CN1720342A - 处理炉渣的方法 - Google Patents
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- 239000002893 slag Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000010949 copper Substances 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 238000003723 Smelting Methods 0.000 claims abstract description 15
- 239000012141 concentrate Substances 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 230000001580 bacterial effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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- 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
- C22B7/04—Working-up slag
-
- 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
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
-
- 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
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0047—Smelting or converting flash smelting or converting
-
- 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
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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
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- Manufacturing & Machinery (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
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Abstract
本发明涉及一种处理悬浮熔炼炉例如闪速熔炼炉中直接从精矿生产粗铜中产生的炉渣以便回收铜的方法,以致至少一部分炉渣在至少一个步骤中浸析。
Description
本发明涉及一种权利要求1前序部分中限定的用于处理粗铜生产中产生的炉渣的方法。
在悬浮反应器例如闪速熔炼炉中直接由硫化矿精矿一步生产粗铜在经济上是合理的,但存在一些限制条件。在直接生产粗铜中,其中一些最明显的问题是铜的成渣和产生大量炉渣。为了确保足够高的铜回收率,在炉渣的清洗时,必需回收炉渣中铜。除了炉渣的数量外,另一问题是在硫化矿精矿的燃烧中产生大量的热量。在这种情况下,使用较低氧富集的工艺空气,这就意味着工艺空气中所含氮气的加热平衡了热收支(heat economy)。但是,这又产生大量工艺气体,它反过来需要大的炉空间以及尤其是大的气体处理装置。
在精矿的铜含量足够高的情况下,通常至少37%Cu,直接按一步生产粗铜在经济上是可能的。通常精矿的热值越低,精矿的铜含量越高。由于高的铜含量,硫化铁矿物的份额低。当加工上述精矿时,可使用足够高的氧富集量,因此气体的数量可维持较低。较低铜含量的精矿也适用于生产粗铜,如果铁含量也低的话,在这种情况下产生的炉渣数量不会很多。
从芬兰专利申请书982818已知一种生产粗铜的方法,在熔炼炉中除了精矿外该方法还用于冷却的研磨铜锍。按生产的粗铜数量计,现在该方法产生比传统的方法少的炉渣量。在炉渣中铜的损失也减少。产生的炉渣或按一步或优选按两步炉渣清理法处理。两步炉渣清理法包括两个电炉或一个电炉和一个炉渣富集装置。在电炉中,炉渣被焦炭还原,以致炉渣相中的有价金属被还原,并分离为在炉渣层下方的单独的铜相。在炉渣在炉渣富集装置中处理的情况下,炉渣精选物可返回熔炼反应器。将粗铜在阳极炉中精炼。
如果炉渣在电炉中一步处理,以致炉渣中铜的数量在经济上不重要,但粗铜中的铁含量仍是如此地高,以致常常需要在转炉中对粗铜进行单独的处理。一种方法是电炉预处理,在那里生成的粗铜与阳极炉中的大量粗铜一起处理,但在炉渣中仍留下很多铜,由于经济原因,它必需用富集技术手段回收。
本发明的目的是要提供一种处理在精矿直接生产粗铜中产生的炉渣的新方法。就总的经济性来说,本发明的一个特定目的是要提供一种用于回收粗铜生产中结渣铜更有效和更有利的方法。
本发明的特征在于权利要求1特征部分。本发明的其他优选实施方案的特征在其余的权利要求中限定。
本发明的方法有许多优点。根据所述的方法,可有利地回收直接从精矿生产粗铜产生的炉渣中所含的铜。本发明的方法简化了铜的回收,此外所述的方法能改进杂质的控制。与电炉还原相比,湿法冶金的炉渣中所含铜的回收降低了能耗。此外,与火法冶金回收相比,气体和粉尘的排放减少。
下面参考附图更详细地描述本发明。
图1为本发明的工艺图。
图1说明本发明一种处理悬浮熔炼炉例如闪速熔炼炉中生产粗铜时产生的炉渣即粗铜炉渣以便回收铜的方法,在所述的情况下,在至少一步中将至少一部分炉渣浸析。将铜精矿、助熔剂和氧富集的空气送入悬浮熔炼炉例如闪速熔炼炉中熔炼1。干燥的精矿颗粒以热悬浮态与氧富集的空气迅速反应。在反应中释放的热量用于本方法。部分硫被氧化成二氧化硫,而铁被氧化成铁氧化物,从而与助熔剂生成炉渣。反应产物沉降到悬浮熔炼炉底部,形成两个单独的熔融相:粗铜和粗铜炉渣。将本方法中产生的气体进一步按已知的方式处理。将悬浮熔炼炉中产生的粗铜送去阳极炉处理2,在那里按已知的方式精炼并铸造成铜阳极。
熔炼1中产生的粗铜炉渣通过提供的流通槽(circulationchannel)例如出渣槽从悬浮熔炼炉出渣,并进一步送去处理,以便回收粗铜炉渣中所含的铜。首先,将粗铜炉渣送去造粒和研磨3。造粒的粗铜炉渣例如在湿法研磨中研磨到一定粒度,以便获得更大的反应表面。在浸析4中,粗铜炉渣中所含的金属被浸析。根据下面的实施例,浸析4在氧化条件下用硫酸进行,生成硫酸铜。加入硫酸的数量最好为500-900克/公斤炉渣。也可用氨溶液、氯化物溶液进行浸析,或细菌浸析。在浸析步骤以后,在铜沉淀5中,铜从含金属硫酸盐的溶液中分离出。在沉淀步骤中,例如通过氢氧化物沉淀或硫化物沉淀使铜从含金属硫酸盐的溶液中沉淀。在氢氧化物沉淀中,用石灰石沉淀铜,并将生成的含铜沉淀物送回熔炼1。在硫化物沉淀中,用硫化氢沉淀铜,并将生成的含铜沉淀物送回熔炼1。铜也可用液-液萃取法回收,并作为阴极铜电解。
实施例
为了验证这一方法,在带盖的2升耐酸反应器中用硫酸进行了溶液实验。反应器装有4个阻流板、1个回流冷凝器和1个搅拌器。在反应器中,还有相连的连续pH值测量仪、温度调节仪和在搅拌器叶片下方的鼓氧设备。加热炉用于加热。
在实验开始时,将炉渣(200克)浸析在水中,水的数量稍小于1升。在所有实验中,水和加入的硫酸总量刚好为1升。溶液的温度为90℃。实验中加入的硫酸(H2SO4)数量为806克/1000克炉渣。
在所有实验中,浸析时间为6小时,并在实验中使用机械搅拌(约770转/分)和氧(0.50升/分)。
逐渐加入浓硫酸(含量95%(重量)),同时将温度调节到90℃。当所有的酸加入后开始测量反应时间。在实验开始0、2、4和6小时时取浆液样。在样品的滤液和沉淀物中,分析铜(Cu)和铁(Fe)。
最初浸析的炉渣含有32.5%Cu和23.9%Fe。下表列出在此基础上得到的分析结果和浸析产率:
时间 | 溶液 | 沉淀物 | 进入溶液中的Cu产率 |
pH Cu,克/升Fe, 克/升 | Cu,% Fe,% | % | |
0小时 | 0.5 59.8 16.8 | 8.8 23.6 | 72.6 |
2小时 | 1.1 80.0 22.4 | 4.1 25.7 | 88.3 |
4小时 | 1.2 82.0 23.6 | 3.4 23.6 | 89.4 |
6小时 | 1.2 87.0 24.6 | 3.1 23.8 | 90.4 |
最后沉淀物的重量为77.4克,铜含量为3.1%,这意味着在溶液中的铜总产率为96.3%。
在类似的条件下对以下炉渣进行重复实验,所述炉渣从熔融状态直接用水造粒代替炉渣缓慢冷却,以致得到的产物为具有相应组成的细颗粒。在类似的条件下,得到的铜总浸析产率为95.8%,当考虑到分析的准确度,它与缓慢冷却的炉渣有相同的数量级。
通过调节酸度,铜从溶液中选择性沉淀,以致铁在第一步中沉淀,而铜在第二步中沉淀,从而不希望的铁可与铜分离。
熟悉本专业的技术人员很清楚,本发明的各种优选实施方案不仅仅限于上述实施例,而可在附后的权利要求书范围内变化。
Claims (10)
1.一种处理悬浮熔炼炉例如闪速熔炼炉中直接从精矿生产粗铜中产生的炉渣以便回收铜的方法,其特征在于,至少一部分炉渣在至少一个步骤中浸析。
2.根据权利要求1的方法,其特征在于,在浸析以前,将炉渣造粒并研磨。
3.根据权利要求1或2的方法,其特征在于,用硫酸进行浸析。
4.根据权利要求1或2的方法,其特征在于,用氨溶液进行浸析。
5.根据权利要求1或2的方法,其特征在于,用氯化物溶液进行浸析。
6.根据权利要求1或2的方法,其特征在于,用细菌溶液进行浸析。
7.根据上述权利要求中任一项的方法,其特征在于,浸析以后,通过氢氧化物沉淀来回收铜。
8.根据上述权利要求1-6中任一项的方法,其特征在于,浸析以后,通过硫化物沉淀来回收铜。
9.根据权利要求1-6中任一项的方法,其特征在于,在浸析以后,在液-液萃取中回收铜,并电解为阴极铜。
10.根据权利要求7或8的方法,其特征在于,将沉淀中得到的含铜炉渣送回悬浮熔炼炉。
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FI20022150A FI115638B (fi) | 2002-12-05 | 2002-12-05 | Menetelmä kuonan käsittelemiseksi |
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EP (1) | EP1579017A1 (zh) |
JP (1) | JP2006509103A (zh) |
KR (1) | KR20050085402A (zh) |
CN (1) | CN1720342A (zh) |
AR (1) | AR042301A1 (zh) |
AU (1) | AU2003283455A1 (zh) |
BR (1) | BR0317061A (zh) |
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Cited By (2)
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CN101903543A (zh) * | 2007-12-17 | 2010-12-01 | 奥图泰有限公司 | 用于精炼铜精矿的方法 |
CN101827951B (zh) * | 2007-10-19 | 2012-12-12 | 保尔伍斯股份有限公司 | 含铜和其他贵金属的残渣的回收 |
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FI116686B (fi) * | 2003-07-17 | 2006-01-31 | Outokumpu Oy | Menetelmä kuparirikasteiden sulattamiseksi |
CN102605191B (zh) * | 2012-04-16 | 2013-12-25 | 阳谷祥光铜业有限公司 | 一种铜精矿直接生产粗铜的方法 |
KR101389430B1 (ko) * | 2012-08-23 | 2014-04-25 | 엘에스니꼬동제련 주식회사 | 동제련 전로슬래그에서의 유가금속 회수처리 공정법 |
KR101502592B1 (ko) * | 2013-04-12 | 2015-03-16 | 주식회사 삼삼 | 실리카 및 마그네시아 추출을 위한 슬래그의 처리방법 |
JP6363035B2 (ja) * | 2015-02-27 | 2018-07-25 | 独立行政法人国立高等専門学校機構 | 銅スラグの処理方法 |
RU2614293C2 (ru) * | 2015-06-04 | 2017-03-24 | Общество с ограниченной ответственностью "Институт Гипроникель" | Способ переработки низкоавтогенного сырья в печах взвешенной плавки |
