CN116813076A - A kind of preparation method of modified polyurethane filler - Google Patents
A kind of preparation method of modified polyurethane filler Download PDFInfo
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Abstract
本发明涉及高分子载体改性技术领域,尤其涉及一种改性聚氨酯填料的制备方法。本发明将过氧化物溶液和二价铁盐溶液混合,对pH进行调节后得到混合溶液;再将聚氨酯填料浸没在混合溶液中进行改性,最终得到了改性聚氨酯填料。通过本发明所述的改性方法得到的新型聚氨酯填料,生物亲和性得到了极大提升,相对于传统的聚氨酯填料具有更大的比表面积,对微生物在填料表面吸附、生长形成生物膜有促进作用,可以提高其用于生物膜法中对废水的处理效率。
The invention relates to the technical field of polymer carrier modification, and in particular to a preparation method of modified polyurethane filler. In the present invention, a peroxide solution and a divalent iron salt solution are mixed, and the pH is adjusted to obtain a mixed solution; then the polyurethane filler is immersed in the mixed solution for modification, and finally a modified polyurethane filler is obtained. The novel polyurethane filler obtained through the modification method of the present invention has greatly improved bioaffinity. Compared with traditional polyurethane filler, it has a larger specific surface area and is effective in adsorbing and growing biofilms on the surface of the filler. The promotion effect can improve the efficiency of wastewater treatment in biofilm method.
Description
技术领域Technical field
本发明涉及高分子载体改性技术领域,尤其涉及一种改性聚氨酯填料的制备方法。The invention relates to the technical field of polymer carrier modification, and in particular to a preparation method of modified polyurethane filler.
背景技术Background technique
生物膜法是一种利用附着在载体材料上生长的微生物进行污水生物处理的水处理技术,载体材料的主要作用是提供微生物生存的微环境,使微生物对各种污染物的抗逆能力大大提高。相比于其它同类材料,聚氨酯填料比表面积大,能在保持足够的菌体数量的同时实现与水良好的分离。但是其固定微生物仅仅是通过物理吸附实现,导致微生物细胞容易脱落,因此需要对其进行改性处理以增加其表面粗糙度,提高表面生物亲和性。Biofilm method is a water treatment technology that uses microorganisms growing on carrier materials for biological treatment of sewage. The main function of the carrier material is to provide a microenvironment for microorganisms to survive, which greatly improves the resistance of microorganisms to various pollutants. . Compared with other similar materials, polyurethane filler has a larger specific surface area and can achieve good separation from water while maintaining a sufficient number of bacteria. However, its immobilization of microorganisms is only achieved through physical adsorption, which causes the microbial cells to easily fall off. Therefore, it needs to be modified to increase its surface roughness and improve surface bioaffinity.
目前填料的改性包括本体改性和表面改性。对聚氨酯填料进行的本体改性大多是向填料中加入纳米材料如纳米SiO2,虽可改善填料对微生物的亲和性、理化稳定性,但是价格昂贵且不易获得,在推广上有一定的局限性。表面改性中机械改性适用于具有金属涂层的填料,表面粗糙法需要在模具中加工填料,均不适用于聚氨酯填料;低温等离子体改性与高能辐射改性环境污染小、加工周期短,但其应用条件较为苛刻,不适于推广。目前应用较广的主要有液相化学氧化法、表面接枝法。后者主要采用海藻酸钠以及明胶蛋白进行接枝。化学氧化后材料表面变得粗糙,许多研究中在氧化后添加离子覆盖或表面接枝以强化改性效果。如使用高锰酸钾氧化-铁离子覆盖改性以及高锰酸钾氧化-明胶蛋白接枝改性,有研究表明,氧化后进行明胶蛋白接枝改性比Fe3+覆盖改性效果稍好一些,但Fe3+改性处理成本更低。The current modification of fillers includes bulk modification and surface modification. Most bulk modifications of polyurethane fillers involve adding nanomaterials such as nano-SiO 2 to the filler. Although it can improve the filler's affinity for microorganisms and physical and chemical stability, it is expensive and difficult to obtain, and has certain limitations in promotion. sex. Among surface modifications, mechanical modification is suitable for fillers with metal coatings. Surface roughening methods require processing of fillers in molds, and are not suitable for polyurethane fillers. Low-temperature plasma modification and high-energy radiation modification have low environmental pollution and short processing cycles. , but its application conditions are relatively harsh and not suitable for promotion. At present, the most widely used ones are liquid phase chemical oxidation method and surface grafting method. The latter mainly uses sodium alginate and gelatin protein for grafting. The material surface becomes rough after chemical oxidation. In many studies, ion covering or surface grafting is added after oxidation to enhance the modification effect. For example, potassium permanganate oxidation-iron ion covering modification and potassium permanganate oxidation-gelatin protein grafting modification are used. Studies have shown that gelatin protein grafting modification after oxidation is slightly better than Fe 3+ covering modification. Some, but the Fe3 + modification process is less expensive.
因此如何提供一种轻污染、较方便且成本更低的改性方法,对聚氨酯填料的生物亲和性进行改性,能够加快微生物在聚氨酯填料表面的挂膜并加强生物膜与填料的稳定性成为本领域亟待解决的技术问题。Therefore, how to provide a modification method that is light-pollution, more convenient and lower-cost to modify the bioaffinity of polyurethane fillers, which can accelerate the deposition of microorganisms on the surface of polyurethane fillers and enhance the stability of biofilms and fillers. It has become an urgent technical problem to be solved in this field.
发明内容Contents of the invention
本发明的目的在于提供一种改性聚氨酯填料的制备方法,对聚氨酯填料的生物亲和性进行改性,从而加快微生物在聚氨酯填料表面的挂膜并加强生物膜与填料的稳定性,从而解决聚氨酯填料生物膜挂膜时间长、生物膜易脱落等问题。The object of the present invention is to provide a preparation method of modified polyurethane filler to modify the bioaffinity of the polyurethane filler, thereby accelerating the deposition of microorganisms on the surface of the polyurethane filler and strengthening the stability of the biofilm and the filler, thereby solving the problem of Polyurethane filler biofilm takes a long time to hang and the biofilm is easy to fall off.
为了实现上述发明目的,本发明提供以下技术方案:In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
本发明提供了一种改性聚氨酯填料的制备方法,包括如下步骤:The invention provides a preparation method of modified polyurethane filler, which includes the following steps:
(1)将过氧化物溶液和二价铁盐溶液混合,对pH进行调节后得到混合溶液;(1) Mix the peroxide solution and the ferrous iron salt solution, and adjust the pH to obtain a mixed solution;
(2)将聚氨酯填料浸没在混合溶液中进行改性,得到改性聚氨酯填料。(2) Immerse the polyurethane filler in the mixed solution for modification to obtain the modified polyurethane filler.
优选的,所述步骤(1)中使用氢氧化钠溶液、盐酸溶液或硫酸溶液对pH进行调节;所述氢氧化钠溶液的浓度为0.1~0.5mol/L;盐酸溶液的浓度为0.1~0.5mol/L;硫酸溶液的浓度为0.1~0.5mol/L;所述混合溶液的pH≤3。Preferably, in step (1), sodium hydroxide solution, hydrochloric acid solution or sulfuric acid solution is used to adjust the pH; the concentration of the sodium hydroxide solution is 0.1~0.5mol/L; the concentration of the hydrochloric acid solution is 0.1~0.5 mol/L; the concentration of the sulfuric acid solution is 0.1-0.5 mol/L; the pH of the mixed solution is ≤ 3.
优选的,所述步骤(1)的混合溶液中过氧化物的浓度为0.1~10mmol/L。Preferably, the concentration of peroxide in the mixed solution of step (1) is 0.1-10 mmol/L.
优选的,所述步骤(1)的混合溶液中二价铁盐的浓度为0.1~10mmol/L。Preferably, the concentration of divalent iron salt in the mixed solution of step (1) is 0.1-10 mmol/L.
优选的,所述步骤(1)中过氧化物溶液包含过氧化氢溶液、过氧乙酸溶液或过硫酸钠溶液。Preferably, the peroxide solution in step (1) includes hydrogen peroxide solution, peracetic acid solution or sodium persulfate solution.
优选的,所述步骤(1)中二价铁盐溶液包含硫酸亚铁溶液和氯化亚铁溶液中的一种或几种。Preferably, the ferrous iron salt solution in step (1) contains one or more of ferrous sulfate solution and ferrous chloride solution.
优选的,所述步骤(2)中改性的温度为15~25℃,时间为1~4h。Preferably, the modification temperature in step (2) is 15 to 25°C, and the modification time is 1 to 4 hours.
优选的,步骤(2)所述改性结束后进行烘干,得到改性聚氨酯填料;所述烘干温度为100~120℃,时间为40~60min。Preferably, drying is performed after the modification in step (2) is completed to obtain the modified polyurethane filler; the drying temperature is 100-120°C and the time is 40-60 minutes.
与现有技术相比,本发明具有如下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
本发明提供了一种适用于水生物处理中的、利用以二价铁离子为催化剂、过氧化物为氧化剂的高级氧化反应过程中生成的羟基自由基与铁离子对聚氨酯填料进行改性的改性方法,该方法具有轻污染、较方便、反应快捷、改性效果好的特点。The present invention provides a method for modifying polyurethane fillers by using hydroxyl radicals and iron ions generated during an advanced oxidation reaction using divalent iron ions as catalysts and peroxides as oxidants, which are suitable for aquatic biological treatment. This method is characterized by light pollution, convenience, fast reaction, and good modification effect.
本发明提供的通过对聚氨酯填料表面结构进行改性的方法,利用所述高级氧化反应过程中产生的羟基自由基氧化填料表面以提高填料表面粗糙度,增大填料的比表面积;由于微生物细胞膜表面多带负电荷,利用反应产生的铁离子修饰填料表面改变填料表面的电位,提高填料的生物亲和性,有利于微生物的富集与固定。The method provided by the invention by modifying the surface structure of the polyurethane filler utilizes the hydroxyl radicals generated during the advanced oxidation reaction to oxidize the filler surface to increase the filler surface roughness and increase the specific surface area of the filler; due to the microbial cell membrane surface It has multiple negative charges and uses the iron ions produced by the reaction to modify the surface of the filler to change the potential of the filler surface, improve the bioaffinity of the filler, and is beneficial to the enrichment and immobilization of microorganisms.
采用本发明的改性方法制得的聚氨酯填料,相对于传统的聚氨酯填料具有更大的比表面积,对微生物在填料表面吸附、生长形成生物膜有促进作用,可以将其应用于生物膜法中,能够提高对废水的处理效率。The polyurethane filler prepared by the modification method of the present invention has a larger specific surface area than the traditional polyurethane filler, and can promote the adsorption and growth of microorganisms on the surface of the filler to form biofilms, and can be used in biofilm methods. , can improve the efficiency of wastewater treatment.
附图说明Description of the drawings
图1为本发明实施例1的聚氨酯填料改性前后生物膜负载量随时间的变化图;Figure 1 is a graph showing changes in biofilm loading with time before and after modification of the polyurethane filler in Example 1 of the present invention;
图2为本发明实施例1的聚氨酯填料改性前后氨氮去除率随时间的变化图;Figure 2 is a graph showing changes in ammonia nitrogen removal rate over time before and after modification of the polyurethane filler in Example 1 of the present invention;
图3为本发明实施例1的聚氨酯填料改性前后COD去除率随时间的变化图。Figure 3 is a graph showing the COD removal rate changing with time before and after modification of the polyurethane filler in Example 1 of the present invention.
具体实施方式Detailed ways
本发明提供了一种改性聚氨酯填料的制备方法,包括如下步骤:The invention provides a preparation method of modified polyurethane filler, which includes the following steps:
(1)将过氧化物溶液和二价铁盐溶液混合,对pH进行调节后得到混合溶液;(1) Mix the peroxide solution and the ferrous iron salt solution, and adjust the pH to obtain a mixed solution;
(2)将聚氨酯填料浸没在混合溶液中进行改性,得到改性聚氨酯填料。(2) Immerse the polyurethane filler in the mixed solution for modification to obtain the modified polyurethane filler.
在本发明中,所述步骤(1)中使用氢氧化钠溶液、盐酸溶液或硫酸溶液对pH进行调节,优选为使用盐酸溶液或硫酸溶液对pH进行调节;In the present invention, in the step (1), a sodium hydroxide solution, a hydrochloric acid solution or a sulfuric acid solution is used to adjust the pH, preferably a hydrochloric acid solution or a sulfuric acid solution is used to adjust the pH;
所述氢氧化钠溶液的浓度为0.1~0.5mol/L,优选为0.2~0.4mol/L,进一步优选为0.25~0.35mol/L;盐酸溶液的浓度为0.1~0.5mol/L,优选为0.2~0.4mol/L,进一步优选为0.25~0.35mol/L;硫酸溶液的浓度为0.1~0.5mol/L,优选为0.2~0.4mol/L,进一步优选为0.25~0.35mol/L;The concentration of the sodium hydroxide solution is 0.1~0.5mol/L, preferably 0.2~0.4mol/L, and further preferably 0.25~0.35mol/L; the concentration of the hydrochloric acid solution is 0.1~0.5mol/L, preferably 0.2 ~0.4mol/L, more preferably 0.25~0.35mol/L; the concentration of the sulfuric acid solution is 0.1~0.5mol/L, preferably 0.2~0.4mol/L, further preferably 0.25~0.35mol/L;
所述混合溶液的pH≤3,优选为pH≤2.5,进一步优选为pH≤2,更进一步优选为pH≤1.5。The pH of the mixed solution is ≤ 3, preferably pH ≤ 2.5, more preferably pH ≤ 2, and even more preferably pH ≤ 1.5.
在本发明中,所述步骤(1)的混合溶液中过氧化物的浓度为0.1~10mmol/L,优选为1~8mmol/L,进一步优选为2~6mmol/L,更进一步优选为4~5mmol/L。In the present invention, the concentration of peroxide in the mixed solution of step (1) is 0.1~10mmol/L, preferably 1~8mmol/L, more preferably 2~6mmol/L, even more preferably 4~ 5mmol/L.
在本发明中,所述步骤(1)的混合溶液中二价铁盐的浓度为0.1~10mmol/L,优选为1~8mmol/L,进一步优选为2~6mmol/L,更进一步优选为4~5mmol/L。In the present invention, the concentration of divalent iron salt in the mixed solution of step (1) is 0.1 to 10 mmol/L, preferably 1 to 8 mmol/L, more preferably 2 to 6 mmol/L, and even more preferably 4 ~5mmol/L.
在本发明中,步骤(1)所述混合溶液中过氧化物溶液与二价铁离子浓度相等。In the present invention, the concentration of the peroxide solution and the ferrous iron ion in the mixed solution described in step (1) are equal.
在本发明中,所述步骤(1)中过氧化物溶液包含过氧化氢溶液、过氧乙酸溶液或过硫酸钠溶液,优选为过氧化氢溶液或过氧乙酸溶液,进一步优选为过氧乙酸溶液。In the present invention, the peroxide solution in step (1) includes hydrogen peroxide solution, peracetic acid solution or sodium persulfate solution, preferably hydrogen peroxide solution or peracetic acid solution, and further preferably peracetic acid. solution.
在本发明中,所述步骤(1)中二价铁盐溶液包含硫酸亚铁溶液和氯化亚铁溶液中的一种或几种,优选为硫酸亚铁溶液。In the present invention, the ferrous iron salt solution in step (1) includes one or more of ferrous sulfate solution and ferrous chloride solution, preferably ferrous sulfate solution.
在本发明中,所述步骤(2)中改性的温度为15~25℃,优选为16~24℃,进一步优选为18~22℃,更进一步优选为20℃;时间为1~4h,优选为1.5~3.5h,进一步优选为2~3h,更进一步优选为2.5h。In the present invention, the modification temperature in step (2) is 15-25°C, preferably 16-24°C, more preferably 18-22°C, even more preferably 20°C; the time is 1-4h, Preferably it is 1.5-3.5h, More preferably, it is 2-3h, Even more preferably, it is 2.5h.
在本发明中,步骤(2)所述改性结束后进行烘干,得到改性聚氨酯填料;所述烘干温度为100~120℃,优选为102~115℃,进一步优选为105~110℃;时间为40~60min,优选为45~55℃,进一步优选为48~53℃,更进一步优选为50℃。In the present invention, drying is performed after the modification in step (2) is completed to obtain the modified polyurethane filler; the drying temperature is 100 to 120°C, preferably 102 to 115°C, and further preferably 105 to 110°C. ; The time is 40 to 60 minutes, preferably 45 to 55°C, more preferably 48 to 53°C, even more preferably 50°C.
下面结合实施例对本发明提供的技术方案进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。The technical solutions provided by the present invention will be described in detail below with reference to the examples, but they should not be understood as limiting the protection scope of the present invention.
实施例1Example 1
将过氧乙酸溶液和硫酸亚铁溶液混合,并采用浓度为0.1mol/L的H2SO4溶液调节所得混合溶液的pH为3,混合溶液中过氧乙酸的浓度为1.0mmol/L、硫酸亚铁的浓度为1.0mmol/L;在温度为20℃的条件下将聚氨酯填料完全浸没在所述混合溶液中,浸泡时间为2h进行改性;改性结束后再将填料在105℃下高温烘干60min,得到改性聚氨酯填料。Mix peracetic acid solution and ferrous sulfate solution, and use H 2 SO 4 solution with a concentration of 0.1 mol/L to adjust the pH of the resulting mixed solution to 3. The concentration of peracetic acid in the mixed solution is 1.0 mmol/L and sulfuric acid. The concentration of ferrous iron is 1.0mmol/L; the polyurethane filler is completely immersed in the mixed solution at a temperature of 20°C, and the soaking time is 2 hours for modification; after the modification is completed, the filler is heated at 105°C Dry for 60 minutes to obtain modified polyurethane filler.
实施例2Example 2
将过氧乙酸溶液和硫酸亚铁溶液混合,并采用浓度为0.1mol/L的H2SO4溶液调节所得混合溶液的pH为3,混合溶液中过氧乙酸的浓度为0.1mmol/L、硫酸亚铁的浓度为0.1mmol/L;在温度为20℃的条件下将聚氨酯填料完全浸没在所述混合溶液中,浸泡时间为1h进行改性;改性结束后再将填料在105℃下高温烘干60min,得到改性聚氨酯填料。Mix peracetic acid solution and ferrous sulfate solution, and use H 2 SO 4 solution with a concentration of 0.1 mol/L to adjust the pH of the resulting mixed solution to 3. The concentration of peracetic acid in the mixed solution is 0.1 mmol/L and sulfuric acid. The concentration of ferrous iron is 0.1mmol/L; the polyurethane filler is completely immersed in the mixed solution at a temperature of 20°C, and the soaking time is 1 hour for modification; after the modification is completed, the filler is heated at 105°C Dry for 60 minutes to obtain modified polyurethane filler.
实施例3Example 3
将过氧乙酸溶液和硫酸亚铁溶液混合,并采用浓度为0.1mol/L的H2SO4溶液调节所得混合溶液的pH为3,混合溶液中过氧乙酸的浓度为10mmol/L、硫酸亚铁的浓度为10mmol/L;在温度为20℃的条件下将聚氨酯填料完全浸没在所述混合溶液中,浸泡时间为4h进行改性;改性结束后再将填料在105℃下高温烘干60min,得到改性聚氨酯填料。Mix peracetic acid solution and ferrous sulfate solution, and use H 2 SO 4 solution with a concentration of 0.1 mol/L to adjust the pH of the resulting mixed solution to 3. The concentration of peracetic acid in the mixed solution is 10 mmol/L, and the ferrous sulfate solution is 10 mmol/L. The concentration of iron is 10mmol/L; the polyurethane filler is completely immersed in the mixed solution at a temperature of 20°C, and the soaking time is 4 hours for modification; after the modification is completed, the filler is dried at a high temperature of 105°C After 60 minutes, the modified polyurethane filler was obtained.
测试例test case
实验方法:experimental method:
以葡萄糖作为碳源、碳酸氢铵作为氮源人工配水,配水COD为340mg/L,氨氮浓度22mg/L。在两个相同的反应器(有效容积为1L)中按填料/溶液填充比(填料体积/溶液体积)为5%分别装填实施例1制备的改性填料与未改性填料。Use glucose as the carbon source and ammonium bicarbonate as the nitrogen source to artificially distribute water. The COD of the water distribution is 340 mg/L, and the ammonia nitrogen concentration is 22 mg/L. The modified filler prepared in Example 1 and the unmodified filler were respectively filled in two identical reactors (effective volume: 1L) at a filler/solution filling ratio (filler volume/solution volume) of 5%.
