CN107442071B - Nano composite material for synchronously and selectively adsorbing phosphorus and nitrate and application - Google Patents

Nano composite material for synchronously and selectively adsorbing phosphorus and nitrate and application Download PDF

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CN107442071B
CN107442071B CN201710854582.3A CN201710854582A CN107442071B CN 107442071 B CN107442071 B CN 107442071B CN 201710854582 A CN201710854582 A CN 201710854582A CN 107442071 B CN107442071 B CN 107442071B
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nitrate
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phosphorus
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CN107442071A (en
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杨文澜
史新星
王继承
腾凤云
杨迪
赵磊
徐国锋
左天培
冯金硕
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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
    • B01J20/28—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
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • 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
    • 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
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    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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
    • 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
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/08—Nanoparticles or nanotubes

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Abstract

The invention discloses a nano composite material for synchronously and selectively adsorbing phosphorus and nitrate and application thereof, belonging to the field of advanced treatment of biochemical tail water of sewage. The nano composite material carrier for synchronously and selectively adsorbing the phosphorus and the nitrate is a quaternized nano-pore polystyrene sphere, and Fe (III) oxide nano-particles are uniformly distributed in pores. The material of the invention can be used for treating the sewage biochemical tail water, can concentrate the adsorption of two pollutants of phosphorus and nitrate in one adsorption material, has simple operation process, stable operation effect and low cost, and can generate environmental benefit and economic benefit at the same time.

Description

Nano composite material for synchronously and selectively adsorbing phosphorus and nitrate and application
Technical Field
The invention belongs to the field of advanced treatment of biochemical tail water of sewage, and particularly relates to a nano composite material for synchronously and selectively adsorbing phosphorus and nitrate and application thereof.
Background
Eutrophication of water bodies is one of the common environmental problems facing countries in the world. Through long-term research, people gradually recognize that the eutrophication of the water body is mainly caused by abnormal development of primary productivity of the water ecosystem caused by overloaded nutrient elements such as nitrogen, phosphorus and the like in the water body. Therefore, the reduction of the discharge of nitrogen, phosphorus and other nutrient substances is an important measure for controlling the eutrophication of the water body.
In recent years, the total amount of sewage discharged in China is gradually increased year by year, the discharge amount of industrial wastewater tends to be stable, and the discharge amount of domestic sewage in cities and towns still continuously increases and tends to be accelerated. Under the influence of the living habits of residents, the pollution load of nitrogen and phosphorus in domestic sewage in China is relatively high, the nitrogen and phosphorus removal of the domestic sewage is enhanced, and the method has a significant effect on the prevention and treatment of the eutrophication of the water body in China. The pollutant discharge standard of urban sewage treatment plants implemented in China at present puts strict requirements on discharge of TN and TP of effluent of the urban sewage treatment plants, wherein TN is required to be less than 15mg/L, and TP is less than 0.5 mg/L.
The biochemical method is the mainstream treatment technology of the domestic sewage at present, and the conventional biochemical treatment process (such as A/O, A)2O, SBR, oxidation ditch, etc.) can reduce most pollutants in domestic sewage, but because the carbon source of inlet water of urban sewage plants in China is low and the water temperature changes in winter and summer are large, the biological nitrogen and phosphorus removal efficiency is low, and nitrogen and phosphorus in outlet water can not reach the standard stably (the operators are in the same direction, the weather is in the same direction, the Fang is in the same direction, the temperature and the added carbon source have influence on the biological nitrogen and phosphorus removal process. the report of environmental engineering, 2013,7(06),2013 and 2018.). The existing research shows that phosphorus mainly exists in the form of phosphate and nitrogen mainly exists in the form of nitrate in biochemical tail water after biological treatment (Liu Shi Jian, Yu Jing, Li Di, etc. the research on the morphological change rule of phosphorus in urban sewage treatment plants, water supply and drainage, 2011,37(02),50-53, plum-TONG, Huohui, Liu Feng, etc. the analysis on the operation effect of nitrogen and phosphorus removal by A/A/O process, the report of environmental engineering, 2011,5(08), 1729-.
For removing phosphorus from sewage, a common treatment method comprises: biological methods, crystallization methods, chemical precipitation methods, adsorption and ion exchange methods and the like, wherein the adsorption and ion exchange methods can not only achieve deep phosphorus removal, but also can realize phosphorus recovery, and are widely concerned by people. For the removal of nitrate from wastewater, common treatment methods include: zero-valent iron reduction, catalytic denitrification, membrane separation, adsorption, ion exchange method and the like, wherein the ion exchange method is widely applied to the deep treatment of nitrate as one of treatment methods recommended by the World Health Organization (WHO) and the United states environmental protection agency (US EPA).
Fe (III) oxide has a strong selective adsorption of phosphate ions in solution, which is well documented in many publications (Khare, N.; Hesterberg, D.; Martin, J.D., XANES agitation of phosphate adsorption in single and bind systems of iron and aluminum oxide Science & Technology,2005,39(7), 2152-. However, the particle size of the Fe (III) oxide particles is extremely small, and the Fe (III) oxide particles directly applied to a flow state processing system such as column adsorption and the like cause great pressure drop, and the Fe (III) oxide particles do not have the capability of removing nitrate. For example, the Chinese patent application No. 201410203733.5, published as 2014, 7, 23, discloses a method for synchronously removing organic matters and phosphorus in sewage biochemical tail water, wherein a composite material HFO-802 adopted in the adsorption process is developed and produced by environmental protection technology limited in south Jiangsu, a carrier adopted by the method is a tertiary aminated ultrahigh crosslinked nano-pore polystyrene sphere, the average pore size distribution is 0.5-5nm, hydrated iron oxide nano-particles with the particle size of 1-5nm are uniformly distributed in pores, and the weight percentage content of the hydrated iron oxide is controlled to be 2-20% (calculated by Fe). The method shows excellent synchronous removal effect of organic matters and phosphorus, but the method does not have the capability of selectively removing nitrate, and the problem that the concentration of the nitrate in the treated water is too high still exists.
