JP2021183671A - Manufacturing method of antifreeze agent derived from plant raw material and antifreeze agent - Google Patents
Manufacturing method of antifreeze agent derived from plant raw material and antifreeze agent Download PDFInfo
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Abstract
Description
本発明は、植物原料由来の凍結防止剤の製造方法及びその方法により製造された凍結防止剤に関するものである。 The present invention relates to a method for producing an antifreeze agent derived from a plant raw material and an antifreeze agent produced by the method.
冬季における道路の凍結を防止するために道路に散布される凍結防止剤として、従来から塩化ナトリウム、塩化カルシウム等の無機塩化物が大量に使用されている。しかしこれらの無機塩化物からなる凍結防止剤については、環境への二次的影響が指摘されている。具体的には、河川などの水質への影響、植物や農地への影響、周辺の鋼構造物や車両の金属腐食等である。特に高速道路や道路橋梁においては、凍結防止剤の塩化物イオンがコンクリートの内部に浸透して鉄筋を保護している不動態被膜を破壊し、鉄筋を錆びさせるのみならず、コンクリートにひび割れを生じさせ、コンクリートの剥離、剥落等の危険な状態を招くおそれがある。 As an antifreeze agent sprayed on roads to prevent roads from freezing in winter, a large amount of inorganic chlorides such as sodium chloride and calcium chloride have been conventionally used. However, it has been pointed out that the antifreeze agent consisting of these inorganic chlorides has a secondary impact on the environment. Specifically, there are effects on water quality such as rivers, effects on plants and agricultural land, and metal corrosion of surrounding steel structures and vehicles. Especially on highways and road bridges, chloride ions, which are antifreeze agents, permeate the inside of concrete and destroy the passivation film that protects the reinforcing bars, which not only rusts the reinforcing bars but also causes cracks in the concrete. There is a risk of causing dangerous conditions such as peeling and peeling of concrete.
この問題を解決するため、塩化物イオンを避けた酢酸カルシウム・マグネシウム、酢酸ナトリウム等の有機酸系凍結防止剤が製造されている。しかし従来の有機酸系の凍結防止剤は無機塩化物系の凍結防止剤に比較して生産コストが数倍となるため、経済的観点から部分的な散布にしか使用することができない。 In order to solve this problem, organic acid-based antifreeze agents such as calcium acetate / magnesium and sodium acetate that avoid chloride ions are manufactured. However, since the production cost of the conventional organic acid-based antifreeze agent is several times higher than that of the inorganic chloride-based antifreeze agent, it can be used only for partial spraying from an economical point of view.
一方、木材の伐採やその加工に伴って散材、廃材などの木質系廃棄物が大量に発生しており、その処分に困っている状況がある。そこでこれらの木質系廃材や稲わらなどの植物原料を用いて凍結防止剤を製造する試みがなされている。 On the other hand, a large amount of wood-based waste such as sprinkled wood and waste wood is generated due to logging and processing of wood, and there are situations where it is difficult to dispose of it. Therefore, attempts have been made to produce antifreeze agents using these wood-based waste materials and plant raw materials such as rice straw.
例えば特許文献１には、枯れた松材を粉砕して熱風乾燥し、乾留により発生させた木ガスから木酢液を回収し、カルシウムと反応させて凍結防止剤を製造する方法が提案されている。また特許文献２には、枯れた松材のセルロースを希硫酸で熱水処理し、中和したうえ発酵処理して得られた有機酸から凍結防止剤を製造する方法が提案されている。しかしこれらの方法は加熱処理や薬剤を必要とすることもあって、やはり凍結防止剤の製造コストが高くなるという問題を持っていた。
For example,
従って本発明の目的は上記した従来の問題点を解決して、木質系廃材などの安価な植物原料を用いて、有機酸系凍結防止剤を低コストで製造することができる新規な技術を提供することである。 Therefore, an object of the present invention is to solve the above-mentioned conventional problems and provide a novel technique capable of producing an organic acid-based antifreeze agent at low cost by using an inexpensive plant raw material such as wood-based waste material. It is to be.
