CN103435142A - General-purpose internal circulation fenton reactor treating difficult-to-degrade organic wastewater - Google Patents
General-purpose internal circulation fenton reactor treating difficult-to-degrade organic wastewater Download PDFInfo
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Abstract
一种处理难降解有机废水的通用型内循环芬顿反应器，其结构包括：进水口、混合区、挡板、第一重套筒、第二重套筒、第三重套筒、紫外灯、溢流槽、出水口、反应器外壁、第一反应区、第二反应区、曝气头、空气入口。所述反应器是上部为圆柱、下部为圆台的加盖筒体，底部设进水口和曝气头，中间设置下部开口的三重套筒，将反应器分隔为混合区、第一反应区和第二反应区，上部设溢流槽和出水口，底部设有倒置喇叭状的挡板，反应器内布置有紫外灯。该反应器对难降解有机废水有较好的处理效果，多相催化剂在反应器各反应区之间循环，可以重复利用，有机污染物矿化度高。
A general-purpose internal circulation Fenton reactor for treating refractory organic wastewater, its structure includes: water inlet, mixing zone, baffle, first heavy sleeve, second heavy sleeve, third heavy sleeve, ultraviolet lamp , overflow tank, water outlet, outer wall of reactor, first reaction zone, second reaction zone, aeration head, air inlet. The reactor is a covered cylinder with a cylinder at the top and a round table at the bottom, with a water inlet and aeration head at the bottom, and a triple sleeve with the lower opening in the middle, which divides the reactor into a mixing zone, a first reaction zone and a second reaction zone. In the second reaction zone, an overflow tank and a water outlet are arranged on the upper part, and an inverted trumpet-shaped baffle is arranged on the bottom, and an ultraviolet lamp is arranged in the reactor. The reactor has a better treatment effect on refractory organic wastewater, and the heterogeneous catalyst circulates among the reaction zones of the reactor, which can be reused, and the organic pollutants have high salinity.
Description
技术领域 technical field
本发明涉及一种处理难降解有机废水的通用型内循环芬顿（Fenton）反应器，属于污水处理领域。 The invention relates to a general-purpose internal circulation Fenton reactor for treating refractory organic wastewater, which belongs to the field of sewage treatment.
背景技术 Background technique
在各种类型的废水中，含有大量难降解有机污染物的废水是水污染的主要元凶。这些难被微生物降解的有机污染物主要来源于石油化工、冶金、印染、制药、造纸等工业行业，以及农村使用的农药和城市生活垃圾。这些难降解有机废水的特点是浓度较高，成分复杂，毒性强，化学耗氧量高、具有“三致”作用或毒性，一旦向环境排放，将会引发严峻的环境污染，并威胁人民的健康。 Among various types of wastewater, wastewater containing a large amount of refractory organic pollutants is the main culprit of water pollution. These organic pollutants that are difficult to be degraded by microorganisms mainly come from industrial industries such as petrochemical, metallurgy, printing and dyeing, pharmaceuticals, and papermaking, as well as pesticides used in rural areas and municipal solid waste. The characteristics of these refractory organic wastewater are high concentration, complex composition, strong toxicity, high chemical oxygen consumption, and "three effects" or toxicity. Once discharged to the environment, it will cause severe environmental pollution and threaten people's health. healthy.
目前难降解有机废水的处理方法主要有三大类，分别是：生物法、物理法和化学氧化法。随着民众环境保护意识的日益增强和国家污染物排放标准的日趋严格，之前大多数企业采用的生物处理技术不能达到最新的行业废水排放标准，目前被广泛接受的工艺是采用生化处理+深度处理相结合的处理方法，生化处理可以在低成本的条件下去除大量污染物，而深度处理则能进一步去除废水中的难降解有机物，保证达到排放标准。目前研究较多的深度处理技术是膜分离技术和高级氧化技术。膜分离技术虽然处理效果不错，但是由于浓缩液难处理、膜易污染以及投资运行成本高等缺点，应用受到很大限制。高级氧化法利用羟基自由基（·OH）将废水中的有毒有机物分解成为无毒或低毒的小分子物质进而提高其可生化性，甚至彻底转化为二氧化碳和水等无机物，是一种彻底处理水中有机污染物的方法。 At present, there are three main types of treatment methods for refractory organic wastewater, namely: biological method, physical method and chemical oxidation method. With the increasing public awareness of environmental protection and the increasingly stringent national pollutant discharge standards, the biological treatment technology used by most enterprises cannot meet the latest industry wastewater discharge standards. The currently widely accepted process is to use biochemical treatment + advanced treatment Combining treatment methods, biochemical treatment can remove a large amount of pollutants at low cost, while advanced treatment can further remove refractory organic matter in wastewater to ensure that discharge standards are met. At present, the advanced treatment technologies that have been studied more are membrane separation technology and advanced oxidation technology. Although the treatment effect of membrane separation technology is good, its application is greatly limited due to the disadvantages of difficult treatment of concentrated liquid, easy membrane fouling and high investment and operation costs. The advanced oxidation method uses hydroxyl radicals (OH) to decompose toxic organic substances in wastewater into non-toxic or low-toxic small molecular substances, thereby improving their biodegradability, and even completely transforming them into inorganic substances such as carbon dioxide and water. Methods for treating organic pollutants in water.
芬顿（Fenton）技术是近年来比较受重视的一种高级氧化技术（AOPs）：Fe2+催化H2O2生成氧化能力极高的·OH，·OH进一步氧化有机物。光助-芬顿体系（Photo-Fenton）则兼具高级氧化技术和光催化氧化技术的优点，降解效率高、二次污染低。在难降解废水处理领域，光助-芬顿体系已经逐渐成为公认的最具应用前景的技术之一。均相光助-芬顿体系和多相光助-芬顿体系各有优缺点，均相光助-芬顿体系存在pH值适用范围窄、铁离子容易流失造成二次污染等问题，多相光助芬顿体系虽然在较广的pH值范围内对难降解有机废水有较好的处理效果，但处理效率低于均相光助芬顿体系。 Fenton technology is an advanced oxidation technology (AOPs) that has received more attention in recent years: Fe 2+ catalyzes H 2 O 2 to generate ·OH with extremely high oxidation ability, and ·OH further oxidizes organic matter. Photo-Fenton system (Photo-Fenton) combines the advantages of advanced oxidation technology and photocatalytic oxidation technology, with high degradation efficiency and low secondary pollution. In the field of refractory wastewater treatment, the photoassisted-Fenton system has gradually become one of the most promising technologies. The homogeneous photo-assisted-Fenton system and the heterogeneous photo-assisted-Fenton system have their own advantages and disadvantages. The homogeneous photo-assisted-Fenton system has problems such as a narrow pH range and easy loss of iron ions causing secondary pollution. Although the photo-assisted Fenton system has a good treatment effect on refractory organic wastewater in a wide pH range, its treatment efficiency is lower than that of the homogeneous photo-assisted Fenton system.
目前极少有光助-芬顿法用于实际废水的工业化处理，除了成本要进一步控制外，急需要解决的就是设计出结构简单、效率高、适于工业化的光反应器。已经研究出的光催化-膜分离反应器和三相内循环流化床光催化反应器都为多相光催化反应器的设计提供了很好的思路，真正应用于废水处理工业化还有很长的路要走。 At present, there are very few photo-assisted-Fenton methods used in the industrial treatment of actual wastewater. In addition to further cost control, an urgent need to solve is to design a photoreactor with a simple structure, high efficiency, and suitable for industrialization. The photocatalytic-membrane separation reactor and the three-phase internal circulating fluidized bed photocatalytic reactor that have been studied have provided a good idea for the design of the heterogeneous photocatalytic reactor, and there is still a long way to go before the industrialization of wastewater treatment. way to go.
发明内容 Contents of the invention
本发明的目的是针对日益严峻的水污染形势以及现有技术的不足提供一种可利用芬顿体系处理难降解有机废水的通用型内循环芬顿反应器。 The object of the present invention is to provide a general-purpose internal circulation Fenton reactor which can use the Fenton system to treat refractory organic wastewater in view of the increasingly severe water pollution situation and the deficiencies of the prior art.
