JP3593650B2 - Vertical fixed bed adsorption tower - Google Patents
Vertical fixed bed adsorption tower Download PDFInfo
- Publication number
- JP3593650B2 JP3593650B2 JP2000044367A JP2000044367A JP3593650B2 JP 3593650 B2 JP3593650 B2 JP 3593650B2 JP 2000044367 A JP2000044367 A JP 2000044367A JP 2000044367 A JP2000044367 A JP 2000044367A JP 3593650 B2 JP3593650 B2 JP 3593650B2
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- adsorption tower
- vertical fixed
- bed adsorption
- fixed bed
- 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.)
- Expired - Lifetime
Links
Landscapes
- Treating Waste Gases (AREA)
- Separation Of Gases By Adsorption (AREA)
Description
【０００１】
【発明が属する技術分野】
本発明は化学産業においてガス吸着等の目的で使用される縦型固定層吸着塔に関するものであり、本発明における吸着塔は、特に塩化ビニルモノマーの製造および塩化ビニル系重合体の製造プロセスにおいて発生する各種廃ガス中の有機塩化化合物、例えば二塩化エチレンまたは塩化ビニルモノマー等の縦型固定層吸着装置として適している。
【０００２】
【従来の技術】
縦型固定層吸着塔の構造骨格は、縦型熱交換器と基本的に同一であり、多数のチューブが塔壁と平行に設けられ、チューブの廻りは温度調節用の媒体の通り路という構成であり、前記チューブ内に活性炭等の吸着材が充填されている。かかる吸着塔においては、吸着材の保持のために、チューブすなわち吸着槽の下部に金網もしくはグレーチィング、またはそれらの併用が必要である。
金網およびグレーチィングを併用する場合、金網で吸着材の落下を防ぎ、グレーチィングで荷重を支えるという使われ方が一般的である。従って、金網の空隙部（一般的に目開きと称される）としては、吸着材の粒子径より若干小さいものが使用され、活性炭等を吸着材とする場合目開きは０．１〜３ｍｍ程度が好適となる。
【０００３】
しかしながら、上記の目開きを有する金網においては、その製造上の理由により、金網を構成する金属線が細くならざるを得ず、その結果上記吸着塔の運転条件によって発生する微量の腐食性ガスとの接触により金網が切れてしまうという問題があった。
すなわち、塩化ビニルモノマーのような有機塩化物を活性炭で吸着する場合では、吸着後に脱着させるとき１５０〜１８０℃の高温度を適用するので、その際に塩化水素ガスのような腐食性ガスが発生し易く、実際に吸着塔を長期にわたり使用することは困難であった。金網の材質として、耐腐食性に優れる金属を使用することもできるが、高価となり工業的に不利である。
本発明においては、吸着材の保持具である上記金網が破損することなく、長期間に亘り運転を継続できる縦型固定層吸着塔を提供することを課題とした。
【０００４】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意検討した結果、本発明を完成するに至った。
すなわち、本発明は、粒状吸着材がチューブ内に充填された縦型固定層吸着塔において、粒状吸着材層と接してその下に該吸着材と同程度の粒径を有する粒状非吸着性材料層が設けられ、さらに該非吸着性材料層と接してその下にそれより粒径の大きい粒状非吸着性材料層が少なくとも１層設けられており、かつこれらの充填材の保持具として線径が０．６ｍｍ以上の金網が使用されていることを特徴とする縦型固定層吸着塔である。
【０００５】
【発明の実施の形態】
本発明における縦型固定層吸着塔の構造は、化学産業等において一般的に使用される縦型固定層吸着塔のそれと同一であり、本発明においては該塔内の各チューブに粒状吸着材が充填され、その下に前記の非吸着性材料層が設けられ、さらにその下に上記の材料を保持するための金網が張られている。
以下、本発明の代表例である塩化ビニルモノマーの吸着用の吸着塔に関して詳述する。吸着材としては粒径０．５〜３ｍｍ程度の粒状活性炭が好ましく、さらに好ましくは平均粒径が２〜３ｍｍの粒状活性炭である。
非吸着性材料としては、セラミックボールまたはステンレスボール等が使用できる。非吸着性材料の粒径に関しては、粒状吸着材層と接して用いられる非吸着性材料の粒径は吸着材と同程度であり、さらにその下に設ける非吸着性材料層用に用いる非吸着性材料の粒径は、その上の充填材の粒径より大きくする必要がある。非吸着性材料層を３つ以上設ける場合には、下の層ほど粒径の大きい材料を使用する。個々の非吸着性材料層の厚みに関しては、特に制約はないが、通常５〜１０ｃｍ程度が好ましい。
【０００６】
上記の手段を採用することによって、本発明においては、金網と接する非吸着性材料の粒径をある程度大きなものにすることができ、その結果目開きの大きな金網すなわち金属線径の太い金網を使用することが可能となった。線径の太い金網を吸着塔の充填材保持具として使用することにより、塩化ビニルモノマーの吸着、脱着の運転を長期間にわたり行っても、金網の破損が起こらなくなった。
【０００７】
縦型固定層吸着塔の充填材を保持する金網としては、線径が０．６ｍｍ以上のものが使用でき、より好ましい線径は０．８〜４．５ｍｍである。特に好ましくは、１．６〜４．５ｍｍである。線径が０．６ｍｍ未満であると塩化ビニルモノマーの吸脱着の運転において金網が短期間の内に切れる。線径が４．５ｍｍを越えると、これに伴い金網の目開きが大きくなり実用的でない。
線径が１．６〜４．５ｍｍの金属線からなる金網の目開きは、通常４〜１０ｍｍである。従って、金網と接する非吸着性材料層を形成する材料の粒径は６〜１２ｍｍ程度にすることが好ましい。
【０００８】
非吸着性材料層を複数個設ける理由は、除々に充填材の粒径を大きくしないと上の層を形成する充填材が落下して層が崩れるからである。平均粒径が２〜３ｍｍの活性炭を吸着材として用いる場合には、非吸着性材料層を２〜３層設けることが好ましい。例えば、吸着材と接する層には粒径が３ｍｍ程度の非吸着性材を用い、その下に粒径が６ｍｍ程度の非吸着性材を用い、最下層として粒径が９ｍｍ程度の非吸着性材を用いる。より粒径の細かい活性炭を使用する場合には、非吸着性材料層を３〜５層設けることが好ましい。
【０００９】
塩化ビニルモノマーの吸脱着の代表的な操作条件は、以下のとおりである。
吸着温度；３０〜５０℃
脱着温度；１２０〜１９０℃
脱着時には、キャリアーガスとしてスチームもしくは窒素ガスを供給するかまたは真空引きにすることが好ましく、さらにはそれらの手段を組み合わせても良い。
【００１０】
本発明における吸着対象のガスとしては、上記塩化ビニルモノマーに限定されない。本発明の目的が吸着材等の塔充填材の保持具の金網の腐食を防止することである点から、吸着対象のガスとして含ハロゲン有機化合物が好ましく、具体的には、塩化ビニルモノマー、ジクロロエタン、四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチル、塩化エチル等の有機塩化物、トリフルオロクロロエチレン、フッ化ビニル、テトラフルオロエチレン、トリフルオロエチレン等の含フッ素化合物等が挙げられる。
以下、実施例および比較例を挙げて本発明を具体的に説明する。
【００１１】
【実施例１】
竪型チューブ式熱交換器のチューブ内最下部に、非吸着性材料として直径６ｍｍのセラミックボールとその上に直径３ｍｍのセラミックボールを、それぞれ充填高さ１０ｃｍに充填し、さらに上部に平均粒径が２〜３ｍｍの粒状活性炭を吸着材として高さ２ｍ充填した。
上記チューブの下に、上記充填物の保持具としてＳＵＳ３１６製の４メッシュ金網（線径１．６５１ｍｍ）を取り付けた。
塩化ビニルモノマーを３０％の濃度で含有する窒素ガスを、３５℃に制御された吸着塔の下部より上昇流速約３ｃｍ／秒で通気することにより，塩化ビニルモノマーの吸着を４時間行った。その後、１８０℃に加熱して脱着を１時間行った。このサイクルで連続的に３年間運転を継続したが、金網の腐食、破損は発生しなかった。
【００１２】
【比較例１】
竪型チューブ式熱交換器式のチューブ内最下部に、非吸着性材料として直径３ｍｍのセラミックボールを充填高さ２０ｃｍに充填し、その上部に平均粒径２〜３ｍｍの粒状活性炭を吸着材として高さ２ｍ充填した。その下に、それらの充填材の保持具としてＳＵＳ３１６製の３メッシュ金網（線径１．６５１ｍｍ）とＳＵＳ３１６製の２０メッシュ金網（線径０．５０８ｍｍ）を重ねて取り付けた。なお、ここで３メッシュ金網を併用している理由は、充填材の荷重に対する補強である。
得られた吸着塔を使用して、実施例１と同様な吸着、脱着の運転を行ったところ、４ケ月後には２０メッシュ金網が腐食、破損して、セラミックボールと活性炭粒子が落下してしまった。
【００１３】
【比較例２】
比較例１において使用したＳＵＳ３１６製の２０メッシュ金網（線径０．５０８ｍｍ）に代えて、モネル製の２０メッシュ金網（線径０．５０８ｍｍ）を使用し、その他はすべて比較例１と同様にして塩化ビニルモノマーの吸着、脱着の運転を行った。
この場合には、６ケ月後には２０メッシュ金網が腐食、破損した。
【００１４】
【発明の効果】
本発明の縦型固定層吸着塔においては、加熱により塩化水素等の腐食性ガスを放出する塩化ビニルモノマー等を長期間吸着、脱着しても、吸着材の保持具として使用される金網の腐食、破損が起こり難い。かかる吸着塔を採用すれば、工場全体の安定操業が可能になる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a vertical fixed bed adsorption tower used for the purpose of gas adsorption and the like in the chemical industry, and the adsorption tower in the present invention is particularly generated in a vinyl chloride monomer production process and a vinyl chloride polymer production process. It is suitable as a vertical fixed-bed adsorption device for organic chloride compounds in various waste gases such as ethylene dichloride or vinyl chloride monomer.
[0002]
[Prior art]
The structure of the vertical fixed-bed adsorption tower is basically the same as that of the vertical heat exchanger. A number of tubes are provided in parallel with the tower wall, and the area around the tubes is a passage for temperature control medium. And the tube is filled with an adsorbent such as activated carbon. In such an adsorption tower, a wire mesh or grating, or a combination thereof, is required at the bottom of a tube, that is, an adsorption tank, for holding the adsorbent.
When a wire mesh and a grating are used together, it is common practice to use a wire mesh to prevent the adsorbent from falling and the grating to support the load. Therefore, as the void portion of the wire mesh (generally called an aperture), one slightly smaller than the particle size of the adsorbent is used, and when activated carbon or the like is used as the adsorbent, the aperture is about 0.1 to 3 mm. Is suitable.
[0003]
However, in a wire mesh having the above-mentioned opening, the metal wire constituting the wire mesh has to be narrowed due to a manufacturing reason, and as a result, there is a small amount of corrosive gas generated due to the operating conditions of the adsorption tower. There is a problem that the wire mesh is cut by the contact of the wire.
That is, when an organic chloride such as a vinyl chloride monomer is adsorbed by activated carbon, a high temperature of 150 to 180 ° C. is applied when desorbing after the adsorption, and corrosive gas such as hydrogen chloride gas is generated at that time. And it was difficult to actually use the adsorption tower for a long time. As the material of the wire netting, a metal having excellent corrosion resistance can be used, but it is expensive and industrially disadvantageous.
An object of the present invention is to provide a vertical fixed-bed adsorption tower capable of continuing operation for a long period of time without damaging the wire mesh, which is a holder for the adsorbent.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
That is, the present invention relates to a vertical fixed bed adsorption tower in which a granular adsorbent is filled in a tube, and a granular non-adsorbent material having a particle size similar to that of the adsorbent below and in contact with the granular adsorbent layer. A layer, and at least one layer of a particulate non-adsorbent material having a larger particle size in contact with and in contact with the non-adsorbent material layer, and having a wire diameter as a holder for these fillers. The vertical fixed bed adsorption tower is characterized in that a wire mesh of 0.6 mm or more is used.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
The structure of the vertical fixed bed adsorption tower in the present invention is the same as that of the vertical fixed bed adsorption tower generally used in the chemical industry and the like.In the present invention, the granular adsorbent is contained in each tube in the tower. It is filled, under which the above-mentioned non-adsorptive material layer is provided, and further below it, a wire mesh for holding the above-mentioned material is provided.
Hereinafter, an adsorption tower for adsorption of a vinyl chloride monomer, which is a typical example of the present invention, will be described in detail. As the adsorbent, granular activated carbon having a particle diameter of about 0.5 to 3 mm is preferable, and more preferably granular activated carbon having an average particle diameter of 2 to 3 mm.
As the non-adsorptive material, ceramic balls, stainless steel balls, or the like can be used. Regarding the particle size of the non-adsorbent material, the particle size of the non-adsorbent material used in contact with the granular adsorbent layer is almost the same as that of the adsorbent, and the non-adsorbent material used for the non-adsorbent material layer provided thereunder The particle size of the conductive material needs to be larger than the particle size of the filler thereon. When three or more non-adsorptive material layers are provided, a material having a larger particle size is used in a lower layer. The thickness of each non-adsorptive material layer is not particularly limited, but is usually preferably about 5 to 10 cm.
[0006]
By adopting the above-mentioned means, in the present invention, the particle size of the non-adsorptive material in contact with the wire mesh can be increased to some extent, and as a result, a wire mesh having a large opening, that is, a wire mesh having a large metal wire diameter is used. It became possible to do. By using a wire mesh having a large wire diameter as a holder for a filler in an adsorption tower, damage to the wire mesh did not occur even if the operation of adsorbing and desorbing the vinyl chloride monomer was performed over a long period of time.
[0007]
As the wire mesh holding the filler of the vertical fixed bed adsorption tower, a wire mesh having a wire diameter of 0.6 mm or more can be used, and a more preferred wire diameter is 0.8 to 4.5 mm. Particularly preferably, it is 1.6 to 4.5 mm. If the wire diameter is less than 0.6 mm, the wire mesh is cut in a short time in the operation of adsorption and desorption of the vinyl chloride monomer. If the wire diameter exceeds 4.5 mm, the mesh size of the wire mesh increases, which is not practical.
The mesh size of a metal mesh formed of a metal wire having a wire diameter of 1.6 to 4.5 mm is usually 4 to 10 mm. Therefore, it is preferable that the particle size of the material forming the non-adsorptive material layer in contact with the wire mesh is about 6 to 12 mm.
[0008]
The reason why a plurality of non-adsorbing material layers are provided is that unless the particle size of the filler is gradually increased, the filler forming the upper layer falls and the layer collapses. When using activated carbon having an average particle size of 2 to 3 mm as an adsorbent, it is preferable to provide two to three non-adsorbent material layers. For example, a non-adsorbent material having a particle size of about 3 mm is used for a layer in contact with the adsorbent, a non-adsorbent material having a particle size of about 6 mm is used thereunder, and a non-adsorbent material having a particle size of about 9 mm is used as a lowermost layer. Use materials. When activated carbon having a smaller particle size is used, it is preferable to provide 3 to 5 non-adsorbent material layers.
[0009]
Typical operating conditions for adsorption and desorption of vinyl chloride monomer are as follows.
Adsorption temperature: 30-50 ° C
Desorption temperature: 120 to 190 ° C
At the time of desorption, it is preferable to supply steam or nitrogen gas as a carrier gas or to evacuate it, and further, these means may be combined.
[0010]
The gas to be adsorbed in the present invention is not limited to the above vinyl chloride monomer. From the viewpoint that the object of the present invention is to prevent corrosion of a wire mesh of a holder for a tower filler such as an adsorbent, a halogen-containing organic compound is preferable as a gas to be adsorbed, and specifically, a vinyl chloride monomer, dichloroethane And organic chlorides such as carbon tetrachloride, chloroform, trichloroethylene, methyl chloride, and ethyl chloride; and fluorine-containing compounds such as trifluorochloroethylene, vinyl fluoride, tetrafluoroethylene, and trifluoroethylene.
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
[0011]
Embodiment 1
A ceramic ball having a diameter of 6 mm as a non-adsorptive material and a ceramic ball having a diameter of 3 mm are filled at a filling height of 10 cm, respectively, at the bottom of the tube of the vertical tube type heat exchanger, and the average particle size is further formed at the top. Was filled with granular activated carbon having a height of 2 to 3 mm as an adsorbent and a height of 2 m.
A 4-mesh SUS316 mesh (diameter 1.651 mm) was attached below the tube as a holder for the filler.
Nitrogen gas containing a vinyl chloride monomer at a concentration of 30% was passed through the lower portion of the adsorption tower controlled at 35 ° C. at an ascending flow rate of about 3 cm / sec to adsorb the vinyl chloride monomer for 4 hours. Thereafter, the sample was heated to 180 ° C. to perform desorption for 1 hour. The operation was continued for three years continuously in this cycle, but no corrosion or breakage of the wire mesh occurred.
[0012]
[Comparative Example 1]
At the bottom of the vertical tube type heat exchanger type tube, a 3 mm diameter ceramic ball is filled as a non-adsorbing material to a filling height of 20 cm, and a granular activated carbon having an average particle size of 2 to 3 mm is used as an adsorbent on the upper portion. Filled 2 m in height. Below this, a SUS316 3-mesh wire mesh (wire diameter 1.651 mm) and a SUS316 20-mesh wire mesh (wire diameter 0.508 mm) were attached as holders for the fillers. The reason why the 3-mesh wire mesh is used in combination here is to reinforce the load of the filler.
Using the obtained adsorption tower, the same adsorption and desorption operations as in Example 1 were performed. After 4 months, the 20-mesh wire mesh was corroded and damaged, and the ceramic balls and activated carbon particles fell. Was.
