技术领域technical field
本发明涉及废水处理方法、以及适用于该废水处理方法的废水处理装置。The invention relates to a wastewater treatment method and a wastewater treatment device suitable for the wastewater treatment method.
背景技术Background technique
对生活废水、工业废水实施除去其中含有的悬浊物质或有机物等的处理之后，排放入河流等中。Domestic wastewater and industrial wastewater are treated to remove suspended substances and organic substances contained therein, and then discharged into rivers and the like.
在含有机物等的废水的处理方法中，相比于以往的标准活性污泥法，膜分离活性污泥法(MBR)是一种有效的方法。在这里，MBR是指，活性污泥法中没有设置最终沉淀槽而是通过分离膜进行固液分离的方法。Membrane activated sludge (MBR) is an effective method for treating wastewater containing organic matter, etc., compared to the conventional standard activated sludge method. Here, MBR refers to a method in which solid-liquid separation is performed through a separation membrane without installing a final sedimentation tank in the activated sludge method.
但是MBR中存在下述事实，如果生物处理过的处理水中含有引起膜阻塞的物质(例如难分解性物质等)，就会发生分离膜的细孔被阻塞从而分离膜被堵塞的情形。However, MBR has the fact that if the biologically treated water contains substances that cause membrane clogging (for example, refractory substances, etc.), the pores of the separation membrane are clogged and the separation membrane is clogged.
因此，一种在通过MBR处理废水时添加脒系凝集剂的方法被提议(例如参照专利文献1)。凝集剂吸附在污泥表面的同时，也将难分解性物质等有机物吸附，因此可以防止膜阻塞。Therefore, a method of adding an amidine coagulant when treating wastewater by MBR has been proposed (for example, refer to Patent Document 1). The coagulant is adsorbed on the sludge surface and also adsorbs organic substances such as refractory substances, so that membrane clogging can be prevented.
现有技术文献prior art literature
专利文献patent documents
[专利文献1]国际公开第2011/016482号[Patent Document 1] International Publication No. 2011/016482
发明内容Contents of the invention
本发明要解决的课题Problems to be solved by the present invention
然而，过量凝集剂添加时或者污泥量相对于凝集剂的量较少时，有着凝集剂在处理水中残存、该凝集剂引起膜阻塞的担忧。此外，处理水中溶解的凝集剂也会通过分离膜。此时凝集剂变成处理水的污染原因，处理水的水质恶化。However, when the coagulant is added in excess or the amount of sludge is small relative to the amount of the coagulant, the coagulant may remain in the treated water and the coagulant may cause membrane clogging. In addition, the coagulant dissolved in the treated water also passes through the separation membrane. At this time, the coagulant becomes a cause of contamination of the treated water, and the quality of the treated water deteriorates.
此外，在凝集剂的添加初期阶段，即使是适宜的凝集剂浓度，也有随着凝集剂的持续添加，凝集剂在活性污泥上的吸附饱和，凝集剂在处理水中残存的担忧。In addition, even at an appropriate concentration of the coagulant at the initial stage of adding the coagulant, there is a concern that the coagulant may remain in the treated water due to the saturation of the adsorption of the coagulant on the activated sludge as the coagulant is continuously added.
本发明是以上述情形为鉴而完成的发明，以提供一种可以抑制分离膜的阻塞、得到高水质的处理水的废水处理方法以及废水处理装置为课题。The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a wastewater treatment method and a wastewater treatment device capable of suppressing clogging of a separation membrane and obtaining high-quality treated water.
解决课题的手段means of solving problems
本发明具有以下形态。The present invention has the following aspects.
[1]一种废水处理方法，该方法是通过膜分离活性污泥法、向槽内添加凝集剂来处理废水，且所述膜分离活性污泥法中，通过活性污泥中的微生物进行的生物处理与通过分离膜进行的固液分离处理在同一所述槽内进行，所述废水处理方法中，相对于所述凝集剂的添加量，添加50倍以上MLSS相当量的活性污泥，所述活性污泥未添加凝集剂。[1] A wastewater treatment method, which is to treat wastewater by adding a coagulant to the tank through the membrane separation activated sludge method, and in the membrane separation activated sludge method, the process is carried out by microorganisms in the activated sludge The biological treatment and the solid-liquid separation treatment carried out by the separation membrane are carried out in the same tank. In the wastewater treatment method, relative to the addition of the coagulant, an amount of activated sludge equivalent to 50 times or more MLSS is added, so The above activated sludge did not add coagulant.
[2]一种废水处理方法，该方法通过膜分离活性污泥法向槽内添加凝集剂来处理废水且所述膜分离活性污泥法中，通过活性污泥中的微生物进行的生物处理与通过分离膜进行的固液分离处理在同一所述槽内进行，所述废水处理方法中，相对于将要供给所述槽内的所述废水中的难分解性物质的量，添加0.1～2.75倍量的凝集剂。[2] A wastewater treatment method, the method adds a coagulant to the tank by the membrane separation activated sludge method to process wastewater and in the membrane separation activated sludge method, the biological treatment carried out by the microorganisms in the activated sludge and The solid-liquid separation treatment by the separation membrane is carried out in the same tank, and in the wastewater treatment method, 0.1 to 2.75 times the amount of the refractory substance in the wastewater to be supplied to the tank is added amount of coagulant.
[3]根据[2]所述的废水处理方法，相对于将要供给所述槽内的废水中的难分解性物质的量，添加0.2～2.5倍量的凝集剂。[3] The method for treating wastewater according to [2], wherein the coagulant is added in an amount of 0.2 to 2.5 times the amount of the refractory substance in the wastewater to be supplied to the tank.
[4]根据[2]或者[3]中所述的废水处理方法，相对于所述凝集剂的添加量，向所述槽中添加50倍以上的MLSS相当量的未添加凝集剂的活性污泥。[4] According to the wastewater treatment method described in [2] or [3], relative to the addition amount of the coagulant, add 50 times or more of MLSS equivalent amount of active sewage without coagulant to the tank mud.
[5]根据[1]或者[4]所述的废水处理方法，通过利用活性污泥中的微生物进行生物处理的标准活性污泥法预先对废水进行处理，再通过膜分离活性污泥法来处理该经过处理的废水，并且将由标准活性污泥法产生的剩余污泥作为所述未添加凝集剂的活性污泥添加到所述槽中。[5] According to the wastewater treatment method described in [1] or [4], the wastewater is treated in advance by using the standard activated sludge method of biological treatment by using microorganisms in the activated sludge, and then separated by the membrane activated sludge method. The treated wastewater was treated and the remaining sludge produced by the standard activated sludge process was added to the tank as the non-coagulant-added activated sludge.
[6]根据[1]、[4]、[5]的任一项中所述的废水处理方法，添加到所述槽中的未添加凝集剂的活性污泥的MLSS为6000～35000mg/L。[6] According to the wastewater treatment method described in any one of [1], [4], [5], the MLSS of the activated sludge without adding a coagulant added to the tank is 6000-35000 mg/L .
[7]一种废水处理方法，使用反渗透膜或者纳米过滤膜来过滤处理通过[1]～[6]的任一项中所述的废水处理方法得到的处理水。[7] A wastewater treatment method, which uses a reverse osmosis membrane or a nanofiltration membrane to filter and treat treated water obtained by the wastewater treatment method described in any one of [1] to [6].
[8]根据[7]所述的废水处理方法，对通过所述过滤处理产生的浓缩水进行浓缩处理。[8] The wastewater treatment method according to [7], wherein the concentrated water produced by the filtration treatment is subjected to concentration treatment.
[9]一种废水处理装置，该废水处理装置具备膜分离活性污泥处理装置且所述膜分离活性污泥处理装置中，通过活性污泥中的微生物进行的生物处理与通过分离膜进行的固液分离处理在同一槽内进行，所述废水处理装置具备向所述槽中添加凝集剂的凝集剂添加装置与添加未添加凝集剂的活性污泥的污泥添加装置，所述污泥添加装置，相对于所述凝集剂的添加量，添加50倍以上MLSS相当量的未添加凝集剂的活性污泥。[9] A wastewater treatment device comprising a membrane separation activated sludge treatment device, and in the membrane separation activated sludge treatment device, biological treatment by microorganisms in the activated sludge and separation membrane The solid-liquid separation process is carried out in the same tank, and the waste water treatment device is equipped with a coagulant adding device for adding a coagulant to the tank and a sludge adding device for adding activated sludge without adding a coagulant, and the sludge adding device, relative to the added amount of the coagulant, add 50 times or more MLSS equivalent amount of activated sludge without adding coagulant.
[10]一种废水处理装置，该废水处理装置具备膜分离活性污泥处理装置，所述膜分离活性污泥处理装置中，通过活性污泥中的微生物进行的生物处理与通过分离膜进行的固液分离处理在同一槽内进行，所述废水处理装置具备向所述槽中添加凝集剂的凝集剂添加装置，所述凝集剂添加装置，相对于将要供给所述槽内的所述废水中的难分解性物质的量，添加0.1～2.75倍量的凝集剂。[10] A kind of waste water treatment device, this waste water treatment device is equipped with membrane separation activated sludge treatment device, in described membrane separation activated sludge treatment device, the biological treatment carried out by the microorganism in the activated sludge and the separation membrane carried out The solid-liquid separation process is carried out in the same tank, and the wastewater treatment device is equipped with a coagulant adding device for adding a coagulant to the tank, and the coagulant adding device is used for the waste water to be supplied to the tank. Add 0.1 to 2.75 times the amount of coagulant to the amount of refractory substances.
[11]根据[10]所述的废水处理装置，所述凝集剂添加装置，相对于将要供给所述槽内的废水中的难分解性物质的量，添加0.2～2.5倍量的凝集剂。[11] The wastewater treatment device according to [10], wherein the coagulant adding device adds a coagulant in an amount of 0.2 to 2.5 times the amount of the refractory substance in the wastewater to be supplied to the tank.
[12]根据[10]或者[11]中所述的废水处理装置，所述废水处理装置还进一步地具有向所述槽内添加未添加凝集剂的活性污泥的污泥添加装置，所述污泥添加装置，相对于所述凝集剂的添加量，向所述槽中添加50倍以上的MLSS相当量的未添加凝集剂的活性污泥。[12] The waste water treatment device according to [10] or [11], further comprising a sludge adding device for adding activated sludge without adding a coagulant to the tank, the The sludge adding device adds activated sludge without adding a coagulant to the tank in an amount equivalent to MLSS that is 50 times or more relative to the added amount of the coagulant.
[13]根据[9]或者[12]所述的废水处理装置，所述废水处理装置在膜分离活性污泥处理装置的上游具备标准活性污泥处理装置，所述标准活性污泥处理装置通过活性污泥中微生物进行生物处理，所述废水处理装置还具有将经过标准活性污泥处理装置处理的废水供给至所述槽中的通道与将通过标准活性污泥处理装置产生的剩余污泥作为所述未添加凝集剂的活性污泥供给至所述槽中的通道。[13] According to the wastewater treatment device described in [9] or [12], the wastewater treatment device is equipped with a standard activated sludge treatment device upstream of the membrane separation activated sludge treatment device, and the standard activated sludge treatment device passes through The microorganisms in the activated sludge carry out biological treatment, and the wastewater treatment device also has a channel for supplying the wastewater treated by the standard activated sludge treatment device to the tank and using the remaining sludge produced by the standard activated sludge treatment device as The activated sludge without adding a coagulant is supplied to the channel in the tank.
[14]根据[9]、[12]、[13]的任一项中所述的废水处理装置，其中，添加到所述槽中的未添加凝集剂的活性污泥的MLSS为6000～35000mg/L。[14] The wastewater treatment device according to any one of [9], [12], and [13], wherein the MLSS of the activated sludge without adding a coagulant added to the tank is 6,000 to 35,000 mg /L.
[15]根据[9]～[14]的任一项所述的废水处理装置，所述废水处理装置还进一步地具备反渗透膜过滤装置或纳米过滤膜过滤装置，所述反渗透膜过滤装置或纳米过滤膜过滤装置对经过膜分离活性污泥处理装置固液分离的处理水进行过滤处理。[15] The wastewater treatment device according to any one of [9] to [14], further comprising a reverse osmosis membrane filtration device or a nanofiltration membrane filtration device, the reverse osmosis membrane filtration device Or the nanofiltration membrane filtration device performs filtration treatment on the treated water that has passed through the solid-liquid separation of the membrane separation activated sludge treatment device.
[16]根据[15]所述的废水处理装置，所述废水处理装置还进一步地具备蒸发浓缩装置，所述蒸发浓缩装置对经过所述反渗透膜过滤装置或者纳米过滤膜过滤装置产生的浓缩水进行浓缩处理。[16] According to the wastewater treatment device described in [15], the wastewater treatment device is further equipped with an evaporation concentration device, and the evaporation concentration device is used to concentrate the concentrated water produced by the reverse osmosis membrane filtration device or the nanofiltration membrane filtration device. Water is concentrated.
发明的效果The effect of the invention
根据本发明的废水处理方法以及废水处理装置，可以得到抑制分离膜阻塞、高水质的处理水。According to the wastewater treatment method and the wastewater treatment apparatus of the present invention, it is possible to obtain high-quality treated water that suppresses clogging of the separation membrane.
附图说明Description of drawings
[图1]显示本发明的废水处理装置的一个实施方式的结构示意图。[ Fig. 1 ] A schematic configuration diagram showing one embodiment of the wastewater treatment apparatus of the present invention.
[图2]显示本发明的废水处理装置的其他实施方式的结构示意图。[ Fig. 2 ] A schematic structural view showing another embodiment of the wastewater treatment device of the present invention.
符号说明Symbol Description
10 膜分离活性污泥处理装置10 Membrane separation activated sludge treatment device
11 膜分离槽11 membrane separation tank
15 膜组件15 membrane components
16 凝集剂添加装置16 Coagulant adding device
17 污泥添加装置17 Sludge adding device
20 标准活性污泥处理装置20 standard activated sludge treatment unit
30 过滤装置30 filter device
40 蒸发浓缩装置40 Evaporation and concentration device
54 上清液通道54 supernatant channels
57 供给污泥通道57 Supply sludge channel
具体实施方式Detailed ways
〔废水处理方法〕〔Wastewater treatment method〕
本发明的废水处理方法，是在通过膜分离活性污泥法(MBR)处理废水时，在进行处理的槽(膜分离槽)中添加凝集剂的方法。作为本发明的废水处理方法，举例如下述第1形态，第2形态。The wastewater treatment method of the present invention is a method of adding a coagulant to a tank (membrane separation tank) where the wastewater is treated by the membrane separation activated sludge process (MBR). The wastewater treatment method of the present invention includes, for example, the following first and second aspects.
(A)本发明的废水处理方法的第1形态：(A) The first form of the wastewater treatment method of the present invention:
一种废水处理方法，相对于凝集剂的添加量，向膜分离槽中添加50倍以上的MLSS相当量的未添加凝集剂的活性污泥。A waste water treatment method, relative to the amount of coagulant added, add 50 times more than MLSS equivalent amount of activated sludge without coagulant to the membrane separation tank.
(B)本发明的废水处理方法的第2形态：(B) The second form of the wastewater treatment method of the present invention:
一种废水处理方法，相对于将要供给膜分离槽的废水中的难分解性物质的量，添加0.1～2.75倍量的凝集剂。A wastewater treatment method comprising adding a coagulant in an amount of 0.1 to 2.75 times the amount of refractory substances in wastewater to be supplied to a membrane separation tank.
以下，针对本发明的第1形态以及第2形态，以具体的实施方式显示并做说明。Hereinafter, specific embodiments of the first and second aspects of the present invention will be shown and described.
<A.第1形态中的废水处理装置的实施方式><A. Embodiment of the wastewater treatment device in the first aspect>
图1是显示本发明的废水处理方法的第1形态中，本发明的废水处理装置的一个实施方式的结构示意图。Fig. 1 is a schematic configuration diagram showing one embodiment of the wastewater treatment apparatus of the present invention in the first embodiment of the wastewater treatment method of the present invention.
该废水处理装置具备膜分离活性污泥处理装置10，该膜分离活性污泥处理装置10在通过活性污泥中的微生物对来自原水槽(省略图示)的废水进行生物处理的同时，还通过膜组件15作为分离膜对污泥与处理水(渗透水)进行固液分离处理。This wastewater treatment device is equipped with a membrane separation activated sludge treatment device 10, and the membrane separation activated sludge treatment device 10 biologically treats wastewater from a raw water tank (not shown) by microorganisms in the activated sludge, and also passes The membrane module 15 is used as a separation membrane to perform solid-liquid separation treatment on sludge and treated water (permeate water).
(膜分离活性污泥处理装置)(Membrane Separation Activated Sludge Treatment Plant)
膜分离活性污泥处理装置10具备：膜分离槽(第1曝气槽)11；配置在膜分离槽11内的底部附近的散气管12；向散气管12中供给空气的送风机13；连接散气管12与送风机13的空气导入管14；配置于膜分离槽11内与散气管12上方的膜组件15；向膜分离槽11中添加凝集剂的凝集剂添加装置16；向膜分离槽11中添加未添加凝集剂的活性污泥的污泥添加装置17；设置于处理水通道51的中间，通过对膜组件15内实施减压从而进行污泥与处理水(渗透水)的固液分离、并且将处理水输送至膜分离槽11外面的抽气泵18；将来自原水槽的废水供给至膜分离活性污泥处理装置10的废水通道50；将来自膜分离活性污泥处理装置10的处理水排出的处理水通道51；将来自膜分离活性污泥处理装置10的剩余污泥排出的剩余污泥通道52。Membrane separation activated sludge treatment device 10 has: membrane separation tank (the first aeration tank) 11; Dispersion pipe 12 arranged near the bottom in membrane separation tank 11; Air blower 13 to supply air in the diffusion pipe 12; The air inlet pipe 14 of the air pipe 12 and the blower 13; the membrane module 15 arranged in the membrane separation tank 11 and above the diffuser pipe 12; the coagulant adding device 16 for adding coagulant to the membrane separation tank 11; A sludge adding device 17 that adds activated sludge without adding a coagulant; it is arranged in the middle of the treatment water channel 51, and the solid-liquid separation of sludge and treatment water (permeate water) is carried out by implementing decompression in the membrane module 15, And the treated water is delivered to the air pump 18 outside the membrane separation tank 11; the waste water from the raw water tank is supplied to the waste water channel 50 of the membrane separation activated sludge treatment device 10; the treated water from the membrane separation activated sludge treatment device 10 is Discharged treatment water channel 51 ; excess sludge channel 52 for discharging excess sludge from membrane separation activated sludge treatment device 10 .
作为膜组件15，举例有具有公知过滤膜的膜组件。As the membrane module 15, a membrane module having a known filtration membrane is exemplified.
作为过滤膜的种类，优选微滤膜(MF膜)或者超滤膜(UF膜)。作为过滤膜的形状，举例有中空丝膜、平膜、管状膜、袋状膜等。这些之中，考虑到以容积为基础进行比较时，可能会有膜面积的高度集积，优选中空丝膜。As the type of filtration membrane, a microfiltration membrane (MF membrane) or an ultrafiltration membrane (UF membrane) is preferable. Examples of the shape of the filtration membrane include a hollow fiber membrane, a flat membrane, a tubular membrane, a bag-shaped membrane, and the like. Among these, hollow fiber membranes are preferable in consideration of the possibility of high accumulation of membrane area when comparing on a volume basis.
作为过滤膜的材质，举例有：有机材料(纤维素、聚烯烃、聚砜、聚乙烯醇、聚甲基丙烯酸甲酯、聚偏氟乙烯、聚四氟乙烯等)，金属(不锈钢等)，无机材料(陶瓷等)。过滤膜的材质可以根据废水性状做适当选择。Examples of filter membrane materials include organic materials (cellulose, polyolefin, polysulfone, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene, etc.), metals (stainless steel, etc.), Inorganic materials (ceramics, etc.). The material of the filter membrane can be properly selected according to the properties of the wastewater.
过滤膜的孔径，可以根据处理的目的做适当选择。MBR中，过滤膜的孔径优选0.001～3μm。孔径如果在0.001μm以上，则可以抑制膜的阻力变大。孔径如果在3μm以下，可以充分地分离活性污泥、维持良好的处理水的水质。过滤膜的孔径，作为微滤膜的范围时更优选0.04～1.0μm。The pore size of the filter membrane can be appropriately selected according to the purpose of treatment. In MBR, the pore diameter of the filter membrane is preferably 0.001 to 3 μm. When the pore diameter is at least 0.001 μm, the resistance of the membrane can be suppressed from increasing. If the pore size is 3 μm or less, the activated sludge can be sufficiently separated and the water quality of the treated water can be maintained at a good level. The pore diameter of the filtration membrane is more preferably 0.04 to 1.0 μm in the range of the microfiltration membrane.
膜分离活性污泥处理装置10中可以使用将散气管12与膜组件15一体化的膜单元。作为这样的膜单元，举例如日本专利特开2013-202524号公报中记载的膜单元等。The membrane unit which integrated the diffuser pipe 12 and the membrane module 15 can be used for the membrane separation activated sludge processing apparatus 10. As such a membrane unit, the membrane unit described in Unexamined-Japanese-Patent No. 2013-202524, etc. are mentioned, for example.
凝集剂添加装置16具有凝集剂通道16a与泵16b，凝集剂通道16a向膜分离槽11中供给凝集剂，泵16b设置于凝集剂通道16a的中途，将凝集剂输送至膜分离槽11。The coagulant adding device 16 has a coagulant channel 16a and a pump 16b. The coagulant channel 16a supplies the coagulant to the membrane separation tank 11, and the pump 16b is installed in the middle of the coagulant channel 16a to deliver the coagulant to the membrane separation tank 11.
污泥添加装置17具有污泥通道17a与泵17b，污泥通道17a将未添加凝集剂的活性污泥供给至膜分离槽11中，泵17b设置于污泥通道17a的中途，将未添加凝集剂的活性污泥输送至膜分离槽11。The sludge adding device 17 has a sludge channel 17a and a pump 17b. The sludge channel 17a supplies the activated sludge without coagulant to the membrane separation tank 11. The activated sludge is transported to the membrane separation tank 11.
(标准活性污泥处理装置)(Standard Activated Sludge Treatment Plant)
废水处理装置，如图2所示，可以进一步地在膜分离活性污泥处理装置10的上游具备标准活性污泥处理装置20，标准活性污泥处理装置20通过活性污泥中的微生物对来自原水槽(省略图示)的废水进行生物处理。Wastewater treatment plant, as shown in Figure 2, can further possess standard activated sludge treatment plant 20 at the upstream of membrane separation activated sludge treatment plant 10, and standard activated sludge treatment plant 20 passes through the microorganism in the activated sludge to from original Wastewater from a water tank (not shown) is subjected to biological treatment.
此外，图2中，与图1在相同的构件上标示了相同的符号，省略对其的说明。In addition, in FIG. 2, the same code|symbol is attached|subjected to the same member as FIG. 1, and the description is abbreviate|omitted.
标准活性污泥处理装置20具有：活性污泥槽(第2曝气槽)21；配置于活性污泥槽21内的靠近底部的散气管22；向散气管22中供给空气的送风机23；连接散气管22与送风机23的空气导入管24；将活性污泥槽21中经过生物处理的活性污泥槽混合水固液分离为污泥与上清液的沉淀槽25；将来自原水槽的废水供给至活性污泥槽21的废水通道50；将活性污泥槽21中经过生物处理的活性污泥槽混合水移送到沉淀槽25内的活性污泥槽混合水通道53；将来自沉淀槽25的上清液移送至膜分离活性污泥处理装置10的上清液通道54；将剩余污泥从沉淀槽25中排出的剩余污泥通道55；将剩余污泥的一部分从沉淀槽25中返送至活性污泥槽21的返送污泥通道56；将剩余污泥的一部分作为未添加凝集剂的活性污泥从沉淀槽25供给至膜分离槽11的供给污泥通道57。Standard activated sludge treatment device 20 has: activated sludge tank (the 2nd aeration tank) 21; Dispersing pipe 22 near the bottom that is configured in activated sludge tank 21; Air blower 23 that supplies air in diffused pipe 22; The air introduction pipe 24 of the diffuser pipe 22 and the blower 23; the sedimentation tank 25 for separating the solid-liquid of the biologically treated activated sludge tank mixed water into sludge and supernatant in the activated sludge tank 21; the waste water from the raw water tank Supply to the wastewater channel 50 of the activated sludge tank 21; the activated sludge tank mixed water through biological treatment in the activated sludge tank 21 is moved to the activated sludge tank mixed water channel 53 in the settling tank 25; The supernatant is transferred to the supernatant channel 54 of the membrane separation activated sludge treatment device 10; the excess sludge is discharged from the excess sludge channel 55 in the settling tank 25; a part of the excess sludge is returned from the settling tank 25 Return sludge passage 56 to activated sludge tank 21 ; supply sludge passage 57 of membrane separation tank 11 from sedimentation tank 25 to supply a part of excess sludge as activated sludge to which coagulant is not added.
沉淀槽25只要是能够通过重力沉淀使由活性污泥槽21移送过来的活性污泥槽混合水固液分离为污泥与上清液的即可以，对其没有特别的限制。沉淀槽25可以是一般的沉淀池。The settling tank 25 is not particularly limited as long as it can separate the mixed water in the activated sludge tank transferred from the activated sludge tank 21 into solid and liquid by gravity sedimentation into sludge and supernatant. The sedimentation tank 25 can be a general sedimentation tank.
图2所示的废水处理装置中，污泥添加装置17由供给污泥通道57与泵17b构成，泵17b设置于供给污泥通道57的中途，其将未添加凝集剂的活性污泥送至膜分离槽11中。In the wastewater treatment plant shown in Figure 2, the sludge addition device 17 is made of a supply sludge passage 57 and a pump 17b, and the pump 17b is arranged in the middle of the supply sludge passage 57, which sends the activated sludge without coagulant to In the membrane separation tank 11.
(过滤装置)(filter device)
废水处理装置，如图2所示，还可以进一步地具备过滤装置30，过滤装置30对通过膜组件15、从处理水通道51排出的处理水(渗透水)进行过滤处理。As shown in FIG. 2 , the waste water treatment device may further include a filter device 30 for filtering the treated water (permeated water) that passes through the membrane module 15 and is discharged from the treated water channel 51 .
过滤装置30具有：过滤装置主体31；将通过过滤装置主体31的纯净水排出的纯净水通道58；将没有通过过滤装置主体31的浓缩水排出的浓缩水通道59。The filter device 30 has: a filter device main body 31 ; a purified water passage 58 for discharging purified water passing through the filter device main body 31 ; and a concentrated water passage 59 for discharging concentrated water that has not passed through the filter device main body 31 .
作为过滤装置主体31，举例有具有反渗透膜组件或者纳米过滤膜组件的过滤装置主体。在这里，将作为过滤装置主体31的具有反渗透膜组件的过滤装置30称为反渗透膜过滤装置，将作为过滤装置主体31的具有纳米过滤膜组件的过滤装置30称为纳米过滤膜过滤装置。As the filter main body 31, a filter main body having a reverse osmosis membrane module or a nanofiltration membrane module is exemplified. Here, the filter device 30 with the reverse osmosis membrane module as the filter device main body 31 is called the reverse osmosis membrane filter device, and the filter device 30 with the nanofiltration membrane module as the filter device main body 31 is called the nanofiltration membrane filter device .
反渗透膜组件只要是能够将通过反渗透膜的纯净水与不通过反渗透膜的浓缩水进行分离的形态即可以，对其没有特别限制。The reverse osmosis membrane module is not particularly limited as long as it can separate the purified water passing through the reverse osmosis membrane and the concentrated water not passing through the reverse osmosis membrane.
作为反渗透膜组件，举例如所谓的螺旋型反渗透膜组件等，其将反渗透膜在集水管的周面上卷绕成的圆柱状的反渗透膜元件收纳至圆筒状的套管中。As the reverse osmosis membrane module, for example, the so-called spiral reverse osmosis membrane module, etc., the cylindrical reverse osmosis membrane element in which the reverse osmosis membrane is wound on the peripheral surface of the water collection pipe is accommodated in a cylindrical casing. .
作为反渗透膜的材质，举例有聚酰胺、聚砜、醋酸纤维素等，优选含有芳香族聚酰胺或者交联芳香族聚酰胺的聚酰胺。Examples of the material of the reverse osmosis membrane include polyamide, polysulfone, and cellulose acetate, and polyamide containing aromatic polyamide or cross-linked aromatic polyamide is preferable.
纳米过滤膜组件只要是能够将通过纳米过滤膜的纯净水与不通过纳米过滤膜的浓缩水进行分离的形态即可以，对其没有特别限制。The nanofiltration membrane module is not particularly limited as long as it can separate the pure water passing through the nanofiltration membrane from the concentrated water not passing through the nanofiltration membrane.
作为纳米过滤膜组件，举例如所谓的螺旋型纳米过滤膜组件等，其将纳米过滤膜在集水管的周面上卷绕成的圆柱状的纳米过滤膜元件收纳至圆筒状的套管中。As the nanofiltration membrane module, for example, the so-called spiral nanofiltration membrane module, etc., the cylindrical nanofiltration membrane element in which the nanofiltration membrane is wound on the peripheral surface of the water collection pipe is accommodated in a cylindrical sleeve .
作为纳米过滤膜的材质，举例有含有聚乙烯系、芳香族聚酰胺系或交联聚酰胺系的聚酰胺系，脂肪胺缩聚物、杂环聚合物系、聚乙烯醇系、醋酸纤维素系聚合物等。Examples of materials for nanofiltration membranes include polyethylene-based, aromatic polyamide-based or cross-linked polyamide-based polyamide-based, aliphatic amine polycondensate, heterocyclic polymer-based, polyvinyl alcohol-based, and cellulose acetate-based polymer etc.
(蒸发浓缩装置)(evaporative concentration device)
废水处理装置，如图2所示，还可以进一步地具备蒸发浓缩装置40，蒸发浓缩装置40对未通过过滤装置主体31的浓缩水进行浓缩处理。As shown in FIG. 2 , the waste water treatment device may further include an evaporation concentration device 40 that concentrates the concentrated water that has not passed through the filter device main body 31 .
蒸发浓缩装置40具有：蒸发器41；将在蒸发器41中蒸发、凝结的凝结水排出的凝结水通道60；将蒸发器41中浓缩的浓缩废水排出的浓缩废水通道61。The evaporation and concentration device 40 has: an evaporator 41 ; a condensed water channel 60 for discharging the condensed water evaporated and condensed in the evaporator 41 ; and a concentrated wastewater channel 61 for discharging the concentrated wastewater concentrated in the evaporator 41 .
蒸发器41只要是可以对浓缩水进行加热浓缩的形态即可以，对其没有特别限制。The evaporator 41 is not particularly limited as long as it can heat and concentrate concentrated water.
<A.第1形态中的废水处理方法的实施方式><A. Embodiment of the wastewater treatment method in the first aspect>
使用图1的废水处理装置的废水处理方法，具有下述步骤(b)，使用图2的废水处理装置的废水处理方法具有下述步骤(b)，根据需要具有下述(a)、(c)、(d)。Use the waste water treatment method of the waste water treatment device of Fig. 1, have following step (b), use the waste water treatment method of Fig. 2 waste water treatment device to have following step (b), have following (a), (c as required ), (d).
(a)标准活性污泥处理装置20中，通过活性污泥中的微生物对来自原水槽(省略图示)的废水进行生物处理的步骤。(a) In the standard activated sludge treatment device 20 , a step of biologically treating wastewater from a raw water tank (not shown) with microorganisms in the activated sludge.
(b)膜分离活性污泥处理装置10中，在通过活性污泥中的微生物对来自原水槽(省略图示)的废水或者步骤(a)中经过处理的废水(上清液)进行生物处理的同时，通过膜组件15进行固液分离成为污泥与处理水(渗透水)的步骤。(b) In the membrane separation activated sludge treatment device 10, the wastewater from the raw water tank (not shown) or the treated wastewater (supernatant) in step (a) is biologically treated by microorganisms in the activated sludge At the same time, the step of solid-liquid separation into sludge and treated water (permeate water) is carried out through the membrane module 15.