The researchers found that the use of anion exchange resins to remove nitrate from wastewater could enhance the Selective adsorption of nitrate to the resin by increasing the alkyl chain length of quaternary amine groups on the surface of the resin (Gu, B.H.; Ku, Y.K.; Jardine, P.M., adsorption and binding exchange of nitrate, sulfate, and urethane ion-exchange resin Environment Science & Technology,2004,38(11), 3184-type 3188; Song, H.O., Zhou, Y.; Li, A.M.; Mueller, S.S., Selective removal of nitrate from a porous bed of strong basic ion exchange resin, degradation, 296,53-60.) however, such ion exchange resins had no alternative to remove phosphate.
Chinese patent application No. 201510556733.8, published as 2015, 12, 9, discloses a method for synthesizing and applying a composite functional resin capable of selectively removing nitrate and phosphate at the same time, the invention synthesizes a composite functional resin simultaneously having pyridine groups and triethylamine groups, the composite functional resin simultaneously has the selective adsorption effect of a pyridine transition metal complex on phosphate and the selective adsorption effect of the triethylamine groups on nitrate, and can selectively adsorb nitrate and phosphate when other soluble coexisting anions exist in a solution, so that the aim of selectively removing nitrate and phosphate at the same time is fulfilled. However, the composite functional resin is obtained by modifying a pyridine group and a triethylamine group on a polystyrene skeleton of the resin at the same time, so that the contents of the pyridine transition metal complex and the triethylamine group are not high (each accounts for about 50%), the pyridine transition metal complex has no adsorption capacity to nitrate, and the triethylamine group has no selective adsorption performance to phosphate, so that the adsorption capacity of the composite resin to nitrate and phosphate is low.
In terms of the mechanism of ion exchange, phosphorus and nitrate both exist in the form of negative ions in sewage, and can be removed simultaneously by anion exchange resin. However, in practical situations, on the one hand, phosphorus and nitrate compete for ion exchange sites, so that the respective removal efficiency is affected; on the other hand, biochemical tail water contains other anions (sulfate, chloride, carbonate, etc.) and soluble organic matters, and these coexisting substances compete for limited ion exchange sites, which results in a great decrease in the removal efficiency of phosphorus and nitrate.
In conclusion, the development of a method for synchronously and selectively removing phosphorus and nitrate in biochemical tail water with low consumption and high efficiency is still a difficult problem faced by the technology in the field.
Disclosure of Invention
1. Problems to be solved
The invention provides a nano composite material for synchronously and selectively adsorbing phosphorus and nitrate and application thereof, aiming at the problem that the existing adsorption/ion exchange material can not synchronously and efficiently and selectively remove the phosphorus and the nitrate.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a nano-class composite material for synchronously and selectively adsorbing P and nitrate is prepared from quaternary ammonium oxide nanoparticles (Fe (III) oxide) through preparing the carrier, and mixing with the carrier.
Furthermore, the quaternary amine group modified on the surface of the polystyrene sphere is triethylamine, tripropylamine or tributylamine, and the amine group content is 4-5 mmoL/g.
Furthermore, the average pore diameter of the polystyrene spheres is 5-50nm, the particle diameter of the Fe (III) oxide nanoparticles is 2-20nm, and the weight percentage content of the Fe (III) oxide is controlled to be 5-20% (calculated by Fe).
Further, the preparation of the nanocomposite material for synchronously and selectively adsorbing the phosphorus and the nitrate comprises the following steps:
(1) taking 50-100g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18 percent) to 100-200mL of deionized water, adding 200mL of triethylamine, tripropylamine or tributylamine solution at 10 ℃, heating to 60 ℃ at the speed of 10-20 ℃/h, and carrying out heat preservation and stirring reaction for 4-8 h; after the reaction is finished, filtering out the polystyrene microspheres and drying for 12h at 60 ℃ to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 20-50g of the quaternary amination polystyrene microsphere prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 5-20 percent, the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 5-10%, and the mass concentration of NaCl is 5%), and stirring and reacting at 25 ℃ for 12 hours;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with a 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 4-8h to obtain the nano composite material.
The nano composite material for synchronously and selectively adsorbing the phosphorus and the nitrate can be applied to the advanced treatment of sewage biochemical tail water.
Furthermore, the application of the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate in the treatment of the biochemical tail water of sewage comprises the following steps:
A. the effluent of the secondary sedimentation tank of the sewage biochemical treatment system passes through a multi-medium filter to remove colloid and suspended particles in the sewage;
B. passing the filtrate from step (a) through an adsorption tower packed with the nanocomposite for synchronously and selectively adsorbing phosphorus and nitrate;
C. when the adsorption reaches the breakthrough point, the concentration of TP in the adsorbed water is more than 0.5mg/L or NO3-Stopping adsorption when the N concentration is more than 5mg/L, and performing desorption regeneration on the nano composite material by using a NaOH-NaCl mixed solution as a desorption agent for recycling;
D. and (C) preparing NaOH-NaCl solution by using the low-concentration desorption solution obtained in the step (C) for the next batch of desorption operation, and concentrating the high-concentration desorption solution for recycling phosphorus and nitrate.
