TW201029938A - Anaerobic biological treatment method and anaerobic biological treatment device - Google Patents

Abstract

An objective of the invention is to reduce the equipment area of the treatment equipment for effluent containing polycarboxylic alkyl ammonium salts such as TMAH, while performing the anaerobic biological treatment for the effluent containing polycarboxylic alkyl ammonium salts such as TMAH, and meanwhile to provide an excellent biological treatment method and a biological treatment device to match economic benefit and environmental protection concerns. The invention is an anaerobic biological treatment method for treating the effluent containing polycarboxylic alkyl ammonium salts by means of an anaerobic biological treatment. While performing the foregoing biological treatment, the concentration of the polycarboxylic alkyl ammonium salts in the effluent containing polycarboxylic alkyl ammonium salts must be below 200000 mg/L.

Description

201029938 VI. Description of the Invention: [Technical Field] The present invention relates to a biological treatment method and a biological treatment apparatus, which is an anaerobic biological treatment comprising a poly-acid-acid base such as TMAH or a biliary test. Discharged water from Alkyl Ammonium Salt and organic water discharged with a small amount of carbon. I [Prior Art] 9 In the past, the semiconductor factory and the liquid crystal factory were used to discharge the used tetrahydrogen hydroxide (Ding 61^11^1^1 oyster 111111〇1111111111; ^(11: 〇Father 1 (16=丁%人) 11) In the case of wastewater, the treatment of the discharge water containing polyalkylammonium salt of polycarboxylate (sometimes due to the presence of a plurality of resins from the resist) and the discharge of water, the method of biological treatment, ion exchange resin Various methods such as method processing and membrane treatment (for example, please refer to Patent Documents 1 to 4) In addition, in the past, when the wood pulp production discharge water project and the chemical plant discharge waste water containing less than 4 carbons, more specifically When the main component is anaerobic treatment of discharged water containing two or less organic substances such as acetic acid, ethanol, or acetaldehyde, the amount of sludge is reduced due to the disintegration of the granular sludge into smaller particles. It 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-polimer which produces acid-producing bacteria of organic acids. Bridge Fruit plays an important role in the formation and maintenance of granules. In addition, the genus-forming genus Methanosaeta is a granule-forming skeleton, which is important for the formation of granules. However, if the organic matter containing less carbon is decomposed, On the contrary, there are fewer hydrolyzed bacteria and acid-producing bacteria, but mainly decane-producing bacteria, and the non-linear snail-forming bacteria Methanosarcina and Methanobacterium genus are more susceptible to decane-producing genus Methanosaeta than methanol and TMAH. Predominantly, the particles of the granular sludge tend to become finer 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 It is a specific countermeasure proposed in the past in order to solve the above problems. PRIOR ART DOCUMENT: Patent Document 1: Special Fair 8 - 2 3 5 Patent Document 2: JP-A-2001- 27 6 825. Patent Literature 3: Japanese Patent No. 2 703 016. Patent Document 4: Japanese Patent Publication No. Hei 1 1 - 2 6 2 7 6 5 Patent Document 5: License No. 4 1 9 3 3 1 0 Patent Document 6: Japanese Laid-Open Patent Publication No. Hei 2 0 0 8 - 2 7 9 3 8 No. 3 Patent Document 7: Patent No. 2 5 3 3 0 No. 4 Patent Document 8: Special Opening 2 0 0 8-2 7 9 3 8 5 [Invention] In the traditional recycling technology, the recovered TMAH is reused in the discharge water containing a high concentration of polyalkylamine ammonium salts such as TMAH, which is an effective method. 'But there are problems with the purity and economic effects of the drug. 4 201029938 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. The lower-cost treatment method of the discharge water containing the TMAH and the like is a biological decomposition treatment method, but in the past, the aerobic biological treatment method was the main flow. The aerobic biological treatment is generally carried out by a bulk method or a dipped membrane activated sludge method. The method of Patent Document 5 is an anaerobic method in which a polymer aggregating agent is added to avoid collapse of the granular sludge after the granular sludge is processed. Sexual biological treatment. 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 flocculant may cause the polymer aggregating agent to collide with the charge of the polymer flocculant, 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. 'This method actively adds the target substance to be treated, nitric acid and nitrous acid, so that raw water fluctuation, device failure, and operation management occur. The problem of 'and therefore' also discharges nitrogen at the same time as the treated water is discharged, which may cause water pollution. In addition, this method must allow denitrifying bacteria to coexist with methane-producing bacteria. If the anaerobic reaction is initiated by the denitrification reaction, the original water may be changed, causing the treated water to deteriorate, and also causing leakage of nitrate and the like into the treated water. The method of Patent Document 7 is an anaerobic treatment method in which a treatment substance, methanol, 4 times the amount of acetic acid is added at the beginning of the treatment, but it is impractical to add a larger amount of acetic acid than the discharged water to the actual installation. . Moreover, the 5 201029938 methods will be stopped after the start of processing (4). After the time of stopping the acetic acid, there will be a problem of characterization and treatment. The method of Patent Document 8 is to switch to an anaerobic treatment method in which sugar is added. 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 tri-carbon (tri〇se) containing 3 carbons, a tetraether (tetrose) containing 4 carbons, a 5-carbon sugar containing 5 carbons, and a hexose containing 6 carbons. This _ plus single-funded (four) oxygen biological treatment may lead to the collapse of granular sludge, so the addition of sugar can not prevent the collapse of granular sludge. This type of method only has the addition of sugar to the temple powder. 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 apply them practically. In addition, most of the above methods are emissions of organic matter containing j stone and sterol in the wood pulp manufacturing process, and do not use TMAH discharge water containing 4 carbons from semiconductor factories such as pure water and ultrapure water ❿ engineering. A case of anaerobic biological treatment of polycarboxyalkylammonium salts discharged water (sometimes containing a resin in a resist or a surfactant-containing agent). Therefore, the object of the present invention is to reduce the anaerobic biological treatment of the discharge water containing polyalkylamine ammonium salts such as TMAH, biliary test, etc., and to reduce the discharge of polyoxic acid-containing salt recorded in TMAH, bile test, etc. The equipment area of the water treatment equipment provides economical and environmentally friendly anaerobic biological treatment and anaerobic biological treatment equipment, which can also properly treat the discharge water containing polycarboxylate alkyl 201029938 ammonium salt and 6 carbons. The discharge water of the following organic substances and the like, in particular, an anaerobic biological treatment method and an anaerobic biological treatment apparatus containing discharged water containing TMAH and Hess, which are discharged from a semiconductor scale. Means for Solving the Problem: The present invention is directed to an anaerobic biological treatment method for discharging water containing a polyalkylamine alkylammonium salt, and a polycarboxylate in the water discharged from the above-mentioned polyoxosulfanyl ammonium salt. The acid alkyl ammonium salt concentration is below 2 〇〇〇 / L. In addition, the present invention is a treatment method for treating water containing poly (ortho-acidic ammonium) (IV) by anaerobic biological treatment, and the organic nitrogen and ammonia in the water discharged from the poly(tetra)alkylammonium salt are used in the above biological treatment. The total concentration of gas (Ammonia Nitrogen) is less than 3 9 〇. In the case of the former oxidizing biological material, it is preferable to circulate the part (4) of the treated water which has been treated by the biological treatment in the above-mentioned (4) Weijiyan salt discharge water. When the above-mentioned biological treatment is carried out, the concentration of the polyweiji-based money contained in the above-mentioned "acid-based base (4) discharged water is preferably less than 10000 mg/L. The present invention relates to an anaerobic biological treatment method for treating ammonium salt discharge water by anaerobic biological treatment, and when the above-mentioned biological treatment is carried out in the aforementioned polycarboxylate-containing alkyl salt discharge water , between pH__6 . 5 ~ 9. 0. The present invention is for the treatment of (4) (iv) quaternary ammonium salt discharge water-type anaerobes, for the treatment of the above-mentioned biological treatment, the water temperature is 2 〇t the above. The present invention relates to an anaerobic biological treatment method for treating polyhydric acid-containing sulphate discharge water by anaerobic biological treatment, and the conditions thereof must meet any of the following two items: (1) in carrying out the aforementioned biological treatment, The concentration of the polyalkyl phthalate salt in the above-mentioned lysine-containing ammonium salt discharge water must be less than 2 〇〇〇 0 mg / L, and the above-mentioned biological treatment of the carboxylic acid-containing ammonium amide is discharged in the same biological treatment. The concentration of polyalkylammonium salt in water shall be less than 2 〇〇〇〇mg/L. After completion of the above biological treatment, part of the treated water shall be placed again in the above-mentioned polyalkylammonium salt-containing discharge water. (2) When carrying out the aforementioned biological treatment, the total concentration of organic nitrogen and ammonia nitrogen in the above-mentioned polyalkylamine-containing ammonium salt-containing discharge water must be less than 3 gOOmg-N/L, and at the time of carrying out the biological treatment The total concentration of organic nitrogen R and ammonia nitrogen in the water discharged from the body containing the acid body of the body should be less than 3 〇〇m gN /L, and after the completion of the above biological treatment, part of the treated water must be placed in the foregoing Circulating water containing polyalkylammonium salt in discharged water; (3) the aforementioned polypyrene The alkylammonium salt discharged water has a pH ranging from 6 · ς ^ to 9.0 in the above biological treatment; (4) the above-mentioned polycarboxylic acid alkyl ammonium salt-containing water is subjected to the aforementioned biological treatment. The temperature must be above 20 °C. Further, in the aforementioned anaerobic biological treatment method, the above polyphosphonium amide is preferably tetraammonium hydroxide (TMAH). The anaerobic biological treatment device of the present invention has a biological treatment method for biological treatment of polyglycolic acid-containing salt discharge water in an anaerobic manner, and a method for adjusting the concentration of poly-alkalic acid alkyl ammonium salt to allow the discharge water to flow in. In the above biological treatment method, the concentration of the polycarboxylic acid 8 201029938 alkyl ammonium salt in the polyalkylamine-containing ammonium salt-containing water can be adjusted to be less than 20 〇〇〇 mg/L. The anaerobic biological treatment device of the present invention has a biological treatment method for performing polyanaerobic acid-based money salt discharge water in an anaerobic manner, and a method for adjusting nitrogen concentration to allow the discharge water to flow into the biological treatment method, the foregoing polycondensation The concentration of organic nitrogen and ammonia nitrogen in the water discharged from the alkylammonium carboxylate is lower than 390 mg-N/L. In the aforementioned anaerobic biological treatment apparatus, it is preferable to have a circulation method φ so that a part of the treated water subjected to the above biological treatment can be re-introduced into the above-mentioned polyalkylamine-containing ammonium salt-containing water discharge cycle. In the aforementioned anaerobic biological treatment device, it is preferred to have a method for adjusting the concentration of the polyalkylamine ammonium salt so as to be able to adjust the aforementioned polycarboxyalkylammonium salt-containing discharge water when the discharged water flows into the biological treatment method. The polyglycolic acid ammonium salt concentration is made lower than l〇〇〇〇mg/L. The anaerobic biological treatment device of the present invention has a biological treatment method for treating the water containing the polysodium sulphate salt by biological treatment, and a set of pH adjustment method for performing the aforementioned polycarboxylic acid-containing The range of the pH of the alkyl ammonium salt discharge water can be adjusted to a range of 6.5 to 9.0. The anaerobic biological treatment device of the present invention has a biological treatment method for treating the discharge water containing the polyalkylammonium salt of the polycarboxylic acid by biological treatment, and a set of the aforementioned water for discharging the polyalkylammonium salt containing polycarboxylate In the case of biological treatment, the temperature adjustment method of adjusting the water temperature in the above biological treatment method to 20 ° C or higher. The anaerobic biological treatment device of the present invention has a biological treatment method for treating effluent water containing polyalkylammonium salts of polycarboxylates by anaerobic biological treatment, and a method of any two or more of cold springs (~) in 201029938: (1) In the process of discharging the biological treatment method, the concentration of the (4) Weijilu salt in the discharged water containing the sulphuric acid-based salt is adjusted to 2 QQQ Qmg or less, and the acid acid-based salt concentration adjustment method is as follows After adjusting the concentration of the acid-saturated ammonium salt and the biological treatment, the partially treated water is again placed in the circulation method of the above-mentioned poly-soil-discharge water, and (2) when the discharged water flows into the biological treatment method, The nitrogen concentration adjustment method for adjusting the total concentration of the organic nitrogen and the ammonia nitrogen in the polyoxosulfate-containing ammonium salt discharge water to 3900 mg-N/L or less, and the nitrogen concentration adjustment method and the biological treatment described above are a part of the treated water is again placed in the circulation of the above-mentioned polyalkylamine ammonium salt-containing effluent water circulation; (3) in carrying out the aforementioned biological treatment of the polycarboxylic acid alkylammonium salt-containing water discharged , adjusting the pH to a pH adjustment range of 6 · 5 to 9 . 0; (4) in carrying out the aforementioned biological treatment of the polyalkylamine ammonium salt-containing water discharged, the biological treatment method described above The temperature is adjusted to 2 〇 above the temperature adjustment method. a In the aforementioned anaerobic biological treatment apparatus, the polyalkylamine ammonium salt is preferably tetraammonium hydroxide (TMAH). The present invention relates to an anaerobic biological treatment method for treating polylactic acid-based salt-containing salt discharge water by anaerobic biological treatment method, in the above-mentioned biological treatment, the above-mentioned polycarboxylate alkylammonium salt discharged water The concentration of alkyl citrate is less than 2 00 mg / L. 'The present invention is an anaerobic biological treatment method for treating polyhydric acid-containing salt discharge water by anaerobic biological treatment'. When performing the aforementioned biological treatment 201029938, the above-mentioned polycarboxylic acid alkyl ammonium salt is discharged. The total concentration of organic nitrogen and ammonia nitrogen in the water is below 3900 mg - ν / L. The present invention relates to an anaerobic biological treatment method for treating effluent water containing polyalkylammonium salts of polycarboxylates by anaerobic biological treatment, and when the above-mentioned biological treatment is carried out on the above-mentioned polyoxosulfate-containing ammonium salt discharged water, The water temperature is above 20 °C. The present invention relates to a biological treatment device comprising a method for treating a discharge water containing a polyalkylammonium salt of a polycarboxylic acid by an anaerobic biological treatment method, wherein the above-mentioned biological treatment method comprises a polyalkylammonium polycarboxylate. The concentration of the polyacid buffer in the salt discharge water is below 20,000 mg/L. The present invention relates to a biological treatment apparatus for treating a polycarboxylic acid-based salt-containing salt discharge water by an anaerobic biological treatment method, 'when the discharged water flows into the biological treatment method', the aforementioned polycarboxylic acid alkylammonium salt The total concentration of organic nitrogen and ammonia nitrogen in the discharged water is below 390 mg — N/L. The present invention relates to a biological treatment device comprising a method for treating a polycarboxylate-containing sulphate-containing effluent water by an anaerobic biological treatment method, and treating the polyalkylammonium-containing ammonium salt-containing water discharged by the biological treatment method described above In the case of the above biological treatment method, the water temperature is 2 Ot: or more. The present invention is an anaerobic biological treatment for treating effluent water containing a polyalkylammonium alkyl salt in an anaerobic biological treatment, which supplies molasses to the aforementioned effluent water. The present invention relates to 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 aforementioned discharge water. 0 11 201029938 In the anaerobic biological treatment method, at the beginning It is preferable to supply the aforementioned molasses at the time of biological treatment and after the start. In the Lishu anaerobic biological treatment method, it is preferable to introduce the anaerobic sludge into the reaction tank for performing the above biological treatment to start the above biological treatment. In the aforementioned anaerobic biological treatment method, the aforementioned discharge water is preferably discharged from a semiconductor factory. In the above anaerobic biological treatment method, the polycarboxylic acid alkylammonium salt and the organic matter containing 6 or less carbon atoms are preferably tetramethylammonium hydroxide (TMAH). In the anaerobic biological treatment method, 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 defeated. The anaerobic biological treatment apparatus of the present invention comprises a reaction tank for treating the discharge water containing the polyalkylammonium salt of the polycarboxylic acid by an anaerobic biological treatment method, and a method for supplying the molasses 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 molasses supply method for supplying the molasses to the discharged water. In the above 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 above anaerobic biological treatment apparatus, it is preferable that the anaerobic sludge is introduced into the reaction tank at the start of the biological treatment described above. In the aforementioned anaerobic biological treatment apparatus, the discharge water is preferably discharged from a semiconductor factory. In the above anaerobic biological treatment apparatus, the polycarboxylic acid alkylammonium salt 12 201029938 and the organic substance having 6 or less carbon atoms or less are preferably tetramethylammonium hydroxide (TMAH). In the above anaerobic biological treatment apparatus, it is preferable to fill the support in the reaction tank in which the biological treatment is carried out when the biological treatment described above is started. EFFECTS OF THE INVENTION According to the present invention, when anaerobic biological treatment of discharged water containing polyalkylamine ammonium salts such as TMAH or choline is carried out, it is possible to reduce the treatment of TMah-containing and bismuth-containing polycondensation The set-up area of the treatment equipment for the discharged water, at the same time has economic benefits and environmental benefits, provides good biological treatment methods and biological treatment devices, and can also well treat the polycarboxylate-containing salt-salted water and 6 carbons. In the discharge water such as the organic matter, the discharge water such as TMAH and choline is discharged from a semiconductor factory. [Embodiment] An embodiment of the present invention will be 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 mode constituting the anaerobic biological treatment apparatus of the present embodiment. As shown in Fig. 1, the anaerobic biological treatment device 1 has a raw water tank 10, a septic tank 1, an anaerobic biological treatment tank 14, a separation tank 16, a nitrogen treatment tank 18, and a treatment tank 2 . The adjustment groove} 2 includes the first adjustment groove 1 2 a and the first adjustment groove 1 2 b, but it does not necessarily have to be a multi-groove or a single groove. Raw water tank 1 0 and adjustment tank 1 2, adjustment tank 1 2 and anaerobic organism 13 201029938 treatment tank 1 4, anaerobic biological treatment tank 4 and tank 1 6 with nitrogen treatment tank 8 , nitrogen 2 6 &quot The cutters are connected by pipes 22a to 22e, respectively. There are pumps 24a, 24b on the 22^). a The first adjustment tank i 2 a is connected with dilution = 彳 inflow line 28, nutrient inflow line 3 Γ 2 = Γ adjuster flow line 2 8 and vapor 2 tube ^ 3 4 are connected. The first-adjusting tank 1 2 a and the b-th loading (four) mixing device 36, 38.帛-tank 1 2 Anaerobic biological treatment tank 1 4 As long as it can be used for anaerobic biological treatment, UASB: base 2: granules upflow sludge bed type anaerobic biological treatment tank can be used Body solid boring or fluidized bed anaerobic biological treatment tanks, etc. Ships used in anaerobic biological treatments are not particularly difficult to manufacture. For example, a foamed support such as Wei, a colloidal support such as polyvinyl alcohol (PVA), a fibrous support, a nonwoven fabric molded article, and a molded article such as 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, calcium salt or fly ash, and a coagulant and an organic substance to promote the particle forming substance when the amount of the particles is not reduced in the operation. According to the present inventors, in the anaerobic biological treatment tank 14 polycarboxylate 201029938 acid-based salt (for example, tmakq 炫, acid ion and ammonia ion, etc.. The following description of the embodiment and anaerobic biological treatment It will be broken down into an anaerobic biological treatment device 1 in the armor due to anaerobic organisms.

Start the pump 24 4 a, and pass the polyphenolic acid (4) in the raw water tank i to the wire W 2 through the pipe 2 2 a. Further, dilution water is supplied from the dilution water inflow line 26 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 polycarboxyalkylammonium salt in the polyalkylamine-containing ammonium salt-containing water must be below 2 〇〇〇〇mg/L. It is best to 丄〇〇◦ 〇mg eight or less. Especially when there is concern about changes in water quality and effects on coexisting substances, when the discharged water flows into the anaerobic biological treatment tank 4 (when biological treatment is carried out), the polycarboxylate containing water in the alkyl ammonium salt of polycarboxylate is discharged. The concentration of the quaternary ammonium salt is preferably less than 5 〇 0 0 mg/L, and more preferably in the range of from 1 〇〇〇 to 3 〇〇〇 mg/L. In the present embodiment, if the concentration of the polycarboxyalkylammonium salt in the polycarboxylate alkylammonium salt-containing water exceeds 2 〇α〇〇mg/]L, it is only necessary to supply dilution water to dilute the concentration to 200 〇. 〇mg/L or less. However, even if the concentration of the polycarboxylic acid sulphate in the water discharged from the polyacid buffer is less than 200 mg/L (for example, above 丄〇〇〇〇mg/L), dilution water can be supplied, for example, diluted. It is also possible to be in the range of χ 〇〇〇〇 mg/L or in the range of 1 000 to 3000 mg/L. When the discharged water flows into the anaerobic biological treatment tank 14 , the concentration of the polycarboxyalkylammonium salt in the polyoxoalkylammonium salt-containing water exceeds 20 〇〇Omg/L, and is collected during biological treatment. The decomposition of the carboxylic acid-based salt is reversed. 15 201029938 The speed should be slower. In the present embodiment, an inductor for inspecting the concentration of ammonia ions in the treated water after biological treatment may be installed at a position such as the pipe 22c. Further, the concentration of the polycarboxyalkylammonium salt can be estimated from the detected ammonia ion concentration, and the amount of the dilution water added can be determined based on the estimation, so that the discharged water flows into the anaerobic biological treatment tank 14, and the polycarboxylate The acid alkyl ammonium salt concentration can be within the above range. Further, an inductor for inducing a concentration of a polyalkylammonium salt of a polycarboxylate may be installed at a position such as the adjustment tank 12 or the pipe 2 2 a. Then, according to the polycarboxylate-based salt salt, the amount of dilution water is determined to be such that when the discharged water flows into the anaerobic biological treatment tank 14, the polyglycolic acid ammonium salt concentration can fall above Within the scope. When the ammonia ion concentration in the anaerobic biological treatment tank 14 exceeds 5 〇〇 0 mg/L, the decomposition reaction rate is lowered, so the ammonia ion concentration in the anaerobic biological treatment tank 14 must be lower than 50 〇〇. Mg/L, preferably below 1000 mg/L. In the anaerobic biological treatment, almost all of the gas components other than nitric acid and nitrous acid in the discharged water are gas ions. Therefore, in the present embodiment, the dilution water is supplied to the adjusting tank 1 through the dilution water inflow line 26. When the discharged water flows into the anaerobic biological treatment tank 14 (when biological treatment is carried out), the total concentration of the organic hydrazine and ammonia nitrogen in the polycarboxylate-containing salt-containing salt discharge water is less than 399 mg-N/L or less. Preferably, the concentration of ammonia ions in the anaerobic biological treatment tank 14 falls within the above range, preferably below 780 mg-N/L. In the present embodiment, if the total concentration of organic nitrogen and ammonia nitrogen in the water containing alkyl ammonium chloride salt exceeds 390 mg-N/L, it is necessary to supply dilution water to dilute the concentration 16 201029938 to 3 9 0 G mg. - N/L or less. However, even if the total concentration of organic nitrogen and ammonia nitrogen in the water discharged from the polyphenolic acid-based salt is less than 3 〇 〇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 steaming ammonia waste liquid and II>A waste liquid if equipment is present in the factory. The water temperature of the distilled water is higher at 40 C, so that the anaerobic biological treatment tank 14 can be warmed to promote the decomposition reaction of the polyalkylene salt. Further, in the present embodiment, the biologically treated partial treated water and the dilution water may be supplied to the conditioning tank 12 in place of the dilution water through the circulation line 34. If the concentration of the polycarboxyalkylammonium salt in the discharged water is too high, the amount of water discharged from the anaerobic biological treatment tank 14 is increased when the dilution water is added to dilute the discharged water. When increasing the amount of water required for dilution and increasing the amount of discharged water, it is best 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 adjusting tank 1 2 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 polycarboxylic acid alkylammonium salt in the polyalkylamine-containing ammonium salt-containing water must be below 20,000 mg/L, preferably at 1 Torr. 〇mg/L or less, more preferably less than 5 〇0 〇mg/L, and further, preferably in the range of 1 〇〇〇~300 〇mg/L, or containing polyalkylammonium phosphate The total concentration of organic nitrogen and ammonia nitrogen in the salt discharge water is less than 3 900 mg - N / L, preferably below 780 mg - N / L. However, in the treated water after biological treatment, the total concentration of organic nitrogen and ammonia nitrogen in the water discharged from the alkylammonium salt containing polycarboxylate is lower than that due to the ammonia ion generated by the decomposition of the acid buffer base salt. 3 9 〇0 mg _ N/L, you can directly recycle the water without using 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 water discharged from the alkylammonium salt of polycarboxylate is less 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 polycarboxylate alkylammonium salt-containing water, the pH adjuster is supplied from the pH adjuster inflow line 28 to the conditioning tank to bring the pH to 6.5 to 9.0. Within the range, preferably between 7 · ❹ 0 ~ 8. 0. If the pH of the water discharged from the alkylammonium salt of the polycarboxylic acid exceeds the above range, the decomposition rate of the polyalkylamine ammonium 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 in the weakly acidic range of 6 · 5 to 7, but the treatment of the polyalkylamine ammonium salt must be weak in the pH of 7 to 8. The degree of alkali can achieve the best treatment effect. This is the first condition discovered by the inventors. Here, in the above pH adjustment, the concentration of the polycarboxylate alkylammonium salt in the polycarboxylate alkylammonium salt-containing water is preferably below 20,000 mg/L, and the total concentration of the organic nitrogen and ammonia nitrogen is preferably at 3 9 . 0 Omg—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 be a sodium bicarbonate or a buffer of citric acid having a buffering action. In the present embodiment, when the biological treatment of the polycarboxylate alkylammonium salt-containing water is carried out, the temperature of the water in the anaerobic biological treatment tank 14 must be adjusted, preferably at 20 C or more. Best at 2 8~3 53⁄4 of the 18 201029938 generation Τη. The anaerobic biological treatment of the polyacid acid sulphate can also be degraded at a low rate of 2%, but if the decomposition rate is lower than the 2nd generation, the water temperature must be adjusted to the above range. The above-mentioned temperature adjustment is particularly limited by the fact that, for example, steam can be supplied from the vapor inflow line 3 2: day 1 2 (such as the second adjustment tank 2 b ) to adjust the water temperature in the anaerobic biological treatment tank 14 Or, add = to the anaerobic biological treatment tank 14, use the heat of the heater to adjust the 厌 in the anaerobic biological treatment tank 14 or "can supply 28 warm lion dilution water to the anaerobic organism Treating the water/dish in the tank 14 or generating the burnt gas when the polyacid acid is decomposed. After the desulfurization treatment according to the general anaerobic treatment, the heat energy of the furnace can be recovered. The heat energy is supplied to the anaerobic biological treatment tank to adjust the water temperature. Here, when the water temperature in the anaerobic biological treatment tank 4 is adjusted to the above range, the water containing the polyacids is recorded in the discharge water. The concentration of polyglycolic acid amide must be less than 2 〇〇〇〇mg / L 'the total concentration of organic nitrogen and ammonia is less than 3 〇〇mg - N / L ·. In this embodiment, in order to To maintain good decomposition activity of anaerobic organisms, it is best to adjust the nutrient into the pipeline 3 to add nutrients. 1 2. The type of the nutrient is not particularly limited, and a carbon source, a gas source, other inorganic salts, etc. may be used. The various methods described above may be used in the anaerobic biological treatment tank 4 In the salt discharge water, polyarsenic acid is used to decompose an alkane (gas), an ammonia ion, etc. In this embodiment, in the present embodiment, the polyanaerobic ammonium salt is decomposed by anaerobic biological treatment, preferably using the foregoing. (1) Adjusting the concentration of the poly-acidic ammonium salt or adjusting the concentration to circulate part of the treated water at 19 201029938; (2) adjusting the total concentration of nitrogen and ammonia nitrogen in the body of M ^ & Or adjusting the total nitrogen concentration and allowing a portion of the treated water to adjust the pH of the polyglycolate-containing salt discharged water to adjust the water temperature of the water containing the polyalkylamine ammonium salt. It can be implemented in either of the above-mentioned ways. Compared with aerobic treatment, the type of raw water that can be treated with anaerobic biological treatment in the past is relatively limited. ' Anaerobic biological treatment of tannins, carbohydrates, and biomaterials can be used. Decomposability 2=: and the substances it constitutes, Foods or beverages containing sugars, alcohols, etc., water discharged from brewing plants, etc. In addition, since the water quality of anaerobic biological treatment cannot reach the concentration of aerobic biological treatment, aerobic biological treatment equipment is generally installed in the latter stage. The practical situation of the anaerobic biological treatment is as described above, but the present inventors have found that the artificial synthetic substance which is difficult to decompose for aerobic biological treatment, the polyalkylamine ammonium salt contained in the substance TMAH, choline, etc. The anaerobic biological treatment embodiment method of (i) to (4) described above is used to treat even under anaerobic treatment conditions, and the treatment speed is faster than that of aerobic biological treatment, and is processed. The water quality 方面 aspect is also significantly better than the anaerobic treatment water quality known in the past, and it is no longer necessary to set up aerobic biological treatment equipment in the latter stage. At the same time, it has been found that the water temperature conditions of the anaerobic treatment are generally lower than the water temperature below 35 ° C, and the polycarboxylate can be well treated under the water temperature of 20 ° C to 35 ° C. Alkalium salt. Moreover, in the anaerobic biological treatment of the resist discharged from the semiconductor factory development project and the surfactant-containing polyalkylammonium salt-containing water, the above description (1) to (4) are used. The anaerobic biological treatment embodiment method can decompose the polycarboxyalkyl group 20 201029938 ammonium salt into TOC (total organic carbon) without significant hindrance. The polycarboxyalkylammonium salt which can be treated in this embodiment includes Tetramethylammonium Hydroxide=TMAH, Tetra ethylammonium Hydroxide 'Tetra propylammonium Hydroxide, Tetra Butylammonium Hydroxide, Methyl triethylammonium Hydroxide 'Trimethyl ethylammonium Hydroxide, Dimethyl diethylammonium Hydroxide , Trimethyl(2-hydroxyethyl)ammonium Hydroxide (also known as cholesteric: ❹), Triethyl(2-hydroxyethyl)ammonium Hydroxide, Dimethyldi(2-hydroxyethyl)ammonium Hydroxide > Diethyldi(2-hydroxyethyl)ammonium Hydroxide 'Methyltris(2- Hydroxyethyl)ammonium Hydroxide 'Ethyltris(2-hydroxyethyl)ammonium Hydroxide 'Tetra(2-hydroxyethyl)ammoniumHydroxid and the like. This embodiment is particularly applicable to φ Tetra methylammonium Hydroxid (TMAH) > discharged from semiconductor factories and liquid crystal factories.

Trimethyl(2-hydroxyethyl)ammonium Hydroxid (also known as bile test) Separation tank 16 is connected to anaerobic biological treatment tank 14 by sludge return line 40, and sludge separated by separation tank 16 It is best to return to the anaerobic biological treatment tank 14 if necessary. When the SS component containing a resist, a surfactant, or the like is contained in the polycarboxyalkylammonium salt discharge water, it is preferable to provide a separation tank capable of separating and removing the SS component in the front stage of the bioprocessing tank. When the anaerobic biological treatment tank 14 is treated with polyalkylamine ammonium salt discharge 21 201029938 water, even if it is mixed with a resist or a surfactant, it does not affect the biological treatment. Processing, but the provision of the separation tank prevents the ss component from causing the processing device to block. The separation tank may be a pressurized float, a precipitation treatment, or the like, and is not particularly limited. In addition, it is preferable to add an antifoaming agent to the treatment tank if it has a significant foaming condition. In the anaerobic biological treatment tank 14, the biologically treated treated water containing the polycarboxylate saddle salt discharge water contains ammonia nitrogen, so it is preferable to provide a nitrogen treatment tank in the latter stage of the anaerobic biological treatment tank 14. 1 8. The nitrogen treatment tank 18 can be a generally known nitrogen treatment apparatus, for example, biological treatment such as nitrification-denitrogenation-reoxidation treatment, nitrosation-Anammox treatment, or ammonia distillation, stripping treatment, or the like. A device such as physical and chemical treatment. In addition, mixing the treated water part with the discharged water, and performing the TMAH treatment after the stripping treatment can also reduce the burden of the nitrogen treatment in the latter stage. After that, the treated water subjected to anaerobic biological treatment, separation treatment, nitrogen treatment, and the like is stored and treated in the water tank. ❹ <Second Embodiment> Fig. 2 is a view showing another mode constituting 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 4, an adjustment tank 44, a raw water second line 46, a reaction tank 48, a treated water discharge line 5, The gas discharge line 5, the treatment water circulation line 5.4, the molasses supply method, the nutrient supply method, and the pH adjuster supply method are comprised. 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 22 201029938 nutrient storage tank 6 〇, nutrient supply camp supply method W 62 constitutes a positive adjustment agent fi, : 槿忠 /, the whole agent storage tank 64, the positive regulator supply line 6 water can be ^ each supply side (four) knot Wei will be supplied to the discharge: = the above structure restrictions. For example, it is preferable to install the Lipu in order to be able to adjust the supply lines of the solvent. In the adjustment tank * 4 = = the device stirring device 6 8 is made uniform by the stirring device 6 8 or the like. The original water guide σ (not shown) of ❹ &"£' slot 4 4 is connected to the raw water No. - Guan Lu 4 2 . The molasses discharge port of the molasses storage tank 56 (not shown) is connected to the molasses supply port (not shown) of the tray adjustment tank 44 through the molasses supply line 58 and the nutrient storage tank of the nutrient storage tank 6 (not shown) The nutrient supply port (not shown) of the adjustment tank 44 is connected to the nutrient supply line 6 2, and the Η adjuster discharge port (not shown) of the adjustment tank 44 is adjusted to the adjustment tank 44. The pH adjuster supply ports (not shown) are connected to each other 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 4 6 . 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 a partition plate 7 〇 a, which is inclined in the opposite direction, and has a solid-liquid separation portion 72 on the inner side thereof. The partition plates 7〇a, 7 0 b are separated to form a communication path 74, and the partition plate 7 0 a, 7 0 b — the lower side of the lower side is covered under the lower end of the other side, this structure The gas that can be floated on the pavilion enters the solid-liquid separation 23 from the communication path 74 in 2010. The solid-liquid separation unit 7 2 is provided with an overflow-type treated water take-out unit 76, and the treated water discharge port (not shown) of the treated water take-out unit 76 processes the water discharge line 5 Q. Further, a treatment water return port (not shown) of the treatment 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 polycarboxyalkylammonium salt by anaerobic biological treatment, it is possible to use a UASB type, an EGSB method or the like to use a particle-flowing sludge bed reactor or a fixed bed using a support. , flow bed reactor, etc. The operation of the anaerobic biological treatment device 2 of the present embodiment and the anaerobic biological treatment method will be described below. The polybasic acid-containing salt water discharge water is supplied to the adjustment tank 44 through the raw water first line 4 2, and the molasses in the molasses storage tank 56 is supplied to the adjustment tank 44 through the molasses supply line 58. Then, the mixed solution (containing polyalkylammonium salt discharge water and molasses) mixed with the mixing device 68 is introduced into the reaction tank 48 through the raw water second line 46, and is circulated upward. According to the study of the present inventors, in the reaction tank 48, the polycarboxyalkylammonium salt (e.g., TMAH) is decomposed into decane, carbonate ion, ammonia ion 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 waste, paper mills, chemical plants, livestock discharge water treatment, etc., anaerobic sludge, granules, and sewage treatment sites will be used. Use digested sludge, etc. It is shown in the data of the conventional technology that the granules containing the anaerobic microorganisms 24 201029938 sludge will be put into the reaction tank 48 when the biological treatment is started, and the lamp is subjected to the atrophic treatment, but in the present embodiment, Added molasses (4) Anaerobic pure lion family, and then cut into the reaction tank 48 to carry out biological treatment. In this embodiment, it is preferable to supply the molasses at the time of starting the biological treatment and after the start of the biological treatment. The amount of molasses supplied is not particularly limited, and the ratio of 乂 乂 0 0 0 0 0 0 0 0 0 0 0 0 0 0 或 或 或 或 或 或 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The present inventors have found that the addition of molasses allows the anaerobic sludge to form granular sludge and suppresses the slimming of the granular sludge during the anaerobic biological treatment, and thus the present invention has been derived. The reason why the addition of molasses can produce the above-mentioned effects is because the molasses is a high-molecular organic substance, which promotes the proliferation of hydrolyzed bacteria and acid-producing bacteria, and produces a biopolymer (bi〇p〇lymer) having a particle bridge structure, and can also be utilized. Drunken acid smoldering produces a bacterial lineage of Methanosaeta. In addition, molasses contains trace elements required for the growth of microorganisms such as organic matter, and the trace elements promote the formation of particles. Pure water and ultrapure water are used in semiconductor factories, so the above-mentioned trace elements contained in the discharge water of such factories are insufficient. Adding honey can supplement the trace elements required for microbial growth. 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 salt of a mother or a fly ash may be added, or a substance such as an aggregating agent or an organic substance which promotes the formation of particles may be added. The term "molasses (including waste molasses)" as used in the present specification refers to the production of sugar by making raw sugar (raw sugar) from sweet juice (Cane) or when making raw sugar or when producing beet sugar from sugar beet. By-products produced at the time (specific gravity 25 201029938 large viscous brownish liquid). Molasses contains 4 〇~6 〇% of sugar, and molasses is generally 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 materials of the molasses are 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 be a waste molasses, and it is preferable to use the molasses from the viewpoint of cost. Further, the starch used in Patent Document 4 (Japanese Laid-Open Patent Publication No. Hei No. 2000-279385) is a generic term for a glucose ruthenium polymer to which D-glucopyranose (Gluc〇Pyranose)-a-i·4 is bonded. As shown in the foregoing description, in the reaction tank 48, (mainly after unfolding biological treatment) polyalkylammonium salts (for example, TMAH) are decomposed into decane, carbonic acid and ammonia ions by anaerobic organisms. Wait. The anaerobic biologically treated discharged water passes through the communication passage 74 to enter the solid-liquid separating portion 72, 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 decane generated in the reaction tank 48 is blocked by the partition plates 7 〇a, 7 Ob, does not flow into the solid-liquid separation portion 7.2, and rises from the reaction tank 48, from the gas discharge line 5 2 outflow. In the present embodiment, a part of the biologically treated treated water is supplied to the adjusting tank 44 through the treated water circulation line 54, and when it flows into the reaction tank 48 (when performing biological treatment), the polycarboxylate is contained. The concentration of the polyphenolic acid-based salt in the quaternary ammonium salt discharge water is preferably lower than 2 QQQ 〇 mg / L ' is more preferably in the range of less than 1 0000 mg / L. In particular, if there is concern about changes in water quality and effects on coexisting substances, the concentration of polyalkylammonium salts of polycarboxylates in the discharge water containing alkylammonium salts of polycarboxylates is the highest when flowing into the reaction tank (8: 26, 201029938 for biological treatment). It is preferably less than 5000 mg/L, and particularly preferably in the range of 1000 to 300 mg/L. In the present embodiment, when the concentration of the polycarboxyalkylammonium salt in the polycarboxylate alkylammonium salt-containing water exceeds 2 〇〇0 0 mg/L, the treated water may be supplied for dilution to a concentration lower than 2 ◦. 000mg/L·. However, even if the concentration of the polycarboxylic acid alkylammonium salt in the polycarboxylate alkylammonium salt-containing water is less than 20 〇〇〇mg/L (for example, more than l〇〇〇〇mg/L), it can be supplied to the treatment. Water, diluted to less than 1 0000 mg / L or 1 〇〇〇 ~ 3 〇〇〇 mg / L range. When flowing into the reaction tank 48, the concentration of the polycarboxyalkylammonium salt in the polycarboxylate alkylammonium salt-containing water exceeds 2 〇〇〇〇mg/L, and the polycarboxylic acid alkylammonium salt is subjected to biological treatment. The decomposition reaction rate sometimes becomes slower. In the present embodiment, an inductor for treating the concentration of ammonia ions in the water after inductive biological treatment may be provided on the treated water discharge line 5 or the like. Further, the concentration of the polycarboxyalkylammonium salt can be estimated from the ammonia ion concentration of the test G, and the amount of the treated water can be determined according to the estimated enthalpy, so that the polyphenolic acid burnt group which flows into the reaction tank 48 can enter the above according to the salt concentration. Within the scope. Further, an inductor for detecting the concentration of the polyphenolic acid salt may be installed in the adjustment tank 44 or the raw water first line 4 2 or the like. At the same time, the added amount of the treated water can be determined according to the concentration of the polyalkylamine ammonium salt which is detected, so that the concentration of the polyphenolic acid salt in the reaction tank 48 can enter the above range. When the concentration of ammonia ions in the reaction tank 48 exceeds 500 〇mg/L, the rate of decomposition reaction will be slowed down. At this time, part of the treated water after biological treatment 27 201029938 can be treated through the treated water circulation line 5 4 The concentration of the ammonia ion supplied to the adjustment tank 4 4 'reaction tank 48 is preferably less than 5 〇〇〇 mg / L ' or even 10 〇 mg / L or less. In addition to the above-mentioned biologically treated treated water, it is also possible to use industrial water, discharge water, or right-hand waste equipment to use distilled water (condensed water) such as ammonia waste liquid and IPA waste liquid. As the dilution water, the discharged water containing the poly-acid-acid base salt is diluted. The water temperature of the treated water is as high as 4 〇 ° C to warm the reaction tank 48 to promote the decomposition reaction of the polycarboxyalkylammonium salt. ❹ In the present embodiment, when the biological treatment of the polyalkylamine ammonium salt-containing water is carried out, the pH is preferably between 6. 5 and 9 · 0, and if it can reach 7. 0 to 8 • 0, it is better. It is preferable to supply the pH adjuster to the adjustment tank 44 through the pH adjuster supply line 66. If the pH of the water discharged from the alkylammonium salt of the polycarboxylic acid is not within the above range, the decomposition reaction rate of the alkylammonium salt of the polycarboxylic acid may be slowed down during the biological treatment. In addition, in the past, in the anaerobic biological treatment, in order to reduce the hindrance of ammonia, the pH was controlled as much as possible in the range of ρΗβ. 5~7 weak ❹ acidic, but the treatment of the polyacid sulphuric acid salt was pH7~8 The weak face processing performance is better. This was confirmed by the inventors for the first time. When the pH is adjusted to the above range, the concentration of (4) acid recording in the water discharged from the ship's salt is preferably less than 2 Q ao Qmg/L, and the ammonia ion concentration is preferably below 5 〇〇 0 mg/L. The pH adjuster used in the present embodiment is not particularly limited as long as it is an acid such as hydrochloric acid or a hydrogen fluoride. Further, the pH adjusting agent can also be used for buffering sodium bicarbonate and citric acid buffer. 28 201029938 Towels In order to maintain good decomposition activity of anaerobic organisms, it is preferable to supply nutrient to the adjustment tank 4 through the nutrient supply line 62. The _ system without a special ship can be a carbon source, a gas source and other inorganic salts. In the present embodiment, in the biological treatment day π containing the polycarboxylic acid-based sulphate-salted water, it is preferable to adjust the water temperature in the reaction tank 48 to 2 〇 ° C or more, and to adjust to 2 8 to 3 5 °. Especially within the scope of C. In the case of anaerobic biodegradation, the temperature may be lower than 2 generations, but if the temperature is lower than 20 C, the decomposition reaction rate will be slower, so it is better to adjust the water temperature to the above fe . The above temperature adjustment has no particular limitation on the method. For example, steam can be supplied to the adjustment tank 4 to adjust the water temperature in the reaction tank 48. Alternatively, the heater can be installed in the reaction tank 48, and the heat of the heater can be utilized. The temperature of the water in the reaction tank 48 is withered. In addition, warmed dilution water may be supplied to adjust the temperature of the water in the reaction tank 48. Methane gas is generated when the polycarboxyalkylammonium salt is decomposed. At this time, the same enthalpy desulfurization treatment in the anaerobic treatment is generally used, and then the decane is recovered to the methane boiler as a heat source, and the heat source is supplied to the reaction tank. 4 8 to adjust the water temperature. Here, when the water temperature in 48 is adjusted to the above range, the concentration of the polycarboxylic acid alkylammonium salt in the polycarboxylate alkylammonium salt-containing water is preferably less than 2 OOOOmg/L, and the ammonia ion concentration is preferably 500. 〇mg/L or less. The problem of the discharged water during the anaerobic treatment in the present embodiment is exemplified by the discharge of the polyalkylamine ammonium salt-containing water, but the organic discharge water containing six or less substances can be similarly subjected to anaerobic treatment. . Projects that use pure water and ultrapure water, such as semiconductor factories, emit emissions containing polychlorinated or hydrous-containing salt (or isopropanol, monoethanolamine, etc.) containing less than 6 carbons. When the conventional anaerobic biological treatment method is used after the treatment of the discharged water, 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), and the long-term Problems such as maintenance of processing performance. In addition to the conventional anaerobic biological treatment method, 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 project such as a semiconductor factory that uses pure water or ultrapure water, the discharge water containing the polyacid-base salt or the organic-containing water containing 6 carbon or less may be discharged. The addition of molasses produces granular sludge at the start of the treatment, maintenance of the granular sludge after the start of the treatment, and maintenance of the long-term treatment performance. A stable effect can be obtained. It is a good anaerobic biological treatment in terms of economic efficiency, operational management and environment. The semiconductor factory discharge water to be used in the present specification also includes discharge water discharged from a manufacturing plant such as a semiconductor such as 1C or LSI or a liquid crystal panel. The polycarboxyalkylammonium salt which can be treated in this embodiment includes Tetramethylammonium Hydroxide=TMAH, Tetra ethylammonium Hydroxide 'Tetra propylammonium Hydroxide, Tetra Butylammonium Hydroxide, Methyl triethylammonium Hydroxide, Trimethyl ethylammonium

Hydroxide, Dimethyl diethylammonium Hydroxide, Trimethyl(2-hydroxyethyl)ammonium Hydroxide (also known as bilis) 'Triethyl(2-hydroxyethyl)ammonium Hydroxide ' 30 201029938

Dimethyldi(2-hydroxyethyl)ammonium Hydroxide, Diethyldi(2-hydroxyethyl)ammonium Hydroxide '

Methyltris (2-hydroxyethyl)ammonium Hydroxide, Ethyltris (2-hydroxyethyl)ammonium Hydroxide, Tetra(2-hydroxyethyl)ammonium Hydroxid, and the like. This embodiment is particularly applicable to Tetra methylammonium Hydroxid (TMAH) discharged from semiconductor factories and liquid crystal factories.

Trimethyl(2-hydroxyethyl)ammonium Hydroxid is also a test. The treatment of the present embodiment is also applicable to treatment with an organic substance containing six carbons or less, for example, the above polycarboxyalkylammonium salt containing six carbons or less, isopropanol (IPA), decyl alcohol, monoethanolamine, citric acid, propylene glycol Ethyl acetate (PGME), cyclohexanone, dimethyl sulfoxide (DMSO), and propylene glycol methyl ether acetate (PGMEA). <Embodiment 3> Fig. 3 is a diagram showing another configuration of an anaerobic biological treatment apparatus according to the embodiment. In the anaerobic biological treatment apparatus 3 shown in Fig. 3, the same components as those of the anaerobic biological treatment apparatus 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 7 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 as the case arises. There is a return line 80. The return line 8 is disposed between the separation tank 7 8 and the reaction tank 48. Through the above structure, when the biological treatment is started, the sludge flowing out of the treated water can be recovered to the separation tank 7 8 due to fluctuations in the raw water or the like, and then returned to the reaction tank 48 through the return line 8 . Separation tank 31 201029938 7 8 The M agglutinating agent can be used for the treatment of the Lai Nian Dian, the pressurized floating treatment, etc. In addition, if it is dependent on the foaming situation, it is preferable to add an antifoaming agent when supplying the knife to the groove 78. In addition, when the SS component of the anti-money agent, interface/tongue U is contained in the discharge water of the poly-capric acid-based salt in the right, it is preferable to provide a separation tank which can remove the SS into a knife before the reaction tank 48. . When the polyhydric acid-containing salt-salted water is treated in the reaction tank 48, even if it contains an anti-agent or a surfactant, it does not affect the biological treatment, so it is not necessary to sit and remove the treatment beforehand, but the separation is set. The tank prevents the SS component from causing blockage of the processing unit. ❿ <Fourth Embodiment> Fig. 4 is a view showing another mode of the anaerobic biological treatment apparatus in the present embodiment. In the anaerobic biological treatment apparatus 4 shown in Fig. 4, the same structures as those of the anaerobic biological treatment apparatus 3 shown in Fig. 3 are denoted by the same reference numerals, and the description thereof will be omitted. The reaction tank 48 of the anaerobic biological treatment apparatus 4 shown in Fig. 4 is filled with a carrier 82. When the biological treatment is carried out, since the support tank 48 is filled with the support 82, the time for forming and retaining 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 in the form of a honeycomb structure such as a honeycomb or a V-shape, a mesh-like thick pad shape, a mesh tube type, or 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. 32 201029938 In the treatment tank, the biological treatment of the sulphide-containing salt-containing salt discharge water in the reaction tank is preferably provided with a nitrogen treatment tank in the latter stage of the reaction tank 48. The nitrogen treatment tank can be used as a general-purpose reduction device, for example, biological treatment such as nitrification, denitrification, reoxidation treatment, nitrosation-Anammox treatment, or ammonia distillation, stripping treatment, etc. Device. In addition, mixing the treated water cycle with the discharged water, and performing the TMAH treatment after stripping treatment can also reduce the burden of nitrogen treatment in the latter stage. EXAMPLES The following examples and comparative examples are given to further illustrate the present invention, but the present invention is not limited to the following embodiments. (Example 1) A glass vial having an internal volume of 100 m L was charged with a discharge water (ρΗ7, containing a microbial nutrient) having a concentration of 5 〇0 0 mg / L TMAH, 47.5 mL, anaerobic stain Mud (sludge concentration 2 〇〇〇〇mg/L β ) 2 · 5 m L 'to make the total liquid volume reach 50 m L. The glass vial was filled with nitrogen, sealed with an aluminum lid, and shake-cultured at 35 °C. Table 1 shows the data of TMAH concentration before and after anaerobic biological treatment in 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. Table 1 TMAH concentration 1 Cmg/L] gas generation amount [mL] decane concentration in gas [%] After treatment treatment Example 1 5000 121 227 88 33 201029938 From Table 1, we confirmed as in Example 1 Anaerobic biological treatment can decompose TMAH. In the following implementation, we will use the anaerobic biological treatment to decompose TMAH when the gas production rate per unit sludge (L/gVSS/d) is used as an indicator of TMAH decomposition activity (the gas generation rate is more representative of TMAH decomposition activity). Higher). (Example 2: Relationship between initial TMAH concentration and maximum gas generation rate)

In a glass vial with an internal volume of 100 m L, a concentration of 1 4 〇〇 5 〇〇〇, loooo, 20000 > 50000 mg / [containing 1 ^ 8 11 discharged water (pH 7, containing microbial nutrient) 4 7 .

5 m L 'anaerobic sludge (sludge concentration 2 〇〇〇〇 mg/L) 2 _ 5 m L 'to make the total liquid volume reach 5 〇 m l. Fill the glass vial with a gas cap and seal it with a face cap to 3 5 . (: Vibration culture. We measure the gas generation rate of each sludge by periodically measuring the amount of gas produced by the syringe.) In order to confirm that the sludge self-digests and does not generate gas, this does not add TMAH. Blank (^ank) test (with microbial nutrient added) Table 2 shows data for initial TMAH concentration and maximum gas production rate within 140 hours after the start of the test.

2-5 Initial TMAH concentration [mg/Ll maximum gas generation rate [L/gVSS/d] 0 0.00 1400 0.42 --------- 5000 0.47 10000 0.44 20000 0.25 — 50000 0.00 34 201029938 According to the embodiment 2 As a result, in the initial TMAH concentration of 5 〇〇Ο 0 mg/L, no gas was generated accompanying the decomposition of hydrazine. Moreover, according to the maximum gas generation rate of Table 2, in the anaerobic biological treatment of bismuth, the concentration of τμαη at the initial stage must be at least less than 20 〇〇0 mg/L, preferably below the work 〇〇〇L. After the water quality changes and other factors, it is confirmed that the TMAH concentration is preferably in the range of 1 400 to 5 0 〇〇mg/L to obtain a higher velocity of the ruthenium decomposition reaction. Further, in Example 2-1., when the measurement was completed, the enthalpy was not detected, and the ammonia ion concentration was about 3 〇 〇 m g/L. From this result, it is understood that after the decomposition of the hydrazine, the final product is ammonia ion and decane. (Example 3.3 ♦ Relationship between initial atmospheric ion concentration and maximum gas generation rate) A 100 mL inner glass vial was filled with a discharge water (pH 7 containing microbial nutrient) containing a concentration of 14 〇 0 mg/L TMAH. 7 · 5 m L, anaerobic sludge (sludge concentration 20000mg/L) treated with sputum-containing effluent water 2 · 5mL ' then add ammonia

The concentration of ions is 0, 1000, 2000, 3000, 5〇〇Q, 1 0 0 0 Omg / L ammonia ion source of ammonia chloride (ammonia ion concentration 0 m g / L means no added ammonia). The glass vial was filled with nitrogen, sealed with an aluminum lid, and shake cultured at 35 °C. Then, the amount of gas generated is measured periodically with a syringe to measure the gas generation rate of each sludge. Table 3 shows the data of the initial ammonia ion concentration and the maximum gas generation rate (within 4 hours after the start of the test). 35 201029938 Table 3 Initial ammonia ion concentration Ammonia nitrogen concentration Maximum gas generation rate [mg/L] [mg-N/L] [L/gYSS/d] Example 3 - 1 0 0 0.42 Example 3 - 2 1000 780 0.36 Implementation Example 3 - 3 2000 1560 0.41 Example 3 - 4 3000 2340 0.31 Example 3 - 5 5000 3900 0.25 Example 3 - 6 10000 7800 0.11 From the results of Example 3, we confirmed the initial ammonia ion concentration of 1 0 0 ❹ 0 0 At mg / L, the rate of gas generation will drop rapidly, so the decomposition rate of TMAH will also drop rapidly. From the maximum gas generation rate in Table 3, it can be known that in the anaerobic biological treatment of TMAH, the initial ammonia ion concentration must be at least 500 〇mg/L (the total nitrogen concentration is 390 mg). N/L or less), preferably below 3000mg/L (

The total nitrogen concentration is below 2 3 4 0 mg — N/L. If it can reach 1 〇〇〇mg/L or less (the total nitrogen concentration is 7 8 〇 mg — N/L or less), it is better. High TMAH decomposition reaction rate. W (Example 4: Relationship between pH of TMAH-containing water and maximum gas generation rate) Filled with a concentration of 2000 mg/L of TMAH-containing water (pH 7, containing microorganisms) in a glass vial with an internal volume of 10 mL Nutritional agent) 4 7 · 5 m L, anaerobic sludge (sludge concentration 2 0 0 0 mg / L) 2 · 5 m L, after the glass vial is filled with nitrogen, add hydrochloric acid or sodium hydroxide Adjust the pH to 5, 6, 6, 5, 7, 8, 9. Then 36 201029938 in the glass bottle again

^, one or two people suffocating, sealed with an aluminum cover, measuring the gas per a / / / 匕 以 以 3 3 3 3 3 3 3 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Table 4 shows the data of enthalpy and maximum gas generation rate (within 40 hours after the start of the test). Gas production Table 4 Example 4 - 1 Example 4 - 2 Example 4 - 3 Example 4 - 4 Example 4 - 5 Example 4 - 6

❹ ❹ will break down Jj and produce f, 'fruit'. We have broken it. When it is 5, it is U, and it is τ: body. Moreover, from the anaerobic biological treatment of the two-two AB: maximum gas generation rate in Table 4, the fastest reaction rate of TMAH decomposition is between 7 and 8. (Bei=Example 5 'Relationship between water temperature and maximum gas generation rate) Fixed bed type filled with 80% filler (2 2m m square polyurethane ion carrier) in the inner and inner 1 · 6 L beaker In the continuous treatment device, the >Slaughter sludge (sludge concentration 2 5 1 7 8 mg/L) of the sewage treatment plant was added as a load of 5 kg - TMAH/m3 /d and a flow concentration of 2 kg was added as a half of the beaker. 0 〇mg/L of TMAH-containing water (pH 7, containing microbial nutrient). The water temperature at the time of circulating the water in Example 5 was changed at 35, 28, 23, 20, 17 eC. Table 5 shows the water TM 37 201029938 temperature and TMAH concentration in TMAH-containing water. Table 5 Water temperature TMAH concentration Decomposition rate [. . ] [mg/L] [%] Example 5 - 1 35 19 99 Example 5 - 2 28 36 98 Example 5 - 3 23 94 95 Example 5 - 4 20 144 93 Example 5 - 5 17 341 84 Implementation The results of Example 5 show that 'when the water temperature is above 2 〇C, the decomposition rate is more than g 〇%, and the treatment is confirmed to be good. In contrast, when the water temperature is 1 7 °C, TMAH will also decompose', but the decomposition rate drops below 9 〇%, and the treated water quality also deteriorates. Therefore, it can be confirmed that the water temperature must be above 20 °C, preferably between 2 8 and 3 5 °C. (Example 6)

A continuous treatment test containing TMAH discharged water was carried out using a UASB (upflow anaerobic sludge system) type reactor having a volume of 2.08 ((p6 〇 mm >< l 〇〇〇 mmH) under the following conditions.

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

MLSS (sludge concentration): 38626mg/L Flow temperature: 3 5 °C The fifth graph shows the relationship between the number of flowing days and the TOC concentration in the TMAH-containing water, the TMAH concentration, the TOC concentration in the treated water, and the TMAH concentration. Figure 6 shows the relationship between the number of flow turns and the TMAH load and the speed of the TMAH removal 38 201029938. It can be seen from the fifth and sixth diagrams that good processing water quality can be obtained in the 5k m condition during the high-load operation of the cold-view AH/mVd (TMAH is lower than the inspection limit, T〇c is 5 〇 〇 忌 八 eight or less). Therefore, it is determined that high-speed processing can be done, which can reduce the space and cost of the county. (Example 7) 调整 Adjust the actual discharge water containing TMAH discharged from the semiconductor factory to 2 〇〇OmgTMAH/L, and add anaerobic sludge to the beaker of internal volume 〇·8 L (sludge concentration 2 5 1 4 8mg/L) As a seed sludge, after adding half a beaker, the above-mentioned actual discharged water was passed through a load of 5 k gTMAH/ /d. The temperature at the time of water supply was adjusted to 35 °C. The pH was adjusted to 7 to 8, and a nutrient (ORGAMIN NP-51, manufactured by ORGANO Co., Ltd.) and trace elements (ORGAMIN10 1.2 manufactured by ORGANO Co., Ltd.) were added. mL/L), Ni, ® C 〇 (each 〇. img/L). In addition, waste molasses (raw material for sweet vegetables and sweet potatoes) is 20〇111 bogey/two (57111 〇/1^, 〇〇 The ratio of the ratio of TMAH to 5.3 % is continuously added to the above-mentioned actual discharge water at the start of the treatment. The waste molasses used in Example 7 has a sugar content of 30 to 40% or more, and a pure sugar ratio of 3 5 More than %% of the sugar is more than 15%, and the pure sugar is more than 55%. The other ingredients are shown in Table 6. 201029938 Table 6 a) Crude % Moisture 26.8 Crude protein crude fat coarse weave 0-6 0.1 0.1 ore Substance (%) Calcium Total Sodium Potassium Sodium Sulfur 1.19 0.11 0.47 3.17 0.37 - - Mineral (mg/kg) Iron, Copper, Cobalt, Zinc, Shovel, Fluoride, Selenium 300 79.4 - 43 56 - 0.1 - - Amino Acid (%) ❹ Arginine glycine histidine isoleucine leucine from amino acid (ly Sine)

Metisinine cystine (phenylalanine) 0.01 0.04 0.01 0.03 0.04 0.01 0.01 0.03 0.03 Tyrosine (Tyrosine)

Tributofen

Barin

Serin 0.01 hydroxybutyrate (Threonine) 0.03 0.03

Total chlorophyll (mg/kg) Vitamin A (IU/kg) Vitamin D (IU/kg) Vitamin E (mg/kg) Vitamin K (mg/kg) - 110 Vitamin B6 Piotine Folic acid choline vitamin B12 (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) 17.5 1.14 0.03 1.2 0.03 Vitamin Bi ^/kg) Vitamin B2 _ (mg/kg) Pantothenic acid (mg/kg) Nicotinic acid (mg /kg) 4.4 51.1 46 ❹ (Comparative Example 1) In Comparative Example 1, except that no molasses was added, the remainder was replaced by Example 40 at 2010 7938 (Comparative Example 2) instead of molasses Comparative Example 2 with ferrous chloride (FeC12) ( Conditional addition of inorganic aggregating agents,

The treatment was carried out in the same manner as in Example 7 at 19 mg/L (iron 6 · 5 mg Fe/L. (Comparative Example 3) Comparative Example with Cation Polymer (polymer condensed state)

The OX-606, manufactured by Ogami Co., Ltd., was replaced by molasses, and _ ^ υ * 5 m g e 10 /L was added, and the rest was treated as in Example 7. Figure 7 shows the sludge of the sludge before the water is passed through the water. Fig. 8 is a 50-fold enlarged photograph of the sludge before the water passing through in Example 7 and Comparative Examples 1 to 3, and the water flowing through the sewage. Figure 9 shows the sludge concentration in the beaker before the water passing through and 5 5 通. Figure 1 shows the interface of the sludge in the beaker before the water passes through the water. 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 Example 〜3, and it was confirmed that the effect of promoting the formation of particles was confirmed. In addition, it can be seen from Fig. 9 and Fig. 10 that the sludge concentration and the sludge interface height are higher in Example 7 than in Comparative Examples 1 to 3, and the amount of sludge in the beaker is increased. . In particular, the effect of Cation Polymer is not clear in comparison with the conventional methanol-to-anaerobic treatment, but the effect of the present Example 7 is clear, and it has been confirmed that it is effective for promoting and maintaining particle formation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram of a 201029938 pattern constituting the 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 t〇c in treated water, and the concentration of TMAH. Figure 6 is a plot of the number of passes through the water and the TMAH load and the removal of the TMAH speed. The stomach 7 is the diameter of the sludge particles after the passage of water and the water-passing day. Fig. 8 is a 50-fold enlarged photograph of the sludge before the water passing, the number of the water passing days, and the sludge of Example 7 and Comparative Examples 1 to 3 after 3 days. Figure 9 is a graph showing the concentration of sludge in a cylinder after 550 days before water passing and water passing days. Figure 10 is a 1% graph of the sludge interface in the cylinder after 5 days from the passing of water and the number of water passing days. [Main component symbol description] 1 to 4 anaesthetic biological treatment device 1 0 original water tank 201029938 12, 12a~12b, 4 4 adjustment tank 14 anaerobic biological treatment tank 1 6 separation tank 1 8 nitrogen treatment tank 2 0 treatment tank 22a to 22e piping 24a to 24b pumping © 2 6 dilution water inflow line 2 8 pH adjusting agent inflow line 3 0 nutrient inflow line 3 2 vapor inflow line 3 4 circulation line. 3 6, 3 8 stirring device 4 0 sludge return line 4 2 raw water first line 10 4 6 raw water second line 4 8 reaction tank 5 0 treatment water discharge line 5 2 gas discharge line 5 4 treatment water circulation line 5 6 molasses storage tank 5 8 Molasses supply line 60 0 nutrient storage tank 6 2 nutrient supply line 43 201029938 6 4 pH adjuster storage tank 6 6 pH adjuster supply line 6 8 stirring device 7 〇a * * 701) partition plate 7 2 solid-liquid separation unit 7 4 communication path 7 6 treatment water extraction part 7 8 separation tank 8 0 return line 8 2 carrier 44

Claims (1)

201029938 VII 1 2 3 4 ❹5 6 Patent application scope: An anaerobic biological treatment method for treating water discharged from a polyalkylammonium salt of a polycarboxylate by biological treatment, the anaerobic biological treatment method is characterized by performing the aforementioned organism During the treatment, the poly-tannic acid-containing salt in the polyalkylamine-containing ammonium salt-containing water is less than 2,000 mg/L. An anaerobic biological treatment method for treating a discharge water containing a polyalkylammonium salt of a polycarboxylic acid by a biological treatment method, wherein the anaerobic biological treatment method is characterized in that the polycarboxylic acid alkylammonium salt is contained in the foregoing biological treatment The total concentration of organic nitrogen and ammonia nitrogen in the discharged water is below 3900mg - N / L. The anaerobic biological treatment method according to claim 1 or 2, wherein a part of the treated water is recirculated into the discharge water containing the polyalkylammonium salt of the polycarboxylic acid after the biological treatment. The anaerobic biological treatment method according to the third aspect of the invention, characterized in that, in the biological treatment, the concentration of the polycarboxylic acid alkylammonium salt in the polycarboxylic acid-containing salt-containing salt discharge water is at 〇 〇〇〇mg/L or less. An anaerobic biological treatment method for treating effluent water containing polyalkylammonium salt of polycarboxylate by anaerobic biological treatment, characterized in that the above-mentioned biological treatment of the alkyl ammonium salt containing polycarboxylate is carried out, The pH range is controlled between 6 · 5 and 9 · 〇. An anaerobic biological treatment method for treating effluent water containing polyalkylammonium salt of polycarboxylate by anaerobic biological treatment, characterized in that the above-mentioned biological treatment of polyglycolic acid-containing salt The water temperature is controlled above 2 〇 °C. An anaerobic biological treatment method for treating water containing polyalkylamine ammonium salt of 45 7 201029938 by anaerobic biological treatment, which is characterized by having the following two or more conditions. (1) In the biological treatment, the concentration of the polycarboxylic acid alkylammonium salt in the above-mentioned polyalkylamine ammonium salt-containing discharge water must be less than 2 〇0 0 0 mg/L, or the above-mentioned polycarboxylate-containing alkane in the above biological treatment. The concentration of the polycarboxyalkylammonium salt in the quaternary ammonium salt discharge water shall be less than 200 mg / L ' while the part of the treated water after the above biological treatment is reintroduced into the aforementioned polycarboxylate alkyl ammonium salt discharged water Circulation, (2) The total concentration of organic nitrogen and ammonia nitrogen in the above-mentioned polyalkylamine ammonium salt-containing effluent water must be 39 〇〇mg-N/]L © below or during the above biological treatment In the foregoing biological treatment, the total concentration of organic nitrogen and ammonia nitrogen in the water discharged from the polyalkylammonium salt of the polycarboxylic acid shall be below 39 〇〇mg - N / L, and the treated water after the biological treatment is re-processed again. Introducing the aforementioned polycarboxylate alkylammonium salt discharge water Medium circulation, (3) The above-mentioned biological treatment of the polyalkylamine ammonium salt-containing water, the pH must be controlled between 6 · 5 and 9 · 0, (4) the above-mentioned polycarboxylic acid alkyl ammonium salt The effluent water is subjected to the aforementioned biological treatment, and the water temperature must be 2 (Tc q or more. 8) The anaerobic biological treatment method according to any one of claims 1 to 7 which is characterized by the aforementioned polycarboxylic acid The alkylammonium salt is tetraammonium ruthenium oxide (TMAH). 9. A biological treatment method for treating water containing polyalkylammonium salt of polycarboxylate by anaerobic biological treatment, and the anaerobic biological treatment device has the following Characteristics: The method for adjusting the concentration of polyalkyl phthalate ammonium salt allows the effluent water to flow the concentration of the polycarboxyalkylammonium salt in the above-mentioned polyalkylamine-containing ammonium salt discharge water 46 201029938 when flowing into the aforementioned biological treatment method Adjusted to below 20 Ο 〇〇 mg / L. 10 - A biological treatment method for treating water containing alkyl ammonium chloride salt of polycarboxylate by anaerobic biological treatment, and the anaerobic biological treatment device has the following characteristics: Have a nitrogen concentration adjustment method 'let the discharge water flow When the biological treatment method is used, the total concentration of organic nitrogen and ammonia nitrogen in the polyalkylamine-containing ammonium salt-containing water can be adjusted to 3900 mg-N/L^ or less. Ref. 11· Patent Application No. 9 or 10 The anaerobic biological treatment device of the present invention is characterized in that it has a circulation method capable of re-introducing the biologically treated part of the treated water into the water containing the polycarboxyalkylammonium salt as follows. The anaerobic biological treatment device according to the above aspect, characterized in that the polycarboxylic acid alkylammonium salt concentration adjustment method is provided, and the discharge water can flow the polycarboxylate containing polycarboxylate when flowing into the biological treatment method. The concentration of the polycarboxyalkylammonium salt in the quaternary ammonium salt discharge water is adjusted to 1.00 mg/L· or less. 13. A biological treatment method for treating water containing polyalkylammonium salt of polycarboxylate by anaerobic biological treatment, and the anaerobic biological treatment device has the following features: having a set of pH adjustment methods for allowing the aforementioned polycarboxylate The acid-saturated ammonium salt discharge water can adjust the pH to a range of 6.5 to 9 〇 when performing the above-described biological treatment. 14. A biological treatment method for treating effluent containing polyalkylammonium salt of polycarboxylate by anaerobic biological treatment, characterized in that the anaerobic biological treatment device has a temperature adjustment method of 47 201029938, allowing the aforementioned polycarboxylic acid to be contained When the above-mentioned biological treatment is carried out, the temperature of the water in the biological treatment method can be adjusted to 2 (TC or more. An organism which treats the water containing polyphosphonic acid-based salt discharge water by an anorectic biological treatment. The treatment method is characterized in that the anaerobic biological treatment device has the following two or more methods (1) to (4): (1) having a set of polycarboxylic acid alkyl ammonium salt concentration adjustment method, and the above-mentioned The poly-acid-acid-salt ammonium salt discharge water can adjust the concentration of the polycarboxylic acid alkylammonium salt in the polyalkylamine-containing ammonium salt-containing water to 200 mg/w when flowing into the aforementioned biological treatment method. L or less, or have a set of the above-mentioned polycarboxyalkylammonium salt concentration adjustment method and a set of recycling methods, so that the treated portion of the biologically treated portion of the treated water is recirculated to the aforementioned poly-acid-acid alkyl ammonium salt Medium; (2). own a set of nitrogen The degree adjustment method is such that the above-mentioned polycarboxylate-containing salt discharge water can be adjusted to the total concentration of the organic gas and the ammonia nitrogen in the water discharged from the polyalkylammonium salt-containing salt to 390Omg when flowing into the above biological treatment method. - N/L or less, or © is a set of the above-mentioned nitrogen concentration adjustment method and a set of circulation method, so that part of the treated water treated by the above biological treatment is recycled to the polypyrrolate salt, (3 ) has a set of pH adjustment method, so that the 1*1 containing the resole acid-based ammonium salt discharge water can adjust the pH to 6. 5~9 in the above biological treatment; (4) own one The temperature adjustment method allows the water containing the polyalkylammonium salt of the polycarboxylate to be adjusted to a temperature of 20 ° C or more in the biological treatment of the above-mentioned biological treatment. 48 201029938 16· The anaerobic biological treatment device described in the above-mentioned ninth aspect of the invention is characterized in that the poly-acid-saturated saddle salt is tetraammonium hydroxide (TMAH). The treatment device is provided with an anaerobic biological treatment The biological treatment method of the bubonic acid base (4), the anaerobic biological device f is characterized in that the above-mentioned polymethane-containing salt discharge water flows into the other biological treatment method. The concentration of poly-acidic acid in the discharge water is below 2 〇〇〇〇mg/L. 1 8 · A biological treatment device has the biological treatment of polyphenolic acid-containing (4) water reduction treatment by anaerobic biological means The method of the simple oxygen biological device is characterized in that the organic nitrogen and ammonia nitrogen in the water discharged from the polycarboxyalkylammonium salt are discharged when the polyalkylamine-containing ammonium salt-containing water is discharged into the delineated biological treatment method. The total concentration is below 3 g〇〇mg_N/Ij. 19. A biological treatment device comprising an anaerobic biological treatment of a polychlorinated ammonium sulphate-depleting method, wherein the county biological treatment device is characterized by the inflow of water from the aforementioned polyalkylamine-containing ammonium salt. When the biological treatment method is described in detail, the water temperature in the biological treatment method is 20 ° C or higher. An oxygen biological treatment method for treating water containing alkyl ammonium chloride salt of polycarboxylate by anaerobic biological treatment, the anaerobic biological treatment method characterized by supplying molasses to said discharged water. 2 1 · - = Anaerobic biological treatment of anaerobic biological treatment of discharged water containing organic matter of six carbons or less. The anaerobic biological treatment method is characterized by the supply of molasses to the aforementioned discharge water for 49 201029938. 2 2 • The anaerobic biological treatment method according to the scope of claim 2, or 2, wherein the molasses is supplied at the start of the biological treatment and after the start. The anaerobic biological treatment method according to the above-mentioned Patent No. 2Q or 2, wherein the anaerobic sludge is introduced into the reaction tank for performing the biological treatment to expand the biological treatment. 24 • The anaerobic biological treatment method described in the second or second application of the patent application is characterized in that the discharge water is discharged from a semiconductor factory ◎ discharged water. 2 5 . The anaerobic biological treatment method according to claim 20 or 21, wherein the polyaluminum sulphate ammonium salt and the organic substance having 6 or less carbon atoms are ruthenium oxynitride. Ammonium (TMAH). The anaerobic biological treatment method according to claim 23, wherein the carrier is filled with a carrier in the reaction vessel for performing the biological treatment when the biological treatment is carried out. An anaerobic biological treatment device, wherein the device has a reaction tank for treating water containing polyalkylammonium salt of polycarboxylate in an anaerobic biological treatment, and a method for supplying molasses for supplying the molasses to the discharged water. An anaerobic biological treatment apparatus, which comprises a reaction tank for treating an organic substance having 6 or less carbons by anaerobic biological treatment, and a method for supplying molasses to the aforementioned discharged water by supplying molasses. An anaerobic biological treatment device as described in claim 2 or claim 28, wherein the molasses supply method is the supply of the aforementioned molasses at the start of the aforementioned biological site 50 201029938 and after the start. An anaerobic biological treatment device according to the invention of claim 2, wherein the anaerobic sludge is introduced into the reaction tank. An anaerobic biological treatment device according to claim 27 or 28, wherein the discharge water is discharged water discharged from a semiconductor process. 3 2 ❿ 3 3 • An anaerobic biological treatment device as described in Shen Qing Patent Fan® No. 2-7 or 28, JL 4 ^, characterized by the aforementioned polycarboxyalkylammonium salt and 6 of the foregoing Slave: The organic matter is tetramethylammonium hydroxide (ΤΜΑΗ). The anaerobic biological treatment device according to the item of claim 30, wherein the biological reaction is carried out in the reaction tank. 51