CN103028445B - Porous carrier as well as preparation method and application thereof - Google Patents
Porous carrier as well as preparation method and application thereof Download PDFInfo
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- CN103028445B CN103028445B CN201110301952.3A CN201110301952A CN103028445B CN 103028445 B CN103028445 B CN 103028445B CN 201110301952 A CN201110301952 A CN 201110301952A CN 103028445 B CN103028445 B CN 103028445B
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Abstract
The invention provides a porous carrier as well as a preparation method and the application of the porous carrier. The porous carrier provided by the invention contains heat-resistant inorganic oxide, and has the most probable aperture of 1-30nm and the aperture concentration ratio of 22-48. The preparation method of the porous carrier comprises the following steps of: mixing precursor capable of forming the heat-resistant inorganic oxide under the condition of roasting, peptizing agent and water to provide a raw material; sending the raw material into an extruding machine, kneading the raw material in the extruding machine, and then extruding to obtain a molded body; and roasting the molded body to obtain the porous carrier, wherein the temperature of the molded body at an outlet of the extruding machine is 40-150 DEG C. The porous carrier not only has larger aperture, but also has higher aperture concentration ratio, thereby being particularly taken as a carrier of catalyst with the function of hydrogenation.
Description
Technical field
The present invention relates to a kind of porous carrier and its preparation method and application.
Background technology
In recent years, in world wide crude oil heaviness and in poor quality tendency day by day obvious, meanwhile, the demand of intermediate oil and reformation, steam crack material is but constantly increased.This impels heavy distillate process technology to be developed rapidly, and catalyst is wherein the most important and crucial factor.
For mink cell focus or catalyst Molecular Cloning greatly, except requiring that catalyst has except larger aperture and enough pore volumes, also require that the pore-size distribution of catalyst mesopore concentrates (that is, aperture concentration degree is high).
Owing to being generally that active component load by having a catalytic action obtains on porous support for the catalyst of mink cell focus or macromolecular conversion, therefore preparation has larger aperture and pore volume, and the key with the catalyst of higher aperture concentration degree is to provide and has large aperture and the porous carrier with higher aperture concentration degree.
At present, the method being generally used for describing aperture concentration degree is: the pore volume calculated in given pore diameter range accounts for the percentage of total pore volume, and this percentage is higher, thinks that aperture concentration degree is also higher.But the aperture concentration degree that the method being accounted for the percentage of total pore volume by the pore volume calculated in given pore diameter range carrys out evaluation carrier is difficult to reflect exactly the pore-size distribution of carrier.
CN101757929A discloses and adopts the specific pore volume that measured by BET method to amass to the differential in aperture with in the distribution curve in aperture, and the ratio of the halfwidth at the height at peak and this peak can the aperture concentration degree of evaluate catalysts exactly.On this basis, CN101757929A also discloses a kind of hydrocracking catalyst, this catalyst contains the IVB race metal component in carrier and load hydrogenation activity composition on this carrier and the periodic table of elements, wherein, the most probable pore size of described carrier is 6 ~ 14nm, and aperture concentration degree is more than 7.Although the aperture concentration degree that CN101757929A discloses described carrier can be more than 7, from embodiment disclosed in CN101757929A, the aperture concentration degree of carrier is up to 21.4, needs to improve further.
To sum up, how to obtain and not only there is larger aperture, and there is the carrier of high aperture concentration degree, so obtain have high catalytic activity and intermediate oil optionally hydrocracking catalyst remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, there is provided a kind of and not only there is larger aperture, and there is the porous carrier of high aperture concentration degree, the hydrocracking catalyst prepared by this porous carrier there is high catalytic activity and intermediate oil selective.
The present inventor finds in practice process, improve the aperture concentration degree of carrier can significantly improve the catalytic activity of the catalyst obtained by this carrier and intermediate oil selective, but adopt the method for prior art can not obtain the carrier with higher aperture concentration degree (such as: aperture concentration degree is more than 22).Thus, the present inventor is on the basis of CN101757929A, carry out more intensive research, find: preparing formed body with extruder by extrusion molding, thus when obtaining porous carrier, make the temperature of described formed body in the exit of extruder be 40 ~ 150 DEG C, can obtain and there is larger aperture and aperture concentration degree is the carrier of more than 22.This completes the present invention.
The invention provides a kind of porous carrier, this porous carrier contains heat-resistant inorganic oxide, the most probable pore size of this porous carrier is 1 ~ 30nm, aperture concentration degree is 22 ~ 48, described most probable pore size adopts BET method to measure, described aperture concentration degree refers to that the dV/dr adopting BET method to measure is with in the distribution curve of varying aperture, and the ratio of the halfwidth at the height at peak and this peak, dV/dr represents that specific pore volume amasss the differential to aperture.
Present invention also offers a kind of preparation method of porous carrier, the method comprises and mixes, the precursor that can form heat-resistant inorganic oxide under roasting condition to supply raw materials with peptizing agent and water; Described raw material is sent in extruder, and extrudes after kneading in described extruder, 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 DEG C.
Invention further provides a kind of porous carrier prepared by method of the present invention.
Invention further provides a kind of porous carrier according to the present invention as the application of carrier of catalyst with hydrogenation.
Can obtain most probable pore size according to the preparation method of porous carrier of the present invention is 1 ~ 30nm, aperture concentration degree is more than 22 (such as: porous carrier 22 ~ 48), this porous carrier not only has larger aperture, and there is higher aperture concentration degree, thus this porous carrier is particularly suitable for the carrier as the catalyst with hydrogenation.
And, the preparation method of porous carrier of the present invention one preferred embodiment in, the temperature of described raw material in the porch of described extruder is made to be 40 ~ 100 DEG C, can not only obtain most probable pore size is 1 ~ 30nm, aperture concentration degree be more than 22 (such as: porous carrier 22 ~ 48), and the porous carrier of preparation also there is higher mechanical strength.
Accompanying drawing explanation
Fig. 1 is that the specific pore volume of porous carrier prepared by the embodiment of the present invention 1 amasss the differential in the aperture distribution curve schematic diagram with aperture.
Detailed description of the invention
The invention provides a kind of porous carrier, this porous carrier contains heat-resistant inorganic oxide.
According to porous carrier of the present invention, described most probable pore size can carry out suitable selection according to the embody rule occasion of the catalyst prepared by this porous carrier.At porous carrier according to the present invention for the preparation of when having the catalyst of hydrogenation, the most probable pore size of described porous carrier can be 1 ~ 30nm, is preferably 2 ~ 20nm, is more preferably 5 ~ 10nm.
According to porous carrier of the present invention, described aperture concentration degree can reach 22 ~ 48, even can reach 25 ~ 48 (can be such as 25 ~ 40).At porous carrier according to the present invention for the preparation of when having the catalyst of hydrogenation, the aperture concentration degree of described porous carrier is preferably 27 ~ 40.
In the present invention, term " most probable pore size " refers to: when adopting BET method to measure the pore structure of sample, and the specific pore volume of acquisition amasss differential (that is, dV/dr) to aperture with in the distribution curve in aperture, the aperture corresponding to the maximum of dV/dr.BET method is adopted to measure the pore structure of porous mass, known in those skilled in the art to obtain that specific pore volume to amass the differential in aperture with the method for the distribution curve in aperture, such as can according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety the first edition, the volumes such as Yang Cuiding) in the RIPP 151-90 that records the method that specifies measure.
In the present invention, term " aperture concentration degree " refers to: when adopting BET method to measure the pore structure of sample, and the specific pore volume of acquisition amasss to the differential in aperture with in the distribution curve in aperture, 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 there is multiple peak in described dV/dr is with the distribution curve of 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 that the specific pore volume of porous carrier prepared by the embodiment of the present invention 1 amasss the differential in the aperture distribution curve schematic diagram with aperture.In Fig. 1, abscissa is the aperture of porous carrier, and adopt logarithmic coordinates, unit is
ordinate is the differential that specific pore volume amasss to aperture.In Fig. 1, M represents peak height (that is, maximum dV/dr), and N represents that (that is, on described distribution curve, ordinate is halfwidth
two points between distance).When calculated hole diameters concentration degree, halfwidth and peak height all adopt identical long measure.
At porous carrier according to the present invention for the preparation of when having the catalyst of hydrogenation, the most probable pore size of described porous carrier can be 1 ~ 30nm, and aperture concentration degree can be 22 ~ 48.Preferably, the most probable pore size of described porous carrier is 2 ~ 20nm, and aperture concentration degree is 25 ~ 48 (being such as 25 ~ 40).Be in the scope of 2 ~ 20nm at the most probable pore size of described porous carrier, and aperture concentration degree is when being in the scope of 25 ~ 48, the catalyst with hydrogenation adopting this porous carrier to prepare when the hydrocracking for hydrocarbon ils, higher catalytic activity can be obtained and intermediate oil selective.The catalytic activity with the catalyst of hydrogenation finally obtained from further raising and intermediate oil optionally angle, the most probable pore size of described porous carrier is more preferably 5 ~ 10nm, and aperture concentration degree is more preferably 27 ~ 40.
Porous carrier according to the present invention contains heat-resistant inorganic oxide.
In the present invention, term " heat-resistant inorganic oxide " refers under oxygen or oxygen-containing atmosphere, and decomposition temperature is not less than the inorganic oxygen-containing compound of 300 DEG C (such as: decomposition temperature is 300 ~ 1000 DEG C).
The present invention is not particularly limited for the kind of described heat-resistant inorganic oxide, can be various heat-resistant inorganic oxide that can be shaping.The active component that load has hydrogenation is used at porous carrier according to the present invention, when having the catalyst of hydrogenation to be formed, described heat-resistant inorganic oxide can be one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and mesoporous Si-Al; Be preferably in aluminium oxide, silica and mesoporous Si-Al one or more; Be more preferably aluminium oxide and/or silica.One of the present invention 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.
In the present invention, the example of described molecular sieve can be but be not limited to: ZRP molecular sieve, MCM-41 molecular sieve, erionite, ZSM-34 molecular sieve, modenite, ZSM-5 molecular sieve, ZSM-11 molecular sieve, ZSM-12 molecular sieve, ZSM-22 molecular sieve, ZSM-23 molecular screen, ZSM-35 molecular sieve, L-type molecular sieve, Y zeolite, X-type molecular sieve, ZSM-3 molecular sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 molecular sieve, ZSM-57 molecular sieve, faujasite, beta-molecular sieve, Ω molecular sieve, phosphate aluminium molecular sieve, HTS and SAPO are (namely, SAPO) molecular sieve.The active component that load has hydrogenation is used at porous carrier according to the present invention, when there is the catalyst of hydrogenation with preparation, described molecular sieve be preferably 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 MCM-22 molecular sieve one or more.
According to the present invention, when described porous carrier contains heat-resistant inorganic oxide and molecular sieve, the ratio between described heat-resistant inorganic oxide and molecular sieve can carry out suitable selection according to the desired use of the catalyst prepared by this porous carrier.Such as, when the hydrocracking of the catalyst prepared by described porous carrier for hydrocarbon ils, with the total amount of described porous carrier for benchmark, the content of described molecular sieve can be 0.1 ~ 66 % by weight, be preferably 0.2 ~ 50 % by weight, be 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, is more preferably 70 ~ 99.5 % by weight, more preferably 80 ~ 99.25 % by weight.
According to the present invention, described porous carrier can have various shape according to concrete application scenario.Such as, described porous carrier can be spherical, bar shaped, annular, cloverleaf pattern, honeycombed and butterfly.
Present invention also offers a kind of preparation method of porous carrier, the method comprises and mixes, the precursor that can form heat-resistant inorganic oxide under roasting condition to supply raw materials with peptizing agent and water; Described raw material is sent in extruder, and extrudes after kneading in an extruder, 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 DEG C.
With extruder, raw material is being extruded, to obtain in the process of formed body, generally the cooling condition of described extruder is controlled as making the temperature of the formed body extruded be room temperature (lower than 40 DEG C), but the present inventor finds in research process, make the temperature of formed body in the exit of described extruder be 40 ~ 150 DEG C and the most probable pore size of the porous carrier prepared by this formed body and aperture concentration degree can be made to meet previously described requirement.Preferably, the temperature of described formed body in the exit of described extruder is 60 ~ 120 DEG C.Further preferably, the temperature of described formed body in the exit of described extruder is 60 ~ 100 DEG C.More preferably, the temperature of described formed body in the exit of described extruder is 60 ~ 98 DEG C, and the porous carrier of so preparation has higher aperture concentration degree.
According to method of the present invention, the formed body that various method can be adopted to make to be extruded by described extruder is within scope mentioned above in the temperature in the exit of this extruder.Such as: described raw material can carried out in an extruder in kneading or the process extruded, by regulating cooling condition or the heating condition of extruder fuselage and/or head, the formed body extruded by described extruder is within scope mentioned above in the temperature in the exit of this extruder.The method regulating the fuselage of extruder and/or the cooling condition of head or heating condition is known in the field, repeats no more herein.
The present inventor finds further 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 DEG C, the most probable pore size of the porous carrier prepared can not only be made to meet previously described requirement, and under the condition that all the other conditions are identical, the porous carrier of preparation has higher aperture concentration degree and mechanical strength.
Therefore, one of the present invention preferred embodiment in, the temperature of described raw material in the porch of described extruder is 40 ~ 100 DEG C.Under guaranteeing that the porous carrier prepared has the prerequisite in the aperture of expection, from the aperture concentration degree of porous carrier and the angle of mechanical strength that improve preparation further, described raw material is preferably 40 ~ 80 DEG C in the temperature of the porch of described extruder, be more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C.
Various method can be adopted to be 40 ~ 100 DEG C (are preferably 40 ~ 80 DEG C, are more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C) to make the temperature of described raw material in the porch of described extruder.
Usually, the process that described precursor, peptizing agent, water and the optional molecular sieve that can form heat-resistant inorganic oxide under roasting condition can be made to carry out mixing is carried out in a heated condition, the condition of described heating makes the temperature of raw material in the porch of described extruder obtained be 40 ~ 100 DEG C and (is preferably 40 ~ 80 DEG C, be more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C).Such as: can by the mixed process of described precursor, peptizing agent, water and the optional molecular sieve that can form heat-resistant inorganic oxide under roasting condition, being undertaken heating by external heat source makes the temperature of the raw material of preparation be in 40 ~ 100 DEG C (preferably 40 ~ 80 DEG C, more preferably 50 ~ 80 DEG C, preferably 55 ~ 80 DEG C further) scope within; Also can by least one heating in described precursor, peptizing agent, water and the optional molecular sieve that can form heat-resistant inorganic oxide under roasting condition, then mix, make the temperature of the described raw material obtained be 40 ~ 100 DEG C and (be preferably 40 ~ 80 DEG C, be more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C), and be 40 ~ 100 DEG C (preferably 40 ~ 80 DEG C by this temperature, be more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C) raw material send in described extruder.
According to method of the present invention, when preparing described raw material, usually first peptizing agent is mixed with water, and then the precursor that the mixture obtained can be formed heat-resistant inorganic oxide with described under roasting condition and optional molecular sieve mix, thus prepare described raw material; Therefore, can by hot water be mixed with peptizing agent, obtain the mixture of heat, the precursor that again mixture of this heat can be formed heat-resistant inorganic oxide with described under roasting condition and optional molecular sieve mix, thus preparation temperature is 40 ~ 100 DEG C (preferably 40 ~ 80 DEG C, be more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C) raw material, and be 40 ~ 100 DEG C (preferably 40 ~ 80 DEG C by this temperature, be more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C) raw material send in extruder.
In addition, it can also be 40 ~ 100 DEG C (preferably 40 ~ 80 DEG C described raw material was heated to temperature by means of external heat source before feeding extruder, be more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C), and be 40 ~ 100 DEG C (preferably 40 ~ 80 DEG C by this temperature, be more preferably 50 ~ 80 DEG C, more preferably 55 ~ 80 DEG C) raw material send in extruder.
One of the present invention more preferred embodiment in, described raw material is preferably 40 ~ 80 DEG C in the temperature of the porch of described extruder, and the temperature of described formed body in the exit of described extruder is 60 ~ 98 DEG C.According to porous carrier prepared by this embodiment, not only there is higher aperture concentration degree, and there is higher mechanical strength.
Method according to the present invention comprises and the precursor that can form described heat-resistant inorganic oxide under roasting condition being mixed with peptizing agent and water, to be provided for the raw material extruded.
The present invention is not particularly limited for the kind of described heat-resistant inorganic oxide, can carry out suitable selection according to the embody rule occasion of the porous carrier finally obtained.Such as, at the porous carrier finally obtained for the preparation of when having the catalyst of hydrogenation, described heat-resistant inorganic oxide can be one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and mesoporous Si-Al; Be preferably in aluminium oxide, silica and mesoporous Si-Al one or more; Be more preferably aluminium oxide and/or silica.One of the present invention 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, suitable selection can be carried out, as long as this precursor can form described heat-resistant inorganic oxide under roasting condition according to the kind of the heat-resistant inorganic oxide of expection.Usually, described precursor can be: can form the hydrous oxide of described heat-resistant inorganic oxide under roasting condition, contain the gel of the precursor that can form heat-resistant inorganic oxide under roasting condition and contain the colloidal sol of the precursor that can form heat-resistant inorganic oxide under roasting condition.In the present invention, term " hydrous oxide " refers to the hydrate of oxide.
Such as, when described heat-resistant inorganic oxide is aluminium oxide, the example of described precursor can include but not limited to: hydrated alumina (such as: aluminium hydroxide, boehmite), the gel containing hydrated alumina and the colloidal sol containing hydrated alumina.
According to method of the present invention, the average particulate diameter that the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition can be commonly used for this area.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 is 30 ~ 100nm, the porous carrier prepared by method of the present invention has higher aperture concentration degree.From the angle of the aperture concentration degree of the porous carrier of raising preparation further, the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is preferably 30 ~ 80nm, is 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.
The various methods that this area can be adopted to commonly use make the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition be within previously described scope.Such as, can by before use, the described precursor that can form heat-resistant inorganic oxide under roasting condition is carried out grinding and/or sieving, thus the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is within previously described scope.
In the present invention, described average particulate diameter adopts XRD method, obtained by the Scherrer formulae discovery shown in formula I,
In formula I, D is average particulate diameter;
λ is the wavelength of X-ray;
β
hKLfor the broadening degree that the high peak intensity place of diffracted ray half causes because of grain size refinement, wherein, β
hKL=B-B
0;
B is the peak width at half height of actual measurement;
B
0for the broadening degree of instrument;
θ is incidence angle.
According to the present invention, for load, there is the active component of hydrogenation at the porous carrier prepared by method of the present invention, thus when preparation has the catalyst of hydrogenation, described raw material is preferably containing the precursor that can form aluminium oxide under roasting condition.Such as, described raw material is preferably containing the boehmite that can form aluminium oxide under roasting condition.Although adopt various boehmite all can form aluminium oxide, and realize object of the present invention, but the present inventor finds in research process: adopt degree of crystallinity be more than 80% boehmite under guaranteeing that the porous carrier of final preparation has the condition of large aperture and pore volume, aperture concentration degree and the mechanical strength of the porous carrier obtained can be improved further.
In the present invention, described degree of crystallinity is relative crystallinity, adopt " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety the first edition, the Yang Cui volume such as surely) in the method that specifies in the RIPP 139-90 that records measure, wherein, the standard specimen used is the sample being numbered S87-16B, the absolute crystallinity of this standard specimen is 98.0%, can be commercially available by Research Inst. of Petroleum Processing, SINOPEC.
One of the present invention preferred embodiment in, the 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%, be preferably more than 90%.From the angle of aperture concentration degree improving the porous carrier obtained further, the relative crystallinity of described boehmite is preferably 90 ~ 110%.
One of the present invention 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 the most preferred embodiment of one of the present invention, the temperature of described raw material in the porch of described extruder is 40 ~ 80 DEG C, the temperature of described formed body in the exit of described extruder is 60 ~ 98 DEG C, 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.According to porous carrier prepared by this embodiment, there is higher aperture concentration degree and the mechanical strength of Geng Gao.
According to method of the present invention, described raw material is also containing peptizing agent.The amount of the peptizing agent in described raw material can carry out suitable selection according to the used kind that can form the precursor of heat-resistant inorganic oxide under roasting condition.Usually, with the total amount of described raw material for benchmark, the content of described peptizing agent can be 0.1 ~ 5 % by weight, is preferably 0.5 ~ 4 % by weight.
The present invention is not particularly limited for the kind of described peptizing agent, can be that the routine of this area is selected.In the present invention, the instantiation of described peptizing agent can be but be not limited to: nitric acid, hydrochloric acid, phosphoric acid, trichloroacetic acid and citric acid.
According to method of the present invention, use water as decentralized medium when preparing described raw material, the precursor that can form heat-resistant inorganic oxide by described under roasting condition and peptizing agent mix.The present invention is not particularly limited for the consumption of described water, can be that the routine of this area is selected, as long as described precursor and peptizing agent can mix by the amount of described water.
According to method of the present invention, described raw material can also contain extrusion aid.The content of described extrusion aid and kind can be that the routine of this area is selected.
Usually, with the total amount of described raw material for benchmark, the consumption of described extrusion aid can be 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 organic carboxyl acid, polyalcohol, organic amine and surfactant.
In the present invention, term " organic carboxyl acid " refers in molecular structure the organic compound with one or more carboxyl, such as " Lan Shi Chemical manual " second edition, the organic carboxyl acid enumerated in 1.26 ~ 1.27.Preferably, described organic carboxyl acid to be carbon number be 1 ~ 20 unary organic carboxylic acid or polybasic organic carboxylic acid's (such as: binary organic carboxyl acid).In the present invention, the example of described organic carboxyl acid can be but be not limited to: formic acid, acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid and benzenpropanoic acid.
In the present invention, term " polyol " refers in molecular structure the organic compound with two or more hydroxyl.The example of described polyalcohol can be but be not limited to: ethylene glycol, glycerine and butanediol.
In the present invention, term " organic amine " refers to the organic compound containing one or more amido in molecular structure.The example of described organic amine can be but be not limited to: monoethanolamine, diethanol amine, triethanolamine, N methyldiethanol amine and urea.
In 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 be but be not limited to: stearic acid and neopelex.The example of described cationic surface active agent can be but be not limited to: quaternary ammonium compound.The example of described amphoteric ionic surfactant can be but be not limited to: lecithin, amino acid type surfactant and betaine type amphoteric surfactant.The example of described nonionic surface active agent can be but be not limited to: fatty glyceride, aliphatic acid sorb smooth (span series), polysorbate (TWEEN Series surfactant), polyoxyethylene-type surfactant and polyox-yethylene-polyoxypropylene block copolymer.
According to method of the present invention, described raw material can also contain molecular sieve.There is no particular limitation for the kind that the present invention sieves for described raw material Middle molecule and consumption, and described molecular sieve can be zeolite molecular sieve and/or non-zeolite molecular sieve.In the present invention, the example of described molecular sieve can be but be not limited to: ZRP molecular sieve, MCM-41 molecular sieve, erionite, ZSM-34 molecular sieve, modenite, ZSM-5 molecular sieve, ZSM-11 molecular sieve, ZSM-12 molecular sieve, ZSM-22 molecular sieve, ZSM-23 molecular screen, ZSM-35 molecular sieve, L-type molecular sieve, Y zeolite, X-type molecular sieve, ZSM-3 molecular sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, beta-molecular sieve, Ω molecular sieve, phosphate aluminium molecular sieve, HTS and SAPO are (namely, SAPO) molecular sieve.The active component that load has hydrogenation is used at porous carrier according to the present invention, when there is the catalyst of hydrogenation with preparation, described molecular sieve be preferably 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 MCM-22 molecular sieve one or more.
According to method of the present invention, the consumption of described molecular sieve can be the conventional amount used of this area.Such as: at obtained porous carrier for the preparation of when there is the catalyst of hydrogenation, the content of described raw material Middle molecule sieve makes in the porous carrier prepared, with the total amount of described porous carrier for benchmark, the content of described molecular sieve can be 0.1 ~ 66 % by weight, be preferably 0.2 ~ 50 % by weight, be 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, is more preferably 70 ~ 99.5 % by weight, more preferably 80 ~ 99.25 % by weight.
Method according to the present invention comprises to be extruded described raw material, to obtain formed body.According to method of the present invention, the various extruders that described extruder can be commonly used for this area.The present invention is also not particularly limited for described kneading and the condition extruded, and can be that the routine of this area is selected.
Also comprise according to method of the present invention and described formed body is carried out roasting, thus 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 DEG C, is preferably 450 ~ 650 DEG C; The time of described roasting can be 1 ~ 10 hour, is preferably 2 ~ 5 hours.Described roasting can be carried out in oxygen-containing atmosphere, also can carry out in an inert atmosphere.
In the present invention, described inert atmosphere refers under drying or roasting condition to be inactive gas, such as: nitrogen and group 0 element gas (as argon gas).
According to method of the present invention, before described formed body is carried out roasting, can also comprise and described formed body is carried out drying, described drying can be carried out under the normal condition of this area, such as: the temperature of described drying can be 100 ~ 200 DEG C, 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 at reduced pressure, be not particularly limited.Described drying can be carried out in oxygen-containing atmosphere, also can carry out in inert atmosphere.
Invention further provides a kind of porous carrier prepared by method of the present invention.
By prepared according to the methods of the invention porous carrier, there is high aperture concentration degree.Usually, the most probable pore size of prepared according to the methods of the invention porous carrier can be 1 ~ 30nm, is preferably 2 ~ 20nm, is more preferably 5 ~ 10nm; Aperture concentration degree can be 22 ~ 48, is preferably 25 ~ 48 (can be such as 25 ~ 40), is more preferably 27 ~ 40.
One of the present invention preferred embodiment in, the most probable pore size of the porous carrier prepared by method of the present invention is 1 ~ 30nm, and aperture concentration degree is 22 ~ 48.One of the present invention more preferred embodiment in, the most probable pore size of the porous carrier prepared by method of the present invention is 2 ~ 20nm, and aperture concentration degree is 25 ~ 48 (can be such as 25 ~ 40).In a kind of further preferred embodiment of the present invention, the most probable pore size of the porous carrier prepared by method of the present invention is 5 ~ 10nm, and aperture concentration degree is 27 ~ 40.
According to porous carrier of the present invention, not only there is large aperture, and there is high aperture concentration degree, be particularly useful for making the catalyst with hydrogenation, especially for the catalyst of the hydrocracking of heavy oil.Thus, the present invention still further provides a kind of porous carrier according to the present invention as the application of carrier of catalyst with hydrogenation.
At porous carrier according to the present invention as when there is the carrier of catalyst of hydrogenation, the method that this area can be adopted to commonly use has the catalyst of hydrogenation described in preparing, such as: by there is the active constituent loading of hydrogenation on porous carrier according to the present invention, thus the catalyst with hydrogenation can be obtained.
According to the present invention, described in there is hydrogenation active component can be group vib metal and group VIII metal.Described group vib metal and group VIII metal can respectively with the various forms load of this area routine on described porous carrier, such as: described group vib metal and group VIII metal can be loaded on described porous carrier respectively in the form of the oxide.
The described load capacity of active component on described porous carrier with hydrogenation can be the conventional amount used of this area.Usually, with the total amount of the catalyst finally obtained for benchmark, with oxide basis, described in there is the active component of hydrogenation amount can be 5 ~ 60 % by weight, be preferably 10 ~ 50 % by weight; The amount of described carrier can be 40 ~ 95 % by weight, is preferably 50 ~ 90 % by weight.The described active component with hydrogenation be group vib metal and group VIII metal time, with the total amount of described catalyst for benchmark, with oxide basis, the content of described group vib metal can be 10 ~ 40 % by weight, be 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 and well known to a person skilled in the art various method by the described active constituent loading with hydrogenation on described porous carrier.
Such as, can by there is the solution impregnation of the compound of the active component of hydrogenation according to porous carrier of the present invention described in containing, and load had the carrier of described compound to carry out drying and roasting, thus by the described active component load with hydrogenation on described porous carrier.The described active component with hydrogenation be group vib metal and group VIII metal time, the compound containing group vib metal that described compound can be commonly used for this area and containing the compound of group VIII metal.Described group vib metal be molybdenum and/or tungsten time, the described compound containing group vib metal is preferably the compound of tungsten and/or the compound of molybdenum.In the present invention, the described example containing the compound of 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.Described group VIII metal be cobalt and/or nickel time, the described compound containing group VIII metal is preferably and is cationic oxysalt with nickel, is cationic anaerobic hydrochlorate with nickel, take cobalt as cationic oxysalt and be one or more in cationic anaerobic hydrochlorate with cobalt.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, the solution of the compound containing described active component prepared by the various solvents that this area can be adopted to commonly use, as long as described compound can be dissolved in described solvent, forms the solution of stable homogeneous.Such as: described solvent can for water or carbon number be 1 ~ 5 alcohol (as: ethanol), be preferably water and/or ethanol, be more preferably water.
The method of described dipping can be the conventional various dipping methods in this area, such as, 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 can guarantee that the amount with the active component of catalytic action on the catalyst that finally obtains meets concrete instructions for use.Usually, the time of described dipping can be 0.5 ~ 12 hour.
According to the present invention, carry out dry condition for load there being the porous carrier of described compound and be not particularly limited.Usually, the temperature of described drying can be 80 ~ 300 DEG C, is preferably 100 ~ 200 DEG C; 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 having the carrier of described compound to carry out roasting the load of drying, can be the normal condition of this area.Usually, the temperature of described roasting can be 350 ~ 700 DEG C, is preferably 400 ~ 650 DEG C; The time of described roasting can be 0.2 ~ 12 hour, is preferably 1 ~ 10 hour.Described roasting can be carried out in oxygen-containing atmosphere, also can carry out in an inert atmosphere.
The present invention is described in detail below in conjunction with embodiment.
The reagent used in following examples and comparative example, except special instruction, is chemically pure reagent.
In following examples and comparative example, being purchased the model from Quantachrome company be
on the six full-automatic specific surfaces in station of-6B and pore size distribution determining instrument, BET method is adopted to measure most probable pore size and the aperture concentration degree of porous carrier according to the method specified in RIPP 151-90.
In following examples and comparative example, adopt the 3271E type Xray fluorescence spectrometer be purchased from Rigaku electric machine industry Co., Ltd., analysiss mensuration is carried out to the content of element each in catalyst.
In following examples and comparative example, being on the X-ray diffractometer of X ' pert being purchased from the model of Philips company, measuring the average particulate diameter of porous carrier and degree of crystallinity, wherein, degree of crystallinity is relative crystallinity, is to measure according to the method specified in RIPP 139-90.
In following examples and comparative example, be the upper crushing strength measuring porous carrier of crushing strength analyzer (manufacture of alkaline research institute of the Ministry of Chemical Industry) of QCY-602 in model according to the method specified in GB3635-1983.
In following examples and comparative example, pressure is all in gauge pressure.
Embodiment 1
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Getting CL powder (is purchased from Chang Ling catalyst plant, contents on dry basis is 71 % by weight, for a kind of boehmite, relative crystallinity is 98.1%, average particulate diameter is 33nm, lower same) (be purchased from sasol company, contents on dry basis is 81 % by weight to 98.6g, aluminum silicon powder SIRAL 70 powder, for the mixture of the hydrate of aluminium oxide and the hydrate of silica, with oxide basis, 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, adding sesbania powder 4g is dry mixed evenly, obtains dry powder.1.5mL red fuming nitric acid (RFNA) (concentration is 65 % by weight, lower same) and 3g triethanolamine are added in the beaker being contained with 110mL deionized water, mixes, obtain acid solution.By acid solution and dry powder blend, and stir, to obtain the raw mixture for extruding, the temperature of described deionized water makes the temperature of the raw mixture obtained be 40 DEG C.Be that in the mixture feeding banded extruder of 40 DEG C, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the temperature of extrudate in the exit of extruder is 72 DEG C by the temperature obtained.By extrudate 105 DEG C of dryings 4 hours.Then, in air atmosphere, at the temperature of 620 DEG C, roasting 2 hours, in roasting process, the flow of air is 12L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A1.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 2
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Getting C1 powder (is purchased from sasol company, contents on dry basis is 74.5 % by weight, for a kind of boehmite, relative crystallinity is 93.1%, average particulate diameter is 53nm) 73.8g, aluminum silicon powder SIRAL 40 powder (is purchased from sasol company, contents on dry basis is 77.5 % by weight, for the mixture of the hydrate of aluminium oxide and the hydrate of silica, with oxide basis, the content of silica is 40 % by weight, the content of aluminium oxide is 60 % by weight, average particulate diameter is 55nm, lower same) 51.6g, (lattice constant is 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.3mL red fuming nitric acid (RFNA) is added in the beaker being contained with 103mL deionized water, mixes, obtain acid solution.By acid solution and dry powder blend, and stirring, obtaining the raw mixture for extruding, the temperature of described deionized water makes the temperature of the raw mixture obtained be 65 DEG C.Be that in the mixture feeding banded extruder of 65 DEG C, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the temperature of extrudate in the exit of extruder is 88 DEG C by the temperature obtained.By extrudate 110 DEG C of dryings 8 hours.Then, in air atmosphere, at the temperature of 600 DEG C, roasting 2 hours, in roasting process, the flow of air is 65L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A2.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 3
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Getting SD powder (is purchased from Shandong Aluminum Plant, contents on dry basis is 64 % by weight, for a kind of boehmite, relative crystallinity is 103%, average particulate diameter is 46nm) 62.5g, aluminum silicon powder SIRAL 10 powder (is purchased from sasol company, contents on dry basis is 74.5 % by weight, is the mixture of the hydrate of aluminium oxide and the hydrate of silica, with oxide basis, the content of silica is 10 % by weight, the content of aluminium oxide is 90 % by weight, and average particulate diameter is 53nm, lower same) 80.5g, adding sesbania powder 4g is dry mixed evenly, to obtain dry powder.2mL red fuming nitric acid (RFNA) and 2g PEG400 (being purchased from Zhengzhou Cheng Xiang Chemical Industry Science Co., Ltd) are added in the beaker being contained with 78mL deionized water, mixes, to obtain acid solution.By acid solution and dry powder blend, and stir, to obtain the raw mixture for extruding, the temperature of described deionized water makes the temperature of the raw mixture obtained be 60 DEG C.Be that 60 DEG C of mixtures are sent in banded extruder by the temperature obtained, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the temperature of extrudate in the exit of extruder is 81 DEG C.By extrudate 115 DEG C of dryings 6 hours.Then, in air atmosphere, at the temperature of 580 DEG C, roasting 3 hours, in roasting process, the flow of air is 200L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A3.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 4
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Get CL powder 91.5g, aluminum silicon powder SIRAL 20 powder (is purchased from sasol company, contents on dry basis is 75 % by weight, for the mixture of the hydrate of aluminium oxide and the hydrate of silica, with oxide basis, the content of silica is 20 % by weight, the content of aluminium oxide is 80 % by weight, average particulate diameter is 53nm) 46.7g, 1.2 grams, Beta molecular sieve (silica alumina ratio is 61.4, and relative crystallinity is 84.2%, and contents on dry basis is 83 % by weight), adding sesbania powder 4g is dry mixed evenly, to obtain dry powder.3.5mL red fuming nitric acid (RFNA) is added in the beaker being contained with 95mL deionized water, mixes, to obtain acid solution.By acid solution and dry powder blend, and stirring, obtaining the raw mixture (temperature of raw mixture is room temperature (25 DEG C)) for extruding.Sent in banded extruder by the mixture obtained (temperature is room temperature (25 DEG C)), be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the extrudate temperature in the exit of described extruder is 64 DEG C.By extrudate 120 DEG C of dryings 5 hours.Then, in air atmosphere, at the temperature of 560 DEG C, roasting 3 hours, in roasting process, the flow of air is 35L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A4.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 5
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
(be purchased from sasol company, contents on dry basis is 75 % by weight, is a kind of boehmite to get SB powder, relative crystallinity is 95.4%, and average particulate diameter is 49nm, lower same) 93.3g, aluminum silicon powder SIRAL40 powder 38.7g, adds sesbania powder 4g and is dry mixed evenly, to obtain dry powder.2.5mL red fuming nitric acid (RFNA) is added in the beaker being contained with 90mL deionized water, mixes, to obtain acid solution.By acid solution and dry powder blend, and stirring, obtaining the raw mixture for extruding, the temperature of described deionized water makes the temperature of the raw mixture obtained be 80 DEG C.Be that 80 DEG C of mixtures are sent in banded extruder by the temperature obtained, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the temperature of extrudate in the exit of extruder is 92 DEG C.By extrudate 125 DEG C of dryings 10 hours.Then, in air atmosphere, at the temperature of 540 DEG C, roasting 4 hours, in roasting process, the flow of air is 105L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A5.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 6
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
The method identical with embodiment 4 is adopted to prepare porous carrier, unlike, the extrudate temperature in the exit of described extruder is 43 DEG C.The porous carrier of the present invention of preparation is designated as porous carrier A6.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 7
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Get C1 powder 67.1g, aluminum silicon powder SIRAL 40 powder 64.5g, add sesbania powder 4g and be dry mixed evenly, to obtain dry powder.The red fuming nitric acid (RFNA) of 3mL is added in the beaker being contained with 106mL deionized water, mixes, to obtain acid solution.By acid solution and dry powder blend, and stir, to obtain the raw mixture for extruding, the temperature of described deionized water makes the temperature of the raw mixture obtained be 45 DEG C.Be that in the mixture feeding banded extruder of 45 DEG C, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the temperature of extrudate in the exit of extruder is 78 DEG C by the temperature obtained.By extrudate 110 DEG C of dryings 6 hours.Then, in air atmosphere, at the temperature of 620 DEG C, roasting 5 hours, in roasting process, the flow of air is 35L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A7.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 8
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Get SB powder 93.3g, aluminum silicon powder SIRAL 20 powder 40g, add sesbania powder 4g and be dry mixed evenly, to obtain dry powder.2mL red fuming nitric acid (RFNA) is added in the beaker being contained with 87mL deionized water, mixes, to obtain acid solution.By acid solution and dry powder blend, and stir, to obtain the raw mixture for extruding, the temperature of described deionized water makes the temperature of the raw mixture obtained be 60 DEG C.Be that in the mixture feeding banded extruder of 60 DEG C, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the temperature of extrudate in the exit of extruder is 84 DEG C by the temperature obtained.By extrudate 115 DEG C of dryings 4 hours.Then, in air atmosphere, at the temperature of 600 DEG C, roasting 5 hours, in roasting process, the flow of air is 200L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A8.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 9
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Get CL powder 119.7g, (lattice constant is 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 5g urea are added in the beaker being contained with 106mL deionized water, mixes, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain raw mixture (temperature of raw mixture is room temperature (25 DEG C)).Sent in banded extruder by the mixture obtained (temperature is room temperature (25 DEG C)), be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the extrudate temperature in the exit of described extruder is 80 DEG C.By extrudate 120 DEG C of dryings 8 hours.Then, in air atmosphere, at the temperature of 580 DEG C, roasting 2 hours, in roasting process, the flow of air is 65L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A9.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 10
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Get C1 powder 100.7g, aluminum silicon powder SIRAL 40 powder 32.3g, add sesbania powder 4g and be dry mixed evenly, to obtain dry powder.2.5mL red fuming nitric acid (RFNA) is added in the beaker being contained with 104mL deionized water, mixes, to obtain acid solution.By acid solution and dry powder blend, and stir, to obtain the raw mixture for extruding, the temperature of described deionized water makes the temperature of the raw mixture obtained be 55 DEG C.Be that in the mixture feeding banded extruder of 55 DEG C, be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the temperature of extrudate in the exit of extruder is 78 DEG C by the temperature obtained.By extrudate 125 DEG C of dryings 7 hours.Then, in air atmosphere, at the temperature of 560 DEG C, roasting 3 hours, in roasting process, the flow of air is 12L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A10.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 11
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
Get SD powder 71.8g, aluminum silicon powder SIRAL 30 powder (is purchased from sasol company, contents on dry basis is 77.5 % by weight, for the mixture of the hydrate of aluminium oxide and the hydrate of silica, with oxide basis, the content of silica is 30 % by weight, 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, adding sesbania powder 4g is dry mixed evenly, to obtain dry powder.1mL red fuming nitric acid (RFNA) is added in the beaker being contained with 92mL deionized water, mixes, to obtain acid solution.By acid solution and dry powder blend, and stir, to obtain the raw mixture (temperature of raw mixture is room temperature (25 DEG C)) for extruding.Sent in banded extruder by the mixture obtained (temperature is room temperature (25 DEG C)), be extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, the extrudate temperature in the exit of described extruder is 60 DEG C.By extrudate 105 DEG C of dryings 5 hours.Then, in air atmosphere, at the temperature of 540 DEG C, roasting 4 hours, in roasting process, the flow of air is 105L hour
-1, obtain after being cooled to room temperature according to porous carrier of the present invention, be designated as porous carrier A11.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 12
The present embodiment is for illustration of porous carrier according to the present invention and preparation method thereof.
The method identical with embodiment 4 is adopted to prepare porous carrier, unlike, the extrudate temperature in the exit of described extruder is 98 DEG C.The porous carrier according to the present invention of preparation is designated as porous carrier A12.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 13
The present embodiment is used for illustrating according to porous carrier of the present invention and preparation method thereof.
The method identical with embodiment 8 is adopted to prepare porous carrier, unlike, dry glue powder (the method preparation disclosed in CN100999328B embodiment 3 used, for a kind of boehmite, relative crystallinity is 76%, average particulate diameter is 36nm) replace SB powder, the porous carrier of preparation is designated as porous carrier A13.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Embodiment 14
The present embodiment is used for illustrating according to porous carrier of the present invention and preparation method thereof.
The method identical with embodiment 2 is adopted to prepare porous carrier, unlike, the temperature of raw mixture when entering described extruder is room temperature (25 DEG C), and the porous carrier obtained is designated as porous carrier A14.The most probable pore size of this porous carrier, aperture concentration degree and intensity are listed in Table 1.
Comparative example 1
The method identical with embodiment 4 is adopted to prepare porous carrier, unlike, the extrudate temperature in the exit of described extruder is 35 DEG C, and the porous carrier obtained is designated as porous carrier B1.Most probable pore size and the aperture concentration degree of this porous carrier are listed in Table 1.
Table 1
| Embodiment is numbered | Porous carrier is numbered | Aperture, most probable hole (nm) | Aperture concentration degree | Crushing strength (N/mm) |
| Embodiment 1 | A1 | 8.8 | 26.7 | 25.8 |
| Embodiment 2 | A2 | 8.2 | 33.4 | 27.3 |
| Embodiment 3 | A3 | 6.6 | 28.3 | 23.3 |
| Embodiment 4 | A4 | 9.1 | 28.1 | 24.5 |
| Embodiment 5 | A5 | 7.4 | 38.4 | 30.8 |
| Embodiment 6 | A6 | 8.8 | 25.7 | 21.2 |
| Embodiment 7 | A7 | 7.8 | 30.6 | 25.4 |
| Embodiment 8 | A8 | 7.1 | 33.7 | 29.9 |
| Embodiment 9 | A9 | 5.8 | 25.4 | 27.7 |
| Embodiment 10 | A10 | 9.3 | 29.8 | 30.6 |
| Embodiment 11 | A11 | 6.4 | 26.9 | 19.8 |
| Embodiment 12 | A12 | 9.1 | 27.0 | 25.3 |
| Embodiment 13 | A13 | 6.2 | 22.0 | 22.4 |
| Embodiment 14 | A14 | 8.1 | 25.8 | 20.1 |
| Comparative example 1 | B1 | 8.9 | 19.0 | 18.8 |
Embodiment 4,6 and 12 and comparative example 1 are compared and can be found out, the porous carrier adopting method of the present invention to prepare not only has larger aperture, but also has higher aperture concentration degree and mechanical strength.
Embodiment 2 and embodiment 14 are compared and can find out, the temperature of described raw material in the porch of described extruder is made to be 40 ~ 80 DEG C, and make the temperature of described formed body in the exit of described extruder be 60 ~ 98 DEG C, the porous carrier of preparation not only has higher most probable pore size and aperture concentration degree, and has higher mechanical strength.
Embodiment 8 and embodiment 13 are compared and can be found out, porous carrier prepared by the raw material that employing is the boehmite of more than 80% containing relative crystallinity has higher aperture concentration degree and mechanical strength.
Embodiment 15 ~ 28
Embodiment 15 ~ 28 is used for illustrating that porous carrier according to the present invention is preparing the application had in the catalyst of hydrogenation.
Ammonium metatungstate (being purchased from Chang Ling catalyst plant) and nickel nitrate (being purchased from the sharp chemical reagent factory of Beijing benefit) are dissolved in the water, be mixed with maceration extract, flood the porous carrier A1 ~ A14 of preparation in embodiment 1 ~ 14 respectively according to hole saturation with this maceration extract, and by the carrier after dipping at 120 DEG C in air atmosphere dry 2 hours, then roasting 5 hours in air atmosphere at 350 DEG C, thus the obtained catalyst with hydrogenation, be designated as catalyst X1 ~ X14 respectively.Ammonium metatungstate and nickel nitrate load capacity on porous support makes with the total amount of catalyst for benchmark, with oxide basis, in catalyst X1 ~ X14, and WO
327.0 % by weight and 2.6 % by weight are respectively with NiO content.
Comparative example 2
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 15 ~ 28, unlike, porous carrier is porous carrier prepared by comparative example 1.Obtained catalyst is designated as CX1.Ammonium metatungstate and nickel nitrate load capacity on porous support makes with the total amount of catalyst for benchmark, with oxide basis, and WO
327.0 % by weight and 2.6 % by weight are respectively with NiO content.
EXPERIMENTAL EXAMPLE 1 ~ 14
EXPERIMENTAL EXAMPLE 1 ~ 14 is used for the performance of catalyst prepared by Evaluation operation example 15 ~ 28.
Evaluating catalyst adopts once by flow process, and feedstock oil adopts sand gently to subtract two, and the density (20 DEG C) of this feedstock oil is 0.9062g/cm
3, refraction index (20 DEG C) is 1.4852; Initial boiling point (IBP) is 299 DEG C, and 5% recovered (distilled) temperature is 359 DEG C, and 50% recovered (distilled) temperature is 399 DEG C, and 95% recovered (distilled) temperature is 436 DEG C.
Diameter is become by catalyst breakage to be the particle of 0.5 ~ 1.0 millimeter, this catalyst 200 milliliters is loaded in 200 milliliters of fixed bed reactors, before logical oil, first catalyst is 15.0MPa in hydrogen dividing potential drop, and temperature is sulfuration 28 hours under the condition of 300 DEG C, is 14.7MPa in hydrogen dividing potential drop afterwards, passes into feedstock oil when temperature is 350 DEG C, hydrogen-oil ratio is 900 volume/volume, and during liquid, volume space velocity is 0.75h
-1, and sample after 400 hours in reaction.
Catalytic activity and the intermediate oil of evaluate catalysts are selective, wherein:
The cracking reaction temperature needed when activity refers to that recovered (distilled) temperature is 60% higher than the conversion ratio of the hydrocarbon ils of 350 DEG C, the catalytic activity of cracking reaction temperature lower explanation catalyst is higher;
Intermediate oil is selective refers to that recovered (distilled) temperature is the percentage that the content of the cut of 132 ~ 371 DEG C accounts for recovered (distilled) temperature and is less than the gross mass of 371 DEG C of cuts.
Experimental comparison's example 1
The performance of the catalyst adopting the method evaluation comparative example 2 identical with EXPERIMENTAL EXAMPLE 1 ~ 14 to prepare.Result is as shown in table 2.
EXPERIMENTAL EXAMPLE 1 ~ 14 and Experimental comparison's example 1 result display, the catalyst with hydrogenation prepared by porous carrier according to the present invention there is higher hydrodesulfurization activity and intermediate oil selective.Table 2 lists hydrodesulfurization activity and the intermediate oil optionally concrete numerical value of EXPERIMENTAL EXAMPLE 2,4,5,7 and 14 and Experimental comparison's example 1.
Table 2
| Numbering | Catalyst | Active (DEG C) | Selective (%) |
| 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 |
| Experimental comparison's example 1 | CX1 | 398.7 | 83.1 |
EXPERIMENTAL EXAMPLE 4 and Experimental comparison's example 1 are compared and can find out, the catalyst with hydrogenation adopting porous carrier according to the present invention to prepare there is higher catalytic activity and intermediate oil selective.
EXPERIMENTAL EXAMPLE 2 and EXPERIMENTAL EXAMPLE 14 are compared and can find out, under the condition that all the other conditions are identical, aperture concentration degree for the preparation of the porous carrier of catalyst is higher, then the catalyst with hydrogenation prepared there is higher catalytic activity and intermediate oil selective.
Claims (16)
1. a preparation method for porous carrier, the method comprises and mixes, the precursor that can form heat-resistant inorganic oxide under roasting condition to supply raw materials with peptizing agent and water; Described raw material is sent in extruder, and extrudes after kneading in described extruder, to obtain formed body; Described formed body is carried out roasting, to obtain described porous carrier, it is characterized in that, the temperature of described formed body in the exit of described extruder is 40 ~ 150 DEG C, and the temperature of described raw material in the porch of described extruder is 40 ~ 100 DEG C.
2. method according to claim 1, wherein, the temperature of described formed body in the exit of described extruder is 60 ~ 120 DEG C.
3. method according to claim 1, wherein, the temperature of described raw material in the porch of described extruder is 40 ~ 80 DEG C.
4. method according to claim 1, wherein, the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is 30 ~ 100nm.
5. method according to claim 4, wherein, the described average particulate diameter that can form the precursor of heat-resistant inorganic oxide under roasting condition is 30 ~ 80nm.
6. method according to claim 1, wherein, described raw material is also containing molecular sieve, the content of described molecular sieve makes in the porous carrier prepared, with the total amount of porous carrier for 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.
7. method according to claim 6, 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 MCM-22 molecular sieve.
8. according to the method in claim 1 and 4 ~ 6 described in any one, wherein, described heat-resistant inorganic oxide is one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and mesoporous Si-Al.
9. according to the method in claim 1,4 and 5 described in any one, wherein, the described precursor that can form heat-resistant inorganic oxide under roasting condition contains the boehmite that relative crystallinity is more than 80%, and described relative crystallinity measures according to the method specified in RIPP 139-90.
10. method according to claim 9, wherein, the relative crystallinity of described boehmite is 90 ~ 110%.
11. methods according to claim 1, wherein, the condition of described roasting comprises: temperature is 350 ~ 800 DEG C, and the time is 1 ~ 10 hour.
12. 1 kinds of porous carriers prepared by the method in claim 1 ~ 11 described in any one.
13. porous carriers according to claim 12, wherein, the most probable pore size of this porous carrier is 1 ~ 30nm, aperture concentration degree is 22 ~ 48, described most probable pore size adopts BET method to measure, described aperture concentration degree refers to that the dV/dr adopting BET method to measure is with in the distribution curve of varying aperture, and the ratio of the halfwidth at the height at peak and this peak, dV/dr represents that specific pore volume amasss the differential to aperture.
14. porous carriers according to claim 13, wherein, the most probable pore size of this porous carrier is 2 ~ 20nm, and aperture concentration degree is 25 ~ 48.
15. porous carriers according to claim 14, wherein, the most probable pore size of this porous carrier is 5 ~ 10nm, and aperture concentration degree is 27 ~ 40.
Porous carrier in 16. claims 12 ~ 15 described in any one is as the application of carrier of catalyst with hydrogenation.
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