CN105692967A - A kind of treatment method of waste water of PVA production plant - Google Patents
A kind of treatment method of waste water of PVA production plant Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及工业生产装置废水处理技术领域，具体说是一种PVA生产装置废水的处理方法。尤指利用“铁碳微电解+Fenton氧化+二级好氧”工艺深度处理PVA生产装置废水的方法。The invention relates to the technical field of industrial production device wastewater treatment, in particular to a method for treating wastewater from a PVA production device. In particular, it refers to the method of advanced treatment of wastewater from PVA production plants using the "iron-carbon micro-electrolysis + Fenton oxidation + secondary aerobic" process.
背景技术Background technique
工业废水是水污染的重要来源，占我国总污水排放量的百分之四五十左右，工业废水中由于含有高浓度的难降解污染物，导致其可生化性较差，盐度大，难以通过常规处理方法实现达标排放，对企业自身和周边环境造成巨大压力。Industrial wastewater is an important source of water pollution, accounting for about 40 to 50 percent of my country's total sewage discharge. Due to the high concentration of refractory pollutants contained in industrial wastewater, its biodegradability is poor, and its salinity is high. The standard discharge is achieved through conventional treatment methods, which puts enormous pressure on the enterprise itself and the surrounding environment.
PVA(聚乙烯醇)是一种用途广泛的水溶性高分子聚合物，分为纤维和非纤维两大用途，具有独特的粘结、耐油以及气体阻绝等特性，应用范围涉及纺织、食品、医药、造纸、印刷等行业。PVA生产过程中伴随产生大量的PVA生产装置废水，该废水具有有机物浓度高、水质水量变化大以及难生物降解等特点，属难处理的工业废水，应用常规的生物方法处理难以实现达标排放。PVA (polyvinyl alcohol) is a water-soluble polymer with a wide range of uses. It is divided into two major uses: fiber and non-fiber. It has unique bonding, oil resistance, and gas barrier properties. Its applications involve textiles, food, and medicine. , papermaking, printing and other industries. During the PVA production process, a large amount of PVA production plant wastewater is produced. The wastewater has the characteristics of high concentration of organic matter, large changes in water quality and quantity, and difficult biodegradation.
以四川某化工厂的生产装置所产生的PVA生产装置废水为例，该废水的pH为7左右，COD浓度为1000～1600mg/L，废水中含有的主要污染物为醋酸根和PVA，其中PVA属难生物降解有机物，含量为400～500mg/L，难以通过普通生化工艺实现达标排放。Taking the waste water from a PVA production plant produced by a production plant in a chemical plant in Sichuan as an example, the pH of the waste water is about 7, the COD concentration is 1000-1600 mg/L, and the main pollutants contained in the waste water are acetate and PVA, among which PVA It is a refractory biodegradable organic matter with a content of 400-500mg/L, and it is difficult to achieve standard discharge through ordinary biochemical processes.
铁碳微电解又称内电解法，是利用Fe/C原电池电解反应对废水进行预处理的技术，Fe/C原电池电解反应过程中产生Fe2+离子和H自由基，通过氧化还原、絮凝吸附、催化氧化以及络合沉积等作用对工业废水进行处理，不仅能去除废水中部分有机物，同时还能降低废水毒性，提高废水的可生化性。铁碳微电解具有适用范围广、处理效果好以及成本低廉等优点，并且利用废铁屑作为原料，具有废物资源再利用的意义。Iron-carbon micro-electrolysis, also known as internal electrolysis, is a technology that utilizes the electrolytic reaction of Fe/C primary battery to pretreat wastewater. During the electrolytic reaction of Fe/C primary battery, Fe 2+ ions and H free radicals are generated, which can The treatment of industrial wastewater by flocculation adsorption, catalytic oxidation and complex deposition can not only remove some organic matter in wastewater, but also reduce the toxicity of wastewater and improve the biodegradability of wastewater. Iron-carbon micro-electrolysis has the advantages of wide application range, good treatment effect and low cost, and the use of scrap iron scraps as raw materials has the significance of recycling waste resources.
Fenton反应是一种高级氧化技术，是指H2O2在Fe2+的催化下发生一些列链反应、生成高活性的羟基自由基的过程，羟基自由基具有很强的氧化能力，通过电子转移、亲电加成、脱氢反应等作用分解废水中的大部分有机污染物，常被用于造纸废水、含油废水、农药、防腐剂以及垃圾渗滤液等难降解废水的预处理。Fenton反应具有操作简单、氧化能力强、处理效率高、不产生二次污染等优势，引起了国内外的重视，成为水处理的研究热点。Fenton reaction is an advanced oxidation technology, which refers to the process in which H 2 O 2 undergoes a series of chain reactions under the catalysis of Fe 2+ to generate highly active hydroxyl radicals. Transfer, electrophilic addition, dehydrogenation reaction, etc. decompose most of the organic pollutants in wastewater, and are often used for pretreatment of refractory wastewater such as papermaking wastewater, oily wastewater, pesticides, preservatives, and landfill leachate. The Fenton reaction has the advantages of simple operation, strong oxidation capacity, high treatment efficiency, and no secondary pollution. It has attracted attention at home and abroad, and has become a research hotspot in water treatment.
好氧是最常见的生物处理工艺，该工艺通过微生物的吸附降解作用，将废水中的有机物转化为H2O和CO2等无害产物，从而实现废水的达标排放，随着废水排放量增大和环保标准的更加严格，采用二级好氧对废水进行处理显得尤为必要，二级好氧不仅降低了COD负荷对污泥系统的冲击，同时进一步的去除废水中的有机物，深度净化废水，实现废水的达标排放。Aerobic is the most common biological treatment process. This process converts organic matter in wastewater into harmless products such as H 2 O and CO 2 through the adsorption and degradation of microorganisms, so as to achieve the discharge of wastewater up to the standard. With the increase of wastewater discharge Daiwa's environmental protection standards are more stringent, and it is particularly necessary to use secondary aerobic treatment of wastewater. Secondary aerobic not only reduces the impact of COD load on the sludge system, but also further removes organic matter in wastewater and deeply purifies wastewater. Discharge of waste water up to standard.
