CN113694899B

CN113694899B - Lanthanum-zirconium bimetallic resin-based nanocomposite and preparation method and application thereof

Info

Publication number: CN113694899B
Application number: CN202111024023.2A
Authority: CN
Inventors: 花铭; 李致霆; 胡煜; 潘丙才; 张炜铭; 吕路
Original assignee: Nanjing University
Current assignee: Nanjing University
Priority date: 2021-09-02
Filing date: 2021-09-02
Publication date: 2022-07-12
Anticipated expiration: 2041-09-02
Also published as: CN113694899A

Abstract

The invention provides a lanthanum-zirconium bimetallic resin-based nanocomposite and a preparation method and application thereof, belonging to the field of environmental functional materials and pollutant removal. In the lanthanum-zirconium bimetallic resin matrix nano composite material, lanthanum-zirconium bimetallic oxide with lanthanum-oxygen-zirconium bonds formed by oxygen bridging lanthanum-zirconium is loaded in the resin, and compared with a single-metal lanthanum resin matrix nano composite material, the lanthanum-zirconium bimetallic resin matrix nano composite material has an XPS spectrum La 3d_5/2The binding energy is positively deflected; compared with a single-metal zirconium resin-based nano composite material, the lanthanum-zirconium double-metal resin-based nano composite material XPS spectrum Zr 3d_5/2The binding energy is negatively shifted. Compared with single metals such as zirconium-based and lanthanum-based resin-based nano composite materials, the lanthanum-zirconium bimetal nano composite material disclosed by the invention has the advantages that the pollutant removal performance is improved by 23.1% -28.1%, the adsorption capacity is large, the adsorption rate is high, the lanthanum-zirconium bimetal nano composite material is easy to separate and recycle, and the lanthanum-zirconium bimetal nano composite material has a wide application prospect.

Description

Lanthanum-zirconium bimetallic resin-based nanocomposite and preparation method and application thereof

Technical Field

The invention belongs to the field of environmental functional materials and pollutant removal, and particularly relates to a method for improving performance of a lanthanum-zirconium bimetallic resin matrix nano composite material and application thereof. The lanthanum-zirconium bimetallic resin-based nano composite material can be applied to removal of pollutants such as copper pyrophosphate, pyrophosphate and orthophosphate in electroplating wastewater.

Background

With the improvement of environmental awareness and the progress of technology, the cyanide-free electroplating technology is gradually selected in the high-pollution electroplating industry, wherein the copper pyrophosphate electroplating technology is most widely applied due to the outstanding dispersing capacity and uniform plating capacity, is usually used for processes such as printed board hole metallization and casting copper plating, and generates a large amount of pyrophosphate, copper pyrophosphate and orthophosphate wastewater along with the processes.

A large amount of phosphorus-containing wastewater such as orthophosphate radicals, pyrophosphate radicals, copper pyrophosphate complex anions and the like is discharged into rivers and lakes through various ways, so that the load of nutrient substances in a water body is increased, and the abnormal reproduction of algae and aquatic plants, namely the eutrophication of the water body, is caused, thereby causing the deterioration of the water quality of the water body, damaging an ecological system and influencing the production and the life of human beings. Phosphorus is one of the important factors for the eutrophication of water body, and is an essential element for the growth of organisms and the most important limiting nutrient. The water body polluted by phosphorus and algae are propagated in a large quantity, the dissolved oxygen is reduced sharply, the water quality is changed into bad smell, the survival of aquatic organisms such as fishes and the like is seriously influenced, the water quality of a water source is deteriorated, the difficulty and the cost of water treatment are increased, and the aesthetic value of the water body is reduced. Excessive phosphorus can seriously harm the marine environment, causing marine red tides.

In the last few years nanostructured metal (hydr) oxides have been widely used for enhanced and selective adsorption of orthophosphates, pyrophosphates, such as nanoscale hydrous zirconium oxides, iron oxides, etc. due to their large specific surface area and abundant surface hydroxyl active sites. However, these nano-oxides are often present as fine or ultra-fine particles and are difficult to separate in solid/liquid systems, which limits their use in fixed bed or other flow-through systems because of excessive pressure drop and flow resistance. To date, many efforts have been made to overcome this technical bottleneck: the metal nano oxide particles are fixed in the traditional large-size adsorbent, such as a method for deeply purifying trace phosphorus in a water body by using composite resin in the prior art with the Chinese patent application publication number of CN101343093A, a nano composite adsorbent for efficiently removing trace phosphorus, arsenic and antimony in the water body in the prior art with the CN101804333A and the like, so that the nano metal oxide can be fixed in a resin pore channel to prepare the single metal resin-based nano composite material, the separation is easy, the high density and the long-term retention are realized, and the adsorption capacity and the adsorption selectivity of the resin are improved.

However, the nano effect of the nano oxide particles of the single metal is limited, the adsorption reaction activity is weak, the capacity of improving the adsorption quantity and the selectivity has a bottleneck, and the deep removal capacity of the target pollutants needs to be further improved.

Therefore, how to improve the adsorption capacity of the metal nanocomposite to pyrophosphate, orthophosphate and copper pyrophosphate, increase the adsorption activity and improve the adsorption selectivity is still a technical problem to be solved urgently.

Disclosure of Invention

1. Problems to be solved

Aiming at the problems that the existing single metal resin-based nano composite material has limited nano effect, weak adsorption reaction activity and bottleneck on improving capacity of adsorption quantity and selectivity, the invention provides a lanthanum-zirconium bimetallic resin-based nano composite material and a preparation method and application thereof, wherein the composite material can be applied to removing complex heavy metal pollution in electroplating wastewater, such as removing heavy metal copper ions, phosphate ions, pyrophosphate ions, copper-phosphorus complex ions and the like, compared with the single metal resin-based nano composite material, the lanthanum-zirconium bimetallic resin-based nano composite material has the advantages that the adsorption performance is greatly improved, the adsorption capacity is improved by 23.1-28.1%, and the adsorption selectivity is greatly enhanced.

2. Technical scheme

In order to solve the problems, the technical scheme adopted by the invention is as follows:

compared with the single metal lanthanum resin matrix nanocomposite, the lanthanum-zirconium bimetallic resin matrix nanocomposite has the XPS spectrum La 3d of the lanthanum-zirconium bimetallic resin matrix nanocomposite_5/2The binding energy is positively deflected; compared with a single-metal zirconium resin-based nano composite material, the lanthanum-zirconium double-metal resin-based nano composite material XPS spectrum Zr 3d_5/2The binding energy is negatively shifted.

Note that, negative bias means that binding energy becomes small; a positive shift means that the binding energy becomes larger.

Preferably, the Zr 3d of said lanthanum zirconium bimetallic resin based nanocomposite is compared to a monometallic zirconium resin based nanocomposite_3/2The binding energy is negatively shifted.

Preferably, the lanthanum zirconium bimetallic resin based nanocomposite material XPS spectrum La 3d is compared to a monometallic lanthanum resin based nanocomposite material_5/2The positive deviation of the binding energy is less than or equal to 0.2 eV; and/or

Compared with a single-metal zirconium resin-based nano composite material, the lanthanum-zirconium double-metal resin-based nano composite material XPS spectrum Zr 3d_5/2The negative bias of the binding energy is less than or equal to 0.2 eV; and/or

Compared with a single-metal zirconium resin-based nano composite material, the lanthanum-zirconium double-metal resin-based nano composite material has XPS spectrum Zr 3d_3/2The negative bias of the binding energy is less than or equal to 0.2 eV.

Preferably, the loading rate of the lanthanum-zirconium bimetallic oxide is 8.21-14.52%.

Preferably, the resin is selected from one of D202, D201, D301.

A preparation method of a lanthanum-zirconium bimetallic resin matrix nano composite material comprises the following steps:

(1) dissolving lanthanum salt and zirconium oxychloride in a certain proportion in an ethanol water solution containing hydrochloric acid;

(2) adding anion exchange resin into the solution obtained in the step (1), and loading lanthanum and zirconium in the pore canal of the anion exchange resin under heating and stirring;

(3) adding a sodium hydroxide solution into the anion exchange resin loaded with lanthanum and zirconium obtained in the step (2), and heating and stirring;

(4) washing the anion exchange resin loaded with lanthanum and zirconium obtained in the step (3) by using a sodium chloride solution for transformation;

(5) and washing the prepared resin with water to be neutral, and drying to obtain the lanthanum-zirconium bimetallic resin nano composite material.

Preferably, the molar ratio of lanthanum to zirconium in the step (1) is (1.32-1.09): 1.

Preferably, the preparation method specifically comprises the following steps:

(1) lanthanum chloride and zirconium oxychloride are added into ultrapure water containing 5-15% hydrochloric acid and 5-15% absolute ethyl alcohol in volume ratio, the molar ratio of lanthanum to zirconium is controlled to be (1.32-1.09): 1, lanthanum chloride and zirconium oxychloride powder is dispersed and dissolved by ultrasonic, the ultrasonic power is controlled to be 50-80%, or the stirring speed is controlled to be 150-250 rmp;

(2) weighing strong-base anion exchange resin or weak-base anion exchange resin, adding the weighed strong-base anion exchange resin or weak-base anion exchange resin into the solution prepared in the step (1), controlling the mass ratio of the solution to the resin to be (10-20): 1, controlling the stirring speed to be 150-250 rmp in a constant-temperature water bath at the temperature of 40-70 ℃, and stirring for 12-24 hours;

(3) adding a solution containing 10-20% by mass of sodium hydroxide powder into the resin filtered in the step (2), forming lanthanum zirconium oxide or hydroxide nanoparticles in a resin pore channel, stirring for 2-5 hours in a constant-temperature water bath at 40-70 ℃ at a stirring speed of 150-250 rmp, and filtering;

(4) preparing a sodium chloride solution with the mass ratio of 5-7%, adding the resin filtered in the step (3) into the sodium chloride solution, and performing salt washing for 1-5 hours for transformation;

(5) and (3) washing the synthesized resin to be neutral, and drying at the temperature of 50-70 ℃ to obtain the lanthanum-zirconium bimetallic resin nano composite material.

The lanthanum-zirconium bimetallic resin-based nano composite material is applied to phosphorus removal and/or heavy metal ion removal.

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that:

(1) compared with the existing single metal resin-based nano composite material, the lanthanum-zirconium bimetallic material of the lanthanum-zirconium bimetallic resin-based nano composite material has better nano effect, more-OH proportion and stronger adsorption reaction activity, and further improves the deep removal capability of target pollutants; when the method is applied to removal of complex heavy metal pollutants in electroplating wastewater, such as removal of pollutants such as heavy metal copper ions, phosphate ions, pyrophosphate ions, copper-phosphorus complex ions and the like, as shown in figures 6, 7 and 8, the adsorption capacity of the lanthanum-zirconium bimetallic resin matrix nanocomposite material is improved by 23.1-28.1% compared with that of the existing single metal lanthanum or zirconium resin matrix nanocomposite material;

(2) according to the invention, by comparing the XPS diagrams of the lanthanum-zirconium bimetallic resin matrix nano composite material and the single metal lanthanum or zirconium resin matrix nano composite material, the XPS diagram La 3d of the lanthanum-zirconium bimetallic resin matrix nano composite material is found to be compared with that of the single metal lanthanum resin matrix nano composite material_5/2The binding energy is positively deflected; compared with a single-metal zirconium resin-based nano composite material, the lanthanum-zirconium double-metal resin-based nano composite material XPS spectrum Zr 3d_5/2The binding energy is negatively shifted; compared with single metal zirconium resin based nano composite material, Zr 3d of lanthanum zirconium bi-metal resin based nano composite material_3/2The binding energy undergoes negative shifts, which indicate that the lanthanum zirconium bimetallic is not present in the resin as the respective oxide or hydroxide, but rather forms a lanthanum-oxygen-zirconium bond and acts to adsorb phosphorus, heavy metal ions in this form;

(3) the lanthanum-zirconium bimetallic resin-based nano composite material disclosed by the invention combines the Donnan film effect (namely enhanced diffusion and enrichment concentration effect) of a carrier charged group and the characteristic of good selective adsorption effect of lanthanum-zirconium oxide on heavy metal pollutants copper ions, phosphate ions, pyrophosphate ions and copper-phosphorus complex ions, and obviously enhances the adsorption capacity and adsorption selectivity of an adsorbent.