Furthermore, anthracite and quartz sand are selected as the filtering medium of the multi-medium filter in the step A, wherein the relative density of the anthracite is 1.4-1.8g/mm3The grain diameter is 1-2mm, the filter is arranged on the upper layer of the filter material layer, and the height of the filter layer is 40-100 cm; the relative density of the quartz sand is 2.4-2.8g/mm3The grain size is 0.6-1.2mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 30-60 cm; the filtration rate is 5-15 m/h.
Furthermore, when the pressure difference between the inlet and the outlet of the multi-media filter in the step (A) reaches 0.08MPa, backwashing is carried out. Adopting gas-water combined back flushing, firstly using air to back flush, and the air strength is as follows: 10-18L/(m)2S), backwash time: 2-4min, filter layer expansion rate: 10 to 20 percent; back flushing with water, and strength of back flushing water: 8-15L/(m)2S), backwash time: 5-10min, filter layer expansion rate: 20 to 40 percent.
Furthermore, in the step B, under the temperature condition of 5-30 ℃, the flow rate of the filtrate is 5-10BV/h (BV is the bed volume), and the treatment capacity of each batch of wastewater is 800-1600 BV.
Furthermore, the concentration of the NaOH-NaCl mixed solution in the step C is 2-12%, and desorption regeneration is carried out at the temperature of 30-60 ℃ and at the flow rate of 0.5-2 BV/h.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate couples the selective adsorption performance of a quaternized polymer carrier on nitrate and the selective phosphorus removal performance of Fe (III) oxide nanoparticles, so that one adsorption material can simultaneously remove phosphorus and nitrate;
(2) the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate can be repeatedly used, and has good regeneration performance and high mechanical strength;
(3) in the preparation process of the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, the quaternary ammonium group with the long alkyl chain is modified on the polystyrene carrier, so that the selective adsorption performance of the nano composite material on nitrate is enhanced; the Fe (III) oxide is immobilized in the pore channels of the polystyrene sphere through in-situ deposition reaction, and the Fe (III) oxide forms nanoparticles by utilizing the mesh confinement effect of the nanometer pore channels of the polystyrene sphere, so that the adsorption performance and the adsorption capacity of the Fe (III) oxide on phosphate ions are improved; meanwhile, the Donnan film pre-enrichment effect of the quaternary ammonium polystyrene sphere is utilized to further enhance the removal effect of the nano composite material on phosphorus and nitrate;
(4) the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate is applied to the treatment of the biochemical tail water of sewage, so that the removal of the phosphorus and the nitrate can be synchronously completed in one adsorbing material, the selectivity of the method for removing the phosphorus and the nitrate avoids the situation that other coexisting substances such as anions (sulfate, chloride, carbonate and the like) in the biochemical tail water compete for limited ion exchange sites to cause the great reduction of the removal efficiency of the phosphorus and the nitrate, the excellent synchronous removal effect of phosphorus and nitrate is shown in the biochemical tail water treatment of sewage, and most of the adsorption/ion exchange materials are only suitable for the independent removal of phosphorus or nitrate at present, and if the adsorption/ion exchange materials are required to simultaneously remove nitrogen and phosphorus in practical application, two sections of independent operation units are needed, so that the investment and operation cost is higher, the adsorption operation process is greatly reduced, and the investment and operation cost is reduced;
(5) the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate is applied to the treatment of the biochemical tail water of sewage, the multi-media filter selects anthracite and quartz sand as filter media, and the anthracite with large particle size and low density is placed on the upper part of the filter, so that large-particle suspended impurities in the sewage can be removed, and the filtering load of a quartz sand filter layer can be reduced; the quartz sand with small particle size and high density is arranged at the lower part of the filter, which is beneficial to further removing small particle colloid and suspended matters in sewage, meanwhile, the anthracite with low density is arranged at the upper part of the filter, the quartz sand with high density is arranged at the lower part of the filter, which can ensure that the filter material can not be disordered when the filter is backwashed, and the design of double filter layers of the anthracite and the quartz sand can ensure that biochemical tail water has higher filtering speed, control the density of media and the like, ensure better treatment effect, ensure that the concentration of suspended particulate matters (SS) in the effluent is less than 5mg/L and the turbidity is less than 3NTU, and ensure that the nano composite material adsorption tower can not be blocked by the suspended matters;
(6) the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate is applied to the treatment of the biochemical tail water of sewage, the low-concentration desorption solution is used for preparing NaOH-NaCl solution and is used for the next batch of desorption operation, and the high-concentration desorption solution is concentrated and then is used for recycling phosphorus and nitrate, so that the cyclic application is realized, and the treatment cost is effectively saved;
(7) the invention relates to an application of a nano composite material for synchronously and selectively adsorbing phosphorus and nitrate in the treatment of biochemical tail water of sewage, which enables the TP of treated effluent to be stably reduced to below 0.5mg/L and NO to be stably reduced to below 0.5mg/L under the conditions that the pH range of the effluent of a secondary sedimentation tank of a biochemical treatment system is 6.0-9.0 and the effluent contains phosphorus, nitrate, sulfate radicals, chloride ions, carbonate ions and other coexisting anions3--N steadily decreases to 5The concentration is below mg/L, so that important guarantee is provided for advanced treatment and comprehensive utilization of sewage, and the unification of environmental benefits and social benefits is realized;
(8) the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate is applied to the treatment of the biochemical tail water of sewage, has large treatment capacity, and can treat the biochemical tail water with the volume of 800-1600 bed layers in each batch under the condition of ensuring better treatment effect.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) taking 50g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18 percent) to 100mL of deionized water, adding 100mL of tributylamine solution at 10 ℃, then heating to 60 ℃ at the speed of 10 ℃/h, and carrying out heat preservation and stirring reaction for 8 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 20g of the quaternary amination polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 15 percent and the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 10 percent, the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 8 hours to obtain the nano composite material. The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.5mg/L, NO)3-N17.4 mg/L) into a multi-media filter, the filter using anthracite and quartz sand as the filter media, wherein the anthracite has a relative density of 1.6g/mm3The particle diameter is 1.5mm, and the mixture is placed on a filter material layerThe height of the filtering layer is 70 cm; the relative density of the quartz sand is 2.6g/mm3The grain size is 0.9mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 40 cm; the filtration rate was controlled to 10 m/h. The concentration of suspended particulate matter (SS) in the effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 15L/(m)2S), backwash time: 3min, expansion rate of filter layer: 15 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 12L/(m)2S), backwash time: 7min, expansion rate of filter layer: 30 percent.