上記の課題を解決するためになされた本発明の植物原料由来の凍結防止剤の製造方法は、植物原料に含まれるリグニンなどの難分解性有機物を白色腐朽菌により好気性分解して低分子化したうえ、これを嫌気性処理して有機酸を生成させ、この嫌気性処理液の上澄み液に含まれる有機酸を溶媒抽出により濃縮し、凍結防止剤とすることを特徴とするものである。 In the method for producing an antifreeze agent derived from a plant material of the present invention, which has been made to solve the above problems, persistent organic substances such as lignin contained in the plant material are aerobically decomposed by white spoilage bacteria to reduce the molecular weight. Further, this is anaerobically treated to generate an organic acid, and the organic acid contained in the supernatant of the anaerobic treatment liquid is concentrated by solvent extraction to obtain an antifreeze agent.
なお、植物原料は木質系廃材又は稲わらなどとすることができる。また、植物原料をマイクロ波または高温高圧で前処理したうえで、白色腐朽菌により好気性分解することにより、分解効率を高めることもできる。また、前記有機酸が、酪酸、プロピオン酸、酢酸などの低級脂肪酸を含有するものであることが好ましい。 The plant material can be wood-based waste wood or rice straw. Further, the decomposition efficiency can be improved by pretreating the plant raw material with microwaves or high temperature and high pressure and then aerobicly decomposing it with white-rot fungi. Further, it is preferable that the organic acid contains lower fatty acids such as butyric acid, propionic acid and acetic acid.
この方法で製造された植物原料由来の凍結防止剤は塩分を含有せず、有機酸を主成分とするものであるため、従来のように環境への二次的影響が生じたり、鉄筋を錆びさせたり、コンクリートにひび割れを生じさせたりすることもない。 Since the antifreeze agent derived from plant raw materials produced by this method does not contain salt and contains organic acid as the main component, it has a secondary impact on the environment and rusts the reinforcing bars as in the past. It does not cause the concrete to crack or crack.
以下に本発明の好ましい実施形態を示す。
図１は本発明の製造工程を示すブロック図である。本発明では凍結防止剤の原料として、植物原料を使用する。植物原料の種類は特に限定されるものではないが、散材、廃材などの木質系廃棄物のほか、稲わらなども用いることができる。これらは安価、または無料で入手できるうえに、木質系廃棄物を用いれば処分に困っていた廃棄物の処理に貢献することもできる。原料となる植物原料は反応を促進するために、微粉砕しておくことが好ましい。
Hereinafter, preferred embodiments of the present invention are shown.
FIG. 1 is a block diagram showing a manufacturing process of the present invention. In the present invention, a plant raw material is used as a raw material for the antifreeze agent. The type of plant raw material is not particularly limited, but wood-based waste such as sprinkles and waste materials, as well as rice straw and the like can be used. These can be obtained cheaply or free of charge, and can also contribute to the disposal of waste that was difficult to dispose of by using wood-based waste. It is preferable that the plant raw material as a raw material is finely pulverized in order to promote the reaction.
木材は主要成分であるセルロース、ヘミセルロース、難分解性のリグニンを含むものである。本発明では木材腐朽菌の一種である白色腐朽菌を用いてこれらを好気性条件下で分解し、低分子化して多糖類とする。白色腐朽菌は木材に含まれる難分解性のリグニンを分解する能力を持ち、リグニンが分解された後に残留する、セルロース、ヘミセルロースの色である白色に変色させることから、白色腐朽菌と呼ばれる。本発明では例えばウスキイロカワタケ（phanerochaete sordida）を利用することができるが、白色腐朽菌の種類はこれに限定されるものではない。 Wood contains the main components cellulose, hemicellulose, and persistent lignin. In the present invention, a white rot fungus, which is a kind of wood rot fungus, is used to decompose these under aerobic conditions to reduce the molecular weight to a polysaccharide. White-rot fungi are called white-rot fungi because they have the ability to decompose persistent lignin contained in wood and change the color to white, which is the color of cellulose and hemicellulose that remains after the decomposition of lignin. In the present invention, for example, Phanerochaete sordida can be used, but the type of white-rot fungus is not limited to this.
寒天あるいは液体培地で予め白色腐朽菌を培養したうえ、上記した植物原料の粉砕物を添加し、室温の好気性条件下に置けば、植物原料に含まれるリグニンを白色腐朽菌が好気性分解して低分子化し、多糖類が生成される。白色腐朽菌を培養するための培地には、リン酸塩などの栄養塩やグルコースなどの易分解性有機物を添加して菌糸の成長を促進することができる。好気性分解を進行させる培地としては水を加えた液体培地を用いることにより、リグニン分解時間を短縮できることが判明した。好ましい含水率は50〜90wt％程度である。 If the white rot fungus is cultivated in advance on agar or a liquid medium, the above-mentioned crushed plant material is added, and the lignin contained in the plant material is aerobicly decomposed by aerobic conditions at room temperature. The molecular weight is reduced to produce polysaccharides. A nutrient salt such as phosphate and an easily degradable organic substance such as glucose can be added to the medium for culturing the white-rot fungus to promote the growth of hyphae. It was found that the lignin decomposition time can be shortened by using a liquid medium containing water as a medium for advancing aerobic decomposition. The preferable water content is about 50 to 90 wt%.
本発明者の実験によれば、２週間で木材中のリグニンの約50wt％が分解された。このように白色腐朽菌によるリグニンの分解にはある程度の時間を要するが、粉砕した植物原料をマイクロ波による前処理を行うことにより、リグニン分解を促進することができる。このほか、粉砕された木質原料に例えば１３０℃、200ｋPaの高温高圧による処理を施せば、さらにリグニン分解を促進することができる。 According to the inventor's experiment, about 50 wt% of lignin in wood was decomposed in 2 weeks. As described above, it takes a certain amount of time for the decomposition of lignin by the white-rot fungus, but the decomposition of lignin can be promoted by pretreating the crushed plant raw material with microwaves. In addition, if the crushed wood-based material is treated with a high temperature and high pressure of, for example, 130 ° C. and 200 kPa, lignin decomposition can be further promoted.
次に、多糖類を含む好気性分解液を嫌気性処理リアクターに送り込み、酸生成菌などの嫌気性菌により嫌気性処理を行うことにより有機酸を生成させる。酸生成菌は汚泥中から採取し、嫌気性処理リアクター内において数日間馴致しておく。実験の結果、pHが比較的高い領域において有機酸の生成量が多くなることが確認されたので、pHを7.3〜7.9のアルカリ側に調整しておくことが好ましい。pHが８を超えると有機酸の生成量が低下する傾向を示す。 Next, an aerobic decomposition solution containing a polysaccharide is sent to an anaerobic treatment reactor, and an organic acid is produced by performing anaerobic treatment with an anaerobic bacterium such as an acid-producing bacterium. Acid-producing bacteria are collected from sludge and allowed to acclimate in an anaerobic treatment reactor for several days. As a result of the experiment, it was confirmed that the amount of organic acid produced increases in the region where the pH is relatively high, so it is preferable to adjust the pH to the alkaline side of 7.3 to 7.9. When the pH exceeds 8, the amount of organic acid produced tends to decrease.
この嫌気性処理はバッチ処理であっても、連続処理であってもよい。連続処理の場合には、例えばスパイラル状の撹拌手段により嫌気性処理リアクターの槽内液を低速で出口側に向けて徐々に移動させながら、嫌気性処理を進行させることができる。この嫌気性処理により、処理液中に酢酸、プロピオン酸、酢酸などの低級脂肪酸を主とする水溶性の有機酸が生成される。 This anaerobic treatment may be a batch treatment or a continuous treatment. In the case of continuous treatment, the anaerobic treatment can be advanced while the liquid in the tank of the anaerobic treatment reactor is gradually moved toward the outlet side at a low speed by, for example, a spiral stirring means. By this anaerobic treatment, a water-soluble organic acid mainly composed of lower fatty acids such as acetic acid, propionic acid and acetic acid is produced in the treatment liquid.
嫌気性処理リアクターには嫌気性汚泥とその上澄み液が発生するが、上記した有機酸は上澄み液中に含まれる。嫌気性処理装置から上澄み液を抽出することによって、処理槽内液に含まれる有機酸の濃度を１０倍程度に濃縮することができる。なお、嫌気性汚泥は酸生成菌などの嫌気性菌を多量に含有するため沈降分離して再使用できるが、必要に応じて余剰汚泥は嫌気性処理リアクターから取り除けばよい。 Anaerobic sludge and its supernatant are generated in the anaerobic treatment reactor, and the above-mentioned organic acid is contained in the supernatant. By extracting the supernatant liquid from the anaerobic treatment apparatus, the concentration of the organic acid contained in the liquid in the treatment tank can be concentrated about 10 times. Since anaerobic sludge contains a large amount of anaerobic bacteria such as acid-producing bacteria, it can be separated and reused by sedimentation, but excess sludge may be removed from the anaerobic treatment reactor if necessary.
