WO2020200215A1 - 一种磁化粉末强化的硝态氮和无机磷去除方法 - Google Patents

一种磁化粉末强化的硝态氮和无机磷去除方法 Download PDF

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WO2020200215A1
WO2020200215A1 PCT/CN2020/082655 CN2020082655W WO2020200215A1 WO 2020200215 A1 WO2020200215 A1 WO 2020200215A1 CN 2020082655 W CN2020082655 W CN 2020082655W WO 2020200215 A1 WO2020200215 A1 WO 2020200215A1
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Prior art keywords
water
nitrate nitrogen
magnetized
treated
powder
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French (fr)
Inventor
双陈冬
李爽爽
李彤
张光
李爱民
王珂
王钧田
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NANJING UNIVERSITY & YANCHENG ACADEMY OF ENVIRONMENTAL PROTECTION TECHNOLOGY AND ENGINEERING
Nanjing University
Nanjing Tech University
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NANJING UNIVERSITY & YANCHENG ACADEMY OF ENVIRONMENTAL PROTECTION TECHNOLOGY AND ENGINEERING
Nanjing University
Nanjing Tech University
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Priority to US17/599,919 priority Critical patent/US12024446B2/en
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    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • 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

Definitions

  • the invention belongs to the technical field of water treatment, and specifically relates to a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder.
  • the pollutants are not from the perspective of the natural environment. Get processed.
  • the reduction of zero-valent iron and ferrous iron has become a cost-effective removal method that has been widely studied due to its simple operation, small footprint and high reduction efficiency.
  • zero-valent iron, divalent iron, green embroidery and Fe 3 O 4 can be used as reducing agents for nitrate nitrogen.
  • the reaction efficiency and reaction products of these reductions are difficult to control. For most practical situations, the reduction products are mostly ammonia nitrogen.
  • the patent discloses a method for reducing nitrate in water, which utilizes the reducibility of green rust and the action of catalyst ions to reduce nitrate, which can significantly remove nitrate.
  • the literature mentions that the magnetic field can generate convection in the solution, enhance the transmission of substances, and stimulate the migration of paramagnetic ions to increase the reaction rate.
  • the patent (application number 201510237845.7) discloses a method for treating sewage using a magnetic field. It is proposed that a magnetic field can effectively increase the rate of pollutant removal, but generally the magnetic source has a small range and short distance, which is difficult to apply to large-scale reaction systems in actual engineering. cost.
  • the purpose of the present invention is to solve the problem that the magnetic field is difficult to be uniformly distributed in large-scale water treatment through the dispersion of hard magnetic powder on the basis of the prior art, and to provide a magnetic field-enhanced method for removing nitrate nitrogen and inorganic phosphorus. Efficient removal of nitrate nitrogen and total nitrogen, while removing inorganic phosphorus, simplifying the process and reducing costs.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder which includes the following steps:
  • the water to be treated enters the water treatment reaction vessel, and in the presence of the reducing agent, a chemical reaction to remove nitrate nitrogen and inorganic phosphorus is carried out, and the water after the reaction is discharged.
  • the invention provides a water treatment method that utilizes permanent magnet materials to provide a magnetic field and promotes the catalytic reduction of nitrate nitrogen to remove total nitrogen by a reducing agent, and the product can be further combined with inorganic phosphorus (phosphate) to coagulate and precipitate to remove inorganic phosphorus.
  • the catalytic reduction removal of nitrate nitrogen in the water to be treated and the degradation efficiency of total nitrogen basically exceed 80%, and the removal rate of inorganic phosphorus in the water to be treated basically exceeds 90%.
  • the Catalytic reduction removal and total nitrogen degradation efficiency reaches more than 90%.
  • step (1) the permanent magnetic material powder and the paramagnetic Fe 3 O 4 need to be mixed, so that it can be in the catalytic reaction position after being added to the water treatment reaction vessel.
  • the water treatment reaction vessel mentioned in the present invention may be a reactor or a reaction tank for water treatment.
  • the concentration of nitrate nitrogen in the water to be treated in the present invention is 40-500 mg/L.
  • the concentration of nitrate nitrogen in the water to be treated It is 80 to 300 mg/L, more preferably 200 to 250 mg/L.
