JP7633301B2 - Liquid fertilizer manufacturing device and liquid fertilizer manufacturing method - Google Patents
Liquid fertilizer manufacturing device and liquid fertilizer manufacturing method Download PDFInfo
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Description
本発明は、液体肥料製造装置及び液体肥料製造方法に関する。 The present invention relates to a liquid fertilizer production device and a liquid fertilizer production method.
液体肥料は穀物、野菜、果物、花卉等、様々な種類の植物の生育に有用である。液体肥料は無機態窒素を含有しており、無機態窒素は、(1)アンモニア態窒素、(2)硝酸態窒素及び亜硝酸態窒素に大別される。
液体肥料の製造において肥料成分(窒素、リン酸、カリウム)を濃縮するために電気透析処理を行う工程がある場合、特に、有機物の消化液を原料として用いる液体肥料の製造において電気透析処理を行う工程がある場合、イオン交換膜付近で溶解度積以上の濃縮がかかると無機成分の析出が生じる。
例えば、消化液中にリン酸とカルシウムが含まれている場合、リン酸カルシウムが析出して、イオン交換膜を閉塞させる。
Liquid fertilizers are useful for the growth of various types of plants, including grains, vegetables, fruits, flowers, etc. Liquid fertilizers contain inorganic nitrogen, which is broadly classified into (1) ammonia nitrogen, (2) nitrate nitrogen, and nitrite nitrogen.
When the production of liquid fertilizer includes a step of performing electrodialysis to concentrate fertilizer components (nitrogen, phosphate, potassium), particularly when the production of liquid fertilizer uses digested liquid of organic matter as a raw material, precipitation of inorganic components occurs when the fertilizer is concentrated near the ion exchange membrane beyond its solubility product.
For example, if the digestive fluid contains phosphoric acid and calcium, calcium phosphate will precipitate and block the ion exchange membrane.
イオン交換膜の閉塞時には、酸性薬剤を用いてイオン交換膜を洗浄することが一般的である。酸性薬剤としては、コスト的なメリットから塩酸を用いることが一般的である。 When an ion exchange membrane becomes clogged, it is common to clean the membrane using an acidic agent. Hydrochloric acid is generally used as the acidic agent due to its cost advantage.
イオン交換膜の洗浄に塩酸を用いることは従来から実施されてきた。
洗浄作業で発生する洗浄液は塩酸を含み、酸性であることから、そのまま公共用水域へ放流することができない。
放流するためには、pHの中和作業が必要であり、中和処理するために作業やコストが発生することは、液体肥料の生産性の向上を考えるうえで、不利になるという課題があった。
また、中和処理後に放流すると、洗浄液に含まれる肥料成分のリン酸も放流することになり、原料中に含まれる肥料成分の一部が液体肥料として利用されないという課題があった。
The use of hydrochloric acid for cleaning ion exchange membranes has been practiced in the past.
The cleaning solution generated during the cleaning process contains hydrochloric acid and is acidic, so it cannot be discharged directly into public waters.
In order to release the fertilizer, the pH must be neutralized, and the work and costs involved in the neutralization process are a disadvantage when considering improving the productivity of liquid fertilizer.
Furthermore, if the fertilizer is discharged after neutralization, the phosphoric acid contained in the washing liquid is also discharged, which poses the problem that some of the fertilizer components contained in the raw material are not utilized as liquid fertilizer.
本発明の主たる目的は、電気透析部のイオン交換膜の洗浄時に発生する洗浄液を液体肥料の成分として利用することができる液体肥料製造装置及び液体肥料製造方法を提供することにある。 The main objective of the present invention is to provide a liquid fertilizer production device and a liquid fertilizer production method that can utilize the cleaning liquid generated when cleaning the ion exchange membrane of the electrodialysis section as a component of liquid fertilizer.
本発明者らは、上記課題の解決について鋭意検討した結果、イオン交換膜の閉塞時に用いる酸性薬剤として硝酸を使用し、硝酸を含む洗浄液を液体肥料の成分として利用することで、上記課題を解決し得ることを見出し、本発明に至った。 As a result of extensive research into solving the above problems, the inventors discovered that the above problems could be solved by using nitric acid as an acidic agent to block the ion exchange membrane and using a cleaning solution containing nitric acid as a component of liquid fertilizer, which led to the invention.
即ち、本発明は以下の特徴を有する。
[1]有機物の消化液を原料として、無機態窒素を含有する液体肥料を製造する液体肥料製造装置であって、
被処理液を濃縮する電気透析部と、
該電気透析部のイオン交換膜を薬品洗浄する薬品洗浄機構と、を有し、
該イオン交換膜の閉塞時に、該薬品洗浄機構が硝酸を用いてイオン交換膜を薬品洗浄する、液体肥料製造装置。
[2]前記薬品洗浄で発生した洗浄液を、前記電気透析部の前段に戻す機構を有する、[1]に記載の液体肥料製造装置。
[3]前記薬品洗浄で発生した洗浄液を、前記電気透析部の電気透析濃縮液と配合する機構を有する、[1]又は[2]に記載の液体肥料製造装置。
[4]前記薬品洗浄で発生した洗浄液を、液体肥料の成分として利用する、[1]~[3]のいずれかに記載の液体肥料製造装置。
[5]前記薬品洗浄で発生した洗浄液を、外部に排出しない、[1]~[3]のいずれかに記載の液体肥料製造装置。
[6]有機物の消化液を原料として、無機態窒素を含有する液体肥料を製造する液体肥料製造方法であって、
下記工程(1)及び(2)を有する、液体肥料製造方法;
工程(1):被処理液を濃縮する電気透析工程、
工程(2):該電気透析工程のイオン交換膜の閉塞時に、硝酸を用いて該イオン交換膜を薬品洗浄する薬品洗浄工程。
[7]前記薬品洗浄工程で発生した洗浄液を、前記電気透析工程の前段に戻す工程を有する、[6]に記載の液体肥料製造方法。
[8]前記薬品洗浄工程で発生した洗浄液を、前記電気透析工程の電気透析濃縮液と配合する工程を有する、[6]又は[7]に記載の液体肥料製造方法。
[9]前記薬品洗浄工程で発生した洗浄液を、液体肥料の成分として利用する、[6]~[8]のいずれかに記載の液体肥料製造方法。
[10]前記薬品洗浄工程で発生した洗浄液を、外部に排出しない、[6]~[8]のいずれかに記載の液体肥料製造方法。
That is, the present invention has the following features.
