CN111154969A - Depolymerization method of fayalite-rich smelting slag - Google Patents

Depolymerization method of fayalite-rich smelting slag Download PDF

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CN111154969A
CN111154969A CN202010057859.1A CN202010057859A CN111154969A CN 111154969 A CN111154969 A CN 111154969A CN 202010057859 A CN202010057859 A CN 202010057859A CN 111154969 A CN111154969 A CN 111154969A
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smelting slag
depolymerization
fayalite
rich
alkali liquor
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朱能武
张思海
张建易
毛扶林
张宇辰
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention belongs to the field of harmless and recycling of bulk solid wastes, and particularly relates to a depolymerization method of fayalite-rich smelting slag, which comprises the following steps: (1) crushing and grinding the smelting slag rich in the fayalite into powder, and carrying out depolymerization reaction on the obtained smelting slag powder in hot alkali liquor; the alkali liquor is sodium hydroxide solution or potassium hydroxide solution; (2) and (2) carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a leaching solution and depolymerization residues. The invention effectively realizes the thermal alkaline depolymerization of the fayalite in the copper smelting slag at a lower temperature to expose the wrapped harmful and valuable components; meanwhile, the invention also provides an effective pretreatment method for the harmless treatment and the reduction recovery of the fayalite-phase-rich smelting slag.

