CN114534717A - Birnessite @ hydrated calcium silicate composite material and preparation and application thereof - Google Patents
Birnessite @ hydrated calcium silicate composite material and preparation and application thereof Download PDFInfo
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- CN114534717A CN114534717A CN202210182445.0A CN202210182445A CN114534717A CN 114534717 A CN114534717 A CN 114534717A CN 202210182445 A CN202210182445 A CN 202210182445A CN 114534717 A CN114534717 A CN 114534717A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to the technical field of formaldehyde catalysis, and particularly relates to a birnessite @ hydrated calcium silicate composite material which comprises a hydrated calcium silicate substrate and birnessite growing on the surface of the substrate in situ. The invention also comprises a preparation method of the material and application of the material in formaldehyde catalytic degradation. The research of the invention finds that the material has good normal-temperature formaldehyde removal capability.
Description
Technical Field
The invention belongs to the technical field of materials for reducing environmental pollution and harm, and particularly relates to a birnessite @ hydrated calcium silicate composite material for efficiently degrading formaldehyde.
Technical Field
With the improvement of the living standard of human beings, people pay more and more attention to interior decoration. But formaldehyde brought by the interior decoration material also becomes a killer harmful to human health. The adhesives used in artificial boards such as plywood, fiberboard and flakeboard for interior decoration all use formaldehyde as the main component. Wall coverings, wall papers, chemical fiber carpets, paints, coatings, and the like also contain formaldehyde components. These building decoration materials containing formaldehyde are gradually released to the surrounding indoor environment, and are the main body of formaldehyde in indoor polluted air. Since human beings are killed by long-term exposure to low-concentration formaldehyde and are recognized as a carcinogen by the world health organization, development and application of materials for catalyzing and oxidizing formaldehyde gas at room temperature are urgently needed.
Most of the prior treatments for indoor formaldehyde gas rely on adsorption substances, but the substances are unstable to the adsorption of formaldehyde, and the formaldehyde is easily released again after the adsorption is saturated. In addition, the formaldehyde gas is degraded by using a photocatalyst, but the formaldehyde gas needs the assistance of external conditions, for example, ultraviolet irradiation is needed to activate the formaldehyde gas, so that the further application of the formaldehyde gas is limited. Therefore, in practical applications, these substances cannot guarantee the treatment of formaldehyde in indoor air.
Birnessite as the most widely distributed manganese oxide ore in soil is composed of a layer of MnO6The octahedron is formed by alternately stacking a water molecule layer containing different cations and has large specific surface area (up to 50-300 m)2Per gram), low zero charge (1.5-2.5), high cation exchange capacity (0.63-2.40mol/Kg), and high oxidizing ability. Due to the unique physical and chemical properties, the catalyst can be applied to various fields, particularly catalytic oxidation. Birnessite has high activity and low toxicity, and the unique d-orbit can easily realize the transition of outer electrons between different energy levels to show the redox characteristic. However, the catalytic performance of birnessite on formaldehyde reported in the prior art is still low at room temperature, and the formaldehyde can be removed at a higher temperature. The prior art also lacks a material which can still show good formaldehyde removal performance under the condition of normal temperature.
Disclosure of Invention
Aiming at the technical problem that the formaldehyde catalytic performance, particularly the room-temperature catalytic performance, of the existing birnessite material is not ideal, the invention provides a birnessite @ hydrated calcium silicate composite material, and aims to provide a new material with good catalytic performance, particularly the room-temperature catalytic performance.
The second purpose of the invention is to provide a preparation method of the birnessite @ calcium silicate hydrate composite material.
The third purpose of the invention is to provide the application of the birnessite @ calcium silicate hydrate composite material in the aspect of formaldehyde degradation. In particular, by utilizing the advantage of wide application of hydrated calcium silicate in building materials and doping birnessite in the hydrated calcium silicate, the novel indoor building material with long-term effective and autocatalytic formaldehyde degradation function is prepared.
The shape uniformity of the conventional birnessite is not ideal, and the conventional birnessite is usually a micron-sized material, the performance of the material in the aspect of formaldehyde catalysis needs to be improved, for example, the formaldehyde degradation performance at normal temperature is poor, and the material is limited in practical application, in addition, the birnessite is black, and is difficult to fully meet modern variable aesthetic requirements, and aiming at the technical problem, the invention provides the following technical scheme:
a birnessite @ calcium silicate hydrate composite material comprises a calcium silicate hydrate substrate and birnessite growing on the surface of the substrate in situ.
The birnessite is innovatively loaded on the hydrated calcium silicate substrate in situ, and based on the cooperation of the components and the in-situ growth structure, the formaldehyde catalytic performance of the material can be effectively improved, particularly the normal-temperature catalytic performance of the material is favorably improved, and the indoor normal-temperature formaldehyde is favorably realized.
In the invention, the birnessite is formed by in-situ epitaxial growth on the surface of a hydrated calcium silicate substrate. In the invention, the birnessite grows on the surface of the substrate in an epitaxial manner, so that the synergistic advantages of components and structures are brought into play, and the formaldehyde removal effect of the material at normal temperature is further improved.
The research of the invention also finds that the morphological structure of the birnessite grown in situ is further controlled, which is beneficial to unexpectedly further improving the cooperativity of the composite components and the in situ load structure, and is beneficial to further improving the formaldehyde catalytic performance of the material, in particular to improving the normal temperature catalytic performance of the material.
The birnessite is a material with a porous secondary structure formed by staggered assembly of birnessite sheet layers growing on the surface of a substrate.
The composite material is a porous spherical birnessite anchored on the surface of hydrated calcium silicate and is firmly combined;
preferably, the calcium silicate hydrate is at least one of amorphous C-S-H (calcium silicate hydrate) solid gel, tobermorite, scolecite, wollastonite and orthosillimanite. The calcium silicate hydrate is a material with a rod-shaped, sheet-shaped and whisker-shaped structure.
Preferably, the mass ratio of the hydrated calcium silicate to the birnessite is 0.5-3: 1.
the invention also provides a preparation method of the birnessite @ calcium silicate hydrate composite material, which comprises the following steps:
the method comprises the following steps:
step (1):
mixing (premixing) a divalent manganese source, calcium silicate hydrate and a surfactant to obtain a suspension;
step (2):
adding permanganate A into the suspension obtained in the step (1) to perform a first reaction; wherein the molar ratio of the permanganate A to the divalent manganese source is 0.5-2: 1;
and (3):
adding permanganate B into the reaction system in the step (2), sealing the mixed solution in a container, heating to perform a second reaction, and separating after the reaction is finished to obtain birnessite @ hydrated calcium silicate composite material;
the molar ratio of the permanganate B to the divalent manganese source is 0.5-5: 1;
the temperature of the second reaction is 160-250 ℃.
The research of the invention finds that how to grow the birnessite on the surface of the hydrated calcium silicate and how to regulate the appearance of the birnessite are key difficulties in successfully preparing the material and improving the catalytic performance of the formaldehyde of the material. Aiming at the preparation difficulty, the inventor finds that the hydrated calcium silicate and the divalent manganese source are premixed under the assistance of a surfactant in advance, then the premixed hydrated calcium silicate and the divalent manganese source are subjected to a first reaction with permanganate A and then subjected to a second reaction with permanganate B, based on the two-stage reaction thought, the control of each condition is further matched, the synergy can be unexpectedly realized, the nucleation and the crystal epitaxial growth can be induced under the induction of the hydrated calcium silicate, the in-situ induced growth of the birnessite on the surface of the hydrated calcium silicate can be facilitated, the structure of the grown birnessite can be regulated, and therefore the formaldehyde catalytic performance of the prepared material can be improved.
In the present invention, the calcium silicate hydrate can be prepared based on the existing method. Researches also find that in order to further facilitate the in-situ epitaxial growth of the birnessite and the formaldehyde catalysis performance of the material, the material is preferably obtained by performing hydrothermal reaction on a mixed aqueous solution of a silicon-calcium raw material and alkali at the temperature of 100-250 ℃.
Preferably, the silicon-calcium raw material comprises a silicon source and a calcium source;
the silicon source is, for example, at least one of high-silicon materials including fly ash, coal gangue, chemical sodium silicate, soil ore, clay, tailings, quartz ore and secondary tailings containing silicon;
the calcium source is at least one of calcium oxide, calcium hydroxide and calcium carbonate;
preferably, the alkali is at least one of sodium hydroxide and potassium hydroxide;
preferably, the molar ratio of silicon to calcium in the mixed aqueous solution is, for example, 1.2 to 5.5:1, and more preferably 1.5 to 2.5: 1;
preferably, the molar ratio of the alkali to the silicon in the silicon-calcium raw material is, for example, 0.5-4: 1, and more preferably 2-3: 1;
preferably, the concentration of the alkali in the mixed water solution is 3-20 g/L, preferably 10-15 g/L;
preferably, the temperature of the hydrothermal reaction is 130-230 ℃. Researches find that the calcium silicate hydrate with a good second reaction structure and appearance is prepared at a preferable temperature, so that the calcium silicate hydrate is beneficial to cooperating with a subsequent treatment process, inducing in-situ epitaxial growth of the birnessite and being beneficial to the formaldehyde catalytic performance of the prepared material.
Preferably, the time of the hydrothermal reaction is 0.5-4 h.
The research of the invention finds that the premixing of the hydrated calcium silicate and the divalent manganese source under the surfactant, the stepwise two-stage reaction idea of the permanganate and the combined control of the synthesis conditions are the key points for improving the structure and the appearance of the material and the degradation performance of the formaldehyde.
In the present invention, calcium silicate hydrate and Mn are preliminarily mixed2+And performing liquid phase mixing under the source and the surfactant, and infiltrating Mn on the surface of the hydrated calcium silicate, so that the in-situ induced growth of the birnessite in the subsequent two-stage range is facilitated.
Preferably, the solvent used for liquid phase mixing is water or a water-organic solvent mixture, and the organic solvent is an organic solvent miscible with water. Examples of the organic solvent include alcohols of C1 to C4, and acetone.
In the invention, the divalent manganese source can ionize Mn2+The water-soluble compound of (1); preferably at least one of manganese sulfate, manganese nitrate, manganese chloride and manganese acetate, or manganese ore extract. The source of divalent manganese may be a commercial chemical feedstock or may be derived from a mineral smelting feed (e.g. a leach solution).
Preferably, Mn in suspension2+The design molar concentration of (A) is 0.1-2M; more preferably 0.1 to 0.5M.
Preferably, the surfactant is at least one of a cationic surfactant, an anionic surfactant and a nonionic surfactant; nonionic surfactants are preferred. The research unexpectedly finds that the nonionic surfactant can synergistically obtain a better preparation effect and further improve the formaldehyde catalytic performance of the prepared material.
Preferably, the cationic surfactant is at least one of cetyl trimethyl ammonium bromide, benzalkonium chloride and benzalkonium bromide;
preferably, the anionic surfactant is at least one of sodium dodecyl benzene sulfonate, ammonium dodecyl sulfate and sodium dodecyl sulfate;
preferably, the nonionic surfactant is at least one of polyethylene glycol, polyhydric alcohol type and polyether type;
preferably, the mass ratio of the calcium silicate hydrate to the surfactant to the divalent manganese source is 0.5-5: 0.1-2: 1; more preferably 2 to 5:0.5 to 1.5: 1.
Preferably, in the step (1), the solvent mixed with the liquid phase is water or a mixed solvent of water and an organic solvent, and the organic solvent is an organic solvent miscible with water.
In the invention, the premixing stage can be carried out at room temperature, the premixing time has no special requirement, and the premixing is uniform, for example, the mixing time can be 0.2-1.5 h.
In the invention, on the basis of the premixing, the subsequent two-stage reaction is further matched, so that the in-situ epitaxial growth of the birnessite on the surface of the calcium silicate bloom can be induced.
The permanganate A can ionize to form MnO4The water-soluble salt of (a) is preferably at least one of potassium permanganate, sodium permanganate, and magnesium permanganate.
The research of the invention finds that the permanganate A is added into the suspension, and the adding proportion is further controlled, so that the morphology of the material prepared under the two-stage reaction mechanism can be further improved unexpectedly, and the formaldehyde degradation performance can be further improved.
Preferably, permanganate A (in MnO)4-in) in a molar ratio of 0.5 to 1:1 with respect to the source of divalent manganese; more preferably 0.5 to 0.6: 1.
The first reaction is performed under stirring, for example, the stirring speed in the first reaction process is 50 to 300 r/min.
In the present invention, the first invention may be carried out at room temperature, for example, the reaction temperature is, for example, 15 to 45 ℃.
Preferably, in the step (1), the time of the first reaction process is 0.5-3 h; more preferably 1 to 2 hours.
In the present invention, permanganate B solid particles are added to a first reaction system, and the mixed solution is placed in a pressure-resistant container, which is then closed and heated to carry out a second reaction. Researches find that the control of the addition amount of the permanganate B in the second reaction stage and the reaction temperature is beneficial to obtaining materials with better formaldehyde catalytic degradation performance.
In the invention, the molar ratio of the permanganate B to the divalent manganese source is 1-2: 1; more preferably 1.5 to 2: 1.
Preferably, the temperature of the second reaction is 180 to 240 ℃.
Preferably, the second reaction time is 12-48 h; further preferably 15 to 24 hours.
In the invention, after the second reaction is finished, the solid-liquid separation is carried out on the product, and the product is obtained after washing and drying.
The invention also provides the birnessite @ calcium silicate hydrate composite material prepared by the preparation method.
The invention also provides application of the birnessite @ calcium silicate hydrate composite material in catalytic degradation of formaldehyde.
The research of the invention finds that the material has good formaldehyde degradation performance, particularly excellent room-temperature formaldehyde catalytic degradation performance, and has more acceptable color and can meet the modern aesthetic requirements.
Preferably, the application is to add the formaldehyde-containing composite into building materials for catalyzing the degradation of formaldehyde.
Advantageous effects
1. The invention provides a birnessite @ calcium silicate hydrate composite material, and the brand new material is found to have good formaldehyde catalytic performance, particularly good normal-temperature catalytic performance;
2. the invention also provides a preparation method of the birnessite @ calcium silicate hydrate composite material, which innovatively uses calcium silicate hydrate and Mn2+The method is characterized in that premixing is carried out under a surfactant, and the two-stage reaction idea of permanganate and the combined control of conditions such as the ratio of two-stage materials, the temperature and the like are further utilized, so that the synergy can be realized unexpectedly, the generation of the birnessite can be induced on the surface of the hydrated calcium silicate in situ, the morphological structure of the birnessite can be regulated, and the electrochemical performance of the prepared material can be improved.
3. The invention has simple preparation process and low cost, does not need to add a modifier and is environment-friendly. The birnessite composite material prepared by the method has the advantages of rich pore canal structure, good stability and higher specific surface area, and can have important application value in various fields such as adsorption, catalysis, oxidative degradation materials, air purification materials and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a birnessite @ calcium silicate hydrate composite prepared in example 1;
FIG. 2 is a scanning electron microscope photograph of the material prepared in comparative example 1;
FIG. 3 is a scanning electron microscope image of the material prepared in comparative example 2;
FIG. 4 is a scanning electron microscope image of the material prepared in comparative example 3;
FIG. 5 is a scanning electron microscope photograph of the material prepared in comparative example 4;
FIG. 6 is a scanning electron microscope photograph of the material prepared in comparative example 5;
FIG. 7 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 2;
FIG. 8 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 3;
FIG. 9 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 4;
FIG. 10 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 5;
FIG. 11 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 6;
FIG. 12 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 7;
FIG. 13 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 8;
FIG. 14 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 9;
FIG. 15 is a scanning electron microscope image of birnessite @ calcium silicate hydrate composite prepared in example 10;
the specific implementation mode is as follows:
the method for recording the catalytic degradation step of formaldehyde and measuring data comprises the following steps:
determination of the catalytic Activity of the catalyst on HCHO (80 ppm): 0.1g of catalyst powder having a particle size of 200-. The total flow rate is 100ml min-1Corresponding to 60 L.h-1·g-1Gas Hourly Space Velocity (GHSV). Once the given reaction temperature was reached, the catalyst was stable for 1 hour. The reaction products were detected on-line using a gas chromatography-mass spectrometer equipped with a thermal conductivity detector. Conversion to CO by HCHO2The catalytic activity of the catalyst was evaluated. HCHO conversion of the sample was calculated using the following formula
Wherein [ HCHO ]]in and [ CO ]2]inRespectively import HCHO and CO2Concentration of [ CO ]2]outRepresenting the outlet CO2And (4) concentration.
