JP6122369B2 - Method for producing organic fertilizer and organic feed - Google Patents
Method for producing organic fertilizer and organic feed Download PDFInfo
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- JP6122369B2 JP6122369B2 JP2013197147A JP2013197147A JP6122369B2 JP 6122369 B2 JP6122369 B2 JP 6122369B2 JP 2013197147 A JP2013197147 A JP 2013197147A JP 2013197147 A JP2013197147 A JP 2013197147A JP 6122369 B2 JP6122369 B2 JP 6122369B2
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- 239000003895 organic fertilizer Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910052793 cadmium Inorganic materials 0.000 claims description 101
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 100
- 239000000835 fiber Substances 0.000 claims description 45
- 239000013522 chelant Substances 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000002699 waste material Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 235000020637 scallop Nutrition 0.000 claims description 11
- 241000237509 Patinopecten sp. Species 0.000 claims description 9
- 239000003337 fertilizer Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 208000035404 Autolysis Diseases 0.000 claims description 2
- 206010057248 Cell death Diseases 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 230000028043 self proteolysis Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 102000004169 proteins and genes Human genes 0.000 description 11
- 108090000623 proteins and genes Proteins 0.000 description 11
- 239000002738 chelating agent Substances 0.000 description 10
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000237503 Pectinidae Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical group OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000000514 hepatopancreas Anatomy 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 108010028690 Fish Proteins Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 108010054866 Shellfish Proteins Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002358 autolytic effect Effects 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 102000038379 digestive enzymes Human genes 0.000 description 1
- 108091007734 digestive enzymes Proteins 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000002149 gonad Anatomy 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- 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
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Landscapes
- Fodder In General (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
- Fertilizers (AREA)
Description
本発明は、ホタテ貝の軟体部からカドミウムを除去した有機肥料及び有機飼料の製造方法に関し、特に酸やアルカリの成分を含まず無添加な有機肥料及び有機飼料を低コストで製造する方法に関する。 The present invention relates to a method for producing an organic fertilizer and an organic feed from which cadmium has been removed from a soft body part of a scallop, and more particularly, to a method for producing an additive-free organic fertilizer and an organic feed that do not contain an acid or alkali component at a low cost.
ホタテ貝は、年間５０万トン余り生産され、日本における総漁獲高のほぼ１０％を占める重要な食用等の資源である。主な可食部分である貝柱は、ホタテ貝の僅か１５重量％に過ぎず、残りの貝殻（５０重量％）と軟体部（３５重量％）とは、加工廃棄物として廃棄されている。この軟体部は、タンパク質やアミノ酸などの有用成分が多量に含まれており、肥料や飼料に再利用することが望ましい。 Scallops are an important edible resource that is produced over 500,000 tons per year and accounts for almost 10% of the total catch in Japan. The main edible portion of the scallop is only 15% by weight of the scallop, and the remaining shell (50% by weight) and soft body part (35% by weight) are discarded as processing waste. This soft body part contains a large amount of useful components such as proteins and amino acids, and it is desirable to reuse it for fertilizer and feed.
しかしながら軟体部に含まれるウロ（中腸腺）には、生物凝縮されたカドミウム（Ｃｄ）が、高い場合には１００ｍｇ／ｋｇ（乾燥状態）も含まれるため、そのままでは、肥料や飼料に再利用することができないだけでなく、加工廃棄物として廃棄することもできない。 However, the uro (midgut gland) contained in the soft body part contains 100 mg / kg (dry state) of biocondensed cadmium (Cd), so it can be reused as it is for fertilizer and feed. Not only can it be done, but it cannot be discarded as processing waste.
そこで軟体部からカドミウムを除去する方法として、加熱せずにキレート樹脂を酸性水溶液中で攪拌混合することで、軟体部と液相から同時にカドミウムを除去できる技術が提案されている（特許文献１参照。）。またｐＨを４以下で２０〜５０℃の温度に調整された醗酵槽で魚貝類タンパク質を自己消化させてこのタンパク質をアミノ酸液まで分解し、キレート剤にこのアミノ酸液に含まれるカドミウム等の重金属類を吸着させる技術が公開されている（特許文献２参照。）。 Therefore, as a method for removing cadmium from the soft body portion, a technique has been proposed in which cadmium can be removed simultaneously from the soft body portion and the liquid phase by stirring and mixing the chelate resin in an acidic aqueous solution without heating (see Patent Document 1). .) In addition, fish and shellfish protein is self-digested in a fermenter adjusted to a temperature of 20 to 50 ° C. with a pH of 4 or less, and this protein is decomposed into an amino acid solution, and heavy metals such as cadmium contained in this amino acid solution are added to the chelating agent. Has been disclosed (see Patent Document 2).
一般的に、カドミウムをタンパク質から遊離化するには、酸を用いてｐＨを４以下にする。さらに一旦遊離したカドミウムがタンパク質に再結合するのを防ぎ、カドミウムの遊離化をさらに高くするには、よりｐＨを低くして酸性にしなければならない。その点、特許文献１では、短時間でカドミウムを除去するためｐＨ５．０〜３．０の条件下で行っている。また特許文献２では、塩酸を添加してｐＨ４．０〜３．８に調整する上、カドミウムを効果的に遊離させるためにプロテアーゼを利用している。すなわちこれらの特許文献では酸性の薬品を用いてカドミウムを遊離化しているため、肥料や飼料の品質低下を招くばかりでなく、薬品コストが嵩む。
Generally, in order to liberate cadmium from a protein, the pH is adjusted to 4 or less using an acid. Furthermore, in order to prevent cadmium once released from rebinding to the protein and further increase the release of cadmium, the pH must be lowered and made acidic. In that respect, in
さらにキレート剤は、金属イオンをｐＨによって選択的に吸着しやすくする性質がある。その点、特許文献１では、最終的にｐＨ５．０〜３．０から中性付近にするためにアルカリを添加するので、その分薬品コストが嵩む。また特許文献２では、ｐＨ４．０からｐＨ８．０〜９．０に調整するためにアルカリを添加するので、その分薬品コストが嵩む。
Further, the chelating agent has a property of easily adsorbing metal ions selectively depending on pH. In that respect, in
また遊離したカドミウムはカドミウムイオンとなる。そのためカドミウムイオンがキレート剤に吸着すれば、タンパク質との再結合を防ぐことができる。しかしながら添加したキレート剤にはカドミウムイオン以外に鉄イオンやマンガンイオンなどの金属イオンも付着するため、単位面積あたりに吸着するカドミウムイオンの量には上限がある。その点、特許文献１及び特許文献２では、キレート剤の添加量はカドミウムの溶存量に応じており、キレート剤が多すぎると有機肥料や有機飼料に必要なミネラルまで除去してしまうばかりでなく、キレート剤のコストが嵩む。さらにキレート剤は極小なため、添加しても回収し難い。
The liberated cadmium becomes cadmium ion. Therefore, if cadmium ions are adsorbed on the chelating agent, rebinding with protein can be prevented. However, since the added chelating agent also attaches metal ions such as iron ions and manganese ions in addition to cadmium ions, there is an upper limit on the amount of cadmium ions adsorbed per unit area. In that respect, in
また軟体部から除去したカドミウムは廃液に混ざっているため、そのまま排水することはできない。この点について特許文献１及び特許文献２に記載はないが、環境を汚染せず低コストで廃液を処理する技術が求められている。
Moreover, since the cadmium removed from the soft body part is mixed in the waste liquid, it cannot be drained as it is. Although there is no description in this point in
そこで本発明の第１の目的は、酸やアルカリの成分を含まず無添加な有機肥料及び有機飼料を低コストで製造する方法を提供することにある。また本発明の第２の目的は、効率的かつ低コストでカドミウムを除去して有機肥料及び有機飼料を製造する方法を提供することにある。また本発明の第３の目的は、環境汚染をせずにカドミウムを含む廃液を処理して有機肥料及び有機飼料を製造する方法を提供することにある。 Therefore, a first object of the present invention is to provide a method for producing an additive-free organic fertilizer and organic feed containing no acid or alkali components at low cost. The second object of the present invention is to provide a method for producing organic fertilizer and organic feed by removing cadmium efficiently and at low cost. The third object of the present invention is to provide a method for producing an organic fertilizer and an organic feed by treating a waste liquid containing cadmium without causing environmental pollution.
上記課題を解決するために、本発明者は、鋭意研究と試験とを重ねた結果、貝殻及び貝柱や紐等の有用な部位の一部を取り分けた軟体部に、適量の水のみ加えて粉砕し一定温度下で加熱することで、この軟体部に含まれる消化酵素の働きを活発化させて、酸などの薬品を使用せずにタンパク質からカドミウムを遊離させることを見出した。また繊維状のキレート剤を使用することで処理液中からカドミウムを除去し易くしたばかりでなく、このキレート繊維を洗浄脱水及び再生処理して使用することで、キレート繊維に吸着したカドミウムを除去することが有機肥料及び有機飼料を製造する上で高効率であると共に、これらを製造する際に生じたカドミウムを含む廃液からカドミウムを分離して安全に処理することを見出した。 In order to solve the above-mentioned problems, the present inventor has intensively studied and tested, and as a result, added only an appropriate amount of water to the soft body part of the shell, shells, strings, and other useful parts, and pulverized. It was found that heating at a constant temperature activates the action of the digestive enzyme contained in the soft body part to release cadmium from the protein without using chemicals such as acids. Moreover, not only has it been easy to remove cadmium from the treatment liquid by using a fibrous chelating agent, but this chelate fiber can be washed, dehydrated and regenerated for use to remove cadmium adsorbed on the chelate fiber. It has been found that it is highly efficient in producing organic fertilizers and organic feeds, and cadmium is separated from the waste liquid containing cadmium produced in the production thereof and can be safely treated.
すなわち本発明による有機肥料及び有機飼料の製造方法は、カドミウムを含むホタテ貝の軟体部に対してＰＨ調整をすることなく所定量の水を加えた上で当該軟体部を粉砕し、前記粉砕した軟体部をＰＨ調整をすることなく攪拌しながら自己消化させる第１工程と、前記第１工程で自己消化した軟体部にキレート繊維を添加して前記カドミウムを吸着させる第２工程と、前記第２工程でカドミウムが除去された軟体部を加熱処理する第３工程とを含むことを特徴とする。 That method of manufacturing the organic fertilizer and organic feed according to the present invention, for the soft body portion of the scallop containing cadmium by grinding the soft body portion on obtained by adding a predetermined amount of water without the PH adjustment, and the crushed A first step of self-digesting the soft body while stirring without adjusting the pH; a second step of adding chelate fibers to the soft body that was self-digested in the first step to adsorb the cadmium; And a third step of heat-treating the soft body part from which the cadmium has been removed in the step.
前記第１工程で加える水が軟体部の１／１０〜３／１０重量であることが望ましい。 The water added in the first step is desirably 1/10 to 3/10 weight of the soft body part.
前記第１工程で粉砕した軟体部の自己消化は、４０〜５５℃で少なくとも５時間攪拌することにより行うことが望ましい。 The autolysis of molluscs portion was ground in the first step is preferably carried out by stirring for at least 5 hours at 40 to 5 5 ° C..
前記第２工程で添加するキレート繊維が自己消化した軟体部の１〜４重量％であることが望ましい。 It is desirable that the chelate fiber added in the second step is 1 to 4% by weight of the soft-digested soft body part.
前記第２工程でキレート繊維を添加して１〜３時間攪拌することによりカドミウムを吸着させることが望ましい。 It is desirable to adsorb cadmium by adding chelate fiber in the second step and stirring for 1 to 3 hours.
前記第２工程でカドミウムが吸着したキレート繊維を再生処理した時に前記カドミウムを含む廃液を収集する第４工程と、前記第４工程で収集した前記カドミウムを含む廃液に金属捕集材及び活性炭を加え、前記金属捕集材に捕集された前記カドミウムを含む活性炭を固液分離する第５工程とをさらに含むことが望ましい。 A fourth step of collecting the waste liquid containing cadmium when the chelate fiber adsorbed with cadmium in the second step is regenerated, and a metal trapping material and activated carbon are added to the waste liquid containing cadmium collected in the fourth step. Preferably, the method further includes a fifth step of solid-liquid separation of the activated carbon containing the cadmium collected by the metal collecting material.
前記第５工程の金属捕集材が前記廃液の９０〜１８１．５重量ｐｐｍ、活性炭が前記廃液の０．２５〜０．５重量％であることが望ましい。 It is desirable that the metal collection material of the fifth step is 90 to 181.5 ppm by weight of the waste liquid and the activated carbon is 0.25 to 0.5% by weight of the waste liquid.
ここでホタテ貝の「軟体部」とは、ホタテ貝の貝殻を除いた軟体部から貝柱や紐等の有用な部位を一部取り分けた後の残りの部分を意味し、具体的には、ウロ（中腸腺）、生殖腺、外套膜、鰓、心臓、及び腎臓等が該当する。「キレート繊維」とは、金属イオンを吸着できるキレート剤を含み、繊維状にしたもの、すなわちキレート型イオン交換繊維のことであり、イオン交換を行う官能基としてイミノ酢酸基を有するものを意味する。「再生処理」とは、キレート繊維のカドミウムの吸着能力が低下した時に、塩酸などの酸を用いて、キレート繊維上のカドミウムなどの金属イオンを取り除くことを意味する。「金属捕集材」とは、廃液に含まれる重金属イオン類に反応して捕捉し、不溶化するものを意味する。 Here, the “soft body” of scallop means the remaining part after separating useful parts such as scallops and strings from the soft body excluding the scallop shell. (Midgut gland), gonad, mantle, sputum, heart, kidney, etc. “Chelating fiber” means a fiber containing a chelating agent capable of adsorbing metal ions, that is, a chelating ion exchange fiber, and means having an iminoacetic acid group as a functional group for performing ion exchange. . “Regeneration treatment” means removal of metal ions such as cadmium on the chelate fiber using an acid such as hydrochloric acid when the cadmium adsorption ability of the chelate fiber is reduced. “Metal trapping material” means a material that reacts with and captures heavy metal ions contained in the waste liquid to insolubilize it.
