CN112108132B - Composite nano material for synchronous nitrogen and phosphorus removal, preparation method and application - Google Patents

Composite nano material for synchronous nitrogen and phosphorus removal, preparation method and application Download PDF

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CN112108132B
CN112108132B CN202010986573.1A CN202010986573A CN112108132B CN 112108132 B CN112108132 B CN 112108132B CN 202010986573 A CN202010986573 A CN 202010986573A CN 112108132 B CN112108132 B CN 112108132B
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nano material
composite nano
polyacrylic acid
wastewater
phosphate
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CN112108132A (en
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杨文澜
许海民
韩路
唐欢
李含
赵雨
史新星
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Jiangsu Chong Chong Environmental Polytron Technologies Inc
Yangzhou University
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Jiangsu Chong Chong Environmental Polytron Technologies Inc
Yangzhou 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia

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Abstract

The invention belongs to the field of wastewater treatment and environmental functional materials, and discloses a composite nano material for synchronously removing nitrogen and phosphorus, a preparation method and application. The composite nano material takes carboxyl (-COOH) modified porous polyacrylic acid microspheres as a carrier, and cerium oxide (CeO) is prepared by a method of introducing a cerium precursor and in-situ alkali deposition2) The nano particles are uniformly loaded into the pore channels of the carrier, so that the organic-inorganic composite nano material CON @ CPM with the functions of nitrogen and phosphorus removal is successfully prepared. The composite nanometer material couples the high-efficiency ammonia nitrogen removal performance of the polymer matrix and cerium oxide (CeO)2) The selective adsorption performance of the nano particles to phosphate realizes the synchronous removal of ammonia nitrogen and phosphate in sewage. The wastewater treatment process taking the composite nano material as the core has simple operation process and low cost, and is beneficial to popularization.

Description

Composite nano material for synchronous nitrogen and phosphorus removal, preparation method and application
Technical Field
The invention belongs to the field of wastewater treatment and environmental functional materials, and particularly relates to a composite nano material for synchronous nitrogen and phosphorus removal, a preparation method and application.
Background
According to 1931 water quality sections (point positions) monitored by national surface water in 2019, the occupation ratio of water quality in IV class, V class and poor V class is up to 25.1%, wherein main pollutant indexes comprise chemical oxygen demand, ammonia nitrogen, total nitrogen, phosphate and the like. Therefore, the method has large and wide amount of nitrogen and phosphorus pollutants, and is the two most common pollutants in the water body. Excessive ammonia nitrogen and phosphate easily cause eutrophication of water, cause phenomena of lake water bloom, offshore red tide and the like, and can cause black and odorous water in urban inland rivers, thereby seriously affecting the ecological balance of the water and the quality of life of people. Therefore, the purification technology of ammonia nitrogen and phosphate in sewage becomes a great environmental protection subject which needs to be solved urgently in China.
The denitrification techniques commonly used at present include biological methods, chemical precipitation methods, stripping methods, membrane separation methods, ion exchange methods and the like. Biological denitrification is the most widely applied sewage treatment technology at present, but because the denitrification process needs more than two reaction tanks, the capital investment cost is high, and the denitrification efficiency is greatly influenced by environmental conditions such as temperature, the index of ammonia nitrogen in the effluent cannot stably reach the standard. The chemical precipitation method is suitable for treating high-concentration ammonia nitrogen wastewater, and has the characteristics of simple and convenient operation, high reaction speed, small influence of temperature and the like, but the dosage of the medicament in the reaction process is large, and secondary pollution is easily caused by incomplete reaction of the precipitator in the water body. The stripping method is mainly used for pretreating high-concentration ammonia nitrogen wastewater, the process is simple, the operation is convenient, a large amount of steam needs to be introduced in the treatment process, the energy consumption is high, and the released ammonia gas easily causes secondary pollution. The membrane separation method has high ammonia nitrogen wastewater treatment efficiency and stable treatment effect, but the membrane is easily polluted in the treatment process, and the membrane needs to be backwashed regularly, so that the treatment cost is increased. The ion exchange method utilizes the solid adsorption material to adsorb the ammonia nitrogen in the water, has low cost and simple process, and is suitable for treating the ammonia nitrogen wastewater with medium and low concentration or carrying out advanced treatment. Research shows that the carboxyl modified ion exchange resin can realize the high-efficiency removal of low-concentration ammonia nitrogen in wastewater (Yangxuexia, octocryst, Yang hong Wei, Zhang Li, high climb, ammonia nitrogen adsorption performance of the ion exchange resin, Qinghua university journal (Nature science edition), 2015,55(6): 660-.
