JP6875973B2 - How to treat marine biological resources - Google Patents
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- JP6875973B2 JP6875973B2 JP2017194676A JP2017194676A JP6875973B2 JP 6875973 B2 JP6875973 B2 JP 6875973B2 JP 2017194676 A JP2017194676 A JP 2017194676A JP 2017194676 A JP2017194676 A JP 2017194676A JP 6875973 B2 JP6875973 B2 JP 6875973B2
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- 229910001385 heavy metal Inorganic materials 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 229910052785 arsenic Inorganic materials 0.000 claims description 38
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 37
- 241001474374 Blennius Species 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 239000013535 sea water Substances 0.000 claims description 11
- 235000015170 shellfish Nutrition 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003337 fertilizer Substances 0.000 claims description 3
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 description 22
- 239000002245 particle Substances 0.000 description 9
- 229910052793 cadmium Inorganic materials 0.000 description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 8
- 239000002440 industrial waste Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 241000195474 Sargassum Species 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 235000014102 seafood Nutrition 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 241000237536 Mytilus edulis Species 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000020638 mussel Nutrition 0.000 description 2
- 210000001835 viscera Anatomy 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000219995 Wisteria Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Description
本発明は、海洋生物資源の処理方法に関する。 The present invention relates to a method for treating marine biological resources.
海水は、食塩やアルカリ金属等を得るための原料や、生活用水、バラスト水、冷却水等に用いられている。海水を得る際には、取水時期や取水場所に応じて様々な海洋生物資源が混入する場合がある。海水の取水時に混入する海洋生物資源としては、海藻類や貝類が挙げられる。 Seawater is used as a raw material for obtaining salt, alkali metals, etc., as well as domestic water, ballast water, cooling water, and the like. When obtaining seawater, various marine biological resources may be mixed depending on the time and place of intake. Examples of marine biological resources mixed in when seawater is taken include seaweeds and shellfish.
海水の取水時に混入するこれらの海洋生物資源は、一般的に産業廃棄物として処理される。海洋生物資源が産業廃棄物として処理される際には、減容化及び腐敗臭の抑制を目的として、海洋生物資源に対して乾燥処理が施される。 These marine biological resources mixed in during the intake of seawater are generally treated as industrial waste. When marine biological resources are treated as industrial waste, they are dried for the purpose of volume reduction and suppression of putrefactive odor.
海藻類にはヒ素が多く含まれ、貝類の貝肉、内臓又はウロにはヒ素、カドミウム、６価クロム等が含まれていることが知られている。また、海洋生物資源のヒ素含有量が多いと、海洋生物資源のヒ素溶出量が増大する傾向がある。このため、海洋生物資源がヒ素を多く含む場合には、乾燥後の海洋生物資源のヒ素溶出量が、産業廃棄物として廃棄可能な法定の基準値を超過することがある。 It is known that seaweeds contain a large amount of arsenic, and shellfish meat, internal organs or uro contain arsenic, cadmium, hexavalent chromium and the like. In addition, when the arsenic content of marine biological resources is high, the arsenic elution amount of marine biological resources tends to increase. Therefore, when marine biological resources contain a large amount of arsenic, the amount of arsenic eluted from the marine biological resources after drying may exceed the legal standard value that can be disposed of as industrial waste.
海洋生物資源中のヒ素は、海洋生物資源が水に浸漬される場合に水中に溶出する。このため、例えば海洋生物資源を沸騰したお湯に投入した後、この海洋生物資源を水洗する処理が採用されれば、海洋生物資源のヒ素含有量は低減される。しかしながら、この処理が採用される場合には、お湯を用意するために多大なエネルギーが必要となり、さらにはヒ素を含有している使用後のお湯及び水洗水の後処理が必要となる。 Arsenic in marine biological resources elutes into water when marine biological resources are immersed in water. Therefore, for example, if a treatment of washing the marine biological resources with water after putting the marine biological resources into boiling water is adopted, the arsenic content of the marine biological resources will be reduced. However, when this treatment is adopted, a large amount of energy is required to prepare hot water, and further, post-treatment of arsenic-containing hot water after use and washing water is required.
一方、魚介廃棄物に菌類を加える魚介廃棄物の処理方法が提案されている（特許文献１）。特許文献１は、魚介廃棄物に加えられた硫化菌、硝酸菌、亜硝酸菌が、魚介廃棄物中に残留しているヒ素やカドミウムを分解し、分解されたヒ素やカドミウムを大気中に放出することにより、魚介廃棄物中の重金属類を除去できるとしている。しかしながら、特許文献１の処理方法は、菌類の活動を活発にするための温度管理を必要とし、さらには処理に多大な時間を必要とする。 On the other hand, a method for treating seafood waste in which fungi are added to the seafood waste has been proposed (Patent Document 1). In Patent Document 1, sulfide bacteria, nitrifying bacteria, and nitrite bacteria added to seafood waste decompose arsenic and cadmium remaining in seafood waste, and release the decomposed arsenic and cadmium into the atmosphere. By doing so, heavy metals in seafood waste can be removed. However, the treatment method of Patent Document 1 requires temperature control for activating the activity of fungi, and further requires a large amount of time for treatment.
