CN103614573B - A kind of low grade lead, antimony complex multi-metal ore deposit produces cubic stibium trioxide technique - Google Patents
A kind of low grade lead, antimony complex multi-metal ore deposit produces cubic stibium trioxide technique Download PDFInfo
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- CN103614573B CN103614573B CN201310668492.7A CN201310668492A CN103614573B CN 103614573 B CN103614573 B CN 103614573B CN 201310668492 A CN201310668492 A CN 201310668492A CN 103614573 B CN103614573 B CN 103614573B
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Abstract
The invention belongs to technical field of wet metallurgy, particularly a kind of low grade lead, antimony complex multi-metal ore deposit produces cubic stibium trioxide technique.Raw material use low grade lead, antimony complex multi-metal ore deposit (antimony content is less than 14.56%), by chlorination leaching extract antimony obtain antimony chloride solution, hydrolysis removal of impurities, drip ammonia neutralization add the stibium trioxide that the processes such as compound modifying agent obtain cubic.The present invention adopts chlorine as leaching agent, and both taken into account the advantage of antimony pentachloride as leaching agent simultaneously, do not introduced metallic impurity ion again, and without sulfur dioxide gas body pollution and dust pollution, energy consumption is lower, the rate of recovery is higher, good product quality, and production cost is lower.Resource can be fully utilized fully, improves resource utilization, reduces waste discharge, preserves the ecological environment, and is especially of great significance at process low-grade complex antimony ore.
Description
One, technical field
The invention belongs to technical field of wet metallurgy, particularly a kind of low grade lead, antimony complex multi-metal ore deposit produces cubic stibium trioxide technique.
Two, background technology
Low-grade antimony ore is due to mineralogical composition complexity, the non-ferrous metal of association is many, and embedding cloth degree is high, sorting difficulty, the rate of recovery of ore dressing is not high, multiple valuable metal separation difficulty, this type of resources development and utilization is more difficult at present, mostly deposits as slack resources, also have and exploit utilization on a small scale, but it is high to there is power consumption, the problems such as cost is high, seriously polluted.
Cubic stibium trioxide (sb
2o
3) production method be divided into pyrogenic process and wet method two kinds, at present based on pyrogenic process, its output accounts for more than 95% of stibium trioxide ultimate production.The raw material that pyrogenic process produces stibium trioxide is generally purer simple substance antimony, and the production of simple substance antimony mostly adopts a step pyrometallurgical smelting process roasting reduction stibnite concentrate, pollutes larger.In pyrogenic process free pollution metallurgy, caustic fusion method has the advantages such as metal recovery rate is high, smelting temperature is low, pollution is few, but ingredient requirement is higher containing antimony amount.And the plumbous antimony sulfide mineral of complex multi-metal, antimony content is not high, containing a large amount of lead, and containing impurity such as iron, copper, calcium, arsenic, silicon-dioxide, to blow the lead antimony alloy often instead of simple substance antimony that obtain with pyrogenic process, further separation difficulty, low-grade antimony ore pyrogenic process direct production stibium trioxide is more difficult.
Current wet processing antimony ore mainly contains following several method: one, sodium sulphite leaching-electrodeposition method, first USSR (Union of Soviet Socialist Republics) La Ziduoliningsiji associated enterprises adopts, domestic also have similar factory processes jamesonite, this method antimony recovery is high, pollute few, but sodium sulphite hyperplasia is serious, and liquid waste disposal amount is large and numerous and diverse, and current efficiency is lower; Two, iron(ic) chloride leaching-electrodeposition method, this method technical process is simple, stronger to raw mineral materials adaptability, the element sulphur be combined with antimony enters in slag with elemental sulfur form, eliminates the pollution of sulfurous gas, but impurities accumulation speed in solution, anion-exchange membrane costly and easily loss, electrodeposition control condition is harsh, magazins' layout difficulty, and industrial applications exists sizable difficulty; Three, chlorination-dry distillation, this technique valuable metal element recovery rate is high, and comprehensive utilization is made good use of, but flow process is numerous and diverse, and production cost is high, is not suitable for large-scale industrial applicability.Also have and adopt antimony pentachloride as leaching agent, just rest on conceptual phase.Central South University adopts chloride-hydrolysis process jamesonite, this method is that the process of the plumbous antimony ore of complex multi-metal provides the necessary technical support, and be only suitable for antimony and be not less than 30%, the antimony sulfide ore of plumbous≤0.1%, does not also have feasible technical study so far for the plumbous antimony-polymetal deposit (antimony is lower than 15%) of low-grade complex.
Cubic stibium trioxide industrially has important and purposes widely, as the fire retardant of resin, plastics, fiber, rubber, weaving, paint, pigment, paper etc.; Enamel, plastics, rubber, knit dye etc. and cover agent, weighting agent, mordant; Finings in glass industry; Catalyzer etc. in organic synthesis industry.Recent photoelectric technology, infrared technique, magnetic strength technical elements are all in the application of exploitation cubic stibium trioxide, and the application development especially in antimony oxygen fireproofing agent is rapid especially.Present cubic stibium trioxide adopts pyrometallurgical smelting direct production more, and the stibium trioxide of wet method direct production is rhombic system, also studies have found that, orthorhombic forms stibium trioxide is temperature 400 DEG C, vacuum-drying time 4h under pressure 666.5Pa, in stibium trioxide, cubic system can reach 99.6%.
Stibium trioxide two kinds of crystalline structure difference determined by its different coordination polyhedron structural motif and mode of connection thereof.Orthorhombic forms stibium trioxide is by simple SbO
3e coordination tetrahedron corner-sharing is formed by connecting, and its basic growth unit is simple SbO
3e coordination tetrahedron, antimony is four-coordination (comprising lone-pair electron).Cubic stibium trioxide is then by four spherical tetrahedron SbO
3+3e corner-sharing is formed by connecting, Sb
4o
6molecule is by peripheral virtual six Sauerstoffatoms and adjacent S b
4o
6point sub-connection reconstructs crystal macromole, and its basic growth unit is SbO
3+3the spherical tetrahedron of E, wherein antimony is seven coordinations (comprising lone-pair electron), Sb
4o
6molecule is then the characteristic structural motifs of cubic stibium trioxide.Sb in orthorhombic forms stibium trioxide unit cell
2o
3molecule number is much smaller than Sb in cubic stibium trioxide unit cell
2o
3molecule number, and orthorhombic forms stibium trioxide structure is more similar to antimony oxychloride, and the Entropy Changes of both phase transformations is less than the Entropy Changes that orthorhombic forms antimony oxychloride is converted into cube stibium trioxide, therefore more easily changes forming orthorhombic forms Sb in hydrolysis with conversion process antimony oxychloride
2o
3nucleus, and corresponding generation orthorhombic forms stibium trioxide.
Three, summary of the invention
Produce cubic stibium trioxide Problems existing for the plumbous antimony-polymetal deposit of current low-grade complex, improve the utilization ratio of the plumbous antimony-polymetal deposit of low-grade complex further, propose the present invention.The technical scheme that the present invention intends taking is: a kind of low grade lead, antimony complex multi-metal ore deposit produces cubic stibium trioxide technique, it is characterized in that low grade lead, antimony complex multi-metal ore deposit to be milled to be less than 150 orders, drop in reactor, add the water of 300% ~ 500% weight of ore deposit amount weight, stir, the chlorine of 11% ~ 19% weight of ore deposit amount weight is passed into bottom reactor, chlorine flow velocity first quick and back slow, temperature controls more than 90 DEG C, reaction 3.5 ~ 4.5h, temperature is reduced to less than 50 DEG C, Filter Press, leaching liquid enters in reactor to stir, the water adding 5 ~ 9 times of leaching liquid weight under normal temperature is hydrolyzed, hydrolysis time 0.5 ~ 2h, after hydrolysis, press filtration is separated, the saturated nacl aqueous solution of 1.5 ~ 2.5 times of weight is added by the weight of gained filter cake, stir immersion 4 ~ 6h deleading, press filtration is separated, filter cake washs with dilute hydrochloric acid more further, washing lotion is with till nothing+divalent iron ion, filter cake reenters in reactor, the water adding 1.5 ~ 3 times of weight of filter cake weight is sized mixing, stir and add stibium trioxide compound modifying agent, stibium trioxide compound modifying agent is sodium tartrate or soluble tartrate or ammonium tartrate, stibium trioxide compound modifying agent is 1:18 ~ 30 with the amount ratio of filter cake, drip ammoniacal liquor under normal temperature to stir, control reaction end PH=7.8 ~ 8.2, reaction times 1.5 ~ 3h, press filtration is separated, filter cake is washed, inspection washing lotion is without chlorion, wet cake after washing dries 1.5 ~ 3h in 100 ~ 120 DEG C, baking oven, namely cubic stibium trioxide is obtained.
Raw material use low grade lead, antimony complex multi-metal ore deposit (antimony content is less than 14.56%), by chlorination leaching extract antimony obtain antimony chloride solution, hydrolysis removal of impurities, drip ammonia neutralization add the stibium trioxide that the processes such as compound modifying agent obtain cubic.The effect of tartrate ion is to change in antimony oxychloride and conversion reaction course, changes Sb by a kind of " location " effect
2o
3growth unit and mode of connection thereof, reaction generates antimony coordination ion and dissolves, coordination ion and OH in solution
-there is directionally hydrolyzing in reaction, makes precipitated product generate stable cubic Sb
2o
3and the concentration that have impact on precipitating ion in solution is combined with antimony ion, the nucleation and growth of precipitation particles is had an impact, simultaneously may because its with electric charge, ionic size inhibit growth and the reunion of precipitation, so generate the particle of single dispersing fine size.
The present invention adopts chlorine as leaching agent, and both taken into account the advantage of antimony pentachloride as leaching agent simultaneously, do not introduced metallic impurity ion again, and without sulfur dioxide gas body pollution and dust pollution, energy consumption is lower, the rate of recovery is higher, good product quality, and production cost is lower.Resource can be fully utilized fully, improves resource utilization, reduces waste discharge, preserves the ecological environment.Especially be of great significance at process low-grade complex antimony ore.
Four, accompanying drawing explanation
Fig. 1 is present invention process schema
Five, embodiment
Example 1: take 150 order low grade lead, antimony complex multi-metal ore deposits 100Kg breeze (containing antimony 14.56%) and directly drop in reactor, the 300kg that adds water stirs, pass into bottom 19Kg chlorine to reactor, flow velocity first quick and back slow, temperature controls more than 90 DEG C, react 3.5 hours, temperature is reduced to less than 50 DEG C and adopts plate-and-frame filter press to filter, leaching process reaction equation:
Sb
2S
3+3Cl
2=2SbCl
3+3S
SbCl
3+Cl
2=SbCl
5
3SbCl
5+Sb
2S
3=5SbCl
3+3S
Leaching slag otherwise processed, obtain leaching liquid 350L to enter in enamel reaction still to stir, 5 times of water yield hydrolysis of leaching liquid weight are added under normal temperature, hydrolysis time 2h, is hydrolyzed laggard row filter press and is separated, add the saturated nacl aqueous solution of 1.5 times of weight by the weight of gained filter cake antimony oxychloride, stir and soak 4h deleading, press filtration is separated, more further with dilute hydrochloric acid washing, washing lotion is with till nothing+divalent iron ion.Hydrolytic process reaction equation:
SbCl
3+H
2O=SbOCl+2HCl
4SbCl
3+5H
2O=Sb
4O
5Cl
2+10HCl
Filter cake is after edulcoration purification washing, obtain purer filter cake antimony oxychloride 20.3Kg, antimony oxychloride drops in reactor the water adding 1.5 times of antimony oxychloride weight again and sizes mixing, and stirs and adds stibium trioxide compound modifying agent sodium tartrate, antimony oxychloride is 18:1 with the amount ratio of sodium tartrate, i.e. 1.53kg, drips ammoniacal liquor under normal temperature, controls reaction end PH=7.8, reaction times 1.5h, press filtration is separated, and filter cake antimonous oxide is after washing, and inspection washing lotion is without chlorion.Ammonification N-process reaction equation is:
2SbOCl+2NH
3·H
2O=Sb
2O
3+2NH
4Cl+H
2O
Sb
4O
5Cl
2+2NH
3·H
2O=2Sb
2O
3+2NH
4Cl+H
2O
Wet cake antimonous oxide after washing dries 3 hours at baking oven 10O DEG C, obtains cubic stibium trioxide 16.78Kg.Cubic stibium trioxide quality reaches GB4062-1998 zero level standard, detected value: Sb
2o
399.65%, As
2o
30.05%, PbO0.06%, Fe
2o
30.002%, CuO0.001%, whiteness 97.
Example 2, take 200 order low grade lead, antimony complex multi-metal ore deposits 100Kg breeze (containing antimony 10.58%) and directly drop in reactor, the 500kg that adds water stirs, pass into bottom 14Kg chlorine to reactor, flow velocity first quick and back slow, temperature controls more than 90 DEG C, react 4.5 hours, temperature is reduced to less than 50 DEG C and adopts plate-and-frame filter press to filter, and leaching process reaction equation is with embodiment 1.
Leaching slag otherwise processed, obtain leaching liquid 510L to enter in enamel reaction still to stir, 9 times of water yield hydrolysis of leaching liquid weight are added under normal temperature, hydrolysis time 0.5h, is hydrolyzed laggard row filter press and is separated, add the saturated nacl aqueous solution of 3 times of weight by the weight of gained filter cake antimony oxychloride, stir and soak 6h deleading, press filtration is separated, more further with dilute hydrochloric acid washing, washing lotion is with till nothing+divalent iron ion.Hydrolytic process reaction equation is with embodiment 1.
Filter cake is after edulcoration purification washing, obtain purer antimony oxychloride 14.5Kg, antimony oxychloride drops in reactor the water adding 3 times of antimony oxychloride weight again and sizes mixing, and stirs and adds stibium trioxide compound modifying agent sodium tartrate, antimony oxychloride is 30:1 with the amount ratio of sodium tartrate, i.e. 0.68kg, drips ammoniacal liquor under normal temperature, controls reaction end PH=8.2, reaction times 3h, press filtration is separated, and filter cake antimonous oxide is after washing, and inspection washing lotion is without chlorion.Ammonification N-process reaction equation is with embodiment 1.
Wet cake after washing dries 1.5 hours in 120 DEG C, baking oven, obtains cubic stibium trioxide 12.45Kg.Cubic stibium trioxide quality reaches GB4062-1998 zero level standard, detected value: Sb
2o
399.75%, As
2o
30.04%, PbO0.07%, Fe
2o
30.002%, CuO0.001%, whiteness 96.
Claims (1)
1. a low grade lead, antimony complex multi-metal ore deposit produces cubic stibium trioxide technique, the low grade lead, antimony complex multi-metal ore deposit that it is characterized in that antimony content to be less than 10.58% is milled to and is less than 150 orders, drop in reactor, add the water of 300% ~ 500% weight of ore deposit amount weight, stir, the chlorine of 11% ~ 19% weight of ore deposit amount weight is passed into bottom reactor, chlorine flow velocity first quick and back slow, temperature controls more than 90 DEG C, reaction 3.5 ~ 4.5h, temperature is reduced to less than 50 DEG C, Filter Press, leaching liquid enters in reactor to stir, the water adding 5 ~ 9 times of leaching liquid weight under normal temperature is hydrolyzed, hydrolysis time 0.5 ~ 2h, after hydrolysis, press filtration is separated, the saturated nacl aqueous solution of 1.5 ~ 2.5 times of weight is added by the weight of gained filter cake, stir immersion 4 ~ 6h deleading, press filtration is separated, filter cake washs with dilute hydrochloric acid more further, washing lotion is with till nothing+divalent iron ion, filter cake reenters in reactor, the water adding 1.5 ~ 3 times of weight of filter cake weight is sized mixing, stir and add stibium trioxide compound modifying agent, stibium trioxide compound modifying agent is sodium tartrate or soluble tartrate or ammonium tartrate, stibium trioxide compound modifying agent is 1:18 ~ 30 with the amount of substance ratio of filter cake, drip ammoniacal liquor under normal temperature to stir, control reaction end pH=7.8 ~ 8.2, reaction times 1.5 ~ 3h, press filtration is separated, filter cake is washed, inspection washing lotion is without chlorion, wet cake after washing dries 1.5 ~ 3h in 100 ~ 120 DEG C, baking oven, namely cubic stibium trioxide is obtained.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1022477C (en) * | 1987-11-25 | 1993-10-20 | 冶金工业部长沙矿冶研究院 | Process for directly producing graded antimony white from antimony ore |
| CN102070194A (en) * | 2011-02-21 | 2011-05-25 | 湖南辰州矿业股份有限公司 | Method for producing antimonous oxide by wet method to improve whiteness |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1022477C (en) * | 1987-11-25 | 1993-10-20 | 冶金工业部长沙矿冶研究院 | Process for directly producing graded antimony white from antimony ore |
| CN102070194A (en) * | 2011-02-21 | 2011-05-25 | 湖南辰州矿业股份有限公司 | Method for producing antimonous oxide by wet method to improve whiteness |
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