CN103028448A - Catalyst and preparation method and application thereof, and hydrocracking method - Google Patents

Abstract

The invention provides a catalyst and a preparation method and an application thereof. The catalyst contains a porous carrier and active ingredients loaded on the porous carrier, wherein the porous carrier contains a heat-resistant inorganic oxide; and the most probable pore diameter of the porous carrier is 1-30 nanometers, and the pore diameter concentration ratio is 22-48. The preparation method of the catalyst comprises loading the active ingredients onto the porous carrier. A preparation method of the porous carrier comprises the following steps of: mixing a precursor which can be used for forming a heat-resistant inorganic oxide with a peptizing agent and water under a roasting condition to provide raw materials; feeding the raw materials into an extruder, and kneading and extruding in the extruder to obtain a formed body, wherein the temperature of the formed body at the outlet of the extruder is 40-150 DEG C; and roasting the formed body to obtain the porous carrier. The invention further provides a hydrocracking method. The hydrocracking method comprises contacting hydrocarbon oil with the catalyst provided by the invention. The catalyst provided by the invention has high catalytic activity and intermediate oil selectivity when applied to catalytic cracking of hydrocarbon oil.

Description

A kind of Catalysts and its preparation method and application and method for hydrogen cracking

Technical field

The present invention relates to a kind of Catalysts and its preparation method and application and method for hydrogen cracking.

Background technology

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

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

Because being used for the catalyst of mink cell focus or macromolecular conversion generally is to load on the porous carrier by the active component that will have catalytic action to obtain, therefore preparation has larger aperture and pore volume, and the key with catalyst of higher aperture concentration degree provides the porous carrier that has large aperture and have higher aperture concentration degree.

At present, the method that is generally used for describing the aperture concentration degree is: calculate the percentage that pore volume in the given pore diameter range accounts for total pore volume, this percentage is higher, thinks that the aperture concentration degree is also higher.But the method that accounts for the percentage of total pore volume by calculating pore volume in the given pore diameter range comes the aperture concentration degree of evaluation carrier to be difficult to reflect exactly the pore-size distribution of carrier.

CN101757929A discloses and has adopted in the long-pending distribution curve of differential with the aperture to the aperture of the specific pore volume of being measured by the BET method, 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 hydrogenation activity composition on this carrier and the 1VB family metal component in the periodic table of elements, wherein, the most probable aperture of described carrier is 6～14nm, and the aperture concentration degree is more than 7.Can be for more than 7 although 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, awaits further to improve.

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

Summary of the invention

The object of the invention is to overcome the prior art above shortcomings, a kind of optionally hydrocracking catalyst of high catalytic activity and intermediate oil that has is provided.

The present inventor finds in practice process, it is selective that the aperture concentration degree that improves carrier can significantly improve catalytic activity and the intermediate oil of the catalyst that is obtained by this carrier, but adopt the method for prior art can not obtain the to have higher aperture concentration degree carrier of (for example: the aperture concentration degree is more than 22).Thereby, the present inventor is on the basis of CN101757929A, carried out more intensive research, find: preparing formed body with extruder by extrusion molding, thereby when obtaining porous carrier, making the temperature of described formed body in the exit of extruder is 40～150 ℃, can obtain to have larger aperture and aperture concentration degree and be the carrier more than 22, the catalyst with hydrogenation by the preparation of this porous carrier not only has higher catalytic activity, and it is selective to have a higher intermediate oil.Finished thus the present invention.

The invention provides a kind of catalyst, this catalyst contains porous carrier and loads on the active component with catalytic action on this porous carrier, described porous carrier contains heat-resistant inorganic oxide, wherein, the most probable aperture of described porous carrier is 1～30nm, the aperture concentration degree of described porous carrier is 22～48, described most probable aperture is to adopt the BET method to measure, described aperture concentration degree refers to adopt in the distribution curve of dV/dr with varying aperture of BET method mensuration, the ratio of the height at peak and the halfwidth at this peak, dV/dr represent the long-pending differential to the aperture of specific pore volume.

The present invention also provides a kind of preparation method of catalyst, the method comprises: the active component that will have catalytic action loads on the porous carrier, wherein, the preparation method of described porous carrier comprises: the precursor that will can form heat-resistant inorganic oxide under roasting condition is mixed with peptizing agent and water, to supply raw materials; Described raw material is sent in the extruder, and in described extruder, after kneading, extruded, to obtain formed body; Described formed body is carried out roasting, and to obtain described porous carrier, wherein, the temperature of described formed body in the exit of described extruder is 40～150 ℃.

The present invention provides again a kind of catalyst by method preparation of the present invention.

The present invention further provides the application of a kind of catalyst according to the invention in the hydrocarbon oil hydrogenation cracking.

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

The employed porous carrier of catalyst according to the invention not only has larger aperture and pore volume, and have higher aperture concentration degree, thereby catalyst according to the invention has high catalytic efficiency when being used for the catalytic cracking of hydrocarbon ils and intermediate oil is selective.

Description of drawings

Fig. 1 is that the long-pending differential to the aperture of the specific pore volume of porous carrier of the embodiment of the invention 1 preparation is with the distribution curve schematic diagram in aperture.

The specific embodiment

The invention provides a kind of catalyst, this catalyst contains porous carrier and loads on the active component with catalytic action on this porous carrier, and described porous carrier contains heat-resistant inorganic oxide.

According to the present invention, suitable selection can be carried out according to the concrete application scenario of described catalyst in the most probable aperture of described porous carrier.Be when having the catalyst of hydrogenation in catalyst according to the invention, the most probable aperture of described porous carrier can be 1～30nm, is preferably 2～20nm, more preferably 5～10nm.

According to the present invention, the aperture concentration degree of described porous carrier can reach 22～48, even can reach 25～48 (for example can be 25～40).Be when having the catalyst of hydrogenation in catalyst according to the invention, the aperture concentration degree of described porous carrier is preferably 27～40.

Among the present invention, term " most probable aperture " refers to: when adopting the BET method to measure the pore structure of sample, the long-pending differential to the aperture of the specific pore volume of acquisition (that is, and dV/dr) in the distribution curve with the aperture, the corresponding aperture of the maximum of dV/dr.Adopt the BET method to measure the pore structure of porous mass, known in those skilled in the art to obtain the long-pending differential to the aperture of specific pore volume with the method for the distribution curve in aperture, for example can be according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety front page, the volumes such as Yang Cuiding) among the RIPP 151-90 of record the method stipulated measure.

Among the present invention, term " aperture concentration degree " refers to: when adopting the BET method to measure the pore structure of sample, and in the long-pending distribution curve of differential with the aperture to the 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 porous carrier is higher.

According to the present invention, when having a plurality of peak in the distribution curve of described dV/dr with varying aperture, the ratio of the peak height at each peak and the halfwidth at this peak all should satisfy above-mentioned requirements.

