JP2021041318A - Method for making wood drying waste liquid colorless - Google Patents
Method for making wood drying waste liquid colorless Download PDFInfo
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- JP2021041318A JP2021041318A JP2019163679A JP2019163679A JP2021041318A JP 2021041318 A JP2021041318 A JP 2021041318A JP 2019163679 A JP2019163679 A JP 2019163679A JP 2019163679 A JP2019163679 A JP 2019163679A JP 2021041318 A JP2021041318 A JP 2021041318A
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- 239000007788 liquid Substances 0.000 title claims abstract description 42
- 238000001035 drying Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 239000002023 wood Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 9
- 230000005291 magnetic effect Effects 0.000 claims abstract description 9
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002440 industrial waste Substances 0.000 claims abstract description 7
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000002916 wood waste Substances 0.000 claims description 5
- 238000005498 polishing Methods 0.000 description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 240000005109 Cryptomeria japonica Species 0.000 description 4
- 238000005562 fading Methods 0.000 description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000013642 negative control Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 241000218645 Cedrus Species 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- KEHCHOCBAJSEKS-UHFFFAOYSA-N iron(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Fe+2] KEHCHOCBAJSEKS-UHFFFAOYSA-N 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000013138 pruning Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
Description
本発明は、木材乾燥機から流出する有色の廃液を退色させ、略無色の廃液に変換する方法に関する。 The present invention relates to a method for fading a colored waste liquid flowing out of a wood dryer and converting it into a substantially colorless waste liquid.
木材は、水分が含まれる生材の状態では変形や割れが生じるため、生材を乾燥して建築用製材などに利用される。生材の乾燥方法としては、天然乾燥のほか、人工的に加熱水蒸気を用いて乾燥させる蒸気式木材乾燥（以下、「蒸気式乾燥」という。）が広く用いられている。蒸気式乾燥においては、木材中の水分が加熱水蒸気と共に蒸気式乾燥機の排気口から大気中へ排出されると共に、蒸気式乾燥機底面から流出する液体（以下、「ドレーン」という。）が廃液として河川などに放流されている。 Since wood is deformed or cracked in the state of a raw material containing water, the raw material is dried and used for construction lumber. As a method for drying raw wood, in addition to natural drying, steam-type wood drying (hereinafter referred to as "steam-type drying"), which artificially dries using heated steam, is widely used. In steam drying, the moisture in the wood is discharged to the atmosphere together with the heated steam from the exhaust port of the steam dryer, and the liquid flowing out from the bottom of the steam dryer (hereinafter referred to as "drain") is waste liquid. It is released into rivers and the like.
蒸気式乾燥処理で排気口から出される蒸気については成分分析などが行われ、該成分を活用した有効利用が図られている。例えば、蒸気式乾燥機から排出される蒸気の有効利用については、加熱温度９０度〜１２０度の蒸気式乾燥で排出される蒸気を自然冷却させて液体を補集し、上部に浮遊した木材精油を除去して消臭剤として利用することが開示されている（特許文献１）。また、このときの排出液は、白濁しており少量の有機層が含まれていることが開示されている（同特許文献１［００１３］段落参照）。 The steam emitted from the exhaust port in the steam-type drying process is subjected to component analysis and the like, and effective utilization of the components is being achieved. For example, regarding the effective use of steam discharged from a steam dryer, the steam discharged by steam drying at a heating temperature of 90 to 120 degrees is naturally cooled to collect the liquid, and the wood essential oil floats on the upper part. Is disclosed to be used as a deodorant by removing the above (Patent Document 1). Further, it is disclosed that the discharged liquid at this time is cloudy and contains a small amount of an organic layer (see paragraph 1 [0013] of the same patent document 1).
また、乾燥機排出口から出る排気を水冷式のコンデンサーを通して液体を回収し、その液体中の油分にセスキテルペンアルコールが含まれること及びこれを用いてナメクジなどの陸生軟体動物の忌避剤とすることが開示されている（特許文献２［００１０］段落参照）。 In addition, the liquid is recovered from the exhaust from the dryer outlet through a water-cooled condenser, and the oil in the liquid contains sesquiterpene alcohol, and this is used as a repellent for terrestrial mollusks such as slugs. Is disclosed (see paragraph 2 [0010] of Patent Document).
一方、ドレーンについては何ら処理されることなく河川へ放流されており、化合物の特定や有効利用は図られていない。なお、ドレーンについての唯一の研究報告（非特許文献１）があるが、これは、スギ柱材の木材乾燥機から排出されるドレーン発生量の経時変化及びｐＨを明らかにしたというものであり、ドレーンにオゾンを添加して黒色を多少淡色化できたこと及びドレーンを微生物培養に利用する可能性が示唆されているのみである。 On the other hand, drains are discharged into rivers without any treatment, and the compounds have not been identified or effectively used. There is only one research report on drains (Non-Patent Document 1), which clarifies the time course and pH of the amount of drainage generated from the wood dryer of cedar pillars. It is only suggested that ozone could be added to the drain to lighten the black color to some extent and that the drain could be used for culturing microorganisms.
このように、ドレーンについての研究は殆どなされておらず、また、ドレーンは、木材由来の廃液であることから、現在は法的な規制もなく放流されているが、濃い黒色の廃液であることから、放流時の水系の景観を損ねてしまうという問題があった。 In this way, little research has been done on drains, and since drains are waste liquids derived from wood, they are currently released without legal restrictions, but they are dark black waste liquids. Therefore, there was a problem that the landscape of the water system at the time of release was spoiled.
本発明は、このような問題点に着目してなされたもので、木材乾燥機から流出する有色の廃液を無色透明にする方法を提供することを目的とする。 The present invention has been made in view of such problems, and an object of the present invention is to provide a method for making colored waste liquid flowing out of a wood dryer colorless and transparent.
本発明の第１の特徴である木材乾燥廃液の無色化方法は、木材の乾燥処理によって排出される廃液に、磁性を有する金属又は金属化合物を接触又は非接触で接するようにしたことである。 The method for decolorizing the wood drying waste liquid, which is the first feature of the present invention, is to bring a magnetic metal or metal compound into contact or non-contact with the waste liquid discharged by the wood drying treatment.
本発明の第２の特徴は、前記金属又は前記金属化合物に係る金属元素を、鉄、コバルト又はニッケルから選ばれる少なくとも１種を含むようにしたことである。 The second feature of the present invention is that the metal element according to the metal or the metal compound contains at least one selected from iron, cobalt and nickel.
本発明の第３の特徴は、前記金属化合物を金属酸化物又は金属水酸化物としたことである。 The third feature of the present invention is that the metal compound is a metal oxide or a metal hydroxide.
本発明の第４の特徴は、前記金属又は前記金属化合物を、鉄、酸化鉄又は水酸化鉄を主成分となるようにしたことである。 A fourth feature of the present invention is that the metal or the metal compound is made to contain iron, iron oxide or iron hydroxide as a main component.
本発明の第５の特徴は、前記酸化鉄又は前記水酸化鉄は、溶液をｐＨ調整して不溶性の鉄化合物として沈殿させたものであり、前記不溶性の鉄化合物と前記廃液とを接触させるようにしたことである。 The fifth feature of the present invention is that the iron oxide or the iron hydroxide is prepared by adjusting the pH of the solution and precipitating it as an insoluble iron compound, so that the insoluble iron compound and the waste liquid are brought into contact with each other. That's what I did.
本発明の第６の特徴は、前記金属又は前記金属化合物が、産業廃棄物から得られる金属屑を原料としたことである。 A sixth feature of the present invention is that the metal or the metal compound is made from metal scraps obtained from industrial waste as a raw material.
