JP7491518B2 - Cured product and method for producing same - Google Patents
Cured product and method for producing same Download PDFInfo
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- JP7491518B2 JP7491518B2 JP2018186077A JP2018186077A JP7491518B2 JP 7491518 B2 JP7491518 B2 JP 7491518B2 JP 2018186077 A JP2018186077 A JP 2018186077A JP 2018186077 A JP2018186077 A JP 2018186077A JP 7491518 B2 JP7491518 B2 JP 7491518B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229920005610 lignin Polymers 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 36
- 229920002101 Chitin Polymers 0.000 claims description 34
- 210000003278 egg shell Anatomy 0.000 claims description 32
- 239000002699 waste material Substances 0.000 claims description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- 102000002322 Egg Proteins Human genes 0.000 claims description 19
- 108010000912 Egg Proteins Proteins 0.000 claims description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims description 16
- 239000012779 reinforcing material Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
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- 241000238421 Arthropoda Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
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- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、軽量、高強度、耐熱性を有する硬化物及びその製造方法に関する。 The present invention relates to a cured product that is lightweight, high strength, and heat resistant, and a method for producing the same.
野菜を使用した食品工場や加工場や野菜生産者、更には木工場からは、植物由来の廃棄物が大量に発生している。植物由来の廃棄物の一部は堆肥として利用されているが、産業廃棄物として廃棄されていることが多いのが現状であり、植物由来の廃棄物のリサイクルのために植物バイオマスの用途拡大が目指されている。 A large amount of plant-derived waste is generated from food factories and processing plants that use vegetables, vegetable growers, and even woodworking factories. Some of the plant-derived waste is used as compost, but the reality is that most of it is discarded as industrial waste, and there are efforts to expand the uses of plant biomass in order to recycle plant-derived waste.
植物バイオマスの利用例として、リサイクルされたセルロース繊維と、充填剤又は顔料とを混合してフィブリル化してナノフィブリルセルロースゲルを含む複合材料を製造する方法がある(特許文献１）。しかし、特許文献１に記載の複合材料の原材料は、木材、または麻、亜麻およびマニラ麻などの植物の茎から加工されたセルロースパルプであり、野菜を使用した食品工場や加工場や野菜生産者から排出される残渣ではない。更に、製造された複合材料はゲル状であり、この複合材料を所定形状に成形するには別途の工程が必要であり、製造コストが高かった。 One example of the use of plant biomass is a method of producing a composite material containing nanofibrillated cellulose gel by mixing recycled cellulose fibers with a filler or pigment and fibrillating them (Patent Document 1). However, the raw material for the composite material described in Patent Document 1 is cellulose pulp processed from wood or the stems of plants such as hemp, flax, and Manila hemp, and is not residues discharged from food factories and processing plants that use vegetables or vegetable growers. Furthermore, the produced composite material is in a gel state, and a separate process is required to mold this composite material into a predetermined shape, resulting in high production costs.
植物バイオマスの一つであるリグニンは、高等植物の木化に関与する高分子のフェノール化合物である。リグニンは、例えば木材中にはおよそ２０～３０％含まれており、地球上に大量に存在しており、上記のような植物由来の廃棄物中にも多く含まれている。このリグニンを有効利用することができれば、環境問題、資源問題の解決策になりうることが期待される。 Lignin, a type of plant biomass, is a polymeric phenolic compound involved in lignification in higher plants. For example, lignin is found in wood at approximately 20-30% and exists in large quantities on Earth. It is also found in large amounts in plant-derived waste materials such as those mentioned above. If this lignin could be effectively utilized, it could be expected to provide a solution to environmental and resource problems.
そこで本発明は、植物バイオマスのひとつであるリグニンの新たな利用形態として、リグニンを含む新規の材料を提供することを目的とするものである。 The present invention aims to provide a new material containing lignin as a new form of utilization of lignin, which is a type of plant biomass.
本発明者らは、上記課題を解決すべく鋭意検討した結果、リグニンとキチンとを含む硬化物が、軽量、高強度、かつ耐熱性であることを見い出し、本発明を完成するに至った。 As a result of intensive research aimed at solving the above problems, the inventors discovered that a cured material containing lignin and chitin is lightweight, has high strength, and is heat resistant, which led to the completion of the present invention.