本发明的结构包括：进水口、混合区、挡板、第一重套筒、第二重套筒、第三重套筒、紫外灯、溢流槽、出水口、反应器外壁、第一反应区、第二反应区、曝气头、空气入口； The structure of the present invention includes: water inlet, mixing area, baffle, first heavy sleeve, second heavy sleeve, third heavy sleeve, ultraviolet lamp, overflow tank, water outlet, reactor outer wall, first reaction zone, second reaction zone, aeration head, air inlet;
所述反应器是上部为圆柱、下部为圆台的加盖筒体，底部设进水口和曝气头，中间设置下部开口的三重套筒，将反应器分隔为混合区、第一反应区和第二反应区，上部设溢流槽和出水口，底部设有倒置喇叭状的挡板，反应器内布置有紫外灯； The reactor is a covered cylinder with a cylinder at the top and a round table at the bottom, with a water inlet and aeration head at the bottom, and a triple sleeve with a lower opening in the middle, which divides the reactor into a mixing zone, a first reaction zone and a second reaction zone. In the second reaction zone, an overflow tank and a water outlet are arranged on the upper part, and an inverted trumpet-shaped baffle is arranged on the bottom, and ultraviolet lamps are arranged in the reactor;
所述反应器中央的第一反应区布置紫外灯束，反应器外围的第二反应区均匀布置数根紫外灯； An ultraviolet lamp beam is arranged in the first reaction zone in the center of the reactor, and several ultraviolet lamps are evenly arranged in the second reaction zone on the periphery of the reactor;
所述系统下部开口的三重套筒，其结构可以是套筒上部为圆柱形，中间为喇叭状，下部为带大缺口的圆柱筒； The structure of the triple sleeve with the lower opening of the system can be that the upper part of the sleeve is cylindrical, the middle is trumpet-shaped, and the lower part is a cylindrical tube with a large gap;
所述反应器的光系统设置为中间一个光源外围一圈光源的多光源形式； The optical system of the reactor is set as a multi-light source form with a light source in the middle and a circle of light sources around it;
所述反应器既适用于多相芬顿体系又适用于均相芬顿体系，既适用于普通芬顿体系又适用于光助-芬顿体系，根据废水的性质和污染物浓度，可以通过加入不同形式的催化剂和开关紫外灯达到不同的处理效果并节约成本，对于均相芬顿体系，加入亚铁离子作为催化剂；对于多相芬顿体系，加入固体催化剂颗粒作为催化剂；对于普通均相芬顿体系，关闭紫外灯；对于光助芬顿体系，打开紫外灯； The reactor is applicable to both heterogeneous Fenton system and homogeneous Fenton system, both common Fenton system and light-assisted-Fenton system, according to the nature of wastewater and the concentration of pollutants, it can be added by adding Different forms of catalysts and switching UV lamps achieve different treatment effects and save costs. For homogeneous Fenton systems, ferrous ions are added as catalysts; for heterogeneous Fenton systems, solid catalyst particles are added as catalysts; for ordinary homogeneous Fenton For the Fenton system, turn off the UV lamp; for the photo-assisted Fenton system, turn on the UV lamp;
反应器底部设有曝气头和进水口，由于上升水流和上浮气泡的作用，在混合区、第一反应区和第二反应区之间出现密度差，驱使待处理溶液和芬顿试剂在三个区之间循环流动，多余的气体从反应器顶部的通气孔溢出，进水、空气、催化剂和过氧化氢在混合区混合，向上进入第一反应区，发生芬顿反应，由于第一重套筒上边沿高于溢流槽上边沿，待处理溶液向下在三重套筒之间形成二级回流即催化剂颗粒在此处可控分级回流，反应液从三重套筒之间流下之后，部分待处理溶液进入外围，废水在第二反应区继续被降解，若使用固相催化剂，催化剂颗粒可以稳定沉降以实现固-液分离，处理后的上清液经溢流槽和出水口排出，部分废水和催化剂经挡板作用回流到底部的混合区，与进水空气混合后向上流动。 There is an aeration head and a water inlet at the bottom of the reactor. Due to the effect of rising water flow and floating air bubbles, there is a density difference between the mixing zone, the first reaction zone and the second reaction zone, which drives the solution to be treated and Fenton’s reagent in the three Circulating flow between the two zones, the excess gas overflows from the vent hole at the top of the reactor, the water, air, catalyst and hydrogen peroxide are mixed in the mixing zone, and enter the first reaction zone upwards, where the Fenton reaction occurs. The upper edge of the sleeve is higher than the upper edge of the overflow tank, and the solution to be treated flows downward between the triple sleeves to form a secondary reflux, that is, the catalyst particles are controlled and graded to reflux here. After the reaction liquid flows down from the triple sleeve, part of the The solution to be treated enters the periphery, and the wastewater continues to be degraded in the second reaction zone. If a solid-phase catalyst is used, the catalyst particles can settle stably to achieve solid-liquid separation. The treated supernatant is discharged through the overflow tank and the water outlet, and some The waste water and catalyst flow back to the mixing zone at the bottom through the baffle, and flow upward after being mixed with the incoming water air.
本发明有益效果是：本发明所述的反应器既适用于多相芬顿体系又适用于均相芬顿体系，既适用于普通芬顿体系又适用于光助-芬顿体系。反应器上部为圆柱，下部为圆台，上部为圆柱型使得反应器有着较高的光利用率和良好的对称性，下部为圆台有利于待处理废水和催化剂颗粒回流。内置三重套筒通过调节高度和间隔宽度，既可以促成颗粒催化剂分粒度回流，又可以按水质条件设计套筒尺寸以控制合理的回流比，延长水力停留时间，三重套筒将反应器分隔成中间的混合区和第一反应区以及外围的第二反应区。为了提高反应器中紫外光与溶液的接触面积，将反应器的光系统设置为中间一个光源外围一圈光源的多光源形式，于是反应器处理水量增大，光强在反应器内分布更加均匀，适合工业实际应用。在较广的pH值范围内，本反应器对难降解有机废水有较好的处理效果，多相催化剂在反应器各反应区之间循环，可以重复利用，有机污染物矿化度高。 The beneficial effects of the present invention are: the reactor described in the present invention is suitable for both heterogeneous Fenton system and homogeneous Fenton system, both common Fenton system and photoassisted-Fenton system. The upper part of the reactor is a cylinder, and the lower part is a circular platform. The upper part is cylindrical so that the reactor has a high light utilization rate and good symmetry. The lower part is a circular platform, which is conducive to the return of wastewater to be treated and catalyst particles. The built-in triple sleeve can not only promote the reflux of the granular catalyst by adjusting the height and interval width, but also design the sleeve size according to the water quality conditions to control a reasonable reflux ratio and prolong the hydraulic retention time. The triple sleeve separates the reactor into the middle The mixing zone and the first reaction zone and the peripheral second reaction zone. In order to increase the contact area between the ultraviolet light and the solution in the reactor, the optical system of the reactor is set as a multi-light source form with a light source in the middle and a circle of light sources around it, so the amount of water treated by the reactor increases, and the light intensity is more evenly distributed in the reactor , suitable for industrial practical applications. Within a wide range of pH values, the reactor has a good treatment effect on refractory organic wastewater, and the heterogeneous catalyst circulates among the reaction zones of the reactor, which can be reused, and the organic pollutants have high salinity.
附图说明 Description of drawings
图1为本发明的结构主视示意图； Fig. 1 is a schematic front view of the structure of the present invention;
图2为本发明的结构俯视示意图； Fig. 2 is a schematic top view of the structure of the present invention;
图中，1-进水口；2-混合区；3-挡板；4-第一重套筒；5-第二重套筒；6-第三重套筒；7-紫外灯；8-溢流槽；9-出水口；10-反应器外壁；11-第一反应区；12-第二反应区；13-曝气头；14-空气入口。 In the figure, 1-water inlet; 2-mixing area; 3-baffle; 4-first heavy sleeve; 5-second heavy sleeve; 6-third heavy sleeve; 7-ultraviolet lamp; 8-overflow Launder; 9-water outlet; 10-outer wall of reactor; 11-first reaction zone; 12-second reaction zone; 13-aeration head; 14-air inlet.
