CN103468659A - Efficient utilization method of activated sludge - Google Patents
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Abstract
本发明公开了一种活性污泥的高效利用方法,包括步骤:将活性污泥进行离心或过滤处理以去除活性污泥中的水分;在脱水后的活性污泥中加入1-4倍量(w/v)的含非离子型表面活性剂的提取溶剂,搅拌或超声波提取0.5-2小时后,离心或过滤得水解酶提取液;在水解酶提取液中加入乙醇或丙酮等有机溶剂至其浓度为60%-90%,4℃-室温静置0.5-1.0小时后离心,取其沉淀,即获得水解酶。通过上述方式,本发明能够实现活性污泥的资源化利用,减少环境污染,同时开发出一种巨量的天然水解酶资源。
The invention discloses a high-efficiency utilization method of activated sludge, comprising the steps of: centrifuging or filtering the activated sludge to remove water in the activated sludge; adding 1-4 times the amount ( w/v) with an extraction solvent containing non-ionic surfactant, after stirring or ultrasonic extraction for 0.5-2 hours, centrifuge or filter to obtain a hydrolase extract; add organic solvents such as ethanol or acetone to the hydrolase extract The concentration is 60%-90%, let stand at 4°C-room temperature for 0.5-1.0 hours, centrifuge, collect the precipitate, and obtain the hydrolase. Through the above method, the present invention can realize resource utilization of activated sludge, reduce environmental pollution, and simultaneously develop a huge amount of natural hydrolytic enzyme resources.
Description
技术领域technical field
本发明涉及环保与生物资源开发利用领域,特别是涉及一种活性污泥的高效利用方法。The invention relates to the fields of environmental protection and development and utilization of biological resources, in particular to an efficient utilization method of activated sludge.
背景技术Background technique
微生物发酵法为常用的污水处理方法,通过微生物的代谢将有机废物分解成CO2和水,同时微生物自身也大量繁殖增长。污水处理过程具体为微生物分泌各种胞外水解酶将大分子有机物水解成小分子物质,小分子物质则可被微生物吸收和代谢,从而达到污水净化的目的。Microbial fermentation is a commonly used sewage treatment method, which decomposes organic waste into CO 2 and water through the metabolism of microorganisms, and at the same time the microorganisms themselves multiply and grow in large numbers. The sewage treatment process is specifically that microorganisms secrete various extracellular hydrolytic enzymes to hydrolyze macromolecular organic matter into small molecular substances, and small molecular substances can be absorbed and metabolized by microorganisms, so as to achieve the purpose of sewage purification.
在污水处理过程中,污水处理厂须定期排出大量的微生物菌体,称为活性污泥或剩余活性污泥。随着城镇化、城市工业化的发展及城市人口的增长,污水及活性污泥量迅速增长,如活性污泥以每年大约10%的速度增长。活性污泥主要由细菌、病毒、真菌、藻类、原生动物及所述生物死亡后的残留物组成,具有高度粘结性、压缩性和腐败性等,处理非常困难。污水处理厂用于活性污泥处理的费用占污水厂总投资和总运行费用的约40%,活性污泥成为一个新的污染源。During the sewage treatment process, the sewage treatment plant must regularly discharge a large amount of microbial cells, which is called activated sludge or residual activated sludge. With the development of urbanization, urban industrialization and the growth of urban population, the amount of sewage and activated sludge is increasing rapidly, such as activated sludge at a rate of about 10% per year. Activated sludge is mainly composed of bacteria, viruses, fungi, algae, protozoa and the residues of the dead organisms. It is highly cohesive, compressible and rotten, and it is very difficult to deal with. The cost of activated sludge treatment in sewage treatment plants accounts for about 40% of the total investment and operating costs of sewage plants, and activated sludge has become a new source of pollution.
现有活性污泥处理方法主要有直接或经过发酵后作为农作物的肥料、填埋或烘干后填埋、焚烧及投海等。各方法的优缺点如下:The existing activated sludge treatment methods mainly include direct or fermented fertilizer for crops, landfill or landfill after drying, incineration and throwing into the sea. The advantages and disadvantages of each method are as follows:
活性污泥中含大量有机态氮和丰富的无机盐,是一种较好的有机肥料,但活性污泥中常含有病原菌、有害虫卵、重金属和有毒物质,不宜作为肥料施用于农田。且活性污泥含水量大,约80%,需脱水浓缩后施加至田地里,在脱水过程中需添加大量的絮凝剂,但絮凝剂会造成土地板结等诸多不良影响。Activated sludge contains a large amount of organic nitrogen and rich inorganic salts. It is a good organic fertilizer. However, activated sludge often contains pathogenic bacteria, harmful insect eggs, heavy metals and toxic substances, so it should not be used as fertilizer for farmland. Moreover, the water content of activated sludge is about 80%, and it needs to be dehydrated and concentrated before being applied to the field. During the dehydration process, a large amount of flocculant needs to be added, but the flocculant will cause many adverse effects such as land compaction.
填埋法工程大,耗费大量土地,且易污染周边环境和地下水源。The landfill method is a large project, consumes a lot of land, and is easy to pollute the surrounding environment and groundwater sources.
焚烧法投资和运行成本高,能源消耗大,且燃烧时有二氧化硫和二恶因等有害物质产生。The incineration method has high investment and operating costs, high energy consumption, and harmful substances such as sulfur dioxide and dioxin are produced during combustion.
投海法易使海水污染,国际上已禁止抛海处理工业废物和污水污泥。The method of throwing into the sea is easy to pollute the seawater, and the throwing of industrial waste and sewage sludge into the sea has been banned internationally.
此外,针对活性污泥处理,还研究出多种热解技术,如低温或压热解制油、微波高压热化学转化等技术,在催化剂的作用下,将污泥中的有机物热分解转化为燃气、燃油和焦油等,但处于研究阶段的热解技术还存在产品品质或生产成本等问题。总的来说,目前的活性污泥处理方法都不能有效地解决活性污泥的处理。In addition, for the treatment of activated sludge, a variety of pyrolysis technologies have been developed, such as low-temperature or pressure pyrolysis oil production, microwave high-pressure thermochemical conversion and other technologies. Under the action of catalysts, the organic matter in the sludge is thermally decomposed and converted into Gas, fuel oil and tar, etc., but the pyrolysis technology in the research stage still has problems such as product quality or production cost. In general, none of the current activated sludge treatment methods can effectively solve the treatment of activated sludge.
发明内容Contents of the invention
本发明主要解决的技术问题是提供一种活性污泥的高效利用方法,能够从活性污泥中制备水解酶,实现活性污泥的资源化利用,减少环境污染。The technical problem mainly solved by the invention is to provide an efficient utilization method of activated sludge, which can prepare hydrolytic enzymes from activated sludge, realize resource utilization of activated sludge, and reduce environmental pollution.
为解决上述技术问题,本发明采用的一个技术方案是:提供一种活性污泥的高效利用方法,包括步骤:将活性污泥进行离心或过滤处理以去除活性污泥中的水分;在脱水后的活性污泥中加入1-4倍量(w/v)的含非离子型表面活性剂的提取溶剂,搅拌或超声波提取0.5-2小时后,离心或过滤得水解酶提取液;在水解酶提取液中加入乙醇或丙酮等有机溶剂至其浓度为60%-90%,4℃-室温静置0.5-1.0小时后离心,取其沉淀,即获得水解酶,实现活性污泥的资源化利用。In order to solve the above-mentioned technical problems, a technical scheme adopted by the present invention is: provide a kind of high-efficiency utilization method of activated sludge, comprising the steps of: centrifuging or filtering the activated sludge to remove the moisture in the activated sludge; Add 1-4 times the amount (w/v) of non-ionic surfactant-containing extraction solvent to the activated sludge, stir or ultrasonically extract for 0.5-2 hours, centrifuge or filter to obtain the hydrolytic enzyme extract; Add organic solvents such as ethanol or acetone to the extract to a concentration of 60%-90%, let stand at 4°C-room temperature for 0.5-1.0 hours, then centrifuge, collect the precipitate, and obtain hydrolytic enzymes to realize resource utilization of activated sludge .
其中,获得水解酶提取液后,还可将水解酶提取液进行膜浓缩以便沉淀水解酶。Wherein, after obtaining the hydrolase extract, the hydrolase extract can also be membrane-concentrated to precipitate the hydrolase.
其中,将获得的水解酶进行干燥或溶解,以制成粉末水解酶制剂或液体水解酶制剂。干燥方式为冷冻干燥、真空干燥或喷雾干燥。Wherein, the obtained hydrolase is dried or dissolved to make powder hydrolase preparation or liquid hydrolase preparation. The drying method is freeze drying, vacuum drying or spray drying.
本发明提取溶剂中的非离子型表面活性剂为0.5%-2%的TritonX-100。The nonionic surfactant in the extraction solvent of the present invention is 0.5%-2% TritonX-100.
本发明可对有机溶剂进行回收利用,具体为获得水解酶沉淀后,对离心后的上清液进行减压蒸馏以回收其中的有机溶剂。The invention can recycle the organic solvent, specifically after obtaining the hydrolytic enzyme precipitation, carry out vacuum distillation on the centrifuged supernatant to recover the organic solvent therein.
本发明的有益效果是:区别于现有的活性污泥处理技术,本发明将活性污泥作为资源利用的方法,可从活性污泥中提取水解酶,具体为首先将活性污泥进行脱水处理,在脱水后的活性污泥中加入含有非离子型表面活性剂的提取溶剂,搅拌或超声波提取后,离心或过滤得水解酶提取液,然后,在水解酶提取液中加入有机溶剂,并静置后离心,获得水解酶沉淀。通过上述方式,本发明能够实现活性污泥的资源化利用,减少环境污染,同时开发出一种巨量的天然水解酶资源。The beneficial effects of the present invention are: different from the existing activated sludge treatment technology, the present invention uses activated sludge as a resource utilization method, and can extract hydrolytic enzymes from activated sludge, specifically dehydrating activated sludge first , adding an extraction solvent containing a non-ionic surfactant to the dehydrated activated sludge, stirring or ultrasonically extracting, centrifuging or filtering to obtain a hydrolytic enzyme extract, then adding an organic solvent to the hydrolytic enzyme extract, and statically Centrifuge after placing to obtain hydrolytic enzyme precipitate. Through the above method, the present invention can realize resource utilization of activated sludge, reduce environmental pollution, and simultaneously develop a huge amount of natural hydrolytic enzyme resources.
附图说明Description of drawings
图1是本发明活性污泥处理方法一实施例的流程示意图;Fig. 1 is a schematic flow sheet of an embodiment of the activated sludge treatment method of the present invention;
图2是图1所示实施例中不同浓度有机溶剂沉淀的水解酶中蛋白酶的活性分析;Fig. 2 is the activity analysis of protease in the hydrolase of different concentration organic solvent precipitation in the embodiment shown in Fig. 1;
图3是图1所示实施例中不同浓度有机溶剂沉淀的水解酶中酯酶的活性分析;Fig. 3 is the activity analysis of esterase in the hydrolase of different concentration organic solvent precipitation in the embodiment shown in Fig. 1;
图4是不同生物材料中蛋白酶的活性分析。Figure 4 is an analysis of protease activity in different biological materials.
具体实施方式Detailed ways
下面结合附图和实施例对本发明进行详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings and embodiments.
