JP4303625B2 - How to remove nitrogen in wastewater - Google Patents
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- JP4303625B2 JP4303625B2 JP2004095400A JP2004095400A JP4303625B2 JP 4303625 B2 JP4303625 B2 JP 4303625B2 JP 2004095400 A JP2004095400 A JP 2004095400A JP 2004095400 A JP2004095400 A JP 2004095400A JP 4303625 B2 JP4303625 B2 JP 4303625B2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 36
- 239000002351 wastewater Substances 0.000 title claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 96
- 239000011593 sulfur Substances 0.000 claims description 92
- 229910052717 sulfur Inorganic materials 0.000 claims description 92
- 238000000034 method Methods 0.000 claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 5
- 230000000813 microbial effect Effects 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 5
- 230000001651 autotrophic effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- 229940006280 thiosulfate ion Drugs 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001509286 Thiobacillus denitrificans Species 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Description
本発明は排水中の生物学的窒素除去方法における還元剤として有用な新規形状の硫黄、その製造法、及びそれを用いた排水中の生物学的窒素除去方法に関する。 The present invention relates to a novel form of sulfur useful as a reducing agent in a method for removing biological nitrogen in wastewater, a method for producing the same, and a method for removing biological nitrogen in wastewater using the sulfur.
排水中の有機物を除去する目的で実施される活性汚泥処理では、窒素、リンなどの栄養塩類の十分な除去は、排水組成、濃度によっては困難で、湖沼、内海などでは富栄養化状態を引き起こす可能性があるといわれている。このため、生物学的な窒素除去方法が研究されており、実用化されている。 In activated sludge treatment carried out for the purpose of removing organic matter in the wastewater, it is difficult to remove nutrients such as nitrogen and phosphorus depending on the composition and concentration of the wastewater and cause eutrophication in lakes and inland seas. It is said that there is a possibility. For this reason, biological nitrogen removal methods have been studied and put into practical use.
この実用化されている生物学的な窒素除去方法では排水中に還元剤となりうる物質が不足している場合、適当な水素供与体の添加が必要である。還元剤としては種々の水素供与体が提案されているが、メタノールが資化性、取り扱い易さ、経済性から優れているとされている。また、メタノールなどの適当な還元剤を用いて脱窒素を行う場合、十分に脱窒素するためには還元剤を過剰に添加する必要がある。このため過剰のメタノールなどの還元剤は、脱窒素反応後は、ＢＯＤ成分として排水中に残存しており、後工程として活性汚泥による好気処理が必要である。 In this practical biological nitrogen removal method, when there is a shortage of substances that can serve as a reducing agent in the waste water, it is necessary to add an appropriate hydrogen donor. Various hydrogen donors have been proposed as reducing agents, but methanol is said to be superior in terms of utilization, ease of handling, and economy. In addition, when denitrification is performed using an appropriate reducing agent such as methanol, it is necessary to add an excessive reducing agent in order to sufficiently denitrify. For this reason, excess reducing agents such as methanol remain in the wastewater as a BOD component after the denitrogenation reaction, and aerobic treatment with activated sludge is necessary as a subsequent step.
また、排水からの脱窒素の方法として、還元型硫黄を用いた硫黄脱窒方法が提案されている。例えば、還元型硫黄として元素状硫黄（特許文献１〜３）、チオ硫酸イオン（特許文献４）及び硫化水素（特許文献５）を利用した方法が提案されている。
メタノールを還元剤として使用する生物学的脱窒素法は、使用するメタノールの薬剤費、設備費が高いという点から一般に普及するには更なるコスト低減が望まれている。さらに用いたメタノールに対して外界への排出がないように管理が必要である。
また、還元型硫黄を用いた硫黄脱窒法においては、チオ硫酸イオンを用いた場合、チオ硫酸中の硫黄の電荷が＋２であり、窒素還元に用いる硫黄の添加量が多くなり、また、チオ硫酸自体の価格が高いことから脱窒素処理における薬剤費の割合が大きくなる。また硫化水素は毒性、臭気の問題から、実用上使用するには、それらの対量を厳密にする必要があり、実際の使用には高度な制御方法が必要になる。
また、元素状硫黄は、安価で、取り扱い性がよいなどの利点がある。しかしながら、脱窒素速度が遅い、さらに、脱窒反応で生じた窒素ガスが硫黄表面を覆うため、長時間安定した脱窒素速度が得られないという問題があり、これらの解決が求められている。
The biological denitrification method using methanol as a reducing agent is required to further reduce costs in order to spread in general because of the high drug cost and equipment cost of the methanol used. Furthermore, management is necessary so that the methanol used does not discharge to the outside world.
In addition, in the sulfur denitrification method using reduced sulfur, when thiosulfate ion is used, the charge of sulfur in thiosulfuric acid is +2, the amount of sulfur used for nitrogen reduction increases, and thiosulfuric acid is added. Since the price of itself is high, the ratio of the chemical cost in the denitrification treatment becomes large. In addition, due to toxicity and odor problems, hydrogen sulfide needs to be strict in terms of the amount to be used in practice, and an advanced control method is required for actual use.
In addition, elemental sulfur has advantages such as being inexpensive and easy to handle. However, there is a problem that the denitrification rate is slow, and further, since nitrogen gas generated by the denitrification reaction covers the sulfur surface, there is a problem that a stable denitrification rate cannot be obtained for a long time, and these solutions are required.
従って、本発明の目的は、安価で、脱窒素速度が大きく、かつ長時間安定した脱窒素速度が得られる還元剤及びそれを用いた排水中の生物学的脱窒素法を提供することにある。 Accordingly, it is an object of the present invention to provide a reducing agent that is inexpensive, has a high denitrification rate, and can obtain a stable denitrification rate for a long time, and a biological denitrification method in waste water using the same. .
そこで本発明者は、脱窒素速度、経済性及び安全性を満足する還元剤を探索した結果、
液体硫黄を温度分布のある油中に滴下して調製した球状硫黄を用いれば、脱窒槽への充填が均一となり、排水の流れが偏流せず効率的な処理が可能であり、固定床では硫黄脱窒中に生成する窒素ガスが硫黄上で気泡となり、硫黄表面を覆うという問題も解消され安定した処理が可能となり、その結果経済的、かつ安定的に排水から窒素除去が可能になることを見出し、本発明を完成するに至った。
Therefore, the present inventors have searched for a reducing agent that satisfies the denitrification rate, economy, and safety,
Using spherical sulfur prepared by dropping liquid sulfur into oil with temperature distribution, the denitrification tank can be uniformly filled, and the wastewater flow does not drift and efficient treatment is possible. Nitrogen gas generated during denitrification becomes bubbles on sulfur and the problem of covering the surface of sulfur is solved, and stable treatment is possible. As a result, nitrogen can be removed from wastewater economically and stably. The headline and the present invention were completed.
すなわち、本発明は、粒子径が０．１〜２０mmである球状硫黄を提供するものである。
また、本発明は、硫黄の融点以上から融点以下までの温度分布のある油の高温部に液体硫黄を滴下し、高温部から低温部に液体硫黄を移動させて硫黄を固化させることを特徴とする球状硫黄の製造法を提供するものである。
さらに本発明は、硝酸態窒素を含む排水を嫌気条件下に生物学的に処理する排水中の窒素除去方法において、還元剤として粒子径が０．１〜２０mmである球状硫黄を使用することを特徴とする排水中の窒素除去方法を提供するものである。
That is, the present invention provides spherical sulfur having a particle size of 0.1 to 20 mm.
Further, the present invention is characterized in that liquid sulfur is dropped into a high temperature part of oil having a temperature distribution from the melting point of sulfur to the melting point of the sulfur, and liquid sulfur is moved from the high temperature part to the low temperature part to solidify the sulfur. A method for producing spherical sulfur is provided.
Furthermore, the present invention uses a spherical sulfur having a particle size of 0.1 to 20 mm as a reducing agent in a method for removing nitrogen in wastewater that biologically treats wastewater containing nitrate nitrogen under anaerobic conditions. A feature of the present invention is to provide a method for removing nitrogen from wastewater.
