CN104923291B - A kind of hydrocracking catalyst and its preparation and application - Google Patents
A kind of hydrocracking catalyst and its preparation and application Download PDFInfo
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Abstract
A kind of hydrocracking catalyst and its preparation and application, the catalyst contains molecular sieve solid acid constituents, the molecular sieve solid acid constituents is the molecular sieve mixture for including MoY types zeolite and at least one y-type zeolite selected from addition to MoY, and MoY types zeolite and at least one weight ratio selected from the y-type zeolite in addition to MoY are 9 in the molecular sieve mixture:1~1:9, wherein the n values of the MoY types zeolite molecular sieve are 0<n<1, n=I/ α I0, characterized in FT IR methods, I is 3625cm in the FT IR spectrograms of MoY type zeolite molecular sieves‑1Absorption peak strength, I0For 3625cm in the FT IR spectrograms of the parent Y-type zeolite molecular sieve of MoY type zeolite molecular sieves‑1Absorption peak strength, α are 3740cm in the FT IR spectrograms of MoY type zeolite molecular sieves‑1Absorption peak strength and 3740cm in the FT IR spectrograms of parent Y-type zeolite molecular sieve‑1The ratio of absorption peak strength.Compared with prior art, when for hydrocracking reaction, the selectivity etc. of the activity of conversion of aromatic hydrocarbons and open-loop products significantly improves catalyst provided by the invention in diesel oil.
Description
Technical field
The present invention is about a kind of hydrocracking catalyst and its preparation and application.
Background technology
To meet increasingly strict fuel oil discharge standard and environmental regulation requirement, need to reduce containing for aromatic hydrocarbons in diesel oil
Amount, especially polycyclic aromatic hydrocarbon, it is considered that fractional saturation+selective opening of aromatic hydrocarbons can obtain height while reducing aromatic hydrocarbons
Cetane value constituents, to obtain the fuel oil products met the requirements.Such as：
201110355795.4 disclosing a kind of hydrocracking catalyst, amorphous silica-alumina and Y types are contained in the catalyst
The compound of molecular sieve, Y type molecular sieve content is 10 weight %-60 weight % in the compound, amorphous silicon aluminium content is 40 weights
Measure %-90 weight %, specific surface area 400m2/g-1000m2/ g, Kong Rongwei 0.6cm3/g-2.0cm3/ g, meleic acid amount are 0.3-
1.0mmol/g, B acid/L acid are 1.5-4.0, and middle strong acid amount accounts for 60% of total acid content or more.
201210548282.X discloses a kind of middle oil type hydrocracking catalyst, and the catalyst is by the sial containing molecular sieve
Carrier and hydrogenation active metals are made, and the content of the silica-alumina supports and hydrogenation active metals containing molecular sieve is respectively 65 weights
Measure %-85 weight % and 15 weight %-35 weight %.Molecular sieve is the height prepared through hydrothermal dealumination and chemical dealuminization method in carrier
SiO2/Al2O3The modified Y molecular sieve of molar ratio, high-specific surface area, high-crystallinity.
CN1178238A discloses a kind of catalyst for hydrocracking diesel oil, the catalyst by aluminium oxide, amorphous silica-alumina and
The hydrogenation active metals of the carrier and load of molecular sieve composition on this carrier form, WO in catalyst3Content be 10-30 weight
The content of amount %, NiO are 2-15 weight %, the content of molecular sieve is 5-45 weight %, the content of aluminium oxide is 30-70 weights
Measure %, amorphous silica-alumina content be 5-25 weight %, the molecular sieve be Y type molecular sieve, infrared total acid content be 0.5-
1.0mmol/g, lattice constant 2.436-2.444nm.It is 0.8-1.1cm that the alumina pore, which holds,3/ g, surface area 230-
400m2The small porous aluminum oxide of/g.
This kind of catalyst category bifunctional catalyst（Add hydrogen and cracking function）, wherein improve aromatic hydrogenation saturation and open loop
Reactivity inhibits the cracking reaction of ideal diesel component, is the problem of such catalyst of research and development is paid special attention to.
Invention content
The technical problem to be solved in the present invention is to provide a kind of hydrocracking catalysts new, catalyst performance is improved
Agent, the catalyst preparation method and applications.
Invention content of the present invention includes：
1, a kind of hydrocracking catalyst contains the carrier of the acid constituents containing molecular sieve solid, the molecular sieve solid acid group
It is divided into including MoY types zeolite and at least one molecular sieve mixture selected from the y-type zeolite in addition to MoY, the molecular sieve is mixed
It is 9 to close MoY types zeolite and at least one weight ratio selected from the y-type zeolite in addition to MoY in object:1~1:9, wherein described
The n values of MoY type zeolite molecular sieves are 0<n<1, n=I/ α I0, characterized in FT-IR methods, I is the FT-IR of MoY type zeolite molecular sieves
3625cm in spectrogram-1Absorption peak strength, I0In FT-IR spectrograms for the parent Y-type zeolite molecular sieve of MoY type zeolite molecular sieves
3625cm-1Absorption peak strength, α are 3740cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorption peak strength and parent Y types
3740cm in the FT-IR spectrograms of zeolite molecular sieve-1The ratio of absorption peak strength.
2, the catalyst according to 1, which is characterized in that MoY types zeolite and at least one in the molecular sieve mixture
Weight ratio selected from the y-type zeolite in addition to MoY is 4:1~1:1.
3, the catalyst according to 1, which is characterized in that the n values of the MoY types zeolite molecular sieve are 0.4≤n≤0.8.
4, the catalyst according to 1, which is characterized in that on the basis of the MoY types zeolite molecular sieve, the MoY boilings
The content of molybdenum in stone molecular sieve in terms of oxide is 0.5-10 weight %.
5, the catalyst according to 4, which is characterized in that on the basis of the MoY types zeolite molecular sieve, the MoY types
The content of molybdenum in zeolite molecular sieve in terms of oxide is 2-8 weight %.
6, the catalyst according to 1, which is characterized in that the parent Y-type zeolite molecular sieve of the MoY type zeolites is selected from
In HY, Rare Earth Y, rare earth HY, super steady Y, hyperastable Y-type RE, the Y of part amorphous, the Y of titaniferous, phosphorous Y-type zeolite molecular sieve
One or more.
