JP4411057B2 - Arsenic removal method from smoke ash - Google Patents
Arsenic removal method from smoke ash Download PDFInfo
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- JP4411057B2 JP4411057B2 JP2003400224A JP2003400224A JP4411057B2 JP 4411057 B2 JP4411057 B2 JP 4411057B2 JP 2003400224 A JP2003400224 A JP 2003400224A JP 2003400224 A JP2003400224 A JP 2003400224A JP 4411057 B2 JP4411057 B2 JP 4411057B2
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- 229910052785 arsenic Inorganic materials 0.000 title claims description 64
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 63
- 239000000779 smoke Substances 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 31
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 claims description 40
- 239000013078 crystal Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 238000002386 leaching Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 9
- -1 iron ions Chemical class 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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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、煙灰からの砒素除去方法に関するものである。 The present invention relates to a method for removing arsenic from smoke ash.
従来、製錬所、例えば、銅製錬所においては、煤煙等による環境汚染が問題となっており、排出される亜硫酸ガス，粉塵，砒素等の削減が強化されている。このような亜硫酸ガスの排出規制に伴い、新たに砒素を含む大量の煙灰が発生し、この煙灰の処理が問題となっている。煙灰中の砒素を除去する方法として、煙灰から砒素を酸浸出し、この浸出液を鉄イオンを含む酸性水溶液と混合し、９０℃に加温して沈殿させ、砒酸鉄の結晶として取り出すことで、煙灰から砒素を除去する方法が知られている（例えば、非特許文献１参照）。 Conventionally, in a smelter, for example, a copper smelter, environmental pollution due to smoke or the like has been a problem, and reduction of sulfurous acid gas, dust, arsenic, and the like emitted has been strengthened. Along with the emission regulation of sulfurous acid gas, a large amount of smoke ash containing arsenic is newly generated, and the treatment of this smoke ash has become a problem. As a method of removing arsenic in the smoke ash, acid leaching of arsenic from the smoke ash, mixing this leaching solution with an acidic aqueous solution containing iron ions, precipitating by heating to 90 ° C., and taking it out as iron arsenate crystals, A method for removing arsenic from smoke ash is known (for example, see Non-Patent Document 1).
ところで、非特許文献１の方法は、砒酸鉄を結晶として取り出す際に、ｐＨ４以下の範囲で、砒素の浸出液に鉄イオンを含む酸性水溶液を複数回に分けて少しずつ添加することによりｐＨが段階的に僅かずつ上がるように制御する必要があった。このとき、鉄イオンを含む酸性水溶液やアルカリ水溶液を添加してｐＨ調整を行うが、ｐＨが急速に上がると、不安定で安全に投棄することが難しい非晶質の砒酸鉄が沈殿してしまう。このため、上記方法は、結晶化のためのｐＨ管理が不可欠で非常に煩雑な手間が掛かるという問題があった。
By the way, in the method of Non-Patent
本発明は、上記に鑑みてなされたものであって、非晶質の砒酸鉄を結晶化させるためのｐＨ管理が不要で、煙灰から安定した砒素を極めて簡単に除去することが可能な煙灰からの砒素除去方法を提供することを目的とする。 The present invention has been made in view of the above, and does not require pH control for crystallizing amorphous iron arsenate, and from smoke ash capable of removing stable arsenic from smoke ash very easily An object of the present invention is to provide a method for removing arsenic.
上記の目的を達成するために、本発明の請求項１に係る煙灰からの砒素除去方法は、砒素を含む煙灰から酸溶液により砒素を浸出する浸出工程と、浸出した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を沈殿させる沈殿反応工程と、該混合液を加温して前記非晶質の砒酸鉄を結晶化する結晶化工程と、を備え、前記混合液を濾過して前記結晶化された砒酸鉄を除去することを特徴とする。
To achieve the above object, a method for removing arsenic from smoke ash according to
請求項１の発明によれば、浸出液に鉄イオンを含む酸性水溶液を混合した後は、ｐＨ調整等、特別の処理が不要であるので、煙灰から砒素を極めて簡単に除去することができる。 According to the first aspect of the present invention, after the acidic aqueous solution containing iron ions is mixed with the leachate, arsenic can be removed very easily from the smoke ash because no special treatment such as pH adjustment is required.
また、請求項２に係る煙灰からの砒素除去方法は、上記の発明において、前記結晶化工程は、鉄と砒素のモル比を１〜１．５、砒素濃度を０．１ｇ／Ｌ以上の条件で開始し、８０〜９５℃に加温した加温状態で所定時間放置することを特徴とする。 According to a second aspect of the present invention, there is provided a method for removing arsenic from smoke ash. In the above invention, the crystallization step is performed under such conditions that the molar ratio of iron to arsenic is 1 to 1.5 and the arsenic concentration is 0.1 g / L or more. It is characterized in that it is left for a predetermined time in a heated state heated to 80 to 95 ° C.
請求項２の発明によれば、浸出液に鉄イオンを含む酸性水溶液を混合した後は、混合液を加温状態で所定時間放置するだけでよいので非常に手間を省略することができる。 According to the second aspect of the present invention, after the acidic aqueous solution containing iron ions is mixed with the leachate, it is only necessary to leave the mixture in a heated state for a predetermined time, so that labor can be saved greatly.
また、請求項３に係る煙灰からの砒素除去方法は、上記の発明において、前記酸溶液は硫酸であり、前記鉄イオンを含む酸性水溶液は、硫酸第二鉄の水溶液であることを特徴とする。 The method for removing arsenic from smoke ash according to claim 3 is characterized in that, in the above invention, the acid solution is sulfuric acid, and the acidic aqueous solution containing iron ions is an aqueous solution of ferric sulfate. .
請求項３の発明によれば、安価な酸を利用して煙灰から砒素を浸出することができる。 According to the invention of claim 3, arsenic can be leached from the smoke ash using an inexpensive acid.
また、請求項４に係る煙灰からの砒素除去方法は、上記の発明において、前記結晶化工程は、種結晶を添加することを特徴とする。 The arsenic removal method from smoke ash according to claim 4 is characterized in that, in the above invention, the crystallization step adds a seed crystal.
請求項４の発明によれば、種結晶を添加することによって前記砒酸鉄の結晶化に要する時間を調整できるので、処理コストと処理時間とを考慮して煙灰中における砒素を除去することができる。 According to the invention of claim 4, since the time required for crystallization of the iron arsenate can be adjusted by adding a seed crystal, arsenic in the smoke ash can be removed in consideration of processing cost and processing time. .
本発明にかかる煙灰からの砒素除去方法は、非晶質の砒酸鉄を結晶化させるためのｐＨ管理が不要で、煙灰から極めて簡単に砒素を除去することができるという効果を奏する。 The method for removing arsenic from smoke ash according to the present invention does not require pH control for crystallizing amorphous iron arsenate, and has the effect of being able to remove arsenic from smoke ash very easily.
以下に添付図面を参照して、本発明に係る煙灰からの砒素除去方法の好適な実施の形態を詳細に説明する。 Exemplary embodiments of a method for removing arsenic from smoke ash according to the present invention will be described below in detail with reference to the accompanying drawings.
（実施の形態）
図１は、本発明の煙灰からの砒素除去方法を示すフローチャートである。本発明方法においては、先ず、硫酸溶液（濃度０．２mol/L）を用いて煙灰から砒素を浸出する（ステップＳ１０）。次に、浸出した酸性の浸出液をろ過し、固液分離する（ステップＳ１２）。得られた残渣は、浮選処理により尾鉱（鉛）と精鉱（銅）とに選別され、尾鉱からは鉛が、精鉱からは銅が、夫々回収される。
(Embodiment)
FIG. 1 is a flowchart showing a method for removing arsenic from smoke ash according to the present invention. In the method of the present invention, first, arsenic is leached from the smoke ash using a sulfuric acid solution (concentration 0.2 mol / L) (step S10). Next, the leached acidic leachate is filtered and separated into solid and liquid (step S12). The obtained residue is sorted into tailings (lead) and concentrates (copper) by flotation, and lead is recovered from the tailings and copper is recovered from the concentrates.
