JP2012180273A - Hollow activated carbon - Google Patents
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- JP2012180273A JP2012180273A JP2012107105A JP2012107105A JP2012180273A JP 2012180273 A JP2012180273 A JP 2012180273A JP 2012107105 A JP2012107105 A JP 2012107105A JP 2012107105 A JP2012107105 A JP 2012107105A JP 2012180273 A JP2012180273 A JP 2012180273A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000002994 raw material Substances 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000000465 moulding Methods 0.000 claims abstract description 26
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- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 15
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- 241001330002 Bambuseae Species 0.000 claims abstract description 15
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 15
- 239000011425 bamboo Substances 0.000 claims abstract description 15
- 229920005610 lignin Polymers 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000002361 compost Substances 0.000 claims abstract description 5
- 239000010802 sludge Substances 0.000 claims abstract description 5
- 240000002834 Paulownia tomentosa Species 0.000 claims abstract description 3
- 241000218645 Cedrus Species 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000012778 molding material Substances 0.000 claims description 4
- 102000006835 Lamins Human genes 0.000 claims description 2
- 108010047294 Lamins Proteins 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 210000005053 lamin Anatomy 0.000 claims description 2
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- 244000043261 Hevea brasiliensis Species 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 21
- 238000001994 activation Methods 0.000 abstract description 17
- 238000003763 carbonization Methods 0.000 abstract description 17
- 230000004913 activation Effects 0.000 abstract description 9
- 238000000197 pyrolysis Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 2
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- 238000004519 manufacturing process Methods 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 230000001877 deodorizing effect Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000007858 starting material Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 244000274847 Betula papyrifera Species 0.000 description 1
- 235000009113 Betula papyrifera Nutrition 0.000 description 1
- 235000009109 Betula pendula Nutrition 0.000 description 1
- 235000010928 Betula populifolia Nutrition 0.000 description 1
- 235000002992 Betula pubescens Nutrition 0.000 description 1
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- 244000290594 Ficus sycomorus Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002531 Rubberwood Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- Y02W30/78—Recycling of wood or furniture waste
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- Treatment Of Sludge (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
本発明は、吸着効率の高い新規な中空活性炭等に関するものである。 The present invention relates to a novel hollow activated carbon having high adsorption efficiency.
活性炭は脱臭装置等に充填されて使用され、大型の脱臭処理施設から家庭用の小型の脱臭機器に至るまで、臭気の除去という用途に広く利用されている。 Activated carbon is used by being filled in a deodorizing apparatus or the like, and is widely used for removing odors from large deodorizing treatment facilities to small household deodorizing equipment.
活性炭はペレット状と呼ばれる略円柱状のものが一般的であるが、内部を軸方向にくり抜いて貫通孔を設けたものや、内部に十字状のリブが構成された中空状の構造が知られている(例えば、特許文献1、2)。これらの構造は圧力損失を低減することができるため、脱臭風量を大きくすることができる。
Activated carbon is generally in the shape of a column called a pellet, but it is known to have a hollow structure with a through-hole by hollowing out the inside in the axial direction and a cross-shaped rib inside. (For example,
一般に、圧力損失の低い活性炭を製造するには、ペレット状活性炭の場合では、外径を太くする方法が考えられる。しかし、外径を太くすると、賦活ガスが内部に到達しにくいため、賦活時間が長くなる結果全体の大きさが小さくなる。これを防ぐために賦活時間を短くすると結果吸着効率が低下する。そこで、吸着性能を上げるために、賦活ガスを内部まで到達させるために、内部を中空状にするという発想が生まれるのである。 In general, in order to produce activated carbon with low pressure loss, in the case of pellet-like activated carbon, a method of increasing the outer diameter can be considered. However, when the outer diameter is increased, the activation gas is difficult to reach the inside, so that the activation time becomes longer and the overall size becomes smaller. If the activation time is shortened to prevent this, the resulting adsorption efficiency decreases. Then, in order to raise adsorption performance, in order to make activation gas reach the inside, the idea of making the inside hollow is born.
ペレット状活性炭は、現在市販されているもので最大7mmφの直径を有し、長さが5mm〜30mm程度のペレット状であるが、内部を軸方向にくり抜いて中空状にすると、賦活工程において賦活ガスが内部に到達しやすいため、賦活時間を短縮して吸着性能を高めることができる。 Pelletized activated carbon is currently commercially available and has a maximum diameter of 7 mmφ and is approximately 5 mm to 30 mm in length. However, when the inside is hollowed out in the axial direction, it is activated in the activation process. Since the gas easily reaches the inside, the activation time can be shortened to enhance the adsorption performance.
