventor
高波
刘昶
王凤来
关明华
杜艳泽
黄薇
赵红
郝文月
曹均丰
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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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • 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
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes 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
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of method being hydrocracked.This method contacts including wax oil raw material with hydrocracking catalyst carries out hydrocracking reaction, and obtained isocrackate obtains heavy naphtha, diesel oil, jet fuel and hydrogenation tail oil through separation；For hydrocracking catalyst wherein used using Modified Zeolite Y, amorphous silica-alumina and aluminum oxide as carrier, Modified Zeolite Y therein is a kind of Y type molecular sieve concentrated rich in mesoporous, effective pore sife distribution.The particularly suitable processing height of this method does wax oil, can effectively convert macromolecular aromatic component therein, the quality of production more excellent transportation fuel and industrial chemicals.

Description

A kind of method being hydrocracked
Technical field
The present invention relates to a kind of method being hydrocracked, particularly a kind of more preferable conversion height is done, the wax oil of high content is former The method for hydrogen cracking of material production clean traffic transport fuel.
Background technology
Whole world petroleum resources is fewer and fewer, and crude quality is also being deteriorated year by year, and this, which will turn into, restricts economic development An important factor for, international crude petroleum continues to run under high price, and the price differential of crude oil with poor quality and high-quality crude widens.Increase is inferior former Oily processing capacity, crude oil cost can be greatly reduced, improve oil refining enterprise's economic benefit.Raw material is done or cut scope is to be hydrocracked The highly important Con trolling index of raw material.It is directly connected to the quantity for being available for raw material, and has with technology level and economy Close.Do raising, there occurs very big change for feedstock oil composition and property：1）Density increase, boiling range increase, and 2）Point of hydrocarbon molecule Son amount increase, structure complicate, and 3）Chain hydrocarbon content is reduced, and cyclic hydrocarbon especially condensed ring hydrocarbon content increases sharply, and 4）BMCI values Increase, 5）Nitrogen, sulphur, carbon residue, asphalitine, metal impurities greatly increase.In addition with the raising done, to hydrocracking reaction Also very big influence is generated：1）Viscosity increase, the colourity increase of feedstock oil, influence diffusion velocity, reduce reaction speed, and 2）It is miscellaneous The increase of matter content, considerably increases the difficulty of hydrogenation, and 3）The increase of condensed ring hydrocarbon content, greatly accelerate the reaction of coking carbon deposit Speed, 4）The stability of influence catalyst, 5）The increase of nitrogen content has influence on the cracking activity of catalyst, and 6）Raw material oil viscosity Increase influence diffusion velocity of the raw material hydrocarbon molecule to catalytic inner, 7）Content liquid increase in gas, liquid, solid phase reaction, no Beneficial to the progress of reaction, 8）Exothermic heat of reaction increase, bed temperature rise increase.
Hydrocracking technology the advantages such as product structure is rationally adjustable, has strong so that its adaptability to raw material is good, good product quality The development prospect of strength.The application of hydrocracking technology will answer as improving petroleum product-quality, reduction environmental pollution, increasing market The effective technology measure of change ability, it has also become the mostly important process unit in modernization refinery.Simultaneously increasingly strict traffic fortune Defeated fuel emission standards make it that processing the problem of inferior heavy oil directly produces high quality clean fuel becomes increasingly conspicuous, maximum production The hydrocracking technology of intermediate oil and its supporting High middle distillate catalyst development are also more active.
Can there are Y types, β types and ZSM type molecules as the molecular sieve of cracking active component in hydrocracking heavy oil field Sieve etc., wherein Y type molecular sieve application is the most universal.The method of industrial production Y type molecular sieve is essentially all using beautiful at present The directing agent method that GRACE companies of state propose in USP 3639099 and USP 4166099, the Y type molecular sieve original powder duct of synthesis Orifice diameter be 0.74nm × 0.74nm, its micropore pore volume accounts for more than the 95% of total pore volume.Wax oil hydrogenation cracked stock In polycyclic heavy constituent molecular diameter generally in more than 1nm, the cracking reaction for heavy constituent macromolecular, be adapted to its reaction and production The preferable duct pore diameter range of thing diffusion is 2nm ~ 10nm macropore range, can be by outside more accessible acid centre Dew, while the also desorption and diffusion of the absorption beneficial to raw material macromolecular and reaction and purpose product, improve molecular sieve cracking choosing Selecting property.To improve the low situation for being unfavorable for wax oil macromolecular reaction of the mesoporous pore volume content of Y type molecular sieve, generally to Y type molecules Sieve former powder and be modified processing, can obtain the Modified Zeolite Y of different pore passage structures and acid distribution.
CN201310240740.8 discloses a kind of ultra-steady Y molecular sieve（USY）Method of modifying.The characteristics of this method be Organic acid and inorganic salts dealuminzation reagent are added in modifying process simultaneously, the combination for carrying out organic acid-inorganic salts is modified.Use this The mesopore volume of USY molecular sieve of the total volume less than 50% made from method reality, its crystallinity is below 85%.
