CN105039730A - Method for recycling iron from metallurgy waste residues of fayalite category through roasting with sulfur dioxide - Google Patents
Method for recycling iron from metallurgy waste residues of fayalite category through roasting with sulfur dioxide Download PDFInfo
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- CN105039730A CN105039730A CN201510572205.1A CN201510572205A CN105039730A CN 105039730 A CN105039730 A CN 105039730A CN 201510572205 A CN201510572205 A CN 201510572205A CN 105039730 A CN105039730 A CN 105039730A
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- iron
- roasting
- fayalite
- sulfurous gas
- metallurgical slag
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for recycling iron from metallurgy waste residues of fayalite category through roasting with sulfur dioxide. The method comprises the steps of introducing sulfur dioxide gas and oxygen into the metallurgy waste residues of the fayalite category, conducting roasting at the temperature of 200-1100 DEG C, then using an acid solution for leaching the iron, wherein the leaching rate reaches 91%, or conducting intensive magnetic separation, wherein the iron content in magnetic concentrate reaches 66%. Through the method, the iron can be effectively recycled from the metallurgy waste residues of the fayalite category through roasting with the sulfur dioxide, and the effect of quantitative reduction for the metallurgy waste residues of fayalite category and the iron resource recycling is obvious.
Description
Technical field:
The invention belongs to metallurgical engineering and environmental engineering crossing domain, relate to a kind of method that sulfurous gas 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 waste residues 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 sulfurous gas roasting fayalite class metallurgical slag to reclaim the method for iron.Pass into sulfurous gas and oxygen, by fayalite thing phase decomposition in metallurgical slag, then reclaim iron by the mode of leaching or magnetic separation.
Sulfurous gas 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 is passed into sulfurous gas and oxygen roasting, after roasting completes, fired slags water or acid solution are carried out leaching and obtain iron content leach liquor, or fired slags is carried out high intensity magnetic separation obtain iron ore concentrate;
(2) fayalite class metallurgical slag is passed into sulfurous gas and oxygen two sections of low-temperature bakes, fired slags with after weak-acid leaching zinc-copper valuable metal, then obtains iron content leach liquor or carries out high intensity magnetic separation obtaining iron ore concentrate with acid solution leaching.
In scheme (1), maturing temperature is 200-1100 DEG C, and roasting time is 15-180min.
In scheme (2), two sections of low-temperature bakes refer to and pass into sulfurous gas and oxygen, at 200-600 DEG C of roasting 30-150min, and preferred roasting 60-90min, then close sulfurous gas and oxygen at 600-700 DEG C of roasting 30-150min, preferred roasting 60min.
SO in two schemes
2/ (SO
2+ O
2) volume ratio is 10-90%.Preferred SO
2/ (SO
2+ O
2) volume ratio is 60-70%.
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 (1) with the leaching condition that water logging is tapped a blast furnace be: the solid mass ratio of leach liquor is (5 ~ 20)/1, extraction time 1 ~ 60min, extraction temperature 50-100 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 valuable metals such as zinc-copper lead 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.
In the sulfurous gas Roasting Decomposition waste residue that the present invention relates to, the chemical reaction of various Fe clusters is as follows:
Fe
3O
4+SO
2(g)+O
2(g)→Fe
2(SO
4)
3(1)
Fe
2O
3+SO
2(g)+O
2(g)→Fe
2(SO
4)
3(2)
FeO+SO
2(g)+O
2(g)→Fe
2(SO
4)
3(3)
Fe+SO
2(g)+O
2(g)→Fe
2(SO
4)
3(4)
2FeO·SiO
2+SO
2(g)+O
2(g)→Fe
2(SO
4)
3+SiO
2(5)
FeO·SiO
2+SO
2(g)+O
2(g)→Fe
2(SO
4)
3+SiO
2(6)
As calcination 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)(7)
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).The thing phase decomposition of iron various in waste residue is ferric sulfate (Fe by reaction (1)-(6) by sulfurous gas
2(SO
4)
3).When controlling maturing temperature < 500 DEG C or high-concentration sulfur dioxide, can control Fe clusters in fired slags is ferric sulfate; As control maturing temperature > 500 DEG C and when closing sulfur dioxide gas, can control Fe clusters in fired slags is ferric oxide (reaction (7)).Therefore sulfurous gas decomposes fayalite metallurgical slag, can control Fe clusters in fired slags according to the condition of subsequent extracted iron.Leaching can be carried out to fired slags to extract iron or fired slags and carry out high intensity magnetic separation and obtain iron ore concentrate.When Fe clusters in fired slags is all ferric sulfate, used water leaches.
In the present invention second sets of plan, when fayalite class metallurgical slag is when carrying out roasting for 200-600 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.
Method provided by the invention can with fayalite in sulfurous gas Roasting Decomposition metallurgical slag below 1000 DEG C, and after roasting, energy water or acid solution extract iron or the means enriched iron with high intensity magnetic separation.
In sum, the invention has the beneficial effects as follows: below 1000 DEG C, fayalite thing effectively can be transformed mutually; The thing phase controllable of iron in fired slags; Without the need to adding carbon or coal, energy consumption is low; Technical process is short; Simple to operate; Separable and the valuable metal such as zinc, copper, lead reclaimed in 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:
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 mixed gas, gas composition SO
2/ (SO
2+ O
2) be 66%, at 300 DEG C of roasting 120min, after roasting completes, fired slags is taken out cooling.
The fired slags aqueous solution leaches, 90 DEG C, and liquid-solid ratio is 10/1, and extraction time 15min has leached rear filtering separation.Iron leaching yield is 91.25%.
Embodiment 2:
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 mixed gas, gas composition SO
2/ (SO
2+ O
2) be 60%, at 400 DEG C of roasting 60min; Close mixed gas again, at 800 DEG C of roasting 30min.After roasting completes, fired slags is taken out cooling.Fired slags is carried 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 completes, 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 5%CO, 800 DEG C of reducing roasting 60min, after roasting completes, 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:
Account for more than 90% by levigate for copper ashes to-200 orders (74um), in copper ashes, the content of Fe is 40.54%.Copper ashes is passed into gas, gas composition SO
2/ (SO
2+ O
2) be 60%, at 1000 DEG C of roasting 60min, after roasting completes, fired slags is taken out cooling.
Fired slags 12% hydrochloric 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 94.73%.
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%.Nickel slag is passed into mixed gas, gas composition SO
2/ (SO
2+ O
2) be 60%, at 600 DEG C of roasting 60min, after roasting completes, fired slags is taken out cooling.
Fired slags 30% sulphuric acid soln leaches, and extraction temperature is 80 DEG C, and liquid-solid ratio is 10/1, and extraction time 15min has leached rear filtering separation.Iron leaching yield is 96.23%.
Embodiment 5:
Account for more than 90% by levigate for copper ashes to-200 orders (74um), in copper ashes, the content of Fe is 40.54%.Copper ashes is passed into mixed gas, mixed gas composition SO
2/ (SO
2+ O
2) be 70%, 500 DEG C of roasting 60min, then close mixed gas at 650 DEG C of roasting 60min, after roasting completes, fired slags is taken out cooling.Fired slags leaches with 2% sulphuric acid soln and carries out pre-treatment.After the sulphuric leachate 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 iron concentrate grade is 66.47%, and in iron ore concentrate, copper content is 0.3%.
Embodiment 6:
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 mixed gas, gas composition SO
2/ (SO
2+ O
2) be 65%, at 400 DEG C of roasting 60min, then close mixed gas at 650 DEG C of roasting 40min, after roasting completes, fired slags is taken out cooling.Fired slags leaches with 2% salpeter solution and carries out pre-treatment.After the leaching solution of 2% carries out circulating leaching, add zinc dust precipitation and reclaim zinc and lead.Carry out high intensity magnetic separation after fired slags pre-treatment, magneticstrength is 1.2 ten thousand Gausses, and iron concentrate grade is 65.05%, Zn content < 1% in iron ore concentrate, and lead content is 0.15%.
From above embodiment, the inventive method is roasting fayalite class metallurgical slag below 1000 DEG C, the leaching yield > 91% of iron after fired slags leaches, after magnetic separation, in iron ore concentrate, iron level reaches 66%, and iron in energy efficient recovery fayalite class metallurgical slag of the present invention is described.In iron ore concentrate, Zn content can be reduced to 1%, lead content 0.15%, copper content 0.3%, for reclaiming lead, zinc, copper after weak-acid leaching liquid carries out circulating leaching, illustrates that the inventive method can also lead, zinc, copper etc. in Separation and Recovery 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. sulfurous gas 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 is passed into sulfurous gas and oxygen roasting, after roasting completes, fired slags water or acid solution are carried out leaching and obtain iron content leach liquor, or fired slags is carried out high intensity magnetic separation obtain iron ore concentrate;
(2) fayalite class metallurgical slag is passed into sulfurous gas and oxygen carries out two sections of low-temperature bakes, fired slags with after weak-acid leaching zinc lead bronze valuable metal, then leaches with acid solution and obtains iron content leach liquor or carry out high intensity magnetic separation obtaining iron ore concentrate.
2. sulfurous gas 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 200-1100 DEG C, and roasting time is 15-180min.
3. sulfurous gas 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 and pass into sulfurous gas and oxygen, at 200-600 DEG C of roasting 30-150min, preferred roasting 60-90min, close sulfurous gas and oxygen again at 600-700 DEG C of roasting 30-150min, preferred roasting 60min.
4. sulfurous gas roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: SO in two schemes
2/ (SO
2+ O
2) volume ratio is 10-90%.Preferred SO
2/ (SO
2+ O
2) volume ratio is 60-70%.
5. sulfurous gas 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.
6. sulfurous gas roasting fayalite class metallurgical slag according to claim 1 reclaims the method for iron, it is characterized in that: in scheme (1) with the leaching condition that water logging is tapped a blast furnace be: the solid mass ratio of leach liquor is (5 ~ 20)/1, extraction time 1 ~ 60min, extraction temperature 50-100 DEG C.
7. sulfurous gas 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.
8. the sulfurous gas roasting fayalite class metallurgical slag according to claim 1 or 7 reclaims the method for iron, it is characterized in that: after in scheme (2), weak-acid leaching liquid carries out circulating leaching, adds zinc dust precipitation and reclaims lead, zinc, copper valuable metal.
9. sulfurous gas 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. sulfurous gas 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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|---|---|---|---|
| CN201510572205.1A CN105039730B (en) | 2015-09-09 | 2015-09-09 | A kind of method that sulfur dioxide roasting fayalite class metallurgical slag reclaims iron |
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| CN201510572205.1A CN105039730B (en) | 2015-09-09 | 2015-09-09 | A kind of method that sulfur dioxide roasting fayalite class metallurgical slag reclaims iron |
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| CN105039730B CN105039730B (en) | 2017-06-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048647A (en) * | 2017-11-07 | 2018-05-18 | 江苏省冶金设计院有限公司 | A kind of processing method of copper ashes |
| CN110357170A (en) * | 2019-08-22 | 2019-10-22 | 昆明理工大学 | A method of slag containing fayalite is handled using yellow phosphoric tail gas |
Citations (3)
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|---|---|---|---|---|
| US3753692A (en) * | 1969-08-20 | 1973-08-21 | Ici Australia Ltd | A process for the coproduction of zinc and sulphuric acid from zinc sulphide ores |
| US4043804A (en) * | 1976-06-16 | 1977-08-23 | The Anaconda Company | Recovery of metal values from copper reverberatory slag |
| CN101519731A (en) * | 2009-04-10 | 2009-09-02 | 山东恒邦冶炼股份有限公司 | Method for extracting high arsenic complicated golden ore concentrate multielement |
-
2015
- 2015-09-09 CN CN201510572205.1A patent/CN105039730B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3753692A (en) * | 1969-08-20 | 1973-08-21 | Ici Australia Ltd | A process for the coproduction of zinc and sulphuric acid from zinc sulphide ores |
| US4043804A (en) * | 1976-06-16 | 1977-08-23 | The Anaconda Company | Recovery of metal values from copper reverberatory slag |
| CN101519731A (en) * | 2009-04-10 | 2009-09-02 | 山东恒邦冶炼股份有限公司 | Method for extracting high arsenic complicated golden ore concentrate multielement |
Non-Patent Citations (2)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048647A (en) * | 2017-11-07 | 2018-05-18 | 江苏省冶金设计院有限公司 | A kind of processing method of copper ashes |
| CN110357170A (en) * | 2019-08-22 | 2019-10-22 | 昆明理工大学 | A method of slag containing fayalite is handled using yellow phosphoric tail gas |
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|---|---|
| CN105039730B (en) | 2017-06-09 |
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