7, the catalyst according to 1, which is characterized in that the y-type zeolite in addition to MoY is selected from HY, Rare Earth Y, dilute
Native HY, super steady Y, hyperastable Y-type RE, the Y of part amorphous, the Y of titaniferous, one kind in phosphorous Y-type zeolite molecular sieve or several
Kind.
8, the catalyst according to 1, which is characterized in that the hydrogenation active metal component in the catalyst is selected from least
A kind of VIII race's metal component and at least one VI B metal components, are counted by oxide and on the basis of the catalyst, VIII race
The content of metal component is 1-10 weight %, and the content of VI B races metal component is 5-50 weight %.
9, the catalyst according to 8, which is characterized in that VIII race metal component is selected from cobalt and/or nickel, VI B metals
Group is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the content of VIII race metal component is 2-8
The content of weight %, VI B races metal component are 10-35 weight %.
10, the catalyst according to 1, which is characterized in that contain heat-resistant inorganic oxide matrix in the carrier, with institute
On the basis of stating carrier, the content of the heat-resistant inorganic oxide matrix is more than 0 to less than equal to 99 weight %.
11, the catalyst according to 10, which is characterized in that the heat-resistant inorganic oxide matrix is selected from aluminium oxide, oxygen
One or more of SiClx and silica-alumina, on the basis of the carrier, the heat-resistant inorganic oxide matrix contains
Amount is 10-90 weight %.
12, the catalyst according to 1 or 10, which is characterized in that on the basis of the catalyst, carried in the catalyst
The content of body is 45-85 weight %, and the content of VIII race metal component in terms of oxide is 1-10 weight %, with oxide
The content of VI B races metal component of meter is 5-50 weight %.
13, the catalyst according to 12, which is characterized in that on the basis of the catalyst, carrier in the catalyst
Content be 55-85 weight %, the content of VIII race metal component in terms of oxide is 2-8 weight %, in terms of oxide
The content of VI B races metal component is 10-35 weight %.
14, a kind of preparation method of hydrocracking catalyst, including the carrier containing the acid constituents containing molecular sieve solid is prepared,
The molecular sieve solid acid constituents be include MoY types zeolite and at least one y-type zeolite selected from addition to MoY molecular sieve it is mixed
Object is closed, MoY types zeolite and at least one weight ratio selected from the y-type zeolite in addition to MoY in the molecular sieve mixture
It is 9:1~1:9, wherein the n values of the MoY types zeolite molecular sieve are 0<n<1, n=I/ α I0, characterized in FT-IR methods, I is
3625cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorption peak strength, I0It is boiled for the parent Y types of MoY type zeolite molecular sieves
3625cm in the FT-IR spectrograms of stone molecular sieve-1Absorption peak strength, α are 3740cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Y-type zeolite molecular sieve-1The ratio of absorption peak strength.
15, the method according to 14, which is characterized in that MoY types zeolite and at least one in the molecular sieve mixture
Weight ratio selected from the y-type zeolite in addition to MoY is 4:1~1:1；The n values of the MoY types zeolite molecular sieve are 0.4≤n
≤0.8。
16, the method according to 14, which is characterized in that on the basis of the MoY types zeolite molecular sieve, the MoY boilings
The content of molybdenum in stone molecular sieve in terms of oxide is 0.5-10 weight %.
17, the method according to 16, which is characterized in that on the basis of the MoY types zeolite molecular sieve, the MoY types
The content of molybdenum in zeolite molecular sieve in terms of oxide is 2-8 weight %.
18, the method according to 14, which is characterized in that the parent Y-type zeolite molecular sieve is selected from HY, Rare Earth Y, rare earth
HY, super steady Y, hyperastable Y-type RE, the Y of part amorphous, the Y of titaniferous, phosphorous one or more of Y-type zeolite molecular sieve.
19, the method according to 14, which is characterized in that the y-type zeolite in addition to MoY is selected from HY, Rare Earth Y, dilute
Native HY, super steady Y, hyperastable Y-type RE, the Y of part amorphous, the Y of titaniferous, one kind in phosphorous Y-type zeolite molecular sieve or several
Kind.
20, the method according to 14, which is characterized in that the preparation method of the MoY types zeolite molecular sieve includes：（1）
Y-type zeolite molecular sieve is mixed with compound containing Mo, obtains a kind of mixture of Y-type zeolite molecular sieve and the compound containing Mo, respectively
The dosage of component makes in final MoY types zeolite molecular sieve, and the molybdenum content in terms of oxide is 0.5-10 weight %；（2）By step
（1）Obtained mixture encloses lower high-temperature process in steam-laden atmosphere, and the condition of the high-temperature process includes that calcination temperature is
200-700 DEG C, roasting time is 1-24 hours, and steam-laden gas flow is 0.3-2 standard cubic meters/kilogram hour,
Obtain MoY type zeolite molecular sieves.
21, the method according to 20, which is characterized in that the step（1）The dosage of middle each component makes final MoY types boil
In stone molecular sieve, the molybdenum content in terms of oxide is 2-8 weight %；The step（2）In high-temperature process condition include roasting
Temperature is 400-650 DEG C, and roasting time is 2-12 hours, and steam-laden gas flow is 0.6-1.5 standard cubic meter/thousand
Gram hour.
22, the method according to 20, which is characterized in that contain diluent gas in the steam-laden atmosphere, wherein
The volume mixture ratio of the vapor and diluent gas is 1：10-100.
23, the method according to 22, which is characterized in that the diluent gas is selected from hydrogen, nitrogen and its gaseous mixture, or
Person is selected from the gaseous mixture of air and air and nitrogen；The volume mixture ratio of the vapor and diluent gas is 1：20-80.
24, the method according to 14, which is characterized in that the method includes introducing hydrogenation activity into the carrier
The step of metal component, the hydrogenation active metal component in the hydrocracking catalyst are selected from least one VIII race's metal component
It at least one VI B metal components, is counted by oxide and on the basis of the catalyst, the introduction volume of VIII race metal component
Making the content of VIII race's metal component in final catalyst be the introduction volume of 1-10 weight %, VI B races metal component makes finally to urge
The content of VI B races metal component is 5-50 weight % in agent.
25, the method according to 24, which is characterized in that VIII race metal component is selected from cobalt and/or nickel, VI B metals
Group is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the introduction volume of VIII race metal component makes most
The content of VIII race's metal component, which is the introduction volume of 2-8 weight %, VI B races metal component, in whole catalyst makes final catalyst
In VI B races metal component content be 10-35 weight %.
26, the method according to 14, which is characterized in that the method includes introducing heat resistant inorganic into the carrier
The step of matrix of oxide, on the basis of the carrier, the introduction volume of the heat-resistant inorganic oxide matrix makes in final carrier
The content of heat-resistant inorganic oxide matrix is more than 0 to less than equal to 99 weight %.
27, the method according to 26, which is characterized in that on the basis of the carrier, the heat-resistant inorganic oxide base
The introduction volume of matter makes the content of heat-resistant inorganic oxide matrix in final carrier be 10-90 weight %.
28, a kind of method for hydrogen cracking is included under hydrocracking condition and contacts hydrocarbon ils with catalyst, wherein is described
Catalyst is the catalyst that aforementioned 1-13 is provided.
3625cm in the FT-IR spectrograms of the Y zeolites-1Absorption peak refers to 3625 ± 10cm in FT-IR spectrograms-1Place
Absorption peak, which belongs to the vibration absorption peak of acid hydroxy group in y-type zeolite supercage.The FT-IR spectrograms of the Y zeolites
In 3740cm-1Absorption peak refers to the 3740cm in FT-IR spectrograms-1±10cm-1The absorption peak at place, the absorption peak belong to Y types
The vibration absorption peak of zeolite end Si-OH.
It was found by the inventors of the present invention that when with n=I/ α I0Indicate that Y-type zeolite molecular sieve introduces FT- before and after Mo metal components
3625cm in IR spectrograms-1When the variation of absorption peak strength, the MoY type zeolite molecular sieves that are prepared using method provided by the invention
The strength reduction of the vibration performance absorption peak of this acid hydroxy group.And to contain this MoY types zeolite molecular sieve and Y type molecular sieve
Molecular sieve mixture be catalyst prepared by acidic components plus hydrogen aromatic hydrocarbons is full is significantly improved with open-loop performance.
In the present invention, the MoY zeolites are one kind 0<n<1, the preferably y-type zeolite of 0.4≤n≤0.8.Preferably, with
On the basis of the MoY types zeolite molecular sieve（In the present invention, the content of molybdenum oxide in MoY type zeolite molecular sieves（Mass fraction）=wait for
Survey measured value/(amount × butt of MoY types zeolite molecular sieve to be measured) of molybdenum oxide in MoY type zeolite molecular sieves.Butt is to be measured
Sample under air atmosphere 600 DEG C roasting 4 hours after weight with roasting before weight ratio）, the content of Mo in the MoY zeolites
For 0.5-10 weight %, further preferably 2-8 weight %.
The parent Y-type zeolite molecular sieve can be HY zeolites, rare-earth type Y zeolites REY, rare-earth type HY zeolites REHY, surpass
Stabilized zeolite USY, the USY of part amorphous, rare-earth type overstable gamma zeolite REUSY, the Y zeolites of titaniferous, phosphorous Y and it is super steady and
One or more of HY types zeolite, dealuminium Y type beta stone.They can be commercially available commodity, can also use arbitrary existing
Method is prepared.
In a specific embodiment, the method for the invention for introducing Mo to Y-type zeolite molecular sieve includes：
（1）Y-type zeolite molecular sieve is mixed with compound containing Mo, obtains a kind of Y-type zeolite molecular sieve and compound containing Mo
Mixture；
（2）By step（1）Obtained mixture encloses lower roasting in steam-laden atmosphere, obtains MoY type zeolite molecular sieves；
Wherein, the step（1）The dosage of middle each component makes in final MoY types zeolite molecular sieve, preferably in terms of oxide
Molybdenum content be 0.5-10 weight %, molybdenum content further preferably in terms of oxide is 2-8 weight %；The molybdate compound is excellent
Oxide, chloride or molybdate selected from molybdenum etc.；The step（2）In roasting condition include：Temperature is 200-700 DEG C,
Preferably 400-650 DEG C, the time is 1-24 hours, and preferably 3-12 hours, steam-laden gas flow was vertical for 0.3-2 standards
Square rice/kilogram hour, preferably 0.6-1.5 standard cubic meters/kilogram hour.
In preceding method, contain diluent gas in the preferably described steam-laden atmosphere, the diluent gas can select
Example such as：Gaseous mixture selected from hydrogen, nitrogen and its gaseous mixture, or selected from air and air and nitrogen, wherein described
The volume mixture ratio of vapor and diluent gas is preferably 1：10-100, further preferably 1：20-80.
According to catalyst provided by the invention, wherein the Y-type zeolite molecular sieve in addition to MoY can be HY zeolites,
The super steady Y boilings of rare-earth type Y zeolites REY, rare-earth type HY zeolites REHY, overstable gamma zeolite USY, the USY of part amorphous, rare-earth type
One or more of stone REUSY, the Y zeolites of titaniferous, phosphorous Y and super steady and HY types zeolite, dealuminium Y type beta stone.They can
To be commercially available commodity, can also be prepared using arbitrary existing method.The y-type zeolite in addition to MoY with it is aforementioned
Both parent Y-type zeolite molecular sieves can be the same or different.
According to catalyst provided by the invention, heat-resistant inorganic oxide is preferably comprised.The heat-resistant inorganic oxide can be with
Selected from arbitrarily frequently as preparing catalyst carrier for hydrgenating（Or matrix）.In a preferred embodiment, the heat resistant inorganic oxygen
Compound is selected from one or more of aluminium oxide, silica and silica-alumina.They can be commercially available commodity or use
Any one existing method obtains.