挂膜阶段:分别接种等量的污水处理厂曝气池污泥,曝气混匀后静置,24h后排出污泥,此时完成接种。重新加入配水后曝气反应,控制溶解氧6~8mg/L,每24h换水,3天后结束挂膜阶段。Film hanging stage: Inoculate equal amounts of sludge from the aeration tank of the sewage treatment plant respectively, aerate and mix evenly and let stand. The sludge will be discharged after 24 hours. At this time, the inoculation is completed. After re-adding the water distribution, aeration reaction is carried out, the dissolved oxygen is controlled to 6-8 mg/L, the water is changed every 24 hours, and the film-hanging stage ends after 3 days.
取样阶段:挂膜完成后进行填料处理废水性能试验,控制溶解氧6~8mg/L,运行周期为24h,其中曝气23h,静置50min,换水10min。每运行周期末换水时检测两反应器出水COD及氨氮值,同时分别取出改性填料与未改性填料用于测试生物膜量。Sampling stage: After the film is completed, perform a filler wastewater performance test to control dissolved oxygen 6 to 8 mg/L. The operation cycle is 24 hours, including 23 hours of aeration, 50 minutes of standing, and 10 minutes of water change. When changing the water at the end of each operating cycle, the COD and ammonia nitrogen values of the effluent from the two reactors were measured, and the modified filler and unmodified filler were taken out to test the amount of biofilm.
分析方法:Analytical method:
(1)生物膜量测试方法:将取出的挂膜填料(填料自重W1,g)放入内衬锡纸包裹的称量瓶中,放入105℃的烘箱中烘干60min,冷却后称重(W2,g),取出填料,置于1mol/L的NaOH溶液中,在70℃条件下水浴加热1h,然后用40Hz超声波处理1h,水洗数遍直至脱落生物膜被清洗掉后,将填料放回称量瓶进行烘干、冷却、称重(W3,g),计算(W2-W3)*1000/W1,即为单位质量填料上的生物膜干重(mg/g)。(1) Biofilm quantity test method: Put the removed film-bearing filler (filler weight W1, g) into a weighing bottle wrapped with tinfoil, place it in an oven at 105°C to dry for 60 minutes, and weigh after cooling ( W2, g), take out the filler, place it in 1mol/L NaOH solution, heat it in a water bath at 70°C for 1 hour, then treat it with 40Hz ultrasonic wave for 1 hour, wash it several times with water until the exfoliated biofilm is washed away, and then put the filler back Dry, cool, and weigh the weighing bottle (W3, g), and calculate (W2-W3)*1000/W1, which is the dry weight of the biofilm on unit mass of filler (mg/g).
(2)COD去除率测试方法:采用重铬酸钾法测量进出水的COD,由COD去除量除以进水COD即为COD去除率。(2) COD removal rate test method: Use the potassium dichromate method to measure COD in the inlet and outlet water. The COD removal rate divided by the inlet water COD is the COD removal rate.
(3)氨氮去除率测试方法:采用纳氏试剂光度法测量进出水的氨氮,由氨氮去除量除以进水氨氮即为氨氮去除率。(3) Ammonia nitrogen removal rate test method: Use Nessler's reagent photometry to measure the ammonia nitrogen in the inlet and outlet water. The ammonia nitrogen removal rate divided by the ammonia nitrogen in the inlet water is the ammonia nitrogen removal rate.
