TWI424970B - Anaerobic Biological Treatment and Anaerobic Biological Treatment - Google Patents

Description

Anaerobic biological treatment method and anaerobic biological treatment device

The present invention relates to a biological treatment method and a biological treatment apparatus, which is an anaerobic biological treatment of discharged water containing an alkylammonium salt such as TMAH or choline, and a small amount of carbon. The organic matter discharges water and the like.

In the past, semiconductor factories and liquid crystal factories used water containing alkylammonium salts when discharging used Tetramethylammonium Hydroxide=TMAH wastewater (sometimes because it contained some resin from the resist). The decomposition treatment and the discharge water recovery treatment include various methods such as biological treatment, ion exchange resin treatment, and membrane treatment (for example, refer to Patent Documents 1 to 4).

In addition, in the past, when the waste water project for wood pulp production and the chemical plant discharge waste water containing less than 4 carbons, more specifically, the discharge water containing organic substances having two or less carbons such as acetic acid, ethanol, and acetaldehyde is used. In the anaerobic treatment, since the granular sludge is disintegrated into smaller particles, the amount of sludge is reduced, and the processing operation becomes unstable.

In general anaerobic treatment, the anaerobic hydrolyzed bacteria used to decompose higher molecular weight saccharides, proteins, and lipids into low molecules, and bio-polymers that produce acid-producing bacteria of organic acids. The bridging effect plays an important role in the generation and maintenance of particles. In addition, methane The genus Methanosaeta, which is a bacterium of the genus Methanosaeta, is a granule-forming skeleton and is important for the formation of granules.

However, if the organic matter with less carbon is decomposed, the hydrolyzed bacteria and the acid-producing bacteria are less, and the methane-producing bacteria are dominant. Moreover, the non-linear methane-producing bacteria Methanosarcina and Methanobacterium are more susceptible than the methane-producing bacteria Methanosaeta, such as methanol and TMAH. It tends to become thinner and collapse. When the granular sludge is crushed and collapsed, the sludge in the reaction tank will flow out, and the treatment becomes unstable.

The methods shown in Patent Documents 5 to 8 are specific measures proposed in the past to solve the above problems.

Previous technical literature:

Patent Document 1: Japanese Patent Publication No. 8-235.

Patent Document 2: JP-A-2001-276825.

Patent Document 3: Patent No. 2730610.

Patent Document 4: Japanese Laid-Open Patent Publication No. H11-262765.

Patent Document 5: Patent No. 4193310.

Patent Document 6: JP-A-2008-279383.

Patent Document 7: Patent No. 2,563,004.

Patent Document 8: JP-A-2008-279385.

In the traditional recycling technology, the recycled TMAH will be reused in Emission of water containing a higher concentration of alkylammonium salts such as TMAH is an effective method, but it has problems in the purity and economic effects of the drug.

In addition, although the traditional physical and chemical decomposition treatment method has a fast response and a small equipment scale, the processing cost is high, which is also a problem.

A lower-cost treatment method for discharging water containing an alkylammonium salt such as TMAH has a biological decomposition treatment method, etc., but in the past, an aerobic biological treatment method was the mainstream. The aerobic biological treatment is generally carried out by a bulk method or an impregnated membrane activated sludge method.

The method of Patent Document 5 is an anaerobic biological treatment method in which a polymer flocculant is added after the completion of the treatment of the granular sludge to avoid collapse of the granular sludge. However, this method is difficult if the anaerobic sludge is put into treatment and the granular sludge is formed in the anaerobic sludge. Moreover, the long-term addition of the polymer agglutinating agent may cause the charge of the polymer flocculant and the polymer flocculant to repel each other, resulting in dispersion of the granular sludge. Another problem is the high price of polymer agglutinators.

The method of Patent Document 6 is a treatment method of adding nitric acid and nitrous acid anaerobic organisms. Since this method actively adds the target substances to be treated - nitric acid and nitrous acid, raw water fluctuations, device defects, and operation management occur. The problem is that the nitrogen is also discharged at the same time when the treated water is discharged, which may cause water pollution. In addition, the method must allow the denitrifying bacteria to coexist with the methane-producing bacteria. If the anaerobic reaction is initiated by the denitrification reaction, the raw water may be changed, the treated water quality may be deteriorated, and the nitric acid or the like may be leaked into the treated water.

The method of Patent Document 7 is to add a treatment substance at the beginning of the treatment. - An anaerobic treatment of methanol 4 times the amount of acetic acid, but it is impractical to add a larger amount of acetic acid than the discharged water in the actual device. Moreover, this method stops injecting acetic acid after the start of the treatment, and the problem of particle stability and handling stability occurs after the injection of acetic acid is stopped for a while.

The method of Patent Document 8 is an anaerobic treatment using sugar addition. These sugars are carbohydrates, including monomeric monosaccharides, complex condensates such as oligosaccharides, polysaccharides composed of a plurality of monosaccharides (starch, cellulose, etc.). The monosaccharide has a triose of 3 carbons, a tetraether (tetrose) containing 4 carbons, a pentose containing 5 carbons, and a hexose containing 6 carbons. . This type of anaerobic biological treatment with monosaccharide addition may cause the collapse of granular sludge, so the addition of sugar does not prevent the collapse of granular sludge. This type of method only has an example of adding sugar to the starch. Since starch is not easily soluble in water, if starch is used, it must be dissolved in hot water to form a starch solution, which can cause problems in operation management.

As mentioned above, various methods have their problems, so it is difficult to practically apply. In addition, most of the above methods are emissions of organic substances such as methanol containing one carbon in the process of wood pulp production, and there is no use of a hydrocarbon containing 4 carbons of TMAH discharged water from a semiconductor factory such as pure water or ultrapure water engineering. Case of anaerobic biological treatment of quaternary ammonium salts (sometimes containing a resin in a resist or a surfactant).

Therefore, the object of the present invention is to reduce the treatment of TMAH by anaerobic biological treatment of discharge water containing alkyl ammonium salts such as TMAH and choline. The equipment area of the alkyl ammonium salt-containing water treatment equipment such as choline provides an economical and environmentally friendly anaerobic biological treatment method and an anaerobic biological treatment device, which can properly treat the discharge water containing alkyl ammonium salts. And an anaerobic biological treatment method and an anaerobic biological treatment apparatus containing discharged water such as TMAH or choline discharged from a semiconductor factory or the like, and the like.

The present invention relates to an anaerobic biological treatment method for discharging water containing an alkylammonium salt, and in the above biological treatment, the alkylammonium salt concentration in the alkylammonium salt-containing discharged water is 20,000 mg/L or less.

In addition, the present invention is a treatment method for treating an alkylammonium salt-containing effluent water by an anaerobic biological treatment method, and the organic nitrogen and ammonia nitrogen in the alkylammonium salt-containing water discharged during the aforementioned biological treatment (Ammonia Nitrogen) The total concentration is below 3900 mg-N/L.

In the aforementioned anaerobic biological treatment method, it is preferred that a part of the biologically treated treated water is recirculated into the aforementioned alkylammonium salt-containing discharge water.

In the aforementioned anaerobic biological treatment method, when the biological treatment is carried out, the concentration of the alkylammonium salt contained in the alkylammonium salt-containing discharge water is preferably less than 10,000 mg/L.

The present invention relates to an anaerobic biological treatment method for treating alkyl ammonium salt-containing discharge water by anaerobic biological treatment, and the pH range is 6.5~ when the aforementioned alkyl ammonium salt-containing water is subjected to the aforementioned biological treatment. Between 9.0.

The invention relates to an anaerobic biological treatment method for treating water containing alkyl ammonium salt discharged by anaerobic biological treatment, and the water temperature is above 20 ° C when the aforementioned biological treatment of the alkyl ammonium salt-containing water is performed. .

The present invention relates to an anaerobic biological treatment method for treating alkyl ammonium salt-containing discharge water by anaerobic biological treatment, and the conditions thereof must meet any of the following two items: (1) the aforementioned alkane is contained in the foregoing biological treatment. The concentration of the alkylammonium salt in the quaternary ammonium salt discharge water must be less than 20000 mg / L, and after the completion of the above biological treatment, part of the treated water must be recirculated into the aforementioned alkyl ammonium salt-containing discharge water; (2) in the foregoing In biological treatment, the total concentration of organic nitrogen and ammonia nitrogen in the above-mentioned alkylammonium salt-containing water shall be less than 3900 mg-N/L, and after completion of the above biological treatment, part of the treated water shall be again placed in the aforementioned alkyl ammonium. Circulating in the salt discharge water; (3) when the aforementioned alkyl ammonium salt-containing water is subjected to the aforementioned biological treatment, the pH ranges from 6.5 to 9.0; (4) the aforementioned alkyl ammonium salt-containing discharge water is subjected to the aforementioned biological treatment. The water temperature must be above 20 °C.

Further, in the aforementioned anaerobic biological treatment method, the alkylammonium salt is preferably tetramethylammonium hydroxide (TMAH).

The anaerobic biological treatment device of the present invention has a biological treatment method for biological treatment of alkylammonium salt-containing water by anaerobic method, and a method for adjusting the concentration of the alkylammonium salt so that the discharged water flows into the aforementioned biological treatment method. The concentration of the alkylammonium salt in the aforementioned alkylammonium salt-containing water can be adjusted to less than 20,000 mg/L.

The anaerobic biological treatment device of the present invention has a biological treatment method for discharging water containing an alkyl ammonium salt by anaerobic method, and a method for adjusting nitrogen concentration In order to allow the discharged water to flow into the aforementioned biological treatment method, the concentration of the organic nitrogen and the ammonia nitrogen in the alkylammonium salt-containing discharged water is lower than 3900 mg-N/L.

In the aforementioned anaerobic biological treatment apparatus, it is preferable to have a circulation method so that a part of the treated water after the biological treatment can be re-introduced into the aforementioned alkyl ammonium salt-containing discharge water cycle.

In the foregoing anaerobic biological treatment device, it is preferred to have a method for adjusting the concentration of the alkylammonium salt so as to adjust the concentration of the alkylammonium salt in the alkylammonium salt-containing discharge water when the discharged water flows into the biological treatment method. , making it lower than 10000mg / L.

The anaerobic biological treatment device of the present invention has a biological treatment method for treating the alkyl ammonium salt-containing discharge water by biological treatment, and a set of pH adjustment methods for carrying out the aforementioned ammonia-containing salt-containing water discharge organism The pH can be adjusted to a range of 6.5 to 9.0 during the treatment.

The anaerobic biological treatment device of the present invention has a biological treatment method for treating the alkyl ammonium salt-containing discharge water by biological treatment, and a set of the above biological treatments for performing the aforementioned alkyl ammonium salt-containing water discharge, The temperature adjustment method in which the water temperature in the biological treatment method is adjusted to 20 ° C or higher.

The anaerobic biological treatment device of the present invention has a biological treatment method for treating an alkylammonium salt-containing effluent water by an anaerobic biological treatment method, and a method of any two or more of the following (1) to (4): (1) When the discharged water flows into the biological treatment method, the alkylammonium salt concentration adjustment method in which the alkylammonium salt concentration in the alkylammonium salt-containing water is adjusted to 20000 mg/L or less, and the alkylammonium salt concentration adjustment method And after the aforementioned biological treatment, the Ministry The treated water is again placed in the circulation method of circulating the alkylammonium salt-containing discharge water; (2) the total concentration of the organic nitrogen and the ammonia nitrogen in the discharged alkylammonium salt-containing water when the discharged water flows into the biological treatment method Adjusting the nitrogen concentration adjustment method to 3900 mg-N/L or less, and the circulation method of recirculating part of the treated water into the aforementioned alkyl ammonium salt-containing discharge water after the nitrogen concentration adjustment method and the foregoing biological treatment; (3) a pH adjustment method for adjusting the pH to a range of 6.5 to 9.0 in the biological treatment of the alkylammonium salt-containing water discharged; (4) when performing the aforementioned biological treatment of the alkylammonium salt-containing water discharged, The temperature adjustment method of adjusting the water temperature in the biological treatment method to 20 ° C or higher.

In the aforementioned anaerobic biological treatment apparatus, the alkylammonium salt is preferably tetramethylammonium hydroxide (TMAH).

The present invention relates to an anaerobic biological treatment method for treating an alkylammonium salt-containing water discharged by an anaerobic biological treatment method, wherein the concentration of the alkylammonium salt in the alkylammonium-containing salt-containing water is lower than that in the biological treatment. 20000 mg / L.

The present invention relates to an anaerobic biological treatment method for treating an alkylammonium salt-containing water by an anaerobic biological treatment method, and the total amount of organic nitrogen and ammonia nitrogen in the alkyl ammonium salt-containing water discharged during the foregoing biological treatment. The concentration is below 3900 mg-N/L.

The invention adopts an anaerobic biological treatment method for treating an anaerobic biological treatment method for discharging water containing an alkyl ammonium salt, and when the biological treatment of the above-mentioned alkyl ammonium salt-containing water is carried out, the water temperature is above 20 ° C. .

The invention relates to the treatment of alkyl ammonium containing by anaerobic biological treatment A biological treatment apparatus for a method of discharging water by salt, wherein when the discharged water flows into the biological treatment method, the concentration of the alkylammonium salt in the alkylammonium-containing salt-containing water is 20,000 mg/L or less.

The present invention relates to a biological treatment device comprising a method for treating an alkylammonium salt-containing discharge water by an anaerobic biological treatment method, wherein the organic nitrogen contained in the alkyl ammonium salt-containing water is discharged when the discharged water flows into the biological treatment method. The total concentration with ammonia nitrogen is below 3900 mg-N/L.

The present invention relates to a biological treatment apparatus comprising a method for treating an alkylammonium salt-containing effluent water by an anaerobic biological treatment method, wherein the biological treatment method comprises the treatment of the alkylammonium salt-containing effluent water by the biological treatment method The water temperature is above 20 °C.

The present invention is an anaerobic biological treatment method for treating discharged water containing an alkyl ammonium salt by an anaerobic biological treatment method, and supplies molasses to the aforementioned discharged water.

The present invention is an anaerobic biological treatment method for treating discharged water containing organic matter of 6 carbons or less by biological treatment, and supplies molasses to the discharged water.

In the aforementioned anaerobic biological treatment method, it is preferable to supply the aforementioned molasses at the time of starting the above biological treatment and after the start of the biological treatment.

In the anaerobic biological treatment method described above, it is preferable that the anaerobic sludge is introduced into the reaction tank for performing the biological treatment to start the biological treatment described above.

In the aforementioned anaerobic biological treatment method, the discharge water is preferably discharged from a semiconductor factory.

In the anaerobic biological treatment method, the alkylammonium salt and the organic substance having 6 or less carbon atoms are preferably tetramethylammonium hydroxide (TMAH).

In the anaerobic biological treatment method described above, it is preferable to fill the carrier in the reaction vessel in which the biological treatment is carried out when the biological treatment described above is started.

The anaerobic biological treatment apparatus of the present invention comprises a reaction tank for treating an alkylammonium salt-containing discharge water by an anaerobic biological treatment method, and a molasses supply method for supplying the molasses to the discharged water.

The anaerobic biological treatment apparatus of the present invention comprises a reaction tank for treating an organic substance containing six or less carbons by an anaerobic biological treatment method, and a method for supplying molasses for supplying the molasses to the discharged water.

In the aforementioned anaerobic biological treatment apparatus, the aforementioned molasses supply method preferably supplies molasses at the start of the biological treatment and after the start of the biological treatment.

In the anaerobic biological treatment apparatus described above, it is preferable that the anaerobic sludge is introduced into the reaction tank when the biological treatment is started.

In the aforementioned anaerobic biological treatment apparatus, the discharge water is preferably discharged from a semiconductor factory.

In the anaerobic biological treatment apparatus, the alkylammonium salt and the organic substance having 6 or less carbon atoms are preferably tetramethylammonium hydroxide (TMAH).

In the anaerobic biological treatment device described above, it is preferable to fill the carrier in the reaction vessel in which the biological treatment is performed when the biological treatment described above is started.

According to the present invention, when anaerobic biological treatment of discharged water containing an alkylammonium salt such as TMAH or choline is carried out, treatment with TMAH, choline, etc. can be reduced. The installation area of the treatment equipment for the discharge of alkylammonium salt, with economic benefits and environmental benefits, provides good biological treatment and biological treatment equipment, and also can well treat the alkyl ammonium salt discharge water and contains 6 Emission water such as organic substances such as carbon emissions, especially from semiconductor factories, emits water such as TMAH and choline.

Embodiments of the present invention are described below. This embodiment is an embodiment of the present invention, but the present invention is not limited to the embodiment.

<Embodiment 1>

Fig. 1 is a schematic view showing a configuration of an anaerobic biological treatment apparatus of the present embodiment. As shown in Fig. 1, the anaerobic biological treatment apparatus 1 includes a raw water tank 10, an adjustment tank 12, an anaerobic biological treatment tank 14, a separation tank 16, a nitrogen treatment tank 18, and a treatment tank 20. The adjustment groove 12 includes the first adjustment groove 12a and the second adjustment groove 12b, but it does not necessarily have to be a plurality of grooves, or only a single groove.

The raw water tank 10 and the adjustment tank 12, the adjustment tank 12 and the anaerobic biological treatment tank, the anaerobic biological treatment tank 14 and the separation tank 16, the separation tank 16 and the nitrogen treatment tank 18, the nitrogen treatment tank 18 and the treatment tank 20 They are connected by pipes 22a to 22e, respectively. Further, pumps 24a, 24b are provided on the pipes 22a, 22b.

The dilution water inflow line 26, the pH adjuster inflow line 28, and the nutrient inflow line 30 are connected to the first adjustment tank 12a. The second adjustment slot 12b is connected The pH adjuster then flows into line 28 and vapor inflow line 32. Further, the piping 22d is connected to the first adjustment tank 12a through the circulation line 34. The first adjusting groove 12a and the second adjusting groove 12b are provided with stirring means 36, 38.