具体实施方式 Detailed ways
结合附图说明如下： In conjunction with the accompanying drawings, the description is as follows:
本发明所述处理难降解有机废水的通用型内循环芬顿反应器的结构包括：进水口、混合区、挡板、第一重套筒、第二重套筒、第三重套筒、紫外灯、溢流槽、出水口、反应器外壁、第一反应区、第二反应区、曝气头、空气入口； The structure of the general-purpose internal circulation Fenton reactor for treating refractory organic wastewater according to the present invention includes: a water inlet, a mixing zone, a baffle, a first heavy sleeve, a second heavy sleeve, a third heavy sleeve, an ultraviolet Lamp, overflow tank, water outlet, outer wall of reactor, first reaction zone, second reaction zone, aeration head, air inlet;
所述反应器上部为圆柱，下部为圆台，上部为圆柱型使得反应器有着较高的光利用率和良好的对称性，下部为圆台有利于待处理水样回流。为了提高反应器光与溶液的接触面积，将反应器的光系统设置为中间一个光源外围一圈光源的多光源形式，于是反应器处理水量增大，光强在反应器内分布更加均匀，适合工业实际应用。利用三重套筒分隔成中间的混合区和第一反应区和外围的第二反应区，中间和外围一圈放置多盏紫外灯。 The upper part of the reactor is a cylinder, and the lower part is a round platform. The upper part is cylindrical so that the reactor has a higher light utilization rate and good symmetry, and the lower part is a round platform, which is conducive to the return of the water sample to be treated. In order to increase the contact area between the light and the solution in the reactor, the optical system of the reactor is set as a multi-light source form with a light source in the middle and a circle of light sources around it, so the amount of water treated by the reactor increases, and the light intensity is distributed more uniformly in the reactor, which is suitable for Industrial practical application. The mixing zone in the middle, the first reaction zone and the second reaction zone in the periphery are separated by a triple sleeve, and multiple ultraviolet lamps are placed in a circle around the middle and the periphery.
反应器底部设有曝气头和进水口，由于上升水流和上浮气泡的作用，在混合区、第一反应区和第二反应区之间出现密度差，驱使待处理溶液和芬顿试剂在三个区之间循环流动，多余的气体从反应器顶部的通气孔溢出。进水、空气、催化剂和过氧化氢在混合区混合，向上进入第一反应区，发生芬顿反应。由于第一重套筒上边沿高于溢流槽上边沿，待处理溶液向下在三重套筒之间形成二级回流（催化剂颗粒在此处可控分级回流）。反应液从三重套筒之间流下之后，部分待处理溶液进入外围，废水在第二反应区继续被降解（若使用固相催化剂，催化剂颗粒可以稳定沉降以实现固-液分离），处理后的上清液经溢流槽和出水口排出，部分废水和催化剂经挡板作用回流到底部的混合区，与进水空气混合后向上流动。 There is an aeration head and a water inlet at the bottom of the reactor. Due to the effect of rising water flow and floating air bubbles, there is a density difference between the mixing zone, the first reaction zone and the second reaction zone, which drives the solution to be treated and Fenton’s reagent in the three The flow is circulated between the two zones, and the excess gas escapes from the vent hole at the top of the reactor. Influent water, air, catalyst and hydrogen peroxide are mixed in the mixing zone, and enter the first reaction zone upwards, where Fenton reaction occurs. Since the upper edge of the first sleeve is higher than the upper edge of the overflow tank, the solution to be treated flows downward between the triple sleeves to form a secondary reflux (where the catalyst particles can be controlled and graded). After the reaction solution flows down between the triple sleeves, part of the solution to be treated enters the periphery, and the wastewater continues to be degraded in the second reaction zone (if a solid-phase catalyst is used, the catalyst particles can settle stably to achieve solid-liquid separation). The supernatant is discharged through the overflow tank and the water outlet, and part of the waste water and catalyst flow back to the bottom mixing area through the baffle, and then flow upward after mixing with the water inlet air.
根据废水性质可选择过氧化氢用量、曝气量、催化剂种类，催化剂用量、紫外灯功率和水力停留时间，以利用本反应器经济高效地处理各种浓度各种成分的有机废水。 The amount of hydrogen peroxide, aeration amount, catalyst type, catalyst amount, UV lamp power and hydraulic retention time can be selected according to the nature of the wastewater, so that the reactor can be used to treat organic wastewater with various concentrations and components economically and efficiently.
对于高浓度废水，出于成本考虑，本反应器比较适合作为生化处理技术的后续深度处理工艺，本反应器可以有效处理生化出水中的难降解有机物，既可以保证达到排放标准，又能保证经济性。 For high concentration wastewater, due to cost considerations, this reactor is more suitable as a follow-up advanced treatment process of biochemical treatment technology. sex.
经试验，本反应器处理染料废水时降解率和矿化率均大于93%，对生化处理后的垃圾渗滤液进行深度处理可以达到最新的渗滤液排放标准。 According to the test, the degradation rate and mineralization rate of this reactor are greater than 93% when treating dye wastewater, and the advanced treatment of landfill leachate after biochemical treatment can meet the latest leachate discharge standards.
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