CN105112676A - Method for recovering iron in fayalite metallurgy slag through roasting of iron pyrite - Google Patents
Method for recovering iron in fayalite metallurgy slag through roasting of iron pyrite Download PDFInfo
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- CN105112676A CN105112676A CN201510568445.4A CN201510568445A CN105112676A CN 105112676 A CN105112676 A CN 105112676A CN 201510568445 A CN201510568445 A CN 201510568445A CN 105112676 A CN105112676 A CN 105112676A
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- iron
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- fayalite
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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
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Abstract
The invention discloses a method for recovering iron in fayalite metallurgy slag through roasting of iron pyrite. The method comprises the steps that the iron pyrite is added into the fayalite metallurgy slag, leaching is conducted by means of an acid solution after oxidizing roasting of the iron pyrite is conducted at the temperature of 300-1100 DEG C, and the leaching rate of iron is equal to or higher than 94%; or strong magnetic separation is conducted, and the content of iron in magnetic concentrate reaches 66%. According to the method, the iron in the fayalite metallurgy slag and iron in pyrite cinder are effectively recovered through natural oxidizing roasting of the iron pyrite, and the method has an obvious effect on minimization and reclamation of the fayalite metallurgy slag and the pyrite cinder.
Description
Technical field:
The invention belongs to metallurgical engineering and environmental engineering crossing domain, relate to a kind of method that pyrite roasting fayalite class metallurgical slag reclaims iron, be specifically related to a kind of method of the fayalite class metallurgical slags such as lead skim, copper ashes, nickel slag being carried out to roasting recovery iron.
Background technology:
China is the first in the world Iron and Steel Production big country, but China's iron ore deposit is poor, and a large amount of iron ore deposits relies on external import, and China's iron ore dependence on import continuous 6 years is more than 60%.Meanwhile, China produces a large amount of metallurgical slag every year, the iron resources that in these metallurgical slags, association is a large amount of.Wherein Copper making industry produces millions of tons of copper ashes every year, iron content 40% in copper ashes; Plumbous smelting industry produces millions of tons of lead skims, iron content 21-31% in lead skim every year; Nickel fibers industry produces millions of tons of nickel slags every year, nickel slag iron content 30-40%.These slags are stored up in a large number at present, cause environmental pollution and the wasting of resources.Reclaim iron resources in the fayalite class metallurgical slag such as copper ashes, lead skim, nickel slag for the minimizing of metallurgical slag and iron resources, the chronic shortage making up China's iron ore resource is significant.
In copper ashes, lead skim, nickel slag, the recovery of iron mainly obtains iron ore concentrate by oxidation/reduction roasting-magnetic separation, direct-reduction-magnetic separation obtains iron ore concentrate, Direct Reductive Melting obtains iron alloy.In copper ashes, lead skim, nickel slag, iron mainly exists mutually with fayalite thing.Fayalite stable in properties, below 1000 DEG C, carry out oxidizing roasting with oxygen or carry out reducing roasting with carbon monoxide/carbon, the transformation efficiency that fayalite is converted into four oxidation two iron or ferric oxide is all not high, therefore oxidation/reduction roasting-magnetic separation process fayalite class metallurgical slag effect is undesirable, and particularly during process lead skim, iron does not have concentration effect.Direct-reduction-magnetic separation then will add a large amount of coals, and 1000-1200 DEG C of reduction, Direct Reductive Melting reduces under the condition of > 1400 DEG C, and energy consumption is high.Fayalite is insoluble to diluted acid, cannot directly leach, and with after concentrated acid pulp, just dissolves under the condition of strong acid high temperature.
In sum, in current fayalite class metallurgical slag, the recycling of iron resources lacks effective means, makes iron resources in these metallurgical slags can not get effective recycling.In fayalite class metallurgical slag, the recycling of iron resources is metallurgical and an environmental area difficult problem urgently to be resolved hurrily, in the urgent need to the iron resources of association in a kind of energy-conservation, efficient, processing method recovery fayalite class metallurgical slag that flow process is short.
Summary of the invention:
The object of the invention is for above-mentioned Problems existing, provide a kind of pyrite roasting fayalite class metallurgical slag to reclaim the method for iron.By adding pyrite roasting by fayalite thing phase decomposition in waste residue, then reclaim iron by the mode of leaching or magnetic separation.
