CN107442071A - A kind of nano composite material and the application of synchronous selective Phosphate Sorption and nitrate - Google Patents

A kind of nano composite material and the application of synchronous selective Phosphate Sorption and nitrate Download PDF

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CN107442071A
CN107442071A CN201710854582.3A CN201710854582A CN107442071A CN 107442071 A CN107442071 A CN 107442071A CN 201710854582 A CN201710854582 A CN 201710854582A CN 107442071 A CN107442071 A CN 107442071A
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nitrate
composite material
nano composite
filter
nano
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CN107442071B (en
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杨文澜
王继承
史新星
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
    • 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
    • B01J20/28054—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
    • 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
    • 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

Abstract

The invention discloses nano composite material and the application of a kind of synchronous selective Phosphate Sorption and nitrate, belongs to biochemical sewage Tailwater Depth process field.The nano composite material carrier of the synchronous selective Phosphate Sorption and nitrate is quaternary ammoniated nano-pore diameter polystyrene spheres, and Fe (III) oxide nano particles are evenly distributed with hole.Using material process biochemical sewage tail water of the present invention, the absorption of phosphorus and the pollutant of nitrate two can be concentrated in a kind of sorbing material and carried out, operating procedure is simple, and operational effect is stable, and cost is cheap, and economic benefit is produced again while generation environment benefit.

Description

A kind of nano composite material and the application of synchronous selective Phosphate Sorption and nitrate
Technical field
The invention belongs to biochemical sewage Tailwater Depth process field, is adsorbed more specifically to a kind of synchronous selective The nano composite material and application of phosphorus and nitrate.
Background technology
Body eutrophication is one of common environmental problem that countries in the world face.It is gradual by long-term research, people Recognize, body eutrophication is mainly due at the beginning of aquatic ecosystem caused by the nutrient such as the nitrogen of excess load, phosphorus in water body Caused by level productivity Abnormal Development.Therefore, the discharge for cutting down the nutriments such as nitrogen, phosphorus is to control the important act of body eutrophication Arrange.
In recent years, China's total amount of sewage discharge cumulative year after year, wherein discharged volume of industrial waste water have been tended towards stability, and cities and towns are given birth to Quantity of wastewater effluent living still sustainable growth simultaneously has the trend of quickening.Influenceed by residents'living habit, nitrogen, phosphorus in China's sanitary sewage Pollutional load is of a relatively high, strengthens the denitrogenation dephosphorizing of sanitary sewage, and the preventing and treating for China's body eutrophication has act foot light The effect of weight.What China implemented at present《Urban wastewater treatment firm pollutant emission standard》, to urban wastewater treatment firm water outlet TN Discharge with TP proposes strict requirements, and wherein TN requirements are less than 15mg/L, and TP is less than 0.5mg/L.
Biochemical process is the main flow treatment technology of current sanitary sewage, conventional biochemical processing process (such as A/O, A2/O、SBR、 Oxidation ditch etc.) although most of pollutant in sanitary sewage can be cut down, because China's municipal wastewater treatment plant water-inlet carbon source is relatively low, the winter Summer water temperature changes greatly, and causes biological denitrification dephosphorization efficiency relatively low, and nitrogen, phosphorus are unable to stably reaching standard and (it is suitable to grasp house, Hou Liang in water outlet Great, Fang Fang waits the influence environmental project journals of temperature and additional carbon to biological carbon and phosphorous removal process, 2013,7 (06), 2013-2018.).Now there are some researches show in the biochemical tail water after biological treatment, phosphorus mainly exists in the form of phosphate, and nitrogen Mainly existing in the form of nitrate (Liu Zhigang, Yu Jingjing, Li Yi, waits the Variation Regularity of Morphological Characteristics of municipal sewage plants phosphorus to grind Study carefully water supply and drainages, 2011,37 (02), 50-53；Lee Pupil, Hao Ruixia, Liu Feng, wait .A/A/O technique denitrogenation dephosphorizings operational effect point Analyse environmental project journals, 2011,5 (08), 1729-1734.), therefore phosphorus and the synchronous of nitrate are removed for municipal wastewater treatment plant The denitrogenation dephosphorizing of biochemical tail water has vital effect.
Removal for phosphor in sewage, conventional processing method include：Bioanalysis, crystallisation, chemical precipitation method, absorption with Ion-exchange etc., wherein absorption can not only reach deep phosphorous removal with ion-exchange, additionally it is possible to the recovery of phosphorus is realized, by The extensive concern of people.Removal for nitrate from waste water, conventional processing method include：Zero-valent Iron reduction, it is catalyzed anti-nitre Change, UF membrane, absorption and ion-exchange etc., its ion exchange methods is as the World Health Organization (WHO) and Environmental Protection Agency One of processing method that (US EPA) recommends, is widely applied in the advanced treating of nitrate.
Fe (III) oxides have very strong selective absorption performance to the phosphate anion in solution, and this is in many documents In have been described (Khare, N.；Hesterberg,D.；Martin,J.D.,XANES investigation of phosphate sorption in single and binary systems of iron and aluminum oxide minerals.Environmental Science&Technology,2005,39(7),2152-2160.).But Fe (III) is aoxidized Composition granule particle diameter is minimum, and very big pressure drop, and Fe (III) oxide will be caused by directly applying in the fluidised form processing systems such as post absorption The ability for removing nitrate is not had.As Chinese Patent Application No. be 201410203733.5, publication date is July 23 in 2014 The patent document of day, a kind of synchronous method for removing biochemical sewage tail Organic substance in water and phosphorus is disclosed, is used in adsorption process Composite HFO-802 be Jiangsu NJU Environmental Technology Co., Ltd.'s development and production, its carrier used is tertiary-aminated super High crosslinking nano hole polystyrene spheroid, average pore size are distributed as 0.5-5nm, and the water that particle diameter is 1-5nm is evenly distributed with hole Close ferric oxide nanometer particle, the weight percent content of hydrated ferric oxide is controlled at 2-20% (in terms of Fe).This method is shown Excellent organic matter and the synchronous removal effect of phosphorus, but it does not possess the ability of selective removal nitrate, the water after processing according to So it there may be the problem of nitrate concentration is too high.
