JPS63166980A - Aqueous composite antiscale agent for foiler - Google Patents
Aqueous composite antiscale agent for foilerInfo
- Publication number
- JPS63166980A JPS63166980A JP31282086A JP31282086A JPS63166980A JP S63166980 A JPS63166980 A JP S63166980A JP 31282086 A JP31282086 A JP 31282086A JP 31282086 A JP31282086 A JP 31282086A JP S63166980 A JPS63166980 A JP S63166980A
- Authority
- JP
- Japan
- Prior art keywords
- potassium
- agent
- aqueous composite
- weight
- corrosion
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 6
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 5
- 239000004302 potassium sorbate Substances 0.000 claims abstract description 5
- 235000010241 potassium sorbate Nutrition 0.000 claims abstract description 5
- 229940069338 potassium sorbate Drugs 0.000 claims abstract description 5
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 235000019252 potassium sulphite Nutrition 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 229940123973 Oxygen scavenger Drugs 0.000 claims 2
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229940075554 sorbate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
この発明は、ボイラー用水系複合清缶剤に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a water-based composite boiler cleaning agent.
ボイラーの水質による事故は、大別すると、３種に分類
される。１番目は、ボイラーの本体の腐食によるもの、
２番目は、スケール付着によるもの、３番目は、溶解固
形物等が多過ぎることによるキャリーオーバーの現象で
ある。この内の３番目に関する問題は、電気伝導度を測
定し、それに見合ったブローを行うことにより十分に防
ぐことが可能である。しかし、１番目と２番目の問題に
ついては、最近ボイラーが高効率となったことに関連し
て、
■ 伝熱面での負荷が高くなり、その部分の水の濃縮度
が増してきている。そのため、さらに高い分散力が要求
される。またその部分でのアルカリ腐食も心配される。Accidents caused by boiler water quality can be broadly classified into three types. The first is due to corrosion of the boiler body.
The second problem is scale adhesion, and the third problem is carryover caused by too much dissolved solid matter. The third problem can be sufficiently prevented by measuring the electrical conductivity and blowing accordingly. However, regarding the first and second problems, as boilers have recently become more efficient, the load on heat transfer has increased, and the concentration of water in that area has increased. Therefore, even higher dispersion power is required. There is also concern about alkali corrosion in that area.
■ 給水が流入する部分と蒸気が排出される部分との温
度・濃縮度に大きな差がみられ、給水が流入する部位で
は温度が低いため、従来の脱酸素力では不十分でピッチ
ング腐食等が問題となる。（特に復水や節炭器を使用し
ない場合）という状況である。■ There is a large difference in temperature and concentration between the part where the feed water flows in and the part where the steam is discharged, and because the temperature is low in the part where the feed water flows in, conventional deoxidizing power is insufficient and pitting corrosion etc. It becomes a problem. (Especially when condensate or energy savers are not used).
そこで発明者らは、この状況に見合った薬品の開発のた
めの多くの実験・研究を重ねた結果、この発明を導く次
の結論を得たものである。As a result of numerous experiments and studies aimed at developing a drug suitable for this situation, the inventors came to the following conclusion that led to this invention.
上記■の問題解決のためには、従来よりポリアクリル酸
ナトリウム（分子ｆｆｉ １０００〜２０００）が分散
剤として用いられてきているが、発明者らの研究の結果
では、ポリアクリル酸ナトリウムの投入量は分散力と経
済性から６〜３０ｐｐｍが適切な値であるとわかった。Sodium polyacrylate (molecular ffi 1000-2000) has traditionally been used as a dispersant to solve the problem (1) above, but according to the results of the inventors' research, the amount of sodium polyacrylate It was found that 6 to 30 ppm is an appropriate value from the viewpoint of dispersion power and economical efficiency.
