CN114632806B - Comprehensive utilization method of high-silicon type iron tailings - Google Patents
Comprehensive utilization method of high-silicon type iron tailings Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention provides a comprehensive utilization method of high-silicon type iron tailings, belonging to the technical field of resource utilization of industrial solid wastes. According to the method for comprehensively utilizing the high-silicon type iron tailings, the mixed flora with the iron-dissolving and desiliconizing functions is used for biologically leaching the high-silicon type iron tailings, iron is recycled for the second time, the leachate can be recycled, the chemical reaction activity of the leached residues can be effectively improved, the leachate can be used as an active admixture for preparing an iron tailing-based cementing material, and the purpose of comprehensively utilizing the high-silicon type iron tailings is achieved.
Description
Technical Field
The invention relates to the technical field of resource utilization of industrial solid wastes, in particular to a comprehensive utilization method of high-silicon type iron tailings.
Background
The iron tailings are powdery or granular industrial solid wastes generated after the ore dressing of the iron ores, and have the problems of large yield, large stacking quantity, low utilization rate, serious environmental pollution, high hidden danger risks and the like (metal mines 2010,412 (10): 142-145). Therefore, the method for comprehensively utilizing the iron tailings with low pollution and high added value is an important target for solving the problem of iron tailing retention in China.
The iron tailings mostly have the particle size of less than 0.5mm and have irregular shapesThen, the characteristics of multi-edge angle and rough surface can be generally divided into five categories: the high-silicon type iron tailings, the high-aluminum type iron tailings, the high-calcium magnesium type iron tailings, the wine steel type iron tailings and the multi-metal type iron tailings are obtained, wherein the high-silicon type iron tailings occupy the largest area. The extremely fine particle size, the angular particle shape and the inert mineral component are main reasons for the difficulty in large-scale comprehensive utilization of the iron tailings. At present, the comprehensive utilization approaches of iron tailings are as follows: the iron tailings are further selected to recover valuable elements, and the iron tailings are used as raw materials to prepare building materials, are used as mesoporous molecular sieves, are used as filling materials, improve saline-alkali soil and the like. Recovery of valuable elements from iron tailings by magnetic separation technology is mainly used for recovering refined iron ores (metal mines, 2018,504 (6): 172-178) or recovering metals from iron tailings by using coal as a reducing agent (material heat treatment science, 2014,35 (9): 16-22). For the high-silicon type iron tailings, the traditional magnetic separation technology is adopted for secondary iron recovery, the operation process difficulty is high, the extraction is difficult, the cost is high, the problems of secondary tailing discharge and the like exist, and therefore the high-silicon type iron tailings are not used for secondary iron recovery generally. SiO of high-silicon type iron tailings 2 The content is more than 70 percent, namely SiO 2 -CaO-Al 2 O 3 The silicate mineral with the main component has potential pozzolanic reactivity through the presumption of the chemical components, and can be used as an admixture to replace cement to prepare the iron tailing-based cementing material. The treatment method for improving the reactivity of the iron tailings and the volcanic ash, which is commonly adopted at present, comprises mechanical force activation (application basis and scientific report, 2019,27 (5): 1149-1157) and a mechanical force activation combined alkali excitation method, wherein the activity index can reach about 81.7 percent in 28 days, but the activation methods still have the problems of insufficient activity excitation, high energy consumption, large pollution and the like.
The microbial leaching technology is an environment-friendly wet metallurgy technology for extracting useful metal components from mineral resources or tailings by utilizing the self oxidation or reduction characteristics of functional microorganisms, and can be used as a potential effective way for solving the problems of reduction of high-grade mineral reserves, increase of tailing stockpiling quantity and the like.
