CN112536027B - Spherical denitration catalyst with lattice structure prepared by 3D printing and preparation method thereof - Google Patents
Spherical denitration catalyst with lattice structure prepared by 3D printing and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- 238000010146 3D printing Methods 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 15
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002562 thickening agent Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 230000001788 irregular Effects 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 32
- 238000001125 extrusion Methods 0.000 claims description 22
- 235000011837 pasties Nutrition 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 8
- 229910000278 bentonite Inorganic materials 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003546 flue gas Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000779 smoke Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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Abstract
The invention relates to the technical field of denitration catalysts, and particularly discloses a spherical denitration catalyst with a lattice structure prepared by 3D printing and a preparation method thereof. The spherical denitration catalyst comprises the following raw materials in parts by weight: 55-60 parts of denitration titanium tungsten powder; 0.5 to 2 parts of ammonium metavanadate; 1-2 parts of lubricant; 0.5-2 parts of thickening agent and 37-42 parts of deionized water, wherein the interior of the spherical denitration catalyst is of a space lattice structure. The spherical denitration catalyst with the lattice structure prepared by 3D printing is a porous spherical denitration catalyst with a space lattice structure in the interior, has high pore density, large specific surface area and high porosity, and the internal irregular columnar structure can effectively block smooth passing of flue gas, so that the contact probability of the catalyst and the flue gas is increased, the effective utilization rate of the catalyst is high, and the flue gas denitration effect is enhanced.
Description
Technical Field
The invention relates to the technical field of denitration catalysts, in particular to a spherical denitration catalyst with a lattice structure prepared by 3D printing and a preparation method thereof.
Background
The denitration catalyst is mainly used for flue gas denitration in coal-fired power plants, steel and cement industries. Commercial catalysts are mainly vanadium-titanium-based series catalysts with higher activity and selectivity, the market share is more than 90%, and the active substances are V 2 O 5 . A Selective Catalytic Reduction (SCR) process has been widely used as a mainstream flue gas denitration technology at home and abroad.
At present, the catalyst for denitration by the SCR method at home and abroad mainly comprises 3 types of honeycomb type, flat type and corrugated type. Compared with other types of catalysts, the honeycomb catalyst has the characteristics of high aperture ratio, reduced pressure, large specific surface area, high activity and long service life, and the market share is more than 60 percent. However, the existing honeycomb catalyst is formed by stacking material lines layer by layer, and the specific surface area and the porosity of the whole honeycomb catalyst are still required to be further improved to improve the effective utilization rate of the catalyst even though the catalyst is in a honeycomb shape.
Although research is carried out on the preparation process of the granular or spherical denitration catalyst by research personnel at home and abroad, and the spherical denitration catalyst is prepared, the contact area of gas and the catalyst can be effectively increased, the ash is easy to remove, the blockage is difficult to occur, the spherical denitration catalyst still does not fully utilize the internal structure of the sphere, and the effective utilization rate of the catalyst is low.
Disclosure of Invention
Aiming at the technical problems of the existing denitration catalyst, the invention provides a spherical denitration catalyst with a lattice structure prepared by 3D printing and a preparation method thereof.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
the spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following raw materials in parts by weight: 55-60 parts of denitration titanium tungsten powder; 0.5 to 2 parts of ammonium metavanadate; 1-2 parts of lubricant; 0.5-2 parts of thickening agent and 37-42 parts of deionized water, wherein the interior of the spherical denitration catalyst is of a space lattice structure.
Compared with the prior art, the spherical denitration catalyst with the lattice structure prepared by 3D printing is prepared based on a material extrusion 3D printing technology, the denitration catalyst is a porous spherical denitration catalyst with a space lattice structure, and has the advantages of high pore density, large specific surface area, high porosity and the like. In addition, the catalyst in the invention can adopt a combined filling method, and the catalyst with the same sphere diameter and pore structure size is placed in the same cuboid filling compartment, so that the catalyst is convenient to combine and disassemble, and the full utilization of the catalysts with different structures is realized.
Further, the space lattice structure of the spherical denitration catalyst comprises a plurality of lattice unit cells which are connected with each other, and the lattice unit cells are arranged in an array manner to form the spherical denitration catalyst with a porous structure, so that the specific surface area and the porosity of the catalyst are further increased, the utilization rate of the catalyst is improved, and the denitration effect is enhanced.
Further, the unit size of the lattice unit cell is 3-10 mm, the diameter of the spherical denitration catalyst is 1-25 cm, the specific surface area and the porosity of the catalyst are ensured, and meanwhile, the size of the catalyst is convenient to combine and fill.
Further, the lattice unit cell is formed by splicing a plurality of column strips, so that an irregular space network structure is formed inside the lattice structure, smooth passing of smoke can be effectively prevented, the contact probability of the catalyst and the smoke is increased, the effective utilization rate of the catalyst is high, and the smoke denitration effect is enhanced.
Further, the length of the column strips is 0.5-2 mm, so that the column strips are convenient to splice with each other to form a space lattice structure.
Further, the wetting agent is one of bentonite, kaolin or attapulgite; the thickener is at least one of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose.
The invention also provides a preparation method of the spherical denitration catalyst with the lattice structure, which is prepared by 3D printing, and comprises the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, a lubricant, a thickener and deionized water, and filtering and pre-extruding to obtain a pasty material;
s2, performing S2; according to the required lattice structure of the spherical denitration catalyst, a 3D printing model and 3D printing parameters are designed, the pasty material is sent into 3D printing equipment, 3D printing is carried out according to a preset 3D printing model, and a catalyst blank body with a preset shape is obtained;
s3, performing S3; and (3) performing two-stage drying treatment on the catalyst blank, and calcining to obtain the spherical denitration catalyst with the lattice structure.
Compared with the prior art, the preparation method of the spherical denitration catalyst with the lattice structure, which is prepared by 3D printing, has the advantages that the SCR denitration catalyst is produced by mutually combining the material extrusion 3D printing technology and the sintering technology, the catalysts with different lattice structures can be designed according to different requirements, and the specification parameters of products such as the specific surface area, the porosity and the like can be correspondingly controlled. The method has the advantages of simple operation, low equipment cost and low processing cost, and can be used for mass production.
Further, in step S1, the mesh number of the filter screen used for filtering is not less than 200 mesh, and the pre-extrusion is realized by using a pre-extruder, so that the obtained pasty material can be smoothly printed in 3D.
Further, in step S2, a 3D model is built for the designed spatial lattice structure of the spherical denitration catalyst by using 3D software, and the 3D model is decomposed into a series of two-dimensional sheet models with the thickness of 0.05-0.4 mm.
Further, in step S2, the 3D printing parameters are: the diameter of the nozzle is 0.1-0.4 mm; the extrusion pressure is 0.3-0.5 MPa; the printing speed is 18-20 mm/s.
Further, in the step S3, the temperature of one section of drying is 45-55 ℃ and the time is 24-48 hours; the temperature of the second-stage drying is 65-75 ℃ and the time is 18-36 h, so that the catalyst blank is fully cured and solidified, and the subsequent calcination is convenient.
Further, in the step S3, the calcining temperature is 450-550 ℃ and the calcining time is 3-5 h, so as to obtain the porous spherical denitration catalyst with the lattice structure.
Drawings
FIG. 1 is a schematic diagram of a unit cell of a lattice cell of different structure according to the present invention;
FIG. 2 is a schematic diagram of spherical denitration catalysts of different sizes;
FIG. 3 is a schematic representation of the combined loading pattern of spherical denitration catalyst in the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a spherical denitration catalyst with a lattice structure, which is prepared by 3D printing, and comprises the following raw materials in parts by weight: 55-60 parts of denitration titanium tungsten powder; 0.5 to 2 parts of ammonium metavanadate; 1-2 parts of lubricant; 0.5-2 parts of thickening agent and 37-42 parts of deionized water, wherein the interior of the spherical denitration catalyst is of a space lattice structure.
