CN113416455B - Method for preparing antibacterial and antiviral paint by adopting sodium dichloroisocyanurate process wastewater - Google Patents
Method for preparing antibacterial and antiviral paint by adopting sodium dichloroisocyanurate process wastewater Download PDFInfo
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- CN113416455B CN113416455B CN202110697401.7A CN202110697401A CN113416455B CN 113416455 B CN113416455 B CN 113416455B CN 202110697401 A CN202110697401 A CN 202110697401A CN 113416455 B CN113416455 B CN 113416455B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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Abstract
The invention discloses a method for preparing an antibacterial and antiviral paint by adopting sodium dichloroisocyanurate process wastewater, which comprises the following steps: 1) preparing an antibacterial and antiviral A component; 2) adding deionized water into a reaction kettle, adding a dispersing agent, titanium dioxide and a defoaming agent while stirring, then adding the antibacterial and antiviral component A, continuously stirring, sequentially adding the water-soluble polymer emulsion, the film-forming aid, the leveling agent and the associative thickener, continuously stirring, and passivating for 2-3h to obtain the antibacterial and antiviral coating. The invention adopts the process wastewater in the chlorination procedure in the production process of the disinfectant sodium dichloroisocyanurate as the production raw material, has low cost, solves the problem of wastewater discharge in the production process of the sodium dichloroisocyanurate and realizes the comprehensive utilization of resources.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of resources and coating processing, in particular to a method for preparing an antibacterial and antiviral coating by adopting sodium dichloroisocyanurate process wastewater.
Background
China is the largest production base of sodium dichloroisocyanurate in the world, the yield of the sodium dichloroisocyanurate in the world is more than 80 percent in China, the total production capacity of the sodium dichloroisocyanurate in China exceeds 26 million tons by 2020, and production enterprises are distributed in Shandong, Henan, Hebei, Anhui, Hubei, inner Mongolia and other areas. Calcium powder, cyanuric acid and chlorine are used as basic raw materials to produce sodium dichloroisocyanurate products, a large amount of process wastewater is generated in the production process, the wastewater comprises chlorinated mother liquor and washing water, wherein dichloroisocyanuric acid and calcium chloride are contained in the wastewater, and the treatment is very troublesome.
The dichloroisocyanuric acid contains available chlorine, is unstable and easy to decompose, and seriously corrodes equipment; at present, the cyanuric acid and the chlorine are converted into cyanuric acid and chlorine by an acidification method, but the cyanuric acid and the chlorine are not easy to treat completely, and a small amount of residual dichloroisocyanuric acid can cause corrosion to equipment. Calcium chloride in the wastewater is generally converted into calcium chloride hexahydrate solid crystals by adopting a multi-effect evaporation process, but due to the special property of the calcium chloride, the calcium chloride has high viscosity when the content is high, and is easy to block equipment and pipelines, so that the calcium chloride is difficult to treat.
Along with the improvement of the living standard of people, the attention on the indoor environment health is gradually improved, so that indoor environment-friendly building material products are continuously updated in an iterative mode, the concept of the bactericidal and antiviral paint is widely proposed under the influence of the epidemic situation of new coronary pneumonia at the end of 2019, more and more paint enterprises are put on the bactericidal and antiviral effects, but the bactericidal and antiviral effects of the current bactericidal and antiviral products on the market are not good, particularly the antiviral performance is high, the virus and the bacteria have different structures and different action mechanisms, the virus has higher destructive power and infectious power compared with the bacteria, the life power of the virus is stronger, various viruses can live in adverse environments for a long time, and the health of human beings is seriously threatened. Therefore, the problem to be solved by those skilled in the art is how to prepare an environment-friendly coating with antibacterial and antiviral properties.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for preparing an antibacterial and antiviral coating by adopting sodium dichloroisocyanurate process wastewater.
