CN112742448B

CN112742448B - Catalyst support and method for producing same

Info

Publication number: CN112742448B
Application number: CN201911055058.5A
Authority: CN
Inventors: 董松涛; 杨平; 赵阳; 赵广乐
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2022-09-23
Anticipated expiration: 2039-10-31
Also published as: CN112742448A

Abstract

The invention relates to the field of carrier preparation, and discloses a catalyst carrier, which contains at least one of heat-resistant inorganic oxide and molecular sieve; the carrier is internally provided with a through hole channel, and the ratio of the cross sectional area of the hole channel to the cross sectional area of the carrier is 0.01-30: 100, respectively; the difference R between the water absorption of the carrier and the BET pore volume is not less than 0.2 mL/g. The catalyst carrier provided by the invention has a super-macroporous channel and high strength, and when the catalyst carrier is used in a catalyst, the catalyst has high strength, and the utilization rate of active components of the catalyst and the activity of the catalyst are improved.

Description

Catalyst support and method for producing same

Technical Field

The invention relates to the field of carrier preparation, in particular to a catalyst carrier and a preparation method thereof.

Background

The catalyst carrier is also called a support (support) and is one of the compositions of the supported catalyst. The catalytically active components are supported on the surface of a carrier, which is mainly used to support the active components and to give the catalyst specific physical properties, whereas the carrier itself generally does not have catalytic activity. Most supports are products in the catalyst industry, and commonly used are alumina supports, silica gel supports, activated carbon supports, and certain natural products such as pumice, diatomaceous earth, and the like.

The support enables the catalyst to be produced with suitable shape, dimensions and mechanical strength to meet the operating requirements of an industrial reactor. The geometric shape and the geometric size of the catalyst have influence on fluid resistance, air flow velocity, bed temperature gradient distribution, concentration gradient distribution and the like, and are also related to the effective utilization rate of active metal of the catalyst, the carrying of reaction heat in the reaction process and the like. To fully exploit the potential of the catalyst, the optimal shape and dimensions should be chosen, which requires the use of the most suitable shaping and preparation methods.

The selection of the geometric shape and dimensions of a commercial catalyst often requires a balance between several aspects and the properties of the catalyst. To achieve different goals, catalysts of a wide variety of morphologies are currently being developed. Usually in the form of spheres, which are commonly used for fluidized catalysts, or catalysts for which the flowability is particularly critical. The strip-shaped and fixed bed catalyst is further developed into cylindrical strips, trilobal strips, quadralobe strips, other multilobal strips and deformed multilobal strips on the basis of the strip-shaped catalyst. Barrel-shaped strips, i.e. strips with holes in the cylinder, such as typical raschig rings, cross rings, pall rings, step rings, etc. Honeycomb carriers, i.e., cordierite or alumina substrates, with regularly arranged channels are commonly used for SCR and automotive exhaust treatment, among others.

In order to improve the diffusion properties of the catalyst, the prior art discloses several methods.

CN101134173A proposes a carrier and a catalyst with special shapes, which are ellipsoids, and one or more grooves are opened on the ellipsoids, so it is said that because of its larger external surface area and good mass transfer performance, it can be widely used in heavy oil processing reaction.

CN1859975A discloses a deformed trilobal strip catalyst.

CN105233880A disclosureAn inner core type cloverleaf-shaped catalyst carrier and a preparation method and application thereof are provided. The carrier is composed of two layers, wherein the outer shell is made of porous structure material, the inner core is made of compact structure material, and the specific surface area of the inner core is less than 1m ² The catalyst has high crushing strength and small diffusion effect when being used in Fischer-Tropsch synthesis catalyst.

From the aspect of utilization rate of the catalyst and active metal, the catalyst with pore channels in the middle, such as Raschig rings or cross rings, has the highest utilization rate of the activity, and is a honeycomb carrier, a strip-shaped catalyst and a spherical catalyst. But the order of the strengths of the catalysts is substantially reversed. In order to balance catalyst utilization and strength, hollow carriers or catalysts such as raschig rings and honeycomb carriers are generally used. The ceramic matrix is adopted, the strength of the catalyst is high, even if the middle part of the catalyst is left empty, the overall strength is still high, the strength of the catalyst is not high, the catalyst is spherical or strip-shaped, the contact surface between the catalyst and the outside is increased by increasing the bending degree of the outer interface of the strip-shaped material, and the activity efficiency of the catalyst is further improved under the condition that the change of the strength is not large.

In addition, in order to improve the catalyst diffusion performance, there is also a method of increasing the amount of macropores or extra-macropores by adding a forming aid.

CN1115388C proposes a hydrogenation protective agent and a preparation method thereof, which adopts carbon black or an organic pore-enlarging agent as a pore-enlarging additive, and is said to have higher catalyst activity, lower carbon deposition amount, better activity stability and higher strength.

CN103418441B discloses a hydrorefining catalyst, the carrier of which is a molding containing carbon, cellulose ether and hydrated alumina. The disclosed hydrorefining catalyst has excellent hydrorefining performance of hydrocarbon oil, and meanwhile, the preparation method is simple and the production cost is low.

CN101890382B proposes a method for preparing a catalyst, which comprises rod-like nano-oxides in addition to alumina materials. The catalyst prepared by the method disclosed by the invention has large pore volume, large pore diameter and good pore canal penetrability, and is particularly suitable for residual oil fixed bed hydrogenation.

The method disclosed by the prior art is suitable for the conditions that the strength of the matrix is high or the specific surface area is small, and cannot be used for the conditions that the strength of the matrix is not high and the specific surface area of the carrier is large; the adopted pore channel modifier is mainly based on filler occupying pore forming, or is added with an auxiliary agent, or adopts water and an alumina precursor with different properties, and the optimization of the pore channel is realized by improving the connection mode between basic units.

As can be seen from the above, the catalysts and carriers in the prior art still have many defects, and it is desirable to provide a catalyst with high strength and large pore diameter, and high utilization rate of active metal.

Disclosure of Invention

The invention aims to solve the problem that the catalyst in the prior art cannot achieve both high strength and high active metal utilization rate, and provides a catalyst carrier and a preparation method thereof. The invention improves the pore structure of the carrier with lower cost, strengthens the diffusion process of macromolecules, and improves the activity of the catalyst and the accessibility of an active center. The catalyst carrier provided by the invention has a super-macroporous channel and high strength, and when the catalyst carrier is used in a catalyst, the catalyst has high strength, and the utilization rate of active components of the catalyst and the activity of the catalyst are improved.

The first aspect of the present invention provides a catalyst carrier comprising at least one of a refractory inorganic oxide and a molecular sieve; the carrier is internally provided with a through hole channel, and the ratio of the cross sectional area of the hole channel to the cross sectional area of the carrier is 0.01-30: 100;

the difference R between the water absorption of the carrier and the BET pore volume is not less than 0.2 mL/g.

In a second aspect, the present invention provides a method for preparing a catalyst carrier, the method comprising:

(I) mixing a carrier precursor, a foaming agent, water, an optional extrusion aid and an optional adhesive to obtain a mixture;

(II) molding the mixture to obtain a molded product with a through pore channel inside;

(III) roasting the formed product obtained in the step (II).

Preferably, the forming in step (II) is performed in a plodder comprising a body and an orifice plate, the body being arranged to enable the mixture to be formed through the orifice plate;

the orifice plate includes: the device comprises a base provided with a forming hole, a bracket provided with at least one material through hole and at least one forming rod; the support and the base are vertically overlapped, and the forming hole is communicated with the material through hole; the support still is provided with at least one and supplies the mounting hole that the shaping pole passed, the shaping pole sets up to run through the shaping hole.

A third aspect of the present invention provides a catalyst support prepared by the above method.

According to the preparation method of the catalyst carrier, the foaming agent is added in the forming process, and the gas component can be wrapped in the forming body due to the addition of the foaming agent, so that the proportion of macropores and super-macropores in the carrier in the whole pore volume is improved, and the smoothness of a pore channel of the carrier is improved; meanwhile, the catalyst carrier with an internal pore channel structure is processed by a one-step method, and the catalyst carrier is internally provided with a through pore channel, so that the catalyst carrier has a larger surface area than a conventional carrier, and the effective utilization rate of active components of the catalyst is further improved. In addition, the carrier provided by the invention has higher strength.

Drawings

FIG. 1 is a schematic diagram of the construction of the base of one embodiment of the orifice plate of the present invention;

FIG. 2 is a schematic diagram of a rack of one embodiment of the orifice plate of the present invention;

FIG. 3 is a schematic diagram of the construction of a shaped rod of one embodiment of the orifice plate of the present invention;

FIG. 4 is a schematic cross-sectional view of a catalyst support SA according to example 1 of the present invention;

FIG. 5 is a schematic diagram of a holder according to an embodiment of the well plate of the present invention;

fig. 6 is a schematic cross-sectional view of catalyst carrier DA of comparative example 1;

FIG. 7 is a schematic cross-sectional view of a catalyst carrier SB according to example 2 of the invention;

FIG. 8 is a schematic cross-sectional view of a catalyst carrier SC according to example 3 of the invention;

fig. 9 is a schematic cross-sectional view of the catalyst carrier SD according to example 4 of the present invention.

Description of the reference numerals

1. Base 2, shaping hole 3, support

4. Forming rod 5, mounting hole 6 and material passing hole

7. First mounting structure 8, second mounting structure 13, head

14. Rod part

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, one or more new ranges of values may be obtained from the combination of the endpoints of each range, the endpoints of each range and the individual values, and the individual values.

In the present invention, the use of the terms of orientation such as "upper, lower, between, and middle" generally means upper, lower, between, and middle as shown in the accompanying drawings, and the use of the terms of orientation such as "inner and outer" means inner and outer with respect to the profile of the respective member itself, unless otherwise specified.

The first aspect of the present invention provides a catalyst carrier comprising at least one of a refractory inorganic oxide and a molecular sieve; the carrier is internally provided with a through hole channel, and the ratio of the cross sectional area of the hole channel to the cross sectional area of the carrier is 0.01-30: 100, respectively;

The through hole in the invention refers to a state that the carrier has unobstructed property due to the pore channel existing in the carrier, and the pore channel penetrates through the carrier.

In the invention, the water absorption rate is wiping water absorption rate. In the invention, unless otherwise specified, the dry water absorption rate is that the dry carrier is soaked in deionized water at room temperature (20-25 ℃) for more than 30 minutes, and after filtration, the dry carrier is wiped by using filter paper to obtain the mass of the carrier after water absorption, and the ratio of the mass difference of the mass and the carrier without water absorption to the carrier without water absorption is the dry water absorption rate.

According to one embodiment of the invention, the dry water absorption of the catalyst support is 0.8 to 2mL/g, preferably 0.9 to 1.5 mL/g.

According to one embodiment of the invention, the BET pore volume of the catalyst support is between 0.6 and 1.2mL/g, preferably between 0.7 and 1.1 mL/g.

In the present invention, the BET pore volume is measured by the method specified in RIPP 151-90, unless otherwise specified.

According to the invention, the difference R between the water absorption of the support and the BET pore volume is preferably between 0.2 and 0.8mL/g, more preferably between 0.2 and 0.5 mL/g. According to the invention, the ratio of the difference R between the water absorption of the carrier and the BET pore volume to the water absorption of the carrier is preferably 10 to 50%, preferably 15 to 35%, more preferably 20 to 35%. The carrier provided by the invention has larger proportion, which shows that the proportion of macropores or super-macropores in the total pore volume of the carrier provided by the invention is larger. In the present invention, the pore volume of the carrier is measured by BET method and the water absorption (wiping water absorption) of the carrier is measured by water absorption method without specific description, and the difference R between the water absorption and the BET pore volume is represented by the pore volume of macropores or macropores and the water absorption is represented by the total pore volume of the carrier.

According to the present invention, preferably, the ratio of the cross-sectional area of the cell channel to the cross-sectional area of the carrier is 0.03 to 20: 100, preferably 0.1 to 15: 100. the carrier provided by the invention has a pore structure inside, so that the active components of the catalyst can be effectively utilized on the basis of ensuring the strength, and the activity of the catalyst is further improved.

According to the invention, the support preferably has a radial crushing strength of 14 to 30N/mm, preferably 18 to 26N/mm. In the present invention, the radial crushing strength of the catalyst carrier was measured on a crushing strength measuring apparatus of type QCY-602 (manufactured by soda research, chemical engineering) according to the method prescribed in GB3635-1983, unless otherwise specified.

Under the optimal condition, the carrier provided by the invention has high mechanical strength and a better pore channel structure, can effectively improve the activity of the catalyst and the accessibility of an active center, and is very suitable for the diffusion of macromolecules.

The catalyst support may have various shapes depending on the particular application. For example, the catalyst support may be spherical, bar-shaped, ring-shaped, honeycomb-shaped, or butterfly-shaped. The strip shape mentioned in the invention can be a cylindrical strip, an elliptical strip (equivalent to a double-leaf strip) or a multi-leaf strip, and the shape of the strip shape is not limited at all. The sphere mentioned in the invention can be regular sphere or irregular sphere, that is, the outline curve of the cross section of the catalyst carrier can be round or not perfect round. The strip-shaped carrier is a three-dimensional structure material which is prepared by extruding or tabletting and the like, has the length of not less than 50 percent of the diameter of the circumscribed circle, and the strip-shaped carrier does not have any limitation on the length and the distribution of the strip-shaped carrier.

Preferably, the carrier is spherical and/or bar-shaped, more preferably bar-shaped, and still more preferably multilobal bar-shaped. In the present invention, the carrier is in the form of a multilobal strip, which means that the cross-sectional shape of the carrier is multilobal. The invention does not limit the size of each blade of the multi-blade shape and the proportion of the size of each blade to the sizes of other blades, namely the multi-blade shape can be a regular multi-blade shape, a non-regular multi-blade shape or a deformed multi-blade shape.

According to the present invention, the multi-lobar strips may be at least one of three-lobar strips, four-lobar strips, five-lobar strips, six-lobar strips, and the like.

According to a preferred embodiment of the invention, the support is spherical and/or in the form of a rod, the equivalent diameter of the support being not more than 5mm, preferably not more than 3mm, more preferably not more than 2mm, still more preferably 0.8-2 mm.

According to one embodiment of the invention, if the carrier is otherwise shaped, the minimum transverse dimension of the outer shape of the carrier is not more than 5mm, preferably not more than 3mm, more preferably not more than 2 mm.

In the present invention, the pore passage may be formed in various reasonable shapes, and may be regular or irregular, and it is preferable that the pore passage has a regular shape from the viewpoint of easiness of processing. The cross section of the channels is the same or different (gradually increasing or gradually decreasing) along the material flow direction, and in the case of gradually increasing cross section of the channels along the material flow direction, the channels include but are not limited to cones; in the case where the cross-section of the cell channel decreases gradually along the direction of flow, the cell channel includes, but is not limited to, an inverted cone.

Preferably, the duct is a channel of uniform cross-section. The cross-section of the channels may be regular or irregular, preferably regular.

The duct may have various shapes that can be machined, and it is preferable that the cross-section of the duct is circular and/or regular polygonal from the viewpoint of easiness of machining. The optimized implementation mode is convenient to process, effectively ensures the stability of the catalyst carrier, and is beneficial to improving the compactness and the strength of the catalyst carrier. It should be noted that, in the present invention, the circle and regular polygon also include an imperfect circle and/or regular polygon.

Further preferably, the diameter of the cylindrical shape and the diameter of the circumscribed circle of the regular polygonal pyramid shape are each independently not less than 5 μm, preferably 0.01 to 0.5mm, and further preferably 0.05 to 0.3 mm.

In the invention, the regular polygonal prisms can be regular polygonal prisms such as triangular prism, quadrangular prism, pentagonal prism and the like, and the cross sections of the pore channels of the catalyst carrier correspondingly obtained are correspondingly formed into regular polygonal structures such as equilateral triangle, square, regular pentagon and the like.

The selection range of the number of the pore channels is wide, and a person skilled in the art can comprehensively consider the number of the pore channels according to the strength and the stacking ratio, and the number of the pore channels can be 1 or more than two, and can be properly selected according to the actual requirement on the number of the pore channels. Preferably, the number of said channels is between 1 and 10, preferably between 1 and 6.

It should be noted that if the number of the cells is 2 or more, the above-defined ratio of the cross-sectional area of the cell to the cross-sectional area of the carrier refers to the ratio of the cross-sectional area of the individual cell to the cross-sectional area of the carrier.

The specific position selection range of the pore canal setting is wide, and the pore canal setting can penetrate through the carrier. When the number of the pore channels is one, the pore channels preferably extend along the central axis of a circumscribed circle of the cross section of the carrier, in this case, when the cross section of the carrier is circular, the pore channels extend along the circular central axis; when the cross section of the carrier is multi-leaf shape, the pore canal extends along the central axis of the circumcircle where the multi-leaf shape is located.

When the number of the pore passages is two or more, the relative arrangement position between the pore passages is not particularly limited, and preferably, the pore passages are uniformly distributed. The preferred implementation mode is more beneficial to ensuring that the stress distribution of the catalyst carrier is more balanced, and further optimizing the overall strength of the catalyst carrier. Preferably, the uniform distribution means that the distances from the pore channels to the center of a circumscribed circle where the cross section of the carrier is located are equal, more preferably, the distances between the pore channels are equal, and more preferably, the distances from the pore channels to the center of the circumscribed circle where the cross section of the carrier is located are equal to the distances from the pore channels to the edge of the carrier.

According to a preferred embodiment of the present invention, the cross-section of the carrier is circular, and the pore channels extend along a central axis of the circular shape and/or are arranged at equal intervals along a circumferential direction of the central axis. The preferred embodiment enables the pore channels to be distributed evenly, effectively avoids the sudden drop of local strength caused by the arrangement of the middle pore channel structure on the catalyst carrier, and can ensure the mechanical strength of the carrier.

According to another preferred embodiment of the invention, the cross-section of the support is multilobal, and the cells extend along the central axis of the circumcircle on which the multilobal vanes lie and/or along the central axis of the circumcircle on which the multilobal vanes lie. The preferred embodiment enables the pore channels to be distributed evenly, effectively avoids the sudden local strength drop of the catalyst carrier caused by the arrangement of the middle pore channel structure, and can ensure the mechanical strength of the carrier.

In the present invention, the composition of the catalyst support may be a composition conventional in the art, and may contain at least one of a refractory inorganic oxide and a molecular sieve.

The specific type of the heat-resistant inorganic oxide is not particularly limited in the present invention, and may be a heat-resistant inorganic oxide generally used in the art. For example, the heat-resistant inorganic oxide may be at least one selected from the group consisting of alumina, silica, titania, magnesia, zirconia, thoria and beryllia. Specific examples thereof may include, but are not limited to, alumina, silica, zirconia, titania, magnesia, thoria, beryllia, alumina-titania, alumina-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania or silica-alumina-magnesia. Preferably, the heat-resistant inorganic oxide is at least one of alumina, silica, titania and zirconia. More preferably, the refractory inorganic oxide is alumina.

The alumina mentioned in the invention refers to available mAl ₂ O ₃ ·nH ₂ O represents a compound of its composition, wherein m and n are arbitrary numbers, and may be integers or fractions. The present invention also does not impose any limitation on the crystalline phase of the alumina.

The molecular sieve of the present invention refers to a material with regular crystal structure and pore channels, which is generally called molecular sieve or zeolite, and the molecular sieve or zeolite has a framework composed of silicon-aluminum elements, and may also contain other elements, such as: at least one of P, Ti, Ge and Ga. The invention is not limited in any way as to the composition of the elements that make up the molecular sieve.

The molecular sieve can be one type, two or more types, or mixed crystal and twin crystal of two types of molecular sieves. The two molecular sieves described herein refer to two different types of molecular sieves, and may be one molecular sieve, but the two molecular sieves have different properties (e.g., different silica to alumina ratios).

The two or more molecular sieves referred to in the present invention are 3 or more molecular sieves, and these molecular sieves may be different types of molecular sieves or the same type of molecular sieves having different properties. The amount of each molecular sieve may be between 0.1 and 80 wt% (based on the catalyst support).

The ratio of the two molecular sieves can be 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 1:1 and the like, and the ratio of the two molecular sieves is arbitrary.

According to the present invention, the molecular sieve may be selected from at least one of a ten-membered ring silicoaluminophosphate molecular sieve, a twelve-membered ring silicoaluminophosphate molecular sieve, a fourteen-membered ring silicoaluminophosphate molecular sieve and an eighteen-membered ring silicoaluminophosphate molecular sieve. The invention does not limit the size of the pore opening and the pore diameter of the molecular sieve.

The invention has no limitation on the silicon-aluminum ratio of the molecular sieve, wherein the silicon-aluminum ratio refers to SiO ₂ /Al ₂ O ₃ 。

According to a preferred embodiment of the present invention, the molecular sieve is selected from at least one of a ZRP molecular sieve, a Y molecular sieve, a beta molecular sieve, mordenite, a ZSM-5 molecular sieve, an MCM-41 molecular sieve, an omega molecular sieve, a ZSM-12 molecular sieve and an MCM-22 molecular sieve, and is further preferably at least one of a Y molecular sieve, beta, ZSM-5 and mordenite.

The molecular sieve can be obtained by commercial purchase or any conventional method.

The Y molecular sieve can be a Y molecular sieve with a cell constant of 2.452-2.475 nanometers and a silica/alumina molar ratio of 3.5-7; can be an ultra-stable Y molecular sieve prepared by performing one or more times of hydrothermal treatment after exchanging the Y molecular sieve with ammonium ions, wherein the unit cell constant of the Y molecular sieve is 2.420-2.455 nanometers, and the molar ratio of silicon oxide to aluminum oxide in a framework can reach 100, preferably 60; or exchanging the Y molecular sieve with one or more inorganic ammonium solutions of phosphide, and carrying out one or more times of hydrothermal treatment to prepare the phosphorus-containing ultrastable Y molecular sieve; or the rare earth Y molecular sieve is prepared by combining the Y molecular sieve treated by the rare earth compound aqueous solution with one or more times of hydrothermal treatment.

According to the present invention, it is preferable that the refractory inorganic oxide is contained in an amount of 1 to 99% by weight and the molecular sieve is contained in an amount of 1 to 99% by weight, based on the total amount of the carrier.

Further preferably, the refractory inorganic oxide is contained in an amount of 70 to 99% by weight and the molecular sieve is contained in an amount of 1 to 30% by weight, based on the total amount of the carrier.

(III) roasting the formed product obtained in the step (II).

According to the invention, the term "optional" means that it may or may not be added. In the mixing process of the step (I), the extrusion aid can be added or not added, and the adhesive can be added or not added.

According to the production method provided by the present invention, the carrier precursor is any substance that can be converted into a carrier by the calcination in the step (II). Specifically, the support precursor may be selected from at least one of refractory inorganic oxide, refractory inorganic oxide precursor, and molecular sieve. The refractory inorganic oxide precursor is any substance that can be converted into a refractory inorganic oxide by the firing in step (II). The refractory inorganic oxide is selected as described above, and the present invention is not described herein again.

The molecular sieve is selected as described above, and the present invention is not described herein.

According to the preparation method provided by the invention, preferably, the refractory inorganic oxide and/or the refractory inorganic oxide precursor and the molecular sieve are used in such amounts that the refractory inorganic oxide content in the prepared carrier is 1-99 wt%, and more preferably 70-99 wt%, based on the total amount of the carrier; the content of the molecular sieve is 1 to 99% by weight, more preferably 1 to 30% by weight. More preferably, the refractory inorganic oxide is alumina and the molecular sieve is a Y molecular sieve.

According to the present invention, specific examples of the precursor of the alumina may include, but are not limited to: hydrated alumina (e.g., aluminum hydroxide, pseudoboehmite), gels containing hydrated alumina, and sols containing hydrated alumina. For example, the precursor of the alumina can be dry glue powder. The dry rubber powder may be obtained commercially (for example, from catalyst Changjingtie), or may be prepared by any conventional method, and the present invention is not particularly limited thereto.

According to the invention, the foaming agent has the capability of encapsulating gas, and can be organic matter, inorganic matter, pure chemical substance or mixture of multiple components. The foaming agent may be selected from at least one of a physical foaming agent, a chemical foaming agent, a synthetic surfactant foaming agent, an animal protein foaming agent, and a plant foaming agent. Preferably, the foaming agent is an animal protein foaming agent and/or a plant foaming agent. The animal protein foaming agent is preferably at least one selected from the group consisting of an animal hoof and horn foaming agent, an animal hair foaming agent, and an animal blood gel foaming agent. The plant foaming agent is preferably at least one selected from rosin soap foaming agent, tea saponin and tea saponin.

According to a preferred embodiment of the invention, the foaming agent is an animal protein foaming agent, such as an animal hoof and horn foaming agent and/or egg white. The inventor of the present invention found in the research process that in the preparation process of the carrier, the animal protein foaming agent has obvious advantages in toughness and stability of the bubbles compared with the traditional physical foaming agent, chemical foaming agent and synthetic surfactant foaming agent.

According to the preparation method provided by the invention, the foaming agent can be introduced in the form of solution, water can be used as a solvent, other organic matters can be used as a solvent, and water is preferred.

According to a preferred embodiment of the present invention, the animal protein foaming agent is introduced in the form of a hydrolysate of the animal protein foaming agent. When protein is hydrolyzed, protein macromolecules of longer peptide chains are changed into soluble small and medium molecular mixtures of short chains, and after the mixture is dissolved in water, a colloidal solution with certain viscosity can be formed.

The method for obtaining the animal protein foaming agent hydrolysate by hydrolyzing the animal protein foaming agent is not particularly limited in the present invention, and those skilled in the art can prepare the animal protein foaming agent hydrolysate by any means on the basis of the above description. For example, the method can be carried out according to the method disclosed in marxiyun, leizuyun, mathematic mine, et al, research on protein-type concrete foaming agents [ J ]. architecture science, 2009,25(5):73-76.

In order to promote the hydrolysis of the animal protein, a hydrolysis promoter may be appropriately added during the hydrolysis process, and the present invention is not particularly limited thereto.

According to the method provided by the invention, preferably, the extrusion aid is at least one selected from sesbania powder, cellulose and derivatives thereof, starch and derivatives thereof, ethylene glycol and diethylene glycol. The derivative of the starch can be one or more of oxidized starch, esterified starch, carboxymethyl starch, cationic starch, hydroxyalkyl starch and multi-component starch; the derivative of cellulose may be one or more of cellulose ether, cellulose ester and cellulose ether ester. The extrusion aid in the embodiment of the invention is exemplified by sesbania powder, and the invention is not limited thereto.

According to the method provided by the invention, the selection range of the type of the adhesive is wide, and the adhesive can be at least one of hydroxymethyl cellulose, inorganic acid, starch and derivatives thereof, silica sol or aluminum sol.

According to the method of the present invention, the specific manner of mixing the carrier precursor, the foaming agent, water, and optionally the extrusion aid, and optionally the binder is not particularly limited as long as the carrier precursor, the foaming agent, water, and optionally the extrusion aid, and optionally the binder are mixed. Preferably, the mixing of step (1) comprises: mixing the carrier precursor and the extrusion aid, and then adding the foaming agent, the adhesive and the water to obtain the mixture. In the preferred embodiment, the carrier precursor and the extrusion aid are mixed to obtain mixed powder, and then the foaming agent, the adhesive and the water are added, so that the catalytic performance of the catalyst prepared from the obtained carrier can be improved.

More preferably, the mixing of step (1) comprises: mixing the carrier precursor and the extrusion aid to obtain mixed powder; foaming a foaming agent, an adhesive and water to obtain a foaming liquid; and mixing the mixed powder and the foaming liquid. In this preferred embodiment, it is more advantageous to improve the catalytic performance of the catalyst obtained from the resulting support. The foaming may be accomplished in a blowing agent.

According to the invention, preferably, the foaming agent is an animal protein foaming agent, and the amount of the foaming agent is 0.1-50mL, preferably 0.5-20mL, relative to 100g of the carrier precursor on a dry basis. With such a preferred embodiment it is more advantageous to have a carrier that combines a higher mechanical strength with a better pore structure.

According to the invention, the blowing agent is preferably a plant blowing agent, which is used in an amount of 0.1 to 5g, relative to 100g of carrier precursor on a dry basis.

According to the present invention, preferably, the amount of the extrusion aid is 0.1 to 6g, preferably 2 to 4g, relative to 100g of the carrier precursor on a dry basis.

According to the present invention, the binder is preferably used in an amount of 0.1 to 10g, preferably 0.5 to 6g, relative to 100g of the carrier precursor on a dry basis.

According to the invention, the water in the mixture is used as a dispersing medium, and the amount of the water is based on the amount of the water capable of uniformly mixing the other components in the mixture.

According to the invention, the mixture may optionally also contain a peptizing agent, preferably no peptizing agent. In the existing preparation process of the catalyst carrier, a peptizing agent such as dilute nitric acid is required to be added, but the peptizing agent can be added or not added in the preparation method of the carrier provided by the invention.

In the present invention, the conditions for baking the shaped product are not particularly limited, and may be conventional conditions in the art. Generally, the temperature of the roasting may be 350-700 ℃, preferably 450-650 ℃; the calcination time may be 1 to 10 hours, preferably 2 to 6 hours. The calcination may be carried out in an oxygen-containing atmosphere (e.g., air) or in an inert atmosphere. The inert atmosphere refers to a gas that is inactive under the drying or firing conditions, for example: nitrogen and group zero element gases (e.g., argon).

Before the shaped object is baked, drying the shaped object can be further included, and the drying can be performed under the conventional conditions in the field, such as: the drying temperature may be 100-200 deg.c and the drying time may be 2-12 hours. The drying may be performed under normal pressure or reduced pressure, and is not particularly limited. The drying may be performed in an oxygen-containing atmosphere or in an inert atmosphere.

According to the preparation method provided by the invention, the method comprises the following steps: and kneading and molding the mixture. Specifically, the mixture may be fed into a bar extruder, kneaded in the bar extruder, and extruded to obtain a molded product.

According to the preparation method provided by the invention, the molded object with the through pore channel inside is obtained through the molding. The method may be selected from a wide range of methods as long as a molded product having a through-hole in the interior can be obtained. Preferably, the forming in step (II) is performed in a plodder comprising a body and an orifice plate for plodding, the body being arranged to enable the mixture to be formed through the orifice plate; as shown in fig. 1-3, the orifice plate includes: the device comprises a base 1 provided with a forming hole 2, a bracket 3 provided with at least one material through hole 6 and at least one forming rod 4; the support 3 and the base 1 are vertically stacked, and the forming holes 2 are communicated with the material through holes 6; the support 3 is further provided with at least one mounting hole 5 for a forming rod 4 to pass through, and the forming rod 4 is arranged to penetrate through the forming hole 2. In this preferred embodiment, the shaping bore 2 of the perforated plate and the shaping rod 4 extending through the shaping bore 2 together form a shaping cavity, through which the material is shaped correspondingly. The preferred embodiment realizes that the catalyst carrier with the internal pore structure is processed and prepared by a one-step method, the operation is simple and convenient, and the prepared catalyst carrier has high strength and high utilization rate of active metal.

According to the invention, the term "for extruding" means that the pore plate is used for extruding, and the term "for extruding" does not limit the pore plate structure of the invention.

According to the present invention, it can be understood by those skilled in the art that the molding hole 2 penetrates through the base 1, so that a carrier with a through hole can be obtained.

According to the invention, the forming rod 4 is arranged to penetrate through the forming hole 2, which is understood to mean that the forming rod 4 has a length such that one end of the forming rod 4 is located at the end of the base 1 far away from the bracket or such that one end of the forming rod 4 is located outside the end of the base 1 far away from the bracket.

According to a preferred embodiment of the invention, the ratio of the cross-sectional area of the shaped rod 4 to the cross-sectional area of the shaped hole 2 corresponds to the above-mentioned ratio of the cross-sectional area of the duct to the cross-sectional area of the carrier. For example, 0.01 to 30: 100, preferably 0.03 to 20: 100, more preferably 0.1 to 15: 100. this preferred embodiment is more advantageous in that the resulting support has both high strength and high active metal utilization.

According to the present invention, it is understood that the shape of the molding holes 2 is actually the shape of the catalyst carrier to be produced. The shape of the shaping opening 2 can be selected according to the above description regarding the shape of the carrier.

According to a preferred embodiment of the invention, the cross-section of the shaping orifice 2 is circular or multilobal. The circle and the multilobal shape are not particularly limited and may be selected in accordance with the above description about the shape of the carrier.

The size of the forming hole 2 is selected in a wide range, and those skilled in the art can select the size appropriately according to the requirement of the size of the carrier, and preferably, the equivalent diameter of the forming hole 2 is not more than 5mm, preferably not more than 3mm, more preferably not more than 2mm, and still more preferably 0.8-2 mm.

The number of the molding rods 4 is selected from a wide range, and may be 1, or two or more, and is appropriately selected according to the requirement of the number of the pore channels in the carrier, and preferably, the number of the molding rods 4 is 1 to 10, and more preferably 1 to 6. It will be appreciated that the number of shaped rods 4 matches the number of channels of the catalyst support described above.

According to the invention, the forming rods are arranged at positions corresponding to the positions of the channels in the catalyst carrier, and the person skilled in the art knows how to arrange the forming rods in the above description of the positions of the channels in the catalyst carrier. Preferably, the cross section of the molding hole 2 is circular, the molding rods 4 may extend along the central axis of the circle center of the circle, and if the number of the molding rods 4 is 2 or more, the different molding rods 4 may be disposed at equal intervals along the circumferential direction of the circle center of the circle. According to a preferred embodiment of the invention, the cross section of the profiled bore 2 is multilobal, the profiled rod 4 extending along the central axis of the circumcircle on which the multilobal is located and/or along the central axis of the vanes of the multilobal. By adopting the preferred implementation, the opening positions of the pore channel structures in the catalyst carrier are designed more reasonably, so that the pore channels are distributed uniformly, the local intensity shock drop caused by the opening of the middle pore channel structure of the catalyst carrier is effectively avoided, and the mechanical strength is improved.

According to an embodiment of the invention, the number of mounting holes 5 is equal to the number of profiled rods 4.

Preferably, the forming rod 4 is detachably connected with the bracket 3 through the mounting hole 5. In the invention, the detachable connection enables the two connected parts not to move mutually during work; and when the device is stopped, the requirements of disassembly and replacement can be met.

The forming rod 4 can be arranged in various reasonable forms, for example, as shown in fig. 3, the head 13 of the forming rod 4 is installed in the installation hole 5, and the rod 14 of the forming rod extends towards the discharge hole of the forming hole to be sleeved (penetrated) in the installation hole 5 and the forming hole 2, so that the forming rod is easy to install and low in cost.

According to the invention, the number of through-openings 6 is selected within a wide range, for example from 1 to 20, preferably from 2 to 20. Preferably, as shown in fig. 2, a plurality of material passing holes 6 are arranged at equal intervals in the circumferential direction of the forming rod 4. By adopting the preferred embodiment, the feeding uniformity of the periphery of the forming rod 4 is more facilitated, the periphery of the forming rod 4 is uniformly stressed, and the service life of the forming rod 4 can be prolonged. On the basis of the above, the number of the through holes 6 arranged in the circumferential direction of each forming rod 4 can be selected by those skilled in the art according to the actual situation. It will be appreciated that the through-flow apertures 6 may be provided in any suitable manner, for example, as shown in figure 2, a plurality of through-flow apertures 6 may be in communication with the mounting apertures 5 or may be isolated from the mounting apertures 5.

Considering that the forming rods 4 are installed on the installation holes 5 formed by the supporting structure of the bracket 3, and the supporting structure covers the distribution area of the forming holes 2, in order to ensure uniform material distribution of the raw material, and in order to simplify the processing technology of the bracket 3, the bracket 3 is preferably set to be of a uniform cross-section structure, so that the thickness of the supporting structure (referred to as the discharging direction of the forming holes) can be maximized, the extrusion effect applied when the supporting structure bears the forming holes to convey the material is enhanced, and the fixing firmness of the forming rods is improved. Preferably, the distribution area of the through holes 6 at least covers the distribution area of the forming holes 2, so that the support 3 can directly and uniformly distribute materials to the forming holes 2 of the base 1 through the through holes 6, and raw materials can enter all areas at the feeding port of the forming holes 2 at the same time. In addition, the overall outer contour of the through hole may be a multi-lobe structure having the same shape as the molding hole.

Preferably, as shown in fig. 3, the portion of the molding rod 4 extending into the molding hole 2 is provided in a uniform cross-sectional structure. The optimized implementation mode effectively ensures the stability of the processing shape of the prepared catalyst carrier and is beneficial to obtaining a compact catalyst carrier with high compactness and high strength.

The molding rod 4 can be formed into various reasonable shapes so as to be convenient for processing and manufacturing the catalyst carrier with the pore channel structure with the corresponding shape. It will be appreciated that the portion of the shaped rod 4 extending into the shaped hole 2 corresponds to the configuration of the pore channel in the catalyst support. Preferably, the part of the forming rod 4 extending into the forming hole 2 is provided as a cylinder. Under the condition, the prepared catalyst carrier can correspondingly form a pore channel structure with a cylindrical structure, so that the inner surface of the catalyst carrier is smoother and more regular, the phenomenon of stress concentration of the catalyst carrier due to the fact that sharp pore walls exist in the pore channel structure is avoided, and the probability of collapse of the catalyst carrier is reduced.

Further preferably, the diameter of the cylinder is set to not less than 5 μm, preferably 0.01 to 0.5mm, further preferably 0.05 to 0.3 mm.

In another preferred case, a portion of the forming rod 4 extending into the forming hole 2 is a regular polygonal prism. Under the condition, the prepared catalyst carrier can correspondingly form a pore channel structure with a regular polyhedral prism structure, so that the inner surface of the catalyst carrier is more regular, the stress distribution of the catalyst carrier is more balanced, and the overall strength of the catalyst carrier is further optimized.

Further preferably, the diameter of the circumscribed cylinder of the regular polygonal prism is set to be not less than 5 μm, preferably 0.01 to 0.5mm, and further preferably 0.05 to 0.3 mm.

According to a preferred embodiment of the invention, the base 1 and the support 3 are arranged in a detachable connection. The detachable connection is such that the base 1 and the bracket 3 do not move relative to each other during operation; and when the device is stopped, the requirements of disassembly and replacement can be met. Preferably, the base 1 and the support 3 are attached to each other to avoid material leakage, for example, a first mounting structure 7 is disposed on an attaching surface of the base 1 and the support 3, and a second mounting structure 8 adapted to the first mounting structure 7 is disposed on an attaching surface of the support 3 and the base 1. For example, one of the first mounting structure 7 and the second mounting structure 8 is provided as a mounting groove, and the other is provided as a mounting protrusion adapted to the mounting groove.

According to one embodiment of the invention, the base 1 and the support 3 have the same overall outer contour. This embodiment facilitates the mounting operation.

According to the present invention, the height of the base 1 and the height of the holder 3 are not particularly limited, and preferably, the ratio of the height of the base 1 to the height of the holder 3 is set to 1 (0.2 to 5).

For ease of understanding, a specific form is now provided, comprising: feeding the mixture obtained in the step (1) into a strip extruding machine, wherein the strip extruding machine comprises a main body and a pore plate, the main body is arranged to be capable of forming the mixture through the pore plate, the mixture enters a forming cavity formed by a forming hole 2 and a forming rod 4 through a material passing hole 6 arranged on a support 3 to obtain a formed object with a through pore passage inside, the number and the shape of the forming rods 4 correspond to the number and the shape of the pore passage, and the shape and the size of the forming hole 2 correspond to the shape and the size of the formed object.

The main body of the plodder can be a component conventionally used in the field, and the invention is not described in detail herein.

The third aspect of the present invention provides a catalyst carrier obtained by the above-mentioned production method. The structural features of the catalyst carrier are as described above and will not be described in detail here.

The catalyst carrier provided by the invention is suitable for being used as a carrier of various hydrogenation catalysts. The carrier can effectively utilize the active components of the catalyst.

For example, the catalyst using the catalyst carrier provided by the invention as a carrier and at least one of the VIB group metal elements (such as Mo and/or W) and at least one of the VIII group metal elements (such as Co and/or Ni) as active components has better catalytic performance and strength.

The present invention will be described in detail below by way of examples.

In the following examples, BET pore volume was measured according to the method specified in RIPP 151-90; the water absorption rate is wiping water absorption rate, the wiping water absorption rate is that the dry carrier is soaked in deionized water for 60 minutes at room temperature (20-25 ℃), the carrier is wiped by using filter paper after filtration, the mass of the carrier after water absorption is obtained, and the ratio of the mass difference between the mass and the carrier not absorbing water to the carrier not absorbing water is wiping water absorption rate; the radial crushing strength of the catalyst support was determined according to the method specified in GB3635-1983 on a crushing strength tester of type QCY-602 (manufactured by soda research, Ministry of chemical industry).

In the following examples and comparative examples, the pressure is in gauge pressure and the dry content is determined by baking the sample at 600 ℃ for 4 hours.

Example 1

(1) 200.0g of dry rubber powder (taken from catalyst Chang Ling division, 68 wt% of dry basis, and the main phase is pseudoboehmite, the same below), 61.5g of HY molecular sieve (taken from catalyst Chang Ling division, 79 wt% of dry basis, FAU type molecular sieve, the same below), and 8g of sesbania powder are uniformly mixed to obtain mixed powder. 15mL of egg white (obtained from fresh eggs) and 1g of hydroxymethyl cellulose were added to 175mL of water, and after completion of foaming in a foaming machine, the mixture was mixed with the mixed powder to obtain a mixture.

(2) The mixture is sent into a strip extruding machine to be repeatedly kneaded for 3 times (15 minutes) and then adopted

And (3) extruding a cored trilobal pore plate strip, wherein the pore plate is provided with 3 forming rods (3 cylinders with the diameter of 0.1 mm), drying the obtained extruded strip at 120 ℃ for 3 hours, and roasting the dried extruded strip at 600 ℃ for 3 hours in the presence of air to obtain the catalyst carrier SA.

The carrier is in a three-blade bar shape, the diameter of an external circle of the cross section is 1.6mm, 3 through ducts (3 cylinders with the diameter of 0.1 mm) are arranged inside the carrier, and the 3 cylindrical ducts respectively extend along the central axis of the external circle where the three blades are located. The cross-sectional view of the catalyst carrier is shown in FIG. 4, and the strength of the carrier is shown in Table 1.

The specific process of forming is as described in the specific embodiments, wherein the forming is performed using a perforated plate, the perforated plate comprising: the support 3 is provided with 12 material through holes 6, the pore plate is provided with 3 forming rods 4, and as shown in fig. 4, every 4 material through holes 6 are arranged at equal intervals along the circumferential direction of one forming rod 4; the support 3 is also provided with 3 mounting holes 5 for the molding rods 4 to pass through. The 3 forming rods 4 respectively extend along the central axis of the circumscribed circle where the three blades are located. As shown in fig. 5.

(3) And (3) measuring the water absorption of the catalyst carrier, preparing a mixed aqueous solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, purchased from Changling catalyst factory) according to the tungsten oxide content of 19.5 wt% and the nickel oxide content of 5.5 wt% in the catalyst, and impregnating the catalyst carrier prepared in the step (2) by adopting a pore saturation method. The impregnated carrier was dried at 120 ℃ for 5 hours, followed by calcination at 400 ℃ for 3 hours to obtain a catalyst CSA.

Comparative example 1

(1) 200.0g of dry rubber powder, 61.5g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. 2.5mL of 68% by weight nitric acid was added to 155mL of water, mixed uniformly, added to the mixed powder, and mixed to obtain a mixture. The mixture is sent into a strip extruding machine to be repeatedly kneaded for 3 times (15 minutes) and then adopted

Three-leaf bar-shaped orifice plateAnd extruding the strips, drying the obtained extruded strips at 120 ℃ for 3 hours, and roasting the extruded strips at 600 ℃ for 3 hours in the presence of air to obtain the solid (without pore channels) catalyst carrier DA.

The carrier is a trefoil strip, and the diameter of a circumscribed circle of the cross section is 1.6 mm. The cross-sectional area of the carrier is shown in figure 6.

(2) And (2) measuring the water absorption of the catalyst carrier, preparing a mixed aqueous solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, purchased from Changling catalyst factory) according to the tungsten oxide content of 19.5 wt% and the nickel oxide content of 5.5 wt% in the catalyst, and impregnating the catalyst carrier prepared in the step (1) by adopting a pore saturation method. The impregnated carrier was dried at 120 ℃ for 5 hours, followed by calcination at 400 ℃ for 3 hours to obtain catalyst CDA.

Example 2

(1) 200.0g of dry rubber powder, 61.5g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. Animal protein foaming agent (preparation method: cow hoof 20g, Ca (OH)) ₂ 6g，NaHSO ₃ 2g, 200mL of water, 80 ℃ of hydrolysis temperature and 6h of hydrolysis time, and preparing foaming liquid from the following sources: study of maleichness, Liyun, Lexuri, Tezui, Jiayonghui, protein type concrete foaming agent [ J]Building science, 2009,25(05):73-76.)6mL (equivalent to 0.6g containing bovine hoof horn) and 1g of hydroxymethyl cellulose, add water to 175mL, and mix with the mixed powder after foaming in a foaming machine to obtain a mixture.

Extruding a four-leaf pore plate with a core to obtain strips, wherein the pore plate is provided with 4 forming rods (4 cylinders with the diameter of 0.1 mm), drying the obtained extruded strips at 120 ℃ for 3 hours, and roasting the dried extruded strips at 600 ℃ for 3 hours in the presence of air to obtain a catalyst carrier SB.

The carrier is in a four-blade strip shape, the diameter of an external circle of the cross section is 1.6mm, 4 through channels (4 cylinders with the diameter of 0.1 mm) are arranged inside the carrier, and the 4 cylindrical channels respectively extend along the central axis of the external circle where the four blades are located. The cross-sectional view of the carrier is shown in FIG. 7, and the strength of the carrier is shown in Table 1.

(3) And (3) measuring the water absorption of the catalyst carrier SB, preparing a mixed aqueous solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, purchased from Changling catalyst factory) according to the tungsten oxide content of 19.5 wt% and the nickel oxide content of 5.5 wt% in the catalyst, and impregnating the catalyst carrier prepared in the step (2) by adopting a pore saturation method. The impregnated carrier was dried at 120 ℃ for 5 hours, followed by calcination at 400 ℃ for 3 hours to obtain catalyst CSB.

Example 3

A carrier and catalyst were prepared as in example 1, except that 5mL of egg white was used. And use

Extruding the cored trilobal pore plate. The carrier is in a three-leaf bar shape, the diameter of an external circle of a cross section is 1.6mm, 4 through holes (1 regular three-sided prism body with the diameter of the external circle of 0.1mm and 3 cylinders with the diameter of 0.1 mm) are formed in the carrier, the central shaft of the external circle of the 1 regular three-sided prism hole is extended along the three-leaf shape, the central shaft of the external circle of the three blades is respectively extended along the 3 cylindrical holes, and the carrier SC and the catalyst CSC are obtained. The cross-sectional area of the carrier is shown in FIG. 8, and the strength of the carrier is shown in Table 1.

Example 4

The carrier and the catalyst were prepared according to the method of example 2, except that the amount of the animal protein foaming agent was 12mL, and the animal protein foaming agent was used

Extruding the cored trilobal pore plate. The carrier is in a three-leaf strip shape, the diameter of an external circle of the cross section is 1.6mm, 3 through holes (a regular hexahedral prism body with the diameter of the external circle of 0.1 mm) are formed in the carrier, and the 3 holes respectively extend along the central axis of the external circle where the three blades are located. The carrier SD and the catalyst CSD are obtained. The cross-sectional area of the support is shown in FIG. 9. The strength of the carrier is shown in Table 1.

Example 5

A carrier and catalyst were prepared as in example 1, except that egg white was used in an amount of 25 mL. The support SE and the catalyst CSE are obtained. The strength of the support is shown in Table 1.

Example 6

The procedure of example 1 was followed except that a vegetable foaming agent was used instead of egg white, specifically:

(1) 200.0g of dry rubber powder, 61.5g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. Mixing 2.0g tea saponin (obtained from feihuang chemical company, ny-yi) with 0.5mL nitric acid with a concentration of 68% by weight, adding water to 175mL, completing foaming in a foaming machine, and mixing with the mixed powder to obtain a mixture.

(2) The extrusion was carried out in accordance with the step (2) of example 1, and the obtained extruded strands were dried at 120 ℃ for 3 hours and then calcined at 600 ℃ for 3 hours under air-introducing conditions to obtain a catalyst carrier SF. The strength of the support is shown in Table 1.

(3) The catalyst was prepared according to the method of example 1 to obtain the catalyst CSF.

Example 7

According to the method of example 1, except that

The cored trilobal orifice plate is extruded, and the orifice plate is provided with 1 molding rod (1 cylinder with the diameter of 0.2 mm). And obtaining the catalyst carrier SG and the catalyst CSG. The carrier is in a trefoil strip shape, the diameter of an external circle of the cross section is 1.6mm, 1 through hole (1 cylindrical hole with the diameter of 0.2 mm) is formed in the carrier, and the cylindrical hole extends along the central axis of the external circle of the trefoil shape. The strengths of the catalyst carrier SG are shown in table 1.

Example 8

Following the procedure of example 1 except that

The cored trilobal orifice plate is extruded, and the orifice plate is provided with 1 molding rod (1 is a cylinder with the diameter of 0.3 mm). To obtain the catalyst carrier SH and the catalyst CSH. The carrierThe body is a trefoil strip, the diameter of the circumscribed circle of the cross section is 1.6mm, 1 through hole (1 cylindrical hole with the diameter of 0.3 mm) is arranged in the carrier, and the cylindrical hole extends along the central axis of the circumscribed circle of the trefoil. The strength of the catalyst carrier SH is shown in table 1.

The physicochemical properties of the support prepared above were characterized and the results are listed in table 1 below.

TABLE 1

Note: the ratio refers to the proportion of the difference R in the water absorption of the carrier; the strength refers to the radial crush resistance of the carrier.

Test examples

This test example is intended to illustrate the catalytic performance of a catalyst prepared using the support provided by the present invention.

The one-pass process is adopted, and the raw oil adopts the property of the Noocene VGO (2011): the density (20 ℃ C.) was 0.9122g/cm ³ ，T _IBP ＝272℃；T _50％＝422℃；T _FBP ＝536℃。

Crushing a catalyst into particles with the length range of 5-8 mm, loading 100g of the catalyst into a 200ml fixed bed reactor, filling the residual space with ceramic balls, before oil introduction, firstly adopting DMDS as a vulcanizing agent under the conditions that the hydrogen partial pressure is 15.0MPa and the temperature is 300 ℃, carrying out gas-phase vulcanization for 28 hours, then introducing raw oil at the temperature of 350 ℃ under the hydrogen partial pressure of 14.7MPa, wherein the hydrogen-oil ratio is 1200 volume/volume, and the liquid hourly volume space velocity is 0.85h ^-1 And a sample was taken after 400 hours of reaction.

The catalytic activity of the catalyst, the yield of the aviation kerosene (distillation range 160-:

the activity refers to the cracking reaction temperature required when the conversion rate of the hydrocarbon oil with the distillation temperature higher than 350 ℃ is 60 percent, and the lower the cracking reaction temperature is, the higher the catalytic activity of the catalyst is;

the 95% temperature of the tail oil is the distillation temperature of 95% of the distillation point in the simulated distillation curve.

TABLE 2

As can be seen from the data in Table 2, the catalyst prepared by the carrier provided by the invention has the advantages of high activity, high aviation kerosene yield and low catalyst bulk ratio.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A catalyst support comprising at least one of a refractory inorganic oxide and a molecular sieve; the carrier is internally provided with a through hole channel, and the ratio of the cross sectional area of the hole channel to the cross sectional area of the carrier is 0.03-20: 100; the equivalent diameter of the carrier is not more than 3 mm;

the cross section of the carrier is circular, and the pore passages extend along the central axis of the circular shape and/or are arranged at equal intervals along the circumferential direction of the central axis;

or the cross section of the carrier is in a multi-leaf shape, and the pore canal extends along the central axis of a circumscribed circle where the multi-leaf shape is located and/or extends along the central axis of a circumscribed circle where the multi-leaf shape is located;

the difference R between the water absorption of the carrier and the BET pore volume is not less than 0.2 mL/g;

the proportion of the difference R between the water absorption of the carrier and the BET pore volume in the water absorption of the carrier is 10-50%;

the radial crushing strength of the carrier is 14-30N/mm;

the preparation method of the catalyst carrier comprises the following steps:

(I) mixing a carrier precursor, a foaming agent, water, an optional extrusion aid and an optional adhesive to obtain a mixture; the foaming agent is an animal protein foaming agent and/or a plant foaming agent; the amount of the foaming agent is 0.1-50mL relative to 100g of the carrier precursor on a dry basis;

(II) molding the mixture to obtain a molded object with through-going pore channels inside, wherein the ratio of the cross-sectional area of the pore channels to the cross-sectional area of the molded object is 0.03-20: 100, respectively;

(III) roasting the formed product obtained in the step (II).

2. The carrier of claim 1 wherein the ratio of the cross-sectional area of the cell channel to the cross-sectional area of the carrier is from 0.1 to 15: 100.

3. the carrier according to claim 1, wherein the difference R between the water absorption of the carrier and the BET pore volume is 0.2-0.8 mL/g.

4. The carrier according to claim 3, wherein the difference R between the water absorption of the carrier and the BET pore volume is 0.2-0.5 mL/g.

5. The carrier according to any one of claims 1 to 4, wherein the ratio of the difference R between the water absorption of the carrier and the BET pore volume to the water absorption of the carrier is 15 to 35%.

6. The vector according to any one of claims 1 to 4,

the carrier is spherical or strip-shaped.

7. The carrier of claim 6, wherein the carrier is in the form of a strip.

8. The carrier of claim 7, wherein the carrier is in the form of a multilobal strip.

9. The vector according to any one of claims 1 to 4,

the equivalent diameter of the support is not more than 2 mm.

10. The carrier according to claim 9, wherein,

the equivalent diameter of the carrier is 0.8-2 mm.

11. The carrier according to any one of claims 1 to 4, wherein the pore channel is a channel of uniform cross section.

12. The carrier according to claim 11, wherein,

the pore canal is cylindrical or regular polygonal prism-shaped.

13. The carrier of claim 12,

the diameter of the cylindrical shape and the diameter of the circumscribed circle of the regular polygonal pyramid shape are each independently not less than 5 μm.

14. The carrier of claim 13, wherein the diameter of the cylindrical shape and the diameter of the circumcircle of the regular polygon are each independently 0.01-0.5 mm.

15. The carrier of claim 14, wherein the diameter of the cylindrical shape and the diameter of the circumcircle of the regular polygon prism are each independently 0.05-0.3 mm.

16. The carrier according to any one of claims 1 to 4, wherein the number of the pores is 1 to 10.

17. The carrier according to claim 16, wherein the number of the pores is 1 to 6.

18. The carrier according to any one of claims 1 to 4, wherein the carrier has a radial crush strength of 18 to 26N/mm.

19. The carrier according to any one of claims 1 to 4, wherein the heat-resistant inorganic oxide is at least one selected from the group consisting of alumina, silica, titania, magnesia, zirconia, thoria and beryllia;

the molecular sieve is selected from at least one of ten-membered ring silicon aluminum molecular sieve, twelve-membered ring silicon aluminum molecular sieve, fourteen-membered ring silicon aluminum molecular sieve and eighteen-membered ring silicon aluminum molecular sieve.

20. The support according to claim 19, wherein the heat-resistant inorganic oxide is selected from at least one of alumina, silica, titania, and zirconia;

the molecular sieve is selected from at least one of a ZRP molecular sieve, a Y molecular sieve, a beta molecular sieve, mordenite, a ZSM-5 molecular sieve, an MCM-41 molecular sieve, an omega molecular sieve, a ZSM-12 molecular sieve and an MCM-22 molecular sieve.

21. The support of claim 20, wherein the molecular sieve is selected from at least one of Y molecular sieve, beta molecular sieve, ZSM-5 and mordenite.

22. The vector according to any one of claims 1 to 4,

based on the total amount of the carrier, the content of the heat-resistant inorganic oxide is 1-99 wt%, and the content of the molecular sieve is 1-99 wt%.

23. The carrier according to claim 22, wherein the refractory inorganic oxide is present in an amount of 70 to 99 wt% and the molecular sieve is present in an amount of 1 to 30 wt%, based on the total amount of the carrier.

24. A method of preparing a catalyst support according to any one of claims 1 to 23, the method comprising:

(II) molding the mixture to obtain a molded object with through-going pore channels inside, wherein the ratio of the cross-sectional area of the pore channels to the cross-sectional area of the molded object is 0.03-20: 100;

(III) roasting the formed product obtained in the step (II).

25. The method of claim 24, wherein the foaming agent is an animal protein foaming agent.

26. The production method according to claim 24,

the animal protein foaming agent is at least one selected from animal hoof and horn foaming agents, animal hair foaming agents and animal blood gel foaming agents.

27. The production method according to claim 24,

the blowing agent is introduced in the form of a solution.

28. The production method according to claim 24, wherein the support precursor is selected from at least one of a refractory inorganic oxide, a refractory inorganic oxide precursor, and a molecular sieve;

the heat-resistant inorganic oxide is at least one selected from alumina, silica, titania, magnesia, zirconia, thoria and beryllia;

29. The production method according to claim 28,

the heat-resistant inorganic oxide is at least one selected from alumina, silica, titania and zirconia;

30. The method of claim 29, wherein,

the molecular sieve is selected from at least one of Y molecular sieve, beta, ZSM-5 and mordenite.

31. The production method according to any one of claims 24 to 30,

the dosage of the heat-resistant inorganic oxide and/or the precursor of the heat-resistant inorganic oxide and the molecular sieve ensures that the content of the heat-resistant inorganic oxide in the prepared carrier is 1 to 99 percent by weight based on the total amount of the carrier; the content of the molecular sieve is 1-99 wt%.

32. The production method according to claim 31, wherein the refractory inorganic oxide and/or the precursor of the refractory inorganic oxide and the molecular sieve are used in such amounts that the refractory inorganic oxide is contained in the resultant carrier in an amount of 70 to 99% by weight, based on the total amount of the carrier; the content of the molecular sieve is 1-30 wt%.

33. The production method according to any one of claims 24 to 30, wherein the extrusion aid is selected from at least one of sesbania powder, cellulose and derivatives thereof, starch and derivatives thereof, ethylene glycol and diethylene glycol;

the adhesive is selected from at least one of hydroxymethyl cellulose, inorganic acid, starch and derivatives thereof, silica sol or aluminum sol.

34. The method of any one of claims 24-30, wherein the mixing of step (I) comprises: mixing the carrier precursor and the extrusion aid, and then adding the foaming agent, the adhesive and the water to obtain the mixture.

35. The production method according to any one of claims 24 to 30,

the amount of the foaming agent is 0.5-20mL relative to 100g of the carrier precursor on a dry basis;

the amount of the extrusion aid is 0.1-6g relative to 100g of the carrier precursor on a dry basis;

the binder is used in an amount of 0.1 to 10g, relative to 100g of the carrier precursor on a dry basis.

36. The production method according to any one of claims 24 to 30,

the roasting conditions comprise: the temperature is 350-700 ℃; the time is 1-10 hours.

37. The production method according to claim 36,

the roasting conditions comprise: the temperature is 450-650 ℃; the time is 2-6 hours.

38. The method of claim 24, wherein the forming in step (II) is performed in a plodder comprising a body and an orifice plate, the body being configured to enable the mixture to be formed through the orifice plate;

the orifice plate includes: the device comprises a base (1) provided with a forming hole (2), a bracket (3) provided with at least one material through hole (6) and at least one forming rod (4); the support (3) and the base (1) are vertically overlapped, and the forming hole (2) is communicated with the material passing hole (6); the support (3) is further provided with at least one mounting hole (5) for the molding rod (4) to penetrate through, and the molding rod (4) is arranged to penetrate through the molding hole (2).

39. A method of manufacturing as claimed in claim 38, wherein the ratio of the cross-sectional area of the shaped rod (4) in the orifice plate to the cross-sectional area of the shaped orifice (2) is 0.03-20: 100, respectively;

and/or the equivalent diameter of the forming hole (2) is not more than 3 mm;

and/or the cross section of the forming hole (2) is circular, oval or multi-leaf; the multi-leaf shape is a trilobal shape, a quadralobal shape or a pentalobal shape; when the cross section of the forming hole (2) is in a multi-leaf shape, the forming rod (4) extends along the central axis of a circumscribed circle where the multi-leaf shape is located and/or extends along the central axis of a blade of the multi-leaf shape;

and/or the number of the molding rods (4) is 1-10;

and/or the number of the mounting holes (5) is equal to the number of the molding rods (4);

and/or the forming rod (4) is detachably connected with the bracket (3) through the mounting hole (5).

40. A production method according to claim 39, wherein the ratio of the cross-sectional area of the shaped rod (4) in the orifice plate to the cross-sectional area of the shaped orifice (2) is 0.1 to 15: 100;

and/or the equivalent diameter of the molding hole (2) is not more than 3 mm;

and/or the number of the forming rods (4) is 1-6.

41. A production method according to claim 39, wherein the equivalent diameter of the molding hole (2) is not more than 2 mm.

42. Preparation process according to claim 39, in which the forming orifice (2) has an equivalent diameter of 0.8-2 mm.

43. A production method according to claim 39, wherein the number of the through-holes (6) is 1 to 20;

and/or a plurality of material through holes (6) are arranged at equal intervals along the circumferential direction of the forming rod (4);

and/or the part of the forming rod (4) extending into the forming hole (2) is set to be of a uniform cross-section structure;

and/or the part of the forming rod (4) extending into the forming hole (2) is arranged to be a cylinder or a regular polygonal prism;

and/or the base (1) and the support (3) have the same overall outer contour;

and/or the base (1) and the bracket (3) are detachably connected.

44. A production method according to claim 43, wherein the number of the through-holes (6) is 2-20;

and/or, the diameter of the cylinder is set to be not less than 5 μm;

and/or the diameter of a circumscribed cylinder of the regular polygonal prism is set to be not less than 5 mu m.

45. The method of claim 44, wherein,

the diameter of the cylinder is set to be 0.01-0.5 mm;

or the diameter of the circumscribed cylinder of the regular polygonal prism is set to be 0.01-0.5 mm.

46. The method of claim 44, wherein,

the diameter of the cylinder is set to be 0.05-0.3 mm;

or the diameter of the circumscribed cylinder where the regular polygonal prisms are located is set to be 0.05-0.3 mm.

47. A catalyst carrier obtained by the production method according to any one of claims 24 to 46.