JPH04280815A - Fine particulate alkali titanate and its production - Google Patents
Fine particulate alkali titanate and its productionInfo
- Publication number
- JPH04280815A JPH04280815A JP12567491A JP12567491A JPH04280815A JP H04280815 A JPH04280815 A JP H04280815A JP 12567491 A JP12567491 A JP 12567491A JP 12567491 A JP12567491 A JP 12567491A JP H04280815 A JPH04280815 A JP H04280815A
- Authority
- JP
- Japan
- Prior art keywords
- pure water
- water
- aqueous solution
- alkali metal
- alkali titanate
- 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.)
- Pending
Links
- 239000003513 alkali Substances 0.000 title claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 5
- 239000004135 Bone phosphate Substances 0.000 claims abstract description 4
- 239000007900 aqueous suspension Substances 0.000 claims abstract 2
- 239000010419 fine particle Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 10
- 239000000725 suspension Substances 0.000 abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 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 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004438 BET method Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 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 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000174 gluconic acid Substances 0.000 description 4
- 235000012208 gluconic acid Nutrition 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007716 flux method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910020288 Na2Ti6O13 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 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
- 238000004458 analytical method Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、微粒子チタン酸アルカ
リ及びその製造法に関するものである。本発明により得
られる微粒子チタン酸アルカリ粉末は、セラミックス、
触媒、イオン交換体等の原料として利用されるものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to fine particles of alkali titanate and a method for producing the same. Fine particle alkali titanate powder obtained by the present invention can be used for ceramics,
It is used as a raw material for catalysts, ion exchangers, etc.
【０００２】0002
【従来の技術】チタン酸アルカリは通常繊維状の形状を
持ち、その比表面積は小さく、活性のある微粒子粉末で
はない。チタン酸アルカリの製造法としては、焼成法、
溶融法、水熱法、フラックス法及び、融体法等が報告さ
れているが、いずれも高温及び（又は）高圧の合成条件
が必要であり、経済的ではない。又、得られたチタン酸
アルカリは通常、繊維状に大きく成長し、堅く凝集して
いる。従つて、その後の粉砕操作が不可欠であるが、機
械的粉砕では超微粒子まで粉砕することは不可能である
。BACKGROUND OF THE INVENTION Alkali titanates usually have a fibrous shape, have a small specific surface area, and are not active fine powder particles. Methods for producing alkali titanate include calcination method,
Melting methods, hydrothermal methods, flux methods, melt methods, etc. have been reported, but all require high temperature and/or high pressure synthesis conditions and are not economical. Further, the obtained alkali titanate usually grows in a large fibrous form and is tightly aggregated. Therefore, a subsequent pulverization operation is essential, but it is impossible to pulverize ultrafine particles by mechanical pulverization.
【０００３】チタン酸アルカリ及び製造法に関しては、
これまでに多くの文献、特許に開示されており、これ等
のチタン酸アルカリは、通常数μｍ〜数十μｍの長径を
もつ繊維状であり、比表面積も約２０ｍ２／ｇ以下と小
さく、活性な表面を持つものではなかつた。又、これ等
の製造法は、焼成法、溶融法、水熱法、フラックス法、
融体法等が知られているが、いずれも高温及び（又は）
、高圧の合成条件が必要であり、実質的に焼結のない表
面活性な微粒子チタン酸アルカリを得ることは困難なば
かりでなく、経済的ではない。Regarding alkali titanate and manufacturing method,
These alkali titanates, which have been disclosed in many documents and patents, are usually fibrous with a long axis of several μm to several tens of μm, have a small specific surface area of about 20 m2/g or less, and are highly active. It didn't have a typical surface. In addition, these manufacturing methods include firing method, melting method, hydrothermal method, flux method,
Melt method etc. are known, but all of them require high temperature and/or
, high-pressure synthesis conditions are required, and it is not only difficult to obtain surface-active fine-particle alkali titanates that are substantially free from sintering, but also uneconomical.
【０００４】0004
【発明が解決しようとする課題】本発明の目的は、従来
技術では得られない表面活性な微粒子チタン酸アルカリ
（粒子径は約０．５μｍ以下であり、比表面積は約１０
０ｍ２／ｇ以上）及び、その製造法を提供することにあ
る。[Problems to be Solved by the Invention] The object of the present invention is to produce surface-active fine particles of alkali titanate (particle size is about 0.5 μm or less, specific surface area is about 10
0 m2/g or more) and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段及び作用】本発明は、粒子
の大きさが０．０１〜０．５μｍ、比表面積が１００ｍ
２／ｇ以上であるという従来技術では得られなかつた表
面活性な微粒子チタン酸アルカリを提供するものであり
、更にその製造法としての二塩基性又は、三塩基性有機
カルボン酸の一種又は、二種以上を溶解した５０℃以上
の水溶液系に四塩化チタンの水溶液を注加し、生成する
水和酸化チタン〜有機酸の反応縮合物を▲ろ▼過、水洗
し、次いで、この水懸濁液に水酸化アルカリ金属を添加
し、ｐＨ８以上、５０℃以上の温度にて、反応せしめた
後、▲ろ▼過、水洗、乾燥することを特徴とする製造法
である。以下に、この微粒子チタン酸アルカリ粉末の具
体的製造方法を説明する。[Means and effects for solving the problems] The present invention provides particles with a size of 0.01 to 0.5 μm and a specific surface area of 100 m
2/g or more, which could not be obtained by conventional techniques, and furthermore, it provides a surface-active fine particle alkali titanate which cannot be obtained by the conventional technology, and furthermore, as a method for producing the same, one type of dibasic or tribasic organic carboxylic acid or dibasic organic carboxylic acid is used. An aqueous solution of titanium tetrachloride is poured into an aqueous solution system at 50°C or higher in which at least one of the above species has been dissolved, and the resulting reaction condensate of hydrated titanium oxide and an organic acid is filtered and washed with water. This is a production method characterized by adding an alkali metal hydroxide to a liquid, reacting at a pH of 8 or higher and a temperature of 50°C or higher, followed by ▲filtration, washing with water, and drying. A specific method for producing this fine-particle alkali titanate powder will be described below.
【０００６】本発明の第一基本は、二塩基性又は、三塩
基性有機カルボン酸、例えばシュウ酸、マロン酸、コハ
ク酸、リンゴ酸、酒石酸、クエン酸、グルコン酸等の一
種又は、二種以上の所定濃度溶液（好ましくは、有機酸
の合計０．５〜５．０モルを純水５〜２０ｌに溶かした
もの）を５０℃〜１００℃の一定温度に加温し、これを
撹拌しつつ四塩化チタンの所定濃度溶液（好ましくは、
四塩化チタンの０．２５〜２．５モルを純水１．０〜５
．０ｌに溶かしたもの）を一定速度（好ましくは、５時
間以内）にて注加し、水和酸化チタン〜有機酸の反応縮
合物として析出せしめ、これを▲ろ▼過、水洗すること
を特徴とする。The first basis of the present invention is to use one or two dibasic or tribasic organic carboxylic acids such as oxalic acid, malonic acid, succinic acid, malic acid, tartaric acid, citric acid, and gluconic acid. The solution with the above predetermined concentration (preferably, a total of 0.5 to 5.0 moles of organic acid dissolved in 5 to 20 liters of pure water) is heated to a constant temperature of 50 to 100 °C, and this is stirred. A predetermined concentration solution of titanium tetrachloride (preferably,
0.25 to 2.5 mol of titanium tetrachloride to 1.0 to 5 mol of pure water
．． 0 liter) at a constant rate (preferably within 5 hours) to precipitate a reaction condensate of hydrated titanium oxide and an organic acid, which is then filtered and washed with water. shall be.
【０００７】本発明の第二基本は、第一基本で得られた
水和酸化チタン〜有機酸の反応縮合物を純水に懸濁させ
（好ましくは、酸化チタンとして５０〜２００ｇを純水
５．０〜１５．０ｌに懸濁させる）、これを５０℃〜１
００℃の一定温度に加温し、撹拌しつつ水酸化アルカリ
金属又は、水と反応して水酸化アルカリ金属となりうる
アルカリ金属化合物の所定濃度溶液（好ましくは、水酸
化アルカリ金属の１．０〜１０．０モルを純水１．０〜
５．０ｌに溶かしたもの）を添加し、懸濁液をｐＨ８以
上とし、１〜５時間の間処理することを特徴とする。こ
の操作により、第一基本で得られた水和酸化チタン〜有
機酸の反応縮合物の有機酸は、反応縮合物から中和、離
脱し、離脱した有機酸の代わりにアルカリ金属が水和酸
化チタンと結合し、ついにはチタン酸アルカリと成り得
るのである。以下、実施例をもつて本発明を更に詳細に
説明するが、本発明はこれらによつて限定されるもので
はない。The second basis of the present invention is to suspend the reaction condensate of hydrated titanium oxide and organic acid obtained in the first basis in pure water (preferably, 50 to 200 g of titanium oxide is suspended in pure water .0 to 15.0 l), and then suspended at 50°C to 15.0 l.
A solution of a predetermined concentration of an alkali metal hydroxide or an alkali metal compound that can react with water to form an alkali metal hydroxide (preferably 1.0 to 1.0% of the alkali metal hydroxide) is heated to a constant temperature of 00°C and stirred. 10.0 mol to pure water 1.0 ~
(dissolved in 5.0 liters) to adjust the pH of the suspension to 8 or higher, and treat for 1 to 5 hours. Through this operation, the organic acid of the reaction condensate of hydrated titanium oxide and organic acid obtained in the first basic process is neutralized and separated from the reaction condensate, and the alkali metal is hydrated and oxidized in place of the separated organic acid. It can combine with titanium and eventually become alkali titanate. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
【０００８】[0008]
【実施例、比較例】実施例１
シュウ酸２．０モルを純水に溶解して９．０ｌとし、撹
拌しつつ９０℃に昇温する。これとは別に四塩化チタン
１．０モルを純水に溶解して１．０ｌとし、これを１０
ｍｌ／ｍｉｎ．の速度で撹拌下のシュウ酸溶液に添加す
ると、四塩化チタンは直ちに加水分解し、白色状の懸濁
液となつて水和酸化チタン〜シュウ酸の反応縮合物の微
粒子が析出する。添加終了後更に１．０時間、９０℃に
維持する。これを▲ろ▼過し、▲ろ▼液がｐＨ５．０に
なるまで純水にて水洗し、この水湿ケーキを純水に懸濁
して５．０ｌとし、撹拌しつつ９０℃に昇温する。次い
で、水酸化カリウム２．０モルを純水に溶解して１．０
ｌとし、上記懸濁液がｐＨ９．０になるまで注加し、更
に１．５時間、９０℃に維持した後、▲ろ▼過し、▲ろ
▼液がｐＨ８．０になるまで純水で水洗して水湿ケーキ
として取り出し、これを９０℃で乾燥すると粉砕を必要
としない良好な粉末となる。これを電子顕微鏡で確認し
たところ、数十〜数百Åの球状粒子の集合体で、大きさ
は０．０３〜０．３μｍであり、ＢＥＴ法による比表面
積の実測値は２２０ｍ２／ｇと非常に大きな数値であつ
た。又、Ｘ線回折分析で確認したところ非晶質であつた
が、７５０℃で１時間処理をしたところ、六チタン酸カ
リＫ２Ｔｉ６Ｏ１３が確認された。[Examples and Comparative Examples] Example 1 2.0 mol of oxalic acid was dissolved in pure water to make 9.0 liters, and the temperature was raised to 90°C while stirring. Separately, 1.0 mol of titanium tetrachloride was dissolved in pure water to make 1.0 liters, and 1.0 mol of titanium tetrachloride was dissolved in pure water.
ml/min. When added to a stirred oxalic acid solution at a rate of 1, titanium tetrachloride is immediately hydrolyzed to form a white suspension in which fine particles of a reaction condensate of hydrated titanium oxide and oxalic acid are precipitated. After the addition is complete, the temperature is maintained at 90°C for an additional 1.0 hour. ▲Filter this, ▲Wash with pure water until the filtrate reaches pH 5.0, suspend this wet cake in pure water to make 5.0L, and raise the temperature to 90℃ while stirring. do. Next, 2.0 mol of potassium hydroxide was dissolved in pure water to give 1.0 mol of potassium hydroxide.
1, and added the suspension until the pH reached 9.0. After maintaining the temperature at 90°C for another 1.5 hours, ▲filtrate, and ▲pour the filtrate with pure water until the pH reached 8.0. The cake is washed with water and taken out as a wet cake, which is then dried at 90°C to form a good powder that does not require pulverization. When this was confirmed using an electron microscope, it was found to be an aggregate of spherical particles of several tens to hundreds of angstroms in size, with a size of 0.03 to 0.3 μm, and the actual value of the specific surface area measured by the BET method was 220 m2/g, which is extremely large. This was a large number. Further, it was confirmed by X-ray diffraction analysis that it was amorphous, but when it was treated at 750° C. for 1 hour, potassium hexatitanate K2Ti6O13 was confirmed.
【０００９】比較例１
シュウ酸を使用しない他は、実施例１と同一条件及び要
領で白色状の粒状物を得たが、非常に固い数ｍｍ前後の
乾燥粒子となつた。これを粉砕し、電子顕微鏡で確認し
たところ、数μｍ〜数百μｍの不定形粒状物であり、微
粒子と言えるものではなかつた。又、ＢＥＴ法による比
表面積の実測値は２．８ｍ２／ｇと非常に小さく、Ｘ線
回折分析で確認したところ実施例１と同様非晶質であつ
たが、７５０℃で１時間処理したところ、アナターゼ型
酸化チタンだけが確認された。Comparative Example 1 White granules were obtained under the same conditions and procedure as in Example 1, except that oxalic acid was not used, but the result was very hard dry particles around several mm in size. When this was crushed and confirmed using an electron microscope, it was found to be irregularly shaped particles with a size of several μm to several hundred μm, and could not be called fine particles. In addition, the actual value of the specific surface area measured by the BET method was very small at 2.8 m2/g, and it was confirmed by X-ray diffraction analysis that it was amorphous as in Example 1, but when treated at 750 ° C. for 1 hour. , only anatase-type titanium oxide was confirmed.
【００１０】実施例２
実施例１で、水酸化カリウムの代わりに水酸化ナトリウ
ムを使用する他は、実施例１と同一条件及び要領で白色
の微粉末を得た。これを電子顕微鏡で確認したところ、
数十〜数百Åの球状粒子の集合体で、大きさは０．０５
〜０．５μｍであり、ＢＥＴ法による比表面積の実測値
は１７５ｍ２／ｇであつた。又、Ｘ線回折分析では、非
晶質であつたが、７５０℃で１時間処理をしたところ、
六チタン酸ナトリウムＮａ２Ｔｉ６Ｏ１３が確認された
。Example 2 A fine white powder was obtained under the same conditions and procedure as in Example 1, except that sodium hydroxide was used instead of potassium hydroxide. When this was confirmed using an electron microscope,
An aggregate of spherical particles of several tens to hundreds of angstroms, with a size of 0.05
~0.5 μm, and the actual value of the specific surface area measured by the BET method was 175 m 2 /g. Also, in X-ray diffraction analysis, it was found to be amorphous, but when treated at 750°C for 1 hour,
Sodium hexatitanate Na2Ti6O13 was confirmed.
【００１１】実施例３
酒石酸１．５モルとグルコン酸０．８モルを純水に溶解
し１５．０ｌとし、撹拌しつつ１００℃に昇温する。こ
れとは別に四塩化チタン１．５モルを純水に溶解し３．
０ｌとし、これを２０ｍｌ／ｍｉｎ．の速度にて、撹拌
下の酒石酸、グルコン酸の混合溶液に添加すると、白色
状の懸濁液となつて水和酸化チタン〜酒石酸〜グルコン
酸の反応縮合物の微粒子が析出する。更に１００℃で１
時間維持した後、▲ろ▼過し純水でｐＨ５．０になるま
で水洗する。この水湿ケーキを純水に懸濁して１０ｌと
し、撹拌しつつ１００℃に昇温する。次いで、水酸化カ
リウム４．０モルを純水で溶解して５．０ｌとし、上記
懸濁液がｐＨ１０．０になるまで注加し、更に１００℃
で２時間処理した後、▲ろ▼過し、純水でｐＨ８．０に
なるまで水洗する。この水湿ケーキを取り出し、７０℃
で乾燥すると、粉砕を必要としない良好な粉末となる。
これを電子顕微鏡で確認したところ、数十〜数百Åの球
状粒子の集合体で、大きさは０．０２〜０．１μｍであ
り、図１にそのトレース図を示す。ＢＥＴ法による比表
面積の実測値は２９０ｍ２／ｇと非常に大きな数値であ
つた。又、Ｘ線回折分析で確認したところ、六チタン酸
カリＫ２Ｔｉ６Ｏ１３が確認された。図２にその分析図
を示す。Example 3 1.5 mol of tartaric acid and 0.8 mol of gluconic acid were dissolved in pure water to make 15.0 liters, and the temperature was raised to 100° C. while stirring. Separately, 1.5 mol of titanium tetrachloride was dissolved in pure water.3.
0 liters, and the flow rate was 20 ml/min. When it is added to a mixed solution of tartaric acid and gluconic acid under stirring at a speed of , fine particles of a reaction condensate of hydrated titanium oxide, tartaric acid, and gluconic acid are precipitated as a white suspension. Furthermore, 1 at 100℃
After maintaining for a certain period of time, ▲filtrate▼ and wash with pure water until the pH becomes 5.0. This wet cake was suspended in pure water to make 10 liters, and the temperature was raised to 100° C. while stirring. Next, 4.0 mol of potassium hydroxide was dissolved in pure water to make 5.0 liters, poured into the suspension until the pH reached 10.0, and further heated at 100°C.
After treating for 2 hours, ▲filter▼ and wash with pure water until the pH becomes 8.0. Take out this wet cake and heat it at 70℃.
When dried, it becomes a good powder that does not require grinding. When this was confirmed using an electron microscope, it was found to be an aggregate of spherical particles of several tens to several hundred angstroms, with a size of 0.02 to 0.1 μm, and a trace diagram thereof is shown in FIG. The actual value of the specific surface area measured by the BET method was 290 m2/g, which was a very large value. Further, when confirmed by X-ray diffraction analysis, potassium hexatitanate K2Ti6O13 was confirmed. Figure 2 shows the analysis diagram.
【００１２】実施例４
シュウ酸１．０モルとクエン酸２．０モルを純水に溶解
し１２．０ｌとし、撹拌しつつ９５℃に昇温する。これ
とは別に四塩化チタン２．０モルを純水に溶解し５．０
ｌとし、これを２０ｍｌ／ｍｉｎ．の撹拌下のシュウ酸
、クエン酸の混合溶液に添加すると、白色状の懸濁液と
なつて水和酸化チタン〜シュウ酸〜クエン酸の反応縮合
物の微粒子が析出する。更に９５℃で２時間維持した後
、▲ろ▼過し、純水で▲ろ▼液がｐＨ５．０になるまで
水洗し、水和酸化チタン〜シュウ酸〜クエン酸の反応縮
合物の水湿ケーキを得る。この水湿ケーキを純水に懸濁
して１０．０ｌとし、撹拌しつつ９５℃に昇温する。
次いで、水酸化カリウム４．０モルを純水で溶解して５
．０ｌとし、上記懸濁液がｐＨ１２．０になるまで注加
し、更に９５℃で１時間処理した後、▲ろ▼過し、ｐＨ
８．０になるまで純水で水洗する。この水湿ケーキを取
り出し、８０℃で乾燥すると、粉砕を必要としない良好
な粉末となる。これを電子顕微鏡で確認したところ、数
十〜数百Åの球状粒子の集合体で、大きさは０．０５〜
０．５μｍであり、ＢＥＴ法による比表面積の実測値は
１４０ｍ２／ｇと非常に大きな数値であつた。又、Ｘ線
回折分析で確認したところ、六チタン酸カリＫ２Ｔｉ６
Ｏ１３が確認された。Example 4 1.0 mol of oxalic acid and 2.0 mol of citric acid were dissolved in pure water to make 12.0 liters, and the mixture was heated to 95° C. with stirring. Separately, 2.0 mol of titanium tetrachloride was dissolved in pure water and 5.0 mol of titanium tetrachloride was dissolved in pure water.
1, and this is 20ml/min. When added to a mixed solution of oxalic acid and citric acid under stirring, fine particles of a reaction condensate of hydrated titanium oxide, oxalic acid, and citric acid are precipitated as a white suspension. After further maintaining the temperature at 95°C for 2 hours, it was filtered and washed with pure water until the pH of the filtrate reached 5.0. get cake. This wet cake was suspended in pure water to make 10.0 liters, and the temperature was raised to 95° C. while stirring. Next, 4.0 mol of potassium hydroxide was dissolved in pure water to give 5.0 mol of potassium hydroxide.
．． 0 liters, and added the above suspension until the pH reached 12.0. After further treatment at 95°C for 1 hour, ▲filtration, and pH
Wash with pure water until it reaches 8.0. When this wet cake is taken out and dried at 80°C, it becomes a good powder that does not require pulverization. When this was confirmed using an electron microscope, it was found to be an aggregate of spherical particles of several tens to hundreds of angstroms, with sizes ranging from 0.05 to several hundred angstroms.
The specific surface area was 0.5 μm, and the actual value of the specific surface area measured by the BET method was 140 m 2 /g, which was a very large value. In addition, as confirmed by X-ray diffraction analysis, potassium hexatitanate K2Ti6
O13 was confirmed.
【００１３】[0013]
【発明の効果】本発明の微粒子チタン酸アルカリは多孔
質ゼオライト微粒子と同程度の比表面積を有し、従来の
繊維状チタン酸アルカリに比べ、表面は非常に活性であ
り、且つ、高温及び（又は）、高圧の合成条件を必要と
しないため、製造方法は非常に経済的である。Effects of the Invention The fine particle alkali titanate of the present invention has a specific surface area comparable to that of porous zeolite fine particles, and has a very active surface compared to the conventional fibrous alkali titanate. or), the production method is very economical as it does not require high pressure synthesis conditions.
【図１】実施例３で得られた本発明の微粒子チタン酸ア
ルカリの形状を示す電子顕微鏡写真のトレース図であり
、倍率は６０，０００倍である。FIG. 1 is a trace diagram of an electron micrograph showing the shape of the fine particle alkali titanate of the present invention obtained in Example 3, and the magnification is 60,000 times.
【図２】実施例３によつて得た六チタン酸カリＫ２Ｔｉ
６Ｏ１３のＸ線回折分析図である。[Figure 2] Potassium hexatitanate K2Ti obtained in Example 3
It is an X-ray diffraction analysis diagram of 6O13.
Claims (2)
、比表面積が１００ｍ２／ｇ以上である微粒子チタン酸
アルカリ粉末。Claim 1: Particle size is 0.01 to 0.5 μm
, a fine particle alkali titanate powder having a specific surface area of 100 m2/g or more.
酸の一種又は、二種以上を溶解した５０℃以上の水溶液
系に四塩化チタンの水溶液を注加し、生成する水和酸化
チタン〜有機酸の反応縮合物を▲ろ▼過、水洗し、次い
で、この水懸濁液に水酸化アルカリ金属を添加し、ｐＨ
８以上、５０℃以上の温度にて、反応せしめた後、▲ろ
▼過、水洗、乾燥することを特徴とする第１項記載の微
粒子チタン酸アルカリ粉末の製造法。Claim 2: Hydrated titanium oxide produced by pouring an aqueous solution of titanium tetrachloride into an aqueous solution system at 50°C or higher in which one or more dibasic or tribasic organic carboxylic acids are dissolved. The reaction condensate of organic acids is filtered and washed with water, and then alkali metal hydroxide is added to this aqueous suspension to adjust the pH.
8. The method for producing fine-particle alkali titanate powder according to item 1, which comprises reacting at a temperature of 8° C. or higher and 50° C. or higher, followed by ▲filtration, washing with water, and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12567491A JPH04280815A (en) | 1991-03-06 | 1991-03-06 | Fine particulate alkali titanate and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12567491A JPH04280815A (en) | 1991-03-06 | 1991-03-06 | Fine particulate alkali titanate and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04280815A true JPH04280815A (en) | 1992-10-06 |
Family
ID=14915856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12567491A Pending JPH04280815A (en) | 1991-03-06 | 1991-03-06 | Fine particulate alkali titanate and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04280815A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0611039A1 (en) * | 1993-02-10 | 1994-08-17 | Tioxide Specialties Limited | Preparation of titanium dioxide |
| EP1036766A1 (en) * | 1999-03-08 | 2000-09-20 | Kawatetsu Mining Co., LTD. | Potassium titanate fine particles |
| JP2001019430A (en) * | 1999-07-06 | 2001-01-23 | Kawatetsu Mining Co Ltd | Potassium titanate particles |
| JP2008110918A (en) * | 2008-01-28 | 2008-05-15 | Jfe Mineral Co Ltd | Nonfibrous potassium titanate |
| JP2009184921A (en) * | 2009-05-25 | 2009-08-20 | Jfe Mineral Co Ltd | Potassium octatitanate particle |
| JP2011256255A (en) * | 2010-06-08 | 2011-12-22 | Akebono Brake Ind Co Ltd | Friction material and granule for friction material |
| WO2014148374A1 (en) | 2013-03-18 | 2014-09-25 | 東邦チタニウム株式会社 | Method for producing potassium titanate |
-
1991
- 1991-03-06 JP JP12567491A patent/JPH04280815A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0611039A1 (en) * | 1993-02-10 | 1994-08-17 | Tioxide Specialties Limited | Preparation of titanium dioxide |
| US5456899A (en) * | 1993-02-10 | 1995-10-10 | Tioxide Specialties Limited | Preparation of titanium dioxide |
| EP1036766A1 (en) * | 1999-03-08 | 2000-09-20 | Kawatetsu Mining Co., LTD. | Potassium titanate fine particles |
| JP2001019430A (en) * | 1999-07-06 | 2001-01-23 | Kawatetsu Mining Co Ltd | Potassium titanate particles |
| JP2008110918A (en) * | 2008-01-28 | 2008-05-15 | Jfe Mineral Co Ltd | Nonfibrous potassium titanate |
| JP2009184921A (en) * | 2009-05-25 | 2009-08-20 | Jfe Mineral Co Ltd | Potassium octatitanate particle |
| JP2011256255A (en) * | 2010-06-08 | 2011-12-22 | Akebono Brake Ind Co Ltd | Friction material and granule for friction material |
| WO2014148374A1 (en) | 2013-03-18 | 2014-09-25 | 東邦チタニウム株式会社 | Method for producing potassium titanate |
| KR20150127110A (en) | 2013-03-18 | 2015-11-16 | 도호 티타늄 가부시키가이샤 | Method for producing potassium titanate |
| US9796598B2 (en) | 2013-03-18 | 2017-10-24 | Toho Titanium Co., Ltd. | Method for producing potassium titanate |
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