According to catalyst provided by the invention, wherein the carrier regard it is different require to can be made into it is various it is easily operated at
Type object, such as microballoon, spherical shape, tablet or bar shaped etc..The molding can carry out by a conventional method, for example, will the zeolite containing MoY
The molecular sieve mixture of molecular sieve and Y-type zeolite molecular sieve, the side with or without heat-resistant inorganic oxide extruded moulding and roasting
It is prepared by method.In carrier extrusion molding, appropriate extrusion aid and/or adhesive, then extrusion molding can be added into carrier.Institute
Field can be selected from by stating extrusion aid, the type of peptizing agent and dosage extrusion aid known to those skilled in the art such as common
One or more of cyanines powder, methylcellulose, starch, polyvinyl alcohol, polyethanol.
According to catalyst provided by the invention, hydrogenation active metal component therein is such catalyst conventional selection, example
Such as, including it is at least one selected from VIII race's metal component and at least one selected from VI B races metal component.Preferred VIII race metal component
For cobalt and/or nickel, VI B races metal component is molybdenum and/or tungsten.It is counted by oxide and on the basis of the catalyst, VIII race
The content of metal component is preferably 1-10 weight %, further preferably 2-8 weight %, and the content of VI B races metal component is excellent
It is selected as 5-50 weight %, further preferably 10-35 weight %.The present invention calculate VI B races metal component content when, including
Mo in MoY zeolite molecular sieves is counted.
Under the premise of being enough the hydrogenation active metal component being carried on the carrier, the present invention is to described negative
Support method is not particularly limited, and preferred method is infusion process, including prepares the dipping solution of the compound containing the metal, it
Afterwards with the solution dipping carrier.The dipping method is conventional method, for example, it may be excessive liquid dipping, hole are satisfied
With method infusion process.It wherein, can be with by the adjusting and control of the concentration of the solution to metallic components, dosage or carrier dosage
The catalyst of specified content is prepared, this is that those skilled in the art are readily appreciated by and realize.
Described one kind or several contained in soluble compound of the metal component compound selected from VI B races in them
Kind, such as one or more of molybdenum oxide, molybdate, paramolybdate, molybdenum oxide, ammonium molybdate, ammonium paramolybdate preferably wherein；Tungsten
One or more of hydrochlorate, metatungstate, ethyl metatungstate, ammonium metatungstate, ethyl ammonium metatungstate preferably wherein.It is described
Containing selected from VIII race's metal component compound be selected from their one or more of soluble compound, such as cobalt nitrate, vinegar
One or more of the soluble complexes of sour cobalt, basic cobaltous carbonate, cobalt chloride and cobalt, preferably cobalt nitrate, basic carbonate
Cobalt；One or more of the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel, preferably nitric acid
Nickel, basic nickel carbonate.
According to catalyst provided by the invention, any present invention that do not influence can also be contained, catalyst catalytic performance is provided
Substance or the substance that catalyst catalytic performance provided by the invention can be improved.Can such as be introduced into phosphorus, one kind in titanium component or
Two kinds, based on the element and on the basis of catalyst, the introduction volume of above-mentioned auxiliary agent is 0-10 weight %, preferably 0.5-5 weight %.
Timesharing is organized selected from one or both of components such as phosphorus, titanium or silicon when that can also contain in the catalyst, it is described
Introducing method selected from components such as phosphorus, titaniums is conventional method, and the compound of auxiliary agent is directly and solid acid as described in can be will contain
Component, is molded and roasts boehmite mixing；Can by the compound containing the auxiliary agent and contain hydrogenation active metals
The compound of component contacts after being configured to mixed solution with the carrier；It can also be and individually prepare the compound containing auxiliary agent
It contacts and roasts with the carrier after solution.When auxiliary agent and hydrogenation active metals introduce the carrier respectively, preferably use first
Contact and roast with the carrier containing auxiliary compound solution, later again with the compound containing hydrogenation active metal component
Solution contacts, such as by the method for dipping, and the calcination temperature is 250-600 DEG C, preferably 350-500 DEG C, roasting time
It is 2-8 hours, preferably 3-6 hours.
Optionally it can be dried, roast or not roast after the metal impregnation step is completed according to the present invention
And etc..The condition of the drying and roasting is conventional, for example, drying temperature is 100-300 DEG C, preferably 100-280
DEG C, drying time is 1-12 hours, preferably 2-8 hours；Calcination temperature is 350-550 DEG C, preferably 400-500 DEG C, is roasted
Time is 1-10 hours, preferably 2-8 hours.
It can also contain selected from one or more of oxygen-containing or organic compounds containing nitrogen in catalyst provided by the invention
Organic compound, preferred oxygen-containing organic compound be selected from one or more of Organic Alcohol and organic acid；It is preferred nitrogenous
Organic compound is selected from one or more of organic amine.For example, oxygen-containing organic compound can enumerate ethylene glycol, glycerine,
Polyethylene glycol（Molecular weight is 200-1500）, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- rings
One or more of hexane diamine tetraacethyl, citric acid, tartaric acid, malic acid, organic compounds containing nitrogen can be ethylenediamine,
EDTA and its ammonium salt.Mole of the organic compound and group VIII and the sum of vib metals component in terms of oxide
Than for 0.03-2, preferably 0.08-1.5.
According to the conventional method in this field, the hydrotreating catalyst before the use, can usually exist in hydrogen
Under, presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140-370 DEG C, this presulfurization can carry out outside device
Also can be In-situ sulphiding in device, convert the active metal component that it is loaded to metal sulfide component.
In process for hydrocracking of hydrocarbonaceous provided by the invention, there is no any special limit to the hydrocracking reaction condition
It is fixed, common reaction condition may be used, such as it is 200-420 DEG C, further preferably 220-400 that can enumerate reaction temperature
DEG C, pressure is 2-18 megapascal, further preferably 2-15 megapascal, liquid hourly space velocity (LHSV) 0.3-10 hours- 1, further preferably 0.3-5
Hour- 1, hydrogen to oil volume ratio 50-5000, further preferably 50-4000.
The device of the hydrotreating reaction can be enough to make the feedstock oil at hydrotreating reaction conditions any
It is carried out with catalytic react in dress device of the catalyst, for example, in the fixed bed reactors, moving-burden bed reactor or boiling
It rises in a reactor and carries out.