(c)过滤装置30中，通过反渗透膜或者纳米过滤膜对通过膜组件15的处理水(渗透水)进行过滤处理的步骤。(c) In the filtration device 30 , a step of filtering the treated water (permeated water) passing through the membrane module 15 through a reverse osmosis membrane or a nanofiltration membrane.
(d)蒸发浓缩装置40中，对没有通过过滤装置主体31的浓缩水进行浓缩处理的步骤。(d) In the evaporative concentration device 40 , a step of concentrating the concentrated water that has not passed through the filter device main body 31 .
(废水)(Wastewater)
在废水处理装置中经过处理的废水通常含有易分解性物质或难分解性物质等有机物。作为这样的废水，举例如生活废水、工业废水(化学、制药、造纸、饮料、炼油、半导体、电子等)、畜业废水等。Wastewater treated in a wastewater treatment plant usually contains organic substances such as readily decomposable substances or hardly decomposable substances. Examples of such wastewater include domestic wastewater, industrial wastewater (chemical, pharmaceutical, paper, beverage, oil refinery, semiconductor, electronics, etc.), livestock wastewater, and the like.
可以对废水预先除去粗大的浮游物、土砂等，调整pH，稀释。It is possible to pre-remove coarse floating solids, soil sand, etc. from wastewater, adjust pH, and dilute.
(步骤(a))(step (a))
步骤(b)中经过处理的废水，也可以预先在标准活性污泥处理装置20中进行处理。The wastewater treated in step (b) can also be treated in a standard activated sludge treatment device 20 in advance.
步骤(a)中，首先将储存在原水槽(省略图示)中的废水经由废水通道50供给至标准活性污泥处理装置20的活性污泥槽21中。In step (a), first, the waste water stored in the raw water tank (not shown in the figure) is supplied to the activated sludge tank 21 of the standard activated sludge treatment device 20 through the waste water channel 50 .
活性污泥槽21中，使送风机23运作，由散气管22引入空气，通过对活性污泥中的微生物供给氧从而进行废水的生物处理。In the activated sludge tank 21, the blower 23 is operated, air is introduced from the diffuser pipe 22, and the biological treatment of waste water is performed by supplying oxygen to microorganisms in the activated sludge.
接着，将活性污泥槽21中经过生物处理的活性污泥槽混合水经由活性污泥槽混合水通道53输送至沉淀槽25中。Next, the biologically treated activated sludge tank mixed water in the activated sludge tank 21 is transported to the sedimentation tank 25 through the activated sludge tank mixed water channel 53 .
沉淀槽25中，通过重力沉淀将活性污泥槽混合水固液分离为污泥与上清液。In the settling tank 25, the mixed water in the activated sludge tank is separated into solid and liquid by gravity sedimentation into sludge and supernatant.
沉淀槽25的上清液，作为步骤(b)中经过处理的废水，经由上清液通道54被输送到膜分离活性污泥处理装置10中。The supernatant from the sedimentation tank 25 is sent to the membrane separation activated sludge treatment device 10 via the supernatant channel 54 as the treated wastewater in step (b).
另一方面，分离出的剩余污泥经由剩余污泥通道55被排出。此外，因为剩余污泥中含有微生物，所以剩余污泥的一部分经由返送污泥通道56被返送至活性污泥槽21中，再次用于废水的生物处理。进一步地，因为标准活性污泥处理装置20中产生的剩余污泥没有添加凝集剂，所以优选剩余污泥的一部分作为未添加凝集剂的活性污泥，经由供给污泥通道57供给到膜分离活性污泥处理装置10的膜分离槽11中。On the other hand, the separated excess sludge is discharged through the excess sludge passage 55 . In addition, since the excess sludge contains microorganisms, a part of the excess sludge is returned to the activated sludge tank 21 via the return sludge passage 56, and is used again for biological treatment of wastewater. Further, because the excess sludge produced in the standard activated sludge treatment device 20 does not have a coagulant added, it is preferable that a part of the excess sludge is supplied to the membrane separation activity via the sludge supply channel 57 as activated sludge without an added coagulant. In the membrane separation tank 11 of the sludge treatment device 10.
(步骤(b))(step (b))
废水处理方法不具有步骤(a)时，将储存在原水槽(省略图示)中的废水经由废水通道50供给至膜分离活性污泥处理装置10的膜分离槽11中。When the wastewater treatment method does not have step (a), the wastewater stored in the raw water tank (not shown) is supplied to the membrane separation tank 11 of the membrane separation activated sludge treatment device 10 through the wastewater channel 50 .
废水处理方法具有步骤(a)时，将步骤(a)中经过处理的废水(上清液)经由上清液通道54供给至膜分离活性污泥处理装置10的膜分离槽11中。When the wastewater treatment method has step (a), the wastewater (supernatant) treated in step (a) is supplied to the membrane separation tank 11 of the membrane separation activated sludge treatment device 10 through the supernatant passage 54 .
膜分离槽11中，使送风机13运作，由散气管12引入空气，通过对活性污泥中的微生物供给氧从而进行废水的生物处理。In the membrane separation tank 11, the air blower 13 is operated, air is introduced from the diffuser pipe 12, and the biological treatment of wastewater is carried out by supplying oxygen to microorganisms in the activated sludge.
此外，膜分离槽11中，通过使抽气泵18运作对膜组件15内减压，将混合水固液分离为污泥与处理水(渗透水)。此时，通过散气管12将空气导入到膜组件15中，可以边洗涤膜组件15的分离膜(例如中空丝膜等)的表面，边高效地进行固液分离。In addition, in the membrane separation tank 11, the inside of the membrane module 15 is decompressed by operating the suction pump 18, and the mixed water is solid-liquid separated into sludge and treated water (permeate water). At this time, air is introduced into the membrane module 15 through the diffuser pipe 12, and solid-liquid separation can be performed efficiently while washing the surface of the separation membrane (such as a hollow fiber membrane) of the membrane module 15.
步骤(b)中，通过凝集剂添加装置16在膜分离槽11中添加凝集剂对废水进行处理。In step (b), the wastewater is treated by adding a coagulant to the membrane separation tank 11 through the coagulant adding device 16 .
凝集剂的添加量，只要是可以凝集废水中的有机物(特别是难分解性物质)的量就没有特别限制，例如相对于将要供给到膜分离槽11中的废水中的难分解性物质的量，优选0.1～2.75倍量，更优选0.2～2.5倍量，特别优选0.25～2.0倍量。The amount of the coagulant added is not particularly limited as long as it is an amount that can coagulate organic matter (especially refractory substances) in wastewater, for example, relative to the amount of refractory substances in wastewater to be supplied to the membrane separation tank 11 , preferably 0.1 to 2.75 times the amount, more preferably 0.2 to 2.5 times the amount, particularly preferably 0.25 to 2.0 times the amount.
此外，步骤(b)中，通过污泥添加装置17向膜分离槽11中添加未添加凝集剂的活性污泥。废水处理方法具有步骤(a)时，优选将标准活性污泥处理装置20中产生的剩余污泥的一部分作为未添加凝集剂的活性污泥，经由供给污泥通道57供给至膜分离活性污泥处理装置10的膜分离槽11中。Moreover, in step (b), the activated sludge to which the coagulant was not added is added to the membrane separation tank 11 by the sludge addition apparatus 17. When the wastewater treatment method has step (a), it is preferable to supply a part of the excess sludge generated in the standard activated sludge treatment device 20 as activated sludge without adding a coagulant to the membrane separation activated sludge through the sludge supply channel 57 In the membrane separation tank 11 of the processing device 10.
未添加凝集剂的活性污泥的添加量，相对于添加到膜分离槽11中的凝集剂的添加量，为50倍以上的MLSS相当量。未添加凝集剂的活性污泥的添加量在50倍以上时，则意味着膜分离槽11内存在充足量的活性污泥，即使向膜分离槽11中过量添加凝集剂，凝集剂也会吸附在活性污泥上，不容易在处理水中残存。而且，凝集剂吸附在活性污泥上时，也吸附难分解性物质等有机物。因此，可以抑制凝集剂或难分解性物质等引起的膜组件15的膜阻塞。此外，如上所述，处理水中溶解的凝集剂透过膜组件15的情况下，凝集剂变成处理水的污染原因。The addition amount of the activated sludge to which no flocculant was added was MLSS equivalent amount 50 times or more with respect to the addition amount of the flocculant added to the membrane separation tank 11. When the amount of activated sludge without coagulant added is more than 50 times, it means that there is a sufficient amount of activated sludge in the membrane separation tank 11. Even if the coagulant is excessively added to the membrane separation tank 11, the coagulant will also adsorb On activated sludge, it is not easy to remain in the treated water. Furthermore, when the coagulant is adsorbed on the activated sludge, it also adsorbs organic substances such as hardly decomposable substances. Therefore, membrane clogging of the membrane module 15 caused by coagulants, refractory substances, and the like can be suppressed. Furthermore, as described above, when the coagulant dissolved in the treated water permeates the membrane module 15, the coagulant becomes a cause of contamination of the treated water.
但是，如果让凝集剂吸附于未添加凝集剂的活性污泥时，处理水中溶解的凝集剂的比例也会减小，所以透过膜组件15的凝集剂的比例减少。因此可以得到水质高的处理水。However, when the coagulant is adsorbed to the activated sludge to which no coagulant has been added, the proportion of the coagulant dissolved in the treated water also decreases, so the proportion of the coagulant permeating the membrane module 15 decreases. Therefore, high-quality treated water can be obtained.
有这样的倾向，未添加凝集剂的活性污泥的添加量越多，越容易得到处理水中的凝集剂的残存抑制效果。只是，过量添加未添加凝集剂的活性污泥有出现下述问题的担忧：(i)污泥添加装置17大型化，(ii)有扰乱膜分离槽11的菌群的风险，从而不能顺利地进行生物处理，(iii)凝集剂优先吸着在活性污泥上，作为凝集剂本来目的的难分解性物质等膜阻塞物质的除去效果下降。因此，未添加凝集剂的活性污泥的添加量，相对于膜分离槽11中添加的凝集剂的添加量，优选200倍以下的MLSS相当量。There is such a tendency that the more the amount of activated sludge to which no coagulant is added is increased, the easier it is to obtain the effect of suppressing the remaining of the coagulant in treated water. However, excessive addition of activated sludge without adding a coagulant may cause the following problems: (i) the sludge addition device 17 is enlarged, (ii) there is a risk of disturbing the flora of the membrane separation tank 11, so that it cannot be smoothly In the case of biological treatment, (iii) the coagulant is preferentially adsorbed on the activated sludge, and the effect of removing membrane clogging substances such as refractory substances, which are the original purpose of the coagulant, is reduced. Therefore, the addition amount of the activated sludge to which no flocculant is added is preferably 200 times or less the equivalent amount of MLSS with respect to the addition amount of the flocculant added to the membrane separation tank 11 .
另外，“未添加凝集剂的活性污泥”是指没有添加凝集剂，即表面等没有附着凝集剂的活性污泥。In addition, "activated sludge to which a coagulant is not added" refers to activated sludge to which no coagulant is added, that is, no coagulant is adhered to the surface or the like.
此外，“MLSS”为活性污泥的浓度指标，按照JIS K 0102测定活性污泥蒸发、干燥后的剩余量后将其求出。In addition, "MLSS" is an indicator of the concentration of activated sludge, which is obtained by measuring the remaining amount of activated sludge after evaporation and drying according to JIS K 0102.
步骤(b)中的膜分离槽11中添加的未添加凝集剂的活性污泥的MLSS，优选为6000～35000mg/L，更优选为8000～12000mg/L。未添加凝集剂的活性污泥的MLSS过稀薄时，则在膜分离槽11中添加大量的未添加凝集剂的活性污泥，增加了成本。另一方面，未添加凝集剂的活性污泥的MLSS过浓时，粘度变高，要花费工夫进行未添加凝集剂的活性污泥的供给。此外，污泥通道17a、供给污泥通道57、泵17b有闭塞的情形。The MLSS of the activated sludge without coagulant added to the membrane separation tank 11 in step (b) is preferably 6000-35000 mg/L, more preferably 8000-12000 mg/L. When the MLSS of the activated sludge without coagulant addition is too thin, a large amount of activated sludge without coagulant addition is added to the membrane separation tank 11, which increases the cost. On the other hand, when the MLSS of the activated sludge which does not add a coagulant is too thick, the viscosity will become high, and it will take time to supply the activated sludge which does not add a coagulant. In addition, the sludge passage 17a, the supply sludge passage 57, and the pump 17b may be blocked.
步骤(b)中，膜组件15中分离出的剩余污泥经由剩余污泥通道52被排出。另外，因为剩余污泥中包含微生物，所以剩余污泥的一部分可以返送至膜分离活性污泥处理装置10中，再次用于废水的生物处理。In step (b), the excess sludge separated from the membrane module 15 is discharged through the excess sludge channel 52 . In addition, because the excess sludge contains microorganisms, a part of the excess sludge can be returned to the membrane separation activated sludge treatment device 10 and used again for biological treatment of wastewater.
作为步骤(b)中所使用的凝集剂没有特别限制，优选高分子凝集剂。高分子凝集剂具有通过使微小凝块交联形成粗大凝块的作用。此外，高分子凝集剂，根据凝集剂具有的吸附活性基团，有非离子系、阴离子系以及阳离子系等。特别是从处理效率方面出发，作为步骤(b)中所使用的凝集剂，优选具有下述式(1)以及/或者(2)所示的脒结构单元的阳离子性聚合体作为其有效成分而含有的脒系凝集剂。The coagulant used in the step (b) is not particularly limited, and a polymer coagulant is preferred. The polymer coagulant has the function of cross-linking micro-clots to form macro-clots. In addition, polymer flocculants include nonionic, anionic, cationic, and the like, depending on the adsorption active groups the flocculant has. Especially from the aspect of processing efficiency, as the coagulant used in the step (b), it is preferable to have a cationic polymer having an amidine structural unit represented by the following formula (1) and/or (2) as its active ingredient. Contains an amidine coagulant.
另外，本发明中“有效成分”意味着100质量％凝集剂中的阳离子性聚合体的含量，通常优选含有10～100质量％。In addition, "active ingredient" in this invention means content of the cationic polymer in 100 mass % of flocculents, Usually, it is preferable to contain 10-100 mass %.
[化1][chemical 1]
式(1)、(2)中，R1～R4分别为氢原子或者甲基，可以相同或者不同。In formulas (1) and (2), R1 to R4 are each a hydrogen atom or a methyl group, and may be the same or different.
X－、Y－分别为阴离子，可以相同或者不同。作为阴离子，举例如Cl－、BR－、1/2SO42－、CH3(CO)O－、H(CO)O－等。其中优选Cl－。X− and Y− are respectively anions, which may be the same or different. Examples of anions include Cl− , BR− , 1/2SO42− , CH3 (CO)O− , H(CO)O− and the like. Among them, Cl− is preferred.
作为这样的阳离子性聚合体的制造方法没有特别限制，举例如下述方法，制造乙烯性不饱和单体与丙烯腈或者甲基丙烯腈的腈类的共聚物，酸水解后，使该共聚物中的氰基与伯胺基反应而脒化的方法，其中，所述乙烯性不饱和单体具有伯胺基或者能够通过转换反应生成伯胺基的取代氨基。The production method of such a cationic polymer is not particularly limited. For example, the following method is used to produce a nitrile copolymer of an ethylenically unsaturated monomer and acrylonitrile or methacrylonitrile, and after acid hydrolysis, make the copolymer The method of reacting the cyano group with the primary amino group for amidinization, wherein the ethylenically unsaturated monomer has a primary amino group or a substituted amino group capable of generating a primary amino group through a conversion reaction.
阳离子性聚合体，优选通过最典型的下述方法制造，令N-乙烯基甲酰胺和丙烯腈共聚，通常在水悬浮液盐酸的存在下加热生成的共聚物，由与取代氨基相邻接的氰基形成脒结构单元而制造。这样的话，根据用于共聚的N-乙烯基甲酰胺与丙烯腈的摩尔比，以及所选的共聚物的脒化条件可以得到各种组成的阳离子性聚合体。The cationic polymer is preferably produced by the most typical method of copolymerizing N-vinylformamide and acrylonitrile, usually by heating the resulting copolymer in the presence of hydrochloric acid in aqueous suspension, composed of adjacent substituted amino groups The cyano group is produced by forming an amidine structural unit. In this way, cationic polymers of various compositions can be obtained depending on the molar ratio of N-vinylformamide to acrylonitrile used for copolymerization and the selected amidineization conditions of the copolymer.
对于阳离子性聚合体，该阳离子性聚合体100摩尔％中，优选含有5～90摩尔％上述式(1)以及/或者(2)所表示的脒结构单元作为重复单元。脒结构单元的含有率不足5摩尔％时，因为脒结构单元的含量太少，当该阳离子性聚合体作为凝集剂使用时，其使用量会变多。另一方面，脒结构单元的含有率超过90摩尔％的阳离子性聚合体，难以通过上述方法制造。脒结构单元的含有率的下限值，更优选在10摩尔％以上，进一步地优选15摩尔％以上，特别优选20摩尔％以上。此外，脒结构单元的含有率的上限值，更优选85摩尔％以下，进一步地优选80摩尔％以下。The cationic polymer preferably contains 5 to 90 mol% of the amidine structural unit represented by the above formula (1) and/or (2) as a repeating unit in 100 mol% of the cationic polymer. When the content of the amidine structural unit is less than 5 mol %, since the content of the amidine structural unit is too small, when the cationic polymer is used as an aggregating agent, the amount used will increase. On the other hand, it is difficult to produce a cationic polymer having an amidine structural unit content of more than 90 mol % by the above method. The lower limit of the content of the amidine structural unit is more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more. In addition, the upper limit of the content rate of the amidine structural unit is more preferably 85 mol% or less, further preferably 80 mol% or less.
另外，阳离子性聚合体通过上述方法制造时，除所述脒结构单元之外，有时还含有下述式(3)～(5)所表示的单位。Moreover, when a cationic polymer is manufactured by the said method, it may contain the unit represented by following formula (3)-(5) other than the said amidine structural unit.
[化2][Chem 2]
式(3)～(5)中，R5、R7、R8分别为氢原子或者甲基，可以相同或者不同。In formulas (3) to (5), R5 , R7 , and R8 are each a hydrogen atom or a methyl group, and may be the same or different.
R6是碳原子数1～4的烷基或者氢原子。R6 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
Z－是阴离子。作为阴离子，与前面在上述式(1)、(2)的说明中示例过阴离子相同。Z- is an anion. As the anion, it is the same as the peranion exemplified above in the description of the above-mentioned formulas (1) and (2).
阳离子性聚合体含有上述式(3)～(5)所表示的单位时，通常，该阳离子性聚合体100摩尔％中，含有上述式(3)所表示的重复单元0～40摩尔％，上述式(4)所表示的重复单元0～70摩尔％，上述式(5)所表示的重复单元0～70摩尔％。When the cationic polymer contains units represented by the above formulas (3) to (5), usually, in 100 mol% of the cationic polymer, 0 to 40 mol% of the repeating unit represented by the above formula (3) is contained, and the above The repeating unit represented by the formula (4) is 0 to 70 mol%, and the repeating unit represented by the above formula (5) is 0 to 70 mol%.
上述式(1)以及/或者(2)所表示的脒结构单元，以及上述式(3)～(5)所表示的单位的组成，可以通过乙烯性不饱和单体与腈类的聚合摩尔比，或脒化反应的条件(温度或时间)来调整。The amidine structural unit represented by above-mentioned formula (1) and/or (2), and the composition of the unit represented by above-mentioned formula (3)～(5), can pass through the polymerization mole ratio of ethylenically unsaturated monomer and nitriles , or the conditions (temperature or time) of the amidinization reaction are adjusted.
此外，这些组成可以通过测定阳离子性聚合体的13C-NMR(13C-核磁共振)来求出，具体地，通过与各重复单元相对应的13C-NMR光谱的峰(信号)的积分值来算出。In addition, these compositions can be determined by measuring the13 C-NMR (13 C-nuclear magnetic resonance) of the cationic polymer, specifically, by integrating the peaks (signals) of the13 C-NMR spectrum corresponding to each repeating unit value to calculate.
(步骤(c))(step (c))
步骤(b)中，虽然通过膜组件15的处理水(渗透水)，可以直接排放到外部，但是优选经由处理水通道51输送至过滤装置30，通过反渗透膜或者纳米过滤膜进行过滤处理。In step (b), although the treated water (permeated water) passing through the membrane module 15 can be directly discharged to the outside, it is preferably sent to the filter device 30 through the treated water channel 51, and filtered through a reverse osmosis membrane or a nanofiltration membrane.
过滤装置30中，通过反渗透膜或者纳米过滤膜的处理水成为纯净水，通过纯净水通道58被排出。另一方面，没有通过反渗透膜或者纳米过滤膜的处理水成为浓缩水，通过浓缩水通道59被排出。In the filter device 30 , the treated water passing through the reverse osmosis membrane or the nanofiltration membrane becomes purified water, and is discharged through the purified water channel 58 . On the other hand, treated water that has not passed through the reverse osmosis membrane or the nanofiltration membrane becomes concentrated water and is discharged through the concentrated water passage 59 .
(步骤(d))(step (d))
步骤(c)中，没有通过反渗透膜或者纳米过滤膜的处理水(浓缩水)虽然可以直接排放到外部，但是优选经由浓缩水通道59输送至蒸发浓缩装置40，进行浓缩处理。In step (c), the treated water (concentrated water) that has not passed through the reverse osmosis membrane or the nanofiltration membrane can be directly discharged to the outside, but it is preferably sent to the evaporative concentration device 40 through the concentrated water channel 59 for concentration treatment.
蒸发浓缩装置40中，送至蒸发器41中的浓缩水，被省略图示的传热器加热后蒸发，成为水蒸气。水蒸气被省略图示的冷却器冷却后凝结，成为凝结水，通过凝结水通道60被排出。蒸发器41中被浓缩的浓缩水作为浓缩废水通过浓缩废水通道61被排出。In the evaporative concentration device 40 , the concentrated water sent to the evaporator 41 is heated by a heat exchanger (not shown) and evaporated to become water vapor. The water vapor is cooled by a cooler (not shown) and then condensed to become condensed water, which is discharged through the condensed water passage 60 . The concentrated water concentrated in the evaporator 41 is discharged through the concentrated waste water passage 61 as concentrated waste water.
蒸发浓缩装置40中对浓缩水进行浓缩处理时，为了防止蒸发浓缩装置40的腐蚀，可以在浓缩水中添加氢氧化钠等碱。When the concentrated water is concentrated in the evaporating and concentrating device 40 , in order to prevent corrosion of the evaporating and concentrating device 40 , an alkali such as sodium hydroxide may be added to the concentrated water.
虽然浓缩废水可以直接排出到外部，但是通常将其干燥后以固体物质的状态被排出。Although the concentrated waste water can be directly discharged to the outside, it is usually discharged in the state of solid matter after being dried.
(作用效果)(Effect)
以上所述的本发明的废水处理方法以及废水处理装置的第1形态中，通过MBR，添加凝集剂处理废水时，在膜分离槽中添加特定量的未添加凝集剂的活性污泥。因此，由于膜分离槽内存在充分量的活性污泥，即使向膜分离槽中过量添加凝集剂，凝集剂也会吸附在活性污泥上，不容易在处理水中残存。而且当凝集剂吸附在活性污泥上时，也会吸附难分解性物质等有机物。因此，可以抑制凝集剂或难分解性物质等引起的膜组件的膜阻塞。此外，如果使凝集剂吸附在未添加凝集剂的活性污泥上，处理水中溶解的凝集剂的比例会减少，所以经过膜组件的凝集剂的比例会减少。因此得到了高水质的处理水。In the first aspect of the wastewater treatment method and wastewater treatment apparatus of the present invention described above, when wastewater is treated by adding a coagulant by MBR, a specific amount of activated sludge without a coagulant is added to the membrane separation tank. Therefore, since there is a sufficient amount of activated sludge in the membrane separation tank, even if the coagulant is excessively added to the membrane separation tank, the coagulant will be adsorbed on the activated sludge and will not easily remain in the treated water. Moreover, when the coagulant is adsorbed on the activated sludge, it will also adsorb organic substances such as refractory substances. Therefore, membrane clogging of the membrane module caused by coagulants, refractory substances, and the like can be suppressed. In addition, if the coagulant is adsorbed on the activated sludge to which no coagulant is added, the proportion of the coagulant dissolved in the treated water decreases, so the proportion of the coagulant passing through the membrane module decreases. Therefore, high-quality treated water is obtained.
(其他的实施方式)(other embodiments)
另外，本发明的废水处理方法以及废水处理装置的第1形态并不限定于图示例的废水处理装置以及利用该装置的废水处理方法。In addition, the first aspect of the waste water treatment method and the waste water treatment apparatus of the present invention is not limited to the waste water treatment apparatus and the waste water treatment method using the apparatus of the illustrated example.
例如，图2所示的废水处理装置中，将标准活性污泥处理装置20所产生的剩余污泥的一部分，作为未添加凝集剂的活性污泥供给到膜分离活性污泥处理装置10的膜分离槽11中，也可以将活性污泥槽21中的活性污泥作为未添加凝集剂的活性污泥供给到膜分离槽11中。只是，因将剩余污泥作为未添加凝集剂的活性污泥添加的这一方，可以减少进行废弃处理的剩余污泥的量，故而优选。For example, in the wastewater treatment plant shown in Figure 2, a part of the excess sludge produced by the standard activated sludge treatment plant 20 is supplied to the membrane of the membrane separation activated sludge treatment plant 10 as activated sludge without adding a coagulant. In the separation tank 11, the activated sludge in the activated sludge tank 21 may be supplied to the membrane separation tank 11 as the activated sludge to which the flocculant was not added. However, it is preferable to add excess sludge as activated sludge to which no flocculant is added because the amount of excess sludge to be disposed of can be reduced.
<B.第2形态中的废水处理装置的实施方式><B. Embodiment of the wastewater treatment device in the second aspect>
本发明的废水处理方法的第2形态中的本发明的废水处理装置，如图1所示，该废水处理装置具备膜分离活性污泥处理装置10，该膜分离活性污泥处理装置10在通过活性污泥中的微生物对来自原水槽(省略图示)的废水进行生物处理的同时，还通过作为分离膜的膜组件15固液分离处理为污泥与处理水(渗透水)。The waste water treatment plant of the present invention in the 2nd aspect of the waste water treatment method of the present invention, as shown in Figure 1, this waste water treatment plant is equipped with membrane separation activated sludge treatment device 10, and this membrane separation activated sludge treatment device 10 passes through The microorganisms in the activated sludge biologically treat the wastewater from the raw water tank (not shown in the figure), and also separate the solid and liquid into sludge and treated water (permeate water) through the membrane module 15 as a separation membrane.
此外，废水处理装置，如图2所示，可以在膜分离活性污泥处理装置10的上游装备标准活性污泥处理装置20，也可以在膜分离活性污泥处理装置10的下游装备过滤装置30或蒸发浓缩装置40。In addition, the wastewater treatment plant, as shown in Figure 2, can be equipped with a standard activated sludge treatment plant 20 upstream of the membrane separation activated sludge treatment plant 10, and can also equip a filter device 30 downstream of the membrane separation activated sludge treatment plant 10 Or evaporative concentration device 40.
作为膜分离活性污泥处理装置10、标准活性污泥处理装置20、过滤装置30、蒸发浓缩装置40，举例有在第1形态中的废水处理装置的实施方式说明中已经例示过的各个装置。As the membrane separation activated sludge treatment device 10 , the standard activated sludge treatment device 20 , the filter device 30 , and the evaporation concentration device 40 , each of the devices already exemplified in the description of the embodiment of the wastewater treatment device in the first embodiment is exemplified.
<B.第2形态中的废水处理方法的实施方式><B. Embodiment of the wastewater treatment method in the second aspect>
使用图1的废水处理装置的废水处理方法，具有下述步骤(b)，使用图2的废水处理装置的废水处理方法具有下述步骤(b)，根据需要具有下述(a)、(c)、(d)。Use the waste water treatment method of the waste water treatment device of Fig. 1, have following step (b), use the waste water treatment method of Fig. 2 waste water treatment device to have following step (b), have following (a), (c as required ), (d).
(a)标准活性污泥处理装置20中，通过活性污泥中的微生物对来自原水槽(省略图示)的废水进行生物处理的步骤。(a) In the standard activated sludge treatment device 20 , a step of biologically treating wastewater from a raw water tank (not shown) with microorganisms in the activated sludge.
(b)膜分离活性污泥处理装置10中，在通过活性污泥中的微生物对来自原水槽(省略图示)的废水或者步骤(a)中经过处理的废水(上清液)进行生物处理的同时，通过膜组件15进行固液分离成为污泥与处理水(渗透水)的步骤。(b) In the membrane separation activated sludge treatment device 10, the wastewater from the raw water tank (not shown) or the treated wastewater (supernatant) in step (a) is biologically treated by microorganisms in the activated sludge At the same time, the step of solid-liquid separation into sludge and treated water (permeate water) is carried out through the membrane module 15.
(c)过滤装置30中，通过反渗透膜或者纳米过滤膜对通过膜组件15的处理水(渗透水)进行过滤处理的步骤。(c) In the filtration device 30 , a step of filtering the treated water (permeated water) passing through the membrane module 15 through a reverse osmosis membrane or a nanofiltration membrane.
(d)蒸发浓缩装置40中，对没有通过过滤装置主体31的浓缩水进行浓缩处理的步骤。(d) In the evaporative concentration device 40 , a step of concentrating the concentrated water that has not passed through the filter device main body 31 .
(废水)(Wastewater)
废水处理装置中经过处理的废水与第1形态中的废水相同，在此省略其说明。The waste water treated in the waste water treatment device is the same as the waste water in the first embodiment, and its description is omitted here.
(步骤(a))(step (a))
步骤(a)与第1形态中的步骤(a)为相同的步骤，在此省略其说明。Step (a) is the same step as step (a) in the first embodiment, and its description is omitted here.
(步骤(b))(step (b))
废水处理方法不具有步骤(a)时，将储存在原水槽(省略图示)中的废水经由废水通道50供给至膜分离活性污泥处理装置10的膜分离槽11中。When the wastewater treatment method does not have step (a), the wastewater stored in the raw water tank (not shown) is supplied to the membrane separation tank 11 of the membrane separation activated sludge treatment device 10 through the wastewater channel 50 .
废水处理方法具有步骤(a)时，经步骤(a)处理的废水(上清液)经由上清液通路54被供给至膜分离活性污泥处理装置10的膜分离槽11中。When the wastewater treatment method has the step (a), the wastewater (supernatant) treated in the step (a) is supplied to the membrane separation tank 11 of the membrane separation activated sludge treatment device 10 through the supernatant passage 54 .
膜分离槽11中，使送风机13运作，由散气管12引入空气，通过对活性污泥中的微生物供给氧从而进行废水的生物处理。In the membrane separation tank 11, the air blower 13 is operated, air is introduced from the diffuser pipe 12, and the biological treatment of wastewater is carried out by supplying oxygen to microorganisms in the activated sludge.
此外，膜分离槽11中，通过使抽气泵18运作对膜组件15内减压，将混合水固液分离为污泥与处理水(渗透水)。此时，通过散气管12将空气导入到膜组件15中，可以边洗涤膜组件15的分离膜(例如中空丝膜等)的表面，边高效地进行固液分离。In addition, in the membrane separation tank 11, the inside of the membrane module 15 is decompressed by operating the suction pump 18, and the mixed water is solid-liquid separated into sludge and treated water (permeate water). At this time, air is introduced into the membrane module 15 through the diffuser pipe 12, and solid-liquid separation can be performed efficiently while washing the surface of the separation membrane (such as a hollow fiber membrane) of the membrane module 15.
步骤(b)中，通过凝集剂添加装置16在膜分离槽11中添加凝集剂对废水进行处理。In step (b), the wastewater is treated by adding a coagulant to the membrane separation tank 11 through the coagulant adding device 16 .
凝集剂的添加量，相对于根据将要供给到膜分离槽11中的废水中的难分解性物质的浓度(CODcr－BOD5)所求出的难分解性物质的量为0.1～2.75倍量，优选0.2～2.5倍量，更优选0.25～2.0倍量。凝集剂的添加量在0.1倍量以上时，可以充分得到凝集剂的效果，即凝集剂吸附在污泥表面上的同时也吸附住难分解性物质等有机物的效果，可以防止难分解性物质等引起的膜组件15的膜阻塞。The amount of the flocculant added is 0.1 to 2.75 times the amount of the hardly decomposable substance obtained from the concentration of the hardly decomposable substance in the wastewater to be supplied to the membrane separation tank 11 (CODcr −BOD5 ). , preferably 0.2 to 2.5 times the amount, more preferably 0.25 to 2.0 times the amount. When the amount of the coagulant added is more than 0.1 times, the effect of the coagulant can be fully obtained, that is, the coagulant is adsorbed on the surface of the sludge and also adsorbs the effect of organic matter such as refractory substances, which can prevent refractory substances, etc. The resulting membrane blockage of the membrane module 15.
有凝集剂的添加量越多，越容易得到凝集剂的效果的倾向。只是，过量添加凝集剂时，如上所述，凝集剂在处理水中残存时，该凝集剂会引起膜阻塞，凝集剂变成处理水污染的原因，有处理水的水质恶化的风险。凝集剂的添加量如果在2.75倍量以下时，凝集剂不容易在处理水中残存，可以抑制凝集剂引起的膜组件15的膜阻塞。此外，得到了高水质的处理水。There is a tendency that the effect of the coagulant tends to be obtained more easily as the amount of the coagulant added is larger. However, if the coagulant is added in excess, as described above, if the coagulant remains in the treated water, the coagulant will cause membrane clogging, and the coagulant will become a cause of pollution of the treated water, and there is a risk of deteriorating the quality of the treated water. When the amount of the coagulant added is 2.75 times or less, the coagulant is less likely to remain in the treated water, and membrane clogging of the membrane module 15 caused by the coagulant can be suppressed. In addition, high-quality treated water was obtained.
另外，“CODcr”为重铬酸钾的耗氧量，根据JIS K 0102进行测定。In addition, "CODcr " is the oxygen consumption of potassium dichromate, and it measures based on JISK0102.
另外，“BOD5”为5天的生化需氧量，根据JIS K 0102进行测定。In addition, "BOD5" is biochemical oxygen demand for5 days, and it measures based on JISK0102.
此外，步骤(b)中，可以通过污泥添加装置17向膜分离槽11中添加未添加凝集剂的活性污泥。废水处理方法具有步骤(a)时，优选将标准活性污泥处理装置20中产生的剩余污泥的一部分作为未添加凝集剂的活性污泥，经由供给污泥通道57供给至膜分离活性污泥处理装置10的膜分离槽11中。In addition, in step (b), the activated sludge to which the coagulant is not added can be added to the membrane separation tank 11 through the sludge adding device 17 . When the wastewater treatment method has step (a), it is preferable to supply a part of the excess sludge generated in the standard activated sludge treatment device 20 as activated sludge without adding a coagulant to the membrane separation activated sludge through the sludge supply channel 57 In the membrane separation tank 11 of the processing device 10.
未添加凝集剂的活性污泥的添加量，相对于添加到膜分离槽11中的凝集剂的添加量，优选为50倍以上的MLSS相当量。未添加凝集剂的活性污泥的添加量在50倍以上时，则意味着膜分离槽11内存在着充分量的活性污泥，即使向膜分离槽11中过量添加凝集剂，凝集剂也会吸附在活性污泥上，不容易在处理水中残存。而且，凝集剂吸附在活性污泥上时，也吸附住难分解性物质等有机物。因此，可以抑制凝集剂或难分解性物质等引起的膜组件15的膜阻塞。此外，令凝集剂吸附在未添加凝集剂的活性污泥上时，处理水中溶解的凝集剂的比例也减少，所以透过膜组件15的凝集剂的比例变少。因此，得到高水质的处理水变得更容易。The amount of activated sludge to which no coagulant is added is preferably 50 times or more the equivalent amount of MLSS relative to the amount of coagulant added to the membrane separation tank 11 . When the amount of activated sludge without coagulant added is more than 50 times, it means that there is a sufficient amount of activated sludge in the membrane separation tank 11. Even if the coagulant is excessively added to the membrane separation tank 11, the coagulant will also Adsorbed on the activated sludge, it is not easy to remain in the treated water. Moreover, when the coagulant is adsorbed on the activated sludge, it also adsorbs organic substances such as refractory substances. Therefore, membrane clogging of the membrane module 15 caused by coagulants, refractory substances, and the like can be suppressed. In addition, when the coagulant is adsorbed on the activated sludge to which no coagulant is added, the ratio of the coagulant dissolved in the treated water is also reduced, so the ratio of the coagulant permeating the membrane module 15 is reduced. Therefore, it becomes easier to obtain high-quality treated water.
有这样的倾向，未添加凝集剂的活性污泥的添加量越多，越容易得到处理水中的凝集剂的残存抑制效果。只是，过量添加未添加凝集剂的活性污泥有出现下述问题的担忧：(i)污泥添加装置17大型化，(ii)有扰乱膜分离槽11的菌群的风险，从而不能顺利地进行生物处理，(iii)凝集剂优先吸附在活性污泥上，作为凝集剂本来目的的除去难分解性物质等膜阻塞物质的效果下降。因此，未添加凝集剂的活性污泥的添加量，相对于膜分离槽11中添加的凝集剂的添加量，优选200倍以下的MLSS相当量。There is such a tendency that the more the amount of activated sludge to which no coagulant is added is increased, the easier it is to obtain the effect of suppressing the remaining of the coagulant in treated water. However, excessive addition of activated sludge without adding a coagulant may cause the following problems: (i) the sludge addition device 17 is enlarged, (ii) there is a risk of disturbing the flora of the membrane separation tank 11, so that it cannot be smoothly In the case of biological treatment, (iii) the coagulant is preferentially adsorbed on the activated sludge, and the effect of removing membrane clogging substances such as refractory substances, which is the original purpose of the coagulant, is reduced. Therefore, the addition amount of the activated sludge to which no flocculant is added is preferably 200 times or less the equivalent amount of MLSS with respect to the addition amount of the flocculant added to the membrane separation tank 11 .
步骤(b)中的膜分离槽11中添加的未添加凝集剂的活性污泥的MLSS，优选为6000～35000mg/L，更优选为8000～12000mg/L。未添加凝集剂的活性污泥的MLSS过稀薄时，则需要在膜分离槽11中添加大量的未添加凝集剂的活性污泥，增加了成本。另一方面，未添加凝集剂的活性污泥的MLSS过浓时，粘度变高，要花费工夫进行未添加凝集剂的活性污泥的供给。此外，污泥通道17a、供给污泥通道57、泵17b有闭塞的情形。The MLSS of the activated sludge without coagulant added to the membrane separation tank 11 in step (b) is preferably 6000-35000 mg/L, more preferably 8000-12000 mg/L. When the MLSS of the activated sludge without adding a coagulant is too thin, it is necessary to add a large amount of activated sludge without adding a coagulant to the membrane separation tank 11, which increases the cost. On the other hand, when the MLSS of the activated sludge which does not add a coagulant is too thick, the viscosity will become high, and it will take time to supply the activated sludge which does not add a coagulant. In addition, the sludge passage 17a, the supply sludge passage 57, and the pump 17b may be blocked.
步骤(b)中，膜组件15中分离出的剩余污泥经由剩余污泥通道52被排出。另外，因为剩余污泥中包含微生物，所以剩余污泥的一部分可以返送至膜分离活性污泥处理装置10中，再次用于废水的生物处理。In step (b), the excess sludge separated from the membrane module 15 is discharged through the excess sludge channel 52 . In addition, because the excess sludge contains microorganisms, a part of the excess sludge can be returned to the membrane separation activated sludge treatment device 10 and used again for biological treatment of wastewater.
作为步骤(b)中所使用的凝集剂，举例有第1形态中说明过的脒系凝集剂。Examples of the coagulant used in the step (b) include the amidine coagulant described in the first aspect.
(步骤(c))(step (c))
步骤(c)与第1形态中的步骤(c)为相同的步骤，在此省略其说明。Step (c) is the same step as step (c) in the first embodiment, and its description is omitted here.
(步骤(d))(step (d))
步骤(d)与第1形态中的步骤(d)为相同的步骤，在此省略其说明。Step (d) is the same step as step (d) in the first embodiment, and its description is omitted here.
(作用效果)(Effect)
上述所说明的本发明的废水处理方法以及废水处理装置的第2形态中，通过MBR处理废水时，以相对于将要供给至膜分离槽的难分解性物质的量向膜分离槽中添加特定量的凝集剂。因此，难分解性物质等有机物会被吸附在凝集剂上，可以防止难分解性物质等引起的膜组件的膜阻塞。而且，由于凝集剂的添加量适量，处理水中的凝集剂也不容易残存，可以抑制凝集剂引起的膜组件的膜封闭。此外，得到了高水质的处理水。In the second embodiment of the wastewater treatment method and the wastewater treatment device of the present invention described above, when the wastewater is treated by MBR, a specific amount is added to the membrane separation tank with respect to the amount of refractory substances to be supplied to the membrane separation tank. coagulant. Therefore, organic substances such as refractory substances are adsorbed on the coagulant, and membrane clogging of the membrane module caused by refractory substances and the like can be prevented. Moreover, since the coagulant is added in an appropriate amount, the coagulant in the treated water is not easy to remain, and the membrane closure of the membrane module caused by the coagulant can be suppressed. In addition, high-quality treated water was obtained.
(其他的实施方式)(other embodiments)
另外，本发明的废水处理方法以及废水处理装置的第2形态并不限定于图示例的废水处理装置以及利用该装置的废水处理方法。In addition, the second aspect of the waste water treatment method and the waste water treatment apparatus of the present invention is not limited to the waste water treatment apparatus and the waste water treatment method using the apparatus of the illustrated example.
例如，图1、2所示的废水处理装置的膜分离活性污泥处理装置10虽然有向膜分离槽11中添加未添加凝集剂的活性污泥的污泥添加装置17，但也可以省略污泥添加装置17。即，本发明的废水处理方法的第2形态中，步骤(a)中，可以不向膜分离槽11中添加未添加凝集剂的活性污泥。For example, although the membrane separation activated sludge treatment device 10 of the wastewater treatment device shown in FIGS. Mud adding device 17. That is, in the second aspect of the wastewater treatment method of the present invention, in the step (a), the activated sludge to which no flocculant is added may not be added to the membrane separation tank 11 .
此外，图2所示的废水处理装置中，将标准活性污泥处理装置20所产生的剩余污泥的一部分，作为未添加凝集剂的活性污泥供给到膜分离活性污泥处理装置10的膜分离槽11中，也可以将活性污泥槽21中的活性污泥作为未添加凝集剂的活性污泥供给到膜分离槽11中。只是，因将剩余污泥作为未添加凝集剂的活性污泥添加的这种方法，可以减少进行废弃处理的剩余污泥的量，故而优选。In addition, in the wastewater treatment device shown in FIG. 2 , a part of the excess sludge generated by the standard activated sludge treatment device 20 is supplied to the membrane of the membrane separation activated sludge treatment device 10 as activated sludge without adding a coagulant. In the separation tank 11, the activated sludge in the activated sludge tank 21 may be supplied to the membrane separation tank 11 as the activated sludge to which the flocculant was not added. However, the method of adding excess sludge as activated sludge to which no flocculant is added is preferable since the amount of excess sludge to be disposed of can be reduced.
[实施例][Example]
以下，根据实施例对本发明作更具体的说明，但是本发明并不限定于此。Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited thereto.
(凝集剂)(coagulant)
作为凝集剂，使用聚脒系高分子凝集剂(三菱丽阳株式会社制，“KP7000”)。As the coagulant, a polyamidine-based polymer coagulant (manufactured by Mitsubishi Rayon Corporation, "KP7000") was used.
〔例1〕〔example 1〕
向膜分离槽中供给100mL的MLSS调整至8000mg/L的未添加凝集剂的活性污泥。相对于该膜分离槽的活性污泥100mL，添加浓度调整为0.3质量％的凝集剂至其在活性污泥中的浓度为30mg/L。即，膜分离槽内的活性污泥的MLSS相当量(MLSS量)为800mg，凝集剂的添加量是3mg。100 mL of activated sludge to which MLSS was adjusted to 8000 mg/L without adding a coagulant was supplied to the membrane separation tank. With respect to 100 mL of activated sludge in this membrane separation tank, a coagulant whose concentration was adjusted to 0.3% by mass was added so that the concentration in the activated sludge became 30 mg/L. That is, the MLSS equivalent amount (MLSS amount) of the activated sludge in a membrane separation tank was 800 mg, and the addition amount of a coagulant was 3 mg.
接着，在磁力搅拌器中缓缓地搅拌30分钟后，通过中空丝膜(三菱丽阳株式会社制，“Suterapoa SADF(ステラポアSADF)”)过滤。Next, after gently stirring for 30 minutes with a magnetic stirrer, it filtered through a hollow fiber membrane (manufactured by Mitsubishi Rayon Corporation, "Suterapoa SADF (Sterapore SADF)").
测定过滤液中的TOC(全有机碳)的浓度。结果在表1中显示。The concentration of TOC (total organic carbon) in the filtrate was measured. The results are shown in Table 1.
另外，例1以及下例2～4相当于实施例，例5～7相当于比较例。In addition, Example 1 and following Examples 2-4 correspond to an Example, and Examples 5-7 correspond to a comparative example.
〔例2～7〕〔Example 2～7〕
如表1所示，活性污泥中的浓度，除了改变凝集剂的添加量之外，与例1同样地测定过滤液中的TOC浓度。结果在表1中显示。As shown in Table 1, the TOC concentration in the filtrate was measured in the same manner as in Example 1 except that the concentration in the activated sludge was changed in the addition amount of the coagulant. The results are shown in Table 1.
[表1][Table 1]
由表1的结果可以明确得知，例1～4中，相对于活性污泥中的凝集剂的添加量，未添加凝集剂的活性污泥的MLSS量为50倍以上，过滤液中的TOC浓度不足1mg/L。这意味着凝集剂被吸附在活性污泥上，其在过滤液中几乎不残存，且过滤液的水质较高。It can be clearly known from the results in Table 1 that in Examples 1 to 4, relative to the amount of coagulant added in the activated sludge, the MLSS amount of the activated sludge without coagulant added is more than 50 times, and the TOC in the filtrate The concentration is less than 1mg/L. This means that the coagulant is adsorbed on the activated sludge, hardly remains in the filtrate, and the water quality of the filtrate is high.
而例5～7中，相对于活性污泥中的凝集剂的添加量，未添加凝集剂的活性污泥的MLSS量不足50倍，过滤液中的TOC浓度在10mg/L以上。In Examples 5 to 7, the MLSS amount of the activated sludge without the addition of the coagulant was less than 50 times the amount of the coagulant added to the activated sludge, and the TOC concentration in the filtrate was above 10 mg/L.
根据这些结果可知，在通过MBR添加凝集剂来处理废水时，如果相对于凝集剂的添加量添加50倍以上的MLSS相当量的未添加凝集剂的活性污泥时，即使在膜分离槽中过量添加凝集剂，凝集剂也会吸附在活性污泥上，不容易在处理水中残存。According to these results, when wastewater is treated by adding a coagulant through MBR, if the activated sludge without coagulant is added in an equivalent amount of MLSS equivalent to 50 times or more relative to the amount of coagulant added, even if the excess in the membrane separation tank Adding a coagulant, the coagulant will also be adsorbed on the activated sludge, and it is not easy to remain in the treated water.
因此，根据本发明的废水处理方法以及废水处理装置的第1形态，可以抑制分离膜阻塞，得到水质高的处理水。Therefore, according to the first aspect of the wastewater treatment method and the wastewater treatment apparatus of the present invention, clogging of the separation membrane can be suppressed, and treated water with high water quality can be obtained.
〔例8〕[Example 8]
作为含有难分解性物质的废水，使用从焦炭制造工序中排出的废水。已知从焦炭制造工序中排出的废水含有腐殖物质等，含有较多的一般不易生物处理的难分解性物质。As wastewater containing hardly decomposable substances, wastewater discharged from a coke manufacturing process was used. It is known that the wastewater discharged from the coke manufacturing process contains humic substances and the like, and contains a large amount of refractory substances that are generally difficult to treat biologically.
本例中使用的废水的CODcr为3500mg/L，BOD5为500mg/L。因此，废水中的难分解性物质的浓度(CODcr－BOD5)为3000mg/L。另外，CODcr及BOD5是根据JIS K 0102测定的。The CODcr of the wastewater used in this example is 3500mg/L, and the BOD5 is 500mg/L. Therefore, the concentration of hardly decomposable substances (CODcr -BOD5 ) in the wastewater was 3000 mg/L. In addition, CODcr and BOD5 were measured based on JISK0102.
向膜分离槽中供给100mL的MLSS调整至8000mg/L的未添加凝集剂的活性污泥。相对于该膜分离槽的活性污泥100mL，添加废水直至活性污泥中的难分解性物质的浓度为100mg/L。即，膜分离槽内的活性污泥的MLSS相当量(MLSS量)为800mg，难分解性物质的量是10mg。100 mL of activated sludge to which MLSS was adjusted to 8000 mg/L without adding a coagulant was supplied to the membrane separation tank. Waste water was added to 100 mL of activated sludge in the membrane separation tank until the concentration of the refractory substance in the activated sludge became 100 mg/L. That is, the MLSS equivalent amount (MLSS amount) of the activated sludge in the membrane separation tank was 800 mg, and the amount of the refractory substance was 10 mg.
接着，在磁力搅拌器中缓缓地搅拌30分钟后，通过中空丝膜(三菱丽阳株式会社制，“Suterapoa SADF(ステラポアSADF)”)过滤。Next, after gently stirring for 30 minutes with a magnetic stirrer, it filtered through a hollow fiber membrane (manufactured by Mitsubishi Rayon Corporation, "Suterapoa SADF (Sterapore SADF)").
根据JIS K 0102测定过滤液的CODcr，结果在表2中显示。The CODcr of the filtrate was measured in accordance with JIS K 0102, and the results are shown in Table 2.
另外，例8以及下例9、15相当于比较例，例10～14相当于实施例。In addition, Example 8 and following Examples 9 and 15 correspond to comparative examples, and Examples 10 to 14 correspond to Examples.
〔例9～15〕[Example 9~15]
添加废水后，添加浓度调整至0.3质量％的凝集剂直至在活性污泥中的浓度为表2所示的值，除此之外，与例8相同地测定过滤液的CODcr。结果在表2中显示。After adding wastewater, the CODcr of the filtrate was measured in the same manner as in Example 8, except that a coagulant whose concentration was adjusted to 0.3% by mass was added until the concentration in the activated sludge became the value shown in Table 2. The results are shown in Table 2.
[表2][Table 2]
表2的结果明确显示，例10～14中，相对于废水中的难分解性物质的量，凝集剂的添加量为0.1～2.75倍量，过滤液中的过滤液的CODcr为10～44mg/L。特别是例11～13中，相对于废水中难分解性物质的量，凝集剂的添加量为0.25～2.0倍量，过滤液中的过滤液的CODcr为3～5mg/L，具有优异的效果。这意味着凝集剂被吸附在活性污泥上时，难分解性物质也被吸附在凝集剂上，几乎不在过滤液中残存，多余的凝集剂几乎不在过滤液中残存，以及过滤液的水质高。The results in Table 2 clearly show that in Examples 10 to 14, the amount of coagulant added is 0.1 to 2.75 times the amount of refractory substances in the wastewater, and the CODcr of the filtrate in the filtrate is 10 to 44 mg /L. Particularly in Examples 11 to 13, the amount of the coagulant added is 0.25 to 2.0 times the amount of refractory substances in the waste water, and the CODcr of the filtrate in the filtrate is 3 to 5 mg/L, which has excellent Effect. This means that when the coagulant is adsorbed on the activated sludge, the refractory substances are also adsorbed on the coagulant, and hardly remain in the filtrate, and the excess coagulant hardly remains in the filtrate, and the water quality of the filtrate is high .
而例8、9、15中，相对于废水中的难分解性物质的量，凝集剂的添加量不足0.1倍量，或者超过2.75倍量，过滤液的CODcr在50mg/L以上。In Examples 8, 9, and 15, the amount of coagulant added was less than 0.1 times or more than 2.75 times the amount of refractory substances in the wastewater, and the CODcr of the filtrate was above 50 mg/L.
由这些结果可知，通过MBR处理废水时，如果相对于将要供给至MBR的废水中的难分解性物质的量，以0.1～2.75倍量添加凝集剂，难分解性物质等有机物被吸附在凝集剂上，可以防止难分解性物质等引起的分离膜的膜阻塞。而且，凝集剂本身也不容易在处理水中残存。From these results, it can be seen that when wastewater is treated by MBR, if a coagulant is added in an amount of 0.1 to 2.75 times the amount of refractory substances in the wastewater to be supplied to the MBR, organic substances such as refractory substances are adsorbed on the coagulant. On the other hand, membrane clogging of the separation membrane caused by hardly decomposable substances and the like can be prevented. Furthermore, the coagulant itself does not easily remain in the treated water.
因此，根据本发明的废水处理方法以及废水处理装置的第2形态，可以抑制分离膜阻塞、得到高水质的处理水。Therefore, according to the second aspect of the wastewater treatment method and the wastewater treatment apparatus of the present invention, clogging of the separation membrane can be suppressed, and high-quality treated water can be obtained.
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