Electro-regeneration adsorption desalting device and method for zirconium phosphate adsorption material, carbon-supported hybrid zirconium phosphate material and application of carbon-supported hybrid zirconium phosphate material

Abstract

The invention discloses an electric regeneration adsorption desalting device and method for a zirconium phosphate adsorption material, a carbon-supported hybrid zirconium phosphate material and application, and belongs to the technical field of water treatment. The technical problems to be solved are that existing ion exchange resin such as zirconium phosphate adsorption materials is complex in regeneration, large in size, high in price and high in waste yield, newly introduced sodium ions are not beneficial to drinking, and the like. According to the technical scheme, the electro-regeneration adsorption desalting device is characterized by comprising an electrolytic bath, a hollow cylindrical anode, a central anode and a cathode, wherein the hollow cylindrical anode, the central anode and the cathode are positioned in the electrolytic bath; wherein the zirconium phosphate adsorption material to be treated is compounded in the carbon rod to serve as an anode, and the electrolyte in the electrolytic bath is water.

Description

Technical Field

[0001] This invention belongs to the field of water treatment technology and provides an electro-regeneration adsorption desalination device and method for zirconium phosphate adsorbent materials, as well as carbon-supported hybrid zirconium phosphate materials and their applications. Background Technology

[0002] Ion exchange resins are insoluble polymeric compounds composed of a three-dimensional network framework and active groups attached to the framework. The active groups ionize upon contact with water, separating into two parts: a fixed portion firmly bound to the framework and unable to move freely, forming fixed ions; and an active portion that can move freely within a certain space and exchange with other ions of the same charge in the surrounding solution, forming exchangeable ions. When a resin loses its ability to exchange ions in water, it becomes ineffective. After ineffectiveness, it must be regenerated to restore its exchange capacity. The degree of resin regeneration significantly affects the resin's working exchange capacity (or lifespan). Regeneration is a necessary means to maximize the resin's adsorption capacity.

[0003] Chinese invention patent application CN101007267A (publication date: August 1, 2007) discloses an in-situ electrochemical regeneration process for adsorption resin. The process involves wrapping the adsorption resin with a cylindrical ion exchange membrane, installing an anode inside the resin, and a cathode outside the membrane. Perforated plates are placed above and below the resin bed to prevent leakage. Once the resin is saturated, an anode regeneration solution is injected into the bed, while a cathode circulating solution is introduced outside the membrane. A DC power supply is then applied to the anode and cathode. The adsorbed organic pollutants are decomposed, and the resin is regenerated, restoring its adsorption capacity. This in-situ electrochemical regeneration process eliminates the need to consume and treat eluents such as acids, alkalis, or organic solvents used in resin regeneration, significantly reducing the regeneration cost and simplifying the process.

[0004] My master's thesis (Experimental and Mechanistic Study on Electrochemical Regeneration of Waste Activated Carbon [D], Yuan Heng, Tianjin University [2025-11-28]) investigated the effects of electrolyte concentration, regeneration time, regeneration current, regeneration region, and electrolyte solution pH on regeneration efficiency, using regeneration efficiency as the objective function. The regeneration mechanism was studied, and a set of relatively optimal regeneration conditions was finally determined: the electrolyte is a 0.1 mol / L Na2SO4 solution, the regeneration time is 6 h, the regeneration current is 0.8 A, the regeneration region is the cathode region, and the electrolyte solution pH is 11.5. Under these conditions, the regeneration efficiency can reach a maximum of 81.7%.

[0005] The prior art represented by the aforementioned documents has at least the following unresolved technical problems or defects: Conventional activated carbon adsorbents or composite adsorbents of activated carbon and other components have poor regeneration effects, or their lifespan decreases after regeneration, and their stability is poor.

[0006] In solving the above problems or overcoming the above defects, the present invention encountered the following difficulties and obstacles: Organic resins release sodium ions into the water when adsorbing calcium and magnesium ions, which is not conducive to drinking. Overcoming the introduction of sodium ions is a difficult problem for current electro-regeneration systems. Summary of the Invention

[0007] The purpose of this invention is to provide: An electro-regeneration adsorption desalination device for zirconium phosphate adsorbent materials, and related technologies, to solve the technical problems of existing ion exchange resins, such as complex regeneration, large size, high price, high waste generation, and the introduction of new sodium ions which are not conducive to drinking water, or a combination thereof.

[0008] Terminology Explanation: Unless otherwise defined, all technical terms in this document have the same meanings as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains. Unless otherwise stated, all patents, patent inventions, and publications cited in this document are incorporated herein by reference in their entirety. If multiple definitions exist for terms in this document, the definitions in this chapter shall prevail.

[0009] It should be understood that the above brief description and the following detailed description are exemplary and for illustrative purposes only, and do not limit the subject matter of the invention in any way. In this invention, the singular is used in conjunction with the plural unless otherwise specifically stated. It should also be noted that, unless otherwise stated, the use of “or” or “or” means “and / or”. Furthermore, the use of the term “comprising” and other forms such as “including,” “containing,” and “contains” are not limiting.

[0010] The definitions of standard chemical terms can be found in the reference "Chemical Industry Dictionary, 2nd Edition. Edited by Wang Zhen. Beijing: Chemical Industry Press, April 1985."

[0011] Unless otherwise stated, conventional methods within the scope of the art shall be used.

[0012] Unless specifically defined herein, the use of all commercially available products herein employs standard techniques. For example, it may be carried out using the manufacturer's instructions for use with the kit, or in accordance with methods known in the art or the description of this invention. The techniques and methods described herein can generally be implemented according to conventional methods well known in the art, based on the descriptions in the various summary and more specific documents cited and discussed in this specification.

[0013] The terms "optional / arbitrary" or "optionally / arbitrarily" mean that the event or condition described below may or may not occur, including both the occurrence and non-occurrence of the event or condition. For example, "any cation exchange membrane" as mentioned below refers to any polymeric membrane material that is selectively permeable to cations.

[0014] The term "activated carbon" as used herein refers to amorphous carbon that has undergone activation treatment. It is available in powder, granular, or pellet form and has strong adsorption capacity. In this invention, its particle size and other properties are not specifically limited.

[0015] The term "adhesive powder" as used in this article refers to a material with certain adhesive properties, used to bind activated carbon and the adsorbent material to be treated together under certain processes.

[0016] The term "cation exchange membrane" as used in this article refers to a polymeric membrane that selectively permeates cations. Its core is a negatively charged fixed group (such as sulfonate), which allows cations to migrate directionally under the influence of an electric field while blocking anions. It is mainly used in electrodialysis, electrolysis, water treatment, and other fields to efficiently separate or concentrate ions in solutions.

[0017] The term "electrolyte" as used in this article refers to a device that can be used for electrolysis, specifically a device that uses an external power source to drive the directional migration of ions in an electrolyte solution or molten electrolyte, thereby initiating a redox reaction.

[0018] In a first aspect, the present invention provides: an electroregenerative adsorption desalination device for zirconium phosphate adsorbent materials, comprising: an electrolytic cell and a hollow cylindrical anode, a central anode and a cathode located within the electrolytic cell; wherein the zirconium phosphate adsorbent material to be treated is loaded onto a carbon rod as the anode, and the electrolyte in the electrolytic cell is water.

[0019] This includes technical features such as device structure, the positional relationship of each electrode, the central anode, and the cathode.

[0020] The device structure is selected from either a single-cavity structure or a double-cavity structure.

[0021] In the single-cavity structure, the positional relationship of the electrodes is as follows: the central anode is located inside the axis of the anode; the cathode is sleeved outside the anode to form a coaxial cylindrical electrode structure.

[0022] In the dual-cavity structure, the positional relationship of the electrodes is as follows: the central anode is located inside the axis of the anode; the cathode and the anode are separated by a cation exchange membrane and placed in the two cavities of the dual-cavity device respectively.

[0023] Furthermore, the electrolyte levels in the two chambers of the dual-chamber device are the same.

[0024] The cation exchange membrane is selected from any one of perfluorosulfonic acid membranes, fluorine-free proton exchange membranes, carboxylic acid type ion exchange membranes, and sulfonated polyether ether ketone membranes.

[0025] The central anode is selected from any one of ruthenium-iridium titanium electrode, titanium-based lead dioxide electrode, titanium-based iridium dioxide electrode, copper electrode, and stainless steel-based composite oxide electrode; preferably, it is a ruthenium-iridium titanium electrode.

[0026] The cathode is selected from any one of titanium mesh electrode, stainless steel mesh electrode, nickel mesh electrode, copper mesh electrode and graphite mesh electrode; preferably, it is a titanium mesh electrode.

[0027] Based on further solutions to the technical problems of the present invention, or simultaneous solutions to multiple technical problems, the preferred solution in the technical solution provided in the first aspect of the present invention includes: The first preferred embodiment: the central anode is selected from any one of a ruthenium-iridium titanium electrode, a titanium-based lead dioxide electrode, a titanium-based iridium dioxide electrode, a copper electrode, and a stainless steel-based composite oxide electrode; preferably a ruthenium-iridium titanium electrode; and / or the cathode is selected from any one of a titanium mesh electrode, a stainless steel mesh electrode, a nickel mesh electrode, a copper mesh electrode, and a graphite mesh electrode; preferably a titanium mesh electrode. In this invention, the central anode is preferably a ruthenium-iridium titanium electrode, which is a good corrosion-resistant material and a good oxygen evolution electrode. As a central anode, it better helps the anode generate hydrogen ions during electrolysis, which is more conducive to the regeneration of the carbon rod.

[0028] The second preferred embodiment is as follows: the electroregenerative adsorption desalination device is a single-chamber device, specifically structured as follows: the central anode is located inside the axis of the anode; the cathode is sleeved outside the anode to form a coaxial cylindrical electrode structure; and / or the electroregenerative adsorption desalination device is a dual-chamber device, specifically structured as follows: the central anode is located inside the axis of the anode; the cathode and the anode are separated by a cation exchange membrane and placed in the cathode chamber and anode chamber of the dual-chamber device respectively.

[0029] The coaxial electrode structure formed by the central anode and the anode in this invention effectively shortens the ion migration path and improves the regeneration efficiency. The carbon rod, as an ion exchange medium carrier, has both conductivity and adsorption properties. The hydrogen ions generated during electrolysis will exchange with the calcium and magnesium ions adsorbed by the zirconium phosphate adsorbent material on the carbon rod, freeing up adsorption sites and thus completing the regeneration. In other words, the hydrogen ions generated by electrolysis are regenerated in situ without the need for additional chemical reagents.

[0030] Secondly, the present invention provides: a method for electro-regeneration and desalination of zirconium phosphate adsorbents using the above-mentioned apparatus, characterized by comprising the following steps: (1) Preparation of anode material: Take the zirconium phosphate adsorbent material to be treated, activated carbon and adhesive powder, mix them thoroughly and evenly, and calcine to obtain the anode material; (2) Assembly of the electro-regenerative adsorption desalination device: The zirconium phosphate adsorbent to be treated is connected as the anode to the ruthenium-iridium titanium electrode as the central anode, and the titanium mesh as the cathode is placed outside the anode, or the anode and cathode connected to the ruthenium-iridium titanium electrode are placed in the two chambers of the electrolytic cell respectively; then the anode is connected to the positive terminal of the external power supply, and the cathode is connected to the negative terminal of the external power supply. (3) Electrolysis process: Apply voltage to perform electrolysis, record the current change during the electrolysis process to monitor the regeneration effect.

[0031] This includes technical features such as the preparation of the anode material carbon rod, the type of adhesive powder, calcination conditions, and electrolysis conditions.

[0032] The carbon rod is made of 20-40% zirconium phosphate adsorbent material, 25-45% activated carbon, and 25-40% adhesive powder by weight percentage; preferably, the carbon rod is made of 30% zirconium phosphate adsorbent material, 35% activated carbon, and 35% adhesive powder. The adhesive powder is selected from any one of polyethylene, polypropylene, high molecular weight polyethylene, polyvinyl chloride, epoxy resin and phenolic resin.

[0033] The outer diameter of the carbon rod is 30-80mm, for example, 30, 40, 50, 60, 70 or 80mm; the inner diameter is 10-60mm, for example, 10, 20, 30, 40, 50 or 60mm; and the length is 10-500mm, for example, 10, 50, 100, 150, 200, 250, 300, 350, 400, 450 or 500mm.

[0034] The density of the carbon rod is 0.55-0.68 g / cm³. 3 For example, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, or 0.68 g / cm³ 3 .

[0035] The calcination temperature is 130-200℃, for example 130, 140, 150, 160, 170, 180, 190 or 200℃, and the time is 60-70min, for example 60, 65 or 70min.

[0036] Electrolysis uses a constant voltage of 2.4-20V, such as 2.4V, 4.8V, 10V, 12V, 14V, 16V, 18V or 20V.

[0037] Based on further solutions to the technical problems of the present invention, or simultaneous solutions to multiple technical problems, the preferred solution in the technical solution provided in the second aspect of the present invention includes: The first preferred embodiment is that, by mass percentage, the carbon rod is made of 20-40% zirconium phosphate adsorbent material, 25-45% activated carbon, and 25-40% adhesive powder.

[0038] A further preferred embodiment of the first preferred embodiment: the carbon rod is made of 30% zirconium phosphate adsorbent, 35% activated carbon, and 35% adhesive powder. In this invention, an excessively high or low proportion of zirconium phosphate adsorbent in the carbon rod will affect the electro-regeneration effect of the zirconium phosphate adsorbent; too little adhesive powder will not guarantee the bonding strength of the carbon rod, while too much will affect the electro-regeneration effect of the zirconium phosphate adsorbent.

[0039] A further preferred embodiment of the first preferred embodiment: the adhesive powder is selected from polyethylene, polypropylene, high molecular weight polyethylene, polyvinyl chloride, epoxy resin and phenolic resin.

[0040] The second preferred embodiment: the outer diameter, inner diameter, and length of the carbon rod are 30-80mm, 10-60mm, and 10-500mm, respectively; and / or the density of the carbon rod is 0.55-0.68g / cm³. 3 .

[0041] The third preferred option is that in step (1), the calcination temperature is 130-200℃ and the time is 6-70min.

[0042] The fourth preferred embodiment is that the electrolysis is performed using a constant voltage of 2.4-20V.

[0043] Thirdly, the present invention provides the application of the above-described electro-regeneration desalination device or the above-described electro-regeneration desalination method in the desalination and regeneration of zirconium phosphate adsorbent materials.

[0044] Fourthly, the present invention provides: a carbon-supported hybrid zirconium phosphate material, wherein the raw materials for preparing the carbon-supported hybrid zirconium phosphate material include: a zirconium source, a phosphorus source, a fluoride ion source, and activated carbon, and the preparation method is as follows: (1) Amorphous zirconium phosphate was prepared by taking zirconium source and phosphorus source and using sol-gel method; (2) Take amorphous zirconium phosphate, fluoride ion source and activated carbon, mix them thoroughly, and heat them to react to obtain carbon-supported hybrid zirconium phosphate.

[0045] This includes technical features such as activated carbon, zirconium source, phosphorus source, fluoride ion source, and their dosage.

[0046] The molar ratio of the zirconium source to the phosphorus source is 1:1-5, including but not limited to 1:1, 1:2, 1:3, 1:4 or 1:5; preferably 1:3-5, including but not limited to 1:3, 1:4 or 1:5; and more preferably 1:3.

[0047] The activated carbon in the carbon-supported hybrid zirconium phosphate has a mass percentage of 15-25%, including but not limited to 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%; preferably 20-25%, including but not limited to 20%, 21%, 22%, 23%, 24% or 25%; and more preferably 20%.

[0048] The zirconium source is selected from one or more of zirconium oxychloride, zirconium nitrate and zirconium chloride; preferably zirconium oxychloride.

[0049] The phosphorus source is selected from one or more of phosphoric acid, diammonium hydrogen phosphate, and sodium dihydrogen phosphate; preferably phosphoric acid.

[0050] The fluoride ion source is selected from one or more of sodium fluoride, potassium fluoride, ammonium fluoride, and calcium fluoride; preferably sodium fluoride.

[0051] Fifthly, the present invention provides a method for preparing the above-mentioned carbon-supported hybrid zirconium phosphate material, comprising the following steps: (1) Dissolve zirconium source and phosphorus source in water respectively to obtain solution 1 and solution 2; (2) Mix solution 1 and solution 2, and prepare amorphous zirconium phosphate by sol-gel method; (3) Take amorphous zirconium phosphate, fluoride ion source and activated carbon, mix them thoroughly, and heat them to react to obtain carbon-supported hybrid zirconium phosphate.

[0052] These include technical features such as the concentrations of solution 1 and solution 2, sol-gel reaction conditions, and temperature-induced reaction conditions.

[0053] In step (1), the concentration of the zirconium source in solution 1 is 0.5-0.7 mol / L, including but not limited to 0.5, 0.55, 0.6, 0.65 or 0.7 mol / L; preferably 0.6 mol / L.

[0054] In step (1), the concentration of the phosphorus source in solution 2 is 1-2 mol / L, including but not limited to 1, 1.2, 1.4, 1.6, 1.8 or 2 mol / L; preferably 1.5 mol / L.

[0055] In step (2), the sol-gel reaction temperature is 20-50℃, including but not limited to 20, 25, 30, 35, 40, 45, or 50℃; and the time is 20-30 hours, including but not limited to 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 hours. Preferably, the sol-gel reaction temperature is 20-30℃, including but not limited to 20, 25, or 30℃; and the time is 24 hours. In step (3), the temperature of the heating reaction is 60-90℃, including but not limited to 60, 65, 70, 75, 80, 85 or 90℃; the time is 5-7h, including but not limited to 5, 5.5, 6, 6.5 or 7h. Preferably, the temperature of the heating reaction is 80℃; the time is 7h.

[0056] In a sixth aspect, the present invention provides the application of the above-described carbon-supported hybrid zirconium phosphate material or the carbon-supported hybrid zirconium phosphate material prepared by the above-described preparation method in water treatment.

[0057] This includes the technical feature: water treatment.

[0058] Among them, water treatment is water desalination treatment.

[0059] The present invention has at least the following beneficial effects: Compared with the prior art, the device of the present invention has a simple structure, low cost of regeneration device and method, and no waste generation; in particular, it does not introduce sodium ions or other problems that are detrimental to drinking water, and has better technical effect.

[0060] Furthermore, based on the results of Example 1, the present invention achieves better regeneration of ion exchange materials by determining the anode and cathode and selecting the position of the central anode conductor (the central anode conductor is placed inside the axis of the anode material carbon rod), providing a prerequisite for the regeneration of ion exchange materials, especially zirconium phosphate materials, and ensuring their application in water treatment.

[0061] Furthermore, existing zirconium phosphate materials have a long lifespan but cannot be stably regenerated; those that can be stably regenerated suffer from short lifespans. The zirconium phosphate material (carbon-supported hybrid zirconium phosphate) provided by this invention not only has a long lifespan but can also be stably regenerated, exhibiting superior overall performance. It is particularly suitable for water treatment, especially for water desalination (Ca... 2+ Mg 2+ It has potential applications in this area. Attached Figure Description

[0062] Figure 1 This is a schematic diagram of the single-cavity electroregeneration system with carbon rod as the anode of the present invention; Figure 2 This is a schematic diagram of the single-cavity electroregeneration system with carbon rod as cathode according to the present invention; Figure 3 This is a photograph of the ruthenium-iridium-titanium electrode of the present invention inside a hollow cylindrical carbon rod; Figure 4 This is a photograph of the ruthenium-iridium-titanium electrode of the present invention on the outside of a hollow cylindrical carbon rod; Figure 5 This is a schematic diagram of the dual-cavity electroregeneration system of the present invention; Figure 6The image shows the SEM morphology of the zirconium phosphate adsorbent material prepared in Example 3 of this invention; where A represents hybrid zirconium phosphate and B represents carbon-supported hybrid zirconium phosphate. Figure 7 The XRD pattern of the zirconium phosphate adsorbent material prepared in Example 3 of this invention is shown below. Figure labels: 1 is ruthenium-iridium-titanium electrode, 2 is carbon rod, 3 is titanium mesh, 4 is electrode, 5 is cation exchange membrane, 6 is anode chamber, 7 is cathode chamber, and 8 is electrolytic cell. Detailed Implementation

[0063] The following non-limiting embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of the present invention, but do not limit the invention in any way. The following content is merely an exemplary description of the scope of protection claimed by the present invention, and those skilled in the art can make various changes and modifications to the present invention based on the disclosed content, and such changes should also fall within the scope of protection claimed by the present invention.

[0064] The present invention will be further described below by way of specific embodiments. Unless otherwise specified, all instruments, devices, equipment, reagents, products, etc., used in the embodiments of the present invention are obtained through conventional commercial means.

[0065] Basic Example 1: Preparation of Amorphous Zirconium Phosphate Using zirconium oxychloride (ZrOCl2·8H2O) as the zirconium source and phosphoric acid (H3PO4) as the phosphorus source, atomized zirconium phosphate was synthesized at room temperature (25℃) by controlling the ion coordination environment. The specific steps are as follows: ZrOCl2·8H2O and H2O were mixed and dissolved in a molar ratio of 1:11 to obtain solution A; H3PO4 and H2O were mixed and diluted in a molar ratio of 1:11 to obtain solution B; solution A and solution B were mixed (wherein, the molar ratio of ZrOCl2·8H2O to H3PO4 was strictly controlled at 1:3 to ensure sufficient reaction), and solution A and solution B were slowly mixed at a matched rate (wherein, solution A: 13.3 mL / min; solution B: 26 mL / min), finally generating amorphous zirconium phosphate with an open porous structure.

[0066] Basic Example 2: Preparation of Layered Zirconium Phosphate Layered zirconium phosphate was prepared using amorphous zirconium phosphate from Basic Example 1 as a precursor and NaF as a fluoride ion source. Specifically, 80 g of amorphous zirconium phosphate and 8.32 g of NaF (mass ratio of approximately 1:0.1) were reacted at 80 °C for 5 h to obtain layered zirconium phosphate.

[0067] Example 1 like Figure 1 , 2As shown, this embodiment provides a single-cavity electroregenerative adsorption desalination device, including: an electrolytic cell 8 and a hollow cylindrical anode 2, a central anode 1 (wire), and a cathode 3 located within the electrolytic cell; the anode 2 is connected to the positive terminal of a power supply, and the cathode 3 is connected to the negative terminal of the power supply. Next, electroregeneration experiments will be conducted on zirconium phosphate adsorbent materials using the following four electroregeneration device structures: Electro-regeneration device structure 1: The zirconium phosphate adsorbent to be treated is loaded onto a carbon rod as the anode, and a titanium mesh is used as the cathode; a ruthenium-iridium titanium electrode is used as the central anode, which is located within the cavity of the anode carbon rod, as shown below. Figure 2 As shown in Figure A, the physical diagram of the positional relationship between the central anode and the anode is as follows. Figure 3 As shown; Electro-regeneration device structure 2: The zirconium phosphate adsorbent to be treated is loaded onto a carbon rod as the anode, and a titanium mesh is used as the cathode. A ruthenium-iridium titanium electrode is located outside the cavity of the anode carbon rod, as shown below. Figure 2 As shown in Figure B, the physical diagram of the relationship between the central anode and the anode positions is as follows. Figure 4 As shown; Structure 3 of the electro-regeneration device: The zirconium phosphate adsorbent to be treated is loaded onto a carbon rod as the cathode, and a titanium mesh is used as the anode; a ruthenium-iridium titanium electrode is used as the central anode, which is located inside the cathode carbon rod cavity, as shown below. Figure 3 As shown in Figure A, the physical diagram of the positional relationship between the central anode and cathode is as follows. Figure 3 As shown; Structure 4 of the electro-regeneration device: The zirconium phosphate adsorbent to be treated is loaded onto a carbon rod as the cathode, and a titanium mesh is used as the anode. A ruthenium-iridium titanium electrode is located outside the cathode carbon rod cavity, as shown below. Figure 3 As shown in Figure B, the physical diagram of the positional relationship between the central anode and cathode is as follows. Figure 4 As shown.

[0068] The method for preparing carbon rods loaded with zirconium phosphate adsorbent material to be treated is as follows: A mixture of 30 wt% zirconium phosphate adsorbent material, 35 wt% activated carbon, and 35 wt% polyethylene was prepared and sintered at 190℃ for 70 min to produce corresponding carbon rods (carbon rod specifications: 41×16×178mm; carbon rod density: 0.67-0.68g / cm³). 3 ).

[0069] The specific process is as follows: (1) First, place the newly prepared carbon rod in hard water (calcium-magnesium molar ratio of 4:1, total hardness (calculated as CaCO3) of 500 mg / L, Ca 2+ Content ≈180 mg / L, Mg 2+The adsorption of calcium and magnesium ions in hard water (national standard hard water with a content of ≈22.5 mg / L) was carried out by passing hard water through the carbon rod at a flow rate of 0.5 mL / min until the removal rate of calcium and magnesium ions in the hard water reached less than 10%, causing the carbon rod to become saturated and ineffective. At the same time, the adsorption end life (cumulative flushing volume) was tested. (2) After adsorption failure, the failed carbon rod is used as an anode with a ruthenium-iridium-titanium electrode, and a titanium mesh electrode is placed over the carbon rod as a cathode. Finally, it is placed in a container with a calcium-magnesium molar ratio of 4:1 and a total hardness (calculated as CaCO3) of 500 mg / L. 2+ Content ≈180 mg / L, Mg 2+ Electrolysis was carried out in a single-chamber electrolytic cell using national standard hard water with a content of ≈22.5 mg / L as the electrolyte; (3) Connect the power supply (the anode is connected to the positive terminal of the power supply, and the cathode is connected to the negative terminal of the power supply), and the power supply operates at a constant voltage of 16V. (4) The water is changed every two hours during the electrolysis process. The water needs to be changed four times in the whole process. The change of current during the electrolysis process needs to be recorded each time the water is changed. (5) After regeneration, the regeneration effect of the carbon rod was measured by flushing with water at a flow rate of 0.5 mL / min.

[0070] Electroregeneration experiments were conducted on the above-mentioned layered zirconium phosphate using the four structures described above, and the hardness removal rate, pH value change, and TDS change during the process were recorded. The results are shown in Table 1; the current data for the four water changes are shown in Table 2.

[0071] Table 1. Electroregeneration performance of layered zirconium phosphate under four different electroregeneration device structures.

[0072] Table 2. Current variation results during water exchange of layered zirconium phosphate under four different electro-regeneration device structures.

[0073] The results in Tables 1 and 2 show that the lifespan of the first electroregeneration device structure is 70L, and that of the second structure is 60L. While there is no significant difference in removal rate between the two structures, the first structure has a higher current and a greater decrease in pH and TDS. The third and fourth structures have a lifespan of 6L, and their pH and TDS increase instead of decreasing. Therefore, it can be concluded that regeneration fails when using carbon rods as cathodes in structures three and four, and the first structure exhibits the best electroregeneration effect.

[0074] The layered zirconium phosphate was regenerated a second and third time using the first two electro-regeneration device structures, and the hardness removal rate, pH value change and TDS change were recorded during the process. The results are shown in Table 3; the current data for the four water changes are shown in Table 4.

[0075] Table 3. Effects of second and third electroregeneration of layered zirconium phosphate under the first two electroregeneration device structures.

[0076] Table 4. Current changes during the water exchange process of the second and third electro-regeneration of layered zirconium phosphate.

[0077] As shown in Tables 3 and 4, based on the second regeneration data, the lifespan of the first electroregeneration device was 50L, while that of the second device was 40L. The first device showed a greater decrease in pH and TDS values, indicating that the first device performed better in the second regeneration. Similarly, based on the third regeneration data, the lifespan of the first device was 40L, while that of the second device was 12.5L. Again, the first device showed a greater decrease in pH and TDS values, again indicating that the first device performed better in the second regeneration.

[0078] Based on the above three regeneration data, the first electro-regeneration device structure 1 in this invention, namely, the device structure in which the ruthenium-iridium-titanium electrode is placed at the axial center of the carbon rod to form the central anode, and the titanium mesh is wrapped around the carbon rod as the cathode, has the best electro-regeneration effect on the zirconium phosphate adsorbent material.

[0079] Example 2 like Figure 5 As shown, this embodiment provides a dual-chamber electroregenerative adsorption desalination device, including: an electrolytic cell 8 and a hollow cylindrical anode 2, a central anode 1, and a cathode 3 located within the electrolytic cell; the central anode 1 is located inside the axis of the anode 2; the cathode 3 and the anode 2 are separated by a cation exchange membrane and placed in the cathode chamber 7 and anode chamber 6 of the dual-chamber device, respectively; the anode 2 is connected to the positive terminal of a power supply, and the cathode 3 is connected to the negative terminal of a power supply. The electrolyte levels in the two chambers of the dual-chamber device are the same.

[0080] The electroregeneration effect of this dual-chamber electroregeneration adsorption desalination device is comparable to that of the first electroregeneration device in Example 1, and it can also be used for the electroregeneration of zirconium phosphate adsorbents. Furthermore, in this dual-chamber electroregeneration adsorption desalination device, if the central anode 1 is placed outside the anode carbon rod chamber, similar to the second electroregeneration device in Example 1, the electroregeneration lifespan is significantly reduced, and the regeneration effect is poor.

[0081] Comparative Example 1: Direct Electroregeneration Experiment of Zirconium Phosphate Adsorbent Particles The dual-chamber electroregeneration device of Example 2 was used, with the difference that the layered zirconium phosphate particles to be treated (with the same mass as the carbon rod in Example 2) were directly placed in the anode chamber 6. The ruthenium-iridium-titanium electrode was immersed in the electrolyte (water) in the anode chamber and connected to the positive terminal of the power supply. The titanium mesh served as the cathode and was connected to the negative terminal of the power supply. Electrolysis was also performed for 8 hours, with the water changed every 4 hours, and the device operated at a constant voltage of 16V. The hardness removal rate, pH change, and TDS change were recorded throughout the electroregeneration process, and the results are shown in Table 5.

[0082] Table 5

[0083] The data in Table 5 show that the test life of granular material is relatively short, and the granular material is easily lost during the water change process in the experiment. Therefore, pure granular material cannot achieve full regeneration of zirconium phosphate material.

[0084] Example 3: Preparation of hybrid zirconium phosphate and carbon-supported hybrid zirconium phosphate 1. Preparation of hybrid zirconium phosphate: The amorphous zirconium phosphate obtained from Basic Preparation Example 1 was thoroughly mixed with a fluoride ion source at a mass ratio of 1:0.1 and reacted at 90°C for 150 min to obtain hybrid zirconium phosphate with the morphology shown below. Figure 6 As shown in A, the XRD pattern is as follows: Figure 7 As shown.

[0085] 2. Preparation of carbon-supported hybrid zirconium phosphate: The amorphous zirconium phosphate obtained from Basic Preparation Example 1, a fluoride ion source in a mass ratio of 1:0.1, and 20 wt% activated carbon were thoroughly mixed and reacted at 90 °C for 150 min to obtain carbon-supported hybrid zirconium phosphate with the morphology shown in Figure 1. Figure 6 As shown in B, the XRD pattern is as follows: Figure 7 As shown.

[0086] The SEM and XRD results show that the carbon-supported hybrid zirconium phosphate (90℃ 150min) exhibits a clear crystal structure similar to that of the hybrid zirconium phosphate (90℃ 150min), but the baseline is unstable, belonging to a hybrid structure containing layered structures in an amorphous form.

[0087] Following the experimental method of Example 1, the two zirconium phosphate materials were subjected to electro-regeneration experiments using electro-regeneration device structure 1, and the hardness removal rate, pH value change, and TDS change were recorded during the process. The electro-regeneration results of hybrid zirconium phosphate are shown in Table 6, and the electro-regeneration results of carbon-supported hybrid zirconium phosphate are shown in Table 7.

[0088] Table 6. Electroregeneration results of hybrid zirconium phosphate

[0089] Table 7. Results of electroregeneration of carbon-supported hybrid zirconium phosphate

[0090] As can be seen from the data in Tables 6 and 7 (with the removal rate below 10% as the end of the lifespan), hybrid zirconium phosphate exhibits good regeneration performance and can be regenerated stably, but its lifespan is relatively short, only 30-40L. In contrast, the carbon-supported hybrid zirconium phosphate of this invention, with the addition of 25wt% activated carbon, also shows good regeneration performance and can be regenerated stably, while its lifespan is significantly improved to 60L, resulting in a substantial improvement in overall performance.

[0091] Example 4: Investigation of the preparation and regeneration processes of carbon-supported hybrid zirconium phosphate 1. Investigation of preparation process conditions In this experiment, carbon-supported hybrid zirconium phosphate with a loading of 25 wt% activated carbon was prepared at different temperatures (120 min, 135 min, 150 min, 165 min, and 180 min) under a reaction temperature of 90℃. Following the electro-regeneration method in Example 1, two electro-regeneration experiments were conducted on the carbon-supported hybrid zirconium phosphate prepared at different temperatures using electro-regeneration device structure 1. The lifetime results are shown in Table 8.

[0092] Table 8. Variation in the electroregeneration lifetime of carbon-supported hybrid zirconium phosphate prepared under different process conditions

[0093] The data in Table 8 show that reaction times of 120 min, 135 min, and 180 min result in significant lifespan decay; reaction time of 165 min shows a slight lifespan decay, but the overall lifespan is shorter; while reaction time of 150 min results in a longer lifespan and stable regeneration, with better overall performance.

[0094] 2. Investigation into the amount of carbon-supported hybrid zirconium phosphate used in the anode carbon rod during the electro-regeneration process. Following the method of Example 1, an electro-regeneration experiment was conducted on the carbon-supported hybrid zirconium phosphate prepared in Example 3 using electro-regeneration device structure 1. The difference was that during the preparation of the carbon rod, the amount of carbon-supported hybrid zirconium phosphate used was 25wt%, 30wt%, and 35wt%, respectively (wherein, the mass of the adhesive powder remained unchanged, and the amount of activated carbon was adjusted accordingly to make the total mass of the three 100%). The aforementioned carbon rod was used as the anode for two electro-regeneration experiments, and the results are shown in Table 9.

[0095] Table 9. Electroregeneration results of carbon-supported zirconium phosphate with different activated carbon loadings.

[0096] As can be seen from the data in Table 9: the carbon-supported hybrid zirconium phosphate accounts for 30% of the entire desalination carbon rod, and its lifespan decreases significantly; the carbon-supported hybrid zirconium phosphate accounts for 35% of the entire desalination carbon rod, and its lifespan decreases slightly and is relatively short; the carbon-supported hybrid zirconium phosphate accounts for 25% of the entire desalination carbon rod, and its lifespan is relatively long and it can be regenerated stably.

[0097] Therefore, the activated carbon-supported zirconium phosphate with high loading provided by this invention, prepared under specific processes, not only has a long lifespan but also possesses stable regeneration capabilities, making it suitable for water treatment, especially for water desalination (Ca). 2+ Mg 2+ It has potential applications in this area.

[0098] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. An electro-regeneration adsorption desalination device for zirconium phosphate adsorbents, characterized in that, include: An electrolytic cell and a hollow cylindrical anode, a central anode, and a cathode located within the electrolytic cell; wherein, the zirconium phosphate adsorbent to be treated is composited within a carbon rod as the anode, and the electrolyte in the electrolytic cell is water.

2. The electro-regenerative adsorption desalination device according to claim 1, characterized in that, The central anode is selected from any one of ruthenium-iridium titanium electrode, titanium-based lead dioxide electrode, titanium-based iridium dioxide electrode, copper electrode, and stainless steel-based composite oxide electrode; preferably, it is a ruthenium-iridium titanium electrode. And / or the cathode is selected from any one of titanium mesh electrode, stainless steel mesh electrode, nickel mesh electrode, copper mesh electrode and graphite mesh electrode; preferably titanium mesh electrode.

3. The electro-regenerative adsorption desalination device according to claim 1 or 2, characterized in that, The electro-regenerative adsorption desalination device is a single-chamber device, specifically structured as follows: the central anode is located inside the axis of the anode; the cathode is sleeved outside the anode to form a coaxial cylindrical electrode structure. Alternatively, the electroregenerative adsorption desalination device may be a dual-chamber device, specifically structured as follows: the central anode is located inside the axis of the anode; the cathode and the anode are separated by a cation exchange membrane and placed in the cathode chamber and anode chamber of the dual-chamber device, respectively.

4. The electro-regenerative adsorption desalination device according to claim 3, characterized in that, The cation exchange membrane is selected from any one of perfluorosulfonic acid membrane, fluorine-free proton exchange membrane, carboxylic acid ion exchange membrane, and sulfonated polyether ether ketone membrane; the electrolyte level in the two chambers of the dual-chamber device is the same.

5. A method for electro-regeneration and desalination of zirconium phosphate adsorbents using the apparatus according to any one of claims 1-4, characterized in that, Includes the following steps: (1) Preparation of anode material: Take the zirconium phosphate adsorbent material to be treated, activated carbon and adhesive powder, mix them thoroughly and evenly, and calcine to obtain the anode material of zirconium phosphate composite carbon rod; (2) Assembly of the electro-regenerative adsorption desalination device: Connect the zirconium phosphate adsorbent material to be treated as the anode to the wire as the central anode, and place the cathode outside the anode, or place the anode and cathode connected by the wire in the two chambers of the electrolytic cell respectively; then connect the anode to the positive terminal of the external power supply and connect the cathode to the negative terminal of the external power supply. (3) Electrolysis process: Apply voltage to perform electrolysis, record the current change during the electrolysis process to monitor the regeneration effect.

6. The electro-regenerative desalination method according to claim 5, characterized in that, The carbon rod is made of 20-40% zirconium phosphate adsorbent material, 25-45% activated carbon, and 25-40% adhesive powder by weight percentage. Preferably, the carbon rod is made of 30% zirconium phosphate adsorbent material, 35% activated carbon, and 35% adhesive powder; More preferably, the adhesive powder is selected from any one of polyethylene, polypropylene, high molecular weight polyethylene, polyvinyl chloride, epoxy resin and phenolic resin.

7. The electro-regenerative desalination method according to claim 5, characterized in that, The outer diameter, inner diameter, and length of the carbon rod are 30-80 mm, 10-60 mm, and 10-500 mm, respectively; and / or the density of the carbon rod is 0.55-0.68 g / cm³. 3 .

8. The electro-regenerative desalination method according to claim 5, characterized in that, In step (1), the calcination temperature is 130-200℃ and the time is 6-70min.

9. The electro-regenerative desalination method according to claim 5, characterized in that, The electrolysis is performed using a constant voltage of 2.4-20V.

10. The application of the electro-regeneration desalination device as described in any one of claims 1-4 or the electro-regeneration desalination method as described in any one of claims 5-9 in the desalination and regeneration of zirconium phosphate adsorbent materials.

11. A carbon-supported hybrid zirconium phosphate material, characterized in that, The raw materials for preparing the carbon-supported hybrid zirconium phosphate material include: a zirconium source, a phosphorus source, a fluoride ion source, and activated carbon. The preparation method is as follows: (1) Amorphous zirconium phosphate was prepared by taking zirconium source and phosphorus source and using sol-gel method; (2) Take amorphous zirconium phosphate, fluoride ion source and activated carbon, mix them thoroughly, and heat them to react to obtain carbon-supported hybrid zirconium phosphate.

12. The carbon-supported hybrid zirconium phosphate material according to claim 11, characterized in that, The molar ratio of the zirconium source to the phosphorus source is 1:1-5; preferably 1:

3. And / or the activated carbon in the carbon-supported hybrid zirconium phosphate has a mass percentage of 15-25%, preferably 20%; And / or the fluoride ion source has a mass percentage of 5-10% in carbon-supported hybrid zirconium phosphate, preferably 7.27%; Preferably, the zirconium source is selected from one or more of zirconium oxychloride, zirconium nitrate, and zirconium chloride; more preferably, zirconium oxychloride; and / or the phosphorus source is selected from one or more of phosphoric acid, diammonium hydrogen phosphate, and sodium dihydrogen phosphate; more preferably, phosphoric acid; and / or the fluoride ion source is selected from one or more of sodium fluoride, potassium ammonium fluoride, and calcium fluoride; more preferably, sodium fluoride.

13. The method for preparing carbon-supported hybrid zirconium phosphate material according to claim 11 or 12, characterized in that, Includes the following steps: (1) Dissolve zirconium source and phosphorus source in water respectively to obtain solution 1 and solution 2; (2) Mix solution 1 and solution 2, and prepare amorphous zirconium phosphate by sol-gel reaction; (3) Take amorphous zirconium phosphate, fluoride ion source and activated carbon, mix them thoroughly, and heat them to react to obtain carbon-supported hybrid zirconium phosphate.

14. The preparation method according to claim 13, characterized in that, In step (1), the concentration of the zirconium source in solution 1 is 0.5-0.7 mol / L; the concentration of the phosphorus source in solution 2 is 1-2 mol / L. And / or in step (2), the temperature of the sol-gel reaction is 20-50℃ and the time is 20-30h; And / or in step (3), the temperature of the heating reaction is 60-90°C and the time is 5-7h.

15. The application of the carbon-supported hybrid zirconium phosphate material according to claim 11 or 12 or the carbon-supported hybrid zirconium phosphate material prepared by the preparation method according to claim 13 or 14 in water treatment.

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