CN114308016A - Manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal and preparation method thereof - Google Patents
Manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal and preparation method thereof Download PDFInfo
- Publication number
- CN114308016A CN114308016A CN202011153059.6A CN202011153059A CN114308016A CN 114308016 A CN114308016 A CN 114308016A CN 202011153059 A CN202011153059 A CN 202011153059A CN 114308016 A CN114308016 A CN 114308016A
- Authority
- CN
- China
- Prior art keywords
- tourmaline
- manganese dioxide
- composite catalyst
- manganese
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229940070527 tourmaline Drugs 0.000 title claims abstract description 109
- 229910052613 tourmaline Inorganic materials 0.000 title claims abstract description 109
- 239000011032 tourmaline Substances 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title abstract description 106
- 230000003115 biocidal effect Effects 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000002696 manganese Chemical class 0.000 claims abstract description 35
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 15
- -1 manganese salt Chemical class 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229940072056 alginate Drugs 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 210000002345 respiratory system Anatomy 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 102000003839 Human Proteins Human genes 0.000 description 1
- 108090000144 Human Proteins Proteins 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- 206010039101 Rhinorrhoea Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000089 gene mutation induction Toxicity 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 208000010753 nasal discharge Diseases 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000004853 protein function Effects 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
Abstract
The invention provides a preparation method of a manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal, which comprises the steps of (1) dispersing tourmaline in an alcohol solvent to obtain a suspension dispersion liquid; (2) adding a manganese salt aqueous solution into the suspension dispersion liquid, and uniformly stirring to obtain a manganese salt/tourmaline mixed solution; (3) adding a hydrogen peroxide solution and an alkali solution into the manganese salt/tourmaline mixed solution to react to generate a manganese dioxide/tourmaline mixture; (4) filtering and washing the manganese dioxide/tourmaline mixture, adding an antibacterial complex and a cross-linking agent into the filtrate, uniformly stirring, and then carrying out heat treatment at a certain temperature under a sealed condition for a certain time to obtain a mixture A; (5) and drying and grinding the mixture A to obtain the manganese dioxide/tourmaline composite catalyst. The invention also provides a manganese dioxide/tourmaline composite catalyst prepared by the preparation method.
Description
Technical Field
The invention relates to the technical field of air purification and catalysis application materials, in particular to a manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal and a preparation method thereof.
Background
Formaldehyde (HCHO) is a common indoor air pollutant and can react with amino in human protein to influence the normal performance of protein functions. Formaldehyde may cause damage to the sensory systems such as the olfactory sensation, respiratory system, immune system and central nervous system of a human body, and may also have adverse effects on human genetics. At low formaldehyde concentrations, the eye and upper respiratory tract may be irritated, causing acute allergic reactions, at moderate concentrations, the respiratory tract may be severely burned, nasal discharge, dyspnea, headache and other symptoms may be caused, and at too high a concentration, pulmonary edema, pneumonia, induction of gene mutation and even death may be caused. The main source of formaldehyde in rooms or vehicles is binders in decorative and furniture materials. Particularly, in newly decorated rooms, a large amount of interior decoration materials can emit a large amount of formaldehyde, so that the content of formaldehyde in indoor air is seriously higher than the national standard.
Manganese dioxide is a novel material for removing formaldehyde, and can effectively decompose pollutants such as formaldehyde in the air at room temperature without any external force. At present, the method for preparing the manganese dioxide catalyst is more, and basically adopts oxidation-reduction reaction. For example, Chinese patent CN105013322B discloses that potassium permanganate or ammonium sulfate is used as an oxidant, manganese sulfate is used as a reducing agent, and manganese dioxide is prepared by hydrothermal reaction; chinese patent CN109513448A discloses that modified activated carbon is used as a carrier, manganese-containing active components are loaded on the activated carbon carrier by an impregnation method, and then the manganese dioxide catalyst is obtained after low-temperature drying and high-temperature roasting in an inert gas atmosphere; chinese patent CN104399486B discloses that potassium permanganate is loaded on acid-modified attapulgite, and then the high catalytic activity manganese dioxide composite catalyst is obtained after coprecipitation and roasting. However, these techniques require a long reaction time at a high temperature of 200 ℃ or more and then a high-temperature calcination at a temperature of 300 ℃ or more, and the preparation process is complicated and the conversion rate of decomposing formaldehyde at room temperature is not high.
