CN115725853B - Arsenic fixing smelting method of high-arsenic copper concentrate - Google Patents
Arsenic fixing smelting method of high-arsenic copper concentrate Download PDFInfo
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- 238000003723 Smelting Methods 0.000 title claims abstract description 101
- 239000012141 concentrate Substances 0.000 title claims abstract description 78
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 69
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000002893 slag Substances 0.000 claims abstract description 170
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003830 anthracite Substances 0.000 claims abstract description 26
- 238000004321 preservation Methods 0.000 claims abstract description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 21
- 239000000155 melt Substances 0.000 claims abstract description 21
- 238000010791 quenching Methods 0.000 claims abstract description 20
- 230000000171 quenching effect Effects 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 62
- 239000000395 magnesium oxide Substances 0.000 claims description 31
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 17
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 17
- 239000004571 lime Substances 0.000 claims description 17
- 229910000514 dolomite Inorganic materials 0.000 claims description 16
- 239000010459 dolomite Substances 0.000 claims description 16
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052802 copper Inorganic materials 0.000 abstract description 37
- 239000010949 copper Substances 0.000 abstract description 37
- 230000008569 process Effects 0.000 abstract description 18
- 230000009467 reduction Effects 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000007711 solidification Methods 0.000 abstract description 4
- 238000009853 pyrometallurgy Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
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- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
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- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
- 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
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Abstract
The invention relates to the technical field of pyrometallurgy copper, in particular to a method for smelting solid arsenic from high-arsenic copper concentrate, which comprises the following steps: placing the high-arsenic copper concentrate, anthracite and slag former into an electric furnace for smelting treatment to obtain a melt; placing the melt into a depletion electric furnace for heat preservation depletion treatment to obtain discharged slag and matte; carrying out water quenching treatment on the discharged slag to obtain final slag; the final slag is SiO containing arsenic 2 ‑CaO‑MgO‑Al 2 O 3 And (5) quaternary slag. According to the invention, the high-arsenic copper concentrate is compounded with the slag former, and the arsenic element is solidified in the final slag by utilizing smelting treatment and heat preservation depletion treatment, so that source reduction of harmful impurity elements such as arsenic is realized; the method has simple process, and arsenic in the high-arsenic copper concentrate enters a slag phase as much as possible through adjustment of the slag former, so that high-solidification arsenic slag is obtained, and the environmental protection pressure is reduced.
Description
Technical Field
The invention relates to the technical field of pyrometallurgy copper, in particular to an arsenic-fixing smelting method of high-arsenic copper concentrate.
Background
With the development of economy, copper mine resources in China are difficult to meet the requirement of continuous and rapid development of economy in China, and copper metal mineral resources in China face a very serious shortage situation. Copper is an important metal resource, and has wide application in national economy and national defense construction, but copper smelting raw materials have serious shortage, concentrate of more than about 60% of each year needs to be imported, along with shortage of resource supply, the treatment proportion of complex materials, especially high-arsenic materials, is continuously increased, and due to mineral properties or mineral separation technical problems, arsenic is difficult to completely separate in the mineral separation process, so that the concentrate contains a certain amount of arsenic.
At present, there are 2 main ways for treating the arsenic-containing material, one way is to make the arsenic-containing material harmless, so that the arsenic is stored in the form of stable ferric arsenate, calcium arsenate and the like; the other is to comprehensively utilize the arsenic-containing material, make the arsenic in the material into arsenic products, comprehensively recover other valuable metals, and achieve the dual purposes of pollution control and comprehensive utilization 2 O 3 Arsenate, arsenic metal, etc.
In general, the harmful impurity elements such as arsenic in the copper smelting process are mainly remained in the aspect of passive treatment after waste is generated, and the development on the aspect of front-end reduction is less.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for smelting arsenic in high-arsenic copper concentrate, which aims to solve the problem that arsenic in the copper concentrate is difficult to enter a slag phase in the existing copper smelting process, so that the environment is polluted.
The technical scheme of the invention is as follows:
an arsenic fixing smelting method of high-arsenic copper concentrate, comprising the following steps:
providing high arsenic copper concentrate, anthracite and a slag former;
placing the high-arsenic copper concentrate, anthracite and slag former into an electric furnace for smelting treatment to obtain a melt;
placing the melt into a depletion electric furnace for heat preservation depletion treatment to obtain discharged slag and matte;
carrying out water quenching treatment on the discharged slag to obtain final slag; the final slag is SiO containing arsenic 2 -CaO-MgO-Al 2 O 3 And (5) quaternary slag.
