JP5989480B2 - Production method of adsorbent - Google Patents
Production method of adsorbent Download PDFInfo
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- JP5989480B2 JP5989480B2 JP2012207910A JP2012207910A JP5989480B2 JP 5989480 B2 JP5989480 B2 JP 5989480B2 JP 2012207910 A JP2012207910 A JP 2012207910A JP 2012207910 A JP2012207910 A JP 2012207910A JP 5989480 B2 JP5989480 B2 JP 5989480B2
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本発明は、石炭灰の湿式脱炭プロセスによって得られる未燃カーボンから吸着剤を製造する方法に関する。 The present invention relates to how to manufacture the adsorbent from the unburned carbon obtained by the coal ash wet decarbonization process.
従来、石炭焚き火力発電所等で発生した石炭灰は、未燃カーボンの少ない石炭灰をセメントの原料等に利用し、未燃カーボン含有率の高い石炭灰は、有効利用することができず、産業廃棄物として埋め立て処理されていた。 Conventionally, coal ash generated at coal-fired thermal power plants, etc. uses coal ash with low unburned carbon as a raw material for cement, etc., and coal ash with a high unburned carbon content cannot be used effectively. Landfilled as industrial waste.
そこで、特許文献1等に記載のように、石炭灰に水を加えてスラリーとし、スラリーに捕集剤を添加し、スラリー及び捕集剤に剪断力を付与して表面改質を行った後、浮選工程において、気泡に石炭灰の未燃カーボンを付着させて浮上させ、浮選分離された未燃カーボンを燃料として、また、未燃カーボン分を1重量%以下とした石炭灰(製品)をセメント用混合材、軽量骨材製造用原料として利用している。
Therefore, as described in
しかし、上記従来の石炭灰の湿式脱炭プロセスで回収される未燃カーボンは、燃料として再利用することはできるが、燃料としての再利用だけでは処理量に制限を受けるため、その他の用途の開発が求められていた。 However, unburned carbon recovered by the above-mentioned conventional coal ash wet decarburization process can be reused as a fuel, but the amount of treatment is limited only by the reuse as a fuel. Development was required.
そこで、本発明は、上記の点に鑑みてなされたものであって、石炭灰の湿式脱炭プロセスによって得られる未燃カーボンの用途を拡大することを目的とする。 Then, this invention is made | formed in view of said point, Comprising: It aims at expanding the use of the unburned carbon obtained by the wet decarburization process of coal ash .
上記目的を達成するため、本発明は、吸着剤の製造方法であって、石炭灰から浮選により未燃カーボンを分離する際に用いられた捕集剤が表面に付着した未燃カーボンを溶媒で洗浄し、該捕集剤を除去した未燃カーボンを得ることを特徴とする。これにより、未燃カーボンの表面に付着した軽油等の捕集剤を取り除いて吸着剤を得ることができる。この吸着剤は、疎水性を有する多孔質の炭素質の粒子である疎水性固体状未燃カーボンを含むため、親油性のダイオキシン類やPCB等の有機塩素化合物を捕捉することができ、燃焼排ガス等に添加してこれらの濃度を低減又は制御することなどが可能となる。 In order to achieve the above object, the present invention is a method for producing an adsorbent, which is a solvent for removing unburned carbon attached to the surface with a scavenger used for separating unburned carbon from coal ash by flotation. To obtain unburned carbon from which the scavenger has been removed. Thereby, collection agents, such as light oil adhering to the surface of unburned carbon, can be removed and an adsorbent can be obtained. Since this adsorbent contains hydrophobic solid unburnt carbon, which is porous carbonaceous particles having hydrophobicity, it can capture lipophilic dioxins, organochlorine compounds such as PCB, and combustion exhaust gas. It is possible to reduce or control these concentrations by adding them.
以上のように、本発明によれば、石炭灰の湿式脱炭プロセスによって回収された未燃カーボンから吸着剤を製造し、未燃カーボンの用途の拡大を図ることができる。 As described above, according to the present invention, it is possible to produce an adsorbent from unburned carbon recovered by a wet decarburization process of coal ash and to expand the use of unburned carbon.
次に、本発明を実施するための形態について図面を参照しながら詳細に説明する。 Next, embodiments for carrying out the present invention will be described in detail with reference to the drawings.
上記特許文献1等に記載されている石炭灰の湿式脱炭プロセスにおいては、石炭灰から浮選により未燃カーボンを分離する際に軽油、灯油、重油等の捕集剤を用いる。そのため、未燃カーボンの表面に捕集剤が付着し、未燃カーボンの細孔(特にミクロ孔)が覆われている。表1及び図2の比較例1は、このような湿式脱炭プロセスから回収された未燃カーボンを示し、口径2nm未満のミクロ孔の容積は、0.0000mL/gであり、比表面積も19.7m2/gと小さく、このままでは吸着剤として使用することはできない。尚、比表面積及びメソ孔の細孔容積の測定は、島津マイクロメリティクスASP-2400(株式会社島津製作所製)を使用して行った。
In wet decarbonization process coal ash which is described in
そこで、図1のステップS1において、上記湿式脱炭プロセスから回収された未燃カーボンを受け入れた後、ステップS2において、受け入れた未燃カーボンをトルエン、ベンゼン、ヘキサン等の溶媒で洗浄する。尚、これら以外にも、捕集剤としての軽油等を溶媒処理することができるものであれば、他の溶媒を使用することもできる。 Therefore, after receiving unburned carbon recovered from the wet decarburization process in step S1 of FIG. 1, the received unburned carbon is washed with a solvent such as toluene, benzene, hexane, etc. in step S2. In addition to these, other solvents can be used as long as they can process light oil or the like as a collecting agent with a solvent.
上記溶媒処理により、未燃カーボンの表面の軽油等の捕集剤が除去され、細孔が復活し、比表面積の大きい疎水性固体状未燃カーボンが得られる。表1及び図2の実施例は、このようにして得られた洗浄品を示し、ミクロ孔の容積は、0.0045mL/gであり、メソ孔及びマクロ孔の容積も比較例1に比較して増加している。また、比表面積も57.5m2/gと比較例1に比較して大幅に増加し、吸着剤として好適に使用することができる。 By the solvent treatment, a scavenger such as light oil on the surface of the unburned carbon is removed, the pores are restored, and a hydrophobic solid unburned carbon having a large specific surface area is obtained. The examples in Table 1 and FIG. 2 show the cleaned product thus obtained, the micropore volume is 0.0045 mL / g, and the mesopore and macropore volumes are also compared to Comparative Example 1. Has increased. Further, the specific surface area is 57.5 m 2 / g, which is significantly increased as compared with Comparative Example 1, and can be suitably used as an adsorbent.
比較例2、3は、別途未燃カーボンを含有する原料を非極性有機溶媒と水とを用いて液液抽出して得られた吸着剤であるが、これらと比較しても実施例の洗浄品は、吸着剤の品質として遜色ないことが判る。尚、比較例2、3は、各々未燃カーボンを含有する原料の由来が異なるため、性状が異なっている。 Comparative Examples 2 and 3 are adsorbents obtained by liquid-liquid extraction of a raw material containing unburnt carbon separately using a nonpolar organic solvent and water. It can be seen that the product is comparable to the quality of the adsorbent. Comparative Examples 2 and 3 have different properties because the origins of raw materials containing unburned carbon are different.
次に、図1のステップS3において、未燃カーボンの洗浄処理を行った後の、軽油等の捕集剤を含む溶媒を、沸点の差(例えば、軽油:約180〜300℃、トルエン:約110℃)によって分離し、分離した軽油等を、石炭灰から未燃カーボンを浮選を介して除去する際に使用する捕集剤として再利用し、分離したトルエン等を溶媒として再利用することができる。 Next, in step S3 of FIG. 1, the solvent containing a scavenger such as light oil after the unburned carbon cleaning process is performed using a difference in boiling points (for example, light oil: about 180 to 300 ° C., toluene: about 110 ° C), and the separated light oil, etc. is reused as a scavenger for removing unburned carbon from coal ash via flotation, and the separated toluene is reused as a solvent. Can do.
以上のように、本発明によれば、石炭灰の湿式脱炭プロセスで回収される未燃カーボンを燃料として再利用するだけでなく、この未燃カーボンを溶媒洗浄して吸着剤としても再利用可能とすることができ、未燃カーボンの用途の拡大を図ることができる。 As described above, according to the present invention, not only the unburned carbon recovered in the wet decarburization process of coal ash is reused as fuel, but also the unburned carbon is washed as a solvent and reused as an adsorbent. It is possible to expand the application of unburned carbon.
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