JPH0261406B2 - - Google Patents
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- Publication number
- JPH0261406B2 JPH0261406B2 JP60011718A JP1171885A JPH0261406B2 JP H0261406 B2 JPH0261406 B2 JP H0261406B2 JP 60011718 A JP60011718 A JP 60011718A JP 1171885 A JP1171885 A JP 1171885A JP H0261406 B2 JPH0261406 B2 JP H0261406B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- particle size
- slurry
- average particle
- size distribution
- 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.)
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Links
- 239000002245 particle Substances 0.000 claims description 91
- 239000000843 powder Substances 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 34
- 239000002002 slurry Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 25
- 239000010419 fine particle Substances 0.000 claims description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- 238000000635 electron micrograph Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000499 gel Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000012530 fluid Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910002012 Aerosil® Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000017 hydrogel Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
- C01B13/363—Mixtures of oxides or hydroxides by precipitation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Description
本発明は無機酸化物及び／又は含水酸化物から
なる粒度分布のシヤープな多孔質真球状微粒子粉
末の製造法に関するものであつて、さらに詳しく
は平均粒子径が１〜20μで、細孔容積が0.1〜0.8
c.c.／ｇである多孔質真球状微粒子粉末の製造法に
係る。
従来知られている微粒子の製造法は、湿式法と
乾式法に大別される。湿式法としては、マイクロ
カプセル法、乳化法、オイル法などが知られてい
る。これらの方法はすべて液体中にて造粒を行う
為、固液分離、洗浄、乾燥等の工程に於て、粒子
の凝集が起り易く、かつ製品粒子の形状がいびつ
になるとか、粒度分布が広くなるなどの欠点があ
る。又これらの方法は固形分濃度の低い所で調整
しないと、微粒子が得られない為、工業的な大量
生産を目論む場合には、装置が大きくなり、コス
トが高くなるなどの欠点もある。
一方、乾式法としては、一度酸化物を固形化
し、これを所望の大きさに粉砕し、その酸化物の
融点以上の高温下に粉砕品を投下する事により球
状の微粒子を得る方法がある。しかし、この方法
では無孔質の粒子しか出来ず、又千数百℃という
高温下で行う為、粒子の付着が発生し易く、又非
常に高価である。
他の乾式法としては、食品、洗剤、触媒等の製
造に用いられている噴霧乾燥法がある。この方法
は通常110℃〜400℃の加熱空気中に原料スラリー
を噴霧し、乾燥粉末を得る方法であるが、乾燥空
気が高温であり、乾燥速度が速い為に、製品粒子
が非球形になるとか、粒子表面の一部が陥没した
りして真球状のものを得るのが困難である。又通
常の噴霧乾燥法は、平均粒子径が40μ〜150μ程度
の粉粒体の製造に適し、且つ粒度分布も20〜
180μと巾が広いのが通例である。
本発明者らは、こうした事情にかんがみ、上記
の欠点を解決すべく、鋭意研究した結果、温度、
湿度、気体の流速、気／液比並びに液中の粒度を
調整する事により、平均粒径が１〜20μで、粒度
分布が0.5〜30μとシヤープな無機酸化物及び／又
は含水酸化物からなる多孔質真球状微粒子粉末が
製造できることを見い出した。
すなわち、本発明によれば、Si，Al，Ti，Zr，
Fe，Sn，Zn，Sb及びMgの酸化物及び／又は含
水酸化物をコロイド分散質とするコロイド液10〜
95部と、無機酸化物のゲル５〜90部をよく混合し
たスラリーが気流中に噴霧される。
無機酸化物及び／又は含水酸化物のコロイド液
には、例えば水硝子等のアルカリ珪酸塩から脱ア
ルカリする方法やエチルシリケートを加水分解す
る方法等で得られるシリカコロイド；鉱酸塩及
び／又は有機酸塩を加水分解及び／又は中和する
方法等で得られるZr，Fe，Ti，Sb，Sn，Zn，
Mgなどのコロイド；H2O2処理など特殊な処理を
行うことにより得られるSnやSbのコロイド等が
使用可能である。但し、コロイドの製造に関して
は上記した製法に限定されるものではなく、いか
なる方法で製造されたものでもよい。
しかし、コロイド液に分散するコロイド粒子
（一次粒子）の平均粒子径は2500Å以下である事
が必要であり、好ましくは800Å以下である。平
均粒子径が2500Å以上であると、乾燥時の粒子間
強度が弱く、乾燥中に破損するため粒度分布が広
くなるばかりでなく、非球状物の混入が起るから
である。又、理由はさだかではないが、粒径の大
きいゾルを使用した場合には、噴霧機が閉塞しや
すく、粒度分布が大きくなり工業的に連続して安
定に真球状微粒子を得ることが困難である。
上記のコロイド液に混合される無機酸化物のゲ
ルは、ヒドロゲル又はキセロゲルのどちらであつ
ても差支えない。例えば、気相酸化法で得られる
シリカのエアロジルとか、水硝子を中和、洗浄し
て得られるホワイトカーボン等が使用可能であ
る。しかし、ゲルの平均粒子径は1μ以下である
ことが必要で、好ましくは、0.5μ以下であること
を可とする。
コロイド液とゲルとの混合状態は出来るだけ均
一であることが好ましい。又その時の粘度は
500cp以下である事が必要であり、好ましくは
50cp以下とすべきである。
通常の噴霧乾燥に使用される噴霧法を、平均粒
子径及び／又は粒度分布の狭い順に列挙すると回
転デイスク法＜加圧ノズル法＜２流体ノズル法の
順である。回転デイスク法では、その極限の回転
数６〜７万rpmを採用しても、得られる粉粒体の
平均粒径は30μ前後であり、平均粒径数μの粉粒
体を歩留りよく作ることはできない。
２流体ノズル法は高粘度なスラリーを噴霧乾燥
して平均粒径70〜120μの粉末を作るのに適して
いる。
本発明に於て噴霧乾燥に用いられる噴霧法は、
例えば空気、チツ素等のマツハ１以上の高速気体
でスラリーを微細な液滴とした後、これをマツハ
１以上の対向流として、液滴同志を衝突させるこ
とにより超音波を発生させ、これにより液滴をよ
り小さくする方法である。この時の液滴径は10μ