CN201510147788.3 discloses Y molecular sieve that a kind of silica alumina ratio is high and second hole is abundant and preparation method thereof. This method includes：Y type molecular sieve is handled into 1 ~ 5h at 300 DEG C ~ 600 DEG C, dry Y type molecular sieve is obtained, is cooled to 200 ~ 600 ℃；In dried over anhydrous environment, it is passed through into dry Y type molecular sieve by the dry gas of dealumination complement silicon agent saturation, reaction 0.5h ~ 7h, or in dried over anhydrous environment, lead to while temperature to be at the uniform velocity warming up to 500 ~ 700 DEG C into dry y-type zeolite Enter by the dry gas of dealumination complement silicon agent saturation, react 0.5h ~ 7h, obtain crude product；By crude product at 30 ~ 100 DEG C at alkali 10min ~ 5h is managed, the solid-liquid mass ratio of alkali process is 1 ~ 50：1, obtain the Y molecular sieve that silica alumina ratio is high and second hole is abundant.
US4401556 discloses a kind of hydrocracking catalyst for being used to produce intermediate oil.The catalyst is to pass through The Y type molecular sieve for crossing dealuminzation is cracking active component, and its silica alumina ratio is 4.5 ~ 35,2.420 ~ 2.445nm of cell parameter, than Surface area is not less than 350m2/g.When the catalyst is to do as 600 DEG C of VGO as raw material, its activity is poor, middle distillates oil selectivity Also it is not high.
US4894142 discloses a kind of hydrocracking catalyst, is mainly used in the technique of voluminous intermediate oil.This is urged Agent contains amorphous silica-alumina and a kind of Y type molecular sieve of Low acid, is to handle raw material point at high temperature the characteristics of the molecular sieve Son sieve, including 680 ~ 780 DEG C of hydro-thermal process or the dry type for the being passed through inert gas heat treatment higher than 700 DEG C.Due to the molecule Acidity is sieved than relatively low, makes the activity of catalyst excessively relatively low, this requires to improve hydrocracking reaction temperature, the hot tearing of molecular sieve Change trend strengthens, but inhibits hydrogenation reaction, the middle distillates oil selectivity of catalyst is improved unobvious, product quality is also by bad Influence.
From the molecular sieve with cracking function from the point of view of the application during Industrial Catalysis, its performance depends primarily on following Two aspects：Selective absorption and reaction.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface It energy barrier, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, at this moment be adsorbed molecule and pass through molecular sieve crystal Hole and cage diffusion serve it is conclusive.Molecular sieve total pore volume and mesoporous pore volume prepared by conventional method of modifying It is less than normal, it is unfavorable for the conversion of raw material macromolecular, therefore the modification point that pore structure is open, mesoporous content is high and acid site exposure is more Son sieve can handle the raw material that molecule is bigger, oil product is heavier, improve macromolecular conversion probability etc. show it is more superior Performance, so as to lift the level of hydrocracking catalyst.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of method being hydrocracked.Present invention side Hydrocracking catalyst used in method be use a kind of Y type molecular sieve more concentrated rich in meso-hole structure, effective pore sife distribution for Cracking Component, can effectively convert height and do heavy aromatics component in wax oil raw material, the more excellent transportation fuel of the quality of production and Industrial chemicals.
The method being hydrocracked of the present invention, including wax oil raw material are contacted with hydrocracking catalyst and be hydrocracked instead Should, obtained isocrackate obtains heavy naphtha, diesel oil, jet fuel and hydrogenation tail oil through separation；Wherein used adds Hydrogen Cracking catalyst, including hydrogenation active metal component and carrier, carrier include Modified Zeolite Y, amorphous silica-alumina and oxygen Change aluminium, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio For 55 ~ 100, cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, is situated between Hole pore volume accounts for more than the 70% of total pore volume, preferably 80% ~ 95%.
The grain size of described Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
In described Modified Zeolite Y, mesoporous bore dia is 2 ~ 10nm.
The specific surface area of described Modified Zeolite Y is 650 ~ 1000m2/ g, preferably 750 ~ 1000m2/g。
The infrared total acid content of described Modified Zeolite Y is 0.1 ~ 0.5mmol/g.
In described Modified Zeolite Y, Na2O weight content is below 0.15wt%.
In described hydrocracking catalyst, described carrier, on the basis of the weight of carrier, Modified Zeolite Y Content is 10% ~ 50%, preferably 15% ~ 45%, and the content of amorphous silica-alumina is 5% ~ 30%, preferably 10% ~ 25%, and aluminum oxide contains Measure as 20% ~ 85%, preferably 30% ~ 75%.
For described hydrogenation active metals typically using vib and the metal of group VIII, vib metals are preferably molybdenum And/or tungsten, group VIII metal are preferably cobalt and/or nickel.In hydrocracking catalyst catalyst of the present invention, with the weight of catalyst On the basis of amount, vib metals（In terms of oxide）Content be 10.0% ~ 30.0%, group VIII metal（In terms of oxide） Content be 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 86.0%.
