CN108913898B - 一种高铋铅阳极泥的处理工艺 - Google Patents
一种高铋铅阳极泥的处理工艺 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 100
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000002893 slag Substances 0.000 claims abstract description 65
- 229910052709 silver Inorganic materials 0.000 claims abstract description 44
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004332 silver Substances 0.000 claims abstract description 42
- 238000003723 Smelting Methods 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 17
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 10
- 238000007670 refining Methods 0.000 claims abstract description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 8
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims abstract description 6
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000779 smoke Substances 0.000 claims abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims abstract description 4
- 239000011133 lead Substances 0.000 claims description 36
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- UDRRLPGVCZOTQW-UHFFFAOYSA-N bismuth lead Chemical compound [Pb].[Bi] UDRRLPGVCZOTQW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 6
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- -1 copper metals Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910001923 silver oxide Inorganic materials 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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Abstract
一种高铋铅阳极泥的处理工艺,包括将高铋铅阳极泥进行富氧还原熔炼,产出贵铋、炉渣(铅渣)和烟尘(粗锑白)。铅渣和粗锑白分别送铅系统和锑系统,贵铋进行真空蒸馏,蒸馏后产出毛银、粗铋和碲渣,粗铋送火法精炼产出精铋,碲渣送碲回收率车间产出精碲,毛银经分银炉吹炼后产出粗银和铋渣,粗银送银电解车间生产白银黄金,铋渣再送转炉进行还原造锍熔炼产出贵铋和冰铜渣,贵铋返回真空蒸馏工序,而冰铜渣送氧压浸出铜电积工序分别产出阴极铜和铅银渣。阴极铜作为产品出售,铅银渣返回铅冶炼系统。本发明具有流程简单,生产效率高,周期短,有价金属回收率高,生产成本低等特点。
Description
技术领域
本发明涉及一种高铋铅阳极泥的处理工艺,属于有色重贵金属冶金领域。
背景技术
铅阳极泥是粗铅电解精炼时的一个副产品,它是生产金银等贵金属的一个主要原料,同时也是回收铋锑铜碲等有价金属的一种主要原料,其中含铋的铅阳极泥是生产精铋的主要原料,含铋铅阳极泥传统的处理方法是将阳极泥用反射炉(或转炉)还原熔炼成贵铅,然后把贵铅在转炉氧化吹炼产出粗银和铋渣,粗银送银电解精炼,产出白银黄金等,而铋渣利用小鼓风炉等炉窑还原熔炼成粗铋,粗铋再经过多个工序的火法精炼产出精铋。传统的工艺虽有设备投资少,上马快,操作方便的优点,但该工艺产出的粗铋主含量低往往只有50-70%,火法精炼时工序多,生产周期长,铋的直收率低,往往只有30-40%,精炼渣量大,滞留的有价金属量多,占用的资金多,生产成本高,所以国内外大多数企业已不用该工艺生产。
2007年12月05日,中国发明专利申请公布号CN101082084A ,公布了(杨跃新等人)从铋渣中回收冶炼精铋的工艺,该工艺是先湿法后火法方法回收转炉铋渣中的铋,即将转炉产出铋渣用机械粉碎后用盐酸溶液浸出,铅金银与铋铜分离效果好,粗铋质量好,易于精炼等优点,但湿法工艺生产线长,操作要求高,同时产出大量的氯化钠溶液需要蒸发导致能源消耗高,生产成本高。
“从阳极泥中回收铋新工艺生产实践”,任建民、黄宪涛等,《中国金属通报》,第24卷,第3期,第42-43页,2017年)介绍了从阳极泥中回收铋新工艺情况,该工艺实际上亦是将铅阳极泥还原熔炼或贵铅,贵铅在分银炉中氧化吹炼产出氧化铋渣,氧化铋再经还原熔炼产出粗铋,粗铋再经除铜,除铅等工序后进行真空蒸馏,蒸馏产物再经高温精炼产出精铋。该工艺前段与传统工艺完全相同,只是在粗铋精炼时用真空蒸馏代替了加锌除银工艺,因此该工艺仍然存在精炼渣量大,滞留有价金属多,铋的直收率较低,生产成本高问题。
发明内容
为了克服上述工艺的不足,本发明提供了一种高铋铅阳极泥的处理工艺,该工艺具有流程简单,生产效率高,周期短,有价金属综合回收率高,加工成本低等特点。
本发明一种高铋铅阳极泥的处理工艺,包括以下步骤:
a高铋铅阳极泥的富氧还原熔炼
所述高铋铅阳极泥含Bi≥8.0%,含Ag5000-60000g/t,Bi:Pb 0.5-5.0;采用富氧熔炼,强化了熔炼过程,提高了效率,在熔炼过程控制适当条件,使绝大部分铋和金银及部分铅铋进入贵铋中,绝大部分锑进入烟尘中,大部分铅进入氧化铅渣中,逐步实现铋和金银与铅锑的分离;
b贵铋的真空蒸馏
利用铋与金银几种金属的沸点差异,在接近真空的状态下控制合理的温度使贵铋中的铋、铅、碲优先挥发出来,金、银和铜金属在残留的合金中,经过真空蒸馏,分别得到粗铋、毛银与碲渣;碲渣和粗铋分别送碲回收车间和铋精炼车间生产精碲和精铋,毛银则送分银炉吹炼,产出粗银和铋渣;
所述贵铋的真空蒸馏包括一次蒸馏、二次蒸馏和三次蒸馏,温度控制一次蒸馏950-1050℃,二次蒸馏900-950℃,三次蒸馏800-900℃,真空度3-10Pa;
c铋渣的还原造锍熔炼
贵铋真空蒸馏产出的毛银经转炉氧化吹炼后,得到粗银和氧化铋渣;由于铋渣中含有较高的铜,铋渣投入转炉中进行还原造锍熔炼,利用硫对铜的亲和力大的特性熔炼时加入硫精矿,铋渣中的铜以硫化物的形式进入冰铜渣中,而铋渣中的铋则被还原进入第二贵铋中;第二贵铋返回真空蒸馏;冰铜渣送氧压浸出和铜电积工序得到阴极铜产品和浸出渣,浸出渣也称铅银渣,返回铅系统回收金银铅金属;
所述的还原造锍熔炼,还原煤率2-5%,硫精矿率8-18%,炉温1250-1300℃。、
所述富氧还原熔炼适当条件是:还原煤率1-5%,氧气浓度92.5%-99.5%,氧压0.15-0.6Mpa,炉温900-1100℃。
所述的烟尘是粗锑白。
所述第二贵铋返回真空蒸馏是:铋渣还原造锍熔炼产出的第二贵铋与a步骤产出的贵铋一道进行真空蒸馏。
本发明具有流程简单,生产效率高,周期短,有价金属回收率高,生产成本低等特点。
附图说明
图1是本发明的工艺流程图。
具体实施方式
实施例1
详细流程见附图1;
1、阳极泥富氧熔炼
将含Bi 38.29%、Pb 22.74%、Sb 16.96%、Cu 0.91%、Te 0.16%、Ag 27597(g/t)、Au41.3(g/t)的阳极泥并配入2.5%的还原煤投入到氧气侧吹炉还原熔炼,采用氧气浓度98%,氧压0.25MPa,炉温900-950℃,得到产物贵铋合金,炉渣和烟尘。炉渣含Pb 35.2%、Sb14.56%、Bi 1.5%、Ag 524(g/t),该渣作为炼铅原料返回铅冶炼系统回收铅银锑等有价金属。烟灰含Sb 61.77%、Pb 8.26%、Bi 2.28%、Ag 635(g/t)、作为炼锑白的原料送至锑冶炼系统;贵铋合金含Bi 73.92%、Pb 14.55%、含Ag 69811(g/t);
2、贵铋的真空蒸馏
将上述贵铋合金置于真空炉内进行蒸馏,控制真空炉真空度3-10Pa,温度一次蒸馏950-1050℃、二次900-950℃、三次800-900℃,得到蒸馏产物毛银、粗铋和碲渣,毛银含Bi10.80%、Pb 16.17%、Sb 10.56%、Cu 9.98%、含银521328(g/t);粗铋含Bi 86.96%、Pb10.93%、Ag 35(g/t)。碲渣含Te28.11%;
3、铋渣的还原造锍熔炼
毛银经分银炉吹炼后,产出Ag+Au>98.0%的合金即粗银,同时产出铋渣;粗银送银电解工序生产白银和黄金。铋渣含Bi 32.6%,Pb21.3%,Cu 10.5%,Ag 3043(g/t),配入3.5%的还原煤,15%的硫精矿投入转炉中在1250-1300℃的温度进行造锍还原熔炼产出贵铋和冰铜渣,贵铋含Bi 56.25%、Pb 25.46%、Cu 1.47%、Ag 52350(g/t),返回真空蒸馏工序。冰铜渣含Cu 31.5%、Bi2.55%、Pb 16.23%、Ag11412(g/t)送氧压浸出和铜电积工序产出Cu99.5%阴极铜和浸出渣即铅银渣,含Pb18.7%、Bi 2.93%、Cu 1.85%、Ag13123(g/t);阴极铜产品直接出售,铅银渣返回铅冶炼做炼铅原料。
本实施例相关指标
铋的回收率 98.51%,直收率81.22%;
银的回收率99.21%,直收率90.55%;
精铋加工成本10218元/t。
Claims (3)
1.一种高铋铅阳极泥的处理工艺,其特征在于:包括以下步骤:
a高铋铅阳极泥的富氧还原熔炼
将含Bi 38.29%、Pb 22.74%、Sb 16.96%、Cu 0.91%、Te 0.16%、Ag 27597(g/t)、Au 41.3(g/t)的阳极泥并配入2.5%的还原煤投入到氧气侧吹炉还原熔炼,采用氧气浓度98%,氧压0.25MPa,炉温900-950℃,得到产物贵铋合金,炉渣和烟尘;炉渣含Pb 35.2%、Sb 14.56%、Bi1.5%、Ag 524(g/t),该渣作为炼铅原料返回铅冶炼系统回收铅银锑等有价金属;烟灰含Sb61.77%、Pb 8.26%、Bi 2.28%、Ag 635(g/t)、作为炼锑白的原料送至锑冶炼系统;贵铋合金含Bi 73.92%、Pb 14.55%、含Ag 69811(g/t);
b贵铋的真空蒸馏
利用铋与金银几种金属的沸点差异,在接近真空的状态下控制合理的温度使贵铋中的铋、铅、碲优先挥发出来,金、银和铜金属在残留的合金中,经过真空蒸馏,分别得到粗铋、毛银与碲渣;碲渣和粗铋分别送碲回收车间和铋精炼车间生产精碲和精铋,毛银则送分银炉吹炼,产出粗银和铋渣;
所述贵铋的真空蒸馏包括一次蒸馏、二次蒸馏和三次蒸馏,温度控制一次蒸馏950-1050℃,二次蒸馏900-950℃,三次蒸馏800-900℃,真空度3-10Pa;
c铋渣的还原造锍熔炼
贵铋真空蒸馏产出的毛银经转炉氧化吹炼后,得到粗银和氧化铋渣;由于铋渣中含有较高的铜,铋渣投入转炉中进行还原造锍熔炼,利用硫对铜的亲和力大的特性熔炼时加入硫精矿,铋渣中的铜以硫化物的形式进入冰铜渣中,而铋渣中的铋则被还原进入第二贵铋中;第二贵铋返回真空蒸馏;冰铜渣送氧压浸出和铜电积工序得到阴极铜产品和浸出渣,浸出渣也称铅银渣,返回铅系统回收金银铅金属;
所述的还原造锍熔炼,还原煤率2-5%,硫精矿率8-18%,炉温1250-1300℃。
2.根据权利要求1所述的一种高铋铅阳极泥的处理工艺,其特征在于:所述的烟尘是粗锑白。
3.根据权利要求1所述的一种高铋铅阳极泥的处理工艺,其特征在于:所述第二贵铋返回真空蒸馏是:铋渣还原造锍熔炼产出的第二贵铋与a步骤产出的贵铋一道进行真空蒸馏。
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