Related scholar's research is found, the nitrate in sewage is removed using anion exchange resin, by increasing resin table The long alkyl chains of face quaternary amine base can lift adsorption selectivity (Gu, B.H. of the resin to nitrate；Ku,Y.K.； Jardine,P.M.,Sorption and binary exchange of nitrate,sulfate,and uranium on an anion-exchange resin.Environmental Science&Technology,2004,38(11),3184- 3188；Song,H.O.；Zhou,Y.；Li,A.M.；Mueller,S.,Selective removal of nitrate from water by a macroporous strong basic anion exchange resin.Desalination,2012, 296,53-60.), but such ion exchange resin does not possess selectivity to phosphate radical, makes its removal capacity to phosphorus and pays no attention to Think.
Chinese invention patent application number is 201510556733.8, and publication date is the patent document on December 9th, 2015, public Synthesis and application process that a kind of simultaneous selection removes nitrate and phosphatic composite function resin, invention synthesis are opened Composite function resin that is a kind of while having pyridine groups and triethylamine group, the composite function resin have pyridine mistake simultaneously Cross metal complex to act on the selective absorption of phosphatic selective absorption effect and triethylamine group to nitrate, molten It is capable of the absorption nitrate and phosphate of selectivity when other dissolubility counter anions in liquid be present, so as to reach simultaneous selection Property remove nitrate and phosphatic purpose.But the composite function resin is on resin polystyrene backbone while modified Pyridine groups and triethylamine group so that the content of pyridine transition metal complex and triethylamine group is not high (respectively to account for 50% Left and right), and pyridine transition metal complex does not have adsorption capacity to nitrate, triethylamine group does not select phosphate to adsorb Performance, cause the compound resin relatively low to nitrate and phosphatic adsorption capacity.
For the mechanism of ion exchange, phosphorus and nitrate exist in sewage in the form of anion, can pass through Anion exchange resin synchronizes removal to it.But under actual conditions, one side phosphorus can competing ions friendship with nitrate itself Exchange point so that respective removal efficiency is affected；On the other hand, other anion (sulphur are contained toward contact in biochemical tail water Acid group, chlorion, carbonate etc.) and dissolved organic matter, these coexisting substances will compete limited ion exchange site, lead The removal efficiency of phosphorus and nitrate is caused to decline to a great extent.
In summary, the synchronous selective for researching and developing low-consumption high-efficiency removes the method for phosphorus and nitrate in biochemical tail water, is still The problem that art technology is faced.
The content of the invention
1. to solve the problems, such as
The problem of phosphorus and nitrate are synchronous, efficient selective removes can not be realized for existing absorption/ion exchange material, The present invention provides a kind of nano composite material and the application of synchronous selective Phosphate Sorption and nitrate, uses the material process sewage Biochemical tail water, the absorption of phosphorus and the pollutant of nitrate two can be concentrated in a kind of sorbing material and carried out, operating procedure letter Single, operational effect is stable, and cost is cheap, and economic benefit is produced again while generation environment benefit.
2. technical scheme
In order to solve the above problems, the technical solution adopted in the present invention is as follows：
A kind of nano composite material of synchronous selective Phosphate Sorption and nitrate, its carrier are quaternary ammoniated nano-pore polyphenyl Ethene spheroid, Fe (III) oxide nano particles are evenly distributed with hole.
Further, the quaternary amine base of described diameter polystyrene spheres surface modification is triethylamine, tripropyl amine (TPA) or tri-n-butylamine, Amine groups content is 4-5mmoL/g.
Further, the average pore size of described diameter polystyrene spheres is 5-50nm, and described Fe (III) oxide is received Rice grain particle diameter is 2-20nm, and the weight percent content of Fe (III) oxide is controlled at 5-20% (in terms of Fe).
Further, the nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared and comprised the following steps：
(1) 50-100g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken to 100-200mL deionizations In water, triethylamine, tripropyl amine (TPA) or tri-n-butylamine solution 100-200mL are added at 10 DEG C, is then heated up with 10-20 DEG C/h speed To 60 DEG C, and insulated and stirred reaction 4-8h；Reaction is completed, and polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to make Obtain quaternary ammoniated nano-pore polystyrene microsphere；
(2) quaternary ammoniated polystyrene microsphere 20-50g made from step (1) is taken, is added to 200mL FeCl3+ HCl's is mixed Close (FeCl in solution3Mass concentration be 5-20%, 10%) HCl mass concentration is, stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (NaOH mass concentration is 5-10%, and NaCl mass concentration is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5%NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 4-8h after 60 DEG C, that is, the nano composite material is made.
The nano composite material of above-mentioned synchronous selective Phosphate Sorption and nitrate can be applied to the depth of biochemical sewage tail water In processing.
