JP2002143640A - Method for removing halogen-containing gas - Google Patents
Method for removing halogen-containing gasInfo
- Publication number
- JP2002143640A JP2002143640A JP2000343696A JP2000343696A JP2002143640A JP 2002143640 A JP2002143640 A JP 2002143640A JP 2000343696 A JP2000343696 A JP 2000343696A JP 2000343696 A JP2000343696 A JP 2000343696A JP 2002143640 A JP2002143640 A JP 2002143640A
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- Prior art keywords
- halogen
- based gas
- particle diameter
- granulated
- gas
- Prior art date
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- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ハロゲン単体又は
ハロゲン化合物からなるハロゲン系ガスの除去方法に関
し、例えば、ハロゲン系ガスを含有するドライエッチン
グ排ガス等からハロゲン系ガスを除去する方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing a halogen-based gas comprising a halogen alone or a halogen compound, for example, a method for removing a halogen-based gas from a dry etching exhaust gas containing a halogen-based gas.
【０００２】[0002]
【従来の技術】従来より、ハロゲン単体又はハロゲン化
合物からなるハロゲン系ガスを含有するドライエッチン
グ排ガスやＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄ
ｅｐｏｓｉｔｉｏｎ）チャンバーの排ガス等の処理方法
として、設備の小型化及び操作の簡便化のため、活性炭
等の吸着剤を使用した乾式による処理方法等が採用され
ている。しかし、ガス吸着時の吸着熱による発火、使用
済み吸着剤の臭気及び固形廃棄物の発生等が問題であっ
た。2. Description of the Related Art Conventionally, dry etching exhaust gas containing a halogen-based gas consisting of a simple substance of halogen or a halogen compound or CVD (Chemical Vapor D) has been used.
As a method for treating exhaust gas from an evaporation chamber, a dry treatment method using an adsorbent such as activated carbon or the like is employed for miniaturization of equipment and simplification of operation. However, there were problems such as ignition due to heat of adsorption during gas adsorption, odor of used adsorbent, generation of solid waste, and the like.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記の問題
に鑑み、吸着剤の発火を抑制し、ハロゲン系ガスの処理
能力が高く、使用済み吸着剤の臭気及び固形廃棄物の発
生を低減した、ハロゲン系ガスの除去方法を提供する。SUMMARY OF THE INVENTION In view of the above problems, the present invention suppresses ignition of an adsorbent, has a high processing capacity for halogen-based gas, and reduces the odor of used adsorbent and the generation of solid waste. And a method for removing a halogen-based gas.
【０００４】[0004]
【課題を解決するための手段】本発明は、一次粒子の平
均粒子径１０〜５００μｍの炭酸水素塩の粉末を圧縮成
形法により造粒し、得られた造粒物を、ハロゲン単体又
はハロゲン化合物からなるハロゲン系ガスに接触させて
ハロゲン系ガスを除去する、ハロゲン系ガスの除去方法
を提供する。According to the present invention, there is provided a method of granulating a bicarbonate powder having an average primary particle diameter of 10 to 500 μm by a compression molding method, and forming the granulated product into a simple halogen or a halogen compound. A halogen-based gas removing method for removing the halogen-based gas by contacting the halogen-based gas with the halogen-based gas.
【０００５】さらに、本発明は、炭酸水素塩の粉末を造
粒してなる平均粒子径０．５〜２０ｍｍの造粒物であっ
て、粒子径０．５〜１．０ｍｍ間の造粒物の平均硬度が
１Ｎ以上、又は、粒子径１．０〜１．５ｍｍ間の造粒物
の平均硬度が４Ｎ以上、又は、粒子径１．５〜２．０ｍ
ｍ間の造粒物の平均硬度が１０Ｎ以上、又は、粒子径
２．０ｍｍ以上の造粒物の平均硬度が３０Ｎ以上、であ
る造粒物を、ハロゲン単体又はハロゲン化合物からなる
ハロゲン系ガスに接触させてハロゲン系ガスを除去す
る、ハロゲン系ガスの除去方法を提供する。Further, the present invention relates to a granulated product having an average particle size of 0.5 to 20 mm obtained by granulating bicarbonate powder, wherein the granulated product has a particle size of 0.5 to 1.0 mm. Has an average hardness of 1N or more, or an average hardness of granules having a particle diameter of 1.0 to 1.5 mm of 4N or more, or a particle diameter of 1.5 to 2.0 m.
The average hardness of the granulated material having a mean particle size of 10 N or more, or the average hardness of the granulated material having a particle size of 2.0 mm or more is 30 N or more, is converted into a halogen-based gas composed of a simple halogen or a halogen compound. Provided is a method for removing a halogen-based gas, wherein the halogen-based gas is removed by contact.
【０００６】[0006]
【発明の実施の形態】本発明において、炭酸水素塩とし
ては、炭酸水素ナトリウム、炭酸水素カリウム等が使用
できる。特に、大量かつ安価に入手できることから工業
的に適していることや、吸湿性がなく、造粒物の製造や
保存にあたって使用しやすいことから、炭酸水素ナトリ
ウムが好ましい。一方、除去処理後の排ガス等へのナト
リウムの混入を防ぎたい場合は炭酸水素カリウムが好ま
しい。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, sodium bicarbonate, potassium bicarbonate and the like can be used as bicarbonate. In particular, sodium bicarbonate is preferred because it is industrially suitable because it can be obtained in large quantities and at low cost, and because it has no hygroscopicity and is easy to use in producing and storing granules. On the other hand, when it is desired to prevent sodium from being mixed into the exhaust gas or the like after the removal treatment, potassium hydrogen carbonate is preferable.
【０００７】本発明において、炭酸水素塩の粉末は造粒
物にする。造粒物は、炭酸水素塩を７０質量％以上含有
することが好ましい。造粒物中において、炭酸水素塩が
７０質量％未満であると、ハロゲン系ガス除去剤として
のガス処理容量が低下し、除去剤充填層の入れ替え頻度
が高くなるので好ましくない。炭酸水素塩の含有量は、
特に８０質量％以上であることが好ましい。なお、造粒
物中において、他に含まれる材料としては、炭酸水素塩
以外の吸着剤、バインダー等が挙げられる。In the present invention, the bicarbonate powder is granulated. The granulated material preferably contains 70% by mass or more of hydrogencarbonate. If the content of bicarbonate in the granulated product is less than 70% by mass, the gas treatment capacity as a halogen-based gas remover decreases, and the frequency of replacement of the remover-filled layer is undesirably increased. The bicarbonate content is
In particular, it is preferably at least 80% by mass. In addition, as a material contained in the granulated material, an adsorbent other than hydrogencarbonate, a binder, and the like are included.
【０００８】本発明における炭酸水素塩の粉末は、一次
粒子の平均粒子径が１０〜５００μｍであるものを使用
する。これは、造粒の容易さ及び工業的規模での入手し
やすさからであり、一次粒子の平均粒子径が１０μｍ未
満であると、圧縮成形において粉体圧縮時の脱気が不良
となることから、硬度の高い造粒物が得難くなり、５０
０μｍ超であると、技術的に造粒物の製造が困難であ
る。なお、一次粒子とは炭酸水素塩の単結晶であり、平
均粒子径とは重量基準による平均粒子径である。The bicarbonate powder used in the present invention has an average primary particle diameter of 10 to 500 μm. This is because of the easiness of granulation and the availability on an industrial scale. If the average particle diameter of the primary particles is less than 10 μm, degassing during powder compaction in compression molding will be poor. From this, it becomes difficult to obtain granules having high hardness, and 50
If it exceeds 0 μm, it is technically difficult to produce a granulated product. The primary particles are a single crystal of hydrogen carbonate, and the average particle diameter is an average particle diameter on a weight basis.
【０００９】本発明において、炭酸水素塩の粉末の造粒
物の平均粒子径は０．５〜２０ｍｍである。造粒物の平
均粒子径が０．５〜２０ｍｍであることにより、ハロゲ
ン系ガスの処理の際、従来から使用されている充填塔等
を使用できる。造粒物の平均粒子径が０．５ｍｍ未満で
あると、ハロゲン系ガス又はそれを含有する被処理ガス
が充填層等を通過する際の圧力損失が高くなり、平均粒
子径が２０ｍｍを超えると、被処理ガスと造粒物との接
触面積が低下し、排ガスの除去性能を低下させる。造粒
物の平均粒子径としては、特に０．５〜１０ｍｍが好ま
しい。In the present invention, the average particle size of the granulated product of the bicarbonate powder is 0.5 to 20 mm. When the average particle diameter of the granulated material is 0.5 to 20 mm, a conventionally used packed tower or the like can be used in treating a halogen-based gas. When the average particle diameter of the granulated material is less than 0.5 mm, the pressure loss when the halogen-based gas or the gas to be treated containing the same passes through a packed bed or the like increases, and when the average particle diameter exceeds 20 mm. In addition, the contact area between the gas to be treated and the granulated material is reduced, and the performance of removing the exhaust gas is reduced. The average particle size of the granulated product is particularly preferably 0.5 to 10 mm.
【００１０】本発明において、造粒物は、圧縮成形法に
よって得る。圧縮成形法は、工程が簡略なため工業的に
簡便であり、バインダーを使用しなくても造粒物を得る
ことができる。また、圧縮成形法により、硬度が高く壊
れにくい、ガス処理容量の大きな造粒物を得ることがで
きる。造粒物を得る方法として、具体的には、圧縮成形
機を使用し、乾式で成形した後、粗粉砕し、篩分ける方
法が挙げられる。また、水溶性のバインダーを使用して
湿式の圧縮成形機で成形し、その後乾燥させる方法も挙
げられる。In the present invention, the granulated product is obtained by a compression molding method. The compression molding method is industrially simple because the process is simple, and a granulated product can be obtained without using a binder. In addition, by the compression molding method, it is possible to obtain a granulated material having a high hardness and a high resistance to breakage and a large gas processing capacity. As a method of obtaining a granulated product, specifically, a method of dry-molding using a compression molding machine, coarsely pulverizing, and sieving is used. Further, there is also a method in which a wet compression molding machine is used to form a water-soluble binder, followed by drying.
【００１１】本発明において、炭酸水素塩の粉末の造粒
物は、ハロゲン系ガスの除去処理をするために、充填層
に充填されて使用される場合、強度が低いと、粉化して
充填層を通過する際の圧力損失が上昇することがある。
このため造粒物の強度は高くする。In the present invention, when the granulated powder of bicarbonate is used by filling it in a packed bed to remove a halogen-based gas, if the strength is low, it is pulverized and becomes powdery. The pressure loss when passing through may increase.
For this reason, the strength of the granulated material is increased.
【００１２】本発明における造粒物の強度評価方法とし
て、硬度が挙げられる。ここで、硬度とは、造粒物粒子
の１個を上方より垂直に荷重をかけて圧縮して破壊する
に必要な力のことである。[0012] As a method of evaluating the strength of the granulated product in the present invention, hardness is mentioned. Here, the hardness is a force required to compress and break one of the granulated particles by applying a load vertically from above.
【００１３】本発明での硬度の評価は、造粒物粒子を分
級して粒子径を揃えた粒子群について行う。例えば、目
開き１．５ｍｍの篩と目開き２．０ｍｍの篩を使用して
篩分け、１．５ｍｍ篩上かつ２．０ｍｍ篩下の粒子を２
０個採取し、各粒子の硬度を測定してその平均値を粒子
強度の評価基準として採用する。The evaluation of hardness in the present invention is carried out on a group of particles having a uniform particle diameter by classifying the granulated particles. For example, sieving is performed using a sieve having a mesh size of 1.5 mm and a sieve having a mesh size of 2.0 mm.
Zero pieces are collected, the hardness of each particle is measured, and the average value is adopted as an evaluation standard of the particle strength.
【００１４】本発明における炭酸水素塩の粉末の造粒物
の硬度は、造粒物粒子を篩分けたときの粒子径０．５〜
１．０ｍｍ間の造粒物の平均硬度が１Ｎ以上、又は、粒
子径１．０〜１．５ｍｍ間の造粒物の平均硬度が４Ｎ以
上、又は、粒子径１．５〜２．０ｍｍ間の造粒物の平均
硬度が１０Ｎ以上、又は、粒子径２．０ｍｍ以上の造粒
物の平均硬度が３０Ｎ以上、である。In the present invention, the hardness of the granulated product of the bicarbonate powder is 0.5 to 0.5% when the granulated particles are sieved.
The average hardness of the granules between 1.0 mm is 1 N or more, or the average hardness of the granules between 1.0 to 1.5 mm is 4 N or more, or between 1.5 to 2.0 mm. The average hardness of the granulated product is 10 N or more, or the average hardness of the granulated product having a particle diameter of 2.0 mm or more is 30 N or more.
【００１５】本発明では、ハロゲン単体又はハロゲン化
合物からなるハロゲン系ガスを除去する。例えば、ハロ
ゲン系ガスを含有するドライエッチング排ガス等を処理
して、該排ガス中のハロゲン系ガスを除去する。ハロゲ
ンとしては、フッ素、塩素、臭素等が挙げられる。具体
的なハロゲン単体又はハロゲン化合物としてはＢＣ
ｌ 3、ＣＣｌ4、Ｃｌ2、ＳｉＣｌ4、ＨＣｌ、ＣＯＣ
ｌ2、Ｆ2、ＳｉＦ4、ＨＦ、ＣＯＦ2、ＮＦ3、ＷＦ6、Ｃ
ｌＦ3及びＨＢｒから選ばれる一種又は二種以上が挙げ
られる。In the present invention, halogen alone or halogenated
The halogen-based gas consisting of the compound is removed. For example, halo
Treatment of dry etching exhaust gas containing gen-based gas
Then, the halogen-based gas in the exhaust gas is removed. Haloge
Examples of fluorine include chlorine, bromine and the like. Concrete
Simple halogen or halogen compound is BC
l Three, CClFour, ClTwo, SiClFour, HCl, COC
lTwo, FTwo, SiFFour, HF, COFTwo, NFThree, WF6, C
IFThreeAnd one or more selected from HBr
Can be
【００１６】本発明における被処理ガスの温度が０℃〜
１００℃であると、効率的に除去処理できる。被処理ガ
スの温度が０℃未満であると、反応速度が低下するので
好ましくない。また、１００℃以下であれば、充填塔等
の設備を高価な耐熱材料又は構造とする必要がなく、操
作及び設備等を簡略化できる。In the present invention, the temperature of the gas to be treated is from 0 ° C.
When the temperature is 100 ° C., the removal treatment can be performed efficiently. If the temperature of the gas to be treated is lower than 0 ° C., the reaction rate is undesirably reduced. When the temperature is 100 ° C. or lower, the equipment such as the packed tower does not need to be made of an expensive heat-resistant material or structure, and the operation and the equipment can be simplified.
【００１７】本発明において、炭酸水素塩は、ハロゲン
単体又はハロゲン化合物と反応し、水溶性の塩を生成す
る。炭酸水素塩自身も水溶性であるために、排ガス中の
ハロゲン系ガスの除去に使用した後の造粒物を水に溶解
できる。また、後述のように、例えば、炭酸水素塩と活
性炭を併用した場合、固形廃棄物を減少できる。In the present invention, the bicarbonate reacts with a simple halogen or a halogen compound to form a water-soluble salt. Since the bicarbonate itself is also water-soluble, the granulated material used for removing the halogen-based gas in the exhaust gas can be dissolved in water. Further, as described later, for example, when a bicarbonate and activated carbon are used in combination, solid waste can be reduced.
【００１８】炭酸水素塩は、ハロゲン単体又はハロゲン
化合物と反応して水溶性の塩を生成するため、活性炭吸
着の場合のようにハロゲン単体又はハロゲン化合物が脱
離して臭気を発生することがないため、充填層等の入れ
替え作業が容易にできる。また、炭酸水素塩自身に消火
性があるため発火の危険性がない。Since bicarbonate reacts with a simple halogen or a halogen compound to form a water-soluble salt, the simple hydrogen or the halogen compound does not desorb to generate odor as in the case of activated carbon adsorption. In addition, the work of replacing the filling layer and the like can be easily performed. In addition, there is no danger of ignition because the bicarbonate itself has a fire extinguishing property.
【００１９】本発明において、前記造粒物を活性炭とと
もに充填塔等の容器に充填してハロゲン系ガスと接触さ
せてハロゲン系ガスを除去するのも好ましい。この方法
により、活性炭を単独使用した場合と比較して、ハロゲ
ン単体又はハロゲン化合物の除去量を増加できるのみで
なく、活性炭からの臭気の発生も低減できる。具体的に
は、炭酸水素塩と活性炭を層状に充填塔等の容器に配置
する等して使用する。In the present invention, it is also preferable that the granulated product is packed in a container such as a packed tower together with activated carbon and brought into contact with a halogen-based gas to remove the halogen-based gas. This method not only can increase the removal amount of the halogen alone or the halogen compound, but also can reduce the generation of odor from the activated carbon, as compared with the case where the activated carbon is used alone. Specifically, the bicarbonate and the activated carbon are used in a layered manner in a container such as a packed tower.
【００２０】[0020]
【実施例】以下の各例において、硬度は、藤原製作所製
の木屋式デジタル硬度計ＫＨＴ−２０型を使用して測定
した。また、硬度は粒子の大きさにより異なるため、篩
分けして粒子径を揃えた。EXAMPLES In the following examples, the hardness was measured using a Kiya type digital hardness tester KHT-20 manufactured by Fujiwara Seisakusho. Since the hardness varies depending on the size of the particles, the particles were sieved to make the particle diameter uniform.
【００２１】[例１]一次粒子の平均粒子径が９１μｍの
食品添加物用炭酸水素ナトリウムの粉末（旭硝子株式会
社製）３００ｋｇをロールプレス式圧縮成形機（ターボ
工業社製、商品名：ローラーコンパクターＷＰ型、ロー
ル外径２３０ｍｍ、ロール長８０ｍｍ）を使用して線圧
３６．８ｋＮ／ｃｍで圧縮成形し、フレーク状の炭酸水
素ナトリウムの粉末の成形体を得た。得られたフレーク
状の成形体をフレークブレーカーで粗砕し、ロータリー
式整粒機のメッシュを４．７５ｍｍに設定して全通させ
た後、回転篩機（ターボ工業社製、商品名：ターボスク
リーナーＴＳ型）を使用して粒子径４．０ｍｍ以上の粒
子と粒子径１．０ｍｍ以下の粒子を除去し、平均粒子径
が２．３ｍｍの炭酸水素ナトリウムの粉末の造粒物を得
た。Example 1 300 kg of sodium bicarbonate powder for food additives (manufactured by Asahi Glass Co., Ltd.) having an average primary particle diameter of 91 μm was roll-pressed with a compression molding machine (manufactured by Turbo Kogyo Co., Ltd., trade name: roller compactor) Using a WP mold, a roll outer diameter of 230 mm, and a roll length of 80 mm), compression molding was performed at a linear pressure of 36.8 kN / cm to obtain a flake-like molded product of sodium bicarbonate powder. The obtained flake-shaped compact was crushed with a flake breaker, and the mesh of a rotary sizing machine was set to 4.75 mm to allow the whole to pass therethrough. Then, a rotary sieving machine (trade name: turbo Particles having a particle diameter of 4.0 mm or more and particles having a particle diameter of 1.0 mm or less were removed using a screener (TS type) to obtain a granulated product of sodium bicarbonate powder having an average particle diameter of 2.3 mm. .
【００２２】また、前述の硬度測定法によって、造粒物
の粒子強度を測定した。すなわち得られた平均粒子径
２．３ｍｍの造粒物を０．５ｍｍ、１．０ｍｍ、１．５
ｍｍ、２．０ｍｍ、２．５ｍｍの目開きの篩で篩分け、
各粒度の硬度を２０個測定し平均値を求めたところ、
０．５〜１．０ｍｍの間の粒子の平均硬度が３Ｎ、１．
０〜１．５ｍｍが１３Ｎ、１．５〜２．０ｍｍが２１
Ｎ、２．０ｍｍ以上が６０Ｎであった。Further, the particle strength of the granulated product was measured by the hardness measurement method described above. That is, the obtained granules having an average particle diameter of 2.3 mm were added to 0.5 mm, 1.0 mm, 1.5 mm
mm, 2.0 mm, sieved with a 2.5 mm mesh sieve,
When the hardness of each particle size was measured 20 and the average value was determined,
The average hardness of the particles between 0.5-1.0 mm is 3N;
13N for 0-1.5mm, 21 for 1.5-2.0mm
N, 2.0N or more was 60N.
【００２３】次に、底面が通気性焼結板で内径２５０ｍ
ｍ、長さ１７００ｍｍのフッ素樹脂ライニング付きステ
ンレス鋼製の充填容器に、充填物として前記造粒物を２
５ｋｇ充填した。被処理ガスとして、組成比がＢＣ
ｌ3：１６体積％、Ｃｌ2：４４体積％、アルゴン：４０
体積％のガスを流量２５０ｃｍ3／分、温度２５℃、常
圧下で、上記充填容器の底部から注入した。充填容器の
上部から流出したガスを分析したところ、ＢＣｌ3は検
出されず、Ｃｌ2は０．０３体積ｐｐｍであった。Next, the bottom surface is made of a permeable sintered plate with an inner diameter of 250 m.
m, 1700 mm in length in a stainless steel-filled container with a fluororesin lining,
5 kg was charged. The composition ratio of the gas to be treated is BC
l 3 : 16% by volume, Cl 2 : 44% by volume, argon: 40
A volume% gas was injected from the bottom of the filled container at a flow rate of 250 cm 3 / min, a temperature of 25 ° C. and normal pressure. Analysis of the gas flowing out from the upper part of the filling container showed that BCl 3 was not detected and Cl 2 was 0.03 ppm by volume.
【００２４】処理開始から３０１時間経過後に流出ガス
中のＣｌ2濃度が上昇し始めた。充填物を取り出したと
ころ、造粒物粒子の粉化や臭気の発生はなかった。ま
た、この充填物を水に溶解したところすべて溶解し、固
形廃棄物の発生はなかった。After a lapse of 301 hours from the start of the treatment, the Cl 2 concentration in the effluent gas began to increase. When the filler was taken out, there was no powdering of the granulated particles or generation of odor. When this filler was dissolved in water, it was completely dissolved, and no solid waste was generated.
【００２５】[例２]例１と同様にして得た炭酸水素ナト
リウムの粉末の造粒物と活性炭とを、例１と同じ充填容
器に、下から順に活性炭５ｋｇ、造粒物１２．５ｋｇ、
活性炭５ｋｇ、造粒物１２．５ｋｇ、計３５ｋｇを充填
して使用する以外は例１と同様にして、流出ガスを分析
したところ、ＢＣｌ3は検出されず、Ｃｌ2は０．０１体
積ｐｐｍであった。Example 2 A granulated product of sodium bicarbonate powder and activated carbon obtained in the same manner as in Example 1 were placed in the same filling container as in Example 1 in an order from the bottom in an amount of 5 kg of activated carbon, 12.5 kg of granulated product,
The effluent gas was analyzed in the same manner as in Example 1 except that 5 kg of activated carbon and 12.5 kg of granulated material, a total of 35 kg, were used. BCl 3 was not detected, and Cl 2 was 0.01 vol ppm. there were.
【００２６】処理開始から３７４時間経過後に流出ガス
中のＣｌ2濃度が上昇し始めた。充填物を取り出したと
ころ、造粒物粒子の粉化や臭気の発生はなかった。ま
た、この充填物の内、造粒物を水に溶解したところすべ
て溶解した。After 374 hours from the start of the treatment, the Cl 2 concentration in the effluent gas began to increase. When the filler was taken out, there was no powdering of the granulated particles or generation of odor. In addition, when the granulated material was dissolved in water, all of the filler was dissolved.
【００２７】[例３]被処理ガスとして、組成比がＢＣｌ
3：１６体積％、ＣＣｌ4：０．６体積％、Ｃｌ2：２
５．３体積％、ＳｉＣｌ4：０．６体積％、ＨＣｌ：
４．８体積％、ＣＯＣｌ2：０．６体積％、Ｆ2：２．７
体積％、ＳｉＦ4：０．６体積％、ＨＦ：４．８体積
％、ＣＯＦ2：０．６体積％、ＮＦ3：０．８体積％、Ｗ
Ｆ6：０．６体積％、ＣｌＦ3：０．６体積％、ＨＢｒ：
４．８体積％、アルゴン：３６．６体積％のガスを使用
する以外は例２と同様にして、流出ガスを分析したとこ
ろ、Ｃｌ2は０．０１体積ｐｐｍであり、ＢＣｌ3、ＣＣ
ｌ4、ＳｉＣｌ4、ＨＣｌ、ＣＯＣｌ2、Ｆ2、ＳｉＦ4、
ＨＦ、ＣＯＦ2、ＮＦ3、ＷＦ6、ＣｌＦ3、ＨＢｒ等は検
出されなかった。Example 3 The gas to be treated has a composition ratio of BCl
3:16 vol%, CCl 4: 0.6 by volume%, Cl 2: 2
5.3 vol%, SiCl 4: 0.6 by volume%, HCl:
4.8 vol%, COCl 2: 0.6 vol%, F 2: 2.7
Vol%, SiF 4: 0.6 by volume%, HF: 4.8 vol%, COF 2: 0.6 vol%, NF 3: 0.8 by volume%, W
F 6 : 0.6% by volume, ClF 3 : 0.6% by volume, HBr:
The effluent gas was analyzed in the same manner as in Example 2 except that a gas of 4.8% by volume and argon: 36.6% by volume was used. Cl 2 was 0.01 ppm by volume, and BCl 3 and CC were analyzed.
l 4 , SiCl 4 , HCl, COCl 2 , F 2 , SiF 4 ,
HF, COF 2 , NF 3 , WF 6 , ClF 3 , HBr, etc. were not detected.
【００２８】処理開始から３７１時間経過後に流出ガス
中のＣｌ2濃度が上昇し始めた。充填物を取り出したと
ころ、造粒物粒子の粉化や臭気の発生はなかった。ま
た、この充填物の内、造粒物を水に溶解したところ９０
質量％以上溶解した。After 371 hours from the start of the treatment, the Cl 2 concentration in the effluent gas began to increase. When the filler was taken out, there was no powdering of the granulated particles or generation of odor. When the granulated material was dissolved in water,
It dissolved by mass% or more.
【００２９】[例４（比較例）]炭酸水素ナトリウムの粉
末の造粒物２５ｋｇのかわりに活性炭のみを３５ｋｇ充
填する以外は例１と同様にして、流出ガスを分析したと
ころ、ＢＣｌ3は検出されず、Ｃｌ2は０．０１体積ｐｐ
ｍであった。Example 4 (Comparative Example) The effluent gas was analyzed in the same manner as in Example 1 except that 35 kg of activated carbon alone was charged instead of 25 kg of a granulated product of sodium hydrogen carbonate powder, and BCl 3 was detected. However, Cl 2 is 0.01 volume pp
m.
【００３０】処理開始から２５１時間経過後に流出ガス
中のＣｌ2濃度が上昇し始めた。充填物を取り出したと
ころ、活性炭からは著しい塩素臭気が発生していた。ま
た、取り出した活性炭は固形廃棄物として処理した。After a lapse of 251 hours from the start of the treatment, the Cl 2 concentration in the effluent gas began to rise. When the filling was taken out, a remarkable chlorine odor was generated from the activated carbon. The activated carbon taken out was treated as solid waste.
【００３１】[0031]
【発明の効果】本発明によれば、使用時に粉化せず、除
去能力が高く、臭気の発生が少ない造粒物を用いてハロ
ゲン系ガスを除去できる。また、本発明によれば、従来
の活性炭を使用する充填塔等にそのまま適用できる。According to the present invention, it is possible to remove a halogen-based gas by using a granulated material which is not powdered at the time of use, has a high removal ability, and generates little odor. Further, according to the present invention, the present invention can be directly applied to a packed tower using activated carbon.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森 要一 福岡県北九州市戸畑区牧山５丁目１番１号 旭硝子株式会社内 (72)発明者 川辺 義勝 愛知県海部郡佐織町大字町方新田字五軒家 東24番地の２ サンワケミカル株式会社内 Ｆターム(参考） 4D002 AA17 AA18 AA19 AA22 AA23 AA24 AA26 AC10 BA03 BA04 CA07 DA02 DA16 DA41 GA01 GB08 GB12 GB20 4G066 AA05B AA13B AA43B AA80B BA09 BA20 BA35 CA31 CA32 DA02 FA02 FA26 FA37 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshikazu Mori 5-1-1 Makiyama, Tobata-ku, Kitakyushu-city, Fukuoka Prefecture Inside Asahi Glass Co., Ltd. 24th east 2 Sanwa Chemical Co., Ltd. F term (reference) 4D002 AA17 AA18 AA19 AA22 AA23 AA24 AA26 AC10 BA03 BA04 CA07 DA02 DA16 DA41 GA01 GB08 GB12 GB20 4G066 AA05B AA13B AA43B AA80B BA09 BA20 BA35 CA31 FA32 FA02 FA02
Claims (6)
炭酸水素塩の粉末を圧縮成形法により造粒し、得られた
造粒物を、ハロゲン単体又はハロゲン化合物からなるハ
ロゲン系ガスに接触させてハロゲン系ガスを除去する、
ハロゲン系ガスの除去方法。A powder of hydrogen carbonate having an average primary particle diameter of 10 to 500 μm is granulated by a compression molding method, and the obtained granule is brought into contact with a halogen-based gas composed of a halogen alone or a halogen compound. To remove halogen-based gas,
Halogen gas removal method.
径０．５〜２０ｍｍの造粒物であって、粒子径０．５〜
１．０ｍｍ間の造粒物の平均硬度が１Ｎ以上、又は、粒
子径１．０〜１．５ｍｍ間の造粒物の平均硬度が４Ｎ以
上、又は、粒子径１．５〜２．０ｍｍ間の造粒物の平均
硬度が１０Ｎ以上、又は、粒子径２．０ｍｍ以上の造粒
物の平均硬度が３０Ｎ以上、である造粒物を、ハロゲン
単体又はハロゲン化合物からなるハロゲン系ガスに接触
させてハロゲン系ガスを除去する、ハロゲン系ガスの除
去方法。2. A granulated product obtained by granulating bicarbonate powder and having an average particle size of 0.5 to 20 mm.
The average hardness of the granules between 1.0 mm is 1 N or more, or the average hardness of the granules between 1.0 to 1.5 mm is 4 N or more, or between 1.5 to 2.0 mm. The average hardness of the granulated material of 10N or more, or the average hardness of the granulated material having a particle diameter of 2.0mm or more is 30N or more, contact with a halogen-based gas consisting of a halogen alone or a halogen compound. A halogen-based gas removing method.
る請求項１又は２に記載のハロゲン系ガスの除去方法。3. The method according to claim 1, wherein the hydrogen carbonate is sodium hydrogen carbonate.
量％以上含有する請求項１又は２に記載のハロゲン系ガ
スの除去方法。4. The method for removing a halogen-based gas according to claim 1, wherein the granulated material contains 70% by mass or more of sodium hydrogencarbonate.
ｌ4、Ｃｌ2、ＳｉＣｌ4、ＨＣｌ、ＣＯＣｌ2、Ｆ2、Ｓ
ｉＦ4、ＨＦ、ＣＯＦ2、ＮＦ3、ＷＦ6、ＣｌＦ3及びＨ
Ｂｒからなる群より選ばれる一種以上であり、前記ハロ
ゲン系ガスの温度が０℃〜１００℃である請求項１〜４
のいずれかに記載のハロゲン系ガスの除去方法。5. The method according to claim 1, wherein the halogen-based gas is BCl 3 , CC
l 4 , Cl 2 , SiCl 4 , HCl, COCl 2 , F 2 , S
iF 4 , HF, COF 2 , NF 3 , WF 6 , ClF 3 and H
The halogen gas is at least one selected from the group consisting of Br, and the temperature of the halogen-based gas is 0 ° C to 100 ° C.
The method for removing a halogen-based gas according to any one of the above.
て前記ハロゲン系ガスと接触させてハロゲン系ガスを除
去する請求項１〜５のいずれかに記載のハロゲン系ガス
の除去方法。6. The method for removing a halogen-based gas according to claim 1, wherein the granulated material is filled in a container together with activated carbon and brought into contact with the halogen-based gas to remove the halogen-based gas.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000343696A JP2002143640A (en) | 2000-11-10 | 2000-11-10 | Method for removing halogen-containing gas |
| DE60117909T DE60117909T2 (en) | 2000-11-10 | 2001-11-09 | Process for removing a gas of the halogen (compound) group |
| EP01126470A EP1205230B1 (en) | 2000-11-10 | 2001-11-09 | Method for removing a halogen-containing gas |
| ES01126470T ES2260144T3 (en) | 2000-11-10 | 2001-11-09 | METHOD TO ELIMINATE A GAS FROM THE HALOGEN SERIES. |
| AT01126470T ATE320300T1 (en) | 2000-11-10 | 2001-11-09 | METHOD FOR REMOVAL OF A HALOGEN CONTAINING GAS |
| US09/986,587 US6685901B2 (en) | 2000-11-10 | 2001-11-09 | Method for removing a halogen series gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000343696A JP2002143640A (en) | 2000-11-10 | 2000-11-10 | Method for removing halogen-containing gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002143640A true JP2002143640A (en) | 2002-05-21 |
Family
ID=18818023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000343696A Pending JP2002143640A (en) | 2000-11-10 | 2000-11-10 | Method for removing halogen-containing gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002143640A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002316018A (en) * | 2001-04-23 | 2002-10-29 | Sanwa Chemical Kk | Method for removing halogen gas |
| WO2003033115A1 (en) * | 2001-10-12 | 2003-04-24 | Asahi Glass Company, Limited | Method for removing halogen-containing gas |
| JP2010064040A (en) * | 2008-09-12 | 2010-03-25 | Asahi Glass Co Ltd | Halogen gas removing agent and method for removing halogen gas |
| JP2011062697A (en) * | 2010-11-26 | 2011-03-31 | Sanwa Chemical Kk | Method for removing halogen gas |
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| JP2000246059A (en) * | 1998-12-28 | 2000-09-12 | Showa Denko Kk | Reactive agent for decomposing hardly decomposable organochlorine compound and method for decomposing it |
| JP2000254438A (en) * | 1999-03-12 | 2000-09-19 | Showa Denko Kk | Treatment, treating agent and treating device for halogen fluoride-containing waste gas |
| JP2000296324A (en) * | 1999-02-09 | 2000-10-24 | Showa Denko Kk | Reaction agent for decomposing nitrogen fluoride and decomposing method |
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| JPS62121621A (en) * | 1985-11-22 | 1987-06-02 | Ube Ind Ltd | Gas adsorbing and trapping device |
| JP2000246059A (en) * | 1998-12-28 | 2000-09-12 | Showa Denko Kk | Reactive agent for decomposing hardly decomposable organochlorine compound and method for decomposing it |
| JP2000296324A (en) * | 1999-02-09 | 2000-10-24 | Showa Denko Kk | Reaction agent for decomposing nitrogen fluoride and decomposing method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002316018A (en) * | 2001-04-23 | 2002-10-29 | Sanwa Chemical Kk | Method for removing halogen gas |
| WO2003033115A1 (en) * | 2001-10-12 | 2003-04-24 | Asahi Glass Company, Limited | Method for removing halogen-containing gas |
| US7306775B2 (en) | 2001-10-12 | 2007-12-11 | Asahi Glass Company, Limited | Method for removing halogen series gas |
| JP2010064040A (en) * | 2008-09-12 | 2010-03-25 | Asahi Glass Co Ltd | Halogen gas removing agent and method for removing halogen gas |
| JP2011062697A (en) * | 2010-11-26 | 2011-03-31 | Sanwa Chemical Kk | Method for removing halogen gas |
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