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CN107381863A - A kind of degraded highly salt containing organic waste water and the method for synchronously preparing iron oxide - Google Patents

A kind of degraded highly salt containing organic waste water and the method for synchronously preparing iron oxide Download PDF

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CN107381863A
CN107381863A CN201710607245.4A CN201710607245A CN107381863A CN 107381863 A CN107381863 A CN 107381863A CN 201710607245 A CN201710607245 A CN 201710607245A CN 107381863 A CN107381863 A CN 107381863A
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iron oxide
reaction
waste water
salt organic
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魏雨
刘辉
周金明
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Hebei Normal University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • C01G49/06Ferric oxide [Fe2O3]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048Purification of waste water by evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/023Reactive oxygen species, singlet oxygen, OH radical

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

Abstract

The present invention relates to technical field of waste water processing, specifically discloses a kind of degraded highly salt containing organic waste water and the method for synchronously preparing iron oxide.Methods described comprises at least following steps:First the pH value of highly salt containing organic waste water is adjusted to 4.0 6.5, ferriferous oxide catalyst is previously added, adds oxidant, Fe2+, reacted, and control pH value in course of reaction to be maintained between 4.0 6.5;Reaction is filtered after terminating, and Fe is added after filter cake plus moisture are dissipated2+, heating response is carried out, generates iron oxide red or iron oxide yellow.After preferential addition catalyst iron oxide of the invention induces reaction, Fe2+Added simultaneously with oxidant, a large amount of nano iron oxide catalysts of in-situ preparation, improve OH generation efficiencies and the degradation speed to organic matter, for TOC clearances more than 80%, degradation effect is excellent, and after the completion of degraded, grade ferric oxide product can be obtained, reaches twice laid.

Description

一种降解高含盐有机废水及同步制备氧化铁的方法A method for degrading high-salt organic wastewater and synchronously preparing iron oxide

技术领域technical field

本发明涉及废水处理技术领域,尤其涉及一种降解高含盐有机废水及同步制备氧化铁的方法。The invention relates to the technical field of wastewater treatment, in particular to a method for degrading high-salt organic wastewater and synchronously preparing iron oxide.

背景技术Background technique

随着我国医药、化工、石油、海产品等工业的迅速发展,高含盐难降解有机废水排放量在不断增多,目前常规处理方法是先脱盐、再生化。对于含高浓度有机物废水的脱盐,蒸发是最简单有效的方法,但是常规蒸发方法仅仅能够实现脱盐的作用,无法将有机污染物降解,存在二次污染等问题。芬顿及类芬顿氧化技术由于反应条件温和、设备操作简单、处理费用相当较低及适用范围广等优点,并且其技术比较成熟,已成功应用于多种工业废水降解处理。但由于现有的芬顿氧化技术仍存在双氧水利用率低及产生一定量污泥等问题。因此,设计一种兼具有机污染物快速降解和不产生污泥的处理方法对解决高盐高浓度有机废水治理难题及环境保护具有重要的意义。With the rapid development of my country's pharmaceutical, chemical, petroleum, seafood and other industries, the discharge of high-salt and refractory organic wastewater is increasing. The current conventional treatment method is desalination and regeneration first. Evaporation is the simplest and most effective method for the desalination of wastewater containing high concentrations of organic matter, but conventional evaporation methods can only achieve desalination and cannot degrade organic pollutants, resulting in secondary pollution and other problems. Due to the advantages of mild reaction conditions, simple equipment operation, relatively low treatment cost and wide application range, Fenton and Fenton-like oxidation technology has been successfully applied to a variety of industrial wastewater degradation treatment due to its relatively mature technology. However, the existing Fenton oxidation technology still has problems such as low utilization rate of hydrogen peroxide and generation of a certain amount of sludge. Therefore, it is of great significance to design a treatment method that combines rapid degradation of organic pollutants and no sludge generation to solve the problem of high-salt and high-concentration organic wastewater treatment and environmental protection.