A kind of pyrite roasting fayalite class metallurgical slag reclaims the method for iron: the one in optional following two schemes:
(1) fayalite class metallurgical slag adds pyrite, roasting under aerobic conditions, after roasting completes, fired slags acid solution is carried out leaching and obtains iron content leach liquor, or fired slags is carried out high intensity magnetic separation obtains iron ore concentrate;
(2) fayalite class metallurgical slag is added pyrite two sections of low-temperature bakes in oxidizing atmosphere, after fired slags waits valuable metal with weak-acid leaching zinc-copper lead, then obtain iron content leach liquor or carry out high intensity magnetic separation obtaining iron ore concentrate with acid solution leaching.
In scheme (1), maturing temperature is 300-1100 DEG C, and preferred 450-900 DEG C roasting time is 15-180min, preferred 60-90min.
In scheme (2), two sections of low-temperature bakes refer to 300-600 DEG C of roasting 30-150min, preferred 30-90min, then at 600-700 DEG C of roasting 30-150min, preferred 30-60min.
Weight of iron in above-mentioned pyrite/fayalite class metallurgical slag is than=1 ~ 8.
Weight of iron in above-mentioned pyrite/fayalite class metallurgical slag is than being preferably 1 ~ 3.
Oxygen concentration in two schemes is 1-100%, and preferably 100%.
The acid solution leaching iron in two schemes is the hydrochloric acid of the sulfuric acid of 20-98%, 8-38%, the nitric acid of 14-69%, any one of the acetic acid of 12-56%; The sulfuric acid of preferred 30-50%, the hydrochloric acid of 12-19%, the nitric acid of 20-35%, the acetic acid of 15-28%; The solid mass ratio of leach liquor is (5 ~ 20)/1, preferably (5 ~ 10)/1; Extraction time 1 ~ 60min; Extraction temperature 25-100 DEG C.
In scheme (2) weakly acid soln of leaching valuable metal be sulfur acid, hydrochloric acid, nitric acid any one, concentration range is 0.1-5%; The solid mass ratio of leach liquor is (5 ~ 20)/1; Extraction time 1 ~ 60min; Extraction temperature 25-100 DEG C; Weak-acid leaching liquid adds zinc dust precipitation and reclaims the plumbous valuable metal of zinc-copper after carrying out circulating leaching.
In two schemes, fired slags carries out the magneticstrength of high intensity magnetic separation is 1.0-1.6 ten thousand Gauss, preferably 1.2 ten thousand Gausses.
Described fayalite class metallurgical slag comprises lead skim, copper ashes or nickel slag.
The chemical reaction process of the oxidation of pyrite burning that the present invention relates to is as follows:
2FeS
2+5.5O
2→Fe
2O
3+3SO
2(g)(1)
2FeS
2+7O
2→Fe
2(SO
4)
3+SO
2(g)(2)
FeS
2+3O
2→FeSO
4+4SO
2(g)(3)
The chemical reaction process that the oxidation of pyrite combustion intermediate product ferric sulfate that the present invention relates to and ferrous sulfate decompose is as follows:
Fe
2(SO
4)
3→Fe
2O
3+3SO
3(g)(4)
2FeSO
4→Fe
2O
3+SO
3(g)+SO
2(g)(5)
2FeSO
4+1/2O
2(g)→Fe
2O
3+2SO
3(g)(6)
The chemical reaction that sulfurous gas of the present invention decomposes various Fe clusters in waste residue is as follows:
Fe
3O
4+SO
2(g)+O
2(g)→Fe
2(SO
4)
3(7)
Fe
2O
3+SO
2(g)+O
2(g)→Fe
2(SO
4)
3(8)
FeO+SO
2(g)+O
2(g)→Fe
2(SO
4)
3(9)
Fe+SO
2(g)+O
2(g)→Fe
2(SO
4)
3(10)
2FeO·SiO
2+SO
2(g)+O
2(g)→Fe
2(SO
4)
3+SiO
2(11)
FeO·SiO
2+SO
2(g)+O
2(g)→Fe
2(SO
4)
3+SiO
2(12)
In sulphur trioxide decomposition waste residue of the present invention, the chemical reaction of various Fe clusters is as follows:
Fe
3O
4+SO
3(g)→Fe
2(SO
4)
3+SO
2(g)(13)
Fe
2O
3+SO
3(g)→Fe
2(SO
4)
3(14)
FeO+SO
3(g)→Fe
2(SO
4)
3+SO
2(g)(15)
Fe+SO
3(g)→Fe
2(SO
4)
3+SO
2(g)(16)
2FeO·SiO
2+SO
3(g)→Fe
2(SO
4)
3+SiO
2(17)
FeO·SiO
2+SO
3(g)→Fe
2(SO
4)
3+SiO
2(18)
As maturing temperature > 500 DEG C, in waste residue, Fe clusters reaction product ferric sulfate is decomposed into ferric oxide:
Fe
2(SO
4)
3→Fe
2O
3+3SO
3(g)(19)
In first set scheme of the present invention, in fayalite class metallurgical slag, iron mainly exists mutually with fayalite thing, also has a small amount of metallic iron, Z 250 (Fe in addition
3o
4), ferric oxide (Fe
2o
3), iron protoxide (FeO).Pyrite carries out oxidizing fire reaction by reaction (1)-(3), release sulfurous gas (SO
