JP4087433B2 - Arsenic-containing solution processing method - Google Patents
Arsenic-containing solution processing method Download PDFInfo
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- JP4087433B2 JP4087433B2 JP2007153621A JP2007153621A JP4087433B2 JP 4087433 B2 JP4087433 B2 JP 4087433B2 JP 2007153621 A JP2007153621 A JP 2007153621A JP 2007153621 A JP2007153621 A JP 2007153621A JP 4087433 B2 JP4087433 B2 JP 4087433B2
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- 229910052785 arsenic Inorganic materials 0.000 title claims description 202
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 193
- 238000000034 method Methods 0.000 title claims description 55
- 238000010129 solution processing Methods 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 161
- 239000007788 liquid Substances 0.000 claims description 82
- 239000000843 powder Substances 0.000 claims description 78
- 229910052742 iron Inorganic materials 0.000 claims description 65
- 238000000926 separation method Methods 0.000 claims description 46
- 150000001495 arsenic compounds Chemical class 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 43
- 238000010828 elution Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 11
- -1 iron ions Chemical class 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 claims description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 132
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000002386 leaching Methods 0.000 description 27
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 25
- 150000001342 alkaline earth metals Chemical class 0.000 description 24
- 238000005259 measurement Methods 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 238000003723 Smelting Methods 0.000 description 19
- 239000007795 chemical reaction product Substances 0.000 description 19
- 239000011701 zinc Substances 0.000 description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 18
- 238000004364 calculation method Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 239000010949 copper Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000003513 alkali Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000012670 alkaline solution Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 9
- 235000012255 calcium oxide Nutrition 0.000 description 9
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- UYZMAFWCKGTUMA-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane;dihydrate Chemical compound O.O.[Fe+3].[O-][As]([O-])([O-])=O UYZMAFWCKGTUMA-UHFFFAOYSA-K 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000007922 dissolution test Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229940093920 gynecological arsenic compound Drugs 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MKOYQDCOZXHZSO-UHFFFAOYSA-N [Cu].[Cu].[Cu].[As] Chemical compound [Cu].[Cu].[Cu].[As] MKOYQDCOZXHZSO-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
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- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical compound S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052964 arsenopyrite Inorganic materials 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 125000001475 halogen functional group Chemical group 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- SGMHGVVTMOGJMX-UHFFFAOYSA-N n-naphthalen-2-yl-2-sulfanylacetamide Chemical compound C1=CC=CC2=CC(NC(=O)CS)=CC=C21 SGMHGVVTMOGJMX-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
本発明は、砒素含有溶液の処理方法に関し、特に、非鉄製錬の製錬中間物などの砒素以外の各種の元素を含む砒素含有物質を処理して得られる高純度で高濃度の砒素含有溶液のような砒素含有溶液の処理方法に関する。 The present invention relates to a method for treating an arsenic-containing solution, and in particular, a high-purity and high-concentration arsenic-containing solution obtained by treating an arsenic-containing substance containing various elements other than arsenic, such as a non-ferrous smelting intermediate. The processing method of the arsenic containing solution like this.
非鉄製錬において生成される各種の製錬中間物や製錬原料には、有価金属が含まれているが、砒素などの好ましくない元素も含まれている。 Various smelting intermediates and smelting raw materials produced in non-ferrous smelting contain valuable metals, but also contain undesirable elements such as arsenic.
従来、砒素を含む製錬中間物などから砒素を浸出して分離して回収する方法として、湿式反応により砒素を分離して砒素含有溶液を回収する方法が提案されている（例えば、特許文献１参照）。また、砒酸鉄溶液中に存在する砒素を鉄との安定な結晶性で且つ不溶出性の鉄・砒素化合物として除去して固定する方法が提案されている（例えば、特許文献２参照）。また、砒素含有溶液に鉄（ＩＩ）溶液および鉄（ＩＩＩ）溶液の少なくとも一方を加えて反応させてスコロダイト（Ｓｃｏｒｏｄｉｔｅ）（ＦｅＡｓＯ４・２Ｈ２Ｏ）を生成させ、固液分離して銅を含む非鉄金属成分を含有するスコロダイトを回収し、得られた銅を含む非鉄金属成分を含有するスコロダイトに水を加えてリパルプし、スコロダイトに含まれる銅を含む非鉄金属成分を液中に溶かしてスコロダイトから分離する方法が提案されている（例えば、特許文献３参照）。さらに、砒素を含む煙灰から酸溶液により砒素を浸出し、その浸出液に鉄イオンを含む酸性水溶液を混合して非晶質の砒酸鉄（ＦｅＡｓＯ４）を沈澱させた後、その混合液を加温して非晶質の砒酸鉄を結晶化し、その混合液をろ過して結晶化された砒酸鉄を除去する方法が提案されている（例えば、特許文献４参照）。また、鉄と砒素の化合物として砒酸鉄などの安定性の評価も報告されている（例えば、非特許文献１参照）。 Conventionally, as a method of leaching arsenic from a smelting intermediate containing arsenic and separating and recovering it, a method of separating arsenic by a wet reaction and recovering an arsenic-containing solution has been proposed (for example, Patent Document 1). reference). Further, a method has been proposed in which arsenic present in an iron arsenate solution is removed and fixed as a stable crystalline and non-eluting iron / arsenic compound with iron (see, for example, Patent Document 2). In addition, at least one of an iron (II) solution and an iron (III) solution is added to the arsenic-containing solution and reacted to form Scorodite (FeAsO 4 .2H 2 O), which is separated into solid and liquid and contains copper. Collect scorodite containing non-ferrous metal component, add water to scorodite containing non-ferrous metal component containing copper and repulp, dissolve non-ferrous metal component containing copper contained in scorodite in liquid and from scorodite A separation method has been proposed (see, for example, Patent Document 3). Further, arsenic is leached from the ash containing arsenic with an acid solution, and an acidic aqueous solution containing iron ions is mixed into the leached solution to precipitate amorphous iron arsenate (FeAsO 4 ), and then the mixture is heated. Then, a method has been proposed in which amorphous iron arsenate is crystallized, and the mixed liquid is filtered to remove the crystallized iron arsenate (see, for example, Patent Document 4). In addition, stability evaluation of iron arsenate as a compound of iron and arsenic has been reported (for example, see Non-Patent Document 1).
しかし、特許文献１は、砒素含有溶液を回収するまでの方法を提案しているが、その回収された砒素含有溶液を安定な不溶出性の物質まで固定する方法について提案していない。また、特許文献２〜４の方法によって生成される従来の鉄と砒素の化合物や、非特許文献１などに報告されている砒酸鉄のような従来の鉄と砒素の化合物よりもさらに安定な不溶出性の鉄と砒素の化合物を生成することが望まれている。特に、特許文献４の方法では、非晶質の砒酸鉄を沈澱させた後に非晶質の砒酸鉄を結晶化するので、非常に長時間を要するという問題がある。 However, Patent Document 1 proposes a method for collecting an arsenic-containing solution, but does not propose a method for fixing the collected arsenic-containing solution to a stable non-eluting substance. Further, it is more stable than conventional iron and arsenic compounds produced by the methods of Patent Documents 2 to 4 and conventional iron and arsenic compounds such as iron arsenate reported in Non-Patent Document 1 and the like. It is desirable to produce leachable iron and arsenic compounds. In particular, the method of Patent Document 4 has a problem that it takes a very long time because amorphous iron arsenate is crystallized after the amorphous iron arsenate is precipitated.
したがって、本発明は、このような従来の問題点に鑑み、非鉄製錬の製錬中間物などの砒素以外の各種の元素を含む砒素含有物質を処理して得られる高純度で高濃度の砒素含有溶液のような砒素含有溶液を処理して、砒素の溶出濃度が非常に小さい鉄と砒素の化合物として回収する方法を提供することを目的とする。 Therefore, in view of such conventional problems, the present invention provides high-purity and high-concentration arsenic obtained by treating an arsenic-containing material containing various elements other than arsenic, such as non-ferrous smelting intermediates. An object of the present invention is to provide a method of treating an arsenic-containing solution such as a containing solution and recovering it as a compound of iron and arsenic with a very low arsenic elution concentration.
本発明者らは、上記課題を解決するために鋭意研究した結果、１０ｇ／Ｌ以上の５価の砒素を含む溶液に２価の鉄イオンを加えて、溶液中の砒素に対する鉄のモル比（Ｆｅ／Ａｓ）を１以上にし、酸化剤を加えて撹拌しながら温度７０℃以上で反応させた後、固液分離して固形分を回収することにより、砒素の溶出濃度が非常に小さい鉄と砒素の化合物として回収することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the inventors of the present invention added a divalent iron ion to a solution containing pentavalent arsenic of 10 g / L or more, and a molar ratio of iron to arsenic in the solution ( Fe / As) is set to 1 or more, and an oxidant is added and reacted at a temperature of 70 ° C. or higher while stirring, and then solid-liquid separation is performed to recover the solid content. The present inventors have found that it can be recovered as an arsenic compound and have completed the present invention.
すなわち、本発明による砒素含有溶液の処理方法は、１０ｇ／Ｌ以上の５価の砒素を含む溶液に２価の鉄イオンを加えて、溶液中の砒素に対する鉄のモル比を１以上にし、酸化剤を加えて撹拌しながら温度７０℃以上で反応させた後、固液分離して固形分を回収することを特徴とする。 That is, in the method for treating an arsenic-containing solution according to the present invention, a divalent iron ion is added to a solution containing 10 g / L or more of pentavalent arsenic so that the molar ratio of iron to arsenic in the solution is 1 or more. It is characterized in that after adding an agent and reacting at a temperature of 70 ° C. or higher with stirring, the solid content is separated by solid-liquid separation.
この砒素含有溶液の処理方法において、大気圧下で撹拌しながら反応が行われるのが好ましく、砒素に対する鉄のモル比が１〜１．５であるのが好ましく、反応温度が９５℃以下であるのが好ましい。また、溶液中の砒素の濃度が２０ｇ／Ｌ以上であるのが好ましい。また、２価の鉄イオンとして硫酸鉄（ＩＩ）七水塩を溶液に加えるのが好ましい。さらに、酸化剤として酸素ガスを使用することができる。 In this method for treating an arsenic-containing solution, the reaction is preferably carried out with stirring at atmospheric pressure, the molar ratio of iron to arsenic is preferably 1 to 1.5, and the reaction temperature is 95 ° C. or lower. Is preferred. The arsenic concentration in the solution is preferably 20 g / L or more. Further, it is preferable to add iron (II) sulfate heptahydrate as a divalent iron ion to the solution. Furthermore, oxygen gas can be used as an oxidizing agent.
また、上記の砒素含有溶液の処理方法において、砒素を含む溶液が、砒素含有物質をアルカリ溶液に加えてｐＨ１０以上にして酸化しながらアルカリ浸出した後に固液分離して砒素を含む浸出液を得る工程と、この浸出液にアルカリ土類金属またはその塩を添加した後に固液分離して砒素とアルカリ土類金属の化合物を含む残渣を得る工程と、この残渣を洗浄して硫酸溶液に添加した後に固液分離して砒素含有溶液を得る工程とを備えた方法によって製造された砒素含有溶液であるのが好ましい。この場合、砒素含有溶液の製造の際に、砒素含有物質として硫黄を含む砒素含有物質を使用するか、あるいは砒素含有物質が硫黄を含まない場合には砒素含有物質または浸出液に硫黄を添加し、さらに、浸出液に添加するアルカリ土類金属またはその塩の量を、砒素とアルカリ土類金属の化合物を生成するのに必要なアルカリ土類金属またはその塩の量以上にするのが好ましい。 In the above arsenic-containing solution treatment method, the arsenic-containing solution is obtained by leaching an alkali while oxidizing the arsenic-containing substance to an alkaline solution at a pH of 10 or higher, and solid-liquid separation to obtain a leachate containing arsenic. A step of adding an alkaline earth metal or a salt thereof to the leachate, followed by solid-liquid separation to obtain a residue containing a compound of arsenic and an alkaline earth metal; and washing and adding the residue to the sulfuric acid solution An arsenic-containing solution produced by a method comprising a step of obtaining a arsenic-containing solution by liquid separation is preferable. In this case, when manufacturing the arsenic-containing solution, use an arsenic-containing substance containing sulfur as the arsenic-containing substance, or if the arsenic-containing substance does not contain sulfur, add sulfur to the arsenic-containing substance or the leachate, Furthermore, it is preferable that the amount of the alkaline earth metal or salt thereof added to the leaching solution is greater than or equal to the amount of the alkaline earth metal or salt thereof necessary for producing a compound of arsenic and the alkaline earth metal.
本発明によれば、非鉄製錬の製錬中間物などの砒素以外の各種の元素を含む砒素含有物質を処理して得られる高純度で高濃度の砒素含有溶液のような砒素含有溶液を処理して、砒素の溶出濃度が非常に小さい鉄と砒素の化合物の粉末として回収することができる。 According to the present invention, an arsenic-containing solution such as a high-purity and high-concentration arsenic-containing solution obtained by treating an arsenic-containing substance containing various elements other than arsenic, such as a non-ferrous smelting intermediate, is treated. Thus, it can be recovered as a powder of an iron and arsenic compound with a very low elution concentration of arsenic.
図１は、本発明による砒素含有溶液の処理方法の実施の形態を概略的に示す工程図である。図１に示すように、本発明による砒素含有溶液の処理方法の実施の形態は、（１）砒素含有物質をアルカリ溶液に加えてｐＨ１０以上、好ましくはｐＨ１２以上にして酸化しながらアルカリ浸出した後に固液分離して砒素を含む浸出液を得るアルカリ浸出・酸化工程と、（２）この浸出液にアルカリ土類金属またはその塩を添加した後に固液分離して砒素とアルカリ土類金属の化合物を含む残渣を得るアルカリ土類金属置換工程と、（３）この残渣を洗浄して付着したアルカリ液を除去する洗浄工程と、（４）この洗浄した残渣を硫酸溶液に添加した後に固液分離して高純度で高濃度の砒素含有溶液を得る硫酸溶解工程とを備えた砒素含有溶液の製造方法によって砒素含有溶液を製造し、（５）この砒素含有溶液にＦｅ塩を添加して反応させた後に固液分離し、洗浄して固液分離して鉄と砒素の化合物を得る工程を備えている。このようにして得られた鉄と砒素の化合物は、結晶粒が粗大であり、砒素の溶出濃度が非常に低く、廃棄、堆積または保管することができる。以下、これらの各工程について説明する。 FIG. 1 is a process diagram schematically showing an embodiment of a method for treating an arsenic-containing solution according to the present invention. As shown in FIG. 1, an embodiment of the method for treating an arsenic-containing solution according to the present invention is as follows. (1) After leaching an alkali while oxidizing it to an pH of 10 or more, preferably 12 or more by adding an arsenic-containing substance to the alkali solution. Alkaline leaching / oxidation step for obtaining a leaching solution containing arsenic by solid-liquid separation, and (2) adding an alkaline earth metal or a salt thereof to the leaching solution, followed by solid-liquid separation and containing a compound of arsenic and alkaline earth metal An alkaline earth metal replacement step for obtaining a residue; (3) a washing step for washing the residue to remove the adhering alkaline solution; and (4) a solid-liquid separation after adding the washed residue to the sulfuric acid solution. An arsenic-containing solution is produced by a method for producing an arsenic-containing solution comprising a sulfuric acid dissolving step for obtaining a high-purity and high-concentration arsenic-containing solution. (5) Fe salt is added to the arsenic-containing solution and reacted. Later solid-liquid separation, washed and subjected to solid-liquid separation and a step of obtaining a compound of iron and arsenic. The compound of iron and arsenic thus obtained has coarse crystal grains and a very low arsenic elution concentration, and can be discarded, deposited or stored. Hereinafter, each of these steps will be described.
なお、上記の砒素含有溶液の製造方法の原料となる砒素含有物質としては、硫化砒素（Ａｓ２Ｓ３）やＦｅＡｓＳなどの硫化物のように硫黄と砒素を含む物質を使用することができる。また、亜鉛製錬工程などにより得られる砒化銅（Ｃｕ３Ａｓ）を主成分とする残渣なども使用することができる。この砒化銅を主成分とする残渣には、亜鉛や鉄などの他にインジウムやガリウムなどの有価金属も含まれている。なお、実施の形態の砒素含有物質の処理方法によって処理する砒素含有物質が硫黄を含まない場合には、アルカリ浸出・酸化工程前にＮａ２ＳＯ４塩のような硫酸塩などを添加するか、あるいは、アルカリ浸出・酸化工程後の浸出液に硫酸塩などを添加して、アルカリ土類金属置換工程前の浸出液中にＳＯ４イオンが存在するようにしておく必要がある。また、砒素含有物質は、砒素（Ａｓ）と硫黄（Ｓ）の他に、銅（Ｃｕ）、亜鉛（Ｚｎ）、鉄（Ｆｅ）、インジウム（Ｉｎ）、ガリウム（Ｇａ）、錫（Ｓｎ）、アンチモン（Ｓｂ）、鉛（Ｐｂ）、カドミウム（Ｃｄ）、ナトリウム（Ｎａ）、カリウム（Ｋ）、マグネシウム（Ｍｇ）およびカルシウム（Ｃａ）の少なくとも一種を含んでもよい。 As the arsenic-containing substance used as a raw material for the method for producing the arsenic-containing solution, a substance containing sulfur and arsenic such as sulfides such as arsenic sulfide (As 2 S 3 ) and FeAsS can be used. Also, such residue composed mainly of the resulting copper arsenide (Cu 3 As) due zinc smelting process can also be used. The residue mainly composed of copper arsenide contains valuable metals such as indium and gallium in addition to zinc and iron. If the arsenic-containing material to be treated by the method for treating an arsenic-containing material of the embodiment does not contain sulfur, a sulfate such as Na 2 SO 4 salt is added before the alkali leaching / oxidation step, or Alternatively, it is necessary to add sulfate or the like to the leaching solution after the alkali leaching / oxidation step so that SO 4 ions are present in the leaching solution before the alkaline earth metal replacement step. In addition to arsenic (As) and sulfur (S), arsenic-containing substances include copper (Cu), zinc (Zn), iron (Fe), indium (In), gallium (Ga), tin (Sn), It may contain at least one of antimony (Sb), lead (Pb), cadmium (Cd), sodium (Na), potassium (K), magnesium (Mg) and calcium (Ca).
（１）アルカリ浸出・酸化工程
まず、上記の砒素含有物質を酸化剤とともにアルカリ溶液に添加してｐＨ１０以上、好ましくはｐＨ１２以上にし、液温５０〜１００℃に加熱して撹拌しながら反応させることにより、砒素含有物質を酸化しながら浸出する。このアルカリ浸出・酸化工程における反応は、ｐＨ１０以上、好ましくはｐＨ１２以上の強アルカリ性で起こる反応であり、反応速度は非常に速い。
(1) Alkali leaching / oxidation step First, the above-mentioned arsenic-containing substance is added to an alkaline solution together with an oxidizing agent so as to have a pH of 10 or more, preferably 12 or more, and the reaction is carried out while stirring at a liquid temperature of 50 to 100 ° C. Leaching while oxidizing the arsenic-containing material. The reaction in the alkali leaching / oxidation step is a reaction that occurs at a strong alkalinity of pH 10 or more, preferably pH 12 or more, and the reaction rate is very fast.
このアルカリ浸出によって、Ｃｕを浸出させずにＡｓを浸出させてＣｕとＡｓを分離することができる。また、このアルカリ浸出では、Ｉｎ、Ｐｂ、ＣｄおよびＭｇも浸出されず、Ｆｅ、Ｓｎ、ＳｂおよびＣａもほとんど浸出されない。しかし、Ｇａはほとんど浸出されるので、この段階では、ＡｓとＧａは分離されない。 By this alkali leaching, Cu and As can be separated by leaching As without leaching Cu. In this alkaline leaching, In, Pb, Cd and Mg are not leached, and Fe, Sn, Sb and Ca are hardly leached. However, since Ga is almost leached, As and Ga are not separated at this stage.
なお、Ｚｎは、アルカリ濃度が高いと浸出されるが、アルカリ濃度が低いと浸出されないので、砒素含有物質中のＺｎの品位、砒素の品位および他の不純物（特にＳｎとＳｂ）の浸出挙動を勘案してアルカリ濃度を決定すればよい。すなわち、ＳｎやＳｂの品位が低ければ、残渣中にＺｎを残しておく方がよいが、ＳｎやＳｂの品位が高いと、ある程度Ｚｎを溶解させた方がよい。 Zn is leached when the alkali concentration is high, but it is not leached when the alkali concentration is low. The alkali concentration may be determined in consideration. That is, if the quality of Sn or Sb is low, it is better to leave Zn in the residue, but if the quality of Sn or Sb is high, it is better to dissolve Zn to some extent.
アルカリ溶液としてＮａＯＨ溶液を使用することができ、その場合、ＮａＯＨ濃度が５０〜３００ｇ／Ｌであるのが好ましい。 A NaOH solution can be used as the alkaline solution, in which case the NaOH concentration is preferably 50 to 300 g / L.
酸化剤としては、過マンガン酸カリウムなどの固形酸化剤の他、過酸化水素やオゾンなどを使用することができるが、空気や濃度を高めた酸素などを使用してもよく、その場合、液中にガスを吹き込んでバブリングして撹拌することによって酸化反応が容易に進む。 As the oxidizing agent, hydrogen peroxide, ozone, etc. can be used in addition to solid oxidizing agents such as potassium permanganate, but air or oxygen with increased concentration may be used. Oxidation reaction proceeds easily by bubbling and stirring the gas.
アルカリ浸出後に固液分離を行う。この固液分離は、フィルタプレス、遠心分離、デカンタ、ベルトフィルタなどの一般的なろ過のいずれでもよく、ろ過性、脱水性、洗浄性などを勘案してその種類および条件が決定される。 Solid-liquid separation is performed after alkali leaching. This solid-liquid separation may be any of general filtration such as a filter press, centrifugal separation, decanter, and belt filter, and its type and conditions are determined in consideration of filterability, dewaterability, washability, and the like.
一方、固液分離後の固形分は、有価なＣｕやＩｎなどを含む金属性化合物と、一部酸化された化合物であるので、製錬工程において有効に活用することができる。なお、銅製錬では、自溶炉や反射炉に直接投入してアノードを作成することができる。 On the other hand, since the solid content after the solid-liquid separation is a metallic compound containing valuable Cu or In and a partially oxidized compound, it can be effectively utilized in the smelting process. In copper smelting, an anode can be created by directly charging into a flash smelting furnace or a reflection furnace.
（２）アルカリ土類金属置換工程
次に、固液分離後の浸出液（主にＮａとＡｓを含む液）にアルカリ土類を添加する。アルカリ浸出後の浸出液にＣａＯなどのアルカリ土類を添加すると、アルカリ土類金属が砒素と反応してアルカリ土類金属と砒素の化合物を生成するとともに、ＮａＯＨのようなアルカリ液を再生する。
(2) Alkaline earth metal replacement step Next, alkaline earth is added to the leachate (mainly a liquid containing Na and As) after solid-liquid separation. When an alkaline earth such as CaO is added to the leachate after alkaline leaching, the alkaline earth metal reacts with arsenic to produce a compound of alkaline earth metal and arsenic, and an alkaline liquid such as NaOH is regenerated.
上記の反応のために過剰のアルカリ土類を添加することによって、再生されたアルカリ液にＳＯ４塩またはイオンを混在させて、アルカリ液へのアルカリ土類金属の混入を防止する。再生されたアルカリ液中にＳＯ４塩がなく、ほぼ純粋なアルカリ液である場合には、過剰にアルカリ土類を添加すると、再生されたアルカリ液中にアルカリ土類金属が溶存してしまう。 By adding an excess of alkaline earth for the above reaction, SO 4 salts or ions are mixed in the regenerated alkaline liquid to prevent the alkaline earth metal from being mixed into the alkaline liquid. In the case where the regenerated alkaline solution has no SO 4 salt and is a substantially pure alkaline solution, if the alkaline earth is added excessively, the alkaline earth metal is dissolved in the regenerated alkaline solution.
再生されたアルカリ液中にアルカリ土類金属が存在すると、そのアルカリ液を砒素の浸出に再利用する際に、砒素とアルカリ土類金属が反応して溶解度が低い沈殿物を生成するので、アルカリ浸出工程における浸出率が極端に悪くなる場合がある。一方、過剰のアルカリ土類金属を加えないと、アルカリ液中に砒素が除去されずに残ってしまうため、砒素の回収効率が非常に悪くなる。また、アルカリ液にＳＯ４が混在していると、アルカリ土類としてＣａＯを使用した場合に、ＣａＯまたはＣａ（ＯＨ）２がその状態で溶解せずに固形分中にとどまる。すなわち、Ｎａ＋とＳＯ４ ２−の濃度を高くすることによって、Ｃａ２＋の溶解度が非常に低く抑制されるため、ＣａＯとして固形分中にとどまる。 If alkaline earth metal is present in the regenerated alkaline liquid, when the alkaline liquid is reused for arsenic leaching, arsenic and alkaline earth metal react to produce a precipitate with low solubility. The leaching rate in the leaching process may become extremely poor. On the other hand, if excess alkaline earth metal is not added, arsenic will remain in the alkaline solution without being removed, and the arsenic recovery efficiency will be very poor. In addition, when SO 4 is mixed in the alkaline solution, when CaO is used as the alkaline earth, CaO or Ca (OH) 2 remains in the solid content without being dissolved in that state. That is, by increasing the concentration of Na + and SO 4 2− , the solubility of Ca 2+ is suppressed to be very low, so that it remains in the solid content as CaO.
アルカリ土類の添加量は、砒素とアルカリ土類金属の化合物を生成するための等当量でもよいが、Ｃａ３（ＡｓＯ４）２に加えてＣａ（ＯＨ）２を生成するように、等当量よりもややアルカリ土類リッチにするのが好ましい。 The amount of alkaline earth added may be equivalent to produce a compound of arsenic and alkaline earth metal, but is equivalent to produce Ca (OH) 2 in addition to Ca 3 (AsO 4 ) 2. It is preferable to make it slightly richer in alkaline earth.
（３）洗浄工程
次に、固形分として得られた砒素とアルカリ土類金属の化合物に付着したアルカリ液を水洗する。この水洗では、固形分中に砒素をとどめておく必要がある。砒素が洗浄排水中に溶出すると、その排水中の砒素を除去するための煩雑な操作が必要になるからである。そのような操作を回避するために、洗浄によってアルカリ液を除去するが砒素を除去しないようにすることが必要である。このような洗浄を可能にするために、上述したようにアルカリ土類を添加する際にアルカリ土類リッチにしてアルカリ性にするのが好ましい。また、アルカリ土類リッチにすると、洗浄によってアルカリ液が洗い流されるだけでなく、アルカリ土類金属が優先的に溶出し、砒素とアルカリ土類金属の化合物はそのまま保持される。なお、アルカリ土類の添加量は、洗浄水の量の増加に伴って多くなるが、Ａｓと反応する量よりも０．５〜１．０質量％だけ過剰にするのが好ましい。
(3) Washing step Next, the alkaline solution adhering to the arsenic and alkaline earth metal compound obtained as a solid content is washed with water. In this water washing, it is necessary to keep arsenic in the solid content. This is because if arsenic elutes into the washing waste water, a complicated operation for removing the arsenic in the waste water becomes necessary. In order to avoid such an operation, it is necessary to remove the alkaline solution by washing but not to remove arsenic. In order to enable such cleaning, it is preferable that the alkaline earth is made rich by alkaline earth when the alkaline earth is added as described above. Further, when the alkaline earth is rich, not only the alkaline solution is washed away but also the alkaline earth metal is preferentially eluted, and the compound of arsenic and alkaline earth metal is retained as it is. In addition, although the addition amount of alkaline-earth increases with the increase in the quantity of washing water, it is preferable to make it 0.5 to 1.0 mass% excess rather than the quantity reacting with As.
（４）硫酸溶解工程
次に、洗浄後の砒素とアルカリ土類金属の化合物を硫酸溶液に添加して、強く撹拌しながら反応させて、砒素を再溶解させるとともに石膏を生成する。この砒素とアルカリ土類金属の化合物は、アルカリ側では不溶性であるが、ｐＨが４以下ではほぼ全量が溶解するので、鉱酸によってｐＨを４以下にすれば、ほぼ全量を溶解させることが可能である。しかし、砒素とアルカリ土類金属を分離するためには、硫酸を用いて石膏と砒素含有溶液に分離するのが好ましい。砒素とアルカリ土類金属の化合物を硫酸溶液に添加すると、砒素の溶解と同時に、アルカリ土類と硫酸塩の析出反応が起こる。
(4) Sulfuric acid dissolution step Next, the washed arsenic and alkaline earth metal compound is added to the sulfuric acid solution and reacted with vigorous stirring to re-dissolve arsenic and produce gypsum. This arsenic and alkaline earth metal compound is insoluble on the alkali side, but almost completely dissolves when the pH is 4 or less. Therefore, if the pH is lowered to 4 or less with mineral acid, almost all of the compound can be dissolved. It is. However, in order to separate arsenic and alkaline earth metal, it is preferable to separate into gypsum and an arsenic-containing solution using sulfuric acid. When a compound of arsenic and alkaline earth metal is added to the sulfuric acid solution, precipitation of alkaline earth and sulfate occurs simultaneously with the dissolution of arsenic.
硫酸溶液の濃度は、１００〜５００ｇ／Ｌであるのが好ましく、１５０〜３００ｇ／Ｌであるのがさらに好ましい。砒素含有溶液中の砒素を高濃度にしたい場合には、硫酸溶液の濃度をより高くする必要があるが、生成する石膏に付着する硫酸溶液の濃度が上昇し、また、溶液の粘度も上昇するので好ましくない。しかし、砒素の未反応を防止する観点では、砒素とアルカリ土類金属の化合物を濃硫酸に添加して、砒素だけでなく石膏も溶解させた後に、水を加えて加水分解により石膏を析出させてもよい。 The concentration of the sulfuric acid solution is preferably 100 to 500 g / L, and more preferably 150 to 300 g / L. To increase the concentration of arsenic in the arsenic-containing solution, it is necessary to increase the concentration of the sulfuric acid solution. However, the concentration of the sulfuric acid solution adhering to the gypsum produced increases, and the viscosity of the solution also increases. Therefore, it is not preferable. However, from the viewpoint of preventing unreacted arsenic, the compound of arsenic and alkaline earth metal is added to concentrated sulfuric acid to dissolve not only arsenic but also gypsum, and then water is added to precipitate gypsum by hydrolysis. May be.
撹拌は強く行うことが好ましい。砒素の溶解反応と石膏の析出反応が同時に起こり、また、ウェットケーキの状態で硫酸溶液に投入するのが好ましく、局部的な中和などを起こし易い系であるので、均一且つ完全に反応させるために、強く撹拌して十分に砒素を硫酸に接触させて高純度で高濃度の砒素含有溶液にする必要があるからである。 Stirring is preferably performed strongly. Arsenic dissolution reaction and gypsum precipitation reaction occur at the same time, and it is preferable to put it into the sulfuric acid solution in the form of a wet cake. In addition, it is necessary to vigorously agitate to sufficiently contact arsenic with sulfuric acid to obtain a high-purity and high-concentration arsenic-containing solution.
（５）ＦｅとＡｓの化合物の生成工程
次に、得られた砒素含有溶液に２価の鉄イオンを加えて、溶液中の砒素に対する鉄のモル比（Ｆｅ／Ａｓ）を１以上にし、酸化剤を加えて撹拌しながら７０℃以上に昇温させて反応させた後、固液分離して得られる固形分を乾燥する。
(5) Step of generating Fe and As compound Next, divalent iron ions are added to the obtained arsenic-containing solution so that the molar ratio of iron to arsenic (Fe / As) in the solution is 1 or more and oxidation is performed. After adding the agent and stirring, the temperature is raised to 70 ° C. or higher to react, and then the solid content obtained by solid-liquid separation is dried.
砒素含有溶液中のＡｓ濃度は、不純物として含まれるＮａなどが１ｇ／Ｌ以下であれば、それほど高くなくてもよいが、Ａｓ濃度が低いとＦｅとＡｓの化合物の析出から成長過程で粒子が粗大化し難くなる傾向があるので、１０ｇ／Ｌ以上であるのが好ましく、２０ｇ／Ｌ以上であるのがさらに好ましい。また、砒素含有溶液のｐＨが２以下であるのが好ましい。なお、砒素含有溶液中のＡｓ濃度が高ければ、溶液中に不純物としてＮａ、Ｍｇ、Ｃｕ、Ｚｎ、Ｍｎなどの塩が共存してもよい。 The concentration of As in the arsenic-containing solution may not be so high as long as the amount of Na contained as an impurity is 1 g / L or less, but if the concentration of As is low, particles are formed during the growth process from precipitation of a compound of Fe and As. Since there exists a tendency which becomes difficult to coarsen, it is preferable that it is 10 g / L or more, and it is further more preferable that it is 20 g / L or more. Further, the pH of the arsenic-containing solution is preferably 2 or less. If the As concentration in the arsenic-containing solution is high, salts such as Na, Mg, Cu, Zn, and Mn may coexist as impurities in the solution.
２価のＦｅ源としては、可溶性のＦｅＳＯ４・７Ｈ２Ｏを使用するのが好ましい。溶液中の砒素に対する鉄のモル比（Ｆｅ／Ａｓ）は１以上であるのが好ましく、１．０〜１．５程度であるのがさらに好ましい。 As the divalent Fe source, soluble FeSO 4 · 7H 2 O is preferably used. The molar ratio of iron to arsenic (Fe / As) in the solution is preferably 1 or more, and more preferably about 1.0 to 1.5.
酸化剤としては、Ｆｅ２＋を酸化することができる酸化剤であれば使用することができるが、酸化速度を制御することができる酸化剤が好ましく、酸素ガスや空気などを使用するのが好ましい。また、酸化剤としてＫＭｎＯ４などを使用しても、添加量を制御することによって酸化速度を制御することができる。 As the oxidizing agent, any oxidizing agent capable of oxidizing Fe 2+ can be used, but an oxidizing agent capable of controlling the oxidation rate is preferable, and oxygen gas, air, or the like is preferably used. Even when KMnO 4 or the like is used as the oxidizing agent, the oxidation rate can be controlled by controlling the amount added.
反応温度は、５０℃以上であればＦｅとＡｓの化合物を析出させることができるが、Ａｓの溶出濃度を低下させるためには、７０℃以上にするのが好ましく、８０〜９５℃程度であるのがさらに好ましい。また、反応時間は１〜３時間でよい。 If the reaction temperature is 50 ° C. or higher, the compound of Fe and As can be precipitated. However, in order to reduce the elution concentration of As, it is preferably 70 ° C. or higher, and is about 80 to 95 ° C. Is more preferable. The reaction time may be 1 to 3 hours.
以下、本発明による砒素含有溶液の処理方法の実施例について詳細に説明する。 Examples of the method for treating an arsenic-containing solution according to the present invention will be described in detail below.
［実施例１］
まず、出発原料として表１に示す組成の砒素含有物質を用意した。この砒素含有物質４００ｇをＮａＯＨ濃度１００ｇ／ＬのＮａＯＨ溶液（Ｎａ濃度５７．５ｇ／Ｌ）４Ｌに入れ、液温９０℃に加熱し、２Ｌ／分の流量で空気（ガス／液比率＝０．５）を吹き込んで、撹拌しながら１時間反応させ、砒素化合物を酸化しながらアルカリ浸出した。なお、砒素含有物質をＮａＯＨ溶液に入れた後のｐＨは約１２であった。
[Example 1]
First, an arsenic-containing material having the composition shown in Table 1 was prepared as a starting material. 400 g of this arsenic-containing substance is placed in 4 L of NaOH solution (Na concentration 57.5 g / L) having a NaOH concentration of 100 g / L, heated to a liquid temperature of 90 ° C., and air (gas / liquid ratio = 0.0) at a flow rate of 2 L / min. 5) was blown in and allowed to react for 1 hour with stirring, and alkali leaching was performed while oxidizing the arsenic compound. The pH after the arsenic-containing substance was added to the NaOH solution was about 12.
次に、液温７０℃まで冷却した後、目開き３ミクロンのＰＴＦＥ（ポリ四フッ化エチレン）からなるメンブランフィルタを用いて、加圧ろ過機によって０．４ＭＰａに加圧して、フィルタ上に残った残渣（浸出残渣）とフィルタを通過したろ液（アルカリ浸出液）に固液分離した。得られた浸出残渣の水分は２０％であり、質量は６００ｇであった。 Next, after cooling to a liquid temperature of 70 ° C., a membrane filter made of PTFE (polytetrafluoroethylene) having an opening of 3 microns is pressurized to 0.4 MPa by a pressure filter and remains on the filter. The solid residue was separated into a residue (leaching residue) and a filtrate (alkaline leachate) that passed through the filter. The obtained leach residue had a water content of 20% and a mass of 600 g.
次に、アルカリ浸出液に純度９５％の工業用生石灰（ＣａＯ）を添加して、液温６０℃に加熱し、撹拌して１時間反応させ、固形分としてＣａとＡｓの化合物を得るとともに、ＮａＯＨ液を再生した。この置換反応によって液温は６０℃から８０℃まで上昇した。なお、工業用生石灰の添加量は、アルカリ浸出の際に加えたＮａＯＨ溶液のＮａＯＨ濃度との関係からアルカリ浸出液を置換するに足りるＣａＯと同当量とした。また、ＣａＯを添加すると水（Ｈ２Ｏ）を消費するので、濃度の上昇を避けるために、アルカリ浸出液が同じ量になるように水を補給して調整した。 Next, 95% pure industrial quicklime (CaO) is added to the alkaline leachate, heated to a liquid temperature of 60 ° C., stirred and reacted for 1 hour to obtain a compound of Ca and As as a solid content, and NaOH. The liquid was regenerated. The liquid temperature rose from 60 ° C. to 80 ° C. by this substitution reaction. The amount of industrial quicklime added was the same as that of CaO sufficient to replace the alkaline leaching solution in relation to the NaOH concentration of the NaOH solution added during the alkaline leaching. Moreover, since water (H 2 O) is consumed when CaO is added, in order to avoid an increase in concentration, water was replenished and adjusted so that the alkaline leachate was the same amount.
次に、液温７０℃まで冷却した後、加圧ろ過機によって固液分離した。得られた残渣（砒素とアルカリ土類金属の塩の固形分）は、２０％の水分を含み、１５８ｇ／Ｌであった。 Next, after cooling to a liquid temperature of 70 ° C., solid-liquid separation was performed with a pressure filter. The resulting residue (solid content of arsenic and alkaline earth metal salt) contained 20% water and was 158 g / L.
次に、固液分離後の固形分に付着したアルカリ成分を除去するために、パルプ濃度２００ｇ／Ｌとしてリパルプ洗浄を３回行った。各々のリパルプ洗浄では、液温を６０℃として撹拌しながら１時間反応させた。その後、目開き３ミクロンのＰＴＦＥからなるメンブランフィルタを用いて、加圧ろ過機によって０．４ＭＰａに加圧して、フィルタ上に残った残渣（洗浄後のカルシウムと砒素を含む固形分）とフィルタを通過したろ液（洗浄后液）に固液分離した。 Next, in order to remove the alkali component adhering to the solid content after solid-liquid separation, repulp washing was performed three times with a pulp concentration of 200 g / L. In each repulp washing, the liquid temperature was 60 ° C. and the reaction was performed for 1 hour with stirring. Then, using a membrane filter made of PTFE having a mesh size of 3 microns, the pressure is reduced to 0.4 MPa by a pressure filter, and the residue (solid content including calcium and arsenic after washing) and the filter remaining on the filter are removed. The filtrate that passed through (liquid after washing) was subjected to solid-liquid separation.
次に、洗浄後の残渣（水分２０％を含むカルシウムと砒素の固形分）１９１２ｇを２００ｇ／Ｌの硫酸溶液５．５９Ｌに添加してｐＨ１になるようにし、液温を５０℃として強く撹拌しながら２時間反応させて残渣を再溶解させた。この置換反応により液温は５０℃から８０℃に上昇した。 Next, 1912 g of the residue after washing (solid content of calcium and arsenic containing 20% water) was added to 5.59 L of a 200 g / L sulfuric acid solution to adjust to pH 1, and the liquid temperature was 50 ° C. and the mixture was vigorously stirred. For 2 hours to redissolve the residue. The liquid temperature rose from 50 ° C. to 80 ° C. by this substitution reaction.
その後、目開き３ミクロンのＰＴＦＥからなるメンブランフィルタを用いて、加圧ろ過機によって０．４ＭＰａに加圧して、フィルタ上に残った残渣（石膏）とフィルタを通過したろ液（砒素含有溶液）に固液分離した。このようにして得られたろ液について組成分析を行ったところ、表２に示すようにアルカリ土類金属などの不純物が非常に少ない高濃度の砒素を含む溶液であり、ｐＨ１．０であった。 After that, using a membrane filter made of PTFE having a mesh size of 3 microns, the pressure (0.4 g) was pressurized by a pressure filter and the residue (gypsum) remaining on the filter and the filtrate that passed through the filter (arsenic-containing solution) Separated into solid and liquid. The composition of the filtrate thus obtained was subjected to composition analysis, and as shown in Table 2, it was a solution containing a high concentration of arsenic such as an alkaline earth metal and had a pH of 1.0.
次に、得られた砒素含有溶液４８６ｍＬと、１級試薬のＦｅＳＯ４・７Ｈ２Ｏに水を加えてＦｅ濃度が１８３ｇ／Ｌになるように調整した溶液２１４ｍＬ（この溶液と砒素含有溶液の合計の液量が７００ｍＬ）とをチタン製の容量１Ｌの密閉容器（反応槽）に入れて（Ａｓ濃度５０．１３ｇ／Ｌ、Ｆｅ濃度５６．００ｇ／Ｌ、Ｆｅ／Ａｓ比＝１．５）、容器内の雰囲気を不活性ガス雰囲気として、１段の平パドルを５００ｒｐｍにして撹拌しながら昇温させた。容器内の温度が１００℃以上になった時点で一旦不活性ガスを脱気し、引き続き、最終的な設定温度１７５℃まで昇温させた。この時点で容器内の圧力は０．８ＭＰａまで上昇した。 Next, 486 mL of the obtained arsenic-containing solution and 214 mL of a solution prepared by adding water to the first grade reagent FeSO 4 .7H 2 O so that the Fe concentration becomes 183 g / L (the total of this solution and the arsenic-containing solution) Is put in a 1 L titanium sealed container (reaction vessel) (As concentration 50.13 g / L, Fe concentration 56.00 g / L, Fe / As ratio = 1.5), The atmosphere in the container was set to an inert gas atmosphere, and the temperature of the single-stage flat paddle was increased to 500 rpm while stirring. When the temperature in the container reached 100 ° C. or higher, the inert gas was once degassed, and then the temperature was raised to a final set temperature of 175 ° C. At this time, the pressure in the container rose to 0.8 MPa.
最終的な設定温度１７５℃に達したときに容器内に純度９９％以上の酸素ガスを吹き込んで、温度と圧力（酸素の分圧を０．２ＭＰａ、容器内の全圧を１．０ＭＰａとした）を保持して５時間反応させた。５時間経過後、容器への加温を停止して、約１時間で容器を１００℃以下まで冷却し、その後、容器を大気に開放して、容器内の溶液を取り出した。この溶液の温度が７０℃になった後、目開き３ミクロンのＰＴＦＥからなるメンブランフィルタを用いて、加圧ろ過機によって０．４ＭＰａに加圧して固液分離を行った。得られたろ液（反応溶液）の量は６４０ｍＬであった。 When the final set temperature reached 175 ° C., oxygen gas with a purity of 99% or more was blown into the container, and the temperature and pressure (the partial pressure of oxygen was 0.2 MPa, and the total pressure in the container was 1.0 MPa). ) Was allowed to react for 5 hours. After 5 hours, heating to the container was stopped, and the container was cooled to 100 ° C. or less in about 1 hour, and then the container was opened to the atmosphere, and the solution in the container was taken out. After the temperature of this solution reached 70 ° C., solid-liquid separation was performed by applying pressure to 0.4 MPa with a pressure filter using a membrane filter made of PTFE having an opening of 3 μm. The amount of the obtained filtrate (reaction solution) was 640 mL.
なお、加圧ろ過の開始から空気が吹き抜けるまでの時間を測定することによって（加圧ろ過機のろ過面積１ｍ２当りの）ろ過速度を測定した。また、固液分離された反応后液のｐＨおよび酸化還元電位（ＯＲＰ）を測定するとともに、ＩＣＰによって反応后液中の硫酸濃度（遊離酸（ＦＡ）の濃度）および各元素の組成分析を行った。これらの条件および結果を表３〜表５に示す。 In addition, the filtration rate (per 1 m < 2 > filtration area of a pressure filter) was measured by measuring the time from the start of pressure filtration until air blows through. In addition, the pH and redox potential (ORP) of the post-reaction solution separated into solid and liquid were measured, and the sulfuric acid concentration (free acid (FA) concentration) in the post-reaction solution and the compositional analysis of each element were performed by ICP. It was. These conditions and results are shown in Tables 3 to 5.
なお、Ａｓの価数分析をチオナリド法によって分析したところ、９９％が５価のＡｓであり、Ｆｅの価数分析を吸光光度法によって分析したところ、全て３価であった。 In addition, when the valence analysis of As was analyzed by the thionalide method, 99% was pentavalent As, and when the valence analysis of Fe was analyzed by the absorptiometry, all were trivalent.
一方、固液分離によって得られた固形分のウェット重量を測定し、ウェットベースで１００ｇの固形分に対して水１Ｌになるように水を加えて、リパルプ洗浄を行なった。このリパルプ洗浄では、液温を３０℃として４００ｒｐｍで１時間撹拌した。この洗浄後、加圧ろ過機を用いて再度固液分離した。 On the other hand, the wet weight of the solid content obtained by solid-liquid separation was measured, and water was added to 1 L of water with respect to 100 g of the solid content on a wet base to perform repulp washing. In this repulp washing, the liquid temperature was set to 30 ° C. and stirred at 400 rpm for 1 hour. After this washing, solid-liquid separation was performed again using a pressure filter.
この固液分離によって固形分として得られたケーキの重量を測定し、６０℃で１８時間乾燥した後、メノウ乳鉢で軽く解砕して得られた粉体について、組成分析、溶出試験、湿式粒度分布測定、Ｎ２ガス吸着法による比表面積測定（ＢＥＴ１点法）、ベックマン式比重測定、１トン加圧による圧縮密度を測定した。組成分析は、一旦水に溶解した後にＩＣＰによって行った。湿式粒度分布は、湿式粒度分布測定器（堀場製作所製のＬＡ５００）を用いて測定した。Ｎ２ガス吸着による比表面積測定は、比表面積測定器（湯浅アイオニクス製のモノソーブ）を用いてＢＥＴ１点法で行った。また、溶出試験は、環境庁告示１３号法に基づいて、固形分１００ｇに対してｐＨ５の水１Ｌを混合し、溶出試験専用しんとう機で６時間しんとうさせた後、０．４５ミクロンのメンブランフィルタを用いて固液分離して得られたろ液（溶出液）中の砒素濃度を分析することによって行った。 The weight of the cake obtained as a solid content by this solid-liquid separation was measured, dried at 60 ° C. for 18 hours, and then lightly crushed in an agate mortar, composition analysis, dissolution test, wet particle size Distribution measurement, specific surface area measurement by N 2 gas adsorption method (BET 1-point method), Beckman type specific gravity measurement, compression density by 1 ton pressurization were measured. The composition analysis was performed by ICP after once dissolving in water. The wet particle size distribution was measured using a wet particle size distribution measuring device (LA500 manufactured by Horiba, Ltd.). Specific surface area measurement by N 2 gas adsorption was performed by a BET one-point method using a specific surface area measuring device (Monosorb manufactured by Yuasa Ionics). In addition, the dissolution test is based on the Environmental Agency Notification No.13. After mixing 1 L of water with a pH of 5 with 100 g of solid content and stirring for 6 hours with a dedicated machine for dissolution test, a 0.45 micron membrane filter is used. The arsenic concentration in the filtrate (eluate) obtained by solid-liquid separation using was analyzed.
また、分析結果から、Ｆｅ／Ａｓ比率、発生残渣量（砒素品位と水分値から求めたＡｓ１トン当りの量）、処理すべき液量（処理液の前後のＡｓ濃度から求めたＡｓ１トンを除去する際に必要とされる液量）を計算した。 From the analysis results, the Fe / As ratio, the amount of generated residue (the amount per 1 ton of As determined from the arsenic quality and moisture value), and the amount of liquid to be processed (As 1 ton determined from the As concentration before and after the treatment solution) are removed. The amount of liquid required for the calculation was calculated.
さらに、得られた粉体について、Ｘ線回折計を用いて粉末Ｘ線回折を行った。この粉末Ｘ線回折では、対陰極をＣｕのＫα、波長λ＝１．５４１８オングストローム、管電圧＝５０ｋＶ（一部４０ｋＶ）、管電流＝３００ｍＡ、走査速度０．０１°／ｓｅｃ、走査角度２θ＝５°〜８５°とし、シンチレーションカウンターを使用した。また、得られた回折像が結晶性であるか否か、低角側を中心としてハローパターンが観察されるか否かによって、非晶質であるか結晶質であるかを判定した。また、走査電子顕微鏡（ＳＥＭ）によって粒子を観察した。 Further, the obtained powder was subjected to powder X-ray diffraction using an X-ray diffractometer. In this powder X-ray diffraction, the counter cathode is Kα of Cu, wavelength λ = 1.5418 angstrom, tube voltage = 50 kV (partial 40 kV), tube current = 300 mA, scanning speed 0.01 ° / sec, scanning angle 2θ = A scintillation counter was used at 5 ° to 85 °. Whether the obtained diffraction image is crystalline or not and whether a halo pattern is observed around the low-angle side was determined to be amorphous or crystalline. The particles were observed with a scanning electron microscope (SEM).
これらの結果を表６〜表８に示す。 These results are shown in Tables 6-8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０１を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０３ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.01, and from the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.03 mg / L, which was much lower than the reference value (0.3 mg / L).
［実施例２］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）を用いて、撹拌速度を１０００ｒｐｍ、反応温度（最終的な設定温度）を９５℃にした以外は、実施例１と同様の方法によって反応させた。
[Example 2]
The same arsenic-containing solution (solution having the composition shown in Table 2) as in Example 1 was used, except that the stirring speed was 1000 rpm and the reaction temperature (final set temperature) was 95 ° C. Reacted by the method.
なお、反応生成物の固液分離の際の加圧ろ過の開始から空気が吹き抜けるまでの時間を測定することによって（加圧ろ過機のろ過面積１ｍ２当りの）ろ過速度を測定した。また、固液分離された反応后液のｐＨおよび酸化還元電位（ＯＲＰ）を測定するとともに、ＩＣＰによって反応后液中の硫酸濃度（遊離酸（ＦＡ）の濃度）および各元素の組成分析を行った。これらの条件および結果を表３〜表５に示す。 In addition, the filtration rate (per 1 m < 2 > filtration area of a pressure filter) was measured by measuring the time from the start of the pressure filtration at the time of the solid-liquid separation of the reaction product until air blows through. In addition, the pH and redox potential (ORP) of the post-reaction solution separated into solid and liquid were measured, and the sulfuric acid concentration (free acid (FA) concentration) in the post-reaction solution and the compositional analysis of each element were performed by ICP. It was. These conditions and results are shown in Tables 3 to 5.
また、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理することによって得られた粉体について、実施例１と同様の測定および計算を行った。その結果を表６〜表８に示す。また、本実施例で得られた粉体の５０００倍の走査電子顕微鏡（ＳＥＭ）写真およびＸ線回折（ＸＲＤ）データをそれぞれ図２および図３に示す。 Moreover, the measurement and calculation similar to Example 1 were performed about the powder obtained by processing the solid content obtained by solid-liquid separation of a reaction product like Example 1. FIG. The results are shown in Tables 6-8. Moreover, the scanning electron microscope (SEM) photograph and X-ray diffraction (XRD) data of 5000 times the powder obtained in this example are shown in FIGS. 2 and 3, respectively.
実施例１および実施例２の結果から、高純度で砒素濃度の高い砒素含有溶液をＦｅと反応させると、反応温度にかかわらず沈殿物が得られ、Ａｓの除去率は９７％と良好で、水分値が低く、固形分の容積が少なくなり、砒素の含有率も高く、ろ過性が良好で、結晶質の析出物を得ることができ、簡単な洗浄で付着塩を除去することができるため、砒素の溶出濃度が基準値（０．３ｍｇ／Ｌ）より非常に低くなっていることがわかる。 From the results of Example 1 and Example 2, when an arsenic-containing solution having a high purity and a high arsenic concentration was reacted with Fe, a precipitate was obtained regardless of the reaction temperature, and the As removal rate was good at 97%. Because the moisture content is low, the volume of solids is small, the arsenic content is high, the filterability is good, crystalline precipitates can be obtained, and the attached salt can be removed by simple washing It can be seen that the elution concentration of arsenic is much lower than the reference value (0.3 mg / L).
［実施例３］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）に４０ｇ／ＬのＺｎを共存させて用いた以外は、実施例１と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 3]
Except for using 40 g / L of Zn in the same arsenic-containing solution as in Example 1 (solution having the composition shown in Table 2), after reacting in the same manner as in Example 1, the reaction product The solid content obtained by solid-liquid separation was treated in the same manner as in Example 1, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は０．９８を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０５ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。 As shown in Table 8, the Fe / As (molar ratio) of the obtained powder was 0.98, and from the results of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.05 mg / L, which was much lower than the reference value (0.3 mg / L).
［実施例４］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）に４０ｇ／ＬのＺｎを共存させて用いた以外は、実施例２と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例２と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 4]
Except for using 40 g / L of Zn in the same arsenic-containing solution (solution having the composition shown in Table 2) as in Example 1, the reaction product was reacted in the same manner as in Example 2 The solid content obtained by solid-liquid separation was treated in the same manner as in Example 2, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０５を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０６ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。この結果から、砒素含有溶液中に亜鉛が共存しても、砒素の溶出濃度が非常に低く、本発明による砒素含有溶液の処理方法を亜鉛製錬の工程液の処理に適用することができるのがわかる。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.05. From the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.06 mg / L, which was much lower than the reference value (0.3 mg / L). From this result, even if zinc coexists in the arsenic-containing solution, the arsenic elution concentration is very low, and the processing method of the arsenic-containing solution according to the present invention can be applied to the treatment of the zinc smelting process liquid. I understand.
［実施例５］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）を容量２Ｌのガラス製の開放容器（反応槽）に入れて、撹拌速度を１０００ｒｐｍ、反応温度（最終的な設定温度）を９５℃、反応時間を７時間にした以外は、実施例１と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 5]
An arsenic-containing solution (solution having the composition shown in Table 2) similar to that in Example 1 was placed in a 2 L glass open container (reaction vessel), the stirring speed was 1000 rpm, and the reaction temperature (final set temperature) was After reacting by the same method as in Example 1 except that the reaction time was 95 ° C. and 7 hours, the solid content obtained by solid-liquid separation of the reaction product was treated in the same manner as in Example 1 to obtain The obtained powder was subjected to the same measurements and calculations as in Example 1. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０７を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０２ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.07. From the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.02 mg / L, which was much lower than the reference value (0.3 mg / L).
［実施例６］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）を水で希釈して溶液中のＡｓ濃度を３０．０２ｇ／Ｌ、Ｆｅ濃度を３３．６３ｇ／Ｌ（Ｆｅ／Ａｓ比＝１．５）にした以外は、実施例５と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 6]
An arsenic-containing solution similar to that in Example 1 (solution having the composition shown in Table 2) was diluted with water, the As concentration in the solution was 30.02 g / L, and the Fe concentration was 33.63 g / L (Fe / As ratio = Except for 1.5), after reacting in the same manner as in Example 5, the solid content obtained by solid-liquid separation of the reaction product was treated in the same manner as in Example 1, and the resulting powder was obtained. The same measurements and calculations as in Example 1 were performed. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０２を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０２ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.02, and from the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.02 mg / L, which was much lower than the reference value (0.3 mg / L).
［実施例７］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）を水で希釈して溶液中のＡｓ濃度を２０．０７ｇ／Ｌ、Ｆｅ濃度を２２．４１ｇ／Ｌ（Ｆｅ／Ａｓ比＝１．５）にした以外は、実施例５と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 7]
The same arsenic-containing solution (solution having the composition shown in Table 2) as in Example 1 was diluted with water, the As concentration in the solution was 20.07 g / L, and the Fe concentration was 22.41 g / L (Fe / As ratio = Except for 1.5), after reacting in the same manner as in Example 5, the solid content obtained by solid-liquid separation of the reaction product was treated in the same manner as in Example 1, and the resulting powder was obtained. The same measurements and calculations as in Example 1 were performed. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０３を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０２ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.03. From the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.02 mg / L, which was much lower than the reference value (0.3 mg / L).
［実施例８］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）の代わりに（５００ｇ／Ｌの砒素を含む）１級試薬の砒素液（５価の砒素液）を希釈して容量５Ｌの密閉容器（反応槽）に入れ、その溶液中のＡｓ濃度を１０．００ｇ／Ｌ、Ｆｅ濃度を１１．１８ｇ／Ｌ（Ｆｅ／Ａｓ比＝１．５）にし、撹拌速度を３６０ｒｐｍ、酸素の分圧を０．３ＭＰａにし、固液分離後のリパルプ洗浄を２回行った以外は、実施例１と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 8]
Instead of the same arsenic-containing solution as in Example 1 (solution having the composition shown in Table 2), the first grade arsenic liquid (pentavalent arsenic liquid) (containing 500 g / L arsenic) was diluted to a capacity of 5 L Put in an airtight container (reaction tank), set As concentration in the solution to 10.00 g / L, Fe concentration to 11.18 g / L (Fe / As ratio = 1.5), stirring speed to 360 rpm, oxygen content The reaction was carried out in the same manner as in Example 1 except that the pressure was 0.3 MPa and the repulp washing after the solid-liquid separation was performed twice, and then the solid content obtained by solid-liquid separation of the reaction product was carried out. The same processing as in Example 1 was carried out, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．２０を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０２ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.20, and it was found from the result of X-ray diffraction that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.02 mg / L, which was much lower than the reference value (0.3 mg / L).
［実施例９］
容量２Ｌのガラス製の開放容器（反応槽）に入れた溶液中のＡｓ濃度を１０．０１ｇ／Ｌ、Ｆｅ濃度を１１．２１ｇ／Ｌ（Ｆｅ／Ａｓ比＝１．５）にした以外は、実施例５と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 9]
Except that the concentration of As in the solution placed in a glass open container (reaction vessel) with a capacity of 2 L was 10.1 g / L and the Fe concentration was 11.21 g / L (Fe / As ratio = 1.5), After reacting by the same method as in Example 5, the solid content obtained by solid-liquid separation of the reaction product was treated in the same manner as in Example 1. The obtained powder was measured in the same manner as in Example 1. Calculated. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０３を示し、Ｘ線回折の結果からアモルファスの鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０１ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。 As shown in Table 8, the Fe / As (molar ratio) of the obtained powder was 1.03. From the result of X-ray diffraction, it was found that an amorphous iron-arsenic compound powder was obtained. . The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.01 mg / L, which was much lower than the reference value (0.3 mg / L).
［比較例１］
１級試薬のＦｅＳＯ４・７Ｈ２Ｏの代わりにポリ鉄（Ｆｅ３＋）を使用し、Ａｓ濃度を４７．９７ｇ／Ｌ、Ｆｅ濃度５３．７７ｇ／Ｌ、Ｆｅ／Ａｓ比＝１．５）にした以外は、実施例１と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Comparative Example 1]
Using polyiron (Fe 3+ ) instead of the primary reagent FeSO 4 · 7H 2 O, As concentration 47.97 g / L, Fe concentration 53.77 g / L, Fe / As ratio = 1.5) Except for the above, after reacting by the same method as in Example 1, the solid content obtained by solid-liquid separation of the reaction product was treated in the same manner as in Example 1. Similar measurements and calculations were performed. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０４を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．４８ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より高かった。なお、この比較例では、平均粒径が大きく、５μｍ以下の粒子の割合が０％であり、ＢＥＴ比表面積が小さくなっているが、ＳＥＭ像の結果から、緻密な結晶形態でなく、凝集しているため、平均粒径、５μｍ以下の粒子の割合およびＢＥＴ比表面積が見掛けの値であることがわかった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.04. From the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.48 mg / L, which was higher than the reference value (0.3 mg / L). In this comparative example, the average particle size is large, the proportion of particles of 5 μm or less is 0%, and the BET specific surface area is small. However, from the result of the SEM image, it is not a dense crystal form but agglomerated. Therefore, it was found that the average particle diameter, the ratio of particles of 5 μm or less, and the BET specific surface area were apparent values.
［比較例２］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）の代わりに、亜砒酸を溶解してＡｓ濃度４７．９７ｇ／Ｌにした溶液を使用した以外は、比較例２と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Comparative Example 2]
A method similar to Comparative Example 2 except that a solution having an As concentration of 47.97 g / L dissolved in arsenous acid was used instead of the arsenic-containing solution similar to Example 1 (solution having the composition shown in Table 2). After the reaction, the solid content obtained by solid-liquid separation of the reaction product was treated in the same manner as in Example 1. The obtained powder was subjected to the same measurements and calculations as in Example 1. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．２１を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は４．４５ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に高かった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.21, and from the results of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 4.45 mg / L, which was much higher than the standard value (0.3 mg / L).
［比較例３］
最終的な設定温度（反応温度）を７０℃にした以外は、実施例５と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Comparative Example 3]
Except for setting the final set temperature (reaction temperature) to 70 ° C., the reaction was carried out in the same manner as in Example 5, and then the solid content obtained by solid-liquid separation of the reaction product was obtained in the same manner as in Example 1. The same measurement and calculation as in Example 1 were performed on the processed powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０６を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．３２ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より高かった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.06. From the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.32 mg / L, which was higher than the reference value (0.3 mg / L).
［比較例４］
最終的な設定温度（反応温度）を５０℃にして酸素ガスの代わりに空気を吹き込んだ以外は、実施例５と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Comparative Example 4]
It was obtained by solid-liquid separation of the reaction product after reacting by the same method as in Example 5 except that the final set temperature (reaction temperature) was 50 ° C. and air was blown in place of oxygen gas. The solid content was treated in the same manner as in Example 1, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０１を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は２２．８４ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に高かった。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.01, and from the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 22.84 mg / L, which was much higher than the standard value (0.3 mg / L).
［実施例１０］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）に８０ｇ／ＬのＺｎを共存させて用いた以外は、実施例１と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 10]
Except for using 80 g / L of Zn in the same arsenic-containing solution (solution having the composition shown in Table 2) as in Example 1, the reaction product was reacted in the same manner as in Example 1 The solid content obtained by solid-liquid separation was treated in the same manner as in Example 1, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は０．９８を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．２１ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より低かった。この結果からわかるように、砒素含有溶液中の亜鉛濃度が８０ｇ／Ｌと高くなっても砒素の溶出濃度が低いので、本発明による砒素含有溶液の処理方法を亜鉛製錬の工程液に適用する場合に、亜鉛製錬の工程液中の亜鉛濃度が高くても適用することができ、工程内のばらつきに対応することができる。 As shown in Table 8, the Fe / As (molar ratio) of the obtained powder was 0.98, and from the results of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.21 mg / L, which was lower than the reference value (0.3 mg / L). As can be seen from this result, even when the zinc concentration in the arsenic-containing solution is as high as 80 g / L, the arsenic elution concentration is low, so the arsenic-containing solution processing method according to the present invention is applied to the zinc smelting process liquid. In this case, it can be applied even if the zinc concentration in the zinc refining process liquid is high, and it can cope with variations in the process.
［実施例１１］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）に４０ｇ／ＬのＺｎを共存させて用いた以外は、実施例５と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例５と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 11]
The reaction product was reacted in the same manner as in Example 5 except that 40 g / L of Zn was used in the same arsenic-containing solution (solution having the composition shown in Table 2) as in Example 1 and then used. The solid content obtained by solid-liquid separation was treated in the same manner as in Example 5, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０４を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０２ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。この結果から、砒素含有溶液中に亜鉛が共存しても砒素の溶出濃度が非常に低く、また、砒素含有溶液中の砒素濃度が高ければ、吹き込まれる酸素の圧力が大気圧であっても影響がないので、本発明による砒素含有溶液の処理方法を通常の亜鉛製錬の工程液の処理に適用することができるのがわかる。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.04. From the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.02 mg / L, which was much lower than the reference value (0.3 mg / L). From this result, even if zinc coexists in the arsenic-containing solution, the arsenic elution concentration is very low, and if the arsenic concentration in the arsenic-containing solution is high, even if the pressure of the injected oxygen is atmospheric pressure, it is not affected. Thus, it can be seen that the method for treating an arsenic-containing solution according to the present invention can be applied to the treatment of a normal zinc smelting process liquid.
［実施例１２］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）に４０ｇ／ＬのＣｕを共存させて用いた以外は、実施例５と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例５と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 12]
The reaction product was reacted in the same manner as in Example 5 except that 40 g / L of Cu was used in the same arsenic-containing solution as in Example 1 (solution having the composition shown in Table 2). The solid content obtained by solid-liquid separation was treated in the same manner as in Example 5, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．００を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０８ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。この結果から、砒素含有溶液中に銅が共存しても砒素の溶出濃度が非常に低く、本発明による砒素含有溶液の処理方法を銅製錬の工程液の処理に適用することができるのがわかる。また、砒素含有溶液中の砒素濃度が高ければ、吹き込まれる酸素の圧力が大気圧であっても影響がないので、本発明による砒素含有溶液の処理方法を通常の銅製錬の工程液の処理に適用することができるのがわかる。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.00, and it was found from the results of X-ray diffraction that a powder of crystalline iron and arsenic compound was obtained. It was. The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.08 mg / L, which was much lower than the reference value (0.3 mg / L). From this result, it can be seen that even if copper coexists in the arsenic-containing solution, the arsenic elution concentration is very low, and the processing method of the arsenic-containing solution according to the present invention can be applied to the processing of the copper smelting process liquid. . In addition, if the arsenic concentration in the arsenic-containing solution is high, there is no effect even if the pressure of the blown oxygen is atmospheric pressure. Therefore, the arsenic-containing solution processing method according to the present invention is used for processing a normal copper smelting process liquid. You can see that it can be applied.
［実施例１３］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）に４０ｇ／ＬのＮａを共存させて用いた以外は、実施例５と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例５と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 13]
The reaction product was reacted in the same manner as in Example 5 except that 40 g / L of Na was used in the same arsenic-containing solution as in Example 1 (solution having the composition shown in Table 2). The solid content obtained by solid-liquid separation was treated in the same manner as in Example 5, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０５を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０７ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。この結果から、砒素含有溶液中にナトリウムが共存しても砒素の溶出濃度が非常に低く、本発明による砒素含有溶液の処理方法をアルカリ廃液の処理や前工程でナトリウムが残存している溶液の処理に適用することができるのがわかる。また、砒素含有溶液中の砒素濃度が高ければ、吹き込まれる酸素の圧力が大気圧であっても影響がないのができるのがわかる。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.05. From the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. The elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.07 mg / L, which was much lower than the reference value (0.3 mg / L). From this result, even if sodium coexists in the arsenic-containing solution, the elution concentration of arsenic is very low, and the arsenic-containing solution treatment method according to the present invention is a solution of alkaline waste liquid or a solution in which sodium remains in the previous step. It can be seen that it can be applied to processing. It can also be seen that if the arsenic concentration in the arsenic-containing solution is high, there is no effect even if the pressure of the oxygen blown is atmospheric pressure.
［実施例１４］
実施例１と同様の砒素含有溶液（表２に示す組成の溶液）に４０ｇ／ＬのＣｕを共存させて用いた以外は、実施例６と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例６と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 14]
The reaction product was reacted in the same manner as in Example 6 except that 40 g / L of Cu was used in the same arsenic-containing solution as in Example 1 (solution having the composition shown in Table 2). The solid content obtained by solid-liquid separation was treated in the same manner as in Example 6, and the same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０２を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０４ｍｇ／Ｌであり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。この結果から、砒素含有溶液中の砒素濃度が３０ｇ／Ｌ程度まで低くなった場合にも、吹き込まれる酸素の圧力が大気圧であっても影響がないので、亜鉛製錬の工程液中の砒素濃度がある程度低くても、本発明による砒素含有溶液の処理方法を通常の亜鉛製錬の工程液の処理に適用することができるのがわかる。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.02, and from the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.04 mg / L, which was much lower than the reference value (0.3 mg / L). From this result, even when the arsenic concentration in the arsenic-containing solution is lowered to about 30 g / L, there is no influence even if the pressure of the blown oxygen is atmospheric pressure. It can be seen that even if the concentration is low to some extent, the method for treating an arsenic-containing solution according to the present invention can be applied to the treatment of an ordinary zinc smelting process liquid.
［実施例１５］
酸素ガスの代わりに空気を吹き込んだ以外は、実施例１２と同様の方法によって反応させた後、反応生成物の固液分離によって得られた固形分を実施例１２と同様に処理し、得られた粉体について実施例１と同様の測定および計算を行った。その条件および結果を表３〜表８に示す。
[Example 15]
After reacting by the same method as in Example 12 except that air was blown in place of oxygen gas, the solid content obtained by solid-liquid separation of the reaction product was treated in the same manner as in Example 12 and obtained. The same measurement and calculation as in Example 1 were performed on the obtained powder. The conditions and results are shown in Tables 3 to 8.
表８に示すように、得られた粉体のＦｅ／Ａｓ（モル比）は１．０１を示し、Ｘ線回折の結果から結晶質の鉄と砒素の化合物の粉末が得られたことがわかった。また、得られた鉄と砒素の化合物の粉末からの砒素の溶出濃度は０．０１ｍｇ／Ｌ以下であり、基準値（０．３ｍｇ／Ｌ）より非常に低かった。この結果からわかるように、砒素含有溶液中の砒素濃度が高ければ、空気のように酸素濃度が低いガスを大気圧で吹き込んでも影響がないので、本発明による砒素含有溶液の処理方法を通常の銅製錬の工程液の処理に適用することができるとともに、コストを削減することもできる。 As shown in Table 8, Fe / As (molar ratio) of the obtained powder was 1.01, and from the result of X-ray diffraction, it was found that a powder of crystalline iron and arsenic compound was obtained. It was. Further, the elution concentration of arsenic from the obtained powder of iron and arsenic compound was 0.01 mg / L or less, which was much lower than the reference value (0.3 mg / L). As can be seen from this result, if the arsenic concentration in the arsenic-containing solution is high, there is no influence even if a gas having a low oxygen concentration such as air is blown at atmospheric pressure. The present invention can be applied to the treatment of copper smelting process liquid, and the cost can be reduced.
Claims (6)
6. The method for treating an arsenic-containing solution according to claim 1, wherein an elution concentration of arsenic from the crystalline iron and arsenic compound powder is lower than 0.3 mg / L.
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