CN112430402A - Photocatalyst shell powder and preparation method thereof - Google Patents

Photocatalyst shell powder and preparation method thereof Download PDF

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Publication number
CN112430402A
CN112430402A CN202011128062.2A CN202011128062A CN112430402A CN 112430402 A CN112430402 A CN 112430402A CN 202011128062 A CN202011128062 A CN 202011128062A CN 112430402 A CN112430402 A CN 112430402A
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photocatalyst
shell powder
equal
water
thermal polymerization
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Inventor
李平
穆广杰
张学雷
崔东波
孙晓光
张余鑫
孙培旺
魏国强
陈维英
徐继任
李佳明
闫敏敏
刘友刚
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Mountain Jingbo Environmental Protection Materials Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/66Additives characterised by particle size
    • C09D7/67Particle size smaller than 100 nm

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plant Pathology (AREA)
  • Nanotechnology (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of building coatings, and particularly provides photocatalyst shell powder and a preparation method thereof, wherein the coating comprises 70-95 wt% of shell powder and 5-30 wt% of photocatalyst, and the photocatalyst takes one of urea, dicyanodiamine and melamine as a raw material and is directly subjected to one-step heat treatment to obtain blocky g-C3N4The photocatalyst is obtained by ball milling and refining; adding shell powder into the photocatalyst, stirring and mixing uniformly to obtain the photocatalytic shell powder coating with high formaldehyde purification performance, wherein the coating can be used for formaldehyde in airThe adsorption and decomposition capacity is strong, the process is environment-friendly, and the method is suitable for batch production; compared with the shell powder coating alone, the g-C added in the material3N4The material has stronger formaldehyde decomposition capability and antibacterial activity.

Description

Photocatalyst shell powder and preparation method thereof
Technical Field
The invention relates to the technical field of building coatings, and particularly provides photocatalyst shell powder and a preparation method thereof.
Background
In recent years, with the development of the economy of China, the living standard of people is continuously improved, more and more families begin to pay attention to the decoration of rooms, due to the existence of inferior materials in the market, when people beautify the rooms, part of building materials containing pollutants such as formaldehyde, benzene series, TVOC and the like pollute the indoor air, and at present, a plurality of home-decoration coatings and purification products for removing toxic gases such as indoor formaldehyde and the like exist in the market. For example, diatom ooze, shell powder, clean aldehyde ooze and other home decoration coatings have certain adsorption capacity to formaldehyde, but experiments prove that the environment-friendly home decoration coatings have limited adsorption capacity to formaldehyde and low efficiency.
In the environment-friendly home decoration coatings on the market at present, the shell powder and the diatom ooze are natural and environment-friendly materials, and are popular and selected by people in recent years. Both have the function of adsorbing formaldehyde, but the safety coefficient of the shell powder is higher compared with that of the shell powder. The shell powder has the functions of adsorption, decomposition and peculiar smell elimination, and has the functions of antibiosis and bacteriostasis, as well as antistatic property, and can adjust air humidity, prevent fire, retard flame, absorb sound, reduce noise and prevent fire pollution. The decorative effect is good, the process variety is multiple, the color is very rich, and the decorative effect is suitable for various decoration styles. However, the purification capability of the shell powder to formaldehyde is limited, and the requirement of decoration purification is difficult to meet, so that how to improve the purification performance and the durability of the shell powder to formaldehyde by using the shell powder as a main material through modification becomes one of the problems to be solved in the field.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a photocatalyst shell powder and a preparation method thereof, wherein the coating comprises 70-95 wt% of shell powder and 5-30 wt% of photocatalyst, the photocatalyst takes one of urea, dicyanodiamine and melamine as raw materials, and the raw materials are directly subjected to one-step heat treatment to obtain blocky g-C3N4The photocatalyst is obtained by ball milling and refining; then adding shell powder into the photocatalyst, stirring and mixing uniformly to obtain the photocatalytic shell powder coating with high formaldehyde purification performance, wherein the coating has extremely strong adsorption and decomposition capacity on formaldehyde in the air, and the process is environment-friendly and suitable for batch production; compared with the shell powder coating alone, the g-C added in the material3N4The material has stronger formaldehyde decomposition capability and antibacterial activity.
The shell powder for the interior wall coating in the prior art mainly has the following problems:
(1) aiming at the existing interior wall coating shell powder, the formaldehyde gas released by interior decoration is mostly removed by adsorption, and the efficiency is low and the speed is slow; (2) aiming at the existing photocatalysis-loaded shell powder coating, the response can be carried out under ultraviolet light; the inventor provides a brand-new technical scheme to solve the problems through long-term research, and the adopted specific technical scheme is as follows:
the photocatalyst shell powder comprises 70-95 wt% of shell powder and 5-30 wt% of photocatalyst;
the shell powder is various commercially available shell powders, and the specific alternative conditions are as follows:
(1) the content of volatile organic compounds is 0-1wt per mill;
(2) the proportion of the particle size distribution of less than or equal to 20 mu m is more than or equal to 45 percent, and the proportion of the particle size distribution of less than or equal to 10 mu m is more than or equal to 25 percent;
(3) the content of the shell raw powder is more than or equal to 35 percent;
the commercially available shell powder is prepared by taking shells as a main raw material and adding a plurality of auxiliary materials such as an adhesive, a thickening agent, a dispersing agent, a defoaming agent, a blending agent, an anti-cracking agent and the like, the higher the content of the shell raw powder is, the better the quality of the shell powder is, and the higher the price is, and the technical scheme of the application can modify various shell powders in the market and obtain corresponding technical effects, so that the quality of the shell powders is obviously improved; the shell powder in the embodiment of the application is directly purchased from the market, and only the alternative conditions are required to be met;
the photocatalyst takes one of urea, dicyanodiamine and melamine as raw material, and the blocky g-C is obtained by direct one-step heat treatment3N4The photocatalyst is obtained by ball milling and refining, and is a nano-scale visible light photocatalyst, so that a good catalytic effect can be achieved without special ultraviolet irradiation, and the application range of the photocatalyst is wider;
the photocatalyst shell powder is prepared by the following specific steps:
(1) doping: weighing shell powder according to the using ratio, adding an application amount of photocatalyst into the shell powder, and then uniformly mixing the two materials by using a mixer;
(2) grinding: grinding the mixed product until the particle size D50 is less than or equal to 20 mu m to ensure that the mixed product is more fully mixed;
(3) adding water and mixing: taking water according to the weight ratio of the powder to the water of 1:1.5, adding the ground product into the water, and stirring for 0.5-2h under the condition of 25r/min-100r/min to obtain the photocatalyst shell powder;
furthermore, the inventor also discloses a more specific preparation method of the nano-scale visible light catalyst, which comprises the following steps:
step 1, direct thermal polymerization method for preparing g-C3N4Photocatalyst: dicyandiamide or urea or melamine is taken as a raw material, and is directly placed at 550-650 ℃ for thermal polymerization for 2-4 h to obtain faint yellow blocky g-C3N4
The thermal polymerization process is completed in a muffle furnace or other high-temperature furnace, and the pressure in the thermal polymerization process is normal pressure;
step 2, ball milling to refine the blocky g-C3N4: wet grinding the block g-C3N4Mixing with deionized water, and ball-milling for 5-10 h; drying the feed liquid to obtain a nano-scale visible light catalyst;
further, in the wet milling method, the lump g-C3N4And deionized water in a mixing ratio of 100 g: 170-300ml, the rotating speed of the ball mill is 250 r/min-380 r/min;
finally prepared nano g-C3N4The band gap is between 2.6 and 2.9eV, and the light absorption edge is between 428 and 477nm, so that the nano g-C prepared by the invention can be seen3N4Good response to visible light; and has a particle diameter of 100nm or less and a specific surface area (BET) of 30.000 to 35.000m2Between/g;
the nano-scale visible light catalyst can be prepared by referring to the technical scheme described in Chinese patent application No. 2019102319669.
By adopting the technical scheme, the invention obtains the following technical effects:
(1) the raw materials adopted by the invention are simple, the sources are wide, the preparation process is simple, the operation conditions are stable, and the operation and the industrial production are easy;
(2) the photocatalyst used in the invention has low cost, small particle size, can reach nano level, has high photocatalytic rate, can adsorb and decompose formaldehyde under natural light, has long service life, can be repeatedly used for more than 5 times under the condition of not reducing the photocatalytic rate, and is easy for scale-up production;
(3) the dry powder of the shell powder sold in the market is used as a carrier, the shell powder belongs to sustainable utilization resources, and g-C is used3N4The photocatalyst does not contain heavy metal, and is nontoxic and harmless to human bodies after long-term use;
(4) the photocatalyst shell powder provided by the invention adsorbs and decomposes formaldehyde under natural illumination, and the concentration of formaldehyde in room air in 48 hours can be reduced to 0.08mg/m3Meets the sanitary standard of formaldehyde in room air, and has better performance than the existing photocatalyst; besides, the deodorant also has the functions of deodorization and bacteriostasis, and has better performance.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention, and the following embodiments are all completed by using the prior art except for the specific description.
The material selection is as follows:
the shell powder adopted in the following examples is commercially available shell powder, and the specific alternative conditions are as follows:
(1) the content of volatile organic compounds is 0-1wt per mill;
(2) the proportion of the particle size distribution of less than or equal to 20 mu m is more than or equal to 45 percent, and the proportion of the particle size distribution of less than or equal to 10 mu m is more than or equal to 25 percent;
(3) the content of shells is more than or equal to 35 percent;
the nano-scale visible light catalyst is prepared by the following method:
step 1, direct thermal polymerization method for preparing g-C3N4Photocatalyst: dicyandiamide or urea or melamine is taken as a raw material, and is directly placed at 550-650 ℃ for thermal polymerization for 2-4 h to obtain faint yellow blocky g-C3N4
The thermal polymerization process is completed in a muffle furnace or other high-temperature furnace, and the pressure in the thermal polymerization process is normal pressure;
step 2, ball milling to refine the blocky g-C3N4: wet grinding the blocks prepared in the previous stepForm g-C3N4Mixing with deionized water, and ball-milling for 5-10 h; and drying the feed liquid to obtain the nano-scale visible light catalyst.
Preferably, the preparation method of the adopted nano-scale visible light catalyst comprises the following specific steps:
step 1, direct thermal polymerization method for preparing g-C3N4Photocatalyst: thermal polymerization of urea at 590 deg.C for 3h to obtain light yellow block g-C3N4(ii) a The yield of this step was about 41.50%;
step 2, ball milling to refine the blocky g-C3N4: wet grinding to obtain block g-C3N4Mixing with deionized water according to a proportion of 50%, and ball-milling for 5 h; the feed was dried to give the product in about 94.88% yield for this step and the overall yield of the product was 39.14%.
Example 1
The photocatalyst shell powder comprises the following components:
according to the mass percentage: g-C3N45% of photocatalyst and 95% of shell powder of a commercial A manufacturer;
the preparation method comprises the following specific steps:
mixing and grinding the raw materials, taking water according to the weight ratio of the powder to the water of 1:1.5, adding the ground product into the water, and stirring for 0.5-2h under the condition of 25-100 r/min to obtain a slurry state, thus obtaining a finished product.
Comparative experiment: according to JC/T1074-2008 'indoor air purification function coating material purification performance' standard, formaldehyde purification experiments are carried out on shell powder of a manufacturer A sold in the market, shell powder of a manufacturer A added with 5 wt% of ultraviolet light catalyst (nano titanium dioxide catalyst) and a product compounded by the shell powder, and the experimental data are as follows:
Figure BDA0002733153180000041
example 2
The photocatalyst shell powder comprises the following components:
according to the mass percentage: g-C3N412% of photocatalyst and 88% of shell powder of a commercial B manufacturer;
the preparation method comprises the following specific steps:
mixing and grinding the raw materials, taking water according to the weight ratio of the powder to the water of 1:1.5, adding the ground product into the water, and stirring for 0.5-2h under the condition of 25-100 r/min to obtain a slurry state, thus obtaining a finished product.
Comparative experiment: according to JC/T1074-2008 'indoor air purification function coating material purification performance' standard, formaldehyde purification experiments are carried out on shell powder of a commercial manufacturer B, shell powder of a manufacturer B added with 12 wt% of ultraviolet light catalyst (nano titanium dioxide catalyst) and a finished product compounded by the shell powder, and the experimental data are as follows:
Figure BDA0002733153180000042
example 3
The photocatalyst shell powder comprises the following components:
according to the mass percentage: g-C3N4The photocatalyst is 22 percent, and the shell powder of a commercial C manufacturer is 78 percent;
the preparation method comprises the following specific steps:
mixing and grinding the raw materials, taking water according to the weight ratio of the powder to the water of 1:1.5, adding the ground product into the water, and stirring for 0.5-2h under the condition of 25-100 r/min to obtain a slurry state, thus obtaining a finished product.
Comparative experiment: according to JC/T1074-2008 'indoor air purification function coating material purification performance' standard, formaldehyde purification experiments are carried out on shell powder of a commercial C manufacturer, shell powder of a C manufacturer added with 22% ultraviolet light catalyst (nano titanium dioxide catalyst) and a product compounded by the shell powder, and the experimental data are as follows:
Figure BDA0002733153180000051
the photocatalyst shell powder provided by the invention can adsorb and decompose formaldehyde under natural illumination, and the concentration of formaldehyde in room air in 48 hours can be reduced to 0.08mg/m3Meets the sanitary standard of formaldehyde in room air, and has better performance than the existing photocatalyst; besides, the deodorant also has the functions of deodorization and bacteriostasis, and has better performance.

Claims (4)

1. A photocatalyst shell powder is characterized in that: the components of the photocatalyst comprise 70 to 95 weight percent of shell powder and 5 to 30 weight percent of photocatalyst;
wherein the shell powder has the following alternative conditions:
(1) the content of volatile organic compounds is 0-1wt per mill;
(2) the proportion of the particle size distribution of less than or equal to 20 mu m is more than or equal to 45 percent, and the proportion of the particle size distribution of less than or equal to 10 mu m is more than or equal to 25 percent;
(3) the content of shells is more than or equal to 35 percent;
the photocatalyst takes one of urea, dicyanodiamine and melamine as raw material, and the blocky g-C is obtained by direct one-step heat treatment3N4The photocatalyst is obtained by ball milling and refining.
2. The photocatalyst shell powder according to claim 1, characterized in that: the preparation method of the photocatalyst comprises the following specific steps:
step 1, direct thermal polymerization method for preparing g-C3N4Photocatalyst: dicyandiamide or urea or melamine is taken as a raw material, and is directly placed at 550-650 ℃ for thermal polymerization for 2-4 h to obtain faint yellow blocky g-C3N4
The thermal polymerization process is completed in a muffle furnace or other high-temperature furnace, and the pressure in the thermal polymerization process is normal pressure;
step 2, ball milling to refine the blocky g-C3N4: wet grinding the block g-C3N4Mixing with deionized water, and ball-milling for 5-10 h; and drying the feed liquid to obtain the nano-scale visible light catalyst.
3. The photocatalyst shell powder according to claim 1, characterized in that:
in the wet milling method, the lump g-C3N4And deionized water in a mixing ratio of 100 g: 170-300ml, and the rotating speed of the ball mill is 250 r/min-380 r/min.
4. A method for producing the photocatalyst shell powder as set forth in claim 1, characterized in that: the method comprises the following specific steps:
(1) doping: weighing shell powder according to the using ratio, adding an application amount of photocatalyst into the shell powder, and then uniformly mixing the two materials by using a mixer;
(2) grinding: grinding the mixed product until the particle size D50 is less than or equal to 20 mu m to ensure that the mixed product is more fully mixed;
(3) adding water and mixing: taking water according to the weight ratio of the powder to the water of 1:1.5, adding the ground product into the water, and stirring for 0.5-2h under the condition of 25r/min-100r/min to obtain the photocatalyst shell powder.
CN202011128062.2A 2020-10-20 2020-10-20 Photocatalyst shell powder and preparation method thereof Pending CN112430402A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669083A (en) * 2015-12-17 2016-06-15 张龙飞 Indoor air purifying material and preparation method thereof
CN106554645A (en) * 2016-03-25 2017-04-05 广东优冠生物科技有限公司 A kind of dry-type ecological interior wall coating based on conch meal
CN106620785A (en) * 2016-12-29 2017-05-10 玛蒂耐特建筑材料有限公司 Indoor air purifying material using shell powder and calcium ferrite complex as main components and preparation method and application of indoor air purifying material
CN109908937A (en) * 2019-03-25 2019-06-21 黄河三角洲京博化工研究院有限公司 A kind of preparation method of nanoscale visible light catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669083A (en) * 2015-12-17 2016-06-15 张龙飞 Indoor air purifying material and preparation method thereof
CN106554645A (en) * 2016-03-25 2017-04-05 广东优冠生物科技有限公司 A kind of dry-type ecological interior wall coating based on conch meal
CN106620785A (en) * 2016-12-29 2017-05-10 玛蒂耐特建筑材料有限公司 Indoor air purifying material using shell powder and calcium ferrite complex as main components and preparation method and application of indoor air purifying material
CN109908937A (en) * 2019-03-25 2019-06-21 黄河三角洲京博化工研究院有限公司 A kind of preparation method of nanoscale visible light catalyst

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