The method for smelting the arsenic from the high-arsenic copper concentrate comprises the steps that the slag former is one or more selected from lime, serpentine, dolomite and silica; the weight percentages are as follows:
the content of CaO in the lime is more than or equal to 85 percent, and SiO 2 The content of MgO is less than or equal to 2 percent, and the content of MgO is less than or equal to 5 percent;
in the dolomite, the content of MgO is more than or equal to 35 percent, the content of CaO is more than or equal to 50 percent, and SiO 2 The content of (2) is less than or equal to 3 percent;
in the serpentine, siO 2 The content of MgO is more than or equal to 35 percent, and the content of MgO is more than or equal to 35 percent.
According to the arsenic-fixing smelting method of the high-arsenic copper concentrate, the slag former is a mixture of magnesia lime, serpentine and dolomite, and the mass ratio of the magnesia lime to the serpentine to the dolomite is (3-4): (1-2): 2.
According to the arsenic-fixing smelting method of the high-arsenic copper concentrate, the mass ratio of the high-arsenic copper concentrate to the anthracite to the slag former is (40-80), the mass ratio of the high-arsenic copper concentrate to the anthracite to the slag former is (5-20), and the mass ratio of the high-arsenic copper concentrate to the anthracite to the slag former is (1-10).
The method for smelting the solid arsenic in the high-arsenic copper concentrate comprises the steps of 2 O 3 The sum of the mass percentages of the components is less than or equal to 35 percent.
According to the arsenic-fixing smelting method of the high-arsenic copper concentrate, the smelting treatment temperature is 1180-1220 ℃, and the smelting treatment time is more than 20 minutes.
According to the arsenic-fixing smelting method of the high-arsenic copper concentrate, the temperature of the heat-preservation depletion treatment is 1150-1250 ℃, and the time of the heat-preservation depletion treatment is more than 2 hours.
The method for smelting the arsenic in the high-arsenic copper concentrate comprises the steps of 2 -CaO-MgO-Al 2 O 3 The quaternary slag comprises SiO by mass percent 2 30-33%, caO 3-6%, mgO 38-43% and Al 2 O 3 24-27％。
According to the arsenic-fixing smelting method of the high-arsenic copper concentrate, the alkalinity of the final slag is more than or equal to 1.6; the melting point of the final slag is 1150-1250 ℃.
The method for smelting the solid arsenic in the high-arsenic copper concentrate comprises the steps of adding the MgO and the Al in the high-arsenic copper concentrate, the anthracite and the slagging constituent 2 O 3 The mass ratio of (2) is 1.5-1.7.
The beneficial effects are that: the invention provides an arsenic fixing smelting method of high-arsenic copper concentrate, which comprises the following steps: placing the high-arsenic copper concentrate, anthracite and slag former into an electric furnace for smelting treatment to obtain a melt; placing the melt into a depletion electric furnace for heat preservation depletion treatment to obtain discharged slag and matte; carrying out water quenching treatment on the discharged slag to obtain final slag; the final slag is SiO containing arsenic 2 -CaO-MgO-Al 2 O 3 And (5) quaternary slag. According to the invention, the high-arsenic copper concentrate is compounded with the slag former, and the arsenic element is solidified in the final slag by utilizing smelting treatment and heat preservation depletion treatment, so that source reduction of harmful impurity elements such as arsenic is realized; the method has simple process, and arsenic in the high-arsenic copper concentrate enters a slag phase as much as possible through adjustment of the slag former, so that high-solidification arsenic slag is obtained, and the environmental protection pressure is reduced.
Drawings
FIG. 1 is a schematic diagram of the process flow of the method for smelting solid arsenic in high-arsenic copper concentrate.
Detailed Description
The invention provides an arsenic fixing smelting method of high-arsenic copper concentrate, which aims to make the purposes, the technical scheme and the effects of the invention clearer and more definite, and is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description and claims, unless the context specifically defines the terms "a," "an," "the," and "the" include plural referents. If there is a description of "first", "second", etc. in an embodiment of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The term "and/or" as used herein includes all or any element and all combination of one or more of the associated listed items.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
At present, china becomes the first large copper producing country and consuming country in the world, the copper production capacity of China is 1002.5 ten thousand tons and the consumption capacity of copper production is 1350 ten thousand tons in 2020, which account for 25% of the global consumption, but the copper mine resource self-sufficiency rate of China is seriously insufficient, and the dependence on the copper mine resource is over 70%. According to the information of the national resource department in 2015, the copper metal resource reserves of 1150 ten thousand tons in China, the reserve basis of 2125 ten thousand tons and the average human reserve of less than half of the world average level are shown. In recent 15 years, the copper ore reserves in China are hardly increased, and the domestic mineral self-sufficiency rate is reduced from 53.78% to 28.8% within 10 years.