For removing phosphate in sewage, the currently common methods include biological methods, chemical precipitation methods, crystallization methods, adsorption methods and the like. The biological phosphorus removal process is economical and feasible, but the process is greatly influenced by the environment, the impact load resistance is weaker, and the effluent quality fluctuation is larger when the phosphorus concentration is higher and the organic matter concentration is lower. The chemical precipitation and crystallization method has the advantages of economic and efficient dephosphorization, convenient operation, reliable effect and difficult influence of the quality of wastewater on the treatment effect, but the chemical dephosphorization agent has generally higher cost. The adsorption dephosphorization is a method for removing phosphorus from water by using the physical and chemical action between an adsorbent and phosphate, has high dephosphorization efficiency, can realize deep removal of phosphorus and recovery of phosphorus resources, and is a sewage dephosphorization method with better development prospect. The research of the adsorbent with high selectivity, high adsorption capacity and renewable reutilization is the main research target of phosphorus removal by an adsorption method. Cerium oxide nanoparticles have high specific surface area and strong surface activity, and can realize selective adsorption of phosphate through surface hydroxyl ligand exchange (Y.F. Feng, H.Y. Lu, Y.Liu, L.H.Xue, D.D.Dionysiou, L.Z.Yang, B.S.Xing, nanoceramide oxide functionalized biochar for phosphate retention, optimization and probability application, Chemosphere 185(2017) 816-825). However, cerium oxide has no ammonia nitrogen adsorption removal performance, and has fine particles, so that technical bottlenecks such as difficulty in solid-liquid separation, easiness in material loss and the like are encountered in engineering application.
In conclusion, the adsorption method is adopted to deeply remove nitrogen and phosphorus in the sewage, so that the method has the advantages of simplicity and convenience in operation, economy, high efficiency, stable performance and the like, and can realize the recovery of nitrogen and phosphorus resources. However, because the adsorption removal mechanisms of ammonia nitrogen and phosphate are different, the common adsorbent is only suitable for respectively removing ammonia nitrogen and phosphate at present, and when the common adsorbent is applied to the denitrification and dephosphorization of actual sewage, two sections of independent treatment units are needed, so that the investment and operation cost is high. Therefore, the development of a novel adsorption material capable of synchronously removing ammonia nitrogen and phosphate in sewage and the application of the adsorption material in the deep removal of nitrogen and phosphorus in sewage to meet the requirement of water eutrophication prevention and control still remain the problems faced by the technology in the field.
Disclosure of Invention
1. Problems to be solved
Aiming at the technical bottleneck that the currently widely used adsorbing material can not realize the synchronous removal of ammonia nitrogen and phosphate in sewage, the invention provides a composite nano material for synchronous nitrogen and phosphorus removal and a preparation method thereof, wherein cerium oxide (CeO) is prepared by a method of cerium precursor introduction-in-situ alkali deposition2) The nano particles are uniformly loaded into a porous polyacrylic acid microsphere pore canal decorated by carboxyl (-COOH) to successfully prepare a novel composite nano material CON @ CPM, and the material couples the high-efficiency ammonia nitrogen removal performance of a polymer matrix and cerium oxide (CeO)2) The selective adsorption performance of the nano particles to phosphate realizes the synchronous removal of ammonia nitrogen and phosphate in sewage. The sewage nitrogen and phosphorus removal technology taking the composite material CON @ CPM adsorption as the core can provide important guarantee for the prevention and control of water eutrophication and realize the unification of environmental benefits and social benefits.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a composite nano material for synchronously removing nitrogen and phosphorus, which comprises the following steps:
1) removing impurities from the carboxyl modified macroporous polyacrylic acid microspheres, drying for later use, adding the carboxyl modified macroporous polyacrylic acid microspheres into a cerium salt solution with a certain concentration, and continuously stirring for reaction to obtain the pre-loaded Ce4+Drying the macroporous polyacrylic acid microspheres for later use;
2) will preSupported Ce4+Adding the macroporous polyacrylic acid microspheres into NaOH solution with a certain concentration, and continuously stirring for reaction to obtain Ce4+In-situ deposition in polyacrylic acid microsphere pore canal to generate Ce (OH)4Granulating to obtain a reaction product;
3) and filtering the obtained reaction product, rinsing the reaction product by using deionized water until the effluent is neutral, transforming the reaction product by using a NaCl solution, and finally, fully soaking the reaction product by using absolute ethyl alcohol and drying the reaction product to obtain the composite nano material.
As a further improvement of the invention, the cation exchange capacity of the carboxyl modified macroporous polyacrylic microspheres in the step 1) is more than or equal to 8 mmol/g.
As a further improvement of the invention, the cerium salt solution in step 1) is Ce (SO)4)2The mass concentration of the aqueous solution is 5-20%; the adding mass of the macroporous polyacrylic acid microspheres in the step 1) is 50-200 g per liter of solution.
As a further improvement of the present invention, the manner of removing impurities in step 1) is: and sequentially rinsing with HCl and NaOH solutions with certain concentrations, and then rinsing with deionized water to neutrality, wherein the mass concentrations of the HCl and NaOH solutions are 4-8%.
As a further improvement of the invention, the reaction conditions of continuous stirring in the step 1) are as follows: controlling the stirring speed to be 150-300 rpm, and continuously stirring for reacting for 4-8 h; and/or the continuous stirring reaction conditions in the step 2) are as follows: the stirring speed is controlled to be 150-300 rpm, and the stirring reaction is continued for 6-12 h.
As a further improvement of the invention, the mass concentration of the NaOH solution in the step 2) is 5-20%.
As a further improvement of the invention, the specific preparation method of the composite nano material for synchronously removing nitrogen and phosphorus comprises the following steps:
(A) sequentially rinsing the carboxyl modified macroporous polyacrylic acid microspheres with HCl and NaOH solutions with certain concentrations to remove impurities, then rinsing the microspheres to be neutral with deionized water, and drying the microspheres for later use;
(B) slowly adding the cleaned and dried macroporous polyacrylic acid microspheres obtained in the step (A) into a cerium salt solution with a certain concentration, and controlling the rotating speed of a stirring paddle to be 150 toContinuously stirring at 300rpm for 4-8 h to react to obtain Ce4+Introducing the precursor into the interior of the polyacrylic acid microsphere in an ion exchange mode;
(C) pre-loading Ce obtained in the step (B)4+Filtering out the macroporous polyacrylic acid microspheres of the precursor, and drying for 12 hours in an air-blast drying oven at the temperature of 40-60 ℃;
(D) carrying the dried Ce obtained in the step (C)4+Slowly adding the macroporous polyacrylic acid microspheres into a NaOH solution with a certain concentration, and continuously stirring and reacting for 6-12 h by controlling the rotating speed of a stirring paddle to be 150-300 rpm so as to ensure that Ce is4+In-situ deposition in polyacrylic acid microsphere pore canal to generate Ce (OH)4Particles;
(E) and (D) filtering out the reaction product obtained in the step (D), rinsing with deionized water until the effluent is neutral, transforming with a 5% NaCl solution, fully soaking with absolute ethyl alcohol, and drying in a forced air drying oven at 50-70 ℃ for 12h to obtain the synchronous nitrogen and phosphorus removal composite nanomaterial CON @ CPM.
As a further improvement, the invention provides the composite nano material prepared by the preparation method of the composite nano material for synchronously removing nitrogen and phosphorus, the carrier of the composite nano material is carboxyl modified macroporous polyacrylic microspheres, and cerium oxide nano particles are uniformly loaded in the pore channels of the carrier.
As a further improvement of the invention, the composite nano material has an average particle size of 0.5-1.0 mm and CeO2The content is 10-30% (mass concentration of Ce).
As a further improvement, the invention provides a method for deeply treating wastewater containing ammonia nitrogen and phosphate, which comprises the following steps:
(A) adjusting the pH value of the wastewater to 7-9, and then adding a composite nanomaterial CON @ CPM into the wastewater, wherein the adding amount is 1000-3000 mg/L, so that ammonia nitrogen and phosphate in the wastewater are synchronously adsorbed by the CON @ CPM;
(B) controlling the rotating speed of the stirring paddle in the step (A) to be 150-300 rpm, carrying out adsorption reaction for 6-12 h, standing and precipitating for 30-60 min to separate the composite nanomaterial CON @ CPM from the wastewater, and discharging the supernatant after the supernatant reaches the standard;
(C) and (3) rinsing and regenerating the composite nano material CON @ CPM precipitated and separated in the step (B) by using 2% dilute hydrochloric acid and 2% NaOH solution in sequence, and then washing the composite nano material CON @ CPM by using 5% NaCl solution and deionized water until the effluent is neutral, wherein the regenerated CON @ CPM can be repeatedly used for adsorption treatment of ammonia nitrogen and phosphate wastewater.
Furthermore, the wastewater containing ammonia nitrogen and phosphate comprises biochemical tail water of a sewage treatment plant, a black and odorous river water body and an eutrophic water body.
Furthermore, the concentration of ammonia nitrogen in the wastewater is 10-20 mg/L, and the concentration of phosphate is 1-5 mg/L.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the composite nano material for synchronously removing nitrogen and phosphorus couples the high-efficiency ammonia nitrogen removal performance of the carboxyl modified porous polyacrylic acid microsphere parent body and the loaded cerium oxide (CeO)2) The selective adsorption performance of the nano particles to phosphate realizes the synchronous and efficient removal of ammonia nitrogen and phosphate in sewage. The cerium oxide (CeO) is added to the mixture2) The nanometer particles are loaded into the polyacrylic acid microsphere pore canal modified by carboxyl, and can break through cerium oxide (CeO)2) Engineering application bottleneck faced by finer nanoparticles, and CeO2Has stronger stability and acid and alkali dissolution resistance, and long-term use of CeO2The nanometer particles are not dissolved out or lost and can be used for a long time.
(2) The synchronous nitrogen and phosphorus removal composite nanomaterial can realize high-efficiency desorption regeneration through acid washing and alkali washing, can be repeatedly used for deeply removing ammonia nitrogen and phosphate in sewage after regeneration, and effectively saves cost. The composite nano material has stable performance, simple and convenient nitrogen and phosphorus removal process operation, economy and high efficiency, and can generate social benefits while generating environmental benefits.
(3) The composite nano material for synchronously removing nitrogen and phosphorus utilizes the carboxyl modified porous polyacrylic acid microspheres as a carrier, so that the removal capability of the material on ammonia nitrogen is improved on one hand, and the carboxyl of the composite nano material is favorable for promoting Ce4+Method for precursor passing through ion exchangeThe formula is loaded in the polyacrylic acid microsphere. Thus promoting CeO2Uniform and high loading of nanoparticles, CeO in the material prepared according to the invention2The content can reach 10-30%, so that the efficient removal of phosphate is promoted, and the efficient synchronous removal capability is realized for ammonia nitrogen and phosphate existing in the wastewater.
Drawings
FIG. 1 is an appearance diagram of the composite nanomaterial CON @ CPM;
FIG. 2 is SEM and TEM images of a cross section of the composite nanomaterial CON @ CPM;
FIG. 3 is a graph comparing the adsorption of the materials of example 5;
Detailed Description
The invention is further described with reference to specific examples.
It should be noted that the terms "upper", "lower", "left", "right" and "middle" used in the present specification are for the sake of clarity, and are not intended to limit the scope of the present invention, and changes or adjustments of the relative relationship thereof may be made without substantial technical changes.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, measure or value. The degree of flexibility for a particular variable can be readily determined by one skilled in the art.
