JP6090665B2 - Sediment improvement and fertilizer and its usage - Google Patents
Sediment improvement and fertilizer and its usage Download PDFInfo
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- JP6090665B2 JP6090665B2 JP2013085278A JP2013085278A JP6090665B2 JP 6090665 B2 JP6090665 B2 JP 6090665B2 JP 2013085278 A JP2013085278 A JP 2013085278A JP 2013085278 A JP2013085278 A JP 2013085278A JP 6090665 B2 JP6090665 B2 JP 6090665B2
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- 239000013049 sediment Substances 0.000 title claims description 52
- 239000003337 fertilizer Substances 0.000 title claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 146
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 81
- 229910052742 iron Inorganic materials 0.000 claims description 77
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 60
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 60
- 239000010883 coal ash Substances 0.000 claims description 37
- 239000011701 zinc Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 33
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000002738 chelating agent Substances 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 229910021645 metal ion Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 235000015170 shellfish Nutrition 0.000 claims description 18
- 239000013522 chelant Substances 0.000 claims description 17
- -1 iron ions Chemical class 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 241000195493 Cryptophyta Species 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000012258 culturing Methods 0.000 claims 3
- 238000012136 culture method Methods 0.000 claims 1
- 238000002474 experimental method Methods 0.000 description 49
- 238000010828 elution Methods 0.000 description 21
- 239000011572 manganese Substances 0.000 description 21
- 229910052748 manganese Inorganic materials 0.000 description 15
- 229910000831 Steel Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 241000207199 Citrus Species 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000020971 citrus fruits Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 235000020083 shōchū Nutrition 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 241000237519 Bivalvia Species 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000269959 Xiphias gladius Species 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009360 aquaculture Methods 0.000 description 2
- 244000144974 aquaculture Species 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 235000020639 clam Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000012364 cultivation method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000020774 essential nutrients Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000037406 food intake Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000021335 sword fish Nutrition 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- ZCUQOPGIJRGJDA-UHFFFAOYSA-N 1-naphthalen-1-ylethane-1,2-diamine Chemical compound C1=CC=C2C(C(N)CN)=CC=CC2=C1 ZCUQOPGIJRGJDA-UHFFFAOYSA-N 0.000 description 1
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- TVVTWOGRPVJKDJ-UHFFFAOYSA-N Befunolol hydrochloride Chemical compound [Cl-].CC(C)[NH2+]CC(O)COC1=CC=CC2=C1OC(C(C)=O)=C2 TVVTWOGRPVJKDJ-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000012901 Milli-Q water Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229960004374 befunolol Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012407 engineering method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium 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
- 244000005700 microbiome Species 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000003784 poor nutrition Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003971 tillage Methods 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
Landscapes
- Fertilizers (AREA)
- Cultivation Of Seaweed (AREA)
- Farming Of Fish And Shellfish (AREA)
- Treatment Of Sludge (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
本発明は、底質改善・施肥材及びその利用方法に関する。 The present invention relates to a bottom quality improving / fertilizing material and a method of using the same.
閉鎖性水域では水の交換が悪いため、陸域負荷の影響を強く受け、有機物含有量の高い底泥が堆積し、還元的な状態になりやすい。このような還元的な環境では、硫化水素の発生を促す。硫化水素は生物に対して猛毒であり、これによって生物生息数が減少し、ほぼ無生物になる場合もある。底泥中の硫化水素を抑えて良好な底質環境を取り戻し、生物の生息を復活させることは、生物多様性や生物生産性を高める観点から極めて重要である。 Since water exchange is poor in closed water areas, it is strongly affected by land loads, and sediment with high organic matter content accumulates and tends to be reduced. In such a reducing environment, the generation of hydrogen sulfide is promoted. Hydrogen sulfide is extremely toxic to living organisms, which reduces the number of living organisms and can be nearly inanimate. It is extremely important from the viewpoint of enhancing biodiversity and bioproductivity to reduce the hydrogen sulfide in the bottom mud and restore the good sediment environment and restore the living organisms.
底質を改善する手法として、耕耘、曝気、浚渫、覆砂など、土木的手法が実施されてきた。しかし、これらの手法では、汚濁物質の拡散、浚渫後の汚泥の処理などの副次的な問題や、高コストであるなどの問題がある。 Civil engineering methods such as tillage, aeration, dredging and sand cover have been implemented as methods for improving sediment quality. However, these methods have secondary problems such as the diffusion of pollutants and the treatment of sludge after dredging, and problems such as high costs.
有機物含量の高い底質中で発生する硫化水素の低減には、鉄鋼スラグ（例えば、特許文献１、２）や石炭灰造粒物（例えば、特許文献３、４）等が効果的であることが知られており、前者は鉄による酸化還元、後者はマンガンによる酸化還元が作用することがわかっている。 Steel slag (for example, Patent Documents 1 and 2), coal ash granulated material (for example, Patent Documents 3 and 4), etc. are effective in reducing hydrogen sulfide generated in sediment with a high organic matter content. It is known that the former is redoxed by iron, and the latter is redoxed by manganese.
また、水質が貧栄養な場合の施肥材として、鉄を溶出させるものがあり、例えば、鉄、炭、及び、焼酎滓或いは柑橘類の滓を含有し、鉄と炭との接触により鉄イオンを溶出し、鉄イオンと焼酎滓或いは柑橘類の滓に含まれるキレート剤により鉄キレートを発生させる鉄キレート発生材が知られている（特許文献５）。 In addition, there are fertilizers that elute iron as a fertilizer when the water quality is poor nutrition. For example, it contains iron, charcoal, and shochu or citrus koji, and iron ions are eluted by contact with iron and charcoal. And the iron chelate generating material which generates an iron chelate by the chelating agent contained in iron ion and shochu or citrus koji is known (Patent Document 5).
特許文献５の鉄キレート発生材では、鉄イオンの溶出量は十分とはいえず、未だ改善の余地がある。また、焼酎滓或いは柑橘類の滓を含有しており、これは有機物含有量を増加させることにもなり、還元的な状態を悪化させるおそれがある。 In the iron chelate generating material of Patent Document 5, the elution amount of iron ions is not sufficient, and there is still room for improvement. In addition, it contains shochu or citrus koji, which increases the organic matter content and may deteriorate the reducing state.
本発明は上記事項に鑑みてなされたものであり、その目的とするところは、有機物含有量を増大させることなく、鉄イオン、亜鉛イオンを多く溶出させるとともに、窒素、リン及び珪素を溶出させ得る底質改善・施肥材及びその利用方法を提供することにある。 The present invention has been made in view of the above matters, and its object is to elute a large amount of iron ions and zinc ions and to elute nitrogen, phosphorus and silicon without increasing the organic content. It is to provide a bottom quality improvement and fertilizer and its usage.
