CN110803787A - Nano composite material and preparation method and application thereof - Google Patents
Nano composite material and preparation method and application thereof Download PDFInfo
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- CN110803787A CN110803787A CN201911257815.7A CN201911257815A CN110803787A CN 110803787 A CN110803787 A CN 110803787A CN 201911257815 A CN201911257815 A CN 201911257815A CN 110803787 A CN110803787 A CN 110803787A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
Abstract
The invention provides a nano composite material and a preparation method and application thereof. The nanocomposite material includes a solid acid support and a chelating agent supported on the solid acid support. The preparation method comprises the following steps: (1) preparing a solid acid carrier suspension; (2) mixing the solid acid carrier suspension with a chelating agent to obtain a mixed suspension; (3) and carrying out solid-liquid separation on the mixed suspension to obtain the nano composite material. The nano composite material provided by the invention firmly fixes the chelating agent on the surface of the carrier through hydrogen bond action, realizes strong combination among monomer materials, widens the application field of the material and has excellent sewage softening performance.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a nano composite material, and a preparation method and application thereof.
Background
When the water contains more soluble calcium and magnesium ions, the water quality is hard, and the water is also called hard water. The use of hard water easily causes the production of incrustation scale, and for equipment, the incrustation scale easily causes pipeline jam, causes equipment trouble, and in addition, the heat conductivity of incrustation scale is 30-40 times less than steel, also can seriously influence heat transfer effect, increases the energy consumption, and even the local overheat of interface that arouses by it can lead to serious consequences such as equipment explosion. In daily life, the use of hard water deteriorates the detergency of a detergent, deteriorates the texture of cooked food, and causes inconvenience in daily life. It is therefore necessary to soften hard water.
The existing technical methods for softening hard water mainly comprise a chemical precipitation method, an ion exchange method, a membrane separation method, an electromagnetic method, a scale inhibitor adding method and an adsorption method, wherein the water treated by the chemical precipitation method still contains high calcium and magnesium ions; the synthetic process of the artificial synthetic resin used by the ion exchange method is complicated, and a large amount of organic waste liquid is generated in the production process, so that secondary pollution is caused; the investment and the operation cost of the membrane separation method are high, and the membrane is easy to pollute and scrap; the softening effect of the electromagnetic method is unstable; the scale inhibitor adding method limits the application range of the scale inhibitor because the medicament is dissolved in water. The adsorption method can thoroughly remove impurities in water through physical and chemical adsorption, and has simple process and high purification rate, but in most reports at present, common adsorbents such as activated carbon, zeolite and the like have poor adsorption performance on calcium and magnesium ions and have poor softening effect on hard water.
Nitrilotriacetic acid trisodium salt is an organic polycarboxylate chelating agent, has the characteristics of small molecules, strong chelating capacity, strong biodegradability and the like, and is widely applied to the industrial fields of catalysis, scale inhibition, electroplating and the like. However, the sodium-based phosphate is usually used for industrial scale inhibition due to high water solubility, and cannot be directly applied to scale inhibition of drinking water, and the like, so that the popularization and the use of the trisodium nitrilotriacetate are limited.
CN102633665A discloses a preparation method of a hydroxyalkylamide type hard water softener, which relates to the technical field of organic chemical synthesis, in particular to a preparation method of a hydroxyalkylamide type hard water softener for water-based metalworking fluids. However, the method is complicated to prepare, and the hard water softening effect is desired to be improved.
CN107720986A discloses an alkaline hard water softener, which is characterized by comprising the following raw materials in percentage by mass: 15-30% of sodium ethylene diamine tetracetate, 5-20% of benzisothiazolinone, 0.5-8% of phosphonobutane tricarboxylic acid and a proper amount of pure water. However, the method has complicated components and is difficult to prepare, and the hard water softening effect needs to be improved.
CN107416987A discloses a hard water softener and a preparation method and application thereof, belongs to the field of tap water treatment, and particularly relates to a hard water softener and a preparation method and application thereof. The hard water softener comprises the following components in percentage by weight: 15-25% of diatomite; 1-5% of sodium carbonate; 1-2% of sodium hydroxide; 10-20% of activated carbon; the balance of deionized water. However, the method has complicated components and is difficult to prepare, and the hard water softening effect needs to be improved.
CN104909473A discloses a hard water softener, which comprises the following raw material formula components, by mass, 10-15 parts of sodium carbonate, 10-15 parts of hydrogen peroxide, 15-20 parts of copperas, 5-8 parts of paraffin, 8-10 parts of propylene glycol, 10-12 parts of polyvinyl chloride, 12-15 parts of polyacrylamide, 15-20 parts of polyaluminium sulfate and 150-200 parts of purified water. However, the method has complicated components and is difficult to prepare, and the hard water softening effect needs to be improved.
CN109721171A discloses a hard water softener, which comprises the following raw material formula components, by mass, 8-10 parts of magnesium hydroxide, 8-10 parts of potassium chloride, 12-15 parts of blue sail, 3-5 parts of rosin, 6-8 parts of butanediol, 8-10 parts of polyethylene terephthalate, 10-12 parts of sodium acetate, 10-15 parts of carboxymethyl cellulose, and 120-150 parts of deionized water. However, the method has complicated components and is difficult to prepare, and the hard water softening effect needs to be improved.
Disclosure of Invention
Aiming at the defects of complicated preparation process, high production cost, large secondary pollution, poor performance and the like of hard water softening materials in the prior art, the invention aims to provide a nano composite material and a preparation method and application thereof. The nano composite material provided by the invention has the advantages of simple synthesis method, low production cost, greenness, reproducibility, wide application range and excellent adsorption performance, and can be industrially produced.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a nanocomposite material comprising a solid acid carrier and a chelating agent supported on the solid acid carrier.
The nano composite material provided by the invention uses the chelating agent to soften hard water, and is firmly fixed on the surface of the carrier through the hydrogen bond effect, so that the monomer materials are strongly combined, the application field of the material is widened, and the sewage softening performance is excellent.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the solid acid carrier is zirconium hydrogen phosphate. The zirconium hydrogen phosphate can firmly fix the nitrilotriacetic acid trisodium salt on the surface of the carrier through hydrogen bonds, so that strong combination among monomer materials is realized, and the application field of the material is widened.
The zirconium hydrogen phosphate is preferably α -zirconium hydrogen phosphate, and α -zirconium hydrogen phosphate has the advantages of easy preparation, better crystal form and larger specific surface area compared with the zirconium hydrogen phosphate with other structures.
Preferably, the chelating agent is nitrilotriacetic acid trisodium salt. Nitrilotriacetic acid trisodium salt is a biodegradable organic scale inhibitor and is very suitable for the invention.
Preferably, the mass ratio of the solid acid carrier to the chelating agent in the nanocomposite is 1:0.1 to 1:5, such as 1:0.1, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, and the like, but is not limited to the recited values, and other values not recited within this range of values are equally applicable. In the present invention, if the mass ratio of the solid acid carrier to the chelating agent is too high (i.e. too much carrier), the chelating agent loading is low, and the composite material has poor water softening performance: if the mass ratio of the solid acid carrier to the chelating agent is too low (i.e., too much chelating agent), the production cost is increased, and unnecessary waste of resources is caused.
In a preferred embodiment of the present invention, the nanocomposite has an average particle size of 300nm to 5 μm, for example, 300nm, 500nm, 1 μm, 2 μm, 3 μm, 4 μm or 5 μm, but the average particle size is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable. The material provided by the invention has the particle size possibly reaching the micron level, but the thickness is all the nanometer level, so the material still works as the nanometer composite material.
In a second aspect, the present invention provides a process for the preparation of a nanocomposite material as defined in the first aspect, comprising the steps of:
(1) preparing a solid acid carrier suspension;
(2) mixing the solid acid carrier suspension liquid obtained in the step (1) with a chelating agent to obtain a mixed suspension liquid;
(3) and (3) carrying out solid-liquid separation on the mixed suspension liquid obtained in the step (2) to obtain the nano composite material.
The preparation method provided by the invention has simple flow, and the nano composite material is synthesized by simple mixing in one step.
As a preferable technical scheme of the invention, the solid acid carrier in the step (1) is zirconium hydrogen phosphate.
Preferably, the zirconium hydrogen phosphate is α -zirconium hydrogen phosphate.
Preferably, the solid acid carrier of step (1) has an average particle size of 300nm to 5 μm, such as 300nm, 500nm, 1 μm, 2 μm, 3 μm, 4 μm or 5 μm, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the solvent of the solid acid carrier suspension of step (1) is water.
Preferably, the solid acid carrier suspension has a mass fraction of solid acid carrier of 15-50 wt%, such as 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%, etc., but is not limited to the recited values, and other unrecited values within the range are equally applicable.
In a preferred embodiment of the present invention, in step (2), the chelating agent is trisodium nitrilotriacetate.
Preferably, in step (2), the mass ratio of the solid acid carrier to the chelating agent is 1:0.1 to 1:5, such as 1:0.1, 1:0.5, 1:1, 1:2, 1:3, 1:4, or 1:5, but not limited to the recited values, and other unrecited values within this range of values are equally applicable.
Preferably, in the step (2), the mixing method is stirring.
Preferably, in step (2), the mixing time is 10min to 24h, such as 10min, 30min, 1h, 6h, 12h, 18h or 24h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, in the step (3), the solid-liquid separation method includes centrifugal separation.
As a preferable embodiment of the present invention, the step (3) further includes: and (4) washing, drying and crushing the solid obtained by solid-liquid separation.
Preferably, the method of washing comprises centrifugal washing.
Preferably, the method of drying comprises forced air drying.
Preferably, the temperature of the drying is 60 to 70 ℃, such as 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃ or 70 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the drying time is 10-14h, such as 10h, 11h, 12h, 13h or 14h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the method of crushing comprises grinding.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) preparing a solid acid carrier suspension;
wherein the solid acid carrier is α -zirconium hydrogen phosphate;
the average particle size of the α -zirconium hydrogen phosphate is 300nm-5 mu m;
the solvent of the solid acid carrier suspension is water;
in the solid acid carrier suspension, the mass fraction of the solid acid carrier is 15-50 wt%;
(2) adding nitrilotriacetic acid trisodium salt into the solid acid carrier suspension in the step (1), and stirring and mixing for 10min-24h to obtain a mixed suspension;
wherein the mass ratio of the solid acid carrier to the nitrilotriacetic acid trisodium salt is 1:0.1-1: 5;
(3) and (3) carrying out centrifugal separation on the mixed suspension liquid obtained in the step (2), carrying out centrifugal washing, carrying out forced air drying at the temperature of 60-70 ℃ for 10-14h, and grinding into powder to obtain the nano composite material.
The further preferable technical proposal adopts a novel inorganic layered nano material zirconium hydrogen phosphate (α -ZrP) as a carrier, adds a biodegradable organic scale inhibitor of nitrilotriacetic acid trisodium salt, takes water as a solvent, and synthesizes the nitrilotriacetic acid trisodium salt/zirconium hydrogen phosphate nano composite material by simple stirring in one step.
In a third aspect, the present invention provides the use of a nanocomposite as described in the first aspect as a hard water softener.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nano composite material provided by the invention uses a chelating agent, particularly preferably a biodegradable organic scale inhibitor nitrilotriacetic acid trisodium salt, and is firmly fixed on the surface of an inorganic layered nano material zirconium hydrogen phosphate (α -ZrP) carrier through hydrogen bonding, so that strong combination among monomer materials is realized, the application field of the material is widened, and the sewage softening performance is excellent.
(2) The preparation method provided by the invention is simple to operate, and the nano composite material is synthesized in one step by simple stirring, so that the industrial production prospect is good.
Drawings
FIG. 1(a) is a scanning electron micrograph of the nanocomposite provided in example 5;
FIG. 1(b) is a scanning electron micrograph of zirconium hydrogen phosphate provided in comparative example 2;
FIG. 2 is an XRD diffractogram of the nanocomposite (NTA/ZrP) provided in example 5, the trisodium nitrilotriacetate (NTA-3Na) used in example 5, and the zirconium hydrogen phosphate (α -ZrP) provided in comparative example 2.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1:
the nanocomposite was prepared as follows:
weighing 1.50g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 300nm, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 1h, then centrifugally washing with deionized water, then drying for 12h by air blowing at 65 ℃, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nano composite material.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 2
The nanocomposite was prepared as follows:
weighing 1.50g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 1.7 mu m, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 1h, then centrifugally washing by deionized water, then drying by air blowing at 65 ℃ for 12h, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nano composite material.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 3
The nanocomposite was prepared as follows:
weighing 1.50g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 5 mu m, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 1h, then centrifugally washing with deionized water, then drying for 12h by air blowing at 65 ℃, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nano composite material.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 4
The nanocomposite was prepared as follows:
weighing 750g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 300nm, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 1h, centrifugally washing with deionized water, then drying by air blowing at 65 ℃ for 12h, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nanocomposite.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 5
The nanocomposite was prepared as follows:
weighing 750g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 1.7 mu m, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 1h, then centrifugally washing with deionized water, then drying for 12h by air blowing at 65 ℃, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nano composite material.
Fig. 1(a) is a scanning electron microscope image of the nanocomposite provided in this embodiment, from which it can be seen that the nanocomposite has a good layered structure, a regular morphology, and a rough surface.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 6
The nanocomposite was prepared as follows:
weighing 750g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 5 mu m, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 1h, then centrifugally washing the suspension by deionized water, then drying for 12h by air blowing at 65 ℃, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nanocomposite.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 7
The nanocomposite was prepared as follows:
weighing 750g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 300nm, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:0.1, stirring for 1h, then centrifugally washing with deionized water, then drying for 12h by air blowing at 65 ℃, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nano composite material.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 8
The nanocomposite was prepared as follows:
weighing 750g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 300nm, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:5, stirring for 1h, centrifugally washing with deionized water, then drying by air blowing at 65 ℃ for 12h, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nanocomposite.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 9
The nanocomposite was prepared as follows:
weighing 750g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 300nm, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 10min, centrifugally washing with deionized water, drying for 12h by air blowing at 65 ℃, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nanocomposite.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 10
The nanocomposite was prepared as follows:
weighing 750g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 300nm, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 0.15, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 24 hours, centrifugally washing with deionized water, then drying by air blowing at 65 ℃ for 12 hours, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nanocomposite.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Example 11
The nanocomposite was prepared as follows:
weighing 1.50g of zirconium hydrogen phosphate (α -zirconium hydrogen phosphate) with the average particle size of 300nm, stirring and dispersing in water to form suspension with the mass fraction (w/w) of 5, then adding the trisodium nitrilotriacetate according to the mass ratio of the zirconium hydrogen phosphate to the trisodium nitrilotriacetate of 1:1, stirring for 1h, centrifugally washing with deionized water, then drying by air blowing at 65 ℃ for 12h, and finally grinding to obtain the powdery trisodium nitrilotriacetate/zirconium hydrogen phosphate nanocomposite.
The nanocomposite provided in this example includes an α -zirconium hydrogen phosphate carrier and trisodium nitrilotriacetate supported on the carrier.
The results of the performance testing of the nanocomposites provided in this example are shown in Table 1.
Comparative example 1
This comparative example used α -zirconium hydrogenphosphate with an average particle size of 300nm for comparison.
The results of the performance tests of the zirconium hydrogen phosphate of this comparative example are shown in Table 1.
Comparative example 2
This comparative example used α -zirconium hydrogenphosphate having an average particle diameter of 1.7 μm as a comparison.
FIG. 1(b) is a scanning electron micrograph of the zirconium hydrogen phosphate provided in this comparative example, from which it can be seen that the zirconium hydrogen phosphate has a uniform morphology and a relatively smooth surface.
FIG. 2 shows XRD diffractograms of the nanocomposite (NTA/ZrP) provided in example 5, the trisodium nitrilotriacetate (NTA-3Na) used in example 5, and the zirconium hydrogen phosphate (α -ZrP) provided in comparative example 2, from which it can be seen that the loading of the trisodium nitrilotriacetate did not affect the crystal form of the zirconium hydrogen phosphate, and the interlayer spacing did not increase, and the reaction proceeded mainly on the surface of the support.
The results of the performance tests of the zirconium hydrogen phosphate of this comparative example are shown in Table 1.
Comparative example 3
This comparative example used α -zirconium hydrogenphosphate with an average particle size of 5 μm for comparison.
The results of the performance tests of the zirconium hydrogen phosphate of this comparative example are shown in Table 1.
Test method
The tri-sodium nitrilotriacetate/zirconium hydrogen phosphate nano composite materials prepared in the same quality examples 1-11 and the zirconium hydrogen phosphate with different particle sizes in the comparative examples 1-3 are respectively used for softening simulated hard water, and the softening effect of the materials on water quality is evaluated by performing an adsorption performance test on calcium and magnesium ions according to GB5750-85 standard test method for domestic drinking water. Wherein the total hardness of the simulated hard water is 450mg/g (calculated by calcium carbonate). The test results are shown in Table 1.
TABLE 1
It can be seen from the above examples and comparative examples that the trisodium nitrilotriacetate/zirconium hydrogen phosphate nanocomposites obtained by compounding zirconium hydrogen phosphate with trisodium nitrilotriacetate prepared in examples 1-11 have a much better softening effect on hard water than the pure zirconium hydrogen phosphate in comparative examples 1-3. Comparing the removal rate of calcium and magnesium ions in hard water for the nitrilotriacetic acid trisodium salt/zirconium hydrogen phosphate nanocomposites prepared in examples 1-3 and examples 4-6, it can be seen that the adsorption property of the composite material remains stable after the reaction system is amplified five hundred times, which directly illustrates that the nitrilotriacetic acid trisodium salt/zirconium hydrogen phosphate nanocomposite can be industrially produced. In addition, the composite materials prepared in examples 1 to 3 or examples 4 to 6 have different adsorption properties, and the composite material has higher removal rate of calcium and magnesium ions by using zirconium hydrogen phosphate with smaller particle size as the carrier, probably because the smaller the particle size, the larger the specific surface area of the carrier per se and the larger the loading amount of trisodium nitrilotriacetate. In contrast, comparing the adsorption performance of the composite materials prepared in examples 4, 7 and 8, it can be seen that when the amount of trisodium nitrilotriacetate added in the reaction system is small, the adsorption performance of the prepared nanocomposite material is poor, probably because the reaction mass concentration is small, the reaction rate is slow, and the loading amount of trisodium nitrilotriacetate is not high. In contrast, it is known that the adsorption performance of the composite materials prepared in examples 4, 9 and 10 is poor when the reaction time is 10min, which is probably due to the short reaction time, insufficient reaction and low trisodium nitrilotriacetate loading. The softening effect of the nitrilotriacetic acid trisodium salt/zirconium hydrogen phosphate nano composite material prepared by the reaction for 1 hour and the reaction for 24 hours on hard water is similar, which indicates that the reaction is complete when the reaction is carried out for 1 hour. Comparing the adsorption effects of the materials prepared in example 1 and example 11, it can be seen that the mass fraction of zirconium hydrogen phosphate in the suspension during the preparation process has little effect on the adsorption performance of the nanocomposite prepared.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A nanocomposite material comprising a solid acid support and a chelating agent supported on the solid acid support.
2. Nanocomposite as claimed in claim 1, characterized in that the solid acid carrier is zirconium hydrogen phosphate;
preferably, the zirconium hydrogen phosphate is α -zirconium hydrogen phosphate;
preferably, the chelating agent is nitrilotriacetic acid trisodium salt;
preferably, in the nanocomposite, the mass ratio of the solid acid carrier to the chelating agent is 1:0.1-1: 5.
3. Nanocomposite as claimed in claim 1, wherein the nanocomposite has an average particle size of from 300nm to 5 μm.
4. A process for the preparation of a nanocomposite material according to any one of claims 1 to 3, comprising the steps of:
(1) preparing a solid acid carrier suspension;
(2) mixing the solid acid carrier suspension liquid obtained in the step (1) with a chelating agent to obtain a mixed suspension liquid;
(3) and (3) carrying out solid-liquid separation on the mixed suspension liquid obtained in the step (2) to obtain the nano composite material.
5. The method according to claim 4, wherein the solid acid carrier in the step (1) is zirconium hydrogen phosphate;
preferably, the zirconium hydrogen phosphate is α -zirconium hydrogen phosphate;
preferably, the solid acid carrier of step (1) has an average particle size of 300nm to 5 μm;
preferably, the solvent of the solid acid carrier suspension of step (1) is water;
preferably, in the solid acid carrier suspension, the mass fraction of the solid acid carrier is 15-50 wt%.
6. The method according to claim 4 or 5, wherein in the step (2), the chelating agent is nitrilotriacetic acid trisodium salt;
preferably, in the step (2), the mass ratio of the solid acid carrier to the chelating agent is 1:0.1-1: 5;
preferably, in the step (2), the mixing method is stirring;
preferably, in the step (2), the mixing time is 10min-24 h.
7. The production method according to any one of claims 4 to 6, wherein in the step (3), the solid-liquid separation method comprises centrifugal separation.
8. The production method according to any one of claims 4 to 7, characterized by further comprising, in step (3): washing, drying and crushing the solid obtained by solid-liquid separation;
preferably, the method of washing comprises centrifugal washing;
preferably, the method of drying comprises forced air drying;
preferably, the drying temperature is 60-70 ℃;
preferably, the drying time is 10-14 h;
preferably, the method of crushing comprises grinding.
9. The method for preparing according to any one of claims 4 to 8, characterized in that it comprises the steps of:
(1) preparing a solid acid carrier suspension;
wherein the solid acid carrier is α -zirconium hydrogen phosphate;
the solvent of the solid acid carrier suspension is water;
the average particle size of the α -zirconium hydrogen phosphate is 300nm-5 mu m;
in the solid acid carrier suspension, the mass fraction of the solid acid carrier is 15-50 wt%;
(2) adding nitrilotriacetic acid trisodium salt into the solid acid carrier suspension in the step (1), and stirring and mixing for 10min-24h to obtain a mixed suspension;
wherein the mass ratio of the solid acid carrier to the nitrilotriacetic acid trisodium salt is 1:0.1-1: 5;
(3) and (3) carrying out centrifugal separation on the mixed suspension liquid obtained in the step (2), carrying out centrifugal washing, carrying out forced air drying at the temperature of 60-70 ℃ for 10-14h, and grinding into powder to obtain the nano composite material.
10. Use of a nanocomposite material according to any one of claims 1 to 3 as a hard water softener.
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