本発明は、上述のような事情に基づいてなされたものであり、重金属類の溶出量を抑制した海洋生物資源を比較的容易に生成できる海洋生物資源の処理方法を提供することを目的とする。 The present invention has been made based on the above circumstances, and an object of the present invention is to provide a method for treating marine biological resources capable of relatively easily producing marine biological resources in which the amount of elution of heavy metals is suppressed. ..
上記課題を解決するためになされた発明は、海水の取水時に混入する海藻類又は貝類を含む海洋生物資源の処理方法であって、水分を含む上記海洋生物資源に重金属類不溶化剤を混合する工程と、上記混合工程後の混合物を乾燥する工程とを備える。 The invention made to solve the above problems is a method for treating marine biological resources including seaweeds or shellfish mixed during the intake of seawater, and is a step of mixing a heavy metal insolubilizer with the above marine biological resources containing water. And a step of drying the mixture after the mixing step.
海洋生物資源に含まれる重金属類は、海洋生物資源が水分を含むことによって、この水分に溶出する。当該海洋生物資源の処理方法は、水分を含んだ状態の海洋生物資源に重金属類不溶化剤を混合する工程を備えているので、海洋生物資源から水分へ重金属類を溶出させた状態で水分に溶出した重金属類を不溶化する。そして当該海洋生物資源の処理方法は、重金属類を不溶化した状態で重金属類不溶化剤を混合した海洋生物資源を乾燥するので、多大なエネルギーや水洗水を必要とせず、重金属類の溶出量を抑制した海洋生物資源を比較的容易に生成できる。 Heavy metals contained in marine biological resources are eluted into this water when the marine biological resources contain water. Since the method for treating marine biological resources includes a step of mixing a heavy metal insolubilizer with the marine biological resources containing water, the heavy metals are eluted from the marine biological resources into water and then eluted into water. Insolubilizes heavy metals. The method for treating marine biological resources dries marine biological resources mixed with heavy metal insolubilizers in a state where heavy metals are insolubilized, so that a large amount of energy or washing water is not required and the amount of heavy metals elution is suppressed. It is relatively easy to generate the marine biological resources.
当該海洋生物資源の処理方法は、上記混合工程前に、水分を含む上記海洋生物資源を加熱する工程をさらに備えるとよい。これにより、当該海洋生物資源の処理方法は、海洋生物資源の重金属類の含有量を大幅に減少させ、水分へ溶出した重金属類を不溶化することにより、重金属類の溶出量を十分に抑制した海洋生物資源を生成できる。 The method for treating the marine biological resource may further include a step of heating the marine biological resource containing water before the mixing step. As a result, the method for treating marine biological resources significantly reduces the content of heavy metals in marine biological resources and insolubilizes the heavy metals eluted in water, thereby sufficiently suppressing the elution amount of heavy metals in the ocean. Can generate biological resources.
上記海洋生物資源がヒ素を含むとよい。これにより、当該海洋生物資源の処理方法は、ヒ素の溶出量を抑制した海洋生物資源を生成できる。 The above marine biological resources should contain arsenic. As a result, the method for treating marine biological resources can generate marine biological resources in which the amount of arsenic elution is suppressed.
上記重金属類不溶化剤が鉄粉であるとよい。鉄は、ヒ素に加えて、鉛、カドミウム、６価クロム、セレン等を吸着により不溶化できるので、当該海洋生物資源の処理方法は、これらの重金属類の溶出量を抑制した海洋生物資源を生成できる。 It is preferable that the heavy metal insolubilizer is iron powder. Since iron can insolubilize lead, cadmium, hexavalent chromium, selenium, etc. by adsorption in addition to arsenic, the method for treating marine biological resources can generate marine biological resources in which the elution amount of these heavy metals is suppressed. ..
本発明の海洋生物資源の処理方法は、重金属類の溶出量を抑制した海洋生物資源を比較的容易に生成できる。 The method for treating marine biological resources of the present invention can relatively easily generate marine biological resources in which the amount of elution of heavy metals is suppressed.
以下、本発明に係る海洋生物資源の処理方法の実施形態について詳説する。 Hereinafter, embodiments of the method for treating marine biological resources according to the present invention will be described in detail.
当該海洋生物資源の処理方法は、海水の取水時に混入する海藻類又は貝類を含む海洋生物資源の処理方法であり、図１に示すように、水分を含む海洋生物資源を加熱する加熱工程Ｓ１と、水分を含む海洋生物資源に重金属類不溶化剤を混合する混合工程Ｓ２と、混合工程Ｓ２後の混合物を乾燥する乾燥工程Ｓ３とを備えている。ここで、水分を含む海洋生物資源とは、未乾燥であり、海水又は水洗水が付着した状態の海洋生物資源を示す。 The method for treating marine biological resources is a method for treating marine biological resources including seaweeds or shellfish mixed during the intake of seawater, and as shown in FIG. 1, the heating step S1 for heating the marine biological resources containing water A mixing step S2 for mixing a heavy metal insolubilizer with a marine biological resource containing water and a drying step S3 for drying the mixture after the mixing step S2 are provided. Here, the marine biological resource containing water refers to a marine biological resource that is undried and has seawater or flush water attached.
＜加熱工程＞
加熱工程Ｓ１は、水分を含んだ状態の海洋生物資源を加熱する工程であり、海洋生物資源に含まれる重金属類の水分への溶出を促すために実施される。水分を含む海洋生物資源の加熱には、特に限定されないが、例えば太陽光の吸収による発熱、化石燃料の燃焼熱、発電所等のプラントからの排熱、地熱等が用いられる。
<Heating process>
The heating step S1 is a step of heating a marine biological resource in a state of containing water, and is carried out in order to promote elution of heavy metals contained in the marine biological resource into water. The heating of marine biological resources including water is not particularly limited, but for example, heat generated by absorption of sunlight, heat of combustion of fossil fuels, exhaust heat from plants such as power plants, geothermal heat and the like are used.
（海洋生物資源）
当該海洋生物資源の処理方法の処理対象となる海洋生物資源は、海水を取水する際に混入する海藻類又は貝類を含む海洋生物資源であり、例えば海中を浮遊している海藻類や、取水装置の水路、ピット又は配管に付着する貝類が挙げられる。これらの海洋生物資源は、取水中又は取水後に海水から取り出されるが、ヒ素、鉛、カドミウム、６価クロム、セレン等の重金属類を有害物質として多く含んでいる場合がある。例えば、ヒジキやホンダワラ属等の海藻類にヒ素が多く含まれ、藤壺やムラサキイガイ等の貝類の貝肉、内臓又はウロにヒ素、カドミウム、６価クロム等が多く含まれることが知られている。当該海洋生物資源の処理方法は、処理対象としてこれらの重金属類を多く含む海洋生物資源を選択すると特に好ましい。なお、海洋生物資源は、海藻類又は貝類の少なくとも一方を含むが、これら以外の例えば魚類等の海洋生物を含んでいてもよい。
(Marine biological resources)
The marine biological resource to be treated by the method for treating the marine biological resource is a marine biological resource including seaweed or shellfish that is mixed when taking in seawater. For example, seaweed floating in the sea or a water intake device. Examples include shellfish that adhere to waterways, pits or pipes. These marine biological resources are taken out from seawater during or after intake, but may contain a large amount of heavy metals such as arsenic, lead, cadmium, hexavalent chromium, and selenium as harmful substances. For example, it is known that seaweeds such as Hijiki and Sargassum contain a large amount of arsenic, and shellfish such as wisteria jars and mussels, viscera or mussels contain a large amount of arsenic, cadmium, hexavalent chromium and the like. .. As the method for treating marine biological resources, it is particularly preferable to select marine biological resources containing a large amount of these heavy metals as the treatment target. The marine biological resources include at least one of seaweeds and shellfish, but may also include other marine organisms such as fish.
加熱工程Ｓ１で水分を含む海洋生物資源を加熱する際の保持温度の下限としては、３０℃が好ましく、３５℃がより好ましく、４０℃がさらに好ましい。一方、保持温度の上限としては、１００℃が好ましく、８０℃がより好ましく、７０℃がさらに好ましい。保持温度が上記下限に満たないと、海洋生物資源に含まれる重金属類の水分への溶出が促進されないおそれがある。逆に、保持温度が上記上限を超えると、過大な加熱エネルギーを必要とするおそれがある。 The lower limit of the holding temperature when heating the marine biological resource containing water in the heating step S1 is preferably 30 ° C., more preferably 35 ° C., and even more preferably 40 ° C. On the other hand, as the upper limit of the holding temperature, 100 ° C. is preferable, 80 ° C. is more preferable, and 70 ° C. is further preferable. If the holding temperature does not reach the above lower limit, the elution of heavy metals contained in marine biological resources into water may not be promoted. On the contrary, if the holding temperature exceeds the above upper limit, excessive heating energy may be required.
加熱工程Ｓ１は、海洋生物資源に含まれる重金属類の種類や重金属類の量に応じて適宜実施されればよく、海洋生物資源に含まれる重金属類の水への溶解度が高い場合や海洋生物資源に含まれる重金属類の量が少ない場合は実施されなくてもよい。 The heating step S1 may be appropriately performed according to the type of heavy metals contained in the marine biological resources and the amount of the heavy metals, and when the heavy metals contained in the marine biological resources have high solubility in water or the marine biological resources. If the amount of heavy metals contained in is small, it may not be carried out.
