CN113559820A - Preparation method, application and recovery method of phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater - Google Patents

Preparation method, application and recovery method of phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater Download PDF

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CN113559820A
CN113559820A CN202110992384.XA CN202110992384A CN113559820A CN 113559820 A CN113559820 A CN 113559820A CN 202110992384 A CN202110992384 A CN 202110992384A CN 113559820 A CN113559820 A CN 113559820A
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phosphorus removal
removal adsorbent
adsorbent
preparation
phosphorus
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李亮
龙学军
万骏
杨加知
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HUBEI XUNDA PHARMACEUTICAL CO Ltd
Wuhan Textile University
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HUBEI XUNDA PHARMACEUTICAL CO Ltd
Wuhan Textile University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0207—Compounds of Sc, Y or Lanthanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

Abstract

The invention provides a preparation method and an application recovery method of a phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater, wherein the preparation process of the phosphorus removal adsorbent comprises the following steps: step 1, preparing a mixed solution of lanthanum salt, aluminum salt and urea; step 2, injecting the mixed solution into a reaction kettle, and preparing an adsorption material by a hydrothermal method; step 3, washing the reactant obtained in the step 2 by deionized water until the supernatant is neutral; step 4, drying and grinding the reactant obtained in the step 3 into powder to obtain the required phosphorus removal adsorbent; the phosphorus removal adsorbent prepared by the preparation method can effectively remove high-concentration organic phosphorus in pharmaceutical wastewater. The invention further discloses a specific application method and a recovery method of the phosphorus removal adsorbent, so that the adsorbent can be repeatedly used, the long-term use cost of the adsorbent is further reduced, the harm of phosphorus in wastewater to a water environment is reduced, and the resource utilization of the phosphorus removal adsorbent is realized.

