Hybrid zirconium phosphate and preparation method and application thereof

Abstract

This invention relates to a method for preparing hybrid zirconium phosphate. The method involves using a portion of the second reaction solution as the third reaction solution, adding the first reaction solution and the remaining second reaction solution to the third reaction solution for reaction, allowing it to stand at a constant temperature, then filtering and washing, and finally evaporating and drying to obtain the hybrid zirconium phosphate. 3‑ 967cm ‑1 ~1200cm ‑1 At the stretching vibration peak, hybrid zirconium phosphate PO4 3‑ The peak is sharp and splits into two smaller peaks, intermediate between α-zirconium phosphate and amorphous zirconium phosphate, exhibiting a hybrid state at the molecular level. It possesses both high ion exchange capacity and ion exchange rate, with a cation exchange capacity of 3.5–4.5 mmol / g and a cation exchange rate of 1.20–2.15 g mmol / g. ‑1 min ‑1 This solves the problems of low exchange capacity of amorphous zirconium phosphate and slow exchange rate of crystalline zirconium phosphate, and has a wider range of applications.

Description

Technical Field

[0001] This invention relates to the field of zirconium phosphate production technology, specifically to a hybrid zirconium phosphate, its preparation method, and its application. Background Technology

[0002] Zirconium phosphate is an excellent inorganic ion exchange material with high exchange capacity, high thermal stability, and radiation stability, and is widely used in ion exchange, catalysis, photochemistry, and biotechnology. Currently, the known types of zirconium phosphate are classified into amorphous zirconium phosphate (HZr₂(PO₄)₃) and crystalline layered zirconium phosphate, including α–Zr(HPO₄)₂·H₂O, θ–Zr(HPO₄)₂·6H₂O, and γ-Zr(PO₄)(H₂PO₄)·2H₂O. Traditional methods for preparing zirconium phosphate include the reflux method, the fluorine coordination method, and the hydrothermal method.

[0003] Crystalline zirconium phosphate structures are all composed of coplanar zirconium atom layers, and consist of phosphate groups (PO4) located above and below the zirconium atom planes. 3- HPO4 2- and H2PO 4- The bridging of adjacent layers creates micropores. Because crystalline zirconium phosphate has a higher exchange capacity than amorphous zirconium phosphate, research has mainly focused on α–Zr(HPO4)2·H2O. However, its ion exchange behavior is limited by its interlayer space and narrow micropores, resulting in a low exchange rate. Furthermore, the synthesis methods generally require high temperature and high pressure conditions, making preparation difficult and limiting practical applications. A common method to overcome this problem is that the hydrogen in α–Zr(HPO4)2·H2O can be absorbed by larger cations (Na+). + The substitution of sodium phosphate to form α–Zr(NaPO4)2·H2O expands the micropores inside α–Zr(HPO4)2·H2O and improves the channels of ion exchange sites. However, the ion exchange rate of disodium-exchanged α–Zr(NaPO4)2·H2O is still significantly slower than that of amorphous zirconium phosphate.

[0004] Amorphous zirconium phosphate can be prepared by precipitation and does not have micropores, so its exchange rate is faster than that of α-zirconium phosphate. Its molecular formula shows a total hydrogen ion content of 6.64 mmol / g. However, below neutral pH, only about half of the hydrogen ions in amorphous ZrP, or about 3.04 mmol / g, can exchange with heavy metals. Its exchange capacity is low and its crystallinity is poor.

[0005] Existing methods for preparing zirconium phosphate involve long reaction times, strict conditions, and difficulty in large-scale production. Furthermore, the resulting zirconium phosphate is unlikely to simultaneously achieve good exchange capacity and exchange rate. Summary of the Invention

[0006] Therefore, it is necessary to provide a hybrid zirconium phosphate, its preparation method, and its application.

[0007] The technical solution of this invention to solve the above-mentioned technical problems is as follows: A method for preparing hybrid zirconium phosphate, comprising the following steps:

[0008] A first reaction solution and a second reaction solution are provided. The first reaction solution comprises zirconium oxychloride, sodium fluoride and deionized water. The second reaction solution comprises disodium hydrogen phosphate and deionized water.

[0009] Take a portion of the second reaction solution as the third reaction solution, add the first reaction solution and the remaining second reaction solution to the third reaction solution to react and obtain the first reaction product;

[0010] The first reaction product was allowed to stand at a constant temperature to obtain the second reaction product;

[0011] The second reaction product was filtered, washed, evaporated and dried to obtain hybrid zirconium phosphate.

