Phosphorus-loaded catalyst regeneration waste liquid recovery treatment method and phosphorus-loaded catalyst regeneration waste liquid recovery treatment device

Abstract

The invention discloses a phosphorus-loaded catalyst regeneration waste liquid recovery treatment method and a phosphorus-loaded catalyst regeneration waste liquid recovery treatment device, and aims to better control the acidity of a regeneration liquid so as to maintain the service life of a phosphorus-loaded catalyst and realize the cyclic utilization of the regeneration liquid and the reduction concentration of phosphorus resources. And the treatment difficulty of the regenerated waste liquid can also be reduced. Comprising the following steps: introducing the phosphorus-loaded catalyst regeneration waste liquid into an adsorption device filled with a regeneration waste liquid dephosphorization adsorbent, separating a phosphorus component in the phosphorus-loaded catalyst regeneration waste liquid, collecting an effluent as a phosphorus-poor regeneration liquid, and recycling the phosphorus-poor regeneration liquid for regeneration of the phosphorus-loaded catalyst, after the regeneration waste liquid dephosphorization adsorbent is saturated in adsorption, hot water is adopted as a desorption medium to replace the stored liquid in the adsorption device, the volume of the desorption medium is controlled to be smaller than the volume of the phosphorus-carrying catalyst regeneration waste liquid capable of being contained in the adsorption device, and the regeneration waste liquid dephosphorization adsorbent is eluted.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of flue gas catalytic oxidation dephosphorization, and particularly relates to a phosphorus-loaded catalyst regeneration waste liquid recovery treatment method and device. BACKGROUND

[0002] The electric furnace method yellow phosphorus production process produces a large amount of tail gas rich in carbon monoxide, which is an excellent heat source and raw material for producing carbon-based chemicals. However, the tail gas contains many impurities in addition to the main component CO, such as inorganic sulfur (H2S, S, SO2), organic sulfur (CH4, SH, COS), SiF4, PH3, AsH3, P4, HF, CH4, CO2, O2, N2, cyanide, and trace dust. For the removal of phosphorus in the tail gas, catalytic oxidation can be used. The basic principle of catalytic oxidation is to heat the tail gas to 80-110 DEG C, add a small amount of air, and pass through the phosphorus-loaded catalyst bed of the fixed bed reactor, so that phosphorus, sulfur and other impurities are oxidized, among which phosphorus and PH3 are oxidized to P2O3, P2O5 and phosphoric acid. These oxidation products are adsorbed on the surface of the phosphorus-loaded catalyst, thereby purifying the tail gas.

[0003] When the phosphorus-loaded catalyst is saturated, water is usually used as a regeneration liquid for elution regeneration to restore the activity of the phosphorus-loaded catalyst. If the regeneration liquid is recycled for catalyst cleaning and regeneration, the concentration of phosphoric acid in the regeneration liquid will continue to accumulate with the increase in the number of cycles. Studies have shown that a higher concentration of phosphoric acid solution can seriously affect the service life of the phosphorus-loaded catalyst. In addition, based on the working principle of the phosphorus-loaded dephosphorization agent "adsorption-oxidation", the active components of the phosphorus-loaded catalyst migrate after the reaction, causing changes in the structure. In the presence of a strong acid regeneration liquid environment, the active components on the phosphorus-loaded catalyst are prone to loss, which not only reduces the regeneration effect of the phosphorus-loaded catalyst, but also makes the regeneration waste liquid contain heavy metal ions, becoming a secondary hazardous waste that is difficult to handle. Therefore, the number of times of recycling the regeneration liquid is limited, and the regeneration waste liquid quickly becomes a regeneration waste liquid containing phosphoric acid and a small amount of metal ions.

[0004] Currently, the treatment of such regeneration waste liquid faces great challenges: on the one hand, the amount of regeneration waste liquid is large, and direct discharge will cause serious environmental pollution and high treatment cost; on the other hand, if resource utilization is to be achieved, the dilute phosphoric acid in the regeneration waste liquid needs to be concentrated and the metal impurities need to be removed, and the existing concentration and purification process is complex, high in energy consumption and difficult. SUMMARY

[0005] The application aims to provide a phosphorus-loaded catalyst regeneration waste liquid recycling treatment method and device to solve the technical problem of how to better control the acidity of the regeneration liquid to maintain the service life of the phosphorus-loaded catalyst, realize the recycling of the regeneration liquid and the reduction and concentration of phosphorus resources, and reduce the difficulty of treating the regeneration waste liquid.

[0006] In a first aspect, a phosphorus-loaded catalyst regeneration waste liquid recycling treatment method includes: introducing the phosphorus-loaded catalyst regeneration waste liquid into an adsorption device filled with a regeneration waste liquid phosphorus removal adsorbent, selectively adsorbing the phosphorus component in the phosphorus-loaded catalyst regeneration waste liquid by using the regeneration waste liquid phosphorus removal adsorbent to separate the phosphorus component in the phosphorus-loaded catalyst regeneration waste liquid, and collecting the effluent as a phosphorus-lean regeneration liquid; the phosphorus-lean regeneration liquid is recycled for the regeneration of the phosphorus-loaded catalyst; the phosphorus component is mainly phosphate; 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-loaded catalyst regeneration waste liquid that can be contained in the adsorption device, and the regeneration waste liquid phosphorus removal adsorbent is eluted; hot water is used to destroy the combination of the regeneration waste liquid phosphorus removal adsorbent and the adsorbed phosphorus component, the adsorbed phosphorus component is transferred to the aqueous phase, a high-concentration phosphorus-containing solution with a reduced volume is obtained, and the eluted regeneration waste liquid phosphorus removal adsorbent is dried to restore the adsorption performance for standby use; wherein the regeneration waste liquid phosphorus removal adsorbent is a supported composite material including a porous activated carbon carrier and an active component loaded on the porous activated carbon carrier; the active component includes iron-lanthanum-copper composite oxide and nitrogen-doped carbon structure, and a C-O-La chemical bond is formed between the active component and the porous activated carbon carrier.

[0007] As an optimization and / or instantiation of the above-mentioned phosphorus-loaded catalyst regeneration waste liquid recycling treatment method, further: the regeneration waste liquid phosphorus removal adsorbent is prepared by a method including 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 on the porous activated carbon carrier, drying and first calcining to obtain a first adsorbent precursor; dissolving a nitrogen-rich organic ligand salt in a second solvent to prepare a nitrogen-containing precursor solution, uniformly loading the nitrogen-containing precursor solution on the first adsorbent precursor, and drying to obtain a second adsorbent precursor; second calcining the second adsorbent precursor in an inert atmosphere to induce the formation of the iron-lanthanum-copper composite oxide, the nitrogen-doped carbon structure, and the C-O-La chemical bond.

[0008] As an optimization and / or instantiation of the above-mentioned phosphorus-loaded catalyst regeneration waste liquid recovery treatment method, further: the iron salt is ferric chloride, the lanthanum salt is lanthanum chloride, and the copper salt is copper chloride; the loading amount of the ferric chloride is 3.0-5.0 parts by weight, the loading amount of the lanthanum chloride is 3.0-9.0 parts by weight, and the loading amount of the copper chloride is 0.5-1.5 parts by weight, based on 100 parts by weight of the mass of the porous activated carbon carrier.

[0009] As an optimization and / or instantiation of the above-mentioned phosphorus-loaded catalyst regeneration waste liquid recovery treatment method, further: the surface of the porous activated carbon carrier contains hydroxyl and / or carbonyl groups, and the lanthanum element in the active component binds with the hydroxyl and / or carbonyl groups to form the C-O-La chemical bond.

[0010] As an optimization and / or instantiation of the above-mentioned phosphorus-loaded catalyst regeneration waste liquid recovery treatment method, further: the nitrogen-rich organic ligand salt is selected from at least one of urea, dicyandiamide, guanidine hydrochloride, or disodium ethylenediaminetetraacetate; and 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 mass of the porous activated carbon carrier.

[0011] As an optimization and / or instantiation of the above-mentioned phosphorus-loaded catalyst regeneration waste liquid recovery treatment method, further: the second calcination is performed by calcining in a nitrogen atmosphere for 1-4 hours at a calcination temperature of 300-700°C.

[0012] As an optimization and / or instantiation of the above-mentioned phosphorus-loaded catalyst regeneration waste liquid recovery treatment method, further: the iodine adsorption value of the porous activated carbon carrier is 700-1200 mg / g, and the average particle size is 3-5 mm.

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

[0014] As an optimization and / or instantiation of the above-mentioned phosphorus-loaded catalyst regeneration waste liquid recovery treatment method, further: the temperature of the hot water is 60-90°C, and the elution time is 24-48 hours; and the volume of the desorption medium is 1 / 4 to 1 / 2 of the volume of the phosphorus-loaded catalyst regeneration waste liquid that can be accommodated in the adsorption device.

[0015] In a second aspect, a phosphorus-loaded catalyst regeneration waste liquid recycling device is provided for implementing the phosphorus-loaded catalyst regeneration waste liquid recycling method of the first aspect; the device comprises: an adsorption device, which is internally filled with the phosphorus removal adsorbent for the regeneration waste liquid; an inlet pipeline, which is connected to the inlet of the adsorption device and used for inputting the phosphorus-loaded catalyst regeneration waste liquid from the fixed-bed reactor for phosphorus removal by catalytic oxidation of flue gas into the adsorption device; a recycling pipeline, one end of which is connected to the outlet of the adsorption device and the other end of which is connected to the phosphorus-loaded catalyst regeneration system of the fixed-bed reactor for phosphorus removal by catalytic oxidation of flue gas, and which is used for recycling the phosphorus-lean regeneration liquid for the regeneration of the phosphorus-loaded catalyst; and a desorption regeneration assembly, which comprises a hot water supply source and a desorption pipeline connecting the hot water supply source and the adsorption device, and which is used for introducing hot water into the adsorption device to elute the phosphorus components adsorbed on the phosphorus removal adsorbent for the regeneration waste liquid, so as to obtain a high-concentration phosphorus-containing solution with reduced volume.

[0016] The phosphorus-loaded catalyst regeneration waste liquid recycling method and device of the present application can produce the following technical effects by introducing a specific phosphorus removal adsorbent for the regeneration waste liquid and combining a hot water desorption process.

[0017] First, the recycling of the regeneration liquid is realized, and the service life of the phosphorus-loaded catalyst is significantly prolonged. The phosphorus components in the phosphorus-loaded catalyst regeneration waste liquid are selectively adsorbed by the phosphorus removal adsorbent for the regeneration waste liquid, which effectively reduces the concentration of phosphoric acid in the regeneration liquid and greatly reduces the acidity of the phosphorus-lean regeneration liquid. The low-acidity phosphorus-lean regeneration liquid is recycled for the regeneration of the phosphorus-loaded catalyst, which avoids the damage of the high-concentration acidic environment to the structure of the phosphorus-loaded catalyst and the loss of the active components, thereby maintaining the activity of the phosphorus-loaded catalyst and prolonging the replacement cycle.

