A method and device for recycling phosphorus-supported catalyst regeneration waste liquid

Abstract

The application discloses a phosphorus-carrying catalyst regeneration waste liquid recycling treatment method and device, and aims to solve the technical problem of how to better control the acidity of the regeneration liquid to maintain the service life of the phosphorus-carrying catalyst, realize the recycling of the regeneration liquid and the concentration reduction of the phosphorus resource, and reduce the treatment difficulty of the regeneration waste liquid. The method comprises the following steps: introducing the phosphorus-carrying catalyst regeneration waste liquid into an adsorption device filled with a regeneration waste liquid phosphorus removal adsorbent, separating the phosphorus component in the phosphorus-carrying catalyst regeneration waste liquid, collecting the effluent as a phosphorus-lean regeneration liquid, recycling the phosphorus-lean regeneration liquid for the regeneration of the phosphorus-carrying catalyst, and mainly using the phosphate as the phosphorus component; when the regeneration waste liquid phosphorus removal adsorbent is saturated, hot water is used as a desorption medium to replace the liquid in the adsorption device, the volume of the desorption medium is controlled to be less than the volume of the phosphorus-carrying catalyst regeneration waste liquid that can be contained in the adsorption device, and the regeneration waste liquid phosphorus removal adsorbent is eluted.

Description

Technical Field

[0001] This invention relates to the field of flue gas catalytic oxidation dephosphorization technology, specifically to a method and device for recovering and treating waste liquid from the regeneration of phosphorus-supported catalysts. Background Technology

[0002] The electric furnace process for producing yellow phosphorus generates a large amount of tail gas rich in carbon monoxide. This tail gas is an excellent heat source and a raw material for producing C1 chemicals. However, this tail gas contains numerous impurities, including not only the main component CO, but also inorganic sulfur (H2S, S, SO2), organic sulfur (CH4, SH, COS), SiF4, PH3, AsH3, P4, HF, CH4, CO2, O2, N2, cyanide, and trace amounts of dust. Catalytic oxidation can be used to remove phosphorus from the tail gas. The basic principle of catalytic oxidation is to heat the tail gas to 80℃-110℃, introduce a small amount of air, and pass it through a phosphorus-supported catalyst bed in a fixed-bed reactor. This causes impurities such as phosphorus and sulfur to be oxidized. Phosphorus and PH3 are oxidized to P2O3, P2O5, and phosphoric acid. These oxidation products are adsorbed onto the surface of the phosphorus-supported catalyst, thereby purifying the tail gas.

[0003] When phosphorus-supported catalysts become saturated, water is typically used as the regeneration solution for rinsing and regeneration to restore their activity. If the regeneration solution is recycled for catalyst cleaning and regeneration, the phosphoric acid concentration in the regeneration solution accumulates with each cycle. Studies have shown that high concentrations of phosphoric acid solution severely affect the lifespan of phosphorus-supported catalysts. Furthermore, based on the "adsorption-oxidation" working principle of phosphorus-supported dephosphorizing agents, the active components of the phosphorus-supported catalyst undergo electron migration after the reaction, leading to structural changes. In a highly acidic regeneration solution environment, the active components on the phosphorus-supported catalyst are easily detached and lost. This not only reduces the regeneration efficiency of the phosphorus-supported catalyst but also results in the regeneration wastewater containing heavy metal ions, becoming a difficult-to-treat secondary hazardous waste. Therefore, the recycling rate of the regeneration solution is limited, and it quickly becomes regeneration wastewater containing phosphoric acid and small amounts of metal ions.

[0004] Currently, the treatment of this type of recycled waste liquid faces significant challenges: on the one hand, the volume of recycled waste liquid is large, and direct discharge will cause serious environmental pollution and high treatment costs; on the other hand, to achieve resource utilization, it is necessary to concentrate the dilute phosphoric acid in the recycled waste liquid and remove metal impurities, and the existing concentration and purification processes are complex, energy-intensive, and difficult. Summary of the Invention

[0005] The purpose of this invention is to provide a method and apparatus for recycling and treating waste liquid from the regeneration of phosphorus-supported catalysts, in order to solve the technical problem of how to better control the acidity of the regeneration liquid to maintain the lifespan of the phosphorus-supported catalyst, realize the recycling of the regeneration liquid and the reduction and concentration of phosphorus resources, and reduce the difficulty of treating the waste liquid.

[0006] Firstly, a method for recovering and treating waste liquid from the regeneration of a phosphorus-supported catalyst includes: introducing the waste liquid from the regeneration of the phosphorus-supported catalyst into an adsorption device filled with a phosphorus removal adsorbent; selectively adsorbing the phosphorus components in the waste liquid using the phosphorus removal adsorbent, thereby separating the phosphorus components; collecting the effluent as a phosphorus-poor regeneration solution; recycling the phosphorus-poor regeneration solution for the regeneration of the phosphorus-supported catalyst; the phosphorus components being mainly phosphate; and when the phosphorus removal adsorbent is saturated, replacing the remaining liquid in the adsorption device with hot water as a desorption medium, controlling the volume of the desorption medium to be smaller than the capacity of the adsorption device. The volume of the phosphorus-supported catalyst regeneration waste liquid is used to elute the phosphorus removal adsorbent in the regeneration waste liquid; hot water is used to break the bond between the phosphorus removal adsorbent and the adsorbed phosphorus components, transferring the adsorbed phosphorus components to the aqueous phase, resulting in a high-concentration phosphorus-containing solution with reduced volume. The eluted phosphorus removal adsorbent is dried to restore its adsorption performance for later use; wherein, the phosphorus removal adsorbent is a supported composite material, including a porous activated carbon support and an active component supported on the porous activated carbon support; the active component includes an iron-lanthanum-copper composite oxide and a nitrogen-doped carbon structure, and a CO-La chemical bond is formed between the active component and the porous activated carbon support.

