JPS63162026A - Advanced treatment for arsine and phosphine - Google Patents
Advanced treatment for arsine and phosphineInfo
- Publication number
- JPS63162026A JPS63162026A JP61310025A JP31002586A JPS63162026A JP S63162026 A JPS63162026 A JP S63162026A JP 61310025 A JP61310025 A JP 61310025A JP 31002586 A JP31002586 A JP 31002586A JP S63162026 A JPS63162026 A JP S63162026A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- gaseous
- absorbing
- absorption
- sodium hypochlorite
- 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.)
- Pending
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 25
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010521 absorption reaction Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 238000009279 wet oxidation reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 34
- 229910000070 arsenic hydride Inorganic materials 0.000 abstract description 7
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 239000007792 gaseous phase Substances 0.000 abstract 2
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、半導体製造工場で使用されている特殊材料ガ
スの中で最も毒性の高いガスとして知られているアルシ
ン（ＡＳＨり及びホスフィン（ＰＨ３）の除去方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention utilizes arsine (ASH) and phosphine (PH3), which are known as the most toxic gases among the special material gases used in semiconductor manufacturing factories. ) related to the removal method.
ＡｓＨ３及びＰＨ，は、従来から半導体の材料ガスとし
て使用されており、その使用量は、半導体素子の生産量
の増加及び多様化に従って、年々増加の傾向にある。AsH3 and PH have traditionally been used as material gases for semiconductors, and their usage tends to increase year by year as the production volume and diversification of semiconductor devices increases.
ＡｓＨ３ガス及びＰＨ，ガスは、特殊材料ガスの中でも
非常に毒性が強く、極めて微量でも人体に有害であるこ
とが知られており、いくつかの除害方法も提案されてい
る。しかし、これらの多くは、固体吸着剤を使用し、化
学反応を伴う固相吸着の方法が多く用いられてきた。AsH3 gas and PH gas are known to be extremely toxic among special material gases, and even in extremely small amounts are harmful to the human body, and several methods have been proposed to eliminate them. However, in many of these methods, solid phase adsorption methods using solid adsorbents and involving chemical reactions have been used.
又、従来の除害方法の中には、ＮａＯＨ等のアルカリ液
又は酸化剤を使用した湿式の吸収法によるものもある。Furthermore, among the conventional methods of abatement, there is also a wet absorption method using an alkaline solution such as NaOH or an oxidizing agent.
吸着法による除害は、微小ガス量の場合には多く用いら
れているが、処理ガス量が大きい場合は、その経済性の
点で多くの実用例は見ない。Harm removal by adsorption method is often used when the amount of gas to be treated is small, but when the amount of gas to be treated is large, there are not many practical examples due to its economical efficiency.
父上記の吸収法は、使用する薬剤の一般性、安全性、経
済性の点で充分ではなく、又、本発明と同様の薬液を使
用しても、本発明と異なる使用条件でＡｓＨ３ガスの除
去を行う（特開昭６０−１１４３２１号）と、除害性能
が低く、高濃度ではＡｓＨ。The absorption method described above is not sufficient in terms of the generality, safety, and economy of the drugs used, and even if the same chemical solution as the present invention is used, AsH3 gas cannot be absorbed under different usage conditions from the present invention. When removed (Japanese Patent Application Laid-Open No. 114321/1983), the removal performance is low, and at high concentrations AsH.
ガスがほとんど除害されず、実用性に乏しい。The gas is hardly removed, making it impractical.
本発明は、かかる現状に鑑み、一般に広く出回っている
酸化剤である次亜塩素酸ナトリウム又は塩素水を湿式吸
収法における吸収剤として使用して、高い除去効果と経
済性とを両車させた、アルシン及びホスフィンの高度処
理方法を提供することを目的としている。In view of the current situation, the present invention uses sodium hypochlorite or chlorine water, which are widely available oxidizing agents, as an absorbent in a wet absorption method, thereby achieving both high removal effects and economic efficiency. , aims to provide an advanced treatment method for arsine and phosphine.
本発明によれば、この目的は、添加剤を加えてｐＨ値を
３以上８未満に安定させた有効塩素濃度０．０５％〜５
％（ｗｔ％）の次亜塩素酸ナトリウム又は塩素水を吸収
液とすることを特徴としたガス中のアルシン及び／又は
ホスフィンの湿式酸化吸収法による除去方法を提供する
ことによって達成される。According to the invention, this purpose is achieved by adding additives to stabilize the pH value between 3 and 8 with an effective chlorine concentration of 0.05% to 5.
This is achieved by providing a method for removing arsine and/or phosphine in a gas by a wet oxidation absorption method, which is characterized by using % (wt%) of sodium hypochlorite or chlorine water as an absorption liquid.
本発明を実施する装置の概略を第１図に示す。FIG. 1 shows an outline of an apparatus for carrying out the present invention.
ＡｓＨ３ガス及び／又はＰＨ３ガスを定量的に供給する
ガス供給箱１から排出されたガスは、導管２を通り、吸
収塔３へ導かれる。吸収塔３には充填剤が充填されてい
て、この吸収塔３を通過したガスは、導管４により吸着
塔５へ導かれる。吸着塔５は、ＡｓＨ３ガス及び／又は
ＰＨ３ガスが吸収塔３で除去されない場合及び緊急用と
して設置されたものであって、本発明を実施するための
必要条件とはならない。吸着塔５を出たガスは、導管６
を通って排気ブロワ−７によって排気される。又、添加
剤を加えて調整された吸収液はタンク８内に蓄えられ、
循環ポンプ９にて導管１１に揚液され、吸収塔３の上部
から充填層上へ散布される。気相が充填層にて接触し、
ガス中のＡｓ！（３及び／又はＰＨ３の吸収を果たした
液は、導管１０を通過してタンク８に戻る。なお、Ｓｌ
は吸収前のガス濃度検出口、Ｓ２は吸収後のガス検出口
を示す。Gas discharged from a gas supply box 1 that quantitatively supplies AsH3 gas and/or PH3 gas passes through a conduit 2 and is led to an absorption tower 3. The absorption tower 3 is filled with a filler, and the gas that has passed through the absorption tower 3 is guided to the adsorption tower 5 through a conduit 4. The adsorption tower 5 is installed in case AsH3 gas and/or PH3 gas is not removed by the absorption tower 3 and for emergency use, and is not a necessary condition for carrying out the present invention. The gas leaving the adsorption tower 5 is transferred to the conduit 6
The air is exhausted through an exhaust blower 7. In addition, the absorption liquid adjusted by adding additives is stored in the tank 8,
The liquid is pumped into the conduit 11 by the circulation pump 9 and distributed from the upper part of the absorption tower 3 onto the packed bed. The gas phase contacts in the packed bed,
As in gas! (The liquid that has absorbed 3 and/or PH3 passes through the conduit 10 and returns to the tank 8.
S2 indicates the gas concentration detection port before absorption, and S2 indicates the gas detection port after absorption.
吸収液は、有効塩素濃度０．０５％〜５％の次亜塩素酸
ナトリウム又は塩素液に適宜の添加剤を加えてｐＨを８
未満３以上に調整したものである。The absorption liquid is made by adding appropriate additives to sodium hypochlorite or chlorine solution with an effective chlorine concentration of 0.05% to 5% and adjusting the pH to 8.
It is adjusted to less than 3 or more.
導管２を通って吸収塔３へ導かれたガスは、吸収塔３の
上部から充填層上に散布された吸収液と充填層において
接触し、気相中のＡｓＨ，ガス及び／又はＰＨ３ガスは
液相に吸収される。The gas led to the absorption tower 3 through the conduit 2 comes into contact with the absorption liquid sprinkled onto the packed bed from the upper part of the absorption tower 3 in the packed bed, and the AsH, gas and/or PH3 gas in the gas phase is Absorbed into the liquid phase.
なお、吸収液のｐＨ値を３未満とするときは、塩素の遊
離が激しく、実用に適さないことがわかった。It has been found that when the pH value of the absorption liquid is less than 3, chlorine is liberated rapidly and is not suitable for practical use.
第１図に示す装置にて本発明を実施した結果は、第１表
、第２表及び第２図に示す通りである。The results of implementing the present invention using the apparatus shown in FIG. 1 are as shown in Tables 1, 2, and FIG.
吸収塔３は、内径１００ｍＩＩｌの円筒状で、充填剤と
して１５ｍｍφのラシヒリングが６００ｍｍ充填されて
いる対抗接触の湿式充填塔である。吸収液として、第１
表及び第２図においては次亜塩素酸ナトリウムを、第２
表においては塩素液を使用した。The absorption tower 3 is a cylindrical wet-packed tower with an inner diameter of 100 mIIl and filled with 600 mm of 15 mmφ Raschig rings as a packing material. As the absorption liquid, the first
In the table and Figure 2, sodium hypochlorite is
In the table, chlorine solution was used.
吸収処理される前のガスをＳｌにて採取し、吸収処理後
のガスを８２にて採取してそれぞれ測定した。ガス分析
には、前処理を行って、理研のＥＣ−５６０ＳＳガス検
知器を使用し、通常の分析方法であるＡｇ−ＤＤＣ法と
併用し、分析値の確認を行った。なお、ガス検知器の検
出限界は０．０５ ｐｐＩｌｌである。The gas before absorption treatment was sampled at SI, and the gas after absorption treatment was sampled at 82 for measurement. For gas analysis, a pretreatment was performed, and a RIKEN EC-560SS gas detector was used in combination with the Ag-DDC method, which is a normal analysis method, to confirm the analytical values. Note that the detection limit of the gas detector is 0.05 ppIll.
従来から、次亜塩素酸ナトリウムを吸収液としたＡＳＨ
：ｌ及びＰＨ３の吸収除害は報告されているが、これら
は、すべて吸収液中の塩素放散を防止するために、吸収
液をアルカリ性として調整したものであり、本発明では
、吸収液を中性から弱酸性域に調整することにより、Ａ
ｓＨ３及びＰｌｈに対する除去効果として、より高い結
果が得られた。吸収液中の有効塩素濃度についても、０
．０５％という低い濃度で充分なる除去効果が得られた
。又、ｐＨ８未満での塩素放散の問題も、適宜の添加剤
を加えることにより解消され、液中有効塩素が安定して
存在することが確認された。即ち、吸収液である次亜塩
素酸ナトリウム又は塩素液の有効塩素濃度を０．０５％
〜５％とし、そのｐＨ値を３以上８未満とするよう添加
剤を加えて調整した結果、湿式吸収法により有効なるＡ
！Ｈ３及びＰＨ３の除去性能が確認された。Traditionally, ASH using sodium hypochlorite as an absorption liquid has been used.
:1 and PH3 absorption and abatement have been reported, but in all of these, the absorption liquid is adjusted to be alkaline in order to prevent chlorine dissipation in the absorption liquid.In the present invention, the absorption liquid is adjusted to be alkaline. By adjusting from acidic to weakly acidic range, A
Higher results were obtained as removal effects for sH3 and Plh. The effective chlorine concentration in the absorption liquid is also 0.
．． A sufficient removal effect was obtained at a concentration as low as 0.05%. Furthermore, the problem of chlorine dissipation at pH below 8 was resolved by adding appropriate additives, and it was confirmed that available chlorine in the liquid existed stably. In other words, the effective chlorine concentration of the absorption liquid, sodium hypochlorite or chlorine liquid, is 0.05%.
~5%, and added additives to adjust the pH value to 3 or more and less than 8.
! The removal performance of H3 and PH3 was confirmed.
第１図は、本発明の実施に使用した装置の概略図、第２
図は、次亜塩素酸ナトリウムによるＡｓＨｚの吸収除害
特性を示す図表である。
第２図FIG. 1 is a schematic diagram of the apparatus used to carry out the present invention, and FIG.
The figure is a chart showing the absorption and removal characteristics of AsHz by sodium hypochlorite. Figure 2
Claims (1)
塩素濃度０．０５％〜５％（ｗｔ％）の次亜塩素酸ナト
リウム又は塩素水を吸収液とすることを特徴としたガス
中のアルシン及び／又はホスフィンの湿式酸化吸収法に
よる除去方法。A gas characterized by using sodium hypochlorite or chlorine water as an absorption liquid with an effective chlorine concentration of 0.05% to 5% (wt%) whose pH value is stabilized at 3 or more and less than 8 by adding additives. A method for removing arsine and/or phosphine in a wet oxidation absorption method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61310025A JPS63162026A (en) | 1986-12-24 | 1986-12-24 | Advanced treatment for arsine and phosphine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61310025A JPS63162026A (en) | 1986-12-24 | 1986-12-24 | Advanced treatment for arsine and phosphine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63162026A true JPS63162026A (en) | 1988-07-05 |
Family
ID=18000252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61310025A Pending JPS63162026A (en) | 1986-12-24 | 1986-12-24 | Advanced treatment for arsine and phosphine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63162026A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006130499A (en) * | 2004-10-07 | 2006-05-25 | Japan Pionics Co Ltd | Method and apparatus for waste gas treatment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5095104A (en) * | 1973-12-26 | 1975-07-29 |
-
1986
- 1986-12-24 JP JP61310025A patent/JPS63162026A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5095104A (en) * | 1973-12-26 | 1975-07-29 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006130499A (en) * | 2004-10-07 | 2006-05-25 | Japan Pionics Co Ltd | Method and apparatus for waste gas treatment |
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