CN109794301A - A kind of ceramic photocatalysis carrier structure based on increasing material manufacturing - Google Patents
A kind of ceramic photocatalysis carrier structure based on increasing material manufacturing Download PDFInfo
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Abstract
The present invention relates to a kind of ceramic photocatalysis carrier structure based on increasing material manufacturing, including carrier matrix and ordered porous carrier, carrier matrix include basal layer and several dislocation layers；Basal layer is obtained by carrying out displacement design based on space positive tetrahedron in three-dimensional space for element, layer misplace by being converted and piling up to obtain circulating type symmetric space positive tetrahedron mono-layer network structure along axial direction, converting content is to change grid height and diameter, piling up mode is using basal layer central axis as rotation center, dislocation is carried out according to deflection angle φ along counterclockwise or clockwise direction to pile up, and obtains several dislocation layers；Carrier matrix is fabricated by 3D printing technique, and ordered porous carrier is microcosmic mesoporous in carrier matrix.Carrier matrix of the invention can improve the utilization rate of light, improve light distribution character, and the manufacturing process using 3D printing technique as carrier matrix breaches the bottleneck of carrier structure existing defects, reduces production and application cost, can be in large-scale application.
Description
Technical field
The present invention relates to increases material manufacturing technology fields, and in particular to a kind of ceramic photocatalysis carrier knot based on increasing material manufacturing
Structure.
Background technique
Research finds that photocatalyst can produce Strong oxdiative reducing power under the action of ultraviolet light, can be catalytically decomposed and be attached to
The gas chromatography and part inorganic matter of physical surface, and catabolite is pollution-free.But current photocatalyst pollutes air indoors
Processing technology field be not widely used, main reason is that there is many restrictions for the carrying method of photocatalyst
Factor:
(1) that there are photocatalyst particle dispersibilities is bad, is difficult to the problems such as recycling for suspension method；
(2) fixation load technology compensates for the difficult disadvantage of suspension method recycling, however with regard to existing common three kinds of carrier knots
For structure, there is also many deficiencies, so that reaction efficiency is lower:
1. slab construction: in the confined space can reaction surface area it is small；
2. unordered porous structure: hindering light propagation, reception light is insufficient, and effective affecting acreage is small；
3. orderly honeycomb: small compared with porous structure specific surface area, arrangement light source is cumbersome.
The photocureable rapid shaping of ceramic material is that had essence for the molding new process of complicated ceramic part over the past two years
Degree is high, speed is fast, material compatibility is high, can form the characteristics of large-size ceramic part, using photosensitive resin as bonding
Agent, ceramic powder is as filler, using light-curing rapid forming equipment, carries out printing shaping to designed threedimensional model.
Porous ceramics application field is very extensive, is mainly used for catalyst carrier, filtering and separation, air-dispersing material, sensitivity
Element, micropore mould etc..But the preparation of current porous ceramic film material mostly uses mold to form, and can only prepare the product of simple structure,
The optimization in shape and structure can not be carried out, is made using being restricted.
Summary of the invention
The technical problem to be solved in the present invention is that being urged for above-mentioned photocatalyst recovery efficiency of the existing technology with light
Change the problem of efficiency can not get both, provides a kind of ceramic photocatalysis carrier structure based on increasing material manufacturing, it, which can reach, compares table
The balance of area and light utilization efficiency improves reaction efficiency.
The present invention is technical solution used by solving technical problem set forth above are as follows:
A kind of ceramic photocatalysis carrier structure based on increasing material manufacturing, including carrier matrix and ordered porous carrier, it is described
Carrier matrix includes basal layer and several dislocation layers；The basal layer is member by being based on space positive tetrahedron in three-dimensional space
Element carries out displacement design and obtains, method particularly includes: the side of space positive tetrahedron is become into accommodation curve, the removal of bottom surface side changes
Highly, then based on bottom surface mirror image space positive tetrahedron is conjugated, obtains surrounding based on two-dimension plane structure and space positive tetrahedron
Type symmetric space positive tetrahedron mono-layer network structure；Several dislocation layers are by by the circulating type symmetric space positive tetrahedron
Mono-layer network structure is converted along axial direction and piles up to obtain, and transformation content is change grid height and diameter, the mode of piling up are
Using basal layer central axis as rotation center, dislocation is carried out according to deflection angle φ along counterclockwise or clockwise direction and is piled up, if obtaining
Dry dislocation layer；The carrier matrix is fabricated by 3D printing technique, and the ordered porous carrier is in the carrier matrix
It is microcosmic mesoporous.
In above scheme, the ceramics photocatalysis carrier structure further includes ultraviolet lamp and reflective inner cavity, the carrier matrix
It is installed in the reflective inner cavity with ultraviolet lamp, the ultraviolet lamp is installed through the centre bore of the carrier matrix.
In above scheme, the reflective inner cavity coats specular layer, and the material of specular layer meets good reflective and not
Participate in the requirement of light-catalyzed reaction；The reflective cavity shape is annular surface structure, and both ends diameter is less than mid diameter, is formed
Light can be carried out aggregation reflection by concave mirror structure.
In above scheme, fluid inlet and fluid outlet is respectively set in the both ends of the reflective inner cavity, wherein fluid inlet
Positioned at close to carrier matrix basal layer one end；The carrier matrix, ultraviolet lamp, reaction inner cavity, fluid inlet, fluid go out
Mouthful, the central axis of ultraviolet lamp support is located on same axis.
In above scheme, the reflective inner cavity is equipped with ultraviolet lamp support and carrier matrix bracket, and ultraviolet lamp support is in annulus
Shape is connected to reflective inner cavity by bracket, for the fixedly secured of ultraviolet lamp；Carrier matrix bracket is located at reflective interior cavity wall,
The number of plies is identical as the number of plies of carrier matrix, the placement for multilayer carrier matrix.
In above scheme, the preparation method of the carrier matrix and ordered porous carrier specifically includes the following steps:
(1) premixed liquid is obtained after prepolymer, reactive diluent and surface modifier being carried out mechanical mixing；
(2) it carries out ceramic powder and pore creating material to be mixed to get porous ceramics powder, and porous ceramics powder is added to step
Suddenly it in premixed liquid obtained in (1), then carries out machinery and is uniformly mixed so as to obtain initial slurry；
(3) photoinitiator is added in initial slurry obtained in step (2), then progress machinery is uniformly mixed so as to obtain photosensitive more
Hole ceramic slurry；
(4) the photosensitive porous ceramics slurry for being obtained step (3) by photocuring 3D printing technique is manufactured into porous ceramics
Green body, that is, the carrier matrix structure designed；
(5) porous ceramics green body obtained in step (4) is subjected to degreasing, sintering processes, obtains porous ceramic film material, i.e.,
The carrier matrix of design.
The beneficial effects of the present invention are:
First, the carrier matrix of photocatalyst of the invention uses space circulating type Multi-layer staggered packing structure, in conjunction with pore-creating
Agent carries out microcosmic controllable pore-creating, has obtained preferable spatial distribution utilization rate and biggish specific surface area, can control catalyst
The specific surface area of carrier makes reaction rate obtain larger raising, is distributed in conjunction with optical path, light is made more to be uniformly distributed in carrier base
Reaction efficiency is improved from physical angle to improve the utilization rate of light in body surface face.It is beaten using the ceramic 3D based on increasing material manufacturing
Manufacturing process of the print technology as carrier matrix, breaches the bottleneck of carrier structure existing defects, and easy to operate, substantially reduces
Production and application cost, can with large-scale promotion application.
Second, the optical reflection curved design of reaction inner cavity of the invention can further improve light utilization.
Third, the present invention is based on the ceramic photocatalysis carrier structure of increasing material manufacturing, the small and exquisite various shapes of entirety, structure is simple
Efficiently, feasibility is high.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples, in attached drawing:
Fig. 1 is the overall structure cross-sectional view of the ceramic photocatalysis carrier structure the present invention is based on increasing material manufacturing；
Fig. 2 is the single layer structure two dimension schematic diagram of carrier matrix；
Fig. 3 is the three-dimensional figure of the circulating type symmetric space positive tetrahedron mono-layer network structure of carrier matrix；
Fig. 4 is that the multilayered structure of carrier matrix piles up top view；
Fig. 5 is the three-dimensional figure of the multilayered structure of carrier matrix；
Fig. 6 is the microcosmic mesoporous figure in carrier matrix；
Fig. 7 is the preparation flow figure of carrier matrix.
In figure: 10, carrier matrix；30, ultraviolet lamp；40, reflective inner cavity；41, fluid inlet；42, fluid outlet；51, purple
Outer lamp support；52, carrier matrix bracket.
Specific embodiment
For a clearer understanding of the technical characteristics, objects and effects of the present invention, now control attached drawing is described in detail
A specific embodiment of the invention.
As shown in Figure 1, it is a preferred embodiment of the present invention the ceramic photocatalysis carrier structure based on increasing material manufacturing, including
Carrier matrix 10, ordered porous carrier, ultraviolet lamp 30 and reflective inner cavity 40.Carrier matrix 10 and ultraviolet lamp 30 are installed in reflective
In chamber 40, ultraviolet lamp 30 is installed through the centre bore of carrier matrix 10.
Fig. 2 shows the two-dimensional surface principles of the circulating type symmetric space positive tetrahedron mono-layer network structure of carrier matrix 10
Figure, each unit as shown in the figure is rhombic quadrangles, and 12 rhombic quadrangles rotate about the axis around axis ring, successively prolong to outer ring
Stretch 3 layers.The two-dimension plane structure is different from honeycomb, while guarantee honeycomb good space utilization rate, tool
There is good circular property further the light of the light source at center can be stopped to shed.
Fig. 3 shows the single layer structure figure of carrier matrix 10, in three-dimensional space based on space positive tetrahedron be element into
Row displacement design obtains, and the side of space positive tetrahedron is become accommodation curve, the removal of bottom surface side changes height, then is based on bottom surface
Mirror image conjugates space positive tetrahedron, obtains the positive four sides of circulating type symmetric space based on two-dimension plane structure and space positive tetrahedron
Body mono-layer network structure.
The method that Fig. 4,5 multilayers for showing carrier matrix 10 change and pile up, just by the circulating type symmetric space of design
Tetrahedron mono-layer network structure is converted and is piled up along axial direction, and transformation particular content is to change grid height and diameter.It piles up
Mode is to carry out dislocation using basal layer central axis as rotation center according to deflection angle φ along counterclockwise or clockwise direction and pile up,
Obtain several dislocation layers.Specifically, layer based on a layers, b-f layers are dislocation layer, the Mesh Diameter of basal layer a in the present embodiment
It is highly 14mm for 2mm, shows that direction successively changes with Fig. 4 arrow, it is α that Mesh Diameter, which changes multiple,1=1.1486984, grid
Height change multiple α2=1.0515475, further, it is highly 18mm that dislocation layer f Mesh Diameter, which is 4mm,.The mode piled up
The deflection angle of φ=5 ° is specially designed, vertical view carries out dislocation in the counterclockwise direction and piles up.
Fig. 6 shows ordered porous carrier, and the carrier matrix 10 in the present invention is fabricated by 3D printing technique, orderly
Porous carrier mixes printing sintering with ceramic powder by pore creating material and is formed, can be used for light to be microcosmic mesoporous in carrier matrix 10
Catalyst TiO2Attachment.
Fig. 7 shows the preparation flow of carrier matrix 10 and ordered porous carrier, specifically includes the following steps:
(1) premixed liquid is obtained after prepolymer, reactive diluent and surface modifier being carried out mechanical mixing；
(2) ceramic powder and pore creating material be mixed to get porous ceramics powder, and by porous ceramics powder be added to
In premixed liquid obtained in step (1), then carries out machinery and be uniformly mixed so as to obtain initial slurry；
(3) photoinitiator is added in initial slurry obtained in step (2), then progress machinery is uniformly mixed so as to obtain photosensitive more
Hole ceramic slurry；
(4) the photosensitive porous ceramics slurry for being obtained step (3) by photocuring 3D printing technique is manufactured into porous ceramics
Green body (10 structure of carrier matrix designed)；
(5) porous ceramics green body obtained in step (4) is subjected to degreasing, sintering processes, obtains porous ceramic film material, i.e.,
The carrier matrix 10 of design has microcosmic mesoporous (i.e. ordered porous carrier) in carrier matrix 10.
Above-mentioned preparation method, the ceramic powder in step (2) select oxide, nitride, carbide, fluoride, carbonate,
Phosphate, rare earth oxide, mullite, spinelle, any one or more mixing in feldspar；Pore creating material is selected inorganic
Any one in pore creating material and organic pore-forming agents or two kinds of mixing.The inorganic pore creating material is selected from ammonium carbonate, ammonium hydrogen carbonate, chlorine
Change ammonium, silicon nitride, coal dust, any one or more mixing in carbon dust；Organic pore-forming agents are selected from sawdust, naphthalene, starch, polyethylene
Alcohol, urea, methyl methacrylate, polyvinyl chloride, any one or more mixing in polystyrene.
Further, the loaded optic catalyst TiO in carrier matrix 102, after infusion process loaded optic catalyst, pass through
550 DEG C of temperature calcination 2-4h, this temperature both can guarantee that anatase titanium dioxide was not transitioning to the poor gold of photocatalysis performance
Red stone-type titanium dioxide, and load performance can be improved.
Carrier matrix 10 of the invention uses space circulating type Multi-layer staggered packing structure, in conjunction with pore creating material carry out it is microcosmic can
Pore-creating is controlled, preferable spatial distribution utilization rate and biggish specific surface area has been obtained, the specific surface of catalyst carrier can be controlled
Product, makes reaction rate obtain larger raising, is distributed in conjunction with optical path, light is made more to be uniformly distributed in carrier matrix surface, thus
The utilization rate for improving light improves reaction efficiency from physical angle.Space circulating type Multi-layer staggered packing structure is used with resistance to
Corrosivity and ceramic increases material manufacturing technology resistant to high temperature are manufactured, and are met calcining and are required the carrier material high temperature resistance determined
With the chemical property required under photocatalysis.Ceramic increases material manufacturing technology can solve optical catalyst carrier and be limited by single knot
There is big structure defect in structure, realizing has the manufacture of tiny ordered porous structural carrier matrix 10, according to carrier base
The performances such as structure, processing, the reaction of body 10 increase in a variety of ceramics and select formed precision and the higher light of consistency solid in material technology
Change rapid shaping printing technique (3D printing technique).
It advanced optimizes, in the present embodiment, about 15W is can be selected between 250-400nm range in the wavelength of ultraviolet lamp 30
Ultraviolet lamp stick, hair can occur effectively as photocatalyst and the treated object on light source catalytic carrier matrix 10 and answer.
It advanced optimizing, in the present embodiment, reflective inner cavity 40 coats specular layer, and the coating of specular layer can select aluminium foil,
Silver-plated, the reflectorized materials such as reflective powder, selection standard must meet good reflective and be not involved in light-catalyzed reaction.Reflective inner cavity
40 shapes are annular surface structure, and both ends diameter is less than mid diameter, forms concave mirror structure, can carry out light to assemble anti-
It penetrates.Reflection light carries out light compensation to 10 outside light fewer parts of carrier matrix and shady face, improve light utilization and
Light-catalyzed reaction rate.Arrow A indicates the flow direction of fluid in Fig. 1, and arrow B indicates light reflection path.Reflective inner cavity 40
Equipped with ultraviolet lamp support 51 and carrier matrix bracket 52, ultraviolet lamp support 51 is in circular ring shape, is connected to reflective inner cavity by bracket
40, for the fixedly secured of ultraviolet lamp 30, carrier matrix bracket 52 is located at reflective 40 inner wall of inner cavity, six layers in total, is used for multilayer
The placement of carrier matrix 10.
It advanced optimizing, in the present embodiment, fluid inlet 41 and fluid outlet 42 is respectively set in the both ends of reflective inner cavity 40,
Wherein fluid inlet 41 is located at close to 10 basal layer one end of carrier matrix.As shown in Figure 1, the left side is fluid inlet 41, the right is
Fluid outlet 42, basal layer a from inlet end face to carrier matrix 10, entire carrier matrix 10, ultraviolet lamp 30, reflective inner cavity 40,
The central axis of ultraviolet lamp support 51 and carrier matrix bracket 52 is located on same axis.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.
The embodiment of the present invention is described with above attached drawing, but the invention is not limited to above-mentioned specific
Embodiment, the above mentioned embodiment is only schematical, rather than restrictive, those skilled in the art
Under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, it can also make very much
Form, all of these belong to the protection of the present invention.
Claims (6)
1. a kind of ceramic photocatalysis carrier structure based on increasing material manufacturing, including carrier matrix and ordered porous carrier, feature
It is,
The carrier matrix includes basal layer and several dislocation layers；
The basal layer is obtained by carrying out displacement design based on space positive tetrahedron in three-dimensional space for element, specific method
Are as follows: the side of space positive tetrahedron is become into accommodation curve, the removal of bottom surface side changes height, then conjugates space based on bottom surface mirror image
Positive tetrahedron obtains the circulating type symmetric space positive tetrahedron mono-layer network knot based on two-dimension plane structure and space positive tetrahedron
Structure；
Several dislocation layers are by converting the circulating type symmetric space positive tetrahedron mono-layer network structure along axial direction
With pile up to obtain, transformation content is to change grid height and diameter, and mode of piling up is the edge using basal layer central axis as rotation center
Counterclockwise or dislocation is carried out according to deflection angle φ clockwise to pile up, obtain several dislocation layers；
The carrier matrix is fabricated by 3D printing technique, and the ordered porous carrier is microcosmic in the carrier matrix
It is mesoporous.
2. the ceramic photocatalysis carrier structure according to claim 1 based on increasing material manufacturing, which is characterized in that the ceramics
Photocatalysis carrier structure further includes ultraviolet lamp and reflective inner cavity, and the carrier matrix and ultraviolet lamp are installed on the reflective inner cavity
In, the ultraviolet lamp is installed through the centre bore of the carrier matrix.
3. the ceramic photocatalysis carrier structure according to claim 2 based on increasing material manufacturing, which is characterized in that described reflective
Inner cavity coats specular layer, and the material of specular layer meets good reflective and the requirement for being not involved in light-catalyzed reaction；It is described anti-
Light cavity shape is annular surface structure, and both ends diameter is less than mid diameter, forms concave mirror structure, can assemble light
Reflection.
4. the ceramic photocatalysis carrier structure according to claim 3 based on increasing material manufacturing, which is characterized in that described reflective
Fluid inlet and fluid outlet is respectively set in the both ends of inner cavity, and wherein fluid inlet is located at close to the carrier matrix basal layer one
End；The carrier matrix, ultraviolet lamp, reaction inner cavity, fluid inlet, fluid outlet, ultraviolet lamp support central axis be located at it is same
On axis.
5. the ceramic photocatalysis carrier structure according to claim 1 based on increasing material manufacturing, which is characterized in that described reflective
Inner cavity is equipped with ultraviolet lamp support and carrier matrix bracket, and ultraviolet lamp support is in circular ring shape, is connected to reflective inner cavity by bracket, uses
In the fixedly secured of ultraviolet lamp；Carrier matrix bracket is located at reflective interior cavity wall, and the number of plies is identical as the number of plies of carrier matrix, is used for
The placement of multilayer carrier matrix.
6. the ceramic photocatalysis carrier structure according to claim 1 based on increasing material manufacturing, which is characterized in that the carrier
The preparation method of matrix and ordered porous carrier specifically includes the following steps:
(1) premixed liquid is obtained after prepolymer, reactive diluent and surface modifier being carried out mechanical mixing；
(2) it carries out ceramic powder and pore creating material to be mixed to get porous ceramics powder, and porous ceramics powder is added to step (1)
Obtained in premixed liquid, then carry out machinery and be uniformly mixed so as to obtain initial slurry；
(3) photoinitiator is added in initial slurry obtained in step (2), then carries out machinery and is uniformly mixed so as to obtain photosensitive porous pottery
Porcelain slurry；
(4) it is manufactured by the photosensitive porous ceramics slurry that photocuring 3D printing technique obtains step (3) into porous ceramics green body,
The carrier matrix structure designed；
(5) porous ceramics green body obtained in step (4) is subjected to degreasing, sintering processes, obtains porous ceramic film material, that is, designs
Carrier matrix.
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| CN110433770A (en) * | 2019-07-17 | 2019-11-12 | 天津大学 | Photocatalysis honeycomb C-base composte material and preparation method |
| CN110743626A (en) * | 2019-10-29 | 2020-02-04 | 中国科学院兰州化学物理研究所 | Method for 3D printing of porous catalytic device and porous catalytic device |
| CN111250010A (en) * | 2020-01-20 | 2020-06-09 | 山东大学 | Catalyst carrier and micro-channel continuous flow reactor |
| CN111558400A (en) * | 2020-05-07 | 2020-08-21 | 朱岳军 | Catalyst porous ceramic carrier with high surface area |
| CN111895532A (en) * | 2020-07-07 | 2020-11-06 | 武汉理工大学 | Photocatalysis air purification device based on polyhedral structure |
| CN114249379A (en) * | 2021-12-24 | 2022-03-29 | 内蒙古工业大学 | Photocatalytic pollutant degradation reaction device |
| CN115116755A (en) * | 2022-06-12 | 2022-09-27 | 西北工业大学 | High-efficiency photothermal conversion material with polyhedral torsion structure, and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110433770A (en) * | 2019-07-17 | 2019-11-12 | 天津大学 | Photocatalysis honeycomb C-base composte material and preparation method |
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| CN111895532B (en) * | 2020-07-07 | 2021-07-16 | 武汉理工大学 | Photocatalysis air purification device based on polyhedral structure |
| CN114249379A (en) * | 2021-12-24 | 2022-03-29 | 内蒙古工业大学 | Photocatalytic pollutant degradation reaction device |
| CN115116755A (en) * | 2022-06-12 | 2022-09-27 | 西北工业大学 | High-efficiency photothermal conversion material with polyhedral torsion structure, and preparation method and application thereof |
| CN115116755B (en) * | 2022-06-12 | 2024-03-29 | 西北工业大学 | Polyhedron torsion structure photo-thermal conversion material and preparation method and application thereof |
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