JPS6126495B2 - - Google Patents
Info
- Publication number
- JPS6126495B2 JPS6126495B2 JP8356578A JP8356578A JPS6126495B2 JP S6126495 B2 JPS6126495 B2 JP S6126495B2 JP 8356578 A JP8356578 A JP 8356578A JP 8356578 A JP8356578 A JP 8356578A JP S6126495 B2 JPS6126495 B2 JP S6126495B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium
- reaction
- potassium
- water
- silicon dioxide
- 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
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 239000002994 raw material Substances 0.000 claims description 36
- 239000004111 Potassium silicate Substances 0.000 claims description 34
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 34
- NYRAVIYBIHCEGB-UHFFFAOYSA-N [K].[Ca] Chemical compound [K].[Ca] NYRAVIYBIHCEGB-UHFFFAOYSA-N 0.000 claims description 33
- 235000019353 potassium silicate Nutrition 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 235000012239 silicon dioxide Nutrition 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 229940043430 calcium compound Drugs 0.000 claims description 17
- 150000001674 calcium compounds Chemical class 0.000 claims description 17
- 239000000292 calcium oxide Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Inorganic Fibers (AREA)
Description
本発明は繊維状珪酸カルシウムカリウムの新規
な製造方法を提供する。詳しくは２酸化珪素又は
２酸化珪素を含む化合物、水酸化カリウム及び水
溶性カルシウム化合物を特定の仕込み割合で仕込
み、加圧下で水熱反応させ繊維状カルシウムカリ
ウムを製造する方法である。
従来２酸化珪素、アルカリ金属塩及びカルシウ
ム化合物の反応は種々研究されているが、反応生
成物が繊維状になる知見はほとんどない。
本発明者等は、長年珪酸カルシウム化合物の合
成研究を鋭意続けて来たが、２酸化珪素、水酸化
カリウム及び水溶性カルシウム化合物を特定の仕
込み割合で特定条件下に反応させることによつ
て、繊維状珪酸カルシウムカリウムを得ることを
見出し本発明を完成させるに至つた。
本発明は２酸化珪素又は２酸化珪素を含む化合
物、水酸化カリウム及び水溶性カルシウム化合物
を、これら原料中のK2OがＸモル、SiO2がＹモル
及びCaOがＺモルとしたとき反応によつてカリウ
ム塩が副生する場合は下記式(A)で、また反応によ
つてカリウム化合物が副生しない場合は下記(B)式
で計算した原料仕込み係数Ｔが1.0〜2.5となり且
つＸ／Ｚが1.5〜６となるように仕込み、加圧
下、150〜250℃の温度で水熱反応させる繊維状珪
酸カルシウムカリウムの製造方法である。
Ｔ＝９Ｙ−３２Ｚ／９Ｘ−１２Ｚ ……(A)
Ｔ＝９Ｙ−３２Ｚ／９Ｘ−３Ｚ ……(B)
ここで、Ｘ，Ｙ，Ｚは当然正数、また(A)，(B)式
における分母，分子も後述の実施例でも示すよう
に夫々正数である。本発明で得られる繊維状珪酸
カルシウムカリウムは、化学分析することにより
一般式がほぼ3K2O・9CaO・32SiO2・nH2O（但
しｎは０〜20の数）で示されると推定される新規
な化合物である。
なお、一般に、各種結晶の一般式は化学分析に
よつて特定できるのが通常である。しかし、本発
明の対象とする珪酸塩等は、次の理由から正確な
一般式は求め難く係数に多少の変動があることを
前提にして推定し得るにとどまる。
その１は、固溶限界以下において結晶の中に分
離困難な不純物が組み込まれる場合が多々みられ
ること。
その２は、イオン交換能を有する結晶は各イオ
ンがイオン交換平衡に従つて結晶中に含まれるた
めPH、液組成によつて組成が変化することであ
る。
例えば本発明において推定される一般式におい
て、Ｋの一部がNaやCaと、またCaの一部がNaや
Ｋなどとイオン交換する例などがあげられる。こ
のように珪酸塩の一般式が特定し難いことは例え
ば特開昭51−114397号にも0.9±0.2M2／oＯ：Ａ
2O3：2.5±0.5SiO2・０〜8H2O（但しＭは金属
カチオン及びｎはその原子価）その他の記載がみ
