CN106906363B - 一种含砷铜渣的处理方法 - Google Patents
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- 239000002893 slag Substances 0.000 title claims abstract description 43
- 229910000563 Arsenical copper Inorganic materials 0.000 title claims abstract description 36
- 238000003672 processing method Methods 0.000 title claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 claims abstract description 63
- 239000010949 copper Substances 0.000 claims abstract description 63
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 40
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000002955 isolation Methods 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 241000234282 Allium Species 0.000 claims 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 33
- 239000011701 zinc Substances 0.000 abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052725 zinc Inorganic materials 0.000 abstract description 17
- 229910052738 indium Inorganic materials 0.000 abstract description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 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 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- -1 Iron ion Chemical class 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002620 method output Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- 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
本发明涉及一种含砷铜渣的处理方法,属于湿法冶金技术领域。本发明针对铜的质量百分数含量为10~70%、砷的质量百分数含量为5~20%、铁的质量百分数含量为5~30%的含砷铜渣提出的处理方法,在含砷铜渣中加入稀硫酸,搅拌均匀形成矿浆;在矿浆中加入氧化介质反应至矿浆的pH值为1~3,沉淀、固液分离即得到富含铜浸出液和砷铁渣。本发明方法同步实现铜、锌及铟等有价金属浸出至溶液和将砷和铁形成稳定的砷铁固化渣,具有实现有价金属回收率高、工艺流程简单、处理过程清洁高效等特点。
Description
技术领域
本发明涉及一种含砷铜渣的处理方法,属于湿法冶金技术领域。
背景技术
锌精矿中通常伴生有数量较可观的铜,尤其在复杂铁闪锌矿中铜的含量可达到1%以上,具有较高经济价值。在湿法炼锌过程中,采用中浸或中浸-弱酸浸出工艺只能回收40~50%的金属铜,其余则留在浸出渣中,采用回转窑挥发法处理浸出渣时铜几乎全部进入窑渣,难以回收;采用热酸浸出技术处理浸出渣时,铜随锌、铁、铟进入热酸浸出液;采用加压浸出工艺处理锌精矿时,铜同样随锌、铁、铟进入氧压浸出液,对于上述两类浸出液大部分冶炼企业采用的是溶剂萃取回收铜和铟-氧化中和沉铁或中和沉铟-氧化沉铁。在浸出液分离除铁工艺中,为了避免沉铁过程锌、铟、铜等有价金属进入铁渣,通常需要先将浸出液中的Fe3+还原为Fe2+。目前常用的方法为在酸性条件下,利用硫化锌精矿还原浸出液中的三价铁离子,但由于精矿利用率低,需添加过量锌精矿,易导致热酸浸出液中的铜生成硫化亚铜沉淀进入渣中,渣中铜、锌含量高。还原后液采用中和法沉铟时部分铜进入沉铟渣,需在铟渣回收铟的工艺过程进行专门铜铟分离处理,其工艺流程较为繁琐,且回收率较低;溶剂萃取法虽能实现较高的铜回收率,但由于浸出液量大、铜浓度低,所需萃取体系庞大,造成大量有机试剂进入浸出液中,需进行专门脱油处理。因此,长期以来锌精矿伴生的铜未能得到较好地回收利用,从而降低了资源的综合利用率,造成了资源的浪费。
为解决锌精矿冶炼过程中锌、铁、铟、铜的高效分离和综合回收的问题,提高金属回收率和资源综合利用率,本发明的发明人在专利CN201310308061和CN201410049421中公开了湿法炼锌过程中提高铜回收率方法,采用铁粉置换法产出了一种含砷铜渣,实现了强酸性溶液中铜的高效回收和砷的有效脱除,且过程无砷化氢产生,含砷铜渣可进一步回收铜。
发明专利CN201410739063.9公开了一种从铜烟尘中回收铜、固化砷的方法,其方法特征是先将铜烟尘进行常压酸浸得到酸浸液,再对酸浸液进行氧压沉砷得到臭葱石和沉砷后的含铜液。该方法较好的实现了浸出溶液中铜与砷的分离,但浸出过程铜砷浸出率较低,浸出渣中铜砷含量高,造成了铜资源浪费和砷污染。
目前现有技术可以完成含砷铜渣中铜、砷分离,但是工艺流程长、过程难以控制,分离效率较低。
发明内容
本发明针对现有技术存在的问题,提供一种含砷铜渣的处理方法,实现有价金属高回收率、工艺流程简单、处理过程清洁高效;本发明针对铜浸出的特性与砷、铁沉淀的特性,将铜的浸出和砷的沉淀在同一反应釜同一过程中完成,利用砷和铁沉淀过程生成的酸浸出铜,满足铜浸出所需的硫酸;利用铜的浸出消耗体系中的酸,维持沉淀反应所需的低酸环境,有效实现含砷铜渣中有价金属的浸出与杂质的沉淀同步进行,达到高效分离回收的目的。
本发明采用的技术方案是:利用稀硫酸对含砷铜渣进行浆化,将所形成的矿浆置于带有搅拌装置的反应釜;在反应釜内通入氧化介质,在高温下反应,将铜及锌、铟等有价金属浸出至溶液,同时将砷和铁形成稳定的砷铁固化渣,液固分离后得到富含铜的溶液和砷铁渣。
一种含砷铜渣的处理方法,其特征在于,具体步骤如下:
(1)按照稀硫酸与含砷铜渣的液固比mL:g为20~100:1的比例,在含砷铜渣中加入稀硫酸,搅拌均匀形成矿浆;
(2)在温度90~180℃的条件下,将步骤(1)所得矿浆中加入氧化介质反应2-4小时至矿浆的pH值为1~3,沉淀、固液分离即得到富含铜浸出液和砷铁渣,砷铁渣的主要物象为无害化的臭葱石和赤铁矿。
所述含砷铜渣中铜的质量百分数含量为10~70%、砷的质量百分数含量为5~20%、铁的质量百分数含量为5~30%;
进一步地,所述含砷铜渣中铜的主要物象为砷化亚铜、氧化亚铜的一种或任意比两种,铁的主要物象为砷化亚铁、砷化铁和/或金属铁;
所述步骤(1)稀硫酸的浓度为10~30g/L;
进一步地,稀硫酸选自工业硫酸的水溶液、湿法炼锌系统的沉铁溶液或湿法冶金的电解液;
所述步骤(2)氧化介质为氧气或空气。
本发明的有益效果是:
(1)本发明利用氧化介质缓慢氧化含砷铜渣,使其中的铜、砷、铁、锌、铟等溶解进入溶液;同时,砷、铁以臭葱石和赤铁矿的形式沉淀为浸出渣,从而将铜、锌、铟的浸出和砷、铁的沉淀在同一反应釜同一过程中完成,有效实现含砷铜渣中有价金属的浸出过程与杂质的沉淀过程同步进行;
(2)本发明的反应过程中利用铁沉淀为赤铁矿所生成的酸浸出铜、锌、铟,保障浸出所需的硫酸;利用铜、锌、铟的浸出消耗体系中的酸,维持沉淀反应所需的低酸环境,既降低了酸耗,又避免了现有技术中添加中和剂来中和沉淀过程生成的硫酸以维持体系pH的不足,有价金属的浸出过程与杂质的沉淀过程无杂质引入,所得含铜溶液易于处理,有价金属回收率高、工艺流程简单、清洁高效、节能环保。
具体实施方式
下面结合具体实施方式,对本发明作进一步说明。
实施例1:本实施例的含砷铜渣中铜的质量百分数含量为69.8%、砷的质量百分数含量为5.04%、铁的质量百分数含量为5.17%;
一种含砷铜渣的处理方法,具体步骤如下:
(1)在常温条件下,按照稀硫酸与含砷铜渣的液固比mL:g为100:1的比例,在含砷铜渣中加入稀硫酸(稀硫酸为湿法冶金的电解液,稀硫酸浓度为20g/L),搅拌均匀,进行浆化形成矿浆;
(2)将步骤(1)所得矿浆输送至带有搅拌装置的加压反应釜中,在温度150℃的条件下,在在反应釜内的矿浆中通入氧气,反应3小时至矿浆的pH值为1.8,沉淀、固液分离即得到富含铜浸出液和砷铁渣;
经测定,富含铜浸出液中铜的浓度为6.54g/L,砷铁渣中砷的质量百分数含量为24.6%、铁的质量百分数含量为20.7%;
本实例中铜浸出率为98.1%,砷的沉淀率为92.9%,铁的沉淀率为76.3%。
实施例2:本实施例的含砷铜渣中铜的质量百分数含量为35.7%、砷的质量百分数含量为9.3%、铁的质量百分数含量为9.7%;
一种含砷铜渣的处理方法,具体步骤如下:
(1)在常温条件下,按照稀硫酸与含砷铜渣的液固比mL:g为20:1的比例,在含砷铜渣中加入稀硫酸(稀硫酸为湿法炼锌系统的沉铁溶液,稀硫酸浓度为30g/L),搅拌均匀,进行浆化形成矿浆;
(2)将步骤(1)所得矿浆输送至带有搅拌装置的加压反应釜中,在温度180℃的条件下,在在反应釜内的矿浆中通入氧气,反应3小时至矿浆的pH值为2.97,沉淀、固液分离即得到富含铜浸出液和砷铁渣;
经测定,富含铜浸出液中铜的浓度为17.1g/L,砷铁渣中砷的质量百分数含量为23.5%、铁的质量百分数含量为29.1%;
本实例中铜浸出率为95.7%,砷的沉淀率为92.6%,铁的沉淀率为99.1%。
实施例3:本实施例的含砷铜渣中铜的质量百分数含量为10.1%、砷的质量百分数含量为19.8%、铁的质量百分数含量为29.6%;
一种含砷铜渣的处理方法,具体步骤如下:
(1)在常温条件下,按照稀硫酸与含砷铜渣的液固比mL:g为50:1的比例,在含砷铜渣中加入稀硫酸(稀硫酸为工业硫酸的水溶液,稀硫酸浓度为10g/L),搅拌均匀,进行浆化形成矿浆;
(2)将步骤(1)所得矿浆输送至带有搅拌装置的加压反应釜中,在温度90℃的条件下,在在反应釜内的矿浆中通入氧气,反应2小时至矿浆的pH值为1.02,沉淀、固液分离即得到富含铜浸出液和砷铁渣;
经测定,富含铜浸出液中铜的浓度为2.11g/L,砷铁渣中砷的质量百分数含量为22.1%、铁的质量百分数含量为21.2%;
本实例中铜浸出率为99.7%,砷的沉淀率为91.3%,铁的沉淀率为58.6%。
Claims (2)
1.一种含砷铜渣的处理方法,其特征在于,具体步骤如下:
(1)按照稀硫酸与含砷铜渣的液固比mL:g为20~100:1的比例,在含砷铜渣中加入稀硫酸,搅拌均匀形成矿浆;其中稀硫酸的浓度为10~30g/L;
(2)在温度90~180℃的条件下,将步骤(1)所得矿浆中加入氧化介质反应至矿浆的pH值为1~3,沉淀、固液分离即得到富含铜浸出液和砷铁渣;砷铁渣的主要物象为无害化的臭葱石和赤铁矿;
所述含砷铜渣中铜的质量百分数含量为10~70%、砷的质量百分数含量为5~20%、铁的质量百分数含量为5~30%;
所述含砷铜渣中铜的主要物象为砷化亚铜与氧化亚铜的混合物或砷化亚铜,铁的主要物象为砷化亚铁、砷化铁和/或金属铁。
2.根据权利要求1所述含砷铜渣的处理方法,其特征在于:步骤(2)氧化介质为氧气或空气。
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