[0013]
[Comparative Example 2]
In place of the SUS316 20 mesh wire mesh (wire diameter 0.508 mm) used in Comparative Example 1, a Monel 20 mesh wire mesh (wire diameter 0.508 mm) was used. The operation of adsorption and desorption of the vinyl chloride monomer was performed.
In this case, the 20-mesh wire net was corroded and damaged after 6 months.
[0014]
【The invention's effect】
In the vertical fixed bed adsorption tower according to the present invention, even if vinyl chloride monomer or the like that releases a corrosive gas such as hydrogen chloride upon heating is adsorbed and desorbed for a long period of time, corrosion of the wire mesh used as a holder for the adsorbent is prevented. It is hard to break. If such an adsorption tower is employed, stable operation of the whole factory can be achieved.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000044367A JP3593650B2 (en) | 2000-02-22 | 2000-02-22 | Vertical fixed bed adsorption tower |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000044367A JP3593650B2 (en) | 2000-02-22 | 2000-02-22 | Vertical fixed bed adsorption tower |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001232133A JP2001232133A (en) | 2001-08-28 |
| JP3593650B2 true JP3593650B2 (en) | 2004-11-24 |
Family
ID=18567123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000044367A Expired - Lifetime JP3593650B2 (en) | 2000-02-22 | 2000-02-22 | Vertical fixed bed adsorption tower |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3593650B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368220A (en) * | 2014-05-20 | 2015-02-25 | 常州大学 | Novel efficient organic waste gas adsorption tower |
-
2000
- 2000-02-22 JP JP2000044367A patent/JP3593650B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368220A (en) * | 2014-05-20 | 2015-02-25 | 常州大学 | Novel efficient organic waste gas adsorption tower |
| CN104368220B (en) * | 2014-05-20 | 2016-08-17 | 常州大学 | A kind of organic exhaust gas adsorption tower |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001232133A (en) | 2001-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1078695C (en) | Low pressure gas source and dispensing apparatus with enhanced diffusive/extractive means | |
| US5704967A (en) | Fluid storage and delivery system comprising high work capacity physical sorbent | |
| AU765365B2 (en) | Air separation using monolith adsorbent bed | |
| JP2008196689A (en) | Fluid storage and delivery system comprising high work capacity physical sorbent | |
| US20120006193A1 (en) | Adsorption-desorption apparatus and process | |
| JP2002515570A (en) | Sorptive gas storage and release system for high purity gas release | |
| KR20010073040A (en) | Process for fabricating a sorbent-based gas storage and dispensing system, utilizing sorbent material pretreatment | |
| JP2013523424A5 (en) | ||
| KR20060045436A (en) | Ingredient and process for producing copper(i) chloride, adsorbent and adsorbing method for reductive gas each with the use of copper(i) chloride, and recovering method of carbon monoxide gas | |
| TW201138932A (en) | Adsorbent bed support | |
| JP3593650B2 (en) | Vertical fixed bed adsorption tower | |
| TW546164B (en) | Cleaning process and cleaning agent for harmful gas | |
| JP2935524B2 (en) | Purification method of sulfuryl fluoride by selective adsorption | |
| JP5700570B2 (en) | Adsorbing / desorbing device for storing and dispensing adsorbing fluid and fluid reagent supply method | |
| US5989314A (en) | Pressure swing adsorption air prepurifier | |
| CA1055405A (en) | Method for prolonging the breakthrough of volatile substances through adsorbent-containing air purifying devices | |
| JP2009008265A5 (en) | ||
| JP2766793B2 (en) | Treatment and recovery of gaseous hydrocarbons contained in waste gas | |
| JPS6013005B2 (en) | Recovery method for halogenated hydrocarbons | |
| JP7166152B2 (en) | Adsorption tower and removal equipment for volatile organic compounds in gas | |
| US7465692B1 (en) | Reactive media, methods of use and assemblies for purifying | |
| JP2009544466A (en) | Sorption system and method with naturally occurring zeolites | |
| US20220128196A1 (en) | Adsorbent-type storage and delivery vessels with high purity delivery of gas, and related methods | |
| US20220112986A1 (en) | Storage and Delivery Veseel for Storing GeH4, Using a Zeolitic Adsorbent | |
| Stavitskaya et al. | Sorption capture of chlorine with carbon adsorbents from waste gases yielded by electrolysis of chloride solutions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040701 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040727 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040819 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3593650 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070910 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080910 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080910 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090910 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090910 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100910 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120910 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120910 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120910 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130910 Year of fee payment: 9 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |