CN114959279B - Utilize rich SO 2 Method for diluting smelting slag by synergy of flue gas and gypsum solid waste - Google Patents
Utilize rich SO 2 Method for diluting smelting slag by synergy of flue gas and gypsum solid waste Download PDFInfo
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Abstract
The invention provides a method for utilizing rich SO 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste comprises the following steps: s1, placing solid or liquid smelting slag in a dilution furnace, and then heating the temperature in the dilution furnace to 1150-1450 ℃; adding a carbonaceous reducing agent and gypsum solid waste into the dilution furnace before or after temperature rise; s2, after the temperature rise is finished, blowing rich SO into a dilution furnace 2 Flue gas to stir the smelting slag in a molten state; in the blowing-in process, the temperature in the furnace is 1150-1450 ℃; s3, after the blowing-in operation is finished, keeping the temperature in the furnace of the depletion furnace for 1.5 to 4 hours to obtain a metal matte phase and a depletion slag phase; in the heat preservation process, the temperature in the furnace is 1150-1450 ℃. The scheme utilizes rich SO 2 The flue gas and the gypsum solid waste are used for cooperatively diluting the smelting slag and recovering valuable metals, so that the environmental pollution is reduced, the economic benefit is created, the practicability is high, and the method is worthy of popularization.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of resources such as metallurgical and industrial solid wastes, waste gas and the like, and particularly relates to a method for utilizing rich SO 2 A method for diluting smelting slag by the synergy of flue gas and gypsum solid waste.
Background
At present, about 2-3 t of slag is generated when 1t of copper, cobalt and nickel metal is produced in the metallurgical industry. The smelting slag can be inevitably melted or mixed with a certain amount of valuable metals such as copper, cobalt, nickel and the like, and also contains toxic elements such as lead, zinc, arsenic and the like, and is listed in a dangerous waste list in China at present. With the continuous development of modern oxygen-enriched enhanced metallurgy technology, more and more secondary resources (waste circuit boards, lithium batteries and the like) of urban mineral products and the like are cooperatively treated in the copper-cobalt-nickel smelting process, so that the types and the contents of valuable metals lost in the slag are greatly improved, from the economic and environmental protection perspectives, the smelting slag needs to be subjected to resource recovery and harmless treatment, and the economic and environmental protection benefits in the early stage of the city are maximized.
SO 2 Is one of the main environmental pollutants which directly causes acid rain and visibility reduction in the world, destroys land and aquatic ecosystems and seriously affects human health. SO in flue gas produced in smelting stage of oxidizing matte making of copper-cobalt-nickel sulfide ore 2 The concentration is generally about 10-40%, and the SO is recovered and dedusted to be subjected to an acid making process 2 Conversion to H 2 SO 4 But the method inevitably overflows in a certain link to cause environmental pollution, while the productivity of the current sulfuric acid industry is seriously excessive, H 2 SO 4 The cost is low, the shortage of the cost occurs at present, and the urgent need for SO 2 A new way of resource recycling.
In addition, the gypsum solid waste refers to a byproduct or waste residue which is generated in industrial production and takes calcium sulfate (mainly calcium sulfate dihydrate) as a main component, and mainly comprises desulfurized gypsum, phosphogypsum, citric acid gypsum, fluorgypsum, salt gypsum, monosodium glutamate gypsum, copper gypsum, titanium gypsum and the like, wherein the desulfurized gypsum and the phosphogypsum account for about 85% of the total amount, and the storage amount of only one ton of phosphogypsum in China reaches 2.96 hundred million tons by 2020. Currently, there are two main ways for solid waste utilization of gypsum: the gypsum slow-setting (adjusting) agent is used as a cement slow-setting (adjusting) agent or a gypsum building material product is produced, but because the quality of industrial byproduct gypsum solid waste is unstable, and the natural gypsum resources in China are rich and the mining cost is low, the comprehensive utilization rate of the gypsum solid waste in China is low, an effective efficient comprehensive utilization way of the gypsum solid waste is lacked, a large amount of stockpiles cause serious waste of land resources, and serious environmental threats are caused to surrounding ecology.
Valuable metals in the copper-cobalt-nickel smelting slag mainly have two loss forms: mechanical inclusions of the particles (sulfides) and chemical dissolution in silicates and magnetic iron compounds (oxide lattice substitution). At present, slow cooling-ore dressing method, reduction smelting method and reduction vulcanization smelting method are mainly adopted in industry.
Such as: in the Chinese invention patent with the publication number of CN111979423B, gypsum solid waste and coke are used for a slag slow cooling-flotation process to promote copper matte particles to aggregate and grow, so that flotation recovery is facilitated. However, the method has the advantages of low slag slow cooling speed, low efficiency, incapability of utilizing slag latent heat, longer slow cooling slag crushing-fine grinding-flotation process, high ore grinding cost and high flotation wastewater treatment difficulty.
In addition, in the former patent of the applicant, although the chinese patent with publication number CN104404259B discloses a method for reduction, matte formation and dilution of copper-cobalt slag by using gypsum solid waste and coke as solvent, the method needs to additionally use N 2 Blowing a solvent into the slag as a carrier; also, in this process, N 2 Does not participate in the reaction and can also take away a large amount of heat. Therefore, this depletion process has at least the following drawbacks: high energy consumption, large smoke discharge amount and high demand on reducing agents.
In view of the above, it is necessary to provide a method for utilizing rich SO 2 A method for the synergistic dilution of smelting slag by flue gas and gypsum solid waste, which aims to solve or at least alleviate the technical defects.
Disclosure of Invention
Aiming at the problems of low efficiency, large energy consumption, large demand of reducing agent and solid waste of gypsum in the smelting process in the prior artAnd SO 2 The invention provides a method for utilizing rich SO 2 A method for diluting smelting slag by the synergy of flue gas and gypsum solid waste. Meanwhile, the invention is actually equivalent to providing a method for treating rich SO 2 Flue gas and gypsum solid waste method.
In order to solve the problems, the invention provides a method for utilizing rich SO 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste comprises the following steps:
s1, placing solid or liquid smelting slag in a depletion furnace, and then heating the temperature in the depletion furnace to 1150-1450 ℃; adding a carbonaceous reducing agent and gypsum solid waste into the dilution furnace before or after temperature rise;
s2, blowing SO into the dilution furnace after the temperature rise is finished 2 To stir said smelting slag in a molten state; in the blowing-in process, the temperature in the furnace is 1150-1450 ℃;
s3, after the blowing-in operation is completed, keeping the temperature in the furnace of the depletion furnace for 1.5 to 4 hours to obtain a metal matte phase and a depletion slag phase; in the heat preservation process, the temperature in the furnace is 1150-1450 ℃.
Further, the smelting slag comprises one or more of copper sulphide ore smelting slag, cobalt sulphide ore smelting slag, nickel sulphide ore smelting slag, matte blowing slag, cobalt matte blowing slag, laterite reduction smelting slag and copper oxide ore reduction smelting slag.
Further, the depletion furnace comprises one of an electric furnace, a reverberatory furnace, a converter, a bottom blowing furnace, a top blowing furnace, a side blowing furnace and a slow-cooling slag ladle.
Further, the SO 2 The sources of (a) include: oxidizing and desulfurizing sulfide ore to obtain rich SO 2 Flue gas;
wherein the sulphide ore comprises one or more of copper sulphide ore, cobalt sulphide ore, nickel sulphide ore, lead sulphide ore and zinc sulphide ore.
Further, the rich SO 2 The blowing speed of the flue gas is 0.2-1.2L/min, and the SO is enriched 2 Time of smoke blow-in50-100 min, the SO is enriched 2 SO in flue gas 2 The concentration is 6-35%.
Further, the carbonaceous reducing agent comprises one or more of coke, pulverized coal and natural gas;
wherein the total adding amount of the carbonaceous reducing agent is 6-25% of the mass of the smelting slag.
Further, the gypsum solid waste comprises one or more of desulfurized gypsum, phosphogypsum, citric acid gypsum, fluorgypsum, salt gypsum, monosodium glutamate gypsum, mirabilite gypsum, copper gypsum and titanium gypsum;
wherein the total adding amount of the gypsum solid waste is 8-35% of the mass of the smelting slag.
Further, the process of adding the carbonaceous reducing agent and the gypsum solid waste into the depletion furnace before the temperature rise comprises: and uniformly mixing the carbonaceous reducing agent and the gypsum solid waste, and then adding the mixture and the smelting slag into the depletion furnace.
Further, the process of adding the carbonaceous reducing agent and the gypsum solid waste to the depletion furnace after the temperature rise comprises: with SO 2 As a carrier, the carbonaceous reducing agent and the gypsum solid waste are blasted into the depletion furnace.
Further, the step S3 further includes: sending the metal matte phase to a value metal recovery system; and discharging the depleted slag phase through a slag tap of the depletion furnace.
The specific reaction principle of the invention comprises:
the smelting slag of copper, cobalt and nickel melted in the furnace undergoes reduction-vulcanization strengthening reaction, and the partial oxidation state valuable metal MeO (Cu) lost in the smelting slag of copper, cobalt and nickel is subjected to reduction-vulcanization strengthening reaction 2 O, coO, niO, znO, etc.) and SO in flue gas 2 The sulfation reaction is carried out in the initial stage of the reaction to generate metal sulfate [ MeSO 4 ]：
(MeO)+SO 2 (g)+0.5O 2 (g)＝[MeSO 4 ] (1)
SO 2 (g)+0.5O 2 (g)＝2SO 3 (2)
(MeO)+SO 3 ＝[MeSO 4 ] (3)
Meanwhile, oxidation state valuable metal (MeO) in the copper-nickel-cobalt smelting slag and CaSO in the gypsum solid waste 4 A series of reduction-sulfidation reactions also occur to form a valuable metal sulfide [ MeS ]]：
(MeO)+CaSO 4 +4C＝[MeS]+(CaO)+4CO(g) (4)
(MeO)+CaSO 4 +4CO(g)＝[MeS]+(CaO)+4CO 2 (g) (5)
With the continuous increase of the reaction temperature of the materials, the sulfate [ MeSO ] 4 ]Will continue to decompose under the reducing atmosphere to generate corresponding metal sulfide [ MeS]：
[MeSO 4 ]+4C＝[MeS]+CO(g) (6)
[MeSO 4 ]+4CO(g)＝[MeS]+4CO 2 (g) (7)
In conclusion, the oxidation state valuable metals MeO lost in the smelting slag of the invention are mixed with the reducing agent, the gypsum solid waste and SO 2 The overall reaction of the flue gas occurring during the depletion process can be briefly expressed as:
(MeO)+0.5CaSO 4 +3.5C+0.5SO 2 (g)＝[MeS]+3.5CO(g)+0.5CaO (8)
(MeO)+0.5CaSO 4 +3.5CO(g)+0.5SO 2 (g)＝[MeS]+3.5CO 2 (g)+0.5CaO (9)
iron oxides and silicates in the copper-cobalt-nickel smelting slag are also reduced and vulcanized into [ FeS ], and further metal oxides in the slag are vulcanized:
(MeO)+[FeS]＝[MeS]+(FeO) (10)
under the strong reducing atmosphere, metal oxides (MeO) in the smelting slag can be reduced into metal simple substances to enter a sulfonium phase:
(MeO)+C＝[Me]+CO(g) (11)
(MeO)+CO(g)＝[Me]+CO 2 (g) (12)
compared with the prior patent of the applicant (with the publication number of CN 104404259B)The invention introduces rich SO 2 After flue gas, the reaction principle of the slag dilution process is changed, and simultaneously, the gypsum solid waste and the carbonaceous reducing agent (reactions (8) and (9)) required by reduction-vulcanization recovery of valuable metal oxides in unit mass of smelting slag are obviously reduced compared with the earlier invention (reactions (4) and (5)), so that the energy-saving and consumption-reducing effects are remarkable.
Compared with the prior art, the invention has the following advantages:
1. the invention carries out oxidative desulfurization on copper, cobalt, nickel, lead, zinc and other sulfide ores to obtain SO-rich after dust removal 2 Introducing the flue gas into the dilution process of the copper-cobalt-nickel slag, and stirring the smelting slag.
On the one hand, the method can strengthen the solid waste of gypsum (CaSO) 4 ) Reduction-vulcanization reaction with smelting slag to regulate and control CaSO 4 While directionally decomposing to produce CaS, making SO 2 The high-efficiency synergistic vulcanization with CaS improves the recovery efficiency of valuable metals in the copper-cobalt-nickel smelting slag, promotes the enrichment and recovery of the valuable metals,
on the other hand, SO in the flue gas can be ensured 2 Taking part in a vulcanization reaction to react SO 2 The sulfur is converted into a depleted product metal sulfonium MeS to promote the regeneration of sulfur resources.
Moreover, the invention effectively utilizes the rich SO generated in the process of treating the sulphide ore 2 Smoke, prevents environmental pollution and creates economic benefit at the same time, provides a SO 2 The novel approach of resource recycling avoids the situation of serious excess of the capacity of the sulfuric acid industry caused by the traditional acid leaching treatment.
2. The depleted product in the invention can naturally settle and stratify, is respectively discharged from the depleted furnace, and can obtain metal matte and depleted slag in one step without other treatment, and compared with the traditional slag slow cooling-flotation technology, the method has the advantages of short flow and high efficiency.
3. The invention overcomes the defect of pure coke and gypsum depletion system N 2 Disadvantages in blowing by introducing SO-rich 2 Flue gas, which provides a vulcanizing atmosphere, can remarkably reduce the carbon consumption (about 12 percent) of reducing agents such as coke and the like, and simultaneously, the N is eliminated 2 The energy consumption is reduced (about 20 percent) by blowing, the emission of the smoke volume is reduced, wherein, the depleted smoke (containing CO/CO) 2 /SO 2 ) Can be efficiently treated in a closed environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 shows the utilization of rich SO according to the present invention 2 A flow schematic diagram of a method for diluting smelting slag by synergy of flue gas and gypsum solid waste.
FIG. 2 is a drawing of a cooled material object of a matte phase and a depleted slag obtained after the copper-cobalt-nickel smelting slag is depleted in example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all 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 and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
As shown in FIG. 1, the present invention provides a method for utilizing rich SO 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste comprises the following steps:
s1, placing solid or liquid smelting slag in a dilution furnace, and then heating the temperature in the dilution furnace to 1150-1450 ℃; and adding a carbonaceous reducing agent and gypsum solid waste into the dilution furnace before or after the temperature is raised.
It can be understood that the temperature of the dilution furnace can be increased and controlled within 1150-1450 ℃ by adjusting and setting the dilution furnace temperature control program, so that the melt in the furnace is in a molten state and the reaction can be efficiently and fully carried out;
preferably, the smelting slag comprises one or more of copper sulphide ore smelting slag, cobalt sulphide ore smelting slag, nickel sulphide ore smelting slag, matte blowing slag, cobalt matte blowing slag, nickel matte blowing slag, laterite reduction smelting slag and copper oxide ore reduction smelting slag.
It should be understood by those skilled in the art that the smelting slag contains one or more of the three valuable metals copper, cobalt and nickel.
Preferably, the dilution furnace is used for diluting the smelting slag, and may comprise one of an electric furnace, a reverberatory furnace, a converter, a bottom-blown furnace, a top-blown furnace, a side-blown furnace and a slow-cooling slag ladle.
Preferably, the reductant comprises one or more of coke, pulverized coal and natural gas; the total adding amount of the carbonaceous reducing agent is 6-25% of the mass of the smelting slag.
Preferably, the gypsum solid waste comprises one or more of desulfurized gypsum, phosphogypsum, citric acid gypsum, fluorgypsum, salt gypsum, monosodium glutamate gypsum, mirabilite gypsum, copper gypsum and titanium gypsum; the total adding amount of the gypsum solid waste is 8-35% of the mass of the copper-cobalt-nickel smelting slag.
Preferably, the process of adding the carbonaceous reducing agent and the gypsum solid waste to the dilution furnace before the temperature rise comprises: and uniformly mixing the carbonaceous reducing agent and the gypsum solid waste, and adding the mixture and solid or liquid slag into a depletion furnace.
Of course, solid or liquid smelting slag can be added into the dilution furnace, and then the compacted and granulated carbonaceous reducing agent and gypsum solid waste are proportionally added into the dilution furnace.