Further, the nano composite material of synchronous selective Phosphate Sorption and nitrate is in the processing of biochemical sewage tail water Application, comprise the following steps：
A. biochemical wastewater treatment system secondary clarifier effluent is removed into colloid and suspension in sewage by more medium filter Grain thing；
B. by the filtrate in step (A), answered by the nanometer for being filled with described synchronous selective Phosphate Sorption and nitrate The adsorption tower of condensation material；
C. it is more than 0.5mg/L or NO when absorption reaches breakthrough point and adsorbs TP concentration in water outlet3-When-N concentration is more than 5mg/L Stop absorption, by the use of NaOH-NaCl mixed solutions as desorbing agent, desorption and regeneration is carried out to above-mentioned nano composite material, for circulation Use；
D. light concentration desorption liquid step (C) obtained is covered for next group desorption behaviour for preparing NaOH-NaCl solution Make, the recycling after high concentration desorption liquid is concentrated for phosphorus and nitrate.
Further, more medium filter selects anthracite and quartz sand as filter medium in the step A, wherein Anthracite relative density is 1.4-1.8g/mm3, particle diameter 1-2mm, it is placed in filter material layer upper strata, filter height 40-100cm；Stone Sand relative density is 2.4-2.8g/mm3, particle diameter 0.6-1.2mm, it is placed in filter material layer lower floor, filter height 30-60cm； Filtering velocity is 5-15m/h.
Further, when the import and export pressure differential of more medium filter reaches 0.08MPa in the step (A), carry out Backwash.Combined using air-water and backwashed, first with air recoil, air intensity：10-18L/(m2S), backwashing time：2- 4min, filtering layer expansion rate：10-20%；Recoiled afterwards with water, backwash water intensity：8-15L/(m2S), backwashing time：5- 10min, filtering layer expansion rate：20-40%.
Further, for the step B under 5-30 DEG C of temperature conditionss, filtrate flow velocity is that (BV is bed body to 5-10BV/h Product), it is 800-1600BV per batch wastewater treatment capacity.
Further, NaOH-NaCl mixed solutions concentration is 2-12% in the step C, at a temperature of 30-60 DEG C with 0.5-2BV/h flow velocity carries out desorption and regeneration.
3. beneficial effect
Compared to prior art, beneficial effects of the present invention are：
(1) nano composite material of synchronous selective Phosphate Sorption and nitrate of the present invention has coupled quaternary ammoniated polymer supported The selective phosphorus removal property of selective absorption performance and Fe (III) oxide nano particles of the body to nitrate so that one kind absorption Material is the removal that can complete phosphorus and nitrate simultaneously；
(2) nano composite material of synchronous selective Phosphate Sorption and nitrate of the present invention is reusable, and regenerability is good It is good, high mechanical strength；
(3) in the nano composite material preparation process of synchronous selective Phosphate Sorption and nitrate of the present invention, by polyphenyl Quaternary amine base of the modification with long alkyl chain, selective absorption performance of the reinforced nano composite to nitrate anion on ethene carrier； It is by in-situ deposition reaction that Fe (III) oxide is immobilized in the duct of diameter polystyrene spheres, utilize diameter polystyrene spheres nanometer The mesh confinement effect in duct so that Fe (III) oxide forms nano particle, improves Fe (III) oxide to phosphate anion Absorption property and adsorption capacity；It is further strong simultaneously using the Donnan film preenrichment effects of quaternary ammoniated diameter polystyrene spheres Change removal effect of the nano composite material to phosphorus and nitrate；
(4) nanocomposite applications of synchronous selective Phosphate Sorption and nitrate of the present invention are in the processing of biochemical sewage tail water In so that the removal of phosphorus and nitrate can be synchronously completed in a kind of sorbing material, and its selectivity to phosphorus and nitrate is kept away Exempt from the coexisting substances such as other anion (sulfate radical, chlorion, carbonate etc.) in biochemical tail water and compete limited ion friendship Exchange point, the situation for causing the removal efficiency of phosphorus and nitrate to decline to a great extent, shown in the processing of biochemical sewage tail water excellent Phosphorus and nitrate synchronous removal effect, and at present most of absorption/ion exchange material be only applicable to phosphorus or nitrate Independent removal, as needed denitrogenation dephosphorizing simultaneously during practical application, then need two sections of independent operating units, cause to invest and run High expensive, it is of the invention then adsorption operations flow is greatly reduced, reduce investment and operating cost；
(5) nano composite material of synchronous selective Phosphate Sorption and nitrate of the present invention is in the processing of biochemical sewage tail water Using more medium filter is placed in filtering from anthracite and quartz sand as filter medium, big particle diameter, the anthracite of low-density The top of device, be advantageous to first remove the suspended impurity of bulky grain in sewage, reduce the filtering load of quartzy sand filter blanket；Granule Footpath, highdensity quartz sand are placed in the bottom of filter, are advantageous to further remove sewage small particles colloid and suspension, together When, the anthracite of low-density is placed in the top of filter, and highdensity quartz sand is placed in the bottom of filter, can ensure that filter In backwash, filtrate will not random layer, and double design of filtering layer of anthracite and quartz sand, it is ensured that biochemical tail water has higher mistake Filtering velocity degree, and Media density etc. is controlled by, ensure preferable treatment effect, use aqueous suspension particulate matter (SS) concentration and be less than 5mg/L, turbidity are less than 3NTU, it is ensured that nano composite material adsorption tower will not be suspended thing blocking；
(6) nano composite material of synchronous selective Phosphate Sorption and nitrate of the present invention is in the processing of biochemical sewage tail water Using, light concentration desorption liquid be used to preparing NaOH-NaCl solution cover it is concentrated for next group desorption manipulation, high concentration desorption liquid It is used for the recycling of phosphorus and nitrate afterwards, realizes cycle applications, be effectively saved processing cost；
(7) nano composite material of synchronous selective Phosphate Sorption and nitrate of the present invention is in the processing of biochemical sewage tail water Using, be 6.0-9.0 in the pH scopes of biochemical treatment system secondary clarifier effluent, containing phosphorus, nitrate and sulfate radical, chlorine from Under conditions of the counter anions such as son, carbonate, water outlet TP is stably down to below 0.5mg/L, NO after making processing3-- N is stably down to Below 5mg/L, important leverage is provided for the advanced treating and comprehensive utilization of sewage, realizes the system of environmental benefit and social benefit One；
(8) nano composite material of synchronous selective Phosphate Sorption and nitrate of the present invention is in the processing of biochemical sewage tail water Using treating capacity is big, and under conditions of preferable treatment effect is ensured, the biochemical tail of 800-1600 bed volumes can be handled per batch Water.
