CN105435836B - A kind of hydrocracking catalyst and its preparation and application - Google Patents
A kind of hydrocracking catalyst and its preparation and application Download PDFInfo
- Publication number
- CN105435836B CN105435836B CN201410437783.XA CN201410437783A CN105435836B CN 105435836 B CN105435836 B CN 105435836B CN 201410437783 A CN201410437783 A CN 201410437783A CN 105435836 B CN105435836 B CN 105435836B
- Authority
- CN
- China
- Prior art keywords
- mobeta
- catalyst
- molecular sieve
- metal component
- zeolite molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
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 ZSM 5 molecular sieve and MoBeta molecular sieves, and the weight ratio of 5 molecular sieves of ZSM and MoBeta molecular sieves is 9 in the molecular sieve mixture:1~1:9, wherein the n values of MoBeta molecular sieves are 0<n<1, n=I/ α I0, characterized in FT IR methods, I is 3610cm in the FT IR spectrograms of MoBeta type zeolite molecular sieves‑1Absorption peak strength, I0For 3610cm in the FT IR spectrograms of the parent Beta type zeolite molecular sieves of MoBeta type zeolite molecular sieves‑1Absorption peak strength, α are 3740cm in the FT IR spectrograms of MoBeta type zeolite molecular sieves‑1Absorption peak strength and 3740cm in the FT IR spectrograms of parent Beta type zeolite molecular sieves‑1The ratio of absorption peak strength.Compared with prior art, the present invention provides catalyst bicyclic in hydrocracking reaction and the conversion of above polycyclic aromatic hydrocarbon and the selectivity etc. of desired product significantly improves.
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 metals.
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 performances to obtain improved hydrocracking catalyst, the catalysis
The preparation method and applications of agent.
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 ZSM-5 molecular sieve and MoBeta molecular sieves, ZSM-5 molecular sieve and Beta in the molecular sieve mixture
The weight ratio of molecular sieve is 9:1~1:9, wherein the n values of MoBeta molecular sieves are 0<n<1, n=I/ α I0, in FT-IR methods
Characterization, I are 3610cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves-1Absorption peak strength, I0For MoBeta type zeolite molecules
3610cm in the FT-IR spectrograms of the parent Beta type zeolite molecular sieves of sieve-1Absorption peak strength, α are MoBeta type zeolite molecular sieves
FT-IR spectrograms in 3740cm-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves-1It absorbs
The ratio of peak intensity.
2, the catalyst according to 1, which is characterized in that ZSM-5 molecular sieve and Beta divide in the molecular sieve mixture
The weight ratio of son sieve is 4:1~1:1.
3, the catalyst according to 1, which is characterized in that the n values of the MoBeta molecular sieves are 0.3≤n≤0.8.
4, the catalyst according to 1, 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 %.
5, the catalyst according to 4, 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 1-9 weight %.
6, 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 %.
7, the catalyst according to 6, 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 1.5-
The content of 6 weight %, VI B races metal component are 10-40 weight %.
8, 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 %.
9, the catalyst according to 8, 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 %.
10, the catalyst according to 1 or 8, which is characterized in that on the basis of the catalyst, carried in the catalyst
The content of body is 45-90 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 %.
11, the catalyst according to 10, 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 1.5-6 weight %, with oxide
The content of VI B races metal component of meter is 10-40 weight %.
12, 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 ZSM-5 molecular sieve and MoBeta molecular sieves, the molecular sieve mixture
The weight ratio of middle ZSM-5 molecular sieve and Beta molecular sieves is 9:1~1:9, wherein the n values of MoBeta molecular sieves are 0<n<1, n
=I/ α I0, characterized in FT-IR methods, I is 3610cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves-1Absorption peak strength,
I0For 3610cm in the FT-IR spectrograms of the parent Beta type zeolite molecular sieves of MoBeta type zeolite molecular sieves-1Absorption peak strength, α
For 3740cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves-1The FT- of absorption peak strength and parent Beta type zeolite molecular sieves
3740cm in IR spectrograms-1The ratio of absorption peak strength.
13, the method according to 12, which is characterized in that ZSM-5 molecular sieve and Beta divide in the molecular sieve mixture
The weight ratio of son sieve is 4:1~1:1；The n values of the MoBeta molecular sieves are 0.3≤n≤0.8.
