JPS60235637A - Adsorbent for gas - Google Patents
Adsorbent for gasInfo
- Publication number
- JPS60235637A JPS60235637A JP59093507A JP9350784A JPS60235637A JP S60235637 A JPS60235637 A JP S60235637A JP 59093507 A JP59093507 A JP 59093507A JP 9350784 A JP9350784 A JP 9350784A JP S60235637 A JPS60235637 A JP S60235637A
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- activated carbon
- natural
- oxides
- gas
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は悪臭ガスの脱臭に有効な吸着剤に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to an adsorbent effective in deodorizing malodorous gases.
し尿処理場、下水処理場、ゴミ処理場などにおいて、臭
覚閾値の低い硫化水素、メチルメルカプタンなどのイオ
ウ化合物、アンモニア、アミン類などのチッ素化合物を
多量に含有する悪臭ガスが発生する事は周知の如くであ
る。It is well known that foul-smelling gases containing large amounts of hydrogen sulfide, sulfur compounds such as methyl mercaptan, and nitrogen compounds such as ammonia and amines, which have low odor thresholds, are generated in human waste treatment plants, sewage treatment plants, garbage treatment plants, etc. It's like this.
これらの悪臭ガスの脱臭方法としては （１）酸、アルカリ液による洗浄吸収方法。 How to deodorize these foul-smelling gases (1) Cleaning and absorption method using acid or alkaline solution.
（２）過マンガン酸カリ、次亜塩素酸塩類、オゾンなど
の酸化剤を用いた常温酸化方法。(2) Room temperature oxidation method using oxidizing agents such as potassium permanganate, hypochlorites, and ozone.
（３）直接燃焼、触媒燃焼を利用した高温酸化方法。(3) High-temperature oxidation method using direct combustion or catalytic combustion.
（４）有効な吸着剤を用いて、悪臭成分を吸着除去させ
る吸着方法。(4) An adsorption method in which malodorous components are adsorbed and removed using an effective adsorbent.
などが良く使用されているが、各々一長一短があり、 （１１についてはその除去効果が充分ではない。are often used, but each has its advantages and disadvantages. (Regarding No. 11, its removal effect is not sufficient.
（２）については処理後にガス中に含まれるガス状酸化
剤（例えばＣＩ□、０３など）のために後処理が必要に
なる。Regarding (2), post-treatment is required due to the gaseous oxidizing agent (for example, CI□, 03, etc.) contained in the gas after treatment.
（３）については高温下で行われるため燃費がかさむ。As for (3), fuel consumption increases because it is carried out at high temperatures.
（４）については吸着容量に制限があるので、高濃度ガ
スの場合には前処理が必要になる。Regarding (4), since there is a limit to the adsorption capacity, pretreatment is required in the case of high concentration gas.
などの欠点があり、いづれの場合も上記方法は単独使用
よりも複数の方法の組み合せにより行うケースが多い。There are drawbacks such as, in each case, the above methods are often used in combination of multiple methods rather than being used alone.
一方（４）の有効な吸着剤を用いる方法において、近年
適当な金属（Ｆｅ、 Ｍｎｓ Ｎ＋、Ｃｏなど）を担持
添着させて、吸着容量の増大を計った活性炭も多く報告
されている。（特開昭５３−１３７０７１号、同５３−
１３７０８９号）
〔発明が解決しようとする問題点〕
上記（４）の吸着剤を用いる方法は、上記金属の酸化物
を利用するために、活性炭表面に上記金属塩類を担持さ
せ、その後不活性ガス、酸化性ガス、還元性ガスなどの
ガス気流中で２００〜９５０℃の高温で５〜４０時間と
いう長時間焼成するため、（後述の比較例１．２および
４においては従来法（４）の加熱処理条件を本発明と同
一の低温、短時間にした場合の、吸着量を示しである。On the other hand, in the method (4) using an effective adsorbent, there have been many reports in recent years of activated carbon in which appropriate metals (Fe, Mns N+, Co, etc.) are supported and impregnated to increase the adsorption capacity. (Unexamined Japanese Patent Publication No. 53-137071, No. 53-
137089) [Problems to be Solved by the Invention] In the method (4) using an adsorbent, in order to utilize the oxides of the metals, the metal salts are supported on the surface of activated carbon, and then an inert gas is applied. , oxidizing gas, reducing gas, etc., at a high temperature of 200 to 950°C for a long time of 5 to 40 hours (in Comparative Examples 1.2 and 4 described below, conventional method (4) The figure shows the amount of adsorption when the heat treatment conditions are the same as those of the present invention at low temperature and short time.
）それに耐えうる特殊な装置および昇温のために燃費が
かさみ、吸着剤を簡便に安価に得ることは出来なかった
。) Due to the need for special equipment that can withstand this and the increased temperature, fuel consumption increases, and the adsorbent cannot be easily obtained at low cost.
本発明者は従来法の上記欠点を考慮し、鋭意研究の結果
Ｔｉｓ Ｚｒｓ Ｓｎから選ばれた金属化合物を多孔性
物質に担持させると、高温、長時間の熱処理の必要もな
く、低コストで吸着容量の大きい吸着剤が得られること
を見出した。Taking into account the above-mentioned drawbacks of the conventional method, the present inventor conducted extensive research and found that by supporting a metal compound selected from TisZrsSn on a porous material, the adsorption process can be achieved at low cost without the need for high-temperature and long-term heat treatment. It has been found that an adsorbent with a large capacity can be obtained.
本発明はＴｉ、 Ｚｒ又はＳｎの金属塩又は酸化物のう
ち一種以上を、活性炭、天然黄土又は天然ゼオライトな
どの多孔性吸着剤に担持添着させた吸着剤に関する。The present invention relates to an adsorbent in which at least one metal salt or oxide of Ti, Zr, or Sn is supported and impregnated on a porous adsorbent such as activated carbon, natural loess, or natural zeolite.
本発明において使用される金属塩としては、ＴｉＣｌ３
、Ｔｉ０Ｃｈ、ＴｉＣｌ４、Ｚｒ０ＣＩｚ、５ｎＣ１
ｚ、５ｎＣＩ４．５ｎＦｚ、５ｎＦｎ、５ｎＢｒｚ 、
５ｎＢｒｎ 、５ｎＩｚ、５ｎｌａなどのハロゲン化物
、ＴｉＳＯａ 、Ｔｉ０３Ｏｎ、ＺｒＯ３Ｏ４、ＳｎＳ
Ｏ４などの硫酸塩、Ｚｒ０（ＮＯｉ）ｚなどの硝酸塩が
あげられ、上記金属の酸化物としてはＴｉ（ｈ、７ｒｒ
Ｏ１、ＳｎＯ、ＳｎＯ，などがあげられる。The metal salt used in the present invention includes TiCl3
, Ti0Ch, TiCl4, Zr0CIz, 5nC1
z, 5nCI4.5nFz, 5nFn, 5nBrz,
Halides such as 5nBrn, 5nIz, 5nla, TiSOa, Ti03On, ZrO3O4, SnS
Examples include sulfates such as O4, nitrates such as Zr0(NOi)z, and oxides of the above metals include Ti(h, 7rr).
Examples include O1, SnO, SnO, and the like.
多孔性物質としては、活性炭、天然黄土又は天然ゼオラ
イト等があげられ、粉末状又は粒状いづれの形態でも使
用可能である。Examples of the porous material include activated carbon, natural loess, and natural zeolite, which can be used in either powder or granule form.
上記金属塩又は酸化物を担持添着した本発明の吸着剤の
具体的製造方法としては、次の樟な方法があげられる。A specific method for producing the adsorbent of the present invention carrying and impregnating the metal salt or oxide is the following method.
（１） 上記金属塩又は酸化物を水又は有機溶媒に溶解
し、これに活性炭、天然黄土又は天然ゼオライトなどの
一種以上を１時間浸漬させる。(1) The above metal salt or oxide is dissolved in water or an organic solvent, and one or more types of activated carbon, natural loess, or natural zeolite are immersed in the solution for 1 hour.
その後８０℃〜１２０℃で１〜２時間加熱乾燥する。を
機溶媒としてはメタノール、エタノール等の低級アルコ
ールがあげられる。Thereafter, it is heated and dried at 80°C to 120°C for 1 to 2 hours. Examples of the solvent include lower alcohols such as methanol and ethanol.
（２） 活性炭、天然黄土又は天然ゼオライト粉末の一
種以上に、上記金属塩又は酸化物を適当量配合し、適当
な粘結剤を用いて混練、造粒、成型後８０〜１２０℃で
１〜２時間加熱乾燥する。粘結剤としては、カルボキシ
メチルセルロース、メチルセルロース、アルギン酸ソー
ダ、ポリビニルアルコール、ピッチ、リグニン、廃糖蜜
など天然および合成粘結剤が使用される。(2) Mix an appropriate amount of the above metal salt or oxide with one or more of activated carbon, natural loess, or natural zeolite powder, knead with an appropriate binder, granulate, and mold at 80 to 120°C. Heat and dry for 2 hours. As binders, natural and synthetic binders are used, such as carboxymethylcellulose, methylcellulose, sodium alginate, polyvinyl alcohol, pitch, lignin, blackstrap molasses.
（３）上記金属塩又は酸化物を水又は有機溶媒に溶解し
た後粘結剤と混合し、活性炭、天然黄土又は天然ゼオラ
イトの一種以上と混練、造粒、成型後８０℃〜１２０℃
で１〜２時間加熱乾燥する。(3) The above metal salt or oxide is dissolved in water or an organic solvent, mixed with a binder, kneaded with one or more of activated carbon, natural loess, or natural zeolite, granulated, and molded at 80°C to 120°C.
Heat and dry for 1 to 2 hours.
これらの金属塩又は酸化物の担持量は多孔性物質に対し
て重量割合でＩ／、。。。以上好ましくは１八。。〜２
である。The amount of these metal salts or oxides supported is I/, based on the weight of the porous material. . . The above is preferably 18. . ~2
It is.
以下実施例および比較例をあげて本発明を説明する。The present invention will be explained below with reference to Examples and Comparative Examples.
実施例−１
４〜６メツシユに整粒された粒状活性炭を０．５χ−Ｚ
ｒＯＳＯ４水溶液に１時間浸漬させ、その後１２０℃で
２時間加熱乾燥させ冷却し吸着剤を得た。Example-1 Granular activated carbon sized to 4 to 6 meshes at 0.5χ-Z
It was immersed in an rOSO4 aqueous solution for 1 hour, then heated and dried at 120° C. for 2 hours, and then cooled to obtain an adsorbent.
このものを１６〜２４メソシユに整粒し、１０％φのガ
ラスカラムに１０ＣＩ１１の高さに充填し、Ｈ２５１０
００ｐｐｍのガスをカラムに導入通気し、出口濃度１ｐ
ｐＩＩｌでのＩｔｓ破過吸着量を測定した。This material was sized to 16 to 24 mesh, packed in a 10%φ glass column to a height of 10CI11, and
00 ppm of gas was introduced into the column and vented, and the outlet concentration was 1 p.
The breakthrough adsorption amount of Its on pIIl was measured.
比較例−１
４〜６メツシユに整粒された粒状活性炭を０．５χＮ１
Ｃｈ水溶液に１時間浸漬させ、その後１２０°Ｃで２時
間乾燥させ、実施例−１と同一にＨａｓの吸着量を測定
した。Comparative Example-1 Granular activated carbon sized to 4 to 6 meshes at 0.5χN1
It was immersed in a Ch aqueous solution for 1 hour, then dried at 120°C for 2 hours, and the amount of Has adsorption was measured in the same manner as in Example-1.
比較例−２
４〜６メツシユに整粒された粒状活性炭を０．５χ−Ｐ
ｅ５ｏ４水溶液に１時間浸漬させ、その後１２０’ｃで
２時間乾燥させ、実施例−１と同様にＨｚＳの吸着量を
測定した。Comparative Example-2 Granular activated carbon sized to 4 to 6 meshes at 0.5χ-P
It was immersed in an e5o4 aqueous solution for 1 hour, and then dried at 120'C for 2 hours, and the adsorption amount of HzS was measured in the same manner as in Example-1.
比較例−３
４〜６メノシユに整粒された粒状活性炭を０．５χＦｅ
Ｓ０ｍ水溶液に１時間浸漬させ、その後５００°Ｃ５時
間で焼成乾燥させ、実施例−１と同様に１１２３の吸着
量を測定した。Comparative Example-3 Granular activated carbon sized to 4 to 6 grains with 0.5χFe
It was immersed in an S0m aqueous solution for 1 hour, then baked and dried at 500°C for 5 hours, and the adsorption amount of 1123 was measured in the same manner as in Example-1.
上記４点の測定結果を表−１に示す。The measurement results of the above four points are shown in Table-1.
表−１
表−１より明らかの様に、実施例−１で得た吸、５着剤
は、同様にして低温（１２０℃）乾燥で得た他の金属塩
（比較例−１，２）を担持した吸着剤よりも５側根度大
きい吸着性能を示し、かつ不活性ガス下にて高温（５０
０℃）焼成して得た吸着剤（比較例−３）よりも大きな
性能を示した。Table 1 As is clear from Table 1, the adhesion agent obtained in Example 1 is similar to other metal salts (Comparative Examples 1 and 2) obtained by drying at low temperature (120°C). It shows a higher adsorption performance than the adsorbent carrying
It exhibited greater performance than the adsorbent obtained by calcination (Comparative Example-3) (0°C).
実施例−２
２００メフシユ以下の活性炭−６００ｇ 、２００メフ
シユ以下の天然黄土−６００ｇ 、 ＴｉＯ□−５ｇを
良く混合する。Example-2 600 g of activated carbon of 200 mf or less, 600 g of natural loess of 200 mf or less, and 5 g of TiO□ are mixed well.
上記粉体混合物に５％カルボキシメチルセルロース溶液
５００ｇを加え、充分混練し造粒、成形する。Add 500 g of a 5% carboxymethyl cellulose solution to the above powder mixture, thoroughly knead, granulate and shape.
その後１２０℃で２時間乾燥させ、実施例−１と同様に
ＵＺＳ吸着量を測定した。Thereafter, it was dried at 120°C for 2 hours, and the amount of UZS adsorption was measured in the same manner as in Example-1.
比較例−４
２００メフシユ以下の活性炭−６００ｇ、２００メフシ
ユ以下の天然黄土−・−６００ｇ、ＣｌｌＳＯ４・・１
０ｇを良く混合する。Comparative Example-4 Activated carbon of 200 mf or less - 600 g, natural loess of 200 mf or less - 600 g, CllSO4...1
Mix well.
上記粉体混合物に５％カルボキシメチルセルロース溶液
５００ｇを加え、充分混練し、造粒、成形する。Add 500 g of a 5% carboxymethyl cellulose solution to the above powder mixture, thoroughly knead, granulate and mold.
その後１２０℃で２時間乾燥させ、実施例−１と同様に
Ｈｔｓ吸着量を測定した。Thereafter, it was dried at 120°C for 2 hours, and the amount of Hts adsorption was measured in the same manner as in Example-1.
比較例−５
２００メフシユ以下の活性炭−６００ｇ、２００メフシ
ユ以下の天然ゼオライト−３００ｇ、Ｃｕ５Ｏ＜ −４
０ｇ １を良く混合する。Comparative Example-5 Activated carbon of 200 mf or less - 600 g, natural zeolite of 200 mf or less - 300 g, Cu5O < -4
Mix 0g 1 well.
上記粉体混合物にピンチ２０ｇを加え、充分混練し、造
粒、成形する。Add 20 g of pinch to the above powder mixture, thoroughly knead, granulate and shape.
その後Ｎ２ガス中で、５５０℃、５時間焼成し、実施例
−１と同様にＨ２Ｓ吸着量を測定した。Thereafter, it was fired in N2 gas at 550°C for 5 hours, and the amount of H2S adsorbed was measured in the same manner as in Example-1.
実施例−３
２００メフシユ以下の活性炭−６００ｇ、 ２００メフ
シユ以下の天然ゼオライト−３００ｇ、を良く混合する
。Example-3 600 g of activated carbon of 200 mf or less and 300 g of natural zeolite of 200 mf or less are mixed well.
次に５％カルボキシメチルセルロースｉ液４００ｇに対
して５ｎＣＩｚ ５ｇを良く溶解させ、上記粉体混合物
と充分混練し、造粒、成形する。Next, 5 g of 5nCIz is well dissolved in 400 g of 5% carboxymethylcellulose I-liquid, thoroughly kneaded with the above powder mixture, and granulated and molded.
その後１２０°Ｃで１時間乾燥し、実施例−１と同様に
Ｈ，Ｓ吸着量を測定した。Thereafter, it was dried at 120°C for 1 hour, and the amount of H and S adsorbed was measured in the same manner as in Example-1.
上記４点の測定結果を表−２に示した。The measurement results for the above four points are shown in Table 2.
表−２
表−２より明らかの様に、本発明の金属塩又は酸化物を
担持添着した吸着剤は低温（１２０℃）下での加熱乾燥
でも他の金属を担持し、高温（５００℃）で焼成して得
た吸着剤と比較し同等な性能を有する事が出来た。Table 2 As is clear from Table 2, the adsorbent impregnated with a metal salt or oxide of the present invention supports other metals even when heated and dried at a low temperature (120°C), and when dried at a high temperature (500°C). Compared to the adsorbent obtained by firing with
本発明の吸着剤は多孔質物質にＴｉ、Ｚｒ又はＳｎの金
属化合物を低温、短時間の加熱処理で担持した新規なガ
ス用吸着剤であり、他の金属化合物を担持し、高温、長
時間で焼成して得た吸着剤と比べて吸着性能も同等又は
それ以上である。The adsorbent of the present invention is a novel gas adsorbent in which a porous material is supported with a metal compound of Ti, Zr, or Sn by a low-temperature, short-time heat treatment. The adsorption performance is the same or better than that of the adsorbent obtained by firing with.
したがって本発明によると加熱処理に特殊な設備を要す
ることもなく低コストで吸着性能の高い新規な吸着剤が
得られる、という画期的な効果がもたらされるものであ
る。Therefore, according to the present invention, a novel adsorbent with high adsorption performance can be obtained at low cost without requiring any special equipment for heat treatment, which is an epoch-making effect.
出願人 日本化成株式会社 （ほか２名）Applicant Nippon Kasei Co., Ltd. (2 others)
Claims (1)
上を、活性炭、天然黄土又は天然ゼオライトなどの多孔
性物質に担持添着させた吸着剤。An adsorbent in which one or more metal salts or oxides of Tis Zr and Sn are supported and impregnated on a porous substance such as activated carbon, natural loess, or natural zeolite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59093507A JPS60235637A (en) | 1984-05-09 | 1984-05-09 | Adsorbent for gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59093507A JPS60235637A (en) | 1984-05-09 | 1984-05-09 | Adsorbent for gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60235637A true JPS60235637A (en) | 1985-11-22 |
| JPS6322184B2 JPS6322184B2 (en) | 1988-05-11 |
Family
ID=14084259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59093507A Granted JPS60235637A (en) | 1984-05-09 | 1984-05-09 | Adsorbent for gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60235637A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01218635A (en) * | 1988-02-29 | 1989-08-31 | Hitachi Ltd | Deodorizing agent, its manufacturing method, deodorizing method, deodorizing apparatus and refrigeration cycle apparatus with said deodorizing apparatus |
| JPH07185337A (en) * | 1993-12-27 | 1995-07-25 | Mototaka Ueno | Deodorizing adsorbent and deodorizing adsorptive sheet |
| KR20020037609A (en) * | 2000-11-15 | 2002-05-22 | 이후근 | The method of manufacturing about adsorbent for harmful gas removal |
| KR100357765B1 (en) * | 1999-11-25 | 2002-10-25 | (주)바이오세라 | Process of preparation of photo-semiconductive filter for deodorization and antibacterial activity and photo-semiconductive filter for deodorization and antibacterial activity used this process |
| KR20030046159A (en) * | 2001-12-05 | 2003-06-12 | 유건상 | Photocatalytic loess deodorant and method for manufacturing the same |
| KR100436109B1 (en) * | 2001-06-25 | 2004-06-23 | 세신전자(주) | Coupling system of low-temperature catalyst and photocatalyst for indoor air quality control |
| KR100465029B1 (en) * | 2002-02-07 | 2005-01-06 | 고종성 | Bioceramic air cleaner and manufacturing method thereof |
| JP2011507783A (en) * | 2007-08-28 | 2011-03-10 | エルジー ハウシス リミテッド | Tile having formaldehyde adsorption performance and method for producing the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01171279U (en) * | 1988-05-20 | 1989-12-04 | ||
| JPH02119084U (en) * | 1989-03-06 | 1990-09-25 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4922390A (en) * | 1972-06-21 | 1974-02-27 | ||
| JPS5474271A (en) * | 1977-11-25 | 1979-06-14 | Takeda Chem Ind Ltd | Odor removal |
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1984
- 1984-05-09 JP JP59093507A patent/JPS60235637A/en active Granted
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4922390A (en) * | 1972-06-21 | 1974-02-27 | ||
| JPS5474271A (en) * | 1977-11-25 | 1979-06-14 | Takeda Chem Ind Ltd | Odor removal |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01218635A (en) * | 1988-02-29 | 1989-08-31 | Hitachi Ltd | Deodorizing agent, its manufacturing method, deodorizing method, deodorizing apparatus and refrigeration cycle apparatus with said deodorizing apparatus |
| JPH06102155B2 (en) * | 1988-02-29 | 1994-12-14 | 株式会社日立製作所 | Deodorant, deodorant manufacturing method, deodorizing method, deodorizing device, and refrigeration cycle device equipped with this deodorizing device |
| JPH07185337A (en) * | 1993-12-27 | 1995-07-25 | Mototaka Ueno | Deodorizing adsorbent and deodorizing adsorptive sheet |
| KR100357765B1 (en) * | 1999-11-25 | 2002-10-25 | (주)바이오세라 | Process of preparation of photo-semiconductive filter for deodorization and antibacterial activity and photo-semiconductive filter for deodorization and antibacterial activity used this process |
| KR20020037609A (en) * | 2000-11-15 | 2002-05-22 | 이후근 | The method of manufacturing about adsorbent for harmful gas removal |
| KR100436109B1 (en) * | 2001-06-25 | 2004-06-23 | 세신전자(주) | Coupling system of low-temperature catalyst and photocatalyst for indoor air quality control |
| KR20030046159A (en) * | 2001-12-05 | 2003-06-12 | 유건상 | Photocatalytic loess deodorant and method for manufacturing the same |
| KR100465029B1 (en) * | 2002-02-07 | 2005-01-06 | 고종성 | Bioceramic air cleaner and manufacturing method thereof |
| JP2011507783A (en) * | 2007-08-28 | 2011-03-10 | エルジー ハウシス リミテッド | Tile having formaldehyde adsorption performance and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6322184B2 (en) | 1988-05-11 |
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