本発明の球状硫黄を還元剤として用いれば、従来の破砕状硫黄を用いた場合に比べて、排水中の窒素除去を安定的かつ効率的に行うことができる。すなわち、１）固定床では球状硫黄を使用することにより硫黄脱窒槽への充填が均一となり、排水の流れが偏流せず効率的な処理が可能となり、２）固定床では硫黄脱窒中に生成する窒素ガスが硫黄上で気泡となり、硫黄表面を覆う問題があるが、球状硫黄を用いることで気泡が硫黄上から抜けやすくなり安定した処理が可能になり、３）球状硫黄の直径を任意に変化可能であり、流れの速さに適した径を調整できる。 If the spherical sulfur of the present invention is used as a reducing agent, nitrogen removal from wastewater can be stably and efficiently performed as compared with the case of using conventional crushed sulfur. That is, 1) By using spherical sulfur in the fixed bed, the sulfur denitrification tank is uniformly filled, and the wastewater flow is not unevenly distributed and can be efficiently treated. 2) In the fixed bed, it is generated during sulfur denitrification. There is a problem that the nitrogen gas to be bubbled on the sulfur and cover the sulfur surface, but using spherical sulfur makes it easier for bubbles to escape from the sulfur, enabling stable treatment 3) Arbitrary spherical sulfur diameter The diameter can be changed, and the diameter suitable for the flow speed can be adjusted.
本発明の球状硫黄は粒子径が０．１〜２０mmであるが、さらに１〜１０mm、特に１〜５mmが好ましい。また本発明で球状とは、真球状及び略球状も含むものである。 The spherical sulfur of the present invention has a particle size of 0.1 to 20 mm, more preferably 1 to 10 mm, and particularly preferably 1 to 5 mm. In the present invention, the term “spherical” includes true spherical and substantially spherical shapes.
本発明の球状硫黄は、硫黄の融点以上から融点以下までの温度分布のある油の高温部に液体硫黄を滴下し、高温部から低温部に液体硫黄を移動させて固化させることにより製造される。この球状硫黄製造装置としては、図１に示すように、上部にヒーターが設けられた筒状の槽に油が充填された装置を用いることができる。この装置の上部のホッパーに粉末状又は破砕状硫黄を充填すれば、ヒーターで加熱された硫黄が液体となり油中に滴下される。油の上部を硫黄の融点以上である１１３℃以上、特に１２０℃以上に加熱しておけば、液体硫黄は油中に液状で滴下される。液体硫黄は下部に沈降するに従って固化し、球状硫黄が生成する。なお、下部は１１２℃以下、好ましくは１００℃以下になっていれば良いが、８０℃以下になっているのが特に好ましい。球状硫黄の粒子径は、滴下装置の口径、周辺温度により簡単に調整可能である。なお、高温部と低温部は、温度差を設けたヒーターなどで段階的に制御してもよく、低温部は冷却水などで冷却して適温に制御しても良い。また、ホッパーを加温しても良い。また、油としては、シリコーン油、フッ素油、ポリグリコール、フェニルエーテル等の合成油；鉱油；植物油；動物油等の融点３０℃以下、沸点１３０℃以上の油が用いられる。 The spherical sulfur of the present invention is produced by dripping liquid sulfur into a high temperature part of an oil having a temperature distribution from the melting point of the sulfur to the melting point of the sulfur and moving the liquid sulfur from the high temperature part to the low temperature part to solidify. . As this spherical sulfur production apparatus, as shown in FIG. 1, an apparatus in which oil is filled in a cylindrical tank provided with a heater at the top can be used. If powdered or crushed sulfur is filled in the upper hopper of this apparatus, the sulfur heated by the heater becomes liquid and is dropped into the oil. If the upper part of oil is heated to 113 ° C. or higher, particularly 120 ° C. or higher, which is higher than the melting point of sulfur, liquid sulfur is dropped into the oil in liquid form. Liquid sulfur solidifies as it settles at the bottom, producing spherical sulfur. In addition, the lower part should just be 112 degrees C or less, Preferably it is 100 degrees C or less, However, It is especially preferable that it is 80 degrees C or less. The particle diameter of the spherical sulfur can be easily adjusted by the diameter of the dropping device and the ambient temperature. The high temperature part and the low temperature part may be controlled stepwise with a heater or the like provided with a temperature difference, and the low temperature part may be cooled with cooling water or the like to be controlled at an appropriate temperature. Further, the hopper may be heated. As the oil, synthetic oils such as silicone oil, fluorine oil, polyglycol, and phenyl ether; mineral oils; vegetable oils; animal oils and the like having an melting point of 30 ° C. or lower and a boiling point of 130 ° C. or higher are used.
次に本発明の球状硫黄を用いた排水中の窒素除去方法について説明する。本発明方法は、各種の窒素化合物含有排水の脱窒素処理に適用できる。排水中に硝酸態窒素を含む場合には本発明の方法を直接適用できる。一方、有機態窒素、アンモニア態窒素を含有する排水の場合には、あらかじめ公知の生物学的処理、化学的処理により硝酸態窒素に変換することにより、本発明方法が適用できる。ここで、硝酸態窒素には、硝酸、硝酸イオン、亜硝酸、亜硝酸イオンが含まれる。 Next, the method for removing nitrogen in waste water using the spherical sulfur of the present invention will be described. The method of the present invention can be applied to denitrification treatment of various nitrogen compound-containing wastewater. When nitrate nitrogen is contained in the waste water, the method of the present invention can be directly applied. On the other hand, in the case of wastewater containing organic nitrogen or ammonia nitrogen, the method of the present invention can be applied by converting it into nitrate nitrogen by a known biological treatment or chemical treatment in advance. Here, nitrate nitrogen includes nitric acid, nitrate ion, nitrous acid, and nitrite ion.
本発明方法は、生物学的処理による排水中の窒素除去方法であり、独立栄養細菌である硫黄脱窒菌による脱窒素作用を利用する方法である。硫黄脱窒細菌（Thiobacillus denitrificans）は、還元態硫黄を酸化することでエネルギーを獲得し、硝酸塩、亜硝酸塩等の硝酸態窒素から、無酸素条件下で脱窒素能を示す細菌である。
従って、本反応は嫌気条件で実施する必要があるが、厳密な操作は必要ではなく空気又は酸素の曝気等により溶存酸素濃度を高める操作をしない条件では、硫黄脱窒槽に流入してきた排水は速やかに溶存酸素が消費され硫黄脱窒反応を行うに十分な嫌気条件となる。
The method of the present invention is a method for removing nitrogen from wastewater by biological treatment, and is a method utilizing the denitrification action by sulfur denitrifying bacteria, which are autotrophic bacteria. Sulfur denitrifying bacteria (Thiobacillus denitrificans) is a bacterium that acquires energy by oxidizing reduced sulfur and exhibits denitrification ability under nitrate-free conditions from nitrate nitrogen such as nitrate and nitrite.
Therefore, this reaction must be carried out under anaerobic conditions, but strict operation is not necessary, and wastewater that has flowed into the sulfur denitrification tank is quickly removed under conditions that do not increase the dissolved oxygen concentration by aeration of air or oxygen. Dissolved oxygen is consumed and the anaerobic conditions are sufficient for the sulfur denitrification reaction.
当該独立栄養細菌は、既存の活性汚泥装置から採取し、嫌気性条件で還元型硫黄を用いて馴養を行うことにより使用することができる。また、実際に嫌気性条件で硫黄脱窒している槽から出る独立栄養細菌の汚泥を用いても良い。 The autotrophic bacterium can be used by collecting from an existing activated sludge apparatus and acclimatizing with reduced sulfur under anaerobic conditions. Moreover, you may use the sludge of an autotrophic bacterium which comes out of the tank which actually carries out sulfur denitrification on anaerobic conditions.
本発明においては、還元剤として球状硫黄を使用することを特徴とする。本発明方法は固定床の場合に特に有利である。すなわち、１）固定床では球状硫黄を使用することにより硫黄脱窒槽への充填が均一となり、排水の流れが偏流せず効率的な処理が可能となり、２）固定床では硫黄脱窒中に生成する窒素ガスが硫黄上で気泡となり、硫黄表面を覆う問題があるが、球状硫黄を用いることで気泡が硫黄上から抜けやすくなり安定した処理が可能になる。 In the present invention, spherical sulfur is used as a reducing agent. The process according to the invention is particularly advantageous in the case of fixed beds. That is, 1) By using spherical sulfur in the fixed bed, the sulfur denitrification tank is uniformly filled, and the wastewater flow is not unevenly distributed and can be efficiently treated. 2) In the fixed bed, it is generated during sulfur denitrification. There is a problem that the nitrogen gas to be formed becomes bubbles on the sulfur and covers the sulfur surface, but the use of spherical sulfur makes it easier for bubbles to escape from the sulfur and a stable treatment is possible.
球状硫黄は、硫黄脱窒反応槽又は硫黄脱窒反応管に充填するが、流通式装置で循環処理しない場合は、球状硫黄を空間速度（ＳＶ）として０．００２〜１ｈ-1、さらに、０．００５〜０．５ｈ-1、特に０．０１〜０．１ｈ-1になるような充填量にすることが好ましい。空間速度が低すぎると、処理量に対する処理槽が大きくなりすぎ、空間速度が高すぎると、十分な脱窒の効果が得られない。また、複数回循環処理する場合は、空間速度を巡回回数で割った値が上記範囲になるような条件とする。 Spherical sulfur is charged into a sulfur denitrification reaction tank or sulfur denitrification reaction tube, but when not circulated by a flow-type apparatus, the spherical sulfur is converted into a space velocity (SV) of 0.002 to 1 h −1 , and 0 .005~0.5h -1, particularly it is preferable that the filling amount such that 0.01~0.1h -1. If the space velocity is too low, the treatment tank for the amount of treatment becomes too large, and if the space velocity is too high, a sufficient denitrification effect cannot be obtained. Further, when the circulation process is performed a plurality of times, the condition is set such that the value obtained by dividing the space velocity by the number of circulations falls within the above range.
本発明における脱窒槽のpHは５．５〜８．５、好ましくは５．８〜８．０、特に好ましくは６．０〜８．０の範囲のとき良好な脱窒活性が得られる。また、脱窒槽の温度は２０℃〜４５℃、好ましくは２５℃〜４５℃、特に好ましくは３０℃〜４５℃で良好な脱窒活性が得られる。 When the pH of the denitrification tank in the present invention is in the range of 5.5 to 8.5, preferably 5.8 to 8.0, particularly preferably 6.0 to 8.0, good denitrification activity can be obtained. The denitrification tank temperature is 20 ° C. to 45 ° C., preferably 25 ° C. to 45 ° C., particularly preferably 30 ° C. to 45 ° C., and good denitrification activity is obtained.
また、本発明においては、球状硫黄に加えて、さらに他の還元型硫黄化合物を併用しても良い。他の還元型硫黄化合物としては、硫化水素、チオ硫酸ナトリウム、硫化水素ナトリウム等が挙げられる。 In the present invention, other reduced sulfur compounds may be used in combination with spherical sulfur. Examples of other reduced sulfur compounds include hydrogen sulfide, sodium thiosulfate, and sodium hydrogen sulfide.
球状硫黄に加えて他の還元型硫黄化合物を用いる場合の脱窒槽のpH及び温度は前記と同様である。 The pH and temperature of the denitrification tank when other reduced sulfur compounds are used in addition to the spherical sulfur are the same as described above.
本発明方法に用いる脱窒槽としては、連続式、回分式、交互切替式のいずれでも良い。また、汚泥の状態として、球状硫黄への固着生物型が良い。なお、硝化槽と連結しても良い。 The denitrification tank used in the method of the present invention may be any of a continuous type, a batch type, and an alternating switching type. Moreover, as a state of sludge, a fixed biotype to spherical sulfur is good. In addition, you may connect with a nitrification tank.
以下、実施例及び比較例により本発明をより詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in more detail, this invention is not limited to these Examples.
実施例１
図１の装置を用いて粉末硫黄から球状硫黄を製造した。図１においては、油としてシリコーン油を用いる。
Example 1
Spherical sulfur was produced from powdered sulfur using the apparatus of FIG. In FIG. 1, silicone oil is used as the oil.
１）液状硫黄滴下口径を２mmφとし、シリコーン油最上部温度を１２０℃に調整し、液状硫黄を滴下した。得られた球状硫黄の平均径は約３．０mmであった。 1) The liquid sulfur dropping diameter was 2 mmφ, the top temperature of the silicone oil was adjusted to 120 ° C., and liquid sulfur was dropped. The average diameter of the obtained spherical sulfur was about 3.0 mm.
２）液状硫黄滴下口径を２mmφとし、シリコーン油最上部温度を１３０℃に調整し、液状硫黄を滴下した。得られた球状硫黄の平均径は約２．２mmであった。 2) The liquid sulfur dropping diameter was set to 2 mmφ, the top temperature of the silicone oil was adjusted to 130 ° C., and liquid sulfur was dropped. The obtained spherical sulfur had an average diameter of about 2.2 mm.
３）液状硫黄滴下口径を３mmφとし、シリコーン油最上部温度を１２０℃に調整し、液状硫黄を滴下した。得られた球状硫黄の平均径は約４．２mmであった。 3) The liquid sulfur dropping diameter was 3 mmφ, the top temperature of the silicone oil was adjusted to 120 ° C., and liquid sulfur was dropped. The average diameter of the obtained spherical sulfur was about 4.2 mm.
実施例２
硝酸態窒素を含む排水として表１に示す組成の人工排水を用いた。
Example 2
Artificial wastewater having the composition shown in Table 1 was used as wastewater containing nitrate nitrogen.
また、生物学的排水処理を行うための独立栄養細菌は、既存の活性汚泥装置から活性汚泥を採取して、元素状硫黄とともに脱窒槽へ充填し人工排水で馴養を行った後、硫黄脱窒活性が安定したことを確認して処理実施に用いた。元素状硫黄としては、球状硫黄又は破砕した硫黄を用いて回分式培養槽で馴養した。 Autotrophic bacteria for biological wastewater treatment are collected from existing activated sludge equipment, filled with elemental sulfur into a denitrification tank and acclimatized with artificial drainage, then sulfur denitrification. After confirming that the activity was stable, it was used for the treatment. As elemental sulfur, spherical sulfur or crushed sulfur was used and conditioned in a batch culture tank.
反応形式は図２に示すように、カラムに微生物菌体と球状硫黄を詰めて、アップフローで排水を通水して実施した。 As shown in FIG. 2, the reaction was carried out by filling the column with microbial cells and spherical sulfur and passing the waste water through upflow.
使用した球状硫黄の平均直径は３mmであった。
検討条件としてＳＶ（空間速度）＝０．５とした。表１の人工排水を処理カラムに通水して処理を実施して、処理後の排水は原水槽に導入して循環させる構造とした。
ＳＶ（空間速度）の単位：「ｈ-1」
The average diameter of the spherical sulfur used was 3 mm.
As an examination condition, SV (space velocity) was set to 0.5. The artificial waste water shown in Table 1 was passed through the treatment column for treatment, and the treated waste water was introduced into the raw water tank and circulated.
SV (space velocity) unit: “h −1 ”
反応条件は、次のとおりとした。
原水（模擬排水）量：１．０Ｌ
カラム：１．０Ｌ
原水中の硝酸態窒素濃度：２０mg／Ｌ
pH７(pHが変化する場合は、ＫＨ2ＰＯ4、ＮａＣＯ3水溶液で調整）
温度：４０℃
The reaction conditions were as follows.
Raw water (simulated drainage) volume: 1.0L
Column: 1.0L
Nitrate nitrogen concentration in raw water: 20mg / L
pH 7 (If pH changes, adjust with KH 2 PO 4 or NaCO 3 aqueous solution)
Temperature: 40 ° C
一定時間ごとに水中の硝酸態窒素を測定し、硝酸態窒素が１mg／Ｌ以下になる時間を比較することにより脱窒性能を検討した。その結果、硝酸態窒素が１mg／Ｌ以下になる時間は、３０時間であった。 Nitrate nitrogen in water was measured at regular intervals, and the denitrification performance was examined by comparing the time when nitrate nitrogen was 1 mg / L or less. As a result, the time for nitrate nitrogen to be 1 mg / L or less was 30 hours.
比較例１
球状硫黄を破砕状硫黄にして実施する以外は実施例２と同様に行った。また、破砕状硫黄の大きさはふるいで２〜４mmとした。
硝酸態窒素が１mg／Ｌ以下になる時間は、５０時間であった。
Comparative Example 1
The same procedure as in Example 2 was performed except that the spherical sulfur was changed to crushed sulfur. The size of the crushed sulfur was 2 to 4 mm with a sieve.
The time for nitrate nitrogen to be 1 mg / L or less was 50 hours.
Claims (3)
還元剤として粒子径が１〜５mmである球状硫黄を使用することを特徴とする排水中の窒素除去方法。 In a method for removing nitrogen in wastewater, in which wastewater containing nitrate nitrogen is biologically treated under anaerobic conditions,
A method for removing nitrogen in wastewater, characterized by using spherical sulfur having a particle diameter of 1 to 5 mm as a reducing agent.
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