CN107285421B - A method for segmented treatment of acidic fluorine-containing wastewater that is beneficial to sludge recycling - Google Patents
A method for segmented treatment of acidic fluorine-containing wastewater that is beneficial to sludge recycling Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 51
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- 238000004062 sedimentation Methods 0.000 claims abstract description 13
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- 230000003750 conditioning effect Effects 0.000 description 5
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
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- 230000015271 coagulation Effects 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/007—Modular design
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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Abstract
一种有利于污泥资源化的酸性含氟废水的分段处理方法，属于水处理技术领域。所述方法步骤如下：（1）沉淀：将酸性含氟废水通入储水池进行储存，在囤积5m3后，利用水泵将含氟废水打到中和沉淀池，向中和沉淀池内加入氧化钙，开启机械搅拌桨搅拌40min，转速为300r/min；（2）吸附：将步骤一反应后的沉淀及废水通入板框压滤机进行泥水分离，得到的污泥外运，上清液泵送到调节池，在调节池内将上清液的pH使用盐酸或氢氧化钠调节至中性，进入吸附塔，吸附塔除水即为达标排放水。本发明的优点是：成本低、钙盐利用率高、操作简单易行，实现了污泥减量化及污泥的资源化利用。
The invention discloses a segmented treatment method for acid fluorine-containing wastewater which is beneficial to sludge resource utilization, and belongs to the technical field of water treatment. The method steps are as follows: (1) Precipitation: pass the acidic fluorine-containing wastewater into a water storage tank for storage, after hoarding 5m 3 , use a water pump to pump the fluorine-containing wastewater into a neutralization and sedimentation tank, and add calcium oxide into the neutralization and sedimentation tank , turn on the mechanical stirring paddle to stir for 40min, and the rotation speed is 300r/min; (2) Adsorption: Pass the precipitation and waste water after the reaction in step 1 into the plate and frame filter press to separate the mud and water, and the obtained sludge is transported out, and the supernatant is pumped. It is sent to the adjustment tank, and the pH of the supernatant is adjusted to neutrality with hydrochloric acid or sodium hydroxide in the adjustment tank, and then enters the adsorption tower. The advantages of the invention are: low cost, high utilization rate of calcium salt, simple and easy operation, realizing sludge reduction and sludge resource utilization.
Description
技术领域technical field
本发明属于水处理技术领域，具体涉及一种有利于污泥资源化的酸性含氟废水的分段处理方法。The invention belongs to the technical field of water treatment, and in particular relates to a staged treatment method for acid fluorine-containing wastewater which is beneficial to sludge resource utilization.
背景技术Background technique
高纯石墨是现代科技与工业发展的重要原料，石墨提纯产生的酸性含氟废水具有环境风险，含氟废水处理是石墨行业健康发展的重要保证。石墨提纯产生的含氟废水水质复杂，氟离子浓度很高，是氢氟酸、盐酸、硫酸、硝酸的混合液，同时含有钙离子、镁离子、铁离子、氟硅酸根离子等成分。含氟废水的主要处理方法包括化学沉淀、混凝沉淀、吸附、离子交换、反渗透和电渗析等。High-purity graphite is an important raw material for modern technology and industrial development. The acid fluorine-containing wastewater produced by graphite purification has environmental risks. The treatment of fluorine-containing wastewater is an important guarantee for the healthy development of the graphite industry. The fluorine-containing wastewater produced by graphite purification is complex in water quality and has a high concentration of fluoride ions. It is a mixture of hydrofluoric acid, hydrochloric acid, sulfuric acid and nitric acid. The main treatment methods of fluorine-containing wastewater include chemical precipitation, coagulation precipitation, adsorption, ion exchange, reverse osmosis and electrodialysis.
化学沉淀法是指在废水中投加沉淀剂，使得废水中的氟与沉淀剂发生沉淀反应，生成难溶于水的氟化物沉淀或者氟化物吸附于形成的沉淀物共同沉淀，通过自然沉降或过滤等方法进行固液分离，从而实现除氟，降低废水中的氟含量，常用的沉淀剂有生石灰、熟石灰、钙盐等。化学沉淀法在含氟废水的处理中应用普遍，尤其是高浓度含氟废水的处理。The chemical precipitation method refers to adding a precipitant to the wastewater, so that the fluorine in the wastewater reacts with the precipitant to form a precipitation of fluoride that is insoluble in water, or the fluoride is adsorbed on the formed precipitate to co-precipitate. The solid-liquid separation is carried out by filtration and other methods, so as to achieve defluorination and reduce the fluorine content in the wastewater. Commonly used precipitants are quicklime, slaked lime, calcium salt, etc. The chemical precipitation method is widely used in the treatment of fluorine-containing wastewater, especially the treatment of high-concentration fluorine-containing wastewater.
混凝沉淀法为在废水中投加混凝剂，在溶液中形成胶体，从而吸附一部分氟离子，同时通过搅拌和混凝剂的作用使胶体脱稳，再经过絮凝过程，形成上清液和沉积的絮体，将水中的氟转移至絮体中，同时促进污泥的沉降。混凝沉淀法经济实用，设备简单，操作也比较容易，但是存在污泥量较大，药剂量较大，出水含无机盐离子等问题。如采用铝盐混凝剂出水往往含有大量溶解铝，而且水中亦含有溶解态的含氟络合物，除氟不彻底，存在安全隐患。The coagulation precipitation method is to add a coagulant to the wastewater to form a colloid in the solution, thereby adsorbing a part of fluoride ions, and at the same time destabilizing the colloid through the action of stirring and coagulant, and then through the flocculation process to form a supernatant and a coagulant. The deposited flocs transfer the fluorine in the water to the flocs, and at the same time promote the sedimentation of the sludge. The coagulation sedimentation method is economical and practical, the equipment is simple, and the operation is relatively easy, but there are problems such as a large amount of sludge, a large amount of chemicals, and inorganic salt ions in the effluent. If aluminum salt coagulant is used, the effluent often contains a large amount of dissolved aluminum, and the water also contains dissolved fluorine-containing complexes. The fluorine removal is not complete, and there are potential safety hazards.
吸附法是将含氟废水通过吸附装置，氟离子与吸附剂上的基团或离子发生离子交换，从而去除废水中的氟离子。吸附法是一种基于接触法的表面过程，通常用于处理氟离子浓度较低的废水，适用于饮用水除氟，或者经过预处理的水的深度处理。The adsorption method is to pass the fluorine-containing wastewater through the adsorption device, and the fluoride ions are ion-exchanged with the groups or ions on the adsorbent, thereby removing the fluoride ions in the wastewater. Adsorption is a contact-based surface process, usually used to treat wastewater with low fluoride ion concentration, suitable for defluoridation of drinking water, or advanced treatment of pretreated water.
离子交换、反渗透和电渗析等方法处理效率高，效果好，出水水质稳定，但需要对原水进行预处理，且建设和运行费用高，技术较复杂，应用较少。Methods such as ion exchange, reverse osmosis and electrodialysis have high treatment efficiency, good effect, and stable effluent quality, but require pretreatment of raw water, and have high construction and operation costs, complex technology, and less application.
发明内容SUMMARY OF THE INVENTION
本发明的目的是为了解决现有技术中存在的污水处理成本高、处理效果不理想、技术较复杂等问题，提供了一种有利于污泥资源化的酸性含氟废水的分段处理方法。The purpose of the present invention is to solve the problems of high sewage treatment cost, unsatisfactory treatment effect, and complicated technology in the prior art, and provide a staged treatment method for acidic fluorine-containing wastewater that is beneficial to sludge recycling.
本发明使用沉淀工艺中的钙盐沉淀法投加氧化钙将废水处理至中性，同时钙离子和氟离子生成氟化钙沉淀，将溶液中的氟离子去除。本发明针对氢氟酸法提纯石墨过程中产生的两种废水进行分别处理，第一种废水氟离子浓度很高在10000mg/L以上，而第二种废水氟离子浓度仅为285mg/L，其他成分如氯离子、硫酸根离子等也是一段水高得多。说明第二种废水较第一种废水是较为纯净的水，杂质含量少，氟离子含量低，相应酸性也较低。本发明通过沉淀+吸附二级处理工艺将废水处理至中性，氟离子浓度在10mg/L以下。The invention uses the calcium salt precipitation method in the precipitation process to add calcium oxide to treat the wastewater to neutrality, and at the same time calcium ions and fluoride ions generate calcium fluoride precipitation, and the fluoride ions in the solution are removed. The present invention separately treats two kinds of waste water produced in the process of purifying graphite by hydrofluoric acid method. Components such as chloride ions, sulfate ions, etc. are also much higher in a section of water. It shows that the second type of wastewater is relatively pure water compared with the first type of wastewater, with less impurity content, lower fluoride ion content, and lower corresponding acidity. In the invention, the wastewater is treated to neutrality through a precipitation + adsorption secondary treatment process, and the fluoride ion concentration is below 10 mg/L.
为实现上述目的，本发明采取的技术方案如下：To achieve the above object, the technical scheme adopted by the present invention is as follows:
一种有利于污泥资源化的酸性含氟废水的分段处理方法，所述方法具体步骤如下：A method for segmented treatment of acidic fluorine-containing wastewater that is conducive to sludge recycling, the specific steps of the method are as follows:
步骤一：沉淀：将高浓度酸性含氟废水通入储水池一进行储存，在囤积5m3后，利用水泵将高浓度含氟废水打到中和沉淀池一，向中和沉淀池一内加入氧化钙120g/L，开启机械搅拌桨搅拌30~40min，转速为250~300r/min；将低浓度酸性含氟废水通入储水池二，在囤积5m3后，利用水泵将低浓度含氟废水打到中和沉淀池二，向中和沉淀池二内加入氧化钙15g/L，开启机械搅拌桨搅拌30~40min，转速为250~300r/min；Step 1: Precipitation: pass the high-concentration acidic fluorine-containing wastewater into the storage tank 1 for storage. After hoarding 5m 3 Calcium oxide 120g/L, turn on the mechanical stirring paddle and stir for 30~40min, and the speed is 250~300r/min; pass the low-concentration acidic fluorine-containing wastewater into the second storage tank, after hoarding 5m3 , use the water pump to remove the low-concentration fluorine-containing wastewater Beat to the second neutralization sedimentation tank, add 15g/L of calcium oxide to the second neutralization sedimentation tank, turn on the mechanical stirring paddle and stir for 30~40min, and the rotation speed is 250~300r/min;
步骤二：吸附：将步骤一反应后的沉淀物及废水通入板框压滤机进行泥水分离，得到的污泥外运，上清液泵送到调节池，在调节池内使用盐酸或氢氧化钠将上清液的pH调节至中性后，进入吸附塔，吸附塔除水即为达标排放水。Step 2: Adsorption: The sediment and waste water after the reaction in step 1 are passed into the plate and frame filter press for mud-water separation, the obtained sludge is transported out, and the supernatant is pumped to the conditioning tank, where hydrochloric acid or hydroxide is used in the conditioning tank After the pH of the supernatant is adjusted to neutral by sodium, it enters the adsorption tower, and the water removed by the adsorption tower is the discharge water that meets the standard.
本发明相对于现有技术的有益效果是：The beneficial effects of the present invention relative to the prior art are:
（1）选择氧化钙作为沉淀剂，比氢氧化钙成本低，比碳酸钙处理调节pH能力强，污泥量少。钙盐沉淀法处理后，出水pH为中性，氟离子浓度在20mg/L左右。(1) Calcium oxide is selected as the precipitant, which is lower in cost than calcium hydroxide, stronger in pH adjustment than calcium carbonate treatment, and less sludge. After calcium salt precipitation treatment, the pH of the effluent is neutral, and the fluoride ion concentration is about 20 mg/L.
（2）通过将废水分段处理，提高了氧化钙的利用率，与废水混合处理相比，分段处理每吨废水氧化钙消耗量减少21kg，节约了成本。(2) The utilization rate of calcium oxide is improved by treating the wastewater in stages. Compared with the mixed treatment of wastewater, the consumption of calcium oxide per ton of wastewater is reduced by 21kg, which saves the cost.
（3）污泥体积减少20%，第一种污泥的氟化钙纯度为80%左右，第二种污泥的氟化钙纯度为20%左右，混合废水的污泥氟化钙纯度为50%左右。污泥纯度的提高有利于其资源化利用如烧制氟铝酸盐水泥、陶瓷烧结、烧砖，或者浮选提取氟化钙等，分段处理实现了污泥减量化，并便于资源化利用。(3) The sludge volume is reduced by 20%, the calcium fluoride purity of the first sludge is about 80%, the calcium fluoride purity of the second sludge is about 20%, and the sludge calcium fluoride purity of the mixed wastewater is 50% or so. The improvement of sludge purity is conducive to its resource utilization, such as sintering fluoroaluminate cement, ceramic sintering, brick burning, or flotation extraction of calcium fluoride, etc. The staged treatment realizes sludge reduction and facilitates resource utilization. use.
（4）吸附处理可以有效地进一步去除氟离子浓度，保证出水氟离子浓度在10mg/L以下。使用氢氧化钠和硫酸铝可以有效的再生吸附饱和的活性氧化铝，吸附量下降不大。(4) The adsorption treatment can effectively further remove the fluoride ion concentration and ensure that the fluoride ion concentration in the effluent is below 10mg/L. The use of sodium hydroxide and aluminum sulfate can effectively regenerate and adsorb saturated activated alumina, and the adsorption capacity does not decrease much.
（5）整体工艺占地面积小，操作简单，方便易行，效果可靠。(5) The overall process occupies a small area, the operation is simple, convenient and easy to operate, and the effect is reliable.
附图说明Description of drawings
图1为本发明处理方法的工艺流程图。FIG. 1 is a process flow diagram of the processing method of the present invention.
具体实施方式Detailed ways
下面结合附图和实施例对本发明的技术方案作进一步说明，但并不局限于此，凡是对本发明技术方案进行修正或等同替换，而不脱离本发明技术方案的精神范围，均应涵盖在本发明的保护范围之中。The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and embodiments, but are not limited thereto. Any modification or equivalent replacement of the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention shall be included in the present invention. within the scope of protection of the invention.
具体实施方式一：本实施方式记载的是一种有利于污泥资源化的酸性含氟废水的分段处理方法，所述方法具体步骤如下：Specific embodiment 1: This embodiment records a method for the staged treatment of acidic fluorine-containing wastewater that is conducive to sludge recycling. The specific steps of the method are as follows:
步骤一：沉淀：将高浓度酸性含氟废水通入储水池一1进行储存，在囤积5m3后，利用水泵将高浓度含氟废水打到中和沉淀池一3，向中和沉淀池一3内加入氧化钙120g/L，开启机械搅拌桨搅拌30~40min，转速为250~300r/min；将低浓度酸性含氟废水通入储水池二2，在囤积5m3后，利用水泵将低浓度含氟废水打到中和沉淀池二4，向中和沉淀池二4内加入氧化钙15g/L，开启机械搅拌桨搅拌30~40min，转速为250~300r/min；Step 1: Precipitation: pass the high-concentration acidic fluorine-containing wastewater into the storage tank-1 for storage, after hoarding 5m 3 3, add calcium oxide 120g/L, turn on the mechanical stirring paddle to stir for 30~40min, and the speed is 250~300r/min; pass the low-concentration acid fluorine-containing waste water into the storage tank 22, after hoarding 5m3 , use the water pump to The concentration of fluorine-containing wastewater is beaten into the neutralization and sedimentation tank 24, and 15g/L of calcium oxide is added to the neutralization and sedimentation tank 24, and the mechanical stirring paddle is turned on to stir for 30~40min, and the rotation speed is 250~300r/min;
步骤二：吸附：将步骤一反应后的沉淀物及废水通入板框压滤机5进行泥水分离，得到的污泥外运，上清液泵送到调节池6，在调节池6内使用盐酸或氢氧化钠将上清液的pH调节至中性后，进入吸附塔7，吸附塔7除水即为达标排放水，吸附塔出水实时检测氟离子浓度，当氟离子浓度超过10mg/L时，对吸附剂进行再生，再生液使用氢氧化钠溶液，活化剂使用硫酸铝溶液。Step 2: Adsorption: The sediment and waste water reacted in step 1 are passed into the plate and frame filter press 5 for mud-water separation, the obtained sludge is transported out, and the supernatant is pumped to the conditioning tank 6 for use in the conditioning tank 6 After the pH of the supernatant is adjusted to neutrality with hydrochloric acid or sodium hydroxide, it enters the adsorption tower 7, and the water removed from the adsorption tower 7 is the discharge water that reaches the standard. The fluoride ion concentration in the effluent of the adsorption tower is detected in real time. When the adsorbent is regenerated, sodium hydroxide solution is used as the regeneration solution, and aluminum sulfate solution is used as the activator.
具体实施方式二：具体实施方式一所述的一种有利于污泥资源化的酸性含氟废水的分段处理方法，步骤一中，所述高浓度酸性含氟废水一中氟离子浓度≧10000mg/L，低浓度酸性含氟废水二中氟离子浓度为285mg/L。Specific embodiment 2: The method for segmented treatment of acidic fluorine-containing wastewater that is beneficial to sludge recycling according to specific embodiment 1, in step 1, the fluoride ion concentration in the high-concentration acidic fluorine-containing wastewater 1 is ≧ 10000mg /L, the fluoride ion concentration in the low-concentration acidic fluorine-containing wastewater II is 285 mg/L.
实施例1Example 1
本实施例以鸡西市奥宇石墨集团的两段含氟废水作为水样，使用分段钙盐沉淀法处理含氟废水，之后用活性氧化铝吸附法进行吸附，具体方案如下：In this example, two stages of fluorine-containing wastewater from Jixi Aoyu Graphite Group are used as water samples, and the fluorine-containing wastewater is treated by segmented calcium salt precipitation method, and then adsorbed by activated alumina adsorption method. The specific scheme is as follows:
一段水进入储水池1，在囤积5m3后，使用水泵打到中和沉淀池，加入氧化钙120g/L，开启机械搅拌桨搅拌40min，转速为300r/min。A section of water enters the storage tank 1. After accumulating 5m 3 , it is pumped to the neutralization sedimentation tank with a water pump, 120 g/L of calcium oxide is added, and the mechanical stirring paddle is turned on to stir for 40 minutes, and the rotation speed is 300 r/min.
一段水进入储水池2，在囤积5m3后，使用水泵打到中和沉淀池，加入氧化钙15g/L，开启机械搅拌桨搅拌40min，转速为300r/min。A section of water enters the storage tank 2. After hoarding 5m 3 , it is pumped to the neutralization sedimentation tank with a water pump, 15g/L of calcium oxide is added, and the mechanical stirring paddle is turned on to stir for 40 minutes, and the rotation speed is 300r/min.
两段水中和反应后通过污泥泵打入板式压滤机，进行泥水分离，污泥外运处理，出水排入调节池。After the two-stage water neutralization reaction, it is pumped into the plate filter press through the sludge pump, and the sludge is separated from the water, and the sludge is transported to the outside for treatment.
调节池内加入盐酸和氢氧化钠调节pH为7。使用过滤泵将调节池中的水打入活性氧化铝吸附塔。Hydrochloric acid and sodium hydroxide were added to the adjustment tank to adjust the pH to 7. Use a filter pump to pump the water in the conditioning tank into the activated alumina adsorption tower.
吸附塔出水进行氟离子浓度检测，当超过10mg/L时，对吸附剂进行再生，再生液选择0.6mol/L的氢氧化钠溶液，再生时间为5小时。再生后用自来水冲洗至出水为中性，再用1%的硫酸铝溶液活化3h，之后用自来水冲洗。The fluoride ion concentration is detected in the effluent of the adsorption tower. When it exceeds 10 mg/L, the adsorbent is regenerated. The regeneration solution is 0.6 mol/L sodium hydroxide solution, and the regeneration time is 5 hours. After regeneration, rinse with tap water until the effluent is neutral, activate with 1% aluminum sulfate solution for 3h, and then rinse with tap water.
经沉淀+吸附处理后，出水pH为中性，氟离子浓度在10mg/L以下。After precipitation + adsorption treatment, the pH of the effluent is neutral, and the fluoride ion concentration is below 10 mg/L.
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