以下であることが好ましい（液滴径の測定は高速
度カメラで写した写真を拡大して測定することが
できる）。すなわち、液滴径はノズルの気／液比
及び／又は気体の流速を調節することにより、コ
ントロールすることができ、同一径の液滴である
場合は、スラリーの固形分濃度が高いと粉体の粒
径が大きくなる。又同一濃度の場合は液滴径を小
さくすれば、得られる粉体の粒径は小さくなる。
又、液滴径、固形分濃度が一定であれば、乾燥速
度を遅くすると、密に充填され、粒径は小さくな
る。従つて目的とする粒径の粉体の得るには、ノ
ズルの気／液比及び／又は気体の流速並びに原料
液の固形分濃度及び／又は乾燥速度を調節する必
要がある。
次に細孔容積に関して説明すると、ゾル（コロ
イド液）は一次粒子が単一に存在している為、乾
燥時に粒子の充填がスムーズに行なわれ最密充填
に近くなる。又ゲルは一次粒子が数ケ〜数百ケ凝
集した網目構造をとつており、乾燥時にこの網目
構造を維持したまま充填される関係で疎の充填構
造となり、細孔容積が大きくなる。しかし、ヒド
ロゲルのみで乾燥すると、球の表面の一部が陥没
するなどのために真球状は得られない。又キセロ
ゲルのみで乾燥すると、粒子の表面活性が低い
為、乾燥時の粒子間強度が弱く、乾燥中に破損す
るとか、分級時に破損し、球状のものが得られな
い。そこでこれらの欠点をなくすために、本発明
ではゾルとゲルを混合して使用する。ゲルにゾル
を混合して用いれば、粒子間強度の弱いキセロゲ
ルに対しては、ゾルが粒子間を繋ぐバインダーと
なり、ヒドロゲルに対しては、ゲルの間にゾルが
入り、乾燥時の球表面の陥没を防ぐので球状の粉
末を得ることができる。この時の混合比は、酸化
物重量比でゾル／ゲル＝10／90〜95／５の範囲に
あけばよく、好ましくはゾル／ゲル＝30／70〜
80／20の範囲にある。またゾルとゲルを混合した
ものは、ゲルが網目構造している為骨材の役目と
してはたらき乾燥収縮が小さくなるため、ゾルの
み乾燥した時より収縮速度と乾燥速度が釣り合う
ものと考えられる。それ故に乾燥温度が150℃以
下であれば真球状微粒子を得ることが可能である
が、処理スピードや乾燥程度から40℃〜120℃が
好ましい。
乾燥雰囲気の湿度は温度によつて大幅に変わ
る。湿度を変えるために温度を変えると、乾燥速
度が変化し、粉末の形状に悪影響を及ぼす。150
℃以上の温度を採用すると収縮速度と乾燥速度の
釣り合いがくずれ、非球状物や粉末の割れが発生
する。湿度は150℃〜10℃の温度範囲であれば
13vol％〜3vol％の範囲を可とするが、処理液量
及び乾燥程度より５〜9vol％の範囲が好ましい。
先に述べたように粉体の粒径をコントロールす
るには、噴霧ノズルの気液比と気体の流速をコン
トロールする必要があり、この意味で本発明での
気／液比は10560〜500の範囲に、好ましくは5200
〜880の範囲にある。気体の流速に関しては、マ
ツハ１以上であれば良く、好ましくはマツナ1.1
〜1.7である。
本発明の方法に於て、スラリーの固形分濃度、
噴霧ノズルの気／液比及び気体の流速、乾燥温度
と湿度を特に調節した場合には、平均粒子径が３
〜10μで、0.7〜25μの粒度分布を有する粉体を製
造することが可能である。
本発明の方法で得られた微粒子粉末は、透明完
全球状で多孔質であり、耐熱性、耐酸耐アルカリ
性、耐溶剤性に優れ、粒度分布が非常に狭く、硬
度が高いので、色々な用途に使用することができ
る。例えば高級滑性フイラーとしてシリカの真球
状微粉末をフアンデーシヨンに使用すれば、非常
に軽くソフトで、のびの良いフアンデーシヨンが
得られる。また、チタンの真球状微粉末を現在使
用されている顔料の代りに使用するか、これと併
用すれば、現在使用されている顔料に較べ非常に
伸展性が良なり隠蔽力も落ちず、爽やかなフアン
デーシヨンが得られる。
このほか、本発明の微粉子粉末の用途として
は、インク用体質顔料、トナー、剥離性改良剤、
潤滑材、自動車用ワツクス等の研磨剤、樹脂・ゴ
ム耐摩耗性改良用高硬度フイラー剤、流動性改良
剤、艶消フイラー、無収縮フイラー、パテ用充填
剤、吸着剤、クロマト用担体、香料包括ビーズ、
殺菌剤・殺虫剤・防黴剤包括ビーズ等が例示でき
る。
本発明で言う真球とは、粉末試料を単一粒子が
重ならないよう分散させて走査型電子顕微鏡
（SEM）にて2000倍に拡大した電子顕微鏡写真を
撮り、これを島津製のイメージアナライザーで画
像解析し、単一粒子１ケ１ケの投影面の面積と円
周を測定し、面積から真円と仮定して得られる相
当直径をHDとし、又円周から真円と仮定して得
られる相当直径をHdとし、これらの２つの比を
形状係数とした。
形状係数＝HD（面積からの相当直径）／Hd（円周からの
相当直径）
そしてこの形状係数の値が0.85〜1.00のものを
真球とした。かつサンプリングしたもののうち、
真球が90％以上認められるものを真球状微粒子と
名付けた。尚、表面上に小さい粒子の付着、陥没
などが認められる粒子は真球としない。
実施例 １
内容積150のタンクに平均粒子径130Åのシリ
カゾル（触媒化成製Cataloid SI−30）100Kg入
れ、これに平均粒子径0.1μのホワイトカーボン
（塩野義製薬カープレツクス）200Kgを入れて良く
撹拌する。ほぼ均一に混合出来たら、これを内容
積50のサンドミル（アシザワ製のパールミル
50STS）に滞留時間が30分になるような流量で
供給して、連続粉砕を行なつた。こうして得られ
たスラリーの粘度は26cpであつた。
このスラリーを対向式２流体ノズルに供給し、
処理液量60／Hr、空／液比＝2100、空気流速
マツハ1.1、乾燥雰囲気温度120℃、湿度7.2vol％
の条件下に噴霧乾燥した。得られた乾燥粉末を
Kett式水分計で測定した時の水分は6.2wt％であ
つた。この粉末を600℃×3Hrs焼成後、堀場製の
粒度分布測定機Capa−500にて粒度分布を測定
し、さらに日本電子製LSM−T20走査形電子顕
微鏡（SEM）にて写真撮影し、前述したところ
に従つて形状係数を求めた。また粉末の細孔容積
をBET法で測定した。
第１図に粒度分布の測定結果を、第２図に粉末
の電子顕微鏡写真（倍率2000倍）を示す。
実施例 ２
ホワイトカーボンの代りに平均粒子径0.05μの
アエロジルー200（日本アエロジル）を使用した以
外は実施例１と全く同一の方法にて粘度28cpの
スラリーを得、さらにシリカの真球状微粉末を製
造し、実施例１と同様にこの粉末の粒度分布及び
細孔容積を測定し、さらに形状係数を求めた。
本実施例で得た粉末の電子顕微鏡写真を第３図
に示する。
実施例 ３
内容積150のタンクに水51.7と30％濃度の
シリカゾル（Cataloid SI−30）33.3Kgを入れ、
良く撹拌しながらこれにアエロジルー200を40Kg
徐々に添加し、ほぼ均一に混合したスラリーを対
向式２流体ノズルに供給し、実施例１と同様な方
法で粘度26cpのスラリーを得、さらにシリカの
真球状微粉末を製造した。この粉末の粒度分布と
細孔容積を実施例１と同様にして測定し、さらに
形状係数を求めた。
本実施例で得た粉末の電子顕微鏡写真を第４図
に示す。
実施例 ４
酸化物として14.2wt％のチタンを含有する硫酸
チタンを内容積500のタンクに300Kg入れ、撹拌
しながら液温が10℃になる様冷却した後、28％ア
ンモニア水205を添加し、含水チタン酸のスラ
リーを作つた。これを0.5％のアンモニア水で
過洗浄する。こうして得られた含水チタン酸スラ
リーに塩酸を加えてPH２以上とし、良く撹拌し
て、TiO2として濃度31.7wt％のチタンゾルを149
Kg調製した。このゾルの平均粒子径は500Åであ
つた。このチタンゾルに平均粒子径は0.3μの顔料
チタンAW−200（帝国化工製）を10Kg加えて良く
混合し、得られたスラリーを対向式２流体ノズル
に供給して実施例１と同様な方法で粘度30cpの
スラリーを得、さらに酸化チタンからなる真球状
微粉末を製造した。この粉末の粒度分布と細孔容
積を実施例１と同様に測定し、また形状係数を求
めた。
本実施例で得た粉末の電子顕微鏡写真を第５図
に示す。
実施例 ５
内容積300のタンクに水50を入れ、撹拌し
つつアルミン酸ソーダ70Kg（Al2O314wt％）と硫
酸アルミニウム90Kg（Al2O37wt％）をPHが7.5に
なる様調節しつつ同時添加した後、これを過洗
浄して平均粒子径0.02のアルミナのヒドロゲルを
得た。このヒドロゲルを内容積500のタンクに
入れ、良く撹拌しつつAl2O3として濃度10wt％の
平均粒子径1000Åアルミナゾル150Kg（触媒化成
製AS−２）を加えて良く混合し、得られたスラ
リーを対向式２流体ノズルに供給して実施例１と
同様な方法により粘度150cpのスラリーを得、さ
らに酸化アルミニウムからなる真球状微粉末を製
造した。この粉末の粒度分布と細孔容積を実施例
１と同様に測定し、さらに形状係数を求めた。
本実施例で得た粉末の電子顕微鏡写真を第６図
に示す。
比較例 １
酸化物として濃度30wt％のシルカゾル
（Cataloid SI−30 5cp）100Kgを対向式２流体ノ
ズルに供給し、実施例１と同一の方法でシリカの
微粉末を製造した。このシリカ粉末の分布粒度と
細孔容積を実施例１と同様に測定し、さらに形状
係数を求めた。
この比較例で得たシリカ粉末の電子顕微鏡写真
を第７図に示す。
比較例 ２
実施例５で調製した粘土120cpのアルミナヒド
ロゲルをそのまま対向式２流体ノズルに供給し、
実施例１と同様な方法にてアルミナの微粉末を製
造した。この粉末の粒度分布と細孔容積を実施例
１と同様に測定し、さらに形状係数を求めた。
この比較例で得たアルミナ粉末の電子顕微鏡写
真を第８図に示す。
比較例 ３
内容積150のタンクに水60を加え、撹拌し
つつアエロジル−200（日本アエロジル）40Kgを
徐々に加えて、良く混合し、得られた粘度15cp
のスラリーを対向式２流体ノズルに供給して実施
例１と同様な方法でシリカ微粉末を製造した。こ
のシリカ粉末の粒度分布と細孔容積を実施例１と
同様にして測定し、さらに形状係数を求めた。
この比較例で得た粉末の電子顕微鏡写真を第９
図に示す。
以上の実施例１〜５及び比較例１〜３で得た各
粉末の細孔容積、平均粒径及び形状係数は表−１
の通りである。
The present invention relates to a method for producing porous true spherical fine particle powder with a sharp particle size distribution made of an inorganic oxide and/or a hydrous oxide, and more specifically, the present invention relates to a method for producing porous true spherical fine particle powder with a sharp particle size distribution, and more specifically, an average particle diameter of 1 to 20 μm and a pore volume of 0.1~0.8
The present invention relates to a method for producing porous true spherical fine particle powder having a particle size of cc/g. Conventionally known methods for producing fine particles are broadly classified into wet methods and dry methods. As wet methods, microcapsule method, emulsification method, oil method, etc. are known. Since all of these methods perform granulation in liquid, particles tend to aggregate during processes such as solid-liquid separation, washing, and drying, and the shape of the product particles may become distorted or the particle size distribution may change. There are disadvantages such as being wider. In addition, these methods cannot obtain fine particles unless they are adjusted at a low solid content concentration, so when aiming at industrial mass production, there are drawbacks such as increased equipment size and higher costs. On the other hand, as a dry method, there is a method in which spherical fine particles are obtained by once solidifying an oxide, pulverizing it to a desired size, and dropping the pulverized product at a high temperature higher than the melting point of the oxide. However, this method produces only non-porous particles, and since it is carried out at a high temperature of several thousand degrees Celsius, particles tend to adhere to each other, and it is very expensive. Other dry methods include spray drying methods used in the production of foods, detergents, catalysts, and the like. In this method, raw material slurry is usually sprayed into heated air at 110°C to 400°C to obtain dry powder, but because the drying air is high temperature and the drying speed is fast, the product particles become non-spherical. In other words, a part of the particle surface is depressed, making it difficult to obtain a truly spherical particle. In addition, the normal spray drying method is suitable for producing powder particles with an average particle size of about 40μ to 150μ, and a particle size distribution of 20 to 150μ.
It is usually as wide as 180μ. In view of these circumstances, the inventors of the present invention have conducted intensive research to solve the above-mentioned drawbacks, and have found that the temperature
By adjusting the humidity, gas flow rate, air/liquid ratio, and particle size in the liquid, it is made of inorganic oxides and/or hydrous oxides with an average particle size of 1 to 20μ and a sharp particle size distribution of 0.5 to 30μ. It has been discovered that porous spherical fine particle powder can be produced. That is, according to the present invention, Si, Al, Ti, Zr,
Colloidal liquid containing oxides and/or hydrous oxides of Fe, Sn, Zn, Sb and Mg as colloidal dispersoids 10~
A well-mixed slurry of 95 parts of inorganic oxide gel and 5 to 90 parts of inorganic oxide gel is sprayed into the air stream. Colloidal liquids of inorganic oxides and/or hydrous oxides include silica colloids obtained by dealkalization from alkali silicates such as water vitreous or hydrolyzing ethyl silicate; mineral salts and/or organic oxides; Zr, Fe, Ti, Sb, Sn, Zn, obtained by hydrolyzing and/or neutralizing acid salts, etc.
Colloids such as Mg; colloids such as Sn and Sb obtained by special treatment such as H 2 O 2 treatment can be used. However, the production of the colloid is not limited to the above-mentioned production method, and any method may be used to produce the colloid. However, the average particle diameter of the colloidal particles (primary particles) dispersed in the colloidal liquid must be 2500 Å or less, preferably 800 Å or less. If the average particle diameter is 2,500 Å or more, the interparticle strength during drying will be weak and breakage will occur during drying, resulting in not only a wide particle size distribution but also non-spherical particles being mixed in. In addition, although the reasons are not trivial, when a sol with a large particle size is used, the atomizer tends to become clogged, and the particle size distribution becomes large, making it difficult to continuously and stably obtain true spherical fine particles industrially. be. The inorganic oxide gel mixed into the above colloidal liquid may be either a hydrogel or a xerogel. For example, silica Aerosil obtained by a gas phase oxidation method, white carbon obtained by neutralizing and washing water glass, etc. can be used. However, the average particle diameter of the gel needs to be 1μ or less, preferably 0.5μ or less. It is preferable that the colloidal liquid and gel be mixed as uniformly as possible. Also, the viscosity at that time is
Must be less than 500cp, preferably
It should be less than 50 cp. The spray methods used in conventional spray drying are listed in descending order of average particle diameter and/or particle size distribution in the following order: rotating disk method <pressure nozzle method <two-fluid nozzle method. In the rotating disk method, even if the maximum rotation speed is 60,000 to 70,000 rpm, the average particle size of the resulting powder is around 30μ, and it is possible to produce powder and granules with an average particle size of several μ with a good yield. I can't. The two-fluid nozzle method is suitable for spray drying a highly viscous slurry to produce powder with an average particle size of 70-120μ. The spray method used for spray drying in the present invention is as follows:
For example, after turning the slurry into fine droplets with a high-velocity gas of Matsuha 1 or higher such as air or nitrogen, this is made into a counterflow of Matsuha 1 or higher and the droplets collide with each other to generate ultrasonic waves. This is a method of making droplets smaller. The droplet diameter at this time is 10μ
It is preferable that the droplet diameter is below (the droplet diameter can be measured by enlarging a photograph taken with a high-speed camera). In other words, the droplet diameter can be controlled by adjusting the air/liquid ratio of the nozzle and/or the gas flow rate, and if the droplets have the same diameter, the slurry with a high solids concentration will be The particle size of the particles increases. Further, in the case of the same concentration, if the droplet size is made smaller, the particle size of the obtained powder becomes smaller.
Furthermore, if the droplet size and solid content concentration are constant, if the drying rate is slowed, the particles will be packed densely and the particle size will become smaller. Therefore, in order to obtain powder having the desired particle size, it is necessary to adjust the air/liquid ratio and/or gas flow rate of the nozzle, as well as the solid content concentration and/or drying rate of the raw material liquid. Next, regarding the pore volume, since a sol (colloidal liquid) has a single primary particle, the particles are smoothly filled during drying, resulting in close packing. In addition, gel has a network structure in which several to hundreds of primary particles aggregate, and when it dries, it is filled while maintaining this network structure, resulting in a loosely packed structure and a large pore volume. However, if only the hydrogel is dried, a true spherical shape cannot be obtained because part of the surface of the sphere is depressed. Furthermore, if only xerogel is dried, since the surface activity of the particles is low, the interparticle strength during drying is weak, and the particles break during drying or break during classification, making it impossible to obtain spherical particles. In order to eliminate these drawbacks, the present invention uses a mixture of sol and gel. If a gel is mixed with a sol, the sol will act as a binder to connect the particles for xerogels, which have weak interparticle strength, and for hydrogels, the sol will enter between the gels, and the spherical surface will change when dry. Since it prevents caving, it is possible to obtain spherical powder. The mixing ratio at this time may be in the range of sol/gel = 10/90 to 95/5 in terms of oxide weight ratio, preferably sol/gel = 30/70 to 95/5.
In the 80/20 range. In addition, in a mixture of sol and gel, the gel has a network structure and acts as an aggregate, reducing drying shrinkage, so it is thought that the shrinkage rate and drying rate are more balanced than when only the sol is dried. Therefore, if the drying temperature is 150°C or less, it is possible to obtain true spherical fine particles, but a drying temperature of 40°C to 120°C is preferable from the viewpoint of processing speed and degree of drying. The humidity of a dry atmosphere varies significantly depending on temperature. Changing the temperature to change the humidity changes the drying rate and negatively affects the shape of the powder. 150
If a temperature higher than ℃ is used, the balance between shrinkage rate and drying rate will be lost, resulting in non-spherical objects and cracks in the powder. If the humidity is in the temperature range of 150℃~10℃
Although a range of 13 vol% to 3 vol% is acceptable, a range of 5 to 9 vol% is preferable based on the amount of processing liquid and degree of drying. As mentioned earlier, in order to control the particle size of the powder, it is necessary to control the gas-liquid ratio of the spray nozzle and the gas flow rate, and in this sense, the gas/liquid ratio in the present invention is 10560 to range, preferably 5200
~880 range. Regarding the gas flow rate, it is sufficient that it is 1 or higher, preferably 1.1.
~1.7. In the method of the present invention, the solid content concentration of the slurry,
When the air/liquid ratio of the spray nozzle, the gas flow rate, the drying temperature and the humidity are specifically adjusted, the average particle size can be reduced to 3.
~10μ, it is possible to produce powders with a particle size distribution of 0.7-25μ. The fine particle powder obtained by the method of the present invention is transparent, completely spherical, porous, has excellent heat resistance, acid resistance, alkali resistance, and solvent resistance, has a very narrow particle size distribution, and has high hardness, so it can be used for various purposes. can be used. For example, if spherical fine powder of silica is used as a high-grade slippery filler in a foundation, a foundation that is extremely light, soft, and spreads easily can be obtained. In addition, if titanium fine spherical powder is used in place of or in combination with the pigments currently used, it will have much better spreadability than the pigments currently used, will not reduce its hiding power, and will have a refreshing effect. Foundation is obtained. In addition, the fine powder of the present invention can be used as extender pigments for inks, toners, release improvers,
Lubricants, abrasives for automobile wax, etc., high-hardness fillers for improving the wear resistance of resins and rubber, fluidity improvers, matte fillers, non-shrink fillers, fillers for putty, adsorbents, carriers for chromatography, fragrances inclusive beads,
Examples include beads containing fungicides, insecticides, and fungicides. In the present invention, a true sphere is defined by dispersing a powder sample so that no single particles overlap, taking an electron micrograph magnified 2000 times with a scanning electron microscope (SEM), and then using a Shimadzu image analyzer to take an electron micrograph. Analyze the image and measure the area and circumference of the projected plane of each single particle.The equivalent diameter obtained from the area assuming that it is a perfect circle is HD, and the equivalent diameter obtained from the circumference assuming that it is a perfect circle. The equivalent diameter was taken as Hd, and the ratio of these two was taken as the shape factor. Shape factor = HD (equivalent diameter from area)/Hd (equivalent diameter from circumference) And those with a shape factor value of 0.85 to 1.00 are considered true spheres. And among those sampled,
Particles with 90% or more true sphericity were named true spherical particles. Particles with small particles attached or depressions on the surface are not considered to be true spheres. Example 1 Put 100 kg of silica sol (Catalyst Kasei Co., Ltd. Cataloid SI-30) with an average particle size of 130 Å into a tank with an internal volume of 150 Å, add 200 kg of white carbon (Shionogi & Co., Ltd. Carplex) with an average particle size of 0.1 μm, and stir well. . Once the mixture is almost uniform, use a sand mill with an internal volume of 50 mm (Ashizawa Pearl Mill).
50STS) at a flow rate that gave a residence time of 30 minutes, and continuous pulverization was performed. The viscosity of the slurry thus obtained was 26 cp. This slurry is supplied to an opposed two-fluid nozzle,
Processing liquid volume 60/Hr, air/liquid ratio = 2100, air flow rate Matsuha 1.1, drying atmosphere temperature 120℃, humidity 7.2vol%
Spray-dried under the following conditions. The obtained dry powder
The moisture content was 6.2wt% when measured with a Kett moisture meter. After firing this powder at 600°C for 3 hours, the particle size distribution was measured using a particle size distribution analyzer Capa-500 manufactured by Horiba, and a photograph was taken using a scanning electron microscope (SEM) manufactured by JEOL LSM-T20. The shape factor was calculated accordingly. In addition, the pore volume of the powder was measured using the BET method. Figure 1 shows the measurement results of particle size distribution, and Figure 2 shows an electron micrograph of the powder (2000x magnification). Example 2 A slurry with a viscosity of 28 cp was obtained in exactly the same manner as in Example 1, except that Aerosil 200 (Nippon Aerosil) with an average particle size of 0.05μ was used instead of white carbon, and a true spherical fine powder of silica was also obtained. The particle size distribution and pore volume of this powder were measured in the same manner as in Example 1, and the shape factor was also determined. FIG. 3 shows an electron micrograph of the powder obtained in this example. Example 3 Put 51.7 kg of water and 33.3 kg of 30% concentration silica sol (Cataloid SI-30) into a tank with an internal volume of 150,
Add 40kg of Aerogirou 200 to this while stirring well.
The slurry that was gradually added and mixed almost uniformly was supplied to an opposed two-fluid nozzle to obtain a slurry with a viscosity of 26 cp in the same manner as in Example 1, and further, a true spherical fine powder of silica was produced. The particle size distribution and pore volume of this powder were measured in the same manner as in Example 1, and the shape factor was also determined. FIG. 4 shows an electron micrograph of the powder obtained in this example. Example 4 300 kg of titanium sulfate containing 14.2 wt% of titanium as an oxide was put into a tank with an internal volume of 500, and after cooling to a liquid temperature of 10°C while stirring, 28% ammonia water 205 was added. A slurry of hydrous titanic acid was made. This is washed with 0.5% ammonia water. Add hydrochloric acid to the thus obtained hydrous titanic acid slurry to make it PH2 or higher, stir well, and prepare a titanium sol with a concentration of 31.7 wt% as TiO 2 at 149
Kg prepared. The average particle diameter of this sol was 500 Å. To this titanium sol, 10kg of pigment titanium AW-200 (manufactured by Teikoku Kako) with an average particle size of 0.3μ was added and mixed well, and the resulting slurry was fed to a facing two-fluid nozzle and treated in the same manner as in Example 1. A slurry with a viscosity of 30 cp was obtained, and a spherical fine powder made of titanium oxide was further produced. The particle size distribution and pore volume of this powder were measured in the same manner as in Example 1, and the shape factor was also determined. FIG. 5 shows an electron micrograph of the powder obtained in this example. Example 5 50% of water was put into a tank with an internal volume of 300%, and while stirring, 70Kg of sodium aluminate (14wt% Al 2 O 3 ) and 90Kg of aluminum sulfate (7wt% Al 2 O 3 ) were adjusted to a pH of 7.5. After addition, this was overwashed to obtain an alumina hydrogel with an average particle size of 0.02. This hydrogel was placed in a tank with an internal volume of 500 ml, and while stirring well, 150 kg of alumina sol with an average particle diameter of 1000 Å with a concentration of 10 wt% as Al 2 O 3 (AS-2 manufactured by Catalyst Kasei Co., Ltd.) was added and mixed well, and the resulting slurry was A slurry having a viscosity of 150 cp was obtained by supplying the slurry to an opposed two-fluid nozzle in the same manner as in Example 1, and further, a true spherical fine powder made of aluminum oxide was produced. The particle size distribution and pore volume of this powder were measured in the same manner as in Example 1, and the shape factor was also determined. FIG. 6 shows an electron micrograph of the powder obtained in this example. Comparative Example 1 A fine silica powder was produced in the same manner as in Example 1 by supplying 100 kg of silca sol (Cataloid SI-30 5 cp) with a concentration of 30 wt% as an oxide to an opposed two-fluid nozzle. The particle size distribution and pore volume of this silica powder were measured in the same manner as in Example 1, and the shape factor was also determined. FIG. 7 shows an electron micrograph of the silica powder obtained in this comparative example. Comparative Example 2 The clay 120 cp alumina hydrogel prepared in Example 5 was supplied as it was to the opposed two-fluid nozzle,
Fine alumina powder was produced in the same manner as in Example 1. The particle size distribution and pore volume of this powder were measured in the same manner as in Example 1, and the shape factor was also determined. FIG. 8 shows an electron micrograph of the alumina powder obtained in this comparative example. Comparative Example 3 Add 60 kg of water to a tank with an internal volume of 150, gradually add 40 kg of Aerosil-200 (Japan Aerosil) while stirring, mix well, and obtain a viscosity of 15 cp.
A fine silica powder was produced in the same manner as in Example 1 by supplying the slurry to an opposed two-fluid nozzle. The particle size distribution and pore volume of this silica powder were measured in the same manner as in Example 1, and the shape factor was determined. The electron micrograph of the powder obtained in this comparative example is
As shown in the figure. The pore volume, average particle size, and shape factor of each powder obtained in Examples 1 to 5 and Comparative Examples 1 to 3 above are shown in Table-1.
It is as follows.
【表】
実施例 ６
平均粒子径が0.03μのシリカゾル（触媒化成製
Cataloid SI−30p）10Kgと、平均粒子径が0.3μの
酸化チタン顔料（帝国化工製、AW−200）２Kg
を良く混合する。これを内容積12のサンドミル
（アシザワ製パールミル12 STS）に滞留時間が
30分になるような流量で供給し、連続粉砕を行な
つた。こうして得られたスラリーの粘度は14cp
であつた。
このスラリーを対向式２流体ノズルに供給し、
処理液量10／hr、空／液比＝2300、空気流速マ
ツハ1.3、乾燥雰囲気温度120℃、湿度6.9vol％の
条件下に噴霧乾燥した。得られた乾燥粉末を
Kett水分計で測定した時の水分は5.9wt％であつ
た。この粉末を600℃で３時間焼成後、実施例１
と同様にして粉末の粒度分布と細孔容積を測定
し、形状係数を求めた。
本実施例で得た粉末の電子顕微鏡写真を第１０
図に示す。
実施例 ７
酸化チタン量を４Kgに増量した以外は実施例６
と全く同様にして粘度12cpのスラリーを得、さ
らに粉末を製造し、その粒度分布及び細孔容積を
測定すると共に形状係数を求めた。この粉末の電
子顕微鏡写真を第１１図に示す。
実施例 ８
酸化チタン量を１Kgに減量した以外は実施例６
同様にして粘度16cpのスラリーを得、さらに粉
末を製造し、その粒度分布及び細孔容積を測定し
て、さらに形状係数を求めた。この粉末の電子顕
微鏡写真を第１２図に示す。
実施例 ９
酸化チタンの代りに、平均粒子径0.02μの酸化
アルミニウム（日本エアロジル・Ｃ）を使用した
以外は実施例６を同様な方法で粘度14cpのスラ
リーを得、さらに粉末を得た。この粉末の粒度分
布及び細孔容積を測定し、さらに形状係数を求め
た。この粉末の電子顕微鏡写真を第１３図に示
す。
実施例 10
シリカゾルの代りに平均粒子径23mμのジルコ
ニアゾル（第一希元素製）を用いた以外は実施例
６と全く同様な方法で粉末を得た。この粉末の粒
度分布と細孔容積を測定し、形状係数を求めた。
この粉末の電子顕微鏡写真を第１４図に示す。
実施例 11
酸化チタンの代りに平均粒子径0.8mmの酸化ア
ルミニウムを用いた以外は実施例６と全く同様な
方法で粘度12cpのスラリーを得、さらに粉末を
得た。この粉末の粒度分布と細孔容積を測定し、
形状係数を求めた。この粉末の電子顕微鏡写真を
第１５図に示す。
実施例 12
実施例６で使用したシリカゾルに代えて平均粒
子径1800Åのシリカゾル（触媒化成製SI−180P）
を使用し、酸化チタンの代りに平均粒子径0.02μ
二酸化チタンのエアロジル（日本エアロジル製・
Ｐ−25）を使用した以外は実施例６と同様な方法
で粘度10cpのスラリーを得、さらに粉末を得た。
この粉末の粒度分布及び細孔容積を測定し、さら
に形状係数を求めた。この粉末の電子顕微鏡写真
を第１６図に示す。
比較例 ４
乾燥雰囲気温度を160℃に、湿度を2vol％に変
えた以外は、実施例６と全く同様にして粉末を得
た。この粉末の粒度分布及び細孔容積を測定し、
形状係数を求めた。この粉末の電子顕微鏡写真を
第１７図に示す。
比較例 ５
乾燥雰囲気温度を80℃に、湿度を15vol％に変
えた以外は実施例６と全く同様にして粉末を得
た。この粉末の粒度分布及び細孔容積を測定し、
形状係数を求めた。
比較例 ６
実施例６に用いたシリカゾルに代えて平均粒子
3000Åのシリカゾル（触媒化成製Cataloid SI−
300p）を使用した以外は実施例６と全く同様に
して粘度10cpのスラリーを得、さらに粉末を得
た。この粉末の粒度分布及び細孔容積を測定し、
形状係数を求めた。この粉末の電子顕微鏡写真を
第１８図に示す。
比較例 ７
酸化チタンに代りに平均粒子径2μの水酸化ア
ルミニウム（昭和電工・Ｈ−42）を使用した以外
は実施例６と全く同様な方法で粘度10cpのスラ
リーを得、さらに粉末を得た。この粉末の粒度分
布及び細孔容積を測定し、形状係数を求めた。こ
の粉末の電子顕微鏡写真を第１９図に示す。
以上の実施例６〜12及び比較例４〜７で得られ
た各粉末の形状係数、平均粒径、粒度分布及び細
孔容積をまとめて表−２に示す。[Table] Example 6 Silica sol with an average particle size of 0.03μ (Catalyst Kasei Co., Ltd.)
Cataloid SI-30p) 10kg and titanium oxide pigment with an average particle size of 0.3μ (Teikoku Kako, AW-200) 2kg
Mix well. The residence time is
Continuous pulverization was performed by supplying at a flow rate that lasted for 30 minutes. The viscosity of the slurry thus obtained was 14 cp
It was hot. This slurry is supplied to an opposed two-fluid nozzle,
Spray drying was carried out under the following conditions: processing liquid volume 10/hr, air/liquid ratio = 2300, air flow rate Matsuha 1.3, drying atmosphere temperature 120°C, humidity 6.9 vol%. The obtained dry powder
The moisture content was 5.9 wt% as measured with a Kett moisture meter. After baking this powder at 600°C for 3 hours, Example 1
In the same manner as above, the particle size distribution and pore volume of the powder were measured, and the shape factor was determined. The 10th electron micrograph of the powder obtained in this example is
As shown in the figure. Example 7 Example 6 except that the amount of titanium oxide was increased to 4 kg.
A slurry with a viscosity of 12 cp was obtained in exactly the same manner as above, and a powder was further produced, and its particle size distribution and pore volume were measured, and its shape factor was determined. An electron micrograph of this powder is shown in FIG. Example 8 Example 6 except that the amount of titanium oxide was reduced to 1 kg.
In the same manner, a slurry with a viscosity of 16 cp was obtained, and a powder was further produced, and its particle size distribution and pore volume were measured, and the shape factor was determined. An electron micrograph of this powder is shown in FIG. Example 9 A slurry with a viscosity of 14 cp was obtained in the same manner as in Example 6, except that aluminum oxide (Nippon Aerosil C) having an average particle size of 0.02 μm was used instead of titanium oxide, and a powder was also obtained. The particle size distribution and pore volume of this powder were measured, and the shape factor was also determined. An electron micrograph of this powder is shown in FIG. Example 10 Powder was obtained in exactly the same manner as in Example 6, except that zirconia sol (manufactured by Daiichi Kigenso Co., Ltd.) having an average particle diameter of 23 mμ was used instead of silica sol. The particle size distribution and pore volume of this powder were measured, and the shape factor was determined.
An electron micrograph of this powder is shown in FIG. Example 11 A slurry with a viscosity of 12 cp was obtained in the same manner as in Example 6, except that aluminum oxide with an average particle size of 0.8 mm was used instead of titanium oxide, and powder was also obtained. Measure the particle size distribution and pore volume of this powder,
The shape factor was determined. An electron micrograph of this powder is shown in FIG. Example 12 Instead of the silica sol used in Example 6, silica sol with an average particle size of 1800 Å (SI-180P manufactured by Catalyst Kasei) was used.
with an average particle size of 0.02μ instead of titanium oxide.
Titanium dioxide Aerosil (manufactured by Nippon Aerosil)
A slurry with a viscosity of 10 cp was obtained in the same manner as in Example 6, except that P-25) was used, and a powder was further obtained.
The particle size distribution and pore volume of this powder were measured, and the shape factor was also determined. An electron micrograph of this powder is shown in FIG. Comparative Example 4 Powder was obtained in exactly the same manner as in Example 6, except that the drying atmosphere temperature was changed to 160° C. and the humidity was changed to 2 vol%. Measure the particle size distribution and pore volume of this powder,
The shape factor was determined. An electron micrograph of this powder is shown in FIG. Comparative Example 5 A powder was obtained in exactly the same manner as in Example 6, except that the drying atmosphere temperature was changed to 80° C. and the humidity was changed to 15 vol%. Measure the particle size distribution and pore volume of this powder,
The shape factor was determined. Comparative Example 6 Average particles were used instead of the silica sol used in Example 6.
3000Å silica sol (Catalyst Kasei Cataloid SI−
A slurry with a viscosity of 10 cp was obtained in exactly the same manner as in Example 6, except that 300 p) was used, and a powder was further obtained. Measure the particle size distribution and pore volume of this powder,
The shape factor was determined. An electron micrograph of this powder is shown in FIG. Comparative Example 7 A slurry with a viscosity of 10 cp was obtained in the same manner as in Example 6, except that aluminum hydroxide (Showa Denko H-42) with an average particle size of 2 μm was used instead of titanium oxide, and a powder was also obtained. . The particle size distribution and pore volume of this powder were measured, and the shape factor was determined. An electron micrograph of this powder is shown in FIG. Table 2 summarizes the shape factor, average particle size, particle size distribution, and pore volume of each powder obtained in Examples 6 to 12 and Comparative Examples 4 to 7.
第１図は実施例１で得た粉末の粒度分布を示す
グラフである。第２〜６図はそれぞれ実施例１〜
５で得た粉末の電子顕微鏡写真であり、第７〜９
図はそれぞれ比較例１〜３で得た粉末の電子顕微
鏡写真である。また、第１０〜１６図はそれぞれ
実施例６〜12で得た粉末の電子顕微鏡写真であ
り、第１７〜１９図はそれぞれ比較例４，６及び
７で得た粉末の電子顕微鏡写真である。
FIG. 1 is a graph showing the particle size distribution of the powder obtained in Example 1. Figures 2 to 6 are examples 1 to 6, respectively.
This is an electron micrograph of the powder obtained in 5, and 7 to 9.
The figures are electron micrographs of powders obtained in Comparative Examples 1 to 3, respectively. Moreover, FIGS. 10 to 16 are electron micrographs of the powders obtained in Examples 6 to 12, respectively, and FIGS. 17 to 19 are electron micrographs of the powders obtained in Comparative Examples 4, 6, and 7, respectively.
Claims (1)
95部と無機酸化物のゲル５〜90部を混合したスラ
リーを気流中に噴霧して乾燥することを特徴とす
る平均粒度１〜20μの多孔質真球状微粒子粉末の
製造法。 ２ 前記のコロイド液における一次粒子の平均粒
径が2500Å以下であることを特徴とする特許請求
の範囲第１項記載の方法。 ３ 前記のコロイド液に混合される無機酸化物の
ゲルの大きさが1μ以下であることを特徴とする
特許請求の範囲第１項記載の方法。 ４ 乾燥雰囲気温度が150℃〜10℃、湿度13vol％
〜3vol％である事を特徴とする特許請求の範囲第
１項記載の方法。 ５ 前記のコロイド液中の分散質がSi，Ti，Al，
Fe，Zr，Sn，Zn，Sb及びMgの酸化物及び含水
酸化物の１種もしくは２種以上であることを特徴
とする特許請求の範囲第１項記載の方法。 ６ 多孔質真球状微粒子粉末の細孔容積が0.1〜
0.8c.c.／ｇであることを特徴とする特許請求の範
囲第１項記載の方法。[Claims] 1 Colloidal liquid of inorganic oxide or hydrous oxide 10~
1. A method for producing porous true spherical fine particles having an average particle size of 1 to 20 μm, which comprises spraying a slurry of 95 parts of inorganic oxide gel and 5 to 90 parts of inorganic oxide gel into an air stream and drying the slurry. 2. The method according to claim 1, wherein the average particle diameter of primary particles in the colloidal liquid is 2500 Å or less. 3. The method according to claim 1, wherein the size of the inorganic oxide gel mixed into the colloidal liquid is 1 μm or less. 4 Drying atmosphere temperature is 150℃~10℃, humidity 13vol%
3. The method according to claim 1, wherein the amount is 3 vol%. 5 The dispersoids in the colloidal liquid include Si, Ti, Al,
The method according to claim 1, characterized in that the method is one or more of oxides and hydrous oxides of Fe, Zr, Sn, Zn, Sb, and Mg. 6 Pore volume of porous true spherical fine particle powder is 0.1~
The method according to claim 1, characterized in that the amount is 0.8 cc/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60011718A JPS61174103A (en) | 1985-01-23 | 1985-01-23 | Production of porous spherical and pulverous powder consisting of metallic oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60011718A JPS61174103A (en) | 1985-01-23 | 1985-01-23 | Production of porous spherical and pulverous powder consisting of metallic oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61174103A JPS61174103A (en) | 1986-08-05 |
| JPH0261406B2 true JPH0261406B2 (en) | 1990-12-20 |
Family
ID=11785819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60011718A Granted JPS61174103A (en) | 1985-01-23 | 1985-01-23 | Production of porous spherical and pulverous powder consisting of metallic oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61174103A (en) |
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| JP2002160907A (en) * | 2000-11-22 | 2002-06-04 | Catalysts & Chem Ind Co Ltd | Spherical porous particles and method for producing the same |
| JP2003012460A (en) * | 2001-06-28 | 2003-01-15 | Catalysts & Chem Ind Co Ltd | Resin-coated spherical porous particles, method for producing the same, and cosmetics incorporating the particles |
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|---|---|---|---|---|
| JPS6279841A (en) * | 1985-10-02 | 1987-04-13 | Teikoku Kako Kk | Production of inorganic spherical body |
| US4837011A (en) * | 1987-09-08 | 1989-06-06 | Revlon, Inc. | Cosmetic powder employing spherical silica particles |
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| JPH0757689B2 (en) * | 1989-05-15 | 1995-06-21 | ニチアス株式会社 | Method for producing porous spherical alumina |
| WO1991002704A1 (en) * | 1989-08-18 | 1991-03-07 | Monsanto Company | Ferritin analogs |
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1985
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|---|---|---|---|---|
| JP2002160907A (en) * | 2000-11-22 | 2002-06-04 | Catalysts & Chem Ind Co Ltd | Spherical porous particles and method for producing the same |
| JP2003012460A (en) * | 2001-06-28 | 2003-01-15 | Catalysts & Chem Ind Co Ltd | Resin-coated spherical porous particles, method for producing the same, and cosmetics incorporating the particles |
| WO2004006873A1 (en) | 2002-07-11 | 2004-01-22 | Catalysts & Chmicals Industries Co.,Ltd. | Cosmetic |
| WO2011155536A1 (en) | 2010-06-09 | 2011-12-15 | 日揮触媒化成株式会社 | Support for protein immobilization, immobilized protein and method for producing same |
| WO2019131873A1 (en) * | 2017-12-27 | 2019-07-04 | 日揮触媒化成株式会社 | Porous silica particles and method for producing same |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPS61174103A (en) | 1986-08-05 |
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