CN107344117B - Hydrocracking catalyst and its preparation method - Google Patents
Hydrocracking catalyst and its preparation method Download PDFInfo
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- CN107344117B CN107344117B CN201610289566.XA CN201610289566A CN107344117B CN 107344117 B CN107344117 B CN 107344117B CN 201610289566 A CN201610289566 A CN 201610289566A CN 107344117 B CN107344117 B CN 107344117B
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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
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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 catalyst and its preparation methods.The catalyst includes hydrogenation active metal component and carrier, and carrier includes Modified Zeolite Y, beta-molecular sieve and aluminium oxide, 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.In the hydrocracking process of the catalyst midbarrel oil product good for high-output qulified low temperature flow, active high and selective good feature, while can and produce good hydrogenation tail oil.
Description
Technical field
The present invention relates to a kind of hydrocracking catalysts and preparation method thereof, especially evaporate for high-output qulified low solidifying centre
Divide the hydrocracking catalyst and preparation method thereof of oil.
Background technique
In recent years, countries in the world refined products market constantly increases always the demand of high-quality middle cut oil product, with
Economic rapid development, this imbalance between supply and demand seem more prominent.Hydrocracking technology is had become with its exclusive advantage attaches most importance to
Oily deep processing produces the best means of high-quality cleaning intermediate oil.Currently, oil type hydrocracking catalyst in countries in the world
Activity be not it is very high, the condensation point of gained diesel oil is also higher, is difficult to meet refinery and is transformed to existing apparatus or increase processing
Amount is to achieve the purpose that further to increase production intermediate oil.
The key for being hydrocracked the low solidifying intermediate oil that raises productivity and improves the quality is to develop and use suitable catalyst.Containing single
Although the hydrocracking catalyst of molecular sieve component has very high activity, its middle distillates oil selectivity is poor, contains composite molecular screen
Catalyst but show can to improve the activity selective synergistic effect of raising again.
Can there are Y type, β type and ZSM type molecule as the molecular sieve of cracking active component in hydrocracking heavy oil field
Sieve etc., wherein Y type molecular sieve application is the most universal.The method of industrial production Y type molecular sieve is essentially all using beauty at present
The directing agent method that GRACE company, state proposes in USP 3639099 and USP 4166099, the Y type molecular sieve original powder duct of synthesis
Orifice diameter be 0.74nm × 0.74nm, micropore pore volume accounts for about 95% of total pore volume or more.Wax oil hydrogenation cracked stock
In polycyclic heavy constituent molecular diameter usually in 1nm or more, cracking reaction for heavy constituent macromolecular is suitble to it to react and produce
The ideal duct pore diameter range of object diffusion is the macropore range of 2nm ~ 10nm, outside the acid centre that will can more can contact
Dew, while also molecular sieve cracking choosing is improved conducive to the desorption and diffusion of the absorption of raw material macromolecular and reaction and purpose product
Selecting property.To improve the mesoporous pore volume content of Y type molecular sieve low the case where being unfavorable for wax oil macromolecular reaction, usually to Y type molecule
Sieve original powder is modified processing, and the Modified Zeolite Y of different cellular structures and acid distribution can be obtained.
CN201310240740.8 discloses a kind of method of modifying of ultra-steady Y molecular sieve (USY).The characteristics of this method be
Organic acid and inorganic salts dealuminzation reagent is added in modifying process simultaneously, it is modified to carry out the combination of organic acid-inorganic salts.Use this
The mesopore volume of USY molecular sieve made from method reality of the total volume 50% hereinafter, its crystallinity below 85%.
CN201510147788.3 discloses that a kind of silica alumina ratio is high and second hole Y molecular sieve abundant and preparation method thereof.
This method comprises: obtaining dry Y type molecular sieve, being cooled to 200 ~ 600 Y type molecular sieve in 300 DEG C ~ 600 DEG C 1 ~ 5h of processing
℃；In dried over anhydrous environment, it is passed through the dry gas being saturated by dealumination complement silicon agent into dry Y type molecular sieve, reacts
0.5h ~ 7.0h, or in dried over anhydrous environment, while temperature to be at the uniform velocity warming up to 500 ~ 700 DEG C into dry y-type zeolite
It is passed through the dry gas being saturated by dealumination complement silicon agent, 0.5h ~ 7.0h is reacted, obtains crude product；By crude product at 30 ~ 100 DEG C
Alkali process 10min ~ 5h, the solid-liquid mass ratio of alkali process are 1 ~ 50:1, obtain silica alumina ratio height and second hole Y molecular sieve abundant.
US 4,820,402 discloses a kind of hydrocracking catalyst of high selectivity to middle distillates, its main feature is that using a kind of high
The molecular sieve of silica alumina ratio such as ZSM-20, Y and β, molecular sieve silica alumina ratio are at least 50:1, preferably 200:1 or more.This method will not
When being used for hydrocracking catalyst with high silica alumina ratio molecular sieve, middle distillates oil selectivity most preferably ZSM-20, followed by β.The catalysis
The activity and middle distillates oil selectivity of agent need to be further improved.
US 4,419,271 discloses a kind of hydrocarbon conversion catalyst.Cracking Component be modified HY molecular sieve (LZ-10) and
Distributed sial, active metal component are tungsten, nickel.Wherein the content of LZ-10 molecular sieve is 10wt% ~ 70wt%, distributed sial
Content be 30wt% ~ 90wt%, WO3Content be 10wt% ~ 30wt%, the content of NiO is 3wt% ~ 10wt%.The catalyst is available
Production intermediate oil (such as turbine fuel and diesel oil) is hydrocracked in heavy gas oil.The catalyst middle distillates oil selectivity is low.
A kind of method using beta-molecular sieve selective hydrogenation cracking is described in CN101578353A.Beta-molecular sieve without
The molar ratio of hydro-thermal process or at relatively low temperatures hydro-thermal process, silica and aluminium oxide is less than 30:1 and at least
The SF of 28wt%6Adsorbance, the catalyst prepared by modified obtained this beta-molecular sieve as cracking component, midbarrel
The selectivity of oil is not high.
US 5,350,501, US 5,447,623, US 5,279,726, US 5,536,687 describe a kind of containing beta molecule
The catalyst of sieve and Y type molecular sieve.When for producing intermediate oil, consisting of: Y type molecular sieve (1wt% ~ 15wt%), β points
Son sieve (1wt% ~ 15wt%), distributed sial, aluminium oxide, metal W and Ni.Y type molecular sieve used in it is that NaY is handed over by ammonium
It changes, the exchange of hydro-thermal process, ammonium, the method preparation of hydro-thermal process, the crystallinity of modified molecular screen is not high, and product selectivity is poor.It should
Catalyst reaction activity and middle distillates oil selectivity be not high, it is difficult to meet manufacturer's aggrandizement apparatus processing capacity, further increase production
The needs of intermediate oil.
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 catalyst using Modified Zeolite Y and beta-molecular sieve collectively as cracking center, used in Modified Zeolite Y
For it is a kind of rich in meso-hole structure, effective pore sife distribution concentrate Y type molecular sieve, for high-output qulified midbarrel oil product plus
In hydrogen cracking process, active high and selective good feature, while can and produce good hydrogenation tail oil.
Hydrocracking catalyst of the present invention, includes hydrogenation active metal component and carrier, and carrier includes modified Y type molecule
Sieve, beta-molecular sieve and aluminium oxide, 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.
The property of the beta-molecular sieve is as follows: average grain diameter is 200 ~ 400nm, and specific surface area is 600 ~ 800m2/
G, pore volume are 0.35 ~ 0.50mL/g, and relative crystallinity 100% ~ 140%, infrared total acid content is 0.1 ~ 0.5mmoL/g, SiO2/
Al2O3Molar ratio is 40 ~ 80.Hydrothermal crystallization method synthesis can be used in the beta-molecular sieve, generally using organic amine as template, then passes through
Conventional ammonium exchanges, acid is handled and the method for hydro-thermal process is modified and obtains.
In the hydrocracking catalyst, the carrier, on the basis of the weight of carrier, Modified Zeolite Y contains
Amount is 10% ~ 40%, and the content of beta-molecular sieve is 5% ~ 20%, and the content of aluminium oxide is 40% ~ 85%.
The hydrogenation active metals generally use the metal of group VIB and group VIII, and vib metals are preferably molybdenum
He ∕ or tungsten, group VIII metal are preferably Gu He ∕ 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%, vector contg is 62.0% ~ 86.0%.
The property of hydrocracking catalyst of the present invention is as follows: specific surface area is 250 ~ 500m2/ 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, beta-molecular sieve, aluminium oxide 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 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%, cell parameter 2.465 ~ 2.470nm, Na2The weight content of O is 6.0wt% ~ 8.0wt%, compares table
Area is 600 ~ 900m2/ g, 0.3 ~ 0.4 mL/g of total pore volume, micropore pore volume account 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
One or more of ammonium hydroxide.Wherein, after evenly mixing by Y type molecular sieve obtained in step (2) and organic formwork agent,
Hydrothermal crystallizing is carried out, process is as follows: Y type molecular sieve obtained in step (2) being beaten in organic formwork agent aqueous solution, liquid is solid
Weight ratio is 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and 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, gauge pressure
For 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 uses Modified Zeolite Y and beta-molecular sieve collectively as cracking center, both sufficiently
The concerted catalysis effect for having played its respective performance characteristics, and two kinds of molecular sieves capable of being made to generate, i.e., beta molecular sieve is to alkane
Long side chain on hydrocarbon or aromatic hydrocarbons has good isomerization, the condensation point of product can be effectively reduced, while Y type molecular sieve is to aromatic hydrocarbons
There is very high selectivity of ring-opening, improves the product property of purpose product.The active height of hydrocracking catalyst of the present invention, can fecund
High-quality midbarrel oil product (jet fuel+diesel oil), while can and produce good hydrogenation tail oil.
By hydrocracking catalyst of the invention be used for heavy oil hydrocracking when, especially condition of high voltage (12 ~
Wax slop (VGO, CGO and DAO) is handled under 20MPa), can also be added poor ignition quality fuel (coker gas oil and catalytic diesel oil etc.), is had
There are very high catalytic activity and intermediate oil selectivity, and the condensation point reduction amplitude of diesel oil distillate is big, intermediate oil
Product property is improved, and is able to satisfy refinery and is increased operating flexibility, increase device processing capacity, further increase production midbarrel
The needs of oil.
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
Aluminium oxide can be using oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention
Change aluminium, such as macroporous aluminium oxide and ∕ or small porous aluminum oxide.0.6 ~ 1.3mL/g of pore volume of macroporous aluminium oxide used, specific surface area
300~450m2/g.The pore volume of small porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/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: by Modified Zeolite Y, beta-molecular sieve, aluminium oxide
Mixing, extruded moulding, then dry and roasting are 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 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.
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 44.44 grams of LAY-1 molecular sieves (butt 90wt%), 22.22 grams of beta-molecular sieves (crystal grain=250nm, SiO2/Al2O3=
50, pore volume 0.45mL/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g, butt 90wt%), 142.7 grams of macropore oxygen
Change aluminium (pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, nitric acid with
The molar ratio of small porous aluminum oxide is 0.4) to be put into mixed grind in roller, adds water, is rolled into paste, and it is dry at 110 DEG C to squeeze out item for extrusion
It dry 4 hours, is then roasted 4 hours at 550 DEG C, obtains carrier ZS-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 Z C-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 6
By 44.44 grams of LAY-2 molecular sieves (butt 90wt%), 33.3 grams of beta-molecular sieves (crystal grain=250nm, SiO2/Al2O3=
50, pore volume 0.45mL/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g, butt 90wt%), 128.6 grams of macropore oxygen
Change aluminium (pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, nitric acid with
The molar ratio of small porous aluminum oxide is 0.4) to be put into mixed grind in roller, adds water, is rolled into paste, and it is dry at 110 DEG C to squeeze out item for extrusion
It dry 4 hours, is then roasted 4 hours at 550 DEG C, obtains carrier ZS-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 Z C-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 7
By 66.66 grams of LAY-3 molecular sieves (butt 90wt%), 11.11 grams of beta-molecular sieves (crystal grain=250nm, SiO2/Al2O3=
50, pore volume 0.45mL/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g, butt 90wt%), 142.7 grams of macropore oxygen
Change aluminium (pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, nitric acid with
The molar ratio of small porous aluminum oxide is 0.4) to be put into mixed grind in roller, adds water, is rolled into paste, and it is dry at 110 DEG C to squeeze out item for extrusion
It dry 4 hours, is then roasted 4 hours at 550 DEG C, obtains carrier ZS-3.
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 Z C-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 8
By 55.55 grams of LAY-4 molecular sieves (butt 90wt%), 44.44 grams of beta-molecular sieves (crystal grain=250nm, SiO2/Al2O3=
50, pore volume 0.45mL/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g, butt 90wt%), 142.7 grams of macropore oxygen
Change aluminium (pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, nitric acid with
The molar ratio of small porous aluminum oxide is 0.4) to be put into mixed grind in roller, adds water, is rolled into paste, and it is dry at 110 DEG C to squeeze out item for extrusion
It dry 4 hours, is then roasted 4 hours at 550 DEG C, obtains carrier ZS-4.
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 Z C-4 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 4 ~ 6
As described in Example 6, change LAY-2 into LDAY-1, LDAY-2, LDAY-3 respectively, be made carrier DZS-1,
DZS-2, DZS-3 and catalyst DZC-1, DZC-2 and DZC-3, carrier and catalyst composition are shown in Table 2.
Embodiment 9 ~ 12
This embodiment describes the Activity evaluations of catalyst Z C-1, ZC-2, ZC-3 and ZC-4 of the present invention.In fixed bed
It is evaluated on hydrogenation test apparatus, evaluation condition are as follows: reaction stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250:1, volume is empty when liquid
Fast 1.5h-1, process flow is once passed through using one-stage serial, uses vacuum distillate (VGO) as feedstock oil, raw material oil nature
It is listed in table 3, evaluation result is listed in table 4.
Comparative example 7 ~ 9
This comparative example describes the Activity evaluation of comparative example catalyst DZC-1, DZC-2 and DZC-3 of the present invention.Solid
It is evaluated on fixed bed hydrogenation test apparatus, evaluation condition are as follows: reaction stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250:1, body when liquid
Product air speed 1.5h-1, process flow is once passed through using one-stage serial, uses vacuum distillate (VGO) as feedstock oil, feedstock oil
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 | ZS-1 | ZS-2 | ZS-3 | ZS-4 |
| Composition | ||||
| Modified Zeolite Y, wt% | 20 | 20 | 30 | 25 |
| Beta-molecular sieve, wt% | 10 | 15 | 5 | 20 |
| Aluminium oxide | Surplus | Surplus | Surplus | Surplus |
| Property | ||||
| Specific surface area, m2/g | 446 | 450 | 489 | 492 |
| Pore volume, mL/g | 0.67 | 0.66 | 0.68 | 0.64 |
| Catalyst composition and property | ||||
| Number | ZC-1 | ZC-2 | ZC-3 | ZC-4 |
| WO3, wt% | 25.51 | 25.53 | 25.35 | 25.37 |
| NiO, wt% | 6.92 | 6.84 | 6.86 | 6.93 |
| Specific surface area, m2/g | 322 | 3367 | 389 | 345 |
| Pore volume, mL/g | 0.47 | 0.42 | 0.43 | 0.44 |
Continued 2
| Carrier composition and property | |||
| Number | DZS-1 | DZS-2 | DZS-3 |
| Composition | |||
| Modified Zeolite Y, wt% | 20 | 20 | 20 |
| Beta-molecular sieve, wt% | 15 | 15 | 15 |
| Aluminium oxide | Surplus | Surplus | Surplus |
| Property | |||
| Specific surface area, m2/g | 388 | 435 | 298 |
| Pore volume, mL/g | 0.55 | 0.53 | 0.42 |
| Catalyst composition and property | |||
| Number | DZC-1 | DZC-2 | DZC-3 |
| WO3, wt% | 25.51 | 25.57 | 25.56 |
| NiO, wt% | 6.82 | 6.87 | 6.85 |
| Specific surface area, m2/g | 256 | 234 | 196 |
| Pore volume, mL/g | 0.28 | 0.26 | 0.29 |
3 raw material oil nature of table
| Feedstock oil | Vacuum distillate (VGO) |
| Density (20 DEG C), g/cm3 | 0.9072 |
| Boiling range, DEG C | |
| IBP/10% | 305/361 |
| 30%/50% | 394/417 |
| 70%/90% | 443/481 |
| 95%/EBP | 509/533 |
| Condensation point, DEG C | 34 |
| Sulphur, wt% | 1.98 |
| Nitrogen, μ g/g | 1228 |
| Carbon, wt% | 85.28 |
| Hydrogen, wt% | 12.46 |
| BMCI value | 45.0 |
4 catalyst performance comparative evaluation's result of table
| Catalyst | ZC-1 | ZC-2 | ZC-3 | ZC-4 |
| Feedstock oil | Vacuum distillate (VGO) | Vacuum distillate (VGO) | Vacuum distillate (VGO) | Vacuum distillate (VGO) |
| Operating condition | ||||
| Volume space velocity when liquid, h-1 | 1.5 | 1.5 | 1.5 | 1.5 |
| React stagnation pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1250 | 1250 | 1250 | 1250 |
| Cracking zone reaction temperature, DEG C | 372 | 370 | 371 | 365 |
| Product yield and property | ||||
| Heavy naphtha | ||||
| Yield, wt% | 9.5 | 9.0 | 8.7 | 8.0 |
| Virtue is latent, wt% | 64.3 | 65.4 | 63.2 | 64.9 |
| Jet fuel | ||||
| Yield, wt% | 47.9 | 47.5 | 48.1 | 47.3 |
| Smoke point, mm | 28 | 28 | 29 | 27 |
| Aromatic hydrocarbons, v% | 5.1 | 4.1 | 3.3 | 4.3 |
| Diesel oil | ||||
| Yield, wt% | 21.6 | 22.6 | 21.2 | 23.5 |
| Condensation point, DEG C | -16 | -18 | -15 | -19 |
| Cetane number | 69.4 | 68.6 | 70.3 | 68.1 |
| Tail oil | ||||
| Yield, wt% | 15.3 | 16.1 | 16.3 | 16.0 |
| Condensation point, DEG C | 11 | 10 | 13 | 10 |
| BMCI value | 10.8 | 11.9 | 9.6 | 10.2 |
| Intermediate oil selectivity, wt% | 82.10 | 83.6 | 82.8 | 84.2 |
| Chemical hydrogen consumption, wt% | 2.48 | 2.45 | 2.46 | 2.47 |
Continued 4
| Catalyst | ZDC-1 | ZDC-2 | ZDC-3 |
| Feedstock oil | Vacuum distillate (VGO) | Vacuum distillate (VGO) | Vacuum distillate (VGO) |
| Operating condition | |||
| Volume space velocity when liquid, h-1 | 1.5 | 1.5 | 1.5 |
| React stagnation pressure, MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1250 | 1250 | 1250 |
| Cracking zone reaction temperature, DEG C | 378 | 387 | 389 |
| Product yield and property | |||
| Heavy naphtha | |||
| Yield, wt% | 11.2 | 11.9 | 12.6 |
| Virtue is latent, wt% | 62.3 | 61.2 | 59.8 |
| Jet fuel | |||
| Yield, wt% | 44.9 | 43.8 | 42.0 |
| Smoke point, mm | 26 | 26 | 24 |
| Aromatic hydrocarbons, v% | 4.8 | 5.3 | 5.6 |
| Diesel oil | |||
| Yield, wt% | 22.5 | 23.5 | 21.6 |
| Condensation point, DEG C | -6 | -6 | -5 |
| Cetane number | 67.3 | 67.4 | 61.7 |
| Tail oil | |||
| Yield, wt% | 15.1 | 14.3 | 16.1 |
| Condensation point, DEG C | 19 | 21 | 20 |
| BMCI value | 14.6 | 14.9 | 15.3 |
| Intermediate oil selectivity, wt% | 80.6 | 78.6 | 77.0 |
| Chemical hydrogen consumption, wt% | 2.72 | 2.73 | 2.75 |
When it can be seen from the evaluation result of table 4 using hydrocracking catalyst of the present invention, intermediate oil selectivity,
Yield and product quality are superior to reference catalyst.
Claims (28)
1. a kind of hydrocracking catalyst, including hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y, β points
Son sieve and aluminium oxide, 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, mesoporous pore volume
Account for 70% or more of total pore 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 beta-molecular sieve is as follows: crystal grain is average
Diameter is 200 ~ 400nm, and specific surface area is 600 ~ 800m2/ g, pore volume be 0.35 ~ 0.50mL/g, relative crystallinity 100% ~
140%, infrared total acid content is 0.1 ~ 0.5mmoL/g, SiO2/Al2O3Molar ratio is 40 ~ 80.
11. 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.
12. 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% ~ 82.0%.
13. according to catalyst described in claim 1 or 12, it is characterised in that: the carrier of hydrocracking catalyst, with
On the basis of the weight of carrier, the content of Modified Zeolite Y is 10% ~ 40%, and the content of beta-molecular sieve is 5% ~ 20%, aluminium oxide
Content is 40% ~ 85%.
14. the preparation method of any catalyst of claim 1 ~ 13, preparation and load hydrogenation active metals including carrier
Component, wherein the preparation process of carrier is as follows: Modified Zeolite Y, beta-molecular sieve, aluminium oxide being mixed, then molding is dried
And roasting, 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.
15. according to the method for claim 14, 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.
16. according to the method for claim 14, 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.
17. 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: brilliant
Granularity is 1.2 ~ 1.8 μm.
18. according to the method for claim 14, it is characterised in that: in step (1), (NH4)2SiF6Additional amount be NaY type
5wt% ~ 20wt% of molecular sieve dry weight.
19. according to the method for claim 14, it is characterised in that: in step (1), (NH4)2SiF6The quality of aqueous solution is dense
Degree is 50 ~ 100g/L.
20. according to the method for claim 14, 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.
21. according to the method for claim 14, it is characterised in that: in step (1), NaY type molecular sieve and (NH4)2SiF6Water
The reaction condition that solution contact is reacted is as follows: temperature is 90 ~ 120 DEG C, and the reaction time is 1.0 ~ 3.0 hours.
22. according to the method for claim 14, 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.
23. according to the method for claim 14, it is characterised in that: in step (3), organic formwork agent is tetraethyl hydroxide
One or more of ammonium, tetramethylammonium hydroxide, tetrapropylammonium hydroxide.
24. according to the method for claim 14, 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.
25. according to the method for claim 14, 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.
26. according to the method for claim 14, it is characterised in that: the aluminium oxide includes macroporous aluminium oxide and/or small
The property of porous aluminum oxide, the macroporous aluminium oxide is as follows: pore volume is 0.6 ~ 1.3mL/g, and specific surface area is 300 ~ 450m2/
g；The property of the small porous aluminum oxide is as follows: pore volume is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
27. according to the method for claim 14, it is characterised in that: the process of the carrier of hydrocracking catalyst preparation
Are as follows:
Modified Zeolite Y, beta-molecular sieve, aluminium oxide are mixed, then molding is dried and roasts, is prepared into carrier, institute
The drying stated is 3 ~ 6 hours dry at a temperature of 80 DEG C ~ 150 DEG C, and roasting is roasted 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
28. according to the method for claim 14, 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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| 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 |
| CN104667969A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | A hydrocracking catalyst and a preparing method thereof |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104667969A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | A hydrocracking catalyst and a preparing method thereof |
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