阅读说明：本技术 加氢催化剂及其应用以及加氢裂化方法 (Hydrogenation catalyst, application thereof and hydrocracking method ) 是由 董松涛 胡志海 赵广乐 杨平 赵阳 于 2019-10-31 设计创作，主要内容包括：本发明涉及加氢催化剂领域,公开了一种加氢催化剂,该催化剂包括载体和负载在载体上的第VIB族金属元素和第VIII族金属元素；所述载体含有耐热无机氧化物和分子筛中的至少一种；所述载体内部具有贯通的孔道,所述孔道的横截面积与所述载体的横截面积的比值为0.05-30：100；该载体的吸水率与BET孔容的差值R不低于0.2mL/g。将本发明提供加氢催化剂用于烃油的加氢裂化时,在获得较高的催化活性的同时,还能够获得高航煤收率。(The invention relates to the field of hydrogenation catalysts, and discloses a hydrogenation catalyst which comprises a carrier, and a VIB group metal element and a VIII group metal element which are loaded on the carrier; the carrier contains at least one of a heat-resistant 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 0.05-30: 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. When the hydrogenation catalyst provided by the invention is used for hydrocracking of hydrocarbon oil, high catalytic activity can be obtained, and high aviation kerosene yield can be obtained.)

1. A hydrogenation catalyst, which comprises a carrier and a VIB group metal element and a VIII group metal element loaded on the carrier;

the carrier contains at least one of a heat-resistant 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 0.05-30: 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.

2. The catalyst according to claim 1, wherein the content of the VIB group metal element is 10-35 wt%, the content of the VIII group metal element is 2-15 wt%, and the content of the carrier is 50-88 wt% calculated as oxide based on the total amount of the catalyst;

preferably, the content of the VIB group metal element is 15-30 wt%, the content of the VIII group metal element is 2.5-10 wt%, and the content of the carrier is 60-82.5 wt% calculated by oxides based on the total amount of the catalyst.

3. The catalyst according to claim 1, wherein the group VIB metal element is Mo and/or W, the group VIII metal element is Co and/or Ni;

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

preferably, the molecular sieve is selected from at least one of ten-membered ring silicoaluminophosphate molecular sieves, twelve-membered ring silicoaluminophosphate molecular sieves, fourteen-membered ring silicoaluminophosphate molecular sieves and eighteen-membered ring silicoaluminophosphate molecular sieves;

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

preferably, the content of the heat-resistant inorganic oxide is 1 to 99 wt% and the content of the molecular sieve is 1 to 99 wt% 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.

4. The catalyst according to any one of claims 1 to 3, wherein the ratio of the cross-sectional area of the cell channels to the cross-sectional area of the support is 0.1 to 20: 100, preferably 0.2 to 10: 100, respectively;

preferably, the difference R between the water absorption of the carrier and the BET pore volume is 0.2-0.8mL/g, and more preferably 0.2-0.5 mL/g;

preferably, 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 10 to 50%, preferably 15 to 35%.

5. The catalyst according to any one of claims 1 to 4,

the carrier is spherical and/or strip-shaped, preferably strip-shaped, and further preferably multi-leaf strip-shaped;

preferably, the equivalent diameter of the support is not more than 5mm, preferably not more than 3mm, more preferably not more than 2mm, still more preferably 0.8-2 mm;

preferably, the duct is a channel with a uniform cross section, and further preferably, the duct is a cylinder and/or a regular polygonal prism;

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

6. The catalyst according to any one of claims 1 to 5, wherein the support has a radial crush strength of 14 to 30N/mm, preferably 18 to 26N/mm;

preferably, the bulk ratio of the catalyst is 0.5 to 1g/mL, more preferably 0.6 to 0.9 g/mL.

7. The catalyst according to any one of claims 1-6, wherein the number of channels is 1-10, preferably 1-6;

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

preferably, the cross-section of the support is multi-lobal, the channels extending along the central axis of the circumscribed circle on which the multi-lobal vanes lie and/or along the central axis of the circumscribed circle on which the multi-lobal vanes lie.

8. The catalyst of any one of claims 1-7, wherein the support is prepared by a 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).

9. The catalyst according to claim 8, wherein the foaming agent is an animal protein foaming agent and/or a plant foaming agent, preferably an animal protein foaming agent;

preferably, the animal protein foaming agent is selected from at least one of an animal hoof and horn foaming agent, an animal hair foaming agent and an animal blood gel foaming agent;

preferably, the blowing agent is used in an amount of 0.1 to 50mL, preferably 0.5 to 20mL, relative to 100g of the carrier precursor on a dry basis;

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

10. The catalyst of claim 8, 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;

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.

11. The catalyst of claim 8, wherein the mixing of step (I) comprises: mixing a carrier precursor and an extrusion aid, and then adding a foaming agent, an adhesive and water to obtain a mixture;

preferably, the roasting conditions in step (II) include: the temperature is 350-700 ℃, preferably 450-650 ℃; the time is 1 to 10 hours, preferably 2 to 6 hours.

12. The catalyst of claim 8, wherein the forming in step (II) is performed in a plodder comprising a body and an orifice plate, the body being configured to enable forming of the mixture 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 stacked, and the forming holes (2) are communicated with the material passing holes (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).

13. The catalyst according to claim 8, wherein the ratio of the cross-sectional area of the shaped rods (4) in the perforated plate to the cross-sectional area of the shaped holes (2) is 0.05-30: 100, preferably 0.1 to 20: 100, more preferably 0.2 to 10: 100, respectively;

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, still more preferably 0.8-2 mm;

preferably, the cross section of the forming hole (2) is circular, oval or multi-leaf; preferably, the multilobal shape is a trilobal, quadralobal or pentalobal shape;

preferably, the number of the forming rods (4) is 1-10, preferably 1-6;

preferably, the cross section of the forming hole (2) is a multi-leaf shape, and the forming rod (4) extends along the central axis of a circumscribed circle of the multi-leaf shape and/or along the central axis of a blade of the multi-leaf shape;

preferably, the number of the mounting holes (5) is equal to the number of the molding rods (4);

preferably, the forming rod (4) is detachably connected with the bracket (3) through the mounting hole (5).

14. Catalyst according to claim 13, wherein the number of through-flow holes (6) is between 1 and 20, preferably between 2 and 20;

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

preferably, the part of the forming rod (4) extending into the forming hole (2) is provided with a uniform cross-section structure;

preferably, the part of the forming rod (4) extending into the forming hole (2) is provided as a cylinder, preferably the diameter of the cylinder is set to be not less than 5 μm, preferably 0.01 to 0.5mm, and further preferably 0.05 to 0.3 mm;

preferably, the part of the forming rod (4) extending into the forming hole (2) is provided with a regular polygonal prism, and the diameter of a circumscribed cylinder of the regular polygonal prism is preferably set to be not less than 5 μm, preferably 0.01-0.5mm, and further preferably 0.05-0.3 mm;

preferably, the base (1) and the support (3) have the same overall outer contour;

preferably, the base (1) and the support (3) are arranged in a detachable connection.

15. Use of a hydrogenation catalyst as claimed in any one of claims 1 to 14 in hydrocracking.

16. A hydrocracking process, comprising: contacting a hydrocarbon oil with a hydrocracking catalyst under hydrocracking conditions, wherein the hydrocracking catalyst is the hydrocracking catalyst of any one of claims 1 to 14.

Technical Field

The invention relates to the field of hydrogenation catalysts, and particularly relates to a hydrogenation catalyst, application thereof and a hydrocracking method.

Background

Increasing awareness of environmental concerns and stricter environmental regulations are forcing the oil refining community to focus more on the development of clean fuel production technologies. The future market of vehicle fuel tends to be ultra-low sulfur, and fuel which can not meet the emission standard can not enter the market. The hydrogenation technology is used as an effective desulfurization means and plays an increasingly important role in the production of clean vehicle fuels, wherein a high-efficiency hydrogenation catalyst is a core technology of the hydrogenation technology, and therefore, the development of a novel hydrocracking catalyst with higher activity and selectivity is one of the most urgent needs of the oil refining industry.

Hydrocracking catalysts are generally prepared by impregnation, i.e., a process in which a support is impregnated with a solution containing the desired active component (e.g., Ni, Mo, Co, W, etc.), followed by drying, calcination, or no calcination. The active component and the carrier in the catalyst are important components 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.

The selection of the geometry and dimensions of a commercial catalyst often requires balancing in several ways while simultaneously taking into account several 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 a cylindrical strip, a trilobal strip, a quadralobe strip, 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 supports, i.e., a matrix of cordierite or alumina on which regularly arranged channels are commonly used for SCR and automotive exhaust treatment, etc.

In order to improve the diffusion properties of the catalyst, the prior art discloses several methods. CN1859975A discloses a deformed trilobal stripe catalyst. CN101134173A proposes a carrier and a catalyst with special shapes, which are ellipsoids, and one or more grooves are opened on the ellipsoids, and said to have large external surface area and good mass transfer performance, so it can be widely used in heavy oil processing reaction. CN105233880A discloses an inner core type cloverleaf-shaped catalyst carrier and a preparation method and application thereof. 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 1m²The 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 the pore canal 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, there is also a method of increasing the amount of macropores or super macropores by adding a forming aid in order to improve the catalyst diffusion performance. 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. 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. CN101890382B proposes a catalyst preparation method, 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 residue 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.

From the above, the catalysts and carriers in the prior art still have many defects, and it is desirable to provide a catalyst which can combine high strength, high activity and high selectivity.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a hydrogenation catalyst, application of the hydrogenation catalyst in hydrocracking and a hydrocracking method.

In order to achieve the above object, a first aspect of the present invention provides a hydrogenation catalyst comprising a carrier and a group VIB metal element and a group VIII metal element supported on the carrier;

the carrier contains at least one of a heat-resistant 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 0.05-30: 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.

Preferably, the content of the VIB group metal element is 10-35 wt%, the content of the VIII group metal element is 2-15 wt%, and the content of the carrier is 50-88 wt% calculated by oxides based on the total amount of the catalyst.

Preferably, the ratio of the cross-sectional area of the channel to the cross-sectional area of the support is 0.1 to 20: 100, preferably 0.2 to 10: 100.

preferably, the equivalent diameter of the support is not more than 5mm, preferably not more than 3mm, more preferably not more than 2mm, still more preferably 0.8-2 mm.

Preferably, the difference R between the water absorption of the carrier and the BET pore volume is 0.2-0.8mL/g, and more preferably 0.2-0.5 mL/g.

In a second aspect, the present invention provides the use of a hydrogenation catalyst as described above in hydrocracking.

In a third aspect, the present invention provides a hydrocracking process comprising: under the hydrocracking condition, the hydrocarbon oil is contacted with a hydrocracking catalyst, wherein the hydrocracking catalyst is the hydrocracking catalyst provided by the invention.

In the forming process of the carrier of the catalyst, the carrier with an internal pore channel structure is processed by a one-step method, and the carrier is internally provided with a through pore channel, so that the effective utilization rate of active components of the catalyst is improved; meanwhile, the foaming agent is added during the forming of the carrier, 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 the pore channel of the carrier is improved. The hydrogenation catalyst provided by the invention adopts the carrier with an improved pore channel structure, so that the diffusion process of macromolecules is enhanced, the activity of the catalyst and the accessibility of an active center are favorably improved, and when the hydrogenation catalyst is used for hydrocracking hydrocarbon oil, not only can a higher aviation kerosene yield be obtained, but also high catalytic activity can be obtained.

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 carrier SA according to example 1 of the present invention;

FIG. 5 is a schematic diagram of a rack of one embodiment of the orifice plate of the present invention;

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

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

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

FIG. 9 is a schematic cross-sectional view of a 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, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, unless otherwise specified, the use of the terms of orientation such as "upper, lower, left, and right" generally means "upper, lower, left, and right" with reference to the drawings, and the use of the terms of orientation such as "inner and outer" means inner and outer with respect to the outline of each component itself.

The first aspect of the invention provides a hydrogenation catalyst, which comprises a carrier and a VIB group metal element and a VIII group metal element loaded on the carrier;

the carrier contains at least one of a heat-resistant 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 0.05-30: 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 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.

The group VIB metal element and the group VIII metal element may be supported on the carrier in various forms that are conventional in the art, respectively, such as: the group VIB metal element and the group VIII metal element may be supported on the support in the form of an oxide and/or a sulfide, respectively. That is, the hydrogenation catalyst of the present invention includes an oxidation state catalyst before sulfiding, and also includes a sulfided state catalyst after sulfiding.

The content selection range of the VIB group metal element and the VIII group metal element in the hydrogenation catalyst is wide. Preferably, the content of the group VIB metal element is from 10 to 35 wt.%, preferably from 15 to 30 wt.%, calculated as oxide, based on the total amount of catalyst; the content of the VIII group metal element is 2 to 15 wt%, preferably 2.5 to 10 wt%; the carrier is present in an amount of 50 to 88 wt.%, preferably 60 to 82.5 wt.%.

According to a preferred embodiment of the present invention, the group VIB metal element is Mo and/or W, and the group VIII metal element is Co and/or Ni.

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

According to one embodiment of the invention, the carrier has a dry water absorption of 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 support is between 0.62 and 1.3mL/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 present invention, the difference R between the water absorption of the carrier and the BET pore volume is preferably 0.2 to 0.8mL/g, more preferably 0.2 to 0.5 mL/g.

According to the invention, the ratio of the difference R between the water absorption of the support and the BET pore volume to the water absorption of the support is preferably from 10 to 50%, preferably from 15 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-dry 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 0.1 to 20: 100, preferably 0.2 to 10: 100. the catalyst provided by the invention has a pore structure in the carrier, 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 carrier was measured on a crushing strength measuring apparatus (available from soda research, chemical industry Co., Ltd.) of QCY-602 according to the method specified in GB 3635-1983.

In the preferable condition, the carrier adopted by the catalyst provided by the invention has higher mechanical strength, so that the mechanical strength of the catalyst is better, and in addition, the carrier adopted by the catalyst provided by the invention has a better pore channel structure, so that the activity of the catalyst and the accessibility of an active center can be effectively improved, and the catalyst is very suitable for the diffusion of macromolecules.

The carrier may have various shapes depending on the specific application. For example, the carrier 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 in any way. The spherical shape mentioned in the invention can be a regular spherical shape or an irregular spherical shape, namely, the outline curve of the cross section of the carrier can be a circular shape or a non-perfect circular shape. The invention does not limit the length and 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.

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% 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.

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 multilobal shape and the proportion of the size of each blade to other blades, namely the multilobal shape can be a regular multilobal shape, a non-regular multilobal shape or a deformed multilobal 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 cross-sectional 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.

According to a preferred embodiment of the present invention, the bulk ratio of the catalyst is 0.5 to 1g/mL, more preferably 0.6 to 0.9 g/mL. The catalyst provided by the invention has a low bulk ratio.

In the invention, the bulk ratio of the catalyst is determined by a conventional method, and the specific method comprises the following steps: crushing the catalyst, screening particles of 16-20 meshes, taking a 500mL measuring cylinder, pouring the screened particles into the measuring cylinder, weighing the weight G and the visual volume V, wherein the bulk ratio of the catalyst is G/V.

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 is regular in 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 the channels include but are not limited to cones when the cross section of the channels is gradually increased along the material flow direction; in the case where the cross-section of the channel decreases progressively along the direction of flow, the 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 in shape. The preferred embodiment is convenient for processing, and simultaneously, the carrier with the through pore channel structure with the corresponding shape is more beneficial to the diffusion of macromolecules.

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 carrier, and is beneficial to improving the compactness and the strength of the carrier. It should be noted that, in the present invention, the circle and regular polygon also include imperfect circle and/or regular polygon.

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.

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.

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 passages of the correspondingly obtained carrier 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 canals is wide, and the number of the pore canals can be 1 or more than two according to the comprehensive consideration of the strength and the stacking ratio by a person skilled in the art, and the pore canals can be properly selected according to the actual requirement on the number of the pore canals. 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 of the pore channel is wide in selection range, and the pore channel can penetrate through the carrier. When the number of the pore channels is one, the pore channels preferably extend along a central axis of a circumscribed circle of the cross section of the support, in which case, when the cross section of the support is circular, the pore channels extend along the central axis of the circle; 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 positioned.

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 embodiment is more favorable for ensuring the stress distribution of the carrier to be more balanced, and further optimizing the overall strength of the 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 distance between the pore channels and the center of the circumscribed circle where the cross section of the carrier is located is equal to the distance between the pore channels and 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 local strength drop caused by the arrangement of the middle pore channel structure on the 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 local strength drop caused by the arrangement of the middle pore channel structure on the carrier, and can ensure the mechanical strength of the catalyst.

In the present invention, the composition of the carrier 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 heat-resistant inorganic oxide is alumina.

The alumina mentioned in the invention refers to available mAl₂O₃·nH₂O 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 of the invention can be one type, or two or more types, or mixed crystal and twin crystal of two molecular sieves. The two molecular sieves described in the present invention 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-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 carrier).

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 ten-membered ring silicoaluminophosphate molecular sieves, twelve-membered ring silicoaluminophosphate molecular sieves, fourteen-membered ring silicoaluminophosphate molecular sieves, and eighteen-membered ring silicoaluminophosphate molecular sieves. 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 SiO₂/Al₂O₃。

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 of the invention can be obtained commercially or prepared by 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 the phosphorus-containing ultrastable Y molecular sieve is prepared by exchanging the Y molecular sieve with one or more inorganic ammonium solutions of phosphide and then carrying out one or more times of hydrothermal treatment; or the rare earth Y molecular sieve is prepared by combining the rare earth compound aqueous solution treatment Y molecular sieve with one or more hydrothermal treatments.

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 content of the heat-resistant inorganic oxide is 70 to 97% by weight based on the total amount of the carrier; the content of the molecular sieve is 3-30 wt%.

The source of the vector is not particularly limited in the present invention as long as the vector having the above structure can be obtained. Preferably, the preparation method of the 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;

(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).

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 catalyst provided by the invention, the carrier precursor is any substance which 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 heat-resistant inorganic oxide precursor is any substance that can be converted into a heat-resistant 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 selection of the molecular sieve is as described above and the present invention is not described herein in detail.

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 may be a 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 also 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 suitably added during the hydrolysis, 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 prepared catalyst is 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 an advantageous 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 foaming agent is preferably a plant foaming agent, and the amount of the foaming agent is 0.1-5 g.

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 carrier preparation process, a peptizing agent, such as dilute nitric acid, is required to be added, but in the carrier preparation method provided by the invention, the peptizing agent can be added or not added.

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 catalyst provided by the invention, the preparation method of the carrier 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 present invention, the molded article having a through-hole in the interior is obtained by the above 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 a hole plate for plodding, the body being configured to enable the mixture to be formed through the hole 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 arranged in an up-down overlapping mode, 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 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 accordingly. The preferred embodiment realizes that the carrier with the internal pore structure is processed and prepared by a one-step method, the operation is simple and convenient, and the prepared carrier has high strength and high utilization rate of active metal.

According to the invention, the term "extruding" means that the pore plate is used for extruding, and the term "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 holes 2 penetrate through the base 1, so that a carrier having through-holes 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 such a length that one end of the forming rod 4 is located at the end of the base 1 away from the bracket or that one end of the forming rod 4 is located outside the end of the base 1 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 channel to the cross-sectional area of the carrier. For example, 0.05 to 30: 100, preferably 0.1 to 20: 100, more preferably 0.2 to 10: 100. this preferred embodiment is more advantageous in that the resulting support has both high strength and high active metal utilization.

According to the invention, it is understood that the shape of the shaping opening 2 is in fact the shape of the carrier 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 multi-lobed shape are not particularly limited and may be selected from those described above with respect to the shape of the support.

The size of the molding holes 2 is selected from a wide range, and those skilled in the art can make appropriate selections according to the requirements of the size of the carrier, and the carrier preparation method of the invention is particularly suitable for preparing small-size carriers, and preferably, the equivalent diameter of the molding holes 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 in the support as described above.

According to the invention, the location of the shaped rods corresponds to the location of the openings in the carrier, and the person skilled in the art knows how to arrange the shaped rods, as described above in relation to the location of the openings in the 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 a multilobal shape, the profiled bar 4 extending along the central axis of the circumscribed circle of the multilobal shape and/or along the central axis of the vanes of the multilobal shape. By adopting the preferred implementation, the arrangement position of the pore structure in the carrier is designed more reasonably, so that the pore distribution is balanced, the local strength drop caused by arranging the middle pore structure on the 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 can be selected within a wide range, for example from 1 to 20, preferably from 2 to 20. Preferably, as shown in fig. 2, the plurality of through 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 material passing holes 6 arranged in the circumferential direction of each forming rod 4 can be selected by those skilled in the art according to actual conditions. It will be appreciated that the through-flow openings 6 may be provided in any suitable manner, for example, as shown in figure 2, a plurality of through-flow openings 6 may be in communication with the mounting openings 5 or may be isolated from the mounting openings 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 forming rod 4 extending into the forming 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 carrier and is beneficial to obtaining a compact 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 carrier with the pore 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 hole in the carrier. Preferably, the part of the forming rod 4 extending into the forming hole 2 is provided as a cylinder. Under the condition, the prepared carrier can correspondingly form a pore structure with a cylindrical structure, so that the inner surface of the carrier is smoother and more regular, the phenomenon of stress concentration of the carrier caused by the existence of sharp pore walls in the pore structure is avoided, and the probability of carrier collapse 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 polygon. Under the condition, the prepared carrier can correspondingly form a pore channel structure with a regular polygonal prism structure, so that the inner surface of the carrier is more regular, the stress distribution of the carrier is more balanced, and the overall strength of the 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.

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 passages of the correspondingly obtained carrier are correspondingly formed into regular polygonal structures such as equilateral triangle, square, regular pentagon and the like.

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 5.0).

For ease of understanding, a specific molding method is now provided, comprising: and (2) 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 through hole 6 arranged on a support 3 so as to obtain a formed object with through pore channels inside, the number and the shape of the forming rods 4 correspond to the number and the shape of the pore channels, 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 catalyst provided by the invention can be prepared by various methods commonly used in the art, for example, an impregnation method can be adopted, a co-impregnation method can be adopted to load the VIB group metal element and the VIII group metal element on the carrier together, or stepwise impregnation can be adopted to respectively charge the VIB group metal element and the VIII group metal element on the carrier, and the introduction sequence of the VIB group metal element and the VIII group metal element is not particularly limited. Specifically, the group VIB metal element and the group VIII metal element may be supported on the carrier by impregnating the carrier with a solution containing a compound of the group VIB metal element and a compound of the group VIII metal element, and drying and calcining the carrier on which the above two compounds are supported. The group VIB metal element compound and the group VIII metal element compound may be selected according to the kinds of the group VIB metal element and the group VIII metal element, respectively. When the group VIB metal element is molybdenum and/or tungsten, the compound of the group VIB metal element may be a compound of tungsten and/or a compound of molybdenum. In the present invention, examples of the compound of the group VIB metal element may include, but are not limited to: one or more of tungstic acid, molybdic acid, metatungstic acid, ethyl metatungstic acid, paramolybdic acid, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate and ammonium ethyl metatungstate. When the group VIII metal element is cobalt and/or nickel, the compound of the group VIII metal element is preferably one or more of an oxysalt using nickel as a cation, an oxysalt using cobalt as a cation, and an oxysalt using cobalt as a cation. In the present invention, examples of the compound of the group VIII metal element may include, but are not limited to: one or more of nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, nickel chloride and cobalt chloride.

According to the present invention, various solvents commonly used in the art may be used to prepare a solution containing a compound of a group VIB metal element and a compound of a group VIII metal element, as long as the compounds are soluble in the solvent to form a uniform and stable solution. For example: the solvent may be water.

The impregnation method may be various impregnation methods commonly used in the art, and for example, may be a pore saturation impregnation method. The time for the impregnation and the number of times of the impregnation are not particularly limited in the present invention, as long as the amounts of the group VIB metal element and the group VIII metal element on the finally obtained catalyst can be ensured to meet specific use requirements. Generally, the time for the impregnation may be 0.5 to 12 hours.

According to the present invention, the conditions for drying the carrier loaded with the group VIB metal element and the group VIII metal element are not particularly limited. Generally, the temperature of the drying may be 80-300 ℃, preferably 100-; the drying time may be 0.5 to 24 hours, preferably 1 to 12 hours.

In the present invention, the conditions for calcining the dried carrier loaded with the group VIB metal element and the group VIII metal element are not particularly limited, and may be conventional conditions in the art. Generally, the temperature of the roasting may be 350-700 ℃, preferably 400-650 ℃; the calcination time may be 0.2 to 12 hours, preferably 1 to 10 hours. The calcination may be performed in an oxygen-containing atmosphere.

The hydrogenation catalyst provided by the invention is suitable for hydrogenation reactions of various hydrocarbon raw materials, including but not limited to hydrodesulfurization, hydrodenitrogenation, olefin saturation, aromatic saturation, hydrocracking and hydroisomerization. The catalyst provided by the invention can also be used as an oxidation catalyst for aromatization reaction, photocatalytic reaction, immobilized enzyme and the like.

The hydrocarbon feedstock may be various heavy mineral oils or synthetic oils or their mixed distillates, such as straight run gas oils (straight run gas oil), vacuum gas oils (vacuum gas oil), demetallized oils (demetalized oils), atmospheric residues (atmospheric residues), deasphalted vacuum residues (deasphalted vacuum residues), coker distillates (coker distillates), catalytic cracker distillates (cat cracker distillates), shale oils (shell oils), tar sand oils (tar sand oil), and coal liquefaction oils (coal liquid).

The inventors of the present invention have found that the catalysts provided by the present invention are particularly suitable for use as hydrocracking catalysts, and thus, in a second aspect the present invention provides the use of the hydrogenation catalysts of the present invention in hydrocracking. The hydrogenation catalyst provided by the invention is used for hydrocracking various hydrocarbon oils to produce hydrocarbon fractions with lower boiling points and lower molecular weights.

According to a third aspect of the present invention, there is provided a hydrocracking process comprising: under the hydrocracking condition, the hydrocarbon oil is contacted with a hydrocracking catalyst, wherein the hydrocracking catalyst is the hydrocracking catalyst provided by the invention.

The hydrogenation catalyst, the preparation method thereof, and the kind of hydrocarbon oil have been described in detail above and will not be described in detail herein.

The hydrocracking process of the present invention is not particularly limited with respect to the remaining conditions for hydrocracking, and may be conditions conventional in the art. Generally, the hydrocracking conditions include: the temperature can be 200-650 ℃, preferably 300-510 ℃; the pressure may be from 3 to 24 MPa, preferably from 4 to 15 MPa, expressed as gauge pressure; the volume ratio of the hydrogen to the oil can be 100-; the liquid hourly volume space velocity can be 0.1-30 h^-1Preferably 0.2 to 5 hours^-1。

According to the hydrocracking process of the present invention, the catalyst is preferably presulfided prior to use. The conditions of the prevulcanisation may be conventional in the art. For example, the conditions of the prevulcanisation may include: presulfiding with sulfur, hydrogen sulfide or a sulfur-containing feedstock in the presence of hydrogen at a temperature of 140 ℃ and 370 ℃. According to the hydrocracking process of the present invention, the presulfiding can be carried out either outside the reactor or in situ within the reactor. The specific conditions for such vulcanization are well known to those skilled in the art and the present invention will not be described herein. The catalyst provided by the invention can be directly used without pretreatment; or may be previously subjected to reduction treatment and reused.

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 dry water absorption rate, the wiping dry water absorption rate is that the carrier which is dry is soaked in deionized water for 60 minutes at room temperature (20-25 ℃), the carrier is wiped dry by using filter paper after filtration, the mass of the carrier after water absorption is obtained, and the ratio of the mass difference of the carrier which does not absorb water to the carrier which does not absorb water is wiping dry water absorption rate; the radial crushing strength of the carrier was measured on a crushing strength tester of model QCY-602 (manufactured by alkali research, Ministry of chemical industry) according to the method specified in GB 3635-1983; the pile ratio of the catalyst was determined according to the method of "Industrial catalyst analysis and test characterization" (edited by Liu Hiso, China petrochemical Press, Beijing, 4 months 1990) p 29. In the invention, the method for testing the bulk ratio of the catalyst comprises the following steps: crushing the catalyst, screening particles of 16-20 meshes, taking a 500mL measuring cylinder, pouring the screened particles into the measuring cylinder, weighing the weight G and the visual volume V, wherein the bulk ratio of the catalyst is G/V.

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

Preparation example 1

(1) 200.0g of dry rubber powder (taken from catalyst Changling division company, 68 wt% of dry basis, and the main phase of pseudoboehmite, the same below), 19.2g of HY molecular sieve (taken from catalyst Changling division company, 79 wt% of dry basis, and FAU type molecular sieve, the same below) and 8g of sesbania powder are uniformly mixed to obtain mixed powder. 10mL of egg white (taken from a fresh egg) and 1g of hydroxymethyl cellulose are added with water to 175mL, and after foaming in a foaming machine, the mixture is mixed with the mixed powder to obtain a mixture.

(2) Feeding the above mixture into a strip extruder, repeatedly kneading for 3 times (15 min), and thenAnd (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-leaf strip shape, the diameter of an external circle of the cross section is 1.6mm, 3 through holes (3 cylinders with the diameter of 0.1 mm) are formed in the carrier, and the 3 cylindrical holes respectively extend along the central axis of the external circle where the three blades are located. The cross-sectional view of the carrier is shown in FIG. 4, and the strength of the carrier is shown in Table 1.

The specific process of the molding is as described in the above specific embodiment, wherein the molding is performed using a perforated plate, the perforated plate including: 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. 5, 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.

Preparation of comparative example 1

(1) 200.0g of dry rubber powder, 19.2g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. 2.5mL of nitric acid with the weight concentration of 68 percent is added with water to 155mL, evenly mixed and then added into the mixed powder, and the mixture is obtained after mixing. The mixture is sent into a strip extruding machine to be repeatedly kneaded for 3 times (15 minutes) and then adoptedAnd (3) extruding the three-leaf strip-shaped pore plate, 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 a solid (without pore channels) carrier DA.

The carrier is in the shape of 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.

Preparation example 2

(1) 200.0g of dry rubber powder, 19.2g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. Animal protein foaming agent (preparation method: cow hoof horn 20g, Ca (OH))₂ 6g，NaHSO₃2g, 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.)10mL (equal to 1.0g of cow hoof) and 1g of hydroxymethyl cellulose, adding water to 175mL, foaming in a foaming machine, and mixing with the mixed powder to obtain a mixture.

(2) Feeding the above mixture into a strip extruder, repeatedly kneading for 3 times (15 min), and thenBelt coreExtruding strips through a four-leaf-shaped orifice plate, wherein the orifice 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 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.

Preparation example 3

A carrier was prepared according to the method of preparation example 1, except that egg white was used in an amount of 5 mL. And useExtruding the cored trilobal pore plate. This carrier is three leaf bar-types, and the circumscribed circle diameter of cross section is 1.6mm, and the carrier is inside to have 4 pore (1 circumscribed circle diameter is the positive trilateral arris body of 0.1mm, 3 cylinders that the diameter is 0.1 mm), the central axis of the circumscribed circle of 1 positive trilateral prism pore along the trilobal extends, 3 cylinder pore extend along the central axis of the circumscribed circle at three blade place respectively. The vector SC is obtained. The cross-sectional area of the carrier is shown in figure 8. The strength of the support is shown in Table 1.

Preparation example 4

The carrier was prepared according to the method of preparation example 2, except that the animal protein foaming agent was used in an amount of 20mL andextruding 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 to obtain the carrier SD. The cross-sectional area of the carrier is shown in FIG. 9, and the strength of the carrier is shown in Table 1.

Preparation example 5

The procedure of preparation example 1 was followed except that 20mL of egg white was used. The support SE was obtained, the strength of which is shown in Table 1.

Preparation example 6

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

(1) 200.0g of dry rubber powder, 19.2g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. Mixing 1.5g 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, foaming in a foaming machine, and mixing with the mixed powder to obtain a mixture.

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

Preparation example 7

The carrier was prepared according to the method of preparation example 1 except thatThe 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). Thus obtaining the catalyst carrier SG. 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 strength of the support is shown in Table 1.

The physicochemical properties of the support obtained above were characterized and the results are shown 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.

Examples 1 to 7 and comparative example 1

This example serves to illustrate the catalytic performance of a catalyst provided by the present invention.

The water absorption of the carrier was measured, and an aqueous mixture of nickel nitrate (analytically pure, from beijing yili chemical reagent factory) and ammonium metatungstate (industrial, available from chandelian catalyst factory) was prepared so that the tungsten oxide content in the catalyst was 21.5 wt% and the nickel oxide content was 2.5 wt%, and the carriers of the above preparation examples and preparation comparative examples were impregnated by a pore saturation method. The impregnated carrier was dried at 120 ℃ for 5 hours and then calcined at 400 ℃ for 3 hours to obtain CSA to CSG catalysts and CDA catalysts, respectively. The measured bulk ratio of each catalyst is shown in Table 2.

The one-pass process is adopted, and the raw oil adopts the properties of the Nominax VGO (2011): the density (20 ℃ C.) was 0.9122g/cm³，T_IBP＝272℃；T_50％＝422℃；T_FBP＝536℃。

Crushing a catalyst into particles with the length range of 3-5 mm, filling 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 320 ℃ and the hydrogen-oil ratio of 1200 volume/volume and the liquid hourly volume space velocity of 0.85 hour at the hydrogen partial pressure of 14.7MPa, wherein the hydrogen partial pressure is 15.0MPa, and the catalyst is subjected to gas-phase vulcanization for 28 hours^-1And 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 the 95% distillation point in the simulated distillation curve.

Example 8

A catalyst CSH was prepared according to the procedure of example 1 except that a mixed aqueous solution of ammonium molybdate, basic nickel carbonate and phosphoric acid was prepared in accordance with the catalyst having a molybdenum oxide content of 16.3 wt%, a nickel oxide content of 2.8 wt% and a phosphorus content of 1.1 wt%, respectively, and the performance data of the catalyst are shown in table 2.

Example 9

According to the method of example 1, except that a mixed aqueous solution of ammonium metatungstate and nickel nitrate was prepared in which the tungsten oxide content and the nickel oxide content were 17.0 wt% and 3.0 wt%, respectively, in the catalyst, catalyst CSI was prepared, and the performance data of the catalyst are shown in table 2.

TABLE 2

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