50mL of nano composite material for synchronously and selectively adsorbing phosphorus and nitrate (the quaternary amino group modified by the nano composite material is tributylamine, the amino group content is 4mmoL/g, the average pore diameter is 25nm, the particle size of Fe (III) oxide nano particles is 10nm, and the weight percentage content of Fe (III) oxide is 15%) is put into a glass adsorption column (32 × 260mm) with a jacket, filtrate filtered by a multi-medium filter passes through a nano composite material bed layer at 10 +/-5 ℃ at the flow rate of 500mL/h (10BV/h), the treatment amount is 60000 mL/batch (1200 BV/batch), after the nano composite material is adsorbed, the effluent TP is reduced to 0.34mg/L, and NO is reduced to 0.34 BV/batch3--N was reduced to 4.1 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, and 50mL of 12% NaOH-NaCl mixed solution and 100mL of 2% NaOH-NaCl mixed solution are sequentially used, and 300mL of tap water passes through the nano composite material bed layer at a temperature of 45 +/-5 ℃ and at a flow rate of 50mL/h (1BV/h) for desorption. The desorbed high-concentration desorption solution (the first 150mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 300mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next batch of desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.
Example 2
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) taking 80g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18 percent) to 150mL of deionized water, adding 150mL of tripropylamine solution at 10 ℃, heating to 60 ℃ at the speed of 15 ℃/h, and carrying out heat preservation and stirring reaction for 6 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 30g of the quaternary amination polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 10 percent, the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 8 percent, and the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 6 hours to obtain the nano composite material.
The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.2mg/L, NO)3-N of 14.4 mg/L) into a multi-media filter, the filter using anthracite and quartz sand as the filter media, wherein the anthracite has a relative density of 1.4g/mm3The grain size is 2mm, the filter material layer is arranged on the upper layer, and the height of the filter layer is 100 cm; the relative density of the quartz sand is 2.8g/mm3The grain size is 0.6mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 30 cm; the filtration speed is controlled to be 15m/h, the concentration of suspended particulate matters (SS) in effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 10L/(m)2S), backwash time: 4min, expansion rate of a filter layer: 10 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 15L/(m)2S), backwash time: 5min, expansion rate of filter layer: 40 percent.
200mL of nano composite material for synchronously and selectively adsorbing phosphorus and nitrate (nano composite material modification)The decorated quaternary ammonium group is tripropylamine, the amino group content is 4.5mmoL/g, the average pore diameter is 10nm, the grain diameter of Fe (III) oxide nano-particles is 5nm, the weight percentage content of Fe (III) oxide is 10 percent, and the decorated quaternary ammonium group is filled into a glass adsorption column (64 × 320mm) with a jacket, the filtrate filtered by a multi-medium filter is taken to pass through a nano-composite material bed layer at the temperature of 15 +/-5 ℃ and the flow rate of 1400mL/h (7BV/h), the treatment amount is 260000 mL/batch (1300 BV/batch), after the nano-composite material is adsorbed, the TP of effluent is reduced to 0.32mg/L, and NO is reduced to 0.32mg/L3--N was reduced to 3.9 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, 200mL of 10% NaOH-NaCl mixed solution and 400mL of 4% NaOH-NaCl mixed solution are sequentially used, 1200mL of tap water flows through the nano composite material bed layer at the temperature of 55 +/-5 ℃ and the flow rate of 300mL/h (1.5BV/h) for desorption. The desorbed high-concentration desorption solution (the first 600mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 1200mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next batch of desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.
Example 3
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) 100g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18%) are taken to be 200mL of deionized water, 200mL of triethylamine solution is added at 10 ℃, then the temperature is raised to 60 ℃ at the speed of 20 ℃/h, and the mixture is kept warm and stirred for reaction for 4 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 50g of the quaternized polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 5 percent and the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 5 percent, the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 4 hours to obtain the nano composite material.