また、本発明の特徴は、前記ｐＨ調整において前記不溶性の鉄化合物を含む溶液のｐＨを１以上１４以下としたことである。
また、本発明の特徴は、前記不溶性の鉄化合物のモル濃度を、５ｍＭより大きく１２５ｍＭ以下としたことである。
Further, a feature of the present invention is that the pH of the solution containing the insoluble iron compound is set to 1 or more and 14 or less in the pH adjustment.
Further, a feature of the present invention is that the molar concentration of the insoluble iron compound is greater than 5 mM and 125 mM or less.
本発明の第１の特徴により、木材の乾燥処理によって排出される廃液に、磁性を有する金属などを接触又は非接触で近接するだけで、木材乾燥廃液中の有色原因物質を金属に吸着させ、有色の廃液を略無色の廃液に変換することができる。
本発明の第２の特徴により、磁性を持つ金属のうち鉄、コバルト又はニッケルであれば安価で容易に入手することができる。
本発明の第３の特徴により、金属化合物を金属酸化物又は金属水酸化物とすれば、木材乾燥廃液の無色化処理に適した結晶形となる。
本発明の第４の特徴により、強磁性の鉄などを用いて吸着させることで効率よく無色化処理を行うことができる。
本発明の第５の特徴により、沈殿によって生じた不溶性の鉄化合物に、廃液中の有色原因物質を直接吸着させることができるため効率よく無色化処理を行うことができる。
本発明の第６の特徴により、産業廃棄物である鉄屑などを原料とすることにより、不要になった廃棄物を利用して木材乾燥廃液を無色にすることができる。
According to the first feature of the present invention, the colored causative substance in the wood drying waste liquid is adsorbed on the metal only by bringing a magnetic metal or the like into contact or non-contact with the waste liquid discharged by the wood drying treatment. Colored waste liquid can be converted into substantially colorless waste liquid.
According to the second feature of the present invention, iron, cobalt or nickel among the magnetic metals can be easily obtained at low cost.
According to the third feature of the present invention, if the metal compound is a metal oxide or a metal hydroxide, the crystal form is suitable for the colorless treatment of the dried wood waste liquid.
According to the fourth feature of the present invention, the colorless treatment can be efficiently performed by adsorbing with ferromagnetic iron or the like.
According to the fifth feature of the present invention, the color-causing substance in the waste liquid can be directly adsorbed on the insoluble iron compound generated by the precipitation, so that the decolorization treatment can be efficiently performed.
According to the sixth feature of the present invention, by using iron scraps, which are industrial wastes, as a raw material, it is possible to make the wood drying waste liquid colorless by using the wastes that are no longer needed.
本発明は、木材の乾燥機から流出する濃い黒色のドレーンを略無色（「略無色」とは、無色透明だけでなく薄黄色などの淡色も含むものとし、以下同じである。）の廃液にする方法を見いだしたものである。下記に、本発明を実施するための形態について説明するが、本発明の範囲は、以下に示す実施例に限定されるものではない。 In the present invention, the dark black drain flowing out of the wood dryer is made into a substantially colorless waste liquid (“substantially colorless” includes not only colorless and transparent but also a light color such as light yellow, and the same applies hereinafter). I found a way. Hereinafter, embodiments for carrying out the present invention will be described, but the scope of the present invention is not limited to the examples shown below.
本実施例におけるドレーンは、スギ、マツ、ヒノキなどの木材の乾燥処理によって廃液として回収される。木材の乾燥処理においては、蒸気式乾燥や高周波減圧式乾燥などがあるが、木材乾燥処理において乾燥機底面から廃液として回収される木材乾燥廃液であれば本発明を利用することができる。 The drain in this example is recovered as a waste liquid by a drying treatment of wood such as sugi, pine, and cypress. In the wood drying treatment, there are steam drying and high frequency decompression type drying, but the present invention can be used as long as the wood drying waste liquid is recovered as waste liquid from the bottom surface of the dryer in the wood drying treatment.