专利“铁-碳微电解预处理含肼及其衍生物废水的方法”(申请号201310672391)介绍了一种铁-碳微电解预处理含肼及其衍生物废水的方法，将含肼及其衍生物废水用稀硫酸调节pH为2～4，然后将含肼及其衍生物废水通过微电解柱，同时向微电解柱中鼓气，含肼及其衍生物废水在微电解柱中的平均停留时间为2～24小时。所述微电解柱为Fe-C微电解柱，采用铁和炭为填料，铁、炭重量比为6:1～30:1，微电解柱中的填料铁为颗粒状或碎屑状的海绵铁、铁刨花或废铁屑铁制品，微电解柱中的填料炭为柱状、颗粒状或碎屑状的活性炭，填料铁和炭的粒径均为1～50mm。该发明简单可行、成本相对低廉，废水中COD去除率能达到70％～80％。The patent "Method for pretreatment of wastewater containing hydrazine and its derivatives by iron-carbon micro-electrolysis" (application number 201310672391) introduces a method for pre-treatment of wastewater containing hydrazine and its derivatives by iron-carbon micro-electrolysis. Use dilute sulfuric acid to adjust the pH of the derivative wastewater to 2-4, then pass the wastewater containing hydrazine and its derivatives through the micro-electrolysis column, and blow air into the micro-electrolysis column at the same time, the average value of the wastewater containing hydrazine and its derivatives in the micro-electrolysis column The residence time is 2 to 24 hours. The micro-electrolysis column is an Fe-C micro-electrolysis column, using iron and carbon as fillers, the weight ratio of iron and carbon is 6:1 to 30:1, and the filler iron in the micro-electrolysis column is granular or debris-like sponge Iron, iron shavings or waste iron scrap iron products, the filler carbon in the micro-electrolysis column is columnar, granular or chip-like activated carbon, and the particle size of the filler iron and carbon is 1-50mm. The invention is simple and feasible, and the cost is relatively low, and the COD removal rate in the waste water can reach 70%-80%.
“反渗透-微电解集成技术处理印染废水”(段晓笛、马宁，内蒙古工业大学学报，2008,27(3):178-181)介绍了一种采用反渗透-微电解集成技术处理印染废水的技术。印染废水先经反渗透膜处理，反渗透膜的透过液达到了再生水的水质，浓缩液再利用铁碳微电解处理，处理后达标排放。实验结果表明，在最佳条件下，铁碳微电解法对印染废水浓缩液处理十分有效，COD、浊度、色度去除率分别达到75％、99％、100％。"Treatment of Printing and Dyeing Wastewater by Reverse Osmosis-Micro-electrolysis Integrated Technology" (Duan Xiaodi, Ma Ning, Journal of Inner Mongolia University of Technology, 2008, 27(3): 178-181) introduces a method of using reverse osmosis-micro-electrolysis integrated technology to treat printing and dyeing wastewater technology. Printing and dyeing wastewater is first treated by reverse osmosis membrane, and the permeate of the reverse osmosis membrane has reached the water quality of reclaimed water. The concentrated solution is then treated by iron-carbon micro-electrolysis, and discharged after treatment. The experimental results show that under the optimal conditions, the iron-carbon micro-electrolysis method is very effective in the treatment of printing and dyeing wastewater concentrate, and the removal rates of COD, turbidity and chroma reach 75%, 99% and 100% respectively.
铁碳微电解处理工业废水具有工艺简单，效果明显优势，但对于一些难处理、难降解的工业废水，单一的铁碳微电解处理并不能达到排放标准或者达到满意的效果，因此，需要结合其他工艺进一步的进行深度处理。Iron-carbon micro-electrolysis treatment of industrial wastewater has the advantages of simple process and obvious effect, but for some difficult-to-treat and refractory industrial wastewater, a single iron-carbon micro-electrolysis treatment cannot meet the discharge standards or achieve satisfactory results. Therefore, it needs to be combined with other The process is further advanced treatment.
发明内容Contents of the invention
针对现有技术中存在的缺陷，本发明的目的在于提供一种PVA生产装置废水的处理方法，可以有效去除PVA生产装置废水中的污染物，实现PVA生产装置废水的达标排放。In view of the deficiencies in the prior art, the object of the present invention is to provide a method for treating wastewater from a PVA production plant, which can effectively remove pollutants in the wastewater from a PVA production plant and realize the discharge of wastewater from a PVA production plant up to standard.