2), oxidation of pyrite combustion intermediate product ferric sulfate and ferrous sulfate decompose release sulfurous gas (SO by (4)-(6) simultaneously
2) and sulphur trioxide (SO
3).The thing phase decomposition of iron various in waste residue is ferric sulfate (Fe by reaction (7)-(12) by intermediate gaseous product sulfurous gas
2(SO
4)
3), the thing phase decomposition of iron various in waste residue is ferric sulfate (Fe by reaction (13)-(18) by sulphur trioxide
2(SO
4)
3).As maturing temperature > 500 DEG C, the product ferric sulfate that in waste residue, iron is obtained by reacting can be decomposed into ferric oxide by reaction (19).From above-mentioned reaction process, add pyrite roasting fayalite class metallurgical slag, in the fired slags finally obtained, Fe clusters is ferric sulfate or ferric oxide.Ore Leaching extraction iron can be carried out or carry out high intensity magnetic separation to fired slags obtaining iron ore concentrate to fired slags.
In the present invention second sets of plan, when fayalite class metallurgical slag is when carrying out roasting for 300-600 DEG C, all Fe clusters can be converted into ferric sulfate.In waste residue, zinc, copper and lead can be separately converted to zinc sulfate, copper sulfate and lead sulfate.Again by waste residue when carrying out roasting for 600-700 DEG C, zinc sulfate and lead sulfate do not transform, and copper sulfate is converted into cupric oxide, and ferric sulfate is converted into ferric oxide, therefore zinc, copper and lead etc. in waste residue can be extracted in advance with weak-acid leaching, be separated with iron.After weak-acid leaching liquid carries out circulating leaching, add the valuable metals such as the recyclable lead of zinc dust precipitation, zinc, copper.
Pyrite is mainly used in oxidizing roasting relieving haperacidity.After oxidation of pyrite roasting, produce a large amount of pyrite cinders, main iron content in pyrite cinder, simultaneously containing valuable metals such as lead, copper, zinc.Current pyrite cinder is mainly stored up, and both to environmental danger, causes the wasting of resources again.Iron resources is reclaimed with oxidation of pyrite roasting fayalite class metallurgical slag, element sulphur in roasting process in pyrite is oxidized the reaction such as iron and lead, zinc, copper in rear and metallurgical slag, in pyrite, ferro element then participates in reaction simultaneously with ferro element in metallurgical slag, is extracted in leaching process or in magnetic separation process.Therefore iron resources in fayalite class metallurgical slag can not only be reclaimed with oxidation of pyrite roasting fayalite class metallurgical slag, realize resource utilization and the minimizing of fayalite class metallurgical slag, the iron resources in pyrite cinder can also be reclaimed simultaneously, realize minimizing and the resource utilization of pyrite cinder, reduce environmental stress.Method provided by the invention with fayalite in oxidation of pyrite Roasting Decomposition metallurgical slag below 1000 DEG C, can extract iron or the means enriched iron with high intensity magnetic separation with acid solution after roasting.
In sum, the invention has the beneficial effects as follows: fayalite thing effectively can be transformed roasting mutually below 1000 DEG C; Without the need to adding carbon or coal, and the heat release of oxidation of pyrite roasting process, energy consumption is low; Technical process is short; Simple to operate; The iron in pyrite cinder and fayalite class metallurgical slag can be reclaimed simultaneously; Separable and the valuable metal such as zinc, copper, lead reclaimed in pyrite cinder and fayalite class metallurgical slag; Fired slags applied range, can be used for preparing various iron salt solutions, also can be used for ironmaking.
Accompanying drawing illustrates:
Fig. 1 is present invention process schema.
Embodiment:
Be described in further details the present invention below in conjunction with specific embodiment, specific embodiment described herein only for explaining the present invention, is not limited to the present invention.
Embodiment 1:
Lead skim and levigate extremely-200 orders (74um) of pyrite are accounted for more than 90%, and in lead skim, the content of Fe is 23.84%.Be 2/1 pyrite and lead skim to be mixed by weight of iron ratio in pyrite/lead skim, oxygen concentration 100%, 450 DEG C of roasting 90min, after roasting completes, take out cooling by the fired slags of pyrite and lead skim mixture.
Fired slags 18% hydrochloric acid soln leaches, 80 DEG C, and liquid-solid ratio is 10/1, and extraction time 15min has leached rear filtering separation.Fired slags iron leaching yield is 94.25%.
Embodiment 2:
Lead skim and levigate extremely-200 orders (74um) of pyrite are accounted for more than 90%, and in lead skim, the content of Fe is 23.84%.Be 2/1 pyrite and lead skim to be mixed by weight of iron ratio in pyrite/lead skim, oxygen concentration 100%, 800 DEG C of roasting 60min, after roasting completes, take out cooling by the fired slags of pyrite and lead skim mixture.Fired slags carries out high intensity magnetic separation, and magneticstrength is 1.2 ten thousand Gausses, and in magnetic separation of iron ore concentrate, iron level is 65.13%.
Contrast experiment 1 (iron is reclaimed in lead skim oxidizing roasting-magnetic separation): account for more than 90% by levigate for lead skim to-200 orders (74um), in lead skim, the content of Fe is 23.84%.Lead skim is passed into the oxygen of 2%, 800 DEG C of oxidizing roasting 30min, after roasting is complete, take out cooling, be carry out magnetic separation under the condition of 0.116T in magneticstrength, in magnetic separation of iron ore concentrate, iron level is 25.4%.
Contrast experiment 2 (iron is reclaimed in lead skim reducing roasting-magnetic separation): account for more than 90% by levigate for lead skim to-200 orders (74um), in lead skim, the content of Fe is 23.84%.Lead skim is passed into the CO of 5%, 800 DEG C of reducing roasting 60min, after roasting is complete, take out cooling, be carry out magnetic separation under the condition of 0.116T in magneticstrength, in magnetic separation of iron ore concentrate, iron level is 35.86%.
Embodiment 3:
Copper ashes and levigate extremely-200 orders (74um) of pyrite are accounted for more than 90%, and in copper ashes, the content of Fe is 40.54%.Be 3/1 pyrite and copper ashes to be mixed by weight of iron ratio in pyrite/copper ashes, oxygen concentration 100%, 700 DEG C of roasting 90min, after roasting completes, take out cooling by the fired slags of pyrite and copper ashes mixture.
Fired slags carries out high intensity magnetic separation, and magneticstrength is 1.2 ten thousand Gausses, and in magnetic separation of iron ore concentrate, iron level is 66.25%.Embodiment 4:
Account for more than 90% by thin for nickel sizing to-200 orders (74um), in nickel slag, the content of Fe is 35.26%.Than 3/2, pyrite and nickel slag are mixed by weight of iron in pyrite/nickel slag, oxygen concentration 100%, 1000 DEG C of roasting 60min, after roasting completes, the fired slags of pyrite and nickel slag mixture is taken out cooling.
Fired slags 40% sulphuric acid soln leaches, and extraction temperature is 80 DEG C, and liquid-solid ratio is 10/1, and extraction time 20min has leached rear filtering separation.Iron leaching yield is 93.72%.
Embodiment 5:
Account for more than 90% by levigate for lead skim to-200 orders (74um), in lead skim, the content of Fe is 23.84%.Than 3/1, pyrite and lead skim are mixed by weight of iron in pyrite/lead skim, oxygen concentration 100%, 500 DEG C of roasting 60min, then at 650 DEG C of roasting 60min, after roasting completes, the fired slags of pyrite and lead skim mixture is taken out cooling.
The fired slags Leaching in Hydrochloric Acid of 5% carries out pre-treatment.After the hydrochloric acid leachate of 5% carries out circulating leaching, add zinc dust precipitation and reclaim plumbous and zinc.
Carry out high intensity magnetic separation after fired slags pre-treatment, magneticstrength is 1.2 ten thousand Gausses, and in magnetic separation of iron ore concentrate, iron level is 66.75%, Zn content < 1% in iron ore concentrate, lead content < 0.5%.
Embodiment 6:
Account for more than 90% by levigate for copper ashes to-200 orders (74um), in copper ashes, the content of Fe is 40.54%.Pyrite and copper ashes are mixed than 3/1 by weight of iron in pyrite/copper ashes, 400 DEG C of roasting 60min, oxygen concentration 100%.Again at 600 DEG C of roasting 60min, after roasting completes, the fired slags of pyrite and copper ashes mixture is taken out cooling.
Pre-treatment is carried out in the fired slags nitric acid leaching of 2%.After the leaching solution of 2% carries out circulating leaching, add zinc dust precipitation and reclaim copper.
Carry out high intensity magnetic separation after fired slags pre-treatment, magneticstrength is 1.2 ten thousand Gausses, and in magnetic separation of iron ore concentrate, iron level is 66.82%, copper content < 0.5% in iron ore concentrate.
From above embodiment, the inventive method uses pyrite roasting fayalite class metallurgical slag below 900 DEG C, after the fired slags of pyrite and fayalite class metallurgical slag mixture leaches, iron leaching yield > 94%, after magnetic separation, in iron ore concentrate, iron level, more than 66%, illustrates iron in energy efficient recovery pyrite of the present invention and fayalite class metallurgical slag.After the pre-treatment of two sections of combination roasting weak-acid leaching, in iron ore concentrate, Zn content can be reduced to 1%, lead content < 0.5%, copper content < 0.5%, for reclaiming lead, zinc, copper after weak-acid leaching liquid carries out circulating leaching, illustrate that the inventive method effectively can also be separated and reclaim lead, zinc, copper etc. in pyrite and fayalite class metallurgical slag.Iron content leach liquor can be used for preparing various ferrite or flocculation agent, and magnetic concentrate can be used as iron-smelting raw material.
Claims (10)
1. pyrite roasting fayalite class metallurgical slag reclaims a method for iron, it is characterized in that, the one in optional following two schemes:
(1) fayalite class metallurgical slag adds pyrite, roasting under aerobic conditions, after roasting completes, fired slags acid solution is carried out leaching and obtains iron content leach liquor, or fired slags is carried out high intensity magnetic separation obtains iron ore concentrate;
(2) fayalite class metallurgical slag is added pyrite two sections of low-temperature bakes in oxidizing atmosphere, fired slags with after the plumbous valuable metal of weak-acid leaching zinc-copper, then obtains iron content leach liquor or carries out high intensity magnetic separation obtaining iron ore concentrate with acid solution leaching.
2. pyrite roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: in scheme (1), maturing temperature is 300-1100 DEG C, preferred 450-900 DEG C roasting time is 15-180min, preferred 60-90min.
3. pyrite roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: in scheme (2), two sections of low-temperature bakes refer to 300-600 DEG C of roasting 30-150min, preferred 30-90min, again at 600-700 DEG C of roasting 30-150min, preferred 30-60min.
4. pyrite roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: the weight of iron in pyrite/fayalite class metallurgical slag is than=1 ~ 8.
5. the pyrite roasting fayalite class metallurgical slag according to claim 1 or 4 reclaims the method for iron, it is characterized in that: the weight of iron ratio in pyrite/fayalite class metallurgical slag is 1 ~ 3.
6. pyrite roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: the oxygen concentration in two schemes is 1-100%, and preferably 100%.
7. pyrite roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: the acid solution leaching iron in two schemes is the sulfuric acid of 20-98%, the hydrochloric acid of 8-38%, the nitric acid of 14-69%, any one of the acetic acid of 12-56%; The sulfuric acid of preferred 30-50%, the hydrochloric acid of 12-19%, the nitric acid of 20-35%, the acetic acid of 15-28%; The solid mass ratio of leach liquor is (5 ~ 20)/1, preferably (5 ~ 10)/1; Extraction time 1 ~ 60min; Extraction temperature 25-100 DEG C.
8. pyrite roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: in scheme (2) weakly acid soln of leaching valuable metal be sulfur acid, hydrochloric acid, nitric acid any one, concentration range is 0.1-5%; The solid mass ratio of leach liquor is (5 ~ 20)/1; Extraction time 1 ~ 60min; Extraction temperature 25-100 DEG C; Weak-acid leaching liquid adds zinc dust precipitation and reclaims the plumbous valuable metal of zinc-copper after carrying out circulating leaching.
9. pyrite roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: in two schemes, fired slags carries out the magneticstrength of high intensity magnetic separation is 1.0-1.6 ten thousand Gauss, preferably 1.2 ten thousand Gausses.
10. pyrite roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: described fayalite class metallurgical slag comprises lead skim, copper ashes or nickel slag.
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| CN105112676B (en) | 2018-03-30 |
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