The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.8mg/L, NO)3-18.8mg/L N) into a multi-media filter, anthracite and quartz sand are selected as filter media of the filter, wherein the relative density of the anthracite is 1.8g/mm3The grain size is 1mm, the filter material layer is arranged on the upper layer, and the height of the filter layer is 40 cm; the relative density of the quartz sand is 2.4g/mm3The grain size is 1.2mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 60 cm; the filtration speed is controlled to be 5m/h, the concentration of suspended particulate matters (SS) in effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 18L/(m)2S), backwash time: 2min, filter layer expansion rate: 20 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 8L/(m)2S), backwash time: 10min, filter layer expansion rate: 20 percent.
500mL of nano composite material for synchronously and selectively adsorbing phosphorus and nitrate (the quaternary amino group modified by the nano composite material is triethylamine, the amino group content is 5mmoL/g, the average pore diameter is 5nm, the particle size of Fe (III) oxide nano particles is 2nm, and the weight percentage content of Fe (III) oxide is 5%) is put into a glass adsorption column (100 × 360mm) with a jacket, filtrate filtered by a multi-medium filter passes through a nano composite material bed layer at 25 +/-5 ℃ at the flow rate of 4000mL/h (8BV/h), the treatment amount is 400000 mL/batch (800 BV/batch), and after the nano composite material is adsorbed, the TP of effluent is reduced to 0.43mg/L and NO is reduced3--N was reduced to 4.1 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, 500mL of 8% NaOH-NaCl mixed solution and 1000mL of 6% NaOH-NaCl mixed solution are sequentially used, and 3000mL of tap water flows through the nano composite material bed layer downstream at the temperature of 35 +/-5 ℃ and the flow rate of 1000mL/h (2BV/h) for desorption. The desorbed high-concentration desorption solution (the first 1500mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 3000mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.
Example 4
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) taking 100g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18 percent) to 200mL of deionized water, adding 200mL of tributylamine solution at 10 ℃, then heating to 60 ℃ at the speed of 20 ℃/h, and carrying out heat preservation and stirring reaction for 8 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 50g of the quaternized polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 20 percent and the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 10 percent, the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 8 hours to obtain the nano composite material.
The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.4mg/L, NO)3-N is 16.2 mg/L) flows into a multi-medium filter, anthracite and quartz sand are selected as filter media of the filter, wherein the relative density of the anthracite is 1.6g/mm3Particle diameter of 15mm, placing the filter material layer on the upper layer, wherein the height of the filter layer is 70 cm; the relative density of the quartz sand is 2.6g/mm3The grain size is 0.9mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 40 cm; the filtration speed is controlled to be 12m/h, the concentration of suspended particulate matters (SS) in effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 15L/(m)2S), backwash time: 3min, expansion rate of filter layer: 15 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 12L/(m)2S), backwash time: 7min, expansion rate of filter layer: 30 percent.
200mL of nano composite material for synchronously and selectively adsorbing phosphorus and nitrate (the quaternary amino group modified by the nano composite material is tributylamine, the amino group content is 4mmoL/g, the average pore diameter is 50nm, the particle size of Fe (III) oxide nano particles is 20nm, and the weight percentage content of Fe (III) oxide is 20%) are put into a glass adsorption column (64 × 320mm) with a jacket, filtrate filtered by a multi-media filter passes through a nano composite material bed layer at 15 +/-5 ℃ at the flow rate of 1600mL/h (8BV/h), the treatment amount is 200000 mL/batch (1200 BV/batch), after the nano composite material is adsorbed, the effluent TP is reduced to 0.37mg/L, NO is reduced to 0.37 BV/batch3-N was reduced to 3.8 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, 200mL of 10% NaOH-NaCl mixed solution and 400mL of 4% NaOH-NaCl mixed solution are sequentially used, 1200mL of tap water flows through the nano composite material bed layer at the temperature of 45 +/-5 ℃ and the flow rate of 200mL/h (1BV/h) for desorption. The desorbed high-concentration desorption solution (the first 600mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 1200mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next batch of desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.
Example 5
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) taking 80g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18 percent) to 150mL of deionized water, adding 150mL of tripropylamine solution at 10 ℃, heating to 60 ℃ at the speed of 15 ℃/h, and carrying out heat preservation and stirring reaction for 6 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 30g of the quaternary amination polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 10 percent, the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 8 percent, and the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 6 hours to obtain the nano composite material.
The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.1mg/L, NO)3-N is 13.6 mg/L) flows into a multi-medium filter, anthracite and quartz sand are selected as filter media of the filter, wherein the relative density of the anthracite is 1.4g/mm3The grain size is 1.8mm, the filter material layer is arranged on the upper layer, and the height of the filter layer is 90 cm; the relative density of the quartz sand is 2.8g/mm3The grain size is 0.6mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 30 cm; the filtration speed is controlled to be 10m/h, the concentration of suspended particulate matters (SS) in effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 12L/(m)2S), backwash time: 4min, expansion rate of a filter layer: 12 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 15L/(m)2S), backwash time: 6min, expansion rate of filter layer: 38 percent.
Nano-compounding 500mL of synchronously and selectively adsorbing phosphorus and nitrateThe material (quaternary amine group modified by the nano composite material is tripropylamine, the amino group content is 4.5mmoL/g, the average pore diameter is 10nm, the particle diameter of Fe (III) oxide nano particles is 5nm, the weight percentage content of Fe (III) oxide is 10%) is filled into a glass adsorption column (100 × 360mm) with a jacket, filtrate filtered by a multi-medium filter is taken to pass through a nano composite material bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 2500mL/h (5BV/h), the treatment capacity is 800000 mL/batch (1600 BV/batch), after the nano composite material is adsorbed, the TP of effluent water is reduced to 0.38mg/L, and NO is reduced to 0.38mg/L3--N was reduced to 4.1 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, 500mL of 8% NaOH-NaCl mixed solution and 1000mL of 6% NaOH-NaCl mixed solution are sequentially used, and 3000mL of tap water flows through the nano composite material bed layer downstream at the temperature of 50 +/-5 ℃ and the flow rate of 250mL/h (0.5BV/h) for desorption. The desorbed high-concentration desorption solution (the first 1500mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 3000mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.
Example 6
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) 100g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18%) are taken to be 200mL of deionized water, 200mL of triethylamine solution is added at 10 ℃, then the temperature is raised to 60 ℃ at the speed of 20 ℃/h, and the mixture is kept warm and stirred for reaction for 4 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 50g of the quaternized polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 5 percent and the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 5 percent, the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 4 hours to obtain the nano composite material.
The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.3mg/L, NO)3-N is 19.3 mg/L) flows into a multi-medium filter, anthracite and quartz sand are selected as filter media of the filter, wherein the relative density of the anthracite is 1.8g/mm3The grain size is 1.2mm, the filter material layer is arranged on the upper layer, and the height of the filter layer is 60 cm; the relative density of the quartz sand is 2.4g/mm3The grain size is 1.0mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 50 cm; the filtration speed is controlled to be 15m/h, the concentration of suspended particulate matters (SS) in effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 18L/(m)2S), backwash time: 2min, filter layer expansion rate: 20 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 10L/(m)2S), backwash time: 8min, expansion rate of filter layer: 25 percent.
50mL of nano composite material for synchronously and selectively adsorbing phosphorus and nitrate (the quaternary amino group modified by the nano composite material is triethylamine, the amino group content is 5mmoL/g, the average pore diameter is 5nm, the particle size of Fe (III) oxide nano particles is 2nm, and the weight percentage content of Fe (III) oxide is 5%) is put into a glass adsorption column (32 × 260mm) with a jacket, filtrate filtered by a multi-medium filter is taken to pass through a nano composite material bed layer at 10 +/-5 ℃ at the flow rate of 500mL/h (10BV/h), the treatment capacity is 60000 mL/batch (1200 BV/batch), and after the nano composite material is adsorbed, the effluent TP is reduced to 0.34mg/L, NO and3--N was reduced to 4.4 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, and 50mL of 12% NaOH-NaCl mixed solution and 100mL of 2% NaOH-NaCl mixed solution are sequentially used, and 300mL of tap water passes through the nano composite material bed layer at a temperature of 45 +/-5 ℃ and at a flow rate of 50mL/h (1BV/h) for desorption. The desorbed high-concentration desorption solution (the first 150mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 300mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next batch of desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.
Example 7
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) taking 50g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18 percent) to 100mL of deionized water, adding 100mL of tributylamine solution at 10 ℃, then heating to 60 ℃ at the speed of 10 ℃/h, and carrying out heat preservation and stirring reaction for 8 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 20g of the quaternary amination polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 15 percent and the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 10 percent, the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 8 hours to obtain the nano composite material.
The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.4mg/L, NO)3-N15.6 mg/L) into a multi-media filter, the filter using anthracite and quartz sand as the filter media, wherein the anthracite has a relative density of 1.6g/mm3The grain size is 1.5mm, the filter material layer is arranged on the upper layer, and the height of the filter layer is 70 cm; the relative density of the quartz sand is 2.6g/mm3The grain size is 0.9mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 40 cm; the filtration speed is controlled to be 12m/h, the concentration of suspended particulate matters (SS) in effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 15L/(m)2S), backwash time: 3min, expansion rate of filter layer: 15 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 12L/(m)2S), backwash time: 7min, expansion rate of filter layer: 30 percent.
500mL of nano composite material for synchronously and selectively adsorbing phosphorus and nitrate (the quaternary amino group modified by the nano composite material is tributylamine, the amino group content is 4mmoL/g, the average pore diameter is 25nm, the particle size of Fe (III) oxide nano particles is 10nm, and the weight percentage content of Fe (III) oxide is 15%) is put into a glass adsorption column (32 × 260mm) with a jacket, filtrate filtered by a multi-media filter passes through a nano composite material bed layer at 10 +/-5 ℃ at the flow rate of 2500mL/h (5BV/h), the treatment amount is 800000 mL/batch (1600 BV/batch), after the nano composite material is adsorbed, the TP of effluent is reduced to 0.4mg/L, NO is reduced to 0.4 BV/batch3-N is reduced to 4.2 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, 500mL of 12% NaOH-NaCl mixed solution and 1000mL of 2% NaOH-NaCl mixed solution are sequentially used, and 3000mL of tap water flows through the nano composite material bed layer downstream at the temperature of 35 +/-5 ℃ and the flow rate of 250mL/h (0.5BV/h) for desorption. The desorbed high-concentration desorption solution (the first 1500mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 3000mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.
Example 8
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) taking 80g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18 percent) to 150mL of deionized water, adding 150mL of tripropylamine solution at 10 ℃, heating to 60 ℃ at the speed of 15 ℃/h, and carrying out heat preservation and stirring reaction for 6 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 30g of the quaternary amination polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 10 percent, the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 8 percent, and the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 6 hours to obtain the nano composite material.
