JPH055762B2 - - Google Patents
Info
- Publication number
- JPH055762B2 JPH055762B2 JP60127627A JP12762785A JPH055762B2 JP H055762 B2 JPH055762 B2 JP H055762B2 JP 60127627 A JP60127627 A JP 60127627A JP 12762785 A JP12762785 A JP 12762785A JP H055762 B2 JPH055762 B2 JP H055762B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum phosphate
- dihydrate
- dihydrogen tripolyphosphate
- condensed
- aluminum
- 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 - Fee Related
Links
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
Description
産業上の利用分野
本発明は、微粒子縮合リン酸アルミニウムの製
造法に関するものである。
縮合リン酸アルミニウムは、水ガラスの硬化剤
に多量に使用されており、また防錆顔料、脱臭剤
に用途が開発されている。
従来の技術
縮合リン酸アルミニウムは、リン酸アルミニウ
ム溶液を蒸発乾固し、得られた正リン酸アルミニ
ウムを種々の温度で熱処理を施すことによつて得
られ、この方法は公知である。
発明が解決しようとする問題点
しかし、公知の方法で得られる縮合リン酸アル
ミニウムは粒径が著しく大きく、水ガラスの硬化
剤や防錆顔料として使用するには、一般に粉砕工
程が必要である。さらに問題は、この縮合リン酸
アルミニウムの硬度が非常に高いことであつて、
粉砕機の磨滅が著しく、しかも所望の粒径まで粉
砕が困難であつた。
この問題点を解決するため、特公昭51−34400
においては、正リン酸アルミニウム溶液または懸
濁液を塔中で250℃以上の温度でスプレー乾燥す
る方法が発明されているが、製造装置が複雑とな
る。
問題を解決するための手段
この問題を解決するため、本発明者らは、縮合
リン酸アルミニウムが生成する過程を詳細に検討
した結果、中間物質として生成するトリポリリン
酸二水素アルミニウム・二水和物（AlH2P3O10・
2H2O）の硬度が小さく、粉砕が容易であること
に着眼して本発明を完成した。
すなわち、本発明者らが各種試料を粉砕した経
験によると、縮合リン酸アルミニウムは石英やガ
ラス、磁器などと同程度のカタサであつて、モー
スカタサは６〜７と推定される。トリポリリン酸
二水素アルミニウム・二水和物を粉砕すると石コ
ウあるいは炭酸カルシウムと同程度、あるいはそ
れ以下のカタサしかなく、モースカタサは２〜３
と推定される。
縮合リン酸アルミニウムは硬度が大きいから、
この粉砕品の粒径が大きく、しかも粗粒が多く含
まれる。粉砕機の摩耗も著しいから、縮合リン酸
アルミニウム粉砕品には鉄分が多く含まれてくる
欠点があるほか、粉砕機の保守や、粉砕した縮合
リン酸アルミニウムの品質管理も容易ではない。
これに対して、トリポリリン酸二水素アルミニウ
ム・二水和物は硬度が小さいから、粉砕品の粒径
が小さく、粒径分布も狭く粗粒を含むことがな
い。粉砕機の摩耗はほとんどないから、粉砕機の
内面に由来する鉄分が混入する危険がなく、粉砕
機の保守や粉砕したトリポリリン酸二水素アルミ
ニウム・二水和物の品質管理はきわめて容易であ
る。得られた微粉砕トリポリリン酸二水素アルミ
ニウム・二水和物を焼成すれば、容易に微粒子縮
合リン酸アルミニウムを製造することができる。
このように、本発明は、縮合リン酸アルミニウ
ムを製造する過程において、トリポリリン酸二水
素アルミニウム無水物を水と接触させることによ
つて微粉砕が容易なトリポリリン酸二水素アルミ
ニウム・二水和物を含む中間物を生成させ、この
中間物を微粉砕したのち熱処理して、水ガラスの
硬化剤や防錆顔料、脱臭剤などに好適な微粒子縮
合リン酸アルミニウムを製造する方法を提供する
ものである。
本発明において、中間物の中に生成させるトリ
ポリリン酸二水素アルミニウム・二水和物の原料
となる無水物の製造方法は公知である。たとえば
特公昭51−560では、アルミニウムまたはアルミ
ニウム含有物質およびリン酸物質からなり、かつ
P2O5／Al2O3のモル比が１〜６の混合物を90〜
450℃の温度で撹拌下に加熱して不透明半固体状
のものを得、ついでこれを300〜450℃の温度に再
加熱して脱水結晶化するとトリポリリン酸二水素
アルミニウム無水物が得られる。この物質の硬度
は高いので、粉砕は必ずしも簡単ではないが、こ
れは容易に水分を吸収して二水和物となる。しか
し本発明のトリポリリン酸二水素アルミニウム・
二水和物の製造方法は上記方法に限定されるもの
ではない。
トリポリリン酸二水素アルミニウム・無水物に
吸水させて水和物とする方法には、空気中の水分
を吸収させる方法、水蒸気を吹付ける方法、水を
スプレーする方法、水中に投入する方法などのい
ずれの方法でもよいが、熱水中に投入すると急速
に水和反応が進行する結果、二水和物の微結晶が
得られるので、本発明の目的の二水和物を得るた
めには好適な方法である。
このようにして得られたトリポリリン酸二水素
アルミニウム・二水和物は六角板状の結晶であつ
て、硬度も小さいから微粉砕が容易である。粉砕
は、空気中で行う乾式粉砕のほか、コイドミルの
ような湿式粉砕も可能であつて、粉砕機の型式に
もとくに制限はない。
微粉砕したトリポリリン酸二水素アルミニウ
ム・二水和物は、さらに高温度で熱処理すると、
水和水の脱水、構造水の脱水縮合反応が生じて、
微粒子縮合リン酸アルミニウムを得ることができ
る。熱処理後の粉砕は、熱処理温度によつて必要
性が異なるが、一般的には解砕程度の粉砕だけで
十分である。
微粒子縮合リン酸アルミニウムを製造するにあ
たつては、上記トリポリリン酸二水素アルミニウ
ム・二水和物が生成するような条件を選び、その
中間生成物中での本物質の含有量が20％以上、で
きれば40％以上が望ましい。本物質の含有量が20
％未満の場合は、中間生成物の微粉砕が困難とな
る。
トリポリリン酸二水素アルミニウム・二水和物
はＸ線（Cu−Kα）によつて2θ＝11.2℃に特徴あ
る鋭い回析線が得られるので、容易に本物質を定
量分析することができる。
実施例
水酸化アルミニウムをリン酸に溶解して、種々
のP2O5／Al2O3モル比の正リン酸アルミニウム溶
液を調製する。この溶液を、特公昭51−560記載
の条件で脱水結晶化する。得られた脱水結晶化物
を熱水中に投入して吸水させ、トリポリリン酸二
水素アルミニウム・二水和物を含む中間物を得
る。
中間物はＸ線（Cu−Kα）回析法によつて該物
質の定量分析を行つたのち、ボールミルを用いて
１昼夜粉砕し、700℃に加熱して脱水縮合反応を
進行させ、ボールミルで再び粉砕して微粒子縮合
リン酸アルミニウムを得た。
微粒子縮合リン酸アルミニウムは島津粒子径解
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing fine particle condensed aluminum phosphate. Condensed aluminum phosphate is used in large quantities as a hardening agent for water glass, and is also being developed for use in rust-preventing pigments and deodorizing agents. BACKGROUND OF THE INVENTION Condensed aluminum phosphate is obtained by evaporating an aluminum phosphate solution to dryness and heat-treating the resulting aluminum orthophosphate at various temperatures, and this method is known. Problems to be Solved by the Invention However, condensed aluminum phosphate obtained by known methods has a significantly large particle size, and generally requires a pulverization step in order to be used as a hardening agent for water glass or as a rust-preventing pigment. Another problem is that the hardness of this condensed aluminum phosphate is extremely high.