乾燥処理は、例えばスギの蒸気式乾燥処理の場合、初期蒸煮工程、ドライングセット工程、乾燥工程及び冷却工程の４工程で行われる。スギの蒸気式乾燥処理で排出されるドレーンは、乾燥処理全工程１８３時間のうち、計５１時間で行われる初期蒸煮工程及びドライングセット工程において、庫内温度９６度から１２０度で大量に回収される。 For example, in the case of steam-type drying treatment of Sugi, the drying treatment is carried out in four steps of an initial steaming step, a drying set step, a drying step and a cooling step. The drain discharged by the steam drying process of Sugi is recovered in large quantities at an internal temperature of 96 to 120 degrees in the initial steaming process and the drying set process, which are performed in a total of 51 hours out of the total 183 hours of the drying process. To.
回収されたドレーンの色は、乾燥機底面から流出したものを回収した時点で濃い黒色を呈しているが、保管状態などによっては、濃い褐色や赤褐色などの有色を呈することもある。また、ドレーンを純水で薄めていくと黒色が淡色化されるものの、黒色の色は保持されたままである。 The color of the collected drain is dark black when it is collected from the bottom of the dryer, but it may be dark brown or reddish brown depending on the storage condition. Further, when the drain is diluted with pure water, the black color is lightened, but the black color is retained.
ドレーンに近接させる金属又は金属化合物は、主に磁性を有する鉄、コバルト、ニッケル、ネオジム若しくはサマリウムなどの金属単体若しくはこれらの金属を主成分とする合金又はこれらの金属の錯体、酸化物、水酸化物若しくは硫化物が挙げられる。なお、磁性を有する金属又は金属化合物が木材乾燥廃液中の有色原因物質を吸着することで該ドレーンを無色透明にするため、該ドレーンと金属又は金属化合物が直接接している場合だけでなく、非接触状態で近接している状態であってもよい。 The metal or metal compound brought close to the drain is mainly a magnetic metal such as iron, cobalt, nickel, neodymium or samarium, an alloy containing these metals as a main component, or a complex, oxide or hydroxylation of these metals. Examples include substances or sulfides. Since the magnetic metal or metal compound adsorbs the color-causing substance in the dried wood waste liquid to make the drain colorless and transparent, not only when the drain is in direct contact with the metal or metal compound, but also non-ferrous metal or metal compound. It may be in a state of being in close contact with each other.
金属酸化物は、例えば金属が鉄である場合は、赤鉄鉱（Ｆｅ２Ｏ３）、磁鉄鉱（Ｆｅ３Ｏ４）、酸化第一鉄（ＦｅＯ）、鉄−チタン酸化物（Ｆｅ２ＴｉＯ４）などが挙げられる。金属水酸化物は、例えば金属が鉄である場合は、水酸化鉄（ＩＩ）Ｆｅ（ＯＨ）２、水酸化鉄（ＩＩＩ）Ｆｅ（ＯＨ）３、酸化水酸化鉄（ＩＩＩ）（ＦｅＯ（ＯＨ））などが挙げられる。このような金属酸化物又は金属水酸化物であれば木材乾燥廃液の無色化処理に適した結晶形となる。 The metal oxides are, for example, red iron ore (Fe 2 O 3 ), magnetic iron ore (Fe 3 O 4 ), ferrous oxide (FeO), and iron-titanium oxide (Fe 2 TIO 4 ) when the metal is iron. And so on. The metal hydroxide is, for example, iron (II) hydroxide Fe (OH) 2 , iron (III) Fe (OH) 3 , iron oxide (III) (FeO (OH)) when the metal is iron. )) And so on. Such a metal oxide or a metal hydroxide has a crystal form suitable for the colorless treatment of the dried wood waste liquid.
産業廃棄物から得られる金属屑を金属原料として使用する場合は、金属の研磨、破砕、切断又は打ち抜きなどの金属加工で生ずる切削屑などを利用することができる。また、金属屑に錆を生じさせる場合は、食塩水、あるいは海水に浸漬させるか食塩水、あるいは海水を吹きかけるなどして金属を腐食させることができる。 When metal scraps obtained from industrial waste are used as a metal raw material, cutting scraps generated by metal processing such as polishing, crushing, cutting or punching of metal can be used. Further, when rusting the metal scraps, the metal can be corroded by immersing it in a salt solution or seawater or by spraying the salt solution or seawater.
