CN1004635B - 用湿法从多金属难选其生矿中提取金属化合物的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000002736 metal compounds Chemical class 0.000 title abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 241000500881 Lepisma Species 0.000 claims description 14
- 229910000679 solder Inorganic materials 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 3
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 239000003337 fertilizer Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 15
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract description 2
- 239000001099 ammonium carbonate Substances 0.000 abstract description 2
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229910000004 White lead Inorganic materials 0.000 abstract 1
- 238000012824 chemical production Methods 0.000 abstract 1
- 239000002516 radical scavenger Substances 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
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- 238000003723 Smelting Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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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- Manufacture And Refinement Of Metals (AREA)
Abstract
一种用湿法从多金属难选共生矿中提取金属化合物的方法。本法以稀硝酸为溶剂,对含低锡高铅高铁的难选共生矿进行酸浸,使铅浸出与锡分离。所得溶液控制pH值分级沉淀脱杂,直接得到化工产品硝酸铅;所得溶液也可直接以碳酸氢铵或氨水对其进行碳化沉铅,制得可转化生产多种铅盐产品的人造白铅矿。酸浸渣则选择盐酸作为铁清除剂进行铁锡分离,得到冶金和化工生产所需的锡石。产生的“废液”为硝酸铵和三氯化铁,均能以化工产品的形式回收。
Description
本发明是一种用湿法从矿石中提取金属化合物的方法,特别适用于难选低锡高铅高铁共生中矿的铅锡铁分离与回收。
目前冶炼高品位锡精矿的工业生产中,由于锡矿石中锡石成细粒分散,又与脉石致密连生,采用现有的选矿方法很难进行有效的分离,选矿回收率只有70%左右或更低,为了获得高品位的锡精矿,选矿厂常常不得不产出一部分不能再分选的锡中矿。这种含锡低的原料如用正常的还原熔炼法,不仅流程复杂,金属回收率较低,而且成本很高。现有技术中尚无用酸浸碳化法分离铅锡铁共生中矿的方法。
本发明人撰写的《从难选共生矿直接生产无机盐》的论文(详见《有色金属》1984.No.P18~21)首次提出了采用酸浸碳化法分离铅锡铁共生中矿的方法,但只对工艺流程作了一般概述。在此之后,发明人对此工艺进行了深入的研究和大量试验,掌握了各项具体的工艺条件,尤其对浸出液的浓度、分级沉淀的pH等技术关键,寻找到了最佳值。
本发明的目的在于提供一种适合工业生产的有效而完整的方法。从难选的铅锡铁共生中矿中,分离制取化工原料,发展锡盐产品,实现矿产综合利用,消除“三废”。
本发明的内容和实施方法,包括酸溶浸铅、碳化沉铅和酸浸除铁三个步骤,现分述如下:
1.酸溶浸铅:以浓度为10~15%的硝酸溶液作为溶剂,在90~98℃的温度下,对磨矿粒度为-75~100目的铅锡混合中矿(Sn5~8%、pb20~30%、Fe20~30%)进行浸出,硝酸用量为固液比=1∶1.5~2.5浸出时间为0.5~1.5小时。经过反应,铅锡铁混合中矿中的铅溶解浸出与锡铁分离。主要化学反应为:
pbCO3+2HNO3=pb(NO3)2+CO2↑+H2O
分离所得的硝酸铅溶液,可直接制取商品硝酸铅,此时只需要进一步简单地分级沉淀、分离杂质,再浓缩结晶即可。
2.碳化沉铅:以饱和碳酸氢铵溶液或浓度为15~25%的氨水对浸出分离后的硝酸铅溶液或制商品硝酸铅的母液进行碳化沉铅,反应的pH值控制在7.5~8.5,温度为常温。主要化学反应为:
3pb(NO3)2+6NH4HCO3=pb3(OH)2(CO3)2↓+6NH4NO3+4CO2↑+2H2O
pb(NO3)2+2NH4OH=pb(OH)2+2NH4NO3
溶液中过量的硝酸与碳铵反应、生成硝铵。
HNO3+NH4HCO3=NH4NO3+CO2↑+H2O
3.酸浸除铁:以浓度为15~30%的盐酸,在90~110℃的温度下,对溶铅后分离出的高铁锡精矿进行酸浸除铁,用酸量为固∶液=1∶2~4,浸出时间1~2小时。主要化学反应为:
Fe2O3+6HCl2FeCl3+3H2O
4.碳化沉铅后硝酸铵“废液”经浓缩结晶得化把硝铵∶酸浸除铁后的三氯化铁“废液”经-2~-6℃冷冻结晶得三氯化铁副产品。
发明的工艺过程示意图,详见附图。
本发明与现有技术相比,主要优点是工艺流程短捷,金属回收率高,总实收率可达80~85%;浸取铅和浸除铁都能较完全地进行,可获得锡含量>50%的锡精矿、为电炉炼锡和生产化工锡盐提供了有利条件;分离所得铅精矿为人造白铅矿(碳酸铅),不仅有利于进一步冶炼铅,而且是生产铅丹、硝酸铅、醋酸盐、三盐基硫酸铅等化工铅盐的极好原料;所得副产品硝铵为高效化把,三氯化铁可作为净水剂,媒染剂及制颜料的原料出售;使所用的硝酸,碳铵或氨水、盐酸在铅锡分离中起作用后又间接产出化工产品,而无“废液”、“废渣”,“废气”无污染,矿产得到综合利用。
例一
铅锡混合中矿的主要化学组分(%)为Sn5.25、pb20.52Fe39.44
主要工艺过程:酸溶浸铅、碳化沉铅、酸浸除铁
酸溶浸铅的反应条件:硝酸溶液的浓度10%
浸出温度96℃
磨矿粒度-85目
硝酸用量为固液比=1∶2
碳化沉铅的反应条件:使用碳酸氨铵的饱和溶液
pH值7.5
反应温度常温
酸浸除铁的反应条件:盐酸溶液的浓度25%
反应温度105℃
用酸量为固∶液=1∶3
浸出时间2小时
投入铅锡混合中矿按1000公斤计,可获得以下产品及指标:
(1)人造白铅矿(92.47公斤):pb57.41%、Sn0.01%、Fe3.21%
(2)硝铵(20公斤):N30%、As0.001%
(3)硝酸铅(215.4公斤):pb(NO)98.01%、水不溶物<0.1%、游离酸0.2%
(4)锡精矿(84.6公斤):Sn50.83%、pb2.51%、Fe4.22%
例二
铅锡混合中矿的主要化学组分(%)为Sn8.14%、pb28.31%
Fe30.21% Fe30.21%
主要工艺过程:同例一
酸溶浸铅的反应条件:硝酸溶液的浓度14%
浸出温度94℃
磨矿粒度-100目
硝酸用量为固液比=1∶2.5
碳化沉铅的反应条件:氨水的浓度20%
pH值8.2
反应温度常温
酸浸除铁的反应条件:盐酸溶液的浓度20%
反应温度105℃
用酸量为固∶液=1∶2.5
浸出时间1.5小时
投入铅锡混合中矿按1000公斤计,可获得以下产品及指标:
(1)人造白铅矿(86.44公斤):pb70.08%、Sn0.03%
Fe1.34%
(2)硝铵(23公斤):N32%、As0.0009%
(3)硝酸铅(309.7公斤):pb(NO3)298.56%水不溶物<0.1%、游离酸0.15%
(4)锡精矿(96.4公斤):Sn70.01%、pb1.05%、Fe2.01%
例三
铅锡混合中矿的主要化学组分(%)为Sn6.5%、pb25.69%、Fe26.47%
主要工艺过程:同例一
酸溶浸铅的反应条件:硝酸溶液的浓度11%
浸出温度94℃目
磨矿粒度-90目
硝酸用量为固液比=1∶2
碳化沉铅的反应条件:氨水的浓度18%
pH值8.0
反应温度常温
酸浸除铁的反应条件:盐酸溶液的浓度18%
反应温度100℃
用酸量为固∶液=1∶2.5
浸出时间1.5小时
投入铅锡混合中矿按1000公斤计,可获得以下产品及指标:
(1)人造白铅矿(95.6公斤):Pb62.13%、Sn0.02%、Fe2.31%
(2)硝铵(19.5公斤):N33%、As0.007%
(3)硝酸铅(272.3公斤):Pb(NO3)298.24%水不溶物<0.1%游离酸0.12%
(4)锡精矿(89.3公斤):Sn60.22%、Pb1.95%、Fe3.05%
Claims (7)
1、一种用湿法分离多金属难选共生矿提取金属化合物的方法,其特征在于以下步骤:
(1)以10~15%的稀硝酸作溶剂,按1∶1.5~2.5的固液比。在90~98℃的温度下,对磨矿粒度-75~-100目的铅锡铁难选共生中矿进行浸出,
(2)依据杂质元素的氢氧化物发生沉淀的pH值调整浸出液的pH值,分级沉淀。分离杂质,浓缩结晶,直接制取商品硝酸铅,
(3)以饱和碳酸氢铵溶液或15~25%的氨水对浸出分离后的硝酸铅浸出原液或制商品硝酸铅的母液进行碳化沉铅,反应的pH值控制在7.5~8.5,温度为常温,
(4)碳化沉铅后的母液蒸发结晶,回收化肥级硝铵,
(5)以浓度为15~30%的盐酸,按1∶2~4的固液比,在90~110℃的条件下,对浸出渣高铁锡精矿进行酸浸除铁,浸出时间1~2小时,
(6)酸浸除铁后的浸出液在-2~-6℃的条件下冷冻结晶,回收工业品级的三氯化铁,
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