一般に、活性炭の性能指標のうち代表的なものは、吸着効率と圧力損失と強度がある。本発明において、吸着効率とは、特定の有機物質(例えばベンゼン)の吸着量で評価される指標を意味する。圧力損失とは、ガス線速度LV(Line Verosity)に対する圧力損失ΔPで表されるもので、脱臭風量を評価するための指標を意味する。圧力損失が高いことは、同じ能力の脱臭ファンを用いた場合には風量が小さくなることを意味する。強度とは、活性炭自体の物理的な破壊強度、すなわち壊れにくさを表す指標を意味する。 In general, typical performance indexes of activated carbon include adsorption efficiency, pressure loss, and strength. In the present invention, the adsorption efficiency means an index evaluated by the amount of adsorption of a specific organic substance (for example, benzene). The pressure loss is expressed by the pressure loss ΔP with respect to the gas linear velocity LV (Line Verosity), and means an index for evaluating the amount of deodorized air. A high pressure loss means that the air volume is reduced when a deodorizing fan having the same capacity is used. The strength means an index representing the physical breaking strength of activated carbon itself, that is, the resistance to breaking.
従来の中空活性炭はいずれも活性炭粉末をバインダーで固めることによって製造されるものであり、圧力損失を低減することができる反面、強度が小さくもろかった。そのため一回だけしか使用できず、再生して繰り返し何度も使用することができなかった。 All of the conventional hollow activated carbons are produced by solidifying activated carbon powder with a binder, and the pressure loss can be reduced, but the strength is small and brittle. Therefore, it could be used only once, and it could not be replayed and used repeatedly.
本発明は、吸着効率が高く、圧力損失が小さく、かつ、強度の大きい、理想的な活性炭を提供することを目的としてなされたものであり、特に、従来の吸着量及び圧力損失を維持しながら、繰り返し再生して使用可能な程度までその強度を十分に大きくすることを主たる技術的課題とするものである。 The present invention has been made for the purpose of providing an ideal activated carbon having high adsorption efficiency, low pressure loss, and high strength. In particular, while maintaining the conventional adsorption amount and pressure loss. Therefore, the main technical problem is to sufficiently increase the strength to the extent that it can be repeatedly reproduced and used.
本発明に係る中空活性炭は、従来のように活性炭粉末をバインダーによって「固める」のではなく、予め原料の段階から中空状に成型し、得られた成型材を後に活性炭化するという方法によって作られる。本明細書では、内部に中空部分が形成された構造を備えた活性炭を総称して「中空活性炭」というが、後述するようにこれには多くの実施形態が考えられる。 The hollow activated carbon according to the present invention is made by a method in which activated carbon powder is not solidified with a binder as in the prior art, but is formed into a hollow shape from the raw material stage in advance, and the obtained molding material is activated carbonized later. . In this specification, activated carbon having a structure in which a hollow portion is formed inside is collectively referred to as “hollow activated carbon”, but many embodiments can be considered as described later.
本発明に係る中空活性炭は、複数の貫通孔を備えた成型原料を同一反応炉内において連続的に炭化・乾留及び賦活することにより得られたことを特徴とする。この中空活性炭は、複数の貫通孔が設けられているため、圧力損失を小さくすることができる。また、成型原料の段階で貫通孔が設けられ、炭化・乾留及び賦活する一連の工程を経ることで、賦活時間を短縮して中空活性炭の寸法の減少を小さくすることができ、従来の中空活性炭よりも強度を大きくすることができる。 The hollow activated carbon according to the present invention is characterized by being obtained by continuously carbonizing, carbonizing and activating a molding material having a plurality of through holes in the same reaction furnace. Since this hollow activated carbon is provided with a plurality of through holes, the pressure loss can be reduced. In addition, through holes are provided at the molding raw material stage, and through a series of steps of carbonization, carbonization and activation, the activation time can be shortened and the reduction in the size of the hollow activated carbon can be reduced. The strength can be increased.
この成型原料は、出発材料として粉末原料を使用してもよく、具体的には、オガ粉、竹粉、オカラ、コーヒーかす、堆肥、製紙スラッジなどが含まれる。また、完成品の強度をより大きくするために、必要により、粉末リグニンを加えてもよい。 This molding raw material may use a powder raw material as a starting material, and specifically includes oga powder, bamboo powder, okara, coffee grounds, compost, papermaking sludge and the like. Further, in order to increase the strength of the finished product, powder lignin may be added as necessary.
また、この成型原料は、出発材料として木片原料を使用してもよい。この木片原料は、炭化・乾留及び賦活工程によって活性炭となりうる原料全般を指す広義に解すべきものであり、例えば、杉、檜、ラワン材、ゴムの木、竹、ラミン、桐など、比較的空隙率の大きい木質が好ましい。すでに活性炭化されているものは「木片原料」には該当しない。 Moreover, this molding raw material may use a wood chip raw material as a starting material. This wood chip raw material should be broadly understood to indicate all raw materials that can be activated carbon by carbonization, carbonization and activation processes. For example, cedar, firewood, lauan, rubber wood, bamboo, lamin, paulownia, etc. High quality wood is preferred. Those that have already been activated carbonized do not fall under “wood chip material”.