As used herein, at least one of the terms "is intended to be synonymous with one or more of. For example, "at least one of A, B and C" explicitly includes a only, B only, C only, and combinations thereof, respectively.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limit values of 1 to about 4.5, but also include individual numbers (such as 2, 3, 4) and sub-ranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed to include all of the aforementioned values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or feature being described.
Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims.
Example 1
The preparation method of the composite material CON @ CPM comprises the following steps:
sequentially rinsing the carboxyl modified macroporous polyacrylic acid microspheres (the cation exchange capacity is more than or equal to 8mmol/g) by using HCl with the mass concentration of 4% and NaOH solution with the mass concentration of 4%, then washing the microspheres to be neutral by using deionized water, and drying the microspheres for later use; 5g of the cleaned and dried polyacrylic acid microspheres are slowly added into 100mL of 5 mass percent Ce (SO)4)2In the solution, the stirring paddle is controlled to rotate at 200rpm for continuous stirring reaction for 4 hours, so that Ce is obtained4+Introducing the precursor into the interior of the polyacrylic acid microsphere in an ion exchange mode; the above-mentioned pre-supported Ce4+Filtering out the macroporous polyacrylic acid microspheres of the precursor, drying for 12h at 40 ℃ in a blast drying oven, slowly adding into 100mL NaOH solution with the mass concentration of 5%, and continuously stirring and reacting for 6h by controlling the rotating speed of a stirring paddle to be 200rpm so as to obtain Ce4+In-situ deposition in polyacrylic acid microsphere pore canal to generate Ce (OH)4Particles; will be reversedFiltering out a reaction product, rinsing with deionized water until the effluent is neutral, transforming with 5% NaCl solution, fully infiltrating with absolute ethyl alcohol, and drying in a forced air drying oven at 50 ℃ for 12h to obtain the synchronous nitrogen and phosphorus removal composite nanomaterial CON @ CPM, wherein the appearance diagram is shown in figure 1.
The composite nanomaterial CON @ CPM prepared in the embodiment is used for synchronous nitrogen and phosphorus removal, and the method comprises the following specific steps:
adding a composite nanomaterial CON @ CPM into wastewater with ammonia nitrogen concentration of 11.4mg/L and phosphate concentration of 1.54mg/L, wherein the adding amount of the CON @ CPM is 1000mg/L, adjusting the pH value of the wastewater to be 7.4, controlling the rotating speed of a stirring paddle to be 150rpm, after adsorption reaction for 12h, standing and precipitating for 60min to separate the composite nanomaterial CON @ CPM from the wastewater, wherein the ammonia nitrogen concentration of a supernatant is 4.3mg/L, and the phosphate concentration is 0.24 mg/L; and rinsing the composite nanomaterial CON @ CPM obtained by precipitation with 2% dilute hydrochloric acid and 2% NaOH solution in sequence for regeneration, washing with 5% NaCl solution and deionized water until the effluent is neutral, and repeatedly removing ammonia nitrogen and phosphate in wastewater by using the regenerated composite nanomaterial CON @ CPM.
Example 2
The preparation method of the composite material CON @ CPM comprises the following steps:
sequentially rinsing the carboxyl modified macroporous polyacrylic acid microspheres (the cation exchange capacity is more than or equal to 8mmol/g) by using HCl with the mass concentration of 5% and NaOH solution with the mass concentration of 5%, then washing the microspheres to be neutral by using deionized water, and drying the microspheres for later use; 10g of the cleaned and dried polyacrylic acid microspheres are slowly added into 200mL of 10 mass percent Ce (SO)4)2In the solution, the stirring paddle is controlled to rotate at 170rpm, and the reaction is continuously stirred for 5 hours, so that Ce is obtained4+Introducing the precursor into the interior of the polyacrylic acid microsphere in an ion exchange mode; the above-mentioned pre-supported Ce4+Filtering out the macroporous polyacrylic acid microspheres of the precursor, drying for 12h at 45 ℃ in a blast drying oven, slowly adding into 200mL NaOH solution with the mass concentration of 10%, and continuously stirring and reacting for 8h by controlling the rotating speed of a stirring paddle to be 170rpm so as to obtain Ce4+In-situ deposition in polyacrylic acid microsphere pore canal to generate Ce (OH)4Particles; reacting the aboveAnd filtering the product, rinsing the product with deionized water until the effluent is neutral, transforming the product with a 5% NaCl solution, fully soaking the product with absolute ethyl alcohol, and drying the product for 12 hours in a blast drying oven at the temperature of 60 ℃ to obtain the synchronous nitrogen and phosphorus removal composite nanomaterial CON @ CPM.