In order to achieve the purpose, the technical scheme of the invention is as follows: a method for preparing antibacterial and antiviral paint by adopting sodium dichloroisocyanurate process wastewater is characterized by comprising the following steps:
1) preparing an antibacterial and antiviral A component:
a. the method comprises the steps of removing process wastewater in a chlorination procedure in the production process of sodium dichloroisocyanurate as a toxin agent, adding the process wastewater into a neutralization kettle, adding superfine calcium hydroxide under stirring for neutralization reaction, wherein the weight ratio of the process wastewater to the superfine calcium hydroxide is 1300: 1500-12, maintaining the pH value at 6.8-7.2, stirring for reaction for 30min, naturally cooling to 15-25 ℃ under stirring, standing for settling for 5-7h, collecting lower-layer suspension settling liquid, and concentrating the lower-layer suspension settling liquid until the effective chlorine content is 29-32% and the calcium chloride content is 9.0-10.5%;
b. adding 65-70 parts of the concentrated solution by weight into a reaction kettle, stirring, adding 4-6 parts of superfine shell powder and 0.4-0.6 part of odor masking agent, adjusting the stirring to 600-plus-material 720rpm, adding 15-18 parts of calcium carbonate, continuously maintaining the 600-plus-material 720rpm for stirring for 1h, supplementing deionized water to the total amount of 100 parts, continuously stirring for more than 60min, and standing and curing for more than 5h to obtain an antibacterial and disease-resistant component A for later use;
2) adding 15-18 parts by weight of deionized water into a reaction kettle, adding 0.4-0.6 part of dispersing agent under stirring, continuously stirring for 30min, adding 15-18 parts of titanium dioxide and 1.5-2.0 parts of defoaming agent, adjusting the stirring speed to 1000rpm, stirring for 30min, adding 30-35 parts of antibacterial and antiviral A component, continuously stirring for 20min, sequentially adding 25-30 parts of water-soluble polymer emulsion, 1.0-1.5 parts of film-forming auxiliary agent, 0.1-0.2 part of flatting agent and 0.5-0.8 part of associative thickener, continuously stirring for 40min, adjusting the stirring speed to 200-300rpm, and passivating for 2-3h to obtain the antibacterial and antiviral coating.
Further, the method comprises the following steps of; the grain diameters of the superfine calcium hydroxide and the superfine shell powder in the step 1) are 1250-2000 meshes.
Further, the method comprises the following steps of; the odor covering agent in the step 1) is one of vanillin, ethyl vanillin or emulsion type essence.
Further, the method comprises the following steps of; the dispersant in the step 2) is an aqueous polyacrylic acid sodium salt dispersant, preferably a German Hangao 5040 dispersant.
Further, the method comprises the following steps of; the defoaming agent in the step 2) is a mineral oil defoaming agent or an organic silicon defoaming agent.
Further, the method comprises the following steps of; the water-soluble polymer emulsion in the step 2) is one or more of pure acrylic emulsion, styrene-acrylic emulsion, vinyl acetate emulsion, tertiary vinegar emulsion, polyethylene acetic emulsion, acrylic ester emulsion and butylbenzene emulsion.
Further, the method comprises the following steps of; the film-forming additive in the step 2) is alcohol ester twelve.
Further, the method comprises the following steps of; the leveling agent in the step 2) is polyether modified polysiloxane, preferably Digao 4100 leveling agent.
Further, the method comprises the following steps of; the associative thickener in the step 2) is a nonionic polyurethane associative thickener, preferably a Dow TT-935 thickener.
The invention has the beneficial effects that:
1) the process waste water in the chlorination procedure in the production process of the sodium dichloroisocyanurate serving as a disinfectant is used as a production raw material, so that the cost is low, the problem of discharge of the waste water in the production process of the sodium dichloroisocyanurate is solved, and the comprehensive utilization of resources is realized.
2) The antibacterial and antiviral coating contains the superfine shell powder, and the superfine shell powder is in a porous structure, so that the dispersibility of the coating is improved, and the release of effective chlorine is facilitated.
3) The main antibacterial and antiviral component in the antibacterial and antiviral paint is calcium dichloroisocyanurate, and the calcium dichloroisocyanurate can stably release available chlorine for 4-5 years at normal temperature after the paint is dried.
4) The calcium chloride, the dichloroisocyanuric acid and the calcium carbonate in the antibacterial and antiviral paint form a coexisting system, have the function of moisturizing, and can ensure the slow and stable release of antibacterial and antiviral components.