The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.1mg/L, NO)3-11.4mg/L of N) into a multi-media filter, the filter selects anthracite and quartz sand as filter media, wherein the relative density of the anthracite is 1.4g/mm3The grain size is 1.8mm, the filter material layer is arranged on the upper layer, and the height of the filter layer is 90 cm; the relative density of the quartz sand is 2.8g/mm3The grain size is 0.6mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 30 cm; the filtration speed is controlled to be 10m/h, the concentration of suspended particulate matters (SS) in effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 12L/(m)2S), backwash time: 4min, expansion rate of a filter layer: 12 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 15L/(m)2S), backwash time: 6min, expansion rate of filter layer: 38 percent.
50mL of the solution is synchronously and selectively adsorbed with phosphorusAnd the nano composite material of nitrate (the quaternary amine group modified by the nano composite material is tripropylamine, the amino group content is 4.5mmoL/g, the average pore diameter is 10nm, the grain diameter of the Fe (III) oxide nano particles is 5nm, the weight percentage content of the Fe (III) oxide is 10%) is filled into a glass adsorption column (32 × 260mm) with a jacket, the filtrate filtered by a multi-medium filter is taken to pass through a nano composite material bed layer at 10 +/-5 ℃ at the flow rate of 500mL/h (10BV/h), the treatment capacity is 60000 mL/batch (1200 BV/batch), after the nano composite material is adsorbed, the effluent TP is reduced to 0.29mg/L, NO is reduced to 0.29mg/L3--N was reduced to 3.2 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, 50mL of 12% NaOH-NaCl mixed solution and 100mL of 2% NaOH-NaCl mixed solution are sequentially used, and 300mL of tap water flows through the nano composite material bed layer at the temperature of 45 +/-5 ℃ and the flow rate of 100mL/h (2BV/h) for desorption. The desorbed high-concentration desorption solution (the first 150mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 300mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next batch of desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.
Example 9
Firstly, preparing the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate, wherein the preparation process comprises the following steps:
(1) taking 100g of chloromethylated polystyrene microspheres (the mass concentration of chlorine is 18 percent) to 200mL of deionized water, adding 200mL of tributylamine solution at 10 ℃, then heating to 60 ℃ at the speed of 20 ℃/h, and carrying out heat preservation and stirring reaction for 8 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 50g of the quaternized polystyrene microspheres prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution (FeCl)3The mass concentration of the HCl is 20 percent and the mass concentration of the HCl is 10 percent), and the mixture is stirred and reacted for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution (the mass concentration of NaOH is 10 percent, the mass concentration of NaCl is 5 percent), and stirring and reacting for 12 hours at 25 ℃;
(4) and (3) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 8 hours to obtain the nano composite material.
The effluent of a secondary sedimentation tank of a biochemical treatment system of a domestic sewage plant (TP is 1.9mg/L, NO)3-N is 19.4 mg/L) flows into a multi-medium filter, anthracite and quartz sand are selected as filter media of the filter, wherein the relative density of the anthracite is 1.8g/mm3The grain size is 1.2mm, the filter material layer is arranged on the upper layer, and the height of the filter layer is 60 cm; the relative density of the quartz sand is 2.4g/mm3The grain size is 1.0mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 50 cm; the filtration speed is controlled to be 15m/h, the concentration of suspended particulate matters (SS) in effluent is less than 5mg/L, and the turbidity is less than 3 NTU.
And when the pressure difference between the inlet and the outlet of the sand filter reaches 0.08MPa, performing back flushing. Firstly, backflushing with air, wherein the air strength is as follows: 18L/(m)2S), backwash time: 2min, filter layer expansion rate: 20 percent; back flushing with water, wherein the strength of the back flushing water is as follows: 10L/(m)2S), backwash time: 8min, expansion rate of filter layer: 25 percent.
200mL of nano composite material for synchronously and selectively adsorbing phosphorus and nitrate (the quaternary amino group modified by the nano composite material is tributylamine, the amino group content is 4mmoL/g, the average pore diameter is 50nm, the particle size of Fe (III) oxide nano particles is 20nm, and the weight percentage content of Fe (III) oxide is 20%) is put into a glass adsorption column (64 × 320mm) with a jacket, filtrate filtered by a multi-medium filter passes through a nano composite material bed layer at 15 +/-5 ℃ at the flow rate of 1600mL/h (8BV/h), the treatment amount is 180000 mL/batch (900 BV/batch), after the nano composite material is adsorbed, the effluent TP is reduced to 0.45mg/L, NO is reduced to 0.45 BV/batch3-N was reduced to 4.7 mg/L.
When the adsorption reaches the breakthrough point, the adsorption is stopped, 200mL of 10% NaOH-NaCl mixed solution and 400mL of 4% NaOH-NaCl mixed solution are sequentially used, 1200mL of tap water flows through the nano composite material bed layer at the temperature of 55 +/-5 ℃ and the flow rate of 300mL/h (1.5BV/h) for desorption. The desorbed high-concentration desorption solution (the first 600mL desorption solution) is concentrated and then used for recycling phosphorus and nitrate, and the desorbed low-concentration solution (the second 1200mL desorption solution) is used for preparing NaOH-NaCl solution and is used for the next batch of desorption operation.
The desorption efficiency of the nano composite material is more than or equal to 95 percent, and the adsorption capacity after regeneration is reduced by less than or equal to 10 percent; the crushing phenomenon of the nano composite material is not seen after long-term operation, and the quality of effluent water is stable, which shows that the material has high mechanical strength and good process stability.