However, at present, due to the nature of minerals or the technical problem of beneficiation, it is difficult to completely separate arsenic in the beneficiation process, so that the concentrate contains a certain amount of arsenic. In the prior art, harmful impurity elements such as arsenic in the copper smelting process are mainly remained in the aspect of passive treatment after waste is generated, and the development of the front-end reduction is less.
According to the research of the invention, the directional regulation technology is adopted to accurately regulate and control the harmful impurity elements in the copper smelting process to gangue phase, thereby realizing source reduction of harmful impurity elements such as arsenic and the like, and having important promotion effect on promoting the healthy and sustainable development of the copper smelting industry.
Based on this, please refer to fig. 1, the invention provides a method for smelting solid arsenic from high-arsenic copper concentrate, comprising the following steps:
step S10: providing high arsenic copper concentrate, anthracite and a slag former;
step S20: placing the high-arsenic copper concentrate, anthracite and slag former into an electric furnace for smelting treatment to obtain a melt;
step S30: placing the melt into a depletion electric furnace for heat preservation depletion treatment to obtain discharged slag and matte;
step S40: carrying out water quenching treatment on the discharged slag to obtain final slag; the final slag is arsenic-containing SiO2-CaO-MgO-Al2O3 quaternary slag.
In the embodiment, high-arsenic copper concentrate, anthracite and a slagging agent are used as main raw materials for smelting, and the high-arsenic copper concentrate and the slagging agent are compounded, so that the arsenic content in the finally obtained matte is low, the arsenic element is effectively fixed in the final slag, the reduction at the source is realized, and the environmental protection pressure is reduced; in addition, the arsenic-fixing smelting method of the high-arsenic copper concentrate is simple in process, and arsenic in the high-arsenic copper concentrate can enter a slag phase as much as possible through adjustment of a slag former, so that the arsenic content in the product matte is low.
In some embodiments, the smelting process in step S20 is performed in an isattva furnace.
Specifically, the melt obtained after smelting is fed into a depletion electric furnace, the melt smelted by the Isa furnace is subjected to heat preservation depletion, after discharging, the discharged slag is subjected to water quenching treatment, copper matte is discharged to enter the next working procedure, and the rest of the final slag is SiO containing arsenic 2 -CaO-MgO-Al 2 O 3 And (5) quaternary slag.
In some embodiments, the slag former is selected from one or more of lime, serpentine, dolomite, silica; the weight percentages are as follows:
the content of CaO in the lime is more than or equal to 85 percent, and SiO 2 The content of MgO is less than or equal to 2 percent, and the content of MgO is less than or equal to 5 percent;
in the dolomite, the content of MgO is more than or equal to 35 percent, the content of CaO is more than or equal to 50 percent, and SiO 2 The content of (2) is less than or equal to 3 percent;
in the serpentine, siO 2 The content of MgO is more than or equal to 35 percent, and the content of MgO is more than or equal to 35 percent.
In a preferred embodiment, the slag former is a mixture of magnesia lime, serpentine and dolomite in a mass ratio of (3-4): (1-2): 2. By adjusting the slag former, arsenic in the high-arsenic copper concentrate enters a slag phase as much as possible, so that high-solidification arsenic slag is obtained.
In some embodiments, the high arsenic copper concentrate, anthracite and slag former are in a mass ratio of (40-80): (5-20): (1-10).
In a specific embodiment, the mass ratio of the high-arsenic copper concentrate to the anthracite to the slag former is (50-70): (8-15): (3-7); preferably, the mass ratio of the high-arsenic copper concentrate to the anthracite to the slag former is 60:12:5. The furnace charging proportion of the high-arsenic copper concentrate, the anthracite and the slag former is regulated, so that the slag former is suitable in quantity, excessive slag quantity is avoided, and the utilization rate of alloy elements is reduced although the impurity removal rate is improved; in the dosage range of the slag former, the phosphorus and sulfur can be ensured to be reduced to the content required by the compounding, and simultaneously, the quaternary slag type with high alkalinity can be obtained.