The property of hydrocracking catalyst of the present invention is as follows：Specific surface area is 250 ~ 450m2/ g, pore volume be 0.30 ~ 0.50mL/g。
The preparation method of hydrocracking catalyst of the present invention, include preparation and the load hydrogenation active metal component of carrier, The preparation process of wherein carrier is as follows：By Modified Zeolite Y, amorphous silica-alumina, aluminum oxide mix, shaping, then dry and Roasting, is made the preparation method of catalyst carrier, wherein Modified Zeolite Y, comprises the following steps：
（1）NaY types molecular sieve with（NH4）2SiF6Aqueous solution contact is reacted, through filtering and drying after reaction；
（2）To step（1）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.20 ~ 0.40MPa, temperature Spend for 600 ~ 800 DEG C, processing time is 0.5 ~ 5.0 hour；
（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing, Ran Houjing under the conditions of existing for organic formwork agent Filter and dry；
（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and the modification Y type molecules of the present invention are made Sieve.
The inventive method step（1）In, the property of NaY type molecular sieves is as follows：
SiO2/Al2O3Mol ratio be 3 ~ 6, preferably 4.5 ~ 5.5, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, relatively Crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, compares surface Product is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4 mL/g, and micropore pore volume accounts for more than the 75% of total pore volume.
The inventive method step（1）In,（NH4）2SiF6Addition for NaY type molecular sieve butt weight 5wt% ~ 20wt%。
The inventive method step（1）In,（NH4）2SiF6The mass concentration of the aqueous solution is 50 ~ 100g/L.NaY type molecular sieves With（NH4）2SiF6The reaction condition that aqueous solution contact is reacted：Temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, during reaction Between be 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
The inventive method step（1）In, NaY types molecular sieve with（NH4）2SiF6After aqueous solution contact is reacted, separation point Son sieve and accessory substance, can wash, refilter, dry, preferably dry after gained Y type molecular sieve butt for 60wt% ~ 80wt%.Dry condition is usually to be dried 0.5 ~ 5.0 hour at 50 ~ 95 DEG C.
The inventive method step（2）In, hydro-thermal process is to use saturated steam processing step（1）In obtained molecular sieve, Treatment conditions：0.20 ~ 0.40MPa of gauge pressure, preferably 0.25 ~ 0.40MPa, preferably 600 ~ 800 DEG C of temperature, 610 ~ 750 DEG C, place Manage 0.5 ~ 5.0 hour time, preferably 1.0 ~ 3.0 hours.
The inventive method step（3）In, organic formwork agent is tetraethyl ammonium hydroxide, TMAH, tetrapropyl One or more in ammonium hydroxide.Wherein, by step（2）In after obtained Y type molecular sieve uniformly mixes with organic formwork agent, Hydrothermal crystallizing is carried out, process is as follows：By step（2）In obtained Y type molecular sieve be beaten in the organic formwork agent aqueous solution, liquid is solid Weight ratio is 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and the mass concentration of the organic formwork agent aqueous solution is 3% ~ 10%, mixed material is then placed in crystallization in crystallizing kettle, crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, gauge pressure For 0.1 ~ 0.2MPa.After crystallization, filtered and drying can use conventional method to carry out, and typically dry condition is as follows：50 ~ 1 ~ 10h is dried at 110 DEG C.
In the inventive method, step（4）It is by step（3）Obtained Y type molecular sieve be calcined under low temperature oxygen-enriched atmosphere, Wherein oxygen-enriched atmosphere refers to that oxygen content is more than 50v%, and sintering temperature is 300 ~ 450 DEG C, and roasting time is 5 ~ 10h.Roasting is general Using the method being calcined under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min.
In the method for hydrogen cracking of the present invention, using one-stage serial technological process, it is necessary to enter before hydrocracking reaction Row hydrofinishing, its used Hydrobon catalyst can use conventional Hydrobon catalyst or be hydrocracked pre- place Catalyst is managed, typically using alumina-based supports, using vib and group VIII metal as hydrogenation active metal component, VI B Race's metal is preferably molybdenum and/or tungsten, and the metal of group VIII is preferably cobalt and/or nickel.On the basis of the weight of catalyst, the Group vib metal（In terms of oxide）Content be 15.0% ~ 30.0%, group VIII metal（In terms of oxide）Content be 4.0% ~8.0%。
The particularly suitable processing height of method for hydrogen cracking of the present invention does wax oil（Also referred to as height does vacuum distillate）, its Property is as follows：Density（20℃）For 0.9 ~ 1.0g/cm3, initial boiling point is 350 ~ 400 DEG C, is done as 700 ~ 750 DEG C, and sulfur content is 2.0wt% ~ 4.0wt%, nitrogen content are 2000 ~ 4000 μ g/g.