また、缶内の腐食防止の目的でＰＨ副調整単に強アルカ
リを用いたのでは、高効率ボイラーにおいて伝熱面での
アルカリ腐食を招くことがわかったため、炭酸塩を構成
要素とし、強アルカリと併用してＰＨ緩衝作用を与える
ことにより、ＰＨの上がり過ぎを防止した。In addition, it was found that simply using a strong alkali to sub-adjust the pH for the purpose of preventing corrosion inside the can would lead to alkali corrosion on the heat transfer surface in high-efficiency boilers. By providing a pH buffering effect when used in combination, excessive rise in pH was prevented.
一方、■の問題解決には、低温で速効性のある脱酸素剤
が必要である０発明者らはこのため、亜硫酸塩を用い、
低温での効果を高めるべく、触媒を種々検討した結果、
コバルト塩を適用すると、効果が高いことを見出した。On the other hand, to solve the problem of
As a result of studying various catalysts to increase the effectiveness at low temperatures, we found that
It has been found that applying cobalt salts is highly effective.
そして、低温での反応性が高まることによって、保存性
が劣下するようになるのを抑制するための安定剤を種々
検討して、ソルビン酸塩を選定した。After examining various stabilizers to suppress the deterioration of storage stability due to increased reactivity at low temperatures, sorbate was selected.
以上の要素をすべて組み合わせた高濃度清缶剤を製造し
ようとすると、溶解度が問題となるが一般にカリウム塩
はナトリウム塩よりも溶解度が高いので、入手可能なも
のはすべてカリウム塩がよい。When trying to produce a highly concentrated can cleaning agent that combines all of the above elements, solubility becomes a problem, but potassium salts generally have higher solubility than sodium salts, so any available potassium salt is preferable.
これらの成分を複合した清缶剤は、分散力と脱酸素力に
優れ、また高効率ボイラーに見出されるボイラー缶内の
部位による濃縮度や温度の差に十分対応できるもので、
ボイラーの腐食とスケールを効果的に防止することがで
きる。Bottle cleaning agents that combine these ingredients have excellent dispersion and deoxidizing power, and can adequately handle differences in concentration and temperature depending on the location within the boiler can found in high-efficiency boilers.
It can effectively prevent boiler corrosion and scale.
例１：ポリアクリル酸を含む組成物Ａ（水酸化カリウム
）と含まない組成物Ｂ（炭酸カリウム）。Example 1: Composition A with polyacrylic acid (potassium hydroxide) and composition B without (potassium carbonate).
また薬品を投入しない場合の分散力を比較した。We also compared the dispersion power when no chemicals were added.
条件 ヒーター：２００Ｖ−３ＫＷ（φ１６ｍａＸ１８
０＋＋ａ）インコネル製バイブ
ヒーター
電 圧 ： １６７Ｖ （２５万Ｋｃａｌ／ ｍ ”ｈ
相当）
水道水硬水（２０ｌ１ｇ／ ｌ ａｓ ＣａＣＯ３の硬
度骨を含む）を１．５倍／ｈの速さで濃縮した。Conditions Heater: 200V-3KW (φ16maX18
0++a) Inconel vibe heater Voltage: 167V (250,000Kcal/m ”h
Equivalent) Tap water hard water (containing hard bones of 20 l1g/las CaCO3) was concentrated at a rate of 1.5 times/h.
このときの実験器具の構造を図−１に示す。The structure of the experimental equipment used at this time is shown in Figure 1.
図−２は、この実施例における結果を示すものであるが
、同図から明らかなように、ポリアクリル酸による分散
効果は、顕著である。Figure 2 shows the results of this example, and as is clear from the figure, the dispersion effect of polyacrylic acid is remarkable.
例２：硫酸コバルトの効果について組成物Ａ（水酸化カ
リウム）とＣ（亜硫酸カリウム）で比較した。Example 2: The effects of cobalt sulfate were compared between compositions A (potassium hydroxide) and C (potassium sulfite).
組成物−〇（χ）
Ｋ ＯＨ４，５
に、Ｃｏ、 ４．７
に、Ｓｏ、 ２８．３
ソルビン酸
カリウム ０．４７
硫酸コバルト ０
ポリアクリル酸
ナトリウム ４．７
純水 ５７．３３
条件 水温 ３０°Ｃ
水 ：蒸留水）
薬品投入！ｊｉ ： ３００ ｍ ｇ ／ Ｑこの例に
用いた実験器具を図−３に示す。図−４の実験結果によ
ると、酸素除去にコバルトが有効な触媒作用を示してい
ることが認められる。Composition-〇(χ) K OH4,5, Co, 4.7, So, 28.3 Potassium sorbate 0.47 Cobalt sulfate 0 Sodium polyacrylate 4.7 Pure water 57.33 Conditions Water temperature 30° C Water: Distilled water) Add chemicals! ji: 300 mg/Q The experimental equipment used in this example is shown in Figure 3. According to the experimental results shown in Figure 4, it is recognized that cobalt exhibits an effective catalytic effect in removing oxygen.
例３：ソルビン酸塩の効果について確認した。Example 3: The effect of sorbate was confirmed.
（）Ｊｌ成物Ｄ：ソルビン酸カリウム、組成物Ｅ：硫酸
コバルト）
組成物りとＥを各々５００ ｃｃのビーカーに２５ｇと
り５００ ｃｃまで純水で希釈して、ＮａｚＳＯｓ濃度
を経時的に測定した。()Jl product D: Potassium sorbate, Composition E: Cobalt sulfate) 25g of each composition Rito E was placed in a 500 cc beaker and diluted with pure water to 500 cc, and the NazSOs concentration was measured over time. .
条件 ：室温放置
図−５の通り、ソルビン酸が保存中の安定化に寄与して
いることは明らかである。Conditions: Storage at room temperature As shown in Figure 5, it is clear that sorbic acid contributes to stabilization during storage.
図−１はこの発明におけるポリアクリル酸を含む組成物
Ａ（水酸化カリウム）と含まない組成物Ｂ（炭酸カリウ
ム）、また薬品を投入しない場合の分散力を比較した実
験器具の構造を示す概略図、図−２は図−１の実験にお
ける結果を示すグラフ、図−３は硫酸コバルトの効果に
ついて組成物Ａ（水酸化カリウム）とＣ（亜硫酸カリウ
ム）で比較した実験器具を示す概略図、図−４は図−３
の実験における結果を示すグラフ、図−５はソルビン酸
塩の効果について実験した結果を示すグラフである。
特許出願人 三浦工業株式会社
図一番
脱醸套力
葉面■へからり一間 （
分）＾ １ ４ 啼 １
〜 − 〇≧Figure 1 is a schematic diagram showing the structure of an experimental device for comparing the dispersion power of composition A (potassium hydroxide) containing polyacrylic acid and composition B (potassium carbonate) not containing polyacrylic acid, as well as when no chemicals are added. Figures and Figure-2 are graphs showing the results of the experiment in Figure-1; Figure-3 is a schematic diagram showing the experimental equipment used to compare compositions A (potassium hydroxide) and C (potassium sulfite) on the effects of cobalt sulfate; Figure-4 is Figure-3
Figure 5 is a graph showing the results of an experiment on the effect of sorbate. Patent applicant: Miura Kogyo Co., Ltd.
minute) ＾ 1 4 啼 1
~ − 〇≧
Claims (1)
の１者又は両者、脱酸素剤として亜硫酸カリウム、その
安定剤としてソルビン酸カリウム、脱酸素剤の触媒とし
て硫酸コバルト、スケール分散剤としてポリアクリル酸
ナトリウム（分子量１０００〜５０００）をそれぞれ含
み、その各々の割合が水酸化カリウム０〜５重量％：炭
酸カリウム２〜６重量％：亜硫酸カリウム１５〜３０重
量％：ソルビン酸カリウム０．１〜０．５重量％：硫酸
コバルト０．００３〜０．０１重量％：ポリアクリル酸
ナトリウム２〜５重量％であることを特徴とする水系複
合清缶剤。One or both of potassium hydroxide and potassium carbonate as a pH adjuster, potassium sulfite as an oxygen scavenger, potassium sorbate as its stabilizer, cobalt sulfate as a catalyst for the oxygen scavenger, and sodium polyacrylate as a scale dispersant. (molecular weight 1000-5000), each of which has a ratio of 0-5% by weight of potassium hydroxide: 2-6% by weight of potassium carbonate: 15-30% of potassium sulfite: 0.1-0.5% of potassium sorbate. A water-based composite can cleaning agent characterized in that the weight percent is: 0.003 to 0.01 weight % of cobalt sulfate: 2 to 5 weight % of sodium polyacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31282086A JPS63166980A (en) | 1986-12-27 | 1986-12-27 | Aqueous composite antiscale agent for foiler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31282086A JPS63166980A (en) | 1986-12-27 | 1986-12-27 | Aqueous composite antiscale agent for foiler |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63166980A true JPS63166980A (en) | 1988-07-11 |
| JPH0141707B2 JPH0141707B2 (en) | 1989-09-07 |
Family
ID=18033809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31282086A Granted JPS63166980A (en) | 1986-12-27 | 1986-12-27 | Aqueous composite antiscale agent for foiler |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63166980A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0774467B2 (en) * | 1990-10-11 | 1995-08-09 | ファイザー・インコーポレーテッド | Removal of oxygen with ketogluconate |
| US6402984B1 (en) * | 1997-03-28 | 2002-06-11 | Miura Co., Ltd. | Composition for preventing corrosion using a sulfite-based oxygen scavenger |
-
1986
- 1986-12-27 JP JP31282086A patent/JPS63166980A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0774467B2 (en) * | 1990-10-11 | 1995-08-09 | ファイザー・インコーポレーテッド | Removal of oxygen with ketogluconate |
| US6402984B1 (en) * | 1997-03-28 | 2002-06-11 | Miura Co., Ltd. | Composition for preventing corrosion using a sulfite-based oxygen scavenger |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0141707B2 (en) | 1989-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4108790A (en) | Corrosion inhibitor | |
| US3766077A (en) | Compositions and method for inhibiting scaling in aqueous systems | |
| DE3445314C2 (en) | A composition for suppressing scale formation and use thereof | |
| JPS60248287A (en) | Deoxidation composition and method | |
| ES2227632T3 (en) | STABILIZERS FOR ADDITIVES IN WATER SYSTEMS CONTAINING OZONE. | |
| US4975219A (en) | Corrosion inhibitor for boiler water systems | |
| US4547294A (en) | Alkaline scale abatement in cooling towers | |
| JP4959062B2 (en) | Water treatment method | |
| JPS57119981A (en) | Method for stabilizing aqueous solution containing chlorine-containing oxidizing agent | |
| US4906384A (en) | No drain acid treatment of pools | |
| JPS63166980A (en) | Aqueous composite antiscale agent for foiler | |
| JPH01155988A (en) | Oxygen collecting agent for boiler water and use thereof | |
| US5254526A (en) | Method to prevent algae growth in pools and spas | |
| KR910002896B1 (en) | Stabilized acidic aqueous solutions containing hydrogen peroxide and metallic ions | |
| JPS6013760B2 (en) | Composition for preventing scale | |
| JP5057030B2 (en) | Dichloroisocyanurate composition with high storage stability | |
| JPH08132093A (en) | Detergent composition | |
| JP2848672B2 (en) | High-temperature water-based corrosion inhibitor | |
| JPH06240477A (en) | Method of suppressing corrosion of metal by using polytartaric acid | |
| KR900003981B1 (en) | Method for corrosion inhibition of metals | |
| US20110293469A1 (en) | Additive formulation for industrial cooling systems | |
| JP3806869B2 (en) | Descaler and inhibitor | |
| JPS63166981A (en) | Aqueous composite antiscale agent for boiler | |
| JP2848671B2 (en) | High-temperature water-based corrosion inhibitor | |
| US4668293A (en) | Phytate corrosion inhibitor system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |