JP2002339020A - High molecular flocculation agent for sulfuric acid leaching separation process in valuable metal recovery method and valuable metal recovery method using the same - Google Patents
High molecular flocculation agent for sulfuric acid leaching separation process in valuable metal recovery method and valuable metal recovery method using the sameInfo
- Publication number
- JP2002339020A JP2002339020A JP2001147226A JP2001147226A JP2002339020A JP 2002339020 A JP2002339020 A JP 2002339020A JP 2001147226 A JP2001147226 A JP 2001147226A JP 2001147226 A JP2001147226 A JP 2001147226A JP 2002339020 A JP2002339020 A JP 2002339020A
- Authority
- JP
- Japan
- Prior art keywords
- water
- sulfuric acid
- salt
- valuable metal
- recovery method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 44
- 238000002386 leaching Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 title abstract description 6
- 238000005189 flocculation Methods 0.000 title abstract description 6
- 230000016615 flocculation Effects 0.000 title abstract description 6
- 238000000926 separation method Methods 0.000 title description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 150000002739 metals Chemical class 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003926 acrylamides Chemical class 0.000 claims abstract description 4
- ABBZJHFBQXYTLU-UHFFFAOYSA-N but-3-enamide Chemical class NC(=O)CC=C ABBZJHFBQXYTLU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 34
- 229920003169 water-soluble polymer Polymers 0.000 claims description 15
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 239000000701 coagulant Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 5
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- -1 alkylalcohol ester Chemical class 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 9
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000284 extract Substances 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、ニッケル、コバル
ト、マンガン等の有価金属を含有する酸化鉱石から硫酸
浸出により有価金属を抽出し、浸出残渣を凝集分離した
後、硫化および炭酸化処理により、これらの有価金属を
回収する方法において、浸出残渣を凝集除去する際に使
用される高分子凝集剤（硫酸浸出液の分離工程用凝集
剤）に関するものである。又、本発明は、硫酸浸出後の
浸出残渣を有価金属溶解液から効率的に凝集分離するこ
とが可能な、上記高分子凝集剤を用いた有価金属の回収
方法に関するものでもある。The present invention relates to a method for extracting valuable metals from oxide ores containing valuable metals such as nickel, cobalt, and manganese by leaching with sulfuric acid, coagulating and separating leaching residues, and then performing sulfidation and carbonation treatments. The present invention relates to a polymer coagulant (coagulant for a sulfuric acid leaching solution separation step) used in coagulating and removing leaching residues in a method of recovering these valuable metals. The present invention also relates to a method for recovering valuable metals using the above-mentioned polymer flocculant, which is capable of efficiently coagulating and separating a leaching residue after sulfuric acid leaching from a valuable metal solution.
【０００２】[0002]
【従来の技術】ニッケル、コバルトを含む酸化鉱石から
硫酸液により、ニッケル、コバルトを回収する方法は、
米国特許第２８７２３０６号やＪｏｕｒｎａｌ ｏｆ
Ｍｅｔａｌｓ，Ｍａｒｃｈ，１９６０，ｐ２０６等でよ
く知られている。また、硫酸浸出により、ニッケル、コ
バルトを抽出する従来方法としては、大気圧下で行う方
法と高温高圧下で行う方法があるが、いずれの場合も、
酸化鉱石中に共存して含有する鉄等の他金属も同時に浸
出されるため、硫酸使用量が増加する等の問題点を抱え
ていた。2. Description of the Related Art A method for recovering nickel and cobalt from an oxide ore containing nickel and cobalt by a sulfuric acid solution is as follows.
U.S. Pat. No. 2,872,306 and the Journal of
Well-known in Metals, March, 1960, p206 and the like. In addition, as a conventional method of extracting nickel and cobalt by sulfuric acid leaching, there are a method performed under atmospheric pressure and a method performed under high temperature and high pressure.
Since other metals such as iron coexisting in the oxidized ore are leached at the same time, there is a problem that the amount of sulfuric acid used increases.
【０００３】そこで、鉄等の他金属の溶出を相対的に抑
制できる高温加圧抽出法と、抽出後により温和な条件
（常圧、１００℃以下）でオートクレーブを用いずに、
硫化アルカリ化合物と反応させ、ニッケル硫化物、コバ
ルト硫化物を短時間で効率良く製造する工法が提案され
た。上記工程において、硫酸浸出後の浸出残渣を有価金
属溶解液から効率的に凝集分離することは経済的にも重
要である。しかし、産業排水の凝集処理に一般的に使用
されているポリアクリルアミドやアクリルアミド‐アク
リル酸共重合体等では凝集分離性能が不充分であった。[0003] Therefore, a high-temperature and pressure extraction method capable of relatively suppressing the elution of other metals such as iron and the like, and using an autoclave under milder conditions (normal pressure, 100 ° C or lower) after extraction without using an autoclave.
A method for efficiently producing nickel sulfide and cobalt sulfide in a short time by reacting with an alkali sulfide compound has been proposed. In the above process, it is economically important to efficiently coagulate and separate the leaching residue after the sulfuric acid leaching from the valuable metal solution. However, polyacrylamide, acrylamide-acrylic acid copolymer, and the like generally used for coagulation treatment of industrial wastewater have insufficient coagulation / separation performance.
【０００４】[0004]
【発明が解決しようとする課題】硫酸浸出後の浸出残渣
を有価金属浸出液から凝集分離するのは、高温、かつ硫
酸による強酸性下という過酷条件下であり、一般産業排
水の凝集処理に広く使用されているポリアクリルアミド
やアクリルアミド‐アクリル酸共重合体タイプの水溶性
高分子では、凝集が不十分であった。凝集剤として有効
に働く薬剤の開発が課題であった。The leaching residue after sulfuric acid leaching is coagulated and separated from valuable metal leaching solution under severe conditions of high temperature and strong acidity with sulfuric acid, and is widely used for coagulation treatment of general industrial wastewater. The water-soluble polymers of the polyacrylamide and acrylamide-acrylic acid copolymer types used here were insufficiently aggregated. The development of a drug that works effectively as a flocculant was an issue.
【０００５】本発明の課題は、加圧浸出液中に懸濁分散
している浸出残渣を高分子凝集剤で凝集除去するにあた
り、高温度下で酸安定性が良く、凝集性能の良好な下記
組成からなる高分子凝集剤を提供することにある。又、
本発明は、このような高分子凝集剤を使用することによ
って、ニッケル、コバルト、マンガン等の有価金属を含
有する酸化鉱石から効率良く、不純物が少ない状態で有
価金属を回収可能な方法を提供することを課題とするも
のでもある。An object of the present invention is to coagulate and remove a leaching residue suspended and dispersed in a pressurized leaching solution with a polymer coagulant at a high temperature under the following conditions. To provide a polymer flocculant comprising: or,
The present invention provides a method capable of efficiently recovering valuable metals from oxide ores containing valuable metals such as nickel, cobalt, and manganese in a state with a small amount of impurities by using such a polymer flocculant. It is also an issue.
【０００６】[0006]
【課題を解決するための手段】本発明の高分子凝集剤
は、有価金属を主として含有する酸化鉱石から硫酸浸出
により有価金属を抽出し、浸出残渣を凝集分離した後、
硫化および炭酸化処理を行って有価金属を回収する方法
における、硫酸浸出残渣を凝集除去する際に使用される
高分子凝集剤（有価金属回収法における硫酸浸出工程用
高分子凝集剤）であって、前記高分子凝集剤が、ｉ）ス
ルホン酸基を有する共重合可能な水溶性モノマー又は、
その塩類２．５〜４０モル％及び、ｉｉ）（メタ）アク
リルアミド又はその誘導体５０モル％以上である組成を
有した水溶性高分子共重合体であり、しかも、当該水溶
性高分子共重合体を０．２％含み、かつＮａＣｌを４％
含む塩水溶液の粘度が５〜４０ｍＰａ・ｓであることを
特徴とする。尚、上記の粘度は、ブルックフィールド型
粘度計を使用し、ローターＮｏ．１、６０ｒｐｍ、３０
℃の条件において測定されたものである。The polymer flocculant of the present invention is obtained by extracting valuable metals from oxide ores mainly containing valuable metals by leaching with sulfuric acid and coagulating and separating leaching residues.
A polymer flocculant (a polymer flocculant for a sulfuric acid leaching step in a valuable metal recovery method) used in a method of recovering valuable metals by performing sulfidation and carbonation treatment, which is used when flocculating and removing sulfuric acid leaching residues. Wherein the polymer coagulant comprises: i) a copolymerizable water-soluble monomer having a sulfonic acid group, or
A water-soluble polymer copolymer having a composition of 2.5 to 40 mol% of its salts and ii) 50 mol% or more of (meth) acrylamide or a derivative thereof, and the water-soluble polymer copolymer. 0.2% and 4% NaCl
The viscosity of the salt aqueous solution is 5 to 40 mPa · s. The above viscosity was measured using a Brookfield viscometer and the rotor No. 1, 60 rpm, 30
It was measured under the condition of ° C.
【０００７】又、本発明は、上記の特徴を有した高分子
凝集剤において、前記スルホン酸基を有する共重合可能
な水溶性モノマーが、２‐アクリルアミド‐２‐メチル
プロパンスルホン酸、又はその塩であることを特徴とす
るものでもある。又、本発明は、上記の特徴を有した高
分子凝集剤において、前記スルホン酸基を有する共重合
可能な水溶性モノマーが、ビニルスルホン酸、又はその
塩であることを特徴とするものでもある。更に本発明
は、上記の特徴を有した高分子凝集剤において、前記高
分子凝集剤が、ｉ）スルホン酸基を有する共重合可能な
水溶性モノマー又は、その塩類及び、ｉｉ）（メタ）ア
クリルアミド又はその誘導体とｉｉｉ）共重合し得るビ
ニルモノマー化合物の少なくとも１種を更に含む組成か
ら成るものであることを特徴とするものでもある。又、
本発明は、上記の特徴を有した高分子凝集剤において、
前記ビニルモノマー化合物が、アクリル酸、メタクリル
酸、及びこれらの塩又はアルキルアルコールエステル、
Ｎ‐アルキル置換アクリルアミド、及びビニルアセトア
ミドから成る群より選ばれたものであることを特徴とす
るものでもある。Further, the present invention provides a polymer flocculant having the above characteristics, wherein the copolymerizable water-soluble monomer having a sulfonic acid group is 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof. It is also characterized by being. The present invention also provides a polymer flocculant having the above characteristics, wherein the copolymerizable water-soluble monomer having a sulfonic acid group is vinylsulfonic acid or a salt thereof. . The present invention further provides a polymer flocculant having the above characteristics, wherein the polymer flocculant comprises: i) a copolymerizable water-soluble monomer having a sulfonic acid group or a salt thereof; and ii) (meth) acrylamide. Or a composition further comprising at least one vinyl monomer compound copolymerizable with a derivative thereof and iii). or,
The present invention provides a polymer flocculant having the above characteristics,
The vinyl monomer compound, acrylic acid, methacrylic acid, and salts or alkyl alcohol esters thereof,
It is also characterized by being selected from the group consisting of N-alkyl-substituted acrylamide and vinylacetamide.
【０００８】又、本発明は、有価金属を主として含有す
る酸化鉱石を微粉砕し、水スラリーを沈降濃縮する第一
工程と、前記第一工程にて得られた濃縮スラリーを硫酸
酸性下で浸出し、分離する第二工程を備えた、前記有価
金属の回収方法であって、前記第二工程において、ｉ）
スルホン酸基を有する共重合可能な水溶性モノマー又
は、その塩類２．５〜４０モル％及び、ｉｉ）（メタ）
アクリルアミド又はその誘導体５０モル％以上である組
成を有した水溶性高分子共重合体で、しかも、当該水溶
性高分子共重合体を０．２％含み、かつＮａＣｌを４％
含む塩水溶液の粘度が５〜４０ｍＰａ・ｓである高分子
凝集剤を、凝集剤として使用することを特徴とするもの
でもある。Further, the present invention provides a first step of finely pulverizing an oxide ore mainly containing valuable metals and settling and concentrating a water slurry, and leaching the concentrated slurry obtained in the first step under sulfuric acid. And recovering said valuable metal, comprising a second step of separating the valuable metal, wherein in the second step, i)
2.5-40 mol% of a copolymerizable water-soluble monomer having a sulfonic acid group or a salt thereof, and ii) (meth)
A water-soluble polymer copolymer having a composition of 50 mol% or more of acrylamide or a derivative thereof, and containing 0.2% of the water-soluble polymer copolymer and 4% of NaCl.
The present invention is also characterized in that a polymer flocculant having a viscosity of a salt aqueous solution containing 5 to 40 mPa · s is used as a flocculant.
【０００９】[0009]
【発明の実施の形態】まず最初に、本発明の硫酸浸出工
程用高分子凝集剤について説明する。この高分子凝集剤
は、ニッケル、コバルト、マンガン等の有価金属を主と
して含有する酸化鉱石をスラリー化し、これに硫酸を加
えて有価金属を浸出（抽出）し、浸出残渣を凝集分離す
る際に使用されるものであって、この凝集分離後に、硫
化処理（硫化アルカリ化合物の添加）を行ってニッケル
及びコバルトを硫化物として回収し、更に炭酸化処理
（炭酸塩の添加）を行うことによってマンガンを炭酸塩
として回収する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the polymer flocculant for the sulfuric acid leaching step of the present invention will be described. This polymer flocculant is used to slurry oxide ore containing mainly valuable metals such as nickel, cobalt, and manganese, add sulfuric acid to this to leach (extract) valuable metals, and use it to coagulate and separate leaching residues. After the coagulation separation, nickel and cobalt are recovered as sulfides by performing a sulfidation treatment (addition of an alkali sulfide compound), and then manganese is reduced by performing a carbonation treatment (addition of a carbonate). Collect as carbonate.
【００１０】本発明の高分子凝集剤は、必須構成成分と
して、ｉ）スルホン酸基を有する共重合可能な水溶性モ
ノマー又は、その塩類を２．５〜４０モル％、好ましく
は５〜４０モル％含み、かつｉｉ）（メタ）アクリルア
ミド又はその誘導体を５０モル％以上含む組成を有し、
この他の任意構成成分として、これら２つの化合物と共
重合可能なビニルモノマーを含む水溶性の高分子共重合
体であり、このような共重合体は、一般的な共重合反応
によって得られる。スルホン酸基を有する共重合可能な
水溶性モノマーとしては、２‐アクリルアミド‐２‐メ
チルプロパンスルホン酸、ビニルスルホン酸、スチレン
スルホン酸、アリルスルホン酸又はその塩類が挙げら
れ、その塩類としては、例えば、アルカリ金属塩、アル
カリ土類金属塩、アンモニウム塩又は、アミン塩が挙げ
られる。この中で、２‐アクリルアミド‐２‐メチルプ
ロパンスルホン酸のアルカリ金属塩又はアンモニウム
塩、又は、ビニルスルホン酸のアルカリ金属塩又はアン
モニウム塩が好ましい。尚、塩としてはアルカリ金属
塩、特にナトリウム塩が工業的に有利に使用できる。
又、（メタ）アクリルアミドの誘導体としては、Ｎ‐ア
ルキル置換（メタ）アクリルアミドが挙げられる。そし
て、上記の組成より成る本発明の高分子凝集剤は、当該
水溶性高分子共重合体を０．２％含み、かつＮａＣｌを
４％含む塩水溶液の粘度５〜４０ｍＰａ・ｓを有する。The polymer coagulant of the present invention contains, as an essential component, i) a copolymerizable water-soluble monomer having a sulfonic acid group or a salt thereof in an amount of 2.5 to 40 mol%, preferably 5 to 40 mol%. %, And ii) a composition containing 50 mol% or more of (meth) acrylamide or a derivative thereof,
Another optional component is a water-soluble polymer copolymer containing a vinyl monomer copolymerizable with these two compounds, and such a copolymer is obtained by a general copolymerization reaction. Examples of the copolymerizable water-soluble monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, allylsulfonic acid and salts thereof. , An alkali metal salt, an alkaline earth metal salt, an ammonium salt or an amine salt. Among these, an alkali metal salt or ammonium salt of 2-acrylamido-2-methylpropanesulfonic acid or an alkali metal salt or ammonium salt of vinylsulfonic acid is preferable. In addition, as a salt, an alkali metal salt, especially a sodium salt can be used industrially advantageously.
Examples of the (meth) acrylamide derivative include N-alkyl-substituted (meth) acrylamide. The polymer flocculant of the present invention having the above composition has a viscosity of a salt aqueous solution containing 0.2% of the water-soluble polymer copolymer and 4% of NaCl having a viscosity of 5 to 40 mPa · s.
【００１１】この際、スルホン酸基を有する共重合可能
な水溶性モノマー又はその塩類の組成割合が２．５モル
％未満では、フロックが壊れ易くなるために凝集剤所要
量が増大し、逆に４０モル％を越えると、フロックが軟
らかくなり沈降効果も低下する傾向にあり、良好な凝集
分離性能が得られない。又、もう一つの成分である（メ
タ）アクリルアミド又はその誘導体の組成割合が５０モ
ル％以下の場合にも、良好な凝集分離性能は得れない。
尚、上記の当該水溶性高分子共重合体を０．２％含み、
かつＮａＣｌを４％含む塩水溶液（０．２％−４％Ｎａ
Ｃｌ溶液）の粘度が５ｍＰａ・ｓ未満であるような共重
合体の場合には、形成されるフロックが小さく壊れ易く
なり、４０ｍＰａ・ｓを越えるものでは、フロックが軟
らかくなり沈降効果も低下する傾向があり、共重合体自
体の製造も困難である。通常、本発明の高分子凝集剤
は、０．１〜０．２％水溶液として硫酸浸出スラリーに
添加して使用されるが、その最適添加率は、該スラリー
の固形分（鉱石）当たり０．０１〜０．２０％、好まし
くは０．０２〜０．１０％程度である。At this time, when the composition ratio of the water-soluble copolymerizable monomer having a sulfonic acid group or its salt is less than 2.5 mol%, the floc is easily broken, so that the required amount of the flocculant increases. If it exceeds 40 mol%, the floc tends to be softened and the sedimentation effect tends to be reduced, so that good coagulation / separation performance cannot be obtained. Also, when the composition ratio of the other component (meth) acrylamide or a derivative thereof is 50 mol% or less, good coagulation / separation performance cannot be obtained.
In addition, the said water-soluble polymer copolymer contains 0.2%,
And a salt aqueous solution containing 4% NaCl (0.2% -4% Na
In the case of a copolymer having a viscosity of less than 5 mPa · s (Cl solution), the formed floc is small and easily broken, and if the viscosity exceeds 40 mPa · s, the floc is softened and the sedimentation effect tends to decrease. And it is difficult to produce the copolymer itself. Usually, the polymer flocculant of the present invention is used by being added to a sulfuric acid leaching slurry as a 0.1 to 0.2% aqueous solution, and the optimum addition rate is 0.1% per solid content (ore) of the slurry. It is about 0.1 to 0.20%, preferably about 0.02 to 0.10%.
【００１２】本発明では、上記の水溶性高分子共重合体
が、上述の必須構成成分の他に任意成分を含んでも良
く、このような任意成分としては、前記成分ｉ）及びｉ
ｉ）と反応して、水溶性高分子となるものであれば何で
も良く、特に限定されないが、好ましいビニルモノマー
化合物としては、アクリル酸、メタクリル酸、及びこれ
らの塩又はアルキルアルコールエステル、マレイン酸、
イタコン酸、これらの塩及びビニルアセトアミドから成
る群より選ばれたものが挙げられる。In the present invention, the above-mentioned water-soluble polymer copolymer may contain optional components in addition to the above-mentioned essential components, and such optional components include the components i) and i
Any compound may be used as long as it reacts with i) to become a water-soluble polymer, and is not particularly limited. Preferred vinyl monomer compounds include acrylic acid, methacrylic acid, and salts or alkyl alcohol esters thereof, maleic acid,
And those selected from the group consisting of itaconic acid, salts thereof and vinylacetamide.
【００１３】本発明の高分子凝集剤が優れた凝集性能を
示す理由は、次のように推定される。即ち、一般の懸濁
排水用凝集剤として使用されるポリアクリルアミドやア
クリルアミド‐アクリル酸共重合体の場合には、通常、
強酸性下においてカルボン酸の解離とアニオン化が抑制
され、したがって、凝集性能が低下するが、本発明の水
溶性高分子凝集剤の場合には、強酸性下においてもイオ
ン化解離でき、そのアニオン電荷で懸濁微粒子のカチオ
ン電荷と結合し、良好な凝集性能を発揮すると考えられ
る。The reason why the polymer flocculant of the present invention exhibits excellent flocculation performance is presumed as follows. That is, in the case of polyacrylamide or acrylamide-acrylic acid copolymer used as a general flocculant for suspended drainage, usually,
Under strongly acidic conditions, dissociation and anionization of the carboxylic acid are suppressed, and thus the coagulation performance is reduced.However, in the case of the water-soluble polymer coagulant of the present invention, it can be ionized and dissociated even under strongly acidic conditions, and its anionic charge Is considered to combine with the cation charge of the suspended fine particles to exhibit good aggregation performance.
【００１４】次に、本発明の有価金属の回収方法につい
て説明する。この方法は、上記有価金属を主として含有
する酸化鉱石を微粉砕し、水スラリーを沈降濃縮する第
一工程と、第一工程により得られた濃縮スラリーを硫酸
酸性下で浸出して分離する第二工程とを含み、この第二
工程での、硫酸浸出後の浸出残渣を有価金属溶解液から
凝集分離する際に、前述の組成及び粘度規定された分子
量を有する高分子凝集剤が使用される。本発明の回収方
法では、前述の高分子凝集剤が鉱石に対して０．０１〜
０．２０％、好ましくは０．０２〜０．１０％の割合で
添加され、この場合において、経済的で、かつ効率的な
凝集分離が達成される。尚、前記の第二工程における硫
酸浸出時のｐＨは一般に０．５〜４の範囲である。以
下、本発明の実施例を挙げて本発明を更に詳細に説明す
るが、本発明はこれらに限定されるものではない。Next, the method for recovering valuable metals according to the present invention will be described. This method comprises a first step of pulverizing an oxide ore mainly containing the valuable metal and sedimenting and concentrating a water slurry, and a second step of leaching and separating the concentrated slurry obtained in the first step under sulfuric acid. When the leaching residue after sulfuric acid leaching is coagulated and separated from the valuable metal solution in the second step, a polymer flocculant having the above-described molecular weight with the specified composition and viscosity is used. In the recovery method of the present invention, the above-described polymer flocculant is added to the ore in an amount of 0.01 to 0.01%.
It is added at a rate of 0.20%, preferably 0.02 to 0.10%, in which case economical and efficient coagulation separation is achieved. The pH at the time of leaching sulfuric acid in the second step is generally in the range of 0.5 to 4. Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention, but the present invention is not limited thereto.
【００１５】[0015]
【実施例】（実施例１）供試凝集剤として、以下の表１
に示される原料モノマー組成及び塩溶液粘度のもの（Ｎ
ｏ．１〜Ｎｏ．１０）をそれぞれ公知の重合方法を用い
て調製した。尚、表１におけるＡＡｍは、アクリルアミ
ドを示し、ＡＡｃＮａは、アクリル酸ナトリウムを示
し、ＡＭＰＳは、２‐アクリルアミド‐２‐メチルプロ
パンスルホン酸のナトリウム塩を示し、ＶＳは、ビニル
スルホン酸のナトリウム塩を示し、ＭＡＡｍはメタクリ
ルアミドを示し、ＤＡＡは、ジメチルアミノエチルアク
リレートを示し、表１に示されている粘度は、ブルック
フィールド型粘度計を用い、ローターＮｏ．１、６０ｒ
ｐｍ、３０℃の条件にて測定したものである。EXAMPLES (Example 1) As a test flocculant, the following Table 1 was used.
Of the raw material monomer composition and salt solution viscosity (N
o. 1 to No. 10) were each prepared using a known polymerization method. In Table 1, AAm indicates acrylamide, AAcNa indicates sodium acrylate, AMPS indicates sodium salt of 2-acrylamido-2-methylpropanesulfonic acid, and VS indicates sodium salt of vinylsulfonic acid. MAAm indicates methacrylamide, DAA indicates dimethylaminoethyl acrylate, and the viscosities shown in Table 1 were measured using a Brookfield viscometer, using a rotor No. 1,60r
pm at 30 ° C.
【００１６】[0016]
【表１】 [Table 1]
【００１７】一方、ニッケル鉱石スラリーとして、ニッ
ケル鉱石（Ｎｉ含有率０．８６％、粒径２ｍｍ以下）に
希硫酸を加え、オートクレーブ内にて２４０℃で１時間
処理したものを調製した。このようにして得られたスラ
リーは、濃度２１０ｇ／ｌ、ｐＨ１．１であった。On the other hand, a nickel ore slurry was prepared by adding dilute sulfuric acid to nickel ore (Ni content: 0.86%, particle size: 2 mm or less) and treating it at 240 ° C. for 1 hour in an autoclave. The slurry thus obtained had a concentration of 210 g / l and a pH of 1.1.
【００１８】凝集試験方法：１００ｍｌメスシリンダー
に、上記ニッケル鉱石スラリー９０ｍｌと、前記表１に
記載される凝集剤（Ｎｏ．１〜Ｎｏ．１０）の０．１％
水溶液をそれぞれ１０ｍｌとり、栓をして１０回倒立攪
拌して凝集させた。この後、形成されたフロックの大き
さを目視評価すると共に、メスシリンダーを静置して５
分後の沈降体積を測定した。これらの試験結果を以下の
表２に示す。Agglomeration test method: In a 100 ml graduated cylinder, 90 ml of the nickel ore slurry and 0.1% of the aggregating agents (No. 1 to No. 10) described in Table 1 above.
Each 10 ml of the aqueous solution was taken, stoppered, and inverted 10 times to coagulate. Thereafter, the size of the formed floc is visually evaluated, and the measuring cylinder is allowed to stand still for 5 minutes.
The sedimentation volume after one minute was measured. The test results are shown in Table 2 below.
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【発明の効果】上記表２に示されるように、特定の構成
比率にて、スルホン酸基を有する共重合可能な水溶性モ
ノマー又はその塩類と、（メタ）アクリルアミド又はそ
の誘導体とを含む本発明の高分子凝集剤は、有価金属の
濃縮スラリーに硫酸浸出液を添加した後の浸出液中に懸
濁分散している浸出残渣を凝集除去する際の凝集性能が
優れており、高温度下でも酸安定性が良好である。又、
このような高分子凝集剤を用いる本発明の有価金属の回
収方法を用いた場合には、ニッケル、コバルト、マンガ
ン等の有価金属を含有する酸化鉱石から効率良く、不純
物が少ない状態で有価金属を回収することができる。As shown in the above Table 2, the present invention contains a copolymerizable water-soluble monomer having a sulfonic acid group or a salt thereof and (meth) acrylamide or a derivative thereof in a specific composition ratio. Polymer flocculant has excellent flocculation performance when flocculating and removing leach residue suspended and dispersed in leachate after adding sulfuric acid leachate to concentrated slurry of valuable metal, and acid stable even at high temperature The properties are good. or,
When the method for recovering valuable metals of the present invention using such a polymer flocculant is used, the valuable metals can be efficiently recovered from oxide ores containing valuable metals such as nickel, cobalt, and manganese in a state with less impurities. Can be recovered.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２２Ｂ 47/00 Ｃ２２Ｂ 3/00 Ｑ 23/04 (72)発明者 伊藤 誠治 青森県八戸市大字河原木字遠山新田５−２ 大平洋金属株式会社八戸製造所内 (72)発明者 岡山 義昭 京都府京都市北区小山上総町５−１ (72)発明者 森 善幸 滋賀県神崎郡能登川町佐野225 Ｆターム(参考） 4D015 BA05 BA19 BB05 CA20 DB02 DB30 4K001 AA07 AA16 AA19 BA02 DB03 DB38 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C22B 47/00 C22B 3/00 Q23 / 04 (72) Inventor Seiji Ito Large character Kawaharagi Toyama, Hachinohe City, Aomori Prefecture 5-2 Nitta Okayo Metal Co., Ltd. Hachinohe Works (72) Inventor Yoshiaki Okayama 5-1 Koyamakamiso-cho, Kita-ku, Kyoto, Kyoto (72) Inventor Yoshiyuki Mori 225 Sano, Notogawa-cho, Kanzaki-gun, Shiga F-term ( Reference) 4D015 BA05 BA19 BB05 CA20 DB02 DB30 4K001 AA07 AA16 AA19 BA02 DB03 DB38
Claims (6)
ら硫酸浸出により前記有価金属を抽出し、浸出残渣を凝
集分離した後、硫化および炭酸化処理を行って前記有価
金属を回収する方法における、硫酸浸出残渣を凝集除去
する際に使用される高分子凝集剤であって、前記高分子
凝集剤が、ｉ）スルホン酸基を有する共重合可能な水溶
性モノマー又は、その塩類２．５〜４０モル％及び、ｉ
ｉ）（メタ）アクリルアミド又はその誘導体５０モル％
以上である組成を有した水溶性高分子共重合体であり、
しかも、当該水溶性高分子共重合体を０．２％含み、か
つＮａＣｌを４％含む塩水溶液の粘度が５〜４０ｍＰａ
・ｓであることを特徴とする有価金属回収法における硫
酸浸出工程用高分子凝集剤。1. A method according to claim 1, wherein said valuable metal is extracted from an oxide ore mainly containing valuable metal by sulfuric acid leaching, and a leaching residue is coagulated and separated, followed by sulfuration and carbonation treatment to recover said valuable metal. A polymer flocculant used for coagulating and removing a leached residue, wherein the polymer flocculant comprises: i) a copolymerizable water-soluble monomer having a sulfonic acid group, or 2.5 to 40 mols of a salt thereof. % And i
i) (Meth) acrylamide or its derivative 50 mol%
A water-soluble polymer copolymer having the composition described above,
Moreover, the salt aqueous solution containing 0.2% of the water-soluble polymer copolymer and 4% of NaCl has a viscosity of 5 to 40 mPa.
A polymer flocculant for a sulfuric acid leaching step in a valuable metal recovery method, wherein
水溶性モノマーが、２‐アクリルアミド‐２‐メチルプ
ロパンスルホン酸、又はその塩であることを特徴とす
る、請求項１に記載の有価金属回収法における硫酸浸出
工程用高分子凝集剤。2. The valuable metal according to claim 1, wherein the copolymerizable water-soluble monomer having a sulfonic acid group is 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof. Polymer flocculant for sulfuric acid leaching process in recovery method.
水溶性モノマーが、ビニルスルホン酸、又はその塩であ
ることを特徴とする、請求項１に記載の有価金属回収法
における硫酸浸出工程用高分子凝集剤。3. The process for recovering valuable metals according to claim 1, wherein the water-soluble copolymerizable monomer having a sulfonic acid group is vinylsulfonic acid or a salt thereof. Polymer flocculant.
を有する共重合可能な水溶性モノマー又は、その塩類及
び、ｉｉ）（メタ）アクリルアミド又はその誘導体とｉ
ｉｉ）共重合し得るビニルモノマー化合物の少なくとも
１種を更に含む組成から成るものであることを特徴とす
る、請求項１〜３のいずれか１項に記載の有価金属回収
法における硫酸浸出工程用高分子凝集剤。4. The polymer coagulant comprises: i) a copolymerizable water-soluble monomer having a sulfonic acid group or a salt thereof; and ii) (meth) acrylamide or a derivative thereof and i.
ii) The sulfuric acid leaching step in the valuable metal recovery method according to any one of claims 1 to 3, wherein the composition further comprises at least one vinyl monomer compound that can be copolymerized. Polymer flocculant.
酸、メタクリル酸、及びこれらの塩又はアルキルアルコ
ールエステル、Ｎ‐アルキル置換アクリルアミド、及び
ビニルアセトアミドから成る群より選ばれたものである
ことを特徴とする、請求項４に記載の有価金属回収法に
おける硫酸浸出工程用高分子凝集剤。5. The method according to claim 1, wherein the vinyl monomer compound is selected from the group consisting of acrylic acid, methacrylic acid, and salts or alkyl alcohol esters thereof, N-alkyl-substituted acrylamide, and vinylacetamide. A polymer flocculant for a sulfuric acid leaching step in the valuable metal recovery method according to claim 4.
微粉砕し、水スラリーを沈降濃縮する第一工程と、前記
第一工程にて得られた濃縮スラリーを硫酸酸性下で浸出
し、分離する第二工程を備えた、前記有価金属の回収方
法であって、前記第二工程において、ｉ）スルホン酸基
を有する共重合可能な水溶性モノマー又は、その塩類
２．５〜４０モル％及び、ｉｉ）（メタ）アクリルアミ
ド又はその誘導体５０モル％以上である組成を有した水
溶性高分子共重合体で、しかも、当該水溶性高分子共重
合体を０．２％含み、かつＮａＣｌを４％含む塩水溶液
の粘度が５〜４０ｍＰａ・ｓである高分子凝集剤を、凝
集剤として使用することを特徴とする有価金属の回収方
法。6. A first step of finely pulverizing an oxide ore mainly containing valuable metals and sedimenting and concentrating a water slurry, and leaching and separating the concentrated slurry obtained in the first step under sulfuric acid. The method for recovering valuable metals, comprising a second step, wherein in the second step, i) 2.5 to 40 mol% of a copolymerizable water-soluble monomer having a sulfonic acid group or a salt thereof; ii) a water-soluble polymer copolymer having a composition of 50 mol% or more of (meth) acrylamide or a derivative thereof, further containing 0.2% of the water-soluble polymer copolymer and 4% of NaCl. A method for recovering valuable metals, comprising using, as a flocculant, a polymer flocculant having a viscosity of a salt aqueous solution containing 5 to 40 mPa · s.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001147226A JP2002339020A (en) | 2001-05-17 | 2001-05-17 | High molecular flocculation agent for sulfuric acid leaching separation process in valuable metal recovery method and valuable metal recovery method using the same |
| AU40670/02A AU775649B2 (en) | 2001-05-17 | 2002-05-16 | Polymer flocculant for sulfuric acid leaching separation in valuable metal recovery method, and valuable metal recovery method using the same polymer flocculant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001147226A JP2002339020A (en) | 2001-05-17 | 2001-05-17 | High molecular flocculation agent for sulfuric acid leaching separation process in valuable metal recovery method and valuable metal recovery method using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002339020A true JP2002339020A (en) | 2002-11-27 |
Family
ID=18992744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001147226A Pending JP2002339020A (en) | 2001-05-17 | 2001-05-17 | High molecular flocculation agent for sulfuric acid leaching separation process in valuable metal recovery method and valuable metal recovery method using the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2002339020A (en) |
| AU (1) | AU775649B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012102265A1 (en) * | 2011-01-25 | 2012-08-02 | 住友金属鉱山株式会社 | Process for production of ore slurry |
| CN103173624A (en) * | 2013-03-06 | 2013-06-26 | 昆明理工大学 | Method for recovery germanium from germanium-containing flue dust |
| JP2014074233A (en) * | 2013-12-05 | 2014-04-24 | Sumitomo Metal Mining Co Ltd | Neutralization treatment plant |
| JP2019000834A (en) * | 2017-06-20 | 2019-01-10 | 住友金属鉱山株式会社 | Solid-liquid separation method of nickel high pressure leach residue |
| CN111663043A (en) * | 2020-04-28 | 2020-09-15 | 西北矿冶研究院 | Method for enriching and recovering valuable metals from acidic sewage in nonferrous smelting process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL2882878T3 (en) * | 2012-08-10 | 2017-06-30 | Basf Se | Metal leach and recovery process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4342653A (en) * | 1979-02-15 | 1982-08-03 | American Cyanamid Company | Process for the flocculation of suspended solids |
| US4587108A (en) * | 1982-10-07 | 1986-05-06 | Allied Colloids Limited | Flocculation of acid leach slurries |
-
2001
- 2001-05-17 JP JP2001147226A patent/JP2002339020A/en active Pending
-
2002
- 2002-05-16 AU AU40670/02A patent/AU775649B2/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012102265A1 (en) * | 2011-01-25 | 2012-08-02 | 住友金属鉱山株式会社 | Process for production of ore slurry |
| JP2012153922A (en) * | 2011-01-25 | 2012-08-16 | Sumitomo Metal Mining Co Ltd | Method for production of ore slurry |
| US9068241B2 (en) | 2011-01-25 | 2015-06-30 | Sumitomo Metal Mining Co., Ltd. | Method of producing ore slurry |
| CN103173624A (en) * | 2013-03-06 | 2013-06-26 | 昆明理工大学 | Method for recovery germanium from germanium-containing flue dust |
| JP2014074233A (en) * | 2013-12-05 | 2014-04-24 | Sumitomo Metal Mining Co Ltd | Neutralization treatment plant |
| JP2019000834A (en) * | 2017-06-20 | 2019-01-10 | 住友金属鉱山株式会社 | Solid-liquid separation method of nickel high pressure leach residue |
| CN111663043A (en) * | 2020-04-28 | 2020-09-15 | 西北矿冶研究院 | Method for enriching and recovering valuable metals from acidic sewage in nonferrous smelting process |
| CN111663043B (en) * | 2020-04-28 | 2022-01-18 | 西北矿冶研究院 | Method for enriching and recovering valuable metals from acidic sewage in nonferrous smelting process |
Also Published As
| Publication number | Publication date |
|---|---|
| AU775649B2 (en) | 2004-08-12 |
| AU4067002A (en) | 2002-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4569768A (en) | Flocculation of suspended solids from aqueous media | |
| US5196052A (en) | Bacterial-assisted heap leaching of ores | |
| JP6448684B2 (en) | Lithium recovery method | |
| CA2803904A1 (en) | Method for dispersing and aggregating components of mineral slurries and high-molecular weight multivalent anionic polymers for clay aggregation | |
| JP6703077B2 (en) | Lithium recovery method | |
| CA2598848A1 (en) | Water-in-oil-in water emulsions of hydroxamated polymers and methods for using the same | |
| US20140080945A1 (en) | Process for Improving the Rheological Properties of an Aqueous Dispersion | |
| JP2002339020A (en) | High molecular flocculation agent for sulfuric acid leaching separation process in valuable metal recovery method and valuable metal recovery method using the same | |
| CN106076656A (en) | A kind of modified carboxy methyl cellulose base mineral floating inhibitor, its preparation method and using method thereof | |
| EP3189169B1 (en) | Wet mineral ore processing in mining applications | |
| IE51418B1 (en) | Process for alumina recovery | |
| AU2012229023B2 (en) | Process for improving the flow rate of an aqueous dispersion | |
| EP2897707A1 (en) | Process for filtration enhancement of aqueous dispersions | |
| JP2548096B2 (en) | Method of treating wastewater containing cadmium | |
| JP3740423B2 (en) | Method for treating waste liquid containing emulsion polymerization polymer | |
| JPH05185074A (en) | Treating agent for multivalent metal-containing water and treatment of the same | |
| JP2002233882A (en) | Method for recovering heavy metal from heavy metal- containing aqueous solution | |
| US5758255A (en) | Opposite phase entrainment reduction in solvent extraction/electrowinning circuits by addition of water soluble cationic polymers | |
| CN114133011B (en) | Multifunctional high-efficiency silicon removing agent and preparation method thereof | |
| JP3932324B2 (en) | Method for recovering heavy metals from aqueous waste liquid | |
| JPH0361514B2 (en) | ||
| PH12019000205A1 (en) | Method of solid-liquid separation treatment | |
| AU2013318187B2 (en) | Process for improving the rheological properties of an aqueous dispersion | |
| OA16593A (en) | Process for improving the flow rate of an aqueous dispersion. | |
| EP3784808A1 (en) | Selective extraction of metals from complex inorganic sources |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040730 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060117 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060302 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20060329 |