表1实施例1的聚氨酯填料改性前后6天内生物模量、COD去除率、氨氮去除率对比Table 1 Comparison of biological modulus, COD removal rate, and ammonia nitrogen removal rate within 6 days before and after polyurethane filler modification in Example 1
根据本发明图1和表1可知改性填料的生物膜量及生物膜生长速率均高于未改性填料,在测量的第6天,每1g改性填料与未改性填料上生物膜量分别为189.50mg与148.05mg;每1g改性填料与未改性填料上生物膜平均每天生长量分别为31.6mg/d与24.7mg/d,改性后填料的生物膜平均每天生长量提高了28.0%,生物膜生长速率更高;According to Figure 1 and Table 1 of the present invention, it can be seen that the biofilm amount and biofilm growth rate of the modified filler are higher than that of the unmodified filler. On the 6th day of measurement, the amount of biofilm per 1g of modified filler and unmodified filler 189.50mg and 148.05mg respectively; the average daily growth of biofilm per 1g of modified filler and unmodified filler was 31.6mg/d and 24.7mg/d respectively. The average daily growth of biofilm on modified filler increased. 28.0%, higher biofilm growth rate;
根据本发明图2和表1可知改性填料对废水的氨氮处理效果明显优于未改性填料改性填料,其氨氮去除率达到了84.8%,而未改性填料的氨氮去除率仅为60.81%;According to Figure 2 and Table 1 of the present invention, it can be seen that the ammonia nitrogen treatment effect of modified filler on wastewater is significantly better than that of unmodified filler. The ammonia nitrogen removal rate of modified filler reaches 84.8%, while the ammonia nitrogen removal rate of unmodified filler is only 60.81 %;
根据本发明图3和表1可知改性填料对废水的COD处理效果明显优于未改性填料改性填料,其COD去除率达到了86.19%,而未改性填料的COD去除率仅为48.46%;According to Figure 3 and Table 1 of the present invention, it can be seen that the COD treatment effect of modified filler on wastewater is significantly better than that of unmodified filler. The COD removal rate of modified filler reaches 86.19%, while the COD removal rate of unmodified filler is only 48.46 %;
两种填料对废水中COD与氨氮的去除效果差异原因,除了图1表示的两者生物膜量的明显差别外,也与改性填料表面覆盖有Fe2O3有关,其弱磁场效应可促进微生物生命活动,同时其也可促进细胞内的酶促反应加快细胞水中营养物质。The reason for the difference in the removal effect of COD and ammonia nitrogen in wastewater between the two fillers is not only the obvious difference in the amount of biofilm between the two shown in Figure 1, but also related to the fact that the surface of the modified filler is covered with Fe 2 O 3 , and its weak magnetic field effect can promote Microbial life activities, and it can also promote enzymatic reactions in cells to accelerate nutrients in cell water.
由以上实施例可知,本发明提供了一种适用于水生物处理中的、利用以二价铁离子为催化剂、过氧化物为氧化剂的高级氧化反应过程中生成的羟基自由基与铁离子对聚氨酯填料进行改性的改性方法。采用本发明的改性方法制得的新型填料,相对于传统的聚氨酯填料具有更大的比表面积,对微生物在填料表面吸附、生长形成生物膜有促进作用,可以将其应用于生物膜法中,能够提高对废水的处理效率。As can be seen from the above examples, the present invention provides a method for aquatic biological treatment that utilizes hydroxyl radicals and iron ions generated during an advanced oxidation reaction using divalent iron ions as catalysts and peroxides as oxidants to react with polyurethane. Modification method for modifying fillers. The new type of filler prepared by the modification method of the present invention has a larger specific surface area than traditional polyurethane fillers, and can promote the adsorption and growth of microorganisms on the surface of the filler to form biofilms, and can be used in biofilm methods. , can improve the efficiency of wastewater treatment.
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 preferred embodiments of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the principles of the present invention. These improvements and modifications can also be made. should be regarded as the protection scope of the present invention.
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CN112520841A (en) * | 2020-11-30 | 2021-03-19 | 武汉森泰环保股份有限公司 | Polyurethane sponge biological filler and preparation method thereof |
CN114181429A (en) * | 2021-12-16 | 2022-03-15 | 浙江工业大学 | Modified polyurethane sponge filler, preparation method and application thereof |
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CN102923846A (en) * | 2012-11-09 | 2013-02-13 | 江苏百纳环境工程有限公司 | Combined type biochar enhanced nitrogen removal filler and preparation method thereof |
CN112520841A (en) * | 2020-11-30 | 2021-03-19 | 武汉森泰环保股份有限公司 | Polyurethane sponge biological filler and preparation method thereof |
CN114181429A (en) * | 2021-12-16 | 2022-03-15 | 浙江工业大学 | Modified polyurethane sponge filler, preparation method and application thereof |
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