[0007] As an optimization and / or instance of the above-mentioned method for recovering and treating phosphorus-loaded catalyst regeneration waste liquid, further: the phosphorus removal adsorbent for the regeneration waste liquid is prepared by a method comprising the following steps: dissolving iron salt, lanthanum salt, and copper salt in a first solvent to prepare a metal salt solution, uniformly loading the metal salt solution onto the porous activated carbon support, and obtaining a first adsorbent precursor by drying and a first calcination; dissolving nitrogen-rich organic ligand salt in a second solvent to prepare a nitrogen-containing precursor solution, uniformly loading the nitrogen-containing precursor solution onto the first adsorbent precursor, and obtaining a second adsorbent precursor by drying; and subjecting the second adsorbent precursor to a second calcination under an inert atmosphere to induce the formation of the iron-lanthanum-copper composite oxide, the nitrogen-doped carbon structure, and the CO-La chemical bond.

[0008] As an optimization and / or instance of the above-mentioned method for recovering and treating waste liquid from the regeneration of phosphorus-supported catalyst, further: the iron salt is ferric chloride, the lanthanum salt is lanthanum chloride, and the copper salt is copper chloride; based on 100 parts by weight of the porous activated carbon support, the loading of ferric chloride is 3.0-5.0 parts by weight, the loading of lanthanum chloride is 3.0-9.0 parts by weight, and the loading of copper chloride is 0.5-1.5 parts by weight.

[0009] As an optimization and / or instance of the above-mentioned method for recovering and treating waste liquid from the regeneration of phosphorus-supported catalysts, further: the porous activated carbon support surface contains hydroxyl and / or carbonyl groups, and the lanthanum element in the active component combines with the hydroxyl and / or carbonyl groups to form the CO-La chemical bond.

[0010] As an optimization and / or instance of the above-mentioned method for recovering and treating waste liquid from the regeneration of phosphorus-supported catalyst, further: the nitrogen-rich organic ligand salt is selected from at least one of urea, dicyandiamide, guanidine hydrochloride, or disodium ethylenediaminetetraacetate; the amount of the nitrogen-rich organic ligand salt is 5.0-15.0 parts by weight, based on 100 parts by weight of the porous activated carbon support.

[0011] As an optimization and / or instance of the above-mentioned method for recovering and treating waste liquid from the regeneration of phosphorus-supported catalyst, further: the second calcination is carried out in a nitrogen atmosphere for 1-4 hours at a calcination temperature of 300℃-700℃.

[0012] As an optimization and / or instance of the above-mentioned method for recovering and treating waste liquid from the regeneration of phosphorus-supported catalysts, further: the porous activated carbon support has an iodine adsorption value of 700 mg / g-1200 mg / g and an average particle size of 3 mm-5 mm.

[0013] As an optimization and / or instance of the above-mentioned method for recovering and treating phosphorus-loaded catalyst regeneration waste liquid, further: the adsorption device is a storage tank filled with the phosphorus removal adsorbent for the regeneration waste liquid; the step of introducing the phosphorus-loaded catalyst regeneration waste liquid into the adsorption device specifically involves: pumping the phosphorus-loaded catalyst regeneration waste liquid into the storage tank, allowing it to stand for adsorption for more than 24 hours, and then discharging the phosphorus-poor regeneration liquid.

[0014] As an optimization and / or instance of the above-mentioned method for recovering and treating the regenerated waste liquid of the phosphorus-supported catalyst, further: the temperature of the hot water is 60℃-90℃, the elution time is 24 hours-48 hours; and the volume of the desorption medium is 1 / 4 to 1 / 2 of the volume of the phosphorus-supported catalyst regenerated waste liquid that can be contained in the adsorption device.

[0015] Secondly, a phosphorus-loaded catalyst regeneration waste liquid recovery and treatment device is provided for implementing the phosphorus-loaded catalyst regeneration waste liquid recovery and treatment method of the first aspect above; comprising: an adsorption device, the adsorption device being filled with the phosphorus removal adsorbent of the regeneration waste liquid; an inlet pipeline connected to the inlet of the adsorption device for inputting the phosphorus-loaded catalyst regeneration waste liquid from the flue gas catalytic oxidation phosphorus removal fixed bed reactor into the adsorption device; a recycling pipeline, one end connected to the outlet of the adsorption device and the other end connected to the phosphorus-loaded catalyst regeneration system of the flue gas catalytic oxidation phosphorus removal fixed bed reactor, for recycling the phosphorus-poor regeneration liquid back for the regeneration of the phosphorus-loaded catalyst; and a desorption regeneration component, including a hot water supply source and a desorption pipeline connecting the hot water supply source and the adsorption device, for introducing hot water into the adsorption device to wash away the phosphorus components adsorbed on the phosphorus removal adsorbent of the regeneration waste liquid, obtaining a high-concentration phosphorus-containing solution with reduced volume.

