CN105413741B - The method of hydrocracking catalyst and preparation method thereof and hydrocracking reaction - Google Patents
The method of hydrocracking catalyst and preparation method thereof and hydrocracking reaction Download PDFInfo
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Abstract
The present invention provides the methods of a kind of hydrocracking catalyst and preparation method thereof He hydrocracking reaction.The hydrocracking catalyst includes the active component of carrier and load on the carrier, wherein, the active component is made of three kinds of molybdenum, cobalt and nickel components, it is counted by oxide and on the basis of the total weight of the hydrocracking catalyst, the content of the molybdenum is 3 20 weight %, the content of the cobalt is 0.5 5 weight %, and the content of the nickel is 0.1 1.5 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 1 10:1；The carrier contains solid acid component and inorganic refractory oxides, and the solid acid component is at least two in amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve.The hydrocracking catalyst is not only not easy carbon distribution, but also can obtain the isocrackate with higher arene content, great prospects for commercial application.
Description
Technical field
The present invention relates to described in a kind of hydrocracking catalyst, the preparation method of the hydrocracking catalyst and use
The method that hydrocracking catalyst carries out hydrocracking reaction.
Background technology
With the aggravation of crude oil heaviness, in poor quality degree, the secondary processing diesel oils such as catalytic cracking diesel oil, coker gas oil evaporate
The quality divided is increasingly worse, is in particular in the aspects such as density is big, nitrogen content is high, arene content is high, Cetane number is low.Therefore this
The hydro-upgrading of a little secondary processing diesel oil fractions rich in aromatic hydrocarbons is increasingly subject to the extensive concern of people.These poor ignition quality fuels are turned
It is one of effective technical way of secondary processing diesel oil to turn to high added value chemical industry material BTX or high octane gasoline component.At present,
Catalyst for hydro-upgrading report as the path core technology is more.
For example, US5,219,814 disclose one kind in 400-1000psi under the conditions of pressure, and the catalysis that will be enriched in aromatic hydrocarbons is split
Change the method that diesel oil is converted into high-octane naphtha fraction, wherein, the hydrocracking catalyst used includes ultrastable
Carrier and the active component selected from group VIII metal component and vib metals component, group VIII metal and molecular sieve
The molar ratio of framework aluminum content is less than 2, is preferably 0.25-0.50:1, the content of vib metals component is 0.25-25 weights
% is measured, wherein, active component is based on molybdenum cobalt or molybdenum nickel system.
US4,738,766 disclose a kind of method using hydrocracking catalyst production high octane gasoline component,
Employed in hydrocracking catalyst contain acidic components and metal component, the acidic components are y-type zeolite, the metal
Component is selected from least one of nickel, cobalt, molybdenum, tungsten and vanadium.In addition, the metal component of the catalyst disclosed in embodiment is molybdenum
Nickel, wherein, total metal contents in soil is 10 weight % or so, and nickel content is 3.8 weight %, and molybdenum content is 6.5 weight %.
CN1295111A discloses a kind of gasoline fraction catalyst for hydro-upgrading zeolite-containing, the catalyst contain molybdenum and/
One or more of tungsten, nickel and/or cobalt, auxiliary agent magnesium, macropore and mesopore zeolite and alumina host；In terms of oxide and to urge
On the basis of the total weight of agent, the total content of molybdenum and tungsten be 3-20 weight %, nickel and cobalt total content be 0.3-2% weight %,
Auxiliary agent content of magnesium is 1-7 weight %, and the content of zeolite is 5-60 weight %, and the auxiliary agent magnesium is present in the form of the oxide urges
In agent.
It is can be seen that from more than patent application using the hydrocarbon ils for being rich in aromatic hydrocarbons and produces high added value chemical industry material BTX as raw material
Or one of key of high octane gasoline component is in generation and the reduction that avoid aromatic hydrocarbons saturated reaction in upgrading processes as far as possible
The loss late of octane number.In order to reduce the hydrogenation activity of hydrocracking catalyst as far as possible to avoid aromatic hydrocarbons saturated reaction and
The loss late of octane number, the content of active metal is usually relatively low in presently used hydrocracking catalyst.However, it thus brings
The problem of be hydrocracking catalyst due to Hydrogenation is weaker and easy carbon distribution inactivates, so as to affect the operation of catalyst week
Phase, it is impossible to meet industrial requirement well.
The content of the invention
The purpose of the invention is to overcome to add the hydrocarbon ils for being rich in aromatic hydrocarbons using existing hydrocracking catalyst
Hydrogen cracking produces the defects of easy carbon distribution inactivation when high added value chemical industry material BTX or high-knock rating gasoline, and provides one kind not only
Be not easy carbon distribution but also can obtain with higher arene content isocrackate hydrocracking catalyst, it is described plus
The preparation method of hydrogen Cracking catalyst and the method that hydrocracking reaction is carried out using the hydrocracking catalyst.
The present invention provides a kind of hydrocracking catalyst, which includes carrier and is supported on the load
Active component on body, wherein, the active component is made of three kinds of molybdenum, cobalt and nickel components, is added in terms of oxide and with described
On the basis of the total weight of hydrogen Cracking catalyst, the content of the molybdenum is 3-20 weight %, and the content of the cobalt is 0.5-5 weights
% is measured, the content of the nickel is 0.1-1.5 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 1-
10:1；The carrier contains solid acid component and inorganic refractory oxides, and the solid acid component is amorphous silica-alumina, macropore boils
At least two in stone molecular sieve and mesopore zeolite molecular sieve.
The present invention also provides a kind of preparation method of hydrocracking catalyst, this method includes active component being supported on
On carrier, the active component is made of three kinds of molybdenum, cobalt and nickel components, in terms of oxide and with the hydrocracking catalyst
On the basis of total weight, the content of the molybdenum is 3-20 weight %, and the content of the cobalt is 0.5-5 weight %, the content of the nickel
For 0.1-1.5 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 1-10:1；The carrier contains
Solid acid component and inorganic refractory oxides, the solid acid component is amorphous silica-alumina, big-hole zeolite molecular sieve and mesoporous boil
At least two in stone molecular sieve.
In addition, the present invention also provides a kind of method of hydrocracking reaction, this method is included in hydrocracking reaction item
Under part, hydrocarbon ils is contacted with above-mentioned hydrocracking catalyst.
The present inventor by further investigation find, will contain simultaneously and only the molybdenum containing certain content, cobalt and
The active component of nickel is used with specific carrier combination, and strictly controls the molar ratio of cobalt atom and nickle atom in active component,
The hydrocracking catalyst so obtained can be avoided effectively in production high added value chemical industry material BTX or high octane gasoline component
The problem of catalyst carbon deposition is serious in the process, while the isocrackate being also possible that has higher arene content,
That is, very perfect optimization balance is realized in terms of the activity and stability of catalyst.
A preferred embodiment of the invention, when the solid acid component contains big-hole zeolite molecular sieve, and institute
It is that n values are 0 to state big-hole zeolite molecular sieve<n<1 MoY type zeolite molecular sieves, n=I/ α I0, characterized in FT-IR methods, I MoY
3625cm in the FT-IR spectrograms of type zeolite molecular sieve-1Absorption peak strength, I0For the parent y-type zeolite point of MoY type zeolite molecular sieves
3625cm in the FT-IR spectrograms of son sieve-1Absorption peak strength, α are 3740cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1It inhales
Receive peak intensity and 3740cm in the FT-IR spectrograms of parent Y-type zeolite molecular sieve-1It, can be further during the ratio of absorption peak strength
The carbon distribution content in hydrocracking catalyst is reduced, and the isocrackate made has higher arene content.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Hydrocracking catalyst provided by the invention includes the active component of carrier and load on the carrier, wherein,
The active component is made of three kinds of molybdenum, cobalt and nickel components, in terms of oxide and with the total weight of the hydrocracking catalyst
On the basis of, the content of the molybdenum is 3-20 weight %, and the content of the cobalt is 0.5-5 weight %, and the content of the nickel is 0.1-
1.5 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 1-10:1；The carrier contains solid acid
Component and inorganic refractory oxides, the solid acid component are amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecule
At least two in sieve.
Wherein, three kinds of molybdenum, cobalt, nickel components can exist in the form of the oxide, can also be in the form of sulfide
In the presence of can also exist in the form of the two mixture.In the presence of three of the above component is in the form of sulfide, meter
It needs first for sulfide to be converted into corresponding oxide during the content for calculating three of the above metal component and calculate again.
The hydrocracking catalyst provided according to the present invention, in order to enable these three components of molybdenum, cobalt and nickel play preferably
Concerted catalysis acts on, it is preferable that is counted by oxide and on the basis of the total weight of the hydrocracking catalyst, the molybdenum contains
It measures as 4-18 weight %, the content of the cobalt is 0.8-3.5 weight %, and the content of the nickel is 0.2-0.9 weight %, and described
The molar ratio of cobalt atom and nickle atom in active component is 1.5-6:1；It is highly preferred that it is split in terms of oxide and with the hydrogenation
On the basis of the total weight for changing catalyst, the content of the molybdenum is 7-11 weight %, and the content of the cobalt is 0.9-1.5 weight %,
The content of the nickel is 0.5-0.8 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 2-4:1.
The present invention is not particularly limited the content of the carrier and active component, and can be split according to the hydrogenation
The dosage for changing the carrier employed in catalyst preparation process and active component is controlled.For example, it is urged with described be hydrocracked
On the basis of the total weight of agent, the content of the carrier can be 70-95 weight %, be preferably 80-95 weight %；The activity
The content of component can be 5-30 weight %, be preferably 5-20 weight %.
The present invention is not particularly limited the content of the solid acid component in the carrier and inorganic refractory oxides, can
Think the conventional selection of this field.The solid acid component main function is that cracking activity is played in being hydrocracked, including isomery,
Open loop and lytic activity, and the main function of inorganic refractory oxides is to provide cementation and provides having for hydrogenation active component
Imitate carrier.In order to enable to hydrocracking catalyst can have both preferable Catalytic Cracking Performance and stability, it is preferable that
On the basis of the total weight of the carrier, the content of the solid acid component is 0.5-95 weight %, more preferably 1-80 weights
Measure %；The content of the inorganic refractory oxides is 5-99.5 weight %, more preferably 20-99 weight %.
The solid acid component can be amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve at least
Two kinds, the particularly preferably mixture of big-hole zeolite molecular sieve and mesopore zeolite molecular sieve, using the preferred solid acid component
The product that the hydrocracking catalyst enabled to is used to be hydrocracked acquisition has higher arene content.It is at this point, described
The weight ratio of large pore molecular sieve and mesoporous molecular sieve is preferably 1-15:1, more preferably 1-13:1.
The amorphous silica-alumina can be the table of the existing various solid acid components that can be used as hydrocracking catalyst
Face has acid silica-alumina, it is however preferred to have the silica-alumina of structure of similar to thin diaspore.Wherein, the nothing
The mass fraction of silica can be 1-80 weight % in amorphous silicon-alumina, be preferably 10-50 weight %.The amorphous silica-alumina
It can be commercially available, the Siral range of commercial products produced such as Condea companies of Germany is with structure of similar to thin diaspore
Silica-alumina.
The species of the large pore molecular sieve can be this field conventional selection, for example, can be modenite (including X
Type zeolite, y-type zeolite and type A zeolite), the one or more in β zeolites and faujasite, be preferably y-type zeolite and/or β boilings
Stone, more preferably y-type zeolite.Wherein, the example of the y-type zeolite includes but not limited to：HY zeolites, rare earth exchanged Y zeolite, rare earth HY
It is zeolite, overstable gamma zeolite, hyperastable Y-type RE zeolite, the Y zeolites of part amorphous, the Y zeolites of titaniferous, phosphorous Y zeolites, super steady
One or more in HY zeolites, rare-earth ultra-steady HY zeolites and dealuminium Y type beta stone.It is particularly preferred that the large pore molecular sieve is
MoY type zeolite molecular sieves, and the n values of the MoY types zeolite molecular sieve are 0<n<1, n=I/ α I0, characterized in FT-IR methods, I
For 3625cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorption peak strength, I0For the parent Y types of MoY type zeolite molecular sieves
3625cm in the FT-IR spectrograms of 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.It needs
It is noted that when the large pore molecular sieve is MoY type zeolite molecular sieves, the content of above-mentioned active component molybdenum is (for 3-20 weights
Measure %, be preferably 4-18 weight %, more preferably 7-11 weight %) include MoY type zeolite molecular sieves in Mo content.
In the present invention, the MoY types zeolite molecular sieve is one kind 0<n<1st, it is preferably the y-type zeolite of 0.3≤n≤0.8.
Preferably, on the basis of the total weight of the MoY types zeolite molecular sieve, in the MoY types zeolite molecular sieve in terms of oxide
The content of molybdenum is 0.5-10 weight %, is preferably 2-8 weight %.In the present invention, molybdenum oxide in the MoY types zeolite molecular sieve
Content (mass fraction)=MoY to be measured type zeolite molecular sieves in molybdenum oxide measured value/(MoY types zeolite molecular sieve to be measured
Amount × butt), wherein, butt for sample to be tested under air atmosphere 600 DEG C roasting 4 it is small when after weight and roasting before weight it
Than.
The parent Y-type zeolite molecular sieve can be HY zeolites, rare-earth type Y zeolites (REY), rare-earth type HY zeolites
(REHY), the Y boilings of overstable gamma zeolite (USY), hyperastable Y-type RE zeolite (REUSY), the Y zeolites (USY) of part amorphous, titaniferous
One or more of stone, phosphorous Y and super steady and HY types zeolite, dealuminium Y type beta stone.They can be commercially available commodity,
Existing various methods may be employed to be prepared.
A kind of specific embodiment according to the present invention, the MoY types zeolite molecular sieve is according to the side comprised the following steps
Method is prepared：
(1) Y-type zeolite molecular sieve with compound containing Mo is mixed, obtains a kind of Y-type zeolite molecular sieve and compound containing Mo
Mixture；
(2) mixture that step (1) obtains is enclosed into lower roasting in steam-laden atmosphere, obtains MoY type zeolite molecular sieves；
Wherein, on the basis of the MoY types zeolite molecular sieve that butt is counted, the dosage of each component makes in the step (1)
In final MoY type zeolite molecular sieves, preferably using the molybdenum content that oxide is counted as 0.5-10 weight %, more preferably in terms of oxide
Molybdenum content is 2-8 weight %.The molybdate compound preferably is selected from oxide, chloride or molybdate of molybdenum etc..The step (2)
In roasting condition include：Temperature is 200-700 DEG C, is preferably 400-650 DEG C；It is preferably 3-12 small when time is 1-24 small
When；Steam-laden gas flow is 0.3-2 standard cubic meters/kilogram hour, is preferably 0.6-1.5 standard cubic meter/thousand
Gram hour.
In the preparation process of above-mentioned MoY types zeolite molecular sieve, carrier gas is preferably comprised in the steam-laden atmosphere
Body.The diluent gas can for example be selected from the mixing of hydrogen, nitrogen, the gaseous mixture of hydrogen and nitrogen, air, air and nitrogen
At least one of gas, wherein, the volume mixture ratio of the vapor and diluent gas is preferably 1：10-100, more preferably
1：20-80.
The species of the mesoporous molecular sieve or the conventional selection of this field, for example, can be ZSM-5, ZSM-11,
One or more in ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50 and MCM-22, preferably
ZSM-5 and/or MCM-22, more preferably ZSM-5.
The species of the inorganic refractory oxides or the conventional selection of this field, for example, can be aluminium oxide, oxygen
Change one or more of zirconium, magnesia, thorium oxide, beryllium oxide, boron oxide, cadmium oxide, particularly preferably aluminium oxide.Wherein,
The aluminium oxide can be one or more of γ, η, θ, δ and χ transition aluminas, or (be selected containing component is dosed
From at least one of silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth) one or more of γ, η, θ, δ and χ transition phase oxidation
Aluminium is preferably gama-alumina and/or contains the above-mentioned gama-alumina for dosing component.The aluminium oxide can be obtained by commercially available
It arrives, can also be prepared according to well known to a person skilled in the art various methods, therefore not to repeat here.
The hydrocracking catalyst provided according to the present invention, the hydrocracking catalyst can also include being supported on carrier
On auxiliary agent, the auxiliary agent can be selected from the one or more in phosphorus, titanium and silicon, the hydrocracking catalyst so enabled to
Agent has higher catalyst activity.Usually, the auxiliary agent exists in the form of its oxide.In addition, it is split with the hydrogenation
On the basis of the total weight for changing catalyst, the content of the auxiliary agent in terms of oxide can be 0.1-10 weight %, be preferably
0.5-5 weight %, more preferably 2-4 weight %.
The preparation method of hydrocracking catalyst provided by the invention includes active component being supported on carrier, the work
Property component is made of three kinds of molybdenum, cobalt and nickel components, is counted by oxide and on the basis of the total weight of the hydrocracking catalyst,
The content of the molybdenum is 3-20 weight %, and the content of the cobalt is 0.5-5 weight %, and the content of the nickel is 0.1-1.5 weights
% is measured, and cobalt atom in the active component and the molar ratio of nickle atom are 1-10:1；The carrier contains solid acid component
With inorganic refractory oxides, the solid acid component is in amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve
At least two.
The preparation method of the hydrocracking catalyst provided according to the present invention, it is preferable that add in terms of oxide and with described
On the basis of the total weight of hydrogen Cracking catalyst, the content of the molybdenum is 4-18 weight %, and the content of the cobalt is 0.8-3.5 weights
% is measured, the content of the nickel is 0.2-0.9 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are
1.5-6:1.It is highly preferred that being counted by oxide and on the basis of the total weight of the hydrocracking catalyst, the content of the molybdenum
For 7-11 weight %, the content of the cobalt is 0.9-1.5 weight %, and the content of the nickel is 0.5-0.8 weight %, and the work
Property component in cobalt atom and nickle atom molar ratio be 2-4:1.
The present invention is not particularly limited the content of the solid acid component in the carrier and inorganic refractory oxides, can
Think the conventional selection of this field.As described above, the solid acid component, which is acted predominantly in being hydrocracked, plays cracking activity, bag
Isomery, open loop and lytic activity are included, and the main function of inorganic refractory oxides is to provide cementation and provides hydrogenation activity
The effective carrier of component.In order to enable to hydrocracking catalyst can have both preferable Catalytic Cracking Performance and stabilization
Property, it is preferable that on the basis of the total weight of the carrier, the content of the solid acid component is 0.5-95 weight %, more preferably
For 1-80 weight %；The content of the inorganic refractory oxides is 5-99.5 weight %, more preferably 20-99 weight %.
The solid acid component can be amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve at least
Two kinds, be preferably the mixture of big-hole zeolite molecular sieve and mesopore zeolite molecular sieve.It can using the preferred solid acid component
The product that the hydrocracking catalyst made is used to be hydrocracked acquisition has higher arene content.At this point, the macropore
The weight ratio of molecular sieve and mesoporous molecular sieve is preferably 1-15:1, more preferably 1-13.In addition, the it is highly preferred that macropore point
Son sieve is MoY type zeolite molecular sieves, and 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.
The amorphous silica-alumina, big-hole zeolite molecular sieve, specific kind of MoY types zeolite molecular sieve and mesopore zeolite molecular sieve
Class can be reasonably selected according to record above, and therefore not to repeat here.
The present invention is not particularly limited the preparation method of the carrier, for example, can be by by amorphous silica-alumina, big
Before at least two and inorganic refractory oxides and/or inorganic refractory oxides in hole zeolite molecular sieve and mesopore zeolite molecular sieve
It roasts and obtains after body mixing.Wherein, the mode of the mixing can be carried out according to existing various modes, for example, can be by nothing
In amorphous silicon-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve at least two with inorganic refractory oxides and/or inorganic
Refractory oxides precursor is placed in the mechanical equipments such as mixer, grinder and is stirred, and can also be incited somebody to action in the case where being enough slurrying conditions
At least two in amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve and inorganic refractory oxides and/or nothing
Machine refractory oxides precursor is mixed with water, is filtered, is dried or moist again afterwards.In addition, the condition of the roasting is usual
It can be 350-950 DEG C including calcination temperature, be preferably 450-900 DEG C；It is preferably 2-8 when roasting time can be 1-12 small
Hour.
The preparation method of the hydrocracking catalyst provided according to the present invention, the carrier can be depending on each using needing to be made
The easily operated molding of kind, for example, can be microballoon, spherical shape, tablet, bar shaped, hollow spherical shape, bar shaped or bulk etc..
In the forming process of carrier, appropriate extrusion aid and/or peptizing agent can be added in order to be molded.The extrusion aid and peptizing agent
Species is known to the skilled person, for example, the extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyethylene
One or more in alcohol and polyethylene glycol.The peptizing agent can be existing various conventional organic acids and/or inorganic acid.This
Outside, the dosage of the extrusion aid and peptizing agent can be the conventional selection of this field, and therefore not to repeat here.
The present invention is not particularly limited the method that the active component is supported on carrier, for example, may be employed
The methods of infusion process, spraying, coprecipitation, carries out.It, can be by carrier with containing when using infusion process load active component
The solution contact of water-soluble molybdenum compound, aqueous cobalt compound and water-soluble nickel compound, by three kinds of active components simultaneously
It is supported on carrier；It can also be by water-soluble molybdenum compound solution, aqueous solution cobalt salt solution and water-soluble nickel compound solution list
It is solely contacted with carrier, three kinds of components is supported on carrier respectively.Preferably, the active component is supported on carrier
Method is to connect the carrier and the solution containing water-soluble molybdenum compound, aqueous cobalt compound and water-soluble nickel compound
It touches, then the carrier after contact is dried and roasted, it is more easy using these preferred carrying methods, be conducive to work
Industry metaplasia is produced.
Specifically, in the preparation process of the hydrocracking catalyst, hydrogenation that the dosage of each substance can cause
In Cracking catalyst, on the basis of the total weight of the hydrocracking catalyst, the content of the carrier is 70-95 weight %,
The content of the active component is 5-30 weight %；Preferably, in the hydrocracking catalyst that the dosage of each substance makes, with
On the basis of the total weight of the hydrocracking catalyst, the content of the carrier is 80-95 weight %, and the active component contains
It measures as 5-20 weight %.
The species of the water-soluble molybdenum compound can be the conventional selection of this field, for example, the nitric acid of molybdenum can be selected from
One or more in salt, acetate, carbonate and soluble complexes.Specifically, the example of the water-soluble molybdenum compound
Including but not limited to：One or more in ammonium molybdate, potassium molybdate, sodium molybdate, nitric acid molybdenum, molybdenum trisulfate etc..
The species of the aqueous cobalt compound can be the conventional selection of this field, for example, the nitric acid of cobalt can be selected from
One or more in salt, acetate, carbonate and soluble complexes.Specifically, the example of the aqueous cobalt compound
Including but not limited to：Cobalt nitrate and/or cobaltous sulfate.
The species of the water-soluble nickel compound or the conventional selection of this field, for example, the nitre of nickel can be selected from
One or more in hydrochlorate, acetate, carbonate and soluble complexes.Specifically, the reality of the water-soluble nickel compound
Example includes but not limited to：Nickel nitrate and/or nickel sulfate.
In addition, the water-soluble molybdenum compound, aqueous cobalt compound and water-soluble nickel compound can contain crystallization
Water can not also contain the crystallization water.
The preparation method of hydrocracking catalyst provided by the invention further preferably includes auxiliary agent being supported on carrier, described
Auxiliary agent can be selected from the one or more in phosphorus, titanium and silicon, and the hydrocracking catalyst so enabled to has higher
Catalyst activity.Usually, the auxiliary agent exists in the form of its oxide.In the preparation process of hydrocracking catalyst,
The auxiliary agent and active component can be supported on carrier simultaneously；First auxiliary agent can also be supported on carrier, then again will
Active component is supported on the carrier for having loaded auxiliary agent；First active component can also be supported on carrier, then will helped again
Agent is supported on the carrier for having loaded active component；It is preferred that using the first mode of loading, i.e. by the auxiliary agent and activearm
Divide and be supported on simultaneously on carrier, can so simplify technique, convenient for industrialized production.Specifically, by carrier with containing water-soluble
Property molybdenum compound, aqueous cobalt compound, water-soluble nickel compound and auxiliary compound solution contact, then will be after contact
Carrier be dried and roast.Wherein, the auxiliary compound can be existing various can be converted into after firing
The substance of corresponding additive, therefore not to repeat here.In addition, the hydrocracking catalyst that the dosage of the auxiliary compound can cause
In agent, on the basis of the total weight of catalyst, the content for the auxiliary agent counted using oxide is preferably as 0.1-10 weight %
0.5-5 weight %, more preferably 2-4 weight %.
The present invention to by the carrier with containing water-soluble molybdenum compound, aqueous cobalt compound, water-soluble nickel compound
And the condition of the solution contact of the auxiliary compound of selectivity is not particularly limited, for example, generally including：Contact Temperature can
Think 0-100 DEG C, be preferably 10-80 DEG C；When time of contact can be 0.1-30 small, when being preferably 1-8 small.The contact can be with
It carries out, can also be carried out in open environment under air-proof condition, the aqueous solvent of loss can be supplemented in contact process, also may be used
Not supplement.Various gases, such as air, nitrogen, vapor etc. can be passed through in contact process, can not also be passed through any
New component.In addition, there is no particular limitation for concentration of the present invention to solution, as long as can ensure the load capacity of various composition i.e.
It can.
The present invention is to the carrier after contact being dried and roasting condition is not particularly limited.It is for example, described dry
It can be 100-300 DEG C that dry condition, which generally includes drying temperature, be preferably 100-280 DEG C；Drying time can be that 1-12 is small
When, when being preferably 2-8 small.It can be 350-550 DEG C that the condition of the roasting, which generally includes calcination temperature, be preferably 400-500
℃；When roasting time can be 1-10 small, when being preferably 2-8 small.
The preparation method of hydrocracking catalyst provided by the invention is additionally may included in before use, by catalyst in
At a temperature of 100-370 DEG C with sulphur, hydrogen sulfide or other carry out presulfurization containing sulfur feedstock, this presulfurization can outside reactor into
Row, also can be In-situ sulphiding in reactor, and active component is converted into sulphided state by oxidation state.
The method of hydrocracking reaction provided by the invention is included under the conditions of hydrocracking reaction, and hydrocarbon ils is added with above-mentioned
Hydrogen Cracking catalyst contacts.
The present invention is not particularly limited the hydrocracking reaction condition, for example, the hydrocracking reaction condition
It can be 200-460 DEG C to generally include reaction temperature, be preferably 220-440 DEG C；Hydrogen partial pressure can be 2-18MPa, be preferably 2-
15MPa；Volume space velocity can be 0.3-10h during the liquid of hydrocarbon ils-1, it is preferably 0.5-5h-1；Hydrogen to oil volume ratio can be 50-
5000:1, it is preferably 50-4000:1.
The hydrocracking reaction can it is existing it is various be enough to make the hydrocarbon ils under the conditions of hydrocracking reaction with
Carried out in the reaction unit of hydrocracking catalyst reaction, for example, can fixed bed reactors, moving-burden bed reactor or
It is carried out in fluidized bed reactor.In addition, during specific hydrocracking reaction, can be split in hydrogenation provided by the present invention
The optional hydrogenation catalyst of hydro-denitrification has been loaded before change catalyst.Reaction stream can be used Xun Huan, once by, string
The conventional hydrocracking technological process such as connection, parallel connection.
The hydrocarbon ils can be existing various heavy mineral oils, synthetic oil or their mixed fraction oil, specifically may be used
To be selected from diesel oil, crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar
With the one or more in heavy deasphalted oil.In addition, hydrocracking catalyst provided by the invention adding especially suitable for diesel oil
Hydrogen cracking reaction.
The present invention will be described in detail by way of examples below.
Embodiment 1
The embodiment is used to illustrate hydrocracking catalyst provided by the invention and preparation method thereof.
It is 76% by boehmite (catalyst Chang Ling branch company) that 78.0 grams of butts are 70%, 131.6 grams of butt
HY types zeolite (catalyst Chang Ling branch company, lattice constant are 24.62 angstroms) and 36.6 grams of butts be 82% ZSM-5 (sial
Than for 60:1) it is uniformly mixed, the three leaf bar shapeds that circumscribed circle diameter is 1.6 millimeters is extruded on banded extruder, then in 120 DEG C of drying
3 it is small when, then at 600 DEG C of roastings 4 it is small when, obtain catalyst carrier Z1, composition is shown in Table 1.
100 grams of above-mentioned carrier Z1,82 milliliters of ammonia spirits containing ammonium molybdate, cobalt nitrate and nickel nitrate (are converted into phase
The oxide answered contains 121.3 g/l of MoO respectively3, 16.2 g/l of CoO, 5.4 g/l of NiO) dipping 1 it is small when, then will be through
The carrier of dipping in 120 DEG C drying 2 it is small when, then at 450 DEG C roasting 3 it is small when, obtain hydrocracking catalyst C1.Using X-fluorescence
Method is measured the composition in hydrocracking catalyst C1, and the results are shown in Table 1.
Comparative example 1
The comparative example is used to illustrate hydrocracking catalyst of reference and preparation method thereof.
Catalyst carrier and hydrocracking catalyst are prepared according to the method for embodiment 1, unlike, in active component
Loading process in, the ammonia spirit containing ammonium molybdate, cobalt nitrate and nickel nitrate (is converted into corresponding oxide respectively to contain
121.3 g/l of MoO3, 16.2 g/l of CoO, 5.4 g/l of NiO) (be converted into the ammonia spirit containing ammonium molybdate and cobalt nitrate
Corresponding oxide contains 121.3 g/l of MoO respectively3With 21.6 g/l of CoO) it substitutes, obtain reference hydrocracking catalyst
DC1.The composition in reference hydrocracking catalyst DC1 is measured using X-fluorescence method, the results are shown in Table 1.
Comparative example 2
The comparative example is used to illustrate hydrocracking catalyst of reference and preparation method thereof.
Catalyst carrier and hydrocracking catalyst are prepared according to the method for embodiment 1, unlike, in active component
Loading process in, the ammonia spirit containing ammonium molybdate, cobalt nitrate and nickel nitrate (is converted into corresponding oxide respectively to contain
121.3 g/l of MoO3, 16.2 g/l of CoO, 5.4 g/l of NiO) (be converted into the ammonia spirit containing ammonium molybdate and nickel nitrate
Corresponding oxide contains 121.3 g/l of MoO respectively3With 21.6 g/l of NiO) it substitutes, obtain reference hydrocracking catalyst
DC2.The composition in reference hydrocracking catalyst DC2 is measured using X-fluorescence method, the results are shown in Table 1.
Embodiment 2
The embodiment is used to illustrate hydrocracking catalyst provided by the invention and preparation method thereof.
It is 75% by boehmite (catalyst Chang Ling branch company) that 46.3 grams of butts are 70%, 191.7 grams of butt
HY zeolites (catalyst Chang Ling branch company, lattice constant are 24.59 angstroms) and 29.8 grams of butts be 80% MCM-22 (sial rubs
You are than being 30:1) it is uniformly mixed, the three leaf bar shapeds that circumscribed circle diameter is 1.6 millimeters is extruded on banded extruder, then in 120 DEG C of bakings
It is dry 3 it is small when, then at 580 DEG C of roastings 3 it is small when, obtain catalyst carrier Z2, composition is shown in Table 1.
100 grams of above-mentioned carrier Z2 are (equivalent with 85 milliliters of ammonia spirits respectively containing ammonium molybdate, cobalt nitrate and nickel nitrate
Contain 169.1 g/l of MoO respectively into corresponding oxide3, 50.7 g/l of CoO, 12.7 g/l of NiO) dipping 1 it is small when, then
By the carrier through dipping in 120 DEG C drying 2 it is small when, then at 450 DEG C roasting 3 it is small when, obtain hydrocracking catalyst C2.Using X
Fluorescence method is measured the composition in hydrocracking catalyst C2, and the results are shown in Table 1.
Embodiment 3
The embodiment is used to illustrate hydrocracking catalyst provided by the invention and preparation method thereof.
It is 79% by boehmite (catalyst Chang Ling branch company) that 66.3 grams of butts are 70%, 180.5 grams of butt
β zeolites (catalyst Chang Ling branch company, silica alumina ratio 50:And ZSM-5 (silica alumina ratios 50 that 13.7 grams of butts are 80% 1):1)
It is uniformly mixed, the three leaf bar shapeds that circumscribed circle diameter is 1.6 millimeters is extruded on banded extruder, then when 120 DEG C of drying 3 are small, then
When 580 DEG C of roastings 3 are small, catalyst carrier Z3 is obtained, composition is shown in Table 1.
100 grams of above-mentioned carrier Z3,85 milliliters of ammonia spirits containing ammonium molybdate, cobalt nitrate and nickel nitrate (are converted into phase
The oxide answered contains 84.5 g/l of MoO respectively3, 21.1 g/l of CoO, 10.6 g/l of NiO) dipping 1 it is small when, then will be through
The carrier of dipping in 120 DEG C drying 2 it is small when, then at 450 DEG C roasting 3 it is small when, obtain hydrocracking catalyst C3.Using X-fluorescence
Method is measured the composition in hydrocracking catalyst C3, and the results are shown in Table 1.
Embodiment 4
The embodiment is used to illustrate hydrocracking catalyst provided by the invention and preparation method thereof.
The β for being 79% by boehmite (catalyst Chang Ling branch company) that 68 grams of butts are 70%, 96.5 grams of butt
Zeolite (catalyst Chang Ling branch company, silica alumina ratio 50:1), the ZSM-5 (silica alumina ratios 50 that 63.5 grams of butts are 80%:1) with
The amorphous silica-alumina (Condea companies, Siral40) that 32.2 grams of butts are 79% is uniformly mixed, and circumscribed circle is extruded on banded extruder
A diameter of 1.6 millimeters of three leaf bar shapeds, then in 120 DEG C drying 3 it is small when, then at 550 DEG C roasting 3 it is small when, obtain catalyst load
Body Z4, composition are shown in Table 1.
By 100 grams of above-mentioned carrier Z4 with 78 milliliters containing molybdenum trioxide, basic cobaltous carbonate, basic nickel carbonate, phosphoric acid water
Solution (is converted into corresponding oxide and contains 244.3 g/l of MoO respectively3, 48.9 g/l of CoO, 4.9 g/l of NiO, 48.9
G/l P2O5) dipping 1 it is small when, then by the carrier through dipping in 120 DEG C drying 2 it is small when, then at 450 DEG C roasting 3 it is small when, obtain
Hydrocracking catalyst C4.The composition in hydrocracking catalyst C4 is measured using X-fluorescence method, result such as 1 institute of table
Show.
Embodiment 5
The embodiment is used to illustrate hydrocracking catalyst provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares hydrocracking catalyst, unlike, in the preparation process of carrier, will
ZSM-5 (the silica alumina ratios 60 that 36.6 grams of butts are 82%:1) with the amorphous silica-alumina that 36.6 grams of butts are 82%, (Condea is public
Department, Siral40) it substitutes, obtain catalyst carrier Z5 and hydrocracking catalyst C5.Wherein, the group of the catalyst carrier Z5
Into being shown in Table 1, the composition in hydrocracking catalyst C5 is measured using X-fluorescence method, the results are shown in Table 1.
Embodiment 6
The embodiment is used to illustrate hydrocracking catalyst provided by the invention and preparation method thereof.
Catalyst carrier and hydrocracking catalyst are prepared according to the method for embodiment 1, unlike, by HY type zeolites
It is substituted with the MoY types zeolite molecular sieve of identical weight part, and adjusts the content of ammonium molybdate in maceration extract so that is finally obtained adds
MoO in hydrogen Cracking catalyst3Total content it is same as Example 1, obtain carrier Z6 and hydrocracking catalyst C6.Wherein, institute
The composition for stating catalyst carrier Z6 is shown in Table 1, and the composition in hydrocracking catalyst C6 is measured using X-fluorescence method, knot
Fruit is as shown in table 1.
The MoY types zeolite molecular sieve is prepared as follows to obtain：
200.0 grams of USY molecular sieves (Chang Ling catalyst branch company product, butt 0.75) is taken to be ground with 6.3 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.Tube furnace flat-temperature zone is subsequently placed in, under hydrogen and steam atmosphere when 450 DEG C of roastings 4 are small,
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
Son sieve, i.e. MoY types zeolite molecular sieve, are denoted as MoUSY1, wherein, n=0.6, and surveyed using X-ray fluorescence spectra analysis (XRF)
Obtain MoO in MoUSY13Content be 4 weight %.
Embodiment 7
The embodiment is used to illustrate hydrocracking catalyst provided by the invention and preparation method thereof.
Catalyst carrier and hydrocracking catalyst are prepared according to the method for embodiment 1, unlike, by HY type zeolites
It is substituted with the MoY types zeolite molecular sieve of identical weight part, and adjusts the content of ammonium molybdate in maceration extract so that is finally obtained adds
MoO in hydrogen Cracking catalyst3Total content it is same as Example 1, obtain carrier Z7 and hydrocracking catalyst C7.Wherein, institute
The composition for stating catalyst carrier Z7 is shown in Table 1, and the composition in hydrocracking catalyst C7 is measured using X-fluorescence method, knot
Fruit is as shown in table 1.
The MoY types zeolite molecular sieve is prepared as follows to obtain：
200.0 grams of USY molecular sieves (Chang Ling catalyst branch company product, butt 0.75) is taken to be ground with 14.8 grams of molybdenum trioxides
It grinds, be uniformly mixed in alms bowl.Tube furnace flat-temperature zone is subsequently placed in, under hydrogen and steam atmosphere when 600 DEG C of roastings 8 are small,
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
Son sieve, i.e. MoY types zeolite molecular sieve, are denoted as MoUSY2, wherein, n=0.35, and surveyed using X-ray fluorescence spectra analysis (XRF)
Obtain MoO in MoUSY23Content be 9 weight %.
Table 1
Test case
Test case is used for the method for illustrating hydrocracking reaction.
Using density as 0.9203g/cm3, sulfur content 6600ppm, nitrogen content 750ppm, total arene content be 85.6 weights
The diesel oil of % is measured as raw material, hydrocracking catalyst C1, C5-C7 are evaluated on 30 milliliters of fixed bed devices and reference hydrogenation is split
Change the performance of catalyst DC1-DC2, industrial catalyst for refining (catalyst Chang Ling is loaded on the wherein top of fixed bed device bed
Branch company's product, trade name RN-10B), hydrocracking catalyst C1, C5-C7 are loaded in lower part respectively and reference is hydrocracked
Catalyst DC1-DC2 (loadings are 15 milliliters).First toward the fixed bed dress for being filled with hydrocracking catalyst before into diesel oil
The kerosene containing 6 weight % carbon disulfide is passed through in putting as sulfurized oil to carry out presulfurization, presulfurization to hydrocracking catalyst
Condition is included first when 110 DEG C of vulcanizations 2 are small, then when 300 DEG C of vulcanizations 4 are small.After presulfurization is completed, it is passed through diesel oil and is hydrogenated with
Cracking reaction, reaction condition include：Reaction temperature is 400 DEG C, the liquid of hydrogen partial pressure 5.0MPa, diesel oil when volume space velocity be 0.7
Hour-1, hydrogen to oil volume ratio 800:1.Arene content in product naphtha cut is measured using liquid chromatography.It will add
Hydrogen Cracking catalyst is stripped after being unloaded from reaction tube with toluene solvant, afterwards in infrared spectroscopic determination extract
Carbon content, wherein, the carbon distribution content of hydrocracking catalyst C1 is defined as 100%.Acquired results are as shown in table 2.
Table 2
| Catalyst | Arene content (weight %) in naphtha cut | Opposite carbon content in catalyst, weight % |
| C1 | 58.2 | 100 |
| C5 | 56.3 | 105 |
| C6 | 62.1 | 85 |
| C7 | 65.3 | 76 |
| DC1 | 42.0 | 138 |
| DC2 | 50.7 | 96 |
From the results shown in Table 2, compared with existing hydrocracking catalyst, split using hydrogenation provided by the invention
Change catalyst and be not only not easy carbon distribution, but also the isocrackate with higher arene content can be obtained, great industry should
Use prospect.From the comparison of embodiment 1 and embodiment 5 can be seen that when the solid acid component for big-hole zeolite molecular sieve and in
During the mixture of hole zeolite molecular sieve, obtained hydrocracking catalyst is used to be hydrocracked the product of acquisition with higher
Arene content.It can be seen that from the result of embodiment 1 and embodiment 6-7 when the solid acid component contains large pore zeolite molecule
Sieve, and the big-hole zeolite molecular sieve is that n values are 0<n<During 1 MoY type zeolite molecular sieves, it can further reduce and be hydrocracked
Carbon distribution content in catalyst, and the isocrackate made has higher arene content.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that the specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (32)
1. a kind of hydrocracking catalyst, the hydrocracking catalyst includes the activearm of carrier and load on the carrier
Point, which is characterized in that the active component is made of three kinds of molybdenum, cobalt and nickel components, is hydrocracked in terms of oxide and with described
On the basis of the total weight of catalyst, the content of the molybdenum is 3-20 weight %, and the content of the cobalt is 0.5-5 weight %, described
The content of nickel is 0.1-1.5 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 1-10:1；It is described
Carrier contains solid acid component and inorganic refractory oxides, and the solid acid component is amorphous silica-alumina, big-hole zeolite molecular sieve
With at least two in mesopore zeolite molecular sieve, the solid acid component contains big-hole zeolite molecular sieve, the large pore molecular sieve
For MoY type zeolite molecular sieves, and the n values of the MoY types zeolite molecular sieve are 0<n<1, n=I/ α I0, it is characterized in FT-IR methods,
I is 3625cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorption peak strength, I0For the parent Y types of MoY type zeolite molecular sieves
3625cm in the FT-IR spectrograms of 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. hydrocracking catalyst according to claim 1, wherein, in terms of oxide and with the hydrocracking catalyst
Total weight on the basis of, the content of the molybdenum is 4-18 weight %, and the content of the cobalt is 0.8-3.5 weight %, the nickel
Content is 0.2-0.9 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 1.5-6:1.
3. hydrocracking catalyst according to claim 2, wherein, in terms of oxide and with the hydrocracking catalyst
Total weight on the basis of, the content of the molybdenum is 7-11 weight %, and the content of the cobalt is 0.9-1.5 weight %, the nickel
Content is 0.5-0.8 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 2-4:1.
4. according to the hydrocracking catalyst described in any one in claim 1-3, wherein, with the hydrocracking catalyst
Total weight on the basis of, the content of the carrier is 70-95 weight %, and the content of the active component is 5-30 weight %.
5. hydrocracking catalyst according to claim 4, wherein, using the total weight of the hydrocracking catalyst as base
Standard, the content of the carrier is 80-95 weight %, and the content of the active component is 5-20 weight %.
6. according to the hydrocracking catalyst described in any one in claim 1-3, wherein, using the total weight of the carrier as
Benchmark, the content of the solid acid component is 0.5-95 weight %, and the content of the inorganic refractory oxides is 5-99.5 weights
Measure %.
7. hydrocracking catalyst according to claim 6, wherein, it is described solid on the basis of the total weight of the carrier
The content of body acid constituents is 1-80 weight %, and the content of the inorganic refractory oxides is 20-99 weight %.
8. according to the hydrocracking catalyst described in any one in claim 1-3, wherein, the solid acid component is macropore
The mixture of zeolite molecular sieve and mesopore zeolite molecular sieve.
9. hydrocracking catalyst according to claim 8, wherein, the weight of the large pore molecular sieve and mesoporous molecular sieve
Than for 1-15:1.
10. hydrocracking catalyst according to claim 1, wherein, the n values of the MoY types zeolite molecular sieve for 0.3≤
n≤0.8。
11. hydrocracking catalyst according to claim 1, wherein, using the total weight of the MoY types zeolite molecular sieve as
Benchmark, the content for the molybdenum counted using oxide in the MoY types zeolite molecular sieve is 0.5-10 weight %.
12. hydrocracking catalyst according to claim 1, wherein, the parent Y-type zeolite molecular sieve is boiled selected from HY
The Y boilings of stone, rare earth exchanged Y zeolite, rare earth HY zeolites, overstable gamma zeolite, hyperastable Y-type RE zeolite, the Y zeolites of part amorphous, titaniferous
One or more in stone and phosphorous Y zeolites.
13. according to the hydrocracking catalyst described in any one in claim 1-3, wherein, the mesoporous molecular sieve is
One kind in ZSM-5, ZSM-11, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50 and MCM-22
It is or a variety of.
14. according to the hydrocracking catalyst described in any one in claim 1-3, wherein, the hydrocracking catalyst
Further include the auxiliary agent of load on the carrier, one or more of the auxiliary agent in phosphorus, titanium and silicon.
15. hydrocracking catalyst according to claim 14, wherein, using the total weight of the hydrocracking catalyst as
Benchmark, the content for the auxiliary agent counted using oxide is 0.1-10 weight %.
16. a kind of preparation method of hydrocracking catalyst, this method includes active component being supported on carrier, the activity
Component is made of three kinds of molybdenum, cobalt and nickel components, is counted by oxide and on the basis of the total weight of the hydrocracking catalyst, institute
The content of molybdenum is stated as 3-20 weight %, the content of the cobalt is 0.5-5 weight %, and the content of the nickel is 0.1-1.5 weight %,
And cobalt atom in the active component and the molar ratio of nickle atom are 1-10:1；The carrier contains solid acid component and inorganic
Refractory oxides, the solid acid component be amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve at least
Two kinds, the solid acid component contains big-hole zeolite molecular sieve, and the large pore molecular sieve is MoY type zeolite molecular sieves, and described
The n values of MoY type zeolite molecular sieves are 0<n<1, n=I/ α I0, characterized in FT-IR methods, I is the FT- of MoY type zeolite molecular sieves
3625cm in IR spectrograms-1Absorption peak strength, I0In FT-IR spectrograms for the parent Y-type zeolite molecular sieve of MoY type zeolite molecular sieves
3625cm-1Absorption peak strength, α are 3740cm in the FT-IR spectrograms of MoY type zeolite molecular sieves-1Absorption peak strength and parent Y types
3740cm in the FT-IR spectrograms of zeolite molecular sieve-1The ratio of absorption peak strength.
17. the method according to claim 11, wherein, in terms of oxide and with the total weight of the hydrocracking catalyst
On the basis of, the content of the molybdenum is 4-18 weight %, and the content of the cobalt is 0.8-3.5 weight %, and the content of the nickel is
0.2-0.9 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 1.5-6:1.
18. the method according to claim 11, wherein, in terms of oxide and with the total weight of the hydrocracking catalyst
On the basis of, the content of the molybdenum is 7-11 weight %, and the content of the cobalt is 0.9-1.5 weight %, and the content of the nickel is
0.5-0.8 weight %, and cobalt atom in the active component and the molar ratio of nickle atom are 2-4:1.
19. the method according to claim 11, wherein, on the basis of the total weight of the carrier, the solid acid component
Content for 0.5-95 weight %, the content of the inorganic refractory oxides is 5-99.5 weight %.
20. the method according to claim 11, wherein, on the basis of the total weight of the carrier, the solid acid component
Content for 1-80 weight %, the content of the inorganic refractory oxides is 20-99 weight %.
21. according to the method described in any one in claim 16-20, wherein, solid acid component is big-hole zeolite molecular sieve
With the mixture of mesopore zeolite molecular sieve.
22. according to the method for claim 21, wherein, the weight ratio of the large pore molecular sieve and mesoporous molecular sieve is 1-
15:1。
23. according to the method for claim 16, wherein, the n values of the MoY types zeolite molecular sieve are 0.3≤n≤0.8.
24. the method according to claim 11, wherein, it is described on the basis of the total weight of the MoY types zeolite molecular sieve
The content for the molybdenum counted in MoY type zeolite molecular sieves using oxide is 0.5-10 weight %.
25. according to the method for claim 16, wherein, the parent Y-type zeolite molecular sieve is selected from HY zeolites, Rare Earth Y is boiled
Stone, rare earth HY zeolites, overstable gamma zeolite, hyperastable Y-type RE zeolite, the Y zeolites of part amorphous, the Y zeolites of titaniferous and phosphorous
One or more in Y zeolites.
26. according to the method described in any one in claim 16-20, wherein, the mesoporous molecular sieve is ZSM-5, ZSM-
11st, the one or more in ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50 and MCM-22.
27. according to the method described in any one in claim 16-20, wherein, the active component is supported on carrier
Method for the carrier and the solution containing water-soluble molybdenum compound, aqueous cobalt compound and water-soluble nickel compound are connect
It touches, then the carrier after contact is dried and roasted.
28. according to the method for claim 27, wherein, in the hydrocracking catalyst that the dosage of each substance makes, with
On the basis of the total weight of the hydrocracking catalyst, the content of the carrier is 70-95 weight %, and the active component contains
It measures as 5-30 weight %.
29. according to the method for claim 28, wherein, in the hydrocracking catalyst that the dosage of each substance makes, with
On the basis of the total weight of the hydrocracking catalyst, the content of the carrier is 80-95 weight %, and the active component contains
It measures as 5-20 weight %.
30. according to the method described in any one in claim 16-20, wherein, this method is further included is supported on institute by auxiliary agent
It states on carrier, one or more of the auxiliary agent in phosphorus, titanium and silicon.
31. the method according to claim 11, wherein, on the basis of the total weight of the hydrocracking catalyst, with oxygen
The content of the auxiliary agent of compound meter is 0.1-10 weight %.
32. a kind of method of hydrocracking reaction, this method are included under the conditions of hydrocracking reaction, by hydrocarbon ils and claim
Hydrocracking catalyst contact in 1-15 described in any one.
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| CN107344111B (en) * | 2016-05-05 | 2020-04-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst for maximum production of low-freezing diesel oil and preparation method and application thereof |
| CN107344110B (en) * | 2016-05-05 | 2020-04-10 | 中国石油化工股份有限公司 | Catalyst for producing hydrocracking tail oil with low straight-chain alkane content and preparation method and application thereof |
| CN107344112B (en) * | 2016-05-05 | 2020-02-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst for producing high-quality catalytic reforming raw material and preparation method and application thereof |
| WO2018047093A1 (en) * | 2016-09-12 | 2018-03-15 | Sabic Global Technologies B.V. | Hydrocracking process |
| CN108262064A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN108262076A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier and preparation method thereof |
| CN112742457B (en) * | 2019-10-30 | 2023-08-08 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| US8334231B2 (en) * | 2005-04-29 | 2012-12-18 | China Petroleum And Chemical Corporation | Hydrocracking catalyst, the preparation process and use of the same |
-
2014
- 2014-09-11 CN CN201410460633.0A patent/CN105413741B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8334231B2 (en) * | 2005-04-29 | 2012-12-18 | China Petroleum And Chemical Corporation | Hydrocracking catalyst, the preparation process and use of the same |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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