Compared with prior art, when the present invention provides catalyst for hydrocracking reaction process, aromatic hydrocarbons turns in diesel oil
The selectivity of change and open-loop products（Reduce the secondary cracking of open-loop products）Etc. significantly improving.Can be directly used for processing it is various not
Same hydrocarbon oil crude material, to carry out hydro-upgrading to it.The hydrocarbon oil crude material include various heavy mineral oils or synthetic oil or they
Mixed fraction oil, for example, selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil,
One or more of frivolous coal tar and heavy deasphalted oil.Particularly suitable for poor ignition quality fuel hydro-upgrading or add hydrogen split
Change.
Specific implementation mode
The present invention will be further described for following example.
Framework of molecular sieve hydroxyl is infrared by Fourier（FT-IR）It measures, sample is roasted into 2h at 350 DEG C first, keep
Vacuum degree 10-6Then Pa is down to the hydroxyl INFRARED SPECTRUM of room temperature measuring molecular sieve.Mo contents are by x-ray fluorescence light in MoY molecular sieves
Spectrometry（XRF）It measures, experimental method is sieve sample compression molding, and rhodium target, laser voltage 50kV, laser current 50mA are adopted
Semi-quantitative analysis is carried out with external standard method.
Embodiment 1
Take 200.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）It is being ground with 1.5 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 24 hours in 300 DEG C under hydrogen and steam atmosphere,
Gas flow therein is 0.5m3The mixed proportion of/(kgh), vapor and hydrogen is 1:40.It obtains Mo and is modified USY types point
Son sieve MoUSY1, is measured using XRF methods（Similarly hereinafter）, MoO in MoUSY13Content and n values be listed in table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 170.4 grams of USY molecular sieves
（Chang Ling catalyst branch product, butt 0.75）It is mixed in 19.1 grams of MoUSY1 samples, it is 1.6 millimeters to be extruded into circumscribed circle diameter
Cloverleaf pattern item, wet bar in 150 DEG C of dry 3h, 550 DEG C roasting 3h, obtain carrier Z1.
100.0 grams of carrier Z1 are taken, contain MoO with 100 milliliters3175.0 grams per liters, NiO75.0 grams per liters ammonium heptamolybdate and nitric acid
The mixed solution of nickel impregnates 4 hours, is roasted 3 hours in 150 DEG C of dry 3h, 400 DEG C, obtains catalyst C1.Using catalyst as base
Quasi- forms as shown in table 2 after the roasting of C1 catalyst（Active metal component is measured using XRF methods, similarly hereinafter）.
Embodiment 2
Take 200.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）It is being ground with 6.3 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 4 hours in 450 DEG C under hydrogen and steam atmosphere,
Gas flow therein is 0.8m3The mixed proportion of/(kgh), vapor and hydrogen is 1:30.It obtains Mo and is modified USY types point
MoO in son sieve MoUSY2, MoUSY23Content and n values be listed in table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 37.9 grams of USY molecular sieves（It is long
Ridge catalyst branch product, butt 0.75）It is mixed with 9.8 grams of MoUSY2 samples, is extruded into three that circumscribed circle diameter is 1.6 millimeters
Clover shape item, wet bar obtain carrier Z2 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
100.0 grams of carrier Z2 are taken, contain MoO with 80 milliliters3645.8 grams per liters, NiO125.0 grams per liters, P2O562.5 grams per liter,
Nickel, the molybdenum complex solution of 135.0 grams per liter citric acids impregnate 4 hours, 3 hours dry in 150 DEG C, obtain catalyst C2.With catalysis
On the basis of agent, formed after the roasting of C2 catalyst as shown in table 2.
Embodiment 3
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）51.0 gram USY molecular sieve（It is long
Ridge catalyst branch product, butt 0.75）It is mixed with 52.6 grams of MoUSY2 samples, it is 1.6 millimeters to be extruded into circumscribed circle diameter
Cloverleaf pattern item, wet bar obtain carrier Z3 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
100.7 grams of carrier Z3 are taken, contain MoO with 90 milliliters3288.5 grams per liters, NiO44.4 grams per liters, P2O529.7 grams per liter,
Nickel, the molybdenum complex solution of 48.0 grams per liter citric acids impregnate 4 hours, 3 hours dry in 150 DEG C, obtain catalyst C3.With catalysis
On the basis of agent, formed after the roasting of C3 catalyst as shown in table 2.
Embodiment 4
Take 200.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）It is being ground with 6.3 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 2 hours in 550 DEG C under hydrogen and steam atmosphere,
Gas flow therein is 1.2m3The mixed proportion of/(kgh), vapor and hydrogen is 1:50.It obtains Mo and is modified USY types point
MoO in son sieve MoUSY3, MoUSY33Content and n values be listed in table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 51.0 grams of USY molecular sieves（It is long
Ridge catalyst branch product, butt 0.75）It is mixed with 52.6 grams of MoUSY3 samples, it is 1.6 millimeters to be extruded into circumscribed circle diameter
Cloverleaf pattern item, wet bar obtain carrier Z4 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
100.7 grams of carrier Z4 are taken, contain MoO with 90 milliliters3288.5 grams per liters, NiO44.4 grams per liters, P2O529.7 grams per liter,
Nickel, the molybdenum complex solution of 48.0 grams per liter citric acids impregnate 4 hours, 3 hours dry in 150 DEG C, obtain catalyst C4.With catalysis
On the basis of agent, formed after the roasting of C4 catalyst as shown in table 2.
Embodiment 5
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 60.9 grams of USY molecular sieves（It is long
Ridge catalyst branch product, butt 0.75）It is mixed with 20.9 grams of MoUSY3 samples, it is 1.6 millimeters to be extruded into circumscribed circle diameter
Cylindrical bar, wet bar obtain carrier Z5 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
100.3 grams of carrier Z5 are taken, contain MoO with 85 milliliters3604.3 grams per liters, NiO117.6 grams per liters, P2O558.8 grams per liter,
Nickel, the molybdenum complex solution of 127.1 grams per liter citric acids impregnate 4 hours, 3 hours dry in 150 DEG C, obtain catalyst C5.With catalysis
On the basis of agent, formed after the roasting of C5 catalyst as shown in table 2.
Embodiment 6
Take 200.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）It is being ground with 14.8 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 8 hours in 600 DEG C under hydrogen and steam atmosphere,
Gas flow therein is 1.8m3The mixed proportion of/(kgh), vapor and hydrogen is 1:90.It obtains Mo and is modified USY types point
MoO in son sieve MoUSY4, MoUSY43Content and n values be listed in table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 51.0 grams of USY molecular sieves（It is long
Ridge catalyst branch product, butt 0.75）It is mixed with 54.8 grams of MoUSY4 samples, it is 1.6 millimeters to be extruded into circumscribed circle diameter
Cloverleaf pattern item, wet bar obtain carrier Z6 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
101.7 grams of carrier Z6 are taken, contain MoO with 88 milliliters3283.7 grams per liters, NiO45.5 grams per liters, P2O530.3 grams per liter,
Nickel, the molybdenum complex solution of 49.1 grams per liter citric acids impregnate 4 hours, 3 hours dry in 150 DEG C, obtain catalyst C6.With catalysis
On the basis of agent, formed after the roasting of C6 catalyst as shown in table 2.
Embodiment 7
Take 200.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）It is being ground with 14.8 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 8 hours in 600 DEG C under hydrogen and steam atmosphere,
Gas flow therein is 0.8m3The mixed proportion of/(kgh), vapor and hydrogen is 1:30.It obtains Mo and is modified USY types point
MoO in son sieve MoUSY5, MoUSY53Content and n values be listed in table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 46.7 grams of silica-oxidations
Aluminium（Chang Ling catalyst branch product, butt 0.76）, 15.8 grams of USY molecular sieves（Chang Ling catalyst branch product, butt
0.75）It is mixed with 67.8 grams of MoUSY5 samples, is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, wet bar is dry in 150 DEG C
Dry 3h, 550 DEG C of roasting 3h, obtain carrier Z7.
102.0 grams of carrier Z7 are taken, contain MoO with 85 milliliters3182.4 grams per liters, NiO88.2 grams per liters ammonium heptamolybdate and nickel nitrate
Mixed solution impregnate 4 hours, in 150 DEG C of dry 3h, 400 DEG C roasting 3 hours, obtain catalyst C7.On the basis of catalyst,
It is formed after the roasting of C7 catalyst as shown in table 2.
Embodiment 8
Take 100.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）With 107.4 grams of MoUSY2 molecules
Sieve, the compression molding on DY-20 powder compressing machines, pressure 10MPa, 150 DEG C of dryings 3 hours prepare carrier Z8.
104.9 grams of Z8 are taken, contain MoO with 75 milliliters3290.2 grams per liters, NiO40 grams per liters, P2O526.7 grams per liters, 43.2 grams/
Rise nickel, the molybdenum complex solution dipping of citric acid 4 hours, it is 3 hours dry in 150 DEG C, obtain catalyst C8.Using catalyst as base
Quasi- forms as shown in table 2 after the roasting of C8 catalyst.
Embodiment 9
Take 200.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）It is being ground with 14.8 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 12 hours in 300 DEG C under air and steam atmosphere,
Gas flow therein is 1.2m3The mixed proportion of/(kgh), vapor and air is 1:15.It obtains Mo and is modified USY types point
MoO in son sieve MoUSY6, MoUSY63Content and n values be listed in table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 12.6 grams of USY molecular sieves（It is long
Ridge catalyst branch product, butt 0.75）It is mixed with 122.0 grams of MoUSY6 samples, is extruded into a diameter of 1.6 millimeters of shape cylinder
Shape item, wet bar obtain carrier Z9 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
103.6 grams of carrier Z9 are taken, contain MoO with 85 milliliters3163.5 grams per liters, NiO88.2 grams per liters ammonium heptamolybdate and nickel nitrate
Mixed solution impregnate 4 hours, in 150 DEG C of dry 3h, 400 DEG C roasting 3 hours, obtain catalyst C9.On the basis of catalyst,
It is formed after the roasting of C9 catalyst as shown in table 2.
Embodiment 10
Take 200.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）It is being ground with 28.1 grams of molybdenum pentachlorides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 24 hours in 300 DEG C under nitrogen and steam atmosphere,
Gas flow therein is 1.2m3The mixed proportion of/(kgh), vapor and nitrogen is 1:15.It obtains Mo and is modified USY types point
MoO in son sieve MoUSY7, MoUSY73Content and n values be listed in table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 31.6 grams of USY molecular sieves（It is long
Ridge catalyst branch product, butt 0.75）It is mixed with 101.7 grams of MoUSY7 samples, is extruded into a diameter of 1.6 millimeters of shape cylinder
Shape item, wet bar obtain carrier Z10 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
100.3 grams of carrier Z10 are taken, contain MoO with 85 milliliters3170.6 grams per liters, NiO88.2 grams per liters ammonium heptamolybdate and nitric acid
The mixed solution of nickel impregnates 4 hours, is roasted 3 hours in 150 DEG C of dry 3h, 400 DEG C, obtains catalyst C10.Using catalyst as base
Quasi- forms as shown in table 2 after the roasting of C10 catalyst.
Embodiment 11
Take 200.0 grams of USY molecular sieves（Chang Ling catalyst branch product, butt 0.75）It is being ground with 14.8 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 8 hours in 300 DEG C under steam atmosphere, it is therein
Gas flow is 0.4m3/(kg·h).It obtains Mo and is modified MoO in USY type molecular sieves MoUSY8, MoUSY83Content and n values row
In table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 63.1 grams of USY molecular sieves（It is long
Ridge catalyst branch product, butt 0.75）It is mixed with 67.8 grams of MoUSY8 samples, is extruded into a diameter of 1.6 millimeters of shape cylinder
Shape item, wet bar obtain carrier Z11 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
102.0 grams of carrier Z11 are taken, contain MoO with 85 milliliters3182.4 grams per liters, NiO88.2 grams per liters ammonium heptamolybdate and nitric acid
The mixed solution of nickel impregnates 4 hours, is roasted 3 hours in 150 DEG C of dry 3h, 400 DEG C, obtains catalyst C11.Using catalyst as base
Quasi- forms as shown in table 2 after the roasting of C11 catalyst.
