JP2020132515A - Solidified body of neutralized schwertmannite and its production method, as well as cleaning method with solidified body of neutralized schwertmannite - Google Patents
Solidified body of neutralized schwertmannite and its production method, as well as cleaning method with solidified body of neutralized schwertmannite Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000004140 cleaning Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 35
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims abstract description 27
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 21
- 239000010440 gypsum Substances 0.000 claims abstract description 19
- 238000000746 purification Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000003463 adsorbent Substances 0.000 abstract description 7
- 238000010586 diagram Methods 0.000 abstract 1
- 229910052785 arsenic Inorganic materials 0.000 description 37
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 229940085991 phosphate ion Drugs 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 arsenate ions Chemical class 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
【課題】処理対象物中の重金属を固定した後、当該処理対象物から容易に分離出来、且つ、製造も容易な重金属の吸着材とその製造方法、並びに当該吸着材を用いた浄化方法と提供する。
【解決手段】中和シュベルトマナイトと石膏とを含む固化体、および、中和シュベルトマナイトと半水石膏とを混合して混合物を得る工程と、前記混合物へ水を添加した後、混合してスラリーを得る工程と、前記スラリーを固化させて、中和シュベルトマナイトと石膏とを含む固化体を得る工程と、を有する固化体の製造方法を提供する。
【選択図】図１PROBLEM TO BE SOLVED: To provide a heavy metal adsorbent which can be easily separated from the object to be treated and easily manufactured after fixing the heavy metal in the object to be treated, a method for producing the same, and a purification method and a method using the adsorbent. To do.
SOLUTION: A solidified body containing neutralized Schwertmanite and gypsum, and a step of mixing neutralized Schwertmanite and hemihydrate gypsum to obtain a mixture, and adding water to the mixture and then mixing. The present invention provides a method for producing a solidified product, which comprises a step of obtaining a slurry and a step of solidifying the slurry to obtain a solidified product containing neutralized Schwertmanite and gypsum.
[Selection diagram] Fig. 1
Description
本発明は、環境中における砒素を初めとする重金属やリンの回収に用いられる吸着材として最適な中和シュベルトマナイトの固化体およびその製造方法、並びに当該中和シュベルトマナイトの固化体を用いた環境の浄化方法に係る。
尚、本発明において固化体とは、大きさが概ね１ｃｍ３以上で塊状または粒状を有し、水に不溶、且つ、水中で崩壊しない固形物の状態となっていることをいう。
The present invention uses a solidified body of neutralized Schwertmanite, a method for producing the same, and a solidified body of the neutralized Schwertmanite, which is optimal as an adsorbent used for recovering heavy metals such as arsenic and phosphorus in the environment. It is related to the purification method of the environment where it was.
In the present invention, the solidified body means a solid substance having a size of about 1 cm 3 or more, having a lump or a granular shape, being insoluble in water, and not disintegrating in water.
環境中における砒素を初めとする重金属等による汚染は世界的な問題であり、様々な浄化技術や浄化方法が検討され提案されている。
例えば特許文献１には、人工ゼオライトと鉄酸化物とをバインダーにて結合した水質浄化剤が提案されている。
また、本出願人も鉄酸化物であるシュベルトマナイトに注目し、これを中和して化学的安定性を増加させた中和シュベルトマナイトに想到した。そして、特許文献２において当該中和シュベルトマナイトを用いた重金属の固定化方法を開示している。
Contamination by heavy metals such as arsenic in the environment is a global problem, and various purification techniques and methods have been studied and proposed.
For example, Patent Document 1 proposes a water purification agent in which an artificial zeolite and an iron oxide are bonded with a binder.
The applicant also paid attention to the iron oxide Schwertmanite, and came up with a neutralized Schwertmanite that neutralized the iron oxide to increase the chemical stability. Then, Patent Document 2 discloses a method for immobilizing heavy metals using the neutralized Schwertmanite.
環境の浄化方法は、確かな浄化効果を挙げられる方法であることは勿論であるが、マテリアルコストや施工コストも低廉であることが強く求められる。当該観点から従来技術を検討した本発明者らは、以下の課題に想到した。 It goes without saying that the method for purifying the environment is a method that can produce a reliable purification effect, but it is strongly required that the material cost and the construction cost are low. The present inventors who have examined the prior art from this point of view have come up with the following problems.
例えば、特許文献１に記載された水質浄化剤は製造工程が長く複雑である。また、原料にマテリアルコストの高いものを用いていると考えられる。この結果、当該水質浄化剤のマテリアルコストはかなり高価なものになることが懸念される。 For example, the water purification agent described in Patent Document 1 has a long and complicated manufacturing process. In addition, it is considered that raw materials with high material cost are used. As a result, there is concern that the material cost of the water purification agent will be considerably high.
一方、特許文献２に記載された中和シュベルトマナイトは低廉な原料を用い、比較的単純な工程で製造可能でありながら、化学的にも安定である。従って、低廉なマテリアルコストを実現できると考えられる。
しかし、中和シュベルトマナイトは微細な粒子である。従って、処理対象物（例えば、汚染水）に含まれる砒素を初めとする重金属を吸着し固定した後、当該処理対象物から重金属を吸着固定した中和シュベルトマナイトを分離する工程迄を考える場合は、処理コストが嵩むことが考えられる。
On the other hand, the neutralized Schwertmanite described in Patent Document 2 uses an inexpensive raw material and can be produced by a relatively simple process, but is also chemically stable. Therefore, it is considered that a low material cost can be realized.
However, neutralized Schwertmanite is a fine particle. Therefore, when considering the process of adsorbing and fixing heavy metals such as arsenic contained in the object to be treated (for example, contaminated water) and then separating the neutralized Schwertmanite adsorbed and fixed to the heavy metal from the object to be treated. Is considered to increase the processing cost.
本発明は上述の状況の下で為されたものであり、その解決しようとする課題は、処理対象物中の重金属を固定した後、当該処理対象物から容易に分離出来、且つ、製造も容易な重金属の吸着材とその製造方法、並びに当該吸着材を用いた処理対象物の浄化方法、とを提供することである。 The present invention has been made under the above-mentioned circumstances, and the problem to be solved is that after fixing the heavy metal in the object to be treated, it can be easily separated from the object to be processed and easily manufactured. It is an object of the present invention to provide an adsorbent for heavy metals, a method for producing the same, and a method for purifying an object to be treated using the adsorbent.
上述の課題を解決する為、本発明者らは研究をおこなった。そして、中和シュベルトマナイトは良好な吸着性能を発揮すると共に化学的に安定である上、マテリアルコストも低廉であって、砒素を初めとする重金属等の吸着物質として優れていることを認識した。
ここで、本発明者らは、重金属を固定した中和シュベルトマナイトを処理対象物から容易に分離する手法について、さらに研究をおこなった。そして、石膏を固化材として用いた中和シュベルトマナイトの固化体に想到し本発明を完成した。
In order to solve the above-mentioned problems, the present inventors conducted research. It was also recognized that neutralized Schwertmannite exhibits good adsorption performance, is chemically stable, has a low material cost, and is excellent as an adsorbent for heavy metals such as arsenic. ..
Here, the present inventors further studied a method for easily separating neutralized Schwertmanite on which a heavy metal is fixed from an object to be treated. Then, he came up with a solidified body of neutralized Schwertmanite using gypsum as a solidifying material, and completed the present invention.
即ち、上述の課題を解決する第１の発明は、
中和シュベルトマナイトと石膏とを含む固化体である。
第２の発明は、
１００質量部の中和シュベルトマナイトに対して、５０質量部以上１５０質量部以下の石膏を含む第１の発明に記載の固化体である。
第３の発明は、
中和シュベルトマナイトと半水石膏とを混合して混合物を得る工程と、
前記混合物へ水を添加した後、混合してスラリーを得る工程と、
前記スラリーを固化させて、中和シュベルトマナイトと石膏とを含む固化体を得る工程
と、を有する固化体の製造方法である。
第４の発明は、
１００質量部の中和シュベルトマナイトに対して、５０質量部以上１５０質量部以下の半水石膏を混合する、第３の発明に記載の固化体の製造方法である。
第５の発明は、
半水石膏１００質量部に対して、２００質量部を超え４００質量部以下の水を添加する、第３または第４の発明に記載の固化体の製造方法である。
第６の発明は、
重金属を含有する処理対象の水中へ、第１または第２の発明に記載の固化体を投入して前記重金属を吸着させた後に、前記水中から前記固化体を分離する浄化方法である。
That is, the first invention that solves the above-mentioned problems is
It is a solidified product containing neutralized Schwertmanite and gypsum.
The second invention is
The solidified body according to the first invention, which comprises 50 parts by mass or more and 150 parts by mass or less of gypsum with respect to 100 parts by mass of neutralized Schwertmanite.
The third invention is
The process of mixing neutralized Schwertmanite and hemihydrate gypsum to obtain a mixture,
A step of adding water to the mixture and then mixing to obtain a slurry.
This is a method for producing a solidified body, which comprises a step of solidifying the slurry to obtain a solidified body containing neutralized Schwertmanite and gypsum.
The fourth invention is
The method for producing a solidified body according to the third invention, wherein 50 parts by mass or more and 150 parts by mass or less of hemihydrate gypsum is mixed with 100 parts by mass of neutralized Schwertmanite.
The fifth invention is
The method for producing a solidified body according to the third or fourth invention, wherein water of more than 200 parts by mass and 400 parts by mass or less is added to 100 parts by mass of hemihydrate gypsum.
The sixth invention is
This is a purification method in which the solidified body according to the first or second invention is put into the water to be treated containing a heavy metal, the heavy metal is adsorbed, and then the solidified body is separated from the water.
本発明に係る中和シュベルトマナイトと石膏とを含む固化体は、処理対象物中の重金属を吸着固定した後、当該処理対象物から容易に分離出来た。 The solidified body containing the neutralized Schwertmanite and gypsum according to the present invention could be easily separated from the object to be treated after adsorbing and fixing the heavy metal in the object to be treated.
本発明は、環境中における砒素を初めとする重金属やリンの回収に用いられる吸着材として最適な中和シュベルトマナイトの固化体およびその製造方法、並びに当該中和シュベルトマナイトの固化体を用いた環境の浄化方法に係るものである。
以下、本発明について［１］中和シュベルトマナイト、［２］中和シュベルトマナイトの固化材、［３］中和シュベルトマナイトの固化体、［４］中和シュベルトマナイトの固化体の製造方法、［５］中和シュベルトマナイトの固化体を用いた処理対象物の浄化方法、の順に説明する。
The present invention uses a solidified body of neutralized Schwertmanite, a method for producing the same, and a solidified body of the neutralized Schwertmanite, which is optimal as an adsorbent used for recovering heavy metals such as arsenic and phosphorus in the environment. It is related to the purification method of the existing environment.
Hereinafter, the present invention relates to [1] neutralized Schwertmanite, [2] neutralized Schwertmanite solidifying material, [3] neutralized Schwertmanite solidified body, and [4] neutralized Schwertmanite solidified body. The production method and [5] the method for purifying the object to be treated using the solidified body of neutralized Schwertmanite will be described in this order.
［１］中和シュベルトマナイト
本発明に係る中和シュベルトマナイトは、Ｆｅ８Ｏ８（ＯＨ）８−２ｘ（ＳＯ４）ｘ（但し、ｘは１≦ｘ≦１．７５である。）構造を示すシュベルトマナイトへ、カルシウム化合物（ＣａＳＯ４、ＣａＣＯ３、ＣａＯ、およびＣａ（ＯＨ）２から選択されるいずれか１種以上）を反応させて、当該シュベルトマナイトの分子構造中に存在する硫酸イオンの少なくとも一部をカルシウムイオンに置換したものである。
以下、（１）シュベルトマナイトおよび中和シュベルトマナイト、（２）中和シュベルトマナイトの製造方法例、（３）重金属の固定化剤としての中和シュベルトマナイト、の順に説明する。
[1] Neutralized Schwertmanite The neutralized Schwertmanite according to the present invention is Fe 8 O 8 (OH) 8-2x (SO 4 ) x (where x is 1 ≦ x ≦ 1.75). Calcium compound (one or more selected from CaSO 4 , CaCO 3 , CaO, and Ca (OH) 2 ) is reacted with Schwertmanite showing the structure and is present in the molecular structure of the Schwertmanite. At least a part of the sulfate ion is replaced with calcium ion.
Hereinafter, (1) Schwertmanite and neutralized Schwertmanite, (2) an example of a method for producing neutralized Schwertmanite, and (3) neutralized Schwertmanite as a fixing agent for heavy metals will be described in this order.
（１）シュベルトマナイトおよび中和シュベルトマナイト
シュベルトマナイトは、砒素を初めとする重金属に対して高い吸着能を有する。しかし、当該シュベルトマナイトは水等に溶解し易く、溶解そして再析出を経ることによりゲータイトへ変異し易い。この結果、当該シュベルトマナイトを、処理対象物である例えば重金属を含有する汚染水へ添加した場合、または、長期間の保存又は輸送を行った場合には、ゲータイトへの変異が起こり、重金属に対する吸着能を発揮できないことがあった。
(1) Schwertmanite and Neutralized Schwertmanite Schwertmanite has a high adsorptive capacity for heavy metals such as arsenic. However, the Schwertmanite is easily dissolved in water or the like, and is easily mutated to goethite through dissolution and reprecipitation. As a result, when the Schwertmanite is added to contaminated water containing a heavy metal, for example, which is the object to be treated, or when it is stored or transported for a long period of time, a mutation to goethite occurs and the heavy metal is mutated. In some cases, the adsorption ability could not be exhibited.
これに対し、本発明に係る中和シュベルトマナイトは、酸性化合物であるシュベルトマナイトを上述したカルシウム化合物で中和し、シュベルトマナイトのカルシウム塩とすることで水との反応性を抑制し耐水性を付与したものである。当該中和反応は容易に進み、生産効率面、コスト面といった観点から実施が容易である。さらに、シュベルトマナイトのカルシウム塩は中性である。この結果、環境へ与える負荷が殆ど無く、好ましい。 On the other hand, the neutralized Schwertmanite according to the present invention suppresses the reactivity with water by neutralizing the acidic compound Schwertmanite with the above-mentioned calcium compound and converting it into a calcium salt of Schwertmanite. It is water resistant. The neutralization reaction proceeds easily, and is easy to carry out from the viewpoints of production efficiency and cost. In addition, the calcium salt of Schwertmanite is neutral. As a result, there is almost no load on the environment, which is preferable.
（２）中和シュベルトマナイトの製造方法例
中和シュベルトマナイトの製造方法例について説明する。
硫化鉄鉱床の鉱山から得られる排水へ第二鉄塩を添加し、さらにアルカリを添加してｐＨを３〜４の範囲とする。そして水酸化第二鉄の沈殿を形成させた後、当該排水を殿物スラリーと上澄水とに分離する（除去工程）。
前記除去工程で得られた上澄水へ鉄酸化細菌を添加し、前記上澄水に含まれる２価鉄を３価鉄へ酸化して処理液を得る（酸化工程）。
前記酸化工程後の処理液をバクテリア酸化殿物スラリーと上澄水とに分離し、得られた酸化工程後の上澄水へ炭酸カルシウムを添加して中和し、ｐＨを４〜５の範囲とする（第一の中和工程）。そして、前記第一の中和工程後の液へ消石灰：２水石膏（ＣａＳＯ４・２Ｈ２Ｏ）および／または半水石膏（ＣａＳＯ４・１／２Ｈ２Ｏ）を添加して中和し、ｐＨを７〜９の範囲とすることで（第二の中和工程）、本発明に係る中和シュベルトマナイトが得られる。
(2) Example of Manufacturing Method of Neutralized Schwert Manite An example of manufacturing method of neutralized Schwert Manite will be described.
A ferric salt is added to the wastewater obtained from the iron sulfide deposit mine, and an alkali is further added to bring the pH in the range of 3 to 4. Then, after forming a ferric hydroxide precipitate, the wastewater is separated into a slurry and a supernatant water (removal step).
Iron-oxidizing bacteria are added to the supernatant water obtained in the removal step, and ferrous iron contained in the supernatant water is oxidized to ferric iron to obtain a treatment liquid (oxidation step).
The treatment liquid after the oxidation step is separated into a bacterial oxidation compound slurry and a supernatant water, and calcium carbonate is added to the obtained supernatant water after the oxidation step to neutralize the solution, and the pH is set in the range of 4 to 5. (First neutralization step). Then, the to the first solution after the neutralization step of hydrated lime: 2 dihydrate gypsum (CaSO 4 · 2H 2 O) and / or hemihydrate gypsum (CaSO 4 · 1 / 2H 2 O) was added for neutralization, By setting the pH in the range of 7 to 9 (second neutralization step), the neutralized gypsum according to the present invention can be obtained.
（３）重金属の固定化剤としての中和シュベルトマナイト
本発明に係る中和シュベルトマナイトは、砒素を初めとする重金属を十分に固定化、不溶化出来るものであった。
このメカニズムは現在確認中であるが、シュベルトマナイトの重金属吸着能とカルシウム塩との相乗効果の発現、添加されたカルシウム塩による中和シュベルトマナイトのさらなる安定化効果の発揮、等によるものではないかと推察できる。
(3) Neutralizing Schwertmanite as an Fixing Agent for Heavy Metals The neutralizing Schwertmanite according to the present invention was capable of sufficiently immobilizing and insolubilizing heavy metals such as arsenic.
This mechanism is currently being confirmed, but it may be due to the synergistic effect of the heavy metal adsorption capacity of Schwertmanite and the calcium salt, and the further stabilization effect of the neutralized Schwertmanite by the added calcium salt. It can be inferred that there is no such thing.
［２］中和シュベルトマナイトの固化材
上述したように本発明に係る中和シュベルトマナイトは、砒素を初めとする重金属に対する優れた固定化剤である。さらに、未中和のシュベルトマナイトに較べ耐水性も有している。しかしながら、中和シュベルトマナイトは粉体形状を有している為、重金属を含有する処理対象の水中へ当該中和シュベルトマナイトを添加し、重金属を吸着させた後、被処理水と重金属を吸着した中和シュベルトマナイトとを分離する操作を求められた場合に課題がある。
[2] Solidifying Material of Neutralized Schwert Manite As described above, the neutralized Schwert Manite according to the present invention is an excellent fixing agent for heavy metals such as arsenic. Furthermore, it has water resistance as compared with unneutralized Schwertmanite. However, since the neutralized Schwertmanite has a powder shape, the neutralized Schwertmanite is added to the water to be treated containing a heavy metal, the heavy metal is adsorbed, and then the water to be treated and the heavy metal are separated. There is a problem when an operation for separating the adsorbed neutralized Schwertmanite is required.
当該分離操作としては、自然沈降による分離、遠心分離、さらには、フィルターを用いた濾過分離等が考えられる。しかし、いずれの分離方法を採るにしても、時間や処理コストが嵩むことが考えられる。 As the separation operation, separation by natural sedimentation, centrifugation, and filtration separation using a filter can be considered. However, whichever separation method is adopted, time and processing cost may increase.
ここで本発明者らは、適宜な固化材により中和シュベルトマナイトを固体成型して固化体とすることが出来れば、重金属を含有する処理対象の水中へ当該中和シュベルトマナイトの固化体を適用した後、重金属を吸着した当該固化体を容易に、被処理水から分離可能となることに想到した。 Here, if the neutralized Schwertmanite can be solid-molded into a solidified body with an appropriate solidifying material, the present inventors can put the neutralized Schwertmanite into the water to be treated containing a heavy metal. After applying the above, it was conceived that the solidified body adsorbed with heavy metals could be easily separated from the water to be treated.
中和シュベルトマナイトを固体成型する為の固化材として、例えば特許文献１：（００５３）〜（００５４）段落に記載されているような有機高分子系バインダーが考えられる。しかし有機高分子系バインダーを使用した場合、当該固形材のマテリアルコストが高い為、結局、製造される固体成型中和シュベルトマナイトの製造コストが上昇してしまうこととなる。 As a solidifying material for solid-molding the neutralized Schwertmanite, for example, an organic polymer-based binder as described in paragraphs 1 (0053) to (0054) of Patent Document can be considered. However, when an organic polymer-based binder is used, the material cost of the solid material is high, so that the production cost of the solid-molded neutralized Schwertmanite to be produced will increase in the end.
ここで、本発明者らは研究を進め、中和シュベルトマナイトの固化剤として半水石膏（ＣａＳＯ４・１／２Ｈ２Ｏ）を使用する構成に想到した。
半水石膏は水と混合されることにより、数１０％以上の気孔率を含んだ状態で固化することから，本手法により中和シュベルトマナイトを内包し、浄化径路を内部に含む中和シュベルトマナイトの固化体を比較的簡便に得ることができるからである。また，原料石膏に廃石膏を活用することで、従来技術よりも安価なマテリアルコストで、環境負荷の低い中和シュベルトマナイトの固化体を用いた、砒素を初めとする重金属やリンの回収技術への応用が期待できることによる。
Here we studying, and conceived as a solidifying agent for neutralizing schwertmannite configurations using hemihydrate gypsum (CaSO 4 · 1 / 2H 2 O).
When hemihydrate gypsum is mixed with water, it solidifies with a porosity of several tens of percent or more. Therefore, this method contains neutralized gypsum and neutralized gypsum containing a purification path inside. This is because a solidified body of manite can be obtained relatively easily. In addition, by utilizing waste gypsum as the raw material gypsum, a technology for recovering heavy metals such as arsenic and phosphorus using a solidified body of neutralized Schwertmanite, which has a lower environmental load at a lower material cost than the conventional technology. Because it can be expected to be applied to.
［３］中和シュベルトマナイトの固化体
特許文献１は、（００５３）段落の１箇所においてバインダーとしての石膏について、文言的に触れている。しかしながら、特許文献１では、処理水への投入後のｐＨ変化を考慮した為に、石膏の使用には消極的な記載がされている。これは、特許文献１では重金属の固定化剤として、本発明とは異なり未中和のシュベルトマナイトを使用している為、当該未中和のシュベルトマナイトおよび固化材の双方がｐＨへ与える影響を考慮しなければならない為であると考えられる。
これに対し、本発明においては重金属の固定化剤として中和シュベルトマナイトを用いる構成である為、固化材として半水石膏を用いても、環境への負荷は殆ど無いものである。
当該観点からも、本発明に係る中和シュベルトマナイトを、適宜量の半水石膏を用いて固化させた中和シュベルトマナイトの固化体、および、当該中和シュベルトマナイトの固化体を用いた被処理対象物からの、砒素を初めとする重金属やリンの回収方法は優れたものであると考えられる。
[3] Solidified body of neutralized Schwertmanite Patent Document 1 literally mentions gypsum as a binder in one paragraph (0053). However, Patent Document 1 makes a reluctant description about the use of gypsum in consideration of the pH change after the addition to the treated water. This is because, unlike the present invention, unneutralized Schwertmanite is used as the fixing agent for heavy metals in Patent Document 1, so that both the unneutralized Schwertmanite and the solidifying material give the pH to pH. It is thought that this is because the impact must be taken into consideration.
On the other hand, in the present invention, since the neutralized Schwertmanite is used as the fixing agent for heavy metals, even if hemihydrate gypsum is used as the solidifying material, there is almost no burden on the environment.
From this point of view as well, a solidified body of the neutralized Schwertmanite obtained by solidifying the neutralized Schwertmanite according to the present invention with an appropriate amount of hemihydrate gypsum and a solidified body of the neutralized Schwertmanite are used. It is considered that the method for recovering heavy metals such as arsenic and phosphorus from the object to be treated is excellent.
［４］中和シュベルトマナイトの固化体の製造方法
中和シュベルトマナイトの固化体の製造方法について、１例を挙げながら説明する。
中和シュベルトマナイトを乳鉢等にて解砕した後、篩にて篩分けして、中和シュベルトマナイト粉体を得る。得られた中和シュベルトマナイト粉体へ半水石膏を加え、十分に混合した後、所定量の脱イオン水を加えて攪拌する。
[4] Method for Producing Solidified Body of Neutralized Schwertmanite A method for producing a solidified body of neutralized Schwertmanite will be described with reference to an example.
Neutralized Schwertmanite is crushed in a mortar or the like and then sieved through a sieve to obtain neutralized Schwertmanite powder. Semi-hydrated gypsum is added to the obtained neutralized Schwertmanite powder and mixed thoroughly, and then a predetermined amount of deionized water is added and stirred.
中和シュベルトマナイト粉体へ半水石膏を加える際、中和シュベルトマナイト粉体と、半水石膏との混合比率は１００：５０〜１００：１５０であることが好ましい。
また、中和シュベルトマナイト粉体と半水石膏との混合物へ、脱イオン水を加える際、中和シュベルトマナイト粉体と半水石膏との混合物と、脱イオン水との混合比率は１００：２００〜１００：４００であることが好ましい。
When adding hemihydrate gypsum to the neutralized Schwertmanite powder, the mixing ratio of the neutralized Schwertmanite powder and the hemihydrate gypsum is preferably 100:50 to 100:150.
When deionized water is added to the mixture of neutralized Schwertmanite powder and hemihydrate gypsum, the mixing ratio of the mixture of neutralized Schwertmanite powder and hemihydrate gypsum and the deionized water is 100. : 200 to 100: 400 is preferable.
中和シュベルトマナイト粉体と半水石膏と脱イオン水とを攪拌し、好ましくは脱泡してスラリーを得る。得られたスラリーを所望の内寸を有する適宜な型に流し込み、室温にて１２時間程度静置して硬化させて固化体を得る。当該固化体を型から離型し、好ましくは５０℃程度の雰囲気下で１２時間程度乾燥させて、本発明に係る中和シュベルトマナイトの固化体を得る。 The neutralized Schwertmanite powder, hemihydrate gypsum and deionized water are stirred and preferably defoamed to obtain a slurry. The obtained slurry is poured into an appropriate mold having a desired inner size, and allowed to stand at room temperature for about 12 hours to be cured to obtain a solidified body. The solidified body is removed from the mold and dried in an atmosphere of preferably about 50 ° C. for about 12 hours to obtain a solidified body of the neutralized Schwertmanite according to the present invention.
［５］中和シュベルトマナイトの固化体を用いた処理対象物の浄化方法
本発明に係る中和シュベルトマナイトの固化体を用いた浄化方法の処理対象物としては、まず、砒素を初めとする重金属やリンを含む水が考えられる。そこで、以下、処理対象物が当該砒素等を含む水である場合を例として、中和シュベルトマナイトの固化体を用いた処理対象物の浄化方法について説明する。
[5] Purification Method of Object to be Treated Using Solidified Body of Neutralized Schwertmanite As the object to be treated by the purification method using the solidified body of neutralized Schwertmanite according to the present invention, first, arsenic is used. Water containing heavy metals and phosphorus can be considered. Therefore, a method for purifying the object to be treated using a solidified body of neutralized Schwertmanite will be described below, taking as an example the case where the object to be treated is water containing the arsenic or the like.
上述したように、本発明に係る中和シュベルトマナイトの固化体は、固化材として半水石膏を用い数１０％以上の気孔率を有し、環境への負荷は殆ど無いものである。
そこで、処理対象物の水へ、本発明に係る中和シュベルトマナイトの固化体の適宜量を直接投入し、当該固化体の内部に含まれる浄化径路において砒素等を吸着させる。当該吸着過程において、中和シュベルトマナイトの固化体は崩壊しない。そこで、当該吸着過程が完了したと考えられる時点で、適宜な目開きを有するメッシュ等を用いて、浄化された処理対象物の水と固化体とを容易に分離することが出来る。
また、中和シュベルトマナイトの固化体の集積体中へ処理対象物の水を通過させて、当該処理対象物の水を浄化することも可能である。
As described above, the solidified body of the neutralized Schwertmanite according to the present invention uses hemihydrate gypsum as a solidifying material and has a porosity of several tens of percent or more, and has almost no burden on the environment.
Therefore, an appropriate amount of the solidified body of the neutralized Schwertmanite according to the present invention is directly added to the water of the object to be treated, and arsenic or the like is adsorbed in the purification path contained inside the solidified body. In the adsorption process, the solidified body of neutralized Schwertmanite does not collapse. Therefore, when it is considered that the adsorption process is completed, the water of the purified object to be treated and the solidified body can be easily separated by using a mesh or the like having an appropriate opening.
It is also possible to purify the water of the object to be treated by passing the water of the object to be treated into the aggregate of the solidified body of the neutralized Schwertmanite.
以下、実施例を参照しながら、本発明をより具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
（実施例１）
実施例１について、〈１〉中和シュベルトマナイトの固化体の製造、〈２〉中和シュベルトマナイトのリン酸イオン除去率測定による固化体の特性評価、〈３〉中和シュベルトマナイトの固化体のリン酸イオン除去率測定による特性評価についての説明、〈４〉中和シュベルトマナイトの固化体の砒素除去率測定による特性評価、の順で説明する。
(Example 1)
Regarding Example 1, <1> production of a solidified body of neutralized Schwertmanite, <2> characteristic evaluation of the solidified body by measuring the phosphate ion removal rate of neutralized Schwertmanite, and <3> neutralized Schwertmanite. The description of the characteristic evaluation by measuring the phosphate ion removal rate of the solidified body and the characteristic evaluation by measuring the arsenic removal rate of the solidified body of the neutralized Schwertmanite will be described in this order.
〈１〉中和シュベルトマナイトの固化体の製造
「［１］中和シュベルトマナイト、（２）中和シュベルトマナイトの製造方法例」にて説明した製造方法により、中和シュベルトマナイトを製造した。
製造した中和シュベルトマナイトをアルミナ製の乳鉢で解砕し、目開き１８０μｍのステンレス製篩にて篩分けして得た、中和シュベルトマナイト粉体１０ｇを準備した。
一方、半水石膏として市販の半水石膏（Ａ級、吉野石膏（株）製）１０ｇを準備した。
当該中和シュベルトマナイト粉体１０ｇと、半水石膏１０ｇとを１００ｍｌのプラスチックカップ内で十分に混合し、そこへ３０ｇの脱イオン水を加えた。
<1> Production of a solidified body of neutralized Schwertmanite Neutralized Schwertmanite is produced by the production method described in "[1] Neutralized Schwertmanite, (2) Example of manufacturing method of neutralized Schwertmanite". Manufactured.
10 g of the neutralized Schwertmanite powder obtained by crushing the produced neutralized Schwertmanite in an alumina mortar and sieving with a stainless steel sieve having an opening of 180 μm was prepared.
On the other hand, as a hemihydrate gypsum, 10 g of commercially available hemihydrate gypsum (class A, manufactured by Yoshino Gypsum Co., Ltd.) was prepared.
10 g of the neutralized Schwertmanite powder and 10 g of hemihydrate gypsum were sufficiently mixed in a 100 ml plastic cup, and 30 g of deionized water was added thereto.
当該カップの内容物を、自転公転ミキサー（ＡＲＥ−３１０、シンキー（株）製）を用いて２０００ｒｐｍで３０秒間攪拌した。次に、２２００ｒｐｍで３０秒間攪拌して脱泡した。その後、プラスチック棒を用い、６０秒間手混ぜ攪拌して、実施例１に係るスラリーとした。
当該スラリーをシリコン製またはプラスチック製の型（内形状：１２×１２×１２ｍｍ３）に流し込み、２５℃にて１２時間静置して硬化させて硬化物とした。得られた硬化物を型から離型し、５０℃の高温槽にて１２時間乾燥させて、実施例１に係る中和シュベルトマナイト固化体（外形状：１２×１２×１２ｍｍ３）を得た。
当該固化体の外観を図１、水中における固化体の外観を図２、物性値を表１に示す。
The contents of the cup were stirred at 2000 rpm for 30 seconds using a rotation / revolution mixer (ARE-310, manufactured by Shinky Co., Ltd.). Next, the bubbles were defoamed by stirring at 2200 rpm for 30 seconds. Then, using a plastic rod, it was manually mixed and stirred for 60 seconds to obtain a slurry according to Example 1.
The slurry was poured into a silicon or plastic mold (inner shape: 12 × 12 × 12 mm 3 ) and allowed to stand at 25 ° C. for 12 hours to be cured to obtain a cured product. The obtained cured product was removed from the mold and dried in a high temperature bath at 50 ° C. for 12 hours to obtain a neutralized Schwertmanite solidified body (outer shape: 12 × 12 × 12 mm 3 ) according to Example 1. It was.
The appearance of the solidified body is shown in FIG. 1, the appearance of the solidified body in water is shown in FIG. 2, and the physical property values are shown in Table 1.
尚、嵩密度（外形）は、固化体試料の乾燥重量を、当該試料の外寸法から求めた体積で割ることで求めた。
比表面積は窒素吸着法によるＢＥＴ多点法で求めた。具体的には、比表面積／細孔分布測定装置（マイクロトラックベル製ＢＥＬＳＯＲＰ−ｍｉｎｉＩＩ）を使用した。そして、１００℃で１０時間の真空脱気を施し、液体窒素温度で窒素を低圧から飽和吸着させ、相対圧０．１０〜０．３５の７点におけるＢＥＴ多点法による解析を行った。
見かけ密度、嵩密度、気孔率はＪＩＳ規格Ｚ８８０７（固体の密度及び比重の測定方法）の「８：液中ひょう量法による密度及び比重の測定方法」に準拠して求めた。
以下、実施例２〜５も同様である。
The bulk density (outer shape) was determined by dividing the dry weight of the solidified sample by the volume obtained from the outer dimensions of the sample.
The specific surface area was determined by the BET multipoint method by the nitrogen adsorption method. Specifically, a specific surface area / pore distribution measuring device (BELSORP-miniII manufactured by Microtrac Bell) was used. Then, vacuum degassing was performed at 100 ° C. for 10 hours, nitrogen was saturated and adsorbed from a low pressure at a liquid nitrogen temperature, and analysis was performed by the BET multipoint method at 7 points with a relative pressure of 0.10 to 0.35.
The apparent density, bulk density, and porosity were determined in accordance with JIS Standard Z8807 (Method for measuring solid density and specific gravity) "8: Method for measuring density and specific gravity by the in-liquid weighing method".
Hereinafter, the same applies to Examples 2 to 5.
〈２〉中和シュベルトマナイトの固化体のリン酸イオン除去率測定による特性評価
リン酸塩としてリン酸二水素カリウム（ＫＨ２ＰＯ４）を用い、所定濃度２００ｐｐｍを有するリン酸溶液を得た。
実施例１に係る中和シュベルトマナイト固化体０．１ｇと、前記リン酸溶液（所定濃度２００ｐｐｍ）１００ｍｌとを混合し、２５℃の下、中和シュベルトマナイト固化体とリン酸溶液とを２４時間反応させ、リン酸を、十分にシュベルトマナイト固化体へ飽和吸着させた。
<2> Evaluation of Characteristics of Neutralized Schwertmanite Solution by Measuring Phosphate Ion Removal Rate Using potassium dihydrogen phosphate (KH 2 PO 4 ) as a phosphate, a phosphate solution having a predetermined concentration of 200 ppm was obtained. ..
0.1 g of the neutralized Schwertmanite solidified product according to Example 1 and 100 ml of the phosphoric acid solution (predetermined concentration 200 ppm) are mixed, and the neutralized Schwertmanite solidified product and the phosphoric acid solution are mixed at 25 ° C. After reacting for 24 hours, phosphoric acid was sufficiently saturated and adsorbed on the Schwertmannite solidified product.
当該吸着反応の後、反応後の溶液を１０ｍｌ分取し、２５ｍｌのメスフラスコへ移した。このとき、実施例１に係る中和シュベルトマナイト固化体は、溶液中でも崩壊しなかったので、反応後の溶液と中和シュベルトマナイト固化体とは容易に分離が出来た。 After the adsorption reaction, 10 ml of the solution after the reaction was taken and transferred to a 25 ml volumetric flask. At this time, the neutralized Schwertmanite solidified product according to Example 1 did not disintegrate even in the solution, so that the solution after the reaction and the neutralized Schwertmanite solidified product could be easily separated.
当該メスフラスコへＭｏ（ｖ）−Ｍｏ（ｖｉ）試薬を１．０ｍｌ加え、標線付近まで脱イオン水を入れた。そして、沸騰水の入ったビーカーに当該メスフラスコを入れ、３０分間程度浸漬して試薬を発色させた。
当該メスフラスコを冷却後、脱イオン水を加えて正確に標線合わせを行い試料溶液とした。当該試料溶液の波長８３０ｎｍの吸光度を吸光光度計（ＵＶ−２４５０、島津製作所（株）製）で測定した。一方、リン酸の標準溶液から得られた検量線から、当該試料溶液のリン酸濃度を求め、実施例１に係る中和シュベルトマナイト固化体のリン酸イオン除去率（１ｇの固化体が除去するリン酸イオン量（ｍｇ））を算出した。当該算出結果を表１に示す。
1.0 ml of Mo (v) -Mo (vi) reagent was added to the volumetric flask, and deionized water was added to the vicinity of the marked line. Then, the volumetric flask was placed in a beaker containing boiling water and immersed for about 30 minutes to develop the color of the reagent.
After cooling the volumetric flask, deionized water was added and the markings were accurately aligned to prepare a sample solution. The absorbance of the sample solution at a wavelength of 830 nm was measured with an absorptiometer (UV-2450, manufactured by Shimadzu Corporation). On the other hand, the phosphoric acid concentration of the sample solution was determined from the calibration line obtained from the standard solution of phosphoric acid, and the phosphate ion removal rate of the neutralized Schwertmanite solidified product according to Example 1 (1 g of the solidified product was removed). The amount of phosphate ion (mg) to be produced was calculated. The calculation results are shown in Table 1.
〈３〉中和シュベルトマナイトの固化体のリン酸イオン除去率測定による特性評価についての説明
実施例１において、中和シュベルトマナイト固化体の吸着性能を評価するにあたり、リン酸イオンを砒酸イオンの代替として用いた測定を行った。
良く知られているように、砒素や砒酸は生物への毒性が高い物質であり、取り扱いには格段の配慮が必要である。この為、一般的な設備を有する実験室や研究所では砒素や砒酸の使用が制限されることも多い。一方、砒素の水中形態である砒酸イオン（ＡｓＯ４ ３−）は正四面体構造を有するオキソニウムイオンであり、リンの水中形態であるリン酸イオン（ＰＯ４ ３−）と同様の構造を有している。また、砒酸はリン酸と同様の３段階の解離性を示す。
この為、砒酸イオンと同型であり挙動もよく似ているリン酸イオンを用いた。
<3> Description of Characteristic Evaluation of Neutralized Schwertmanite Solidified Body by Measuring Phosphate Ion Removal Rate In Example 1, in evaluating the adsorption performance of the neutralized Schwertmanite solidified body, phosphate ions were used as arsenate ions. The measurement used as an alternative to was performed.
As is well known, arsenic and arsenic are substances that are highly toxic to living organisms, and special care must be taken when handling them. For this reason, the use of arsenic and arsenic is often restricted in laboratories and laboratories with general equipment. On the other hand, arsenate ion in-water form of arsenic (AsO 4 3-) is the oxonium ion with a tetrahedral structure, have a phosphate ion (PO 4 3-) and similar structures in-water form of phosphorus are doing. In addition, arsenic acid exhibits three levels of dissociability similar to phosphoric acid.
Therefore, phosphate ion, which is the same type as arrate ion and has similar behavior, was used.
〈４〉中和シュベルトマナイトの固化体の砒素除去率測定による特性評価
本発明に係る中和シュベルトマナイトの固化体の特性評価を、さらに確認する為、上述した中和シュベルトマナイトの固化体のリン酸イオン除去率測定による特性評価に続けて、砒素除去率測定による特性評価を実施した。
<4> Characteristic evaluation by measuring the arsenic removal rate of the solidified body of neutralized Schwertmanite In order to further confirm the characteristic evaluation of the solidified body of neutralized Schwertmanite according to the present invention, the above-mentioned solidification of neutralized Schwertmanite Following the characterization by measuring the phosphate ion removal rate of the body, the characterization was performed by measuring the arsenic removal rate.
砒素溶液として、市販のひ素標準液（Ａｓ１０００）［富士フィルム和光純薬（株）製］を用いて、砒素濃度２００ｐｐｍを有する砒素水溶液を調製した。
実施例１に係る中和シュベルトマナイト固化体０．１ｇと、前記砒素水溶液（砒素濃度２００ｐｐｍ）１００ｍｌとを混合し、２５℃の下、中和シュベルトマナイト固化体とリン酸溶液とを２４時間反応させ、砒素を、十分にシュベルトマナイト固化体へ飽和吸着させた。
As an arsenic solution, a commercially available arsenic standard solution (As1000) [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] was used to prepare an arsenic aqueous solution having an arsenic concentration of 200 ppm.
0.1 g of the neutralized Schwertmanite solidified product according to Example 1 and 100 ml of the arsenic aqueous solution (arsenic concentration 200 ppm) are mixed, and the neutralized Schwertmanite solidified product and the phosphoric acid solution are mixed at 25 ° C. After a time reaction, arsenic was sufficiently saturated and adsorbed on the Schwertmannite solidified product.
当該吸着反応の後、反応後の溶液を分取した。このとき、実施例１に係る中和シュベルトマナイト固化体は、溶液中でも崩壊しなかったので、反応後の溶液と中和シュベルトマナイト固化体とは容易に分離が出来た。
分取された反応後の溶液中の砒素濃度を、誘導結合プラズマ（ＩＣＰ）質量分析装置（アジレントテクノロジー社製、Ａｇｉｌｅｎｔ ７９００ ＩＣＰ−ＭＳ）を用いて分析し、実施例１に係る中和シュベルトマナイト固化体の砒素除去率（１ｇの固化体が除去する砒素量（ｍｇ））を算出した。当該算出結果を表１に示す。
After the adsorption reaction, the solution after the reaction was separated. At this time, since the neutralized Schwertmanite solidified body according to Example 1 did not disintegrate even in the solution, the solution after the reaction and the neutralized Schwertmanite solidified body could be easily separated.
The arsenic concentration in the separated solution after the reaction was analyzed using an inductively coupled plasma (ICP) mass spectrometer (Agilent 7900 ICP-MS manufactured by Agilent Technologies), and the neutralized Schwertma according to Example 1. The arsenic removal rate of the night solidified product (the amount of arsenic removed by 1 g of the solidified product (mg)) was calculated. The calculation results are shown in Table 1.
（実施例２）
シリコン製またはプラスチック製の型として（内形状：１０×１０×１０ｍｍ３）を用いた以外は、実施例１と同様の操作を行って、実施例２に係る中和シュベルトマナイト固化体（外形状：１０×１０×１０ｍｍ３）を得た。
当該固化体は、水中でも崩壊しなかった。
当該固化体の外観を図３、水中における固化体の外観を図４、物性値を表１に示す。
(Example 2)
The same operation as in Example 1 was performed except that a silicon or plastic mold (inner shape: 10 × 10 × 10 mm 3 ) was used, and the neutralized Schwertmanite solidified body (outer) according to Example 2 was performed. Shape: 10 × 10 × 10 mm 3 ) was obtained.
The solidified body did not collapse even in water.
The appearance of the solidified body is shown in FIG. 3, the appearance of the solidified body in water is shown in FIG. 4, and the physical property values are shown in Table 1.
そして実施例１と同様に、当該固化体のリン酸イオン除去率および砒素除去率を測定した。当該測定結果を表１に示す。 Then, in the same manner as in Example 1, the phosphate ion removal rate and the arsenic removal rate of the solidified body were measured. The measurement results are shown in Table 1.
（実施例３）
自転公転ミキサーを用いた攪拌および脱泡しない以外は実施例２と同様の条件にて、実施例３に係る中和シュベルトマナイト固化体（形状：１０×１０×１０ｍｍ３）を得た。
当該固化体は、水中でも崩壊しなかった。物性値を表１に示す。
(Example 3)
A neutralized Schwertmanite solidified body (shape: 10 × 10 × 10 mm 3 ) according to Example 3 was obtained under the same conditions as in Example 2 except that stirring and defoaming were not performed using a rotation / revolution mixer.
The solidified body did not collapse even in water. The physical property values are shown in Table 1.
そして実施例１と同様に、当該固化体のリン酸イオン除去率および砒素除去率を測定した。当該測定結果を表１に示す。 Then, in the same manner as in Example 1, the phosphate ion removal rate and the arsenic removal rate of the solidified body were measured. The measurement results are shown in Table 1.
（実施例４）
中和シュベルトマナイト粉体１２．５ｇと、半水石膏１０ｇとを１００ｍｌのプラスチックカップ内で十分に混合し、そこへ３０ｇの脱イオン水を加えた。そして、自転公転ミキサーを用いた攪拌および脱泡しない以外は、実施例２と同様の条件にて、実施例４に係る中和シュベルトマナイト固化体（形状：１０×１０×１０ｍｍ３）を得た。
当該固化体は、水中でも崩壊しなかった。物性値を表１に示す。
(Example 4)
12.5 g of neutralized Schwertmanite powder and 10 g of hemihydrate gypsum were thoroughly mixed in a 100 ml plastic cup, and 30 g of deionized water was added thereto. Then, a neutralized Schwertmanite solidified body (shape: 10 × 10 × 10 mm 3 ) according to Example 4 was obtained under the same conditions as in Example 2 except that stirring and defoaming were not performed using a rotation / revolution mixer. It was.
The solidified body did not collapse even in water. The physical property values are shown in Table 1.
そして実施例１と同様に、当該固化体のリン酸イオン除去率および砒素除去率を測定した。当該測定結果を表１に示す。 Then, in the same manner as in Example 1, the phosphate ion removal rate and the arsenic removal rate of the solidified body were measured. The measurement results are shown in Table 1.
（実施例５）
中和シュベルトマナイト粉体１５ｇと、半水石膏１０ｇとを１００ｍｌのプラスチックカップ内で十分に混合し、そこへ３０ｇの脱イオン水を加えた。そして、自転公転ミキサーを用いた攪拌および脱泡しない以外は、実施例２と同様の条件にて、実施例５に係る中和シュベルトマナイト固化体（形状：１０×１０×１０ｍｍ３）を得た。
当該固化体は、水中でも崩壊しなかった。物性値を表１に示す。
(Example 5)
15 g of neutralized Schwertmanite powder and 10 g of hemihydrate gypsum were thoroughly mixed in a 100 ml plastic cup, and 30 g of deionized water was added thereto. Then, a neutralized Schwertmanite solidified body (shape: 10 × 10 × 10 mm 3 ) according to Example 5 was obtained under the same conditions as in Example 2 except that stirring and defoaming were not performed using a rotation / revolution mixer. It was.
The solidified body did not collapse even in water. The physical property values are shown in Table 1.
そして実施例１と同様に、当該固化体のリン酸イオン除去率および砒素除去率を測定した。当該測定結果を表１に示す。 Then, in the same manner as in Example 1, the phosphate ion removal rate and the arsenic removal rate of the solidified body were measured. The measurement results are shown in Table 1.
（参考例１）
実施例において中和シュベルトマナイト固化体の作成時に用いた、市販の半水石膏自体のリン酸イオン除去率および砒素除去率を測定した。
半水石膏として市販の半水石膏（Ａ級、吉野石膏（株）製）２１０ｇを準備した。
当該半水石膏２０ｇを１００ｍｌのプラスチックカップ内へ入れ、中和シュベルトマナイト粉体を加えることなく、３０ｇの脱イオン水を加えた以外は、実施例１と同様の操作を実施した。
得られた固化体の物性値を表１に示す。
(Reference example 1)
The phosphate ion removal rate and arsenic removal rate of the commercially available hemihydrate gypsum itself used in the preparation of the neutralized Schwertmanite solidified body in the examples were measured.
As a hemihydrate gypsum, 210 g of commercially available hemihydrate gypsum (class A, manufactured by Yoshino Gypsum Co., Ltd.) was prepared.
The same operation as in Example 1 was carried out except that 20 g of the hemihydrate gypsum was placed in a 100 ml plastic cup and 30 g of deionized water was added without adding the neutralized Schwertmanite powder.
Table 1 shows the physical property values of the obtained solidified product.
そして実施例１と同様に、当該固化体のリン酸イオン除去率および砒素除去率を測定した。当該測定結果を表１に示す。 Then, in the same manner as in Example 1, the phosphate ion removal rate and the arsenic removal rate of the solidified body were measured. The measurement results are shown in Table 1.
Claims (6)
前記混合物へ水を添加した後、混合してスラリーを得る工程と、
前記スラリーを固化させて、中和シュベルトマナイトと石膏とを含む固化体を得る工程と、を有する固化体の製造方法。 The process of mixing neutralized Schwertmanite and hemihydrate gypsum to obtain a mixture,
A step of adding water to the mixture and then mixing to obtain a slurry.
A method for producing a solidified body, which comprises a step of solidifying the slurry to obtain a solidified body containing neutralized Schwertmanite and gypsum.
A purification method in which the solidified body according to claim 1 or 2 is put into water to be treated containing a heavy metal to adsorb the heavy metal, and then the solidified body is separated from the water.
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