In some embodiments, mgO and Al in the high-arsenic copper concentrate 2 O 3 The sum of the mass percentages of the components is less than or equal to 35 percent; mgO and Al are charged into the furnace 2 O 3 The mass percentage of the slag is controlled within the range, so that the conductivity of the raw material fed into the furnace can be improved, and the corrosion of the thin slag to the furnace lining is inhibited; meanwhile, the melting point of the slag is moderately reduced by adjusting the slag type, so that the fluidity of the slag is improved, the yield is increased, and the electricity consumption is reduced.
In some embodiments, the temperature of the smelting process is 1180-1220 ℃, and the time of the smelting process is greater than 20 minutes.
In a specific embodiment, the temperature of the smelting process is 1190-1220 ℃, and the time of the smelting process is 30-50min; preferably, the temperature of the smelting treatment is 1200-1210 ℃, and the time of the smelting treatment is 35min; the selective reduction effect of copper ores can be improved within the smelting treatment temperature and time.
In some embodiments, the temperature of the soak lean treatment is 1150-1250 ℃, and the time of the soak lean treatment is greater than 2 hours.
In a specific embodiment, the temperature of the heat preservation and depletion treatment is 1200-1250 ℃, and the time of the heat preservation and depletion treatment is 3-5h; preferably, the temperature of the heat preservation and depletion treatment is 1220-1250 ℃, and the time of the heat preservation and depletion treatment is 4 hours; the heat preservation and depletion treatment is carried out at the temperature and the time, so that the effect of selective reduction of copper ores can be improved.
In some embodiments, the arsenic-containing SiO 2 -CaO-MgO-Al 2 O 3 The quaternary slag comprises SiO by mass percent 2 30-33%, caO 3-6%, mgO 38-43% and Al 2 O 3 24-27％。
In some embodiments, the final slag has an alkalinity of 1.6 or greater.
In some embodiments, mgO and Al in the high-arsenic copper concentrate, anthracite and slag former 2 O 3 The mass ratio of (2) is 1.5-1.7.
In the embodiment, the heat conduction performance and the activity of slag can be simultaneously achieved by compounding copper concentrate and slag forming agent, adjusting the magnesium-aluminum ratio of the charged slag to be between 1.5 and 1.7 and the alkalinity of the final slag to be more than or equal to 1.6.
In some embodiments, the final slag has a melting point of 1150-1250 ℃; the melting point of the final slag is ensured to be within the range, and the smelting effect can be effectively ensured.
Specifically, according to the magnesium-aluminum ratio (1.5-1.7) of the furnace,adjusting the final slag to make the final slag be arsenic-containing SiO 2 -CaO-MgO-Al 2 O 3 The quaternary slag type and the alkalinity are more than or equal to 1.6, the content of Si in the melt is controlled to be lower through high alkalinity operation, and the melting point of slag is moderately reduced through adjusting the quaternary slag type so as to be converted into uniform liquid at a lower temperature, thereby improving the fluidity of slag, reducing the viscosity of slag and accelerating the transfer of substances between molten steel and slag; and simultaneously avoid the erosion of the furnace lining caused by too low melting point and too low viscosity.
In a preferred embodiment, the final slag has an alkalinity between 1.6 and 2.0; by high alkalinity operation, the Si content in the melt can be controlled to be low, and the melting point of the slag is moderately reduced by adjusting the quaternary slag type.
Specifically, in the step S40, the discharged slag is subjected to water quenching treatment, so that arsenic element can be solidified into final slag, the arsenic element is reduced from entering the flue gas, and the amount of final arsenic waste acid is reduced, so that the cost for treating the waste acid is greatly saved. The water quenching treatment of copper slag is to put the blast furnace slag in a hot melting state into water for rapid cooling, limit crystallization and generate granulation. The water quenching method commonly adopted at present comprises two types of slag pool water quenching and stokehold water quenching.
1. Pool-type water quenching: the locomotive is used for pulling the slag tank beside the water tank, crushing the surface slag shell, slowly pouring the slag into the water tank, and cooling the molten slag into granular water slag rapidly when meeting water. The water slag is grabbed out by a crane and placed in a slag stacking field, and is loaded and transported outside after dehydration.
The pool type water quenching process equipment is simple and reliable, and the water consumption is low. But generates a large amount of steam, slag cotton and H 2 S gas, environmental pollution is large; about 15% of the slag shells of the sticking tank cannot be quenched by water; facilities such as slag tanks, railway special lines and the like are required to be specially arranged. The process belongs to a process which is gradually eliminated.
2. Water quenching in front of the furnace: a slag flushing groove is arranged in front of a blast furnace hearth to form a groove, slag is quenched into particles in the slag flushing groove (groove) by high-pressure water, the particles are conveyed to a slag sedimentation tank, water slag is grabbed out by a grab bucket, and the particles are piled up, dehydrated and then transported outwards.
The following examples are further illustrative of the invention. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Example 1
The embodiment provides an arsenic fixing smelting method of high-arsenic copper concentrate, which comprises the following steps:
(1) Respectively proportioning according to the mass ratio of the copper concentrate, the anthracite and the slag former of 60:12:5; the slag former is magnesia lime, serpentine and dolomite with the mass ratio of 3:1:2.
(2) Feeding the raw materials into an electric furnace for smelting, wherein the smelting temperature is 1200 ℃, the smelting time is 30min, the raw materials enter a depletion electric furnace after smelting, the heat preservation depletion is carried out on the melt smelted by the Isa furnace, the water quenching treatment is carried out on the discharged slag after the discharging is completed, and the copper matte is discharged to enter the next working procedure. The smelting temperature of the depletion electric furnace is 1220 ℃, the depletion smelting time is 2.5h, and the final slag is SiO 2 -CaO-MgO-Al 2 O 3 And a quaternary slag type.
Example 2
The embodiment provides an arsenic fixing smelting method of high-arsenic copper concentrate, which comprises the following steps:
(1) Respectively proportioning according to the mass ratio of the copper concentrate, the anthracite and the slag former of 50:8:3; the slag former is magnesia lime, serpentine and dolomite with the mass ratio of 3:1:2.
(2) Feeding the raw materials into an electric furnace for smelting, wherein the smelting temperature is 1200 ℃, the smelting time is 30min, the raw materials enter a depletion electric furnace after smelting, the heat preservation depletion is carried out on the melt smelted by the Isa furnace, the water quenching treatment is carried out on the discharged slag after the discharging is completed, and the copper matte is discharged to enter the next working procedure. The smelting temperature of the depletion electric furnace is 1220 ℃, the depletion smelting time is 2.5h, and the final slag is SiO 2 -CaO-MgO-Al 2 O 3 And a quaternary slag type.
Example 3
The embodiment provides an arsenic fixing smelting method of high-arsenic copper concentrate, which comprises the following steps:
(1) Respectively proportioning according to the mass ratio of the copper concentrate, the anthracite and the slag former of 70:15:7; the slag former is magnesia lime, serpentine and dolomite with the mass ratio of 3:1:2.
(2) Feeding the raw materials into an electric furnace for smelting, wherein the smelting temperature is 1200 ℃, the smelting time is 30min, the raw materials enter a depletion electric furnace after smelting, the heat preservation depletion is carried out on the melt smelted by the Isa furnace, the water quenching treatment is carried out on the discharged slag after the discharging is completed, and the copper matte is discharged to enter the next working procedure. The smelting temperature of the depletion electric furnace is 1220 ℃, the depletion smelting time is 2.5h, and the final slag is SiO 2 -CaO-MgO-Al 2 O 3 And a quaternary slag type.
Example 4
The embodiment provides an arsenic fixing smelting method of high-arsenic copper concentrate, which comprises the following steps:
(1) Respectively proportioning according to the mass ratio of the copper concentrate, the anthracite and the slag former of 40:5:1; the slag former is magnesia lime, serpentine and dolomite with the mass ratio of 3:1:2.
(2) Feeding the raw materials into an electric furnace for smelting, wherein the smelting temperature is 1200 ℃, the smelting time is 30min, the raw materials enter a depletion electric furnace after smelting, the heat preservation depletion is carried out on the melt smelted by the Isa furnace, the water quenching treatment is carried out on the discharged slag after the discharging is completed, and the copper matte is discharged to enter the next working procedure. The smelting temperature of the depletion electric furnace is 1220 ℃, the depletion smelting time is 2.5h, and the final slag is SiO 2 -CaO-MgO-Al 2 O 3 And a quaternary slag type.