14, the method according to 12, 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 %.
15, the method 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 type zeolite molecular sieves in terms of oxide is 1-9 weight %.
16, the method according to 12, 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) mixture for obtaining step (1) 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.
17, the method according to 16, which is characterized in that on the basis of the MoBeta types zeolite molecular sieve, the step
Suddenly the dosage of each component makes in final MoBeta types zeolite molecular sieve in (1), and the molybdenum content in terms of oxide is 1-9 weight %；
The condition of high-temperature process in the step (2) includes that calcination temperature is 400-650 DEG C, and roasting time is 2-12 hours, aqueous
The gas flow of steam is 0.6-1.5 standard cubic meters/kilogram hour.
18, the method according to 17, 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.
19, the method according to 18, which is characterized in that the diluent gas is selected from hydrogen, nitrogen and its gaseous mixture, excellent
It is selected as hydrogen, or the gaseous mixture selected from air and air and nitrogen；The volumetric mixture ratio of the vapor and diluent gas
Example is 1：20-80.
20, the method according to 12, 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
The content of VI B races metal component is 5-50 weight % in catalyst.
21, the method according to 20, 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 1.5-6 weight %, VI B races metal component, in whole catalyst makes finally to be catalyzed
The content of VI B races metal component is 10-40 weight % in agent.
22, the method according to 12, 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 %.
23, the method according to 22, 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 %.
24, 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 1-11 is provided.
In present invention description as described in molecular sieve, Beta (or MoBeta, ZSM-5 etc.) the type zeolite molecular sieve, Beta
The meaning of (or MoBeta, ZSM-5 etc.) zeolite or Beta (or MoBeta, ZSM-5 etc.) molecular sieve is identical.
In the present invention, the 3610cm in the FT-IR spectrograms of the Beta zeolites-1Absorption peak refers in FT-IR spectrograms
3610±10cm-1The absorption peak at place, the absorption peak belong to the vibration absorption peak of Beta type zeolite acidity hydroxyls.The Beta boilings
3740cm in the FT-IR spectrograms of stone-1Absorption peak refers to the 3740cm in FT-IR spectrograms-1±10cm-1The absorption peak at place, the suction
Receive the vibration absorption peak that peak belongs to Beta type zeolites Si-OH.
Inventor has found, when with n=I/ α I0FT-IR is composed before and after indicating Beta type zeolite molecular sieves introducing Mo metal components
3610cm in figure-1When the variation of absorption peak strength, the Mo-Beta 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 use urging for this Mo-Beta types zeolite molecular sieve preparation
Agent adds hydrogen aromatic hydrocarbons is full to be significantly improved with open loop, cracking performance.
In the present invention, the Mo-Beta zeolites are one kind 0<n<1, preferably the Beta type zeolites of 0.3≤n≤0.8.It is excellent
Selection of land, (in the present invention, molybdenum oxide contains in Mo-Beta type zeolite molecular sieves on the basis of the Mo-Beta types zeolite molecular sieve
Measure measured value/(Mo-Beta types zeolite molecules to be measured of molybdenum oxide in (mass fraction)=Mo-Beta to be measured type zeolite molecular sieves
Amount × butt of sieve).Butt be sample to be tested under air atmosphere 600 DEG C roasting 4 hours after weight with roasting before weight it
Than), the content of Mo is 0.5-10 weight %, further preferably 1-9 weight % in the Mo-Beta zeolites.
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) mixture that step (1) obtains is enclosed into lower roasting in steam-laden atmosphere, obtains Mo-Beta type zeolites point
Son sieve；
Wherein, on the basis of the Mo-Beta types zeolite molecular sieve that butt is counted, the use of each component in the step (1)
Amount makes in final Mo-Beta types zeolite molecular sieve, and the molybdenum content preferably in terms of oxide is 0.5-10 weight %, further preferably
Molybdenum content in terms of oxide is 1-6 weight %；The molybdate compound preferably is selected from the oxide, chloride or molybdate of molybdenum
Deng；Roasting condition in the step (2) includes：Temperature is 200-700 DEG C, and preferably 400-650 DEG C, the time is that 1-24 is small
When, preferably 3-12 hours, steam-laden gas flow was 0.3-2 standard cubic meters/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 it is preferred that
For hydrogen, wherein the volume mixture ratio of the vapor and diluent gas is preferably 1：10-100, further preferably 1：
20-80。
In the present invention, the ZSM-5 is not particularly limited, commodity can be commercially available or by arbitrary prior art system
It is standby.
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, described will be boiled containing ZSM-5
The composite molecular screen of stone molecular sieve and MoBeta type zeolite molecular sieves with or without heat-resistant inorganic oxide extruded moulding and roasts
Method prepare.In extrusion molding, appropriate extrusion aid and/or adhesive can be added into material to be formed, then squeeze out
Molding.The extrusion aid, the type of peptizing agent and dosage extrusion aid known to those skilled in the art such as common can be with
Selected from one or more of sesbania powder, methylcellulose, starch, polyvinyl alcohol, polyethanol, the peptizing agent can be selected from nothing
One or more of machine acid, organic acid.
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 group VIII metal group
It is divided into cobalt and/or nickel, metal component of group VIB is molybdenum and/or tungsten.It is counted by oxide and on the basis of the catalyst, it is described
The content of VIII race's metal component is preferably 1-10 weight %, further preferably 1.5-6 weight %, VI B races metal component
Content be preferably 5-50 weight %, further preferably 10-40 weight %.The present invention is calculating containing for VI B races metal component
Include counting the Mo in MoBeta molecular sieves when amount.
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.
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.
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.
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 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 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 rich in aromatic hydrocarbons oil product or poor ignition quality fuel plus hydrogen
Modification.
Specific implementation mode
The present invention will be further described for following example.
Framework of molecular sieve hydroxyl is measured by Fourier infrared (FT-IR), and sample is roasted 2h at 350 DEG C first, is kept
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) measures, and 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 Beta molecular sieves (Chang Ling catalyst branch product, silicon/aluminium 30, butt 0.81) and 0.8 gram of three oxygen
Change molybdenum to grind, be uniformly mixed in mortar.It is subsequently placed in tube furnace flat-temperature zone, in 420 DEG C of roastings under hydrogen and steam atmosphere
It burns 24 hours, gas flow therein is 0.5m3The mixed proportion of/(kgh), vapor and hydrogen is 1:40.Mo is obtained to change
MoO in property Beta type molecular sieve MoBeta1, Mo-Beta13Content and its n values be listed in table 1.
By 200.0 grams of boehmites (Chang Ling catalyst branch product, butt 0.71) and 19.1 grams of (Chang Lings ZSM-5
Catalyst branch product, silicon/aluminium 60, butt 0.94), the mixing of 159.1 grams of MoBeta1 samples, it is 1.6 to be extruded into circumscribed circle diameter
The cloverleaf pattern item of millimeter, wet bar obtain carrier Z1 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
100.2 grams of carrier Z1 are taken, contain MoO with 95 milliliters3182.1 grams per liters, 78.9 grams per liter ammonium heptamolybdates of NiO 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
Standard, composition is as shown in table 2 after the roasting of C1 catalyst (active metal component is measured using X-ray fluorescence spectra analysis (XRF), under
Together).
Embodiment 2
Take 200.0 grams of Beta molecular sieves (Chang Ling catalyst branch product, silicon/aluminium 30, butt 0.81) and 8.5 gram of three oxygen
Change molybdenum to grind, be uniformly mixed in mortar.It is subsequently placed in tube furnace flat-temperature zone, in 450 DEG C of roastings under hydrogen and steam atmosphere
It burns 4 hours, gas flow therein is 0.8m3The mixed proportion of/(kgh), vapor and hydrogen is 1:30.Obtain Mo modifications
MoO in Beta type molecular sieves MoBeta2, MoBeta23Content and its n values be listed in table 1..
By 200.0 grams of boehmites (Chang Ling catalyst branch product, butt 0.71) with 9.8 grams of BZSM-5 (with real
Apply example 1), the mixing of 36.6 grams of MoBeta2 samples, be extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, wet bar is in 150 DEG C
Dry 3h, 550 DEG C of roasting 3h, obtain carrier Z2.
101.0 grams of carrier Z2 are taken, contain MoO with 78 milliliters3648.9 grams per liters, 128.2 grams per liters of NiO, 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 2.