Claims (6)

1. The application of the nano composite material for synchronously and selectively adsorbing phosphorus and nitrate in the treatment of the biochemical tail water of sewage is characterized in that: the carrier of the nano composite material is a quaternized nano-pore polystyrene sphere, and trivalent Fe oxide nano-particles are uniformly distributed in pores;
the quaternary amine group modified on the surface of the polystyrene sphere is triethylamine, tripropylamine or tributylamine, and the amine group content is 4-5 mmol/g;
the average pore diameter of the polystyrene sphere is 5-50nm, the particle diameter of the trivalent Fe oxide nano particle is 2-20nm, the weight percentage content of the trivalent Fe oxide is 5-20%, and the weight percentage content is calculated by Fe;
the preparation method of the nano composite material comprises the following steps:
(1) taking 50-100g of chloromethylated polystyrene microspheres into 100-200mL of deionized water, wherein the mass concentration of chlorine in the chloromethylated polystyrene microspheres is 18%, adding 200mL of triethylamine, tripropylamine or tributylamine solution at 10 ℃, heating to 60 ℃ at the speed of 10-20 ℃/h, and carrying out heat preservation and stirring reaction for 4-8 h; after the reaction is finished, filtering out the polystyrene microspheres and drying the polystyrene microspheres at 60 ℃ for 12 hours to prepare quaternary amination nano-pore polystyrene microspheres;
(2) taking 20-50g of the quaternary amination polystyrene microsphere prepared in the step (1), and adding 200mL of FeCl3+ HCl mixed solution, in which FeCl3Of 5-20% by mass of HClThe mass concentration is 10 percent, and the stirring reaction is carried out for 12 hours at the temperature of 25 ℃;
(3) filtering out the polystyrene microspheres reacted in the step (2), adding the polystyrene microspheres into 200mL of NaOH + NaCl mixed solution, wherein the mass concentration of NaOH is 5-10%, the mass concentration of NaCl is 5%, and stirring and reacting for 12h at 25 ℃;
(4) filtering out the polystyrene microspheres reacted in the step (3), washing with 5% NaCl solution, washing with deionized water until the effluent is neutral, soaking with absolute ethyl alcohol, and drying at 60 ℃ for 4-8h to obtain the nano composite material;
TP in the biochemical tail water of the sewage is 1.1-1.9 mg/L, and NO is3 -the-N is 11.4-19.4 mg/L.
2. The application of the nanocomposite for synchronously and selectively adsorbing phosphorus and nitrate in the treatment of the biochemical tail water of sewage, which is disclosed by claim 1, is characterized in that: the method comprises the following steps:
A. the effluent of the secondary sedimentation tank of the sewage biochemical treatment system passes through a multi-medium filter to remove colloid and suspended particles in the sewage;
B. passing the filtrate of step a through an adsorption tower packed with the nanocomposite for simultaneous selective adsorption of phosphorus and nitrate according to claim 1;
C. stopping adsorption when the adsorption reaches a breakthrough point, and performing desorption regeneration on the nanocomposite by using a NaOH-NaCl mixed solution as a desorption agent for recycling;
D. and D, using the low-concentration desorption solution obtained in the step C to prepare a NaOH-NaCl solution for the next batch of desorption operation, and concentrating the high-concentration desorption solution for recycling the phosphorus and the nitrate.
3. The application of the nanocomposite for synchronously and selectively adsorbing phosphorus and nitrate in the treatment of the biochemical tail water of sewage, which is disclosed by claim 2, is characterized in that: in the step A, anthracite and quartz sand are selected as filter media of the multi-media filter, wherein the relative density of the anthracite is 1.4-1.8 g/cm3The particle diameter is 1-2mm, and the particles are placed in a filter material layerThe height of the upper layer and the filtering layer is 40-100 cm; the relative density of the quartz sand is 2.4-2.8 g/cm3The grain size is 0.6-1.2mm, the filter material layer is arranged at the lower layer, and the height of the filter layer is 30-60 cm; the filtration rate is 5-15 m/h.
4. The application of the nanocomposite for synchronously and selectively adsorbing phosphorus and nitrate in the treatment of the biochemical tail water of sewage, which is disclosed by claim 3, is characterized in that: when the pressure difference between the inlet and the outlet of the multi-media filter in the step A reaches 0.08MPa, performing backwashing; adopting gas-water combined back flushing, firstly using air to back flush, and the air strength is as follows: 10-18L/(m)2S), backwash time: 2-4 min; back flushing with water, and strength of back flushing water: 8-15L/(m)2S), backwash time: 5-10 min.
5. The application of the nanocomposite for synchronously and selectively adsorbing phosphorus and nitrate in the treatment of the biochemical tail water of sewage, which is disclosed by claim 2, is characterized in that: and in the step B, under the temperature condition of 5-30 ℃, the flow rate of the filtrate is 5-10BV/h, BV is the volume of the bed layer, and the treatment capacity of wastewater in each batch is 800-1600 BV.
6. The application of the nanocomposite for synchronously and selectively adsorbing phosphorus and nitrate in the treatment of the biochemical tail water of sewage, which is disclosed by claim 2, is characterized in that: in the step C, the concentration of the NaOH-NaCl mixed solution is 2-12%, and desorption regeneration is carried out at the temperature of 30-60 ℃ and at the flow rate of 0.5-2 BV/h.
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