CN104923292B - 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 the carrier of the acid constituents containing molecular sieve solid, the molecular sieve solid acid constituents is the mixture for including MoY types zeolite and Beta type molecular sieves, and the weight ratio of MoY types zeolite and Beta zeolites is 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, in the hydrocracking reaction for aromatic hydrocarbons, reactivity and open loop crackate selectivity of aromatic hydrocarbons etc. significantly improve catalyst provided by the invention.
Description
Technical field
The present invention is about a kind of hydrotreating catalyst and its preparation and application.
Background technology
The world's crude oil heaviness, in poor quality increasingly, sulfur content and arene content gradually increase, and clean fuel oil and high-quality
The demand of industrial chemicals but gradually increases.It is hydrocracked one of the main technique as heavy oil lighting, and uniquely can be in original
The important technical of clean fuel and high-quality industrial chemicals is directly produced while material lighting.Currently, how to realize aromatic hydrocarbons
Maximization, which is converted to fuel oil ideal composition or high-quality industrial chemicals, becomes one of the difficult point that is hydrocracked and must capture.Example
Such as：
20120352307.9 disclose a kind of hydrocracking catalyst of the molecular sieves of Beta containing multi-stage porous, the catalyst
Carrier is collectively constituted by multi-stage porous Beta molecular sieves, modified Y molecular sieve, aluminium oxide and amorphous silica-alumina, and hydrogenation active component is
The oxide of W metal, W, auxiliary agent are P or F.The characteristics of catalyst is that have abundant meso-hole structure and divide with middle strong acid
Cloth.
201110350783.2 disclose a kind of hydrocracking catalyst, and the catalyst is by being modified Beta molecular sieves, modified Y
The carrier and hydrogenation metal component of type molecular sieve, aluminium oxide composition, modified Beta molecular sieves are by the Beta molecular sieves after crystallization
After slurries directly carry out ammonium exchange, de- template agent processing, first hydrothermal treatment is handled by aluminum salt solution, it is therefore an objective to kept
Under conditions of Beta molecular sieve high-crystallinities, part non-framework aluminum is uniformly removed, optimizes the acid distribution and pore size distribution of molecular sieve.
201110369112.0 disclose the catalyst that a kind of polycyclic aromatic hydrocarbon is converted into mononuclear aromatics, which includes
34.5-60 weight %FAU types zeolite and the mixture selected from least one of MOR, BEA, MFI or MCM-22 molecular sieve,
39.5-65 weight % is selected from gama-alumina, η-at least one of aluminium oxide or boehmite is binder and 0.05-0.9%
Selected from least one of Pt, Pd or Ir metal.
In hydrocracking process realize aromatic hydrocarbons Efficient Conversion difficult point be improve desired product selectivity and inhibit green coke,
Extend catalyst service life.The desired product of the bicyclic and above aromatic hydrocarbons conversion is benzene,toluene,xylene i.e. BTX contour additional
Value and long side chain n- alkyl benzene grade height cetane value constituents.The key for improving desired product selectivity is to realize hydrogenating function and cracking
Collaboration on function high level and matching.
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 the mixture including MoY types zeolite and Beta type molecular sieves, MoY types zeolite and Beta zeolites in the molecular sieve mixture
Weight ratio be 9:1~1:9, wherein the n values of the MoY types zeolite molecular sieve are 0<n<1, n=I/ α I0, in FT-IR methods
Characterization, I are 3625cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorption peak strength, I0For the mother of MoY type zeolite molecular sieves
3625cm in the FT-IR spectrograms of body Y-type zeolite molecular sieve-1Absorption peak strength, α are in the FT-IR spectrograms of MoY type zeolite molecular sieves
3740cm-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Y-type zeolite molecular sieve-1The ratio of absorption peak strength.
2, the catalyst according to 1, which is characterized in that MoY types zeolite and Beta zeolites in the molecular sieve mixture
Weight ratio be 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 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 %.
8, the catalyst according to 7, 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 %.
9, 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 %.
10, the catalyst according to 9, which is characterized in that the heat-resistant inorganic oxide matrix is selected from aluminium oxide, oxidation
One or more of silicon and silica-alumina, on the basis of the carrier, the content of the heat-resistant inorganic oxide matrix
For 10-90 weight %.
11, the catalyst according to 1 or 9, 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 %.