实施例1Example 1
请参阅图1,图1是本发明活性污泥利用方法一实施例的流程示意图,如图1所示,活性污泥的利用方法为提取其中的水解酶,实现活性污泥的资源化利用。活性污泥在提取水解酶之前,对其进行脱水处理,脱水方式为离心或过滤。然后,在脱水后的活性污泥中加入1-4倍量(w/v)提取溶剂,搅拌或超声波提取0.5-2小时后,离心或过滤后得水解酶提取液。Please refer to Fig. 1. Fig. 1 is a schematic flow chart of an embodiment of the activated sludge utilization method of the present invention. As shown in Fig. 1, the utilization method of the activated sludge is to extract the hydrolytic enzyme therein to realize the resource utilization of the activated sludge. Before the hydrolytic enzyme is extracted from the activated sludge, it is dehydrated by centrifugation or filtration. Then, add 1-4 times the amount (w/v) of extraction solvent to the dehydrated activated sludge, stir or ultrasonically extract for 0.5-2 hours, centrifuge or filter to obtain a hydrolytic enzyme extract.
其中,提取溶剂中含非离子型表面活性剂。在本实施例中,提取溶剂为含0.5%-2%的Triton X-100水溶液。Wherein, the extraction solvent contains a nonionic surfactant. In this embodiment, the extraction solvent is an aqueous solution containing 0.5%-2% Triton X-100.
在水解酶提取液中加入乙醇或丙酮等有机溶剂至其浓度为60%-90%,室温或冰上静置0.5-1.0小时后离心,获得水解酶沉淀。Add organic solvents such as ethanol or acetone to the hydrolytic enzyme extract to a concentration of 60%-90%, leave it at room temperature or on ice for 0.5-1.0 hours and then centrifuge to obtain hydrolytic enzyme precipitates.
在其他实施例中,可利用硫酸铵沉淀水解酶。In other embodiments, ammonium sulfate can be used to precipitate the hydrolase.
在其他实施例中,可将水解酶提取液先进行膜浓缩,然后沉淀处理。In other embodiments, the hydrolytic enzyme extract can be concentrated by membrane first, and then precipitated.
沉淀出的水解酶可进行干燥,以获得粉末水解酶制剂;或进行溶解,以获得液体水解酶制剂。The precipitated hydrolase can be dried to obtain a powder hydrolase preparation; or dissolved to obtain a liquid hydrolase preparation.
其中,干燥的方式可以为冷冻干燥、真空干燥或喷雾干燥。Wherein, the drying method may be freeze drying, vacuum drying or spray drying.
在本实施例中,还可对离心后的上清液进行减压蒸馏以回收其中的有机溶剂。In this embodiment, the centrifuged supernatant can also be distilled under reduced pressure to recover the organic solvent therein.
其中,在没有限定温度的情况下,本实施例的操作通常在4℃-室温下进行。Wherein, under the condition that the temperature is not limited, the operation of this embodiment is usually carried out at 4° C. to room temperature.
在本实施例中,对获得的水解酶活性进行了检测。In this example, the obtained hydrolase activity was tested.
如图2所示,图2是图1所示实施例中不同浓度有机溶剂沉淀的水解酶中蛋白酶的活性分析,其中,1为活性污泥水解酶提取液的蛋白酶活性,2-8为不同浓度乙醇沉淀水解酶提取液获得的蛋白酶活性。其分析方法采用中性酪蛋白水解法和含0.1%-0.5%明胶的聚丙烯酰胺电泳凝胶自显影法测定蛋白酶活性。As shown in Figure 2, Fig. 2 is the activity analysis of protease in the hydrolase of different concentration organic solvent precipitation in the embodiment shown in Fig. 1, and wherein, 1 is the protease activity of activated sludge hydrolase extraction solution, and 2-8 is different Protease activity obtained by ethanol precipitation of hydrolytic enzyme extracts. The analysis method adopts neutral casein hydrolysis method and polyacrylamide electrophoresis gel autographic method containing 0.1%-0.5% gelatin to measure protease activity.
图3是图1所示实施例中不同浓度有机溶剂沉淀的水解酶中酯酶的活性分析,如图3所示,1-6为不同浓度有机溶剂沉淀的酯酶活性,7-10作为对照,为不同浓度有机溶剂沉淀的花生中酯酶活性。其分析方法采用对硝基苯酚法和坚牢蓝RR盐染色的聚丙烯酰胺电泳凝胶自显影法测定酯酶活性。Fig. 3 is the activity analysis of esterase in the hydrolase of different concentration organic solvent precipitation in the embodiment shown in Fig. 1, as shown in Figure 3, 1-6 is the esterase activity of different concentration organic solvent precipitation, 7-10 is as contrast , is the esterase activity in peanuts precipitated with different concentrations of organic solvents. The analysis method adopts p-nitrophenol method and Fast Blue RR salt-stained polyacrylamide electrophoresis gel autographic method to determine esterase activity.
图4是不同生物材料中蛋白酶的活性分析,如图4所示,8为活性污泥中蛋白酶活性,10为木瓜中蛋白酶活性。Fig. 4 is the activity analysis of protease in different biological materials, as shown in Fig. 4, 8 is protease activity in activated sludge, 10 is protease activity in papaya.
实施例2Example 2
在100g污水处理厂的活性污泥中加入400ml提取溶剂,搅拌提取1小时,离心后得水解酶提取液。在水解酶提取液中加入丙酮至丙酮终浓度为80%,4℃冰箱中静置1小时,离心得水解酶沉淀,沉淀溶解后得液态水解酶制剂,或经冷冻干燥后得高活性水解酶制剂粉。Add 400ml of extraction solvent to 100g of activated sludge from a sewage treatment plant, stir and extract for 1 hour, and centrifuge to obtain a hydrolytic enzyme extract. Add acetone to the hydrolytic enzyme extract until the final concentration of acetone is 80%, put it in a refrigerator at 4°C for 1 hour, centrifuge to obtain a hydrolytic enzyme precipitate, and obtain a liquid hydrolytic enzyme preparation after the precipitate dissolves, or obtain a high-activity hydrolytic enzyme after freeze-drying Preparation powder.
分离制备的液态和粉末水解酶制剂经酪蛋白水解法和含0.1%明胶的聚丙烯酰胺电泳凝胶自显影法测定其蛋白酶活性,经对硝基苯酚法和坚牢蓝RR盐染色的聚丙烯酰胺电泳凝胶自显影法测定其酯酶活性,通过测定,蛋白酶和酯酶的提取和回收率都很高。The protease activity of the liquid and powder hydrolytic enzyme preparations prepared by separation was determined by casein hydrolysis and polyacrylamide electrophoresis gel autography containing 0.1% gelatin, and the polypropylene was stained by p-nitrophenol method and fast blue RR salt The esterase activity was measured by amide electrophoresis gel autographic method, and the extraction and recovery rates of protease and esterase were high.
用上述方法提取和制备酶制剂,每千克活性污泥可获得30,000酶活单位的中性蛋白酶和38.2酶活单位的酯酶。或每千克活性污泥可制备13克粉末酶制剂,每克酶粉中含中性蛋白酶800酶活性单位和酯酶11.6酶活性单位。或每克蛋白质含6800酶活性单位的中性蛋白酶和94酶活性单位的酯酶。Using the above method to extract and prepare the enzyme preparation, 30,000 enzyme activity units of neutral protease and 38.2 enzyme activity units of esterase can be obtained per kilogram of activated sludge. Or 13 grams of powdered enzyme preparation can be prepared per kilogram of activated sludge, containing 800 enzyme activity units of neutral protease and 11.6 enzyme activity units of esterase in each gram of enzyme powder. Or every gram of protein contains 6800 enzyme activity units of neutral protease and 94 enzyme activity units of esterase.
综上所述,本发明活性污泥利用方法可将污水处理厂排放的活性污泥变废为宝,从根本上解决污泥带来的环境危害,同时也开发出一种巨量的天然水解酶资源,具有良好的经济和社会效益。此方法的优点如下:In summary, the activated sludge utilization method of the present invention can turn the activated sludge discharged from the sewage treatment plant into treasure, fundamentally solve the environmental hazards caused by the sludge, and also develop a huge amount of natural hydrolysis Enzyme resources have good economic and social benefits. The advantages of this method are as follows:
A.首次利用活性污泥提取和制备高活性水解酶制剂。A. It is the first time to use activated sludge to extract and prepare high activity hydrolytic enzyme preparation.
B.从活性污泥中提取和制备的蛋白酶活性高于目前常用植物材料木瓜中提取的蛋白酶活性。活性污泥是制备高活性蛋白酶等水解酶的优质资源,其含大量降解蛋白质、多糖和油脂等大分子有机物的水解酶。B. The protease activity extracted and prepared from activated sludge is higher than the protease activity extracted from papaya, a commonly used plant material. Activated sludge is a high-quality resource for the preparation of hydrolytic enzymes such as high-activity proteases, which contain a large number of hydrolytic enzymes that degrade macromolecular organic substances such as proteins, polysaccharides, and oils.
C.本发明的从活性污泥中提取水解酶的方法,设备投资少,操作简单,产品生产成本低,便于大规模生产。C. The method for extracting hydrolytic enzymes from activated sludge of the present invention has less investment in equipment, simple operation, low production cost, and is convenient for large-scale production.
D.本发明将活性污泥高效利用,变废为宝,从根本上解决污水处理厂排放的活性污泥带来的环境危害,具有巨大的经济和社会效益。D. The invention makes efficient use of activated sludge, turns waste into treasure, fundamentally solves the environmental hazards caused by activated sludge discharged from sewage treatment plants, and has huge economic and social benefits.
E.沉淀水解酶用的有机溶剂可完全回收重复利用,生产过程安全环保、无污染物产生。E. The organic solvent used to precipitate the hydrolytic enzyme can be completely recycled and reused, and the production process is safe and environmentally friendly, and no pollutants are produced.
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。The above is only an embodiment of the present invention, and does not limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made by using the description of the present invention and the contents of the accompanying drawings, or directly or indirectly used in other related technologies fields, all of which are equally included in the scope of patent protection of the present invention.
Claims (6)
- An active sludge efficiently utilize method, it is characterized in that, comprise the following steps:Active sludge is carried out to centrifugal or filtration treatment to remove the moisture in active sludge;In active sludge after dehydration, add 1-4 doubly measure (w/v) containing the extraction solvent of nonionic surface active agent, stir or after ultrasonic extraction 0.5-2 hour, centrifugal or filter to obtain the lytic enzyme extracting solution;Adding ethanol or acetone and other organic solvent to its concentration in the lytic enzyme extracting solution is 60%-90%, centrifugal after the standing 0.5-1.0 of 4 ℃-room temperature hour, gets its precipitation, obtains lytic enzyme, realizes the recycling treatment of active sludge.
- 2. method according to claim 1, is characterized in that, after the step of described acquisition lytic enzyme extracting solution, the lytic enzyme extracting solution carried out to membrane concentration.
- 3. according to claim 1, the described method of 2 any one, it is characterized in that, after the step of described acquisition lytic enzyme, described lytic enzyme is carried out to drying or dissolving, to make powder lytic enzyme preparation or liquid hydrolysis zymin.
- 4. method according to claim 3, is characterized in that, the drying mode of described lytic enzyme is lyophilize, vacuum-drying or spraying drying.
- 5. method according to claim 4, is characterized in that, the Triton X-100 that the nonionic surface active agent in described extraction solvent is 0.5%-2%.
- 6. method according to claim 5, is characterized in that, after described acquisition lytic enzyme step, described supernatant liquor after centrifugal carried out to underpressure distillation to reclaim organic solvent wherein.
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