为达到以上目的，本发明采取的技术方案是：For achieving above object, the technical scheme that the present invention takes is:
一种PVA生产装置废水的处理方法，其特征在于，包括如下步骤：A kind of processing method of PVA production plant wastewater, is characterized in that, comprises the steps:
步骤1，预处理：向PVA生产装置废水中加入酸，将其pH调节到2～4；Step 1, pretreatment: adding acid to the waste water of the PVA production plant to adjust its pH to 2-4;
步骤2，铁碳微电解：预处理后的PVA生产装置废水，进入铁碳微电解反应池，曝气反应，气水比为6:1～10:1，停留0.5～4h，对PVA生产装置废水进行处理，处理后PVA生产装置废水中Fe2+浓度为100～300mg/L；Step 2, iron-carbon micro-electrolysis: the pretreated waste water from the PVA production unit enters the iron-carbon micro-electrolysis reaction pool for aeration reaction, the gas-water ratio is 6:1-10:1, and the PVA production unit The wastewater is treated, and the concentration of Fe 2+ in the wastewater of the PVA production plant after treatment is 100-300mg/L;
步骤3，Fenton氧化：经铁碳微电解处理后的PVA生产装置废水，进入Fenton氧化反应池，加入H2O2，浓度为500～1500mg/L，充分搅拌进行反应，停留1～6h；Step 3, Fenton oxidation: PVA production plant wastewater treated by iron-carbon micro-electrolysis enters the Fenton oxidation reaction pool, adds H 2 O 2 at a concentration of 500-1500mg/L, fully stirs for reaction, and stays for 1-6 hours;
步骤4，絮凝沉降：向Fenton氧化反应池的出水中加入碱，调节该出水的pH至7～8之间，充分搅拌，絮凝沉降该出水中的铁离子；Step 4, flocculation and sedimentation: add alkali to the effluent of the Fenton oxidation reaction tank, adjust the pH of the effluent to between 7 and 8, stir fully, and flocculate and settle the iron ions in the effluent;
步骤5，一级好氧：絮凝沉降后，Fenton氧化反应池的出水进入一级好氧反应池，污泥浓度为1.5～2.5g/L，采用微孔爆气法曝气，维持氧含量在2～4mg/L，停留8～22h；Step 5, first-level aerobic: After flocculation and settlement, the effluent from the Fenton oxidation reaction tank enters the first-level aerobic reaction tank. 2~4mg/L, stay for 8~22h;
步骤6，二级好氧：一级好氧反应池的出水进入二级好氧反应池，污泥浓度为2～3g/L，采用微孔爆气法曝气，维持氧含量在2～4mg/L，停留时间为3～17h，二级好氧反应池的出水经过二沉池沉降后，二沉池的出水达标排放。Step 6, secondary aerobic: the effluent of the primary aerobic reaction tank enters the secondary aerobic reaction tank, the sludge concentration is 2-3g/L, and the microporous gas explosion method is used for aeration to maintain the oxygen content at 2-4mg /L, and the residence time is 3 to 17 hours. After the effluent from the secondary aerobic reaction tank is settled in the secondary settling tank, the effluent from the secondary settling tank reaches the standard for discharge.
在上述技术方案的基础上，步骤1中，所述PVA生产装置废水的水质为：COD浓度为1000～1600mg/L，pH为6.5～7.5，PVA含量为300～400mg/L，主要污染物为PVA和醋酸根。On the basis of the above-mentioned technical scheme, in step 1, the water quality of the wastewater from the PVA production plant is: the COD concentration is 1000-1600 mg/L, the pH is 6.5-7.5, the PVA content is 300-400 mg/L, and the main pollutants are PVA and acetate.
在上述技术方案的基础上，步骤1中，加入的酸为硫酸。On the basis of the above technical scheme, in step 1, the acid added is sulfuric acid.
在上述技术方案的基础上，步骤2中，停留时间为1～2h。On the basis of the above technical solution, in step 2, the residence time is 1 to 2 hours.
在上述技术方案的基础上，步骤3中，停留时间为2～4h。On the basis of the above technical solution, in step 3, the residence time is 2 to 4 hours.
在上述技术方案的基础上，步骤4中，加入的碱为氢氧化钠或者氢氧化钾。On the basis of the above-mentioned technical scheme, in step 4, the alkali added is sodium hydroxide or potassium hydroxide.
在上述技术方案的基础上，步骤5中，停留时间为10～20h。On the basis of the above technical solution, in step 5, the residence time is 10 to 20 hours.
在上述技术方案的基础上，步骤6中，停留时间为5～15h。On the basis of the above technical solution, in step 6, the residence time is 5 to 15 hours.
在上述技术方案的基础上，步骤6中，所述二沉池的出水，其COD小于60mg/L，满足《污水综合排放标准(GB8978-1996)》二类污染物一级排放标准要求。On the basis of the above technical solution, in step 6, the COD of the effluent from the secondary settling tank is less than 60 mg/L, which meets the requirements of the first-level discharge standard for second-class pollutants in the "Integrated Wastewater Discharge Standard (GB8978-1996)".
本发明所述的PVA生产装置废水的处理方法，采用“铁碳微电解+Fenton氧化+二级好氧”组合工艺，该组合工艺可以弥补单一工艺对PVA生产装置废水COD去除不彻底的缺陷，深度处理PVA生产装置废水，最终实现PVA生产装置废水的达标排放，该组合工艺具有处理效果显著，维护简单，投资少，成本低等优势。The method for treating waste water from a PVA production plant according to the present invention adopts the combined process of "iron-carbon micro-electrolysis + Fenton oxidation + secondary aerobic", which can make up for the incomplete removal of COD from the waste water of a PVA production plant by a single process. Advanced treatment of wastewater from PVA production equipment, and finally achieve the standard discharge of wastewater from PVA production equipment. This combined process has the advantages of remarkable treatment effect, simple maintenance, less investment, and low cost.
本发明所述的PVA生产装置废水的处理方法，创新点在于利用铁碳微电解和Fenton氧化反应降低PVA生产装置废水的COD，提高PVA生产装置废水的可生化性，通过二级好氧的深度处理实现PVA生产装置废水达标排放，解决了难降解化工废水的排放和治理难题，实现PVA生产装置废水的达标排放，具有显著的经济和社会效益。The method for treating waste water from a PVA production plant according to the present invention is innovative in that it utilizes iron-carbon micro-electrolysis and Fenton oxidation to reduce the COD of the waste water from a PVA production plant, improves the biodegradability of the waste water from a PVA production plant, and passes through the depth of secondary aerobic The treatment realizes the standard discharge of wastewater from PVA production equipment, solves the difficult problem of discharge and treatment of refractory chemical wastewater, and realizes the discharge of wastewater from PVA production equipment up to standard, which has significant economic and social benefits.
附图说明Description of drawings
本发明有如下附图：The present invention has following accompanying drawing:
图1本发明的工艺流程示意图。Fig. 1 is a schematic process flow diagram of the present invention.
具体实施方式detailed description
以下结合附图对本发明作进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings.
如图1所示，本发明所述的PVA生产装置废水的处理方法，包括如下步骤：As shown in Figure 1, the processing method of PVA production plant waste water of the present invention, comprises the steps:
步骤1，预处理：向PVA生产装置废水中加入酸，将其pH调节到2～4；Step 1, pretreatment: adding acid to the waste water of the PVA production plant to adjust its pH to 2-4;
步骤2，铁碳微电解：预处理后的PVA生产装置废水，进入铁碳微电解反应池，曝气反应，气水比为6:1～10:1，停留0.5～4h，对PVA生产装置废水进行处理，处理后PVA生产装置废水中Fe2+浓度为100～300mg/L；Step 2, iron-carbon micro-electrolysis: the pretreated waste water from the PVA production unit enters the iron-carbon micro-electrolysis reaction pool for aeration reaction, the gas-water ratio is 6:1-10:1, and the PVA production unit The wastewater is treated, and the concentration of Fe 2+ in the wastewater of the PVA production plant after treatment is 100-300mg/L;
步骤3，Fenton氧化：经铁碳微电解处理后的PVA生产装置废水，进入Fenton氧化反应池，加入H2O2，浓度为500～1500mg/L，充分搅拌进行反应，停留1～6h；Step 3, Fenton oxidation: PVA production plant wastewater treated by iron-carbon micro-electrolysis enters the Fenton oxidation reaction pool, adds H 2 O 2 at a concentration of 500-1500mg/L, fully stirs for reaction, and stays for 1-6 hours;
步骤4，絮凝沉降：向Fenton氧化反应池的出水中加入碱，调节该出水的pH至7～8之间，充分搅拌，絮凝沉降该出水中的铁离子；Step 4, flocculation and sedimentation: add alkali to the effluent of the Fenton oxidation reaction tank, adjust the pH of the effluent to between 7 and 8, stir fully, and flocculate and settle the iron ions in the effluent;
步骤5，一级好氧：絮凝沉降后，Fenton氧化反应池的出水进入一级好氧反应池，污泥浓度为1.5～2.5g/L，采用微孔爆气法曝气，维持氧含量在2～4mg/L，停留8～22h；Step 5, first-level aerobic: After flocculation and settlement, the effluent from the Fenton oxidation reaction tank enters the first-level aerobic reaction tank. 2~4mg/L, stay for 8~22h;
步骤6，二级好氧：一级好氧反应池的出水进入二级好氧反应池，污泥浓度为2～3g/L，采用微孔爆气法曝气，维持氧含量在2～4mg/L，停留时间为3～17h，二级好氧反应池的出水经过二沉池沉降后，二沉池的出水达标排放。Step 6, secondary aerobic: the effluent of the primary aerobic reaction tank enters the secondary aerobic reaction tank, the sludge concentration is 2-3g/L, and the microporous gas explosion method is used for aeration to maintain the oxygen content at 2-4mg /L, and the residence time is 3 to 17 hours. After the effluent from the secondary aerobic reaction tank is settled in the secondary settling tank, the effluent from the secondary settling tank reaches the standard for discharge.
在上述技术方案的基础上，步骤1中，所述PVA生产装置废水的水质为：COD浓度为1000～1600mg/L，pH为6.5～7.5，PVA含量为300～400mg/L，主要污染物为PVA和醋酸根。On the basis of the above-mentioned technical scheme, in step 1, the water quality of the wastewater from the PVA production plant is: the COD concentration is 1000-1600 mg/L, the pH is 6.5-7.5, the PVA content is 300-400 mg/L, and the main pollutants are PVA and acetate.
在上述技术方案的基础上，步骤1中，加入的酸为硫酸。On the basis of the above technical scheme, in step 1, the acid added is sulfuric acid.
在上述技术方案的基础上，步骤2中，优选停留时间为1～2h。On the basis of the above technical solution, in step 2, the preferred residence time is 1 to 2 hours.
在上述技术方案的基础上，步骤3中，优选停留时间为2～4h。On the basis of the above technical solution, in step 3, the preferred residence time is 2 to 4 hours.
在上述技术方案的基础上，步骤4中，加入的碱为氢氧化钠或者氢氧化钾。On the basis of the above-mentioned technical scheme, in step 4, the alkali added is sodium hydroxide or potassium hydroxide.
在上述技术方案的基础上，步骤5中，优选停留时间为10～20h。On the basis of the above technical solution, in step 5, the preferred residence time is 10-20 h.
在上述技术方案的基础上，步骤6中，优选停留时间为5～15h。On the basis of the above technical solution, in step 6, the preferred residence time is 5 to 15 hours.
在上述技术方案的基础上，步骤6中，所述二沉池的出水，其COD小于60mg/L，满足《污水综合排放标准(GB8978-1996)》二类污染物一级排放标准要求。On the basis of the above technical solution, in step 6, the COD of the effluent from the secondary settling tank is less than 60 mg/L, which meets the requirements of the first-level discharge standard for second-class pollutants in the "Integrated Wastewater Discharge Standard (GB8978-1996)".
本发明有如下突出的实质性特点和进步：The present invention has following outstanding substantive features and progress:
1)利用铁碳微电解对PVA生产装置废水进行处理，不但可以去除一部分有机物，降低COD负荷对后续工艺的冲击，避免了常规生化工艺处理PVA生产装置废水时，PVA析出，污泥粘连，使污泥上浮结块的问题，而且在铁碳微电解处理过程中会产生大量的亚铁离子，这些亚铁离子可以直接作为后续Fenton反应的催化剂，从而节省了Fenton反应的成本；1) Using iron-carbon micro-electrolysis to treat PVA production plant wastewater can not only remove part of the organic matter, reduce the impact of COD load on the subsequent process, and avoid the precipitation of PVA and sludge adhesion when conventional biochemical processes are used to treat PVA production plant wastewater. The problem of floating and agglomerating sludge, and a large amount of ferrous ions will be produced during the iron-carbon micro-electrolysis treatment process. These ferrous ions can be directly used as catalysts for the subsequent Fenton reaction, thereby saving the cost of the Fenton reaction;
2)Fenton氧化能够进一步去除PVA生产装置废水中的有机物，并且可以氧化PVA生产装置废水中的COD，提高可生化性，降低对后续生化处理系统的冲击；2) Fenton oxidation can further remove the organic matter in the wastewater of the PVA production plant, and can oxidize the COD in the wastewater of the PVA production plant, improve the biodegradability and reduce the impact on the subsequent biochemical treatment system;
3)一级好氧主要通过微生物的作用去除PVA生产装置废水中的大部分有机物；3) First-level aerobic mainly removes most of the organic matter in the wastewater of the PVA production plant through the action of microorganisms;
4)二级好氧可以进一步降解废水中残留的COD，对PVA生产装置废水进行深度处理，实现PVA生产装置废水的达标排放。4) The secondary aerobic can further degrade the residual COD in the wastewater, carry out advanced treatment of the wastewater from the PVA production plant, and realize the standard discharge of the wastewater from the PVA production plant.
本发明与专利“铁-碳微电解预处理含肼及其衍生物废水的方法”(申请号201310672391)相比，本工艺调节PVA生产装置废水的pH，利用铁碳微电解的处理，降低了PVA生产装置废水中的COD，随后的Fenton反应充分利用铁碳微电解产生的亚铁离子，节约了成本，对PVA生产装置废水进一步氧化，提高了PVA生产装置废水的可生化性，最后通过二级好氧的深度处理实现PVA生产装置废水达标排放。Compared with the patent "Method for Pretreatment of Wastewater Containing Hydrazine and Its Derivatives by Iron-Carbon Micro-electrolysis" (Application No. 201310672391), the present invention adjusts the pH of wastewater from a PVA production plant, and utilizes iron-carbon micro-electrolysis to reduce the The COD in the wastewater of the PVA production plant, the subsequent Fenton reaction fully utilizes the ferrous ions produced by iron-carbon micro-electrolysis, which saves the cost, further oxidizes the wastewater of the PVA production plant, improves the biodegradability of the wastewater of the PVA production plant, and finally passes the two Advanced aerobic treatment to achieve the standard discharge of wastewater from PVA production plants.
实施例如下：Examples are as follows:
实施例1：某企业的PVA生产装置废水，COD为1600mg/L，pH为7.5，主要污染物为PVA和醋酸根，处理步骤如下：Embodiment 1: the PVA production plant waste water of certain enterprise, COD is 1600mg/L, and pH is 7.5, and main pollutant is PVA and acetate, and processing steps are as follows:
步骤1：预处理，向PVA生产装置废水中加入硫酸，将其pH调节到2；Step 1: pretreatment, adding sulfuric acid to the waste water of the PVA production plant to adjust its pH to 2;
步骤2：铁碳微电解，上述预处理后的PVA生产装置废水进入铁碳微电解反应池，曝气反应，气水比为6:1，停留1h，处理后PVA生产装置废水中Fe2+浓度为100mg/L；Step 2: Iron-carbon micro-electrolysis, the wastewater from the PVA production unit after the above pretreatment enters the iron-carbon micro-electrolysis reaction tank, aeration reaction, the gas-water ratio is 6:1, and stays for 1h. Fe 2+ in the wastewater from the PVA production unit after treatment The concentration is 100mg/L;
步骤3：Fenton氧化，经铁碳微电解处理的PVA生产装置废水进入Fenton氧化反应池，加入H2O2，浓度为1500mg/L，搅拌进行反应，停留4h；Step 3: Fenton oxidation, the wastewater from the PVA production plant treated by iron-carbon micro-electrolysis enters the Fenton oxidation reaction pool, adds H 2 O 2 at a concentration of 1500 mg/L, stirs for reaction, and stays for 4 hours;
步骤4：絮凝沉降，Fenton氧化后出水中加入氢氧化钠，调节pH至8，充分搅拌，絮凝沉降PVA生产装置废水中的铁离子；Step 4: Flocculation and sedimentation, add sodium hydroxide to the effluent after Fenton oxidation, adjust the pH to 8, stir fully, and flocculate and settle the iron ions in the wastewater of the PVA production plant;
步骤5：一级好氧，PVA生产装置废水絮凝沉降后进入一级好氧反应池，采用微孔爆气法曝气，维持氧含量在4mg/L，污泥浓度为1.5g/L，充分曝气，停留20h；Step 5: First-level aerobic, the wastewater from the PVA production unit enters the first-level aerobic reaction tank after flocculation and sedimentation, and is aerated by the microporous gas explosion method to maintain the oxygen content at 4mg/L and the sludge concentration at 1.5g/L. Aeration, stay 20h;
步骤6：二级好氧，PVA生产装置废水经一级好氧反应池处理后，进入二级好氧反应池，采用微孔爆气法曝气，维持氧含量在2mg/L，污泥浓度为3g/L，停留时间为5h，经过二沉池沉降后出水。检测出水COD为55mg/L，达到排放标准要求。Step 6: Secondary aerobic, the wastewater from the PVA production unit is treated in the primary aerobic reaction tank, and then enters the secondary aerobic reaction tank, and is aerated by the microporous gas explosion method to maintain the oxygen content at 2mg/L and the sludge concentration The concentration is 3g/L, the residence time is 5h, and the water comes out after settling in the secondary settling tank. The water COD was detected to be 55mg/L, meeting the requirements of the discharge standard.
