JPH0123416B2 - - Google Patents
Info
- Publication number
- JPH0123416B2 JPH0123416B2 JP58093453A JP9345383A JPH0123416B2 JP H0123416 B2 JPH0123416 B2 JP H0123416B2 JP 58093453 A JP58093453 A JP 58093453A JP 9345383 A JP9345383 A JP 9345383A JP H0123416 B2 JPH0123416 B2 JP H0123416B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- acid
- particle size
- alumina sol
- colloidal
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- -1 alkali metal aluminate Chemical class 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000004965 peroxy acids Chemical group 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 31
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 24
- 239000000243 solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 10
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BWGOLNLROKJSGE-UHFFFAOYSA-N 3-hydroxypropylphosphonic acid Chemical compound OCCCP(O)(O)=O BWGOLNLROKJSGE-UHFFFAOYSA-N 0.000 description 1
- QXKAIJAYHKCRRA-JJYYJPOSSA-N D-arabinonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(O)=O QXKAIJAYHKCRRA-JJYYJPOSSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【発明の詳細な説明】
本発明はアルミナゾルの新規な製造法、更に詳
細にはアルミン酸アルカリ金属塩の水溶液と分子
中に少なくとも１個以上の水酸基を有する有機ヒ
ドロキシル酸の水溶液とを中和反応せしめて、粒
子や微細で、広いPH範囲において凝集を惹起する
ことなく長期間安定に保持できるアルミナゾルを
製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel method for producing alumina sol, more specifically, a neutralization reaction between an aqueous solution of an alkali metal salt of aluminate and an aqueous solution of an organic hydroxyl acid having at least one hydroxyl group in the molecule. At least, it relates to a method for producing an alumina sol that is particulate or fine and can be stably maintained for a long period of time without causing agglomeration in a wide pH range.
アルミナゾルは、電気、電子工業及び陶磁器、
鋳物工業における耐熱性バインダー、化粧品、医
薬品における軟膏類の配合ベース、エアゾール製
品、繊維工業における風合改良、毛玉防止、ペイ
ント、顔料、印刷インクの乳化剤、安定剤、接着
性向上剤、樹脂、紙類の表面コーテイング剤、サ
イズ剤、石油工業における触媒担体等として有用
なものである。 Alumina sol is used in electrical, electronic industry and ceramics,
Heat-resistant binders in the foundry industry, formulation bases for ointments in cosmetics and pharmaceuticals, aerosol products, texture improvement in the textile industry, anti-pilling, emulsifiers, stabilizers, adhesion improvers for paints, pigments, and printing inks, resins, It is useful as a surface coating agent for paper, a sizing agent, a catalyst carrier in the petroleum industry, etc.
従来、アルミナゾルを製造する方法としては次
のものが知られている。 Conventionally, the following methods are known as methods for producing alumina sol.
アルミン酸水溶液中に炭酸ガスを吹き込み、
生成したアルミナ水和物スラリーを酸根／Al
（モル比）が0.05〜0.2の一価無機強酸中に分散
させる方法（英国特許第1440194号）。 Blow carbon dioxide gas into an aluminic acid aqueous solution,
The generated alumina hydrate slurry is
(British Patent No. 1440194).
塩化アルミニウム、硝酸アルミニウムのよう
な酸性で水溶性のアルミニウム正塩と炭酸ナト
リウム、水酸化ナトリウム等のアルカリ物質と
を中和反応せしめて得られるアルミナゲルを酸
根／Al（モル比）が0.001〜0.12の一価無機酸又
は有機酸の存在下水熱処理する方法（特開昭５
−112299号、同54−116398号、同55−23034号、
同55−27824号）。 Alumina gel obtained by neutralizing acidic, water-soluble aluminum normal salts such as aluminum chloride and aluminum nitrate with alkaline substances such as sodium carbonate and sodium hydroxide, and having an acid radical/Al (molar ratio) of 0.001 to 0.12. A method of hydrothermal treatment in the presence of a monovalent inorganic acid or an organic acid (JP-A-5
−112299, No. 54-116398, No. 55-23034,
No. 55-27824).
アルミン酸ナトリウム水溶液と酸性の水溶性
アルミニウム塩溶液とをPH９〜10になるように
中和反応させ、生成したアルミナゲルに一価無
機酸又は有機酸を酸根／Al（モル比）が0.15以
上になるように添加して水熱処理する方法（特
公昭40−8409号）。 A sodium aluminate aqueous solution and an acidic water-soluble aluminum salt solution are neutralized to a pH of 9 to 10, and a monovalent inorganic acid or an organic acid is added to the resulting alumina gel so that the acid group/Al (molar ratio) is 0.15 or more. (Special Publication No. 1984-8409).
塩酸、酢酸の希薄水溶液中に金属アルミニウ
ム粉末を加えて加熱下反応させ、粗大粒子を
別後、液を濃縮してアルミナゾルを得る方法
（特許第439196号、特公昭45−3658号）。 A method of obtaining alumina sol by adding metallic aluminum powder to a dilute aqueous solution of hydrochloric acid and acetic acid, reacting under heating, separating coarse particles, and concentrating the liquid (Patent No. 439196, Japanese Patent Publication No. 45-3658).
アルミニウムは両性金属であり、酸及びアルカ
リ溶液に可溶であるため、アルカリ性を示す水溶
性アルミニウム塩に酸性物質を、また酸性を示す
水溶性アルミニウム塩にアルカリ性物質を作用せ
しめて中和反応を行えばアルミナ水和物（水酸化
アルミニウム）が生成される。しかしながら上記
〜の中和反応により生成されるアルミナ水和
物は一次粒子は微細でも二次粒子は粗大であるた
め、酸を添加して水熱下解膠処理を施してコロイ
ド状のアルミナゾルを得ている。またの方法で
得られるアルミナゾルは低PHではゲル化を生起す
ることなく流動安定性を保持できるが、中性〜ア
ルカリ性領域では凝集してしまう。 Aluminum is an amphoteric metal and is soluble in acid and alkaline solutions. Therefore, a neutralization reaction is performed by allowing an acidic substance to act on an alkaline water-soluble aluminum salt and an alkaline substance acting on an acidic water-soluble aluminum salt. For example, alumina hydrate (aluminum hydroxide) is produced. However, the alumina hydrate produced by the above neutralization reaction has fine primary particles but coarse secondary particles, so a colloidal alumina sol is obtained by adding an acid and performing hydrothermal peptization treatment. ing. The alumina sol obtained by the above method can maintain fluidity stability without gelation at low pH, but it aggregates in the neutral to alkaline range.
しかしながら、従来公知の方法では、経時安定
性の優れたアルミナゾル、また再分散性の優れた
アルミナ粉末を与えるアルミナゾルを得ることが
できなかつた。 However, with conventionally known methods, it has not been possible to obtain an alumina sol with excellent stability over time or an alumina sol that provides alumina powder with excellent redispersibility.
そこで、本発明者は、コロイド粒子径が微細
で、かつ経時的に凝集、ゲル化を惹起することが
できないアルミナゾルを提供すべく鋭意研究を行
つた結果、アルミン酸アルカリ金属塩の水溶液
と、次の一般式（）又は（）
Ｒ（OH）ｍ（COOH）ｎ （）
Ｒ（OH）ｍ（PO3H2）ｎ （）
（式中、ｍ及びｎは１以上の数を示し、Ｒは炭素
数１〜10の飽和又は不飽和の脂肪族基を示し、酸
基１個当たりの分子量が200以下であるものとす
る）
で表わされる有機ヒドロキシル酸の水溶液とを中
和反応せしめると、従来法のような水熱下解膠処
理を行うことなく、透明性に優れ、コロイド粒子
径が超微細で、しかもPH４〜11の広い範囲で凝集
を生起することなく長期間安定なアルミナゾルを
得ることができることを見出し、本発明を完成し
た。 Therefore, the present inventor conducted intensive research to provide an alumina sol that has a fine colloidal particle size and does not cause aggregation or gelation over time. General formula () or () R(OH)m(COOH)n () R(OH)m(PO 3 H 2 )n () (In the formula, m and n represent a number of 1 or more, and R is A saturated or unsaturated aliphatic group having 1 to 10 carbon atoms and a molecular weight of 200 or less per acid group) is subjected to a neutralization reaction with an aqueous solution of an organic hydroxyl acid represented by To obtain an alumina sol that has excellent transparency, ultra-fine colloid particle size, and is stable for a long period of time without causing aggregation in a wide pH range of 4 to 11 without performing hydrothermal peptization treatment as in the method. They discovered that it is possible to do this, and completed the present invention.
本発明において、アルミン酸アルカリ金属塩と
しては、アルミン酸ナトリウム、アルミン酸カリ
ウムあるいはこれらの混合物を挙げることがで
き、その組成は、M2O／Al2O3＝1.0〜1.7（モル
比）（Ｍはアルカリ金属を示す）の範囲のものが
好ましい。 In the present invention, examples of the alkali metal aluminate include sodium aluminate, potassium aluminate, or a mixture thereof, and the composition thereof is M 2 O/Al 2 O 3 = 1.0 to 1.7 (molar ratio) ( M represents an alkali metal).
一般式（）及び（）で表わされる有機ヒド
ロキシル酸において、Ｒが炭素数10を超える脂肪
族基で表わされるものは一般的でなく入手が困難
であり、また酸基１個当りの分子量が200を超え
るものは使用するヒドロキシル酸量が多くなり、
経済的に好ましくない。実際には、当該分子量が
100以下のものが好適である。有機ヒドロキシル
酸の好ましい具体例としては、例えばグリコール
酸、乳酸、グリセリン酸、ヒドロアクリル酸、オ
キシ酪酸、酒石酸、リンゴ酸、アラボン酸、グル
コン酸、クエン酸等のオキシカルボン酸；１−ヒ
ドロキシエチリデン−１，１−ジホスホン酸、２
−ヒドロキシプロピルホスホン酸等のオキシホス
ホン酸が挙げられる。 Among the organic hydroxyl acids represented by the general formulas () and (), those in which R is an aliphatic group having more than 10 carbon atoms are uncommon and difficult to obtain, and the molecular weight per acid group is 200. If it exceeds , the amount of hydroxyl acid used will be large,
Economically unfavorable. In reality, the molecular weight is
A value of 100 or less is preferred. Preferred specific examples of organic hydroxyl acids include oxycarboxylic acids such as glycolic acid, lactic acid, glyceric acid, hydroacrylic acid, oxybutyric acid, tartaric acid, malic acid, arabonic acid, gluconic acid, and citric acid; 1-hydroxyethylidene- 1,1-diphosphonic acid, 2
-oxyphosphonic acids such as hydroxypropylphosphonic acid.
本発明の中和方法は特に制限されないが、アル
ミン酸アルカリ金属塩の水溶液中に有機ヒドロキ
シル酸の水溶液を滴下するのが好ましい。アルミ
ン酸アルカリ金属塩の水溶液の濃度は２〜40重量
％、また有機ヒドロキシル酸の水溶液の濃度は５
〜50重量％のものが好ましい。 Although the neutralization method of the present invention is not particularly limited, it is preferable to drop an aqueous solution of an organic hydroxyl acid into an aqueous solution of an alkali metal aluminate. The concentration of the aqueous solution of alkali metal aluminate is 2 to 40% by weight, and the concentration of the aqueous solution of organic hydroxyl acid is 5% by weight.
~50% by weight is preferred.
アルミン酸アルカリ金属塩水溶液に有機ヒドロ
キシル酸水溶液を滴下して中和反応を行う場合、
生成するアルミナゾルのコロイド粒子径は、使用
する酸の種類、濃度、添加方法、撹拌方法、中和
温度等によつて異なるが、就中特に中和温度が大
きな影響を与える。例えば、10重量％のアルミン
酸カリウム塩水溶液（1.6K2O・Al2O3として10重
量％）中に、10重量％のグルコース酸水溶液を滴
下して中和する場合、中和温度が30℃で0.05μｍ
45℃で0.18μｍ、60℃で0.48μｍの粒子径のものが
得られる。従つて、本発明方法においては中和温
度を一定に保つて行うのが好ましい。また、この
ようにして得られたコロイド粒子はその後PHを変
化させてもその粒径に影響を与えないと共に、広
いPH範囲で安定であるので、コロイド粒子生成後
はリン酸等の適当な酸でPHを調整することができ
る。 When performing a neutralization reaction by dropping an organic hydroxyl acid aqueous solution into an alkali metal aluminate salt aqueous solution,
The colloidal particle size of the alumina sol produced varies depending on the type and concentration of the acid used, the addition method, the stirring method, the neutralization temperature, etc., but the neutralization temperature has a particularly large influence. For example, when neutralizing a 10% by weight aqueous solution of glucose acid into a 10% by weight aqueous solution of potassium aluminate salt (10% by weight as 1.6K 2 O・Al 2 O 3 ), the neutralization temperature is 30% by weight. 0.05μm at °C
A particle size of 0.18 μm at 45°C and 0.48 μm at 60°C is obtained. Therefore, in the method of the present invention, it is preferable to maintain the neutralization temperature constant. In addition, the colloidal particles obtained in this way have no effect on their particle size even if the pH is subsequently changed, and they are stable over a wide pH range, so after colloidal particle generation, an appropriate acid such as phosphoric acid is used. PH can be adjusted with.
斯くの如く、本発明方法によれば、中和時の条
件、特に中和温度を適宜調節することにより0.1μ
ｍ以下の微細な粒径から1μｍを超える粒径のも
のまでの任意の粒径をもつたアルミナゾルを得る
ことができ、かつPH４〜11の広い範囲で凝集を惹
起しないアルミナゾルとすることができる。 As described above, according to the method of the present invention, by appropriately adjusting the conditions during neutralization, especially the neutralization temperature,
It is possible to obtain an alumina sol having any particle size from a fine particle size of 1 μm or less to a particle size of more than 1 μm, and it is possible to obtain an alumina sol that does not cause agglomeration in a wide range of pH from 4 to 11.
アルミナゾルの微粒子化に有機ヒドロキシル酸
が特異的であることの作用機構は必ずしも明確で
ないが、次のように考えられる。すなわち、アル
ミン酸アルカリ金属塩の水溶液中に有機ヒドロキ
シル酸の水溶液を添加してPHを徐々に下げて行く
とこれにつれてアルミナ水和物が析出して一次粒
子が形成するが、この際有機ヒドロキシル酸が強
く水和した層に何らかの形で関与し、一次粒子の
核としての成長及び一次粒子から二次粒子への凝
集がある程度抑制されること、また有機ヒドロキ
シル酸はAl3+とキレートを生成し得るので、ア
ルミナ水和物から溶出してくるAl3+を捕捉し、
コロイド粒子の高次な凝集を防止すること等によ
るものと思われる。 Although the mechanism of action of the specificity of organic hydroxyl acids in making alumina sol into fine particles is not necessarily clear, it is thought to be as follows. That is, when an aqueous solution of an organic hydroxyl acid is added to an aqueous solution of an alkali metal aluminate and the pH is gradually lowered, alumina hydrate precipitates and primary particles are formed. is somehow involved in the strongly hydrated layer, suppressing the growth of primary particles as nuclei and aggregation of primary particles into secondary particles to some extent, and that organic hydroxyl acids form chelates with Al 3+ . Therefore, the Al 3+ eluted from the alumina hydrate is captured,
This seems to be due to the prevention of high-order aggregation of colloidal particles.
而して、有機ヒドロキシル酸以外のキレート化
剤、例えばポリリン酸、アミノトリ（メチレンホ
スホン酸）等のアルコール性水酸基を有さないキ
レート化剤を用いてアルミン酸アルカリ金属塩水
溶液を中和反応せしめて、粒子径が粗大で、保存
中に凝集、沈降を惹起する不安定なアルミナゾル
が得られるにすぎない。 Then, the aqueous solution of alkali metal aluminate is subjected to a neutralization reaction using a chelating agent other than organic hydroxyl acid, for example, a chelating agent having no alcoholic hydroxyl group such as polyphosphoric acid or aminotri(methylenephosphonic acid). However, only an unstable alumina sol is obtained which has a coarse particle size and causes aggregation and sedimentation during storage.
次に本発明の実施例及び比較例を挙げて説明す
る。 Next, examples and comparative examples of the present invention will be described.
尚、コロイド粒子の粒径は、実施例については
コールターサブミクロンアナライザーモデルN4
（コールター社）を、また比較例については遠心
式自動粒度分布測定装置CAPA−500（堀場製作
所）を用いて測定した。このように測定装置を変
えた理由は、実施例のごとく粒径が0.1μ以下のア
ルミナゾルは透明度が高く、遠心式測定装置では
原理上測定不可能であるからである。 In addition, the particle size of the colloidal particles was determined using Coulter Submicron Analyzer Model N4 in the examples.
(Coulter), and comparative examples were measured using a centrifugal automatic particle size distribution analyzer CAPA-500 (Horiba, Ltd.). The reason for changing the measuring device in this way is that alumina sol with a particle size of 0.1 μm or less, as in the example, has high transparency and cannot be measured using a centrifugal measuring device in principle.
実施例 １
アルミン酸カリウム水溶液（Al2O316％、
K2O／Al2O3モル比1.63）100ｇを300mlビーカー
にとり、ホモミキサーで撹拌しながら30℃に保つ
た。次に、このアルミン酸カリウム水溶液中に40
％クエン酸水溶液100ｇを徐々に滴下しながら添
加し、PH10.0とした。得られた液は無色透明であ
るが、赤色レーザー光を照射するとチンダル光が
観察されることから、コロイド溶液であることが
確認された。このコロイド溶液（Al2O38％）は
粒径0.015μであり、５ケ月間静置しておいても粒
径、性状ともに変化はなかつた。Example 1 Potassium aluminate aqueous solution (Al 2 O 3 16%,
100 g of K 2 O/Al 2 O 3 molar ratio 1.63) was placed in a 300 ml beaker and kept at 30° C. while stirring with a homomixer. Next, in this potassium aluminate aqueous solution, 40
% citric acid aqueous solution was gradually added dropwise to adjust the pH to 10.0. The obtained liquid was clear and colorless, but Tyndall light was observed when irradiated with red laser light, confirming that it was a colloidal solution. This colloidal solution (Al 2 O 3 8%) had a particle size of 0.015μ, and there was no change in particle size or properties even after it was left standing for 5 months.
実施例 ２
アルミン酸ナトリウム水溶液（Al2O316.7％、
Na2O／Al2O3モル比1.30）100ｇを30mlビーカー
にとり、ホモミキサーで撹拌しながら、20℃に保
つた。次にこのアルミン酸ナトリウム水溶液中に
30％グリコール酸水溶液125ｇを徐々に滴下しな
がら添加し、PH7.5とした。得られた液は無色透
明であるが、赤色レーザー光を照射するとチンダ
ル光が観察されることから、コロイド溶液である
ことが確認された。このコロイド溶液（Al2O37.4
％）は粒径0.010μであり、５ケ月間静置しておい
ても粒径、性状ともに変化はなかつた。Example 2 Sodium aluminate aqueous solution (Al 2 O 3 16.7%,
100 g of Na 2 O/Al 2 O 3 molar ratio 1.30) was placed in a 30 ml beaker and kept at 20° C. while stirring with a homomixer. Next, in this sodium aluminate aqueous solution
125 g of a 30% aqueous glycolic acid solution was gradually added dropwise to adjust the pH to 7.5. The obtained liquid was clear and colorless, but Tyndall light was observed when irradiated with red laser light, confirming that it was a colloidal solution. This colloidal solution (Al 2 O 3 7.4
%) had a particle size of 0.010μ, and there was no change in particle size or properties even after it was left standing for 5 months.
実施例 ３
アルミン酸ナトリウム水溶液（Al2O32.8％、
Na2O／Al2O3モル比1.30）100ｇを300mlビーカー
にとり、ホモミキサーで撹拌しながら20℃に保つ
た。次にこのアルミン酸ナトリウム水溶液中に５
％１−ヒドロキシエチリデン−１，１−ジホスホ
ン酸水溶液160ｇを徐々に滴下しながら添加し、
PH7.3とした。得られた液は青味を帯びた乳光色
透明であつた。このコロイド溶液（Al2O31.1％）
は粒径0.050μであり、５ケ月間静置しておいても
粒径、性状ともに変化はなかつた。Example 3 Sodium aluminate aqueous solution (Al 2 O 3 2.8%,
100 g of Na 2 O/Al 2 O 3 molar ratio 1.30) was placed in a 300 ml beaker and kept at 20° C. while stirring with a homomixer. Next, in this sodium aluminate aqueous solution, 5
% 1-hydroxyethylidene-1,1-diphosphonic acid aqueous solution was gradually added dropwise,
The pH was set to 7.3. The resulting liquid was clear and opalescent with a bluish tinge. This colloidal solution (Al 2 O 3 1.1%)
The particle size was 0.050μ, and there was no change in particle size or properties even after it was left standing for 5 months.
実施例 ４
アルミン酸カリウム水溶液（Al2O38.0％、
K2O／Al2O3モル比1.63）100ｇを300mlビーカー
にとり、ホモミキサーで撹拌しながら30℃に保つ
た。次にこのアルミン酸カリウム水溶液中に20％
乳酸水溶液130ｇを従々に滴下しながら添加し、
PH8.0とした。得られた液は乳光色透明であつた。
このコロイド溶液（Al2O33.5％）は粒径0.040μで
あり、５ケ月間静置しておいても粒径、性状とも
に変化はなかつた。Example 4 Potassium aluminate aqueous solution (Al 2 O 3 8.0%,
100 g of K 2 O/Al 2 O 3 molar ratio 1.63) was placed in a 300 ml beaker and kept at 30° C. while stirring with a homomixer. Next, add 20% to this potassium aluminate aqueous solution.
Add 130g of lactic acid aqueous solution dropwise,
The pH was set to 8.0. The resulting liquid was transparent and opalescent.
This colloidal solution (3.5% Al 2 O 3 ) had a particle size of 0.040 μm, and there was no change in particle size or properties even after it was allowed to stand for 5 months.
実施例 ５
アルミン酸ナトリウム水溶液（Al2O322.2％、
Na2O／Al2O3モル比1.30）100ｇを300mlビーカー
にとり、ホモミキサーで撹拌しながら30℃に保つ
た。次にこのアルミン酸ナトリウム水溶液中に40
％グルコン酸水溶液300ｇを徐々に滴下しながら
添加し、PH8.0とした。得られた液は透明である
が赤色レーザー光を照射するとチンダル光が観察
されることから、コロイド溶液であることが確認
された。このコロイド溶液（Al2O35.6％）は粒径
0.010μであり、５ケ月間静置しておいても粒径、
性状ともに変化はなかつた。Example 5 Sodium aluminate aqueous solution (Al 2 O 3 22.2%,
100g of Na2O / Al2O3 molar ratio 1.30) was placed in a 300ml beaker and kept at 30°C while stirring with a homomixer. Next, in this sodium aluminate aqueous solution, 40
% gluconic acid aqueous solution was gradually added dropwise to adjust the pH to 8.0. Although the obtained liquid was transparent, Tyndall light was observed when irradiated with red laser light, which confirmed that it was a colloidal solution. This colloidal solution (Al 2 O 3 5.6%) has a particle size of
The particle size is 0.010μ, and the particle size remains unchanged even after being left standing for 5 months.
There was no change in properties.
実施例 ６
アルミン酸カリウム水溶液（Al2O312.0％、
K2O／Al2O3モル比1.63）100ｇを300mlビーカー
にとり、ホモミキサーで撹拌しながら30℃に保つ
た。次にこのアルミン酸カリウム水溶液中に30％
クエン酸水溶液75ｇを徐々に滴下しながら添加し
たところ、反応系全体が乳光色を帯び、コロイド
粒子が発生してきた。（粒径0.025μ）。次にこのア
ルミナゾルコロイド溶液に30％リン酸水溶液30ｇ
を添加し、PHを7.8に調整した。得られた液は乳
光色透明であつた。このコロイド溶液（Al2O35.9
％）は粒径0.028μであり、５ケ月間静置しておい
ても粒径、性状ともに変化はなかつた。Example 6 Potassium aluminate aqueous solution (Al 2 O 3 12.0%,
100 g of K 2 O/Al 2 O 3 molar ratio 1.63) was placed in a 300 ml beaker and kept at 30° C. while stirring with a homomixer. Next, add 30% to this potassium aluminate aqueous solution.
When 75 g of citric acid aqueous solution was gradually added dropwise, the entire reaction system became opalescent and colloidal particles were generated. (particle size 0.025μ). Next, add 30g of 30% phosphoric acid aqueous solution to this alumina sol colloid solution.
was added to adjust the pH to 7.8. The resulting liquid was transparent and opalescent. This colloidal solution (Al 2 O 3 5.9
%) had a particle size of 0.028μ, and there was no change in particle size or properties even after it was left standing for 5 months.
比較例 １
アルミン酸カリウム水溶液（Al2O34.0％、
K2O／Al2O3、モル比1.63）100ｇを300mlビーカ
ーにとり、ホモミキサーで撹拌しながら30℃に保
つた。次にこのアルミン酸カリウム水溶液中に10
％リン酸水溶液82ｇを滴下しながら添加し、PH
7.8とした。得られた液は白濁していた。Comparative Example 1 Potassium aluminate aqueous solution (Al 2 O 3 4.0%,
100 g of K 2 O/Al 2 O 3 (molar ratio 1.63) was placed in a 300 ml beaker and kept at 30° C. while stirring with a homomixer. Next, in this potassium aluminate aqueous solution, 10
% phosphoric acid aqueous solution was added dropwise, and the pH
It was set at 7.8. The resulting liquid was cloudy.
この溶液（Al2O32.2％）のアルミナゾルの粒径
は2.5μであり、不安定で１週間以内に凝集固化し
た。 The alumina sol of this solution (2.2% Al 2 O 3 ) had a particle size of 2.5 μm and was unstable and coagulated and solidified within one week.
比較例 ２
アルミン酸ナトリウム水溶液（Al2O311.1％、
Na2O／Al2O3モル比1.30）100ｇを300mlビーカー
にとり、ホモミキサーで撹拌しながら30℃に保つ
た。次にこのアルミン酸ナトリウム水溶液中に30
％アミノトリ（メチレンホルホン酸）95ｇを徐々
に滴下しながら添加し、PH7.5とした。得られた
液は白濁していた。この溶液（Al2O35.7％）のア
ルミナゾルの粒径は1.4μであり、静置すると数時
間でアルミナゾルが底部に沈降し分層した。Comparative Example 2 Sodium aluminate aqueous solution (Al 2 O 3 11.1%,
100g of Na2O / Al2O3 molar ratio 1.30) was placed in a 300ml beaker and kept at 30°C while stirring with a homomixer. Next, in this sodium aluminate aqueous solution, 30
% aminotri(methylene phosphonic acid) was gradually added dropwise to adjust the pH to 7.5. The resulting liquid was cloudy. The particle size of the alumina sol in this solution (5.7% Al 2 O 3 ) was 1.4 μ, and when it was allowed to stand still, the alumina sol settled to the bottom and separated into layers within several hours.
Claims (1)
一般式（）又は（） Ｒ（OH）ｍ（COOH）ｎ （） Ｒ（OH）ｍ（PO3H2）ｎ （） （式中、ｍ及びｎは１以上の数を示し、Ｒは炭素
数１〜10の飽和又は不飽和の脂肪族基を示し、酸
基１個当たりの分子量が200以下であるものとす
る） で表わされる有機ヒドロキシル酸の水溶液とを中
和反応せしめることを特徴とするアルミナゾルの
製造法。[Claims] 1. An aqueous solution of alkali metal aluminate and the following general formula () or () R(OH)m(COOH)n () R(OH)m(PO 3 H 2 )n () (In the formula, m and n represent numbers of 1 or more, R represents a saturated or unsaturated aliphatic group having 1 to 10 carbon atoms, and the molecular weight per acid group is 200 or less) 1. A method for producing alumina sol, which comprises carrying out a neutralization reaction with an aqueous solution of an organic hydroxyl acid represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58093453A JPS59223223A (en) | 1983-05-27 | 1983-05-27 | Manufacture of alumina sol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58093453A JPS59223223A (en) | 1983-05-27 | 1983-05-27 | Manufacture of alumina sol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59223223A JPS59223223A (en) | 1984-12-15 |
| JPH0123416B2 true JPH0123416B2 (en) | 1989-05-02 |
Family
ID=14082741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58093453A Granted JPS59223223A (en) | 1983-05-27 | 1983-05-27 | Manufacture of alumina sol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59223223A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005032427A1 (en) * | 2005-07-12 | 2007-01-18 | Degussa Ag | Aluminum oxide dispersion |
| JP5733758B2 (en) * | 2011-12-27 | 2015-06-10 | 多木化学株式会社 | Binding method of inorganic material |
| CN110015674B (en) * | 2019-02-03 | 2021-05-28 | 中海油天津化工研究设计院有限公司 | Preparation method of pure beta-type aluminum hydroxide |
| JPWO2022123979A1 (en) | 2020-12-09 | 2022-06-16 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5213800A (en) * | 1975-07-22 | 1977-02-02 | Shigeki Yamada | Method to be used for pasting shrink-film made label |
| JPS5213799A (en) * | 1975-07-23 | 1977-02-02 | Hochiki Corp | Disconnection detection method |
-
1983
- 1983-05-27 JP JP58093453A patent/JPS59223223A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5213800A (en) * | 1975-07-22 | 1977-02-02 | Shigeki Yamada | Method to be used for pasting shrink-film made label |
| JPS5213799A (en) * | 1975-07-23 | 1977-02-02 | Hochiki Corp | Disconnection detection method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59223223A (en) | 1984-12-15 |
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