12, the catalyst according to 11, 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 %.
13, the catalyst according to 1, which is characterized in that the Beta zeolite molecular sieve is MoBeta zeolite molecular sieves,
The n values of the MoBeta types zeolite molecular sieve are 0<n<1, n=I/ α I0, characterized in FT-IR methods, I is MoBeta type zeolites point
3610cm in the FT-IR spectrograms of son sieve-1Absorption peak strength, I0For the parent Beta type zeolite molecules of MoBeta type zeolite molecular sieves
3610cm in the FT-IR spectrograms of sieve-1Absorption peak strength, α are 3740cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves-1It inhales
Receive peak intensity and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves-1The ratio of absorption peak strength.
14, the catalyst according to 13, which is characterized in that the n values of the MoBeta types zeolite molecular sieve are 0.3≤n
≤0.6。
15, the catalyst according to 14, which is characterized in that described on the basis of the MoBeta types zeolite molecular sieve
The content of molybdenum in MoBeta zeolite molecular sieves in terms of oxide is 0.5-10 weight %.
16, the catalyst according to 15, which is characterized in that described on the basis of the MoBeta types zeolite molecular sieve
The content of molybdenum in MoBeta type zeolite molecular sieves in terms of oxide is 1-6 weight %.
17, 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 is the mixture for including MoY types zeolite and Beta type molecular sieves, in the molecular sieve mixture
The weight ratio of MoY types zeolite and Beta zeolites is 9:1~1:9, wherein the n values of the MoY types zeolite molecular sieve are 0<n<1,
n=I/αI0, 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 MoY type zeolites
3740cm in the FT-IR spectrograms of molecular sieve-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Y-type zeolite molecular sieve-1
The ratio of absorption peak strength.
18, the method according to 17, which is characterized in that MoY types zeolite and Beta zeolites in the molecular sieve mixture
Weight ratio be 4:1~1:1；The n values of the MoY types zeolite molecular sieve are 0.4≤n≤0.8.
19, the method according to 17, 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 %.
20, the method according to 19, 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 %.
21, the method according to 17, 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.
22, the method according to 17, 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.
23, the method according to 22, 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.
24, the method according to 22, 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.
25, the method according to 24, 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.
26, the method according to 17, 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.
27, the method according to 26, 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 %.
28, the method according to 17, 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 %.
29, the method according to 28, 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 %.
30, the method according to 17, which is characterized in that the Beta zeolite molecular sieve is MoBeta zeolite molecular sieves,
The n values of the MoBeta types zeolite molecular sieve are 0<n<1, n=I/ α I0, characterized in FT-IR methods, I is MoBeta type zeolites point
3610cm in the FT-IR spectrograms of son sieve-1Absorption peak strength, I0For the parent Beta type zeolite molecules of MoBeta type zeolite molecular sieves
3610cm in the FT-IR spectrograms of sieve-1Absorption peak strength, α are 3740cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves-1It inhales
Receive peak intensity and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves-1The ratio of absorption peak strength.
31, the method according to 30, which is characterized in that the preparation method of the MoBeta types zeolite molecular sieve includes：
（1）Beta types zeolite molecular sieve is mixed with compound containing Mo, obtains a kind of Beta types zeolite molecular sieve and the compound containing Mo
Mixture, on the basis of the MoBeta types zeolite molecular sieve, the dosage of each component makes in final MoBeta types zeolite molecular sieve,
Molybdenum content in terms of oxide is 0.5-10 weight %；（2）By step（1）Obtained mixture is in the case where steam-laden atmosphere is enclosed
High-temperature process, 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, aqueous steaming
The gas flow of gas is 0.3-2 standard cubic meters/kilogram hour, obtains MoBeta type zeolite molecular sieves.
32, the method according to 31, which is characterized in that on the basis of the MoBeta types zeolite molecular sieve, the step
Suddenly（1）The dosage of middle each component makes in final MoBeta types zeolite molecular sieve, and the molybdenum content in terms of oxide is 1-6 weight %；Institute
State step（2）In high-temperature process condition include calcination temperature be 400-650 DEG C, roasting time be 2-12 hours, aqueous steaming
The gas flow of gas is 0.6-1.5 standard cubic meters/kilogram hour.
33, the method according to 32, 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.
34, the method according to 33, 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.
35, 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 1-16 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
The catalyst that composite molecular screen is prepared for acidic components adds hydrogen aromatic hydrocarbons is full to be 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.
In a preferred embodiment, Beta zeolite molecular sieve of the present invention is preferably a kind of MoBeta molecular sieves.
The further preferred MoBeta zeolites are one kind 0<n<1, preferably the Beta type zeolites of 0.3≤n≤0.6.Preferably, with institute
On the basis of stating MoBeta type zeolite molecular sieves（In the present invention, the content of molybdenum oxide in MoBeta type zeolite molecular sieves（Quality point
Number）The measured value of molybdenum oxide in=MoBeta types zeolite molecular sieve to be measured/(amount of MoBeta types zeolite molecular sieve to be measured × it is dry
Base).Butt be sample to be tested under air atmosphere 600 DEG C roasting 4 hours after weight with roasting before weight ratio）, described
The content of Mo is 0.5-10 weight %, further preferably 1-6 weight % in MoBeta zeolites.
3610cm in the FT-IR spectrograms of the Beta zeolites-1Absorption peak refers to 3610 ± 10cm in FT-IR spectrograms-1
The absorption peak at place, the absorption peak belong to the vibration absorption peak of Beta type zeolite acidity hydroxyls.The FT-IR of the Beta zeolites is composed
3740cm in figure-1Absorption peak refers to the 3740cm in FT-IR spectrograms-1±10cm-1The absorption peak at place, the absorption peak belong to
The vibration absorption peak of Beta type zeolites Si-OH.
The present invention to Beta type zeolite molecular sieves introduce Mo method include：
（1）Beta types zeolite molecular sieve is mixed with compound containing Mo, obtain a kind of Beta types zeolite molecular sieve and contains Mo
The mixture of compound；
（2）By step（1）Obtained mixture encloses lower roasting in steam-laden atmosphere, obtains MoBeta type zeolite molecules
Sieve；
Wherein, on the basis of the MoBeta types zeolite molecular sieve that butt is counted, the step（1）The dosage of middle each component
Make in final MoBeta types zeolite molecular sieve, the molybdenum content preferably in terms of oxide is 0.5-10 weight %, further preferably with oxygen
The molybdenum content of compound meter is 1-6 weight %；The molybdate compound preferably is selected from oxide, chloride or molybdate of molybdenum etc.；It is described
Step（2）In roasting condition include：Temperature is 200-700 DEG C, and preferably 400-650 DEG C, the time is 1-24 hours, preferably
3-12 hours, steam-laden gas flow was 0.3-2 standard cubic meters/kilogram hour, preferably 0.6-1.5 standard cubes
Rice/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 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 composite molecular screen of molecular sieve and Beta type zeolite molecular sieves, 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 and MoBeta composite molecular screens 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 also containing in the catalyst, it is described to be selected from
The introducing method of the components such as phosphorus, titanium be conventional method, as described in can be will contain the compound of auxiliary agent directly with solid acid component,
Boehmite mixing is molded and roasts；Can by the compound containing the auxiliary agent and contain hydrogenation active metal component
Compound be configured to mixed solution after contacted with the carrier；It can also be and the compound containing auxiliary agent is individually prepared into solution
It contacts and roasts with the carrier afterwards.When auxiliary agent and hydrogenation active metals introduce the carrier respectively, preferably first with containing
Auxiliary compound solution is contacted and is roasted with the carrier, later the solution with the compound containing hydrogenation active metal component again
Contact, such as by the method for dipping, the calcination temperature are 250-600 DEG C, preferably 350-500 DEG C, roasting time 2-8
Hour, 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.
Compared with prior art, when the present invention provides catalyst and is used for hydrocracking reaction process, it is bicyclic in raw material and with
The conversion of upper polycyclic aromatic hydrocarbon and the selectivity of desired product etc. significantly improve.It can be directly used for processing a variety of different hydrocarbon ils originals
Material, to carry out hydro-upgrading to it.The hydrocarbon oil crude material includes various heavy mineral oils or synthetic oil or their mixed fraction
Oil, for example, selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar
One or more of with heavy deasphalted oil.Particularly suitable for being hydrocracked or the hydro-upgrading of poor ignition quality fuel.
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 be listed in table 1.
Take 200.0 grams of Beta molecular sieves（Chang Ling catalyst branch product, butt 0.81）It is being ground with 0.8 gram of molybdenum trioxide
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 Beta types point
MoO in son sieve MoBeta1, MoBeta13Content be listed in table 2.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）With 19.1 grams of MoUSY1,
The mixing of 159.1 grams of MoBeta1 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 Z1.
100.2 grams of carrier Z1 are taken, contain MoO with 95 milliliters3182.1 grams per liters, NiO78.9 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 C1.On the basis of catalyst,
It is formed after the roasting of C1 catalyst as shown in table 3（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 be listed in table 1.
Take 200.0 grams of Beta molecular sieves（Chang Ling catalyst branch product, butt 0.81）It is being ground with 8.5 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.It is subsequently placed in tube furnace flat-temperature zone, is roasted 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 Beta types point
MoO in son sieve MoBeta2, MoBeta23Content be listed in table 2.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）With 9.8 grams of MoUSY2,36.6
The mixing of gram MoBeta2 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
3h is roasted, carrier Z2 is obtained.
101.0 grams of carrier Z2 are taken, contain MoO with 78 milliliters3648.9 grams per liters, NiO128.2 grams per liters, P2O564.1 grams per liter,
Nickel, the molybdenum complex solution of 138.5 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 3.
Embodiment 3
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）With 52.6 grams of MoUSY2,49.2
The mixing of gram MoBeta2 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
3h is roasted, carrier Z3 is obtained.
101.7 grams of carrier Z3 are taken, contain MoO with 90 milliliters3277.4 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 3.
Embodiment 4
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 MoUSY3, MoUSY43Content be listed in table 1.
Take 200.0 grams of Beta molecular sieves（Chang Ling catalyst branch product, butt 0.81）Exist with 14.1 grams of molybdenum trioxides
It grinds, be uniformly mixed in mortar.It is subsequently placed in tube furnace flat-temperature zone, it is small in 600 DEG C of roastings 8 under hydrogen and steam atmosphere
When, gas flow therein is 0.8m3The mixed proportion of/(kgh), vapor and hydrogen is 1:30.It obtains Mo and is modified Beta
MoO in type molecular sieve MoBeta3, MoBeta33Content be listed in table 2.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）With 54.8 grams of MoUSY3,50.5
The mixing of gram MoBeta3 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
3h is roasted, carrier Z3 is obtained.
103.3 grams of carrier Z4 are taken, contain MoO with 88 milliliters3265.5 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 C4.With catalysis
On the basis of agent, formed after the roasting of C4 catalyst as shown in table 3.
Embodiment 5
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 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 MoUSY4, MoUSY43Content be listed in table 1.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）With 69.7 grams of MoUSY4,16.1
The mixing of gram MoBeta3 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
3h is roasted, carrier Z5 is obtained.
102.9 grams of carrier Z5 are taken, contain MoO with 90 milliliters3541.9 grams per liters, NiO101.0 grams per liters, P2O555.6 grams per liter,
Nickel, the molybdenum complex solution of 109.2 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 3.
Embodiment 6
Take 200.0 grams of Beta molecular sieves（Chang Ling catalyst branch product, butt 0.81）Exist with 14.1 grams of molybdenum trioxides
It grinds, be uniformly mixed in mortar.It is subsequently placed in tube furnace flat-temperature zone, it is small in 300 DEG C of roastings 12 under air and steam atmosphere
When, gas flow therein is 1.2m3The mixed proportion of/(kgh), vapor and air is 1:15.It obtains Mo and is modified Beta
MoO in type molecular sieve MoBeta4, MoBeta43Content be listed in table 2.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）With 73.0 grams of MoUSY4,33.7
The mixing of gram MoBeta4 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
3h is roasted, carrier Z6 is obtained.
103.3 grams of carrier Z4 are taken, contain MoO with 88 milliliters3265.5 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 3.
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 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 MoUSY5, MoUSY53Content be listed in table 1.
Take 200.0 grams of Beta molecular sieves（Chang Ling catalyst branch product, butt 0.81）Exist with 26.8 grams of molybdenum pentachlorides
It grinds, be uniformly mixed in mortar.It is subsequently placed in tube furnace flat-temperature zone, it is small in 300 DEG C of roastings 24 under nitrogen and steam atmosphere
When, gas flow therein is 1.2m3The mixed proportion of/(kgh), vapor and nitrogen is 1:15.It obtains Mo and is modified Beta
MoO in type molecular sieve MoBeta5, MoBeta53Content be listed in table 2.
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 76%）It mixes, is extruded into external with 28.2 grams of MoUSY5,52.2 grams of MoBeta samples
The cloverleaf pattern item that circular diameter is 1.6 millimeters, wet bar obtain carrier Z7 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
102.3 grams of carrier Z7 are taken, contain MoO with 95 milliliters3160.0 grams per liters, NiO78.9 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 3.
Embodiment 8
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 MoUSY6, MoUSY63Content be listed in table 1.
Take 200.0 grams of Beta molecular sieves（Chang Ling catalyst branch product, butt 0.81）Exist with 14.1 grams of molybdenum trioxides
It grinds, be uniformly mixed in mortar.It is subsequently placed in tube furnace flat-temperature zone, is roasted 8 hours in 300 DEG C under steam atmosphere, wherein
Gas flow be 0.4m3/(kg·h).It obtains Mo and is modified MoO in Beta type molecular sieves MoBeta6, MoBeta63Content row
In table 2.
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 122.0 grams of MoUSY6 with
12.6 grams of MoBeta6 samples mixing are extruded into a diameter of 1.6 millimeters of shape cylindrical bar, and wet bar is in 150 DEG C of dry 3h, 550 DEG C of roastings
3h is burnt, carrier Z8 is obtained.
103.9 grams of carrier Z8 are taken, contain MoO with 90 milliliters3151.1 grams per liters, NiO83.3 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 C8.On the basis of catalyst,
It is formed after the roasting of C8 catalyst as shown in table 3.
Embodiment 9
150.0 grams of MoUSY2 molecular sieves are taken to be uniformly mixed with 93.0 grams of MoBeta molecular sieves, on DY-20 powder compressing machines
Compression molding, pressure 10MPa, 150 DEG C of dryings 3 hours prepare carrier Z9.
105.2 grams of Z9 are taken, contain MoO with 75 milliliters3286.2 grams per liters, NiO53.3 grams per liters, P2O535.6 grams per liters, 57.6
Nickel, the molybdenum complex solution of grams per liter citric acid impregnate 4 hours, 3 hours dry in 150 DEG C, obtain catalyst C9.It is with catalyst
Benchmark forms as shown in table 3 after the roasting of C9 catalyst.
Comparative example 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）With 47.2 grams of Beta molecular sieves（Chang Ling catalyst branch product, butt 0.81）
Mixing, is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, and wet bar is carried in 150 DEG C of dry 3h, 550 DEG C of roasting 3h
Body 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
By 200.0 grams of boehmites（Chang Ling catalyst branch product, butt 0.71）, 54.8 grams of MoUSY3 molecular sieves
With 47.2 grams of Beta molecular sieves（Chang Ling catalyst branch product, butt 0.81）Mixing, 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 DZ2.
101.7 grams of carrier DZ2 are taken, contain MoO with 88 milliliters3283.7 grams per liters, NiO45.4 grams per liters, P2O530.4 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 DC2.With catalysis
On the basis of agent, formed after the roasting of DC2 catalyst as shown in table 2.
The composition information of table 1Mo modified Y molecular sieves
Table 2Mo is modified Beta molecular sieves and forms information
3 carrier of table and catalyst form information
Embodiment 10 and embodiment 11
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, loaded catalyst are 1.0 grams, and reaction condition is 330 DEG C~390 DEG C, pressure 4.0MPa.
It provides following three performance indicators preferably to carry out comparison and is defined, the results are shown in Table 3.
Conversion ratio：
Open-loop products selectivity：
BTX selectivity：
Comparative example 3 and comparative example 4
DC1 and DC2 is evaluated using with embodiment 10 and 11 same procedure of embodiment, 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
22%~48%；Under same conversion, opposite open-loop products selectively improve 15%~28%, opposite BTX selectively improve 18%~
38%.Compared with comparative catalyst DC2, under same conversion, opposite open-loop products selectively improve 7%~20%, opposite BTX
Selectivity improves 15%~27%.
