JP2018094553A - Sulfur material for denitrification - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sulfur material for denitrification which has both hydrophilic property and alkalinity supply function, simple to be used, having high denitrification performance.SOLUTION: The present invention relates to a sulfur material for denitrification and a denitrifying treatment device that includes powdery sulfur, an alkali agent and a surface-active agent.SELECTED DRAWING: None

Description

  The present invention relates to a denitrification sulfur material for removing nitrate nitrogen and nitrite nitrogen contained in swine drainage and the like, a denitrification treatment apparatus and a denitrification treatment method using the same.

It is known that nitrate nitrogen (NO ₃ ⁻ —N) contained in wastewater has an effect on human health and environmental pollution (mainly groundwater pollution). As a health hazard due to nitrate nitrogen, methemoglobinemia and the like are known.

Environmental criteria item health protection of persons according to the water pollution of ground water and water bodies in 1999, _NO ³ - -N and nitrite nitrogen - reference value of the sum of _(NO ² -N) within 10 mg / L Was set. However, the excess rate of environmental standards in groundwater is still high. Causes of groundwater contamination include excessive fertilization, improper treatment of livestock excrement, underground penetration of untreated domestic wastewater, etc. Contamination from livestock excrement is the second highest after overfertilization.

Based on this background, wastewater standards for “ammonia, ammonium compounds, nitrite compounds and nitrate compounds” contained in wastewater in livestock have been established by the Water Pollution Control Law. The general reference value for this item is 100 mg / L, but in the case of livestock production, a provisional reference value of 1500 mg / L was established in 2001 because it is difficult to achieve with conventional processing techniques. Since then, it has been reduced to 900 mg / L in 2004, 700 mg / L in 2013, and 600 mg / L in 2016, and in the future, it is required to tackle sewage treatment aiming at general standard values in livestock. In this specification, to a "ammonia, ammonium compounds, nitrites and nitric acid compounds" described as "nitrate nitrogen, etc.", also NO 3 _- ^-N and NO 2 _- are collectively ^-N It is described as “NOx-N”.

Among livestock, especially for swine drainage, nitrogen reduction technology utilizing sulfur denitrification has been developed. The sulfur denitrification, sulfur oxides denitrifying bacteria which is a type of autotrophic bacteria such as Thiobacillus denitrificans is, _NO ³ while oxidizing the sulfur with an oxygen-free conditions - reducing -N nitrogen gas - -N and _NO ² In this method, sulfur material is used.

  However, in the case of using powdered sulfur as a sulfur material in the sulfur denitrification method, it cannot be used for wastewater treatment because it has water repellency as it is, and a surfactant such as a neutral detergent for household use after pouring powdered sulfur into water. There is a problem that this work has a great amount of labor. On the other hand, if crude sulfur (including coarse particles with a particle size of about 40 mm) that is distributed as an industrial raw material is used instead of powdered sulfur, it will settle in water as it is and no hydrophilization treatment is required. There is a problem that the denitrification activity is lower than that of powdered sulfur because of the small contact area.

In addition, in the sulfur denitrification method, it is required to prevent the pH of treated water from decreasing due to sulfate ions (SO ₄ ²⁻ ) that increase with the progress of denitrification activity, and to supply alkalinity necessary for denitrification activity. If an addition device is provided to replenish the alkalinity, the system may be complicated.

  In Patent Document 1, as a sulfur material that does not require additional alkalinity supplementation, heat-melted sulfur is uniformly stirred and mixed with calcium carbonate to cool and solidify, and the solidified product obtained by this cooling is crushed. A composition is described which is in the form of a granular or massive solid in which calcium carbonate and sulfur coexist in a single particle. However, the composition described in Patent Document 1 requires a special molding process, and has a problem that the contact area per unit weight is small as compared with powdered sulfur, and further improvement has been demanded. .

Japanese Patent No. 3430364

  In view of the above circumstances, an object of the present invention is to provide a sulfur material for denitrification that has both hydrophilicity and alkalinity replenishment function, can be used easily, has high denitrification performance, and is easy to manufacture. .

  One embodiment of the present invention relates to the following items.

1. Sulfur materials for denitrification, including powdered sulfur, alkaline agent, and surfactant.

2. The sulfur material for denitrification according to 1 above, wherein the alkaline agent contains calcium carbonate and / or magnesium carbonate.

3. The sulfur material for denitrification according to 1 or 2 above, wherein the alkaline agent comprises natural magnesite and / or synthetic magnesite.

4). The sulfur material for denitrification according to any one of the above 1 to 3, wherein the surfactant includes a nonionic surfactant.

5. The content of the powdered sulfur is 30 to 69.5% by weight, the content of the alkaline agent is 30 to 69.5% by weight, and the surface activity is based on the total weight of the sulfur material for denitrification. The sulfur material for denitrification according to any one of the above 1 to 4, wherein the content of the agent is 0.5 to 5% by weight.

6). The sulfur material for denitrification according to any one of 1 to 5 above, wherein the alkaline agent contains calcium carbonate, and the content of calcium mesh particles of 60 mesh pass with respect to the total weight of calcium carbonate is 10% by weight or less.

7). A method for producing a sulfur material for denitrification, comprising a step of kneading powdered sulfur, an alkali agent, and a surfactant.

8). A denitrification method for waste water, comprising a step of bringing the denitrification sulfur material according to any one of 1 to 6 above into contact with waste water.

9. The denitrification processing apparatus containing the sulfur material for denitrification in any one of said 1-6.

10. A tank capable of containing liquid;
In the tank, a first compartment and a second compartment that are partitioned by a partition in the vertical direction and communicated by a liquid passing space immediately below the partition,
The sulfur material layer in which the denitrification sulfur material according to any one of the above 1 to 6 is deposited to a height above the liquid passing space in the lower part in the first compartment, the lower part in the second compartment, and the liquid passing space. When,
A pressurized air supply pipe which communicates with the vicinity of the liquid passing space and supplies pressurized air to the sulfur material layer of the first section and the sulfur material layer of the second section;
9. The denitrification apparatus according to 8 above, comprising:

11. A tank capable of containing liquid;
In the tank, a first compartment and a second compartment that are partitioned by a partition in the vertical direction and communicated by a liquid passing space immediately below the partition,
Sulfur in which the sulfur material for denitrification according to any one of the above 1 to 6 is deposited to a height above the liquid passing space in the lower part in the first compartment, the lower part in the second compartment, and the liquid passing space. The material layer,
A vibrator installed on the outer surface of the tank and / or in the sulfur material layer;
10. The denitrification apparatus as described in 9 above.

12 A tank capable of containing liquid;
A sulfur material layer in which the denitrification sulfur material according to any one of 1 to 6 is deposited in a lower part of the tank;
Means for supplying liquid into the sulfur material layer from outside the tank;
Have
10. The denitrification apparatus according to 9 above, wherein the supplied liquid is reversed at the bottom in the bed and becomes an upward flow.

  According to one embodiment of the present invention, it is possible to provide a sulfur material for denitrification that can be easily used in a sulfur denitrification method in a swine wastewater treatment facility or the like, has high denitrification performance, and is easy to manufacture.

It is a schematic diagram which shows the one aspect | mode of a denitrification processing apparatus. It is a schematic diagram which shows another one aspect | mode of a denitrification processing apparatus. It is a schematic diagram which shows another one aspect | mode of a denitrification processing apparatus. It is a schematic diagram of a T-shaped member. It is a schematic diagram of the denitrification processing apparatus used in the Example. It is a graph which shows transition of the raw | natural water inflow amount and hydraulic residence time (HRT) in a test period in an Example. In Example, _NO ³ of the raw water and the treated water during the study - -N, _NO ² - is a graph showing a change in the concentration of -N. It is a graph which shows transition of the reactor water temperature and NOx-N load amount during a test period in an Example. It is a graph which shows the relationship between the NOx-N load amount after the test start 21st day and a NOx-N removal rate in an Example. It is a graph which shows the relationship between the water temperature in a reactor after the test start 21st day, and a NOx-N removal rate in an Example. In the embodiment, it is a graph showing the relationship between ΔSO ₄ ^2- and ΔNOx-N. It is a graph which shows transition of the pH of the raw | natural water and treated water during a test period in an Example. In the embodiment (Example B), in the case of changing the type of alkaline agents, NO 3 for denitrification days _- is a graph showing a change in the concentration of ^-N.

<Sulfur materials for denitrification>
The denitrification sulfur material (also simply referred to as “sulfur material”) of the present embodiment includes powdered sulfur, an alkali agent, and a surfactant. Since the denitrification sulfur material of this embodiment is in a powder form, the contact area per unit weight is large, and a high denitrification effect can be obtained. Moreover, the sulfur material for denitrification of this embodiment is easy to adapt to waste water because powder sulfur is coated with a surfactant and has high hydrophilicity, and can be used for denitrification treatment by simply throwing it into the waste water. Furthermore, since the denitrification sulfur material of the present embodiment contains an alkali agent in advance, it is not necessary to supplement the alkalinity separately. Therefore, the denitrification sulfur material of the present embodiment can be used for drainage denitrification treatment very easily. In addition, the denitrification sulfur material of this embodiment has a very simple manufacturing method.

  In addition, pure sulfur usually falls under the category of dangerous materials (combustible materials) under the Fire Service Law, and transportation and storage must comply with legally stipulated conditions, but the sulfur material for denitrification of this embodiment is The coexistence of the surfactant and the alkali agent makes it nonflammable (that is, it is treated as a non-hazardous material in the Fire Service Law) and is easier to handle than pure sulfur.

  Hereinafter, the raw material etc. which are contained in the sulfur material for denitrification of this embodiment are demonstrated in detail. In the present specification, waste water before performing denitrification to remove NOx-N is referred to as “raw water”, and waste water after denitrification is referred to as “treated water”.

(Powder sulfur)
The particle size of the powdered sulfur contained in the denitrification sulfur material of the present embodiment is preferably at least 90% by weight or more preferably 100% by weight of the powdered sulfur, and the lower limit is not particularly limited. For example, 50% by weight or more is preferably 500 mesh on. When the particle size of the powdered sulfur is 150 mesh pass, the contact area per unit weight of the sulfur material is increased, and a high denitrification effect can be obtained. The “particle size” in the present specification is a measurement result based on JIS K6222-1.

  The content of powdered sulfur with respect to the total weight of the denitrification sulfur material is preferably 30% by weight or more, more preferably 40% by weight or more, preferably 70% by weight or less, more preferably 69.5% by weight or less, 60% by weight or less is more preferable. When the content of powder sulfur is within this range, a sufficient denitrification effect can be obtained, and a denitrification sulfur material excellent in balance with the effect of the alkaline agent can be obtained.

(Alkaline agent)
The denitrification sulfur material of this embodiment includes an alkaline agent. The alkaline agent reacts with sulfate ions (SO ₄ ²⁻ ) that increase as the denitrification activity progresses, thereby preventing a decrease in the pH of the treated water and suppressing a decrease in the denitrification activity. As the alkali agent, weak alkali powder is preferable. As an alkaline agent, what can hold | maintain pH of treated water becomes like this. Preferably it is 6.5-8.5, More preferably, it is 7.0-8.5, More preferably, it is 7.2-8.5.

The alkali agent is not particularly limited, for example, sodium hydrogen carbonate (NaHCO _3), sodium carbonate _(Na 2 _CO 3), calcium oxide (CaO), calcium hydroxide (Ca _(OH) 2), calcium carbonate (CaCO ₃ ), and magnesium carbonate (MgCO ₃ ). Of these, sodium hydrogen carbonate, calcium carbonate, and magnesium carbonate are preferred from the viewpoint that, in addition to preventing pH reduction, the carbonate ions necessary for the growth and denitrification of sulfur-oxidizing denitrifying bacteria can be supplied. From the viewpoint of low cost, calcium carbonate is more preferable.

  As one embodiment of the present invention, it is preferable to use magnesium carbonate as the alkaline agent. When an alkaline agent containing calcium such as calcium carbonate is used, insoluble calcium sulfate (gypsum) is formed in the denitrification reaction, and insoluble components are deposited in the denitrification treatment device (denitrification reactor). This may cause problems such as solidification of the material layer and reduced denitrification ability. On the other hand, magnesium carbonate is preferable for wastewater treatment because it is insoluble in water before the denitrification reaction. Further, magnesium sulfate formed by the denitrification reaction is easily dissolved in water and hardly causes insoluble components. Therefore, when magnesium carbonate is used, the problem that the material layer solidifies is less likely to occur than when calcium carbonate is used, which may be preferable.

As the magnesium carbonate, high-purity magnesium carbonate or magnesite containing magnesium carbonate as a main component is preferable. For example, the content of MgCO _{3 in} magnesite is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more. The magnesite may be natural magnesite (mineral) or synthetic magnesite. When a sulfur material containing magnesite is used as the alkaline agent, it can be maintained at a pH that facilitates the denitrification reaction.

However, as shown in Examples described later, basic magnesium carbonate (generally, mMgCO ₃ .Mg (OH) ₂ .nH ₂ O (where m = 3 to 5, n = 3 to 8) as magnesium carbonate. When a magnesium carbonate compound having a hydroxy group is used as in ()), the denitrification reaction is difficult to proceed, which may be undesirable. The content of the magnesium carbonate compound having a hydroxy group in the alkaline agent is preferably 5% by weight or less, and may be 0% by weight.

  These alkaline agents may be used alone or in combination of two or more.

  The shape of the alkali agent is preferably powdery or granular. The average particle diameter of the alkali agent (particularly calcium carbonate) is not particularly limited, but is preferably 60 mesh on and 5 mesh pass, more preferably 50 mesh on and 5 mesh pass.

  In addition, if the content of fine particles having a small particle size as an alkaline agent is too large, white turbidity may occur in the treated water, which may cause problems with drainage, and a separate step is required before draining the treated water. There is a case. The preferable particle diameter of the alkali agent can be determined depending on the type of the alkali agent. For example, if the content of fine particles with a particle size of 60 mesh pass is too large in an alkali agent (especially calcium carbonate), white turbidity may occur in the treated water, resulting in problems with drainage. In some cases, a separate step of precipitation is required. Therefore, in the total weight of the alkali agent (especially calcium carbonate), the weight ratio of the 60 mesh pass particles is preferably 10% by weight or less, more preferably less than 5% by weight, and even 0% by weight. Good.

  The blending amount of the alkaline agent is not particularly limited, but is preferably 30% by weight or more, more preferably 40% by weight or more, and preferably 70% by weight or less based on the total weight of the denitrification sulfur material. 5 wt% or less is more preferable, and 60 wt% or less is more preferable.

  Further, the mixing ratio (weight ratio) of the powdered sulfur and the alkali agent in the denitrification sulfur material is not particularly limited, but the ratio (powder sulfur: alkali agent) is preferably 3: 7 to 7: 3, More preferably, it is 4: 6-6: 4, More preferably, it is 5: 5. When the blending ratio is within this range, the balance between denitrification activity and suppression of pH reduction is excellent.

(Surfactant)
The denitrification sulfur material of this embodiment includes a surfactant. By including a surfactant, hydrophilicity is imparted to the powdered sulfur, and even if the sulfur material is in powder form, the sulfur material can be easily adapted to wastewater such as swine drainage, so it is only necessary to put this sulfur material into the wastewater. Easy to use.

  The surfactant is not particularly limited and may be any of nonionic, anionic, cationic and amphoteric, but the main component (preferably 50% by weight or more based on the total weight of the surfactant, (It may be 100% by weight) is preferably a nonionic surfactant. If it is nonionic, there is little foaming and it is hard to be influenced by pH and temperature change in treated water, and it becomes easy to handle sulfur materials. The HLB value of the surfactant is not particularly limited, but is preferably about 10 to 13.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene carboxylic acid ester, sorbitan ester, polyoxyethylene Examples thereof include ethylene sorbitan ester and acetylene glycol.

  Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, {(mono, di, tri) alkyl} naphthalene sulfonates. Etc.

  Examples of the cationic surfactant include quaternary ammonium salts or pyridinium salts. Specifically, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt Dimethylbenzyl lauryl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl benzyl ammonium salt, trimethyl benzyl ammonium salt, triethyl benzyl ammonium salt, dimethyl diphenyl ammonium salt, benzyl dimethyl phenyl ammonium salt, hexadecyl pyridinium salt, lauryl pyridinium salt, dodecyl Pyridinium salt, stearylamine acetate, laurylamine acetate, octadecyla Such as emissions acetate, and the like.

  Examples of amphoteric surfactants include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid.

  These surfactants may be used alone or in combination of two or more.

  When mixing the surfactant and other raw materials, the surfactant may be diluted with a solvent such as water or may be used as it is without being diluted with a solvent or the like.

  The content of the surfactant is preferably 0.5 to 5% by weight and more preferably 1 to 3% by weight with respect to the total weight of the denitrification sulfur material.

  The sulfur material for denitrification of the present embodiment is preferably in a powder form or a mixed form of a powder form and a granular form, and as one aspect, a powder form sulfur of 150 mesh pass, 60 mesh on and 5 mesh pass. A mixture with a powdery and / or granular alkaline agent (especially calcium carbonate) is more preferred. The sulfur material for denitrification of this embodiment has a large contact area per unit weight and can achieve a high denitrification effect as compared to a conventional sulfur material in the form of coarsely crushed or pellets.

<Method for producing sulfur material for denitrification>
The method for producing a denitrification sulfur material of the present embodiment includes a step of kneading powdered sulfur, a surfactant, and an alkali agent (hereinafter also simply referred to as “kneading step”). The kneading step can be performed using a known ribbon blender, Henschel mixer, tumbler blender, biaxial stirrer, or the like. In the kneading step, the mixing order of the raw materials is not limited, and all the raw materials may be mixed at the same time or may be kneaded while mixing stepwise. The kneading step is not particularly limited, but is preferably performed under normal temperature and normal pressure conditions. In this specification, normal temperature refers to 20 ° C. ± 20 ° C. (0 ° C. to 40 ° C.), and normal pressure refers to pressure that is neither particularly pressurized nor depressurized, and is usually at atmospheric pressure. Equivalent pressure (about 1 atm). In addition, the kneading step may be performed using a solvent such as water. The manufacturing method of the denitrification sulfur material of this embodiment does not include a special molding process as described in Patent Document 1, and is a simple method.

<Denitrification treatment method>
The sulfur material for denitrification of the present embodiment can be used for removing nitrate nitrogen and the like from wastewater from the livestock industry, agriculture, fishery industry (including aquaculture industry, fish breeding industry, etc.). It is suitably used for removing nitrate nitrogen from wastewater in the field of animal husbandry such as swine drainage. Here, hog raising drainage means drainage containing pig manure and washing water. In swine sewage wastewater, there is a sulfur oxidative denitrifying bacterium that performs a sulfur denitrification reaction (a reaction that uses sulfate to reduce nitrate nitrogen to nitrogen gas and at the same time generates sulfate ions). When the sulfur material for denitrification of this embodiment is used, sulfur-oxidizing bacteria in the swine wastewater grow on the surface of the material, nitrate nitrogen is converted into nitrogen gas by the metabolic reaction, and nitrogen is released out of the system. be able to. The sulfur material for denitrification of this embodiment can also be used when removing nitrate nitrogen or the like in wastewater treatment of fish breeding water such as an aquarium.

  The denitrification method of the present embodiment includes a step of bringing the denitrification sulfur material into contact with wastewater containing nitrate nitrogen such as swine wastewater. It is preferable to cause a denitrification reaction by bringing a sulfur material for denitrification and waste water containing nitrate nitrogen into contact with each other in a tank capable of accommodating a liquid.

  As one embodiment of the present invention, it is preferable to use a denitrification treatment apparatus (also referred to as “denitrification reactor”) when performing denitrification treatment of waste water or the like using a denitrification sulfur material. A denitrification processing apparatus is installed in the back | latter stage of a pig raising wastewater treatment facility, for example, and performs a denitrification process for the discharge water (hog raising wastewater) of the said facility.

  An embodiment of the denitrification apparatus includes: a tank capable of storing a liquid; a first section and a second section defined in the tank by a partition wall in a vertical direction and communicated by a liquid passing space immediately below the partition wall; It is preferable to have a sulfur material layer in which the sulfur material for denitrification is deposited to a height above the liquid passing space in the lower part in the first compartment, the lower part in the second compartment, and the liquid passing space. As the denitrification treatment apparatus, preferably, a sediment precipitation tank (notch tank) for civil engineering can be used.

  In FIG. 1, the schematic diagram of an example of a denitrification processing apparatus is shown. The denitrification processing apparatus 10 is divided into three sections (first section 10a, second section 10b, and third section 10c) by vertical partition walls 12a and 12b, and is separated by a liquid passing space immediately below the partition wall 12a. The first section 10a and the second section 10b communicate with each other. In the lower part in the first compartment 10a, the lower part in the second compartment 10b, and the liquid passing space, the sulfur material layer 11 in which the sulfur material for denitrification of the present embodiment is deposited to a height above the liquid passing space exists. To do. In addition, although the sulfur material for denitrification of this embodiment is a powder form, since it contains a surfactant in advance and is hydrophilic, it should be directly put into the denitrification apparatus 10 without performing a hydrophilic treatment. Can do. Although the denitrification sulfur material 11 is not particularly limited, for example, 100 to 250 kg is charged per notch tank having an effective volume of 500 L.

  In the denitrification process, the raw water 1 such as swine sewage drainage flows into the first section 10a and is allowed to flow down naturally to the third section 10c. During the flow, the liquid passes through the sulfur material layer 11, and at this time, nitrate nitrogen or the like is changed to nitrogen gas by the sulfur denitrification reaction, and is discharged out of the system.

  The raw water is continuously fed, for example, with an inflow rate of 100 to 1500 mL / min and a hydraulic residence time (HRT) per effective water volume of 0.2 to 3.5 days. Sulfur oxidation and denitrification bacteria grow on the surface of the denitrification sulfur material in the sulfur material layer 11 in the tank, and denitrification using sulfur proceeds. Sulfur oxidizing denitrifying bacteria use sulfur to reduce nitrate nitrogen and the like to nitrogen gas and at the same time generate sulfate ions. Here, since the sulfur material for denitrification of this embodiment contains an alkali agent, it is possible to prevent the pH of the treated water from being lowered even if an alkali agent such as calcium carbonate is not added separately. If necessary, an alkaline agent such as calcium carbonate may be added to at least one section selected from the first section 10a, the second section 10b, and the third section 10c in the denitrification reactor, and may be input to a plurality of sections. May be.

  In addition, although the number of the sulfur material injection | throwing division divided by the partition shows the aspect which is 2 divisions of the 1st division 10a and the 2nd division 10b in FIG. 1, the number of divisions is increased further, Preferably it is 3 divisions More preferably, if the number of stages is increased to 4 or more, the processing performance can be improved.

  The denitrification treatment equipment (for example, the upper open-type water tank partitioned into multiple compartments by a partition wall (baffle) having a drainage flow gap at the bottom) gradually increases the flow resistance due to consolidation. However, the water level in the upstream section (first section 10a) rises and may eventually overflow the upper part of the partition wall 12a. If overflow occurs, the raw water will flow out of the tank of the denitrification apparatus without passing through the sulfur material layer 11, and the denitrification effect will be greatly reduced. As one mode for solving this problem, by increasing the difference in water level between the upstream section 10a and the downstream section (preferably 25 cm, more preferably 50 cm, and even more preferably 75 cm), a material layer with increased water resistance can be formed. It is preferable to allow the liquid to penetrate and pass. Moreover, the amount of the sulfur material layer 11 is adjusted so that the amount of the sulfur material input to the denitrification apparatus is adjusted so that the water level does not rise above the set water level difference and the treatment target liquid overflows the partition wall 12a. It is also preferable to adjust the thickness.

  As another mode for preventing raw water from overflowing the upper part of the partition wall 12a in the denitrification treatment apparatus, it is preferable to periodically release the consolidation of the sulfur material layer. There is a method of arranging a perforated PVC pipe) on the entire bottom surface and supplying air with a blower. However, there is a tendency that the consolidation of the sulfur material strongly proceeds immediately below the partition wall 12a. It was not enough for release and prevention of overflow. Therefore, the present inventors have conducted intensive studies to solve this problem, and that the denitrification apparatus is divided into a tank capable of storing a liquid; a vertical partition wall in the tank, and a passage directly under the partition wall. The first and second compartments communicated by the liquid space; and the denitrification sulfur material is deposited to a height above the fluid passage space in the lower portion in the first compartment, the lower portion in the second compartment, and the liquid passage space. A sulfur material layer comprising: a sulfur material layer; and a pressurized air supply pipe that communicates with the vicinity of the liquid passing space and supplies pressurized air to the sulfur material layer of the first section and the sulfur material layer of the second section. It was found that 11 consolidation could be released.

  FIG. 2A shows a schematic diagram of an example of a denitrification apparatus excellent in releasing the consolidation of the sulfur material layer.

