JP2000051691A - Oil adsorbing element and its production - Google Patents
Oil adsorbing element and its productionInfo
- Publication number
- JP2000051691A JP2000051691A JP10238024A JP23802498A JP2000051691A JP 2000051691 A JP2000051691 A JP 2000051691A JP 10238024 A JP10238024 A JP 10238024A JP 23802498 A JP23802498 A JP 23802498A JP 2000051691 A JP2000051691 A JP 2000051691A
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- Japan
- Prior art keywords
- oil
- water
- extruded
- absorbing
- heat treatment
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、油吸着素材及びそ
の製造方法に関し、特にスターチ、活性炭等の自然物を
含む押し出し成型品へ対して加熱による加工を施すこと
により特殊な立体構造を備えた油吸着素材及びその製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-adsorbing material and a method for producing the same, and more particularly to an oil having a special three-dimensional structure by subjecting an extruded product containing natural substances such as starch and activated carbon to processing by heating. The present invention relates to an adsorption material and a method for producing the same.
【０００２】[0002]
【従来の技術】今日、種々の油脂類が我々の生活の末端
にまで入り込んでいる。そしてその多くが船舶、車両等
により搬送され、巨大なタンクへ収容備蓄されている。
しかしてこれらの搬送手段又は収容手段等が、何らかの
原因によって損傷を受け、これらの油脂類が環境へ漏出
した場合には環境汚染を防止するために迅速にその回収
を図る必要がある。かかる場合に使用されるものに油吸
着素材がある。2. Description of the Related Art Today, various fats and oils have entered the end of our lives. Many of them are transported by ships, vehicles, etc., and stored in huge tanks.
If these transportation means or storage means are damaged for some reason and these fats and oils leak into the environment, it is necessary to promptly recover them in order to prevent environmental pollution. An oil-adsorbing material is used in such a case.
【０００３】従来知られている油吸着素材を大別する
と、第１に油との親和性が非常に高く油へ投下すると素
早く油を寄せ集め油の流動性を無くしてしまうようにそ
れ自体が膨張することにより油を内部へ取り込む形態の
もの、第２にゲル化材として樹脂を加熱溶解した後冷却
して櫛の歯状の長鎖アルキル基が油に中で配向してゆる
やかな網目を形成し油を一緒に抱き込みながら析出する
形態のもの、第３には素材内部のゆるやかな三次元架橋
構造を持つ当該構造の隙間に主に油との親和力即ちファ
ンデルワールス力によって物理的に油を保持する形態の
もの、の３つに分別することが出来る。[0003] The oil-absorbing materials known in the art can be roughly classified into firstly that they have a very high affinity for oil, so that when they are dropped into oil, the oil is quickly collected and loses the fluidity of the oil itself. Secondly, the resin is heated and dissolved as a gelling material and then cooled to form a loose mesh with long-chain comb-shaped alkyl groups oriented in the oil. Formed and deposited while embracing the oil together. Thirdly, the material has a gradual three-dimensional cross-linking structure inside the material, and is physically separated mainly by affinity with oil, that is, van der Waals force. Oil holding type can be classified into three types.
【０００４】しかるに流出した油が少量の場合、又はそ
の流出した区域が狭い場合には上記第１及び第２の形態
の油吸着素材が有効に使用され得るが、流出した油が多
量の場合、又はその流出した区域が広い場合には、上記
第１及び第２の形態の油吸着素材では十分な回収作業が
困難となり、第３の形態の油吸着素材の使用が必要とな
る。この第３の形態の油吸着素材としては、例えば、特
許第２５９４５０７号がある。[0004] However, when the amount of spilled oil is small, or when the spilled area is narrow, the oil adsorbing materials of the first and second forms can be used effectively. Alternatively, when the area from which the oil has flowed out is large, it is difficult to sufficiently recover the oil-absorbing material of the first and second embodiments, and the use of the oil-absorbing material of the third embodiment is required. As the oil adsorbing material of the third embodiment, for example, there is Japanese Patent No. 2594507.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、第３の
形態の油吸着素材は、第１及び第２のものに比較して優
れた吸収性はあるが未だ十分ではなく、また価格も一般
に高価である。そのため、該第３の形態の油吸着素材に
あって、より一層効果的に油を吸収保持することが出
来、かつこれまでよりも安価に生産出来る油吸収素材の
開発が望まれている。本件発明は、かかる要求を満たす
ものである。However, the oil-absorbing material of the third form has excellent absorbency as compared with the first and second oil-absorbing materials, but it is still insufficient, and the price is generally high. is there. Therefore, there is a demand for an oil-absorbing material of the third embodiment that can absorb and hold oil more effectively and that can be produced at lower cost than before. The present invention satisfies such a demand.
【０００６】[0006]
【課題を解決するための手段】本件発明は、ポリオレフ
ィン系樹脂からなる基材と、スターチ類からなる接合及
び潤滑材料と、活性炭からなる機能材と、より構成され
る出発材料を準備し、これらの出発材料を押し出し成型
可能な状態に混合し、これらの材料を所定の形状に押し
出し、蒸気発泡体よりなる押し出し成型体を形成し、そ
の後、当該押し出し成型体を加熱処理することにより内
部に油を吸収保持するための撥水性の特殊立体構造を形
成することより油吸着素材を製造する。The present invention provides a starting material comprising a base material made of a polyolefin resin, a joining and lubricating material made of starch, and a functional material made of activated carbon. The starting materials are mixed in an extrudable state, and these materials are extruded into a predetermined shape to form an extruded body made of a steam foam, and thereafter, the extruded body is subjected to a heat treatment to thereby form an oil therein. The oil-absorbing material is manufactured by forming a water-repellent special three-dimensional structure for absorbing and retaining oil.
【０００７】[0007]
【発明の実施の形態】以下、本発明の実施例につき図面
を参照しながら詳細に述べる。図１は本件発明にかかる
油吸着素材を製造するための方法を示すフローチャート
である。本件発明に係る油吸着素材即ち最終目的材料
は、出発材料を混合しこれを押し出し成形し、次いで必
要に応じてこれを所定寸法又は形状に裁断し、加熱処理
例えば燻煙処理を施すことにより製造され得る。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a flowchart showing a method for producing an oil-adsorbing material according to the present invention. The oil-adsorbing material according to the present invention, that is, the final target material, is manufactured by mixing the starting materials, extruding them, cutting them into predetermined dimensions or shapes as necessary, and subjecting them to heat treatment, for example, smoke treatment. Can be done.
【０００８】出発材料は、ペレット状基材と、接合及び
潤滑材料と、機能材と、からなる混合材料により構成さ
れている。ここで基材は、本件油吸収素材のベースをな
すもので、具体的にはポリオレフィン系樹脂、例えばポ
リプロピレン（ＰＰ）、ポリブタジエン（ＰＢ）または
それらの共重合体等から成ることが好ましい。接合及び
潤滑材料は、基材と機能材とを互いに接合するための固
化材又は糊剤及び押し出し作業時の潤滑材としての働き
をするものであり、出発材料を加熱処理した場合に簡単
に縮合消失しかつ流動時に配向し易い材料より構成さ
れ、具体的にはスターチ類、例えば米粉、植物蛋白グル
テン、更にはフスマ、米糠等が好ましい。また、機能材
は、油分を吸収しかつ撥水性を付与し基材へ隙間構造を
形成しファンデルワールスの親和力を発生するための主
剤であり、具体的には活性炭、例えば微粉炭若しくは生
木、枝等のチップ、炭酸カルシウム等から成ることが好
ましい。ここで機能材を構成する微粉炭は、木炭をクラ
ッシャー等の粉砕機へ入れ、その寸法が約２〜１００ミ
クロン程度になるまで粉砕する。同様に生木や枝、又は
その他の木質材（例えば木炭）を同様の手段によって超
微細な状態に加工して、連続押し出し作業が容易に出来
るように予め準備する。[0008] The starting material is composed of a mixed material comprising a pellet-shaped base material, a joining and lubricating material, and a functional material. Here, the base material forms the base of the present oil-absorbing material, and is preferably made of a polyolefin resin, for example, polypropylene (PP), polybutadiene (PB), or a copolymer thereof. The joining and lubricating material functions as a solidifying or gluing agent for joining the base material and the functional material to each other and as a lubricant during extrusion work, and easily condenses when the starting material is heat-treated. It is composed of a material that disappears and is easily oriented when flowing, and specific examples thereof include starches, such as rice flour, vegetable protein gluten, bran, and rice bran. Further, the functional material is a main agent for absorbing oil and imparting water repellency, forming a gap structure in the base material and generating affinity for Van der Waals, and specifically, activated carbon, for example, pulverized coal or raw wood , A branch or the like, calcium carbonate or the like. Here, the pulverized coal constituting the functional material is obtained by putting charcoal into a pulverizer such as a crusher and pulverizing the pulverized coal to a size of about 2 to 100 microns. Similarly, raw wood, branches, or other wood materials (for example, charcoal) are processed into a very fine state by similar means, and are prepared in advance so that continuous extrusion can be easily performed.
【０００９】これらの出発材料は、それ自体公知のミキ
サーによって、該出発材料構成要素が互いに均一な混練
状態になるまで混合される。The starting materials are mixed by a mixer known per se until the starting material components are homogeneously kneaded with one another.
【００１０】その後、これらの出発材料は、それ自体公
知の押し出し機によって、用途に応じて、それぞれ連続
する円形断面押し出し体（ロープ状）または薄板押し出
し体（マット、シート状）その他の形態に押し出し成形
される。押し出し作業は、蒸気の背圧による戻りを防止
する程度の圧力で加圧力を出来るだけ少なくし、水蒸気
が解放可能な圧力下によっておこなうことが好ましい。
かかる条件下での押し出し作業により、出発材料は押し
出し機のダイス内部を通る際に適切に流動配向して所定
の二次元構造を提供する。The starting materials are then extruded by means of an extruder known per se into a continuous extruded body (rope-shaped) or a thin sheet extruded (mat, sheet) or other forms, depending on the application. Molded. It is preferable that the pushing operation is performed under a pressure at which the steam can be released, with the pressing force being reduced as much as possible with a pressure that prevents the return due to the back pressure of the steam.
By the extrusion operation under such conditions, the starting material is appropriately flow-oriented as it passes through the inside of the die of the extruder to provide a predetermined two-dimensional structure.
【００１１】ついで、ダイスから押し出されるとき、押
し出し加熱用の水蒸気及び飛散ブローの発生により、蒸
気発泡体を形成し、素材内部に入り込んだ蒸気の放出、
貫通通路又は気泡空間の発生を確保する。これらの空所
が油との親和性（ファンデルワールス力）を高度に利用
することが出来るスペースを確保するものである。Then, when extruded from the die, steam for extrusion heating and generation of scattered blow form a steam foam to release steam entering the material.
Ensure the generation of through passages or bubble spaces. These voids secure a space where oil affinity (van der Waals force) can be used to a high degree.
【００１２】またこの押し出し製品の表面には基材によ
る薄い表皮が形成されると同時に横方向の膨らみが同時
に発生し、これが力学的な強度としてのクッション性を
付与することになる。こうして素材に対して引っ張り試
験時の靭性を提供する二次元構造を備えた素材が形成出
来る。Further, a thin skin by the base material is formed on the surface of the extruded product, and at the same time, a lateral swelling is generated, which gives cushioning as a mechanical strength. In this way, a material having a two-dimensional structure that provides the material with toughness during a tensile test can be formed.
【００１３】更に、この押し出し製品が押し出し機のダ
イス出口から離れるとダイス内圧力から解放されること
により接合材料が熱変化を発生して、該出発材料は三次
元構造を有する押し出し発泡成形体を提供する。Further, when the extruded product is separated from the die outlet of the extruder, the extruded product is released from the pressure in the die, so that the joining material generates a thermal change, and the starting material is an extruded foam having a three-dimensional structure. provide.
【００１４】ついでこの押し出し成形体は必要に応じて
所定の長さに裁断又は粉砕される。勿論、長いロープ状
態又はシート状態のまま巻き取り、裁断工程を必要とし
ない場合もある。Next, the extruded product is cut or pulverized to a predetermined length as required. Needless to say, there is a case where a long rope state or a sheet state is wound up and a cutting step is not required.
【００１５】その後、この押し出し発泡成形体は所定の
加熱炉等において加熱処理好ましくは燻煙処理される。
この加熱処理の目的は、ダイスから押し出されただけの
成形体は軸線方向へ材料の流れ特性が残っているため、
その方向への引き裂き特性が強く残っており、従ってこ
の引き裂き特性を解消して当該押し出し成形体に適度の
靭性を付与すること、及び出発材料中に存在している可
燃性材料を加熱燻煙させることにより該押し出し成型体
中に安定した特殊立体構造を形成することである。Thereafter, the extruded foamed article is subjected to a heat treatment, preferably a smoke treatment, in a predetermined heating furnace or the like.
The purpose of this heat treatment is that the molded body just extruded from the die retains the material flow characteristics in the axial direction,
The tearing property in that direction remains strong, so that the tearing property is eliminated to give the extruded article a proper toughness, and the combustible material present in the starting material is heated and smoked. This is to form a stable special three-dimensional structure in the extruded product.
【００１６】ここで、特殊立体構造とは、内部に疎水性
又は撥水性を有しているが、ファンデルワールスの親和
力により大量の油を吸収保持することが出来る無数の空
洞部分を提供している、あたかもグルテン様組織の絡み
合ったような構造をいう。これらの特殊立体構造の形状
は図２〜図５から明らかである。ここで図２は例えば円
形断面を有するロープ形状に成形した本件発明の製品の
断面写真であり、図３平坦なシート形状に成形した本件
発明の製品の断面写真であり、図４は図２の一部の拡大
断面写真であり、図５は図４の一部を更に拡大した拡大
断面写真である。これらの断面写真に示すように、本件
発明の油吸着素材製品１０は、表面部分１２に通水性を
有する無数の通路１４を有し、内部１６に撥水性を有し
かつファンデルワールスの親和力により大量の油を吸収
保持する無数の空洞部分１８を有している。Here, the special three-dimensional structure refers to an infinite number of hollow portions which have hydrophobic or water repellent inside but can absorb and hold a large amount of oil by the affinity of Van der Waals. Is a structure in which gluten-like tissues are intertwined. The shapes of these special three-dimensional structures are clear from FIGS. Here, FIG. 2 is a cross-sectional photograph of the product of the present invention formed into, for example, a rope shape having a circular cross section, FIG. 3 is a cross-sectional photograph of the product of the present invention formed into a flat sheet shape, and FIG. FIG. 5 is an enlarged cross-sectional photograph showing a part of FIG. As shown in these cross-sectional photographs, the oil-adsorbing material product 10 of the present invention has a myriad of passages 14 having water permeability in the surface portion 12, having water repellency in the interior 16, and having the affinity of Van der Waals. It has a myriad of hollow portions 18 that absorb and retain a large amount of oil.
【００１７】この特殊立体構造は、出発材料中の機能材
が燻煙処理等の加熱処理によって加熱減量化され、その
部分に空洞部を形成すると同時に、その加熱減量化の際
に発生するタール成分が基材の樹脂等に含まれるＯＨを
変化させ当該空洞部を疎水性とするものであり、これに
より水の中に分散される油類を回収し得る油吸収素材と
して極めて重要な機能を提供するものである。This special three-dimensional structure is characterized in that the functional material in the starting material is heated and reduced by a heat treatment such as a smoke treatment to form a cavity in that portion and, at the same time, a tar component generated at the time of the heating and reduction. Changes the OH contained in the resin of the base material to make the cavity hydrophobic, thereby providing an extremely important function as an oil-absorbing material capable of collecting oils dispersed in water. Is what you do.
【００１８】更にこの加熱処理において、出発材料中の
基材が溶融し、当該押し出し成型品の外形を保持しかつ
成型品内部の空洞形状を安定なものとする。Further, in this heat treatment, the base material in the starting material is melted, the external shape of the extruded product is maintained, and the cavity shape inside the molded product is stabilized.
【００１９】このような加熱処理によって、本件発明の
素材は、自由な曲げが可能であり、持ち運び及び取り扱
いに極めて便利な軽量の素材となる。更に図２〜図４に
示すように、本件発明の素材は、内部に無数の疎水性の
空洞部分１８が形成されているので、重量比で３〜３０
倍程度の油吸着性及び油保持性を提供することが、判明
している。By such a heat treatment, the material of the present invention can be freely bent and becomes a lightweight material which is extremely convenient to carry and handle. Further, as shown in FIGS. 2 to 4, the material of the present invention has an infinite number of hydrophobic hollow portions 18 formed therein, so that the weight ratio is 3 to 30.
It has been found to provide about twice as much oil absorption and oil retention.
【００２０】なお、この加熱処理工程における処理温度
によっては、当該素材に対してかなり異なる特性が付与
されることが判明している。即ち、加熱処理条件が２０
０〜３５０°Ｃ／５〜６０分の時には、素材が燻蒸炭化
を行う温度であり当該素材に対する水分除去と加熱処理
とにより、内部に十分な空間を持つグルテン様組織の絡
み合った軽量な素材を提供する。一方、加熱処理条件が
２００〜３５０°Ｃ／５〜６０分の時には、成型時の構
造を残しながら立体方向のスペースを構築するような組
織構造を提供し、この温度範囲における加熱処理におい
ては、素材が繰り返し使用に適するような靭性を確保す
ることが出来、いわゆる加熱圧縮等の強度に耐え得る素
材を提供することが出来る。そのため、油を吸収した素
材を例えば手で押し付けたり足で踏み付けたりして又は
圧搾による回収が出来ることにより該素材が吸収した油
を当該素材から分離し、その後、繰り返し当該素材を油
回収に再使用することも出来る。もしこれ以上高い温度
での加熱処理を施した場合には、素材が焼き締まりを発
生し、特殊三次元構造の隙間部分へ溶融した樹脂が流れ
込み該隙間部分を縮小させ、それに伴って靭性が低下
し、押圧したとき素材がバラバラに損傷しかつ崩壊する
ような状態となり、再使用は困難となろう。この場合は
回収後に焼却処分となり、繰り返し使用は望めない。It has been found that considerably different characteristics are imparted to the material depending on the processing temperature in the heat treatment step. That is, the heat treatment condition is 20
At a temperature of 0 to 350 ° C./5 to 60 minutes, the material is at a temperature at which fumigation and carbonization is performed. By removing water and heating the material, a light material in which a gluten-like tissue having a sufficient space inside is entangled can be obtained. provide. On the other hand, when the heat treatment conditions are 200 to 350 ° C./5 to 60 minutes, a texture structure that builds a three-dimensional space while leaving the structure at the time of molding is provided. In the heat treatment in this temperature range, It is possible to provide a material that can secure toughness such that the material is suitable for repeated use and that can withstand the strength of so-called heat compression. Therefore, the oil-absorbed material can be recovered by pressing, for example, by pressing or stepping on the foot, or by pressing, to separate the oil absorbed by the material from the material, and then repeatedly reusing the material for oil recovery. Can also be used. If heat treatment is performed at a higher temperature than this, the material will shrink and the molten resin will flow into the gaps in the special three-dimensional structure, reducing the gaps and reducing the toughness. However, when pressed, the material will break apart and collapse, making reuse difficult. In this case, it is incinerated after collection, and repeated use cannot be expected.
【００２１】かかる加熱処理を行った後、最後に素材を
加熱炉から取り出す。After the heat treatment, the material is finally taken out of the heating furnace.
【００２２】本件，発明による油吸着素材を使用する場
合には、当該素材をオイルフェンスの場合と同様に漏出
した油の外周囲に配置し、順次その周囲を狭めていく。
これにより油は瞬時に素材の持つ親和力と疎水性を有す
るために、当該素材の三次元空間内へ吸着される。又
は、本件素材を、直接、漏出した油面へ投下することに
よっても同様の吸着効果を提供することが出来る。油吸
着後の素材はこれを一個所へ集め前述のように油類を分
離した後、再使用することも出来るし、又は、油と一緒
に焼却処分することも出来る。In the case of using the oil adsorbing material according to the present invention, the material is arranged around the outside of the leaked oil as in the case of the oil fence, and the surrounding is gradually narrowed.
As a result, the oil instantly has the affinity and hydrophobicity of the material, and is thus adsorbed into the three-dimensional space of the material. Alternatively, the same adsorptive effect can be provided by dropping the material directly onto the leaked oil surface. The oil-adsorbed material can be collected at one place, separated into oils as described above, and then reused or incinerated together with the oil.
【００２３】本件発明による油吸収素材の出発材料の例
を、原料混合比率（Ｋｇ）によって示す。しかし出発材
料の配合はこれに限定されるものではない。Examples of the starting material of the oil-absorbing material according to the present invention are shown by the raw material mixing ratio (Kg). However, the composition of the starting materials is not limited to this.
【００２４】 表１： 基材： ＰＰ １５．０ 〜 ２４．０ 接合潤滑材： スターチ ２２．５ 〜 ３６．０ 機能材： 炭酸カルシウム １．０ 〜 １６．０ 活性炭、微粉炭 ２０．０ 〜 ５０．０ 以下に、本件発明により形成された油吸収素材がもたら
す油吸収量に関する測定値を表２〜表７に記載する。 Table 1: Base material: PP 15.0 to 24.0 Bonding lubricant: Starch 22.5 to 36.0 Functional material: Calcium carbonate 1.0 to 16.0 Activated carbon, pulverized coal 20.0 to 50 0.0 The following Tables 2 to 7 show measured values relating to the amount of oil absorbed by the oil-absorbing material formed according to the present invention.
【００２５】表２：本件素材試料は瞬時に油類を吸収す
るものであるが、以下においては下記の油分に５分間投
入して油類を吸収させた。その後、重量法にて〜毎
に吸収油量を測定した。 ：引き上げ後、直ちに重量を測定。 ：キムワイプ上に５分間放置後、重量を測定。 ：キムワイプ３枚を２つ折りにして手押しにより圧搾
後、重量を測定。 サラダ油 リグロイン トリクロロエチレン Ａ重油 １４．６８ ９．２２ １６．２３ １１．０３ １２．４１ ８．１８ １４．０５ ９．８８ ４．０４ １．９１ ３．１５ ２．３７ ／残留％ ８８．４４ ８９．３４ ８７．６７ ８９．５７ ／残留％ ２７．４７ ２２．２２ １９．６４ ２１．４９ Table 2: The material sample of the present invention absorbs oils instantly. In the following, the oils were absorbed in the following oils for 5 minutes. Thereafter, the amount of absorbed oil was measured by the weight method every time. : Measure the weight immediately after lifting. : After leaving on Kimwipe for 5 minutes, the weight was measured. : Three Kimwipes were folded in two, pressed by hand and weighed. Salad oil ligroin trichloroethylene A heavy oil 14.68 9.22 16.23 11.03 12.41 8.18 14.05 9.88 4.04 1.91 3.15 2.37 /% residual 88.44 89.34 87.67 89.57 /% residual 27.47 22.22 19.64 21.49
【００２６】表３：本件素材試料を押し出し成形した後
と加熱処理した後の当該試料の重量減少（％）を測定し
た。 試料 加熱温度 残存率 加熱減量率 Ｓ ３５０°Ｃ ２８．３４ ７１．６６ Ａ ２８０°Ｃ ５３．００ ４７．００ Ｂ ２５０°Ｃ ７０．４３ ２９．５７ Ｃ ２２５°Ｃ ８７．４７ １２．５３ Ｄ ２２０°Ｃ ９０．１９ ９．８１ Table 3: The weight loss (%) of the material sample after extrusion molding and after heat treatment was measured. Sample heating temperature residual rate Heating loss rate S 350 ° C 28.34 71.66 A 280 ° C 53.00 47.00 B 250 ° C 70.43 29.57 C 225 ° C 87.47 12.53 D 220 ° C 90.19 9.81
【００２７】表４：ここに示す各試料をＡ重油吸収素材
とした時の結果を、重量法にて、表２に示すと同様に
〜毎に吸収油量を測定した。 試料Ａ 試料Ｂ 試料Ｃ 試料Ｄ １１．０３ １３．００ １２．０１ １０．３５ ９．８８ １１．１０ １０．６４ ９．３５ ２．３７ ２．４１ １．９０ １．９６ ／残留％ ８９．５７ ８５．３８ ８８．５９ ９０．３４ ／残留％ ２１．４９ １８．５４ １５．８２ １８．９４ Table 4: The results obtained when each of the samples shown here were used as the A heavy oil-absorbing material were measured by the gravimetric method in the same manner as shown in Table 2 for the amount of absorbed oil. Sample A Sample B Sample C Sample D 11.03 13.00 12.01 10.35 9.88 11.10 10.64 9.35 2.37 2.41 1.90 1.96 / Residual% 89.57 85.38 88.59 90.34 /% residual 21.49 18.54 15.82 18.94
【００２８】表５：上記加熱試料Ｓを吸収素材とした時
の各油類の吸収量を重量比にて示す。 サラダ油 リグロイン トリクロロエチレン Ａ重油 ３．２３ ２．２２ ２．６１ ＊１３．００ ２．０９ １．８４ ２．１４ １１．１０ ー − − ２．４１ ここで＊は試料Ｂによる試験値である。 Table 5: The amount of each oil absorbed when the above heated sample S is used as an absorbing material is shown by weight ratio. Salad oil ligroin trichloroethylene A heavy oil 3.23 2.22 2.61 * 13.00 2.09 1.84 2.14 11.10 --- 2.41 where * is the test value for sample B.
【００２９】 表６： 本件素材Ｓを、一晩（１２時間）油類中へ浸けた後に測定した結果は以下の通 りである。 サラダ油 リグロイン トリクロロエチレン Ａ重油 ４．１３ ２．６９ ３．７７ ー ３．１９ ２．３８ ３．２５ ー Table 6: The results obtained by immersing the present material S in oils overnight (12 hours) are as follows. Salad oil ligroin trichloroethylene A heavy oil 4.13 2.69 3.77-3.19 2.38 3.25-
【００３０】表７：純粋パルプに近い素材を３５０°Ｃ
／１５分間、加熱処理したパルプを参考として、油吸収
材料と見立て、これを金網（銅製）に入れ、リグロイン
油液中へ投入して該リグロインを吸収させ、その重量比
を測定した。方法は表２に示すと同様。 以上の結果より、以下の事実が明白となった。即ち、表
２から、本件の素材は油の垂れ戻りによる離脱が少な
く、油保持性が極めて高く（８８．４〜８９．６％を保
持）、また、加圧による油離脱特性に富む（７３〜８０
％が離脱）ことが判明した。そのため、油類の回収利用
を図る素材として、加圧回収に適合したものとなる。ま
た、表３から、加熱温度が高くなるに従い、素材が焼き
締まりにより重量変動を起こして容積を減少しこれによ
り吸油量が変動することが判明した。表４及び表５はそ
れらの変動状況を明示している。従って、これらのこと
から、加熱処理温度が低いほど油保持性が極めて高く、
また、加圧による油離脱特性に富むことが判明した。さ
らに、表６から、本件発明にかかる油吸収素材の油吸収
量は、該素材が油液中に浸けられている時間には正比例
せず、約１０秒〜５分間以内でほぼピーク状態に達しそ
れ以降は、徐々に吸収量が増加することが判明した。ま
た、表７から、純粋パルプに近い素材ではいわゆる垂れ
戻り量が本件発明品よりも多く、更に搾り出した後にお
いても半分以上が素材中へ残存油量として存置すること
が明らかとなった。更に、以上の結果からＡ重油に関す
る吸収重量比では試料Ａ〜Ｄの処理素材にあって１０〜
１３倍の吸収を示している。この結果、２２５°Ｃ〜２
５０°Ｃの加熱処理が原料の押し出し成形後の重量減少
から判断出来る歩留まり（利用率）として良好であるこ
とが判明した。 Table 7: Material near pure pulp at 350 ° C
The pulp heat-treated for 15 minutes was regarded as an oil-absorbing material with reference to the pulp, which was put into a wire mesh (made of copper), poured into a ligroin oil solution to absorb the ligroin, and the weight ratio was measured. The method is the same as shown in Table 2. From the above results, the following facts became clear. That is, as shown in Table 2, the material of the present invention has a small amount of separation due to oil dripping, has an extremely high oil retention property (keeps 88.4 to 89.6%), and has a high oil separation characteristic by pressurization (73). ~ 80
% Withdrawal). Therefore, as a material for collecting and utilizing oils, the material is suitable for pressure recovery. Further, from Table 3, it was found that as the heating temperature was increased, the raw material was changed in weight due to shrinkage and the volume was reduced, and the oil absorption was fluctuated. Tables 4 and 5 show these fluctuation situations. Therefore, from these facts, as the heat treatment temperature is lower, the oil retention is extremely high,
In addition, it was found that the oil releasing property by pressurization was rich. Further, from Table 6, the oil absorption amount of the oil-absorbing material according to the present invention is not directly proportional to the time during which the material is immersed in the oil solution, and almost reaches a peak state within about 10 seconds to 5 minutes. Thereafter, it was found that the amount of absorption gradually increased. Also, from Table 7, it is clear that the so-called sagging amount of the material close to pure pulp is larger than that of the product of the present invention, and even after squeezing, more than half remains in the material as the residual oil amount. Further, from the above results, the absorption weight ratio for Fuel Oil A was 10 to 10 for the treated materials of Samples A to D.
It shows a 13-fold absorption. As a result, 225 ° C. to 2
It has been found that the heat treatment at 50 ° C. has a good yield (utilization rate) which can be judged from the weight loss after extrusion of the raw material.
【００３１】図６は、本件発明にかかる油吸収素材の、
常温試料（Ａ）と、加熱試料（２３０°Ｃ）（Ｂ）と、
をフーリエ変換赤外線分光分析法（ＦＴＩＲ）にて、常
法通り、分析した結果（山形県工業技術センターにおけ
る）を示す。この結果より、上記特許にかかるパルプの
加熱品よりも、本件発明の素材ではＯＨ基、ＣＯ基のシ
グナルが少なく、あまり変わらない状態であり、また加
熱処理後、赤外吸収帯の１７２０ｎｍでの振幅を特長と
したＣＯや炭酸エステル（脂肪族）が増加している状態
を特徴とする。このことは、２２０°Ｃ以上の加熱状態
においては素材が加熱燻煙された状態になっており、疎
水性を獲得した特殊立体構造の形成がみられるものと判
断出来る。更には透過率Ｔ％で表示してあり、波数１０
００カイザー付近に見られるスターチ類が入っているこ
とに留意が必要であろう。即ち、このことにより、本件
発明における立体構造形成に不可欠な要素が含まれてい
ることが明らかである。なおＳＣＡＮ５０回である。FIG. 6 shows the oil absorbing material according to the present invention.
A normal temperature sample (A), a heated sample (230 ° C.) (B),
Is shown by Fourier Transform Infrared Spectroscopy (FTIR) as usual, and the result (at Yamagata Prefectural Industrial Technology Center) is shown. From these results, the signal of the OH group and the CO group is less in the material of the present invention than in the heated product of the pulp according to the above patent, and the signal is not changed much. After the heat treatment, the infrared absorption band at 1720 nm is obtained. It is characterized by a state in which CO and carbonate (aliphatic), which are characterized by amplitude, are increasing. This means that the material is heated and smoked in the heating state of 220 ° C. or more, and it can be determined that formation of a special three-dimensional structure having acquired hydrophobicity is observed. Further, the transmittance is indicated by T%, and the wave number is 10%.
It should be noted that there are starches found near 00 Kaiser. That is, it is apparent from this that the essential elements for the formation of the three-dimensional structure in the present invention are included. Note that SCAN is 50 times.
【００３２】これまで述べた内容は、例えば、油が海上
等に拡散流出し未だ水面を浮遊しているような状態の油
の回収の際に使用される油回収素材についての例に関す
るものである。しかしながら本件発明の素材は、例えば
炭酸カルシュウム等で比重調整を図ることによって水底
等に沈んでいる油の回収においても有用に使用されうる
ものである。The contents described so far relate to, for example, an example of an oil recovery material used for recovering oil in a state where oil diffuses and flows out onto the sea or the like and is still floating on the water surface. . However, the material of the present invention can be usefully used for recovery of oil submerged on the water bottom or the like by adjusting the specific gravity with, for example, calcium carbonate.
【００３３】本件発明に関する油回収素材を水底等で機
能させるためには、特に表１に示す出発材料中に沈下の
ための比重増加のためにトリクロロエチレン等の化学物
質に対して有効な１〜１６Ｋｇ程度の炭酸カルシュウム
を添加し、更に再浮上のために１０〜１６Ｋｇ程度のス
ターチ類を添加する。次いで図１に示す加熱処理工程に
おいて、当該素材の一部が親水性を提示するように加熱
処理温度を低く（約２００°〜３００°Ｃ）設定する
か、又は出発材料中へパルプ等を加えるとき重量で約３
〜１５％、１０〜６０分加熱するときに水分を余分に添
加する。こうした条件下で成形した素材を混合状態又は
単独で水面に浮かしたとき、該素材の親水性基が周囲の
水分を呼びよせ、素材は浮力に抗して沈下し水底へ達す
る。しかるに、素材中の特殊立体構造は多くは疎水性及
び親油性の双方の性質を保有させることが出来るためで
あり、水底へ堆積している油分を迅速に吸収する。その
後、しばらくすると、添加した炭酸カルシュウムが水中
に溶解して放散し、比重が小さくなる。このときスター
チ類のグルコース発酵等親水部分が分解されることによ
って炭酸ガスが生成され、このため素材が水底の油を吸
収したまま水面まで浮上する。浮上したなら、それらの
素材を収集し、焼却等所定の処理を施す。In order for the oil recovery material according to the present invention to function at the bottom of the water or the like, 1 to 16 kg that is effective against a chemical substance such as trichlorethylene in the starting materials shown in Table 1 in particular to increase the specific gravity due to sedimentation. About 10 to 16 kg of starch is added for resurfacing. Next, in the heat treatment step shown in FIG. 1, the heat treatment temperature is set low (about 200 to 300 ° C.) so that a part of the material exhibits hydrophilicity, or pulp or the like is added to the starting material. When about 3 by weight
Add extra water when heating ~ 15%, 10-60 minutes. When the raw material formed under such conditions is floated on the water surface in a mixed state or alone, the hydrophilic groups of the raw material call the surrounding water, and the raw material sinks against the buoyancy and reaches the water bottom. However, the special three-dimensional structure in the raw material can have both hydrophobic and lipophilic properties in many cases, and quickly absorbs oil deposited on the water bottom. After a while, the added calcium carbonate dissolves in the water and diffuses, and the specific gravity decreases. At this time, carbonic acid gas is generated by the decomposition of the hydrophilic portion such as glucose fermentation of the starch, and the material floats up to the water surface while absorbing the oil at the bottom of the water. If the surface is raised, the materials are collected and subjected to predetermined treatment such as incineration.
【００３４】[0034]
【発明の効果】本件発明にかかる油吸収素材は、油吸収
量がこれまでの素材の１０〜２０倍が可能である。また
必要に応じて吸収した油の８０％程度を搾りだし回収す
ることが可能であり、素材の再使用が可能であり、また
焼却処分することも出来る。そのためこの素材の取り扱
いが容易である。そのうえ、比重が１．０以上の油類の
回収も可能であり、多方面での使用に適用出来る。The oil-absorbing material according to the present invention can absorb 10 to 20 times as much oil as before. If necessary, about 80% of the absorbed oil can be squeezed out and collected, so that the material can be reused and can be incinerated. Therefore, handling of this material is easy. In addition, oils having a specific gravity of 1.0 or more can be recovered, and can be used in various fields.
【００３５】更に、本件発明にかかる油吸収素材は、災
害等の発生現場、又は用法等に適宜迅速に対応すること
ができるように、その形状は、細長いロープ状、広い不
織布様のシート状又はマット状、取り扱い易い球状、そ
の他の形状に成形することが可能であり、どのような状
態においても、常に簡単に効果的に使用することが可能
である。Further, the oil-absorbing material according to the present invention has a shape of an elongated rope, a sheet of a wide non-woven fabric, or the like so that it can respond promptly to a site where a disaster or the like occurs, or to its usage. It can be formed into a mat shape, a spherical shape that is easy to handle, or other shapes, and can be used easily and effectively in any state.
【図１】本発明にかかる油吸収素材の成形方法を開示し
たフローチャートである。FIG. 1 is a flowchart showing a method for molding an oil-absorbing material according to the present invention.
【図２】円形断面を有するロープ形状に成形した本発明
にかかる油吸収素材の断面写真である。FIG. 2 is a cross-sectional photograph of an oil-absorbing material according to the present invention formed into a rope shape having a circular cross section.
【図３】平坦なシート形状に成形した本発明にかかる油
吸収素材の断面写真である。FIG. 3 is a cross-sectional photograph of the oil absorbing material according to the present invention formed into a flat sheet shape.
【図４】図２の一部の拡大断面写真である。FIG. 4 is an enlarged cross-sectional photograph of a part of FIG.
【図５】図４の一部を更に拡大した拡大断面写真であ
る。FIG. 5 is an enlarged sectional photograph in which a part of FIG. 4 is further enlarged.
【図６】本発明にかかる油吸収素材の常温時及び２３０
°Ｃまで加熱した時におけるＦＴＩＲによる結果を示す
図である。FIG. 6 shows the oil absorbing material of the present invention at room temperature and at 230 ° C.
It is a figure which shows the result by FTIR at the time of heating to ° C.
１０：油吸着素材 １２：表面部分 １
４：通路 １６：内部 １８：空洞部分10: Oil adsorption material 12: Surface part 1
4: Passage 16: Inside 18: Cavity
Claims (6)
スターチ類からなる接合及び潤滑材料と、活性炭からな
る機能材と、より構成される出発材料を準備すること、
これらの出発材料を押し出し成型可能な状態に混合する
こと、これらの材料を所定の形状に押し出し、蒸気発泡
体よりなる押し出し成型体を形成すること、その後、当
該押し出し成型体を加熱処理することにより内部に撥水
性の特殊立体構造を形成すること、より成る油吸着素材
の製造方法。1. A substrate comprising a polyolefin resin,
Preparing a starting material composed of a joining and lubricating material made of starch, and a functional material made of activated carbon,
By mixing these starting materials into a state that can be extruded, extruding these materials into a predetermined shape, forming an extruded body made of a steam foam, and then subjecting the extruded body to a heat treatment A method for producing an oil-absorbing material, comprising forming a water-repellent special three-dimensional structure inside.
していることを特徴とする請求項１に記載の油吸着素材
の製造方法。2. The method according to claim 1, wherein the starting material further comprises calcium carbonate.
体を所定の形状に裁断する工程を含むことを特徴とする
請求項１又は２に記載の油吸着素材の製造方法。3. The method for producing an oil-absorbing material according to claim 1, further comprising a step of cutting the molded body into a predetermined shape after forming the extruded molded body.
徴とする請求項１、２又は３に記載の油吸着素材の製造
方法。4. The method for producing an oil adsorbing material according to claim 1, wherein the heat treatment step is a smoke treatment.
有し、内部に撥水性を有しかつファンデルワールスの親
和力により大量の油を吸収保持する無数の空洞部分を有
していることを特徴とする油吸着素材。5. A surface part having a myriad of water-permeable passages, a water-repellent interior, and a myriad of cavities that absorb and retain a large amount of oil due to the affinity of Van der Waals. Characterized by an oil-adsorbing material.
している油分を吸収し、その後、水面まで浮上してくる
ことを特徴とする請求項５に記載の油吸着素材。6. The oil-absorbing material according to claim 5, wherein the oil sinks from the water surface to the water bottom, absorbs oil deposited on the water bottom, and then floats to the water surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23802498A JP3929614B2 (en) | 1998-08-10 | 1998-08-10 | Production method of oil-absorbing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23802498A JP3929614B2 (en) | 1998-08-10 | 1998-08-10 | Production method of oil-absorbing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000051691A true JP2000051691A (en) | 2000-02-22 |
| JP3929614B2 JP3929614B2 (en) | 2007-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP23802498A Expired - Fee Related JP3929614B2 (en) | 1998-08-10 | 1998-08-10 | Production method of oil-absorbing material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254915A (en) * | 2015-10-27 | 2016-01-20 | 南京理工大学 | Preparation method for super-hydrophobic super-oleophilic magnetic polystyrene function foam |
| CN105289534A (en) * | 2015-10-27 | 2016-02-03 | 南京理工大学 | Magnetic polystyrene foam and preparation method and application thereof |
| WO2016123155A1 (en) * | 2015-01-26 | 2016-08-04 | Pioneer Pet Products, Llc | Extruded granular oil sorbent |
| JP2017202484A (en) * | 2017-07-21 | 2017-11-16 | 株式会社 アクセスジャパン | Oil-water separation device to separate oil from oil-water mixture and oil-water separation system to separate oil from oil-water mixture including the device |
| US10028481B2 (en) | 2012-09-11 | 2018-07-24 | Pioneer Pet Products, Llc | Granular absorbent and system and method for treating or processing granular absorbent during granular absorbent transport |
| US10098317B2 (en) | 2012-09-11 | 2018-10-16 | Pioneer Pet Products, L.L.P. | Method of making animal litter |
| US10882238B2 (en) | 2014-01-25 | 2021-01-05 | Pioneer Pet Products, Llc | Method for making quenched granular absorbent |
| US11457605B2 (en) | 2012-09-11 | 2022-10-04 | Pioneer Pet Products, Llc | Extruded self-clumping cat litter |
| US11470811B2 (en) | 2012-09-11 | 2022-10-18 | Pioneer Pet Products, Llc | Extruded granular absorbent |
| US11602120B2 (en) | 2012-09-11 | 2023-03-14 | Pioneer Pet Products, Llc | Lightweight coated extruded granular absorbent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5138769A (en) * | 1974-09-26 | 1976-03-31 | Mitsubishi Rayon Co | Haisuishorizai oyobi sonoseiho |
| JPH0465193U (en) * | 1990-10-16 | 1992-06-05 | ||
| JPH11217510A (en) * | 1997-11-29 | 1999-08-10 | Yasuhiro Miyoshi | Oil-absorbing sheet composition and production of oil-absorbing sheet from the composition, oil-absorbing float, production of oil-absorbing textile, oil-absorbing mat |
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- 1998-08-10 JP JP23802498A patent/JP3929614B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5138769A (en) * | 1974-09-26 | 1976-03-31 | Mitsubishi Rayon Co | Haisuishorizai oyobi sonoseiho |
| JPH0465193U (en) * | 1990-10-16 | 1992-06-05 | ||
| JPH11217510A (en) * | 1997-11-29 | 1999-08-10 | Yasuhiro Miyoshi | Oil-absorbing sheet composition and production of oil-absorbing sheet from the composition, oil-absorbing float, production of oil-absorbing textile, oil-absorbing mat |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10028481B2 (en) | 2012-09-11 | 2018-07-24 | Pioneer Pet Products, Llc | Granular absorbent and system and method for treating or processing granular absorbent during granular absorbent transport |
| US10098317B2 (en) | 2012-09-11 | 2018-10-16 | Pioneer Pet Products, L.L.P. | Method of making animal litter |
| US10368527B2 (en) | 2012-09-11 | 2019-08-06 | Pioneer Pet Products, Llc | Animal litter |
| US11457605B2 (en) | 2012-09-11 | 2022-10-04 | Pioneer Pet Products, Llc | Extruded self-clumping cat litter |
| US11470811B2 (en) | 2012-09-11 | 2022-10-18 | Pioneer Pet Products, Llc | Extruded granular absorbent |
| US11602120B2 (en) | 2012-09-11 | 2023-03-14 | Pioneer Pet Products, Llc | Lightweight coated extruded granular absorbent |
| US10882238B2 (en) | 2014-01-25 | 2021-01-05 | Pioneer Pet Products, Llc | Method for making quenched granular absorbent |
| WO2016123155A1 (en) * | 2015-01-26 | 2016-08-04 | Pioneer Pet Products, Llc | Extruded granular oil sorbent |
| CN105254915A (en) * | 2015-10-27 | 2016-01-20 | 南京理工大学 | Preparation method for super-hydrophobic super-oleophilic magnetic polystyrene function foam |
| CN105289534A (en) * | 2015-10-27 | 2016-02-03 | 南京理工大学 | Magnetic polystyrene foam and preparation method and application thereof |
| JP2017202484A (en) * | 2017-07-21 | 2017-11-16 | 株式会社 アクセスジャパン | Oil-water separation device to separate oil from oil-water mixture and oil-water separation system to separate oil from oil-water mixture including the device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3929614B2 (en) | 2007-06-13 |
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