Example 5
The embodiment provides an arsenic fixing smelting method of high-arsenic copper concentrate, which comprises the following steps:
(1) Respectively proportioning according to the mass ratio of the copper concentrate, the anthracite and the slag former of 8:2:1;
the slag former is magnesia lime, serpentine and dolomite with the mass ratio of 3:1:2.
(2) Feeding the raw materials into an electric furnace for smelting, wherein the smelting temperature is 1200 ℃, the smelting time is 30min, the raw materials enter a depletion electric furnace after smelting, the heat preservation depletion is carried out on the melt smelted by the Isa furnace, after the furnace discharging is finished,and (5) carrying out water quenching treatment on the discharged slag, and discharging copper matte to enter the next working procedure. The smelting temperature of the depletion electric furnace is 1220 ℃, the depletion smelting time is 2.5h, and the final slag is SiO 2 -CaO-MgO-Al 2 O 3 And a quaternary slag type.
Example 6
This embodiment is substantially the same as embodiment 1, except that: the smelting temperature is 1220 ℃, and the smelting time is 40min.
Example 7
This embodiment is substantially the same as embodiment 1, except that: the smelting temperature is 1230 ℃, and the smelting time is 50min.
Example 8
This embodiment is substantially the same as embodiment 1, except that: the slag former is magnesia lime, silica and dolomite with the mass ratio of 3:1:2.
Example 9
This embodiment is substantially the same as embodiment 1, except that: the proportion of copper concentrate, coke and slag former is adjusted to be 4:1:1.
Example 10
This embodiment is substantially the same as embodiment 1, except that: the proportion of copper concentrate, coke and slag former is adjusted to be 50:8:2.
Example 11
This example is essentially the same as example 1, except that the ratio of copper concentrate, coke and slag former is adjusted to be 5:1:1.
Comparative example 1
Comparative example 1 reference example 1, which is different in that the final slag was adjusted to CaO-SiO using a 3:1 ratio of lime to silica as a slag former 2 -Al 2 O 3 Ternary slag type.
For comparative description of the smelting methods of the embodiments and comparative examples of the present invention, mgO/Al of the raw materials charged into the furnace during smelting is measured 2 O 3 The ratio and final slag basicity were measured, and the specific test results are shown in table 1 below.
TABLE 1 MgO/Al of raw materials charged into furnace for different smelting methods 2 O 3 Ratio and final slag basicity table
| Reference numerals | MgO/Al 2 O 3 Ratio of | Final slag basicity |
| Example 1 | 1.53 | 1.78 |
| Example 2 | 1.51 | 1.72 |
| Example 3 | 1.62 | 1.77 |
| Example 4 | 1.50 | 1.61 |
| Example 5 | 1.68 | 1.80 |
| Example 6 | 1.53 | 1.73 |
| Example 7 | 1.53 | 1.74 |
| Example 8 | 1.50 | 1.71 |
| Example 9 | 1.81 | 1.86 |
| Example 10 | 1.33 | 1.61 |
| Example 11 | 1.92 | 2.03 |
| Comparative example 1 | 1.19 | 1.28 |
For comparative explanation of the smelting methods of the present invention in each example and comparative example, arsenic content of slag phases prepared in each example and comparative example was tested, and specific test results are shown in table 2 below.
TABLE 2 arsenic-containing SiO 2 -CaO-MgO-Al 2 O 3 Arsenic content data table in quaternary slag
| Reference numerals | As/％ |
| Example 1 | 0.55 |
| Example 2 | 0.50 |
| Example 3 | 0.60 |
| Example 4 | 0.67 |
| Example 5 | 0.66 |
| Example 6 | 0.57 |
| Example 7 | 0.53 |
| Example 8 | 0.58 |
| Example 9 | 0.61 |
| Example 10 | 0.63 |
| Example 11 | 0.52 |
| Comparative example 1 | 0.22 |
As can be seen from tables 1 and 2, the arsenic-fixing smelting method of the high-arsenic copper concentrate can effectively improve the slag-in rate of element As, improve the economic benefit and reduce the environmental protection pressure.
In summary, the method for smelting arsenic from high-arsenic copper concentrate provided by the invention comprises the following steps: placing the high-arsenic copper concentrate, anthracite and slag former into an electric furnace for smelting treatment to obtain a melt; placing the melt into a depletion electric furnace for heat preservation depletion treatment to obtain discharged slag and matte; carrying out water quenching treatment on the discharged slag to obtain final slag; the final slag is SiO containing arsenic 2 -CaO-MgO-Al 2 O 3 And (5) quaternary slag. According to the invention, the high-arsenic copper concentrate is compounded with the slag former, and the arsenic element is solidified in the final slag by utilizing smelting treatment and heat preservation depletion treatment, so that source reduction of harmful impurity elements such as arsenic is realized; the method has simple process, and arsenic in the high-arsenic copper concentrate enters a slag phase as much as possible through adjustment of the slag former, so that high-solidification arsenic slag is obtained, and the environmental protection pressure is reduced.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (6)
1. The method for smelting the solid arsenic of the high-arsenic copper concentrate is characterized by comprising the following steps of:
providing high arsenic copper concentrate, anthracite and a slag former;
placing the high-arsenic copper concentrate, anthracite and slag former into an Isa furnace for smelting treatment to obtain a melt;
placing the melt into a depletion electric furnace for heat preservation depletion treatment to obtain discharged slag and matte;
carrying out water quenching treatment on the discharged slag to obtain final slag; the final slag is SiO containing arsenic 2 -CaO-MgO-Al 2 O 3 Quaternary slag;
the slag former is a mixture of magnesia lime, serpentine and dolomite, and the mass ratio of the magnesia lime to the serpentine to the dolomite is (3-4): 1-2): 2; the weight percentages are as follows:
in the magnesia lime, the CaO content is more than or equal to 85 percent, and the SiO content is more than or equal to 2 The content of MgO is less than or equal to 2 percent, and the content of MgO is less than or equal to 5 percent;
in the dolomite, the content of MgO is more than or equal to 35 percent, the content of CaO is more than or equal to 50 percent, and SiO 2 The content of (2) is less than or equal to 3 percent;
in the serpentine, siO 2 The content of MgO is more than or equal to 35 percent;
the smelting treatment temperature is 1180-1220 ℃, and the smelting treatment time is more than 20min; the temperature of the heat preservation and depletion treatment is 1150-1250 ℃, and the time of the heat preservation and depletion treatment is more than 2h;
the alkalinity of the final slag is between 1.6 and 2.0.
2. The method for smelting high-arsenic copper concentrate according to claim 1, wherein the mass ratio of the high-arsenic copper concentrate to anthracite to the slag former is (40-80): (5-20): (1-10).
3. The method for smelting high-arsenic copper concentrate according to claim 1, wherein MgO and Al in the high-arsenic copper concentrate 2 O 3 The sum of the mass percentages of the components is less than or equal to 35 percent.
4. The method for smelting high-arsenic copper concentrate according to claim 1, wherein the arsenic-containing SiO 2 -CaO-MgO-Al 2 O 3 The quaternary slag comprises SiO by mass percent 2 30-33%, caO 3-6%, mgO 38-43% and Al 2 O 3 24-27％。
5. The method for smelting high-arsenic copper concentrate according to claim 1, wherein the melting point of the final slag is 1150-1250 ℃.
6. The method for smelting high-arsenic copper concentrate according to claim 1, wherein MgO and Al in the high-arsenic copper concentrate, anthracite and slag former are as follows 2 O 3 The mass ratio of (2) is 1.5-1.7.
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| WO2010034085A1 (en) * | 2008-09-23 | 2010-04-01 | Georgi Atanasov Gyurov | Method for recycling of slag from copper production |
| CN106086461A (en) * | 2016-08-18 | 2016-11-09 | 紫金矿业集团股份有限公司 | A kind of method of Copper making process slag making arsenic removal |
| CN111041225A (en) * | 2019-12-12 | 2020-04-21 | 吉林紫金铜业有限公司 | Oxygen-enriched side-blown smelting method for lean high-silicon copper concentrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010034085A1 (en) * | 2008-09-23 | 2010-04-01 | Georgi Atanasov Gyurov | Method for recycling of slag from copper production |
| CN106086461A (en) * | 2016-08-18 | 2016-11-09 | 紫金矿业集团股份有限公司 | A kind of method of Copper making process slag making arsenic removal |
| CN111041225A (en) * | 2019-12-12 | 2020-04-21 | 吉林紫金铜业有限公司 | Oxygen-enriched side-blown smelting method for lean high-silicon copper concentrate |
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| 云铜艾萨熔炼技术应用浅析;华宏全;;矿冶工程;第31卷(第06期);88-91 * |
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