[1] A liquid fertilizer manufacturing apparatus for producing liquid fertilizer containing inorganic nitrogen using digestive liquid of organic matter as a raw material,
an electrodialysis unit for concentrating the liquid to be treated;
and a chemical cleaning mechanism for chemically cleaning the ion exchange membrane of the electrodialysis unit,
When the ion exchange membrane becomes clogged, the chemical cleaning mechanism uses nitric acid to chemically clean the ion exchange membrane.
[2] The liquid fertilizer manufacturing apparatus described in [1], which has a mechanism for returning the cleaning liquid generated during the chemical cleaning to the upstream stage of the electrodialysis section.
[3] A liquid fertilizer manufacturing apparatus as described in [1] or [2], having a mechanism for mixing the cleaning liquid generated by the chemical cleaning with the electrodialysis concentrate of the electrodialysis section.
[4] A liquid fertilizer manufacturing apparatus described in any of [1] to [3], in which the cleaning liquid generated by the chemical cleaning is utilized as a component of liquid fertilizer.
[5] A liquid fertilizer manufacturing apparatus as described in any of [1] to [3], in which the cleaning liquid generated during the chemical cleaning is not discharged to the outside.
[6] A method for producing a liquid fertilizer containing inorganic nitrogen using a digestive liquid of organic matter as a raw material, comprising:
A method for producing a liquid fertilizer, comprising the following steps (1) and (2):
Step (1): An electrodialysis step of concentrating the liquid to be treated;
Step (2): A chemical cleaning step of chemically cleaning the ion exchange membrane with nitric acid when the ion exchange membrane becomes clogged in the electrodialysis step.
[7] The liquid fertilizer production method described in [6], further comprising a step of returning the cleaning liquid generated in the chemical cleaning step to the upstream stage of the electrodialysis step.
[8] A liquid fertilizer production method according to [6] or [7], comprising a step of mixing the cleaning liquid generated in the chemical cleaning step with the electrodialysis concentrate from the electrodialysis step.
[9] A liquid fertilizer production method described in any one of [6] to [8], in which the cleaning liquid generated in the chemical cleaning process is used as a component of liquid fertilizer.
[10] A liquid fertilizer production method described in any of [6] to [8], in which the cleaning liquid generated in the chemical cleaning process is not discharged to the outside.
本発明の製造装置によれば、電気透析部のイオン交換膜の洗浄時に発生する洗浄液を液体肥料の成分として利用することができる。
本発明の製造方法によれば、電気透析部のイオン交換膜の洗浄時に発生する洗浄液の処理に煩わされることがなく、また、その洗浄液を液体肥料の成分として利用することができる。
According to the manufacturing apparatus of the present invention, the cleaning liquid generated during cleaning of the ion exchange membrane of the electrodialysis section can be used as a component of the liquid fertilizer.
According to the manufacturing method of the present invention, there is no need to deal with the trouble of disposing of the cleaning liquid generated when cleaning the ion exchange membrane of the electrodialysis section, and the cleaning liquid can be used as a component of liquid fertilizer.
以下、本発明の実施の形態について、図面を参照しつつ説明する。以下の実施の形態は本発明を説明するための単なる例示であって、本発明をこの実施の形態にのみ限定することは意図されない。
本発明は、その趣旨を逸脱しない限り、様々な態様で実施することが可能である。また、使用する図面は実施の形態の一例を説明するためのものであり、実際の大きさを表すものではない。
Hereinafter, embodiments of the present invention will be described with reference to the drawings. The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention to these embodiments.
The present invention can be implemented in various forms without departing from the spirit of the present invention. The drawings are for the purpose of explaining an example of an embodiment, and are not intended to represent the actual size.
<液体肥料製造装置>
本発明の液体肥料製造装置は、有機物の消化液を原料として、無機態窒素を含有する液体肥料を製造する液体肥料製造装置であって、被処理液を濃縮する電気透析部と、電気透析部のイオン交換膜を薬品洗浄する薬品洗浄機構と、を有し、イオン交換膜の閉塞時に、該薬品洗浄機構が硝酸を用いてイオン交換膜を薬品洗浄する。
<Liquid fertilizer manufacturing equipment>
The liquid fertilizer manufacturing apparatus of the present invention is a liquid fertilizer manufacturing apparatus that produces liquid fertilizer containing inorganic nitrogen using digested liquid of organic matter as a raw material, and has an electrodialysis section that concentrates the treated liquid, and a chemical cleaning mechanism that chemically cleans the ion exchange membrane of the electrodialysis section, and when the ion exchange membrane becomes clogged, the chemical cleaning mechanism chemically cleans the ion exchange membrane using nitric acid.
本発明の液体肥料製造装置は、電気透析部と、薬品洗浄機構とを有し、後述する洗浄液を電気透析部の前段に戻す機構、又は、洗浄液を電気透析部の処理水と配合する機構を有することが好ましい。これらの他にも、一般的な液体肥料製造装置に付帯する設備を有することができる。 The liquid fertilizer production apparatus of the present invention preferably has an electrodialysis section and a chemical cleaning mechanism, and has a mechanism for returning the cleaning liquid to the upstream stage of the electrodialysis section, as described below, or a mechanism for mixing the cleaning liquid with the treated water from the electrodialysis section. In addition to these, it may also have equipment that is ancillary to general liquid fertilizer production apparatuses.