The room temperature is, for example, 20 to 35 ℃.
In the following cases, the temperature of the premixing step (2) is not particularly required, and is, for example, 15 to 45 ℃. The premixing process is preferably carried out under stirring, and the rotation speed of the stirring is not particularly required, and may be, for example, 100 to 500 r/min.
The temperature of the first reaction process of step (3) may be at room temperature, for example, 15 to 45 ℃. The stirring speed in the reaction stage is, for example, 200 to 500 r/min.
Example 1
(1) Mixing sodium silicate, calcium oxide and sodium hydroxide with water to perform hydrothermal reaction, wherein the molar ratio of silicon to calcium in the raw material solution is 2: 1; the molar ratio of sodium hydroxide to silicon is 2: 1. the initial concentration of the alkali is 10 g/L; hydrothermal temperature of 150 ℃ and hydrothermal time of 3h, separating after reaction to obtain calcium silicate hydrate, and drying at 105 ℃ to obtain a calcium silicate hydrate base material;
(2) uniformly mixing calcium silicate hydrate powder, manganese nitrate and polyethylene glycol according to the mass ratio of 6:2:1, adding 100mL of water, stirring for 1h (premixing) to obtain a suspension (the concentration of Mn is 1M);
(3) stirring the suspension to obtain a suspension with a molar ratio of KMnO4：Mn2+(the manganese nitrate in the step (2) is added with potassium permanganate in a ratio of 0.57:1 to carry out a first reaction for 0.5 h;
(4) continuously adding the amount of the potassium permanganate and the Mn into the solution under the condition of rapid stirring2+(the molar ratio of the manganese nitrate in the step (2)) is 1.71:1, the mixture is uniformly stirred, the mixed solution is sealed in a container, the temperature is raised to 200 ℃ (second reaction), and the reaction is carried out for 20 hours;
(5) and (3) carrying out suction filtration and washing on the obtained turbid solution, transferring the powder into an oven, and drying for 10 hours at the temperature of 80 ℃ to obtain the birnessite composite material, wherein a scanning electron microscope picture of the birnessite composite material is shown in an attached figure 1, and the degradation rate of the birnessite composite material on formaldehyde gas is shown in a table 1.
Comparative example 1
The only difference compared to example 1 is that the pre-mixing of step (2) was not performed in advance, but calcium silicate hydrate was added to the system after the first reaction of step (3);
the scanning electron microscope picture is shown in the attached figure 2, and the degradation rate of the formaldehyde gas is shown in the table 1.
Comparative example 2
Compared with example 1, the difference is only that no surfactant is added in step (2);
the scanning electron microscope picture of the birnessite composite material with high efficiency formaldehyde degradation prepared in the embodiment is shown in the attached figure 3, and the degradation rate of formaldehyde gas is shown in table 1.
Comparative example 3
Compared with example 1, the difference is only that Mn in step (3)2+The molar ratio of the potassium permanganate to the potassium permanganate is 1: 0.01; the total amount was the same as in example 1, the balance being added in the second reaction stage;
the scanning electron microscope picture is shown in figure 4, and the degradation rate of the formaldehyde gas is shown in table 1.
Comparative example 4
Compared with example 1, the difference is only that the second reaction temperature in step (4) is 40 ℃;
the scanning electron microscope picture of the birnessite composite material with high efficiency formaldehyde degradation prepared in the embodiment is shown in figure 5, and the degradation rate of formaldehyde gas is shown in table 1.
Comparative example 5
Compared with example 1, the difference is only that the second reaction temperature in step (4) is 120 ℃;
the scanning electron microscope picture of the birnessite composite material with high efficiency formaldehyde degradation prepared in the embodiment is shown in figure 6, and the degradation rate of formaldehyde gas is shown in table 1.
Example 2
Compared with example 1, the difference is only that the calcium silicate hydrate substrate in step (1) is prepared at 130 ℃;
the scanning electron microscope picture of the birnessite composite material with high formaldehyde degradation efficiency prepared in the embodiment is shown in the attached figure 7, and the degradation rate of the birnessite composite material to formaldehyde gas is shown in the table 1.
Example 3
Compared with example 1, the difference is only that the calcium silicate hydrate in the step (1) is prepared at 230 ℃;
the scanning electron microscope picture of the birnessite composite material capable of efficiently degrading formaldehyde prepared by the embodiment is shown in the attached figure 8, and the degradation rate of the birnessite composite material on formaldehyde gas is shown in table 1.
Example 4
Compared with example 1, the difference is only that the calcium silicate hydrate substrate in step (1) is prepared at 170 ℃;
the scanning electron microscope picture of the birnessite composite material with high efficiency formaldehyde degradation prepared in the embodiment is shown in figure 9, and the degradation rate of formaldehyde gas is shown in table 1.
Example 5
Compared with the example 1, the difference is only that the surfactant added in the step (1) is sodium dodecyl benzene sulfonate;
the scanning electron microscope picture is shown in figure 10, and the degradation rate of the formaldehyde gas is shown in table 1.
Example 6
Compared with example 1, the difference is only that Mn in step (3)2+The molar ratio of the potassium permanganate to the potassium permanganate is 1: 0.6; other parameters and operations were the same as in example 1.
The scanning electron microscope picture of the birnessite composite material with high efficiency degradation of formaldehyde prepared in the embodiment is shown in the attached figure 11, and the degradation rate of formaldehyde gas is shown in table 1.
Example 7
Compared with example 1, the difference is only that Mn in step (3)2+The molar ratio of the potassium permanganate to the potassium permanganate is 1: 0.5; other parameters and operations were the same as in example 1.
The scanning electron microscope picture of the birnessite composite material with high efficiency degradation of formaldehyde prepared in the embodiment is shown in figure 12, and the degradation rate of formaldehyde gas is shown in table 1.
Example 8
Compared with example 1, the difference is only that Mn in step (3)2+The molar ratio of the potassium permanganate to the potassium permanganate is 1: 2; other parameters and operations were the same as in example 1.
The scanning electron microscope picture of the birnessite composite material with high efficiency formaldehyde degradation prepared in the embodiment is shown in the attached figure 13, and the degradation rate of formaldehyde gas is shown in table 1.
Example 9
Compared with example 1, the difference is only that the second reaction temperature in step (4) is 240 ℃;
the scanning electron microscope picture of the birnessite composite material with high efficiency degradation of formaldehyde prepared in the embodiment is shown in the attached figure 14, and the degradation rate of formaldehyde gas is shown in table 1.
Example 10
Compared with example 1, the difference is only that the second reaction temperature in step (4) is 180 ℃;
the scanning electron microscope picture of the birnessite composite material with high efficiency formaldehyde degradation prepared in the embodiment is shown in the attached figure 15, and the degradation rate of the birnessite composite material to formaldehyde gas is shown in table 1.
The conversion data of formaldehyde of examples 1 to 10 and comparative examples 1 to 5 at different temperatures are shown in Table 1
As can be seen from table 1, the calcium silicate hydrate of the present invention is added in the first stage reaction process, and further, in combination with the addition amount and the addition rate of the first stage reaction, the addition of the surfactant type, and the cooperative control of the second reaction temperature of the second stage reaction, the catalytic oxidation performance of the material can be greatly improved, and the present invention is helpful for improving the low-temperature and high-temperature catalytic oxidation performance, particularly, the catalytic performance at room temperature can be effectively improved, and the present invention has a greater practical application prospect. In addition, compared with the single birnessite, the composite material disclosed by the invention can obtain equivalent or even better effect under the condition of lower birnessite content, and moreover, the composite material is lighter in color and can meet the aesthetic requirements of modern indoor decoration.
Claims (10)
1. The birnessite @ calcium silicate hydrate composite material is characterized by comprising a calcium silicate hydrate substrate and birnessite growing on the surface of the substrate in situ.
2. The birnessite @ calcium silicate hydrate composite material of claim 1, wherein the birnessite is formed by in-situ epitaxial growth on the surface of a calcium silicate hydrate substrate;
preferably, the hydrated calcium silicate is at least one of amorphous C-S-H solid gel, tobermorite, scolecite, wollastonite and clinoptilolite;
preferably, the birnessite is a material of a porous secondary structure formed by assembling birnessite lamella primary structures growing on the surface of the substrate in a staggered mode;
preferably, the mass ratio of the calcium silicate hydrate to the birnessite is 0.5-3: 1.
3. the method of preparing birnessite @ calcium silicate hydrate composite material of claim 1, comprising the steps of:
step (1):
mixing a divalent manganese source, calcium silicate hydrate and a surfactant to obtain a suspension;
step (2):
adding permanganate A into the suspension obtained in the step (1) to perform a first reaction; wherein the molar ratio of the permanganate A to the divalent manganese source is 0.5-2: 1;
and (3):
adding permanganate B into the reaction system in the step (2), sealing the mixed solution in a container, heating to perform a second reaction, and separating after the reaction is finished to obtain birnessite @ hydrated calcium silicate composite material;
the molar ratio of the permanganate B to the divalent manganese source is 0.5-5: 1;
the temperature of the second reaction is 160-250 ℃.
4. The preparation method of birnessite @ calcium silicate hydrate composite material as claimed in claim 3, wherein the calcium silicate hydrate is obtained by hydrothermal reaction of a mixed aqueous solution of a silicon-calcium raw material and an alkali at a temperature of 100-250 ℃;
preferably, the silicon-calcium raw material comprises a silicon source and a calcium source;
the silicon source is at least one of high-silicon materials including fly ash, coal gangue, chemical sodium silicate, soil ore, clay, tailings, quartz ore and secondary tailings containing silicon;
the calcium source is at least one of calcium oxide, calcium hydroxide and calcium carbonate;
preferably, the alkali is at least one of sodium hydroxide and potassium hydroxide;
preferably, in the mixed aqueous solution, the molar ratio of silicon to calcium is 1.2-5.5: 1;
preferably, the molar ratio of the alkali to the silicon in the silicon-calcium raw material is 0.5-4: 1;
preferably, the concentration of alkali in the mixed aqueous solution is 3-20 g/L;
preferably, the time of the hydrothermal reaction is 0.5-4 h.
5. The method for preparing birnessite @ calcium silicate hydrate composite material of claim 3, wherein the surfactant is at least one of cationic surfactant, anionic surfactant and nonionic surfactant; preferably a nonionic surfactant;
preferably, the cationic surfactant is at least one of cetyl trimethyl ammonium bromide, benzalkonium chloride and benzalkonium bromide;
preferably, the anionic surfactant is at least one of sodium dodecyl benzene sulfonate, ammonium dodecyl sulfate and sodium dodecyl sulfate;
preferably, the nonionic surfactant is at least one of polyethylene glycol, polyhydric alcohol type and polyether type;
preferably, the divalent manganese source is Mn2+Water-soluble salts of (a);
preferably, the mass ratio of the calcium silicate hydrate to the surfactant to the divalent manganese source is 0.5-5: 0.1-2: 1; further preferably 2-5: 0.5-1.5: 1;
preferably, in the step (1), the liquid-phase mixed solvent is water or a water-organic solvent mixed solvent, and the organic solvent is an organic solvent miscible with water;
preferably, Mn in suspension2+The design molar concentration of (a) is 0.1-2M.
6. The method for preparing birnessite @ calcium silicate hydrate composite material of claim 3, wherein the permanganate A and the permanganate B are capable of ionizing to obtain MnO4The water-soluble salt of (a) is preferably at least one of potassium permanganate, sodium permanganate, and magnesium permanganate.
7. The method for preparing birnessite @ calcium silicate hydrate composite material according to claim 3, wherein the temperature in the first reaction stage is 15-45 ℃;
preferably, the time of the first reaction is 0.5-3 h.
8. The preparation method of birnessite @ calcium silicate hydrate composite material as claimed in claim 3, wherein the time of the second reaction stage is 8-30 h.
9. The application of birnessite @ calcium silicate hydrate composite material as defined in any one of claims 1-2 or birnessite @ calcium silicate hydrate composite material prepared by the preparation method as defined in any one of claims 3-8 is characterized in that the birnessite @ calcium silicate hydrate composite material is used as a catalyst for catalytic degradation of formaldehyde gas.
10. Use according to claim 9, for the catalytic degradation of formaldehyde gas, directly prepared as building material for indoor use or added to building material.
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