The anaerobic biological treatment tank 14 may be an anaerobic biological treatment such as an alkylammonium salt or the like, and a most representative granule-upflow sludge bed type anaerobic biological treatment such as UASB type or EGSB type may be used. The tank and the fixed bed type or fluidized bed type anaerobic biological treatment tank using the support. The type of the carrier to be used in the anaerobic biological treatment is not particularly limited. For example, a foamed carrier such as urethane, a gel-like carrier such as polyvinyl alcohol (PVA), a fibrous carrier, a nonwoven fabric molded article, or a molded article made of polypropylene. In addition, the sludge used for anaerobic biological treatment is not particularly limited, and for example, anaerobic sludge, granules or sewage treatment used in food factories, beverage factories, paper factories, chemical factories, and livestock discharge water treatments. Field digested sludge and so on. In addition, it is preferable to add a core substance such as iron, a calcium salt, and fly ash, and a flocculating agent, an organic substance, or the like to promote the particle forming material when the amount of the particles is not increased or decreased during the operation.

According to the present inventors, in the anaerobic biological treatment tank 14, an alkylammonium salt (for example, TMAH) is decomposed into methane, carbonate ions, ammonia ions and the like due to anaerobic organisms.

The operation of the anaerobic biological treatment apparatus 1 and the anaerobic biological treatment method in the present embodiment will be described below.

The pump 24a is started, and the alkylammonium-containing salt discharge water in the raw water tank 10 is supplied to the adjustment tank 12 through the pipe 22a. In addition, the dilution water flows into the line 26 Supply dilution water to the adjustment tank 12. When the discharged water flows into the anaerobic biological treatment tank 14 (when biological treatment is carried out), the concentration of the alkylammonium salt in the alkylammonium salt-containing water must be 20,000 mg/L or less, preferably 10,000 mg/L or less. Especially when there is concern about changes in water quality and effects on coexisting substances, the concentration of alkylammonium salts in alkylammonium-containing discharge water is preferably low when the discharged water flows into the anaerobic biological treatment tank 14 (when biological treatment is carried out). More preferably, it is in the range of 1000 to 3000 mg/L at 5000 mg/L. In the present embodiment, if the concentration of the alkylammonium salt in the alkylammonium salt-containing water exceeds 20,000 mg/L, it is only necessary to supply dilution water to dilute the concentration to 20,000 mg/L or less. However, even if the concentration of the alkylammonium salt in the alkylammonium salt-containing water is less than 20,000 mg/L (for example, above 10,000 mg/L), the dilution water may be supplied, for example, diluted to 10000 mg/L or 1000 to 3000 mg/L. Also within the scope. When the discharged water flows into the anaerobic biological treatment tank 14, if the concentration of the alkylammonium salt in the alkylammonium salt-containing discharge water exceeds 20,000 mg/L, the decomposition reaction rate of the alkylammonium salt becomes slow during the biological treatment.

In the present embodiment, an inductor for inspecting the concentration of ammonia ions in the treated water after biological treatment may be attached to a position such as the pipe 22c. Further, the concentration of the alkylammonium salt can be estimated from the detected ammonia ion concentration, and the amount of the dilution water added can be determined based on the estimated value so that the concentration of the alkylammonium salt when the discharged water flows into the anaerobic biological treatment tank 14 Can be within the above range. Further, an inductor that senses the concentration of the alkylammonium salt may be attached to the adjustment tank 12 or the pipe 22a. Then, the addition amount of the dilution water is determined according to the determined concentration of the alkyl ammonium salt, so that the alkyl ammonium salt is concentrated when the discharged water flows into the anaerobic biological treatment tank 14. The degree of energy falls within the above range.

When the ammonia ion concentration in the anaerobic biological treatment tank 14 exceeds 5000 mg/L, the decomposition reaction rate is lowered, so the ammonia ion concentration in the anaerobic biological treatment tank 14 must be less than 5000 mg/L, preferably 1000 mg/min. L or less. In the anaerobic biological treatment, almost all of the nitrogen components other than nitric acid and nitrous acid in the discharged water are ammonia ions. Therefore, in the present embodiment, the dilution water is supplied to the adjustment tank 12 through the dilution water inflow line 26 to allow the discharge water to be discharged. When flowing into the anaerobic biological treatment tank 14 (when performing biological treatment), the total concentration of organic nitrogen and ammonia nitrogen in the alkylammonium salt-containing water is less than 3900 mg-N/L, preferably below 780 mg-N/L. The ammonia ion concentration in the anaerobic biological treatment tank 14 falls within the above range. In the present embodiment, if the total concentration of the organic nitrogen and the ammonia nitrogen in the alkylammonium salt-containing water exceeds 3,900 mg-N/L, the dilution water must be supplied to dilute the concentration to 3,900 mg-N/L or less. However, even if the total concentration of organic nitrogen and ammonia nitrogen in the alkylammonium salt-containing water is less than 3900 mg-N/L, it can be diluted with dilution water.

The dilution water used in the present embodiment may be industrial water, discharged water, or distilled water (condensed water) obtained by distilling ammonia waste liquid and IPA waste liquid if equipment is present in the factory. The water temperature of the distilled treated water is higher at 40 ° C, so that the anaerobic biological treatment tank 14 can be warmed to promote the decomposition reaction of the alkyl ammonium salt.

Further, in the present embodiment, the biologically treated partial treated water and the dilution water may be supplied to the adjustment tank 12 in place of the dilution water through the circulation line 34. If the concentration of alkylammonium salt in the discharged water is too high, it is diluted emission at this time. When water is added to the dilution water, the amount of water discharged from the anaerobic biological treatment tank 14 is increased. When increasing the amount of water required for dilution and increasing the amount of water discharged, it is preferable to recycle the treated water to dilute the discharged water.

In the present embodiment, the biologically treated partial treated water may be supplied to the adjustment tank 12 together with the dilution water or the dilution water through the circulation line 34. When flowing into the anaerobic biological treatment tank 14 (when performing biological treatment), the concentration of the alkylammonium salt in the alkylammonium salt-containing water must be below 20,000 mg/L, preferably below 10,000 mg/L, and more preferably at low levels. At 5000mg/L, further, preferably in the range of 1000~3000mg/L, or the total concentration of organic nitrogen and ammonia nitrogen in the alkylammonium salt-containing water is less than 3900mg-N/L, preferably 780mg -N/L or less is also possible. However, in the treated water after biological treatment, since the ammonia ion generated by decomposing the alkyl ammonium salt is contained, the total concentration of the organic nitrogen and the ammonia nitrogen in the water discharged from the alkyl ammonium salt is less than 3900 mg-N/L. Direct circulation of water does not require the use of dilution water, it is best to dilute the discharge water. In addition, even if the total concentration of organic nitrogen and ammonia nitrogen in the alkylammonium salt-containing water is lower than 3900 mg-N/L, dilution water (and treated water) may be supplied to dilute the discharged water.

In the present embodiment, in the biological treatment of the alkylammonium salt-containing water, the pH adjuster is supplied from the pH adjuster inflow line 28 to the adjustment tank so that the pH falls within the range of 6.5 to 9.0, preferably Between 7.0 and 8.0. If the pH of the alkylammonium salt-containing water is out of the above range, the decomposition reaction rate of the alkylammonium salt in the biological treatment is slowed down. In addition, in the past, in order to reduce the hindrance of ammonia in the anaerobic biological treatment, the pH is preferably a weak acid of 6.5 to 7.0. The range of properties, but the treatment of alkyl ammonium salts must be at a pH of 7.0 ~ 8.0 to achieve the best treatment results. This is the first condition discovered by the inventors. Here, in the above-mentioned pH adjustment, the concentration of the alkylammonium salt in the alkylammonium salt-containing water is preferably 20,000 mg/L or less, and the total concentration of the organic nitrogen and the ammonia nitrogen is preferably 3,900 mg-N/L or less.

The pH adjuster used in the present embodiment is not particularly limited to an acid agent such as hydrochloric acid or an alkaline agent such as sodium hydride. Further, the pH adjuster may also be a sodium bicarbonate buffer, a citric acid buffer or the like having a buffering action.

In the present embodiment, when the biological treatment of the alkylammonium salt-containing water is performed, the temperature of the water in the anaerobic biological treatment tank 14 is adjusted to a temperature of preferably 20 ° C or higher, and more preferably 28 °. Within the range of 35 °C. The decomposition of the alkylammonium salt of the anaerobic biological treatment can also be carried out in an environment below 20 ° C, but if the decomposition reaction rate is slowed below 20 ° C, the water temperature must be adjusted to the above range. The above temperature adjustment method is not particularly limited. For example, steam may be supplied from the vapor inflow line 32 to the adjustment tank 12 (e.g., the second adjustment tank 12b) to adjust the water temperature in the anaerobic biological treatment tank 14, or A heater is placed on the oxygen biological treatment tank 14, and the temperature of the water in the anaerobic biological treatment tank 14 is adjusted by the heat of the heater. Alternatively, the heated dilution water may be supplied to adjust the temperature of the water in the anaerobic biological treatment tank 14. Alternatively, methane gas is generated when the alkylammonium salt is decomposed, and after the desulfurization treatment according to the general anaerobic treatment, the heat energy of the methane boiler can be recovered, and the heat energy is supplied to the anaerobic biological treatment tank 14 to adjust the water temperature. Here, when the temperature of the water in the anaerobic biological treatment tank 14 is adjusted to the above range, the alkylammonium salt in the alkylammonium salt-containing water is concentrated. The degree must be less than 20000 mg / L, and the total concentration of organic nitrogen and ammonia nitrogen is lower than 3900 mg-N / L.

In the present embodiment, in order to maintain good decomposition activity of the anaerobic organism, it is preferable to add a nutrient to the adjustment tank 12 through the nutrient inflow line 30. The type of the nutrient is not particularly limited, and a carbon source, a nitrogen source, or other inorganic salts can be used.

The alkylammonium salt in the alkylammonium salt-containing water can be decomposed into methane (gas), ammonia ion or the like in the anaerobic biological treatment tank 14 by the various methods described above. In this regard, in the present embodiment, the alkylammonium salt is decomposed by anaerobic biological treatment, and it is preferred to adjust the concentration of the alkylammonium salt by using (1) as described above or to adjust the concentration to be partially treated with water. Circulating; (2) adjusting the total concentration of nitrogen and ammonia nitrogen in the organism or adjusting the total nitrogen concentration and circulating part of the treated water; (3) adjusting the pH of the water containing alkyl ammonium salt; (4) adjusting the alkyl group After the ammonium salt discharges the water temperature of the water; it is carried out in either of the above methods.

Compared with aerobic treatment, the type of raw water that can be treated with anaerobic biological treatment in the past is relatively limited, and the raw water that uses anaerobic biological treatment mainly contains biodegradable polymer organic substances such as protein, carbohydrate, fat, etc. Substances such as foods or beverages containing sugars, alcohols, etc., and water discharged from brewing factories. In addition, since the treated water quality of the anaerobic biological treatment cannot reach the concentration of the aerobic biological treatment, the aerobic biological treatment equipment is generally disposed in the latter stage. The practical situation of anaerobic biological treatment is as described above, but the inventors have found that it is difficult for aerobic biological treatment. The alkylammonium salt contained in the decomposed synthetic material TMAH, choline, etc., is subjected to the anaerobic biological treatment embodiment method (1) to (4) described above, so that even under anaerobic treatment conditions It can be processed, and the processing speed is faster than that of aerobic biological treatment, and in terms of water quality treatment, it is also significantly better than the anaerobic treatment water quality known in the past, and it is no longer necessary to set aerobic biological treatment equipment in the latter stage. At the same time, it has been found that the alkyl ammonium salt can be well treated under the water temperature condition of the anaerobic treatment generally, below the water temperature below 35 ° C, and at a water temperature of 20 ° C to 35 ° C. Moreover, in the anaerobic biological treatment of the resist discharged from the semiconductor factory development project and the alkylammonium salt-containing water containing the surfactant, the anaerobic (1) to (4) described above may be used. The biological treatment of the embodiment method allows the alkylammonium salt to be decomposed into TOC (total organic carbon) without significant hindrance.

The alkylammonium salt which can be treated in this embodiment includes tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrahydric hydroxide. Tetrabutylammonium hydroxidee, methyl triethylammonium hydroxide, trimethyl ethylammonium hydroxide, dimethyl diethylammonium hydroxide ), trimethyl (2-hydroxyethyl) ammonium hydroxide (also known as choline), diethyl (2-hydroxyethyl) ammonium hydroxide, Dihydroxyethyl dimethyl chloride Dimethyldi(2-hydroxyethyl)ammonium hydroxide, diethyldi(2-hydroxyethyl)ammonium hydroxide, dihydroxyethylmethylammonium chloride (methyltris(2-hydroxyethyl) Ammonium hydroxide), ethyltris(2-hydroxyethyl)ammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxid, and the like. This embodiment is particularly suitable for tetramethylammonium hydroxid (TMAH) and trimethyl(2-hydroxyethyl)ammonium hydroxide discharged from semiconductor factories and liquid crystal factories (ie, choline).

The separation tank 16 and the anaerobic biological treatment tank 14 are connected by a sludge return line 40, and the sludge separated by the separation tank 16 is preferably returned to the anaerobic biological treatment tank 14 if necessary. When the alkyl group-containing ammonium salt-containing water contains an SS component such as a resist or a surfactant, it is preferable to provide a separation tank capable of separating and removing the SS component in the front stage of the biological treatment tank. When the anaerobic biological treatment tank 14 is treated with the alkyl ammonium salt-containing water, even if the resist or the surfactant is mixed, the biological treatment is not affected, and it is not necessary to perform the treatment for the prior removal, but the separation is provided. The slot prevents the SS component from causing a blocking condition in the processing device. The separation tank may be in the form of pressurized floating, precipitation treatment, or the like, and is not particularly limited. In addition, if the treated water has a significant foaming condition, it is preferable to add an antifoaming agent before supplying it to the separation tank.

In the anaerobic biological treatment tank 14, the biologically treated treated water containing alkylammonium salt discharged water contains ammonia nitrogen and is therefore subjected to anaerobic biological treatment. Preferably, the nitrogen treatment tank 18 is provided in the rear section of the tank 14. The nitrogen treatment tank 18 can be a generally known nitrogen treatment apparatus, for example, biological treatment such as nitrification-denitrogenation-reoxidation treatment, nitrous acidation-anammox treatment, or ammonia distillation or removal. (stripping) A device such as physical and chemical processing such as processing. In addition, mixing the treated water portion with the discharged water, and performing the TMAH treatment after the stripping treatment can also reduce the burden of the downstream nitrogen biological treatment.

After that, the treated water subjected to anaerobic biological treatment, separation treatment, nitrogen treatment, or the like is stored in the water tank 20.

<Second embodiment>

Fig. 2 is a view showing another mode of the anaerobic biological treatment apparatus in the present embodiment. As shown in Fig. 2, the anaerobic biological treatment device 2 is composed of a raw water first line 42, an adjustment tank 44, a raw water second line 46, a reaction tank 48, a treated water discharge line 50, and a gas discharge line 52. The treatment water circulation line 54, the molasses supply method, the nutrient supply method, and the pH adjuster supply method are configured. The molasses supply method is composed of a molasses storage tank 56 and a molasses supply line 58. The nutrient supply method is composed of a nutrient solution storage tank 60 and a nutrient supply line 62. The pH adjusting agent supply method is a pH adjuster storage tank 64. The pH adjuster supply line 66 is constructed. However, the structure of each supply method is not limited to the above structure as long as it can supply the solution to the discharged water. For example, in order to be able to arbitrarily adjust the flow rate of the solution, it is preferable to install a pump on each supply line. Preferably, the agitating means 68 is provided in the adjusting tank 44, and the concentration is more uniform by the stirring means 68 or the like.

The raw water introduction port of the adjustment tank 44 (not shown) is connected to the raw water first tube Road 42. The molasses discharge port (not shown) of the molasses storage tank 56 is connected to the molasses supply port (not shown) of the adjustment tank 44 through the molasses supply line 58, and the nutrient discharge port of the nutrient storage tank 60 (not shown) and The nutrient supply ports (not shown) of the adjustment tank 44 are connected through the nutrient supply line 62, and the pH adjuster discharge port (not shown) of the pH adjustment tank 44 and the pH adjuster supply port of the adjustment tank 44 ( Illustrated between the figures is connected through a pH adjuster supply line 66. Further, the raw water discharge port (not shown) of the adjustment tank 44 is connected to the reaction tank 48 through the raw water second line 46. Further, the connection position of the raw water second line 46 on the side of the reaction tank 48 is preferably located below the reaction tank 48.

A gas-solid liquid separation device (hereinafter referred to as GSS) is provided in the reaction tank 48. The gas-solid liquid separation device has partition plates 70a, 70b inclined in opposite directions, and a solid-liquid separation portion 72 on the inner side thereof. Below the partition plates 70a, 70b, the communication passages 74 are formed to be spaced apart, and the lower ends of the partition plates 70a, 70b are disposed below the lower end of the other side, and this structure can form a gas from the cabinet. 74 enters the solid-liquid separation unit 72. The solid-liquid separation unit 72 is provided with an overflow-type treated water take-out unit 76, and the treated water discharge line 50 is connected to the treated water discharge port (not shown) of the treated water take-out unit 76. Further, the treated water return port (not shown) of the treated water take-out portion 76 is connected to the treated water supply port (not shown) of the adjustment tank 44 through the treated water circulation line 54. A gas discharge line 52 is connected to the top of the reaction tank 48.

As long as the reaction tank 48 can treat the alkyl ammonium salt by anaerobic biological treatment, it is possible to use the UASB type, the EGSB method, etc. A bed type reaction tank or a fixed bed type using a support, a fluidized bed type reaction tank, or the like.

The operation of the anaerobic biological treatment device 2 of the present embodiment and the anaerobic biological treatment method will be described below.

The alkylammonium salt-containing discharge water is supplied to the adjustment tank 44 through the raw water first line 42 while the molasses in the molasses storage tank 56 is supplied to the adjustment tank 44 through the molasses supply line 58. Then, the mixed liquid (containing alkyl ammonium salt discharged water and molasses) mixed by the stirring device 68 is introduced into the reaction tank 48 through the raw water second line 46, and is circulated upward. According to the study by the present inventors, in the reaction tank 48, an alkylammonium salt (for example, TMAH) is decomposed into methane, carbonate ions, ammonia ions or the like due to the relationship of anaerobic organisms. The sludge used in anaerobic biological treatment is not particularly limited. In general food factories, beverage factories, paper factories, chemical factories, livestock discharge water treatment, etc., anaerobic sludge and granules will be used, and the sewage treatment plant will be used. Digested sludge, etc.

In the data of the conventional art, it is shown that the granular sludge containing the anaerobic microorganisms is started to be put into the reaction tank 48 at the time of starting the biological treatment, and is subjected to anaerobic treatment, but in the present embodiment, since the molasses may be added The anaerobic sludge is formed into granular sludge, so that the anaerobic sludge can be directly introduced into the reaction tank 48 for biological treatment.

In this embodiment, it is preferable to supply molasses at the time of starting the biological treatment and after the start of the biological treatment. The supply of molasses is not particularly limited, and can be calculated from the total organic carbon ratio, and is supplied to the molasses in a ratio of 0.5 to 20% of the discharged water, or to the molasses in a ratio of 1 to 10% of the discharged water in terms of the total organic carbon ratio.

The inventors have found that when performing anaerobic biological treatment, adding molasses can The invention can be derived by allowing the anaerobic sludge to form a granular sludge and suppressing the slimming of the granular sludge. The reason why the addition of molasses can produce the above effects is because molasses is a high molecular organic substance, which promotes the proliferation of hydrolyzed bacteria and acid-producing bacteria, and produces a bio-polymer having a particle bridge structure, and can also utilize tannic acid. Methane-producing bacteria, Methanosaeta, proliferate. In addition, molasses contains trace elements required for the growth of microorganisms such as organic substances, and the trace elements can promote the formation of particles. In the semiconductor factory, pure water and ultrapure water are used. Therefore, the above-mentioned trace elements contained in the discharge water of such factories are insufficient, and the addition of honey can supplement the trace elements required for the growth of microorganisms.

Further, at the time of starting the biological treatment, in order to increase the amount of the particles, a substance such as activated carbon, iron or a calcium salt or fly ash may be added, or a substance such as a coagulant or an organic substance which promotes the formation of the particles may be added.

The term "molasses (containing waste molasses)" as used in this specification refers to the production of sugar when sugar cane (sweet sugar) is produced from sugar cane (Cane) or when raw sugar is refined, or when sugar beet is produced from sugar beet. Produced as a by-product (a brownish liquid with a viscosity that is more viscous). Molasses contains 40-60% sugar, and in general molasses is a by-product of the refining process, so the main ingredient is sucrose (glucose and fructose 2 kinds of sugar). And molasses contains protein, fat, minerals, amino acids and vitamins. The raw material of the molasses is not particularly limited, and may be sugar cane (sucrose), sweet potato, brown sugar, corn, raw sugar, and sugar beet. The molasses used in the present embodiment may also use waste molasses, and it is also preferable to use waste molasses from the viewpoint of cost. In addition, Patent Document 4 (Specially Open 2008-279385) The starch used in the publication is a general term for a glucose polymer to which D-glucopyranose (Glucopyranose) is a-1.4.

As shown in the foregoing description, in the reaction tank 48, an alkylammonium salt (e.g., TMAH) is decomposed into methane, carbonate ions, ammonia ions, and the like due to anaerobic organisms (mainly after unfolding biological treatment). The anaerobic biologically treated discharged water enters the solid-liquid separating unit 72 through the communication passage 74, and the solid-liquid separated treated water overflows to the treated water take-out portion 76 and flows out from the treated water discharge line 50. The gas such as methane generated in the reaction tank 48 is blocked by the partition plates 70a and 70b, does not flow into the solid-liquid separation unit 72, and rises from the reaction tank 48 and flows out from the gas discharge line 52.

In the present embodiment, a portion of the biologically treated treated water is supplied to the conditioning tank 44 through the treated water circulation line 54, and when flowing into the reaction tank 48 (when performing biological treatment), the alkylammonium salt-containing water is discharged. The alkylammonium salt concentration is preferably less than 20,000 mg/L, more preferably in the range of 10,000 mg/L or less. In particular, if there is concern about changes in water quality and effects on coexisting substances, the concentration of alkylammonium salts in the alkylammonium-containing discharge water is preferably less than 5000 mg/L when flowing into the reaction tank 48 (when biological treatment is carried out). Especially in the range of ~3000 mg / L. In the present embodiment, when the concentration of the alkylammonium salt in the alkylammonium salt-containing discharge water exceeds 20,000 mg/L, the treated water can be supplied and diluted to have a concentration of less than 20,000 mg/L. However, even if the concentration of the alkylammonium salt in the alkylammonium salt-containing water is less than 20,000 mg/L (for example, more than 10,000 mg/L), the treated water may be supplied and diluted to a range of 10000 mg/L or less and 1000 to 3000 mg/L. . When flowing into the reaction tank 48, the alkyl group is contained When the concentration of the alkylammonium salt in the ammonium salt discharge water exceeds 20,000 mg/L, the decomposition reaction rate of the alkylammonium salt may be slowed down during biological treatment.

In the present embodiment, an inductor for treating the concentration of ammonia ions in the water after the induction biological treatment may be provided on the treated water discharge line 50 or the like. Further, the concentration of the alkylammonium salt can be estimated from the detected concentration of the ammonia ion, and the amount of the treated water can be determined based on the estimated value so that the concentration of the alkylammonium salt flowing into the reaction vessel 48 can enter the above range. Further, an inductor for detecting the concentration of the alkylammonium salt may be installed in the adjustment tank 44 or the raw water first line 42 or the like. At the same time, the added amount of the treated water can be determined according to the determined concentration of the alkylammonium salt so that the concentration of the alkylammonium salt can enter the above range when flowing into the reaction tank 48.

When the concentration of the ammonia ion in the reaction tank 48 exceeds 5000 mg/L, the decomposition reaction rate is slowed down. At this time, part of the biologically treated treated water can be supplied to the adjustment tank 44 through the treated water circulation line 54. The concentration of ammonia ions in 48 is preferably less than 5000 mg/L or even less than 1000 mg/L.

In addition to the above-mentioned biologically treated treated water, industrial water, discharged water, or distilled water (condensed water) obtained by distilling ammonia waste liquid and IPA waste liquid may be used as a dilution. Water to dilute the discharge water containing alkyl ammonium salts. The water temperature of the distilled treated water is as high as 40 ° C to warm the reaction tank 48 to promote the decomposition reaction of the alkyl ammonium salt.

In the present embodiment, when the biological treatment of the alkylammonium salt-containing water is carried out, the pH is preferably between 6.5 and 9.0, and more preferably 7.0 to 8.0, and preferably the pH is supplied through the pH adjuster supply line 66. The conditioning agent is supplied to the adjustment tank 44. If the pH of the alkylammonium salt-containing water is not within the above range, biological treatment is carried out. Sometimes the decomposition rate of the alkylammonium salt is slowed down. In addition, in the past, in the anaerobic biological treatment, in order to reduce the inhibition of ammonia, the pH was controlled to a range of pH 6.5 to 7.0 weakly acidic, but the treatment of the alkyl ammonium salt was weakly alkaline with a pH of 7.0 to 8.0. Processing performance is better. This point was first confirmed by the inventors. When the pH is adjusted to the above range, the concentration of the alkylammonium salt in the alkylammonium salt-containing water is preferably less than 20,000 mg/L, and the ammonia ion concentration is preferably 5,000 mg/L or less.

The pH adjuster used in the present embodiment is not particularly limited as long as it is an acid agent such as hydrochloric acid or an alkali agent such as sodium hydride. Further, as the pH adjuster, sodium bicarbonate, a buffer of citric acid or the like having a buffering action can also be used.

In the present embodiment, in order to maintain good decomposition activity of the anaerobic organism, it is preferable to supply the nutrient to the adjustment tank 44 through the nutrient supply line 62. The type of the nutrient agent is not particularly limited and may be a carbon source, a nitrogen source, and other inorganic salts.

In the present embodiment, in the biological treatment of the alkylammonium salt-containing water, it is preferred to adjust the water temperature in the reaction tank 48 to 20 ° C or higher, and it is preferably adjusted to a range of 28 to 35 ° C. In the case of anaerobic biodegradation of alkylammonium salts, the temperature may be lower than 20 ° C, but if the temperature is lower than 20 ° C, the decomposition reaction rate will be slow, so it is preferable to adjust the water temperature to the above range. The temperature adjustment described above is not particularly limited in terms of method. For example, steam may be supplied to the adjustment tank 44 to adjust the temperature of the water in the reaction tank 48, or a heater may be installed in the reaction tank 48, and the heat of the heater may be used to adjust the reaction. The temperature of the water in the tank 48. Further, warmed dilution water may be supplied to adjust the temperature of the water in the reaction tank 48. When the alkylammonium salt is decomposed, methane gas is generated. At this time, the same desulfurization treatment as in the general anaerobic treatment can be utilized, and then the methane is recovered to the methane boiler as a heat source, and the heat source is supplied to the reaction tank 48 to adjust the water. temperature. Here, when the water temperature in 48 is adjusted to the above range, the concentration of the alkylammonium salt in the alkylammonium salt-containing water is preferably less than 20,000 mg/L, and the ammonia ion concentration is preferably 5,000 mg/L or less.

The problem of the discharged water during the anaerobic treatment in the present embodiment is described by taking the alkylammonium salt-containing water as an example. However, the organic discharged water containing six or less carbons can be similarly subjected to anaerobic treatment.

In projects such as semiconductor plants that use pure water and ultrapure water, they emit emissions containing alkylammonium salts, or those containing less than 6 carbons (such as isopropanol, monoethanolamine, etc.). When the conventional anaerobic biological treatment method is used after the treatment, the generation of the granular sludge at the start of the treatment, the maintenance of the granular sludge after the start of the treatment (that is, the suppression of the granular sludge), the maintenance of the long-term treatment performance, and the like occur. problem. In addition to the conventional anaerobic biological treatment methods, other treatment methods include distillation concentration treatment, ion exchange resin treatment, membrane treatment, and the like, but all have economical, operational, and environmental problems. However, in the case of the present embodiment, even if it is a plant such as a semiconductor factory that uses pure water or ultrapure water, it discharges water containing alkylammonium salts, or contains organic carbon or water containing less than 6 carbons, as long as it is added with molasses. The formation of the granular sludge at the beginning, the maintenance of the granular sludge after the start of the treatment, and the maintenance of the long-term treatment performance can all achieve a stable effect. Regardless of economic efficiency, operational management and the environment Good anaerobic biological treatment. The semiconductor factory discharge water referred to in the present specification also includes discharge water discharged from a manufacturing plant such as a semiconductor such as an IC or an LSI or a liquid crystal panel.

The alkylammonium salt which can be treated in this embodiment includes tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide. Tetrabutylammonium hydroxide, methyl triethylammonium hydroxide, trimethyl ethylammonium hydroxide, dimethyl diethylammonium hydroxide , trimethyl(2-hydroxyethyl)ammonium hydroxide (also known as choline), diethyl(2-hydroxyethyl)ammonium hydroxide, Dimethyldi(2-hydroxyethyl)ammonium hydroxide, diethyldi(2-hydroxyethyl)ammonium hydroxide, dihydroxyethylmethyl trichloride Ammonium (methyltris(2-hydroxyethyl)ammonium hydroxide), ethyltris(2-hydroxyethyl)ammonium hydroxide, dihydroxyethylammonium chloride (tetra(2-hydroxyethyl)ammoniu m hydroxide) and such salts. This embodiment is particularly suitable for tetramethylammonium hydroxide (TMAH) and dihydroxyethyltrimethylammonium chloride (trimethyl) discharged from semiconductor factories and liquid crystal factories. (2-hydroxyethyl)ammonium hydroxide, also known as choline).

The treatment of the present embodiment is also applicable to treatment with an organic substance containing six carbons or less, for example, the above alkylammonium salt containing six carbons or less, isopropanol (IPA), methanol, monoethanolamine, citric acid, propylene glycol methyl ether acetate ( PGME), cyclohexanone, dimethyl hydrazine (DMSO), and propylene glycol methyl ether acetate (PGMEA).

<Embodiment 3>

Fig. 3 is a view showing another configuration mode of the anaerobic biological treatment apparatus of the embodiment. In the anaerobic biological treatment device 3 shown in Fig. 3, the same components as those of the anaerobic biological treatment device 2 shown in Fig. 2 are denoted by the same reference numerals, and the description thereof will be omitted. In the anaerobic biological treatment apparatus 3 shown in Fig. 3, a separation tank 78 is attached to the rear stage of the reaction tank 48, and the sludge separated by the separation tank 78 is returned to the reaction tank 48 depending on the situation, so that there is a return pipe. Road 80. The return line 80 is disposed between the separation tank 78 and the reaction tank 48. According to the above configuration, when the biological treatment is started, the sludge flowing out of the treated water can be recovered to the separation tank 78 due to fluctuations in the raw water, and then returned to the reaction tank 48 through the return line 80. The separation tank 78 can be subjected to a coagulation treatment, a pressurized floating treatment, or the like which is treated by adding a coagulant, and is not particularly limited. Further, if there is a significant foaming condition, it is preferable to add an antifoaming agent to the separation tank 78.

Further, when the alkylammonium salt-containing water contains SS components such as a resist and a surfactant, it is preferable to provide a separation tank capable of separating and removing the SS component in the front stage of the reaction vessel 48. When the alkylammonium salt-containing effluent water is treated in the reaction tank 48, even if it contains a resist or a surfactant, it does not affect the growth. The material is processed, so it is not necessary to do the removal processing beforehand, but the separation tank can prevent the SS component from causing the processing device to block.

<Embodiment 4>

Fig. 4 is a view showing another mode of the configuration of the anaerobic biological treatment apparatus in the present embodiment. In the anaerobic biological treatment device 4 shown in Fig. 4, the same components as those of the anaerobic biological treatment device 3 shown in Fig. 3 are denoted by the same reference numerals, and the description thereof will be omitted. The support tank 48 of the anaerobic biological treatment apparatus 4 shown in Fig. 4 is filled with a support 82. When the biological treatment is carried out, since the reaction tank 48 is filled with the support 82, the time for forming and holding the granular sludge and starting the biological treatment can be shortened, and the stability of the discharge water treatment can be improved. The type of the carrier to be used in the present embodiment is not particularly limited, and a foamed sponge carrier such as urethane or a gel-like carrier such as polyvinyl alcohol (PVA), a fibrous carrier, a nonwoven fabric molded article, and a polypropylene resin can be used. Molded products, etc. The form of the molded article is not particularly limited, and may be various forms such as a honeycomb structure such as a honeycomb shape or a V shape, a mesh thick pad shape, a mesh tube shape, and a mesh shape. Further, although not shown in the drawings, it is preferable to provide a gas-solid liquid separation device above the reaction tank in which the monomer is filled.

The treated water containing the alkylammonium salt discharged water which has been biologically treated in the reaction tank 48 contains ammonia nitrogen, so that it is preferable to provide a nitrogen treatment tank in the latter stage of the reaction tank 48. The nitrogen treatment tank can be generally used as a nitrogen treatment device, for example, biological treatment such as nitrification-denitrogenation-reoxidation treatment, nitrous acid-anammox treatment, or ammonia distillation or removal. (stripping) processing and other devices. In addition, the treated water is partially recycled and discharged. Water mixing, after stripping treatment and then TMAH treatment can also reduce the burden of nitrogen bioprocessing in the latter stage.

Example:

The present invention will be further illustrated by the following examples and comparative examples, but the present invention is not limited to the following embodiments.

(Example 1)

In a glass vial with an internal volume of 100 mL, 47.5 mL of effluent water (pH 7, containing microbial nutrient) containing concentration of 5000 mg/L TMAH, and 2.5 mL of anaerobic sludge (sludge concentration: 20000 mg/L) were charged to make the total liquid amount. Up to 50mL. The glass vial was filled with nitrogen, sealed with an aluminum lid, and cultured at 35 ° C with shaking. Table 1 is the data of the TMAH concentration before and after the anaerobic biological treatment of Example 1. Since anaerobic biological treatment decomposes TMAH, a methane-containing gas is produced. Therefore, we also periodically measure the amount of gas generated by a syringe, and integrate the amount of gas generated with the concentration of methane in the gas in Table 1.

From Table 1, we confirmed the anaerobic biological treatment as in Example 1, which can decompose TMAH. In the following implementation, when we decompose TMAH by anaerobic biological treatment, the gas generation rate per unit sludge (L/gVSS/d) is used as an indicator of TMAH decomposition activity (the higher the gas generation rate represents TMAH decomposition activity) Higher).

(Example 2: Relationship between initial TMAH concentration and maximum gas generation rate)

In a 100 mL glass vial containing 4,500 mL of TMAH-containing water (pH 7.0, microbial-containing nutrient) at a concentration of 1400, 5000, 10,000, 20,000, and 50,000 mg/L, anaerobic sludge (sludge concentration) 20000mg / L) 2.5mL, so that the total liquid volume reached 50mL. The glass vial was filled with nitrogen, sealed with an aluminum lid, and cultured at 35 ° C with shaking. We measure the amount of gas generated by the syringe periodically and measure the gas generation rate of each sludge. In addition, in order to confirm that the sludge is self-digested and does not generate gas, we also tested it with a blank without adding TMAH (adding a microbial nutrient). Table 2 shows the data for the initial TMAH concentration and the maximum gas generation rate (within 140 hours after the start of the test).

According to the results of Example 2, in the initial TMAH concentration of 5000 mg/L, no gas generated by decomposition of TMAH occurred. Moreover, according to the value of the maximum gas generation rate in Table 2, in the anaerobic biological treatment of TMAH, it is considered that the initial TMAH concentration must be at least less than 20,000 mg/L, preferably less than 10,000 mg/L, and the water quality is changed. , confirm that the TMAH concentration is preferably in the range of 1400~5000mg/L. In order to obtain a faster rate of TMAH decomposition reaction. Further, in Example 2-1, when the test completed the measurement of the water quality, TMAH was not detected, and the ammonia ion concentration was about 300 mg/L. From this result, it is understood that after the decomposition of TMAH, the final product is ammonia ion and methane.

(Example 3: Relationship between initial ammonia ion concentration and maximum gas generation rate)

In a 100 mL glass vial containing 4 mL of discharged water (pH 7.0, containing microbial nutrient) containing 1400 mg/L TMAH, anaerobic sludge (sludge concentration) domesticated with TMAH-containing water 20000mg/L) 2.5mL, then add ammonia ion source - ammonia chloride with ammonia ion concentration of 0, 1000, 2000, 3000, 5000, 10000mg / L (ammonia ion concentration 0mg / L means no added ammonia chloride). The glass vial was filled with nitrogen, sealed with an aluminum lid, and cultured at 35 ° C with shaking. Then, the amount of gas generated by the syringe is periodically measured, and the gas generation rate of each sludge is measured. Table 3 shows the data of the initial ammonia ion concentration and the maximum gas generation rate (within 40 hours after the start of the test).

From the results of Example 3, we confirmed that when the initial ammonia ion concentration is 10000 mg/L, the gas generation rate rapidly drops, so the decomposition reaction rate of TMAH also drops rapidly. It can be seen from the value of the maximum gas generation rate in Table 3 that in the anaerobic biological treatment of TMAH, the initial ammonia ion concentration must be at least 5000 mg/L or less (the total nitrogen concentration is below 3900 mg-N/L), preferably. It is below 3000mg/L (the total nitrogen concentration is below 2340mg-N/L), and if it can reach the range of 1000mg/L or less (the total nitrogen concentration is 780mg-N/L or less), it is possible to obtain a high TMAH. Decompose the reaction rate.

(Example 4: Relationship between pH of TMAH-containing water and maximum gas generation rate)

In a glass vial with an internal volume of 100 mL, 47.5 mL of TMAH-containing water (pH 7.0, containing microbial nutrient) having a concentration of 2000 mg/L, and 2.5 mL of anaerobic sludge (sludge concentration: 20000 mg/L) were placed in the glass. After the vial was filled with nitrogen, the pH was adjusted to 5.0, 6.0, 6.5, 7.0, 8.0, 9.0 by adding hydrochloric acid or sodium hydroxide. Then, the glass vial was refilled with nitrogen once, sealed with an aluminum lid, and cultured at 35 ° C with shaking. Then, the amount of gas generated by the syringe is periodically measured, and the gas generation rate of each sludge is measured. Table 4 shows the data of pH and maximum gas generation rate (within 40 hours after the start of the test).

From the results of Example 4, we confirmed that when pH is 5, TMAH will decompose and simultaneously generate gas. Moreover, it can be seen from the value of the maximum gas generation rate in Table 4 that in the anaerobic biological treatment of TMAH, the optimum pH for the fastest decomposition reaction of TMAH is between 7.0 and 8.0.

(Example 5: Relationship between water temperature and maximum gas generation rate)

Adding a digested sludge (sludge concentration 25,178 mg/L) of a sewage treatment plant to a fixed-bed continuous treatment device filled with an 80% filler (22 mm square polyurethane carrier) in an inner volume 1.6L beaker After adding a half beaker amount, TMAH-containing water (pH 7.0, containing a microbial nutrient) having a concentration of 2000 mg/L at a load of 5 kg TMAH/m ³ /d was applied. The water temperature at the time of circulating the water in Example 5 was changed at 35, 28, 23, 20, and 17 °C. Table 5 shows the data of water temperature and TMAH concentration in TMAH-containing water.

The results of Example 5 showed that when the water temperature was 20 ° C or more, the decomposition rate was 90% or more, and it was confirmed that the treatment was good. In contrast, when the water temperature is 17 ° C, TMAH will also decompose, but the decomposition rate falls below 90%, and the treated water quality also deteriorates. Therefore, it can be confirmed that the water temperature must be above 20 ° C, preferably between 28 and 35 ° C.

(Example 6)

A continuous treatment test containing TMAH discharged water was carried out under the following conditions using a UASB (upflow anaerobic sludge system) type reactor having a volume of 2.8 L (φ 60 mm × 1000 mmH).

TMAH concentration in TMAH-containing water: 500~2200mg/L

MLSS (sludge concentration): 38626mg/L

Running water temperature: 35 ° C

Figure 5 shows the relationship between the number of running days and the concentration of TOC in TMAH-containing water, the concentration of TMAH, the concentration of TOC in treated water, and the concentration of TMAH. Figure 6 shows the relationship between the number of running days and the TMAH load and the TMAH removal rate.

It can be seen from Fig. 5 and Fig. 6 that good treatment water quality can be obtained with a high load operation condition of 5 kg TMAH/m ³ /d in one month of running water (TMAH is lower than the inspection limit, TOC is 50 mg/L) the following). Therefore, it is determined that high speed processing can be performed, which can reduce the space and cost required for the processing apparatus.

(Example 7)

The actual discharge water containing TMAH discharged from the semiconductor factory was adjusted to 2000 mg TMAH/L, and anaerobic sludge (sludge concentration 25148 mg/L) was added to the beaker with an internal volume of 0.8 L as a seed sludge, and half a beaker was added. Thereafter, the above-mentioned actual discharged water was passed through a load of 5 kg TMAH/m ³ /d. The temperature at the time of water supply was adjusted to 35 ° C, the pH was adjusted to 7.0 to 8.0, and a nutrient (ORGAMIN NP-51, manufactured by ORGANO Co., Ltd.) and trace elements (ORGAMIN10 1.2 mL manufactured by ORGANO Co., Ltd.) were added. /L), Ni, Co (0.1 mg/L each). In addition, the waste molasses (raw sugar cane and sweet potato) is treated at a ratio of 200 mg/L (57 mg C/L, TOC ratio to 5.5%). It is continuously added to the above-mentioned actual discharge water. The waste molasses component used in Example 7 has a sugar content of 30 to 40% or more, a pure sugar rate of 35% or more, a reconstituted sugar of 15% or more, and a pure sugar content of 55% or more. 6 is shown.

(Comparative Example 1)

Comparative Example 1 was compared to Example 7 except that no molasses was added. Reason.

(Comparative Example 2)

Comparative Example 2 was prepared by substituting ferrous chloride (FeCl2) (inorganic aggregating agent) for molasses at 19 mg/L (iron 6.5 mg Fe/L), and the rest were treated as in Example 7.

(Comparative Example 3)

In the comparative example, the molasses was replaced by Cation Polymer (OX-606, manufactured by ORGANO Co., Ltd.), and 0.5 mg/L was added, and the rest was treated in the same manner as in Example 7.

Figure 7 shows the sludge particle diameter before and after 36 days of water passing. Fig. 8 is a 50-fold enlarged photograph of the sludge before the water flow in Example 7 and Comparative Examples 1 to 3 and the sludge after the passage of water for 36 days. Figure 9 shows the sludge concentration in the beaker before and after 55 days of water passing. The first picture shows the interface height of the sludge in the beaker before and after 55 days of water passing.

As can be seen from Fig. 7 and Fig. 8, in Example 7, the particle diameter of the sludge was larger than that of Comparative Examples 1 to 3, and it was confirmed that the effect of promoting the formation of particles was confirmed. Further, as can be seen from Fig. 9 and Fig. 10, in Example 7, the sludge concentration and the sludge interface height were higher than those of Comparative Examples 1 to 3, and it was confirmed that the amount of sludge in the beaker was increased. In particular, the effect of Cation Polymer is not clear in comparison with the anaerobic treatment using methanol in the past, but the effect of the present Example 7 is very clear, and it has been confirmed that it is very effective for promoting and maintaining particle formation.

1~4‧‧‧ Anaerobic biological treatment device

10‧‧‧ original sink

12,12a~12b, 44‧‧‧ adjustment slot

14‧‧‧ Anaerobic biological treatment tank

16‧‧‧Separation tank

18‧‧‧Nitrogen treatment tank

20‧‧‧Processing sink

22a~22e‧‧‧Pipe

24a~24b‧‧‧ pump

26‧‧‧Dilution water inflow line

28‧‧‧pH adjuster inflow line

30‧‧‧Nutrition agent inflow line

32‧‧‧Vapor inflow line

34‧‧‧Circulation line

36,38‧‧‧Agitator

40‧‧‧Sludge return line

42‧‧‧ Raw water first pipeline

46‧‧‧Second water second pipeline

48‧‧‧Reaction tank

50‧‧‧Processing water discharge line

52‧‧‧ gas discharge line

54‧‧‧Processing water circulation pipeline

56‧‧‧ molasses storage tank

58‧‧‧ molasses supply line

60‧‧‧Nutrition tank

62‧‧‧Nutrition supply line

64‧‧‧pH adjuster storage tank

66‧‧‧pH adjuster supply line

68‧‧‧Agitator

70a, 70b‧‧‧ divider

72‧‧‧ Solid-liquid separation department

74‧‧‧Connected Road

76‧‧‧Processing Water Removal Department

78‧‧‧Separation tank

80‧‧‧Return line

82‧‧‧Support

Fig. 1 is a schematic view showing a configuration of an anaerobic biological treatment apparatus of the present embodiment.

Fig. 2 is a view showing another mode constituting the anaerobic biological treatment apparatus of the present embodiment.

Fig. 3 is a view showing another mode constituting the anaerobic biological treatment apparatus of the present embodiment.

Fig. 4 is a view showing another mode constituting the anaerobic biological treatment apparatus of the present embodiment.

Figure 5 is a graph showing the relationship between the number of water passing days and the concentration of TOC in TMAH-containing water, the concentration of TMAH, the concentration of TOC in treated water, and the concentration of TMAH.

Figure 6 is a graph showing the relationship between the number of water passing days and the TMAH load and the removal of the TMAH speed.

Figure 7 is a graph showing the diameter of sludge particles before and after 36 days of water passing.

Fig. 8 is a 50-fold enlarged photograph of the sludge before the water passing, the sludge of Example 7 and the sludges of Comparative Examples 1 to 3 after 36 days.

Figure 9 is a graph showing the concentration of sludge in the cylinder after 55 days before the passing of water and the number of days of water passing.

Figure 10 is a plot of the interface height of the sludge in the cylinder after 55 days before the water passing.

1‧‧‧ Anaerobic biological treatment device

10‧‧‧ original sink

12,12a~12b‧‧‧Adjustment slot

14‧‧‧ Anaerobic biological treatment tank

16‧‧‧Separation tank

18‧‧‧Nitrogen treatment tank

20‧‧‧Processing sink

22a~22e‧‧‧Pipe

24a~24b‧‧‧ pump

26‧‧‧Dilution water inflow line

28‧‧‧pH adjuster inflow line

30‧‧‧Nutrition agent inflow line

32‧‧‧Vapor inflow line

34‧‧‧Circulation line

36,38‧‧‧Agitator

40‧‧‧Sludge return line

Claims (29)

An anaerobic biological treatment method for treating an alkylammonium salt-containing effluent water and producing methane gas by an anaerobic biological treatment method, wherein: in the foregoing biological treatment, the alkylammonium salt in the alkylammonium salt-containing water is discharged The salt concentration is below 20,000 mg/L. The anaerobic biological treatment method according to claim 1, wherein the part of the treated water after the biological treatment is recycled to the alkylamine-containing salt discharge water to dilute water and the foregoing One part of the water is treated to adjust the alkyl ammonium salt concentration of the discharged water. The anaerobic biological treatment method according to the first aspect of the invention, wherein the total concentration of the organic nitrogen and the ammonia nitrogen in the alkylammonium salt-containing discharge water is 3900 mg-N/L or less in the biological treatment. The anaerobic biological treatment method according to claim 2, wherein, in the biological treatment, the concentration of the alkylammonium salt in the alkylammonium-containing salt-containing water is 10,000 mg/L or less. The anaerobic biological treatment method according to claim 1, wherein the pH range of the alkylated ammonium salt-containing water is controlled to be between 6.5 and 9.0. The anaerobic biological treatment method according to claim 1, wherein the water temperature is controlled to be 20 ° C or higher when the alkylamine-containing salt-containing water is subjected to the biological treatment described above. An anaerobic biological treatment method for treating alkyl ammonium salt-containing discharge water and generating methane gas by anaerobic biological treatment, wherein the following two At least one of the conditions: (1) in the foregoing biological treatment, the concentration of the alkylammonium salt in the alkylammonium-containing salt-containing water must be less than 20,000 mg/L, or the portion after the biological treatment at the same time The treated water is re-introduced into the above-mentioned alkyl ammonium salt-containing discharge water to circulate; (2) the total concentration of organic nitrogen and ammonia nitrogen in the alkylammonium-containing discharge water is required to be below 3900 mg-N/L during the biological treatment described above, Or at the same time, the part of the treated water after the biological treatment is re-introduced into the aforementioned alkyl ammonium salt-containing discharge water; wherein, the alkyl ammonium salt-containing discharge water is subjected to the aforementioned biological treatment, and the pH must be controlled at 7.0-8.0. In the case where the aforementioned alkylammonium salt-containing water is subjected to the aforementioned biological treatment, the water temperature must be in the range of 28 to 35 °C. The anaerobic biological treatment method according to any one of claims 1 to 7, wherein the alkylammonium salt is tetramethylammonium hydroxide (TMAH). An anaerobic biological treatment device comprising an anaerobic biological treatment method for treating a liquid containing alkylammonium salt and generating methane gas together, the anaerobic biological treatment device further comprising a monoalkylammonium salt concentration The adjustment method is such that when the discharged water is subjected to the biological treatment method, the concentration of the alkylammonium salt in the alkylammonium salt-containing water can be adjusted to 20,000 mg/L or less. The anaerobic biological treatment device according to claim 9, further comprising a nitrogen concentration adjustment method for allowing the discharged water to perform the biological treatment method by a circulation method The treated water is again introduced into the aforementioned alkyl ammonium salt-containing discharge water to circulate The total concentration of organic nitrogen and ammonia nitrogen in the alkylammonium salt-containing discharged water is adjusted to 3900 mg-N/L or less and the alkylammonium salt concentration is adjusted to 20,000 mg/L or less. The anaerobic biological treatment device according to claim 9, which further comprises a method for adjusting the concentration of the alkylammonium salt, so that the discharged alkyl chloride can be discharged into the water when flowing into the biological treatment method. The alkylammonium salt concentration is adjusted to below 10,000 mg/L. The anaerobic biological treatment device according to claim 9, further comprising a pH adjustment method for allowing the alkylammonium salt-containing water to be adjusted to a pH of 6.5 to 9.0 when performing the biological treatment described above. Within the scope. The anaerobic biological treatment device according to claim 9, further comprising a temperature adjustment method for allowing the aforementioned alkyl ammonium salt-containing water to be used in the biological treatment method The temperature is adjusted to above 20 °C. An anaerobic biological treatment device comprising a biological treatment method, a pH adjustment method and a temperature adjustment method for treating an alkylammonium salt-containing water discharged by an anaerobic biological treatment, and a temperature adjustment method, wherein The alkylammonium salt discharge water is subjected to the aforementioned biological treatment, and the pH adjustment method adjusts the pH to a range of 7.0 to 8.0, and the temperature adjustment method adjusts the water temperature in the biological treatment method to 28-35 ° C. Within the scope of the anaerobic biological treatment device, including (1) and (2) At least one of the methods: (1) a monoalkylammonium salt concentration adjustment method, wherein the alkylammonium salt-containing effluent water can flow the alkylammonium salt in the alkylammonium salt-containing water when flowing into the biological treatment method Adjusting the salt concentration to below 20,000 mg/L, or having the foregoing method for adjusting the concentration of the alkylammonium salt and a cycle method, allowing the partially treated water treated by the biological treatment to be recycled to the alkylammonium salt again; 2) having a nitrogen concentration adjustment method, wherein the above-mentioned biological treatment method for the alkyl ammonium salt-containing water can adjust the total concentration of organic nitrogen and ammonia nitrogen in the alkyl ammonium salt-containing water to 3900 mg-N. Below /L, or having the aforementioned nitrogen concentration adjustment method and a circulation method, the partially treated water treated by the above biological treatment is recycled to the aforementioned alkyl ammonium salt. The anaerobic biological treatment device according to any one of claims 9 to 14, wherein the alkylammonium salt is tetramethylammonium hydroxide (TMAH). An anaerobic biological treatment method for treating alkyl ammonium salt-containing discharge water by anaerobic biological treatment, wherein molasses is added to the discharged water to perform anaerobic biological treatment of methane gas together, and the biological treatment is cycled One part of the treated water is used, and the ammonium ion concentration at the time of performing the aforementioned anaerobic biological treatment is 5000 mg/L or less. The anaerobic biological treatment method according to claim 16, which processes the discharged water containing organic matter of 6 carbons or less. The anaerobic biological treatment method according to claim 16 or 17, wherein the aforementioned molasses is supplied at the start and after the start of the biological treatment. The anaerobic biological treatment method according to claim 16 or 17, wherein the anaerobic sludge is introduced into the reaction tank for performing the biological treatment to expand the biological treatment. The anaerobic biological treatment method according to claim 16 or 17, wherein the discharge water is discharged water discharged from a semiconductor factory. The anaerobic biological treatment method according to claim 16 or 17, wherein the alkylammonium salt and the organic substance having 6 or less carbon atoms are tetramethylammonium hydroxide (TMAH). The anaerobic biological treatment method according to claim 19, wherein when the biological treatment is carried out, the carrier is filled in the reaction vessel in which the biological treatment is performed. An anaerobic biological treatment device comprising a reaction tank for treating an alkylammonium salt-containing water by anaerobic biological treatment, and a method for supplying molasses for supplying the molasses to the discharged water, wherein the anaerobic biological treatment device is used for combination An anaerobic biological treatment of methane gas is generated, and one part of the treated water after the biological treatment is circulated, and the ammonium ion concentration at the time of performing the anaerobic biological treatment is 5,000 mg/L or less. The anaerobic biological treatment device according to claim 23, wherein the device has an organic structure containing 6 carbons or less by anaerobic biological treatment. a reaction tank for the substance, and a method of supplying molasses to the aforementioned discharged water by supplying molasses. The anaerobic biological treatment device according to claim 23, wherein the molasses supply method is to supply the molasses at the time of starting and starting the biological treatment. The anaerobic biological treatment apparatus according to claim 23, wherein the anaerobic sludge is introduced into the reaction tank when the biological treatment is started. The anaerobic biological treatment device according to claim 23, wherein the discharge water is discharged water discharged from a semiconductor factory. The anaerobic biological treatment device according to claim 23, wherein the alkylammonium salt and the organic substance having 6 or less carbon atoms are tetramethylammonium hydroxide (TMAH). The anaerobic biological treatment device according to claim 26, wherein when the biological treatment is started, the carrier is filled in the reaction tank.