JP3125808B2 - Activated carbon honeycomb structure and manufacturing method thereof - Google Patents
Activated carbon honeycomb structure and manufacturing method thereofInfo
- Publication number
- JP3125808B2 JP3125808B2 JP03340071A JP34007191A JP3125808B2 JP 3125808 B2 JP3125808 B2 JP 3125808B2 JP 03340071 A JP03340071 A JP 03340071A JP 34007191 A JP34007191 A JP 34007191A JP 3125808 B2 JP3125808 B2 JP 3125808B2
- Authority
- JP
- Japan
- Prior art keywords
- honeycomb structure
- activated carbon
- carbon honeycomb
- radius
- pore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000011148 porous material Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 16
- 239000003077 lignite Substances 0.000 claims description 12
- 239000011306 natural pitch Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 description 15
- 230000004913 activation Effects 0.000 description 11
- 238000001994 activation Methods 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 238000004042 decolorization Methods 0.000 description 4
- 235000019256 formaldehyde Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、吸着剤や触媒担体とし
て優れた特性を有する活性炭ハニカム構造体およびその
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an activated carbon honeycomb structure having excellent properties as an adsorbent and a catalyst carrier, and a method for producing the same.
【０００２】[0002]
【従来の技術】活性炭は、シリカゲル、シリカ−アルミ
ナ、アルミナ、ゼオライトなどに比べて高比表面積を有
し、吸着能に優れているため吸着剤、触媒担体として各
種の用途に広く利用されている。従来このような目的に
用いられる活性炭は、一般にはペレット状、球状、顆粒
状などの粒子形状に成型されて使用されていた。2. Description of the Related Art Activated carbon has a higher specific surface area than silica gel, silica-alumina, alumina, zeolite and the like, and is excellent in adsorptivity, so that it is widely used as an adsorbent and a catalyst carrier for various uses. . Conventionally, activated carbon used for such a purpose has been generally used after being molded into a particle shape such as a pellet, a sphere, and a granule.
【０００３】例えば、活性炭を吸着剤として用いるとき
は粒子形状によってその性能が大きな影響を受けるもの
であり、粒子を小さくして吸着能を高めることは吸着効
率の改善方法として特に有効な方法である。しかしなが
ら、流体を流してその中の所定成分を吸着するような場
合には上記のように細粒化した吸着剤を使用すること
は、流体の圧力損失を招くという問題点を引き起こす。For example, when activated carbon is used as an adsorbent, its performance is greatly affected by the particle shape, and reducing the particles to increase the adsorbing ability is a particularly effective method for improving the adsorption efficiency. . However, in the case where a fluid is caused to flow and a predetermined component therein is adsorbed, the use of the adsorbent finely divided as described above causes a problem of causing a pressure loss of the fluid.
【０００４】そこで、最近では上記の問題点を解決する
ために活性炭をハニカム構造体として用いることが試み
られている。ハニカム構造体は、多数の並行した流通路
を有するため、流体を流す場合に圧力損失が小さいうえ
に単位体積当たりの見掛け比表面積を大きくとることが
できるので、流通流体中の有効成分の吸着を行なうに際
して、その吸着性能を改善し得るとともに圧力損失を大
幅に削減し得ることが期待される。Therefore, recently, in order to solve the above-mentioned problems, an attempt has been made to use activated carbon as a honeycomb structure. Since the honeycomb structure has a large number of parallel flow passages, when flowing a fluid, the pressure loss is small and the apparent specific surface area per unit volume can be increased. In carrying out, it is expected that the adsorption performance can be improved and the pressure loss can be greatly reduced.
【０００５】一般に、活性炭で実用可能な強度を持たせ
たハニカム構造体を得る方法としては、褐炭粉に補強材
としてカーボン、ロックウール、アルミナ等のファイバ
ー状のものまたは無機物質粒子を加え、さらに成型助剤
を加えて水とともに混練し、この混練物をハニカム形状
に成型し、乾燥、焼結、賦活等の工程を経て製造する方
法が提案されている。[0005] In general, a method for obtaining a honeycomb structure having a strength that can be practically used with activated carbon is to add a fibrous material such as carbon, rock wool, or alumina or an inorganic substance particle to a brown coal powder as a reinforcing material. There has been proposed a method of adding a molding aid, kneading the mixture with water, molding the kneaded material into a honeycomb shape, and performing processes such as drying, sintering, and activation.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、カーボ
ンファイバー等のファイバー状物質を補強材として用い
た場合には、ファイバーがハニカム構造のダイス目に目
詰まりを起こしてセル数（１平方インチ当たりの升目の
数）が１００セル以上の細かい升目のハニカム構造体が
得られないという欠点がある。また無機物質粒子を補強
材として添加すると比表面積が著しく減少してしまう欠
点がある。However, when a fibrous substance such as carbon fiber is used as a reinforcing material, the fibers are clogged in the honeycomb-structured dies and the number of cells (the number of cells per square inch) increases. Has a drawback that a honeycomb structure having fine cells of 100 cells or more cannot be obtained. In addition, there is a disadvantage that the addition of inorganic material particles as a reinforcing material significantly reduces the specific surface area.