The method for hydrogen cracking of the present invention, used hydrocracking operation condition are as follows：Reaction stagnation pressure 12.0 ~ 20.0MPa, 0.5 ~ 2.0h of volume space velocity during liquid-1, hydrogen to oil volume ratio 1000：1~2000：1,370 ~ 435 DEG C of reaction temperature.
Hydrocracking catalyst used by the inventive method, wherein Y type molecular sieve are to use（NH4）2SiF6To NaY points Son sieve is modified processing, while modulation molecular sieve silica alumina ratio is realized, can take off the sodium ion in NaY molecular sieve together Go out, hydrothermal crystallizing then is carried out to the molecular sieve after hydro-thermal process in the presence of organic formwork agent, can so make part silicon atom Enter framework of molecular sieve structure under organic formwork agent effect with aluminium atom, in bone that is further stable and improving modified molecular screen While frame structure, caused non-skeleton structure in zeolite-water heat treatment process, unimpeded pore passage structure, the organic mould in part are eliminated Plate agent can be also entered in the duct of molecular sieve, coordinate follow-up oxygen-enriched low-temperature treatment, can be by the organic formwork in molecular sieve The controllable removing in order of agent, so as to produce a large amount of ordered mesopore structures, and pore size distribution is more concentrated.
Y type molecular sieve is acid suitably in hydrogen Cracking catalyst used by the inventive method, crystallinity is high, mesoporous institute's accounting Example is high, pore-size distribution is more concentrated.Because the Y type molecular sieve has bigger pore volume and mesopore volume, in more acidity The heart is exposed, and is advantageous to raw material heavy oil macromolecular and is cracked, but also with more preferably pore size distribution range, can be effective Ground controls the cracking degree of reactant, and is advantageous to product and is diffused in duct, so in cracking reaction, relative can increase Add activated centre, and heavy oil macromolecular can be made to carry out the cracking reaction of suitable degree, both improve the cracking capability of heavy oil, simultaneously Coke yield is reduced, catalyst can show good cracking activity and product selectivity.
When the inventive method is done in wax oil hydrogenation process especially suitable for height inferior, particularly under elevated pressure conditions When processing height does VGO feedstock, there is very high catalytic activity and transportation fuel yield, and product quality is obtained into one Step improves, while the stability of catalyst is preferable, the service life length of hydrocracking catalyst, can meet refinery's increase operation spirit Activity, increase device disposal ability, the economic benefit for further improving refinery.
Brief description of the drawings
Fig. 1 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of embodiment 1；
Fig. 2 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of comparative example 1；
Fig. 3 is the XRD diffraction patterns of the gained Modified Zeolite Y of embodiment 1.
Embodiment
Aluminum oxide can use oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention Change aluminium, such as macroporous aluminium oxide and small porous aluminum oxide, the mass ratio of general macroporous aluminium oxide and small porous aluminum oxide is 1：8~8：1.Institute The property for the macroporous aluminium oxide stated is as follows：Pore volume is 0.6 ~ 1.3mL/g, and specific surface area is 300 ~ 450m2/g。
Adhesive therefor of the present invention is made up of small porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used Aluminium pore volume is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
Amorphous silica-alumina used can be prepared by coprecipitation or grafting copolymerization process in catalyst carrier of the present invention, by document It is prepared by middle conventional method.In obtained amorphous silica-alumina, SiO2Weight content be 10% ~ 60%, preferably 20% ~ 55%, The pore volume of amorphous silica-alumina is 0.6 ~ 1.1mL/g, preferably 0.8 ~ 1.0mL/g, and specific surface area is 300 ~ 500m2/ g, preferably For 350 ~ 500m2/g。
Detailed process prepared by catalyst carrier for hydrgenating of the present invention is as follows：By Modified Zeolite Y, amorphous silica-alumina, oxygen Change aluminium mixing, shaping, then dry and be calcined, be prepared into carrier；It is small that drying can dry 3 ~ 6 at a temperature of 80 DEG C ~ 150 DEG C When, roasting is calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
Carrier of hydrocracking catalyst of the present invention loads hydrogenation active metal component by conventional methods（Vib and Group VIII metal component such as Co, Ni, Mo, W etc.）, it is prepared into hydrocracking catalyst.Using load side conventional in the prior art Method, preferably infusion process, can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnation catalyst containing required active component Agent carrier, carrier after dipping are then small in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour When, final catalyst is made.
The following examples are used to technical scheme be described in more detail, but the scope of the present invention is not limited solely to this The scope of a little embodiments.In the present invention, wt% is mass fraction.
Analysis method of the present invention：Specific surface area, pore volume, mesoporous pore volume use low temperature liquid nitrogen determination of adsorption method, relatively Crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio uses XRF methods（X ray fluorescence spectrometry）Measure, molecular sieve Grain size use SEM（SEM）Mode determine.Meleic acid amount uses Pyridine adsorption IR spectra method, sodium Content uses plasma emission spectrometry.