  • step (3) before or after the water to be treated enters the water treatment reaction vessel, the reducing agent is added in batches or continuously, and the water to be treated enters the water treatment reaction vessel continuously, and one end enters the other One end is discharged, and the chemical reaction is carried out in the flow process; or, the water to be treated enters the water treatment reaction vessel and stays in the water treatment reaction vessel for a period of time for chemical reaction, and the water after the reaction is discharged.
  • the permanent magnetic material powder is one or more of rare earth permanent magnetic materials, metal permanent magnetic materials, or ferrite permanent magnetic materials.
  • the rare earth permanent magnet material can be one or more of Sm-Co series, Nd-Fe-B, La-Ce or Re-Fe-B; metal permanent magnet material It can be Al-Ni-Co, Fe-Cr-Co or a combination thereof; the ferrite permanent magnet material can be one or more of ⁇ -Fe 2 O 3 , BaFe 12 O 19 or SrFe 12 O 19 .
  • the mass ratio of the permanent magnetic material powder to the paramagnetic Fe 3 O 4 powder is 1:0.01 to 1:150; for example, without affecting the effect of the present invention , May preferably be 1:5 to 1:100, particularly preferably 1:10 to 1:40.
  • the ratio of the amount of the magnetized powder added in step (2) to the amount of nitrate nitrogen in the water to be treated in step (3) is 1:0.01 to 1:100; it does not affect the effect of the present invention In the case of, it may be preferably 1:10 to 1:100; more preferably 1:30 to 1:80.
  • the reducing agent added in step (3) of the present invention is a reducing substance that can react with nitrate nitrogen and the oxidation product has a coagulation effect, for example, elemental zerovalent iron, elemental zerovalent aluminum, elemental zerovalent zinc, elemental zero One or more of valence manganese, elemental zero valence magnesium, ferrous compounds, cuprous compounds, green embroidery or Fe 3 O 4 .
  • ferrous compounds mentioned in the present invention can be, but are not limited to, ferrous chloride, ferrous sulfate and ferrous hydroxide.
  • cuprous compounds mentioned in the present invention can be, but are not limited to, cuprous chloride, cuprous sulfate and cuprous hydroxide.
  • Patina (GR) according to the present invention may be mentioned, but not limited GR (SO 4 2-), GR (CO 3 2-), GR (Cl -) of one or GR (SO 3 2-) or several Kind.
  • the ratio of the amount of the reducing agent to the amount of nitrate nitrogen in the water to be treated is 1:0.1 to 1:150; if the effect of the present invention is not affected, it can be preferably 1 : 0.8 to 1:80, more preferably 1:10 to 1:50.
  • the water treatment reaction vessel mentioned in step (2) of the present invention may be provided with a mud discharge system at the bottom to regularly clean the iron mud generated when inorganic phosphorus is removed.
  • step (3) of the present invention the water to be treated entering the water treatment reaction vessel does not contain sodium hypochlorite, chloramine, ozone, sodium persulfate or potassium permanganate, or the strong oxidant in the water to be treated is pre-treated, otherwise it will It reacts with reducing agent and affects the reaction of reducing agent with nitrate nitrogen.
  • step (3) the reducing agent is added in batches or continuously to ensure the reduction of nitrate nitrogen.
  • the time for each batch of adding the reducing agent in the batch mentioned in the present invention is 5 min to 1000 min; preferably 30 min to 500 min.
  • the flow rate of the water to be treated continuously entering the water treatment reaction vessel mentioned in step (3) of the present invention is 0.1L/h to 1000L/h.
  • the residence time in the water treatment reaction vessel is 1 to 600 minutes; preferably 1 to 300 minutes; more preferably 1 to 50 minutes.
  • the stirring is mechanical stirring or hydraulic stirring.
  • the magnetized permanent magnetic material powder provides a magnetic field to provide a uniform and dense magnetic field in the water treatment reaction vessel, which improves the reaction efficiency and is beneficial to the catalytic reduction and removal of nitrate nitrogen and the degradation of total nitrogen.
  • Fe 3 O 4 powder can be used as a catalyst to increase the selectivity of total nitrogen removal, and the mixing of magnetized powder and reducing agent can improve the stability of the reduction system.