发明内容Contents of the invention

针对现有高含盐工业废水处理中氧化剂利用率低及产生污泥等问题,本发明提供一种降解高含盐有机废水及同步制备氧化铁的方法。Aiming at the problems of low oxidant utilization rate and sludge generation in the existing high-salt industrial wastewater treatment, the invention provides a method for degrading high-salt organic wastewater and synchronously preparing iron oxide.

为达到上述发明目的,本发明实施例采用了如下的技术方案:In order to achieve the above-mentioned purpose of the invention, the embodiment of the present invention adopts the following technical solutions:

一种降解高含盐有机废水及同步制备氧化铁的方法,至少包括以下步骤:A method for degrading high-salt organic wastewater and synchronously preparing iron oxide comprises at least the following steps:

步骤1、将高含盐有机废水的pH值调节至4.0-6.5,预先加入铁氧化物催化剂,再加入氧化剂、Fe2+,进行反应,且控制反应过程中pH值保持在4.0-6.5之间;Step 1. Adjust the pH value of high-salt organic wastewater to 4.0-6.5, add iron oxide catalyst in advance, then add oxidant and Fe 2+ to carry out the reaction, and control the pH value during the reaction process to maintain between 4.0-6.5 ;

步骤2、反应结束后过滤,收集滤饼,将滤饼加水分散后加入催化剂Fe2+得混合溶液,将所述混合溶液的pH值调节到6.5-7之间,进行加热反应,生成氧化铁红或氧化铁黄。Step 2, filter after the reaction is over, collect the filter cake, disperse the filter cake with water, add catalyst Fe 2+ to obtain a mixed solution, adjust the pH value of the mixed solution to between 6.5-7, and perform a heating reaction to generate iron oxide Red or iron oxide yellow.

相对于现有技术,本发明提供的降解高含盐有机废水及同步制备氧化铁的方法,具有以下优势:Compared with the prior art, the method for degrading high-salt organic wastewater and synchronously preparing iron oxide provided by the present invention has the following advantages:

(1)本发明预先加入催化剂氧化铁,再加入Fe2+,此时Fe2+会与催化剂氧化铁表面的三价铁发生电子转移,催化剂表面会有“新生态”二价铁生成,由于该二价铁具有超常的还原的能力,可以优先从H2O2得到电子生成•OH,所以理论上H2O2产生•OH的效率为100%,同时加入的Fe2+电子转移后成为了Fe3+,快速水解原位生成亚稳态铁黄或铁红,又成为电子转移催化剂。(1) In the present invention, the catalyst iron oxide is added in advance, and then Fe 2+ is added. At this time, Fe 2+ will undergo electron transfer with the ferric iron on the surface of the catalyst iron oxide, and the catalyst surface will have "new ecology" ferrous iron. The ferrous iron has extraordinary reduction ability, and can preferentially obtain electrons from H 2 O 2 to generate •OH, so theoretically the efficiency of H 2 O 2 to generate •OH is 100%, and at the same time, the added Fe 2+ electron transfers to become Fe 3+ , rapid hydrolysis in situ to generate metastable iron yellow or iron red, and become an electron transfer catalyst.

(2)本发明可以在实现对高含盐高浓度有机废水氧化降解、脱盐的同时制备出颜料级氧化铁产品,着色力可达到95%以上,指标符合国家标准,可作为产品销售。(2) The present invention can produce pigment-grade iron oxide products while achieving oxidative degradation and desalination of high-salt and high-concentration organic wastewater. The tinting power can reach more than 95%, and the indicators meet the national standards, which can be sold as products.

具体实施方式detailed description

为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

本发明实施例提供一种降解高含盐有机废水及同步制备氧化铁的方法,所述方法至少包括以下步骤:An embodiment of the present invention provides a method for degrading high-salt organic wastewater and synchronously preparing iron oxide, the method at least including the following steps:

步骤1、将高含盐有机废水的pH值调节至4.0-6.5,预先加入铁氧化物催化剂,再加入氧化剂、Fe2+,进行反应,且控制反应过程中pH值保持在4.0-6.5之间;Step 1. Adjust the pH value of high-salt organic wastewater to 4.0-6.5, add iron oxide catalyst in advance, then add oxidant and Fe 2+ to carry out the reaction, and control the pH value during the reaction process to maintain between 4.0-6.5 ;

步骤2、反应结束后过滤,收集滤饼,将滤饼加水分散后加入催化剂Fe2+得混合溶液,将所述混合溶液的pH值调节到6.5-7之间,进行加热反应,生成氧化铁红或氧化铁黄。Step 2, filter after the reaction is over, collect the filter cake, disperse the filter cake with water, add catalyst Fe 2+ to obtain a mixed solution, adjust the pH value of the mixed solution to between 6.5-7, and perform a heating reaction to generate iron oxide Red or iron oxide yellow.

降解有机废水主要以•OH与有机物发生反应,•OH的产生速率以及•OH与有机物的反应速率决定的,本发明中优先加入催化剂氧化铁诱发反应后,亚铁与H2O2同时加入,同时又原位生成大量纳米氧化铁催化剂,•OH产生效率得到提高,降解速率快。降解完成后,滤饼经过加热反应后,能得到颜料级氧化铁产品。The degradation of organic wastewater is mainly determined by the reaction between OH and organic matter, the production rate of OH and the reaction rate between OH and organic matter. In the present invention, after the catalyst iron oxide is preferentially added to induce the reaction, ferrous iron and H 2 O 2 are added at the same time, At the same time, a large number of nano-iron oxide catalysts are generated in situ, the efficiency of OH generation is improved, and the degradation rate is fast. After the degradation is completed, the filter cake can be heated and reacted to obtain pigment-grade iron oxide products.

优选地,所述氧化铁催化剂为氧化铁红、氧化铁黄、氧化铁黑、氢氧化铁、中的至少一种,加入量为0.5-2 g/L。Preferably, the iron oxide catalyst is at least one of iron oxide red, iron oxide yellow, iron oxide black, and iron hydroxide, and the amount added is 0.5-2 g/L.

优选地,所述步骤1中所述氧化剂为H2O2、O2、空气、过硫酸盐中的至少一种。所述步骤1中氧化剂与Fe2+同时加入,反应过程中pH值保持在5.0-5.5之间,所述步骤1中所述Fe2+与氧化剂的摩尔比为0.8-1.2:1。Preferably, the oxidizing agent in the step 1 is at least one of H 2 O 2 , O 2 , air, and persulfate. In the step 1, the oxidant and Fe 2+ are added at the same time, the pH value is kept between 5.0-5.5 during the reaction, and the molar ratio of the Fe 2+ to the oxidant in the step 1 is 0.8-1.2:1.

本发明中对的有机废水降解主要以•OH与有机物发生反应,H2O2、O2、空气或过硫酸盐均可以与Fe2+发生电子转移,迅速生成•OH,氧化剂过多会造成浪费,过少会产生的•OH太少,有机废水降解不彻底,因此Fe2+的量可以适当调整,保证将氧化剂全部生成•OH。The degradation of organic waste water in the present invention is mainly based on the reaction between OH and organic matter. H 2 O 2 , O 2 , air or persulfate can all undergo electron transfer with Fe 2+ to quickly generate OH. Too many oxidants will cause Waste, too little will produce too little •OH, and the degradation of organic wastewater will not be complete, so the amount of Fe 2+ can be adjusted appropriately to ensure that all oxidants will be generated •OH.

本发明为改进的异相类芬顿反应,同步加入氧化剂和Fe2+,pH值低于4时,不利于Fe3+水解,pH值高于6.5时,加入的Fe2+容易形成Fe(OH)2,在整个反应过程中一直保持pH在5.0-5.5,大大提高了降解效率,TOC的去除率均能达到80%以上。The present invention is an improved heterogeneous Fenton-like reaction, adding oxidant and Fe 2+ synchronously. When the pH value is lower than 4, it is not conducive to the hydrolysis of Fe 3+ . When the pH value is higher than 6.5, the added Fe 2+ is easy to form Fe( OH) 2 , keep the pH at 5.0-5.5 throughout the reaction process, which greatly improves the degradation efficiency, and the removal rate of TOC can reach more than 80%.

优选地,所述步骤1中所述氧化剂为H2O2,加入量为10-200mL/L。Preferably, the oxidizing agent in the step 1 is H 2 O 2 , and the amount added is 10-200 mL/L.

H2O2的加入量依据高含盐有机废水中有机物的含量。The amount of H 2 O 2 added is based on the content of organic matter in high-salt organic wastewater.

优选地,所述Fe2+是氯化亚铁、硫酸亚铁或钢铁酸洗废液中的一种。Preferably, the Fe 2+ is one of ferrous chloride, ferrous sulfate or steel pickling waste liquor.

Fe2+可以选择钢铁酸洗废液,既能废物利用,降低成本,还能达到优异的降解效果。Fe 2+ can be selected from iron and steel pickling waste, which can not only make waste utilization, reduce costs, but also achieve excellent degradation effect.

优选地,所述步骤3中,滤饼与水的质量比为1:0.5,加热反应温度95-100℃,加热反应时间2-3h。Preferably, in step 3, the mass ratio of filter cake to water is 1:0.5, the heating reaction temperature is 95-100°C, and the heating reaction time is 2-3h.

优选地,所述步骤2中,反应结束后过滤,将滤液蒸发出水分,留下盐份。Preferably, in the step 2, after the reaction is completed, filter, and evaporate the filtrate to remove water and leave salt.

所述步骤2中,滤液进行蒸发,水分会蒸发出去,冷凝得到处理后的COD含量低,无盐分的工业废水,同时蒸发留下的盐分中有机杂质的含量低,回收的盐分纯度更高。In the step 2, the filtrate is evaporated, the water evaporates, and the treated industrial wastewater with low COD content and no salt is obtained by condensation. At the same time, the content of organic impurities in the salt left by evaporation is low, and the recovered salt has higher purity.

优选地,所述高含盐有机废水来源于生物医药和/或精细化工产生的有机废水。Preferably, the high-salt organic wastewater is from biomedicine and/or fine chemical industry organic wastewater.

为了更好的说明本发明实施例提供的,下面通过实施例做进一步的举例说明。In order to better illustrate what the embodiments of the present invention provide, the following examples will be used for further illustration.

实施例1Example 1

本实施例提供一种降解高含盐有机废水及同步制备氧化铁的方法,高含盐有机废水选自生产DSD酸氧化阶段产生的工业废水,其中含NaSO4含量约为10wt%,总有机碳(TOC)为9438mg/L。取废水200 mL置于带搅拌的反应器中,加入0.5g氧化铁红催化剂,氧化剂为H2O2,然后分别取30wt% 的H2O2 30mL和3.7mol/L的氯化亚铁75mL,用蠕动泵同步加入到反应器中,反应液pH值用碱液控制在5.0-5.5,进行降解反应,降解后TOC为669mg/L,降解效率为92.9%。蒸出盐份后水样COD 为76 mg/L。滤饼铁氧化物经回流转化生成的氧化铁红产品着色力达到92%(511 nm),产品颜料性能良好。This embodiment provides a method for degrading high-salt organic wastewater and synchronously preparing iron oxide. The high-salt organic wastewater is selected from the industrial wastewater produced in the acid oxidation stage of the production of DSD, wherein the NaSO content is about 10wt%, and the total organic carbon (TOC) is 9438mg/L. Take 200 mL of waste water and place it in a stirred reactor, add 0.5 g of red iron oxide catalyst, the oxidant is H 2 O 2 , then take 30 mL of 30 wt% H 2 O 2 and 75 mL of 3.7 mol/L ferrous chloride , was added to the reactor synchronously with a peristaltic pump, the pH value of the reaction solution was controlled at 5.0-5.5 with lye, and the degradation reaction was carried out. After degradation, the TOC was 669mg/L, and the degradation efficiency was 92.9%. The COD of the water sample was 76 mg/L after the salt was evaporated. The coloring power of the iron oxide red product produced by the reflux transformation of the filter cake iron oxide reaches 92% (511 nm), and the product has good pigment performance.

实施例2Example 2

本实施例提供一种降解高含盐有机废水及同步制备氧化铁的方法,高含盐有机废水选自生产DSD酸氧化阶段产生的工业废水,其中含NaSO4含量约为10wt%,总有机碳(TOC)为9438mg/L。取废水200 mL置于带搅拌的反应器中,加入0.5g氧化铁红催化剂,氧化剂为Na2S2O8,然后分别取含有130g Na2S2O8的水溶液和3.7mol/L的氯化亚铁150 mL,蠕动泵同步加入到反应器中,反应液pH值用碱控制在5.0-5.5,进行降解反应,降解后TOC为366mg/L,降解效率为91.3%。蒸出盐份后水样COD 为49mg/L。滤饼铁氧化物经回流转化生成的氧化铁红,着色力达到97%(511 nm),产品颜料性能良好。This embodiment provides a method for degrading high-salt organic wastewater and synchronously preparing iron oxide. The high-salt organic wastewater is selected from the industrial wastewater produced in the acid oxidation stage of the production of DSD, wherein the NaSO content is about 10wt%, and the total organic carbon (TOC) is 9438mg/L. Take 200 mL of waste water and place it in a stirred reactor, add 0.5 g of iron oxide red catalyst, the oxidant is Na 2 S 2 O 8 , then take the aqueous solution containing 130 g of Na 2 S 2 O 8 and 3.7 mol/L chlorine 150 mL of ferrous oxide was added to the reactor simultaneously by a peristaltic pump. The pH value of the reaction solution was controlled at 5.0-5.5 with alkali, and the degradation reaction was carried out. After degradation, the TOC was 366 mg/L, and the degradation efficiency was 91.3%. The COD of the water sample was 49mg/L after the salt was evaporated. Iron oxide red produced by reflux conversion of filter cake iron oxide has a coloring power of 97% (511 nm), and the product has good pigment performance.

实施例3Example 3

本实施例提供一种降解高含盐有机废水及同步制备氧化铁的方法,高含盐有机废水选自生产DSD酸氧化阶段产生的工业废水,其中含NaSO4含量约为10wt%,总有机碳(TOC)为9438mg/L。取废水200 mL置于带搅拌的反应器中,加入0.5g氧化铁红催化剂,氧化剂为O2,取3.7mol/L的氯化亚铁105mL,用蠕动泵加入到反应器中,反应液pH值用碱控制在5.0-5.5,进行降解反应,降解后TOC为519mg/L,降解效率为96%。蒸出盐份后水样COD 为64mg/L。滤饼铁氧化物经回流转化生成的氧化铁红,着色力达到99%(511 nm),产品颜料性能良好。This embodiment provides a method for degrading high-salt organic wastewater and synchronously preparing iron oxide. The high-salt organic wastewater is selected from the industrial wastewater produced in the acid oxidation stage of the production of DSD, wherein the NaSO content is about 10wt%, and the total organic carbon (TOC) is 9438mg/L. Take 200 mL of waste water and place it in a stirred reactor, add 0.5 g of red iron oxide catalyst, the oxidant is O 2 , take 105 mL of 3.7 mol/L ferrous chloride, and add it to the reactor with a peristaltic pump, the reaction solution pH The value is controlled at 5.0-5.5 with alkali, and the degradation reaction is carried out. After degradation, the TOC is 519mg/L, and the degradation efficiency is 96%. After distilling off the salt, the COD of the water sample is 64mg/L. Iron oxide red produced by reflux conversion of the filter cake iron oxide has a coloring power of 99% (511 nm), and the product has good pigment performance.

实施例4Example 4

本实施例提供一种降解高含盐有机废水及同步制备氧化铁的方法,高含盐有机废水选自生产农药原料药产生的的工业废水,其中含NaCl含量约为11wt%,COD为57900mg/L。取废水200 mL置于带搅拌的反应器中,加入0.5g氧化铁黄催化剂,氧化剂为H2O2,然后分别取30wt% 的H2O2 8mL和3.7mol/L的氯化亚铁20.6mL,用蠕动泵同步加入到反应器中,反应过程中pH值用碱液控制在5.0-5.5。蒸出盐份后水样COD 为10520mg/L,降解效率为81%。滤饼铁氧化物经回流转化生成的氧化铁黄,着色力达到95%(511 nm),产品颜料性能良好。This embodiment provides a method for degrading high-salt organic wastewater and synchronously preparing iron oxide. The high-salt organic wastewater is selected from the industrial wastewater produced by the production of pesticide raw materials, wherein the NaCl content is about 11wt%, and the COD is 57900mg/ L. Take 200 mL of waste water and place it in a stirred reactor, add 0.5 g of iron oxide yellow catalyst, the oxidant is H 2 O 2 , then take 30 wt% H 2 O 2 8 mL and 3.7 mol/L ferrous chloride 20.6 mL was added to the reactor synchronously with a peristaltic pump, and the pH value was controlled at 5.0-5.5 with lye during the reaction. After steaming out the salt, the COD of the water sample is 10520mg/L, and the degradation efficiency is 81%. Iron oxide yellow produced by reflux conversion of the filter cake iron oxide has a coloring power of 95% (511 nm), and the product has good pigment performance.

实施例5Example 5

本实施例提供一种降解高含盐有机废水及同步制备氧化铁的方法,高含盐有机废水选自医药中间体生产过程中产生的的工业废水,其中NaCl和氯化铵含量约为13wt%、氯化亚铁为1.2mol/L和COD约为11000mg/L。取废水50mL置于带搅拌的反应器中,加入0.5g氧化铁红催化剂,然后将200mL含亚铁盐废水和30wt% 的H2O2 10mL同步加入反应器中,反应液pH值用碱液控制在5.0-5.5。蒸出盐份后冷却水COD 为280mg/L,降解效率为98%。滤饼铁氧化物经回流转化生成的氧化铁红,着色力达到101%(511 nm),产品颜料性能良好。This embodiment provides a method for degrading high-salt organic wastewater and synchronously preparing iron oxide. The high-salt organic wastewater is selected from industrial wastewater produced during the production of pharmaceutical intermediates, wherein the NaCl and ammonium chloride content is about 13 wt%. , Ferrous chloride is 1.2mol/L and COD is about 11000mg/L. Take 50mL of wastewater and place it in a stirred reactor, add 0.5g of red iron oxide catalyst, then add 200mL of ferrous salt-containing wastewater and 10mL of 30wt% H 2 O 2 into the reactor simultaneously, and the pH value of the reaction solution is adjusted with lye Control it at 5.0-5.5. After the salt is evaporated, the COD of the cooling water is 280mg/L, and the degradation efficiency is 98%. Iron oxide red produced by reflux conversion of the filter cake iron oxide has a coloring power of 101% (511 nm), and the product has good pigment performance.

以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换或改进等,均应包含在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement or improvement made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.

Claims (10)

1.一种降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述方法至少包括以下步骤:1. A method for degrading high-salt organic waste water and synchronously preparing iron oxide, characterized in that: the method at least comprises the following steps: 步骤1、将高含盐有机废水的pH值调节至4.0-6.5,预先加入铁氧化物催化剂,再加入氧化剂、Fe2+,进行反应,且控制反应过程中pH值保持在4.0-6.5之间;Step 1. Adjust the pH value of high-salt organic wastewater to 4.0-6.5, add iron oxide catalyst in advance, then add oxidant and Fe 2+ to carry out the reaction, and control the pH value during the reaction process to maintain between 4.0-6.5 ; 步骤2、反应结束后过滤,收集滤饼,将滤饼加水分散后加入催化剂Fe2+得混合溶液,将所述混合溶液的pH值调节到6.5-7之间,进行加热反应,生成氧化铁红或氧化铁黄。Step 2, filter after the reaction is over, collect the filter cake, disperse the filter cake with water, add catalyst Fe 2+ to obtain a mixed solution, adjust the pH value of the mixed solution to between 6.5-7, and perform a heating reaction to generate iron oxide Red or iron oxide yellow. 2.如权利要求1所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述氧化铁催化剂为氧化铁红、氧化铁黄、氧化铁黑、氢氧化铁、中的至少一种,加入量为0.5-2 g/L。2. the method for degrading high-salt organic waste water and synchronously preparing iron oxide as claimed in claim 1, is characterized in that: described iron oxide catalyst is iron oxide red, iron oxide yellow, iron oxide black, ferric hydroxide, medium At least one of them, the amount added is 0.5-2 g/L. 3.如权利要求1所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述步骤1中所述氧化剂为H2O2、O2、空气、过硫酸盐中的至少一种。3. The method for degrading high-salt organic wastewater and synchronously preparing iron oxide as claimed in claim 1, characterized in that: the oxidizing agent in the step 1 is H 2 O 2 , O 2 , air, persulfate at least one of . 4.如权利要求1所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述步骤1中氧化剂与Fe2+同时加入,反应过程中pH值保持在5.0-5.5之间。4. The method for degrading high-salt organic waste water and synchronously preparing iron oxide as claimed in claim 1, characterized in that: in the step 1, oxidant and Fe are added simultaneously, and the pH value remains at 5.0-5.5 during the reaction between. 5.如权利要求1所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述步骤1中所述Fe2+与氧化剂的摩尔比为0.8-1.2:1。5. The method for degrading high-salt organic waste water and synchronously preparing iron oxide as claimed in claim 1, characterized in that: the mol ratio of Fe described in step 1 to oxidant is 0.8-1.2 :1. 6.如权利要求5所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述步骤1中所述氧化剂为H2O2,加入量为10-200mL/L。6 . The method for degrading high-salt organic wastewater and synchronously preparing iron oxide as claimed in claim 5 , wherein the oxidizing agent in the step 1 is H 2 O 2 , and the amount added is 10-200 mL/L. 7.如权利要求1所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述Fe2+是氯化亚铁、硫酸亚铁或钢铁酸洗废液中的一种。7. The method for degrading high-salt organic waste water and synchronously preparing ferric oxide as claimed in claim 1, is characterized in that: said Fe 2+ is one of ferrous chloride, ferrous sulfate or iron and steel pickling waste liquid kind. 8.如权利要求1所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述步骤3中,滤饼与水的质量比为1:0.5,加热反应温度95-100℃,加热反应时间2-3h。8. The method for degrading high-salt organic waste water and synchronously preparing iron oxide as claimed in claim 1, characterized in that: in said step 3, the mass ratio of filter cake to water is 1:0.5, and the heating reaction temperature is 95- 100°C, heating reaction time 2-3h. 9.如权利要求1所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述步骤2中,反应结束后过滤,将滤液蒸发出水分,留下盐份。9. The method for degrading high-salt organic wastewater and synchronously preparing iron oxide as claimed in claim 1, characterized in that: in the step 2, after the reaction is completed, filter, evaporate the filtrate to remove water, and leave salt. 10.如权利要求1所述的降解高含盐有机废水及同步制备氧化铁的方法,其特征在于:所述高含盐有机废水来源于生物医药和/或精细化工产生的有机废水。10. The method for degrading high-salt organic wastewater and synchronously preparing iron oxide as claimed in claim 1, wherein the high-salt organic wastewater is derived from organic wastewater produced by biomedicine and/or fine chemical industry.
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CN110237481A (en) * 2018-07-10 2019-09-17 华东理工大学 A kind of harmless treatment method of waste salt
CN112875762A (en) * 2021-01-30 2021-06-01 嘉诚环保工程有限公司 Method for preparing iron oxide red by using iron-containing pickling waste liquid

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CN110237481A (en) * 2018-07-10 2019-09-17 华东理工大学 A kind of harmless treatment method of waste salt
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CN112875762B (en) * 2021-01-30 2022-05-17 河北粤海水务集团有限公司 Method for preparing iron oxide red by using iron-containing pickling waste liquid

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