[0016] The above-mentioned method and apparatus for recovering and treating phosphorus-supported catalyst regeneration waste liquid of the present invention, by introducing a specific phosphorus removal adsorbent to adsorb and treat the regeneration waste liquid and combining it with a hot water desorption process, can achieve the following technical effects:

[0017] First, it enables the recycling of the regenerated liquid, significantly extending the service life of the phosphorus-supported catalyst. By using a phosphorus adsorbent to selectively adsorb phosphorus components in the regeneration waste liquid of the phosphorus-supported catalyst, the phosphoric acid concentration in the regenerated liquid is effectively reduced, resulting in a significant decrease in the acidity of the outflowing phosphorus-poor regenerated liquid. Recycling this low-acidity, phosphorus-poor regenerated liquid for the regeneration of the phosphorus-supported catalyst avoids the damage to the catalyst structure and the loss of active components caused by a high-concentration acidic environment, thus maintaining the activity of the phosphorus-supported catalyst and extending its replacement cycle.

[0018] Secondly, this invention achieves volume reduction of regenerated wastewater and enrichment of phosphorus resources, thereby lowering treatment costs. The invention uses hot water, with a volume smaller than that of the adsorption device, as the desorption medium to transfer phosphorus components dispersed in a large amount of phosphorus-supported catalyst regeneration wastewater to at least a small amount of the aqueous phase, resulting in a high-concentration phosphorus-containing solution with reduced volume. This process not only solves the problem of large quantities of low-concentration regeneration wastewater being difficult to utilize directly and incurring high treatment costs, but also provides convenient conditions for the subsequent resource utilization of phosphorus resources through concentration and enrichment.

[0019] Third, the phosphorus removal adsorbent for regenerated wastewater exhibits stable structure, large adsorption capacity, and strong acid resistance. The phosphorus removal adsorbent used in this invention is a supported composite material. Its active components (iron-lanthanum-copper composite oxide and nitrogen-doped carbon structure) form stable CO-La chemical bonds with the porous activated carbon support. This chemical bonding not only improves the adsorbent's affinity for phosphate and its adsorption capacity, but more importantly, it enhances the binding force between the active components and the porous activated carbon support. This effectively prevents the loss of active components in acidic regenerated wastewater environments, ensuring the structural stability and phosphorus removal performance of the phosphorus removal adsorbent during multiple "adsorption-regeneration" cycles.

[0020] Fourth, the process is simple and environmentally friendly. The method for recovering and treating the waste liquid from the regeneration of the phosphorus-supported catalyst in this invention only requires adsorption and hot water elution, without the need for adding complex chemical precipitants, thus avoiding secondary pollution. Furthermore, adsorbent regeneration only requires hot water, resulting in low energy consumption, simple operation, and easy industrial application.

[0021] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Additional aspects and advantages provided by the present invention will be set forth in part in the description which follows, and in part will be obvious from the description or may be learned by practice. Attached Figure Description

[0022] The accompanying drawings, which form part of this specification, are used to aid in understanding the invention. The contents provided in the drawings and their related descriptions in this specification can be used to explain the invention, but do not constitute an undue limitation of the invention.

[0023] Figure 1 This is a photomicrograph of the phosphorus removal adsorbent for the regenerated waste liquid in Experimental Example 2 of the present invention.

[0024] Figure 2 The image shows the X-ray photoelectron spectrum (C 1s high-resolution spectrum) of the phosphorus removal adsorbent in the regenerated waste liquid of Experimental Example 2 of the present invention.

[0025] Figure 3 The image shows the X-ray photoelectron spectrum (N 1s high-resolution spectrum) of the phosphorus removal adsorbent in the regenerated waste liquid of Experimental Example 2 of the present invention.

[0026] Figure 4 The X-ray photoelectron spectrum (O 1s high-resolution spectrum) of the phosphorus removal adsorbent in the regenerated waste liquid of Experimental Example 2 of the present invention is shown.

[0027] Figure 5 The image shows the X-ray photoelectron spectrum (La 3d5 / 2 high-resolution spectrum) of the phosphorus removal adsorbent in the regenerated waste liquid of Experimental Example 2 of the present invention. Detailed Implementation

[0028] The present invention will now be clearly and completely described in conjunction with the accompanying drawings. Those skilled in the art will be able to implement the present invention based on these descriptions. Before describing the present invention in conjunction with the accompanying drawings, it should be particularly noted that:

[0029] The technical solutions and features provided in the various sections, including the following description, can be combined with each other without conflict. Furthermore, where possible, these technical solutions, features, and related combinations can be given specific technical subject matter and protected by relevant patents.

[0030] The embodiments of the present invention described below are generally only some embodiments and not all embodiments. Based on these embodiments, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of patent protection.

[0031] The term "comprising" and any variations thereof in this specification, the corresponding claims, and related sections are intended to cover a non-exclusive inclusion. Other related terms and units can be reasonably interpreted based on the relevant content provided in this specification.

[0032] Experimental Example 1

[0033] (1) Preparation of phosphorus removal adsorbent for regenerated waste liquid

[0034] First, 3.8g of ferric chloride, 3.9g of lanthanum chloride, and 1.0g of copper chloride were weighed and dissolved in 50mL of distilled water (the first solvent) to prepare a metal salt solution. This metal salt solution was then uniformly sprayed onto 100g of porous activated carbon carrier (iodine adsorption value of 960mg / g, average particle size of 4mm), thoroughly stirred, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80℃ for 4 hours. Then, it was placed in a muffle furnace for the first calcination (temperature set at 350℃, nitrogen atmosphere, calcination for 2 hours) to obtain the first adsorbent precursor.

[0035] Then, 10.0 g of urea (nitrogen-rich organic ligand salt) was weighed and dissolved in 50 mL of distilled water (second solvent) to prepare a nitrogen-containing precursor solution. This nitrogen-containing precursor solution was uniformly sprayed onto the first adsorbent precursor prepared above, stirred thoroughly, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80°C for 4 hours to obtain the second adsorbent precursor. The second adsorbent precursor was placed in a muffle furnace, and nitrogen gas was introduced for a second calcination. The calcination temperature was set at 500°C, and the calcination time was 2 hours. After cooling to room temperature, the final phosphorus removal adsorbent for regenerated wastewater was obtained.