Comparative example 1
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）It is mixed with 100.5 grams of USY samples
It closes, is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, wet bar obtains carrier in 150 DEG C of dry 3h, 550 DEG C of roasting 3h
DZ1。
100.0 grams of carrier DZ1 are taken, contain MoO with 90 milliliters3296.3 grams per liters, NiO44.4 grams per liters, P2O529.7 grams per liter,
Nickel, the molybdenum complex solution of 48.0 grams per liter citric acids impregnate 4 hours, 3 hours dry in 150 DEG C, obtain catalyst DC1.With catalysis
On the basis of agent, formed after the roasting of DC1 catalyst as shown in table 2.
Comparative example 2
Take 200.0 grams of USY type molecular sieves（Chang Ling catalyst branch product, butt 0.75）With containing 18.4 grams of ammonium heptamolybdates
Solution iso volumetric impregnation 4 hours, 150 DEG C of dryings 3 hours, 550 DEG C roast 3 hours, obtain being modified using Mo prepared by infusion process
USY type molecular sieves DMoUSY.On the basis of Mo is modified USY type sieve samples, MoO3Content and n values are shown in Table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 51.0 grams of USY molecular sieves with
The mixing of 54.6 grams of DMoUSY samples, is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, wet bar in 150 DEG C of dry 3h,
550 DEG C of roasting 3h, obtain carrier DZ2.
101.7 grams of carrier DZ2 are taken, contain MoO with 80 milliliters3312.1 grams per liters, NiO45.0 grams per liters, P2O533.4 grams per liter,
Nickel, the molybdenum complex solution of 54.0 grams per liter citric acids impregnate 4 hours, 3 hours dry in 150 DEG C, obtain catalyst DC2.With catalysis
On the basis of agent, formed after the roasting of DC2 catalyst as shown in table 2.
The composition information of 1 modified molecular screen of table
The composition information of 2 carrier of table and catalyst
Embodiment 12-14
The following examples illustrate the performance of catalyst provided by the invention.
Using the naphthane of purity 99% as raw material（It analyzes pure）, catalyst provided by the invention is evaluated in miniature fixed bed
The naphthane reactivity worth of C3, C4, C6, loaded catalyst are 1.0 grams, and reaction condition is 330 DEG C~390 DEG C, pressure
4.0MPa.It provides following two performance indicators preferably to carry out comparison and is defined, the results are shown in Table 3.
Comparative example 3 and comparative example 4
DC1, DC2 are evaluated using with embodiment 12-14 same procedures, the results are shown in Table 3.
The naphthane of 3 catalyst of table is hydrocracked evaluation result
Table 3 the result shows that, compared with comparative catalyst DC1：The relative conversion rate that the present invention provides patent naphthane improves
10%~48%；Under same conversion, opposite open-loop products selectively improve 18%~30%.Compared with comparative catalyst DC2, this hair
The bright relative conversion rate for providing patent naphthane improves 4%~42%, and opposite open-loop products selectively improve 6%~26%.
Claims (25)
1. a kind of hydrocracking catalyst contains the carrier of the acid constituents containing molecular sieve solid, the hydrogenation activity in the catalyst
Metal component is selected from least one VIII race's metal component and at least one VI B metal components, and the molecular sieve solid acid constituents is
Including MoY types zeolite molecular sieve and at least one molecular sieve mixture selected from the y-type zeolite in addition to MoY, the molecular sieve
MoY types zeolite molecular sieve and at least one weight ratio selected from the y-type zeolite in addition to MoY are 9 in mixture:1~1:9,
In, the MoY types zeolite molecular sievenValue is 0<n <1,n=I/αI0, characterized in FT-IR methods, I is MoY type zeolites point
3625cm in the FT-IR spectrograms of son sieve-1Absorption peak strength, I0For the parent Y-type zeolite molecular sieve of MoY type zeolite molecular sieves
3625cm in FT-IR spectrograms-1Absorption peak strength,αFor 3740cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorb peak intensity
Degree and 3740cm in the FT-IR spectrograms of parent Y-type zeolite molecular sieve-1The ratio of absorption peak strength；The MoY type zeolite molecules
The parent Y-type zeolite molecular sieve of sieve is HY zeolites, overstable gamma zeolite USY, the USY of part amorphous, super steady HY types zeolite, takes off
One or more of aluminium y-type zeolite.
2. catalyst according to claim 1, which is characterized in that MoY types zeolite molecular sieve in the molecular sieve mixture
It is 4 at least one weight ratio selected from the y-type zeolite in addition to MoY:1~1:1.
3. catalyst according to claim 1, which is characterized in that the MoY types zeolite molecular sievenValue for 0.4≤n
≤0.8。
4. catalyst according to claim 1, which is characterized in that described on the basis of the MoY types zeolite molecular sieve
The content of molybdenum in MoY zeolite molecular sieves in terms of oxide is 0.5-10 weight %.
5. catalyst according to claim 4, which is characterized in that described on the basis of the MoY types zeolite molecular sieve
The content of molybdenum in MoY type zeolite molecular sieves in terms of oxide is 2-8 weight %.
6. catalyst according to claim 1, which is characterized in that the y-type zeolite in addition to MoY is selected from HY, rare earth
Y, one kind in rare earth HY, super steady Y, hyperastable Y-type RE, the Y of part amorphous, the Y of titaniferous, phosphorous Y-type zeolite molecular sieve
Or it is several.
7. catalyst according to claim 1, which is characterized in that counted by oxide and on the basis of the catalyst, institute
The content for stating VIII race's metal component is 1-10 weight %, and the content of VI B races metal component is 5-50 weight %.
8. catalyst according to claim 7, which is characterized in that VIII race metal component is selected from cobalt and/or nickel, VI B
Metal component is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the content of VIII race metal component is
The content of 2-8 weight %, VI B races metal component are 10-35 weight %.
9. catalyst according to claim 1, which is characterized in that contain heat-resistant inorganic oxide matrix in the carrier,
On the basis of the carrier, the content of the heat-resistant inorganic oxide matrix is more than 0 to less than equal to 99 weight %.
10. catalyst according to claim 9, which is characterized in that the heat-resistant inorganic oxide matrix be selected from aluminium oxide,
One or more of silica and silica-alumina, on the basis of the carrier, the heat-resistant inorganic oxide matrix
Content is 10-90 weight %.
