JP2020196913A - Recovery method of tin - Google Patents
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- JP2020196913A JP2020196913A JP2019102451A JP2019102451A JP2020196913A JP 2020196913 A JP2020196913 A JP 2020196913A JP 2019102451 A JP2019102451 A JP 2019102451A JP 2019102451 A JP2019102451 A JP 2019102451A JP 2020196913 A JP2020196913 A JP 2020196913A
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- tellurium
- selenium
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000011084 recovery Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 52
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000002386 leaching Methods 0.000 claims description 36
- 239000011575 calcium Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 abstract description 124
- 229910052785 arsenic Inorganic materials 0.000 abstract description 31
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052711 selenium Inorganic materials 0.000 abstract description 30
- 239000011669 selenium Substances 0.000 abstract description 30
- 229910052714 tellurium Inorganic materials 0.000 abstract description 30
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 29
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 abstract description 29
- HNQGTZYKXIXXST-UHFFFAOYSA-N calcium;dioxido(oxo)tin Chemical compound [Ca+2].[O-][Sn]([O-])=O HNQGTZYKXIXXST-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 15
- 229910052787 antimony Inorganic materials 0.000 description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- 239000002893 slag Substances 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003002 pH adjusting agent Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 210000000416 exudates and transudate Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 2
- 229910004767 CaSn Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 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
Abstract
Description
本発明は、錫と、砒素、テルル、セレンのうち少なくとも一種とを含む溶液から、錫を分離、回収する錫の回収方法に関する。 The present invention relates to a method for recovering tin, which separates and recovers tin from a solution containing tin and at least one of arsenic, tellurium, and selenium.
例えば、銅の製錬工程や鉛を含む製品のリサイクル工程で産出される鉛製錬原料から鉛を乾式製錬する際には、鉛製錬原料を溶鉱炉等で溶融して粗鉛を得る。そして、この粗鉛をハリス炉に導入して溶融し、水酸化ナトリウムや硝酸ナトリウムなどを加えて粗鉛をハリス法による処理（ハリス処理：粗鉛精製）を行うことにより、電解精製用の鉛陽極材を製造する。 For example, when lead is pyrometallurgical from a lead smelting raw material produced in a copper smelting process or a product recycling process containing lead, the lead smelting raw material is melted in a smelting furnace or the like to obtain crude lead. Then, this crude lead is introduced into a Harris furnace, melted, and sodium hydroxide, sodium nitrate, etc. are added to treat the crude lead by the Harris method (Harris treatment: crude lead purification), thereby leading lead for electrolytic refining. Manufacture anode material.
こうした粗鉛のハリス処理を行う過程において、ハリスドロス（粗鉛をハリス処理した際に生じる固体残渣）が生じる。こうしたハリスドロスは、例えば、２０〜３０ｗｔ％程度の鉛、１５〜２５ｗｔ％程度の錫、５〜１０ｗｔ％程度のアンチモン、および１０ｗｔ％以下の砒素、テルル、セレンなどを含む固体である。 In the process of Harris treatment of crude lead, Harris dross (solid residue generated when crude lead is Harris treated) is generated. Such Harris dross is, for example, a solid containing about 20 to 30 wt% lead, about 15 to 25 wt% tin, about 5 to 10 wt% antimony, and 10 wt% or less of arsenic, tellurium, selenium and the like.
ハリスドロスは、錫の含有率が比較的高いため、ハリスドロスから錫を選択的に回収ができれば、その錫半製品は錫の製錬原料として用いることができる。しかしながら、ハリスドロスから錫を分離、回収する際には、錫と錫以外の不純物元素、例えば砒素、テルル、セレンなどを高精度に分離する必要がある。 Since Harris dross has a relatively high tin content, if tin can be selectively recovered from Harris dross, the tin semi-finished product can be used as a raw material for tin smelting. However, when separating and recovering tin from Harris dross, it is necessary to separate tin and impurity elements other than tin, such as arsenic, tellurium, and selenium, with high accuracy.
従来、錫と砒素、テルル、セレンなどが共存した固体やこれを含む溶液から、錫を選択的に分離して回収する方法として、例えば、特許文献１には、錫含有アルカリ性溶液に対して硫化処理、および還元用金属、例えば金属錫を添加することにより不純物を除去したのち、電解分離によって錫を回収する方法が記載されている。 Conventionally, as a method for selectively separating and recovering tin from a solid in which tin and arsenic, tellurium, selenium, etc. coexist or a solution containing the same, for example, Patent Document 1 describes sulfide for a tin-containing alkaline solution. A method of removing impurities by adding a metal for treatment and reduction, for example, metallic tin, and then recovering tin by electrolytic separation is described.
また、特許文献２には、錫を含むアルカリ性溶液に、還元剤として錫よりもイオン化傾向が高い金属、例えば金属アルミニウムを添加することで、砒素等の不純物と錫を分離して、錫を選択的に回収する方法が記載されている。 Further, in Patent Document 2, tin is selected by adding a metal having a higher ionization tendency than tin, for example, metallic aluminum, as a reducing agent to an alkaline solution containing tin to separate impurities such as arsenic from tin. The method of collecting the metal is described.
また、特許文献３には、錫を主成分とするはんだなどから錫を含む酸性溶液を生成し、これを中和することで錫を含む中和残滓を回収し、その中和残滓をアルカリで溶解して錫含有アルカリ液を生成し、電解分離により錫を回収する方法が記載されている。 Further, in Patent Document 3, an acidic solution containing tin is generated from a solder containing tin as a main component, and the neutralized residue is recovered by neutralizing the solution, and the neutralized residue is alkaline. A method of dissolving to generate a tin-containing alkaline solution and recovering tin by electrolytic separation is described.
しかしながら、特許文献１に開示された方法では、硫化処理及び還元用金属の添加において複数の処理工程が必要であり、また、こうした処理工程において、硫化剤や還元用金属などの高コストな添加物が必要になる。このため、低コストで効率的に錫含有溶液から錫を高精度に分離することが困難であった。 However, the method disclosed in Patent Document 1 requires a plurality of treatment steps in the sulfurization treatment and the addition of the reducing metal, and in such treatment steps, high-cost additives such as a sulfurizing agent and a reducing metal are added. Is required. Therefore, it has been difficult to efficiently separate tin from the tin-containing solution at low cost with high accuracy.
また、特許文献２に開示された方法では、還元用金属としてアルミニウムを添加することで、錫と砒素とを分離することは可能であるが、テルル、セレンなどは錫と共に還元されるため分離ができないという課題があった。 Further, in the method disclosed in Patent Document 2, it is possible to separate tin and arsenic by adding aluminum as a reducing metal, but tellurium, selenium and the like are reduced together with tin, so that separation is possible. There was a problem that it could not be done.
また、特許文献３に開示された方法では、処理工程が中和やアルカリ溶解という複数の操作が必要であるため、高コストで手間が掛かるという課題があった。 Further, the method disclosed in Patent Document 3 has a problem that it is costly and time-consuming because the treatment step requires a plurality of operations such as neutralization and alkali dissolution.
本発明は、このような事情を考慮してなされたものであり、錫と、砒素、テルル、セレンのうち少なくとも一種とを含む溶液から、錫だけを選択的に、かつ低コストに分離、回収することが可能な錫の回収方法を提供することを目的とする。 The present invention has been made in consideration of such circumstances, and only tin is selectively and low-cost separated and recovered from a solution containing tin and at least one of arsenic, tellurium, and selenium. It is an object of the present invention to provide a method for recovering tin that can be obtained.
上記課題を解決するために、この発明は以下の手段を提案している。
即ち、本発明の錫の回収方法は、錫と、砒素、テルル、セレンのうち少なくとも一種とを含む溶液に、炭酸カルシウムを添加して、前記溶液に含まれる錫を、錫酸カルシウムを含む化合物にして沈殿回収する錫回収工程を有し、前記錫回収工程では、ｐＨを１１．０以上、１３．５以下の範囲にすることを特徴とする。
In order to solve the above problems, the present invention proposes the following means.
That is, in the method for recovering tin of the present invention, calcium carbonate is added to a solution containing tin and at least one of arsenic, tellurium, and selenium, and the tin contained in the solution is a compound containing calcium tinate. The tin recovery step is characterized in that the pH is set to a range of 11.0 or more and 13.5 or less.
本発明によれば、錫回収工程において、水に難溶性の炭酸カルシウムを前記第１溶液に加えることにより、Ｃａ２＋イオンが生じない。錫は炭酸カルシウムとの固液反応により、難溶性の錫酸カルシウムを生成するが、錫以外の不純物元素は炭酸カルシウムと反応することがなく、難溶性の沈殿物を生成しない。よって、錫と、不純物である砒素、テルル、セレンとを確実に分離することが可能になる。 According to the present invention, Ca 2+ ions are not generated by adding calcium carbonate, which is sparingly soluble in water, to the first solution in the tin recovery step. Tin produces sparingly soluble calcium tinate by a solid-liquid reaction with calcium carbonate, but impurity elements other than tin do not react with calcium carbonate and do not form a sparingly soluble precipitate. Therefore, it is possible to reliably separate tin from impurities such as arsenic, tellurium, and selenium.
また、前記溶液は、ハリスドロスを水で浸出する浸出工程により得られた浸出液であり、前記浸出工程では、ｐＨを１１．０以上、１３．５以下の範囲にして浸出を行ってもよい。 Further, the solution is an leaching solution obtained by an leaching step of leaching Harris dross with water, and in the leaching step, leaching may be performed with a pH in the range of 11.0 or more and 13.5 or less.
また、前記錫回収工程では、前記炭酸カルシウムの添加量（ｍｏｌ）を、前記溶液に含まれる錫の含有量（ｍｏｌ）の１倍以上、４倍以下にしてもよい。 Further, in the tin recovery step, the amount of calcium carbonate added (mol) may be 1 times or more and 4 times or less of the tin content (mol) contained in the solution.
本発明によれば、錫と、砒素、テルル、セレンのうち少なくとも一種とを含む溶液から、錫だけを選択的に、かつ低コストに分離、回収することが可能な錫の回収方法を提供することができる。 According to the present invention, there is provided a method for recovering tin, which can selectively and inexpensively separate and recover only tin from a solution containing tin and at least one of arsenic, tellurium, and selenium. be able to.
以下、図面を参照して、本発明の一実施形態の錫の回収方法について説明する。なお、以下に示す実施形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。 Hereinafter, a method for recovering tin according to an embodiment of the present invention will be described with reference to the drawings. It should be noted that the embodiments shown below are specifically described in order to better understand the gist of the invention, and do not limit the present invention unless otherwise specified.
図１は、本発明の一実施形態の錫の回収方法を段階的に示したフローチャートである。
本実施形態に係る錫の回収方法は、図１に示すように、例えば、ハリスドロスを水で浸出する浸出工程Ｓ１で得られた、錫と、砒素、テルル、セレンのうち少なくとも一種とを含む浸出液に、炭酸カルシウムを反応させて錫酸カルシウムを含む化合物を沈殿させる錫回収工程Ｓ２を有している。なお、前記溶液を得る工程は、上述したハリスドロスを水で浸出する浸出工程Ｓ１に限定されるものではない。
FIG. 1 is a flowchart showing a stepwise method for recovering tin according to an embodiment of the present invention.
As shown in FIG. 1, the method for recovering tin according to the present embodiment is, for example, an exudate containing tin and at least one of arsenic, tellurium, and selenium obtained in the leaching step S1 in which Harris dross is leached with water. It also has a tin recovery step S2 in which calcium carbonate is reacted to precipitate a compound containing calcium tinate. The step of obtaining the solution is not limited to the leaching step S1 in which the above-mentioned Harris dross is leached with water.
＜ハリスドロス＞
本実施形態の錫の回収方法における原料となるハリスドロスは、例えば、銅の製錬工程や、鉛を含む製品のリサイクル工程で産出される鉛製錬原料から鉛を乾式製錬する際に、粗鉛を水酸化ナトリウムや硝酸ナトリウムなどによって処理する際に生じるものであり、乾燥状態では不定形の粒状固体である。
<Harris Dross>
Harris dross, which is a raw material in the tin recovery method of the present embodiment, is crude in, for example, when lead is dry-smelted from a lead smelting raw material produced in a copper smelting process or a lead-containing product recycling process. It is produced when lead is treated with sodium hydroxide, sodium nitrate, etc., and is an amorphous granular solid in a dry state.
こうしたハリスドロスは、再生利用に有用な金属や非金属を多く含んでおり、具体的には、鉛及び錫を主体とし、その他にアンチモン、砒素、テルル、セレンなどを含んでいる。これら元素のハリスドロスに含まれる組成比の一例としては、鉛２４．４ｗｔ％、錫１８．３ｗｔ％、アンチモン７．８ｗｔ％、砒素４．１ｗｔ％、テルル１．８ｗｔ％、セレン０．３ｗｔ％である。 Such Harris dross contains a large amount of metals and non-metals useful for recycling, and specifically, it is mainly composed of lead and tin, and also contains antimony, arsenic, tellurium, selenium and the like. As an example of the composition ratio contained in Harris dross of these elements, lead is 24.4 wt%, tin is 18.3 wt%, antimony is 7.8 wt%, arsenic is 4.1 wt%, tellurium is 1.8 wt%, and selenium is 0.3 wt%. is there.
＜浸出工程＞
本実施形態の錫の回収方法のうち浸出工程Ｓ１では、上述したハリスドロスから、鉛、およびアンチモンと、その他の元素とを分離する。
浸出工程Ｓ１は、ハリスドロスに水を加えて、例えば８時間以上撹拌する。そして、減圧ろ過、加圧ろ過、遠心分離等の固液分離手段、例えばフィルタープレスなどを用いて固液分離を行い、鉛、アンチモン以外の元素である錫、砒素、テルル、セレン等が水に浸出した浸出液と、鉛、アンチモンを含む浸出残渣とを分離、回収する。
<Leaching process>
In the leaching step S1 of the tin recovery method of the present embodiment, lead, antimony, and other elements are separated from the above-mentioned Harris dross.
In the leaching step S1, water is added to Harris dross and stirred for, for example, 8 hours or more. Then, solid-liquid separation is performed using solid-liquid separation means such as vacuum filtration, pressure filtration, and centrifugation, such as a filter press, and tin, arsenic, tellurium, selenium, and other elements other than lead and antimony are added to water. The exudate and the exudate residue containing lead and antimony are separated and recovered.
こうした浸出工程Ｓ１では、ハリスドロスに水を加えた状態でのｐＨが１３．５以下、好ましくは１３．０以下になるようにする。ハリスドロスの浸出時にｐＨが１３．５を超えると、鉛、アンチモンが溶出する。このため、ｐＨを１３．５以下、好ましくは１３．０以下に保って浸出を行うことにより、鉛、アンチモンを含まない浸出液を得ることができる。 In such a leaching step S1, the pH of Harris dross with water added is adjusted to 13.5 or less, preferably 13.0 or less. If the pH exceeds 13.5 during the leaching of Harris dross, lead and antimony will elute. Therefore, by performing leaching while keeping the pH at 13.5 or less, preferably 13.0 or less, an leaching solution containing no lead or antimony can be obtained.
通常、ハリスドロスの多くは水酸化ナトリウムが含まれており、水を加えると液性は強アルカリ性を示す。このため、ｐＨが１３．５を超える場合には、ｐＨ調整剤を添加してｐＨを１３．５以下にする。ｐＨを下げるｐＨ調整剤としては、酸を用いればよい。酸の具体例としては、例えば、塩酸、硫酸、硝酸等、汎用的な酸をｐＨ調整剤として用いることができる。 Most of Harris dross usually contains sodium hydroxide, and when water is added, the liquid becomes strongly alkaline. Therefore, when the pH exceeds 13.5, a pH adjuster is added to bring the pH to 13.5 or less. An acid may be used as the pH adjuster for lowering the pH. As a specific example of the acid, a general-purpose acid such as hydrochloric acid, sulfuric acid, nitric acid and the like can be used as the pH adjuster.
また、浸出工程Ｓ１では、浸出時のｐＨを１１．０以上、好ましくは１２．０以上に保つとよい。
ハリスドロスの浸出時にｐＨが１１．０未満では錫の浸出率が低下する。このため、ｐＨを１１．０以上、好ましくは１２．０以上に保って浸出を行うことにより、錫の浸出率の低下を防止し、ハリスドロスに含まれる錫の多くを浸出液に移行させることができる。
Further, in the leaching step S1, the pH at the time of leaching should be maintained at 11.0 or higher, preferably 12.0 or higher.
If the pH is less than 11.0 at the time of leaching of Harris dross, the leaching rate of tin decreases. Therefore, by leaching while keeping the pH at 11.0 or higher, preferably 12.0 or higher, it is possible to prevent a decrease in the leaching rate of tin and transfer most of the tin contained in Harris dross to the leaching solution. ..
ハリスドロスに水を加えた際のｐＨが１１．０未満である場合には、ｐＨ調整剤を添加してｐＨを１１．０以上、好ましくは１２．０以上にする。ｐＨを上げるｐＨ調整剤としては、一般的なアルカリを用いればよい。例えば、水酸化ナトリウムをｐＨ調整剤として用いることができる。 If the pH when water is added to Harris dross is less than 11.0, a pH adjuster is added to bring the pH to 11.0 or higher, preferably 12.0 or higher. As a pH adjuster for raising the pH, a general alkali may be used. For example, sodium hydroxide can be used as a pH adjuster.
以上のような浸出工程Ｓ１によって得られた浸出液は、鉛、アンチモンの元素濃度が例えば５００ｐｐｍ未満であり、鉛、アンチモンの殆どは浸出残渣に移行する。これにより、錫と、鉛、アンチモンとの高精度な分離が行われる。 The leachate obtained by the leaching step S1 as described above has an elemental concentration of lead and antimony of less than 500 ppm, and most of the lead and antimony are transferred to the leaching residue. As a result, tin, lead, and antimony are separated with high precision.
＜錫回収工程＞
本実施形態の錫の回収方法のうち錫回収工程Ｓ２では、例えば、上述した浸出工程Ｓ１によって得られた浸出液から、錫と、錫以外元素とを分離する。なお、錫と、砒素、テルル、セレンのうち少なくとも一種とを含む溶液の生成は、上述したハリスドロスを原料とした浸出工程に限定されるものではない。
<Tin recovery process>
In the tin recovery step S2 of the tin recovery method of the present embodiment, for example, tin and elements other than tin are separated from the leachate obtained by the above-mentioned leaching step S1. The formation of a solution containing tin and at least one of arsenic, tellurium, and selenium is not limited to the above-mentioned leaching step using Harris dross as a raw material.
錫回収工程Ｓ２は、浸出液に炭酸カルシウム（ＣａＣＯ３）を加えて、例えば５時間以上撹拌し、浸出液に含まれる錫を錫滓として回収する。錫滓中の錫の形態は、水に難溶性の錫酸カルシウムを含む化合物（ＣａＳｎＯ３、ＣａＳｎ（ＯＨ）６）である。添加する炭酸カルシウムの性状は、粉末、顆粒、スラリーなど、どのような状態でもよい。 In the tin recovery step S2, calcium carbonate (CaCO 3 ) is added to the leachate and stirred for, for example, 5 hours or more, and tin contained in the leachate is recovered as tin residue. The form of tin in the tin slag is a compound containing calcium tinate, which is sparingly soluble in water (CaSnO 3 , CaSn (OH) 6 ). The properties of the calcium carbonate to be added may be any state such as powder, granules, and slurry.
そして、減圧ろ過、加圧ろ過、遠心分離等の固液分離手段、例えばフィルタープレスなどを用いて固液分離を行い、錫滓と、錫以外の元素である砒素、テルル、セレン等を含む残液とを分離、回収する。 Then, solid-liquid separation is performed using solid-liquid separation means such as vacuum filtration, pressure filtration, and centrifugation, for example, a filter press, and the residue containing tin slag and elements other than tin such as arsenic, tellurium, and selenium. Separate and collect the liquid.
こうした錫回収工程Ｓ２において、錫を固相に移行させるための薬剤として、水に難溶性の炭酸カルシウムを用いることによって、浸出液中にＣａ２＋イオンが生じることを防止する。これにより、例えば水に易溶性の水酸化カルシウムや塩化カルシウムを用いた場合に生じるＣａ２＋イオンと、浸出液に含まれる錫以外の元素である砒素、テルル、セレンが反応して生じる水に難溶性の沈殿物（Ｃａ３（ＡｓＯ４）２、Ｃａ３ＴｅＯ６、ＣａＳｅＯ３など）が生成されず、砒素、テルル、セレン等を液相に留めることができる。よって、錫回収工程Ｓ２において炭酸カルシウムを用いることで、錫だけを選択的に固相（錫滓）に移行させて回収することができる。 In the tin recovery step S2, Ca 2+ ions are prevented from being generated in the leachate by using calcium carbonate, which is poorly soluble in water, as a chemical for transferring tin to the solid phase. As a result, for example, Ca 2+ ions generated when easily soluble calcium hydroxide or calcium chloride is used in water reacts with arsenic, tellurium, and selenium, which are elements other than tin contained in the leachate, and are poorly soluble in water. Precipitates (Ca 3 (AsO 4 ) 2 , Ca 3 TeO 6 , CaSeO 3, etc.) are not formed, and arsenic, tellurium, selenium and the like can be retained in the liquid phase. Therefore, by using calcium carbonate in the tin recovery step S2, only tin can be selectively transferred to the solid phase (tin residue) and recovered.
錫回収工程Ｓ２に用いる炭酸カルシウムは、他の一般的なカルシウム系薬剤である水酸化カルシウム（消石灰）や塩化カルシウムと比較して安価であり、低コストで浸出液からの錫の回収を可能にする。また、炭酸カルシウムによって生じた錫滓のろ過性は良好であり、固液分離を容易にできる。 Calcium carbonate used in the tin recovery step S2 is cheaper than other general calcium-based agents such as calcium hydroxide (slaked lime) and calcium chloride, and enables tin recovery from the leachate at low cost. .. In addition, the filterability of tin slag generated by calcium carbonate is good, and solid-liquid separation can be facilitated.
また、錫回収工程Ｓ２では、浸出液のｐＨを１３．５以下、好ましくは１３．０以下になるようにする。浸出液のｐＨが１３．５を超えると、炭酸カルシウムを添加した際の錫酸カルシウムを含む化合物の生成率が減少し、錫の回収率が低下する虞がある。 Further, in the tin recovery step S2, the pH of the leachate is adjusted to 13.5 or less, preferably 13.0 or less. If the pH of the leachate exceeds 13.5, the production rate of the compound containing calcium tinate when calcium carbonate is added decreases, and the recovery rate of tin may decrease.
また、錫回収工程Ｓ２では、浸出液のｐＨを１１．０以上、好ましくは１２．０以上に保つとよい。
浸出液のｐＨが１１．０未満では中和効果によって錫が水酸化物（水酸化錫、Ｓｎ（ＯＨ）２）として沈殿する虞がある。浸出液に含まれる砒素、テルル、セレンは、水酸化錫と共沈するため、錫と砒素、テルル、セレンとの分離を困難にする。浸出液のｐＨを１１．０以上、好ましくは１２．０以上に保ち、炭酸カルシウムを添加することにより、錫だけを固相に、砒素、テルル、セレンを液相に移行させて分離することができる。
Further, in the tin recovery step S2, the pH of the leachate may be kept at 11.0 or higher, preferably 12.0 or higher.
If the pH of the leachate is less than 11.0, tin may precipitate as hydroxides (tin hydroxide, Sn (OH) 2 ) due to the neutralizing effect. Arsenic, tellurium, and selenium contained in the leachate coprecipitate with tin hydroxide, which makes it difficult to separate tin from arsenic, tellurium, and selenium. By keeping the pH of the leachate at 11.0 or higher, preferably 12.0 or higher, and adding calcium carbonate, tin alone can be transferred to the solid phase and arsenic, tellurium, and selenium can be transferred to the liquid phase for separation. ..
なお、錫回収工程Ｓ２では、浸出液に添加する炭酸カルシウムの添加量（ｍｏｌ）は、浸出液の錫の含有量（ｍｏｌ）の１倍以上、４倍以下、好ましくは２倍以上、３倍以下にするとよい。炭酸カルシウムの添加量（ｍｏｌ）が、浸出液の錫の含有量（ｍｏｌ）未満では、浸出液に含まれる錫の全量を固相に移行させて回収することができない。一方、４倍よりも多い場合、未反応の炭酸カルシウムが錫滓に混入するため、相対的に錫滓の錫濃度が低下する虞がある。 In the tin recovery step S2, the amount of calcium carbonate added to the leachate (mol) is 1 times or more and 4 times or less, preferably 2 times or more and 3 times or less the tin content (mol) of the leachate. It is good to do. If the amount of calcium carbonate added (mol) is less than the tin content (mol) of the leachate, the entire amount of tin contained in the leachate cannot be transferred to the solid phase and recovered. On the other hand, if the amount is more than 4 times, unreacted calcium carbonate is mixed in the tin residue, so that the tin concentration of the tin residue may decrease relatively.
この後、錫回収工程Ｓ２で分離された錫滓（固相）は、錫の製錬原料として用いることができる。また、残液（液相）は、希少元素回収用の原料液として用いることができる。具体的にはテルル、セレンは還元剤の添加によりメタルとして回収ができ、砒素は鉄薬剤の添加により砒酸鉄化合物として回収ができる。 After that, the tin slag (solid phase) separated in the tin recovery step S2 can be used as a raw material for tin smelting. Further, the residual liquid (liquid phase) can be used as a raw material liquid for recovering rare elements. Specifically, tellurium and selenium can be recovered as a metal by adding a reducing agent, and arsenic can be recovered as an iron arsenate compound by adding an iron chemical.
以上、本発明の一実施形態を説明したが、この実施形態は例として提示したものであり、発明の範囲を限定することは意図していない。この実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。この実施形態やその変形は、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。 Although one embodiment of the present invention has been described above, this embodiment is presented as an example and is not intended to limit the scope of the invention. This embodiment can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. This embodiment and its modifications are included in the scope and gist of the invention as well as in the scope of the invention described in the claims and the equivalent scope thereof.
本発明の効果を検証した。
（実施例１）
浸出工程として、水４００ｇにハリスドロス１００ｇを添加したのち、９８ｗｔ％硫酸を添加してｐＨを１３．０に調製し２０時間撹拌した。撹拌終了後、減圧ろ過により固液分離し、浸出液４２９ｇ、浸出残渣５５．７ｇ（乾燥重量）を回収した。次に、錫回収工程として、浸出液４２９ｇに９８ｗｔ％硫酸を添加してｐＨを１２．５に調製した。そして、浸出液中の錫の物質量に対して２倍の物質量（Ｃａ（ｍｏｌ）／Ｓｎ（ｍｏｌ）＝２）の炭酸カルシウムの粉末２２．３ｇを添加して５時間撹拌した。その後、減圧ろ過により固液分離し、錫滓４５．６ｇ（乾燥重量）、残液３８３ｇを回収した。
（実施例２）
錫回収工程でのｐＨを１３．２にした以外は、実施例１と同様の条件である。
（実施例３）
錫回収工程でのｐＨを１１．３にし、浸出液中の錫の物質量に対して５倍の物質量（Ｃａ（ｍｏｌ）／Ｓｎ（ｍｏｌ）＝５）の炭酸カルシウムを添加した以外は、実施例１と同様の条件である。
（実施例４）
浸出工程のｐＨを１３．８にした以外は、実施例１と同様の条件である。
（比較例１）
錫回収工程のｐＨを１０．８にした以外は、実施例１と同様の条件である。
（比較例２）
錫回収工程のｐＨを１３．８にした以外は、実施例１と同様の条件である。
（比較例３）
錫回収工程において、炭酸カルシウムでなく塩化カルシウムを添加した以外は、実施例１と同様の条件である。
以上の各実施例および比較例のそれぞれの条件を表１に纏めて示す。
The effect of the present invention was verified.
(Example 1)
As a leaching step, 100 g of Harris dross was added to 400 g of water, 98 wt% sulfuric acid was added to adjust the pH to 13.0, and the mixture was stirred for 20 hours. After completion of stirring, solid-liquid separation was performed by vacuum filtration, and 429 g of leaching solution and 55.7 g of leaching residue (dry weight) were recovered. Next, as a tin recovery step, 98 wt% sulfuric acid was added to 429 g of the leachate to adjust the pH to 12.5. Then, 22.3 g of calcium carbonate powder having twice the amount of substance (Ca (mol) / Sn (mol) = 2) with respect to the amount of substance of tin in the leachate was added and stirred for 5 hours. Then, solid-liquid separation was performed by vacuum filtration, and 45.6 g (dry weight) of tin slag and 383 g of residual liquid were recovered.
(Example 2)
The conditions are the same as in Example 1 except that the pH in the tin recovery step is set to 13.2.
(Example 3)
Conducted except that the pH in the tin recovery step was set to 11.3 and calcium carbonate was added in a substance amount (Ca (mol) / Sn (mol) = 5) that was five times the amount of substance in tin in the leachate. The conditions are the same as in Example 1.
(Example 4)
The conditions are the same as in Example 1 except that the pH of the leaching step is set to 13.8.
(Comparative Example 1)
The conditions are the same as in Example 1 except that the pH of the tin recovery step is set to 10.8.
(Comparative Example 2)
The conditions are the same as in Example 1 except that the pH of the tin recovery step is set to 13.8.
(Comparative Example 3)
The conditions are the same as in Example 1 except that calcium chloride is added instead of calcium carbonate in the tin recovery step.
Table 1 summarizes the conditions of each of the above Examples and Comparative Examples.
そして、各実施例および比較例で得られた錫滓に含まれる元素（Ｓｎ，Ａｓ，Ｔｅ，Ｓｅ，Ｐｂ，Ｓｂ）の濃度（ｗｔ％）はＩＣＰ−ＡＥＳを用いて測定した。この結果を表２に示す。 Then, the concentration (wt%) of the elements (Sn, As, Te, Se, Pb, Sb) contained in the tin slag obtained in each Example and Comparative Example was measured using ICP-AES. The results are shown in Table 2.
表２に示す結果によれば、実施例１〜実施例４は、錫回収工程として炭酸カルシウムを用い、ｐＨを１１．０以上、１３．５以下の範囲にしたので、砒素、セレン、テルルなどを高精度に分離、除去できることが確認された。実施例３では浸出液中の錫の物質量に対して５倍の物質量（Ｃａ（ｍｏｌ）／Ｓｎ（ｍｏｌ）＝５）の炭酸カルシウムを添加したために、未反応の炭酸カルシウムが錫滓に混入し、相対的に錫滓の錫濃度が低下しているが、残液に移行する錫のロスは殆どなく、砒素、セレン、テルルなどの濃度は低い。また、実施例４では浸出工程でのｐＨを１３．８にしたため、浸出工程で鉛、アンチモンが溶出し、錫滓の鉛、アンチモン濃度が高くなった。比較例１は、錫回収工程のｐＨを１０．８にしたため、錫の一部が水酸化物として沈殿した。浸出液に含まれる砒素、テルル、セレンは、錫の水酸化物と共沈するため、錫滓の砒素、テルル、セレン濃度が高くなった。比較例２は、錫回収工程のｐＨを１３．８にしたため、錫酸カルシウムの生成率が減少し、残液に錫が移行し、錫のロスとなった。比較例３は、錫回収工程として塩化カルシウムを用いたため、錫酸カルシウムの他にＣａ３（ＡｓＯ４）２、Ｃａ３ＴｅＯ６、ＣａＳｅＯ３などが生成し、錫滓の砒素、テルル、セレン濃度が高くなった。
以上の結果から、本発明によれば、錫と、砒素、テルル、セレンのうち少なくとも一種とを含む溶液から、錫だけを高精度に分離できることが確認された。
According to the results shown in Table 2, in Examples 1 to 4, calcium carbonate was used as the tin recovery step, and the pH was set in the range of 11.0 or more and 13.5 or less, so that arsenic, selenium, tellurium, etc. It was confirmed that it can be separated and removed with high accuracy. In Example 3, unreacted calcium carbonate was mixed into the tin slag because calcium carbonate was added in an amount of substance (Ca (mol) / Sn (mol) = 5) five times the amount of substance of tin in the leachate. However, although the tin concentration in the tin slag is relatively low, there is almost no loss of tin transferred to the residual liquid, and the concentrations of arsenic, selenium, tellurium, etc. are low. Further, in Example 4, since the pH in the leaching step was set to 13.8, lead and antimony were eluted in the leaching step, and the concentration of lead and antimony in the tin slag was increased. In Comparative Example 1, since the pH of the tin recovery step was set to 10.8, a part of tin was precipitated as a hydroxide. Since arsenic, tellurium, and selenium contained in the leachate coprecipitate with the hydroxide of tin, the concentrations of arsenic, tellurium, and selenium in the tin slag increased. In Comparative Example 2, since the pH of the tin recovery step was set to 13.8, the production rate of calcium tinate decreased, tin was transferred to the residual liquid, and tin was lost. In Comparative Example 3, since calcium chloride was used as the tin recovery step, Ca 3 (AsO 4 ) 2 , Ca 3 TeO 6 , CaSeO 3 and the like were generated in addition to calcium tinate, and the arsenic, tellurium, and selenium concentrations in the tin slag Has become higher.
From the above results, it was confirmed that according to the present invention, only tin can be separated with high accuracy from a solution containing tin and at least one of arsenic, tellurium and selenium.
Claims (3)
前記錫回収工程では、ｐＨを１１．０以上、１３．５以下の範囲にすることを特徴とする錫の回収方法。 It has a tin recovery step of adding calcium carbonate to a solution containing tin to precipitate and recover the tin contained in the solution as a compound containing calcium tinate.
A method for recovering tin, which comprises setting the pH in the range of 11.0 or more and 13.5 or less in the tin recovery step.
The tin recovery step according to claim 1 or 2, wherein the addition amount (mol) of the calcium carbonate is 1 times or more and 4 times or less the tin content (mol) contained in the solution. The method for recovering tin described.
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| JPS575829A (en) * | 1980-06-14 | 1982-01-12 | Dowa Mining Co Ltd | Separating and recovering method for tin in lead refining process |
| JPS59156915A (en) * | 1983-02-25 | 1984-09-06 | Sony Corp | Manufacture of fine calcium stannate particle |
| JPH05501100A (en) * | 1989-07-21 | 1993-03-04 | アルカン・インターナショナル・リミテッド | Method for producing metal stannate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314643A (en) * | 2021-12-13 | 2022-04-12 | 广东先导稀贵金属材料有限公司 | Preparation method and application of calcium stannate |
| CN114314643B (en) * | 2021-12-13 | 2024-02-27 | 广东先导稀贵金属材料有限公司 | Preparation method and application of calcium stannate |
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