Claims (33)
1. a kind of hydrocracking catalyst contains the carrier and hydrogenation active metal component of the acid constituents containing molecular sieve solid, described
Hydrogenation active metal component is selected from least one VIII race's metal component and at least one VI B races metal component, and the molecular sieve is solid
Body acid constituents is the mixture for including MoY types zeolite molecular sieve and Beta type zeolite molecular sieves, MoY in the molecular sieve mixture
The weight ratio of type zeolite molecular sieve and Beta type zeolite molecular sieves is 9:1~1:9, wherein the MoY types zeolite molecular sievenValue is 0<n <1,n=I/αI0, characterized in FT-IR methods, I is 3625cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1
Absorption peak strength, I0For 3625cm in the FT-IR spectrograms of the parent Y-type zeolite molecular sieve of MoY type zeolite molecular sieves-1Absorb peak intensity
Degree,αFor 3740cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1The FT-IR of absorption peak strength and parent Y-type zeolite molecular sieve
3740cm in spectrogram-1The ratio of absorption peak strength；The parent Y-type zeolite molecular sieve is overstable gamma zeolite USY, part amorphous
One or more of USY of change.
2. catalyst according to claim 1, which is characterized in that MoY types zeolite molecular sieve in the molecular sieve mixture
Weight ratio with Beta type zeolite molecular sieves is 4:1~1:1.
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 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 %.
7. catalyst according to claim 6, which is characterized in that VIII race metal component is selected from cobalt and/or nickel, VI B
Race's 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
Content for 2-8 weight %, VI B races metal component is 10-35 weight %.
8. 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 %.
9. catalyst according to claim 8, 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 %.
10. the catalyst according to claim 1 or 8, 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 %.
11. catalyst according to claim 10, 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 %.
12. catalyst according to claim 1, which is characterized in that the Beta types zeolite molecular sieve boils for MoBeta types
Stone molecular sieve, the MoBeta types zeolite molecular sievenValue is 0<n <1,n=I/αI0, characterized in FT-IR methods, I is
3610cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves-1Absorption peak strength, I0For the parent of MoBeta type zeolite molecular sieves
3610cm in the FT-IR spectrograms of Beta type zeolite molecular sieves-1Absorption peak strength,αIt is composed for the FT-IR of MoBeta type zeolite molecular sieves
3740cm in figure-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves-1Absorption peak strength
Ratio.
13. catalyst according to claim 12, which is characterized in that the MoBeta types zeolite molecular sievenValue is
0.3≤n≤0.6。
14. catalyst according to claim 13, which is characterized in that on the basis of the MoBeta types zeolite molecular sieve,
The content of molybdenum in the MoBeta types zeolite molecular sieve in terms of oxide is 0.5-10 weight %.
15. catalyst according to claim 14, which is characterized in that on the basis of the MoBeta types zeolite molecular sieve,
The content of molybdenum in the MoBeta types zeolite molecular sieve in terms of oxide is 1-6 weight %.
16. a kind of preparation method of hydrocracking catalyst, including the carrier containing the acid constituents containing molecular sieve solid is prepared, it is described
Molecular sieve solid acid constituents is the mixture for including MoY types zeolite molecular sieve and Beta type zeolite molecular sieves, and the molecular sieve is mixed
It is 9 to close MoY types zeolite molecular sieve and the weight ratio of Beta zeolite molecular sieve in object:1~1:9, wherein the MoY types zeolite
Molecular sievenValue is 0<n <1,n=I/αI0, characterized in FT-IR methods, I is the FT-IR spectrograms of MoY type zeolite molecular sieves
Middle 3625cm-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,αFor 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；The parent Y-type zeolite molecular sieve is super steady Y boilings
One or more of the USY of stone USY, part amorphous；
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；
（2）By step（1）Obtained mixture encloses lower roasting in steam-laden atmosphere, obtains MoY type zeolite molecular sieves.
17. according to the method for claim 16, which is characterized in that MoY types zeolite molecular sieve in the molecular sieve mixture
Weight ratio with Beta type zeolite molecular sieves is 4:1~1:1；The MoY types zeolite molecular sievenValue for 0.4≤n≤0.8。
18. according to the method for claim 16, 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 %.
19. according to the method for claim 18, 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 %.
20. according to the method for claim 16, 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 0.5-10 weight %；The step（2）Middle 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.
21. according to the method for claim 20, 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）Middle calcination temperature is 400-650 DEG C,
Roasting time is 2-12 hours, and steam-laden gas flow is 0.6-1.5 standard cubic meters/kilogram hour.
22. according to the method for claim 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. according to the method for claim 22, 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。
24. according to the method for claim 16, which is characterized in that the method includes introducing to add hydrogen into the carrier
The step of active metal component, the hydrogenation active metal component in the hydrocracking catalyst are selected from least one VIII race's metal
Component and at least one VI B races metal component, are counted by oxide and on the basis of the catalyst, VIII race metal component
Introduction volume, which makes the content of VIII race's metal component in final catalyst be the introduction volume of 1-10 weight %, VI B races metal component, to be made
The content of VI B races metal component is 5-50 weight % in final catalyst.
25. according to the method for claim 24, which is characterized in that VIII race metal component is selected from cobalt and/or nickel, VI B
Race's metal component is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the introducing of VIII race metal component
Amount, which makes the content of VIII race's metal component in final catalyst be the introduction volume of 2-8 weight %, VI B races metal component, to be made finally
The content of VI B races metal component is 10-35 weight % in catalyst.
26. according to the method for claim 16, 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.
27. according to the method for claim 26, 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 %.
28. according to the method for claim 16, which is characterized in that the Beta zeolite molecular sieve is MoBeta type zeolites point
Son sieve, the MoBeta types zeolite molecular sievenValue is 0<n <1,n=I/αI0, characterized in FT-IR methods, I MoBeta
3610cm in the FT-IR spectrograms of type zeolite molecular sieve-1Absorption peak strength, I0For the parent Beta types of MoBeta type zeolite molecular sieves
3610cm in the FT-IR spectrograms of zeolite molecular sieve-1Absorption peak strength,αIn FT-IR spectrograms for MoBeta type zeolite molecular sieves
3740cm-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves-1The ratio of absorption peak strength.
29. according to the method for claim 28, which is characterized in that the preparation method packet of the MoBeta types zeolite molecular sieve
It includes：（1）Beta types zeolite molecular sieve is mixed with compound containing Mo, obtains a kind of Beta types zeolite molecular sieve and compound containing Mo
Mixture, on the basis of the MoBeta types zeolite molecular sieve, the dosage of each component makes final MoBeta types zeolite molecular sieve
In, the molybdenum content in terms of oxide is 0.5-10 weight %；（2）By step（1）Obtained mixture is enclosed in steam-laden atmosphere
Lower high-temperature process, 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, aqueous
The gas flow of steam is 0.3-2 standard cubic meters/kilogram hour, obtains MoBeta type zeolite molecular sieves.
30. according to the method for claim 29, which is characterized in that on the basis of the MoBeta types zeolite molecular sieve, institute
State step（1）The dosage of middle each component makes in final MoBeta types zeolite molecular sieve, and the molybdenum content in terms of oxide is 1-6 weights
Measure %；The step（2）In high-temperature process condition include calcination temperature be 400-650 DEG C, roasting time be 2-12 hours,
Steam-laden gas flow is 0.6-1.5 standard cubic meters/kilogram hour.
31. according to the method for claim 30, 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.
32. according to the method for claim 31, 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。
33. 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 1-15 any one provides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410109863.2A CN104923292B (en) | 2014-03-21 | 2014-03-21 | A kind of hydrocracking catalyst and its preparation and application |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5866742A (en) * | 1997-08-04 | 1999-02-02 | Phillips Petroleum Company | Transalkylation/hydrodealkylation of C9 + aromatic compounds with a zeolite |
| CN1351121A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Hydrocracing catalyst containing modified beta zeolite and its preparing process |
| CN1356380A (en) * | 2000-12-05 | 2002-07-03 | 中国石油化工股份有限公司 | Hydrorefining catalyst for heavy oil |
| 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 |
| CN103418428A (en) * | 2012-05-15 | 2013-12-04 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing heteropoly acid and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866742A (en) * | 1997-08-04 | 1999-02-02 | Phillips Petroleum Company | Transalkylation/hydrodealkylation of C9 + aromatic compounds with a zeolite |
| CN1351121A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Hydrocracing catalyst containing modified beta zeolite and its preparing process |
| CN1356380A (en) * | 2000-12-05 | 2002-07-03 | 中国石油化工股份有限公司 | Hydrorefining catalyst for heavy oil |
| 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 |
| CN103418428A (en) * | 2012-05-15 | 2013-12-04 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing heteropoly acid and application thereof |
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