（実験例１）
以下に、酸化金属として酸化鉄を用い、各種モル濃度に調整した酸化鉄（ＩＩＩ）（以下、単に「酸化鉄」という。）にドレーンを添加した場合の色の変化について実験を行った例について説明する。実験に使用したドレーンは、スギの蒸気式乾燥処理の初期蒸煮工程及びドライングセット工程において回収された木材乾燥廃液であり、濃い黒色を呈したドレーン原液である。
(Experimental Example 1)
The following is an example of an experiment on the color change when drain is added to iron (III) oxide (hereinafter, simply referred to as "iron oxide") adjusted to various molar concentrations using iron oxide as a metal oxide. explain. The drain used in the experiment was a wood drying waste liquid recovered in the initial steaming step and the drying set step of the steam-type drying treatment of Sugi, and was a drain stock solution exhibiting a dark black color.
まず、酸化鉄の調整について説明する。塩化鉄（ＩＩＩ）六水和物（富士フィルム和光純薬株式会社製）を水に溶解させた溶液に水酸化ナトリウム（富士フィルム和光純薬株式会社製）を加えてｐＨを中性付近に調整すると茶褐色の酸化鉄が沈殿する（沈殿する物質は温度や脱水状況などによって酸化鉄や水酸化鉄となるが、以下単に「酸化鉄」という。）。遠心分離により、上清を廃棄し、超純水で沈殿物の不溶性酸化鉄を懸濁後、再度遠心分離し、上清を廃棄する。この作業を３回〜４回繰り返し、０．５Ｍの不溶性酸化鉄溶液を準備した。 First, the adjustment of iron oxide will be described. Add sodium hydroxide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) to a solution of iron (III) chloride hexahydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in water to adjust the pH to near neutrality. Then, brown iron oxide precipitates (the precipitated substance becomes iron oxide or iron hydroxide depending on the temperature and dehydration conditions, but hereinafter simply referred to as "iron oxide"). The supernatant is discarded by centrifugation, the insoluble iron oxide in the precipitate is suspended in ultrapure water, and the supernatant is centrifuged again and the supernatant is discarded. This operation was repeated 3 to 4 times to prepare a 0.5 M insoluble iron oxide solution.
次に、０．５Ｍの不溶性酸化鉄溶液：超純水を合計５ｍＬとなるよう（１）０：５（２）０．１：４．９（３）０．５：４．５（４）０．７５：４．２５（５）１：４（６）１．５：３．５（７）２．５：２．５の割合で混合し、不溶性酸化鉄の終濃度が（１）０ｍＭ（２）５ｍＭ（３）２５ｍＭ（４）３７．５ｍＭ（５）５０ｍＭ（６）７５ｍＭ（７）１２５ｍＭとなるようドレーン５ｍＬを添加した結果を図１に示す。 Next, 0.5 M insoluble iron oxide solution: ultrapure water so as to make a total of 5 mL (1) 0: 5 (2) 0.1: 4.9 (3) 0.5: 4.5 (4) Mix at a ratio of 0.75: 4.25 (5) 1: 4 (6) 1.5: 3.5 (7) 2.5: 2.5, and the final concentration of insoluble iron oxide is (1) 0 mM. (2) The result of adding 5 mL of drain to 5 mM (3) 25 mM (4) 37.5 mM (5) 50 mM (6) 75 mM (7) 125 mM is shown in FIG.
写真にて明らかなように、不溶性酸化鉄終濃度が（３）２５ｍＭで明白な効果があり、（４）３７．５ｍＭ〜（６）５０ｍＭで高い効果、（７）１２５ｍＭで逆効果であった。しかし、（７）１２５ｍＭであっても（１）０ｍＭ、即ち不溶性酸化鉄溶液を加えていないドレーンの黒色より退色されており、黒色ではない薄黄色〜薄茶色へ変換されていることから一定の効果が得られているといえる。よって、酸化鉄のモル濃度は、５ｍＭを超えると黒色のドレーンを退色して淡色化することができ、２５ｍＭ以上１２５ｍＭ以下で黒色を薄黄色〜薄茶色に淡色化し、３７．５ｍＭ以上７５ｍＭ以下とすることにより無色透明にすることができる。 As is clear from the photograph, the final concentration of insoluble iron oxide was (3) 25 mM, which had a clear effect, (4) 37.5 mM to (6) 50 mM, which had a high effect, and (7) 125 mM, which had an adverse effect. .. However, even if it is (7) 125 mM, it is constant because it is (1) 0 mM, that is, the color is faded from the black color of the drain to which the insoluble iron oxide solution is not added, and it is converted from light yellow to light brown, which is not black. It can be said that the effect has been obtained. Therefore, when the molar concentration of iron oxide exceeds 5 mM, the black drain can be faded and lightened, and when it is 25 mM or more and 125 mM or less, the black color is lightened from light yellow to light brown, and 37.5 mM or more and 75 mM or less. By doing so, it can be made colorless and transparent.
（実験例２）
次に、各種ｐＨによるドレーンの不溶性酸化鉄への吸着に与える影響について実験を行った例について説明する。なお、ドレーン、不溶性酸化鉄及び水酸化ナトリウムなどは実験例１と同様に準備し、以下の実験例においても同じである。まず、水酸化ナトリウム又は塩酸を添加してそれぞれｐＨ１，３，５，７，９，１１となるよう調整し、濃度が１００ｍＭの不溶性酸化鉄溶液を５ｍＬ準備した。これに、同量のドレーン５ｍＬを添加したとき（不溶性酸化鉄の最終濃度５０ｍＭ）の変化についての結果を図２に示す。写真左のサンプルは、ネガティブコントロールとして示したものであり、ドレーンに同量の超純水のみを加えたものである。写真から明らかなように、ｐＨ１において効果はなく、ｐＨ３以上でドレーンの黒色が退色され、ｐＨ３とｐＨ５にいては黒色が無色透明となった。
(Experimental Example 2)
Next, an example in which an experiment was conducted on the effect of various pHs on the adsorption of drains on insoluble iron oxide will be described. The drain, insoluble iron oxide, sodium hydroxide and the like were prepared in the same manner as in Experimental Example 1, and the same applies to the following Experimental Examples. First, sodium hydroxide or hydrochloric acid was added to adjust the pH to 1,3,5,7,9,11, respectively, and 5 mL of an insoluble iron oxide solution having a concentration of 100 mM was prepared. The results of the change when the same amount of
このことから、ｐＨを１より大きくすることにより黒色を退色させることができ、ｐＨ２以上６以下で無色化するが、ｐＨ７以上で僅かに濁り、ｐＨ９、ｐＨ１１と高ｐＨになるほど次第に有色化されていくことが確認できた。なお、添加後から写真撮影までの経過日数を写真下方に示しているが、不溶性酸化鉄が沈殿して落ち着くまでは常に数時間であった。また、不溶性酸化鉄が可溶化するｐＨ１の条件では、黒色の退色が確認できなかったことから、ドレーンは不溶性の酸化鉄に吸着することが明らかとなった。
From this, the black color can be faded by increasing the pH above 1, and it becomes colorless at
（実験例３）
次に産業廃棄物である金属製品にて同様に吸着されるか実験を行った例について説明する。金属製品は鉄を多量に含む剪定ばさみの研磨屑を用い、これを酸化させて錆を生じさせたものを使用した。図３は、超純水に同量のドレーンを混合し、該研磨屑を添加したときのドレーンの色の変化について示した写真である。また、右の写真は、左の写真撮影時から１４日経過後の色の変化を示したものである。写真左のサンプルＡは、ネガティブコントロールとして示したものであり、超純水５ｍＬに同量のドレーン５ｍＬのみを加えたものである。Ｂは、超純水５ｍＬに同量のドレーン５ｍＬを混合し研磨屑を添加したものである。Ｃは、超純水５ｍＬに同量のドレーン５ｍＬを混合し、５％食塩水に浸漬させ、錆を生じさせた研磨屑を添加したものである。Ｄは、超純水５ｍＬに同量のドレーン５ｍＬを混合し、５％食塩水に吹きかけ、錆を生じさせた研磨屑を添加したものである。
(Experimental Example 3)
Next, an example in which an experiment was conducted to see if the metal product, which is an industrial waste, is similarly adsorbed will be described. For metal products, we used abrasive scraps of pruning shears containing a large amount of iron, which were oxidized to cause rust. FIG. 3 is a photograph showing a change in the color of the drain when the same amount of drain is mixed with ultrapure water and the polishing debris is added. The photo on the right shows the color change 14 days after the photo was taken on the left. Sample A on the left of the photograph is shown as a negative control, and is obtained by adding only 5 mL of the same amount of drain to 5 mL of ultrapure water. B is obtained by mixing 5 mL of ultrapure water with 5 mL of the same amount of drain and adding polishing debris. In C, the same amount of
左の写真から確認できるように、Ｂの研磨屑は効果がなく黒色に懸濁しているが、錆を生じさせた研磨屑Ｃ及びＤは退色が示された。また、ＤよりもＣの方が退色されていることから、研磨屑に食塩水を吹きかけて錆を生じさせるより食塩水に浸漬させて錆を生じさせた方がドレーンの黒色が退色されていることが確認できた。さらに、１４日経過後の右の写真にて確認できるように、錆を生じさせた研磨屑Ｃ及びＤは、さらに退色され、より無色に近づいたことが確認できた。以上より、産業廃棄物である研磨屑に錆を生じさせることでドレーンの黒色原因物質の吸着に利用できることが示された。また、ドレーンの黒色をより退色させるには、研磨屑と食塩水との接触面積を増やして錆を生じさせること及びドレーンと研磨屑との接触時間を長くすることが好ましいことが確認できた。 As can be confirmed from the photograph on the left, the polishing debris of B had no effect and was suspended in black, but the polishing debris C and D that caused rust showed fading. Further, since C is more faded than D, the black color of the drain is faded when the polishing debris is immersed in the saline solution to cause rust rather than being sprayed with saline solution to cause rust. I was able to confirm that. Further, as can be confirmed in the photograph on the right after 14 days, it was confirmed that the rusted polishing chips C and D were further faded and became more colorless. From the above, it was shown that it can be used for adsorbing black-causing substances in drains by causing rust on polishing debris, which is an industrial waste. Further, it was confirmed that in order to further fade the black color of the drain, it is preferable to increase the contact area between the polishing debris and the saline solution to cause rust and to lengthen the contact time between the drain and the polishing debris.
また、酸化鉄は鉄にできる錆を構成する化合物であり磁性を有することから、ドレーンの黒色原因物質は特有の磁性を有する金属を含んでいると考えられ、また、ドレーン中の該金属と磁性を有する金属又は金属化合物とを接触又は非接触で接することにより、ドレーンの黒色原因物質が磁性を有する金属又は金属化合物に吸着・除去され、黒色のドレーンを無色化すると考えられる。 Further, since iron oxide is a compound that constitutes rust formed in iron and has magnetism, it is considered that the black-causing substance of the drain contains a metal having a peculiar magnetism, and the metal and the magnetism in the drain are considered to be contained. It is considered that the black-causing substance of the drain is adsorbed and removed by the magnetic metal or the metal compound by contacting or non-contacting the metal or the metal compound having the above, and the black drain becomes colorless.
（実験例４）
次に、錆びた研磨屑を洗浄したものにドレーンを添加したときの色の変化について実験を行った例について説明する。図４は、食塩水で錆びさせた研磨屑を一度真水（塩分を含まない水）で洗浄し、これにドレーンを添加したときの色の変化を示した写真である。写真から分かるように、食塩水で錆びさせた研磨屑をそのまま添加するよりも、食塩水で錆びさせた研磨屑を一度真水で洗浄して使用した方が、ドレーンの黒色をより退色することが明らかとなった。
(Experimental Example 4)
Next, an example in which an experiment was conducted on the color change when a drain was added to a washed rusted polishing debris will be described. FIG. 4 is a photograph showing a change in color when a polishing debris rusted with a saline solution is once washed with fresh water (water containing no salt) and a drain is added thereto. As can be seen from the photograph, the black color of the drain can be further faded by washing the polishing debris rusted with saline solution once with fresh water and using it, rather than adding the polishing debris rusted with salt solution as it is. It became clear.
以上、本発明の実施例を図面により説明してきたが、具体的な構成はこれら実施例に限られるものではなく、本発明の要旨を逸脱しない範囲における変更や追加があっても本発明に含まれる。 Although examples of the present invention have been described above with reference to the drawings, the specific configuration is not limited to these examples, and any changes or additions within the scope of the gist of the present invention are included in the present invention. Is done.
本発明は、木材乾燥時に木材乾燥機から流出する有色の廃液を退色させ、略無色に処理することができるため、木材製造現場において利用することができる。 INDUSTRIAL APPLICABILITY The present invention can be used at a wood manufacturing site because the colored waste liquid flowing out of the wood dryer when the wood is dried can be faded and treated substantially colorless.
Claims (6)
The method for decolorizing a dry wood waste liquid according to claim 1 to 5, wherein the metal or the metal compound is made from metal scraps obtained from industrial waste.
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| JPS52135553A (en) * | 1976-05-03 | 1977-11-12 | Commw Scient Ind Res Org | Clarification of water |
| JPS54137853A (en) * | 1978-04-18 | 1979-10-25 | Kawasaki Steel Corp | Purification of waste water resulting from fumigation of lumber |
| JPH01503764A (en) * | 1986-09-16 | 1989-12-21 | コモンウエルス・サイエンティフィック・アンド・インダストリアル・リサーチ・オーガニゼイション | Sewage treatment |
| JP2010201279A (en) * | 2009-02-09 | 2010-09-16 | Univ Of Miyazaki | Method and apparatus for decoloring livestock waste liquid |
| JP2011016048A (en) * | 2009-07-07 | 2011-01-27 | Act Co Ltd | Method of decoloring and purifying wastewater containing lignin and/or tannin |
| JP2021023917A (en) * | 2019-08-09 | 2021-02-22 | 国立大学法人 宮崎大学 | Metal replenisher obtainable from wood drying waste liquid, method of decolorizing wood drying waste liquid and method of recovering heartwood components |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS52135553A (en) * | 1976-05-03 | 1977-11-12 | Commw Scient Ind Res Org | Clarification of water |
| JPS54137853A (en) * | 1978-04-18 | 1979-10-25 | Kawasaki Steel Corp | Purification of waste water resulting from fumigation of lumber |
| JPH01503764A (en) * | 1986-09-16 | 1989-12-21 | コモンウエルス・サイエンティフィック・アンド・インダストリアル・リサーチ・オーガニゼイション | Sewage treatment |
| JP2010201279A (en) * | 2009-02-09 | 2010-09-16 | Univ Of Miyazaki | Method and apparatus for decoloring livestock waste liquid |
| JP2011016048A (en) * | 2009-07-07 | 2011-01-27 | Act Co Ltd | Method of decoloring and purifying wastewater containing lignin and/or tannin |
| JP2021023917A (en) * | 2019-08-09 | 2021-02-22 | 国立大学法人 宮崎大学 | Metal replenisher obtainable from wood drying waste liquid, method of decolorizing wood drying waste liquid and method of recovering heartwood components |
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