CN115124186A - Method for treating aged micro-plastic wastewater by using microalgae - Google Patents
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- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 26
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- 239000004033 plastic Substances 0.000 title claims abstract 8
- 229920000426 Microplastic Polymers 0.000 claims abstract description 54
- 230000032683 aging Effects 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003698 anagen phase Effects 0.000 claims abstract description 5
- 238000012258 culturing Methods 0.000 claims abstract 3
- 239000002253 acid Substances 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims 2
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- 241000195661 Scenedesmus quadricauda Species 0.000 claims 1
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Abstract
Description
技术领域technical field
本发明属于废水处理领域，具体涉及一种微藻处理老化微塑料废水的方法。The invention belongs to the field of wastewater treatment, and in particular relates to a method for microalgae to treat aging microplastic wastewater.
背景技术Background technique
微藻的生物聚合物净化老化微塑料是一种由日光驱动、低成本且环境友好的技术。近年来，由于污水排放标准的提升以及在碳中和背景下对环境友好技术的需求使得利用微藻净化老化微塑料技术获得越来越多的关注。微藻在高浓度老化微塑料的环境中会由于适应性反应产生胞外聚合物(EPS)，老化微塑料的疏水性促进了两者之间的聚集，这体现了微藻具有净化高浓度老化微塑料废水的潜力。Biopolymers of microalgae purify aging microplastics is a sunlight-driven, low-cost and environmentally friendly technology. In recent years, the use of microalgae to purify aging microplastics has gained more and more attention due to the improvement of sewage discharge standards and the need for environmentally friendly technologies in the context of carbon neutrality. Microalgae will produce extracellular polymers (EPS) due to adaptive reactions in an environment with high concentrations of aged microplastics, and the hydrophobicity of aged microplastics promotes the aggregation between the two, which reflects the ability of microalgae to purify high-concentration aged microalgae. Potential of microplastic wastewater.
尽管基于微藻的生物聚合物的污染物净化技术拥有许多优点，但是自然界中存在种类繁多的污染物，该技术无法保证无选择性地净化污染物，因此需要寻求与其他绿色的手段联合来强化微藻修复技术的净化能力。Although the pollutant purification technology based on microalgae biopolymers has many advantages, there are a wide variety of pollutants in nature, and this technology cannot guarantee the non-selective purification of pollutants, so it needs to be combined with other green means to strengthen The purifying power of microalgae remediation technology.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术中的缺点，提供一种微藻处理老化微塑料废水的方法。The purpose of the present invention is to overcome the shortcomings in the prior art, and to provide a method for microalgae to treat aging microplastic wastewater.
为实现上述目的，本发明采用的技术方案为：To achieve the above object, the technical scheme adopted in the present invention is:
一种微藻处理老化微塑料废水的方法，包括下述步骤：A method for microalgae treatment of aging microplastic waste water, comprising the following steps:
1)、将功能性微藻进行预先培养，使其达到对数生长期；1), pre-cultivate the functional microalgae to make it reach the logarithmic growth phase;
2)、利用强酸或者强碱分别对微塑料废水老化处理；2), use strong acid or strong alkali to treat microplastic wastewater respectively;
3)、将步骤1)培养后的功能性微藻接入到步骤2)中强酸或者强碱分别预处理后的微塑料废水，进行高浓度老化微塑料废水的净化。3), connect the functional microalgae cultured in step 1) to the microplastic wastewater pretreated by strong acid or strong alkali in step 2), and purify the high-concentration aging microplastic wastewater.
步骤1)中功能性微藻为四尾栅藻或者小球藻。In step 1), the functional microalgae is Scenedesmus or Chlorella.
步骤1)中预先培养的条件为:全天光照，光照强度4800-5200Lux，培养温度24-26℃，持续通入CO2和N2的混合气，CO2所占的体积分数为3％-5％，通气量30-40mL/min。The pre-cultivation conditions in step 1) are: all-day light, light intensity of 4800-5200Lux, culture temperature of 24-26°C, continuous introduction of a mixture of CO 2 and N 2 , and the volume fraction of CO 2 is 3%- 5%, ventilation volume 30-40mL/min.
步骤2)中所述的强酸为盐酸、硫酸或者硝酸；所述的强碱为氢氧化钠或者氢氧化钾。The strong acid described in step 2) is hydrochloric acid, sulfuric acid or nitric acid; and the strong base is sodium hydroxide or potassium hydroxide.
强酸或者强碱的浓度均为5-20mol/L，处理时间为24-48h。The concentration of strong acid or strong base is 5-20mol/L, and the treatment time is 24-48h.
强酸或者强碱的浓度均为10mol/L，处理时间为48h。The concentration of strong acid or strong base is 10mol/L, and the treatment time is 48h.
步骤2)中微塑料为聚对苯二甲酸乙二醇酯，尺寸为5-50μm，强酸或者强碱处理后微塑料的浓度为20-200mg/L。In step 2), the microplastics are polyethylene terephthalate, the size is 5-50 μm, and the concentration of the microplastics after the strong acid or strong alkali treatment is 20-200 mg/L.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本申请提供了一种绿色环保、经济有效且可持续的方法净化高浓度老化微塑料废水的方法。利用微藻净化含高浓度老化微塑料废水，利用微藻的光合作用，使污染物得到净化，并且得到微藻生物量以及细胞色素。微藻净化方式能够使微藻产生更多的带负电荷的胞外聚合物(EPS)，对于老化微塑料具有潜在的净化潜力。同时利用强酸或者强碱预先处理老化微塑料废水，使得其短期内达到自然老化程度。The present application provides a method for purifying high-concentration aged microplastic waste water in an environmentally friendly, cost-effective and sustainable method. Using microalgae to purify wastewater containing high-concentration aging microplastics, using microalgae photosynthesis to purify pollutants, and obtain microalgae biomass and cytochromes. Microalgae purification methods can make microalgae produce more negatively charged extracellular polymers (EPS), which have potential purification potential for aging microplastics. At the same time, the aging microplastic wastewater is pretreated with strong acid or strong alkali, so that it can reach the natural aging level in a short period of time.
附图说明Description of drawings
图1是实施案例中由小球藻(培养8天后)产生的EPS中糖醛酸峰强度图；Fig. 1 is the peak intensity map of uronic acid in EPS produced by Chlorella (after 8 days of culture) in the implementation case;
图2是实施案例中加入强碱老化微塑料废水中小球藻OD680变化图。Figure 2 is a graph showing the change of Chlorella OD 680 in the aged microplastic wastewater by adding strong alkali in the implementation case.
图3是实施案例中加入强酸老化微塑料废水中小球藻OD680变化图；Fig. 3 is a graph showing the change of Chlorella OD 680 in the aged microplastic wastewater by adding strong acid in the implementation case;
图4是实施案例中加入强碱老化微塑料废水中叶绿素浓度变化图；Fig. 4 is a graph showing the change of chlorophyll concentration in the aged microplastic wastewater by adding strong alkali in the implementation case;
图5是实施案例中加入强酸老化微塑料废水中叶绿素浓度变化图；Fig. 5 is a graph showing the change of chlorophyll concentration in the aged microplastic wastewater by adding strong acid in the implementation case;
图6是实施案例中加入强碱老化微塑料废水中类胡萝卜素浓度变化图；Fig. 6 is a graph showing the change of carotenoid concentration in the aged microplastic wastewater by adding strong alkali in the implementation case;
图7是实施案例中加入强酸老化微塑料废水中类胡萝卜素浓度变化图。Fig. 7 is a graph showing the change of carotenoid concentration in the aged microplastic wastewater by adding strong acid in the implementation case.
具体实施方式Detailed ways
为了使本技术领域的技术人员更好地理解本发明的技术方案，下面结合附图和最佳实施例对本发明作进一步的详细说明。In order to make those skilled in the art better understand the technical solutions of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and the best embodiments.
实施案例：一种微藻处理老化微塑料废水的方法，包括如下步骤：Implementation case: a method for microalgae to treat aging microplastic wastewater, including the following steps:
(1)将小球藻UTEX1602接种至含有200mL灭菌后的BG-11培养基中，将其置于生化培养箱中进行预先培养，使小球藻达到对数生长期，之后将其作为工作藻液；预先培养的条件设置为：全天光照，光照强度4800-5200Lux，培养温度24-26℃，通气量30-40mL/min，通入的气体为CO2和N2的混合气，CO2所占的体积分数为5％。(1) Inoculate Chlorella UTEX1602 into BG-11 medium containing 200 mL of sterilized BG-11 medium, and place it in a biochemical incubator for pre-cultivation, so that Chlorella can reach the logarithmic growth phase, and then use it as a work Algae liquid; pre-cultivation conditions are set as: all day light, light intensity of 4800-5200Lux, culture temperature of 24-26°C, ventilation volume of 30-40mL/min, the gas introduced is a mixture of CO 2 and N 2 , CO The volume fraction occupied by 2 is 5%.
(2)分别利用48h盐酸或者氢氧化钠处理人工模拟含高浓度老化微塑料废水进行处理，获得废水处理液；盐酸或者氢氧化钠均为浓度10mol/L；(2) Use 48h hydrochloric acid or sodium hydroxide to treat artificially simulated waste water containing high-concentration aging microplastics to obtain a wastewater treatment solution; hydrochloric acid or sodium hydroxide are both at a concentration of 10mol/L;
人工模拟含高浓度老化微塑料废水的配置方式为将一定量4g/L老化微塑料母液(微塑料为聚对苯二甲酸乙二醇酯，尺寸为10μm；)加入到200mL BG-11培养基中，获得含20、100和200mg/L老化微塑料废水；The configuration method of artificially simulating high-concentration aging microplastic wastewater is to add a certain amount of 4g/L aging microplastic mother liquor (the microplastic is polyethylene terephthalate, with a size of 10 μm;) into 200 mL of BG-11 medium. , obtained wastewater containing 20, 100 and 200 mg/L of aged microplastics;
(3)步骤(1)获得的藻液经过3次去离子水洗涤离心后，再接种至含有步骤(2)强酸或者强碱处理后的人工模拟含高浓度老化微塑料废水中，置于微藻培养架上培养，确保初始接种微藻在680nm波长下吸光度为0.1，全天光照，光照强度4800-5200Lux，培养温度24-26℃，培养周期8天，取样测定微藻EPS中糖醛酸含量。(3) The algal liquid obtained in step (1) is washed and centrifuged with deionized water for 3 times, and then inoculated into the artificially simulated waste water containing high-concentration aging microplastics treated with strong acid or strong alkali in step (2), and placed in microplastic waste water. Culture on an algae culture rack to ensure that the initial inoculated microalgae has an absorbance of 0.1 at a wavelength of 680nm, all day light, light intensity of 4800-5200Lux, culture temperature of 24-26°C, and a culture period of 8 days. Sampling and determination of uronic acid in microalgae EPS content.
(4)定期收集步骤(3)培养的藻液，测定其在680nm波长下的吸光度。(4) Periodically collect the algal liquid cultured in step (3), and measure its absorbance at a wavelength of 680 nm.
(5)定期收集步骤(3)培养的藻液，经过离心后弃去上清液，获得藻泥，将收获的藻泥重新悬浮在同等体积下的甲醇-水溶液中，在4℃下保存16-24h，之后离心测定上清液多波长下的吸光度，测定细胞内光合色素浓度。(5) Periodically collect the algal fluid cultured in step (3), discard the supernatant after centrifugation to obtain algal mud, resuspend the harvested algal mud in methanol-water solution at the same volume, and store at 4°C for 16 -24h, after centrifugation, the absorbance of the supernatant at multiple wavelengths was measured, and the intracellular photosynthetic pigment concentration was measured.
对照组与实施案例的区别在于培养基不需要添加老化微塑料。The difference between the control group and the implementation case is that the medium does not need to add aged microplastics.
即一种微藻处理废水的方法，包括如下步骤：That is, a method for treating wastewater by microalgae, comprising the steps of:
(1)将小球藻UTEX1602接种至含有200mL灭菌后的BG-11培养基中，将其置于生化培养箱中进行预先培养，使小球藻达到对数生长期，之后将其作为工作藻液；预先培养的条件设置为：全天光照，光照强度4800-5200Lux，培养温度24-26℃，通气量30-40mL/min，通入的气体为CO2和N2的混合气，CO2所占的体积分数为5％。(1) Inoculate Chlorella UTEX1602 into BG-11 medium containing 200 mL of sterilized BG-11 medium, and place it in a biochemical incubator for pre-cultivation, so that Chlorella can reach the logarithmic growth phase, and then use it as a work Algae liquid; pre-cultivation conditions are set as: all day light, light intensity of 4800-5200Lux, culture temperature of 24-26°C, ventilation volume of 30-40mL/min, the gas introduced is a mixture of CO 2 and N 2 , CO The volume fraction occupied by 2 is 5%.
(2)步骤(1)获得的藻液经过3次去离子水洗涤离心后，再接种至水中，置于微藻培养架上培养，确保初始接种微藻在680nm波长下吸光度为0.1，全天光照，光照强度4800-5200Lux，培养温度24-26℃，培养周期8天，取样测定微藻EPS中糖醛酸含量。(2) After the algal liquid obtained in step (1) is washed and centrifuged with deionized water for 3 times, it is then inoculated into water and placed on a microalgae culture rack for cultivation to ensure that the absorbance of the initial inoculated microalgae is 0.1 at a wavelength of 680 nm, and the whole day Light, light intensity of 4800-5200Lux, culture temperature of 24-26°C, culture period of 8 days, sampling and determination of uronic acid content in microalgae EPS.
(3)定期收集步骤(2)培养的藻液，测定其在680nm波长下的吸光度。(3) Periodically collect the algal liquid cultured in step (2), and measure its absorbance at a wavelength of 680 nm.
(4)定期收集步骤(2)培养的藻液，经过离心后弃去上清液，获得藻泥，将收获的藻泥重新悬浮在同等体积下的甲醇-水溶液中，在4℃下保存16-24h，之后离心测定上清液多波长下的吸光度，测定细胞内光合色素浓度。(4) Periodically collect the algal fluid cultured in step (2), discard the supernatant after centrifugation to obtain algal mud, resuspend the harvested algal mud in methanol-water solution at the same volume, and store at 4°C for 16 -24h, after centrifugation, the absorbance of the supernatant at multiple wavelengths was measured, and the intracellular photosynthetic pigment concentration was measured.
图1所示分别加入强酸或者强碱老化微塑料处理后，经过8天的培养，微藻对于20、100和200mg/L人工模拟废水中老化微塑料所产生的EPS中糖醛酸含量比对照组分别低8.36％、高45.48％。As shown in Figure 1, after adding strong acid or strong alkali to the aging microplastics, after 8 days of culture, the content of uronic acid in EPS produced by microalgae for aging microplastics in 20, 100 and 200 mg/L artificial simulated wastewater was higher than that of the control. The groups were 8.36% lower and 45.48% higher.
图2所示分别加入强碱老化微塑料处理后，经过8天的培养，微藻在净化20、100和200mg/L人工模拟废水中老化微塑料过程中OD680分别为0.553、0.436和0.447，相比于对照组，分别提升了17.41％和降低了7.43％、5.10％。As shown in Figure 2, after adding strong alkali and aging microplastics, after 8 days of culture, the OD 680 of microalgae in the process of purifying 20, 100 and 200 mg/L artificially simulated wastewater and aging microplastics were 0.553, 0.436 and 0.447, respectively. Compared with the control group, it increased by 17.41% and decreased by 7.43% and 5.10%, respectively.
图3所示分别加入强酸老化微塑料处理后，经过8天的培养，微藻在净化20、100和200mg/L人工模拟废水中老化微塑料过程中OD680分别为0.551、0.539和0.605，相比于对照组，分别提升了16.99％、14.44％和28.45％。As shown in Figure 3, after adding strong acid and aging microplastics, after 8 days of culture, the OD 680 of microalgae in the process of purifying 20, 100 and 200 mg/L artificial simulated wastewater and aging microplastics were 0.551, 0.539 and 0.605, respectively. Compared with the control group, it increased by 16.99%, 14.44% and 28.45% respectively.
图4所示分别加入强碱老化微塑料处理后，经过8天的培养，微藻在净化20、100和200mg/L人工模拟废水中老化微塑料过程中叶绿素含量分别为2.56mg/L、2.14mg/L和2.00mg/L，相比于对照组，分别提升了19.63％和降低了0.09％和6.54％。As shown in Figure 4, after adding strong alkali and aging microplastics, after 8 days of culture, the chlorophyll content of microalgae in the process of purifying 20, 100 and 200 mg/L artificial simulated wastewater and aging microplastics was 2.56 mg/L and 2.14 mg/L, respectively. Compared with the control group, mg/L and 2.00mg/L increased by 19.63% and decreased by 0.09% and 6.54%, respectively.
图5所示分别加入强酸老化微塑料处理后，经过8天的培养，微藻在净化20、100和200mg/L人工模拟废水中老化微塑料过程中叶绿素含量分别为2.47mg/L、2.79mg/L和2.81mg/L，相比于对照组，分别提升了15.42％和降低了30.37％和31.31％。As shown in Figure 5, after adding strong acid and aging microplastics, after 8 days of culture, the chlorophyll content of microalgae in the process of purifying 20, 100 and 200 mg/L artificial simulated wastewater and aging microplastics was 2.47 mg/L and 2.79 mg, respectively. /L and 2.81mg/L, compared with the control group, increased by 15.42% and decreased by 30.37% and 31.31%, respectively.
图6所示分别加入强碱老化微塑料处理后，经过8天的培养，微藻在净化20、100和200mg/L人工模拟废水中老化微塑料过程中类胡萝卜素含量分别为0.74mg/L、0.63mg/L和0.61mg/L，相比于对照组，分别提升了17.46％和降低了1.11％和3.17％。As shown in Figure 6, after adding strong alkali and aging microplastics, after 8 days of culture, the carotenoid content of microalgae in the process of purifying 20, 100 and 200 mg/L artificially simulated wastewater and aging microplastics was 0.74 mg/L, respectively. , 0.63mg/L and 0.61mg/L, which were increased by 17.46% and decreased by 1.11% and 3.17%, respectively, compared with the control group.
图7所示分别加入强酸老化微塑料处理后，经过8天的培养，微藻在净化20、100和200mg/L人工模拟废水中老化微塑料过程中类胡萝卜素含量分别为0.77mg/L、0.80mg/L和0.82mg/L，相比于对照组，分别提升了22.22％、26.98％和30.16％。As shown in Figure 7, after adding strong acid and aging microplastics, after 8 days of culture, the carotenoid contents of microalgae in the process of purifying 20, 100 and 200 mg/L artificial simulated wastewater were 0.77 mg/L, 0.77 mg/L and 200 mg/L, respectively. 0.80mg/L and 0.82mg/L, compared with the control group, increased by 22.22%, 26.98% and 30.16% respectively.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.
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| CN113943054A (en) * | 2021-10-25 | 2022-01-18 | 常熟理工学院 | A method for efficiently cleaning fluorine-containing microplastics in water using spirulina |
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| WO2017130106A1 (en) * | 2016-01-25 | 2017-08-03 | Bio-P S.R.L. | Process for producing starch from microalgae |
| CN113943054A (en) * | 2021-10-25 | 2022-01-18 | 常熟理工学院 | A method for efficiently cleaning fluorine-containing microplastics in water using spirulina |
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