CN1249257C - 铁的水解沉淀方法 - Google Patents
铁的水解沉淀方法 Download PDFInfo
- Publication number
- CN1249257C CN1249257C CNB018201938A CN01820193A CN1249257C CN 1249257 C CN1249257 C CN 1249257C CN B018201938 A CNB018201938 A CN B018201938A CN 01820193 A CN01820193 A CN 01820193A CN 1249257 C CN1249257 C CN 1249257C
- Authority
- CN
- China
- Prior art keywords
- iron
- solution
- zinc
- neutral
- leaching
- 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.)
- Expired - Lifetime
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 69
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052935 jarosite Inorganic materials 0.000 claims abstract description 27
- 238000001556 precipitation Methods 0.000 claims abstract description 23
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- 238000002386 leaching Methods 0.000 claims description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 21
- 230000007935 neutral effect Effects 0.000 claims description 21
- 238000006386 neutralization reaction Methods 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 19
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000004576 sand Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- 240000005373 Panax quinquefolius Species 0.000 claims 1
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 150000003818 basic metals Chemical class 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 239000004291 sulphur dioxide Substances 0.000 claims 1
- 235000010269 sulphur dioxide Nutrition 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 5
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- -1 this Chemical compound 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 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
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacture Of Iron (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Basic Packing Technique (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种从硫酸盐溶液中将铁作为黄钾铁矾水解沉淀的方法。含有硫酸盐的溶液中铁以二价的形式存在,将该溶液安排到铁沉淀阶段,用含氧气的气体将铁氧化到三价的形式。在沉淀阶段存在的还有Na,K或者NH4离子和黄钾铁矾核。
Description
本发明涉及一种从硫酸盐溶液中将铁以黄钾铁矾的形式水解沉淀的方法。含有硫酸盐的溶液中铁以二价的形式存在,将该溶液安排到铁沉淀阶段,用含氧气的气体将铁氧化到三价的形式。在沉淀阶段存在的还有Na,K或者NH4离子和黄钾铁矾核。