Embodiment
The present invention is further described below with reference to specific embodiment.
Embodiment 1
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 50g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 100mL deionized waters, Tri-n-butylamine solution 100mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 8h are then warming up to 10 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 20g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 15%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 10%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 8h after 60 DEG C, that is, the nano composite material is made.Will Sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.5mg/L, NO3-- N is 17.4mg/L) flow into multi-medium filtering Device, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.6g/mm3, particle diameter is 1.5mm, it is placed in filter material layer upper strata, filter height 70cm；Quartz sand relative density is 2.6g/mm3, particle diameter 0.9mm, it is placed in Filter material layer lower floor, filter height 40cm；Filtering velocity control is 10m/h.Water outlet suspended particulate substance (SS) concentration is less than 5mg/L, turbid Degree is less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：15L/(m2S), backwashing time：3min, filtering layer expansion rate：15%；Recoiled again with water, backwash water intensity：12L/(m2· S), backwashing time：7min, filtering layer expansion rate：30%.
By the nano composite material of 50mL synchronous selectives Phosphate Sorption and nitrate (the quaternary amine base of nano composite material modification For tri-n-butylamine, amino content 4mmoL/g, average pore size 25nm, Fe (III) oxide nano particles particle diameter is 10nm, Fe (III) weight percent content of oxide is 15%) it is fitted into the glass adsorption column of jacketed (32 × 260mm).Learn from else's experience be situated between more Filtrate after mass filter filtering passes through nano composite material bed, place in 10 ± 5 DEG C, with 500mL/h (10BV/h) flow velocity Reason amount is 60000mL/ batches (1200BV/ batches).After nano composite material is adsorbed, water outlet TP is down to 0.34mg/L, NO3-- N is down to 4.1mg/L。
Stop absorption when absorption reaches breakthrough point, successively with 50mL 12% NaOH-NaCl mixed solutions and 100mL 2% NaOH-NaCl mixed solutions, 300mL running water is at a temperature of 45 ± 5 DEG C, with 50mL/h (1BV/h) flow velocity following current It is desorbed by nano composite material bed.The concentrated rear use of high concentration desorption liquid (preceding 150mL desorption liquids) being desorbed In the recycling of phosphorus and nitrate, light concentration desorption liquid (rear 300mL desorption liquids) is used to prepare NaOH-NaCl solution and cover to be used for Next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.
Embodiment 2
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 80g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 150mL deionized waters, Tripropyl amine (TPA) solution 150mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 6h are then warming up to 15 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 30g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 10%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 8%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 6h after 60 DEG C, that is, the nano composite material is made.
By sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.2mg/L, NO3-- N is 14.4mg/L) flow into More medium filter, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.4g/ mm3, particle diameter 2mm, it is placed in filter material layer upper strata, filter height 100cm；Quartz sand relative density is 2.8g/mm3, particle diameter is 0.6mm, it is placed in filter material layer lower floor, filter height 30cm；Filtering velocity control is 15m/h, and water outlet suspended particulate substance (SS) concentration is small In 5mg/L, turbidity is less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：10L/(m2S), backwashing time：4min, filtering layer expansion rate：10%；Recoiled again with water, backwash water intensity：15L/(m2· S), backwashing time：5min, filtering layer expansion rate：40%.
By the nano composite material of the 200mL synchronous selectives Phosphate Sorption and nitrate (quaternary amine of nano composite material modification Base is tripropyl amine (TPA), and amino content 4.5mmoL/g, average pore size 10nm, Fe (III) oxide nano particles particle diameter is 5nm, The weight percent content of Fe (III) oxide is 10%) it is fitted into the glass adsorption column of jacketed (64 × 320mm).Learn from else's experience more Filtrate after medium filter filtering is in 15 ± 5 DEG C, with 1400mL/h (7BV/h) flow velocity by nano composite material bed, Treating capacity is 260000mL/ batches (1300BV/ batches).After nano composite material is adsorbed, water outlet TP is down to 0.32mg/L, NO3--N It is down to 3.9mg/L.
Stop absorption when absorption reaches breakthrough point, successively with 200mL 10% NaOH-NaCl mixed solutions and 400mL 4% NaOH-NaCl mixed solutions, 1200mL running water is at a temperature of 55 ± 5 DEG C, with 300mL/h (1.5BV/h) flow velocity It is desorbed downstream through nano composite material bed.The high concentration desorption liquid (preceding 600mL desorption liquids) being desorbed is concentrated It is used for the recycling of phosphorus and nitrate afterwards, light concentration desorption liquid (rear 1200mL desorption liquids) is used to prepare NaOH-NaCl solution Cover and be used for next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.
Embodiment 3
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 100g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 200mL deionized waters, Triethylamine solution 200mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 4h are then warming up to 20 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 50g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 5%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 5%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 4h after 60 DEG C, that is, the nano composite material is made.
By sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.8mg/L, NO3-- N is 18.8mg/L) flow into More medium filter, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.8g/ mm3, particle diameter 1mm, it is placed in filter material layer upper strata, filter height 40cm；Quartz sand relative density is 2.4g/mm3, particle diameter is 1.2mm, it is placed in filter material layer lower floor, filter height 60cm；Filtering velocity control is 5m/h, and water outlet suspended particulate substance (SS) concentration is less than 5mg/L, turbidity are less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：18L/(m2S), backwashing time：2min, filtering layer expansion rate：20%；Recoiled again with water, backwash water intensity：8L/(m2· S), backwashing time：10min, filtering layer expansion rate：20%.
By the nano composite material of the 500mL synchronous selectives Phosphate Sorption and nitrate (quaternary amine of nano composite material modification Base is triethylamine, and amino content 5mmoL/g, average pore size 5nm, Fe (III) oxide nano particles particle diameter is 2nm, Fe (III) weight percent content of oxide is 5%) it is fitted into the glass adsorption column of jacketed (100 × 360mm).Learn from else's experience be situated between more Filtrate after mass filter filtering passes through nano composite material bed, place in 25 ± 5 DEG C, with 4000mL/h (8BV/h) flow velocity Reason amount is 400000mL/ batches (800BV/ batches).After nano composite material is adsorbed, water outlet water outlet TP is down to 0.43mg/L, NO3--N It is down to 4.1mg/L.
Stop absorption when absorption reaches breakthrough point, successively with 500mL 8% NaOH-NaCl mixed solutions and 1000mL 6% NaOH-NaCl mixed solutions, 3000mL running water is at a temperature of 35 ± 5 DEG C, with 1000mL/h (2BV/h) flow velocity It is desorbed downstream through nano composite material bed.The high concentration desorption liquid (preceding 1500mL desorption liquids) being desorbed is concentrated It is used for the recycling of phosphorus and nitrate afterwards, light concentration desorption liquid (rear 3000mL desorption liquids) is used to prepare NaOH-NaCl solution Cover and be used for next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.
Embodiment 4
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 100g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 200mL deionized waters, Tri-n-butylamine solution 200mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 8h are then warming up to 20 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 50g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 20%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 10%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 8h after 60 DEG C, that is, the nano composite material is made.
By sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.4mg/L, NO3-- N is 16.2mg/L) flow into More medium filter, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.6g/ mm3, particle diameter 1.5mm, it is placed in filter material layer upper strata, filter height 70cm；Quartz sand relative density is 2.6g/mm3, particle diameter is 0.9mm, it is placed in filter material layer lower floor, filter height 40cm；Filtering velocity control is 12m/h, and water outlet suspended particulate substance (SS) concentration is small In 5mg/L, turbidity is less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：15L/(m2S), backwashing time：3min, filtering layer expansion rate：15%；Recoiled again with water, backwash water intensity：12L/(m2· S), backwashing time：7min, filtering layer expansion rate：30%.
By the nano composite material of the 200mL synchronous selectives Phosphate Sorption and nitrate (quaternary amine of nano composite material modification Base is tri-n-butylamine, and amino content 4mmoL/g, average pore size 50nm, Fe (III) oxide nano particles particle diameter is 20nm, Fe (III) weight percent content of oxide is 20%) it is fitted into the glass adsorption column of jacketed (64 × 320mm).Learn from else's experience be situated between more Filtrate after mass filter filtering passes through nano composite material bed, place in 15 ± 5 DEG C, with 1600mL/h (8BV/h) flow velocity Reason amount is 200000mL/ batches (1200BV/ batches).After nano composite material is adsorbed, water outlet TP is down to 0.37mg/L, NO3-- N drops To 3.8mg/L.
Stop absorption when absorption reaches breakthrough point, successively with 200mL 10% NaOH-NaCl mixed solutions and 400mL 4% NaOH-NaCl mixed solutions, 1200mL running water are suitable with 200mL/h (1BV/h) flow velocity at a temperature of 45 ± 5 DEG C Stream is desorbed by nano composite material bed.After the high concentration desorption liquid (preceding 600mL desorption liquids) that is desorbed is concentrated For the recycling of phosphorus and nitrate, light concentration desorption liquid (rear 1200mL desorption liquids) is used to prepare NaOH-NaCl solution sets For next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.
Embodiment 5
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 80g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 150mL deionized waters, Tripropyl amine (TPA) solution 150mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 6h are then warming up to 15 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 30g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 10%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 8%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 6h after 60 DEG C, that is, the nano composite material is made.
By sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.1mg/L, NO3-- N is 13.6mg/L) flow into More medium filter, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.4g/ mm3, particle diameter 1.8mm, it is placed in filter material layer upper strata, filter height 90cm；Quartz sand relative density is 2.8g/mm3, particle diameter is 0.6mm, it is placed in filter material layer lower floor, filter height 30cm；Filtering velocity control is 10m/h, and water outlet suspended particulate substance (SS) concentration is small In 5mg/L, turbidity is less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：12L/(m2S), backwashing time：4min, filtering layer expansion rate：12%；Recoiled again with water, backwash water intensity：15L/(m2· S), backwashing time：6min, filtering layer expansion rate：38%.
By the nano composite material of the 500mL synchronous selectives Phosphate Sorption and nitrate (quaternary amine of nano composite material modification Base is tripropyl amine (TPA), and amino content 4.5mmoL/g, average pore size 10nm, Fe (III) oxide nano particles particle diameter is 5nm, The weight percent content of Fe (III) oxide is 10%) it is fitted into the glass adsorption column of jacketed (100 × 360mm).Learn from else's experience Filtrate after more medium filter filtering passes through nano composite material bed in 25 ± 5 DEG C with 2500mL/h (5BV/h) flow velocity Layer, treating capacity are 800000mL/ batches (1600BV/ batches).After nano composite material is adsorbed, water outlet water outlet TP is down to 0.38mg/ L, NO3-- N is down to 4.1mg/L.