Disclosure of Invention
In view of this, in order to solve the technical problems of low comprehensive utilization rate of the iron tailings, difficult activity excitation, secondary tailing discharge, large energy consumption, heavy environmental pollution and the like in the prior art, the invention provides a comprehensive utilization method of high-silicon type iron tailings, which utilizes mixed flora with the iron-releasing and desiliconization functions to carry out biological leaching on the high-silicon type iron tailings, secondarily recovers iron, can recycle a leaching solution, can effectively improve the chemical reaction activity of leaching residues, can be used as an active admixture for preparing an iron tailing-based cementing material, and aims to realize the comprehensive utilization of the high-silicon type iron tailings.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for comprehensively utilizing high-silicon type iron tailings comprises the following steps:
firstly, ball milling and sieving high-silicon type iron tailings to obtain high-silicon type iron tailing powder;
secondly, mixing the culture solution containing the mixed flora with the iron-decomposing and desiliconizing functions with the leaching solution according to the volume ratio of (1-2): 10 to obtain a mixed solution; wherein the mixed flora is Paracoccus ferrooxidans (ATCC 17741), pseudomonas stutzeri (CGMCC 1.15316) and Arthrobacter neoxitans (CGMCC 1.15651);
the culture solution is prepared by separately culturing Paracoccus ferrooxidans (Paracoccus ferrooxidans), pseudomonas stutzeri (Pseudomonas stutzeri) and Arthrobacter neodiarrhoea (Arthrobacter nicotinianae) in a culture solution of iron bacteria to 10 7 ～10 8 CFU/ml bacterial liquid, and the volume ratio is 5:3:2 mixing, continuously transferring and culturing for 5 generations in the iron bacteria culture solution to obtain a mixed flora culture solution, wherein the bacteria concentration reaches 10 7 ～10 8 CFU/ml；
Thirdly, adding the high-silicon iron tailing powder obtained in the first step into the mixed solution obtained in the second step, and stirring and leaching the ore under an aerobic condition for 7-15 days to obtain leached ore pulp;
fourthly, adding hydrochloric acid into the leached ore pulp obtained in the third step until the pH value is less than 2, adding a hydroxylamine hydrochloride solution with the mass fraction of 10% after the color of the leaching solution is completely changed from reddish brown to yellow, heating, standing and cooling to room temperature after the color of the solution is changed from yellow to pale green, and filtering to obtain filtrate and filter residues, wherein the filtrate is the crude iron recovery solution, and the filter residues are leaching residues;
fifthly, adding oxalic acid solution with the mass fraction of 2% into the filtrate obtained in the fourth step, precipitating ferrous oxalate precipitate under illumination, and recycling the filtered filtrate to the fourth step for use;
and sixthly, rinsing the leaching residue obtained in the fourth step to be neutral by using distilled water, drying to be constant weight, and using the residue as an admixture for preparing the iron tailing-based gelling material.
Furthermore, in the first step, the ball milling time is 30min, and the particle size of the high-silicon type iron tailing powder is less than 45 μm.
Further, in the second step, the leachate comprises the following components: 8.5g/L of citric acid, 0.5g/L of anhydrous magnesium sulfate, 0.5g/L of ferrous sulfate heptahydrate, 0.5g/L of dipotassium phosphate, 0.2g/L of calcium chloride dihydrate, 0.5g/L of sodium nitrate, 4.0g/L of ammonium sulfate and pH of 7.0.
Further, in the second step, the iron bacteria culture solution comprises the following components: 10g/L ferric ammonium citrate, 0.5g/L anhydrous magnesium sulfate, mo Eryan 0.5.5 g/L, 0.5g/L dipotassium hydrogen phosphate, 0.2g/L calcium chloride dihydrate, 0.5g/L sodium nitrate and pH of 7.0.
Further, in the third step, the stirring temperature is 25-35 ℃, the stirring speed is 150-220 r/min, and the solid-to-liquid ratio of the high-silicon type iron tailing powder to the mixed solution is (1-5): (8 to 20).
Further, in the fourth step, the concentration of hydrochloric acid is 4mol/L, and the volume ratio of the hydroxylamine hydrochloride solution to the leaching solution is 1:10.
furthermore, in the fourth step, the heating mode is microwave heating for 3-5 min or heating and boiling for 30 min-1 h.
Further, in the fifth step, the volume ratio of the oxalic acid solution to the filtrate is 1:50.
furthermore, in the fifth step, the illumination intensity is 5000Lux, and the illumination time is 6 h-10 h.
Further, in the sixth step, the drying temperature is 100-110 ℃.