本発明による有機肥料及び有機飼料の製造方法では、有機酸も無機酸も一切使わず軟体部の自己消化酵素でカドミウムを遊離化するため、有機肥料及び有機飼料の品質を保持できるばかりでなく、薬品代が嵩まないため低コストで処理することができる。また水の添加量もできるだけ少なくして処理しているので、乾燥時における重油などの燃料を少なくできる。またカドミウムを除去するキレート繊維は、洗浄脱水してカドミウムの吸着能力が低下するまで連続使用でき、さらにカドミウムの吸着能力が低下したキレート繊維は、再生処理を行い、カドミウムを取り除いて再生することができ、キレート繊維のコストも抑えることができる。 In the method for producing organic fertilizer and organic feed according to the present invention, cadmium is liberated by the self-digesting enzyme of the soft part without using any organic acid or inorganic acid, so that the quality of the organic fertilizer and organic feed can be maintained, Since the cost of chemicals does not increase, it can be processed at low cost. Also, since the amount of water added is reduced as much as possible, fuel such as heavy oil during drying can be reduced. The chelating fiber that removes cadmium can be used continuously until it is washed and dehydrated until the adsorption capacity of the cadmium decreases, and the chelating fiber that has further decreased the adsorption capacity of the cadmium can be regenerated, removed and regenerated by removing the cadmium. And the cost of the chelate fiber can be reduced.
図１を参照しつつ、本発明による有機肥料及び有機飼料の製造方法を説明する。図１ではＡ〜Ｃ工程が図示してある。図１のＡ工程に示すように、ホタテ貝から、貝殻と貝柱と紐等の有用な部位の一部とを取り分けた残りの軟体部を採取する（Ａ１）。次に（Ａ１）で採取した軟体部の１／１０〜３／１０重量の水を、この軟体部に加えてミキサーで粉砕する（Ａ２）。そして（Ａ２）で粉砕した軟体部を４０〜５０℃で５〜２５時間攪拌することにより自己消化させる（Ａ３）。 With reference to FIG. 1, the manufacturing method of the organic fertilizer and organic feed by this invention is demonstrated. In FIG. 1, steps A to C are shown. As shown in step A of FIG. 1, the remaining soft body part obtained by separating a shell, a scallop, and a part of a useful part such as a string is collected from a scallop (A1). Next, water of 1/10 to 3/10 weight of the soft part collected in (A1) is added to the soft part and pulverized with a mixer (A2). And the soft body part grind | pulverized by (A2) is self-digested by stirring at 40-50 degreeC for 5 to 25 hours (A3).
ここで、軟体部は流動性が低くドロドロしているため攪拌しにくい。このため適量の水を軟体部に加えることで、流動性がよくなり攪拌効率が上がる。したがって自己消化酵素が軟体部全体で働きやすくなり、タンパク質からカドミウムが遊離しやすくなる。また粉砕した軟体部の流動性がよいと遊離したカドミウムがキレート繊維に吸着しやすくなるため、除去効率があがる。 Here, since the soft body part is low in fluidity and muddy, it is difficult to stir. Therefore, by adding an appropriate amount of water to the soft body part, the fluidity is improved and the stirring efficiency is increased. Therefore, the self-digesting enzyme becomes easy to work in the entire soft body part, and cadmium is easily released from the protein. Moreover, if the fluidity of the pulverized soft body part is good, the liberated cadmium is easily adsorbed on the chelate fiber, so that the removal efficiency is improved.
すなわち軟体部に加える水の量は、カドミウムの遊離化とキレート繊維への吸着性に影響を与える。水の量が少なすぎると、粉砕した軟体部の流動性が低くなり、攪拌が不十分となる。そのため自己消化酵素による処理が長くなるばかりでなく、カドミウムの遊離化も不十分となる恐れがある。一方、水の量が多すぎると、自己消化酵素の濃度が下がるので、タンパク質との反応が遅れる恐れがある。また雑菌の活動が盛んになり、腐敗する。さらにキレート繊維でカドミウムを除去したタンパク質を含む液体から肥料又は飼料を製造するとき、水分を乾燥させるエネルギーコストが嵩む。このため軟体部に加える水の量は、軟体部の１／１０〜３／１０重量がよく、望ましくは１／５重量がよい。換算すると、処理する軟体部が含む水分量の変動を考慮すると、軟体部１００ｇに対して、水の量は１０ｇ〜３０ｇがよく、望ましくは２０ｇがよい。 That is, the amount of water added to the soft body part affects the liberation of cadmium and the adsorptivity to the chelate fiber. When the amount of water is too small, the fluidity of the pulverized soft body part becomes low and stirring becomes insufficient. For this reason, not only the treatment with the self-digesting enzyme becomes longer, but also the liberation of cadmium may be insufficient. On the other hand, if the amount of water is too large, the concentration of the autolytic enzyme will decrease, and the reaction with the protein may be delayed. In addition, the activity of various bacteria becomes active and it rots. Furthermore, when manufacturing a fertilizer or feed from the liquid containing the protein which removed the cadmium with the chelate fiber, the energy cost which dries a moisture increases. For this reason, the amount of water added to the soft body part is preferably 1/10 to 3/10 weight, more preferably 1/5 weight of the soft body part. In terms of conversion, in consideration of fluctuations in the amount of water contained in the soft body part to be processed, the amount of water is preferably 10 g to 30 g, more preferably 20 g, relative to 100 g of the soft body part.
攪拌する粉砕した軟体部の温度は、低すぎると酵素の働きが弱まってしまうため、カドミウムの遊離化が不十分となる恐れがある。一方、粉砕した軟体部の温度が高すぎるとタンパク質が変性してしまうため、自己消化酵素が失活してカドミウムの遊離化が不十分となる恐れがある。このため攪拌する粉砕した軟体部の温度は、４０〜５５℃がよく、望ましくは４５℃がよい。 If the temperature of the pulverized soft body part to be stirred is too low, the function of the enzyme is weakened, so that there is a possibility that the liberation of cadmium may be insufficient. On the other hand, if the temperature of the pulverized soft body part is too high, the protein is denatured, so that the self-digesting enzyme may be deactivated and cadmium may be insufficiently liberated. For this reason, the temperature of the pulverized soft body part to be stirred is preferably 40 to 55 ° C, and preferably 45 ° C.
粉砕した軟体部を攪拌する時間は、自己消化の進度を考慮すれば少なくとも５時間は必要であり、１５〜２５時間でもよく、望ましくは２０時間がよい。 The time for stirring the pulverized soft body part is required to be at least 5 hours in consideration of the progress of self-digestion, may be 15 to 25 hours, and preferably 20 hours.
Ｂ工程は、Ａ工程後に続けて行う。すなわち軟体部の自己消化液に１重量％のキレート繊維を添加する（Ｂ１）。次に（Ｂ１）でキレート繊維が添加された軟体部を常温で１〜３時間攪拌する（Ｂ２）。そして（Ｂ２）で軟体部を攪拌後、キレート繊維を自己消化液から取り出し、キレート繊維を脱水処理する（Ｂ３）。なお（Ｂ３）にて脱水処理した後、（１）カドミウムを除去した軟体部、（２）カドミウムが吸着したキレート繊維が得られる。 The B process is performed after the A process. That is, 1% by weight of chelate fiber is added to the soft digestion liquid of the soft body part (B1). Next, the soft body part to which the chelate fiber is added in (B1) is stirred at room temperature for 1 to 3 hours (B2). And after a soft body part is stirred by (B2), a chelate fiber is taken out from a self-digestion liquid, and a chelate fiber is dehydrated (B3). After dehydration in (B3), (1) a soft body part from which cadmium has been removed and (2) a chelate fiber to which cadmium has been adsorbed are obtained.
キレート繊維はタンパク質から遊離した液中のカドミウムイオンを中性付近の条件下で優先的に吸着させる機能を持ち、キレート繊維状のイミノ酢酸基にはナトリウムイオンが結合している。ナトリウムよりも結合しやすい金属イオンが液中に存在すると、ナトリウムイオンを液中に放出し、金属イオンを吸着させていく。キレート繊維は、カドミウムイオンを優先的に吸着するが、カドミウムイオンの液中濃度が低下した後に、鉄イオンやマンガンイオンなどのキレート繊維に比較的吸着しやすい金属イオンも、カドミウムイオンの液中濃度が低下した後に、吸着してしまう。カドミウム以外の金属イオンがキレート繊維に吸着してしまうと、その分カドミウムイオンを吸着する能力が早く低下するため、キレート繊維の再生処理の頻度が増えてしまう恐れがある。また、カドミウム以外の金属イオンには、ミネラルとして植物に有用なものもあり、キレート繊維に吸着して取り除いてしまうと、得られる肥料のミネラル分が低下してしまう。尚、カドミウムの吸着する能力が低下したキレート繊維は、塩酸などの酸で洗浄することで、再生処理をすれば、再度使用できる。 The chelate fiber has a function of preferentially adsorbing cadmium ions in the liquid released from the protein under conditions near neutrality, and sodium ions are bound to the chemifiber-like iminoacetic acid groups. When metal ions that are easier to bind than sodium are present in the liquid, sodium ions are released into the liquid and the metal ions are adsorbed. Chelate fibers preferentially adsorb cadmium ions, but metal ions that are relatively easy to adsorb to chelate fibers such as iron ions and manganese ions after the concentration of cadmium ions in the solution is reduced. Adsorbs after the drop. If metal ions other than cadmium are adsorbed on the chelate fiber, the ability to adsorb cadmium ions will be reduced accordingly, and the frequency of the chelate fiber regeneration process may increase. Moreover, some metal ions other than cadmium are useful for plants as minerals. If they are adsorbed and removed by chelating fibers, the mineral content of the resulting fertilizer will be reduced. The chelate fiber having a reduced ability to adsorb cadmium can be reused if it is regenerated by washing with an acid such as hydrochloric acid.
添加するキレート繊維が少なすぎると、カドミウムの除去が不十分になる恐れがある。一方、キレート繊維が多すぎると、上述したように他の金属イオンが吸着してしまうためキレート繊維の添加量に比例してカドミウムの除去率が上がるわけではない。そこでカドミウムの除去率、ミネラルなど植物に必要な養分及びコストを考慮すると、キレート繊維の添加量は軟体部の１〜４重量％がよく、望ましくは１重量％がよい。 If too little chelating fiber is added, cadmium removal may be insufficient. On the other hand, when there are too many chelate fibers, other metal ions are adsorbed as described above, so the removal rate of cadmium does not increase in proportion to the amount of chelate fibers added. In view of the removal rate of cadmium, nutrients necessary for plants such as minerals, and cost, the amount of chelate fiber added is preferably 1 to 4% by weight, more preferably 1% by weight of the soft body.
キレート繊維を添加しただけでは、溶液中に含まれるカドミウムを除去しきれない。繊維状のキレート表面にカドミウムイオンが引き寄せられるわけではなく、キレート表面にカドミウムを接触させなければ吸着しないからである。そこで軟体部を攪拌する時間は、カドミウムの除去度合に応じて変更してもよい。しかしながら長く処理すると自己消化が進み雑菌の繁殖や腐敗などの影響があるため、望ましくは１〜３時間がよく、より望ましくは２時間がよい。 Cadmium contained in the solution cannot be removed simply by adding the chelating fiber. This is because cadmium ions are not attracted to the fibrous chelate surface, and are not adsorbed unless cadmium is brought into contact with the chelate surface. Then, you may change the time which stirs a soft body part according to the removal degree of cadmium. However, if the treatment is carried out for a long time, self-digestion progresses and there is an influence such as propagation of bacteria and spoilage. Therefore, it is preferably 1 to 3 hours, more preferably 2 hours.
Ｃ工程は、Ｂ工程後に続けて行う。すなわちカドミウムを除去した軟体部を加熱処理する（Ｃ１）。この加熱処理により軟体部の酵素は失活するため、肥料や飼料が雑菌で汚染されるのを防げる。そして有機肥料及び有機飼料の原料となる（Ｃ２）。 The C process is performed after the B process. That is, the soft body part from which cadmium has been removed is subjected to heat treatment (C1). This heat treatment inactivates the enzyme in the soft body part, so that the fertilizer and feed can be prevented from being contaminated with bacteria. And it becomes a raw material of organic fertilizer and organic feed (C2).
図２は、キレート繊維を再生処理した時に発生するカドミウムを含む廃液を処理する流れ図である。図２では、Ｄ工程が図示してある。Ｄ工程の（Ｄ１）は、図１のＢ工程（Ｂ３）（２）カドミウムが吸着したキレート繊維を再生処理した後に残ったカドミウムを含む廃液である。まずカドミウムを含む廃液に、重金属捕集材９０〜１８１．５重量ｐｐｍ加えて５分間攪拌する（Ｄ２）。次に（Ｄ２）で攪拌したカドミウムを含む廃液に、この廃液に対して活性炭０．２５〜０．５重量％加えて３０分間攪拌する（Ｄ３）。最後に（Ｄ３）で攪拌したカドミウムを含む廃液を３５００Ｇで１０分間遠心分離をかけ、カドミウムを含む活性炭を分離する（Ｄ４）。 FIG. 2 is a flowchart for treating a waste liquid containing cadmium generated when the chelate fiber is regenerated. In FIG. 2, the process D is illustrated. Step D (D1) is a waste liquid containing cadmium remaining after regenerating the chelate fiber adsorbed with B step (B3) (2) cadmium in FIG. First, 90 to 181.5 ppm by weight of heavy metal collection material is added to a waste liquid containing cadmium and stirred for 5 minutes (D2). Next, 0.25 to 0.5% by weight of activated carbon is added to the waste liquid containing cadmium stirred in (D2) and stirred for 30 minutes (D3). Finally, the waste liquid containing cadmium stirred in (D3) is centrifuged at 3500 G for 10 minutes to separate activated carbon containing cadmium (D4).
廃液はカドミウムを含むので、工場排水としてそのまま放流することができない。そこで一般的には金属捕集材を廃液に添加してカドミウムと結合させる。その後高分子凝集材を添加し、カドミウムと結合した金属捕集剤を凝集し沈殿させる。
しかしながらこのやり方では特殊な設備で凝集沈殿を確実に行う必要があり汎用性に欠ける。そこで特殊な設備が必要なく比較的安価な活性炭を高分子凝集材の代替品として用いたところ、カドミウムの収集効果があることを発見した。
Since the waste liquid contains cadmium, it cannot be discharged as factory wastewater. Therefore, in general, a metal collecting material is added to the waste liquid and combined with cadmium. Thereafter, a polymer aggregating agent is added to agglomerate and precipitate the metal scavenger bound to cadmium.
However, in this method, it is necessary to reliably perform the coagulation sedimentation with special equipment, and lacks versatility. Therefore, when using relatively cheap activated carbon, which does not require special equipment, as an alternative to polymer agglomerates, it was discovered that it has a cadmium collection effect.
図３は、取り分けた軟体部（１０ｋｇ）に、この軟体部の１／５重量の水（２ｋｇ）を加えてミキサーで粉砕した後、２０時間・４５℃で自己消化処理した軟体部の試験結果を示す。図３（１）は軟体部に含まれる窒素の量の割合を示し、窒素の量が１．８６％、図３（２）は軟体部に含まれるカドミウムの量を示し、カドミウムの量が２．７７ｍｇ／ｋｇ、図３（３）は軟体部のカドミウム濃度を示し、カドミウム濃度は１．４９ｐｐｍ／窒素１％であることが確認できた。肥料のカドミウム含有量の基準値は、窒素１％あたり０．８ｐｐｍ以下であるため、基準値より高い。
Fig. 3 shows the test results of the soft body part that was self-digested at 45 ° C for 20 hours after adding 1/5 weight of water (2 kg) to the soft body part (10 kg) and pulverizing with a mixer. Indicates. 3 (1) shows the ratio of the amount of nitrogen contained in the soft body part, the amount of nitrogen is 1.86%, FIG. 3 (2) shows the amount of cadmium contained in the soft body part, and the amount of cadmium is 2 .77 mg / kg, FIG. 3 (3) shows the cadmium concentration of the soft body part, and it was confirmed that the cadmium concentration was 1.49 ppm /
図４は、軟体部の自己消化に費やす時間及び温度と、それぞれの軟体部に１重量％キレート繊維を添加して除去したカドミウムとの関係を示す。本試験では自己消化の時間を５時間，１０時間，１５時間，２０時間、温度を４０℃，４５℃，５０℃，５５℃、それぞれの状態で１重量％キレート繊維（ニチビイオン交換繊維（キレート型：IEF-IAc(H),(Na)）を添加している。この繊維は、中性付近でカドミウムと結合し易く、他の金属イオンよりも優先的に吸着させることができる。図４（１）は軟体部のカドミウム濃度を示し、４５℃で自己消化したときにカドミウム濃度の平均値は低く、時間を費やすほどこのカドミウム濃度は低くなることがわかった。図４（２）は軟体部の窒素１％当りのカドミウム濃度を示し、４５℃で自己消化したときに窒素１％当りのカドミウム濃度の平均値は低く、時間を費やすほどカドミウム濃度は低くなることがわかった。図４（３）はカドミウムの除去率を示し、４５℃で自己消化したときにカドミウムの除去率の平均値が高く、時間を費やすほどカドミウムの除去率は高くなることがわかった。 FIG. 4 shows the relationship between the time and temperature spent for soft body self-digestion and cadmium removed by adding 1 wt% chelate fiber to each soft body part. In this test, the self-digestion time was 5 hours, 10 hours, 15 hours, and 20 hours, and the temperatures were 40 ° C., 45 ° C., 50 ° C., and 55 ° C., respectively, and 1 wt% chelate fiber (Nichibi ion exchange fiber (chelate type) : IEF-IAc (H), (Na)) This fiber easily binds to cadmium near neutrality and can be preferentially adsorbed over other metal ions. 1) shows the cadmium concentration of the soft body part, and it was found that the average value of the cadmium concentration was low when self-digested at 45 ° C., and this cadmium concentration became lower as time was spent. The cadmium concentration per 1% of nitrogen was shown, and the average value of the cadmium concentration per 1% of nitrogen was low when self-digested at 45 ° C. It was found that the cadmium concentration decreased as time was spent. ) Excludes cadmium Indicates the rate, high average value of the removal rate of cadmium when autolyzed at 45 ° C., was found to be higher removal rate of cadmium as time consuming.
図５は、図２のＤ工程で処理したカドミウムを含む廃液のカドミウム量を測定した試験データと比較データを示す。図５にて、試験試料１〜６及び比較試料７〜８の試験結果を示す。重金属捕集剤は、ミヨシ油脂製エポフロックを使用している。試験試料１〜３では、重金属捕集材を１８１．５重量ｐｐｍ、活性炭を０．７５重量％、０．５重量％、０．２５重量％それぞれ添加した場合のカドミウム濃度を測った。この場合、カドミウム濃度は全て０．０４ｍｇ／ｋｇだった。また試験試料４〜６では、重金属捕集材を９０．７５重量ｐｐｍ、活性炭を０．７５重量％、０．５重量％、０．２５重量％それぞれ添加した場合のカドミウム濃度を測った。この場合、カドミウム濃度は０〜０．１ｍｇ／ｋｇに収まることがわかった。
FIG. 5 shows test data and comparison data obtained by measuring the amount of cadmium in the waste liquid containing cadmium processed in step D of FIG. In FIG. 5, the test results of
一方、比較試料７では、重金属捕集材を１８１．５重量ｐｐｍ、高分子凝結剤を０．１重量％添加し、活性炭を添加しない場合のカドミウム濃度を測った。この場合、カドミウム濃度は０．２８ｍｇ／ｋｇだった。比較試料８では、重金属捕集材、高分子凝結剤、活性炭どれも添加しない場合のカドミウム濃度を測ったところ、８．０５ｍｇ／ｋｇだった。
On the other hand, in Comparative Sample 7, the cadmium concentration was measured when 181.5 ppm by weight of the heavy metal collecting material and 0.1% by weight of the polymer coagulant were added, and no activated carbon was added. In this case, the cadmium concentration was 0.28 mg / kg. In
Claims (5)
前記第１工程で自己消化した軟体部にキレート繊維を添加して前記カドミウムを吸着させる第２工程と、
前記第２工程でカドミウムが除去された軟体部を加熱処理する第３工程とを含んでなり、
前記第１工程で加える水の量は、前記軟体部の１／１０〜３／１０重量であり、
前記第１工程で粉砕した軟体部の自己消化は、４０〜５５℃で少なくとも５時間攪拌することにより行う
ことを特徴とする有機肥料及び有機飼料の製造方法。 For the soft body portion of the scallop containing cadmium by grinding the soft body portion on obtained by adding a predetermined amount of water without the PH adjustment, it is autolyzed with stirring without a soft body portion and the pulverized to PH adjustment The first step;
A second step of adsorbing the cadmium by adding a chelate fiber to the soft body part that is self-digested in the first step;
And a third step of heat-treating the soft body portion cadmium is removed in the second step becomes Nde including,
The amount of water added in the first step is 1/10 to 3/10 weight of the soft body part,
The method for producing an organic fertilizer and organic feed, wherein the autolysis of the soft body part pulverized in the first step is performed by stirring at 40 to 55C for at least 5 hours .
ことを特徴とする請求項１に記載の有機肥料及び有機飼料の製造方法。 The method for producing an organic fertilizer and organic feed according to claim 1, wherein the chelate fiber added in the second step is 1 to 4% by weight of the self-digested soft body part .
ことを特徴とする請求項１又は２に記載の有機肥料及び有機飼料の製造方法。 The method for producing organic fertilizer and organic feed according to claim 1 or 2, wherein chelate fibers are added in the second step and cadmium is adsorbed by stirring for 1 to 3 hours .
前記第４工程で収集した前記カドミウムを含む廃液に金属捕集材及び活性炭を加え、前記金属捕集材に捕集された前記カドミウムを含む活性炭を固液分離する第５工程と
をさらに含む
ことを特徴とする請求項１乃至３のいずれか１項に記載の有機肥料及び有機飼料の製造方法。 A fourth step of collecting waste liquid containing the cadmium when the chelate fiber adsorbed with cadmium in the second step is regenerated.
A fifth step of solid-liquid separation of the activated carbon containing cadmium collected in the metal collecting material by adding a metal collecting material and activated carbon to the waste solution containing cadmium collected in the fourth step;
The method for producing organic fertilizer and organic feed according to any one of claims 1 to 3 , further comprising :
ことを特徴とする請求項４に記載の有機肥料及び有機飼料の製造方法。 Organic claim 4 metal collecting material of the fifth step is from 90 to 181.5 ppm by weight of the waste, activated carbon, wherein 0.25-0.5 wt% der Rukoto of the waste Manufacturing method of fertilizer and organic feed.
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| 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 |
| JP2002336818A (en) * | 2001-05-17 | 2002-11-26 | Tamura Kagaku Kenkyusho:Kk | Method for treating processing residue of mollusk food, treatment process and treatment device used therefor |
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