すなわち本発明は、
［１］キチンと、リグニンとを含む硬化物、
［２］さらに、強化材の微粉を含む［１］の硬化物、
［３］強化材として炭酸カルシウムを含む［２］の硬化物、
［４］リグニンが、植物由来である、［１］～［３］のいずれかの硬化物、
［５］炭酸カルシウム及びキチンが、卵殻由来である、［３］又は［４］の硬化物、
［６］卵殻の微粉と、リグニンとの海島構造を備える、［５］の硬化物、
［７］熱硬化物である、［１］～［６］のいずれかの硬化物、
［８］キチンを含む材料の微粉と、リグニンを含む材料の微粉との混合物を加熱しながら加圧する硬化物の製造方法、
［９］混合物が、さらに強化材の微粉を含む［８］の硬化物の製造方法、
［１０］キチンを含む材料の微粉及び強化物の微粉が、卵殻の微粉である［９］の硬化物の製造方法。
［１１］卵殻の微粉の粒径が０．１～１００μｍである、［１０］の硬化物の製造方法、
［１２］リグニンを含む材料の微粉の粒径が０．１μｍ～１ｍｍである、［８］～［１１］の硬化物の製造方法、
［１３］加熱温度が１４０～２４０℃である、［８］～［１２］のいずれかの硬化物の製造方法、
である。
That is, the present invention provides:
[1] A hardened material containing chitin and lignin,
[2] A cured product according to [1], further comprising fine powder of a reinforcing material.
[3] A hardened product according to [2] containing calcium carbonate as a reinforcing material.
[4] The hardened material according to any one of [1] to [3], wherein the lignin is derived from a plant.
[5] The hardened material according to [3] or [4], wherein the calcium carbonate and chitin are derived from eggshell.
[6] The hardened material according to [5], which has a sea-island structure of eggshell fine powder and lignin.
[7] A cured product of any one of [1] to [6], which is a thermosetting product.
[8] A method for producing a hardened product by heating and pressurizing a mixture of fine powder of a material containing chitin and fine powder of a material containing lignin;
[9] The method for producing a cured product according to [8], wherein the mixture further contains fine powder of a reinforcing material.
[10] The method for producing a hardened material according to [9], wherein the fine powder of the chitin-containing material and the fine powder of the reinforcement material are fine powder of eggshells.
[11] The method for producing a cured product according to [10], wherein the particle size of the fine powder of eggshell is 0.1 to 100 μm.
[12] The method for producing a cured product according to any one of [8] to [11], wherein the particle size of the fine powder of the lignin-containing material is 0.1 μm to 1 mm;
[13] The method for producing a cured product according to any one of [8] to [12], wherein the heating temperature is 140 to 240° C.;
It is.
本発明の硬化物は、キチンと、リグニンとを含む構造体である。これらの成分は、例えば、食品工場等から排出される植物由来の廃棄物又は残渣から得ることができ、食品のリサイクルに資することができる。硬化物は、軽量、高強度、耐熱性を有し、柱、壁材、床材、芯材、タイル、舗装材、ブロック、塀、屋根材などの建材等に使用することができる。
本発明の硬化物の製造方法は、上記硬化物を容易に製造することができる。
The cured product of the present invention is a structure containing chitin and lignin. These components can be obtained from waste or residues derived from plants discharged from food factories, for example, and can contribute to food recycling. The cured product is lightweight, high-strength, and heat-resistant, and can be used for building materials such as pillars, wall materials, floor materials, core materials, tiles, paving materials, blocks, fences, and roofing materials.
The method for producing a cured product of the present invention can easily produce the above cured product.
以下、本発明の硬化物及びその製造方法を、より具体的に説明する。
本発明の硬化物は、キチンと、リグニンとを含み、好ましくは、さらに強化材の微粉を含む。強化材は、例えば炭酸カルシウムである。
The cured product of the present invention and the method for producing the same will now be described in more detail.
The hardened material of the present invention contains chitin and lignin, and preferably further contains fine powder of a reinforcing material, such as calcium carbonate.