The working principle of the invention is as follows:
iron bacteria are a type of microorganism which oxidizes Fe (II) into Fe (III) under aerobic or anoxic/anaerobic conditions, obtains energy therefrom to synthesize organic matters, and widely exists in fresh water, seawater, sediments and various minerals. Paracoccus ferrooxidans (Paracoccus ferrooxidans), pseudomonas stutzeri (Pseudomonas stutzeri) and Arthrobacter neodiarrhoea (Arthrobacter nicotinianae) used in the present invention are all neutrophilic iron bacteria. The high-silicon type iron tailings are silicate minerals composed of elements such as Si, fe, al and Ca, and the elements Si and Fe on the surface of the high-silicon type iron tailings usually exist in an oxidation state and are connected with each other through intermolecular chemical bonds. The mixed flora used in the invention can secrete extracellular polymers, can adsorb and form a thin layer of biomembrane to wrap the outer surface layer of the high-silicon type iron tailings, and forms a biochemical reaction microenvironment between the biomembrane and the mineral surface. Under the environment, the oxidation-reduction action, the extracellular electron transfer chain and other characteristics of the mixed flora are utilized to change the valence state of the iron element, cause the breakage of intermolecular chemical bonds, change the lattice structure of the iron tailings, ensure that the Fe element in the iron tailings forms ferric hydroxide to be deposited on the surface of the mineral and in the leachate in a large amount, and the insoluble Si in the mineral is dissociated into soluble SiO 2 And the element such as Al, ca and the like with more stable lattice structure is reserved. In addition, the leached ore pulp can be acidified by hydrochloric acid and reduced by hydroxylamine hydrochloride solution, so that insoluble red brown iron hydroxide is changed into stable Fe (II) to be dissolved in the leached liquid, and a crude iron recovery liquid and high-calcium high-aluminum type residues are finally obtained, thereby improving the Al/Si ratio and Ca/Si ratio of the leached residues and obviously increasing the chemical reaction activity of the leached residues. The crude iron recovery liquid can form ferrous oxalate precipitate with oxalic acid under the condition of acidic illumination, so that the iron can be effectively recycled. The ferrous oxalate powder can be used as raw materials of paint, dye, ceramics, optical glass and the like. Compared with Gao Guixing iron tailings, the high-calcium high-aluminum type residues have the advantages that the proportion of active components in the minerals is increased, the volcanic ash reaction activity is greatly improved, and the high-calcium high-aluminum type residues can be used as a mixed material of cement and an active admixture of concrete.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for comprehensively utilizing the high-silicon type iron tailings provided by the invention utilizes the mixed flora with the iron-removing and desiliconization functions to carry out biological leaching on the high-silicon type iron tailings, and then the iron is recycled for the second time, so that the leachate can be recycled, the chemical reaction activity of the leaching residue can be effectively improved, the leachate can be used as an active admixture for preparing the iron tailing-based cementing material, and the purpose of comprehensively utilizing the high-silicon type iron tailings is realized.
2. The invention adopts the microbial leaching-photochemical combined method to treat the high-silicon type iron tailings and the leachate thereof, can effectively recover iron from the high-silicon type iron tailings for the second time, the leachate can be recycled, the iron leaching rate can reach more than 70 percent, the chemical composition of the leaching residue is changed from a high-silicon type to a high-calcium high-aluminum type, the proportion of active components in minerals is obviously improved, the chemical reaction activity of the leaching residue is increased, the leaching residue is used as a blending material for preparing the iron tailing-based cementing material, the strength activity index can reach 95 percent in 28 days, which is higher than that of the existing iron tailing activation method. Compared with the traditional magnetic separation method for recycling iron, the method disclosed by the invention omits a magnetic separation step and magnetic separation equipment, is simple and convenient in process operation, low in equipment requirement, low in cost and energy consumption, and does not discharge secondary tailings.
3. The alkalinity of the high-silicon type iron tailings can be continuously increased under a water environment, the final pH value can reach 10, and the system is difficult to maintain under a neutral environment due to the general composition of the leachate, so that the function of iron bacteria is difficult to exert.
4. The mixed flora used in the invention has good desiliconization capacity besides the iron-removing function. Therefore, the method can effectively extract iron element from the low-grade high-silicon type iron tailings, has high leaching rate, simultaneously converts the inert high-silicon type iron tailings into high-activity high-calcium high-aluminum type leaching residues, meets the use requirement as an active admixture, has no secondary tailings discharge in the whole treatment process, has relatively low cost and simple and convenient operation, realizes the comprehensive cyclic utilization of high-silicon type iron tailings resources, and conforms to the green metallurgy concept of energy conservation and emission reduction.
Description of the drawings:
FIG. 1 is a photograph of mixed flora leached Gao Guixing iron tailings; wherein, the left is a 7-day leaching control group added with high-silicon type iron tailing powder but not with mixed flora; and the right part is a 7-day leaching experimental group of the mixed flora on the high-silicon type iron tailing powder.
Fig. 2 is a technical route diagram for comprehensive utilization of high-silicon type iron tailings.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings 1-2 of the present specification and examples, which are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 2 shows a technical scheme for comprehensive utilization of high-silicon type iron tailings, and the following examples are all implemented according to the technical scheme of fig. 2 in the specification of the invention.