The preparation method of the spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, a lubricant, a thickener and deionized water, and filtering and pre-extruding to obtain a pasty material;
s2, performing S2; according to the required lattice structure (shown in figure 1) of the spherical denitration catalyst, designing a 3D printing model and 3D printing parameters, sending the pasty material into 3D printing equipment, and performing 3D printing according to a preset 3D printing model to obtain a catalyst blank body with a preset shape;
s3, performing S3; and (3) performing two-stage drying treatment on the catalyst blank, and calcining to obtain the porous spherical denitration catalyst with the lattice structure (shown in figure 2).
Specifically, in step S2, the paste material is loaded into an extrusion device of a material extrusion 3D printing apparatus, the paste material is extruded through a nozzle of an extrusion head by pressure, the extrusion head accurately moves along the contour of each section of a catalyst preset structural part, and the extruded semi-flowing material is deposited and solidified into an accurate actual part thin layer; after one layer is printed, the part is lowered by one layer thickness, the extrusion head accurately moves along the contour of a new section of the part to solidify and deposit, and the process is repeated until the catalyst blank is finished.
The obtained denitration catalyst is filled in a combined mode, porous spherical denitration catalysts with lattice structures and different sphere diameters and different pore structure sizes are mixed and filled, the catalysts with the same sphere diameters and pore structure sizes are placed in the same cuboid filling compartment, the compartment is composed of a steel wire mesh and a frame, the pore structure sizes are the same as the mesh sizes of the steel wires, and the arrangement mode of the compartments is as follows: from top to bottom, the pore structure size of the porous spherical denitration catalyst is from small to large (as shown in fig. 3).
In order to better illustrate the spherical denitration catalyst with the lattice structure prepared by 3D printing provided by the embodiment of the invention, the following is further exemplified by the embodiment.
Example 1
The spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following raw materials in parts by weight: 55 parts of denitration titanium tungsten powder; 0.5 parts of ammonium metavanadate; 2 parts of bentonite; 1 part of carboxymethyl cellulose and 41.5 parts of deionized water, wherein the spherical denitration catalyst has a space lattice structure.
The preparation method of the spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, bentonite, carboxymethyl cellulose and deionized water, uniformly stirring, filtering, and adding the filtered material into a pre-extruder for pre-extrusion treatment to obtain a pasty material;
s2, performing S2; the required spherical denitration catalyst has a diameter of 1cm, wherein the lattice unit size is 3mm, the length of a column bar used for splicing to form the lattice unit is 1mm (shown as a in figure 1 a), a 3D model is built for the designed space lattice structure of the spherical denitration catalyst by using 3D software, the obtained 3D model is decomposed into a series of two-dimensional sheet models with a thickness of 0.1mm, then the two-dimensional sheet model data of each layer are converted into a scanning path, 3D printing parameters (the diameter of a nozzle is 0.2mm, the extrusion pressure is 0.4MPa, the layering thickness is 0.1mm and the printing speed is 18 mm/s) are set, the pasty materials are sent into 3D printing equipment, and 3D printing is carried out according to a preset 3D printing model to obtain a catalyst blank with a preset shape;
s3, performing S3; drying the obtained catalyst blank for 48 hours at 45 ℃, drying for 36 hours at 65 ℃, and calcining for 5 hours at 450 ℃ to obtain the porous spherical denitration catalyst with the lattice structure.
Example 2
The spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following raw materials in parts by weight: 60 parts of denitration titanium tungsten powder; 1 part of ammonium metavanadate; 1.5 parts of kaolin; 0.5 part of hydroxyethyl cellulose and 37 parts of deionized water, wherein the spherical denitration catalyst has a space lattice structure.
The preparation method of the spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, kaolin, hydroxyethyl cellulose and deionized water, uniformly stirring, filtering, and adding the filtered material into a pre-extruder for pre-extrusion treatment to obtain a pasty material;
s2, performing S2; the diameter of the spherical denitration catalyst is 1.5cm, the size of lattice unit cells is 3mm, the length of column strips used for splicing to form the lattice unit cells is 1.5mm (shown as c in figure 1), a 3D model is built for the space lattice structure of the designed spherical denitration catalyst by using 3D software, the obtained 3D model is decomposed into a series of two-dimensional sheet models with the thickness of 0.2mm, then the two-dimensional sheet model data of each layer are converted into a scanning path, 3D printing parameters (the diameter of a nozzle is 0.2mm, the extrusion pressure is 0.3MPa, the layering thickness is 0.2mm and the printing speed is 20 mm/s) are set, the pasty materials are sent into 3D printing equipment, and 3D printing is carried out according to a preset 3D printing model, so that a catalyst blank with the preset shape is obtained;
s3, performing S3; drying the obtained catalyst blank for 27 hours at 55 ℃, drying for 20 hours at 75 ℃, and calcining for 4 hours at 450 ℃ to obtain the porous spherical denitration catalyst with the lattice structure.
Example 3
The spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following raw materials in parts by weight: 58 parts of denitration titanium tungsten powder; 1.5 parts of ammonium metavanadate; 1 part of attapulgite; 0.5 part of hydroxypropyl cellulose and 39 parts of deionized water, wherein the spherical denitration catalyst has a space lattice structure.
The preparation method of the spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, attapulgite, hydroxypropyl cellulose and deionized water, uniformly stirring, filtering, and adding the filtered material into a pre-extruder for pre-extrusion treatment to obtain a pasty material;
s2, performing S2; the required spherical denitration catalyst has a diameter of 2cm, wherein the size of lattice unit cells is 4mm, the length of column strips used for splicing to form the lattice unit cells is 2mm (shown as m in figure 1), a 3D model is built for the designed space lattice structure of the spherical denitration catalyst by using 3D software, the obtained 3D model is decomposed into a series of two-dimensional sheet models with a thickness of 0.3mm, then the two-dimensional sheet model data of each layer are converted into a scanning path, 3D printing parameters (the diameter of a nozzle is 0.4mm, the extrusion pressure is 0.3MPa, the layering thickness is 0.3mm and the printing speed is 18 mm/s) are set, the pasty materials are sent into 3D printing equipment, and 3D printing is carried out according to a preset 3D printing model to obtain a catalyst blank with a preset shape;
s3, performing S3; drying the obtained catalyst blank for 36 hours at 50 ℃, drying for 24 hours at 70 ℃, and calcining for 4 hours at 500 ℃ to obtain the porous spherical denitration catalyst with the lattice structure.
Example 4
The spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following raw materials in parts by weight: 57 parts of denitration titanium tungsten powder; 2 parts of ammonium metavanadate; 1.5 parts of bentonite; 1 part of hydroxypropyl methyl cellulose and 38.5 parts of deionized water, wherein the spherical denitration catalyst has a space lattice structure.
The preparation method of the spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, bentonite, hydroxypropyl methyl cellulose and deionized water, uniformly stirring, filtering, and adding the filtered material into a pre-extruder for pre-extrusion treatment to obtain a pasty material;
s2, performing S2; the diameter of the spherical denitration catalyst is 2cm, the size of lattice unit cells is 4mm, the length of column strips used for splicing to form the lattice unit cells is 1mm (shown as v in figure 1), a 3D model is built for the space lattice structure of the designed spherical denitration catalyst by using 3D software, the obtained 3D model is decomposed into a series of two-dimensional sheet models with the thickness of 0.3mm, 3D printing parameters (the diameter of a nozzle is 0.4mm, the extrusion pressure is 0.5MPa, the layering thickness is 0.3mm, the printing speed is 20 mm/s) are set, the pasty materials are sent into 3D printing equipment, 3D printing is carried out according to a preset 3D printing model, and a catalyst blank with the preset shape is obtained;
s3, performing S3; drying the obtained catalyst blank for 48 hours at 45 ℃, drying for 36 hours at 65 ℃, and calcining for 3 hours at 550 ℃ to obtain the porous spherical denitration catalyst with the lattice structure.
Example 5
The spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following raw materials in parts by weight: 56 parts of denitration titanium tungsten powder; 2 parts of ammonium metavanadate; 2 parts of kaolin; 2 parts of hydroxyethyl cellulose and 38 parts of deionized water, wherein the spherical denitration catalyst has a space lattice structure.
The preparation method of the spherical denitration catalyst with the lattice structure prepared by 3D printing comprises the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, kaolin, hydroxyethyl cellulose and deionized water, uniformly stirring, filtering, and adding the filtered material into a pre-extruder for pre-extrusion treatment to obtain a pasty material;
s2, performing S2; the diameter of the spherical denitration catalyst is 2cm, the size of lattice unit cells is 4mm, the length of column strips used for splicing to form the lattice unit cells is 1mm (shown as i in figure 1), a 3D model is built for the space lattice structure of the designed spherical denitration catalyst by using 3D software, the obtained 3D model is decomposed into a series of two-dimensional sheet models with the thickness of 0.2mm, 3D printing parameters (the diameter of a nozzle is 0.2mm, the extrusion pressure is 0.4MPa, the layering thickness is 0.2mm, the printing speed is 18 mm/s) are set, the pasty materials are sent into 3D printing equipment, 3D printing is carried out according to a preset 3D printing model, and a catalyst blank with the preset shape is obtained;
s3, performing S3; drying the obtained catalyst blank for 24 hours at 55 ℃, drying for 18 hours at 75 ℃, and calcining for 4 hours at 450 ℃ to obtain the porous spherical denitration catalyst with the lattice structure.
In order to better illustrate the technical solutions of the present invention, the following is further compared with examples of the present invention.
Comparative example 1
The honeycomb denitration catalyst prepared by 3D printing comprises the following raw materials in parts by weight: 55 parts of denitration titanium tungsten powder; 0.5 parts of ammonium metavanadate; 2 parts of bentonite; 1 part of carboxymethyl cellulose and 41.5 parts of deionized water.
The preparation method of the honeycomb denitration catalyst prepared by 3D printing comprises the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, bentonite, carboxymethyl cellulose and deionized water, uniformly stirring, filtering, and adding the filtered material into a pre-extruder for pre-extrusion treatment to obtain a pasty material;
s2, performing S2; 3D model is built on the structure of the honeycomb denitration catalyst by utilizing 3D software, the obtained 3D model is decomposed into a series of two-dimensional sheet models with the thickness of 0.1mm, then two-dimensional sheet model data of each layer are converted into a scanning path, 3D printing parameters (the diameter of a nozzle is 0.2mm, the extrusion pressure is 0.4MPa, the layering thickness is 0.1mm and the printing speed is 18 mm/s) are set, the pasty material is sent into 3D printing equipment, 3D printing is carried out according to a preset 3D printing model, and a catalyst blank with a preset shape is obtained;
s3, performing S3; the obtained catalyst blank is dried for 48 hours at 45 ℃, then dried for 36 hours at 65 ℃, and then calcined for 5 hours at 450 ℃ to obtain the honeycomb denitration catalyst.
In order to better illustrate the characteristics of the spherical denitration catalyst with the lattice structure prepared by 3D printing provided by the embodiment of the present invention, the spherical denitration catalysts prepared in examples 1 to 5 and the honeycomb denitration catalyst in comparative example 1 were subjected to flue gas denitration performance test.
Catalyst performance evaluation: the denitration condition of the catalyst is tested by using simulated flue gas, and the simulated flue gas comprises the following components: NO:500ppm, NH 3 ：500ppm、O 2 ：5％vol、N 2 Is the balance of qi. The flue gas flow is 100mL/min, catalysts with different volumes are taken and put into a fixed bed reactor for testing, the denitration efficiency of the catalysts at different temperatures is tested, and the reaction temperature is controlled to be 50-400 ℃. Detection reactor using flue gas analyzerNO concentration at the outlet. The denitration rate was calculated as follows:
the results of flue gas denitration using the spherical denitration catalysts prepared in examples 1 to 5, the combined filler of the spherical denitration catalysts in examples 1, 2, and 3, and the honeycomb denitration catalyst in comparative example 1 are shown in table 1.
TABLE 1
From the above data, it can be seen that the spherical denitration catalyst with a lattice structure prepared by 3D printing provided by the embodiment of the invention is a porous spherical denitration catalyst with a space lattice structure in the interior, the pore density is high, the specific surface area is large, the porosity is high, the smooth passing of smoke can be effectively blocked by the internal irregular columnar structure, the contact probability of the catalyst and the smoke is increased, the effective utilization rate of the catalyst is high, and the smoke denitration effect is enhanced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (6)
1. The spherical denitration catalyst with the lattice structure prepared by 3D printing is characterized by comprising the following raw materials in parts by weight: 55-60 parts of denitration titanium tungsten powder; 0.5-2 parts of ammonium metavanadate; 1-2 parts of a lubricant; 0.5-2 parts of thickener and 37-42 parts of deionized water, wherein the interior of the spherical denitration catalyst is of a space lattice structure;
the space lattice structure of the spherical denitration catalyst comprises a plurality of lattice unit cells which are connected with each other, and the lattice unit cells are arranged in an array manner to form the spherical denitration catalyst with a porous structure;
the lattice unit cell is formed by splicing a plurality of column strips, so that an irregular space network structure is formed inside the lattice structure;
the unit size of the lattice unit cell is 3-10 mm, and the diameter of the spherical denitration catalyst is 1-25 cm;
the lubricant is one of bentonite, kaolin or attapulgite; the thickener is at least one of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose.
2. A method for preparing the spherical denitration catalyst with a lattice structure prepared by 3D printing as claimed in claim 1, which is characterized by comprising the following steps:
s1, performing S1; mixing the denitration titanium tungsten powder, ammonium metavanadate, a lubricant, a thickener and deionized water, and filtering and pre-extruding to obtain a pasty material;
s2, performing S2; according to the required lattice structure of the spherical denitration catalyst, a 3D printing model and 3D printing parameters are designed, the pasty material is sent into 3D printing equipment, 3D printing is carried out according to a preset 3D printing model, and a catalyst blank body with a preset shape is obtained;
s3, performing S3; and (3) performing two-stage drying treatment on the catalyst blank, and calcining to obtain the spherical denitration catalyst with the lattice structure.
3. The method for preparing the spherical denitration catalyst with the lattice structure by 3D printing as claimed in claim 2, which is characterized by comprising the following steps: in the step S2, a 3D model is established for the space lattice structure of the designed spherical denitration catalyst by utilizing 3D software, and the 3D model is decomposed into a series of two-dimensional sheet models with the thickness of 0.05-0.4 mm.
4. The method for preparing the spherical denitration catalyst with the lattice structure by 3D printing as claimed in claim 2, which is characterized by comprising the following steps: in step S2, the 3D printing parameters are: the diameter of the nozzle is 0.1-0.4 mm; the extrusion pressure is 0.3-0.5 MPa; the printing speed is 18-20 mm/s.
5. The method for preparing the spherical denitration catalyst with the lattice structure by 3D printing as claimed in claim 2, which is characterized by comprising the following steps: in the step S3, the temperature of one section of drying is 45-55 ℃ and the time is 24-48 h; the temperature of the second-stage drying is 65-75 ℃ and the time is 18-36 h.
6. The method for preparing the spherical denitration catalyst with the lattice structure, which is prepared by 3D printing according to any one of claims 2 to 5, is characterized in that: in the step S3, the calcination temperature is 450-550 ℃ and the calcination time is 3-5 h.
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| CN107530696A (en) * | 2015-04-14 | 2018-01-02 | 庄信万丰股份有限公司 | The catalyst granules of shaping |
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