CN102464397A - Composite zinc removing agent for treating wastewater containing zinc - Google Patents

Composite zinc removing agent for treating wastewater containing zinc Download PDF

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CN102464397A
CN102464397A CN 201110319359 CN201110319359A CN102464397A CN 102464397 A CN102464397 A CN 102464397A CN 201110319359 CN201110319359 CN 201110319359 CN 201110319359 A CN201110319359 A CN 201110319359A CN 102464397 A CN102464397 A CN 102464397A
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zinc
percent
sodium
removing
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CN 201110319359
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范璐璐
雷思宇
雷春生
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常州亚环环保科技有限公司
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Abstract

The invention discloses a composite zinc removing agent for treating wastewater containing zinc, belonging to the field of sewage treatment in environmental protection. The composite zinc removing agent is prepared by compounding organic matters and inorganic matters, wherein the organic matters comprise one or two of sodium citrate, tricalcium citrate, sodium oxalate, potassium oxalate and hydroxyethylidene bisphosphonate, and the inorganic matters comprise two or more of sodium sulfide, magnesium sulfide, ferrous sulfate and aluminum sulfate; in terms of mass ration, the sodium citrate accounts for 20 to 80 percent, the tricalcium citrate accounts for 20 to 80 percent, the sodium oxalate accounts for 20 to 80 percent, the potassium oxalate accounts for 20 to 80 percent, the hydroxyethylidene bisphosphonate accounts for 20 to 80 percent, the sodium sulfide accounts for 10 to 40 percent, the magnesium sulfide accounts for 10 to 40 percent, the ferrous sulfate accounts for 10 to 40 percent, and the aluminum sulfate accounts for 10 to 40 percents; and the composite zinc removing agent prepared according to the proportion is added into the wastewater containing the zinc under the condition that a pH value is between 4.0 and 6.0, the wastewater is stirred for 10 to 30 minutes and is subjected to air flotation treatment, a layer of residue floating on the surface of the wastewater is finally scraped by using a scraping machine, and yielding water can be lower the national discharge standard I. The composite zinc removing agent has the characteristics of simple process flow, lower running cost, no sludge generation, high zinc removing effect and the like.

Description

一种处理含锌废水的复合除锌剂 Compounded with a zinc-containing waste water in addition to zinc

技术领域 FIELD

[0001] 本发明涉及一种处理含锌废水的复合除锌剂,特别涉及处理锌浓度在10〜 100mg/L范围内的废水,属于环境保护中废水处理领域。 [0001] The present invention relates to a composite for treating wastewater containing zinc addition to zinc, the zinc concentration in the process relates particularly 10~ 100mg / L range wastewater, wastewater treatment belongs to environmental protection.

背景技术 Background technique

[0002] 含锌废水的排放对人体健康和工农业活动具有严重危害,具有持久性、毒性大、污染严重等危害,一旦进入环境后不能被生物降解,大多数参与食物链循环,并最终在生物体内积累,破坏生物体正常生理代谢活动,危害人体健康。 [0002] discharged wastewater containing zinc has a serious harm to human health and agricultural and industrial activities, with persistence, toxicity, severe pollution and other hazards, once into the environment can not be biodegradable, most involved in the food chain cycle, and ultimately in the biological accumulate, disruption of normal physiological metabolic activity of organisms harmful to human health. 随着人类对重金属的开采、冶炼、力口工等生产活动的日益增加,产生的重金属废水无论是从数量上还是种类上都大大增加,造成了严重的环境污染和资源浪费。 With the increasing human heavy metals mining, smelting, power port workers and other production activities, heavy metal waste water generated from either greatly increase the quantity and species, causing serious environmental pollution and waste of resources. 因此含锌废水的治理在世界环保领域中仍是一个有待解决的问题。 Therefore, zinc waste water treatment in the world in the field of environmental protection is still a problem to be solved.

[0003] 目前,国内外根据其处理手段的不同,可分为物化法和生物法,根据锌在溶液中存在的形态不同,常用的处理方法分两类:第一类是使废水中呈溶解状态的锌离子转变为不溶的重金属化合物,经过沉淀或浮上法从废水中除去,具体方法有化学沉淀法、离子交换法、吸附法等;第二类是使废水中的重金属在不改变其化学形态的条件下进行浓缩和分离,具体方法有反渗透法、电渗析法、蒸发浓缩法。 [0003] Currently, depending on their domestic and processing means can be divided into chemical and physical and biological methods, depending on the form of zinc present in the solution in different treatment methods commonly used two types: the first is that the wastewater was dissolved zinc ion into insoluble state, heavy metal compounds, removed from the wastewater after precipitation or floating method, the specific method of chemical precipitation, ion exchange, adsorption and the like; second category of heavy metals in the waste water does not change its chemical and concentrated under separation conditions forms, specific methods are reverse osmosis, electrodialysis, and concentrated by evaporation method. 这类方法能有效的去除废水中的锌,但都存在着投资大,运行费用高,治理后的水难以达标,污泥产量大等问题。 Such method can effectively remove zinc wastewater, but there is a large investment, high operating costs, water governance difficult to compliance, large sludge production and other issues.

[0004] 因此为克服现有技术的不足,本发明提供了一种处理含锌废水的复合除锌剂,该发明方法工艺流程简单,运行成本低,处理效果显著,经一次处理后水中残留锌离子浓度低于0. ang/L,低于国家规定的一级排放标准;无沉淀产生,不会引起二次污染,且出水和废水中的金属氧化物均可回收利用。 [0004] Therefore to overcome the deficiencies of the prior art, the present invention provides a compound for treating zinc-containing waste water in addition to zinc, the method of the invention process is simple, low operating costs, a significant treatment effect, the post-treatment of zinc remaining water ion concentration of less than 0. ang / L, an emission below the national standard; no precipitate, does not cause secondary pollution, water and wastewater and the metal oxide can be recycled.

发明内容 SUMMARY

[0005] 本发明的目的是为克服现有技术的不足,提供了一种处理废水中含锌浓度为10mg/L〜100mg/L的复合除锌剂,该复合除锌剂工艺流程简单,运行成本低,处理效果显著,经一次处理后水中残留锌离子浓度低于0. ang/L,低于国家规定的一级排放标准;无沉淀产生,不会引起二次污染,且出水和废水中的金属氧化物均可回收利用。 [0005] The object of the present invention is to overcome the disadvantages of the prior art, there is provided a process wastewater containing zinc at a concentration of 10mg / L~100mg / L compound in addition to zinc, the zinc compound in addition to the process is simple, low cost, a significant treatment effect, the water remaining after treatment by a zinc ion concentration of less than 0. ang / L, an emission below the national standard; no precipitate, does not cause secondary pollution, and water and wastewater metal oxides can be recycled.

[0006] 本发明采用的技术方案是: [0006] aspect of the present invention is that:

该复合除锌剂由有机物和无机物复配而成。 In addition to the zinc complex with the organic and inorganic complex formed.

[0007] 所述的有机物是柠檬酸钠、柠檬酸三钙、草酸钠、草酸钾、羟基而乙叉二膦酸盐中的一种或两种。 The organics [0007] is sodium citrate, tricalcium citrate, sodium oxalate, potassium oxalate, hydroxyl ethylidene one or both of the bisphosphonate.

[0008] 所述的无机物是硫化钠、硫化镁、硫酸亚铁、硫酸铝中的两种或两种以上。 [0008] said inorganic substance is sodium sulfide, magnesium sulfide, ferrous sulfate, aluminum sulfate of two or more.

[0009] 按占复合除锌剂总质量百分比计,所述的有机物是柠檬酸钠20%〜80%、柠檬酸三钙20%〜80%、草酸钠20%〜80%、草酸钾20%〜80%、羟基而乙叉二膦酸盐20%〜 80% ;所述的无机物是硫化钠10%〜40%、硫化镁10%〜40%、硫酸亚铁10%〜40%、硫酸铝10%〜40%。 [0009] According to the proportion of zinc compound in addition to the total mass percentage of the organic matter is 20% ~ 80% sodium citrate, tricalcium citrate 20% ~ 80%, ~ 80% 20% sodium oxalate, 20% potassium oxalate ~ 80%, hydroxy ethylidene diphosphonic acid and 20% to 80%; the inorganic sulfide is 10% ~ 40%, ~ 40% 10% magnesium sulfate, ferrous sulfate 10% ~ 40% sulfuric acid 10% ~ 40% aluminum. [0010] 该复合除锌剂的应用方法是:将有机物和无机物复配而成的除锌剂加入到含锌废水中,加入的量为5〜20ppm,用酸将PH值调节至4. 0〜6. 0,搅拌10〜30min之后,所得的废水再进行气浮处理,最后把浮在废水表面的一层残渣用刮渣机刮除,出水即可达到国家一级排放标准。 [0010] In addition to the application of the method zinc compound is: The compound from organic and inorganic substances in addition to zinc is added to the zinc-containing waste water is added in an amount 5~20ppm, with an acid value was adjusted to PH 4. 0~6. 0, followed by stirring 10~30min, then the resulting wastewater flotation process, and finally the surface of the layer of floating waste residue with a scraper scraping residue, water can reach the discharge national standard.

[0011] 本发明的有益效果是: [0011] Advantageous effects of the present invention are:

(1)工艺流程简单,运行成本低; (1) process is simple, low operating costs;

(2)处理效果显著,经一次处理后水中残留锌离子浓度低于O.aiig/L,低于国家规定的一级排放标准; (2) a significant treatment effect, the water remaining after treatment by a zinc ion concentration below O.aiig / L, less than an emission standard state;

(3)无沉淀产生,不会引起二次污染,且出水和废水中的金属氧化物均可回收利用。 (3) no precipitation is generated, it does not cause secondary pollution, water and wastewater and the metal oxide can be recycled. 具体实施方式 detailed description

[0012] 本发明复合除锌剂由有机物和无机物复配而成,所述的有机物是柠檬酸钠、柠檬酸三钙、草酸钠、草酸钾、羟基而乙叉二膦酸盐中的一种或两种;所述的无机物是硫化钠、硫化镁、硫酸亚铁、硫酸铝中的两种或两种以上。 [0012] In addition to the composite of the present invention is a zinc compound from organic and inorganic substances, it said organic material is sodium citrate, tricalcium citrate, sodium oxalate, potassium oxalate, and hydroxy ethylidene diphosphonic acid in a species or both; the mineral is sodium sulfide, magnesium sulfide, ferrous sulfate, aluminum sulfate of two or more.

[0013] 上述复合除锌剂所占的质量比分别为:所述的有机物是柠檬酸钠20 %〜80 %、 柠檬酸三钙20%〜80%、草酸钠20%〜80%、草酸钾20%〜80%、羟基而乙叉二膦酸盐20%〜80% ;所述的无机物是硫化钠10%〜40%、硫化镁10%〜40%、硫酸亚铁10%〜 40%、硫酸铝10%〜40%。 [0013] In addition to the above-described composite mass ratio of zinc are occupied: organics is 20% ~ 80% sodium citrate, tricalcium citrate 20% ~ 80%, ~ 80% 20% sodium oxalate, potassium oxalate 20% ~ 80%, hydroxy ethylidene diphosphonic acid and 20% ~ 80%; the inorganic sulfide is 10% ~ 40%, ~ 40% 10% magnesium sulfate, ferrous sulfate 10% to 40% , 10% ~ 40% aluminum sulfate.

[0014] 处理含锌废水的除锌方法是:将上述比例所配的复合除锌剂加入到含锌浓度在10mg/L〜100mg/L范围内的废水中,加入量为5〜20ppm ;用酸将废水调节pH至4. 0〜 6. 0,搅拌10〜30min之后,所得的废水再进行气浮处理,最后把浮在废水表面的一层残渣用刮渣机刮除,出水即可达到国家一级排放标准。 [0014] The method for treating wastewater containing zinc addition to zinc is: the above-described proportion with other zinc compound is added to the zinc concentration in the wastewater 10mg / L~100mg / L range, an amount of 5~20ppm; with acid wastewater adjusted to pH 4. 0~ 6.0, followed by stirring 10~30min, then the resulting wastewater flotation process, and finally the surface of the layer of floating waste residue with a scraper scraping residue, water can reach national emission standards.

[0015]实例 1 [0015] Example 1

按占复合除锌剂总质量百分比计,将草酸钠20%、硫化镁40%、硫酸亚铁40%配成复合除锌剂,对某制药废水中含锌进行处理,废水中含锌量100mg/L,试验时取15mL除锌剂加入到含锌废水中,将PH值调节到4. 5,搅拌15min,所得的废水再进行气浮处理,最后把浮在废水表面的一层残渣用刮渣机刮除,出水中未检测出锌。 According to the proportion of zinc compound in addition to the total mass percentage, 20% of the sodium oxalate, 40% magnesium sulfate, ferrous sulfate 40% zinc scavenger compound formulated for a pharmaceutical zinc treated wastewater, wastewater zinc 100mg / L, when taking the test agent is added to 15mL in addition to zinc in the zinc-containing waste water, the PH value was adjusted to 4.5, was stirred for 15min, then the resulting flotation process wastewater, waste floating on the surface of the last layer of the residue by scraping slag scraping, the water was not detected zinc.

[0016]实例 2 [0016] Example 2

按占复合除锌剂总质量百分比计,将将草酸钾80%、硫化镁10%、硫酸铝10%配成复合除锌剂,对某化工废水中含锌进行处理,废水中含锌量80mg/L,试验时取13mL除锌剂加入到含锌废水中,将PH值调节到5. 0,搅拌20min,所得的废水再进行气浮处理,最后把浮在废水表面的一层残渣用刮渣机刮除,出水中锌含量0. (Mmg/L。 According to the proportion of zinc compound in addition to the total mass percentage would be 80% potassium oxalate, magnesium sulfate 10%, 10% aluminum sulfate in addition to zinc formulated compound agent, a chemical wastewater treated zinc, zinc wastewater 80mg / L, when taking the test agent is added to 13mL in addition to zinc in the zinc-containing waste water, the PH value is adjusted to 5.0, was stirred for 20min, then the resulting flotation process wastewater, waste floating on the surface of the last layer of the residue by scraping slag scraping, the zinc content of the water 0. (Mmg / L.

[0017]实例 3 [0017] Example 3

按占复合除锌剂总质量百分比计,将柠檬酸钠35%、羟基而乙叉二膦酸盐30%、硫化钠15%、硫化镁20%配成复合除锌剂,对某化工废水中含锌进行处理,废水中含锌量70mg/ L,试验时取16mL除锌剂加入到含锌废水中,将pH值调节到5. 3,搅拌25min,所得的废水再进行气浮处理,最后把浮在废水表面的一层残渣用刮渣机刮除,出水未检测出锌。 According to the proportion of zinc compound in addition to the total mass percentage of 35% sodium citrate, hydroxy ethylidene diphosphonic acid and 30% and 15% of sodium sulfide, magnesium sulfide complex dubbed 20% zinc scavenger, a chemical for wastewater treated zinc, zinc 70mg / L, zinc is added in addition to taking into 16mL zinc-containing wastewater, wastewater to adjust the pH of the test to 5.3, was stirred for 25min, then the resulting wastewater flotation process, and finally the surface layer of floating waste residue was purified by scraping residue scraping, the water was not detected zinc.

[0018] 实例4 [0018] Example 4

按占复合除锌剂总质量百分比计,将羟基而乙叉二膦酸盐45%、草酸钾25%、硫酸亚铁10%、硫酸铝20%配成复合除锌剂,对某制药废水中含锌进行处理,废水中含锌量50mg/ L,试验时取15mL除锌剂加入到含锌废水中,将pH值调节到5. 6,搅拌20min,所得的废水再进行气浮处理,最后把浮在废水表面的一层残渣用刮渣机刮除,出水中锌含量为0. 05mg/L。 In addition to accounting for the total mass of the composite by zinc percentage, hydroxy ethylidene diphosphonic acid and 45%, 25% potassium oxalate, ferrous sulfate 10%, 20% aluminum sulfate, zinc scavenger compound formulated, to a pharmaceutical wastewater treated zinc, zinc 50mg / L, zinc is added in addition to taking into 15mL zinc-containing wastewater, wastewater to adjust the pH of the test to 5.6, was stirred for 20min, then the resulting wastewater flotation process, and finally the surface layer of floating waste residue was purified by scraping residue scraping, the zinc content of the water of 0. 05mg / L. [0019] 实例5 [0019] Example 5

按占复合除锌剂总质量百分比计,将羟基而乙叉二膦酸盐55%、草酸钠20%、硫化钠10%、硫酸铝15%配成复合除锌剂,对某化工废水中含锌进行处理,废水中含锌量20mg/L, 试验时取15mL除锌剂加入到含锌废水中,将pH值调节到5. 8,搅拌30min,所得的废水再进行气浮处理,最后把浮在废水表面的一层残渣用刮渣机刮除,出水未检测出锌。 In addition to accounting for the total mass of the composite by zinc percentage, hydroxy ethylidene diphosphonic acid and 55% to 20% sodium oxalate, sodium sulfide 10%, 15% aluminum sulfate in addition to zinc formulated composite agent containing a chemical for wastewater treated zinc, zinc 20mg / L, zinc is added in addition to taking into 15mL zinc-containing wastewater, wastewater to adjust the pH of the test to 5.8, was stirred for 30min, then the resulting wastewater flotation process, and finally floating on the surface layer of the wastewater residue was purified by scraping residue scraping, the water was not detected zinc.

Claims (6)

  1. 1. 一种处理含锌废水的复合除锌剂,其特征在于:该复合除锌剂由有机物和无机物复配而成,所述的有机物是柠檬酸钠、柠檬酸三钙、草酸钠、草酸钾、羟基而乙叉二膦酸盐中的一种或两种;所述的无机物是硫化钠、硫化镁、硫酸亚铁、硫酸铝中的两种或两种以上。 A composite zinc-containing waste water in addition to zinc, wherein: the zinc complex by the addition compound from organic and inorganic substances, said organic materials are sodium citrate, tricalcium citrate, sodium oxalate, potassium oxalate, hydroxyl groups or both ethylidene bisphosphonate; said inorganic material is sodium sulfide, magnesium sulfide, ferrous sulfate, aluminum sulfate of two or more.
  2. 2.根据权利要求1所述的一种处理含锌废水的复合除锌剂,其特征在于:按占复合除锌剂总质量百分比计,将草酸钠20 %、硫化镁40 %、硫酸亚铁40 %配成复合除锌剂。 2. The composite of claim 1 for treating waste water containing zinc in addition to zinc claim, characterized in that: According to the proportion of zinc compound in addition to the total mass percentage, 20% of the sodium oxalate, 40% magnesium sulfate, ferrous sulfate 40% of the formulated compound in addition to zinc.
  3. 3.根据权利要求1所述的一种处理含锌废水的复合除锌剂,其特征在于:按占复合除锌剂总质量百分比计,将草酸钠80%、硫化镁10%、硫酸铝10%配成复合除锌剂。 3. The composite of claim 1 for treating waste water containing zinc in addition to zinc claim, characterized in that: According to the proportion of zinc compound in addition to the total mass percentage, 80% of the sodium oxalate, 10% magnesium sulfate, aluminum sulfate 10 % in addition to zinc formulated compound.
  4. 4.根据权利要求1所述的一种处理含锌废水的复合除锌剂,其特征在于:按占复合除锌剂总质量百分比计,将柠檬酸钠35%、羟基而乙叉二膦酸盐30%、硫化钠15%、硫化镁20%配成复合除锌剂。 4. The composite of claim 1 for treating waste water containing zinc in addition to zinc claim, characterized in that: According to the proportion of zinc compound in addition to the total mass percentage, 35% sodium citrate, hydroxy ethylidene diphosphonic acid and 30% salt, 15% sodium sulfide, magnesium sulfide complex dubbed 20% zinc scavenger.
  5. 5.根据权利要求1所述的一种处理含锌废水的复合除锌剂,其特征在于:按占复合除锌剂总质量百分比计,将羟基而乙叉二膦酸盐45%、草酸甲25%、硫酸亚铁10%、硫酸铝20%配成复合除锌剂。 5. The composite of claim 1 for treating waste water containing zinc in addition to zinc claim, characterized in that: According to the proportion of the total mass of the composite in addition to zinc percentage, hydroxy ethylidene diphosphonic acid and 45% oxalic acid A 25%, 10% ferrous sulfate, aluminum sulfate, 20% zinc compound formulated scavenger.
  6. 6.根据权利要求1所述的一种处理含锌废水的复合除锌剂,其特征在于:按占复合除锌剂总质量百分比计,将羟基而乙叉二膦酸盐阳%、草酸钠20%、硫化钠10%、硫酸铝15% 配成复合除锌剂。 6. The composite of claim 1 for treating waste water containing zinc in addition to zinc claim, characterized in that: According to the proportion of the total mass of the composite in addition to zinc percentage, hydroxy ethylidene diphosphonic acid and the% male, sodium oxalate 20%, 10% sodium sulfide, aluminum sulfate 15% zinc complex dubbed scavenger.
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CN103043769A (en) * 2012-12-07 2013-04-17 常州大学 Compound agent for removing lead from waste water
CN102976466A (en) * 2012-12-11 2013-03-20 常州大学 Compound barium remover for treating baric wastewater
CN103014760A (en) * 2013-01-09 2013-04-03 广西有色金属集团汇元锰业有限公司 Production method of electrolytic manganese metal
CN103074490A (en) * 2013-01-09 2013-05-01 广西有色金属集团汇元锰业有限公司 Purification method in electrolytic metal manganese production process by multi-mine method
CN103074490B (en) 2013-01-09 2014-03-12 广西有色金属集团汇元锰业有限公司 Purification method in electrolytic metal manganese production process by multi-mine method
CN103014760B (en) * 2013-01-09 2015-04-15 广西有色金属集团汇元锰业有限公司 Production method of electrolytic manganese metal
CN105399215A (en) * 2015-12-18 2016-03-16 苏州市金星工艺镀饰有限公司 Wastewater treatment agent used for electroplating wastewater treatment
CN105565507A (en) * 2015-12-18 2016-05-11 苏州市金星工艺镀饰有限公司 Method for preparing electroplating wastewater treating agent

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