Drawings

FIG. 1 is an appearance view of a lanthanum zirconium bimetallic resin-based nanocomposite prepared in example 1 of the present invention;

FIG. 2 is an SEM-EDS spectrum of a lanthanum zirconium bimetallic resin-based nanocomposite prepared in example 1 of the invention, showing the loading elements;

FIG. 3 is an XRD pattern of a lanthanum zirconium bimetallic resin based nanocomposite prepared in example 1 of the present invention, a monometallic supported nanocomposite prepared in comparative example 1A and comparative example 1B, showing the supported crystalline form;

FIG. 4 is an XPS spectra of lanthanum and zirconium for lanthanum-zirconium bimetallic doped resin-based nanocomposites prepared in example 1(La-Zr-201), comparative example 1A (Zr-201), and comparative example 1B (La-201);

FIG. 5 is an XPS spectrum for oxygen for the lanthanum zirconium bimetallic resin based nanocomposites prepared in example 1, comparative example 1A, comparative example 1B and the monometallic zirconium lanthanum resin based nanocomposites;

FIG. 6 is a comparison of the effect of adsorbing pyrophosphate of the lanthanum zirconium bimetallic resin-based nanocomposite prepared in example 4, comparative example 1A and comparative example 1B with that of the monometallic zirconium and lanthanum resin-based nanocomposite;

FIG. 7 is a graph showing the comparison of the adsorption effect of orthophosphate on lanthanum zirconium bimetallic resin-based nanocomposites prepared in example 5, comparative example 1A and comparative example 1B with that of single metal zirconium and lanthanum resin-based nanocomposites;

FIG. 8 is a graph showing the comparison of the adsorption effect of copper pyrophosphate on lanthanum zirconium bimetallic resin-based nanocomposites prepared in example 6, comparative example 1A and comparative example 1B with that of single metal zirconium and lanthanum resin-based nanocomposites;

FIG. 9 is a comparison of the adsorption selectivity effect of the lanthanum zirconium bimetallic resin-based nanocomposite prepared in example 7 and comparative example 1B on copper pyrophosphate adsorption of the single metal lanthanum resin-based nanocomposite.

Detailed Description

The present invention will now be described in detail with reference to specific examples, but the invention is not limited thereto.

Example 1

The specific preparation process of the lanthanum-zirconium bimetallic resin matrix nano composite material comprises the following steps:

(1) respectively adding 26.6g and 21.2g of lanthanum chloride and zirconium oxychloride (the molar ratio of lanthanum to zirconium is 1.09:1) into a 500ml beaker, then adding 300ml of water, 15ml of hydrochloric acid and 30ml of ethanol, and stirring and dissolving under ultrasonic conditions;

(2) weighing strong-base anion exchange resin D201 produced by Hangzhou resin factory with the mass ratio of solution to resin being 15:1, adding into the solution, setting the temperature at 60 ℃, and stirring at 150rpm under sealed condition for 12 hours.

(3) Then, the resin was filtered off, and the filtered resin was added to 300ml of a 10% sodium hydroxide solution, the temperature was set at 60 ℃, and the mixture was stirred at 150rpm for 2 hours.

(4) The resin after mixing was added to 300ml of 5% sodium chloride solution and stirred at 150rpm for 1 hour.

(5) Filtering out the resin after stirring, washing the resin by using a large amount of clear water until the resin is neutral, and drying the resin in an oven at the temperature of 60 ℃ to obtain the lanthanum-zirconium bimetallic resin matrix nano composite material. The appearance of the lanthanum-zirconium bimetallic resin matrix nanocomposite is shown in figure 1, the loading elements are shown in figure 2, the total loading rate is 8.2%, the loading crystal form is shown in figure 3, and the composite material is different from the amorphous form of a single zirconium metal loading composite resin.

Comparative example 1A

The specific preparation process of the zirconium single metal resin-based nano composite material comprises the following steps:

(1) adding 52.22g of zirconium oxychloride into a 500ml beaker, then adding 300ml of water, 15ml of hydrochloric acid and 30ml of ethanol, and stirring and dissolving under ultrasonic conditions;

(5) Filtering out the resin after stirring, washing with a large amount of clear water until the resin is neutral, and drying the zirconium monometal resin-based nanocomposite material in a drying oven at 60 ℃ to obtain the zirconium-doped resin-based nanocomposite material, wherein the zirconium loading rate is 8.6%.

Comparative example 1B

The specific preparation process of the lanthanum single metal resin-based nano composite material comprises the following steps:

(1) adding 42.2g of lanthanum chloride into a 500ml beaker, then adding 300ml of water, 15ml of hydrochloric acid and 30ml of ethanol, and stirring and dissolving under ultrasonic conditions;

(5) Filtering out the resin after stirring, washing the resin by using a large amount of clear water until the resin is neutral, and drying the lanthanum single metal resin matrix nano composite material in a drying oven at 60 ℃ to obtain the lanthanum-doped resin matrix nano composite material, wherein the total loading rate of lanthanum is 7.9%.

Example 2

This example is XPS spectra (fig. 4) of lanthanum and zirconium metal of lanthanum and zirconium-doped resin-based nanocomposite, single metal zirconium and lanthanum resin-based nanocomposite prepared in example 1 and comparative examples 1A and 1B, and fig. 4 shows the electronic structure of La — Zr-201. La 3d of La-Zr-201 composite material compared with pure Zr-201_5/2Positive shifts in binding energies from 835.1eV to 835.2eV and 838.5eV to 838.7eV, respectively, indicate that electrons move toward Zr⁴⁺The direction is moved. Zr 3d_5/2From 184.5 to 184.3eV,3d_3/2Moving from 182.1 to 181.9eV, the electron cloud is transferred from one kind of cation to another kind of cation, showing that the electron is extracted from La atom to form new La-O-Zr bond, and the charge transfer between La and Zr is realized through oxygen bridge, showing that the bimetallic doping load is not the La and Zr metals which are simply mixed and respectively loaded of two kinds of single metals, but is the La and Zr overall load to form new La-O-Zr, further producing the effect as in examples 3-6, compared with the single metal resin-based nano composite material, the lanthanum-zirconium bimetallic resin-based nano composite material can effectively improve the pollutant adsorption effect.

Example 3

This example is an XPS spectrum (FIG. 5) of the La-Zr bimetallic resin-based nanocomposites, the single metal zirconium, the La resin-based nanocomposites prepared in example 1 and comparative examples 1A, 1B with respect to oxygen, and oxygen inside the nanomaterial can be classified into-OH with a binding energy of around 530.1eV and O with a binding energy of around 532.2eV^2-And C-O with a binding energy around 533 eV. FIG. 5 shows that the lanthanum-zirconium bimetallic resin matrix nanocomposite has a higher oxygen vacancy (-OH) ratio than single metal zirconium and lanthanum resin matrix nanocomposites, namely La-Zr-201 (36.7%), La-201 (31.7%) and Zr-201 (15.3%), and has a better nano effect, a higher proportion of-OH and a stronger adsorption reaction activity.

Example 4

(1) respectively adding 26.6g and 21.2g of lanthanum chloride and zirconium oxychloride (the molar ratio of lanthanum to zirconium is 1.09:1) into a 500ml beaker, then adding 300ml of water, 20ml of hydrochloric acid and 40ml of ethanol, and stirring and dissolving under ultrasonic conditions;

(2) weighing strong-base anion exchange resin D201 produced by Hangzhou resin factory, wherein the mass ratio of the solution to the resin is 20:1, adding into the solution, setting the temperature at 60 ℃, and stirring at 200rpm under sealed condition for 12 hours.

(3) Then, the resin was filtered off, and the filtered resin was added to 300ml of a 10% sodium hydroxide solution, the temperature was set at 60 ℃, and the mixture was stirred at 200rpm for 2 hours.

(4) The resin after mixing was added to 300ml of 5% sodium chloride solution and stirred at 200rpm for 1 hour.

(5) Filtering out the resin after stirring, washing with a large amount of clear water until the resin is neutral, and drying the lanthanum-zirconium bimetallic resin matrix nanocomposite in a drying oven at 60 ℃ to obtain the bimetallic doped resin matrix nanocomposite. The lanthanum-zirconium bimetallic resin-based nano composite material has the total lanthanum-zirconium loading rate of 9.32% (wherein the lanthanum accounts for 65.5%, and the zirconium accounts for 34.5%).

Second, adsorption experiment of lanthanum zirconium bimetallic resin based nano composite material on pyrophosphate

(1) Preparing simulated wastewater containing the pyrophosphate, wherein the concentration of the pyrophosphate is 300mg/L, and the pH value of the simulated wastewater is 8.5.

(2) Weighing 0.05g of single metal resin-based nano composite material Zr-201 (comparative example 1A), La-201 (comparative example 1B) and D201 in corresponding parts, weighing 0.02g of lanthanum-zirconium double metal resin-based nano composite material La-Zr-201 (embodiment), respectively placing the materials into a 50mL centrifuge tube, adding 40mL of pyrophosphate solution, oscillating at the constant temperature of 25 ℃ for 24 hours, measuring the positive phosphorus in the solution after adsorption equilibrium and calculating the adsorption capacity, as shown in figure 6, in the pyrophosphate removal process, the adsorption capacity of the lanthanum-zirconium double metal resin-based nano composite material is 64mg/mmol, the adsorption capacity of the single metal lanthanum-based nano composite material is 53mg/mmol, the adsorption capacity of the single metal zirconium-based nano composite material is 32mg/mmol, and the percentage content of lanthanum and zirconium in the lanthanum-zirconium double metal resin-based nano composite material and lanthanum, The adsorption capacity of the zirconium monometallic nanocomposite as an adsorbent was calculated to be improved by about 26.9% compared to the adsorption capacity of the lanthanum-zirconium bimetallic resin-based nanocomposite when the same amount of the respective oxides of lanthanum and zirconium were added (64-53 × 65.5% -32 × 34.5% ═ 17.21 mg/mmol).

Example 5

(2) weighing strong-base anion exchange resin D201 produced by Hangzhou resin factory, wherein the mass ratio of the solution to the resin is 18:1, adding into the solution, setting the temperature at 70 ℃, and stirring at 150rpm for 12 hours.

(3) Then, the resin was filtered off, and the filtered resin was added to 300ml of a 10% sodium hydroxide solution, the temperature was set at 70 ℃ and stirred at 150rpm for 2 hours.

(4) After the completion of the mixing, the resin was filtered off to be air-dried, and then added to 150ml of a 5% sodium chloride solution, and stirred at 150rpm for 1 hour.

(5) Filtering out the resin after stirring, washing the resin by using a large amount of clear water until the resin is neutral, and drying the resin in an oven at the temperature of 60 ℃ to obtain the lanthanum-zirconium bimetallic resin matrix nano composite material. The total loading of the lanthanum zirconium metal resin based nanocomposite was 11.23% (where lanthanum was 61.2% and zirconium was 38.8%).

Second, lanthanum zirconium bimetallic resin based nano composite material adsorption experiment of orthophosphate

(1) Orthophosphate simulated wastewater with the concentration of 50mg/L is prepared, and the pH value of the simulated wastewater is 7.5.

(2) Weighing corresponding parts of 0.05g of single metal resin-based nano composite material Zr-201 (comparative example 1A), La-201 (comparative example 1B) and D201, weighing corresponding parts of 0.02g of lanthanum-zirconium double metal resin-based nano composite material La-Zr-201 (the embodiment), respectively placing in a 50mL centrifuge tube, adding 40mL of orthophosphate solution, oscillating at constant temperature of 25 deg.C for 24 hr, measuring total phosphorus in the solution after adsorption equilibrium and calculating adsorption capacity, as shown in FIG. 7, in the removal of orthophosphoric acid pollutants, the adsorption capacity of the lanthanum-zirconium bimetallic resin-based nanocomposite is 50mg/mmol, the adsorption capacity of the monometallic lanthanum-based nanocomposite is 41mg/mmol, the adsorption capacity of the monometallic zirconium-based nanocomposite is 28mg/mmol, and the adsorption capacity is improved by about 28.1% (50-41 × 61.2% -28 × 38.8% ═ 14.04 mg/mmol).

Example 6

(1) respectively adding 32.2g and 21.2g of lanthanum chloride and zirconium oxychloride (the molar ratio of lanthanum to zirconium is 1.32:1) into a 500ml beaker, then adding 300ml of water, 15ml of hydrochloric acid and 40ml of ethanol, and stirring and dissolving under ultrasonic conditions;

(2) weighing strong-base anion exchange resin D201 produced by Hangzhou resin factory with the mass ratio of solution to resin being 17:1, adding into the solution, setting the temperature at 65 ℃, and stirring at 150rpm under sealed condition for 12 hours.

(3) Then, the resin was filtered off, and the filtered resin was added to 300ml of a 10% sodium hydroxide solution, the temperature was set at 65 ℃ and stirred at 150rpm for 2 hours.

(5) Filtering out the resin after stirring, washing the resin by using a large amount of clear water until the resin is neutral, and drying the resin in an oven at the temperature of 60 ℃ to obtain the lanthanum-zirconium bimetallic resin matrix nano composite material. The total loading rate of the lanthanum-zirconium bimetallic resin-based nanocomposite material is 14.52% (wherein the lanthanum accounts for 75.2%, and the zirconium accounts for 24.8%).

Second, adsorption experiment of lanthanum-zirconium bimetallic resin-based nanocomposite material on focusing copper phosphate

(1) Preparing copper ion-containing copper pyrophosphate simulated wastewater with the concentration of 30mg/L, keeping the molar ratio of copper to pyrophosphate of 1:1, and controlling the pH value of the simulated wastewater to be 8.5.

(2) Weighing corresponding parts of 0.05g of single metal resin-based nano composite material Zr-201 (comparative example 1A), La-201 (comparative example 1B) and D201, weighing corresponding parts of 0.02g of lanthanum-zirconium double metal resin-based nano composite material La-Zr-201 (the embodiment), respectively placing in a 50mL centrifuge tube, 40mL of copper pyrophosphate solution was added, the solution was shaken at a constant temperature of 25 ℃ for 24 hours, after the equilibrium of adsorption, copper ions in the solution were measured and the adsorption capacity was calculated, as shown in FIG. 8, in the removal of copper pyrophosphate pollutants, the adsorption capacity of the lanthanum-zirconium bimetallic resin-based nanocomposite is 68mg/mmol, the adsorption capacity of the monometallic lanthanum-based nanocomposite is 56mg/mmol, the adsorption capacity of the monometallic zirconium-based nanocomposite is 41mg/mmol, and the adsorption capacity is improved by about 23.1% (68-56 × 75.2% -41 × 24.8% ═ 15.72 mg/mmol).

Example 7

(1) in a 500ml beaker, 26.6g and 21.2g of lanthanum chloride and zirconium oxychloride respectively (molar ratio of lanthanum to zirconium is 1.09:1) are added, 300ml of water, 20ml of hydrochloric acid and 30ml of ethanol are added,

(2) weighing strong base anion exchange resin D201 from Hangzhou resin factory, adding into the solution, setting temperature at 65 deg.C, and stirring at 150rpm for 12 hr.

(4) After the completion of the mixing, the resin was filtered off, air-dried, and then added to 150ml of a 10% sodium chloride solution, and stirred at 150rpm for 1 hour.

(5) Filtering out the resin after stirring, washing the resin by using a large amount of clear water until the resin is neutral, and drying the resin in an oven at the temperature of 60 ℃ to obtain the lanthanum-zirconium bimetallic resin matrix nano composite material. The total loading rate of the lanthanum-zirconium bimetallic resin-based nanocomposite material is 8.21%.

Second, adsorption experiment of lanthanum-zirconium bimetallic resin-based nanocomposite on focusing copper phosphate under condition of containing competitive ions

(1) Preparing simulated wastewater containing copper pyrophosphate with the same concentration, wherein the concentration of copper ions is 15mg/L respectively, keeping the molar ratio of copper to pyrophosphate at 1:1, adding nitrate ions with different concentrations, wherein the concentrations are 300mg/L, 500mg/L, 700mg/L, 1000mg/L and 1500mg/L, and the pH value of the simulated wastewater is 8.5.

(2) Weighing corresponding parts of 0.05g of single metal resin-based nano composite materials La-201 (comparative example 1B) and D201, weighing corresponding parts of 0.02g of lanthanum-zirconium bimetallic resin-based nano composite materials La-Zr-201 (embodiment), respectively placing the materials into 50mL centrifuge tubes, adding the materials into 40mL copper pyrophosphate solution containing competitive ions with different concentrations, oscillating the materials at a constant temperature of 25 ℃ for 24 hours, measuring the total phosphorus in the solution after adsorption equilibrium and calculating the adsorption capacity, as shown in figure 9, the adsorption rate of the lanthanum-zirconium bimetallic resin-based nano composite materials to the whole copper pyrophosphate can still be kept at about 15% under the condition that the competitive ions are gradually increased, and the adsorption rate of the single metal lanthanum resin-based nano composite materials can only be kept at about 5%.

In some examples, a lanthanum zirconium bimetallic resin based nanocomposite was prepared using the same other conditions as in example 1, except that the lanthanum zirconium molar ratio was 1.3:1,1.2:1,1.1: 1.

The above description is illustrative of the present invention and its embodiments, and is not to be construed as limiting, and the embodiments shown in the examples are only one embodiment of the present invention, and the actual embodiments are not limited thereto. Therefore, if the person skilled in the art receives the teaching, the embodiment and the embodiment similar to the technical solution should be designed without creativity without departing from the spirit of the invention, and shall fall within the protection scope of the invention.

Claims

1. The lanthanum-zirconium bimetallic resin matrix nano composite material is characterized in that lanthanum-zirconium bimetallic oxide with lanthanum-oxygen-zirconium bonds, which is formed by oxygen bridging lanthanum-zirconium, is loaded in the resin, and compared with a single-metal lanthanum resin matrix nano composite material, the lanthanum-zirconium bimetallic resin matrix nano composite material has an XPS spectrum La 3d_5/2The binding energy is positively shifted; compared with a single-metal zirconium resin-based nano composite material, the lanthanum-zirconium double-metal resin-based nano composite material XPS spectrum Zr 3d_5/2The binding energy is negatively shifted.

2. The lanthanum zirconium bimetallic resin-based nanocomposite material as claimed in claim 1, characterized in that the lanthanum zirconium bimetallic resin-based nanocomposite material has Zr 3d compared to a monometallic zirconium resin-based nanocomposite material_3/2The binding energy is negatively shifted。

3. The lanthanum zirconium bimetallic resin-based nanocomposite material according to claim 2, characterized in that the lanthanum zirconium bimetallic resin-based nanocomposite material has an XPS spectrum La 3d as compared to a monometallic lanthanum resin-based nanocomposite material_5/2The positive deviation of the binding energy is less than or equal to 0.2 eV; and/or

Compared with a single-metal zirconium resin-based nano composite material, the lanthanum-zirconium double-metal resin-based nano composite material XPS spectrum Zr 3d_5/2The negative bias of the binding energy is less than or equal to 0.2 eV.

4. The lanthanum zirconium bimetallic resin-based nanocomposite material according to claim 3, characterized in that the lanthanum zirconium bimetallic resin-based nanocomposite material XPS spectrum Zr 3d is comparable to that of a monometallic zirconium resin-based nanocomposite material_3/2The negative bias of the binding energy is less than or equal to 0.2 eV.

5. The lanthanum zirconium bimetallic resin-based nanocomposite material as claimed in claim 4, characterized in that the loading rate of the lanthanum zirconium bimetallic oxide is 8.21-14.52%.

6. The lanthanum zirconium bimetallic resin-based nanocomposite material as in claim 3, characterized in that the resin is selected from one of D202, D201, D301.

7. The preparation method of the lanthanum zirconium bimetallic resin matrix nanocomposite material as claimed in any one of claims 1 to 6, characterized in that the preparation method comprises the following steps:

(1) adding lanthanum chloride and zirconium oxychloride into ultrapure water containing 5-15% hydrochloric acid and 5-15% absolute ethyl alcohol in volume ratio, controlling the molar ratio of lanthanum to zirconium to be (1.09-1.32): 1, ultrasonically dispersing and dissolving lanthanum chloride and zirconium oxychloride powder, and controlling the ultrasonic power to be 50-80% or controlling the stirring speed to be 150-250 rpm;

(2) weighing strong-base anion exchange resin or weak-base anion exchange resin, adding the weighed strong-base anion exchange resin or weak-base anion exchange resin into the solution prepared in the step (1), controlling the mass ratio of the solution to the resin to be (10-20): 1, controlling the stirring speed to be 150-250 rpm in a constant-temperature water bath at 40-70 ℃, and stirring for 12-24 hours;

(3) adding a solution containing 10-20% by mass of sodium hydroxide powder into the resin filtered in the step (2), forming lanthanum zirconium oxide or hydroxide nanoparticles in a resin pore channel, stirring for 2-5 hours in a constant-temperature water bath at 40-70 ℃ at a stirring speed of 150-250 rpm, and filtering;

(4) preparing a sodium chloride solution with the mass ratio of 5-7%, and adding the resin filtered in the step (3) into the sodium chloride solution for salt washing for 1-5 hours for transformation;

8. The use of the lanthanum zirconium bimetallic resin based nanocomposite material according to any one of claims 1 to 6 for phosphorus removal and/or heavy metal ion removal.