CN101407355B - Method for comprehensively utilizing iron vitriol dreg of yellow sodium - Google Patents
Method for comprehensively utilizing iron vitriol dreg of yellow sodium Download PDFInfo
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- CN101407355B CN101407355B CN2008102284407A CN200810228440A CN101407355B CN 101407355 B CN101407355 B CN 101407355B CN 2008102284407 A CN2008102284407 A CN 2008102284407A CN 200810228440 A CN200810228440 A CN 200810228440A CN 101407355 B CN101407355 B CN 101407355B
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- iron
- slag
- iron vitriol
- yellow sodium
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Abstract
The invention relates to a comprehensive utilization method of amarillite slag, which is characterized by including the following steps: (1) the valuable metals in the amarillite slag are selectively leached by using sulfuric acid solution, thus obtaining the leaching slag and the leaching agent; (2) the leaching slag and sulphuric acid are mixed then heated under microwave radiation; (3) water and a substance containing iron are added into the material after microwave radiation, quiescence and slaking are carried out at normal temperature condition and (4) the material is heated, ferrous iron in the solution is oxidized by using an oxidant, then the polymerization ferric sulfate is prepared through hydrolysis and polymerization by ferric iron. The invention effectively retrieves the valuable metals in the amarillite slag, reduces reagent consumption and energy consumption during amarillite slag treatment process, shortens the treatment time, has no environmental pollution during the treatment process, obtains the water treatment agent polymerization ferric sulfate with good quality, and can effectively solve the problems of the stockpiling and pollution of the amarillite slag.
Description
Technical field
The invention belongs to the industrial waste residue disposal field, particularly a kind of method that fully utilizes iron vitriol dreg of yellow sodium.
Background technology
In the hydrometallurgy process of non-ferrous metals such as copper, nickel, cobalt, zinc, often adopt yellow modumite method to remove iron in the solution, the waste residue that this method for removing iron produces is iron vitriol slag.Because lack rational treatment process, a large amount of iron vitriol slags is stacked near the factory, land occupation not only, and environment worked the mischief.Though other method for removing iron as hematite process, goethite process etc., also are widely used, because technology and economic aspect, many hydrometallurgies factory still adopts the deironing of siderotil method, thereby annually still has a large amount of iron vitriol slags to produce.Therefore, the comprehensive utilization iron vitriol dreg of yellow sodium has become one of focus of industrial waste residue disposal.
In order to reclaim wherein valuable metal, people take iron vitriol slag roasting, leaching, the method for separation of iron and valuable metal.Propose the iron vitriol slag roasting as patent CN1221800,350～900 ℃ of maturing temperatures separate indium iron through leaching, Centrifugical extraction, reclaim the method for indium; Patent EP1098999-A1 proposes under 400～800 ℃ iron vitriol slag to be carried out sulfurization roasting, with product of roasting water-soluble after, adopt neutralization precipitation, sulfide precipitation, ion-exchange or method of extraction to reclaim valuable metal.
Since bigger to control and the intractability that produces flue gas in the roasting process, environmental pollution caused easily, and people take the method for hydrometallurgy to handle iron vitriol slag.Propose earlier iron vitriol slag to be adopted alkaline purification as patent US2004118248-A1, with acid ore pulp after the alkaline purification is adjusted to acidity then, the method that makes the valuable metal stripping and reclaim owing to relate to acid-base neutralisation, causes reagent consumption big; It is 150～220 ℃ that patent WO8803911-A proposes in temperature, under the condition of pH=1.2～3.5, uses CaCl
2Leach, reclaim the method for valuable metal in the iron vitriol slag, recovering effect is better, but needs the high pressure leaching plant, the production cost height.
The major issue that above method exists is after treatment, and the iron in the iron vitriol slag is still with the form discharging of waste residue, does not thoroughly solve the storing up of scum, pollution problem.For this reason, people also propose to utilize iron vitriol slag to produce the method for other products.Propose to adopt the auxiliary leaching of nitric acid iron vitriol slag as patent WO9730936-A, produce the method that ferric sulfate is used for water treatment, reach purpose, but do not propose the efficient recovery valuable metal and reduce the method that acid consumes with dirty pollution treatment.In addition, patent KR8902856-B proposes the iron vitriol slag roasting, adds the alkali neutralization precipitation after water leaches, and will precipitate with activated carbon etc. and mix as hydrogen sulfide adsorbent; Patent SU1507830-A proposition 500～900 ℃ of roastings, obtains iron oxide red pigment with iron vitriol slag after cleaning, drying; Patent SU1255607-A proposes after with 300～400 ℃ of roastings of siderotil, the method for and material batching sticking as building, and there are weak points such as baking flue gas pollution, complex process in these treatment processs.
Problem at present iron vitriol dreg of yellow sodium treatment process existence, especially in order to solve the technical barrier of comprehensive utilization iron vitriol dreg of yellow sodium, the present invention proposes with diluted acid the valuable metal selectivity in the iron vitriol dreg of yellow sodium to be leached, effective realization valuable metal separates with yellow modumite, main component in the leached mud is yellow modumite, after leached mud and the mixing of a certain amount of sulfuric acid, adopt microwave heating method, yellow modumite is decomposed into vitriol, after allocating a certain amount of water and waste iron filing or iron plate then into and carrying out slaking, use oxygenant (hydrogen peroxide or sodium chlorate etc.) with the oxidation of divalent in the solution, through hydrolysis, polymerization obtains the water conditioner bodied ferric sulfate.The present invention has separated the valuable metal in the iron vitriol dreg of yellow sodium effectively, the characteristics of utilizing microwave rapid heating and body to heat have reduced the reagent consumption and the energy consumption of iron vitriol slag treating processes, shortened the treatment time, the treating processes environmentally safe, the water conditioner polyaluminum sulfate weight of iron for preparing is good, the pollution problem of storing up that can solve iron vitriol dreg of yellow sodium effectively.
Summary of the invention
The object of the invention is to provide a kind of method that fully utilizes iron vitriol dreg of yellow sodium.
The method of comprehensive utilization iron vitriol dreg of yellow sodium of the present invention, concrete steps are:
1, be that 1%～5% sulphuric acid soln leaches the valuable metal selectivity in the iron vitriol dreg of yellow sodium with mass concentration, control liquid-solid ratio 3: 1～10: 1 obtains leached mud and contains the leach liquor of valency metal (copper, nickel, cobalt or zinc).Reaction formula is:
MSO
4→M
2++SO
4 2-
M=Ni, Cu, Co or Zn in the formula.
2, leached mud is mixed with sulfuric acid, the vitriolic consumption is 30～60% of a leached mud quality; Heat 6～15min then under microwave radiation, microwave frequency is 2450 ± 50MHz or 916 ± 18MHz.Reaction formula is:
Na
2Fe
6(SO
4)
4(OH)
12+6H
2SO
4→3Fe
2(SO
4)
3+Na
2SO
4+12H
2O
3, add the material of entry and containing metal iron in the material after microwave radiation, leave standstill slaking 2～8h under normal temperature condition, the full concentration of iron of material after the adjusting slaking is 160～180g/L, and wherein ferrous ion content accounts for 20～40% of all iron content.Reaction formula is:
Fe
3++Fe→3Fe
2+
Fe+2H
+→Fe
2++H
2↑
The material of containing metal iron is waste iron filing or scrap iron sheet etc. among the present invention.
By the add-on of control containing metal iron substance and water, full concentration of iron in the regulator solution and ferrous ion proportion.
4, the material that step 3 is generated is heated to 40～80 ℃, add oxygenant, the oxygenant consumption all is oxidized to 1～1.5 times of theoretical consumption of ferric ion by ferrous ion in the material, reaction times is 1～3h, wherein oxygenant is oxygenants commonly used such as hydrogen peroxide or sodium chlorate, is prepared into bodied ferric sulfate through ferric iron hydrolysis, polymerization.The principal reaction formula is:
2FeSO
4+H
2O
2+(1-n/2)H
2SO
4→Fe
2(OH)
n(SO
4)
3-n/2+(2-n)H
2O)
6FeSO
4+NaClO
3+3(1-n/2)H
2SO
4→3[Fe
2(OH)
n(SO
4)
3-n/2]+3(1-n)H
2O+NaCl
N≤2 wherein.
The present invention is different from existing iron vitriol dreg of yellow sodium treatment process, in order to fully utilize iron vitriol slag effectively, cut down the consumption of energy simultaneously and supplies consumption, obtain environmental benefit and economic benefit preferably, the present invention proposes with diluted acid the valuable metal selectivity in the iron vitriol slag to be leached, make it to be recycled, the main component in the leached mud is yellow modumite; Then, after leached mud and the mixing of a certain amount of sulfuric acid, adopt microwave heating method, be decomposed into vitriol; The material of allocating a certain amount of water and containing metal iron then into carries out slaking; Re-use oxygenant with the oxidation of divalent iron ion in the solution, obtain the water conditioner bodied ferric sulfate through ferric iron hydrolysis, polymerization.
Present method has reclaimed the valuable metal in the iron vitriol slag effectively, the characteristics of utilizing microwave rapid heating and body to heat have reduced the reagent consumption and the energy consumption of iron vitriol slag treating processes, shortened the treatment time, the treating processes environmentally safe, the water conditioner polyaluminum sulfate weight of iron for preparing is good, the pollution problem of storing up that can solve iron vitriol dreg of yellow sodium effectively.
The present invention also is applicable to the processing of other ihleite slag.
Figure of description
Fig. 1 is the schematic flow sheet of the method for comprehensive utilization iron vitriol dreg of yellow sodium of the present invention.
Embodiment
For the content of patent of the present invention better is described, provide following examples.Iron vitriol dreg of yellow sodium in the present embodiment is the mixture from the iron vitriol slag of heavy metal hydrometallurgy system, and wherein iron level is 24.5%, and nickel content is 1.43%, and copper content is 0.53%, and cobalt contents is 0.13%, and zinc content is 2.03%.
Embodiment 1
Being 1% sulphuric acid soln with mass concentration leaches the valuable metal selectivity in the iron vitriol dreg of yellow sodium by liquid-solid ratio 3: 1, and the average leaching yield of valuable metal is 80%.
With leached mud and sulfuric acid thorough mixing, the sulfuric acid consumption is 30% of an iron vitriol dreg of yellow sodium quality, heats 15min under microwave radiation, decomposes yellow modumite, and wherein microwave frequency is 2450 ± 50MHz.
Material after microwave radiation adds entry and scrap iron sheet, slaking 8h, and the full concentration of iron in the regulator solution is 160g/L, ferrous ion content accounts for 20% of all iron content; Then under 40 ℃ temperature, use oxidant hydrogen peroxide that the oxidation of divalent iron ion in the above-mentioned solution is ferric ion, reaction times 1h; Wherein the consumption of hydrogen peroxide is that whole oxidation of divalent iron ion are 1.5 times of ferric ion institute expense.Obtain the water conditioner bodied ferric sulfate through ferric iron hydrolysis, polymerization, all iron content 11.24% of bodied ferric sulfate, reducing substances is (with Fe
2+Meter) content 0.02%, basicity 8.13%.
Embodiment 2
Being 3% dilute sulphuric acid with mass concentration leaches the valuable metal selectivity in the iron vitriol dreg of yellow sodium by liquid-solid ratio 5: 1, and the average leaching yield of valuable metal is 90%.
With leached mud and sulfuric acid thorough mixing, the sulfuric acid consumption is 40% of an iron vitriol dreg of yellow sodium quality, heats 10min under microwave radiation, decomposes yellow modumite, and wherein microwave frequency is 2450 ± 50MHz.
Material after the microwave radiation is added entry and scrap iron sheet, slaking 5h, the full concentration of iron in the regulator solution is 170g/L, ferrous ion content accounts for 30% of all iron content; Then under 60 ℃ temperature, use oxidant hydrogen peroxide that the oxidation of divalent iron ion in the above-mentioned solution is ferric ion, reaction times 2h; Wherein the consumption of hydrogen peroxide is that whole oxidation of divalent iron ion are 1.0 times of ferric ion institute expense.Obtain the water conditioner bodied ferric sulfate through ferric iron hydrolysis, polymerization, all iron content 11.67% of bodied ferric sulfate, reducing substances is (with Fe
2+Meter) content 0.01%, basicity 12.02%.
Embodiment 3
Being 5% dilute sulphuric acid with mass concentration leaches the valuable metal selectivity in the iron vitriol dreg of yellow sodium by liquid-solid ratio 10: 1, and the average leaching yield of valuable metal is 93%.
With leached mud and sulfuric acid thorough mixing, the sulfuric acid consumption is 60% of an iron vitriol dreg of yellow sodium quality, heats 6min under microwave radiation, decomposes yellow modumite; Wherein microwave frequency is 916 ± 18MHz.
Material after microwave radiation adds entry and iron filings, slaking 2h, and the full concentration of iron in the regulator solution is 180g/L, ferrous ion content accounts for 40% of all iron content; Then under 80 ℃ temperature, use oxygenant chloric acid sodium the oxidation of divalent iron ion in the above-mentioned solution to be ferric ion, reaction times 3h; Wherein the consumption of sodium chlorate is that whole oxidation of divalent iron ion are 1.0 times of ferric ion institute expense.Obtain the water conditioner bodied ferric sulfate through ferric iron hydrolysis, polymerization, all iron content 12.25% of bodied ferric sulfate, reducing substances is (with Fe
2+Meter) content 0.01%, basicity 14.03%.
Claims (5)
1. method that fully utilizes iron vitriol dreg of yellow sodium, it is characterized in that may further comprise the steps: to be 1%～5% sulphuric acid soln with mass concentration leach the valuable metal selectivity in the iron vitriol dreg of yellow sodium by liquid-solid ratio 3: 1～10: 1 (1), obtains leached mud and contain the leach liquor of valency metal; (2) leached mud is mixed with sulfuric acid, the vitriolic consumption is 30～60% of a leached mud quality; Heat 6～15min then under microwave radiation, microwave frequency is 2450 ± 50MHz or 916 ± 18MHz; (3) add the material of entry and containing metal iron in the material after microwave radiation, leave standstill slaking 2～8h under normal temperature condition, the full concentration of iron in the regulator solution is 160～180g/L, and wherein ferrous ion content accounts for 20～40% of all iron content; (4) material with step (3) is heated to 40～80 ℃, add oxygenant, the oxygenant consumption all is oxidized to 1～1.5 times of theoretical consumption of ferric ion by ferrous ion in the material, the reaction times is 1～3h, is prepared into bodied ferric sulfate through ferric iron hydrolysis, polymerization.
2. the method for comprehensive utilization iron vitriol dreg of yellow sodium according to claim 1 is characterized in that the valuable metal in the described iron vitriol slag is copper, nickel, cobalt or zinc.
3. the method for comprehensive utilization iron vitriol dreg of yellow sodium according to claim 1 is characterized in that described iron vitriol dreg of yellow sodium is ihleite slag from heavy metal hydrometallurgy system and composition thereof.
4. the method for comprehensive utilization iron vitriol dreg of yellow sodium according to claim 1 is characterized in that described containing metal iron substance is waste iron filing or scrap iron sheet.
5. the method for comprehensive utilization iron vitriol dreg of yellow sodium according to claim 1 is characterized in that described oxygenant for oxygenant commonly used, comprises hydrogen peroxide or sodium chlorate.
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|---|---|---|---|
| CN2008102284407A CN101407355B (en) | 2008-10-31 | 2008-10-31 | Method for comprehensively utilizing iron vitriol dreg of yellow sodium |
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|---|---|---|---|
| CN2008102284407A CN101407355B (en) | 2008-10-31 | 2008-10-31 | Method for comprehensively utilizing iron vitriol dreg of yellow sodium |
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| CN101407355B true CN101407355B (en) | 2010-09-29 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888515A (en) * | 2012-10-12 | 2013-01-23 | 金川集团股份有限公司 | Comprehensive utilization method of amarillite slag |
| CN103114205B (en) * | 2012-12-07 | 2014-06-25 | 金川集团股份有限公司 | Two-step method for extracting valuable metal nickel and copper from sodium jarosite slag |
| CN103589861B (en) * | 2013-11-27 | 2015-07-22 | 昆明理工大学 | Method for microwave sulfating roasting-water leaching treatment of jarosite slag |
| CN103966431A (en) * | 2014-05-15 | 2014-08-06 | 王平 | Technology for catalyzing nickel and cobalt leaching reaction by microwave heating |
| CN105385858B (en) * | 2015-11-03 | 2017-08-25 | 中南大学 | A kind of iron vitriol slag prepares iron oxide red and the method for reclaiming silver |
| CN105800694A (en) * | 2016-02-01 | 2016-07-27 | 四川大学 | Method for preparing micaceous iron oxide from ihleite through hydrothermal conversion |
| CN110724824B (en) * | 2019-10-29 | 2020-11-10 | 中南大学 | Method for extracting valuable heavy metals from jarosite slag through ferrous catalytic conversion |
| CN112359212B (en) * | 2020-11-24 | 2022-03-08 | 江西佳纳能源科技有限公司 | Method for recovering cobalt, copper and iron from cobalt slag |
| CN113136488B (en) * | 2021-04-22 | 2022-10-18 | 中化化工科学技术研究总院有限公司 | Wet treatment process for iron vitriol slag in zinc hydrometallurgy |
| CN114045397A (en) * | 2021-10-26 | 2022-02-15 | 广东佳纳能源科技有限公司 | Method for recovering wet smelting iron slag |
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