Description

Preparation method, application and recovery method of phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater
Technical Field
The invention belongs to the technical field of adsorbent material preparation and wastewater purification, and particularly relates to a preparation method, application and a recovery method of a high-concentration fosfomycin pharmaceutical wastewater phosphorus removal adsorbent.
Background
Phosphorus is an indispensable element in human life and is widely used in agriculture and industry. However, excessive phosphorus inevitably enters the aquatic environment through municipal wastewater, agricultural and industrial runoff, resulting in eutrophication of the water body. Therefore, the removal of phosphorus from wastewater is very important for the prevention and control of eutrophication of water bodies. The method for removing the phosphorus in the wastewater mainly comprises a biological method, a chemical precipitation method, a crystallization method, a membrane separation method, an adsorption method and the like. Among them, the adsorption method is a method that can effectively remove phosphorus from wastewater. One key technical problem in the application of adsorption processes to remove phosphorus from wastewater is the selection of suitable adsorbent materials.
At present, the production of fosfomycin mainly utilizes a chemical synthesis-chiral resolution technology. The fosfomycin pharmaceutical wastewater is mother liquor wastewater generated in the process of producing fosfomycin by a chemical synthesis process, main pollutants in the wastewater are organic phosphorus compounds containing C-P bonds (intermediate products and byproducts synthesized by the fosfomycin such as propinyl phosphoric acid, cis-propenyl phosphoric acid, epoxy cis-propenyl phosphoric acid and the like), alcohols, anilines, EDTA and other raw materials and solvents, the wastewater has complex components and strong antibacterial property, the COD of the wastewater is as high as tens of thousands to hundreds of thousands mg/L, the total phosphorus is as high as thousands of mg/L, and the organic matter in the wastewater has high concentration, is extremely difficult to degrade and has high toxicity to microorganisms. How to remove the total phosphorus in the pharmaceutical wastewater of high-concentration fosfomycin with high efficiency is a technical problem.
Figure BDA0003232844610000011
Is a lanthanum modified bentonite, and Douglas (US,6350383B 1.2002-2-26) introduces the main synthesis method: adding 0.1M LaCl3Mixing and stirring the solution and high-purity bentonite according to a liquid-solid ratio of 100:1 for 24 hours to perform an ion exchange reaction; centrifuging, and repeating the ion exchange step 1 time to ensure La3+Fully replacing cations among bentonite layers; distilled water was washed three times to remove residual La3+And carrying out centrifugal separation and drying to obtain the final product. The product has lanthanum loading of about 5 percent and phosphorus removal capacity of about 10mg-P/g, has good phosphorus locking effect because the phosphorus removal advantage of lanthanum is fully exerted, and has relatively simple synthesis principle and operation steps, and easy realization of industrialization, thereby obtaining large-scale application. However, the medicament still has some defects in practical application: for example, the lanthanum loading is not high, the isoelectric point is low, and the unit phosphorus removal capability is limited; la3+The combination with the carrier is weak, and the humic acid and the like in the water body are easy to cause La3+Dissolution increases the ecological risk; at higher basicity, CO3 2+And HCO3 -The combination of lanthanum and phosphorus is easily interfered, so that the phosphorus removal efficiency is reduced; the carrier bentonite has lower isoelectric point, weak phosphorus removal capability and no flocculation promotion capability; poor removal of particulate phosphorus and organic phosphorus, and the like. At present, various lanthanide phosphorus removal agents are developed for advanced treatment of phosphorus-containing wastewater and water environment restoration, including lanthanum-loaded zeolite, lanthanum hydroxide, lanthanum oxide, lanthanum molybdate and the like, but the lanthanide phosphorus removal agents mainly aim at orthophosphate adsorption in water and have poor removal capability on organic phosphorus. In addition, considering the complex water quality condition of high-concentration fosfomycin pharmaceutical wastewater, a novel lanthanide phosphorus removal material and a novel lanthanide phosphorus removal method are needed to be developed to effectively remove the total phosphorus.
After the phosphate is adsorbed, enrichment can be realized through a desorption technology, and then recovery is realized through an immobilization technology, and the method mainly comprises a calcium phosphate precipitation method and an ammonium magnesium phosphate crystallization method. Phosphorus removal and resource recovery of wastewater are hot spots of domestic and foreign researches, and the technology has high phosphorus removal efficiency, is stable and reliable, and is applied to phosphorus-rich wastewater such as anaerobic sludge supernatant, livestock and poultry breeding wastewater and the like at present. However, the concentration of organic phosphorus in high-concentration fosfomycin pharmaceutical wastewater is high, and a new method needs to be developed to realize the recovery of high-concentration phosphorus resources.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method, application and recovery of a high-concentration fosfomycin pharmaceutical wastewater phosphorus removal adsorbent. Considering that the main component of the high-concentration fosfomycin pharmaceutical wastewater is organic phosphorus, the efficient removal and recovery of the phosphorus can be realized by adopting the synergy of oxidation, adsorption and desorption.
The technical scheme adopted for solving the problems in the prior art is as follows:
a preparation method of a phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater comprises the following steps:
step 1, preparing a mixed solution of lanthanum salt, aluminum salt and urea;
step 2, injecting the mixed solution into a reaction kettle, and preparing an adsorption material by a hydrothermal method;
step 3, washing the reactant obtained in the step 2 by deionized water until the supernatant is neutral;
step 4, drying and grinding the reactant obtained in the step 3 into powder to obtain the required phosphorus removal adsorbent;
la in lanthanum salt and aluminum salt in the step 1: the molar ratio of Al is 1:1-10:1, the total concentration of the two metal salts is 0.05-0.5mol/L, and the concentration of urea is 1-14 mol/L.
The lanthanum salt in the step 1 is lanthanum chloride, lanthanum nitrate and the like; the aluminum salt is aluminum chloride, aluminum nitrate, aluminum sulfate, etc.
The reaction temperature of the hydrothermal method in the step 2 is 80-160 ℃, and the reaction time is more than 12 hours.
And (3) performing solid-liquid separation by using centrifugation during cleaning in the step 3.
And 4, drying at the drying temperature of 50-80 ℃ for 10-24 hours in the step 4, and grinding the prepared lanthanum aluminum carbonate composite material into powder with the particle size of less than 0.1 mm.
The application method of the phosphorus removal adsorbent prepared by the preparation method of the phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater comprises the following steps:
adding the prepared phosphorus removal adsorbent into high-concentration fosfomycin pharmaceutical wastewater according to the adding amount of 20-100g/L, simultaneously adding a hydrogen peroxide solution, wherein the content of active ingredients of the hydrogen peroxide solution is 300g/L, the adding amount ratio of the hydrogen peroxide solution to the high-phosphorus wastewater is 2:1-1:10, simultaneously injecting the obtained mixture into a reactor, and placing the reactor on a rotary table concentrator for reacting for 18-36 hours.
The rotating speed of the rotary table is 10-50 r/min, and the temperature is 10-35 ℃.
The recovery process of the adsorbent comprises the following steps: after natural precipitation of the adsorbent, separating the precipitate from the liquid, or carrying out centrifugal acceleration separation at the rotation speed of 3000-10000rpm, treating the precipitate for 24 hours by using 0.5-10M sodium hydroxide solution, washing the obtained regenerated material to be neutral by using deionized water, drying the regenerated material, and then repeatedly using the regenerated material.
The recovery process of the phosphate comprises the following steps: according to the Ca: adding calcium salt into the liquid separated in the adsorbent recovery process at a P molar ratio of 2:1, adding acid and alkali solution into the wastewater to maintain the pH value to be 8.5-10.0, stirring and reacting for 10-60 min, standing for 10-30 min, performing solid-liquid separation to obtain a phosphate recovery product and a supernatant, discharging the supernatant into a comprehensive wastewater treatment plant for biological treatment to achieve standard discharge, wherein the phosphate recovery product is calcium phosphate, and the recovered product can be used as a fine chemical raw material or used for preparing plant slow-release fertilizer.
The calcium salt comprises calcium chloride, calcium sulfate, calcium hydroxide or calcium oxide.
The invention has the following advantages:
(1) the prepared phosphorus removal adsorbent can effectively remove high-concentration organic phosphorus in pharmaceutical wastewater through coupling oxidation, adsorption and desorption treatment processes under the condition that an existing wastewater treatment unit is not required to be changed. After the aluminum salt is added, the isoelectric point of the material is improved, compared with a single lanthanide material, the material is easy to attract phosphate to be beneficial to dephosphorization due to the higher isoelectric point, and meanwhile, the preparation cost of the material is reduced.
(2) After the method is used for treating the high-concentration fosfomycin pharmaceutical wastewater, the phosphate in the wastewater can be immobilized and recovered through a calcium phosphate precipitation process, the harm of phosphorus in the wastewater to a water environment is reduced, and the resource utilization of the phosphorus is realized.
(3) The recovery method of the phosphorus removal adsorbent for the high-concentration fosfomycin pharmaceutical wastewater is provided, and the phosphorus removal adsorbent can be recovered through a desorption process after the adsorbent is used, so that the adsorbent can be repeatedly used, and the long-term use cost of the adsorbent is further reduced.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the present invention;
FIG. 2 is an adsorption isotherm diagram of a phosphorus removal adsorbent prepared according to an example of the present invention; wherein the abscissa is concentration and the ordinate is adsorption capacity;
FIG. 3 is a bar graph of the present invention for 10mg/L phosphate removal experiments; wherein, the abscissa is the dosage of the phosphorus removal adsorbent, and the ordinate is the removal rate.
Fig. 4 is an XRD pattern of the phosphorous removal adsorbent prepared by the example of the present invention, wherein the abscissa is scanning angle and the ordinate is intensity;
FIGS. 5 and 6 are TEM images of phosphorus removal adsorbents made according to examples of the present invention;
FIG. 7 is a schematic of the adsorption kinetics of the present invention; wherein, the abscissa is adsorption time, and the ordinate is adsorption capacity;
FIG. 8 is a bar graph of the total phosphorus removal experiment of the present invention; wherein the abscissa represents the type of the drug (H)2O2Hydrogen peroxide, Adsorbent) and the ordinate is the removal rate;
FIG. 9 is a histogram of the recycling performance of the present invention; wherein the abscissa is the number of recycling times and the ordinate is the removal rate.
Detailed Description
The technical scheme of the invention is further specifically described by the following embodiments and the accompanying drawings.
The preparation process flow of the preparation method of the phosphorus removal adsorbent for high-concentration fosfomycin pharmaceutical wastewater is shown in figure 1, and the specific steps and parameters are as follows:
step 1) preparation of 0.167 mol. L-1LaCl3、0.033mol·L-1AlCl3And 20 mol. L-1A mixed solution of urea;
step 2) injecting the prepared mixed solution into a reaction kettle, and reacting for 12 hours at 150 ℃;
and 3) washing the reaction product obtained in the step 2) to be neutral by using deionized water, drying and grinding into powder to obtain the required material.
The phosphorus removal adsorbent prepared in this example is white powder, and XRD test is performed on the sample, and the result is shown in FIG. 3, which indicates that LaAl (OH) may exist in the phosphorus removal adsorbent2(CO3)2、La2O3、La2CO3·8H2O、LaCO3OH、La2O2CO3. TEM testing is carried out on the sample, and the result is shown in FIG. 4, which shows that the particle size of the phosphorus removal adsorbent is 50-200 nm.
The application example is that the phosphorus removal adsorbent has the effect of removing phosphate: the concentration of phosphate was fixed at 10 mg-P.L-1. The adsorption reaction time is 24h, the temperature is 25 ℃, and the dosage of the phosphorus removal adsorbent is 0.1-0.5 g.L-1The initial pH was 7.0. The results show that the phosphate adsorption by the phosphorus removal adsorbent is multilayer adsorption, and the removal efficiency is higher than that of Phoslock (see fig. 2). When the addition amount of the phosphorus removing agent is 0.1 g.L-1When the phosphate removal rate is 70%, the addition amount of the phosphorus removing agent is 0.5 g.L-1When the removal rate of phosphate is more than 90 percent (as shown in figure 3), the above results show that the material has better effect on removing phosphate.
Weighing a certain amount of the phosphorus removal adsorbent obtained in the embodiment, mixing the phosphorus removal adsorbent with 10.8mg-P/L solution in an adding amount of 0.5g/L, adjusting the pH to about 7.0, oscillating in a shaking table rotating at 180rpm and at the temperature of 25 ℃, sampling the solution at certain intervals, and measuring the phosphorus concentration in the solution after filtering. As shown in fig. 6, the adsorption rate of the composite material to phosphate is high, the composite material can reach equilibrium within 2h, and the quasi-second order kinetic model fits the experimental result better, which indicates that the adsorption process of the composite material to phosphorus is mainly chemical adsorption.
The phosphorus removal adsorbent obtained in the example is used for testing the phosphorus removal effect on the actual high-concentration fosfomycin pharmaceutical wastewater: the organic phosphorus in the actual wastewater is about 1800 mg.L-1Total phosphorus of 2000 mg.L-1. Other water quality indexes are as follows: COD is 56934 mg.L-1，NH4 +-N＝317mg·L-1，pH＝4.6。
Adding actual high-concentration fosfomycin pharmaceutical wastewater and hydrogen peroxide according to the volume ratio of 1:2 for mixing reaction, wherein the adding amount of the phosphorus removal adsorbent is 50 g.L-1. The purpose of adding hydrogen peroxide is to convert organic phosphorus in the high-phosphorus wastewater into inorganic phosphorus and promote the phosphorus removal adsorbent to adsorb the phosphorus. After reacting for 18 hours, carrying out solid-liquid separation, and measuring that the removal rate of the total phosphorus and the organic phosphorus is about 79 percent, wherein the removal efficiency is better than the sum of the adsorption material and the hydrogen peroxide which are added independently (see figure 8).
And (3) injecting a sodium hydroxide solution with the concentration of 5mol/L into the reactor after the dephosphorization operation, desorbing the material after adsorbing the phosphate for 6-24h, separating and collecting the adsorbing material, washing the adsorbing material to be neutral by using deionized water, drying the adsorbing material, and then repeatedly using the adsorbing material. As shown in fig. 9, the phosphorus removal adsorbent of the present invention can still achieve a total phosphorus removal rate of 68.1% after four times of adsorption-desorption recycling.
Adding calcium chloride into the wastewater subjected to the phosphorus removal adsorbent recovery operation according to the molar ratio of Ca to P of 2:1, adjusting the pH value of a reaction system to be about 9.0, stirring for reaction for 30min, standing for 30min, performing solid-liquid separation, collecting precipitates, and performing biological treatment on supernatant to achieve standard discharge.
After treatment in the above-described manner of operation, the recovered phosphate is present in the form of precipitated calcium phosphate. In the present embodiment, sodium hydroxide may be replaced by potassium persulfate, sodium hypochlorite, ozone, and the like; similar results can be obtained when calcium chloride is replaced by magnesium chloride and magnesium sulfate, in which case the phosphorus recovery product is primarily struvite (magnesium ammonium phosphate). The dephosphorization composite adsorbent can be repeatedly used after being desorbed, so that the use cost of the adsorbent is reduced.
The protective scope of the present invention is not limited to the above-described embodiments, and it is apparent that various modifications and variations can be made to the present invention by those skilled in the art without departing from the scope and spirit of the present invention. It is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (10)