CN116555571B (zh) * | 2023-04-27 | 2024-05-10 | 上海开鸿环保科技有限公司 | 危废污泥电热熔融资源化处理装置 |
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US4152142A (en) * | 1977-02-28 | 1979-05-01 | Kennecott Copper Corporation | Recovery of copper values from iron-containing ore materials as mined and smelted |
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US5616168A (en) * | 1994-02-28 | 1997-04-01 | Kennecott Utah Copper Corporation | Hydrometallurgical processing of impurity streams generated during the pyrometallurgy of copper |
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CA2363969C (en) * | 2001-11-26 | 2009-01-13 | Walter Curlook | Process for the recovery of residual metal values from smelter waste slags, and from converter slags |
FI114808B (fi) * | 2002-05-03 | 2004-12-31 | Outokumpu Oy | Menetelmä jalometallirikasteen jalostamiseksi |
-
2002
- 2002-12-05 FI FI20022150A patent/FI115638B/fi not_active IP Right Cessation
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2003
- 2003-11-24 WO PCT/FI2003/000898 patent/WO2004050925A1/en not_active Application Discontinuation
- 2003-11-24 US US10/536,631 patent/US20060037435A1/en not_active Abandoned
- 2003-11-24 EP EP20030775423 patent/EP1579017A1/en not_active Withdrawn
- 2003-11-24 PL PL37693203A patent/PL376932A1/pl not_active Application Discontinuation
- 2003-11-24 JP JP2004556365A patent/JP2006509103A/ja not_active Abandoned
- 2003-11-24 KR KR1020057010244A patent/KR20050085402A/ko not_active Application Discontinuation
- 2003-11-24 CN CNA2003801049585A patent/CN1720342A/zh active Pending
- 2003-11-24 BR BR0317061A patent/BR0317061A/pt not_active IP Right Cessation
- 2003-11-24 EA EA200500756A patent/EA200500756A1/ru unknown
- 2003-11-24 MX MXPA05005997A patent/MXPA05005997A/es unknown
- 2003-11-24 AU AU2003283455A patent/AU2003283455A1/en not_active Abandoned
- 2003-12-02 PE PE2003001224A patent/PE20040630A1/es not_active Application Discontinuation
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101827951B (zh) * | 2007-10-19 | 2012-12-12 | 保尔伍斯股份有限公司 | 含铜和其他贵金属的残渣的回收 |
CN101903543A (zh) * | 2007-12-17 | 2010-12-01 | 奥图泰有限公司 | 用于精炼铜精矿的方法 |
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US20060037435A1 (en) | 2006-02-23 |
FI20022150A0 (fi) | 2002-12-05 |
BR0317061A (pt) | 2005-10-25 |
AR042301A1 (es) | 2005-06-15 |
FI20022150A (fi) | 2004-06-06 |
EA200500756A1 (ru) | 2005-12-29 |
JP2006509103A (ja) | 2006-03-16 |
FI115638B (fi) | 2005-06-15 |
EP1579017A1 (en) | 2005-09-28 |
PL376932A1 (pl) | 2006-01-09 |
AU2003283455A1 (en) | 2004-06-23 |
PE20040630A1 (es) | 2004-11-11 |
KR20050085402A (ko) | 2005-08-29 |
MXPA05005997A (es) | 2005-08-18 |
WO2004050925A1 (en) | 2004-06-17 |
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