JPH0576751A - Nitrogen oxide adsorbent for psa - Google Patents
Nitrogen oxide adsorbent for psaInfo
- Publication number
- JPH0576751A JPH0576751A JP3241642A JP24164291A JPH0576751A JP H0576751 A JPH0576751 A JP H0576751A JP 3241642 A JP3241642 A JP 3241642A JP 24164291 A JP24164291 A JP 24164291A JP H0576751 A JPH0576751 A JP H0576751A
- Authority
- JP
- Japan
- Prior art keywords
- psa
- adsorbent
- amount
- nitrogen oxide
- zeolite
- 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
Landscapes
- Treating Waste Gases (AREA)
- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、大気汚染物質である窒
素酸化物を圧力スィング吸着法（以下、ＰＳＡ法とい
う）で除去するための吸着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbent for removing nitrogen oxide, which is an air pollutant, by a pressure swing adsorption method (hereinafter referred to as PSA method).
【０００２】[0002]
【従来の技術】従来、排気ガス中の窒素酸化物を除去す
る方法としては、専ら湿式法が用いられてきたが、除去
効率の向上や排水処理等二次汚染の回避の観点から、乾
式法の開発要請が高まっていた。一般に、乾式法には膜
分離法と吸着分離法があり、膜分離法は膜性能の向上も
あって、広範な利用が期待されているが、膜の透過速度
には限界があるため、大容量のガス分離には適していな
い。他方、ゼオライトや活性炭等の吸着剤の改良もあっ
て、近年、吸着分離法が利用されるようになった。その
中でも、大気圧近傍の低圧で吸着させ、真空ポンプで真
空再生を行うＰＳＡ法がエネルギーコストの上から種々
のガス分離に利用されている。2. Description of the Related Art Conventionally, a wet method has been mainly used as a method for removing nitrogen oxides in exhaust gas, but a dry method is used from the viewpoint of improving removal efficiency and avoiding secondary pollution such as wastewater treatment. The demand for development was increasing. Generally, the dry method includes a membrane separation method and an adsorption separation method. The membrane separation method is expected to be widely used because of its improved membrane performance. Not suitable for volumetric gas separation. On the other hand, due to improvements in adsorbents such as zeolite and activated carbon, the adsorption separation method has come into use in recent years. Among them, the PSA method of adsorbing at a low pressure near atmospheric pressure and performing vacuum regeneration with a vacuum pump is used for various gas separations from the viewpoint of energy cost.
【０００３】[0003]
【発明が解決しようとする課題】しかし、窒素酸化物を
ＰＳＡ法で除去する技術は未だ完成していない。特に、
低濃度窒素酸化物の除去に適した、可逆吸着量の大きな
吸着剤が未だ見出されていないことがその要因の１つで
あった。因みに、これまで窒素酸化物の吸着量が多いと
されていた活性炭（比表面積：５８ｍ2/ｇ）をＰＳＡ装
置に適用して可逆吸着量を測定すると０．１７ｃｍ3/ｇ
であり、シリカ／アルミナ比２３．３のモービル社製の
ＺＳＭ−５を水素イオンで１００％イオン交換したゼオ
ライトを同様にＰＳＡ装置に適用して可逆吸着量を測定
すると０．１２ｃｍ3/ｇであり、共に可逆吸着量が少な
いために低濃度窒素酸化物を除去するのに十分なもので
はなかった。そこで、本発明は、低濃度窒素酸化物をＰ
ＳＡ法で除去するのに適した可逆吸着量の大きな吸着剤
を提供しようとするものである。However, the technique for removing nitrogen oxides by the PSA method has not been completed yet. In particular,
One of the factors was that an adsorbent having a large reversible adsorption amount suitable for removing low-concentration nitrogen oxides has not been found yet. By the way, when the reversible adsorption amount was measured by applying activated carbon (specific surface area: 58 m 2 / g), which was said to have a large adsorption amount of nitrogen oxides, to the PSA device, the reversible adsorption amount was 0.17 cm 3 / g.
When a reversible adsorption amount is measured by similarly applying a zeolite obtained by subjecting ZSM-5 manufactured by Mobil Co. having a silica / alumina ratio of 23.3 to 100% ion exchange with hydrogen ions to a PSA device and measuring the reversible adsorption amount, it is 0.12 cm 3 / g. However, both were not sufficient to remove low-concentration nitrogen oxides because the reversible adsorption amount was small. Therefore, in the present invention, the low concentration nitrogen oxide is added to P
It is intended to provide an adsorbent having a large reversible adsorption amount suitable for removal by the SA method.
【０００４】[0004]
【課題を解決するための手段】本発明は、ペンタシル型
ゼオライトに対し、Ｃｕ，Ａｇ，Ｓｒ，Ｃａ，Ｃｏ，Ｍ
ｎ，Ｎｉ，Ｚｎの中のいずれか１つ以上の金属をイオン
交換により担持させたことを特徴とするＰＳＡ用窒素酸
化物吸着剤である。The present invention is directed to Cu, Ag, Sr, Ca, Co, and M for pentasil type zeolite.
The nitrogen oxide adsorbent for PSA is characterized in that any one or more of n, Ni, and Zn metals are supported by ion exchange.
【０００５】[0005]
【作用】本発明者等は、低濃度窒素酸化物をＰＳＡ法で
除去するのに適した吸着剤、即ち、可逆吸着量の大きな
窒素酸化物吸着剤をゼオライトを中心にして鋭意研究を
重ねてきた。水素型のＺＳＭ−５の可逆吸着量は、上記
のように僅か０．１２ｃｍ3/ｇであり、フォージャサイ
トの１種であるＹ型ゼオライトにＡｇを４２％イオン交
換させた吸着剤の可逆吸着量は、０．４４ｃｍ3/ｇであ
り、同じＹ型ゼオライトにＣｕを８３％イオン交換させ
た吸着剤の可逆吸着量は、０．８６ｃｍ3/ｇであり、い
ずれも低濃度窒素酸化物の除去には十分なものでなかっ
た。しかし、モービル社製のＺＳＭ−５に代表されるペ
ンタシル型ゼオライトを中心に、これに対して種々の金
属をイオン交換させて可逆吸着量の大きな吸着剤を研究
したところ、Ｃｕ，Ａｇ，Ｓｒ，Ｃａ，Ｃｏ，Ｍｎ，Ｎ
ｉ，Ｚｎ等の金属をイオン交換したペンタシル型ゼオラ
イトが極めて大きな可逆吸着量を示すことを見出した。The present inventors have conducted extensive studies mainly on zeolites as an adsorbent suitable for removing low-concentration nitrogen oxides by the PSA method, that is, a nitrogen oxide adsorbent having a large reversible adsorption amount. It was The reversible adsorption amount of hydrogen-type ZSM-5 is only 0.12 cm 3 / g as described above, and the reversibility of the adsorbent obtained by ion-exchanging 42% of Ag with Y-type zeolite which is one of faujasite. The adsorption amount was 0.44 cm 3 / g, and the reversible adsorption amount of the adsorbent obtained by ion exchange of Cu with 83% of the same Y-type zeolite was 0.86 cm 3 / g. Was not sufficient for the removal of. However, when an adsorbent having a large reversible adsorption amount was studied centering on a pentasil-type zeolite represented by ZSM-5 manufactured by Mobil Co. by ion-exchange of various metals, Cu, Ag, Sr, Ca, Co, Mn, N
It has been found that a pentasil-type zeolite in which a metal such as i or Zn is ion-exchanged exhibits an extremely large reversible adsorption amount.
【０００６】本発明で使用されるペンタシル型ゼオライ
トとは、上記のＺＳＭ−５と同じ基本構成単位を有する
ゼオライトであって、モルデナイト、フェリエライト、
シリカライト等のシリカ／アルミナ比が大きなゼオライ
トを言う。また、ペンタシル型ゼオライトに対するイオ
ン交換金属の交換量は、金属の種類により若干の違いが
あるが、約５０％以上であることが好ましい。なお、１
００％を越えてイオン交換する場合は、例えば、目的の
金属塩水溶液でイオン交換した後、アンモニア水溶液で
処理することにより、錯体の形で１００％以上の交換量
を容易に確保することができる。交換量はＩＣＰ法（Ｉ
ｏｎ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ法）で測定した。The pentasil-type zeolite used in the present invention is a zeolite having the same basic constitutional unit as ZSM-5, and includes mordenite, ferrierite,
Zeolite having a large silica / alumina ratio such as silicalite. The amount of ion-exchanged metal exchanged with the pentasil-type zeolite varies slightly depending on the type of metal, but is preferably about 50% or more. 1
In the case of performing ion exchange in excess of 00%, for example, by performing ion exchange with an intended metal salt aqueous solution and then treating with an aqueous ammonia solution, it is possible to easily secure an exchange amount of 100% or more in the form of a complex. .. The exchange amount is the ICP method (I
on Coupled Plasma method).
【０００７】[0007]
〔実施例１〕 （吸着剤の調製）モービル社製のＺＳＭ−５（シリカ／
アルミナ＝２３．３）ゼオライトを硝酸第２銅水溶液に
浸漬し、必要に応じてさらに、アンモニア水中に移して
浸漬し、最後に、Ｈｅガス中で５００℃で５時間加熱処
理し、Ｃｕ(II)イオン交換量が、０％，２５％，６０
％，７８％，１４０％，１５７％である６種類の吸着剤
を得た。[Example 1] (Preparation of adsorbent) ZSM-5 (silica /
Alumina = 23.3) Zeolite is immersed in an aqueous solution of cupric nitrate, and if necessary, further transferred and immersed in ammonia water, and finally, heat treated in He gas at 500 ° C for 5 hours to obtain Cu (II ) The amount of ion exchange is 0%, 25%, 60
%, 78%, 140%, 157% of 6 kinds of adsorbents were obtained.
【０００８】（可逆吸着量の測定）上記吸着剤０．５ｇ
を充填した吸着筒を吸着温度０℃に保ち、ＮＯ濃度９９
７ｐｐｍの空気をガス流量１００ｃｍ3/ｍｉｎで４５分
間流し、その間の吸着圧力１．２ａｔｍに調整して吸着
させ、その後、Ｈｅガスで６０分間逆流パージを行い、
窒素酸化物を脱着させた。この吸着・脱着操作を繰り返
して定常状態になった後の吸着量を可逆吸着量として測
定した。なお、出口のガス濃度及び組成はＴＣＤ及びマ
ススペクトルにより連続的に測定し、吸着量並びに脱着
量はＴＣＤより得られた破過曲線から求めた。得られた
吸着剤について、Ｃｕ(II)イオンの交換率（％）と可逆
吸着量（ｃｍ 3/ｇ）の関係を図１に示した。(Measurement of the amount of reversible adsorption) 0.5 g of the above adsorbent
Keep the adsorption temperature of the adsorption cylinder filled with
Air flow of 7ppm 100cm345 minutes at / min
Adsorb by adjusting the adsorption pressure to 1.2 atm
And then back-flow purging with He gas for 60 minutes,
The nitrogen oxide was desorbed. Repeat this adsorption / desorption operation
Then, the amount of adsorption after reaching a steady state is measured as the amount of reversible adsorption.
Decided The gas concentration and composition at the outlet are TCD and
Continuously measured by absorption spectrum, adsorption amount and desorption
The amount was determined from the breakthrough curve obtained from TCD. Got
Regarding the adsorbent, Cu (II) ion exchange rate (%) and reversibility
Adsorption amount (cm 3The relationship of / g) is shown in FIG.
【０００９】〔実施例２〕実施例１におけるＣｕ(II)の
代わりに、表１記載の金属でイオン交換し、その他の条
件は実施例１と同様にして可逆吸着量を測定したところ
表１の通りであり、上記の活性炭（比表面積：５８ｍ2/
ｇ）や水素イオンで１００％イオン交換したＺＳＭ−５
（シリカ／アルミナ比２３．３）ゼオライトと比較し
て、多量の窒素酸化物を可逆吸着することが分った。Example 2 In place of Cu (II) in Example 1, the metals shown in Table 1 were used for ion exchange, and the reversible adsorption amount was measured in the same manner as in Example 1 under other conditions. The above-mentioned activated carbon (specific surface area: 58 m 2 /
g) or ZSM-5 ion-exchanged with hydrogen ion 100%
It was found that a large amount of nitrogen oxide was reversibly adsorbed as compared with zeolite (silica / alumina ratio 23.3).
【００１０】[0010]
【表１】 [Table 1]
【００１１】〔実施例３〕実施例１におけるＺＳＭ−５
ゼオライトの代わりに、モルデナイト並びにフェリエラ
イトを用い、Ｃｕ(II)並びにＡｇでそれぞれイオン交換
し、その他の条件は実施例１と同様にして可逆吸着量を
測定したところ表２の通りであり、上記のＣｕ(II)並び
にＡｇでそれぞれイオン交換したＹ型ゼオライトや水素
イオンでイオン交換したＺＳＭ−５ゼオライトと比較し
て、多量の窒素酸化物を可逆吸着することが分った。[Third Embodiment] ZSM-5 in the first embodiment.
Mordenite and ferrierite were used in place of zeolite, ion exchange was performed with Cu (II) and Ag, and the other conditions were as shown in Table 2 when the reversible adsorption amount was measured in the same manner as in Example 1. It was found that a large amount of nitrogen oxide was reversibly adsorbed as compared with Y-type zeolite ion-exchanged with Cu (II) and Ag and ZSM-5 zeolite ion-exchanged with hydrogen ions.
【００１２】[0012]
【表２】 [Table 2]
【００１３】[0013]
【発明の効果】本発明は、上記の構成を採用することに
より、多量の窒素酸化物を可逆吸着することのできるペ
ンタシル型ゼオライト吸着剤を提供することができ、低
濃度窒素酸化物をＰＳＡ法で除去することができるよう
になった。EFFECTS OF THE INVENTION The present invention can provide a pentasil-type zeolite adsorbent capable of reversibly adsorbing a large amount of nitrogen oxides by adopting the above-mentioned constitution, and a low concentration nitrogen oxides can be PSA-processed. Can now be removed.
【図１】本発明の実施例１で得たＺＳＭ−５ゼオライト
吸着剤のＣｕ(II)イオン交換率（％）と可逆吸着量（ｃ
ｍ3/ｇ）の関係を示したグラフである。FIG. 1 is a Cu (II) ion exchange rate (%) and a reversible adsorption amount (c) of the ZSM-5 zeolite adsorbent obtained in Example 1 of the present invention.
3 is a graph showing the relationship of m 3 / g).
Claims (1)
Ａｇ，Ｓｒ，Ｃａ，Ｃｏ，Ｍｎ，Ｎｉ，Ｚｎの中のいず
れか１つ以上の金属をイオン交換により担持させたこと
を特徴とする圧力スィング吸着法用の窒素酸化物吸着
剤。1. In addition to pentasil-type zeolite, Cu,
A nitrogen oxide adsorbent for a pressure swing adsorption method, characterized in that one or more metals selected from Ag, Sr, Ca, Co, Mn, Ni and Zn are supported by ion exchange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24164291A JP3153820B2 (en) | 1991-09-20 | 1991-09-20 | Nitrogen oxide adsorbent for PSA |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24164291A JP3153820B2 (en) | 1991-09-20 | 1991-09-20 | Nitrogen oxide adsorbent for PSA |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0576751A true JPH0576751A (en) | 1993-03-30 |
| JP3153820B2 JP3153820B2 (en) | 2001-04-09 |
Family
ID=17077354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24164291A Expired - Fee Related JP3153820B2 (en) | 1991-09-20 | 1991-09-20 | Nitrogen oxide adsorbent for PSA |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3153820B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5407651A (en) * | 1991-02-15 | 1995-04-18 | Tosoh Corporation | Catalyst for and method of purifying exhaust gas |
| FR2834915A1 (en) * | 2002-01-21 | 2003-07-25 | Air Liquide | Removal or nitrogen oxides and unsaturated hydrocarbons from gas stream, especially air, comprises contacting the gas stream with adsorbent containing first-series transition metal |
| US7824474B2 (en) | 2005-09-09 | 2010-11-02 | Taiyo Nippon Sanso Corporation | Molded Cu-ZSM5 zeolite adsorbent, method of activating the same, temperature swing adsorption apparatus, and method of purifying gas |
-
1991
- 1991-09-20 JP JP24164291A patent/JP3153820B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5407651A (en) * | 1991-02-15 | 1995-04-18 | Tosoh Corporation | Catalyst for and method of purifying exhaust gas |
| FR2834915A1 (en) * | 2002-01-21 | 2003-07-25 | Air Liquide | Removal or nitrogen oxides and unsaturated hydrocarbons from gas stream, especially air, comprises contacting the gas stream with adsorbent containing first-series transition metal |
| US7824474B2 (en) | 2005-09-09 | 2010-11-02 | Taiyo Nippon Sanso Corporation | Molded Cu-ZSM5 zeolite adsorbent, method of activating the same, temperature swing adsorption apparatus, and method of purifying gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3153820B2 (en) | 2001-04-09 |
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