  • the dissolved iron ions produced after the reaction of the iron-based reducing agent during the reaction can be used as a coagulant to further remove inorganic phosphorus in the water to be treated, so as to achieve nitrogen and phosphorus removal.
  • Figure 1 is a schematic diagram of a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder of the present invention.
  • the water treatment reaction vessel mentioned in the present invention is a reactor or a reaction tank with a stirring device, water in one end and water out at the other end, which is convenient to pass in the water to be treated and discharge it in time after chemical reaction as needed. water.
  • the following embodiments all use the above-mentioned reactor or reaction tank.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • the reducing agent elemental zero-valent iron is continuously added, and the mechanical stirring is started at the same time.
  • the ratio of the amount of reducing agent to the amount of nitrate nitrogen in the water to be treated is 1:0.1.
  • the nitrate nitrogen in the water to be treated is 40mg/L
  • the nitrate nitrogen in the effluent is 14mg/L
  • the total phosphorus in the water to be treated is 3mg/L
  • the total phosphorus in the effluent is 0.4mg/L.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • the nitrate nitrogen in the water to be treated is 80mg/L
  • the nitrate nitrogen in the effluent is 12mg/L
  • the total phosphorus in the water to be treated is 3mg/L
  • the total phosphorus in the effluent is 0.2mg/L.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • La-Ce rare earth permanent magnetic powder and paramagnetic Fe 3 O 4 powder are mixed at a mass ratio of 1:1 to form a mixed powder, which is magnetized in a magnetic field to make a magnetized powder;
  • the reducing agent elemental zero-valent zinc is continuously added, and the hydraulic stirring is started at the same time.
  • the ratio of the amount of the reducing agent to the amount of nitrate nitrogen in the water to be treated is 1:3. Water enters the reactor continuously at a flow rate of 100L/h, and is discharged from the other end, and reacts during the flow.
  • the nitrate nitrogen in the water to be treated is 50mg/L
  • the nitrate nitrogen in the effluent is 4mg/L
  • the total phosphorus in the water to be treated is 5mg/L
  • the total phosphorus in the effluent is 0.1mg/L.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • the above-mentioned magnetized powder is prepared into granular filler and added to the reaction tank, the ratio of the amount of the magnetized powder to the amount of nitrate nitrogen in the water to be treated is 1:10;
  • the nitrate nitrogen in the water to be treated is 100 mg/L
  • the nitrate nitrogen in the effluent is 11 mg/L
  • the total phosphorus in the water to be treated is 8 mg/L
  • the total phosphorus in the effluent is 0.4 mg/L.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • the Al-Ni-Co metal permanent magnetic powder and the paramagnetic Fe 3 O 4 powder are mixed with a mass ratio of 1:10 to form a mixed powder, which is magnetized in a magnetic field to form a magnetized powder;
  • the nitrate nitrogen in the water to be treated is 60mg/L
  • the nitrate nitrogen in the effluent is 4mg/L
  • the total phosphorus in the water to be treated is 9mg/L
  • the total phosphorus in the effluent is 0.3mg/L.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • the reducing agent ferrous chloride is added in batches, every 500 minutes is a batch, and the hydraulic stirring is started at the same time.
  • the total amount of the reducing agent and the nitrate nitrogen in the water to be treated The amount ratio is 1:30.
  • the water to be treated enters the reactor and stays for a period of time for chemical reaction. The residence time is 30 minutes, and the water after the reaction is discharged.
  • the nitrate nitrogen in the water to be treated is 200mg/L
  • the nitrate nitrogen in the effluent is 13mg/L
  • the total phosphorus in the water to be treated is 15mg/L
  • the total phosphorus in the effluent is 0.2mg/L.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • the ⁇ -Fe 2 O 3 ferrite permanent magnetic powder and the paramagnetic Fe 3 O 4 powder are mixed with a mass ratio of 1:40 to form a mixed powder, which is magnetized in a magnetic field to produce a magnetized powder;
  • the nitrate nitrogen in the water to be treated is 80mg/L
  • the nitrate nitrogen in the effluent is 7mg/L
  • the total phosphorus in the water to be treated is 20mg/L
  • the total phosphorus in the effluent is 0.4mg/L.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • the nitrate nitrogen in the water to be treated is 120mg/L
  • the nitrate nitrogen in the effluent is 13mg/L
  • the total phosphorus in the water to be treated is 8mg/L
  • the total phosphorus in the effluent is 0.2mg/L.
  • a method for removing nitrate nitrogen and inorganic phosphorus enhanced by magnetized powder comprising the following steps:
  • the nitrate nitrogen in the water to be treated is 250 mg/L
  • the nitrate nitrogen in the effluent is 14 mg/L
  • the total phosphorus in the water to be treated is 10 mg/L
  • the total phosphorus in the effluent is 0.2 mg/L.

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract

一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：(1)将永磁材料粉末与顺磁Fe 3O 4粉末混合后，置于磁场中进行磁化，制成磁化粉末；(2)将磁化粉末直接或制成颗粒状填料加入水处理反应容器中；(3)待处理水进入水处理反应容器中，在还原剂存在的条件下，进行去除硝态氮和无机磷的化学反应，完成反应后的水排出即可。

Description

一种磁化粉末强化的硝态氮和无机磷去除方法 技术领域
本发明属于水处理技术领域，具体涉及一种磁化粉末强化的硝态氮和无机磷去除方法。
背景技术
随着人口的增长和工业化、城市化进程的加快，自然界水体中的氮素具有高度硝化的趋势，其在水体中可转化为亚硝胺等物质，对生态环境、动植物以及人体生命健康造成威胁，世界卫生组织和多个国家、地区都对其制定了污染限制指标。从报道或公开情况来看，世界各地地表水、地下水、饮用水、废水的硝态氮超标情况较为严重。
在废水处理中，最为常见的硝酸盐去除方法是反硝化法，其缺陷在于反硝化细菌需要一定的温度和可生化的碳源，因此，在温度较低地区或者碳源不足的废水难以规模化推广应用，升高温度和补充碳源则会导致成本大幅增加。而且，该方法对于地表水、地下水、饮用水并不适用。常规的物理化学方法主要有反渗透、离子交换、和还原法等，各技术均有其优缺点。反渗透和离子交换法都是分离法，并未从根本上消除硝酸盐，而仅仅是通过物理、化学作用将污染物分离出来，如不采取进一步处理，从自然环境角度来看污染物并未得到处理。零价铁和亚铁还原由于其操作简单、占地面积小和还原效率高成为广泛研究关注的一种经济高效的去除方法。其中，零价铁、二价铁、绿绣和Fe 3O 4等均可作为硝态氮的还原剂。但这些还原的反应效率和反应产物均较难控制，对于大部分实际情形，其还原产物多为氨氮。
专利(申请号201310505699.2)所公开的一种还原处理水中硝酸盐的方法，利用绿锈的还原性和催化剂离子的作用对硝酸盐进行还原处理，对硝酸盐具有显著的去除。但对于总氮的去除，仍存在提升的空间，而且其对总磷的去除也并未涉及。文献(Environ.Sci.Technol.,2015,49(24),14401-14408)中提到磁场能使溶液中产生对流，增强物质的传输，且刺激顺磁离子迁移，提高反应速率。专利(申请号201510237845.7)公开的利用磁场处理污水的方法，提出磁场能够有效提高去除污染物的速率，但一般磁源作用范围小、距离短，在实际工程中难以适用于大规模反应体系，增加成本。
发明内容
本发明的目的是在现有技术的基础上，通过硬磁粉末的分散解决了磁场难以在大规模水处理中均匀分布的难题，提供一种磁场强化的硝态氮和无机磷去除方法，实现硝态氮和总氮的高效去除，同时去除无机磷，简化工艺和降低成本。
本发明的技术方案如下：
一种磁化粉末强化的硝态氮和无机磷去除方法，它包括以下步骤：
(1)将永磁材料粉末与顺磁Fe 3O 4粉末混合后，置于磁场中进行磁化，制成磁化粉末；
(2)将磁化粉末直接或制成颗粒状填料加入水处理反应容器中；
(3)待处理水进入水处理反应容器中，在还原剂存在的条件下，进行去除硝态氮和无机磷的化学反应，完成反应后的水排出即可。
本发明提供了一种利用永磁材料提供磁场，并促进还原剂催化还原硝态氮去除总氮，其产物可以进一步与无机磷(磷酸根)结合混凝沉淀去除无机磷的水处理方法。其中，待处理水中硝态氮的催化还原去除和总氮的降解效率基本上超过80％，待处理水中的无机磷的去除率基本上超过90％，在一些优选的方案中，硝态氮的催化还原去除和总氮的降解效率达到90％以上。
本发明提供的去除水中硝态氮和无机磷的方法，在步骤(1)中，永磁材料粉末与顺磁Fe 3O 4需混合，以便在后续加入水处理反应容器中能在催化反应位点附近提供均匀细密的磁场。本发明提及的水处理反应容器可以是进行水处理的反应器或者反应池。
在一种方案中，本发明所提及的待处理水中硝态氮的浓度为40～500mg/L，在其他条件的配合下，在一种优选的方案中，待处理水中硝态氮的浓度为80～300mg/L，更进一步优选为200～250mg/L。
在一种优选方案中，在步骤(3)中，在待处理水进入水处理反应容器之前或之后，批次或连续加入还原剂，待处理水连续式进入水处理反应容器中，一端进入另一端排出，在流动过程中进行化学反应；或者，待处理水进入水处理反应容器中，在水处理反应容器中停留一段时间进行化学反应，完成反应后的水排出即可。
在一种方案中，永磁材料粉末为稀土永磁材料、金属永磁材料或铁氧体永磁材料中的一种或几种。例如，在不影响本发明效果的情况下，稀土永磁材料可以为Sm-Co系、Nd-Fe-B、La-Ce或Re-Fe-B中的一种或几种；金属永磁材料可以为Al-Ni-Co、Fe-Cr-Co或者其组合物；铁氧体永磁材料可以为α-Fe 2O 3、BaFe 12O 19或SrFe 12O 19中的一种或几种。
在一种更优选方案中，在步骤(1)中，永磁材料粉末与顺磁Fe 3O 4粉末的质量比为1:0.01～1:150；例如，在不影响本发明效果的情况下，可以优选为1:5～1:100，特别优选为1:10～1:40。
在一种优选方案中，在步骤(2)中加入的磁化粉末与步骤(3)中待处理水中硝态氮的物质的量之比为1:0.01～1:100；在不影响本发明效果的情况下，可以优选为1:10～1:100；更优选为1:30～1:80。
本发明在步骤(3)中加入的还原剂为能与硝态氮反应且氧化产物具有混凝效果的还原性物质，例如，单质零价铁、单质零价铝、单质零价锌、单质零价锰、单质零价镁、亚铁化合 物、亚铜化合物、绿绣或Fe 3O 4中的一种或几种。
本发明提及的亚铁化合物可以但不局限于氯化亚铁、硫酸亚铁和氢氧化亚铁。
本发明提及的亚铜化合物可以但不局限于氯化亚铜、硫酸亚铜和氢氧化亚铜。
本发明提及的绿锈(GR)可以但不局限于GR(SO 4 2-)、GR(CO 3 2-)、GR(Cl -)或GR(SO 3 2-)中的一种或几种。
进一步的，在步骤(3)中，还原剂的用量与待处理水中硝态氮的物质的量之比为1:0.1～1:150；在不影响本发明效果的情况下，可以优选为1:0.8～1:80，更优选为1:10～1:50。
在一种优选方案中，本发明在步骤(2)中提及的水处理反应容器，可以在底部设置有排泥系统，定时清理去除无机磷时产生的铁泥。
本发明在步骤(3)中，进入水处理反应容器中的待处理水中不含有次氯酸钠、氯胺、臭氧、过硫酸钠或高锰酸钾，或将待处理水中的强氧化剂预先处理，否则会与还原剂反应，影响还原剂与硝态氮的反应。
在一种优选方案中，在步骤(3)中，批次或连续加入还原剂，以保证对硝态氮的还原。
本发明提及的批次加入还原剂的每批次时间为5min～1000min；优选为30min～500min。
本发明在步骤(3)中提及的待处理水连续式进入水处理反应容器的流速为0.1L/h～1000L/h。
本发明提及的待处理水进入水处理反应容器后，在水处理反应容器中停留的时间为1～600分钟；优选为1～300分钟；更优选为1～50分钟。
进一步的，在步骤(3)中，搅拌为机械搅拌或水力搅拌。
采用本发明的技术方案，优势如下：
(1)磁化后的永磁材料粉末提供磁场，在水处理反应容器中提供均匀细密的磁场，提高了反应效率，有利于硝态氮的催化还原去除和总氮的降解。
(2)Fe 3O 4粉末可作为催化剂，增加对总氮去除的选择性，并且磁化粉末与还原剂的混合能提高还原体系的稳定性。
(3)在反应过程中铁系还原剂反应后产生的溶解态铁离子可以作为混凝剂进一步去除待处理水中的无机磷，实现脱氮除磷。
(4)整个催化还原反应在一个反应体系中完成，体系一端进水一端出水，占地面积小，且通过定时停水和投加还原剂，可恢复还原体系的活性，使反应体系持续循环使用，节省成本。
附图说明
图1是本发明的一种磁化粉末强化的硝态氮和无机磷去除方法的示意图。
具体实施方式
通过以下实施例并结合附图对本发明的磁化粉末强化的硝态氮和无机磷去除方法作进一步的说明，但这些实施例不对本发明构成任何限制。
如图1所示，本发明提及的水处理反应容器为具有搅拌装置，一端进水和另一端出水的反应器或者反应池，便于通入待处理水并按照需要及时排出进行化学反应后的水。以下实施例均采用上述提及的反应器或者反应池。
实施例1：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
(1)将Sm-Co系稀土永磁粉末与顺磁Fe 3O 4粉末以质量比1:0.01混合，形成混合粉末，并置于磁场中磁化，制成磁化粉末；
(2)将上述磁化粉末直接加入到反应器中，磁化粉末与待处理水中硝态氮的物质的量之比为1:0.01；
(3)在待处理水进入上述反应器前，连续式加入还原剂单质零价铁，同时开始机械搅拌，还原剂用量与待处理水中硝态氮的物质的量比例为1:0.1，待处理水以0.1L/h的流速连续进入反应器中，从另一端排出，在流动的过程中反应。
装置运行后，待处理水中硝态氮40mg/L，出水中硝态氮14mg/L，待处理水中总磷3mg/L，出水中总磷0.4mg/L。
实施例2：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
(1)将Nd-Fe-B稀土永磁粉末与顺磁Fe 3O 4粉末以质量比1:0.1混合，形成混合粉末，并置于磁场中磁化，制成磁化粉末；
(2)将上述磁化粉末直接加入到反应器中，磁化粉末与待处理水中硝态氮的物质的量之比为1:0.1；
(3)在待处理水进入上述反应器后，分批次加入还原剂单质零价铝，每5min为一批次，同时开始水力搅拌，还原剂用量与待处理水中硝态氮的物质的量比例为1:1，待处理水以5L/h的流速连续进入反应器中，从另一端排出，在流动的过程中反应。
装置运行后，待处理水中硝态氮80mg/L，出水中硝态氮12mg/L，待处理水中总磷进水3mg/L，出水中总磷0.2mg/L。
实施例3：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
经过以下步骤进行处理：
(1)将La-Ce稀土永磁粉末与顺磁Fe 3O 4粉末以质量比1:1混合，形成混合粉末，并置于磁场中磁化，制成磁化粉末；
(2)将上述磁化粉末制备成颗粒状填料加入到反应器中，磁化粉末与待处理水中硝态氮的物质的量之比为1:1；
(3)在待处理水进入上述反应器前，连续式加入还原剂单质零价锌，同时开始水力搅拌，还原剂用量与待处理水中硝态氮的物质的量比例为1:3，待处理水以100L/h的流速连续进入反应器中，从另一端排出，在流动的过程中反应。
装置运行后，待处理水中硝态氮50mg/L，出水中硝态氮4mg/L，待处理水中总磷5mg/L，出水中总磷0.1mg/L。
实施例4：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
经过以下步骤进行处理：
(1)将Re-Fe-B稀土永磁粉末与顺磁Fe 3O 4粉末以质量比1:5混合，形成混合粉末，并置于磁场中磁化，制成磁化粉末；
(2)将上述磁化粉末制备成颗粒状填料加入到反应池中，磁化粉末与待处理水中硝态氮的物质的量之比为1:10；
(3)在待处理水进入上述反应池前，连续式加入还原剂单质零价锰和单质零价镁(物质的量比例为1:1)，同时开始机械搅拌，还原剂总用量与待处理水中硝态氮的物质的量比例为1:8，待处理水以1000L/h的流速连续进入反应池中，从另一端排出，在流动的过程中反应。
装置运行后，待处理水中硝态氮100mg/L，出水中硝态氮11mg/L，待处理水中总磷8mg/L，出水中总磷0.4mg/L。