【０００７】また、さらに云えば活性炭を用いて吸着お
よび／または触媒反応を行なわせる場合に、通常流通さ
せる反応物質の成分中には大小さまざまな分子が存在し
ているために、径の小さい細孔のみで形成されている活
性炭を用いて吸着および／または触媒反応を行なわせる
と、大きい分子は細孔内に拡散できず細孔表面を塞いで
しまうので早期に失活してしまう。逆に径の大きい細孔
のみで形成されている活性炭を用いてこれらの反応を行
なわせると小さい分子が反応せずに通過してしまい性能
が低下するのでいずれの場合も好ましくなく、したがっ
て活性炭を吸着剤、あるいは触媒担体とし広い範囲に適
用するのは小径の細孔と大径の細孔が適当な比率で存在
することが望ましい。[0007] In addition, when the adsorption and / or catalytic reaction is carried out using activated carbon, fine particles having a small diameter are present due to the presence of various large and small molecules in the components of the reactants which are usually circulated. When the adsorption and / or catalytic reaction is carried out using activated carbon formed only of pores, large molecules cannot diffuse into the pores and block the pore surface, so that they are deactivated early. Conversely, if these reactions are performed using activated carbon formed only of large-diameter pores, small molecules will pass without reacting and the performance will be reduced. For application to a wide range as an adsorbent or a catalyst carrier, it is desirable that small pores and large pores are present in an appropriate ratio.
【０００８】また、一般的に吸着剤または触媒担体とし
て必要なハニカム担体の実用破壊強度は、ハニカム担体
を縦横各１ｃｍ、長さ２ｃｍ程度の長方形にカットした
もので２ｋｇ以上であり、比表面積は１０００ｍ２／ｇ
以上であることが必要であるとされている。The practical breaking strength of a honeycomb carrier generally required as an adsorbent or a catalyst carrier is 2 kg or more when the honeycomb carrier is cut into a rectangle of about 1 cm in length and width and about 2 cm in length. 1000 m 2 / g
It is necessary to be above.
【０００９】本発明は吸着剤または触媒担体として適切
な細孔分布を有し、吸着能に優れ、且つ破壊強度の優れ
た活性炭ハニカム構造担体およびその製造方法を提供す
ることを目的とするものである。An object of the present invention is to provide an activated carbon honeycomb structure carrier having a pore distribution suitable as an adsorbent or a catalyst carrier, having excellent adsorption capacity and excellent breaking strength, and a method for producing the same. is there.
【００１０】[0010]
【課題を解決するための手段】上記の目的を達成するた
めの本発明は、水銀圧入法で測定した細孔構造が半径２
０オングストローム以上の細孔容積が０．４５ｍｌ／ｇ
以上で、半径３０００オングストローム以上の細孔容積
が０．２０〜０．３５ｍｌ／ｇである活性炭ハニカム構
造体、および該活性炭ハニカム構造体を得るに際し、褐
炭粉に有機質成型助剤と炭化付与剤と水を添加して混練
し、ハニカム構造体に押出し成型して乾燥した後、５０
０〜６００℃の温度範囲で焼成して炭化し、次いで７０
０〜１０００℃の温度範囲で賦活することを特徴とする
活性炭ハニカム構造体の製造方法である。In order to achieve the above object, the present invention provides a liquid crystal display device having a pore structure having a radius of 2 as measured by a mercury intrusion method.
0.45 ml / g pore volume of 0 Å or more
As described above, in order to obtain an activated carbon honeycomb structure having a pore volume having a radius of 3000 angstroms or more of 0.20 to 0.35 ml / g and an activated carbon honeycomb structure, an organic molding aid and a carbonizing agent are added to brown coal powder. Water is added and kneaded, extruded into a honeycomb structure, dried and then dried.
Calcined by firing in a temperature range of 0 to 600 ° C .;
A method for producing an activated carbon honeycomb structure, wherein activation is performed in a temperature range of 0 to 1000 ° C.
