WO2012128212A1

WO2012128212A1 - Water treatment method and ultrapure water production method

Info

Publication number: WO2012128212A1
Application number: PCT/JP2012/056876
Authority: WO
Inventors: 新井　伸説; 繁樹藤島; 太郎飯泉; 育野　望
Original assignee: 栗田工業株式会社
Priority date: 2011-03-18
Filing date: 2012-03-16
Publication date: 2012-09-27
Also published as: JP2012196588A

Abstract

Raw water (W) which is treated in a pretreatment system (1) is supplied to a biological treatment means (3). Treated water (W1) which is treated in the biological treatment means (3) is supplied to a primary pure water device. A pH sensor, which is not shown in the drawing, and a first supply mechanism (5) are provided at the upstream part of the biological treatment means (3), so that an ammoniacal nitrogen source (NH₃-N) and sulfuric acid can be added from the first supply mechanism (5). In tandem with the first supply mechanism (5), a second supply mechanism (6) that can add an oxidizing agent and/or a disinfecting agent is provided. By employing this constitution, nitrifying bacteria can become a predominant species in the biological treatment means (3). This water treatment method enables the decomposition of TOC, particularly urea, in raw water at a high level.

Description

Water treatment method and ultrapure water production method

The present invention relates to a water treatment method for raw water such as city water, groundwater, and industrial water, and a method for producing ultrapure water using treated water treated by this water treatment method, and in particular, it can highly remove urea in raw water. The present invention relates to a water treatment method that can be performed and a method for producing ultrapure water using treated water treated by the water treatment method.

Conventionally, an ultrapure water production apparatus that produces ultrapure water from raw water such as city water, groundwater, and industrial water basically includes a pretreatment apparatus, a primary pure water production apparatus, and a secondary pure water production apparatus. . Among these, the pretreatment device is composed of agglomeration, levitation, and filtration devices. The primary pure water production apparatus includes, for example, two reverse osmosis membrane separation devices and a mixed bed ion exchange device, or an ion exchange pure water device and a reverse osmosis membrane separation device. Further, the secondary pure water production apparatus is composed of, for example, a low-pressure ultraviolet oxidizer, a mixed bed ion exchanger, and an ultrafiltration membrane separator.

In such an ultrapure water production apparatus, there is an increasing demand for improvement in the purity, and accordingly, removal of the TOC component is required. Of the TOC components in ultrapure water, it is particularly difficult to remove urea, and the lower the TOC component, the greater the influence of urea removal on the TOC component content. Therefore, Patent Documents 1 to 3 describe that TOC in ultrapure water is sufficiently reduced by removing urea from the water supplied to the ultrapure water production apparatus.

Patent Document 1 discloses that a biological treatment device is incorporated in a pretreatment device and urea is decomposed by this biological treatment device. Further, in Patent Document 2, a biological treatment apparatus is incorporated in a pretreatment apparatus, mixed water of treated water (industrial water) and semiconductor cleaning / collecting water is passed through, and organic substances contained in the semiconductor cleaning / collecting water are disclosed. It has been disclosed that it becomes a carbon source for biological treatment reactions and improves the decomposition rate of urea. In addition, there are cases where a large amount of ammonium ions (NH ₄ ⁺ ) are contained in this semiconductor cleaning / recovered water, which becomes a nitrogen source in the same manner as urea and may inhibit the decomposition of urea. Further, in Patent Document 3, in order to solve the above-mentioned problem of Patent Document 2, the water to be treated (industrial water) and the semiconductor cleaning / collecting water are mixed after being biologically treated separately, It is described that water is passed through a secondary pure water production apparatus.

JP-A-6-63592 JP-A-6-233997 JP 7-313994 A

However, as in the water treatment method described in Patent Document 1, when a carbon source is added to the water to be treated, although the urea decomposition and removal efficiency in the biological treatment apparatus is improved, the amount of bacterial cells in the biological treatment apparatus is increased. There is a problem that the amount of bacterial cells flowing out from the biological treatment apparatus increases.

Further, as the water containing carbon source as in the water treatment method described in Patent Document 2, when semiconductor cleaning / collecting water having a high ammonium ion content is used, ammonium ions inhibit the decomposition of urea. There is.

The present invention has been made in view of the above problems, and an object thereof is to provide a water treatment method capable of highly decomposing TOC in raw water, particularly urea. Moreover, an object of this invention is to provide the ultrapure water manufacturing method using this water treatment method.

In order to solve the above problems, first, the present invention provides a water treatment method for biologically treating raw water containing an organic substance, wherein the biological treatment is obtained by predominating species of nitrifying bacteria. A processing method is provided (Invention 1).

According to the above invention (Invention 1), the nitrifying bacteria group is involved in the removal of urea. By adding an ammonia nitrogen source to the raw water, the nitrifying bacteria group (ammonia-oxidizing bacteria) becomes ammoniacal nitrogen. By oxidizing the source to nitrite ions (NO ²⁻ ), the activity of the nitrifying bacteria group can be maintained and urea can be decomposed and removed. That is, in the water treatment method described in Patent Document 2, urea and urea derivatives are used as nitrogen sources when BOD-assimilating bacteria (heterotrophic bacteria) decompose and assimilate organic matter, not nitrifying bacteria (autotrophic bacteria). It is presumed that this is a treatment mechanism that removes urea and urea derivatives by decomposing and taking in as ammonia. On the other hand, in the invention 1, the mechanism in which urea and urea derivatives are removed by oxidizing urea and urea derivatives directly to ammonia or nitrous acid in the process of nitrifying bacteria oxidizing ammonia to nitrous acid and nitric acid. It is done. Thus, even when an ammoniacal nitrogen source is added to the biologically treated feed water in which the nitrifying bacteria are dominant, the decomposition of urea is not inhibited, but rather the growth of these nitrifying bacteria. It becomes a factor which raises activity. As a result, urea and urea derivatives are decomposed by nitrifying bacteria with increased activity. It is assumed that the removal performance is improved.

In addition, the present inventors have compared the biological treatment in which the nitrifying bacteria group has been predominated with the biological treatment in which the BOD-utilizing bacterium has become dominant species, in which the former has reduced urea to a lower concentration in a short time. It was also found that the urea derivative can be decomposed and removed. The details of the bacterial species that contribute to the degradation of urea and urea derivatives are not clear, but it has been confirmed that one of the ammonia-oxidizing bacteria among the nitrifying bacteria group has contributed. However, it is particularly preferable to perform a biological treatment in which ammonia-oxidizing bacteria are dominant. Furthermore, in biological treatment in which BOD-utilizing bacteria have become dominant species, a considerable amount of BOD (biochemical oxygen demand) is required to decompose and remove urea. In general, the relationship of BOD: nitrogen: phosphorus = 100: 5: 1 is known, and 20 times the amount of BOD is necessary for nitrogen of urea. When the BOD of the raw water is small, it is necessary to add BOD corresponding to the urea removal amount as a daily standard, which leads to an increase in operation cost. Furthermore, since BOD-assimilating bacteria grow significantly, the amount of bacterial cells flowing into the biologically treated water increases, resulting in the adverse effects on the subsequent treatment, and the amount of sludge from the biological treatment increases. On the other hand, in biological treatment in which nitrifying bacteria are dominant species, BOD is not necessary for decomposing and removing urea, and the amount of bacterial cell growth is small compared to the case of BOD-utilizing bacteria. The amount of bacterial cells flowing out into the water is small and suitable.

