JP4666452B2 - Compressed activated carbon block - Google Patents
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- JP4666452B2 JP4666452B2 JP2004148539A JP2004148539A JP4666452B2 JP 4666452 B2 JP4666452 B2 JP 4666452B2 JP 2004148539 A JP2004148539 A JP 2004148539A JP 2004148539 A JP2004148539 A JP 2004148539A JP 4666452 B2 JP4666452 B2 JP 4666452B2
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Description
本発明は,水道水の浄化に適用する浄水器用フィルタに関するものである。 The present invention relates to a water purifier filter applied to the purification of tap water.
従来の圧縮活性炭ブロックの構造を図2に示す。この従来ブロック10はふる
い分級により粒径を250μm程度に均一化した破砕炭11を用い,ポリエチレ
ン12をバインダとして完全混合した後,200℃程度で中空円柱状に加圧成形
していた。
The structure of a conventional compressed activated carbon block is shown in FIG. This
このようにして成形されたブロック10は,直径10μm程度の細孔13を有
する浄水用フィルタとして使用される。この圧縮活性炭ブロックでは,前記細孔
径を上回る大きさの微粒子,例えば,浮遊有機成分,微生物,鉄サビ,砂利など
の水道水に混入した異物をふるい効果によって物理的に捕捉できる。
さらに,活性炭の吸着性能を利用し,次亜塩素酸などの遊離塩素成分や溶解性の
有機物,例えば,発ガン性を有するトリハロメタン類をはじめとする有機塩素化
合物,2−メチルイソボルネオール等のカビ臭成分,農薬成分などを除去する。
また,近年は,微量の溶解性鉛が含まれたことを想定して,活性炭に20〜30%
の陽イオン交換樹脂を配合して使用されることも多い。
The
Furthermore, by utilizing the adsorption performance of activated carbon, free chlorine components such as hypochlorous acid and soluble organic substances such as organochlorine compounds such as carcinogenic trihalomethanes, 2-methylisoborneol and other molds. Remove odorous and agrochemical ingredients.
In recent years, it has been assumed that a small amount of soluble lead is contained, and the activated carbon is 20-30%.
Often used in combination with other cation exchange resins.
前記活性炭ブロックに使用される破砕炭は,木炭,ヤシ殻炭,石炭などの炭素
質原料を用い,水蒸気,二酸化炭素,空気などのガス混合下において700〜1
000℃で焼成した後,破砕され,洗浄・乾燥処理を経て製造される。また,前
記過程を経て製造された破砕炭は,粒度分布の均一化を図るためにふるい分け操
作が行われる。
前記活性炭ブロックに使用される破砕炭の粒度は10〜60メッシュであり,
最も細かな60メッシュの破砕炭を採用した場合,粒径は0.25mm以下とな
る。図3に破砕炭の拡大図を示す。破砕炭の平坦な破砕面14上に前記遊離塩素
成分や溶解性の有機物を吸着するための無数の細孔15が形成されている。
また,図4に前記圧縮活性炭ブロックの細孔分布図を示す。圧縮活性炭ブロッ
クは1×10−2〜1×102μmの範囲の幅広い細孔径を有しているが,10μ
m付近に大きな占有率をもつ分布となっている。
The crushed charcoal used for the activated carbon block uses carbonaceous raw materials such as charcoal, coconut shell charcoal, and coal, and is 700 to 1 in a gas mixture such as water vapor, carbon dioxide, and air.
After firing at 000 ° C, it is crushed and manufactured through washing and drying. The crushed coal produced through the above process is subjected to a sieving operation in order to make the particle size distribution uniform.
The particle size of the crushed coal used for the activated carbon block is 10-60 mesh,
When the finest 60 mesh crushed coal is employed, the particle size is 0.25 mm or less. Fig. 3 shows an enlarged view of crushed coal.
FIG. 4 shows a pore distribution diagram of the compressed activated carbon block. The compressed activated carbon block has a wide pore diameter ranging from 1 × 10 −2 to 1 × 10 2 μm, but 10 μm.
The distribution has a large occupation rate in the vicinity of m.
なお,特許文献1には,35〜200μmの基材活性炭に粒径が30μm以下
の超微粉活性炭を配合した活性炭をセラミックス系バインダを用いて加圧成形,
焼成することで10−1〜8μm間に主要細孔分布を有する焼成活性炭ブロック
フィルタを製造し,前記細菌およびウイルスを捕捉する技術が記載されている。
A technique for producing a fired activated carbon block filter having a main pore distribution between 10 −1 and 8 μm by firing and capturing the bacteria and viruses is described.
