JP2007296463A - Hydroxyapatite silica composite porous adsorbent and its manufacturing method - Google Patents
Hydroxyapatite silica composite porous adsorbent and its manufacturing method Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 100
- 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 100
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000003463 adsorbent Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000011575 calcium Substances 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000378 calcium silicate Substances 0.000 claims abstract description 63
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 63
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 50
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 41
- -1 calcium silicate compound Chemical class 0.000 claims abstract description 29
- 230000035699 permeability Effects 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims description 46
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 37
- 239000011148 porous material Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- 102000004169 proteins and genes Human genes 0.000 abstract description 7
- 108090000623 proteins and genes Proteins 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001027 hydrothermal synthesis Methods 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 9
- 239000000920 calcium hydroxide Substances 0.000 description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 9
- 235000011116 calcium hydroxide Nutrition 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 102000018832 Cytochromes Human genes 0.000 description 4
- 108010052832 Cytochromes Proteins 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 3
- 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 3
- 239000000843 powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Abstract
Description
本発明は、ヒドロキシアパタイトシリカ複合多孔質体からなる吸着剤であって、例えば重金属や蛋白質に対して高い吸着性を有し、かつ複合多孔質体が水に溶解し難く優れた耐水性と透水性を有する吸着剤とその製造方法に関する。 The present invention is an adsorbent comprising a hydroxyapatite silica composite porous body, and has high water resistance and water permeability, for example, having high adsorptivity to heavy metals and proteins, and the composite porous body is difficult to dissolve in water. The present invention relates to an adsorbent having a property and a production method thereof.
ヒドロキシアパタイト〔Ｃａ10(ＰＯ4)6(ＯＨ)2〕はそのカルシウムイオンとの置換により、例えばカドミウムや水銀あるいは鉛などの有害重金属に対して吸着能を持つことはよく知られている（非特許文献１）。しかし、ヒドロキシアパタイトは結晶性が高いとそのカルシウムイオンの溶出が効率的でなく、重金属に対する吸着能を十分に活かし得ないという問題もあった。 It is well known that hydroxyapatite [Ca 10 (PO 4 ) 6 (OH) 2 ] has an ability to adsorb toxic heavy metals such as cadmium, mercury or lead by substitution with calcium ions (non-non-crystalline). Patent Document 1). However, when hydroxyapatite has high crystallinity, the elution of calcium ions is not efficient, and there is a problem that the adsorption ability for heavy metals cannot be fully utilized.
このような欠点を改善したものとして、多数の細孔を有する多孔質基材にヒドロキシアパタイトを含有させて吸着表面積を増加させ、また非晶質のヒドロキシアパタイトを用いることによってカルシウムイオンの溶出を促し、重金属に対する吸着能を高めようとしたものがある（特許文献１参照）。なお、結晶質アパタイトよりも非晶質アパタイトのほうがカドミウムイオンの取り込み量が多いことが従来から報告されている（非特許文献２）。 As a solution to these disadvantages, hydroxyapatite is added to a porous substrate having a large number of pores to increase the adsorption surface area, and by using amorphous hydroxyapatite, elution of calcium ions is promoted. Some have attempted to increase the adsorption capacity for heavy metals (see Patent Document 1). In addition, it has been conventionally reported that amorphous apatite has a larger amount of cadmium ion incorporation than crystalline apatite (Non-patent Document 2).
しかし、この吸着剤を浄水器などに用いる場合、水に対して吸着剤の溶解度が高いと多量の水を処理する間に吸着剤が溶解して消失すると云う問題が生じる。例えば、ヒドロキシアパタイトの水に対する溶解度が１０mg/lの場合、水を１０ｍ3処理する間に１００ｇの吸着剤は溶解してしまい、実用に適さない。このように、実用に適う吸着剤としては重金属に対する吸着能が高いだけでなく、水に対する溶解度が低いことが要求される。一般に非晶質のものは結晶質のものに比べて溶解度が高いので、非晶質ヒドロキシアパタイトは不都合である。 However, when this adsorbent is used in a water purifier or the like, if the solubility of the adsorbent in water is high, there arises a problem that the adsorbent dissolves and disappears during the treatment of a large amount of water. For example, when the solubility of hydroxyapatite in water is 10 mg / l, 100 g of the adsorbent dissolves during the treatment of 10 m 3 of water, which is not suitable for practical use. Thus, an adsorbent suitable for practical use is required not only to have a high adsorption capacity for heavy metals but also to have a low solubility in water. In general, amorphous hydroxyapatite is inconvenient because amorphous ones have higher solubility than crystalline ones.
次に、ヒドロキシアパタイト系重金属吸着剤を安価に製造する方法として、発泡気泡コンクリート等の廃材をリン酸水溶液中に浸潰し、珪酸カルシウムとリン酸を反応させる方法が提案されている（特許文献２）。しかし、この方法では、コンクリート廃材などの珪酸カルシウム系の基材表面しかアパタイト化されないので、重金属イオンの交換容量が低く、またヒドロシキアパタイトの結晶性が劣るため、水に対する溶解度も高いと云う問題がある。さらに、コンクリート廃材を粉砕して用いると、これをリン酸に浸漬したときに、珪酸カルシウムが分解して微細なシリカが遊離するので、生成したスラリーの濾過性および沈降性が非常に劣るものになり、製造上の問題があるばかりではなく、透水性が劣るので水処理用吸着剤として適しない。 Next, as a method for producing a hydroxyapatite heavy metal adsorbent at a low cost, a method is proposed in which waste materials such as foamed concrete are crushed in a phosphoric acid aqueous solution and calcium silicate and phosphoric acid are reacted (Patent Document 2). ). However, in this method, only the surface of calcium silicate base material such as concrete waste is apatite, so the exchange capacity of heavy metal ions is low, and the crystallinity of Hydroxiapatite is poor, so the solubility in water is also high. There is. Furthermore, when concrete waste is pulverized and used, when it is immersed in phosphoric acid, calcium silicate is decomposed and fine silica is liberated, so the filterability and sedimentation of the resulting slurry is very poor. In addition to manufacturing problems, the water permeability is inferior, making it unsuitable as an adsorbent for water treatment.
このように、従来のヒドロキシアパタイト系吸着剤は吸着性と耐水性、ならびに透水性を同時に満足させるものがなかった。
本発明は、従来のヒドロキシアパタイト系吸着剤における上記問題を解決したものであり、高い吸着性を有し、かつ優れた耐水性と透水性を有するヒドロキシアパタイトシリカ複合多孔質体からなる吸着剤とその製造方法を提供する。 The present invention solves the above-mentioned problems in conventional hydroxyapatite-based adsorbents, and has an adsorbent comprising a hydroxyapatite silica composite porous body having high adsorbability and excellent water resistance and water permeability. A manufacturing method thereof is provided.
