WO2018188407A1 - 一种化工废水生化出水的深度处理及回用方法 - Google Patents

一种化工废水生化出水的深度处理及回用方法 Download PDF

Info

Publication number
WO2018188407A1
WO2018188407A1 PCT/CN2018/075353 CN2018075353W WO2018188407A1 WO 2018188407 A1 WO2018188407 A1 WO 2018188407A1 CN 2018075353 W CN2018075353 W CN 2018075353W WO 2018188407 A1 WO2018188407 A1 WO 2018188407A1
Authority
WO
WIPO (PCT)
Prior art keywords
chemical wastewater
reuse
effluent
magnetic resin
chemical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/075353
Other languages
English (en)
French (fr)
Inventor
周庆
金晶
李爱民
徐林镇
程加德
周伟伟
冯天宇
黄艳
王未
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University
Nanjing Tech University
Nanjing University Yancheng Environmental Protection Technology and Engineering Research Institute
Original Assignee
Nanjing University
Nanjing Tech University
Nanjing University Yancheng Environmental Protection Technology and Engineering Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University, Nanjing Tech University, Nanjing University Yancheng Environmental Protection Technology and Engineering Research Institute filed Critical Nanjing University
Publication of WO2018188407A1 publication Critical patent/WO2018188407A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C02F1/325—Irradiation devices or lamp constructions
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/481—Treatment of water, waste water, or sewage with magnetic or electric fields using permanent magnets
    • 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
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • 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
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Definitions

