JP3730987B2 - Bromine impregnated activated carbon and method for producing the same - Google Patents
Bromine impregnated activated carbon and method for producing the same Download PDFInfo
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本発明は、臭素添着活性炭及びその製造方法に関する。より詳細には、硫化アルキル類を低濃度で含有する気体中から硫化アルキル類を効率よく除去するために有用な臭素添着活性炭及びその製造方法に関する。 The present invention relates to bromine-impregnated activated carbon and a method for producing the same. More specifically, the present invention relates to a bromine-impregnated activated carbon useful for efficiently removing alkyl sulfides from a gas containing alkyl sulfides at a low concentration and a method for producing the same.
下水処理場、し尿処理場、ゴミ処理場などから排出されるガス又は石油精製、石油化学、紙パルプなどの化学工場、食品工場などの工程で排出されるガス中には硫化水素、メルカプタン類、硫化アルキル類などの硫黄化合物が含まれている。従来から、このようなガス中の硫黄化合物を除去する方法として、例えばアルカリ吸収法、湿式酸化法、オゾン酸化法、活性炭吸着法、燃焼法など種々の方法が知られている。
しかし、これらの従来法でもいくつかの硫黄化合物は除去できるが、特定悪臭物質である硫化ジメチル、二硫化ジメチルのような硫化アルキル類は十分満足できるまで除去することができなかった。
Gas released from sewage treatment plants, human waste treatment plants, garbage treatment plants, etc., or gas emitted in processes such as oil refining, petrochemical, paper pulp chemical factories, food factories, etc. include hydrogen sulfide, mercaptans, Sulfur compounds such as alkyl sulfides are included. Conventionally, various methods such as an alkali absorption method, a wet oxidation method, an ozone oxidation method, an activated carbon adsorption method, and a combustion method are known as methods for removing sulfur compounds in such a gas.
However, although some sulfur compounds can be removed by these conventional methods, alkyl sulfides such as dimethyl sulfide and dimethyl disulfide, which are specific malodorous substances, cannot be removed until they are sufficiently satisfactory.
これに対して、一般の活性炭とは別に予め臭素を添着させた臭素添着活性炭を用いた場合には、前者による物理吸着とは異なる機構、つまり硫化ジメチル、二硫化ジメチルを化学吸着することにより除去できることが報告されている（特許文献１〜４）。 In contrast to this, when using bromine-impregnated activated carbon with bromine added in advance separately from general activated carbon, it is removed by chemical adsorption of dimethyl sulfide and dimethyl disulfide, which are different from the physical adsorption by the former. It is reported that it can be done (patent documents 1 to 4).
確かに、臭素を添着させた活性炭は、臭素を添着していない活性炭に比較してより多くの硫化ジメチル、二硫化ジメチル等の特定悪臭物質を除去することができるが、従来の臭素添着活性炭における活性炭の品質が、活性炭の物性、含有している物質、添着される臭素量等に起因して均一でなく、硫化ジメチル、二硫化ジメチル等の硫化アルキルを常に満足できる程度において除去することができないというのが現状である。
本発明は、上記課題に鑑み鋭意研究を行う過程で、種々の臭素添着活性炭の含有成分、性状及び物性等を詳細に検討した結果、臭素添着活性炭の保水率と臭素担持量及び活性炭に含まれる塩化物の多少が、硫化ジメチル、二硫化ジメチル等の特定悪臭物質の吸着除去と高い相関関係があることを見出し、本発明を完成するに至った。 In the process of conducting intensive research in view of the above-mentioned problems, the present invention has been studied in detail on the components, properties, physical properties, and the like of various bromine-impregnated activated carbons. It has been found that some of the chloride has a high correlation with the adsorption and removal of specific malodorous substances such as dimethyl sulfide and dimethyl disulfide, and the present invention has been completed.
即ち本発明は、
（１）活性炭を高温雰囲気に加熱された炉に投入し、保水率が44.0〜60.0重量％となるように水蒸気賦活した後、水又はイオン水で洗浄するか、又は酸素不存在下に熱処理して含まれる塩化物の含有率を0.01重量％未満とし、この活性炭に臭素を３〜２０重量％添着することにより製造された臭素添着活性炭、
（２）活性炭を高温雰囲気に加熱された炉に投入し、保水率が44.0〜56.0重量％となるように水蒸気賦活した後、水又はイオン水で洗浄するか、又は酸素不存在下に熱処理して含まれる塩化物の含有率を0.005重量％未満とし、この活性炭に臭素を３〜２０重量％添着することにより製造された（１）記載の臭素添着活性炭、
（３）臭素添着活性炭の細孔容積が0.50〜1.2ｍｌ／ｇである（１）又は（２）記載の臭素添着活性炭、
（４）硫化アルキル類除去用である（１）〜（３）のいずれかに記載の臭素添着活性炭、
（５）活性炭を高温雰囲気に加熱された炉に投入し、保水率が44.0〜60.0重量％となるように水蒸気賦活した後、水又はイオン水で洗浄するか、又は酸素不存在下に熱処理して含まれる塩化物の含有率を0.01重量％未満とし、この活性炭に臭素を３〜２０重量％添着する臭素添着活性炭の製造法、
（６）活性炭を高温雰囲気に加熱された炉に投入し、保水率が44.0〜56.0重量％となるように水蒸気賦活した後、水又はイオン水で洗浄するか、又は酸素不存在下に熱処理して含まれる塩化物の含有率を0.005重量％未満とし、この活性炭に臭素を３〜２０重量％添着する（５）記載の臭素添着活性炭の製造法、
（７）臭素添着活性炭の細孔容積が0.50〜1.2ｍｌ／ｇである（５）又は（６）記載の臭素添着活性炭の製造法、及び
（８）硫化アルキル類除去用である（５）〜（７）のいずれかに記載の臭素添着活性炭の製造法、
である。
That is, the present invention
(1) Activated carbon is put into a furnace heated to a high temperature atmosphere, activated with water vapor so that the water retention rate is 44.0 to 60.0% by weight, then washed with water or ionic water, or heat treated in the absence of oxygen. A bromine-impregnated activated carbon produced by adhering 3 to 20% by weight of bromine to the activated carbon;
(2) Activated carbon is put into a furnace heated to a high temperature atmosphere, activated with water vapor so that the water retention rate is 44.0 to 56.0% by weight, then washed with water or ionic water, or heat treated in the absence of oxygen. The bromine-impregnated activated carbon according to (1), produced by adhering 3 to 20% by weight of bromine to the activated carbon, with a chloride content of less than 0.005% by weight,
(3) Bromine-impregnated activated carbon according to (1) or (2), wherein the pore volume of bromine-impregnated activated carbon is 0.50 to 1.2 ml / g,
(4) The bromine-impregnated activated carbon according to any one of (1) to (3), which is for removing alkyl sulfides,
(5) Activated carbon is put into a furnace heated to a high temperature atmosphere, activated with water vapor so that the water retention rate is 44.0 to 60.0% by weight, then washed with water or ionic water, or heat treated in the absence of oxygen. A method for producing a bromine-impregnated activated carbon in which the content of chloride contained is less than 0.01% by weight, and 3-20% by weight of bromine is attached to the activated carbon;
(6) Activated carbon is put into a furnace heated to a high temperature atmosphere, activated with water vapor so that the water retention rate is 44.0 to 56.0% by weight, then washed with water or ionic water, or heat treated in the absence of oxygen. The bromine-impregnated activated carbon production method according to (5), wherein the content of chloride contained is less than 0.005% by weight, and 3 to 20% by weight of bromine is impregnated to the activated carbon.
(7) The method for producing bromine-impregnated activated carbon according to (5) or (6), wherein the pore volume of bromine-impregnated activated carbon is 0.50 to 1.2 ml / g, and (8) for removing alkyl sulfides (5) to (7) A method for producing a bromine-impregnated activated carbon according to any one of
It is.
本発明における保水率とは、活性炭に水を加え、充分に浸漬し、脱水した後の活性炭重量当たりに含まれる水の含量（重量）を求めたものである。この保水率は、物質の吸着に直接寄与するミクロ孔の容積と活性炭の表面の通路として役割を果たすマクロ孔の容積との総和と高い相関関係がある。
また塩化物とは、活性炭を水で煮沸した後、試料溶液中に含まれる塩化物イオン（Ｃｌ−）をイオンクロマト法によって定量し、活性炭重量当たりの塩化物の含量（重量）を求めたものである。この塩化物は、臭素と同じハロゲン属に属する物質であるが、硫化アルキルの除去性能はなく、したがって塩化物が臭素より先に活性炭細孔部内に存在すると臭素が添着され難く硫化ジメチルなどの硫化アルキルの除去性能が低下する。
すなわち、本発明によれば、活性炭の保水率が４４.０〜６０.０重量％であり、塩化物が０．０１重量％未満の活性炭に臭素を３〜２０重量%添着させてなる臭素添着活性炭が提供される。
The water retention rate in the present invention refers to the content (weight) of water contained per activated carbon weight after adding water to activated carbon, sufficiently immersing and dehydrating. This water retention rate has a high correlation with the sum of the volume of micropores that directly contributes to the adsorption of substances and the volume of macropores that serve as passages on the surface of activated carbon.
The chloride is obtained by boiling the activated carbon with water and then quantifying the chloride ion (Cl − ) contained in the sample solution by ion chromatography to determine the chloride content (weight) per activated carbon weight. It is. This chloride is a substance belonging to the same halogen genus as bromine, but has no ability to remove alkyl sulfides. Therefore, if the chloride is present in the pores of the activated carbon prior to bromine, bromine is difficult to be adsorbed and sulfide such as dimethyl sulfide. Alkyl removal performance decreases.
That is, according to the present invention, the water retention of activated carbon is 44.0 to 60.0% by weight, and bromine impregnation is obtained by impregnating 3 to 20% by weight of bromine to activated carbon having a chloride content of less than 0.01% by weight. Activated carbon is provided.
本発明の臭素添着活性炭を製造するための原料活性炭は、 例えば、木材、木紛、ヤシ殻、パルプ製造時の副産物、バカス、廃糖蜜、泥炭、亜炭、褐炭、瀝青炭、有煙炭、無煙炭、石油蒸留残渣成分、石油ピッチ、コークス、コールタールなどの植物系原料や化石系原料、フェノール樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、メラミン樹脂、尿素樹脂、レゾルシノール樹脂、ポリアミド樹脂などの各種合成樹脂、ポリブチレン、ポリブタジエン、ポリクロロプレンなどの合成ゴム、その他合成木材や合成パルプなどを原料として公知の方法により製造されたものであって、その細孔容積が０.５０〜１．２０ｍｌ／ｇ、好ましくは０．５５〜０．９０ｍｌ／ｇ程度のものであれば、いかなるものでもよい。その形状は、たとえば球状、円柱状、破砕状、粉末状、顆粒状、繊維状、ハニカム状などのいずれでもよい。 Raw material activated carbon for producing the bromine-impregnated activated carbon of the present invention is, for example, wood, wood powder, coconut shell, by-product during pulp production, bacas, waste molasses, peat, lignite, lignite, bituminous coal, anthracite, anthracite, Various raw materials such as petroleum distillation residue components, petroleum pitch, coke, coal tar, and other synthetic resins such as phenolic resin, vinyl chloride resin, vinyl acetate resin, melamine resin, urea resin, resorcinol resin, polyamide resin, A synthetic rubber such as polybutylene, polybutadiene, or polychloroprene, or other synthetic wood or synthetic pulp is used as a raw material, and the pore volume is 0.50 to 1.20 ml / g, preferably Any one of about 0.55 to 0.90 ml / g may be used. The shape may be any of, for example, a spherical shape, a cylindrical shape, a crushed shape, a powder shape, a granular shape, a fiber shape, and a honeycomb shape.
本発明の臭素担持活性炭の原料活性炭においては、保水率が通常４４．０〜６０.０重量％、好ましくは４４．０〜５６．０重量％、より好ましくは４６．０〜５２．０重量％のものである。原料活性炭の保水率と硫化アルキル類の除去性能との間には高い相関関係があり、保水率が高いほど臭素担持活性炭の硫化アルキルの除去性能は高まる。しかし、保水率が６０．０重量％を越えると活性炭の強度、耐磨耗性が弱くなる。 In the raw material activated carbon of the bromine-supported activated carbon of the present invention, the water retention is usually 44.0 to 60.0% by weight, preferably 44.0 to 56.0% by weight, more preferably 46.0 to 52.0% by weight. belongs to. There is a high correlation between the water retention rate of the raw material activated carbon and the alkyl sulfide removal performance. The higher the water retention rate, the higher the alkyl sulfide removal performance of the bromine-supported activated carbon. However, when the water retention rate exceeds 60.0% by weight, the strength and wear resistance of the activated carbon become weak.
市販されている活性炭の通常の保水率は４４．０重量％未満であるが、本発明のような保水率４４．０〜６０．０重量％のものを得るためには、通常知られている活性炭の製造方法を応用しながら賦活の度合をより深く進めることにより製造することができる。たとえば、活性炭を９００〜１０００℃の高温雰囲気に加熱された炉に投入し通常より長時間水蒸気賦活する方法や、活性炭原料に石炭化度の若い褐炭、瀝青炭、有煙炭などを使用して十分に水蒸気賦活する方法などがある。もちろん保水率の高い活性炭を得るために、ここで述べた高温雰囲気下での水蒸気賦活や原料を選択しての水蒸気賦活だけに限定されず、それ以外の製造方法も用いることができる。しかしながら、活性炭の保水率が高くなり過ぎると、活性炭の充てん密度は軽くなり強度的にも脆くなる。 The normal water retention rate of commercially available activated carbon is less than 44.0% by weight, but it is usually known to obtain a water retention rate of 44.0-60.0% by weight as in the present invention. It can manufacture by advancing the degree of activation more deeply, applying the manufacturing method of activated carbon. For example, it is sufficient to use activated carbon in a furnace heated to a high temperature atmosphere of 900 to 1000 ° C. to activate steam for a longer time than usual, or to use activated carbon raw material with young coal, young bituminous coal, anthracite coal, etc. There is a method of steam activation. Of course, in order to obtain activated carbon having a high water retention rate, the present invention is not limited to the steam activation under the high temperature atmosphere described above or the steam activation by selecting raw materials, and other production methods can also be used. However, when the water retention rate of the activated carbon becomes too high, the packing density of the activated carbon becomes light and the strength becomes brittle.
本発明の臭素添着活性炭は、臭素の触媒酸化作用によって硫化ジメチル、二硫化ジメチルを酸化し、吸着するのであるが、塩素すなわち塩化物にはこの作用はない。従って、塩化物が臭素より先に活性炭中に存在すると臭素の触媒酸化作用を弱めることになるため、塩化物は、極力存在しない方が好ましい。具体的には、塩化物は、活性炭に対して０．０１重量％未満、好ましくは、０．００５重量％未満である。
本発明の臭素添着活性炭の製造方法において、臭素添着前の担体活性炭中の塩化物濃度を低減する方法は、原料活性炭を、水もしくはイオン交換水により洗浄する方法や酸素不存在下、５００〜１１００℃、好ましくは７００〜９００℃で熱処理する方法が挙げられる。
水もしくはイオン交換水による洗浄方法は、具体的には、原料活性炭を３０〜８０℃、好ましくは４０〜７０℃の温水もしくはイオン交換水に浸漬し、一定時間放置、空気バブリングによる攪拌及び／又は下方から水蒸気や空気を導入しながら攪拌する方法、原料活性炭を攪拌しながら水もしくはイオン交換水を連続的又は間欠的に供給する方法等が挙げられる。このような処理は、１回でもよいし、２回以上繰り返し行ってもよい。
The bromine-impregnated activated carbon of the present invention oxidizes and adsorbs dimethyl sulfide and dimethyl disulfide by the catalytic oxidation action of bromine, but chlorine, chloride, does not have this action. Accordingly, if the chloride is present in the activated carbon prior to bromine, the catalytic oxidation action of bromine is weakened. Therefore, it is preferable that the chloride is not present as much as possible. Specifically, the chloride is less than 0.01% by weight, preferably less than 0.005% by weight, based on the activated carbon.
In the method for producing bromine-impregnated activated carbon according to the present invention, the method for reducing the chloride concentration in the carrier activated carbon before bromine-impregnation is a method of washing raw material activated carbon with water or ion-exchanged water, or 500 to 1100 in the absence of oxygen. The method of heat-processing at (degreeC), Preferably 700-900 degreeC is mentioned.
Specifically, the cleaning method using water or ion-exchanged water is performed by immersing the raw material activated carbon in warm water or ion-exchanged water at 30 to 80 ° C., preferably 40 to 70 ° C., leaving it for a certain time, stirring by air bubbling and / or A method of stirring while introducing water vapor or air from below, a method of supplying water or ion-exchanged water continuously or intermittently while stirring raw material activated carbon, and the like can be mentioned. Such processing may be performed once or may be repeated twice or more.
熱処理による活性炭中の塩化物濃度低減法としては、例えば、高温熱分解法がある。高温熱分解法は、例えば、窒素、アルゴンガス等の酸素を含有しない不活性ガス中又は真空下で、原料活性炭を熱処理し、塩化物を熱分解する方法である。この際の熱処理濃度は、高温であるほど効率がよいが、使用する原料活性炭によっては、１２００℃程度を越える温度で細孔が閉塞するものもあるので、５００〜１１００℃程度が適当であり、好ましくは７００〜９００℃程度である。また、処理時間は、原料活性炭の処理量等により適宜調節することができ、例えば０．1〜１０時間程度が適当である。水又はイオン交換水で洗浄した後上記熱処理を行ってもよい。 An example of a method for reducing the chloride concentration in activated carbon by heat treatment is a high-temperature pyrolysis method. The high temperature pyrolysis method is a method in which a raw material activated carbon is heat-treated in an inert gas not containing oxygen such as nitrogen or argon gas or under vacuum to pyrolyze chloride. The heat treatment concentration at this time is more efficient as the temperature is higher, but depending on the raw material activated carbon used, pores may be blocked at a temperature exceeding about 1200 ° C., so about 500 to 1100 ° C. is appropriate, Preferably it is about 700-900 degreeC. The treatment time can be appropriately adjusted depending on the amount of raw material activated carbon, etc., for example, about 0.1 to 10 hours is appropriate. The heat treatment may be performed after washing with water or ion exchange water.
また、本発明の臭素添着炭における臭素の添着量は、通常活性炭に対して３〜２０重量％、好ましくは３〜１２重量％、さらに好ましくは３〜１０重量％である。臭素の添着量が少なすぎると硫化アルキルに対する吸着性能が低くなり、多くなり過ぎると操作時に臭素が脱離し、周囲の装置を腐食することがある。
臭素の活性炭への添着は、自体公知の添着法により行うことができる。
例えば、臭素ガスを含有したキャリアガスを熱処理が施された活性炭に接触させる気相添着法、処理された活性炭を臭素水に浸漬する液相添着法、処理された活性炭に液体臭素を直接散布して添着する方法等が挙げられる。
The amount of bromine added in the bromine-impregnated coal of the present invention is usually 3 to 20% by weight, preferably 3 to 12% by weight, and more preferably 3 to 10% by weight with respect to the activated carbon. If the amount of bromine added is too small, the adsorption performance for alkyl sulfide will be low, and if it is too large, bromine may be detached during operation, and the surrounding equipment may be corroded.
The addition of bromine to the activated carbon can be performed by an addition method known per se.
For example, a vapor phase deposition method in which a carrier gas containing bromine gas is brought into contact with activated carbon that has been heat treated, a liquid phase deposition method in which the treated activated carbon is immersed in bromine water, or liquid bromine is directly sprayed on the treated activated carbon. And a method of attaching them.
気相添着法では通常、キャリアガスとして例えば、空気、窒素ガス等を用い、接触温度を約１５０℃以下、好ましくは約８０℃以下に調節し、活性炭の流動床、移動床、噴霧床等を用いて連続的に気相添着させる。なお、この方法においては、臭素含有ガスを流通させて活性炭に臭素を添着させた後、キャリアガスのみを流通させて、添着されていない臭素ガスを除去することが好ましい。 In the vapor deposition method, usually, for example, air, nitrogen gas or the like is used as a carrier gas, the contact temperature is adjusted to about 150 ° C. or lower, preferably about 80 ° C. or lower, and the activated carbon fluidized bed, moving bed, spray bed, etc. And continuously vapor-phase-added. In this method, it is preferable that after adding bromine-containing gas to add bromine to the activated carbon, only carrier gas is passed to remove unattached bromine gas.
液相添着法では通常、臭素濃度が１〜５％程度の臭素水に所定量の活性炭を１〜１０時間程度浸漬するか、または臭素水を活性炭の流動床、移動床、固定床、噴霧床等を用いて流通／接触させて臭素を添着させた後、ろ別、乾燥する。なお、この際の温度は約８０℃以下が好ましく、さらに好ましいのは約５０℃以下である。 In the liquid phase addition method, a predetermined amount of activated carbon is usually immersed in bromine water having a bromine concentration of about 1 to 5% for about 1 to 10 hours, or bromine water is immersed in a fluidized bed, moving bed, fixed bed, or spray bed of activated carbon. The bromine is impregnated by being distributed / contacted using the like, and then filtered and dried. In this case, the temperature is preferably about 80 ° C. or less, and more preferably about 50 ° C. or less.
液体臭素等を散布して添着する方法としては、処理された活性炭を攪拌しながら、直接液体臭素又は臭素水等を散布し、必要により乾燥することにより行われる。その際の接触温度は約５０℃程度以下が好ましい。
本発明の臭素添着活性炭を用いて硫化アルキル類、とりわけ硫化ジメチル、二硫化ジメチルを含有する気体中からこれら硫化アルキル類を吸着／除去する方法は、例えば、固定床、移動床、流動床、スラリー方式、バッチ式接触攪拌法等の公知の方法により、被処理ガスを臭素添着活性炭と接触させる方法が挙げられる。この際の接触時間は、硫化アルキル類の濃度、使用する臭素添着活性炭の粒度、接触方式等により適宜加減することができるが、例えば約５０℃以下の温度で、０．１秒から１分間程度が普通である。
臭素の添着量が低すぎると、活性炭による硫化アルキル類の除去性能が低い。臭素の添着量が２０重量％を越えると、硫化アルキルの除去性能がそれ以上向上しないばかりか、操作中に臭素が漏れだして人畜にとって危険となることがある。
As a method of spraying and attaching liquid bromine or the like, it is carried out by spraying liquid bromine or bromine water directly while stirring the treated activated carbon, and drying it if necessary. The contact temperature at that time is preferably about 50 ° C. or less.
The method for adsorbing / removing alkyl sulfides from a gas containing alkyl sulfides, particularly dimethyl sulfide and dimethyl disulfide, using the bromine-impregnated activated carbon of the present invention is, for example, fixed bed, moving bed, fluidized bed, slurry. Examples of the method include a method in which a gas to be treated is brought into contact with bromine-impregnated activated carbon by a known method such as a method or a batch contact stirring method. The contact time at this time can be appropriately adjusted depending on the concentration of alkyl sulfides, the particle size of the bromine-impregnated activated carbon used, the contact method, etc. For example, at a temperature of about 50 ° C. or less, about 0.1 second to 1 minute. Is normal.
If the amount of bromine added is too low, the ability to remove alkyl sulfides by activated carbon is low. If the amount of bromine added exceeds 20% by weight, not only the performance of removing alkyl sulfide will not be improved, but also bromine leaks during operation, which may be dangerous for livestock.
本発明の臭素添着活性炭によれば、従来技術によって調整された臭素添着活性炭においては不十分とされていた硫化アルキル類に対する吸着性能を著しく向上させることができるとともに、その吸着性能のバラツキをもなくし、長期に亘り安定した硫化アルキル類の除去性能を発揮させることができる。 According to the bromine-impregnated activated carbon of the present invention, it is possible to remarkably improve the adsorption performance for alkyl sulfides, which has been considered insufficient in the bromine-impregnated activated carbon prepared by the prior art, and to eliminate variations in the adsorption performance. In addition, stable removal performance of alkyl sulfides can be exhibited over a long period of time.
以下に実施例、試験例等をあげて本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples and test examples.
（１）塩化物含有率が同等で、保水率が異なる活性炭の調製
各２００ｇの活性炭を管状炉にて９００℃に加熱し、水蒸気３ミリリットル／分を加えながら、所定の保水率になるよう賦活時間を調整して、水蒸気賦活を行った。次いで各々の活性炭各２００ｇに５重量％の塩酸１０００ｇを加えて３０分間煮沸した後、１００倍量のイオン交換水（６０℃）を用い、上向流で攪拌洗浄処理して、表１に示す塩化物含有率が同等で保水率が異なる活性炭を調製した。
なお、活性炭の保水率、塩化物含有率および細孔容積の測定法の概要は次の通りである。
(1) Preparation of activated carbon with the same chloride content and different water retention rate 200g of activated carbon each was heated to 900 ° C in a tubular furnace, and activated to achieve a predetermined water retention rate while adding water vapor 3ml / min. The steam was activated by adjusting the time. Next, 1000 g of 5% by weight hydrochloric acid was added to 200 g of each activated carbon and boiled for 30 minutes. Then, 100 times the amount of ion-exchanged water (60 ° C.) was used for stirring and washing treatment in an upward flow, as shown in Table 1. Activated carbons having the same chloride content and different water retention rates were prepared.
In addition, the outline | summary of the measuring method of the water retention, chloride content, and pore volume of activated carbon is as follows.
活性炭の保水率の測定法
１．試料活性炭を、１２０℃で３時間、電機乾燥器で乾燥し、デシケーター中で室温まで冷却し、その各５０ｇを５００ｍｌの三角フラスコにはかり取る。
２． 精製水２００ｍｌを加え、５０℃に保った振盪機で２０分間振とうする。
３．ナイロンメッシュ袋に活性炭を取り、脱水機で１分間脱水する。
４．脱水後の重量Ｗｅ（ｇ）を測定する。
５．保水率(％)＝(Ｗｅ−５０)÷Ｗｅ×１００
の式により保水率を計算する。
Method for measuring water retention rate of activated carbon The sample activated carbon is dried with an electric dryer at 120 ° C. for 3 hours, cooled to room temperature in a desiccator, and 50 g of each is weighed into a 500 ml Erlenmeyer flask.
2. Add 200 ml of purified water and shake with a shaker kept at 50 ° C. for 20 minutes.
3. Take activated carbon in a nylon mesh bag and dehydrate for 1 minute with a dehydrator.
4). The weight We (g) after dehydration is measured.
5. Water retention rate (%) = (We−50) ÷ We × 100
Calculate the water retention rate using the following formula.
活性炭中の塩化物含有率の測定法
ＪＩＳ Ｋ １４７４に従い、イオンクロマトグラフ法により測定を行う。
３ｇの活性炭に、１００ｍｌの水を加え、５分間ほど静かに沸騰させ、冷後濾過して、その濾液中の塩化物イオン量をイオンクロマトグラフ法により求め、試料中の塩化物含有量を算出する。
Method for measuring chloride content in activated carbon According to JIS K 1474, measurement is performed by ion chromatography.
Add 100 ml of water to 3 g of activated carbon, gently boil for about 5 minutes, cool and filter, calculate the chloride ion content in the filtrate by ion chromatography, and calculate the chloride content in the sample To do.
活性炭の細孔容積の測定法
細孔分布測定装置である（株）島津製作所製ＡＳＡＰ２４００（Ｎ２吸着法）を用い、細孔容積はCI法により求める。
Using a measurement pore distribution measuring apparatus of the pore volume of the activated carbon by Shimadzu Corp. ASAP 2400 (N 2 adsorption method), pore volume determined by CI method.
（２）保水率が同等で、塩化物濃度が異なる活性炭の調製
各２００ｇの活性炭を管状炉にて９００℃に加熱し、水蒸気３ミリリットル／分を加えながら、所定の保水率になるよう賦活時間を調整して、水蒸気賦活を行った。ついで次いで各々の活性炭各２００ｇに５重量％の塩酸１０００ｇを加えて３０分間煮沸した後、活性炭の２０〜１００倍量のイオン交換水（６０℃）を用い、上向流で攪拌洗浄処理して、表２に示す保水率が同等で塩化物濃度が異なる表２に示す活性炭を調製した。
（３）保水率が高い活性炭の調製
水蒸気による賦活時間をさらに延長した以外は上記（２）と同様にして表２に示す高い保水率の活性炭を調製した。
(2) Preparation of activated carbon with the same water retention rate and different chloride concentrations 200g of activated carbon each was heated to 900 ° C in a tubular furnace and added with water vapor 3ml / min. The water vapor activation was performed by adjusting. Next, 1000 g of 5% by weight hydrochloric acid was added to 200 g of each activated carbon and boiled for 30 minutes. Then, using ion-exchanged water (60 ° C.) 20 to 100 times the amount of activated carbon, the mixture was stirred and washed in an upward flow. The activated carbons shown in Table 2 having the same water retention rate and different chloride concentrations as shown in Table 2 were prepared.
(3) Preparation of activated carbon having a high water retention rate Activated carbon having a high water retention rate shown in Table 2 was prepared in the same manner as in the above (2) except that the activation time with water vapor was further extended.
臭素添着活性炭の調整
実施例１で調製した各活性炭を、１１５℃にて３時間、電気乾燥器で乾燥し、デシケーター中で室温まで冷却した。所定量の活性炭を秤量し、ついで各試料を１リットル容のガラス製三角フラスコに移した。活性炭層を平坦にした上にシリカウール各約３ｇを置き、その上に所定量の試薬特級の臭素１０ｇを滴下し、フラスコを振盪攪拌して蒸発した臭素ガスを活性炭試料に添着し、試料Ａ〜Ｐを調製した。得られた活性炭粒子は十分な機械的強度を備えていた。なお、臭素添着炭における臭素吸着量は、臭素がすべて添着され、フラスコ内が無色透明になってから試料を取出した際の重量増加から算出した。
それらの結果を表１および２に記載した。
［試験例１］
Preparation of bromine-impregnated activated carbon Each activated carbon prepared in Example 1 was dried with an electric dryer at 115 ° C. for 3 hours and cooled to room temperature in a desiccator. A predetermined amount of activated carbon was weighed and then each sample was transferred to a 1 liter glass Erlenmeyer flask. About 3 g of each silica wool is placed on a flat activated carbon layer, 10 g of a specified amount of reagent-grade bromine is dropped thereon, and the bromine gas evaporated by shaking and stirring the flask is attached to the activated carbon sample. ~ P was prepared. The obtained activated carbon particles had sufficient mechanical strength. The bromine adsorption amount in the bromine-impregnated coal was calculated from the weight increase when the sample was taken out after all bromine was impregnated and the flask became colorless and transparent.
The results are shown in Tables 1 and 2.
[Test Example 1]
実施例２で調製した臭素添着活性炭Ａ〜Ｐを用いて、硫化ジメチルの吸着性能を破過時間によって判定した。
硫化ジメチルの吸着性能の測定
実施例２で得られた各臭素添着活性炭を１６〜２２メッシュに破砕整粒し、内径１５.６ｍｍのガラスカラムに１００ｍｍ層高（１９.１ｍｌ）で充てんし、硫化ジメチル３ｐｐｍを含有する相対湿度８０％の空気を２５℃において４０ｃｍ／ｓｅｃの流速で流通させた。
各活性炭層の入口における硫化ジメチルのガス濃度（Ｃｏ）と出口における同ガス濃度（Ｃ）とをＦＰＤ検出器付ガスクロマトグラフィで経時測定し、各試料の破過率Ｃ/Ｃｏが０.０５になるまでのガス流通時間（破過時間）を求めた。
その結果を表１および２に纏めた。
Using the bromine-impregnated activated carbons A to P prepared in Example 2, the adsorption performance of dimethyl sulfide was determined by the breakthrough time.
Measurement of adsorption performance of dimethyl sulfide Each bromine-impregnated activated carbon obtained in Example 2 was crushed and sized to 16 to 22 mesh, filled in a glass column with an inner diameter of 15.6 mm with a layer height of 100 mm (19.1 ml), and sulfided. 80% relative humidity air containing 3 ppm of dimethyl was circulated at 25 ° C. at a flow rate of 40 cm / sec.
The gas concentration (Co) of dimethyl sulfide at the inlet of each activated carbon layer and the gas concentration (C) at the outlet were measured over time by gas chromatography with an FPD detector, and the breakthrough rate C / Co of each sample was 0.05. The gas circulation time (breakthrough time) to be was calculated.
The results are summarized in Tables 1 and 2.
表１、表２に示された結果から明らかなように、保水率が４４〜６０％の範囲内にあり、しかも塩化物の含有量が０．０１重量％より少なく、活性炭の臭素添着量が３〜２０％の範囲で添着した活性炭（Ｂ、Ｃ、Ｄ、Ｆ、Ｇ、Ｈ、Ｋ、Ｌ及びＮ）は、高い硫化ジメチル除去性能を示した。しかし、活性炭Ｏを用いた実験では、高い硫化ジメチル除去性能を示したものの、試験期間を通じて装置出口ガスに臭素臭があり、活性炭からの臭素の漏出が認められた。
一方、保水率が４４％未満であるか、塩化物の含有率が０．０１重量％を超えているか、あるいは活性炭の臭素添着量が３％未満の活性炭（Ａ、Ｅ、Ｉ、Ｊ、Ｍ及びＰ）では充分な硫化ジメチル除去性能が示されなかった。
As is apparent from the results shown in Tables 1 and 2, the water retention rate is in the range of 44 to 60%, the chloride content is less than 0.01% by weight, and the bromine loading amount of activated carbon is Activated carbon (B, C, D, F, G, H, K, L, and N) impregnated in the range of 3 to 20% exhibited high dimethyl sulfide removal performance. However, in the experiment using activated carbon O, although high dimethyl sulfide removal performance was shown, bromine odor was found in the apparatus outlet gas throughout the test period, and leakage of bromine from the activated carbon was observed.
On the other hand, activated carbon (A, E, I, J, M, whose water retention rate is less than 44%, whose chloride content exceeds 0.01% by weight, or whose bromine loading of activated carbon is less than 3%. And P) did not show sufficient dimethyl sulfide removal performance.
下水処理場、し尿処理場、ゴミ処理場などの排ガス又は石油精製、石油化学、紙パルプなどの化学工場、食品工場などの工程ガス又は排ガス中には硫化水素、メルカプタン類、硫化アルキル類などの硫黄化合物が含まれている。本発明の臭素添着活性炭は、これらの事業場や施設で発生する硫化アルキル類含有気体中から硫化アルキル類を効率的且つ長期に亘り安定して除去することができる。
Exhaust gas from sewage treatment plants, human waste treatment plants, garbage treatment plants, etc., chemical refineries such as petroleum refining, petrochemical, paper pulp, etc., and process gases or exhaust gases from food factories, etc. include hydrogen sulfide, mercaptans, alkyl sulfides, etc. Contains sulfur compounds. The bromine-impregnated activated carbon of the present invention can efficiently and stably remove alkyl sulfides from the alkyl sulfide-containing gas generated at these business sites and facilities.
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