CN108251459B - A method of recovering struvite from wastewater - Google Patents

A method of recovering struvite from wastewater Download PDF

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CN108251459B
CN108251459B CN201810296839.2A CN201810296839A CN108251459B CN 108251459 B CN108251459 B CN 108251459B CN 201810296839 A CN201810296839 A CN 201810296839A CN 108251459 B CN108251459 B CN 108251459B
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struvite
magnesium oxide
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activated bacterial
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周根陶
罗毅
姚奇志
李涵
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University of Science and Technology of China USTC
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Abstract

本发明属于环保领域,尤其涉及一种从废水中回收鸟粪石的方法。本发明提供的方法包括以下步骤:a)将奥奈达希瓦氏菌进行活化,得到活化菌液;b)将所述活化菌液、氧化镁和废水混合,好氧培养,得到鸟粪石;所述废水中含有磷元素和氮元素。本发明以价格低廉的氧化镁作为合成鸟粪石的镁源,利用奥奈达希瓦氏菌的代谢活动促进氧化镁在水中溶解,同时为鸟粪石的合成提供必要的环境条件,不必再额外添加碱源,从而大幅降低了从废水中回收鸟粪石的成本。实验结果表明,本发明提供的方法能够实现氧化镁的高效利用,氧化镁的转化率最高可达97.6%。The invention belongs to the field of environmental protection, and in particular relates to a method for recovering struvite from waste water. The method provided by the invention comprises the following steps: a) activating Oneida Shewanella to obtain an activated bacterial solution; b) mixing the activated bacterial solution, magnesium oxide and waste water, and aerobic cultivation to obtain struvite ; The wastewater contains phosphorus and nitrogen elements. The invention uses low-cost magnesium oxide as the magnesium source for synthesizing struvite, utilizes the metabolic activity of Oneida Shewanella to promote the dissolution of magnesium oxide in water, provides necessary environmental conditions for the synthesis of struvite, and does not need to An additional source of alkalinity is added, thereby significantly reducing the cost of recovering struvite from wastewater. The experimental results show that the method provided by the invention can realize the efficient utilization of magnesium oxide, and the conversion rate of magnesium oxide can reach up to 97.6%.

Description

一种从废水中回收鸟粪石的方法A method of recovering struvite from wastewater

技术领域technical field

本发明属于环保领域,尤其涉及一种从废水中回收鸟粪石的方法。The invention belongs to the field of environmental protection, and in particular relates to a method for recovering struvite from waste water.

背景技术Background technique

磷是所有生物体不可缺少的元素,在生物体的生长、发育和繁殖中起着不可替代的作用。磷矿石作为磷在自然界中的主要存在形式,是一种不可再生资源。同时,磷过量输入水体将引起水体富营养化,影响水质并对人体健康构成威胁。在过去半个世纪,约有5亿吨磷矿石在人为干预下输入水圈,由此产生的水污染问题亟待解决。随着污水营养物质排放标准的不断提高以及可持续发展战略下资源循环利用的需求日益迫切,污水处理技术已经开始向除氮磷同时能够回收氮磷的方向发展。鸟粪石结晶回收工艺正是在此背景下产生的。Phosphorus is an indispensable element for all organisms and plays an irreplaceable role in the growth, development and reproduction of organisms. As the main form of phosphorus in nature, phosphate rock is a non-renewable resource. At the same time, excessive phosphorus input into water bodies will cause eutrophication of water bodies, affecting water quality and posing a threat to human health. In the past half century, about 500 million tons of phosphate rock have been imported into the hydrosphere under human intervention, and the resulting water pollution problem needs to be solved urgently. With the continuous improvement of sewage nutrient discharge standards and the increasingly urgent need for resource recycling under the sustainable development strategy, sewage treatment technology has begun to develop in the direction of removing nitrogen and phosphorus while recovering nitrogen and phosphorus. It is against this background that the struvite crystallization recovery process is produced.

鸟粪石,也称磷酸铵镁(MgNH4PO4·6H2O),是一种难溶于水的白色晶体。鸟粪石含有氮磷镁三种营养元素,是一种较为理想的缓释肥。鸟粪石结晶回收工艺是在控制条件下,通过沉淀鸟粪石实现同时去除污水中的氮和磷,并将产物鸟粪石回收用作肥料。因此,该工艺具有潜在的环境效益和经济效益,成为当前水处理研究的热点。与之相关的专利申请不断出现,例如中国专利申请201210145002“一种用鸟粪石生产工艺回收磷化工废水中磷的方法”、中国专利申请201410012829“一种鸟粪石沉淀法处理氨氮废水的工艺方法”以及中国专利申请201610084036“一种从污泥中回收鸟粪石的方法及系统”等。但是,污水中往往富含氮磷而缺少镁,并且鸟粪石结晶沉淀还需要较高的pH,理想的范围是8.5~9.5。因此,鸟粪石结晶工艺需要向含有氮磷的污水中添加镁源,并通过加入碱源调节pH到合适范围,从而促进鸟粪石沉淀。其中,镁试剂(如MgCl2、MgSO4)和碱试剂的添加将大大增加鸟粪石结晶回收的成本,从而降低了鸟粪石结晶法回收氮磷的经济可行性。Struvite, also known as magnesium ammonium phosphate (MgNH 4 PO 4 ·6H 2 O), is a white crystal that is poorly soluble in water. Struvite contains three nutrients, nitrogen, phosphorus and magnesium, and is an ideal slow-release fertilizer. The struvite crystallization recovery process is to simultaneously remove nitrogen and phosphorus from sewage by precipitating struvite under controlled conditions, and recycling the product struvite as fertilizer. Therefore, this process has potential environmental and economic benefits, and has become a hot spot in current water treatment research. Patent applications related to it continue to appear, such as Chinese patent application 201210145002 "A method for recovering phosphorus in phosphorous chemical wastewater by struvite production process", Chinese patent application 201410012829 "A kind of struvite precipitation process for ammonia nitrogen wastewater treatment process"Method" and Chinese patent application 201610084036 "A method and system for recovering struvite from sludge", etc. However, sewage is often rich in nitrogen and phosphorus but lacks magnesium, and struvite crystal precipitation also requires a high pH, the ideal range is 8.5-9.5. Therefore, the struvite crystallization process needs to add a magnesium source to the sewage containing nitrogen and phosphorus, and adjust the pH to an appropriate range by adding an alkali source, thereby promoting struvite precipitation. Among them, the addition of magnesium reagents (such as MgCl 2 , MgSO 4 ) and alkali reagents will greatly increase the cost of struvite crystallization recovery, thereby reducing the economic feasibility of struvite crystallization to recover nitrogen and phosphorus.