この中空活性炭は、具体的には、加熱炉内に成型原料を設置し、酸素を遮断した状態で昇温し、この状態を一定時間保持する工程を段階的に繰り返すことによって、水素及び酸素原子を脱離する炭化・乾留工程と、その後更に加熱すると共に水を注入することで水性化反応を生ぜしめる賦活工程とを連続的にかつ同一の反応炉内で行うことにより得られる。従来は炭化・乾留工程と、賦活工程とが別々の炉で実施されることが通常であったが、このように本発明では、これらの工程を同一の反応炉内で連続的に行うことができる。 Specifically, this hollow activated carbon has hydrogen and oxygen atoms by repeating the process of placing the molding raw material in a heating furnace, raising the temperature in a state where oxygen is shut off, and maintaining this state for a certain period of time. The carbonization / dry distillation process for desorbing water and the activation process for generating an aqueous reaction by injecting water after further heating are performed continuously and in the same reactor. Conventionally, the carbonization / dry distillation process and the activation process are usually performed in separate furnaces. In the present invention, these processes can be continuously performed in the same reactor. it can.
本発明に係る中空活性炭によると、高い吸着性能と低い圧力損失を維持しながら従来の中空活性炭よりも強度を大きくすることができ、繰り返し再生して使用することができる。 According to the hollow activated carbon according to the present invention, the strength can be increased as compared with the conventional hollow activated carbon while maintaining high adsorption performance and low pressure loss, and it can be regenerated and used repeatedly.
図1は、本実施形態の中空活性炭を製造するための工程を示す図である。各ステップの詳細は後述するが、ここでは全体的な流れについて説明する。本実施形態の中空活性炭を製造する製造方法は、予め原料の段階から中空状に成型し、得られた成型材を後に活性炭化するという方法によって作られることが特徴である。 FIG. 1 is a diagram illustrating a process for producing the hollow activated carbon of the present embodiment. Although details of each step will be described later, an overall flow will be described here. The production method for producing the hollow activated carbon of the present embodiment is characterized in that it is produced by a method in which the hollow activated carbon is molded in advance from the raw material stage, and the obtained molding material is activated carbonized later.
ステップS1は、成型工程である。この工程を行う目的は、本発明における出発材料として用いる「活性炭化される前の原料」を予め中空状に成型するためである。出発材料にどのような原料を用いるかによって、大きく2つの方法に分けられる。すなわち、
(1)粉末原料を用いる場合
(2)木片原料を用いる場合
の2つである。なお、出発材料は異なっても成型工程後の原料(本明細書では、これを「成型原料」という。)の形状はほぼ同じになる。但し、大きさは異なっていてもよい。
Step S1 is a molding process. The purpose of performing this step is to previously mold the “raw material before being activated carbonized” used as a starting material in the present invention into a hollow shape. Depending on what raw material is used for the starting material, there are roughly two methods. That is,
(1) When using powder raw material (2) When using wood chip raw material. In addition, even if the starting materials are different, the shape of the raw material after the molding step (this is referred to as “molding raw material” in this specification) is substantially the same. However, the size may be different.
(1)の粉末原料を用いる場合は、オガ粉、竹粉、オカラ、コーヒーかす、堆肥、製紙スラッジなどの粉末原料を中空状に押し出し成型する工程がこれにあたる。押し出し成型の温度条件は常温から200℃までの温度範囲で行うことが好ましい。(2)の木片原料の場合は、杉や檜などの木材を予め中空状に金型などを用いて機械加工して成型する工程がこれにあたる。 When the powder raw material of (1) is used, this is a process of extruding and molding powder raw materials such as oga powder, bamboo powder, okara, coffee grounds, compost, and paper sludge into a hollow shape. The temperature condition of the extrusion molding is preferably performed in a temperature range from room temperature to 200 ° C. (2) In the case of a wood chip material, this corresponds to a process in which wood such as cedar and straw is previously machined into a hollow shape using a mold or the like.
図2(a)〜(c)は、ステップS1の成型工程後に得られる成型原料1の形状の一例を示している。図2(a)は成型工程後の斜視図であり(b)は正面図、(c)は断面図である。これらの図より、成型原料1は、全体が略円柱状(ペレット状)であって直径D1の底面に軸方向に沿って直径D2の貫通孔2が形成されていることが分かる。柱の長さをLとすると、Lは概ね5mm〜30mm程度である。従来の製法と異なり、この段階ではまだ活性炭化されていない。
2A to 2C show an example of the shape of the forming
なお、製造のしやすさ等の理由からペレット状が作りやすいが、金型などを工夫すれば角柱など他の形状も可能である。そのため、後述の実施例では図3に示すような角柱に貫通孔を設けた後活性炭化した中空活性炭を一例試作し、その性能評価を行っている。 In addition, although it is easy to make a pellet shape for reasons such as ease of manufacturing, other shapes such as a prism can be formed by devising a mold or the like. Therefore, in the examples described later, a hollow activated carbon activated by carbonization after providing a through hole in a prism as shown in FIG. 3 is prototyped and its performance is evaluated.
図3(a)〜(c)は、図2のペレット状を角柱状に変更した場合の例を示している。図3(a)は成型工程後の斜視図であり(b)は正面図、(c)は断面図である。これらの図より、成型原料3は、全体が略角柱状であって一辺Sの正方形の底面に軸方向に沿って直径D2の貫通孔4が形成されている。柱の長さをLとすると、Lは概ね5mm〜30mm程度である。従来の製法と異なり、この段階ではまだ活性炭化されていない。
3A to 3C show an example in which the pellet shape of FIG. 2 is changed to a prism shape. 3A is a perspective view after the molding step, FIG. 3B is a front view, and FIG. 3C is a cross-sectional view. From these figures, the molding
ステップS2は、炭化・乾留工程である。この工程を行う目的は、ステップS1で得られた成型原料を活性炭化するためにまず原料をグルコース分解させるためである。これによって水素(H)及び酸素(O)その他の不純物を脱離して、緻密な炭素構造が得られる。炭化と乾留は厳密には異なる意味を持つが、共に酸素(O2)を遮断した状態で一定時間毎に昇温する工程である点で共通するので、本明細書では両者を区別せず、「炭化・乾留工程」と表記する。 Step S2 is a carbonization / dry distillation process. The purpose of performing this process is to first subject the raw material to glucose decomposition in order to carbonize the molding raw material obtained in step S1. Thereby, hydrogen (H), oxygen (O) and other impurities are eliminated, and a dense carbon structure is obtained. Strictly speaking, carbonization and dry distillation have different meanings, but both are common in that the temperature is raised every certain time in a state where oxygen (O 2 ) is shut off, so in this specification, the two are not distinguished. It is expressed as “carbonization / dry distillation process”.
ステップS3は、賦活工程である。この工程を行う目的は、ステップS2で炭化・乾留された成型原料に水(H2O)を注入することで水性化反応を行うためである。これによって緻密な炭素構造から二酸化炭素(CO2)の形で炭素が離脱し、多孔質の炭素構造が得られる。この工程は一般に賦活工程と呼ばれている。 Step S3 is an activation process. The purpose of performing this step is to perform an aqueous reaction by injecting water (H 2 O) into the molding raw material carbonized and carbonized in step S2. As a result, carbon is released from the dense carbon structure in the form of carbon dioxide (CO 2 ), and a porous carbon structure is obtained. This process is generally called an activation process.
ステップS4は、篩い分け工程である。この工程を行う目的は、ステップ3で得られた原料を大きさや品質などの基準で篩い分けするためである。
Step S4 is a sieving step. The purpose of performing this process is to screen the raw material obtained in
ちなみに、木片原料を出発材料とする従来の製造方法では、出発材料となる原料(例えば、ヤシガラや石炭など)を粉砕した後、篩い分けし、炭化・乾留した後、再度篩い分けをし、その後、賦活する。最後にもう一度篩い分けを行って製品が完成する。このように、工程が多くしかも篩い分け作業が3回もあるので、最終製品は原料の1/9乃至1/10の量となることが通常であった。これに対し、本実施形態の中空活性炭を製造する製造方法では、篩い分け工程はたった1回でよく、歩留まりが極めて高い。 By the way, in the conventional manufacturing method using wood chip raw material as a starting material, the starting material (for example, coconut husk and coal) is pulverized, sieved, carbonized and carbonized, and then sieved again. , Activate. Finally, another sieving is performed to complete the product. Thus, since there are many steps and the sieving operation is performed three times, the final product is usually 1/9 to 1/10 of the raw material. On the other hand, in the production method for producing the hollow activated carbon of the present embodiment, the sieving step is only required once, and the yield is extremely high.
本実施形態の中空活性炭を製造する製造方法では、ステップS2及びステップS3の間に篩い分け工程が不要となるため、いずれも同一の反応炉で連続的に行うことができる。これは工程を大幅に簡略化させることに大きく寄与する。 In the production method for producing the hollow activated carbon according to the present embodiment, a sieving step is not necessary between Step S2 and Step S3, and both can be performed continuously in the same reactor. This greatly contributes to greatly simplifying the process.
次に、具体的なヒートカーブについて説明する。このヒートカーブは後述する実施例で説明するサンプルを製造した際に用いたものである。 Next, a specific heat curve will be described. This heat curve is used when a sample described in an example described later is manufactured.
図4は、ステップS2とステップS3の工程における加熱炉内の温度の時間経過を示すヒートカーブの一例である。横軸は経過時間、縦軸は炉内温度をそれぞれ示している。但し、厳密なものではなく、実際には温度制御装置の性能に依存する設定値とのズレは許容するものとする。 FIG. 4 is an example of a heat curve showing the passage of time of the temperature in the heating furnace in the steps S2 and S3. The horizontal axis represents the elapsed time, and the vertical axis represents the furnace temperature. However, this is not a strict one, and in fact, a deviation from the set value depending on the performance of the temperature control device is allowed.
この図に示すように、酸素(O2)を遮断した状態で、約3時間かけて300℃まで昇温し、次に、300℃を3時間維持する。更に、1時間かけて400℃まで昇温し、400℃を3時間維持する。更に、2時間かけて600℃まで昇温し、3時間維持する。ここまでの工程が、ステップS2で説明した炭化・乾留工程である。 As shown in this figure, with the oxygen (O 2 ) shut off, the temperature is raised to 300 ° C. over about 3 hours, and then 300 ° C. is maintained for 3 hours. Further, the temperature is raised to 400 ° C. over 1 hour and maintained at 400 ° C. for 3 hours. Further, the temperature is raised to 600 ° C. over 2 hours and maintained for 3 hours. The process so far is the carbonization / dry distillation process described in step S2.
従来はここで一旦篩い分けのために降温していたが、本発明ではそのまま温度を上げて賦活工程に入る。炭化・乾留工程の後、更に3時間かけて800℃まで昇温し、800℃に達した後、約28時間保温する。賦活工程中は一定間隔で水(H2O)を注入する。これによって水性化反応が起こり、多孔質構造が得られる。 Conventionally, the temperature is once lowered for sieving here, but in the present invention, the temperature is increased as it is and the activation process is started. After the carbonization / dry distillation step, the temperature is further raised to 800 ° C. over 3 hours, and after reaching 800 ° C., the temperature is kept for about 28 hours. Water (H 2 O) is injected at regular intervals during the activation process. As a result, an aqueous reaction occurs, and a porous structure is obtained.
なお、ヒートカーブはこれ以外のパターンも当然考えられるので、図4は本実施形態の中空活性炭を製造する製造方法の一例を示したものにすぎない。 In addition, since a heat curve can also consider patterns other than this, FIG. 4 only showed an example of the manufacturing method which manufactures the hollow activated carbon of this embodiment.
(実施例)
表1は、製造条件の異なる種々の活性炭サンプルについて、仕上がり形状、ベンゼン吸着量、強度、圧力損失を調べた結果を示している。なお、形状は以下の通りとした。
本発明の実施例として、
・ペレット状の活性炭に貫通孔を設けたもの(ペレット状中空炭)
・角柱状の活性炭に貫通孔を設けたもの(角状中空炭)
比較例として、
・ペレット状の活性炭(ペレット炭)
・ペレット炭に貫通孔を設けその内部に十字状のリブが形成されたもの(リブ付中空炭)
・薄片状のもの(破砕炭)
(Example)
Table 1 shows the results of examining the finished shape, benzene adsorption amount, strength, and pressure loss for various activated carbon samples having different production conditions. The shape was as follows.
As an example of the present invention,
・ Pellet-shaped activated carbon with through-holes (pellet-shaped hollow charcoal)
・ A prismatic activated carbon with through holes (square hollow charcoal)
As a comparative example,
・ Pellets in activated carbon (pellet charcoal)
・ Pellet charcoal with through-holes with cross-shaped ribs formed inside (ribboned hollow charcoal)
・ Flame (crushed charcoal)
表1に示す各サンプルA〜Lの詳細は、以下の通りである。
[粉末原料](本発明)
A オガ粉100%、成型原料の寸法が、底面外径D1=25mmφ、底面内径=10mmφ、長さL=25mmのペレット状中空炭
B オガ粉:竹粉=4:1(重量比)、成型原料の寸法が、底面外径D1=25mmφ、底面内径=10mmφ、長さL=25mmのペレット状中空炭
C オガ粉100%、成型原料の寸法が、底面外径D1=20mmφ、底面内径=8mmφ、長さL=20mmのペレット状中空炭
D オガ粉:竹粉=1:1(重量比)、成型原料の寸法が、底面外径D1=15mmφ、底面内径=6mmφ、長さL=15mmのペレット状中空炭
Details of the samples A to L shown in Table 1 are as follows.
[Powder material] (Invention)
A Pellet hollow charcoal with 100% sawdust, bottom outer diameter D1 = 25mmφ, bottom inner diameter = 10mmφ, length L = 25mm B Butter: bamboo powder = 4: 1 (weight ratio), molding The raw material dimensions are the bottom outer diameter D1 = 25mmφ, the bottom inner diameter = 10mmφ, the length L = 25mm pellet-shaped hollow charcoal C 100% powder, the molding raw material dimensions are the bottom outer diameter D1 = 20mmφ, the bottom inner diameter = 8mmφ , Length L = 20 mm pellet-shaped hollow charcoal D Oga powder: bamboo powder = 1: 1 (weight ratio), the dimensions of the molding raw material are bottom outer diameter D1 = 15 mmφ, bottom inner diameter = 6 mmφ, length L = 15 mm Pelleted hollow charcoal
[木片原料](本発明)
E 杉材を金型により加工し、成型原料の寸法が、底面外径D1=25mmφ、底面内径=10mmφ、長さL=25mmのペレット状中空炭
F ラワン材を金型により加工し、成型原料の寸法が、底面外径D1=12mmφ、底面内径=4mmφ、長さL=12mmのペレット状中空炭
G 白樺材を金型により加工し、底面が25mm×25mmの角柱状で底面内径=10mmφの貫通孔を設けた長さL=16mmの角状中空炭
[Raw material] (Invention)
E Cedar wood is processed with a mold, and the molding raw material has a pellet-shaped hollow charcoal with a bottom outer diameter D1 = 25 mmφ, a bottom inner diameter = 10 mmφ, and a length L = 25 mm. Is a pellet-shaped hollow charcoal G having a bottom outer diameter D1 = 12 mmφ, a bottom inner diameter = 4 mmφ, and a length L = 12 mm. Square hollow charcoal with a length L = 16 mm provided with through holes
上記サンプルのうち、サンプルA〜Fの形状は概ね図2に示すペレット状中空炭、サンプルGの形状は概ね図3に示す角状中空炭であり、いずれも内径D2の貫通孔が設けられている。 Among the above samples, the shapes of samples A to F are generally pelleted hollow charcoal as shown in FIG. 2, and the shape of sample G is generally rectangular hollow charcoal as shown in FIG. 3, each having a through hole having an inner diameter D2. Yes.
[比較例](従来例)
以下の比較例H〜Lはいずれも従来の製法で製造したものである。
H ヤシガラ活性炭を約4mm〜5mmの薄片状にしたヤシガラ破砕炭
I 仕上がり形状が約4mmφの石炭ペレット炭、貫通孔なし
J 仕上がり形状が約7mmφの石炭ペレット炭、貫通孔なし
K ヤシガラ活性炭粉末の粉末をバインダーで固めて造粒し、貫通孔を設けたペレット状中空炭(いわゆる「マカロニ炭(製品名及び登録商標)」)
L ヤシガラ活性炭粉末の粉末をバインダーで固めて造粒し、貫通孔と十字状のリブを設けたリブ付中空炭(いわゆる「マカロニ十字炭(製品名及び登録商標)」)
[Comparative example] (Conventional example)
The following Comparative Examples H to L are all manufactured by a conventional manufacturing method.
H Coconut husk activated carbon made into thin flakes of about 4 mm to 5 mm I Coal pellet charcoal with a finished shape of about 4 mmφ, no through holes J Coal pellet charcoal with a finished shape of about 7 mmφ, no through holes K Powder of coconut shell activated carbon powder Pelletized hollow charcoal that has been granulated by solidifying with a binder (so-called “macaroni charcoal (product name and registered trademark)”)
L Coconut charcoal powder is solidified with a binder, granulated, and ribbed hollow charcoal (so-called “macaroni cross charcoal (product name and registered trademark)”) provided with through-holes and cross-shaped ribs
(結果)
なお、表1における「形状」は、ペレット状中空炭、角状中空炭、ペレット炭、リブ付中空炭、破砕炭の概略形状を示している。また、「仕上がり形状」とは、本発明においては成型原料を活性炭化した後の最終形状の寸法を、比較例においては活性炭化された最終製品を篩い分けして得られた形状の寸法を指す。また、ベンゼン吸着量は吸着性能を表す指標であり、数値が大きいほど吸着性能が高いことを示す。また、強度とは、木屋式硬度計で測定した測定値であり、数値が大きいほど強度が大きいことを示す。 In addition, "shape" in Table 1 has shown the schematic shape of pellet-shaped hollow charcoal, square hollow charcoal, pellet charcoal, hollow charcoal with a rib, and crushed charcoal. In addition, the “finished shape” in the present invention refers to the size of the final shape after the active carbonization of the molding raw material, and in the comparative example, refers to the size of the shape obtained by sieving the activated carbonized final product. . Further, the benzene adsorption amount is an index representing the adsorption performance, and the larger the value, the higher the adsorption performance. Further, the strength is a measured value measured with a Kiyama-type hardness meter, and indicates that the larger the numerical value, the higher the strength.
図5は、種々の活性炭の圧力損失を調べたグラフを示している。サンプルは表1のA、D、H、I、J、Lとした。このグラフは両対数で表示され、横軸はガス線速度LV[m/s]、縦軸は圧力損失ΔP[kPa:H2O/m・Bed]を表している。表2は、図5から読み取ったガス線速度LVの大きさが、0.1、0.3及び1[m/s]の3点における圧力損失の値を示している。 FIG. 5 is a graph showing the pressure loss of various activated carbons. The samples were A, D, H, I, J, and L in Table 1. This graph is displayed as a logarithm, the horizontal axis represents the gas linear velocity LV [m / s], and the vertical axis represents the pressure loss ΔP [kPa: H 2 O / m · Bed]. Table 2 shows pressure loss values at three points where the magnitude of the gas linear velocity LV read from FIG. 5 is 0.1, 0.3, and 1 [m / s].
(評価)
−吸着性能について−
吸着性能についてはラワン材(サンプルF)が良好であり、白樺(サンプルG)が若干低かった。また、粉末原料についていえば、竹粉を一定量加えるとやや吸着量が増加する傾向が見られたが、全体的にそれほど顕著な差異はみられなかった。もっとも、従来の製法で作られたサンプルKやサンプルLより、吸着性能が高いことが分かった。
(Evaluation)
-Adsorption performance-
Regarding the adsorption performance, the Lauan material (Sample F) was good, and the white birch (Sample G) was slightly low. In addition, regarding the powder raw material, when a certain amount of bamboo powder was added, the amount of adsorption slightly increased, but overall there was no significant difference. But it turned out that adsorption performance is higher than the sample K and the sample L which were made by the conventional manufacturing method.
−強度について−
粉末原料については原料構成比の等しいものの比較から、サイズが大きいものほど強度も大きくなる傾向が明らかとなった。また、オガ粉と竹粉の混合比の比較から、吸着量は竹粉を加えるほど増加するが、反面強度が低下することも明らかとなった。これは、オガ粉にはバインダーとしての働きを持つリグニンが含まれているが、竹粉にはリグニンが殆ど含まれていないためと考えられる。換言すると、粉末原料については、強度を高めるためにリグニンが有効であることが分かる。この意味において、粉末原料として可能なものは、リグニンを含む有機物の粉末(これには、「粉末リグニン」を混合した粉末も含まれる。)が適用できる。具体的には、オガ粉、竹粉、オカラ、コーヒーかすなどに必要な場合は粉末リグニンを添加したものである。その他の可能性としては、堆肥や製紙スラッジなども有効である。実験で試作したサンプルA、C、D及びGについては、いずれも再生利用可能な程度に十分な強度を備えていた。
-Strength-
From the comparison of powder raw materials having the same raw material composition ratio, it became clear that the larger the size, the higher the strength. Moreover, it became clear from the comparison of the mixing ratio of oga powder and bamboo powder that the amount of adsorption increases as bamboo powder is added, but the strength decreases. This is probably because oga powder contains lignin that functions as a binder, but bamboo powder contains almost no lignin. In other words, it is understood that lignin is effective for increasing the strength of the powder raw material. In this sense, organic powders containing lignin (including powders mixed with “powder lignin”) can be applied as possible powder raw materials. Specifically, powder lignin is added when necessary for oga powder, bamboo powder, okara, coffee grounds and the like. Other possibilities include compost and papermaking sludge. Samples A, C, D, and G that were experimentally produced had sufficient strength to be recyclable.
−圧力損失について−
図5及び表2によると、風量を大きくするほど圧力損失が大きくなる傾向が読み取れるが、特に試料1(オガ粉100%)及び試料2(オガ粉:竹粉=1:1)及びリブ付中空炭(それぞれ、サンプルA、D、Lに対応)は、いずれも圧力損失が極めて小さいことが読み取られる。
-Pressure loss-
According to FIG. 5 and Table 2, it can be seen that the pressure loss tends to increase as the air volume increases, but in particular, sample 1 (100% sawdust), sample 2 (slag flour: bamboo powder = 1: 1) and hollow with ribs. It is read that charcoal (corresponding to samples A, D, and L, respectively) has a very small pressure loss.
−まとめ−
以上の実験により、吸着性能と強度と圧力損失という3つの評価基準のそれぞれが数値で表されたが、これらの全てが平均的に良好だったのは、サンプルA、C、D及びGであった。
-Summary-
From the above experiments, each of the three evaluation criteria of adsorption performance, strength, and pressure loss was expressed numerically, but all of these were average on samples A, C, D, and G. It was.
(中空活性炭の実施例)
活性炭化後に形状を加工することは殆ど不可能であるため、従来は完成した活性炭を形状・寸法毎に篩い分けして分別し希望の形状を得ていたが、この方法は、歩留まりが非常に低かった。これに対し、杉や檜などの木片原料自体を出発材料とする場合、活性炭化する前の状態の木を加工するため、加工の自由度は非常に大きく、よって、様々な形状が可能である。
(Example of hollow activated carbon)
Since it is almost impossible to process the shape after activated carbonization, conventionally, the finished activated carbon was sieved for each shape and size to obtain the desired shape, but this method has a very high yield. It was low. On the other hand, when the raw material itself of wood such as cedar and persimmon is used as a starting material, since the wood before active carbonization is processed, the degree of freedom of processing is very large, and thus various shapes are possible. .
図6は、本実施形態の中空活性炭の実施例について説明するための図であり、成型原料の実施態様を例示している。すなわち、図6(a)のように、ペレット状の木片原料5aに複数の貫通孔6aを設けたもの、図6(b)のように、球状の木片原料5bに複数の貫通孔6bを設けたもの、図6(c)のように、ハート型の木片原料5cに複数の貫通孔6cを設けたもの、などが考えられる。その他、図示を省略するが、星形など多くのパターンが考えられる。
Drawing 6 is a figure for explaining the example of hollow activated carbon of this embodiment, and has illustrated the embodiment of the forming raw material. That is, as shown in FIG. 6 (a), a pellet-shaped wood piece
このように木片原料を任意に加工してそこから炭化・乾留工程を行えば、任意の形状の中空活性炭を製造することができる。特に、複数の貫通孔を設けることにより、圧力損失が一層小さくなることはもちろん、更に、賦活時間が短縮化されるため寸法の減少が小さくなるという利点がある。 In this way, if the wood chip raw material is arbitrarily processed and the carbonization / dry distillation process is performed therefrom, a hollow activated carbon having an arbitrary shape can be produced. In particular, by providing a plurality of through holes, the pressure loss can be further reduced, and further, the activation time is shortened, so that there is an advantage that the reduction in size is reduced.
本実施形態の中空活性炭は、吸着効率が高く、圧力損失が小さく、かつ、強度の大きい、理想的な活性炭であり、以下のような産業上の利用可能性を備えている。 The hollow activated carbon of the present embodiment is an ideal activated carbon having high adsorption efficiency, small pressure loss, and high strength, and has the following industrial applicability.
(1)脱臭風量の大きい大型脱臭装置への利用
既設の脱臭装置に充填されている活性炭を本発明に係る中空活性炭に置き換えると設備はそのままで風量が大幅に増大する。従来は風量を増大させる必要が生じた場合はもう一基増設しなければならなかった。
(2)家庭用の分野において、居室用の脱臭機器やエアコンなどの吹き出し口に装着する脱臭カートリッジとしての利用
(3)排ガス対策を可能にした屋上排気ファンなどへの利用
(1) Use for large-sized deodorizing apparatus with large deodorizing air volume When the activated carbon filled in the existing deodorizing apparatus is replaced with the hollow activated carbon according to the present invention, the air volume is greatly increased without changing the facilities. In the past, when it was necessary to increase the air flow, another unit had to be added.
(2) Use as a deodorizing cartridge to be installed in the air outlet of a deodorizing device for a living room or an air conditioner in the field of home use. (3) Use for a rooftop exhaust fan that enables exhaust gas countermeasures.
本実施形態の中空活性炭は、従来の吸着量及び圧力損失を維持しながら、しかも、繰り返し何度も再生できる強度を有しているため、ランニングコストを抑えることができる。従って、本発明が実施された場合の産業上の利用可能性は極めて大きい。 Since the hollow activated carbon of this embodiment has the intensity | strength which can be reproduced | regenerated many times, maintaining the conventional adsorption amount and pressure loss, it can suppress a running cost. Therefore, the industrial applicability when the present invention is implemented is extremely large.
1、3、5 成型原料
2、4、6 貫通孔
1, 3, 5 Molding
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CN105903460A (en) * | 2016-05-09 | 2016-08-31 | 东华大学 | Powdered activated carbon ectopic self generation and regeneration method for hard-degradation organic wastewater treatment |
CN109336106A (en) * | 2018-10-29 | 2019-02-15 | 宿州学院 | A kind of preparation method of bean dregs base nitrogen boron codope porous carbon materials |
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