JPH0221429B2

JPH0221429B2 -

Info

Publication number: JPH0221429B2
Application number: JP56200120A
Authority: JP
Inventors: Shiro Ida; Mitsuyoshi Yano
Original assignee: Mitsui Mining Co Ltd
Current assignee: Mitsui Mining Co Ltd
Priority date: 1981-12-14
Filing date: 1981-12-14
Publication date: 1990-05-14
Also published as: JPS58101737A

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は石灰を原料とした安価な中空の炭素粒
子からなる油捕集用粒状炭材及びその製造法に関
するものである。更に詳しくは瀝青炭又は亜瀝青
炭から選ばれる灰分が8wt％以下で、ボタン指数
４以上の粘結性の高い石炭を、温度範囲400〜750
℃、乾留時間15分以下で乾留して得られるカサ比
重0.2〜0.4、比表面積50〜220m²／ｇである油捕
集用粒状炭材。及び瀝青炭又は亜瀝青炭から選ば
れる灰分が8wt％以下で、ボタン指数４以上の粘
結性の高い石炭を粉砕し、その大きさが0.25mm以
下が15wt％を超えないように粒度調整し、流動
乾留炉を使用し、温度範囲400〜750℃、乾留時間
15分以下で乾留することを特徴とする油捕集用粒
状炭材の製造方法である。水に浮遊した油あるいは懸濁した油を除去する
油捕集用炭材及びその製造法に関しては、従来石
油ピツチやフエノールマイクロバルンなどを原料
とし、これらに予備処理を施した後、加熱を行う
方法がある。すなわち原料の高軟化及び高粘度化
対策を講ずる工程を終えたものを瞬間的に加熱処
理し、原料を中空化する方法である。この方法は高価な原料とその予備処理費が嵩む
とともに、原料中の揮発分が石炭に比べ高いため
油捕集用炭材の歩留りが低く、そのため価格が高
いという欠点がある。本発明者らは、長年にわたる各種石炭の特性調
査研究の結果、コークス用炭はその物性を利用す
ることにより、これから容易に新しい炭材を製造
し得ることを見い出し本発明に到つた。すなわち本発明の炭材は、カサ比重0.2〜0.4、
比表面積50〜220m²／ｇ（以下BET法による測定）
の物性を有し、ほゞ球形に近い中空体の半成コー
クスである。炭材はすべて水に浮き、水面に浮い
た油を効果的に捕集し、しかも相互に凝集する現
象を示す物性を有している。油捕集後の炭材を水
蒸気気流中で蒸留して油を回収すると、残つた炭
材は再使用ができ、これを数回繰返しても油捕集
能力は殆んど低下せず、第３図に示すような成積
を示す。炭材の比表面積が50m²／ｇ未満であれば油捕集
能力が著しく低下し本発明の目的が達成出来ず、
220m²／ｇを超えるものは本発明の方法では製造
出来ない。又、この時のカサ比重は0.2〜0.4とな
る。本明細書中の石炭とは瀝青炭、亜瀝青炭から選
ばれた少くとも１種の石炭で粘結性の高い石炭を
いう。ここでいう粘結性の高い石炭とはボタン指
数４以上のものをさす。この石炭の灰分が8wt％
を超えるものは、製品である炭材のカサ比重が大
きく、水面に浮かなくなり好ましくない。本発明の製造法としては、乾燥した石炭を篩分
けずそのまま粉砕機にかける通常粉砕法で粉砕す
るより、ある所望の粒度の篩にかけ篩上のものを
その粒度以下に粉砕し、これと先の篩下のものを
混合する篩分け粉砕法を採用して粉砕することが
好ましい。篩分け粉砕法を採用する場合、第１表
に示すように通常粉砕法の場合より中間粒度分が
多くなり微粉が少くなるので、本発明の炭材歩留
りを向上させることが出来る。一方、0.25mm以下
の微粉が15wt％を超えると、本発明の製造法で
はサイクロンでの製品捕集率が低く経済的でな
い。 The present invention relates to an oil-trapping granular carbon material made of inexpensive hollow carbon particles made from lime, and a method for producing the same. More specifically, coal with an ash content of 8 wt% or less selected from bituminous coal or sub-bituminous coal and a highly caking coal with a Button index of 4 or more is used at a temperature range of 400 to 750.
A granular carbonaceous material for oil collection having a bulk specific gravity of 0.2 to 0.4 and a specific surface area of 50 to 220 m ² /g obtained by carbonization at a temperature of 15 minutes or less. and bituminous coal or sub-bituminous coal with an ash content of 8 wt% or less and a highly caking coal with a Button index of 4 or more. Using a carbonization furnace, temperature range 400-750℃, carbonization time
This is a method for producing granular carbonaceous material for oil trapping, which is characterized by carbonization in 15 minutes or less. Regarding oil-trapping carbon materials that remove oil floating or suspended in water, and their production methods, conventionally oil pits, phenol micro balloons, etc. are used as raw materials, which are pretreated and then heated. There is a way. That is, this is a method of instantaneously heat-treating the raw material after the process of taking measures to soften and increase its viscosity, thereby hollowing out the raw material. This method has the drawbacks of expensive raw materials and high pre-treatment costs, and because the volatile content of the raw materials is higher than that of coal, the yield of oil-trapping carbonaceous material is low, and therefore the price is high. As a result of many years of investigation and research on the characteristics of various types of coal, the present inventors have discovered that by utilizing the physical properties of coking coal, new carbon materials can be easily produced from it, and have arrived at the present invention. That is, the carbon material of the present invention has a bulk specific gravity of 0.2 to 0.4,
Specific surface area 50-220m ² /g (hereinafter measured by BET method)
It is a semi-formed coke with the physical properties of a hollow body that is almost spherical. All carbonaceous materials have physical properties that allow them to float on water, effectively collect oil floating on the water surface, and cause them to coagulate with each other. After collecting the oil, the carbonaceous material is distilled in a steam stream to recover the oil, and the remaining carbonaceous material can be reused. Even if this process is repeated several times, the oil-capturing ability hardly decreases, and the This shows the formation as shown in Figure 3. If the specific surface area of the carbonaceous material is less than 50 m ² /g, the oil collecting ability will be significantly reduced and the object of the present invention cannot be achieved.
Items exceeding 220 m ² /g cannot be produced by the method of the present invention. Moreover, the bulk specific gravity at this time is 0.2 to 0.4. Coal in this specification refers to at least one type of coal selected from bituminous coal and sub-bituminous coal, which has a high caking property. Highly caking coal here refers to coal with a Button index of 4 or more. The ash content of this coal is 8wt%
If it exceeds this value, the bulk specific gravity of the product, charcoal material, will be too large and it will not float on the water surface, which is undesirable. In the production method of the present invention, rather than pulverizing dry coal by passing it directly through a pulverizer without sieving it in the usual pulverizing method, it passes through a sieve of a certain desired particle size and pulverizes the material on the sieve to a particle size below that particle size. It is preferable to use a sieve pulverization method in which the material under the sieve is mixed. When the sieve pulverization method is adopted, as shown in Table 1, the intermediate particle size is larger and the fine powder is smaller than in the case of the normal pulverization method, so that the yield of carbonaceous material of the present invention can be improved. On the other hand, if the fine powder of 0.25 mm or less exceeds 15 wt%, the production method of the present invention has a low product collection rate in the cyclone and is not economical.

【表】本発明に使用する流動乾留炉としては内熱式撹
拌流動炉が特に好ましく、第１図に示すように乾
留温度は400〜750℃でなければならない。乾留温
度400℃未満のときは比表面積50m²／ｇ以上の良
好な炭材を製造出来ず、750℃を超えると比表面
積が減少する。しかも炭材の炭素配列が等方性主
体から異方性主体に移り油捕集能力が低下し本発
明の目的が達成されない。又乾留時間は15分以下
が好ましく、15分を超えると炭素配列が異方性主
体となると共に石炭粒子間の融着がおこり好まし
くない。流動炉への給炭量、乾留時間、乾留時間
等の運転条件は実施者において、原料石炭の種
類、粒度等を勘案して適宜選択出来る。流動炉か
ら出た炭材はサイクロン等で捕集する。サイクロ
ン上部から出る副産物のタール、ガス、粉じん等
は燃料等に別途使用出来る。乾留温度500℃、乾留時間10分の場合の原料石
炭重量に対する炭材歩留りは、通常粉砕法で75〜
85wt％、篩分け粉砕法で80〜90wt％であつた。又、本発明の炭材の比表面積と石油系軽油捕集
重量との関係を第２図に示す。以下、実施例により本発明を更に詳しく説明す
るが、これに限定されるものではない。実施例１瀝青炭（灰分1.33wt％、揮発分33.25wt％、固
定炭素63.93wt％、全硫黄1.53wt％、ボタン指数
9.0）を６mmの篩で篩分け、篩上をほとんどの粒
子が６mm以下になるように砕いて篩下と混合し
た。このものの粒度分布wt％次のようであつた。[Table] As the fluidized carbonization furnace used in the present invention, an internally heated stirred fluidized bed furnace is particularly preferred, and the carbonization temperature must be 400 to 750°C as shown in FIG. When the carbonization temperature is less than 400°C, a good carbon material with a specific surface area of 50 m ² /g or more cannot be produced, and when it exceeds 750°C, the specific surface area decreases. Moreover, the carbon arrangement of the carbonaceous material changes from predominantly isotropic to predominantly anisotropic, resulting in a decrease in oil-capturing ability, making it impossible to achieve the object of the present invention. Further, the carbonization time is preferably 15 minutes or less; if it exceeds 15 minutes, the carbon arrangement becomes mainly anisotropic and fusion between coal particles occurs, which is not preferable. Operating conditions such as the amount of coal fed to the fluidized bed furnace, the carbonization time, and the carbonization time can be appropriately selected by the operator, taking into consideration the type of coking coal, particle size, etc. The carbonaceous materials discharged from the fluidized fluidized furnace are collected using a cyclone, etc. Byproducts such as tar, gas, and dust produced from the upper part of the cyclone can be used separately as fuel. When the carbonization temperature is 500℃ and the carbonization time is 10 minutes, the yield of carbonaceous material based on the weight of raw coal is 75 to 75% using the normal pulverization method.
It was 85 wt%, and 80-90 wt% by the sieving and crushing method. Further, FIG. 2 shows the relationship between the specific surface area of the carbon material of the present invention and the weight of petroleum-based light oil collected. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 Bituminous coal (ash content 1.33wt%, volatile content 33.25wt%, fixed carbon 63.93wt%, total sulfur 1.53wt%, Button index
9.0) was sieved with a 6 mm sieve, the top of the sieve was crushed so that most of the particles were 6 mm or less, and mixed with the bottom of the sieve. The particle size distribution wt% of this product was as follows.

【表】この石炭粒子を内熱撹拌式流動乾留炉に装入
し、乾留温度500℃で10分間乾留して炭材をつく
つた。この炭材の歩留りは88wt％であり、この
カサ比重は0.35、比表面積は134m²／ｇであつた。この炭材各5gを石油系軽油、石炭系軽油、石
油系重油がそれぞれ十分に分散している水中に投
入し炭材の油捕集能力を試べたところ石油系軽油
では0.98goil／ｇ炭材であり、石炭系軽油では
0.75goil／ｇ炭材であり、又石油系重油について
は0.90goil／ｇ炭材であつた。実施例２実施例１に使用した瀝青炭粒子を内熱撹拌式流
動炉で600℃で10分間乾留して炭材をつくつた。
この炭材の歩留りは85wt％であり、カサ比重は
0.30で比表面積は165m²／ｇであつた。該炭材の
油捕集能力は石油系軽油で1.05goil／ｇ炭材であ
つた。実施例３実施例１に使用した瀝青炭粒子を内熱撹拌式流
動炉で700℃で10分間乾留して炭材をつくつた。
この炭材の歩留りは80wt％であり、カサ比重は
0.26で比表面積は200m²／ｇであつた。該炭材の
油捕集能力は石油系軽油で1.10goil／ｇ炭材であ
つた。この炭材を水蒸気蒸留にかけて軽油を追い
出し、再使用を５回繰り返した。その時の油捕集
能力は次のようであつた。[Table] The coal particles were charged into an internally stirred fluidized carbonization furnace and carbonized at a carbonization temperature of 500°C for 10 minutes to produce carbonaceous material. The yield of this carbon material was 88 wt%, the bulk specific gravity was 0.35, and the specific surface area was 134 m ² /g. We put 5g each of this carbonaceous material into water in which petroleum-based light oil, coal-based light oil, and petroleum-based heavy oil were sufficiently dispersed to test the oil-capturing ability of the carbonaceous material. For coal-based diesel oil,
It was 0.75 goil/g carbon material, and 0.90 goil/g carbon material for petroleum heavy oil. Example 2 A carbon material was produced by carbonizing the bituminous coal particles used in Example 1 at 600° C. for 10 minutes in an internally heated stirring fluidized bed furnace.
The yield of this carbon material is 85wt%, and the bulk specific gravity is
0.30 and the specific surface area was 165 m ² /g. The oil-capturing ability of the carbon material was 1.05 goil/g of petroleum-based light oil. Example 3 The bituminous coal particles used in Example 1 were carbonized at 700° C. for 10 minutes in an internally stirred fluidized furnace to produce carbon material.
The yield of this carbon material is 80wt%, and the bulk specific gravity is
0.26, and the specific surface area was 200 m ² /g. The oil collecting capacity of the carbon material was 1.10 goil/g of petroleum-based light oil. This carbon material was subjected to steam distillation to remove light oil and was reused five times. The oil collection capacity at that time was as follows.

【表】【table】【図面の簡単な説明】[Brief explanation of drawings]

第１図は乾留温度と炭材の比表面積の関係を示
す。第２図は炭材の比表面積と石油系軽油捕集能
力との関係を示す。第３図は炭材の繰り返し使用
回数と石油系軽油捕集能力との関係を示す。 Figure 1 shows the relationship between carbonization temperature and specific surface area of carbonaceous material. Figure 2 shows the relationship between the specific surface area of carbonaceous material and the ability to capture petroleum-based light oil. Figure 3 shows the relationship between the number of repeated uses of carbonaceous material and the ability to capture petroleum-based light oil.

Claims

【特許請求の範囲】１瀝青炭又は亜瀝青炭から選ばれる灰分が8wt
％以下で、ボタン指数４以上の粘結性の高い石炭
を、温度範囲400〜750℃、乾留時間15分以下で乾
留して得られるカサ比重0.2〜0.4、比表面積50〜
220m²／ｇである油捕集用粒状炭材。２瀝青炭又は亜瀝青炭から選ばれる灰分が8wt
％以下で、ボタン指数４以上の粘結性の高い石炭
を粉砕し、その大きさが0.25mm以下が15wt％を超
えないように粒度調整し、流動乾留炉を使用し、
温度範囲400〜750℃、乾留時間15分以下で乾留す
ることを特徴とする油捕集用粒状炭材の製造方
法。[Claims] 1. Ash content selected from bituminous coal or sub-bituminous coal is 8wt.
% or less and a highly caking coal with a button index of 4 or more, the bulk specific gravity is 0.2 to 0.4 and the specific surface area is 50 to 50.
Granular carbonaceous material for oil collection with 220m ² /g. 2 Ash content selected from bituminous or sub-bituminous coal is 8wt
% or less, highly caking coal with a button index of 4 or more is pulverized, the particle size is adjusted so that the size is 0.25 mm or less does not exceed 15 wt%, and a fluidized carbonization furnace is used.
A method for producing a granular carbonaceous material for oil collection, characterized by carbonization in a temperature range of 400 to 750°C and a carbonization time of 15 minutes or less.