1. A preparation method of a phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater is characterized by comprising the following steps:
step 1, preparing a mixed solution of lanthanum salt, aluminum salt and urea;
step 2, injecting the mixed solution into a reaction kettle, and preparing an adsorption material by a hydrothermal method;
step 3, washing the reactant obtained in the step 2 by deionized water until the supernatant is neutral;
step 4, drying and grinding the reactant obtained in the step 3 into powder to obtain the required phosphorus removal adsorbent;
la in lanthanum salt and aluminum salt in the step 1: the molar ratio of Al is 1:1-10:1, the total concentration of the two metal salts is 0.05-0.5mol/L, and the concentration of urea is 1-14 mol/L.
2. The preparation method of the phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater as claimed in claim 1, wherein the preparation method comprises the following steps: the lanthanum salt in the step 1 is lanthanum chloride or lanthanum nitrate; the aluminum salt is aluminum chloride, aluminum nitrate or aluminum sulfate.
3. The preparation method of the phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater as claimed in claim 1, wherein the preparation method comprises the following steps: the reaction temperature of the hydrothermal method in the step 2 is 80-160 ℃, and the reaction time is more than 12 hours.
4. The preparation method of the phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater as claimed in claim 1, wherein the preparation method comprises the following steps: and (3) performing solid-liquid separation by using centrifugation during cleaning in the step 3.
5. The preparation method of the phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater as claimed in claim 1, wherein the preparation method comprises the following steps: and 4, drying at the drying temperature of 50-80 ℃ for 10-24 hours in the step 4, and grinding the prepared lanthanum aluminum carbonate composite material into powder with the particle size of less than 0.1 mm.
6. The application method of the phosphorus removal adsorbent prepared by the preparation method of the phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater according to any one of claims 1 to 5, is characterized in that the specific application method comprises the following steps:
adding the prepared phosphorus removal adsorbent into high-concentration fosfomycin pharmaceutical wastewater according to the adding amount of 20-100g/L, simultaneously adding a hydrogen peroxide solution, wherein the content of active ingredients of the hydrogen peroxide solution is 300g/L, the adding amount ratio of the hydrogen peroxide solution to the high-phosphorus wastewater is 2:1-1:10, simultaneously injecting the obtained mixture into a reactor, and placing the reactor on a rotary table concentrator for reacting for 18-36 hours.
7. The application method of the phosphorus removal adsorbent for the fosfomycin pharmaceutical wastewater as claimed in claim 6, wherein the application method comprises the following steps: the rotating speed of the rotary table is 10-50 r/min, and the temperature is 10-35 ℃.
8. The method for recovering the phosphorus removal adsorbent prepared by the method for preparing the phosphorus removal adsorbent for the fosfomycin pharmaceutical wastewater according to any one of claims 1 to 5, wherein the recovery process of the phosphorus removal adsorbent is as follows: after natural precipitation of the adsorbent, separating the precipitate from the liquid, or carrying out centrifugal acceleration separation at the rotation speed of 3000-10000rpm, treating the precipitate for 24 hours by using 0.5-10M sodium hydroxide solution, washing the obtained regenerated material to be neutral by using deionized water, drying the regenerated material, and then repeatedly using the regenerated material.
9. The method for recovering the phosphorus removal adsorbent for the fosfomycin pharmaceutical wastewater as claimed in claim 8, wherein the recovery process of the phosphate in the liquid comprises the following steps: according to the Ca: adding calcium salt into the liquid separated in the adsorbent recovery process at a P molar ratio of 2:1, adding acid and alkali solution into the wastewater to maintain the pH value of 8.5-10.0, stirring and reacting for 10-60 min, standing for 10-30 min, performing solid-liquid separation to obtain a phosphate recovery product and a supernatant, discharging the supernatant into a comprehensive wastewater treatment plant for biological treatment to achieve standard discharge, wherein the phosphate recovery product is calcium phosphate, and the recovered product is used as a fine chemical raw material or for manufacturing plant slow-release fertilizer.
10. The method for recovering the phosphorus removal adsorbent for the fosfomycin pharmaceutical wastewater as claimed in claim 9, wherein the method comprises the following steps: the calcium salt comprises calcium chloride, calcium sulfate, calcium hydroxide or calcium oxide.
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CN114146689A (en) * 2021-11-10 2022-03-08 华侨大学 Aluminum/cerium bimetal organic framework material, preparation method and application thereof in phosphorus adsorption and removal
CN114669270A (en) * 2022-04-19 2022-06-28 中南民族大学 Composite material for efficiently passivating deposit phosphorus and preparation method thereof

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CN114146689A (en) * 2021-11-10 2022-03-08 华侨大学 Aluminum/cerium bimetal organic framework material, preparation method and application thereof in phosphorus adsorption and removal
CN114669270A (en) * 2022-04-19 2022-06-28 中南民族大学 Composite material for efficiently passivating deposit phosphorus and preparation method thereof
CN114669270B (en) * 2022-04-19 2024-04-02 中南民族大学 Composite material for efficiently passivating sediment phosphorus and preparation method thereof

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