[0036] (2) Preparation of saturated phosphorus-supported catalyst

[0037] To test the regeneration effect, a phosphorus-supported catalyst with adsorption saturation was first prepared. This experiment simulated the composition of the tail gas from the electric furnace process for yellow phosphorus. Fresh phosphorus-supported catalyst was placed in a quartz tube reactor (1.8 mm in diameter), and preheated and purged to remove adsorbed water. The reaction temperature was set at 80℃. The total gas flow rate entering the quartz tube reactor was approximately 800 mL / min. -1 The inlet concentration of phosphine (PH3) was 2000 ppm. The concentration of PH3 in the outlet gas was continuously monitored using a gas detector until the phosphorus-supported catalyst penetration efficiency reached 99.9% (i.e., the outlet concentration was close to the inlet concentration), at which point the phosphorus-supported catalyst was considered saturated. The phosphorus capacity of this phosphorus-supported catalyst was determined to be 245 mg(PH3)·gsorbent. -1 .

[0038] (3) Regeneration of phosphorus-supported catalyst and adsorption treatment of regeneration waste liquid

[0039] The saturated phosphorus-supported catalyst was regenerated by in-situ water washing. A two-stage regeneration method was adopted, with each stage taking 30 minutes.

[0040] The saturated catalyst was washed with water in the first stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This first-stage regeneration waste liquid was pumped into a primary storage tank (primary adsorption unit) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for 24 hours for adsorption, and the phosphorus removal adsorbent was used to selectively adsorb phosphate ions from the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 11527 mg / L (corresponding to a phosphoric acid mass percentage of 1.11%). The adsorption efficiency of the phosphorus removal adsorbent in the primary adsorption unit was calculated to be 77%.

[0041] The saturated catalyst was washed with water in the second stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the second stage of regeneration was pumped into a secondary storage tank (secondary adsorption device) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for 24 hours for adsorption, and the phosphorus removal adsorbent was used to selectively adsorb phosphate ions in the phosphorus-loaded catalyst regeneration waste liquid. The content of phosphorus species (calculated as phosphate) in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 5098 mg / L (corresponding to a phosphoric acid mass percentage of 0.47%). The adsorption efficiency of the phosphorus removal adsorbent in the secondary adsorption device was calculated to be 81%.

[0042] (4) Desorption and regeneration of phosphorus adsorbent in regenerated wastewater

[0043] After multiple "adsorption" cycles, when the phosphorus adsorbent in the regenerated waste liquid reaches saturation and no longer effectively adsorbs phosphorus species, a desorption operation is performed.

[0044] Hot water was pumped into each storage tank as the desorption medium, with the volume of hot water controlled to be 1 / 3 of the volume of the phosphorus-loaded catalyst regeneration waste liquid that the storage tank could hold. Immersion desorption was carried out at 80℃ for 48 hours. The hot water disrupted the bond between the adsorbent and the phosphorus component, transferring the phosphorus component into the aqueous phase.

[0045] After desorption is completed, the phosphorus adsorbent in the regenerated waste liquid is dried for later use to restore its adsorption performance. At the same time, a high-concentration phosphorus (phosphate) solution with reduced volume is collected, thus achieving the enrichment of phosphorus resources.

[0046] Experiment Example 2

[0047] (1) Preparation of phosphorus removal adsorbent for regenerated waste liquid

[0048] First, 3.8g of ferric chloride, 7.8g of lanthanum chloride, and 1.0g of copper chloride were weighed and dissolved in 50mL of distilled water (the first solvent) to prepare a metal salt solution. This metal salt solution was then uniformly sprayed onto 100g of porous activated carbon carrier (iodine adsorption value of 960mg / g, average particle size of 4mm), thoroughly stirred, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80℃ for 4 hours. Then, it was placed in a muffle furnace for the first calcination (temperature set at 350℃, nitrogen atmosphere, calcination for 2 hours) to obtain the first adsorbent precursor.

[0049] Then, 10.0 g of urea (nitrogen-rich organic ligand salt) was weighed and dissolved in 50 mL of distilled water (second solvent) to prepare a nitrogen-containing precursor solution. This nitrogen-containing precursor solution was uniformly sprayed onto the first adsorbent precursor prepared above, stirred thoroughly, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80°C for 4 hours to obtain the second adsorbent precursor. The second adsorbent precursor was placed in a muffle furnace, and nitrogen gas was introduced for a second calcination. The calcination temperature was set at 500°C, and the calcination time was 2 hours. After cooling to room temperature, the final phosphorus removal adsorbent for regenerated wastewater was obtained.

[0050] (2) Preparation of saturated phosphorus-supported catalyst

[0051] Same as Experiment 1.

[0052] (3) Regeneration of phosphorus-supported catalyst and adsorption treatment of regeneration waste liquid

[0053] The saturated phosphorus-supported catalyst was regenerated by in-situ water washing. A two-stage regeneration method was adopted, with each stage taking 30 minutes.

[0054] The saturated catalyst was washed with water in the first stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a primary storage tank (primary adsorption device) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for 24 hours for adsorption, and the phosphorus removal adsorbent was used to selectively adsorb phosphate ions from the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 4009 mg / L (corresponding to a phosphoric acid mass percentage of 0.5%). The adsorption efficiency of the phosphorus removal adsorbent in the primary adsorption device was calculated to be 92%.

[0055] The saturated catalyst was washed with water in the second stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a secondary storage tank (secondary adsorption device) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for 24 hours for adsorption, and the phosphorus removal adsorbent was used to selectively adsorb phosphate ions in the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 2146 mg / L (corresponding to a phosphoric acid mass percentage of 0.22%). The adsorption efficiency of the phosphorus removal adsorbent in the secondary adsorption device was calculated to be 92%.

[0056] (4) Desorption and regeneration of phosphorus adsorbent in regenerated wastewater

[0057] Same as Experiment 1.

[0058] Experimental Example 3

[0059] (1) Preparation of phosphorus removal adsorbent for regenerated waste liquid

[0060] First, 3.0 g of ferric chloride, 9.0 g of lanthanum chloride, and 0.5 g of copper chloride were weighed and dissolved in 50 mL of distilled water (the first solvent) to prepare a metal salt solution. This metal salt solution was then uniformly sprayed onto 100 g of porous activated carbon carrier (iodine adsorption value of 960 mg / g, average particle size of 4 mm), thoroughly stirred, and allowed to stand for 2 hours. After standing, the carbon was dried in an oven at 80°C for 4 hours. It was then removed and placed in a muffle furnace for the first calcination (temperature set at 350°C, nitrogen atmosphere, calcination for 2 hours) to obtain the first adsorbent precursor.

[0061] Then, 5.0 g of urea (nitrogen-rich organic ligand salt) was weighed and dissolved in 50 mL of distilled water (second solvent) to prepare a nitrogen-containing precursor solution. This nitrogen-containing precursor solution was uniformly sprayed onto the first adsorbent precursor prepared above, stirred thoroughly, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80°C for 4 hours to obtain the second adsorbent precursor. The second adsorbent precursor was placed in a muffle furnace, and nitrogen gas was introduced for a second calcination. The calcination temperature was set at 500°C, and the calcination time was 2 hours. After cooling to room temperature, the final phosphorus removal adsorbent for regenerated wastewater was obtained.

[0062] (2) Preparation of saturated phosphorus-supported catalyst

[0063] Same as Experiment 1.

[0064] (3) Regeneration of phosphorus-supported catalyst and adsorption treatment of regeneration waste liquid

[0065] The saturated phosphorus-supported catalyst was regenerated by in-situ water washing. A two-stage regeneration method was adopted, with each stage taking 30 minutes.

[0066] The saturated catalyst was washed with water in the first stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This first-stage regeneration waste liquid was pumped into a primary storage tank (primary adsorption unit) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for adsorption for 24 hours. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 5512 mg / L (corresponding to a phosphoric acid mass percentage of 0.53%). Calculations showed that the adsorption efficiency of the phosphorus removal adsorbent in the primary adsorption unit reached 89%.

[0067] The saturated catalyst was washed with water in the second stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a secondary storage tank (secondary adsorption device) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for adsorption for 24 hours. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 3757 mg / L (corresponding to a phosphoric acid mass percentage of 0.36%). Calculations showed that the adsorption efficiency of the phosphorus removal adsorbent in the secondary adsorption device reached 86%.

[0068] (4) Desorption and regeneration of phosphorus adsorbent in regenerated wastewater

[0069] Same as Experiment 1.

[0070] Experiment Example 4

[0071] (1) Preparation of phosphorus removal adsorbent for regenerated waste liquid

[0072] First, 4.5g of ferric chloride, 9.0g of lanthanum chloride, and 1.5g of copper chloride were weighed and dissolved in 50mL of distilled water (the first solvent) to prepare a metal salt solution. This metal salt solution was then uniformly sprayed onto 100g of porous activated carbon carrier (iodine adsorption value of 960mg / g, average particle size of 4mm), thoroughly stirred, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80℃ for 4 hours. Then, it was placed in a muffle furnace for the first calcination (temperature set at 350℃, nitrogen atmosphere, calcination for 2 hours) to obtain the first adsorbent precursor.

[0073] Then, 15.0 g of urea (nitrogen-rich organic ligand salt) was weighed and dissolved in 50 mL of distilled water (second solvent) to prepare a nitrogen-containing precursor solution. This nitrogen-containing precursor solution was uniformly sprayed onto the first adsorbent precursor prepared above, stirred thoroughly, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80°C for 4 hours to obtain the second adsorbent precursor. The second adsorbent precursor was placed in a muffle furnace, and nitrogen gas was introduced for a second calcination. The calcination temperature was set at 500°C, and the calcination time was 2 hours. After cooling to room temperature, the final phosphorus removal adsorbent for regenerated wastewater was obtained.

[0074] (2) Preparation of saturated phosphorus-supported catalyst

[0075] Same as Experiment 1.

[0076] (3) Regeneration of phosphorus-supported catalyst and adsorption treatment of regeneration waste liquid

[0077] The saturated phosphorus-supported catalyst was regenerated by in-situ water washing. A two-stage regeneration method was adopted, with each stage taking 30 minutes.

[0078] The saturated catalyst was washed with water in the first stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a primary storage tank (primary adsorption unit) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for adsorption for 24 hours. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 4510 mg / L (corresponding to a phosphoric acid mass percentage of 0.43%). Calculations showed that the adsorption efficiency of the phosphorus removal adsorbent in the primary adsorption unit reached 91%.

[0079] The saturated catalyst was washed with water in the second stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a secondary storage tank (secondary adsorption device) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for adsorption for 24 hours. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 2952 mg / L (corresponding to a phosphoric acid mass percentage of 0.28%). Calculations showed that the adsorption efficiency of the phosphorus removal adsorbent in the secondary adsorption device reached 89%.