The grinder was severely worn out, and it was difficult to grind the particles to the desired particle size. In order to solve this problem, the Special Publication No. 51-34400
A method has been invented in which an aluminum orthophosphate solution or suspension is spray-dried in a column at a temperature of 250° C. or higher, but the manufacturing equipment becomes complicated. Means for Solving the Problem In order to solve this problem, the present inventors investigated in detail the process of producing condensed aluminum phosphate, and as a result, aluminum dihydrogen tripolyphosphate dihydrate, which is produced as an intermediate substance, was found. (AlH 2 P 3 O 10・
The present invention was completed by focusing on the fact that 2H 2 O) has low hardness and is easy to crush. That is, according to the experience of the present inventors in pulverizing various samples, it is estimated that condensed aluminum phosphate has a roughness comparable to that of quartz, glass, porcelain, etc., and the Mohs roughness is 6 to 7. When aluminum dihydrogen tripolyphosphate dihydrate is crushed, it has the same degree of roughness as gypsum or calcium carbonate, or less, and the Mohs crusher is 2 to 3.
It is estimated to be. Because condensed aluminum phosphate has high hardness,
This pulverized product has a large particle size and contains many coarse particles. Since the grinder wears out considerably, the pulverized condensed aluminum phosphate product has the drawback of containing a large amount of iron, and it is also difficult to maintain the pulverizer and control the quality of the pulverized condensed aluminum phosphate.
On the other hand, since aluminum dihydrogen tripolyphosphate dihydrate has a low hardness, the particle size of the pulverized product is small and the particle size distribution is narrow and does not contain coarse particles. Since there is almost no wear on the pulverizer, there is no risk of contamination with iron from the inner surface of the pulverizer, and maintenance of the pulverizer and quality control of the pulverized aluminum dihydrogen tripolyphosphate dihydrate are extremely easy. By calcining the obtained finely pulverized aluminum dihydrogen tripolyphosphate dihydrate, fine particle condensed aluminum phosphate can be easily produced. As described above, the present invention produces aluminum dihydrogen tripolyphosphate dihydrate, which can be easily pulverized, by bringing aluminum dihydrogen tripolyphosphate anhydride into contact with water in the process of producing condensed aluminum phosphate. The present invention provides a method for producing fine particle condensed aluminum phosphate suitable for use as a hardening agent for water glass, an anti-rust pigment, a deodorizing agent, etc., by producing an intermediate containing the same, finely pulverizing the intermediate, and then heat-treating the intermediate. . In the present invention, the method for producing anhydride, which is a raw material for aluminum dihydrogen tripolyphosphate dihydrate produced in the intermediate, is known. For example, in Japanese Patent Publication No. 51-560, the
A mixture with a molar ratio of P 2 O 5 /Al 2 O 3 of 1 to 6 is
Heating with stirring at a temperature of 450°C gives an opaque semi-solid which is then reheated to a temperature of 300-450°C for dehydration and crystallization to obtain anhydrous aluminum dihydrogen tripolyphosphate. Due to the high hardness of this material, it is not always easy to grind, but it easily absorbs water and becomes a dihydrate. However, the aluminum dihydrogen tripolyphosphate of the present invention
The method for producing the dihydrate is not limited to the above method. There are several methods for making aluminum dihydrogen tripolyphosphate/anhydride absorb water to form a hydrate, including absorbing moisture from the air, spraying water vapor, spraying water, and placing it in water. However, when placed in hot water, the hydration reaction proceeds rapidly and microcrystals of the dihydrate are obtained, so this method is suitable for obtaining the dihydrate that is the object of the present invention. It's a method. The thus obtained aluminum dihydrogen tripolyphosphate dihydrate is a hexagonal plate-shaped crystal and has low hardness, so it can be easily pulverized. In addition to dry pulverization carried out in air, wet pulverization such as a coid mill is also possible, and there are no particular restrictions on the type of pulverizer. When finely ground aluminum dihydrogen tripolyphosphate dihydrate is further heat-treated at a high temperature,
Dehydration of hydration water and dehydration condensation reaction of structured water occur,
Fine particle condensed aluminum phosphate can be obtained. The necessity of pulverization after heat treatment differs depending on the heat treatment temperature, but pulverization to the level of crushing is generally sufficient. When producing particulate condensed aluminum phosphate, conditions are selected so that the above aluminum dihydrogen tripolyphosphate dihydrate is produced, and the content of this substance in the intermediate product is 20% or more. , preferably 40% or more. The content of this substance is 20
If it is less than %, it becomes difficult to pulverize the intermediate product. Aluminum dihydrogen tripolyphosphate dihydrate gives a characteristic sharp diffraction line at 2θ=11.2°C using X-rays (Cu-Kα), so this substance can be easily quantitatively analyzed. Examples Aluminum orthophosphate solutions with various P 2 O 5 /Al 2 O 3 molar ratios are prepared by dissolving aluminum hydroxide in phosphoric acid. This solution is dehydrated and crystallized under the conditions described in Japanese Patent Publication No. 51-560. The obtained dehydrated crystallized product is poured into hot water to absorb water to obtain an intermediate containing aluminum dihydrogen tripolyphosphate dihydrate. The intermediate was subjected to quantitative analysis of the substance by X-ray (Cu-Kα) diffraction, then ground using a ball mill for a day and night, heated to 700°C to proceed with the dehydration condensation reaction, and then milled using a ball mill. It was ground again to obtain fine particles of condensed aluminum phosphate. Fine particle condensed aluminum phosphate is determined by Shimadzu particle size analysis.
【表】
すなわち、縮合リン酸アルミニウムを製造する
にあたり、トリポリリン酸二水素アルミニウム・
二水和物を含む中間物を生成させ、この中間物を
微粉砕したのち焼成すると、微粒子縮合リン酸ア
ルミニウムが得られる。中間物に含まれるトリポ
リリン酸二水素アルミニウム・二水和物が多いほ
ど、中間物の粉砕は容易であるから最終的に得ら
れる縮合リン酸アルミニウムの粒径も小さい。こ
れに対して中間物を経由せずに熱処理して得た縮
合リン酸アルミニウムは、同一条件で粉砕しても
平均粒径は10〜20μにとどまつていた。
顕微鏡によつて観察すると、トリポリリン酸二
水素アルミニウム・二水和物を粉砕して熱処理す
る本発明の方法によつて得られる微粒子縮合リン
酸アルミニウムは、粒径がよく揃つており、粗粒
は全く認められなかつた。これに対して中間物を
経由せずに熱処理して得た縮合リン酸アルミニウ
ム粉末には数10μの粗粒の混在が認められた。
なお、市販の縮合リン酸アルミニウムの平均粒
子径の一例は12.4μで多くの粗粒が認められた。
発明の効果
実施例に見られるように、縮合リン酸アルミニ
ウムを製造する過程において、トリポリリン酸二
水素アルミニウム・二水和物を含む中間物を生成
させ、この中間物を微粉砕したのち熱処理する本
発明の方法によつて微粒子縮合リン酸アルミニウ
ムが得られる。本発明の方法によつて得られる縮
合リン酸アルミニウムは、粒径が小さく粒度分布
が鋭く、粗粒を含まない上、粉砕機からくる鉄分
等の汚染がない。比表面積も大きくなるから水ガ
ラスの硬化剤に使用するときは、均一に分散して
一様に硬化が進行し、しかも反応速度が大きい。
また防錆顔料として使用するときは、塗料中に均
一に分散して沈澱することがないから塗料の貯蔵
安定性が良好であり、緻密な塗膜が得られるから
防錆性をすぐれている。脱臭剤に使用するときは
単位重量当たりの吸着量が大きくなり経済的であ
る。
このように本発明の方法によつて、水ガラスの
硬化剤や防錆顔料、脱臭剤に好適な微粒子縮合リ
ン酸アルミニウムを得ることができる。[Table] In other words, when producing condensed aluminum phosphate, aluminum dihydrogen tripolyphosphate
When an intermediate containing a dihydrate is produced, this intermediate is pulverized, and then calcined, fine particulate condensed aluminum phosphate is obtained. The larger the amount of aluminum dihydrogen tripolyphosphate dihydrate contained in the intermediate, the easier the pulverization of the intermediate will be, and the smaller the particle size of the condensed aluminum phosphate finally obtained will be. On the other hand, condensed aluminum phosphate obtained by heat treatment without passing through an intermediate had an average particle size of 10 to 20 microns even when pulverized under the same conditions. When observed under a microscope, the fine particle condensed aluminum phosphate obtained by the method of the present invention, in which aluminum dihydrogen tripolyphosphate dihydrate is pulverized and heat-treated, has a well-uniformed particle size, with no coarse particles. It was not recognized at all. On the other hand, in the condensed aluminum phosphate powder obtained by heat treatment without passing through an intermediate, coarse particles of several tens of microns were observed. An example of the average particle size of commercially available condensed aluminum phosphate was 12.4μ, and many coarse particles were observed. Effects of the Invention As can be seen in the examples, this book involves producing an intermediate containing aluminum dihydrogen tripolyphosphate dihydrate in the process of producing condensed aluminum phosphate, pulverizing this intermediate, and then heat-treating it. By the method of the invention, fine particulate condensed aluminum phosphate is obtained. The condensed aluminum phosphate obtained by the method of the present invention has a small particle size and a sharp particle size distribution, does not contain coarse particles, and is free from contamination such as iron from the crusher. Since the specific surface area is also large, when used as a hardening agent for water glass, it is uniformly dispersed and hardening progresses uniformly, and the reaction rate is high.
Furthermore, when used as a rust-preventing pigment, it is uniformly dispersed in a paint and does not precipitate, so the paint has good storage stability, and a dense coating film is obtained, giving it excellent rust-prevention properties. When used as a deodorizer, the adsorption amount per unit weight is large, making it economical. As described above, by the method of the present invention, fine particle condensed aluminum phosphate suitable for use as a hardening agent for water glass, a rust preventive pigment, and a deodorizing agent can be obtained.
Claims (1)
法において、トリポリリン酸二水素アルミニウム
無水物を水と接触させることによつてトリポリリ
ン酸二水素アルミニウム・二水和物を含む中間物
を生成させ、この中間物を微粉砕したのち熱処理
することを特徴とする微粒子縮合リン酸アルミニ
ウムの製造方法。 ２ 中間物に含まれるトリポリリン酸二水素アル
ミニウム・二水和物が20％以上である特許請求の
範囲第１項に記載の微粒子縮合リン酸アルミニウ
ムの製造方法。[Claims] 1. In a method for producing particulate condensed aluminum phosphate, an intermediate containing aluminum dihydrogen tripolyphosphate dihydrate is produced by contacting anhydrous aluminum dihydrogen tripolyphosphate with water. A method for producing fine-particle condensed aluminum phosphate, which comprises pulverizing this intermediate and then heat-treating it. 2. The method for producing particulate condensed aluminum phosphate according to claim 1, wherein the intermediate contains 20% or more of aluminum dihydrogen tripolyphosphate dihydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12762785A JPS61286209A (en) | 1985-06-11 | 1985-06-11 | Production of condensed aluminum phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12762785A JPS61286209A (en) | 1985-06-11 | 1985-06-11 | Production of condensed aluminum phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61286209A JPS61286209A (en) | 1986-12-16 |
| JPH055762B2 true JPH055762B2 (en) | 1993-01-25 |
Family
ID=14964760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12762785A Granted JPS61286209A (en) | 1985-06-11 | 1985-06-11 | Production of condensed aluminum phosphate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61286209A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10113287A1 (en) * | 2001-03-16 | 2002-10-02 | Bk Giulini Chem Gmbh & Co Ohg | Use of polymeric aluminum phosphates in plaster formulations |
| US7763359B2 (en) | 2004-08-30 | 2010-07-27 | Bunge Fertilizantes S.A. | Aluminum phosphate, polyphosphate and metaphosphate particles and their use as pigments in paints and method of making same |
| BRPI0403713B1 (en) | 2004-08-30 | 2021-01-12 | Universidade Estadual De Campinas - Unicamp | manufacturing process of a white pigment based on the synthesis of hollow particles of aluminum orthophosphate or polyphosphate |
| US9023145B2 (en) | 2008-02-12 | 2015-05-05 | Bunge Amorphic Solutions Llc | Aluminum phosphate or polyphosphate compositions |
| US9371454B2 (en) | 2010-10-15 | 2016-06-21 | Bunge Amorphic Solutions Llc | Coating compositions with anticorrosion properties |
| US9005355B2 (en) | 2010-10-15 | 2015-04-14 | Bunge Amorphic Solutions Llc | Coating compositions with anticorrosion properties |
| US9611147B2 (en) | 2012-04-16 | 2017-04-04 | Bunge Amorphic Solutions Llc | Aluminum phosphates, compositions comprising aluminum phosphate, and methods for making the same |
| US9078445B2 (en) | 2012-04-16 | 2015-07-14 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| US9155311B2 (en) | 2013-03-15 | 2015-10-13 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| CN103523765A (en) * | 2012-07-04 | 2014-01-22 | 广东先导稀材股份有限公司 | Preparation method of aluminum dihydrogen tripolyphosphate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53133232A (en) * | 1977-04-26 | 1978-11-20 | Taki Chem Co Ltd | Coating material |
-
1985
- 1985-06-11 JP JP12762785A patent/JPS61286209A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61286209A (en) | 1986-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hong et al. | Preparation of bioactive glass ceramic nanoparticles by combination of sol–gel and coprecipitation method | |
| Aglietti et al. | Mechanochemical effects in kaolinite grinding. I. Textural and physicochemical aspects | |
| US5653782A (en) | Process for the manufacture of sulfur-containing fertilizers | |
| JPH055762B2 (en) | ||
| JPH04214024A (en) | Manufacture of crystalline sodium silicate | |
| Karimi et al. | A facile and sustainable method based on deep eutectic solvents toward synthesis of amorphous calcium phosphate nanoparticles: the effect of using various solvents and precursors on physical characteristics | |
| CN106866207A (en) | With the alkali metal ion source of moderate ion release rate and forming method | |
| JPS5864207A (en) | Manufacture of water glass cement hardening agent | |
| Singh et al. | Synthesis of brushite nanoparticles at different temperatures | |
| Boonchom | Parallelogram-like microparticles of calcium dihydrogen phosphate monohydrate (Ca (H2PO4) 2· H2O) obtained by a rapid precipitation route in aqueous and acetone media | |
| Nasri et al. | Recrystallization of industrial triple super phosphate powder | |
| Albulym et al. | Antimicrobial activity of Ga-doped hydroxyapatite nanostructures: synthesis, morphological, spectroscopic, and dielectric properties | |
| JP4988187B2 (en) | Method for producing zeolite | |
| US3531278A (en) | Process for preparing sodium borate compositions | |
| JPS58181718A (en) | Novel synthetic silicate and its manufacture | |
| JPH0470273B2 (en) | ||
| Mi et al. | Effects of Milling of a Mixture of Calcium Oxide and Silica-gel on Formation of Dicalcium Silicate by Heating and its Hydration | |
| JP2584877B2 (en) | Method for producing tetracalcium phosphate | |
| TOYAMA et al. | Mechanochemical synthesis of amorphous calcium phosphate from bovine bone | |
| DE4401527A1 (en) | Production of crystalline sodium disilicate from melted and crushed amorphous soda water glass | |
| JP7824392B2 (en) | Method for producing swellable layered silicate and method for reducing cristobalite | |
| JP2016153351A (en) | Particle containing crystal of phyllosilicate and method for producing the same | |
| CN1098827C (en) | Natural phosphate fertilizer and its wet preperation process | |
| Zhang et al. | Non-thermal production of a powder containing magnesium hydroxide from dolomite by means of mechanochemical treatment | |
| US1094857A (en) | Process of producing available phosphoric acid. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |