CN104043478A - Hydrocracking catalyst, preparation and application thereof - Google Patents

Abstract

The invention relates to a hydrocracking catalyst, preparation and application thereof. The catalyst contains a carrier containing a heatproof inorganic oxide matrix, a Y type molecular sieve and a Beta molecular sieve. Specifically, the carrier has a most probable aperture of 1-30nm and an aperture concentration degree of 22-48. The most probable aperture is measured by a BET method. The aperture concentration degree refers to the ratio of a peak height to the peak's full width half maximum in a BET method measured distribution curve about the change of a specific pore volume along with the aperture. The preparation method of the catalyst includes preparation of the carrier containing the heatproof inorganic oxide matrix, the Y type molecular sieve and the Beta molecular sieve. The preparation method of the carrier includes subjecting a precursor of the heatproof inorganic oxide, the Y type molecular sieve and the Beta molecular sieve, a peptizer and water to mixing and extrusion molding, with the temperature of molded body at the outlet of the extruder being 40-150DEG C. Compared with the prior art, the hydrocracking catalyst provided by the invention has high catalytic activity and middle distillate selectivity when used for hydrocarbon oil processing.

Description

A kind of hydrocracking catalyst and preparation and application

Technical field

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

Background technology

In recent years, crude oil heaviness and in poor quality tendency are day by day obvious in world wide, meanwhile, the demand of intermediate oil and reformation, steam crack material are but constantly increased.This impels heavy distillate process technology to be developed rapidly, and catalyst is wherein the most important and crucial factor.

The catalyst transforming for mink cell focus or large molecule, except requiring catalyst to have larger aperture and enough pore volume, also requires the pore-size distribution of catalyst mesopore to concentrate (, aperture concentration degree is high).

Because the catalyst for mink cell focus or macromolecular conversion is generally by the active component with catalytic action is loaded on carrier and obtained, therefore preparation has larger aperture and pore volume, and the key with the catalyst of higher aperture concentration degree is to provide the carrier that has large aperture and have higher aperture concentration degree.

At present, the method that is generally used for describing aperture concentration degree (or referred to as hole concentration degree) is: calculate pore volume in given pore diameter range and account for the percentage of total pore volume, this percentage is higher, thinks that aperture concentration degree is also higher.But the aperture concentration degree that the method that accounts for the percentage of total pore volume by calculating pore volume in given pore diameter range is carried out evaluation carrier is difficult to reflect exactly the pore-size distribution of carrier.

CN101757929A discloses and has adopted in the distribution curve of the specific pore volume long-pending (dV/dlog (D)) of being measured by BET method with aperture, and the ratio of the height at peak and the halfwidth at this peak is the aperture concentration degree of evaluate catalysts exactly.On this basis, CN101757929A also discloses a kind of hydrocracking catalyst, this catalyst contains carrier and loads on the IV B family metal component in hydrogenation activity composition and the periodic table of elements on this carrier, wherein, the most probable aperture of described carrier is 6～14nm, and aperture concentration degree is more than 7.Although it can be more than 7 that CN101757929A discloses the aperture concentration degree of described carrier, from the disclosed embodiment of CN101757929A, the aperture concentration degree of carrier is up to 21.4, needs further to improve.

To sum up, how to obtain have high catalytic activity and intermediate oil optionally hydrocracking catalyst remain a technical problem urgently to be resolved hurrily.

Summary of the invention

The object of the invention is to overcome prior art above shortcomings, provide a kind of and there is high catalytic activity and optionally hydrocracking catalyst of intermediate oil, and the preparation method and application of this catalyst.

The present inventor finds in practice process, and it is selective that the aperture concentration degree that improves carrier can significantly improve activity and the intermediate oil of catalyst of the hydrocracking of being prepared by this carrier.But, adopt the method (for example, the disclosed method of CN101757929A) of prior art not obtain to there is higher aperture concentration degree the carrier of (for example, aperture concentration degree is more than 22).The present inventor's research is found: preparing formed body with extruder by extrusion molding, thereby while obtaining carrier, making described formed body is 40～150 DEG C in the temperature in the exit of extruder, can obtain to have larger aperture and aperture concentration degree is more than 22 carrier.While adopting the carrier of hydrocracking catalyst of being prepared by the method to prepare hydrocracking catalyst, catalyst not only has higher catalytic activity, and it is selective to have higher intermediate oil.

The invention provides a kind of hydrocracking catalyst, this catalyst contains containing heat-resistant inorganic oxide matrix, Y zeolite and the Beta molecular sieve carrier of (also claiming beta-molecular sieve), wherein, the most probable aperture of described carrier is 1～30nm, aperture concentration degree is 22～48, aperture, described most probable hole is to adopt BET method to measure, described aperture concentration degree refers to and adopts the specific pore volume that BET method is measured to amass in (dV/dlog (D)) distribution curve with varying aperture, the ratio of the height at peak and the halfwidth at this peak.

The present invention also provides the preparation method of described hydrocracking catalyst, comprise the carrier of preparation containing heat-resistant inorganic oxide matrix, Y zeolite and Beta molecular sieve, the preparation method of this carrier comprises the following steps: (1) mixes the precursor of heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve, peptizing agent and water, to supply raw materials; (2) described raw material is sent in extruder, and after kneading, extruded in described extruder, to obtain formed body; (3) described formed body is carried out to roasting, to obtain described carrier, wherein, described formed body is 40～150 DEG C in the temperature in the exit of described extruder.

The present invention further provides a kind of method for hydrogen cracking, the method is included under hydrocracking condition, and hydrocarbon ils is contacted with catalyst, and wherein, described catalyst is catalyst provided by the invention.

Not only there is larger aperture and pore volume according to carrier of the present invention, and there is higher aperture concentration degree.The hydrocracking catalyst containing Y zeolite and Beta molecular sieve of being prepared by this carrier is adding man-hour for hydrocarbon ils, has high catalytic activity and intermediate oil selective.

Brief description of the drawings

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

Detailed description of the invention

According to catalyst provided by the invention, wherein said carrier contains heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve.The most probable aperture of described carrier can be 1～30nm, is preferably 2～20nm, more preferably 5～10nm.The aperture concentration degree of described carrier is 22～48, is preferably 25～48, more preferably 27～40.Taking described carrier as benchmark, in described carrier, the content of heat-resistant inorganic oxide is 50～98 % by weight, be preferably 60～95 % by weight, the content of Y zeolite is for being greater than 0 % by weight to being less than or equal to 40 % by weight, be preferably 0.5～35 % by weight, more preferably 0.5～30 % by weight, the content of beta-molecular sieve is for being greater than 0 % by weight to being less than or equal to 40 % by weight, be preferably 0.5～35 % by weight, more preferably 0.5～25 % by weight.

In the present invention, term " aperture, most probable hole " refers to: in the time adopting BET method to measure the pore structure of sample, in the distribution curve of the specific pore volume long-pending (dV/dlog (D)) obtaining with aperture, the corresponding aperture of maximum of specific pore volume long-pending (dV/dlog (D)).Adopt BET method to measure the pore structure of porous mass, known in those skilled in the art with the method that obtains the long-pending distribution curve with aperture of specific pore volume, for example can be according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety the first edition, the volumes such as Yang Cuiding) in the RIPP151-90 that records the method that specifies measure.

In the present invention, term " aperture concentration degree " refers to: in the time adopting BET method to measure the pore structure of sample, and in the long-pending distribution curve with aperture of the specific pore volume of acquisition, the ratio of the halfwidth at peak height and this peak.The ratio of the halfwidth at peak height and this peak is larger, shows that the aperture intensity of carrier is higher.Aperture concentration degree can be referred to as hole concentration degree.

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

Fig. 1 is the long-pending distribution curve schematic diagram with aperture of specific pore volume.In Fig. 1, abscissa is the aperture of carrier, adopts logarithmic coordinates, and unit is ordinate is that specific pore volume is long-pending.In Fig. 1, M represents peak height (, maximum dV/dlog (D)), and N represents that (,, on described distribution curve, ordinate is half-peak breadth (halfwidth) two points between distance).In the time of calculated hole diameters concentration degree, halfwidth and peak height all adopt identical long measure.

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

According to the present invention, described heat-resistant inorganic oxide is selected from and can be used as arbitrarily the heat-resistant inorganic oxide that hydrogenation class catalyst carrier is used, for example, can be selected from one or more in aluminium oxide, silica-alumina, silica, titanium oxide, zirconia, preferably one or more in self-alumina, silica-alumina, silica, more preferably aluminium oxide, silica-alumina and their mixture.They can be that commercially available commodity can be also to adopt existing method preparation arbitrarily.

The silica alumina ratio of described Beta molecular sieve can carry out suitable selection according to the concrete application scenario of final Kaolinite Preparation of Catalyst, is not particularly limited.In a preferred embodiment, preferably silica alumina ratio is 25～200, more preferably 25～150 Beta molecular sieve.They can be commercially available commodity, can be also to adopt existing method preparation arbitrarily.

Described Y zeolite can, for the conventional various Y zeolites in this area, be not particularly limited.For example, be selected from HY, USY, REY, USREY one or more etc.In a preferred embodiment, preferably wherein lattice constant is y zeolite.They can be that commercially available commodity can be also to adopt existing method preparation arbitrarily.

According to the present invention, described carrier can have various shapes according to concrete application scenario.For example, described carrier can be spherical, bar shaped, annular, cloverleaf pattern, honeycombed and butterfly.

According to hydrocracking catalyst provided by the invention, hydrogenation active metals component wherein can be to can be used as arbitrarily the hydrogenation active metals that hydrocracking catalyst uses, for example, be selected from the noble metal component of group VIII, be selected from least one group VIII base metal and the combination that is selected from least one group vib metal.In the time that described hydrogenation active metals component is selected from least one group VIII base metal and is selected from the combination of at least one group vib metal, the metal component of preferred group VIII is nickel and/or cobalt, the metal component of preferred group vib is molybdenum and/or tungsten, in oxide and taking described catalyst as benchmark, the content of described group vib metal component is 10～40 % by weight, be preferably 15～30 % by weight, the content of described group VIII metal is 2～10 % by weight, is preferably 2.5～6.5 % by weight.

According to catalyst provided by the invention, can also contain any material that does not affect the performance that the invention provides catalyst and maybe can improve catalyst performance provided by the invention.As contained one or both in the components such as phosphorus, boron or fluorine, in element and taking catalyst as benchmark, the content of above-mentioned auxiliary agent is no more than 10 % by weight, is preferably 0.5-5 % by weight; Also can contain organic matter, wherein organic type includes but not limited to alcohols (comprising polyalcohol), amine (comprising polyamine), acid and ester class etc.In carbon and taking described catalyst as benchmark, the content of described organic additive is no more than 20 % by weight of total catalyst weight.

According to method for preparing catalyst provided by the invention, wherein the preparation method of carrier comprises the following steps: (1) mixes the precursor of heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve, peptizing agent and water, to supply raw materials; (2) described raw material is sent in extruder, and after kneading, extruded in described extruder, to obtain formed body; (3) described formed body is carried out to roasting, to obtain described carrier, wherein, described formed body is 40～150 DEG C in the temperature in the exit of described extruder.

With extruder, raw material is being extruded, to obtain in the process of formed body, conventionally especially extrusion temperature is not controlled to (be generally room temperature or lower than 40 DEG C), but the present inventor finds in research process, making formed body is 40～150 DEG C in the temperature in the exit of described extruder, can make the most probable aperture of the carrier of being prepared by this formed body and aperture concentration degree meet previously described requirement.Preferably, described formed body is 50～120 DEG C in the temperature in the exit of described extruder.Further preferably, described formed body is 60～100 DEG C in the temperature in the exit of described extruder, can obtain so higher aperture concentration degree.More preferably, described formed body is 60～98 DEG C in the temperature in the exit of described extruder.

According to the present invention, can step (2) adopt the whole bag of tricks make the formed body extruded by described extruder in the temperature in the exit of this extruder within scope mentioned above.For example: can be in the process of described raw material being carried out to kneading in extruder or extrude, by regulating cooling condition or the heating condition of extruder or kneading machine fuselage and/or head, make the formed body extruded by described extruder in the temperature in the exit of this extruder within scope mentioned above.It is known in the field regulating the method for extruder or the fuselage of kneading machine and/or the cooling condition of head or heating condition, repeats no more herein.

The present inventor further finds in research process, in described step (1) by the temperature of described raw material (, described raw material is in the temperature of the porch of described extruder) be 40～100 DEG C, not only can make the most probable aperture of the carrier of preparation meet previously described requirement, but also can make the carrier of preparation there is higher aperture concentration degree, the carrier of preparation also has higher mechanical strength simultaneously.

Therefore, one of the present invention preferred embodiment in, the described raw material that described step (1) obtains is 40～100 DEG C in the temperature of the porch of described extruder.Have under the aperture of expection and the prerequisite of aperture concentration degree at the carrier of guaranteeing preparation, the angle of the mechanical strength of the carrier of preparing from further raising, the described raw material that described step (1) obtains is preferably 40～80 DEG C in the temperature of the porch of described extruder, more preferably 50～80 DEG C.

Can adopt the whole bag of tricks to make described raw material is 40～100 DEG C (being preferably 40～80 DEG C, more preferably 50～80 DEG C) in the temperature of the porch of described extruder.

Usually, the process that the precursor of described heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve, peptizing agent and water can be mixed is carried out under heating condition, it is 40～100 DEG C (being preferably 40～80 DEG C, more preferably 50～80 DEG C) in the temperature of the porch of described extruder that the condition of described heating makes the raw material obtaining.For example: can be in the mixed process of the precursor of heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve, peptizing agent and water, within the scope of the temperature of raw material that heats to make preparation by external heat source in 40～100 DEG C (preferably 40～80 DEG C, more preferably 50～80 DEG C); Also can be by least one heating in the precursor of described heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve, peptizing agent and water, then mix, the temperature that makes the described raw material obtaining is 40～100 DEG C and (is preferably 40～80 DEG C, more preferably 50～80 DEG C), and the raw material that is 40～100 DEG C (being preferably 40～80 DEG C, more preferably 50～80 DEG C) by this temperature is sent in described extruder.For example, peptizing agent is mixed with water, and then the mixture obtaining is mixed with precursor, Y zeolite and the Beta molecular sieve of described heat-resistant inorganic oxide, afterwards described compound is sent into extruder for shaping.Wherein, can be by hot water be mixed with peptizing agent, obtain hot mixture, again this hot mixture is mixed with precursor, Y zeolite and the Beta molecular sieve of described heat-resistant inorganic oxide, thereby preparation temperature is 40～100 DEG C (is preferably 40～80 DEG C, more preferably 50～80 DEG C) raw material, and the raw material that is 40～100 DEG C (being preferably 40～80 DEG C, more preferably 50～80 DEG C) by this temperature is sent in extruder.

Wherein, at described raw material, comprise in precursor, Y zeolite and the Beta molecular sieve mixture material of heat-resistant inorganic oxide, the consumption of each component can be selected according to the heat-resistant inorganic oxide in the carrier of expection and the content of molecular sieve.Taking described carrier as benchmark, in a preferred embodiment, it is 50～98 % by weight that the consumption of each component makes the content of heat-resistant inorganic oxide in final carrier, be preferably 60～95 % by weight, the content of Y zeolite, for being greater than 0 % by weight to being less than or equal to 40 % by weight, is preferably 0.5～35 % by weight, more preferably 0.5～30 % by weight, the content of Beta molecular sieve, for being greater than 0 % by weight to being less than or equal to 40 % by weight, is preferably 0.5～35 % by weight, more preferably 0.5～25 % by weight.

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

Described Y zeolite can be the conventional various Y zeolites in this area, for example, be selected from HY, USY, REY, USREY one or more etc., be not particularly limited.In a preferred embodiment, preferably lattice constant is y zeolite.They can be that commercially available commodity can be also to adopt existing method preparation arbitrarily.

Described heat-resistant inorganic oxide is selected from and can be used as arbitrarily the heat-resistant inorganic oxide that hydrogenation class catalyst carrier is used, for example, can be selected from one or more in aluminium oxide, silica-alumina, silica, titanium oxide, zirconia, preferably one or more in self-alumina, silica-alumina, silica.They can be that commercially available commodity can be also to adopt existing method preparation arbitrarily.

In the present invention, the precursor of described heat-resistant inorganic oxide refers to the hydrous oxide that can form described heat-resistant inorganic oxide under roasting condition.Taking aluminium oxide as example, its precursor is hydrated alumina, comprises aluminium hydroxide, boehmite, boehmite, gibbsite, and the gel or the colloidal sol etc. that contain above-mentioned hydrated alumina.They can be that commercially available commodity can be also to adopt existing method preparation arbitrarily.

In detailed description of the invention, the average particulate diameter that the present invention prepares the precursor of the described heat-resistant inorganic oxide of described carrier use can be the conventional average particulate diameter in this area.The present inventor finds in research process: when the average particulate diameter of the precursor of described heat-resistant inorganic oxide is 30～100nm, the carrier of being prepared by method of the present invention has higher aperture concentration degree.Prepare the angle of the aperture concentration degree of carrier from further raising, the average particulate diameter of the precursor of described heat-resistant inorganic oxide is preferably 30～80nm, more preferably 30～60nm.Further preferably, the average particulate diameter of the precursor of described heat-resistant inorganic oxide is 40～60nm.

The precursor of the heat-resistant inorganic oxide of average particulate diameter within previously described scope, can be selected from the commercially available commodity that meet this requirement, also can adopt the conventional the whole bag of tricks in this area that the average particulate diameter of the precursor of described heat-resistant inorganic oxide is met the demands.For example, by before use the precursor of described heat-resistant inorganic oxide being ground and/or sieved, thereby the average particulate diameter of the precursor of described heat-resistant inorganic oxide is met the demands.

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

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

In formula I, D is average particulate diameter;

λ is the wavelength of X ray;

β _hKLthe broadening degree causing because of grain size refinement for diffraction maximum, wherein, β _hKL=B-B ₀;

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

B ₀for the broadening degree of instrument;

θ is incidence angle.

According to the present invention, the precursor of described heat-resistant inorganic oxide preferably contains the precursor of aluminium oxide.Wherein, the precursor of described aluminium oxide is preferably boehmite.Although adopt various boehmites all can form aluminium oxide, and realize object of the present invention, but the present inventor finds in research process: employing degree of crystallinity is that more than 80% boehmite can have under the condition of large aperture and pore volume at the carrier that guarantee final preparation, further improve the aperture concentration degree of the carrier obtaining, and then make catalyst of the present invention there is higher catalytic activity and intermediate oil selective, can also improve the mechanical strength of the carrier of preparation simultaneously.

In the present invention, described degree of crystallinity is relative crystallinity, to adopt " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety the first edition, the Yang Cui volume such as surely) in the method that specifies in the RIPP139-90 that records measure, wherein, the standard specimen using is the sample that is numbered S87-16B, the absolute crystallinity of this standard specimen is 98.0%, can be commercially available by Research Inst. of Petroleum Processing, SINOPEC.

One of the present invention preferred embodiment in, the precursor of described heat-resistant inorganic oxide contains boehmite, and the relative crystallinity of described boehmite is more than 80%, to be preferably more than 90%.The angle of the aperture concentration degree of the carrier obtaining from further raising, the relative crystallinity of described boehmite is preferably 90～110%.

One of the present invention more preferred embodiment in, the precursor of described heat-resistant inorganic oxide contains boehmite, the relative crystallinity of described boehmite is more than 80%, and the average particulate diameter of described boehmite is 30～100nm.

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

In the most preferred embodiment of one of the present invention, described raw material is 40～80 DEG C in the temperature of the porch of described extruder, described formed body is 60～98 DEG C in the temperature in the exit of described extruder, and the precursor of described heat-resistant inorganic oxide contains boehmite, the relative crystallinity of described boehmite is 90～110%, and the average particulate diameter of described boehmite is 30～80nm.The carrier of preparing according to this embodiment has higher aperture concentration degree and the mechanical strength of Geng Gao.

According to method of the present invention, in the described described raw material that the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve, peptizing agent and water are mixed to get, the amount of peptizing agent wherein can be carried out suitable selection according to the kind of the precursor of used heat-resistant inorganic oxide.Usually, taking the total amount of described raw material as benchmark, the content of described peptizing agent can be 0.1～5 % by weight, is preferably 0.5～4 % by weight.The present invention is not particularly limited for the kind of described peptizing agent, can be that the routine of this area is selected.In the present invention, the instantiation of described peptizing agent can be but be not limited to: nitric acid, hydrochloric acid, phosphoric acid, trichloroacetic acid and citric acid.

According to method of the present invention, at the described raw material that is enough to make the precursor of described heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve, peptizing agent and water to be mixed to get, under the prerequisite of extruding through described extruder, the present invention is not particularly limited for the consumption of described water, can be that the routine of this area is selected.

According to method of the present invention, described raw material can also contain extrusion aid.The content of described extrusion aid and kind can be that the routine of this area is selected.Usually, taking described raw material as benchmark, the consumption of described extrusion aid is 0.1～5 % by weight, is preferably 1～3 % by weight.In the present invention, the example of described extrusion aid can be but be not limited to: one or more in starch, cellulose, organic carboxyl acid, polyalcohol, organic amine and surfactant.

Wherein, described starch includes but not limited to sesbania powder, and described cellulose includes but not limited to methylcellulose etc.

Described organic carboxyl acid refers to the organic compound in molecular structure with one or more carboxyls, for example " Lan Shi chemistry handbook " second edition, the organic carboxyl acid of enumerating in 1.26～1.27.Preferably, described organic carboxyl acid is that carbon number is 1～20 unary organic carboxylic acid or polynary organic carboxyl acid (for example: binary organic carboxyl acid).In the present invention, the example of described organic carboxyl acid can be but be not limited to: formic acid, acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid and benzenpropanoic acid.

Described polyalcohol refers to the organic compound in molecular structure with more than two hydroxyl.The example of described polyalcohol can be but be not limited to: ethylene glycol, glycerine and butanediol.

Described organic amine refers to the organic compound that contains one or more amidos in molecular structure.The example of described organic amine can be but be not limited to: monoethanolamine, diethanol amine, triethanolamine, N methyldiethanol amine and urea.

Described surfactant can be anionic surfactant, cationic surface active agent, amphoteric ionic surfactant and nonionic surface active agent.The example of described anionic surfactant can be but be not limited to: stearic acid and neopelex.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 be not limited to: lecithin, amino acid type surfactant and betaine type amphoteric surfactant.The example of described nonionic surface active agent can be but be not limited to: fatty glyceride, aliphatic acid sorb ester (span series), polysorbate (tween series of surfactants), polyoxyethylene-type surfactant and polyox-yethylene-polyoxypropylene block copolymer.

In the present invention, described extruder can be the various extruders of this area use.The present invention is not particularly limited this, can be that the routine of this area is selected.

In the present invention, described method and the condition that formed body is carried out to roasting being not particularly limited, can be 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, is preferably 2～5 hours.Described roasting can be carried out in will and spirit atmosphere in office, can be oxygen-containing atmosphere, also can in oxygen-free atmosphere, carry out, and can contain water vapour, can be also air or other gas of bone dry.This patent does not do any restriction to calcination atmosphere.

According to the preparation method of carrier of the present invention, before described formed body is carried out to roasting, can also comprise described formed body is dried, described dry can carrying out under the normal condition of this area, for example: described dry temperature can be 100～200 DEG C, the described dry time can be 2～12 hours.Described dry can carrying out under the condition of normal pressure also can carry out under the condition of decompression, is not particularly limited.Described dry can carrying out in will and spirit atmosphere in office, can be oxygen-containing atmosphere, and this patent does not do any restriction to dry atmosphere.

Usually, the most probable aperture of prepared according to the methods of the invention carrier can be 1～30nm, is preferably 2～20nm, more preferably 5～10nm; Aperture concentration degree can be 22～48, and being preferably 25～48(can be for example 25～40), more preferably 27～40.

According to the preparation method of hydrocracking catalyst provided by the invention, comprise to the step of introducing hydrogenation active metals component on described carrier, hydrogenation active metals component wherein can be the hydrogenation active metals that Chang Zuowei hydrocracking catalyst uses arbitrarily, for example, be selected from the noble metal component of group VIII, be selected from least one group VIII base metal and the combination that is selected from least one group vib metal.

In the time that described hydrogenation active metals component is selected from least one group VIII base metal and is selected from the combination of at least one group vib metal, the metal component of preferred group VIII is nickel and/or cobalt, the metal component of preferred group vib is molybdenum and/or tungsten, in oxide and taking described catalyst as benchmark, it is 10～40 % by weight that the introduction volume of described group vib metal component makes the content of group vib metal component in final catalyst, be preferably 15～30 % by weight, making the introduction volume of described group VIII metal component make the content of group VIII metal component in final catalyst is 2～10 % by weight, be preferably 2.5～6.5 % by weight.

Can be any means that those skilled in the art inform to what introduce hydrogenation active metals component on described carrier, for example, carrier described in the solution impregnation of the compound that can contain described hydrogenation active metals component by use, is dried, the step of roasting or not roasting afterwards.

In the present invention, the example of the described compound that contains group vib metal can be but be not limited to: one or more in wolframic acid, molybdic acid, metatungstic acid, ethyl metatungstic acid, para-molybdic acid, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate and ethyl ammonium metatungstate.

The described compound containing group VIII metal is preferably taking nickel as cationic oxysalt, one or more in cationic anaerobic hydrochlorate taking nickel as cationic anaerobic hydrochlorate, taking cobalt as cationic oxysalt with taking cobalt.In the present invention, the example of the described compound containing group VIII metal can be but be not limited to: one or more in nickel nitrate, nickelous sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, nickel chloride and cobalt chloride.

According to the present invention, can adopt the conventional various solvents in this area to prepare the solution of the compound that contains described active component, as long as described compound can be dissolved in described solvent, form the solution of stable homogeneous.For example: described solvent can be the alcohol (as: ethanol) that water or carbon number are 1～5, is preferably water and/or ethanol, more preferably water.

The method of described dipping can for the conventional various dipping methods in this area, for example, can be the saturated infusion process in hole.The present invention was not particularly limited for the time of described dipping and the number of times of dipping, as long as the amount of the active component with catalytic action on the catalyst that can guarantee finally to obtain meets concrete instructions for use.Usually, the time of described dipping can be 0.5～12 hour.

According to the present invention, carry out dry method and condition is not particularly limited for the carrier of compound that load is had to described hydrogenation active metals component.Usually, described dry temperature can be 80～350 DEG C, is preferably 100～300 DEG C; The described dry time can be 0.5～24 hour, is preferably 1～12 hour.

In the time that catalyst after drying need to carry out roasting, the present invention is not particularly limited described method of roasting and condition, can be conventional method and the condition of this area.Usually, the temperature of described roasting can be 350～700 DEG C, is preferably 400～650 DEG C; The time of described roasting can be 0.2～12 hour, is preferably 1～10 hour.Described roasting can be carried out in will and spirit atmosphere in office, and this patent does not limit calcination atmosphere.

According to preparation method provided by the invention, when in described catalyst, also contain in components such as being selected from boron, phosphorus or fluorine one or both adjuvant components time, also comprise and introduce the step that is selected from one or more components in the components such as boron, phosphorus or fluorine, the described introducing method that is selected from the components such as boron, phosphorus or fluorine can pass through number of ways, for example, can be by directly mixing with silicon-containing compound containing the compound of described auxiliary agent, moulding roasting; Can be to contact with described carrier after the compound that contains described auxiliary agent is mixed with to mixed solution with the compound that contains hydrogenation active metals component; Can also be after independent the compound that contains auxiliary agent obtain solution, to contact with described carrier and roasting.In the time that auxiliary agent and hydrogenation active metals are introduced described carrier respectively, preferably first with containing, auxiliary compound solution contacts with described carrier and roasting, contact with the solution of the compound that contains hydrogenation active metals component more afterwards, for example, by the method for dipping, described sintering temperature is 250-600 DEG C, be preferably 350-500 DEG C, roasting time is 2-8 hour, is preferably 3-6 hour.

The carrier that catalyst provided by the invention adopts, not only has large aperture, and has high aperture concentration degree, is particularly suitable for the hydrocracking catalyst as hydrocarbon ils, thereby produces the hydrocarbon system cut having compared with low boiling and lower molecular weight.

According to method for hydrogen cracking of the present invention, described hydrocarbon ils can be various heavy mineral oils, artificial oil or their mixture.Particularly, the example of described hydrocarbon ils can be but be not limited to: vacuum gas oil (VGO), metal removal oil, reduced crude, depitching 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, improves the conversion ratio of hydrocarbon ils in hydrocracking and intermediate oil optionally, be not particularly limited for all the other conditions of hydrocracking, and can be the normal condition of this area.Usually, described hydrocracking condition comprises: temperature can be 200～650 DEG C, is preferably 300～510 DEG C; In gauge pressure, pressure can be 3～24 MPas, is preferably 4～15 MPas; Hydrogen to oil volume ratio can be 150～2500; When liquid, volume space velocity can be 0.1～30 hour ^-1, be preferably 0.2～10 hour ^-1.

According to method for hydrogen cracking of the present invention, described catalyst preferably carries out presulfurization before use.The condition of described presulfurization can be the normal condition of this area.For example, the condition of described presulfurization can comprise: under hydrogen exists, at the temperature of 140～370 DEG C, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material.According to method for hydrogen cracking of the present invention, described presulfurization can be carried out outward at reactor, also can original position sulfuration in reactor.

Describe the present invention in detail below in conjunction with embodiment.

The reagent using in following examples and comparative example, except special instruction, is chemically pure reagent.

In following examples and comparative example, in the model being purchased from Quantachrome company be full-automatic specific surface and pore size distribution determining instrument on, adopt BET method to measure most probable aperture and the aperture concentration degree of carrier according to the method specifying in RIPP151-90.

In following examples and comparative example, adopt the 3271E type Xray fluorescence spectrometer being purchased from Rigaku electric machine industry Co., Ltd., the content of each element in catalyst is analyzed to mensuration.

In following examples and comparative example, on the X-ray diffractometer that to be purchased from the model of Philips company be X ' pert, measure average particulate diameter and the degree of crystallinity of carrier, wherein, degree of crystallinity is relative crystallinity, is to measure according to the method specifying in RIPP139-90.

In following examples and comparative example, the upper crushing strength of measuring carrier of the crushing strength analyzer that is QCY-602 in model according to the method specifying in GB3635-1983 (manufacture of alkaline research institute of the Ministry of Chemical Industry).

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

Embodiment 1

Get SB powder and (be purchased the company from SASOL, relative crystallinity 95.4%, grain size 49.0nm, contents on dry basis is 75%) 84.0g, Siral40 powder (is purchased the company from SASOL, silica content is 40%, contents on dry basis is 77.5%) 32.2g, (be purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4 to Beta molecular sieve, contents on dry basis is 83 % by weight) 8.4 grams, Y zeolite A(lattice constant degree of crystallinity 81.4%, Na ₂o0.02%, butt 86%, preparation method is referring to ZL01118446.9, embodiment 6, molecular sieve I) 6.1g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.2mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 91mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of raw mixture is 40 DEG C) for extruding).The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 68 DEG C.Extrudate is dried to 5 hours at 120 DEG C.Then, in air atmosphere, at the temperature of 560 DEG C, roasting 3 hours, in roasting process, the flow of air is 35L hour ^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A1.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 2

Get CL powder and (take from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm, contents on dry basis is 71%) 77.4g, Siral30 powder (is purchased the company from SASOL, silica content is 30%, contents on dry basis is 76%) 53.3g, (be purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4 to Beta molecular sieve, contents on dry basis is 83 % by weight) 3.7 grams, Y zeolite A(lattice constant degree of crystallinity 81.4%, Na ₂o0.02%, butt 86%, preparation method is referring to ZL01118446.9, embodiment 6, molecular sieve I) 2.4g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.3mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 101mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of raw mixture is 55 DEG C) for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 79 DEG C.Extrudate is dried to 5 hours at 110 DEG C.Then, in air atmosphere, at the temperature of 570 DEG C, roasting 3 hours, in roasting process, the flow of air is 35L hour ^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A2.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 3

Get C1 powder and (be purchased the company from SASOL, relative crystallinity 93.1%, grain size is 53.0nm, and contents on dry basis is 74.5%) 79.2g, Siral30 powder (is purchased the company from SASOL, silica content is 30%, contents on dry basis is 76%) 40.3g, (be purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4 to Beta molecular sieve, contents on dry basis is 83 % by weight) 3.6 grams, Y zeolite B(lattice constant degree of crystallinity 87.1%, Na ₂o0.094%, butt 83%, preparation method is referring to ZL01118446.9, embodiment 1, molecular sieve-4 A) 9.8g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.3.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 94mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 42 DEG C.Extrudate is dried to 8 hours at 115 DEG C.Then, in air atmosphere, at the temperature of 560 DEG C, roasting 4 hours, in roasting process, the flow of air is 200L hour ^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A3.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 4

Get SB powder and (be purchased the company from SASOL, relative crystallinity 95.4%, grain size 49.0nm, contents on dry basis is 75%) 60.0g, Siral10 powder (is purchased the company from SASOL, silica content is 10%, contents on dry basis is 74.5%) 67.1g, (be purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4 to Beta molecular sieve, contents on dry basis is 83 % by weight) 1.2 grams, Y zeolite B(lattice constant degree of crystallinity 87.1%, Na ₂o0.094%, butt 83%, preparation method is referring to ZL01118446.9, embodiment 1, molecular sieve-4 A) 4.9g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.1mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 85mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of raw mixture is 42 DEG C) for extruding).The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 70 DEG C.Extrudate is dried to 12 hours at 105 DEG C.Then, in air atmosphere, at the temperature of 580 DEG C, roasting 2 hours, in roasting process, the flow of air is 35L hour ^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A4.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 5

Get C1 powder and (be purchased the company from SASOL, relative crystallinity 93.1%, grain size is 53.0nm, and contents on dry basis is 74.5%) 41.6g, Siral10 powder (is purchased the company from SASOL, silica content is 10%, contents on dry basis is 74.5%) 70.9g, (be purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4 to Beta molecular sieve, contents on dry basis is 83 % by weight) 10.7 grams, Y zeolite A(lattice constant degree of crystallinity 81.4%, Na ₂o0.02%, butt 86%, preparation method is referring to ZL01118446.9, embodiment 6, molecular sieve I) 6.1g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.1.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 84mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 44 DEG C.Extrudate is dried to 5 hours at 120 DEG C.Then, in air atmosphere, at the temperature of 560 DEG C, roasting 3 hours, in roasting process, 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.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 6

Get SB powder and (be purchased the company from SASOL, relative crystallinity 95.4%, grain size 49.0nm, contents on dry basis is 75%) 80.0g, Siral30 powder (is purchased the company from SASOL, silica content is 30%, contents on dry basis is 76%) 19.7g, (be purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4 to Beta molecular sieve, contents on dry basis is 83 % by weight) 11.8 grams, Y zeolite C (lattice constant degree of crystallinity 85.7%, Na ₂o0.032%, butt 85%, preparation method is referring to ZL01118446.9, embodiment 3, molecular sieve C) 18.3g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.2.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 86mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of raw mixture is 40 DEG C) for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 68 DEG C.Extrudate is dried to 4 hours at 125 DEG C.Then, in air atmosphere, at the 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 A6.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 7

Get CL powder and (take from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm) 46.4g, Siral10 powder (be purchased the company from SASOL, silica content is 10%, and contents on dry basis is 74.5%) 80.5g, Beta molecular sieve (is purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4, and contents on dry basis is 83%) 1.2 grams, Y zeolite D (lattice constant degree of crystallinity 72.5%, Na ₂o0.13%, butt 81%, Chang Ling catalyst plant is produced) 6.25g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.3.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 91mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of raw mixture is 70 DEG C) for extruding).The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 91 DEG C.Extrudate is dried to 5 hours at 120 DEG C.Then, in air atmosphere, at the temperature of 560 DEG C, roasting 3 hours, in roasting process, the flow of air is 35L hour ^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A7.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 8

Get CL powder and (take from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm) 59.2g, Siral20 powder (be purchased the company from SASOL, silica content is 10%, and contents on dry basis is 75%) 66.6g, Beta molecular sieve (is purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4, and contents on dry basis is 83%) 1.2 grams, Y zeolite E(lattice constant degree of crystallinity 70.9%, Na ₂o0.18%, butt 79%, Chang Ling catalyst plant is produced) 3.7g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.3.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 95mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of raw mixture is 31 DEG C) for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 58 DEG C.Extrudate is dried to 3 hours at 130 DEG C.Then, in air atmosphere, at the 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.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 9

Get CL powder and (take from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm) 57.7g, Siral70 powder (be purchased the company from SASOL, silica content is 70%, and contents on dry basis is 81%) 55.5g, Beta molecular sieve (is purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4, and contents on dry basis is 83%) 1.2 grams, Y zeolite F(lattice constant degree of crystallinity 79.9%, Na ₂o0.09%, butt 79%, Chang Ling catalyst plant is produced) 2.5g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.3.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 102mL deionized water, mix, 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 extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 93 DEG C.Extrudate is dried to 5 hours at 110 DEG C.Then, in air atmosphere, at the temperature of 570 DEG C, roasting 3 hours, in roasting process, the flow of air is 35L hour ^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A9.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 10

Get CL powder and (take from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm) 39.4g, Siral10 powder (be purchased the company from SASOL, silica content is 10%, and contents on dry basis is 74.5%) 80.5g, Beta molecular sieve (is purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4, and contents on dry basis is 83 % by weight) 1.2 grams, Y zeolite D (lattice constant degree of crystallinity 72.5%, Na ₂o0.13%, butt 81%, Chang Ling catalyst plant is produced) 6.25g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.3.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 82mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 43 DEG C.Extrudate is dried to 4 hours at 120 DEG C.Then, in air atmosphere, at the temperature of 550 DEG C, roasting 4 hours, in roasting process, the flow of air is 105L hour ^-1, obtain support according to the present invention after being cooled to room temperature, be designated as A10.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 11

Getting SD powder (is purchased from Shandong Aluminum Plant, relative crystallinity 103%, grain size 46.0nm) 92.9g, Siral20 powder (be purchased the company from SASOL, silica content is 10%, and contents on dry basis is 75%) 46.6g, Beta molecular sieve (is purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4, and contents on dry basis is 83%) 6.0 grams, Y zeolite E(lattice constant degree of crystallinity 70.9%, Na ₂o0.18%, butt 79%, Chang Ling catalyst plant is produced) 0.62g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.2mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 82mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of raw mixture is 25 DEG C) for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 58 DEG C.Extrudate is dried to 4 hours at 125 DEG C.Then, in air atmosphere, at the 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.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Embodiment 12

Getting SD powder (is purchased from Shandong Aluminum Plant, relative crystallinity 103%, grain size 46.0nm) 40.0g, Siral70 powder (be purchased the company from SASOL, silica content is 70%, and contents on dry basis is 81%) 43.2g, Beta molecular sieve (is purchased from Hunan Jianchang Petrochemical Co., Ltd, silica alumina ratio is 63.4, and contents on dry basis is 83%) 17.6 grams, Y zeolite A(lattice constant degree of crystallinity 81.4%, Na ₂o0.02%, butt 86%, preparation method is referring to ZL01118446.9, embodiment 6, molecular sieve I) 24.1g, add sesbania powder 3g and be dry mixed evenly, to obtain dry powder.2.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) is added in the beaker that is contained with 88mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of raw mixture is 40 DEG C) for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described extruder is 66 DEG C.Extrudate is dried to 5 hours at 115 DEG C.Then, in air atmosphere, at the temperature of 550 DEG C, roasting 3 hours, in roasting process, 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 A 12.Most probable aperture, aperture concentration degree and the intensity of being somebody's turn to do are listed in table 1.

Comparative example 1

Adopt the method identical with embodiment 7 to prepare carrier, different, the temperature of raw mixture in the time entering described extruder is room temperature (25 DEG C), and the carrier obtaining is designated as B1.Most probable aperture, aperture concentration degree and the intensity of this carrier are listed in table 1.

Table 1

Embodiment 7 is compared and can be found out with comparative example 1, adopt carrier prepared by method of the present invention not only to there is larger aperture, but also there is higher aperture concentration degree and mechanical strength.

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

Embodiment 13～24

Ammonium metatungstate (being purchased from Chang Ling catalyst plant) and nickel nitrate (being purchased from the sharp chemical reagent factory of Beijing benefit) are dissolved in the water, be mixed with maceration extract, flood respectively the carrier A 1～A12 of preparation in preparation example 1～12 according to hole saturation with this maceration extract, and the carrier after dipping is dried to 2 hours at 120 DEG C in air atmosphere, then roasting 5 hours in air atmosphere at 350 DEG C, thereby make the catalyst with hydrogenation, be designated as respectively catalyst X1～X12.The load capacity on carrier of ammonium metatungstate and nickel nitrate makes, taking the total amount of catalyst as benchmark, and in oxide, in catalyst X1～X12, WO ₃be respectively 27.0 % by weight and 2.6 % by weight with NiO content.

Comparative example 2

Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 13～24, different, carrier is carrier B 1 prepared by comparative example 1.The catalyst making is designated as CX.The load capacity on carrier of ammonium metatungstate and nickel nitrate makes, taking the total amount of catalyst as benchmark, and in oxide, WO ₃be respectively 27.0 % by weight and 2.6 % by weight with NiO content.

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 adopts and once passes through flow process, and feedstock oil adopts sand gently to subtract two, and the density (20 DEG C) of this feedstock oil is 0.9062g/cm ³, refraction index (20 DEG C) is 1.4852; Initial boiling point (IBP) is 299 DEG C, and 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.

It is the particle of 0.5～1.0 millimeter that catalyst breakage is become to diameter, in 200 milliliters of fixed bed reactors, pack 200 milliliters of this catalyst into, before logical oil, first catalyst is 15.0MPa in hydrogen dividing potential drop, and temperature is to vulcanize 28 hours under the condition of 300 DEG C, is 14.7MPa afterwards in hydrogen dividing potential drop, passes into feedstock oil in the time that temperature is 350 DEG C, hydrogen-oil ratio is 900 volume/volume, and when liquid, volume space velocity is 0.75h ^-1, and in reaction sampling after 400 hours.

Catalytic activity and the intermediate oil of evaluate catalysts are selective, wherein:

Activity refers to the cracking reaction temperature needing when recovered (distilled) temperature is 60% higher than the conversion ratio of the hydrocarbon ils of 350 DEG C, and wherein, the catalytic activity of the lower explanation catalyst of cracking reaction temperature is higher;

Intermediate oil selectively refers to that recovered (distilled) temperature is that the content of the cut of 132～371 DEG C accounts for the percentage that recovered (distilled) temperature is less than the gross mass of 371 DEG C of cuts.The results are shown in table 2.

Comparative example 2

Adopt the performance of catalyst prepared by the method evaluation comparative example 2 identical with embodiment 25～28.The results are shown in table 2.

Table 2

Embodiment	Catalyst	Active (DEG C)	Selectively (%)
				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 the result providing from table 1, the hole concentration degree of catalyst X7 used carrier A7 is apparently higher than the carrier B 1 of catalyst CX.The result of being listed by table 2 sees that the activity and selectivity that the invention provides catalyst is all higher than reference catalyst.

Claims (27)

1. a hydrocracking catalyst, this catalyst contains the carrier containing heat-resistant inorganic oxide matrix, Y zeolite and Beta molecular sieve, wherein, the most probable aperture of described carrier is 1～30nm, aperture concentration degree is 22～48, described most probable aperture is to adopt BET method to measure, and described aperture concentration degree refers in the long-pending distribution curve with varying aperture of the specific pore volume that adopts BET method to measure, the ratio of the height at peak and the halfwidth at this peak.

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

3. according to the catalyst described in 2, it is characterized in that, the most probable aperture of described carrier is 5～10nm, and aperture concentration degree is 27～40.

4. according to the catalyst described in 1, it is characterized in that, taking described carrier as benchmark, in described carrier, the content of heat-resistant inorganic oxide is 50-98 % by weight, the content of Y zeolite is for being greater than 0 % by weight to being less than or equal to 40 % by weight, and the content of Beta molecular sieve is for being greater than 0 % by weight to being less than or equal to 40 % by weight.

5. according to the catalyst described in 4, it is characterized in that, taking described carrier as benchmark, in described carrier, the content of heat-resistant inorganic oxide is 60-95 % by weight, and the content of Y zeolite is 0.5-35 % by weight, and the content of Beta molecular sieve is 0.5-35 % by weight.

6. according to the catalyst described in 1, it is characterized in that, taking described carrier as benchmark, in described carrier, the content of heat-resistant inorganic oxide is 60-95 % by weight, and the content of Y zeolite is 0.5-30 % by weight, and the content of Beta molecular sieve is 0.5-25 % by weight.

7. according to the catalyst described in 1, it is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica-alumina, silica, titanium oxide, zirconia.

8. according to the catalyst described in 7, it is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica-alumina, silica.

9. according to the catalyst described in 8, it is characterized in that, described heat-resistant inorganic oxide is aluminium oxide, silica-alumina and their mixture.

10. according to the catalyst described in 1, it is characterized in that, hydrogenation active metals component in described catalyst is selected from the metal component of at least one group VIII and at least one group vib, in oxide and taking described catalyst as benchmark, the content of described group VIII metal component is 2～10 % by weight, and the content of described group vib metal component is 10～40 % by weight.

11. according to the catalyst described in 10, it is characterized in that, described group VIII metal component is selected from nickel and/or cobalt, described group vib metal component is selected from molybdenum and/or tungsten, in oxide and taking described catalyst as benchmark, the content of described group VIII metal component is 2.5～6.5 % by weight, and the content of described group vib metal component is 15～30 % by weight.

12. according to the preparation method of the hydrocracking catalyst described in 1, comprise the carrier of preparation containing heat-resistant inorganic oxide matrix, Y zeolite and Beta molecular sieve, the preparation method of this carrier comprises the following steps: (1) mixes the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, Y zeolite and Beta molecular sieve, peptizing agent and water, to supply raw materials; (2) described raw material is sent in extruder, and after kneading, extruded in described extruder, to obtain formed body; (3) described formed body is carried out to roasting, to obtain described carrier, wherein, described formed body is 40～150 DEG C in the temperature in the exit of described extruder.

13. according to the method described in 12, it is characterized in that, described formed body is 50～120 DEG C in the temperature in the exit of described extruder.

14. according to the method described in 13, it is characterized in that, described formed body is 60～100 DEG C in the temperature in the exit of described extruder.

15. according to the method described in 14, it is characterized in that, described formed body is 60～98 DEG C in the temperature in the exit of described extruder.

16. according to the method described in 12, it is characterized in that, taking described carrier as benchmark, in described step (1), to make the content of heat-resistant inorganic oxide in final described carrier be 50-98 % by weight to the consumption of each component, the content of Y zeolite is for being greater than 0 % by weight to being less than or equal to 40 % by weight, and the content of Beta molecular sieve is for being greater than 0 % by weight to being less than or equal to 40 % by weight.

17. according to the method described in 16, it is characterized in that, taking described carrier as benchmark, in described step (1), to make the content of heat-resistant inorganic oxide in final described carrier be 60-95 % by weight to the consumption of each component, the content of Y zeolite is 0.5-35 % by weight, and the content of Beta molecular sieve is 0.5-35 % by weight.

18. according to the method described in 17, it is characterized in that, taking described carrier as benchmark, in described step (1), to make the content of heat-resistant inorganic oxide in final described carrier be 60-95 % by weight to the consumption of each component, the content of Y zeolite is 0.5-30 % by weight, and the content of Beta molecular sieve is 0.5-25 % by weight.

19. according to the method described in 12, it is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica-alumina, silica, titanium oxide, zirconia.

20. according to the method described in 19, it is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica-alumina, silica.

21. according to the method described in 20, it is characterized in that, described heat-resistant inorganic oxide is aluminium oxide, silica-alumina and their mixture.

22. according to the method described in 12, it is characterized in that, the average particulate diameter of the precursor of described heat-resistant inorganic oxide is 30～100nm.

23. according to the method described in 22, it is characterized in that, the average particulate diameter of the precursor of described heat-resistant inorganic oxide is 30～80nm.

24. according to the method described in 12 or 22, it is characterized in that, the precursor of described heat-resistant inorganic oxide contains boehmite, and the relative crystallinity of described boehmite is more than 80%.

25. according to the method described in 24, it is characterized in that, the precursor of described heat-resistant inorganic oxide contains boehmite, and the relative crystallinity of described boehmite is more than 90%.

26. according to the method described in 25, it is characterized in that, the precursor of described heat-resistant inorganic oxide contains boehmite, and the relative crystallinity of described boehmite is more than 90～110%.

27. 1 kinds of method for hydrogen cracking, are included under hydrocracking condition hydrocarbon ils are contacted with catalyst, and wherein, described catalyst is aforementioned 1～11 catalyst providing.