JP2017154047A - Phosphorus recovery material - Google Patents
Phosphorus recovery material Download PDFInfo
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- JP2017154047A JP2017154047A JP2016037523A JP2016037523A JP2017154047A JP 2017154047 A JP2017154047 A JP 2017154047A JP 2016037523 A JP2016037523 A JP 2016037523A JP 2016037523 A JP2016037523 A JP 2016037523A JP 2017154047 A JP2017154047 A JP 2017154047A
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- phosphorus
- calcium silicate
- silicate hydrate
- csh
- phosphorus recovery
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000011574 phosphorus Substances 0.000 title claims abstract description 111
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 111
- 238000011084 recovery Methods 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000000378 calcium silicate Substances 0.000 claims abstract description 59
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 59
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 48
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 47
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 46
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 46
- 239000011575 calcium Substances 0.000 claims abstract description 37
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- JLDKGEDPBONMDR-UHFFFAOYSA-N calcium;dioxido(oxo)silane;hydrate Chemical compound O.[Ca+2].[O-][Si]([O-])=O JLDKGEDPBONMDR-UHFFFAOYSA-N 0.000 description 56
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SQPVQGHHSGWUEP-UHFFFAOYSA-N O.[P] Chemical compound O.[P] SQPVQGHHSGWUEP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- -1 carbonate anhydride Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004889 fertilizer analysis Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
本発明は、微細結晶質の珪酸カルシウムリン水和物からなり、回収率が高く、ク溶性リン酸の含有量が高いリン回収材およびその製造方法に関する。 The present invention relates to a phosphorus recovery material made of fine crystalline calcium silicate phosphorus hydrate, having a high recovery rate and a high content of soluble phosphoric acid, and a method for producing the same.
珪酸カルシウムを主成分とする脱リン剤が従来から知られている。例えば、特開昭６１−２６３６３６号公報（特許文献１）にはＣａＯ/ＳｉＯ２モル比が１.５〜５の珪酸カルシウム水和物を主成分とする水処理剤が記載されている。また、特公平０２−２０３１５号公報（特許文献２）には空隙率５０〜９０％の独立気泡を有する珪酸カルシウム水和物からなる脱リン材が記載されている。さらに、特開平１０−２３５３４４号公報（特許文献３）には珪酸カルシウム水和物を主成分とした直径数ミリ程度の球状または中空状に成形した脱リン材が記載されている。特開２０００−１３５４９３号公報（特許文献４）には珪灰石を用いた脱リン方法が提案されている。 A dephosphorizing agent mainly composed of calcium silicate is conventionally known. For example, JP 61-263636 (Patent Document 1) describes a water treatment agent CaO / SiO 2 molar ratio is mainly composed of calcium silicate hydrate 1.5-5. Japanese Patent Publication No. 02-20315 (Patent Document 2) describes a dephosphorization material made of calcium silicate hydrate having closed cells with a porosity of 50 to 90%. Furthermore, Japanese Patent Laid-Open No. 10-235344 (Patent Document 3) describes a dephosphorization material formed into a spherical or hollow shape having a diameter of about several millimeters, the main component of which is calcium silicate hydrate. JP 2000-135493 A (Patent Document 4) proposes a dephosphorization method using wollastonite.
従来の珪酸カルシウムを主成分とする脱リン材を用いる処理方法は、回収物の脱水性や有機物混入の問題をある程度回避できるものの、リンとの反応速度が遅いため、回収物のリン濃度を上げるためには長い反応時間を必要とする。また、回収物に含まれるリン含有量が少ないため、リン酸肥料として有効に利用できないなどの問題がある。 Although the conventional treatment method using a dephosphorization material mainly composed of calcium silicate can avoid the problem of dehydration and organic matter contamination of the recovered material to some extent, the reaction rate with phosphorus is slow, so the phosphorus concentration of the recovered material is increased. This requires a long reaction time. Moreover, since there is little phosphorus content contained in collection | recovery, there exists a problem that it cannot utilize effectively as a phosphate fertilizer.
この問題を解決するリン回収資材として、平均粒子径(メジアン径)１５０μm以下の微粉末であって細孔容積０.３cm３/ｇ以上の多孔質珪酸カルシウム水和物からなるリン回収資材（特許文献５）、あるいはＢＥＴ比表面積８０m２/ｇ以上、細孔容積０.５cm３/ｇ以上の多孔質の珪酸カルシウム水和物からなるリン回収資材が知られている（特許文献６）。
また、リン発生源の排水中のリンを非晶質ケイ酸カルシウム系の材料からなるリン回収材に吸着させて回収することを特徴とするリン回収方法（特許文献７）、珪酸ナトリウム水溶液と石灰を、非加熱下で混合して生成した非晶質珪酸カルシウム水和物単体または非晶質珪酸カルシウム水和物とＣａ(ＯＨ)２との複合物からなり、該水和物単体または該複合物のＣａ/Ｓｉモル比が０.８〜１.５であるリン回収材（特許文献８）が知られている。
As a phosphorus recovery material that solves this problem, a phosphorus recovery material made of porous calcium silicate hydrate having a mean particle diameter (median diameter) of 150 μm or less and a pore volume of 0.3 cm 3 / g or more (patented) Document 5), or a phosphorus recovery material made of porous calcium silicate hydrate having a BET specific surface area of 80 m 2 / g or more and a pore volume of 0.5 cm 3 / g or more is known (Patent Document 6).
In addition, a phosphorus recovery method (Patent Document 7) characterized by adsorbing and recovering phosphorus in wastewater from a phosphorus generation source by a phosphorus recovery material made of an amorphous calcium silicate-based material, sodium silicate aqueous solution and lime Consisting of an amorphous calcium silicate hydrate simple substance or a composite of amorphous calcium silicate hydrate and Ca (OH) 2 produced by mixing without heating. A phosphorus recovery material (Patent Document 8) having a Ca / Si molar ratio of 0.8 to 1.5 is known.
特許文献５〜特許文献８に記載されているリン回収材は非晶質の珪酸カルシウム水和物であり、非晶質珪酸カルシウム水和物は結晶質の珪酸カルシウム水和物よりもリンとの反応性が良いことを利点にしている。例えば、特許文献１の珪酸カルシウム水和物は、非晶質と記載されているが、実際は結晶格子サイズが約９０nm前後の結晶質珪酸カルシウム水和物であるためリンとの反応が遅い。一方、特許文献５〜特許文献８に記載されているリン回収資材は、リンとの反応性が高く、リン濃度を急激に低減することができ、リンの回収率が高い利点を有している。 The phosphorus collection | recovery material described in patent document 5-patent document 8 is an amorphous calcium silicate hydrate, and an amorphous calcium silicate hydrate is a thing with phosphorus rather than crystalline calcium silicate hydrate. The advantage is good reactivity. For example, although the calcium silicate hydrate of Patent Document 1 is described as being amorphous, the reaction with phosphorus is slow because it is actually a crystalline calcium silicate hydrate having a crystal lattice size of about 90 nm. On the other hand, the phosphorus collection | recovery material described in patent document 5-patent document 8 has the high reactivity with phosphorus, can reduce phosphorus concentration rapidly, and has the advantage that the recovery rate of phosphorus is high. .
しかし、本発明において、結晶質の珪酸カルシウム水和物についても、一定範囲の結晶子サイズであればリンとの反応性が良く、高いリン回収率を有することが確認された。本発明は、一定範囲の結晶子サイズからなる珪酸カルシウム水和物を一定量以上含むことによって、リンとの反応性が良く、高いリン回収率を有するリン回収材およびその製造方法を提供する。 However, in the present invention, it was confirmed that crystalline calcium silicate hydrate has good reactivity with phosphorus and a high phosphorus recovery rate if the crystallite size is within a certain range. The present invention provides a phosphorus recovery material having a high reactivity with phosphorus and a high phosphorus recovery rate, and a method for producing the same, by containing a certain amount or more of calcium silicate hydrate having a crystallite size within a certain range.
本発明は以下の構成からなるリン回収材とその製造方法に関する。
〔１〕結晶が６.０nm〜１６.０nmの微細結晶質の珪酸カルシウム水和物を５０wt％以上含有し、Ｃａ／Ｓｉモル比が０.５〜３.５であることを特徴とするリン回収材。
〔２〕珪酸カルシウム水和物の結晶子サイズが６.５nm〜１０.０nmであって、Ｃａ／Ｓｉモル比が０.８〜１.５である上記[１]に記載するリン回収材。
〔３〕生成する珪酸カルシウム水和物のＣａ／Ｓｉモル比が０.５〜３.５になる量の消石灰スラリーと水ガラスを用い、常温下、消石灰スラリーに水ガラスを３分以上の時間で添加し、あるいは消石灰スラリーと水ガラスを同時に３分以上の時間で添加することによって結晶子サイズが６.０ｎｍ〜１６.０ｎｍの微細結晶質の珪酸カルシウム水和物を生成させ、該珪酸カルシウム水和物を固液分離してリン回収材を得ることを特徴とするリン回収材の製造方法。
The present invention relates to a phosphorus recovery material having the following configuration and a method for producing the same.
[1] Phosphorus characterized in that it contains 50 wt% or more of fine crystalline calcium silicate hydrate of 6.0 nm to 16.0 nm and a Ca / Si molar ratio of 0.5 to 3.5. Collected material.
[2] The phosphorus recovery material according to the above [1], wherein the crystallite size of calcium silicate hydrate is 6.5 nm to 10.0 nm, and the Ca / Si molar ratio is 0.8 to 1.5.
[3] Using slaked lime slurry and water glass in such an amount that the Ca / Si molar ratio of the calcium silicate hydrate to be generated is 0.5 to 3.5, and water glass is added to the slaked lime slurry at room temperature for 3 minutes or more. Or by adding slaked lime slurry and water glass at the same time for 3 minutes or more to produce fine crystalline calcium silicate hydrate having a crystallite size of 6.0 nm to 16.0 nm. A method for producing a phosphorus recovery material, characterized by obtaining a phosphorus recovery material by solid-liquid separation of a hydrate.
〔具体的な説明〕
本発明のリン回収材は、Ｃａ／Ｓｉモル比が０.５〜３.５、好ましくはＣａ／Ｓｉモル比が０.８〜１.５であって、結晶子サイズが６.０ｎｍ〜１６.０ｎｍ、好ましくは結晶子サイズが６.５ｎｍ〜１０.０ｎｍの微細結晶質の珪酸カルシウム水和物（ＣＳＨと云う）を５０wt％以上含有することを特徴とするリン回収材である。
[Specific description]
The phosphorus recovery material of the present invention has a Ca / Si molar ratio of 0.5-3.5, preferably a Ca / Si molar ratio of 0.8-1.5, and a crystallite size of 6.0 nm-16. A phosphorus recovery material characterized by containing 50 wt% or more of fine crystalline calcium silicate hydrate (referred to as CSH) having a crystallite size of 6.5 nm to 10.0 nm.
〔リン回収材：珪酸カルシウム水和物〕
本発明のリン回収材として用いられる珪酸カルシウム水和物（ＣＳＨ）は、結晶子サイズが６.０nm〜１６.０nm、好ましくは結晶子サイズが６.５nm〜１０.０nmの微細結晶質の珪酸カルシウム水和物である。
実施例で示すように、結晶子サイズが６.０nm〜１６.０nmの珪酸カルシウム水和物からなる本発明のＣＳＨはリンとの反応性が良いので、リンを含む排水など（リン含有水と云う）に使用したときに、リンと反応して良く溶解し、高いリン回収率を得ることができる。なお、珪酸カルシウム水和物の結晶子サイズは、珪酸カルシウム水和物の乾燥体について、Ｘ線回折ピークの半値幅からシェラー式に従って求められる。
[Phosphorus recovery material: calcium silicate hydrate]
The calcium silicate hydrate (CSH) used as the phosphorus recovery material of the present invention has a fine crystalline silicic acid having a crystallite size of 6.0 nm to 16.0 nm, preferably a crystallite size of 6.5 nm to 10.0 nm. Calcium hydrate.
As shown in the examples, the CSH of the present invention comprising calcium silicate hydrate having a crystallite size of 6.0 nm to 16.0 nm has good reactivity with phosphorus, so that waste water containing phosphorus (phosphorus-containing water and When it is used, it reacts with phosphorus and dissolves well, and a high phosphorus recovery rate can be obtained. In addition, the crystallite size of calcium silicate hydrate is calculated | required according to the Scherrer formula from the half value width of an X-ray diffraction peak about the dried body of calcium silicate hydrate.
一方、結晶子サイズが６.０nm未満の珪酸カルシウム水和物からなるＣＳＨは含水固形物の含水率が高く、珪酸カルシウム水和物を脱水乾燥するコストがかかるので好ましくない。また、珪酸カルシウム水和物の結晶子サイズが１６.０nmを上回るとＣＳＨとリンの反応性が低くなり、結晶子サイズが２０.０nmより大きいとＣＳＨのリン回収率が大幅に低下する傾向がある。 On the other hand, CSH made of calcium silicate hydrate having a crystallite size of less than 6.0 nm is not preferable because the water content of the hydrated solid is high and the cost of dehydrating and drying the calcium silicate hydrate is high. In addition, when the crystallite size of calcium silicate hydrate exceeds 16.0 nm, the reactivity of CSH and phosphorus decreases, and when the crystallite size exceeds 20.0 nm, the CSH phosphorus recovery rate tends to decrease significantly. is there.
本発明のＣＳＨのＣａ／Ｓｉモル比は０.５〜３.５であり、好ましくは０.８〜１.５である。該Ｃａ／Ｓｉモル比が０.５未満では、リンと反応するＣａ量が少なく、リン回収率が低下する。リン回収率を高めるにはＣａ／Ｓｉモル比は０.８以上が好ましい。一方、該Ｃａ／Ｓｉモル比が３.５を上回ると、リンと炭酸が共存する液に使用したときに、Ｃａと炭酸の反応が進行してＣａとリンの反応が抑制されるため、リン回収率が低下する傾向がある。リンと炭酸が共存する液に使用する場合には、ＣＳＨのＣａ／Ｓｉモル比は０.８〜１.５が好ましい。 The CSH Ca / Si molar ratio of the present invention is 0.5 to 3.5, preferably 0.8 to 1.5. If the Ca / Si molar ratio is less than 0.5, the amount of Ca that reacts with phosphorus is small, and the phosphorus recovery rate decreases. In order to increase the phosphorus recovery rate, the Ca / Si molar ratio is preferably 0.8 or more. On the other hand, when the Ca / Si molar ratio exceeds 3.5, when used in a liquid in which phosphorus and carbonic acid coexist, the reaction between Ca and carbonic acid proceeds to suppress the reaction between Ca and phosphorus. Recovery tends to decrease. When used in a liquid in which phosphorus and carbonic acid coexist, the Ca / Si molar ratio of CSH is preferably 0.8 to 1.5.
本発明のリン回収材は上記ＣＳＨを５０wt％以上、好ましくは８０wt％以上含有する。消石灰スラリーと水ガラスを水和反応させて珪酸カルシウム水和物を生成させる場合、未反応の消石灰[Ｃａ(ＯＨ２)]が残留すると、生成物が上記ＣＳＨと消石灰を含むが、ＣＳＨ含有量が５０wt％以上、好ましくは８０wt％以上であれば良い。ＣＳＨ含有量が５０wt％未満ではＣＳＨによるリン回収効果が不十分になるので好ましくない。 The phosphorus recovery material of the present invention contains 50 wt% or more, preferably 80 wt% or more of the CSH. When calcium silicate hydrate is produced by hydrating slaked lime slurry and water glass, if unreacted slaked lime [Ca (OH 2 )] remains, the product contains the above CSH and slaked lime, but the CSH content Is 50 wt% or more, preferably 80 wt% or more. If the CSH content is less than 50 wt%, the phosphorus recovery effect by CSH becomes insufficient, which is not preferable.
本発明のリン回収材は、リン含有水に対して使用したときに、リンがＣＳＨと反応してリン酸カルシウムを生成することによってリンがＣＳＨに取り込まれ、リンを回収することができる。 When the phosphorus recovery material of the present invention is used for phosphorus-containing water, phosphorus reacts with CSH to produce calcium phosphate, whereby phosphorus is taken into CSH, and phosphorus can be recovered.
〔製造方法〕
本発明のリン回収材は、生成する珪酸カルシウム水和物のＣａ／Ｓｉモル比が０.５〜３.５になる量、好ましくはＣａ／Ｓｉモル比が０.８〜１.５になる量の消石灰スラリーと水ガラスを用い、常温下、消石灰スラリーに水ガラスを３分以上の時間で添加し、あるいは消石灰スラリーと水ガラスを同時に３分以上の時間で添加することによって結晶子サイズが６.０nm〜１６.０nmの微細結晶質の珪酸カルシウム水和物を生成させ、該珪酸カルシウム水和物を固液分離することによって製造される。
〔Production method〕
The phosphorus recovery material of the present invention is such that the Ca / Si molar ratio of the calcium silicate hydrate to be produced is 0.5 to 3.5, preferably the Ca / Si molar ratio is 0.8 to 1.5. Using a quantity of slaked lime slurry and water glass, the crystallite size can be reduced by adding water glass to the slaked lime slurry at room temperature for a period of 3 minutes or more, or by simultaneously adding the slaked lime slurry and water glass for a period of 3 minutes or more. It is produced by producing a fine crystalline calcium silicate hydrate of 6.0 nm to 16.0 nm and solid-liquid separation of the calcium silicate hydrate.
本発明の製造方法は、消石灰スラリーと水ガラス（珪酸ナトリウム水溶液：Ｎａ２ＳｉＯ３）を用いる。未反応の消石灰残量が少なく、結晶子サイズが６.０nm〜１６.０nmの微細結晶の珪酸カルシウムを生成させるには、珪酸が十分に溶解した状態で消石灰と反応させる必要があるので、珪酸源としては水ガラスが好ましい。他の珪酸化合物を用い、反応時に溶解させて消石灰と反応させる方法では、珪酸の溶解が十分ではなく、未反応の珪酸が残留するため目的の微細結晶の珪酸カルシウムを生成させるのが難しい。 The production method of the present invention uses slaked lime slurry and water glass (sodium silicate aqueous solution: Na 2 SiO 3 ). In order to produce calcium carbonate silicate with a small amount of unreacted slaked lime and a crystallite size of 6.0 nm to 16.0 nm, it is necessary to react with slaked lime in a state where silicic acid is sufficiently dissolved. Water glass is preferred as the source. In the method of using other silicic acid compounds and dissolving them in the reaction and reacting with slaked lime, the silicic acid is not sufficiently dissolved, and unreacted silicic acid remains, so that it is difficult to produce the desired fine crystalline calcium silicate.
消石灰スラリーの濃度は３wt％〜１０wt％が好ましい。水ガラスの濃度は珪酸濃度として１wt％〜１０wt％が好ましい。また、消石灰スラリーと水ガラスの反応量は、生成する珪酸カルシウム水和物のＣａ／Ｓｉモル比が０.５〜３.５になる量、好ましくはＣａ／Ｓｉモル比が０.８〜１.５になる量である。 The concentration of the slaked lime slurry is preferably 3 wt% to 10 wt%. The concentration of water glass is preferably 1 wt% to 10 wt% as the silicic acid concentration. The reaction amount of the slaked lime slurry and water glass is such that the Ca / Si molar ratio of the calcium silicate hydrate to be generated is 0.5 to 3.5, preferably the Ca / Si molar ratio is 0.8 to 1. It is the quantity which becomes .5.
本発明の製造方法では、消石灰スラリーに水ガラスを３分以上の時間で添加し、あるいは消石灰スラリーと水ガラスを同時に３分以上の時間で添加する。消石灰スラリーと水ガラスを少量ずつ用い、３分以上の時間をかけて、消石灰スラリーに水ガラスを添加し、あるいは消石灰スラリーと水ガラスを互いに同時に添加することによって、未反応の消石灰残量が少なく、結晶子サイズが６.０nm〜１６.０nm、好ましくは６.５nm〜１０.０nmの珪酸カルシウムを生成させることができる。なお、消石灰スラリーと水ガラスについて少量ずつとは、３分以上の時間をかけて添加する量であり、例えば、上記Ｃａ／Ｓｉモル比になるように、消石灰スラリー１Ｌあたり、水ガラス９００〜１２００mlを３分以上の時間をかけて消石灰スラリーに添加する。あるいは、消石灰スラリー１０００mlと水ガラス９００〜１２００mlを同時に３分以上の時間をかけて添加すると良い。 In the production method of the present invention, the water glass is added to the slaked lime slurry in a time of 3 minutes or more, or the slaked lime slurry and the water glass are simultaneously added in a time of 3 minutes or more. By using slaked lime slurry and water glass in small amounts, spend 3 minutes or more, add water glass to slaked lime slurry, or add slaked lime slurry and water glass to each other at the same time, thereby reducing the amount of unreacted slaked lime. , Calcium silicate having a crystallite size of 6.0 nm to 16.0 nm, preferably 6.5 nm to 10.0 nm can be produced. The small amount of slaked lime slurry and water glass is an amount to be added over 3 minutes or more, for example, 900 to 1200 ml of water glass per liter of slaked lime slurry so as to have the above Ca / Si molar ratio. Is added to the slaked lime slurry over a period of 3 minutes or more. Alternatively, 1000 ml of slaked lime slurry and 900 to 1200 ml of water glass may be added simultaneously over 3 minutes or more.
一方、水ガラスに消石灰スラリーを添加する方法では、生成する珪酸カルシウム水和物の結晶子サイズが６.０nmよりも小さくなり、さらには非晶質になる傾向がある。さらに、水ガラスに消石灰スラリーを添加する方法で生成させた珪酸カルシウム水和物は、リン含有水に使用したときに、リン回収率およびク溶性リン酸の含有率が低い。 On the other hand, in the method of adding slaked lime slurry to water glass, the crystallite size of the resulting calcium silicate hydrate tends to be smaller than 6.0 nm and further becomes amorphous. Furthermore, the calcium silicate hydrate produced | generated by the method of adding slaked lime slurry to water glass has a low phosphorus collection | recovery rate and the content rate of a soluble phosphoric acid, when it uses for phosphorus containing water.
また、消石灰スラリーに水ガラスを添加する方法、あるいは消石灰スラリーと水ガラスを同時に添加する方法でも、消石灰スラリーの全量と水ガラスの全量を一気に添加すると、珪酸カルシウム水和物の結晶子サイズが６.０nmよりも小さくなり、さらには非晶質になる傾向があるので、何れの方法も好ましくない。 Moreover, even if the method of adding water glass to slaked lime slurry or the method of adding slaked lime slurry and water glass simultaneously, when the total amount of slaked lime slurry and the total amount of water glass are added all at once, the crystallite size of calcium silicate hydrate is 6 Neither method is preferred because it tends to be smaller than 0.0 nm and even amorphous.
本発明のリン回収材は、結晶子サイズが６.０nm〜１６.０nmの微細結晶の珪酸カルシウム水和物（ＣＳＨ）を５０wt％以上、好ましくは８０wt％以上含み、Ｃａ／Ｓｉモル比が０.５〜３.５であるので、リンとの反応性が良く、リン含有水に使用したときに、ＣＳＨの溶解率が５５％以上であり、７０％以上の高いリン回収率を得ることができる。また、リン回収材のＣａ／Ｓｉモル比が０.５〜１.５であってＣＳＨの結晶子サイズが６.０nm〜１０.０nmであるリン回収材は、リン含有水に使用したときに、６０％以上のＣＳＨ溶解率を示し、８０％以上のリン回収率を得ることができ、リン含有水に炭酸が共存している場合でも、７５％以上のリン回収率を得ることができる。 The phosphorus recovery material of the present invention contains fine crystal calcium silicate hydrate (CSH) having a crystallite size of 6.0 nm to 16.0 nm in an amount of 50 wt% or more, preferably 80 wt% or more, and has a Ca / Si molar ratio of 0. Since it is .5 to 3.5, the reactivity with phosphorus is good, and when used in phosphorus-containing water, the dissolution rate of CSH is 55% or more, and a high phosphorus recovery rate of 70% or more can be obtained. it can. Further, when the phosphorus recovery material having a Ca / Si molar ratio of the phosphorus recovery material of 0.5 to 1.5 and the CSH crystallite size of 6.0 nm to 10.0 nm is used for phosphorus-containing water, It exhibits a CSH dissolution rate of 60% or higher, a phosphorus recovery rate of 80% or higher, and a phosphorus recovery rate of 75% or higher even when carbonic acid coexists in phosphorus-containing water.
さらに、本発明のリン回収材は、リン含有水に使用したときに、高いリン回収率を有すると共に、生成したリン酸カルシウムの大部分がク溶性リン酸であり、ク溶性リン酸の含有率が１５wt％以上であるので、使用後のリン回収材を副産リン酸肥料として利用することができる。 Further, the phosphorus recovery material of the present invention has a high phosphorus recovery rate when used in phosphorus-containing water, and most of the generated calcium phosphate is soluble phosphonic acid, and the soluble soluble phosphoric acid content is 15 wt. % Or more, the used phosphorus recovery material can be used as a by-product phosphate fertilizer.
以下、本発明の実施例を比較例と共に示す。以下の例において、珪酸カルシウム水和物(ＣＳＨ)の結晶子サイズ、ＣＳＨ溶解率、リン回収率は以下のようにして測定した。使用後のク溶性リン酸含有率は回収物を肥料分析法に従って測定した。 Examples of the present invention are shown below together with comparative examples. In the following examples, the crystallite size, CSH dissolution rate, and phosphorus recovery rate of calcium silicate hydrate (CSH) were measured as follows. The content of soluble phosphonic acid after use was measured according to the fertilizer analysis method.
ＣＳＨの結晶子サイズ(Ｄ）は、ＣＳＨでは２９°付近に特徴的なピークが見られるため、ＣＳＨ乾燥物についてＸ線回折の解析ピークの半値幅からシェラー式に従って求めた。
シェラー式：Ｄ(ｎｍ)＝Ｋ×λ（β×cosθ）/１０
Ｋはシェラー定数０.９４、λは使用Ｘ線管球の波長、βは結晶子の大きさによる回折線の拡がり、θは回折角２θ／θである。
Ｘ線回折装置はBruker社製品（D8 Advance）を使用した。測定条件は電流３５０mA、電圧３５kV、スキャンスピード０.１３sec/step、測定範囲５°〜６５°とした。
Since the CSH crystallite size (D) has a characteristic peak around 29 ° in CSH, the CSH dried product was determined from the half-value width of the X-ray diffraction analysis peak according to the Scherrer equation.
Scherrer formula: D (nm) = K × λ (β × cos θ) / 10
K is the Scherrer constant 0.94, λ is the wavelength of the X-ray tube used, β is the spread of the diffraction line depending on the crystallite size, and θ is the diffraction angle 2θ / θ.
The X-ray diffractometer was a Bruker product (D8 Advance). The measurement conditions were a current of 350 mA, a voltage of 35 kV, a scan speed of 0.13 sec / step, and a measurement range of 5 ° to 65 °.
リン回収率は、濾液のリン酸濃度を規格（JIS K 0102「工場排水試験方法」）に規定するモリブデン青吸光光度法に準拠して測定し、次式によってリン回収率を求めた。
リン回収率(％)＝（１−濾液のＰ濃度／初期Ｐ濃度）×１００
The phosphorus recovery rate was measured in accordance with the molybdenum blue spectrophotometry method stipulated in the standard (JIS K 0102 “Factory drainage test method”), and the phosphorus recovery rate was determined by the following formula.
Phosphorus recovery (%) = (1−P concentration of filtrate / initial P concentration) × 100
ＣＳＨ溶解率は、規格（JIS R 5202「ポルトランドセメントの化学分析方法」）に準拠してＣＳＨ量を定量し、使用前のＣＳＨ量を全量とし、使用前後のＣＳＨ量に基づき、次式〔１〕によって求めた。
ＣＳＨ溶解率(％)＝(使用前ＣＳＨ量−使用後ＣＳＨ量)／使用前ＣＳＨ量×100・・〔１〕
The CSH dissolution rate is determined according to the standard (JIS R 5202 “Chemical analysis method for Portland cement”). The CSH amount before use is defined as the total amount of CSH before use. ].
CSH dissolution rate (%) = (CSH amount before use-CSH amount after use) / CSH amount before use x 100 ··· [1]
ＣＳＨ量は次式〔２〕によって求めた。
CSH量(％)＝(全SiO２−未反応SiO２)＋(全CaO−炭酸カルシウムCaO−消石灰CaO)＋(Ig-Loss−炭酸カルシウムCO２−消石灰H2O)・・・〔２〕
未反応ＳｉＯ２は塩酸不溶解分を未反応ＳｉＯ２とした。結合水はIg-Loss(1000℃)から炭酸カルシウム由来のＣＯ２と消石灰由来のＨ２Ｏを差し引いた分をＣＳＨの結合水と見なした。ＣＯ２は工業用石灰の無水炭酸迅速定量方法に準拠して炭酸カルシウム量を求めた。消石灰ＣａＯはセメント協会標準試験方法の遊離酸化カルシウムの定量方法に準拠して測定した。
The amount of CSH was determined by the following equation [2].
CSH amount (%) = (total SiO 2 −unreacted SiO 2 ) + (total CaO−calcium carbonate CaO−slaked lime CaO) + (Ig-Loss−calcium carbonate CO 2 −slaked lime H 2 O) (2)
In the unreacted SiO 2, the insoluble portion of hydrochloric acid was regarded as unreacted SiO 2 . The amount of bound water obtained by subtracting calcium carbonate-derived CO 2 and slaked lime-derived H 2 O from Ig-Loss (1000 ° C.) was regarded as CSH-bound water. CO 2 was determined a calcium carbonate content in compliance with the carbonate anhydride Rapid determination method of industrial lime. Slaked lime CaO was measured in accordance with a method for determining free calcium oxide in a standard test method of the Cement Association.
ＣＳＨおよびリン回収物のろ過時間は、スラリー１００ｍｌを減圧吸引ろ過するのに要した時間とした。また、含水率は減圧吸引ろ過により得た固形分について、乾燥前の重量と１５０℃で３時間加熱した後の重量に基づいて求めた。汚泥沈降率(ＳＶ)は、３０分静置した後の沈殿汚泥の容積(ｍｌ)の割合(％)を示す。 The filtration time of the CSH and the phosphorus recovery product was the time required for vacuum filtration of 100 ml of the slurry. Moreover, the water content was calculated | required based on the weight after drying for 3 hours at 150 degreeC and the weight before drying about the solid content obtained by vacuum suction filtration. The sludge sedimentation rate (SV) indicates the ratio (%) of the volume (ml) of the precipitated sludge after standing for 30 minutes.
〔実施例１〕
試料１〜８を表１に示した条件で合成した。試料１〜６は、表１に示すＣａ／Ｓｉモル比になるように、ケイ酸源として３号水ガラス（ＳｉＯ２２９％）を用い、石灰源として消石灰を用い、表１に記載する水量の半量で水ガラスを希釈し、残りの水量で消石灰をスラリーにし、この消石灰スラリーに水ガラスの希釈液を３分の時間をかけて添加して撹拌し、珪酸カルシウム水和物(ＣＳＨ)を生成させた。反応温度と反応時間は表１に示した通りである。
試料７はケイ酸源として珪質頁岩（ＳiＯ２量 ５０wt％）を用い、試料８はケイ酸源として非晶質ケイ酸（ＳiＯ２量 ５５wt％）を用い、おのおの外割りで０.５wt％のＮａＯＨを添加して８５℃に加熱し、そのシリカ懸濁液に消石灰を添加して、８５℃の温度で６時間撹拌して珪酸カルシウム水和物(ＣＳＨ)を生成させた。
生成条件を表１に示す。生成したＣＳＨの組成を表２に示す。試料１〜６はＣＳＨ含有量が５０wt％以上であり、そのうち試料１〜３はＣＳＨ含有量が８０wt％以上である。何れも未反応のシリカを含まない。試料４はＣａ／Ｓｉモル比が高いので消石灰量が多い。
生成したＣＳＨを回収して乾燥し、ＣＳＨの結晶子サイズを測定した。この結晶子サイズを表２に示す。さらに、回収したＣＳＨをリン回収材として用い、リン含有水（ＰＯ4 −３３００ｍｇ/Ｌ）２Ｌに対して、Ｃａ/Ｐモル比が２.０に相当する量のリン回収材を投入して撹拌し、３０分間反応させて、ＣＳＨにリンを取り込ませて回収した。リン回収率、ＣＳＨ溶解率、ク溶性リン酸含有率を表２に示す。
[Example 1]
Samples 1 to 8 were synthesized under the conditions shown in Table 1. Samples 1 to 6 use No. 3 water glass (SiO 2 29%) as the silicic acid source and slaked lime as the lime source so that the Ca / Si molar ratio shown in Table 1 is obtained. Dilute the water glass with half the amount of water, make slaked lime into a slurry with the remaining amount of water, add the water glass dilution to the slaked lime slurry over a period of 3 minutes, stir, and add calcium silicate hydrate (CSH). Generated. The reaction temperature and reaction time are as shown in Table 1.
Sample 7 uses siliceous shale (SiO 2 content 50 wt%) as the silicic acid source, and sample 8 uses amorphous silicic acid (SiO 2 content 55 wt%) as the silicic acid source, each 0.5% by weight. Of NaOH was added and heated to 85 ° C., slaked lime was added to the silica suspension and stirred for 6 hours at a temperature of 85 ° C. to produce calcium silicate hydrate (CSH).
Table 1 shows the generation conditions. The composition of the produced CSH is shown in Table 2. Samples 1 to 6 have a CSH content of 50 wt% or more, and Samples 1 to 3 have a CSH content of 80 wt% or more. None contain unreacted silica. Since sample 4 has a high Ca / Si molar ratio, the amount of slaked lime is large.
The produced CSH was recovered and dried, and the crystallite size of CSH was measured. The crystallite size is shown in Table 2. Further, using the recovered CSH as a phosphorus recovery material, an amount of phosphorus recovery material corresponding to a Ca / P molar ratio of 2.0 is added to 2 L of phosphorus-containing water (PO 4 -3 300 mg / L). The mixture was stirred and allowed to react for 30 minutes, and phosphorus was taken up into CSH and collected. Table 2 shows phosphorus recovery rate, CSH dissolution rate, and soluble phosphoric acid content.
表２に示すように、珪酸カルシウム水和物の結晶子サイズが１６.０nmよりも大きい試料７、試料８はＣＳＨ溶解率が低く、４０％台であるためリン回収率が低く６５.９％以下である。一方、本発明の試料１〜６は、珪酸カルシウム水和物の結晶子サイズが１６.０nm以下であり、ＣＳＨ溶解率は高く５５％以上であるため、７０％以上の高いリン回収率を有する。さらに、珪酸カルシウムの結晶格子サイズが１０.０nm以下の試料１〜３は８０％以上の高いリン回収率を有する。 As shown in Table 2, Sample 7 and Sample 8 in which the crystallite size of calcium silicate hydrate is larger than 16.0 nm have a low CSH dissolution rate and are in the 40% range, so that the phosphorus recovery rate is low and 65.9%. It is as follows. On the other hand, samples 1 to 6 of the present invention have a high phosphorus recovery rate of 70% or more because the crystallite size of calcium silicate hydrate is 16.0 nm or less and the CSH dissolution rate is 55% or more. . Furthermore, Samples 1 to 3 having a calcium silicate crystal lattice size of 10.0 nm or less have a high phosphorus recovery rate of 80% or more.
〔実施例２〕
実施例１のリン回収材（試料１〜４）について、炭酸を含むリン含有水（ＰＯ4 −３３００ｍｇ/Ｌ、炭酸濃度１g/L）２Ｌに対して、Ｃａ/Ｐモル比が２.０に相当する量のリン回収材を投入して撹拌し、３０分間反応させて、ＣＳＨにリンを取り込ませて回収した。リン回収率、ク溶性リン酸含有率を表３に示す。試料１〜３（Ｃａ/Ｓｉモル比＝０.８〜１.５）は何れもリン回収率が７５％以上であり、ク溶性リン酸量（C-P２O５量）は１７％以上である。一方、試料４（Ｃａ/Ｓｉモル比＝３.５）はリン回収率が５３％であり、Ｃａ/Ｓｉモル比＝３.５になるとリン回収率が低下する。従って、本発明のリン回収材をリンと炭酸が共存する排水等に使用する場合には、リン回収材のＣａ／Ｓｉモル比は０.８〜１.５が好ましい。
[Example 2]
Phosphorus recovery material of Example 1 (Samples 1-4), phosphorus-containing water containing carbonate (PO 4 -3 300mg / L, carbonate concentration 1 g / L) against 2L, Ca / P molar ratio of 2.0 An amount of phosphorus recovery material corresponding to 1 was added and stirred, reacted for 30 minutes, and phosphorus was taken into CSH and recovered. Table 3 shows the phosphorus recovery rate and the soluble phosphoric acid content. Samples 1 to 3 (Ca / Si molar ratio = 0.8 to 1.5) all have a phosphorus recovery rate of 75% or more and a soluble phosphonic acid amount (CP 2 O 5 amount) of 17% or more. . On the other hand, Sample 4 (Ca / Si molar ratio = 3.5) has a phosphorus recovery rate of 53%, and when the Ca / Si molar ratio = 3.5, the phosphorus recovery rate decreases. Therefore, when using the phosphorus collection | recovery material of this invention for the waste_water | drain etc. in which phosphorus and carbonic acid coexist, the Ca / Si molar ratio of a phosphorus collection | recovery material has preferable 0.8-1.5.
〔実施例３〕
消石灰スラリー（Ｃａ濃度３.７wt％）と水ガラス（珪酸濃度４.９wt％）を用い、Ｃａ／Ｓｉモル比が１.０になるように、消石灰スラリーに水ガラスを３分以上の時間をかけて添加し撹拌して珪酸カルシウム水和物(ＣＳＨ)を生成させた（標準添加：試料１０〜１２）。また、この消石灰スラリーと水ガラスを３分以上の時間をかけて同時に連続的に添加し撹拌して珪酸カルシウム水和物(ＣＳＨ)を生成させた（同時添加：試料２０〜２１）。一方、試料１０〜１２とは逆に、水ガラスに消石灰スラリーを添加して撹拌し珪酸カルシウム水和物(ＣＳＨ)を生成させた（逆添加：試料３０〜３２）。試料の添加順序および添加時間を表４に示す。これらのＣＳＨのろ過時間、含水率、汚泥沈降率(ＳＶ) 、結晶子サイズを測定し、表４に示した。
生成したＣＳＨを回収して乾燥して得たリン回収材を、実施例１と同様にしてリン含有水に使用し、反応時間３０分後のリン回収率およびク溶性リン酸量を調べた。また、使用後のＣＳＨについて、ろ過時間、含水率、汚泥沈降率(ＳＶ)を使用前のＣＳＨと同様の方法で測定した。この結果を表５に示した。
Example 3
Use slaked lime slurry (Ca concentration 3.7 wt%) and water glass (silicic acid concentration 4.9 wt%), and add water glass to the slaked lime slurry for 3 minutes or more so that the Ca / Si molar ratio is 1.0. And stirred to produce calcium silicate hydrate (CSH) (standard addition: samples 10-12). Moreover, this slaked lime slurry and water glass were added continuously continuously over 3 minutes or more and stirred to produce calcium silicate hydrate (CSH) (simultaneous addition: samples 20 to 21). On the other hand, contrary to samples 10-12, slaked lime slurry was added to water glass and stirred to produce calcium silicate hydrate (CSH) (reverse addition: samples 30-32). Table 4 shows the sample addition sequence and the addition time. The filtration time, water content, sludge sedimentation rate (SV) and crystallite size of these CSH were measured and shown in Table 4.
The phosphorus recovery material obtained by recovering and drying the produced CSH was used in phosphorus-containing water in the same manner as in Example 1, and the phosphorus recovery rate and the amount of soluble phosphoric acid after 30 minutes of reaction time were examined. Moreover, about CSH after use, the filtration time, the moisture content, and the sludge sedimentation rate (SV) were measured by the same method as CSH before use. The results are shown in Table 5.
標準添加の試料１０〜１２は結晶子サイズが７.０nm〜７.２nmであるのでリンとの反応性が良く、７６.６％〜８５.１％の高いリン回収率を示す。また同時添加の試料２０〜２１も結晶子サイズが６.３nm〜８.５nmであるのでリン回収率は高く、７４.４％〜８４.５％である。一方、逆添加の試料３０〜３１は何れも結晶子サイズが６.０nm未満であるためリン回収率は低く、５７.９％〜７２.７％であり、またク溶性リン酸量も低い。この結果から、７５％以上の高いリン回収率を得るにはＣＳＨの結晶子サイズは６.０nm以上が好ましいことが分かる。
なお、逆添加の試料３２は結晶子サイズが６.０nm以上であるが、リン回収後の含水率が１０.６ｇ/ｇであり、試料１〜２，２０〜２２の約２倍であるので脱水に時間がかかる。同様に、逆添加の試料３０〜３２は、ＣＳＨの汚泥沈降率(ＳＶ)と含水率が高く、固液分離や乾燥コストがかさむため望ましくない。一方、同時添加の試料２０〜２１は、ＣＳＨの含水率が３.０g／g未満であり、標準添加の試料より低いので有利であり、さらに逆添加の試料より含水率が格段に低く、逆添加の試料よりも脱水の負担を大幅に低減することができる。
Samples 10 to 12 with standard addition have a crystallite size of 7.0 nm to 7.2 nm, and thus have good reactivity with phosphorus, and show a high phosphorus recovery rate of 76.6% to 85.1%. In addition, the samples 20 to 21 added simultaneously have a crystallite size of 6.3 nm to 8.5 nm, so that the phosphorus recovery rate is high, ie, 74.4% to 84.5%. On the other hand, the reverse addition samples 30 to 31 each have a crystallite size of less than 6.0 nm, so that the phosphorus recovery rate is low, 57.9% to 72.7%, and the amount of soluble phosphoric acid is also low. From this result, it can be seen that the crystallite size of CSH is preferably 6.0 nm or more in order to obtain a high phosphorus recovery rate of 75% or more.
The reverse addition sample 32 has a crystallite size of 6.0 nm or more, but the water content after phosphorus recovery is 10.6 g / g, which is about twice that of samples 1-2 and 20-22. Dehydration takes time. Similarly, the reverse addition samples 30 to 32 are not desirable because they have high CSH sludge sedimentation rate (SV) and moisture content, and increase the cost of solid-liquid separation and drying. On the other hand, the samples 20 to 21 added at the same time are advantageous because the moisture content of CSH is less than 3.0 g / g, which is lower than that of the standard addition sample, and the moisture content is much lower than that of the sample added reversely. The burden of dehydration can be greatly reduced as compared with the added sample.
Claims (3)
Using water slaked lime slurry and water glass in an amount such that the Ca / Si molar ratio of the calcium silicate hydrate to be generated is 0.5 to 3.5, water glass is added to the slaked lime slurry at room temperature for 3 minutes or more. Alternatively, by adding slaked lime slurry and water glass at the same time for 3 minutes or more, fine crystalline calcium silicate hydrate having a crystallite size of 6.0 nm to 16.0 nm is formed, and the calcium silicate hydrate A method for producing a phosphorus recovery material, characterized in that a phosphorus recovery material is obtained by solid-liquid separation.
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