[0080] (4) Desorption and regeneration of phosphorus adsorbent in regenerated wastewater

[0081] Same as Experiment 1.

[0082] Experimental Example 5

[0083] (1) Preparation of phosphorus removal adsorbent for regenerated waste liquid

[0084] First, 3.8g of ferric chloride, 7.8g of lanthanum chloride, and 1.0g of copper chloride were weighed and dissolved in 50mL of distilled water (the first solvent) to prepare a metal salt solution. This metal salt solution was then uniformly sprayed onto 100g of porous activated carbon carrier (iodine adsorption value of 960mg / g, average particle size of 4mm), thoroughly stirred, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80℃ for 4 hours. Then, it was placed in a muffle furnace for the first calcination (temperature set at 350℃, nitrogen atmosphere, calcination for 2 hours) to obtain the first adsorbent precursor.

[0085] Then, 10.0 g of dicyandiamide (a nitrogen-rich organic ligand salt) was weighed and dissolved in 50 mL of distilled water (a second solvent; heating may be applied to aid dissolution depending on the solubility) to prepare a nitrogen-containing precursor solution. This nitrogen-containing precursor solution was uniformly sprayed onto the first adsorbent precursor prepared above, stirred thoroughly, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80°C for 4 hours to obtain the second adsorbent precursor. The second adsorbent precursor was placed in a muffle furnace, and nitrogen gas was introduced for a second calcination. The calcination temperature was set at 500°C, and the calcination time was 2 hours. After cooling to room temperature, the final phosphorus removal adsorbent for the regenerated wastewater was obtained.

[0086] (2) Preparation of saturated phosphorus-supported catalyst

[0087] Same as Experiment 1.

[0088] (3) Regeneration of phosphorus-supported catalyst and adsorption treatment of regeneration waste liquid

[0089] The saturated phosphorus-supported catalyst was regenerated by in-situ water washing. A two-stage regeneration method was adopted, with each stage taking 30 minutes.

[0090] The saturated catalyst was washed with water in the first stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a primary storage tank (primary adsorption unit) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for adsorption for 24 hours. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 6265 mg / L (corresponding to a phosphoric acid mass percentage of 0.60%). Calculations showed that the adsorption efficiency of the phosphorus removal adsorbent in the primary adsorption unit reached 87.5%.

[0091] The saturated catalyst was washed with water in the second stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a secondary storage tank (secondary adsorption device) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for adsorption for 24 hours. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 4025 mg / L (corresponding to a phosphoric acid mass percentage of 0.39%). Calculations showed that the adsorption efficiency of the phosphorus removal adsorbent in the secondary adsorption device reached 85%.

[0092] (4) Desorption and regeneration of phosphorus adsorbent in regenerated wastewater

[0093] Same as Experiment 1.

[0094] Experimental Example 6

[0095] (1) Preparation of phosphorus removal adsorbent for regenerated waste liquid

[0096] First, 3.8g of ferric chloride, 7.8g of lanthanum chloride, and 1.0g of copper chloride were weighed and dissolved in 50mL of distilled water (the first solvent) to prepare a metal salt solution. This metal salt solution was then uniformly sprayed onto 100g of porous activated carbon carrier (iodine adsorption value of 960mg / g, average particle size of 4mm), thoroughly stirred, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80℃ for 4 hours. Then, it was placed in a muffle furnace for the first calcination (temperature set at 350℃, nitrogen atmosphere, calcination for 2 hours) to obtain the first adsorbent precursor.

[0097] Then, 10.0 g of urea (nitrogen-rich organic ligand salt) was weighed and dissolved in 50 mL of distilled water (second solvent) to prepare a nitrogen-containing precursor solution. This nitrogen-containing precursor solution was uniformly sprayed onto the first adsorbent precursor prepared above, stirred thoroughly, and allowed to stand for 2 hours. After standing, it was placed in an oven and dried at 80°C for 4 hours to obtain the second adsorbent precursor. The second adsorbent precursor was placed in a muffle furnace, and nitrogen gas was introduced for a second calcination. The calcination temperature was set at 350°C, and the calcination time was 2 hours. After cooling to room temperature, the final phosphorus removal adsorbent for regenerated wastewater was obtained.

[0098] (2) Preparation of saturated phosphorus-supported catalyst

[0099] Same as Experiment 1.

[0100] (3) Regeneration of phosphorus-supported catalyst and adsorption treatment of regeneration waste liquid

[0101] The saturated phosphorus-supported catalyst was regenerated by in-situ water washing. A two-stage regeneration method was adopted, with each stage taking 30 minutes.

[0102] The saturated catalyst was washed with water in the first stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a primary storage tank (primary adsorption unit) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for adsorption for 24 hours. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 7517 mg / L (corresponding to a phosphoric acid mass percentage of 0.72%). Calculations showed that the adsorption efficiency of the phosphorus removal adsorbent in the primary adsorption unit reached 85%.

[0103] The saturated catalyst was washed with water in the second stage of regeneration, and the effluent after washing was the phosphorus-loaded catalyst regeneration waste liquid. This phosphorus-loaded catalyst regeneration waste liquid was pumped into a secondary storage tank (secondary adsorption device) containing 20g of the phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the storage tank for adsorption for 24 hours. The phosphorus species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was measured. Before adsorption treatment, the phosphate content in the phosphorus-loaded catalyst regeneration waste liquid was 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after adsorption treatment, the phosphate content in the effluent phosphorus-poor regeneration liquid decreased to 4830 mg / L (corresponding to a phosphoric acid mass percentage of 0.46%). Calculations showed that the adsorption efficiency of the phosphorus removal adsorbent in the secondary adsorption device reached 82%.

[0104] (4) Desorption and regeneration of phosphorus adsorbent in regenerated wastewater

[0105] Same as Experiment 1.

[0106] The data on the adsorption treatment of the phosphorus-supported catalyst regeneration waste liquid in the above experimental examples are summarized in Table 1.

[0107] Table 1 – Summary of Adsorption Treatment Data for Regenerated Waste Liquid from Phosphorus-supported Catalysts

[0108]

[0109] As can be seen from Table 1, different preparation parameters have a significant impact on the phosphorus removal performance of the phosphorus removal adsorbent for regenerated waste liquid.

[0110] The main difference between Experiment 1 and Experiment 2 lies in the Fe / La molar ratio during adsorbent preparation. Compared to Experiment 1 (Fe / La = 1:0.25), Experiment 2 adjusted the Fe / La ratio to 1:0.5. With the increase in La doping amount, the adsorbent performance was significantly improved. Calculations show that the adsorption efficiency of Experiment 1 in the first stage was approximately 77%, while the adsorption efficiency of Experiment 2 increased to approximately 92%. The mechanism of this performance leap may be that the adsorbent support surface has abundant active groups such as hydroxyl and carbonyl groups, which can form stable CO-La chemical bonds with the introduced La. In Experiment 1, although a CO-La structure was formed, the active sites on the support surface were not fully filled due to the limited La content. In Experiment 2, with the increase of La content, the density of CO-La chemical bonds formed on the support surface increased significantly, not only fully utilizing the surface functional groups of the support but also greatly increasing the abundance of phosphophilic active sites (La species) on the adsorbent surface. This high density of active sites exposed to the phosphoric acid environment greatly enhances the ability to complex and capture phosphate ions, thereby achieving a qualitative change in adsorption efficiency.

[0111] To further confirm the above-specified mechanism and the occurrence state of the active component, especially to verify the formation of key chemical bonds between the active component and the support, the present invention performed microscopic characterization on the phosphorus removal adsorbent for regenerated wastewater prepared in Experimental Example 2. For example... Figure 1 As shown, the micrographs reveal the surface microstructure of the adsorbent. Figures 2 to 5 X-ray photoelectron spectroscopy (XPS) analysis further revealed its fine surface chemical composition: combined Figure 2 C1s spectrum and Figure 4 The O 1s spectrum clearly shows characteristic peaks at approximately 286.6 eV and 531.5 eV, corresponding to the presence of CO-La chemical bonds. This strongly suggests that the lanthanide active components are firmly anchored to the activated carbon support surface through chemical bonds, rather than through simple physical stacking. This is highly consistent with the inferences regarding CO-La bonding in the aforementioned mechanistic analysis. Meanwhile, Figure 4 The lattice oxygen (MO) peak at 529.7 eV is coordinated with Figure 5 The characteristic peaks of La 3d5 / 2 confirmed the formation of a stable iron-lanthanum-copper composite oxide phase on the surface. Furthermore, Figure 3 The N 1s spectra show that nitrogen was successfully doped into the carbon framework in the form of pyridine nitrogen, pyrrole nitrogen, and graphitic nitrogen. This nitrogen-doped structure helps to further disperse the metal oxide and provides auxiliary active sites. These characterization results fully explain why Experimental Example 2 has the best phosphorus removal performance.

[0112] Experiments 3 and 4 further investigated the effect of the second calcination temperature on the performance of the phosphorus removal adsorbent in the regenerated wastewater during the preparation process. Data showed that the adsorption effect of Experiment 2 (second calcination temperature of 400℃) was slightly better than that of Experiment 4 (500℃) and Experiment 3 (300℃). This indicates that there is an optimal window for the second calcination temperature. Too low a temperature (as in Experiment 3) may lead to incomplete crystallization of the iron-lanthanum-copper composite oxide and insufficient formation of active components; while too high a temperature (as in Experiment 4) may cause the pore structure of the porous activated carbon support to collapse or the specific surface area to decrease, thus slightly reducing the adsorption efficiency (the efficiency of Experiment 4 was approximately 91%, slightly lower than the 92% of Experiment 2).

[0113] Experiments 5 and 6 investigated the variation in the loading ratio of the active component to the porous activated carbon support. The results showed that when deviating from the optimal ratio in Experiment 2, the concentration of residual phosphorus components (mainly phosphate) in the phosphorus-poor regeneration solution increased (6265 mg / L in Experiment 5 and 7517 mg / L in Experiment 6), and the adsorption efficiency decreased to 87.5% and 85%, respectively. This indicates that a suitable porous activated carbon support ratio is crucial for dispersing the active component, preventing agglomeration, and providing sufficient mass transfer channels.

[0114] Comparing Experiments 1 to 6, the phosphorus removal adsorbent prepared in Experiment 2 exhibited the best adsorption performance in the regenerated wastewater. In the first-stage treatment, it reduced the high concentration of phosphate (50118 mg / L) in the phosphorus-supported catalyst regeneration wastewater to 4009 mg / L, achieving the highest removal rate. This demonstrates that by precisely controlling the Fe / La molar ratio, the second calcination temperature, and the loading ratio of the porous activated carbon support, the CO-La chemical bonds on the material surface can be maximized to achieve highly efficient and selective adsorption of phosphorus components in the phosphorus-supported catalyst regeneration wastewater. This effectively solves the problem of large wastewater volume caused by acid accumulation during the recycling of phosphorus-poor regeneration liquid.

[0115] The data on the desorption treatment of phosphorus-loaded adsorbents are summarized in Table 2.

[0116] Table 2 – Summary of data on phosphorus-supported catalyst desorption treatment

[0117]

[0118] As can be seen from the desorption data of the phosphorus-supported catalyst in Table 2, when hot water with a volume of 1 / 3 of the regenerated waste liquid was used for elution and concentration, the concentration of the first-stage desorbent in Experiments 1-6, from highest to lowest, was: Experiment 2 (12.70%) > Experiment 5 (12.48%) > Experiment 6 (12.39%) > Experiment 3 (12.15%) ≈ Experiment 4 (12.14%) > Experiment 1 (11.70%). The concentration of the second-stage desorbent, from highest to lowest, was: Experiment 2 (7.26%) > Experiment 5 (6.99%) > Experiment 3 (6.71%) > Experiment 4 (6.65%) > Experiment 1 (6.59%) > Experiment 6 (6.40%).

[0119] All experimental examples used an "adsorption-thermal desorption" process to concentrate the 4.8% original first-stage washing solution to a 11.7%-12.9% phosphoric acid solution (first-stage desorption solution). The second-stage desorption solution also yielded a concentrated phosphoric acid solution of about 6%. This demonstrates that the present invention can realize a phosphoric acid adsorption-hot water desorption concentration process, utilizing the synergistic effect of ternary metals to achieve highly selective adsorption. At the same time, the local pH of the material surface is adjusted by doping with N element, and the combination of gentle heating weakens the partial binding of Fe, La and phosphate ions, causing them to dissociate in hot water.

[0120] The present invention has been described above. Those skilled in the art will be able to implement the present invention based on these descriptions. All other embodiments obtained by those skilled in the art based on the above description without inventive effort should fall within the scope of the present invention.

Claims

1. A method for recovering and treating waste liquid from the regeneration of phosphorus-supported catalysts, characterized in that: include: The phosphorus-supported catalyst regeneration waste liquid is introduced into an adsorption device filled with a phosphorus removal adsorbent for the regeneration waste liquid. The phosphorus component in the phosphorus-supported catalyst regeneration waste liquid is selectively adsorbed by the phosphorus removal adsorbent, thereby separating the phosphorus component in the phosphorus-supported catalyst regeneration waste liquid. The effluent is collected as a phosphorus-poor regeneration liquid, which is recycled for the regeneration of the phosphorus-supported catalyst. The phosphorus component is mainly phosphate. When the phosphorus removal adsorbent in the regenerated waste liquid is saturated, hot water at a temperature of 60℃-90℃ is used as the desorption medium to replace the liquid in the adsorption device. The elution time is 24-48 hours. The volume of the desorption medium is controlled to be 1 / 4 to 1 / 2 of the volume of the phosphorus-loaded catalyst regeneration waste liquid that can be contained in the adsorption device to elute the phosphorus removal adsorbent in the regenerated waste liquid. Hot water is used to break the bond between the phosphorus adsorbent in the regenerated waste liquid and the adsorbed phosphorus components, transferring the adsorbed phosphorus components to the aqueous phase, resulting in a high-concentration phosphorus-containing solution with reduced volume. The phosphorus adsorbent in the regenerated waste liquid after elution is dried to restore its adsorption performance for later use. The phosphorus removal adsorbent for the regenerated waste liquid is prepared by a method comprising the following steps: Ferric chloride, lanthanum chloride, and copper chloride are dissolved in a first solvent to prepare a metal salt solution. Based on 100 parts by weight of porous activated carbon support, the loading of ferric chloride is 3.0-5.0 parts by weight, the loading of lanthanum chloride is 3.0-9.0 parts by weight, and the loading of copper chloride is 0.5-1.5 parts by weight. The metal salt solution is uniformly loaded onto the porous activated carbon support, and after drying and a first calcination, a first adsorbent precursor is obtained. A nitrogen-rich organic ligand salt is dissolved in a second solvent to prepare a nitrogen-containing precursor solution. The nitrogen-rich organic ligand salt is selected from at least one of urea, dicyandiamide, guanidine hydrochloride, or disodium ethylenediaminetetraacetate. The amount of nitrogen-rich organic ligand salt is 5.0-15.0 parts by weight, based on 100 parts by weight of the porous activated carbon carrier. The nitrogen-containing precursor solution is uniformly loaded onto the first adsorbent precursor and dried to obtain the second adsorbent precursor. The second adsorbent precursor is subjected to a second calcination in a nitrogen atmosphere. The calcination temperature is 300℃-700℃ and the calcination time is 1 hour-4 hours, which induces the formation of iron-lanthanum-copper composite oxide, nitrogen-doped carbon structure and CO-La chemical bond. The porous activated carbon support has hydroxyl and / or carbonyl groups on its surface, and the lanthanum element in the iron-lanthanum-copper composite oxide combines with the hydroxyl and / or carbonyl groups to form the CO-La chemical bond.

2. The method for recovering and treating waste liquid from the regeneration of phosphorus-supported catalyst as described in claim 1, characterized in that: The porous activated carbon carrier has an iodine adsorption value of 700 mg / g-1200 mg / g and an average particle size of 3 mm-5 mm.

3. The method for recovering and treating waste liquid from the regeneration of phosphorus-supported catalyst as described in claim 1, characterized in that: The adsorption device is a storage tank filled with the phosphorus removal adsorbent of the regenerated waste liquid; the step of introducing the phosphorus-loaded catalyst regeneration waste liquid into the adsorption device specifically involves: pumping the phosphorus-loaded catalyst regeneration waste liquid into the storage tank, allowing it to stand for adsorption for more than 24 hours, and then discharging the phosphorus-poor regeneration liquid.

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