  • the invention relates to the technical field of industrial wastewater treatment, in particular to a method for deep treatment and reuse of biochemical effluent of chemical wastewater.
  • the chemical industry is one of the pillar industries in China, but at the same time the environmental pollution brought by the industry is also very serious. According to the annual environmental statistics report in recent years, the discharge of chemical wastewater is ranked in the top three of industrial wastewater discharge, more important.
  • the chemical wastewater is not only large in water, but also contains many organic substances that are too toxic and difficult to degrade.
  • COD and other indicators are difficult to meet the standard emission, and it is often necessary to add a deep treatment process to supplement.
  • Conventional processes such as coagulation, although it can reduce COD to a certain extent, but highly toxic substances are difficult to be effective.
  • Advanced oxidation technology is often used as one of the advanced treatment processes for the degradation of organic matter in biochemical effluent.
  • Fenton technology is the most mature advanced oxidation technology, but it brings a lot of iron mud to become a bottleneck problem that limits the application of this technology.
  • the researchers improved the original homogeneous reaction to a heterogeneous reaction, using a carrier to immobilize the ferrous ion, and after inputting the reaction, reduce the iron ions in the solution by recovering the carrier, and finally realize the iron mud.
  • Some researchers have used magnetic nano-ferric oxide as a catalyst to directly carry out the Fenton reaction, and finally recovered the nanoparticles to reduce the production of iron mud.
  • Fenton oxidation technology does not allow the organic matter to be completely carbonized, easily producing intermediate products or by-products of different structures, and even some intermediate products are much more toxic than the original materials. Therefore, on the basis of Fenton oxidation, other technologies should be combined to effectively treat the biochemical tail water of chemical wastewater.
  • the object of the present invention is to provide an advanced treatment and reuse method for biochemical effluent of chemical wastewater, which can not only effectively remove the problem of organic matter refractory degradation in the biochemical effluent of chemical wastewater, but also reduce the toxicity thereof, and finally achieve the reused water quality standard and safety. Sexual requirements.
  • the present invention adopts the following technical solutions:
  • An advanced treatment and reuse method for biochemical effluent of chemical wastewater comprising the following steps:
  • volume ratio of the magnetic resin to the biochemical effluent of the chemical wastewater is 0.1% to 5%.
  • the magnetic resin has a specific surface area of 500 to 700 m 2 /g, and the mass fraction of Fe 3 O 4 nanoparticles in the magnetic resin is 30% to 50%.
  • the magnetic resin is prepared by using a nozzle having a pore diameter of 20 to 50 ⁇ m, and slowly dispersing the oil phase and the Fe 3 O 4 nanoparticle mixture in the aqueous phase at 0.1 MPa to form an emulsion at 150 r/min. At the stirring speed, the temperature was raised to 70 ° C for 2 hours, and then the temperature was raised to 85 ° C for 12 hours, followed by washing with deionized water, ethanol, acetone, and finally drying.
  • the monomer is divinylbenzene
  • the porogen is toluene
  • the initiator is azobisisobutyronitrile
  • the ratio of the divinylbenzene to toluene is 1:2 to 1:3.
  • the mass fraction of the azobisisobutyronitrile was 1%.
  • the dispersing agent is sodium lauryl sulfate and polyvinylpyrrolidone, and the ratio of sodium lauryl sulfate to polyvinylpyrrolidone is 1:3 to 1: 6.
  • the mass fraction of the dispersant is 0.5% to 2%.
  • the Fe 3 O 4 nanoparticles are modified by oleic acid coating, and the mass ratio of the Fe 3 O 4 nanoparticles to the oil phase is 1:1 to 1:2.
  • the mixed wastewater is adjusted to pH 5-7 by using hydrochloric acid and sodium hydroxide.
  • the disinfection treatment is a combination of ultraviolet and chlorine disinfection, which is ultraviolet light and NaClO disinfectant; the amount of the NaClO disinfectant is 5 mg/L according to Cl 2 , and the ultraviolet light is a mercury light source, ultraviolet light
  • the radiation intensity is 30 W and the reaction time is 100 to 1800 seconds.
  • the method further comprises mixing the magnetic resin separated in the step (3) with a regeneration liquid, wherein the regeneration liquid component is: sodium hydroxide: 5 wt.% to 15 wt.%, methanol: 20 wt.% to 70 wt.%. Or: sodium hydroxide: 5 wt.% to 15 wt.%, ethanol: 50 wt.%, and the magnetic resin is mixed with the regenerating liquid for 20 to 180 minutes, and then allowed to stand for 55 to 65 minutes, and the magnetic resin is separated and recovered.
  • the regeneration liquid component is: sodium hydroxide: 5 wt.% to 15 wt.%, methanol: 20 wt.% to 70 wt.%.
  • sodium hydroxide 5 wt.% to 15 wt.%
  • ethanol 50 wt.%
  • the Fe 3 O 4 is fixed by using a resin adsorption material, and after the reaction is input, the magnetic resin can be recovered, the iron ions in the solution are reduced, and the iron sludge is reduced;
