JP4710033B2 - Arsenic content treatment method - Google Patents
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- JP4710033B2 JP4710033B2 JP2006126586A JP2006126586A JP4710033B2 JP 4710033 B2 JP4710033 B2 JP 4710033B2 JP 2006126586 A JP2006126586 A JP 2006126586A JP 2006126586 A JP2006126586 A JP 2006126586A JP 4710033 B2 JP4710033 B2 JP 4710033B2
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- 229910052785 arsenic Inorganic materials 0.000 title claims description 98
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 94
- 238000000034 method Methods 0.000 title claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 117
- 239000007788 liquid Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 38
- 239000003513 alkali Substances 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 36
- 238000002386 leaching Methods 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 description 30
- 238000002425 crystallisation Methods 0.000 description 26
- 230000008025 crystallization Effects 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000001556 precipitation Methods 0.000 description 15
- 238000003723 Smelting Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 125000000223 arsonoyl group Chemical group [H][As](*)(*)=O 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-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
- 229940000488 arsenic acid Drugs 0.000 description 2
- 150000001495 arsenic compounds Chemical class 0.000 description 2
- 229940103357 calcium arsenate Drugs 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 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
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229940000489 arsenate Drugs 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
Classifications
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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、砒素含有物質の処理方法に関し、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砒素を回収する方法に関する。 The present invention relates to a method for treating an arsenic-containing substance, and more particularly to a method for treating an arsenic-containing substance containing various elements other than arsenic, such as a non-ferrous smelting intermediate, and recovering arsenic.
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分離して回収する方法としては、製錬中間物などを焼成することによってＡｓ２Ｏ３として回収する方法が提案されている。しかし、この方法では、ＣＯ雰囲気の制御やＡｓ２Ｏ３の粉塵の回収などが技術的に容易ではなく、大規模な設備が必要である。 Conventionally, as a method for separating and recovering arsenic from a smelting intermediate containing arsenic, a method of recovering As 2 O 3 by firing the smelting intermediate has been proposed. However, in this method, control of the CO atmosphere and recovery of As 2 O 3 dust are not technically easy, and a large-scale facility is required.
また、砒素を含む製錬中間物から砒素を浸出して分離する方法として、湿式反応により砒素を分離して回収する方法が提案されている（例えば、特許文献１参照）。この方法は、砒素を含む硫化物態の銅製錬中間物をスラリー化し、これに空気を吹き込みながらアルカリを添加し、スラリーの温度を５０℃以上、ｐＨ５〜８に保持しながら浸出処理を行って、製錬中間物中の砒素を酸性砒酸塩として含有する溶液を生成し、この溶液と不溶解残渣を分離する第１工程と、この第１工程で得られた水溶液に消石灰を添加して、生成する砒酸カルシウム沈澱とアルカリの水溶液とを分離し、アルカリの水溶液を第１工程に再循環する第２工程と、この第２工程で得られた砒酸カルシウムの沈澱を硫酸に溶解し、得られた砒酸と石膏とを分離する第３工程と、この第３工程で得られた砒酸を亜硫酸ガスで還元し、得られた亜砒酸と硫酸溶液とを分離し、硫酸溶液を第３工程に再循環する第４工程とからなる。この特許文献１では、アルカリとして水酸化ナトリウムを使用した場合に砒素が酸化抽出される反応式として、以下の反応式を推定している。
Ａｓ２Ｓ３＋３／２Ｏ２＋Ｈ２Ｏ→２ＨＡｓＯ２＋３Ｓ （１）
ＨＡｓＯ２＋１／２Ｏ２＋ＮａＯＨ→ＮａＨ２ＡｓＯ４ （２）
ＨＡｓＯ２＋１／２Ｏ２＋２ＮａＯＨ→Ｎａ２ＨＡｓＯ４＋Ｈ２Ｏ （３）
Ａｓ２Ｓ３＋６Ｏ２＋４Ｈ２Ｏ→２ＨＡｓＯ２＋３Ｈ２ＳＯ４ （４）
Further, as a method of leaching and separating arsenic from a smelting intermediate containing arsenic, a method of separating and recovering arsenic by a wet reaction has been proposed (for example, see Patent Document 1). In this method, a sulfide-type copper smelting intermediate containing arsenic is slurried, and alkali is added while blowing air thereto, and leaching is performed while maintaining the temperature of the slurry at 50 ° C. or higher and pH 5-8. A first step of producing a solution containing arsenic in the smelting intermediate as an acidic arsenate, separating the solution and the insoluble residue, and adding slaked lime to the aqueous solution obtained in the first step, The resulting calcium arsenate precipitate is separated from the aqueous alkali solution, the second step of recycling the aqueous alkali solution to the first step, and the calcium arsenate precipitate obtained in the second step is dissolved in sulfuric acid. A third step of separating arsenic acid and gypsum, reducing the arsenic acid obtained in this third step with sulfurous acid gas, separating the resulting arsenous acid and sulfuric acid solution, and recycling the sulfuric acid solution to the third step And a fourth step. In this patent document 1, the following reaction formula is estimated as a reaction formula in which arsenic is oxidized and extracted when sodium hydroxide is used as an alkali.
As 2 S 3 + 3 / 2O 2 + H 2 O → 2HAsO 2 + 3S (1)
HAsO 2 + 1 / 2O 2 + NaOH → NaH 2 AsO 4 (2)
HAsO 2 + 1 / 2O 2 + 2NaOH → Na 2 HAsO 4 + H 2 O (3)
As 2 S 3 + 6O 2 + 4H 2 O → 2HAsO 2 + 3H 2 SO 4 (4)
また、特許文献１には、抽出反応時のｐＨを高くして上記の反応式（４）に従ってもよいが、この反応式（４）に従うと、原料中の硫黄分が硫酸にまで酸化され、生成する硫酸を中和するために余分なアルカリの消費が行われるが、抽出反応時の水溶液のｐＨを５〜８に制御して反応式（１）に従って砒素を抽出すると、原料中の硫黄分は硫酸まで酸化されずに元素状態の硫黄でとどまるので、水溶液を中和するための余分なアルカリの消費を避けることができると記載されている。 Further, in Patent Document 1, the pH during the extraction reaction may be increased and the above reaction formula (4) may be followed, but according to this reaction formula (4), the sulfur content in the raw material is oxidized to sulfuric acid, Excess alkali is consumed to neutralize the sulfuric acid produced. When arsenic is extracted according to the reaction formula (1) while controlling the pH of the aqueous solution during the extraction reaction to 5 to 8, the sulfur content in the raw material is reduced. Is not oxidized to sulfuric acid but remains in elemental sulfur, so that it is possible to avoid consumption of excess alkali to neutralize the aqueous solution.
しかし、反応式（１）の反応は極めて遅い反応であり、また、アルカリ溶液中におけるＡｓの酸化反応はアルカリ濃度が高いほど速くなるので（例えば、非特許文献１参照）、アルカリ濃度を高くして反応を速くすることが望ましい。 However, the reaction of the reaction formula (1) is an extremely slow reaction, and the oxidation reaction of As in an alkaline solution becomes faster as the alkali concentration is higher (for example, see Non-Patent Document 1). It is desirable to speed up the reaction.
しかし、上述したように、アルカリ濃度を高くすると反応式（４）に従って原料中の硫黄分が硫酸にまで酸化されて、生成する硫酸を中和するために余分なアルカリが必要になるので、使用したアルカリを効率的に回収することができる方法が望まれている。また、特許文献１の方法では、浸出処理後の溶液中に消石灰を添加してアルカリ溶液を分離回収しているが、消石灰を添加することによって工程が複雑になるため、浸出処理後の溶液中に消石灰などの添加物を添加することなく、砒素とアルカリを容易に分離する方法が望まれている。 However, as described above, when the alkali concentration is increased, the sulfur content in the raw material is oxidized to sulfuric acid in accordance with the reaction formula (4), and extra alkali is required to neutralize the sulfuric acid to be produced. A method that can efficiently recover the alkali thus obtained is desired. Further, in the method of Patent Document 1, slaked lime is added to the solution after the leaching treatment to separate and recover the alkaline solution. However, the process becomes complicated by adding slaked lime, so the solution in the solution after the leaching treatment There is a demand for a method for easily separating arsenic and alkali without adding additives such as slaked lime.
したがって、本発明は、このような従来の問題点に鑑み、砒素含有物質を処理して砒素を効率的且つ容易に回収することができるとともに、再生されるアルカリ液への砒素の混入を防止して再利用可能なアルカリ液を効率的且つ容易に回収することができる、砒素含有物質の処理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 can efficiently and easily recover arsenic by treating an arsenic-containing substance and prevent arsenic from being mixed into the regenerated alkaline liquid. Another object of the present invention is to provide a method for treating an arsenic-containing substance, which can efficiently and easily recover an alkaline liquid that can be reused.
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、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得られた砒素を含む浸出液を冷却晶析することにより、砒素含有物質を処理して砒素を効率的且つ容易に回収することができるとともに、再生されるアルカリ液への砒素の混入を防止して再利用可能なアルカリ液を効率的且つ容易に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-mentioned problems, the present inventors have found that an leaching solution containing arsenic obtained by solid-liquid separation after alkali leaching while oxidizing an arsenic-containing substance to an alkaline solution by oxidizing to pH 10 or higher By cooling and crystallizing, the arsenic-containing substance can be treated to recover arsenic efficiently and easily, and an alkaline liquid that can be reused by preventing arsenic from being mixed into the regenerated alkaline liquid. The inventors have found that it can be efficiently and easily recovered, and have completed the present invention.
すなわち、本発明による砒素含有物質の処理方法は、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、この浸出液を冷却して析出物を得た後に固液分離して、砒素とアルカリ金属の化合物を得るとともにアルカリ溶液を回収する工程とを備えたことを特徴とする。 That is, the method for treating an arsenic-containing substance according to the present invention includes a step of adding an arsenic-containing substance to an alkaline solution to obtain a leachate containing arsenic by solid-liquid separation after alkali leaching while oxidizing to pH 10 or more and oxidizing the leached liquid. The method is characterized by comprising a step of solid-liquid separation after cooling to obtain a precipitate to obtain a compound of arsenic and an alkali metal and collecting an alkali solution.
この砒素含有物質の処理方法において、アルカリ溶液が水酸化ナトリウム溶液であるのが好ましく、水酸化ナトリウム溶液中の水酸化ナトリウム濃度が１５０〜３００ｇ／Ｌであるのが好ましい。また、砒素含有物質の酸化および浸出の際の温度が７０℃以上であるのが好ましく、７０〜９８℃であるのがさらに好ましい。また、浸出液の冷却の際の温度が５０℃以下であるのが好ましく、１０℃以下であるのがさらに好ましい。さらに、浸出液の冷却の際に浸出液を撹拌するのが好ましい。また、砒素含有物質が、銅、亜鉛、鉄、インジウム、ガリウム、錫、アンチモン、鉛、カドミウム、ナトリウム、カリウム、マグネシウムおよびカルシウムの少なくとも一種を含んでもよい。 In this method for treating an arsenic-containing substance, the alkaline solution is preferably a sodium hydroxide solution, and the sodium hydroxide concentration in the sodium hydroxide solution is preferably 150 to 300 g / L. Further, the temperature at the time of oxidation and leaching of the arsenic-containing substance is preferably 70 ° C. or higher, more preferably 70 to 98 ° C. Further, the temperature during cooling of the leachate is preferably 50 ° C. or less, more preferably 10 ° C. or less. Furthermore, it is preferable to stir the leachate when cooling the leachate. The arsenic-containing material may contain at least one of copper, zinc, iron, indium, gallium, tin, antimony, lead, cadmium, sodium, potassium, magnesium, and calcium.
本発明によれば、砒素含有物質を処理して砒素を効率的且つ容易に回収することができるとともに、再生されるアルカリ液への砒素の混入を防止して再利用可能なアルカリ液を効率的且つ容易に回収することができる。 According to the present invention, arsenic can be efficiently and easily recovered by treating an arsenic-containing substance, and the reusable alkaline liquid can be efficiently prevented by preventing arsenic from being mixed into the regenerated alkaline liquid. And it can collect | recover easily.
以下、添付図面を参照して、本発明による砒素含有物質の処理方法の実施の形態について説明する。 Embodiments of a method for treating an arsenic-containing material according to the present invention will be described below with reference to the accompanying drawings.
図１は、本発明による砒素含有物質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物質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）この浸出液の冷却晶析を行った後に固液分離して砒素とアルカリ金属の化合物を得るとともにアルカリ溶液を回収する冷却晶析工程とを備えている。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 substance according to the present invention. As shown in FIG. 1, an embodiment of the method for treating an arsenic-containing material according to the present invention is as follows. (1) After leaching the alkali while oxidizing it to pH 10 or more, preferably pH 12 or more by adding the arsenic-containing material to an alkaline solution. An alkaline leaching / oxidation step for obtaining a leaching solution containing arsenic by solid-liquid separation, and (2) cooling and crystallization of the leaching solution, followed by solid-liquid separation to obtain a compound of arsenic and an alkali metal and collecting an alkaline solution. Cooling crystallization process. Hereinafter, each of these steps will be described.
なお、本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。また、本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。 Note that as the arsenic-containing substance to be processed by the method for processing an arsenic-containing substance of the present embodiment, a substance containing sulfur and arsenic such as sulfides such as arsenic sulfide (As 2 S 3 ) and FeAsS may be used. it can. 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. In addition to arsenic (As) and sulfur (S), the arsenic containing material to be treated by the method for treating an arsenic containing material of this embodiment is copper (Cu), zinc (Zn), iron (Fe), indium (In), gallium (Ga), tin (Sn), antimony (Sb), lead (Pb), cadmium (Cd), sodium (Na), potassium (K), magnesium (Mg) and calcium (Ca) One kind may be included.
（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 is not leached when the alkali concentration is low. Therefore, the quality of Zn in the arsenic-containing material, the quality of arsenic, and the leaching behavior of other impurities (especially Sn and Sb) are affected. 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１５０〜３００ｇ／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 150 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 an oxidizing agent, hydrogen peroxide, ozone, etc. can be used in addition to a solid oxidizing agent such as potassium permanganate, but air or oxygen with increased concentration may be used. Oxidation reaction proceeds easily by bubbling and stirring the gas.
浸出の際の反応温度が高いほど素早く浸出されるが、後に冷却晶析を行うためには５０℃以上にする必要があり、また、熱エネルギー消費の増加を防止するためには高過ぎる温度にしない方がよいので、反応温度は７０〜９８℃であるのが好ましい。 The higher the reaction temperature during leaching, the quicker the leaching. However, in order to perform cooling crystallization later, the temperature must be 50 ° C. or higher, and the temperature is too high to prevent an increase in heat energy consumption. Since it is better not to do so, the reaction temperature is preferably 70 to 98 ° C.
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）冷却晶析工程
次に、得られた浸出液の冷却晶析を行う。上述したアルカリ浸出・酸化工程で使用したＮａＯＨ溶液のＮａＯＨ濃度が高いと、この浸出液中のＮａＯＨ濃度が高くなり、砒素の化合物の形態が変化すると考えられる。すなわち、希薄な溶液の場合と、ＮａＯＨ濃度が若干高くなった場合のＮａとＡｓの形態は、以下の反応式で表される。
４ＮａＯＨ＋２Ａｓ２Ｓ３＋５Ｏ２＋２Ｈ２Ｏ → ４ＮａＨ２ＡｓＯ４＋６Ｓ
８ＮａＯＨ＋２Ａｓ２Ｓ３＋５Ｏ２ → ４Ｎａ２ＨＡｓＯ４＋６Ｓ＋２Ｈ２Ｏ
(2) Cooling crystallization process Next, the obtained leachate is cooled and crystallized. If the NaOH concentration of the NaOH solution used in the alkali leaching / oxidation step described above is high, the NaOH concentration in the leaching solution increases, and the form of the arsenic compound is considered to change. That is, the form of Na and As in the case of a dilute solution and when the NaOH concentration is slightly increased is expressed by the following reaction formula.
4NaOH + 2As 2 S 3 + 5O 2 + 2H 2 O → 4NaH 2 AsO 4 + 6S
8NaOH + 2As 2 S 3 + 5O 2 → 4Na 2 HAsO 4 + 6S + 2H 2 O
このように、ＮａＯＨ濃度が高くなると、砒素化合物の形態が変化して、砒素とナトリウムの反応の割合が変化する。さらにＮａＯＨ濃度を高くすると、以下の反応が起こる。
１２ＮａＯＨ＋２Ａｓ２Ｓ３＋５Ｏ２ → ４Ｎａ３ＡｓＯ４＋６Ｓ＋６Ｈ２Ｏ
Thus, as the NaOH concentration increases, the form of the arsenic compound changes, and the reaction rate between arsenic and sodium changes. When the NaOH concentration is further increased, the following reaction occurs.
12NaOH + 2As 2 S 3 + 5O 2 → 4Na 3 AsO 4 + 6S + 6H 2 O
そのため、冷却晶析によって析出物を得るためには、アルカリ浸出・酸化工程で使用するＮａＯＨ溶液のＮａＯＨ濃度を高くしておく必要がある。すなわち、アルカリ浸出可能なＺｎなどもある程度浸出させる程度のＮａＯＨ濃度にしなければ、ＮａＨ２ＡｓＯ４やＮａ２ＨＡｓＯ４の形態でＡｓが浸出されるため、冷却晶析が進行しないので、ＮａＯＨ濃度をある程度高くする必要がある。また、上記の反応式では、砒素１モルに対してＮａＯＨが２モルまでは、Ｎａ２ＨＡｓＯ４の形態で生成され、砒素の量がそれ以上になると、Ｎａ３ＡｓＯ４の形態になるので、１モルの砒素に対して３モルのＮａＯＨにすると、砒素とアルカリ金属の化合物が好ましい形態になる。 Therefore, in order to obtain a precipitate by cooling crystallization, it is necessary to increase the NaOH concentration of the NaOH solution used in the alkali leaching / oxidation step. That is, unless the NaOH concentration that allows alkali leaching to some extent is leached to some extent, As is leached in the form of NaH 2 AsO 4 or Na 2 HAsO 4 , cooling crystallization does not proceed, so the NaOH concentration is reduced. It needs to be raised to some extent. Further, in the above reaction formula, up to 2 moles of NaOH with respect to 1 mole of arsenic is generated in the form of Na 2 HAsO 4 , and when the amount of arsenic is more than that, it is in the form of Na 3 AsO 4 . When 3 mol of NaOH is used per 1 mol of arsenic, a compound of arsenic and an alkali metal is a preferred form.
また、冷却によって析出物を得ることができる冷却温度は５０℃以下であり、室温程度まで冷却すれば晶析がほぼ完了するので、冷却温度を２５℃以下にするのが好ましいが、冷却温度が低いほど砒素の析出率が上昇するので、冷却温度を１０℃以下にするのがさらに好ましい。 In addition, the cooling temperature at which precipitates can be obtained by cooling is 50 ° C. or lower, and crystallization is almost completed if cooled to about room temperature. Therefore, the cooling temperature is preferably 25 ° C. or lower. The lower the value, the higher the arsenic precipitation rate. Therefore, the cooling temperature is more preferably 10 ° C. or lower.
また、冷却晶析の際に撹拌するのが好ましい。撹拌しないと、晶析物が溶液内で網目状に析出して固形化し易くなり、固液分離の際に移液できない場合がある。 Further, it is preferable to stir during cooling crystallization. Without stirring, the crystallized product precipitates in the form of a network in the solution and becomes solidified easily, and there are cases where the liquid cannot be transferred during solid-liquid separation.
なお、アルカリ薬品は非常に高価な薬品であるので、前工程に繰返し使用するのが好ましい。また、アルカリ浸出液は、ＮａとＡｓの他にＧａなどを含んだ液であり、Ｇａは繰り返しの工程中で濃縮されていくので、Ｇａがある程度高濃度になった後にアルカリ電解採取を行って、Ｇａを回収することができる。 In addition, since alkaline chemicals are very expensive chemicals, they are preferably used repeatedly in the previous step. In addition, the alkaline leaching solution is a solution containing Ga and the like in addition to Na and As. Since Ga is concentrated in the repeated process, alkaline electrowinning is performed after Ga reaches a certain concentration. Ga can be recovered.
以下、本発明による砒素含有物質の処理方法の実施例について詳細に説明する。 Hereinafter, embodiments of the method for treating an arsenic-containing material according to the present invention will be described in detail.
［実施例１］
まず、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８０ｇをＮａＯＨ濃度２００ｇ／ＬのＮａＯＨ溶液（Ｎａ濃度１１５ｇ／Ｌ）８００ｍＬに入れ（ＮａＯＨ溶液１Ｌ当りの砒素含有物質１００ｇ（パルプ濃度ＰＤ＝１００ｇ／Ｌ））、液温９８℃に加熱し、０．４Ｌ／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、砒素含有物質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. 80 g of this arsenic-containing substance is put into 800 mL of NaOH solution (Na concentration 115 g / L) with a NaOH concentration of 200 g / L (100 g of arsenic-containing substance per 1 L of NaOH solution (pulp concentration PD = 100 g / L)), and the liquid temperature reaches 98 ° C. The mixture was heated, and air (gas / liquid ratio = 0.5) was blown at a flow rate of 0.4 L / min. The mixture was allowed to react for 1 hour with stirring, and alkali leaching was performed while oxidizing the arsenic-containing substance. 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に加圧して固液分離した。この固液分離後のフィルタを通過したろ液（アルカリ浸出液）についてＩＣＰによって組成分析を行った。これらの条件および分析結果をそれぞれ表２および表３に示す。 Next, after cooling to a liquid temperature of 70 ° C., solid-liquid separation was performed using a membrane filter made of PTFE (polytetrafluoroethylene) having an opening of 3 μm and pressurizing to 0.4 MPa with a pressure filter. Composition analysis was performed by ICP on the filtrate (alkaline leachate) that passed through the filter after the solid-liquid separation. These conditions and analysis results are shown in Table 2 and Table 3, respectively.
次に、固液分離後のアルカリ浸出液を３００ｒｐｍで撹拌しながら１時間で１０℃まで冷却した後、さらに１時間保持したところ、白色の結晶が塊となって析出した。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に加圧して固液分離した。この冷却晶析によって、砒素を析出させて分離するとともに、ＮａＯＨ液を再生した。 Next, the alkali leachate after solid-liquid separation was cooled to 10 ° C. over 1 hour while stirring at 300 rpm, and then kept for 1 hour. As a result, white crystals precipitated as a lump. Thereafter, using a membrane filter made of PTFE having an opening of 3 microns, solid-liquid separation was performed by applying pressure to 0.4 MPa with a pressure filter. By this cooling crystallization, arsenic was precipitated and separated, and the NaOH solution was regenerated.
この固液分離後のフィルタを通過したろ液（冷却晶析后液）とフィルタに残った固形分（冷却晶析物）についてＩＣＰによって組成分析を行った。なお、冷却晶析后液の量は７１８ｍＬであった。また、固液分離後によって固形分として得られたケーキを６０℃で乾燥した。なお、この乾燥前後の重量を測定することによって水分値を算出するとともに、冷却晶析による各々の元素の析出率を算出した。これらの条件および分析結果をそれぞれ表４および表５に示し、析出率の計算値を表６に示す。なお、乾燥前の固形分の重量は７５ｇであり、水分は４５％であった。 Composition analysis was performed by ICP on the filtrate (liquid after cooling crystallization) that passed through the filter after this solid-liquid separation and the solid content (cooled crystallized product) remaining on the filter. The amount of the solution after cooling crystallization was 718 mL. Moreover, the cake obtained as solid content after solid-liquid separation was dried at 60 ° C. The moisture value was calculated by measuring the weight before and after drying, and the precipitation rate of each element by cooling crystallization was calculated. These conditions and analysis results are shown in Table 4 and Table 5, respectively, and the calculated precipitation rate is shown in Table 6. In addition, the weight of the solid content before drying was 75 g, and the water content was 45%.
［比較例１］
液温を９０℃とし、反応液中に空気を吹き込まなかった以外は、実施例１と同様の方法で、砒素含有物質を酸化しながらアルカリ浸出した後、固液分離し、組成分析を行った。これらの条件および分析結果をそれぞれ表２および表３に示す。なお、冷却晶析后液の量は７８７ｍＬであった。
[Comparative Example 1]
Except that the liquid temperature was 90 ° C. and no air was blown into the reaction solution, the arsenic-containing substance was leached with alkali while oxidizing, and then the solid-liquid separation was performed and the composition analysis was performed in the same manner as in Example 1. . These conditions and analysis results are shown in Table 2 and Table 3, respectively. The amount of the solution after cooling crystallization was 787 mL.
また、実施例１と同様の方法によって冷却晶析を行った後、固液分離し、組成分析および析出率の算出を行った。これらの条件および分析結果をそれぞれ表４および表５に示し、析出率の計算値を表６に示す。なお、乾燥前の固形分の重量は１２ｇであり、水分は５４．５％であった。 Further, after cooling crystallization by the same method as in Example 1, solid-liquid separation was performed, and a composition analysis and a precipitation rate were calculated. These conditions and analysis results are shown in Table 4 and Table 5, respectively, and the calculated precipitation rate is shown in Table 6. In addition, the weight of the solid content before drying was 12 g, and the water content was 54.5%.
［実施例２］
砒素含有物質の量を１６０ｇ（ＮａＯＨ溶液１Ｌ当りの砒素含有物質２００ｇ（パルプ濃度ＰＤ＝２００ｇ／Ｌ））とした以外は、実施例１と同様の方法で、砒素含有物質を酸化しながらアルカリ浸出した後、固液分離し、組成分析を行った。これらの条件および分析結果をそれぞれ表２および表３に示す。なお、冷却晶析后液の量は６０６ｍＬであった。
[Example 2]
Alkaline leaching while oxidizing the arsenic-containing material in the same manner as in Example 1 except that the amount of the arsenic-containing material was 160 g (200 g of arsenic-containing material per liter of NaOH solution (pulp concentration PD = 200 g / L)). After that, solid-liquid separation was performed and composition analysis was performed. These conditions and analysis results are shown in Table 2 and Table 3, respectively. The amount of the solution after cooling crystallization was 606 mL.
また、実施例１と同様の方法によって冷却晶析を行った後、固液分離し、組成分析および析出率の算出を行った。これらの条件および分析結果をそれぞれ表４および表５に示し、析出率の計算値を表６に示す。なお、乾燥前の固形分の重量は１７６．１ｇであり、水分は３７．５％であった。 Further, after cooling crystallization by the same method as in Example 1, solid-liquid separation was performed, and a composition analysis and a precipitation rate were calculated. These conditions and analysis results are shown in Table 4 and Table 5, respectively, and the calculated precipitation rate is shown in Table 6. In addition, the weight of the solid content before drying was 176.1 g, and the water content was 37.5%.
［実施例３］
砒素含有物質の量を２４０ｇ（ＮａＯＨ溶液１Ｌ当りの砒素含有物質３００ｇ（パルプ濃度ＰＤ＝３００ｇ／Ｌ））とした以外は、実施例１と同様の方法で、砒素含有物質を酸化しながらアルカリ浸出した後、固液分離し、組成分析を行った。これらの条件および分析結果をそれぞれ表２および表３に示す。なお、冷却晶析后液の量は５６２ｍＬであった。
[Example 3]
Alkaline leaching while oxidizing the arsenic containing material in the same manner as in Example 1 except that the amount of the arsenic containing material was 240 g (300 g of arsenic containing material per liter of NaOH solution (pulp concentration PD = 300 g / L)) After that, solid-liquid separation was performed and composition analysis was performed. These conditions and analysis results are shown in Table 2 and Table 3, respectively. The amount of the liquid after cooling crystallization was 562 mL.
また、実施例１と同様の方法によって冷却晶析を行った後、固液分離し、組成分析および析出率の算出を行った。これらの条件および分析結果をそれぞれ表４および表５に示し、析出率の計算値を表６に示す。なお、乾燥前の固形分の重量は２１６．７ｇであり、水分は４６％であった。 Further, after cooling crystallization by the same method as in Example 1, solid-liquid separation was performed, and a composition analysis and a precipitation rate were calculated. These conditions and analysis results are shown in Table 4 and Table 5, respectively, and the calculated precipitation rate is shown in Table 6. The solid content before drying was 216.7 g, and the water content was 46%.
実施例１〜３および比較例１から、１時間という短時間でＡｓを効率的に浸出していることがわかる。また、実施例１〜３のように空気を吹き込まなければ酸化反応が進まないので、比較例１では、浸出が半分しか進んでいないのがわかる。さらに、実施例１〜３のようにＮａＯＨ溶液１Ｌ当りの砒素含有物質１００〜３００ｇであれば、ほぼ全ての砒素を浸出させることができるのがわかる。また、実施例１〜３から、ＮａＯＨ溶液１Ｌ当りの砒素含有物質の量にかかわらず、浸出した砒素の９０％以上を冷却晶析によって析出させて除去することができるのがわかる。 From Examples 1 to 3 and Comparative Example 1, it can be seen that As was efficiently leached in a short time of 1 hour. Further, since the oxidation reaction does not proceed unless air is blown as in Examples 1 to 3, it can be seen that in Comparative Example 1, leaching proceeds only half. Further, it can be seen that almost 100% of arsenic can be leached if the arsenic-containing substance is 100 to 300 g per liter of NaOH solution as in Examples 1 to 3. Further, from Examples 1 to 3, it can be seen that 90% or more of the leached arsenic can be precipitated and removed by cooling crystallization regardless of the amount of arsenic-containing substance per 1 L of NaOH solution.
［実施例４］
ＮａＯＨ濃度を１５０ｇ／Ｌにした以外は、実施例２と同様の方法で、砒素含有物質を酸化しながらアルカリ浸出した後、固液分離し、組成分析を行った。これらの条件および分析結果をそれぞれ表２および表３に示す。なお、冷却晶析后液の量は６３２ｍＬであった。
[Example 4]
Except for changing the NaOH concentration to 150 g / L, the arsenic-containing material was leached with alkali while oxidizing, followed by solid-liquid separation and composition analysis in the same manner as in Example 2. These conditions and analysis results are shown in Table 2 and Table 3, respectively. The amount of the solution after cooling crystallization was 632 mL.
また、実施例１と同様の方法によって冷却晶析を行った後、固液分離し、組成分析および析出率の算出を行った。これらの条件および分析結果をそれぞれ表４および表５に示し、析出率の計算値を表６に示す。なお、乾燥前の固形分の重量は１５２．７ｇであり、水分は３６．４％であった。 Further, after cooling crystallization by the same method as in Example 1, solid-liquid separation was performed, and a composition analysis and a precipitation rate were calculated. These conditions and analysis results are shown in Table 4 and Table 5, respectively, and the calculated precipitation rate is shown in Table 6. In addition, the weight of the solid content before drying was 152.7 g, and the water content was 36.4%.
［比較例２］
ＮａＯＨ濃度を１００ｇ／Ｌにした以外は、実施例２と同様の方法で、砒素含有物質を酸化しながらアルカリ浸出した後、固液分離し、組成分析を行った。これらの条件および分析結果をそれぞれ表２および表３に示す。なお、冷却晶析后液の量は７２５ｍＬであった。
[Comparative Example 2]
Except that the NaOH concentration was set to 100 g / L, the arsenic-containing material was leached with alkali while oxidizing, followed by solid-liquid separation and composition analysis in the same manner as in Example 2. These conditions and analysis results are shown in Table 2 and Table 3, respectively. The amount of the liquid after cooling crystallization was 725 mL.
また、実施例１と同様の方法によって冷却晶析を行った後、固液分離し、組成分析および析出率の算出を行った。これらの条件および分析結果をそれぞれ表４および表５に示し、析出率の計算値を表６に示す。なお、乾燥前の固形分の重量は６８ｇであり、水分は４７．４％であった。 Further, after cooling crystallization by the same method as in Example 1, solid-liquid separation was performed, and a composition analysis and a precipitation rate were calculated. These conditions and analysis results are shown in Table 4 and Table 5, respectively, and the calculated precipitation rate is shown in Table 6. In addition, the weight of the solid content before drying was 68 g, and the water content was 47.4%.
［比較例３］
ＮａＯＨ濃度を５０ｇ／Ｌにした以外は、実施例２と同様の方法で、砒素含有物質を酸化しながらアルカリ浸出した後、固液分離し、組成分析を行った。これらの条件および分析結果をそれぞれ表２および表３に示す。また、実施例１と同様の方法によって冷却晶析を試みたが、析出物が全くなかったため、その後の固液分離を行わず、組成分析および析出率の計算値も行わなかった。
[Comparative Example 3]
Except that the NaOH concentration was changed to 50 g / L, the arsenic-containing substance was leached with alkali while oxidizing in the same manner as in Example 2, followed by solid-liquid separation and composition analysis. These conditions and analysis results are shown in Table 2 and Table 3, respectively. Moreover, although cooling crystallization was tried by the same method as Example 1, since there was no precipitate at all, subsequent solid-liquid separation was not performed, and the compositional analysis and the calculated value of the precipitation rate were not performed.
［比較例４］
ＮａＯＨ濃度を２５ｇ／Ｌにした以外は、実施例２と同様の方法で、砒素含有物質を酸化しながらアルカリ浸出した後、固液分離し、組成分析を行った。これらの条件および分析結果をそれぞれ表２および表３に示す。また、実施例１と同様の方法によって冷却晶析を試みたが、析出物が全くなかったため、その後の固液分離を行わず、組成分析および析出率の計算値も行わなかった。
[Comparative Example 4]
Except for changing the NaOH concentration to 25 g / L, the arsenic-containing substance was leached with alkali while oxidizing in the same manner as in Example 2, followed by solid-liquid separation and composition analysis. These conditions and analysis results are shown in Table 2 and Table 3, respectively. Moreover, although cooling crystallization was tried by the same method as Example 1, since there was no precipitate at all, subsequent solid-liquid separation was not performed, and the compositional analysis and the calculated value of the precipitation rate were not performed.
実施例４および比較例２〜４から、ＮａＯＨ溶液１Ｌ当りの砒素含有物質２００ｇとしてアルカリ浸出させる場合には、ＮａＯＨ濃度を１００ｇ／Ｌ以上にすれば、砒素を完全に浸出させることができるのがわかる。また、実施例４および比較例２〜４から、ＮａＯＨ溶液１Ｌ当りの砒素含有物質２００ｇとしてアルカリ浸出させる場合には、ＮａＯＨ濃度を５０ｇ／Ｌより高くしなければ、冷却晶析によって析出物を得ることができないのがわかる。 From Example 4 and Comparative Examples 2 to 4, when alkali leaching as 200 g of an arsenic-containing substance per liter of NaOH solution, arsenic can be completely leached if the NaOH concentration is 100 g / L or more. Recognize. Also, from Example 4 and Comparative Examples 2 to 4, when alkali leaching as 200 g of an arsenic-containing substance per 1 L of NaOH solution, a precipitate is obtained by cooling crystallization unless the NaOH concentration is higher than 50 g / L. I can't understand.
Claims (7)
7. The arsenic-containing material includes at least one of copper, zinc, iron, indium, gallium, tin, antimony, lead, cadmium, sodium, potassium, magnesium, and calcium. A method for treating an arsenic-containing substance as described in 1.
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| JP2011161386A (en) * | 2010-02-10 | 2011-08-25 | Akita Univ | Method for treating thioarsenite |
| RU2483129C1 (en) * | 2012-03-02 | 2013-05-27 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский, проектный и конструкторский институт горного дела и металлургии цветных металлов" ФГУП "Гипроцветмет" | Method of neutralising arsenic-containing sulfide cakes |
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| JPS6124329B2 (en) * | 1978-06-09 | 1986-06-10 | Sumitomo Metal Mining Co | |
| JPH09241776A (en) * | 1996-03-08 | 1997-09-16 | Nikko Kinzoku Kk | Separation of arsenic container in smelting intermediate material and recovering method of arsenic |
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