一方、ろ過された砒素を含む浸出液は、硫酸第二鉄水溶液（鉄イオン（Ｆｅ3+）濃度８０〜９０ｇ／Ｌ）を用いて沈殿反応によって砒酸鉄を沈殿させる（ステップＳ１４）。この沈殿反応工程は、ｐＨ１．０〜１．５の硫酸第二鉄(Ｆｅ2(ＳＯ4)3)水溶液を、鉄と砒素のモル比が１〜１．５となるようにｐＨ１．０〜１．５の浸出液に添加し、砒素濃度が０．１ｇ／Ｌ以上の条件で開始する。このとき、図２に模式的に示すように、固定された砒酸鉄（ＦｅＡｓＯ4・２Ｈ2Ｏ）は、当初は混合液Ｌm中に非晶質Ａmとして沈殿する。 On the other hand, the filtered leachate containing arsenic precipitates iron arsenate by a precipitation reaction using an aqueous ferric sulfate solution (iron ion (Fe 3+ ) concentration of 80 to 90 g / L) (step S14). In this precipitation reaction step, a ferric sulfate (Fe 2 (SO 4) 3) aqueous solution having a pH of 1.0 to 1.5 is adjusted to a pH of 1.0 to 1 so that the molar ratio of iron to arsenic is 1 to 1.5. No. 5 is added to the leachate, and the process is started under the condition that the arsenic concentration is 0.1 g / L or more. At this time, as schematically shown in FIG. 2, the fixed iron arsenate (FeAsO 4 .2H 2 O) initially precipitates as amorphous Am in the mixed solution Lm.
そして、砒素を含む浸出液と硫酸第二鉄水溶液の混合液を８０〜９５℃に加温し、沈殿した砒酸鉄を結晶化する（ステップＳ１６）。このとき、この加温状態において、固定された非晶質Ａmの砒酸鉄（ＦｅＡｓＯ4・２Ｈ2Ｏ）が、混合液Ｌm中において経時的に酸に溶け難く安定した結晶Ｃrに改質され、図３に模式的に示す結晶Ｃrの沈殿となる。 Then, the mixture of the leaching solution containing arsenic and the aqueous ferric sulfate solution is heated to 80 to 95 ° C. to crystallize the precipitated iron arsenate (step S16). At this time, in this heated state, the fixed amorphous Am iron arsenate (FeAsO4 · 2H2O) is modified into a stable crystal Cr which hardly dissolves in acid with time in the mixed solution Lm, and is shown in FIG. This is a precipitation of the crystalline Cr schematically shown.
この結晶化工程においては、鉄酸化菌によって鉄スクラップを酸化して作った水酸化第二鉄を硫酸処理して得られる硫酸第二鉄を用いると、硫酸第二鉄を工業的に非常に安価に入手することができる。また、結晶化工程は、種結晶（ＦｅＡｓＯ4・２Ｈ2Ｏ）を混合液Ｌm中に添加すると、砒酸鉄の結晶化に要する時間を調整することができるので好ましい。種結晶の添加量としては、５０〜１５０ｇ／Ｌ程度が好ましい。 In this crystallization process, ferric sulfate obtained by oxidizing ferric hydroxide produced by oxidizing iron scrap with iron-oxidizing bacteria is used, and ferric sulfate is industrially very inexpensive. Can be obtained. In the crystallization step, it is preferable to add seed crystals (FeAsO4 · 2H2O) to the mixed solution Lm because the time required for crystallization of iron arsenate can be adjusted. The amount of seed crystals added is preferably about 50 to 150 g / L.
このようにして結晶化処理が終了したら、混合液Ｌmをろ過する（ステップＳ１８）。そして、酸に溶け難く安定した砒酸鉄（ＦｅＡｓＯ4・２Ｈ2Ｏ）結晶を回収することにより、煙灰に含まれていた砒素が除去される。このとき、砒酸鉄（ＦｅＡｓＯ4・２Ｈ2Ｏ）の結晶は、酸に溶け難く安定していることからろ過性が良いので、効率良く混合液Ｌmから分離することができる。 When the crystallization process is thus completed, the mixed solution Lm is filtered (step S18). Then, by recovering stable iron arsenate (FeAsO4 · 2H2O) crystals which are hardly dissolved in acid, arsenic contained in the smoke ash is removed. At this time, the crystals of iron arsenate (FeAsO4 · 2H2O) are hardly soluble in acid and stable, and thus have good filterability, and therefore can be efficiently separated from the mixed solution Lm.
一方、砒酸鉄（ＦｅＡｓＯ4・２Ｈ2Ｏ）の結晶をろ過して得られる脱砒液は、溶媒抽出によって銅溶液と粗亜鉛液とに分離され、銅溶液は電解工程によって銅が回収される。粗亜鉛液は、一次中和処理された後、固液分離されて残液と非晶質の砒素を含む鉄・砒素沈殿物とに分けられ、残液は所定の処理が施される。そして、非晶質の砒素を含む鉄・砒素沈殿物は、再度、浸出液に加えられ、ステップＳ１４の結晶化処理が施される。 On the other hand, the dearsenic solution obtained by filtering the crystals of iron arsenate (FeAsO4 · 2H2O) is separated into a copper solution and a crude zinc solution by solvent extraction, and copper is recovered from the copper solution by an electrolysis process. The crude zinc solution is subjected to a primary neutralization treatment and then solid-liquid separation to divide the residue into an iron / arsenic precipitate containing amorphous arsenic, and the residue is subjected to a predetermined treatment. Then, the iron / arsenic precipitate containing amorphous arsenic is added again to the leaching solution, and the crystallization process in step S14 is performed.
以上のように、本発明方法によれば、煙灰から砒素を酸浸出した浸出液に硫酸第二鉄水溶液を添加した後は、ｐＨ調整を行うことなく加温状態にするだけで、非晶質の砒酸鉄が、酸に溶け難く安定した結晶の砒酸鉄に改質されるので、煙灰から安定した砒素を非常に簡単、かつ、安価に回収することができる。 As described above, according to the method of the present invention, after the aqueous ferric sulfate solution is added to the leachate obtained by acid leaching of arsenic from the smoke ash, the amorphous state can be obtained simply by heating to a heated state without adjusting the pH. Since iron arsenate is reformed into stable crystalline iron arsenate that is hardly soluble in acid, stable arsenic can be recovered from smoke ash very easily and inexpensively.
硫酸溶液を用いて煙灰から砒素を浸出し、ろ過して得たｐＨ１．０の浸出液に、ｐＨ１．０の硫酸第二鉄水溶液（鉄イオン（Ｆｅ3+）濃度８０ｇ／Ｌ）を、鉄と砒素のモル比が１〜１．５となるように添加し、砒素濃度が１０ｇ／Ｌ以上の条件下で、混合液を９５℃に加温して非晶質の砒酸鉄を結晶化した。このとき、混合後、３，９，１２，２２時間後の各時点で混合液中の沈殿をサンプリングし、Ｘ線結晶回折装置により回折角と回折強度（ピーク比）との関係を測定した。その結果を図４−１〜図４−４に示す。 Leaching arsenic from smoke ash using a sulfuric acid solution, and adding the pH 1.0 leachate obtained by filtration to a ferric sulfate aqueous solution (iron ion (Fe 3+ ) concentration 80 g / L) Arsenic was added so that the molar ratio was 1 to 1.5, and the mixture was heated to 95 ° C. under the condition that the arsenic concentration was 10 g / L or more to crystallize amorphous iron arsenate. At this time, after mixing, the precipitate in the mixed solution was sampled at each time point after 3, 9, 12, and 22 hours, and the relationship between the diffraction angle and the diffraction intensity (peak ratio) was measured by an X-ray crystal diffractometer. The results are shown in FIGS.
図４−１に示す結果から明らかなように、混合後３時間の場合には、沈殿が非晶質の砒酸鉄からなることを示すように、回折強度の分布が緩やかで、結晶に起因したピークが見られない。これに対し、混合後９時間経過すると、図４−２に示すように、回折角が１５°〜３０°に亘る範囲に回折強度が突出し、砒酸鉄の結晶の存在を示すピークが発生し始める。そして、混合後１２時間以上経過すると、図４−２及び図４−４に示すように、回折角を測定した全範囲に亘って回折強度が突出し、特に回折角が１５°〜３０°に亘る範囲においては、砒酸鉄の結晶の存在を示す急峻なピークが出現する。これにより、混合液においては、非晶質からなる砒酸鉄（ＦｅＡｓＯ4・２Ｈ2Ｏ）の沈殿が、混合液中において、経時的に酸に溶け難く安定した結晶の沈殿に改質されることが分かった。 As is apparent from the results shown in FIG. 4-1, in the case of 3 hours after mixing, the distribution of diffraction intensity was gentle and was attributed to crystals, indicating that the precipitate was composed of amorphous iron arsenate. There is no peak. On the other hand, when 9 hours have elapsed after mixing, as shown in FIG. 4B, the diffraction intensity protrudes in a range where the diffraction angle ranges from 15 ° to 30 °, and a peak indicating the presence of iron arsenate crystals starts to appear. . And when 12 hours or more pass after mixing, as shown to FIGS. 4-2 and 4-4, diffraction intensity protrudes over the whole range which measured the diffraction angle, and especially a diffraction angle covers 15 degrees-30 degrees. In the range, a steep peak indicating the presence of iron arsenate crystals appears. As a result, it was found that in the mixed solution, the precipitate of amorphous iron arsenate (FeAsO4 · 2H2O) was modified into a stable crystalline precipitate that hardly dissolves in acid over time in the mixed solution. .
ここで、本発明方法においては、煙灰から砒素を酸浸出した浸出液に硫酸第二鉄水溶液を添加した混合液に種結晶を添加すると、砒酸鉄の結晶化に要する時間が加速される。このため、本発明方法においては、種結晶を使用することにより、砒酸鉄の結晶化に要する時間を調整することができる。図５−１〜図５−３は、種結晶を種々の量添加した場合における、反応時間（hr）と混合液中における砒素濃度（ｍｇ／Ｌ）との関係を、混合液の初期ｐＨが１．０，１．２５，１．５の場合について測定した図である。 Here, in the method of the present invention, when a seed crystal is added to a mixture obtained by adding ferric sulfate aqueous solution to a leachate obtained by leaching arsenic from smoke ash, the time required for crystallization of iron arsenate is accelerated. For this reason, in the method of the present invention, the time required for crystallization of iron arsenate can be adjusted by using a seed crystal. 5-1 to 5-3 show the relationship between the reaction time (hr) and the arsenic concentration (mg / L) in the mixed solution when various amounts of seed crystals are added. It is the figure measured about the case of 1.0, 1.25, 1.5.
図５−１〜図５−３に示す結果から明らかなように、種結晶が多くなる程、非晶質からなる砒酸鉄の沈殿が、早く結晶化することが分かる。従って、本発明方法においては、煙灰から砒素を酸浸出した浸出液に硫酸第二鉄水溶液を添加した混合液に種結晶を添加することによって、非晶質からなる砒酸鉄の結晶化に要する時間を調整することができる。このとき、ｐＨ値が小さい程、種結晶を添加することの効果は大きいが、ｐＨ値を小さくする程、後述するように砒酸鉄結晶除去後における溶液のｐＨ調整のための費用が嵩んでしまう。 As is apparent from the results shown in FIGS. 5-1 to 5-3, it can be seen that the more seed crystals, the faster the precipitation of amorphous iron arsenate crystallizes. Therefore, in the method of the present invention, the time required for crystallization of amorphous iron arsenate is obtained by adding seed crystals to a mixture obtained by adding ferric sulfate aqueous solution to a leachate obtained by acid leaching of arsenic from smoke ash. Can be adjusted. At this time, the smaller the pH value, the greater the effect of adding the seed crystal, but the lower the pH value, the higher the cost for adjusting the pH of the solution after removing the iron arsenate crystals, as will be described later. .
ここで、本発明方法によって結晶化された砒酸鉄（ＦｅＡｓＯ4・２Ｈ2Ｏ）に関する混合液からの除去率と安定性について調べ、その結果を表１に示した。用いた試験溶液（浸出液）は、表１に示すように、初期ｐＨが０．５，１．０，１．５の３種類を用い、種結晶を４５〜１９０ｇ／Ｌ添加すると共に、鉄と砒素のモル比が１．３〜１．５となるように硫酸第二鉄水溶液を添加し、砒素濃度が１５ｇ／Ｌの条件下で、混合液を９５℃に加温して非晶質の砒酸鉄を結晶化した。このとき、除去率は、混合溶液中の砒素の何％が砒酸鉄結晶として沈殿除去された割合（％）を示す。また、安定性は、前記非特許文献に開示されたように、結晶化された砒酸鉄に関し、常温、ｐＨ約５．０における砒素の浸出量（ｍｇ／Ｌ）がインデックスとして与えられる。 Here, the removal rate and stability of the iron arsenate (FeAsO4 · 2H2O) crystallized by the method of the present invention were examined, and the results are shown in Table 1. As shown in Table 1, the test solutions used (leachate) were three types having an initial pH of 0.5, 1.0, and 1.5, and 45 to 190 g / L of seed crystals were added. An aqueous ferric sulfate solution was added so that the molar ratio of arsenic was 1.3 to 1.5, and the mixture was heated to 95 ° C. under the condition that the arsenic concentration was 15 g / L. Iron arsenate was crystallized. At this time, the removal rate indicates the percentage (%) at which% of arsenic in the mixed solution is precipitated and removed as iron arsenate crystals. As disclosed in the above non-patent document, the stability is given as an index of the leaching amount of arsenic (mg / L) at room temperature and pH of 5.0 with respect to crystallized iron arsenate.
表１に示す結果から明らかなように、種結晶を添加する場合、初期ｐＨが１．０であると、前記混合液における砒素の除去率（％）並びに砒素の浸出量（ｍｇ／Ｌ）の点で優れた効果が得られることが分かる。 As is apparent from the results shown in Table 1, when seed crystals are added, if the initial pH is 1.0, the arsenic removal rate (%) and the arsenic leaching amount (mg / L) in the mixed solution It turns out that the outstanding effect is acquired at a point.
以上のようにして非晶質の砒酸鉄を結晶化した混合液は、前述のように溶媒抽出によって銅溶液と粗亜鉛液とに分離されるが、溶媒抽出の際に酸化カルシウム（ＣａＯ）によってｐＨ２に調整される。このため、煙灰１ｔの処理する際に要するｐＨ調整剤（酸化カルシウム）の量（ｋｇ）を初期ｐＨとの関係で求めたところ表２に示す結果が得られた。このとき、表２には、非晶質の砒酸鉄を結晶化した後における混合液の最終ｐＨ値を併せて示してある。
The mixed liquid obtained by crystallizing amorphous iron arsenate as described above is separated into a copper solution and a crude zinc liquid by solvent extraction as described above, but by the calcium oxide (CaO) during solvent extraction.
ここで、本発明方法においては、上述のように種結晶を添加するときには、初期ｐＨが１．０であると、前記混合液における砒素の除去率（％）並びに砒素の浸出量（ｍｇ／Ｌ）の点で優れた効果が得られることが分かった。しかし、表２に示す結果から明らかなように、ｐＨ値を小さくすると、その分脱砒液のｐＨ調整に要するｐＨ調整剤（酸化カルシウム）の量が増え、ｐＨ調整のための費用が嵩んでしまう。このため、初期ｐＨは、処理コストとの関係を考慮して決めることが望ましい。 Here, in the method of the present invention, when the seed crystal is added as described above, if the initial pH is 1.0, the arsenic removal rate (%) and the arsenic leaching amount (mg / L) in the mixed solution It was found that an excellent effect was obtained in terms of However, as is clear from the results shown in Table 2, when the pH value is reduced, the amount of the pH adjusting agent (calcium oxide) required for adjusting the pH of the dearsenic solution increases accordingly, and the cost for adjusting the pH increases. End up. For this reason, it is desirable to determine the initial pH in consideration of the relationship with the processing cost.
以上のように、本発明にかかる煙灰からの砒素除去方法は、砒素の除去に有用であり、特に、製錬所等において排出される煙灰から安定した砒素をｐＨ調整等の特別な管理をすることなく容易に除去するのに適している。 As described above, the method for removing arsenic from smoke ash according to the present invention is useful for removing arsenic, and in particular, performs special management such as pH adjustment of stable arsenic from smoke ash discharged from a smelter or the like. Suitable for easy removal without.
Ａm 非晶質
Ｃr 結晶
Ｌm 混合液
Am Amorphous Cr Crystal Lm Mixture
Claims (4)
浸出した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を沈殿させる沈殿反応工程と、
該混合液を常圧下で加温して前記非晶質の砒酸鉄を結晶化する結晶化工程と、
を備え、前記混合液を濾過して前記結晶化された砒酸鉄を除去することを特徴とする煙灰からの砒素除去方法。 A leaching step of leaching arsenic from ash containing arsenic with an acid solution;
A precipitation reaction step in which an acidic aqueous solution containing iron ions is mixed with the leached leachate to precipitate amorphous iron arsenate;
A crystallization step of heating the mixture under normal pressure to crystallize the amorphous iron arsenate;
And removing the crystallized iron arsenate by filtering the mixed solution.
前記結晶化工程は、前記混合液を８０〜９５℃に加温した加温状態で所定時間放置することを特徴とする請求項１に記載の煙灰からの砒素除去方法。 The precipitation reaction step is started under conditions where the molar ratio of iron to arsenic is 1 to 1.5 and the arsenic concentration is 0.1 g / L or more.
2. The method for removing arsenic from smoke ash according to claim 1, wherein in the crystallization step, the mixed solution is allowed to stand for a predetermined time in a heated state in which the mixture is heated to 80 to 95 ° C. 3.
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