Therefore, it is necessary to provide a manganese dioxide/tourmaline composite catalyst for room temperature antibacterial and formaldehyde removal and a preparation method thereof to solve the above problems.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a manganese dioxide/tourmaline composite catalyst for room-temperature antibacterial formaldehyde removal, the preparation process is simple, the production efficiency is high, and the prepared manganese dioxide/tourmaline composite catalyst can improve the efficiency of removing high-concentration formaldehyde in air and has an antibacterial function.
The invention also aims to provide a manganese dioxide/tourmaline composite catalyst prepared by the preparation method of the room-temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst.
In order to realize the aim, the invention provides a preparation method of a manganese dioxide/tourmaline composite catalyst for resisting bacteria and removing formaldehyde at room temperature, which comprises the following steps:
(1) dispersing tourmaline in an alcohol solvent to obtain a suspension dispersion liquid;
(2) adding a manganese salt aqueous solution into the suspension dispersion liquid, and uniformly stirring to obtain a manganese salt/tourmaline mixed solution;
(3) adding a hydrogen peroxide solution and an alkali solution into the manganese salt/tourmaline mixed solution to react to generate a manganese dioxide/tourmaline mixture;
(4) filtering and washing the manganese dioxide/tourmaline mixture, adding an antibacterial complex and a cross-linking agent into the filtrate, uniformly stirring, and then carrying out heat treatment at a certain temperature under a sealed condition for a certain time to obtain a mixture A;
(5) and drying and grinding the mixture A to obtain the manganese dioxide/tourmaline composite catalyst.
Compared with the prior art, the preparation method of the manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal, provided by the invention, comprises the steps of dispersing tourmaline in an alcohol solvent, adding a manganese salt aqueous solution, taking manganese salt as a reducing agent, taking tourmaline as a load, then adding a hydrogen peroxide aqueous solution and an alkali solution, taking the hydrogen peroxide aqueous solution as an oxidant, adjusting the pH value by the alkali solution, reacting to generate a manganese dioxide/tourmaline mixture, avoiding directly adopting manganese dioxide to be mixed with other materials, and adopting a precursor to be mixed with the tourmaline for reaction, so that the manganese dioxide grows on the tourmaline one by one, and the bonding force and the compatibility are better. Furthermore, the manganese salt precursor is used, so that the manganese salt precursor is not easy to agglomerate, the specific surface area of the manganese dioxide is increased, and the large contact area with formaldehyde is realized. Meanwhile, the tourmaline is used as a load, and adsorbs formaldehyde in the air and is subjected to decomposition reaction on the manganese dioxide, so that the room-temperature formaldehyde removal capability of the manganese dioxide is improved. In addition, the antibacterial complex is combined into the manganese dioxide/tourmaline mixture through the cross-linking agent, so that the manganese dioxide/tourmaline composite catalyst has antibacterial performance. Therefore, the preparation method of the room-temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst has the advantages of simple preparation process and high production efficiency, and the prepared manganese dioxide/tourmaline composite catalyst can improve the efficiency of removing high-concentration formaldehyde in air and has an antibacterial function.
Preferably, in the step (1), the tourmaline is dispersed in the alcohol solvent by using a dispersing agent. In specific embodiments, dispersants can be used, but are not limited to, BYK-190, BYK-194, Tego-270, and Tego-652.
Preferably, the alcohol solvent is at least one selected from the group consisting of absolute ethanol, isopropanol, n-propanol and n-butanol.
Preferably, the dosage ratio of the tourmaline powder and the alcohol solvent is 1: 4 to 8. The dosage of the dispersing agent can be 1-5% of the tourmaline.
Preferably, manganese salt, alkali and hydrogen peroxide are respectively added into deionized water to respectively prepare 0.2-2.5 mol/L of the manganese salt aqueous solution, 1-3 mol/L of the alkali solution and 5-15% of the hydrogen peroxide aqueous solution.
Preferably, the manganese salt in the manganese salt aqueous solution is selected from at least one of manganese sulfate, manganese chloride and manganese nitrate. When manganese sulfate is adopted, the manganese dioxide/tourmaline mixture is generated by reaction, and the binding force and the compatibility are better.
Preferably, the alkali in the alkali solution is at least one of sodium hydroxide, potassium hydroxide, ammonia water and ammonium bicarbonate.
Preferably, the mass ratio of the manganese salt to the tourmaline is kept between 3 and 6: 1.
preferably, the antibacterial complex is at least one selected from alginate and chitosan.
Preferably, the crosslinking agent is at least one selected from the group consisting of ethyl orthosilicate, tetrabutyl titanate, ethylene glycol dimethacrylate and polytetrahydrofuran glycol.
Preferably, in the step (4), the heat treatment is performed for 1 to 3 hours under a sealed condition at 50 to 75 ℃.
Preferably, in the step (5), the drying is performed in an oven at 60-120 ℃ for 12-24 hours.
Correspondingly, the application also provides a room-temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst, which is prepared by adopting the preparation method of the room-temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst.
Detailed Description
The technical solutions of the present invention are further illustrated by the following specific embodiments, but the present invention is not limited thereto.
Example 1
A preparation method of a manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal comprises the following steps:
(1) firstly, adding a water-based wetting dispersant BYK-190 into an absolute ethyl alcohol solvent, uniformly stirring at a low speed, adding tourmaline powder of more than 2000 meshes into the system, and stirring at a high speed, wherein the ratio of the tourmaline powder to the absolute ethyl alcohol solvent is 1: 4, the dosage of the dispersant is 1 percent of the tourmaline powder, the stirring speed is 800rpm, and the stirring time is 2 hours, so as to form stable suspension dispersion liquid;
(2) adding a manganese salt aqueous solution into the suspension dispersion, and uniformly stirring to obtain a manganese salt/tourmaline mixed solution, wherein the manganese salt aqueous solution is 0.5mol/L of manganese salt aqueous solution prepared by adding manganese sulfate into deionized water, and the mass ratio of manganese salt to tourmaline is 4: 1;
(3) dropwise adding a hydrogen peroxide solution and an alkali solution into a manganese salt/tourmaline mixed solution until precipitates are generated, then carrying out reflux stirring reaction for 8 hours at 50 ℃, rotating speed of 120rpm, and generating a manganese dioxide/tourmaline mixture by reaction, wherein the hydrogen peroxide solution is a 5% hydrogen peroxide solution obtained by adding hydrogen peroxide into deionized water, and the alkali solution is a 1mol/L alkali solution obtained by adding ammonia water into deionized water;
(4) cooling the manganese dioxide/tourmaline mixture to room temperature, performing suction filtration and washing, removing the filtrate, adding chitosan and tetrabutyl titanate into the filtrate, stirring uniformly to be viscous, and performing heat treatment for 2h at 50 ℃ under a sealed condition to obtain a mixture A;
(5) and drying the mixture A in an oven at 80 ℃ for 12h to completely dry the mixture A, and then grinding the mixture A into powder to obtain the manganese dioxide/tourmaline composite catalyst.
Example 2
A preparation method of a manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal comprises the following steps:
(1) firstly, adding the aqueous wetting dispersant Tego-652 into an n-butyl alcohol solvent, uniformly stirring at a low speed, adding tourmaline powder of more than 2000 meshes into the system, and stirring at a high speed, wherein the ratio of the tourmaline powder to the absolute ethyl alcohol solvent is 1: 6, the using amount of the dispersing agent is 3 percent of the tourmaline powder, the stirring speed is 500rpm, and the stirring time is 1h, so that a stable suspension dispersion liquid is formed;
(2) adding a manganese salt aqueous solution into the suspension dispersion, and uniformly stirring to obtain a manganese salt/tourmaline mixed solution, wherein the manganese salt aqueous solution is a 1mol/L manganese salt aqueous solution prepared by adding manganese chloride into deionized water, and the mass ratio of manganese salt to tourmaline is 6: 1;
(3) dropwise adding a hydrogen peroxide solution and an alkali solution into a manganese salt/tourmaline mixed solution until precipitates are generated, then carrying out reflux stirring reaction for 5 hours at the temperature of 70 ℃, rotating at the speed of 200rpm, and reacting to generate a manganese dioxide/tourmaline mixture, wherein the hydrogen peroxide solution is a 10% hydrogen peroxide solution obtained by adding hydrogen peroxide into deionized water, and the alkali solution is a 2mol/L alkali solution obtained by adding potassium hydroxide into deionized water;
(4) cooling the manganese dioxide/tourmaline mixture to room temperature, performing suction filtration and washing, removing the filtrate, adding alginate and ethylene glycol dimethacrylate into the filtrate, stirring to obtain a viscous state, and performing heat treatment at 70 deg.C under sealed condition for 1h to obtain a mixture A;
(5) and drying the mixture A in an oven at 100 ℃ for 18h to completely dry the mixture A, and then grinding the mixture A into powder to obtain the manganese dioxide/tourmaline composite catalyst.
Example 3
A preparation method of a manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal comprises the following steps:
(1) firstly, adding a water-based wetting dispersant BYK-194 into an isopropanol solvent, uniformly stirring at a low speed, adding tourmaline powder of more than 2000 meshes into the system, and stirring at a high speed, wherein the ratio of the tourmaline powder/absolute ethanol solvent is 1: 8, the using amount of the dispersing agent is 5 percent of that of the tourmaline powder, the stirring speed is 1000rpm, and the stirring time is 1h, so as to form stable suspension dispersion liquid;
(2) adding a manganese salt aqueous solution into the suspension dispersion, and uniformly stirring to obtain a manganese salt/tourmaline mixed solution, wherein the manganese salt aqueous solution is a 2mol/L manganese salt aqueous solution prepared by adding manganese chloride into deionized water, and the mass ratio of manganese salt to tourmaline is 5: 1;
(3) dropwise adding a hydrogen peroxide solution and an alkali solution into a manganese salt/tourmaline mixed solution until precipitates are generated, then carrying out reflux stirring reaction for 6 hours at the temperature of 80 ℃, rotating at the speed of 300rpm, and reacting to generate a manganese dioxide/tourmaline mixture, wherein the hydrogen peroxide solution is a 15% hydrogen peroxide solution obtained by adding hydrogen peroxide into deionized water, and the alkali solution is a 3mol/L alkali solution obtained by adding potassium hydroxide into deionized water;
(4) cooling the manganese dioxide/tourmaline mixture to room temperature, performing suction filtration and washing, removing the filtrate, adding alginate and ethylene glycol dimethacrylate into the filtrate, stirring uniformly to be viscous, and performing heat treatment at 60 ℃ for 2h under a sealed condition to obtain a mixture A;
(5) and drying the mixture A in an oven at 120 ℃ for 24 hours to completely dry the mixture A, and then grinding the mixture A into powder to obtain the manganese dioxide/tourmaline composite catalyst.
Comparative example 1
A preparation method of a manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal comprises the following steps:
(1) firstly, adding a water-based wetting dispersant BYK-190 into an absolute ethyl alcohol solvent, uniformly stirring at a low speed, adding tourmaline powder of more than 2000 meshes into the system, and stirring at a high speed, wherein the ratio of the tourmaline powder to the absolute ethyl alcohol solvent is 1: 4, the dosage of the dispersant is 1 percent of the tourmaline powder, the stirring speed is 800rpm, and the stirring time is 2 hours, so as to form stable suspension dispersion liquid;
(2) adding manganese dioxide into the suspension dispersion liquid, and uniformly stirring to obtain a manganese dioxide/tourmaline mixture;
(3) cooling the manganese dioxide/tourmaline mixture to room temperature, performing suction filtration and washing, removing the filtrate, adding chitosan and tetrabutyl titanate into the filtrate, stirring uniformly to be viscous, and performing heat treatment for 2h at 50 ℃ under a sealed condition to obtain a mixture A;
(4) and drying the mixture A in an oven at 80 ℃ for 12h to completely dry the mixture A, and then grinding the mixture A into powder to obtain the manganese dioxide/tourmaline composite catalyst.
Comparative example 2
A preparation method of a manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal comprises the following steps:
(1) firstly, adding a water-based wetting dispersant BYK-190 into an absolute ethyl alcohol solvent, uniformly stirring at a low speed, adding tourmaline powder of more than 2000 meshes into the system, and stirring at a high speed, wherein the ratio of the tourmaline powder to the absolute ethyl alcohol solvent is 1: 4, the dosage of the dispersant is 1 percent of the tourmaline powder, the stirring speed is 800rpm, and the stirring time is 2 hours, so as to form stable suspension dispersion liquid;
(2) adding a manganese salt aqueous solution into the suspension dispersion, and uniformly stirring to obtain a manganese salt/tourmaline mixed solution, wherein the manganese salt aqueous solution is 0.5mol/L of manganese salt aqueous solution prepared by adding manganese sulfate into deionized water, and the mass ratio of manganese salt to tourmaline is 4: 1;
(3) dropwise adding a hydrogen peroxide solution and an alkali solution into a manganese salt/tourmaline mixed solution until precipitates are generated, then carrying out reflux stirring reaction for 8 hours at 50 ℃, rotating speed of 120rpm, and generating a manganese dioxide/tourmaline mixture by reaction, wherein the hydrogen peroxide solution is a 5% hydrogen peroxide solution obtained by adding hydrogen peroxide into deionized water, and the alkali solution is a 1mol/L alkali solution obtained by adding ammonia water into deionized water;
(4) cooling the manganese dioxide/tourmaline mixture to room temperature, performing suction filtration and washing, removing the filtrate, drying the filtrate in an oven at 80 deg.C for 12 hr, oven drying completely, and grinding into powder to obtain manganese dioxide/tourmaline composite catalyst.
Comparative example 3
A preparation method of a manganese dioxide composite catalyst for room-temperature antibiosis and formaldehyde removal comprises the following steps:
(1) dropwise adding a hydrogen peroxide solution and an alkali solution into a manganese salt aqueous solution until a precipitate is generated, and then carrying out reflux stirring reaction for 8 hours at 50 ℃, wherein the rotation speed is 120rpm, and a manganese dioxide mixture is generated by reaction, wherein the hydrogen peroxide solution is a 5% hydrogen peroxide solution obtained by adding hydrogen peroxide into deionized water, the alkali solution is a 1mol/L alkali solution obtained by adding ammonia water into deionized water, and the manganese salt aqueous solution is a 0.5mol/L manganese salt aqueous solution prepared by adding manganese sulfate into deionized water;
(2) cooling the manganese dioxide mixture to room temperature, performing suction filtration and washing, removing the filtrate, adding chitosan and tetrabutyl titanate into the filtrate, uniformly stirring to be viscous, and performing heat treatment for 2 hours at 50 ℃ under a closed condition to obtain a mixture A;
(3) and drying the mixture A in an oven at 80 ℃ for 12h to completely dry the mixture A, and then grinding the mixture A into powder to obtain the manganese dioxide composite catalyst.
The manganese dioxide/tourmaline composite catalysts prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to formaldehyde removal rate and antibacterial property tests, and the results are shown in table 1.
Wherein, the formaldehyde removal rate test refers to the method of GB/T35239-2017: in a closed volume of 1m3The test is carried out in the test chamber, 1g of test sample is placed in the test chamber, 200 mu L of formaldehyde release source is put into the test chamber at one time, and a fan is started to uniformly mix the air in the chamber; turning off the fan, and sampling and detecting the concentration of formaldehyde in the air in the cabin to be an initial concentration value; the fan is turned on to keep the air volume at 100m3Closing the fan after 6 hours, and sampling and detecting the concentration of formaldehyde in the air in the cabin; the formaldehyde removal rate can be obtained after the comparison and calculation of the two.
The antibacterial performance test is carried out by GB/T21510-2008.
TABLE 1 results of tests on formaldehyde removal rate and antibacterial property of manganese dioxide/tourmaline composite catalyst
| Test of | Formaldehyde removal rate (after 6 h) | Antibacterial rate (after 24 h) |
| Example 1 | 96.5％ | 99.5％ |
| Example 2 | 97.1％ | 99.6％ |
| Example 3 | 96.9％ | 99.7％ |
| Comparative example 1 | 73.2％ | 97.2％ |
| Comparative example 2 | 95.3％ | 3.7％ |
| Comparative example 3 | 77.7％ | 92.6％ |
As can be seen from table 1, the manganese dioxide/tourmaline composite catalyst prepared by the preparation method of the present application has excellent formaldehyde removal rate and antibacterial property.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the best embodiments, the present invention is not limited to the above disclosed embodiments, but should cover various modifications, equivalent combinations, made according to the essence of the present invention.
Claims (10)
1. A preparation method of a room-temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst is characterized by comprising the following steps:
(1) dispersing tourmaline in an alcohol solvent to obtain a suspension dispersion liquid;
(2) adding a manganese salt aqueous solution into the suspension dispersion liquid, and uniformly stirring to obtain a manganese salt/tourmaline mixed solution;
(3) adding a hydrogen peroxide solution and an alkali solution into the manganese salt/tourmaline mixed solution to react to generate a manganese dioxide/tourmaline mixture;
(4) filtering and washing the manganese dioxide/tourmaline mixture, adding an antibacterial complex and a cross-linking agent into the filtrate, uniformly stirring, and then carrying out heat treatment at a certain temperature under a sealed condition for a certain time to obtain a mixture A;
(5) and drying and grinding the mixture A to obtain the manganese dioxide/tourmaline composite catalyst.
2. The method for preparing room temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in claim 1, wherein said alcohol solvent is at least one selected from the group consisting of absolute ethyl alcohol, isopropyl alcohol, n-propyl alcohol and n-butyl alcohol.
3. The method for preparing room temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in claim 1, wherein the manganese salt in the manganese salt aqueous solution is selected from at least one of manganese sulfate, manganese chloride and manganese nitrate.
4. The method for preparing room temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in claim 1, wherein the alkali in the alkali solution is derived from at least one of sodium hydroxide, potassium hydroxide, ammonia water and ammonium bicarbonate.
5. The method for preparing room temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in claim 1, wherein said antibacterial complex is selected from at least one of alginate or chitosan.
6. The method for preparing room temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in claim 1, wherein said crosslinking agent is at least one selected from the group consisting of ethyl orthosilicate, tetrabutyl titanate, ethylene glycol dimethacrylate and polytetrahydrofuran diol.
7. The preparation method of the room-temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in claim 1, wherein a manganese salt, an alkali and hydrogen peroxide are added to deionized water to prepare 0.2-2.5 mol/L of the manganese salt aqueous solution, 1-3 mol/L of the alkali solution and 5-15% of the hydrogen peroxide aqueous solution respectively.
8. The preparation method of the room temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in claim 1, wherein in the step (4), the heat treatment is performed for 1-3 hours under a closed condition of 50-75 ℃.
9. The method for preparing room temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in claim 1, wherein in the step (1), the tourmaline is dispersed in the alcohol solvent using a dispersing agent.
10. A room-temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst, which is characterized by being prepared by the preparation method of the room-temperature antibacterial formaldehyde-removing manganese dioxide/tourmaline composite catalyst as claimed in any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011153059.6A CN114308016A (en) | 2020-10-26 | 2020-10-26 | Manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011153059.6A CN114308016A (en) | 2020-10-26 | 2020-10-26 | Manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114308016A true CN114308016A (en) | 2022-04-12 |
Family
ID=81032993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011153059.6A Pending CN114308016A (en) | 2020-10-26 | 2020-10-26 | Manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114308016A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327424A (en) * | 2008-04-29 | 2008-12-24 | 上海博物馆 | Formaldehyde adsorbing agent containing chitosan |
| CN107243343A (en) * | 2016-08-12 | 2017-10-13 | 宁波钛安新材料科技有限公司 | A kind of air cleaning catalytic composite material and preparation method thereof |
| CN107362823A (en) * | 2017-09-22 | 2017-11-21 | 临沂恺峰生物科技有限公司 | A kind of catalysis material of room temperature degraded indoor formaldehyde and preparation method thereof |
| CN107537473A (en) * | 2017-07-20 | 2018-01-05 | 中山大学 | A kind of nanometer Mn catalyst of room temperature catalytic oxidation formaldehyde and preparation method thereof |
| CN107697952A (en) * | 2017-10-27 | 2018-02-16 | 上海纳米技术及应用国家工程研究中心有限公司 | For removing preparation method of manganese bioxide material of low concentration formaldehyde and products thereof and application in air |
| WO2018143782A1 (en) * | 2017-02-06 | 2018-08-09 | 주식회사 오투엠 | Highly functional solid oxygen composition and method for preparing same |
| CN110115935A (en) * | 2019-06-14 | 2019-08-13 | 南京长三角绿色发展研究院有限公司 | A kind of preparation method of low concentration formaldehyde scavenging material |
-
2020
- 2020-10-26 CN CN202011153059.6A patent/CN114308016A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327424A (en) * | 2008-04-29 | 2008-12-24 | 上海博物馆 | Formaldehyde adsorbing agent containing chitosan |
| CN107243343A (en) * | 2016-08-12 | 2017-10-13 | 宁波钛安新材料科技有限公司 | A kind of air cleaning catalytic composite material and preparation method thereof |
| WO2018143782A1 (en) * | 2017-02-06 | 2018-08-09 | 주식회사 오투엠 | Highly functional solid oxygen composition and method for preparing same |
| CN107537473A (en) * | 2017-07-20 | 2018-01-05 | 中山大学 | A kind of nanometer Mn catalyst of room temperature catalytic oxidation formaldehyde and preparation method thereof |
| CN107362823A (en) * | 2017-09-22 | 2017-11-21 | 临沂恺峰生物科技有限公司 | A kind of catalysis material of room temperature degraded indoor formaldehyde and preparation method thereof |
| CN107697952A (en) * | 2017-10-27 | 2018-02-16 | 上海纳米技术及应用国家工程研究中心有限公司 | For removing preparation method of manganese bioxide material of low concentration formaldehyde and products thereof and application in air |
| CN110115935A (en) * | 2019-06-14 | 2019-08-13 | 南京长三角绿色发展研究院有限公司 | A kind of preparation method of low concentration formaldehyde scavenging material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2020507445A (en) | Transition metal and nitrogen co-doped carbon composite material used for formaldehyde purification and its preparation method | |
| CN110479317B (en) | VOCs catalytic combustion catalyst and preparation method and application thereof | |
| CN102658135B (en) | Ruthenium supported perovskite-type-oxide ammonia synthesis catalyst and preparation method thereof | |
| CN103191712A (en) | Cerium oxide and zirconium oxide based composite rare earth oxide with favorable ageing resistance and high reduction activity and preparation method of cerium oxide and zirconium oxide based composite rare earth oxide | |
| CN111085241B (en) | Method for preparing aniline by nitrobenzene hydrogenation and preparation method of catalyst thereof | |
| CN111939896B (en) | Liquid catalyst for catalyzing ozonolysis at normal temperature and preparation method and application thereof | |
| CN110075831B (en) | Iridium supported catalyst for catalytic combustion of low-concentration methane and preparation method thereof | |
| CN111450876A (en) | Low-temperature SCR denitration catalyst using carriers with different particle sizes to load Mn and preparation method thereof | |
| CN113145163A (en) | All-silicon molecular sieve supported palladium methane oxidation catalyst and preparation method thereof | |
| CN105327699A (en) | Air cleaning material | |
| CN109772288B (en) | Surface cerium-rich nano cerium-zirconium composite oxide and preparation and application thereof | |
| CN102989521B (en) | Zirconium-containing spinel supported honeycomb monolithic catalyst for selective hydrogenation of benzene and preparation method for same | |
| CN114471585A (en) | Ozone catalyst with acetate as precursor and preparation method and application thereof | |
| CN110252375B (en) | Iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound, preparation method and application as photocatalyst | |
| CN114308016A (en) | Manganese dioxide/tourmaline composite catalyst for room-temperature antibiosis and formaldehyde removal and preparation method thereof | |
| CN114797841B (en) | Mn (Mn) 4+ And Ce (Ce) 3+ Preparation method of enhanced Mn-M-Ti-O ultralow temperature denitration catalyst | |
| CN109701591B (en) | Catalyst for alpha-pinene isomerization reaction and preparation method thereof | |
| CN111167281A (en) | Manganese cerium oxide/active carbon composite material for formaldehyde decomposition and preparation method thereof | |
| CN109046324B (en) | Medium-low temperature denitration catalyst with mesoporous cerium oxide as carrier and preparation method thereof | |
| CN110947396A (en) | Spherical manganese oxide coated iron oxide core-shell structure compound and preparation method and application thereof | |
| CN111318296A (en) | Preparation method and application of supported cobalt/carbon nanotube material derived from zeolite imidazole framework material | |
| CN110975898A (en) | Platinum catalyst loaded on hydroxyapatite composite cobaltosic oxide and preparation method thereof | |
| CN108176349B (en) | Al (aluminum)2O3@TiO2Preparation method of core-shell structure simultaneous desulfurization and denitrification adsorbent | |
| CN114191981B (en) | Harmless treatment method for industrial waste gas | |
| CN111250078B (en) | MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |