CN112642452A - Functional heating slurry capable of degrading organic pollutants and preparation method and application thereof - Google Patents
Functional heating slurry capable of degrading organic pollutants and preparation method and application thereof Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 104
- 239000002002 slurry Substances 0.000 title claims abstract description 94
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 71
- 230000000593 degrading effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 76
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 76
- 238000005485 electric heating Methods 0.000 claims abstract description 40
- 238000004887 air purification Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 187
- 239000000243 solution Substances 0.000 claims description 66
- 238000002156 mixing Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 235000015110 jellies Nutrition 0.000 claims description 20
- 239000008274 jelly Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 abstract description 39
- 238000006731 degradation reaction Methods 0.000 abstract description 39
- 230000000694 effects Effects 0.000 abstract description 18
- 239000012855 volatile organic compound Substances 0.000 abstract description 7
- 235000019441 ethanol Nutrition 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2045—Calcium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
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Abstract
The invention discloses functional heating slurry capable of degrading organic pollutants, and a preparation method and application thereof. The functional heating slurry comprises electric heating slurry and hydroxyapatite. The functional heating slurry has the functions of electric heating and organic pollutant degradation, has the advantages of simple preparation, low cost, stable heating performance, high organic pollutant degradation speed and the like, and can realize the effects of heating and degrading volatile organic compounds in air simultaneously when being used in the fields of heating and air purification.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to functional heating slurry capable of degrading organic pollutants, and a preparation method and application thereof.
Background
As is well known, air is an essential substance for human life, but at present, more and more volatile organic compounds, such as formaldehyde, benzene and the like, are mixed in the air, and the volatile organic compounds cause great damage to human bodies and seriously affect the physiological functions of the human bodies, so that research on degradation of the volatile organic compounds is indispensable. The electrothermal film heating is a novel clean heating mode with energy conservation, environmental protection, strong comfort and high safety, and is developed rapidly in recent years. Therefore, how to take heating and degrade organic pollutants into consideration has very important significance for energy conservation, environmental protection and human health.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, it is an object of the present invention to propose a functionally heated slurry capable of degrading organic pollutants, a method for its preparation and its use. The functional heating slurry has the functions of electric heating and organic pollutant degradation, has the advantages of simple preparation, low cost, stable heating performance, high organic pollutant degradation speed and the like, and can realize the effects of heating and degrading volatile organic compounds in air simultaneously when being used in the fields of heating and air purification.
The present application is proposed based on the following findings of the inventors:
the electrothermal slurry is used as the raw material of the electrothermal film and is the main factor influencing the performance of the electrothermal film. If the organic pollutant degradation substance is added into the electric heating slurry, the functional slurry with both organic pollutant degradation and heating can be prepared, the types of the functional slurry can be enriched, and the blank of products in the market can be filled.
To this end, according to a first aspect of the invention, a functionally heated slurry capable of degrading organic contaminants is provided. According to an embodiment of the invention, the functionally heated paste comprises an electrically heated paste and hydroxyapatite.
The inventor finds that the hydroxyapatite can remove the surrounding O under the ultraviolet irradiation2And H2Catalytic oxidation of O molecules to O2-Or OH, both of which can oxidize organic pollutants and ultimately degrade them to CO2And H2O, and no harmful substances are generated; and the hydroxyapatite also has stronger adsorbability under the influence of crystal structure and surface characteristics. Therefore, the hydroxyapatite is used as the organic pollutant degradation substance to be mixed with the electric heating slurry to prepare the functional heating slurry, so that the functional heating slurry has the functions ofThe electrothermal film has the advantages of simple preparation, low cost, stable heating performance, high degradation speed of organic pollutants, suitability for mass production and the like, and can effectively adsorb the organic pollutants and carry out catalytic degradation on the organic pollutants in the use process when the electrothermal film is prepared by utilizing the functional heating slurry, so that the aim of heating can be fulfilled, air can be purified, and the electrothermal film has wide application value.
In addition, the functional heating slurry capable of degrading organic pollutants according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the hydroxyapatite is doped in an amount of 1 to 20 wt% of the electric heating paste.
In some embodiments of the present invention, the hydroxyapatite is doped in an amount of 3 to 10 wt% of the electric heating paste.
In some embodiments of the present invention, the electrothermal paste is a carbon-based conductive paste and/or a metal conductive paste.
In some embodiments of the present invention, the hydroxyapatite has a particle size of 1 to 500 nm.
According to a second aspect of the present invention, there is provided a method of preparing the above-mentioned functionally heated slurry capable of degrading organic contaminants. According to an embodiment of the invention, the method comprises:
(1) respectively adding Ca (NO)3)2·4H2O and P2O5Mixing with anhydrous ethanol to obtain Ca (NO)3)2·4H2Oethanol solution and P2O5Ethanol solution;
(2) under stirring, adding said P2O5Dripping ethanol solution into the Ca (NO)3)2·4H2In an O ethanol solution to obtain a mixed solution;
(3) gelling and aging the mixed solution under the condition of water bath so as to obtain jelly;
(4) drying, calcining and grinding the jelly in sequence so as to obtain nano-grade hydroxyapatite;
(5) and mixing the hydroxyapatite with the electric heating slurry according to a preset proportion so as to obtain the functional heating slurry capable of degrading organic pollutants.
According to the method of preparing a functionally heated slurry of the above embodiment of the present invention, Ca (NO) is previously added3)2·4H2O and P2O5Respectively mixing with absolute ethyl alcohol and then adding P2O5Adding Ca (NO) dropwise into ethanol solution3)2·4H2In O ethanol solution, Ca (NO) can be effectively controlled3)2·4H2O and P2O5The reaction rate of the method avoids the difficulty in forming uniform and stable sol and jelly due to the excessively high reaction rate of the sol and the jelly, and the obtained jelly is dried, calcined and ground to obtain uniform and high-purity nano hydroxyapatite; and finally, mixing the hydroxyapatite with the electric heating slurry to obtain the functional heating slurry which has the functions of electric heating and organic pollutant degradation, has stable heating performance and high degradation speed of the organic pollutants. In conclusion, the method is simple in process, low in cost and suitable for mass production, and the obtained functional heating slurry can achieve the purpose of heating, can purify air and has wide application value.
In some embodiments of the invention, in step (1), the Ca (NO) is3)2·4H2The concentration of the O ethanol solution is 0.5-2 mol/L, and the P is2O5The concentration of the ethanol solution is 0.2-1 mol/L.
In some embodiments of the invention, in step (2), the Ca (NO) is3)2·4H2O ethanol solution and the P2O5The mixing volume ratio of the ethanol solution is (0.4-3): 1.
in some embodiments of the invention, in the step (2), the stirring speed is 200 to 400r/min, and the stirring time is 0.5 to 2 hours.
In some embodiments of the invention, in step (2), the P is added using an acid burette under magnetic stirring2O5Dripping ethanol solution into the Ca (NO)3)2·4H2And (4) in the O ethanol solution, continuously stirring for 0.5-2 h after the mixing is finished.
In some embodiments of the invention, in the step (3), the water bath temperature is 30-70 ℃, the gelling time is 12-36 hours, and the aging time is 12-36 hours.
In some embodiments of the invention, in the step (4), the drying temperature is 80 to 150 ℃, the calcining temperature is 400 to 800 ℃, and the calcining time is 0.5 to 4 hours.
According to a third aspect of the present invention, the present invention provides the use of the above functional heating slurry capable of degrading organic pollutants or the functional heating slurry capable of degrading organic pollutants obtained by the above preparation method in heating and air purification. The functional heating slurry has the functions of degrading and heating organic pollutants, is stable in heating performance and high in degradation speed of the organic pollutants, can achieve the effects of heating and degrading volatile organic compounds in air when being used in the fields of heating and air purification, and compared with the existing functional heating slurry, the functional heating slurry not only meets the requirements of human health and environmental protection, but also has wide application scenes and very attractive use value.
According to a fourth aspect of the present invention, an electrothermal film is provided. According to the embodiment of the invention, the electrothermal film is prepared by adopting the functional heating slurry capable of degrading the organic pollutants or the functional heating slurry capable of degrading the organic pollutants obtained by adopting the preparation method. The electrothermal film has the functions of degrading and heating organic pollutants, has stable heating performance and high degradation speed of the organic pollutants, can achieve the purpose of heating, can purify air, and has wide application value.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is an XRD pattern of hydroxyapatite prepared in example 1 of the present invention.
Fig. 2 is an SEM image of hydroxyapatite prepared in example 1 of the present invention.
FIG. 3 is a photograph of the heat generation at a voltage of 20V after screen printing of the functionally heated paste prepared in example 1 of the present invention.
FIG. 4 is a formaldehyde degradation curve of the functional heating paste prepared in example 1 of the present invention at a heating temperature of 80 ℃.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to a first aspect of the present invention, a functionally heated slurry capable of degrading organic contaminants is provided. According to an embodiment of the invention, the functionally heated paste comprises an electrically heated paste and hydroxyapatite. The inventor finds that the hydroxyapatite can remove the surrounding O under the ultraviolet irradiation2And H2Catalytic oxidation of O molecules to O2-Or OH, both of which can oxidize organic pollutants and ultimately degrade them to CO2And H2O, and no harmful substances are generated; and the hydroxyapatite also has stronger adsorbability under the influence of crystal structure and surface characteristics. Therefore, the functional heating slurry is prepared by mixing the hydroxyapatite serving as the organic pollutant degradation substance with the electric heating slurry, so that the functional heating slurry has the functions of electric heating and organic pollutant degradation, has the advantages of simple preparation, low cost, stable heating performance, high organic pollutant degradation speed, suitability for mass production and the like, and can effectively adsorb and catalyze the organic pollutants in the using process of the electric heating film when the electric heating film is prepared by using the functional heating slurry, thereby achieving the aim of heating and purifying air and having the functions of heating and purifying airHas wide application value.
The functional heating paste capable of degrading organic contaminants according to the above-described embodiment of the present invention will be described in detail.
According to an embodiment of the present invention, the amount of the hydroxyapatite may be 1 to 20 wt% of the electrothermal slurry, for example, 1%, 2%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, or the like. The inventor finds that when the functional heating slurry is used for preparing the electrothermal film, if the adding amount of the hydroxyapatite is too small, the degradation effect on organic pollutants is poor; if the added amount of the hydroxyapatite is too much, the conductivity of the electrothermal film can be influenced, particularly when the nano hydroxyapatite is adopted, the added amount of the hydroxyapatite can cause agglomeration in the slurry, the electrothermal performance of the electrothermal film can be obviously influenced, the effective contact between the hydroxyapatite and air can be greatly reduced, and the degradation effect of the electrothermal film on organic pollutants is reduced. Preferably, the doping amount of the hydroxyapatite can be 3-10 wt% of the electrothermal slurry, so that the adverse effects on the electrothermal performance and the organic pollutant degradation effect of the finally prepared electrothermal film due to excessive addition amount of the hydroxyapatite can be further avoided, and the utilization rate of the hydroxyapatite can be further improved on the premise of ensuring that the electrothermal film has better electrothermal performance and the capability of rapidly degrading organic pollutants.
According to still another embodiment of the present invention, the type of the electric heating paste in the present invention is not particularly limited, and those skilled in the art can select it according to actual needs. For example, the electrothermal paste is a carbon-based conductive paste and/or a metal conductive paste.
According to still another embodiment of the present invention, the particle size of the hydroxyapatite may be 1 to 500nm, for example, 1nm, 5nm, 10nm, 15nm, 20nm, 50nm, 65nm, 80nm, 100nm, 200nm, 300nm, 400nm, or 500nm, and if the particle size of the hydroxyapatite is too large, the uniformity of the slurry after mixing is deteriorated. According to the invention, the nano-grade hydroxyapatite with the particle size range is selected, so that on one hand, the mixing uniformity of the hydroxyapatite and the electric heating slurry can be improved, the hydroxyapatite is further uniformly distributed in the electric heating film, and the electric conduction stability of the electric heating film is improved; on the other hand can show the specific surface area who improves the hydroxyapatite, increase the effective area of contact of hydroxyapatite and air in the electric heat membrane, and then can show the absorption and the catalytic degradation effect that improve the electric heat membrane to organic pollutant.
According to a second aspect of the present invention, there is provided a method of preparing the above-mentioned functionally heated slurry capable of degrading organic contaminants. According to an embodiment of the invention, the method comprises:
(1) respectively adding Ca (NO)3)2·4H2O and P2O5Mixing with anhydrous ethanol to obtain Ca (NO)3)2·4H2Oethanol solution and P2O5Ethanol solution. The inventors found that if P is directly reacted with2O5With Ca (NO)3)2Aqueous solution or Ca (NO)3)2·4H2O mixing, which can cause the reaction rate to be too fast and out of control, can adopt absolute ethyl alcohol as a diluent to inhibit the reaction.
According to one embodiment of the invention, Ca (NO)3)2·4H2The concentration of the O ethanol solution can be 0.5-2 mol/L, and P2O5The concentration of the ethanol solution can be 0.2-1 mol/L. The inventors found that if Ca (NO)3)2·4H2O ethanol solution or P2O5Too high a concentration of the ethanol solution, mixing of the two would also lead to a runaway reaction rate, if Ca (NO) were used3)2·4H2O ethanol solution or P2O5The reaction efficiency is influenced by too small concentration of the ethanol solution, and the reaction rate can be further controlled on the basis of ensuring the preparation efficiency by controlling the concentration range.
(2) Under stirring, adding P2O5Adding Ca (NO) dropwise into ethanol solution3)2·4H2In the O ethanol solution, adding the mixture into an O ethanol solution,to obtain a mixed solution. The inventors have found that by mixing P under stirring conditions2O5Slowly dripping Ca (NO) into the ethanol solution3)2·4H2In the O ethanol solution, the two can be fully mixed, and the reaction rate can be further controlled, so that the hydrolysis reaction rate is effectively controlled and maintained in a stable state, and more uniform and stable sol mixed liquor can be obtained.
According to one embodiment of the invention, Ca (NO)3)2·4H2O ethanol solution and P2O5The mixing volume ratio of the ethanol solution can be (0.4-3): 1, the inventors found that Ca (NO)3)2·4H2O ethanol solution and P2O5The volume ratio of the ethanol solution is too large or too small, which affects the uniformity and stability of the colloid mixed solution and the yield of the hydroxyapatite. Preferably, Ca (NO) can be controlled simultaneously3)2·4H2The concentration of the O ethanol solution is 0.5-2 mol/L, P2O5The concentration of the ethanol solution is 0.2-1 mol/L, Ca (NO)3)2·4H2O ethanol solution and P2O5The mixing volume ratio of the ethanol solution is (0.4-3): 1, thereby further improving the utilization rate of raw materials and the yield and uniformity of the hydroxyapatite.
According to yet another embodiment of the present invention, P is2O5Adding Ca (NO) dropwise into ethanol solution3)2·4H2When the mixture is in an O ethanol solution, the stirring speed can be controlled to be 200-400 r/min, and the stirring time is 0.5-2 h. Specifically, P can be added using an acid burette under magnetic stirring2O5Adding Ca (NO) dropwise into ethanol solution3)2·4H2And (4) in the O ethanol solution, continuously stirring for 0.5-2 h after the mixing is finished. Whereby P can be further secured2O5Ethanol solutionCa (NO) is added dropwise3)2·4H2The O ethanol solution can be uniformly mixed and fully reacted, so that the problem that the uniformity and the purity of the sol are influenced due to incomplete reaction is avoided.
(3) Gelling and aging the mixed solution under the condition of water bath to obtain jelly
According to an embodiment of the invention, the water bath temperature can be 30-70 ℃, the gelling time can be 12-36 h, and the aging time is 12-36 h. The inventor finds that if the water bath temperature is too low or the gel time is too short, the problem that the purity and the uniformity of the jelly are affected due to insufficient reaction is easy to occur, and if the temperature is too high or the gel time is too long, the reaction rate is too high or excessive, and the uniform jelly cannot be formed; further, if the aging time is too short, the stability of the obtained jelly is poor, and if the aging time is too long, the preparation efficiency is obviously influenced.
(4) Drying, calcining and grinding the jelly in sequence to obtain the nano-grade hydroxyapatite
According to an embodiment of the invention, the drying temperature can be 80-150 ℃, and the drying time can be 12-36 hours, so that the drying efficiency can be ensured, and the removal of ethanol in jelly is facilitated. Furthermore, the calcination temperature can be 400-800 ℃, and the calcination time can be 0.5-4 h. The inventor finds that if the calcining temperature is too low, the desired hydroxyapatite product cannot be obtained, and if the calcining temperature is too high, the degradation activity of the hydroxyapatite is reduced; in addition, if the calcination time is too short, the reaction will be incomplete, and if the calcination time is too long, the energy will be wasted. The invention can further improve the purity of the finally obtained hydroxyapatite by controlling the calcination to be the above conditions.
According to one embodiment of the invention, the jelly is dried in a forced air drying oven, calcined in a box furnace, cooled and ground to obtain hydroxyapatite. The calcined product can be ground to 1-500 nm, and the inventor finds that the uniformity of the mixed slurry is poor if the particle size of the hydroxyapatite is too large, and the nano-grade hydroxyapatite in the particle size range is selected, so that the uniformity of the mixture of the hydroxyapatite and the electric heating slurry can be improved, the hydroxyapatite is uniformly distributed in the electric heating film, and the electric conduction stability of the electric heating film is improved; on the other hand can show the specific surface area who improves the hydroxyapatite, increase the effective area of contact of hydroxyapatite and air in the electric heat membrane, and then can show the absorption and the catalytic degradation effect that improve the electric heat membrane to organic pollutant.
(5) Mixing hydroxyapatite and electric heating slurry according to a predetermined proportion to obtain functional heating slurry capable of degrading organic pollutants
According to an embodiment of the present invention, the amount of the hydroxyapatite may be 1 to 20 wt% of the electrothermal slurry, for example, 1%, 2%, 5%, 7%, 10%, 12%, 15%, 17%, 20%, or the like. The inventor finds that when the functional heating slurry is used for preparing the electrothermal film, if the adding amount of the hydroxyapatite is too small, the degradation effect on organic pollutants is poor; if the added amount of the hydroxyapatite is too much, the conductivity of the electrothermal film can be influenced, particularly when the nano hydroxyapatite is adopted, the added amount of the hydroxyapatite can cause agglomeration in the slurry, the electrothermal performance of the electrothermal film can be obviously influenced, the effective contact between the hydroxyapatite and air can be greatly reduced, and the degradation effect of the electrothermal film on organic pollutants is reduced. Preferably, the doping amount of the hydroxyapatite can be 3-10 wt% of the electrothermal slurry, so that the adverse effects on the electrothermal performance and the organic pollutant degradation effect of the finally prepared electrothermal film due to excessive addition amount of the hydroxyapatite can be further avoided, and the utilization rate of the hydroxyapatite can be further improved on the premise of ensuring that the electrothermal film has better electrothermal performance and the capability of rapidly degrading organic pollutants.
According to still another embodiment of the present invention, the type of the electric heating paste in the present invention is not particularly limited, and those skilled in the art can select it according to actual needs. For example, the electrothermal paste is a carbon-based conductive paste and/or a metal conductive paste.
In summary, according to the method for preparing a functional heating paste of the above embodiment of the present invention, Ca (NO) is preliminarily added3)2·4H2O and P2O5Respectively mixing with absolute ethyl alcohol and then adding P2O5Adding Ca (NO) dropwise into ethanol solution3)2·4H2In O ethanol solution, Ca (NO) can be effectively controlled3)2·4H2O and P2O5The reaction rate of the method avoids the difficulty in forming uniform and stable sol and jelly due to the excessively high reaction rate of the sol and the jelly, and the obtained jelly is dried, calcined and ground to obtain uniform and high-purity nano hydroxyapatite; and finally, mixing the hydroxyapatite with the electric heating slurry to obtain the functional heating slurry which has the functions of electric heating and organic pollutant degradation, has stable heating performance and high degradation speed of the organic pollutants. In conclusion, the method is simple in process, low in cost and suitable for mass production, and the obtained functional heating slurry can achieve the purpose of heating and purify air, and has a wide application value. It should be noted that the features and effects described for the functional heating slurry capable of degrading organic pollutants are also applicable to the method for preparing the functional heating slurry capable of degrading organic pollutants, and are not described in detail herein.
According to a third aspect of the present invention, the present invention provides the use of the above functional heating slurry capable of degrading organic pollutants or the functional heating slurry capable of degrading organic pollutants obtained by the above preparation method in heating and air purification. The functional heating slurry has the functions of degrading and heating organic pollutants, is stable in heating performance and high in degradation speed of the organic pollutants, can achieve the effects of heating and degrading volatile organic compounds in air when being used in the fields of heating and air purification, and compared with the existing functional heating slurry, the functional heating slurry not only meets the requirements of human health and environmental protection, but also has wide application scenes and very attractive use value. It should be noted that the features and effects described for the above functional heating slurry capable of degrading organic pollutants and the method for preparing the functional heating slurry capable of degrading organic pollutants are also applicable to the use of the functional heating slurry, and are not repeated herein.
According to a fourth aspect of the present invention, an electrothermal film is provided. According to the embodiment of the invention, the electrothermal film is prepared by adopting the functional heating slurry capable of degrading the organic pollutants or the functional heating slurry capable of degrading the organic pollutants obtained by adopting the preparation method. The electrothermal film has the functions of degrading and heating organic pollutants, has stable heating performance and high degradation speed of the organic pollutants, can achieve the purpose of heating, can purify air, and has wide application value. It should be noted that the characteristics and effects described for the functional heating slurry capable of degrading organic pollutants and the method for preparing the functional heating slurry capable of degrading organic pollutants are also applicable to the electric heating film, and are not repeated herein.
According to an embodiment of the present invention, the type of the electric heating film is not particularly limited, and those skilled in the art can select the electric heating film according to actual needs, for example, the electric heating film may be a low-temperature electric heating film, a high-temperature electric heating film, an electric heating greenhouse film, an electric heating wall film, an electric heating mulching film, and the like.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) 23.615g of Ca (NO) was accurately weighed3)2·4H2O, adding into 100ml of absolute ethyl alcohol to prepare the concentration of1mol/L Ca (NO)3)2·4H2O ethanol solution; accurately weighing 4.258g of P2O5Adding into 100ml of absolute ethyl alcohol to prepare P with the concentration of 0.3mol/L2O5Ethanol solution;
(2) 50mL of Ca (NO) was measured3)2·4H2Adding O ethanol solution into Ca (NO) solution at 30 deg.C under magnetic stirring at 300r/min with acid burette3)2·4H2Slowly dripping 50ml of P into the O ethanol solution2O5After the ethanol solution is added dropwise, continuously stirring for 1 h;
(3) gelling the uniformly stirred mixed solution in a water bath at 30 ℃ for 24h, and aging for 24h to obtain jelly;
(4) drying the colloidal substance in a forced air drying oven at 100 ℃ for 24h, then calcining in a box-type furnace at 600 ℃ for 2h, cooling and grinding to obtain hydroxyapatite;
(5) adding hydroxyapatite into the graphene conductive slurry according to the doping amount of 5 wt%, and uniformly mixing to obtain the functional heating slurry for degrading organic pollutants.
Example 2
(1) 35.423g of Ca (NO) was accurately weighed3)2·4H2O, adding into 100ml of absolute ethyl alcohol to prepare Ca (NO) with the concentration of 1.5mol/L3)2·4H2O ethanol solution; accurately weighing 4.258g of P2O5Adding into 100ml of absolute ethyl alcohol to prepare P with the concentration of 0.3mol/L2O5Ethanol solution;
(2) 50ml of Ca (NO) was measured3)2·4H2O ethanol solution, under the magnetic stirring environment of 250r/min at 50 ℃, Ca (NO) is added by an acid burette3)2·4H2Slowly dropping 75ml of P into the O ethanol solution2O5After the ethanol solution is added dropwise, stirring for 2 hours;
(3) gelling the uniformly stirred mixed solution in a water bath at 40 ℃ for 36h, and aging for 24h to obtain jelly;
(4) drying the colloidal substance in a forced air drying oven at 100 ℃ for 20h, then calcining in a box-type furnace at 700 ℃ for 1.5h, cooling and grinding to obtain hydroxyapatite;
(5) adding hydroxyapatite into the graphene conductive slurry according to the doping amount of 8 wt%, and uniformly mixing to obtain the functional heating slurry for degrading organic pollutants.
Example 3
(1) 35.423g of Ca (NO) was accurately weighed3)2·4H2O, adding into 100ml of absolute ethyl alcohol to prepare Ca (NO) with the concentration of 1.5mol/L3)2·4H2O ethanol solution; 8.516g of P are accurately weighed2O5Adding into 100ml of absolute ethyl alcohol to prepare P with the concentration of 0.6mol/L2O5Ethanol solution;
(2) 75ml of Ca (NO) was measured3)2·4H2Adding alcohol solution of O, stirring at 40 deg.C and 300r/min under magnetic stirring, and adding acid burette to Ca (NO)3)2·4H2Slowly dropping 75ml of P into the O ethanol solution2O5After the ethanol solution is added dropwise, stirring for 2 hours;
(3) gelling the uniformly stirred mixed solution in a water bath at 50 ℃ for 24h, and aging for 30h to obtain jelly;
(4) drying the colloidal substance in a blast drying oven at 120 ℃ for 16h, calcining in a box furnace at 700 ℃ for 1.5h, cooling and grinding to obtain hydroxyapatite;
(5) adding hydroxyapatite into the graphene conductive slurry according to the doping amount of 4 wt%, and uniformly mixing to obtain the functional heating slurry for degrading organic pollutants.
The functional heating slurries prepared in examples 1 to 3 were subjected to an electric heating capacity test and an organic pollutant degradation capacity test under the same conditions, respectively. Wherein the electrothermal capability test is to observe the temperature distribution of the functional heating slurry under the voltage of 20V after the functional heating slurry is printed by a screen; the organic pollutant degradation capability test is to test the formaldehyde degradation capability of the functionally heated slurry at a heating temperature of 80 ℃. Tests show that the functional heating slurry prepared in the embodiments 1 to 3 has better electric heating capacity and organic matter degradation capacity, wherein fig. 1 is an XRD (X-ray diffraction) diagram of hydroxyapatite prepared in the embodiment 1 of the invention, and fig. 2 is an SEM (scanning Electron microscope) diagram of hydroxyapatite prepared in the embodiment 1 of the invention, which illustrates that nano-scale hydroxyapatite can be successfully prepared by using the preparation method in the embodiment of the invention; FIG. 3 is a photograph of a heating image at a voltage of 20V after screen printing of the functional heating paste prepared in example 1 of the present invention, which shows that the thermal conductive paste still has good and stable heating ability after adding a proper amount of hydroxyapatite to the thermal conductive paste; fig. 4 is a formaldehyde degradation curve of the functional heating slurry prepared in example 1 of the present invention at a heating temperature of 80 ℃, which illustrates that after a proper amount of hydroxyapatite is added to the thermal conductive slurry, the thermal conductive slurry can rapidly decompose formaldehyde, and has a strong degradation capability on organic pollutants. Therefore, the functional heating slurry prepared by the embodiment of the invention has the advantages of good electric heating function and organic pollutant degradation function, simple preparation, low cost, stable heating performance and high organic pollutant degradation speed.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A functional heating slurry capable of degrading organic pollutants is characterized by comprising an electric heating slurry and hydroxyapatite.
2. The functionally heated paste according to claim 1, wherein the hydroxyapatite is added in an amount of 1 to 20 wt% based on the electrically heated paste,
optionally, the doping amount of the hydroxyapatite is 3-10 wt% of the electrothermal slurry.
3. Functionally heated slurry according to claim 1 or 2, characterized in that at least one of the following conditions is fulfilled:
the electric heating slurry is carbon-based conductive slurry and/or metal conductive slurry;
the particle size of the hydroxyapatite is 1-500 nm.
4. A method of preparing the functionally heated slurry of any one of claims 1 to 3, comprising:
(1) respectively adding Ca (NO)3)2·4H2O and P2O5Mixing with anhydrous ethanol to obtain Ca (NO)3)2·4H2Oethanol solution and P2O5Ethanol solution;
(2) under stirring, adding said P2O5Dripping ethanol solution into the Ca (NO)3)2·4H2In an O ethanol solution to obtain a mixed solution;
(3) gelling and aging the mixed solution under the condition of water bath so as to obtain jelly;
(4) drying, calcining and grinding the jelly in sequence so as to obtain nano-grade hydroxyapatite;
(5) and mixing the hydroxyapatite with the electric heating slurry according to a preset proportion so as to obtain the functional heating slurry capable of degrading organic pollutants.
5. The method of claim 4, wherein in step (1), the step (c) is performed by a computerCa(NO3)2·4H2The concentration of the O ethanol solution is 0.5-2 mol/L, and the P is2O5The concentration of the ethanol solution is 0.2-1 mol/L.
6. The method of claim 4, wherein at least one of the following conditions is satisfied:
in the step (2), the Ca (NO)3)2·4H2O ethanol solution and the P2O5The mixing volume ratio of the ethanol solution is (0.4-3): 1;
in the step (2), the stirring speed is 200-400 r/min, and the stirring time is 0.5-2 h;
in the step (2), under the condition of magnetic stirring, the P is added by using an acid burette2O5Dripping ethanol solution into the Ca (NO)3)2·4H2And (4) in the O ethanol solution, continuously stirring for 0.5-2 h after the mixing is finished.
7. The method as claimed in claim 5 or 6, wherein in the step (3), the water bath temperature is 30-70 ℃, the gelling time is 12-36 h, and the aging time is 12-36 h.
8. The method according to claim 7, wherein in the step (4), the drying temperature is 80 to 150 ℃, the calcining temperature is 400 to 800 ℃, and the calcining time is 0.5 to 4 hours.
9. Use of the functional heating paste according to any one of claims 1 to 3 or the functional heating paste obtained by the production method according to any one of claims 4 to 8 for heating and air purification.
10. An electrothermal film, characterized in that it is prepared by using the functional heating paste of any one of claims 1 to 3 or the functional heating paste obtained by the preparation method of any one of claims 4 to 8.
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