本発明の第一の態様に係る底質改善・施肥材は、
石炭灰と鉄とキレート剤とを含有し、
前記石炭灰と前記鉄との配合比が重量比で３：７〜７：３であり、
前記キレート剤がクエン酸であり、
水中で鉄イオン及び亜鉛イオンを溶出して、前記キレート剤とで鉄キレート及び亜鉛キレートを形成するとともに、窒素、リン及び珪素を溶出する、
ことを特徴とする。
Sediment improvement / fertilizer according to the first aspect of the present invention,
Contains coal ash, iron and chelating agent,
The mixing ratio of the coal ash and the iron is 3: 7 to 7: 3 by weight,
The chelating agent is citric acid;
Eluting iron ions and zinc ions in water, forming iron chelate and zinc chelate with the chelating agent, and eluting nitrogen, phosphorus and silicon,
It is characterized by that.
また、前記クエン酸を３重量％以上７重量％含有することが好ましい。 The citric acid is preferably contained in an amount of 3 to 7% by weight.
本発明の第二の態様に係る底質改善方法は、
石炭灰と鉄とキレート剤とを含有し、水中で鉄イオン及び亜鉛イオンを溶出して、前記キレート剤とで鉄キレート及び亜鉛キレートを形成するとともに、窒素、リン及び珪素を溶出する底質改善・施肥材を閉鎖水域に施工し、
前記底質改善・施肥材から金属イオンを溶出させ、前記金属イオンを錯体として溶存させ、
前記金属イオンと底泥で生じる硫化水素との反応により金属硫化物を形成させて硫化水素濃度を低減させる、
ことを特徴とする。
また、前記石炭灰と前記鉄との配合比が重量比で３：７〜７：３である前記底質改善・施肥材を用いることが好ましい。
また、前記キレート剤がクエン酸である前記底質改善・施肥材を用いることが好ましい。
また、前記クエン酸を３重量％以上７重量％含有する前記底質改善・施肥材を用いることが好ましい。
The bottom sediment improvement method according to the second aspect of the present invention,
Contains coal ash, iron and chelating agent, elutes iron ions and zinc ions in water, forms iron chelate and zinc chelate with the chelating agent, and improves bottom sediment to elute nitrogen, phosphorus and silicon・ Construct fertilizer in closed water area,
The metal ions are eluted from the bottom material improving and fertilizer, the metal ions are dissolved as a complex,
Reducing the hydrogen sulfide concentration by forming a metal sulfide by the reaction between the metal ions and hydrogen sulfide generated in the bottom mud,
It is characterized by that.
Moreover, it is preferable to use the said bottom sediment improving and fertilizing material whose compounding ratio of the said coal ash and the said iron is 3: 7-7: 3 by weight ratio.
In addition, it is preferable to use the bottom sediment improving / fertilizing material in which the chelating agent is citric acid.
Moreover, it is preferable to use the bottom material improving / fertilizing material containing 3% by weight or more of the citric acid.
本発明の第三の態様に係る水生生物の養殖方法は、
石炭灰と鉄とキレート剤とを含有し、水中で鉄イオン及び亜鉛イオンを溶出して、前記キレート剤とで鉄キレート及び亜鉛キレートを形成するとともに、窒素、リン及び珪素を溶出する底質改善・施肥材を貝類或いは藻類の養殖水域に配置し、
前記底質改善・施肥材から金属イオンを溶出させて前記金属イオンを錯体として溶存させるとともに、窒素、リン及び珪素を溶出させて、これらを前記貝類或いは前記藻類に直接的或いは間接的に摂取させて前記貝類或いは前記藻類の成長を促進させる、
ことを特徴とする。
また、前記石炭灰と前記鉄との配合比が重量比で３：７〜７：３である前記底質改善・施肥材を用いることが好ましい。
また、前記キレート剤がクエン酸である前記底質改善・施肥材を用いることが好ましい。
また、前記クエン酸を３重量％以上７重量％含有する前記底質改善・施肥材を用いることが好ましい。
The aquatic organism cultivation method according to the third aspect of the present invention comprises:
Contains coal ash, iron and chelating agent, elutes iron ions and zinc ions in water, forms iron chelate and zinc chelate with the chelating agent, and improves bottom sediment to elute nitrogen, phosphorus and silicon・ Place fertilizer in shellfish or algae culture waters,
The metal ions are eluted from the sediment improvement / fertilizer to dissolve the metal ions as a complex, and nitrogen, phosphorus, and silicon are eluted, and these are taken directly or indirectly by the shellfish or the algae. Promote the growth of the shellfish or the algae,
It is characterized by that.
Moreover, it is preferable to use the said bottom sediment improving and fertilizing material whose compounding ratio of the said coal ash and the said iron is 3: 7-7: 3 by weight ratio.
In addition, it is preferable to use the bottom sediment improving / fertilizing material in which the chelating agent is citric acid.
Moreover, it is preferable to use the bottom material improving / fertilizing material containing 3% by weight or more of the citric acid.
本発明に係る底質改善・施肥材では、金属イオンの溶出量が高く、生じた金属イオンがキレート剤と錯体を形成し溶存する。溶存する金属イオンは、閉鎖性水域において、硫化水素と反応して金属硫化物を形成することで、硫化水素濃度を低減させる。これにより、閉鎖性水域の還元的な環境を酸化的環境に改善させ得る。また、底質改善・施肥材は、無機の窒素、リン、珪素を溶出するが、有機物含有量を高めることがなく、還元的な環境を悪化させるおそれもない。 In the sediment improvement / fertilizer according to the present invention, the elution amount of metal ions is high, and the generated metal ions form a complex with the chelating agent and dissolve. The dissolved metal ions react with hydrogen sulfide to form metal sulfides in a closed water area, thereby reducing the hydrogen sulfide concentration. Thereby, the reducing environment of a closed water area can be improved to an oxidative environment. Further, the bottom sediment improving / fertilizing material elutes inorganic nitrogen, phosphorus, and silicon, but does not increase the organic content and does not deteriorate the reducing environment.
（底質改善・施肥材）
本実施の形態に係る底質改善・施肥材は、石炭灰と鉄とキレート剤を含有する。底質改善・施肥材は、水中にて鉄から鉄イオンを、石炭灰から亜鉛イオンを溶出し、これらがキレート剤と錯体を形成するので、鉄及び亜鉛をイオン状態で溶存させ得る。また、石炭灰からは、窒素、リン、珪素を溶出させる。
(Bottom quality improvement and fertilizer)
The sediment improvement / fertilizer according to the present embodiment contains coal ash, iron, and a chelating agent. The bottom sediment improving / fertilizing material elutes iron ions from iron and zinc ions from coal ash in water and forms a complex with a chelating agent, so that iron and zinc can be dissolved in an ionic state. Further, nitrogen, phosphorus and silicon are eluted from the coal ash.
石炭灰は、石炭を燃焼する際に生じる灰である。石炭灰は、一般に、シリカ（ＳｉＯ２）、アルミナ（Ａｌ２Ｏ３）を主成分とし、その他、亜鉛やマンガン等を微量成分として含んでいる。石炭灰は、石炭を原料に発電を行っている火力発電所で生じるものをそのまま用いればよい。火力発電所で生じる石炭灰は、ガス流れにより飛散するほどの球状の微粒子であり、そのままの状態で好適に用いられ得る。 Coal ash is ash generated when coal is burned. Coal ash generally contains silica (SiO 2 ) and alumina (Al 2 O 3 ) as main components, and also contains zinc, manganese, and the like as trace components. What is necessary is just to use what is produced in the thermal power plant which is generating electricity using coal as a raw material for coal ash. Coal ash generated in a thermal power plant is spherical fine particles that are scattered by a gas flow, and can be suitably used as it is.
鉄は、屑鉄などが用いられ、不純物が１０重量％以下、好ましくは５重量％以下、より好ましくは９９重量％以下のほぼ純粋な鉄であることが好ましい。鉄は、粉末状であることが好ましい。 As the iron, scrap iron or the like is used, and it is preferable to use substantially pure iron with impurities of 10% by weight or less, preferably 5% by weight or less, more preferably 99% by weight or less. Iron is preferably in powder form.
キレート剤は、鉄からの鉄イオンの溶出、並びに、石炭灰からの亜鉛イオンの溶出を促進させる。また、生じた鉄イオン及び亜鉛イオンと錯体を形成し、鉄キレート及び亜鉛キレートを形成する。このため、溶出した各金属イオンをそれぞれイオン状態で水中に溶存させることができる。キレート剤として、上記機能を果たし得るものであれば特に限定されず、一例としてクエン酸が挙げられる。 The chelating agent promotes the elution of iron ions from iron as well as the elution of zinc ions from coal ash. Moreover, it forms a complex with the generated iron ion and zinc ion to form an iron chelate and a zinc chelate. For this reason, each eluted metal ion can be dissolved in water in an ionic state. The chelating agent is not particularly limited as long as it can fulfill the above function, and citric acid is an example.
上述した底質改善・施肥材は、鉄粉と石炭灰とキレート剤を混合し、所定の形状に成形することで得られる。底質改善・施肥材は、球形状、多角形状、ブリケット形状等、どのような形状であってもよい。成形は、種々の公知の手法を用いることができ、例えば、原料を回転ドラムに入れ、水等の液体を加えつつ、所定の大きさに造粒する方法が挙げられる。 The above-mentioned bottom material improving / fertilizing material is obtained by mixing iron powder, coal ash, and a chelating agent and molding the mixture into a predetermined shape. The bottom quality improving / fertilizing material may have any shape such as a spherical shape, a polygonal shape, and a briquette shape. Various known methods can be used for the molding, and examples thereof include a method in which a raw material is put in a rotating drum and granulated to a predetermined size while adding a liquid such as water.
鉄と石炭灰の配合割合は、重量比で３：７〜７：３が好ましく、４：６〜６：４であることがより好ましい。 The weight ratio of iron and coal ash is preferably 3: 7 to 7: 3, and more preferably 4: 6 to 6: 4.
キレート剤の配合割合は、鉄及び石炭灰の総量に対して、３重量％以上であることが好ましい。なお、キレート剤の配合割合を増加すれば、各金属イオンの溶出量が増加する一方で、成型される底質改善・施肥材が脆くなりやすい。このため、金属イオンの溶出量及び底質改善・施肥材の成型性、並びに、形状維持性の観点から、底質改善・施肥材がキレート剤を３重量％以上７重量％以下含有していることがより好ましい。 The mixing ratio of the chelating agent is preferably 3% by weight or more with respect to the total amount of iron and coal ash. In addition, if the blending ratio of the chelating agent is increased, the amount of each metal ion eluted increases, while the bottom sediment improvement / fertilizer to be molded tends to become brittle. For this reason, from the viewpoints of metal ion elution, bottom sediment improvement / fertilizer formability, and shape maintenance, the bottom sediment improvement / fertilizer contains a chelating agent in an amount of 3 wt% to 7 wt%. It is more preferable.
また、底質改善・施肥材では、上述した鉄及び亜鉛に加え、マンガン、窒素、リン、シリカなども溶出する。これらは、石炭灰から溶出される。 In addition to the above-described iron and zinc, manganese, nitrogen, phosphorus, silica and the like are also eluted in the bottom sediment improving / fertilizing material. These are eluted from the coal ash.
（底質改善方法）
本実施の底質改善方法は、上述した底質改善・施肥材を閉鎖性水域の底泥に施工することにより行われる。底質改善・施肥材の施工は、海や湖沼にそのまま散布すればよく、干潟等では、底泥に鋤き込んでもよい。
(Sediment improvement method)
The bottom sediment improvement method of the present embodiment is performed by applying the above-described bottom sediment improvement / fertilizer to the bottom mud of the closed water area. For the improvement of bottom sediment and fertilizer, it can be applied to the sea or lake as it is, and in tidal flats, it may be poured into the bottom mud.
ここで、閉鎖性水域とは、地理的要因で水の流出入の機会が乏しい環境におかれている内湾、入り江、干潟等の海やダム湖、池、堀等の湖沼をいう。閉鎖性水域の底泥は有機物の堆積が顕著であり、微生物等による有機物の酸化的分解によって溶存酸素が消費されるため、底泥は還元的な環境になりやすい。還元的な環境下では、硫酸還元菌によって硫酸イオンが還元され、硫化水素が発生する。硫化水素は水中で酸化され、青潮や貧酸素水塊の発生などにより、底質及び水質悪化を招く。 Here, the closed water area means a sea such as an inner bay, a bay, a tidal flat, or a lake such as a dam lake, a pond, a moat, etc., which are in an environment where there are few opportunities for water inflow and outflow due to geographical factors. The bottom mud in a closed water area has a remarkable accumulation of organic matter, and dissolved oxygen is consumed by oxidative decomposition of the organic matter by microorganisms and the like, so the bottom mud tends to be a reducing environment. Under a reducing environment, sulfate ions are reduced by sulfate-reducing bacteria, and hydrogen sulfide is generated. Hydrogen sulfide is oxidized in water, causing bottom sediment and water quality deterioration due to generation of blue tide and anoxic water mass.
また、硫化水素は生物への毒性が強い。閉鎖性水域では、微細藻類、ベントス、魚類などの様々な生物が生息し、それらの食物連鎖によって物質が循環し、生態系が形成されている。しかし、この食物連鎖が毒性の強い硫化水素によって破壊され、生物多様性や漁業生産性の低下につながる。 Hydrogen sulfide is highly toxic to living organisms. In closed waters, various organisms such as microalgae, bentos and fish live, and materials are circulated through their food chain to form an ecosystem. However, this food chain is destroyed by highly toxic hydrogen sulfide, leading to a decline in biodiversity and fishery productivity.
このような閉鎖性水域の底泥に底質改善・施肥材を介在させることで、底質改善・施肥材から溶出した鉄イオン等の金属イオンが錯体としてイオン状態のまま溶存する。この金属イオンが底泥中及び水中の硫化水素と反応し、硫化鉄（ＦｅＳ）や硫化亜鉛（ＺｎＳ）等の金属硫化物となる。これにより、底泥中、水中の硫化水素濃度が低減し、還元的な環境が改善され、底質及び水質悪化を改善することができる。 By interposing the sediment improvement / fertilizer material in the bottom mud of such closed water areas, metal ions such as iron ions eluted from the sediment improvement / fertilizer material are dissolved in an ionic state as a complex. This metal ion reacts with hydrogen sulfide in the bottom mud and water to form metal sulfides such as iron sulfide (FeS) and zinc sulfide (ZnS). As a result, the concentration of hydrogen sulfide in the water in the bottom mud is reduced, the reducing environment is improved, and the bottom sediment and water quality deterioration can be improved.
更には、底質改善・施肥材から、栄養素として窒素、リン、珪素を適度に溶出するので、水中の生態系の健全性回復に寄与する。 In addition, nitrogen, phosphorus, and silicon are appropriately eluted as nutrients from the bottom sediment improvement and fertilizer, contributing to the restoration of the health of the underwater ecosystem.
（水生生物の養殖方法）
本実施の形態に係る水生生物の養殖方法は、貝類或いは藻類の養殖を行う水域に底質改善・施肥材を施工する。底質改善・施肥材の施工は、養殖を行う水域に散布することや、網状の袋に入れて配置することなど、種々の方法で行い得る。
(Aquaculture method)
In the aquatic organism cultivation method according to the present embodiment, bottom sediment improvement / fertilizer is applied to a water area where shellfish or algae are cultured. Bottom sediment improvement and fertilizer application can be performed by various methods such as spraying in the aquaculture area or placing them in a net-like bag.
鉄や亜鉛、或いは窒素、リン等は、貝類や藻類の成長に欠かせない必須栄養源である。底質改善・施肥材は上述したように、各種金属イオン等を溶出し、錯体としてイオン状態で水中に溶存させることができるので、これらを貝類、藻類が直接的或いは間接的に体内へ取り込むことができる。これにより、貝類、藻類の成長を促進させることができる。貝類として、牡蠣やアサリ、シジミ等が挙げられる。また、藻類として、海苔、昆布等の有用藻類（食用藻類）及び貝類の餌となる微細藻類が挙げられる。 Iron, zinc, nitrogen, phosphorus, etc. are essential nutrient sources essential for the growth of shellfish and algae. As mentioned above, the bottom sediment improvement and fertilizer can elute various metal ions, etc., and can be dissolved in water as a complex in an ionic state, so these are taken directly into the body by shellfish and algae. Can do. Thereby, the growth of shellfish and algae can be promoted. Examples of shellfish include oysters, clams and swordfish. Examples of algae include useful algae (edible algae) such as seaweed and kelp, and microalgae that serve as food for shellfish.
また、牡蠣やアサリ、シジミ等の貝類では、健康成分として身肉中の亜鉛含有量が高いことが特徴である。亜鉛は、ヒトにとって不可欠であるとともに、摂取し難い栄養素である。亜鉛含有量の高い貝類を生産できれば、それだけ亜鉛の摂取量を高められる。 In addition, shellfish such as oysters, clams and swordfish are characterized by a high zinc content in the meat as a health ingredient. Zinc is an essential nutrient for humans and difficult to take. If shellfish with a high zinc content can be produced, the intake of zinc can be increased accordingly.
亜鉛は水中では金属塩となり、このままでは貝類に取り込まれない。しかしながら、上述した底質改善・施肥材では、亜鉛イオンが溶出し、亜鉛イオンはキレート剤により錯体として溶存する。これにより、貝類が亜鉛イオンを直接摂取、或いは、亜鉛イオンを摂取した植物プランクトンの摂食による間接的摂取により、貝類の身肉中に取り込まれ得るので、貝類の商品価値を高めることができる。 Zinc becomes a metal salt in water and cannot be taken up by shellfish. However, in the above-mentioned bottom material improving / fertilizing material, zinc ions are eluted, and zinc ions are dissolved as a complex by the chelating agent. Thereby, since shellfish can be taken in into the flesh of shellfish by ingestion directly by intake of zinc ion or ingestion of phytoplankton which ingested zinc ion, the commercial value of shellfish can be raised.
以下、実施例に基づき、底質改善・施肥材について更に説明する。 Hereinafter, based on Examples, the bottom sediment improvement / fertilizer will be further described.
（供試材料）
石炭灰は、（株）エネルギア・エコ・マテリア製であり、粒子径は５０μｍ以下のものを用いた。用いた石炭灰の成分組成を表１に示す。
(Test material)
Coal ash was manufactured by Energia Eco Materia Co., Ltd., and a particle size of 50 μm or less was used. Table 1 shows the composition of the coal ash used.
鉄鋼スラグは日新製鋼（株）呉製鉄所製の粒子径が５ｍｍ以下のものを用いた。用いた鉄鋼スラグの成分組成を表２に示す。 As the steel slag, a particle having a particle diameter of 5 mm or less manufactured by Nisshin Steel Kure Works was used. Table 2 shows the composition of the steel slag used.
鉄粉は日の丸産業（株）製で、Ｆｅ含有量が９９％、粒子径が６０μｍのものを用いた。炭素は粒径１ｍｍ以下の高純度ピッチコークスを用いた。クエン酸は和光純薬（株）製（食品添加物、結晶状）を用いた。 The iron powder manufactured by Hinomaru Sangyo Co., Ltd. was used with an Fe content of 99% and a particle size of 60 μm. As the carbon, high-purity pitch coke having a particle diameter of 1 mm or less was used. Citric acid was manufactured by Wako Pure Chemical Industries, Ltd. (food additive, crystalline).
（サンプルの製造）
以下の各実験においてそれぞれに記す配合割合で原料を混合し、ドラム式造粒機に入れ、造粒機を回転させながら少しずつ水を加えて造粒し、直径１ｃｍ程度の球状のサンプルを作製して用いた。
(Sample production)
In each of the following experiments, the raw materials are mixed at the blending ratios described below, put into a drum granulator, and granulated by adding water little by little while rotating the granulator to produce a spherical sample with a diameter of about 1 cm. Used.
（実験１）
鉄粉と鉄鋼スラグによる鉄イオンの溶出量及び硫化水素の低減効果について検証した。
(Experiment 1)
The amount of iron ions eluted by iron powder and steel slag and the reduction effect of hydrogen sulfide were verified.
本実験で用いたサンプル１〜６の原料の配合割合を表３に示す。 Table 3 shows the mixing ratio of the raw materials of Samples 1 to 6 used in this experiment.
（硫化水素溶液の調製）
ビーカーに超純水（Ｍｉｌｌｉ−Ｑ水）を１Ｌ入れ、窒素で空気をパージし、溶存酸素濃度を０．１ｍｇ／Ｌ以下にした。これにＮａ２Ｓ・９Ｈ２Ｏ（試薬特級，ナカライテスク社製）を０，５０，１００ｍｇ−Ｓ／ｌとなるよう添加し、更にｐＨの緩衝剤として１Ｍ Ｔｒｉｓ−ＨＣｌ（分子生物学用，和光純薬製）を３０ｍｌ加えてｐＨを８．３±０．１に調節し、硫化水素溶液を調製した。以下、それぞれＨ２Ｓ０、Ｈ２Ｓ５０、Ｈ２Ｓ１００と記す。
(Preparation of hydrogen sulfide solution)
1 L of ultrapure water (Milli-Q water) was put into a beaker, and the air was purged with nitrogen so that the dissolved oxygen concentration was 0.1 mg / L or less. To this was added Na 2 S · 9H 2 O (special reagent grade, manufactured by Nacalai Tesque) to a concentration of 0, 50, 100 mg-S / l, and 1M Tris-HCl (for molecular biology, as a pH buffering agent). 30 ml of Wako Pure Chemical Industries, Ltd.) was added to adjust the pH to 8.3 ± 0.1 to prepare a hydrogen sulfide solution. Hereinafter, they are referred to as H2S0, H2S50, and H2S100, respectively.
ガスクロマトグラフィー用ガラス製バイアル瓶（１５０ｍｌ，マルエム社製）に、サンプルを０．２ｇ加えた後、硫化水素溶液を１００ｍｌ入れ、瓶内の気相を窒素ガスで置換してゴム栓およびアルミ金具で密閉した。その後、ＭＡＧＩＣ ＶＡＣ（アズワン株式会社，２０×３０ｃｍ，ポリアミド・ナイロン／ポリエチレン製）にバイアル瓶を入れて密封し、２５℃，４０ｒｐｍの条件で７日間振とうした。 After adding 0.2 g of sample to a glass vial for gas chromatography (150 ml, manufactured by Maruemu), put 100 ml of hydrogen sulfide solution, replace the gas phase in the bottle with nitrogen gas, rubber stopper and aluminum fittings And sealed. Thereafter, the vial was placed in MAGIC VAC (As One Co., Ltd., 20 × 30 cm, made of polyamide, nylon / polyethylene), sealed, and shaken for 7 days at 25 ° C. and 40 rpm.
７日後に硫化水素溶液中の硫化水素濃度を北川式検知管（光明理化学工業社製，２００ＳＡ，２−１０００ｐｐｍ用）で測定した。 Seven days later, the concentration of hydrogen sulfide in the hydrogen sulfide solution was measured with a Kitagawa detector tube (manufactured by Komyo Chemical Co., Ltd., for 200 SA, 2-1000 ppm).
更に、７日後のそれぞれの硫化水素溶液を０．４５μｍシリンジフィルター（ＭＥＲＣＫ ＭＩＬＬＩＰＯＲＥ社，Ｍｉｌｌｅｘ−ＨＮ，ナイロン製）でろ過したろ液について、Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ Ａｔｏｍｉｃ Ｅｍｉｓｓｉｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ（ＩＣＰ−ＡＥＳ）分析装置（Ｐｅｒｋｉｎ−Ｅｌｍｅｒ社製、Ｏｐｔｉｍａ７３００ＤＶ）により、溶出したＦｅ、Ｍｎ、Ｚｎの各濃度を測定した。 Further, an Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) analyzer (ICP-AES) analyzer was used for the filtrate obtained by filtering each hydrogen sulfide solution after 7 days with a 0.45 μm syringe filter (MERCK MILLIPORE, Millex-HN, nylon). -Elmer Co., Optima 7300 DV) was used to measure each concentration of eluted Fe, Mn, and Zn.
図１にサンプル１〜３を加えた硫化水素溶液中の硫化水素濃度の測定結果を、図２にサンプル４〜６を加えた硫化水素溶液中の硫化水素濃度の測定結果をそれぞれに示す。また、サンプル１〜３を加えた硫化水素溶液中のＦｅ、Ｍｎ、Ｚｎの濃度をそれぞれ図３、図４、図５に示す。また、サンプル４〜６を加えた硫化水素溶液中のＦｅ、Ｍｎ、Ｚｎの濃度をそれぞれ図６、図７、図８に示す。なお、各サンプルについて、それぞれ同じ実験を３回行っており、図１〜図８のシンボルが平均値、エラーバーが標準偏差を表している。また、後述の実験２〜実験５についても同様である。 FIG. 1 shows the measurement result of the hydrogen sulfide concentration in the hydrogen sulfide solution to which samples 1 to 3 are added, and FIG. 2 shows the measurement result of the hydrogen sulfide concentration in the hydrogen sulfide solution to which samples 4 to 6 are added. Moreover, the density | concentration of Fe, Mn, and Zn in the hydrogen sulfide solution which added the samples 1-3 is shown in FIG.3, FIG.4, FIG.5, respectively. Moreover, the density | concentration of Fe, Mn, and Zn in the hydrogen sulfide solution which added samples 4-6 is shown in FIG.6, FIG.7, FIG.8, respectively. Note that the same experiment was performed three times for each sample, the symbols in FIGS. 1 to 8 represent the average value, and the error bar represents the standard deviation. The same applies to Experiments 2 to 5 described later.
鉄鋼スラグを含有するサンプル１〜３でも、硫化水素はある程度減少しているが、鉄を含有するサンプル４〜６では、Ｈ２Ｓ５０、Ｈ２Ｓ１００のいずれについても、硫化水素はほぼ消失した。 In Samples 1 to 3 containing steel slag, hydrogen sulfide was reduced to some extent, but in Samples 4 to 6 containing iron, hydrogen sulfide was almost lost in both H2S50 and H2S100.
鉄の溶出量は、鉄粉を含有するサンプル４〜６では鉄鋼スラグを含有するサンプル１〜３に比べていずれも多い。また、他のＺｎ、Ｍｎ、Ｍｇについても、サンプル４〜６の方がサンプル１〜３よりも溶出量が多い。これらは鉄粉に含まれていない成分であるため、石炭灰から溶出しており、石炭灰と鉄との相性により、溶出量が高まったものと考えられる。 The amount of iron elution is larger in Samples 4 to 6 containing iron powder than in Samples 1 to 3 containing steel slag. Moreover, about other Zn, Mn, and Mg, the elution amount of the samples 4-6 is larger than the samples 1-3. Since these are components not contained in the iron powder, they are eluted from the coal ash, and it is considered that the amount of elution increased due to the compatibility between the coal ash and iron.
これらの結果から、石炭灰と鉄を組み合わせることが鉄鋼スラグと組み合わせることよりも適切であることがわかった。 From these results, it was found that combining coal ash and iron is more appropriate than combining steel slag.
（実験２）
金属イオンの溶出促進の補助剤として、クエン酸、炭素を用い、その影響について検証した。本実験で用いたサンプル１１〜１６の原料の配合割合を表４に示す。
(Experiment 2)
Citric acid and carbon were used as auxiliary agents for promoting the elution of metal ions, and their effects were verified. Table 4 shows the mixing ratio of the raw materials of Samples 11 to 16 used in this experiment.
サンプル１１〜１６、硫化水素溶液Ｈ２Ｓ０を用いて実験１と同様に実験を行った。そして、実験１と同様に硫化水素溶液中のＦｅ濃度を測定した。Ｆｅ濃度の測定結果を図９に示す。 Experiments were performed in the same manner as Experiment 1 using Samples 11 to 16 and the hydrogen sulfide solution H2SO. Then, as in Experiment 1, the Fe concentration in the hydrogen sulfide solution was measured. The measurement result of Fe concentration is shown in FIG.
炭素を含有するサンプル１２、１３では、炭素を含有しないサンプル１１に比べて鉄の溶出が促進されたものの、鉄の溶出量は炭素を３０重量％添加してもわずか３．６％程度の増加に留まった。 In the samples 12 and 13 containing carbon, the elution of iron was promoted compared to the sample 11 containing no carbon, but the iron elution amount increased by only 3.6% even when 30% by weight of carbon was added. Stayed in.
一方、クエン酸を添加した場合、０．１重量％添加したサンプル１４では、サンプル１１に比べ、鉄の溶出量が１０％程度増加しており、１．０重量％添加したサンプル１６では、鉄の溶出量が２８％程度増加した。この結果から、クエン酸は炭素よりも鉄の溶出を促進させることがわかった。 On the other hand, in the case of adding citric acid, in the sample 14 added with 0.1% by weight, the elution amount of iron increased by about 10% compared to the sample 11, and in the sample 16 added with 1.0% by weight, the iron Increased by about 28%. From this result, it was found that citric acid promotes elution of iron rather than carbon.
（実験３）
鉄粉と石炭灰の配合割合による影響について検証した。本実験で用いたサンプル２１〜２３の原料の配合割合を表５に示す。
(Experiment 3)
The effect of the mixing ratio of iron powder and coal ash was verified. Table 5 shows the mixing ratio of the raw materials of Samples 21 to 23 used in this experiment.
サンプル２１〜２３をそれぞれ用い、実験１と同様に実験を行った。そして、実験１と同様に、硫化水素溶液中の硫化水素濃度、並びに、Ｆｅ、Ｚｎ及びＭｎ濃度を測定した。硫化水素溶液中の硫化水素濃度、並びに、Ｆｅ、Ｚｎ及びＭｎ濃度の測定結果を図１０、図１１、図１２、図１３にそれぞれ示す。 Experiments were performed in the same manner as Experiment 1 using Samples 21 to 23, respectively. Then, as in Experiment 1, the hydrogen sulfide concentration and the Fe, Zn, and Mn concentrations in the hydrogen sulfide solution were measured. The measurement results of the hydrogen sulfide concentration and the Fe, Zn, and Mn concentrations in the hydrogen sulfide solution are shown in FIGS. 10, 11, 12, and 13, respectively.
Ｈ２Ｓ１００の試験区においては、サンプル２１、２２では硫化水素濃度は５０ｐｐｍ程度の減少、サンプル２３では３０ｐｐｍ程度の減少が見られたが、Ｈ２Ｓ５０の試験区においては、いずれのサンプルについても７０〜８０ｐｐｍ程度の減少であった。 In the test plot of H2S100, in samples 21 and 22, the hydrogen sulfide concentration decreased by about 50 ppm, and in sample 23, a decrease of about 30 ppm was observed, but in the test plot of H2S50, about 70 to 80 ppm for all samples. Decrease.
また、Ｆｅの溶出量は石炭灰を多く含有するサンプル２３で最大であり、５ｐｐｍほどの溶出が見られた。また、Ｚｎ、Ｍｎについても、Ｆｅと同様に石炭灰を多く含有するサンプル２３で多く溶出していた。 Moreover, the amount of Fe elution was maximum in Sample 23 containing a large amount of coal ash, and about 5 ppm was observed. Further, Zn and Mn were also eluted in a large amount in the sample 23 containing a large amount of coal ash as in the case of Fe.
これらの結果から、石炭灰と鉄粉の配合比率は、３：７〜７：３であればいずれでも硫化水素の低減効果が得られる。なお、石炭灰を多く含有するサンプル２３では、崩れがみられたことや、Ｍｎ、Ｚｎの溶出量からすると、石炭灰：鉄粉の配合比率は４：６〜６：４が好ましいと考えられる。 From these results, the reduction ratio of hydrogen sulfide can be obtained at any ratio of coal ash and iron powder in the range of 3: 7 to 7: 3. In addition, in the sample 23 containing much coal ash, it is thought that the blending ratio of coal ash: iron powder is preferably 4: 6 to 6: 4 from the fact that collapse was observed and the elution amounts of Mn and Zn. .
（実験４）
続いて、クエン酸の配合割合による影響について検証した。本実験で用いたサンプル３１〜３７の原料の配合割合を表６に示す。
(Experiment 4)
Then, it verified about the influence by the mixture ratio of a citric acid. Table 6 shows the mixing ratio of the raw materials of Samples 31 to 37 used in this experiment.
サンプル３１〜３７を用い、実験１と同様にして実験を行った。そして、実験１と同様に硫化水素濃度、並びに、Ｆｅ、Ｚｎ及びＭｎ濃度を測定した。更に、Ｈ２Ｓ０を用いて行ったものについては、ＮＯ３＋ＮＯ２−Ｎ、ＮＯ２−Ｎ、ＮＨ４−Ｎ、ＰＯ４−Ｐ、ＳｉＯ２−Ｓｉをオートアナライザー（ＳＷＡＡＴ，ＢＬＴＥＣ社製）で測定し、それぞれＣｕ−Ｃｄ還元法、ナフチルエチレンジアミン法、インドフェノール法、モリブデンブルー法、モリブデンブルー法で分析した。 Experiments were performed in the same manner as Experiment 1 using Samples 31 to 37. Then, as in Experiment 1, the hydrogen sulfide concentration and the Fe, Zn, and Mn concentrations were measured. Furthermore, for those conducted with H2S0 is determined NO 3 + NO 2 -N, NO 2 -N, NH 4 -N, PO 4 -P, the SiO 2 -Si auto analyzer (SWAAT, manufactured BLTEC Co.) Then, analysis was performed by Cu-Cd reduction method, naphthylethylenediamine method, indophenol method, molybdenum blue method, and molybdenum blue method, respectively.
硫化水素濃度、並びに、Ｆｅ、Ｚｎ及びＭｎ濃度の測定結果を図１４、図１５、図１６、図１７にそれぞれ示す。また、ＮＯ３＋ＮＯ２−Ｎ、ＮＯ２−Ｎ、ＮＨ４−Ｎ、ＰＯ４−Ｐ、ＳｉＯ２−Ｓｉのそれぞれの濃度の測定結果を図１８、図１９、図２０、図２１、図２２に示す。 The measurement results of the hydrogen sulfide concentration and the Fe, Zn, and Mn concentrations are shown in FIGS. 14, 15, 16, and 17, respectively. Further, the measurement results of the respective concentrations of NO 3 + NO 2 —N, NO 2 —N, NH 4 —N, PO 4 —P, and SiO 2 —Si are shown in FIG. 18, FIG. 19, FIG. 20, FIG. Shown in
図１４から、全てのサンプルで硫化水素低減傾向が見られ、クエン酸の含有量が多いほど硫化水素の低減効果が高いことがわかる。また、図１５〜図１７から、Ｆｅ、Ｚｎ、Ｍｎの溶出量についても、クエン酸の含有量が多いほど増加していることがわかる。なお、ＭｎはＨ２Ｓ０、Ｈ２Ｓ５０、Ｈ２Ｓ１００の各試験区において、濃度に大きな差がなく、また、Ｆｅ、Ｚｎについては、Ｈ２Ｓ０における濃度とＨ２Ｓ５０、Ｈ２Ｓ１００における濃度との差が大きかったことから、硫化水素の低減はＦｅ、Ｚｎの溶出による効果が大きいものと考えられる。なお、このことは、図１１〜図１３でも示されている。 FIG. 14 shows that all samples show a tendency to reduce hydrogen sulfide, and that the higher the citric acid content, the higher the effect of reducing hydrogen sulfide. 15 to 17, it can be seen that the elution amounts of Fe, Zn, and Mn increase as the citric acid content increases. Note that Mn has no significant difference in concentration in each of the test groups of H2S0, H2S50, and H2S100, and that of Fe and Zn has a large difference between the concentration in H2S0 and the concentration in H2S50 and H2S100. It is considered that the reduction of the effect of elution of Fe and Zn is large. This is also shown in FIGS.
また、Ｈ２Ｓ５０試験区において、クエン酸を３重量％以上含有するサンプル３４〜３７で硫化水素濃度はほぼ０になっていたことから、底質改善・施肥材はクエン酸を３重量％以上含有していることが好ましい。また、クエン酸を１０重量％含有するサンプル３７は脆く崩れやすかったことから、底質改善・施肥材の成形性及び形状維持性の観点から、底質改善・施肥材のクエン酸含有量が７重量％以下であることが好ましいと考えられる。 In the H2S50 test area, samples 34 to 37 containing citric acid in an amount of 3% by weight or more had a hydrogen sulfide concentration of approximately 0, so that the bottom sediment improving / fertilizing material contained citric acid in an amount of 3% by weight or more. It is preferable. Further, since the sample 37 containing 10% by weight of citric acid was brittle and easily collapsed, the citric acid content of the bottom improvement / fertilizer was 7 from the viewpoint of bottom sediment improvement / formability of the fertilizer and shape maintenance. It is considered that it is preferable to be not more than% by weight.
また、図１８〜図２２から、Ｎ、Ｐ、Ｓｉの溶出量についても、クエン酸の含有量が多いほど増加している。Ｎ、Ｐ、Ｓｉは生態系の栄養素として機能する一方で、有機物負荷の原因にもつながることから、富栄養化した底質では多く溶出させない方がよいと考えられる。しかしながら、多く溶出したＮＨ４でも１０数μモルであり、富栄養化を促進するほどの濃度ではない。また、クエン酸を１０重量％含有するサンプル３７において、溶出したＮ、Ｐ、Ｓｉ、Ｆｅのモル濃度比をとると、２０：０．８：１６：１であり、レッドフィールド比と比較すると、Ｆｅが１０００倍過剰であり、その他の元素はほぼ同じである。なお、レッドフィールド比とは、微細藻類の成長に最適な元素比を表すもので、生物体中の物質比率と環境水中の物質比率がほぼ同じで、生産と分解に係る物質のバランスに過不足がない状態を示す元素比の概念である。このように、Ｎ、Ｐ、Ｓｉの溶出量はレッドフィールド比と同様であるため、富栄養化した底質を更に悪化させるおそれもないと考えられるとともに、Ｆｅ等を多量に溶出させて硫化水素を低減させつつ、且つ、適度にＮ、Ｐ、Ｓｉを溶出させて栄養素を供給できることから水中における生態系の健全性回復のために好適であると言える。 From FIG. 18 to FIG. 22, the elution amounts of N, P, and Si also increase as the citric acid content increases. N, P, and Si function as ecosystem nutrients, but also cause organic load, so it is better not to elute them in eutrophic sediments. However, even a large amount of NH 4 eluted is a few tens of moles, which is not a concentration that promotes eutrophication. Further, in the sample 37 containing 10% by weight of citric acid, the molar concentration ratio of eluted N, P, Si, Fe is 20: 0.8: 16: 1, and compared with the red field ratio, Fe is 1000 times excess, and other elements are almost the same. The red field ratio is the optimal elemental ratio for the growth of microalgae. The substance ratio in the organism and the substance ratio in the environmental water are almost the same, and the balance of substances related to production and decomposition is too short or large. It is a concept of the element ratio indicating a state where there is no. Thus, since the elution amounts of N, P, and Si are the same as the red field ratio, it is considered that there is no possibility of further worsening the eutrophic bottom sediment, and a large amount of Fe and the like are eluted to generate hydrogen sulfide. It can be said that it is suitable for the restoration of the health of the ecosystem in the water because it can supply nutrients by appropriately eluting N, P and Si while reducing the amount of water.
（実験５）
実験４におけるサンプル３４（鉄粉：４８．５重量％、石炭灰：４８．５重量％、クエン酸：３重量％）を用い、海水での効果について検証した。
(Experiment 5)
Sample 34 in Experiment 4 (iron powder: 48.5% by weight, coal ash: 48.5% by weight, citric acid: 3% by weight) was used to verify the effect on seawater.
超純水１Ｌに人工海水粉末（レッドシーソルト，レッドシーソルト社）を３３ｇ入れて、３３ｐｓｕの人工海水を調製した。更に、Ｎ２ガスを吹き込んで空気をパージし、溶存酸素濃度を０．１ｍｇ／ｌ以下にした。これにＮａ２Ｓ・９Ｈ２Ｏを０、５０、１００ｍｇ−Ｓ／ｌとなるよう添加し、硫化水素溶液を調製した。この硫化水素溶液をそれぞれＳａ−Ｈ２Ｓ０、Ｓａ−Ｈ２Ｓ５０、Ｓａ−Ｈ２Ｓ１００と記す。 33 g of artificial seawater powder (Red Sea Salt, Red Sea Salt) was added to 1 L of ultrapure water to prepare 33 psu artificial seawater. Further, N 2 gas was blown in to purge the air, and the dissolved oxygen concentration was reduced to 0.1 mg / l or less. To this was added Na 2 S · 9H 2 O to 0, 50, 100 mg-S / l to prepare a hydrogen sulfide solution. This hydrogen sulfide solution is referred to as Sa-H2S0, Sa-H2S50, and Sa-H2S100, respectively.
１５０ｍｌバイアル瓶に上記の硫化水素溶液を１００ｍｌ入れた。これにサンプル３４を０．２ｇ静かに加えた後、ゴム栓およびアルミ金具で密閉した。ＭＡＧＩＣ ＶＡＣに１５０ｍｌバイアル瓶を入れ、密封用パックで密封し、２５℃、４０ｒｐｍで７日間振とうした後、硫化水素濃度を検知管で測定した。更に、０．４５μｍシリンジフィルターでろ過したろ液についてＦｅ、Ｚｎ、Ｍｎの各濃度をＩＣＰ−ＡＥＳで測定した。 100 ml of the above hydrogen sulfide solution was placed in a 150 ml vial. After 0.2 g of sample 34 was gently added thereto, it was sealed with a rubber stopper and an aluminum fitting. A 150 ml vial was placed in the MAGIC VAC, sealed with a sealing pack, shaken at 25 ° C. and 40 rpm for 7 days, and then the hydrogen sulfide concentration was measured with a detector tube. Furthermore, each density | concentration of Fe, Zn, and Mn was measured by ICP-AES about the filtrate filtered with the 0.45 micrometer syringe filter.
図２３に硫化水素溶液中の硫化水素濃度の測定結果を示す。また、Ｆｅ、Ｚｎ、Ｍｎ濃度を図２４〜図２６にそれぞれに示す。 FIG. 23 shows the measurement result of the hydrogen sulfide concentration in the hydrogen sulfide solution. The Fe, Zn, and Mn concentrations are shown in FIGS.
実験４において超純水で調製したＨ２Ｓ０、Ｈ２Ｓ５０、Ｈ２Ｓ１００で行った場合に比べると、Ｆｅ、Ｚｎ、Ｍｎの溶出は減少し、硫化水素の低減効果は若干劣る結果となったが、海水中においても硫化水素の低減効果を発揮することを確認した。 Compared to the case of H2S0, H2S50, and H2S100 prepared with ultrapure water in Experiment 4, the elution of Fe, Zn, and Mn decreased, and the effect of reducing hydrogen sulfide was slightly inferior. Has also been confirmed to exert the effect of reducing hydrogen sulfide.
本発明に係る底質改善・施肥材は、水中にて、鉄イオン等の金属イオンの溶出量が多く、金属イオンを錯体としてイオン状態のまま溶存させることができる。金属イオンは硫化水素と反応して金属硫化物を形成するので、閉鎖水域等にて硫化水素濃度を低減することができる。このため、閉鎖性水域における還元的な環境の改善に利用可能である。 The bottom improvement / fertilizer according to the present invention has a large amount of elution of metal ions such as iron ions in water, and can be dissolved in an ionic state as a complex of metal ions. Since metal ions react with hydrogen sulfide to form metal sulfide, the concentration of hydrogen sulfide can be reduced in a closed water area or the like. For this reason, it can be used to improve the reducing environment in closed waters.
Claims (10)
前記石炭灰と前記鉄との配合比が重量比で３：７〜７：３であり、
前記キレート剤がクエン酸であり、
水中で鉄イオン及び亜鉛イオンを溶出して、前記キレート剤とで鉄キレート及び亜鉛キレートを形成するとともに、窒素、リン及び珪素を溶出する、
ことを特徴とする底質改善・施肥材。 Contains coal ash, iron and chelating agent,
The mixing ratio of the coal ash and the iron is 3: 7 to 7: 3 by weight,
The chelating agent is citric acid;
Eluting iron ions and zinc ions in water, forming iron chelate and zinc chelate with the chelating agent, and eluting nitrogen, phosphorus and silicon,
Bottom sediment improvement and fertilizer.
ことを特徴とする請求項１に記載の底質改善・施肥材。 Containing 3 wt% or more and 7 wt% of the citric acid,
The bottom quality improving / fertilizing material according to claim 1 .
前記底質改善・施肥材から金属イオンを溶出させ、前記金属イオンを錯体として溶存させ、
前記金属イオンと底泥で生じる硫化水素との反応により金属硫化物を形成させて硫化水素濃度を低減させる、
ことを特徴とする底質改善方法。 Contains coal ash, iron and chelating agent, elutes iron ions and zinc ions in water, forms iron chelate and zinc chelate with the chelating agent, and improves bottom sediment to elute nitrogen, phosphorus and silicon・ Construct fertilizer in closed water area,
The metal ions are eluted from the bottom material improving and fertilizer, the metal ions are dissolved as a complex,
Reducing the hydrogen sulfide concentration by forming a metal sulfide by the reaction between the metal ions and hydrogen sulfide generated in the bottom mud,
The bottom quality improvement method characterized by this.
ことを特徴とする請求項３に記載の底質改善方法。The method for improving bottom sediment according to claim 3.
ことを特徴とする請求項３又は４に記載の底質改善方法。The method for improving bottom sediment according to claim 3 or 4, wherein:
ことを特徴とする請求項５に記載の底質改善方法。The method for improving bottom sediment according to claim 5.
前記底質改善・施肥材から金属イオンを溶出させて前記金属イオンを錯体として溶存させるとともに、窒素、リン及び珪素を溶出させて、これらを前記貝類或いは前記藻類に直接的或いは間接的に摂取させて前記貝類或いは前記藻類の成長を促進させる、
ことを特徴とする水生生物の養殖方法。 Contains coal ash, iron and chelating agent, elutes iron ions and zinc ions in water, forms iron chelate and zinc chelate with the chelating agent, and improves bottom sediment to elute nitrogen, phosphorus and silicon・ Place fertilizer in shellfish or algae culture waters,
The metal ions are eluted from the sediment improvement / fertilizer to dissolve the metal ions as a complex, and nitrogen, phosphorus, and silicon are eluted, and these are taken directly or indirectly by the shellfish or the algae. Promote the growth of the shellfish or the algae,
An aquatic culture method characterized by the above.
ことを特徴とする請求項７に記載の水生生物の養殖方法。The method for culturing aquatic organisms according to claim 7.
ことを特徴とする請求項７又は８に記載の水生生物の養殖方法。The method for culturing aquatic organisms according to claim 7 or 8.
ことを特徴とする請求項９に記載の水生生物の養殖方法。The method for culturing aquatic organisms according to claim 9.
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