【００１１】[0011]
【作用】本発明の活性炭ハニカム構造体は水銀圧入法に
よる細孔構造が上記した細孔径と細孔容積との関係を有
するものであるが、このように半径２０オングストロー
ム以上の細孔の容積を０．４５ｍｌ／ｇ以上としたの
は、吸着剤および／または触媒担体としての性能を長期
に亘って接続させるためである。また半径３０００オン
グストローム以上の細孔の容積を０．２０〜０．３５ｍ
ｌ／ｇとしたのは、０．２０ｍｌ／ｇ未満では吸着剤お
よび／または触媒としての性能を長期に維持できず、
０．３５ｍｌ／ｇを超えると破壊強度が低下するからで
ある。The activated carbon honeycomb structure of the present invention has a pore structure obtained by a mercury intrusion method having a relationship between the pore diameter and the pore volume as described above. The reason for setting it to be 0.45 ml / g or more is to connect the performance as an adsorbent and / or a catalyst carrier for a long period of time. Further, the volume of pores having a radius of 3000 Å or more is set to 0.20 to 0.35 m.
The l / g is that if it is less than 0.20 ml / g, the performance as an adsorbent and / or a catalyst cannot be maintained for a long time,
If it exceeds 0.35 ml / g, the breaking strength decreases.
【００１２】本発明においては、市販の褐炭を粉砕して
所定の粒径範囲に篩い分けして得られた褐炭粉末に適量
の有機質成型助剤と炭化付与剤としての天然ピッチ３０
〜５０重量％とを水とともに混練して可塑化した後、真
空押出し成型機を用いて所望の形状のハニカムダイスを
通して成型し、多数の貫通孔を有するハニカム構造体に
成型する。次に得られた成型体を温度７０〜９０℃、湿
度８０〜９０％で乾燥させ、次いで５００〜６００℃の
温度範囲で焼成して炭化をした後、７００〜１０００℃
の温度で水蒸気賦活することで、上記したような細孔構
造を有する活性炭ハニカム構造体を得ることができるの
である。In the present invention, a commercially available lignite is pulverized and sieved to a predetermined particle size range.
５０50% by weight is kneaded with water and plasticized, and then molded through a honeycomb die having a desired shape using a vacuum extrusion molding machine to form a honeycomb structure having a large number of through holes. Next, the obtained molded body is dried at a temperature of 70 to 90 ° C and a humidity of 80 to 90%, and then calcined in a temperature range of 500 to 600 ° C to be carbonized.
By activating the steam at the above temperature, the activated carbon honeycomb structure having the above-described pore structure can be obtained.
【００１３】本発明においては、篩い分けによって得ら
れる褐炭粉末の粒径を２００メッシュ以下３５０メッシ
ュ以上とするのが適当である。その理由は２００メッシ
ュを超えると、ハニカム成型を行なうに際して混練物の
ダイス内での送りが悪くなるので均質なハニカム構造体
が得られなくなるからであり、３５０メッシュ未満では
ハニカム成型後の乾燥工程においてハニカム構造体の表
面および／または内部に亀裂を発生するからである。In the present invention, the particle size of the lignite powder obtained by sieving is suitably 200 mesh or less and 350 mesh or more. The reason for this is that if it exceeds 200 mesh, it becomes impossible to obtain a uniform honeycomb structure because the feeding of the kneaded material in the die becomes poor when performing the honeycomb molding, and if it is less than 350 mesh, the drying process after the honeycomb molding is performed. This is because cracks occur on the surface and / or inside of the honeycomb structure.
【００１４】本発明のハニカム構造体に成型する際に添
加する有機質成型助剤としては、水溶性のものであれば
如何なるものであってもよいが、セルローズ系のものが
特に好ましい。The organic molding aid to be added when molding the honeycomb structure of the present invention may be any water-soluble one, but a cellulose-based one is particularly preferred.
【００１５】また、炭化付与剤として天然産ピッチを用
いるのはハニカム構造体の破壊強度を向上させ、かつ細
孔構造を容易に調整することができるからであり、固定
炭素量１０〜１５重量％、軟化温度１２０〜１４０℃の
ものが特に好ましい。各種の市販品のピッチは固定炭素
量が多いために軟化温度も高くなり、ハニカム構造体の
乾燥、賦活工程で構造体の表面および／または内部に亀
裂を発生させる恐れがあるからである。天然ピッチの添
加量は３０〜５０重量％の範囲が好ましい。添加量が３
０重量％未満では破壊強度が低下してくるし、また５０
重量を超えると活性炭ハニカム構造体の細孔構造で孔径
の大きい細孔の数が減少するので破壊強度は向上するが
一方では半径３０００オングストローム以上の細孔容積
が減少するので吸着能が著しく低下してしまい、何れの
場合も好ましくない。The reason why natural pitch is used as the carbonizing agent is that the breaking strength of the honeycomb structure can be improved and the pore structure can be easily adjusted, and the fixed carbon content is 10 to 15% by weight. And those having a softening temperature of 120 to 140 ° C are particularly preferred. This is because pitches of various commercial products have a high softening temperature due to a large amount of fixed carbon, and may cause cracks on the surface and / or inside of the honeycomb structure in the drying and activation steps of the honeycomb structure. The added amount of the natural pitch is preferably in the range of 30 to 50% by weight. 3 added
If the content is less than 0% by weight, the breaking strength is reduced, and 50% or less.
If the weight is exceeded, the number of pores having a large pore diameter in the pore structure of the activated carbon honeycomb structure is reduced, so that the breaking strength is improved. Either case is not preferred.
【００１６】成型したハニカム構造体を温度７０〜９０
℃、湿度８０〜９０％の条件で乾燥するのは、上記条件
の範囲内で乾燥を行なえば亀裂の発生のないハニカム構
造体が得られるからである。The formed honeycomb structure is heated to a temperature of 70 to 90.
The reason why the drying is performed at a temperature of 80 ° C. and a humidity of 80 to 90% is that if the drying is performed within the above range, a honeycomb structure without cracks can be obtained.
【００１７】また、ハニカム構造体の炭化温度を５００
〜６００℃の温度範囲としたのは、上記の温度範囲は天
然産ピッチを完全に炭化し得る温度であるからであり、
加熱は窒素雰囲気中で１時間以上行なうことが望まし
い。なお、炭化が不十分であるときは次の賦活工程でハ
ニカム構造体に亀裂を発生することがあるので十分に炭
化させることが肝要である。The carbonization temperature of the honeycomb structure is set to 500
The reason for setting the temperature range to 600 ° C. is that the above temperature range is a temperature at which the natural pitch can be completely carbonized,
The heating is desirably performed for one hour or more in a nitrogen atmosphere. When the carbonization is insufficient, a crack may be generated in the honeycomb structure in the next activation step, so it is important to sufficiently carbonize the honeycomb structure.
【００１８】炭化したハニカム構造体を７００〜１００
０℃の温度範囲で賦活するのは７００℃未満では完全な
賦活を行なうのに長時間を要し、また１０００℃を超え
ると活性炭としての比表面積が減少するので好ましくな
いからである。賦活方法としては、薬品賦活法、ガス賦
活法、水蒸気賦活法等どのような賦活法を採用してもよ
い。[0018] The carbonized honeycomb structure is 700 to 100
The activation in the temperature range of 0 ° C. is because if it is less than 700 ° C., it takes a long time to perform complete activation, and if it exceeds 1000 ° C., the specific surface area as activated carbon decreases, which is not preferable. As the activation method, any activation method such as a chemical activation method, a gas activation method, and a steam activation method may be employed.
【００１９】[0019]
【実施例】次に本発明の実施例について述べる。 実施例１ ２００メッシュ以下３２５メッシュ以上の褐炭粉２００
０ｇにメチルセルローズ１５０ｇと天然産ピッチ１００
０ｇ（褐炭粉に対して５０重量％）と水１４００ｍｌを
加えニーダー中で十分に混練し可塑化した後、セル形状
が正方形で１００セル／インチのハニカム金型を通して
ハニカム構造体に成型し、温度８５℃、湿度９０％の雰
囲気条件で４８時間乾燥した後、Ｎ２ガス雰囲気中で６
００℃の温度で２時間焼成して炭化を行なった。Next, an embodiment of the present invention will be described. Example 1 Lignite powder 200 of 200 mesh or less and 325 mesh or more
0g of methylcellulose 150g and natural pitch 100
After adding 0 g (50% by weight based on the brown coal powder) and 1400 ml of water, sufficiently kneading and plasticizing in a kneader, the mixture was molded into a honeycomb structure through a honeycomb mold having a square cell shape of 100 cells / inch. After drying under an atmosphere condition of 85 ° C. and a humidity of 90% for 48 hours, the resultant was dried in an N 2 gas atmosphere for 6 hours.
Carbonization was performed by firing at a temperature of 00 ° C. for 2 hours.
