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 PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 150000003839 salts Chemical class 0.000 title claims abstract description 13
- 239000010815 organic waste Substances 0.000 title claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- 239000012065 filter cake Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000000593 degrading effect Effects 0.000 claims description 20
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000012847 fine chemical Substances 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 230000015556 catabolic process Effects 0.000 abstract description 19
- 239000000047 product Substances 0.000 abstract description 10
- 239000005416 organic matter Substances 0.000 abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241001274216 Naso Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- 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
- C02F2305/023—Reactive 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
Description
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.
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