Example 1
Grinding experiment of high-silicon type iron tailings
Ball-milling the high-silicon type iron tailings on a planetary ball mill for 30min, passing the ball-milled mineral powder through a 45-micrometer square-hole copper mesh screen by using an electric vibrating screen machine, and collecting the high-silicon type iron tailings powder with the particle size smaller than 45 micrometers.
Example 2
Mixed flora culture with iron-dissolving and desiliconizing functions
Respectively thawing cryopreserved paracoccus ferrooxidans, pseudomonas stutzeri and arthrobacter neoxides at normal temperature, respectively taking 1.0mL of thawed bacterial liquid to respectively transfer into 100mL of iron bacteria culture solution, performing shaking culture at 30 ℃ for 24h at 180r/min, respectively taking 1.0mL of bacterial liquid from each bacterium to respectively transfer into 100mL of iron bacteria culture solution, performing shaking culture at 30 ℃ for 180r/min for 24h, and enabling each bacterial liquid to be respectivelyThe concentration reaches 10 7 ～10 8 CFU/ml. Then, mixing the activated paracoccus ferrooxidans bacterial liquid, the pseudomonas stutzeri bacterial liquid and the new diarrheal bacterial liquid according to the volume ratio of 5:3:2, mixing, and continuously transferring and culturing the mixed flora in the iron bacteria culture solution for 5 generations.
Wherein the iron bacteria culture solution comprises the following components: 10g/L ferric ammonium citrate, 0.5g/L anhydrous magnesium sulfate, mo Eryan 0.5.5 g/L, 0.5g/L dipotassium hydrogen phosphate, 0.2g/L calcium chloride dihydrate, 0.5g/L sodium nitrate and pH7.0.
Example 3
Leaching effect of mixed flora on high-silicon type iron tailing powder
Transferring the mixed flora cultured for 5 generations in example 2 into 100mL of leachate at an inoculation amount of 10%, adding 5.0g of the high-silicon iron tailing powder in example 1, leaching the ore for 7 days at 30 ℃ under oscillation at 180r/min, adding 4mol/L hydrochloric acid until the pH value of the leachate is less than 2, and adding 10% by mass of hydroxylamine hydrochloride solution after the color of the leachate is completely changed from red brown to yellow, so that the volume ratio of the hydroxylamine hydrochloride solution to the leachate is 1: and 10, then heating for 5min by microwave, changing the color of the solution from yellow to light green, standing, cooling to room temperature, filtering for the first time, recovering the primary filtrate, adding an oxalic acid solution with the mass fraction of 2% into the primary filtrate, and enabling the volume ratio of the oxalic acid solution to the primary filtrate to be 1:50, then irradiating for 6 hours under the illumination intensity of 5000Lux, filtering for the second time, wherein the secondary filter residue is ferrous oxalate precipitate, and recycling the secondary filter liquor into the primary filter liquor for continuous use; rinsing the primary filter residue with distilled water to be neutral, drying the primary filter residue at 105 ℃ to constant weight to obtain leaching residue, weighing, and calculating the residue rate and the iron leaching rate.
Wherein, the components of the leaching solution are as follows: 8.5g/L of citric acid, 0.5g/L of anhydrous magnesium sulfate, 0.5g/L of ferrous sulfate heptahydrate, 0.5g/L of dipotassium phosphate, 0.2g/L of calcium chloride dihydrate, 0.5g/L of sodium nitrate, 4.0g/L of ammonium sulfate and pH of 7.0.
Example 4
Leaching effect of mixed flora on high-silicon type iron tailing powder
Transferring the mixed flora cultured for 5 generations in example 2 into 100mL of leachate at an inoculation amount of 10%, adding 5.0g of the high-silicon iron tailing powder in example 1, leaching the ore for 15 days at 30 ℃ under oscillation at 180r/min, adding 4mol/L hydrochloric acid until the pH value of the leachate is less than 2, and adding 10% by mass of hydroxylamine hydrochloride solution after the color of the leachate is completely changed from red brown to yellow, so that the volume ratio of the hydroxylamine hydrochloride solution to the leachate is 1: and 10, then heating for 5min by microwave, changing the color of the solution from yellow to light green, standing, cooling to room temperature, filtering for the first time, recovering the primary filtrate, adding an oxalic acid solution with the mass fraction of 2% into the primary filtrate, and enabling the volume ratio of the oxalic acid solution to the primary filtrate to be 1:50, then irradiating for 6 hours under the illumination intensity of 5000Lux, filtering for the second time, wherein the secondary filter residue is ferrous oxalate precipitate, and recycling the secondary filter liquor into the primary filter liquor for continuous use; rinsing the primary filter residue with distilled water to be neutral, drying the primary filter residue at 105 ℃ to constant weight to obtain leaching residue, weighing, and calculating the residue rate and the iron leaching rate.