Stop absorption when absorption reaches breakthrough point, successively with 500mL 8% NaOH-NaCl mixed solutions and 1000mL 6% NaOH-NaCl mixed solutions, 3000mL running water is at a temperature of 50 ± 5 DEG C, with 250mL/h (0.5BV/h) flow velocity It is desorbed downstream through nano composite material bed.The high concentration desorption liquid (preceding 1500mL desorption liquids) being desorbed is concentrated It is used for the recycling of phosphorus and nitrate afterwards, light concentration desorption liquid (rear 3000mL desorption liquids) is used to prepare NaOH-NaCl solution Cover and be used for next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.
Embodiment 6
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 100g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 200mL deionized waters, Triethylamine solution 200mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 4h are then warming up to 20 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 50g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 5%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 5%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 4h after 60 DEG C, that is, the nano composite material is made.
By sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.3mg/L, NO3-- N is 19.3mg/L) flow into More medium filter, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.8g/ mm3, particle diameter 1.2mm, it is placed in filter material layer upper strata, filter height 60cm；Quartz sand relative density is 2.4g/mm3, particle diameter is 1.0mm, it is placed in filter material layer lower floor, filter height 50cm；Filtering velocity control is 15m/h, and water outlet suspended particulate substance (SS) concentration is small In 5mg/L, turbidity is less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：18L/(m2S), backwashing time：2min, filtering layer expansion rate：20%；Recoiled again with water, backwash water intensity：10L/(m2· S), backwashing time：8min, filtering layer expansion rate：25%.
By the nano composite material of 50mL synchronous selectives Phosphate Sorption and nitrate (the quaternary amine base of nano composite material modification For triethylamine, amino content 5mmoL/g, average pore size 5nm, Fe (III) oxide nano particles particle diameter is 2nm, Fe (III) The weight percent content of oxide is 5%) to be fitted into the glass adsorption column of jacketed (32 × 260mm).Learn from else's experience multimedium mistake Filtrate after filter filtering passes through nano composite material bed, treating capacity in 10 ± 5 DEG C with 500mL/h (10BV/h) flow velocity For 60000mL/ batches (1200BV/ batches).After nano composite material is adsorbed, water outlet TP is down to 0.34mg/L, NO3-- N is down to 4.4mg/L。
Stop absorption when absorption reaches breakthrough point, successively with 50mL 12% NaOH-NaCl mixed solutions and 100mL 2% NaOH-NaCl mixed solutions, 300mL running water is at a temperature of 45 ± 5 DEG C, with 50mL/h (1BV/h) flow velocity following current It is desorbed by nano composite material bed.The concentrated rear use of high concentration desorption liquid (preceding 150mL desorption liquids) being desorbed In the recycling of phosphorus and nitrate, light concentration desorption liquid (rear 300mL desorption liquids) is used to prepare NaOH-NaCl solution and cover to be used for Next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.
Embodiment 7
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 50g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 100mL deionized waters, Tri-n-butylamine solution 100mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 8h are then warming up to 10 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 20g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 15%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 10%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 8h after 60 DEG C, that is, the nano composite material is made.
By sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.4mg/L, NO3-- N is 15.6mg/L) flow into More medium filter, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.6g/ mm3, particle diameter 1.5mm, it is placed in filter material layer upper strata, filter height 70cm；Quartz sand relative density is 2.6g/mm3, particle diameter is 0.9mm, it is placed in filter material layer lower floor, filter height 40cm；Filtering velocity control is 12m/h, and water outlet suspended particulate substance (SS) concentration is small In 5mg/L, turbidity is less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：15L/(m2S), backwashing time：3min, filtering layer expansion rate：15%；Recoiled again with water, backwash water intensity：12L/(m2· S), backwashing time：7min, filtering layer expansion rate：30%.
By the nano composite material of the 500mL synchronous selectives Phosphate Sorption and nitrate (quaternary amine of nano composite material modification Base is tri-n-butylamine, and amino content 4mmoL/g, average pore size 25nm, Fe (III) oxide nano particles particle diameter is 10nm, Fe (III) weight percent content of oxide is 15%) it is fitted into the glass adsorption column of jacketed (32 × 260mm).Learn from else's experience be situated between more Filtrate after mass filter filtering passes through nano composite material bed, place in 10 ± 5 DEG C, with 2500mL/h (5BV/h) flow velocity Reason amount is 800000mL/ batches (1600BV/ batches).After nano composite material is adsorbed, water outlet TP is down to 0.4mg/L, NO3-- N is down to 4.2mg/L。
Stop absorption when absorption reaches breakthrough point, successively with 500mL 12% NaOH-NaCl mixed solutions and 1000mL2% NaOH-NaCl mixed solutions, 3000mL running water is at a temperature of 35 ± 5 DEG C, with 250mL/h (0.5BV/h) Flow velocity be desorbed downstream through nano composite material bed.The high concentration desorption liquid (preceding 1500mL desorption liquids) being desorbed Recycling after concentrated for phosphorus and nitrate, light concentration desorption liquid (rear 3000mL desorption liquids) are used to prepare NaOH- NaCl solution is covered for next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.
Embodiment 8
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 80g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 150mL deionized waters, Tripropyl amine (TPA) solution 150mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 6h are then warming up to 15 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 30g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 10%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 8%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 6h after 60 DEG C, that is, the nano composite material is made.
By sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.1mg/L, NO3-- N is 11.4mg/L) flow into More medium filter, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.4g/ mm3, particle diameter 1.8mm, it is placed in filter material layer upper strata, filter height 90cm；Quartz sand relative density is 2.8g/mm3, particle diameter is 0.6mm, it is placed in filter material layer lower floor, filter height 30cm；Filtering velocity control is 10m/h, and water outlet suspended particulate substance (SS) concentration is small In 5mg/L, turbidity is less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：12L/(m2S), backwashing time：4min, filtering layer expansion rate：12%；Recoiled again with water, backwash water intensity：15L/(m2· S), backwashing time：6min, filtering layer expansion rate：38%.
By the nano composite material of 50mL synchronous selectives Phosphate Sorption and nitrate (the quaternary amine base of nano composite material modification For tripropyl amine (TPA), amino content 4.5mmoL/g, average pore size 10nm, Fe (III) oxide nano particles particle diameter is 5nm, Fe (III) weight percent content of oxide is 10%) it is fitted into the glass adsorption column of jacketed (32 × 260mm).Learn from else's experience be situated between more Filtrate after mass filter filtering passes through nano composite material bed, place in 10 ± 5 DEG C, with 500mL/h (10BV/h) flow velocity Reason amount is 60000mL/ batches (1200BV/ batches).After nano composite material is adsorbed, water outlet TP is down to 0.29mg/L, NO3-- N is down to 3.2mg/L。
Stop absorption when absorption reaches breakthrough point, successively with 50mL 12% NaOH-NaCl mixed solutions and 100mL 2% NaOH-NaCl mixed solutions, 300mL running water are suitable with 100mL/h (2BV/h) flow velocity at a temperature of 45 ± 5 DEG C Stream is desorbed by nano composite material bed.After the high concentration desorption liquid (preceding 150mL desorption liquids) that is desorbed is concentrated For the recycling of phosphorus and nitrate, light concentration desorption liquid (rear 300mL desorption liquids) is applied mechanically for preparing NaOH-NaCl solution In next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.
Embodiment 9
The nano composite material of synchronous selective Phosphate Sorption and nitrate is prepared first, and preparation process is as follows：
(1) 100g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken into 200mL deionized waters, Tri-n-butylamine solution 200mL is added at 10 DEG C, 60 DEG C, and insulated and stirred reaction 8h are then warming up to 20 DEG C/h speed；Reaction After the completion of, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to which quaternary ammoniated nano-pore polystyrene microsphere be made；
(2) quaternary ammoniated polystyrene microsphere 50g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixing is molten (FeCl in liquid3Mass concentration be 20%, HCl mass concentration for 10%), stirring reaction 12h at 25 DEG C；
(3) step (2) reacted polystyrene microsphere is filtered out, added into 200mL NaOH+NaCl mixed solutions (mass concentration that NaOH mass concentration is 10%, NaCl is 5%) stirring reaction 12h at 25 DEG C；
(4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then use deionization Water is rinsed to water outlet in neutrality, is finally infiltrated with absolute ethyl alcohol and is dried 8h after 60 DEG C, that is, the nano composite material is made.
By sanitary sewage plant biochemical treatment system secondary clarifier effluent (TP 1.9mg/L, NO3-- N is 19.4mg/L) flow into More medium filter, for filter from anthracite and quartz sand as filter medium, wherein anthracite relative density is 1.8g/ mm3, particle diameter 1.2mm, it is placed in filter material layer upper strata, filter height 60cm；Quartz sand relative density is 2.4g/mm3, particle diameter is 1.0mm, it is placed in filter material layer lower floor, filter height 50cm；Filtering velocity control is 15m/h, and water outlet suspended particulate substance (SS) concentration is small In 5mg/L, turbidity is less than 3NTU.
When the import and export pressure differential of sand filter reaches 0.08MPa, backwashed.First use air recoil, air is strong Degree：18L/(m2S), backwashing time：2min, filtering layer expansion rate：20%；Recoiled again with water, backwash water intensity：10L/(m2· S), backwashing time：8min, filtering layer expansion rate：25%.
By the nano composite material of the 200mL synchronous selectives Phosphate Sorption and nitrate (quaternary amine of nano composite material modification Base is tri-n-butylamine, and amino content 4mmoL/g, average pore size 50nm, Fe (III) oxide nano particles particle diameter is 20nm, Fe (III) weight percent content of oxide is 20%) it is fitted into the glass adsorption column of jacketed (64 × 320mm).Learn from else's experience be situated between more Filtrate after mass filter filtering passes through nano composite material bed, place in 15 ± 5 DEG C, with 1600mL/h (8BV/h) flow velocity Reason amount is 180000mL/ batches (900BV/ batches).After nano composite material is adsorbed, water outlet TP is down to 0.45mg/L, NO3-- N is down to 4.7mg/L。
Stop absorption when absorption reaches breakthrough point, successively with 200mL 10% NaOH-NaCl mixed solutions and 400mL 4% NaOH-NaCl mixed solutions, 1200mL running water is at a temperature of 55 ± 5 DEG C, with 300mL/h (1.5BV/h) flow velocity It is desorbed downstream through nano composite material bed.The high concentration desorption liquid (preceding 600mL desorption liquids) being desorbed is concentrated It is used for the recycling of phosphorus and nitrate afterwards, light concentration desorption liquid (rear 1200mL desorption liquids) is used to prepare NaOH-NaCl solution Cover and be used for next group desorption manipulation.