本発明は、以下に示す構成によって上記課題を解決したヒドロキシアパタイトシリカ複合体多孔質吸着剤とその製造方法に関する。
（１）結晶質ヒドロキシアパタイトと多孔質シリカとの複合体からなることを特徴とするヒドロキシアパタイトシリカ複合多孔質体吸着剤。
（２）ヒドロキシアパタイトとシリカの複合体からなり、全細孔容積０.５ml/g以上の多孔質体であり、リン溶解度が３.５ppm以下の低溶解性であることを特徴とするヒドロキシアパタイトシリカ複合多孔質体吸着剤。
（３）透水率が１〜１００×１０-4cm/sである上記(１)または上記(２)に記載するヒドロキシアパタイトシリカ複合多孔質体吸着剤。
（４） 平均粒径１０〜６０μmであって、ＢＥＴ比表面積１００m2/g以上である上記(１)〜上記(３)の何れかに記載するヒドロキシアパタイトシリカ複合多孔質体吸着剤。
（５）ヒドロキシアパタイトのカルシウムとリンのモル比（Ｃａ/Ｐ）が１.９未満である上記(１)〜上記(４)の何れかに記載するヒドロキシアパタイトシリカ複合多孔質体吸着剤。
（６）カルシウムとシリカのモル比（Ｃａ/Ｓｉ）が０.１〜０.８である珪酸カルシウム化合物を原料とする上記(１)〜上記(５)の何れかに記載するヒドロキシアパタイトシリカ複合多孔質体吸着剤。
（７）珪酸カルシウム化合物にリン酸を反応させて、カルシウム分を結晶質ヒドロキシアパタイトに転化させると共に、シリカ分を多孔質シリカに転化させることを特徴とするヒドロキシアパタイトシリカ複合多孔質体の製造方法。
（８）珪酸カルシウム化合物に、ＰＨ７.０以上になるようにリン酸を徐々に添加し反応させて結晶質ヒドロキシアパタイトと多孔質シリカの複合体を製造する上記(７)に記載する製造方法。
（９）珪酸カルシウム化合物にまず酸を反応させて珪酸カルシウム化合物のカルシウムを部分的に溶解除去し、次いでリン酸を反応させて結晶質ヒドロキシアパタイトを生成させてヒドロキシアパタイトシリカ複合多孔質体を製造する上記(７)または上記(８)に記載する製造方法。
（１０）珪酸カルシウムスラリーにリン酸を添加し、このときカルシウムとリンのモル比(Ｃａ/Ｐ)が１.９未満になるリン酸量とし、スラリーを撹拌しながらリン酸を徐々に添加して反応させ、ヒドロキシアパタイトシリカ複合多孔質体を製造する上記(７)〜上記(９)の何れかに記載する製造方法。
（１１）珪酸カルシウム化合物を温水に浸漬し、加温下でリン酸を添加し、このときカルシウムとリンのモル比(Ｃａ/Ｐ)が１.９未満になるリン酸量とし、温水を撹拌しながらリン酸を徐々に添加して反応させ、ヒドロキシアパタイトシリカ複合多孔質体を製造する上記(７)〜上記(９)の何れかに記載する製造方法。
The present invention relates to a hydroxyapatite silica composite porous adsorbent and a method for producing the same, which have solved the above-described problems with the following configuration.
(1) A hydroxyapatite silica composite porous material adsorbent comprising a composite of crystalline hydroxyapatite and porous silica.
(2) A hydroxyapatite comprising a composite of hydroxyapatite and silica, a porous body having a total pore volume of 0.5 ml / g or more, and low solubility with a phosphorus solubility of 3.5 ppm or less Silica composite porous material adsorbent.
(3) The hydroxyapatite silica composite porous material adsorbent described in the above (1) or (2) having a water permeability of 1 to 100 × 10 −4 cm / s.
(4) The hydroxyapatite silica composite porous material adsorbent according to any one of (1) to (3), which has an average particle size of 10 to 60 μm and a BET specific surface area of 100 m 2 / g or more.
(5) The hydroxyapatite silica composite porous material adsorbent according to any one of (1) to (4) above, wherein the molar ratio of calcium to phosphorus (Ca / P) of hydroxyapatite is less than 1.9.
(6) The hydroxyapatite silica composite as described in any one of (1) to (5) above, wherein a calcium silicate compound having a calcium to silica molar ratio (Ca / Si) of 0.1 to 0.8 is used as a raw material Porous material adsorbent.
(7) A method for producing a hydroxyapatite-silica composite porous body, wherein phosphoric acid is reacted with a calcium silicate compound to convert the calcium content to crystalline hydroxyapatite and the silica content is converted to porous silica. .
(8) The production method according to the above (7), wherein phosphoric acid is gradually added to the calcium silicate compound so as to have a pH of 7.0 or more and reacted to produce a composite of crystalline hydroxyapatite and porous silica.
(9) Calcium silicate compound is first reacted with acid to partially dissolve and remove calcium of calcium silicate compound, then phosphoric acid is reacted to produce crystalline hydroxyapatite to produce a hydroxyapatite silica composite porous body The production method according to (7) or (8) above.
(10) Phosphoric acid is added to the calcium silicate slurry. At this time, the phosphoric acid amount is such that the molar ratio of calcium to phosphorus (Ca / P) is less than 1.9, and phosphoric acid is gradually added while stirring the slurry. The production method according to any one of the above (7) to (9), wherein a hydroxyapatite silica composite porous body is produced by reacting with each other.
(11) Immerse the calcium silicate compound in warm water and add phosphoric acid under heating. At this time, adjust the amount of phosphoric acid so that the molar ratio of calcium to phosphorus (Ca / P) is less than 1.9, and stir the warm water. The production method according to any one of (7) to (9) above, wherein phosphoric acid is gradually added and reacted to produce a hydroxyapatite silica composite porous body.
本発明の吸着剤は、結晶質ヒドロキシアパタイトと多孔質シリカとの複合体からなるヒドロキシアパタイトシリカ複合多孔質体吸着剤であるので、非晶質ヒドロキシアパタイトに比べて水に対して溶解し難く、耐水性に優れる。また、高多孔質体であって透水性が良いので、優れた吸着性を有する。 Since the adsorbent of the present invention is a hydroxyapatite silica composite porous adsorbent composed of a composite of crystalline hydroxyapatite and porous silica, it is less soluble in water than amorphous hydroxyapatite, Excellent water resistance. Moreover, since it is a highly porous body and has good water permeability, it has excellent adsorptivity.
本発明の吸着剤は、好ましくは、例えば、全細孔容積０.５ml/g以上の多孔質体であるので優れた吸着性を有し、かつリン溶解度が３.５ppm以下の低溶解性であるので耐水性に優れている。また、本発明の吸着剤は、例えば、平均粒径１０〜６０μmの適度な粒子径を有しながらＢＥＴ比表面積１００m2/g以上の大きな比表面積を有するので、優れた吸着性と共に高い透水性を有しており、具体的には例えば、透水率が１〜１００×１０-4cm/sであるので目詰りを生じ難く、長時間安定に使用することができる。 The adsorbent of the present invention is preferably a porous body having a total pore volume of 0.5 ml / g or more, for example, and thus has excellent adsorptivity and low solubility with a phosphorus solubility of 3.5 ppm or less. It has excellent water resistance. The adsorbent of the present invention has a large specific surface area of BET specific surface area of 100 m 2 / g or more while having an appropriate particle diameter of, for example, an average particle diameter of 10 to 60 μm. Specifically, for example, since the water permeability is 1 to 100 × 10 −4 cm / s, clogging hardly occurs, and it can be used stably for a long time.