通过焙烧硫化锌浓缩物得到的锌焙砂,通常作为电解制备锌的起始材料。焙烧物的主要成分是氧化锌,ZnO,但也有一些锌与铁以铁酸锌ZnOFe2O3的形式结合。铁酸锌的数量通常是相当可观的以致于不可避免的要从中进行锌的回收。氧化锌甚至在高的pH值(3-5)下仍是易溶的,然而铁酸盐必须在更高的酸含量下才能浸出。铁酸盐浸出采用一个单独的阶段进行,此时锌和铁都按如下反应而溶解:
在将所得溶液返回进行中性浸出之前,必须将铁从溶液中沉淀出来,并在浸出后进行硫酸锌溶液的提纯和电解。对于到底有多少铁存在于溶液中时才能返回进行中性浸出并没有明确的标准,但通常地,5g/l水平的Fe被认为是可以接受的。上述方法在如US专利3434947和3493365中得到了描述。
在工业方法中,氧化锌浸出,中性浸出,通常在pH为2-5的情况下分两阶段进行,且当酸含量在30-100g/l时,铁酸盐浸出也能分两阶段进行。由铁酸盐浸出得到的沉淀物中含有来自焙烧物的铅,银和金。在顺利的条件下,这些物质的回收是有益的。由铁酸盐浸出得到的溶液含有溶解的锌和铁,在铁从中沉淀出之前,即使经常进行预中和,该溶液也是酸性很强的。有三种可用的沉淀铁的方法,在这些方法中,铁以黄钾铁矾Na[Fe3(SO4)2(OH)6],针铁矿FeOOH或者赤铁矿Fe2O3沉淀。
当铁以黄钾铁矾或者针铁矿沉淀时,在沉淀中要使用一种中和试剂以中和反应中释放出来的硫酸。通常地,中和试剂是一种焙烧物。当用焙烧物进行中和时,包含在溶液中的铟,镓和大多数的锗会与锌,铜和镉以及包含在焙烧物铁酸盐中的铟,镓,银,金和铅以相同的方式,保留在黄钾铁矾沉淀物中。在大多数情况下,这些有价值的金属丢失在铁的沉淀物中。为了使中和所用焙烧物的数量最小,由此使损失尽可能的最小化,预中和是值得进行的。
当铁以赤铁矿沉淀时,在没有中和的溶液中,赤铁矿通过氧化水解产生,该溶液中的铁首先由三价还原成了二价的形式:
在赤铁矿沉淀中避免了如上所述的有价值的金属的损失。然而,铁的沉淀必需在温度大约为200℃的反应釜中进行,这基本上限制了该方法的应用,尽管赤铁矿实际上是最环境友好的铁沉淀物形式。
在大气条件下的未中和的铁的水解沉淀将产生很大好处,US专利4305915中描述了一种以黄钾铁矾的形式沉淀铁的某种方法。该方法基于这样的事实,黄钾铁矾在酸性很强的溶液中是稳定的,而且,当始于中性的三价铁溶液时,铁的部分沉淀可能通过如下的平衡反应:
在铁酸盐浸出之后,将溶液冷却,剩余的酸例如用焙烧物进行中和。中和后,将溶液加热,在存在钠,钾或者铵离子和回收的黄钾铁矾,而没有加中和试剂时,铁可以从溶液中沉淀出来。然而由于该方法经济上不盈利,该方法的工业实现一直没有成功。首先,由铁酸盐浸出得到的含有三价铁的溶液在预中和前必须冷却,以使这一阶段的铁不会发生沉淀。第二个重要因素是,由于反应产生的大量的硫酸使沉淀速率下降,铁在沉淀阶段不能沉淀到足够低的含量。为了使沉淀成功,溶液在沉淀前必须稀释为大约一半。铁从热溶液中沉淀是最成功的,这意味着溶液必须再加热到几乎达到沸点。冷却和加热与溶液稀释一样,使该方法不经济。
这里开发的方法将消除上述方法中的缺点,使得从硫酸盐溶液中以非常纯的黄钾铁矾水解沉淀铁成为可能。在硫酸盐溶液中,铁以二价的亚铁形式溶解,将该溶液安排到铁沉淀阶段,铁被含氧气的气体氧化到三价的形式。在沉淀阶段存在碱性离子,如钠,钾或者铵离子和黄钾铁矾核,而且溶液的温度至多为该溶液的沸点。这样,沉淀在大气条件下进行。该沉淀方法适用于铁以黄钾铁矾沉淀的工艺。本发明的必要特征将在所附权利要求中明确。
用该方法廉价地处理例如所有的市场上的锌浓缩物是可能的。在技术上容易控制的条件下,用该方法回收包含在锌焙砂中的所有有价值的金属是可能的。在上述的方法中,铁总是从三价溶液中以黄钾铁矾沉淀。本发明的方法基于这样的事实,在沉淀出铁的溶液中,铁是以二价亚铁的形式存在的。当从二价铁溶液中进行沉淀时,与例如在US专利4305914中描述的方法相比,可以获得相当可观的更大的沉淀速率。铁能够从二价铁溶液中沉淀出来,而不需单独的氧化阶段。在最终所得黄钾铁矾中的锌的数量是非常少的,仅仅0.1-0.3%。
本发明方法用流程图1进行说明。
在流程图1中,本发明方法是与一种电解锌的方法相结合的,但请注意本方法能够适用于从其它非铁金属,如那些铜和镍金属的回收方法中沉淀铁。在流程图1所示的方法中,用锌焙砂1作原料,所述锌焙砂通常也含有其它有价值的金属。焙烧物中的锌通常以氧化锌的形式存在,但有一些也与铁结合成铁酸锌。锌焙砂1首先进行的处理阶段是中性浸出,正如通常实践中所用的,该处理阶段优选分两个阶段进行。在中性浸出阶段,焙烧物用稀释的电解返回酸溶液浸出,这样溶液的pH保持在2-5的范围。由第一中性浸出阶段2得到硫酸锌溶液3,该溶液通过溶液提纯(在图中没有详细表明)后将其拿去进行电解。由第一浸出阶段得到的沉淀物4拿去进行第二中性浸出阶段5,此时,焙烧物中剩余的氧化锌溶解。
由第二中性浸出阶段5得到的沉淀物6安排利用返回酸进行铁酸盐浸出,也就是强酸浸出7。该阶段也可以单步或者多步的。在强酸浸出时,溶液中的H2SO4含量在大约30-100g/l。由铁酸盐浸出得到的沉淀物8主要包含铅,银,金和其它不溶的化合物,如硅酸盐,石膏。该沉淀物可以拿去进行有价值的金属的回收处理。
由铁酸盐浸出产生的溶液9中的焙烧铁一般主要是三价的,但此时该溶液不进行通常的预中和和铁沉淀,而是根据本发明,在还原阶段10,铁被还原成二价的形式。优选地,还原用锌浓缩物进行,或者可能的用例如二氧化硫进行。依赖于还原剂,在还原中发生如下反应:
由还原阶段10生成的沉淀物11中包含还原中形成的硫和可能的所用浓缩物的剩余物,其可以返回进行焙烧。
还原阶段的溶液12是酸性的,在铁沉淀之前必须中和。现在该溶液包含二价铁,即使在高温下也不会有沉淀的危险。因此在预中和前无需将溶液冷却。该溶液可以像通常一样采用锌焙砂进行中和,由于氢氧化亚铁比氢氧化锌更易溶解,因此铁保留在了溶液中。
预中和可以在本方法的许多不同的阶段里进行,但最有利的是在第二阶段中性浸出5里进行,这里,含有铁(II)的溶液在尽可能高的pH值下进行中和。通常,在本阶段的pH值会升到3左右。当中和在第二阶段中性浸出进行时,中和剂是第一步的沉淀物,即不溶的锌焙砂,其与铁酸盐一起在本步中作为原料。第二阶段中性浸出5的溶液13拿去进行铁沉淀阶段14。在含有可形成黄钾铁矾的离子(Na,K,NH4等)的溶液中,用含氧气的气体将铁氧化成三价。然后根据如下反应,铁以黄钾铁矾的形式形成沉淀:
由于在预中和阶段5中铁没有沉淀出来,仅有在中性浸出中保持不溶的铁酸盐沉淀物拿去进行强酸浸出阶段7,这样就避免了铁在强酸浸出和还原阶段的内部循环。中和后的含铁溶液13直接拿去进行铁沉淀阶段14。在铁沉淀阶段生成了不含有价值的金属的黄钾铁矾沉淀和硫酸锌溶液15,该溶液里面含有的铁数量很少,以致可将该溶液进行第一步中性浸出阶段。
已知以少量存在于锌浓缩物中的诸如镓,铟和锗的金属,在铁酸盐浸出时会溶解,而且总会和三价铁离子一起沉淀。如果在整个过程里,铁都保持在三价的形式,这些金属的分离是非常困难的。由于在将进行预中和的溶液中,铁是二价的,上述金属的回收就是可能的,例如在将溶液拿去进行实际的中和阶段5之前对一些溶液进行单独的中和。在这种情况下,优选地,该溶液至少要中和到pH值为4,由此可以得到含Ga,In和Ge的不含铁的沉淀物。
当用本发明的方法时,可以看出,包含在锌浓缩物中的有价值的物质可以在不同的阶段得到很好的回收,且最终所得的黄钾铁矾是纯的。铁由二价铁溶液中进行沉淀时,如反应(6)所示,生成的硫酸的数量仅是如反应(3)所示的从三价铁溶液中生成的一半。如果在三价铁还原阶段10中使用的是锌浓缩物,还原反应就不会生成硫酸,这样,就仅生成传统的方法一半的硫酸。
流程图表明的方法中,铁酸盐浸出所得溶液在一个单独的还原阶段进行还原,但还原也可以和强酸浸出阶段一块儿进行,而无需单独的还原阶段。
从溶液中沉淀二价铁,用如下的例子作进一步的描述。
实施例1
被处理的溶液包含对应于100g/l的Zn2+的硫酸锌和另外25g/l的二价铁,2.5g/l的NH4和10g/l的硫酸,再加上200g/l的黄钾铁矾核。在封闭容器中将该溶液加热到100℃。料浆充分混合,在推进器的作用下向内部供给O2气,以使氧气的分压保持在0.5bar。全部的铁和二价铁通过取样检测,结果在下表中显示。这些结果也明显表明,在几个小时之内,铁可以被沉淀到一个很低的水平,以致于将溶液返回到第一中性浸出阶段是可能的。根据X光衍射分析,所得到的沉淀物是黄钾铁矾。该黄钾铁矾沉淀的过滤性能很好。留在最终沉淀物中的锌是极少的。
该例表明,尽管溶液仅仅中和到仍然包含10g/l的硫酸,这对应着pH值为大约1,仍然可以使铁充分沉淀。本领域技术人员知道如果该溶液进一步中和,例如,pH值为2-4,结果将会有相当可观的改善,这是完全现实的。另外,本例中的铵含量比通常的锌方法中的要低。所需的铵离子,NH4,也可以在沉淀阶段通过氨NH3来供给,此时有略微更少量的酸生成:
也可以使用氢氧化钠NaOH来代替铵。既然在这种不利的条件下仍获得了好的结果,那么绝对显而易见的,在更高水平的pH下,结果可以更好。
表1
时间 | 铁总量 | Fe2+ | NH4 | H2SO4 | Fe3+ |
h | g/l | g/l | g/l | g/l | g/l |
0 | 25.0 | 25.0 | 2.5 | 10.0 | 0.0 |
0.25 | 22.5 | 17.1 | 5.4 | ||
0.5 | 19.0 | 12.8 | 6.2 | ||
1 | 9.6 | 7.1 | 2.5 | ||
2 | 5.8 | 3.1 | 2.7 | ||
3 | 4.5 | 1.9 | 2.6 | ||
4 | 3.7 | 1.3 | 2.4 | ||
最终沉淀物 | Fe | Zn | S | RDX:黄钾铁矾 | |
% | 34.2 | 0.26 | 13.8 |
Claims (4)
1.一种从含有硫酸盐的溶液中将铁作为黄钾铁矾水解沉淀,并从锌焙砂中回收锌的方法,该回收包括中性浸出,铁酸盐浸出,锌电解和铁沉淀阶段,其特征在于
-首先将该焙砂在两个阶段(2,5)中浸出,并将在该第一浸出阶段中形成的硫酸锌溶液通过溶液提纯供入锌电解;
-将在中性浸出过程中未溶解的焙砂中含有的铁酸盐在铁酸盐浸出(7)中用锌电解中的返回酸浸出;
-将铁酸盐浸出中生成的三价铁溶液在还原阶段(10)用硫化锌浓缩物或二氧化硫还原到二价铁形式;
-通过将二价铁溶液(12)送到第二中性浸出(5)将其中和,且
-将来自第二中性浸出(5)的溶液送到铁沉淀阶段(14),其中使用含氧气体将中和的二价铁氧化成三价形式,该阶段中存在钠、钾或铵离子和黄钾铁矾核,且该沉淀阶段的温度最高为该溶液的沸点。
2.权利要求1的方法,其特征在于,将在含硫酸锌的溶液中包含的二价铁用锌焙砂中和。
3.权利要求1的方法,其特征在于,将在第二中性浸出中的含硫酸锌的溶液中包含的二价铁中和至少到pH为4的水平,以沉淀镓、铟和锗。
4.权利要求1的方法,其特征在于在铁酸盐浸出中溶解的三价铁还原成二价的形式,此后生成的沉淀物送至锌焙烧,溶液送至第二阶段中性浸出,其中该溶液用从第一中性浸出阶段得到的剩余物来中和;对第二中和阶段得到的剩余物送至铁酸盐浸出,已中和的溶液送至铁沉淀阶段,其中在存在碱金属或者铵离子和黄钾铁矾核的情况下,铁在氧气的作用下作为黄钾铁矾沉淀。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20002699 | 2000-12-08 | ||
FI20002699A FI20002699A0 (fi) | 2000-12-08 | 2000-12-08 | Menetelmä raudan hydrolyyttiseksi saostamiseksi |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1479793A CN1479793A (zh) | 2004-03-03 |
CN1249257C true CN1249257C (zh) | 2006-04-05 |
Family
ID=8559678
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB018201938A Expired - Lifetime CN1249257C (zh) | 2000-12-08 | 2001-12-07 | 铁的水解沉淀方法 |
Country Status (18)
Country | Link |
---|---|
US (1) | US7118719B2 (zh) |
EP (1) | EP1339883B1 (zh) |
JP (1) | JP4094949B2 (zh) |
KR (1) | KR100845169B1 (zh) |
CN (1) | CN1249257C (zh) |
AT (1) | ATE336595T1 (zh) |
AU (2) | AU1717102A (zh) |
BR (1) | BR0116028B1 (zh) |
CA (1) | CA2429889C (zh) |
DE (1) | DE60122370D1 (zh) |
EA (1) | EA005237B1 (zh) |
ES (1) | ES2269520T3 (zh) |
FI (1) | FI20002699A0 (zh) |
MX (1) | MXPA03005114A (zh) |
NO (1) | NO333462B1 (zh) |
PE (1) | PE20020807A1 (zh) |
WO (1) | WO2002046481A1 (zh) |
ZA (1) | ZA200304050B (zh) |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI116071B (fi) * | 2003-02-26 | 2005-09-15 | Outokumpu Oy | Menetelmä sinkin talteenottamiseksi vastavirtaliuotuksella |
FI20030612A (fi) * | 2003-04-23 | 2004-10-24 | Outokumpu Oy | Menetelmä metallurgisessa prosessissa syntyvän jätemateriaalin käsittelemiseksi |
FI118226B (fi) | 2005-12-29 | 2007-08-31 | Outokumpu Technology Oyj | Menetelmä harvinaisten metallien talteenottamiseksi sinkin liuotusprosessissa |
AU2007204591B2 (en) * | 2006-01-10 | 2010-07-22 | Murrin Murrin Operations Pty Ltd | Hematite precipitation |
JP4961603B2 (ja) * | 2006-07-14 | 2012-06-27 | Dowaメタルマイン株式会社 | ガリウム含有溶液の処理方法 |
WO2008128278A2 (en) * | 2007-04-19 | 2008-10-30 | Metallica Minerals Ltd | Treatment of nickel-containing solutions |
CN102268559A (zh) | 2007-05-21 | 2011-12-07 | 奥贝特勘探Vspa有限公司 | 从铝土矿石中提取铝的工艺 |
FI122676B (fi) | 2010-10-12 | 2012-05-15 | Outotec Oyj | Menetelmä sinkkisulfaattipitoisen liuoksen käsittelemiseksi |
AU2012231686B2 (en) | 2011-03-18 | 2015-08-27 | Orbite Aluminae Inc. | Processes for recovering rare earth elements from aluminum-bearing materials |
CN103210099A (zh) * | 2011-04-15 | 2013-07-17 | 泰姆5有限公司 | 从硫化锌精矿开始回收含硫介质中的锌的湿法冶金方法 |
EP3141621A1 (en) | 2011-05-04 | 2017-03-15 | Orbite Aluminae Inc. | Processes for recovering rare earth elements from various ores |
CN103842296B (zh) | 2011-06-03 | 2016-08-24 | 奥贝特科技有限公司 | 用于制备赤铁矿的方法 |
EP2755918A4 (en) | 2011-09-16 | 2015-07-01 | Orbite Aluminae Inc | PROCESS FOR PRODUCING TONERDE AND VARIOUS OTHER PRODUCTS |
US9023301B2 (en) | 2012-01-10 | 2015-05-05 | Orbite Aluminae Inc. | Processes for treating red mud |
AU2013203808B2 (en) | 2012-03-29 | 2016-07-28 | Orbite Aluminae Inc. | Processes for treating fly ashes |
RU2597096C2 (ru) | 2012-07-12 | 2016-09-10 | Орбит Алюминэ Инк. | Способы получения оксида титана и различных других продуктов |
MX349844B (es) * | 2012-07-16 | 2017-08-16 | Tam 5 S L * | Metodo hidrometalurgico para la recuperacion de zinc en medio sulfurico a partir de concentrados de zinc sulfurados con alto contenido en hierro. |
CN102766765B (zh) * | 2012-08-07 | 2014-12-24 | 四川四环电锌有限公司 | 氧化锌粉回收利用方法 |
BR112015006536A2 (pt) | 2012-09-26 | 2017-08-08 | Orbite Aluminae Inc | processos para preparar alumina e cloreto de magnésio por lixiviação com hcl de vários materiais. |
CN102899502A (zh) * | 2012-10-08 | 2013-01-30 | 来宾华锡冶炼有限公司 | 一种从高锡高铟锌浸出渣中提取锌铟及回收锡的方法 |
CN102899491B (zh) * | 2012-10-12 | 2013-12-04 | 中南大学 | 一种浮选分离硫酸锌浸出液中高浓度铁离子的方法 |
CA2891427C (en) | 2012-11-14 | 2016-09-20 | Orbite Aluminae Inc. | Methods for purifying aluminium ions |
CN103936080B (zh) * | 2013-03-20 | 2015-10-07 | 江苏理工学院 | 一种黄钾铁矾的制备方法 |
CN103290214A (zh) * | 2013-05-28 | 2013-09-11 | 中国恩菲工程技术有限公司 | 从含铁硫酸锌溶液中沉铁的方法 |
CN103695657A (zh) * | 2013-12-24 | 2014-04-02 | 广西博士海意信息科技有限公司 | 一种从湿法炼锌废渣中富集回收镓锗的方法 |
EP2902510A1 (en) * | 2014-01-29 | 2015-08-05 | Canbekte, Hüsnü Sinan | A new method for leaching of electric arc furnace dust (EAFD) with sulphuric acid |
CN109970105B (zh) * | 2019-04-24 | 2021-04-16 | 西南科技大学 | 一种湿法炼锌工艺中清洁回收铁的方法 |
CN110079676B (zh) * | 2019-05-05 | 2020-10-09 | 昆明理工大学 | 一种富含锗的氧化锌烟尘梯级浸出工艺 |
CN110764545B (zh) * | 2019-10-24 | 2020-11-27 | 中南大学 | 一种湿法炼锌中性浸出过程中pH值的控制方法 |
CN112795795B (zh) * | 2020-12-15 | 2023-10-03 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | 一种在硫酸浸出液中加压氧化分离镓锗的方法 |
CN113088710A (zh) * | 2021-03-29 | 2021-07-09 | 云南驰宏资源综合利用有限公司 | 一种铜锗置换渣中铜锗分离的方法 |
CN114634257A (zh) * | 2022-03-04 | 2022-06-17 | 太原碧蓝水利工程设计股份有限公司 | 一种处理酸性矿坑水的方法及由酸性矿坑水合成的羟基硫酸铁钾 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE673023A (zh) * | 1965-04-30 | 1900-01-01 | ||
IE32587B1 (en) * | 1968-11-20 | 1973-09-19 | Mines Fond Zinc Vieille | Improvements in or relating to valorization |
ES407811A2 (es) | 1972-10-20 | 1976-02-01 | Asturiana De Zinc Sa | Un procedimiento de recuperacion de zinc de las ferritas existentes en residuos. |
US4042474A (en) * | 1973-08-02 | 1977-08-16 | Pako Corporation | Separating nickel, cobalt and chromium from iron in metallurgical products |
US4305914A (en) * | 1977-05-09 | 1981-12-15 | Electrolytic Zinc Company | Process for precipitating iron as jarosite with a low non-ferrous metal content |
US4128617A (en) * | 1977-07-11 | 1978-12-05 | Newmont Exploration Limited | Treatment of zinc calcines for zinc recovery |
CA1094326A (en) * | 1977-08-19 | 1981-01-27 | Verner B. Sefton | Process for the precipitation of iron as jarosite |
DE3935362A1 (de) * | 1989-10-24 | 1991-04-25 | Ruhr Zink Gmbh | Verfahren zur aufarbeitung von jarosit-haltigen rueckstaenden |
CA2104736A1 (en) * | 1993-08-24 | 1995-02-25 | Lucy Rosato | Process for high extraction of zinc from zinc ferrites |
FI98073C (fi) | 1995-08-14 | 1997-04-10 | Outokumpu Eng Oy | Menetelmä nikkelin talteenottamiseksi hydrometallurgisesti kahdesta eri nikkelikivestä |
FI100806B (fi) * | 1996-08-12 | 1998-02-27 | Outokumpu Base Metals Oy | Menetelmä sinkkirikasteen liuottamiseksi atmosfäärisissä olosuhteissa |
-
2000
- 2000-12-08 FI FI20002699A patent/FI20002699A0/fi not_active IP Right Cessation
-
2001
- 2001-11-28 PE PE2001001194A patent/PE20020807A1/es active IP Right Grant
- 2001-12-07 EA EA200300648A patent/EA005237B1/ru not_active IP Right Cessation
- 2001-12-07 JP JP2002548197A patent/JP4094949B2/ja not_active Expired - Lifetime
- 2001-12-07 AT AT01999677T patent/ATE336595T1/de not_active IP Right Cessation
- 2001-12-07 CN CNB018201938A patent/CN1249257C/zh not_active Expired - Lifetime
- 2001-12-07 KR KR1020037007661A patent/KR100845169B1/ko active IP Right Grant
- 2001-12-07 AU AU1717102A patent/AU1717102A/xx active Pending
- 2001-12-07 WO PCT/FI2001/001065 patent/WO2002046481A1/en active IP Right Grant
- 2001-12-07 EP EP01999677A patent/EP1339883B1/en not_active Expired - Lifetime
- 2001-12-07 MX MXPA03005114A patent/MXPA03005114A/es active IP Right Grant
- 2001-12-07 DE DE60122370T patent/DE60122370D1/de not_active Expired - Lifetime
- 2001-12-07 ES ES01999677T patent/ES2269520T3/es not_active Expired - Lifetime
- 2001-12-07 US US10/450,921 patent/US7118719B2/en not_active Expired - Lifetime
- 2001-12-07 AU AU2002217171A patent/AU2002217171B2/en not_active Expired
- 2001-12-07 CA CA2429889A patent/CA2429889C/en not_active Expired - Lifetime
- 2001-12-07 BR BRPI0116028-1A patent/BR0116028B1/pt not_active IP Right Cessation
-
2003
- 2003-05-26 ZA ZA200304050A patent/ZA200304050B/en unknown
- 2003-06-03 NO NO20032509A patent/NO333462B1/no not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EA200300648A1 (ru) | 2003-12-25 |
EP1339883B1 (en) | 2006-08-16 |
AU2002217171B2 (en) | 2006-03-16 |
US7118719B2 (en) | 2006-10-10 |
ATE336595T1 (de) | 2006-09-15 |
CA2429889A1 (en) | 2002-06-13 |
KR100845169B1 (ko) | 2008-07-09 |
ES2269520T3 (es) | 2007-04-01 |
NO20032509D0 (no) | 2003-06-03 |
CN1479793A (zh) | 2004-03-03 |
KR20030059326A (ko) | 2003-07-07 |
NO20032509L (no) | 2003-06-03 |
ZA200304050B (en) | 2004-02-19 |
FI20002699A0 (fi) | 2000-12-08 |
EP1339883A1 (en) | 2003-09-03 |
CA2429889C (en) | 2011-02-08 |
WO2002046481A1 (en) | 2002-06-13 |
BR0116028B1 (pt) | 2010-09-08 |
NO333462B1 (no) | 2013-06-17 |
AU1717102A (en) | 2002-06-18 |
BR0116028A (pt) | 2003-10-07 |
US20040067183A1 (en) | 2004-04-08 |
JP4094949B2 (ja) | 2008-06-04 |
EA005237B1 (ru) | 2004-12-30 |
JP2004515439A (ja) | 2004-05-27 |
PE20020807A1 (es) | 2002-10-02 |
MXPA03005114A (es) | 2003-09-05 |
DE60122370D1 (de) | 2006-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1249257C (zh) | 铁的水解沉淀方法 | |
CN100558918C (zh) | 从溶液中回收有价值金属和砷的方法 | |
EP1966401B1 (en) | Method for recovering rare metals in a zinc leaching process | |
US20090019970A1 (en) | Process for recovery of metal values from materials containing arsenic and/or antimony | |
AU2002217171A1 (en) | Method for the hydrolytic precipitation of iron | |
ZA200505981B (en) | Method for recovery of zinc by countercurrent leaching | |
KR20000029886A (ko) | 대기조건에서아연농축물의침출방법 | |
US4107265A (en) | Treating residues from the leaching of roasted zinc blende | |
US10689732B2 (en) | Methods for controlling iron via magnetite formation in hydrometallurgical processes | |
SE504959C2 (sv) | Förfarande för rening av metallinnehållande lösningar, som innehåller järn- och zinksalter | |
CN116103494B (zh) | 一种矿石堆浸中降低浸出液杂质离子含量的方法 | |
WO1988003912A1 (en) | Process for recovering metal values from ferrite wastes | |
CN114635046A (zh) | 湿法炼锌过程中降低沉铁渣中锌含量的方法 | |
WO2019175838A1 (en) | Iron control in copper- and zinc-containing process solutions | |
ANATASE | PROCESS FOR RECOVERING GOLD FROM THIOSULFATE LEACH SOLUTIONS AND SLURRIES WITH ION EXCHANGE RESIN | |
MXPA97009728A (en) | Hydrometalurgical extraction of metal assisted porclor | |
AU2006303814A1 (en) | Process for recovery of metal values from materials containing arsenic and/or antimony | |
MX2008008457A (en) | Method for recovering rare metals in a zinc leaching process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
ASS | Succession or assignment of patent right |
Owner name: OUTOTEC GMBH Free format text: FORMER OWNER: OUTOKUMPU OYJ Effective date: 20121212 |
|
C41 | Transfer of patent application or patent right or utility model | ||
TR01 | Transfer of patent right |
Effective date of registration: 20121212 Address after: Espoo, Finland Patentee after: Outokumpu Technology Oyj Address before: Espoo, Finland Patentee before: Outokumpu Oyj |
|
CX01 | Expiry of patent term |
Granted publication date: 20060405 |
|
CX01 | Expiry of patent term |