JP3830247B2 - 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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Description
【０００１】
【発明の属する技術分野】
本発明は、臭素添着活性炭及びその製造方法に関し、より詳細には、低濃度で硫化アルキル類を含有する気体中から硫化アルキル類を除去するために使用される臭素添着活性炭及びその製造方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
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。
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。
【０００３】
しかし、これらの従来法では多く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。
これに対して、活性炭吸着法において、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、例えば、特開昭５４−１３２４７０号公報、特公昭５５−２０７３２号公報及び特開昭５５−５１４２２号公報などにより提案されている。
【０００４】
確かに、臭素を添着させた活性炭を用いた場合には、従来法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、臭素添着活性炭における活性炭の品質が、添着される臭素量等、種々のパラメータに起因して均一でなく、硫化ジメチル、二硫化ジメチルを必ずしも満足できる程度まで除去することができていないというのが現状である。
【０００５】
【課題を解決するための手段】
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成分、性状及び物性等を詳細に検討した結果、活性炭中に含まれる不純物、すなわち炭素以外の元素、特に活性炭表面に存在する酸化物の多少が、臭素添着活性炭の吸着性能の低下に影響していることを見い出し、本発明に至った。
【０００６】
すなわち、本発明によれば、表面酸化物の含量が酸素として２．５ｗｔ％以下であり、臭素が３ｗｔ％以上で添着されてなる臭素添着活性炭（分子篩炭を除く）が提供される。
また、原料活性炭を、酸素不存在下で５００〜１１００℃で熱処理して担体活性炭とした後、該担体活性炭に臭素を添着させる上記臭素添着活性炭の製造方法が提供される。
【０００７】
【発明の実施の形態】
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、石炭、コークス、木炭、ヤシガラ、樹脂、石油残渣などを原料として公知の方法により製造されたもので、その比表面積が１００〜２０００ｍ2 ／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。
【０００８】
本発明の臭素添着活性炭において、その含量が制限される表面酸化物としては、例えば一酸化炭素、二酸化炭素、アルカリ金属又はアルカリ土類金属の酸化物等の種々の酸化物が挙げられる。酸化物の含量は、臭素未添着の担体活性炭に対して、酸素として、２．５ｗｔ％以下が好ましく、より好ましくは２ｗｔ％以下、さらに好ましくは１．５ｗｔ％以下である。なお、本発明の臭素添着活性炭は、臭素の酸化作用によって、臭素添着時や経時により活性炭を酸化し、その表面酸化物が若干増える傾向があるため、最終的に得られる臭素添着活性炭の表面酸化物の含量を、臭素未添着の担体活性に対する重量で、上記のように制限している。
【０００９】
本発明の臭素添着活性炭における臭素の含量は、臭素未添着の担体活性炭に対して約３ｗｔ％以上、より好ましくは５ｗｔ％以上、さらに好ましくは５ｗｔ％以上であって５０ｗｔ％以下、最も好ましくは５ｗｔ％以上であって２０ｗｔ％以下である。
【００１０】
また、本発明の臭素添着活性炭の製造方法においては、最終的に得られる臭素添着活性炭の表面酸化物の含量を上記の範囲にするために、臭素添着前の担体活性炭の表面酸化物の含量を、この担体活性炭に対して、酸素として２．０ｗｔ％以下にすることが好ましく、より好ましくは１．５ｗｔ％以下、さらに好ましくは１．０ｗｔ％以下である。
【００１１】
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の表面酸化物の含量を酸素として２．０ｗｔ％以下とする方法は、原料活性炭を、酸素不存在下で５００〜１１００℃で熱処理する方法が挙げられる。熱処理方法としては、例えば、高温熱分解法、高温水素還元法等の種々の方法がある。また、酸素不存在下で熱処理する方法のほかにも、例えば、液相還元法等が挙げられる。しかし、効率的に担体活性炭の表面酸化物の含量を制限する方法としては、高温熱分解法、高温水素還元法等が好ましい。
【００１２】
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、酸化物を熱分解する方法である。この際の熱処理温度は、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℃程度をこ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７００〜９５０℃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。
【００１３】
高温水素還元法は、例えば水素含有ガス雰囲気下で、原料活性炭を熱処理し、酸化物を還元する方法である。この際の熱処理温度は４００〜１０００℃程度が適当であり、好ましくは５００〜８５０℃程度、より好ましくは７００℃前後である。処理時間は、例えば０．１〜１０時間程度が適当である。
【００１４】
液相還元法は、例えば、ヒドラジン等の還元性溶媒中に、常温〜１００℃程度の温度範囲で、原料活性炭を浸漬又は攪拌／混合する方法である。
【００１５】
このような処理は、同一工程を１回又は２回以上繰り返し行ってもよいし、異なる工程の組み合わせによる多段工程で行ってもよい。
【００１６】
また、本発明の臭素添着活性炭における臭素添着は、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、所望の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等を直接散布して添着する方法等が挙げられる。
【００１７】
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、炭素ガス等を用い、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。
【００１８】
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℃程度以下が好ましく、さらに好ましいのは約５０℃以下である。
【００１９】
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、ことに硫化ジメチル、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、バッチ式の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。
【００２０】
以下に、本発明の臭素添着活性炭の調製例及び使用例について説明する。
【００２１】
実施例：
活性炭の熱処理
表１に示した各種の原料および形状の活性炭を管状炉にて８５０℃、窒素５リットル／分、３０分間、３００ｇ仕込の条件で熱処理を行った。熱処理後は窒素ガスで冷却した。
【００２２】
臭素添着炭の調製
熱処理した活性炭を、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、１００ｇを秤取した。
【００２３】
次いで、各試料を１リットル容のガラス製三角フラスコに移し、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〜試料Ｃを調製した。なお、臭素の添着量は、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、表１に示した。
【００２４】
【表１】
硫化ジメチルの吸着性能
上記で得られた各臭素添着活性炭（試料Ａ〜試料Ｃ）を１６〜２４ｍｅｓｈに破砕整粒し、内径１５．６ｍｍのガラスカラムに１００ｍｍ層厚（１９．１ｍｌ）で充填し、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。
【００２６】
各活性炭層の入口における硫化ジメチルのガス濃度（Ｃ0 ）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／Ｃ0 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２に示す。
【００２７】
【表２】
活性炭の表面酸化物の測定
φ２０×１０００ｍｍの石英カラムに臭素添着炭の試料３ｇを入れ、試料の前後は十分に乾燥させたガラスウールで固定し、電気管状炉にセットした。また石英カラムにはゴム栓で前後に蓋をして窒素を導入するための孔と排出するための孔を空けた。１００ｍｌ／分の流速で窒素を石英カラムに流しながら、１００℃まで加熱昇温し、次いで、出口ガスを２リットルのテトラバックに接続し、４００℃／時間の速度で９００℃まで昇温加熱した。９００℃になってから、さらに３０分間９００℃で保持した後、テトラバックを外し、捕集したガス量を測定するとともに、捕集されたガスにおけるＣＯとＣＯ2の総濃度を、水素コンバータ付きのＦＩＤ検出器付ガスクロマトグラフィーで測定し、表面酸化物の酸素としての含量を算出した。その結果を表３に示す。
【００２９】
【表３】
比較例：
臭素添着炭の調製
熱処理を行わない未処理の活性炭を、実施例と同様の方法で臭素添着炭とした。その結果を表４に示した。
【００３１】
【表４】
硫化ジメチルの吸着性能
上記で得られた各臭素添着活性炭（試料Ａ’〜試料Ｃ’）について、実施例と同様の方法で破過時間を求めた。その結果を表５に示す。
【００３３】
【表５】
活性炭の表面酸化物の測定
未処理の活性炭を使用した臭素添着試料の表面酸化物について、実施例と同様の方法により測定した。その結果を表６に示す。
【００３５】
【表６】
【発明の効果】
本発明の臭素添着活性炭によれば、従来技術によって調製された臭素添着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改善す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、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。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a bromine-impregnated activated carbon and a method for producing the same, and more particularly to a bromine-impregnated activated carbon used for removing alkyl sulfides from a gas containing alkyl sulfides at a low concentration and a method for producing the same.
[0002]
[Prior art and problems to be solved by the invention]
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.
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.
[0003]
However, although many 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.
On the other hand, in the activated carbon adsorption method, when bromine-impregnated activated carbon with bromine previously added is used in addition to general activated carbon, a mechanism different from the physical adsorption by the former, that is, dimethyl sulfide and dimethyl disulfide are chemically treated. can be removed by adsorption, for example, JP 54-132470 and JP proposed by like Japanese public Sho 55-20732 and JP 55-51422 JP.
[0004]
Certainly, when activated carbon impregnated with bromine is used, more specific malodorous substances such as dimethyl sulfide and dimethyl disulfide can be removed as compared with the conventional method. The current situation is that the quality is not uniform due to various parameters such as the amount of bromine added, and dimethyl sulfide and dimethyl disulfide cannot be removed to a satisfactory level.
[0005]
[Means for Solving the Problems]
In the process of conducting intensive research in view of the above problems, the present invention has studied in detail the components, properties, physical properties, and the like of various bromine-impregnated activated carbons. As a result, impurities contained in the activated carbon, that is, elements other than carbon, particularly the activated carbon surface As a result, it was found that some of the oxides present in the sample affected the decrease in the adsorption performance of the bromine-impregnated activated carbon, resulting in the present invention.
[0006]
That is, according to the present invention, the content of surface oxides is not more than 2.5 wt% as oxygen, bromine impregnated activated carbon which bromine is being added wearing 3 wt% or more (excluding the molecular sieve carbon) is provided.
Moreover, the raw material activated carbon is heat-treated at 500 to 1100 ° C. in the absence of oxygen to form a supported activated carbon, and then the brominated sorbed activated carbon is produced by adding bromine to the supported activated carbon.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The raw material activated carbon for producing the bromine-impregnated activated carbon of the present invention is manufactured by a known method using, for example, coal, coke, charcoal, coconut husk, resin, petroleum residue, etc., and its specific surface area is 100 to 2000 m. Any material of about 2 / 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.
[0008]
In the bromine-impregnated activated carbon of the present invention, examples of the surface oxide whose content is limited include various oxides such as carbon monoxide, carbon dioxide, alkali metal or alkaline earth metal oxides. The content of the oxide is preferably 2.5 wt% or less, more preferably 2 wt% or less, and further preferably 1.5 wt% or less as oxygen with respect to the carrier activated carbon not doped with bromine. The bromine-impregnated activated carbon of the present invention oxidizes the activated carbon with bromine by oxidation or over time due to the oxidizing action of bromine, and the surface oxide tends to slightly increase. The content of the product is limited as described above by the weight relative to the carrier activity which is not brominated.
[0009]
The bromine content in the bromine-impregnated activated carbon of the present invention is about 3 wt% or more, more preferably 5 wt% or more, still more preferably 5 wt% or more and 50 wt% or less, most preferably 5 wt% with respect to the carrier activated carbon not doped with bromine. % Or more and 20 wt% or less.
[0010]
In addition, in the method for producing bromine-impregnated activated carbon of the present invention, in order to make the content of surface oxide of the bromine-impregnated activated carbon finally obtained within the above range, the content of surface oxide of the carrier activated carbon before bromine-impregnation is adjusted. The oxygen content of the carrier activated carbon is preferably 2.0 wt% or less, more preferably 1.5 wt% or less, and even more preferably 1.0 wt% or less.
[0011]
In the method for producing bromine-impregnated activated carbon of the present invention, the method of setting the surface oxide content of the carrier activated carbon before bromine addition to 2.0 wt% or less as oxygen is that the raw material activated carbon is 500 to 1100 ° C. in the absence of oxygen. The method of heat-processing is mentioned. Examples of the heat treatment method include various methods such as a high temperature pyrolysis method and a high temperature hydrogen reduction method. In addition to the method of heat treatment in the absence of oxygen, for example, a liquid phase reduction method and the like can be mentioned. However, as a method for efficiently limiting the surface oxide content of the supported activated carbon, a high temperature pyrolysis method, a high temperature hydrogen reduction method, or the like is preferable.
[0012]
The high temperature pyrolysis method is a method in which raw material activated carbon is heat-treated in an inert gas not containing oxygen such as nitrogen or argon gas or under vacuum to thermally decompose the oxide. The heat treatment temperature at this time is more efficient as the temperature is higher, but depending on the raw material activated carbon used, there are those in which the pores are blocked at a temperature exceeding about 1200 ° C., so about 500 to 1100 ° C. is appropriate, Preferably it is about 700-950 degreeC. Further, the treatment time can be appropriately adjusted depending on the amount of raw material activated carbon, etc., and for example, about 0.1 to 10 hours is appropriate.
[0013]
The high-temperature hydrogen reduction method is a method in which, for example, a raw material activated carbon is heat-treated in a hydrogen-containing gas atmosphere to reduce oxides. The heat treatment temperature at this time is suitably about 400 to 1000 ° C., preferably about 500 to 850 ° C., more preferably around 700 ° C. The treatment time is suitably about 0.1 to 10 hours, for example.
[0014]
The liquid phase reduction method is a method of immersing or stirring / mixing raw material activated carbon in a reducing solvent such as hydrazine in a temperature range of about room temperature to about 100 ° C.
[0015]
Such a treatment may be performed once or twice or more times, or may be performed in a multi-step process by a combination of different processes.
[0016]
Further, bromine addition in the bromine-impregnated activated carbon of the present invention can be carried out by an addition method known per se. For example, a gas phase deposition method in which a carrier gas containing bromine gas is brought into contact with activated carbon that has been subjected to a desired treatment, a liquid phase deposition method in which the treated activated carbon is immersed in bromine water, a liquid bromine in the treated activated carbon, etc. And a method of directly spraying and attaching.
[0017]
In the vapor deposition method, usually, for example, air, nitrogen gas, carbon gas, or the like is used as a carrier gas, and the contact temperature is adjusted to about 150 ° C. or lower, preferably about 80 ° C. or lower. Vapor deposition is performed continuously using a floor or the like. In this method, it is preferable that after adding bromine-containing gas and adding bromine to the activated carbon, only carrier gas is passed to remove unattached bromine gas.
[0018]
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.
[0019]
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.
Bromine-impregnated activated carbon of alkyl sulfides with the present invention, in particular dimethyl sulfide, two of these alkyl sulfides dimethyl sulfide from gaseous containing Ru intake Chakusu method, for example, fixed bed, moving bed, fluidized bed, A method of bringing the gas to be treated into contact with the bromine-impregnated activated carbon by a known method such as a slurry method or a batch-type contact stirring method may be mentioned. 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.
[0020]
Below, the preparation example and use example of the bromine impregnation activated carbon of this invention are demonstrated.
[0021]
Example:
850 ° C. The various ingredients and the shape of the activated carbon shown in heat treatment Table 1 of the activated carbon in the tube-like furnace, nitrogen 5 l / min, 30 min, heat treatment was performed under the conditions of 300g charged. After the heat treatment, it was cooled with nitrogen gas.
[0022]
Preparation of bromine-impregnated carbon The heat-treated activated carbon was dried with an electric dryer at 115C for 3 hours, cooled to room temperature in a desiccator, and 100 g was weighed.
[0023]
Next, each sample was transferred to a 1 liter glass Erlenmeyer flask, and the activated carbon layer was flattened, and about 3 g of silica wool was placed thereon. On top of that, 10 g of reagent-grade bromine was dropped, and the flask was shaken and stirred. The evaporated bromine gas was attached to the activated carbon sample to prepare Sample A to Sample C. The amount of bromine added was calculated from the weight increase when the sample was taken out after all bromine was added and the inside of the flask became colorless and transparent, and is shown in Table 1.
[0024]
[Table 1]
Adsorption performance of dimethyl sulfide Each bromine-impregnated activated carbon (sample A to sample C) obtained above was crushed and sized to 16 to 24 mesh, and a 100 mm layer thickness (19.1 ml) was placed on a glass column having an inner diameter of 15.6 mm. ), And air having a relative humidity of 80% and containing 3 ppm of dimethyl sulfide was circulated at 25 ° C. at a flow rate of 40 cm / sec.
[0026]
The gas concentration (C 0 ) 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 / C 0 of each sample was 0. The gas circulation time (breakthrough time) until 05 was obtained. The results are shown in Table 2.
[0027]
[Table 2]
The sample was placed 3g of bromine impregnated charcoal quartz column measuring ø20 × 1000 mm of the surface oxides of activated carbon, before and after the sample was fixed with glass wool was sufficiently dried and set in an electric tube-like furnace. In addition, the quartz column was covered with a rubber stopper before and after, and a hole for introducing nitrogen and a hole for discharging were formed. While flowing nitrogen through the quartz column at a flow rate of 100 ml / min, the temperature was raised to 100 ° C., and then the outlet gas was connected to a 2-liter tetrabac and heated to 900 ° C. at a rate of 400 ° C./hour. . After reaching 900 ° C., hold at 900 ° C. for another 30 minutes, then remove the tetraback, measure the amount of gas collected, and add the total concentration of CO and CO 2 in the collected gas with a hydrogen converter. The content of surface oxide as oxygen was calculated by gas chromatography with FID detector. The results are shown in Table 3.
[0029]
[Table 3]
Comparative example:
Preparation of bromine-impregnated carbon Untreated activated carbon not subjected to heat treatment was converted to bromine-impregnated carbon in the same manner as in the examples. The results are shown in Table 4.
[0031]
[Table 4]
Adsorption performance of dimethyl sulfide For each bromine-impregnated activated carbon (sample A ′ to sample C ′) obtained above, breakthrough time was determined in the same manner as in the example. The results are shown in Table 5.
[0033]
[Table 5]
Measurement of surface oxide of activated carbon The surface oxide of a bromine-impregnated sample using untreated activated carbon was measured by the same method as in the examples. The results are shown in Table 6.
[0035]
[Table 6]
【The invention's effect】
According to the bromine-impregnated activated carbon of the present invention, it is possible to improve the adsorption performance for alkyl sulfides, which has been considered insufficient in bromine-impregnated coal prepared by the prior art, and to eliminate variations in the adsorption performance, Stable removal performance of alkyl sulfides can be exhibited.
Claims (3)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29744097A JP3830247B2 (en) | 1997-10-29 | 1997-10-29 | Bromine impregnated activated carbon and method for producing the same |
| US09/121,836 US6514907B2 (en) | 1997-07-25 | 1998-07-24 | Bromine-impregnated activated carbon and process for preparing the same |
| SG1998002664A SG65087A1 (en) | 1997-07-25 | 1998-07-24 | Bromine-impregnated activated carbon and process for preparing the same |
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| Application Number | Priority Date | Filing Date | Title |
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| JP29744097A JP3830247B2 (en) | 1997-10-29 | 1997-10-29 | Bromine impregnated activated carbon and method for producing the same |
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| Publication Number | Publication Date |
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| JPH11128737A JPH11128737A (en) | 1999-05-18 |
| JP3830247B2 true JP3830247B2 (en) | 2006-10-04 |
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| JP29744097A Expired - Fee Related JP3830247B2 (en) | 1997-07-25 | 1997-10-29 | Bromine impregnated activated carbon and method for producing the same |
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| CN103172064A (en) * | 2013-04-12 | 2013-06-26 | 宁夏大学 | Low-ash coal-based activated carbon quick activation production technology |
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| JP2002095927A (en) * | 2000-07-21 | 2002-04-02 | Nikko Plant:Kk | Deodorizing method |
| CN100340683C (en) * | 2002-05-06 | 2007-10-03 | 吸附技术公司 | Sorbents and methods for the removal of mercury from combustion gases |
| JP5069838B2 (en) * | 2003-05-14 | 2012-11-07 | 株式会社キャタラー | Method for producing activated carbon for deodorizer and activated carbon for deodorizer |
| UA109399C2 (en) | 2009-04-01 | 2015-08-25 | THERMALLY ACTIVATED COAL RESISTANT TO SELF-IGNITION | |
| US8198210B2 (en) * | 2010-05-27 | 2012-06-12 | Corning Incorporated | Halogenated activated carbon materials for high energy density ultracapacitors |
| WO2015072263A1 (en) * | 2013-11-13 | 2015-05-21 | 日本エンバイロケミカルズ株式会社 | Adsorbent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103172064A (en) * | 2013-04-12 | 2013-06-26 | 宁夏大学 | Low-ash coal-based activated carbon quick activation production technology |
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