【００２０】次に得られたハニカム構造体をＮ２ガスと
水温９０℃の温水を用いて水蒸気を０．５ｍｌ／ｍｉｎ
（Ｎ２流量当たり）流通させ、８５０℃の温度で５時間
保持して賦活を行ない活性炭ハニカム構造体Ａを得た。Then, the obtained honeycomb structure was steamed at a rate of 0.5 ml / min using N 2 gas and hot water at a water temperature of 90 ° C.
(Per flow rate of N 2 ) and activated at a temperature of 850 ° C. for 5 hours to obtain an activated carbon honeycomb structure A.
【００２１】得られた活性炭ハニカム構造体Ａについ
て、水銀圧入法による細孔構造の測定を行なったとこ
ろ、半径２０オングストローム以上の細孔容積は０．４
７ｍｌ／ｇであり、半径３０００オングストローム以上
の細孔容積は０．２８ｍｌ／ｇであった。また、ガス吸
着によるＢＥＴ法で比表面積を測定したところその値は
１１９０ｍ２／ｇであり、破壊強度については、活性炭
ハニカム構造体を縦横各１ｃｍ、長さ２ｃｍの長方形試
料にカットしたものを、木屋式硬度計を用いて測定した
ところ４．３ｋｇであった。When the pore structure of the obtained activated carbon honeycomb structure A was measured by a mercury intrusion method, the pore volume having a radius of 20 Å or more was 0.4 mm.
The volume of pores having a radius of 3000 Å or more was 0.28 ml / g. When the specific surface area was measured by the BET method by gas adsorption, the value was 1190 m 2 / g. Regarding the breaking strength, the activated carbon honeycomb structure was cut into a rectangular sample 1 cm in length and width and 2 cm in length. It was 4.3 kg when measured using a Kiya hardness meter.
【００２２】またさらに、この試料についてヨード吸着
力を評価した結果、１０１０ｍｇ／ｇであり、ＪＷＷＡ
法によるメチレンブルー脱色力（６５０ｍｍの波長で吸
光度により定量）評価したところ２３０ｍｌであった。 実施例２ 褐炭粉に添加するメチルセルローズを１００ｇ、天然産
ピッチを６００ｇ（褐炭粉に対し３０重量％）、カルボ
ワックス２００ｇと水を１０００ｍｌ加えたこと以外は
実施例１と同様の手順で活性炭ハニカム構造体Ｂを得
た。Further, the iodine adsorption power of this sample was evaluated to be 1010 mg / g.
The methylene blue decolorizing power (determined by absorbance at a wavelength of 650 mm) by the method was 230 ml. Example 2 Activated carbon honeycomb was prepared in the same manner as in Example 1 except that 100 g of methylcellulose, 600 g of natural pitch (30% by weight based on the lignite powder), 200 g of carbowax and 1000 ml of water were added to the lignite powder. Structure B was obtained.
【００２３】得られた活性炭ハニカム構造体Ｂについ
て、実施例１と同様の方法で実施例１と同様の特性値の
測定を行なったところ、半径２０オングストローム以上
の細孔容積は０．５５ｍｌ／ｇ、半径３０００オングス
トローム以上の細孔容積は０．３４ｍｌ／ｇであり、比
表面積は１２３０ｍ２／ｇ、破壊強度は２．７ｋｇであ
った。またヨード吸着力は１０５０ｍｇ／ｇ、メチレン
グリコール脱色力は２５０ｍｌの値を示した。上記の結
果より天然産ピッチの量を３０重量％に減らし、成型助
剤にカルボワックスを使用しても本発明の細孔構造に適
合し、優れた吸着特性を有する活性炭ハニカム構造体を
得ることができることが判かる。 比較例１ 褐炭粉に添加する天然産ピッチの添加量を２０重量％に
したこと以外は実施例１の活性炭ハニカム構造体Ａを得
る手順とほぼ同様の手順で活性炭ハニカム構造体Ｒ−１
を得た。The obtained activated carbon honeycomb structure B was measured for characteristic values in the same manner as in Example 1. The pore volume with a radius of 20 Å or more was 0.55 ml / g. The pore volume with a radius of 3000 Å or more was 0.34 ml / g, the specific surface area was 1230 m 2 / g, and the breaking strength was 2.7 kg. Further, the iodine adsorption power showed a value of 1050 mg / g and the methylene glycol decolorization power showed a value of 250 ml. From the above results, it is possible to obtain an activated carbon honeycomb structure having a reduced amount of natural pitch to 30% by weight and conforming to the pore structure of the present invention even if carbowax is used as a molding aid, and having excellent adsorption characteristics. You can see that it can be done. Comparative Example 1 Activated carbon honeycomb structure R-1 was obtained in substantially the same procedure as that for obtaining activated carbon honeycomb structure A of Example 1, except that the amount of the natural pitch added to the brown coal powder was 20% by weight.
I got
【００２４】得られた活性炭ハニカム構造体Ｒ−１につ
いて、実施例１と同様の方法で実施例１と同様の特性値
の測定を行なったところ、半径２０オングストローム以
上の細孔容積は０．６４ｍｌ／ｇ、半径３０００オング
ストローム以上の細孔容積は０．４２ｍｌ／ｇであり、
比表面積は１２４０ｍ２／ｇ、破壊強度は１．７ｋｇで
あった。また、ヨード吸着力およびメチレングリコール
脱色力を測定したところ、それぞれ１０９０ｍｇ／ｇ、
２７０ｍｌの値を示した。The obtained activated carbon honeycomb structure R-1 was measured for characteristic values in the same manner as in Example 1. The pore volume having a radius of 20 Å or more was 0.64 ml. / G, the pore volume with a radius of 3000 Å or more is 0.42 ml / g,
The specific surface area was 1240 m 2 / g, and the breaking strength was 1.7 kg. When the iodine adsorption power and the methylene glycol decolorization power were measured, they were 1090 mg / g, respectively.
A value of 270 ml was shown.
【００２５】以上の結果より天然産ピッチの添加量を本
発明に定めた添加量３０重量％未満にした場合には、細
孔構造において半径３０００オングストローム以上の細
孔容積が本発明に定めた値よりも大きくなり、それとと
もに破壊強度が著しく低下してしまうことが判かる。 比較例２ 褐炭粉に添加する天然産ピッチの添加量を６０重量％に
したこと以外は実施例１の活性炭ハニカム構造体Ａを得
る手順とほぼ同様の手順で活性炭ハニカム構造体Ｒ−２
を得た。From the above results, when the amount of the natural pitch added is less than 30% by weight as defined in the present invention, the pore volume with a radius of 3000 Å or more in the pore structure becomes the value defined in the present invention. It can be seen that the breaking strength is significantly reduced. Comparative Example 2 Activated carbon honeycomb structure R-2 was obtained in substantially the same procedure as that for obtaining activated carbon honeycomb structure A of Example 1 except that the amount of natural pitch added to the brown coal powder was changed to 60% by weight.
I got
【００２６】得られた活性炭ハニカム構造体Ｒ−２につ
いて、実施例１と同様の方法で実施例１と同様の特性値
の測定を行なったところ、半径２０オングストローム以
上の細孔容積は０．３２ｍｌ／ｇ、半径３０００オング
ストローム以上の細孔容積は０．１８ｍｌ／ｇであり、
比表面積は１１２０ｍ２／ｇ、破壊強度は５．５ｋｇで
あった。また、ヨード吸着力およびメチレングリコール
脱色力を測定したところ、それぞれ９６０ｍｇ／ｇ、２
０５ｍｌの値を示した。The obtained activated carbon honeycomb structure R-2 was measured for characteristic values in the same manner as in Example 1. The pore volume having a radius of 20 Å or more was 0.32 ml. / G, the pore volume with a radius of 3000 Å or more is 0.18 ml / g,
The specific surface area was 1120 m 2 / g, and the breaking strength was 5.5 kg. The iodine adsorption power and methylene glycol decolorization power were measured to be 960 mg / g, 2
It showed a value of 05 ml.
【００２７】以上の結果より、天然産ピッチの添加量を
本発明に定めた添加量の５０重量％を超えた場合には、
細孔構造において半径２０オングストローム以上の細孔
容積、半径３０００オングストローム以上の細孔容積と
もに本発明に定めた値に達せず、それに伴って吸着能が
著しく低下してしまうことが判かる。 比較例３ 従来市販されている活性炭ハニカム構造体（ハニカムセ
ル数５０）について、実施例１と同様の方法で実施例１
と同様の特性値の測定を行なったところ、細孔構造にお
いては半径２０オングストローム以上の細孔容積は０．
３９ｍｌ／ｇ、半径３０００オングストローム以上の細
孔容積は０．１５ｍｌ／ｇであり、比表面積は、１１８
０ｍ２／ｇ、破壊強度は５．５ｋｇであった。またヨー
ド吸着力およびメチレングリコール脱色力の値は、それ
ぞれ９６０ｍｇ／ｇ、２００ｍｌであった。From the above results, when the amount of the natural pitch exceeds 50% by weight of the amount specified in the present invention,
It can be seen that in the pore structure, the volume of pores having a radius of 20 Å or more and the volume of pores having a radius of 3000 Å or more do not reach the values specified in the present invention, and accordingly the adsorption capacity is significantly reduced. Comparative Example 3 A commercially available activated carbon honeycomb structure (having a honeycomb cell number of 50) which was conventionally commercially available was produced in the same manner as in Example 1.
When the same characteristic values were measured, the pore volume with a radius of 20 angstroms or more in the pore structure was 0.1 mm.
The pore volume of 39 ml / g and a radius of 3000 Å or more is 0.15 ml / g, and the specific surface area is 118
0 m 2 / g, and the breaking strength was 5.5 kg. The iodine adsorption power and methylene glycol decolorization power were 960 mg / g and 200 ml, respectively.
【００２８】以上の結果より本発明の細孔構造よりも逸
脱する細孔構造を有する既存の市販活性炭ハニカム構造
体は吸着能および脱色能において本発明品よりも遥かに
劣る値を示すものであることが判かる。また、上記した
実施例および比較例を通じて云えることは、本発明の細
孔構造を有する活性炭ハニカム構造体は破壊強度、比表
面積、吸着能等の特性値を全て満足するものであるのに
対し、細孔構造が本発明の範囲外にある場合には、強度
面や吸収能の面において若干の問題があり実用性におい
て劣ると云うことである。なお、参考に資するため上記
実施例並びに比較例における特性値測定結果を表１に纏
めて示す。From the above results, the existing commercial activated carbon honeycomb structure having a pore structure deviating from the pore structure of the present invention shows much lower values in the adsorptive capacity and the decolorizing ability than the product of the present invention. You can see that. Further, it can be said through the above Examples and Comparative Examples that the activated carbon honeycomb structure having a pore structure of the present invention satisfies all the characteristic values such as breaking strength, specific surface area, and adsorption ability. On the other hand, when the pore structure is out of the range of the present invention, there are some problems in terms of strength and absorption capacity, and the practicality is inferior. In addition, the characteristic value measurement results in the above Examples and Comparative Examples are summarized in Table 1 for reference.
【００２９】[0029]
【表１】 ─────────────────────────────────── 実施例１ 実施例２ 比較例１ 比較例２ 比較例３ ─────────────────────────────────── 供試構造体記号 Ａ Ｂ Ｒ−１ Ｒ−２ 市販品 ─────────────────────────────────── ハニカムセル数 １００ １００ １００ １００ ５０ ─────────────────────────────────── 細孔容積（ｍｌ／ｇ） 半径２０オング ストローム以上 ０．４７ ０．５５ ０．６４ ０．３２ ０．３９ 半径３０００オン グストローム以上 ０．２８ ０．３４ ０．４２ ０．１８ ０．１５ ─────────────────────────────────── 比表面積（ｍ２／ｇ） １１９０ １２３０ １２４０ １１２０ １１８０ ─────────────────────────────────── 破壊強度（ｋｇ） ４．３ ２．７ １．７ ５．５ ５．５ ─────────────────────────────────── ヨード吸着力 １０１０ １０５０ １０９０ ９８０ ９６０ （ｍｇ／ｇ） ─────────────────────────────────── メチレンブルー脱色力 ２３０ ２５０ ２７０ ２０５ ２００ （ｍｌ） ───────────────────────────────────[Table 1] ─────────────────────────────────── Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 記号 Test structure symbol ABR-1R -2 Commercial product {Honeycomb cell number 100 100 100 100 50} ──────────────────────────────── Pore volume (ml / g) Radius 20 angstrom or more 0.47 0. 55 0.64 0.32 0.39 Radius 3000 angstrom or more 0.28 0.34 0.42 0.18 0.15 ────────────────────比 Ratio table Product (m 2 / g) 1190 1230 1240 1120 1180 ─────────────────────────────────── breaking strength ( kg) 4.3 2.7 1.7 5.5 5.5 ─────────────────────────────────ヨ ー Iodine adsorption power 1010 1050 1090 980 960 (mg / g) ─────────────────────────────────── Methylene blue decolorizing power 230 250 270 205 200 (ml) ───────────────────────────────────
【００３０】[0030]
【発明の効果】本発明は、触媒担体、吸着剤として優れ
た特性を有する活性炭ハニカム構造体およびその製造方
法を提供し得たものでありその工業的価値は高い。Industrial Applicability The present invention has provided an activated carbon honeycomb structure having excellent properties as a catalyst carrier and an adsorbent and a method for producing the same, and its industrial value is high.
フロントページの続き (56)参考文献 特開 昭62−72509（ＪＰ，Ａ) 特開 昭58−84180（ＪＰ，Ａ) 特開 昭56−168824（ＪＰ，Ａ) 特開 昭49−72192（ＪＰ，Ａ) 特開 平２−175607（ＪＰ，Ａ) 特開 昭62−152533（ＪＰ，Ａ) 特開 昭62−152534（ＪＰ，Ａ) 実開 昭60−74716（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/00 - 20/34 C01B 31/08 Continuation of the front page (56) References JP-A-62-72509 (JP, A) JP-A-58-84180 (JP, A) JP-A-56-168824 (JP, A) JP-A-49-72192 (JP, A) JP-A-2-175607 (JP, A) JP-A-62-152533 (JP, A) JP-A-62-152534 (JP, A) JP-A-60-74716 (JP, U) (58) Field surveyed (Int. Cl. 7 , DB name) B01J 20/00-20/34 C01B 31/08
Claims (4)
０オングストローム以上の細孔容積が０．４５ｍｌ／ｇ
以上で、半径３０００オングストローム以上の細孔容積
が０．２０〜０．３５ｍｌ／ｇである活性炭ハニカム構
造体。1. The pore structure measured by a mercury intrusion method has a radius of 2
0.45 ml / g pore volume of 0 Å or more
As described above, an activated carbon honeycomb structure having a pore volume of 3000 Å or more in radius of 0.20 to 0.35 ml / g.
得るに際し、褐炭粉に有機質成型助剤と炭化付与剤と水
を添加して混練し、ハニカム構造体に押出し成型して乾
燥した後、５００〜６００℃の温度範囲で焼成して炭化
し、次いで７００〜１０００℃の温度範囲で賦活するこ
とを特徴とする活性炭ハニカム構造体の製造方法。2. To obtain the activated carbon honeycomb structure according to claim 1, an organic molding aid, a carbonizing agent and water are added to brown coal powder, kneaded, extruded into a honeycomb structure, and dried. A method for producing an activated carbon honeycomb structure, characterized in that it is fired and carbonized in a temperature range of 500 to 600C, and then activated in a temperature range of 700 to 1000C.
％、軟化温度１２０〜１４０℃の天然産ピッチであり、
該炭化付与剤の添加量が３０〜５０重量％の範囲である
請求項２記載の活性炭ハニカム構造体の製造方法。3. A natural pitch having a carbon content of 10 to 15% by weight and a softening temperature of 120 to 140 ° C.
The method for producing an activated carbon honeycomb structure according to claim 2, wherein the amount of the carbonizing agent added is in the range of 30 to 50% by weight.
２５メッシュ以上の範囲である請求項３記載の活性炭ハ
ニカム構造体の製造方法。4. The brown coal powder has a particle size of 200 mesh or less,
The method for producing an activated carbon honeycomb structure according to claim 3, wherein the size is 25 mesh or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03340071A JP3125808B2 (en) | 1991-11-29 | 1991-11-29 | Activated carbon honeycomb structure and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03340071A JP3125808B2 (en) | 1991-11-29 | 1991-11-29 | Activated carbon honeycomb structure and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05146678A JPH05146678A (en) | 1993-06-15 |
| JP3125808B2 true JP3125808B2 (en) | 2001-01-22 |
Family
ID=18333445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03340071A Expired - Fee Related JP3125808B2 (en) | 1991-11-29 | 1991-11-29 | Activated carbon honeycomb structure and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3125808B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0767947A (en) * | 1993-09-07 | 1995-03-14 | Daiso Co Ltd | Processing method for odor given from marine organism, device and adsorbent therefor |
| US6706658B2 (en) * | 2001-12-21 | 2004-03-16 | Engelhard Corporation | Catalyst for purification of aromatic acids |
| JP5240791B2 (en) * | 2007-09-07 | 2013-07-17 | クラレケミカル株式会社 | Adsorbent and method for producing the same, canister and method for using the same |
| US8691722B2 (en) | 2008-07-03 | 2014-04-08 | Corning Incorporated | Sorbent comprising activated carbon particles, sulfur and metal catalyst |
| JP6863732B2 (en) * | 2016-12-26 | 2021-04-21 | 株式会社マーレ フィルターシステムズ | Honeycomb adsorbent and its manufacturing method and canister |
| CN115671972B (en) * | 2022-09-21 | 2023-06-27 | 保利长大工程有限公司 | Treatment method for waste gas and waste smoke of asphalt station |
-
1991
- 1991-11-29 JP JP03340071A patent/JP3125808B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05146678A (en) | 1993-06-15 |
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