  • the invention adopts the combination of resin adsorption and Fenton advanced oxidation, and the pH can be controlled at 5 to 7 to achieve the best effect, reducing the use of the acid reagent and reducing the cost;
  • the adsorption process of the adsorption-advance oxidation-adsorption-disinfection method can effectively remove the refractory organic matter in the biochemical effluent of the chemical wastewater and reduce the toxicity thereof, thereby achieving the reuse water quality standard and safety requirements;
  • ultraviolet-chlorine simultaneous disinfection can not only kill pathogenic bacteria in water, but also effectively remove organic pollutants by various actions such as hydroxyl radicals, chlorine radicals and hypochlorous acid oxidation. To reduce the toxicity of effluent and ensure the ecological safety of recycled water;
  • the adsorption-advanced oxidation-adsorption-disinfection treatment process provided by the invention is stable in operation, easy to operate, and has high water quality standards, and the effluent water quality is stable and safe.
  • the method for deep treatment and reuse of biochemical effluent of chemical wastewater is a coupling process of resin adsorption, Fenton advanced oxidation and ultraviolet chlorine disinfection, and enriching the hardly degradable materials in the biochemical effluent of chemical wastewater by resin adsorption method, Under the catalysis of Fe 3 O 4 nanoparticles, H 2 O 2 was added to carry out the advanced oxidative decomposition of Fenton-like, and the partially decomposed products were removed by resin adsorption, and the organic substances remaining in the solution were further removed by ultraviolet disinfection.
  • the volume of the magnetic resin accounted for 2% of the chemical wastewater effluent volume, and the H 2 O 2 concentration was 4 mmol/L, after reacting for 300 minutes, solid-liquid separation was carried out.
  • the NaClO disinfectant was added to the separated chemical wastewater effluent, which was 5 mg/L according to Cl 2 and simultaneously irradiated with a 30 W UV lamp for 600 seconds.
  • the effluent water quality is shown in Table 1.
  • the separated magnetic resin was mixed and regenerated with 5 wt.% sodium hydroxide and 70 wt.% methanol for a regeneration time of 130 minutes, and then allowed to stand for 55 minutes; the regenerated magnetic resin was used as a fresh magnetic resin.
  • Table 1 the water quality standard for washing water in urban sewage recycling-industrial water quality (GB/T19923-2005) is used as a reference, and the wastewater of the plant meets the recycling water recycling standard.
  • the volume of the magnetic resin accounted for 1.5% of the chemical wastewater effluent volume, and the H 2 O 2 concentration was After 3 minutes of reaction at 3 mmol/L, solid-liquid separation was carried out.
  • the NaClO disinfectant was added to the separated chemical waste water biochemical effluent, which was 5 mg/L according to Cl 2 , and was irradiated by a 30 W ultraviolet lamp for 120 seconds.
  • the effluent water quality is shown in Table 2.
  • the separated magnetic resin was mixed and regenerated with 15 wt.% of sodium hydroxide and 20 wt.% of methanol, and the regeneration time was 60 minutes, followed by standing for 60 minutes; the regenerated magnetic resin was used as a fresh magnetic resin.
  • Table 2 the boiler feed water quality standard in urban sewage recycling-industrial water quality (GB/T19923-2005) is used as a reference, and the wastewater of the plant meets the reclaimed water reuse standard.
  • the volume of the magnetic resin accounted for 3% of the chemical wastewater effluent volume, and the H 2 O 2 concentration was 5 mmol/L, after 550 minutes of reaction, solid-liquid separation was carried out.
  • the NaClO disinfectant was added to the separated chemical waste water biochemical effluent, which was 5 mg/L according to Cl 2 , and the 30 W ultraviolet lamp was turned on for 1800 seconds.
  • the effluent water quality is shown in Table 3.
  • the separated magnetic resin was mixed and regenerated with 10 wt.% sodium hydroxide and 50 wt.% ethanol for a regeneration time of 100 minutes, and then allowed to stand for 65 minutes; the regenerated magnetic resin was used as a fresh magnetic resin.
  • Table 3 the wastewater of the process and product water quality of urban sewage recycling-industrial water quality (GB/T19923-2005) is used as a reference, and the wastewater of the plant meets the reclaimed water reuse standard.
  • the method for deep treatment and reuse of the biochemical effluent of chemical wastewater can utilize the higher specific surface area thereof to effectively enrich the pollutants by adsorption;
  • Fe 3 O 4 acts as a catalyst to promote the oxidative decomposition of Fenton, and the decomposition product can be adsorbed and removed by a magnetic resin.
  • the oxidation process is strengthened by adding an ultraviolet light source and adding chlorine, and disinfection is performed to kill the pathogenic bacteria, so as to further realize the reuse of the water.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Physical Water Treatments (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

一种化工废水生化出水的深度处理及回用方法，包括以下步骤：(1)通过喷射悬浮聚合法制备高负载Fe 3O 4的磁性树脂；(2)利用步骤(1)中制备的磁性树脂对化工废水生化出水进行深度处理，并在化工废水生化出水中加入3～5mmol/L的H 2O 2，混合反应，反应时间为60～600分钟；(3)先将步骤(2)处理后的混合废水进行固液分离，再对分离后的化工废水生化出水进行消毒处理。该方法可有效去除废水中难降解有机污染物并削减其毒性，达到回用水质标准要求，并能保证其回用过程中的生态安全。

Description

一种化工废水生化出水的深度处理及回用方法 技术领域
本发明涉及工业废水处理技术领域，具体涉及一种化工废水生化出水的深度处理及回用方法。
背景技术
化工行业是我国的支柱产业之一，但同时该行业带来的环境污染也非常严重，据近年来的环境统计年报显示，化工废水排放量稳居在工业废水排放量的前三位，更重要的是，化工废水不仅水量大，而且其所含的有机物毒性大，难以降解，如今更是成为人们关注的重点。化工废水在生化处理后，COD等指标难以达标排放，往往需要增加深度处理工艺来进行补充，常规的工艺如混凝等，尽管能在一定程度上降低COD，但其中高毒性的物质很难有效去除，这些有机毒物虽然对COD、氨氮等综合指标贡献很小，但因其具有致癌、致畸、致突变特性和遗传毒性，其随着废水排放进入到环境体系中，对生态环境与人体健康造成危害。
针对生化出水中有机物难降解的特性，高级氧化技术常被用来作为深度处理的工艺之一。其中，芬顿技术是最为成熟的一种高级氧化技术，但其带来大量的铁泥成为限制该技术应用的瓶颈问题。针对这一实际问题，研究者们将原先的均相反应改进为非均相反应，利用载体将亚铁离子固载，投入反应后通过对载体的回收减少溶液中的铁离子，最终实现铁泥的减量化。也有研究者使用磁性纳米四氧化三铁作为催化剂，直接进行芬顿反应，最后回收纳米粒子以减少铁泥的产生。然而，芬顿氧化技术并不能使得有机物完全碳化，容易产生结构不一的中间产物或副产物，甚至有些中间产物毒性还会远远大于原物质。为此，在芬顿氧化的基础上，还应当结合其他技术，才能有效地对化工废水的生化尾水进行有效处理。
发明内容
本发明的目的是提供一种化工废水生化出水的深度处理及回用方法，不 仅能有效去除化工废水生化出水中的有机物难降解问题，还能削减其毒性，最终能达到回用水质标准及安全性要求。
为解决上述技术问题，本发明采用了以下技术方案：
一种化工废水生化出水的深度处理及回用方法，包括以下步骤：
(1)通过喷射悬浮聚合法制备高负载Fe 3O 4的磁性树脂；
(2)利用步骤(1)中制备的磁性树脂对化工废水生化出水进行深度处理，并在化工废水生化出水中加入3～5mmol/L的H 2O 2，混合反应，反应时间为60～600分钟；
(3)先将步骤(2)处理后的混合废水进行固液分离，再对分离后的化工废水生化出水进行消毒处理。
进一步地，所述磁性树脂与化工废水生化出水的体积比为0.1％～5％。
进一步地，所述磁性树脂的比表面积为500～700m 2/g，磁性树脂中Fe 3O 4纳米粒子的质量分数为30％～50％。
进一步地，所述磁性树脂的制备是利用孔径为20～50μm的喷头，在0.1MPa下缓慢将油相与Fe 3O 4纳米粒子混合液均匀分散至水相中，形成乳液，在150r/min的搅拌速度下，升温至70℃反应2小时，再升温至85℃反应12小时，之后依次使用去离子水、乙醇、丙酮洗涤，最后烘干。
进一步地，所述油相中，单体为二乙烯苯，致孔剂为甲苯，引发剂为偶氮二异丁腈，所述二乙烯苯与甲苯的比例为1:2～1:3，所述偶氮二异丁氰的质量分数为1％。
进一步地，所述水相中，分散剂为十二烷基硫酸钠与聚乙烯比咯烷酮，且十二烷基硫酸钠与聚乙烯比咯烷酮两者比例为1:3～1:6，所述分散剂的质量分数为0.5％～2％。
进一步地，所述Fe 3O 4纳米粒子是油酸包覆修饰的，所述Fe 3O 4纳米粒子与油相的质量比为1:1～1:2。
进一步地，所述深度处理过程中，将所述混合废水采用盐酸和氢氧化钠调节pH至5～7。
进一步地，所述消毒处理是紫外和氯联合消毒，为紫外光和NaClO消毒 剂；所述NaClO消毒剂用量为按Cl 2计为5mg/L，所述紫外光以汞灯为光源，紫外光辐射强度为30W，反应时间为100～1800秒。
更进一步地，还包括将步骤(3)分离得到的磁性树脂与再生液进行混合，所述再生液成分为：氢氧化钠：5wt.％～15wt.％、甲醇：20wt.％～70wt.％，或者为：氢氧化钠：5wt.％～15wt.％、乙醇：50wt.％，磁性树脂与再生液混合20～180分钟后，静置55～65分钟，分离出磁性树脂进行回收再利用。
上述技术方案中提供的化工废水生化出水的深度处理及回用方法，有益效果如下：