The composite nanomaterial CON @ CPM prepared in the embodiment is used for synchronous nitrogen and phosphorus removal, and the method comprises the following specific steps:
adding a composite nanomaterial CON @ CPM into wastewater with ammonia nitrogen concentration of 14.3mg/L and phosphate concentration of 2.64mg/L, wherein the adding amount of the CON @ CPM is 1500mg/L, adjusting the pH value of the wastewater to 8.0, controlling the rotating speed of a stirring paddle to be 200rpm, performing adsorption reaction for 10 hours, standing and precipitating for 50min to separate the composite nanomaterial CON @ CPM from the wastewater, wherein the ammonia nitrogen concentration of a supernatant is 4.1mg/L, and the phosphate concentration is 0.18 mg/L; and rinsing the composite nanomaterial CON @ CPM obtained by precipitation with 2% dilute hydrochloric acid and 2% NaOH solution in sequence for regeneration, washing with 5% NaCl solution and deionized water until the effluent is neutral, and repeatedly removing ammonia nitrogen and phosphate in wastewater by using the regenerated composite nanomaterial CON @ CPM.
Example 3
The preparation method of the composite material CON @ CPM comprises the following steps:
sequentially rinsing the carboxyl modified macroporous polyacrylic acid microspheres with 6% HCl and 6% NaOH solutions by mass concentration, then rinsing the microspheres to be neutral by using deionized water, and drying the microspheres for later use; 20g of the cleaned and dried polyacrylic acid microspheres are slowly added into 400mL of Ce (SO) with the mass concentration of 15%4)2In the solution, the stirring paddle is controlled to rotate at 150rpm for continuous stirring reaction for 6 hours, so that Ce is obtained4+Introducing the precursor into the interior of the polyacrylic acid microsphere in an ion exchange mode; the above-mentioned pre-supported Ce4+Filtering out the macroporous polyacrylic acid microspheres of the precursor, drying for 12h at 50 ℃ in a blast drying oven, slowly adding into 400mL NaOH solution with the mass concentration of 15%, and continuously stirring and reacting for 10h by controlling the rotating speed of a stirring paddle to be 150rpm so as to obtain Ce4+In-situ deposition in polyacrylic acid microsphere pore canal to generate Ce (OH)4Particles; filtering the reaction product, rinsing with deionized water until the effluent is neutral, and adding 5%And transforming the obtained product by using a NaCl solution, fully soaking the obtained product by using absolute ethyl alcohol, and drying the obtained product for 12 hours in a forced air drying oven at the temperature of 65 ℃ to obtain the synchronous nitrogen and phosphorus removal composite nanomaterial CON @ CPM.
The composite nanomaterial CON @ CPM prepared in the embodiment is used for synchronous nitrogen and phosphorus removal, and the method comprises the following specific steps:
adding a composite nano material CON @ CPM into wastewater with ammonia nitrogen concentration of 16.8mg/L and phosphate concentration of 3.75mg/L, wherein the adding amount of the CON @ CPM is 2000mg/L, adjusting the pH value of the wastewater to 8.4, controlling the rotating speed of a stirring paddle to be 250rpm, after adsorption reaction for 8 hours, standing and precipitating for 40min to separate the composite nano material CON @ CPM from the wastewater, wherein the ammonia nitrogen concentration of supernatant is 3.8mg/L, and the phosphate concentration is 0.22 mg/L; and rinsing the composite nanomaterial CON @ CPM obtained by precipitation with 2% dilute hydrochloric acid and 2% NaOH solution in sequence for regeneration, washing with 5% NaCl solution and deionized water until the effluent is neutral, and repeatedly removing ammonia nitrogen and phosphate in wastewater by using the regenerated composite nanomaterial CON @ CPM.
