CN106622390B - A kind of carrier and its application and a kind of catalyst and its preparation method and application and a kind of method for hydrogen cracking - Google Patents

Abstract

The invention discloses a kind of carrier and its application, which contains dealuminzation Y type molecular sieve and heat-resistant inorganic oxide.The invention also discloses the catalyst and its preparation method and application using the carrier.The present invention further discloses the method for hydrogen cracking using the catalyst.Molecular sieve in support according to the present invention, not only crystallinity with higher and secondary pore abundant, but also there is lower non-framework aluminum content.Catalyst prepared by carrier loaded group VIII metallic element of the invention and vib metals element, better catalytic performance is shown in hydrocarbon ils plus hydrogen cracking reaction, can obtain good balance between catalytic activity, intermediate oil selectivity and tail oil BMCI value.

Description

A kind of carrier and its application and a kind of catalyst and its preparation method and application and one Kind method for hydrogen cracking

Technical field

The present invention relates to hydrocarbon oil hydrogenation cracking technology fields, in particular it relates to a kind of carrier and its application, this hair It is bright to further relate to a kind of catalyst and its preparation method and application using the carrier, institute is used the invention further relates to a kind of State the method for hydrogen cracking of catalyst.

Background technique

In recent years, crude oil heaviness and in poor quality tendency are increasingly apparent in world wide, at the same time, to intermediate oil It is but continuously increased with the demand of reformation, steam crack material.This promotes heavy distillate processing technology to be rapidly developed, and Catalyst is wherein mostly important and crucial factor.

For hydrocracking technology in addition to it can produce the intermediate oil of high quality, product variety and yield can be according to markets Demand is adjusted, and produces the stone of high fragrant potential content according to the actual state of refinery by the combination and gradation of multiple catalysts Cerebrol does reformer feed production aromatic hydrocarbons, the tail oil of low aromatic index (BMCI) makees steam crack material production ethylene or makees isomery drop Solidifying raw material production base oil of high viscosity index lubricant etc., further increases economic benefit.

Often there is activity, tail oil BMCI value and intermediate oil choosing in the hydrocracking catalyst for producing low BMCI value Contradiction between selecting property, activity is high, and intermediate oil is selectively low, and vice versa.But intermediate oil selectivity and tail oil Also always the people having the same aspiration and interest is not synchronous between BMCI value, and the intermediate oil selectivity of some catalyst is high, and tail oil BMCI value is also higher.Such as What takes into account several characteristics, crucial still to lean on catalyst.

Hydrocracking catalyst is typical bifunctional catalyst, by having the function of hydrogenating function (metal component) and cracking The group of (acid carrier) is grouped as.Metal component is generally made of VIII group and group vib element, can be divided into noble metal (Pt, ) and two class of base metal (Ni, Co, Mo, W) Pd；Acid carrier is usually SiO₂-Al₂O₃、SiO₂The amorphous heat-resisting nothing such as-MgO In addition to this machine oxide and molecular sieve can also include some auxiliary elements such as adhesive, auxiliary agent in catalyst.One high property The hydrogenating function and cracking function of the hydrocracking catalyst of energy should match, when being used to produce intermediate oil, in addition to tool There is high intermediate oil selectivity outer, also to there is very high activity.Reach these requirements, on the one hand needs function admirable Acid material and hydrogenation material, on the other hand also to consider cooperateing between application material and cooperation.

Acidic components can be generally divided into amorphous oxide (such as SiO according to crystalline condition₂-Al₂O₃, SiO₂-MgO Deng) and two class of molecular sieve, they respectively have feature.It is well known that crystalline aluminosilicate (or referred to as molecular sieve or zeolite), such as Y, ZSM-5 or modenite etc., they perhaps directly as catalyst or as a component part of catalyst, are answered extensively For hydrocarbon manufacture field, the Y type molecular sieve applied in hydrocracking catalyst is usually modified.

Molecular sieve be usually by oxygen-octahedron and aluminum-oxygen tetrahedron form (it is former that some molecular sieves also contain other skeletons Son, such as phosphorus, titanium) crystalline material with regular cellular structure.Oxygen-octahedron and aluminum-oxygen tetrahedron are by sharing one Oxygen atom links together, and by this mode, forms chain or cyclic structural unit, and then form cage structure, these cages Shape structure often has pore size, and equal aperture, these apertures do not interconnect again, and inside is interconnected, most end form At duct.Different with the type and preparation method of molecular sieve, the duct connection type inside aperture size and molecular sieve is also Difference, the aperture of common molecular sieve is in 1nm or less.Since the aluminium atom in aluminum-oxygen tetrahedron is the+coordination of trivalent 4, for balance electricity Lotus, each aluminum-oxygen tetrahedron will have a positive charge to compensate, and common compensating cation is sodium ion and potassium ion, this The metal cation of a little compensation charges can generally be exchanged into other ions by way of ion exchange, such as: NH₄ ⁺、H⁺Or Rare earth ion etc..

Molecular sieve used in hydrocracking catalyst is generally macropore Si-Al molecular sieve, mainly include Y type molecular sieve and Beta molecular sieve, wherein Y type molecular sieve has the features such as at low cost, adjustable range is big, answers in current hydrocracking catalyst With more.

US4925820 proposes a kind of preparation method of midbarrel oil type catalyst, is less than using lattice constantAnd Y type molecular sieve of the water adsorption capacity not less than 8%, amorphous silica-alumina and alumina adhesive composition. JP2007313409 proposes similar catalyst, is existed using lattice constantY type molecular sieve, comparison knot Fruit shows that lattice constant is less thanMolecular sieve intermediate oil selectivity it is high.US20020160906 proposes one The preparation method of the acid amorphous silica-alumina of kind, it is believed that the hydrocracking catalyst for preparing the material and Modified Zeolite Y together Agent has high intermediate oil selectivity.Wherein the lattice constant of Modified Zeolite Y is less than

In order to improve the activity and selectivity of PETROLEUM PROCESSING catalyst, usually zeolite used in it is modified, it is known that Method of modifying include: that the cation of zeolite is changed by ion exchange and improves the sial of zeolite by the framework modification of zeolite Than, wherein aluminium content is low in zeolite obtained by latter method of modifying, lattice constant reduces, and zeolite skeleton silica alumina ratio improves, thus Sour density is reduced, acid strength is improved, improves the thermal stability and hydrothermal stability of catalyst.

The processing method that can achieve this purpose in prior art has: hydrothermal dealumination and chemical dealuminization；The former is in water In the presence of steam, high-temperature roasting NH₄High-silicon Y-Zeolite, referred to as overstable gamma zeolite (USY) is made in NaY zeolite；The latter is with containing fluorination Object, such as ammonium fluosilicate or other fluorine-containing salts are closed, such as ammonium fluoride, ammonium fluoroborate, ammonium titanium fluoride are removed as dealumination agent NH₃Aluminium in Y or NaY zeolite skeleton, in addition, move into silicon on the vacancy in skeleton after dealuminzation, referred to as skeleton rich silicon Y zeolite (FSEY)；Or use EDTA (ethylenediamine tetra-acetic acid) etc. as dealumination agent, high-silicon Y-Zeolite (DAY) obtained；Chemical dealuminization and water Heat treatment combines and new-type high silicon Y zeolite processed (NHSY) is used alternatingly.

When chemical dealuminization skeleton rich silicon Y zeolite, using EDTA, when degree of dealumination is more than the 30% of framework aluminum content, boiling Stone crystallinity is begun to decline, and more than 50%, decline is more serious, simultaneously because the acidity of EDTA is stronger, solubility in water is small, With Al³⁺Complexing power it is weak, therefore in dealumination reaction, for the crystallinity for keeping zeolite, it is necessary to very dilute solution with extremely slow Speed be added reaction system.Using SiCl₄The shortcomings that isomorphous substitution method is that corrosivity is strong, and reaction is not easy uniformly to carry out, and is generated Non-framework aluminum be difficult to elute, the duct patency of zeolite is reduced, in addition, SiCl₄The secondary pore that isomorphous substitution method generates is seldom, Secondary pore is not generated even.Utilize (NH₄)₂SiF₆Same order elements are carried out, although reaction condition is mild, in the dealuminated zeolite of preparation Non-framework aluminum content is low, and rejected region is few in crystal structure, but when zeolite skeleton aluminium removes 50-60% or more, zeolite crystal Structure is still seriously damaged, and the indissoluble fluoride being mingled in zeolite is not easy to wash most, can destroy under remaining fluoride high temperature The crystal structure of zeolite.

Summary of the invention

The purpose of the present invention is to provide a kind of catalyst with the effect that is hydrocracked, which is used for hydrocarbon oil hydrogenation When cracking, preferable balance can be obtained between activity, intermediate oil selectivity and tail oil BMCI value.

According to the first aspect of the invention, the present invention provides a kind of carrier, the carrier contain dealuminzation Y type molecular sieve with And heat-resistant inorganic oxide, wherein the dealuminzation Y type molecular sieve is the dealuminzation Y type prepared using method comprising the following steps Molecular sieve:

It (1) is the raw material of alkali metal ion by the ion exchange liquid containing ion-exchanger and at least partly compensating cation Y type molecular sieve carries out ion exchange, molecular sieve after being exchanged；

(2) molecular sieve after the exchange is subjected to hydro-thermal process, obtains molecular sieve after the first hydro-thermal process, at the hydro-thermal The condition of reason makes after the first hydro-thermal process in the infrared spectrogram of molecular sieve, the antisymmetric vibration frequency σ of structure sensitive₁Meet The following conditions:

35≤0.766 × (1086- σ₁)≤42；

(3) under the conditions of dealumination reaction, by molecular sieve after first hydro-thermal process and contain dealumination agent and ion exchange The dealuminzation solution of agent contacts, and obtains dealuminzation molecular sieve, and the dealumination agent is selected from acid, the dealumination agent and first hydro-thermal process Afterwards the ratio of molecular sieve be 0.0005-0.005, the dealumination agent in mol, after first hydro-thermal process molecular sieve with gram Meter, and the molar ratio of the dealumination agent and the ion-exchanger is 0.2-0.8；

(4) the dealuminzation molecular sieve is subjected to hydro-thermal process, obtains molecular sieve after the second hydro-thermal process；

(5) under the conditions of dealumination reaction, by molecular sieve after second hydro-thermal process and contain ion-exchanger and fluorine silicon The dealuminzation solution contact of acid, obtains dealuminzation Y type molecular sieve.

According to the second aspect of the invention, the present invention provides carriers described in first aspect of the present invention as load The application of the carrier of type catalyst.

According to the third aspect of the present invention, the present invention provides a kind of catalyst, which includes carrier and bears Carry group VIII metallic element and vib metals element on the carrier, wherein the carrier is the present invention first Carrier described in aspect.

According to the fourth aspect of the present invention, the present invention provides a kind of preparation method of catalyst, this method is included in The supported on carriers group VIII metallic element and vib metals element, wherein the carrier is first side of the invention Carrier described in face.

According to the fifth aspect of the present invention, it is prepared the present invention provides the method as described in the 4th aspect of the present invention Catalyst.

According to the sixth aspect of the invention, the present invention provides described in third aspect of the present invention or the 5th aspect Catalyst as hydrocracking reaction catalyst application.

According to the seventh aspect of the present invention, the present invention provides a kind of method for hydrogen cracking, this method is included in plus hydrogen Under the conditions of cracking reaction, hydrocarbon ils is contacted with catalyst, the catalyst is third aspect of the present invention or the 5th aspect The catalyst.

Molecular sieve in support according to the present invention, not only crystallinity with higher and secondary pore abundant, but also tool There is lower non-framework aluminum content.

Catalyst prepared by carrier loaded group VIII metallic element of the invention and vib metals element, Hydrocarbon ils plus hydrogen cracking reaction in show better catalytic performance, can catalytic activity, intermediate oil selectivity and Preferably balance is obtained between tail oil BMCI value.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

According to the first aspect of the invention, the present invention provides a kind of carrier, the carrier contain dealuminzation Y type molecular sieve with And heat-resistant inorganic oxide.In the present invention, " carrier ", which refers to, can support substance and the effigurate formed solid body of tool.That is, The carrier is the porous former of the mixture containing molecular sieve and heat-resistant inorganic oxide.

Support according to the present invention, the dealuminzation Y type molecular sieve are the dealuminzation Y prepared using method comprising the following steps Type molecular sieve:

It (1) is the raw material of alkali metal ion by the ion exchange liquid containing ion-exchanger and at least partly compensating cation Y type molecular sieve carries out ion exchange, molecular sieve after being exchanged；

(2) molecular sieve after the exchange is subjected to hydro-thermal process, obtains molecular sieve after the first hydro-thermal process, at the hydro-thermal The condition of reason makes after the first hydro-thermal process in the infrared spectrogram of molecular sieve, the antisymmetric vibration frequency σ of structure sensitive₁Meet The following conditions:

35≤0.766 × (1086- σ₁)≤42；

(3) under the conditions of dealumination reaction, by molecular sieve after first hydro-thermal process and contain dealumination agent and ion exchange The dealuminzation solution of agent contacts, and obtains dealuminzation molecular sieve, and the dealumination agent is selected from acid, the dealumination agent and first hydro-thermal process Afterwards the ratio of molecular sieve be 0.0005-0.005, the dealumination agent in mol, after first hydro-thermal process molecular sieve with gram Meter, and the molar ratio of the dealumination agent and the ion-exchanger is 0.2-0.8；

(4) the dealuminzation molecular sieve is subjected to hydro-thermal process, obtains molecular sieve after the second hydro-thermal process；

(5) under the conditions of dealumination reaction, by molecular sieve after second hydro-thermal process and contain ion-exchanger and fluorine silicon The dealuminzation solution contact of acid, obtains dealuminzation Y type molecular sieve.

In step (1), at least partly compensating cation of the raw material Y type molecular sieve is alkali metal ion, the alkali gold Belonging to ion can be sodium ion and/or potassium ion, preferably sodium ion (that is, raw material Y type molecular sieve is NaY molecular sieve).It is described Depending on the content of alkali metal ion in raw material Y type molecular sieve is with the source of the Y type molecular sieve, it is not particularly limited.Generally, In terms of oxide, in the raw material Y type molecular sieve as the content of the alkali metal ion of compensating cation be 10-20 weight %, Such as 12-16 weight %.

The silica alumina ratio of raw material Y type molecular sieve is not particularly limited in the present invention, can be conventional selection.Generally, institute The silica alumina ratio for stating raw material Y type molecular sieve is 4 hereinafter, as 3.5 hereinafter, generally 2.5-3.5.

The crystallinity of raw material Y type molecular sieve is not particularly limited in the present invention.Using the above method to raw material Y type molecule Sieve carries out dealuminzation, can obtain while the aluminium content, particularly non-framework aluminum content for being effectively reduced raw material Y type molecular sieve Higher crystallinity retention rate.It can be according to the use occasion of the dealuminzation Y type molecular sieve finally prepared to raw material Y type molecular sieve Crystallinity is selected.Generally, the relative crystallinity of the raw material Y type molecular sieve is 85% or more (such as 85-120%), excellent It is selected as 90% or more, such as 90-95%.

The specific surface area and Kong Rong of raw material Y type molecular sieve is not particularly limited in the present invention.Specifically, the raw material Y The specific surface area of type molecular sieve can be 650-850m²/ g, preferably 680-800m²/ g, more preferably 700-750m²/g；It is described The Kong Rongke of raw material Y type molecular sieve is with for 0.3-0.45mL/g, preferably 0.32-0.4mL/g.

In step (1), the ion-exchanger and raw material Y type molecular sieve carry out ion exchange, so that raw material Y type molecular sieve In part compensating cation be ion exchanged replaced the ion-exchange group of agent.Can by by raw material Y type molecular sieve with Ion exchange liquid contact containing the ion-exchanger, to realize ion exchange.The solvent of the ion exchange liquid does not have It is particularly limited to, can be selected according to the dissolubility of ion-exchanger, generally water.

Support according to the present invention, from the crystallinity retention rate for further increasing the dealuminzation Y type molecular sieve finally prepared Angle is set out, and in step (1), the condition of ion exchange makes the alkali metal ion content measured after exchanging in molecular sieve be raw material Y type The 20-40% of alkali metal ion content measured in molecular sieve, preferably 25-35%, more preferably 28-35%, such as 30-33%.

Regulation can be carried out by the condition to ion exchange to obtain expected ion exchange degree, after exchanging Alkali metal ion content measured in molecular sieve controls within above range.In a preferred embodiment of the invention, institute State ion exchange not higher than 60 DEG C at a temperature of carry out.It is highly preferred that the ion exchange 20-55 DEG C at a temperature of into Row.

In the preferred embodiment, relative to 100 raw material Y type molecular sieves, the use of the ion-exchanger Amount can be 20-60 parts by weight, preferably 30-55 parts by weight, more preferably 35-50 parts by weight.

In the preferred embodiment, concentration of the ion-exchanger in ion exchange liquid can be conventional choosing It selects, preferably 0.05-10mol/L, more preferably 0.1-8mol/L, further preferably 1-7mol/L, such as 1.5-6mol/L.? In the preferred embodiment, the duration of the ion exchange can hand over according to the temperature and ion for implementing ion exchange The concentration for changing liquid is selected, and expected ion exchange degree can be obtained by being subject to.Generally, the ion exchange it is lasting when Between can be 1-500min, preferably 5-300min, more preferably 10-150min, further preferably 20-60min.The present invention In, " duration of ion exchange " refers to that raw material Y type molecular sieve starts to contact to what contact was completed with ion-exchanger and continues Time.In the actual operation process, the ion exchange liquid containing ion-exchanger can be added drop-wise to containing raw material Y type molecular sieve Slurries in, ion exchange is carried out during dropwise addition, time for adding is the duration of above-mentioned ion exchange at this time.

It in step (1), after the completion of ion exchange, can be separated by solid-liquid separation, thus molecular sieve after being exchanged.The friendship Changing rear molecular sieve can be dried under normal conditions, to remove remaining ion exchange liquid.It generally, can be in 50-200 DEG C, preferably 80-180 DEG C, it is 100-150 DEG C more preferable, 105-130 DEG C further preferred at a temperature of be dried.The drying It can be carried out in air atmosphere, it can also be in inert atmosphere (such as group 0 element gas and/or nitrogen, the zero group gas Can be argon gas and/or helium) in carry out, be not particularly limited.The drying can (usually 1 standard be big in environmental pressure Air pressure) or decompression (be lower than environmental pressure) under conditions of carry out.The duration of the drying can according to dry temperature with And dry concrete mode carries out selectivity, the ion exchange liquid in molecular sieve after exchange can be removed by being subject to, generally can be with It is 1-10 hours, it is preferably 1.5-6 hours, 2-4 hours more preferable.

In the present invention, hydro-thermal process can be realized and being heat-treated molecular sieve in steam-laden atmosphere, Such as it can continue to be passed through steam-laden atmosphere into the container filled with molecular sieve during hydro-thermal process；It can also be with It is realized and being heat-treated aqueous molecular sieve pulp in closed container；It can also be the group of above two mode It closes.In the present invention, hydro-thermal process can carry out at a temperature of 500-700 DEG C.The steam-laden atmosphere can be all Vapor.The steam-laden atmosphere can also contain carrier gas, such as air, group 0 element gas (such as argon gas and/or helium Gas) and one or more of nitrogen combination.By adjusting carrier gas in atmosphere content can to the degree of reaction with And reaction rate is adjusted.

According to the method for the present invention, the condition of step (2) described hydro-thermal process makes molecular sieve after the first hydro-thermal process In infrared spectrogram, the antisymmetric vibration frequency σ of structure sensitive₁Meet the following conditions:

35≤0.766 × (1086- σ₁)≤42。

It can make the dealuminzation Y type molecular sieve finally prepared that there is secondary pore abundant in this way and obtain higher crystallization Degree retention rate and lower sodium oxide content, the carrier containing the dealuminzation Y type molecular sieve are particularly suitable as hydrocracking catalyst The carrier of agent.

Preferably, the condition of step (2) described hydro-thermal process makes the infrared spectrogram of molecular sieve after the first hydro-thermal process In, the antisymmetric vibration frequency σ of structure sensitive₁Meet the following conditions:

38≤0.766 × (1086- σ₁)≤41.8。

It is highly preferred that the condition of step (2) described hydro-thermal process makes the infrared spectroscopy of molecular sieve after the first hydro-thermal process In figure, the antisymmetric vibration frequency σ of structure sensitive₁Meet the following conditions:

38≤0.766 × (1086- σ₁)≤40。

The antisymmetric vibration frequency σ of the structure sensitive₁Refer to after the first hydro-thermal process in the infrared spectrogram of molecular sieve Vibration peak within the scope of 1050-1150cm.

In a kind of embodiment of step (2), hydro-thermal process is carried out in steam-laden atmosphere.The containing water vapor Atmosphere can not contain carrier gas, carrier gas can also be contained.When the steam-laden atmosphere contains carrier gas, the content of carrier gas Can be 10-99 volume %, preferably 30-98.5 volume %, preferably 50 volume % or more, more preferably 80 volume % with On, further preferably 90 volume % or more, such as 95 volume % or more.In this embodiment, at relative to the first hydro-thermal of 1g Molecular sieve after reason, the intake of vapor can be 0.1-1mL/min, preferably 0.2-0.5mL/min.Preferably In, the hydro-thermal process can carry out at a temperature of 500-700 DEG C, preferably 550-680 DEG C at a temperature of carry out, the water The duration of heat treatment can be selected according to expected hydro-thermal process degree, generally can be 0.5-5 hours, preferably 1-4 hours, more preferably 2-4 hours.

In the another embodiment of step (2), aqueous molecular sieve pulp is heat-treated in closed container. Water content in aqueous molecular sieve pulp can be 30-85 weight %, preferably 45-70 weight %, more preferably 50-65 weight Measure %, further preferably 52-58 weight %.In this embodiment, the temperature of heat treatment can be 480-700 DEG C, preferably It is 500-650 DEG C, more preferably 520-580 DEG C, further preferably 540-560 DEG C.The duration of heat treatment can basis Expected heat treatment degree is selected, and generally can be 0.5-5 hours, preferably 1-4 hours, more preferably 1.5-3 hours. In this embodiment, it can not additionally apply pressure, i.e., be heat-treated under pressure itself；Pressure can also additionally be applied Power.When additionally applying pressure, the pressure in closed container being heat-treated can be 0.05-0.3MPa.

In step (3), the dealumination agent is selected from acid.The acid can be organic and or inorganic acids.Specifically, described Dealumination agent can be ethylenediamine tetra-acetic acid, oxalic acid, sulfosalicylic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid and fluosilicic acid One or more of.Preferably, the dealumination agent is oxygen-containing inorganic acid and/or hydrochloric acid.It is highly preferred that the dealuminzation Agent is one or more of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and phosphoric acid.It is further preferred that the dealumination agent is Hydrochloric acid, sulfuric acid and nitric acid.

The solvent of the dealuminzation solution can be selected according to the dissolubility of dealumination agent and ion-exchanger, can make to take off Aluminium agent and ion-exchanger dissolve to be formed subject to solution.Preferably, the solvent of the dealuminzation solution is water.

In step (3), the ratio of molecular sieve (in gram) after the dealumination agent (in mol) and first hydro-thermal process Value is 0.0005-0.005, preferably 0.0008-0.004, more preferably 0.001-0.0035.The dealumination agent and the ion The molar ratio of exchanger is 0.2-0.8, and preferably 0.6 hereinafter, more preferably 0.5 hereinafter, further preferably 0.45 hereinafter, more Further preferably 0.4 hereinafter, particularly preferably 0.35 hereinafter, such as 0.25 or less.

As a preferred embodiment of the invention, molecule after the dealumination agent (in mol) and first hydro-thermal process The ratio of (in gram) is sieved as 0.001-0.0035, the molar ratio of the dealumination agent and the ion-exchanger is 0.2-0.45. According to the preferred embodiment, higher relative crystallinity is can still be maintained in the dealuminzation Y type molecular sieve finally prepared.

In the dealuminzation solution, the concentration of dealumination agent can be 0.1-5mol/L, preferably 0.2-4mol/L, more preferably 0.4-3mol/L, further preferably 0.5-2.5mol/L are still more preferably 0.6-2mol/L.

Described in step (3) contact can 10-100 DEG C, preferably 15-50 DEG C, it is more preferable 20-40 DEG C at a temperature of into Row.In step (3), the duration of the contact can be selected according to the dosage of temperature and dealumination agent and ion-exchanger It selects, expected exposure level can be obtained by being subject to.Generally, the duration of the contact can be 0.25-5 hours, excellent It is selected as 0.5-3 hours, more preferably 0.8-2.5 hours." duration of contact " refers to molecule after the first hydro-thermal process It sieves and starts to contact the time completed to contact with the liquid phase containing dealumination agent and ion-exchanger.It, can be in actual mechanical process By dealumination agent and ion-exchanger be configured to solution be added dropwise to containing after the first hydro-thermal process in the slurries of molecular sieve after, continue to stir It mixes a period of time, the duration of the contact is the total duration for being added dropwise and stirring.The time of the dropwise addition typically constitutes from institute The 30-80% of the duration of contact is stated, the 40-60% of the duration of the contact is preferably accounted for.

In step (4), the hydro-thermal process can carry out under normal conditions, be not particularly limited.

In a kind of embodiment of step (4), hydro-thermal process is carried out in steam-laden atmosphere.The containing water vapor Atmosphere can not contain carrier gas, carrier gas can also be contained.When the steam-laden atmosphere contains carrier gas, relative to being passed through Speed is the water vapour of 1mL/min, and the speed that is passed through of carrier gas can be 20-80L/min, preferably 40-70L/min.In the reality It applies in mode, relative to 1g dealuminzation molecular sieve, the speed that is passed through of vapor can be 0.1-1mL/min, preferably 0.2- 0.5mL/min.In this embodiment, the hydro-thermal process can carry out at a temperature of 500-700 DEG C, preferably in 600- It is carried out at a temperature of 680 DEG C.The duration of the hydro-thermal process can be selected according to the temperature being heat-treated, generally It can be 1-5 hours, preferably 2-3 hours.

In the another embodiment of step (4), aqueous molecular sieve pulp is heat-treated in closed container. Water content in aqueous molecular sieve pulp can be 30-85 weight %, preferably 45-70 weight %, more preferably 60-68 weight Measure %.In this embodiment, the temperature of heat treatment can be 480-700 DEG C, preferably 500-650 DEG C, more preferably 520- 580 DEG C, further preferably 540-560 DEG C.The duration of heat treatment can be selected according to the temperature being heat-treated, It generally can be 0.5-5 hours, preferably 1-4 hours, more preferably 2-4 hours.It in this embodiment, can be not additional Apply pressure, i.e., is heat-treated under pressure itself；Pressure can also additionally be applied.When additionally applying pressure, heat is carried out Pressure in the closed container of processing can be 0.05-0.3MPa.

Preferably, second hydro-thermal process carries out in steam-laden atmosphere.

In step (5), the solvent of the dealuminzation solution is not particularly limited, can be according to ion-exchanger and fluosilicic acid Dissolubility is selected, and the ion-exchanger and fluosilicic acid can be dissolved by being subject to.Generally, step (5) the dealuminzation solution Solvent be water.

In step (5), the molar ratio of ion-exchanger and fluosilicic acid can be 0.1-8, preferably 0.2-7, more preferably 0.4-6.In step (5), the ratio of ion-exchanger (in mol) and dealuminzation molecular sieve (in gram) can be 0.0005- 0.01, preferably 0.001-0.008.

In step (5) the dealuminzation solution, the concentration of fluosilicic acid can be conventional selection.Preferably, step (5) is described de- In aluminum solutions, the content of fluosilicic acid can be 0.1-5mol/L, preferably 0.5-2.5mol/L, more preferably 0.6-1.5mol/ L。

Step (5) can carry out under the conditions of conventional dealumination reaction.It generally, can be at 40-100 DEG C, preferably 50-95 DEG C, it is 55-80 DEG C more preferable, 60-70 DEG C further preferred at a temperature of molecular sieve after second hydro-thermal process and ion are handed over Change agent and fluosilicic acid contact.The duration of the contact can be according to the temperature and fluosilicic acid of contact and ion-exchanger Dosage is selected.Generally, the duration of the contact can be 0.5-5 hours, preferably 0.8-3.5 hours.It is described Molecular sieve starts to connect with the liquid phase containing fluosilicic acid and ion-exchanger after " duration of contact " refers to the second hydro-thermal process The time that touching is completed to contact.In actual mechanical process, fluosilicic acid and ion-exchanger can be configured to solution and are added dropwise to contain After having after the second hydro-thermal process in the slurries of molecular sieve, continue stirring a period of time, the duration of the contact be added dropwise and The total duration of stirring.The time of the dropwise addition typically constitutes from the 30-60% of the duration of the contact, preferably accounts for described connect The 40-50% of the duration of touching.

In the present invention, step (1) ion-exchanger, step (3) ion-exchanger and step (5) it is described from The type of sub- exchanger can be identical or different, and specific type is not particularly limited, can be according to it is contemplated that drawing in Y type molecular sieve The type of the compensating cation entered is selected.Specifically, it is catalyzed in the dealuminzation Y type molecular sieve finally prepared for catalytic cracking When agent, step (1) ion-exchanger, step (3) ion-exchanger and step (5) described ion-exchanger are respectively It can be ammonium salt (that is, ammonium ion is introduced as compensating cation by ion exchange).The ammonium salt can be organic ammonium salt And/or inorganic ammonium salt, specific example can include but is not limited to ammonium oxalate, ammonium citrate, ammonium acetate, ammonium tartrate, sulfuric acid One or more of ammonium, ammonium chloride and ammonium nitrate.Preferably, the ammonium salt is inorganic ammonium salt, such as ammonium sulfate, ammonium chloride One or more of with ammonium nitrate.

Dealumination agent described in ion-exchanger described in step (3) and step (3) can have identical anion, can also To be not particularly limited with different anion.

Not only aluminium content, particularly non-framework aluminum content are low for the dealuminzation Y type molecular sieve prepared using the above method, but also have There is higher crystallinity retention rate, while the alkali metal ion content measured in molecular sieve as compensating cation is low.

Support according to the present invention also contains heat-resistant inorganic oxide.In the present invention, term " heat-resistant inorganic oxide " is Refer under oxygen or oxygen-containing atmosphere, inorganic oxygen-containing of the decomposition temperature not less than 300 DEG C (such as: decomposition temperature be 300-1000 DEG C) Compound.

The specific type of the heat-resistant inorganic oxide is not particularly limited in the present invention, can usually make for this field Heat-resistant inorganic oxide.The specific example of the heat-resistant inorganic oxide can include but is not limited to aluminium oxide, silica, Titanium oxide, magnesia, zirconium oxide, thorium oxide and silica-alumina.Preferably, the heat-resistant inorganic oxide be aluminium oxide, One or more of silica and silica-alumina.It is highly preferred that the heat-resistant inorganic oxide is aluminium oxide And/or silica-alumina.

Support according to the present invention, on the basis of the total amount of the carrier, the content of the dealuminzation Y type molecular sieve can be 0.1-70 weight %, the content of the heat-resistant inorganic oxide can be 30-99.9 weight %.

In of the invention one preferred example, on the basis of the total amount of carrier, the content of the dealuminzation Y type molecular sieve For 1-8 weight %, preferably 2-7 weight %, more preferably 3-6 weight %；The content of the heat-resistant inorganic oxide is 92-99 Weight %, preferably 93-98 weight %, more preferably 94-97 weight %.In the preferred example, the heat resistant inorganic oxygen Changing oxide is preferably aluminium oxide and silica-alumina.In the preferred embodiment, with the total of heat-resistant inorganic oxide On the basis of amount, the content of aluminium oxide can be 30-80 weight %, preferably 40-75 weight %, more preferably 45-72 weight %； The content of silica-alumina can be 20-70 weight %, preferably 25-60 weight %, more preferably 28-55 weight %.This In invention, in silica-alumina, the content of silica can be 20-50 weight %, preferably 25-45 weight %, aluminium oxide Content can be 50-80 weight %, preferably 55-75 weight %.

Support according to the present invention, the carrier can have various shape according to specifically used occasion.For example, the load Body can be spherical shape, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.

Support according to the present invention can be prepared using conventional method.Specifically, will containing the dealuminzation Y type molecular sieve with And the mixture molding of at least one of precursor of heat-resistant inorganic oxide and heat-resistant inorganic oxide, the molding that will be obtained Object is successively dried and roasts, to obtain the carrier.

The precursor of the heat-resistant inorganic oxide refers to the object that heat-resistant inorganic oxide can be formed during molding Matter.The precursor of the heat-resistant inorganic oxide can be selected according to the type of heat-resistant inorganic oxide.Generally, described The precursor of heat-resistant inorganic oxide can be with are as follows: is capable of forming the aqua oxidation of the heat-resistant inorganic oxide under the roasting condition Object, the gel containing the precursor for being capable of forming heat-resistant inorganic oxide under the roasting condition and containing under the roasting condition It is capable of forming the colloidal sol of the precursor of heat-resistant inorganic oxide.In the present invention, term " hydrous oxide " refers to the water of oxide Close object.

For example, the example of the precursor can include but is not limited to when the heat-resistant inorganic oxide is aluminium oxide: Hydrated alumina (such as: aluminium hydroxide, boehmite), the gel containing hydrated alumina and contain hydrated alumina Colloidal sol.

It can be using conventional method by the dealuminzation Y type molecular sieve and heat-resistant inorganic oxide and heat-resistant inorganic oxide At least one of precursor is mixed and is formed, to obtain carrier.Specifically, the molding mode can be extrusion, spray Mist, round as a ball, tabletting or their combination.In a preferred embodiment of the invention, it is formed by way of extrusion.

The condition of the drying and the roasting is not particularly limited in the present invention, can be the conventional strip of this field Part.Generally, the temperature of the drying can be with 80-300 DEG C, preferably 90-250 DEG C, more preferably 100-150 DEG C, such as 110- 120℃.The time of the drying can make appropriate choice according to dry temperature, to enable to finally obtained molding Volatile matter content meets subject to requirement in object.Generally, the time of the drying can be 1-48 hours, preferably 2-24 Hour, more preferably 2-12 hours, further preferably 3-6 hours.Generally, the temperature of the roasting can be 350-800 DEG C, preferably 450-650 DEG C, more preferably 500-600 DEG C, such as 550-600 DEG C；The time of the roasting can be small for 1-10 When, preferably 2-5 hours.The roasting can carry out in oxygen-containing atmosphere, or carry out in inert atmosphere.

According to the second aspect of the invention, the present invention provides carriers described in first aspect of the present invention as load The application of the carrier of type catalyst.

Active constituent can be supported on supported catalyst to be common by the loaded catalyst.Preferably, institute Stating loaded catalyst is the catalyst with hydrogenation.It is highly preferred that the loaded catalyst is with being hydrocracked The catalyst of effect.

According to the third aspect of the present invention, the present invention provides a kind of catalyst, which includes carrier and bears Carry group VIII metallic element and vib metals element on the carrier, wherein the carrier is the present invention first Carrier described in aspect.

The type of catalyst according to the invention, the group VIII metallic element and vib metals element is without spy It does not limit, the metallic element of function can be hydrocracked for usually used the having in hydrocracking technology field.Generally, described Group VIII metallic element is preferably nickel and/or cobalt；The vib metals element is preferably molybdenum and/or tungsten.

The present invention does not limit the load capacity of group VIII metallic element and vib metals element on carrier especially It is fixed, it can be conventional selection.Generally, the vib metals on the basis of the total amount of the catalyst, in terms of oxide Content can be 10-40 weight %, preferably 20-30 weight %；The content of the group VIII metal in terms of oxide It can be 2-10 weight %, preferably 2.5-8 weight %；The content of the carrier can be 50-88 weight %, preferably 62- 77.5 weight %.

According to the fourth aspect of the present invention, the present invention provides a kind of preparation method of catalyst, this method is included in The supported on carriers group VIII metallic element and vib metals element, wherein the carrier is first side of the invention Carrier described in face.

Group VIII metallic element and vib metals element can be supported on carrier using conventional method.At this It invents in a kind of preferred embodiment, is born group VIII metallic element and vib metals element using the method for dipping It is loaded on carrier.

In the preferred embodiment, the dipping can be saturation dipping, or excessive dipping, without special It limits.

In the preferred embodiment, the group VIII metallic element and vib metals element can be born simultaneously It is loaded on carrier, group VIII metallic element and vib metals element can also be supported on carrier respectively.By When group VIII metal element and vib metals element are supported on carrier respectively, group VIII metallic element and group VIB gold The Mo-Co catalyst for belonging to element is not particularly limited, can first load regulation group VIII metal element back loading vib metals element, Group VIB metallic element back loading group VIII metallic element can also be first loaded, load regulation group VIII metal can also be spaced Element and vib metals element.It is spaced load regulation group VIII metal element and vib metals element is suitable for several times to Group VIII metallic element and vib metals element are supported on the situation on carrier.Preferably, by group VIII metallic element It is supported on carrier simultaneously with vib metals element, the terseness of technique can be improved in this way, improve efficiency.

It, can be using the compound of the metallic element containing group VIII and containing group VIB gold in the preferred embodiment The compound for belonging to element prepares maceration extract.The compound of the metallic element containing group VIII and it is described contain vib metals The specific type of the compound of element can be selected according to the solvent of maceration extract, stable can disperse to be formed in a solvent Subject to maceration extract.Preferably, the solvent of the maceration extract is water, at this point, the compound of the metallic element containing group VIII is excellent It is selected as the water dissolvable compound of the metallic element containing group VIII, the compound of the element containing vib metals preferably contains The water dissolvable compound of vib metals element.

Specifically, the compound of the element containing vib metals can selected from ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, Molybdenum oxide and tungsten oxide.

The compound of the metallic element containing group VIII can be selected from nitrate, the Section VIII of group VIII metallic element The chloride of race's metallic element, the sulfate of group VIII metallic element, group VIII metallic element formates, group VIII The acetate of metallic element, the phosphate of group VIII metallic element, group VIII metallic element citrate, group VIII The oxalates of metallic element, the carbonate of group VIII metallic element, the subcarbonate of group VIII metallic element, Section VIII The hydroxide of race's metallic element, the phosphate of group VIII metallic element, the phosphide of group VIII metallic element, Section VIII The sulfide of race's metallic element, the aluminate of group VIII metallic element, group VIII metallic element molybdate, group VIII The tungstates of metallic element and the water-soluble oxide of group VIII metallic element.

Preferably, the compound of the metallic element containing group VIII is selected from the oxalates of group VIII metallic element, the The nitrate of group VIII metal element, the sulfate of group VIII metallic element, the acetate of group VIII metallic element, The chloride of group VIII metal element, the carbonate of group VIII metallic element, group VIII metallic element subcarbonate, The hydroxide of group VIII metallic element, the phosphate of group VIII metallic element, group VIII metallic element molybdate, The tungstates of group VIII metallic element and the water-soluble oxide of group VIII metallic element.

Specifically, the compound of the metallic element containing group VIII can be selected from but not limited to: nickel nitrate, nickel sulfate, Nickel acetate, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.

The compound of the metallic element containing group VIII and the compound of the element containing vib metals are in maceration extract Content can be selected according to the number of dipping, carrying group VIII metallic element and vib metals element Subject to load capacity on body is met the requirements.

The maceration extract can also have more excellent containing at least one organic additive, the catalyst thus prepared Catalytic performance.The organic additive is selected from organic acid and organic amine.The organic acid, which refers to, contains at least one in molecular structure The organic compound of a carboxyl (- COOH), the organic amine, which refers to, contains at least one amido (- NH in molecular structure₂) have Machine compound.Preferably, at least two carboxyls are contained in the molecular structure of the organic acid, in the molecular structure of the organic amine Contain at least two amidos.The organic additive is preferably selected from citric acid, aminotriacetic acid, ethylenediamine and ethylenediamine tetrem Acid.It is highly preferred that the organic additive is selected from organic carboxyl acid, such as citric acid.

The content of the organic additive can be selected according to the content of the compound of the metallic element containing group VIII. Generally, the molar ratio of the organic additive and group VIII metallic element based on the element can be 0.1-10, preferably 0.4-8, more preferably 0.5-4, further preferably 0.8-2 are still more preferably 0.9-1.5, such as 0.95-1.2.

It, can be into when being impregnated using the method that excessively impregnates, after the completion of dipping in the preferred embodiment Row filtering, to remove extra liquid phase.

In the preferred embodiment, after the completion of dipping and optional filtering, solid matter can be dried And optional roasting, to obtain the catalyst with the effect that is hydrocracked according to the present invention.

Method according to the invention it is possible to roasted, it can also be without roasting.

The condition of the drying and roasting is not particularly limited in the present invention, can be conventional selection.Generally, described Drying can 50-300 DEG C, preferably 80-280 DEG C, it is 100-250 DEG C more preferable, it is further preferred 110-180 DEG C at a temperature of into Row.The duration of the drying can be selected according to dry temperature, and volatile materials can be deviate from by being subject to.Generally Ground, the time of the drying can be 1-12 hours, preferably 2-8 hours.The drying can at different temperatures stage by stage It carries out.Such as: can not higher than 150 DEG C at a temperature of carry out it is first dry, then higher than 150 DEG C at a temperature of carry out the Two is dry.First drying can 50-150 DEG C, preferably 80-130 DEG C, it is further preferred 90-120 DEG C at a temperature of into Row, the described first dry duration can be 1-3 hours.Second drying can be higher than 150 DEG C to 250 DEG C of temperature Degree is lower to carry out, preferably 160-200 DEG C at a temperature of carry out, more preferably 165-180 DEG C at a temperature of carry out, described second is dry The dry duration can be 1-5 hours, preferably 2-4 hours.The roasting can be at 350-550 DEG C, preferably 400-500 DEG C At a temperature of carry out.The duration of the roasting can be 1-8 hours, preferably 2-6 hours.

According to the fifth aspect of the present invention, it is prepared the present invention provides the method as described in the 4th aspect of the present invention Catalyst.

According to the sixth aspect of the invention, the present invention provides described in third aspect of the present invention or the 5th aspect Catalyst as hydrocracking reaction catalyst application.

According to the seventh aspect of the present invention, the present invention provides a kind of method for hydrogen cracking, this method is included in plus hydrogen Under the conditions of cracking reaction, hydrocarbon ils is contacted with catalyst, the catalyst is third aspect of the present invention or the 5th aspect The catalyst.

Method for hydrogen cracking according to the present invention, the hydrocarbon ils can for various heavy mineral oils, synthetic oil or they Mixture.Specifically, the example of the hydrocarbon ils can be but be not limited to: vacuum gas oil (VGO), metal removal oil, reduced crude, de- drip Green decompression residuum, decompression residuum, coker distillate, shale oil, asphalt sand oil and liquefied coal coil.

The present invention is by using catalyst according to the invention, and Lai Tigao is hydrocracked conversion ratio and the centre of middle hydrocarbon ils The selectivity of distillate, remaining condition being hydrocracked is not particularly limited, can be the normal condition of this field.It is excellent Selection of land, the hydrocracking condition include: that temperature is 200-650 DEG C, preferably 300-510 DEG C；In terms of gauge pressure, pressure 3- 24MPa, preferably 4-15MPa；Hydrogen to oil volume ratio can be 150-2500；Volume space velocity can be 0.1-30h when liquid^-1, preferably For 0.2-10h^-1。

Method for hydrogen cracking according to the present invention, the catalyst are using preceding preferred carry out presulfurization.The presulfurization Condition can be this field normal condition.For example, the condition of the presulfurization may include: in presence of hydrogen, in At a temperature of 140-370 DEG C, presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock.Method for hydrogen cracking according to the present invention, institute Stating presulfurization can carry out outside reactor, can also be In-situ sulphiding in reactor.

The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.

In following embodiment and comparative example, X-ray diffraction method is the model X ' pert's for being commercially available from Philips company It is carried out on X-ray diffractometer；X-ray fluorescence spectra is analyzed in the 3271E type X for being commercially available from Rigaku electric machine industry Co., Ltd. It is carried out on ray fluorescence spectrometer.

In following embodiment and comparative example, crystallinity is relative crystallinity, and using " petrochemical analysis method ", (science goes out Version society, the nineteen ninety first edition, Yang Cui is surely equal to be compiled) in method measurement specified in the RIPP 139-90 that records, wherein made Standard specimen is the sample that number is 79Y16.

In following embodiment and comparative example, in unit structure cell non-framework aluminum number using document (Breck D.W., Flanigen F.M.etc, Molecular Sieves Soc.Chem.Ind., 1968, p47) the method measurement recorded, specifically Operating procedure is as follows.

Step (1): using the silica alumina ratio of x-ray fluorescence spectrometry Y type molecular sieve, Y is measured using X-ray diffraction method The lattice constant of type molecular sieve.

Step (2): the silica alumina ratio measured according to step (1), by determining lattice constant corresponding with the silica alumina ratio in the following table 1 With unit structure cell aluminium atom number, for the unwritten silica alumina ratio of table 1, using in table 1 with the silica alumina ratio of step (1) measurement most Lattice constant corresponding to close silica alumina ratio and unit structure cell aluminium atom number (are denoted as N_Al ¹), it is closest if there is two Silica alumina ratio, the lesser silica alumina ratio of selecting unit structure cell aluminium atom number.

Step (3): the lattice constant measured according to step (1) determines that unit corresponding with the lattice constant is brilliant by the following table 1 Born of the same parents' aluminium atom number, for the unwritten lattice constant of table 1, using immediate with the lattice constant of step (1) measurement in table 1 Unit structure cell aluminium atom number corresponding to lattice constant (is denoted as N_Al ²), when there are two immediate lattice constants, selection Numerical value smaller in unit structure cell aluminium atom number.

Step (4): the absolute value of the difference for the unit structure cell aluminium atom number that step (2) and step (3) are determined as Non-framework aluminum content in unit structure cell, that is, non-framework aluminum content=∣ N in unit structure cell_Al ¹- N_Al ²∣。

Table 1

In following embodiment and comparative example, specific surface area, Kong Rong, secondary hole area and secondary pore hole, which hold, uses BET method In the model for being commercially available from Quantachrome companyThe full-automatic specific surface in six stations and pore-size distribution of -6B measures It is tested on instrument.

In following embodiment, infrared spectrum analysis is in the model NICOLET 6700 for being purchased from Thermo Scientific Infrared spectrometer on carry out, scanning range 400-4000cm^-1, scanning times are 20 times, using absorption mode.

In following embodiment and comparative example, butt is by measuring sample and 600 DEG C roast 4 hours.Following reality It applies in example and comparative example, pressure is in terms of gauge pressure.

Preparation embodiment 1-6 is used to prepare dealuminzation Y type molecular sieve.

Prepare embodiment 1

(1) by 100g (butt) NaY molecular sieve, (middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company is produced, physico-chemical property parameter point Do not listed in table 2 and table 3) it is scattered in 1500mL water, with stirring, at the uniform velocity it is added dropwise under environment temperature (25 DEG C, similarly hereinafter) The aqueous solution of 200mL ammonium sulfate containing 50g (purchased from the sharp chemical reagent factory of Beijing benefit) (control time for adding is 30min).To sulfuric acid After aqueous ammonium is added dropwise to complete, stop stirring and being filtered mixed liquor, after solid phase is washed with deionized 3 times, at 105 DEG C Normal pressure (1 standard atmospheric pressure, similarly hereinafter) dries 3h in air atmosphere, thus molecular sieve after being exchanged, sodium ions content is in table 4 In list.

(2) molecular sieve after the exchange of step (1) preparation is placed in tube furnace, vapor is continually fed into tube furnace (speed that is passed through of vapor is 0.35mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 650 DEG C, it carries out The hydro-thermal process of 2h.It is naturally cooling to take out after environment temperature, obtains molecular sieve after the first hydro-thermal process, infrared spectrogram In, the antisymmetric vibration frequency σ of structure sensitive₁It lists in table 4.

(3) molecular sieve after the first hydro-thermal process of 80g (butt) is dispersed in 800mL distilled water, with stirring, in environment At a temperature of 150mL ammonium chloride containing 60g (purchased from the sharp chemical reagent factory of Beijing benefit) is at the uniform velocity added dropwise and the aqueous solution of 10g HCl (controls Time for adding is 30min).After being added dropwise to complete, continue to stir 30min.Then, it is filtered, solid phase is washed with deionized 3 times Afterwards, the constant pressure and dry 2h in 105 DEG C of air atmospheres, to obtain dealuminzation molecular sieve.

(4) the dealuminzation molecular sieve that step (3) obtains is placed in tube furnace, vapor (water is continually fed into tube furnace The speed that is passed through of steam is 0.20mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 650 DEG C, carry out 2h's Hydro-thermal process.After the completion of hydro-thermal process, it is naturally cooling to take out after environment temperature (being 25 DEG C, similarly hereinafter), obtains the second hydro-thermal Molecular sieve after processing.

(5) molecular sieve after the second hydro-thermal process of 60g (butt) step (4) preparation is dispersed in 600mL distilled water, it will Mixed liquor is heated to 60 DEG C, with stirring, at the uniform velocity aqueous solution (the control drop of dropwise addition 150mL ammonium sulfate containing 10g and 27g fluosilicic acid It is 30min between added-time).After being added dropwise to complete, continue to stir 30min.After temperature is down to environment temperature naturally, mixture is carried out Filtering, after solid phase is washed with deionized 3 times, the constant pressure and dry 2.5h in 105 DEG C of air atmospheres, to obtain according to the present invention Dealuminzation Y type molecular sieve, physico-chemical property parameter lists in table 2 and table 3 respectively.

Prepare comparative example 1

Dealuminzation Y type molecular sieve is prepared using method identical with preparation embodiment 1, unlike, in step (5), do not make With ammonium sulfate and fluosilicic acid, but uses the ammonium fluoride aqueous solution that 45mL concentration be 0.65mol/L (controlling time for adding is 30min).The lattice constant of the dealuminzation Y type molecular sieve finally prepared is 2.437nm, relative crystallinity 57%, mol sieve unit The number of non-framework aluminum is 2.2 in structure cell, and the relative crystallinity of the dealuminzation Y type molecular sieve is lower, so that being not used to that hydrogen is added to split Change catalyst.

Prepare comparative example 2

Dealuminzation Y type molecular sieve is prepared using method identical with preparation embodiment 1, unlike, in step (3), HCl is used The fluosilicic acid of equimolar amounts replaces.The lattice constant of the dealuminzation Y type molecular sieve finally prepared is 2.443nm, Kong Rongwei The relative crystallinity of 0.410mL/g, relative crystallinity 62.4%, the dealuminzation Y type molecular sieve are lower, so that being not used to add hydrogen Cracking catalyst.

Prepare comparative example 3

Prepare dealuminzation Y type molecular sieve using with the identical method of preparation embodiment 1, unlike, without step (3) and (4), but molecular sieve after the first hydro-thermal process that step (2) obtains is sent directly into step (5) and is handled, to prepare Dealuminzation Y type molecular sieve, lattice constant 2.454nm, sodium oxide content are 4.4 weight %, the oxidation of the dealuminzation Y type molecular sieve Sodium content is higher, so that being not used to hydrocracking catalyst.

Prepare comparative example 4

Dealuminzation Y type molecular sieve is prepared using method identical with preparation embodiment 1, unlike, in step (5), do not make With ammonium sulfate and fluosilicic acid, but uses the aqueous solution of the 0.5mol/L ammonium fluosilicate of 110mL (control time for adding is 30min).The lattice constant of the dealuminzation Y type molecular sieve finally prepared is 2.436nm, relative crystallinity 74.4%, molecular sieve list The number of non-framework aluminum is 2.4 in first structure cell.

Prepare comparative example 5

Dealuminzation Y type molecular sieve is prepared using method identical with preparation embodiment 1, unlike, using following technique stream Journey prepares dealuminzation Y type molecular sieve.

(1) 100g (butt) NaY molecular sieve (with embodiment 1) is dispersed in 950mL distilled water, mixed liquor is heated to 60 DEG C, with stirring, at the uniform velocity (control time for adding is the aqueous solution of dropwise addition 60mL ammonium sulfate containing 30g and 25g fluosilicic acid 30min).After being added dropwise to complete, continue to stir 30min.After temperature is down to environment temperature naturally, mixture is filtered, Gu After being mutually washed with deionized 3 times, the constant pressure and dry 2.5h in 105 DEG C of air atmospheres.

(2) molecular sieve after the exchange of step (1) preparation is placed in tube furnace, vapor is continually fed into tube furnace (speed that is passed through of vapor is 0.35mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 650 DEG C, it carries out The hydro-thermal process of 2h.It is naturally cooling to take out after environment temperature.

(3) molecular sieve that 80g (butt) step (2) obtains is dispersed in 800mL distilled water, with stirring, in environment At a temperature of the aqueous solution of 70mL ammonium chloride containing 10g and 10g HCl is at the uniform velocity added dropwise (control time for adding is 30min).It is added dropwise to complete Afterwards, continue to stir 30min.Then, it is filtered, after solid phase is washed with deionized 3 times, the normal pressure in 105 DEG C of air atmospheres Dry 2h.

(4) molecular sieve that step (3) obtains is placed in tube furnace, vapor (vapor is continually fed into tube furnace The speed that is passed through be 0.20mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 600 DEG C, carries out the hydro-thermal of 3h Processing.After the completion of hydro-thermal process, it is naturally cooling to environment temperature.

(5) it disperses the molecular sieve that 70g (butt) step (4) obtains in 1500mL water, with stirring, in environment temperature Under 100mL ammonium sulfate solution containing 40g (control time for adding be 30min) is at the uniform velocity added dropwise.It is added dropwise to complete to ammonium sulfate solution Afterwards, stop stirring and being filtered mixed liquor, after solid phase is washed with deionized 3 times, normal pressure is dry in 105 DEG C of air atmospheres Dry 3h, so that dealuminzation Y type molecular sieve, lattice constant 2.441nm, crystallinity 68.2%, mol sieve unit structure cell be made The number of middle non-framework aluminum is 7.2.

Prepare comparative example 6

Dealuminzation Y type molecular sieve is prepared using method identical with CN1388064A specification disclosed embodiment 1, it is specific to grasp It is as follows to make condition.

(1) 50g ammonium sulfate is dissolved in 1500mL water, takes 100g (butt) NaY molecular sieve (with embodiment 1), is added to In prepared above-mentioned solution, 30min is stirred at 20 DEG C, is filtered, and is beaten and is washed with deionized water, refiltered, selected Property ammonium exchange Y type molecular sieve.

(2) gained molecular sieve is put into the tube furnace that temperature is 650 DEG C, in 50 weight % (surplus is nitrogen) vapor Hydrothermal calcine 2h under atmosphere.

(3) the zeolite 20g after taking above-mentioned roasting, which is added in 300mL distilled water together with 20g ammonium sulfate, to stir evenly, so The hydrochloric acid 30mL of 0.1mol/L is added within the time of 60min under stiring afterwards, filtering is beaten with water, is refiltered, in 105 DEG C Lower dry 3h.

It carries out hydrothermal calcine (that is, step (2)) and HCl treatment (step (3)) again according to above-mentioned steps, is taken off Aluminium Y type molecular sieve, lattice constant 2.437nm, sodium oxide content are 0.094 weight %, and silica/alumina mass ratio is 6.4, aluminium atom content is 7.5 in mol sieve unit structure cell.

Prepare embodiment 2

(1) it disperses 100g (butt) NaY molecular sieve (with preparation embodiment 1) in 1500mL water, with stirring, Yu Huan The aqueous solution of 300mL ammonium nitrate containing 50g (purchased from the sharp chemical reagent factory of Beijing benefit) is at the uniform velocity added dropwise at border temperature (25 DEG C, similarly hereinafter) (control time for adding is 50min).After aqueous ammonium nitrate solution is added dropwise to complete, stop stirring and being filtered mixed liquor, Gu After being mutually washed with deionized 3 times, the constant pressure and dry 3h in 120 DEG C of air atmospheres, thus molecular sieve after being exchanged, sodium from Sub- content is listed in table 4.

(2) molecular sieve after the exchange of step (1) preparation is mixed with water, obtaining the slurry containing molecular sieve, (butt is 55 weights Measure %).Slurry containing molecular sieve is seated in crucible (specification of crucible: interior diameter 40mm, a height of 40mm, similarly hereinafter), it is close Envelope crucible is placed in Muffle furnace, is warming up to 550 DEG C, is kept 2h at such a temperature.It is naturally cooling to after environment temperature, obtains Molecular sieve after first hydro-thermal process, in infrared spectrogram, the antisymmetric vibration frequency σ of structure sensitive₁It lists in table 4.

(3) molecular sieve after the first hydro-thermal process of 85g (butt) is dispersed in 900mL distilled water, with stirring, in environment At a temperature of 100mL ammonium sulfate containing 30g and 6g HNO is at the uniform velocity added dropwise₃Aqueous solution (control time for adding be 30min).It is added dropwise to complete Afterwards, continue to stir 20min.Then, it is filtered, after solid phase is washed with deionized 3 times, the normal pressure in 120 DEG C of air atmospheres Dry 3h, to obtain dealuminzation molecular sieve.

(4) dealuminzation molecular sieve prepared by step (3) is mixed with water, obtaining the slurry containing molecular sieve, (water content is 65 weights Measure %).Slurry containing molecular sieve is seated in crucible, sealed crucible is placed in Muffle furnace, 550 DEG C is warming up to, in the temperature Degree is lower to keep 2h.It after the completion of hydro-thermal process, is naturally cooling to after environment temperature, obtains molecular sieve after the second hydro-thermal process.

(5) molecular sieve after the second hydro-thermal process of 80g (butt) step (4) preparation is dispersed in 800mL distilled water, it will Mixed liquor is heated to 70 DEG C, with stirring, at the uniform velocity aqueous solution (the control drop of dropwise addition 100mL ammonium chloride containing 20g and 10g fluosilicic acid It is 30min between added-time).After being added dropwise to complete, continue to stir 40min.After temperature is down to environment temperature naturally, mixture is carried out Filtering, after solid phase is washed with deionized 3 times, the constant pressure and dry 4h in 120 DEG C of air atmospheres, to obtain according to the present invention Dealuminzation Y type molecular sieve, physico-chemical property parameter are listed in table 2 and table 3 respectively.

Prepare comparative example 7

Dealuminzation Y type molecular sieve is prepared using method identical with preparation embodiment 2, unlike, in step (3), it is added dropwise Solution are as follows: 100mL ammonium sulfate containing 15g and 6g HNO₃Aqueous solution (control time for adding be 30min).It is last obtained de- The lattice constant of aluminium Y type molecular sieve is 2.442nm, relative crystallinity 62.3%, the relative crystallinity of the dealuminzation Y type molecular sieve It is lower, so that being not used to hydrocracking catalyst.

Prepare comparative example 8

Dealuminzation Y type molecular sieve is prepared using method identical with preparation embodiment 2, unlike, in step (2), it will walk Suddenly molecular sieve is mixed with water after the exchange of (1) preparation, obtains the slurry containing molecular sieve (butt is 55 weight %).Molecular sieve will be contained Slurry be seated in crucible, sealed crucible is placed in Muffle furnace, is warming up to 450 DEG C, is kept 2h at such a temperature.Naturally it drops After temperature to environment temperature, molecular sieve after the first hydro-thermal process is obtained, wherein the knot of molecular sieve after the first obtained hydro-thermal process The antisymmetric vibration frequency of structure sensitivity is 1030.5cm^-1, 0.766 × (1086- σ₁)=42.5.Its lattice constant is 2.456nm, sodium oxide content are 4.4 weight %, and the sodium oxide content of the dealuminzation Y type molecular sieve is higher, so that being not used to add Hydrogen Cracking catalyst.

Prepare embodiment 3

(1) by 100g (butt) NaY molecular sieve, (middle Effect of Catalysis In Petrochemistry agent Zhou village branch company is produced, physico-chemical property parameter point Do not listed in table 2 and table 3) it is scattered in 1300mL water, with stirring, 100mL ammonium nitrate containing 45g is at the uniform velocity added dropwise at 35 DEG C (purchased from the sharp chemical reagent factory of Beijing benefit) aqueous solution (control time for adding is 40min).After aqueous solution is added dropwise to complete, stop stirring It mixes and is filtered mixed liquor, after solid phase is washed with deionized 3 times, the constant pressure and dry 3.5h in 110 DEG C of air atmospheres, from And molecular sieve after being exchanged, sodium ions content are listed in table 4.

(2) molecular sieve after the exchange of 85g (butt) step (1) preparation is placed in tube furnace, is persistently led into tube furnace Enter vapor (speed that is passed through of vapor is 0.30mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 600 DEG C, carry out the hydro-thermal process of 2.5h.It is naturally cooling to take out after environment temperature, obtains molecular sieve after the first hydro-thermal process.

(3) molecular sieve after the first hydro-thermal process of 80g (butt) is dispersed in 1000mL distilled water, with stirring, in 35 The aqueous solution of 150mL ammonium sulfate containing 60g and 10g sulfuric acid is at the uniform velocity added dropwise at DEG C (control time for adding is 45min).It is added dropwise to complete Afterwards, continue to stir 60min.Then, it is filtered, after solid phase is washed with deionized 2 times, the normal pressure in 110 DEG C of air atmospheres Dry 3h, to obtain dealuminzation molecular sieve.

(4) 60g (butt) step (3) is obtained molecular sieve to be placed in tube furnace, vapor is continually fed into tube furnace (speed that is passed through of vapor is 0.3mL/ (ming molecular sieve), and the intake of air is 15mL/ with the gaseous mixture of air (ming molecular sieve)), and the temperature in tube furnace is maintained 620 DEG C, carry out the hydro-thermal process of 3h.Hydro-thermal process is completed Afterwards, it is naturally cooling to environment temperature and obtains molecular sieve after the second hydro-thermal process.

(5) molecular sieve after the second hydro-thermal process of 60g (butt) step (4) preparation is dispersed in 650mL distilled water, it will Mixed liquor is heated to 60 DEG C, with stirring, at the uniform velocity aqueous solution (the control drop of dropwise addition 100mL ammonium chloride containing 25g and 15g fluosilicic acid It is 25min between added-time).After being added dropwise to complete, continue to stir 30min.After temperature is down to environment temperature naturally, mixture is carried out Filtering, after solid phase is washed with deionized 2 times, the constant pressure and dry 3h in 110 DEG C of air atmospheres, to obtain according to the present invention Dealuminzation Y type molecular sieve, physico-chemical property parameter are listed in table 2 and table 3 respectively.

Prepare embodiment 4

(1) it disperses 100g (butt) NaY molecular sieve (with preparation embodiment 3) in 1100mL water, with stirring, in 45 The aqueous solution of 150mL ammonium chloride containing 40g (purchased from the sharp chemical reagent factory of Beijing benefit, similarly hereinafter) is at the uniform velocity added dropwise at DEG C (when control is added dropwise Between be 30min).After aqueous solution is added dropwise to complete, stop stirring and being filtered mixed liquor, solid phase is washed with deionized 2 After secondary, the constant pressure and dry 3h in 115 DEG C of air atmospheres, so that molecular sieve after being exchanged, sodium ions content arrange in table 4 Out.

(2) molecular sieve after the exchange of 85g (butt) step (1) preparation is placed in tube furnace, is persistently led into tube furnace Enter vapor (speed that is passed through of vapor is 0.4mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 580 DEG C, carry out the hydro-thermal process of 3h.It is naturally cooling to take out after environment temperature, obtains molecular sieve after the first hydro-thermal process.

(3) molecular sieve after the first hydro-thermal process of 80g (butt) is dispersed in 900mL distilled water, with stirring, in environment At a temperature of the aqueous solution of 150mL ammonium nitrate containing 40g and 8g nitric acid is at the uniform velocity added dropwise (control time for adding is 40min).It is added dropwise to complete Afterwards, continue to stir 45min.Then, it is filtered, after solid phase is washed with deionized 3 times, the normal pressure in 130 DEG C of air atmospheres Dry 2h, to obtain dealuminzation molecular sieve.

(4) 60g step (3) is obtained molecular sieve (butt) to be placed in tube furnace, vapor is continually fed into tube furnace (speed that is passed through of vapor is 0.4mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 670 DEG C, carry out 2h Hydro-thermal process.After the completion of hydro-thermal process, it is naturally cooling to environment temperature and obtains molecular sieve after the second hydro-thermal process.

(5) molecular sieve after the second hydro-thermal process of 60g (butt) step (4) preparation is dispersed in 700mL distilled water, it will Mixed liquor is heated to 60 DEG C, with stirring, at the uniform velocity aqueous solution (the control drop of dropwise addition 120mL ammonium oxalate containing 15g and 23g fluosilicic acid It is 35min between added-time).After being added dropwise to complete, continue to stir 45min.After temperature is down to environment temperature naturally, mixture is carried out Filtering, after solid phase is washed with deionized 3 times, the constant pressure and dry 3.5h in 120 DEG C of air atmospheres, to obtain according to the present invention Dealuminzation Y type molecular sieve, physico-chemical property parameter lists in table 2 and table 3 respectively.

Prepare comparative example 9

Dealuminzation Y type molecular sieve is prepared using method identical with preparation embodiment 4, unlike, in step (3), it is added dropwise Solution are as follows: the aqueous solution of 150mL ammonium nitrate containing 60g and 8g nitric acid.Finally the lattice constant of dealuminzation Y type molecular sieve obtained is The relative crystallinity of 2.441nm, crystallinity 63.7%, the dealuminzation Y type molecular sieve are lower, urge so that being not used to be hydrocracked Agent.

Prepare embodiment 5

(1) it disperses 100g (butt) NaY molecular sieve (with preparation embodiment 1) in 1000mL water, with stirring, in 55 120mL ammonium chloride containing 35g (purchased from the sharp chemical reagent factory of Beijing benefit) aqueous solution is at the uniform velocity added dropwise at DEG C, and (controlling time for adding is 45min).After aqueous solution is added dropwise to complete, stop stirring and being filtered mixed liquor, after solid phase is washed with deionized 2 times, The constant pressure and dry 2h in 120 DEG C of air atmospheres, so that molecular sieve after being exchanged, sodium ions content are listed in table 4.

(2) molecular sieve after the exchange of 85g (butt) step (1) preparation is placed in tube furnace, is persistently led into tube furnace Enter vapor (speed that is passed through of vapor is 0.25mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 620 DEG C, carry out the hydro-thermal process of 3h.It is naturally cooling to take out after environment temperature, obtains molecular sieve after the first hydro-thermal process.

(3) molecular sieve after the first hydro-thermal process of 80g (butt) is dispersed in 850mL distilled water, with stirring, in 40 DEG C Under the aqueous solution of 150mL ammonium sulfate containing 60g and 17g fluosilicic acid is at the uniform velocity added dropwise (control time for adding is 60min).It is added dropwise to complete Afterwards, continue to stir 75min.Then, it is filtered, after solid phase is washed with deionized 3 times, the normal pressure in 120 DEG C of air atmospheres Dry 3h, to obtain dealuminzation molecular sieve.

(4) the dealuminzation molecular sieve that 60g (butt) step (3) obtains is placed in tube furnace, is continually fed into tube furnace (speed that is passed through of vapor is 0.25mL/ (ming molecular sieve) to the gaseous mixture of vapor and air, and the intake of air is 10L/ (ming molecular sieve)), and the temperature in tube furnace is maintained 600 DEG C, carry out the hydro-thermal process of 3.5h.Hydro-thermal process After the completion, it is naturally cooling to take out after environment temperature, obtains molecular sieve after the second hydro-thermal process.

(5) molecular sieve after the second hydro-thermal process of 60g (butt) step (4) preparation is dispersed in 750mL distilled water, it will Mixed liquor is heated to 60 DEG C, with stirring, at the uniform velocity aqueous solution (the control drop of dropwise addition 130mL ammonium chloride containing 20g and 20g fluosilicic acid It is 30min between added-time).After being added dropwise to complete, continue to stir 40min.After temperature is down to environment temperature naturally, mixture is carried out Filtering, after solid phase is washed with deionized 2 times, the constant pressure and dry 3h in 115 DEG C of air atmospheres, to obtain according to the present invention Dealuminzation Y type molecular sieve, physico-chemical property parameter are listed in table 2 and table 3 respectively.

Prepare embodiment 6

(1) it disperses 100g (butt) NaY molecular sieve (with preparation embodiment 3) in 1200mL water, with stirring, in 20 The aqueous solution of 200mL ammonium sulfate containing 50g (purchased from the sharp chemical reagent factory of Beijing benefit) is at the uniform velocity added dropwise at DEG C, and (control time for adding is 25min).After aqueous solution is added dropwise to complete, stop stirring and being filtered mixed liquor, after solid phase is washed with deionized 4 times, The constant pressure and dry 2h in 130 DEG C of air atmospheres, so that molecular sieve after being exchanged, sodium ions content are listed in table 4.

(2) molecular sieve after the exchange of 85g (butt) step (1) preparation is placed in tube furnace, is persistently led into tube furnace Enter vapor (speed that is passed through of vapor is 0.45mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 670 DEG C, carry out the hydro-thermal process of 2h.It is naturally cooling to take out after environment temperature, obtains molecular sieve after the first hydro-thermal process.

(3) molecular sieve after the first hydro-thermal process of 80g (butt) is dispersed in 950mL distilled water, with stirring, in environment At a temperature of the aqueous solution of 150mL ammonium nitrate containing 60g and 15g oxalic acid is at the uniform velocity added dropwise (control time for adding is 45min).It is added dropwise to complete Afterwards, continue to stir 60min.Then, it is filtered, after solid phase is washed with deionized 2 times, the normal pressure in 120 DEG C of air atmospheres Dry 3h, to obtain dealuminzation molecular sieve.

(4) the dealuminzation molecular sieve that 60g (butt) step (3) obtains is placed in tube furnace, is continually fed into tube furnace (speed that is passed through of vapor is 0.3mL/ (ming molecular sieve) to the gaseous mixture of vapor and air, and the intake of air is 20L/ (ming molecular sieve)), and the temperature in tube furnace is maintained 645 DEG C, carry out the hydro-thermal process of 2.5h.Hydro-thermal process After the completion, it is naturally cooling to take out after environment temperature, obtains molecular sieve after the second hydro-thermal process.

(5) molecular sieve after the second hydro-thermal process of 60g (butt) step (4) preparation is dispersed in 650mL distilled water, it will Mixed liquor is heated to 60 DEG C, with stirring, at the uniform velocity aqueous solution (the control drop of dropwise addition 110mL ammonium nitrate containing 15g and 10g fluosilicic acid It is 25min between added-time).After being added dropwise to complete, continue to stir 35min.After temperature is down to environment temperature naturally, mixture is carried out Filtering, after solid phase is washed with deionized 3 times, the constant pressure and dry 3h in 120 DEG C of air atmospheres, to obtain according to the present invention Dealuminzation Y type molecular sieve, physico-chemical property parameter are listed in table 2 and table 3 respectively.

Prepare comparative example 10

Dealuminzation Y type molecular sieve is prepared using method identical with preparation embodiment 6, unlike, in step (2), by 85g (butt) step (1) preparation exchange after molecular sieve be placed in tube furnace, be continually fed into tube furnace vapor (vapor Being passed through speed is 0.45mL/ (ming molecular sieve)), and the temperature in tube furnace is maintained 750 DEG C, at the hydro-thermal for carrying out 2h Reason.It is naturally cooling to take out after environment temperature, obtains molecular sieve after the first hydro-thermal process, wherein at the first obtained hydro-thermal The antisymmetric vibration frequency of the structure sensitive of molecular sieve is 1041.1cm after reason^-1, 0.766 × (1086- σ₁)=34.4.Finally The lattice constant of dealuminzation Y type molecular sieve obtained is 2.448nm, relative crystallinity 57.3%, the phase of the dealuminzation Y type molecular sieve It is lower to crystallinity, so that being not used to hydrocracking catalyst.

Table 2

Table 3

Table 4

Prepare embodiment 1-6's as a result, it was confirmed that aluminium, the spy of molecular sieve can not only be effectively reduced using method of the invention Other non-framework aluminum content, and higher crystallinity retention rate can be obtained, while can also be formed in molecular sieve abundant secondary Hole.

Embodiment 1-6 is used to prepare the catalyst with the effect that is hydrocracked according to the present invention.

Embodiment 1

(1) by 120.3g C powder, (middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company is produced, and is determined as boehmite through XRD test Object phase, relative crystallinity 91.7%, contents on dry basis be 74.7 weight %, similarly hereinafter), 40 powder of 67.0g Siral (Sasol company Production is silica-alumina powder, wherein 41.2 weight % of silica content, alumina content are 58.8 weight %, butt Content be 79.6 weight %, similarly hereinafter) and 8.4g preparation embodiment 1 prepare dealuminzation Y type molecular sieve (contents on dry basis be 81 weights Measure %) it is uniformly mixed, obtain hybrid solid material.By 3.3mL concentrated nitric acid (HNO₃Concentration is 65 weight %) it is added to 141mL In ionized water, mixed liquor is made.After above-mentioned hybrid solid material and mixed liquor kneading 15min, it is with banded extruder extrusion molding Circumscribed circle diameter is the trilobal item of 1.6mm.Wet bar is dried 3 hours at 110 DEG C, then, 600 DEG C in air atmosphere Roasting temperature 3 hours, obtain catalyst carrier.

It (2) is 26 weight % according to tungsten oxide content in catalyst, nickel oxide content is 2.7 weight % by basic nickel carbonate (purchased from the sharp chemical reagent factory of Beijing benefit, the content of nickel is 40 weight % based on the element), citric acid are (purchased from Beijing benefit benefit chemistry examination The mass ratio of agent factory, citric acid and nickel oxide is that 3:1) and ammonium metatungstate (being purchased from middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company) are mixed It closes, obtains dipping solution, the catalyst carrier prepared using hole saturation impregnation steps (1), wherein dipping temperature is 25 DEG C, Dip time is 1.5 hours.It is after the completion of dipping, mixture is 5 hours dry in 120 DEG C, continue thereafter small in 180 DEG C of dryings 3 When, to obtain catalyst.

(4) performance of catalyst prepared by step (2) is evaluated using following methods.

Evaluating catalyst is using once by process, feedstock oil gently subtracts two using sand, and the density (20 DEG C) of the feedstock oil is 0.9062g/cm³, (20 DEG C) of refraction index are 1.4852；Initial boiling point (IBP) be 299 DEG C, 5% recovered (distilled) temperature be 359 DEG C, 50% Recovered (distilled) temperature is 399 DEG C, and 95% recovered (distilled) temperature is 436 DEG C.

The particle for being 0.5-1.0 millimeters at diameter by catalyst breakage, is packed into this in 200 milliliters of fixed bed reactors and urges 200 milliliters of agent, before leading to oil, catalyst is first 15.0MPa in hydrogen partial pressure, and temperature be 300 DEG C under conditions of vulcanization it is 28 small When, it is later 14.7MPa in hydrogen partial pressure, is passed through feedstock oil when temperature is 350 DEG C, hydrogen-oil ratio is 900 volume/volumes, when liquid Volume space velocity is 0.75h^-1, and sampled after reaction 400 hours.

Catalytic activity, intermediate oil selectivity, tail oil BMCI value and the tail oil paraffinicity of catalyst are evaluated, In:

Activity refers to the cracking reaction temperature needed when the conversion ratio of hydrocarbon ils of the recovered (distilled) temperature higher than 350 DEG C is 60%, splits It is higher to change the lower catalytic activity for illustrating catalyst of reaction temperature；

Intermediate oil selectively refers to that recovered (distilled) temperature is that the content of 132-371 DEG C of fraction accounts for recovered (distilled) temperature less than 371 The percentage of the gross mass of DEG C fraction；

Tail oil BMCI value reference " petroleum refining engineering " (the woods generation ruler of great talent and bold vision compiles, petroleum industry publishing house, Beijing, and 2000.07, The third edition) the method measurement recorded of page 74, and it is calculated using the following equation BMCI value,

Wherein, t_vFor the volume average boiling point (DEG C) of tail oil；

For the density relative to water of tail oil.

Experimental result is listed in table 5.

Comparative example 1

Catalyst is prepared using method same as Example 1, unlike, the dealuminzation Y type molecular sieve in step (1) is used Etc. weight preparation comparative example 4 prepare dealuminzation Y type molecular sieve preparation.Experimental result is listed in table 5.

Comparative example 2

Catalyst is prepared using method same as Example 1, unlike, the dealuminzation Y type molecular sieve in step (1) is used Etc. weight preparation comparative example 6 prepare dealuminzation Y type molecular sieve preparation.Experimental result is listed in table 5.

Embodiment 2

Catalyst is prepared using method same as Example 1 and the performance of the catalyst of preparation is evaluated, it is different , in step (1), dealuminzation Y type molecular sieve is the molecular sieve for preparing embodiment 2 and preparing.Experimental result is listed in table 5.

Embodiment 3

(1) by 145.8g CL powder, (middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company is produced, and is determined as boehmite through XRD test Object phase, relative crystallinity 98.1%, contents on dry basis is 71.1 weight %), (middle Effect of Catalysis In Petrochemistry agent Chang Ling point is public for 52.6g N2 powder Department's production is silica-alumina powder, wherein 25.7 weight % of silica content, alumina content are 74.3 weight %, are done Base content is 79.5 weight %) and 5.6g preparation embodiment 3 prepare dealuminzation Y type molecular sieve (contents on dry basis be 81 weight %) mix It closes uniformly, obtains hybrid solid material.By 3.3mL concentrated nitric acid (HNO₃Concentration is 65 weight %) it is added to 144mL deionized water In, mixed liquor is made.It is circumscribed circle with banded extruder extrusion molding after above-mentioned hybrid solid material and mixed liquor kneading 15min Diameter is the trilobal item of 1.6mm.Wet bar is dried 3 hours at 110 DEG C, then, in air atmosphere 600 DEG C at a temperature of Roasting 3 hours, obtains catalyst carrier.

It (2) is 25.2 weight % according to tungsten oxide content in catalyst, nickel oxide content is 4.8 weight % by basic carbonate Nickel (purchased from the sharp chemical reagent factory of Beijing benefit, the content of nickel is 40 weight % based on the element), citric acid are (purchased from Beijing benefit benefit chemistry The mass ratio of chemical reagent work, citric acid and nickel oxide is that 2.5:1) and ammonium metatungstate (being purchased from middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company) are mixed It closes, obtains dipping solution, the catalyst carrier prepared using hole saturation impregnation steps (1), wherein dipping temperature is 40 DEG C, Dip time is 1.0 hours.It is after the completion of dipping, mixture is 3 hours dry in 120 DEG C, continue thereafter small in 170 DEG C of dryings 4 When, to obtain catalyst according to the invention.

(3) using identical method evaluates the performance of catalyst with 1 step of embodiment (3), experimental result is in table 5 In list.

Embodiment 4

Catalyst is prepared using method same as Example 3 and the performance of catalyst is evaluated, unlike, step Suddenly in (1), dealuminzation Y type molecular sieve is the dealuminzation Y type molecular sieve for preparing embodiment 4 and preparing.Experimental result is listed in table 5.

Embodiment 5

Catalyst is prepared using method same as Example 3 and the performance of catalyst is evaluated, unlike, step Suddenly in (1), dealuminzation Y type molecular sieve is the dealuminzation Y type molecular sieve for preparing embodiment 5 and preparing.Experimental result is listed in table 5.

Embodiment 6

(1) the dealuminzation Y type molecular sieve for preparing 90.2g C powder, 40 powder of 93.0g Siral and 9.5g preparation embodiment 6 (contents on dry basis is 81 weight %) is uniformly mixed, and obtains hybrid solid material.By 3.3mL concentrated nitric acid (HNO₃Concentration is 65 weights Amount %) it is added in 141mL deionized water, mixed liquor is made.After above-mentioned hybrid solid material and mixed liquor kneading 15min, It is the trilobal item that circumscribed circle diameter is 1.6mm with banded extruder extrusion molding.Wet bar is dried 4 hours at 120 DEG C, then, 580 DEG C of roasting temperature 4 hours in air atmosphere, to obtain catalyst carrier.

It (2) is 24.5 weight % according to tungsten oxide content in catalyst, nickel oxide content is 7.0 weight % by nickel nitrate (purchased from the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (being purchased from middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company) mixing, obtains impregnating molten Liquid, the catalyst carrier prepared using hole saturation impregnation steps (1), wherein dipping temperature is 35 DEG C, dip time 1.5 Hour.It is after the completion of dipping, mixture is 5 hours dry in 120 DEG C, it is roasted 3 hours in air atmosphere at 400 DEG C thereafter, from And obtain catalyst according to the invention.

(3) using identical method evaluates the performance of catalyst with 1 step of embodiment (3), experimental result is in table 5 In list.

Embodiment 7

Catalyst is prepared using method same as Example 1, the difference is that the dipping solution that step (2) is prepared is free of lemon Lemon acid.Experimental result is listed in table 5.

Table 5

Table 5 as a result, it was confirmed that catalyst according to the invention in the hydrocracking reaction for hydrocarbon ils, can catalysis live Property, preferable balance is obtained between intermediate oil selectivity and tail oil BMCI value.

Claims (60)

1. a kind of carrier, which contains dealuminzation Y type molecular sieve and heat-resistant inorganic oxide, which is characterized in that the dealuminzation Y Type molecular sieve is the dealuminzation Y type molecular sieve prepared using method comprising the following steps:

It (1) is the raw material Y type of alkali metal ion by the ion exchange liquid containing ion-exchanger and at least partly compensating cation Molecular sieve carries out ion exchange, molecular sieve after being exchanged；

(2) molecular sieve after the exchange is subjected to hydro-thermal process, obtains molecular sieve after the first hydro-thermal process, the hydro-thermal process Condition makes after the first hydro-thermal process in the infrared spectrogram of molecular sieve, the antisymmetric vibration frequency σ of structure sensitive₁Meet following Condition:

35≤0.766 × (1086- σ₁)≤42；

(3) under the conditions of dealumination reaction, by molecular sieve after first hydro-thermal process with containing dealumination agent and ion-exchanger The contact of dealuminzation solution, obtains dealuminzation molecular sieve, and the dealumination agent is selected from acid, divides after the dealumination agent and first hydro-thermal process Son sieve ratio be 0.0005-0.005, the dealumination agent in mol, after first hydro-thermal process molecular sieve in gram, and The molar ratio of the dealumination agent and the ion-exchanger is 0.2-0.8；

(4) the dealuminzation molecular sieve is subjected to hydro-thermal process, obtains molecular sieve after the second hydro-thermal process；

(5) under the conditions of dealumination reaction, by molecular sieve after second hydro-thermal process with containing ion-exchanger and fluosilicic acid The contact of dealuminzation solution, obtains dealuminzation Y type molecular sieve.

2. carrier according to claim 1, wherein in step (1), the condition of ion exchange makes molecule after the exchange Alkali metal element content in sieve is the 20-40% of the alkali metal element content in the raw material Y type molecular sieve, the alkali metal Constituent content is in terms of oxide.

3. carrier according to claim 2, wherein in step (1), the condition of ion exchange makes molecule after the exchange Alkali metal element content in sieve is the 25-35% of the alkali metal element content in the raw material Y type molecular sieve, the alkali metal Constituent content is in terms of oxide.

4. carrier according to claim 3, wherein in step (1), the condition of ion exchange makes molecule after the exchange Alkali metal element content in sieve is the 28-35% of the alkali metal element content in the raw material Y type molecular sieve, the alkali metal Constituent content is in terms of oxide.

5. carrier described in any one of -4 according to claim 1, wherein in step (1), the ion exchange is being not higher than It is carried out at a temperature of 60 DEG C.

6. carrier according to claim 5, wherein in step (1), the ion exchange 20-55 DEG C at a temperature of into Row.

7. carrier according to claim 1, wherein in step (2), the condition of the hydro-thermal process makes first water After heat treatment in the infrared spectrogram of molecular sieve, the antisymmetric vibration frequency σ of structure sensitive₁Meet the following conditions:

38≤0.766 × (1086- σ₁)≤41.8。

8. carrier according to claim 7, wherein in step (2), the antisymmetric vibration frequency σ of structure sensitive₁Meet with Lower condition:

38≤0.766 × (1086- σ₁)≤40。

9. according to claim 1, carrier described in any one of 7 and 8, wherein step (2) carries out one of in the following ways Hydro-thermal process:

Mode one: molecular sieve after the first hydro-thermal process is subjected to hydro-thermal process, the hydro-thermal process in steam-laden atmosphere It carries out at a temperature of 500-700 DEG C, the duration of the hydro-thermal process is 0.5-5 hours；

Mode two: aqueous molecular sieve pulp is heat-treated in closed container, and the water in aqueous molecular sieve pulp contains Amount is 30-85 weight %, the hydro-thermal process 480-700 DEG C at a temperature of carry out, the duration of the hydro-thermal process is 0.5-5 hours.

10. carrier according to claim 9, wherein in mode one, the hydro-thermal process 550-680 DEG C at a temperature of It carries out, the duration of the hydro-thermal process is 1-4 hours.

11. carrier according to claim 10, wherein in mode one, the duration of the hydro-thermal process is that 2-4 is small When.

12. carrier according to claim 9, wherein in mode two, the water content in aqueous molecular sieve pulp is 45- 70 weight %, the hydro-thermal process 500-650 DEG C at a temperature of carry out, duration of the hydro-thermal process is 1-4 hours.

13. carrier according to claim 12, wherein in mode two, the water content in aqueous molecular sieve pulp is 50- 65 weight %, the hydro-thermal process 520-580 DEG C at a temperature of carry out, duration of the hydro-thermal process is that 1.5-3 is small When.

14. carrier according to claim 13, wherein in mode two, the hydro-thermal process 540-560 DEG C at a temperature of It carries out.

15. carrier according to claim 1, wherein in step (3), after the dealumination agent and first hydro-thermal process The ratio of molecular sieve is 0.0008-0.004, and molecular sieve is in gram in mol, after first hydro-thermal process for the dealumination agent； And the molar ratio of the dealumination agent and the ion-exchanger is 0.6 or less.

16. carrier according to claim 15, wherein in step (3), after the dealumination agent and first hydro-thermal process The ratio of molecular sieve is 0.001-0.0035, and molecular sieve is in gram in mol, after first hydro-thermal process for the dealumination agent； And the molar ratio of the dealumination agent and the ion-exchanger is 0.4 or less.

17. carrier according to claim 16, wherein in step (3), and the dealumination agent and the ion-exchanger Molar ratio is 0.25 or less.

18. according to claim 1 with the carrier described in any one of 15-17, wherein in step (3) the dealuminzation solution, institute The concentration for stating dealumination agent is 0.1-5mol/L.

19. carrier according to claim 18, wherein in step (3) the dealuminzation solution, the concentration of the dealumination agent is 0.2-4mol/L。

20. carrier according to claim 19, wherein in step (3) the dealuminzation solution, the concentration of the dealumination agent is 0.4-3mol/L。

21. carrier according to claim 20, wherein in step (3) the dealuminzation solution, the concentration of the dealumination agent is 0.5-2.5mol/L。

22. according to claim 1 with the carrier described in any one of 15-17, wherein in step (3), the dealumination agent is hydrogen One or more of chloric acid, sulfuric acid, nitric acid and fluosilicic acid.

23. according to claim 1 with the carrier described in any one of 15-17, wherein in step (3), the contact is in 10- It is carried out at a temperature of 100 DEG C.

24. carrier according to claim 23, wherein in step (3), it is described contact 15-50 DEG C at a temperature of carry out.

25. carrier according to claim 24, wherein in step (3), it is described contact 20-40 DEG C at a temperature of carry out.

26. carrier according to claim 1, wherein in step (4), the hydro-thermal process one of in the following ways into Row:

Mode one: dealuminzation molecular sieve is subjected to hydro-thermal process in steam-laden atmosphere, the hydro-thermal process is at 500-700 DEG C At a temperature of carry out, duration of the hydro-thermal process is 1-5 hours；

Mode two: aqueous dealuminzation molecular sieve pulp is heat-treated in closed container, aqueous dealuminzation molecular sieve pulp In water content be 30-85 weight %, the temperature of heat treatment is 480-700 DEG C, and the duration of hydro-thermal process is that 0.5-5 is small When.

27. carrier according to claim 26, wherein in mode one, the hydro-thermal process 600-680 DEG C at a temperature of It carries out, the duration of the hydro-thermal process is 2-3 hours.

28. carrier according to claim 26, wherein the water content in mode two, in aqueous dealuminzation molecular sieve pulp For 45-70 weight %, the temperature of heat treatment is 500-650 DEG C, and the duration of hydro-thermal process is 1-4 hours.

29. carrier according to claim 28, wherein the water content in mode two, in aqueous dealuminzation molecular sieve pulp For 60-68 weight %, the temperature of heat treatment is 520-580 DEG C, and the duration of hydro-thermal process is 2-4 hours.

30. carrier according to claim 29, wherein in mode two, the temperature of heat treatment is 540-560 DEG C.

31. carrier according to claim 1, wherein in step (5), it is described contact 40-100 DEG C at a temperature of carry out, The duration of the contact is 0.5-5 hours.

32. carrier according to claim 31, wherein in step (5), it is described contact 50-95 DEG C at a temperature of carry out, The duration of the contact is 0.8-3.5 hours.

33. carrier according to claim 32, wherein in step (5), it is described contact 55-80 DEG C at a temperature of carry out.

34. carrier according to claim 33, wherein in step (5), it is described contact 60-70 DEG C at a temperature of carry out.

35. according to claim 1-4,7,8, carrier described in any one of 15-17 and 26-34, wherein institute in step (1) It states ion-exchanger described in ion-exchanger described in ion-exchanger, step (3) and step (5) and is respectively organic ammonium salt One or more of with inorganic ammonium salt.

36. carrier according to claim 35, wherein ion-exchanger described in step (1), described in step (3) from Ion-exchanger described in sub- exchanger and step (5) is respectively one of ammonium oxalate, ammonium sulfate, ammonium chloride and ammonium nitrate Or it is two or more.

37. according to claim 1-4,7,8, carrier described in any one of 15-17 and 26-34, wherein the raw material Y type In molecular sieve, in terms of oxide, the content of the alkali metal ion as compensating cation is 10-20 weight %.

38. the carrier according to claim 37, wherein in the raw material Y type molecular sieve, in terms of oxide, as compensation The content of the alkali metal ion of cation is 12-16 weight %.

39. according to claim 1-4,7,8, carrier described in any one of 15-17 and 26-34, wherein as compensation sun from The alkali metal ion of son is sodium ion.

40. according to claim 1-4,7,8, carrier described in any one of 15-17 and 26-34, wherein the raw material Y type The relative crystallinity of molecular sieve is 85-120%；The mass ratio of the silica/alumina of the raw material Y type molecular sieve is 4 or less.

41. carrier according to claim 40, wherein the relative crystallinity of the raw material Y type molecular sieve is 90-95%； The mass ratio of the silica/alumina of the raw material Y type molecular sieve is 2.5-3.5.

42. according to claim 1-4,7,8, carrier described in any one of 15-17 and 26-34, wherein with the carrier On the basis of total amount, the content of the dealuminzation Y type molecular sieve is 1-8 weight %；The content of the heat-resistant inorganic oxide is 92-99 Weight %.

43. carrier according to claim 42, wherein on the basis of the total amount of the carrier, the dealuminzation Y type molecular sieve Content be 2-7 weight %；The content of the heat-resistant inorganic oxide is 93-98 weight %.

44. carrier according to claim 43, wherein on the basis of the total amount of the carrier, the dealuminzation Y type molecular sieve Content be 3-6 weight %；The content of the heat-resistant inorganic oxide is 94-97 weight %.

45. according to claim 1-4,7,8, carrier described in any one of 15-17 and 26-34, wherein the heat resistant inorganic Oxide is one of aluminium oxide, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide and silica-alumina or two Kind or more.

46. carrier according to claim 45, wherein the heat-resistant inorganic oxide is aluminium oxide and/or silica-oxygen Change aluminium.

47. carrier according to claim 46, wherein the heat-resistant inorganic oxide is aluminium oxide and silica-oxidation Aluminium, on the basis of the total amount of the heat-resistant inorganic oxide, the content of aluminium oxide is 30-80 weight %；Silica-alumina Content is 20-70 weight %.

48. carrier according to claim 47, wherein the heat-resistant inorganic oxide is aluminium oxide and silica-oxidation Aluminium, on the basis of the total amount of the heat-resistant inorganic oxide, the content of aluminium oxide is 40-75 weight %；Silica-alumina Content is 25-60 weight %.

49. application of the carrier as the carrier of loaded catalyst described in any one of claim 1-48.

50. a kind of catalyst, which includes carrier and load group VIII metallic element on the carrier and the Group vib metallic element, which is characterized in that the carrier is carrier described in any one of claim 1-48.

51. catalyst according to claim 50, wherein on the basis of the total amount of catalyst, in terms of oxide described in The content of group VIII metallic element is 2-10 weight %, and the content of the vib metals element in terms of oxide is 10- 40 weight %, the content of the carrier are 50-88 weight %.

52. catalyst according to claim 51, wherein on the basis of the total amount of catalyst, in terms of oxide described in The content of group VIII metallic element is 2.5-8 weight %；The content of the vib metals element in terms of oxide is 20-30 weight %；The content of the carrier is 62-77.5 weight %.

53. the catalyst according to any one of claim 50-52, wherein the group VIII metallic element is nickel And/or cobalt, the vib metals element are molybdenum and/or tungsten.

54. a kind of preparation method of catalyst, this method is included in the supported on carriers group VIII metallic element and Section VI B Race's metallic element, which is characterized in that the carrier is carrier described in any one of claim 1-48.

55. method according to claim 54, wherein load group VIII gold on the carrier using the method for dipping Belong to element and vib metals element, and the carrier through impregnating is dried and is optionally roasted.

56. method according to claim 55, wherein the drying 80-300 DEG C at a temperature of carry out, the drying Duration be 1-48 hours；

The roasting 350-550 DEG C at a temperature of carry out, duration of the roasting is 1-10 hours.

57. method according to claim 56, wherein it is described roasting 450-650 DEG C at a temperature of carry out.

58. a kind of catalyst of the preparation of the method as described in any one of claim 54-57.

59. application of the catalyst as the catalyst of hydrocracking reaction described in any one of claim 50-53 and 58.

60. a kind of method for hydrogen cracking, this method are included under hydrocracking condition, hydrocarbon ils is contacted with catalyst, it is described to urge Agent is catalyst described in any one of claim 50-53 and 58.