  The denitrification processing apparatus 20 is further provided with a compressor 21 and a pressurized air introduction pipe 23 in addition to the configuration of the above-described denitrification processing apparatus 10 of FIG. The pressurized air introduction pipe 23 communicates with the vicinity of the liquid passing space immediately below the partition wall 12a, and the end thereof is coupled to the T-shaped member 24 that is an air blowing member near the liquid passing space. The denitrification apparatus 20 may further include an electromagnetic valve 22 on the pressurized air introduction pipe 23 to adjust the inflow of pressurized air from the compressor 21.

As shown in FIG. 3, the T-shaped member 24 has a horizontal bar portion 24a and a vertical bar portion 24b that is vertically connected to the central portion thereof, and the three ends are open and the inside is a continuous space. . The vertical bar portion 24b of the T-shaped member 24 is connected to the pressurized air introducing tube 23, and the horizontal bar portion 24a of the T-shaped member 24 has one end within the first compartment 10a and the other end of the both ends. It is preferably fixed in the vicinity of the bottom of the denitrification reactor 20 so that it is located in the second section 10b and the length direction of the horizontal bar portion 24a is substantially perpendicular to the wall surface of the partition wall 12a. The size of the T-shaped member 24 is not particularly limited. For example, when the total capacity of the denitrification apparatus is about 2 m ³ , the length of the horizontal bar portion and the vertical bar portion is 3 to 10 cm, respectively. The diameter of the hole is preferably about 3 to 10 mm.

  In the denitrification treatment apparatus 20, the air pressurized by the compressor 21 passes through the pressurized air introduction pipe 23 from both ends of the horizontal bar portion 24 a of the T-shaped member 24 and enters the first compartment and the second compartment. Is injected into the sulfur material layer (jet air 4), and the consolidation of the sulfur material layer is released. The injection time and frequency of this pressurized air injection are not particularly limited. For example, it may be set to 3 to 6 seconds per time, and the number of times may be set to 1 to 4 times a day. You may control the solenoid valve 22 installed in by a timer.

  The denitrification apparatus 20 may include two or more of the compressor 21, the electromagnetic valve 22, the pressurized air introduction pipe 23, and the T-shaped member 24 as necessary, and includes at least two T-shaped members 24. It is preferable to provide the above. When two T-shaped members 24 are installed, for example, the T-shaped members 24 are connected to the two ends of the pressurized air introduction pipe branched in a T-shape, and the two T-shaped members 24 are respectively connected to the denitrification reactor 20. It may be fixed near the bottom.

  Furthermore, the denitrification treatment apparatus is provided with a stirrer in which a stirring blade is positioned at the bottom height of the sulfur material layer as another aspect of the release method that is used in place of or in combination with the release of consolidation by the above-described pressurized air. Or you may continuously stir slowly.

  As yet another aspect, the denitrification apparatus can be configured by installing a submersible pump below the surface of the final section (third section 10c) and discharging the sucked liquid to the vicinity of the material layer below the partition wall using the introduction pipe. Reduces layer consolidation. At this time, if a flow path of a short circuit flow is formed in the sulfur material layer, the denitrification treatment of the raw water becomes insufficient, so the liquid discharge position, the discharge direction, and the discharge flow rate are adjusted to be appropriate. Is preferred.

  The denitrification processing apparatus 20 may further include a means for disposing a perforated pipe (for example, a perforated PVC pipe) over the entire bottom surface and supplying air with a blower to release the consolidation of the sulfur material layer.

  In the present embodiment, a plurality of methods may be used in combination in order to release the consolidation in the denitrification apparatus.

  On the other hand, when releasing the consolidation of the sulfur material layer as described above, if the air flow rate is too high, a tunnel-shaped void is formed in the material layer in the liquid passage space below the partition wall 12a, and the liquid penetrates the material layer. The denitrification performance may be reduced due to the flow down. As one mode for preventing this, an air blowing member may be installed at the bottom of the partition 12a at a position away from the liquid passing space, and the sulfur material may be periodically blown back to the bottom of the partition.

  FIG. 2B shows an embodiment of a denitrification apparatus that can prevent the formation of tunnel-like voids in the material layer in the liquid passing space when releasing the consolidation of the sulfur material layer. The denitrification processing apparatus 30 of FIG. 2B is provided with two gradients 31 on the bottom surface of the denitrification processing apparatus of FIG. 2A. A T-shaped member is provided by providing a gradient 31 on the left and right (first compartment 10a and second compartment 10b) bottom surfaces of the partition 12a in the denitrification treatment 30 so that the bottom of the partition 12a is the deepest portion of the recess. The sulfur material that has been soared by the ventilation from 24 sinks while being guided by the gradient 31 and can naturally return to the deposited state in the lower part of the partition wall.

  The denitrification processing apparatus may include a vibrator (not shown). The vibrator vibrates the sulfur material layer constantly or periodically to prevent nitrogen bubbles generated from the surface of the denitrification sulfur material from being buried in the sulfur material layer and hindering contact between the sulfur material and raw water. It is possible to defoam and release the consolidation of the sulfur material layer and prevent the formation of a short-circuit flow path. The vibrator is disposed on the outer surface of the denitrification apparatus such as a notch tank and / or in the sulfur material layer with a vibrator or a knocker, for example, pneumatic or electric.

  The denitrification apparatus may further include means (heating means) for heating the liquid temperature in the sulfur material-containing tank (the first section 10a and the second section 10b). Denitrification can be carried out from swine sewage wastewater throughout the year while suppressing the decrease in denitrification activity caused by nitrifying bacteria. The liquid temperature in the tank of the denitrification reactor is preferably 10 to 40 ° C., more preferably 30 to 40 ° C. at which sulfur-oxidizing denitrifying bacteria can act.

  One aspect of the denitrification apparatus provided with the heating means will be described below. A circulation line in which a submersible pump is installed as a circulation pump in the final section (the most downstream section) of the denitrification treatment device, and a part of the liquid (circulated liquid) in the final section is returned to the first section (the most upstream section). And a heating means is provided on the circulation line. For example, in the denitrification apparatus of FIG. 1, a submersible pump is installed in the third section 10c, and a circulation line connected to the submersible pump passes through the heating means and enters the first section 10a from the terminal liquid discharge port. It is installed so that the circulating fluid can be discharged. As a result, a part of the liquid in the third compartment 10c is supplied into the first compartment 10a in a heated state, and a decrease in denitrification activity can be suppressed.

  As a heating means, for example, an existing pig farm wastewater treatment facility includes an aeration tank for supplying the pig farm wastewater to the activated sludge method, and a method of using the heat of the liquid in the aeration tank is preferable. In the aeration tank, a high water temperature (for example, 15 ° C. or higher in winter) is often maintained throughout the year due to the heat of the blower and the ground temperature. As one aspect, for example, a part of the circulation line is made into a stainless steel flexible pipe having a length of about 5 to 10 m (preferably 10 m), wound in a coil shape in the liquid in the aeration tank, and immersed in the circulation liquid. Is preferably heated. Thereby, the liquid temperature in the aeration tank can be transferred to the denitrification apparatus, and a constant water temperature can be maintained even in winter. Further, when the liquid discharge port of this circulation line is installed in the vicinity of the liquid passing space in the first section of the denitrification processing apparatus (in the first section 10a in the case of the apparatus of FIG. 1), the sulfur material is simultaneously heated. The consolidation of the layer can also be released, which is preferable.

  As one aspect of this embodiment, two or more denitrification reactors as shown in FIG. 1, FIG. 2A, or FIG. 2B may be arranged in series or in parallel.

  As another aspect of the denitrification apparatus, a tank capable of storing liquid; a sulfur material layer in which sulfur material for denitrification is deposited in the lower part of the tank; and a liquid from outside the tank into the sulfur material layer An upward flow type denitrification treatment apparatus (denitrification reactor) having a supply means is preferable. FIG. 4 shows a schematic diagram of an example of an upflow type denitrification apparatus.

  The denitrification apparatus of FIG. 4 includes a tower-shaped tank 41 that can contain a liquid, a sulfur material layer 42 in which sulfur material is deposited in the lower part of the tank 41, and raw water from outside the tank in the sulfur material layer 42. The raw water supply pipe 43 is provided. One end of the raw water supply pipe 43 is preferably disposed in the sulfur material layer 42, and the end of the raw water supply pipe 43 in the sulfur material layer is close to the bottom, for example, from the bottom of the tank 41 to the height of the sulfur material layer 42. It is preferably arranged at a position of 1/2 or less, more preferably 1/4 or less. The shape of the tank 41 of the denitrification apparatus is not limited to a cylindrical shape, and may be, for example, a rectangular shape with a rectangular bottom surface. In addition, the size of the tank 41 is not limited to the numbers shown in FIG. 4. For example, in the case of a cylindrical shape, in an actual wastewater treatment facility or the like, the diameter of the bottom surface may be about 50 cm to 4 m, and the height is About 150 cm to 3 m. Although the amount of the sulfur material is not particularly limited, for example, 200 g to 600 g is introduced per 1 L of the volume of the tank 41.

  A plurality of raw water supply pipes 43 may be provided. Further, the end of the raw water supply pipe 43 on the side where the raw water flows and / or the end on the side where the raw water is discharged may be branched.

  In the denitrification apparatus of FIG. 4, raw water is continuously supplied in a downward flow through the raw water supply pipe 43. Although the supply method of raw | natural water is not specifically limited, You may supply with a pump and you may utilize a water head difference. The raw water released into the sulfur material layer 42 is reversed at the bottom of the tank 41 and becomes an upward flow. While the raw water passes through the sulfur material layer 42, nitrate nitrogen or the like in the raw water is caused by a sulfur denitrification reaction. It changes to nitrogen gas and is discharged out of the system as treated water. Here, in this denitrification treatment apparatus, if a short-circuit flow path is formed, the denitrification treatment of the raw water becomes insufficient. Therefore, for example, the pressurized water is supplied from the raw water supply pipe 43 as necessary. Is preferably inserted into the sulfur material layer 42 to make the sulfur material layer uniform.

  As one aspect of this embodiment, two or more upward flow denitrification treatment apparatuses as shown in FIG. 4 may be arranged in series or in parallel.

  Examples The present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

<Example A>
(1) Sulfur material for denitrification Based on sulfur powder (99.5% sulfur, 150 mesh pass), calcium carbonate (30 mesh pass and 50 mesh on), and nonionic surfactant (lipophilic) with viscosity adjustment A base material having 22 carbon atoms and an HLB value of 12.8) were kneaded using a ribbon blender or a biaxial stirrer to produce a denitrification sulfur material 1 (hereinafter also simply referred to as “sulfur material 1”). The blending ratio of each raw material is 48.5% by weight of powdered sulfur, 48.5% by weight of calcium carbonate, and 3% by weight of nonionic surfactant. Sulfur material 1 is sulfur of 150 mesh pass and 30 mesh pass and 50 mesh. It was in the form of powder containing calcium carbonate on.

(2) Experimental apparatus As the denitrification reactor, a cylindrical plastic column (about 8 cmφ × about 48 cm H) having an effective volume of the liquid part of 2.23 L shown in FIG. 4 was used. 1 kg of the developed sulfur material 1 (apparent volume: 1.12 L, layer thickness: 22.7 cm) was charged into this denitrification reactor. The activated sludge treated water discharged from the sewage treatment facility of the pig farmer was used as the raw water for the test. However, from the 23rd day after the start of the test, it became impossible to enter the farm due to the problem of prevention of epidemics, so 2.0 g / L of sodium nitrate was added to the activated sludge treated water of the Chiba Prefectural Livestock Research Center. Raw water was used. The raw water is transferred to the raw water storage tank, and from there, the reactor is fed by a diaphragm metering pump with an inflow of 1.0 to 6.5 mL / min and a hydraulic residence time (HRT) per effective liquid volume of 0.2 to 1.5 days. Was continuously injected from the lower part of (Fig. 5). The influence on denitrification activity was examined by changing the NO _x -N load by adjusting the raw water inflow. The injected raw water passed through the sulfur material layer deposited on the bottom of the reactor and was discharged as treated water from the top of the reactor. In addition, in order to maintain the water temperature of raw | natural water constant, the water temperature was adjusted to about 20 degreeC by throwing the underwater heater into the raw | natural water storage tank from the 7th day after the test start. Sulfur oxidizing denitrifying bacteria were not planted. The reactor was operated for 62 days from November 18, 2015 to January 19, 2016.

(3) Analysis method The pH was measured by the glass electrode method. NO ₃ ⁻ —N, NO ₂ ⁻ —N, ammonium nitrogen (NH ₄ ⁺ —N), SO ₄ ²⁻ are obtained by chromotropic acid method, diazotization method, salicylic acid method, barium sulfate / turbidimetric method, respectively. It was measured with an absorbance type multi-item water quality meter (PhotoFlex STD; Central Science, Tokyo). The M-alkalinity was measured by a drop test M-alkalinity (WAD-AL-M; Kyoritsu Riken, Tokyo).

  Table 1 shows the quality of raw water and treated water. In addition, the water quality of Table 1 represents the average value during the period processed by the denitrification reactor.

When the sulfur material 1 was put into a denitrification reactor filled with a liquid, it was confirmed that the entire amount settled quickly. Immediately after settling, the liquid in the reactor was clouded but gradually faded over time. The raw water NO ₃ ⁻ −N during the test period was 207.7 ± 53.1 mg / L (mean ± standard deviation), and NO ₂ ⁻ −N and NH ₄ ⁺ −N were hardly detected (Table 1). ).

Treated water NO ₃ ⁻ −N began to decrease after the 16th day from the start of the test, and on the 19th day it was reduced to 100 mg / L or less, which is a general reference value such as nitrate nitrogen in the water pollution control method (FIG. 6). . _NO ³ The treated water 23 after day - -N was below the detection limit. Thereafter, 100 mg / L or less could be maintained until the 62nd day when the test was completed. The water temperature during the test period changed in the range of 12.6 to 22.7 ° C., and the average was 18.6 ° C. (FIG. 7). Moreover, the NOx-N load amount fluctuated in the range of 0.28 to 1.95 kg-N / ton-material / day (FIG. 7). In particular, from the 21st day after the denitrification activity was expressed, the NOx-N load was gradually increased with the elapsed days in the range of 0.28 to 0.91 kg-N / ton-material / day. As a result, in the 62 days NOx-N load 0.91 kg-N / ton-material-date, the treated water _NO ³ - -N is increased to 44.4mg / L, NOx-N removal rate Even if the load increased to 83.1%, a high denitrification effect was maintained. Moreover, in the relationship between the NOx-N load amount and the NOx-N removal rate after the 21st day, the removal rate tended to increase as the load amount decreased (FIG. 8). It has been reported that the removal rate of about 80% was obtained using pure powder sulfur under the condition of NOx-N load 0.55kg-N / ton-material / day (Heragawa Teruaki, Tanaka Yasuo) 2015) Development of sulfur denitrification technology for swine sewage wastewater using a sedimentation tank diversion reactor equipped with a simple heating system: Journal of the Japanese Society of Animal Husbandry Environment: 14 (1): 47-55.). A removal rate of nearly 100% was obtained even at 57 kg-N / ton-material / day or less. The relationship between the water temperature after the 21st day and the NOx-N removal rate showed a tendency that the higher the water temperature, the higher the removal rate (FIG. 9). Therefore, it is speculated that the denitrification activity increases as the water temperature increases.

In the sulfur denitrification treatment, sulfur is oxidized by sulfur oxidative denitrification bacteria along with denitrification to generate SO ₄ ²⁻ . In the relationship between the amount of SO ₄ ²⁻ generated (ΔSO ₄ ²⁻ ) and the amount of nitrogen removed (ΔNOx−N), ΔSO ₄ ²⁻ tends to increase as the amount of removal increases, and there is a high correlation. (R ² = 0.9825, P <0.01) (FIG. 10).

Usually, when ΔSO ₄ ²⁻ increases, the pH of the treated water tends to be acidic. It is known that when SO ₄ ² —S reaches about 1000 mg / L, the pH of the treated water decreases to around 5.8. In this test, the pH of the raw water was 7.5 to 8.3, whereas the pH of the treated water was changed in the range of 6.8 to 7.9 (Table 1, FIG. 11). Although ΔSO ₄ ²⁻ increased significantly, it was shown that the pH of the treated water was maintained almost neutral. This neutralization effect is presumed to have contributed to the formation of calcium sulfate by combining calcium carbonate blended with the denitrification sulfur material with sulfate ions.

  In addition, alkalinity is an important factor for maintaining the denitrification activity in the sulfur denitrification treatment. The M-alkalinity of the treated water during the test period was 160 ± 38.4 mg / L (Table 1), but since sufficient denitrification activity was expressed, it can be said that the blending amount of calcium carbonate was sufficient.

  From the above results, it was shown that the denitrification sulfur material of the present embodiment is easy to handle and is effective for supplying the alkalinity necessary for sulfur denitrification and for the neutralization function.

In the survey of nitrate nitrogen and the like in Chiba Prefecture pig sewage treatment facilities, NO 3 of activated sludge treated water _- ^-N it has been reported that an average 184 mg / L. On the other hand, in this test, NOx-N was reduced by approximately 200 mg / L after 21 days from the start of the test. From this, it is thought that it can be expected to reduce nitrate nitrogen in the field.

<Example B>
Next, the alkali agent used for sulfur materials was examined.

(Example B1)
The activated sludge treated water of a pig farmer was used as test raw water, and 900 mL was charged into a 1 L beaker, and 450 g of the sulfur material 1 (using calcium carbonate as an alkaline agent) was filled therein. The raw water and the sulfur material 1 were stirred and mixed with a glass stirring bar and then allowed to stand. Later, pH, and _NO ³ with the passage of days - the -N concentrations were determined by analysis method of the above Example A. The test period was 54 days from September 1, 2017 to October 25, 2017. The pH of the treated water according to the elapsed days is shown in Table 2, and the NO ₃ ⁻ —N concentration is shown in FIG.

(Example B2)
A sulfur material 2 was prepared in the same manner as the method for producing the sulfur material 1 except that natural magnesite (particle size: 60 mesh pass, 200 mesh on) was used instead of calcium carbonate as the alkaline agent. Raw water was treated in the same manner as in Example B1 except that the sulfur material 2 was used in place of the sulfur material 1, and the pH and NO ₃ ⁻ —N concentration were measured. The results are shown in Table 2 and FIG.

(Example B3)
A sulfur material 3 was prepared in the same manner as the method for producing the sulfur material 1 except that synthetic magnesite (particle size: 150 mesh pass) was used instead of calcium carbonate as the alkaline agent. Raw water was treated in the same manner as in Example B1 except that the sulfur material 3 was used in place of the sulfur material 1, and the pH and NO ₃ ⁻ —N concentration were measured. The results are shown in Table 2 and FIG.

(Reference Example B4)
A sulfur material 4 was prepared in the same manner as the method for producing the sulfur material 1 except that basic magnesium carbonate (particle size: 200 mesh pass) was used instead of calcium carbonate as the alkaline agent. Raw water was treated in the same manner as in Example B1 except that the sulfur material 4 was used in place of the sulfur material 1, and the pH and NO ₃ ⁻ —N concentration were measured. The results are shown in Table 2 and FIG.

(Reference Example B5)
A sulfur material 5 was prepared in the same manner as the method for producing the sulfur material 1 except that granular basic magnesium carbonate was used instead of calcium carbonate as the alkaline agent. Raw water was treated in the same manner as in Example B1 except that the sulfur material 5 was used in place of the sulfur material 1, and the pH and NO ₃ ⁻ —N concentration were measured. The results are shown in Table 2 and FIG.

  Table 2 shows the pH in each denitrification treatment day in Examples B1 to B3 and Reference Examples B4 and B5.

FIG. 12 shows the concentration of NO ₃ ⁻ —N in each of the denitrification treatment days in Examples B1 to B3 and Reference Examples B4 and B5.

As shown in FIG. 12, the concentration of NO ₃ ⁻ —N in the raw water (before denitrification treatment) was 236.8 mg / L. Since the start of the test, the concentration of NO ₃ ⁻ —N in each example and reference example was reduced, and the concentration and removal rate of NO ₃ ⁻ —N on day 54 were as follows.
Example B1: 7.2 mg / L (removal rate 97%)
Example B2: 5.4 mg / L (removal rate 97.7%)
Example B3: 60.4 mg / L (removal rate 74.5%)
Reference Example B4: 145.6 mg / L (removal rate 38.5%)
Reference Example B5: 221.6 mg / L (removal rate 6.4%)

From Examples B1 to B3, it was shown that the sulfur material using natural magnesite or synthetic magnesite as an alkaline agent has a high removal rate of NO ₃ ⁻ —N as in the case of using calcium carbonate. On the other hand, the sulfur material using basic magnesium carbonate had a low removal rate of NO ₃ ⁻ —N. The reason for this is not clear, but it is presumed that when a sulfur material containing natural magnesite or synthetic magnesite was used, the pH at which the denitrification reaction easily proceeded could be maintained.

  When a sulfur material containing calcium carbonate is used, an insoluble component (calcium sulfate) formed by the denitrification reaction may be deposited, which may hinder the denitrification treatment. On the other hand, when a sulfur material containing magnesite is used as in Examples B2 and B3, the main component of magnesite is magnesium carbonate, and magnesium sulfate formed by the denitrification reaction is easily soluble in water. The problem of sedimentation of insoluble components as in the case of using is difficult to occur.

  Therefore, it can be said that a sulfur material containing natural magnesite or synthetic magnesite as an alkaline agent is preferable from the viewpoint of having a high denitrification effect and hardly generating insoluble components.

  INDUSTRIAL APPLICABILITY The present invention can be used for removing nitrate nitrogen and the like in pig farm wastewater treatment facilities.

1: Raw water 2: Treated water 3: Pressurized air 4: Blowing air 10: Denitrification treatment apparatus 10a: First section 10b: Second section 10c: Third section 11: Sulfur material layer 12a: Partition wall 12b: Partition wall 20: Denitrification treatment device 21: Compressor 22: Solenoid valve 23: Pressurized air introduction tube 24: T-shaped member 24a: Horizontal bar portion 24b: Vertical bar portion 30: Denitrification treatment device 31: Gradient 41: Tank 42: Sulfur material layer 43: Raw water supply pipe

Claims (12)

  Sulfur materials for denitrification, including powdered sulfur, alkaline agent, and surfactant.   The sulfur material for denitrification according to claim 1, wherein the alkaline agent contains calcium carbonate and / or magnesium carbonate.   The sulfur material for denitrification according to claim 1 or 2, wherein the alkaline agent includes natural magnesite and / or synthetic magnesite.   The sulfur material for denitrification as described in any one of Claims 1-3 in which the said surfactant contains a nonionic surfactant.   The content of the powdered sulfur is 30 to 69.5% by weight, the content of the alkaline agent is 30 to 69.5% by weight, and the surface activity is based on the total weight of the sulfur material for denitrification. The sulfur material for denitrification as described in any one of Claims 1-4 whose content of an agent is 0.5 to 5 weight%.   The denitrification according to any one of claims 1 to 5, wherein the alkaline agent contains calcium carbonate, and a content of 60 mesh pass calcium carbonate particles is 10 wt% or less based on a total weight of calcium carbonate. Sulfur material.   A method for producing a sulfur material for denitrification, comprising a step of kneading powdered sulfur, an alkali agent, and a surfactant.   A method for denitrifying wastewater, comprising a step of bringing the sulfur material for denitrification according to any one of claims 1 to 6 into contact with wastewater.   The denitrification processing apparatus containing the sulfur material for denitrification as described in any one of Claims 1-6. A tank capable of containing liquid;
In the tank, a first compartment and a second compartment that are partitioned by a partition in the vertical direction and communicated by a liquid passing space immediately below the partition,
The denitrification sulfur material according to any one of claims 1 to 6 is deposited to a height above the liquid passing space in the lower part in the first compartment, the lower part in the second compartment, and the liquid passing space. A sulfur material layer,
A pressurized air supply pipe which communicates with the vicinity of the liquid passing space and supplies pressurized air to the sulfur material layer of the first section and the sulfur material layer of the second section;
The denitrification processing apparatus according to claim 9, comprising: A tank capable of containing liquid;
In the tank, a first compartment and a second compartment that are partitioned by a partition in the vertical direction and communicated by a liquid passing space immediately below the partition,
The denitrification sulfur material according to any one of claims 1 to 6 is deposited to a height above the liquid passing space in the lower part in the first compartment, the lower part in the second compartment, and the liquid passing space. A sulfur material layer,
A vibrator installed on the outer surface of the tank and / or in the sulfur material layer;
The denitrification processing apparatus according to claim 9, comprising: A tank capable of containing liquid;
A sulfur material layer in which the sulfur material for denitrification according to any one of claims 1 to 6 is deposited at a lower portion in the tank,
Means for supplying liquid into the sulfur material layer from outside the tank;
Have
The denitrification processing apparatus according to claim 9, wherein the supplied liquid is reversed at the bottom in the layer and becomes an upward flow.