られることからも理解される。本本発明で得られ
る繊維状珪酸カルシウムカリウムは、分子中に含
有されるK2Oに基因してイオン交換能を有する。
また、一般に製造後の繊維状珪酸カルシウムカリ
ウムは結晶水を有するが、250〜300℃で該結晶水
は離脱し、水と接触すると結晶水が復水する性質
を有する。これらの性質を利用して、該繊維状珪
酸カルシウムカリウムはイオン交換体或いは乾燥
剤として広く利用出来る物質である。
また前記結晶水、後述する方法で製造した珪酸
カルシウムナトリウムを100℃で８時間乾燥させ
ると一般に12％程度のものとなる。この水は前記
した如く250〜300℃で離脱されるが、復水する性
状を有し該水の全部又は１部を離脱させても珪酸
カルシウムカリウムの性状については変りはな
い。従つて、本発明によつて得られる珪酸カルシ
ウムナトリウムの結晶水はフツ石水の性質を有す
るものと言える。
本発明の原料は２酸化珪素又は２酸化珪素を含
む化合物、水酸化カリウム及び水溶性カルシウム
化合物の少くとも３成分である。２酸化珪素は一
般に珪酸アルカリを鉱酸と反応させて得られる湿
式法の２酸化珪素、即ち含水珪酸が一般に好適に
使用される。また２酸化珪素を含む化合物は反応
系で可溶性であれば特に限定的ではなく公知の化
合物が使用出来、一般には白土、石英等の天然物
或いはシリコンダストなどの化合物が好適に使用
出来る。更にまた、水溶性カルシウム化合物は水
溶性であれば特に限定されず、公知の化合物が用
いうる。一般に好適に使用される代表的なものを
例示すれば水酸化カルシウム、酸化カルシウム、
塩化カルシウム、硝酸カルシウム、硫酸カルシウ
ム等である。即ち水溶性のカルシウム化合物は、
例えば硫酸カルシウムの如く水に対する溶解度が
比較的小さいものも使用しうるが、これは反応に
際し珪酸カルシウムカリウムの生成に消費された
量だけのものが溶解するので、十分に工業的に原
料として使用出来る。しかしながら、水に不溶性
のカルシウム化合物、例えば炭酸カルシウムなど
はほとんど水に溶解しないため、工業的に繊維状
珪酸カルシウムを得ることが出来ない。
本発明に於ける原料は前記の少くとも３成分を
用いる必要があるが、工業的に繊維状珪酸カルシ
ウムカリウムを得ようとする場合は次の記す特定
の原料仕込み係数を選ぶことが必要である。即
ち、原料中のK2OをＸモル、SiO2をＹモル、及び
CaOをＺモルとするとき反応によつてカリウム塩
が副生する場合は下記(A)式で、反応によつてカリ
ウム塩が副生しない場合は下記(B)式で計算した原
料仕込み係数Ｔが1.0〜2.5好ましくは1.2〜1.9の
範囲となり且つＸ／Ｚが1.5〜６となるように原
料を仕込むことが必要である。
Ｔ＝９Ｙ−３２Ｚ／９Ｘ−１２Ｚ ……(A)
Ｔ＝９Ｙ−３２Ｚ／９Ｘ−３Ｚ ……(B)
（但しＸ，Ｙ，Ｚは当然正数であり、また(A)，
(B)式における分母，分子も後述の実施例でも示す
ように夫々正数である）
前記の反応によつてカリウム塩が副生する場合
と水溶性カルシウム化合物が塩化カルシウム、硫
酸カルシウム等を用いる場合で、これらの陰イオ
ンがカリウムと化合してカリウム塩例えば塩化カ
リウム、硝酸カリウム、硫酸カリウム等を副生す
る場合である。また前記の反応によつてカリウム
塩が副生しない場合とは、水溶性カルシウム化合
物として水酸化カルシウム、酸化カルシウム等を
用いる時が相当し、カリウムと反応してカリウム
塩を生成することがない場合である。
前記の原料仕込み係数Ｔが前記の下限値より小
さい場合は繊維状珪酸カルシウムカリウムが生成
したとしても反応に長時間、例えば数日〜拾数日
を要するので工業的に選ぶことが出来ない。また
原料仕込み係数Ｔが前記の上限値より大きい場合
は繊維状珪酸カルシウムカリウムは生成するが、
同時に結晶性のK2O・4SiO2・H2Oで示される珪
酸カリウムが多量副生することがあり、また繊維
状珪酸カルシウムカリウムから分離出来なくなる
場合がある。
また原料中の２酸化珪素成分及びカリウム成分
は、繊維状珪酸カルシウムカリウムの生成に必要
な量より過剰に存在させるのが好ましい。一般に
上記の過剰量は原料中のK2O／CaOモル比、即ち
前記Ｘ／Ｚが1.6〜６好ましくは２〜４の範囲と
なる如く選ぶことが必要である。Ｘ／Ｚが上記の
下限値より小さい場合は、繊維状珪酸カルシウム
カリウムの生成速度がおそく工業的に不利になる
場合がある。また逆にＸ／Ｚが前記上限値より大
きい場合は、目的生成物である繊維状珪酸カルシ
ウムカリウムは得られるが、未反応の珪酸カリウ
ムの回収量が多くなり装置面でも不利になるので
工業的には有利とは云えない。
前記に原料仕込み係数Ｔ及び原料中のK2O／
CaOモル比につき好適な基準を説明したが、これ
らの数値は原料の種類、反応条件等によつて異な
り一概に決定出来るものではない。従つて予め原
料の種類、反応条件等によつて好適な値を決定し
て実施するのがよい。
本発明に於ける原料中の水溶性カルシウム化合
物は、ほゞ100％繊維状珪酸カルシウムカリウム
の生成に消化される。このことは後述する実施例
でも明らかであるが、反応によつて生成した繊維
状珪酸カルシウムカリウムを濾別したあと、濾液
中にカルシウム成分がほとんど認められないこと
が明白となる。従つてカルシウム成分はほゞ100
％前記の珪酸カルシウムカリウムを形成するもの
と考えて、原料仕込みの組成を決定することが出
来る。
更に具体的に前記原料仕込み割合の決定につい
て一例を挙げて説明すると次ぎのようにして決定
すればよい。前記した如く、水溶性カルシウム化
合物はほゞ全ての量が繊維状珪酸カルシウムカリ
ウムに消化されることが明らかであるので、該珪
酸カルシウムカリウムを得る量を決定すれば、必
要とする水溶性カルシウム化合物の量は決定す
る。即ち、原料中の必要とするCaOモル（前記Ｚ
モル）が決定する。次いで、K2O／CaOモル比即
ちＸ／Ｚの値を適宜決定する。仮りにK2O／CaO
モル比が３となるように設定すれば、必要なK2O
モルが決定される。K2Oは原料である水酸化カリ
ウムにのみ由来するものであるから、必要とする
水酸化カリウムの量が決する。次いで前記の原料
仕込み量Ｔの算出式に応じてSiO2モルを算出出
来る。この結果より、使用する２酸化珪素又は２
酸化珪素を含む化合物の使用量を決めればよい。
本発明に於ける原料の仕込みは前記した必要の
要件以外は特に限定されるものではなく、各成分
の添加順序も特に限定的ではない。一般には水溶
液中に各原料を添加してもよく、各原料毎に水溶
液或いはスラリー溶液を調整し、これらの液を混
合してもよい。
前記の少くとも３成分の原料を仕込んだ水溶液
は、加圧下で水熱反応させることによつて繊維状
珪酸カルシウムカリウムが得られる。水熱下の反
応温度はあまりに低いと反応時間が極端に長くな
る場合があり、逆に温度が高い場合は熱エネルギ
ーの損失だけでなく耐圧容器の製作などが高価に
なるので経済的ではなくなる。一般には150〜250
℃の範囲で選ぶのが最も好適である。反応圧力は
一般に反応温度に於ける蒸気圧で実施すれば十分
で、通常は密封容器例えばオートクレーブ中でで
実施するのが好ましい。このような条件下での反
応であれば、通常は10時間〜40時間程度の反応時
間で繊維状珪酸カルシウムカリウムが得られる。
前記の加圧下で水熱反応させて得た繊維状珪酸
カルシウムカリウムは濾過することにより分離出
来る。濾過分離された繊維状珪酸カルシウムカリ
ウムは必要に応じて水洗後乾燥して製品とすれば
よい。また繊維状珪酸カルシウムカリウムを濾別
分離した濾液は、未反応の２酸化珪素及び水酸化
カリウムを含むのでそのまゝ又は他の副生成物を
除去して１部又は全部を原料として循環使用する
ことが出来る。一般に水溶性カルシウム化合物と
して水酸化カルシウム又は酸化カルシウムを用い
る場合は、副生成物が通常生成しないのでその
まゝ循環することが出来るが、水溶性カルシウム
化合物として塩化カルシウム、硝酸カルシウム、
硫酸カルシウム等を用いると前記した如くカリウ
ム塩が副生する。カリウム塩が副生する場合は原
料として濾液を循環するに先きだちこれらのカリ
ウム塩を除去するのが好ましい。
本発明を更に具体的に説明するため以下実施例
を挙げて説明するが本発明はこれらの実施例に限
定されるものではない。
実施例 １
1.0モル／の水酸化カリウム溶液100c.c.と0.25
モル／の消石灰スラリー100c.c.を混合し、この
スラリーに含水珪酸トクシールGu（商品名、
SiO2含有量85％）17.65ｇを加え良く撹拌した。
この場合の前記(B)式より算出された原料仕込み係
数Ｔは1.76であつた。このスラリーを、オートク
レーブに入れ密閉し、200℃の温度下に20時間反
応させた。反応物は濾過しイオン交換水100c.c.で
３回くりかえして水洗した後、100℃で８時間乾
燥させた。この乾燥物の収量は8.6ｇであつた。
この生成物は、化学分析によれば、ほぼ
3K2O・9CaO・32SiO2・20H2Oと推定される組成
であつた。電子顕微鏡による観察により、長さ約
220μ、アスペクト比120の繊維状物であることが
確認された。尚、反応物を濾過した濾液にはカル
シウム分がほとんど含まれていなかつた。
実施例 ２
実施例１における原料比、反応条件を第１表に
示すように変化させた意外は、実施例１と同様に
実施した。その結果は第１表に示す通りである。
全体の仕込み容積は、実施例１と同様200c.c.であ
る。
The present invention provides a novel method for producing fibrous calcium potassium silicate. Specifically, it is a method of preparing fibrous calcium potassium by charging silicon dioxide or a compound containing silicon dioxide, potassium hydroxide, and a water-soluble calcium compound at a specific charging ratio, and causing a hydrothermal reaction under pressure. Conventionally, various studies have been conducted on the reactions of silicon dioxide, alkali metal salts, and calcium compounds, but there is almost no knowledge that the reaction products become fibrous. The present inventors have been diligently researching the synthesis of calcium silicate compounds for many years, and found that by reacting silicon dioxide, potassium hydroxide, and a water-soluble calcium compound at a specific charging ratio under specific conditions, They discovered that fibrous calcium potassium silicate could be obtained and completed the present invention. In the present invention, silicon dioxide or a compound containing silicon dioxide, potassium hydroxide, and a water-soluble calcium compound are reacted when K 2 O in these raw materials is X moles, SiO 2 is Y moles, and CaO is Z moles. Therefore, if potassium salt is by-produced, the raw material charging coefficient T calculated by the following formula (A), and if no potassium compound is by-produced by the reaction, by the following formula (B), is 1.0 to 2.5, and X/ In this method, fibrous calcium potassium silicate is produced by charging the mixture so that Z is 1.5 to 6, and carrying out a hydrothermal reaction under pressure at a temperature of 150 to 250°C. T=9Y-32Z/9X-12Z...(A) T=9Y-32Z/9X-3Z...(B) Here, X, Y, and Z are of course positive numbers, and formulas (A) and (B) The denominator and numerator in are also positive numbers, respectively, as will be shown in the examples below. Through chemical analysis, it is estimated that the fibrous calcium potassium silicate obtained in the present invention has a general formula of approximately 3K 2 O・9CaO・32SiO 2・nH 2 O (where n is a number from 0 to 20). It is a new compound. In general, the general formula of each type of crystal can be determined by chemical analysis. However, for the silicates and the like that are the object of the present invention, it is difficult to obtain an accurate general formula for the following reasons, and it can only be estimated on the assumption that there are some fluctuations in the coefficients. The first is that impurities that are difficult to separate are often incorporated into the crystal below the solid solubility limit. The second problem is that in a crystal having ion exchange ability, each ion is contained in the crystal according to the ion exchange equilibrium, so the composition changes depending on the pH and liquid composition. For example, in the general formula estimated in the present invention, there are examples in which a part of K is ion-exchanged with Na or Ca, and a part of Ca is ion-exchanged with Na, K, or the like. The fact that the general formula of silicate is difficult to specify is explained in Japanese Patent Application Laid-Open No. 114397/1983, for example, 0.9±0.2M2/ o O:A.
2 O 3 :2.5±0.5SiO 2 .0 to 8H 2 O (where M is a metal cation and n is its valence) This is also understood from the other descriptions. The fibrous calcium potassium silicate obtained in the present invention has ion exchange ability due to K 2 O contained in the molecule.
Furthermore, although fibrous calcium potassium silicate generally has water of crystallization after production, the water of crystallization separates at 250 to 300°C, and has the property of condensing when it comes into contact with water. Utilizing these properties, the fibrous calcium potassium silicate is a substance that can be widely used as an ion exchanger or a desiccant. Further, when the crystallization water is dried at 100° C. for 8 hours, the crystallization water generally becomes about 12%. As mentioned above, this water is separated at 250 to 300°C, but since it has the property of condensing, the properties of calcium potassium silicate remain unchanged even if all or part of the water is removed. Therefore, it can be said that the crystallization water of calcium sodium silicate obtained by the present invention has the properties of fluorite water. The raw materials of the present invention are at least three components: silicon dioxide or a compound containing silicon dioxide, potassium hydroxide, and a water-soluble calcium compound. As the silicon dioxide, wet-processed silicon dioxide obtained by reacting an alkali silicate with a mineral acid, that is, hydrated silicic acid, is generally preferably used. Further, the compound containing silicon dioxide is not particularly limited as long as it is soluble in the reaction system, and any known compound can be used, and in general, natural substances such as clay and quartz, or compounds such as silicon dust can be suitably used. Furthermore, the water-soluble calcium compound is not particularly limited as long as it is water-soluble, and any known compound can be used. Typical examples that are commonly used are calcium hydroxide, calcium oxide,
These include calcium chloride, calcium nitrate, and calcium sulfate. That is, water-soluble calcium compounds are
For example, calcium sulfate, which has a relatively low solubility in water, can be used, but only the amount consumed to produce calcium potassium silicate during the reaction dissolves, so it can be used as a raw material for industrial purposes. . However, since water-insoluble calcium compounds such as calcium carbonate hardly dissolve in water, fibrous calcium silicate cannot be obtained industrially. It is necessary to use at least the above-mentioned three components as raw materials in the present invention, but when attempting to obtain fibrous calcium potassium silicate industrially, it is necessary to select the following specific raw material charging coefficients. . That is, K 2 O in the raw material is X mol, SiO 2 is Y mol, and
When CaO is Z moles, if potassium salt is by-produced by the reaction, use the formula (A) below, and if potassium salt is not by-produced by the reaction, calculate the raw material charging coefficient T by the formula (B) below. It is necessary to charge the raw materials so that the ratio is in the range of 1.0 to 2.5, preferably 1.2 to 1.9, and X/Z is in the range of 1.5 to 6. T=9Y-32Z/9X-12Z...(A) T=9Y-32Z/9X-3Z...(B) (However, X, Y, and Z are of course positive numbers, and (A),
(The denominator and numerator in formula (B) are also positive numbers, respectively, as shown in the examples below.) When potassium salt is produced as a by-product by the above reaction, and when the water-soluble calcium compound is calcium chloride, calcium sulfate, etc. In some cases, these anions combine with potassium to produce potassium salts such as potassium chloride, potassium nitrate, potassium sulfate, etc. as by-products. In addition, the case where potassium salt is not produced as a by-product in the above reaction corresponds to the case where calcium hydroxide, calcium oxide, etc. are used as the water-soluble calcium compound, and the case where potassium salt is not produced by reacting with potassium. It is. When the raw material charging coefficient T is smaller than the lower limit value, even if fibrous calcium potassium silicate is produced, the reaction requires a long time, for example, several days to a few days, so it cannot be selected industrially. Moreover, when the raw material preparation coefficient T is larger than the above upper limit value, fibrous calcium potassium silicate is produced, but
At the same time, a large amount of potassium silicate represented by crystalline K 2 O.4SiO 2.H 2 O may be produced as a by-product, and it may not be possible to separate it from the fibrous calcium potassium silicate. Further, it is preferable that the silicon dioxide component and the potassium component in the raw materials are present in excess of the amount necessary for producing fibrous calcium potassium silicate. Generally, it is necessary to select the above-mentioned excess amount so that the molar ratio of K 2 O/CaO in the raw material, ie, the above-mentioned X/Z, is in the range of 1.6 to 6, preferably 2 to 4. If X/Z is smaller than the above lower limit, the production rate of fibrous calcium potassium silicate may be slow, which may be industrially disadvantageous. On the other hand, if X/Z is larger than the above upper limit, the desired product, fibrous calcium potassium silicate, can be obtained, but the amount of unreacted potassium silicate recovered will be large, which will be disadvantageous in terms of equipment, so it is not suitable for industrial use. It cannot be said that it is advantageous. In the above, the raw material preparation coefficient T and K 2 O in the raw material /
Although suitable criteria for the CaO molar ratio have been explained, these values vary depending on the type of raw materials, reaction conditions, etc., and cannot be determined unconditionally. Therefore, it is preferable to determine a suitable value in advance depending on the type of raw materials, reaction conditions, etc. before carrying out the reaction. The water-soluble calcium compounds in the raw materials in the present invention are digested to produce nearly 100% fibrous calcium potassium silicate. This will be clear from the examples described below, but after filtering off the fibrous calcium potassium silicate produced by the reaction, it becomes clear that almost no calcium component is observed in the filtrate. Therefore, the calcium content is approximately 100
% The composition of the raw material charge can be determined by considering that the above-mentioned calcium potassium silicate is formed. More specifically, the determination of the raw material charging ratio can be explained by citing an example as follows. As mentioned above, it is clear that almost all of the water-soluble calcium compound is digested into fibrous calcium potassium silicate, so once the amount of calcium potassium silicate to be obtained is determined, the amount of water-soluble calcium compound required can be determined. The amount of is determined. That is, the required CaO mole in the raw material (the above Z
mole) is determined. Next, the K 2 O/CaO molar ratio, ie, the value of X/Z, is determined as appropriate. If K 2 O/CaO
If the molar ratio is set to 3, the necessary K 2 O
The moles are determined. Since K 2 O is derived only from the raw material potassium hydroxide, the amount of potassium hydroxide required is determined. Next, 2 moles of SiO 2 can be calculated according to the formula for calculating the amount T of raw material charged. From this result, the silicon dioxide or 2
The amount of the compound containing silicon oxide to be used may be determined. The preparation of raw materials in the present invention is not particularly limited except for the necessary requirements described above, and the order of addition of each component is also not particularly limited. Generally, each raw material may be added to an aqueous solution, or an aqueous solution or slurry solution may be prepared for each raw material, and these liquids may be mixed. Fibrous calcium potassium silicate can be obtained by subjecting the aqueous solution containing the above-mentioned at least three raw materials to a hydrothermal reaction under pressure. If the reaction temperature under hydrothermal conditions is too low, the reaction time may become extremely long; on the other hand, if the temperature is high, not only is there a loss of thermal energy, but the production of a pressure-resistant container becomes expensive, making it uneconomical. Generally 150-250
It is most preferable to select the temperature within the range of ℃. It is generally sufficient to carry out the reaction at a vapor pressure at the reaction temperature, and it is usually preferable to carry out the reaction in a sealed container, such as an autoclave. If the reaction is carried out under such conditions, fibrous calcium potassium silicate can usually be obtained in a reaction time of about 10 to 40 hours. The fibrous calcium potassium silicate obtained by the hydrothermal reaction under pressure can be separated by filtration. The fibrous calcium potassium silicate separated by filtration may be washed with water and dried as required to obtain a product. In addition, the filtrate obtained by separating the fibrous calcium potassium silicate by filtration contains unreacted silicon dioxide and potassium hydroxide, so it can be recycled as it is or after removing other by-products, part or all can be recycled as a raw material. I can do it. In general, when calcium hydroxide or calcium oxide is used as a water-soluble calcium compound, no by-products are usually generated and it can be recycled as is.However, as a water-soluble calcium compound, calcium chloride, calcium nitrate,
When calcium sulfate or the like is used, potassium salt is produced as a by-product as described above. If potassium salts are produced as a by-product, it is preferable to remove these potassium salts before circulating the filtrate as a raw material. EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 1.0 mol/potassium hydroxide solution 100 c.c. and 0.25
Mix 100 c.c. of slaked lime slurry and add hydrated silicate Toxil Gu (trade name) to this slurry.
17.65 g (SiO 2 content: 85%) was added and stirred well.
In this case, the raw material charging coefficient T calculated from the above formula (B) was 1.76. This slurry was placed in an autoclave, sealed, and reacted at a temperature of 200° C. for 20 hours. The reaction product was filtered, washed three times with 100 c.c. of ion-exchanged water, and then dried at 100°C for 8 hours. The yield of this dried product was 8.6 g. According to chemical analysis, this product is approximately
The composition was estimated to be 3K 2 O・9CaO・32SiO 2・20H 2 O. Observation using an electron microscope reveals that the length is approx.
It was confirmed that it was a fibrous material with a diameter of 220μ and an aspect ratio of 120. Incidentally, the filtrate obtained by filtering the reaction product contained almost no calcium. Example 2 The same procedure as in Example 1 was carried out except that the raw material ratio and reaction conditions in Example 1 were changed as shown in Table 1. The results are shown in Table 1.
The total charging volume was 200 c.c. as in Example 1.
【表】
No.7は、少量のK2O・4SiO2・H2Oが混入して
いることが確認されたが、主成分は珪酸カルシウ
ムカリウムであることがＸ線回析、化学分析によ
り確認された。No.7以外は、殆んど不純物のな
い珪酸カルシウムカリウムであることが確認でき
た。
実施例 ３
水酸化カリウム溶液、前記の含水珪酸及び塩化
カルシウム溶液を全体の仕込容積を200c.c.となる
ように第２表に示すように混合し、強く撹拌した
後オートクレーブに入れ密閉し、200℃で20時間
反応させた、尚、仕込み条件及び結果は第２表に
示す通りであつた。いずれの結果もほゞ100％の
珪酸カルシウムカリウム繊維であることが確認さ
れた。[Table] Although it was confirmed that No. 7 contained a small amount of K 2 O・4SiO 2・H 2 O, X-ray diffraction and chemical analysis showed that the main component was calcium potassium silicate. confirmed. It was confirmed that all samples other than No. 7 were calcium potassium silicate with almost no impurities. Example 3 Potassium hydroxide solution, the above-mentioned hydrated silicic acid, and calcium chloride solution were mixed as shown in Table 2 so that the total volume was 200 c.c., and after stirring strongly, the mixture was placed in an autoclave and sealed. The reaction was carried out at 200° C. for 20 hours. The charging conditions and results were as shown in Table 2. In all cases, it was confirmed that the fibers were almost 100% calcium potassium silicate fibers.
【表】
実施例 ４
実施例３のNo.2の原料を変えた以外は、同様
の仕込み条件、同様の処理をして第３表の様な結
果を得た。いずれも収率よく珪酸カルシウムカリ
ウム繊維が合成できたことを確認した。[Table] Example 4 The same preparation conditions and the same treatment were carried out except that the No. 2 raw material of Example 3 was changed, and the results shown in Table 3 were obtained. It was confirmed that calcium-potassium silicate fibers could be synthesized with good yield in both cases.
【表】
尚、含水珪酸は前記のもの、白土は別府白土で
SiO2含有量90％、325メツシユ全通のもの、石英
はSiO2含有量99.1％で325メツシユ全通のものを
使用した。
実施例 ５
1.4ｇの酸化カルシウムを100メツシユ全通に粉
砕して100c.c.の水に投入する。このスラリーを1.0
モル／の水酸化カリウム溶液100c.c.とを混合す
る。このスラリーに更に含水珪酸トクシールGu
（商品名、SiO2含有量85％）17.65ｇを加え良く撹
拌した。この場合の前記(B)式より算出された原料
仕込係数Ｔは1.76であつた。このスラリーを実施
例１と同様に処理した。この場合の生成物は、化
学分析の結果珪酸カルシウムカリウムであり、顕
微鏡によると長さ200μの繊維であることが確認
された。収量は8.6ｇであつた。[Table] The hydrated silicic acid is the one mentioned above, and the white clay is Beppu white clay.
The quartz used had a SiO 2 content of 90% and a 325-mesh structure, and the quartz had a SiO 2 content of 99.1% and a 325-mesh structure. Example 5 1.4 g of calcium oxide was ground into 100 meshes and poured into 100 c.c. of water. This slurry is 1.0
Mix with 100 c.c. of mol/potassium hydroxide solution. This slurry is further added with hydrated silicate Toxil Gu.
(Product name, SiO 2 content 85%) 17.65 g was added and stirred well. In this case, the raw material charging coefficient T calculated from the above formula (B) was 1.76. This slurry was treated in the same manner as in Example 1. The product in this case was found to be calcium potassium silicate as a result of chemical analysis, and was confirmed to be fibers with a length of 200 μm using a microscope. The yield was 8.6g.
Claims (1)
酸化カリウム及び水溶性カルシウム化合物を、こ
れらの原料中のK2OがＸモル、SiO2がＹモル及び
CaOがＺモルとしたとき反応によつてカリウム塩
が副生する場合は下記(A)式で、また反応によつて
カリウム塩が副生しない場合は下記(B)式で計算し
た原料仕込み係数Ｔが1.0〜2.5となり、且つＸ／
Ｚが1.5〜６となるように仕込み、加圧下、150〜
250℃の温度で反応させることを特徴とする繊維
状珪酸カルシウムカリウムの製造方法 Ｔ＝９Ｙ−３２Ｚ／９Ｘ−１２Ｚ ……(A) Ｔ＝９Ｙ−３２Ｚ／９Ｘ−３Ｚ ……(B) 但し(A)，(B)式においてＸ，Ｙ，Ｚ，分母，分子
は夫々正数である。 ２ ２酸化珪素が含水珪酸である特許請求の範囲
１記載の方法 ３ ２酸化珪素を含む化合物が白土又は石英であ
る特許請求の範囲１記載の方法。 ４ 水溶性カルシウム化合物が水酸化カルシウ
ム、酸化カルシウム、硝酸カルシウム及び硫酸カ
ルシウムよりなる群から選ばれた１種である特許
請求の範囲１記載の方法。 ５ 原料仕込み係数Ｔが1.2〜1.9である特許請求
の範囲１記載の方法。 ６ 反応温度が150〜250℃である特許請求の範囲
１記載の方法。[Scope of Claims] 1. Silicon dioxide or a compound containing silicon dioxide, potassium hydroxide, and a water-soluble calcium compound, in which K 2 O in these raw materials is X moles, SiO 2 is Y moles, and SiO 2 is Y moles,
When CaO is Z moles, if potassium salt is by-produced by the reaction, use the formula (A) below, and if potassium salt is not by-produced by the reaction, calculate the raw material charging coefficient by formula (B) below. T is 1.0 to 2.5, and X/
Prepare so that Z is 1.5~6, under pressure, 150~
A method for producing fibrous calcium potassium silicate characterized by reaction at a temperature of 250°C T=9Y-32Z/9X-12Z...(A) T=9Y-32Z/9X-3Z...(B) However ( In formulas A) and (B), X, Y, Z, denominator, and numerator are each positive numbers. 2. The method according to claim 1, wherein the silicon dioxide is hydrated silicic acid. 3. The method according to claim 1, wherein the compound containing silicon dioxide is clay or quartz. 4. The method according to claim 1, wherein the water-soluble calcium compound is one selected from the group consisting of calcium hydroxide, calcium oxide, calcium nitrate, and calcium sulfate. 5. The method according to claim 1, wherein the raw material charging coefficient T is 1.2 to 1.9. 6. The method according to claim 1, wherein the reaction temperature is 150 to 250°C.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8356578A JPS5510465A (en) | 1978-07-11 | 1978-07-11 | Production of fibrous calcium potassium silicate |
| US06/054,810 US4277457A (en) | 1978-07-07 | 1979-07-05 | Alkali calcium silicates and process for preparation thereof |
| GB7923656A GB2031393B (en) | 1978-07-07 | 1979-07-06 | Alkali calcium silicates and process for preparation thereof |
| DE19792927444 DE2927444A1 (en) | 1978-07-07 | 1979-07-06 | ALKALICALCIUMSILIKATE AND METHOD FOR THE PRODUCTION THEREOF |
| FR7917768A FR2434117A1 (en) | 1978-07-07 | 1979-07-09 | NOVEL CALCOALCALIN SILICATE AND PROCESS FOR ITS PREPARATION |
| US06/125,186 US4294810A (en) | 1978-07-07 | 1980-02-27 | Alkali calcium silicates and process for preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8356578A JPS5510465A (en) | 1978-07-11 | 1978-07-11 | Production of fibrous calcium potassium silicate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5510465A JPS5510465A (en) | 1980-01-24 |
| JPS6126495B2 true JPS6126495B2 (en) | 1986-06-20 |
Family
ID=13806031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8356578A Granted JPS5510465A (en) | 1978-07-07 | 1978-07-11 | Production of fibrous calcium potassium silicate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5510465A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60140952U (en) * | 1984-02-29 | 1985-09-18 | 大日本印刷株式会社 | film storage container |
-
1978
- 1978-07-11 JP JP8356578A patent/JPS5510465A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5510465A (en) | 1980-01-24 |
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