In the above invention (Invention 1), in the biological treatment, the concentration of ammonia nitrogen (NH ₃ -N) in the biological treatment is 1/5 or more of the concentration of the total organic carbon (TOC) in the raw water. (Invention 2)

According to the above invention (Invention 2), when ammonia nitrogen is contained in the raw water for biological treatment as described above, or when an ammonia nitrogen source is added to the raw water for biological treatment, the nitrifying bacteria group is superior. It is possible to occupy the species, thereby improving ammonia nitrogen removal performance in biological treatment. In the biological treatment in which the nitrifying bacteria group has become dominant, urea and ammonia nitrogen are decomposed and reduced, and nitrous acid or nitric acid is generated. TOC decreases due to the decomposition of urea and organic nitrogen, and also due to the decomposition of organic matter by partially existing BOD-utilizing bacteria, but the amount of decrease is small. As a result, the concentration of ammonia nitrogen (NH ₃ -N) in the biological treatment is reduced to 1/5 or more of the total concentration of organic carbon (TOC) in the raw water, thereby efficiently reducing to a lower concentration. Urea and urea derivatives can be decomposed and removed, and ultrapure water with a reduced TOC concentration can be produced. On the other hand, in the biological treatment in which the assimilating bacteria have become dominant species, when the BOD assimilating bacteria degrades urea, as described above, 20 times the amount of BOD is assimilated relative to the nitrogen of the decomposed urea. BOD (biochemical oxygen demand) indicates the amount of oxygen (O ₂ ) that is required (consumed) when decomposing organic substances that can be decomposed by BOD-assimilating bacteria. C) If all the components are carbon dioxide (CO ₂ ), there is a correlation between the decrease in BOD and the decrease in total organic carbon (TOC), and the relationship of BOD: N described above is the relationship of TOC: N. It can be replaced and corresponds to TOC: N = 7.5: 5. That is, in biological treatment in which BOD-utilizing bacteria have become dominant species, efficient urea removal is performed unless the TOC reduction concentration is 7.5 times or more the ammonia nitrogen (NH ₃ -N) reduction concentration. It will be impossible.

In the above invention (Invention 1), the biological treatment is performed when the sum of the production concentration of nitrite nitrogen (NO ₂ -N) and the production concentration of nitrate nitrogen (NO ₃ -N) in the biological treatment is It is preferably one that is 1/5 or more of the reduced concentration of total organic carbon (TOC) in water (Invention 3).

According to the above invention (Invention 3), in the biological treatment in which the nitrifying bacteria group has become dominant species, urea is decomposed to generate nitrous acid or nitric acid, and the nitrite nitrogen or nitrate nitrogen concentration increases. Moreover, when organic nitrogen other than ammonia nitrogen and urea is contained in the raw water, the concentration of nitrite nitrogen or nitrate nitrogen resulting from the decomposition thereof increases. TOC decreases due to decomposition of urea and organic nitrogen, and also due to decomposition of organic substances by BOD-assimilating bacteria that are partly present, but the decrease is small. Therefore, the condition of the biological treatment is defined as the sum of the production concentration of nitrite nitrogen (NO ₂ -N) and the production concentration of nitrate nitrogen (NO ₃ -N) in the biological treatment is the total organic carbon in the raw water ( By setting the concentration to 1/5 or more of the reduced concentration of TOC, it is possible to achieve the dominant species of the nitrifying bacteria group, and to efficiently decompose and remove urea and urea derivatives to a lower concentration. Reduced ultrapure water can be produced.

In the above invention (Invention 1), the biological treatment is such that the reduced concentration of organic nitrogen in the biological treatment is 1/5 or more of the reduced concentration of total organic carbon (TOC) in the raw water. Is preferred (Invention 4).

According to the above invention (Invention 4), in the biological treatment in which the nitrifying bacteria group has become dominant species, the reduction range of organic nitrogen is larger than the reduction range of TOC. Therefore, by controlling the biological treatment conditions so that the reduced concentration of organic nitrogen in the biological treatment is 1/5 or more of the reduced concentration of total organic carbon (TOC) in the raw water, Thus, urea and urea derivatives can be efficiently decomposed and removed, and ultrapure water with a reduced TOC concentration can be produced.

In the above inventions (Inventions 1 to 4), it is preferable to add an ammoniacal nitrogen source to the biological treatment water (Invention 5).

According to the above invention (Invention 5), the growth and activity of the nitrifying bacteria group can be increased, and thereby the decomposition and removal performance of urea and urea derivatives can be improved by the nitrifying bacteria group having increased activity. .

In the above inventions (Inventions 1 to 5), it is preferable to adjust the feed water for the biological treatment to pH 5 to 6.5 (Invention 6).

According to the above invention (Invention 6), it is considered that the nitrifying bacteria group that decomposes and removes urea basically has an optimum value in the pH neutral range (pH = 7 to 8). Therefore, when the pH is adjusted to 5 to 6.5, both the ammonia oxidation activity and the urea decomposition activity decrease. However, comparing the decrease in ammonia oxidation activity with the decrease in urea decomposition activity, the decrease in urea decomposition activity is less. Further, under the condition of pH 5 to 6.5, ionic ammonia is increased and the amount of ammonia taken into the nitrifying bacteria group is decreased. As a result, the amount of urea decomposed / removed by the nitrifying bacteria group increases, so that the activity of the nitrifying bacteria group can be maintained even when the urea concentration fluctuates, and urea is efficiently decomposed / Can be removed.

In the above inventions (Inventions 1 to 6), it is preferable to add a chlorine-based oxidizing agent and / or bactericidal agent to the biological treatment water (Invention 7).

According to the above invention (Invention 7), it has been confirmed that the decomposition / removal performance of urea is improved by adding a chlorine-based oxidizing agent and / or bactericidal agent to the biological treatment water. The details of the mechanism for improving the decomposition and removal performance of urea by adding a chlorine-based oxidizing agent and / or bactericidal agent to biological treatment water are not clear, but nitrifying bacteria that efficiently perform urea decomposition It is inferred that the group has higher resistance to chlorinated oxidants and / or fungicides than other species including BOD-utilizing bacteria. As a result, when chlorinated oxidants and / or bactericides are added to biological treatment water, nitrifying bacteria that contribute to urea decomposition can maintain activity while other bacterial species are inactivated. It is assumed that the decomposition and removal performance of urea is improved by seeding.

In the above inventions (Inventions 1 to 7), it is preferable to reduce the TOC concentration of the biological treatment feed water (Invention 8).

According to the above invention (Invention 8), when the organic matter (TOC) concentration of the raw water for biological treatment is high, especially when the readily biodegradable organic matter is high, the growth / activity of BOD-utilizing bacteria (heterotrophic bacteria) is increased. Therefore, the growth / activity of the nitrifying bacteria group decreases, the urea decomposition efficiency decreases, and urea may not be sufficiently reduced. Specifically, the growth and activity of BOD-assimilating bacteria increases, so that the nitrogen source added as a nutrient source is used by BOD-assimilating bacteria, and phosphorus and trace amounts contained in other biological treatment water supply Due to the fact that nutrient sources such as metals (mineral components, etc.) are also used by BOD-assimilating bacteria, the growth and activity of the nitrifying bacteria group are reduced. As a countermeasure, it is preferable to remove organic substances in biological treatment water in advance, particularly easily biodegradable organic substances in advance. By removing readily biodegradable organic matter in advance, the growth and activity of BOD-utilizing bacteria can be suppressed in biological treatment, and biological treatment mainly consisting of nitrifying bacteria that decompose and remove urea can be performed. it can. Thereby, high urea decomposition efficiency can be obtained. Moreover, since the consumption of the nutrient by BOD assimilating bacteria is also suppressed, there is an effect that the treatment can be performed with fewer nutrient sources.

Further, secondly, the present invention produces ultrapure water by treating the treated water obtained by the water treatment method according to any one of claims 1 to 8 with a primary pure water device and a secondary pure water device. An ultrapure water production method is provided (Invention 9).

According to the above invention (Invention 9), since urea is sufficiently decomposed and removed in the biological treatment (water treatment) in the first stage of the primary pure water device and the secondary pure water device, high purity ultrapure water is removed. It can be manufactured efficiently. In particular, the concentration of total organic carbon (TOC) in the raw water is reduced to 1/5 or more, the concentration of nitrite nitrogen (NO ₂ —N) in the biological treatment, and nitrate nitrogen (NO ₃ ) — N) the sum of the generated concentrations is 1/5 or more of the reduced concentration of total organic carbon (TOC) in the raw water, and the reduced concentration of organic nitrogen in the biological treatment is less than the total organic carbon ( TOC) can be increased to 1/5 or more of the reduced concentration, and by adding an ammoniacal nitrogen source to the biological treatment water, the growth and activity of the nitrifying bacteria group can be increased. The ability to decompose and remove urea and urea derivatives can be improved by the group of nitrifying bacteria having increased activity.

According to the water treatment method of the present invention, the nitrifying bacteria are predominated in biological treatment, whereby the ammoniacal nitrogen source is oxidized to nitrite ions (NO ²⁻ ), thereby The activity can be maintained and urea can be decomposed and removed. At this time, the concentration is reduced to 1/5 or more of the total organic carbon (TOC) concentration in the raw water, the nitrite nitrogen (NO ₂ —N) production concentration and nitrate nitrogen (NO ₃ —) in the biological treatment. N) the sum of the generated concentrations is 1/5 or more of the reduced concentration of total organic carbon (TOC) in the raw water, and the reduced concentration of organic nitrogen in the biological treatment is less than the total organic carbon ( Since the amount of urea consumed by the nitrifying bacteria group increases when the concentration of TOC is reduced to 1/5 or more, the activity of the nitrifying bacteria group can be maintained even if the urea concentration varies greatly. Can be effectively decomposed and removed.

It is a systematic diagram which shows the water treatment method which concerns on one Embodiment of this invention. It is a systematic diagram which shows the ultrapure water manufacturing method using the water treatment method which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. FIG. 1 is a schematic view showing a water treatment method according to the first embodiment of the present invention.

In FIG. 1, reference numeral 1 denotes a pretreatment system for raw water W supplied from a raw water storage tank (not shown). After the raw water W treated by the pretreatment system 1 is adjusted to a predetermined temperature by the heat exchanger 2, Supplied to the biological treatment means 3. And this biological treatment means 3 is following the microbial cell separation apparatus 4, and after processing with these various apparatuses, it is supplied to a primary pure water apparatus as treated water W1.

In the apparatus configuration as described above, a pH sensor (not shown) and the first supply mechanism 5 are provided in the preceding stage of the biological treatment means 3, and an ammoniacal nitrogen source serving as a nutrient source from the first supply mechanism 5. (NH ₃ —N) and sulfuric acid as a pH adjusting agent can be added. A second supply mechanism 6 for adding an oxidizing agent and / or a bactericidal agent is provided in parallel with the first supply mechanism 5. Further, a third supply mechanism 7 for supplying a reducing agent and / or a slime control agent is provided at the subsequent stage of the biological treatment means 3. Reference numeral 8 denotes a pipe for feeding the raw water W or the like.

In the biological treatment apparatus configured as described above, as raw water W to be treated, ground water, river water, city water, other industrial water, recovered water from a semiconductor manufacturing process, or the like can be used. The urea concentration in the raw water (treatment target water) W is preferably about 5 to 200 μg / L, particularly about 5 to 100 μg / L.

Further, as the pretreatment system 1, a general pretreatment system in the production process of ultrapure water or a treatment similar to this is suitable. Specifically, a treatment system comprising agglomeration, pressurized levitation, filtration, or the like can be used. Further, for the purpose of reducing in advance the TOC (easy degradable organic matter) concentration of the feed water of the biological treatment means 3, the biological treatment means may be configured in two stages using the biological treatment means. Furthermore, you may use a reverse osmosis membrane processing apparatus, an ion exchange processing apparatus, etc. In particular, since urea does not have ionicity, the removal rate in reverse osmosis membrane treatment and ion exchange treatment is low, while organic substances other than urea (TOC component) can be removed to some extent by reverse osmosis membrane treatment and ion exchange treatment. Therefore, it is preferable to employ a reverse osmosis membrane treatment device or an ion exchange treatment device in the pretreatment system 1 so that the biological treatment means 3 can perform treatment in which the component to be removed is narrowed down to urea.

The biological treatment means 3 is a means for performing a treatment for decomposing and stabilizing pollutants in wastewater such as sewage by biological action, and is classified into an aerobic treatment and an anaerobic treatment. In general, organic matter is decomposed by biological treatment through oxygen respiration, nitric acid respiration, fermentation processes, etc., and is gasified or taken into the body of microorganisms and removed as sludge. Moreover, the removal process of nitrogen (nitrification denitrification method) and phosphorus (biological phosphorus removal method) can also be performed. A means for performing such biological treatment is generally called a biological reaction tank. Such a biological treatment means 3 is not particularly limited, but preferably has a fixed bed of a biological carrier. In particular, a fixed bed of a downward flow type with less bacterial cell outflow is preferred.

When the biological treatment means 3 is a fixed bed, it is preferable to wash the fixed bed as necessary. As a result, it is possible to prevent the occurrence of blockage of the fixed bed, mudballing, a decrease in the decomposition and removal efficiency of urea, and the like due to the growth of organisms (bacteria). There is no particular limitation on this cleaning method. For example, backwashing, that is, flowing the cleaning water in the direction opposite to the direction of passing raw water to fluidize the carrier, discharging sediment out of the system, It is preferable to perform pulverization, exfoliation of a part of the organism, and the like.

In addition, there is no particular limitation on the type of carrier for the fixed bed, and activated carbon, anthracite, sand, zeolite, ion exchange resin, plastic molded product, etc. are used, but in order to carry out biological treatment in the presence of an oxidizing agent. It is preferable to use a carrier that consumes less oxidant. However, when there is a possibility that a high concentration of oxidant flows into the biological treatment means, it is preferable to use a carrier such as activated carbon that can decompose the oxidant. Thus, when activated carbon etc. are used, even if it is a case where the density | concentration of the oxidizing agent in to-be-processed water is high, it is prevented that a microbial cell is inactivated and killed.

The water flow rate to the biological treatment means 3 is preferably about SV5 to 50 hr ⁻¹ . The temperature of the water supplied to the biological treatment means 3 is preferably normal temperature, for example, 10 to 35 ° C. Therefore, it is preferable to provide a heat exchanger before the biological treatment means as necessary.

There is no restriction | limiting in particular as an ammoniacal nitrogen source as a nutrient source added to this biological treatment means 3 from the 1st supply mechanism 5, Both organic and inorganic ammonia nitrogen sources are used suitably. it can. Among these, even if the added ammonia nitrogen source cannot be treated and remains in the biologically treated water, it is easy to remove in the subsequent treatment, so ammonium chloride, which is an ionic ammonia nitrogen source Ammonium salts such as ammonium sulfate are preferred.

Note that the object of the present invention is urea removal, and it is preferable to obtain and retain cells having better urea removal properties. From this viewpoint, urea and urea derivatives may be added as an ammoniacal nitrogen source. . However, since some urea and urea derivatives are not ionic and cannot be expected to be removed in subsequent treatments, when added in a large amount, they cannot be removed even in biological treatment and later treatment, and remain at the end. There is a high possibility that it will end. Therefore, when urea and urea derivatives are added, a method is preferred in which the addition concentration is minimized and the necessary amount as an ammoniacal nitrogen source is supplemented with an ammonium salt or the like.

Of the oxidizing agent and / or bactericidal agent added to the biological treatment means 3 from the second supply mechanism 6, a chlorine-based oxidizing agent such as sodium hypochlorite or chlorine dioxide is used as the oxidizing agent. be able to. Furthermore, as the disinfectant, for example, a combined chlorine agent (a combined chlorine agent having higher stability than chloramine) composed of a chlorine-based oxidizing agent and a sulfamic acid compound, hydrogen peroxide, and the like can be used.

Further, among the reducing agent and / or slime control agent added from the third supply mechanism 7 in the subsequent stage of the biological treatment means 3, examples of the reducing agent include gases such as hydrogen gas and lower oxides such as sulfur dioxide. , Lower oxygen acid salts such as thiosulfate, sulfite, bisulfite and nitrite, low valent metal salts such as iron (II) salt, organic acids such as formic acid, oxalic acid and L-ascorbic acid or salts thereof Hydrazine, aldehydes, saccharides and the like can be used, and sodium sulfite, sodium bisulfite and the like are preferable.

As the slime control agent, the same oxidant as described above can be used, and a bactericide that does not have an adverse effect due to oxidative deterioration in the RO membrane treatment, ion exchange treatment, etc., which will be described later, specifically, A bonded chlorinating agent composed of a chlorine-based oxidizing agent and a sulfamic acid compound (a bonded chlorinating agent having higher stability than chloramine), hydrogen peroxide, and the like are preferable.

Furthermore, when microbial cell outflow is recognized from the treated water of the biological treatment means 3, it is desirable to provide the microbial cell separation device 4 as in this embodiment. This bacterial cell separation device 4 is an obstacle (clogging of piping) in a subsequent process such as a primary pure water device caused by bacterial cells contained in the treated water of the biological treatment means 3 (microbial cells detached from the biological carrier). In order to avoid slime damage such as increased differential pressure, biofouling of RO membrane, etc., it is provided as needed. Specifically, membrane filtration (with a cartridge filter with a pore size of about 0.1 to 10 μm) Membrane filtration treatment used), ultrafiltration membrane treatment, coagulation filtration and the like can be used.

These reducing agents, slime control agents, and bacterial cell separation devices 4 are not necessarily required, and any one or more of them can be appropriately provided depending on the situation.

Next, a water treatment method using the above-described apparatus and additives will be described.

First, by supplying the raw water W to the pretreatment system 1 and removing the turbid component in the raw water W, the organic substance decomposition and removal efficiency in the biological treatment means 3 in the subsequent stage is reduced by the turbid component. While suppressing, the increase in the pressure loss of the biological treatment means 3 is suppressed.

The heat exchanger 2 adjusts the temperature of the pretreated raw water W as necessary so that the raw water W is heated when the water temperature of the raw water W is low, and is cooled to a predetermined water temperature when the water temperature is high. carry out. That is, the higher the water temperature of the raw water W, the higher the reaction rate and the higher the decomposition efficiency. On the other hand, when the water temperature is high, it is necessary to impart heat resistance to the treatment tank, the pipe 8 and the like of the biological treatment means, leading to an increase in equipment cost. Moreover, when the water temperature of the raw | natural water W is low, it leads to the increase in heating cost. Specifically, if the water temperature of the biological reaction is 40 ° C. or lower, basically, the higher the water temperature, the higher the biological activity and removal rate. However, when the water temperature exceeds 40 ° C., the biological activity and removal efficiency may tend to decrease. For the above reasons, the treatment water temperature is preferably about 20 to 40 ° C. Therefore, if the initial temperature of the raw water W is within the above range, nothing needs to be done.

In this way, raw water W whose temperature has been adjusted as necessary is supplied to the biological treatment means 3. At this time, the first supply mechanism 5 supplies the biological treatment means 3 with an ammoniacal nitrogen source (NH ₃ -N). And sulfuric acid as a pH adjuster is added to adjust the pH of the raw water W to 5 to 6.5.

Here, the addition amount of the ammoniacal nitrogen source (NH ₃ —N) may be 0.1 to 5 mg / L (in terms of NH ₄ ⁺ ). If the ammonium ion concentration in the raw water W is less than 0.1 mg / L (NH ₄ ⁺ conversion), it will be difficult to maintain the activity of the nitrifying bacteria group, while if it exceeds 5 mg / L (NH ₄ ⁺ ), Not only is the activity of a further nitrifying bacteria group not obtained, but the amount of leakage from the biological treatment means 3 is too large, which is not preferable. Thus, by adding the ammoniacal nitrogen source at the front stage of the biological treatment means 3, the growth and activity of the nitrifying bacteria group in the biological treatment means 3 can be enhanced. As a result, the ability to decompose and remove urea and urea derivatives can be improved by the group of nitrifying bacteria having increased activity.

At this time, the reason why the pH is adjusted to 5 to 6.5 by adding sulfuric acid as a pH adjusting agent to the raw water W is as follows. That is, the nitrifying bacteria group (ammonia-oxidizing bacteria) having urea resolution can assimilate both urea and ammonia, and the substrate to be used preferentially varies depending on the environmental conditions. For example, when the pH is high or the ammonia / urea ratio is high, ammonia is preferentially used and the urea resolution is rather lowered. Therefore, by adjusting the pH of the raw water W to 5 to 6.5, the nitrifying bacteria group having the optimum value in the neutral range has both ammonia oxidation activity and urea decomposition activity decreased compared to the optimum pH. The decrease in urea decomposition activity is less than the decrease in ammonia oxidation activity. Furthermore, ammonia in an ionic state increases, and the amount of ammonia taken into the ammonia oxidizing bacteria decreases. As a result, urea decomposed by nitrifying bacteria increases. By these actions, the activity of the nitrifying bacteria group can be maintained even if the urea concentration largely fluctuates, and urea can be effectively decomposed and removed. In addition, about the minimum of pH, when the pH of raw | natural water W shall be less than 5, the activity of a nitrifying bacteria group will fall.

Also, an oxidizing agent and a bactericidal agent are added to the raw water W from the second supply mechanism 6. The amount of oxidizer added varies depending on the type of oxidizer used. For example, when a chlorinated oxidizer is used, the total residual chlorine concentration remaining at the stage of the biological treatment means 3 is 0.2 to 1 mg / L. It is preferable to do so. Alternatively, the total residual chlorine concentration remaining in the treated water W1 supplied to the primary pure water apparatus after various treatments is preferably 0.02 to 0.1 mg / L. Note that the disinfectant avoids obstacles in the subsequent treatment caused by the bacteria contained in the treated water W1 of the biological treatment means 3 (slime troubles such as clogging of pipes, increased differential pressure, biofouling of RO membranes, etc.). May be added as needed for the purpose.

Subsequently, the raw water W subjected to such treatment is supplied to the biological treatment means 3 as feed water, and a reducing agent and / or a slime control agent is supplied from the third supply mechanism 7 to the treated raw water W.

Specifically, when free chlorine is present in the biological treatment water and ammonium salt or the like is added as an ammoniacal nitrogen source, the free chlorine and ammonium ions react to produce combined chlorine (chloramine). Bound chlorine is a component that is harder to remove even with activated carbon than free chlorine, and the bound chlorine leaks into biologically treated water. Bound chlorine is said to be a component with low oxidizing power compared to free chlorine, but it is also known that free chlorine is generated again from bound chlorine by an equilibrium reaction. May cause oxidative degradation. For example, when the reducing agent is sodium sulfite, the reducing agent may be added so that the sulfite ion (SO ₃ ²⁻ ) and the hypochlorite ion (ClO ⁻ ) are equimolar or more. In consideration of safety, it may be added in an amount of 1.2 to 3.0 times. Since there is a variation in the oxidizing agent concentration of the treated water, it is more preferable to monitor the oxidizing agent concentration of the treating water and control the amount of reducing agent according to the oxidizing agent concentration. For simplicity, a method may be used in which the oxidant concentration is measured periodically and the addition amount corresponding to the measured concentration is set appropriately. As a means for detecting the oxidant concentration, an oxidation-reduction potential (ORP) can be used. For residual chlorine, a residual chlorine meter (such as a polarographic method) can be used.

In addition, slime control agent is a slime disorder such as clogging of pipes and increased differential pressure caused by cells contained in the treated water of biological treatment means 3 (cells detached from the biological carrier). , RO membrane bio-fouling, etc.) may be added as needed for the purpose of avoidance.

Furthermore, the cells contained in the treated water of the biological treatment means 3 are removed by the cell separation device 4 as necessary.

The addition of the reducing agent and / or slime control agent and the treatment by the bacterial cell separation device 4 may be appropriately performed in accordance with the quality of the biologically treated water from the biological treatment means 3, and the water quality is good. It is not necessary to do it.

In the water treatment method of this embodiment, treated water W1 from which urea is highly removed can be obtained by nitrifying bacteria becoming dominant species in the biological treatment means 3. In particular, the biological treatment means 3 is compared with the raw water W so that the reduced concentration of ammonia nitrogen (NH ₃ -N) is 1/5 or more of the reduced concentration of total organic carbon (TOC) in the raw water W. It is preferable to control. That is, the biological treatment means 3 is controlled so that the relationship of condition A: (NH ₃ -N concentration decreased in the biological treatment means 3)> (TOC concentration reduced in the biological treatment means 3) / 5 is satisfied. preferable.

This is due to the following reasons. That is, by adding ammoniacal nitrogen to the raw water W in the previous stage of the biological treatment means 3 as in the present embodiment, the nitrifying bacteria group can be made dominant, thereby removing ammoniacal nitrogen in the biological treatment. Performance can also be improved. In the biological treatment means 3 in which the nitrifying bacteria group has become dominant species, urea and ammonia nitrogen in the raw water W are decomposed and reduced, and nitrous acid or nitric acid is generated. TOC is also reduced by the decomposition of urea and organic nitrogen, and by the decomposition of organic matter by partially existing BOD-assimilating bacteria, but the decrease is small. Therefore, by making the decrease concentration of ammonia nitrogen (NH ₃ -N) in the biological treatment means 3 to be 1/5 or more of the decrease concentration of total organic carbon (TOC) in the raw water, it can be efficiently reduced to a lower concentration. Urea and urea derivatives can be decomposed and removed, and ultrapure water with a reduced TOC concentration can be produced.

Further, the biological treatment means 3 is configured such that the sum of the concentration of nitrite nitrogen (NO ₂ -N) and the concentration of nitrate nitrogen (NO ₃ -N) in the treated water W1 relative to the raw water W is It is preferable to control so that it becomes 1/5 or more of the reduced concentration of total organic carbon (TOC). That is, condition B: (concentration of (NO ₂ −N) produced in biological treatment means 3) + (concentration of (NO ₃ ) −N produced in biological treatment means 3)> (decreased by biological treatment means 3) It is preferable to control the biological treatment means 3 so that the relationship of (TOC concentration) / 5 is established.

This is due to the following reasons. That is, by adding ammoniacal nitrogen to the raw water W in the previous stage of the biological treatment means 3 as in this embodiment, in the biological treatment means 3 in which the nitrifying bacteria group prevails, urea is decomposed and nitrous acid or Nitric acid is generated, and nitrite nitrogen or nitrate nitrogen concentration increases. Moreover, when organic nitrogen other than ammonia nitrogen and urea is contained in the raw water W, the nitrite nitrogen or nitrate nitrogen concentration resulting from the decomposition thereof increases. TOC decreases due to decomposition of urea and organic nitrogen, and also due to decomposition of organic substances by BOD-assimilating bacteria that are partly present, but the decrease is small. Therefore, the condition of the biological treatment is defined as the sum of the production concentration of nitrite nitrogen (NO ₂ -N) and the production concentration of nitrate nitrogen (NO ₃ -N) in the biological treatment is the total organic carbon in the raw water ( By setting the concentration to 1/5 or more of the reduced concentration of TOC, it is possible to achieve the dominant species of the nitrifying bacteria group, and to efficiently decompose and remove urea and urea derivatives to a lower concentration. Reduced ultrapure water can be produced.

Furthermore, the biological treatment means 3 is controlled so that the reduced concentration of organic nitrogen in the treated water W1 with respect to the raw water W is 1/5 or more of the reduced concentration of total organic carbon (TOC) in the raw water W. preferable. That is, it is preferable to control the biological treatment means 3 so that the relationship of condition C: (organic nitrogen concentration decreased in the biological treatment means 3)> (TOC concentration reduced in the biological treatment means 3) / 5 is satisfied. .

This is due to the following reasons. That is, in the biological treatment means 3 in which the nitrifying bacteria group has become dominant by adding ammoniacal nitrogen to the raw water W in the previous stage of the biological treatment means 3 as in the present embodiment, compared with the reduction range of TOC. The decrease in organic nitrogen increases. Therefore, in the water treatment method for biologically treating raw water containing organic matter as the biological treatment condition, the biological treatment has a reduced concentration of organic nitrogen in the biological treatment of total organic carbon (TOC) in the raw water. By setting it to 1/5 or more of the reduced concentration, urea and urea derivatives can be efficiently decomposed and removed down to a lower concentration, and ultrapure water with a reduced TOC concentration can be produced.

Next, an ultrapure water production method using a water treatment method according to an embodiment of the present invention will be described with reference to FIG. In the ultrapure water production method in the present embodiment, the raw water W is treated by the water treatment device 21 provided with the biological treatment device 3 described above, and then the treated water W1 is treated with the primary pure water device 22 and the subsystem (secondary pure water). Further processing is performed with a pure water production apparatus equipped with the apparatus 23).

The primary pure water device 22 includes a first reverse osmosis membrane (RO) separation device 24, a mixed bed ion exchange device 25, and a second reverse osmosis membrane (RO) separation device 26 in this order. . However, the device configuration of the primary pure water device 22 is not limited to such a configuration. For example, a reverse osmosis membrane separation device, an ion exchange treatment device, an electrodeionization exchange treatment device, a UV oxidation treatment device, etc. You may comprise suitably combining.

The sub-system 23 includes a sub-tank 27, a heat exchanger 28, a low-pressure ultraviolet oxidizer 29, a membrane degasser 30, a mixed bed ion exchanger 31, and an ultrafiltration membrane device (fine particle removal) 32. Arranged in this order. However, the apparatus configuration of the subsystem 23 is not limited to such a configuration, and is configured by combining, for example, a UV oxidation processing apparatus, an ion exchange processing apparatus (non-regenerative type), a UF membrane separation apparatus, and the like. May be.

An ultrapure water production method using such an ultrapure water production system will be described below. First, the treated water W1 treated by the water treatment device 21 is converted into a primary pure water device 22, a first reverse osmosis membrane (RO) separation device 24, a mixed bed ion exchange device 25, a second reverse osmosis membrane ( RO) Separation device 26 removes ion components and the like remaining in treated water W1.

Furthermore, in the sub-system 23, the treated water of the primary pure water device 22 is introduced into the low-pressure ultraviolet oxidizer 29 through the sub-tank 27 and the heat exchanger 28, and the contained TOC component is ionized or decomposed. Further, oxygen and carbon dioxide gas are removed by the membrane deaerator 30, and then the ionized organic substance is removed by the mixed bed ion exchanger 31 at the subsequent stage. The treated water of the mixed bed type ion exchange device 31 is further subjected to membrane separation treatment by an ultrafiltration membrane device (fine particle removal) 32, and ultrapure water can be obtained.

According to the ultrapure water production method as described above, the biological treatment means 3 sufficiently decomposes and removes urea, and the TOC component, metal ions, and other inorganic substances in the primary pure water device 22 and the subsystem 23 in the subsequent stage. -By removing the organic ion component, highly pure ultrapure water can be efficiently produced.

The present invention has been described above with reference to the accompanying drawings. However, the present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the biological treatment means 3 may be a normal biological treatment apparatus, and the nutrient source is not limited to the ammoniacal nitrogen source, and other nitrogen sources may be added. An organic substance may be added.

The following examples further illustrate the present invention.

[Example 1]
As simulated raw water W, municipal water (Nogi-cho water: average urea concentration 10 μg / L, average TOC concentration 0.8 mg / L (asC), ammonium ion concentration less than 0.1 mg / L (asN), nitrite nitrogen concentration 0 0.03 mg / L (asN), average nitrate nitrogen concentration 1.8 mg / L (asN), average free residual chlorine concentration 0.3 ng / L (asCl ₂ ), average total residual chlorine concentration 0.9 mg / L (asCl ₂ ) A reagent urea (manufactured by Kishida Chemical Co., Ltd.) added with an appropriate amount as needed was used.

Since the water temperature of the city water was 20 ° C. or lower during the test period, the water temperature was adjusted to about 20 ° C. using the heat exchanger 2. The city water had a pH of 6.8 to 7.3, but sulfuric acid as a pH adjuster was not added.

In the apparatus having the configuration shown in FIG. 1, the biological treatment means 3 is a fixed bed obtained by filling a cylindrical container with 2 L of granular activated carbon (“Crycol WG160, 10/32 mesh”, manufactured by Kurita Kogyo Co., Ltd.) as a biological carrier. Was used. In addition, the granular activated carbon of the biological treatment means 3 was filled by immersing in 2 L of city water to which 200 mL of nitrified sludge was added after washing the new charcoal, and then water flow was started.

In such a biological treatment apparatus, ammonium chloride (manufactured by Kishida Chemical Co., Ltd.) is added as ammoniacal nitrogen source from the first supply mechanism 5 to the simulated raw water W adjusted to a urea concentration of about 100 μg / L by adding reagent urea. The ammoniacal nitrogen concentration was adjusted to about 0.5 mg / L (asN).

This raw water (water supply) W was passed through the biological treatment means 3 in a downward flow. The water flow rate SV was 20 / hr (water flow rate per hour ÷ filled activated carbon amount). In the water flow treatment, back washing was performed once a day for 10 minutes. Backwashing was performed with biologically treated water in an upward flow from the lower part of the cylindrical container to LV = 25 m / hr (per hour water flow rate ÷ cylinder container sectional area).

When the continuous water flow of the raw water W was carried out under the water flow conditions as described above, the urea concentration of the treated water W1 tended to gradually decrease, and after 3 weeks from the start of water flow, the urea of the treated water W1. The concentration was less than 2 μg / L.

The procedure for analyzing the urea concentration is as follows. That is, first, the total residual chlorine concentration of the test water is measured by the DPD method and reduced with a considerable amount of sodium bisulfite (then, the total residual chlorine is measured by the DPD method, and less than 0.02 mg / L). Confirm that it is.) Next, this reduced test water was passed through an ion exchange resin (“KR-UM1”, Kurita Kogyo Co., Ltd.) at SV50 / hr, deionized and concentrated 10 to 100 times with a rotary evaporator. Thereafter, the urea concentration is quantified by the diacetyl monooxime method.

Table 1 shows the results of measuring the urea concentration, TOC concentration, and ammonia nitrogen concentration of the feed water (raw water W) and the urea concentration, TOC concentration, and ammonia nitrogen concentration of the treated water W1 in such continuous operation.

As apparent from Table 1, the TOC concentration of the treated water W1 was 0.6 mg / L (asC), and the ammoniacal nitrogen concentration was less than 0.1 mg / L (asN). That is, the concentration of ammoniacal nitrogen decreased by the biological treatment means 3 is (0.5− <0.1) => 0.4 mg / L (asN), and the decreased TOC concentration is (0.8). −0.6) = 0.2 mg / L (asC), Condition A: (NH ₃ −N concentration decreased in biological treatment means 3)> (TOC concentration reduced in biological treatment means 3) / 5 It was an operating condition to do.

[Comparative Example 1]
In Example 1, treatment was performed in the same manner except that the feed water in which ammonium chloride was not added from the first supply mechanism 5 to the simulated raw water W was supplied to the biological treatment means 3, and treatment after 3 weeks from the start of water flow The results of measuring the urea concentration, the TOC concentration, and the ammonia nitrogen concentration of the water W1 are also shown in Table 1.

As is clear from Table 1, the urea concentration of the treated water W1 is 67 μg / L, the TOC concentration is 0.4 mg / L (asC), and the ammoniacal nitrogen concentration is less than 0.1 mg / L (asN). It was. That is, the concentration of ammoniacal nitrogen reduced by the biological treatment means 3 is (<0.1- <0.1) ≈0 mg / L (asN), and similarly the reduced TOC concentration is (0.8-0 .4) = 0.4 mg / L (asC), which was not an operating condition satisfying the above-described condition A relationship.

[Comparative Example 2]
In Comparative Example 1, addition of ammonium chloride from the first supply mechanism 5 to the simulated raw water W after the elapse of 3 weeks under the same conditions as in Example 1 and the urea concentration and the TOC concentration of the treated water W1 after the elapse of 2 days The results of measurement of ammonia nitrogen concentration are also shown in Table 1.

As is clear from Table 1, the urea concentration of the treated water W1 was 70 μg / L, the TOC concentration was 0.4 mg / L (asC), and the ammoniacal nitrogen concentration was 0.3 mg / L (asN). . That is, the concentration of ammoniacal nitrogen decreased by the biological treatment means 3 is (0.4−0.3) = 0.1 mg / L (asN), and the decreased TOC concentration is (0.9−0). .4) = 0.5 mg / L (asC), which was not an operating condition satisfying the above-described condition A relationship.

As is clear from Example 1 and Comparative Examples 1 and 2, the urea concentration of the treated water W1 was less than 2 μg / L and the urea concentration could be kept low under the operating conditions of Example 1 that satisfied Condition A. On the other hand, in Comparative Examples 1 and 2 not satisfying the condition A, the urea concentrations in the treated water W1 were 67 μg / L and 70 μg / L, respectively, and the urea concentration could not be sufficiently reduced.

Subsequently, the water flow of Example 1 and Comparative Example 2 was stopped, the granular activated carbon that was the biological carrier that had been filled was extracted, the lower 2/3 of the fixed bed was collected, and the bacterial cells adhering to the granular activated carbon Numbers were analyzed and estimated by quantitative PCR. The results are shown in Table 2. The reason why the lower 2/3 of the fixed bed of granular activated carbon was collected is that the upper side of the fixed bed is exposed to residual chlorine contained in the simulated raw water W, so there is a high possibility that the cells are not attached. is there.

As is apparent from Table 2, in Example 1, about 2% of the total number of bacteria adhering to the granular activated carbon was ammonia-oxidizing bacteria. In contrast, in Comparative Example 2, ammonia-oxidizing bacteria accounted for only about 0.4% of the total number of bacteria attached to the granular activated carbon. From this result, in Example 1, the nitrifying bacteria group (ammonia-oxidizing bacteria) that efficiently decomposes urea is dominant species, and the nitrifying bacteria group that efficiently decomposes and removes urea is dominant species. Thus, while sufficient urea decomposition performance can be maintained, in Comparative Example 2, since these nitrifying bacteria are not dominant species, it is considered that sufficient urea removal performance cannot be obtained.

[Example 2]
In Example 1, the reagent urea is added to the simulated raw water W, the urea concentration is adjusted to about 1 mg / L, and pretreatment is performed by the pretreatment system 1, and then ammonium chloride (as an ammoniacal nitrogen source is supplied from the first supply mechanism 5). (Kishida Chemical Co., Ltd.) was added, and the treatment was performed in the same manner except that the ammoniacal nitrogen concentration was adjusted to about 1.0 mg / L (asN).

When the continuous water flow of the raw water W was carried out under the water flow conditions as described above, the urea concentration of the treated water W1 became less than 2 μg / L about one month after the start of water flow. At this point, the addition of ammonium chloride was stopped and continuous water flow was continued for another 2 weeks.

In such continuous operation, the urea concentration, TOC concentration, ammonia nitrogen concentration, nitrite nitrogen concentration, nitrate nitrogen concentration and organic nitrogen concentration of the feed water (raw water W) and the treated water W1 were measured. The results are shown in Table 3.

As apparent from Table 3, the TOC concentration of the treated water W1 is 0.5 mg / L (asC), the nitrite nitrogen concentration is less than 0.03 mg / L (asN), and the nitrate nitrogen concentration is 2. The organic nitrogen concentration was 6 mg / L (asN) and less than 0.1 mg / L (asN). That is, the sum of the nitrite nitrogen concentration and the nitrate nitrogen concentration produced by the biological treatment means 3 was not changed, so that (2.6−2.0) = 0.6 mg / L (asN) and the TOC concentration decreased similarly is (1.1−0.5) = 0.6 mg / L (asC), and condition B: (generated in the biological treatment means 3 (NO ₂ -N) concentration) + (concentration of (NO ₃ -N) produced in biological treatment means 3)> (TOC concentration decreased by biological treatment means 3) / 5.

[Comparative Example 3]
In Example 1, the treatment was performed in the same manner except that ammonium chloride was not added to the simulated raw water W from the first supply mechanism 5. The urea concentration, TOC concentration, ammonia nitrogen concentration, nitrite nitrogen concentration, nitrate nitrogen concentration and organic nitrogen concentration of the treated water W1 after about 1.5 months from the start of water flow were measured. The results are shown in Table 3.

As is apparent from Table 3, the urea concentration of the treated water W1 is 800 μg / L, the TOC concentration is 0.4 mg / L (asC), and the nitrite nitrogen concentration is less than 0.03 mg / L (asN). Yes, the nitrate nitrogen concentration was 2.1 mg / L (asN), and the organic nitrogen concentration was 0.5 mg / L (asN). That is, the sum of the nitrite nitrogen concentration and the nitrate nitrogen concentration generated by the biological treatment means 3 was not changed, so that (2.1−2.0) = 0.1 mg / Similarly, the TOC concentration decreased in the same manner as L (asN) was (1.1−0.4) = 0.7 mg / L (asC), which was not an operating condition satisfying the above-described condition B.

As is clear from Example 2 and Comparative Example 3 above, the urea concentration of the treated water W1 could be kept low at less than 2 μg / L under the operating conditions of Example 1 that satisfied Condition B. On the other hand, in Comparative Example 3 not satisfying the condition B, the urea concentration of the treated water W1 was 800 μg / L, and the urea concentration could not be reduced much.

Example 3
Reagents urea (manufactured by Kishida Chemical Co., Ltd.) and ammonium chloride are added to city water to adjust the urea concentration to about 50 μg / L and ammoniacal nitrogen concentration to about 0.4 mg / L (asN), and the average urea concentrations shown in Table 4 Simulated raw water W having an average TOC concentration, an ammonium ion concentration, an average free residual chlorine concentration and an average total residual chlorine concentration was prepared.

During the test period, the water temperature of the city water was 20 ° C. or lower, so the water temperature was adjusted to about 20 ° C. using the heat exchanger 2. The city water had a pH of 6.8 to 7.3, but sulfuric acid as a pH adjuster was not added.

The simulated raw water W was passed through a carbonner (“CF25”, manufactured by Kurita Kogyo Co., Ltd.), and the water from which residual chlorine had been removed was fed as a feed water to the same biological treatment means 3 as in Example 1 in a downward flow. The water flow rate SV was 20 / hr (water flow rate per hour ÷ filled activated carbon amount). In the water flow treatment, back washing was performed once a day for 10 minutes. Backwashing was performed with biologically treated water in an upward flow from the lower part of the cylindrical container to LV = 25 m / hr (per hour water flow rate ÷ cylinder container sectional area).

Under the water flow conditions as described above, when the raw water W was continuously passed, the urea concentration, the TOC concentration, the ammonia nitrogen concentration, the average free residual chlorine concentration, and the average total residual chlorine in the treated water W1 at the start of the water flow. The concentration was as shown in Table 4.

As is apparent from Table 4, at the start of water flow, the ammoniacal nitrogen concentration decreased by the biological treatment means 3 was (0.4− <0.1) => 0.3 mg / L (asN), and decreased similarly. The TOC concentration is (1.1−0.5) = 0.6 mg / L (asC). Condition A: (NH ₃ −N concentration decreased in biological treatment means 3)> (decreased in biological treatment means 3) TOC concentration) / 5
This is the operating condition that satisfies the above relationship.

After that, as the continuous water flow continued, the urea concentration of biologically treated water showed an increasing trend, and the ammonia nitrogen concentration also increased, and a decrease in urea removal performance and ammonia nitrogen removal performance was observed.

Furthermore, continuous water supply of raw water W was conducted for 2 weeks. Table 4 shows the urea concentration, the TOC concentration, the ammonia nitrogen concentration, the average free residual chlorine concentration, and the average total residual chlorine concentration in the raw water W and the treated water W1 after two weeks.

As apparent from Table 4, at the time when two weeks passed, the urea concentration of the treated water W1 was 22 μg / L, the TOC concentration was 0.5 mg / L (asC), and the ammoniacal nitrogen concentration was 0.3 mg / L. It was less than (asN). Therefore, the ammoniacal nitrogen concentration decreased by the biological treatment means 3 is (0.4−0.3) = 0.1 mg / L (asN), and the decreased TOC concentration is (1.1−0.1. 5) = 0.6 mg / L (asC), which is no longer an operating condition that satisfies the above-described condition A.

Example 4
In Example 3, sodium hypochlorite (trade name: Sunlac, industrial 12% sodium hypochlorite, manufactured by Honmachi Chemical Industry Co., Ltd.) was added to the raw water treated with carboner after 2 weeks from the start of water flow. The free residual chlorine concentration was adjusted to about 0.3 mg / L (asCl ₂ ), the total residual chlorine concentration was adjusted to about 1.0 mg / L (asCl ₂ ), and water flow was continued.

After the addition of sodium hypochlorite, the urea concentration and ammoniacal nitrogen concentration in biologically treated water showed a gradual decline, and the urea removal performance and ammonia nitrogen removal performance were improved.

Urea concentration, TOC concentration, ammonia nitrogen concentration, average free residual chlorine concentration and average total residual chlorine in raw water W and treated water W1 5 weeks after the start of water flow (3 weeks after the start of sodium hypochlorite addition) The concentration was as shown in Table 4.

As is clear from Table 4, when 5 weeks passed, the urea concentration of the treated water W1 was less than 2 μg / L, the TOC concentration was 0.5 mg / L (asC), and the ammoniacal nitrogen concentration was 0.1 mg / L (asN ). Therefore, the ammoniacal nitrogen concentration decreased by the biological treatment means 3 is (0.5− <0.1) => 0.4 mg / L (asN), and the decreased TOC concentration is (1.0− 0.5) = 0.5 mg / L (asC), and the operating conditions were restored to satisfy the above-described condition A.

As is clear from Example 3 and Example 4 above, under the operating conditions of Example 4 that satisfied Condition A, the urea concentration of the treated water W1 could be maintained as low as less than 2 μg / L even after 5 weeks. On the other hand, in Example 3, the urea concentration was less than 2 μg / L in the initial state. However, when the condition A is not satisfied, the urea concentration of the treated water W1 becomes 22 μg / L in two weeks, and the urea concentration is reduced. It could not be reduced sufficiently.

In Example 4, by adding sodium hypochlorite (oxidant) to biological treatment water, the growth and activity of BOD-assimilating bacteria can be suppressed, and urea is efficiently decomposed and removed. In contrast to the fact that the nitrifying bacteria group having a resistance of 1000 to oxidants could be dominant, in Example 3, since there is no oxidant, the growth and activity of BOD-utilizing bacteria is increased, so that It is thought that with the progress, the nitrifying bacteria group with high urea removal efficiency was deactivated, and the urea removal performance was lowered.

Example 5
Reagent urea and sodium acetate were added to city water to adjust the urea concentration to about 50 μg / L and the TOC concentration to about 20 mg / L (asC) to obtain raw water W.

This raw water W is passed through a carbonner (“CF25”, manufactured by Kurita Kogyo Co., Ltd.) to remove residual chlorine, and further treated with a reverse osmosis membrane (“ES20-D4” (manufactured by Nitto Denko Corporation) to obtain a urea concentration of 41 μg. / L, TOC concentration of 90 μg / L (asC), and organic nitrogen concentration of 40 μg / L (asN) were obtained, and this water supply was passed through the same biological treatment means 3 as in Example 1 in a downward flow. The water flow rate SV was 20 / hr (water flow rate per hour ÷ filled activated carbon amount) In the above water flow treatment, backwashing was performed once a day for 10 minutes. In the treated water, an upward flow from the lower part of the cylindrical container to the upper part was performed at LV = 25 m / hr (per hour water flow rate ÷ cylindrical container cross-sectional area).

Under the water flow conditions as described above, the raw water W was continuously passed, and the urea concentration, the TOC concentration, and the organic nitrogen concentration of the treated water W1 after 2 weeks from the start of the water flow were measured. Table 5 shows the TOC concentration and organic nitrogen concentration.

As is clear from Table 5, the urea concentration at the time when two weeks passed was less than 2 μg / L, the TOC concentration was 70 μg / L (asC), and the organic nitrogen concentration was 10 μg / L (asN). Therefore, the organic nitrogen concentration decreased by the biological treatment means 3 is (40-10) = 30 μg / L (asN), and similarly, the decreased TOC concentration is (90-70) = 20 μg / L (asC). Yes, the operating conditions satisfy the above-mentioned condition C.

[Comparative Example 4]
In Example 4, the raw water W was not treated with a reverse osmosis membrane, and the feed water having a urea concentration of 52 μg / L, a TOC concentration of 1800 μg / L (asC), and an organic nitrogen concentration of 110 μg / L (asN) was treated in the same manner. Processed. Table 5 shows the results of measuring the urea concentration, TOC concentration, and organic nitrogen concentration of the treated water W1 two weeks after the start of water flow, together with the urea concentration, TOC concentration, and organic nitrogen concentration of the feed water.

As is apparent from Table 5, the urea concentration at the time when two weeks passed was less than 37 μg / L, the TOC concentration was 500 μg / L (asC), and the organic nitrogen concentration was 60 μg / L (asN). Therefore, the organic nitrogen concentration decreased by the biological treatment means 3 is (110-60) = 50 μg / L (asN), and similarly, the decreased TOC concentration is (1800-500) = 1300 μg / L (asC). Yes, the operating conditions did not satisfy the above-mentioned condition C.

As can be seen from Table 5, under the operating conditions of Example 5 that satisfied Condition C, the urea concentration of biologically treated water was less than 2 μg / L and the urea concentration could be kept low. On the other hand, in Comparative Example 4 not satisfying the condition C, the urea concentration of the treated water was 37 μ g / L, and it was confirmed that the urea concentration could not be sufficiently reduced.

In Example 4, the increase in the growth and activity of BOD assimilating bacteria can be suppressed by using the reverse osmosis membrane treatment to remove the readily biodegradable organic matter from the raw water W as the water supply for the biological treatment means 3. In contrast, the nitrifying bacteria group capable of efficiently decomposing and removing urea could be dominant, whereas in Comparative Example 5, the water supply contains a lot of readily biodegradable organic substances. It is considered that the nitrifying bacteria group having high urea removal efficiency could not be predominated due to the increase in the growth and activity of, and the urea removal performance was lowered.

DESCRIPTION OF SYMBOLS 1 ... Pretreatment system 3 ... Biological treatment means 5 ... 1st supply mechanism 6 ... 2nd supply mechanism 21 ... Water treatment apparatus 22 ... Primary pure water apparatus 23 ... Subsystem (secondary pure water apparatus)
W ... Raw water W1 ... treated water

Claims

In a water treatment method for biologically treating raw water containing organic matter,
A water treatment method, wherein the biological treatment is a preferential species of nitrifying bacteria.
The biological treatment is characterized in that the reduced concentration of ammonia nitrogen (NH 3 -N) in the biological treatment is 1/5 or more of the reduced concentration of total organic carbon (TOC) in the raw water. The water treatment method according to claim 1.
In the biological treatment, the sum of the production concentration of nitrite nitrogen (NO 2 -N) and the production concentration of nitrate nitrogen (NO 3 -N) in the biological treatment is the total organic carbon (TOC) in the raw water. The water treatment method according to claim 1, wherein the water treatment method is 1/5 or more of the reduced concentration.
2. The biological treatment according to claim 1, wherein the reduced concentration of organic nitrogen in the biological treatment is 1/5 or more of the reduced concentration of total organic carbon (TOC) in the raw water. Water treatment method.
The water treatment method according to any one of claims 1 to 4, wherein an ammoniacal nitrogen source is added to the biological treatment water.
The water treatment method according to any one of claims 1 to 4, wherein the feed water for the biological treatment is adjusted to pH 5 to 6.5.
The water treatment method according to any one of claims 1 to 4, wherein a chlorine-based oxidizing agent and / or a bactericidal agent is added to the water for biological treatment.
The water treatment method according to any one of claims 1 to 4, wherein the TOC concentration of the biological treatment feed water is reduced.
Ultrapure water production characterized in that ultrapure water is produced by treating the treated water obtained by the water treatment method according to any one of claims 1 to 8 with a primary pure water device and a secondary pure water device. Method.