Example 4
The preparation method of the composite material CON @ CPM comprises the following steps:
sequentially rinsing the carboxyl modified macroporous polyacrylic acid microspheres with HCl with the mass concentration of 8% and NaOH solution with the mass concentration of 8%, then rinsing the microspheres with deionized water to be neutral, and drying the microspheres for later use; 40g of the cleaned and dried polyacrylic acid microspheres are slowly added into 800mL of 20 mass percent Ce (SO)4)2In the solution, the stirring paddle is controlled to rotate at 120rpm for continuous stirring reaction for 8 hours, so that Ce is obtained4+Introducing the precursor into the interior of the polyacrylic acid microsphere in an ion exchange mode; the above-mentioned pre-supported Ce4+Filtering out the macroporous polyacrylic acid microspheres of the precursor, drying for 12h at 60 ℃ in a blast drying oven, slowly adding into 800mL NaOH solution with the mass concentration of 20%, and continuously stirring and reacting for 12h by controlling the rotating speed of a stirring paddle to be 120rpm so as to obtain Ce4+In-situ deposition in polyacrylic acid microsphere pore canal to generate Ce (OH)4Particles; filtering out the above reaction product, rinsing with deionized water until the effluent is neutral, transforming with 5% NaCl solution, soaking with anhydrous ethanol, and packagingAnd drying for 12h at 70 ℃ in an air drying oven to obtain the synchronous nitrogen and phosphorus removal composite nanomaterial CON @ CPM.
The composite nanomaterial CON @ CPM prepared in the embodiment is used for synchronous nitrogen and phosphorus removal, and the method comprises the following specific steps:
adding a composite nanomaterial CON @ CPM into wastewater with ammonia nitrogen concentration of 19.5mg/L and phosphate concentration of 4.74mg/L, wherein the adding amount of the CON @ CPM is 3000mg/L, adjusting the pH value of the wastewater to 8.7, controlling the rotating speed of a stirring paddle to be 300rpm, after an adsorption reaction is carried out for 6 hours, standing and precipitating for 30min to separate the composite nanomaterial CON @ CPM from the wastewater, wherein the ammonia nitrogen concentration of a supernatant is 4.5mg/L, and the phosphate concentration is 0.28 mg/L; and rinsing the composite nanomaterial CON @ CPM obtained by precipitation with 2% dilute hydrochloric acid and 2% NaOH solution in sequence for regeneration, washing with 5% NaCl solution and deionized water until the effluent is neutral, and repeatedly removing ammonia nitrogen and phosphate in wastewater by using the regenerated composite nanomaterial CON @ CPM.
The composite nano-materials prepared in the detection examples 1-4 have an average particle size of 0.5-1.0 mm (mass concentration calculated by Ce) of CeO2The content is 10-30%. FIG. 1 is an appearance diagram of the composite nanomaterial CON @ CPM; FIG. 2 is SEM and TEM images of a cross section of the composite nanomaterial CON @ CPM;
example 5
In this example, a comparative experiment for nitrogen and phosphorus removal was performed on various materials, which respectively include granular activated carbon, an adsorbent resin XAD4, a carrier CPM, and the CON @ CPM material prepared in example 1, where the carrier CPM is the carboxyl-modified macroporous polyacrylic acid microsphere without loading nano cerium oxide described in example 1.
Several experimental groups were set up according to the above materials: the method comprises the following specific steps:
respectively adding the 4 materials into wastewater with ammonia nitrogen concentration of 40mg/L and phosphate concentration of 20mg/L, wherein the adding amount is 0.5g/L, adjusting the pH value of the wastewater to be 8 +/-0.1, controlling the rotating speed of a stirring paddle to be 300rpm, after adsorption reaction for 6 hours, measuring the ammonia nitrogen concentration and the phosphate concentration in a supernatant, and calculating the corresponding adsorption amount of each adsorption material according to the ammonia nitrogen concentration and the phosphate concentration to obtain a result shown in figure 3. As can be seen from FIG. 3, the removal capability of phosphorus and ammonia nitrogen of the single granular activated carbon and the adsorption resin is weak, the adsorption capability of the material to ammonia nitrogen in a water body is obviously improved by the macroporous polyacrylic acid microspheres modified by carboxyl, however, the adsorption capability to phosphorus is still relatively limited, and after the CON and the CPM are organically compounded, the synchronous removal performance of the material to ammonia nitrogen and phosphate is greatly improved.