NaY molecular sieve original powder employed in the embodiment of the present invention and comparative example is industrially prepared, and property is as follows：SiO2/ Al2O3Mol ratio is 5.1, and grain size is ~ 1.7 μm, relative crystallinity 95%, cell parameter 2.468nm, Na2O weight content For 6.5wt%, specific surface area 856m2/ g, total pore volume 0.32mL/g, micropore pore volume account for the 81.3% of total pore volume, butt 72.0wt%。
Embodiment 1
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6 The aqueous solution, it is 72g/L's that 307mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature stirs after completion of dropwise addition 2 hours, constant temperature was filtered and dried after terminating, and the butt of molecular sieve is 65.3wt% after drying；By above-mentioned dried molecule Sieve is added in hydrothermal treatment device, in gauge pressure 0.25MPa, 610 DEG C of temperature, under the conditions of 1.0 hours processing times molecular sieve is entered Water-filling is heat-treated；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide that 520mL mass concentrations are 5.3% In the aqueous solution, constant temperature is stirred 4 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 90 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 10 hours, crystallization is filtered after terminating and drying process；Hydro-thermal is brilliant To change obtained drying sample to be calcined under oxygen-enriched state, oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/min, Constant temperature calcining temperature is 420 DEG C, and the constant temperature calcining time is 6 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-1, molecular sieve Property is listed in table 1.
Embodiment 2
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 55g/L's that 182mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition Stirring 2 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.0wt% after drying；Will be above-mentioned dried Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.30MPa, 670 DEG C of temperature, under the conditions of 2.0 hours processing times to point Son sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetrapropyl hydrogen that 910mL mass concentrations are 7.5% Aoxidize in aqueous ammonium, constant temperature is stirred 4 hours under the conditions of 90 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal Crystallization, 110 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 10 hours, crystallization is filtered after terminating and drying process；Will The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, and oxygen content is 65v% in calcination atmosphere, heating rate 1 DEG C/min, constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY- 2, molecular sieve property is listed in table 1.
Embodiment 3
Take NaY original powder 278g to be put into 1000mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 85g/L's that 417mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition Stirring 3 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 67.2wt% after drying；Will be above-mentioned dried Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.35MPa, 700 DEG C of temperature, under the conditions of 3.0 hours processing times to molecule Sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl hydrogen-oxygen that 1040mL mass concentrations are 3.5% Change in aqueous ammonium, constant temperature is stirred 3 hours under the conditions of 85 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal crystalline substance Change, 80 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 5 hours, crystallization is filtered after terminating and drying process；By hydro-thermal The drying sample that crystallization obtains is calcined under oxygen-enriched state, and oxygen content is 75v% in calcination atmosphere, and heating rate is 1 DEG C/ Min, constant temperature calcining temperature are 320 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-3, point Son sieve property is listed in table 1.
Embodiment 4
Take NaY original powder 278g to be put into 1400mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 60g/L's that 200mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition Stirring 2 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.1wt% after drying；Will be above-mentioned dried Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.30MPa, 750 DEG C of temperature, under the conditions of 2.0 hours processing times to point Son sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetrapropyl hydrogen that 520mL mass concentrations are 6.8% Aoxidize in aqueous ammonium, constant temperature is stirred 3 hours under the conditions of 90 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal Crystallization, 95 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 8 hours, crystallization is filtered after terminating and drying process；By water The drying sample that thermal crystallisation obtains is calcined under oxygen-enriched state, and oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/ Min, constant temperature calcining temperature are 380 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-4, Molecular sieve property is listed in table 1.
Comparative example 1
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature stirring 2 hours, constant temperature was filtered, washed and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming will divide Son sieve is calcined 3 hours at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；After taking second of ammonium of 100g to exchange Molecular sieve be put into 650mL mass concentrations be 7.5% the tetraethyl ammonium hydroxide aqueous solution in, constant temperature stirs under the conditions of 80 DEG C Mix 2 hours, then mixed material is transferred in crystallizing kettle and carries out crystallization, 100 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization 8 hours time, crystallization is filtered after terminating and drying process；The drying sample that crystallization obtains is calcined under oxygen-enriched state, Oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 8 hours, obtain molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.
Comparative example 2
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature stirring 2 hours, constant temperature divides after terminating to be filtered, washed and dried, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming will Molecular sieve is calcined 3 hours at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；Second of ammonium of 100g is taken to exchange Molecular sieve afterwards is put into the dust technology that 800mL concentration is 0.3mol/L, and constant temperature stirs 2 hours under the conditions of 80 DEG C, constant temperature Filtered after end and drying process；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 670 DEG C of temperature, molecular sieve is obtained to molecular sieve progress hydro-thermal process under the conditions of 2.0 hours processing times；Sample is compiled Number LDAY-2, molecular sieve property are listed in table 1.