本発明者らは、リグニンの硬化について研究開発を進めた結果、リグニンを含有する植物の茎や葉やおがくず等の植物由来の廃棄物又は残渣と、キチンとを混合して硬化させると、予想外にも軽量、高強度、耐熱性を有する硬化物が得られることが分かった。キチンを含む物質として、例えば、卵殻が挙げられるが、卵殻は、動物由来の廃棄物又は残渣であり、一方、植物の茎や葉やおがくず等は植物由来の廃棄物又は残渣であり、これらをミックスして特有の硬化物が得られることなど思いもよらなかったことである。 As a result of the research and development of lignin hardening, the inventors discovered that by mixing and hardening chitin with waste or residues of plant origin, such as plant stems, leaves, and sawdust, which contain lignin, a hardened product that is lightweight, strong, and heat-resistant can be obtained. An example of a substance that contains chitin is eggshell, but eggshells are waste or residues of animal origin, while plant stems, leaves, and sawdust are also waste or residues of plant origin, and it was unthinkable that a unique hardened product could be obtained by mixing these.
そこから更に硬化物を分析し、硬化作用の解明を図った。硬化作用は、必ずしも明確ではないが、リグニンの材料として植物由来の廃棄物又は残渣を用いた加熱加圧反応による硬化を例に説明すると、キチンが熱分解し接着効果を発現させ、また、植物由来の廃棄物又は残渣から発生する過熱水蒸気によりリグニンがその骨格を維持したまま低温で反応し、圧密効果と相乗的に作用することによって、硬化物が製造できるものと考えられる。熱硬化反応は、リグニン等に含まれるフェノール性の高分子間で反応活性点が誘発することにより進行する。つまり、硬化物としてみるとリグニンが熱硬化し、キチンがバインダーとして作用して、硬度の高い硬化物が得られたものと考えられる。 The hardened material was then further analyzed to clarify the hardening action. The hardening action is not entirely clear, but taking the example of hardening by a heat and pressure reaction using plant-derived waste or residue as the lignin material, chitin thermally decomposes and exerts an adhesive effect, and the lignin reacts at low temperatures while maintaining its skeleton due to the superheated steam generated from the plant-derived waste or residue, and this acts synergistically with the compaction effect to produce a hardened material. The thermal hardening reaction proceeds by inducing reactive sites between phenolic polymers contained in lignin, etc. In other words, when viewed as a hardened material, it is thought that the lignin hardens due to heat, and the chitin acts as a binder to produce a hardened material with high hardness.
本発明の硬化物が含むリグニンは、特に限定されるものではなく、例えば、イネ科植物由来、針葉樹由来、広葉樹由来のものが挙げられる。また、Ｈ型モノマー、Ｇ型モノマー、Ｓ型モノマーといったモノマーの種類も限定されず、これらの１種あるいは２種以上を含むモノマーが重合した構造を有する。また、これらのモノマー以外のモノマーを重合単位として含んでいてもよい。一般には、Ｈ型モノマー、Ｇ型モノマー及びＳ型モノマーの１種以上が重合した重合単位が検出されれば、リグニンが含有されていることが推定される。原材料として、純度の高いリグニンを用いてもよく、リグニンを含む植物体、植物の廃棄物や残渣を用いてもよい。 The lignin contained in the cured product of the present invention is not particularly limited, and examples thereof include those derived from grasses, conifers, and broadleaf trees. The type of monomer, such as H-type monomer, G-type monomer, and S-type monomer, is also not limited, and the product has a structure in which one or more of these monomers are polymerized. The product may also contain monomers other than these monomers as polymerization units. In general, if polymerization units in which one or more of H-type monomers, G-type monomers, and S-type monomers are polymerized are detected, it is presumed that lignin is contained. As the raw material, high-purity lignin may be used, or lignin-containing plants, plant waste, or residues may be used.