嫌気性処理リアクターから取り出される上澄み液は黒色の液体であるうえ有機酸の濃度が低いため、そのままでは凍結防止剤として道路に散布することはできない。そこでさらに溶媒抽出により、上澄み液から水溶性の有機酸を抽出する。溶媒としては、例えばトリブチルリン酸を使用することができる。この結果、酢酸、プロピオン酸、酪酸などの有機酸をさらに１０倍程度濃縮することができる。また黒色の色素は抽出されないため無色となり、そのまま道路に散布することができる凍結防止剤が得られる。 The supernatant liquid taken out from the anaerobic treatment reactor is a black liquid and has a low concentration of organic acids, so that it cannot be sprayed on the road as an antifreeze agent as it is. Therefore, a water-soluble organic acid is further extracted from the supernatant by solvent extraction. As the solvent, for example, tributyl phosphoric acid can be used. As a result, organic acids such as acetic acid, propionic acid, and butyric acid can be further concentrated about 10 times. Further, since the black pigment is not extracted, it becomes colorless, and an antifreeze agent that can be sprayed on the road as it is can be obtained.
このようにして得られた植物原料由来の凍結防止剤は塩分を含有せず、有機酸を主成分とするものである。その凍結効果を確認したところ、本発明の凍結防止剤を用いることにより、４℃における融氷速度が水道水に比較して８％速くなり、また凍結時間は水道水の６倍となることが確認された。 The antifreeze agent derived from the plant raw material thus obtained does not contain salt and contains an organic acid as a main component. As a result of confirming the freezing effect, by using the antifreeze agent of the present invention, the ice melting speed at 4 ° C. is 8% faster than that of tap water, and the freezing time is 6 times faster than that of tap water. confirmed.
以上に説明した通り、本発明によれば植物原料を白色腐朽菌による好気性処理したうえで酸生成菌による嫌気性処理を行うことにより有機酸を生成することができ、塩分を含有しない植物原料由来の凍結防止剤を安価に製造することができる。以下に本発明の実施例を示す。 As described above, according to the present invention, an organic acid can be produced by aerobic treatment with a white-rot fungus and then anaerobic treatment with an acid-producing bacterium, and the plant raw material does not contain salt. The derived antifreeze agent can be produced at low cost. Examples of the present invention are shown below.
菌類キノコ遺伝資源研究センターから分譲された白色腐朽菌（ウスキイロカワタケ、phanerochaete sordida）を（ポテト・デキストロース・寒天）培地に接種して７日間培養した。 The white-rot fungus (phanerochaete sordida) distributed from the Fungal Mushroom Genetic Resources Research Center was inoculated into a (potato, dextrose, agar) medium and cultured for 7 days.
杉と檜の混合物である木質系散材を汎用粉砕機を用いて粉砕して粒子径を１mm以下に調整し、三角フラスコに入れ、通気性の蓋で密閉した。これをオートクレーブ処理（１２０℃、３０分）して滅菌したうえ、超純水で散材木粉の含水率を50wt％に調整した。上記の培地から直径５mmのコルクボーラーで白色腐朽菌を培地とともに打ち抜き、得られた円板を散材木粉の入った三角フラスコの中央部に１枚ずつ接種した。コントロールサンプルとして散材木粉のみの三角フラスコを作成した。双方を２５℃のインキュベータ内にて好気性条件下で２週間培養した。 A wood-based powder, which is a mixture of cedar and cypress, was crushed using a general-purpose crusher to adjust the particle size to 1 mm or less, placed in an Erlenmeyer flask, and sealed with a breathable lid. This was autoclaved (120 ° C., 30 minutes) and sterilized, and the water content of the sprinkled wood powder was adjusted to 50 wt% with ultrapure water. White-rot fungi were punched out from the above medium with a cork borer having a diameter of 5 mm together with the medium, and the obtained discs were inoculated one by one into the central part of an Erlenmeyer flask containing wood flour. An Erlenmeyer flask containing only wood flour was prepared as a control sample. Both were cultured in an incubator at 25 ° C. under aerobic conditions for 2 weeks.
その後、散材木粉のリグニン量を測定した。リグニン量の測定手順は次の通りである。 Then, the amount of lignin in the wood flour was measured. The procedure for measuring the amount of lignin is as follows.
先ず、木粉サンプル1gを入れた円筒形ろ紙をエタノールとベンゼンの混合有機溶媒で、６時間ソックスレー抽出を行い、有機溶媒可溶分を抽出し、混合有機溶媒を除去した後に円筒形ろ紙とともに秤量して有機溶媒可用分を測定した。 First, a cylindrical filter paper containing 1 g of a wood flour sample is soxhlet-extracted with a mixed organic solvent of ethanol and benzene for 6 hours to extract an organic solvent-soluble component, and after removing the mixed organic solvent, weighed together with the cylindrical filter paper. Then, the usable amount of the organic solvent was measured.
上述の有機溶媒可溶分を抽出した後の脱脂木粉約0.3ｇを氷上にて4.5ｍｌの７２％H2SO4と合わせ、３０℃で1時間インキュベーションした。次に蒸留水でH2SO4の濃度を３％にまで薄め、オートクレーブで３０分間加熱処理した後、ろ過吸引した。残渣を秤量してリグニン量とした。またこのろ液0.3mLに2.7mLの３％H2SO4を加えて１０倍希釈し、分光光度計を用いて205〜210nm近傍の吸光度を測定し、酸溶解性リグニン量を求めた。 After extracting the above-mentioned organic solvent-soluble component, about 0.3 g of degreased wood powder was combined with 4.5 ml of 72% H 2 SO 4 on ice and incubated at 30 ° C. for 1 hour. Next, the concentration of H 2 SO 4 was diluted to 3% with distilled water, heat-treated in an autoclave for 30 minutes, and then filtered and suctioned. The residue was weighed to give the amount of lignin. Further, 2.7 mL of 3% H 2 SO 4 was added to 0.3 mL of this filtrate to dilute it 10-fold, and the absorbance near 205 to 210 nm was measured using a spectrophotometer to determine the amount of acid-soluble lignin.
その結果は、図２、図３に示すとおりであった。図２はリグニン量を示し、コントロールサンプルでは１４日経過後もリグニン量は変化しなかったが、白色腐朽菌を接種したサンプルではリグニン量が顕著に低下し、分解率は約５０％であった。一方、図３に示す酸溶解性リグニンは１４日経過後に少量ながら増加した。これにより、白色腐朽菌の存在により難分解性でしかも高分子のリグニンが低分子の有機物である酸溶解性リグニンに分解されていることが確認された。 The results are as shown in FIGS. 2 and 3. FIG. 2 shows the amount of lignin. In the control sample, the amount of lignin did not change even after 14 days, but in the sample inoculated with the white-rot fungus, the amount of lignin was significantly reduced and the decomposition rate was about 50%. On the other hand, the acid-soluble lignin shown in FIG. 3 increased slightly after 14 days. From this, it was confirmed that the persistent and high molecular weight lignin was decomposed into acid-soluble lignin, which is a low molecular weight organic substance, due to the presence of white-rot fungi.
次に、嫌気性処理リアクターに馴致した嫌気性汚泥を採取し、好気性処理された散材木粉含有液を投入して室温で嫌気性処理を行った。有機酸生成量を毎日測定した結果、図４の通りの結果が得られた。酢酸、プロピオン酸、イソ酪酸、酪酸が生成されたことを示している。 Next, the anaerobic sludge acclimatized to the anaerobic treatment reactor was collected, and the aerobic-treated sprinkled wood powder-containing liquid was added to perform the anaerobic treatment at room temperature. As a result of daily measurement of the amount of organic acid produced, the results shown in FIG. 4 were obtained. It shows that acetic acid, propionic acid, isobutyric acid, and butyric acid were produced.
この嫌気性処理リアクターから上澄み液を抽出し、トリブチルリン酸による溶媒抽出を行った。得られた凍結防止剤は無色であり塩分を含有しないものである。凍結防止効果を確認したところ、前記した通りこの凍結防止剤を添加することにより４℃における融氷速度が水道水に比較して８％速くなり、また凍結時間は水道水の６倍となった。これにより本発明の凍結防止剤の融雪効果、凍結防止効果が確認された。 The supernatant was extracted from this anaerobic treatment reactor, and the solvent was extracted with tributyl phosphate. The obtained antifreeze agent is colorless and does not contain salt. As a result of confirming the antifreezing effect, as described above, by adding this antifreezing agent, the ice melting speed at 4 ° C. was 8% faster than that of tap water, and the freezing time was 6 times that of tap water. .. As a result, the snow melting effect and the antifreezing effect of the antifreezing agent of the present invention were confirmed.
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