Comparative example 3
Molecular sieve, sample number into spectrum LDAY-3, molecular sieve property row are prepared using the method for embodiment in CN201510147788.3 1 In table 1.
The property of the Y type molecular sieve of table 1
Production code member LAY-1 LAY-2 LAY-3 LAY-4
Specific surface area, m2/g 912 887 941 923
Pore volume, cm3/g 0.74 0.69 0.88 0.72
Lattice constant, nm 2.433 2.431 2.428 2.426
Relative crystallinity, % 131 119 140 132
Average crystallite size, μm 1.7 1.7 1.7 1.7
SiO2/Al2O3Mol ratio 73.6.3 62.3 81.9 65.8
Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % 86 83 91 87
Infrared total acid content, mmol/g 0.45 0.33 0.30 0.21
Na2O, wt% 0.05 0.06 0.03 0.07
Continued 1
Production code member LDAY-1 LDAY-2 LDAY-3
Specific surface area, m2/g 633 703 603
Pore volume, cm3/g 0.44 0.37 0.38
Lattice constant, nm 2.439 2.433 2.449
Relative crystallinity, % 98 103 86
Average crystallite size, μm 1.7 1.7 1.7
SiO2/Al2O3Mol ratio 7.5 33.5 8.6
Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % 47 31 37
Infrared total acid content, mmol/g 0.77 0.35 0.71
Na2O, wt% 0.21 0.19 0.45
Embodiment 5
By 100 grams of LAY-1 molecular sieves（Butt 90wt%）, 64.3 grams of amorphous silica-aluminas（SiO2Content 25wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 150 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 200 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into stone roller Mixed grind in press, adds water, is rolled into paste, extrusion, and extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, Obtain carrier ZS-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst HC-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 6
By 50 grams of LAY-1 molecular sieves（Butt 90wt%）, 50 grams of amorphous silica-aluminas（SiO2Content 25wt%, pore volume 0.85mL/g, Specific surface area 370m2/ g, butt 70wt%）, 214.3 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, do Base 70wt%）, 200 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into roller and mixes Grind, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier ZS- 2。
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst HC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 7 ~ 8
As described in Example 5, change LAY-1 into LAY-2, LAY-3 respectively, carrier ZS-3, ZS-4 and catalyst HC- is made 3 and HC-4, carrier and catalyst composition are shown in Table 2.
Comparative example 4 ~ 6
As described in Example 5, change LAY-1 into LDAY-1, LDAY-2, LDAY-2 respectively, be made carrier DZS-1, DZS-2, DZS-3 and catalyst DHC-1, DHC-2 and DHC-3, carrier and catalyst composition are shown in Table 3.
Embodiment 9 ~ 12
This embodiment describes catalyst HC-1, HC-2, HC-3 and HC-4 of the present invention Activity evaluation.In fixed bed hydrogenation Evaluated on experimental rig, Hydrobon catalyst uses 3936 catalyst, is tried on fixed bed hydrogenation experimental rig Test, using vacuum distillate as feedstock oil, feedstock property is listed in table 3, and evaluation result is listed in table 4.
Comparative example 7 ~ 9
This comparative example describes comparative example catalyst DHC-1, DHC-2 and DHC-3 of the present invention Activity evaluation.In fixed bed Evaluated on hydrogenation test apparatus, Hydrobon catalyst uses 3936 catalyst, enterprising in fixed bed hydrogenation experimental rig Row experiment, using vacuum distillate as feedstock oil, feedstock property is listed in table 3, and evaluation result is listed in table 4.
The composition and physico-chemical property of the catalyst carrier of table 2 and catalyst
Carrier forms and property
Numbering ZS-1 ZS-2 ZS-3 ZS-4
Composition
Modified Zeolite Y, wt% 30.0 15.0 30.0 30.0
Amorphous silica-alumina, wt% 15.0 15.0 15.0 15.0
Macroporous aluminium oxide, wt% 35.0 50.0 35.0 35.0
Adhesive, wt% Surplus Surplus Surplus Surplus
Property
Pore volume, mL/g 0.65 0.70 0.67 0.69
Specific surface area, m2/g 529 445 538 521
Catalyst forms and property
Numbering HC-1 HC-2 HC-3 HC-4
WO3, wt% 22.52 23.52 21.94 23.15
NiO, wt% 5.71 5.98 5.84 5.83
Pore volume, mL/g 0.42 0.45 0.41 0.44
Specific surface area, m2/g 429 386 425 433
Continued 2
Carrier forms and property
Numbering DZS-1 DZS-2 DZS-3
Composition
Modified Zeolite Y, wt% 30.0 30.0 30.0
Amorphous silica-alumina, wt% 15.0 15.0 15.0
Macroporous aluminium oxide, wt% 35.0 35.0 35.0
Adhesive, wt% Surplus Surplus Surplus
Property
Pore volume, mL/g 0.51 0.50 0.54
Specific surface area, m2/g 422 433 428
Catalyst forms and property
Numbering DHC-1 DHC-2 DHC-3
WO3, wt% 22.49 22.50 22.56
NiO, wt% 5.81 5.78 5.89
Pore volume, mL/g 0.30 0.30 0.27
Specific surface area, m2/g 322 335 305
The feedstock oil main character of table 3
Feedstock oil Vacuum distillate
Density（20℃）, kg/m3 959.3
Boiling range, DEG C
IBP/10% 360/382
30%/50% 436/484
70%/90% 531/---
95%/EBP ---/705
Nitrogen, μ g/g 2800
Carbon, wt% 84.78
Hydrogen, wt% 11.94
Sulphur, wt% 2.97
Carbon residue, wt% 0.35
The comparative evaluation's result of table 4
Hydrocracking catalyst HC-1 HC-2 HC-3 HC-4
Feedstock oil Vacuum distillate Vacuum distillate Vacuum distillate Vacuum distillate
Operating condition
Volume space velocity during liquid, h-1 1.0 1.0 1.0 1.0
Hydrogen to oil volume ratio 1200:1 1200:1 1200:1 1200:1
React stagnation pressure, MPa 15.0 15.0 15.0 15.0
Reaction temperature, DEG C 372 384 373 378
Product yield and property
Heavy naphtha
Yield, wt% 8.7 9.2 8.9 9.0
Virtue is latent, wt% 62.5 61.0 61.8 60.9
Jet fuel
Yield, wt% 33.7 34.0 33.9 34.5
Smoke point, mm 28 29 27 28
Aromatic hydrocarbons, v% 4.0 3.6 4.3 3.5
Diesel oil
Yield, wt% 20.8 20.1 20.4 20.0
Cetane number 62.0 62.0 61.0 63.0
Tail oil
Yield, wt% 33.2 32.5 33.0 32.1
BMCI values 11.1 10.8 10.7 10.1
Chemical hydrogen consumption, wt% 2.55 2.57 2.57 2.59
Liquid is received, wt% 98.5 98.1 98.4 98.0
Continued 4
Hydrocracking catalyst DHC-1 DHC-2 DHC-3
Feedstock oil Vacuum distillate Vacuum distillate Vacuum distillate
Operating condition
Volume space velocity during liquid, h-1 1.0 1.0 1.0
Hydrogen to oil volume ratio 1200:1 1200:1 1200:1
React stagnation pressure, MPa 15.0 15.0 150.
Reaction temperature, DEG C 391 395 392
Product yield and property
Heavy naphtha
Yield, wt% 9.8 10.0 10.2
Virtue is latent, wt% 55.3 54.9 54.8
Jet fuel
Yield, wt% 31.1 30.3 32.4
Smoke point, mm 25 24 25
Aromatic hydrocarbons, v% 5.8 6.9 5.7
Diesel oil
Yield, wt% 19.8 18.8 18.7
Cetane number 58.0 57.0 58.0
Tail oil
Yield, wt% 32.0 31.2 31.5
BMCI values 12.9 12.8 12.6
Chemical hydrogen consumption, wt% 2.88 2.89 2.89
Liquid is received, wt% 97.6 97.0 97.3
Continued 4（Catalyst stability is tested）
Hydrocracking catalyst HC-1 HC-1 DHC-1 DHC-1
Feedstock oil Vacuum distillate Vacuum distillate Vacuum distillate Vacuum distillate
Operating condition
Keep sample the time, h 400 3000 400 3000
Volume space velocity during liquid, h-1 1.0 1.0 1.0 1.0
Hydrogen to oil volume ratio 1200:1 1200:1 1200:1 1200:1
React stagnation pressure, MPa 15.0 15.0 15.0 15.0
Reaction temperature, DEG C 372 373 391 398
Product yield and property
Heavy naphtha
Yield, wt% 8.7 8.8 9.8 10.2
Virtue is latent, wt% 62.5 62.4 55.3 53.6
Jet fuel
Yield, wt% 33.7 33.6 31.1 31.5
Smoke point, mm 28 28 25 24
Aromatic hydrocarbons, v% 4.0 4.1 5.8 7.6
Diesel oil
Yield, wt% 20.8 20.7 19.8 19.2
Cetane number 62.0 61.8 58.0 56
Tail oil
Yield, wt% 33.2 33.3 32.0 32.1
BMCI values 11.1 11.0 12.9 13.5
Chemical hydrogen consumption, wt% 2.55 0.55 2.88 1.95
Liquid is received, wt% 98.5 98.4 97.6 96.9

Claims (14)

1. a kind of method being hydrocracked, including wax oil raw material contact with hydrocracking catalyst and carry out hydrocracking reaction, obtain To heavy naphtha, diesel oil, jet fuel and hydrogenation tail oil；Wherein described hydrocracking catalyst, including hydrogenation active metals Component and carrier, carrier includes Modified Zeolite Y, amorphous silica-alumina and aluminum oxide, wherein described Modified Zeolite Y, Its property is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio be 55 ~ 100, cell parameter be 2.425 ~ 2.435nm, total pore volume are 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.
2. in accordance with the method for claim 1, it is characterised in that：The property of the Modified Zeolite Y is as follows：Total pore volume For 0.6 ~ 1.0mL/g, mesoporous pore volume accounts for the 80% ~ 95% of total pore volume.
3. in accordance with the method for claim 1, it is characterised in that：The grain size of the Modified Zeolite Y is 1.0 ~ 2.5 μ M, preferably 1.2 ~ 1.8 μm.
4. in accordance with the method for claim 1, it is characterised in that：The mesoporous bore dia of the Modified Zeolite Y is 2nm ~10nm。
5. in accordance with the method for claim 1, it is characterised in that：The specific surface area of the Modified Zeolite Y is 650m2/g~ 1000m2/ g, preferably 750m2/g~1000m2/g。
6. in accordance with the method for claim 1, it is characterised in that：The infrared total acid content of the Modified Zeolite Y be 0.1 ~ 0.5mmol/g。
7. in accordance with the method for claim 1, it is characterised in that：In the Modified Zeolite Y, Na2O weight content is Below 0.15wt%.
8. in accordance with the method for claim 1, it is characterised in that：The property of the hydrocracking catalyst is as follows：Compare surface Product is 250 ~ 450m2/ g, pore volume are 0.30 ~ 0.50mL/g.
9. in accordance with the method for claim 1, it is characterised in that：Described hydrogenation active metals are vib and VIII The metal of race, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Using the weight of catalyst as base Standard, using the content that oxide is counted as 10.0% ~ 30.0%, content of the group VIII metal in terms of oxide is vib metals 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 82.0%.
10. according to the method described in claim 1 or 9, it is characterised in that：Described carrier of hydrocracking catalyst, with carrier Weight on the basis of, the content of Modified Zeolite Y is 10% ~ 50%, and the content of amorphous silica-alumina is 5% ~ 30%, and aluminum oxide contains Measure as 20% ~ 85%, be preferably as follows：The content of Modified Zeolite Y is 15% ~ 45%, and the content of amorphous silica-alumina is 10% ~ 25%, The content of aluminum oxide is 30% ~ 75%.
11. in accordance with the method for claim 1, it is characterised in that：In described amorphous silica-alumina, SiO2Weight content be 10% ~ 60%, preferably 20% ~ 55%, the property of amorphous silica-alumina are as follows：Pore volume is 0.6 ~ 1.1mL/g, specific surface area is 300 ~ 500m2/ g, is preferably as follows：Pore volume is 0.8 ~ 1.0mL/g, and specific surface area is 350 ~ 500m2/g。
12. in accordance with the method for claim 1, it is characterised in that：The method for hydrogen cracking uses one-stage serial technique stream Hydrobon catalyst is to use alumina-based supports used by journey, wherein hydrofinishing, with vib and group VIII gold It is molybdenum and/or tungsten to belong to for hydrogenation active metal component, vib metals, and the metal of group VIII is cobalt and/or nickel, with catalysis On the basis of the weight of agent, vib metals are using the content that oxide is counted as 15.0% ~ 30.0%, and group VIII metal is with oxide The content of meter is 4.0% ~ 8.0%.
13. according to the method described in claim 1 or 12, it is characterised in that：The method for hydrogen cracking uses one-stage serial work Skill flow, used operating condition are as follows：Reaction stagnation pressure is 12.0 ~ 20.0MPa, and volume space velocity is 0.5 ~ 2.0h during liquid-1, hydrogen Oil volume ratio is 1000：1~2000：1, reaction temperature is 370 ~ 435 DEG C.
14. in accordance with the method for claim 1, it is characterised in that：Described wax oil is that height does wax oil, and its property is as follows： 20 DEG C of density are 0.9 ~ 1.0g/cm3, initial boiling point is 350 ~ 400 DEG C, is done as 700 ~ 750 DEG C, sulfur content be 2.0wt% ~ 4.0wt%, nitrogen content are 2000 ~ 4000 μ g/g.
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Publication number Priority date Publication date Assignee Title
CN111632620A (en) * 2020-06-16 2020-09-08 中化泉州石化有限公司 Medium oil type hydrocracking catalyst

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CN101450319A (en) * 2007-12-04 2009-06-10 中国石油化工股份有限公司 Hydrocracking catalyst for moderate oil and preparation thereof
CN104667966A (en) * 2013-11-26 2015-06-03 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN101450319A (en) * 2007-12-04 2009-06-10 中国石油化工股份有限公司 Hydrocracking catalyst for moderate oil and preparation thereof
CN104667966A (en) * 2013-11-26 2015-06-03 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111632620A (en) * 2020-06-16 2020-09-08 中化泉州石化有限公司 Medium oil type hydrocracking catalyst
CN111632620B (en) * 2020-06-16 2023-08-25 中化泉州石化有限公司 Medium oil type hydrocracking catalyst

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