Embodiment 3
By 200.0 grams of boehmites (Chang Ling catalyst branch product, butt 0.71) with 52.6 grams of ZSM-5 (with real
Apply example 1), the mixing of 49.2 grams of MoBeta2 samples, be extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, wet bar is in 150 DEG C
Dry 3h, 550 DEG C of roasting 3h, obtain carrier Z3.
101.7 grams of carrier Z3 are taken, contain MoO with 90 milliliters3277.4 grams per liters, 44.4 grams per liters of NiO, 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 Beta molecular sieves (Chang Ling catalyst branch product, silicon/aluminium 30, butt 0.81) and 14.1 gram three
Molybdenum oxide grinds in mortar, is uniformly mixed.It is subsequently placed in tube furnace flat-temperature zone, in 450 DEG C under hydrogen and steam atmosphere
Roasting 8 hours, gas flow therein are 0.8m3The mixed proportion of/(kgh), vapor and hydrogen is 1:30.Mo is obtained to change
MoO in property Beta type molecular sieve MoBeta3, MoBeta33Content and its n values be listed in table 1.
By 200.0 grams of boehmites (Chang Ling catalyst branch product, butt 0.71) with 54.8 grams of ZSM-5 (with real
Apply example 1), the mixing of 50.5 grams of MoBeta3 samples, be extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, wet bar is in 150 DEG C
Dry 3h, 550 DEG C of roasting 3h, obtain carrier Z3.
103.3 grams of carrier Z4 are taken, contain MoO with 88 milliliters3265.5 grams per liters, 45.5 grams per liters of NiO, 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 2.
Embodiment 5
200.0 grams of boehmites (Chang Ling catalyst branch product, butt 0.71) (are urged Chang Ling with 69.7 grams of Beta
Agent branch company product, silicon/aluminium 30, butt 0.81), the mixing of 16.1 grams of MoBeta3 samples, it is 1.6 millis to be extruded into circumscribed circle diameter
The cloverleaf pattern item of rice, wet bar obtain carrier Z5 in 150 DEG C of dry 3h, 550 DEG C of roasting 3h.
102.9 grams of carrier Z5 are taken, contain MoO with 90 milliliters3541.9 grams per liters, 101.0 grams per liters of NiO, 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 2.
Embodiment 6
Take 200.0 grams of Beta molecular sieves (Chang Ling catalyst branch product, silicon/aluminium 30, butt 0.81) and 14.1 gram three
Molybdenum oxide grinds in mortar, is uniformly mixed.It is subsequently placed in tube furnace flat-temperature zone, in 450 DEG C under air and steam atmosphere
Roasting 12 hours, gas flow therein are 1.2m3The mixed proportion of/(kgh), vapor and air is 1:15.Obtain Mo
MoO in modified Beta type molecular sieves MoBeta4, MoBeta43Content and its n values be listed in table 1.
By 200.0 grams of boehmites (Chang Ling catalyst branch product, butt 0.71) with 73.0 grams of ZSM-5 (with real
Apply example 1), the mixing of 33.7 grams of MoBeta4 samples, be extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, wet bar is in 150 DEG C
Dry 3h, 550 DEG C of roasting 3h, obtain carrier Z6.
103.3 grams of carrier Z4 are taken, contain MoO with 88 milliliters3265.5 grams per liters, 45.5 grams per liters of NiO, 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 Beta molecular sieves (Chang Ling catalyst branch product, silicon/aluminium 30, butt 0.81) and 26.8 gram five
Molybdenum chloride grinds in mortar, is uniformly mixed.It is subsequently placed in tube furnace flat-temperature zone, in 300 DEG C under nitrogen and steam atmosphere
Roasting 24 hours, gas flow therein are 1.2m3The mixed proportion of/(kgh), vapor and nitrogen is 1:15.Obtain Mo
MoO in modified Beta type molecular sieves MoBeta5, MoBeta53Content and its 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 76%) and 28.2 grams of ZSM-5 (with embodiment 1), 52.2 grams of MoBeta samples are mixed
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
Z7。
102.3 grams of carrier Z7 are taken, contain MoO with 95 milliliters3160.0 grams per liters, 78.9 grams per liter ammonium heptamolybdates of NiO 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 C7.Using catalyst as base
Quasi- forms as shown in table 2 after the roasting of C7 catalyst.
Embodiment 8
Take 200.0 grams of Beta molecular sieves (Chang Ling catalyst branch product, silicon/aluminium 30, butt 0.81) and 14.1 gram three
Molybdenum oxide grinds in mortar, is uniformly mixed.It is subsequently placed in tube furnace flat-temperature zone, it is small in 300 DEG C of roastings 8 under steam atmosphere
When, gas flow therein is 0.4m3/(kg·h).It obtains Mo and is modified MoO in Beta type molecular sieves MoBeta6, MoBeta63's
Content and its n values are listed in table 1.
By 200.0 grams of boehmites (Chang Ling catalyst branch product, butt 0.71), 122.0 grams of ZSM-5 (with real
Apply example 1) it is mixed with 12.6 grams of MoBeta6 samples, it is extruded into a diameter of 1.6 millimeters of shape cylindrical bar, wet bar is in 150 DEG C of dryings
3h, 550 DEG C of roasting 3h, obtain carrier Z8.
103.9 grams of carrier Z8 are taken, contain MoO with 90 milliliters3151.1 grams per liters, 83.3 grams per liter ammonium heptamolybdates of NiO 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 C8.Using catalyst as base
Quasi- forms as shown in table 2 after the roasting of C8 catalyst.
Embodiment 9
150.0 grams of ZSM-5 (with embodiment 1) molecular sieves are taken to be uniformly mixed with 93.0 grams of 1 molecular sieves of MoBeta, in DY-20
Compression molding on powder compressing machine, 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, 53.3 grams per liters of NiO, 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 2 after the roasting of C9 catalyst.
Comparative example 1
Take 180.0 grams of Beta types molecular sieves (Chang Ling catalyst branch product, butt 0.75) with containing 11.7 gram of seven molybdic acid
The solution iso volumetric impregnation of ammonium 4 hours, 150 DEG C of dryings 3 hours, 450 DEG C roast 3 hours, obtain changing using Mo prepared by infusion process
Property Beta type molecular sieves DMoBeta.It obtains Mo and is modified MoO in Beta type molecular sieves DMoBeta, DMoBeta3Content and its n
Value is listed in table 1.
By 200.0 grams of boehmites (Chang Ling catalyst branch product, butt 0.71), 78.9 grams of ZSM-5 (with implementation
Example 1) and 94.6 grams of DMoBeta molecular sieves mixing, it is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters, wet bar is in 150 DEG C
Dry 3h, 550 DEG C of roasting 3h, obtain carrier DZ1.
100.0 grams of carrier DZ1 are taken, contain MoO with 90 milliliters3287.3 grams per liters, 44.4 grams per liters of NiO, 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.
1 Mo of table is modified Beta molecular sieves and forms information
2 carrier of table and catalyst form information
Embodiment 10-12
The following examples illustrate the performance of catalyst provided by the invention.
Using the naphthane of purity 99% as raw material (analysis is pure), catalyst provided by the invention is evaluated in miniature fixed bed
The naphthane reactivity worth of C3, C4, C6, loaded catalyst are 1.2 grams, and reaction condition is 330 DEG C~390 DEG C, pressure
4.0MPa.It provides following two performance indicators (conversion ratio, BTX selectivity) preferably to carry out comparison and is defined.With ginseng
Reaction result than catalyst DC1 is absolutely, to calculate the relative conversion rate of the different catalysts under same reaction temperature, with
And under same conversion different catalysts opposite SBTXValue, the results are shown in Table 3.
Comparative example 2
DC1 is evaluated using with embodiment 10-12 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
12%~23%；Under same conversion, opposite BTX selectively improves 37%~48%.
Claims (20)
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 metal components, in terms of oxide and with
On the basis of the catalyst, the content of VIII race metal component is 1-10 weight %, and the content of VI B races metal component is 5-50
Weight %；The molecular sieve solid acid constituents is the mixture for including ZSM-5 molecular sieve and MoBeta type zeolite molecular sieves, described
The weight ratio of ZSM-5 molecular sieve and MoBeta type zeolite molecular sieves is 9 in molecular sieve mixture:1~1:9, wherein MoBeta
Type zeolite molecular sievenValue is 0<n <1,n=I/αI0, characterized in FT-IR methods, I is MoBeta type zeolite molecular sieves
3610cm in FT-IR spectrograms-1Absorption peak strength, I0For the parent Beta type zeolite molecular sieves of MoBeta type zeolite molecular sieves
3610cm in FT-IR spectrograms-1Absorption peak strength,αFor 3740cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves-1Absorption peak
Intensity and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves-1The ratio of absorption peak strength；With the MoBeta types
On the basis of zeolite molecular sieve, the content of the molybdenum in the MoBeta types zeolite molecular sieve in terms of oxide is 0.5-10 weight %.
2. catalyst according to claim 1, which is characterized in that in the molecular sieve mixture ZSM-5 molecular sieve and
The weight ratio of Beta type zeolite molecular sieves is 4:1~1:1.
3. catalyst according to claim 1, which is characterized in that the MoBeta types zeolite molecular sievenValue is 0.3
≤n≤0.8。
4. catalyst according to claim 1, which is characterized in that on the basis of the MoBeta types zeolite molecular sieve, institute
The content for stating the molybdenum in MoBeta type zeolite molecular sieves in terms of oxide is 1-9 weight %.
5. catalyst according to claim 1, 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 1.5-6 weight %, VI B races metal component is 10-40 weight %.
6. 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 %.
7. catalyst according to claim 6, 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 %.
8. catalyst according to claim 1 or 6, which is characterized in that on the basis of the catalyst, in the catalyst
The content of carrier is 45-90 weight %.
9. catalyst according to claim 8, which is characterized in that on the basis of the catalyst, carried in the catalyst
The content of body is 55-85 weight %, and the content of VIII race metal component in terms of oxide is 1.5-6 weight %, with oxide
The content of VI B races metal component of meter is 10-40 weight %.
10. 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 races metal component, the molecular sieve solid acid constituents be include ZSM-5
The mixture of molecular sieve and MoBeta molecular sieves, ZSM-5 molecular sieve and Beta type zeolite molecular sieves in the molecular sieve mixture
Weight ratio be 9:1~1:9, wherein MoBeta type zeolite molecular sievesnValue is 0<n <1,n=I/αI0, with FT-IR
Method characterizes, and I is 3610cm in the FT-IR spectrograms of MoBeta type zeolite molecular sieves-1Absorption peak strength, I0For MoBeta type zeolites
3610cm in the FT-IR spectrograms of the parent Beta type zeolite molecular sieves of molecular sieve-1Absorption peak strength,αFor MoBeta type zeolites point
3740cm in the FT-IR spectrograms of son sieve-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves-1
The ratio of absorption peak strength；
The preparation method of the MoBeta types zeolite molecular sieve includes：（1）Beta types zeolite molecular sieve and compound containing Mo are mixed
It closes, a kind of mixture of Beta types zeolite molecular sieve and the compound containing Mo is obtained, using the MoBeta types zeolite molecular sieve as base
The dosage of standard, each component makes in final MoBeta 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 roasting
Temperature be 200-700 DEG C, roasting time be 1-24 hour, steam-laden gas flow for 0.3-2 standard cubic meters/kilogram
Hour, obtain MoBeta type zeolite molecular sieves；
In described the step of being introduced into hydrogenation active metal component into the carrier, counted using oxide and using the catalyst as base
The introduction volume of standard, VIII race metal component makes the content of VIII race's metal component in final catalyst for 1-10 weight %, and described VI
The introduction volume of B races metal component makes the content of VI B races metal component in final catalyst be 5-50 weight %.
11. according to the method described in claim 10, it is characterized in that, in the molecular sieve mixture ZSM-5 molecular sieve and
The weight ratio of Beta molecular sieves is 4:1~1:1；The MoBeta types zeolite molecular sievenValue for 0.3≤n≤0.8。
12. according to the method described in claim 10, it is characterized in that, on the basis of the MoBeta types zeolite molecular sieve, respectively
The dosage of component makes in final MoBeta types zeolite molecular sieve, and the molybdenum content in terms of oxide is 1-9 weight %.
13. according to the method described in claim 10, it 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.
14. 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.
15. according to the method for claim 14, 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。
16. according to the method for claim 15, which is characterized in that the diluent gas is hydrogen.
17. according to the method described in claim 10, it 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 1.5-6 weight %, VI B races metal component, to be made most
The content of VI B races metal component is 10-40 weight % in whole catalyst.
18. according to the method described in claim 10, it 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.
19. according to the method for claim 18, 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 %.
20. 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 1-9 any one provides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410437783.XA CN105435836B (en) | 2014-08-29 | 2014-08-29 | A kind of hydrocracking catalyst and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410437783.XA CN105435836B (en) | 2014-08-29 | 2014-08-29 | A kind of hydrocracking catalyst and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105435836A CN105435836A (en) | 2016-03-30 |
| CN105435836B true CN105435836B (en) | 2018-07-31 |
Family
ID=55546728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410437783.XA Active CN105435836B (en) | 2014-08-29 | 2014-08-29 | A kind of hydrocracking catalyst and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105435836B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433211B (en) | 2020-10-19 | 2024-05-31 | 中国石油化工股份有限公司 | Chemical hydrocracking catalyst and its prepn and application |
| CN116064132B (en) * | 2021-10-29 | 2024-05-07 | 中国石油化工股份有限公司 | Diesel catalytic separation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1552818A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Monox-alumina containnig hydrocracking catalyst |
| CN1782034A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for simultanesusly reducing sulfur and olefine content in gasoline |
| CN103028445A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Porous carrier as well as preparation method and application thereof |
-
2014
- 2014-08-29 CN CN201410437783.XA patent/CN105435836B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1552818A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Monox-alumina containnig hydrocracking catalyst |
| CN1782034A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for simultanesusly reducing sulfur and olefine content in gasoline |
| CN103028445A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Porous carrier as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Structural studies of MoY zeolite catalysts by EXAFS;Wei Shiqiang et al.;《Chinese Science Bulletin》;19950930;第40卷(第17期);第1434-1437页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105435836A (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hédoire et al. | Support effect in hydrotreating catalysts: hydrogenation properties of molybdenum sulfide supported on β-zeolites of various acidities | |
| CN105413741B (en) | The method of hydrocracking catalyst and preparation method thereof and hydrocracking reaction | |
| US10252255B2 (en) | Method for preparing noble metal hydrogenation catalyst, noble metal hydrogenation catalyst and use thereof | |
| CN108055832A (en) | The midbarrel hydrocracking catalyst of β zeolites containing USY zeolite and with Low acid and big crystal domain size | |
| CN105435836B (en) | A kind of hydrocracking catalyst and its preparation and application | |
| CN105709802B (en) | A kind of high metal dispersion degree hydrocracking catalyst and preparation method thereof | |
| CN104923291B (en) | A kind of hydrocracking catalyst and its preparation and application | |
| CN105435835B (en) | A kind of hydrocracking catalyst and its preparation and application | |
| CN107345155A (en) | A kind of method for hydrogen cracking | |
| CN103191774A (en) | Method for preparing hydrocracking catalyst | |
| CN105363488B (en) | A kind of hydrocracking catalyst and its preparation and application | |
| CN105435837B (en) | A kind of hydrocracking catalyst and its preparation and application | |
| CN108262063A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN105709805B (en) | A kind of chemical industry type hydrocracking catalyst and preparation method thereof | |
| CN112275310A (en) | Heavy aromatic hydrocarbon lightening catalyst based on VIB and VIII group composite metal elements and preparation method and application thereof | |
| CN104923290B (en) | A kind of hydrocracking catalyst and its preparation method and application | |
| CN107345154B (en) | A kind of method for hydrogen cracking of poor ignition quality fuel | |
| CN104923292B (en) | A kind of hydrocracking catalyst and its preparation and application | |
| CN106140313B (en) | A kind of hydrogenation catalyst and its application in hydrocarbon hydrogenation reaction | |
| CN105457672B (en) | The method of hydrocracking catalyst and preparation method thereof and hydrocracking reaction | |
| CN105709807B (en) | A kind of hydrocracking catalyst and preparation method thereof | |
| CN105709801B (en) | A kind of preparation method of chemical industry type hydrocracking catalyst | |
| CN112742460B (en) | Hydrocracking catalyst, and preparation method and application thereof | |
| CN112295607B (en) | Processing method for light conversion of heavy aromatics and heavy aromatics selective hydrogenation catalyst | |
| CN104043474B (en) | A kind of hydrocracking catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |