CN112827481B - Catalyst alumina carrier material with gradient structure and preparation method thereof - Google Patents

Catalyst alumina carrier material with gradient structure and preparation method thereof Download PDF

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CN112827481B
CN112827481B CN201911163752.9A CN201911163752A CN112827481B CN 112827481 B CN112827481 B CN 112827481B CN 201911163752 A CN201911163752 A CN 201911163752A CN 112827481 B CN112827481 B CN 112827481B
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powder
aluminum hydroxide
alumina
raw material
carrier material
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CN112827481A (en
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南洋
霍存宝
刘俊涛
全民强
杨红强
刘肖飞
李燕
景志刚
常晓昕
谢元
马好文
边虎
薛文利
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Petrochina Co Ltd
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Abstract

The invention relates to a catalyst alumina carrier material with a gradient structure and a preparation method thereof. The pore diameter of the carrier material is 20-2000 nm, and the specific surface area is 1-140 m 2 Per g, pore volume 0.1-1.2 ml/g, and crushing strength 10-200N/cm. The aluminum hydroxide powder is mainly used as a raw material and is prepared by a powder bed fusion 3D printing technology. Dividing a three-dimensional model of the alumina porous material into different areas according to gradient functional requirements, processing raw material powder by adopting different laser energy densities in the different areas, and obtaining the alumina carrier material with the gradient structure in the inner space through changing the laser energy densities. The invention solves the problem that the structural change range of the material is limited after the alumina is taken as the raw material and irradiated by different laser energy densities.

Description

Catalyst alumina carrier material with gradient structure and preparation method thereof
Technical Field
The invention relates to a catalyst alumina carrier material and a preparation method thereof.
Background
The supported catalyst is applied to a plurality of petrochemical production processes, wherein the supported catalyst taking alumina material as a carrier is of a very wide application type, such as pyrolysis gasoline hydrogenation catalyst and C 2 Hydrogenation catalysts, ethylene epoxidation catalysts for the production of ethylene oxide, and the like. The preparation process of the supported catalyst is to soak the catalyst carrier material in the soaking liquid containing active component metal ion, and heat treat the soaked carrier material to make the outer surface and the inner surface of the microscopic holes of the carrier to support active component metal, so as to obtain the catalyst with corresponding catalytic reaction capacity. The catalyst carrier material provides a platform for immobilizing active components and also provides a transmission pore path for the internal diffusion process of the components and products in the catalytic reaction. Thus, for supported catalysts supported on alumina materials, the structure and pore properties of the alumina support material often greatly influence the outcome of the catalytic reaction.
Many catalytic reactions, the target product of which is not the final step that the reaction can proceed to, for example, the hydrogenation of vinyl acetylene, do not wish to obtain butane that is obtained by complete hydrogenation, but rather wish to obtain butadiene that is the one step in the middle of the hydrogenation process; as another example, ethylene epoxidation processes are intended to obtain ethylene oxide by partial oxidation without the intention of letting ethylene oxide continue to undergo deep oxygenFormation into CO of no economic value 2 And water.
In order to obtain these selective reaction products by using these supported catalysts with alumina material as carrier, it is important to optimize the transfer effect during the catalytic reaction besides optimizing the ratio of the catalyst active component and the auxiliary component. For this reason, researchers have tried many methods, for example, by controlling the impregnation conditions, adjusting the loading depth of the active ingredient on the carrier, so as to control the reaction time during the diffusion inside the carrier, so that the reaction process stays as far as possible in the selective product formation stage without continuing the deep reaction. The pore size distribution of the alumina carrier is changed to optimize the diffusion effect inside the carrier, so that the reaction can effectively occur, and the selective product can be separated from the inside of the catalyst in time, so that the condition that the product is adsorbed again by an active center to deeply react in the process of diffusing from the inside of the catalyst to the outside is reduced, and the yield of the target product is improved. The above schemes are all optimized in the technical aspect of the transmission space inside the catalyst, and have certain effects, but the catalyst alumina carrier is made of the same material from outside to inside, the crystal structure and the pore channel structure are uniform, the carrier material is changed as a whole due to the change of technical conditions, and the structural adjustment optimization from outside to inside of the carrier cannot be achieved, so the improvement of the reaction performance of the catalyst is still limited.
The gradient functional material is a novel composite material in which two or more materials are compounded and the components and the structure are continuously changed in gradient. Its design requirement function and performance can be changed according to the change of internal position of material, and can be satisfied by optimizing the whole performance of component.
3D printing is a technology which has been rapidly developed in recent years, and which is capable of precisely manufacturing 3D devices having a desired structure, and has a great application potential in manufacturing gradient functional materials. The powder bed melting is a rapid forming method widely applied to 3D printing technology, and mainly uses polymer, ceramic and metal powder as raw materials, so that the polymer, ceramic and metal powder are sintered layer by layer under the radiation heating of laser, the rapid manufacturing of a complex structure can be realized, the whole manufacturing process does not need the assistance of other mechanical processing of a die, the product development period is greatly shortened, and the integration from free design to manufacturing is realized. 3D printing of the alumina material is performed by adopting a powder bed melting process, pores are formed in the manufactured part through interaction between laser and powder in the manufacturing process, and the pores caused by the process provide a new thought for preparing the porous material.
If the catalyst alumina carrier material with the gradient function structure can be manufactured by adopting the powder bed fusion 3D printing process, the structure adjustment optimization from the outside to the inside of the carrier is realized, so that the reaction performance of the catalyst is improved.
Through the search of the prior literature and patent, we find that no research on a catalyst alumina carrier material with a gradient functional structure has been reported in the field of manufacturing alumina porous materials by a powder bed melting process at present. In the patent of 'a preparation method of porous ceramic with complex structure based on laser selective sintering' (patent number: CN 201610687672.3), although the patent can directly perform 3D printing by using ceramic materials such as alumina or cordierite, the scheme only prepares a macroscopic complex appearance structure, the material properties are uniform, and a gradient functional structure with the material properties is not formed. In the preparation of laser sintering 3D printing rapid prototyping alumina powder (patent number: CN 201510284342.5), the preparation of alumina powder is mainly focused; in the patent of the integrated laser sintering and 3DP 3D printing system and printing method (patent number: CN 105397088A), the description of the equipment is mainly focused, and neither patent describes how to prepare the gradient functional material. In addition, the technical proposal uses alumina as raw material to carry out powder laser sintering and melting, and the alumina has a relatively stable structure and limited range of changing crystal and pore structure after irradiation of laser energy, so that the alumina carrier material with a large gradient structure range is difficult to directly prepare.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a catalyst alumina carrier material with a gradient structure and a preparation method thereof.
The preparation method of the catalyst alumina carrier material with the gradient structure mainly comprises the following steps:
1) Preparing raw material powder: the raw material powder is prepared by uniformly mixing aluminum hydroxide powder and inorganic additive powder, wherein the aluminum hydroxide powder accounts for 65-98 wt% of the total mass of the raw material powder, the inorganic additive powder accounts for 2-35 wt% of the total mass of the raw material powder, the inorganic additive powder consists of boron carbide and one or more of silicon powder, silicon oxide and magnesium oxide, and the boron carbide accounts for 3-100 wt% of the total mass of the inorganic additive powder;
2) Establishing a three-dimensional model of the alumina porous material in modeling software, dividing the model into different areas according to gradient function requirements, slicing the model by adopting slicing software, and introducing a slicing file into powder bed melting 3D printing equipment for processing;
3) And (3) processing the raw material powder by adopting different laser energy densities for different partitions in the step (2) according to different functional requirements. The laser energy density and the structural properties of the alumina material are as follows: the higher the laser energy density used for printing and irradiation, the larger the microscopic aperture of the alumina material formed by the irradiated area, the lower the specific surface area and the larger Kong Rongyue; the lower the laser energy density used for printing and irradiation, the smaller the microscopic pore diameter of the alumina material formed by the irradiated area, the higher the specific surface area and the smaller Kong Rongyue; alumina carrier material with gradient structure in the inner space can be obtained by changing the laser energy density in the printing process;
4) And (3) post-treatment sintering process: in order to stabilize the material performance, the alumina gradient functional porous material formed in the step (3) is subjected to a post-treatment sintering process, wherein the treatment temperature is 400-900 ℃.
The aluminum hydroxide material in the step (1) is aluminum hydroxide with a chemical formula capable of being written as AlOOH and aluminum hydroxide with a chemical formula capable of being written as Al (OH) 3 One or more of the aluminum hydroxides.
The aluminum hydroxide with the chemical formula capable of being written as AlOOH in the step (1) is preferably pseudo-boehmite, and the chemical formula capable of being written as Al (OH) 3 Preferably alpha-alumina trihydrate.
The D50 particle size of the aluminum hydroxide powder in the step (1) is preferably 20-60 μm. In the powder bed melting process, the particle size of the powder is between 20 and 100 mu m, agglomeration occurs if the particle size is too small, the surface quality of a formed part is reduced if the particle size is too large, and the D50 particle size of the aluminum hydroxide powder is preferably between 20 and 60 mu m, and the forming quality is the best through experiments.
The inorganic additive powder in the step (1) consists of boron carbide and one or more of carbon powder, silicon oxide and magnesium oxide, and the addition of the boron carbide can reduce the energy density required by sintering the powder.
The D50 particle size of the inorganic additive powder in the step (1) is 5-20 μm, in theory, the smaller the D50 particle size of the inorganic additive powder is, the better the sintering efficiency is, but experiments show that the agglomeration phenomenon can occur when the particle size of the inorganic additive powder is smaller than 5 μm, so that the D50 particle size of the inorganic additive powder is 5-20 μm.
The uniform mixing method of the powder in the step (1) is any method capable of uniformly mixing the powder, such as a mechanical mixing method, a wet ball milling method or a solution precipitation method.
Wherein the preferred homogeneous mixing method is a wet ball milling method: pouring aluminum hydroxide powder with corresponding mass into a ball mill as a raw material at the volume ratio of the raw material powder to the dispersant to the grinding medium of 0.5-1:1-2, adding inorganic additive powder with corresponding mass into the ball mill as a raw material, pouring ethanol into the ball mill as a dispersant, adding alumina or zirconia ceramic balls (with the diameter of 3-10 mm) into the ball mill as a grinding medium, and performing ball milling for 3-24 hours in the ball mill; filtering the obtained slurry by using a screen with a mesh size of more than 100 meshes; drying the slurry at 50 ℃ for more than 24 hours; crushing the powder obtained after drying, and sieving the crushed powder by using a sieve with more than 100 meshes to obtain the mixed powder for preparing the alumina porous material.
The mode in the step (2) is divided into different areas mainly according to gradient function requirements, and the structural properties of materials in different areas can be continuously or discontinuously.
The powder bed fusion forming process parameters in the step (3) are as follows: the diameter of the light spot is 0.2-0.3 mm, the thickness of the layer is 0.1-0.2 mm, and the preheating temperature is 150-180 ℃. The different laser energy densities are mainly the adjustment of laser power, scanning speed and scanning interval. The laser power is 10 to 60W, the scanning speed is 20 to 2000mm/s, the scanning interval is 0.05 to 0.13mm, and 38 to 200J/cm can be obtained 2 Continuously varying laser energy. The laser energy with the continuous variation can obtain the laser with the aperture of 20-2000 nm and the specific surface area of 1-140 m 2 And/g, pore volume of 0.1-1.2 ml/g, and crushing strength of 10-200N/cm. Characterization data of pore diameter, specific surface area and pore volume in the above description are obtained by BET method, and crush strength is obtained by the method in standard HG/T2782-2011.
In the step (4), in order to further stabilize the material performance, the alumina gradient functional porous material formed in the step (3) is burned to 400-900 ℃ at a heating rate of 6-10 ℃/min, is preserved for 2-3 hours, and is cooled to room temperature along with a furnace.
Compared with the prior art, the invention has the following advantages:
1. the invention creatively provides a method for preparing the catalyst alumina carrier material with a gradient function structure by utilizing the change of laser irradiation energy density of a powder melting process to scan different areas of the same part and realize the conversion from aluminum hydroxide to alumina with different structural characteristics;
2. the raw material formula can take aluminum hydroxide powder as a matrix material of a powder fusion sintering 3D printing process, overcomes the problem that the structural change range of the material is limited after aluminum oxide is taken as a raw material and irradiated by different laser energy densities, and makes the preparation of the aluminum oxide carrier material with a gradient structure possible.
Drawings
Fig. 1 is a schematic diagram and a model of an embodiment of the present invention.
Fig. 2 is a graph showing the parameter change used in example 1.
Fig. 3 is a graph showing the parameter change in the region a used in example 5.
Fig. 4 is a graph showing the parameter change in the region B used in example 5.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Example 1
1) Mixing the raw material powder by a wet ball milling method: under the proportion of the volume ratio of the raw material powder to the dispersant to the grinding medium of 1:1:1, 900g of aluminum hydroxide powder (D50 particle size of 25 mu m), 50g of boron carbide powder (D50 particle size of 5 mu m) and 50g of silicon powder (D50 particle size of 5 mu m) are taken as raw material powder and added into a ball mill according to the sequence, ethanol is taken as the dispersant and added into the ball mill, zirconia porcelain balls (diameter of 3-10 mm) are taken as the grinding medium and added into the ball mill, and the ball milling time is 3 hours in the ball mill; drying the slurry at 50 ℃ for 24 hours; crushing the powder obtained after drying, and sieving the crushed powder by using a 100-mesh screen to obtain mixed powder which can be used for preparing the alumina porous material;
2) And establishing a three-dimensional model of the alumina carrier material in modeling software. The carrier material is hollow cylindrical, the length of the cylinder is 7mm, and the outer diameter is D 1 =7mm, wherein Kong Waijing is d 1 According to the gradient function requirement, the model is divided into regions with continuous gradient change of material properties from the outer ring to the inner ring of the middle hole, and the outermost layer (namely, from the central axis D of the cylinder 1 And/2) designing the material performance index as follows:
average pore diameter=1500 nm, specific surface area=1.5m 2 Per gram, pore volume=0.9 ml/g, intensity=160N/cm.
Innermost layer (i.e. spaced from the central axis d of the cylinder 1 And/2) designing the material performance index as follows:
average pore diameter=30 nm, specific surface area=120 m 2 Per gram, pore volume=0.2 ml/g, intensity=50N/cm.
3) Placing the powder obtained in step 1) in a powder fusion bed 3D printer, setting the initial printing parameters to have a spot diameter of 0.2mm and a layer thickness of 0.1mm, and a preheating temperature of 150deg.C, and setting the material gradient properties in step (2) from the outermost layer (i.e. from the cylinder center axis D 1 At/2) to the innermost layer (i.e. d from the cylinder axis 1 And/2) processing the raw material powder with successively different laser energy densities. For convenience of description, the continuous change of parameters is shown in fig. 2;
4) And (3) burning the alumina porous material formed in the step (3) to 900 ℃ at a heating rate of 6 ℃/min, preserving the heat at the temperature for 3 hours, and cooling to room temperature along with a furnace. A catalyst carrier 1 was obtained.
Comparative example 1
Comparative example 1 differs from example 1 in that the model in step 2) was not provided with a region of continuous gradient change in material properties, the printing laser energy density in step 3) was unchanged, the parameters were set to laser power=52W, scan speed=400 mm/s, and scan pitch=0.13 mm. The catalyst carrier 2 was prepared.
Comparative example 2
The difference from example 1 is that in step 1), aluminum hydroxide was entirely replaced with alpha alumina powder having a D50 particle diameter of 30 μm, to prepare catalyst carrier 3.
Comparative example 3
Weighing 12.0 g of pseudo-boehmite into a beaker, adding 50ml of deionized water, and uniformly dispersing the pseudo-boehmite by adopting magnetic stirring; dropwise adding a nitric acid solution into the solution to adjust the pH=2 of the solution, and continuously stirring until the solution is gradually dissolved to form a semitransparent sol system; then 0.722 g of tetraethyl orthosilicate is added dropwise into the sol system at room temperatureStirring for 1h, heating to 60 ℃ and keeping the temperature for 2 h; the sol was transferred to a crucible and placed in an oven to be dried at 80 ℃ for 8 hours. The solid obtained after drying is programmed to be heated from room temperature to 550 ℃ at a heating rate of 15 ℃/min, and is roasted for 2 hours at 550 ℃ to obtain the uniformly mixed alpha-Al 2 O 3 And SiO 2 Is a nanoparticle of (a). The mixed nano particles are heated to 1200 ℃ at a speed of 15 ℃/min, and are kept at the temperature of 1200 ℃ for roasting for 6 hours, thus forming the alpha-Al-containing nano particles 2 O 3 And a mullite phase. alpha-Al 2 O 3 Adding the composite oxide mixed with mullite phase into 50ml of 20% hydrofluoric acid aqueous solution, heating and soaking for 6h at 60 ℃ to realize alpha-Al reaction 2 O 3 Chemical etching to dope alpha-Al 2 O 3 And removing the medium mullite. Washing the etched solid by deionized water until the pH=7, transferring the solid powder into an oven, drying at 80 ℃ for 6 hours, and roasting the dried sample for 4 hours under the condition of 700 ℃ in an air atmosphere to obtain the carrier 4.
Example 2
Step 1) mixing raw material powder by using a wet ball milling method: under the proportion of the volume ratio of the raw material powder to the dispersant to the grinding medium of 1:1:1, 800g of aluminum hydroxide powder (with the D50 particle size of 25 mu m), 100g of boron carbide (with the D50 particle size of 5 mu m) and 100g of silicon dioxide (with the D50 particle size of 20 mu m) are taken as raw material powder and added into a ball mill according to the sequence, ethanol is taken as the dispersant and added into the ball mill, zirconia porcelain balls (with the diameter of 3-10 mm) are taken as the grinding medium and added into the ball mill, and the ball milling time is 3 hours in the ball mill; drying the obtained slurry at 50 ℃ for 24 hours; crushing the powder obtained after drying, and sieving the crushed powder by using a 100-mesh screen to obtain mixed powder which can be used for preparing the alumina porous material; steps 2) and 3) are the same as in example 1;
and 4) burning the alumina porous material formed in the step (3) to 700 ℃ at a heating rate of 6 ℃/min, preserving heat for 3 hours at the temperature, and cooling to room temperature along with a furnace to obtain the carrier 5.
Example 3
Step 1) mixing raw material powder by using a wet ball milling method: under the proportion of the volume ratio of the raw material powder to the dispersant to the grinding medium of 1:1:1, 980g of aluminum hydroxide powder (D50 particle size of 25 mu m), 20g of boron carbide (D50 particle size of 5 mu m) and 5g of silicon dioxide are taken as raw material powder to be added into a ball mill according to the sequence, ethanol is taken as the dispersant to be added into the ball mill, zirconia porcelain balls (diameter of 3-10 mm) are taken as the grinding medium to be added into the ball mill, and the ball milling time is 3 hours in the ball mill; drying the obtained slurry at 50 ℃ for 24 hours; crushing the powder obtained after drying, and sieving the crushed powder by using a 100-mesh screen to obtain mixed powder which can be used for preparing the alumina porous material; steps 2) and 3) are the same as in example 1; and 4) burning the alumina porous material formed in the step (3) to 700 ℃ at a heating rate of 6 ℃/min, preserving heat for 3 hours at the temperature, and cooling to room temperature along with a furnace to obtain the carrier 6.
Example 4
Step 1) mixing raw material powder by using a wet ball milling method: under the proportion of the volume ratio of the raw material powder to the dispersant to the grinding medium of 1:1:1, 650g of aluminum hydroxide powder (with the D50 particle size of 25 mu m), 10.5g of boron carbide (with the D50 particle size of 5 mu m), 139.5g of silicon powder (with the D50 particle size of 5 mu m) and 200g of silicon dioxide (with the D50 particle size of 20 mu m) are taken as raw material powder and added into a ball mill according to the sequence, ethanol is taken as the dispersant and added into the ball mill, zirconia porcelain balls (with the diameter of 3-10 mm) are taken as the grinding medium and added into the ball mill, and the ball milling time is 3 hours in the ball mill; drying the obtained slurry at 50 ℃ for 24 hours; crushing the powder obtained after drying, and sieving the crushed powder by using a 100-mesh screen to obtain mixed powder which can be used for preparing the alumina porous material; steps 2) and 3) are the same as in example 1; and 4) burning the alumina porous material formed in the step (3) to 700 ℃ at a heating rate of 10 ℃/min, preserving heat for 3 hours at the temperature, and cooling to room temperature along with a furnace to obtain the carrier 7.
Example 5
The difference from example 1 is that in step 2), the mold is divided from the outer ring to the inner ring of the middle hole into the outermost layers (i.e., from the cylinder center axis D 1 At/2) to a distance D from the central axis of the cylinder 2 At/2 (D) 2 =4 mm) and from the cylinder central axis D 2 From/2 to the innermost layer (i.e. from the cylinderBody center axis d 1 Zone B of/2), in which the raw material powder is processed with continuously different laser energy densities, the continuous variation of the parameters being shown in figure 3; the catalyst support 8 is also prepared in region B by using continuously different laser energy densities, with continuous variation of parameters as shown in fig. 4.
And respectively taking 20 samples from the carriers 1-8 at random, wherein 10 samples are taken by cutting by using a small blade according to the areas A, B and C marked in fig. 1, wherein the area A refers to an annular part from the outermost side of the carrier to a position 2.5mm away from the axis of the carrier, the area B refers to an annular part from a position 2.5mm away from the axis of the carrier to a position 1.5mm away from the axis of the carrier, the area C refers to a position 1.5mm away from the axis of the carrier, and 10 pieces of carrier materials for taking the samples are collected together to serve as one carrier sample to be taken, and the average pore diameter, specific surface area and pore volume are measured by adopting a BET method. The 10 samples of each carrier were averaged after testing their side pressure strength using a particle side pressure intensity meter. The test characterization results are shown in table 1:
TABLE 1
Examples 9 to 13:
108 g of silver nitrate are dissolved in 250 ml of water, and 50g of ammonium oxalate are dissolved in 680 ml of water. The two solutions are subjected to precipitation reaction at room temperature, the obtained silver oxalate precipitate is washed by distilled water until no nitrate ions exist, 50% (V/V) ethylenediamine aqueous solution is added dropwise after filtration until complete dissolution, and 0.012 g cesium nitrate is added to prepare silver oxalate-ethylenediamine mixed impregnating solution A. Mixing 10% of soaking solution A with carriers 1,5,6,7,8 thoroughly, oven drying, sequentially treating in air flow at 150deg.C for 30 min and water vapor-air flow with water content of 10% at 500deg.C for 30 min, and cooling to room temperature under air flow. And (3) fully mixing the rest 90% impregnating solution A with the silver-loaded alpha-Al 2O3, carrying out secondary impregnation, drying, and carrying out thermal decomposition treatment for 30 minutes in an air atmosphere at 150 ℃ to obtain the silver-loaded catalyst 1,5,6,7 and 8 with the silver grain size of 100-200 nm. These catalysts were tested for initial ethylene conversion and selectivity using a laboratory microreaction evaluation device. The reactor is a stainless steel reaction tube with the inner diameter of 10mm, and the reaction tube is arranged in a heating furnace sleeve. The catalyst loading volume was 4ml and the relevant reaction conditions were as follows:
molar composition of raw material gas:
C 2 H 4 :30％；O 2 :8％；CO 2 3 percent; inhibitors: a trace amount; n (N) 2 : the rest are
Pressure (gauge pressure): 1.6MPa
Airspeed: 2500h -1
Catalysts 1,5,6,7,8 were obtained to obtain reaction data.
Comparative examples 4 to 6:
the carriers 2,3,4 were prepared to obtain catalysts 2,3,4, respectively, in the same manner as in examples 9 to 13, and the catalysts were subjected to performance evaluation in the same manner as in examples 9 to 13 to obtain reaction data.
The reaction data for the evaluation of catalysts 1-8 are summarized in Table 2:
table 2 catalyst evaluation reaction data
The invention uses the change of laser irradiation energy density of powder melting process to scan different areas of the same part, thereby realizing the conversion from aluminum hydroxide to alumina with different structural characteristics and obtaining the catalyst alumina carrier material with gradient function structure. From the test characterization result, the aperture of the carrier material is 24.52-1999.91 nm, and the specific surface area is 1-142.36 m 2 The pore volume is continuously changed within the range of 0.1-1.15 ml/g, and the alumina carrier material with a larger gradient structure range is proved to be prepared by the invention. Therefore, the raw material formula can take aluminum hydroxide powder as a matrix material of a powder fusion sintering 3D printing process, solves the problem that the structural change range of the material is limited after aluminum oxide is taken as a raw material and irradiated by different laser energy densities, and prepares the aluminum oxide carrier material with a gradient structure.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (6)

1. A catalyst alumina carrier material with a gradient structure is characterized in that the pore diameter of the carrier material is 20-2000 nm, and the specific surface area is 1-140 m 2 Per gram, the pore volume is 0.1-1.2 ml/g, and the crushing strength is continuously changed within the range of 10-200N/cm;
the preparation method of the catalyst alumina carrier material with the gradient structure comprises the following steps:
(1) Preparing raw material powder: the raw material powder is prepared by uniformly mixing aluminum hydroxide powder and inorganic additive powder, wherein the aluminum hydroxide powder accounts for 65-98 wt% of the total mass of the raw material powder;
(2) Modeling: establishing a three-dimensional model of the alumina porous material in modeling software, dividing the model into different areas according to gradient function requirements, slicing the model by adopting slicing software, and introducing a slicing file into powder bed melting 3D printing equipment for processing;
(3) 3D printing: processing the raw material powder by adopting different laser energy densities for different partitions in the step (2), and obtaining an alumina carrier material with a gradient structure in the inner space through changing the laser energy density in the printing process;
(4) Post-treatment: performing a post-treatment sintering process on the alumina gradient functional porous material formed in the step (3), wherein the treatment temperature is 400-900 ℃;
wherein, the inorganic additive powder in the step (1) consists of boron carbide and one or more of silicon powder, silicon oxide and magnesium oxide, wherein the boron carbide accounts for 3-100 wt% of the total mass of the inorganic additive powder;
the powder bed fusion forming process parameters in the step (3) are as follows: the diameter of the light spot is 0.2-0.3 mm, and the thickness of the layer is 0.1-02, mm, wherein the preheating temperature is 150-180 ℃; different laser energy densities are obtained through adjustment of laser power, scanning speed and scanning interval, the laser power is 10-60W, the scanning speed is 20-2000 mm/s, the scanning interval is 0.05-0.13 mm, and 38-200J/cm can be obtained 2 A continuously varying laser energy;
the aluminum hydroxide in the step (1) is aluminum hydroxide with a chemical formula written as AlOOH and aluminum hydroxide with a chemical formula written as Al (OH) 3 One or more of the aluminum hydroxides.
2. A method for preparing the catalyst alumina carrier material with gradient structure as claimed in claim 1, which is characterized by mainly comprising the following steps:
(1) Preparing raw material powder: the raw material powder is prepared by uniformly mixing aluminum hydroxide powder and inorganic additive powder, wherein the aluminum hydroxide powder accounts for 65-98 wt% of the total mass of the raw material powder;
(2) Modeling: establishing a three-dimensional model of the alumina porous material in modeling software, dividing the model into different areas according to gradient function requirements, slicing the model by adopting slicing software, and introducing a slicing file into powder bed melting 3D printing equipment for processing;
(3) 3D printing: processing the raw material powder by adopting different laser energy densities for different partitions in the step (2), and obtaining an alumina carrier material with a gradient structure in the inner space through changing the laser energy density in the printing process;
(4) Post-treatment: performing a post-treatment sintering process on the alumina gradient functional porous material formed in the step (3), wherein the treatment temperature is 400-900 ℃;
wherein, the inorganic additive powder in the step (1) consists of boron carbide and one or more of silicon powder, silicon oxide and magnesium oxide, wherein the boron carbide accounts for 3-100 wt% of the total mass of the inorganic additive powder;
the powder bed fusion forming process parameters in the step (3) are as follows: the diameter of the light spot is 0.2-0.3 mm, the thickness of the layer is 0.1-0.2 mm, and the preheating temperature is 150-180 ℃; different laser energyThe measuring density is obtained by adjusting the laser power, the scanning speed and the scanning interval, the laser power is 10-60W, the scanning speed is 20-2000 mm/s, the scanning interval is 0.05-0.13 mm, and 38-200J/cm can be obtained 2 A continuously varying laser energy;
the aluminum hydroxide in the step (1) is aluminum hydroxide with a chemical formula written as AlOOH and aluminum hydroxide with a chemical formula written as Al (OH) 3 One or more of the aluminum hydroxides.
3. The method for preparing a catalyst alumina support material with a gradient structure according to claim 2, wherein the aluminum hydroxide with a chemical formula of AlOOH is pseudo-boehmite and the chemical formula of AlOOH is Al (OH) 3 The aluminum hydroxide of (2) is alpha-alumina trihydrate.
4. The preparation method of the catalyst alumina carrier material with the gradient structure according to claim 2, wherein the D50 particle size of the aluminum hydroxide powder in the step (1) is 20-60 μm.
5. The method for preparing a catalyst alumina carrier material with a gradient structure according to claim 2, wherein the model in the step (2) is divided into different areas, and the structural properties of the material between the different areas can be continuously or discontinuously according to the gradient function requirement.
6. The preparation method of the catalyst alumina carrier material with the gradient structure according to claim 2, wherein the step (4) is characterized in that the temperature is raised to 400-900 ℃ at a heating rate of 6-10 ℃/min, the temperature is kept for 2-3 hours, and the catalyst alumina carrier material is cooled to room temperature along with a furnace.
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