Desorption efficiency >=95% of nano composite material, adsorption capacity declines≤10% after regeneration；Longtime running, which has no, to be received The Fragmentation Phenomena of nano composite material, stable effluent quality, illustrate that the mechanical strength is high, technology stability is good.

Claims (10)

  1. A kind of 1. nano composite material of synchronous selective Phosphate Sorption and nitrate, it is characterised in that：Its carrier is quaternary ammoniated Nano-pore diameter polystyrene spheres, Fe (III) oxide nano particles are evenly distributed with hole.
  2. 2. the nano composite material of synchronous selective Phosphate Sorption according to claim 1 and nitrate, it is characterised in that：Institute The quaternary amine base for the diameter polystyrene spheres surface modification stated is triethylamine, tripropyl amine (TPA) or tri-n-butylamine, amine groups content 4-5mmoL/g.
  3. 3. the nano composite material of synchronous selective Phosphate Sorption according to claim 1 or 2 and nitrate, its feature exist In：The average pore size of described diameter polystyrene spheres is 5-50nm, and described Fe (III) oxide nano particles particle diameter is 2- 20nm, the weight percent content of Fe (III) oxide is 5-20% (in terms of Fe).
  4. 4. the nano composite material of synchronous selective Phosphate Sorption according to claim 3 and nitrate, it is characterised in that：Its Preparation comprises the following steps：
    (1) 50-100g chloromethylated polystyrenes microballoon (mass concentration of chlorine is 18%) is taken to 100-200mL deionized waters In, triethylamine, tripropyl amine (TPA) or tri-n-butylamine solution 100-200mL are added at 10 DEG C, is then warming up to 10-20 DEG C/h speed 60 DEG C, and insulated and stirred reaction 4-8h；After the completion of reaction, polystyrene microsphere is filtered out and dries 12h in 60 DEG C, so as to be made Quaternary ammoniated nano-pore polystyrene microsphere；
    (2) quaternary ammoniated polystyrene microsphere 20-50g made from step (1) is taken, is added to 200mL FeCl3+ HCl mixed solution In (FeCl3Mass concentration be 5-20%, 10%) HCl mass concentration is, stirring reaction 12h at 25 DEG C；
    (3) step (2) reacted polystyrene microsphere is filtered out, adds (the NaOH into 200mL NaOH+NaCl mixed solutions Mass concentration be 5-10%, 5%) NaCl mass concentration is, stirring reaction 12h at 25 DEG C；
    (4) step (3) reacted polystyrene microsphere is filtered out, first rinsed with 5% NaCl solution, then rushed with deionized water Water outlet is washed till in neutrality, is finally infiltrated with absolute ethyl alcohol and dries 4-8h after 60 DEG C, that is, the nano composite material is made.
  5. 5. the nano composite material of a kind of the synchronous selective Phosphate Sorption and nitrate described in claim 1 is in biochemical sewage tail water Application in processing.
  6. 6. the nano composite material of a kind of synchronous selective Phosphate Sorption according to claim 5 and nitrate is in biochemical sewage Application in tail water processing, it is characterised in that：Comprise the following steps：
    A. biochemical wastewater treatment system secondary clarifier effluent is removed into colloid and suspended particulate in sewage by more medium filter Thing；
    B. by the filtrate in step (A), receiving for the synchronous selective Phosphate Sorption that is filled with described in claim 1 and nitrate is passed through The adsorption tower of nano composite material；
    C. absorption is stopped when absorption reaches breakthrough point, by the use of NaOH-NaCl mixed solutions as desorbing agent, to above-mentioned nano combined Material carries out desorption and regeneration, for recycling；
    D. light concentration desorption liquid step (C) obtained is covered for next group desorption manipulation for preparing NaOH-NaCl solution, high Recycling after concentration desorption liquid is concentrated for phosphorus and nitrate.
  7. 7. the nano composite material of a kind of synchronous selective Phosphate Sorption according to claim 6 and nitrate is in biochemical sewage Application in tail water processing, it is characterised in that：More medium filter is used as filtering from anthracite and quartz sand in the step A Medium, wherein anthracite relative density are 1.4-1.8g/mm3, particle diameter 1-2mm is placed in filter material layer upper strata, and filter height is 40-100cm；Quartz sand relative density is 2.4-2.8g/mm3, particle diameter 0.6-1.2mm, it is placed in filter material layer lower floor, filter height For 30-60cm；Filtering velocity is 5-15m/h.
  8. 8. the nano composite material of a kind of synchronous selective Phosphate Sorption according to claim 7 and nitrate is in biochemical sewage Application in tail water processing, it is characterised in that：The import and export pressure differential of more medium filter reaches in the step (A) During 0.08MPa, backwashed.Combined using air-water and backwashed, first with air recoil, air intensity：10-18L/(m2· S), backwashing time：2-4min；Recoiled afterwards with water, backwash water intensity：8-15L/(m2S), backwashing time：5-10min.
  9. 9. the nano composite material of a kind of synchronous selective Phosphate Sorption according to claim 6 and nitrate is in biochemical sewage Application in tail water processing, it is characterised in that：For the step B under 5-30 DEG C of temperature conditionss, filtrate flow velocity is 5-10BV/h (BV For bed volume), it is 800-1600BV per batch wastewater treatment capacity.
  10. 10. the nano composite material of a kind of synchronous selective Phosphate Sorption according to claim 6 and nitrate is given birth in sewage Change the application in tail water processing, it is characterised in that：NaOH-NaCl mixed solutions concentration is 2-12% in the step C, in 30- Desorption and regeneration is carried out with 0.5-2BV/h flow velocity at a temperature of 60 DEG C.
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