Description

Depolymerization method of fayalite-rich smelting slag
Technical Field
The invention belongs to the technical field of harmlessness and recycling of metallurgical and bulk industrial smelting slag wastes, and particularly relates to a depolymerization method of fayalite-rich smelting slag.
Background
The output of smelting slag in 2017 years in China is 3.5 hundred million tons, most of the smelting slag is piled up and placed, great environmental risk is caused, and resource waste is caused. Typical bulk solid smelting wastes such as copper smelting slag, nickel smelting slag and the like have a large amount of dangerous components and valuable components at the same time, so that the reasonable harmless and recycling technical requirements are urgent. At present, the treatment modes of copper smelting slag and nickel smelting slag are mainly represented by high-temperature roasting and wet pressure leaching. The prior art is mainly based on recycling of resources (Li, S., et al, A novel process to upper the chip slice by direct reduction-magnetic separation with the addition of Na2CO3 and CaO. powder Technology,2019.347: p.159-169.), but neglects the environmental risk of these large solid wastes due to their harmful elements. Meanwhile, as slagging is required in the smelting process, a large amount of iron and silicon form a compact fayalite structure and wrap a large amount of harmful and valuable components such as arsenic, lead, zinc, copper and the like. Owing to their compact structure, the harmful and valuable constituents enclosed therein are difficult to release (Perederiy, i.and v.g. papangelakis, where amophorus FeO-SiO2 flakes do not acid-leach at high temperature regulation. j Hazard Mater,2017.321: p.737-744), and rational disposal of copper smelting slags faces great challenges. Therefore, effective depolymerizing agents are searched, efficient depolymerization methods of the fayalite in the smelting slag are developed, the successful realization of the fayalite depolymerization of the fayalite in the smelting slag is a difficult problem facing to the harmlessness and reduction of the current bulk smelting waste, and the demand is very urgent.
Disclosure of Invention
Aiming at solving the defects of the prior art, the invention provides a depolymerization method of smelting slag. The depolymerization method is suitable for the smelting slag rich in the fayalite phase, NaOH is used as a depolymerization agent, the fayalite in the copper smelting slag can be effectively depolymerized in hot alkali liquor, and the coated harmful components (arsenic, lead and the like) and valuable components (copper, iron, zinc and the like) are released.
The purpose of the invention is realized by the following technical scheme:
a depolymerization method of fayalite-rich smelting slag comprises the following steps:
(1) crushing and grinding the smelting slag rich in the fayalite into powder, and carrying out depolymerization reaction on the obtained smelting slag powder in hot alkali liquor; the alkali liquor is sodium hydroxide solution or potassium hydroxide solution;
(2) and (2) carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a leaching solution and depolymerization residues.
Preferably, the liquid-solid ratio of the alkali liquor to the smelting slag powder in the step (1) is 3:1-10: 1.
Preferably, the liquid-solid ratio of the alkali liquor to the smelting slag powder in the step (1) is 5:1 ml/g.
Preferably, the mass ratio of the smelting slag powder to NaOH or KOH in the step (1) is 1:1-2.5: 1.
Preferably, the mass ratio of the smelting slag powder to NaOH or KOH in the step (1) is 1: 1.5.
Preferably, the concentration of the alkali liquor in the step (1) is 0.2-0.5 g/ml.
Preferably, the concentration of the alkali liquor in the step (1) is 0.3-0.4 g/ml.
Preferably, the reaction temperature of the step (1) is 70-140 ℃, and the reaction time is at least 2 h.
Preferably, the reaction conditions in step (1) are: the temperature is 110-.
Preferably, the particle size of the smelting slag powder is 50-250 meshes.
Preferably, the particle size of the smelting slag powder is 80-100 meshes.
Preferably, the solid-liquid separation in step (2) is centrifugation under the following conditions: centrifuging at 10000 +/-2000 rpm for 1-5 min.
Preferably, the depolymerized slag obtained by separation in the step (2) is washed 3 times by deionized water, and is subjected to characterization or subsequent treatment after being dried for 12 hours at 75 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method utilizes the characteristics of strong basicity, low volatility and the like of the sodium hydroxide, has good depolymerization effect on the fayalite in the copper smelting slag, can realize effective depolymerization of the fayalite in the copper slag under the optimal condition, inhibits leaching of heavy metals and valuable metals, and realizes depolymerization of the fayalite-rich copper smelting slag and release of harmful valuable components.
(2) The thermal alkali liquor used by the invention can simultaneously realize depolymerization of the fayalite in the copper smelting slag and synchronous leaching of alkaline substances, and an effective depolymerization system and method for the fayalite in the copper smelting slag by the thermal alkali liquor are constructed.
(3) The depolymerization slag used in the invention can be treated in a harmless and reducing way. Compared with the traditional high-temperature roasting or high-pressure acid leaching and other processes, the method has the advantages of simple operation, low energy consumption and safe process, reduces the difficulty of subsequent harmless and quantitative treatment processes, improves the efficiency and promotes the development of circular economy.
Drawings
FIG. 1 is a graph showing the relationship between depolymerization efficiency and depolymerization temperature (a), depolymerization liquid-solid ratio (b), alkali-residue ratio (c) and reaction time (d) selected in example 1.
FIG. 2 is an XRD pattern of the copper smelting slag and the depolymerization residue of example 1, a is an XRD pattern before and after depolymerization, and b is a partial enlarged view of the XRD pattern between 34.5 and 37 degrees before and after depolymerization.
FIG. 3 is SEM and Mapping graphs of copper smelting slag and depolymerization residues in example 1, wherein a and b are surface morphology electron micrographs before and after alkaline depolymerization, respectively, and (a-a) - (a-f) and (b-a) - (b-f) are surface main component distribution graphs of smelting slag morphology before and after alkaline depolymerization, respectively.
FIG. 4 is an FTIR chart of copper smelting slag and disaggregated residues from example 1.
Fig. 5 is a graph of the total efficiency in example 1 and example 2 or 3 or 4.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1: depolymerization of fayalite in copper smelting slag in thermokalite system
By adopting a single-factor variable control method, 30-75g of NaOH with different masses is researched to be dissolved in 150ml of deionized water, the mixed solution is placed in a special solid waste reactor, copper smelting slag with different particle sizes below 15g, 30g, 45g and 60g of 50-200 meshes is added, the stirring rate is 400rmp, different heating temperatures of 70, 90, 110 and 130 ℃ and the depolymerization effect (in terms of silicon leaching) of the copper smelting slag under different time sequence conditions of 0.5, 1, 2, 3, 4h and the like are arranged on a heating plate, and the optimal experimental conditions are determined. Under a specific time series condition, a part of liquid is taken out by an injector and is subjected to high-speed centrifugation, so that solid-liquid separation is realized. The obtained depolymerized liquid is diluted by 5 (v/v)% nitric acid and then analyzed for metal content by an inductively coupled plasma emission spectrometer. The effect of different depolymerization conditions on the leaching efficiency of harmful and valuable components is shown in figure 1. FIG. 1(a) shows that the time to achieve a higher depolymerization effect varies at different temperatures, where an effective depolymerization of fayalite in copper smelting slag is achieved at 130 ℃ for 4h, and at 110 ℃ the efficiency is lower. Fig. 1(b) shows that with increasing liquid-to-solid ratio, a liquid-to-solid ratio of 5:1 still achieves a better depolymerization of the copper smelting slag. FIG. 1(c) shows that an increase in the NaOH dosage is beneficial in improving the depolymerization of copper smelting slag, with the release of silicon being maximized at 45g NaOH. Optimized, optimal depolymerization conditions: 45g of NaOH system, the liquid-solid ratio of 5:1, the temperature of 130 ℃ and 4 hours can realize the effective depolymerization of the fayalite in 30g of copper smelting slag.
The raw material and the residue of solid-liquid separation of the hot NaOH solution system were subjected to material characterization, and the dried residue was cleaned by XRD analysis, with the results shown in FIG. 2. Fig. 2(a) shows that the original copper smelting slag powder mainly contains an iron olivine phase, and the phase of the depolymerized copper smelting slag is changed after depolymerization with a hot alkaline solution. As is clear from the enlarged view in FIG. 2(b), the fayalite phase gradually disappeared from the slag. The surface morphology of the copper smelting slag before and after the observation of the reaction by a Scanning Electron Microscope (SEM) is shown in figures 3(a) and 3(b), and the result shows that a large number of holes are formed after thermal alkaline depolymerization compared with the compact surface in the original copper smelting slag. The images of the electron spectroscopy (mapping) are shown in fig. 3 and table 1, and after the copper smelting slag is treated by the hot alkali liquor, a large amount of harmful and valuable components are exposed on the surface of the copper smelting slag. Thus, the depolymerization of fayalite in copper smelting slag can be effectively achieved using hot sodium hydroxide solution.
TABLE 1 comparison of the content of elements of the copper smelting slag and the depolymerization residue in the energy spectrum of example 1
Figure BDA0002373416150000051
Example 2
The depolymerization residues are subjected to enhanced leaching by adopting a liquid-solid ratio of 10:1 and 1.2M sulfuric acid and 0.6M hydrogen peroxide, and are stirred and leached for 4 hours under the condition of a stirring speed of 400 rmp. The total leaching rate of arsenic is 99.7%, the total leaching rate of lead is 1.61%, and the decrement rate is 57.1% by calculation.
Example 3
The depolymerization residues are subjected to enhanced leaching by adopting a liquid-solid ratio of 10:1 and 1.8M of dilute hydrochloric acid and 0.6M of hydrogen peroxide, and are stirred and leached for 4 hours under the condition that the stirring speed is 400 rmp. The total leaching rate of arsenic is 99.7%, the total leaching rate of lead is 99.9%, and the decrement rate is 46.3%.
Example 4
The depolymerization residues are subjected to enhanced leaching by adopting a liquid-solid ratio of 10:1 and 1.4M of dilute nitric acid and 0.6M of hydrogen peroxide, and are stirred and leached for 4 hours under the condition that the stirring speed is 400 rmp. The total leaching rate of arsenic is 99.7%, the total leaching rate of lead is 99.9%, and the decrement rate is 48.1% through calculation.
Table 2 shows the residual amounts of the respective components in the slag after the reaction of examples 1 and 2 to 4
Figure BDA0002373416150000061
As can be seen from Table 2, the contents of arsenic and copper in the slag after the treatment of example 2 are only 8.3mg/kg and 27.5mg/kg through the combined leaching process of thermal alkaline depolymerization and dilute acid oxidation, and lead is enriched after the treatment because lead sulfate precipitates are easily formed in a sulfuric acid system. After the treatment of the embodiment 3 or the embodiment 4, arsenic and copper achieve better extraction effect, and lead is extracted from slag. The harmlessness and the reduction of the fayalite smelting slag are synchronously realized. The harmless effect of the invention is the leaching rate of harmful or valuable components, the leaching rate is calculated by the ratio of the leaching amount of each component to the content of smelting slag, and the total leaching rate is the sum of the alkaline depolymerization efficiency and the dilute acid strengthening efficiency. The reduction effect is the comparison of the difference value of the leached slag and the original slag.
Therefore, the hot sodium hydroxide solution can be used for realizing the effective depolymerization of the fayalite in the copper smelting slag, the effective extraction of harmful components and valuable components of the depolymerized smelting slag can be realized under dilute acid, and the harmlessness and the reduction of the smelting slag rich in the fayalite structure can be realized.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.

Claims (10)

1. A depolymerization method of fayalite-rich smelting slag is characterized by comprising the following steps:
(1) crushing and grinding the smelting slag rich in the fayalite into powder, and carrying out depolymerization reaction on the obtained smelting slag powder in hot alkali liquor; the alkali liquor is sodium hydroxide solution or potassium hydroxide solution;
(2) and (2) carrying out solid-liquid separation on the reaction product obtained in the step (1) to obtain a leaching solution and depolymerization residues.
2. The method according to claim 1, characterized in that the liquid-solid ratio of the lye to the smelting slag powder of step (1) is 3:1-10: 1.
3. The method according to claim 2, characterized in that the liquid-solid ratio of the lye to the smelting slag powder of step (1) is 5:1 ml/g.
4. The method as claimed in claim 1, 2 or 3, wherein the concentration of the lye of step (1) is 0.2-0.5 g/ml.
5. The method as claimed in claim 4, wherein the concentration of the alkali liquor in the step (1) is 0.3-0.4 g/ml.
6. The method of claim 5, wherein the reaction temperature in step (1) is 70-140 ℃ and the reaction time is at least 2 h.
7. The method of claim 6, wherein the reaction conditions in step (1) are: the temperature is 110-.
8. The method according to claim 7, characterized in that the particle size of the smelting slag powder is 50-250 mesh.
9. The method according to claim 8, characterized in that the particle size of the smelting slag powder is 80-100 mesh.
10. The method according to claim 9, wherein the solid-liquid separation in step (2) is centrifugation under the following conditions: centrifuging at 10000 +/-2000 rpm for 1-5 min.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112695203A (en) * 2020-12-07 2021-04-23 鹰潭盛发铜业有限公司 Efficient and environment-friendly recovery method of copper slag

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103343225A (en) * 2013-06-27 2013-10-09 中国铝业股份有限公司 Comprehensive utilization method of ferriferous fayalite material
CN110629015A (en) * 2019-09-11 2019-12-31 武汉理工大学 Iron olivine type slag desiliconization method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103343225A (en) * 2013-06-27 2013-10-09 中国铝业股份有限公司 Comprehensive utilization method of ferriferous fayalite material
CN110629015A (en) * 2019-09-11 2019-12-31 武汉理工大学 Iron olivine type slag desiliconization method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112695203A (en) * 2020-12-07 2021-04-23 鹰潭盛发铜业有限公司 Efficient and environment-friendly recovery method of copper slag

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Application publication date: 20200515