図1では、本発明に関する設備として、電気透析部40、薬品洗浄機構43、洗浄液の第1の流路44、洗浄液の第2の流路45、洗浄液の第3の流路46を示している。
この他に、一般的な設備として、消化液タンク10、膜分離部20、処理水タンク30、第1の流路11、第2の流路21、第3の流路31等を示している。
In FIG. 1, an
In addition, as general equipment, a digestive
無機態窒素は、前述した通り、(1)アンモニア態窒素、(2)硝酸態窒素及び亜硝酸態窒素に大別される。本発明の液体肥料は、前記無機態窒素を含有する液体肥料である。
ここで硝酸態窒素とは、硝酸又は硝酸塩を指す。
As described above, inorganic nitrogen is roughly classified into (1) ammonia nitrogen, and (2) nitrate nitrogen and nitrite nitrogen. The liquid fertilizer of the present invention is a liquid fertilizer containing the inorganic nitrogen.
Here, nitrate nitrogen refers to nitric acid or nitrates.
<消化液>
本発明で用いる消化液は、有機物の消化液であり、し尿等の有機物を発酵処理した後の液である。
消化液としては、嫌気性発酵の消化液、好気性発酵の消化液が挙げられる。嫌気性発酵の消化液とは、空気を遮断した無酸素の状態下で発酵処理した液である。好気性発酵の消化液とは、空気で曝気した状態下での発酵処理液である。
<Digestive fluids>
The digestive fluid used in the present invention is a digestive fluid of organic matter, and is a liquid obtained after fermentation of organic matter such as human waste.
The digestive liquid includes digestive liquid from anaerobic fermentation and digestive liquid from aerobic fermentation. The digestive liquid from anaerobic fermentation is a liquid fermented under oxygen-free conditions with air blocked off. The digestive liquid from aerobic fermentation is a liquid fermented under air aeration conditions.
<被処理液>
電気透析部で処理される被処理液は、有機物の消化液を原料とするものであればよい。
有機物の消化液を直接、電気透析部で処理することも可能ではあるが、電気透析部の閉塞を避けるためにも、電気透析処理をする前に、前処理を実施することが好ましい。
前処理としては、例えば、砂濾過、沈降分離、精密濾過膜又は限外濾過膜等の膜を用いた膜分離、メンブレンバイオリアクターが挙げられる。
これらの中では、液体肥料が含有する無機態窒素の組成比を調節可能であることから、メンブレンバイオリアクターが好ましい。
<Liquid to be treated>
The liquid to be treated in the electrodialysis section may be any liquid whose raw material is digested liquid of organic matter.
Although it is possible to treat the organic digestive liquid directly in the electrodialysis section, it is preferable to carry out pretreatment before electrodialysis in order to avoid clogging of the electrodialysis section.
Examples of pretreatment include sand filtration, sedimentation, membrane separation using a membrane such as a microfiltration membrane or an ultrafiltration membrane, and a membrane bioreactor.
Among these, the membrane bioreactor is preferred because it is possible to adjust the composition ratio of inorganic nitrogen contained in the liquid fertilizer.
メンブレンバイオリアクターは、「膜分離活性汚泥法」とも称される。
メンブレンバイオリアクターは、処理水と活性汚泥の入った処理槽と、精密濾過膜又は限外濾過膜等の膜を用いるものである。
メンブレンバイオリアクターで、消化液を活性汚泥で処理することにより、好気性細菌による硝化が進行し、アンモニア態窒素が、硝酸態窒素及び亜硝酸態窒素に変換される。処理後の消化液は前記膜で濾過され、前記膜を透過した分離液が電気透析部に送られる。
これ以降、「メンブレンバイオリアクター」を、「MBR」と称する場合もある。
The membrane bioreactor is also called a "membrane separation activated sludge process."
A membrane bioreactor uses a treatment tank containing treated water and activated sludge, and a membrane such as a microfiltration membrane or an ultrafiltration membrane.
In the membrane bioreactor, the digestive liquid is treated with activated sludge, whereby nitrification by aerobic bacteria progresses and ammonia nitrogen is converted into nitrate nitrogen and nitrite nitrogen. The treated digestive liquid is filtered through the membrane, and the separated liquid that permeates the membrane is sent to the electrodialysis section.
Hereinafter, "membrane bioreactor" may be referred to as "MBR."
<電気透析部>
本発明の電気透析部は、膜分離部で濾過された分離液を濃縮する。電気透析部としては、公知の電気透析装置を用いればよい。
電気透析装置としては、例えば、AGCエンジニアリング社製のDW-1が挙げられる。
<Electrodialysis section>
The electrodialysis unit of the present invention concentrates the separated liquid filtered in the membrane separation unit. As the electrodialysis unit, a known electrodialysis device may be used.
An example of the electrodialysis device is DW-1 manufactured by AGC Engineering Co., Ltd.
電気透析装置とは、陽イオン交換膜と陰イオン交換膜を交互に、スペーサーを介して多数組積層し、その両端に1対の電極を配置し、陽極側の陰イオン交換膜と陰極側の陽イオン交換膜で仕切られたスペースである脱塩室(D室)と、それとは反対に陽極側の陽イオン交換膜と陰極側の陰イオン交換膜で仕切られたスペースである濃縮室(C室)が交互に配置されたものである。
D室に原液を供給すると陽イオンは陰極に向かって陽イオン交換膜を透過して陰極よりのC室に移動する。その際、C室の陰極側は陰イオン交換膜で仕切られているため、さらに隣のD室に移動することはできない。
同様に、陰イオンはD室から陽極側のC室に移動する。結果としてD室で脱塩され、C室で濃縮される。
An electrodialysis device is a device in which multiple sets of cation exchange membranes and anion exchange membranes are alternately stacked with spacers between them, with a pair of electrodes disposed at both ends, and deionization chambers (chambers D), which are spaces partitioned by the anion exchange membrane on the anode side and the cation exchange membrane on the cathode side, and concentration chambers (chambers C), which are spaces partitioned by the cation exchange membrane on the anode side and the anion exchange membrane on the cathode side, are arranged alternately.
When the stock solution is supplied to compartment D, the cations pass through the cation exchange membrane toward the cathode and move to compartment C, which is closer to the cathode. At that time, the cathode side of compartment C is separated by an anion exchange membrane, so the cations cannot move further to the adjacent compartment D.
Similarly, anions move from compartment D to compartment C on the anode side. As a result, they are desalted in compartment D and concentrated in compartment C.
電気透析部では、処理対象である分離液を、電気透析濃縮液と、電気透析脱塩液に分ける。電気透析濃縮液は、処理前の分離液よりも塩濃度が高く、電気透析脱塩液は、処理前の分離液よりも塩濃度が低い。 In the electrodialysis section, the separated liquid to be treated is separated into an electrodialysis concentrate and an electrodialysis desalted liquid. The electrodialysis concentrate has a higher salt concentration than the separated liquid before treatment, and the electrodialysis desalted liquid has a lower salt concentration than the separated liquid before treatment.
被処理液にリン酸成分とカルシウム成分が含まれる場合、これらの成分が電気透析の工程で反応してリン酸カルシウムを形成する。
例えば、被処理液中に、水溶性のリン酸塩と、水溶性のカルシウム塩を含む場合、電気透析の工程でリン酸イオンとカルシウムイオンが反応して、水に対して不溶性のリン酸カルシウムを形成する。このリン酸カルシウムがイオン交換膜に付着することで、イオン交換膜の閉塞が起こり得る。
このイオン交換膜に付着したリン酸カルシウムを除去するため、酸性薬剤でイオン交換膜を洗浄することが一般的であり、従来はコスト的なメリットから塩酸が用いられてきた。
When the liquid to be treated contains phosphoric acid and calcium components, these components react with each other in the electrodialysis process to form calcium phosphate.
For example, when the liquid to be treated contains a water-soluble phosphate salt and a water-soluble calcium salt, the phosphate ions react with the calcium ions in the electrodialysis process to form water-insoluble calcium phosphate, which may adhere to the ion exchange membrane and cause clogging of the ion exchange membrane.
In order to remove calcium phosphate adhering to the ion exchange membrane, the ion exchange membrane is generally washed with an acidic agent, and hydrochloric acid has traditionally been used due to its cost advantage.
<薬品洗浄機構>
本発明の薬品洗浄機構は、電気透析部のイオン交換膜を薬品洗浄する機構であり、イオン交換膜の閉塞時に、硝酸を用いてイオン交換膜を薬品洗浄する機構である。
薬品洗浄機構は、イオン交換膜の閉塞を検知し、イオン交換膜の閉塞時に必要量の硝酸を供給できるものであればよく、自動の洗浄機構でも、手動の洗浄機構でもよい。
薬品洗浄機構は、硝酸に耐性があることが必要であるが、それ以外の点では、公知の機構を用いればよい。
<Chemical cleaning mechanism>
The chemical cleaning mechanism of the present invention is a mechanism for chemically cleaning the ion exchange membrane of the electrodialysis section, and is a mechanism for chemically cleaning the ion exchange membrane by using nitric acid when the ion exchange membrane is clogged.
The chemical cleaning mechanism may be any mechanism capable of detecting clogging of the ion exchange membrane and supplying a required amount of nitric acid when the ion exchange membrane is clogged, and may be an automatic cleaning mechanism or a manual cleaning mechanism.
The chemical cleaning mechanism must be resistant to nitric acid, but in other respects, any known mechanism may be used.
<硝酸>
薬品洗浄機構で用いる硝酸は、特に限定されるものではなく、市販の硝酸であればよい。
硝酸の純度は、特に限定されるものではない。
硝酸の濃度も、特に限定されるものではないが、イオン交換膜を含む電気透析部に使用されている部材の耐薬品性と、電気透析部の接液部の洗浄効果の点から、0.5~5質量%であることが好ましい。
<Nitric acid>
The nitric acid used in the chemical cleaning mechanism is not particularly limited, and any commercially available nitric acid may be used.
The purity of the nitric acid is not particularly limited.
The concentration of nitric acid is not particularly limited, but is preferably 0.5 to 5 mass % from the viewpoints of the chemical resistance of the members used in the electrodialysis unit, including the ion exchange membrane, and the cleaning effect of the liquid-contacting parts of the electrodialysis unit.
<洗浄液>
本発明で得られる洗浄液は、電気透析部のイオン交換膜を硝酸で洗浄したものであり、その成分としては、イオン交換膜の閉塞物であったリン酸カルシウムが溶解して生じたリン酸イオンとカルシウムイオン、そして硝酸イオンを含む。硝酸を用いていることから、洗浄液は、酸性を示す。
なお、ここではイオン交換膜の閉塞物をリン酸カルシウムとしているが、閉塞物はリン酸カルシウムに限定されるものではない。消化液に含まれる成分により、リン酸マグネシウムや炭酸カルシウム等が閉塞物となる場合もあり、洗浄液に含まれる成分は様々である。
<Cleaning solution>
The cleaning solution obtained in the present invention is obtained by cleaning the ion exchange membrane of the electrodialysis unit with nitric acid, and contains as its components phosphate ions and calcium ions produced by dissolving calcium phosphate, which was a blockage in the ion exchange membrane, and nitrate ions. Because nitric acid is used, the cleaning solution is acidic.
In this example, the blocking material in the ion exchange membrane is calcium phosphate, but the blocking material is not limited to calcium phosphate. Depending on the components contained in the digestive fluid, magnesium phosphate, calcium carbonate, etc. may become blocking material, and the components contained in the cleaning fluid are various.
硝酸イオンは、液体肥料が含有する無機態窒素の1つである硝酸態窒素であり、リン酸イオンは、肥料成分として有用なリン成分であることから、本発明で得られる洗浄液は、液体肥料として有用な成分を含んでいる。このため、この洗浄液も液体肥料として利用できる。
従来の塩酸を用いた洗浄液は、塩素イオンを含むことから肥料としては不適切であり、液体肥料として利用することは困難であった。
本発明の洗浄液を液体肥料として利用するには、洗浄液を電気透析部の前段に戻す場合と、洗浄液を電気透析部の電気透析濃縮液と配合する場合がある。
Nitrate ions are nitrate nitrogen, which is one of the inorganic nitrogens contained in liquid fertilizers, and phosphate ions are phosphorus components that are useful as fertilizer components, so the cleaning solution obtained in the present invention contains components that are useful as liquid fertilizers, and therefore this cleaning solution can also be used as liquid fertilizer.
Conventional cleaning solutions using hydrochloric acid contain chloride ions, making them unsuitable as fertilizers, and it has been difficult to use them as liquid fertilizers.
To utilize the cleaning solution of the present invention as a liquid fertilizer, the cleaning solution may be returned to the upstream stage of the electrodialysis section, or may be mixed with the concentrated electrodialysis solution in the electrodialysis section.
洗浄液を電気透析部の前段に戻す場合としては、例えば、図1に示す消化液タンク10に戻す場合、膜分離部20に戻す場合、処理水タンク30に戻す場合が挙げられる。
なお、洗浄液を戻す場所は限定されるものではなく、電気透析部の前段であればよい。
The cleaning liquid may be returned to the upstream stage of the electrodialysis section, for example, to the
The place where the cleaning liquid is returned is not limited, and may be any place upstream of the electrodialysis section.
洗浄液を膜分離部20に戻す場合、図1に示す洗浄液の第1の流路44に代表される、洗浄液を膜分離部20に戻す機構を設ければよい。
洗浄液を膜分離部20に戻す場合、洗浄液が酸性であることから、膜分離部の処理に影響を与える可能性がある。
例えば、膜分離部がMBRである場合、酸性の洗浄液を戻すことでMBRでの消化液の処理pHが変動し、MBRでの硝化の進行に影響を与える可能性がある。反対に、MBRの消化液のpHが高い(アルカリ性)場合には、酸性の洗浄液をpH調節剤として用いることができる。
When returning the cleaning liquid to the
When the cleaning liquid is returned to the
For example, when the membrane separation unit is an MBR, returning the acidic washing liquid may cause the pH of the digestive liquid in the MBR to fluctuate, which may affect the progress of nitrification in the MBR. Conversely, when the pH of the digestive liquid in the MBR is high (alkaline), the acidic washing liquid can be used as a pH adjuster.
洗浄液を処理水タンク30に戻す場合、図1に示す洗浄液の第2の流路45に代表される、洗浄液を処理水タンク30に戻す機構を設ければよい。
洗浄液を処理水タンク30に戻す場合、洗浄液が酸性であることの影響を受けない設計をしておくことが好ましい。例えば、処理水タンクの容量を大きくすること、処理水タンク内のpHを監視して洗浄液を戻すタイミングを制御すること、が挙げられる。
洗浄液を処理水タンクに戻した後は、特段の処理を必要とせず、そのまま電気透析部に送り、電気透析処理をすればよい。
In the case where the cleaning liquid is returned to the treated
When returning the cleaning liquid to the treated
After the cleaning solution is returned to the treated water tank, no special treatment is required, and it may be sent directly to the electrodialysis section for electrodialysis treatment.
洗浄液を電気透析部の電気透析濃縮液と配合する場合、図1に示す洗浄液の第3の流路46に代表される、洗浄液を電気透析濃縮液と配合する機構を設ければよい。
洗浄液を電気透析濃縮液と配合する場合、洗浄液が酸性であることから、得られる液体肥料のpHが変動する可能性はあるが、電気透析濃縮液のpH変動の影響は小さいため、新たに電気透析濃縮液のpHを調整する必要はない。
When the cleaning liquid is mixed with the electrodialysis concentrate in the electrodialysis section, a mechanism for mixing the cleaning liquid with the electrodialysis concentrate, as represented by the third cleaning
When the cleaning solution is mixed with the electrodialysis concentrate, the pH of the resulting liquid fertilizer may fluctuate because the cleaning solution is acidic. However, since the effect of the pH fluctuation of the electrodialysis concentrate is small, there is no need to adjust the pH of the electrodialysis concentrate.
本発明の洗浄液を液体肥料として利用するには、洗浄液が酸性であることの影響を受けず、特段の処理を必要としないことから、洗浄液を処理水タンク30に戻すことが好ましい。
上述の通り、本発明の液体肥料製造装置は、薬品洗浄で発生した洗浄液を、液体肥料の成分として利用することを特徴とする。
また、本発明の液体肥料製造装置は、薬品洗浄で発生した洗浄液を、外部に排出しないことを特徴とする。
In order to utilize the cleaning solution of the present invention as liquid fertilizer, it is preferable to return the cleaning solution to the treated
As described above, the liquid fertilizer manufacturing apparatus of the present invention is characterized in that the cleaning liquid generated during chemical cleaning is utilized as a component of liquid fertilizer.
The liquid fertilizer manufacturing apparatus of the present invention is also characterized in that the cleaning liquid generated during the chemical cleaning is not discharged to the outside.
<液体肥料製造方法>
本発明の液体肥料製造方法は、有機物の消化液を原料として、無機態窒素を含有する液体肥料を製造する液体肥料製造方法であって、下記工程(1)及び(2)を有する;
工程(1):被処理液を濃縮する電気透析工程、
工程(2):該電気透析工程のイオン交換膜の閉塞時に、硝酸を用いて該イオン交換膜を薬品洗浄する薬品洗浄工程。
<Liquid fertilizer manufacturing method>
The liquid fertilizer production method of the present invention is a liquid fertilizer production method for producing a liquid fertilizer containing inorganic nitrogen using a digestive liquid of organic matter as a raw material, and includes the following steps (1) and (2):
Step (1): An electrodialysis step of concentrating the liquid to be treated;
Step (2): A chemical cleaning step of chemically cleaning the ion exchange membrane with nitric acid when the ion exchange membrane becomes clogged in the electrodialysis step.
<工程(1)>
工程(1)は、被処理液を濃縮する電気透析工程であり、その主旨は、液体肥料製造装置の項目で説明した「電気透析部」と同様である。
一方、工程(1)においては、電気透析部ではなく、電気透析工程としていることからも明らかなように、電気透析部という特定の設備を指すものではなく、電気透析する操作、電気透析する行為も含めて、電気透析工程とする。
<Step (1)>
Step (1) is an electrodialysis step for concentrating the liquid to be treated, and its gist is the same as that of the "electrodialysis section" explained in the section on the liquid fertilizer production apparatus.
On the other hand, as is clear from the fact that it is referred to as an electrodialysis step rather than an electrodialysis unit in step (1), the electrodialysis step does not refer to a specific facility called an electrodialysis unit, but includes the operation and act of electrodialysis.
<工程(2)>
工程(2)は、電気透析工程のイオン交換膜の閉塞時に、硝酸を用いて該イオン交換膜を薬品洗浄する薬品洗浄工程であり、その主旨は、液体肥料製造装置の項目で説明した「薬品洗浄機構」と同様である。
一方、工程(2)においては、薬品洗浄機構ではなく、薬品洗浄工程としていることからも明らかなように、薬品洗浄機構という特定の設備を指すものではなく、薬品洗浄する操作、薬品洗浄する行為も含めて、薬品洗浄工程とする。
<Step (2)>
Step (2) is a chemical cleaning step in which nitric acid is used to chemically clean the ion exchange membrane when it becomes clogged during the electrodialysis step. The gist of this step is the same as the "chemical cleaning mechanism" described in the section on the liquid fertilizer production equipment.
On the other hand, as is clear from the fact that it is referred to as a chemical cleaning process rather than a chemical cleaning mechanism in process (2), the chemical cleaning process does not refer to a specific piece of equipment called a chemical cleaning mechanism, but rather includes the operation and act of chemical cleaning.
<洗浄液を電気透析工程の前段に戻す工程>
洗浄液を電気透析工程の前段に戻す工程の主旨は、液体肥料製造装置の項目で説明した内容と同様である。
一方、液体肥料製造方法の発明においては、「工程」としていることからも明らかなように、洗浄液を電気透析部の前段に戻す特定の設備を指すものではなく、洗浄液を電気透析工程の前段に戻す操作、洗浄液を電気透析工程の前段に戻す行為も含めて、洗浄液を電気透析工程の前段に戻す工程とする。
<Step of returning the cleaning solution to the front stage of the electrodialysis step>
The purpose of the process of returning the cleaning liquid to the upstream stage of the electrodialysis process is the same as that explained in the section on the liquid fertilizer manufacturing apparatus.
On the other hand, in the invention of the liquid fertilizer manufacturing method, as is clear from the term "process," the process of returning the cleaning liquid to the upstream stage of the electrodialysis section does not refer to a specific facility for returning the cleaning liquid to the upstream stage of the electrodialysis process, but includes the operation of returning the cleaning liquid to the upstream stage of the electrodialysis process and the act of returning the cleaning liquid to the upstream stage of the electrodialysis process.
<洗浄液を電気透析工程の電気透析濃縮液と配合する工程>
洗浄液を電気透析濃縮液と配合する工程の主旨は、液体肥料製造装置の項目で説明した内容と同様である。
一方、液体肥料製造方法の発明においては、「工程」としていることからも明らかなように、洗浄液を電気透析濃縮液と配合する特定の設備を指すものではなく、洗浄液を電気透析濃縮液と配合する操作、洗浄液を電気透析濃縮液と配合する行為も含めて、洗浄液を電気透析濃縮液と配合する工程とする。
<Step of blending the cleaning solution with the electrodialysis concentrate from the electrodialysis step>
The purpose of the process of mixing the cleaning liquid with the electrodialysis concentrate is the same as that described in the section on the liquid fertilizer production apparatus.
On the other hand, in the invention of the liquid fertilizer production method, as is clear from the term "step," the step does not refer to a specific facility for mixing the cleaning liquid with the electrodialysis concentrate, but includes the operation of mixing the cleaning liquid with the electrodialysis concentrate and the act of mixing the cleaning liquid with the electrodialysis concentrate.
上述の通り、本発明の液体肥料製造方法は、薬品洗浄で発生した洗浄液を、液体肥料の成分として利用することを特徴とする。
また、本発明の液体肥料製造方法は、薬品洗浄で発生した洗浄液を、外部に排出しないことを特徴とする。
As described above, the liquid fertilizer production method of the present invention is characterized in that the cleaning liquid generated during chemical cleaning is utilized as a component of the liquid fertilizer.
Furthermore, the liquid fertilizer manufacturing method of the present invention is characterized in that the cleaning liquid generated during the chemical cleaning is not discharged to the outside.
<液体肥料>
本発明の液体肥料は、本発明の液体肥料製造装置、又は、液体肥料製造方法で得られるものであり、無機態窒素を含有する。
液体肥料は、前記無機態窒素以外に、肥料として一般的な添加剤を後から配合してもよい。
<Liquid fertilizer>
The liquid fertilizer of the present invention is obtained by the liquid fertilizer production apparatus or the liquid fertilizer production method of the present invention, and contains inorganic nitrogen.
In addition to the inorganic nitrogen, the liquid fertilizer may contain other additives that are generally used as fertilizers.
<用途>
本発明における液体肥料は、一般的な肥料として使用可能であるが、特に、植物の生育条件や植物の種類に応じた、土耕及び水耕栽培における元肥、追肥として好適に用いられる。
<Applications>
The liquid fertilizer of the present invention can be used as a general fertilizer, but is particularly suitable for use as a base fertilizer or top dressing in soil culture or hydroponic culture depending on the growing conditions and type of plant.
以下に実施例を示し、本発明を更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例により限定されるものではない。
以下の実施例及び比較例においては、下記の方法により各種物性を測定した。
The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
In the following examples and comparative examples, various physical properties were measured by the following methods.
[評価方法]
(1)電気伝導度
堀場製作所社製「HE-480H」を使用し、電気伝導度を測定した。
[Evaluation method]
(1) Electrical Conductivity Electrical conductivity was measured using "HE-480H" manufactured by Horiba, Ltd.
[実施例]
原水として、有機物の消化液を用いた。この消化液は、し尿由来の好気発酵消化液である。
膜分離部として、三菱ケミカル社製の限外濾過膜(膜素材:ポリフッ化ビニリデン、公称孔径0.05μm、膜形状:中空糸)を備えた、容積2m3の水槽を用いた。
消化液を水槽に投入し、限外濾過膜を消化液に浸漬させた。この状態で、連続で吸引濾過をして、限外濾過膜で濾過された分離液と、濾過されなかった汚泥を含む分散液に分けた。
得られた分離液の電気伝導度は7mS/cmであった。分離液の電気伝導度は、液体肥料の有用成分である窒素、リン酸、カリウム等の溶解成分の濃度に比例する。
得られた分離液を処理水タンクに貯槽した。
[Example]
The raw water used was a digestive liquid of organic matter, which was a digestive liquid derived from aerobic fermentation of human waste.
As the membrane separation section, a water tank having a volume of 2 m3 and equipped with an ultrafiltration membrane manufactured by Mitsubishi Chemical Corporation (membrane material: polyvinylidene fluoride, nominal pore size: 0.05 μm, membrane shape: hollow fiber) was used.
The digestive liquid was poured into a water tank and the ultrafiltration membrane was immersed in the digestive liquid. In this state, continuous suction filtration was performed to separate the separated liquid filtered through the ultrafiltration membrane from a dispersion containing sludge that was not filtered.
The electrical conductivity of the separated liquid was 7 mS/cm. The electrical conductivity of the separated liquid is proportional to the concentration of dissolved components such as nitrogen, phosphoric acid, and potassium, which are useful components of the liquid fertilizer.
The separated liquid obtained was stored in a treated water tank.
分離液を被処理水とし、AGCエンジニアリング社製の電気透析装置「DW-1型」(カチオンイオン交換膜:CMVN、アニオンイオン交換膜:AMVN)で処理した。電気透析電圧は13~15Vとし、電気透析濃縮液と電気透析脱塩液に分けた。
電気透析脱塩液は、1.1m3/hの流量で処理水タンクに戻し、循環運転とした。
The separated liquid was treated as water to be treated with an electrodialysis device "DW-1 type" (cation ion exchange membrane: CMVN, anion ion exchange membrane: AMVN) manufactured by AGC Engineering Co., Ltd. The electrodialysis voltage was set to 13 to 15 V, and the separated liquid was separated into an electrodialysis concentrate and an electrodialysis desalted liquid.
The electrodialysis desalted liquid was returned to the treated water tank at a flow rate of 1.1 m 3 /h for circulating operation.
図2に示すように、2022年の6月8日に電気透析の連続運転を開始した。このときの電気透析電圧は15Vである。
連続運転を継続することで、電気伝導度から算出した濃縮倍率(EC濃縮倍率)が低下する傾向が見られた。この濃縮倍率の低下は、電気透析装置のイオン交換膜の閉塞によるものである。イオン交換膜の閉塞時には、電気透析濃縮液側に液が流出せず、濃縮率は低下する。
As shown in Figure 2, continuous operation of electrodialysis was started on June 8, 2022. The electrodialysis voltage at this time was 15V.
As the operation continued, the concentration ratio calculated from the electrical conductivity (EC concentration ratio) tended to decrease. This decrease in concentration ratio was due to the clogging of the ion exchange membrane of the electrodialysis device. When the ion exchange membrane was clogged, no liquid flowed out to the electrodialysis concentrate side, and the concentration ratio decreased.
電気透析濃縮液の電気伝導度が46.1mS/cmまで低下し、EC濃縮倍率が6.6倍となったところで、電気透析装置の運転を停止した。
濃度1.5質量%の硝酸水溶液50Lを用意し、電気透析装置の濃縮液側の出口と、電気透析装置の入口の循環運転とすることで、イオン交換膜を薬品洗浄した。
その後、水洗、濃度1質量%のNaOH水溶液での洗浄、水洗を経て、電圧13Vで電気透析の連続運転を再開した。再開時の電気透析濃縮液の電気伝導度は81.6mS/cm、EC濃縮倍率は11.7倍まで回復しており、硝酸洗浄によってイオン交換膜の閉塞が解消したことを確認した。詳細は表1及び図2に示す。
When the electrical conductivity of the electrodialysis concentrate had decreased to 46.1 mS/cm and the EC concentration rate had reached 6.6 times, the operation of the electrodialysis apparatus was stopped.
50 L of an aqueous solution of nitric acid having a concentration of 1.5% by mass was prepared, and the solution was circulated between the outlet of the concentrated liquid side of the electrodialysis device and the inlet of the electrodialysis device, thereby chemically cleaning the ion exchange membrane.
Thereafter, the electrodialysis was washed with water, washed with a 1% by mass aqueous NaOH solution, and washed with water again, and then the continuous operation of electrodialysis was resumed at a voltage of 13 V. When the electrodialysis concentrate was resumed, the electrical conductivity was 81.6 mS/cm, and the EC concentration rate had recovered to 11.7 times, confirming that the clogging of the ion exchange membrane was eliminated by the nitric acid washing. Details are shown in Table 1 and FIG. 2.
連続運転を継続し、8月24日には濃度2質量%の硝酸水溶液を用いてイオン交換膜を薬品洗浄した。9月26日には濃度1質量%の硝酸水溶液を用いてイオン交換膜を薬品洗浄した。いずれの場合も薬品洗浄後の運転再開でEC濃縮倍率は回復しており、各種濃度の硝酸洗浄によってイオン交換膜の閉塞が解消したことを確認した。 Continuing the operation, the ion exchange membrane was chemically cleaned using a 2% by mass aqueous solution of nitric acid on August 24th. On September 26th, the ion exchange membrane was chemically cleaned using a 1% by mass aqueous solution of nitric acid. In both cases, the EC concentration ratio was restored when operation was resumed after the chemical cleaning, and it was confirmed that the blockage of the ion exchange membrane was eliminated by cleaning with nitric acid at various concentrations.
さらに連続運転を継続し、11月14日には濃度3質量%の塩酸水溶液を用いてイオン交換膜を薬品洗浄した。薬品洗浄後の運転再開でEC濃縮倍率は回復した。この回復の程度は、硝酸洗浄と塩酸洗浄で差が見られなかったことから、硝酸を用いた場合であっても、従来の塩酸を用いる場合と同様に、イオン交換膜の閉塞を解消できることを確認した。
また、硝酸を用いてイオン交換膜を洗浄した場合、洗浄液には液体肥料として有用な成分が含まれることから、洗浄液を液体肥料として利用できることを確認した。
The operation was continued, and on November 14, the ion exchange membrane was chemically washed using a 3% by mass aqueous hydrochloric acid solution. The EC concentration ratio recovered when operation was resumed after the chemical washing. Since there was no difference in the degree of recovery between washing with nitric acid and washing with hydrochloric acid, it was confirmed that the blockage of the ion exchange membrane could be eliminated even when nitric acid was used, just as in the case of using conventional hydrochloric acid.
In addition, it was confirmed that when an ion exchange membrane is cleaned with nitric acid, the cleaning solution contains components that are useful as liquid fertilizer, and therefore the cleaning solution can be used as liquid fertilizer.
10 消化液タンク、11 第1の流路
20 膜分離部(MBR)、21 第2の流路、22 汚泥引抜流路
30 処理水タンク、31 第3の流路
40 電気透析部、41 電気透析脱塩液流路、42 電気透析濃縮液流路、43 薬品洗浄機構、44 洗浄液の第1の流路、45 洗浄液の第2の流路、46 洗浄液の第3の流路
REFERENCE SIGNS
Claims (14)
被処理液を濃縮する電気透析部と、
該電気透析部のイオン交換膜を薬品洗浄する薬品洗浄機構と、
前記薬品洗浄で発生した洗浄液を、前記電気透析部の前段に戻す機構と、を有し、
該イオン交換膜の閉塞時に、該薬品洗浄機構が硝酸を用いてイオン交換膜を薬品洗浄する、液体肥料製造装置。 A liquid fertilizer manufacturing apparatus that produces liquid fertilizer containing inorganic nitrogen using digestive liquid of organic matter as a raw material,
an electrodialysis unit for concentrating the liquid to be treated;
a chemical cleaning mechanism for chemically cleaning the ion exchange membrane of the electrodialysis unit;
A mechanism for returning the cleaning liquid generated in the chemical cleaning to a stage upstream of the electrodialysis unit ,
When the ion exchange membrane becomes clogged, the chemical cleaning mechanism uses nitric acid to chemically clean the ion exchange membrane.
被処理液を濃縮する電気透析部と、
該電気透析部のイオン交換膜を薬品洗浄する薬品洗浄機構と、
前記薬品洗浄で発生した洗浄液を、前記電気透析部から出た電気透析濃縮液と配合する機構と、を有し、
該イオン交換膜の閉塞時に、該薬品洗浄機構が硝酸を用いてイオン交換膜を薬品洗浄する、液体肥料製造装置。 A liquid fertilizer manufacturing apparatus that produces liquid fertilizer containing inorganic nitrogen using digestive liquid of organic matter as a raw material,
an electrodialysis unit for concentrating the liquid to be treated;
a chemical cleaning mechanism for chemically cleaning the ion exchange membrane of the electrodialysis unit;
a mechanism for mixing the cleaning solution generated by the chemical cleaning with the electrodialysis concentrate discharged from the electrodialysis unit,
When the ion exchange membrane becomes clogged, the chemical cleaning mechanism uses nitric acid to chemically clean the ion exchange membrane .
前記電気透析部の前段に戻す機構は、前記洗浄液を前記膜分離部に戻す機構である、請求項1に記載の液体肥料製造装置。The liquid fertilizer manufacturing apparatus according to claim 1 , wherein the mechanism for returning the cleaning solution to the upstream stage of the electrodialysis unit is a mechanism for returning the cleaning solution to the membrane separation unit.
前記電気透析部の前段に戻す機構は、前記洗浄液を前記処理水タンクに戻す機構である、請求項1に記載の液体肥料製造装置。The liquid fertilizer manufacturing apparatus according to claim 1 , wherein the mechanism for returning the cleaning solution to the upstream stage of the electrodialysis unit is a mechanism for returning the cleaning solution to the treated water tank.
被処理液を濃縮する電気透析工程と、
該電気透析工程のイオン交換膜の閉塞時に、硝酸を用いて該イオン交換膜を薬品洗浄する薬品洗浄工程とを有し、
前記薬品洗浄工程で発生した洗浄液を、液体肥料の成分として利用する、液体肥料製造方法。 A liquid fertilizer production method for producing liquid fertilizer containing inorganic nitrogen using digestive liquid of organic matter as a raw material,
an electrodialysis step of concentrating the liquid to be treated;
and a chemical cleaning step of chemically cleaning the ion exchange membrane with nitric acid when the ion exchange membrane is clogged in the electrodialysis step .
A liquid fertilizer manufacturing method, in which the cleaning liquid generated in the chemical cleaning step is utilized as a component of liquid fertilizer.
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Citations (3)
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| JP2007260561A (en) | 2006-03-28 | 2007-10-11 | Asahi Kasei Chemicals Corp | Ion processing apparatus and method |
| JP2016527162A (en) | 2013-05-02 | 2016-09-08 | イージーマイニング スウェーデン アクチエボラグ | Production of phosphate compounds from materials containing phosphorus and at least one of iron and aluminum |
| CN114560722A (en) | 2022-02-28 | 2022-05-31 | 同济大学 | A method for resource utilization of kitchen waste anaerobic fermentation liquid |
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| JP2007260561A (en) | 2006-03-28 | 2007-10-11 | Asahi Kasei Chemicals Corp | Ion processing apparatus and method |
| JP2016527162A (en) | 2013-05-02 | 2016-09-08 | イージーマイニング スウェーデン アクチエボラグ | Production of phosphate compounds from materials containing phosphorus and at least one of iron and aluminum |
| CN114560722A (en) | 2022-02-28 | 2022-05-31 | 同济大学 | A method for resource utilization of kitchen waste anaerobic fermentation liquid |
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