(1)使用树脂吸附材料将Fe 3O 4固载，投入反应后可对磁性树脂进行回收，减少溶液中的铁离子，实现铁泥的减量化；
(2)本发明采用树脂吸附与芬顿高级氧化同时联合作用，pH只需控制在5～7即可达到最佳效果，减少了酸试剂的使用，降低了成本；
(3)本发明通过吸附－高级氧化－吸附－消毒的耦合工艺，可以有效去除化工废水生化出水中的难降解有机物并削减其毒性，达到回用水质标准及安全性要求；
(4)本发明中采用紫外－氯同时联合消毒，不仅可以杀灭水中病原菌，还可以通过羟基自由基、氯自由基以及次氯酸氧化等多种作用，对有机污染物进行有效的再次去除，降低出水毒性，保证回用水的生态安全；
(5)本发明提供的吸附－高级氧化－吸附－消毒处理工艺运行稳定，易于操作，且水质标准高，出水水质稳定、安全。
具体实施方式
为了使本发明的目的及优点更加清楚明白，以下结合实施例对本发明进行具体说明。应当理解，以下文字仅仅用以描述本发明的一种或几种具体的实施方式，并不对本发明具体请求的保护范围进行严格限定。
本发明提供的化工废水生化出水深度处理及回用方法，是树脂吸附、芬顿高级氧化和紫外氯消毒的耦合工艺，利用树脂吸附法对化工废水生化出水中的难降解物进行富集，在Fe 3O 4纳米粒子的催化作用下，加入H 2O 2进行类 芬顿高级氧化分解，部分分解产物再通过树脂吸附进行去除，残留于溶液中的有机物经过紫外氯消毒过程进一步去除。
实施例1
一大型化工废水处理厂生化出水，调节pH值为6后，向该水样中依次加入磁性树脂和H 2O 2，磁性树脂体积占化工废水生化出水体积的2％，H 2O 2浓度为4mmol/L，反应300分钟后，进行固液分离。向分离后的化工废水生化出水中加入NaClO消毒剂，按Cl 2计为5mg/L，同时打开30W的紫外灯照射600秒，其出水水质如表1所示。最后再将分离得到的磁性树脂与5wt.％氢氧化钠、70wt.％的甲醇进行混合再生，再生时间130分钟，后静置55分钟；再生后的磁性树脂作为新鲜磁性树脂进行使用。如表1所示，以城市污水再生利用－工业用水水质(GB/T19923-2005)中的洗涤用水水质标准作为参考，该厂废水符合再生水回用标准。
表1 本发明方法出水水质与洗涤用水水质标准比较
Figure PCTCN2018075353-appb-000001
实施例2
一大型化工废水处理厂生化出水，调节pH值为5后，向该水样中依次加入磁性树脂和H 2O 2，磁性树脂体积占化工废水生化出水体积的1.5％，H 2O 2浓度为3mmol/L，反应100分钟后，进行固液分离。向分离后的化工废水生化出水中加入NaClO消毒剂，按Cl 2计为5mg/L，同时打开30W的紫外灯照射120秒，其出水水质如表2所示。最后再将分离得到的磁性树脂与15wt.％氢氧化钠、20wt.％的甲醇进行混合再生，再生时间60分钟，后静置60分钟；再生后的磁性树脂作为新鲜磁性树脂进行使用。如表2所示，以城市污水再生利用－工业用水水质(GB/T19923-2005)中的锅炉补给水水质标准作为参考，该厂废水符合再生水回用标准。
表2 本发明方法出水水质与锅炉补给水水质标准比较
Figure PCTCN2018075353-appb-000002
实施例3
一大型化工废水处理厂生化出水，调节pH值为7后，向该水样中依次加入磁性树脂和H 2O 2，磁性树脂体积占化工废水生化出水体积的3％，H 2O 2浓度为5mmol/L，反应550分钟后，进行固液分离。向分离后的化工废水生化出水中加入NaClO消毒剂，按Cl 2计为5mg/L，同时打开30W的紫外灯照射1800秒，其出水水质如表3所示。最后再将分离得到的磁性树脂与10wt.％氢氧化钠、50wt.％的乙醇进行混合再生，再生时间100分钟，后静置65分钟；再生后的磁性树脂作为新鲜磁性树脂进行使用。如表3所示，以城市污水再生利用－工业用水水质(GB/T19923-2005)中的工艺与产品用水水质标准作为参考，该厂废水符合再生水回用标准。
表3 本发明方法出水水质与工艺及产品用水水质标准比较
Figure PCTCN2018075353-appb-000003
综上所述，本发明提供的化工废水生化出水的深度处理及回用方法，一方面能利用其较高的比表面积，通过吸附作用可以将污染物有效进行富集；另一方面通过负载于其中的Fe 3O 4作为催化剂，促进芬顿氧化分解，而分解产物又可以通过磁性树脂进行吸附去除。同时，通过外加紫外光源以及加氯强化其氧化过程，并起到消毒作用，杀灭病原菌，以便于进一步实现中水回用。
以上实施例对本发明的实施方式作了详细说明，但是本发明并不限于上 述实施方式，对于本技术领域的普通技术人员来说，在获知本发明中记载内容后，在不脱离本发明原理的前提下，还可以对其作出若干同等变换和替代，这些同等变换和替代也应视为属于本发明的保护范围。

Claims (10)

  1. 一种化工废水生化出水的深度处理及回用方法，其特征在于包括以下步骤：
    (1)通过喷射悬浮聚合法制备高负载Fe 3O 4的磁性树脂；
    (2)利用步骤(1)中制备的磁性树脂对化工废水生化出水进行深度处理，并在化工废水生化出水中加入3～5mmol/L的H 2O 2，混合反应，反应时间为60～600分钟；
    (3)先将步骤(2)处理后的混合废水进行固液分离，再对分离后的化工废水生化出水进行消毒处理。
  2. 根据权利要求1所述的化工废水生化出水的深度处理及回用方法，其特征在于：所述磁性树脂与化工废水生化出水的体积比为0.1％～5％。
  3. 根据权利要求1所述的化工废水生化出水的深度处理及回用方法，其特征在于：所述磁性树脂的比表面积为500～700m 2/g，磁性树脂中Fe 3O 4纳米粒子的质量分数为30％～50％。
  4. 根据权利要求2所述的化工废水生化出水的深度处理及回用方法，其特征在于：所述磁性树脂的制备是利用孔径为20～50μm的喷头，在0.1MPa下缓慢将油相与Fe 3O 4纳米粒子混合液均匀分散至水相中，形成乳液，在150r/min的搅拌速度下，升温至70℃反应2小时，再升温至85℃反应12小时，之后依次使用去离子水、乙醇、丙酮洗涤，最后烘干。
  5. 根据权利要求3所述的化工废水生化出水的深度处理及回用方法，其特征在于：所述油相中，单体为二乙烯苯，致孔剂为甲苯，引发剂为偶氮二异丁腈，所述二乙烯苯与甲苯的比例为1:2～1:3，所述偶氮二异丁氰的质量分数为1％。
  6. 根据权利要求3所述的化工废水生化出水的深度处理及回用方法，其特征在于：所述水相中，分散剂为十二烷基硫酸钠与聚乙烯比咯烷酮，且十二烷基硫酸钠与聚乙烯比咯烷酮两者比例为1:3～1:6，所述分散剂的质量分数为0.5％～2％。
  7. 根据权利要求3所述的化工废水生化出水的深度处理及回用方法，其 特征在于：所述Fe 3O 4纳米粒子是油酸包覆修饰的，所述Fe 3O 4纳米粒子与油相的质量比为1:1～1:2。
  8. 根据权利要求1所述的化工废水生化出水的深度处理及回用方法，其特征在于：所述深度处理过程中，将所述混合废水采用盐酸和氢氧化钠调节pH至5～7。
  9. 根据权利要求1所述的化工废水生化出水的深度处理及回用方法，其特征在于：所述消毒处理是紫外和氯联合消毒，为紫外光和NaClO消毒剂；所述NaClO消毒剂用量为按Cl 2计为5mg/L，所述紫外光以低压汞灯为光源，紫外光辐射强度为30W，反应时间为100～1800秒。
  10. 根据权利要求1所述的化工废水生化出水的深度处理及回用方法，其特征在于：还包括将步骤(3)分离得到的磁性树脂与再生液进行混合，所述再生液成分为：氢氧化钠：5wt.％～15wt.％、甲醇：20wt.％～70wt.％，或者为：氢氧化钠：5wt.％～15wt.％、乙醇：50wt.％，磁性树脂与再生液混合20～180分钟后，静置55～65分钟，分离出磁性树脂进行回收再利用。
PCT/CN2018/075353 2017-04-11 2018-02-06 一种化工废水生化出水的深度处理及回用方法 Ceased WO2018188407A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710232216.4 2017-04-11
CN201710232216.4A CN106882896B (zh) 2017-04-11 2017-04-11 一种化工废水生化出水的深度处理及回用方法

Publications (1)

Publication Number Publication Date
WO2018188407A1 true WO2018188407A1 (zh) 2018-10-18

Family

ID=59183462

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/075353 Ceased WO2018188407A1 (zh) 2017-04-11 2018-02-06 一种化工废水生化出水的深度处理及回用方法

Country Status (3)

Country Link
US (1) US20170275194A1 (zh)
CN (1) CN106882896B (zh)
WO (1) WO2018188407A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106882896B (zh) * 2017-04-11 2021-04-09 南京大学 一种化工废水生化出水的深度处理及回用方法
CN107698113B (zh) * 2017-12-04 2024-08-27 清远市龙湾工业投资有限公司 一种工业废水集中处理系统及方法
CN108405592A (zh) * 2018-01-30 2018-08-17 南京师范大学 一种利用磁性铁基尖晶石结构材料同时修复有机物和汞污染土壤的方法
CN108358297A (zh) * 2018-03-12 2018-08-03 南京科技职业学院 一种印染废水二级生化出水深度处理方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6337700A (en) * 1999-06-24 2001-01-09 University Of Chicago, The Method for the decontamination of metallic surfaces
CN101708876A (zh) * 2009-12-25 2010-05-19 南京中电联环保工程有限公司 水力射流磁性树脂吸附反应器
CN102107965A (zh) * 2011-01-18 2011-06-29 南京大学 一种铁、锰超标水源水的应急预处理系统及其处理方法
CN103435181A (zh) * 2013-08-19 2013-12-11 南京大学 一种化工废水生化出水的高效处理及回用方法
CN105036486A (zh) * 2015-08-17 2015-11-11 台州学院 基于磁性类芬顿树脂深度处理抗生素类制药废水的方法
CN204939202U (zh) * 2015-08-17 2016-01-06 台州学院 基于磁性类芬顿树脂深度处理抗生素类化工废水的装置
CN106882896A (zh) * 2017-04-11 2017-06-23 南京大学 一种化工废水生化出水的深度处理及回用方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103523900A (zh) * 2013-10-24 2014-01-22 中山大学 一种紫外光和自由氯联用去除水中微污染物的方法
CN103739764A (zh) * 2013-12-09 2014-04-23 何小刚 一种磁性大孔吸附树脂微球及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6337700A (en) * 1999-06-24 2001-01-09 University Of Chicago, The Method for the decontamination of metallic surfaces
CN101708876A (zh) * 2009-12-25 2010-05-19 南京中电联环保工程有限公司 水力射流磁性树脂吸附反应器
CN102107965A (zh) * 2011-01-18 2011-06-29 南京大学 一种铁、锰超标水源水的应急预处理系统及其处理方法
CN103435181A (zh) * 2013-08-19 2013-12-11 南京大学 一种化工废水生化出水的高效处理及回用方法
CN105036486A (zh) * 2015-08-17 2015-11-11 台州学院 基于磁性类芬顿树脂深度处理抗生素类制药废水的方法
CN204939202U (zh) * 2015-08-17 2016-01-06 台州学院 基于磁性类芬顿树脂深度处理抗生素类化工废水的装置
CN106882896A (zh) * 2017-04-11 2017-06-23 南京大学 一种化工废水生化出水的深度处理及回用方法

Also Published As

Publication number Publication date
US20170275194A1 (en) 2017-09-28
CN106882896A (zh) 2017-06-23
CN106882896B (zh) 2021-04-09

Similar Documents

Publication Publication Date Title
Shiraz et al. Photo-Fenton like degradation of catechol using persulfate activated by UV and ferrous ions: Influencing operational parameters and feasibility studies
Mahtab et al. Zero Fenton sludge discharge: a review on reuse approach during wastewater treatment by the advanced oxidation process
Hsueh et al. Degradation of azo dyes using low iron concentration of Fenton and Fenton-like system
Kordestani et al. A new study on photocatalytic degradation of meropenem and ceftriaxone antibiotics based on sulfate radicals: Influential factors, biodegradability, mineralization approach
CN103755097B (zh) 难生物降解废水的高级氧化-生物法处理装置
Asl et al. Removal of metronidazole from aqueous solution using ozonation process
WO2018188407A1 (zh) 一种化工废水生化出水的深度处理及回用方法
CN101774673B (zh) 一种难降解有机物的处理方法
CN104024168A (zh) 焦化废水处理
Khan et al. Advanced oxidation processes for wastewater remediation: An overview
Qin et al. Advanced treatment of pharmaceutical wastewater with combined micro-electrolysis, Fenton oxidation, and coagulation sedimentation method
Emam Effect of ozonation combined with heterogeneous catalysts and ultraviolet radiation on recycling of gas-station wastewater
CN103803695B (zh) 零价铁与TiO2光催化耦合的类芬顿光催化反应体系的方法
Kamal et al. Comparative study of organics removal from refinery wastewater by photocatalytic Fenton reaction coupled with visible light and ultraviolet irradiation
CN103601332B (zh) 一种低温等离子体和微电解联合处理硝基甲苯生产污水的方法
CN104944648B (zh) 一种治理废水的高压溶氧氧化处理工艺
CN103708648B (zh) 还原-Fenton氧化耦合处理偶氮印染废水的方法
Nguyen et al. Utilization of modified biochar for removal of dyes from industrial effluent
CN105174423A (zh) 一种煤化工生化尾水处理方法
CN102976567B (zh) 一种紫外—可见光多级光催化处理油漆废水的工艺
KR101379374B1 (ko) 염색폐수 철염환원 처리방법
CN102863069A (zh) 除草剂类农药废水的复合Fenton处理方法
Firdous et al. GENERAL AND PHYSICAL
CN106587325B (zh) 一种利用CoxFe1-xP材料非均相活化单过硫酸氢盐处理难降解废水的方法
CN105036238A (zh) 一种光催化氧化处理苯胺类废水的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18785045

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18785045

Country of ref document: EP

Kind code of ref document: A1