CN104043479A - Hydrocracking catalyst and preparation and application thereof - Google Patents
Hydrocracking catalyst and preparation and application thereof Download PDFInfo
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- CN104043479A CN104043479A CN201310083009.9A CN201310083009A CN104043479A CN 104043479 A CN104043479 A CN 104043479A CN 201310083009 A CN201310083009 A CN 201310083009A CN 104043479 A CN104043479 A CN 104043479A
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Abstract
The invention relates to a hydrocracking catalyst and its preparation and application. The catalyst contains a matrix containing a heatproof inorganic oxide, a Y-type molecular sieve and a carrier of an MFI-structured molecular sieve, wherein the most probable pore of the carrier is 1-30 nm; and pore concentration ratio is 22-48. The most probable pore is measured by a BET method. The pore concentration ratio is the ratio of height of a peak to half-width of the peak in a distribution curve of volume of the pore measured by the BET method changing with the pore. The preparation method of the catalyst comprises preparation of matrix containing the heatproof inorganic oxide, the Y-type molecular sieve and the carrier of the MFI-structured molecular sieve. A preparation method of the carrier comprises mixing of a precursor of the heatproof inorganic oxide, the Y-type molecular sieve, the MFI-structured molecular sieve, a peptizer and water and extrusion molding, wherein temperature of a molded body at the exit of an extruder is 40-150 DEG C. In comparison with the prior art, the hydrocracking catalyst provided by the invention has high catalytic activity and middle distillate selectivity when used in hydrocarbon oil processing and has stronger ability of reducing condensation point of tail oil.
Description
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 (that is, 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 the percentage that pore volume in given pore diameter range accounts for total pore volume, this percentage is higher, thinks that aperture concentration degree is also higher.But the method that accounts for the percentage of total pore volume by calculating pore volume in 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 the specific pore volume of being measured by BET method to amass in (dV/dlog (D)) distribution curve 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 hydrogenation activity composition on this carrier and the IVB family metal component in the periodic table of elements, wherein, the most probable aperture of described carrier is 6～14nm, and 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, needs further to improve.
To sum up, how to obtain there is high catalytic activity, high intermediate oil is selective, the hydrocracking catalyst simultaneously with high reduction tail oil condensation point ability remains a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, a kind of hydrocracking catalyst with high catalytic activity and the selective and high reduction tail oil condensation point ability of intermediate oil is provided, 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: with extruder, by extrusion molding, preparing formed body, thereby while obtaining 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 is more than 22 carrier.When the carrier of hydrocracking catalyst that employing is prepared by the method is prepared 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 has the carrier of the molecular sieve of MFI structure, 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 and prepare the carrier that contains heat-resistant inorganic oxide matrix, Y zeolite and there is the molecular sieve of MFI structure, the preparation method of this carrier comprises the following steps: (1) mixes the precursor of heat-resistant inorganic oxide, Y zeolite and molecular sieve, peptizing agent and the water with MFI structure, 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, the temperature of described formed body in the exit of described extruder is 40～150 ℃.
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.
According to carrier of the present invention, not only there is larger aperture and pore volume, and there is higher aperture concentration degree.That by this carrier, is prepared is adding man-hour containing Y zeolite and the hydrocracking catalyst with the molecular sieve of MFI structure for hydrocarbon ils, has high catalytic activity and intermediate oil selective.
Accompanying drawing explanation
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.
The specific embodiment
According to catalyst provided by the invention, wherein said carrier contains heat-resistant inorganic oxide, Y zeolite and has the molecular sieve of MFI structure.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.Take 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, 0.5～30 % by weight more preferably, has the content of molecular sieve of MFI structure 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 1～15 % by weight.
In the present invention, term " aperture, most probable hole " refers to: when 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, to obtain the method for the long-pending distribution curve with aperture of specific pore volume, be known in those skilled in the art, for example can be according to < < Petrochemical Engineering Analysis method > > (Science Press, nineteen ninety front page, the volumes such as Yang Cuiding) in the method stipulated in the RIPP151-90 that records measure.
In the present invention, term " aperture concentration degree " refers to: when 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 a plurality of 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 (that is, maximum dV/dlog (D)), and N represents that (that is,, on described distribution curve, ordinate is half-peak breadth (halfwidth)
two points between distance).When 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 ℃ (for example: decomposition temperature is 300～1000 ℃).
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, one or more in preferred 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 described molecular sieve with MFI structure is preferably from ZSM-5, ZRP-5 and their mixture, described in the silica alumina ratio that has in the molecular sieve of MFI structure can carry out suitable selection according to the concrete application scenario of the catalyst of final preparation, be not particularly limited.In a preferred embodiment, preferably silica alumina ratio is 25～200, more preferably 25～150 described in there is the molecular sieve molecular sieve of MFI structure.They can be that 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 according to concrete application scenario various shapes.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 is used, 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.When 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 take 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 performance that the invention provides catalyst that do not affect and maybe can improve the material of catalyst performance provided by the invention.As contained one or both in the components such as phosphorus, boron or fluorine, in element and take 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 take 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 molecular sieve, peptizing agent and the water with MFI structure, 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, the temperature of described formed body in the exit of described extruder is 40～150 ℃.
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 ℃), yet the present inventor finds in research process, make the temperature of formed body in the exit of described extruder be 40～150 ℃ and can make most probable aperture and the aperture concentration degree of the carrier prepared by this formed body meet previously described requirement.Preferably, the temperature of described formed body in the exit of described extruder is 50～120 ℃.Further preferably, the temperature of described formed body in the exit of described extruder is 60～100 ℃, can obtain so higher aperture concentration degree.More preferably, the temperature of described formed body in the exit of described extruder is 60～98 ℃.
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 extruding, 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 ℃, 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, of the present invention a kind of preferred embodiment in, the temperature of the described raw material that described step (1) obtains in the porch of described extruder is 40～100 ℃.At the carrier of guaranteeing preparation, have under the aperture of expection and the prerequisite of aperture concentration degree, the angle of the mechanical strength of the carrier of preparing from further raising, the temperature of the described raw material that described step (1) obtains in the porch of described extruder is preferably 40～80 ℃, more preferably 50～80 ℃.
Can adopt the whole bag of tricks to make the temperature of described raw material in the porch of described extruder is 40～100 ℃ (being preferably 40～80 ℃, more preferably 50～80 ℃).
Usually, can and have by the precursor of described heat-resistant inorganic oxide, Y zeolite the process that molecular sieve, peptizing agent and the water of MFI structure mixes carries out under heating condition, it is 40～100 ℃ (being preferably 40～80 ℃, more preferably 50～80 ℃) that the condition of described heating makes the raw material that the obtains temperature in the porch of described extruder.For example: can and have in the mixed process of molecular sieve, peptizing agent and water of MFI structure at precursor, the Y zeolite of heat-resistant inorganic oxide, within the scope of the temperature of raw material that heats to make preparation by external heat source in 40～100 ℃ (preferably 40～80 ℃, more preferably 50～80 ℃); Also can and there is at least one heating in molecular sieve, peptizing agent and the water of MFI structure by the precursor of described heat-resistant inorganic oxide, Y zeolite, then mix, make the temperature of the described raw material that obtains be 40～100 ℃ and (be preferably 40～80 ℃, more preferably 50～80 ℃), and the raw material that is 40～100 ℃ (being preferably 40～80 ℃, more preferably 50～80 ℃) by this temperature is sent in described extruder.For example, peptizing agent is mixed with water, and then precursor, the Y zeolite of the mixture obtaining and described heat-resistant inorganic oxide and the molecular sieve with MFI structure are mixed, afterwards described compound is sent into extruder for shaping.Wherein, can be by hot water be mixed with peptizing agent, obtain hot mixture, again precursor, the Y zeolite of this hot mixture and described heat-resistant inorganic oxide and the molecular sieve with MFI structure are mixed, thereby preparation temperature is 40～100 ℃ (is preferably 40～80 ℃, more preferably 50～80 ℃) raw material, and the raw material that is 40～100 ℃ (being preferably 40～80 ℃, more preferably 50～80 ℃) by this temperature is sent in extruder.
Wherein, at described raw material, comprise precursor, the Y zeolite of heat-resistant inorganic oxide and have in the molecular sieve mixture material of MFI structure, 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.Take 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, 0.5～30 % by weight more preferably, there is the content of molecular sieve of MFI structure 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 1～15 % by weight.
The silica alumina ratio of the molecular sieve of the described MFI of having structure 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 described in preferably with the molecular sieve of MFI structure 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 various Y zeolites that this area is conventional, 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.Take aluminium oxide as example, and its precursor is hydrated alumina, comprises aluminium hydroxide, boehmite, boehmite, gibbsite, and the gel that contains above-mentioned hydrated alumina or colloidal sol etc.They can be that commercially available commodity can be also to adopt existing method preparation arbitrarily.
In the specific embodiment, the average particulate diameter that the present invention prepares the precursor of the described heat-resistant inorganic oxide that described carrier uses 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.From further raising, prepare the angle of the aperture concentration degree of carrier, 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, by the Scherrer formula shown in formula I, calculated,
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
0broadening degree for 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 front page, Yang Cui is the volume such as surely) in the method stipulated 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.
Of the present invention a kind of 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%.
Of the present invention a kind of 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 a kind of most preferred embodiment of the present invention, the temperature of described raw material in the porch of described extruder is 40～80 ℃, the temperature of described formed body in the exit of described extruder is 60～98 ℃, 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, described by the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, Y zeolite with have in the described raw material that molecular sieve, peptizing agent and the water of MFI structure is 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, the total amount of described raw material of take is benchmark, and 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.In 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.
According to method of the present invention, be enough to make precursor, the Y zeolite of described heat-resistant inorganic oxide and/or heat-resistant inorganic oxide and thering is the described raw material that molecular sieve, peptizing agent and the water of MFI structure are 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 select for the routine of this area.
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 selected for the routine of this area.Usually, take 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 for 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, < < Lan Shi chemistry handbook > > second edition for example, 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: binary organic carboxyl acid).In 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.
Described polyalcohol refers to the organic compound in molecular structure with two above hydroxyls.The example of described polyalcohol can for 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 for 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 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: 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 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 select for the routine of this area.
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 ℃, 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 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 is not done 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 ℃, 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 is not done 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 is used 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.
When 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 take 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.
To what introduce hydrogenation active metals component on described carrier, it can be any means that those skilled in the art inform, 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 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 ethyl ammonium metatungstate.
The described compound containing group VIII metal be preferably take nickel as cationic oxysalt, take nickel as cationic anaerobic hydrochlorate, take cobalt as cationic oxysalt and one or more in cationic anaerobic hydrochlorate of cobalt of take.In the present invention, the example of the described compound containing 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 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, for water or the carbon number alcohol (as: ethanol) that is 1～5, be 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, for the carrier that load is had to the compound of described hydrogenation active metals component, carry out dry method and condition is not particularly limited.Usually, described dry temperature can be 80～350 ℃, is preferably 100～300 ℃; The described dry time can be 0.5～24 hour, is preferably 1～12 hour.
When 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 ℃, 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 will and spirit atmosphere in office, and this patent does not limit calcination atmosphere.
According to preparation method provided by the invention, while also containing one or both adjuvant components in components such as being selected from boron, phosphorus or fluorine in described catalyst, 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 the independent obtain solution of the compound that contains auxiliary agent, to contact with described carrier and roasting.When 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 ℃, be preferably 350-500 ℃, 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 produce, has the hydrocarbon system cut 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 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 hydrocracking and intermediate oil optionally, for all the other conditions of hydrocracking, be not particularly limited, and can be the normal condition of this area.Usually, described hydrocracking condition comprises: temperature can be 200～650 ℃, is preferably 300～510 ℃; In gauge pressure, pressure can be 3～24 MPas, is preferably 4～15 MPas; Hydrogen to oil volume ratio can be 150～2500; During 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 ℃, with sulphur, hydrogen sulfide or sulfur-bearing raw material, carry out presulfurization.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.
Below in conjunction with embodiment, describe the present invention in detail.
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 according to the method for stipulating in RIPP151-90, to measure most probable aperture and the aperture concentration degree of carrier.
In following examples and comparative example, adopt and be purchased the 3271E type Xray fluorescence spectrometer 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 is X ' pert in the model being purchased from Philips company, 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 for stipulating 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 for stipulating 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 (take from Chang Ling catalyst plant, SASOL company produces, relative crystallinity 95.4%, grain size 49.0nm, contents on dry basis is 75%, lower same) 84.0g, Siral40 powder (is purchased the company from SASOL, silica content is 40%, and contents on dry basis is 77.5%) 25.8g, Y zeolite A(lattice constant
, degree of crystallinity 81.4%, Na
2o0.02%, butt 86%, preparation method is referring to ZL01118446.9, embodiment 6, and molecular sieve I is lower same) 18.1g, ZRP-5 molecular sieve-4 A (is taken from Chang Ling catalyst plant, containing rare earth, there is MFI structure, silica alumina ratio 60.6, contents on dry basis is 83%, lower same) 2.4g, add sesbania powder 3g to be dry mixed evenly, obtain dry powder.3mL red fuming nitric acid (RFNA) is added in the beaker that is contained with 90mL deionized water, mix, obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of mixture is 40 ℃) 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 temperature of extrudate in the exit of extruder is 67 ℃.Extrudate is dried to 4 hours at 125 ℃.Then, in air atmosphere, at the temperature of 600 ℃, roasting 3 hours, in roasting process, the flow of air is 65L hour
-1, obtain, according to porous carrier of the present invention, being designated as porous carrier A1 after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.
Embodiment 2
Get CL powder (take from Chang Ling catalyst plant, relative crystallinity 98.1%, grain size 33.0nm, contents on dry basis is 71%, lower same) 45.1g, (be purchased the company from SASOL, silica content is 30% to Siral30 powder, contents on dry basis is 76%, lower same) 46.6g, 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) 30.1g, ZRP-5 molecular sieve B(takes from Chang Ling catalyst plant, containing rare earth, there is MFI structure, silica alumina ratio 35.6, contents on dry basis is 81%, lower same) 9.9g, add sesbania powder 3g and be dry mixed evenly, obtain dry powder.1.5mL red fuming nitric acid (RFNA) is added in the beaker that is contained with 87mL deionized water, mix, 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 temperature of extrudate in the exit of extruder is 41 ℃.Extrudate is dried to 5 hours at 110 ℃.Then, in air atmosphere, at the temperature of 570 ℃, roasting 3 hours, in roasting process, the flow of air is 35L hour
- 1, obtain, according to porous carrier of the present invention, being designated as porous carrier A2 after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.
Embodiment 3
Get C1 powder (take from Chang Ling catalyst plant, SASOL company produces, relative crystallinity 93.1%, grain size is 53.0nm, contents on dry basis is 74.5%, lower with) 51.0g, Siral30 powder 53.7g, 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) 12.3g, ZRP-5 molecular sieve-4 A 14.5g, adds sesbania powder 3g and is dry mixed evenly, obtains dry powder.1mL red fuming nitric acid (RFNA) is added in the beaker that is contained with 93mL deionized water, mix, obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of mixture is 25 ℃) 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 temperature of extrudate in the exit of extruder is 50 ℃.Extrudate is dried to 5 hours at 120 ℃.Then, in air atmosphere, at the temperature of 560 ℃, roasting 3 hours, in roasting process, the flow of air is 35L hour
-1, obtain, according to porous carrier of the present invention, being designated as porous carrier A3 after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.
Embodiment 4
Get SB powder 69.3g, Siral10 powder (be purchased the company from SASOL, silica content is 10%, and contents on dry basis is 74.5%, lower same) 53.7g, Y zeolite E(lattice constant
, degree of crystallinity 70.9%, Na
2o0.18%, butt 79%, Chang Ling catalyst plant is produced) 1.3g, ZRP-5 molecular sieve B8.6g, adds sesbania powder 3g and is dry mixed evenly, obtains dry powder.2mL red fuming nitric acid (RFNA) is added in the beaker that is contained with 81mL deionized water, mix, obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of mixture is 66 ℃) 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 temperature of extrudate in the exit of extruder is 90 ℃.Extrudate is dried to 4 hours at 120 ℃.Then, in air atmosphere, at the temperature of 550 ℃, roasting 4 hours, in roasting process, the flow of air is 105L hour
-1, obtain, according to porous carrier of the present invention, being designated as porous carrier A4 after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.
Embodiment 5
Get C1 powder 42.9g, Siral10 powder 77.4g, Y zeolite F(lattice constant 24.53A, degree of crystallinity 79.9%, Na
2o0.09%, butt 79%, Chang Ling catalyst plant is produced) 3.6g, ZRP-5 molecular sieve-4 A 5.9g, adds sesbania powder 3g and is dry mixed evenly, obtains dry powder.3.5mL red fuming nitric acid (RFNA) is added in the beaker that is contained with 82mL deionized water, mix, obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of mixture is 66 ℃) 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 temperature of extrudate in the exit of extruder is 91 ℃.Extrudate is dried to 5 hours at 110 ℃.Then, in air atmosphere, at the temperature of 570 ℃, roasting 3 hours, in roasting process, the flow of air is 35L hour
-1, obtain, according to porous carrier of the present invention, being designated as porous carrier A5 after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.
Embodiment 6
Get CL powder 61.9g, Siral10 powder 60.4g, Y zeolite D (lattice constant
, degree of crystallinity 72.5%, Na
2o0.13%, butt 81%, Chang Ling catalyst plant is produced) 10.0g, ZRP-5 molecular sieve B3.7g, adds sesbania powder 3g and is dry mixed evenly, obtains dry powder.2.5mL red fuming nitric acid (RFNA) is added in the beaker that is contained with 86mL deionized water, mix, obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture (temperature of mixture is 42 ℃) 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 temperature of extrudate in the exit of extruder is 72 ℃.Extrudate is dried to 12 hours at 105 ℃.Then, in air atmosphere, at the temperature of 580 ℃, roasting 2 hours, in roasting process, the flow of air is 35L hour
-1, obtain, according to porous carrier of the present invention, being designated as porous carrier A6 after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.
Comparative example
Get C1 powder 42.9g, Siral10 powder 77.4g, Y zeolite F3.6g, ZRP-5 molecular sieve-4 A 5.9g, adds sesbania powder 3g and is dry mixed evenly, obtains dry powder.3.5mL red fuming nitric acid (RFNA) is added in the beaker that is contained with 84mL deionized water, mix, 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 temperature of extrudate in the exit of extruder is 31 ℃.Extrudate is dried to 5 hours at 120 ℃.Then, in air atmosphere, at the temperature of 560 ℃, roasting 3 hours, in roasting process, the flow of air is 35L hour
-1, obtain, according to porous carrier of the present invention, being designated as porous carrier B1 after being cooled to room temperature.The most probable aperture of this porous carrier, aperture concentration degree and intensity are listed in table 1.
Table 1
Embodiment 5 is compared and can be found out with comparative example 1, adopt porous 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 7～12 is used for illustrating catalyst according to the invention and application and method for hydrogen cracking.
Embodiment 7～12
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, with this maceration extract, according to hole saturation, flood respectively the porous carrier A1～A6 of preparation in preparation example 1～6, and the carrier after dipping is dried to 2 hours at 120 ℃ in air atmosphere, then roasting 5 hours in air atmosphere at 350 ℃, thereby make the catalyst with hydrogenation, be designated as respectively catalyst X1～X6.The load capacity on porous carrier of ammonium metatungstate and nickel nitrate makes, and the total amount of catalyst of take is benchmark, in oxide, and in catalyst X1～X6, 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 7～12, different, porous carrier is the porous carrier B1 of comparative example 1 preparation.The catalyst making is designated as CX.The load capacity on porous carrier of ammonium metatungstate and nickel nitrate makes, and the total amount of catalyst of take is benchmark, in oxide, and WO
3be respectively 27.0 % by weight and 2.6 % by weight with NiO content.
Embodiment 13～15 is used for illustrating application and the method for hydrogen cracking of catalyst according to the invention.
Embodiment 13～15
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 ℃.
Catalyst is X1, X3, X5.
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 ℃, is 14.7MPa afterwards in hydrogen dividing potential drop, passes into feedstock oil when temperature is 350 ℃, hydrogen-oil ratio is 900 volume/volume, and during 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 that recovered (distilled) temperature needs while being 60% higher than the conversion ratio of the hydrocarbon ils of 350 ℃, 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 ℃ accounts for the percentage that recovered (distilled) temperature is less than the gross mass of 371 ℃ of cuts.The results are shown in table 2.
Comparative example 3
Adopt the performance of the catalyst of the method evaluation comparative example identical with embodiment 13～15 2 preparations.The results are shown in table 2.
Table 2
Catalyst X5 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 X5 used carrier A5 is apparently higher than the carrier B 1 of catalyst CX.The result of being listed by table 2 is seen and be the invention provides the selective and ability that reduces tail oil condensation point of the activity, intermediate oil of catalyst all higher than reference catalyst.
Claims (27)
1. a hydrocracking catalyst, this catalyst contains containing heat-resistant inorganic oxide matrix, Y zeolite and has the carrier of the molecular sieve of MFI structure, 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, take 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, has the content of molecular sieve of MFI structure 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, take described carrier as benchmark, in described carrier, the content of heat-resistant inorganic oxide is 60-95 % by weight, the content of Y zeolite is 0.5-35 % by weight, and the content with the molecular sieve of MFI structure is 0.5-35 % by weight.
6. according to the catalyst described in 1, it is characterized in that, take 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 with the molecular sieve of MFI structure is 1-15 % 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 take 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 take 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 and prepare the carrier that contains heat-resistant inorganic oxide matrix, Y zeolite and there is the molecular sieve of MFI structure, 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 molecular sieve, peptizing agent and the water with MFI structure, 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, the temperature of described formed body in the exit of described extruder is 40～150 ℃.
13. according to the method described in 12, it is characterized in that, the temperature of described formed body in the exit of described extruder is 50～120 ℃.
14. according to the method described in 13, it is characterized in that, the temperature of described formed body in the exit of described extruder is 60～100 ℃.
15. according to the method described in 14, it is characterized in that, the temperature of described formed body in the exit of described extruder is 60～98 ℃.
16. according to the method described in 12, it is characterized in that, take 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, has the content of molecular sieve of MFI structure 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, take 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 with the molecular sieve of MFI structure is 0.5-35 % by weight.
18. according to the method described in 17, it is characterized in that, take 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 with the molecular sieve of MFI structure is 1-15 % 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.
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| CN114433193A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and method for producing low freezing point diesel oil |
| CN114433193B (en) * | 2020-10-30 | 2023-12-12 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and method for producing low-freezing diesel oil |
| CN114433052A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst carrier, waterproof hydrogenation catalyst and hydrogenation modification method of high-oxygen-content biomass oil |
| CN114433052B (en) * | 2020-10-31 | 2023-12-12 | 中国石油化工股份有限公司 | Catalyst carrier, water-tolerant hydrogenation catalyst and hydro-upgrading method of high-oxygen-content biomass oil |
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