11. the catalyst according to claim 1 or 9, which is characterized in that on the basis of the catalyst, the catalyst
The content of middle carrier is 45-85 weight %, and the content of VIII race metal component in terms of oxide is 1-10 weight %, with oxygen
The content of VI B races metal component of compound meter is 5-50 weight %.
12. catalyst according to claim 11, which is characterized in that on the basis of the catalyst, in the catalyst
The content of carrier is 55-85 weight %, and the content of VIII race metal component in terms of oxide is 2-8 weight %, with oxide
The content of VI B races metal component of meter is 10-35 weight %.
13. a kind of preparation method of hydrocracking catalyst, including prepare the carrier containing the acid constituents containing molecular sieve solid and to
In the carrier the step of introducing hydrogenation active metal component, the hydrogenation active metal component choosing in the hydrocracking catalyst
From at least one VIII race's metal component and at least one VI B metal components, the molecular sieve solid acid constituents be include the boiling of MoY types
The molecular sieve mixture of stone molecular sieve and at least one y-type zeolite selected from addition to MoY, MoY in the molecular sieve mixture
Type zeolite molecular sieve and at least one weight ratio selected from the y-type zeolite in addition to MoY are 9:1~1:9, wherein described
MoY type zeolite molecular sievesnValue is 0<n <1,n=I/αI0, characterized in FT-IR methods, I is MoY type zeolite molecular sieves
3625cm in FT-IR spectrograms-1Absorption peak strength, I0For the FT-IR spectrums of the parent Y-type zeolite molecular sieve of MoY type zeolite molecular sieves
3625cm in figure-1Absorption peak strength,αFor 3740cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorption peak strength and parent
3740cm in the FT-IR spectrograms of Y-type zeolite molecular sieve-1The ratio of absorption peak strength；The parent of the MoY type zeolite molecular sieves
Y-type zeolite molecular sieve is HY zeolites, overstable gamma zeolite USY, the USY of part amorphous, super steady HY types zeolite, dealuminium Y type beta stone
One or more of；
The preparation method of the MoY types zeolite molecular sieve includes：（1）Y-type zeolite molecular sieve is mixed with compound containing Mo, is obtained
A kind of mixture of Y-type zeolite molecular sieve and the compound containing Mo, the dosage of each component make in final MoY types zeolite molecular sieve, with
The molybdenum content of oxide meter is 0.5-10 weight %；（2）By step（1）Obtained mixture encloses lower height in steam-laden atmosphere
Temperature processing, it is 200-700 DEG C that the condition of the high-temperature process, which includes calcination temperature, and roasting time is 1-24 hours, containing water vapor
Gas flow be 0.3-2 standard cubic meters/kilogram hour, obtain MoY type zeolite molecular sieves.
14. according to the method for claim 13, which is characterized in that MoY types zeolite molecular sieve in the molecular sieve mixture
It is 4 at least one weight ratio selected from the y-type zeolite in addition to MoY:1~1:1；The MoY types zeolite molecular sieven
Value for 0.4≤n≤0.8。
15. according to the method for claim 13, which is characterized in that described on the basis of the MoY types zeolite molecular sieve
The content of molybdenum in MoY zeolite molecular sieves in terms of oxide is 0.5-10 weight %.
16. according to the method for claim 15, which is characterized in that described on the basis of the MoY types zeolite molecular sieve
The content of molybdenum in MoY type zeolite molecular sieves in terms of oxide is 2-8 weight %.
17. according to the method for claim 13, which is characterized in that the y-type zeolite in addition to MoY is selected from HY, rare earth
Y, one kind in rare earth HY, super steady Y, hyperastable Y-type RE, the Y of part amorphous, the Y of titaniferous, phosphorous Y-type zeolite molecular sieve
Or it is several.
18. according to the method for claim 13, which is characterized in that the step（1）The dosage of middle each component makes final MoY
In type zeolite molecular sieve, the molybdenum content in terms of oxide is 2-8 weight %；The step（2）In the condition of high-temperature process include
Calcination temperature be 400-650 DEG C, roasting time be 2-12 hour, steam-laden gas flow for 0.6-1.5 standard cubic meters/
Kilogram hour.
19. according to the method for claim 13, which is characterized in that contain diluent gas in the steam-laden atmosphere,
Wherein, the volume mixture ratio of the vapor and diluent gas is 1：10-100.
20. according to the method for claim 19, which is characterized in that the diluent gas is selected from hydrogen, nitrogen and its mixing
Gas, or the gaseous mixture selected from air and air and nitrogen；The volume mixture ratio of the vapor and diluent gas is 1：
20-80。
21. according to the method for claim 13, which is characterized in that counted by oxide and on the basis of the catalyst, institute
Stating the introduction volume of VIII race's metal component makes the content of VIII race's metal component in final catalyst be 1-10 weight %, VI B races gold
Belonging to the introduction volume of component makes the content of VI B races metal component in final catalyst be 5-50 weight %.
22. according to the method for claim 21, which is characterized in that VIII race metal component is selected from cobalt and/or nickel, VI B
Metal component is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the introduction volume of VIII race metal component
Making the content of VIII race's metal component in final catalyst be the introduction volume of 2-8 weight %, VI B races metal component makes finally to urge
The content of VI B races metal component is 10-35 weight % in agent.
23. according to the method for claim 13, which is characterized in that the method include introduced into the carrier it is heat-resisting
The step of inorganic oxide matrix, on the basis of the carrier, the introduction volume of the heat-resistant inorganic oxide matrix makes finally to carry
The content of heat-resistant inorganic oxide matrix is more than 0 to less than equal to 99 weight % in body.
24. according to the method for claim 23, which is characterized in that on the basis of the carrier, the heat resistant inorganic oxidation
The introduction volume of object matrix makes the content of heat-resistant inorganic oxide matrix in final carrier be 10-90 weight %.
25. a kind of method for hydrogen cracking is included under hydrocracking condition and contacts hydrocarbon ils with catalyst, wherein the catalysis
Agent is the catalyst that preceding claims 1-12 any one provides.
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