また、本発明のヒドロキシアパタイトシリカ複合体は多孔質であるので、水との接触面積が大きく、吸着速度が非常に速く、重金属除去用水処理剤として用いた場合、回分方式では処理時間を短くすることができ、カラム方式ではＳＶ（空塔速度）を上げることができる。具体的には、本発明における多孔質複合体の吸着速度は、従来のヒドロキシアパタイト等に比べると、飽和吸着量までに達する時間が非常に短く、２０分程度で一定値に達する。また、重金属だけでなく、蛋白質の吸着量も従来のヒドロキシアパタイトに比べて数倍程度高い値を示す。 Further, since the hydroxyapatite silica composite of the present invention is porous, the contact area with water is large, the adsorption rate is very fast, and when used as a water treatment agent for heavy metal removal, the batch method shortens the treatment time. In the column system, SV (superficial velocity) can be increased. Specifically, the adsorption rate of the porous composite in the present invention is much shorter than the conventional hydroxyapatite and the like until reaching the saturated adsorption amount, and reaches a constant value in about 20 minutes. In addition to heavy metals, the amount of protein adsorbed is several times higher than that of conventional hydroxyapatite.
さらに、本発明のヒドロキシアパタイトシリカ複合体は多孔質体であるので、上記平均粒径の範囲でありながらＢＥＴ比表面積１００m2/g以上の大きな比表面積を有することができ、従って、長時間、目詰りを生じることなく、高い吸着性能を維持することができる。 Furthermore, since the hydroxyapatite silica composite of the present invention is a porous body, it can have a large specific surface area of BET specific surface area of 100 m 2 / g or more while being in the above average particle diameter range. High adsorption performance can be maintained without causing clogging.
本発明のヒドロキシアパタイトシリカ複合多孔質体は、珪酸カルシウム化合物にリン酸を反応させて、カルシウム分を結晶質ヒドロキシアパタイトに転化させると共に、シリカ分を多孔質シリカに転化させることによって製造することができる。この製造方法によれば、結晶性が高い多孔質のヒドロキシアパタイトシリカ複合体を製造することができる。 The hydroxyapatite silica composite porous body of the present invention can be produced by reacting a calcium silicate compound with phosphoric acid to convert the calcium content to crystalline hydroxyapatite and to convert the silica content to porous silica. it can. According to this production method, a porous hydroxyapatite silica composite having high crystallinity can be produced.
以下、本発明について最良の実施形態と共に具体的に説明する。
本発明の吸着剤は、結晶質ヒドロキシアパタイトと多孔質シリカとの複合体からなることを特徴とするヒドロキシアパタイトシリカ複合多孔質体吸着剤である。
本発明の吸着剤は、結晶質ヒドロキシアパタイトによる複合体であるので、水に対して溶解性が低く、例えば、リン溶解度が３.５ppm以下、好ましくは１.０ppm以下であるので、耐水性に優れている。
Hereinafter, the present invention will be specifically described together with the best embodiment.
The adsorbent of the present invention is a hydroxyapatite silica composite porous material adsorbent characterized by comprising a composite of crystalline hydroxyapatite and porous silica.
Since the adsorbent of the present invention is a complex of crystalline hydroxyapatite, it has low solubility in water, for example, its phosphorus solubility is 3.5 ppm or less, preferably 1.0 ppm or less, so that it is water resistant. Are better.
本発明のヒドロキシアパタイトシリカ複合体は孔質シリカとの複合体であり、例えば、全細孔容積０.５ml/g以上の多孔質体である。また、本発明のヒドロキシアパタイトシリカ複合体は、例えば、平均粒径１０〜６０μmの適度な粒子径を有し、透水率１〜１００×１０-4cm/s、好ましくは１５×１０-4cm/sの透水率を有するものが好ましい。本発明のヒドロキシアパタイトシリカ複合体は多孔質体であるので、上記平均粒径の範囲でありながらＢＥＴ比表面積１００m2/g以上の大きな比表面積を有することができる。 The hydroxyapatite silica composite of the present invention is a composite with porous silica, for example, a porous body having a total pore volume of 0.5 ml / g or more. Further, the hydroxyapatite silica composite of the present invention has an appropriate particle diameter of, for example, an average particle diameter of 10 to 60 μm, and a water permeability of 1 to 100 × 10 −4 cm / s, preferably 15 × 10 −4 cm. Those having a water permeability of / s are preferred. Since the hydroxyapatite silica composite of the present invention is a porous body, the hydroxyapatite silica composite can have a large specific surface area of BET specific surface area of 100 m 2 / g or more in the above average particle diameter range.
本発明のヒドロキシアパタイトシリカ複合多孔質体は、珪酸カルシウム化合物にリン酸を反応させて、カルシウム分を結晶質ヒドロキシアパタイトに転化させると共にシリカ分を多孔質シリカとして析出させることによって製造することができる。 The hydroxyapatite silica composite porous body of the present invention can be produced by reacting a calcium silicate compound with phosphoric acid to convert the calcium content into crystalline hydroxyapatite and deposit the silica content as porous silica. .
従来の製造方法は、主に多孔質シリカ等の多孔質材料にヒドロキシアパタイトを含浸させ、または析出させる方法であるが、このような従来方法では、基材の表面がヒドロシキアパタイトによって覆われるため、基材が多孔質でもヒドロシキアパタイトの析出によってその多孔性が損なわれてしまう。 The conventional manufacturing method is mainly a method in which a porous material such as porous silica is impregnated with or precipitated with hydroxyapatite. However, in such a conventional method, the surface of the substrate is covered with hydroxyapatite. Even if the substrate is porous, the porosity is impaired by the precipitation of hydroxyapatite.
一方、本発明の製造方法では、ヒドロキシアパタイトの生成と共に多孔質なシリカが生成するので、多孔性を損なうことなく、ヒドロキシアパタイトと多孔質シリカとの複合体が形成される。また、珪酸カルシウム化合物とリン酸との反応方法を工夫することにより、珪酸カルシウム化合物の酸分解により生じる多孔質シリカを、もとの珪酸カルシウム化合物粒子から遊離させず、その粒子表面にヒドロキシアパタイトと同時に析出させることによって、良好な濾過過性、沈降性、透水性を有する複合多孔質体を得ることができる。さらに、本発明の製造方法によって生成するヒドロキシアパタイトは結晶性が良いため、水に対する溶解牲も低いという利点を有する。 On the other hand, in the production method of the present invention, porous silica is generated together with the generation of hydroxyapatite, so that a composite of hydroxyapatite and porous silica is formed without impairing the porosity. In addition, by devising a reaction method between the calcium silicate compound and phosphoric acid, the porous silica generated by acid decomposition of the calcium silicate compound is not released from the original calcium silicate compound particles, and hydroxyapatite and By precipitating at the same time, a composite porous body having good filterability, sedimentation and water permeability can be obtained. Furthermore, since the hydroxyapatite produced by the production method of the present invention has good crystallinity, it has an advantage of low solubility in water.