[0012] In one embodiment, in the first reaction solution, the molar ratio of zirconium oxychloride, sodium fluoride and deionized water, based on zirconium ions, is 1:(0.3-1):(10-30).

[0013] In one embodiment, the molar ratio of the disodium hydrogen phosphate to the deionized water in the second reaction solution is 1:(25-45).

[0014] In one embodiment, the molar ratio of zirconium oxychloride to disodium hydrogen phosphate, based on zirconium ions, is 1:(1.5-4).

[0015] In one embodiment, the molar ratio of zirconium oxychloride to disodium hydrogen phosphate is 1:(2-3).

[0016] In one embodiment, when the first reaction solution and the remaining second reaction solution are added to the third reaction solution to carry out the reaction, the reaction temperature is controlled at 50℃-70℃ and the reaction time is 100min-200min.

[0017] In one embodiment, when the first reaction product is subjected to constant temperature standing, the temperature of constant temperature standing is controlled at 50℃-70℃, and the constant temperature standing is maintained for more than 30 minutes.

[0018] In one embodiment, when the second reaction product is filtered, washed, and then evaporated and dried, the evaporation and drying temperature is controlled at 70℃-95℃, and the evaporation and drying time is 7h-9h.

[0019] A hybrid zirconium phosphate is prepared by the hybrid zirconium phosphate preparation method described in any of the above embodiments.

[0020] An application of the aforementioned hybrid zirconium phosphate in the preparation of purification carbon rods.

[0021] Compared with the prior art, the present invention has the following advantages and technical effects:

[0022] (1) In this invention, a portion of the second reaction solution is used as the third reaction solution. The first reaction solution and the remaining second reaction solution are added to the third reaction solution for reaction. After being kept at a constant temperature and allowed to stand, the mixture is filtered, washed, and finally evaporated and dried to obtain a hybrid zirconium phosphate. Its microcrystalline structure has zirconium atoms as the basal plane, with each zirconium atom connected to an oxygen atom. Each phosphorus atom carries a P-OH residue or an active group PG and is connected to oxygen atoms on both sides of the basal plane. In PO4 3- 967cm -1 ~1200cm -1 At the stretching vibration peak, hybrid zirconium phosphate PO4 3- The peak is sharp and splits into two smaller peaks, intermediate between α-zirconium phosphate and amorphous zirconium phosphate, exhibiting a hybrid state at the molecular level. It possesses both high ion exchange capacity and ion exchange rate, with a cation exchange capacity of 3.5-4.5 mmol / g and a cation exchange rate of 1.20-2.15 g mmol / g. -1 min -1 This solves the problems of low exchange capacity of amorphous zirconium phosphate and slow exchange rate of crystalline zirconium phosphate, and has a wider range of applications.

[0023] (2) By setting the molar ratio of zirconium oxychloride to sodium fluoride to 1:(0.3-1) and the molar ratio of zirconium oxychloride to disodium hydrogen phosphate to 1:(1.5-4), controlling the reaction temperature to 50℃-70℃ and the reaction time to 100min-200min, hybrid zirconium phosphate can be prepared in batches using sodium fluoride as a reaction catalyst in a low-temperature hydrothermal manner. The required reaction temperature is low, the reaction time is short, the equipment requirements are low, and the preparation is simple and efficient.

[0024] (3) The prepared hybrid zirconium phosphate has a large particle size, with a D50 range of 10-25 μm. It has better physical stability, provides more internal space, which is conducive to ion diffusion and exchange, thus having better ion exchange performance. At the same time, it is easier to control the growth and formation of particles, thereby simplifying the preparation process.

[0025] (4) The prepared hybrid zirconium phosphate has broad-spectrum cationic adsorption performance and good removal performance for heavy metals such as chromium, manganese, iron, copper, arsenic, cadmium, barium, mercury, lead and selenium. In particular, it has excellent lead removal effect and also has good effects in reducing pH, TDS and scale inhibition. The purification carbon rod prepared by using it as raw material has significant purification effect in water purification applications. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This is a schematic flowchart of a method for preparing hybrid zirconium phosphate according to an embodiment of the present invention;

[0028] Figure 2 This is a scanning electron microscope image of the hybrid zirconium phosphate of Example 1;

[0029] Figure 3 This is a scanning electron microscope image of the hybrid zirconium phosphate of Example 3;

[0030] Figure 4 This is a scanning electron microscope image of the hybrid zirconium phosphate of Example 5;

[0031] Figure 5 The image shows the FIR spectrum of the hybrid zirconium phosphate from Example 1.

[0032] Figure 6 The scale inhibition effect of boiling water samples during the flushing test of carbon rods containing hybrid zirconium phosphate powder from Example 2.

[0033] Figure 7 The image shows the scale inhibition effect of boiling water samples during the flushing test of the kettle filter cartridge containing the hybrid zirconium phosphate powder of Example 3. Detailed Implementation

[0034] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to limit the invention. Where specific techniques or conditions are not specified herein, they shall be performed in accordance with the techniques or conditions described in the literature in the art or according to product instructions. Where the manufacturer of reagents or instruments is not specified, they are commercially available products. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0036] In one embodiment, such as Figure 1 As shown, a method for preparing hybrid zirconium phosphate includes the following steps:

[0037] Step 110: Provide a first reaction solution and a second reaction solution. The first reaction solution includes zirconium oxychloride, sodium fluoride, and deionized water. The second reaction solution includes disodium hydrogen phosphate and deionized water.

[0038] In this embodiment, in the first reaction solution, the molar ratio of zirconium oxychloride, sodium fluoride, and deionized water, based on zirconium ions, is 1:(0.3-1):(10-30), with a preferred molar ratio of 1:(0.3-0.5):(11-16). The relative molecular mass of zirconium oxychloride is 322.25, its molecular formula is ZrOCl2·8H2O, and its CAS number is 13520-92-8. The first reaction solution is prepared by uniformly mixing zirconium chloride, sodium fluoride, and deionized water. For example, zirconium oxychloride can be added to deionized water first to form an aqueous solution of zirconium oxychloride, and then a fluoride salt can be added to obtain the first reaction solution; alternatively, sodium fluoride can be added to deionized water first to form an aqueous solution containing sodium fluoride, and then zirconium oxychloride can be added to the aqueous solution containing sodium fluoride to obtain the first reaction solution. Simultaneously, zirconium oxychloride and sodium fluoride can also be added to deionized water simultaneously to obtain the first reaction solution.

[0039] In this embodiment, the molar ratio of disodium hydrogen phosphate to deionized water in the second reaction solution is 1:(25-45), with a preferred molar ratio of 1:(25-35). The second reaction solution is prepared by uniformly mixing disodium hydrogen phosphate and deionized water. Based on zirconium ions, the molar ratio of zirconium oxychloride in the first reaction solution to disodium hydrogen phosphate in the second reaction solution is 1:(1.5-4), with a preferred molar ratio of 1:(2-3). All reagents and raw materials used in this invention are commercially available.

[0040] Step 120: Take a portion of the second reaction solution as the third reaction solution, add the first reaction solution and the remaining second reaction solution to the third reaction solution to react and obtain the first reaction product.

[0041] In this embodiment, when the first reaction solution and the remaining second reaction solution are added to the third reaction solution for reaction, the rate of addition of the first reaction solution is controlled within the range of 10-15 ml / min, and the rate of addition of the second reaction solution is matched with the rate of addition of the first reaction solution, so that both can be added simultaneously, and the addition of the first reaction solution and the remaining second reaction solution is completed within 30 minutes. Simultaneously, controlling the reaction temperature at 50℃-70℃ and the reaction time at 100min-200min ensures that both react fully.

[0042] In this embodiment, the mass ratio of the third reaction solution to the remaining second reaction solution is 1:(2.8-3.4). By taking a portion of the second reaction solution as the third reaction solution and adding it to the reaction vessel first, the concentration of disodium hydrogen phosphate can be kept stable and controllable during the reaction process, which is conducive to the formation of larger particle size, thus having better physical stability and providing a larger internal space.

[0043] Step 130: The first reaction product is kept at a constant temperature to obtain the second reaction product.

[0044] In this embodiment, when the first reaction product is kept at a constant temperature, the temperature is controlled to be 50℃-70℃, and the temperature is kept at a constant temperature for more than 30 minutes.

[0045] Step 140: The second reaction product is filtered, washed, evaporated and dried to obtain hybrid zirconium phosphate.

[0046] In this embodiment, when the second reaction product is filtered and washed, 15-40 times the mass of the hybrid zirconium phosphate solid is used for washing. After dehydration, the hybrid zirconium phosphate is obtained. When evaporating and drying, the temperature of evaporation and drying is controlled at 70℃-95℃ and the time of evaporation and drying is 7h-9h.

