JP2006104002A - Activated carbon and its manufacturing method - Google Patents
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本発明は、活性炭及びその製造方法に関する。さらに詳細には、糖液などの溶液から色素成分を効率的に除去するのに適した活性炭及びその製造方法に関する。 The present invention relates to activated carbon and a method for producing the same. More specifically, the present invention relates to activated carbon suitable for efficiently removing a pigment component from a solution such as a sugar solution and a method for producing the same.
活性炭は、各種物質の吸着に優れた能力を有し、従来より家庭用、工業用を問わず多くの分野で吸着剤として使用されている。活性炭にはこのように優れた吸着能力があるが、その吸着能力は、活性炭の比表面積、細孔容積、細孔分布などの特性が、その吸着対象物質や、処理の対象となる液体の特性と適合しているかどうかに大きく左右される。 Activated carbon has an excellent ability to adsorb various substances and has been conventionally used as an adsorbent in many fields regardless of household use or industrial use. Activated carbon has such an excellent adsorption capacity, but the adsorption capacity depends on the specific surface area, pore volume, pore distribution, etc. of the activated carbon, and the characteristics of the substance to be adsorbed and the liquid to be treated. It greatly depends on whether or not it fits.
これまで、上記したような活性炭の特性を調整する方法が種々提案されており、例えば、比較的大分子量の化合物を除去するにはトランジショナル域（直径５０〜１００ｎｍ）の細孔容積を増大させた活性炭が適すること、及びかかる活性炭は炭素質材料に特定量の金属化合物を添加した後賦活することによって得られることが開示されている（特許文献１）。
一方、金属化合物を用いて活性炭を製造することも良く知られており、例えば、水酸化カリウムおよび／または水酸化ナトリウムまたはその塩で亜炭を処理してヘキサン作業能力を向上させる活性炭の製造方法が知られている（特許文献２）。
特許文献１にはトランジショナル域の細孔容積を増大させると脱色能力が向上することが記載されているが、トランジショナル域の細孔容積を増大させても脱色能力が向上しないことがあり、単にトランジショナル域の細孔容積を増大させるのみでは必ずしも脱色能力を向上させることができるとはいえない。また、脱色能力を向上させるべくトランジショナル域の細孔容積を増大させると、必然的に硬度が低下するため、高い脱色能力と高い硬度を両立させることは極めて困難である。 Patent Document 1 describes that increasing the pore volume in the transitional region improves the decolorization ability, but increasing the pore volume in the transitional region may not improve the decolorization ability. Simply increasing the pore volume in the transitional region does not necessarily improve the decolorization ability. Further, if the pore volume in the transitional region is increased in order to improve the decolorization capability, the hardness is inevitably lowered, so it is extremely difficult to achieve both high decolorization capability and high hardness.
また、特許文献２には、アルカリ金属及び／又はアルカリ土類金属を炭素質材料に添着した後賦活することによって活性炭を製造し、さらにアルカリ金属及び／又はアルカリ土類金属を添着することで活性炭の特性を調整することが記載されているが、どのような条件を取ることで糖液などの脱色に有用な特定構造の活性炭を製造できるかは記載されていない。しかも、これらの方法にしたがって、脱色能力を上げるために総細孔容積を増加させると、硬度が著しく低下し、充填時及び使用時に活性炭が破損するという問題に加え、再生ロスが多いという問題があった。 Patent Document 2 discloses that activated carbon is produced by adding an alkali metal and / or alkaline earth metal to a carbonaceous material and then activating, and further adding activated metal by adding an alkali metal and / or alkaline earth metal. However, it does not describe what conditions can be used to produce activated carbon having a specific structure useful for decolorization of sugar solutions and the like. In addition, when the total pore volume is increased in order to increase the decolorization ability according to these methods, the hardness is remarkably lowered, and the activated carbon is damaged at the time of filling and use, and there is a problem that the regeneration loss is large. there were.
従って、本発明の目的は、高い脱色性能を有し、かつ強度の高い活性炭及びその工業的に有利な製造方法を提供することにある。 Accordingly, an object of the present invention is to provide an activated carbon having high decolorization performance and high strength and an industrially advantageous production method thereof.
本発明者らは、上記目的を達成するため、活性炭の細孔構造と脱色性能との関係について詳細に検討した結果、従来吸着性能に大きな影響はないとされていた比較的直径の大きな細孔が意外にも脱色性能に有効であることを見出し、好ましくは活性炭原料である炭素質材料として、２種類の石炭を用いることで、上記活性炭を効率よく製造できることを見出し、本発明を完成するに至った。 In order to achieve the above object, the present inventors have studied in detail the relationship between the pore structure of the activated carbon and the decolorization performance. As a result, the pores having a relatively large diameter that have not been significantly affected by the conventional adsorption performance. Is surprisingly effective for decolorization performance, and preferably finds that the activated carbon can be efficiently produced by using two types of coal as the carbonaceous material that is a raw material for the activated carbon, to complete the present invention. It came.
すなわち、本発明は、細孔直径２００〜１０００ｎｍの領域における活性炭充填容積あたりの細孔容積が０．０６０ｃｍ３／ｃｍ３以上で、硬度が９４．０％以上の活性炭である。 That is, the present invention is the pore volume per activated carbon filling volume in the region of pore diameters 200~1000nm is 0.060cm 3 / cm 3 or more, a hardness of activated carbon than 94.0%.
本発明のもう一つの発明は、少なくとも、弱粘結性以上を有する炭素質材料と、アルカリ金属及び／又はアルカリ土類金属を含有する炭素質材料とを乾式混合粉砕し、得られた混合粉体を加圧成型した後破砕し、熱処理した後賦活する活性炭の製造方法である。 Another invention of the present invention is a mixed powder obtained by dry-mixing and pulverizing at least a carbonaceous material having weak cohesiveness or more and a carbonaceous material containing an alkali metal and / or alkaline earth metal. This is a method for producing activated carbon that is activated after being pressure-molded, crushed and heat-treated.