实施例2：某企业的PVA生产装置废水，COD为1000mg/L，pH为6.5，主要污染物为PVA和醋酸根，处理步骤如下：Embodiment 2: the PVA production plant waste water of certain enterprise, COD is 1000mg/L, and pH is 6.5, and main pollutant is PVA and acetate, and processing steps are as follows:
步骤1：预处理，向PVA生产装置废水中加入硫酸，将其pH调节到4；Step 1: pretreatment, adding sulfuric acid to the waste water of the PVA production plant to adjust its pH to 4;
步骤2：铁碳微电解，上述预处理后的PVA生产装置废水进入铁碳微电解反应池，曝气反应，气水比为10:1，停留2h，处理后PVA生产装置废水中Fe2+浓度为300mg/L；Step 2: Iron-carbon micro-electrolysis, the wastewater from the PVA production plant after the above pretreatment enters the iron-carbon micro-electrolysis reaction tank, aeration reaction, the gas-water ratio is 10:1, and stays for 2 hours. The concentration is 300mg/L;
步骤3：Fenton氧化，经铁碳微电解处理的PVA生产装置废水进入Fenton氧化反应池，加入H2O2，浓度为500mg/L，搅拌进行反应，停留2h；Step 3: Fenton oxidation, the wastewater from the PVA production plant treated by iron-carbon micro-electrolysis enters the Fenton oxidation reaction pool, adds H 2 O 2 at a concentration of 500 mg/L, stirs for reaction, and stays for 2 hours;
步骤4：絮凝沉降，Fenton氧化后出水中加入氢氧化钾，调节pH至7，充分搅拌，絮凝沉降PVA生产装置废水中的铁离子；Step 4: flocculation and sedimentation, adding potassium hydroxide to the effluent after Fenton oxidation, adjusting the pH to 7, stirring fully, flocculation and sedimentation of iron ions in the wastewater of the PVA production plant;
步骤5：一级好氧，PVA生产装置废水絮凝沉降后进入一级好氧反应池，采用微孔爆气法曝气，维持氧含量在2mg/L，污泥浓度为2.5g/L，充分曝气，停留10h；Step 5: First-level aerobic, the wastewater from the PVA production unit enters the first-level aerobic reaction tank after flocculation and sedimentation, and is aerated by the microporous gas explosion method to maintain the oxygen content at 2mg/L and the sludge concentration at 2.5g/L. Aeration, stay 10h;
步骤6：二级好氧，PVA生产装置废水经一级好氧反应池处理后，进入二级好氧反应池，采用微孔爆气法曝气，维持氧含量在4mg/L，污泥浓度为2g/L，停留时间为15h，经过二沉池沉降后出水。检测出水COD为40mg/L，达到排放标准要求。Step 6: Secondary aerobic, the waste water from the PVA production unit is treated in the primary aerobic reaction tank, then enters the secondary aerobic reaction tank, and is aerated by the microporous gas explosion method to maintain the oxygen content at 4mg/L and the sludge concentration The concentration is 2g/L, the residence time is 15h, and the water comes out after settling in the secondary settling tank. The water COD was detected to be 40mg/L, meeting the requirements of the discharge standard.
实施例3：某企业的PVA生产装置废水，COD为1300mg/L，pH为7，主要污染物为PVA和醋酸根，处理步骤如下：Embodiment 3: the PVA production plant waste water of certain enterprise, COD is 1300mg/L, and pH is 7, and main pollutant is PVA and acetate, and processing steps are as follows:
步骤1：预处理，向PVA生产装置废水中加入硫酸，将其pH调节到3；Step 1: pretreatment, adding sulfuric acid to the waste water of the PVA production plant to adjust its pH to 3;
步骤2：铁碳微电解，上述预处理后的PVA生产装置废水进入铁碳微电解反应池，曝气反应，气水比为8:1，停留1.5h，处理后PVA生产装置废水中Fe2+浓度为200mg/L；Step 2: Iron-carbon micro-electrolysis, the wastewater from the PVA production plant after the above pretreatment enters the iron-carbon micro-electrolysis reaction tank, aeration reaction, the gas-water ratio is 8: 1 , and stays for 1.5h. After the treatment, Fe in the wastewater from the PVA production plant + The concentration is 200mg/L;
步骤3：Fenton氧化，经铁碳微电解处理的PVA生产装置废水进入Fenton氧化反应池，加入H2O2，浓度为1000mg/L，搅拌进行反应，停留3h；Step 3: Fenton oxidation, the wastewater from the PVA production plant treated by iron-carbon micro-electrolysis enters the Fenton oxidation reaction pool, adds H 2 O 2 at a concentration of 1000 mg/L, stirs for reaction, and stays for 3 hours;
步骤4：絮凝沉降，Fenton氧化后出水中加入氢氧化钠，调节pH至7.5，充分搅拌，絮凝沉降PVA生产装置废水中的铁离子；Step 4: Flocculation and sedimentation, add sodium hydroxide to the effluent after Fenton oxidation, adjust the pH to 7.5, stir fully, and flocculate and settle the iron ions in the wastewater of the PVA production plant;
步骤5：一级好氧，PVA生产装置废水絮凝沉降后进入一级好氧反应池，采用微孔爆气法曝气，维持氧含量在3mg/L，污泥浓度为2g/L，充分曝气，停留15h；Step 5: First-level aerobic, the wastewater from the PVA production unit enters the first-level aerobic reaction tank after flocculation and sedimentation, and is aerated by the microporous gas explosion method to maintain the oxygen content at 3mg/L and the sludge concentration at 2g/L. Gas, stay for 15h;
步骤6：二级好氧，PVA生产装置废水经一级好氧反应池处理后，进入二级好氧反应池，采用微孔爆气法曝气，维持氧含量在3mg/L，污泥浓度为2.5g/L，停留时间为10h，经过二沉池沉降后出水。检测出水COD为50mg/L，达到排放标准要求。Step 6: Secondary aerobic, the wastewater from the PVA production plant is treated in the primary aerobic reaction tank, and then enters the secondary aerobic reaction tank, and is aerated by the microporous gas explosion method to maintain the oxygen content at 3mg/L and the sludge concentration The concentration is 2.5g/L, the residence time is 10h, and the water comes out after settling in the secondary settling tank. The water COD was detected to be 50mg/L, meeting the requirements of the discharge standard.
实施例4：某企业的PVA生产装置废水，COD为1300mg/L，pH为6.7，主要污染物为PVA和醋酸根，处理步骤如下：Embodiment 4: the PVA production plant waste water of certain enterprise, COD is 1300mg/L, and pH is 6.7, and main pollutant is PVA and acetate, and processing steps are as follows:
步骤1预处理，向PVA生产装置废水中加入硫酸，将其pH调节到2.5；Step 1 pretreatment, adding sulfuric acid to the waste water of the PVA production plant to adjust its pH to 2.5;
步骤2：铁碳微电解，上述预处理后的PVA生产装置废水进入铁碳微电解反应池，曝气反应，气水比为7:1，停留1.3h，处理后PVA生产装置废水中Fe2+浓度为160mg/L；Step 2: Iron-carbon micro-electrolysis, the wastewater from the PVA production plant after the above pretreatment enters the iron-carbon micro-electrolysis reaction tank, aeration reaction, the gas-water ratio is 7:1, and stays for 1.3h. After the treatment, Fe 2 in the wastewater from the PVA production plant + The concentration is 160mg/L;
步骤3：Fenton氧化，经铁碳微电解处理的PVA生产装置废水进入Fenton氧化反应池，加入H2O2，浓度为700mg/L，搅拌进行反应，停留2.5h；Step 3: Fenton oxidation, the wastewater from the PVA production plant treated by iron-carbon micro-electrolysis enters the Fenton oxidation reaction pool, adds H 2 O 2 at a concentration of 700 mg/L, stirs for reaction, and stays for 2.5 hours;
步骤4：絮凝沉降，Fenton氧化后出水中加入氢氧化钾，调节pH至7.7，充分搅拌，絮凝沉降PVA生产装置废水中的铁离子；Step 4: flocculation and sedimentation, adding potassium hydroxide to the effluent after Fenton oxidation, adjusting the pH to 7.7, stirring fully, flocculation and sedimentation of iron ions in the wastewater of the PVA production plant;
步骤5：一级好氧，PVA生产装置废水絮凝沉降后进入一级好氧反应池，采用微孔爆气法曝气，维持氧含量在2.5mg/L，污泥浓度为1.8g/L，充分曝气，停留13h；Step 5: First-level aerobic, the wastewater from the PVA production unit enters the first-level aerobic reaction tank after flocculation and sedimentation, and is aerated by the microporous gas explosion method to maintain the oxygen content at 2.5mg/L and the sludge concentration at 1.8g/L. Fully aerate and stay for 13 hours;
步骤6：二级好氧，PVA生产装置废水经一级好氧反应池处理后，进入二级好氧反应池，采用微孔爆气法曝气，维持氧含量在3.5mg/L，污泥浓度为2.3g/L，停留时间为7h，经过二沉池沉降后出水。检测出水COD为53mg/L，达到排放标准要求。Step 6: Secondary aerobic, the wastewater from the PVA production unit is treated in the primary aerobic reaction tank, then enters the secondary aerobic reaction tank, and is aerated by the microporous gas explosion method to maintain the oxygen content at 3.5mg/L, and the sludge The concentration is 2.3g/L, the residence time is 7h, and the water comes out after settling in the secondary settling tank. The water COD was detected to be 53mg/L, meeting the discharge standard requirements.
实施例5：某企业的PVA生产装置废水，COD为1400mg/L，pH为7.3，主要污染物为PVA和醋酸根，处理步骤如下：Embodiment 5: the PVA production plant waste water of certain enterprise, COD is 1400mg/L, and pH is 7.3, and main pollutant is PVA and acetate, and processing steps are as follows:
步骤1：预处理，向PVA生产装置废水中加入硫酸，将其pH调节到3.5；Step 1: pretreatment, adding sulfuric acid to the waste water of the PVA production plant to adjust its pH to 3.5;
步骤2：铁碳微电解，上述预处理后的PVA生产装置废水进入铁碳微电解反应池，曝气反应，气水比为9:1，停留1.7h，处理后PVA生产装置废水中Fe2+浓度为240mg/L；Step 2: Iron-carbon micro-electrolysis, the wastewater from the PVA production plant after the above pretreatment enters the iron-carbon micro-electrolysis reaction tank, aeration reaction, the gas-water ratio is 9:1, and stays for 1.7h. After the treatment, Fe 2 in the wastewater from the PVA production plant + The concentration is 240mg/L;
步骤3：Fenton氧化，经铁碳微电解处理的PVA生产装置废水进入Fenton氧化反应池，加入H2O2，浓度为1300mg/L，搅拌进行反应，停留3.5h；Step 3: Fenton oxidation, the wastewater from the PVA production plant treated by iron-carbon micro-electrolysis enters the Fenton oxidation reaction pool, adds H 2 O 2 at a concentration of 1300 mg/L, stirs for reaction, and stays for 3.5 hours;
步骤4：絮凝沉降，Fenton氧化后出水中加入氢氧化钠，调节pH至7.3，充分搅拌，絮凝沉降PVA生产装置废水中的铁离子；Step 4: Flocculation and sedimentation, add sodium hydroxide to the effluent after Fenton oxidation, adjust the pH to 7.3, stir fully, and flocculate and settle the iron ions in the wastewater of the PVA production plant;
步骤5：一级好氧，PVA生产装置废水絮凝沉降后进入一级好氧反应池，采用微孔爆气法曝气，维持氧含量在3.5mg/L，污泥浓度为2.2g/L，充分曝气，停留17h；Step 5: First-level aerobic, the wastewater from the PVA production unit enters the first-level aerobic reaction tank after flocculation and sedimentation, and is aerated by the microporous gas explosion method to maintain the oxygen content at 3.5mg/L and the sludge concentration at 2.2g/L. Fully aerate, stay for 17h;
步骤6：二级好氧，PVA生产装置废水经一级好氧反应池处理后，进入二级好氧反应池，采用微孔爆气法曝气，维持氧含量在2.5mg/L，污泥浓度为2.8g/L，停留时间为13h，经过二沉池沉降后出水。检测出水COD为45mg/L，达到排放标准要求。Step 6: Secondary aerobic, the wastewater from the PVA production plant is treated in the primary aerobic reaction tank, then enters the secondary aerobic reaction tank, and is aerated by the microporous gas explosion method to maintain the oxygen content at 2.5mg/L, and the sludge The concentration is 2.8g/L, the residence time is 13h, and the water comes out after settling in the secondary settling tank. The water COD was detected to be 45mg/L, meeting the requirements of the discharge standard.
对比例1:某企业的PVA生产装置废水，COD为1600mg/L，pH为7.5，主要污染物为PVA和醋酸根，处理步骤如下：Comparative example 1: the PVA production plant waste water of certain enterprise, COD is 1600mg/L, and pH is 7.5, and main pollutant is PVA and acetate, and processing steps are as follows:
步骤1：预处理，向PVA生产装置废水中加入硫酸，将其pH调节到2；Step 1: pretreatment, adding sulfuric acid to the waste water of the PVA production plant to adjust its pH to 2;
步骤2：铁碳微电解，上述预处理后的PVA生产装置废水进入铁碳微电解反应池，曝气反应，气水比为6:1，停留1h，处理后PVA生产装置废水中Fe2+浓度为100mg/L；Step 2: Iron-carbon micro-electrolysis, the wastewater from the PVA production unit after the above pretreatment enters the iron-carbon micro-electrolysis reaction tank, aeration reaction, the gas-water ratio is 6:1, and stays for 1h. Fe 2+ in the wastewater from the PVA production unit after treatment The concentration is 100mg/L;
步骤3：絮凝沉降，铁碳微电解出水中加入氢氧化钠，调节pH至8，充分搅拌，絮凝沉降PVA生产装置废水中的铁离子；Step 3: Flocculation and sedimentation, add sodium hydroxide to the water effluent from iron-carbon micro-electrolysis, adjust the pH to 8, stir fully, and flocculate and settle the iron ions in the wastewater of the PVA production plant;
步骤4：一级好氧，PVA生产装置废水絮凝沉降后进入一级好氧反应池，采用微孔爆气法曝气，维持氧含量在4mg/L，污泥浓度为1.5g/L，充分曝气，停留20h；Step 4: First-level aerobic, the wastewater from the PVA production unit enters the first-level aerobic reaction tank after flocculation and sedimentation, and is aerated by the microporous gas explosion method to maintain the oxygen content at 4mg/L and the sludge concentration at 1.5g/L. Aeration, stay 20h;
步骤5：二级好氧，PVA生产装置废水经一级好氧反应池处理后，进入二级好氧反应池，采用微孔爆气法曝气，维持氧含量在2mg/L，污泥浓度为3g/L，停留时间为5h，经过二沉池沉降后出水，检测出水COD为120mg/L。与实施例1相比，未经过Fenton氧化处理的PVA生产装置废水，仅经过铁碳微电解+二级好氧，出水COD超标。Step 5: Secondary aerobic, the wastewater from the PVA production unit is treated in the first-level aerobic reaction tank, then enters the second-level aerobic reaction tank, and is aerated by the microporous gas explosion method to maintain the oxygen content at 2mg/L and the sludge concentration It is 3g/L, and the residence time is 5h. After settling in the secondary sedimentation tank, the water is discharged, and the COD of the water is detected to be 120mg/L. Compared with Example 1, the PVA production plant wastewater that has not been treated by Fenton oxidation has only undergone iron-carbon micro-electrolysis + secondary aerobic, and the COD of the effluent exceeds the standard.
对比例2：某企业的PVA生产装置废水，COD为1400mg/L，pH为7.3，主要污染物为PVA和醋酸根，处理步骤如下：Comparative example 2: Wastewater from a PVA production plant in a certain company, COD is 1400mg/L, pH is 7.3, and the main pollutants are PVA and acetate. The treatment steps are as follows:
步骤1：预处理，向PVA生产装置废水中加入硫酸，将其pH调节到3.5；Step 1: pretreatment, adding sulfuric acid to the waste water of the PVA production plant to adjust its pH to 3.5;
步骤2：铁碳微电解，上述预处理后的PVA生产装置废水进入铁碳微电解反应池，曝气反应，气水比为9:1，停留1.7h，处理后PVA生产装置废水中Fe2+浓度为240mg/L；Step 2: Iron-carbon micro-electrolysis, the wastewater from the PVA production plant after the above pretreatment enters the iron-carbon micro-electrolysis reaction tank, aeration reaction, the gas-water ratio is 9:1, and stays for 1.7h. After the treatment, Fe 2 in the wastewater from the PVA production plant + The concentration is 240mg/L;
步骤3：Fenton氧化，经铁碳微电解处理的PVA生产装置废水进入Fenton氧化反应池，加入H2O2，浓度为1300mg/L，搅拌进行反应，停留3.5h；Step 3: Fenton oxidation, the wastewater from the PVA production plant treated by iron-carbon micro-electrolysis enters the Fenton oxidation reaction pool, adds H 2 O 2 at a concentration of 1300 mg/L, stirs for reaction, and stays for 3.5 hours;
步骤4：絮凝沉降，Fenton氧化后出水中加入氢氧化钠，调节pH至7.3，充分搅拌，絮凝沉降PVA生产装置废水中的铁离子；Step 4: Flocculation and sedimentation, add sodium hydroxide to the effluent after Fenton oxidation, adjust the pH to 7.3, stir fully, and flocculate and settle the iron ions in the wastewater of the PVA production plant;
步骤5：好氧，PVA生产装置废水絮凝沉降后进入好氧反应池，采用微孔爆气法曝气，维持氧含量在2.5mg/L，污泥浓度为2.8g/L，停留时间为13h，经过二沉池沉降后出水，检测出水COD为90mg/L，与实施例5相比，采用一级好氧，PVA生产装置废水出水COD大于60mg/L，无法实现达标排放。Step 5: Aerobic, the wastewater from the PVA production unit enters the aerobic reaction tank after flocculation and sedimentation, and is aerated by the microporous gas explosion method to maintain the oxygen content at 2.5mg/L, the sludge concentration at 2.8g/L, and the residence time at 13h , after the secondary settling tank subsides, the water is discharged, and the detected water COD is 90mg/L. Compared with Example 5, the first-level aerobic method is adopted, and the COD of the PVA production plant wastewater effluent is greater than 60mg/L, which cannot achieve the standard discharge.
本说明书中未作详细描述的内容属于本领域专业技术人员公知的现有技术。The content not described in detail in this specification belongs to the prior art known to those skilled in the art.
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