[0047] In one embodiment, the present invention also provides a hybrid zirconium phosphate, in PO4 3- 967cm -1 ~1200cm -1 At the stretching vibration peak, hybrid zirconium phosphate PO4 3- The peak is sharp and splits into two smaller peaks, while the PO4 of α-zirconium phosphate... 3- The sharp peaks split into three smaller peaks, reflecting multiple vibrational modes of phosphate groups on the lamellar surface, exhibiting a layered structure, and indicating the presence of amorphous zirconium phosphate PO4. 3-The peaks are not segmented, exhibiting an amorphous structure, intermediate between α-zirconium phosphate and amorphous zirconium phosphate. At the molecular level, it is in a hybrid state, with large particle size, while also possessing high ion exchange capacity and ion exchange rate.

[0048] In one embodiment, the present invention also provides the application of hybrid zirconium phosphate in the preparation of purification carbon rods. The purification carbon rods prepared from zirconium phosphate have significant purification effects in water purification applications. They have broad-spectrum cation adsorption properties and good removal performance for heavy metals such as chromium, manganese, iron, copper, arsenic, cadmium, barium, mercury, lead, and selenium. They are particularly effective in removing lead and also have good effects in reducing pH, TDS, and scale inhibition.

[0049] Compared with the prior art, the present invention has at least the following advantages:

[0050] (1) In this invention, a portion of the second reaction solution is used as the third reaction solution. The first reaction solution and the remaining second reaction solution are added to the third reaction solution for reaction. After being kept at a constant temperature and allowed to stand, the mixture is filtered, washed, and finally evaporated and dried to obtain a hybrid zirconium phosphate. Its microcrystalline structure has zirconium atoms as the basal plane, with each zirconium atom connected to an oxygen atom. Each phosphorus atom carries a P-OH residue or an active group PG and is connected to oxygen atoms on both sides of the basal plane. In PO4 3- 967cm -1 ~1200cm -1 At the stretching vibration peak, hybrid zirconium phosphate PO4 3- The peak is sharp and splits into two smaller peaks, intermediate between α-zirconium phosphate and amorphous zirconium phosphate, exhibiting a hybrid state at the molecular level. It possesses both high ion exchange capacity and ion exchange rate, with a cation exchange capacity of 3.5-4.5 mmol / g and a cation exchange rate of 1.20-2.15 g mmol / g. -1 min -1 This solves the problems of low exchange capacity of amorphous zirconium phosphate and slow exchange rate of crystalline zirconium phosphate, and has a wider range of applications.

[0051] (2) By setting the molar ratio of zirconium oxychloride to sodium fluoride to 1:(0.3-1) and the molar ratio of zirconium oxychloride to disodium hydrogen phosphate to 1:(1.5-4), controlling the reaction temperature to 50℃-70℃ and the reaction time to 100min-200min, hybrid zirconium phosphate can be prepared in batches using sodium fluoride as a reaction catalyst in a low-temperature hydrothermal manner. The required reaction temperature is low, the reaction time is short, the equipment requirements are low, and the preparation is simple and efficient.

[0052] (3) The prepared hybrid zirconium phosphate has a large particle size, with a D50 range of 10-25 μm. It has better physical stability, provides more internal space, which is conducive to ion diffusion and exchange, thus having better ion exchange performance. At the same time, it is easier to control the growth and formation of particles, thereby simplifying the preparation process.

[0053] (4) The prepared hybrid zirconium phosphate has broad-spectrum cationic adsorption performance and good removal performance for heavy metals such as chromium, manganese, iron, copper, arsenic, cadmium, barium, mercury, lead and selenium. In particular, it has excellent lead removal effect and also has good effects in reducing pH, TDS and scale inhibition. The purification carbon rod prepared by using it as raw material has significant purification effect in water purification applications.

[0054] The present invention will be further described below with reference to specific embodiments.

[0055] Example 1

[0056] 5.2 g of sodium fluoride and 80 g of zirconium oxychloride octahydrate were dissolved sequentially in 48 g of pure water to obtain the first reaction solution. 106 g of disodium hydrogen phosphate was dissolved in 405 g of pure water to obtain the second reaction solution. 160 g of the second reaction solution was weighed to obtain mixture C. At 70 °C, the first and second reaction solutions were added to mixture C by a peristaltic pump at flow rates of 13.1 ml / min and 30 ml / min, respectively, allowing the addition and mixing of the first and second reaction solutions to be completed simultaneously within 30 minutes. After the addition was complete, the reaction was carried out at 70 °C for 150 min. After the reaction was completed, the mixture was kept at 70 °C and allowed to stand for half an hour. After standing, the hybrid zirconium phosphate was washed with 20 times its mass of deionized water and dehydrated to obtain hybrid zirconium phosphate. The obtained hybrid zirconium phosphate was dried at 80 °C for 7 hours, with a moisture content of 14%, to obtain hybrid zirconium phosphate powder.

[0057] Example 2

[0058] 3.12 g of sodium fluoride and 80 g of zirconium oxychloride octahydrate were dissolved sequentially in 48 g of pure water to obtain the first reaction solution. 106 g of disodium hydrogen phosphate was dissolved in 405 g of pure water to obtain the second reaction solution. 160 g of the second reaction solution was weighed to obtain mixture C. At 65 °C, the first and second reaction solutions were added to mixture C by a peristaltic pump at flow rates of 13.1 ml / min and 30 ml / min, respectively, allowing the addition and mixing of the first and second reaction solutions to be completed simultaneously within 30 minutes. After the addition was complete, the reaction was carried out at 65 °C for 100 min. After the reaction was complete, the mixture was kept at 65 °C and allowed to stand for half an hour. After standing, the hybrid zirconium phosphate was washed with 20 times its mass of deionized water and dehydrated to obtain hybrid zirconium phosphate. The obtained hybrid zirconium phosphate was dried at 80 °C for 7 hours, with a moisture content of 16.7%, to obtain hybrid zirconium phosphate powder.

[0059] Example 3

[0060] 5.2 g of sodium fluoride and 80 g of zirconium oxychloride octahydrate were dissolved sequentially in 48 g of pure water to obtain the first reaction solution. 134 g of disodium hydrogen phosphate was dissolved in 450 g of pure water to obtain the second reaction solution. 183 g of the second reaction solution was weighed to obtain mixture C. At 70 °C, the first and second reaction solutions were added to mixture C by a peristaltic pump at flow rates of 13.1 ml / min and 37 ml / min, respectively, allowing the addition and mixing of the first and second reaction solutions to be completed simultaneously within 30 minutes. After the addition was complete, the reaction was carried out at 70 °C for 120 min. After the reaction was completed, the mixture was kept at 70 °C and allowed to stand for half an hour. After standing, the hybrid zirconium phosphate was washed with 20 times its mass of deionized water and dehydrated to obtain hybrid zirconium phosphate. The obtained hybrid zirconium phosphate was dried at 80 °C for 7 hours, with a moisture content of 15.1%, to obtain hybrid zirconium phosphate powder.

[0061] Example 4

[0062] 5.2 g of sodium fluoride and 80 g of zirconium oxychloride octahydrate were dissolved sequentially in 48 g of pure water to obtain the first reaction solution. 98.68 g of disodium hydrogen phosphate was dissolved in 398 g of pure water to obtain the second reaction solution. 155 g of the second reaction solution was weighed to obtain mixture C. At 70 °C, the first and second reaction solutions were added to mixture C by a peristaltic pump at flow rates of 13.1 ml / min and 28 ml / min, respectively, allowing the addition and mixing of the first and second reaction solutions to be completed simultaneously within 30 minutes. After the addition was complete, the reaction was carried out at 70 °C for 120 min. After the reaction was completed, the mixture was kept at 70 °C and allowed to stand for half an hour. After standing, the hybrid zirconium phosphate was washed with 20 times its mass of deionized water and dehydrated to obtain hybrid zirconium phosphate. The obtained hybrid zirconium phosphate was dried at 80 °C for 7 hours, with a moisture content of 13.14%, to obtain hybrid zirconium phosphate powder.

[0063] Example 5

[0064] 5.2 g of sodium fluoride and 80 g of zirconium oxychloride octahydrate were dissolved sequentially in 48 g of pure water to obtain the first reaction solution. 106 g of disodium hydrogen phosphate was dissolved in 405 g of pure water to obtain the second reaction solution. 160 g of the second reaction solution was weighed to obtain mixture C. At 50 °C, the first and second reaction solutions were added to mixture C by a peristaltic pump at flow rates of 13.1 ml / min and 30 ml / min, respectively, allowing the addition and mixing of the first and second reaction solutions to be completed simultaneously within 30 minutes. After the addition was complete, the reaction was carried out at 50 °C for 120 min. After the reaction was completed, the mixture was kept at 50 °C and allowed to stand for half an hour. After standing, the hybrid zirconium phosphate was washed with 20 times its mass of deionized water and dehydrated to obtain hybrid zirconium phosphate. The obtained hybrid zirconium phosphate was dried at 80 °C for 7 hours, with a moisture content of 18%, to obtain hybrid zirconium phosphate powder.

[0065] The ion exchange capacity and exchange rate of the hybrid zirconium phosphates prepared in Examples 1-5 were tested. The specific methods are shown below:

[0066] (1) The adsorption capacity of hybrid zirconium phosphate as an ion exchanger for ammonium ions.

[0067] Take 0.1g of the hybrid zirconium phosphate obtained in Examples 1-5 into an Erlenmeyer flask, then add 100ml of 20mmol / L ammonium carbonate solution, seal the Erlenmeyer flask with sealing film, and simultaneously prepare a blank control group. Shake at 160rppm for 2 hours on a HY-5A gyroscopic shaker, take a sample, filter the sample through a 0.45um microporous membrane, and use a UV spectrophotometer to test the ammonium concentration before and after adsorption, and calculate the exchange capacity. Accordingly, 0.1 g of amorphous zirconium phosphate, α-zirconium phosphate, and amorphous zirconium phosphate and α-zirconium phosphate physically mixed in different proportions were taken as comparative examples and tested accordingly to calculate the exchange capacity. Among them, amorphous zirconium phosphate was comparative example 1, α-zirconium phosphate was comparative example 2, amorphous zirconium phosphate and α-zirconium phosphate mixed in a 1:1 ratio was comparative example 3, amorphous zirconium phosphate and α-zirconium phosphate mixed in a 1:2 ratio was comparative example 4, and amorphous zirconium phosphate and α-zirconium phosphate mixed in a 2:1 ratio was comparative example 5.

[0068] (2) Determination of ion exchange rate.

[0069] Take 0.5g of the hybrid zirconium phosphate obtained in Examples 1-5 into an Erlenmeyer flask, then add 100ml of 27mmol / L ammonium chloride solution, seal the Erlenmeyer flask with sealing film, and simultaneously prepare a blank control group. Take samples at 5min, 10min, 20min, 30min, 60min, 90min, 120min, 150min, 210min, and 240min on a HY-5A gyroscope at a speed of 160rppm. Filter the samples through a 0.45um microporous membrane and test the ammonium concentration using a UV spectrophotometer. Calculate the exchange rate using a pseudo-second-order kinetic model. Accordingly, 0.5 g of amorphous zirconium phosphate, α-zirconium phosphate, and amorphous zirconium phosphate and α-zirconium phosphate mixed in different proportions were taken as comparative examples and tested accordingly to calculate the exchange rate. Among them, amorphous zirconium phosphate was comparative example 1, α-zirconium phosphate was comparative example 2, amorphous zirconium phosphate and α-zirconium phosphate physically mixed in a 1:1 ratio was comparative example 3, amorphous zirconium phosphate and α-zirconium phosphate mixed in a 1:2 ratio was comparative example 4, and amorphous zirconium phosphate and α-zirconium phosphate mixed in a 2:1 ratio was comparative example 5.

[0070] Simultaneously, samples of the hybrid zirconium phosphate prepared in Examples 1-5 were subjected to scanning electron microscopy (SEM) observation and particle size analysis, with the hybrid zirconium phosphate prepared in Example 1 undergoing FIR detection. Specific performance test results are shown in Table 1, and the SEM images of Examples 1, 3, and 5 are shown in the table below. Figure 2 , Figure 3 and Figure 4 As shown, the FIR spectrum of the hybrid zirconium phosphate in Example 1 is as follows. Figure 5As shown.

[0071] Table 1. Results of particle size and performance tests

[0072] Test Project D50 particle size (µm) <![CDATA[K2(g·mmol -1 min -1 )]]> <![CDATA[Q m (mmolg -1 )]]> Example 1 13.1 <![CDATA[1.22×10 -2 ]]> 4.26 Example 2 16.3 <![CDATA[1.43×10 -2 ]]> 3.86 Example 3 14.2 <![CDATA[1.81×10 -2 ]]> 4.00 Example 4 15.2 <![CDATA[1.62×10 -2 ]]> 3.75 Example 5 25.3 <![CDATA[2.12×10 -2 ]]> 3.56 Comparative Example 1 / <![CDATA[0.89×10 -1 ]]> 3.04 Comparative Example 2 / <![CDATA[0.56×10 -2 ]]> 5.5 Comparative Example 3 / <![CDATA[1.01×10 -2 ]]> 2.95 Comparative Example 4 / <![CDATA[0.60×10 -2 ]]> 3.14 Comparative Example 5 / <![CDATA[0.95×10 -2 ]]> 2.81

[0073] As shown in Table 1, the hybrid zirconium phosphate in Examples 1-5 has a higher exchange capacity than amorphous zirconium phosphate and a faster exchange rate than α-zirconium phosphate. In contrast, the exchange capacity and exchange rate of simply physically mixing zirconium phosphate in different proportions are both lower than those of the hybrid zirconium phosphate, indicating a mutual constraint between the two. Figure 5 It can be seen that in PO4 3- 967cm -1 ~1200cm -1 At the stretching vibration peak, PO4 of α-zirconium phosphate 3- The sharp peaks split into three smaller peaks, reflecting multiple vibrational modes of phosphate groups on the lamellar surface, exhibiting a layered structure, and indicating the presence of amorphous zirconium phosphate PO4. 3- The peaks are not segmented, exhibiting an amorphous structure. Example 1 shows the hybrid zirconium phosphate PO4... 3- The peak is sharp and splits into two smaller peaks, which are intermediate between α-zirconium phosphate and amorphous zirconium phosphate, and are in a hybrid state at the molecular structure level.

[0074] The broad-spectrum cation exchange capacity of the hybrid zirconium phosphate prepared in Example 1 was tested. The specific method is as follows:

[0075] According to the "Standard Examination Methods for Drinking Water" (GB / T 5750-2023), the sanitary functionality of the carbon rod with added Example 1 was tested. At a water production flow rate of 2 L / min, the removal rates of arsenic, barium, cadmium, hexavalent chromium, copper, mercury, selenium, lead, iron, and manganese in artificially prepared water were measured using the carbon rod containing hybrid zirconium phosphate powder from Example 1. The carbon rod with added hybrid zirconium phosphate powder from Example 1 had dimensions of 66.9*21*224 mm and a density of 0.627. The amount of hybrid zirconium phosphate powder added in Example 1 was 200 g. Specific performance test results are shown in Table 2.

[0076] Table 2 Performance Test Results

[0077]

[0078] As can be seen from Table 2, the carbon rod with the hybrid zirconium phosphate powder added in Example 1 has the advantage of broad-spectrum cation adsorption performance, and has good removal performance for heavy metals chromium (hexavalent), manganese, iron, copper, arsenic, cadmium, barium, mercury, lead and selenium at a water production rate of 6000L.

[0079] The water purification effect of the hybrid zirconium phosphate prepared in Example 2 was tested. The specific method is as follows:

[0080] Under test conditions of a flushing flow rate of 2 L / min and a flushing method of 5 minutes of flushing followed by a 10-minute pause, the carbon rod containing the hybrid zirconium phosphate powder of Example 2 was subjected to a flushing test. The pH and TDS of the water samples were tested at the initial cumulative flow, 100 L, 400 L, and 750 L. Simultaneously, a portion of the water sample was boiled to observe the scale inhibition effect. The carbon rod containing the hybrid zirconium phosphate powder of Example 2 had dimensions of 66.9*21*224 mm and a density of 0.634 g. The amount of hybrid zirconium phosphate powder added in Example 2 was 200 g. Specific performance test results are shown in Table 3.

[0081] Table 3 Performance Test Results

[0082]

[0083] From Table 3 and Figure 6 It can be seen that the carbon rod with added hybrid zirconium phosphate powder from Example 2 has the effect of reducing pH, TDS and removing scale in water purification applications.

[0084] The water purification effect of the hybrid zirconium phosphate prepared in Example 3 was tested. The specific method is as follows:

[0085] The water bottle filter cartridge was flushed daily with 30L of spiked water, divided into three time periods (3-4 hours apart). In each time period, 10L of water was continuously added at a flow rate of 420ml / min. pH and TDS were tested on water samples at the initial flow rate, 10L, 30L, and 60L. The water bottle filter cartridge contained 40g of activated carbon and 60g of the hybrid zirconium phosphate powder from Example 3. Specific performance test results are shown in Table 4.

[0086] Table 4 Performance Test Results

[0087]

[0088] From Table 4 and Figure 7 It can be seen that the addition of hybrid zirconium phosphate particles from Example 3 has the effect of reducing pH, TDS and removing scale in water purification applications.

[0089] The water purification effect of the hybrid zirconium phosphate prepared in Example 4 was tested. The specific method is as follows:

[0090] Lead was spiked according to the NSF53 standard for alkaline lead, with a 10-minute flush followed by a 10-minute rest, and a flushing flow rate of 2 L / min. Samples were taken at different flushing points to test the lead removal rate. The carbon rod containing the hybrid zirconium phosphate powder from Example 4 had dimensions of 45*16*207 mm, and the amount of hybrid zirconium phosphate powder added in Example 4 was 80 g. Specific performance test results are shown in Table 5.

[0091] Table 5 Performance Test Results

[0092] Cumulative flushing flow rate (L) Lead removal rate (%) initial 100 500L 100 1000L 100 1500L 100 2000L 100

[0093] The flushing was stopped at 2000L. The carbon rod with the added hybrid zirconium phosphate powder of Example 4 had a lifespan of >2000L. As can be seen from Table 5, the carbon rod with the added hybrid zirconium phosphate powder of Example 4 has excellent lead removal effect.

[0094] The hybrid zirconium phosphate prepared in Example 5 was subjected to NH4 removal. + Test. The specific method is as follows:

[0095] An adsorption column was provided, the structure of which, from top to bottom, consisted of a nylon mesh, a 30g carbon powder layer, a 500g hybrid zirconium phosphate layer (as described in Example 5), a 20g zirconium hydroxide layer, and the nylon mesh. 60L of dialysate was provided, comprising: 351.52g sodium chloride, 8.9g potassium chloride, 12.2g calcium chloride, 9g magnesium chloride hexahydrate, 7.5g glacial acetic acid, 168g sodium bicarbonate, and 40g ammonium carbonate. The dialysate flow rate was set to 30ml / min. Specific performance test results are shown in Table 6.

[0096] Table 6 Performance Test Results

[0097] Time (h) <![CDATA[NH4 + Removal rate (%) 0 100 1.5 100 10.5 100 21.5 100 25.5 100 28.5 100 35 100

[0098] As can be seen from Table 6, the addition of the hybrid zirconium phosphate powder of Example 5 has an excellent effect on removing ammonium ions, and can meet the challenge of 60L of dialysis solution.

[0099] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0100] The embodiments described above are merely illustrative of several implementations of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A method for preparing hybrid zirconium phosphate, characterized in that, Includes the following steps: A first reaction solution and a second reaction solution are provided. The first reaction solution comprises zirconium oxychloride, sodium fluoride and deionized water, and the second reaction solution comprises disodium hydrogen phosphate and deionized water. Take a portion of the second reaction solution as the third reaction solution, add the first reaction solution and the remaining second reaction solution to the third reaction solution to carry out the reaction, control the reaction temperature at 50℃-70℃ and the reaction time at 100min-200min, and obtain the first reaction product; The first reaction product was allowed to stand at a constant temperature to obtain the second reaction product; The second reaction product was filtered, washed, evaporated and dried to obtain hybrid zirconium phosphate; In the first reaction solution, the molar ratio of zirconium oxychloride, sodium fluoride and deionized water, based on zirconium ions, is 1:(0.3-1):(10-30), and in the second reaction solution, the molar ratio of disodium hydrogen phosphate and deionized water is 1:(25-45). Based on zirconium ions, the molar ratio of zirconium oxychloride to disodium hydrogen phosphate is 1:(1.5-4), and the mass ratio of the third reaction solution to the remaining second reaction solution is 1:(2.8-3.4).

2. The method for preparing hybrid zirconium phosphate according to claim 1, characterized in that, The molar ratio of zirconium oxychloride to disodium hydrogen phosphate is 1:(2-3).

3. The method for preparing hybrid zirconium phosphate according to claim 1, characterized in that, When the first reaction product is kept at a constant temperature, the temperature is controlled at 50℃-70℃ and kept at a constant temperature for more than 30 minutes.

4. The method for preparing hybrid zirconium phosphate according to claim 1, characterized in that, When the second reaction product is filtered, washed, and then evaporated and dried, the evaporation and drying temperature is controlled at 70℃-95℃, and the evaporation and drying time is 7h-9h.

5. A hybrid zirconium phosphate, characterized in that, It is prepared by the hybrid zirconium phosphate preparation method according to any one of claims 1-4.

6. The application of the hybrid zirconium phosphate as described in claim 5 in the preparation of purification carbon rods.

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