技术领域technical field
本发明属于废水处理领域，具体涉及一种利用耐酸硫酸盐菌处理吡啶硫酮锌生产废水，并将生活污水和吡啶硫酮锌生产废水混合以增加可生化性。The invention belongs to the field of waste water treatment, and in particular relates to treating waste water produced by zinc pyrithione by using acid-resistant sulfate bacteria, and mixing domestic sewage and waste water produced by zinc pyrithione to increase biodegradability.
技术背景technical background
吡啶硫酮锌作为优良、广谱、低毒、环保的真菌和细菌的抑菌剂，可广泛用于民用涂料、胶粘剂和地毯、洗发和护发化妆品等领域。已有很多研究表明吡啶硫酮锌即使在低浓度下对水生动物也有很大的毒性。生产吡啶硫酮锌的原料有吡啶硫酮钠、硫酸锌。由于原料的过量添加和反应不完全等问题，生产完的废水中含有高浓度的吡啶硫酮钠、硫酸锌、硫酸钠和少量的产品吡啶硫酮锌。这些物质中，吡啶硫酮钠和吡啶硫酮锌都是一种抗菌剂，但是吡啶硫酮钠属于低毒化合物，对水生生物的毒性很小。锌离子在低浓度时对细菌的生命活动有促进作用，但随着浓度的增大，反而会抑制细菌的生长。有研究表明在锌离子浓度达到20mg/L时，它就会对硫酸盐还原菌的代谢过程产生影响；低浓度的硫酸钠虽然对细菌没有明显影响，但随着硫酸钠的浓度的提高，废水盐度变高，不利于硫酸盐还原菌的生长。Zinc pyrithione is an excellent, broad-spectrum, low-toxicity, and environmentally friendly antibacterial agent for fungi and bacteria, and can be widely used in the fields of civil coatings, adhesives and carpets, shampoos and hair care cosmetics. Many studies have shown that zinc pyrithione is very toxic to aquatic animals even at low concentrations. The raw materials for producing zinc pyrithione include sodium pyrithione and zinc sulfate. Due to problems such as excessive addition of raw materials and incomplete reaction, the waste water after production contains high concentrations of sodium pyrithione, zinc sulfate, sodium sulfate and a small amount of product zinc pyrithione. Among these substances, pyrithione sodium and pyrithione zinc are both antibacterial agents, but pyrithione sodium is a low-toxic compound with little toxicity to aquatic organisms. Zinc ions can promote the life activities of bacteria at low concentrations, but as the concentration increases, it will inhibit the growth of bacteria. Studies have shown that when the concentration of zinc ions reaches 20mg/L, it will affect the metabolic process of sulfate-reducing bacteria; although low-concentration sodium sulfate has no obvious effect on bacteria, as the concentration of sodium sulfate increases, wastewater High salinity is not conducive to the growth of sulfate-reducing bacteria.
吡啶硫酮锌生产废水的处理难度很高，国内外这方面的研究较少。处理这种废水的方法有物理化学法和生物法，物理化学的方法主要为通过加入某些离子使得锌离子和硫酸根离子形成沉淀去除，具有处理效率高等优点，但是物理化学方法不仅成本高而且会产生二次污染，给后续的处理增加了难度，而且处理成本太高，某些小工厂为了节约成本，直接将废水排入水体，吡啶硫酮锌和高浓度的硫酸锌会对水体造成很严重的污染。The treatment of wastewater from zinc pyrithione production is very difficult, and there are few studies in this area at home and abroad. There are physical chemical methods and biological methods to treat this kind of wastewater. The physical chemical method is mainly to form precipitation and remove zinc ions and sulfate ions by adding certain ions. It has the advantages of high treatment efficiency, but the physical chemical method is not only costly but also It will produce secondary pollution, which will increase the difficulty of subsequent treatment, and the treatment cost is too high. In order to save costs, some small factories directly discharge wastewater into the water body. Zinc pyrithione and high-concentration zinc sulfate will cause serious damage to the water body. pollution.
微生物处理技术相对于其他技术而言，具有成本低、无二次污染等特点，可操作性强。根据废水的特点，硫酸钠和硫酸锌的含量较高，可以采用硫酸盐还原菌来处理。硫酸盐还原菌能够将SO42-还原生成H2S还可进一步生成单质S或者同废水中存在的重金属如Zn2+生成ZnS沉淀下来。同时硫酸盐反应过程中也会消耗体系中存在的H+，进一步沉淀锌离子。将生活污水和吡啶硫酮锌生产废水混合不仅能降低废水中锌离子和硫酸根离子的浓度，提高废水的pH值，还能为硫酸盐还原菌提供碳源、氮源和微量元素。有效的解决了硫酸盐还原菌应用条件苛刻和处理成本高的问题。该方法能经济有效的处理吡啶硫酮锌生产废水，且无二次污染，具有良好的经济效益和环境效益。Compared with other technologies, microbial treatment technology has the characteristics of low cost, no secondary pollution, etc., and strong operability. According to the characteristics of wastewater, the content of sodium sulfate and zinc sulfate is relatively high, and sulfate-reducing bacteria can be used to treat it. Sulfate-reducing bacteria can reduce SO42- to generate H2 S and further generate elemental S, or form ZnS with heavy metals such as Zn2+ in the wastewater to precipitate. At the same time, the H+ present in the system will be consumed during the sulfate reaction, and zinc ions will be further precipitated. Mixing domestic sewage with zinc pyrithione production wastewater can not only reduce the concentration of zinc ions and sulfate ions in wastewater, increase the pH value of wastewater, but also provide carbon sources, nitrogen sources and trace elements for sulfate-reducing bacteria. The problem of harsh application conditions and high treatment cost of sulfate-reducing bacteria is effectively solved. The method can economically and effectively treat the wastewater produced by zinc pyrithione without secondary pollution, and has good economic and environmental benefits.
发明内容Contents of the invention
本发明的目的在于克服现在技术成本高及难以达到处理效果，采用从垃圾渗滤液中筛选出硫酸盐还原 菌，并通过逐级驯化后得到耐高浓度锌离子的菌种，最后利用该菌种对ZPT废水的处理。同时，为增加处理效果，本发明将生活污水和吡啶硫酮锌生产废水混合，稀释吡啶硫酮锌生产废水中的吡啶硫酮钠、硫酸锌、硫酸钠和吡啶硫酮锌，使该废水更适合硫酸盐还原菌的生长。The purpose of the present invention is to overcome the high cost of the current technology and the difficulty in achieving the treatment effect. It uses sulfate-reducing bacteria to be screened out from the landfill leachate, and the strains resistant to high-concentration zinc ions are obtained through step-by-step domestication. Finally, the strains are used Treatment of ZPT wastewater. Simultaneously, in order to increase the treatment effect, the present invention mixes domestic sewage and zinc pyrithione production waste water, dilutes pyrithione sodium, zinc sulfate, sodium sulfate and pyrithione zinc in the production waste water of pyrithione zinc, makes this waste water more Suitable for the growth of sulfate reducing bacteria.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
一种利用硫酸盐还原菌处理吡啶硫酮锌生产废水的方法，是通过垃圾填埋场的垃圾渗滤液中筛选出硫酸盐还原菌，再经过逐级驯化之后优化的菌种，最后将驯化后的菌种处理吡啶硫酮锌生产废水和生活污水的混合废水中。此方法包括以下步骤：A method for treating waste water produced by zinc pyrithione by using sulfate-reducing bacteria, is to screen out sulfate-reducing bacteria from landfill leachate, and then domesticate the optimized strains step by step, and finally the domesticated Strain treatment of zinc pyrithione in the mixed wastewater of production wastewater and domestic wastewater. This method includes the following steps:
(1)将从垃圾填埋场采集的垃圾渗滤液接种至硫酸盐还原菌专属培养液中进行培养，渗滤液与培养液的体积比为1:20，培养液配方为：无水硫酸钠0.5g/L、氯化铵1.0g/L、氯化钙0.1g/L、磷酸氢二钾0.5g/L、七水合硫酸镁2.0g/L、乳酸钠3.5g/L、酵母浸膏1.0g/L、硫酸亚铁铵0.5g/L、抗坏血酸0.5g/L，调pH至7.0，厌氧30～37℃静置培养至培养液由澄清变至墨汁色，将培养出的菌液加入专属培养液中传代培养3次，获得富集的微生物。(1) Inoculate the landfill leachate collected from the landfill into the exclusive culture medium for sulfate-reducing bacteria for cultivation. The volume ratio of the leachate to the culture medium is 1:20, and the formula of the culture medium is: anhydrous sodium sulfate 0.5 g/L, Ammonium Chloride 1.0g/L, Calcium Chloride 0.1g/L, Dipotassium Hydrogen Phosphate 0.5g/L, Magnesium Sulfate Heptahydrate 2.0g/L, Sodium Lactate 3.5g/L, Yeast Extract 1.0g/L L. Ferrous ammonium sulfate 0.5g/L, ascorbic acid 0.5g/L, adjust the pH to 7.0, anaerobic 30-37 ℃ static culture until the culture liquid changes from clarification to ink color, and add the cultured bacteria liquid to the exclusive culture Subcultured in liquid for 3 times to obtain enriched microorganisms.
(2)将富集的微生物以10％的接种量接种至驯化培养液中进行驯化，驯化温度为20℃，pH为6.5，一个驯化周期为5天，驯化过程以添加不同质量的ZnSO4控制锌离子浓度，分别为100、150、200、250、300mg/L，从最低锌离子浓度100mg/L进行驯化，逐级增加培养液内锌离子的浓度，当培养液的颜色能在第二天变成黑灰色，认为硫酸盐还原菌达到此相应锌离子浓度下的活性，进入下一个锌离子浓度梯度下的驯化，当硫酸盐还原菌达到最高锌离子浓度300mg/L要求的活性时，驯化完成。(2) Inoculate the enriched microorganisms with 10% inoculum size into the domestication medium for domestication. The domestication temperature is 20° C., the pH is 6.5, and one domestication cycle is5 days. The domestication process is controlled by adding ZnSO of different quality The concentration of zinc ions is 100, 150, 200, 250, 300mg/L respectively, and the minimum zinc ion concentration is 100mg/L for domestication, and the concentration of zinc ions in the culture medium is gradually increased. Turn into black gray, it is considered that the sulfate-reducing bacteria have reached the activity of the corresponding zinc ion concentration, and enter the next step of domestication under the zinc ion concentration gradient. Finish.
(3)将驯化完成后的SRB放入发酵罐中培养，培养三天后以10％的接种量接种至混合废水中，混合废水为吡啶硫酮锌生产废水和生活废水，比例为1:2.5～1:4.5。(3) Put the SRB after domestication into a fermenter for cultivation, and inoculate it into mixed wastewater with an inoculum of 10% after three days of cultivation. The mixed wastewater is zinc pyrithione production wastewater and domestic wastewater, and the ratio is 1:2.5～ 1:4.5.
本发明与现有技术相比，具有如下显出效果：Compared with the prior art, the present invention has the following effects:
本发明的方法是直接从垃圾渗滤液中提纯并驯化耐高浓度锌离子的硫酸盐还原菌，并将该菌种用于吡啶硫酮锌生产废水的处理，处理成本较低，操作简单；The method of the present invention is to directly purify and domesticate sulfate-reducing bacteria resistant to high-concentration zinc ions from landfill leachate, and use the strains to treat waste water from zinc pyrithione production, with low treatment cost and simple operation;
进一步的，本发明方法采用了混合吡啶硫酮锌生产废水和生活污水，在引入碳氮磷及其他微量元素的同时，也可以稀释吡啶硫酮锌生产废水中锌离子和吡啶硫酮钠、降低废水的盐度并提高废水的pH值，降低了吡啶硫酮锌生产废水处理难度，而且节约了成本；Further, the method of the present invention adopts mixed zinc pyrithione production wastewater and domestic sewage, while introducing carbon, nitrogen, phosphorus and other trace elements, it can also dilute zinc ions and pyrithione sodium in the zinc pyrithione production wastewater, reducing Increase the salinity of wastewater and increase the pH value of wastewater, which reduces the difficulty of wastewater treatment from zinc pyrithione production and saves costs;
进一步的，本发明的方法利用了硫酸盐还原菌的特性，即将硫酸盐还原成硫化氢因而沉淀废水中的锌离子，经过处理，废水中锌离子的处理率可达95％，硫酸盐的去除率也能达到80％，吡啶硫酮锌浓度低于检测限(1mg/L)，对吡啶硫酮锌生产废水提供一种高效的去除方法。Further, the method of the present invention has utilized the characteristic of sulfate-reducing bacteria, is about to reduce sulfate to hydrogen sulfide thus precipitates the zinc ion in wastewater, after treatment, the treatment rate of zinc ion in wastewater can reach 95%, the removal of sulfate The efficiency can also reach 80%, and the zinc pyrithione concentration is lower than the detection limit (1mg/L), providing an efficient removal method for the zinc pyrithione production wastewater.
附图说明:Description of drawings:
图1是硫酸盐还原菌处理吡啶硫酮锌生产废水机理图Figure 1 is a schematic diagram of the sulfate-reducing bacteria treatment of zinc pyrithione production wastewater
图2是硫酸盐还原菌处理吡啶硫酮锌生产废水流程图Figure 2 is a flow chart of sulfate-reducing bacteria treating wastewater from zinc pyrithione production
具体实施方式：detailed description:
下面结合附图和实施例对本发明进一步的详细说明：Below in conjunction with accompanying drawing and embodiment the present invention is described in further detail:
实施例1吡啶硫酮锌生产废水的处理The treatment of embodiment 1 zinc pyrithione production waste water
此次所用菌种来源XXX垃圾填埋场中的渗滤液，将样品收集后运回实验室，立即保存于4℃冰箱中，所处理的废水为湖南省XXX公司吡啶硫酮锌生产废水，具体步骤如下：The strains used this time come from the leachate in the XXX landfill. The samples were collected and transported back to the laboratory, where they were immediately stored in a refrigerator at 4°C. The treated wastewater was from the production of zinc pyrithione in XXX Company in Hunan Province. Specifically Proceed as follows:
a.将从垃圾填埋场采集的垃圾渗滤液接种至硫酸盐还原菌专属培养液中进行培养，渗滤液与培养液的体积比为1:20，培养液配方为：无水硫酸钠0.5g/L、氯化铵1.0g/L、氯化钙0.1g/L、磷酸氢二钾0.5g/L、七水合硫酸镁2.0g/L、乳酸钠3.5g/L、酵母浸膏1.0g/L、硫酸亚铁铵0.5g/L、抗坏血酸0.5g/L，调pH至7.0，厌氧30～37℃静置培养至培养液由澄清变至墨汁色，将培养出的菌液加入专属培养液中传代培养3次，获得富集的微生物；a. Inoculate the landfill leachate collected from the landfill into the exclusive culture solution for sulfate-reducing bacteria for cultivation. The volume ratio of the leachate to the culture solution is 1:20, and the formula of the culture solution is: anhydrous sodium sulfate 0.5g /L, ammonium chloride 1.0g/L, calcium chloride 0.1g/L, dipotassium hydrogen phosphate 0.5g/L, magnesium sulfate heptahydrate 2.0g/L, sodium lactate 3.5g/L, yeast extract 1.0g/L , ferrous ammonium sulfate 0.5g/L, ascorbic acid 0.5g/L, adjust the pH to 7.0, anaerobically culture at 30-37°C until the culture liquid changes from clarification to ink color, and add the cultured bacteria liquid to the exclusive culture liquid Subcultured in medium for 3 times to obtain enriched microorganisms;
b.将富集的微生物以10％的接种量接种至驯化培养液中进行驯化，驯化温度为20℃，pH为6.5，一个驯化周期为5天，驯化过程以添加不同质量的ZnSO4控制锌离子浓度，分别为100、150、200、250、300mg/L，从最低锌离子浓度100mg/L进行驯化，逐级增加培养液内锌离子的浓度，当培养液的颜色能在第二天变成黑灰色，认为硫酸盐还原菌达到此相应锌离子浓度下的活性，进入下一个锌离子浓度梯度下的驯化，当硫酸盐还原菌达到最高锌离子浓度300mg/L要求的活性时，驯化完成。b. Inoculate the enriched microorganisms with 10% inoculum amount into the domestication medium for domestication, the domestication temperature is 20°C, the pH is 6.5, and one domestication cycle is5 days, and the domestication process is controlled by adding ZnSO of different qualities The ion concentration is 100, 150, 200, 250, and 300 mg/L, respectively. The minimum zinc ion concentration is 100 mg/L for domestication, and the concentration of zinc ions in the culture solution is gradually increased. When the color of the culture solution can change in the next day It turns black and gray, it is considered that the sulfate-reducing bacteria have reached the activity of the corresponding zinc ion concentration, and enter the next step of domestication under the zinc ion concentration gradient. When the sulfate-reducing bacteria reach the activity required by the highest zinc ion concentration of 300mg/L, the domestication is completed .
c.将驯化完成后的SRB放入发酵罐中培养，培养三天后以10％的接种量接种至混合废水中，混合废水为吡啶硫酮锌生产废水和生活废水，比例为1:2.5；c. Put the SRB after domestication into a fermenter for cultivation, and inoculate it into mixed wastewater with a 10% inoculation amount after three days of cultivation. The mixed wastewater is zinc pyrithione production wastewater and domestic wastewater, and the ratio is 1:2.5;
SO42-和硫酸盐还原菌生成的S2-与锌离子结合成淡黄色的硫化锌沉淀，酸性的吡啶硫酮锌生产废水中的锌离子的去除率能达到95％，硫酸根的去除率能达到80％，吡啶硫酮锌浓度低于检测限(1mg/L)，出水的pH为7.0。SO42- and S2- produced by sulfate-reducing bacteria combine with zinc ions to form pale yellow zinc sulfide precipitates. The removal rate of zinc ions in acidic zinc pyrithione production wastewater can reach 95%, and the removal of sulfate The yield can reach 80%, the zinc pyrithione concentration is lower than the detection limit (1mg/L), and the pH of the effluent is 7.0.
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| CN201610443238.0ACN106045056B (en) | 2016-06-21 | 2016-06-21 | A method of waste water is produced using sulfate reducing bacteria processing zinc pyrithione |
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