Wherein, the components of the leaching solution are as follows: 8.5g/L of citric acid, 0.5g/L of anhydrous magnesium sulfate, 0.5g/L of ferrous sulfate heptahydrate, 0.5g/L of dipotassium phosphate, 0.2g/L of calcium chloride dihydrate, 0.5g/L of sodium nitrate, 4.0g/L of ammonium sulfate and pH of 7.0.
Example 5
Leaching effect of mixed flora on high-silicon type iron tailing powder
Transferring the mixed flora cultured for 5 generations in example 2 into 800mL of leachate at an inoculation amount of 10%, adding 100.0g of the high-silicon iron tailing powder in example 1, leaching the leachate at 30 ℃ for 15 days under oscillation at 180r/min, measuring the pH value of the leachate, adding 4mol/L hydrochloric acid until the pH value of the leachate is less than 2, adding 10% by mass of hydroxylamine hydrochloride solution after the color of the leachate is completely changed from reddish brown to yellow, and enabling the volume ratio of the hydroxylamine hydrochloride solution to the leachate to be 1: and 10, then heating for 5min by microwave, changing the color of the solution from yellow to light green, standing, cooling to room temperature, filtering for the first time, recovering the primary filtrate, adding an oxalic acid solution with the mass fraction of 2% into the primary filtrate, and enabling the volume ratio of the oxalic acid solution to the primary filtrate to be 1:50, then, after the mixture is illuminated for 10 hours under the illumination intensity of 5000Lux, secondary filtration is carried out, secondary filter residue is ferrous oxalate precipitate, and secondary filtrate is recycled into primary filtrate for continuous use; rinsing the primary filter residue with distilled water to neutrality, drying the primary filter residue at 105 ℃ to constant weight to obtain leaching residue, weighing, and calculating the residue rate.
Wherein, the components of the leaching solution are as follows: 8.5g/L of citric acid, 0.5g/L of anhydrous magnesium sulfate, 0.5g/L of ferrous sulfate heptahydrate, 0.5g/L of dipotassium phosphate, 0.2g/L of calcium chloride dihydrate, 0.5g/L of sodium nitrate, 4.0g/L of ammonium sulfate and pH of 7.0.
Example 6
Leaching effect of mixed flora on high-silicon type iron tailing powder
Transferring the mixed flora cultured for 5 generations in example 2 into 800mL of leachate at an inoculation amount of 10%, adding 200.0g of the high-silicon type iron tailing powder in example 1, performing shaking leaching at 30 ℃ for 15 days at 180r/min, measuring the pH value of the leachate, adding 4mol/L hydrochloric acid until the pH value of the leachate is less than 2, and after the color of the leachate is completely changed from reddish brown to yellow, adding 10% by mass of hydroxylamine hydrochloride solution to ensure that the volume ratio of the hydroxylamine hydrochloride solution to the leachate is 1: and 10, then heating for 5min by microwave, changing the color of the solution from yellow to light green, standing, cooling to room temperature, filtering for the first time, recovering the primary filtrate, adding an oxalic acid solution with the mass fraction of 2% into the primary filtrate, and enabling the volume ratio of the oxalic acid solution to the primary filtrate to be 1:50, then, after the mixture is illuminated for 10 hours under the illumination intensity of 5000Lux, secondary filtration is carried out, secondary filter residue is ferrous oxalate precipitate, and secondary filtrate is recycled into primary filtrate for continuous use; rinsing the primary filter residue with distilled water to neutrality, drying the primary filter residue at 105 ℃ to constant weight to obtain leaching residue, weighing, and calculating the residue rate.
Wherein, the components of the leaching solution are as follows: 8.5g/L of citric acid, 0.5g/L of anhydrous magnesium sulfate, 0.5g/L of ferrous sulfate heptahydrate, 0.5g/L of dipotassium phosphate, 0.2g/L of calcium chloride dihydrate, 0.5g/L of sodium nitrate, 4.0g/L of ammonium sulfate and pH of 7.0.
Example 7
Leaching effect of mixed flora on high-silicon type iron tailing powder
Transferring the mixed flora cultured for 5 generations in example 2 into 800mL of leachate at an inoculation amount of 10%, adding 300.0g of the high-silicon iron tailing powder in example 1, leaching the leachate at 30 ℃ for 15 days under oscillation at 180r/min, measuring the pH value of the leachate, adding 4mol/L hydrochloric acid until the pH value of the leachate is less than 2, adding 10% by mass of hydroxylamine hydrochloride solution after the color of the leachate is completely changed from reddish brown to yellow, and enabling the volume ratio of the hydroxylamine hydrochloride solution to the leachate to be 1: and 10, then heating for 5min by microwave, changing the color of the solution from yellow to light green, standing, cooling to room temperature, filtering for the first time, recovering the primary filtrate, adding an oxalic acid solution with the mass fraction of 2% into the primary filtrate, and enabling the volume ratio of the oxalic acid solution to the primary filtrate to be 1:50, then, after the mixture is illuminated for 10 hours under the illumination intensity of 5000Lux, secondary filtration is carried out, secondary filter residue is ferrous oxalate precipitate, and secondary filtrate is recycled into primary filtrate for continuous use; rinsing the primary filter residue with distilled water to neutrality, drying the primary filter residue at 105 ℃ to constant weight to obtain leaching residue, weighing, and calculating the residue rate.
Wherein, the components of the leaching solution are as follows: 8.5g/L of citric acid, 0.5g/L of anhydrous magnesium sulfate, 0.5g/L of ferrous sulfate heptahydrate, 0.5g/L of dipotassium phosphate, 0.2g/L of calcium chloride dihydrate, 0.5g/L of sodium nitrate, 4.0g/L of ammonium sulfate and pH of 7.0.
Example 8
Leaching effect of mixed flora on high-silicon iron tailing powder
Transferring the mixed flora cultured for 5 generations in example 2 into 800mL of leachate at an inoculation amount of 10%, adding 400.0g of the high-silicon iron tailing powder in example 1, leaching the leachate at 30 ℃ for 15 days under oscillation at 180r/min, measuring the pH value of the leachate, adding 4mol/L hydrochloric acid until the pH value of the leachate is less than 2, adding 10% by mass of hydroxylamine hydrochloride solution after the color of the leachate is completely changed from reddish brown to yellow, and enabling the volume ratio of the hydroxylamine hydrochloride solution to the leachate to be 1: and 10, then heating for 5min by microwave, changing the color of the solution from yellow to light green, standing, cooling to room temperature, filtering for the first time, recovering the primary filtrate, adding an oxalic acid solution with the mass fraction of 2% into the primary filtrate, and enabling the volume ratio of the oxalic acid solution to the primary filtrate to be 1:50, then, after the mixture is illuminated for 10 hours under the illumination intensity of 5000Lux, secondary filtration is carried out, secondary filter residue is ferrous oxalate precipitate, and secondary filtrate is recycled into primary filtrate for continuous use; rinsing the primary filter residue with distilled water to neutrality, drying the primary filter residue at 105 ℃ to constant weight to obtain leaching residue, weighing, and calculating residue rate.
Wherein, the components of the leaching solution are as follows: 8.5g/L of citric acid, 0.5g/L of anhydrous magnesium sulfate, 0.5g/L of ferrous sulfate heptahydrate, 0.5g/L of dipotassium phosphate, 0.2g/L of calcium chloride dihydrate, 0.5g/L of sodium nitrate, 4.0g/L of ammonium sulfate and pH of 7.0.
Comparative example 1
Adding 5.0g of the high-silicon type iron tailing powder obtained in the example 1 into 100mL of leaching solution, carrying out shaking leaching at 30 ℃ for 15 days at 180r/min, then, not causing a reddish brown precipitation phenomenon, filtering, recovering the filtrate, rinsing the filter residue for 2 times by using distilled water, drying the filter residue at 105 ℃ to constant weight, thus obtaining leaching residue, weighing, and calculating the residue rate and the iron leaching rate.
Wherein, the components of the leaching solution are as follows: 8.5g/L of citric acid, 0.5g/L of magnesium sulfate heptahydrate, 0.5g/L of ferrous sulfate heptahydrate, 0.5g/L of dipotassium phosphate, 0.2g/L of calcium chloride, 0.5g/L of sodium nitrate, 4.0g/L of ammonium sulfate and pH of 7.0.
Comparative example 2
Comparative example 2 is the high-silicon type iron ore tailings powder of example 1.
The leaching residues obtained in examples 3, 4 and 1 were subjected to the pozzolanic reaction activity measurement by the method of GB/T2847-2005 pozzolanic mixed material for cement, the mixing amount of the high-silicon type iron tailing powder in the comparative examples and examples was 30%, the test samples were put in an incubator at 40 ℃ ± 1 ℃ and cured for 8 days, and the results are shown in table 1.
TABLE 1 tailing leach effect and pozzolanic properties of leach residue
As shown in fig. 1, the mineral powder in the leachate changed from gray black to reddish brown after the mixed bacterial population was added, as compared with comparative example 1 in which the mixed bacterial population was not added. As seen from table 1, the leaching effect of the mixed bacterial flora in examples 3 and 4 on the high-silica type iron tailings powder is significantly improved, the residue rate is reduced with the extension of the leaching time, and the iron leaching rate is increased with the extension of the leaching time, compared with the comparative example 1 without adding the mixed bacterial flora. The lower hydroxide concentration and calcium oxide concentration of example 4 compared to example 3 in the pozzolan reaction system, the more pozzolanic reactivity is, indicating that the longer leaching time is beneficial for increasing the pozzolanic reactivity of the leach residue. The result shows that the mixed flora can effectively leach the high-silicon type iron tailings, and the chemical composition of the tailings can be changed, so that the volcanic ash reaction activity of the leaching residues is obviously improved.
The leaching residue and the high-silicon type iron ore tailings powder of example 4 and comparative example 2 were further subjected to X-ray fluorescence spectroscopic analysis, and the chemical compositions thereof are shown in table 2.
TABLE 2 chemical composition (wt%) of leach residue and high-silicon type iron ore tailings powder
As seen from Table 2, siO in the leaching residue of example 4 is compared with that of comparative example 2 2 And Fe 2 O 3 The ratio is remarkably reduced, while CaO and Al 2 O 3 The proportion of the active components is obviously increased, which proves that the chemical composition of the tailings can be obviously changed after the mixed flora leaches the high-silicon type iron tailings for 15 days, not only can the iron element be dissociated from the high-silicon type iron tailings, but also the desilication can be carried out, and simultaneously, the active component ratio of the residues, such as CaO and Al, is improved 2 O 3 Thereby remarkably improving the volcanic ash reaction activity of the leaching residue.
Mortar test pieces were prepared according to the mortar mixing ratio of JG/T486-2015 composite admixture for concrete in examples 5 to 8 and comparative example 2, the mixing amount of the test pieces in the comparative example and the example was guaranteed to be 30%, and the prepared test pieces were cured under standard conditions, and the results are shown in Table 3.
TABLE 3 Strength Activity index of high-silicon type iron tailings powder and leach residue
As seen from Table 3, as the solid-to-liquid ratio in the leachate increases, the pH value of the leachate shows a trend of decreasing after 15 days, the residue rate is continuously increased, and the strength activity indexes of the obtained leaching residue as an admixture at 7 days and 28 days are also reduced, which indicates that the excessive addition of the high-silicon type iron tailing powder has an inhibiting effect on the leaching capacity of the mixed flora, so that the leaching effect is poor and the activity of the leaching residue cannot be well excited. The results also reflect that the pH value of the leachate is increased while the mixed flora is leaching ores, the leaching effect is better when the final pH value is more than 9.0, and the strength activity index of the mixed flora in 28 days can reach more than 88%. The high-silicon type iron tailing powder which is simply ball-milled for 30min has almost no activity, so the strength activity index of the high-silicon type iron tailing powder in 28 days is reduced. Under the condition of low solid-to-liquid ratio, the activity of the residue leached by the mixed flora can be obviously improved. Therefore, the mixed flora leached high-silicon type iron tailings can effectively recycle the iron element, can obviously improve the volcanic ash reaction activity of the leached residues, meets the use requirement of an active admixture, has no secondary tailing discharge, is simple and convenient to operate, has relatively low cost, is environment-friendly, and realizes the comprehensive utilization of the high-silicon iron tailings.
The above-mentioned embodiments only represent a few of the embodiments of the present invention, and although the description is specific and detailed, the invention should not be construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A method for comprehensively utilizing high-silicon type iron tailings is characterized by comprising the following steps:
firstly, ball milling and sieving high-silicon type iron tailings to obtain high-silicon type iron tailing powder;
secondly, mixing the culture solution containing the mixed flora with the iron-decomposing and desiliconizing functions with the leaching solution according to the volume ratio of (1-2): 10 to obtain a mixed solution; wherein the mixed flora is Paracoccus ferrooxidans (Paracoccus ferrooxidans), the collection number of the mixed flora is DSM 18071, the collection number of the mixed flora is Pseudomonas stutzeri (Pseudomonas stutzeri), the collection number of the mixed flora is CGMCC 1.15316, the collection number of the mixed flora is Arthrobacter neocathayensis (Arthrobacter niigatensis), and the collection number of the mixed flora is CGMCC 1.15651;
the culture solution is prepared by separately culturing Paracoccus ferrooxidans (Paracoccus ferrooxidans), pseudomonas stutzeri (Pseudomonas stutzeri) and Arthrobacter neodiarrhoea (Arthrobacter niigatenensis) in a ferrobacteria culture solution to obtain a bacterial solution with the concentration of 107-108 CFU/ml, wherein the volume ratio of the Paracoccus ferrooxidans to the Pseudomonas stutzeri to the Pseudomonas neoformans is 5:3:2, mixing, and continuously transferring and culturing for 5 generations in the iron bacteria culture solution to obtain a mixed flora culture solution, wherein the bacteria concentration reaches 107-108 CFU/ml;
thirdly, adding the high-silicon iron tailing powder obtained in the first step into the mixed solution obtained in the second step, and stirring and leaching the ore under an aerobic condition to obtain leached ore pulp;
fourthly, adding hydrochloric acid into the leached ore pulp obtained in the third step until the pH value is less than 2, adding a hydroxylamine hydrochloride solution with the mass fraction of 10% after the color of the leaching solution is completely changed from reddish brown to yellow, heating, standing and cooling to room temperature after the color of the solution is changed from yellow to light green, and filtering to obtain filtrate and filter residues, wherein the filtrate is the crude iron recovery solution, and the filter residues are leaching residues;
fifthly, adding oxalic acid solution with the mass fraction of 2% into the filtrate obtained in the fourth step, precipitating ferrous oxalate precipitate under illumination, and recycling the filtered filtrate to the fourth step for use;
and sixthly, rinsing the leaching residue obtained in the fourth step to be neutral by using distilled water, drying to be constant weight, and using the residue as an admixture for preparing the iron tailing-based gelling material.
2. The method for comprehensively utilizing the high-silicon type iron tailings according to claim 1, wherein in the first step, the ball milling time is 30min, and the particle size of the high-silicon type iron tailings powder is less than 45 μm.
3. The method for comprehensively utilizing the high-silicon type iron tailings according to claim 1, wherein in the second step, the leaching solution comprises the following components: citric acid 8.5g/L, anhydrous magnesium sulfate 0.5g/L, ferrous sulfate heptahydrate 0.5g/L, dipotassium hydrogen phosphate 0.5g/L, calcium chloride dihydrate 0.2g/L, sodium nitrate 0.5g/L, ammonium sulfate 4.0g/L, and pH7.0.
4. The method for comprehensively utilizing the high-silicon type iron tailings according to claim 1, wherein in the second step, the iron bacteria culture solution comprises the following components: ammonium ferric citrate 10g/L, anhydrous magnesium sulfate 0.5g/L, mo Eryan 0.5g/L, dipotassium hydrogen phosphate 0.5g/L, calcium chloride dihydrate 0.2g/L, sodium nitrate 0.5g/L, pH7.0.
5. The method for comprehensively utilizing the high-silicon type iron tailings according to claim 1, wherein in the third step, the stirring temperature is 25-35 ℃, the stirring speed is 150 r/min-220 r/min, and the solid-to-liquid ratio of the high-silicon type iron tailings powder to the mixed liquor is (1-5): (8-20) leaching time is 7-15 days.
6. The method for comprehensively utilizing high-silicon type iron tailings according to claim 1, wherein in the fourth step, the concentration of hydrochloric acid is 4mol/L, and the volume ratio of the hydroxylamine hydrochloride solution to the leaching solution is 1:10.
7. the method for comprehensively utilizing the high-silicon type iron tailings according to claim 1, wherein in the fourth step, the heating mode is microwave heating for 3-5 min or heating and boiling for 30 min-1 h.
8. The method for comprehensively utilizing high-silicon type iron tailings according to claim 1, wherein in the fifth step, the volume ratio of the oxalic acid solution to the filtrate is 1:50.
9. the method for comprehensively utilizing the high-silicon type iron tailings according to claim 1, wherein in the fifth step, the illumination intensity is 5000Lux, and the illumination time is 6 h-10 h.
10. The method for comprehensively utilizing the high-silicon type iron tailings according to claim 1, wherein in the sixth step, the drying temperature is 100-110 ℃.
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