＜混合工程＞
混合工程Ｓ２は、水分を含む海洋生物資源に重金属類不溶化剤を混合する工程であり、海洋生物資源から水分に溶出した重金属類を不溶化するために実施される。水分を含む海洋生物資源と重金属類不溶化剤との混合には、特に限定されないが、例えばバッチ式混合機を用いる手法又は搬送装置で搬送中の水分を含む海洋生物資源にホッパから重金属類不溶化剤を連続供給する手法が採用される。
<Mixing process>
The mixing step S2 is a step of mixing a heavy metal insolubilizer with a marine biological resource containing water, and is carried out to insolubilize the heavy metals eluted in water from the marine biological resource. The mixing of the marine biological resource containing water and the heavy metal insolubilizer is not particularly limited, but for example, the heavy metal insolubilizer from the hopper to the marine biological resource containing water being transported by a method using a batch type mixer or a transport device. Is adopted continuously.
（重金属類不溶化剤）
重金属類不溶化剤は、水分に溶出した重金属類を不溶化する機能を持つ添加剤である。重金属類不溶化剤としては、例えば鉄粉や、石灰系、マグネシア系、セメント系等の固化剤や、塩化第二鉄や、ポリ塩化アルミニウム等が用いられる。ただし、固化剤を採用する場合は、水分で固化する前に海洋生物資源から重金属類を溶出させる必要があり、塩化第二鉄やポリ塩化アルミニウムを採用する場合は、これらが重金属類と共沈するまでこれらを液体の状態に保持する必要がある。一方、鉄粉は、特別な操作を必要としない上に、ヒ素とともに、鉛、カドミウム、６価クロム、セレン等の重金属類を吸着しこれらを不溶化できる。このため、当該海洋生物資源の処理方法に用いられる重金属類不溶化剤が鉄粉であると特に好ましい。
(Heavy metals insolubilizer)
The heavy metal insolubilizer is an additive having a function of insolubilizing heavy metals eluted in water. As the heavy metal insolubilizer, for example, iron powder, lime-based, magnesia-based, cement-based solidifying agents, ferric chloride, polyaluminum chloride and the like are used. However, when using a solidifying agent, it is necessary to elute heavy metals from marine biological resources before solidifying with water, and when using ferric chloride or polyaluminum chloride, these coprecipitate with heavy metals. These need to be kept in a liquid state until On the other hand, iron powder does not require any special operation and can adsorb heavy metals such as lead, cadmium, hexavalent chromium and selenium together with arsenic to insolubilize them. Therefore, it is particularly preferable that the heavy metal insolubilizer used in the method for treating marine biological resources is iron powder.
重金属類不溶化剤として鉄粉が採用される場合、この鉄粉としては、例えば還元鉄粉、アトマイズ鉄粉、合金鋼粉、酸化鉄粉又はスラグ粉が採用される。ただし、重金属類の吸着能力の観点から、鉄粉における金属鉄の含有量は、８０質量％以上が好ましく、９０質量％以上がより好ましい。ここで、金属鉄とは、価数ゼロの状態の鉄を示す。 When iron powder is adopted as the heavy metal insolubilizer, for example, reduced iron powder, atomized iron powder, alloy steel powder, iron oxide powder or slag powder is adopted as the iron powder. However, from the viewpoint of the adsorption capacity of heavy metals, the content of metallic iron in the iron powder is preferably 80% by mass or more, more preferably 90% by mass or more. Here, metallic iron refers to iron in a state of zero valence.
重金属類不溶化剤としての鉄粉の平均粒子径は、鉄粉の重金属類を吸着する能力や混合作業の容易性の考慮により選択される。鉄粉の平均粒子径の下限としては、０．０２ｍｍが好ましく、０．０７ｍｍがより好ましく、０．１０ｍｍがさらに好ましい。一方、鉄粉の平均粒子径の上限としては、１ｍｍが好ましく、０．８ｍｍがより好ましく、０．５ｍｍがさらに好ましい。鉄粉の平均粒子径が上記下限に満たないと、水分を含む海洋生物資源に鉄粉を混合する際の取り扱いが困難になるおそれがある。逆に、鉄粉の平均粒子径が上記上限を超えると、鉄粉の比表面積が小さくなり、重金属類を吸着する能力が低下するおそれがある。なお、鉄粉の平均粒子径は、例えばレーザ回折式の粒度分布測定装置によって測定される粒度分布により求められる体積平均粒子径（Ｄ５０）である。 The average particle size of iron powder as a heavy metal insolubilizer is selected in consideration of the ability of iron powder to adsorb heavy metals and the ease of mixing work. The lower limit of the average particle size of the iron powder is preferably 0.02 mm, more preferably 0.07 mm, and even more preferably 0.10 mm. On the other hand, as the upper limit of the average particle size of the iron powder, 1 mm is preferable, 0.8 mm is more preferable, and 0.5 mm is further preferable. If the average particle size of iron powder is less than the above lower limit, it may be difficult to handle when iron powder is mixed with marine biological resources containing water. On the contrary, when the average particle size of the iron powder exceeds the above upper limit, the specific surface area of the iron powder becomes small, and the ability to adsorb heavy metals may decrease. The average particle size of the iron powder is, for example, the volume average particle size (D50) obtained from the particle size distribution measured by a laser diffraction type particle size distribution measuring device.
重金属類不溶化剤としての鉄粉の添加量は、鉄粉の重金属類を吸着する能力や経済性の考慮により選択される。鉄粉と海洋生物資源との混合比の下限としては、質量基準で、１：５０が好ましく、１：３０がより好ましく、１：２０がさらに好ましい。一方、上記混合比の上限としては、２：１が好ましく、１．５：１がより好ましく、１：１がさらに好ましい。上記混合比が上記下限に満たないと、鉄粉の重金属類を吸着する能力が不足し、乾燥工程Ｓ３後の海洋生物資源からの重金属類の溶出が抑制されないおそれがある。逆に、上記混合比が上記上限を超えると、混合に用いる鉄粉の量が増大し、コストが過大となるおそれがある。 The amount of iron powder added as a heavy metal insolubilizer is selected in consideration of the ability of iron powder to adsorb heavy metals and economic efficiency. The lower limit of the mixing ratio of iron powder and marine biological resources is preferably 1:50, more preferably 1:30, and even more preferably 1:20 on a mass basis. On the other hand, as the upper limit of the mixing ratio, 2: 1 is preferable, 1.5: 1 is more preferable, and 1: 1 is further preferable. If the mixing ratio does not reach the above lower limit, the ability to adsorb heavy metals of iron powder is insufficient, and the elution of heavy metals from marine biological resources after the drying step S3 may not be suppressed. On the contrary, if the mixing ratio exceeds the upper limit, the amount of iron powder used for mixing increases, and the cost may become excessive.
＜乾燥工程＞
乾燥工程Ｓ３は、混合工程Ｓ２後の混合物を乾燥する工程であり、重金属類不溶化剤を混合した海洋生物資源の減容化及び腐敗臭の抑制を目的として実施される。混合物の乾燥には、特に限定されないが、例えばオーブン炉等のバッチ式乾燥機又はロータリキルン等の連続式乾燥機が用いられる。混合物は、乾燥により水分を取り除かれた乾燥品となる。
<Drying process>
The drying step S3 is a step of drying the mixture after the mixing step S2, and is carried out for the purpose of reducing the volume of marine biological resources mixed with the heavy metal insolubilizer and suppressing the putrid odor. The drying of the mixture is not particularly limited, and for example, a batch dryer such as an oven or a continuous dryer such as a rotary kiln is used. The mixture is a dried product from which water has been removed by drying.
乾燥工程Ｓ３後の乾燥品は、フレキシブルコンテナやバケットに充填又はトラックの荷台に直積み可能であり、産業廃棄物として廃棄される場合は処分場へ搬送され、有効成分の抽出素材、肥料又は飼料として再利用される場合は再生工場へ搬送される。 The dried product after the drying step S3 can be filled in a flexible container or bucket or directly loaded on the truck bed, and when it is disposed of as industrial waste, it is transported to a disposal site, where the active ingredient extract material, fertilizer or feed is used. If it is reused as a waste, it will be transported to a recycling factory.
（利点）
当該海洋生物資源の処理方法は、水分を含んだ状態の海洋生物資源に重金属類不溶化剤を混合する混合工程Ｓ２を備えているので、海洋生物資源から水分へ重金属類を溶出させた状態で水分に溶出した重金属類を不溶化する。そして当該海洋生物資源の処理方法は、乾燥工程Ｓ３で、重金属類を不溶化した状態で重金属類不溶化剤を混合した海洋生物資源を乾燥するので、多大なエネルギーや水洗水を必要とせず、重金属類の溶出量を抑制した海洋生物資源を比較的容易に生成できる。
(advantage)
Since the method for treating the marine biological resource includes a mixing step S2 in which the heavy metal insolubilizer is mixed with the marine biological resource containing water, the water content is in a state where the heavy metal is eluted from the marine biological resource into water. Insolubilizes heavy metals eluted in. The method for treating marine biological resources is that in the drying step S3, the marine biological resources mixed with the heavy metals insolubilizer are dried in the state where the heavy metals are insolubilized, so that heavy metals do not require a large amount of energy or washing water. It is relatively easy to generate marine biological resources in which the amount of elution of water is suppressed.
また、当該海洋生物資源の処理方法は、混合工程Ｓ２の前に、水分を含む海洋生物資源を加熱する加熱工程Ｓ１を備えているので、海洋生物資源の重金属類の含有量を大幅に減少させ、水分へ溶出した重金属類を不溶化することにより、重金属類の溶出量を十分に抑制した海洋生物資源を生成できる。 Further, since the method for treating marine biological resources includes a heating step S1 for heating marine biological resources containing water before the mixing step S2, the content of heavy metals in marine biological resources is significantly reduced. By insolubilizing heavy metals eluted in water, it is possible to generate marine biological resources in which the amount of heavy metals eluted is sufficiently suppressed.
特に、当該海洋生物資源の処理方法は、重金属類不溶化剤として鉄粉を採用することで、ヒ素に加えて、鉛、カドミウム、６価クロム、セレン等を鉄の吸着作用により不溶化できる。このため、当該海洋生物資源の処理方法は、ヒ素を含む様々な重金属類の溶出量を抑制した海洋生物資源を生成できる。 In particular, in the method for treating marine biological resources, by adopting iron powder as a heavy metal insolubilizer, lead, cadmium, hexavalent chromium, selenium and the like can be insolubilized by the adsorption action of iron in addition to arsenic. Therefore, the method for treating marine biological resources can generate marine biological resources in which the elution amount of various heavy metals including arsenic is suppressed.
当該海洋生物資源の処理方法により生成され、重金属類の溶出量を抑制された海洋生物資源は、産業廃棄物として廃棄可能となるだけでなく、必要な条件を満たせば、ビタミン、ミネラル、食物繊維等の有効成分の抽出素材、田畑への肥料又は動物への飼料として再利用可能となる。このため、当該海洋生物資源の処理方法は、環境負荷の低減にも寄与できる可能性がある。 Marine biological resources produced by the method for treating marine biological resources and whose elution amount of heavy metals is suppressed can be disposed of as industrial waste, and if necessary conditions are met, vitamins, minerals, and dietary fiber. It can be reused as an extraction material for active ingredients such as, fertilizer for fields, or feed for animals. Therefore, the method for treating marine biological resources may contribute to the reduction of environmental load.
＜その他の実施形態＞
本発明の海洋生物資源の処理方法は、上記実施形態に限定されない。
<Other Embodiments>
The method for treating marine biological resources of the present invention is not limited to the above embodiment.
上記実施形態では、混合工程Ｓ２前に、加熱工程Ｓ１で水分を含む海洋生物資源を加熱するものについて説明したが、水分を含む海洋生物資源の加熱タイミングは、混合工程Ｓ２後であってもよく、例えば、海洋生物資源の処理方法が、乾燥工程Ｓ３前に、混合工程Ｓ２後の混合物を加熱する工程を備えるものであってもよい。ただし、加熱時の海洋生物資源からの重金属類の溶出及び重金属類不溶化剤による重金属類の不溶化には一定の時間が必要となるので、時間効率の観点から、上記実施形態のように、混合工程Ｓ２前に水分を含む海洋生物資源を加熱する方が好ましい。 In the above embodiment, the heating of the marine biological resource containing water in the heating step S1 has been described before the mixing step S2, but the heating timing of the marine biological resource containing water may be after the mixing step S2. For example, the method for treating marine biological resources may include a step of heating the mixture after the mixing step S2 before the drying step S3. However, since a certain amount of time is required for elution of heavy metals from marine biological resources during heating and insolubilization of heavy metals by a heavy metal insolubilizer, a mixing step is performed as in the above embodiment from the viewpoint of time efficiency. It is preferable to heat marine biological resources containing water before S2.
以下、実施例によって本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
［加熱試験］
まず、産業廃棄物に含まれる金属等の検定方法（昭和４８年環境庁告示第１３号試験）に基づいて、ホンダワラ属の海藻のヒ素溶出量を測定した。海藻のヒ素溶出量は１．２ｍｇ／Ｌであった。
[Heating test]
First, the amount of arsenic elution of seaweed of the genus Sargassum was measured based on the verification method for metals and the like contained in industrial waste (Ministry of the Environment Notification No. 13 test in 1973). The amount of arsenic eluted from seaweed was 1.2 mg / L.
次に、純水を１００℃に沸騰させたお湯５０００ｇに水分を含んだ状態のホンダワラ属の海藻１００ｇを投入し、１００℃のまま１２０分間保持した。その後、お湯から取り出した海藻を２５℃の水洗水に投入し、３分間保持した。水洗後の海藻を１８０℃の恒温炉に挿入し、３０分間乾燥した。お湯及び水洗水のヒ素濃度を測定すると、それぞれ０．７２ｍｇ／Ｌ及び０．００８ｍｇ／Ｌであった。また、乾燥後の海藻の質量は４３ｇであった。さらに、昭和４８年環境庁告示第１３号試験に基づいて、乾燥後の海藻のヒ素溶出量を測定した結果、ヒ素溶出量は０．０６ｍｇ／Ｌであった。 Next, 100 g of seaweed of the genus Sargassum in a state of containing water was added to 5000 g of hot water in which pure water was boiled at 100 ° C., and the temperature was kept at 100 ° C. for 120 minutes. Then, the seaweed taken out from the hot water was put into washing water at 25 ° C. and held for 3 minutes. The seaweed after washing with water was inserted into a constant temperature furnace at 180 ° C. and dried for 30 minutes. The arsenic concentrations of hot water and flush water were measured and found to be 0.72 mg / L and 0.008 mg / L, respectively. The mass of the dried seaweed was 43 g. Furthermore, as a result of measuring the arsenic elution amount of the seaweed after drying based on the Ministry of the Environment Notification No. 13 test in 1973, the arsenic elution amount was 0.06 mg / L.
［Ｎｏ．１〜Ｎｏ．４の試験］
水分を含んだ状態のホンダワラ属の海藻１００ｇと様々な量の鉄粉とをバット上で均一に混合した後、この混合物を１０５℃の恒温炉に挿入し、６時間乾燥した。その後、昭和４８年環境庁告示第１３号試験に基づいて、乾燥物のヒ素溶出量を測定した。処理前の海藻状態、海藻と混合した鉄粉の重量及び乾燥物のヒ素溶出量を表１に示す。なお、Ｎｏ．４は、鉄粉を混合しなかった試験である。
[No. 1-No. Test of 4]
After 100 g of seaweed of the genus Sargassum containing water and various amounts of iron powder were uniformly mixed on a vat, this mixture was inserted into a constant temperature furnace at 105 ° C. and dried for 6 hours. After that, the amount of arsenic eluted from the dried product was measured based on the Ministry of the Environment Notification No. 13 test in 1973. Table 1 shows the state of seaweed before treatment, the weight of iron powder mixed with seaweed, and the amount of arsenic eluted from the dried product. In addition, No. No. 4 is a test in which iron powder was not mixed.
［Ｎｏ．５〜Ｎｏ．８の試験］
予め乾燥したホンダワラ属の海藻１００ｇと様々な量の鉄粉とをビニル袋内で均一に混合した。その後、昭和４８年環境庁告示第１３号試験に基づいて、混合物のヒ素溶出量を測定した。処理前の海藻状態、海藻と混合した鉄粉の重量及び混合物のヒ素溶出量を表１に示す。なお、Ｎｏ．８は、鉄粉を混合しなかった試験である。
[No. 5-No. 8 tests]
Pre-dried 100 g of Sargassum seaweed and various amounts of iron powder were uniformly mixed in a vinyl bag. Then, the amount of arsenic eluted from the mixture was measured based on the Ministry of the Environment Notification No. 13 test in 1973. Table 1 shows the state of seaweed before treatment, the weight of iron powder mixed with seaweed, and the amount of arsenic eluted from the mixture. In addition, No. Reference numeral 8 denotes a test in which iron powder was not mixed.
表１に示すように、海藻に加える鉄粉の量を増加させると海藻のヒ素溶出量が減少することが確認された。また、水分を含んだ状態の海藻に鉄粉を加えたＮｏ．１〜Ｎｏ．３の試験は、予め乾燥した海藻に鉄粉を加えたＮｏ．５〜Ｎｏ．７の試験と比較して、海藻のヒ素溶出量を大幅に減少させることが確認された。 As shown in Table 1, it was confirmed that increasing the amount of iron powder added to the seaweed reduces the amount of arsenic eluted from the seaweed. In addition, No. 1 in which iron powder was added to seaweed in a water-containing state. 1-No. In the test No. 3, iron powder was added to pre-dried seaweed. 5-No. It was confirmed that the amount of arsenic eluted from seaweed was significantly reduced as compared with the test of No. 7.
さらに、Ｎｏ．３〜Ｎｏ．８の試験では、乾燥物又は混合物のヒ素溶出量が、日本国の廃棄物処理法で規定されているヒ素溶出量の基準上限値０．３ｍｇ／Ｌ以上の値を示し、Ｎｏ．１及びＮｏ．２の試験では、乾燥物のヒ素溶出量が、この基準上限値未満の値を示すことが確認された。 Furthermore, No. 3 to No. In the test No. 8, the arsenic elution amount of the dried product or mixture showed a value of 0.3 mg / L or more, which is the standard upper limit value of the arsenic elution amount specified by the Waste Management Law of Japan, and No. 1 and No. In the second test, it was confirmed that the arsenic elution amount of the dried product showed a value less than this standard upper limit value.
以上の結果から、水分を含んだ状態の海藻に鉄粉を一定量以上加えた場合に、海藻からのヒ素の溶出量を効果的に抑制できるといえる。また、加熱試験から、海藻を加熱することで海藻に含まれるヒ素が水分へ効果的に溶出するといえるので、水分を含んだ状態の海藻を加熱した後に鉄粉を加える場合には、より高いヒ素溶出量の抑制効果が期待される。 From the above results, it can be said that when a certain amount or more of iron powder is added to the seaweed containing water, the amount of arsenic eluted from the seaweed can be effectively suppressed. In addition, from the heating test, it can be said that the arsenic contained in the seaweed is effectively eluted into the water by heating the seaweed. Therefore, when iron powder is added after heating the seaweed in a water-containing state, the arsenic content is higher. The effect of suppressing the amount of elution is expected.
本発明の海洋生物資源の処理方法は、海水の取水時に混入する海藻類又は貝類を含む海洋生物資源から重金属類の溶出量を抑制した海洋生物資源を比較的容易に生成できる。このため、当該海洋生物資源の処理方法は、重金属類を多く含む海洋生物資源であっても、産業廃棄物としての処理や資源としての再利用を可能とする。 The method for treating marine biological resources of the present invention can relatively easily generate marine biological resources in which the amount of heavy metals elution is suppressed from marine biological resources including seaweeds or shellfish mixed during the intake of seawater. Therefore, the method for treating marine biological resources enables treatment of marine biological resources containing a large amount of heavy metals as industrial waste and reuse as resources.
Claims (3)
水分を含む上記海洋生物資源に重金属類不溶化剤を混合する工程と、
上記混合工程後の混合物を乾燥する工程と
を備え、
上記重金属類不溶化剤が鉄粉であり、
上記鉄粉が還元鉄粉、アトマイズ鉄粉、合金鋼粉、酸化鉄粉又はスラグ粉であり、
上記乾燥工程後の混合物が肥料又は飼料に用いられる海洋生物資源の処理方法。 A method for treating marine biological resources including seaweeds or shellfish that are mixed in when seawater is taken in.
The process of mixing heavy metals insolubilizer with the above marine biological resources containing water,
A step of drying the mixture after the above mixing step is provided .
The heavy metal insolubilizer is iron powder,
The iron powder is reduced iron powder, atomized iron powder, alloy steel powder, iron oxide powder or slag powder.
Method of processing marine living resources mixture after the drying step that is used in the fertilizer or feed.
をさらに備える請求項１に記載の海洋生物資源の処理方法。 The method for treating marine biological resources according to claim 1, further comprising a step of heating the marine biological resources containing water before the mixing step.
The method for treating a marine biological resource according to claim 1 or 2, wherein the marine biological resource contains arsenic.
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| JPH08187488A (en) * | 1995-01-10 | 1996-07-23 | S F Plan:Kk | Treatment of marine products containing cadmium |
| JP4547516B2 (en) * | 2000-11-28 | 2010-09-22 | 独立行政法人 日本原子力研究開発機構 | How to remove harmful metals from scallop scales |
| JP2010057442A (en) * | 2008-09-05 | 2010-03-18 | Hokkaido Univ | Method for removing heavy metal from fish and shellfish containing harmful heavy metal in short time, and manufacturing method of foodstuff obtained by the same |
| CN101905910A (en) * | 2009-06-05 | 2010-12-08 | 中国科学院生态环境研究中心 | Reactor for removing arsenic in water on basis of iron-based composite oxide |
| CN101637709A (en) * | 2009-07-10 | 2010-02-03 | 广东海洋大学 | Methods for preparing carboxymethyl chitosan magnetic microspheres and adsorbing cadmium in oyster meat by using carboxymethyl chitosan magnetic microspheres |
| CN101607996B (en) * | 2009-07-21 | 2012-02-15 | 大连工业大学 | Method for removing heavy metal ions from marine shellfish polysaccharide |
| CN101999330A (en) * | 2010-11-17 | 2011-04-06 | 天津师范大学 | Method for purifying noxious substances in edible bivalves |
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| CN104026652A (en) * | 2014-02-28 | 2014-09-10 | 国家海洋局第三海洋研究所 | Preparing method of food grade marine-organism-sourced shell micro powder |
| CN104651066A (en) * | 2015-02-02 | 2015-05-27 | 天津市朴优科技有限公司 | Detergent capable of removing heavy metals from aquatic product and preparation method of detergent |
| CN106281331A (en) * | 2015-05-18 | 2017-01-04 | 南京凯杰环境技术有限公司 | A kind of manufacture method of ferrum system heavy metal-polluted soil immobilization material |
| JP6688576B2 (en) * | 2015-08-20 | 2020-04-28 | Ｄｏｗａエコシステム株式会社 | Decontamination method for contaminated soil |
| CN106583422B (en) * | 2016-12-25 | 2019-04-09 | 中南林业科技大学 | A kind of solidification arsenic slag technique with high salt |
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