Claims (7)

1. A preparation method of a composite nano material for synchronously removing nitrogen and phosphorus is characterized by comprising the following steps: the method comprises the following steps:
1) removing impurities from the carboxyl modified macroporous polyacrylic acid microspheres, drying for later use, adding the carboxyl modified macroporous polyacrylic acid microspheres into a cerium salt solution with a certain concentration, and continuously stirring for reaction to obtain the pre-loaded Ce4+Drying the macroporous polyacrylic acid microspheres for later use; the cerium salt solution is Ce (SO)4)2The mass concentration of the aqueous solution is 5-20%; the adding mass of the macroporous polyacrylic acid microspheres is 50-200 g per liter of solution;
2) will pre-load Ce4+Adding the macroporous polyacrylic acid microspheres into NaOH solution with a certain concentration, and continuously stirring for reaction to obtain Ce4+In-situ deposition in polyacrylic acid microsphere pore canal to generate Ce (OH)4Granulating to obtain a reaction product;
3) and filtering the obtained reaction product, rinsing the reaction product by using deionized water until the effluent is neutral, transforming the reaction product by using a NaCl solution, and finally, fully soaking the reaction product by using absolute ethyl alcohol and drying the reaction product to obtain the composite nano material.
2. The method for preparing the composite nano material for synchronously removing nitrogen and phosphorus according to claim 1, which is characterized in that: the cation exchange capacity of the carboxyl modified macroporous polyacrylic acid microspheres in the step 1) is more than or equal to 8 mmol/g.
3. The method for preparing the composite nano material for synchronously removing nitrogen and phosphorus according to claim 2, which is characterized in that: the impurity removal mode in the step 1) is as follows: and sequentially rinsing with HCl and NaOH solutions with certain concentrations, and then rinsing with deionized water to neutrality, wherein the mass concentrations of the HCl and NaOH solutions are 4-8%.
4. The method for preparing the composite nano material for synchronously removing nitrogen and phosphorus according to claim 3, which is characterized in that: the reaction conditions of continuous stirring in the step 1) are as follows: controlling the stirring speed to be 150-300 rpm, and continuously stirring for reacting for 4-8 h; and/or the continuous stirring reaction conditions in the step 2) are as follows: controlling the stirring speed to be 150-300 rpm, and continuously stirring and reacting for 6-12 h.
5. The method for preparing the composite nano material for simultaneous nitrogen and phosphorus removal according to claim 4, wherein the method comprises the following steps: the mass concentration of the NaOH solution in the step 2) is 5-20%.
6. A method for deeply treating wastewater containing ammonia nitrogen and phosphate is characterized by comprising the following steps: the method comprises the following steps:
(A) adjusting the pH value of the wastewater, and then adding the composite nano material into the wastewater to ensure that ammonia nitrogen and phosphate in the wastewater are synchronously adsorbed by the composite nano material obtained by the preparation method of any one of claims 1 to 5;
(B) after the adsorption reaction is carried out under the stirring condition, standing and precipitating for a period of time to separate the composite nano material from the wastewater, and discharging the supernatant after reaching the standard;
(C) and (C) rinsing the composite nano material precipitated and separated in the step (B) by using hydrochloric acid and NaOH solution in sequence for regeneration, then washing the composite nano material by using NaCl solution and deionized water until the effluent is neutral, and repeatedly using the regenerated composite nano material for adsorption treatment of ammonia nitrogen and phosphate wastewater.
7. The method for deeply treating the wastewater containing ammonia nitrogen and phosphate according to claim 6, characterized by comprising the following steps: the concentration of ammonia nitrogen in the wastewater is 10-20 mg/L, and the concentration of phosphate is 1-5 mg/L.
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