实施例5：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
经过以下步骤进行处理：
(1)将Al-Ni-Co金属永磁粉末与顺磁Fe 3O 4粉末以质量比1:10混合，形成混合粉末，并置于磁场中磁化，制成形成磁化粉末；
(2)将上述磁化粉末直接加入到反应池中，磁化粉末与待处理水中硝态氮的物质的量之比为1:30；
(3)在待处理水进入上述反应池后，分批次加入还原剂单质铁和单质铝(物质的量比例为1:100)，每100min为一批次，同时开始机械搅拌，还原剂用量与待处理水中硝态氮的物质的量比例为1:10，待处理水进入反应池中停留一段时间进行化学反应，停留的时间为1分钟， 完成反应后的水排出。
装置运行后，待处理水中硝态氮60mg/L，出水中硝态氮4mg/L，待处理水中总磷9mg/L，出水中总磷0.3mg/L。
实施例6：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
经过以下步骤进行处理：
(1)将Fe-Cr-Co金属永磁粉末与顺磁Fe 3O 4粉末以质量比1:20混合，形成混合粉末，并置于磁场中磁化，制成磁化粉末；
(2)将上述磁化粉末直接加入到反应器中，磁化粉末与待处理水中硝态氮的物质的量之比为1:50；
(3)在待处理水进入上述反应器后，分批次加入还原剂氯化亚铁，每500min为一批次，同时开始水力搅拌，还原剂总用量与待处理水中硝态氮的物质的量比例为1:30，待处理水进入反应器中停留一段时间进行化学反应，停留的时间为30分钟，完成反应后的水排出。
装置运行后，待处理水中硝态氮200mg/L，出水中硝态氮13mg/L，待处理水中总磷15mg/L，出水中总磷0.2mg/L。
实施例7：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
经过以下步骤进行处理：
(1)将α-Fe 2O 3铁氧体永磁粉末与顺磁Fe 3O 4粉末以质量比1:40比例混合，形成混合粉末，并置于磁场中磁化，制成磁化粉末；
(2)将上述磁化粉末制备成颗粒状填料加入到反应器中，磁化粉末与待处理水中硝态氮的物质的量之比为1:80；
(3)在待处理水进入上述反应器前，连续式加入还原剂GR(Cl -)，同时开始水力搅拌，还原剂总用量与待处理水中硝态氮的物质的量比例为1:50，待处理水进入反应器中停留一段时间进行化学反应，停留的时间为50分钟，完成反应后的水排出。
装置运行后，待处理水中硝态氮80mg/L，出水中硝态氮7mg/L，待处理水中总磷20mg/L，出水中总磷0.4mg/L。
实施例8：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
经过以下步骤进行处理：__
(1)将BaFe 12O 19铁氧体永磁粉末与顺磁Fe 3O 4粉末以质量比1:100混合，形成混合粉 末，并置于磁场中磁化，制成磁化粉末；
(2)将上述磁化粉末直接加入到反应池中，磁化粉末与待处理水中硝态氮的物质的量之比为1:100；
(3)在待处理水进入上述反应池后，分批次加入Fe 3O 4，每批次为1000min，同时开始水力搅拌，还原剂总用量与待处理水中硝态氮的物质的量比例为1:80，待处理水进入反应池中停留一段时间进行化学反应，停留的时间为300分钟，完成反应后的水排出。
装置运行后，待处理水中硝态氮120mg/L，出水中硝态氮13mg/L，待处理水中总磷8mg/L，出水中总磷0.2mg/L。
实施例9：
一种磁化粉末强化的硝态氮和无机磷去除方法，包括以下步骤：
经过以下步骤进行处理：
(1)将SrFe 12O 19铁氧体永磁粉末与顺磁Fe 3O 4粉末以质量比1:100混合，形成混合粉末，并置于磁场中磁化，制成磁化粉末；
(2)将上述磁化粉末直接加入到反应器中，磁化粉末与待处理水中硝态氮的物质的量之比为1:100；
(3)在待处理水进入上述反应器前，连续式加入还原剂GR(SO 4 2-)和Fe 3O 4(物质的量比例为5:1)，同时开始水力搅拌，还原剂用量与待处理水中硝态氮的物质的量比例为1:100，待处理水进入反应器中停留一段时间进行化学反应，停留的时间为600分钟，完成反应后的水排出。
装置运行后，待处理水中硝态氮250mg/L，出水中硝态氮14mg/L，待处理水中总磷10mg/L，出水中总磷0.2mg/L。

Claims (10)

  1. 一种磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，它包括以下步骤：
    (1)将永磁材料粉末与顺磁Fe 3O 4粉末混合后，置于磁场中进行磁化，制成磁化粉末；
    (2)将磁化粉末直接或制成颗粒状填料加入水处理反应容器中；
    (3)待处理水进入水处理反应容器中，在还原剂存在的条件下，进行去除硝态氮和无机磷的化学反应，完成反应后的水排出即可。
  2. 根据权利要求1所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(1)中，所述永磁材料粉末为稀土永磁材料、金属永磁材料或铁氧体永磁材料中的一种或几种；所述永磁材料粉末与所述顺磁Fe 3O 4粉末的质量比为1:0.01～1:150；优选为1:5～1:100；更优选为1:10～1:40。
  3. 根据权利要求1所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(1)中，所述稀土永磁材料为Sm-Co系、Nd-Fe-B、La-Ce或Re-Fe-B中的一种或几种；所述金属永磁材料为Al-Ni-Co、Fe-Cr-Co或者其组合物；所述铁氧体永磁材料为α-Fe 2O 3、BaFe 12O 19或SrFe 12O 19中的一种或几种。
  4. 根据权利要求1所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(2)中加入的磁化粉末与步骤(3)中待处理水中硝态氮的物质的量之比为1:0.01～1:100；优选为1:10～1:100；更优选为1:30～1:80。
  5. 根据权利要求1所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(3)中，所述还原剂为单质零价铁、单质零价铝、单质零价锌、单质零价锰、单质零价镁、亚铁化合物、亚铜化合物、绿绣或Fe 3O 4中的一种或几种；优选的，所述亚铁化合物为氯化亚铁、硫酸亚铁或氢氧化亚铁中的一种或几种；所述亚铜化合物为氯化亚铜、硫酸亚铜或氢氧化亚铜中的一种或几种。
  6. 根据权利要求5所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(3)中，所述还原剂的用量与待处理水中硝态氮的物质的量之比为1:0.1～1:150；优选为1:0.8～1:80，更优选为1:10～1:50。
  7. 根据权利要求1所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(3)中，在待处理水进入水处理反应容器之前或之后，批次或连续加入还原剂，待处理水连续式进入水处理反应容器中，一端进入另一端排出，在流动过程中进行化学反应；或者，待处理水进入水处理反应容器中，在水处理反应容器中停留一段时间进行化学反应，完成反应后的水排出即可。
  8. 根据权利要求1所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(3)中，所述待处理水中不含有次氯酸钠、氯胺、臭氧、过硫酸钠或高锰酸钾。
  9. 根据权利要求7所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(3)中，批次加入还原剂时每批次时间为5min～1000min；优选为30min～500min；待处理水连续式进入水处理反应容器的流速为0.1L/h～1000L/h；待处理水在水处理反应容器中停留的时间为1～600分钟；优选为1～300分钟；更优选为1～50分钟。
  10. 根据权利要求1所述的磁化粉末强化的硝态氮和无机磷去除方法，其特征在于，在步骤(2)中，水处理反应容器的底部设置有排泥系统，定时清理去除无机磷时产生的铁泥。
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