以下、本発明の製造方法を具体的に説明する。
本発明のヒドロキシアパタイトシリカ複合体の基材となる珪酸カルシウムは、珪酸原料と石灰原料とを水性スラリーとしたものを、例えばオートクレーブ中において水熱反応を行なって合成した一般的によく知られているものを好適に用いることができる。その種類としては、珪酸カルシウム化合物であれば特に限定されず、例えば、トバモライト、ジャイロライト、ゾノトライトなどの結晶質珪酸カルシウム、あるいは非晶質珪酸カルシウムなど何れの珪酸カルシウムを用いることができる。これらは単独で用いても良いし、２種以上を組み合わせて用いても良い。また、これらの珪酸カルシウム化合物は粉体の状態だけではなく、これらの珪酸カルシウム化合物を適当な方法で成型した板状物あるいは塊状物を用いることができる。
Hereinafter, the production method of the present invention will be specifically described.
The calcium silicate used as the base material of the hydroxyapatite silica composite of the present invention is generally well-known that is prepared by hydrothermal reaction in an autoclave, for example, in which an aqueous slurry of a silicate raw material and a lime raw material is used. Can be used suitably. The type is not particularly limited as long as it is a calcium silicate compound. For example, any calcium silicate such as crystalline calcium silicate such as tobermorite, gyrolite, and zonotlite, or amorphous calcium silicate can be used. These may be used alone or in combination of two or more. These calcium silicate compounds can be used not only in the form of powder, but also in the form of plates or lumps obtained by molding these calcium silicate compounds by an appropriate method.
本発明のヒドロキシアパタイトシリカ複合体の基材となる珪酸カルシウムは、カルシウムとシリカのモル比（Ｃａ/Ｓｉ）が０.１〜０.８であるものが好ましく、０.４前後のモル比であるものがより好ましい。カルシウムとシリカのモル比（Ｃａ/Ｓｉ）が上記範囲であるものは、図４に示すように、丸味を帯びた粒子形になり、透水性の良い多孔質複合体を得ることができる。 The calcium silicate used as the base material of the hydroxyapatite silica composite of the present invention preferably has a calcium to silica molar ratio (Ca / Si) of 0.1 to 0.8, and a molar ratio of around 0.4. Some are more preferred. When the molar ratio of calcium to silica (Ca / Si) is in the above range, as shown in FIG. 4, a rounded particle shape is obtained, and a porous composite with good water permeability can be obtained.
次に珪酸カルシウム化合物のヒドロシキアパタイト化を行う。これは水熱反応により生成した珪酸カルシウム化合物のスラリーあるいは成型品を浸漬した水性溶液に、リン酸を添加することによって行うことができる。この場合のリン酸濃度は２〜５０％、好ましくは５〜４０％の範囲がよい。リン酸濃度が２％未満では処理すべき液の量が増大して不都合であり、５０％より高い場合は、局部的な液のｐＨの低下によって微細なヒドロシキアパタイトやシリカ粒子が発生しやすくなるので不都合である。リン酸の替わりに、リン酸アンモニウムやリン酸ナトリウムのような水溶性リン酸塩を用いることもできる。 Next, the calcium silicate compound is converted to hydroxyapatite. This can be performed by adding phosphoric acid to a slurry of a calcium silicate compound produced by a hydrothermal reaction or an aqueous solution in which a molded product is immersed. In this case, the phosphoric acid concentration is 2 to 50%, preferably 5 to 40%. If the phosphoric acid concentration is less than 2%, the amount of the liquid to be treated increases, which is inconvenient. If it is higher than 50%, fine hydroxyapatite and silica particles are likely to be generated due to a local decrease in pH of the liquid. This is inconvenient. Instead of phosphoric acid, water-soluble phosphates such as ammonium phosphate and sodium phosphate can be used.
リン酸の添加量は、珪酸カルシウム化合物中のカルシウムと添加するリン酸のモル比（Ｃａ/Ｐ）が１.９未満になるように定めることが望ましい。このモル比が１.９以上であると、重金属の吸着能力が低下するだけでなく、透水性も低下する。一方、このモル比が低い場合は、吸着剤のリンの溶解度が上がる傾向を示すので、工業的にみてＣａ/Ｐモル比１.３以上が推奨される。 The addition amount of phosphoric acid is preferably determined so that the molar ratio (Ca / P) of calcium to phosphoric acid to be added is less than 1.9 in the calcium silicate compound. When this molar ratio is 1.9 or more, not only the adsorption ability of heavy metals is lowered, but also the water permeability is lowered. On the other hand, when this molar ratio is low, the solubility of phosphorus in the adsorbent tends to increase, so a Ca / P molar ratio of 1.3 or more is recommended from an industrial viewpoint.
リン酸の添加に際しては、珪酸カルシウム化合物の分解に見合った速度で徐々にリン酸を加えていくことが肝要である。リン酸液に珪酸カルシウムを浸漬する方法、あるいは珪酸カルシウムのスラリーにリン酸を添加していく方法においても添加速度が速すぎる場合には、液のｐＨが急激に下がるため、珪酸カルシウム化合物の粒子形状が崩れ、微細なヒドロシキアパタイトやシリカ粒子が発生し、透水性が劣化する。反応中の溶液のｐＨが７.０以上、好ましくは８.０以上を維持するようにリン酸を添加することによって結晶性の良いヒドロシキアパタイトが生成し、かつ透水性に優れた複合多孔質体を得ることができる。 When adding phosphoric acid, it is important to gradually add phosphoric acid at a rate commensurate with the decomposition of the calcium silicate compound. In the method of immersing calcium silicate in the phosphoric acid solution, or in the method of adding phosphoric acid to the calcium silicate slurry, if the addition rate is too fast, the pH of the solution will drop sharply, so the particles of calcium silicate compound The shape collapses, fine hydroxyapatite and silica particles are generated, and water permeability deteriorates. A composite porous material having excellent crystallinity produced by the addition of phosphoric acid so that the pH of the solution during the reaction is maintained at 7.0 or higher, preferably 8.0 or higher, and having excellent crystallinity. You can get a body.
上記反応において、液温を４０〜１００℃の範囲で上げ、また液を攪拌して反応速度を促進することができる。ヒドロシキアパタイト化の反応時間は、原料の種類や粒度、粉体であるか成型体かなどによって異なり、一概に定めることはできないが、通常は０.５〜１２時間程度で十分である． In the above reaction, the liquid temperature can be raised in the range of 40 to 100 ° C., and the liquid can be stirred to accelerate the reaction rate. Hydroxiapatite reaction time varies depending on the type and particle size of the raw material, whether it is a powder or a molded body, and cannot be determined in general, but usually about 0.5 to 12 hours is sufficient.
珪酸カルシウム化合物にリン酸を反応させることによって、ヒドロシキアパタイトと多孔質シリカとの複合体を得ることができるが、この複合体の多孔質度をさらに上げたい場合には、リン酸の添加に先立ち、珪酸カルシウム化合物にリン酸以外の酸を予め作用させ、カルシウム分を酸処理によって除去することによって、細孔容積の高い複合体を得ることができる。 By reacting the calcium silicate compound with phosphoric acid, a composite of hydroxyapatite and porous silica can be obtained. However, if it is desired to further increase the porosity of the composite, it is necessary to add phosphoric acid. First, an acid other than phosphoric acid is allowed to act on the calcium silicate compound in advance, and the calcium content is removed by acid treatment, whereby a complex having a high pore volume can be obtained.
珪酸カルシウム化合物のカルシウム分をあらかじめ部分的に除去しておくと、多孔質シリカの割合が高くなり、多孔質度の高い複合体が得られるので、この複合体を例えば蛋白質の吸着剤などに用いる場合には吸着量を高めることができる。珪酸カルシウムの大部分のカルシウムを予め除去することによって、表層のみがヒドロシキアパタイトで覆われた多孔質シリカを得ることもできる。 If the calcium content of the calcium silicate compound is partially removed in advance, the proportion of porous silica increases and a complex with a high degree of porosity can be obtained. This complex is used, for example, as a protein adsorbent. In some cases, the amount of adsorption can be increased. By removing most of the calcium silicate in advance, porous silica in which only the surface layer is covered with hydroxyapatite can also be obtained.
カルシウム分を予め除去する際に用いる酸としては塩酸、硝酸等の無機酸、酢酸などの有機酸が用いられ、また二酸化炭素を吹き込む方法でもよい。さらに酸処理の替わりに酸性陽イオン交換樹脂も用いることもできる。 As an acid used for removing the calcium content in advance, an inorganic acid such as hydrochloric acid or nitric acid, an organic acid such as acetic acid, or a method of blowing carbon dioxide may be used. Further, an acidic cation exchange resin can be used instead of the acid treatment.
カルシウム分を予め除去するための酸の添加も、先に述べたように珪酸カルシウム化合物からカルシウムが溶出する速度に見合った速度、具体的にはｐＨ５.０以上を保持する速度で徐々に酸を加えていくことが好ましい。ｐＨ５.０を下回ると、微細なシリカ粒子が発生し、濾過処理に時間がかかるようになるので好ましくない。なお、液温を４０〜１００℃の範囲で上げたり、液を攪拌することによって反応速度を促進することができる。カルシウム除去の反応時間は、原料の種類や粒度、粉体であるか成型体かなどによって異なり、一概に定めることはできないが、通常は０.５〜３時間程度で十分である。 Addition of an acid for removing the calcium content in advance is also performed at a rate commensurate with the rate at which calcium is eluted from the calcium silicate compound as described above, specifically at a rate that maintains pH of 5.0 or higher. It is preferable to add. If the pH is less than 5.0, fine silica particles are generated and it takes time for the filtration treatment, which is not preferable. In addition, reaction rate can be accelerated | stimulated by raising liquid temperature in the range of 40-100 degreeC, or stirring a liquid. The reaction time for removing calcium varies depending on the type and particle size of the raw material, whether it is a powder or a molded body, and cannot be generally defined, but usually about 0.5 to 3 hours is sufficient.
反応後、このスラリーまたは成型体を固液分離し、水洗した後、再び水性スラリーあるいは水に浸漬してリン酸を添加し、ヒドロキシアパタイト化を行なうと良い。このようにして得たヒドロキシアパタイトシリカ複合多孔質体は、濾過あるいは遠心分離等の公知の手段によって固液分離した後に乾燥処理して吸着剤として使用することができる。 After the reaction, the slurry or the molded product is separated into solid and liquid, washed with water, and then immersed in an aqueous slurry or water again to add phosphoric acid to perform hydroxyapatite. The thus obtained hydroxyapatite silica composite porous body can be used as an adsorbent after being subjected to solid-liquid separation by a known means such as filtration or centrifugation, followed by drying treatment.
以下に本発明の実施例を比較例と共に示す。なお、製造した複合多孔質体の物性は以下に示す方法によって測定した。
（１）ＢＥＴ比表面積、全細孔容積及び平均細孔径
ＢＥＴ比表面積測定装置を用い、２５０℃で十分に加熱脱気した試料について、窒素ガスを吸着させる多点法による比表面積、全細孔容積及び平均細孔径を求めた。
（２）重金属の吸着
Ｐｂイオン濃度７５ppmに調製した硝酸鉛水溶液１００mlに対し、試料０.０５ｇを添加し、１８０rpmの回転数のシェーカーで一定時間振盪を行なった後に濾過して濾液中のＰｂを原子吸光分析装置で分析した。このＰｂ濃度を各実施例および各比較例について図１および図２に示した。
Examples of the present invention are shown below together with comparative examples. In addition, the physical property of the manufactured composite porous body was measured by the method shown below.
(1) BET specific surface area, total pore volume and average pore diameter Using a BET specific surface area measuring device, a specific surface area, total pores by a multipoint method for adsorbing nitrogen gas on a sample sufficiently heated and degassed at 250 ° C Volume and average pore diameter were determined.
(2) Adsorption of heavy metal To 100 ml of an aqueous lead nitrate solution adjusted to a Pb ion concentration of 75 ppm, 0.05 g of a sample is added, shaken with a shaker at 180 rpm for a certain period of time, and filtered to remove Pb in the filtrate. Analysis was performed with an atomic absorption spectrometer. The Pb concentration is shown in FIG. 1 and FIG. 2 for each example and each comparative example.
（３）透水性
ＪＩＳＡ・１２１８（土の透水試験方法）によって透水性を測定した。
（４）溶解度
脱イオン水１００mlに対し、試料０.０５ｇを添加し、２５℃の温度条件で１８０rpmの回転数のシェ−カーで２０時間振盪を行なった後、濾過して濾液中のＣａを原子吸光分析装置で分析し、Ｐを比色法で分析して溶解度を求めた。
（５）チトクロームＣの吸着率（蛋白質吸着量）
ｐＨ７に調製した５００ppmのチトクロームＣ水溶液１００mlに対し、試料０.３ｇを添加し、３０℃の恒温インキュベータで１時間振盪後、５Ｂの濾紙で濾過して、濾液中のチトクロームＣの残量を分光光度計で吸光度（波長４１０ｎｍ）の測定を行ない、初期濃度との差から吸着率を求めた。
(3) Water permeability The water permeability was measured by JISA 1218 (soil permeability test method).
(4) Solubility 0.05g of sample is added to 100ml of deionized water, shaken for 20 hours with a shaker at 180rpm under the temperature condition of 25 ° C, and then filtered to remove Ca in the filtrate. The solubility was determined by analyzing with an atomic absorption spectrometer and analyzing P with a colorimetric method.
(5) Cytochrome C adsorption rate (protein adsorption amount)
To 100 ml of 500 ppm cytochrome C aqueous solution adjusted to pH 7, add 0.3 g of sample, shake for 1 hour in a constant temperature incubator at 30 ° C., filter with 5B filter paper, and spectroscopically analyze the remaining amount of cytochrome C in the filtrate. Absorbance (wavelength: 410 nm) was measured with a photometer, and the adsorption rate was determined from the difference from the initial concentration.
〔実施例１〕
非晶質の珪酸原料（平均粒径２０μm）５００ｇと消石灰２５７ｇ（Ｃａ／Ｓｉモル比０.４）を、水中固形分比１０相当分の水を加え、オートクレーブ中で攪拌しながら１８０℃、４時間水熱反応を行なった。生成した非晶質珪酸カルシウムスラリーを予め７０℃に加熱して、非晶質珪酸カルシウムのカルシウム分に対してＣａ/Ｐモル比１.６７に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した．添加後、１時間攪拌し、スラリーを濾過、乾燥してヒドロキシアパタイトシリカ複合多孔質体を得た。このＢＥＴ比表面積、細孔容積、平均細孔径、重金属吸着性、透水率、水に対する溶解度、および蛋白質(チトクロームＣ)吸着率を表１に示し、Ｘ線回折の結果を図３に示し、走査型電子顕徹鏡写真を図４に示した。図３によれば、ヒドロキシアパタイトのピークが観察され、結晶質であることが確認された。一方、シリカについては結晶性を示すピークは観察されず、非晶質であることが確認された。
[Example 1]
500 g of an amorphous silicic acid raw material (average particle size 20 μm) and 257 g of slaked lime (Ca / Si molar ratio 0.4) were added with water corresponding to a solid content ratio of 10 in water, and stirred at 180 ° C. at 4 ° C. while stirring in an autoclave. The hydrothermal reaction was performed for an hour. The produced amorphous calcium silicate slurry was heated to 70 ° C. in advance, and phosphoric acid corresponding to a Ca / P molar ratio of 1.67 with respect to the calcium content of the amorphous calcium silicate was stirred for 1 hour while stirring the slurry. Added over time. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyapatite silica composite porous body. The BET specific surface area, pore volume, average pore diameter, heavy metal adsorptivity, water permeability, water solubility, and protein (cytochrome C) adsorption rate are shown in Table 1, and the X-ray diffraction results are shown in FIG. A type electron microscope photograph is shown in FIG. According to FIG. 3, the peak of hydroxyapatite was observed and confirmed to be crystalline. On the other hand, no peak showing crystallinity was observed for silica, and it was confirmed to be amorphous.
〔実施例２〕
非晶質の珪酸原料（平均粒径２０μm）５００ｇと消石灰６３５ｇ（Ｃａ／Ｓｉモル比１．０）を、水−固形分比１０相当分の水を加え、オートクレーブ中で攪拌しながら１８０℃、４時間水熱反応を行なった．生成した非晶質珪酸カルシウムスラリーを予め７０℃に加熱して、非晶質珪酸カルシウムのカルシウム分に対してＣａ/Ｐモル比１.６７に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した。添加後、１時間攪拌し、スラリーを濾過、乾燥して多孔性ヒドロキシアパタイトシリカ複合吸着剤を得た．この物性値を表１に示す。
[Example 2]
Amorphous silicic acid raw material (average particle size 20 μm) 500 g and slaked lime 635 g (Ca / Si molar ratio 1.0) were added with water corresponding to a water-solid content ratio of 10 and stirred at 180 ° C. in an autoclave. The hydrothermal reaction was performed for 4 hours. The produced amorphous calcium silicate slurry was heated to 70 ° C. in advance, and phosphoric acid corresponding to a Ca / P molar ratio of 1.67 with respect to the calcium content of the amorphous calcium silicate was stirred for 1 hour while stirring the slurry. Added over time. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a porous hydroxyapatite silica composite adsorbent. The physical property values are shown in Table 1.
〔実施例３〕
非晶質の珪酸原料（平均粒径２０μm）５００ｇと消石灰１２７０ｇ（Ｃａ／Ｓｉモル比２．０）を、水−固形分比１０相当分の水を加え、オートクレーブ中で攪拌しながら１８０℃、４時間水熱反応を行なった。生成した非晶質珪酸カルシウムスラリーを予め７０℃に加熱して、非晶質珪酸カルシウムのカルシウム分に対してＣａ/Ｐモル比１.６７に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した。添加後、１時間撹拌し、スラリーを濾過、乾燥してヒドロキシアパタイトシリカ複合多孔質体を得た。この物性値を表１に示す。
Example 3
Amorphous silicic acid raw material (average particle size 20 μm) 500 g and slaked lime 1270 g (Ca / Si molar ratio 2.0) are added with water corresponding to a water-solid content ratio of 10 and stirred at 180 ° C. in an autoclave. Hydrothermal reaction was performed for 4 hours. The produced amorphous calcium silicate slurry was heated to 70 ° C. in advance, and phosphoric acid corresponding to a Ca / P molar ratio of 1.67 with respect to the calcium content of the amorphous calcium silicate was stirred for 1 hour while stirring the slurry. Added over time. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyapatite silica composite porous body. The physical property values are shown in Table 1.
〔実施例４〕
実施例３と同様の水熱反応を行なって得た非晶質珪酸カルシウムスラリーについて、非晶質珪酸カルシウムのカルシウム分に対して、Ｃａ/ＨＣｌモル比１.５に相当す塩酸を添加して、非晶質珪酸カルシウムのカルシウムの３/４を脱カルシウムしたスラリーを得た。これを濾過、水洗後、ケーキに適量の水を加えて再びスラリーとし、残ったカルシウムに対してＣa/Ｐモル比１.６７に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した。添加後、１時間攪拌し、スラリーを濾過、乾燥してヒドロキシアパタイトシリカ複合多孔質体を得た。この物性値を表１に示す。
Example 4
About the amorphous calcium silicate slurry obtained by performing the hydrothermal reaction similar to Example 3, hydrochloric acid corresponding to a Ca / HCl molar ratio of 1.5 was added to the calcium content of the amorphous calcium silicate. Then, a slurry obtained by decalcifying 3/4 of calcium of amorphous calcium silicate was obtained. After filtering and washing with water, an appropriate amount of water was added to the cake to make a slurry again, and phosphoric acid corresponding to a Ca / P molar ratio of 1.67 with respect to the remaining calcium was added over 1 hour while stirring the slurry. did. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyapatite silica composite porous body. The physical property values are shown in Table 1.
〔実施例５〕
非晶質の珪酸原料（平均粒径２０μm）５００ｇと消石灰２５７ｇ（Ｃａ/Ｓｉモル比０.４）を、水中固形分比１０相当分の水を加え、オートクレーブ中で攪拌しながら１８０℃、４時間水熱反応を行なった。生成した非晶質珪酸カルシウムスラリーを予め７０℃に加熱して、非晶質珪酸カルシウムのカルシウム分に対してＣａ/Ｐモル比１.３０に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した。添加後、１時間攪拌し、スラリーを濾過、乾燥してヒドロキシキシアパタイトシリカ複合多孔質体を得た。この物性値を表１に示す。
Example 5
Amorphous silicic acid raw material (average particle size 20 μm) 500 g and slaked lime 257 g (Ca / Si molar ratio 0.4) were added with water corresponding to a solid content ratio of 10 in water and stirred at 180 ° C., 4 ° C. while stirring in an autoclave. The hydrothermal reaction was performed for an hour. The produced amorphous calcium silicate slurry was heated to 70 ° C. in advance, and phosphoric acid corresponding to a Ca / P molar ratio of 1.30 with respect to the calcium content of the amorphous calcium silicate was stirred for 1 hour while stirring the slurry. Added over time. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyxiapatite silica composite porous body. The physical property values are shown in Table 1.
〔実施例６〕
非晶質の珪酸原料（平均粒径２０μm）５００ｇと消石灰２５７ｇ（Ｃａ/Ｓｉモル比０.４）を、水一固形分比１０相当分の水を加え、オートクレーブ中で攪拌しながら１８０℃、４時間水熱反応を行なった。生成した非晶質珪酸カルシウムスラリーを予め７０℃に加熱して、非晶質珪酸カルシウムのカルシウム分に対してＣａ/Ｐモル比１.５０に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した．添加後、１時間攪拌し、スラリーを濾過、乾燥してヒドロキシアパタイトシリカ複合多孔質体を得た。この物性値を表１に示す。
Example 6
Amorphous silicic acid raw material (average particle size 20 μm) 500 g and slaked lime 257 g (Ca / Si molar ratio 0.4) were added with water equivalent to a water-solids ratio of 10 and stirred at 180 ° C. in an autoclave. Hydrothermal reaction was performed for 4 hours. The produced amorphous calcium silicate slurry was heated in advance to 70 ° C., and phosphoric acid corresponding to a Ca / P molar ratio of 1.50 with respect to the calcium content of the amorphous calcium silicate was stirred for 1 hour while stirring the slurry. Added over time. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyapatite silica composite porous body. The physical property values are shown in Table 1.
〔実施例７〕
結晶質の珪酸原料（平均粒径１０μm）５００ｇと消石灰４９８ｇ（Ｃａ/Ｓｉモル比０.８）を、水−固形分比１０相当分の水を加え、オートクレーブ中で攪拌しながら１８０℃、８時間水熱反応を行なった。生成した非晶質珪酸カルシウムスラリーを予め７０℃に加熱して、非晶質珪酸カルシウムのカルシウム分に対してＣａ/Ｐモル比１.６７に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した．添加後、１時間攪拌し、スラリーを濾過、乾燥してヒドロキシアパタイトシリカ複合多孔質体を得た。この物性値を表１に示す。
Example 7
A crystalline silicic acid raw material (average particle size 10 μm) 500 g and slaked lime 498 g (Ca / Si molar ratio 0.8) were added water corresponding to a water-solid content ratio of 10 and stirred at 180 ° C., 8 ° C. while stirring in an autoclave. The hydrothermal reaction was performed for an hour. The produced amorphous calcium silicate slurry was heated to 70 ° C. in advance, and phosphoric acid corresponding to a Ca / P molar ratio of 1.67 with respect to the calcium content of the amorphous calcium silicate was stirred for 1 hour while stirring the slurry. Added over time. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyapatite silica composite porous body. The physical property values are shown in Table 1.
〔実施例８〕
実施例７と同様の水熱反応を行なって得た非晶質珪酸カルシウムスラリーについて、非晶質珪酸カルシウムのカルシウム分に対して、Ｃａ/ＨＣｌモル比１.０に相当する塩酸を添加して、非晶質珪酸カルシウムの半量を脱カルシウムしたスラリーを得た。これを濾過・水洗後、適量の水を加えてスラリーとし、残ったカルシウムに対してＣａ/Ｐモル比１.６７に相当するリン酸を、スラリーを７０℃に加温・攪拌しつつ１時間かけて添加した。添加後、１時間攪拌し、スラリーを濾過、乾燥してヒドロキシアパタイトシリカ複合多孔質体を得た。この物性値を表１に示す。
Example 8
About the amorphous calcium silicate slurry obtained by performing the hydrothermal reaction similar to Example 7, hydrochloric acid corresponding to a Ca / HCl molar ratio of 1.0 was added to the calcium content of the amorphous calcium silicate. A slurry obtained by decalcifying half of the amorphous calcium silicate was obtained. After filtering and washing with water, an appropriate amount of water was added to form a slurry, and phosphoric acid corresponding to a Ca / P molar ratio of 1.67 with respect to the remaining calcium was added to the slurry at 70 ° C. for 1 hour while heating and stirring. Added over time. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyapatite silica composite porous body. The physical property values are shown in Table 1.
〔実施例９〕
非晶質の珪酸原料（平均粒径２０μm）シリカ５００ｇと消石灰５０８ｇ（Ｃａ/Ｓｉモル比０.８）を、水−固形分比２０相当分の水を加え、オートクレーブ中で２２０℃、２０時間水熱反応を行なった。生成したトバモライトスラリーを予め７０℃に加熱して、トバモライトのカルシウム分に対してＣａ/Ｐモル比１.６７に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した。添加後、１時間攪拌し、スラリーを濾過、乾燥して多孔性ヒドロキシアパタイトシリカ複合吸着剤を得た。この物性値を表１に示す。
Example 9
Amorphous silicic acid raw material (average particle size 20 μm) 500 g of silica and 508 g of slaked lime (Ca / Si molar ratio 0.8) were added with water corresponding to a water-solid content ratio of 20 and in an autoclave at 220 ° C. for 20 hours. Hydrothermal reaction was performed. The produced tobermorite slurry was heated to 70 ° C. in advance, and phosphoric acid corresponding to a Ca / P molar ratio of 1.67 with respect to the calcium content of tobermorite was added over 1 hour while stirring the slurry. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a porous hydroxyapatite silica composite adsorbent. The physical property values are shown in Table 1.
〔実施例１０〕
耐火被覆建材用ゾノトライト成型板（１５０×１００×２５ｍｍ、嵩密度０.２５g/cm3）を６０℃に加温した温水に浸現し、ゾノトライトのカルシウム分に対してＣａ/Ｐモル比１.６７に相当するリン酸を、緩やかに液を攪拌しつつ６時間かけて添加した。添加後、１２時間浸漬養生した後、成型板を乾燥してヒドロキシアパタイトシリカ複合多孔質体からなる成形板を得た。この物性値を表１に示す。
Example 10
A zonotlite molded board for fireproof coating materials (150 × 100 × 25 mm, bulk density of 0.25 g / cm 3 ) is immersed in warm water heated to 60 ° C., and the Ca / P molar ratio is 1.67 with respect to the calcium content of zonotlite. Was added over 6 hours while gently stirring the solution. After the addition, after curing for 12 hours, the molded plate was dried to obtain a molded plate made of a hydroxyapatite silica composite porous body. The physical property values are shown in Table 1.
〔比較例１〕
非晶質の珪酸原料（平均粒径２０μm）５００ｇと消石灰２５７ｇ（Ｃａ/Ｓｉモル比０.４）を、水−固形分比１０相当分の水を加え、オートクレーブ中で攪拌しながら１８０℃、４時間水熱反応を行なった。生成した非晶質珪酸カルシウムスラリーを予め７０℃に加熱して、非晶質珪酸カルシウムのカルシウム分に対してＣａ/Ｐモル比１.９０に相当するリン酸を、スラリーを攪拌しつつ１時間かけて添加した。添加後、１時間攪拌し、スラリーを濾過、乾燥してヒドロキシアパタイトシリカ複合多孔質体を得た。この物性値を表１に示す。
[Comparative Example 1]
Amorphous silicic acid raw material (average particle size 20 μm) 500 g and slaked lime 257 g (Ca / Si molar ratio 0.4) were added with water corresponding to a water-solid content ratio of 10 and stirred at 180 ° C. in an autoclave. Hydrothermal reaction was performed for 4 hours. The produced amorphous calcium silicate slurry was heated in advance to 70 ° C., and phosphoric acid corresponding to a Ca / P molar ratio of 1.90 with respect to the calcium content of the amorphous calcium silicate was stirred for 1 hour while stirring the slurry. Added over time. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyapatite silica composite porous body. The physical property values are shown in Table 1.
〔比較例２〕
非晶質の珪酸原料（平均粒径２０μm）５００ｇと消石灰２５７ｇ（Ｃａ/Ｓｉモル比０.４）を、水−固形分比１０相当分の水を加え、オートクレーブ中で攪拌しながら１８０℃、４時間水熱反応を行なった。生成した非晶質珪酸カルシウムスラリーを予め７０℃に加熱して、非晶質珪酸カルシウムのカルシウム分に対してＣａ/Ｐモル比１.６７に相当するリン酸を、スラリーを攪拌しつつ２分間で添加した。添加後、１時間攪拌し、スラリーを濾過、乾燥してヒドロキシアパタイトシリカ複合多孔質体を得た。この物性値を表１に示す。
[Comparative Example 2]
Amorphous silicic acid raw material (average particle size 20 μm) 500 g and slaked lime 257 g (Ca / Si molar ratio 0.4) were added with water corresponding to a water-solid content ratio of 10 and stirred at 180 ° C. in an autoclave. Hydrothermal reaction was performed for 4 hours. The produced amorphous calcium silicate slurry was heated in advance to 70 ° C., and phosphoric acid corresponding to a Ca / P molar ratio of 1.67 with respect to the calcium content of the amorphous calcium silicate was stirred for 2 minutes while stirring the slurry. Added at. After the addition, the mixture was stirred for 1 hour, and the slurry was filtered and dried to obtain a hydroxyapatite silica composite porous body. The physical property values are shown in Table 1.
〔比較例３〕
発泡軽量コンクリートの廃材を粒径０.５〜２ｍｍに粉砕し、この粉砕物中のカルシウムに対してＣａ/Ｐモル比１.６７に相当するリン酸（２０％）中に粉砕物を浸漬し、その後６０℃にて１５時間水中養生して、表面をヒドロキシアパタイト化したヒドロキシアパタイトシリカ複合多孔質体を得た。このものの物性値を表１に示す。
[Comparative Example 3]
The foamed lightweight concrete waste material is pulverized to a particle size of 0.5 to 2 mm, and the pulverized product is immersed in phosphoric acid (20%) corresponding to a Ca / P molar ratio of 1.67 with respect to calcium in the pulverized product. Then, it was cured in water at 60 ° C. for 15 hours to obtain a hydroxyapatite silica composite porous body having a hydroxyapatite surface. The physical properties of this product are shown in Table 1.
〔比較例４〜６〕
比較のため、市販のクロマト用ヒドロキシアパタイト（比較例４〜６）について実施例と同様の測定値を表１に示した。
[Comparative Examples 4 to 6]
For comparison, Table 1 shows measured values similar to those of Examples for commercially available hydroxyapatite for chromatography (Comparative Examples 4 to 6).
図１に示すように、比較例３、４、６では２０分経過後のＰｂ濃度は何れも２０ppm以上であるが、本発明の実施例１、３、７、８、９、１０は何れも１０分経過後には１０ppm以下、２０分経過後のＰｂ濃度は実質的にゼロであり、重金属に対して短時間に優れた吸着効果を有することが判る。この傾向は図２においても同様であり、ヒドロキシアパタイトのカルシウムとリンのモル比（Ｃａ/Ｐ）が１.９０である比較例１は６０分経過後のＰｂ濃度が４０ppm以上であるのに対して、本発明の実施例１、５、６は２０分経過後のＰｂ濃度は実質的にゼロであり、優れた吸着効果を有している。 As shown in FIG. 1, in Comparative Examples 3, 4, and 6, the Pb concentration after 20 minutes is 20 ppm or more, but in Examples 1, 3, 7, 8, 9, and 10 of the present invention, After 10 minutes, 10 ppm or less and the Pb concentration after 20 minutes are substantially zero, indicating that the heavy metal has an excellent adsorption effect in a short time. This tendency is the same in FIG. 2, whereas in Comparative Example 1 in which the molar ratio of calcium to phosphorus (Ca / P) of hydroxyapatite is 1.90, the Pb concentration after 60 minutes is 40 ppm or more. In Examples 1, 5, and 6 of the present invention, the Pb concentration after 20 minutes is substantially zero, and has an excellent adsorption effect.
表１に示すように、比較例の細孔容積は大部分が０.４ml/g以下であるが、本発明のヒドロキシアパタイトシリカ複合多孔質体は何れも細孔容積０.５ml/g以上であって、平均細孔径が何れも２０nm以下であり、微細な多数の細孔を有する多孔質体である。従って、高い吸着性を有し、６０分経過後の残留Ｐｂ濃度は何れも０.２５ppm以下である。また、蛋白質の吸着率も５０％以上であり、高い吸着率を示している。 As shown in Table 1, the pore volume of the comparative example is mostly 0.4 ml / g or less, but the hydroxyapatite silica composite porous body of the present invention has a pore volume of 0.5 ml / g or more. The average pore diameter is 20 nm or less, and the porous body has a large number of fine pores. Therefore, it has high adsorptivity and the residual Pb concentration after 60 minutes is 0.25 ppm or less. The protein adsorption rate is also 50% or more, indicating a high adsorption rate.
また、本発明のヒドロキシアパタイトシリカ複合多孔質体は溶解性が低く、Ｐの溶解度は３.５ppm以下であり、Ｃａの溶解度も実施例１０を除き３.０ppm以下である。
さらに、本発明のヒドロキシアパタイトシリカ複合多孔質体は、平均粒径が約１４μm〜６０μmであって、ＢＥＴ比表面積が１６０ｍ2/g以上であり、適度な粒径を有しながら大きな比表面積を有しており、優れた吸着性と共に良好な透水性を有している。具体的には、実施例１〜１０は何れも１.５×１０-4cm/s以上の透水率を有し、特に実施例１、５〜８は１５×１０-4〜８４×１０-4cm/sの高い透水率を有する。一方、比較例の透水率は１６×１０-4cm/s以下である。
The hydroxyapatite silica composite porous body of the present invention has low solubility, the solubility of P is 3.5 ppm or less, and the solubility of Ca is 3.0 ppm or less except in Example 10.
Furthermore, the hydroxyapatite silica composite porous body of the present invention has an average particle size of about 14 μm to 60 μm, a BET specific surface area of 160 m 2 / g or more, and has a large specific surface area while having an appropriate particle size. And has good water permeability as well as excellent adsorptivity. Specifically, each of Examples 1 to 10 has a water permeability of 1.5 × 10 −4 cm / s or more, and in particular, Examples 1 and 5 to 8 are 15 × 10 −4 to 84 × 10 −. It has a high water permeability of 4 cm / s. On the other hand, the water permeability of the comparative example is 16 × 10 −4 cm / s or less.
Claims (11)
A calcium silicate compound is immersed in warm water and phosphoric acid is added under heating. At this time, the amount of phosphoric acid is such that the molar ratio of calcium to phosphorus (Ca / P) is less than 1.9. The production method according to any one of claims 7 to 9, wherein an acid is gradually added and reacted to produce a hydroxyapatite silica composite porous body.
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