JP5072001B2 - Oil adsorbent and method for producing the same - Google Patents

Oil adsorbent and method for producing the same Download PDF

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JP5072001B2
JP5072001B2 JP2006042069A JP2006042069A JP5072001B2 JP 5072001 B2 JP5072001 B2 JP 5072001B2 JP 2006042069 A JP2006042069 A JP 2006042069A JP 2006042069 A JP2006042069 A JP 2006042069A JP 5072001 B2 JP5072001 B2 JP 5072001B2
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oil
plant fiber
calcined coke
fiber
carbon material
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JP2007216184A (en
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保 田野
歳隆 藤井
隆 大山
雅規 村上
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Eneos Corp
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JXTG Nippon Oil and Energy Corp
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Description

本発明は油吸着材およびその製造方法に関する。より詳細には、優れた油吸着能を有し、水面上に流出した油や、地上での運送中もしくは貯蔵中に流出した油、あるいは作業現場などで漏出した油を速やかに吸着し、しかも環境に優しく、かつコストの安い油吸着材、およびその製造方法を提供するものである。   The present invention relates to an oil adsorbent and a method for producing the same. More specifically, it has an excellent oil adsorption capacity, and quickly adsorbs oil that has flowed out onto the surface of the water, oil that has been spilled during transportation or storage on the ground, or oil that has leaked from work sites, etc. The present invention provides an oil adsorbent that is environmentally friendly and inexpensive, and a method for producing the same.

従来、オイルタンカーの遭難事故、工場、船舶からの含油廃水や油流出事故などに対して、海洋や港湾、河川などを油汚染から守るために、水面上に浮遊する油を回収除去する目的で、あるいは地上での運送中や貯蔵中に流出したり、作業場などで漏出した油を回収除去する目的で、油吸着材が使用されている。しかしながら、現状の油吸着材は、化学繊維から製造されたものが多く、使用後の廃棄時に焼却処理される場合、ダイオキシン等の有害ガスの発生が考えられ、環境汚染の要因となっている。これらの対応として、ピーナッツ、コーヒー豆等の植物性繊維を粉砕し、しかるのち、パラフィンワックス等をコーティングしたもの(特許文献1参照)、ポリオレフィン系樹脂からなる基材とスターチ類および活性炭を混合し、所定の形状に押し出したのち加熱処理したもの(特許文献2参照)等が提案されている。しかしながら、これらの発明は環境汚染の面では改善されたが、油吸着量、およびコストの面から更に改善が望まれていた。
特開2004−167481号公報 特開2000−51691号公報
For the purpose of recovering and removing oil floating on the water surface to protect the ocean, harbors, rivers, etc. from oil pollution in the past, oil tanker distress accidents, factories, oily wastewater from oil and oil spill accidents, etc. Alternatively, an oil adsorbent is used for the purpose of recovering and removing oil that has been spilled during transportation or storage on the ground or leaked at a work place. However, many of the current oil adsorbents are manufactured from chemical fibers, and when incinerated at the time of disposal after use, generation of harmful gases such as dioxins is considered, which causes environmental pollution. To cope with these problems, plant fibers such as peanuts and coffee beans are pulverized and then coated with paraffin wax or the like (see Patent Document 1), a base material made of polyolefin resin, starches and activated carbon are mixed. In addition, a material that has been extruded into a predetermined shape and then heat-treated (see Patent Document 2) has been proposed. However, although these inventions have been improved in terms of environmental pollution, further improvements have been desired in terms of the amount of adsorbed oil and cost.
Japanese Patent Laid-Open No. 2004-167481 JP 2000-51691 A

本発明はこのような実状に鑑み成されたものであり、油吸着能に優れ、しかも環境に優しく、かつコストの安い油吸着材を提供するものである。   The present invention has been made in view of such a situation, and provides an oil adsorbent that is excellent in oil adsorbing ability, is environmentally friendly, and inexpensive.

すなわち、本発明は、炭素質材料を1000〜1500℃でか焼することにより得られる油吸着用炭素材料、表面の一部または全部が撥水剤でコーティングされた植物繊維、および油吸着用炭素材料と植物繊維間に分散接着する化学繊維からなり、植物繊維に対する油吸着用炭素材料の質量比率が0.3〜0.6であり、油吸着用炭素材料と植物繊維の和に対する化学繊維の質量比率が0.4以下であることを特徴とする油吸着材に関する。   That is, the present invention relates to an oil-adsorbing carbon material obtained by calcining a carbonaceous material at 1000 to 1500 ° C., a vegetable fiber having a part or all of its surface coated with a water repellent, and an oil-adsorbing carbon. It consists of chemical fibers that are dispersed and bonded between the material and the plant fiber, and the mass ratio of the carbon material for oil adsorption to the plant fiber is 0.3 to 0.6, and the chemical fiber to the sum of the carbon material for oil adsorption and the plant fiber The present invention relates to an oil adsorbent characterized by having a mass ratio of 0.4 or less.

また、本発明は、油吸着用炭素材料の粒径が3mm以下であることを特徴とする前記記載の油吸着材に関する。   The present invention also relates to the oil adsorbent described above, wherein the oil adsorbing carbon material has a particle size of 3 mm or less.

さらに、本発明は、紙質材を粉砕して所定サイズの植物繊維を得るための粉砕工程、得られた植物繊維の表面に撥水層を形成させる撥水剤コーティング工程、撥水剤でコーティングされた植物繊維、炭素質材料を1000〜1500℃でか焼することにより得られる油吸着用炭素材料および化学繊維を所定の割合で混合分散させる工程、および得られた混合分散物を加熱およびプレス成形する工程を包含する油吸着材の製造方法に関する。   Furthermore, the present invention provides a pulverization step for pulverizing a paper material to obtain a plant fiber of a predetermined size, a water repellent coating step for forming a water repellent layer on the surface of the obtained plant fiber, and a coating with a water repellent. Plant fiber, carbonaceous material for oil adsorption obtained by calcining carbonaceous material at 1000-1500 ° C. and chemical fiber are mixed and dispersed at a predetermined ratio, and the obtained mixed dispersion is heated and pressed. It is related with the manufacturing method of the oil-adsorbing material including the process to do.

本発明の油吸着材は、環境に優しく、かつ油吸着能に優れる。従って、本発明の油吸着材は環境汚染防止にきわめて有効である。   The oil adsorbing material of the present invention is environmentally friendly and excellent in oil adsorbing ability. Therefore, the oil adsorbent of the present invention is extremely effective for preventing environmental pollution.

以下、本発明について詳述する。
本発明に用いられる油吸着用炭素材料は、炭素質材料を1000〜1500℃でか焼することにより得られる。
原料として用いられる炭素質材料は特に制限されるものではないが、か焼により得られる油吸着用炭素材料に、水を脱着しやすく且つ油分を吸着しやすいという表面特性を付与する観点から、コークスや黒鉛(膨張黒鉛を含む)などの非多孔性材料を用いることが好ましく、特にコークスが好ましい。
Hereinafter, the present invention will be described in detail.
The carbon material for oil adsorption used in the present invention is obtained by calcining a carbonaceous material at 1000 to 1500 ° C.
The carbonaceous material used as a raw material is not particularly limited, but it is coke from the viewpoint of imparting surface characteristics such as easy desorption of water and easy adsorption of oil to the carbon material for oil adsorption obtained by calcination. And non-porous materials such as graphite (including expanded graphite) are preferably used, and coke is particularly preferable.

コークスとしては特に制限されず、例えば、常圧残油、減圧残油、タールサンド、ビチューメン、シェールオイル、流動接触分解装置残油などの重質油、コールタール、コールタールピッチなどを原料として得られる石炭系又は石油系コークス、あるいは木材、おがくず、やしからなどを原料として得られる木炭系コークスが挙げられる。これらの原料は、1種を単独で用いてもよく、また、2種以上を組み合わせて用いてもよい。また、コークスを製造する際のコーキングプロセスとしては特に制限されず、フルードコーキングプロセス、フレキシコーキングプロセス、ディレードコーキングプロセスなどが適用可能である。コーキングプロセスにおける熱処理温度は、通常400〜600℃である。本発明においては、ディレードコーキングプロセスを経て得られるニードルコークスが好ましく用いられる。   Coke is not particularly limited. For example, heavy oil such as atmospheric residual oil, vacuum residual oil, tar sand, bitumen, shale oil, fluid contact cracker residual oil, coal tar, coal tar pitch, etc. are used as raw materials. Coal-based or petroleum-based coke, or charcoal-based coke obtained using wood, sawdust, coconut, etc. as raw materials. These raw materials may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, it does not restrict | limit especially as a coking process at the time of manufacturing coke, A fluid coking process, a flexi coking process, a delayed coking process, etc. are applicable. The heat treatment temperature in the coking process is usually 400 to 600 ° C. In the present invention, needle coke obtained through a delayed coking process is preferably used.

炭素質材料をか焼する装置としては、例えば、ロータリーキルン等の横型か焼装置、あるいはリードハンマー炉やロータリーハース(回転炉床式カルサイナー)等の縦型か焼装置などを用いて実施することができる。
か焼を行う際の処理温度は、1000〜1500℃の範囲であることが必要であり、好ましくは1200〜1450℃、より好ましくは1300〜1400℃である。処理温度が1000℃未満であると、得られる油吸着用炭素材料の表面に十分な疎水性を付与することができない。他方、処理温度が1500℃を超えると、得られる油吸着用炭素材料の表面において水を脱着しやすく且つ油分を吸着しやすい親水性−疎水性バランスを達成することが困難となる。また、か焼を行う際の処理時間は、好ましくは1分〜5時間であり、より好ましくは5分〜3時間の範囲である。
As an apparatus for calcining the carbonaceous material, for example, a horizontal calcination apparatus such as a rotary kiln or a vertical calcination apparatus such as a lead hammer furnace or a rotary hearth (rotary hearth calsiner) may be used. it can.
The processing temperature at the time of calcination needs to be in the range of 1000 to 1500 ° C, preferably 1200 to 1450 ° C, more preferably 1300 to 1400 ° C. When the treatment temperature is less than 1000 ° C., sufficient hydrophobicity cannot be imparted to the surface of the obtained carbon material for adsorbing oil. On the other hand, when the treatment temperature exceeds 1500 ° C., it becomes difficult to achieve a hydrophilic-hydrophobic balance where water is easily desorbed and oil is easily adsorbed on the surface of the obtained carbon material for adsorbing oil. Moreover, the processing time at the time of performing calcination is preferably 1 minute to 5 hours, more preferably 5 minutes to 3 hours.

か焼を行う際の雰囲気は、炭素質材料の表面からの極性基の除去が可能であれば特に制限されないが、窒素などの不活性ガス雰囲気中で行うことが好ましい。   The atmosphere for calcination is not particularly limited as long as polar groups can be removed from the surface of the carbonaceous material, but it is preferably performed in an inert gas atmosphere such as nitrogen.

か焼温度まで昇温する際の昇温速度は、好ましくは100〜1000℃/hの範囲であり、より好ましくは200〜800℃/hの範囲である。
また、か焼処理後に、か焼コークスを冷却する際には、か焼コークスの酸化防止及び極性基の生成の抑制の観点から、か焼装置(キルンなど)の出口付近の温度を500℃以下とすることが好ましく、300℃以下とすることがより好ましい。また、冷却方法は特に制限されず、放置による自然冷却等を行ってもよいが、処理効率向上の観点から、水冷による強制冷却を行うことが好ましい。
The rate of temperature rise when raising the temperature to the calcination temperature is preferably in the range of 100 to 1000 ° C./h, more preferably in the range of 200 to 800 ° C./h.
In addition, when cooling the calcined coke after the calcining treatment, the temperature near the outlet of the calcining apparatus (kiln, etc.) is 500 ° C. or less from the viewpoint of preventing the calcined coke from being oxidized and suppressing the formation of polar groups. It is preferable to set it as 300 degreeC or less. Further, the cooling method is not particularly limited, and natural cooling or the like may be performed by leaving it alone, but it is preferable to perform forced cooling by water cooling from the viewpoint of improving processing efficiency.

例えば、石炭系、石油系又は木炭系コークスを1000〜1500℃でか焼する場合、得られるか焼コークス(カルサインド コークス)のBET表面積は20m/g以下であり、好ましくは1〜10m/gである。このように、本発明にかかるか焼コークスは、従来の活性炭や活性コークスの表面積が、通常1000m/g程度であるのに比較して表面積がきわめて小さいものである。ところが、本発明者らの検討によれば、かかるか焼コークスからなる炭素材料は、含油排水中の油分に対して、従来の活性炭や活性コークスよりも高い吸着能を示す。このような対比からも、本発明の油吸着用炭素材料の吸着能が、か焼により改質された表面の特性に起因するものであることが示唆される。 For example, when coal-based, petroleum-based, or charcoal-based coke is calcined at 1000 to 1500 ° C., the BET surface area of the obtained calcined coke (calcined coke) is 20 m 2 / g or less, preferably 1 to 10 m 2 / g. Thus, the calcined coke according to the present invention has a very small surface area as compared with the surface area of conventional activated carbon and activated coke, which is usually about 1000 m 2 / g. However, according to the study by the present inventors, the carbon material composed of such calcined coke exhibits higher adsorption capacity than the conventional activated carbon and activated coke for the oil content in the oil-containing wastewater. From such a comparison, it is suggested that the adsorption ability of the carbon material for oil adsorption of the present invention is due to the characteristics of the surface modified by calcination.

本発明において用いられる油吸着用炭素材料の粒径は3mm以下であることが好ましく、1mm以下であることがより好ましい。これは製品吸着材マットの厚さが粒径が5mm〜10mmであるため、油吸着用炭素材料の粒径が大きいと吸着マットの凹凸が目立ち、操作性も悪くなるためである。   The particle size of the carbon material for oil adsorption used in the present invention is preferably 3 mm or less, and more preferably 1 mm or less. This is because the product adsorbent mat has a thickness of 5 mm to 10 mm, and if the oil adsorbing carbon material has a large particle size, the unevenness of the adsorbing mat becomes conspicuous and the operability deteriorates.

本発明において用いられる植物繊維は、紙質材を粉砕することにより得られる。具体的には、紙管や古紙等の廃紙製品、おがくず、木材チップ、ヤシガラ、もみがら等を切断したり、粉砕したりして繊維に分解して綿状にしたもの等を挙げることができる。
粉砕方法としては、公知の手段を使用することができる。使用済みの紙管や古紙等の紙質材をシュレッダーを用いて綿状に粉砕して、これを篩いにより分級調整して所定のサイズ、例えばその平均繊維長が3〜10mmの植物繊維を得ることが行われる。
The plant fiber used in the present invention is obtained by pulverizing a paper material. Specific examples include waste paper products such as paper tubes and waste paper, sawdust, wood chips, coconut shells, rice husks, etc. cut or pulverized into fibers that are decomposed into cotton. it can.
As the pulverization method, known means can be used. A paper material such as a used paper tube or used paper is pulverized into a cotton shape using a shredder and classified by a sieve to obtain a plant fiber having a predetermined size, for example, an average fiber length of 3 to 10 mm. Is done.

次に、植物繊維の表面に撥水層を形成させるため、植物繊維に撥水剤を作用させて植物繊維の表面の一部または全部を撥水剤でコーティングする。
本発明に用いられる撥水剤としては、パラフィンワックス、石油樹脂、アスファルト、シリコーン樹脂、フッ素系樹脂等を挙げることができる。中でもパラフィンワックス、とくにアニオン系のパラフィンワックスはその撥水性と価格面から望ましい。その融点が65〜75℃のアニオン系パラフィンワックスをエマルジョン化したものが好ましく用いられる。撥水剤の融点が65℃より低くなると、水中における撥水コーティングの耐久性が不足する傾向が現れ、逆に75℃より高くなると植物繊維表面への被覆性が悪くなって油吸着性のばらつきなどのおそれが生じるので好ましくない。
Next, in order to form a water-repellent layer on the surface of the plant fiber, a part or all of the surface of the plant fiber is coated with the water-repellent agent by applying a water-repellent agent to the plant fiber.
Examples of the water repellent used in the present invention include paraffin wax, petroleum resin, asphalt, silicone resin, and fluorine resin. Of these, paraffin wax, particularly anionic paraffin wax, is desirable from the viewpoint of water repellency and price. An emulsion of an anionic paraffin wax having a melting point of 65 to 75 ° C. is preferably used. When the melting point of the water repellent is lower than 65 ° C, the durability of the water-repellent coating in water tends to be insufficient, and conversely, when the temperature is higher than 75 ° C, the covering property to the surface of the plant fiber is deteriorated and the oil adsorbability varies. This is not preferable because it may cause

植物繊維に対する撥水剤の構成比率は質量比で、0.05〜0.10であることが好ましく、より好ましくは0.06〜0.08である。植物繊維に対する撥水剤の構成比率が0.05より少なくなると撥水効果が十分に得られず、一方0.10を超えると逆に油吸着性が減少する傾向が現れるので好ましくない。   The constituent ratio of the water repellent to the plant fiber is preferably 0.05 to 0.10, more preferably 0.06 to 0.08, in terms of mass ratio. If the composition ratio of the water repellent to the plant fiber is less than 0.05, a sufficient water repellent effect cannot be obtained. On the other hand, if it exceeds 0.10, the oil adsorbability tends to decrease.

本発明においては、前述の本発明にかかる油吸着用炭素材料、撥水剤でコーティングされた植物繊維、および接着用の化学繊維を攪拌気流中あるいはスクリュー攪拌機中で分散混合させ、油吸着用炭素材料と植物繊維間に化学繊維が分散接着した交絡組織を形成させる。
植物繊維に対する油吸着用炭素材料の質量比率は、0.3〜0.6の範囲であることが必要であり、好ましくは0.4〜0.5である。また、油吸着用炭素材料と撥水剤でコーティングされた植物繊維との和に対する化学繊維の質量比率は0.4以下であることが必要である。
In the present invention, the oil adsorbing carbon material according to the present invention, the plant fiber coated with a water repellent, and the chemical fiber for adhesion are dispersed and mixed in a stirring airflow or in a screw stirrer. A entangled tissue in which chemical fibers are dispersed and bonded between the material and the plant fiber is formed.
The mass ratio of the carbon material for adsorbing oil to the plant fiber needs to be in the range of 0.3 to 0.6, preferably 0.4 to 0.5. Further, the mass ratio of the chemical fiber to the sum of the carbon material for adsorbing oil and the plant fiber coated with the water repellent agent needs to be 0.4 or less.

本発明において用いられる化学繊維としては、油吸着材として適用されるものであれば特に限定されるものではないが、例えば、ポリプロピレン、ナイロン、ポリエステル等を挙げることができる。   The chemical fiber used in the present invention is not particularly limited as long as it is applied as an oil adsorbent, and examples thereof include polypropylene, nylon, and polyester.

上記で得られた分散混合物は、次いで加熱プレス成形処理が施される。例えば、箱状または円筒状に形成された充填型枠の上部開口に前記分散混合物を供給し、底部に沈降堆積した分散混合積層物をその積層方向に加熱しながらプレス成形する。このときのプレス成形圧力、プレス成形温度、プレス成形時間は、とくに限定されず、前記材料の種類、および混合割合により適宜選択される。
加熱プレス成形により、ボード状またはバルク状に形成された本発明の油吸着材が得られる。
The dispersion mixture obtained above is then subjected to a hot press molding treatment. For example, the dispersion mixture is supplied to an upper opening of a filling mold formed in a box shape or a cylindrical shape, and the dispersion mixture laminate settled and deposited on the bottom is press-molded while being heated in the lamination direction. The press molding pressure, press molding temperature, and press molding time at this time are not particularly limited, and are appropriately selected depending on the kind of the material and the mixing ratio.
The oil adsorbent of the present invention formed in a board shape or a bulk shape is obtained by hot press molding.

ボード状等に形成された油吸着材は、その用途に応じて裁断機等により裁断、加工され、1)マット状、2)油水分離槽の濾過材として多用されるリボン状、3)複雑な箇所にフィット可能なチューブ状、4)水面流出油回収に使用されるオイルフェンス状等、種々の形態のものとして用いることができる。   The oil adsorbent formed in a board shape or the like is cut and processed by a cutting machine or the like according to its use, 1) a mat shape, 2) a ribbon shape that is frequently used as a filter material for an oil / water separation tank, and 3) a complicated It can be used in various forms such as a tube shape that can be fitted to a location, and 4) an oil fence shape that is used for recovering water spilled oil.

以下に実施例を挙げ、本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[参考例]
不活性ガス雰囲気中、ニードルコークス(S−JAカルサインド粉コークス)を、昇温速度約180〜240℃/hで1300℃まで昇温し、1300℃で4時間か焼した。その後、水冷による強制冷却を行い、か焼炉の出口温度を120℃に保持し、BET表面積3m/gのか焼コークスを得た。
[Reference example]
In an inert gas atmosphere, needle coke (S-JA calcined powder coke) was heated to 1300 ° C. at a temperature increase rate of about 180 to 240 ° C./h and calcined at 1300 ° C. for 4 hours. Then, forced cooling by water cooling was performed, the exit temperature of the calcination furnace was maintained at 120 ° C., and calcined coke having a BET surface area of 3 m 2 / g was obtained.

このようにして得られたか焼コークスを、実施例の吸着剤として、以下の試験に供した。
油吸着用炭素材料として上記で得られたか焼コークス、植物繊維として廃棄物である紙管を粉砕したもの、および接着用化学繊維としてポリエステルファイバー(品名テピルス:帝人ファイバー(株)製)を使用し、表1に示す試験片を作成した。
各試験片を、灯油、およびA重油に浸漬し、油吸着能を評価した。
The calcined coke thus obtained was subjected to the following test as an adsorbent for the examples.
Use the calcined coke obtained above as carbon material for oil adsorption, pulverized paper tube as waste as plant fiber, and polyester fiber (product name Tepyrus: manufactured by Teijin Fibers Ltd.) as chemical fiber for adhesion Test pieces shown in Table 1 were prepared.
Each test piece was immersed in kerosene and A heavy oil, and oil adsorption ability was evaluated.

なお、油吸着能(油保持量:g/cm)の評価はつぎのようにして行った。
試験片(10cm角、厚さ10mm)を灯油、または重油に5分間浸漬したのち、試験片マットの4隅の一つを掴んで菱形にして5分間吊るした。試験片への残存油量を求め、容積当たりの油保持量を算出した。
The oil adsorption capacity (oil retention amount: g / cm 3 ) was evaluated as follows.
A test piece (10 cm square, 10 mm thick) was immersed in kerosene or heavy oil for 5 minutes, and then one of the four corners of the test piece mat was grasped and formed into a diamond shape and hung for 5 minutes. The amount of oil remaining on the test piece was determined, and the amount of oil retained per volume was calculated.

Figure 0005072001
Figure 0005072001

[実施例1]
試験片A(か焼コークスの粒径が1mm、植物繊維量に対するか焼コークス量の比率が0.42、およびか焼コークス量と植物繊維量の和に対する接着用化学繊維量の比率が0.25)を灯油に浸漬したところ、油保持量は0.67g/cmと、優れた油吸着能を示した。
[Example 1]
Specimen A (particle diameter of calcined coke is 1 mm, ratio of calcined coke to plant fiber is 0.42, and ratio of chemical fiber for adhesion to the sum of calcined coke and plant fiber is 0.00. When 25) was immersed in kerosene, the oil retention was 0.67 g / cm 3 , indicating an excellent oil adsorption capacity.

[実施例2]
試験片B(か焼コークスの粒径が2mm、植物繊維量に対するか焼コークス量の比率が0.42、およびか焼コークス量と植物繊維量の和に対する接着用化学繊維量の比率が0.25)を灯油に浸漬したところ、油保持量は0.62g/cmと、優れた油吸着能を示した。
[Example 2]
Test piece B (particle diameter of calcined coke is 2 mm, ratio of calcined coke amount to vegetable fiber amount is 0.42, and ratio of chemical fiber amount for adhesion to the sum of calcined coke amount and vegetable fiber amount is 0.00. When 25) was immersed in kerosene, the oil retention was 0.62 g / cm 3 , indicating an excellent oil adsorption capacity.

[比較例1]
試験片C(か焼コークスの粒径が2mm、植物繊維量に対するか焼コークス量の比率が0.69、およびか焼コークス量と植物繊維量の和に対する接着用化学繊維量の比率が0.21)を灯油に浸漬したところ、油保持量は0.53g/cmと、実施例1、2に比較して油吸着能は劣っていた。植物繊維量に対するか焼コークス量の比率が0.69と、大きすぎることによると考えられる。
[Comparative Example 1]
Specimen C (particle diameter of calcined coke is 2 mm, ratio of calcined coke to plant fiber is 0.69, and ratio of chemical fiber for bonding to the sum of calcined coke and plant fiber is 0. When 21) was immersed in kerosene, the oil retention was 0.53 g / cm 3, which was inferior in oil adsorption capacity compared to Examples 1 and 2. The ratio of the calcined coke amount to the plant fiber amount is 0.69, which is considered to be too large.

[比較例2]
試験片D(か焼コークスの粒径が0.35mm、植物繊維量に対するか焼コークス量の比率が0.14、およびか焼コークス量と植物繊維量の和に対する接着用化学繊維量の比率が0.32)を灯油に浸漬したところ、油保持量は0.54g/cmと、実施例1、2に比較して油吸着能は劣っていた。植物繊維量に対するか焼コークス量の比率が0.14と、少なすぎたことによると考えられる。
[Comparative Example 2]
Test piece D (particle diameter of calcined coke is 0.35 mm, the ratio of calcined coke to the amount of plant fiber is 0.14, and the ratio of chemical fiber for adhesion to the sum of calcined coke and plant fiber is When 0.32) was immersed in kerosene, the oil retention was 0.54 g / cm 3, which was inferior to that of Examples 1 and 2. The ratio of the calcined coke amount to the plant fiber amount is 0.14, which is considered to be too small.

[比較例3]
市販のポリプロピレン製の油吸着材を灯油に浸漬したところ、油保持量は0.30g/cmと、実施例1、2に比較して油吸着能は劣っていた。
[Comparative Example 3]
When a commercially available polypropylene oil adsorbent was immersed in kerosene, the oil retention was 0.30 g / cm 3, which was inferior to that of Examples 1 and 2.

[実施例3]
試験片A(か焼コークスの粒径が1mm、植物繊維量に対するか焼コークス量の比率が0.42、およびか焼コークス量と植物繊維量の和に対する接着用化学繊維量の比率が0.25)をA重油に浸漬したところ、油保持量は0.77g/cmと、優れた油吸着能を示した。
[Example 3]
Specimen A (particle diameter of calcined coke is 1 mm, ratio of calcined coke to plant fiber is 0.42, and ratio of chemical fiber for adhesion to the sum of calcined coke and plant fiber is 0.00. When 25) was immersed in A heavy oil, the oil retention was 0.77 g / cm 3 , indicating an excellent oil adsorption capacity.

[実施例4]
試験片B(か焼コークスの粒径が2mm、植物繊維量に対するか焼コークス量の比率が0.42、およびか焼コークス量と植物繊維量の和に対する接着用化学繊維量の比率が0.25)をA重油に浸漬したところ、油保持量は0.65g/cmと、優れた油吸着能を示した。
[Example 4]
Test piece B (particle diameter of calcined coke is 2 mm, ratio of calcined coke amount to vegetable fiber amount is 0.42, and ratio of chemical fiber amount for adhesion to the sum of calcined coke amount and vegetable fiber amount is 0.00. When 25) was immersed in A heavy oil, the oil retention was 0.65 g / cm 3 , indicating an excellent oil adsorption capacity.

[比較例4]
試験片C(か焼コークスの粒径が2mm、植物繊維量に対するか焼コークス量の比率が0.69、およびか焼コークス量と植物繊維量の和に対する接着用化学繊維量の比率が0.21)をA重油に浸漬したところ、油保持量は0.65g/cmであった。試験片Cは、試験片Bに比較して、A重油吸着能は同等であったが、灯油吸着能は劣っていた。
[Comparative Example 4]
Specimen C (particle diameter of calcined coke is 2 mm, ratio of calcined coke to plant fiber is 0.69, and ratio of chemical fiber for bonding to the sum of calcined coke and plant fiber is 0. 21) was immersed in A heavy oil, the amount of oil retained was 0.65 g / cm 3 . Compared to test piece B, test piece C had the same A-heavy oil adsorption capacity but was inferior in kerosene adsorption capacity.

[比較例5]
試験片D(か焼コークスの粒径が0.35mm、植物繊維量に対するか焼コークス量の比率が0.14、およびか焼コークス量と植物繊維量の和に対する接着用化学繊維量の比率が0.32)をA重油に浸漬したところ、油保持量は0.57g/cmと、実施例3,4に比較して油吸着能は劣っていた。植物繊維量に対するか焼コークス量の比率が0.14と、少なすぎたことによると考えられる。
[Comparative Example 5]
Test piece D (particle diameter of calcined coke is 0.35 mm, the ratio of calcined coke to the amount of plant fiber is 0.14, and the ratio of chemical fiber for adhesion to the sum of calcined coke and plant fiber is When 0.32) was immersed in A heavy oil, the oil retention was 0.57 g / cm 3, which was inferior to those in Examples 3 and 4. The ratio of the calcined coke amount to the plant fiber amount is 0.14, which is considered to be too small.

[比較例6]
試験片E(か焼コークスを使用しない場合)をA重油に浸漬したところ、油保持量は0.57g/cmと、実施例3,4に比較して油吸着能は劣っていた。
[Comparative Example 6]
When specimen E (when calcined coke was not used) was immersed in heavy oil A, the oil retention was 0.57 g / cm 3, which was inferior in oil adsorption capacity compared to Examples 3 and 4.

[比較例7]
市販のポリプロピレン製の油吸着材を灯油に浸漬したところ、油保持量は0.38g/cmと、実施例3,4に比較して油吸着能は劣っていた。
[Comparative Example 7]
When a commercially available polypropylene oil adsorbent was immersed in kerosene, the oil retention was 0.38 g / cm 3, which was inferior in oil adsorption capacity compared to Examples 3 and 4.

実施例および比較例の結果を表2にまとめた。

Figure 0005072001
The results of Examples and Comparative Examples are summarized in Table 2.
Figure 0005072001

Claims (2)

炭素質材料を1000〜1500℃でか焼することにより得られる油吸着用炭素材料、表面の一部または全部が撥水剤でコーティングされた植物繊維、および油吸着用炭素材料と植物繊維間に分散接着する化学繊維からなり、植物繊維に対する油吸着用炭素材料の質量比率が0.3〜0.6であり、油吸着用炭素材料と植物繊維の和に対する化学繊維の質量比率が0.4以下であることを特徴とする油吸着材。   Oil-adsorbing carbon material obtained by calcining a carbonaceous material at 1000 to 1500 ° C., plant fiber having a part or all of its surface coated with a water repellent, and between the oil-adsorbing carbon material and plant fiber It consists of chemical fibers that are dispersed and bonded, the mass ratio of the carbon material for oil adsorption to the plant fiber is 0.3 to 0.6, and the mass ratio of the chemical fiber to the sum of the carbon material for oil adsorption and the plant fiber is 0.4. An oil adsorbent characterized by: 油吸着用炭素材料の粒径が3mm以下であることを特徴とする請求項1に記載の油吸着材。   The oil adsorbent according to claim 1, wherein the particle diameter of the oil adsorbing carbon material is 3 mm or less.
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