发明内容SUMMARY OF THE INVENTION

有鉴于此,本发明的目的在于提供一种从废水中回收鸟粪石的方法,该方法成本低廉。In view of this, the object of the present invention is to provide a method for recovering struvite from waste water, and the method is low in cost.

本发明提供了一种从废水中回收鸟粪石的方法,包括以下步骤:The invention provides a method for reclaiming struvite from waste water, comprising the following steps:

a)将奥奈达希瓦氏菌进行活化,得到活化菌液;a) activating Oneida Shewanella to obtain an activated bacterial solution;

b)将所述活化菌液、氧化镁和废水混合,好氧培养,得到鸟粪石;b) mixing described activated bacterial liquid, magnesium oxide and waste water, and aerobic cultivation to obtain struvite;

所述废水中含有磷元素和氮元素。The wastewater contains phosphorus and nitrogen.

优选的,步骤a)中,所述活化菌液中的细菌密度为1×109~15×109CFU/mL。Preferably, in step a), the bacterial density in the activated bacterial solution is 1×10 9 to 15×10 9 CFU/mL.

优选的,所述步骤a)具体包括:Preferably, the step a) specifically includes:

将保藏在固体培养基上的奥奈达希瓦氏菌接种到液体培养基中,好氧培养,得到活化菌液。Shewanella Oneida stored on the solid medium is inoculated into the liquid medium and cultured aerobically to obtain an activated bacterial liquid.

优选的,步骤a)中,所述液体培养基为LB培养基。Preferably, in step a), the liquid medium is LB medium.

优选的,步骤a)中,所述好氧培养的温度为25~35℃;所述好氧培养的时间为8~16h。Preferably, in step a), the temperature of the aerobic cultivation is 25-35° C.; the time of the aerobic cultivation is 8-16 h.

优选的,步骤b)中,所述氧化镁和废水的用量比为(0.1~1.2)g:1L。Preferably, in step b), the dosage ratio of the magnesium oxide to the waste water is (0.1-1.2) g: 1L.

优选的,步骤b)中,所述活化菌液和废水的体积比为(0.1~5):100。Preferably, in step b), the volume ratio of the activated bacterial solution to the waste water is (0.1-5):100.

优选的,步骤b)中,所述好氧培养的温度为25~35℃;所述好氧培养的时间为48~96h。Preferably, in step b), the temperature of the aerobic cultivation is 25-35° C.; the time of the aerobic cultivation is 48-96 h.

优选的,步骤b)中,所述废水的总磷含量为170~425mg/L;所述废水的总氮含量为625~1560mg/L。Preferably, in step b), the total phosphorus content of the wastewater is 170-425 mg/L; the total nitrogen content of the wastewater is 625-1560 mg/L.

优选的,步骤b)中,所述废水的有机磷含量为100~250mg/L;所述废水的有机氮含量为560~1400mg/L。Preferably, in step b), the organic phosphorus content of the wastewater is 100-250 mg/L; the organic nitrogen content of the wastewater is 560-1400 mg/L.

与现有技术相比,本发明提供了一种从废水中回收鸟粪石的方法。本发明提供的方法包括以下步骤:a)将奥奈达希瓦氏菌进行活化,得到活化菌液;b)将所述活化菌液、氧化镁和废水混合,好氧培养,得到鸟粪石;所述废水中含有磷元素和氮元素。本发明以价格低廉的氧化镁作为合成鸟粪石的镁源,利用奥奈达希瓦氏菌的代谢活动促进氧化镁在水中溶解,同时为鸟粪石的合成提供必要的环境条件,不必再额外添加碱源,从而大幅降低了从废水中回收鸟粪石的成本。实验结果表明,本发明提供的方法能够实现氧化镁的高效利用,氧化镁的转化率最高可达97.6%。Compared with the prior art, the present invention provides a method for recovering struvite from wastewater. The method provided by the invention comprises the following steps: a) activating Oneida Shewanella to obtain an activated bacterial solution; b) mixing the activated bacterial solution, magnesium oxide and waste water, and aerobic cultivation to obtain struvite ; The wastewater contains phosphorus and nitrogen elements. The invention uses low-cost magnesium oxide as the magnesium source for synthesizing struvite, utilizes the metabolic activity of Oneida Shewanella to promote the dissolution of magnesium oxide in water, provides necessary environmental conditions for the synthesis of struvite, and does not need to An additional source of alkalinity is added, thereby significantly reducing the cost of recovering struvite from wastewater. The experimental results show that the method provided by the invention can realize the efficient utilization of magnesium oxide, and the conversion rate of magnesium oxide can reach up to 97.6%.

附图说明Description of drawings

为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to the provided drawings without creative work.

图1是本发明提供的实施例1~3制备的鸟粪石的XRD图;Fig. 1 is the XRD figure of the struvite prepared by embodiment 1~3 provided by the invention;

图2是本发明实施例1提供的鸟粪石FESEM图;Fig. 2 is the struvite FESEM figure that the embodiment of the present invention 1 provides;

图3是本发明实施例2提供的鸟粪石FESEM图;Fig. 3 is the struvite FESEM figure that the embodiment of the present invention 2 provides;

图4是本发明实施例3提供的鸟粪石FESEM图;Fig. 4 is the struvite FESEM figure that the embodiment of the present invention 3 provides;

图5是本发明实施例4提供的鸟粪石的XRD图;Fig. 5 is the XRD figure of the struvite provided by the embodiment of the present invention 4;

图6是本发明实施例4提供的氧化镁添加量为0.16g/L时制备的鸟粪石的FESEM图;Fig. 6 is the FESEM image of the struvite prepared when the magnesium oxide addition amount that the embodiment of the present invention 4 provides is 0.16g/L;

图7是本发明实施例4提供的氧化镁添加量为0.64g/L时制备的鸟粪石的FESEM图;Fig. 7 is the FESEM image of the struvite prepared when the magnesium oxide addition amount that the embodiment of the present invention 4 provides is 0.64g/L;

图8是本发明实施例4提供的氧化镁添加量为0.96g/L时制备的鸟粪石的FESEM图。Fig. 8 is the FESEM image of the struvite prepared when the addition amount of magnesium oxide provided in Example 4 of the present invention is 0.96 g/L.

具体实施方式Detailed ways

下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

本发明提供了一种从废水中回收鸟粪石的方法,包括以下步骤:The invention provides a method for reclaiming struvite from waste water, comprising the following steps:

a)将奥奈达希瓦氏菌进行活化,得到活化菌液;a) activating Oneida Shewanella to obtain an activated bacterial solution;

b)将所述活化菌液、氧化镁和废水混合,好氧培养,得到鸟粪石;b) mixing described activated bacterial liquid, magnesium oxide and waste water, and aerobic cultivation to obtain struvite;

所述废水中含有磷元素和氮元素。The wastewater contains phosphorus and nitrogen.

在本发明提供的方法中,首先对奥奈达希瓦氏菌进行活化,得到活化菌液。其中,所述奥奈达希瓦氏菌(Shewanella oneidensis MR-1,ATCC 700550)为杆状革兰氏阴性的兼性厌氧菌,在淡水沉积物、海湾沉积物和其他各种环境中广泛存在;所述活化菌液中的细菌密度优选为1×109~15×109CFU/mL,具体可为6×109CFU/mL。在本发明中,所述活化的方式优选为:In the method provided by the present invention, the Oneida Shewanella is first activated to obtain an activated bacterial solution. Among them, the Shewanella oneidensis MR-1 (ATCC 700550) is a rod-shaped gram-negative facultative anaerobic bacteria, which is widely found in freshwater sediments, bay sediments and other various environments exists; the bacterial density in the activated bacterial solution is preferably 1×10 9 to 15×10 9 CFU/mL, specifically 6×10 9 CFU/mL. In the present invention, the activation mode is preferably:

将保藏在固体培养基上的奥奈达希瓦氏菌接种到液体培养基中,好氧培养,得到活化菌液。Shewanella Oneida stored on the solid medium is inoculated into the liquid medium and cultured aerobically to obtain an activated bacterial liquid.

在本发明提供的上述活化方式中,所述液体培养基优选为LB培养基,所述LB培养基由胰蛋白胨、酵母浸膏、NaCl和水组成,LB培养基中胰蛋白胨的含量为10g/L,酵母浸膏的含量为5g/L,NaCl的含量为5g/L;所述奥奈达希瓦氏菌的接种量以保藏在固体培养基上的菌落数计优选为1~3个菌落;所述好氧培养的温度优选为25~35℃,具体可为30℃;所述好氧培养的时间优选为8~16h,具体可为12h;所述好氧培养优选在摇床上进行,所述摇床的转速优选为100~300rpm,具体可为200rpm。In the above-mentioned activation method provided by the present invention, the liquid medium is preferably LB medium, and the LB medium is composed of tryptone, yeast extract, NaCl and water, and the content of tryptone in the LB medium is 10 g/ L, the content of the yeast extract is 5g/L, and the content of NaCl is 5g/L; the inoculum of the Oneida Shewanella is preferably 1 to 3 colonies in terms of the number of colonies preserved on the solid medium The temperature of the aerobic cultivation is preferably 25-35°C, specifically 30°C; the aerobic cultivation time is preferably 8-16h, specifically 12h; the aerobic cultivation is preferably carried out on a shaking table, The rotating speed of the shaker is preferably 100-300 rpm, specifically 200 rpm.

得到活化菌液后,将所述活化菌液、氧化镁和废水混合,好氧培养。其中,所述废水中含有磷元素和氮元素。在本发明提供的一个实施例中,所述废水的总磷含量优选为100~500mg/L,更优选为170~425mg/L,具体可为170mg/L、340mg/L或425mg/L;所述废水的总氮含量为优选为500~1700mg/L,更优选为625~1560mg/L,具体可为625mg/L、1250mg/L或1560mg/L。在本发明提供的一个实施例中,所述废水的有机磷含量为优选为50~300mg/L,更优选为100~250mg/L,具体可为100mg/L、200mg/L或250mg/L;所述废水的有机氮含量为优选为400~1500mg/L,更优选为560~1400mg/L,具体可为560mg/L、1120mg/L或1400mg/L。在本发明提供的一个实施例中,所述废水中还含有氯化钠,所述氯化钠的含量优选为1~10g/L,具体可为5g/L。在本发明提供的一个实施例中,所述废水的pH值为6~8,具体可为7。在本发明提供的一个实施例中,以LB培养基或改良LB培养基作为模拟废水,所述改良LB培养基由胰蛋白胨、酵母浸膏、NaCl和水组成,改良LB培养基中胰蛋白胨的含量优选为10~25g/L,具体可为10g/L、20g/L或25g/L;改良LB培养基中酵母浸膏的含量优选为5~12.5g/L,具体可为5g/L、10g/L或12.5g/L;改良LB培养基中NaCl的含量优选为5g/L。在本发明中,所述氧化镁和所述废水的用量比优选为(0.1~1.2)g:1L,具体可为0.16g:1L、0.32g:1L、0.64g:1L或0.96g:1L;所述活化菌液和废水的体积比优选为(0.1~5):100,具体可为1:10;所述好氧培养的温度优选为25~35℃,具体可为30℃;所述好氧培养的时间优选为48~96h,具体可为72h。After the activated bacterial solution is obtained, the activated bacterial solution, magnesium oxide and waste water are mixed for aerobic cultivation. Wherein, the waste water contains phosphorus element and nitrogen element. In an embodiment provided by the present invention, the total phosphorus content of the wastewater is preferably 100-500 mg/L, more preferably 170-425 mg/L, specifically 170 mg/L, 340 mg/L or 425 mg/L; The total nitrogen content of the wastewater is preferably 500-1700 mg/L, more preferably 625-1560 mg/L, specifically 625 mg/L, 1250 mg/L or 1560 mg/L. In an embodiment provided by the present invention, the organic phosphorus content of the wastewater is preferably 50-300 mg/L, more preferably 100-250 mg/L, specifically 100 mg/L, 200 mg/L or 250 mg/L; The organic nitrogen content of the wastewater is preferably 400-1500 mg/L, more preferably 560-1400 mg/L, specifically 560 mg/L, 1120 mg/L or 1400 mg/L. In an embodiment provided by the present invention, the wastewater also contains sodium chloride, and the content of the sodium chloride is preferably 1-10 g/L, specifically 5 g/L. In an embodiment provided by the present invention, the pH value of the wastewater is 6-8, specifically 7. In an embodiment provided by the present invention, LB medium or improved LB medium is used as simulated wastewater, and the improved LB medium is composed of tryptone, yeast extract, NaCl and water, and the content of tryptone in the improved LB medium is The content is preferably 10-25g/L, specifically 10g/L, 20g/L or 25g/L; the content of yeast extract in the improved LB medium is preferably 5-12.5g/L, specifically 5g/L, 10g/L or 12.5g/L; the content of NaCl in the modified LB medium is preferably 5g/L. In the present invention, the dosage ratio of the magnesium oxide to the waste water is preferably (0.1-1.2) g:1L, specifically 0.16g:1L, 0.32g:1L, 0.64g:1L or 0.96g:1L; The volume ratio of the activated bacterial solution and the waste water is preferably (0.1-5):100, specifically 1:10; the temperature of the aerobic cultivation is preferably 25-35°C, specifically 30°C; The oxygen culture time is preferably 48-96 hours, specifically 72 hours.

好氧培养培养结束后,对培养液中的产物进行分离,得到鸟粪石粗品。对所述鸟粪石粗品进行洗涤和干燥,得到纯净的鸟粪石制品。其中,所述洗涤的试剂优选为无水乙醇;所述干燥的温度优选为20~30℃,具体可为25℃;所述干燥的时间优选为24~72h,具体可为48h。After the aerobic culture is completed, the products in the culture solution are separated to obtain crude struvite. The crude struvite product is washed and dried to obtain a pure struvite product. Wherein, the washing reagent is preferably absolute ethanol; the drying temperature is preferably 20-30°C, specifically 25°C; the drying time is preferably 24-72h, specifically 48h.

本发明以价格低廉的氧化镁作为合成鸟粪石的镁源,利用奥奈达希瓦氏菌的代谢活动促进氧化镁在水中溶解,同时为鸟粪石的合成提供必要的环境条件,不必再额外添加碱源,从而大幅降低了从废水中回收鸟粪石的成本。具体而言,本发明提供的方法可取得如下积极效果:The invention uses low-cost magnesium oxide as the magnesium source for synthesizing struvite, utilizes the metabolic activity of Oneida Shewanella to promote the dissolution of magnesium oxide in water, provides necessary environmental conditions for the synthesis of struvite, and does not need to An additional source of alkalinity is added, thereby significantly reducing the cost of recovering struvite from wastewater. Specifically, the method provided by the invention can achieve the following positive effects:

1)氧化镁价格低廉,能够显著降低从污水中回收鸟粪石的成本。1) Magnesium oxide is cheap and can significantly reduce the cost of recovering struvite from sewage.

2)氧化镁作为镁源虽然在水中的溶解度较低,但奥奈达希瓦氏菌及其代谢产物可促进氧化镁的溶解,从而为鸟粪石合成提供充足的镁离子,实现氧化镁资源的高效利用。2) Magnesium oxide as a magnesium source has low solubility in water, but Oneida Shewanella and its metabolites can promote the dissolution of magnesium oxide, thereby providing sufficient magnesium ions for struvite synthesis and realizing magnesium oxide resources. efficient use.

3)氧化镁在水中溶解液可以释放出氢氧根离子,促使溶液pH的升高,结合奥奈达希瓦氏菌自身代谢对提升pH的作用,因此可避免额外碱源的添加,进一步降低鸟粪石的生产成本。3) The dissolved solution of magnesium oxide in water can release hydroxide ions, which promotes the increase of pH of the solution, combined with the effect of Oneida Shewanella's own metabolism on raising pH, so the addition of additional alkali sources can be avoided and further reduced Production cost of struvite.

4)奥奈达希瓦氏菌的代谢活动还能够将废水中的有机磷和有机氮转化为无机氮磷,促进鸟粪石沉淀,而传统的鸟粪石结晶工艺只能处理无机氮磷,因此本发明提供的方法有助于推动污水氮磷去除工艺与鸟粪石结晶工艺的联合,实现更加有效、低成本的氮磷去除和鸟粪石回收,并有望大幅减少污水处理过程中产生的污泥量。4) The metabolic activity of Shewanella Oneida can also convert organic phosphorus and organic nitrogen in wastewater into inorganic nitrogen and phosphorus, and promote struvite precipitation, while the traditional struvite crystallization process can only process inorganic nitrogen and phosphorus, Therefore, the method provided by the present invention helps to promote the combination of the nitrogen and phosphorus removal process of sewage and the struvite crystallization process, realizes more effective and low-cost nitrogen and phosphorus removal and struvite recovery, and is expected to greatly reduce the amount of nitrogen and phosphorus generated in the sewage treatment process. amount of sludge.

5)本发明提供的方法通过控制氧化镁的不同添加量,可获得不同形貌及粒径的鸟粪石,有望为工业生产不同规格的鸟粪石提供新途径。5) The method provided by the present invention can obtain struvite with different shapes and particle sizes by controlling different addition amounts of magnesium oxide, and is expected to provide a new approach for industrial production of struvite with different specifications.

为更清楚起见,下面通过以下实施例进行详细说明。For the sake of clarity, detailed description will be given below through the following examples.

下述实施例中涉及的活化后的菌液按照以下方法获得:The activated bacterial liquid involved in the following examples is obtained according to the following methods:

将斜面培养基上保存的奥奈达希瓦氏菌用接种环刮取1个菌落,接种于装有100mLLB培养基(10g/L胰蛋白胨,5g/L酵母浸膏,5g/L氯化钠)的培养瓶中,在温度为30℃转速为200rpm的摇床上好氧培养12小时,使得最终细菌密度达到6×109CFU/mL,即获得活化后的菌液。One colony of Oneida Shewanella preserved on the slant medium was scraped with an inoculation loop, and inoculated into 100 mL of LB medium (10 g/L tryptone, 5 g/L yeast extract, 5 g/L sodium chloride) ) in a culture bottle with a temperature of 30°C and a rotating speed of 200rpm for 12 hours aerobic cultivation, so that the final bacterial density reaches 6×10 9 CFU/mL, that is, the activated bacterial liquid is obtained.

实施例1Example 1

在250mL培养瓶中加入100mL LB培养基(10g/L胰蛋白胨,5g/L酵母浸膏,5g/L氯化钠)作为模拟废水,121℃高压灭菌20分钟。其中,模拟废水总磷含量为170mg/L,总氮含量为625mg/L;有机磷含量为100mg/L,有机氮含量为560mg/L。同时,将0.032g氧化镁粉末置于电热恒温鼓风干燥箱中,170℃干热灭菌2小时。之后将1mL活化后的菌液接种于装有干热灭菌后的氧化镁和100mL LB培养基的培养瓶中,在转速为200rpm的摇床上好氧培养,温度为30℃。培养72h后,测定培养液的pH,对产物进行沉降分离,然后用无水乙醇对产物洗涤三次,置于真空干燥箱中室温干燥48小时。对产物进行X-射线衍射和扫描电镜分析,如图1和图2所示,图1是本发明提供的实施例1~3制备的鸟粪石的XRD图,图1中S-1表示实施例1制备的鸟粪石,S-2表示实施例2制备的鸟粪石,S-3表示实施例3制备的鸟粪石,JCPDS-77-2303表示鸟粪石的国际标准X射线衍射数据卡片,图2是本发明实施例1提供的鸟粪石FESEM图。通过图2可以看出,本实施例制备的产物为大量假四方锥形鸟粪石。100 mL of LB medium (10 g/L tryptone, 5 g/L yeast extract, 5 g/L sodium chloride) was added to a 250 mL culture flask as simulated wastewater, and autoclaved at 121 °C for 20 minutes. Among them, the total phosphorus content of the simulated wastewater was 170 mg/L, and the total nitrogen content was 625 mg/L; the organic phosphorus content was 100 mg/L, and the organic nitrogen content was 560 mg/L. At the same time, 0.032 g of magnesium oxide powder was placed in an electric heating constant temperature blast drying oven, and sterilized by dry heat at 170° C. for 2 hours. Then, 1 mL of the activated bacterial liquid was inoculated into a culture flask containing dry-heat sterilized magnesium oxide and 100 mL of LB medium, and aerobic cultivation was performed on a shaking table with a rotation speed of 200 rpm and a temperature of 30 °C. After culturing for 72 hours, the pH of the culture solution was measured, the product was separated by sedimentation, and then the product was washed three times with absolute ethanol, and dried in a vacuum drying box at room temperature for 48 hours. The product is analyzed by X-ray diffraction and scanning electron microscope, as shown in Figure 1 and Figure 2, Figure 1 is the XRD pattern of the struvite prepared in Examples 1 to 3 provided by the present invention, and S-1 in Figure 1 represents the implementation of The struvite prepared in Example 1, S-2 represents the struvite prepared in Example 2, S-3 represents the struvite prepared in Example 3, and JCPDS-77-2303 represents the international standard X-ray diffraction data of struvite Card, Figure 2 is the FESEM image of struvite provided in Example 1 of the present invention. It can be seen from FIG. 2 that the product prepared in this example is a large number of false square conical struvite.

进行三次平行实验,确定获得鸟粪石的平均产量为121.0mg,对应氧化镁的转化率为61.8%。Three parallel experiments were carried out, and it was determined that the average yield of struvite was 121.0 mg, corresponding to a conversion rate of magnesium oxide of 61.8%.

实施例2Example 2

在250mL培养瓶中加入100mL改良的LB培养基(20g/L胰蛋白胨,10g/L酵母浸膏,5g/L氯化钠)作为模拟废水,121℃高压灭菌20分钟。其中,模拟废水总磷含量为340mg/L,总氮含量为1250mg/L;有机磷含量为200mg/L,有机氮含量为1120mg/L。同时,将0.032g氧化镁粉末置于电热恒温鼓风干燥箱中,170℃干热灭菌2小时。之后将1mL活化后的菌液接种于装有干热灭菌后的氧化镁和100mL培养基的培养瓶中,在转速为200rpm的摇床上好氧培养,温度为30℃。培养72h后,测定培养液的pH,对产物进行沉降分离,然后用无水乙醇对产物洗涤三次,置于真空干燥箱中室温干燥48小时。对产物进行X-射线衍射(XRD)和扫描电镜分析,如图1和图3所示,图3是本发明实施例2提供的鸟粪石FESEM图。通过图3可以看出,本实施例制备的产物均为假四方锥形鸟粪石。100 mL of modified LB medium (20 g/L tryptone, 10 g/L yeast extract, 5 g/L sodium chloride) was added to a 250 mL culture flask as simulated wastewater, and autoclaved at 121 °C for 20 minutes. Among them, the total phosphorus content of the simulated wastewater was 340 mg/L, and the total nitrogen content was 1250 mg/L; the organic phosphorus content was 200 mg/L, and the organic nitrogen content was 1120 mg/L. At the same time, 0.032 g of magnesium oxide powder was placed in an electric heating constant temperature blast drying oven, and sterilized by dry heat at 170° C. for 2 hours. Then, 1 mL of the activated bacterial liquid was inoculated into a culture flask containing dry-heat sterilized magnesium oxide and 100 mL of culture medium, and aerobic culture was performed on a shaking table with a rotating speed of 200 rpm and a temperature of 30 °C. After culturing for 72 hours, the pH of the culture solution was measured, the product was separated by sedimentation, and then the product was washed three times with absolute ethanol, and dried in a vacuum drying box at room temperature for 48 hours. The product is analyzed by X-ray diffraction (XRD) and scanning electron microscope, as shown in Figures 1 and 3, and Figure 3 is a FESEM image of struvite provided in Example 2 of the present invention. It can be seen from Fig. 3 that the products prepared in this example are all pseudo-square conical struvite.

进行三次平行实验,确定获得鸟粪石的平均产量为173.3mg,对应氧化镁的转化率为88.4%。Three parallel experiments were carried out, and it was determined that the average yield of struvite was 173.3 mg, corresponding to a conversion rate of magnesium oxide of 88.4%.

实施例3Example 3

在250mL培养瓶中分别加入100mL改良的LB培养基(25g/L胰蛋白胨,12.5g/L酵母浸膏,5g/L氯化钠)作为模拟废水,121℃高压灭菌20分钟。其中,模拟废水总磷含量为425mg/L,总氮含量为1560mg/L;有机磷含量为250mg/L,有机氮含量为1400mg/L同时,将0.032g氧化镁粉末置于电热恒温鼓风干燥箱中,170℃干热灭菌2小时。之后将1mL活化后的菌液分别接种于装有干热灭菌后的氧化镁和100mL培养基的培养瓶中,在转速为200rpm的摇床上好氧培养,温度为30℃。培养72h后,测定培养液的pH,对产物进行沉降分离,然后用无水乙醇对产物洗涤三次,置于真空干燥箱中室温干燥48小时。对产物进行X-射线衍射(XRD)和扫描电镜分析,如图1和图4所示,图4是本发明实施例3提供的鸟粪石FESEM图。通过图4可以看出,本实施例制备的产物均为假四方锥形鸟粪石。100 mL of modified LB medium (25 g/L tryptone, 12.5 g/L yeast extract, 5 g/L sodium chloride) was added to a 250 mL culture flask as simulated wastewater, and autoclaved at 121 °C for 20 minutes. Among them, the total phosphorus content of the simulated wastewater was 425 mg/L, and the total nitrogen content was 1560 mg/L; the organic phosphorus content was 250 mg/L, and the organic nitrogen content was 1400 mg/L. At the same time, 0.032 g of magnesium oxide powder was placed in an electric heating constant temperature blast drying Dry heat sterilization at 170°C for 2 hours. Afterwards, 1 mL of the activated bacterial liquid was inoculated into culture flasks containing dry-heat sterilized magnesium oxide and 100 mL of culture medium, respectively, and aerobically cultivated on a shaking table with a rotational speed of 200 rpm and a temperature of 30°C. After culturing for 72 hours, the pH of the culture solution was measured, the product was separated by sedimentation, and then the product was washed three times with absolute ethanol, and dried in a vacuum drying box at room temperature for 48 hours. The product was analyzed by X-ray diffraction (XRD) and scanning electron microscope, as shown in FIG. 1 and FIG. 4 , and FIG. 4 is the FESEM image of struvite provided in Example 3 of the present invention. It can be seen from FIG. 4 that the products prepared in this example are all pseudo-square conical struvite.

进行三次平行实验,确定获得鸟粪石的平均产量为192.2mg,对应氧化镁的转化率为97.6%。Three parallel experiments were carried out, and it was determined that the average yield of struvite was 192.2 mg, corresponding to a conversion rate of 97.6% of magnesium oxide.

实施例4Example 4

在250mL培养瓶中加入100mL LB培养基(10g/L胰蛋白胨,5g/L酵母浸膏,5g/L氯化钠)作为模拟废水,121℃高压灭菌20分钟。其中,模拟废水总磷含量为170mg/L,总氮含量为625mg/L;有机磷含量为100mg/L,有机氮含量为560mg/L。同时,将不同质量(0.016g、0.064g、0.096g)的氧化镁粉末置于电热恒温鼓风干燥箱中,170℃干热灭菌2小时。之后将1mL活化后的菌液接种于装有干热灭菌后的氧化镁和100mL培养基的培养瓶中,在转速为200rpm的摇床上好氧培养,温度为30℃。培养72h后,测定培养液的pH,对产物进行沉降分离,然后用无水乙醇对产物洗涤三次,置于真空干燥箱中室温干燥48小时。对产物进行X-射线衍射(XRD)和扫描电镜分析,如图5~8所示,图5是本发明实施例4提供的鸟粪石的XRD图,图6是本发明实施例4提供的氧化镁添加量为0.16g/L时制备的鸟粪石的FESEM图,图7是本发明实施例4提供的氧化镁添加量为0.64g/L时制备的鸟粪石的FESEM图,图8是本发明实施例4提供的氧化镁添加量为0.96g/L时制备的鸟粪石的FESEM图。通过图5~8可以看出,奥奈达希瓦氏菌可利用MgO为镁源,专一地矿化鸟粪石,且添加的MgO对鸟粪石纯度无影响;氧化镁添加量较低时,鸟粪石粒径大,反之,粒径小;在氧化镁的添加量不同时,鸟粪石呈现不一样的形貌。100 mL of LB medium (10 g/L tryptone, 5 g/L yeast extract, 5 g/L sodium chloride) was added to a 250 mL culture flask as simulated wastewater, and autoclaved at 121 °C for 20 minutes. Among them, the total phosphorus content of the simulated wastewater was 170 mg/L, and the total nitrogen content was 625 mg/L; the organic phosphorus content was 100 mg/L, and the organic nitrogen content was 560 mg/L. At the same time, magnesium oxide powders of different masses (0.016g, 0.064g, 0.096g) were placed in an electric heating constant temperature blast drying oven, and sterilized by dry heat at 170° C. for 2 hours. Then, 1 mL of the activated bacterial liquid was inoculated into a culture flask containing dry-heat sterilized magnesium oxide and 100 mL of culture medium, and aerobic culture was performed on a shaking table with a rotating speed of 200 rpm and a temperature of 30 °C. After culturing for 72 hours, the pH of the culture solution was measured, the product was separated by sedimentation, and then the product was washed three times with absolute ethanol, and dried in a vacuum drying box at room temperature for 48 hours. The product is analyzed by X-ray diffraction (XRD) and scanning electron microscope, as shown in Figures 5 to 8, Figure 5 is the XRD pattern of the struvite provided by Example 4 of the present invention, and Figure 6 is provided by Example 4 of the present invention. The FESEM image of the struvite prepared when the addition amount of magnesium oxide is 0.16g/L, Fig. 7 is the FESEM image of the struvite prepared when the addition amount of magnesium oxide provided in Example 4 of the present invention is 0.64g/L, Fig. 8 It is the FESEM image of the struvite prepared when the magnesium oxide addition amount provided in Example 4 of the present invention is 0.96 g/L. It can be seen from Figures 5 to 8 that Oneida Shewanella can use MgO as a magnesium source to exclusively mineralize struvite, and the added MgO has no effect on the purity of struvite; the amount of magnesium oxide added is relatively low When the particle size of struvite is large, on the contrary, the particle size is small; when the addition amount of magnesium oxide is different, the struvite has different appearances.

进行三次平行实验,确定氧化镁添加量为0.16g/L、0.64g/L和0.96g/L时所得鸟粪石的平均产量分别为79.9mg、122.3mg和124.6mg,氧化镁的转化率分别为81.5%、31.3%和21.2%。Three parallel experiments were carried out to determine that the average yields of struvite obtained when the amount of magnesium oxide was 0.16g/L, 0.64g/L and 0.96g/L were 79.9mg, 122.3mg and 124.6mg, respectively. The conversion rates of magnesium oxide were were 81.5%, 31.3% and 21.2%.

为便于比较不同实施例的实验条件和结果差异,将实施例1~4的物料组成和产量数据整合到表1中:For the convenience of comparing the experimental conditions and results of different embodiments, the material composition and yield data of Examples 1 to 4 are integrated into Table 1:

表1不同实施例的物料组成和产量The material composition and output of different embodiments of table 1

Figure BDA0001617145330000081
Figure BDA0001617145330000081

通过表1可知,随着培养基中有机氮磷的浓度增加,鸟粪石产量及氧化镁的转化率大幅度提升,氧化镁转化率可高达97.6%,说明该方法可适用于含有不同浓度有机氮磷的污水处理,具有经济、高效地处理高浓度有机氮磷并回收鸟粪石的潜力。It can be seen from Table 1 that with the increase of the concentration of organic nitrogen and phosphorus in the medium, the yield of struvite and the conversion rate of magnesium oxide are greatly improved, and the conversion rate of magnesium oxide can be as high as 97.6%. Nitrogen and phosphorus wastewater treatment has the potential to economically and efficiently treat high concentrations of organic nitrogen and phosphorus and recover struvite.

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.

Claims (8)

1.一种从废水中回收鸟粪石的方法,包括以下步骤:1. a method for reclaiming struvite from waste water, comprising the following steps: a)将奥奈达希瓦氏菌进行活化,得到活化菌液;a) activating Oneida Shewanella to obtain an activated bacterial solution; b)将所述活化菌液、氧化镁和废水混合,好氧培养,得到鸟粪石;b) mixing described activated bacterial liquid, magnesium oxide and waste water, and aerobic cultivation to obtain struvite; 所述废水的总磷含量为170~425mg/L,总氮含量为625~1560mg/L;The total phosphorus content of the wastewater is 170-425 mg/L, and the total nitrogen content is 625-1560 mg/L; 所述氧化镁和废水的用量比为(0.1~1.2)g:1L。The dosage ratio of the magnesium oxide to the waste water is (0.1-1.2) g: 1L. 2.根据权利要求1所述的方法,其特征在于,步骤a)中,所述活化菌液中的细菌密度为1×109~15×109CFU/mL。2 . The method according to claim 1 , wherein in step a), the bacterial density in the activated bacterial solution is 1×10 9 to 15×10 9 CFU/mL. 3 . 3.根据权利要求1所述的方法,其特征在于,所述步骤a)具体包括:3. The method according to claim 1, wherein the step a) specifically comprises: 将保藏在固体培养基上的奥奈达希瓦氏菌接种到液体培养基中,好氧培养,得到活化菌液。Shewanella Oneida stored on the solid medium is inoculated into the liquid medium and cultured aerobically to obtain an activated bacterial liquid. 4.根据权利要求3所述的方法,其特征在于,步骤a)中,所述液体培养基为LB培养基。4. method according to claim 3, is characterized in that, in step a), described liquid medium is LB medium. 5.根据权利要求3所述的方法,其特征在于,步骤a)中,所述好氧培养的温度为25~35℃;所述好氧培养的时间为8~16h。5 . The method according to claim 3 , wherein, in step a), the temperature of the aerobic cultivation is 25-35° C.; the time of the aerobic cultivation is 8-16 h. 6 . 6.根据权利要求1所述的方法,其特征在于,步骤b)中,所述活化菌液和废水的体积比为(0.1~5):100。6 . The method according to claim 1 , wherein in step b), the volume ratio of the activated bacterial solution to the waste water is (0.1-5):100. 7 . 7.根据权利要求1所述的方法,其特征在于,步骤b)中,所述好氧培养的温度为25~35℃;所述好氧培养的时间为48~96h。7 . The method according to claim 1 , wherein, in step b), the temperature of the aerobic cultivation is 25-35° C.; the time of the aerobic cultivation is 48-96 h. 8 . 8.根据权利要求1所述的方法,其特征在于,步骤b)中,所述废水的有机磷含量为100~250mg/L;所述废水的有机氮含量为560~1400mg/L。The method according to claim 1, wherein in step b), the organic phosphorus content of the wastewater is 100-250 mg/L; the organic nitrogen content of the wastewater is 560-1400 mg/L.
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