なお,前記従来の圧縮活性炭ブロックは次の問題を有していた。
(1)体形が10μm以上である原生動物や節足動物などの微小動物は完全に除
去できるが,1μm以下の細菌類,例えば,体径が0.5〜1μmの大腸菌や0.
5〜0.8μmの緑膿菌および0.01〜0.2μmのウイルスを捕捉すること
は不可能であった。
(2)10μm以下の細孔径を有しているものの,細孔分布は10μmの近傍に
偏りを生じていること,原料とする破砕炭の表面が極めて平坦であることから,
本圧縮活性炭ブロックのろ過性能は表面近傍の細孔による10μmのふるい効果
のみに依存しているため,異物の捕捉容量が乏しく,短期間で閉塞を生じる欠点
をもっていた。
The conventional compressed activated carbon block has the following problems.
(1) Micro-animals such as protozoa and arthropods whose body shape is 10 μm or more can be completely removed, but bacteria of 1 μm or less, for example, E. coli having a body diameter of 0.5 to 1 μm, and 0.
It was impossible to capture 5-0.8 μm Pseudomonas aeruginosa and 0.01-0.2 μm virus.
(2) Although it has a pore diameter of 10 μm or less, the pore distribution is biased in the vicinity of 10 μm, and the surface of the crushed coal used as a raw material is extremely flat.
Since the filtration performance of this compressed activated carbon block depends only on the 10 μm sieving effect due to the pores near the surface, the trapping capacity of foreign matter is poor and it has the disadvantage of causing clogging in a short period of time.
また,前述の特許文献1に記載の微小な細孔径を有する焼成活性炭ブロックフ
ィルタを用いた場合は,前記超微粉活性炭の配合量に対し,バインダの添加量が
少なくなると超微粉活性炭の脱落やブロックフィルタの欠け等が生じるため,実
用面を加味した焼成活性炭ブロックフィルタの強度を確保するためにバインダの
添加率を高くする必要があった。
なお,バインダ添加率の増加は活性炭量の低下を意味し,これによって,有機塩
素化合物,カビ臭成分,農薬等に対する吸着容量の低下を招き,浄水器用フィル
タとしての期待寿命が減少する課題が生じた。
さらに,焼成活性炭ブロックフィルタは,加圧成形後,バインダと活性炭が数1
0wt%の水分を含有しており,この水分を焼成前に加湿および加熱乾燥して焼
き固めるため,バインダに大きな容積変化(収縮)が生じ,前述の細孔分布に大
きなばらつきを与える要因となる。
In addition, when the calcined activated carbon block filter having the fine pore diameter described in Patent Document 1 is used, if the amount of the binder is decreased with respect to the blended amount of the ultrafine activated carbon, the ultrafine powder activated carbon is removed or blocked. Since chipping of the filter occurs, it is necessary to increase the additive rate of the binder in order to ensure the strength of the fired activated carbon block filter taking practical aspects into consideration.
An increase in the binder addition rate means a decrease in the amount of activated carbon, which leads to a decrease in the adsorption capacity for organochlorine compounds, musty odor components, agricultural chemicals, etc., resulting in a decrease in the expected life of the filter for water purifiers. It was.
Furthermore, the calcined activated carbon block filter is composed of a binder and activated carbon after pressure molding.
It contains 0wt% of moisture, and this moisture is humidified and dried by heating before baking, which causes a large volume change (shrinkage) in the binder and causes a large variation in the pore distribution described above. .
本発明の主要な目的は,上記課題を解決し,微生物や有機物による汚染のない
水道水を安定供給する圧縮活性炭ブロックを提供することにある。
The main object of the present invention is to provide a compressed activated carbon block that solves the above-mentioned problems and stably supplies tap water free from contamination by microorganisms and organic substances.
上記の課題を解決するために,本発明の圧縮活性炭ブロックは,10〜100
μmの粒度範囲をもつ破砕炭をSiO2及びAl2O3を主成分とする粘土によ
り加湿条件下で造粒し,焼成して,50〜200μm付近に主要粒度分布をもつ
造粒炭を生成し,前記造粒炭にポリエチレンをバインダとして混合し,中空円柱
状に加熱,加圧成形する。
In order to solve the above-mentioned problems, the compressed activated carbon block of the present invention is 10 to 100.
Pulverized coal with a particle size range of μm is granulated under humidified conditions with clay mainly composed of SiO 2 and Al 2 O 3 and calcined to produce granulated coal with a main particle size distribution around 50 to 200 μm Then, the granulated coal is mixed with polyethylene as a binder, and heated and pressed into a hollow cylindrical shape.
本発明の圧縮活性炭ブロックでは,原料の破砕炭について100μm以上と1
0μm以下の2工程のふるい分け操作を行うことで均一な粒径をもつ破砕炭とし,
この破砕炭を粘土によって造粒する。また,この粒子を焼成後,再度,ふるい分
け操作を行うことで50〜200μm付近を中心とした極めてばらつきの少ない
均一な粒度分布をもつ造粒炭を生成できる。
なお,前記造粒炭は球状で平坦な粘土の表面に前記破砕炭がランダムに散りばめ
られたもので,造粒炭の表面には破砕炭による多数の突起が形成された構造をと
り,この造粒炭とポリエチレンバインダを完全混合した後,中空円柱状に加温条
件下で加圧成形する。
In the compressed activated carbon block of the present invention, the raw crushed coal is 100 μm or more and 1
A crushed charcoal with a uniform particle size is obtained by sieving in two steps of 0 μm or less.
This crushed charcoal is granulated with clay. Further, by performing the sieving operation again after firing the particles, granulated coal having a uniform particle size distribution with very little variation around 50 to 200 μm can be generated.
The granulated coal has a structure in which a large number of protrusions are formed on the surface of the granulated coal, the crushed coal being randomly scattered on a spherical and flat clay surface. After complete mixing of granular charcoal and polyethylene binder, press molding into a hollow cylindrical shape under heating conditions.
本発明に係る圧縮活性炭ブロックでは,焼成後に初期の粒度分布をもった造粒
炭を使用でき,かつ,バインダが完全溶融し,浸透して接合するポリエチレンを
使用しているため,バインダの粒径が成形後の細孔分布に影響を及ぼすことはな
い。さらに,バインダの添加率も低く抑えることができ,造粒炭の配合率を高め
た長寿命の浄水フィルタを提供できる。
In the compressed activated carbon block according to the present invention, granulated coal having an initial particle size distribution after firing can be used, and since the binder is completely melted and penetrated and joined to polyethylene, the particle size of the binder is used. Does not affect the pore distribution after molding. Furthermore, the additive rate of the binder can be kept low, and a long-life water filter with an increased granulated coal content can be provided.
また,細孔内部の至る所に破砕炭の突起がせり出しているため,細孔径が1×
10−3〜10μmの広範,かつ,平滑な細孔分布を与えることができ,0.1μ
m以下の微小細孔を数多く備えることができる。
よって,本発明の圧縮活性炭ブロックによれば,10μmを超過する原生動物や
節足動物などの微小動物は無論のこと,体径が0.5〜1μmの大腸菌や0.5
〜0.8μmの緑膿菌などの細菌類および0.01〜0.2μmのウイルスに対
しても高い捕捉性能を発揮することが可能となる。
In addition, since the protrusions of crushed coal protrude everywhere inside the pores, the pore diameter is 1 ×
Can provide a wide and smooth pore distribution of 10 −3 to 10 μm, and 0.1 μm
Many fine pores of m or less can be provided.
Therefore, according to the compressed activated carbon block of the present invention, it is a matter of course that protozoa and arthropods exceeding 10 μm are small animals such as Escherichia coli and 0.5 to 1 μm in diameter.
High capture performance can be exhibited even for bacteria such as ~ 0.8 μm of Pseudomonas aeruginosa and viruses of 0.01 to 0.2 μm.
さらに,前記圧縮活性炭ブロックの細孔分布は,1×10−3〜10μmの範囲
内で際だった偏りを持たず,1×10−3〜1×10−1μmの微小領域の占有率
を大きくすることで,各種サイズの異物の捕捉に対して細孔利用率を高めること
ができるため,異物の捕捉容量が高く,ろ過寿命の長い圧縮活性炭ブロックを実
現することができる。
Furthermore, pore distribution of said compressed activated carbon block, 1 × 10 no bias was pronounced in the range of -3 10 .mu.m, the 1 × 10 -3 ~1 × 10 -1 μm occupancy of minute regions of the By increasing the size, it is possible to increase the pore utilization rate for capturing foreign substances of various sizes, so that it is possible to realize a compressed activated carbon block having a high capacity for capturing foreign substances and a long filtration life.
以下,本発明で具体化した一実施形態を図に基づいて説明する。図1に示すよ
うに,本発明の圧縮活性炭ブロック1は,造粒炭2がバインダのポリエチレン4
によって接合された形態をとり,前記造粒炭2の間隙で構成される細孔5の内部
には造粒炭2の表面に散りばめられた破砕炭3が至る所に突出している。
前記破砕炭3は,前述の従来技術と同様に木炭,ヤシ殻炭,石炭などの炭素質
を原料として焼成,破砕,洗浄,乾燥の過程を経て製造するが,ふるい分け操作
を100μm以上と10μm以下の2工程とすることで粒径の均一化を図る。
また,次工程で行う混粘作業を効率化し,かつ,均質なものとするため,前述の
粒径が整えられた破砕炭3に水分を加え,湿潤させる。このとき,過剰な水分を
与えた場合,破砕炭3が凝集して均質な混粘が行われないため,含水率を30〜
50wt%程度に調湿することが望ましい。
Hereinafter, an embodiment embodied in the present invention will be described with reference to the drawings. As shown in FIG. 1, the compressed activated carbon block 1 of the present invention comprises a polyethylene 4 having a granulated coal 2 as a binder.
The crushed
The crushed
In addition, in order to make the mixing work performed in the next process more efficient and uniform, moisture is added to the crushed
It is desirable to adjust the humidity to about 50 wt%.
さらに,SiO2及びAl2O3を主成分とする粘土粉をふるい分け操作を行い,
200μm以下の粒径に調整する。なお,50μm以下の極めて微細な粘土粉が
混在しても後述の造粒過程で大きな粒子に吸収されるため,問題ではない。
Furthermore, a clay powder mainly composed of SiO 2 and Al 2 O 3 is screened.
The particle size is adjusted to 200 μm or less. Even if extremely fine clay powder of 50 μm or less is mixed, it is not a problem because it is absorbed by large particles in the granulation process described later.
前記,調湿後の破砕炭3と粘土粉とを2:1〜4:1の配合でミキシングして混
合粉を作製し,造粒機に投入する。造粒機は,上部に前記混合粉と造粒のための
調湿に必要な水分の供給口を備え,下部に回転平板を備える。
前記混合粉は,回転平板上を転がりつつ,突起に衝突を繰り返すことで球状粒子
を形成し,粒径の小さな破砕炭3が粒子の表面に捕集されて造粒炭が生成される。
なお,造粒過程では形成された粒子の粉砕を防止し,かつ,破砕炭3の捕集促進
や脱落防止の目的で水分の添加が必要となり,前記混合粉に対し,10〜20w
t%程度の水分を供給することが望ましい。
The crushed
The mixed powder forms spherical particles by repeatedly colliding with the protrusions while rolling on a rotating flat plate, and the crushed
In the granulation process, it is necessary to add water to prevent the formed particles from being pulverized and to promote the collection of crushed
It is desirable to supply about t% of moisture.
また,この造粒炭を1000℃程度の高温で焼成を行った後,再度,ふるい分け
操作を行うことで,50〜200μm付近に主要粒度分布をもつ極めてばらつき
の少ない均一な粒径の造粒炭2を生成する。
In addition, this granulated coal is fired at a high temperature of about 1000 ° C. and then subjected to a sieving operation again, so that the granulated coal has a main particle size distribution around 50 to 200 μm and a uniform particle size with very little variation. 2 is generated.
図5に焼成後の造粒炭2の拡大図を示す。前述したように造粒炭2の表面には前
記破砕炭3がランダムに散りばめられた形状を構成する。
なお,造粒に使用する粘土6は,焼成後の減容による粒度分布のばらつきを抑え,
かつ,浄水器への適用を加味して,有機物含有量および鉄分が少なく,さらに,
鉛,砒素などの有害物質を含まない原料を選定することが望ましい。
FIG. 5 shows an enlarged view of the granulated coal 2 after firing. As described above, the surface of the granulated coal 2 has a shape in which the crushed
The clay 6 used for granulation suppresses the dispersion of the particle size distribution due to volume reduction after firing,
In addition, considering the application to water purifiers, the organic matter content and iron content are low.
It is desirable to select raw materials that do not contain harmful substances such as lead and arsenic.
上記造粒炭2を70〜80wt%,バインダとするポリエチレン4を30〜2
0wt%の配合として,充分に混合した後,ポリエチレン4の溶融温度である約
200℃以上に加熱し,加圧して,中空円筒状に成形する。このようにして製造
された圧縮活性炭ブロック1に形成された細孔5は前記破砕炭3の突起部3aの
存在で外表面から内部に向かって,開孔部の形状,大きさが著しく変化している。
この細孔径の変化を細孔分布図(図6)に基づいて説明する。1×10−3〜10
μmの広範な細孔径を有し,かつ,1×10−1μm以上の比較的大きな細孔につ
いては平滑化した分布をもたせ,1×10−1μm未満の微小細孔については,前
者に比較して減少傾向をとるものの,幅広く,かつ高い占有率を確保している。
Polyethylene 4 containing 70 to 80 wt% of the
As a 0 wt% blend, after mixing well, it is heated to about 200 ° C. or higher, which is the melting temperature of polyethylene 4, and pressed to form a hollow cylinder. The
The change in the pore diameter will be described based on the pore distribution diagram (FIG. 6). 1 × 10 −3 to 10
For pores with a wide pore size of μm and relatively large pores of 1 × 10 −1 μm or more, a smooth distribution is given. For micropores of less than 1 × 10 −1 μm, the former Although it tends to decrease in comparison, it has a wide and high occupation rate.
従って,この実施形態の圧縮活性炭ブロックによれば,次のような作用効果を
期待することができる。
(1)粒度分布の均一な焼成後の造粒炭を使用し,かつ,バインダが完全溶融し,
浸透して接合するポリエチレンを使用しているため,バインダの粒径が成形後の
細孔分布に影響を及ぼすことはなく,1×10−3〜10μm間の広範,かつ,平
滑化された細孔分布を有する圧縮活性炭ブロックを提供できる。
さらに,バインダの添加率も低く抑えることができ,造粒炭の配合率を高められ
るため,遊離塩素や有機塩素化合物,カビ臭成分,農薬成分等の有機物に対して
長寿命の浄水性能を確保できる。
(2)1×10−3〜10μmの広範,かつ,平滑化された細孔分布を有するとと
もに,1×10−1μm未満の微小細孔の占有率も高いことから,体径が10μm
を超過する微小動物をはじめ,1×10−1μmオーダーの細菌類や1×10−2
μmオーダーのウイルスに対しても高い捕捉性能を発揮できる。
(3)異物のサイズに応じて,ろ過機能を発揮する細孔が異なるため,細孔利用
率が向上し,異物の捕捉容量が高められることで,ろ過寿命の長い圧縮活性炭ブ
ロックを実現することができる。
Therefore, according to the compressed activated carbon block of this embodiment, the following effects can be expected.
(1) Using granulated charcoal after firing with uniform particle size distribution, and the binder is completely melted,
Since polyethylene that penetrates and joins is used, the particle size of the binder does not affect the pore distribution after molding, and it is a wide and smooth surface between 1 × 10 −3 and 10 μm. A compressed activated carbon block having a pore distribution can be provided.
In addition, since the binder addition rate can be kept low and the blending rate of granulated coal can be increased, long-term water purification performance is ensured for organic substances such as free chlorine, organic chlorine compounds, mold odor components, and agricultural chemical components. it can.
(2) Since it has a wide and smooth pore distribution of 1 × 10 −3 to 10 μm and a high occupation rate of micropores of less than 1 × 10 −1 μm, the body diameter is 10 μm.
1 × 10 −1 μm order bacteria and 1 × 10 −2
High capture performance can be demonstrated even for viruses of μm order.
(3) Realize a compressed activated carbon block with a long filtration life by improving the pore utilization rate and increasing the trapping capacity of the foreign matter because the pores that perform the filtration function differ depending on the size of the foreign matter. Can do.
また,本圧縮活性炭ブロックでは破砕炭の造粒材にSiO2及びAl2O3を豊
富に含んだ粘土を使用している。SiO2及びAl2O3は陽イオン交換剤として
利用されるゼオライトの原料となり,水中の鉛,クロム等の有害な重金属イオン
を除去する特性をもっていることから,陽イオン交換樹脂を配合しなくとも鉛イ
オンの除去性能を確保することができる。
In this compressed activated carbon block, clay containing abundant SiO 2 and Al 2 O 3 is used as a granulated material for crushed coal. Since SiO 2 and Al 2 O 3 are raw materials for zeolites used as cation exchangers and have the property of removing harmful heavy metal ions such as lead and chromium in water, there is no need to add a cation exchange resin. Lead ion removal performance can be ensured.
1 圧縮活性炭ブロック
2 造粒炭
3 破砕炭
3a 突起
4 ポリエチレン
5 細孔
6 粘土
1 Compressed activated carbon block 2
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