Fig. 1 is that the long-pending differential to the aperture of the specific pore volume of porous carrier of the embodiment of the invention 1 preparation is with the distribution curve schematic diagram in aperture.Among Fig. 1, abscissa is the aperture of porous carrier, adopts logarithmic coordinates, and unit is

Ordinate is the long-pending differential to the aperture of specific pore volume.Among Fig. 1, M represents peak height (that is, maximum dV/dr), and N represents that (that is, on the described distribution curve, ordinate is halfwidth

Two points between distance).When the calculated hole diameters concentration degree, halfwidth all adopts identical long measure with peak height.

Be when having the catalyst of hydrogenation in catalyst according to the invention, the most probable aperture of described porous carrier can be 1～30nm, and the aperture concentration degree can be 22～48.Preferably, the most probable aperture of described porous carrier is 2～20nm, and the aperture concentration degree is 25～48.Be in the scope of 2～20nm in the most probable aperture of described porous carrier, and when the aperture concentration degree is in 25～48 the scope, catalyst according to the invention can obtain higher catalytic activity and intermediate oil selective when being used for the hydrocracking of hydrocarbon ils.The catalytic activity of the catalyst that finally obtains from further raising and intermediate oil be angle optionally, and the most probable aperture of described porous carrier is 5～10nm more preferably, aperture concentration degree more preferably 27～40.

According to the present invention, described porous carrier contains heat-resistant inorganic oxide.

Among 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 ℃ (for example: decomposition temperature is 300～1000 ℃).

The present invention is not particularly limited for the kind of described heat-resistant inorganic oxide, can be various heat-resistant inorganic oxides that can moulding.Be used for load at porous carrier according to the present invention and have the active component of hydrogenation, when having the catalyst of hydrogenation with formation, described heat-resistant inorganic oxide can be in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and the mesoporous Si-Al one or more; Be preferably in aluminium oxide, silica and the mesoporous Si-Al one or more; More preferably aluminium oxide and/or silica.Of the present invention a kind of preferred embodiment in, described heat-resistant inorganic oxide contains aluminium oxide.

According to the present invention, described porous carrier can also contain molecular sieve.The present invention is not particularly limited for the kind of described molecular sieve, and described molecular sieve can be zeolite molecular sieve and/or non-zeolite molecular sieve.

Among the present invention, the example of described molecular sieve can for but be not limited to: the ZRP molecular sieve, the MCM-41 molecular sieve, erionite, the ZSM-34 molecular sieve, modenite, ZSM-5 molecular sieve, the ZSM-11 molecular sieve, the ZSM-12 molecular sieve, the ZSM-22 molecular sieve, ZSM-23 molecular screen, ZSM-35 molecular sieve, the L-type molecular sieve, Y zeolite, the X-type molecular sieve, the ZSM-3 molecular sieve, the ZSM-4 molecular sieve, the ZSM-18 molecular sieve, the ZSM-20 molecular sieve, the ZSM-48 molecular sieve, the ZSM-57 molecular sieve, faujasite, beta-molecular sieve, the Ω molecular sieve, phosphate aluminium molecular sieve, HTS and SAPO (that is, SAPO) molecular sieve.Be used for the active component that load has hydrogenation at porous carrier according to the present invention, when having the catalyst of hydrogenation with preparation, described molecular sieve is preferably one or more in ZRP molecular sieve, Y zeolite, beta-molecular sieve, modenite, ZSM-5 molecular sieve, MCM-41 molecular sieve, Ω molecular sieve, ZSM-12 molecular sieve and the MCM-22 molecular sieve.

According to the present invention, when described porous carrier contained heat-resistant inorganic oxide and molecular sieve, the ratio between described heat-resistant inorganic oxide and the molecular sieve can be carried out suitable selection according to the desired use of described catalyst.For example, when described catalyst is used for the hydrocracking of hydrocarbon ils, take the total amount of described porous carrier as benchmark, the content of described molecular sieve can be 0.1～66 % by weight, be preferably 0.2～50 % by weight, more preferably 0.5～30 % by weight, more preferably 0.75～20 % by weight; The content of described heat-resistant inorganic oxide can be 34～99.9 % by weight, is preferably 50～99.8 % by weight, more preferably 70～99.5 % by weight, more preferably 80～99.25 % by weight.

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

Catalyst according to the invention also contains the active component with catalytic action that loads on the described porous carrier.The kind of the active component with catalytic action in the catalyst according to the invention can be carried out suitable selection according to the concrete application scenario of described catalyst.

For example, when catalyst according to the invention was used for the hydrocracking of hydrocarbon ils, described active component can be for having the active component of hydrogenation, for example: group vib metal and group VIII metal.Described group vib metal and group VIII metal can be respectively load on the described porous carrier, for example with the various forms of this area routine: described group vib metal and group VIII metal can be respectively be loaded on the described porous carrier with the form of oxide.

The described load capacity of active component on described porous carrier with hydrogenation can be the conventional amount used of this area.Usually, be when having the active component of hydrogenation at described active component, take the total amount of the catalyst that finally obtains as benchmark, in oxide, the amount of described active component can be 5～60 % by weight, is preferably 10～50 % by weight; The amount of described carrier can be 40～95 % by weight, is preferably 50～90 % by weight.When described active component was group vib metal and group VIII metal, in the catalyst that finally obtains, take the total amount of described catalyst as benchmark, in oxide, the content of described group vib metal can be 10～40 % by weight, is preferably 15～30 % by weight; The content of described group VIII metal can be 2～10 % by weight, is preferably 2.5～6.5 % by weight; The content of described porous carrier can be 50～88 % by weight, is preferably 63.5～82.5 % by weight.

The present invention also provides a kind of preparation method of catalyst, and the method comprises: the active component that will have catalytic action loads on the porous carrier.

The method according to this invention, described porous carrier prepares by the following method: the precursor that will can form heat-resistant inorganic oxide under roasting condition is mixed with peptizing agent and water, to supply raw materials; Described raw material is sent in the extruder, and in extruder, after kneading, extruded, to obtain formed body; Described formed body is carried out roasting, and to obtain described porous carrier, wherein, the temperature of described formed body in the exit of described extruder is 40～150 ℃.

According to the present invention, with extruder raw material is being extruded, in the process that obtains formed body, it is (to be lower than 40 ℃) about room temperature that general cooling condition with described extruder is controlled to be the temperature that makes the formed body of extruding, yet the present inventor finds in research process, make the temperature of formed body in the exit of described extruder be 40～150 ℃ can be so that satisfy previously described requirement by most probable aperture and the aperture concentration degree of the porous carrier of this formed body preparation.Preferably, the temperature of described formed body in the exit of described extruder is 60～120 ℃.Further preferably, the temperature of described formed body in the exit of described extruder is 60～100 ℃.More preferably, the temperature of described formed body in the exit of described extruder is 60～98 ℃.When the temperature of described formed body in the exit of described extruder is 60～98 ℃, by the catalyst of the present invention of this formed body preparation have higher catalytic activity and intermediate oil selective.

According to the present invention, the whole bag of tricks can be adopted so that the temperature of formed body in the exit of this extruder of being extruded by described extruder is within the scope mentioned above.For example: can be in the process of described raw material being carried out kneading or extruding in extruder, by regulating cooling condition or the heating condition of extruder fuselage and/or head, so that the temperature of formed body in the exit of this extruder of being extruded by described extruder is within the scope mentioned above.It is known in the field regulating the fuselage of extruder and/or the cooling condition of head or the method for heating condition, and this paper repeats no more.

The present inventor further finds in research process, when described raw material is sent into extruder, make the temperature of raw material (namely, described raw material is in the temperature of the porch of described extruder) be 40～100 ℃, under the identical condition of all the other conditions, not only can be so that previously described requirement be satisfied in the most probable aperture of porous carrier of preparation, and the porous carrier of preparation has higher aperture concentration degree and mechanical strength.

Therefore, of the present invention a kind of preferred embodiment in, the temperature of described raw material in the porch of described extruder is 40～100 ℃.Have at the porous carrier of guaranteeing to prepare under the prerequisite in aperture of expection, from the aperture concentration degree of the porous carrier of further raising preparation and the angle of mechanical strength, the temperature of described raw material in the porch of described extruder is preferably 40～80 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃.

Can adopt the whole bag of tricks to make the temperature of described raw material in the porch of described extruder is 40～100 ℃ (are preferably 40～80 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃).

Usually, the process that described precursor, peptizing agent, water and the optional molecular sieve that can form heat-resistant inorganic oxide under roasting condition mixed is carried out under heating condition, the condition of described heating (is preferably 40～80 ℃ so that the temperature of the raw material that obtains in the porch of described extruder is 40～100 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃).For example: can be in the mixed process with the described precursor that under roasting condition, can form heat-resistant inorganic oxide, peptizing agent, water and optional molecular sieve, heat to make the temperature of the raw material of preparation to be in 40～100 ℃ (preferred 40～80 ℃ by external heat source, more preferably 50～80 ℃, further preferred 55～80 ℃) scope within; Also can be with at least one heating in the described precursor that under roasting condition, can form heat-resistant inorganic oxide, peptizing agent, water and the optional molecular sieve, then mix, the temperature that makes the described raw material that obtains is 40～100 ℃ and (is preferably 40～80 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃), and this temperature is 40～100 ℃ (is preferably 40～80 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃) raw material send in the described extruder.

The method according to this invention, when preparing described raw material, usually first peptizing agent is mixed with water, and then the mixture that obtains can be formed the precursor of heat-resistant inorganic oxide and optional molecular sieve mixes with described under roasting condition, thereby prepare described raw material; Therefore, can be by hot water be mixed with peptizing agent, obtain the mixture of heat, mixture that again should heat can form the precursor of heat-resistant inorganic oxide and optional molecular sieve mixes with described under roasting condition, thereby preparation temperature is 40～100 ℃ (is preferably 40～80 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃) raw material, and this temperature is 40～100 ℃ (is preferably 40～80 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃) raw material send in the extruder.

In addition, can also be before described raw material is being sent into extruder being heated to temperature by means of external heat source is 40～100 ℃ and (is preferably 40～80 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃), and this temperature is 40～100 ℃ (is preferably 40～80 ℃, more preferably 50～80 ℃, more preferably 55～80 ℃) raw material send in the extruder.

Of the present invention a kind of more preferred embodiment in, the temperature of described raw material in the porch of described extruder is preferably 40～80 ℃, and the temperature of described formed body in the exit of described extruder is 60～98 ℃.Porous carrier according to this embodiment preparation not only has higher aperture concentration degree, and has higher mechanical strength.

According to the present invention, the preparation method of described porous carrier also comprises the precursor that can form described heat-resistant inorganic oxide under roasting condition is mixed with peptizing agent and water, with the raw material that is provided for extruding.

The present invention is not particularly limited for the kind of described heat-resistant inorganic oxide, can carry out suitable selection according to the concrete application scenario of the porous carrier that finally obtains.For example, when having the catalyst of hydrogenation, described heat-resistant inorganic oxide can be in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and the mesoporous Si-Al one or more at the porous carrier that finally obtains; Be preferably in aluminium oxide, silica and the mesoporous Si-Al one or more; And more preferably aluminium oxide and/or silica.Of the present invention a kind of preferred embodiment in, described heat-resistant inorganic oxide contains aluminium oxide.

The present invention is not particularly limited for the described kind that can form the precursor of heat-resistant inorganic oxide under roasting condition, can carry out suitable selection according to the kind of the heat-resistant inorganic oxide of expecting, as long as this precursor can form described heat-resistant inorganic oxide under roasting condition.Usually, described precursor can for: at the hydrous oxide that can form described heat-resistant inorganic oxide under the roasting condition, contain at the gel of the precursor that can form heat-resistant inorganic oxide under the roasting condition and contain the colloidal sol that under roasting condition, can form the precursor of heat-resistant inorganic oxide.Among the present invention, term " hydrous oxide " refers to hydrated oxide.

For example, when described heat-resistant inorganic oxide was aluminium oxide, the example of described precursor can include but not limited to: hydrated alumina (for example: aluminium hydroxide, boehmite), the colloidal sol that contains the gel of hydrated alumina and contain hydrated alumina.

The method according to this invention, the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition can be this area average particulate diameter commonly used.The present inventor finds in research process: when the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition was 30～100nm, the porous carrier that is prepared by method of the present invention had higher aperture concentration degree.From the angle of the aperture concentration degree of the porous carrier of further raising preparation, the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is preferably 30～80nm, more preferably 30～60nm.Further preferably, the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is 40～60nm.

Can adopt this area the whole bag of tricks commonly used that the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is within the previously described scope.For example, can be by before use, the described precursor that can form heat-resistant inorganic oxide under roasting condition is ground and/or sieved, thereby the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is within the previously described scope.

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

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

Among the formula I, D is average particulate diameter;

λ is the wavelength of X ray;

β _HKLThe broadening degree that causes because of the grain size refinement for diffracted ray half high peak intensity place, wherein, β _HKL=B-B ₀

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

B ₀Broadening degree for instrument;

θ is incidence angle.

According to the present invention, be that described raw material preferably contains the precursor that can form aluminium oxide under roasting condition when having the catalyst of hydrogenation at described catalyst.For example, described raw material preferably contains the boehmite that can form aluminium oxide under roasting condition.Although adopt various boehmites all can form aluminium oxide, and realize purpose of the present invention, but the present inventor finds in research process: employing degree of crystallinity is that the boehmite more than 80% can have under the condition in large aperture at the porous carrier that guarantee final preparation, further improve aperture concentration degree and the mechanical strength of the porous carrier that obtains, and then so that catalyst of the present invention has higher catalytic activity and intermediate oil is selective.

Among the present invention, described degree of crystallinity is relative crystallinity, to adopt " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety front page, Yang Cui waits volume surely) in the method stipulated is measured among the RIPP 139-90 of record, wherein, employed standard specimen 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.

Of the present invention a kind of preferred embodiment in, the described precursor that can form heat-resistant inorganic oxide under roasting condition 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 porous carrier that obtains from further raising, the relative crystallinity of described boehmite is preferably 90～110%.

Of the present invention a kind of more preferred embodiment in, the described precursor that can form heat-resistant inorganic oxide under roasting condition 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 described precursor that can form heat-resistant inorganic oxide under roasting condition contains boehmite, the relative crystallinity of described boehmite is 90～110%, and the average particulate diameter of described boehmite is 30～80nm.

In a kind of most preferred embodiment of the present invention, the temperature of described raw material in the porch of described extruder is preferably 40～80 ℃, the temperature of described formed body in the exit of described extruder is 60～98 ℃, and the described precursor that can form heat-resistant inorganic oxide under roasting condition contains boehmite, the relative crystallinity of described boehmite is 90～110%, and the average particulate diameter of described boehmite is 30～80nm.Porous carrier according to this embodiment preparation has higher aperture concentration degree and the mechanical strength of Geng Gao.

The method according to this invention, described raw material also contains peptizing agent.The amount of the peptizing agent in the described raw material can be carried out suitable selection according to the employed kind that can form the precursor of heat-resistant inorganic oxide under roasting condition.Usually, take 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 select for the routine of this area.Among the present invention, the instantiation of described peptizing agent can for but be not limited to: nitric acid, hydrochloric acid, phosphoric acid, trichloroacetic acid and citric acid.

The method according to this invention makes water as decentralized medium when the described raw material of preparation, and described precursor and the peptizing agent that can form heat-resistant inorganic oxide under roasting condition mixed.The present invention is not particularly limited for the consumption of described water, can select for the routine of this area, as long as the amount of described water can mix described precursor and peptizing agent.

The method according to this invention, described raw material can also contain extrusion aid.The content of described extrusion aid and kind can be selected for the routine of this area.

Usually, take the total amount of described raw material as benchmark, the consumption of described extrusion aid can be 0.1～5 % by weight, is preferably 1～3 % by weight.Among the present invention, the example of described extrusion aid can for but be not limited to: one or more in organic carboxyl acid, polyalcohol, organic amine and the surfactant.

Among the present invention, term " organic carboxyl acid " refers to have in the molecular structure organic compound of 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 be carbon number be 1～20 unary organic carboxylic acid or polynary organic carboxyl acid (for example: the binary organic carboxyl acid).Among the present invention, the example of described organic carboxyl acid can for 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.

Among the present invention, term " polyol " refers to have in the molecular structure organic compound of two above hydroxyls.The example of described polyalcohol can for but be not limited to: ethylene glycol, glycerine and butanediol.

Among the present invention, term " organic amine " refers to contain in the molecular structure organic compound of one or more amidos.The example of described organic amine can for but be not limited to: monoethanolamine, diethanol amine, triethanolamine, N methyldiethanol amine and urea.

Among the present invention, 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 for but be not limited to: stearic acid and neopelex.The example of described cationic surface active agent can for but be not limited to: the quaternary ammonium compound.The example of described amphoteric ionic surfactant can for but be not limited to: lecithin, amino acid type surfactant and betaine type amphoteric surfactant.The example of described nonionic surface active agent can for but be not limited to: fatty glyceride, aliphatic acid sorb smooth (span series), polysorbate (tween series of surfactants), polyoxyethylene-type surfactant and polyox-yethylene-polyoxypropylene block copolymer.

The method according to this invention, described raw material can also contain molecular sieve.There is no particular limitation for the kind of molecular sieve in the described raw material and consumption in the present invention, and described molecular sieve can be zeolite molecular sieve and/or non-zeolite molecular sieve.Among the present invention, the example of described molecular sieve can for but be not limited to: the ZRP molecular sieve, the MCM-41 molecular sieve, erionite, the ZSM-34 molecular sieve, modenite, ZSM-5 molecular sieve, the ZSM-11 molecular sieve, the ZSM-12 molecular sieve, the ZSM-22 molecular sieve, ZSM-23 molecular screen, ZSM-35 molecular sieve, the L-type molecular sieve, Y zeolite, the X-type molecular sieve, the ZSM-3 molecular sieve, the ZSM-4 molecular sieve, the ZSM-18 molecular sieve, the ZSM-20 molecular sieve, the ZSM-48 zeolite, the ZSM-57 zeolite, faujasite, beta-molecular sieve, the Ω molecular sieve, phosphate aluminium molecular sieve, HTS and SAPO (that is, SAPO) molecular sieve.Be when having the catalyst of hydrogenation at described catalyst, described molecular sieve is preferably one or more in ZRP molecular sieve, Y zeolite, beta-molecular sieve, modenite, ZSM-5 molecular sieve, MCM-41 molecular sieve, Ω molecular sieve, ZSM-12 molecular sieve and the MCM-22 molecular sieve.

The method according to this invention, the consumption of described molecular sieve can be the conventional amount used of this area.For example: at the porous carrier that makes when having the catalyst of hydrogenation, the content of the molecular sieve in the described raw material is so that in the porous carrier of preparation, take the total amount of described porous carrier as benchmark, the content of described molecular sieve can be 0.1～66 % by weight, be preferably 0.2～50 % by weight, more preferably 0.5～30 % by weight, more preferably 0.75～20 % by weight; The content of described heat-resistant inorganic oxide can be 34～99.9 % by weight, is preferably 50～99.8 % by weight, more preferably 70～99.5 % by weight, more preferably 80～99.25 % by weight.

Comprise according to the preparation method of porous carrier of the present invention described raw material is extruded, to obtain formed body.According to the present invention, described extruder can be this area various extruders commonly used.The present invention also is not particularly limited for described kneading and the condition of extruding, and can be that the routine of this area is selected.

Also comprise according to the preparation method of porous carrier of the present invention described formed body is carried out roasting, thereby obtain porous carrier.

The present invention is not particularly limited for the condition of described roasting, can be the normal condition of this area.Usually, the temperature of described roasting can be 350～800 ℃, is preferably 450～650 ℃; The time of described roasting can be 1～10 hour, is preferably 2～5 hours.Described roasting can be carried out in oxygen-containing atmosphere, also can be for carrying out in the inert atmosphere.

Among the present invention, described inert atmosphere refers to be inactive gas under drying or roasting condition, for example: nitrogen and group 0 element gas (such as argon gas).

The method according to this invention, before described formed body is carried out roasting, can also comprise described formed body is carried out drying, described drying can be carried out under the normal condition of this area, for example: the temperature of described drying can be 100～200 ℃, and the time of described drying can be 2～12 hours.Described drying can be carried out under the condition of normal pressure, also can carry out under the condition of decompression, is not particularly limited.Described drying can be carried out in oxygen-containing atmosphere, also can carry out in inert atmosphere.

The preparation method of catalyst according to the invention comprises that the active component that will have catalytic action loads on the porous carrier.

The method according to this invention, the described load capacity of active component on described porous carrier with catalytic action can be carried out suitable selection according to the kind of described active component.Usually, be when having the active component of hydrogenation at described active component with catalytic action, take the total amount of the catalyst that finally obtains as benchmark, in oxide, the amount of described active component can be 5～60 % by weight, is preferably 10～50 % by weight; The amount of described carrier can be 40～95 % by weight, is preferably 50～90 % by weight.

The method according to this invention, described active component with catalytic action can be carried out suitable selection according to the concrete application scenario of the catalyst of final preparation.When catalyst according to the invention was used for the hydrocracking of hydrocarbon ils, described composition with catalytic activity was preferably group vib metal and group VIII metal.Described group vib metal and group VIII metal can be respectively load on the described porous carrier, for example with the various forms of this area routine: described group vib metal and group VIII metal can be respectively be loaded on the described porous carrier with the form of oxide.

The method according to this invention is when described active component is group vib metal and group VIII metal, in the catalyst that finally obtains, take the total amount of described catalyst as benchmark, in oxide, the content of described group vib metal can be 10～40 % by weight, is preferably 15～30 % by weight; The content of described group VIII metal can be 2～10 % by weight, is preferably 2.5～6.5 % by weight; The content of described porous carrier can be 50～88 % by weight, is preferably 63.5～82.5 % by weight.

According to the present invention, can adopt well known to a person skilled in the art the whole bag of tricks with described active constituent loading on described porous carrier.

For example, can contain by usefulness the described porous carrier of solution impregnation of the compound of described active component, and have the carrier of described compound to carry out drying and roasting load, thereby described active component is loaded on the described porous carrier.When described active component was group vib metal and group VIII metal, described compound can be this area compound that contains the group vib metal and the compound that contains the group VIII metal commonly used.When described group vib metal was molybdenum and/or tungsten, the described compound that contains the group vib metal was preferably the compound of tungsten and/or the compound of molybdenum.Among the present invention, the example of the described compound that contains the group vib metal can for 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 the ethyl ammonium metatungstate.When described group VIII metal was cobalt and/or nickel, the described compound that contains the group VIII metal was preferably take nickel as cationic oxysalt, take nickel as cationic anaerobic hydrochlorate, take cobalt as cationic oxysalt and in take cobalt as cationic anaerobic hydrochlorate one or more.Among the present invention, the example of the described compound that contains the group VIII metal can for 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 the cobalt chloride.

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

The method of described dipping can for this area various dipping methods commonly used, 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 satisfies concrete instructions for use.Usually, the time of described dipping can be 0.5～12 hour.

According to the present invention, carry out dry condition for the porous carrier that load is had described compound and be not particularly limited.Usually, the temperature of described drying can be 80～300 ℃, is preferably 100～200 ℃; The time of described drying can be 0.5～24 hour, is preferably 1～12 hour.

The present invention is not particularly limited for the condition that the load with drying has the carrier of described compound to carry out roasting, can be the normal condition of this area.Usually, the temperature of described roasting can be 350～700 ℃, is preferably 400～650 ℃; The time of described roasting can be 0.2～12 hour, is preferably 1～10 hour.Described roasting can be carried out in oxygen-containing atmosphere, also can carry out in inert atmosphere.

The present invention provides again a kind of catalyst by method preparation of the present invention.

Porous carrier in the prepared according to the methods of the invention catalyst has high aperture concentration degree.Usually, the most probable aperture of described porous carrier can be 1～30nm, is preferably 2～20nm, more preferably 5～10nm; The aperture concentration degree can be 22～48, is preferably 25～48 (for example can be 25～40), more preferably 27～40.

Of the present invention a kind of preferred embodiment in, the most probable aperture of the porous carrier in the catalyst according to the invention is 1～30nm, the aperture concentration degree is 22～48.Of the present invention a kind of more preferred embodiment in, the most probable aperture of the porous carrier in the catalyst according to the invention is 2～20nm, the aperture concentration degree is 25～48.In a kind of further preferred embodiment of the present invention, the most probable aperture of the porous carrier in the catalyst according to the invention is 5～10nm, and the aperture concentration degree is 27～40.

The porous carrier that catalyst according to 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 that has than low boiling and lower molecular weight.

Thus, the present invention also further provides the application of a kind of catalyst according to the invention in the hydrocarbon oil hydrogenation cracking.

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

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 for 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 the hydrocracking and intermediate oil optionally, is not particularly limited for all the other conditions of hydrocracking, can be the normal condition of this area.Preferably, described hydrocracking condition comprises: temperature is 200～650 ℃, is preferably 300～510 ℃; In gauge pressure, pressure is 3～24 MPas, is preferably 4～15 MPas; Hydrogen to oil volume ratio can be 150～2500; Volume space velocity can be 0.1～30 hour during liquid ^-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: in the presence of hydrogen, under 140～370 ℃ temperature, 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 outside reactor, also can original position sulfuration in reactor.

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

Employed reagent in following examples and the Comparative Examples except specifying, is chemically pure reagent.

In following examples and the Comparative Examples, in the model that is purchased from Quantachrome company be

The full-automatic specific surface in six stations and pore size distribution determining instrument on, adopt the BET method to measure most probable aperture and the aperture concentration degree of porous carrier according to the method for stipulating among the RIPP 151-90.

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

In following examples and the Comparative Examples, be on the X-ray diffractometer of X ' pert in the model that is purchased from Philips company, measure average particulate diameter and the degree of crystallinity of porous carrier, wherein, degree of crystallinity is relative crystallinity, is to measure according to the method for stipulating among the RIPP 139-90.

In following examples and the Comparative Examples, be the crushing strength of crushing strength analyzer (manufacturing of alkaline research institute of the Ministry of Chemical Industry) the mensuration porous carrier of QCY-602 in model according to the method for stipulating among the GB3635-1983.

In following examples and the Comparative Examples, pressure is all in gauge pressure.

Preparation example 1

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Getting the CL powder (is purchased from the Chang Ling catalyst plant, contents on dry basis is 71 % by weight, be a kind of boehmite, relative crystallinity is 98.1%, average particulate diameter is 33nm, lower same) 98.6g, (be purchased the company from sasol, contents on dry basis is 81 % by weight to aluminum silicon powder SIRAL 70 powder, mixture for the hydrate of the hydrate of aluminium oxide and silica, in oxide, the content of silica is 70 % by weight, and the content of aluminium oxide is 30 % by weight, average particulate diameter is 57nm, lower same) 37.1g, add sesbania powder 4g to be dry mixed evenly, obtain dry powder.1.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, and is lower same) and the adding of 3g triethanolamine are contained with in the beaker of 110mL deionized water, mix, obtain acid solution.With acid solution and dry powder blend, and stir, obtaining be used to the raw mix of extruding, the temperature of described deionized water is so that the temperature of the raw mix that obtains is 40 ℃.Be that 40 ℃ mixture is sent in the banded extruder with the temperature that obtains, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the temperature of extrudate in the exit of extruder is 72 ℃.With extrudate 105 ℃ of dryings 4 hours.Then, in air atmosphere, under 620 ℃ temperature, roasting 2 hours, in the roasting process, the flow of air is 12L hour ^-1, obtain being designated as A1 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 2

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Get the C1 powder and (be purchased the company from sasol, contents on dry basis is 74.5 % by weight, be a kind of boehmite, relative crystallinity is 93.1%, average particulate diameter is 53nm) 73.8g, aluminum silicon powder SIRAL 40 powder (are purchased the company from sasol, contents on dry basis is 77.5 % by weight, be the mixture of the hydrate of the hydrate of aluminium oxide and silica, in oxide, the content of silica is 40 % by weight, the content of aluminium oxide is 60 % by weight, average particulate diameter is 55nm, and is lower same) 51.6g, (lattice constant is the USY molecular sieve

Relative crystallinity is 74.6%, and contents on dry basis is 76.9 % by weight) 6.5g, add sesbania powder 4g and be dry mixed evenly, obtain dry powder.The adding of 3mL red fuming nitric acid (RFNA) is contained with in the beaker of 103mL deionized water, mixes, obtain acid solution.With acid solution and dry powder blend, and stir, obtain be used to the raw mix of extruding, the temperature of described deionized water is so that the temperature of the raw mix that obtains is 65 ℃.Be that 65 ℃ mixture is sent in the banded extruder with the temperature that obtains, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the temperature of extrudate in the exit of extruder is 88 ℃.With extrudate 110 ℃ of dryings 8 hours.Then, in air atmosphere, under 600 ℃ temperature, roasting 2 hours, in the roasting process, the flow of air is 65L hour ^-1, obtain being designated as A2 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 3

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Getting the SD powder (is purchased from Shandong Aluminum Plant, contents on dry basis is 64 % by weight, be a kind of boehmite, relative crystallinity is 103%, average particulate diameter is 46nm) 62.5g, aluminum silicon powder SIRAL 10 powder (are purchased the company from sasol, contents on dry basis is 74.5 % by weight, for the mixture of the hydrate of the hydrate of aluminium oxide and silica, in oxide, the content of silica is 10 % by weight, the content of aluminium oxide is 90 % by weight, and average particulate diameter is 53nm, and is lower same) 80.5g, add sesbania powder 4g and be dry mixed evenly, to obtain dry powder.2mL red fuming nitric acid (RFNA) and 2g PEG400 (being purchased the sincere auspicious Chemical Industry Science Co., Ltd from Zhengzhou) adding are contained with in the beaker of 78mL deionized water, mix, to obtain acid solution.With acid solution and dry powder blend, and stir, obtaining be used to the raw mix of extruding, the temperature of described deionized water is so that the temperature of the raw mix that obtains is 60 ℃.Be that 60 ℃ of mixtures are sent in the banded extruder with the temperature that obtains, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the temperature of extrudate in the exit of extruder is 81 ℃.With extrudate 115 ℃ of dryings 6 hours.Then, in air atmosphere, under 580 ℃ temperature, roasting 3 hours, in the roasting process, the flow of air is 200L hour ^-1, obtain being designated as A3 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 4

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Get CL powder 91.5g, (be purchased the company from sasol, contents on dry basis is 75 % by weight to aluminum silicon powder SIRAL 20 powder, mixture for the hydrate of the hydrate of aluminium oxide and silica, in oxide, the content of silica is 20 % by weight, and the content of aluminium oxide is 80 % by weight, average particulate diameter is 53nm) 46.7g, Beta molecular sieve (silica alumina ratio is 61.4, and relative crystallinity is 84.2%, and contents on dry basis is 83 % by weight) 1.2g, add sesbania powder 4g and be dry mixed evenly, to obtain dry powder.The adding of 3.5mL red fuming nitric acid (RFNA) is contained with in the beaker of 95mL deionized water, mixes, to obtain acid solution.With acid solution and dry powder blend, and stir, obtain be used to the raw mix of extruding (temperature of raw mix is room temperature (25 ℃)).The mixture (temperature is room temperature (25 ℃)) that obtains is sent in the banded extruder, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the extrudate temperature in the exit of described extruder is 64 ℃.With extrudate 120 ℃ of dryings 5 hours.Then, in air atmosphere, under 560 ℃ temperature, roasting 3 hours, in the roasting process, the flow of air is 35L hour ^-1, obtain being designated as A4 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 5

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

(be purchased the company from sasol, contents on dry basis is 75 % by weight, is a kind of boehmite to get the SB powder, relative crystallinity is 95.4%, and average particulate diameter is 49nm, and is lower same) 93.3g, aluminum silicon powder SIRAL40 powder 38.7g adds sesbania powder 4g and is dry mixed evenly, to obtain dry powder.The adding of 2.5mL red fuming nitric acid (RFNA) is contained with in the beaker of 90mL deionized water, mixes, to obtain acid solution.With acid solution and dry powder blend, and stir, obtain be used to the raw mix of extruding, the temperature of described deionized water is so that the temperature of the raw mix that obtains is 80 ℃.Be that 80 ℃ of mixtures are sent in the banded extruder with the temperature that obtains, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the temperature of extrudate in the exit of extruder is 92 ℃.With extrudate 125 ℃ of dryings 10 hours.Then, in air atmosphere, under 540 ℃ temperature, roasting 4 hours, in the roasting process, the flow of air is 105L hour ^-1, obtain being designated as A5 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 6

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Adopt the method identical with preparation example 4 to prepare porous carrier, different is that the extrudate temperature in the exit of described extruder is 43 ℃.The porous carrier of the present invention of preparation is designated as A6.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 7

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Get C1 powder 67.1g, aluminum silicon powder SIRAL 40 powder 64.5g add sesbania powder 4g and are dry mixed evenly, to obtain dry powder.The adding of 3mL red fuming nitric acid (RFNA) is contained with in the beaker of 106mL deionized water, mixes, to obtain acid solution.With acid solution and dry powder blend, and stir, obtaining be used to the raw mix of extruding, the temperature of described deionized water is so that the temperature of the raw mix that obtains is 45 ℃.Be that 45 ℃ mixture is sent in the banded extruder with the temperature that obtains, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the temperature of extrudate in the exit of extruder is 78 ℃.With extrudate 110 ℃ of dryings 6 hours.Then, in air atmosphere, under 620 ℃ temperature, roasting 5 hours, in the roasting process, the flow of air is 35L hour ^-1, obtain being designated as A7 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 8

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Get SB powder 93.3g, aluminum silicon powder SIRAL 20 powder 40g add sesbania powder 4g and are dry mixed evenly, to obtain dry powder.The adding of 2mL red fuming nitric acid (RFNA) is contained with in the beaker of 87mL deionized water, mixes, to obtain acid solution.With acid solution and dry powder blend, and stir, obtaining be used to the raw mix of extruding, the temperature of described deionized water is so that the temperature of the raw mix that obtains is 60 ℃.Be that 60 ℃ mixture is sent in the banded extruder with the temperature that obtains, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the temperature of extrudate in the exit of extruder is 84 ℃.With extrudate 115 ℃ of dryings 4 hours.Then, in air atmosphere, under 600 ℃ temperature, roasting 5 hours, in the roasting process, the flow of air is 200L hour ^-1, obtain being designated as A8 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 9

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Get CL powder 119.7g, (lattice constant is the USY molecular sieve

Relative crystallinity is 74.6%, and contents on dry basis is 76.9 % by weight) 19.5g, add sesbania powder 4g and be dry mixed evenly, to obtain dry powder.3.5mL red fuming nitric acid (RFNA) and the adding of 5g urea are contained with in the beaker of 106mL deionized water, mix, to obtain acid solution.With acid solution and dry powder blend, and stir, obtain raw mix (temperature of raw mix is room temperature (25 ℃)).The mixture (temperature is room temperature (25 ℃)) that obtains is sent in the banded extruder, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the extrudate temperature in the exit of described extruder is 80 ℃.With extrudate 120 ℃ of dryings 8 hours.Then, in air atmosphere, under 580 ℃ temperature, roasting 2 hours, in the roasting process, the flow of air is 65L hour ^-1, obtain being designated as A9 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 10

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Get C1 powder 100.7g, aluminum silicon powder SIRAL 40 powder 32.3g add sesbania powder 4g and are dry mixed evenly, to obtain dry powder.The adding of 2.5mL red fuming nitric acid (RFNA) is contained with in the beaker of 104mL deionized water, mixes, to obtain acid solution.With acid solution and dry powder blend, and stir, obtaining be used to the raw mix of extruding, the temperature of described deionized water is so that the temperature of the raw mix that obtains is 55 ℃.Be that 55 ℃ mixture is sent in the banded extruder with the temperature that obtains, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the temperature of extrudate in the exit of extruder is 78 ℃.With extrudate 125 ℃ of dryings 7 hours.Then, in air atmosphere, under 560 ℃ temperature, roasting 3 hours, in the roasting process, the flow of air is 12L hour ^-1, obtain being designated as A10 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 11

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Get SD powder 71.8g, (be purchased the company from sasol, contents on dry basis is 77.5 % by weight to aluminum silicon powder SIRAL 30 powder, mixture for the hydrate of the hydrate of aluminium oxide and silica, in oxide, the content of silica is 30 % by weight, and the content of aluminium oxide is 70 % by weight, average particulate diameter is 53nm) 59.2g, ZSM-5 molecular sieve (silica alumina ratio is 51%, and relative crystallinity is 77.3%, and contents on dry basis is 81 % by weight) 11.1g, add sesbania powder 4g and be dry mixed evenly, to obtain dry powder.The adding of 1mL red fuming nitric acid (RFNA) is contained with in the beaker of 92mL deionized water, mixes, to obtain acid solution.With acid solution and dry powder blend, and stir, to obtain be used to the raw mix of extruding (temperature of raw mix is as room temperature (25 ℃)).The mixture (temperature is room temperature (25 ℃)) that obtains is sent in the banded extruder, be extruded into circumscribed circle diameter and be 1.4 millimeters butterfly bar, the extrudate temperature in the exit of described extruder is 60 ℃.With extrudate 105 ℃ of dryings 5 hours.Then, in air atmosphere, under 540 ℃ temperature, roasting 4 hours, in the roasting process, the flow of air is 105L hour ^-1, obtain being designated as A11 according to porous carrier of the present invention after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 12

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Adopt the method identical with preparation example 4 to prepare porous carrier, different is that the extrudate temperature in the exit of described extruder is 98 ℃.The porous carrier according to the present invention of preparation is designated as A12.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 13

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Adopt the method identical with embodiment 8 to prepare porous carrier, different is, the dry glue powder that uses is (according to CN100999328B embodiment 3 disclosed method preparations, be a kind of boehmite, relative crystallinity is 76%, average particulate diameter is 36nm) replace the SB powder, the porous carrier of preparation is designated as A13.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation example 14

This preparation example is used for preparing the porous carrier in the catalyst according to the invention.

Adopt the method identical with preparation example 2 to prepare porous carrier, different is, the temperature of raw mix when entering described extruder is room temperature (25 ℃), and the porous carrier that obtains is designated as A14.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.

Preparation Comparative Examples 1

Adopt the method identical with preparation example 4 to prepare porous carrier, different is, the extrudate temperature in the exit of described extruder is 35 ℃, and the porous carrier that obtains is designated as B1.Most probable aperture and the aperture concentration degree of this porous carrier are listed in table 1.

Table 1

The preparation example numbering	The porous carrier numbering	Aperture, most probable hole (nm)	The aperture concentration degree	Crushing strength (N/mm)
					Preparation example 1	A1	8.8	26.7	25.8
Preparation example 2	A2	8.2	33.4	27.3
					Preparation example 3	A3	6.6	28.3	23.3
Preparation example 4	A4	9.1	28.1	24.5
					Preparation example 5	A5	7.4	38.4	30.8
Preparation example 6	A6	8.8	25.7	21.2
					Preparation example 7	A7	7.8	30.6	25.4
Preparation example 8	A8	7.1	33.7	29.9
					Preparation example 9	A9	5.8	25.4	27.7
Preparation example 10	A10	9.3	29.8	30.6
					Preparation example 11	A11	6.4	26.9	19.8
Preparation example 12	A12	9.1	27.0	25.3
					Preparation example 13	A13	6.2	22.0	22.4
Preparation example 14	A14	8.1	25.8	20.1
					Preparation Comparative Examples 1	B1	8.9	19.0	18.8

Embodiment 1～14

Embodiment 1～14 is used for illustrating catalyst according to the invention and application and method for hydrogen cracking.

Ammonium metatungstate (being purchased from the 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 porous carrier A1～A14 of preparation in the preparation example 1～14 according to the hole saturation with this maceration extract, and the carrier after will flooding under 120 ℃ in air atmosphere dry 2 hours, then roasting 5 hours in air atmosphere under 350 ℃, thereby make the catalyst with hydrogenation, be designated as respectively catalyst X1～X14.Ammonium metatungstate and the nickel nitrate load capacity on porous carrier is so that take the total amount of catalyst as benchmark, in oxide, and among catalyst X1～X14, WO ₃Be respectively 27.0 % by weight and 2.6 % by weight with NiO content.

Comparative Examples 1

Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1～14, different is the porous carrier that porous carrier prepares for preparation Comparative Examples 1.The catalyst that makes is designated as CX.Ammonium metatungstate and the nickel nitrate load capacity on porous carrier is so that take the total amount of catalyst as benchmark, in oxide, and WO ₃Be respectively 27.0 % by weight and 2.6 % by weight with NiO content.

EXPERIMENTAL EXAMPLE 1～14

EXPERIMENTAL EXAMPLE 1～14 is used for the performance of catalyst of Evaluation operation example 1～14 preparation.

Evaluating catalyst adopts and once passes through flow process, and feedstock oil adopts sand gently to subtract two, and the density of this feedstock oil (20 ℃) is 0.9062g/cm ³, refraction index (20 ℃) is 1.4852; Initial boiling point (IBP) is 299 ℃, and 5% recovered (distilled) temperature is 359 ℃, and 50% recovered (distilled) temperature is 399 ℃, and 95% recovered (distilled) temperature is 436 ℃.

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

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

The cracking reaction temperature of needs when activity refers to that conversion ratio that recovered (distilled) temperature is higher than 350 ℃ hydrocarbon ils is 60%, wherein, the catalytic activity of the lower explanation catalyst of cracking reaction temperature is higher;

Intermediate oil refers to that selectively recovered (distilled) temperature is that the content of 132～371 ℃ cut accounts for recovered (distilled) temperature less than the percentage of the gross mass of 371 ℃ of cuts.

Experiment Comparative Examples 1

Adopt the performance of the catalyst that the method evaluation Comparative Examples 1 identical with EXPERIMENTAL EXAMPLE 1～14 prepare.

EXPERIMENTAL EXAMPLE 1～14 shows with the result of experiment Comparative Examples 1, and the porous carrier according to the present invention in the catalyst has higher aperture concentration degree, so catalyst according to the invention has higher catalytic activity and intermediate oil is selective.Table 2 has been listed EXPERIMENTAL EXAMPLE 2,4,5,7 and 14 and the experimental result of experiment Comparative Examples 1.

Table 2

Numbering	Catalyst	Active (℃)	Selectively (%)
				EXPERIMENTAL EXAMPLE 2	X2	384.4	82.8
EXPERIMENTAL EXAMPLE 4	X4	395.0	83.4
				EXPERIMENTAL EXAMPLE 5	X5	415.3	85.0
EXPERIMENTAL EXAMPLE 7	X7	410.8	84.8
				EXPERIMENTAL EXAMPLE 14	X14	386.5	82.6
Experiment Comparative Examples 1	CX1	398.7	83.1

EXPERIMENTAL EXAMPLE 4 and experiment Comparative Examples 1 are compared and can find out, catalyst according to the invention have higher catalytic activity and intermediate oil selective.

EXPERIMENTAL EXAMPLE 2 and EXPERIMENTAL EXAMPLE 14 are compared and can find out, under the identical condition of all the other conditions, aperture concentration degree for the preparation of the porous carrier of catalyst is higher, then the catalyst with hydrogenation of preparation have higher catalytic activity and intermediate oil selective.

Claims (29)

1. catalyst, this catalyst contains porous carrier and loads on the active component with catalytic action on this porous carrier, described porous carrier contains heat-resistant inorganic oxide, it is characterized in that, the most probable aperture of described porous carrier is 1～30nm, the aperture concentration degree of described porous carrier is 22～48, described most probable aperture is to adopt the BET method to measure, described aperture concentration degree refers to adopt in the distribution curve of dV/dr with varying aperture of BET method mensuration, the ratio of the height at peak and the halfwidth at this peak, dV/dr represent the long-pending differential to the aperture of specific pore volume.

2. catalyst according to claim 1, wherein, take the total amount of described catalyst as benchmark, in oxide, the content of described active component is 5～60 % by weight, the content of described porous carrier is 40～95 % by weight.

3. catalyst according to claim 1 and 2, wherein, the most probable aperture of described porous carrier is 2～20nm, the aperture concentration degree is 25～48.

4. catalyst according to claim 3, wherein, the most probable aperture of described porous carrier is 5～10nm, the aperture concentration degree is 27～40.

5. catalyst according to claim 1, wherein, described porous carrier also contains molecular sieve, and take the total amount of described porous carrier as benchmark, the content of described molecular sieve is 0.1～66 % by weight, and the content of described heat-resistant inorganic oxide is 34～99.9 % by weight.

6. catalyst according to claim 5, wherein, described molecular sieve is one or more in ZRP molecular sieve, Y zeolite, beta-molecular sieve, modenite, ZSM-5 molecular sieve, MCM-41 molecular sieve, Ω molecular sieve, ZSM-12 molecular sieve and the MCM-22 molecular sieve.

7. catalyst according to claim 1 or 5, wherein, described heat-resistant inorganic oxide is one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and the mesoporous Si-Al.

8. catalyst according to claim 1 or 5, wherein, described heat-resistant inorganic oxide contains aluminium oxide.

9. catalyst according to claim 1 and 2, wherein, described active component is group vib metal and group VIII metal.

10. catalyst according to claim 9, wherein, in oxide, take the total amount of described catalyst as benchmark, the content of described group vib metal is 10～40 % by weight, and the content of described group VIII metal is 2～10 % by weight, and the content of described porous carrier is 50～88 % by weight.

11. the preparation method of a catalyst, the method comprises that the active component that will have catalytic action loads on the porous carrier, it is characterized in that, described porous carrier prepares by the following method: the precursor that will can form heat-resistant inorganic oxide under roasting condition is mixed with peptizing agent and water, to supply raw materials; Described raw material is sent in the extruder, and in described extruder, after kneading, extruded, to obtain formed body; Described formed body is carried out roasting, and to obtain described porous carrier, wherein, the temperature of described formed body in the exit of described extruder is 40～150 ℃.

12. method according to claim 11, wherein, the load capacity of described active component on described porous carrier is so that take the total amount of catalyst as benchmark, in oxide, the content of described active component is 5～60 % by weight, and the content of described porous carrier is 40～95 % by weight.

13. according to claim 11 or 12 described methods, wherein, described active component is group vib metal and group VIII metal.

14. method according to claim 13, wherein, in oxide, take the total amount of described catalyst as benchmark, the content of described group vib metal is 10～40 % by weight, and the content of described group VIII metal is 2～10 % by weight, and the content of described porous carrier is 50～88 % by weight.

15. method according to claim 11, wherein, the temperature of described formed body in the exit of described extruder is 60～120 ℃.

16. according to claim 11 or 15 described methods, wherein, the temperature of described raw material in the porch of described extruder is 40～100 ℃.

17. method according to claim 16, wherein, the temperature of described raw material in the porch of described extruder is 40～80 ℃.

18. method according to claim 11, wherein, the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is 30～100nm.

19. method according to claim 18, wherein, the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is 30～80nm.

20. method according to claim 11, wherein, described raw material also contains molecular sieve, the content of described molecular sieve in described raw material is so that in the porous carrier of preparation, take the total amount of described porous carrier as benchmark, the content of described molecular sieve is 0.1～66 % by weight, and the content of described heat-resistant inorganic oxide is 34～99.9 % by weight.

21. method according to claim 20, wherein, described molecular sieve is one or more in ZRP molecular sieve, Y zeolite, beta-molecular sieve, modenite, ZSM-5 molecular sieve, MCM-41 molecular sieve, Ω molecular sieve, ZSM-12 molecular sieve and the MCM-22 molecular sieve.

22. according to claim 11 with 18～20 in the described method of any one, wherein, described heat-resistant inorganic oxide is one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and the mesoporous Si-Al.

23. according to claim 11, the described method of any one in 18 and 19, wherein, it is boehmite more than 80% that the described precursor that can form heat-resistant inorganic oxide under roasting condition contains relative crystallinity, and described relative crystallinity is to measure according to the method for stipulating among the RIPP 139-90.

24. method according to claim 23, wherein, the relative crystallinity of described boehmite is 90～110%.

25. method according to claim 11, wherein, the condition of described roasting comprises: temperature is 350～800 ℃, and the time is 1～10 hour.

26. catalyst by the described method preparation of any one in the claim 11～25.

27. according to claim 1～10 and the application of the described catalyst of any one in the hydrocarbon oil hydrogenation cracking in 26.

28. a method for hydrogen cracking, the method is included under the hydrocracking condition, and hydrocarbon ils is contacted with catalyst, it is characterized in that, described catalyst is the described catalyst of any one in claim 1～10 and 26.

29. method according to claim 28, wherein, described hydrocracking condition comprises: temperature is 200～650 ℃, and in gauge pressure, pressure is 3～24 MPas, and hydrogen to oil volume ratio is 150～2500, and volume space velocity is 0.1～30 hour during liquid ^-1