[0018] Second, the volume reduction and enrichment of the phosphorus resources of the regeneration waste liquid are realized, and the treatment cost is reduced. The present application uses hot water with a volume smaller than the volume of the adsorption device as a desorption medium to transfer the phosphorus components dispersed in a large amount of phosphorus-loaded catalyst regeneration waste liquid into a small amount of aqueous phase, thereby obtaining a high-concentration phosphorus-containing solution with reduced volume. This process not only solves the problem of difficult direct utilization of a large amount of low-concentration regeneration waste liquid and high treatment cost, but also provides convenient conditions for the resource utilization of the subsequent phosphorus resources.

[0019] Thirdly, the regenerated waste liquid phosphorus removal adsorbent has stable structure, large adsorption capacity and strong acid resistance. The regenerated waste liquid phosphorus removal adsorbent used in the application is a supported composite material, and a stable C-O-La chemical bond is formed between the active component (iron-lanthanum-copper composite oxide and nitrogen-doped carbon structure) and the porous active carbon carrier. The chemical bond cooperation not only improves the affinity and adsorption capacity of the adsorbent to phosphate, but more importantly, enhances the binding force of the active component and the porous active carbon carrier, effectively prevents the loss of the active component in the acidic regenerated waste liquid environment, and ensures the structural stability and phosphorus removal performance of the regenerated waste liquid phosphorus removal adsorbent in multiple "adsorption-regeneration" cycles.

[0020] Fourthly, the process flow is simple and green. The phosphorus-loaded catalyst regenerated waste liquid recovery treatment method of the application can be completed only by adsorption and hot water elution, without adding complex chemical precipitants, avoiding secondary pollution. And the adsorbent regeneration only needs hot water, which is low in energy consumption, simple in operation and easy to industrialize.

[0021] The application will be further described below in combination with the drawings and specific embodiments. Additional aspects and advantages of the application will be partially given in the following description, partially become obvious from the following description, or be understood by practice. BRIEF DESCRIPTION OF DRAWINGS

[0022] The drawings constituting a part of this specification are used to assist the understanding of the application, and the contents provided by the drawings and the related description in the specification can be used to explain the application, but do not constitute an improper limitation on the application.

[0023] Figure 1 It is a micrograph of the regenerated waste liquid phosphorus removal adsorbent of experimental example 2 of the application.

[0024] Figure 2 It is an X-ray photoelectron spectrum (C 1s high-resolution spectrum) of the regenerated waste liquid phosphorus removal adsorbent of experimental example 2 of the application.

[0025] Figure 3 It is an X-ray photoelectron spectrum (N 1s high-resolution spectrum) of the regenerated waste liquid phosphorus removal adsorbent of experimental example 2 of the application.

[0026] Figure 4 It is an X-ray photoelectron spectrum (O 1s high-resolution spectrum) of the regenerated waste liquid phosphorus removal adsorbent of experimental example 2 of the application.

[0027] Figure 5 It is an X-ray photoelectron spectrum (La 3d5 / 2 high-resolution spectrum) of the regenerated waste liquid phosphorus removal adsorbent of experimental example 2 of the application. DETAILED DESCRIPTION

[0028] The application will be described in detail below with reference to the drawings. Those skilled in the art will be able to implement the application based on these descriptions. Before the application is described in conjunction with the drawings, it should be particularly pointed out that:

[0029] The technical solutions and technical features provided in the various parts including the following description can be combined with each other without conflict. In addition, in the case of possibility, these technical solutions, technical features and related combinations can be given a specific technical subject and protected by a related patent.

[0030] The embodiments of the application involved in the following description are generally only a part of the embodiments and not all the embodiments. Based on these embodiments, all other embodiments obtained by those skilled in the art without creative labor should belong to the scope of patent protection.

[0031] The term "comprising" and any variation thereof in the specification and corresponding claims and related parts is intended to cover non-exclusive inclusion. Other related terms and units can be reasonably interpreted based on the related content provided in the specification.

[0032] Experimental Example 1

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

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

[0035] Then, 10.0 g of urea (nitrogen-rich organic ligand salt) was dissolved in 50 mL of distilled water (second solvent) to prepare a nitrogen-containing precursor solution. The nitrogen-containing precursor solution was uniformly sprayed onto the first adsorbent precursor prepared above, and stirred thoroughly. After standing for 2 hours, it was dried in an oven at 80°C for 4 hours to obtain a second adsorbent precursor. The second adsorbent precursor was placed in a muffle furnace and nitrogen was introduced for 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 waste liquid was obtained.

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

[0037] To test the regeneration effect, first prepare the adsorption saturated phosphorus-loaded catalyst. The experiment simulates the composition of the electric furnace method yellow phosphorus tail gas for testing. Fresh phosphorus-loaded catalyst is placed in a quartz tube reactor (diameter 1.8 mm), and the adsorbed water is removed by preheating and sweeping. The reaction temperature is set to 80°C. The total gas flow into the quartz tube reactor is about 800 mL·min -1 , where the inlet concentration of PH3 is 2000 ppm. The concentration of PH3 in the outlet gas is continuously detected by a gas detector until the breakthrough efficiency of the phosphorus-loaded catalyst is 99.9% (i.e., the outlet concentration approaches the inlet concentration), at which point the phosphorus-loaded catalyst is considered saturated. The phosphorus capacity of the phosphorus-loaded catalyst is measured to be 245 mg (PH3)·g sorbent -1 .

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

[0039] The above saturated phosphorus-loaded catalyst is regenerated by in-situ water washing. Two-stage regeneration is used, and the single-stage regeneration time is 30 min.

[0040] The first stage of regeneration uses water to wash the saturated catalyst, and the effluent after water washing is the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the first stage is pumped into a first liquid storage tank (first adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in this experiment. The phosphorus-loaded catalyst regeneration waste liquid is allowed to stand in the storage tank for 24 hours, and the regeneration waste liquid phosphorus removal adsorbent selectively adsorbs the phosphate in the phosphorus-loaded catalyst regeneration waste liquid. The P species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment is detected. The phosphate content in the phosphorus-loaded catalyst regeneration waste liquid before adsorption treatment is 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out is reduced to 11527 mg / L (corresponding to a phosphoric acid mass percentage of 1.11%). It is calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the first adsorption device is 77%.

[0041] The second-stage regenerated water washes the saturated catalyst, and the effluent after water washing is the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the above second-stage regeneration is pumped into a second-stage liquid storage tank (second-stage adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in the present experimental example. The phosphorus-loaded catalyst regeneration waste liquid is allowed to stand in the liquid storage tank for 24 hours of adsorption, and the regeneration waste liquid phosphorus removal adsorbent selectively adsorbs the phosphate in the phosphorus-loaded catalyst regeneration waste liquid. The content of P species (calculated as phosphate) in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment is detected. The content of phosphate in the phosphorus-loaded catalyst regeneration waste liquid before adsorption treatment is 26836 mg / L (corresponding to a mass percentage of phosphoric acid of 2.6%); after adsorption treatment, the content of phosphate in the phosphorus-lean regeneration liquid flowing out is reduced to 5098 mg / L (corresponding to a mass percentage of phosphoric acid of 0.47%). It is calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the second-stage adsorption device reaches 81%.

[0042] (4) Desorption and regeneration of the regeneration waste liquid phosphorus removal adsorbent

[0043] After multiple "adsorption" cycles, when the regeneration waste liquid phosphorus removal adsorbent reaches saturation and no longer effectively adsorbs P species, desorption is performed.

[0044] Hot water is pumped into each liquid storage tank as a desorption medium, and the volume of hot water is controlled to be 1 / 3 of the volume of the phosphorus-loaded catalyst regeneration waste liquid that can be contained in the liquid storage tank. Soak in hot water at 80°C for 48 hours. The hot water is used to destroy the combination of the adsorbent and the phosphorus component, and transfer the phosphorus component to the aqueous phase.

[0045] After desorption is completed, the regeneration waste liquid phosphorus removal adsorbent is dried for standby and recovery of adsorption performance. At the same time, the volume-reduced high-concentration phosphorus (phosphoric acid) containing solution is collected, and the enrichment of phosphorus resources is achieved.

[0046] Experimental Example 2

[0047] (1) Preparation of the regeneration waste liquid phosphorus removal adsorbent

[0048] First, 3.8 g of iron chloride, 7.8 g of lanthanum chloride, and 1.0 g of copper chloride are dissolved in 50 mL of distilled water (first solvent) to prepare a metal salt solution. The metal salt solution is uniformly sprayed onto 100 g of porous activated carbon carriers (iodine adsorption value of 960 mg / g, average particle size of 4 mm), stirred thoroughly, and then placed in an oven for drying at 80°C for 4 hours. After drying, the carriers are taken out and placed in a muffle furnace for first calcination (temperature set to 350°C, nitrogen atmosphere, calcination time of 2 hours) to obtain a first adsorbent precursor.

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

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

[0051] The same as Experimental Example 1.

[0052] (3) Regeneration of the phosphorus-loaded catalyst and adsorption treatment of the regenerated waste liquid

[0053] The saturated phosphorus-loaded catalyst was regenerated by in-situ water washing. Two-stage regeneration was used, and the single-stage regeneration time was 30 min.

[0054] The saturated catalyst was water washed using water in the first stage of regeneration, and the effluent after water washing was the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the first stage of regeneration was pumped into a first liquid storage tank (first adsorption device) filled with 20 g of the regenerated waste liquid phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand in the liquid storage tank for 24 hours of adsorption, and the regenerated waste liquid phosphorus removal adsorbent was used to selectively adsorb phosphate in the phosphorus-loaded catalyst regeneration waste liquid. The content of P species (calculated as phosphate) in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was detected. The phosphate content in the phosphorus-loaded catalyst regeneration waste liquid before adsorption treatment was 50118 mg / L (corresponding to a mass percentage of phosphoric acid of 4.8%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out was reduced to 4009 mg / L (corresponding to a mass percentage of phosphoric acid of 0.5%). It was calculated that the adsorption efficiency of the regenerated waste liquid phosphorus removal adsorbent in the first adsorption device reached 92%.

[0055] The second-stage regenerated water washes the saturated catalyst, and the effluent after the water washing is the phosphorus-laden catalyst regeneration waste liquid. The phosphorus-laden catalyst regeneration waste liquid generated in the second-stage regeneration is pumped into a second-stage liquid storage tank (second-stage adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in the present experimental example. The phosphorus-laden catalyst regeneration waste liquid is allowed to stand in the liquid storage tank for 24 hours of adsorption, and the regeneration waste liquid phosphorus removal adsorbent is used to selectively adsorb the phosphate in the phosphorus-laden catalyst regeneration waste liquid. The content of P species (calculated as phosphate) in the phosphorus-laden catalyst regeneration waste liquid before and after the adsorption treatment is detected. The content of phosphate in the phosphorus-laden catalyst regeneration waste liquid before the adsorption treatment is 26836 mg / L (corresponding to a mass percentage of phosphoric acid of 2.6%); after the adsorption treatment, the content of phosphate in the phosphorus-lean regeneration liquid flowing out is reduced to 2146 mg / L (corresponding to a mass percentage of phosphoric acid of 0.22%). It is calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the second-stage adsorption device is 92%.

[0056] (4) Desorption and regeneration of the regeneration waste liquid phosphorus removal adsorbent

[0057] The same as Experimental Example 1.

[0058] Experimental Example 3

[0059] (1) Preparation of the regeneration waste liquid phosphorus removal adsorbent

[0060] First, 3.0 g of ferric chloride, 9.0 g of lanthanum chloride, and 0.5 g of copper chloride are dissolved in 50 mL of distilled water (first solvent) to prepare a metal salt solution. The metal salt solution is uniformly sprayed onto 100 g of a porous activated carbon carrier (iodine adsorption value of 960 mg / g, average particle size of 4 mm), stirred thoroughly, and then placed in an oven for drying at 80°C for 4 hours. After being taken out, the first adsorbent precursor is obtained by being placed in a muffle furnace for first calcination (temperature set at 350°C, nitrogen atmosphere, and calcination for 2 hours).

[0061] Then, 5.0 g of urea (nitrogen-rich organic ligand salt) is dissolved in 50 mL of distilled water (second solvent) to prepare a nitrogen-containing precursor solution. The nitrogen-containing precursor solution is uniformly sprayed onto the first adsorbent precursor prepared above, stirred thoroughly, and then placed in an oven for drying at 80°C for 4 hours to obtain a second adsorbent precursor. The second adsorbent precursor is placed in a muffle furnace, nitrogen is introduced, and second calcination is performed. The calcination temperature is set at 500°C, and the calcination time is 2 hours. After being cooled to room temperature, the final regeneration waste liquid phosphorus removal adsorbent is obtained.

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

[0063] The same as Experimental Example 1.

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

[0065] The saturated phosphorus-loaded catalyst was regenerated by in-situ water washing. Two-stage regeneration was adopted, and the single-stage regeneration time was 30 min.

[0066] The saturated catalyst was water washed with water for the first-stage regeneration, and the effluent after water washing was the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the first-stage regeneration was pumped into a first-stage liquid storage tank (first-stage adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand and adsorb in the liquid storage tank for 24 hours. The P species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was detected. The phosphate content in the phosphorus-loaded catalyst regeneration waste liquid before adsorption treatment was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out was reduced to 5512 mg / L (corresponding to a phosphoric acid mass percentage of 0.53%). It was calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the first-stage adsorption device reached 89%.

[0067] The saturated catalyst was water washed with water for the second-stage regeneration, and the effluent after water washing was the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the second-stage regeneration was pumped into a second-stage liquid storage tank (second-stage adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid was allowed to stand and adsorb in the liquid storage tank for 24 hours. The P species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment was detected. The phosphate content in the phosphorus-loaded catalyst regeneration waste liquid before adsorption treatment was 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out was reduced to 3757 mg / L (corresponding to a phosphoric acid mass percentage of 0.36%). It was calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the second-stage adsorption device reached 86%.

[0068] (4) Desorption and regeneration of regeneration waste liquid phosphorus removal adsorbent

[0069] The same as Experimental Example 1.

[0070] Experimental Example 4

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

[0072] First, 4.5 g of ferric chloride, 9.0 g of lanthanum chloride, and 1.5 g of copper chloride were dissolved in 50 mL of distilled water (first solvent) to prepare a metal salt solution. The metal salt solution was uniformly sprayed onto 100 g of porous activated carbon carriers (iodine adsorption value: 960 mg / g, average particle size: 4 mm) and stirred thoroughly. After being left to stand for 2 hours, the carriers were dried in an oven at 80°C for 4 hours, and then taken out and placed in a muffle furnace for first calcination (temperature setting: 350°C, nitrogen atmosphere, calcination time: 2 hours) to obtain a first adsorbent precursor.

[0073] Then, 15.0 g of urea (nitrogen-rich organic ligand salt) was dissolved in 50 mL of distilled water (second solvent) to prepare a nitrogen-containing precursor solution. The nitrogen-containing precursor solution was uniformly sprayed onto the first adsorbent precursor prepared above, and stirred thoroughly. After being left to stand for 2 hours, the carriers were dried in an oven at 80°C for 4 hours to obtain a second adsorbent precursor. The second adsorbent precursor was placed in a muffle furnace and subjected to second calcination under a nitrogen atmosphere. The calcination temperature was set to 500°C, and the calcination time was 2 hours. After being cooled to room temperature, the final regenerated spent liquor phosphorus removal adsorbent was obtained.

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

[0075] The same as Experimental Example 1.

[0076] (3) Regeneration of phosphorus-loaded catalyst and adsorption treatment of regenerated spent liquor

[0077] The saturated phosphorus-loaded catalyst was regenerated by in-situ water washing. Two-stage regeneration was adopted, and the single-stage regeneration time was 30 minutes.

[0078] The saturated catalyst was water-washed with water in the first stage of regeneration, and the effluent after water washing was the regenerated spent liquor of the phosphorus-loaded catalyst. The regenerated spent liquor of the phosphorus-loaded catalyst produced in the first stage of regeneration was pumped into a first liquid storage tank (first adsorption device) filled with 20 g of the regenerated spent liquor phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration spent liquor was left to stand in the storage tank for 24 hours of adsorption. The P species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration spent liquor before and after adsorption treatment was detected. The phosphate content in the phosphorus-loaded catalyst regeneration spent liquor before adsorption treatment was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out was reduced to 4510 mg / L (corresponding to a phosphoric acid mass percentage of 0.43%). It was calculated that the adsorption efficiency of the regenerated spent liquor phosphorus removal adsorbent in the first adsorption device reached 91%.

[0079] The second-stage regenerated water washes the saturated catalyst, and the effluent after the water washing is the phosphorus-laden catalyst regeneration waste liquid. The phosphorus-laden catalyst regeneration waste liquid generated in the second-stage regeneration is pumped into a second-stage liquid storage tank (second-stage adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in the present experimental example. The phosphorus-laden catalyst regeneration waste liquid is allowed to stand in the liquid storage tank for 24 hours for adsorption. The P species (calculated as phosphate) content in the phosphorus-laden catalyst regeneration waste liquid before and after the adsorption treatment is detected. The phosphate content in the phosphorus-laden catalyst regeneration waste liquid before the adsorption treatment is 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after the adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out is reduced to 2952 mg / L (corresponding to a phosphoric acid mass percentage of 0.28%). It is calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the second-stage adsorption device is 89%.

[0080] (4) Desorption and regeneration of the regeneration waste liquid phosphorus removal adsorbent

[0081] The same as Experimental Example 1.

[0082] Experimental Example 5

[0083] (1) Preparation of the regeneration waste liquid phosphorus removal adsorbent

[0084] First, 3.8 g of iron chloride, 7.8 g of lanthanum chloride, and 1.0 g of copper chloride are dissolved in 50 mL of distilled water (first solvent) to prepare a metal salt solution. The metal salt solution is uniformly sprayed onto 100 g of a porous activated carbon carrier (iodine adsorption value of 960 mg / g, average particle size of 4 mm), stirred thoroughly, and then placed in an oven for drying at 80°C for 4 hours. After being taken out, the carrier is placed in a muffle furnace for first calcination (temperature set at 350°C, nitrogen atmosphere, and calcination time of 2 hours) to obtain a first adsorbent precursor.

[0085] Then, 10.0 g of dicyandiamide (a nitrogen-rich organic ligand salt) is dissolved in 50 mL of distilled water (second solvent, which can be appropriately heated to aid dissolution according to the dissolution condition) to prepare a nitrogen-containing precursor solution. The nitrogen-containing precursor solution is uniformly sprayed onto the first adsorbent precursor prepared above, stirred thoroughly, and then placed in an oven for drying at 80°C for 4 hours to obtain a second adsorbent precursor. The second adsorbent precursor is placed in a muffle furnace, nitrogen is introduced, and second calcination is performed. The calcination temperature is set at 500°C, and the calcination time is 2 hours. After being cooled to room temperature, the final regeneration waste liquid phosphorus removal adsorbent is obtained.

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

[0087] The same as Experimental Example 1.

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

[0089] The saturated phosphorus-loaded catalyst is regenerated by in-situ water washing. Two-stage regeneration is adopted, and the single-stage regeneration time is 30 min.

[0090] The saturated catalyst is washed with water in the first-stage regeneration, and the effluent after water washing is the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the first-stage regeneration is pumped into a first-stage liquid storage tank (first-stage adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid is allowed to stand in the liquid storage tank for 24 hours of adsorption. The P species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment is detected. The phosphate content in the phosphorus-loaded catalyst regeneration waste liquid before adsorption treatment is 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out is reduced to 6265 mg / L (corresponding to a phosphoric acid mass percentage of 0.60%). It is calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the first-stage adsorption device is 87.5%.

[0091] The saturated catalyst is washed with water in the second-stage regeneration, and the effluent after water washing is the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the second-stage regeneration is pumped into a second-stage liquid storage tank (second-stage adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration waste liquid is allowed to stand in the liquid storage tank for 24 hours of adsorption. The P species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment is detected. The phosphate content in the phosphorus-loaded catalyst regeneration waste liquid before adsorption treatment is 26836 mg / L (corresponding to a phosphoric acid mass percentage of 2.6%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out is reduced to 4025 mg / L (corresponding to a phosphoric acid mass percentage of 0.39%). It is calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the second-stage adsorption device is 85%.

[0092] (4) Desorption and regeneration of the regeneration waste liquid phosphorus removal adsorbent

[0093] The same as Experimental Example 1.

[0094] Experimental Example 6

[0095] (1) Preparation of the regeneration waste liquid phosphorus removal adsorbent

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

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

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

[0099] The same as Experimental Example 1.

[0100] (3) Regeneration of phosphorus-loaded catalyst and adsorption treatment of regenerated spent liquor

[0101] The saturated phosphorus-loaded catalyst was regenerated by in-situ water washing. Two-stage regeneration was adopted, and the single-stage regeneration time was 30 minutes.

[0102] The saturated catalyst was water-washed with water in the first stage of regeneration, and the effluent after water washing was the regenerated spent liquor of the phosphorus-loaded catalyst. The regenerated spent liquor of the phosphorus-loaded catalyst produced in the first stage of regeneration was pumped into a first liquid storage tank (first adsorption device) filled with 20 g of the regenerated spent liquor phosphorus removal adsorbent prepared in this experimental example. The phosphorus-loaded catalyst regeneration spent liquor was allowed to stand in the storage tank for 24 hours of adsorption. The P species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration spent liquor before and after adsorption treatment was detected. The phosphate content in the phosphorus-loaded catalyst regeneration spent liquor before adsorption treatment was 50118 mg / L (corresponding to a phosphoric acid mass percentage of 4.8%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid was reduced to 7517 mg / L (corresponding to a phosphoric acid mass percentage of 0.72%). It was calculated that the adsorption efficiency of the regenerated spent liquor phosphorus removal adsorbent in the first adsorption device reached 85%.

[0103] The second-stage regenerated water washes the saturated catalyst, and the effluent after water washing is the phosphorus-loaded catalyst regeneration waste liquid. The phosphorus-loaded catalyst regeneration waste liquid generated in the second-stage regeneration is pumped into a second-stage liquid storage tank (second-stage adsorption device) filled with 20 g of the regeneration waste liquid phosphorus removal adsorbent prepared in the present experimental example. The phosphorus-loaded catalyst regeneration waste liquid is allowed to stand in the liquid storage tank for 24 hours of adsorption. The P species (calculated as phosphate) content in the phosphorus-loaded catalyst regeneration waste liquid before and after adsorption treatment is detected. The phosphate content in the phosphorus-loaded catalyst regeneration waste liquid before adsorption treatment is 26836 mg / L (corresponding to a mass percentage of phosphoric acid of 2.6%); after adsorption treatment, the phosphate content in the phosphorus-lean regeneration liquid flowing out is reduced to 4830 mg / L (corresponding to a mass percentage of phosphoric acid of 0.46%). It is calculated that the adsorption efficiency of the regeneration waste liquid phosphorus removal adsorbent in the second-stage adsorption device reaches 82%.

[0104] (4) Desorption and regeneration of the regeneration waste liquid phosphorus removal adsorbent

[0105] The same as experimental example 1.

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

[0107] Table 1 - Adsorption treatment data summary table of phosphorus-loaded catalyst regeneration waste liquid

[0108]

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

[0110] The main difference between experimental example 1 and experimental example 2 is the different Fe / La molar ratio in the preparation of the adsorbent. Compared with experimental example 1 (Fe / La = 1:0.25), the Fe / La ratio in experimental example 2 is adjusted to 1:0.5, and with the increase of the amount of La doping, the performance of the adsorbent is significantly improved. It is calculated that the adsorption efficiency of experimental example 1 in the first stage is about 77%, while the adsorption efficiency of experimental example 2 is increased to about 92%. The mechanism of this performance leap may be that there are rich active groups such as hydroxyl and carbonyl groups on the surface of the adsorbent carrier, which can form stable C-O-La chemical bonds with the introduced La. In experimental example 1, although the C-O-La structure is formed, the active sites on the surface of the carrier are not fully filled due to the limited amount of La. In experimental example 2, with the increase of the content of La, the density of the C-O-La chemical bonds formed on the surface of the carrier is significantly increased, not only fully utilizing the surface functional groups of the carrier, but also greatly improving the abundance of the phosphorus-philic active sites (La species) on the surface of the adsorbent. This high-density active site is exposed to the phosphoric acid environment, greatly enhancing the complex capture ability of phosphate, thereby realizing the qualitative change of the 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] Compared with Examples 1 to 6, the regenerated waste liquid phosphorus removal adsorbent prepared in Example 2 exhibits the best adsorption performance. In the first stage treatment, it can reduce the high concentration of phosphate (50118 mg / L) in the phosphorus-loaded catalyst regeneration waste liquid to 4009 mg / L, with the highest removal rate. This proves that by precisely adjusting the molar ratio of Fe / La, the second calcination temperature and the loading ratio of the porous activated carbon carrier, the C-O-La chemical bond on the surface of the material can be maximized to achieve high-efficiency selective adsorption of the phosphorus component in the phosphorus-loaded catalyst regeneration waste liquid, thereby effectively solving the problem of large amount of waste liquid caused by accumulation of acid content during recycling of the phosphorus-poor regeneration liquid.

[0115] The desorption treatment data of the phosphorus-loaded adsorbent are shown in Table 2.

[0116] Table 2 - Summary of desorption treatment data of the phosphorus-loaded catalyst

[0117]

[0118] As can be seen from the desorption data of the phosphorus-loaded catalyst in Table 2, when using hot water to elute and concentrate 1 / 3 of the volume of the regeneration waste liquid, the first-stage eluate concentration of Examples 1-6 from high to low is: Example 2 (12.70%) > Example 5 (12.48%) > Example 6 (12.39%) > Example 3 (12.15%) ≈ Example 4 (12.14%) > Example 1 (11.70%). The second-stage eluate concentration from high to low is: Example 2 (7.26%) > Example 5 (6.99%) > Example 3 (6.71%) > Example 4 (6.65%) > Example 1 (6.59%) > Example 6 (6.40%).

[0119] All the examples are treated by the "adsorption-thermal desorption" process to concentrate the 4.8% original solution of the first-stage washing liquid to a 11.7%-12.9% phosphoric acid solution (first-stage eluate), and the second-stage eluate also obtains a concentrated phosphoric acid solution of about 6%, which shows that the present application can realize the phosphoric acid adsorption-thermal water desorption concentration process, utilize the synergistic effect of ternary metals to obtain high selectivity adsorption, and at the same time, adjust the local pH of the material surface by doping N element, and weaken the combination of Fe, La and phosphate by mild heating, so that they are dissociated in hot water.

[0120] The above describes the relevant content of the present application. Those skilled in the art will be able to implement the present application based on these descriptions. Based on the above content of the present description, all other embodiments obtained by those skilled in the art without creative labor shall fall within the scope of the present application.

Claims

1. A method for recovering and treating a phosphorus-carrying catalyst regeneration waste liquid, characterized by comprising the steps of: The method comprises the following steps: ​ The phosphorus-containing catalyst regeneration waste liquid is introduced into an adsorption device filled with a phosphorus-removing adsorbent for regeneration waste liquid, and the phosphorus component in the phosphorus-containing catalyst regeneration waste liquid is selectively adsorbed by the phosphorus-removing adsorbent for regeneration waste liquid, so that the phosphorus component in the phosphorus-containing catalyst regeneration waste liquid is separated, and the effluent is collected as a phosphorus-lean regeneration liquid, which is recycled to the regeneration of the phosphorus-containing catalyst, and the phosphorus component is mainly phosphate; When the phosphorus-removing adsorbent for regeneration waste liquid 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-containing catalyst regeneration waste liquid that can be contained in the adsorption device, and the phosphorus-removing adsorbent for regeneration waste liquid is eluted; The combination of the phosphorus-removing adsorbent for regeneration waste liquid and the adsorbed phosphorus component is destroyed by using hot water, the adsorbed phosphorus component is transferred to the water phase, a high-concentration phosphorus-containing solution with a reduced volume is obtained, and the eluted phosphorus-removing adsorbent for regeneration waste liquid is dried to recover the adsorption performance and is ready for use. The phosphorus-removing adsorbent for regeneration waste liquid is a kind of supported composite material, which comprises a porous activated carbon carrier and an active component supported on the porous activated carbon carrier; the active component comprises iron-lanthanum-copper composite oxide and nitrogen-doped carbon structure, and a C-O-La chemical bond is formed between the active component and the porous activated carbon carrier.

2. The method for recovering phosphorus-containing catalyst regeneration waste liquid according to claim 1, characterized in that: The phosphorus-removing adsorbent for regeneration waste liquid is prepared by a method comprising the following steps: A metal salt solution is prepared by dissolving iron salt, lanthanum salt and copper salt in a first solvent, the metal salt solution is uniformly supported on the porous activated carbon carrier, and a first adsorbent precursor is obtained through drying and first calcination; A nitrogen-containing precursor solution is prepared by dissolving a nitrogen-rich organic ligand salt in a second solvent, the nitrogen-containing precursor solution is uniformly supported on the first adsorbent precursor, and a second adsorbent precursor is obtained through drying; The second adsorbent precursor is subjected to second calcination in an inert atmosphere to induce the formation of the iron-lanthanum-copper composite oxide, the nitrogen-doped carbon structure and the C-O-La chemical bond.

3. The method for recovering phosphorus-containing catalyst regeneration waste liquid according to claim 2, characterized in that: The iron salt is ferric chloride, the lanthanum salt is lanthanum chloride, and the copper salt is copper chloride; the loading amount of the ferric chloride is 3.0-5.0 parts by weight, the loading amount of the lanthanum chloride is 3.0-9.0 parts by weight, and the loading amount of the copper chloride is 0.5-1.5 parts by weight, based on 100 parts by weight of the mass of the porous activated carbon carrier.

4. The method for recovering phosphorus-containing catalyst regeneration waste liquid according to claim 2, characterized in that: The surface of the porous activated carbon carrier 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 C-O-La chemical bond.

5. The method for recovering phosphorus-containing catalyst regeneration waste liquid according to claim 2, characterized in that: 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 mass of the porous activated carbon carrier.

6. The method for recovering phosphorus-containing catalyst regeneration waste liquid according to claim 2, characterized in that: The second calcination is performed by calcination in a nitrogen atmosphere for 1-4 hours, and the calcination temperature is 300-700℃.

7. The method for recovering phosphorus-containing catalyst regeneration waste liquid according to claim 1, characterized in that: The iodine adsorption value of the porous activated carbon carrier is 700-1200 mg / g, and the average particle size is 3-5 mm.

8. The method for recovering phosphorus-containing catalyst regeneration waste liquid according to claim 1, characterized in that: The adsorption device is a liquid storage tank filled with the phosphorus-removing adsorbent for the regeneration waste liquid; the step of introducing the phosphorus-carrying catalyst regeneration waste liquid into the adsorption device is specifically pumping the phosphorus-carrying catalyst regeneration waste liquid into the liquid storage tank, standing for 24 hours or more, and then discharging the phosphorus-lean regeneration liquid.

9. The method for recovering phosphorus-containing catalyst regeneration waste liquid according to Claim 1, characterized in that: The temperature of the hot water is 60-90℃, the elution time is 24-48 hours, and the volume of the desorption medium is 1 / 4-1 / 2 of the volume of the phosphorus-carrying catalyst regeneration waste liquid that can be contained in the adsorption device.

10. A device for recovering and treating phosphorus-laden catalyst regeneration waste liquid, characterized by comprising: A method for treating phosphorus-carrying catalyst regeneration waste liquid, as claimed in any one of claims 1-9; Comprise: An adsorption device filled with the phosphorus-removing adsorbent for the regeneration waste liquid; A liquid inlet pipeline connected to the inlet of the adsorption device for inputting the phosphorus-carrying catalyst regeneration waste liquid from the fixed-bed dephosphorization reactor of the flue gas catalytic oxidation method into the adsorption device; A recycling pipeline connected at one end to the outlet of the adsorption device and at the other end to the phosphorus-carrying catalyst regeneration system of the fixed-bed dephosphorization reactor of the flue gas catalytic oxidation method for recycling the phosphorus-lean regeneration liquid for the regeneration of the phosphorus-carrying catalyst; and A desorption regeneration assembly comprising 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 elute the adsorbed phosphorus components on the phosphorus-removing adsorbent for the regeneration waste liquid, thereby obtaining a high-concentration phosphorus-containing solution with reduced volume.

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