本発明の脱色用活性炭によれば、糖液などに含まれる着色成分を高い容積効率で除去することができる。また、本発明の活性炭は高硬度を有するので、充填時や使用時における活性炭の損傷が少なく、再生ロスを低減化することができる。また、本発明の方法によれば、このような活性炭を工業的に有利に製造することができる。 According to the activated carbon for decolorization of the present invention, it is possible to remove a coloring component contained in a sugar solution or the like with high volumetric efficiency. Moreover, since the activated carbon of the present invention has high hardness, the activated carbon is less damaged at the time of filling and use, and the regeneration loss can be reduced. Moreover, according to the method of this invention, such activated carbon can be manufactured industrially advantageously.
本発明の活性炭における第１の特徴は、細孔直径２００〜１０００ｎｍの領域における活性炭充填容積あたりの細孔容積が０．０６０ｃｍ３／ｃｍ３以上で、かつ硬度が９４．０％以上あることにある。 The first feature of the activated carbon of the present invention is the pore volume per activated carbon filling volume in the region of pore diameters 200~1000nm is 0.060cm 3 / cm 3 or more, and that the hardness is not less than 94.0% is there.
従来、糖液などの脱色に対しては、活性炭のトランジショナル域（細孔直径５０〜１００ｎｍ）の細孔容積が関係すると言われていた。しかしながら、本発明者らが詳細に検討を行ったところ、トランジショナル域の細孔容積は想定よりも少なくてよく、むしろさらに大きな細孔直径の領域の細孔容積を増大させることにより、脱色能力が向上することが明らかになった。 Conventionally, it has been said that decolorization of a sugar solution or the like is related to the pore volume in the transitional region (pore diameter 50 to 100 nm) of activated carbon. However, when the present inventors examined in detail, the pore volume of the transitional region may be smaller than expected, but rather, the decolorizing ability is increased by increasing the pore volume of the region having a larger pore diameter. It became clear that improved.
現実に液体の脱色を行う場合、活性炭の脱色能力はその重量あたりの能力より、容器に充填した際の体積（充填容積）あたりの能力の方が重要であるため、本発明においては活性炭の細孔容積を充填容積あたりの細孔容積で評価した。 When actually decolorizing a liquid, the decolorization ability of activated carbon is more important per volume (filling volume) when the container is filled than the capacity per weight. The pore volume was evaluated by the pore volume per filling volume.
活性炭の充填容積あたりの細孔容積は、以下の方法で算出する。まず、活性炭の重量当たりの細孔容積を、ポロシメーターを用い、水銀圧入法により、水銀圧は０．４５ｐｓiから３００００ｐｓｉで測定する。一方、ＪＩＳ−１４７４に準拠して該活性炭の充填比重を求め、前記重量あたりの細孔容積に充填比重を乗じて充填容積あたりの細孔容積を算出する。 The pore volume per packed volume of activated carbon is calculated by the following method. First, the pore volume per weight of the activated carbon is measured from 0.45 psi to 30000 psi by a mercury intrusion method using a porosimeter. On the other hand, the filling specific gravity of the activated carbon is obtained based on JIS-1474, and the pore volume per filling volume is calculated by multiplying the pore volume per weight by the filling specific gravity.
本発明の活性炭は上記方法によって算出された細孔直径２００〜１０００ｎｍの領域における活性炭充填容積あたりの細孔容積が０．０６０ｃｍ３／ｃｍ３以上の活性炭である。この領域の細孔容積は大きい方が物質の拡散が容易になるため脱色能力が上がる傾向があるので、この細孔容積は０．０６５ｃｍ３／ｃｍ３以上が好ましく、０．０７０ｃｍ３／ｃｍ３以上がさらに好ましい。一方、あまり細孔容積が大きいと、硬度が低下したり微分が発生したりしやすくなる傾向があるため、細孔直径２００〜１０００ｎｍの領域における活性炭充填容積あたりの細孔容積は０．２０ｃｍ３／ｃｍ３以下であることが好ましく、０．１２５ｃｍ３／ｃｍ３以下であることがさらに好ましい。 Activated carbon of the present invention are activated carbon pore volume per activated carbon filling volume in the region of the pore diameter 200~1000nm calculated is 0.060cm 3 / cm 3 or more by the above method. Since the pore volume of this region larger tends to go up bleaching ability for easier diffusion of substances, the pore volume is preferably 0.065cm 3 / cm 3 or more, 0.070cm 3 / cm 3 The above is more preferable. On the other hand, if the pore volume is too large, hardness tends to decrease or differentiation tends to occur, so the pore volume per activated carbon filling volume in the region of pore diameter 200 to 1000 nm is 0.20 cm 3. / preferably cm 3 or less, still more preferably 0.125 cm 3 / cm 3 or less.
本発明の活性炭の硬度は９４．０％以上である。この程度の硬度があれば、活性炭は通常の使用範囲では粉化せず高い再生収率が得られる。硬度は高い方がよく、９６．０％以上とするのがより好ましい。硬度の上限はとくに限られるものではない。なお、本発明における活性炭の硬度とはＪＩＳ−１４７４に準拠して測定されたものを指す。 The activated carbon of the present invention has a hardness of 94.0% or more. With this degree of hardness, the activated carbon is not pulverized in the normal use range, and a high regeneration yield can be obtained. The hardness should be high, and more preferably 96.0% or more. The upper limit of the hardness is not particularly limited. In addition, the hardness of activated carbon in this invention points out what was measured based on JIS-1474.
本発明の活性炭においては、２００〜１０００ｎｍの領域の細孔容積が一定以上あることに加え、この全領域の細孔が一定の範囲で存在することが好ましい。一般に、２００〜６００ｎｍの領域に比べ６００〜１０００ｎｍの範囲に細孔容積の小さい領域ができやすいが、高い脱色性能を得るためには、６００〜１０００ｎｍの領域においても一定の細孔容積が存在する事が好ましい。即ち、細孔直径６００〜１０００ｎｍの領域における活性炭充填容積あたり細孔容積が０．０２３ｃｍ３／ｃｍ３以上が好ましい。 In the activated carbon of the present invention, the pore volume in the region of 200 to 1000 nm is preferably not less than a certain value, and the pores in this entire region are preferably present in a certain range. In general, a region having a small pore volume is easily formed in a range of 600 to 1000 nm compared to a region of 200 to 600 nm, but in order to obtain high decolorization performance, a constant pore volume exists in the region of 600 to 1000 nm. Things are preferable. That is, the activated carbon packed volume per pore volume in the region of pore diameters 600~1000nm is 0.023cm 3 / cm 3 or more.
一方、本発明の活性炭におけるミクロ域からトランジショナル域の細孔に関しては、吸着能力を確保するためある程度以上あればよく、それ以上に多くても吸着能力はあまり向上しない。一定以上の吸着能力を得るためには細孔直径１０〜２００ｎｍの領域の細孔容積は０．０２３ｃｍ３／ｃｍ３以上あればよく、０．０３０ｃｍ３／ｃｍ３以上であればより好ましい。逆にこの領域の細孔容積があまり大きいと硬度が低下したり微粉の脱落が起こりやすくなる傾向があり実用上不利になる場合があるため、０．１５０ｃｍ３／ｃｍ３以下が好ましく、０．１００ｃｍ３／ｃｍ３以下がさらに好ましい。 On the other hand, with respect to the pores in the micro range to the transitional range in the activated carbon of the present invention, it is sufficient if it is more than a certain level in order to secure the adsorption capability. The pore volume of the region of pore diameters 10~200nm in order to obtain a certain level of adsorption capacity is sufficient if 0.023cm 3 / cm 3 or more, more preferably equal to 0.030 cm 3 / cm 3 or more. Because in some cases reverse the pore volume of the space is too large and the hardness tends to easily occur shedding of fine lowered practical disadvantage is preferably 0.150cm 3 / cm 3 or less, 0. 100 cm 3 / cm 3 or less is more preferable.
本発明の活性炭は、植物系、果実殻系、鉱物系などの各種炭素質材料を原料として製造できるが、活性炭の硬度を高くしやすく、一定品質のものを容易に、安価に入手できる点から中でも石炭系の炭素質材料を原料とするのが好ましい。石炭系の炭素質材料としては微粘炭、弱粘炭、強粘炭などを例示することができる。 The activated carbon of the present invention can be produced from various carbonaceous materials such as plant-based, fruit shell-based, and mineral-based materials. However, it is easy to increase the hardness of the activated carbon, and a certain quality can be obtained easily and inexpensively. Among them, it is preferable to use a coal-based carbonaceous material as a raw material. Examples of the coal-based carbonaceous material include slightly viscous coal, weakly viscous coal, and strongly viscous coal.
脱色の対象となる液体の粘度は限定されるものではなく、種々の粘度のものに対応することが出来る。細孔に吸着される物質の拡散状態にもよるが、一般に粘性の高い液の脱色は粘性の低い液の脱色に比べ困難が増すが、本発明の活性炭は適切な細孔分布を有することから２５℃における粘度が２０ｍＰａ・秒以上という比較的高粘度の溶液の脱色にも好適に使用できる。なお、ここでいう粘度とはＢ型粘度計により測定した粘度である。 The viscosity of the liquid to be decolorized is not limited, and can correspond to various viscosities. Although it depends on the diffusion state of the substance adsorbed in the pores, in general, decolorization of liquids with high viscosity is more difficult than decolorization of liquids with low viscosity, but the activated carbon of the present invention has an appropriate pore distribution. It can be suitably used for decolorization of a relatively high viscosity solution having a viscosity at 25 ° C. of 20 mPa · second or more. In addition, the viscosity here is a viscosity measured with a B-type viscometer.
本発明の活性炭は、弱粘結性以上を有する炭素質材料と、アルカリ金属及び／又はアルカリ土類金属を含有する炭素質材料とを乾式混合し、熱処理した後賦活することによって製造することができる。ここで、弱粘結性以上を有する炭素質材料とは、ボタン指数が１．０以上である炭素質材料である。なお、ボタン指数は、ＪＩＳ Ｍ ８８０１ ６のるつぼ膨張試験方法に準拠し、試料を所定のるつぼに入れて所定の条件で加熱し、生成した残渣を標準輪郭と比較して測定される。 The activated carbon of the present invention can be produced by dry-mixing a carbonaceous material having weak cohesiveness or higher and a carbonaceous material containing an alkali metal and / or alkaline earth metal, heat-treating and then activating. it can. Here, the carbonaceous material having a weak caking property or more is a carbonaceous material having a button index of 1.0 or more. The button index is measured in accordance with the crucible expansion test method of JIS M88016, in which a sample is placed in a predetermined crucible and heated under predetermined conditions, and the generated residue is compared with a standard contour.
弱粘結性以上を有する炭素質材料としては、植物系、果実殻系、鉱物系などを挙げることができるが、なかでも石炭系の炭素質材料が前述の理由から好ましい。このような石炭系の炭素質材料としては、ボタン指数が１〜３の弱粘炭が好ましく用いられるが、粘結性が不足して成型性が良くない場合にはボタン指数が３以上の強粘炭およびピッチなどを適切な割合で混合して用いることもできる。 Examples of the carbonaceous material having weak cohesiveness or more include plant-based, fruit shell-based, and mineral-based materials, and among them, coal-based carbonaceous materials are preferable for the above-described reasons. As such a coal-based carbonaceous material, weakly viscous coal having a button index of 1 to 3 is preferably used, but if the caking property is insufficient and the moldability is not good, the button index is a strong index of 3 or more. It is also possible to mix and use lignite and pitch at an appropriate ratio.
アルカリ金属及び／又はアルカリ土類金属を含有する炭素質材料としては、石炭系の炭素質材料が好ましい。アルカリ金属としては、カリウム、ナトリウムなどを挙げることができる。また、アルカリ土類金属としては、カルシウムなどを挙げることができる。アルカリ金属及び／又はアルカリ土類金属を含有する炭素質材料中のアルカリ金属とアルカリ土類金属は金属原子総量として、３００ｐｐｍ以上、１１００ｐｐｍ以下が好ましい。アルカリ金属及びアルカリ土類金属の中でも特にカルシウムが好ましく、カルシウムの含有量は３００ｐｐｍ以上、１０００ｐｐｍ以下の炭素質材料を使用するのが脱色能力、硬度、成型性の観点から好ましい。 As the carbonaceous material containing an alkali metal and / or alkaline earth metal, a coal-based carbonaceous material is preferable. Examples of the alkali metal include potassium and sodium. Examples of the alkaline earth metal include calcium. The alkali metal and alkaline earth metal in the carbonaceous material containing an alkali metal and / or alkaline earth metal is preferably 300 ppm or more and 1100 ppm or less as the total amount of metal atoms. Among alkali metals and alkaline earth metals, calcium is particularly preferable, and the use of a carbonaceous material having a calcium content of 300 ppm or more and 1000 ppm or less is preferable from the viewpoint of decolorization ability, hardness, and moldability.
本発明の活性炭の製造方法においては、炭素質材料の組織中にアルカリ金属及び／又はアルカリ土類金属が均質かつ高分散に分布している原料が用いられるため、炭素質材料に特定量の金属化合物を添加した後賦活する方法と比較して、細孔形成の局在化が起こりにくく均質な細孔形成が成されるため、適切な細孔分布が得られ、硬度も高くすることができる。 In the method for producing activated carbon of the present invention, since a raw material in which alkali metal and / or alkaline earth metal is homogeneously and highly dispersed is used in the structure of the carbonaceous material, a specific amount of metal is used as the carbonaceous material. Compared with the method of activation after the addition of the compound, the pore formation is less likely to be localized and uniform pore formation is achieved, so that an appropriate pore distribution can be obtained and the hardness can be increased. .
本発明の活性炭を製造するには、先ず弱粘結性以上を有する炭素質材料（以下材料１ということがある）とアルカリ金属及び／又はアルカリ土類金属を含有する炭素質材料（以下材料２ということがある）とを乾式混合粉砕する。これらの炭素質材料１及び２の他、本発明の効果を阻害しない範囲で強粘炭あるいはピッチなどを添加するのは差し支えない。乾式混合粉砕する方法は、両炭素質材料の比率がほぼ一定になるように混合粉砕できれば特に制限はないが、ボールミル、ロットミルあるいは高速ミキサーなどにより容易に実施することができる。 In order to produce the activated carbon of the present invention, first, a carbonaceous material having weak cohesiveness or higher (hereinafter sometimes referred to as material 1) and a carbonaceous material containing alkali metal and / or alkaline earth metal (hereinafter referred to as material 2). May be dry mixed and pulverized. In addition to these carbonaceous materials 1 and 2, it is possible to add strong coal or pitch within a range that does not impair the effects of the present invention. The dry mixing and pulverization method is not particularly limited as long as the ratio of both carbonaceous materials can be mixed and pulverized so as to be almost constant, but can be easily implemented by a ball mill, a lot mill, a high speed mixer or the like.
材料１と材料２の混合比率は原料となる炭素質材料と目的とする脱色能力や硬度に応じて定めればよいが、材料１の比率があまり高すぎると硬度は増大する一方、細孔直径が２００ｎｍ以上の細孔形成が抑制され、脱色性能が低下する傾向にあり、また材料１の比率があまり低すぎると成型性が低下し、硬度が低下する傾向があるので、材料１と材料２は、重量比で１：９〜９：１が好ましく、より好ましくは４：６〜３：７の割合で混合するのが好ましい。 The mixing ratio of the material 1 and the material 2 may be determined according to the carbonaceous material used as a raw material and the target decolorization ability and hardness. However, if the ratio of the material 1 is too high, the hardness increases, but the pore diameter However, when the ratio of the material 1 is too low, the moldability tends to be lowered and the hardness tends to be lowered. Is preferably in a weight ratio of 1: 9 to 9: 1, more preferably in a ratio of 4: 6 to 3: 7.
成形工程においては、材料１と材料２は乾式混合粉砕された後、１８０ｋｇ/ｃｍ２以上の圧力で加圧することにより、成型物を得ることができ好ましい。加圧成型するための装置はとくに限定されるものではなく、例えばロールプレス式、ディスク方ペレッター式、リング型ペレッター式、押し出し式などの成型装置が使用可能である。また、圧力や成型物の形状もとくに限定されるものではなく、円柱状、円筒状、ペレット状、球状、シート状など目的に応じて適宜決めればよい。これらの大きさもとくに限定されない。 In the molding step, the material 1 and the material 2 are preferably dry-mixed and pulverized and then pressed at a pressure of 180 kg / cm 2 or more to obtain a molded product. An apparatus for pressure molding is not particularly limited, and for example, a roll press type, a disk side pelleter type, a ring type pelleter type, an extrusion type, or the like can be used. Further, the pressure and the shape of the molded product are not particularly limited, and may be appropriately determined according to the purpose such as a columnar shape, a cylindrical shape, a pellet shape, a spherical shape, or a sheet shape. These sizes are not particularly limited.
得られた成型物は公知の粉砕機、例えば上述したボールミル、ロットミルあるいは高速ミキサーなどにより粉砕される。粉砕物は８／３０メッシュなど所定の大きさに整粒されるが、活性炭としての平均粒径として０．３〜３０ｍｍ程度、好ましくは０．５〜１．０ｍｍ程度になるように整粒するのが実用的であり、好ましい。整粒された粉砕物は熱処理に付される。熱処理は、還元ガス雰囲気下で５５０〜７５０℃まで加熱すればよい。より高性能、より高強度の炭化物又は活性炭を得るには、二段階での熱処理、例えば、２００〜４００℃まで酸化ガス雰囲気下５〜３０℃／分で昇温し、さらに５５０〜７５０℃まで還元ガス雰囲気下５〜３０℃/分で昇温するのが好ましい。 The obtained molded product is pulverized by a known pulverizer such as the above-described ball mill, lot mill or high-speed mixer. The pulverized product is sized to a predetermined size such as 8/30 mesh, but is sized so that the average particle size as activated carbon is about 0.3 to 30 mm, preferably about 0.5 to 1.0 mm. Is practical and preferred. The sized pulverized product is subjected to heat treatment. The heat treatment may be performed up to 550 to 750 ° C. in a reducing gas atmosphere. In order to obtain a higher-performance, higher-strength carbide or activated carbon, heat treatment in two stages, for example, 200 to 400 ° C., raised to 5 to 30 ° C./min in an oxidizing gas atmosphere, and further to 550 to 750 ° C. It is preferable to raise the temperature at 5 to 30 ° C./min in a reducing gas atmosphere.
乾留された粉砕物はさらに賦活されて活性炭となる。賦活は、水蒸気、二酸化炭素、空気、プロパン燃焼排ガス、これら混合ガス等の酸化性ガスの雰囲気下４００〜１０００℃で実施するガス賦活や塩化亜鉛、リン酸、塩化カルシウム、硫化カリウムなどの薬剤の存在下４００〜８００℃程度で実施する薬品賦活が採用される。なかでも、空気とＬＰＧの比率が１対０．０４２５程度の燃焼ガス流通下９００〜１０００℃で行う燃焼ガス賦活を採用するのが好ましい。賦活収率は、脱色能力と硬度の関係から必要に応じて適宜決定すればよい。 The dry-pulverized pulverized product is further activated to become activated carbon. Activation is performed at 400 to 1000 ° C. in an atmosphere of oxidizing gas such as water vapor, carbon dioxide, air, propane combustion exhaust gas, and mixed gas thereof, and chemicals such as zinc chloride, phosphoric acid, calcium chloride, potassium sulfide, etc. Chemical activation carried out at about 400 to 800 ° C. in the presence is employed. Especially, it is preferable to employ | adopt the combustion gas activation performed at 900-1000 degreeC under the combustion gas distribution | circulation whose ratio of air and LPG is about 1 to 0.0425. The activation yield may be appropriately determined as necessary from the relationship between the decolorization ability and the hardness.
賦活後、活性炭は希塩酸などで酸水洗され、ｐＨ５．０以上７．０以下に調整することで、本発明の活性炭を得ることができる。ここでいう活性炭のｐＨとは、ＪＩＳ−Ｋ１４７４に準拠して測定されたｐＨである。 After activation, the activated carbon is washed with dilute hydrochloric acid and adjusted to pH 5.0 or more and 7.0 or less, whereby the activated carbon of the present invention can be obtained. The pH of the activated carbon here is a pH measured in accordance with JIS-K1474.
本発明の活性炭は用途に応じて、表面を化学修飾する、表面に物理的に機能性物質を担持させるなどの後処理を施しても良い。このような表面修飾の例としては、銀、鉄などの金属の塩や酸化物、鉱酸を添着する他、表面を酸性にする処理なども挙げられる。 The activated carbon of the present invention may be subjected to post-treatment such as chemical modification of the surface or physical loading of a functional substance on the surface depending on the application. Examples of such surface modification include treatment of making the surface acidic in addition to adding a salt or oxide of a metal such as silver or iron, or a mineral acid.
本発明の活性炭は、例えば、糖液を強酸性カチオン交換樹脂に接触させて糖液の脱塩処理又は転化処理を行った後、酸性の糖液中に残存する色素成分を効率的に除去するために用いられる。 For example, the activated carbon of the present invention efficiently removes the dye component remaining in the acidic sugar liquid after the sugar liquid is brought into contact with a strongly acidic cation exchange resin and subjected to desalting or conversion treatment of the sugar liquid. Used for.
活性炭を脱色用に使用する場合、活性炭をカラムなどの容器に充填し、バッチ式又は連続式で実施される。連続式で行う場合は向流方式で実施することが多い。脱色性能が低下した活性炭は所定の処理を施して再生され、再使用される。 When activated carbon is used for decolorization, the activated carbon is packed in a container such as a column and is carried out batchwise or continuously. When using the continuous method, the countercurrent method is often used. The activated carbon having a reduced decolorization performance is regenerated after being subjected to a predetermined treatment and reused.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、各物性値は次の方法により測定した。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Each physical property value was measured by the following method.
ヨウ素吸着量（ＩＡ）、硬度はＪＩＳ−Ｋ１４７４に準拠して測定した。また、細孔分布の測定には株式会社島津製作所製のオートポアＩＶ９５１０型を使用した。また、溶液の粘度は（株）東京計器製のＢ型粘度計で測定した。 The iodine adsorption amount (IA) and hardness were measured according to JIS-K1474. Moreover, Shimadzu Corporation auto-pore IV9510 type | mold was used for the measurement of pore distribution. The viscosity of the solution was measured with a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.
先ず、材料１として固定炭素分５９．５重量％、かつ灰分０．７重量％の弱粘結性を有する瀝青炭（ボタン指数３）を、材料２として固定炭素分４８．３重量％以上、かつ灰分０．７重量％でありかつナトリウム４５ｐｐｍ、カルシウム８００ｐｐｍを含む微粘結性の瀝青炭（ボタン指数０．５）を使用し、材料１と材料２を重量比３：７でボールミルを用いて混合粉砕し、得られた粉体を（株）山本水圧工業所製の加圧成形機を用いて直径４ｃｍ、長さ１５ｃｍの容器に充填し、１００℃、２８０ｋｇ/ｃｍ２の圧力で加圧成型した後ジョークラッシャーで破砕し、粒径範囲０．１〜２．０ｍｍ、平均粒径０．９５ｍｍの顆粒に整粒した。 First, bituminous coal (button index 3) having a fixed carbon content of 59.5% by weight and an ash content of 0.7% by weight as material 1 and a fixed carbon content of 48.3% by weight or more as material 2; Using a bituminous bituminous coal (button index 0.5) with an ash content of 0.7% by weight and containing 45 ppm of sodium and 800 ppm of calcium, mixing the materials 1 and 2 using a ball mill at a weight ratio of 3: 7 The powder obtained is pulverized and filled into a container with a diameter of 4 cm and a length of 15 cm using a pressure molding machine manufactured by Yamamoto Hydraulic Industry Co., Ltd., and pressure molded at a pressure of 100 ° C. and 280 kg / cm 2. After that, it was crushed with a jaw crusher and sized into granules having a particle size range of 0.1 to 2.0 mm and an average particle size of 0.95 mm.
次いでこの顆粒を外熱式ロータリーキルンに投入し、３００℃まで酸化ガス雰囲気下５℃／分の昇温を施し２時間保持し、続いて６５０℃まで還元ガス雰囲気下８．７５℃/分の昇温を実施して炭化した。揮発分０ｇベースに換算したこの炭化炭７５．０ｇを内径５７ｍｍ、高さ６００ｍｍの流動炉に仕込み、空気２０Ｌ（リットル、以下同じ）／分、ＬＰＧ ０．８５Ｌ／分の燃焼ガス流通下９５０℃で賦活収率５０％となるように燃焼ガス賦活を行い活性炭を得た。 Next, the granules are put into an externally heated rotary kiln, heated up to 300 ° C. under an oxidizing gas atmosphere at 5 ° C./min, held for 2 hours, and then up to 650 ° C. under a reducing gas atmosphere at 8.75 ° C./min. Carbonization was performed by heating. 75.0 g of this charcoal converted to a base of 0 g of volatile matter was charged into a fluidized furnace having an inner diameter of 57 mm and a height of 600 mm, and 950 ° C. under a combustion gas flow of 20 L (liter, the same applies hereinafter) / min and LPG 0.85 L / min The activated gas was obtained by activating the combustion gas so that the activation yield was 50%.
得られた活性炭を酸水洗し、６回の煮沸水洗浄を行い、ｐＨを６．５±０．５に調整した後１２０℃で２〜３時間乾燥した。活性炭の充填密度ρＢ（ｇ／ｃｍ３）、ヨウ素吸着量ＩＡ（ｍｇ／ｇ）、脱色能（％）、充填容積あたりの細孔直径２００〜１０００ｎｍおよび６００〜１０００ｎｍの領域における細孔容積（ｃｍ３／ｃｍ３）、硬度（％）を測定した。 The obtained activated carbon was washed with acid water, washed 6 times with boiling water, adjusted to pH 6.5 ± 0.5, and dried at 120 ° C. for 2 to 3 hours. Charging density ρB (g / cm 3 ) of activated carbon, iodine adsorption amount IA (mg / g), decolorization ability (%), pore volume per packing volume in the range of 200 to 1000 nm and 600 to 1000 nm (cm 3 / cm 3 ) and hardness (%).
内径２．０７ｃｍ、高さ４０ｃｍのカラムに上記活性炭を充填し、三井製糖（株）製三温糖：イオン交換水＝１：１（重量比）からなる原液を２５℃、ＳＶ＝２ｈｒ−１の条件下、アップフローで通流し、脱色テストを行った。この原液の粘度は２５℃において３０ｍＰａ・秒であった。充填した活性炭の２０倍通液した時点でサンプルを採取し、１０ｍｍセルを使用し、波長λ＝４２０ｎｍで吸光度を測定し、次の式で脱色能を算出した。
脱色能（％）＝〔（原液吸光度−２０倍通液後の処理液の吸光度）／原液吸光度〕×１００。
The activated carbon is packed in a column having an inner diameter of 2.07 cm and a height of 40 cm, and a stock solution made of Mitsui Sugar Co., Ltd., tri-warm sugar: ion exchange water = 1: 1 (weight ratio) is 25 ° C., SV = 2 hr −1. Under the above conditions, a decolorization test was conducted by passing the product up-flow. The viscosity of this stock solution was 30 mPa · sec at 25 ° C. A sample was taken when the charged activated carbon was passed 20 times, the absorbance was measured at a wavelength λ = 420 nm using a 10 mm cell, and the decolorization ability was calculated by the following formula.
Decolorization ability (%) = [(absorbance of stock solution−absorbance of treated solution after passing through 20 times) / absorbance of stock solution] × 100.
得られた活性炭の充填密度、ヨウ素吸着量、脱色能、各細孔直径領域における細孔容積、硬度を表１に示す。実施例１の活性炭は硬度も高く、実用上充分な良好な脱色能力を示した。 Table 1 shows the packing density, iodine adsorption amount, decolorizing ability, pore volume and hardness in each pore diameter region of the obtained activated carbon. The activated carbon of Example 1 had a high hardness and exhibited a good decolorizing ability sufficient for practical use.
材料１と、材料２を重量比で４：６とする以外は実施例１と同様にして活性炭を得た。同様に活性炭の充填密度ρＢ（ｇ／ｃｃ）、ヨウ素吸着量ＩＡ（ｍｇ／ｇ）、脱色能（％）、充填密度より求めた体積あたりの細孔直径２００〜１０００ｎｍおよび６００〜１０００ｎｍの領域における細孔容積（ｃｍ３／ｃｍ３）、硬度（％）を測定した。結果を表１に示す。硬度、脱色性能とも良好である。 Activated carbon was obtained in the same manner as in Example 1 except that the weight ratio of Material 1 and Material 2 was 4: 6. Similarly, the packing density of activated carbon ρB (g / cc), iodine adsorption amount IA (mg / g), decolorization ability (%), pore diameter per volume determined from the packing density in the region of 200 to 1000 nm and 600 to 1000 nm. The pore volume (cm 3 / cm 3 ) and hardness (%) were measured. The results are shown in Table 1. Both hardness and decolorization performance are good.
材料１及び２を、ボールミルで粉砕する際に、材料１及び２の合計１００重量部に対し、固定炭素分６０．９重量％、かつ灰分６．２重量％の強粘結炭（ボタン指数９）２０重量部を添加する以外は実施例１と同様にして活性炭を得た。同様に活性炭の充填密度ρＢ（ｇ／ｃｃ）、ヨウ素吸着量ＩＡ（ｍｇ／ｇ）、脱色能（％）、充填密度より求めた体積あたりの細孔直径２００〜１０００ｎｍおよび６００〜１０００ｎｍの領域における細孔容積（ｃｍ３／ｃｍ３）、硬度（％）を測定した。結果を表１に示す。硬度、脱色性能とも良好である。 When materials 1 and 2 are pulverized by a ball mill, strong coking coal having a fixed carbon content of 60.9% by weight and an ash content of 6.2% by weight (button index 9) with respect to 100 parts by weight of materials 1 and 2 in total. ) Activated carbon was obtained in the same manner as in Example 1 except for adding 20 parts by weight. Similarly, the packing density of activated carbon ρB (g / cc), iodine adsorption amount IA (mg / g), decolorization ability (%), pore diameter per volume determined from the packing density in the region of 200 to 1000 nm and 600 to 1000 nm. The pore volume (cm 3 / cm 3 ) and hardness (%) were measured. The results are shown in Table 1. Both hardness and decolorization performance are good.
材料１及び２の合計１００重量部に対し、強粘結炭２５重量部を添加する以外は実施例１と同様にして活性炭を得た。同様に活性炭の充填密度ρＢ（ｇ／ｃｃ）、ヨウ素吸着量ＩＡ（ｍｇ／ｇ）、脱色能（％）、充填密度より求めた体積あたりの細孔直径２００〜１０００ｎｍおよび６００〜１０００ｎｍの領域における細孔容積（ｃｍ３／ｃｍ３）、硬度（％）を測定した。結果を表１に示す。実施例４で得られた活性炭は、実施例１〜３で得られた活性炭に比べ、脱色能力でやや劣るが、実用上問題のないレベルである。 Activated carbon was obtained in the same manner as in Example 1 except that 25 parts by weight of strong caking coal was added to 100 parts by weight of the total of materials 1 and 2. Similarly, the packing density of activated carbon ρB (g / cc), iodine adsorption amount IA (mg / g), decolorization ability (%), pore diameter per volume determined from the packing density in the region of 200 to 1000 nm and 600 to 1000 nm. The pore volume (cm 3 / cm 3 ) and hardness (%) were measured. The results are shown in Table 1. The activated carbon obtained in Example 4 is slightly inferior in decoloring ability as compared with the activated carbon obtained in Examples 1 to 3, but is at a level having no practical problem.
比較例１
炭素質材料として材料１のみを使用し、賦活を９００℃で行う以外は実施例１と同様にして活性炭を得た。同様に活性炭の充填密度ρＢ（ｇ／ｃｃ）、ヨウ素吸着量ＩＡ（ｍｇ／ｇ）、脱色能（％）、充填密度より求めた体積あたりの細孔直径２００〜１０００ｎｍおよび６００〜１０００ｎｍの領域における細孔容積（ｃｍ３／ｃｍ３）、硬度（％）を測定した。結果を表１に示す。実施例１〜４で得られた活性炭に比べ２００〜１０００ｎｍの範囲の細孔容積がかなり小さく、脱色能力に大きく劣っている。
Comparative Example 1
Activated carbon was obtained in the same manner as in Example 1 except that only the material 1 was used as the carbonaceous material and activation was performed at 900 ° C. Similarly, the packing density of activated carbon ρB (g / cc), iodine adsorption amount IA (mg / g), decolorization ability (%), pore diameter per volume determined from the packing density in the region of 200 to 1000 nm and 600 to 1000 nm. The pore volume (cm 3 / cm 3 ) and hardness (%) were measured. The results are shown in Table 1. Compared with the activated carbon obtained in Examples 1 to 4, the pore volume in the range of 200 to 1000 nm is considerably small, and the decolorization ability is greatly inferior.
比較例２
炭素質材料を粉砕する工程において、Ｃａ（ＯＨ）２を１重量％添加して混合粉砕する以外は比較例１と同様にして活性炭を得た。同様に活性炭の充填密度ρＢ（ｇ／ｃｃ）、ヨウ素吸着量ＩＡ（ｍｇ／ｇ）、脱色能（％）、充填密度より求めた体積あたりの細孔直径２００〜１０００ｎｍおよび６００〜１０００ｎｍの領域における細孔容積（ｃｍ３／ｃｍ３）、硬度（％）を測定した。結果を表１に示す。脱色能力については実施例の活性炭と同等であるが硬度で大きく劣るものとなっている。
Comparative Example 2
In the step of pulverizing the carbonaceous material, activated carbon was obtained in the same manner as in Comparative Example 1 except that 1% by weight of Ca (OH) 2 was added and mixed and pulverized. Similarly, the packing density of activated carbon ρB (g / cc), iodine adsorption amount IA (mg / g), decolorization ability (%), pore diameter per volume determined from the packing density in the region of 200 to 1000 nm and 600 to 1000 nm. The pore volume (cm 3 / cm 3 ) and hardness (%) were measured. The results are shown in Table 1. The decolorizing ability is the same as that of the activated carbon of the example, but the hardness is greatly inferior.
本発明の活性炭は、糖液などに含まれる着色成分の除去に好適である。また、本発明の活性炭は、高硬度を有するので、充填時や使用時における活性炭の損傷が少なく、再生ロスを低減化することができる。本発明の活性炭は、好ましくは、弱粘結性以上を有する炭素質材料と、アルカリ金属及び／又はアルカリ土類金属を含有する炭素質材料とを乾式混合粉砕し、得られた混合粉体を加圧成型した後破砕し、熱処理した後賦活するという簡単な方法で製造することができ、産業上有用である。
The activated carbon of the present invention is suitable for removing colored components contained in a sugar solution or the like. Moreover, since the activated carbon of this invention has high hardness, there is little damage to activated carbon at the time of filling and use, and it can reduce a regeneration loss. The activated carbon of the present invention is preferably obtained by dry-mixing and grinding a carbonaceous material having weak cohesiveness or higher and a carbonaceous material containing an alkali metal and / or an alkaline earth metal, and It can be produced by a simple method of crushing after pressure molding, activation after heat treatment, and industrially useful.
Claims (11)
The mixing ratio of the carbonaceous material having the weak caking property or more and the carbonaceous material containing an alkali metal and / or an alkaline earth metal is 1: 9 to 9: 1 by weight. The manufacturing method of activated carbon in any one.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007331986A (en) * | 2006-06-15 | 2007-12-27 | Japan Enviro Chemicals Ltd | Activated carbon |
| JP5159970B1 (en) * | 2012-05-16 | 2013-03-13 | 株式会社アルメディオ | Activated carbon and manufacturing method thereof |
| CN107913689A (en) * | 2017-11-16 | 2018-04-17 | 于伟军 | A kind of dangerous waste solid waste method for regenerating activated carbon |
| WO2019131209A1 (en) | 2017-12-27 | 2019-07-04 | 株式会社クラレ | Activated carbon and production method thereof |
| WO2019131208A1 (en) | 2017-12-27 | 2019-07-04 | 株式会社クラレ | Activated carbon and production method thereof |
| WO2020170985A1 (en) | 2019-02-18 | 2020-08-27 | 株式会社クラレ | Activated carbon and method for producing same |
| CN115124037A (en) * | 2021-03-29 | 2022-09-30 | 内蒙古浦瑞芬环保科技有限公司 | High-sugar honey briquette crushed charcoal and method for producing high-sugar honey briquette crushed charcoal |
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| JPH05302216A (en) * | 1992-04-27 | 1993-11-16 | Kunitaro Kawazoe | Modification of carbonaceous fiber |
| JPH09187648A (en) * | 1996-01-11 | 1997-07-22 | Mitsubishi Chem Corp | Active carbon for refining dry cleaning solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05302216A (en) * | 1992-04-27 | 1993-11-16 | Kunitaro Kawazoe | Modification of carbonaceous fiber |
| JPH09187648A (en) * | 1996-01-11 | 1997-07-22 | Mitsubishi Chem Corp | Active carbon for refining dry cleaning solvent |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007331986A (en) * | 2006-06-15 | 2007-12-27 | Japan Enviro Chemicals Ltd | Activated carbon |
| JP5159970B1 (en) * | 2012-05-16 | 2013-03-13 | 株式会社アルメディオ | Activated carbon and manufacturing method thereof |
| JP2013237595A (en) * | 2012-05-16 | 2013-11-28 | Almedio Inc | Activated carbon and method for producing the same |
| CN107913689A (en) * | 2017-11-16 | 2018-04-17 | 于伟军 | A kind of dangerous waste solid waste method for regenerating activated carbon |
| WO2019131209A1 (en) | 2017-12-27 | 2019-07-04 | 株式会社クラレ | Activated carbon and production method thereof |
| WO2019131208A1 (en) | 2017-12-27 | 2019-07-04 | 株式会社クラレ | Activated carbon and production method thereof |
| US11857943B2 (en) | 2017-12-27 | 2024-01-02 | Kuraray Co., Ltd. | Activated carbon and production method thereof |
| US11945724B2 (en) | 2017-12-27 | 2024-04-02 | Kuraray Co., Ltd. | Activated carbon and production method thereof |
| WO2020170985A1 (en) | 2019-02-18 | 2020-08-27 | 株式会社クラレ | Activated carbon and method for producing same |
| CN115124037A (en) * | 2021-03-29 | 2022-09-30 | 内蒙古浦瑞芬环保科技有限公司 | High-sugar honey briquette crushed charcoal and method for producing high-sugar honey briquette crushed charcoal |
| CN115124037B (en) * | 2021-03-29 | 2023-09-22 | 内蒙古浦瑞芬环保科技有限公司 | Broken carbon prepared by high molasses briquettes and method for producing broken carbon prepared by high molasses briquettes |
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