Detailed Description
Example 1:
a method for preparing antibacterial and antiviral paint by adopting sodium dichloroisocyanurate process wastewater comprises the following steps:
1) preparing an antibacterial and antiviral A component:
a. 1395kg of process wastewater (the content of available chlorine is 1.52 percent, the content of calcium chloride is 10.7 percent and the temperature is 32.5 ℃) in the chlorination procedure in the production process of sodium dichloroisocyanurate without toxicant, the process wastewater is added into a neutralization kettle, 10.8kg of superfine calcium hydroxide with the particle size of 1250 meshes is added under stirring for neutralization reaction, the PH value is 7.02 after the stirring reaction is carried out for 30min, the temperature is naturally reduced to 20 ℃ under stirring, then the process wastewater is kept still and settled for 5.5h, the supernatant is drained to the wastewater treatment procedure, the lower layer suspension settlement concentrated solution is collected for standby, the mass of the concentrated solution is 67.2kg, the content of available chlorine is 30.6 percent, the content of calcium chloride is 9.82 percent and the PH value is 7.14;
b. adding 67.2kg of the concentrated solution into a 150L opening neutralization kettle, stirring at a low speed of 120rpm for 15min, adding 4.5kg of superfine shell powder with the particle size of 1250 meshes and 0.5kg of vanillin, then adjusting the stirring speed to be 600-plus-720 rpm, adding 17.8kg of calcium carbonate, continuously maintaining the 600-plus-720 rpm and stirring for 1h, supplementing 10kg of deionized water, continuously stirring for more than 60min to obtain slurry with the effective chlorine content of 20.30%, the solid content of 48.26% and the pH value of 7.14, and then storing the slurry for static curing for more than 5h to obtain 100kg of an antibacterial and disease-resistant A component for later use;
2) adding 34Kg of deionized water into a 300L reaction kettle, adding 1Kg of a German Hangao 5040 dispersing agent under the stirring of 600rpm, continuously stirring for 30min, adding 38.3Kg of titanium dioxide and 1.2Kg of an organic silicon defoaming agent, adjusting the stirring speed to be 1000rpm, stirring for 30min, adding 66Kg of an antibacterial and disease-resistant A component, continuously stirring for 20min, sequentially adding 55.5Kg of acrylate emulsion, 2.5Kg of an alcohol ester dodecafilming aid, 0.3Kg of a Digao 4100 leveling agent, 1.2Kg of a Dow TT-935 thickening agent, continuously stirring for 40min, adjusting the stirring speed to be 200rpm, and passivating for 3h to obtain 200Kg of the antibacterial and antiviral coating.
Example 2:
a method for preparing antibacterial and antiviral paint by adopting sodium dichloroisocyanurate process wastewater comprises the following steps:
1) preparing an antibacterial and antiviral A component:
a. 1420kg of process wastewater (the content of available chlorine is 1.45 percent, the content of calcium chloride is 10.4 percent and the temperature is 31.0 ℃) in a chlorination procedure in the production process of sodium dichloroisocyanurate without toxicant, the process wastewater is added into a neutralization kettle, 10.5kg of superfine calcium hydroxide with the particle size of 1250 meshes is added under stirring for neutralization reaction, the pH value is 6.98 after stirring reaction for 30min, the temperature is naturally reduced to 20 ℃ under stirring, then the process wastewater is kept stand and settled for 6.0h, supernatant is drained to a wastewater treatment procedure, lower layer suspension settlement concentrated solution is collected for standby, the mass of the concentrated solution is 66.4kg, the content of available chlorine is 30.7 percent, the content of calcium chloride is 9.75 percent and the pH value is 7.06;
b. adding 66.4kg of the concentrated solution into a 150L opening neutralization kettle, stirring at a low speed of 120rpm for 15min, adding 4.7kg of superfine shell powder with the particle size of 1250 meshes and 0.4kg of ethyl vanillin, then adjusting the stirring speed to 600-720rpm, adding 18.0kg of calcium carbonate, continuously maintaining the 600-720rpm and stirring for 1h, supplementing 10.5kg of deionized water, continuously stirring for more than 60min to obtain slurry with the effective chlorine content of 20.24%, the solid content of 49.06% and the PH value of 7.17, and then storing the slurry for static curing for more than 5h to obtain 100kg of an antibacterial and disease-resistant A component for later use;
2) adding 35Kg of deionized water into a 300L reaction kettle, adding 0.9Kg of German Hangao 5040 dispersing agent under stirring at 600rpm, continuously stirring for 30min, adding 39.5Kg of titanium dioxide and 1.1Kg of organic silicon defoaming agent, adjusting the stirring speed to 1000rpm, stirring for 30min, adding 64Kg of antibacterial and disease-resistant A component, continuously stirring for 20min, sequentially adding 55.3Kg of acrylate emulsion, 2.4Kg of alcohol ester dodeca film-forming additive, 0.4Kg of Digao 4100 leveling agent and 1.4Kg of Dow TT-935 thickening agent, continuously stirring for 40min, adjusting the stirring speed to 300rpm, and passivating for 2h to obtain 200Kg of antibacterial and antiviral coating.
Performance testing of the antibacterial and antiviral coatings prepared in examples 1 and 2
The test method comprises the following steps: the detection is carried out according to the detection method specified in the Community Standard T/CNCIA01014-2020 of antibacterial and antiviral paint, and the test results are shown in tables 1-3:
table 1: antibacterial property
Table 2: antiviral Performance (test 24h)
Table 3: antiviral durability Performance (test 24h)
From tables 1 to 3, it can be seen that: the antibacterial and antiviral paint disclosed by the invention has excellent antibacterial and antiviral properties, and exceeds the requirements of the community standard T/CNCIA01014-2020 antibacterial and antiviral paint.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for preparing antibacterial and antiviral paint by adopting sodium dichloroisocyanurate process wastewater is characterized by comprising the following steps:
1) preparing an antibacterial and antiviral A component:
a. the method comprises the steps of removing process wastewater in a chlorination procedure in the production process of sodium dichloroisocyanurate as a toxin agent, adding the process wastewater into a neutralization kettle, adding superfine calcium hydroxide under stirring for neutralization reaction, wherein the weight ratio of the process wastewater to the superfine calcium hydroxide is 1300: 1500-12, maintaining the pH value at 6.8-7.2, stirring for reaction for 30min, naturally cooling to 15-25 ℃ under stirring, standing for settling for 5-7h, collecting lower-layer suspension settling liquid, and concentrating the lower-layer suspension settling liquid until the effective chlorine content is 29-32% and the calcium chloride content is 9.0-10.5%;
b. adding 65-70 parts of the concentrated solution by weight into a reaction kettle, stirring, adding 4-6 parts of superfine shell powder and 0.4-0.6 part of odor masking agent, adjusting the stirring to 600-plus-material 720rpm, adding 15-18 parts of calcium carbonate, continuously maintaining the 600-plus-material 720rpm for stirring for 1h, supplementing deionized water to the total amount of 100 parts, continuously stirring for more than 60min, and standing and curing for more than 5h to obtain an antibacterial and disease-resistant component A for later use;
2) adding 15-18 parts by weight of deionized water into a reaction kettle, adding 0.4-0.6 part of dispersing agent under stirring, continuously stirring for 30min, adding 15-18 parts of titanium dioxide and 1.5-2 parts of defoaming agent, adjusting the stirring speed to 1000rpm, stirring for 30min, adding 29-34 parts of antibacterial and antiviral A component, continuously stirring for 20min, sequentially adding 24.5-29 parts of water-soluble polymer emulsion, 1.0-1.5 parts of film-forming auxiliary agent, 0.1-0.2 part of flatting agent and 0.5-0.8 part of associative thickener, continuously stirring for 40min, adjusting the stirring speed to 200-300rpm, and passivating for 2-3h to obtain the antibacterial and antiviral coating.
2. The method for preparing the antibacterial and antiviral paint by adopting the sodium dichloroisocyanurate process wastewater as claimed in claim 1, which is characterized in that: the particle sizes of the superfine calcium hydroxide and the superfine shell powder in the step 1) are 1250-2000 meshes.
3. The method for preparing the antibacterial and antiviral paint by adopting the sodium dichloroisocyanurate process wastewater as claimed in claim 1, which is characterized in that: the odor covering agent in the step 1) is one of vanillin, ethyl vanillin or emulsion type essence.
4. The method for preparing the antibacterial and antiviral paint by adopting the sodium dichloroisocyanurate process wastewater as claimed in claim 1, which is characterized in that: the dispersant in the step 2) is a water-based sodium polyacrylate dispersant.
5. The method for preparing the antibacterial and antiviral paint by adopting the sodium dichloroisocyanurate process wastewater as claimed in claim 1, which is characterized in that: the defoaming agent in the step 2) is a mineral oil defoaming agent or an organic silicon defoaming agent.
6. The method for preparing the antibacterial and antiviral paint by adopting the sodium dichloroisocyanurate process wastewater as claimed in claim 1, which is characterized in that: the water-soluble polymer emulsion in the step 2) is one or more of styrene-acrylic emulsion, vinyl acetate emulsion, tertiary vinegar emulsion, acrylate emulsion and butylbenzene emulsion.
7. The method for preparing the antibacterial and antiviral paint by adopting the sodium dichloroisocyanurate process wastewater as claimed in claim 1, which is characterized in that: the film-forming additive in the step 2) is alcohol ester twelve.
8. The method for preparing the antibacterial and antiviral paint by adopting the sodium dichloroisocyanurate process wastewater as claimed in claim 1, which is characterized in that: the leveling agent in the step 2) is polyether modified polysiloxane.
9. The method for preparing the antibacterial and antiviral paint by adopting the sodium dichloroisocyanurate process wastewater as claimed in claim 1, which is characterized in that: the associative thickener in the step 2) is a nonionic polyurethane associative thickener.
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| CN100494097C (en) * | 2006-11-06 | 2009-06-03 | 诸城泰盛化工有限公司 | Method for treating wastewater from production of chlorated fulminuric acid |
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