JPH0576752A - Nitrogen oxide adsorbent for ptsa or tsa - Google Patents
Nitrogen oxide adsorbent for ptsa or tsaInfo
- Publication number
- JPH0576752A JPH0576752A JP3241643A JP24164391A JPH0576752A JP H0576752 A JPH0576752 A JP H0576752A JP 3241643 A JP3241643 A JP 3241643A JP 24164391 A JP24164391 A JP 24164391A JP H0576752 A JPH0576752 A JP H0576752A
- Authority
- JP
- Japan
- Prior art keywords
- adsorption
- adsorbent
- ptsa
- tsa
- amount
- 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
- 239000003463 adsorbent Substances 0.000 title claims abstract description 23
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 48
- 238000001179 sorption measurement Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 20
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000000809 air pollutant Substances 0.000 description 2
- 231100001243 air pollutant Toxicity 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001142 circular dichroism spectrum Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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温度吸着法（以下、ＰＴＳＡ法
という）若しくは温度スィング吸着法（以下、ＴＳＡ法
という）で除去するための吸着剤に関する。The present invention relates to adsorption for removing nitrogen oxides, which are air pollutants, by a pressure swing temperature adsorption method (hereinafter referred to as PTSA method) or a temperature swing adsorption method (hereinafter referred to as TSA method). Regarding agents.
【０００２】[0002]
【従来の技術】ＰＳＡ法は吸着圧と脱着圧の圧力差を吸
着と再生の駆動源にして、吸着剤の物理吸着（可逆吸
着）によりガス分離を行う方法である。これに対して、
最近研究されているＰＴＳＡ法若しくはＴＳＡ法は、Ｐ
ＳＡ法では利用することができない不可逆吸着量（化学
吸着）を基にして装置設計を行うことができる利点があ
る。しかし、再生工程で吸着剤を加熱し、吸着工程に移
る以前に吸着剤を冷却する必要があり、吸着剤に対する
熱の授受をいかに短時間に円滑に行うことができるか
が、ＰＴＳＡ法若しくはＴＳＡ法を完成するための鍵に
なる。他方、大気汚染物質である窒素酸化物をＰＴＳＡ
法若しくはＴＳＡ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吸着剤がな
いこともその要因の１つである。2. Description of the Related Art The PSA method is a method of separating a gas by physical adsorption (reversible adsorption) of an adsorbent using a pressure difference between the adsorption pressure and the desorption pressure as a driving source for adsorption and regeneration. On the contrary,
The PTSA method or TSA method that has been recently studied is
There is an advantage that the device can be designed based on the irreversible adsorption amount (chemical adsorption) that cannot be used in the SA method. However, it is necessary to heat the adsorbent in the regeneration step and to cool the adsorbent before moving to the adsorption step, and how to transfer heat to and from the adsorbent smoothly in a short time depends on the PTSA method or the TSA method. It is the key to completing the law. On the other hand, nitrogen oxides that are air pollutants
The technique of removing by TSA method or TSA method has not been completed yet. In particular, the lack of an adsorbent suitable for removing low-concentration nitrogen oxides is one of the causes.
【０００３】[0003]
【発明が解決しようとする課題】本発明者等は、不可逆
吸着量の大きな吸着剤があれば、使用する吸着剤量を相
当に減少することができ、吸着剤に対する熱の授受を短
時間で行えるので、ＰＴＳＡ法若しくはＴＳＡ法で低濃
度窒素酸化物の除去法を実用化することができると考
え、ゼオライト吸着剤を中心に鋭意研究を行った。即
ち、本発明は、低濃度窒素酸化物をＰＴＳＡ法若しくは
ＴＳＡ法で除去するのに適した可逆吸着量の大きなゼオ
ライト吸着剤を提供することを目的とする。The present inventors have found that if an adsorbent having a large amount of irreversible adsorption can be used, the amount of adsorbent used can be considerably reduced, and heat transfer to and from the adsorbent can be achieved in a short time. Since it can be performed, it was thought that the method for removing low-concentration nitrogen oxides could be put to practical use by the PTSA method or the TSA method, and therefore, earnest research was conducted centering on the zeolite adsorbent. That is, an object of the present invention is to provide a zeolite adsorbent having a large reversible adsorption amount suitable for removing low-concentration nitrogen oxides by the PTSA method or the TSA 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、Ｃｏ，Ｃｕ，Ｎｉ，Ｍｎ，Ｆｅ，Ｃ
ａ，Ｃｒ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ＰＴＳＡ法若しくはＴ
ＳＡ法用の窒素酸化物吸着剤である。The present invention is based on pentasil-type zeolite and is composed of Co, Cu, Ni, Mn, Fe and C.
PTSA method or T characterized by carrying one or more metals of a and Cr by ion exchange
It is a nitrogen oxide adsorbent for the SA method.
【０００５】[0005]
【作用】本発明者等は、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窒素酸化物の
不可逆吸着に優れた吸着剤を種々研究したが、例えば、
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
用いて、吸着平衡に達するでの不可逆吸着量を測定した
ところ、０．３２ｃｍ3/ｇであり、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。しかし、このゼ
オライトに対して種々の金属をイオン交換し、可逆吸着
量との関係を研究したところ、Ｃｏ，Ｃｕ，Ｎｉ，Ｍ
ｎ，Ｆｅ，Ｃａ，Ｃｒ等の金属が、ＰＴＳＡ法若しくは
ＴＳＡ法で窒素酸化物を吸着除去するのに適した極めて
多量の不可逆吸着量を示すことを見出した。The present inventors have studied various adsorbents excellent in irreversible adsorption of nitrogen oxides, mainly pentasil-type zeolite represented by ZSM-5 manufactured by Mobil Co.
ZSM-made by Mobil with a silica / alumina ratio of 23.3
The amount of irreversible adsorption to reach the adsorption equilibrium was measured using zeolite in which 5 was 100% ion-exchanged with hydrogen ions, and was 0.32 cm 3 / g, which was sufficient to remove low-concentration nitrogen oxides. It wasn't something. However, when various metals were ion-exchanged with this zeolite and the relationship with the reversible adsorption amount was studied, Co, Cu, Ni, M
It has been found that metals such as n, Fe, Ca, and Cr exhibit an extremely large amount of irreversible adsorption suitable for adsorbing and removing nitrogen oxides by the PTSA method or TSA method.
【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／アルミナ比の大きなゼオライ
トを言う。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、１００
％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。なお、交換量はＩＣＰ法
（Ｉｏｎ 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. In addition, 100
When the amount of ion exchange exceeds 100%, 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 was measured by the ICP method (Ion 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】（不可逆吸着量の測定）上記吸着剤０．５
ｇを充填した吸着筒を吸着温度０℃に保ち、ＮＯ濃度９
９７ｐｐｍ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
り返して初回から定常状態になるまでの吸着量と脱着量
の差を不可逆吸着量として測定した。また、定常状態に
なった後、加熱したＨｅガスで逆流パージを行ったとこ
ろ、上記の不可逆吸着量とほぼ同量の窒素酸化物を回収
することができた。なお、出口のガス濃度及び組成はＴ
ＣＤ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
（％）と不可逆吸着量（ｃｍ3/ｇ）の関係を図１に示し
た。(Measurement of Irreversible Adsorption) The above adsorbent 0.5
The adsorption column filled with g was kept at an adsorption temperature of 0 ° C, and the NO concentration was 9
45 ppm of 97 ppm air at a gas flow rate of 100 cm 3 / min
After flowing for 1 minute, the adsorption pressure during that time was adjusted to 1.2 atm for adsorption, and then He gas was back-flow purged for 60 minutes to desorb nitrogen oxides. By repeating this adsorption / desorption operation, the difference between the adsorption amount and the desorption amount from the first time to the steady state was measured as the irreversible adsorption amount. Further, when the backflow purge was performed with the heated He gas after the steady state was reached, almost the same amount of nitrogen oxide as the above irreversible adsorption amount could be recovered. The gas concentration and composition at the outlet is T
The amount of adsorption and the amount of desorption were determined from the breakthrough curve obtained from TCD by continuously measuring by CD and mass spectrum. The relationship between the exchange rate (%) of Cu (II) ions and the irreversible adsorption amount (cm 3 / g) of the obtained adsorbent 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と同様にして不可逆吸着量を測定したとこ
ろ表１の通りであり、上記の水素イオンで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不可逆吸着
していることが分かる。Example 2 Instead of Cu (II) in Example 1, the metals shown in Table 1 were used for ion exchange, and the irreversible adsorption amount was measured in the same manner as in Example 1 under other conditions. And ZSM-5 (silica / alumina ratio 23.3) which is 100% ion-exchanged with the above hydrogen ions.
It can be seen that a large amount of nitrogen oxide is irreversibly adsorbed as compared with zeolite.
【００１０】[0010]
【表１】 [Table 1]
【００１１】[0011]
【発明の効果】本発明は、上記の構成を採用することに
より、従来の吸着剤と比べて極めて多量の窒素酸化物を
不可逆吸着でき、吸着剤の使用量を大幅に減少させるこ
とが可能になり、ＰＴＳＡ法若しくはＴＳＡ法による低
濃度窒素酸化物の除去を容易にした。According to the present invention, by adopting the above-mentioned constitution, it is possible to irreversibly adsorb an extremely large amount of nitrogen oxide as compared with the conventional adsorbent, and it is possible to greatly reduce the amount of adsorbent used. Therefore, removal of low-concentration nitrogen oxides by the PTSA method or TSA method was facilitated.
【図１】本発明の実施例１で得た吸着剤のＣｕ(II)イオ
ン交換率（％）と不可逆吸着量（ｃｍ3/ｇ）の関係を示
したグラフである。FIG. 1 is a graph showing the relationship between the Cu (II) ion exchange rate (%) and the irreversible adsorption amount (cm 3 / g) of the adsorbent obtained in Example 1 of the present invention.
Claims (1)
Ｃｕ，Ｎｉ，Ｍｎ，Ｆｅ，Ｃａ，Ｃｒ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
とする窒素酸化物の圧力温度スィング吸着法用若しくは
温度スィング吸着法用の吸着剤。1. In contrast to pentasil-type zeolite, Co,
Any one of Cu, Ni, Mn, Fe, Ca, Cr
An adsorbent for pressure-temperature swing adsorption method or temperature-swing adsorption method for nitrogen oxides, characterized in that one or more metals are supported by ion exchange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24164391A JP3153821B2 (en) | 1991-09-20 | 1991-09-20 | Adsorbent for PTSA or TSA of nitrogen oxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24164391A JP3153821B2 (en) | 1991-09-20 | 1991-09-20 | Adsorbent for PTSA or TSA of nitrogen oxides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0576752A true JPH0576752A (en) | 1993-03-30 |
| JP3153821B2 JP3153821B2 (en) | 2001-04-09 |
Family
ID=17077369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24164391A Expired - Fee Related JP3153821B2 (en) | 1991-09-20 | 1991-09-20 | Adsorbent for PTSA or TSA of nitrogen oxides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3153821B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2728806A1 (en) * | 1994-12-29 | 1996-07-05 | Inst Francais Du Petrole | ADSORBENTS USEFUL IN PROCESSES FOR PURIFYING ATMOSPHERES POLLUTED WITH NITROGEN OXIDE |
| FR2834915A1 (en) * | 2002-01-21 | 2003-07-25 | Air Liquide | AIR PURIFICATION IN NxOy AND CnHm ON ADSORBENT WITH TRANSITIONAL METALS |
| JP2007245050A (en) * | 2006-03-17 | 2007-09-27 | Toyota Central Res & Dev Lab Inc | Nitrogen oxide adsorbent, method for producing the same, and method for removing nitrogen oxide using the same |
| JP2008064135A (en) * | 2006-09-05 | 2008-03-21 | Matsushita Electric Ind Co Ltd | Insulation |
| JP2011524405A (en) * | 2008-06-17 | 2011-09-01 | ツィルム・ベタイリグングスゲゼルシャフト・エムベーハー・ウント・コ・パテンテ・ツヴァイ・カーゲー | Method for separating NOx from a gas stream containing an epoxide |
-
1991
- 1991-09-20 JP JP24164391A patent/JP3153821B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2728806A1 (en) * | 1994-12-29 | 1996-07-05 | Inst Francais Du Petrole | ADSORBENTS USEFUL IN PROCESSES FOR PURIFYING ATMOSPHERES POLLUTED WITH NITROGEN OXIDE |
| BE1010539A3 (en) * | 1994-12-29 | 1998-10-06 | Inst Francais Du Petrole | Method of treatment of polluted by an atmosphere of nitrogen oxide. |
| FR2834915A1 (en) * | 2002-01-21 | 2003-07-25 | Air Liquide | AIR PURIFICATION IN NxOy AND CnHm ON ADSORBENT WITH TRANSITIONAL METALS |
| JP2007245050A (en) * | 2006-03-17 | 2007-09-27 | Toyota Central Res & Dev Lab Inc | Nitrogen oxide adsorbent, method for producing the same, and method for removing nitrogen oxide using the same |
| JP2008064135A (en) * | 2006-09-05 | 2008-03-21 | Matsushita Electric Ind Co Ltd | Insulation |
| JP2011524405A (en) * | 2008-06-17 | 2011-09-01 | ツィルム・ベタイリグングスゲゼルシャフト・エムベーハー・ウント・コ・パテンテ・ツヴァイ・カーゲー | Method for separating NOx from a gas stream containing an epoxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3153821B2 (en) | 2001-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3693626B2 (en) | Adsorbent | |
| US8597584B2 (en) | Gas purifying process and device | |
| EP2680944B1 (en) | Pressure-temperature swing adsorption process | |
| JP5585873B2 (en) | Environmental purification method and apparatus using ionic liquid | |
| US3689212A (en) | Method of purifying gaseous mixtures | |
| TW200417512A (en) | Carbon dioxide purification for the semiconductor industry | |
| JPH11226335A (en) | Method for refining inert fluid by adsorption on lsx zeolite | |
| WO2008065633A1 (en) | Xenon retrieval system and retrieval device | |
| US6572681B1 (en) | Purification of gases | |
| WO2017219043A1 (en) | Apparatus, methods and systems for multi-stage scrubbing of gas mixtures | |
| JPH11290635A (en) | Removal of carbon dioxide from gas flow | |
| JP2004202393A (en) | How to desorb carbon dioxide | |
| JP3153821B2 (en) | Adsorbent for PTSA or TSA of nitrogen oxides | |
| CN116568382A (en) | Catalyst use and method for removing aldehydes | |
| JP2008212845A (en) | Carbon monoxide adsorbent, gas purification method and gas purification apparatus | |
| JP2002321912A (en) | Zeolite for adsorption and gas removal device using the same | |
| JP4174298B2 (en) | Gas purification method and apparatus | |
| JP2005021891A (en) | Gas purification method and apparatus | |
| JP3153820B2 (en) | Nitrogen oxide adsorbent for PSA | |
| JP6549969B2 (en) | Air purification apparatus and air purification method | |
| JP2017080665A (en) | Adsorbent, production method of adsorbent, carbon monoxide removal device and carbon monoxide removal method | |
| JP6655645B2 (en) | Purified gas production apparatus and purified gas production method | |
| JP4256216B2 (en) | Gas processing apparatus and gas processing method | |
| JPH01138106A (en) | Production of nitrogen | |
| JP4602202B2 (en) | Gas processing method and gas processing apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20001226 |
|
| LAPS | Cancellation because of no payment of annual fees |