本発明の硬化物が含むキチンは、生体のクチクラ層などに含まれる含窒素多糖高分子であり、その由来は特に限定されない。例えば、鳥類又は爬虫類の卵殻、節足動物や甲殻類の外骨格、軟体動物の殻皮などの無脊椎動物のクチクラ層や、菌類の細胞壁由来のキチンが挙げられ、これらのいずれかを材料として用いることができる。原材料として、純度の高いキチンを用いても良く、キチンを含む生体材料を用いてもよい。特に、キチンを含む材料として、入手の容易性や炭酸カルシウムも含むことから卵殻が好ましい。卵殻を用いる場合には、卵殻の微粉を用いることが好ましく、この場合、本発明の硬化物は、卵殻の微粉或いは卵殻の微粉由来の成分とリグニンとを含有することになる。
また、キチンと似たような物質として、キトサンがある。本発明の硬化物は、キチンと併用して、又はキチンの代わりに、キトサンを含むこともできる。
The chitin contained in the hardened product of the present invention is a nitrogen-containing polysaccharide polymer contained in the cuticle layer of a living organism, and its origin is not particularly limited. For example, chitin derived from the cuticle layer of invertebrates such as eggshells of birds or reptiles, the exoskeletons of arthropods and crustaceans, and the shell skin of mollusks, or from the cell walls of fungi can be used as the material. As the raw material, chitin with high purity may be used, or a biological material containing chitin may be used. In particular, eggshell is preferred as a material containing chitin because it is easily available and also contains calcium carbonate. When eggshell is used, it is preferable to use fine powder of eggshell, and in this case, the hardened product of the present invention contains fine powder of eggshell or a component derived from fine powder of eggshell and lignin.
Furthermore, chitosan is a substance similar to chitin. The cured product of the present invention may contain chitosan in combination with chitin or instead of chitin.
本発明の硬化物は、卵殻の微粉と、植物由来の原材料とから製造される場合には、卵殻を強化材成分とする複合材料と考えることができる。この場合、卵殻の微粉が島部、植物由来の原材料が海部となる海島構造を有していると考えられる。 When the cured product of the present invention is produced from fine powder of eggshell and raw materials derived from plants, it can be considered to be a composite material with eggshell as a reinforcing component. In this case, it is considered to have a sea-island structure in which the fine powder of eggshell is the island portion and the raw materials derived from plants are the sea portion.
本発明の硬化物は、好ましくは、強化材を含む。強化材として、例えば軽量な炭酸カルシウムが挙げられる。強化材を含むことにより、強度が高く、比強度が大きい材料とすることができる。また、炭酸カルシウムを用いると、高い耐熱性が得られる。したがって、建材等の用途にも好適である。 The cured product of the present invention preferably contains a reinforcing material. An example of a reinforcing material is lightweight calcium carbonate. By containing a reinforcing material, a material with high strength and high specific strength can be obtained. Furthermore, the use of calcium carbonate provides high heat resistance. Therefore, it is also suitable for applications such as building materials.
本発明の硬化物は、さらに、セルロースやヘミセルロースを含んでいてもよい。セルロースやヘミセルロースは、様々な植物体中に含まれる多糖類であり、接着作用を呈することから、本発明の硬化物に含有させることで、バインダーとして機能し、硬化物の硬度、強度を高めることが期待できる。 The hardened product of the present invention may further contain cellulose or hemicellulose. Cellulose and hemicellulose are polysaccharides found in various plants and have adhesive properties. By including them in the hardened product of the present invention, they are expected to function as binders and increase the hardness and strength of the hardened product.
本発明の硬化物は、炭酸カルシウムやキチンの粒径が、０．１～１００μｍであることが好ましい。０．１μｍ程度よりも小さいと、微粉末にする製造コストが高くなる。１００μｍ程度よりも大きいと、硬化物中の強化材の分散度が低くなり好ましくない。 In the hardened product of the present invention, the particle size of calcium carbonate or chitin is preferably 0.1 to 100 μm. If it is smaller than about 0.1 μm, the manufacturing cost of turning it into fine powder will be high. If it is larger than about 100 μm, the degree of dispersion of the reinforcing material in the hardened product will be low, which is not preferable.
本発明の硬化物は、リグニンを１０質量％程度以上含むことが好ましい。１０質量％程度以上を含むことにより硬度の高い硬化物とすることができる。リグニン含有量の上限は、特に限定されないが、リグニンはバインダー又は複合材料のマトリックスとして考えられるために、適切な量で含むことが好ましい。本発明者らの実験により５０質量％程度を含有させていても十分な特性を有する硬化物が得られることが確認されている。 The cured product of the present invention preferably contains 10% by mass or more of lignin. By containing 10% by mass or more, a cured product with high hardness can be obtained. There is no particular upper limit to the lignin content, but since lignin can be considered as a binder or a matrix for a composite material, it is preferable to contain an appropriate amount. Experiments by the present inventors have confirmed that a cured product with sufficient properties can be obtained even if the content is about 50% by mass.
本発明の硬化物は、キチン、リグニン、炭酸カルシウムなどの強化材、セルロース、ヘミセルロース以外の成分を含むことができる。例えば植物の廃棄物又は残渣に含まれる成分を含むことができ、これによりリサイクル率が向上する。他の強化材や接着剤、接着助剤、着色剤などを含むこともできる。また、原材料に含まれるか又は硬化物の製造時に添加されることがある水分を含む場合がある。 The hardened product of the present invention may contain components other than reinforcing materials such as chitin, lignin, and calcium carbonate, cellulose, and hemicellulose. For example, it may contain components contained in plant waste or residues, which improves the recycling rate. It may also contain other reinforcing materials, adhesives, adhesive assistants, colorants, and the like. It may also contain moisture that is contained in the raw materials or that may be added during the production of the hardened product.
本発明の硬化物は、軽量、高強度、耐熱性を有し、建材等に有用である。また、比熱が低いので断熱効率が高い点でも建材等の用途に有利である。更に、後述するように加熱しながら加圧するという工程により製造することができるので、大量生産に向いており、プレス型により種々の形状の製品を製造することができ、また、プレス機の大きさにもよるが、大型の製品も製造することができる。
また、キチン、リグニンを含み、さらには炭酸カルシウムを含むことができる本発明の硬化物は、生分解性を有しているので、地球環境に優しい材料としての用途に有利である。
The cured product of the present invention is lightweight, has high strength, and is heat resistant, and is useful as a building material, etc. In addition, since the specific heat is low, the heat insulating efficiency is high, which is advantageous for applications such as building materials. Furthermore, since it can be produced by a process of applying pressure while heating as described below, it is suitable for mass production, and products of various shapes can be produced by a press mold, and large products can also be produced, depending on the size of the press machine.
Furthermore, the hardened product of the present invention, which contains chitin, lignin, and may further contain calcium carbonate, is biodegradable and therefore advantageous for use as an environmentally friendly material.
次に、本発明の硬化物の製造方法の例を説明する。
硬化物は、例えば、キチンの微粉と、リグニンを含む材料の微粉との混合物を加熱しながら加圧する工程により製造することができる。動物由来の廃棄物又は残渣のリサイクルを考えると、強化材としての炭酸カルシウムと、キチンを含む卵殻を原材料として用いることが好ましい。植物由来の廃棄物又は残渣のリサイクルを考えると、リグニンを含む材料として植物由来の廃棄物又は残渣を原材料として用いることが好ましい。また、リグニンを含む材料として工業残渣を用いることもできる。
Next, an example of the method for producing the cured product of the present invention will be described.
The hardened material can be produced, for example, by a process of heating and pressurizing a mixture of fine powder of chitin and fine powder of a material containing lignin. In consideration of recycling animal-derived waste or residue, it is preferable to use calcium carbonate as a reinforcing material and eggshells containing chitin as raw materials. In consideration of recycling plant-derived waste or residue, it is preferable to use plant-derived waste or residue as a raw material containing lignin. Also, industrial residues can be used as the material containing lignin.
卵殻を原材料として用いる場合には、卵殻膜を予め除去しておくことが好ましい。もっとも、卵殻膜の除去処理を行わないで原材料としても用いることを排除するものではない。卵殻を用いる場合にも、上述した好適な粒径範囲に粉砕して微粉にすることが好ましい。 When using eggshells as a raw material, it is preferable to remove the eggshell membrane beforehand. However, this does not exclude the use of eggshells as a raw material without removing the eggshell membrane. Even when using eggshells, it is preferable to pulverize them into a fine powder in the preferred particle size range described above.
リグニンを含む植物由来の廃棄物又は残渣としては、野菜を使用した食品工場や加工場や野菜生産者、更には木工場から排出される植物由来の廃棄物又は残渣、例えば野菜の茎や葉やおがくず等を用いることができる。原材料に植物由来の廃棄物又は残渣を用いる場合にも粉砕して微粉にすることが好ましい。 Plant-derived waste or residues containing lignin can be waste or residues of plant origin discharged from food factories, processing plants, vegetable producers, and even woodworking factories, such as vegetable stems, leaves, and sawdust. When using plant-derived waste or residues as raw materials, it is also preferable to pulverize them into fine powder.
リグニンを含む材料、例えば植物由来の廃棄物又は残渣の粒径は０．１μｍ～１ｍｍ程度とすることが好ましい。０．１μｍ程度よりも小さいと、微粉末にする製造コストが高くなる。１ｍｍ程度よりも大きいと、硬化物中のリグニンの分散度が低くなり好ましくない。 The particle size of the lignin-containing material, such as waste or residue derived from plants, is preferably about 0.1 μm to 1 mm. If it is smaller than about 0.1 μm, the manufacturing cost of turning it into a fine powder will be high. If it is larger than about 1 mm, the degree of dispersion of the lignin in the hardened material will be low, which is not preferable.
卵殻の微粉と、リグニンを含む材料の微粉とを所定割合で混合する。混合する手段は特に限定されず、各種のミキサーを用いることができる。また、ミキサーは、原材料を所定の粒径まで粉砕する機能を有するものであってもよく、この場合は卵殻の粉砕及び微粉化と、植物由来の廃棄物又は残渣の粉砕及び微粉化と、混合とを一つの装置で行うことができる。 Eggshell fine powder and lignin-containing material fine powder are mixed in a specified ratio. There are no particular limitations on the mixing means, and various mixers can be used. The mixer may also have the function of pulverizing the raw materials to a specified particle size, in which case the crushing and pulverization of eggshells, and the crushing and pulverization and mixing of plant-derived waste or residues can be performed in a single device.
卵殻の微粉と、植物由来の廃棄物又は残渣中の微粉との混合比は、質量比で卵殻の最大値で９：１の割合から、卵殻の最小値で０．０１：９．９９の割合の範囲とすることができる。 The mixing ratio of eggshell fine powder to the fine powder in the plant-derived waste or residue can be in the range of 9:1 for the maximum eggshell value to 0.01:9.99 for the minimum eggshell value, by mass ratio.
また混合時に、水分を添加することができる。水分は、次工程の加熱加圧時に、植物由来の廃棄物又は残渣から発生する過熱水蒸気によりリグニンがその骨格を維持したまま低温で反応するのを促進させることができる。つまり、植物由来の廃棄物又は残渣中に含まれる水分が少ない場合には、混合時に水分を添加して補うことができる。混合物に対する水の含有量は、１～１０質量％程度（廃棄物又は残渣中の水分を含む）、好ましくは１～５質量％程度である。 Moisture can also be added during mixing. Moisture can promote the reaction of lignin at low temperatures while maintaining its skeleton by superheated steam generated from the plant-derived waste or residue during the next heating and pressurizing process. In other words, if the plant-derived waste or residue contains a small amount of moisture, moisture can be added during mixing to make up for this. The water content of the mixture is about 1 to 10% by mass (including moisture in the waste or residue), preferably about 1 to 5% by mass.
混合後に原材料を加熱しながら加圧することが好ましい。
加熱温度は１４０～２４０℃程度とすることが好ましい。１４０～２４０℃の範囲で、卵殻中のキチンや、植物由来の廃棄物又は残渣の繊維成分であるセルロースやヘミセルロースが含まれている場合には、そのセルロースやヘミセルロースも熱分解し接着効果を発現させ、また、植物由来の廃棄物又は残渣から発生する過熱水蒸気によりリグニンが反応し、圧密効果と相乗的に作用することによって、硬化物が製造できる。加熱温度は、１６０～２００℃がより好ましい。
After mixing, the raw materials are preferably pressurized while being heated.
The heating temperature is preferably about 140 to 240° C. In the range of 140 to 240° C., when chitin in eggshells or cellulose or hemicellulose, which are fiber components of waste or residue derived from plants, are contained, the cellulose or hemicellulose is also pyrolyzed to exert an adhesive effect, and lignin reacts with superheated steam generated from waste or residue derived from plants, and a hardened product can be produced by acting synergistically with the compaction effect. The heating temperature is more preferably 160 to 200° C.
加圧力は好ましくは２～８ｔであり、より好ましくは３～６ｔである。かかる加圧力によりリグニンがその骨格を維持したまま低温で反応し、圧密効果と相乗的に作用することによって硬化物が製造できる。加熱・加圧時間は１～６０分が好ましく、より好ましくは１０～２０分である。 The pressure is preferably 2 to 8 tons, more preferably 3 to 6 tons. This pressure causes the lignin to react at a low temperature while maintaining its skeleton, and this acts synergistically with the compaction effect to produce a hardened product. The heating and pressurizing time is preferably 1 to 60 minutes, more preferably 10 to 20 minutes.
加熱しながら加圧する装置は、所定温度に加圧しながら加熱することができる装置であれば特に限定されず、特に硬化物を所定の形状に成形することができる型を有する装置が好ましい。また、上述した混合するための装置と組み合わせて、硬化物の製造装置として構成することができる。 The device for applying pressure while heating is not particularly limited as long as it is capable of heating while applying pressure to a predetermined temperature, and is preferably equipped with a mold capable of forming the cured product into a predetermined shape. In addition, it can be combined with the above-mentioned mixing device to configure a device for manufacturing a cured product.
加熱・加圧成型を行った後は、得られた硬化物を４０～５０℃以下に冷却する。冷却は、送風機等を用いても良いし、硬化物を４０～５０℃以下に冷却することができる装置であればどのような装置でもよく、水冷ジャケットからの伝熱により冷却してもよい。冷却温度はこの温度よりも冷却温度が高いと接着効果が低下し、硬度の低下の原因となるおそれがある。冷却時間は３０～６０分程度かけることが好ましい。急速に冷却すると製造された硬化物表面にひび割れ等が生じ、硬度が低下するおそれがある。 After heating and pressure molding, the resulting cured product is cooled to below 40-50°C. Cooling can be done using a fan or any other device capable of cooling the cured product to below 40-50°C, or by heat transfer from a water-cooled jacket. If the cooling temperature is higher than this, the adhesive effect may decrease, which may cause a decrease in hardness. The cooling time is preferably about 30-60 minutes. If the product is cooled too quickly, cracks may appear on the surface of the cured product, resulting in a decrease in hardness.
卵殻膜を分離した卵殻を５μｍに微粉砕した。また、植物由来の廃棄物としてトマトの茎及び葉を５μｍに微粉砕した。これらの卵殻及び植物由来の廃棄物を質量比で８：２の割合で混合するともに、水を加えて全体の含水率を２．６質量％とした。
次いで加熱プレス装置の成形型内に混合物を入れ、１６０℃に加熱するとともに加圧力４ｔで加圧する状態を１５分保持した。保持後に硬化物を６０分かけて５０℃以下に冷却した。かくして直径８０ｍｍ、高さ４０ｍｍの円柱状の硬化物が得られた。
The eggshells from which the eggshell membranes were separated were pulverized to 5 μm. In addition, tomato stems and leaves were pulverized to 5 μm as plant-derived waste. The eggshells and plant-derived waste were mixed in a mass ratio of 8:2, and water was added to adjust the overall moisture content to 2.6 mass%.
The mixture was then placed in a mold of a hot press machine, heated to 160°C, and pressed with a pressure of 4t for 15 minutes. After this state, the cured product was cooled to 50°C or lower over 60 minutes. Thus, a cylindrical cured product with a diameter of 80 mm and a height of 40 mm was obtained.
また、植物由来の廃棄物としてトマトの茎及び葉の代わりに、おがくずを用いて同様の実験を行ったところ、同様に硬化物が得られた。
In addition, a similar experiment was conducted using sawdust instead of tomato stems and leaves as plant-derived waste, and a hardened material was similarly obtained.
Claims (12)
キチンを含む卵殻の微粉が島部、前記リグニンが海部となる海島構造を備える、熱硬化物。 A thermoset of lignin containing chitin,
A thermoset material having a sea-island structure in which chitin-containing eggshell fine powder constitutes the islands and the lignin constitutes the sea .
リグニンを含有する植物由来の廃棄物又は残渣と、卵殻の微粉とを含む混合物を加熱しながら加圧する熱硬化物の製造方法。A method for producing a thermoset product, comprising heating and pressurizing a mixture containing lignin-containing plant-derived waste or residue and eggshell fine powder.
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