CN107344105A - Hydrocracking catalyst and preparation method thereof - Google Patents

Hydrocracking catalyst and preparation method thereof Download PDF

Info

Publication number
CN107344105A
CN107344105A CN201610289567.4A CN201610289567A CN107344105A CN 107344105 A CN107344105 A CN 107344105A CN 201610289567 A CN201610289567 A CN 201610289567A CN 107344105 A CN107344105 A CN 107344105A
Authority
CN
China
Prior art keywords
molecular sieve
catalyst
pore volume
carrier
type molecular
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610289567.4A
Other languages
Chinese (zh)
Other versions
CN107344105B (en
Inventor
刘昶
王凤来
关明华
杜艳泽
黄薇
赵红
郝文月
曹均丰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201610289567.4A priority Critical patent/CN107344105B/en
Publication of CN107344105A publication Critical patent/CN107344105A/en
Application granted granted Critical
Publication of CN107344105B publication Critical patent/CN107344105B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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

Landscapes

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

Abstract

The invention discloses a kind of hydrocracking catalyst and preparation method thereof.The hydrocracking catalyst includes hydrogenation active metal component and carrier, and carrier includes Modified Zeolite Y and amorphous silica-alumina, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.Oil type hydrocracking catalyst during the catalyst is suitably used as, has higher activity and middle distillates oil selectivity, and the quality of produced intermediate oil is good.

Description

Hydrocracking catalyst and preparation method thereof
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, is particularly used to be hydrocracked production high quality Hydrocracking catalyst of intermediate oil and preparation method thereof.
Background technology
The recovery and development of World Economics, make countries in the world refined products market to high-quality middle cut oil product（That is aviation The power fuel of industry：Jet fuel, and the major impetus fuel of sea-lanes of communication industry：Diesel oil）Demand be continuously increased always. At the same time, the reserves of World's Oil and Gas Resources are reduced year by year, and quality is deteriorated year by year, and the requirement to finished product oil quality is got over Come higher.Therefore, hydrocracking technology turns into the optimal oil refining skill for producing high-quality intermediate oil with its exclusive technical advantage Art.
Hydrocracking catalyst is a kind of bifunctional catalyst, and it has cracking activity and hydrogenation activity simultaneously, i.e., simultaneously Contain acidic components and hydrogenation active component.It is wherein acid mainly by various molecular sieves and/or to form the heat resistant inorganic of carrier Oxide provides, and the property of acidic components has very heavy to the activity of hydrocracking catalyst and the selectivity of intermediate oil The influence wanted.Hydrogenation active component be selected generally from group VIB and the metal of the VIIIth race in the periodic table of elements, metal oxide and/ Or metal sulfide.The key component that cracking is played in hydrocracking catalyst is mostly molecular sieve, the quality of molecular sieve performance, Catalyst performance and oil quality will be directly affected.
The method of industrial production Y type molecular sieve is essentially all in the Hes of USP 3639099 using GRACE companies of the U.S. at present The directing agent method proposed in USP 4166099, the orifice diameter in the Y type molecular sieve original powder duct of synthesis for 0.74nm × 0.74nm, its micropore pore volume account for more than the 95% of total pore volume.Polycyclic restructuring fractionated molecule in wax oil hydrogenation cracked stock is straight Footpath generally in more than 1nm, the cracking reaction for heavy constituent macromolecular, is adapted to the preferable duct aperture that it reacts and product spreads Scope is 2nm ~ 10nm macropore range, can be exposed by more accessible acid centre, while is also divided greatly beneficial to raw material The absorption of son and the desorption and diffusion of reaction and purpose product, improve molecular sieve cracking selectivity.It is situated between to improve Y type molecular sieve The low situation for being unfavorable for wax oil macromolecular reaction of hole pore volume content, is generally modified processing to Y type molecular sieve original powder, can obtain To the Modified Zeolite Y of different pore passage structures and acid distribution.
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 using VGO as raw material, its activity is poor, and middle distillates oil selectivity is not also 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.
The method that CN200610001864.0 discloses the Modified Zeolite Y under a kind of surfactant protection.The party The characteristics of method is that surfactant is added in sour dealumination process, i.e., using industrial NaY molecular sieve as raw material, is carried out before hydro-thermal process Ammonium exchanges twice, by hydro-thermal process twice before being chemically treated, sour dealuminzation is then carried out under the protection of surfactant, is obtained HY sieve samples silica alumina ratio（SiO2/Al2O3）For 9 ~ 18, while keep 75% ~ 95% crystallinity, the molecular sieve intermediary hole The more industrial NaY molecular sieve of ratio has a certain amount of raising.
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 hydrocracking catalyst and its preparation side Method.The hydrocracking catalyst uses and is rich in meso-hole structure, the Modified Zeolite Y that effective pore sife distribution is concentrated is used as and mainly split Change component, using amorphous silica-alumina as the second Cracking Component, Modified Zeolite Y acts synergistically with amorphous silica-alumina, makes the present invention Hydrocracking catalyst there is good activity and intermediate oil selectivity, and the product quality of gained intermediate oil It is good.
The hydrocracking catalyst of the present invention, comprising hydrogenation active metal component and carrier, wherein carrier includes modified Y types The property of molecular sieve and amorphous silica-alumina, wherein Modified Zeolite Y is as follows：Relative crystallinity is 110% ~ 150%, SiO2/ Al2O3Mol ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, mesoporous pore volume account 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 5% ~ 25%, preferably 5% ~ 20%, and the content of amorphous silica-alumina is 75% ~ 95%, preferably 80% ~ 95%.
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 catalyst of the present invention, on the basis of the weight of catalyst, VI B Race's metal（In terms of oxide）Content be 10.0% ~ 30.0%, group VIII metal（In terms of oxide）Content for 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：Modified Zeolite Y, amorphous silica-alumina are mixed, shaping, then dries and is calcined, system Into the preparation method of catalyst carrier, wherein Modified Zeolite Y, comprise 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 Y type molecular sieve of the present invention is made.
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 The one or more of ammonium hydroxide.Wherein, by step（2）In after obtained Y type molecular sieve uniformly mixes with organic formwork agent, enter Water-filling thermal crystallisation, process are as follows：By step（2）In obtained Y type molecular sieve be beaten in the organic formwork agent aqueous solution, liquid weighs admittedly Amount is than being 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, the mass concentration of the organic formwork agent aqueous solution for 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, and gauge pressure is 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.
Y type molecular sieve in hydrocracking catalyst of the present invention is to use（NH4）2SiF6Place is modified to NaY molecular sieve Reason, while modulation molecular sieve silica alumina ratio is realized, can deviate from the sodium ion in NaY molecular sieve together, then in organic mould Hydrothermal crystallizing is carried out to the molecular sieve after hydro-thermal process in the presence of plate agent, can so make part silicon atom and aluminium atom in organic mould Plate agent effect enters framework of molecular sieve structure down, while further stablizing and improving the skeleton structure of modified molecular screen, disappears Except caused non-skeleton structure, unimpeded pore passage structure, part organic formwork agent can also enter in zeolite-water heat treatment process Into the duct of molecular sieve, coordinate follow-up oxygen-enriched low-temperature treatment, can by the organic formwork agent in molecular sieve it is controllable in order removing, So as to produce a large amount of ordered mesopore structures, and pore size distribution is more concentrated.
Y type molecular sieve in hydrocracking catalyst of the present invention, acidity is suitable, crystallinity is high, mesoporous proportion is high, hole Footpath distribution is more concentrated, suitably as Cracking Component.Because the Y type molecular sieve has bigger pore volume and mesopore volume, more More acid centres are exposed, and are advantageous to raw material heavy oil macromolecular and are cracked, but also with more preferably pore-size distribution model Enclose, the cracking degree of reactant can be efficiently controlled, and be advantageous to product and be diffused in duct, so in cracking reaction In, can relative increase activated centre, and can make heavy oil macromolecular carry out suitable degree cracking reaction, both improved splitting for heavy oil Change ability, while coke yield is reduced, catalyst can show good cracking activity and product selectivity.
Hydrocracking catalyst of the present invention is hydrocracked the high-quality intermediate oil of production especially suitable for heavy wax oil, is adopted Hydrocracking operation condition is as follows：Using one-stage serial technological process, 12.0 ~ 20.0MPa of stagnation pressure is reacted, volume is empty during liquid 0.5 ~ 2.0h of speed-1, hydrogen to oil volume ratio 1000：1~2000：1,370 ~ 435 DEG C of reaction temperature.
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
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.SiO in obtained amorphous silica-alumina2Weight content be 10% ~ 60%, preferably 20% ~ 55%, nothing The pore volume of amorphous silicon-alumina is 0.6 ~ 1.1ml/g, preferably 0.8 ~ 1.0ml/g, and specific surface area is 300 ~ 500m2/ g, it is preferably 350~500m2/g。
Conventional shaping assistant such as peptization acid, extrusion aid can also be added in catalyst carrier preparation process of the present invention Deng.
Detailed process prepared by catalyst carrier for hydrgenating of the present invention is as follows：Modified Zeolite Y, amorphous silica-alumina are mixed Close, extruded moulding, 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 to 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 13.3 grams of LAY-1 molecular sieves（Butt 90wt%）, 268.6 grams of amorphous silica-aluminas（SiO2Content 35wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 162.5 grams of peptizing agents（4g nitric acid/100g peptizing agents）It is put into and rolls Mixed grind in machine, 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, obtains carrier ZYS-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 33.3 grams of LAY-2 molecular sieves（Butt 90wt%）, 242.9 grams of amorphous silica-aluminas（SiO2Content 35wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 168.2 grams of peptizing agents（4g nitric acid/100g peptizing agents）It is put into and rolls Mixed grind in machine, 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, obtains carrier ZYS-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-3, LAY-4 respectively, carrier ZYS-3, ZYS-4 and catalyst is made HC-3, 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-3 respectively, carrier DZYS-1, DZYS- is made 2nd, DZYS-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 plus Evaluated on hydrogen experimental rig, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1. during liquid 0h-1, using VGO 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, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity during liquid 1.0h-1, using VGO 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 ZYS-1 ZYS-2 ZYS-3 ZYS-4
Composition
Modified Zeolite Y, wt% 15 6 15 15
Amorphous silica-alumina, wt% 85 94 85 85
Property
Specific surface area, m2/g 473 450 451 444
Pore volume, mL/g 0.63 0.66 0.59 0.69
Catalyst forms and property
Numbering HC-1 HC-2 HC-3 HC-4
WO3, wt% 23.54 23.21 23.17 23.24
NiO, wt% 5.98 6.00 6.01 5.94
Specific surface area, m2/g 338 369 319 311
Pore volume, mL/g 0.44 0.42 0.41 0.43
Continued 2
Carrier forms and property
Numbering DZYS-1 DZYS-2 DZYS-3
Composition
Modified Zeolite Y, wt% 15 15 15
Amorphous silica-alumina, wt% 85 85 85
Property
Specific surface area, m2/g 388 401 368
Pore volume, mL/g 0.50 0.48 0.45
Catalyst forms and property
Numbering DHC-1 DHC-2 DHC-3
WO3, wt% 23.71 23.58 23.69
NiO, wt% 5.79 6.03 5.73
Specific surface area, m2/g 251 262 254
Pore volume, mL/g 0.30 0.30 0.31
The feedstock oil main character of table 3
Feedstock oil Vacuum distillate（VGO）
Density（20℃）, kg/m3 920.6
Boiling range, DEG C
IBP/10% 328/413
30%/50% 450/471
70%/90% 493/522
95%/EBP 534/545
Nitrogen, μ g/g 1575
Carbon, wt% 85.25
Hydrogen, wt% 11.96
Carbon residue, wt% 0.35
The catalyst performance comparative evaluation's result of table 4
Catalyst HC-1 HC-2 HC-3 HC-4
Feedstock oil VGO VGO VGO VGO
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 14.7 14.7 14.7 14.7
Reaction temperature, DEG C 380 385 391 394
Product yield and property
Heavy naphtha
Yield, wt% 9.1 8.8 8.7 8.6
Virtue is latent, wt% 61.3 62.7 62.9 63.0
Jet fuel
Yield, wt% 23.9 23.1 23.0 22.8
Smoke point, mm 24 23 24 23
Aromatic hydrocarbons, v% 9.8 10.0 9.6 10.1
Diesel oil
Yield, wt% 35.1 35.5 35.9 35.2
Cetane number 63.0 62.0 61.5 62.0
Tail oil
Yield, wt% 28.5 28.9 28.7 28.1
BMCI values 8.8 9.0 8.5 9.2
Chemical hydrogen consumption, wt% 2.10 2.08 2.07 2.14
Liquid is received, wt% 98.1 98.4 98.5 98.7
Continued 4
Catalyst DHC-1 DHC-2 DHC-3
Feedstock oil VGO VGO VGO
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 14.7 14.7 14.7
Reaction temperature, DEG C 401 405 409
Product yield and property
Heavy naphtha
Yield, wt% 9.9 10.3 10.5
Virtue is latent, wt% 61.6 58.6 57.3
Jet fuel
Yield, wt% 22.6 22.1 20.6
Smoke point, mm 22 21 21
Aromatic hydrocarbons, v% 12.5 13.6 14.2
Diesel oil
Yield, wt% 33.2 32.1 31.6
Cetane number 60.1 59.6 60.3
Tail oil
Yield, wt% 28.0 27.9 27.6
BMCI values 10.8 11.5 12.0
Chemical hydrogen consumption, wt% 2.24 2.32 2.36
Liquid is received, wt% 97.6 96.5 95.9
When it can be seen from the evaluation result of table 4 using hydrocracking catalyst of the present invention, midbarrel oil yield and product matter Amount is superior to reference catalyst.

Claims (22)

1. a kind of hydrocracking catalyst, including hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y and nothing Amorphous silicon-alumina, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Rub You are than being 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for total hole More than the 70% of volume.
2. according to the catalyst described in claim 1, it is characterised in that：The property of the Y type molecular sieve is as follows：Total pore volume is 0.6 ~ 1.0mL/g, mesoporous pore volume account for the 80% ~ 95% of total pore volume.
3. according to the catalyst described in claim 1, it is characterised in that：The grain size of the Y type molecular sieve is 1.0 ~ 2.5 μm, Preferably 1.2 ~ 1.8 μm.
4. according to the catalyst described in claim 1, it is characterised in that：The mesoporous bore dia of the Y type molecular sieve be 2nm ~ 10nm。
5. according to the catalyst described in claim 1, it is characterised in that：The specific surface area of the Y type molecular sieve is 650m2/g~ 1000m2/ g, preferably 750m2/g~1000m2/g。
6. according to the catalyst described in claim 1, it is characterised in that：The infrared total acid content of the Y type molecular sieve be 0.1 ~ 0.5mmol/g。
7. according to the catalyst described in claim 1, it is characterised in that：In the Y type molecular sieve, Na2O weight content is Below 0.15wt%.
8. according to the catalyst described in claim 1, it is characterised in that：The property of the hydrocracking catalyst is as follows：Compare table Area is 250 ~ 450m2/ g, pore volume are 0.30 ~ 0.50mL/g.
9. according to the catalyst described in claim 1, it is characterised in that：Described hydrogenation active metals are vib and the The metal of VIII, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；With the weight of catalyst On the basis of, vib metals are using the content that oxide is counted as 10.0% ~ 30.0%, content of the group VIII metal in terms of oxide For 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 86.0%.
10. according to the catalyst described in claim 1, it is characterised in that：Described carrier of hydrocracking catalyst, with carrier Weight on the basis of, the content of Modified Zeolite Y is 5% ~ 25%, and the content of amorphous silica-alumina is 75% ~ 95%, is preferably as follows： The content of Modified Zeolite Y is 5% ~ 20%, and the content of amorphous silica-alumina is 80% ~ 95%.
11. according to the catalyst described in claim 1, it is characterised in that：In described amorphous silica-alumina, SiO2Weight content It is as follows for 10% ~ 60%, preferably 20% ~ 55%, the property of amorphous silica-alumina：Pore volume is 0.6 ~ 1.1mL/g, and 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. the preparation method of any catalyst of claim 1 ~ 11, include preparation and the load hydrogenation active metals of carrier The preparation process of component, wherein carrier is as follows：Modified Zeolite Y, amorphous silica-alumina are mixed, shaping, then dries and roasts Burn, the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, 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, and preferably hydrothermal conditions are as follows：Gauge pressure is 0.25 ~ 0.40MPa, Temperature is 610 ~ 750 DEG C, and processing time is 1.0 ~ 3.0 hours；
（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 Modified Zeolite Y is made.
13. in accordance with the method for claim 12, it is characterised in that：Step（1）In, the property of NaY type molecular sieves is as follows：
SiO2/Al2O3Mol ratio be 3 ~ 6, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, relative crystallinity be 80% ~ 110%, cell parameter is 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, specific surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4mL/g, and micropore pore volume accounts for more than the 75% of total pore volume.
14. in accordance with the method for claim 12, it is characterised in that：Step（1）In,（NH4）2SiF6Addition be NaY types 5wt% ~ 20wt% of molecular sieve butt weight.
15. in accordance with the method for claim 12, it is characterised in that：Step（1）In,（NH4）2SiF6The quality of the aqueous solution is dense Spend for 50 ~ 100g/L.
16. in accordance with the method for claim 12, it is characterised in that：Step（1）In, NaY types molecular sieve with（NH4）2SiF6Water The reaction condition that solution contact is reacted：Temperature is 80 ~ 150 DEG C, and the reaction time is 0.1 ~ 5.0 hour, preferred reaction conditions It is as follows：Temperature is 90 ~ 120 DEG C, and the reaction time is 1.0 ~ 3.0 hours.
17. in accordance with the method for claim 12, it is characterised in that：Step（1）In, dry condition is at 50 ~ 95 DEG C Dry 0.5 ~ 5.0 hour, the butt of the Y type molecular sieve of gained is 60wt% ~ 80wt% after drying.
18. in accordance with the method for claim 12, it is characterised in that：Step（3）In, organic formwork agent is tetraethyl hydroxide One or more in ammonium, TMAH, TPAOH.
19. in accordance with the method for claim 12, it is characterised in that：By step（2）In obtained Y type molecular sieve and organic mould Plate agent uniformly after mixing, carries out hydrothermal crystallizing, and process is as follows：By step（2）In obtained Y type molecular sieve in organic formwork agent water It is beaten in solution, solvent and solute weight ratio 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and organic formwork agent is water-soluble The mass concentration of liquid is 3% ~ 10%, and mixed material then is placed in into crystallization in crystallizing kettle, and crystallization temperature is 80 ~ 120 DEG C, during crystallization Between be 4 ~ 10h, gauge pressure is 0.1 ~ 0.2MPa.
20. in accordance with the method for claim 12, it is characterised in that：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, Roasting time is 5 ~ 10h.
21. in accordance with the method for claim 12, it is characterised in that：Process prepared by the carrier of hydrocracking catalyst For：
Modified Zeolite Y, amorphous silica-alumina are mixed, shaping, is then dried and is calcined, be prepared into carrier, it is described Dry and dried 3 ~ 6 hours at a temperature of 80 DEG C ~ 150 DEG C, roasting is calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
22. in accordance with the method for claim 12, it is characterised in that：In the hydrocracking catalyst, active metal is born Load uses infusion process, i.e., with the solution impregnated catalyst carrier containing active metal component, in 100 DEG C ~ 150 DEG C dryings after dipping 1 ~ 12 hour, then it is calcined 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C, hydrocracking catalyst is made.
CN201610289567.4A 2016-05-05 2016-05-05 Hydrocracking catalyst and preparation method thereof Active CN107344105B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610289567.4A CN107344105B (en) 2016-05-05 2016-05-05 Hydrocracking catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610289567.4A CN107344105B (en) 2016-05-05 2016-05-05 Hydrocracking catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107344105A true CN107344105A (en) 2017-11-14
CN107344105B CN107344105B (en) 2019-11-15

Family

ID=60253883

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610289567.4A Active CN107344105B (en) 2016-05-05 2016-05-05 Hydrocracking catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107344105B (en)

Cited By (2)

* 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
CN112717983A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 Distillate oil hydrocracking catalyst, preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101380589A (en) * 2007-09-04 2009-03-11 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof
CN103100417A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101380589A (en) * 2007-09-04 2009-03-11 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof
CN103100417A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112717983A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 Distillate oil hydrocracking catalyst, preparation method and application thereof
CN112717983B (en) * 2019-10-28 2022-04-08 中国石油化工股份有限公司 Distillate oil hydrocracking catalyst, preparation method and application thereof
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

Also Published As

Publication number Publication date
CN107344105B (en) 2019-11-15

Similar Documents

Publication Publication Date Title
CN101450320B (en) Hydrocracking catalyst containing Y molecular sieve and preparation method thereof
CN101450319B (en) Hydrocracking catalyst for moderate oil and preparation thereof
CN107344720B (en) A kind of Y type molecular sieve and preparation method thereof
CN103889572B (en) Process for preparing a mesoporized catalyst, catalyst thus obtained and use thereof in a catalytic process
CN107345161B (en) A kind of method for hydrogen cracking of coal tar
CN107344106B (en) A kind of hydrocracking catalyst and preparation method thereof
CN107344105B (en) Hydrocracking catalyst and preparation method thereof
CN107344102B (en) A kind of hydrocracking catalyst and its preparation method
CN107345154B (en) A kind of method for hydrogen cracking of poor ignition quality fuel
CN105713657B (en) Hydrocracking method
CN105709820B (en) A kind of hydrocracking catalyst and preparation method thereof
CN107345153A (en) A kind of method for hydrogen cracking for producing low-coagulation diesel oil
CN107345155B (en) A kind of method for hydrogen cracking
CN107344120B (en) Carrier of hydrocracking catalyst and its preparation method
CN107344117B (en) Hydrocracking catalyst and its preparation method
CN107345156B (en) A method of it is hydrocracked
CN108452839A (en) A kind of Jie's mesoporous-microporous composite molecular sieve, catalyst and its preparation method and application
CN107345159B (en) A kind of method for hydrogen cracking producing low-coagulation diesel oil
CN107344121B (en) A kind of catalyst for hydro-upgrading carrier and preparation method thereof
CN107344119A (en) A kind of carrier of hydrocracking catalyst and preparation method thereof
CN107344107B (en) A kind of catalyst for hydro-upgrading and preparation method thereof
CN107345160B (en) A kind of production method of lube base oil
CN114433213A (en) Composite carrier and preparation method and application thereof
CN106947521B (en) A kind of processing method of poor ignition quality fuel
CN105709845A (en) Hydrocracking catalyst carrier and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant