JPS62260708A - Production of high purity hydroxyapatite - Google Patents
Production of high purity hydroxyapatiteInfo
- Publication number
- JPS62260708A JPS62260708A JP9828886A JP9828886A JPS62260708A JP S62260708 A JPS62260708 A JP S62260708A JP 9828886 A JP9828886 A JP 9828886A JP 9828886 A JP9828886 A JP 9828886A JP S62260708 A JPS62260708 A JP S62260708A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- phosphoric acid
- reaction vessel
- hydroxyapatite
- heavy metals
- 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
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 12
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 229940043430 calcium compound Drugs 0.000 claims abstract description 7
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 229940085991 phosphate ion Drugs 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims 1
- 229940023913 cation exchange resins Drugs 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003456 ion exchange resin Substances 0.000 abstract description 7
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 7
- -1 phosphoric acid ion Chemical class 0.000 abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 3
- 150000003016 phosphoric acids Chemical class 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 16
- 229910052586 apatite Inorganic materials 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002367 phosphate rock Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000392 octacalcium phosphate Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、人工骨、人工歯根等のバイオセラミックスの
111=)として用いうるヒドロキシアパタイト(Ca
、、、(OH)、(PO4)6、以下単にアパタイトと
いう)を製造する方法に関するものでりろ。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to hydroxyapatite (Ca
, (OH), (PO4)6 (hereinafter simply referred to as apatite).
従来、バイオセラミックスの’INNとなるアパタイト
2製欲する方法としては、乾式法と湿式法とがあるが、
いずれの方法においてもアパタイト’r’M造する際の
リン源として1riあるや1のリン酸塩が使用されてい
る。そして、このリン酸塩中には、リンi浚製造用原料
であるリン鉱石に由来する重金属、或いはリン酸等の製
造工程で混入してくる重金属が含有されてお9、アパタ
イトの生成反応の過程において、リン酸塩中に含有され
ている重金属例えばFe、Cd又はPbなどがCaと喧
換されアパタイト構造中に入り込み、生体材料としては
好ましくない。Conventionally, there are two methods for producing apatite 2, which is the 'INN' of bioceramics: a dry method and a wet method.
In either method, every 1 ri of phosphate is used as a phosphorus source when producing apatite 'r'M. This phosphate contains heavy metals derived from phosphate rock, which is the raw material for phosphorus i dredging, or heavy metals mixed in during the manufacturing process of phosphoric acid, etc. 9 In the process, heavy metals such as Fe, Cd, or Pb contained in the phosphate are mixed with Ca and enter the apatite structure, making it undesirable as a biomaterial.
そして、従来アパタイト製造後ンて洗浄等にょり純化す
る方法が試みられているが、重金属の除去法としては十
分なものではなかった。Conventionally, attempts have been made to purify apatite by washing or other methods after manufacturing it, but these methods have not been sufficient to remove heavy metals.
本発明は、不純物特に重金属含有量の極めて少ないアパ
タイトの製造方法を提供することを目的とするう
〔発明の構成〕
本発明は、重金61を含有しないリン酸イオン含有夜中
のリン酸イオンを、pH6以上でカルシウム化合物と反
応させることにより高純度アノ(タイ)1製1告する方
?去でちる。An object of the present invention is to provide a method for producing apatite with an extremely low content of impurities, particularly heavy metals. High purity Ano (Thailand) 1 made by reacting with calcium compounds at pH 6 or higher? I'm leaving.
本発明者らは重金属その他の不純物含有量の少ない高純
度アパタイトの製法について鋭意研究した結果、重合慎
を除去したリン酸イオン含有夜中のリン酸イオンとカル
シウム化合物とを反応させることにより重金属を含有し
ていない高純度のアパタイト?製造しうろことを見いだ
した。The inventors of the present invention have conducted extensive research on the production method of high-purity apatite with low content of heavy metals and other impurities. As a result, we have found that by reacting phosphate ions containing phosphate ions from which polymerization particles have been removed with calcium compounds, heavy metals can be produced. Not high purity apatite? I found a manufacturing scale.
前記重金属イオンを含有していないり/駿イオン含有液
は、各種の水溶性リン化合物を、強酸性イオン交換、樹
脂、ヒドロキシアパタイトを含有する固体、その他の重
金(1イオンを吸着する性f″11分有吸着剤等で従触
処理することにより容易に得ることができる。The heavy metal ion-free/Shun ion-containing liquid can be used to exchange various water-soluble phosphorus compounds with strong acid ion exchange, resin, solid containing hydroxyapatite, and other heavy metals (with the ability to adsorb one ion). It can be easily obtained by contact treatment with a 11-minute adsorbent or the like.
つぎに、第1図に基いて本発明を説明する。Next, the present invention will be explained based on FIG.
反応容器6に細氷導管10より純水を仕込んだ後、液中
のリン酸イオン1度が所定の濃度になるように、リン酸
塩溶液導入管1からリン酸塩溶液を強酸性イオン交換樹
脂塔2を通過せしめて重金属イオンを除去した後反応容
器6に供給する、
ついでCa塩水溶液導入管4及びアルカリ水溶夜導入管
5から所定量のCa塩水溶夜及びアルカリ水溶液を添加
し、攪拌機7で攪拌しながら反応さする。。After charging pure water into the reaction vessel 6 through the thin ice conduit 10, the phosphate solution is subjected to strong acid ion exchange through the phosphate solution introduction tube 1 so that the phosphate ions in the liquid reach a predetermined concentration. After passing through the resin tower 2 to remove heavy metal ions, the resin is supplied to the reaction vessel 6. Next, predetermined amounts of Ca salt aqueous solution and alkali aqueous solution are added from the Ca salt aqueous solution introduction tube 4 and the alkali aqueous solution introduction tube 5, and 7. React while stirring. .
生成した反応生成物(アパタイト)は反応容器中を沈降
し、生成物排出管8よりアパタイト製品が得られろ。The generated reaction product (apatite) settles in the reaction vessel, and an apatite product is obtained from the product discharge pipe 8.
第1図は回分式装置を示すものであるが、第2図に示す
如き連続反応装置を使用してアパタイトを製造すること
も出来る。Although FIG. 1 shows a batch-type reactor, apatite can also be produced using a continuous reactor as shown in FIG.
即ち、リン酸塩溶液導入管1から供給されるリン酸塩溶
液を強酸性イオン交換樹脂塔2に通過せしめ重金属イオ
ンを除去した後、管10を経て供給される純水及び管4
から供給されるCa化合物溶液と所定の割合で混合した
後流動反応槽6′の底部に供給し、撹拌器7で攪拌しな
がら反応させるっ 一方、反応液のpHを調整するため
に管5からアルカリ溶液が反応液中に供給される。That is, the phosphate solution supplied from the phosphate solution introduction tube 1 is passed through the strongly acidic ion exchange resin tower 2 to remove heavy metal ions, and then the pure water and tube 4 are supplied through the tube 10.
After mixing with the Ca compound solution supplied from An alkaline solution is fed into the reaction solution.
反応生成物は反応物排出管8から連続的に抜き出される
1、リン源としてはHaPo4. Na5PO,。The reaction product is continuously extracted from the reactant discharge pipe 8, and HaPo4 is used as the phosphorus source. Na5PO,.
K7 HP 04 、 NH4H,PO2などを使用し
うる。K7 HP 04 , NH4H, PO2, etc. can be used.
反応容器中におけるリンイオン濃度は500〜2000
ppmの範囲のものが好ましいが、強酸性イオン交換
樹脂の効率を向上せしめるため、高a度のリン酸@孜と
して強酸性イオン交換樹脂14に通した汝、純水と混合
して前記ジ度となるようにするO′つ:好ましい。強酸
性イオン交換園哨′φ臀′こ・市すリン酸イオン溶夜中
のリン酸イオン4度は[1,5〜1.4%の範囲の濃度
のものが好ましい。The phosphorus ion concentration in the reaction vessel is 500-2000
ppm range is preferred, but in order to improve the efficiency of the strongly acidic ion exchange resin, high a degree phosphoric acid may be passed through the strongly acidic ion exchange resin 14 and mixed with pure water. O': Preferable. The concentration of phosphate ions in the strongly acidic ion exchange solution is preferably in the range of 1.5 to 1.4%.
また、Ca化合物はCa2+とじてt o 〜s、 o
%の範囲の濃度のものを用いるのが好ましく、反応は
常温〜100℃の範囲内の温度で行うのが好ましい。In addition, Ca compounds are t o ~ s, o as Ca2+
%, and the reaction is preferably carried out at a temperature within the range of room temperature to 100°C.
重金属を含有するリン酸イオン含有液を強酸性イオン交
換樹脂と接触させる場合、夜中の重金属イオンが交換除
去され、液中に水素イオンが放出される。このことによ
り、アパタイトになりきれないリン酸8カルシウムの溶
解を促進し、アパタイトの熟成化を進もうる。When a phosphate ion-containing liquid containing heavy metals is brought into contact with a strongly acidic ion exchange resin, the heavy metal ions are exchanged and removed during the night, and hydrogen ions are released into the liquid. This promotes the dissolution of octacalcium phosphate that cannot be converted into apatite, and promotes the ripening of apatite.
また、ヒドロキシアパタイトを含有する固体、例えばリ
ン鉱石や骨炭を充填した層を通過させる場合には、リン
酸イオン含有液中の重金属イオン類はヒドロキシアパタ
イト層に吸着固定され、Oa”+イオンが放出される。In addition, when passing through a layer filled with solids containing hydroxyapatite, such as phosphate rock or bone char, heavy metal ions in the phosphate ion-containing liquid are adsorbed and fixed on the hydroxyapatite layer, and Oa''+ ions are released. be done.
Ca 源としては、CaC/2、アルカリ源としては
NaOHが使用でき、また、Ca源としては、重金属を
含有していない消石灰?用いても:い。CaC/2 can be used as a Ca source, NaOH can be used as an alkali source, and slaked lime, which does not contain heavy metals, can be used as a Ca source. Even if you use it: No.
用水としては、水道水も使用できるが、高純度の製品を
得るためには、純水又は超純水を使用するのが好ましい
。Although tap water can be used as water, it is preferable to use pure water or ultrapure water in order to obtain a highly purified product.
つぎに、本発明の実施例並びに比較例を記載するっ
実施例1
aOtの開放容器に純水50/を張り込み、該容器内に
NH,H,PO,の3〜4チ純水溶液を8717時で強
酸性イオン交換樹脂層(Dowec HGR−W、 、
I A〜40メツシュ)を通過させた後導入し、Pと
して1000η/lの濃度の溶液を調整した。次K 0
aC12の7%純水溶液を加えCa9度2200〜/l
とした後NaOH1チ純水溶液でpHを&5とし80m
φX40mの2枚羽根で15 Or、p、mの速度で攪
拌した。Next, Examples and Comparative Examples of the present invention will be described. A strongly acidic ion exchange resin layer (Dowec HGR-W,
After passing through IA~40 mesh), a solution with a P concentration of 1000 η/l was prepared. Next K 0
Add 7% pure aqueous solution of aC12 to Ca9 degree 2200~/l
After that, the pH was adjusted to &5 with 1 H pure water solution of NaOH and the pH was adjusted to 80 m
Stirring was carried out at a speed of 15 Or, p, m using two blades of φX40 m.
生成した沈殿を分離し、N2雰囲気下に100℃で乾燥
し、製品の組成を分析した。The formed precipitate was separated and dried at 100° C. under N2 atmosphere, and the composition of the product was analyzed.
なお、比較のため、リン化合物としてNlk&Po。For comparison, Nlk&Po is used as a phosphorus compound.
(比較例1)及びH,PO,(比較例2)を用い、イオ
ン交換樹脂による処理を行なわなかった以外は、実施例
1と同様にアパタイトを製造し組成を分析した。(Comparative Example 1) and H, PO, (Comparative Example 2), apatite was produced in the same manner as in Example 1, except that the treatment with the ion exchange resin was not performed, and the composition was analyzed.
結果を表−1に示す。The results are shown in Table-1.
表−1
実施例2
NH,H,PO,溶液をsv 17時で、北アフリカ
産リン鉱石(有効径0.4.5 rm )に流過させた
以外は、実施例1と同様の操作を行なったところ、表−
1と同等の製品が得られた。Table-1 Example 2 The same operation as in Example 1 was carried out, except that the NH, H, PO, solution was passed through North African phosphate rock (effective diameter 0.4.5 rm) at sv 17:00. When I did it, the table-
A product equivalent to 1 was obtained.
第1図はバッチ方式で本発明のアパタイトを製造する方
法を説明するための装置の概略フロー図、第2図は連続
的に製造する方法を説明するだめの装置の概略フロー図
である。
1・・・・リン化合物溶液供給管、2−・・イオン交換
塔、4−カルシウム化合物溶液供給管、5−アルカリ溶
液供給管、6 、6’−・・反応容器、7−攪拌機、8
−・・生成物排出管FIG. 1 is a schematic flow diagram of an apparatus for explaining a method for producing apatite of the present invention in a batch manner, and FIG. 2 is a schematic flow diagram for a second apparatus for explaining a method for producing apatite continuously. 1... Phosphorus compound solution supply pipe, 2-... Ion exchange tower, 4- Calcium compound solution supply pipe, 5- Alkaline solution supply pipe, 6, 6'-... Reaction vessel, 7- Stirrer, 8
−・Product discharge pipe
Claims (1)
以上でカルシウム化合物と反応させることにより純度ヒ
ドロキシアパタイトの製造する方法において、リン酸イ
オン含有液を、重金属イオンの除去能力を有する固体粒
子層を通過せしめて重金属を除去した後カルシウム化合
物と反応させることを特徴とする高純度ヒドロキシアパ
タイトの製造方法。 2、重金属イオンの除去能力を有する固体粒子が強酸性
陽イオン交換樹脂である特許請求の範囲記載の高純度ヒ
ドロキシアパタイトの製造方法。 3、重金属イオンの除去能力を有する固体粒子が、ヒド
ロキシアパタイトを含有する固体粒子である特許請求の
範囲記載の高純度ヒドロキシアパタイトの製造方法。[Claims] 1. The phosphate ions in the phosphate ion-containing solution are adjusted to pH 6.
In the above method for producing pure hydroxyapatite by reacting with a calcium compound, the phosphate ion-containing solution is passed through a solid particle layer having the ability to remove heavy metal ions to remove heavy metals, and then reacted with a calcium compound. A method for producing high-purity hydroxyapatite, characterized by: 2. The method for producing high-purity hydroxyapatite according to the claims, wherein the solid particles having the ability to remove heavy metal ions are strongly acidic cation exchange resins. 3. The method for producing high-purity hydroxyapatite according to the claims, wherein the solid particles having the ability to remove heavy metal ions are solid particles containing hydroxyapatite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9828886A JPS62260708A (en) | 1986-04-30 | 1986-04-30 | Production of high purity hydroxyapatite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9828886A JPS62260708A (en) | 1986-04-30 | 1986-04-30 | Production of high purity hydroxyapatite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62260708A true JPS62260708A (en) | 1987-11-13 |
Family
ID=14215738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9828886A Pending JPS62260708A (en) | 1986-04-30 | 1986-04-30 | Production of high purity hydroxyapatite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62260708A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01218579A (en) * | 1988-02-25 | 1989-08-31 | Sekisui Plastics Co Ltd | Decoloring agent for whisky |
| US6000341A (en) * | 1989-05-24 | 1999-12-14 | American Dental Association Health Foundation | Methods and composition for mineralizing and fluoridating calcified tissues |
| US6056930A (en) * | 1989-05-24 | 2000-05-02 | American Dental Association Health Foundation | Methods and compositions for mineralizing and fluoridating calcified tissues |
| CN1077454C (en) * | 1997-06-06 | 2002-01-09 | 武汉化工学院 | Technology of activating carbon-fluorine apatite to remove toxic metal ions from waste water |
| WO2003072496A1 (en) * | 2002-02-26 | 2003-09-04 | Hyun-Man Kim | Calcium phosphate colloids, dots, islands, thin films or granules and its preparation |
| CN103754851A (en) * | 2014-01-08 | 2014-04-30 | 瓮福(集团)有限责任公司 | Preparation method of battery grade crystal ammonium dihydrogen phosphate |
| JP2014177399A (en) * | 2014-04-28 | 2014-09-25 | Asahi Kasei Chemicals Corp | Recovery phosphorus |
| JP2022150640A (en) * | 2021-03-26 | 2022-10-07 | 株式会社北匠 | Method for producing phosphorus compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55167114A (en) * | 1979-06-16 | 1980-12-26 | Mitsubishi Mining & Cement Co Ltd | Manufacture of hydroxyapatite |
| JPS5645814A (en) * | 1979-09-25 | 1981-04-25 | Kureha Chem Ind Co Ltd | Hydroxyapatite, its ceramic material and its manufacture |
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1986
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| JPS55167114A (en) * | 1979-06-16 | 1980-12-26 | Mitsubishi Mining & Cement Co Ltd | Manufacture of hydroxyapatite |
| JPS5645814A (en) * | 1979-09-25 | 1981-04-25 | Kureha Chem Ind Co Ltd | Hydroxyapatite, its ceramic material and its manufacture |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01218579A (en) * | 1988-02-25 | 1989-08-31 | Sekisui Plastics Co Ltd | Decoloring agent for whisky |
| US6000341A (en) * | 1989-05-24 | 1999-12-14 | American Dental Association Health Foundation | Methods and composition for mineralizing and fluoridating calcified tissues |
| US6056930A (en) * | 1989-05-24 | 2000-05-02 | American Dental Association Health Foundation | Methods and compositions for mineralizing and fluoridating calcified tissues |
| CN1077454C (en) * | 1997-06-06 | 2002-01-09 | 武汉化工学院 | Technology of activating carbon-fluorine apatite to remove toxic metal ions from waste water |
| WO2003072496A1 (en) * | 2002-02-26 | 2003-09-04 | Hyun-Man Kim | Calcium phosphate colloids, dots, islands, thin films or granules and its preparation |
| JP2005518327A (en) * | 2002-02-26 | 2005-06-23 | キム,ヒュン−マン | Calcium phosphate colloids, dots, islands, thin films or granules, and their preparation |
| CN103754851A (en) * | 2014-01-08 | 2014-04-30 | 瓮福(集团)有限责任公司 | Preparation method of battery grade crystal ammonium dihydrogen phosphate |
| JP2014177399A (en) * | 2014-04-28 | 2014-09-25 | Asahi Kasei Chemicals Corp | Recovery phosphorus |
| JP2022150640A (en) * | 2021-03-26 | 2022-10-07 | 株式会社北匠 | Method for producing phosphorus compound |
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