CN104043478B - A kind of hydrocracking catalyst and preparation thereof and application - Google Patents

Abstract

A kind of hydrocracking catalyst and preparation thereof and application, described catalyst contains containing heat-resistant inorganic oxide matrix, Y type molecular sieve and the carrier of Beta molecular sieve, wherein, the most probable pore size of described carrier is 1～30nm, aperture concentration degree is 22～48, described most probable pore size is to use BET method to measure, and described aperture concentration degree refers to that the specific pore volume using BET method to measure is long-pending with in the distribution curve of varying aperture, the ratio of the height at peak and the halfwidth at this peak.The preparation method of described catalyst includes that preparation is containing heat-resistant inorganic oxide matrix, Y type molecular sieve and the carrier of Beta molecular sieve, the preparation method of this carrier includes the precursor of heat-resistant inorganic oxide, Y type molecular sieve and Beta molecular sieve, peptizer and water mixing extrusion molding, wherein, the described molded body temperature in the exit of described extruder is 40～150 DEG C.Compared with prior art, the hydrocracking catalyst that the present invention provides is adding man-hour for hydrocarbon ils, has high catalysis activity and intermediate oil selectivity.

Description

A kind of hydrocracking catalyst and preparation thereof and application

Technical field

The present invention relates to a kind of hydrocracking catalyst and preparation thereof and application.

Background technology

In recent years, in world wide, crude oil heaviness and in poor quality tendency are day by day obvious, meanwhile, and centering Between the demand of distillate and reformation, steam crack material be but continuously increased.This promotes heavy distillate to add Work technology is developed rapidly, and catalyst is the most mostly important and crucial factor.

The catalyst converted for mink cell focus or macromole, except requiring that catalyst has bigger aperture and foot Outside enough pore volumes, also require that the pore-size distribution of catalyst mesopore concentrates (that is, aperture concentration degree is high).

Due to for the catalyst of the conversion of mink cell focus or macromole generally by there is catalytic action Active component is supported on carrier and obtains, and therefore prepares and has bigger aperture and pore volume, and has relatively The catalyst of high aperture concentration degree it is crucial that provide to there is big aperture and there is higher aperture and concentrate The carrier of degree.

At present, the method being generally used for describing aperture concentration degree (or referred to as hole concentration degree) is: calculate given Pore volume in pore diameter range accounts for the percentage ratio of total pore volume, and this percentage ratio is the highest, it is believed that aperture concentration degree is also got over High.But, the method being given the percentage ratio that the pore volume in the range of aperture accounts for total pore volume by calculating evaluates load The aperture concentration degree of body is difficult to reflect exactly the pore-size distribution of carrier.

CN101757929A discloses and uses the specific pore volume measured by BET method long-pending (dV/dlog (D)) with hole In the distribution curve in footpath, the ratio of the height at peak and the halfwidth at this peak can evaluate the hole of catalyst exactly Footpath concentration degree.On this basis, CN101757929A also discloses a kind of hydrocracking catalyst, and this is urged Agent contains carrier and the IVth B race gold loaded in hydrogenation activity composition on this carrier and the periodic table of elements Belonging to component, wherein, the most probable pore size of described carrier is 6～14nm, and aperture concentration degree is more than 7.To the greatest extent It can be more than 7 that pipe CN101757929A discloses the aperture concentration degree of described carrier, but from From the point of view of CN101757929A disclosed embodiment, the aperture concentration degree of carrier is up to 21.4, needs Improve further.

To sum up, how to obtain and there is high catalysis activity and intermediate oil is optionally hydrocracked and urges Agent remains a technical problem urgently to be resolved hurrily.

Summary of the invention

It is an object of the invention to overcome deficiencies of the prior art, it is provided that a kind of have high catalysis Activity and the selective hydrocracking catalyst of intermediate oil, and the preparation method of this catalyst and should With.

The present inventor finds in practice process, and the aperture concentration degree improving carrier can significantly improve The activity of the catalyst being hydrocracked prepared by this carrier and intermediate oil selectivity.But, use The method (such as, method disclosed in CN101757929A) of prior art can not obtain has higher aperture The carrier of concentration degree (such as, aperture concentration degree is more than 22).The research of the present inventor is sent out Existing: to prepare molded body with extruder by extrusion molding, thus when obtaining carrier, making described molded body Temperature in the exit of extruder is 40～150 DEG C, it is possible to obtains and has bigger aperture and aperture concentration Degree is the carrier of more than 22.The carrier of hydrocracking catalyst prepared by the method preparation is used to be hydrocracked During catalyst, catalyst not only has higher catalysis activity, and has higher intermediate oil and select Property.

The present invention provides a kind of hydrocracking catalyst, this catalyst contain containing heat-resistant inorganic oxide matrix, Y type molecular sieve and the carrier of Beta molecular sieve (also referred to as beta-molecular sieve), wherein, may be used of described carrier Several apertures are 1～30nm, and aperture concentration degree is 22～48, and aperture, described most probable hole is to use BET method Measuring, described aperture concentration degree refers to that the specific pore volume long-pending (dV/dlog (D)) using BET method to measure is with hole In the distribution curve of footpath change, the height at peak and the ratio of the halfwidth at this peak.

Present invention also offers the preparation method of described hydrocracking catalyst, including preparation oxygen Han heat resistant inorganic Compound substrate, Y type molecular sieve and the carrier of Beta molecular sieve, the preparation method of this carrier includes following step Rapid: (1) by the precursor of heat-resistant inorganic oxide, Y type molecular sieve and Beta molecular sieve, peptizer and Water mixes, to provide raw material；(2) described raw material is sent in extruder, and through mixed in described extruder Extrude after pinching, to obtain molded body；(3) described molded body is carried out roasting, to obtain described carrier, its In, the described molded body temperature in the exit of described extruder is 40～150 DEG C.

Invention further provides a kind of method for hydrogen cracking, the method is included under hydrocracking condition, Hydrocarbon ils is contacted with catalyst, wherein, the catalyst that described catalyst provides for the present invention.

According to the carrier of the present invention, not only there is bigger aperture and pore volume, and there is higher aperture and concentrate Degree.The hydrocracking catalyst containing Y type molecular sieve and Beta molecular sieve prepared by this carrier is for hydrocarbon Oil adds man-hour, has high catalysis activity and intermediate oil selectivity.

Accompanying drawing explanation

Fig. 1 be the long-pending distribution curve with aperture (the aperture finger-hole diameter in the application) of the specific pore volume of carrier with And peak height M, the schematic diagram of half peak breadth N.

Detailed description of the invention

The catalyst provided according to the present invention, wherein said carrier contains heat-resistant inorganic oxide, Y type divides Son sieve and Beta molecular sieve.The most probable pore size of described carrier can be 1～30nm, preferably 2～ 20nm, more preferably 5～10nm.The aperture concentration degree of described carrier is 22～48, preferably 25～ 48, more preferably 27～40.On the basis of described carrier, heat-resistant inorganic oxide in described carrier Content be 50～98 weight %, preferably 60～95 weight %, the content of Y type molecular sieve is more than 0 Weight % to less than or equal to 40 weight %, preferably 0.5～35 weight %, more preferably 0.5～30 Weight %, the content of beta-molecular sieve is to less than or equal to 40 weight % more than 0 weight %, preferably 0.5～ 35 weight %, more preferably 0.5～25 weight %.

In the present invention, term " aperture, most probable hole " refers to: using the hole knot of BET method measuring samples During structure, it is thus achieved that specific pore volume long-pending (dV/dlog (D)) with in the distribution curve in aperture, specific pore volume amasss The aperture corresponding to maximum of (dV/dlog (D)).BET method is used to measure the hole knot of porous mass Structure, is known in those skilled in the art to obtain specific pore volume and to amass with the method for the distribution curve in aperture, example As can (Yang Cui be fixed for Science Press, the nineteen ninety first edition according to " Petrochemical Engineering Analysis method " Compile) described in RIPP151-90 in regulation method measure.

In the present invention, term " aperture concentration degree " refers to: in the pore structure using BET method measuring samples Time, it is thus achieved that specific pore volume long-pending with in the distribution curve in aperture, the ratio of peak height and the halfwidth at this peak.Peak height The biggest with the ratio of the halfwidth at this peak, show that the aperture intensity of carrier is the highest.Aperture concentration degree is permissible Referred to as hole concentration degree.

According to the present invention, deposit in described specific pore volume long-pending (dV/dlog (D)) is with the distribution curve of varying aperture When multiple peak, the peak height at each peak all should meet above-mentioned requirements with the ratio of the halfwidth at this peak.

Fig. 1 is the long-pending distribution curve schematic diagram with aperture of specific pore volume.In Fig. 1, abscissa is the hole of carrier Footpath, uses logarithmic coordinates, and unit isVertical coordinate is that specific pore volume amasss.In Fig. 1, M represents peak height (that is, maximum dV/dlog (D)), N represent half-peak breadth (halfwidth) (that is, on described distribution curve, Vertical coordinate isTwo points between distance).When calculated hole diameters concentration degree, halfwidth and peak height are equal Use identical long measure.

In the present invention, term " heat-resistant inorganic oxide " refers under oxygen or oxygen-containing atmosphere, decomposition temperature It is not less than the inorganic oxygen-containing compound of 300 DEG C (such as: decomposition temperature is 300～1000 DEG C).

According to the present invention, described heat-resistant inorganic oxide is selected from arbitrarily can be as adding hydrogen species catalyst carrier Use heat-resistant inorganic oxide, for example, it is possible to selected from aluminium oxide, silica-alumina, silicon oxide, One or more in titanium oxide, zirconium oxide, preferably are selected from aluminium oxide, silica-alumina, silicon oxide One or more, more preferably aluminium oxide, silica-alumina and their mixture.It Can be commercially available commodity can also be use arbitrary existing method prepare.

The silica alumina ratio of described Beta molecular sieve can be carried out according to the concrete application scenario finally preparing catalyst Suitable selection, is not particularly limited.In a preferred embodiment, preferably silica alumina ratio is 25～200, The Beta molecular sieve of more preferably 25～150.They can be commercially available commodity, it is also possible to is to use to appoint Prepared by the existing method of meaning.

Described Y type molecular sieve can be various Y type molecular sieves commonly used in the art, is not particularly limited. Such as, selected from HY, USY, REY, USREY one or more etc..Preferred embodiment In, lattice constant is preferably whereinY type molecular sieve.They can be commercially available business Product can also be to use arbitrary existing method to prepare.

According to the present invention, described carrier can have variously-shaped according to concrete application scenario.Such as, Described carrier can be spherical, bar shaped, annular, cloverleaf pattern, honeycombed and butterfly.

The hydrocracking catalyst provided according to the present invention, hydrogenation active metals component therein can be any The hydrogenation active metals that can use as hydrocracking catalyst, such as, selected from your gold of group VIII Belong to component, selected from least one group VIII base metal and the group selected from least one vib metals Close.When described hydrogenation active metals component is selected from least one group VIII base metal and selected from least one When planting the combination of vib metals, the metal component of preferred group VIII is nickel and/or cobalt, preferably The metal component of vib is molybdenum and/or tungsten, counts and on the basis of described catalyst by oxide, described The content of vib metals component is 10～40 weight %, preferably 15～30 weight %, described The content of group VIII metal is 2～10 weight %, preferably 2.5～6.5 weight %.

The catalyst provided according to the present invention, it is also possible to provide the property of catalyst containing any present invention that do not affects Maybe can improve the material of the catalyst performance that the present invention provides.As contained in the components such as phosphorus, boron or fluorine One or both, count and on the basis of catalyst by element, the content of above-mentioned auxiliary agent be less than 10 weight %, preferably 0.5-5 weight %；Can also contain Organic substance, the most organic type includes but does not limits In alcohols (including polyhydric alcohol), amine (including polyamine), acid and esters etc..In terms of carbon and with On the basis of described catalyst, the content of described organic additive is less than 20 weight of total catalyst weight %。

The method for preparing catalyst provided according to the present invention, wherein the preparation method of carrier comprises the following steps: (1) precursor of heat-resistant inorganic oxide, Y type molecular sieve and Beta molecular sieve, peptizer and water are mixed Close, to provide raw material；(2) described raw material is sent in extruder, and in described extruder after kneading Extrusion, to obtain molded body；(3) described molded body is carried out roasting, to obtain described carrier, wherein, The described molded body temperature in the exit of described extruder is 40～150 DEG C.

Raw material is being extruded, during obtaining molded body, the most especially to extrusion temperature with extruder It is controlled (usually room temperature or less than 40 DEG C), but the present inventor sends out in research process Existing, making the molded body temperature in the exit of described extruder is 40～150 DEG C, it is possible to make by this molding Most probable pore size and the aperture concentration degree of carrier prepared by body meet previously described requirement.Preferably, described The molded body temperature in the exit of described extruder is 50～120 DEG C.It is further preferred that described molding The body temperature in the exit of described extruder is 60～100 DEG C, is so obtained in that higher aperture is concentrated Degree.It is highly preferred that the temperature that described molded body is in the exit of described extruder is 60～98 DEG C.

According to the present invention, various method can be used to make the one-tenth extruded by described extruder in step (2) The type body temperature in the exit of this extruder is within the scope of mentioned above.Such as: can be by institute State raw material carry out in an extruder kneading or extrusion during, by regulation extruder or kneading machine fuselage and / or the cooling condition of head or heating condition so that the molded body extruded by described extruder is in this extrusion The temperature in the exit of machine is within the scope of mentioned above.Regulation extruder or kneading machine fuselage and/ Or the method for the cooling condition of head or heating condition is to it is known in the art, to repeat no more herein.

The present inventor in research process it has furthermore been found that in described step (1) by described raw material Temperature (that is, the described raw material temperature in the porch of described extruder) be 40～100 DEG C, can not only The most probable pore size enough making the carrier of preparation meets previously described requirement, but also enables to preparation Carrier has higher aperture concentration degree, and the carrier simultaneously prepared also has higher mechanical strength.

Therefore, the present invention one preferred embodiment in, it is described former that described step (1) obtains The material temperature in the porch of described extruder is 40～100 DEG C.Have intended at the carrier guaranteeing preparation On the premise of aperture and aperture concentration degree, go out from the angle of the mechanical strength of the carrier improving preparation further Send out, the described raw material that described step (1) the obtains temperature in the porch of described extruder be preferably 40～ 80 DEG C, more preferably 50～80 DEG C.

Can use various method is 40～100 to make the described raw material temperature in the porch of described extruder DEG C (preferably 40～80 DEG C, more preferably 50～80 DEG C).

Usually, can be by the precursor of described heat-resistant inorganic oxide, Y type molecular sieve and Beta molecule The process that sieve, peptizer and water carry out mixing is carried out in a heated condition, and the condition of described heating makes to obtain The raw material temperature in the porch of described extruder be 40～100 DEG C (preferably 40～80 DEG C, more preferably It it is 50～80 DEG C).Such as: can divide at the precursor of heat-resistant inorganic oxide, Y type molecular sieve and Beta In the mixed process of son sieve, peptizer and water, carry out heating the temperature of the raw material making preparation by external heat source Degree is within the scope of 40～100 DEG C (preferably 40～80 DEG C, more preferably 50～80 DEG C)；Can also By in the precursor of described heat-resistant inorganic oxide, Y type molecular sieve and Beta molecular sieve, peptizer and water At least one heating, then carry out mixing so as to get the temperature of described raw material be 40～100 DEG C (excellent Elect 40～80 DEG C as, more preferably 50～80 DEG C), and by this temperature be 40～100 DEG C (preferably 40～ 80 DEG C, more preferably 50～80 DEG C) raw material send in described extruder.Such as, by peptizer and water Mixing, the most again by the mixture that obtains and the precursor of described heat-resistant inorganic oxide, Y type molecular sieve and Beta molecular sieve mixes, and afterwards described compound is sent into extruder for shaping.Wherein it is possible to by inciting somebody to action Hot water mixes with peptizer, obtains the mixture of heat, then is aoxidized with described heat resistant inorganic by the mixture of this heat The precursor of thing, Y type molecular sieve and Beta molecular sieve mixing, thus preparation temperature be 40～100 DEG C (excellent Elect 40～80 DEG C as, more preferably 50～80 DEG C) raw material, and by this temperature be 40～100 DEG C (excellent Elect 40～80 DEG C as, more preferably 50～80 DEG C) raw material send in extruder.

Wherein, at described raw material, the precursor of heat-resistant inorganic oxide, Y type molecular sieve and Beta are i.e. included In molecular sieve mixture material, the consumption of each component can according to the heat-resistant inorganic oxide in intended carrier and The content of molecular sieve selects.On the basis of described carrier, in a preferred embodiment, each component Consumption makes the content of heat-resistant inorganic oxide in final carrier be 50～98 weight %, preferably 60～95 weights Amount %, the content of Y type molecular sieve be more than 0 weight % extremely less than or equal to 40 weight %, preferably 0.5～ 35 weight %, more preferably 0.5～30 weight %, the content of Beta molecular sieve is more than 0 weight % Extremely less than or equal to 40 weight %, preferably 0.5～35 weight %, more preferably 0.5～25 weight %。

The silica alumina ratio of described Beta molecular sieve can enter according to the concrete application scenario of the catalyst of final preparation The selection that row is suitable, is not particularly limited.In a preferred embodiment, the most described Beta molecular sieve Silica alumina ratio be 25～200, more preferably 25～150.They can be commercially available commodity can also be to adopt Prepare by arbitrary existing method.

Described Y type molecular sieve can be various Y type molecular sieves commonly used in the art, such as, selected from HY, One or more in USY, REY, USREY etc., are not particularly limited.Preferred embodiment In, preferably lattice constant isY type molecular sieve.They can be commercially available commodity also Can be to use arbitrary existing method to prepare.

Described heat-resistant inorganic oxide is selected from arbitrarily can be as adding the heat-resisting nothing that hydrogen species catalyst carrier uses Machine oxide, for example, it is possible to selected from aluminium oxide, silica-alumina, silicon oxide, titanium oxide, oxidation One or more in zirconium, preferably are selected from the one in aluminium oxide, silica-alumina, silicon oxide or several Kind.They can be commercially available commodity can also be use arbitrary existing method prepare.

In the present invention, the precursor of described heat-resistant inorganic oxide refers to can be formed under roasting condition described The hydrous oxide of heat-resistant inorganic oxide.As a example by aluminium oxide, its precursor is hydrated alumina, including Aluminium hydroxide, boehmite, boehmite, gibbsite, and coagulating containing above-mentioned hydrated alumina Glue or colloidal sol etc..They can be commercially available commodity can also be use arbitrary existing method prepare.

In a specific embodiment, before the present invention prepares the described heat-resistant inorganic oxide that described carrier uses The average particulate diameter of body thing can be average particulate diameter commonly used in the art.The present inventor is grinding Find during studying carefully: the average particulate diameter of the precursor of described heat-resistant inorganic oxide is 30～100nm Time, the method for the present invention carrier prepared has higher aperture concentration degree.Carry from improving preparation further The angle of the aperture concentration degree of body is set out, and the average particulate diameter of the precursor of described heat-resistant inorganic oxide is excellent Elect 30～80nm as, more preferably 30～60nm.It is further preferred that described heat-resistant inorganic oxide The average particulate diameter of precursor is 40～60nm.

Average particulate diameter is in the precursor of the heat-resistant inorganic oxide within the scope of described previously, permissible Selected from the commercially available commodity meeting this requirement, it would however also be possible to employ various methods commonly used in the art make described resistance to The average particulate diameter of the precursor of hot inorganic oxide meets requirement.Such as, by before use by described The precursor of heat-resistant inorganic oxide is ground and/or sieves, so that described heat-resistant inorganic oxide The average particulate diameter of precursor meets requirement.

In the present invention, described average particulate diameter is to use XRD method, by the Scherrer formula shown in Formulas I It is calculated,

$D=\frac{0.89\mathrm{\λ}}{{\mathrm{\β}}_{\mathrm{HKL}}\cos \mathrm{\θ}}---\left(I\right)$

In Formulas I, D is average particulate diameter；

λ is the wavelength of X-ray；

β_HKLThe widthization degree caused, wherein, β is refined because of grain size for diffraction maximum_HKL=B-B₀；

B is the peak width at half height of actual measurement；

B₀Widthization degree for instrument；

θ is angle of incidence.

According to the present invention, the precursor of described heat-resistant inorganic oxide preferably comprises the precursor of aluminium oxide.Its In, the precursor of described aluminium oxide is preferably boehmite.All can shape although with various boehmites Become aluminium oxide, and realize the purpose of the present invention, but the present inventor finds in research process: adopt Big aperture can be had at the carrier guaranteeing finally to prepare with the boehmite that degree of crystallinity is more than 80% Under conditions of pore volume, improve the aperture concentration degree of the carrier obtained further, and then make urging of the present invention Agent has higher catalysis activity and intermediate oil selectivity, can also improve the carrier of preparation simultaneously Mechanical strength.

In the present invention, described degree of crystallinity is relative crystallinity, is to use " Petrochemical Engineering Analysis method " (section Learn publishing house, the nineteen ninety first edition, Yang Cui surely wait compile) described in RIPP139-90 in regulation method Measuring, wherein, the standard specimen used is the sample of numbered S87-16B, the absolute crystallinity of this standard specimen It is 98.0%, can be commercially available by Research Inst. of Petroleum Processing, SINOPEC.

The present invention one preferred embodiment in, the precursor of described heat-resistant inorganic oxide contains plan Boehmite, and the relative crystallinity of described boehmite is more than 80%, preferably more than 90%. From the angle of the aperture concentration degree improving the carrier obtained further, the relative knot of described boehmite Crystalline substance degree is preferably 90～110%.

In a kind of embodiment being more highly preferred to of the present invention, the precursor of described heat-resistant inorganic oxide contains Having boehmite, the relative crystallinity of described boehmite is more than 80%, and described plan thin water aluminum The average particulate diameter of stone is 30～100nm.

In a kind of further preferred embodiment of the present invention, the precursor of described heat-resistant inorganic oxide Containing boehmite, the relative crystallinity of described boehmite is 90～110%, and the thin water of described plan The average particulate diameter of aluminum stone is 30～80nm.

In a kind of most preferably embodiment of the present invention, described raw material is in the porch of described extruder Temperature is 40～80 DEG C, and the described molded body temperature in the exit of described extruder is 60～98 DEG C, and The precursor of described heat-resistant inorganic oxide contains boehmite, the relative crystallinity of described boehmite Being 90～110%, the average particulate diameter of described boehmite is 30～80nm.According to this embodiment party Carrier prepared by formula has higher aperture concentration degree and higher mechanical strength.

According to the method for the present invention, described by heat-resistant inorganic oxide and/or the predecessor of heat-resistant inorganic oxide In the described raw material that thing, Y type molecular sieve and Beta molecular sieve, peptizer and water are mixed to get, therein The amount of peptizer can carry out suitable choosing according to the kind of the precursor of the heat-resistant inorganic oxide used Select.Usually, on the basis of the total amount of described raw material, the content of described peptizer can be 0.1～5 weights Amount %, preferably 0.5～4 weight %.The present invention is not particularly limited for the kind of described peptizer, can Think the conventional selection of this area.In the present invention, the instantiation of described peptizer can be but be not limited to: Nitric acid, hydrochloric acid, phosphoric acid, trichloroacetic acid and citric acid.

According to the method for the present invention, make described heat-resistant inorganic oxide and/or heat-resistant inorganic oxide being enough to The described raw material that is mixed to get of precursor, Y type molecular sieve and Beta molecular sieve, peptizer and water, warp On the premise of described extruder extrusion, the present invention is not particularly limited for the consumption of described water, can be this The conventional selection in field.

According to the method for the present invention, described raw material can also contain extrusion aid.The content of described extrusion aid and kind Class can be the conventional selection of this area.Usually, on the basis of described raw material, the consumption of described extrusion aid It is 0.1～5 weight %, preferably 1～3 weight %.In the present invention, the example of described extrusion aid can be But it is not limited to: the one in starch, cellulose, organic carboxyl acid, polyhydric alcohol, organic amine and surfactant Or it is multiple.

Wherein, described starch includes but not limited to that sesbania powder, described cellulose include but not limited to Methyl cellulose Element etc..

Described organic carboxyl acid refers to the organic compound in molecular structure with one or more carboxyl, such as " Lan Shi Chemical manual " second edition, the organic carboxyl acid enumerated in 1.26～1.27.Preferably, described organic Carboxylic acid be carbon number be 1～20 unary organic carboxylic acid or polybasic organic carboxylic acid (such as: the organic carboxylic of binary Acid).In the present invention, the example of described organic carboxyl acid can be but be not limited to: formic acid, acetic acid, second two Acid, propanoic acid, malonic acid, butanoic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, benzoic acid, phthalic acid and benzene Propanoic acid.

Described polyhydric alcohol refers to the organic compound in molecular structure with two or more hydroxyl.Described polynary The example of alcohol can be but be not limited to: ethylene glycol, glycerol and butanediol.

Described organic amine refers to the organic compound in molecular structure containing one or more amidos.Described have The example of machine amine can be but be not limited to: monoethanolamine, diethanolamine, triethanolamine, N-methyl diethanol Amine and carbamide.

Described surfactant can be anionic surfactant, cationic surface active agent, both sexes Ionic surfactant and nonionic surfactant.The example of described anionic surfactant can Think but be not limited to: stearic acid and dodecylbenzene sodium sulfonate.The example of described cationic surface active agent Can be but be not limited to: quaternary ammonium compound.The example of described amphoteric ionic surfactant can be but not limit In: lecithin, amino acid type surfactant and betaine type amphoteric surfactant.Described non-ionic surface The example of activating agent can be but be not limited to: fatty glyceride, fatty acid Pyrusussuriensis ester (Span series surface Activating agent), Polysorbate (TWEEN Series surfactant), polyoxyethylene-type surfactant and polyoxy Ethylene-polyoxypropylene block copolymers.

In the present invention, described extruder can be the various extruders that this area uses.This is not had by the present invention It is particularly limited to, can be the conventional selection of this area.

In the present invention, the described method that molded body carries out roasting and condition are not particularly limited, Ke Yiwei The normal condition of this area.Usually, the temperature of described roasting can be 350～800 DEG C, is preferably 450～650 DEG C；The time of described roasting can be 1～10 hour, preferably 2～5 hours.Described roasting Burning can be able to be oxygen-containing atmosphere, it is also possible to carry out in an oxygen-free atmosphere to carry out in will and spirit atmosphere in office, permissible Containing water vapour, it is also possible to be the air being completely dried or other gas.Calcination atmosphere is not appointed by this patent What limits.

According to the preparation method of the carrier of the present invention, before described molded body is carried out roasting, it is also possible to bag Including and be dried by described molded body, described being dried can be carried out, such as under the normal condition of this area: Described dry temperature can be 100～200 DEG C, and the described dry time can be 2～12 hours.Institute State and be dried and can carry out under conditions of normal pressure, it is also possible to carry out at reduced pressure, limit the most especially Fixed.Described being dried can be able to be oxygen-containing atmosphere to carry out in will and spirit atmosphere in office, and this patent is to dry atmosphere not Do any restriction.

Usually, the most probable pore size of prepared according to the methods of the invention carrier can be 1～30nm, excellent Elect 2～20nm as, more preferably 5～10nm；Aperture concentration degree can be 22～48, preferably 25～ 48(can be such as 25～40), more preferably 27～40.

According to the preparation method of the hydrocracking catalyst that the present invention provides, add including introducing on described carrier The step of hydrogen activity metal component, hydrogenation active metals component therein can be to split frequently as hydrogenation arbitrarily Change the hydrogenation active metals that catalyst uses, such as, selected from the noble metal component of group VIII, selected from extremely Few a kind of group VIII base metal and the combination selected from least one vib metals.

When described hydrogenation active metals component is selected from least one group VIII base metal and selected from least one When planting the combination of vib metals, the metal component of preferred group VIII is nickel and/or cobalt, preferably The metal component of vib is molybdenum and/or tungsten, counts and on the basis of described catalyst by oxide, described The introduction volume of vib metals component makes the content of group vib metal component in final catalyst be 10～40 Weight %, preferably 15～30 weight %, make the introduction volume of described group VIII metal component make finally to urge In agent, the content of group VIII metal component is 2～10 weight %, preferably 2.5～6.5 weight %.

On described carrier introduce hydrogenation active metals component can be those skilled in the art inform any Method, for example, it is possible to by with described in the solution impregnation of the compound containing described hydrogenation active metals component Carrier, is dried, roasting or the step of not roasting afterwards.

In the present invention, the example of the described compound containing vib metals can be but be not limited to: tungsten Acid, molybdic acid, metatungstic acid, ethyl metatungstic acid, para-molybdic acid, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate and second One or more in base ammonium metatungstate.

The described compound containing group VIII metal is preferably the oxysalt with nickel as cation, with nickel is In the anaerobic hydrochlorate of cation, the oxysalt with cobalt as cation and the anaerobic hydrochlorate with cobalt as cation One or more.In the present invention, the example of the described compound containing group VIII metal can be but not limit In: nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobaltous acetate, alkali formula One or more in cobalt carbonate, Nickel dichloride. and cobaltous chloride.

According to the present invention, various solvents commonly used in the art can be used to prepare containing described active component The solution of compound, as long as described compound can be dissolved in described solvent, forms the solution of stable homogeneous ?.Such as: described solvent can be water or alcohol (such as: ethanol) that carbon number is 1～5, is preferably Water and/or ethanol, more preferably water.

The method of described dipping can be various dipping methods commonly used in the art, such as, can be the saturated leaching in hole Stain method.The present invention was not particularly limited for the time of described dipping and the number of times of dipping, as long as being able to ensure that The amount of the active component with catalytic action on the catalyst finally given meets concrete use and requires i.e. Can.Usually, the time of described dipping can be 0.5～12 hour.

According to the present invention, the carrier for the compound by being loaded with described hydrogenation active metals component is done Dry method and condition are not particularly limited.Usually, described dry temperature can be 80～350 DEG C, It is preferably 100～300 DEG C；The described dry time can be 0.5～24 hour, and preferably 1～12 is little Time.

When catalyst after drying needs to carry out roasting, described method of roasting and condition are not had by the present invention It is particularly limited to, can be conventional method and the condition of this area.Usually, the temperature of described roasting is permissible It is 350～700 DEG C, preferably 400～650 DEG C；The time of described roasting can be 0.2～12 hour, It is preferably 1～10 hour.Described roasting can be to carry out in will and spirit atmosphere in office, and calcination atmosphere is not done by this patent Limit.

According to the present invention provide preparation method, when in described catalyst possibly together with selected from groups such as boron, phosphorus or fluorine During one or both adjuvant components in Fen, also include introducing the one in the components such as boron, phosphorus or fluorine or The step of several components, the described introducing method selected from components such as boron, phosphorus or fluorine can pass through multiple way Footpath, for example, it may be the compound containing described auxiliary agent is directly mixed with silicon-containing compound, molding roasting Burn；Can be that the compound containing described auxiliary agent is configured to the compound containing hydrogenation active metals component Contact with described carrier after mixed solution；Can also is that the compound containing auxiliary agent is individually prepared after solution with The contact of described carrier roasting.When auxiliary agent introduces described carrier respectively with hydrogenation active metals, first Contact with described carrier and roasting with containing auxiliary compound solution, the most again with containing hydrogenation active metals group The solution contact of the compound divided, such as by the method for dipping, described sintering temperature is 250-600 DEG C, Being preferably 350-500 DEG C, roasting time is 2-8 hour, preferably 3-6 hour.

The carrier that the catalyst that the present invention provides is used, not only has big aperture, and has high hole Footpath concentration degree, is particularly suitable as the hydrocracking catalyst of hydrocarbon ils, thus produces and have relatively low boiling and relatively The hydrocarbon system fraction of low-molecular-weight.

According to the method for hydrogen cracking of the present invention, described hydrocarbon ils can be various heavy mineral oil, artificial oil or Their mixture.Specifically, the example of described hydrocarbon ils can be but be not limited to: vacuum gas oil (VGO), de-gold Belong to oil, reduced crude, de-asphalted vacuum residue, decompression residuum, coker distillate, shale oil, tar sand Oil and liquefied coal coil.

The present invention is by using catalyst according to the invention, improving the conversion ratio being hydrocracked middle hydrocarbon ils Selective with intermediate oil, remaining condition being hydrocracked is not particularly limited, can be ability The normal condition in territory.Usually, described hydrocracking condition includes: temperature can be 200～650 DEG C, It is preferably 300～510 DEG C；In terms of gauge pressure, pressure can be 3～24 MPas, preferably 4～15,000,000 Handkerchief；Hydrogen to oil volume ratio can be 150～2500；During liquid, volume space velocity can be 0.1～30 hour^-1, preferably It it is 0.2～10 hour^-1。

According to the method for hydrogen cracking of the present invention, described catalyst the most preferably carries out presulfurization.Described The condition of presulfurization can be the normal condition of this area.Such as, the condition of described presulfurization may include that In presence of hydrogen, at a temperature of 140～370 DEG C, carry out pre-sulfur with sulfur, hydrogen sulfide or sulfur-bearing raw material Change.According to the method for hydrogen cracking of the present invention, described presulfurization can be carried out outside reactor, it is possible in reaction In device In-situ sulphiding.

The present invention is described in detail below in conjunction with embodiment.

Reagent used in following example and comparative example, except special instruction, is chemically pure reagent.

In following example and comparative example, in the model commercially available from Quantachrome company it isFull-automatic specific surface and pore size distribution determining instrument on, use BET method according to RIPP In 151-90, the method for regulation measures most probable pore size and the aperture concentration degree of carrier.

In following example and comparative example, use the 3271E commercially available from Rigaku electric machine industry Co., Ltd. Type Xray fluorescence spectrometer, is analyzed measuring to the content of element each in catalyst.

In following example and comparative example, in the X-ray that model is X ' pert commercially available from Philips company On diffractometer, measuring average particulate diameter and the degree of crystallinity of carrier, wherein, degree of crystallinity is relative crystallinity, It is to measure according to the method for regulation in RIPP139-90.

In following example and comparative example, it is QCY-according to the method for regulation in GB3635-1983 in model The resistant to breakage of crushing strength analyzer (the Ministry of Chemical Industry's alkaline institute manufactures) the upper mensuration carrier of 602 is strong Degree.

In following example and comparative example, pressure is all in terms of gauge pressure.

Embodiment 1

Take SB powder (commercially available from SASOL company, relative crystallinity 95.4%, grain size 49.0nm, to do Base content is 75%) 84.0g, Siral40 powder (commercially available from SASOL company, silica content is 40%, Contents on dry basis is 77.5%) 32.2g, Beta molecular sieve (builds the limited public affairs of feldspathization share commercially available from Hunan Department, silica alumina ratio is 63.4, and contents on dry basis is 83 weight %) 8.4 grams, Y type molecular sieve A(lattice constantDegree of crystallinity 81.4%, Na₂O0.02%, butt 86%, preparation method sees ZL01118446.9, embodiment 6, molecular sieve I) 6.1g, add sesbania powder 3g and be dry mixed uniformly, to obtain dry powder. 2mL concentrated nitric acid (concentration is 65 weight %, lower same) is added the beaker being contained with 91mL deionized water In, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain for extruding Raw mixture (temperature of raw mixture is 40 DEG C)).The mixture obtained is sent into banded extruder In, it is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the extrudate temperature in the exit of described extruder It it is 68 DEG C.Extrudate is dried 5 hours at 120 DEG C.Then, in air atmosphere, the temperature of 560 DEG C Under degree, roasting 3 hours, in roasting process, the flow of air is 35L hour^-1, after being cooled to room temperature Obtain support according to the present invention, be designated as A1.The most probable pore size of this carrier, aperture concentration degree and intensity List in Table 1.

Embodiment 2

Take CL powder (to take from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm, do Base content is 71%) 77.4g, Siral30 powder (commercially available from SASOL company, silica content is 30%, Contents on dry basis is 76%) 53.3g, Beta molecular sieve (commercially available from Hunan Jianchang Petrochemical Co., Ltd, Silica alumina ratio is 63.4, and contents on dry basis is 83 weight %) 3.7 grams, Y type molecular sieve A(lattice constantDegree of crystallinity 81.4%, Na₂O0.02%, butt 86%, preparation method sees ZL01118446.9, embodiment 6, molecular sieve I) 2.4g, add sesbania powder 3g and be dry mixed uniformly, to obtain dry powder. 3mL concentrated nitric acid (concentration is 65 weight %, lower same) is added the beaker being contained with 101mL deionized water In, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain for extruding Raw mixture (temperature of raw mixture is 55 DEG C).The mixture obtained is sent in banded extruder, Being extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the extrudate temperature in the exit of described extruder is 79 ℃.Extrudate is dried 5 hours at 110 DEG C.Then, in air atmosphere, the temperature of 570 DEG C Under, roasting 3 hours, in roasting process, the flow of air is 35L hour^-1, obtain after being cooled to room temperature To support according to the present invention, it is designated as A2.The most probable pore size of this carrier, aperture concentration degree and intensity exist Table 1 is listed.

Embodiment 3

Take C1 powder (commercially available from SASOL company, relative crystallinity 93.1%, grain size is 53.0nm, Contents on dry basis is 74.5%) (commercially available from SASOL company, silica content is 79.2g, Siral30 powder 30%, contents on dry basis is 76%) 40.3g, Beta molecular sieve (builds the limited public affairs of feldspathization share commercially available from Hunan Department, silica alumina ratio is 63.4, and contents on dry basis is 83 weight %) 3.6 grams, Y type molecular sieve B(lattice constantDegree of crystallinity 87.1%, Na₂O0.094%, butt 83%, preparation method sees ZL01118446.9, embodiment 1, molecular sieve-4 A) 9.8g, add sesbania powder 3g and be dry mixed uniformly, to be done Powder.3.5mL concentrated nitric acid (concentration is 65 weight %, lower same) is added and is contained with 94mL deionized water Beaker in, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir, used Raw mixture in extrusion.Being sent in banded extruder by the mixture obtained, being extruded into circumscribed circle diameter is 1.4 The butterfly bar of millimeter, the extrudate temperature in the exit of described extruder is 42 DEG C.By extrudate at 115 DEG C It is dried 8 hours.Then, in air atmosphere, at a temperature of 560 DEG C, roasting 4 hours, roasting Cheng Zhong, the flow of air is 200L hour^-1, obtain support according to the present invention after being cooled to room temperature, note For A3.The most probable pore size of this carrier, aperture concentration degree and intensity are listed in Table 1.

Embodiment 4

Take SB powder (commercially available from SASOL company, relative crystallinity 95.4%, grain size 49.0nm, to do Base content is 75%) 60.0g, Siral10 powder (commercially available from SASOL company, silica content is 10%, Contents on dry basis is 74.5%) 67.1g, Beta molecular sieve (builds the limited public affairs of feldspathization share commercially available from Hunan Department, silica alumina ratio is 63.4, and contents on dry basis is 83 weight %) 1.2 grams, Y type molecular sieve B(lattice constantDegree of crystallinity 87.1%, Na₂O0.094%, butt 83%, preparation method sees ZL01118446.9, embodiment 1, molecular sieve-4 A) 4.9g, add sesbania powder 3g and be dry mixed uniformly, to be done Powder.1mL concentrated nitric acid (concentration is 65 weight %, lower same) is added and is contained with 85mL deionized water In beaker, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain for The raw mixture (temperature of raw mixture is 42 DEG C) of extrusion).The mixture obtained is sent into extrusion In machine, it is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the extrudate temperature in the exit of described extruder Degree is 70 DEG C.Extrudate is dried 12 hours at 105 DEG C.Then, in air atmosphere, at 580 DEG C At a temperature of, roasting 2 hours, in roasting process, the flow of air is 35L hour^-1, it is cooled to room Obtain support according to the present invention after temperature, be designated as A4.The most probable pore size of this carrier, aperture concentration degree and Intensity is listed in Table 1.

Embodiment 5

Take C1 powder (commercially available from SASOL company, relative crystallinity 93.1%, grain size is 53.0nm, Contents on dry basis is 74.5%) (commercially available from SASOL company, silica content is 41.6g, Siral10 powder 10%, contents on dry basis is 74.5%) 70.9g, Beta molecular sieve (builds feldspathization share commercially available from Hunan limited Company, silica alumina ratio is 63.4, and contents on dry basis is 83 weight %) 10.7 grams, Y type molecular sieve A(structure cell ConstantDegree of crystallinity 81.4%, Na₂O0.02%, butt 86%, preparation method sees ZL01118446.9, embodiment 6, molecular sieve I) 6.1g, add sesbania powder 3g and be dry mixed uniformly, to obtain dry powder. 1.5mL concentrated nitric acid (concentration is 65 weight %, lower same) is added the burning being contained with 84mL deionized water In Bei, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain for squeezing The raw mixture gone out.Being sent in banded extruder by the mixture obtained, being extruded into circumscribed circle diameter is 1.4 millimeters Butterfly bar, the extrudate temperature in the exit of described extruder is 44 DEG C.Extrudate is dried at 120 DEG C 5 hours.Then, in air atmosphere, at a temperature of 560 DEG C, roasting 3 hours, roasting process In, the flow of air is 35L hour^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A5.The most probable pore size of this carrier, aperture concentration degree and intensity are listed in Table 1.

Embodiment 6

Take SB powder (commercially available from SASOL company, relative crystallinity 95.4%, grain size 49.0nm, to do Base content is 75%) 80.0g, Siral30 powder (commercially available from SASOL company, silica content is 30%, Contents on dry basis is 76%) 19.7g, Beta molecular sieve (commercially available from Hunan Jianchang Petrochemical Co., Ltd, Silica alumina ratio is 63.4, and contents on dry basis is 83 weight %) 11.8 grams, Y type molecular sieve C (lattice constantDegree of crystallinity 85.7%, Na₂O0.032%, butt 85%, preparation method sees ZL01118446.9, embodiment 3, molecular sieve C) 18.3g, add sesbania powder 3g and be dry mixed uniformly, to be done Powder.2.5mL concentrated nitric acid (concentration is 65 weight %, lower same) is added and is contained with 86mL deionized water Beaker in, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir, used Raw mixture (temperature of raw mixture is 40 DEG C) in extrusion.The mixture obtained is sent into extrusion In machine, it is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the extrudate temperature in the exit of described extruder Degree is 68 DEG C.Extrudate is dried 4 hours at 125 DEG C.Then, in air atmosphere, at 600 DEG C At a temperature of, roasting 3 hours, in roasting process, the flow of air is 65L hour^-1, it is cooled to room temperature After obtain support according to the present invention, be designated as A6.The most probable pore size of this carrier, aperture concentration degree and strong Degree is listed in Table 1.

Embodiment 7

Take CL powder (taking from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm) (commercially available from SASOL company, silica content is 10% to 46.4g, Siral10 powder, and contents on dry basis is 74.5%) (commercially available from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 80.5g, Beta molecular sieve 63.4, contents on dry basis is 83%) 1.2 grams, Y type molecular sieve D (lattice constantDegree of crystallinity 72.5%, Na₂O0.13%, butt 81%, Chang Ling catalyst plant produces) 6.25g, add sesbania powder 3g and be dry mixed Uniformly, to obtain dry powder.3.5mL concentrated nitric acid (concentration is 65 weight %, lower same) is added and is contained with In the beaker of 91mL deionized water, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir Mix uniformly, obtain the raw mixture (temperature of raw mixture is 70 DEG C) for extrusion).To obtain Mixture send in banded extruder, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, described extruder The extrudate temperature in exit is 91 DEG C.Extrudate is dried 5 hours at 120 DEG C.Then, at air gas In atmosphere, at a temperature of 560 DEG C, roasting 3 hours, in roasting process, the flow of air is that 35L is little Time^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A7.The most probable pore size of this carrier, Aperture concentration degree and intensity are listed in Table 1.

Embodiment 8

Take CL powder (taking from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm) 59. 2g, Siral20 powder (commercially available from SASOL company, silica content is 10%, and contents on dry basis is 75%) (commercially available from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4 to 66.6g, Beta molecular sieve, dry Base content is 83%) 1.2 grams, Y type molecular sieve E(lattice constantDegree of crystallinity 70.9%, Na₂O0.18%, butt 79%, Chang Ling catalyst plant produces) 3.7g, add sesbania powder 3g and be dry mixed uniformly, To obtain dry powder.3.5mL concentrated nitric acid (concentration is 65 weight %, lower same) is added and is contained with 95mL In the beaker of deionized water, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir all Even, obtain the raw mixture (temperature of raw mixture is 31 DEG C) for extrusion.The mixing that will obtain Thing is sent in banded extruder, is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the exit of described extruder Extrudate temperature be 58 DEG C.Extrudate is dried 3 hours at 130 DEG C.Then, in air atmosphere, At a temperature of 620 DEG C, roasting 2 hours, in roasting process, the flow of air is 155L hour^-1, Obtain support according to the present invention after being cooled to room temperature, be designated as A8.The most probable pore size of this carrier, aperture Concentration degree and intensity are listed in Table 1.

Embodiment 9

Take CL powder (taking from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm) (commercially available from SASOL company, silica content is 70% to 57.7g, Siral70 powder, and contents on dry basis is 81%) (commercially available from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 55.5g, Beta molecular sieve 63.4, contents on dry basis is 83%) 1.2 grams, Y type molecular sieve F(lattice constantDegree of crystallinity 79.9%, Na₂O0.09%, butt 79%, Chang Ling catalyst plant produces) 2.5g, add sesbania powder 3g and be dry mixed Uniformly, to obtain dry powder.3.5mL concentrated nitric acid (concentration is 65 weight %, lower same) is added and is contained with In the beaker of 102mL deionized water, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and Stir, obtain the raw mixture (temperature of raw mixture is 66 DEG C) for extrusion.To obtain Mixture send in banded extruder, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, described extruder The extrudate temperature in exit is 93 DEG C.Extrudate is dried 5 hours at 110 DEG C.Then, at air gas In atmosphere, at a temperature of 570 DEG C, roasting 3 hours, in roasting process, the flow of air is that 35L is little Time^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A9.The most probable pore size of this carrier, Aperture concentration degree and intensity are listed in Table 1.

Embodiment 10

Take CL powder (taking from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm) (commercially available from SASOL company, silica content is 10% to 39.4g, Siral10 powder, and contents on dry basis is 74.5%) (commercially available from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 80.5g, Beta molecular sieve 63.4, contents on dry basis is 83 weight %) 1.2 grams, Y type molecular sieve D (lattice constantDegree of crystallinity 72.5%, Na₂O0.13%, butt 81%, Chang Ling catalyst plant produces) 6.25g, add sesbania powder 3g and be dry mixed Uniformly, to obtain dry powder.3.5mL concentrated nitric acid (concentration is 65 weight %, lower same) is added and is contained with In the beaker of 82mL deionized water, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir Mix uniformly, obtain the raw mixture for extrusion.The mixture obtained is sent in banded extruder, outside being extruded into Connecing the butterfly bar that circular diameter is 1.4 millimeters, the extrudate temperature in the exit of described extruder is 43 DEG C.Will Extrudate is dried 4 hours at 120 DEG C.Then, in air atmosphere, at a temperature of 550 DEG C, roasting 4 hours, in roasting process, the flow of air was 105L hour^-1, obtain after being cooled to room temperature according to this The carrier of invention, is designated as A10.The most probable pore size of this carrier, aperture concentration degree and intensity arrange in Table 1 Go out.

Embodiment 11

Take SD powder (commercially available from Shandong Aluminum Plant, relative crystallinity 103%, grain size 46.0nm) (commercially available from SASOL company, silica content is 10% to 92.9g, Siral20 powder, and contents on dry basis is 75%) (commercially available from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 46.6g, Beta molecular sieve 63.4, contents on dry basis is 83%) 6.0 grams, Y type molecular sieve E(lattice constantDegree of crystallinity 70.9%, Na₂O0.18%, butt 79%, Chang Ling catalyst plant produces) 0.62g, add sesbania powder 3g and do It is mixed even, to obtain dry powder.2mL concentrated nitric acid (concentration is 65 weight %, lower same) is added and is contained with In the beaker of 82mL deionized water, mix homogeneously, to obtain acid solution.By acid solution and dry powder blend, and stir Mix uniformly, obtain the raw mixture (temperature of raw mixture is 25 DEG C) for extrusion.By obtain Mixture is sent in banded extruder, is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, going out of described extruder Extrudate temperature at Kou is 58 DEG C.Extrudate is dried 4 hours at 125 DEG C.Then, at air atmosphere In, at a temperature of 600 DEG C, roasting 3 hours, in roasting process, the flow of air is 65L hour^{- 1}, obtain support according to the present invention after being cooled to room temperature, be designated as A11.The most probable pore size of this carrier, Aperture concentration degree and intensity are listed in Table 1.

Embodiment 12

Take SD powder (commercially available from Shandong Aluminum Plant, relative crystallinity 103%, grain size 46.0nm) (commercially available from SASOL company, silica content is 70% to 40.0g, Siral70 powder, and contents on dry basis is 81%) (commercially available from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 43.2g, Beta molecular sieve 63.4, contents on dry basis is 83%) 17.6 grams, Y type molecular sieve A(lattice constantDegree of crystallinity 81.4%, Na₂O0.02%, butt 86%, preparation method sees ZL01118446.9, embodiment 6, molecule Sieve I) 24.1g, add sesbania powder 3g and be dry mixed uniformly, to obtain dry powder.By 2.5mL concentrated nitric acid, (concentration is 65 weight %, lower same) add in the beaker being contained with 88mL deionized water, mix homogeneously, to obtain acid Liquid.By acid solution and dry powder blend, and stirring, (raw material mixes to obtain the raw mixture for extrusion The temperature of thing is 40 DEG C).Being sent in banded extruder by the mixture obtained, being extruded into circumscribed circle diameter is 1.4 millis The butterfly bar of rice, the extrudate temperature in the exit of described extruder is 66 DEG C.Extrudate is done at 115 DEG C Dry 5 hours.Then, in air atmosphere, at a temperature of 550 DEG C, roasting 3 hours, roasting process In, the flow of air is 115L hour^-1, obtain support according to the present invention after being cooled to room temperature, be designated as Carrier A12.Most probable pore size, aperture concentration degree and the intensity be somebody's turn to do are listed in Table 1.

Comparative example 1

Using method same as in Example 7 to prepare carrier, except for the difference that, raw mixture is described in entrance Temperature during extruder is room temperature (25 DEG C), and the carrier obtained is designated as B1.The most probable pore size of this carrier, Aperture concentration degree and intensity are listed in Table 1.

Table 1

Embodiment 7 and comparative example 1 are compared it can be seen that use carrier prepared by the method for the present invention Not only there is bigger aperture, but also there is higher aperture concentration degree and mechanical strength.

Embodiment 13～24 is used for catalyst according to the invention and application thereof and method for hydrogen cracking are described.

Embodiment 13～24

By ammonium metatungstate (commercially available from Chang Ling catalyst plant) and nickel nitrate (commercially available from Beijing benefit profit chemical reagent Factory) it is dissolved in the water, it is configured to impregnation liquid, impregnates preparation example with this impregnation liquid respectively according to hole saturation Carrier A1～A12 of preparation in 1～12, and the carrier after dipping is done at 120 DEG C in air atmosphere Dry 2 hours, then at 350 DEG C in air atmosphere roasting 5 hours, thus prepare there is hydrogenation Catalyst, be designated as catalyst X1～X12 respectively.Ammonium metatungstate and the load on carrier of nickel nitrate Amount makes, on the basis of the total amount of catalyst, in terms of oxide, in catalyst X1～X12, and WO₃With NiO content is respectively 27.0 weight % and 2.6 weight %.

Comparative example 2

Using and prepare catalyst with the identical method of embodiment 13～24, except for the difference that, carrier is comparative example The carrier B 1 of 1 preparation.The catalyst prepared is designated as CX.Ammonium metatungstate and the bearing on carrier of nickel nitrate Carrying capacity makes, on the basis of the total amount of catalyst, in terms of oxide, and WO₃It is respectively with NiO content 27.0 weight % and 2.6 weight %.

Embodiment 25～28 is used for illustrating application and the method for hydrogen cracking of catalyst according to the invention.

Embodiment 25～28

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

Catalyst is X1, X5, X7, X11.

Catalyst breakage is become the granule of a diameter of 0.5～1.0 millimeter, in 200 milliliters of fixed bed reactors Loading this catalyst 200 milliliters, before logical oil, first catalyst is 15.0MPa in hydrogen dividing potential drop, and temperature is Vulcanize under conditions of 300 DEG C 28 hours, be 14.7MPa in hydrogen dividing potential drop afterwards, logical when temperature is 350 DEG C Entering raw oil, hydrogen-oil ratio is 900 volume/volume, and during liquid, volume space velocity is 0.75h^-1, and in reaction 400 Sample after hour.

Evaluate catalysis activity and the intermediate oil selectivity of catalyst, wherein:

Activity refers to that recovered (distilled) temperature is higher than the cracking reaction temperature of needs when the conversion ratio of the hydrocarbon ils of 350 DEG C is 60% Degree, wherein, the catalysis activity of cracking reaction temperature the lowest explanation catalyst is the highest；

Intermediate oil selectivity refers to that the content of the fraction that recovered (distilled) temperature is 132～371 DEG C accounts for recovered (distilled) temperature Percentage ratio less than the gross mass of 371 DEG C of fractions.Result is listed in table 2.

Comparative example 2

The method identical with embodiment 25～28 is used to evaluate the performance of catalyst prepared by comparative example 2.Knot Fruit is listed in table 2.

Table 2

Embodiment	Catalyst	Activity (DEG C)	Selectivity (%)
				25	X1	381.1	82.9
26	X5	384.4	83.9
				27	X7	387.8	83.9
28	X11	386.4	83.5
				Comparative example 2	CX	391.6	83.1

Catalyst X7 is identical with the content of hydrogenation active metals component with catalyst CX carrier composition, but In terms of the result that table 1 is given, the hole concentration degree of catalyst X7 used carrier A7 is apparently higher than catalyst The carrier B 1 of CX.The result listed by table 2 sees that the present invention provides the activity and selectivity of catalyst the highest In reference catalyst.

Claims (26)

1. a hydrocracking catalyst, this catalyst contains containing heat-resistant inorganic oxide matrix, Y type Molecular sieve and the carrier of Beta molecular sieve, on the basis of described carrier, heat resistant inorganic oxygen in described carrier The content of compound is 50-98 weight %, and the content of Y type molecular sieve is to being less than more than 0 weight % In 40 weight %, the content of Beta molecular sieve is extremely less than or equal to 40 weight % more than 0 weight %, Wherein, the most probable pore size of described carrier is 1～30nm, and aperture concentration degree is 22～48, described Can several apertures be to use BET method to measure, described aperture concentration degree refers to use BET method to measure Specific pore volume is long-pending with in the distribution curve of varying aperture, the ratio of the height at peak and the halfwidth at this peak.

Catalyst the most according to claim 1, it is characterised in that the most probable of described carrier Aperture is 2～20nm, and aperture concentration degree is 22～48.

Catalyst the most according to claim 2, it is characterised in that the most probable of described carrier Aperture is 5～10nm, and aperture concentration degree is 27～40.

Catalyst the most according to claim 1, it is characterised in that with described carrier as base Standard, in described carrier, the content of heat-resistant inorganic oxide is 60-95 weight %, containing of Y type molecular sieve Amount is 0.5-35 weight %, and the content of Beta molecular sieve is 0.5-35 weight %.

Catalyst the most according to claim 1, it is characterised in that with described carrier as base Standard, in described carrier, the content of heat-resistant inorganic oxide is 60-95 weight %, containing of Y type molecular sieve Amount is 0.5-30 weight %, and the content of Beta molecular sieve is 0.5-25 weight %.

Catalyst the most according to claim 1, it is characterised in that described heat resistant inorganic aoxidizes Thing one or several in aluminium oxide, silica-alumina, silicon oxide, titanium oxide, zirconium oxide Kind.

Catalyst the most according to claim 6, it is characterised in that described heat resistant inorganic aoxidizes One or more in aluminium oxide, silica-alumina, silicon oxide of thing.

Catalyst the most according to claim 7, it is characterised in that described heat resistant inorganic aoxidizes Thing is aluminium oxide, silica-alumina and their mixture.

Catalyst the most according to claim 1, it is characterised in that adding in described catalyst Hydrogen activity metal component is selected from least one group VIII and the metal group of at least one vib Point, to count and on the basis of described catalyst by oxide, the content of described group VIII metal component is 2～10 weight %, the content of described vib metals component is 10～40 weight %.

Catalyst the most according to claim 9, it is characterised in that described group VIII metal Component is selected from nickel and/or cobalt, and described vib metals component is selected from molybdenum and/or tungsten, in terms of oxide And on the basis of described catalyst, the content of described group VIII metal component is 2.5～6.5 weights Amount %, the content of described vib metals component is 15～30 weight %.

The preparation method of 11. hydrocracking catalysts according to claim 1, contains including preparation Heat-resistant inorganic oxide matrix, Y type molecular sieve and the carrier of Beta molecular sieve, the preparation side of this carrier Method comprises the following steps: (1) by heat-resistant inorganic oxide and/or the precursor of heat-resistant inorganic oxide, Y type molecular sieve and Beta molecular sieve, peptizer and water mixing, to provide raw material；(2) by described former Material is sent in extruder, and extrudes after kneading in described extruder, to obtain molded body；(3) Described molded body is carried out roasting, and to obtain described carrier, wherein, described molded body is in described extrusion The temperature in the exit of machine is 40～150 DEG C.

12. methods according to claim 11, it is characterised in that described molded body squeezes described The temperature in the exit going out machine is 50～120 DEG C.

13. methods according to claim 12, it is characterised in that described molded body is described The temperature in the exit of extruder is 60～100 DEG C.

14. methods according to claim 13, it is characterised in that described molded body is described The temperature in the exit of extruder is 60～98 DEG C.

15. method according to claim 11, it is characterised in that on the basis of described carrier, The content of heat-resistant inorganic oxide during the consumption of each component makes final described carrier in described step (1) For 50-98 weight %, the content of Y type molecular sieve is to less than or equal to 40 weights more than 0 weight % The content of amount %, Beta molecular sieve is to less than or equal to 40 weight % more than 0 weight %.

16. methods according to claim 15, it is characterised in that with described carrier as base Standard, heat-resistant inorganic oxide during the consumption of each component makes final described carrier in described step (1) Content is 60-95 weight %, and the content of Y type molecular sieve is 0.5-35 weight %, Beta molecular sieve Content is 0.5-35 weight %.

17. methods according to claim 16, it is characterised in that with described carrier as base Standard, heat-resistant inorganic oxide during the consumption of each component makes final described carrier in described step (1) Content is 60-95 weight %, and the content of Y type molecular sieve is 0.5-30 weight %, Beta molecular sieve Content is 0.5-25 weight %.

18. methods according to claim 11, it is characterised in that described heat-resistant inorganic oxide One or several in aluminium oxide, silica-alumina, silicon oxide, titanium oxide, zirconium oxide Kind.

19. methods according to claim 18, it is characterised in that described heat resistant inorganic aoxidizes One or more in aluminium oxide, silica-alumina, silicon oxide of thing.

20. methods according to claim 19, it is characterised in that described heat resistant inorganic aoxidizes Thing is aluminium oxide, silica-alumina and their mixture.

21. methods according to claim 11, it is characterised in that described heat-resistant inorganic oxide The average particulate diameter of precursor be 30～100nm.

22. methods according to claim 21, it is characterised in that described heat resistant inorganic aoxidizes The average particulate diameter of the precursor of thing is 30～80nm.

23. according to the method described in claim 11 or 21, it is characterised in that described heat resistant inorganic The precursor of oxide contains boehmite, the relative crystallinity of described boehmite be 80% with On.

24. methods according to claim 23, it is characterised in that described heat resistant inorganic aoxidizes The precursor of thing contains boehmite, and the relative crystallinity of described boehmite is more than 90%.

25. methods according to claim 24, it is characterised in that described heat resistant inorganic aoxidizes The precursor of thing contains boehmite, the relative crystallinity of described boehmite be 90～ 110%.

26. 1 kinds of method for hydrogen cracking, are included under hydrocracking condition and are connect with catalyst by hydrocarbon ils Touch, wherein, the catalyst that described catalyst provides for any one in aforementioned claim 1～10.