JP2018058057A - Carbon-containing waste treatment method - Google Patents
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Landscapes
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、炭素含有廃棄物、特に、炭素繊維を含む廃プラスチックを焼却して処理する方法に関する。 The present invention relates to a method for incinerating and treating carbon-containing wastes, in particular waste plastics containing carbon fibers.
近年、軽量且つ高強度な構造材料として、樹脂又は金属等のマトリックス材料と炭素化合物とで形成された複合材料の需要が、飛躍的に増大している。特に、熱硬化性樹脂又は熱可塑性樹脂からなるマトリックス材料と炭素繊維とを複合化した炭素繊維強化プラスチック（ＣＦＲＰ：Carbon Fiber reinforced plastics）の需要の増大は、目覚ましいものがある。 In recent years, as a lightweight and high-strength structural material, the demand for a composite material formed of a matrix material such as a resin or metal and a carbon compound has increased dramatically. In particular, the demand for carbon fiber reinforced plastics (CFRP) in which a matrix material made of a thermosetting resin or a thermoplastic resin and carbon fibers are combined is remarkable.
その一方で、その需要の増大に伴い、炭素繊維を含む廃プラスチックをはじめ、ＢＯＦ（Biomass oil fuel）、ＡＳＲ（Automobile shredder residue）、ＲＰＦ（Refuse derived paper and plastics densified fuel）、ＲＤＦ（Refuse derived fuel）、木屑、廃タイヤ、ゴム屑、吸水性ポリマーの廃棄物、都市ゴミ、熱硬化性・熱可塑性樹脂の廃棄物、廃ＦＲＰ（Fiber reinforced plastics）、カーボンファイバーの廃棄物、光ファイバーの廃棄物、太陽電池の廃棄物等の炭素化合物を含有する廃棄物の廃棄量も増大している。 On the other hand, along with the increasing demand, waste plastic including carbon fiber, BOF (Biomass oil fuel), ASR (Automobile shredder residue), RPF (Refuse derived paper and plastics densified fuel), RDF (Refuse derived fuel) ), Wood waste, waste tires, rubber waste, water-absorbing polymer waste, municipal waste, thermosetting and thermoplastic resin waste, waste FRP (Fiber reinforced plastics), carbon fiber waste, optical fiber waste, The amount of waste containing carbon compounds such as solar cell waste is also increasing.
このような炭素含有廃棄物の処理方法としては、セメント製造プロセスにおいて、炭素含有廃棄物等を代替燃料として有効利用しながら焼却して処理する方法がある。 As a method of treating such carbon-containing waste, there is a method of incineration while effectively using carbon-containing waste as an alternative fuel in a cement manufacturing process.
しかし、炭素含有廃棄物を焼却して処理すると、炭素含有廃棄物が難燃性であった場合等には、炭素含有廃棄物に含まれる炭素化合物が燃え残り、その燃え残った炭素化合物が、排ガス中に混入してしまうことがあった。その結果、排ガスの集塵設備（電気集塵機、バグフィルタ等）において、それらに付着した炭素化合物に起因する故障（電気短絡事故、フィルタの損傷等）が生じるおそれがあるという問題があった。 However, if the carbon-containing waste is incinerated and treated, if the carbon-containing waste is incombustible, etc., the carbon compound contained in the carbon-containing waste remains unburned, and the unburned carbon compound is In some cases, it was mixed in the exhaust gas. As a result, there has been a problem in the exhaust gas dust collection equipment (electric dust collector, bag filter, etc.) that a failure (electric short circuit accident, filter damage, etc.) due to the carbon compounds adhering to them may occur.
そのような問題を回避する方法としては、セメント製造プロセスによる処理を行う前に、炭素含有廃棄物から炭素繊維等の炭素化合物を除去する処理を行うという方法があるが、事前の処理を行うことは非常に煩雑であった。 As a method of avoiding such a problem, there is a method of removing a carbon compound such as carbon fiber from the carbon-containing waste before performing the treatment by the cement manufacturing process. Was very cumbersome.
そこで、事前に炭素化合物を除去する処理を省略することができる処理方法として、炭素含有廃棄物の平均粒子径が３ｍｍ以下になるように粉砕した後、その粉砕した炭素含有廃棄物を、セメントキルンの内部温度が１２００℃以上である位置に供給するという方法が提案されている（例えば、特許文献１参照）。 Therefore, as a treatment method that can omit the treatment of removing the carbon compound in advance, the carbon-containing waste is pulverized so that the average particle diameter is 3 mm or less, and then the pulverized carbon-containing waste is treated with a cement kiln. Has been proposed (see, for example, Patent Literature 1).
しかし、特許文献１に記載の方法は、高強度の炭素含有廃棄物を平均粒子径が３ｍｍ以下の極めて小さい粒子となるまで細かく粉砕する必要があり、その粉砕のために多大な労力が必要になるという問題があった。 However, in the method described in Patent Document 1, it is necessary to finely pulverize a high-strength carbon-containing waste until it becomes extremely small particles having an average particle diameter of 3 mm or less, and much labor is required for the pulverization. There was a problem of becoming.
本発明は以上の点に鑑みてなされたものであり、少ない労力で炭素含有廃棄物に含まれる炭素化合物を十分に燃焼させることができる炭素含有廃棄物処理方法を提供することを目的とする。 This invention is made | formed in view of the above point, and it aims at providing the carbon containing waste processing method which can fully burn the carbon compound contained in a carbon containing waste with little effort.
上記目的を達成するために、本発明の炭素含有廃棄物処理方法は、炭素含有廃棄物を焼却する炭素含有廃棄物処理方法であって、前記炭素含有廃棄物と、界面活性剤及び過酸化水素とを接触させた後、該炭素含有廃棄物を焼却することを特徴とする。 In order to achieve the above object, the carbon-containing waste treatment method of the present invention is a carbon-containing waste treatment method for incinerating carbon-containing waste, comprising the carbon-containing waste, a surfactant, and hydrogen peroxide. And then incinerating the carbon-containing waste.
本発明の炭素含有廃棄物処理方法では、界面活性剤によって炭素含有廃棄物の濡れ性が改善するので、過酸化水素（Ｈ２Ｏ２）が炭素含有廃棄物（すなわち、それに含まれる炭素化合物）に十分に接触する。そして、焼却時には、その過酸化水素に含まれる酸素と炭素含有廃棄物に含まれる炭素化合物が効率よく反応するので、炭素化合物のサイズ（すなわち、炭素含有廃棄物の平均粒子径）を極めて小さくしなくても、炭素化合物を十分に燃焼させることができる。 In the carbon-containing waste treatment method of the present invention, the wettability of the carbon-containing waste is improved by the surfactant, so hydrogen peroxide (H 2 O 2 ) is added to the carbon-containing waste (that is, the carbon compound contained therein). Fully contact. At the time of incineration, the oxygen contained in the hydrogen peroxide and the carbon compound contained in the carbon-containing waste react efficiently, so the size of the carbon compound (that is, the average particle size of the carbon-containing waste) is extremely reduced. Even if not, the carbon compound can be burned sufficiently.
したがって、本発明の炭素含有廃棄物処理方法によれば、事前に炭素化合物の除去を行う必要がなく、また、炭素含有廃棄物の平均粒子径を３ｍｍ以下の極めて小さいサイズにしなくてもよいので、少ない労力で炭素含有廃棄物に含まれる炭素化合物を十分に燃焼させることができる。 Therefore, according to the carbon-containing waste treatment method of the present invention, it is not necessary to remove the carbon compound in advance, and the average particle size of the carbon-containing waste does not have to be as small as 3 mm or less. The carbon compound contained in the carbon-containing waste can be sufficiently burned with little effort.
なお、本発明における過酸化水素による炭素化合物の燃焼性改善効果は、詳細は不明であるものの、焼却の処理（例えば、セメントキルン等の焼却設備）に供給された過酸化水素が比較的低い温度域で解離して活性酸素ラジカルを放出し、その活性酸素ラジカルが炭素化合物の燃焼反応を促進することに起因する効果であると推測される。 In addition, although the details of the effect of improving the flammability of the carbon compound by hydrogen peroxide in the present invention are not clear, the hydrogen peroxide supplied to the incineration process (for example, incineration equipment such as cement kiln) has a relatively low temperature. It is presumed that the effect is caused by dissociating in the region and releasing active oxygen radicals, which promote the combustion reaction of the carbon compound.
本発明は、他の観点においては、炭素含有廃棄物を焼却する炭素含有廃棄物処理方法であって、前記炭素含有廃棄物に界面活性剤を接触させて小径化し、これに更に過酸化水素を接触させた後、該炭素含有廃棄物を焼却することを特徴とする炭素含有廃棄物処理方法を提供する。 In another aspect, the present invention is a carbon-containing waste treatment method for incinerating a carbon-containing waste, wherein the carbon-containing waste is contacted with a surfactant to reduce the diameter, and hydrogen peroxide is further added thereto. Provided is a method for treating carbon-containing waste characterized by incinerating the carbon-containing waste after contact.
上記の観点の炭素含有廃棄物処理方法では、界面活性剤及び過酸化水素を用いるので、上述したとおり、炭素含有廃棄物に含まれる炭素化合物の燃焼反応を促進し、これにより燃焼性改善効果が得られる。加えて、炭素含有廃棄物を小径化して過酸化水素を接触させるので、燃焼性改善効果がより高められる。また、炭素含有廃棄物に界面活性剤を接触させて小径化するので、その界面活性剤により、炭素含有廃棄物の小径化の際、あるいは炭素含有廃棄物の小径化後の発塵を抑制することができる。 In the carbon-containing waste treatment method of the above aspect, since the surfactant and hydrogen peroxide are used, as described above, the combustion reaction of the carbon compound contained in the carbon-containing waste is promoted, thereby improving the combustibility improvement effect. can get. In addition, since the carbon-containing waste is reduced in size and brought into contact with hydrogen peroxide, the combustibility improving effect is further enhanced. In addition, since the surfactant is brought into contact with the carbon-containing waste to reduce the diameter, the surfactant suppresses dust generation when reducing the diameter of the carbon-containing waste or after reducing the diameter of the carbon-containing waste. be able to.
本発明の炭素含有廃棄物処理方法においては、前記過酸化水素の量は、前記炭素含有廃棄物の量を１００質量部としたとき、１５質量部以上、且つ、１００質量部以下であることが好ましい。炭素含有廃棄物の量を１００質量部としたときに、過酸化水素の量が１５質量部未満であると、十分に炭素含有廃棄物の燃焼性改善効果を得られないことがある。一方、過酸化水素の量の上限については、炭素含有廃棄物の燃焼性改善の観点からは制約が生じない。しかし、薬剤コスト等の観点から、炭素含有廃棄物の量を１００質量部としたときに、過酸化水素の量が１００質量部を超えると、コストが増加してしまうので好ましくない。 In the carbon-containing waste treatment method of the present invention, the amount of the hydrogen peroxide is 15 parts by mass or more and 100 parts by mass or less when the amount of the carbon-containing waste is 100 parts by mass. preferable. When the amount of carbon-containing waste is 100 parts by mass, if the amount of hydrogen peroxide is less than 15 parts by mass, the effect of improving the combustibility of the carbon-containing waste may not be obtained. On the other hand, the upper limit of the amount of hydrogen peroxide is not restricted from the viewpoint of improving the combustibility of the carbon-containing waste. However, from the viewpoint of drug cost and the like, when the amount of carbon-containing waste is 100 parts by mass, if the amount of hydrogen peroxide exceeds 100 parts by mass, the cost increases, which is not preferable.
また、本発明の炭素含有廃棄物処理方法においては、前記界面活性剤の量は、前記過酸化水素の量を１００質量部としたとき、０．０１質量部以上、且つ、２５質量部以下であることが好ましい。過酸化水素の量を１００質量部としたときに、界面活性剤の量が０．０１質量部未満であると、十分に炭素含有廃棄物の燃焼性改善効果を得られないことがある。一方、過酸化水素の量の上限については、炭素含有廃棄物の燃焼性改善の観点からは制約が生じない。しかし、薬剤コスト等の観点から、過酸化水素の量を１００質量部としたときに、界面活性剤の量が２５質量部を超えると、コストが増加してしまうので好ましくない。 In the carbon-containing waste treatment method of the present invention, the amount of the surfactant is 0.01 parts by mass or more and 25 parts by mass or less when the amount of the hydrogen peroxide is 100 parts by mass. Preferably there is. When the amount of hydrogen peroxide is 100 parts by mass, if the amount of the surfactant is less than 0.01 parts by mass, the effect of improving the combustibility of the carbon-containing waste may not be obtained. On the other hand, the upper limit of the amount of hydrogen peroxide is not restricted from the viewpoint of improving the combustibility of the carbon-containing waste. However, from the viewpoint of drug cost and the like, when the amount of hydrogen peroxide is 100 parts by mass, if the amount of the surfactant exceeds 25 parts by mass, the cost increases, which is not preferable.
また、本発明の炭素含有廃棄物処理方法においては、前記炭素含有廃棄物の平均粒子径は、１０ｍｍ以下であることが好ましい。燃焼性改善効果は、炭素含有廃棄物の平均粒子径を極めて小さくしなくても得ることができるが、平均粒子径を１０ｍｍ程度まで小さくすると、特にその効果が大きくなる。 Moreover, in the carbon containing waste processing method of this invention, it is preferable that the average particle diameter of the said carbon containing waste is 10 mm or less. The combustibility improving effect can be obtained without extremely reducing the average particle size of the carbon-containing waste, but the effect is particularly increased when the average particle size is reduced to about 10 mm.
また、本発明の炭素含有廃棄物処理方法においては、前記炭素含有廃棄物は、炭素繊維強化プラスチック（ＣＦＲＰ：Carbon Fiber reinforced plastics）の廃棄物（以下、「廃ＣＦＲＰ」という。）、ＢＯＦ（Biomass oil fuel）、ＡＳＲ（Automobile shredder residue）、ＲＰＦ（Refuse derived paper and plastics densified fuel）、ＲＤＦ（Refuse derived fuel）、木屑、廃タイヤ、ゴム屑、吸水性ポリマーの廃棄物、都市ゴミ、熱硬化性・熱可塑性樹脂の廃棄物、廃ＦＲＰ（Fiber reinforced plastics）、カーボンファイバーの廃棄物、光ファイバーの廃棄物、及び、太陽電池の廃棄物からなる群から選択される一以上の廃棄物であることが好ましい。 In the carbon-containing waste treatment method of the present invention, the carbon-containing waste is carbon fiber reinforced plastics (CFRP) waste (hereinafter referred to as “waste CFRP”), BOF (Biomass). oil fuel), ASR (Automobile shredder residue), RPF (Refuse derived paper and plastics densified fuel), RDF (Refuse derived fuel), wood waste, waste tire, rubber waste, water-absorbing polymer waste, municipal waste, thermosetting -It must be at least one waste selected from the group consisting of thermoplastic resin waste, waste FRP (Fiber reinforced plastics), carbon fiber waste, optical fiber waste, and solar cell waste. preferable.
これらの廃棄物には炭素化合物が含まれているので、これらの廃棄物が処理対象物である場合には、上記の方法によって効果的に処理することができる。 Since these wastes contain carbon compounds, when these wastes are treatment objects, they can be treated effectively by the above method.
また、本発明の炭素含有廃棄物処理方法においては、前記炭素含有廃棄物は、炭素繊維を含むものであることが好ましい。処理対象物が炭素化合物を含む廃棄物であれば燃焼促進効果を得ることができるものであるが、炭素化合物が炭素繊維であるものに対して、特に高い燃焼促進効果を得ることができる。 Moreover, in the carbon containing waste processing method of this invention, it is preferable that the said carbon containing waste contains a carbon fiber. If the object to be treated is a waste containing a carbon compound, a combustion promoting effect can be obtained. However, a particularly high combustion promoting effect can be obtained with respect to the carbon compound being carbon fiber.
また、本発明の炭素含有廃棄物処理方法においては、前記炭素含有廃棄物と、界面活性剤及び過酸化水素とを接触させた後、該炭素含有廃棄物をセメント製造設備で焼却するようにしてもよい。 Moreover, in the carbon-containing waste treatment method of the present invention, after bringing the carbon-containing waste into contact with a surfactant and hydrogen peroxide, the carbon-containing waste is incinerated in a cement production facility. Also good.
本発明は、炭素含有廃棄物を焼却して処理する炭素含有廃棄物処理方法に関する。 The present invention relates to a carbon-containing waste treatment method for incinerating and treating carbon-containing waste.
その処理対象物としては、炭素化合物を含有する廃棄物であればよく、特に制限はないが、具体的には、例えば、廃ＣＦＲＰ、ＢＯＦ、ＡＳＲ、ＲＰＦ、ＲＤＦ、木屑、廃タイヤ、ゴム屑、吸水性ポリマーの廃棄物、都市ゴミ、熱硬化性・熱可塑性樹脂の廃棄物、廃ＦＲＰ、カーボンファイバーの廃棄物、光ファイバーの廃棄物、太陽電池の廃棄物などが挙げられる。廃棄物は１種類を処理対象物としてもよく、あるいは２種以上を処理対象物としてもよい。 The treatment object may be any waste containing a carbon compound and is not particularly limited. Specifically, for example, waste CFRP, BOF, ASR, RPF, RDF, wood waste, waste tire, rubber waste Water-absorbing polymer waste, municipal waste, thermosetting / thermoplastic resin waste, waste FRP, carbon fiber waste, optical fiber waste, solar cell waste, and the like. One type of waste may be a processing target, or two or more types may be processing targets.
本発明の処理方法においては、上記炭素含有廃棄物に、界面活性剤と過酸化水素とを接触させる。 In the treatment method of the present invention, a surfactant and hydrogen peroxide are brought into contact with the carbon-containing waste.
界面活性剤としては、アニオン系、ノニオン系及びカチオン系の各種界面活性剤のうちから選択される１種以上であればよく、特に、アニオン系又はノニオン系の界面活性剤を用いることが好ましい。 The surfactant may be one or more selected from anionic, nonionic and cationic surfactants, and anionic or nonionic surfactants are particularly preferable.
アニオン系の界面活性剤としては、例えば、アルキルエーテル硫酸エステルナトリウム、アルキル硫酸エステルナトリウム、直鎖アルキルベンゼンスルホン酸ナトリウム（ＬＡＳ）、脂肪酸ナトリウム、脂肪酸カリウム、アルファスルホ脂肪酸エステルナトリウム、アルファオレフィンスルホン酸ナトリウム、アルキルスルホン酸ナトリウム等が挙げられる。 Anionic surfactants include, for example, sodium alkyl ether sulfate, sodium alkyl sulfate, sodium linear alkylbenzene sulfonate (LAS), fatty acid sodium, fatty acid potassium, alpha sulfo fatty acid ester sodium, alpha olefin sulfonic acid sodium salt, Examples include sodium alkyl sulfonate.
また、ノニオン系の界面活性剤としては、例えば、しょ糖脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸アルカノールアミド、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル等が挙げられる。 Examples of the nonionic surfactant include sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and the like.
界面活性剤の量は、炭素含有廃棄物の量を１００質量部としたときに、０．１質量部以上１０質量部以下、好ましくは０．５量部以上６質量部以下、より好ましくは１質量部以上３質量部以下である。 The amount of the surfactant is from 0.1 parts by weight to 10 parts by weight, preferably from 0.5 parts by weight to 6 parts by weight, more preferably 1 when the amount of the carbon-containing waste is 100 parts by weight. It is not less than 3 parts by mass.
また、界面活性剤の量は、過酸化水素の量を１００質量部としたときに、０．０１質量部以上２５質量部以下、好ましくは０．２量部以上２０質量部以下、より好ましくは０．３質量部以上１５質量部以下である。 The amount of the surfactant is 0.01 parts by mass or more and 25 parts by mass or less, preferably 0.2 parts by mass or more and 20 parts by mass or less, more preferably when the amount of hydrogen peroxide is 100 parts by mass. 0.3 parts by mass or more and 15 parts by mass or less.
界面活性剤の量が上記の範囲でない場合には、十分に炭素含有廃棄物の燃焼性改善効果を得られないことがある。 When the amount of the surfactant is not in the above range, the effect of improving the combustibility of the carbon-containing waste may not be obtained sufficiently.
過酸化水素は、純度等が特に限定されるものではなく、３０％水溶液等、通常に入手が可能なものを用いればよい。 Hydrogen peroxide is not particularly limited in its purity and the like, and a normally available one such as a 30% aqueous solution may be used.
過酸化水素の量は、炭素含有廃棄物の量を１００質量部としたときに、１５質量部以上、好ましくは３０質量部以上、より好ましくは４５質量部以上である。 The amount of hydrogen peroxide is 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 45 parts by mass or more when the amount of carbon-containing waste is 100 parts by mass.
過酸化水素の量の下限については、炭素含有廃棄物の量を１００質量部としたときに、過酸化水素の量が１５質量部未満であると、十分に炭素含有廃棄物の燃焼性改善効果を得られないことがある。 Regarding the lower limit of the amount of hydrogen peroxide, when the amount of carbon-containing waste is 100 parts by mass, if the amount of hydrogen peroxide is less than 15 parts by mass, the carbon-containing waste is sufficiently improved in combustibility. May not be obtained.
過酸化水素の量の上限については、炭素含有廃棄物の燃焼性改善の観点からは制約が生じない。しかし、薬剤コスト等の観点から炭素含有廃棄物の量を１００質量部としたときに、過酸化水素の量が１００質量部を超えると、コストが増加してしまうので好ましくない。 The upper limit of the amount of hydrogen peroxide is not restricted from the viewpoint of improving the combustibility of the carbon-containing waste. However, from the viewpoint of drug cost and the like, when the amount of carbon-containing waste is 100 parts by mass, if the amount of hydrogen peroxide exceeds 100 parts by mass, the cost increases, which is not preferable.
本発明の処理方法において、上記炭素含有廃棄物と、上記界面活性剤及び過酸化水素とを接触させる方法に、特に制限はない。すなわち、炭素含有廃棄物に、界面活性剤と過酸化水素とが作用するようにすればよい。具体的には、例えば、炭素含有廃棄物に対して、界面活性剤及び／又は過酸化水素を滴下、噴霧、塗布等したりすればよく、必要に応じてそれとともに混合、攪拌等の操作を施してもよい。あるいは、炭素含有廃棄物を界面活性剤及び／又は過酸化水素を含んだ溶液に含浸させたり、必要に応じてその炭素含有廃棄物を揺動させながらその含浸を行ったりしてもよい。あるいは、また、界面活性剤及び／又は過酸化水素が気化した雰囲気下に炭素含有廃棄物を静置して曝露したり、必要に応じてその炭素含有廃棄物を揺動させながらその雰囲気下に曝露したりしてもよい。より典型的には、例えば、焼却設備の内部で炭素含有廃棄物の周囲で過酸化水素の熱分解が生じる環境が構成される方法などであってもよい。 In the treatment method of the present invention, the method for bringing the carbon-containing waste into contact with the surfactant and hydrogen peroxide is not particularly limited. That is, the surfactant and hydrogen peroxide may act on the carbon-containing waste. Specifically, for example, a surfactant and / or hydrogen peroxide may be dropped, sprayed, applied, or the like on a carbon-containing waste, and if necessary, operations such as mixing and stirring are performed. You may give it. Alternatively, the carbon-containing waste may be impregnated in a solution containing a surfactant and / or hydrogen peroxide, or the carbon-containing waste may be impregnated while the carbon-containing waste is swung as necessary. Alternatively, the carbon-containing waste can be left and exposed in an atmosphere in which the surfactant and / or hydrogen peroxide is vaporized, or the carbon-containing waste can be swung as necessary in the atmosphere. Or may be exposed. More typically, for example, a method in which an environment in which thermal decomposition of hydrogen peroxide occurs around the carbon-containing waste inside the incineration facility may be used.
界面活性剤と過酸化水素とは、混合状態で用いてもよく、各別の形態で用いてもよい。両者を混合状態で用いる場合には、その混合方法は特に限定されず、液体の混合方法として一般的なものであればどのような方法であってもよい。例えば、混合割合の多い過酸化水素に所定量の界面活性剤を添加した後、撹拌すれることによって混合すればよい。また、両者をともに含有する水溶液を調製して用いてもよい。一方、界面活性剤と過酸化水素とを各別の形態で用いる場合にも、水溶液の形態を別々に調製して用いることができる。ただし、界面活性剤を含む水溶液を調製する場合には、かかる水溶液の粘性を大きくしない観点から、水１００質量部に対して界面活性剤を０．１質量部〜３０質量部添加して調製されたものであることが好ましく、１質量部〜１０質量部添加して調製されたものであることがより好ましい。 The surfactant and hydrogen peroxide may be used in a mixed state or in different forms. When both are used in a mixed state, the mixing method is not particularly limited, and any method may be used as long as it is a general liquid mixing method. For example, a predetermined amount of surfactant may be added to hydrogen peroxide having a high mixing ratio, and then mixed by stirring. Moreover, you may prepare and use the aqueous solution which contains both. On the other hand, even when the surfactant and hydrogen peroxide are used in different forms, the form of the aqueous solution can be prepared and used separately. However, when preparing an aqueous solution containing a surfactant, from the viewpoint of not increasing the viscosity of the aqueous solution, 0.1 to 30 parts by mass of a surfactant is added to 100 parts by mass of water. It is preferable that it is prepared by adding 1 part by mass to 10 parts by mass.
また、界面活性剤と過酸化水素とを、炭素含有廃棄物に接触させるタイミングについては、特に制限はない。すなわち、例えば、炭素含有廃棄物を焼却のための設備に投入する前であってもよく、投入と同時であってもよく、投入した後であってもよい。加えて、界面活性剤と過酸化水素とを各別の形態で用いる場合にも、それらを炭素含有廃棄物に接触させるタイミングについては、特に制限はない。すなわち、過酸化水素より先に界面活性剤を炭素含有廃棄物に接触させてもよく、同時に接触させてもよく、過酸化水素よりあとに界面活性剤を炭素含有廃棄物に接触させてもよい。ただし、炭素含有廃棄物に十分な濡れ性を付与する観点からは、界面活性剤を過酸化水素より先に炭素含有廃棄物に接触させることが好ましい。 Moreover, there is no restriction | limiting in particular about the timing which makes surfactant and hydrogen peroxide contact carbon-containing waste. That is, for example, it may be before the carbon-containing waste is put into the incineration facility, at the same time as the input, or after the input. In addition, even when the surfactant and hydrogen peroxide are used in different forms, there is no particular limitation on the timing of bringing them into contact with the carbon-containing waste. That is, the surfactant may be brought into contact with the carbon-containing waste prior to hydrogen peroxide, may be brought into contact at the same time, or the surfactant may be brought into contact with the carbon-containing waste after hydrogen peroxide. . However, from the viewpoint of imparting sufficient wettability to the carbon-containing waste, it is preferable to bring the surfactant into contact with the carbon-containing waste prior to hydrogen peroxide.
一方、本発明の他の態様では、炭素含有廃棄物に界面活性剤を接触させて小径化し、これに更に過酸化水素を接触させる。これによれば、その小径化により、燃焼性改善効果がより高められる。また、界面活性剤により、炭素含有廃棄物の小径化の際、あるいは炭素含有廃棄物の小径化後の発塵が抑制される。 On the other hand, in another embodiment of the present invention, a surfactant is brought into contact with the carbon-containing waste to reduce the diameter, and hydrogen peroxide is further brought into contact therewith. According to this, the combustibility improvement effect is further enhanced by the small diameter. Further, the surfactant suppresses the generation of dust when the carbon-containing waste is reduced in diameter or after the carbon-containing waste is reduced in diameter.
上記の形態においても、界面活性剤と過酸化水素とを、炭素含有廃棄物に接触させるタイミングについては、特に制限はない。すなわち、例えば、炭素含有廃棄物を焼却のための設備に投入する前であってもよく、投入と同時であってもよく、投入した後であってもよい。より具体的には、例えば、小径化した炭素含有廃棄物に界面活性剤及び過酸化水素を滴下した後、又は、界面活性剤及び過酸化水素を含む溶液に小径化した炭素含有廃棄物を含浸した後、又は、界面活性剤を滴下して小径化した炭素含有廃棄物に過酸化水素を滴下した後、又は、界面活性剤を滴下して小径化した炭素含有廃棄物を過酸化水素に含浸した後、焼却設備にそれらを投入する方法であってもよいし、焼却設備に小径化した炭素含有廃棄物を投入する際に、もしくは投入した後に、焼却設備の内部に界面活性剤及び過酸化水素を噴霧して、焼却設備の内部でそれらを接触させる、又は、界面活性剤を滴下して小径化した炭素含有廃棄物を焼却設備に投入した後、焼却設備の内部に過酸化水素を噴霧して、焼却設備の内部でそれらを接触させる方法などであってもよい。 Also in the above embodiment, there is no particular limitation on the timing of bringing the surfactant and hydrogen peroxide into contact with the carbon-containing waste. That is, for example, it may be before the carbon-containing waste is put into the incineration facility, at the same time as the input, or after the input. More specifically, for example, after adding a surfactant and hydrogen peroxide dropwise to a carbon-containing waste having a reduced diameter, or impregnating a carbon-containing waste having a reduced diameter in a solution containing the surfactant and hydrogen peroxide. Or after adding hydrogen peroxide to carbon-containing waste that has been reduced in diameter by adding a surfactant, or impregnating hydrogen-containing waste that has been reduced in diameter by adding surfactant to hydrogen peroxide. Then, it may be a method of introducing them into the incineration facility, or when introducing the carbon-containing waste having a reduced diameter into the incineration facility, or after the introduction, the surfactant and the peroxide inside the incineration facility. After spraying hydrogen and bringing them into contact with the inside of the incineration facility, or introducing a carbon-containing waste reduced in diameter by adding a surfactant to the incineration facility, spraying hydrogen peroxide inside the incineration facility Connect them inside the incinerator. It may be a method of.
以下、本発明の炭素含有廃棄物処理方法について、処理対象物を廃ＣＦＲＰ又は廃タイヤとし、その処理対象物をセメントキルンでサーマルリサイクル又はケミカルリサイクルするために、本発明の処理を行う場合を例として、更に詳細に説明する。 Hereinafter, with respect to the carbon-containing waste treatment method of the present invention, the treatment object is waste CFRP or waste tire, and the treatment object of the present invention is subjected to thermal recycling or chemical recycling with a cement kiln as an example. Will be described in more detail.
まず、処理対象物である廃ＣＦＲＰについて説明する。炭素繊維強化プラスチック（ＣＦＲＰ：Carbon Fiber reinforced plastics）は、軽量でありながら機械的特性や耐蝕性に非常に優れた構造材料である。炭素繊維の含有率は、一般的に、３０質量％〜８０質量％程度とされている。なお、ＣＦＲＰの炭素繊維の含有率は、ＪＩＳ Ｋ ７０７５「炭素繊維強化プラスチックの繊維含有率及び空洞率試験方法」に準拠した試験方法で求めることができる。 First, the waste CFRP that is a processing target will be described. Carbon fiber reinforced plastics (CFRPs) are structural materials that are extremely lightweight but have excellent mechanical properties and corrosion resistance. The carbon fiber content is generally about 30% to 80% by mass. The carbon fiber content of CFRP can be determined by a test method based on JIS K 7075 “Test method for fiber content and void ratio of carbon fiber reinforced plastic”.
ＣＦＲＰで用いられる炭素繊維としては、グラファイト状の炭素から形成され、剛性等の機械的特性に優れた繊維が用いられている。具体的には、炭素繊維としては、例えば、ポリアクリロニトリル系、ピッチ系又はセルロース系繊維等を酸化性雰囲気中で１５０℃〜４００℃に加熱して耐炎化処理を行なった後、不活性雰囲気中で３００℃〜２５００℃で炭化又は黒鉛化処理をして得られたものの他、水蒸気等の半活性雰囲気で賦活化した活性炭素繊維等が挙げられる。 As the carbon fiber used in CFRP, a fiber formed from graphite-like carbon and having excellent mechanical properties such as rigidity is used. Specifically, as the carbon fiber, for example, a polyacrylonitrile-based, pitch-based, or cellulose-based fiber is heated to 150 ° C. to 400 ° C. in an oxidizing atmosphere to perform a flame resistance treatment, and then in an inert atmosphere. In addition to those obtained by carbonization or graphitization at 300 ° C. to 2500 ° C., activated carbon fibers activated in a semi-active atmosphere such as water vapor are listed.
ＣＦＲＰで用いられるマトリックス材料としては、熱可塑性樹脂又は熱硬化性樹脂が用いられている。具体的には、熱可塑性樹脂としては、例えば、ポリアミド樹脂、またはポリプロピレン樹脂、ナイロン樹脂等が挙げられる。また、熱硬化性樹脂としては、例えば、エポキシ樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、ビスマレイミド樹脂、フェノール樹脂等が挙げられる。 As a matrix material used in CFRP, a thermoplastic resin or a thermosetting resin is used. Specifically, examples of the thermoplastic resin include polyamide resin, polypropylene resin, nylon resin, and the like. Moreover, as a thermosetting resin, an epoxy resin, unsaturated polyester resin, a polyimide resin, a bismaleimide resin, a phenol resin etc. are mentioned, for example.
次に、廃タイヤについて説明する。タイヤの材料構成は、トラック用等の大型タイヤは天然ゴム（ｃｉｓ１，４−ポリイソプレン）、乗用車用等の小型タイヤは合成ゴム（ＳＢＲ、スチレン−ブタジエンランダム共重合体）と大まかに主原料が異なるが、ゴムが４０質量％〜６０質量％、カーボンブラックや硫黄等の配合剤が２０質量％〜４０質量％、スチール及びテキスタイルから成るタイヤコードが１０質量％〜２０質量％、ビードワイヤーが３質量％〜１０質量％とされる。 Next, the waste tire will be described. The main material of the tire is the natural rubber (cis1,4-polyisoprene) for large tires for trucks, and synthetic rubber (SBR, styrene-butadiene random copolymer) for small tires for passenger cars. Although different, rubber is 40 mass% to 60 mass%, carbon black, sulfur and other compounding agents are 20 mass% to 40 mass%, steel and textile tire cords are 10 mass% to 20 mass%, and bead wires are 3 mass%. It is set as 10 mass%-10 mass%.
本実施形態においては、まず、上記のような構成成分からなる廃ＣＦＲＰ又は廃タイヤを、回転型カッター式剪断粗砕機等の粉砕設備で５０ｍｍ以下に粗砕した後、ジョークラッシャ、ロールミル、ローラーミル、破砕機等の粉砕設備によって所定の大きさに小径化する。なお、廃タイヤ等の燃焼性の良好な成分を比較的多く含む廃棄物については、５０ｍｍ以下に粗砕した段階で粉砕を終了してもよい。また、廃ＣＦＲＰ等の比較的硬い廃棄物の粉砕作業を効率的に行うためには、後段の粉砕設備にはセパレーター等の分級装置を付設すると好ましい。 In the present embodiment, first, waste CFRP or waste tire composed of the above components is crushed to 50 mm or less with a pulverization facility such as a rotary cutter type shear crusher, and then a jaw crusher, roll mill, roller mill The diameter is reduced to a predetermined size by crushing equipment such as a crusher. In addition, about the waste which contains comparatively many combustible components, such as a waste tire, you may complete | finish grinding | pulverization in the stage coarsely crushed to 50 mm or less. Further, in order to efficiently perform the pulverization work of relatively hard waste such as waste CFRP, it is preferable to attach a classification device such as a separator to the subsequent pulverization equipment.
ここで、小径化処理後の廃ＣＦＲＰ又は廃タイヤの平均粒子径は、小径化処理後に乾燥させたそれらをＪＩＳ Ｚ ８８０１「試験用ふるい−第１部：金属製網ふるい」に規定された篩を使用してふるい分けし、その篩上に残分した試料の５０質量％に相当する径を算出することにより求めることができる。 Here, the average particle diameter of the waste CFRP or the waste tire after the diameter reduction treatment is the sieve defined in JIS Z 8801 “Sieving for testing—Part 1: Metal mesh sieve” after drying the diameter reduction treatment. Can be obtained by calculating the diameter corresponding to 50% by mass of the sample remaining on the sieve.
なお、本発明の処理方法においては、過度に労力のかかる小径化は必ずしも、必要ではないが、効率的に処理を行うためには、廃ＣＦＲＰ又は廃タイヤをある程度小径化することが好ましい。具体的には、廃ＣＦＲＰの場合１０ｍｍ以下、好ましくは７ｍｍ以下とするとよい。廃タイヤの場合、５０ｍｍ以下、好ましくは３０ｍｍ以下とするとよい。 In the treatment method of the present invention, it is not always necessary to reduce the diameter, which is excessively labor intensive. However, in order to perform the treatment efficiently, it is preferable to reduce the diameter of the waste CFRP or the waste tire to some extent. Specifically, in the case of waste CFRP, it is 10 mm or less, preferably 7 mm or less. In the case of a waste tire, it is 50 mm or less, preferably 30 mm or less.
次に、小径化した廃ＣＦＲＰ又は廃タイヤと界面活性剤及び過酸化水素とを接触させる。この接触の方法としては、上述したように、廃ＣＦＲＰ又は廃タイヤの周囲で過酸化水素の熱分解が生じる環境がセメントキルンの内部で構成される方法等であればよい。さらに、廃ＣＦＲＰ又は廃タイヤの小径化において、界面活性剤を滴下した廃ＣＦＲＰ又は廃タイヤを小径化して、界面活性剤を含む廃ＣＦＲＰ又は廃タイヤを得た後、この界面活性剤を含む廃ＣＦＲＰ又は廃タイヤと過酸化水素を接触させる方法でもよい。 Next, waste CFRP or waste tire having a reduced diameter is brought into contact with a surfactant and hydrogen peroxide. As the contact method, as described above, an environment in which the thermal decomposition of hydrogen peroxide around the waste CFRP or the waste tire is configured inside the cement kiln may be used. Further, in reducing the diameter of the waste CFRP or the waste tire, the waste CFRP or the waste tire to which the surfactant is dropped is reduced in diameter to obtain the waste CFRP or the waste tire containing the surfactant, and then the waste containing the surfactant. A method of contacting CFRP or waste tire with hydrogen peroxide may also be used.
具体的には、例えば、小径化した廃ＣＦＲＰ又は廃タイヤに界面活性剤及び過酸化水素を滴下した後、又は、界面活性剤及び過酸化水素に小径化した廃ＣＦＲＰ又は廃タイヤを含浸した後、又は、界面活性剤を滴下して小径化した廃ＣＦＲＰ又は廃タイヤに過酸化水素を滴下した後、又は、界面活性剤を滴下して小径化した廃ＣＦＲＰ又は廃タイヤを過酸化水素に含浸した後、セメントキルンにそれらを投入する方法であってもよいし、セメントキルンに小径化したＣＦＲＰ又は廃タイヤを投入した後、セメントキルンの内部に界面活性剤及び過酸化水素を噴霧して、セメントキルンの内部でそれらを接触させる、又は、界面活性剤を滴下して小径化した廃ＣＦＲＰ又は小径化したタイヤを焼却設備に投入した後、焼却設備の内部に過酸化水素を噴霧して、焼却設備の内部でそれらを接触させる方法であってもよい。セメントキルンへの廃ＣＦＲＰ又は廃タイヤの投入箇所は、特に限定されるものではなく、窯前側（キルンバーナー側）からでも、窯尻側からでも、仮焼炉からのいずれであってもよい。 Specifically, for example, after a surfactant and hydrogen peroxide are dropped onto waste CFRP or waste tire having a reduced diameter, or after impregnating waste CFRP or waste tire having a reduced diameter on a surfactant and hydrogen peroxide. Or after adding hydrogen peroxide to the waste CFRP or waste tire that has been reduced in diameter by adding a surfactant, or impregnating the waste CFRP or waste tire that has been reduced in diameter by adding a surfactant to hydrogen peroxide. Then, it may be a method of throwing them into the cement kiln, or after introducing CFRP or waste tires with a reduced diameter into the cement kiln, spraying a surfactant and hydrogen peroxide inside the cement kiln, After contacting the waste inside the cement kiln or dropping the surfactant to drop the diameter of the waste CFRP or the reduced diameter tire into the incineration facility, the peroxide water is put inside the incineration facility. By spraying, or a method of contacting them within the incinerator. The place where the waste CFRP or the waste tire is charged into the cement kiln is not particularly limited, and may be from the front side of the kiln (kiln burner side), from the kiln bottom side, or from the calcining furnace.
ただし、過酸化水素の沸点が１４１℃（純度９０％）であり、過酸化水素はセメントキルンに投入すると直ちに熱分解するので、過酸化水素による燃焼性改善効果を効率的に利用するためには、セメントキルンの内部で接触させる方法を用いる場合には、廃ＣＦＲＰ又は廃タイヤと、界面活性剤及び過酸化水素とを、共通のもしくはごく近傍の箇所から、同時にもしくは実質的に同時にセメントキルンへ投入することが好ましい。 However, since the boiling point of hydrogen peroxide is 141 ° C. (purity 90%) and hydrogen peroxide is thermally decomposed immediately when it is put into a cement kiln, in order to efficiently use the effect of improving the combustibility by hydrogen peroxide. When using the method of contacting inside the cement kiln, the waste CFRP or waste tire, the surfactant and hydrogen peroxide are simultaneously or substantially simultaneously sent from a common or very close location to the cement kiln. It is preferable to input.
具体的には、例えば、キルンバーナー等に廃ＣＦＲＰ又は廃タイヤの第１の吹込み用ポートを設置するとともに、その第１の吹込み用ポートに隣り合うように界面活性剤及び過酸化水素、または過酸化水素のみの第２の吹込み用ポートを設置するようにすればよい。 Specifically, for example, the first blowing port of waste CFRP or waste tire is installed in a kiln burner or the like, and a surfactant and hydrogen peroxide are adjacent to the first blowing port. Alternatively, a second blowing port made of only hydrogen peroxide may be installed.
最後に、廃ＣＦＲＰ又は廃タイヤを、これに接触させた界面活性剤及び過酸化水素と共に、セメントキルンの内部で加熱する。加熱温度は、固定炭素の燃焼温度域（５００℃〜８００℃）を超える温度にすることが好ましい。ここで、固定炭素とは、炭素含有廃棄物中に揮発しない形態で存在する炭素化合物のことをいい、廃ＣＦＲＰに含まれる炭素繊維などが含まれる。 Finally, the waste CFRP or waste tire is heated inside the cement kiln with the surfactant and hydrogen peroxide in contact therewith. The heating temperature is preferably set to a temperature exceeding the combustion temperature range of fixed carbon (500 ° C. to 800 ° C.). Here, fixed carbon refers to a carbon compound that exists in a form that does not volatilize in the carbon-containing waste, and includes carbon fibers contained in the waste CFRP.
以上説明したように、本発明の処理方法では、界面活性剤によって炭素含有廃棄物の濡れ性が改善するので、過酸化水素（Ｈ２Ｏ２）が炭素含有廃棄物（すなわち、それに含まれる炭素化合物）に十分に接触する。そして、焼却時には、その過酸化水素に含まれる酸素と炭素含有廃棄物に含まれる炭素化合物とが効率よく反応するので、炭素化合物のサイズ（すなわち、廃ＣＦＲＰ又は廃タイヤの平均粒子径）を極めて小さくしなくても、炭素化合物を十分に燃焼させることができる。 As described above, in the treatment method of the present invention, the wettability of the carbon-containing waste is improved by the surfactant, so that hydrogen peroxide (H 2 O 2 ) is contained in the carbon-containing waste (that is, the carbon contained therein). Compound). At the time of incineration, the oxygen contained in the hydrogen peroxide and the carbon compound contained in the carbon-containing waste efficiently react, so that the size of the carbon compound (that is, the average particle size of the waste CFRP or the waste tire) Even if it is not reduced, the carbon compound can be burned sufficiently.
したがって、本発明の処理方法によれば、事前に炭素化合物の除去を行う必要もなく、また、廃ＣＦＲＰの平均粒子径を３ｍｍ以下の極めて小さいサイズにしなくてもよいので、少ない労力で廃ＣＦＲＰに含まれる炭素化合物を十分に燃焼させることができる。同様に、廃タイヤでは、１０ｍｍ以下の極めて小さいサイズにしなくても、短時間で十分に燃焼させることができる。 Therefore, according to the treatment method of the present invention, it is not necessary to remove the carbon compound in advance, and the waste CFRP does not have to have an average particle size of 3 mm or less, so the waste CFRP can be made with less labor. The carbon compound contained in can be sufficiently burned. Similarly, waste tires can be burned sufficiently in a short time without having to be very small in size of 10 mm or less.
なお、本実施形態においては、炭素含有廃棄物の焼却設備としてセメント製造設備であるセメントキルンの例を説明したが、本発明の処理方法においては、セメントキルン以外の焼却設備を用いてもよい。 In the present embodiment, an example of a cement kiln that is a cement manufacturing facility has been described as an incineration facility for carbon-containing waste. However, in the treatment method of the present invention, an incineration facility other than a cement kiln may be used.
また、処理対象物の１つとして、廃ＣＦＲＰの例を説明したが、これは、本発明に係る方法が、炭素化合物が炭素繊維であるものに対して、特に高い燃焼促進効果を得ることができるものであるためである。しかし、本発明に係る方法の処理対象物は、炭素化合物として炭素繊維を含む廃棄物に限定されるものではなく、炭素繊維以外の炭素化合物を含むものであってもよい。 Moreover, although the example of waste CFRP was demonstrated as one of the process target objects, this is that the method according to the present invention can obtain a particularly high combustion promotion effect for the carbon compound being carbon fiber. This is because it is possible. However, the object to be treated by the method according to the present invention is not limited to a waste containing carbon fiber as a carbon compound, and may contain a carbon compound other than carbon fiber.
次に、本発明の処理方法に係る試験結果（すなわち、本発明の処理方法の実施例）について説明する。 Next, test results (that is, examples of the processing method of the present invention) related to the processing method of the present invention will be described.
［試験例１］
まず、炭素含有廃棄物の大きさを一定とし、界面活性剤及び過酸化水素の量を変化させて試験を行うことにより、界面活性剤及び過酸化水素の量による影響を評価した。以下、この試験を「燃焼性評価試験」という。
[Test Example 1]
First, the effect of the amount of the surfactant and the hydrogen peroxide was evaluated by performing the test while changing the amount of the surfactant and the hydrogen peroxide while keeping the size of the carbon-containing waste constant. Hereinafter, this test is referred to as “flammability evaluation test”.
具体的には、以下に示すようにして各試験水準を設定した。 Specifically, each test level was set as follows.
《試験１》
炭素含有廃棄物：廃ＣＦＲＰ（炭素繊維含有率：５８質量％）
廃ＣＦＲＰの試料サイズ：平均粒子径１ｍｍ
過酸化水素：和光純薬工業製試薬特級（純度３０％）
界面活性剤：直鎖アルキルベンゼンスルホン酸ナトリウム、直鎖アルキルベンゼンスルホン酸、及びアルキルエーテル硫酸エステルナトリウム混合物（ライオン株式会社製：ママレモン（商品名））
界面活性剤及び過酸化水素の使用方法：界面活性剤及び過酸化水素が気化した雰囲気下に炭素含有廃棄物を曝露した条件を想定し、廃ＣＦＲＰを事前に過酸化水素に含侵させることなく、該廃ＣＦＲＰの周囲に界面活性剤を添加した過酸化水素を滴下して、同時に加熱した。過酸化水素への界面活性剤の添加量は、表１のとおりとした。
<< Test 1 >>
Carbon-containing waste: Waste CFRP (carbon fiber content: 58% by mass)
Sample size of waste CFRP: average particle diameter 1mm
Hydrogen peroxide: Wako Pure Chemical Industries special reagent grade (30% purity)
Surfactant: Sodium linear alkylbenzene sulfonate, linear alkylbenzene sulfonic acid, and sodium alkyl ether sulfate ester (Lion Corporation: Mama Lemon (trade name))
Method of using surfactant and hydrogen peroxide: Assuming the condition where carbon-containing waste is exposed in an atmosphere where surfactant and hydrogen peroxide are vaporized, waste CFRP is not impregnated with hydrogen peroxide in advance. Then, hydrogen peroxide added with a surfactant was dropped around the waste CFRP and heated at the same time. The amount of surfactant added to hydrogen peroxide was as shown in Table 1.
《試験２》
炭素含有廃棄物：廃タイヤ
廃タイヤの試料サイズ：３×３×３ｍｍ
過酸化水素：試験１と同じ
界面活性剤：試験１と同じ
界面活性剤及び過酸化水素の使用方法：過酸化水素が気化した雰囲気下に界面活性剤が塗布された炭素含有廃棄物を曝露した条件を想定し、界面活性剤を廃タイヤに滴下し、混合することによって、その表面に界面活性剤を塗布した該廃タイヤを、事前に過酸化水素に含侵させることなく、その周囲に過酸化水素を滴下して、同時に加熱した。廃タイヤへの界面活性剤の塗布量は、廃タイヤ１００質量部に対し、１質量部とした。
<< Test 2 >>
Carbon-containing waste: Waste tire Sample size of waste tire: 3 x 3 x 3 mm
Hydrogen peroxide: Same as Test 1 Surfactant: Same as Test 1 Usage of surfactant and hydrogen peroxide: Exposed carbon-containing waste with surfactant applied in an atmosphere where hydrogen peroxide was vaporized Assuming the conditions, the surfactant is dropped onto the waste tire and mixed, so that the waste tire coated with the surfactant on its surface is not allowed to be impregnated with hydrogen peroxide in advance. Hydrogen oxide was added dropwise and heated simultaneously. The amount of the surfactant applied to the waste tire was 1 part by mass with respect to 100 parts by mass of the waste tire.
試験１、試験２共に、上記試料を昇温速度１０℃／分で加熱し、１５０〜１０００℃の温度域で、重量減少率を測定した。重量減少率の測定は、熱重量・示差熱測定装置（ネッチ・ジャパン株式会社製：ＴＧ−ＤＴＡ ２０２０ＳＲ（商品名））を用いて行い、室温での重量に対する重量減少率（質量％）、及び、固定炭素（揮発しない形態の炭素：ＣＦＲＰではほとんどが炭素繊維）の重量（熱重量曲線において、５００℃〜６００℃に生じる緩勾配の始点の重量と、８００℃付近の重量減少が生じなくなった地点での重量との差分）において、かかる固定炭素の重量を１００％とした場合の重量減少率（質量％）を算出した。前者（室温重量に対する重量減少率）はＣＦＲＰ又は廃タイヤの全燃焼率に相当し、後者（固定炭素の重量に対する重量減少率）は廃ＣＦＲＰ中又は廃タイヤ中の固定炭素の燃焼率に相当する。 In both Test 1 and Test 2, the sample was heated at a heating rate of 10 ° C./min, and the weight loss rate was measured in a temperature range of 150 to 1000 ° C. The weight reduction rate is measured using a thermogravimetric / differential heat measuring device (manufactured by Netch Japan KK: TG-DTA 2020SR (trade name)), and the weight reduction rate (% by mass) relative to the weight at room temperature, and The weight of fixed carbon (carbon in non-volatile form: mostly carbon fiber in CFRP) (the thermogravimetric curve shows that the weight of the starting point of the gentle gradient that occurs between 500 ° C. and 600 ° C. and the weight reduction near 800 ° C. no longer occur. The difference in weight with respect to the weight at the point) was calculated as a weight reduction rate (mass%) when the weight of the fixed carbon was 100%. The former (weight reduction rate with respect to room temperature weight) corresponds to the total combustion rate of CFRP or waste tire, and the latter (weight reduction rate with respect to the weight of fixed carbon) corresponds to the combustion rate of fixed carbon in waste CFRP or waste tire. .
燃焼性評価試験の試験結果を、廃ＣＦＲＰについては表１に示し、廃タイヤについては表２に示す。 The test results of the flammability evaluation test are shown in Table 1 for waste CFRP and in Table 2 for waste tires.
表１に示すように、７００℃まで加熱した段階で、過酸化水素及び界面活性剤を接触させた廃ＣＦＲＰ（実施例１〜実施例５）は、ほぼ燃え切っていたのに対し、過酸化水素及び界面活性剤を接触させなかった廃ＣＦＲＰ（比較例１）や、界面活性剤を接触させずに過酸化水素のみを接触させた廃ＣＦＲＰ（比較例２）では、その段階でおよそ３割が燃え残っていた。さらに、固定炭素（炭素繊維）の燃焼性を比較すると、過酸化水素及び界面活性剤を使用した実施例１〜実施例５では、７００℃まで加熱した段階で廃ＣＦＲＰの固定炭素（炭素繊維）がほぼ燃えきっていたのに対し、過酸化水素及び界面活性剤を使用しなかった比較例１や、界面活性剤を使用せずに過酸化水素のみを使用した比較例２では、その段階で廃ＣＦＲＰの固定炭素（炭素繊維）のおよそ７割が燃え残っていた。 As shown in Table 1, the waste CFRP (Examples 1 to 5) in which hydrogen peroxide and the surfactant were brought into contact with each other at the stage of heating to 700 ° C. was almost burned out. About 30% of waste CFRP (Comparative Example 1) in which hydrogen and a surfactant were not contacted and waste CFRP (Comparative Example 2) in which only a hydrogen peroxide was contacted without contacting a surfactant. Left unburned. Furthermore, when combustibility of fixed carbon (carbon fiber) is compared, in Examples 1 to 5 using hydrogen peroxide and a surfactant, fixed carbon (carbon fiber) of waste CFRP at the stage of heating to 700 ° C. In Comparative Example 1 in which hydrogen peroxide and a surfactant were not used, and in Comparative Example 2 in which only hydrogen peroxide was used without using a surfactant, Approximately 70% of the fixed carbon (carbon fiber) of the waste CFRP remained unburned.
また、表２に示すように、６００℃まで加熱した段階で、過酸化水素及び界面活性剤を接触させた廃タイヤ（実施例６）は、ほぼ燃え切っていたのに対し、過酸化水素及び界面活性剤を接触させなかった廃タイヤ（比較例３）は、その段階でおよそ２割が燃え残っていた。さらに、固定炭素（炭素繊維）の燃焼性を比較すると、過酸化水素及び界面活性剤を使用した実施例６では、６００℃まで加熱した段階で廃タイヤの固定炭素がほぼ燃え切っていたのに対し、過酸化水素及び界面活性剤を使用しなかった比較例３では、その段階で廃タイヤの固定炭素のおよそ６割が燃え残っていた。 Further, as shown in Table 2, the waste tire (Example 6) in which hydrogen peroxide and the surfactant were brought into contact with each other when heated to 600 ° C. was almost burned out, whereas hydrogen peroxide and About 20% of the waste tire (Comparative Example 3) that was not brought into contact with the surfactant remained unburned at that stage. Furthermore, when comparing the flammability of fixed carbon (carbon fiber), in Example 6 using hydrogen peroxide and a surfactant, the fixed carbon of the waste tire was almost burned out when heated to 600 ° C. On the other hand, in Comparative Example 3 in which hydrogen peroxide and a surfactant were not used, approximately 60% of the fixed carbon of the waste tire remained unburned at that stage.
図１には、実施例３、比較例１及び比較例２の加熱プロセスにおける重量減少曲線を示す。また、図２には、実施例６及び比較例３の加熱プロセスにおける重量減少曲線を示す。ここで、図中の重量減少曲線において重量減少が生じている３つの領域のうち、低温側の２つの領域（３００〜４００℃に対応する領域及び４５０〜５５０℃に対応する領域）が、おもに樹脂等の揮発性炭素の燃焼による重量減少であり、最も高温側の減量域（５５０℃以上も領域）が、おもに炭素繊維等の固定炭素の燃焼による重量減少である。よって、図１及び図２より、本発明の方法（実施例３、実施例６）は、特に固定炭素の燃焼性促進に有効であることがわかる。さらに、図１より、過酸化水素を添加しただけ（比較例２）では、十分な燃焼促進効果を得ることはできないことがわかる。 In FIG. 1, the weight reduction curve in the heating process of Example 3, the comparative example 1, and the comparative example 2 is shown. FIG. 2 shows weight loss curves in the heating processes of Example 6 and Comparative Example 3. Here, of the three regions where weight reduction occurs in the weight reduction curve in the figure, two regions on the low temperature side (regions corresponding to 300 to 400 ° C. and regions corresponding to 450 to 550 ° C.) are mainly It is a weight reduction due to combustion of volatile carbon such as resin, and the weight loss region (region of 550 ° C. or higher) on the highest temperature side is mainly weight reduction due to combustion of fixed carbon such as carbon fiber. Therefore, it can be seen from FIGS. 1 and 2 that the methods of the present invention (Example 3 and Example 6) are particularly effective in promoting the flammability of fixed carbon. Furthermore, it can be seen from FIG. 1 that only by adding hydrogen peroxide (Comparative Example 2), a sufficient combustion promoting effect cannot be obtained.
［試験例２］
次に、炭素含有廃棄物の平均粒子径を変化させ、界面活性剤及び過酸化水素の量を一定として試験を行うことにより、炭素含有廃棄物の平均粒子径による影響を評価した。以下、この試験を「粒子径評価試験」という。
[Test Example 2]
Next, the influence of the average particle size of the carbon-containing waste was evaluated by changing the average particle size of the carbon-containing waste and performing the test with constant amounts of the surfactant and hydrogen peroxide. Hereinafter, this test is referred to as a “particle size evaluation test”.
具体的には、以下の《試験３》に示すようにして各試験水準を設定した。 Specifically, each test level was set as shown in << Test 3 >> below.
《試験３》
炭素含有廃棄物：試験例１と同じ廃ＣＦＲＰ（炭素繊維含有率：５８質量％）
廃ＣＦＲＰの試料サイズ：平均粒子径が１６ｍｍ、９．５ｍｍ、６．７ｍｍ、４．７５ｍｍ、２．８ｍｍの５種類
過酸化水素：試験例１と同じ
界面活性剤：試験例１と同じ
界面活性剤及び過酸化水素の使用方法：各廃ＣＦＲＰに接触させる過酸化水素及び界面活性剤の量は、廃ＣＦＲＰの量を１００質量部としたときに、過酸化水素（純度３０％）の量を１５０質量部、界面活性剤の量を５質量部とした（試験例１の実施例３の試験水準とした。）。
<< Test 3 >>
Carbon-containing waste: Waste CFRP as in Test Example 1 (carbon fiber content: 58% by mass)
Sample size of waste CFRP: 5 types of average particle diameters of 16 mm, 9.5 mm, 6.7 mm, 4.75 mm and 2.8 mm Hydrogen peroxide: Same as Test Example 1 Surfactant: Same as Test Example 1 Surface activity Agent and hydrogen peroxide use method: The amount of hydrogen peroxide and surfactant to be contacted with each waste CFRP is the amount of hydrogen peroxide (purity 30%) when the amount of waste CFRP is 100 parts by mass. 150 parts by mass and the amount of the surfactant were 5 parts by mass (the test level of Example 3 of Test Example 1 was used).
上記廃ＣＦＲＰ及び過酸化水素及び界面活性剤を、以下に述べる加熱用電気炉に入れる直前に同一試料容器に入れ、１４００℃に温度設定された大気雰囲気の電気炉で３分間加熱し、加熱後の廃ＣＦＲＰの未燃炭素繊維の有無を評価した。この加熱条件は、セメントキルンの窯前部に投入して燃焼処理を行った場合を模した条件である。未燃炭素繊維有無の評価は、加熱後の試料について、上記燃焼性評価試験と同様に熱重量減少を測定して、固定炭素（炭素繊維）の燃焼温度域（５００〜８００℃）の重量減少率を求めて、別途、加熱前の試料についても、同様に、固定炭素（炭素繊維）の燃焼温度域（５００〜８００℃）の重量減少率を求め、加熱前から加熱後にわたる燃え残りの割合を未燃炭素繊維含油流率（質量％）として評価した。 The waste CFRP, hydrogen peroxide, and surfactant are placed in the same sample container immediately before being put into the heating electric furnace described below, and heated in an electric furnace in an air atmosphere set at 1400 ° C. for 3 minutes, after heating. The presence or absence of unburned carbon fiber in the waste CFRP was evaluated. This heating condition is a condition that simulates the case where the combustion treatment is performed by putting the cement kiln in the front part of the kiln. For the evaluation of the presence or absence of unburned carbon fiber, the weight reduction in the combustion temperature range (500 to 800 ° C.) of fixed carbon (carbon fiber) is measured for the sample after heating by measuring the thermal weight loss in the same manner as the above-described flammability evaluation test. For the sample before heating, the rate of weight reduction in the combustion temperature range (500 to 800 ° C.) of fixed carbon (carbon fiber) is also obtained separately, and the ratio of unburned residue before heating to after heating Was evaluated as the unburned carbon fiber oil content rate (mass%).
粒子径評価試験の試験結果を、以下の表３に示す。
表３に示すように、平均粒子径が１０ｍｍ以下、好ましくは、７ｍｍ以下であれば、燃焼性改善効果がより大きいことが明らかとなった。 As shown in Table 3, when the average particle diameter is 10 mm or less, preferably 7 mm or less, it is clear that the effect of improving combustibility is greater.
Claims (8)
前記炭素含有廃棄物と、界面活性剤及び過酸化水素とを接触させた後、該炭素含有廃棄物を焼却することを特徴とする炭素含有廃棄物処理方法。 A carbon-containing waste treatment method for incinerating carbon-containing waste,
A method for treating carbon-containing waste, comprising bringing the carbon-containing waste into contact with a surfactant and hydrogen peroxide, and then incinerating the carbon-containing waste.
前記炭素含有廃棄物に界面活性剤を接触させて小径化し、これに更に過酸化水素を接触させた後、該炭素含有廃棄物を焼却することを特徴とする炭素含有廃棄物処理方法。 A carbon-containing waste treatment method for incinerating carbon-containing waste,
A carbon-containing waste treatment method, wherein a surface-active agent is brought into contact with the carbon-containing waste to reduce the diameter, and hydrogen peroxide is further brought into contact therewith, and then the carbon-containing waste is incinerated.
前記過酸化水素の量は、前記炭素含有廃棄物の量を１００質量部としたとき、１５質量部以上、且つ、１００質量部以下であることを特徴とする炭素含有廃棄物処理方法。 In the carbon-containing waste disposal method according to claim 1 or 2,
The amount of the hydrogen peroxide is 15 parts by mass or more and 100 parts by mass or less when the amount of the carbon-containing waste is 100 parts by mass.
前記界面活性剤の量は、前記過酸化水素の量を１００質量部としたとき、０．０１質量部以上、且つ、２５質量部以下であることを特徴とする炭素含有廃棄物処理方法。 In the carbon-containing waste disposal method according to any one of claims 1 to 3,
The amount of the surfactant is 0.01 parts by mass or more and 25 parts by mass or less when the amount of the hydrogen peroxide is 100 parts by mass.
前記炭素含有廃棄物の平均粒子径は、１０ｍｍ以下であることを特徴とする炭素含有廃棄物処理方法。 In the carbon-containing waste disposal method according to any one of claims 1 to 4,
The carbon-containing waste treatment method, wherein an average particle size of the carbon-containing waste is 10 mm or less.
前記炭素含有廃棄物は、廃ＣＦＲＰ、ＢＯＦ、ＡＳＲ、ＲＰＦ、ＲＤＦ、木屑、廃タイヤ、ゴム屑、吸水性ポリマーの廃棄物、都市ゴミ、熱硬化性・熱可塑性樹脂の廃棄物、廃ＦＲＰ、カーボンファイバーの廃棄物、光ファイバーの廃棄物、及び、太陽電池の廃棄物からなる群から選択される一以上の廃棄物であることを特徴とする炭素含有廃棄物処理方法。 In the carbon-containing waste disposal method according to any one of claims 1 to 5,
The carbon-containing waste includes waste CFRP, BOF, ASR, RPF, RDF, wood waste, waste tire, rubber waste, water-absorbing polymer waste, municipal waste, thermosetting / thermoplastic resin waste, waste FRP, A carbon-containing waste treatment method, wherein the waste material is one or more wastes selected from the group consisting of carbon fiber waste, optical fiber waste, and solar cell waste.
前記炭素含有廃棄物は、炭素繊維を含むものであることを特徴とする炭素含有廃棄物処理方法。 In the carbon-containing waste processing method of any one of Claims 1-6,
The carbon-containing waste processing method, wherein the carbon-containing waste contains carbon fibers.
前記炭素含有廃棄物と、界面活性剤及び過酸化水素とを接触させた後、該炭素含有廃棄物をセメント製造設備で焼却することを特徴とする炭素含有廃棄物処理方法。 In the carbon-containing waste disposal method according to any one of claims 1 to 7,
A method for treating carbon-containing waste, comprising bringing the carbon-containing waste into contact with a surfactant and hydrogen peroxide, and then incinerating the carbon-containing waste in a cement production facility.
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