CN107344105B - Hydrocracking catalyst and preparation method thereof - Google Patents

Hydrocracking catalyst and preparation method thereof Download PDF

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Publication number
CN107344105B
CN107344105B CN201610289567.4A CN201610289567A CN107344105B CN 107344105 B CN107344105 B CN 107344105B CN 201610289567 A CN201610289567 A CN 201610289567A CN 107344105 B CN107344105 B CN 107344105B
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molecular sieve
catalyst
type molecular
carrier
pore volume
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CN107344105A (en
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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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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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    • 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

Abstract

The invention discloses a kind of hydrocracking catalysts 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 the Modified Zeolite Y, property are as follows: relative crystallinity is 110% ~ 150%, SiO2/Al2O3Molar 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 70% of total pore volume or more.The catalyst is suitable for oil type hydrocracking catalyst in being used as, activity with higher and middle distillates oil selectivity, and produced intermediate oil is high-quality.

Description

Hydrocracking catalyst and preparation method thereof
Technical field
The present invention relates to a kind of hydrocracking catalysts and preparation method thereof, especially for being hydrocracked production high quality Hydrocracking catalyst of intermediate oil and preparation method thereof.
Background technique
The recovery and development of world economy make countries in the world refined products market to high-quality middle cut oil product (i.e. aviation The power fuel of industry: the major impetus fuel of jet fuel and 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 becomes the best oil refining skill for producing high-quality intermediate oil with its exclusive technical advantage Art.
Hydrocracking catalyst is a kind of bifunctional catalyst, 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 constitute the heat resistant inorganic of carrier Oxide provides, and the property of acidic components has the activity of hydrocracking catalyst and the selectivity of intermediate oil very heavy 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 using GRACE company, the U.S. in 3639099 He of USP at present The directing agent method proposed in USP 4166099, the orifice diameter in the Y type molecular sieve original powder duct of synthesis be 0.74nm × 0.74nm, micropore pore volume account for about 95% of total pore volume or more.Polycyclic recombination fractionated molecule in wax oil hydrogenation cracked stock is straight Diameter is usually in 1nm or more, cracking reaction for heavy constituent macromolecular, it is suitble to react and the ideal duct aperture of product diffusion Range is the macropore range of 2nm ~ 10nm, can be exposed by more accessible acid centre, while being also conducive to raw material and dividing greatly 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 Hole pore volume content low the case where being unfavorable for wax oil macromolecular reaction, processing usually is modified to Y type molecular sieve original powder, can be obtained To the Modified Zeolite Y of different cellular structures and acid distribution.
US4401556 discloses a kind of for producing the hydrocracking catalyst of intermediate oil.The catalyst is to pass through Cross dealuminzation Y type molecular sieve be cracking active component, silica alumina ratio be 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, 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 The characteristics of agent contains amorphous silica-alumina and a kind of Y type molecular sieve of Low acid, the molecular sieve is processing raw material point at high temperature Son sieve, the dry type heat treatment for being passed through inert gas including 680 ~ 780 DEG C of hydro-thermal process or higher than 700 DEG C.Due to the molecule Sieve acidity is relatively low, keeps the activity of catalyst excessively relatively low, this requires improve hydrocracking reaction temperature, the hot tearing of molecular sieve The enhancing of change trend, but hydrogenation reaction is inhibited, improve the middle distillates oil selectivity of catalyst unobvious, product quality is also by bad It influences.
CN200610001864.0 discloses the method for the Modified Zeolite Y under a kind of protection of surfactant.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, carries 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 sample silica alumina ratio (SiO2/Al2O3) it is 9 ~ 18, while keeping 75% ~ 95% crystallinity, the molecular sieve intermediary hole The more industrial NaY molecular sieve of ratio has a certain amount of raising.
From the point of view of application of the molecular sieve with cracking function during Industrial Catalysis, 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 Energy barrier can just diffuse into molecular sieve pore passage, and specific catalysis reaction occurs, is at this moment adsorbed molecule across molecular sieve crystal Hole and cage diffusion serve it is conclusive.The molecular sieve total pore volume and mesoporous pore volume of conventional method of modifying preparation 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 is capable of handling the raw material that molecule is bigger, oil product is heavier, and raising macromolecular conversion probability etc. shows more superior Performance, to promote the level of hydrocracking catalyst.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of hydrocracking catalyst and its preparation sides 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 splits Change component, with amorphous silica-alumina for the second Cracking Component, Modified Zeolite Y and amorphous silica-alumina act synergistically, and make the present invention Hydrocracking catalyst there is good activity and intermediate oil selectivity, and the product quality of gained intermediate oil It is good.
Hydrocracking catalyst of the invention includes hydrogenation active metal component and carrier, and wherein carrier includes modified Y type Molecular sieve and amorphous silica-alumina, wherein the property of Modified Zeolite Y is as follows: relative crystallinity is 110% ~ 150%, SiO2/ Al2O3Molar ratio be 55 ~ 100, cell parameter be 2.425 ~ 2.435nm, total pore volume be 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, mesoporous pore volume account for 70% of total pore volume or more, preferably 80% ~ 95%.
The grain size of the Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
In the Modified Zeolite Y, mesoporous bore dia is 2 ~ 10nm.
The specific surface area of the Modified Zeolite Y is 650 ~ 1000m2/ g, preferably 750 ~ 1000m2/g。
The infrared total acid content of the Modified Zeolite Y is 0.1 ~ 0.5mmol/g.
In the Modified Zeolite Y, Na2The weight content of O is 0.15wt% or less.
In the hydrocracking catalyst, the 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%.
The hydrogenation active metals generally use the metal of group VIB and group VIII, and 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, Section VI B The content of race's metal (in terms of oxide) is 10.0% ~ 30.0%, the content of group VIII metal (in terms of oxide) is 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, preparation and load hydrogenation active metal component including carrier, Wherein the preparation process of carrier is as follows: Modified Zeolite Y, amorphous silica-alumina being mixed, molding, then dry and roasting, system At catalyst carrier, wherein the preparation method of Modified Zeolite Y, includes the following steps:
(1) NaY type molecular sieve and (NH4)2SiF6Aqueous solution contact is reacted, and is filtered and is dried after reaction；
(2) hydro-thermal process is carried out to Y type molecular sieve obtained by step (1)；Hydrothermal conditions: gauge pressure be 0.20 ~ 0.40MPa, temperature are 600 ~ 800 DEG C, and the processing time is 0.5 ~ 5.0 hour；
(3) hydrothermal crystallizing processing is carried out under the conditions of by Y type molecular sieve obtained by step (2) existing for the organic formwork agent, so By filtering and drying；
(4) step (3) resulting Y type molecular sieve is roasted under low temperature oxygen-enriched atmosphere, Y type molecule of the invention is made Sieve.
In the method for the present invention step (1), the property of NaY type molecular sieve is as follows:
SiO2/Al2O3Molar ratio be 3 ~ 6, preferably 4.5 ~ 5.5, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, Relative crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2The weight content of O is 6.0wt% ~ 8.0wt%, than Surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4 mL/g, and micropore pore volume accounts for 75% of total pore volume or more.
In the method for the present invention step (1), (NH4)2SiF6Additional amount be NaY type molecular sieve dry weight 5wt% ~ 20wt%。
In the method for the present invention step (1), (NH4)2SiF6The mass concentration of aqueous solution is 50 ~ 100g/L.NaY type molecular sieve With (NH4)2SiF6Aqueous solution contacts the reaction condition that is reacted: temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, when reaction Between be 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
In the method for the present invention step (1), NaY type molecular sieve and (NH4)2SiF6After aqueous solution contact is reacted, separation point Son sieve and by-product, can wash, refilter, dry, it is preferably dry after resulting Y type molecular sieve butt be 60wt% ~ 80wt%.Dry condition is usually 0.5 ~ 5.0 hour dry at 50 ~ 95 DEG C.
In the method for the present invention step (2), hydro-thermal process is the molecular sieve obtained in saturated steam processing step (1), Treatment conditions: 0.20 ~ 0.40MPa of gauge pressure, preferably 0.25 ~ 0.40MPa, 600 ~ 800 DEG C of temperature, preferably 610 ~ 750 DEG C, place The reason time 0.5 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
In the method for the present invention step (3), organic formwork agent is tetraethyl ammonium hydroxide, tetramethylammonium hydroxide, tetrapropyl The one or more of ammonium hydroxide.Wherein, after evenly mixing by Y type molecular sieve obtained in step (2) and organic formwork agent, into Row hydrothermal crystallizing, process are as follows: Y type molecular sieve obtained in step (2) being beaten in organic formwork agent aqueous solution, liquid weighs admittedly Amount is than being 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, the mass concentration of 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, and gauge pressure is 0.1~0.2MPa.After crystallization, being filtered and being dried can be carried out using conventional method, and generally dry condition is as follows: 50 ~ Dry 1 ~ 10h at 110 DEG C.
In the method for the present invention, step (4) is roast under low temperature oxygen-enriched atmosphere by the Y type molecular sieve that step (3) obtains, Wherein oxygen-enriched atmosphere refers to that oxygen content is greater than 50v%, and maturing temperature is 300 ~ 450 DEG C, and calcining time is 5 ~ 10h.Roasting is general Using the method roasted 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 using (NH4)2SiF6Place is modified to NaY molecular sieve Reason, while realizing modulation molecular sieve silica alumina ratio, can deviate from together the sodium ion in NaY molecular sieve, then in organic mould Hydrothermal crystallizing is carried out to the molecular sieve after hydro-thermal process in the presence of plate agent, part silicon atom and aluminium atom can be made in organic mould in this way Plate agent effect is lower to enter framework of molecular sieve structure, while further stablizing and improving the skeleton structure of modified molecular screen, disappears Except the non-skeleton structure generated in zeolite-water heat treatment process, unimpeded cellular structure, part organic formwork agent is also able to enter Into the duct of molecular sieve, cooperates subsequent oxygen-enriched low-temperature treatment, the organic formwork agent in molecular sieve controllably can orderly be removed, To generate 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 for, crystallinity is high, mesoporous proportion is high, hole Diameter distribution is more concentrated, and is suitable for as Cracking Component.Since the Y type molecular sieve has bigger pore volume and mesopore volume, more More acid centres are exposed, and are conducive to raw material heavy oil macromolecular and are cracked, but also have more preferably pore-size distribution model It encloses, the cracking degree of reactant can be efficiently controlled, and be conducive to product and be diffused in duct, in this way 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 process flow, reacts 12.0 ~ 20.0MPa of stagnation pressure, volume is empty when liquid 0.5 ~ 2.0h of speed-1, hydrogen to oil volume ratio be 1000:1 ~ 2000:1,370 ~ 435 DEG C of reaction temperature.
Detailed description of the invention
Fig. 1 is the SEM electromicroscopic photograph of 1 gained Modified Zeolite Y of embodiment；
Fig. 2 is the SEM electromicroscopic photograph of 1 gained Modified Zeolite Y of comparative example；
Fig. 3 is the XRD diffraction pattern of 1 gained Modified Zeolite Y of embodiment.
Specific embodiment
Amorphous silica-alumina used in catalyst carrier of the present invention can be prepared by coprecipitation or grafting copolymerization process, by document Middle conventional method preparation.SiO in amorphous silica-alumina obtained2Weight content be 10% ~ 60%, preferably 20% ~ 55%, nothing The pore volume of amorphous silicon-alumina is 0.6 ~ 1.1ml/g, and preferably 0.8 ~ 1.0ml/g, specific surface area is 300 ~ 500m2/ g, 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 is as follows for catalyst carrier for hydrgenating preparation of the present invention: Modified Zeolite Y, amorphous silica-alumina are mixed It closes, extruded moulding, then dry and roasting is prepared into carrier；Drying can be small in 80 DEG C to 150 DEG C of at a temperature of drying 3 ~ 6 When, roasting is roasted 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 (group VIB and by conventional methods 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 for containing required active component Agent carrier, carrier after dipping 100 DEG C ~ 150 DEG C drying 1 ~ 12 hour, it is then small in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 When, final catalyst is made.
The following examples are for being described in more detail technical solution of the present invention, but the scope of the present invention is not limited solely to this The range 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 is measured using XRF method (x ray fluorescence spectrometry), molecular sieve Grain size using SEM(scanning electron microscope) by the way of measure.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 be it is industrially prepared, property is as follows: SiO2/ Al2O3Molar ratio is 5.1, and grain size is ~ 1.7 μm, relative crystallinity 95%, cell parameter 2.468nm, Na2The weight content of O 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
It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 95 DEG C, start that (NH is added dropwise into molecular sieve pulp4)2SiF6Aqueous solution dropped evenly the (NH that 307mL solution concentration is 72g/L at 60 minutes4)2SiF6Solution, constant temperature after completion of dropwise addition Stirring 2 hours, is filtered and is dried after constant temperature, and the butt of molecular sieve is 65.3wt% after drying；After above-mentioned drying Molecular sieve is added in hydrothermal treatment device, to molecule under the conditions of gauge pressure 0.25MPa, 610 DEG C of temperature, processing the time 1.0 hours Sieve carries out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into the tetraethyl hydrogen-oxygen that 520mL mass concentration is 5.3% Change in aqueous ammonium, constant temperature stirs 4 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal crystalline substance Change, 90 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and is dried after crystallization；By hydro-thermal The drying sample that crystallization obtains roasts under oxygen-enriched state, in calcination atmosphere oxygen content be 70v%, heating rate be 1 DEG C/ Min, constant temperature calcining temperature are 420 DEG C, and the constant temperature calcining time is 6 hours, obtain molecular sieve of the present invention.Sample number into spectrum LAY-1, point Son sieve property is listed in table 1.
Embodiment 2
It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp (NH4)2SiF6Aqueous solution dropped evenly the (NH that 182mL solution concentration is 55g/L at 60 minutes4)2SiF6Solution, completion of dropwise addition Constant temperature stirs 2 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 68.0wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 670 DEG C of temperature, processing 2.0 hours time condition Under to molecular sieve carry out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into four that 910mL mass concentration is 7.5% In propyl ammonium hydroxide aqueous solution, under the conditions of 90 DEG C constant temperature stir 4 hours, then by mixed material be transferred in crystallizing kettle into Row hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and dries place after crystallization Reason；The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 65v%, heating rate in calcination atmosphere For 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 are listed in table 1.
Embodiment 3
It takes NaY original powder 278g to be put into 1000mL water purification, is warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp (NH4)2SiF6Aqueous solution dropped evenly the (NH that 417mL solution concentration is 85g/L at 60 minutes4)2SiF6Solution, completion of dropwise addition Constant temperature stirs 3 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 67.2wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, under the conditions of gauge pressure 0.35MPa, 700 DEG C of temperature, processing the time 3.0 hours Hydro-thermal process is carried out to molecular sieve；Molecular sieve after taking 130g hydro-thermal process is put into the tetrem that 1040mL mass concentration is 3.5% In base ammonium hydroxide aqueous solution, constant temperature is stirred 3 hours under the conditions of 85 DEG C, and then mixed material is transferred in crystallizing kettle and is carried out Hydrothermal crystallizing, 80 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 5 hours, is filtered and is dried after crystallization； The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 75v%, heating rate 1 in calcination atmosphere DEG C/min, constant temperature calcining temperature is 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, molecular sieve property is listed in table 1.
Embodiment 4
It takes NaY original powder 278g to be put into 1400mL water purification, is warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp (NH4)2SiF6Aqueous solution dropped evenly the (NH that 200mL solution concentration is 60g/L at 60 minutes4)2SiF6Solution, completion of dropwise addition Constant temperature stirs 2 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 68.1wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 750 DEG C of temperature, processing 2.0 hours time condition Under to molecular sieve carry out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into four that 520mL mass concentration is 6.8% In propyl ammonium hydroxide aqueous solution, under the conditions of 90 DEG C constant temperature stir 3 hours, then by mixed material be transferred in crystallizing kettle into Row hydrothermal crystallizing, 95 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 8 hours, is filtered and dries place after crystallization Reason；The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 70v%, heating rate in calcination atmosphere For 1 DEG C/min, constant temperature calcining temperature is 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 are listed in table 1.
Comparative example 1
It takes NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concn is 1.5mol/L, is warming up to 95 DEG C, constant temperature Stirring 2 hours, is filtered after constant temperature, washs and dries, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming Molecular sieve is roasted 3 hours at 600 DEG C；Then repeat an ammonium exchange, and filtering and drying；Second of ammonium of 100g is taken to hand over Molecular sieve after changing is put into the tetraethyl ammonium hydroxide aqueous solution that 650mL mass concentration is 7.5%, permanent under the conditions of 80 DEG C Mixed material, is then transferred in crystallizing kettle and carries out crystallization by temperature stirring 2 hours, and 100 DEG C of crystallization temperature, gauge pressure 0.1MPa, It crystallization time 8 hours, is filtered and is dried after crystallization；The drying sample that crystallization obtains is roasted under oxygen-enriched state It burns, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, when constant temperature calcining Between be 8 hours, obtain molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.
Comparative example 2
It takes NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concn is 1.5mol/L, is warming up to 95 DEG C, constant temperature Stirring 2 hours divides after constant temperature and is filtered, washs and dries, and the butt of molecular sieve is 63.8wt% after drying；Program liter Temperature roasts molecular sieve 3 hours at 600 DEG C；Then repeat an ammonium exchange, and filtering and drying；Take second of ammonium of 100g Molecular sieve after exchange 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, It is filtered and is dried after constant temperature；Molecular sieve after above-mentioned drying is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 670 DEG C of temperature obtain molecular sieve to molecular sieve progress hydro-thermal process under the conditions of the 2.0 hours time of processing；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 are prepared using the method for embodiment 1 in CN201510147788.3 Matter is listed in table 1.
The property of 1 Y type molecular sieve of table
Product number 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/Al2O3Molar ratio 73.6.3 62.3 81.9 65.8
Mesoporous pore volume (bore dia 2nm ~ 10nm) accounts 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
Product number 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/Al2O3Molar ratio 7.5 33.5 8.6
Mesoporous pore volume (bore dia 2nm ~ 10nm) accounts 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-alumina (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 agent) are put into and roll Mixed grind in machine is rolled into paste, and extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier ZYS-1。
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4 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-alumina (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 agent) are put into and roll Mixed grind in machine is rolled into paste, and extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier ZYS-2。
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4 Hour, catalyst HC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 7 ~ 8
As described in Example 5, it changes LAY-1 into LAY-3, LAY-4 respectively, carrier ZYS-3, ZYS-4 is made and urges Agent 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, be made carrier DZYS-1, DZYS-2, 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 the Activity evaluations of catalyst HC-1, HC-2, HC-3 and HC-4 of the present invention.In fixation It is evaluated on bed hydroprocessing experimental rig, evaluation condition are as follows: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume is empty when liquid 1. 0h of speed-1, use 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 the Activity evaluation of comparative example catalyst DHC-1, DHC-2 and DHC-3 of the present invention.Solid It is evaluated on fixed bed hydrogenation test apparatus, evaluation condition are as follows: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume when liquid Air speed 1.0h-1, use 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 2 catalyst carrier of table and catalyst
Carrier composition and property
Number 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 composition and property
Number 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 composition and property
Number 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 composition and property
Number 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
3 feedstock oil main character of table
Feedstock oil Vacuum distillate (VGO)
Density (20 DEG C), 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
4 catalyst performance comparative evaluation's result of table
Catalyst HC-1 HC-2 HC-3 HC-4
Feedstock oil VGO VGO VGO VGO
Operating condition
Volume space velocity when 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 value 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 when 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 value 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 production Quality is superior to reference catalyst.

Claims (29)

1. a kind of hydrocracking catalyst, including hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y and nothing Amorphous silicon-alumina, wherein the Modified Zeolite Y, property are as follows: relative crystallinity is 110% ~ 150%, SiO2/Al2O3It rubs , than being 55 ~ 100, cell parameter is 2.425 ~ 2.435nm for you, and total pore volume is 0.55 ~ 1.0mL/g, the mesoporous total hole pore volume Zhan 70% or more of volume.
2. catalyst described in accordance with the 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. catalyst described in accordance with the claim 1, it is characterised in that: the grain size of the Y type molecular sieve is 1.0 ~ 2.5 μm.
4. catalyst described in accordance with the claim 1, it is characterised in that: the grain size of the Y type molecular sieve is 1.2 ~ 1.8 μm.
5. catalyst described in accordance with the claim 1, it is characterised in that: the mesoporous bore dia of the Y type molecular sieve be 2nm ~ 10nm。
6. catalyst described in accordance with the claim 1, it is characterised in that: the specific surface area of the Y type molecular sieve is 650m2/g~ 1000m2/g。
7. catalyst described in accordance with the claim 1, it is characterised in that: the specific surface area of the Y type molecular sieve is 750m2/g~ 1000m2/g。
8. catalyst described in accordance with the claim 1, it is characterised in that: the infrared total acid content of the Y type molecular sieve be 0.1 ~ 0.5mmol/g。
9. catalyst described in accordance with the claim 1, it is characterised in that: in the Y type molecular sieve, Na2The weight content of O is 0.15wt% or less.
10. catalyst described in accordance with the claim 1, it is characterised in that: the property of the hydrocracking catalyst is as follows: comparing table Area is 250 ~ 450m2/ g, pore volume are 0.30 ~ 0.50mL/g.
11. catalyst described in accordance with the claim 1, it is characterised in that: the hydrogenation active metals are group VIB and the The metal of VIII group, 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, content of the vib metals in terms of oxide is 10.0% ~ 30.0%, content of the group VIII metal in terms of oxide It is 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 86.0%.
12. catalyst described in accordance with the claim 1, it is characterised in that: the carrier of hydrocracking catalyst, with carrier On the basis of weight, the content of Modified Zeolite Y is 5% ~ 25%, and the content of amorphous silica-alumina is 75% ~ 95%.
13. catalyst described in accordance with the claim 1, it is characterised in that: the carrier of hydrocracking catalyst, with carrier On the basis of weight, the content of Modified Zeolite Y is 5% ~ 20%, and the content of amorphous silica-alumina is 80% ~ 95%.
14. catalyst described in accordance with the claim 1, it is characterised in that: in the amorphous silica-alumina, SiO2Weight content Be 10% ~ 60%, the property of amorphous silica-alumina is as follows: pore volume is 0.6 ~ 1.1mL/g, and specific surface area is 300 ~ 500m2/g。
15. catalyst described in accordance with the claim 1, it is characterised in that: in the amorphous silica-alumina, SiO2Weight content Be 20% ~ 55%, the property of amorphous silica-alumina is as follows: pore volume is 0.8 ~ 1.0mL/g, and specific surface area is 350 ~ 500m2/g。
16. the preparation method of any catalyst of claim 1 ~ 15, preparation and load hydrogenation active metals including carrier Component, wherein the preparation process of carrier is as follows: Modified Zeolite Y, amorphous silica-alumina being mixed, molding, then dry and roasting It burns, catalyst carrier is made, wherein the preparation method of Modified Zeolite Y, includes the following steps:
(1) NaY type molecular sieve and (NH4)2SiF6Aqueous solution contact is reacted, and is filtered and is dried after reaction；
(2) hydro-thermal process is carried out to Y type molecular sieve obtained by step (1)；Hydrothermal conditions: gauge pressure is 0.20 ~ 0.40MPa, temperature Degree is 600 ~ 800 DEG C, and the processing time is 0.5 ~ 5.0 hour；
(3) hydrothermal crystallizing processing is carried out under the conditions of by Y type molecular sieve obtained by step (2) existing for the organic formwork agent, is then passed through Filtering and drying；
(4) step (3) resulting Y type molecular sieve is roasted under low temperature oxygen-enriched atmosphere, Modified Zeolite Y is made.
17. according to the method for claim 16, it is characterised in that hydrothermal conditions described in step (2) are as follows: gauge pressure For 0.25 ~ 0.40MPa, temperature is 610 ~ 750 DEG C, and the processing time is 1.0 ~ 3.0 hours.
18. according to the method for claim 16, it is characterised in that: in step (1), the property of NaY type molecular sieve is as follows:
SiO2/Al2O3Molar ratio is 3 ~ 6, and grain size is 1.0 ~ 2.5 μm, and relative crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2The weight content of O is 6.0wt% ~ 8.0wt%, and specific surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4mL/g, micropore pore volume account for 75% of total pore volume or more.
19. according to the method for claim 18, it is characterised in that in step (1), the property of NaY type molecular sieve is as follows: brilliant Granularity is 1.2 ~ 1.8 μm.
20. according to the method for claim 16, it is characterised in that: in step (1), (NH4)2SiF6Additional amount be NaY type 5wt% ~ 20wt% of molecular sieve dry weight.
21. according to the method for claim 16, it is characterised in that: in step (1), (NH4)2SiF6The quality of aqueous solution is dense Degree is 50 ~ 100g/L.
22. according to the method for claim 16, it is characterised in that: in step (1), NaY type molecular sieve and (NH4)2SiF6Water Solution contacts the reaction condition reacted: temperature is 80 ~ 150 DEG C, and the reaction time is 0.1 ~ 5.0 hour.
23. according to method described in claim 16, it is characterised in that: in step (1), NaY type molecular sieve and (NH4)2SiF6It is water-soluble Liquid contacts the reaction condition reacted: temperature is 90 ~ 120 DEG C, and the reaction time is 1.0 ~ 3.0 hours.
24. according to the method for claim 16, it is characterised in that: in step (1), dry condition is at 50 ~ 95 DEG C 0.5 ~ 5.0 hour dry, the butt of resulting Y type molecular sieve is 60wt% ~ 80wt% after drying.
25. according to the method for claim 16, it is characterised in that: in step (3), organic formwork agent is tetraethyl hydroxide One or more of ammonium, tetramethylammonium hydroxide, tetrapropylammonium hydroxide.
26. according to the method for claim 16, it is characterised in that: by Y type molecular sieve obtained in step (2) and organic mould Plate agent after evenly mixing, carries out hydrothermal crystallizing, and process is as follows: by Y type molecular sieve obtained in step (2) in organic formwork agent water It is beaten in solution, solvent and solute weight ratio is 3:1 ~ 8:1, and 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 is then placed in crystallization in crystallizing kettle, and crystallization temperature is 80 ~ 120 DEG C, when crystallization Between be 4 ~ 10h, gauge pressure be 0.1 ~ 0.2MPa.
27. according to the method for claim 16, it is characterised in that: step (4) is the Y type molecular sieve for obtaining step (3) Roasted under low temperature oxygen-enriched atmosphere, wherein oxygen-enriched atmosphere refers to that oxygen content is greater than 50v%, and maturing temperature is 300 ~ 450 DEG C, Calcining time is 5 ~ 10h.
28. according to the method for claim 16, it is characterised in that: the process of the carrier of hydrocracking catalyst preparation Are as follows:
Modified Zeolite Y, amorphous silica-alumina are mixed, then molding is dried and roasts, is prepared into carrier, described Dry 3 ~ 6 hours dry at a temperature of 80 DEG C ~ 150 DEG C, roasting is roasted 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
29. according to the method for claim 16, it is characterised in that: in the hydrocracking catalyst, active metal is born It carries and 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 It 1 ~ 12 hour, is then roasted 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C, hydrocracking catalyst is made.
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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

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