It can be understood that, in the laboratory smelting process, smelting slag, gypsum solid waste and reducing agent can be firstly loaded into a crucible, and then the crucible is placed into a semi-industrial dilution furnace for treatment, and the main functions are as follows: on one hand, the crucible material has high temperature resistance and stable mechanical property, can protect the furnace body in the high-temperature smelting process and prolong the service life of the furnace body; on the other hand, the crucible is favorable for taking and placing samples in the furnace, and real-time detection is convenient.
It can also be understood that, in general, after the solid or liquid slag, the briquetting, the granulated reducing agent and the gypsum solid waste are put into the furnace, the temperature is raised to 1150-1450 ℃, after the temperature is constant, SO-enriched slag is blown into the dilution furnace 2 The flue gas is specifically described in step S2.
S2, after the temperature rise is finished, blowing SO into a dilution furnace 2 Stirring the copper-cobalt-nickel smelting slag in a molten state; in the blowing process, the temperature in the furnace is 1150-1450 ℃.
Preferably, the SO 2 The sources of (a) include: oxidizing and desulfurizing sulfide ore to obtain rich SO 2 And (4) flue gas.
Wherein the sulphide ore comprises one or more of copper sulphide ore, cobalt sulphide ore, nickel sulphide ore, lead sulphide ore and zinc sulphide ore.
Preferably, the SO is enriched 2 The blowing speed of the flue gas is 0.2-1.2L/min, and the SO is enriched 2 The blowing-in time of the flue gas is 50-100 min, and the SO is enriched 2 SO in flue gas 2 The concentration is 6-35%.
It will be understood by those skilled in the art that in examples 3, 4, 5 and 6 of the present application, different ratios N are entered 2 、O 2 And SO 2 One or more of the above-mentioned materials are mainly used for simulating SO in flue gas under the actual working condition 2 Actual composition and concentration, i.e. actual SO-enrichment 2 Flue gas is mainly N 2 -SO 2 Mixtures or N 2 -O 2 -SO 2 A mixture, wherein the oxygen promotes combustion of the reductant during the enleanment process to produce a CO reducing gas, facilitating the reduction reaction.
As another feeding mode of the present invention, the process of adding the carbonaceous reducing agent and the gypsum solid waste into the depletion furnace after the temperature rise may further include: to enrich SO 2 And (3) blowing the carbonaceous reducing agent and the gypsum solid waste into the smelting slag in the dilution furnace by taking the flue gas as a carrier.
During the bubbling, the carbonaceous reducing agent and the gypsum solid waste are treated with the SO-rich 2 The flue gas is a carrier and is blown into the dilution furnace, so that the stirring amplitude can be increased, the contact area of the flue gas, the flue gas and the smelting slag is enlarged, and the mass transfer process is strengthened.
It is clear that the carbonaceous reducing agent and the gypsum solid waste are added before the temperature is raised, and then SO is blown in after the temperature is raised 2 (ii) a Or blowing SO from the blast nozzle simultaneously after the temperature is raised 2 And carbonaceous reducing agent, gypsum solid waste, said SO 2 Can intensively stir the melt in the furnace SO as to produce the SO 2 The carbonaceous reducing agent and the gypsum solid waste stir the smelting slag in a molten state, so that the purposes of promoting mass transfer and heat transfer and improving the reaction efficiency are achieved.
Before the carbonaceous reducing agent and the gypsum solid waste are blown, the carbonaceous reducing agent and the gypsum solid waste may be subjected to a preheating treatment at 200 to 900 ℃.
It should be understood that the preheating treatment is only a preferred item of the present invention, and the carbonaceous reducing agent and the gypsum solid waste can be mixed and preheated, or the carbonaceous reducing agent and the gypsum solid waste can be directly mixed with the cold materials according to a preset proportion and then mixed with SO without preheating treatment 2 For the purpose of blowing the carriers from the tuyeres into the depletion furnace.
S3, after the blowing-in operation is completed, keeping the temperature in the furnace of the depletion furnace for 1.5 to 4 hours to obtain a metal matte phase and a depletion slag phase; in the heat preservation process, the temperature in the furnace is 1150-1450 ℃.
It will be understood by those skilled in the art that the molten smelting slag after the reaction in the furnace is mostly generated and converted into copper cobalt nickel sulfide, a small amount of the copper cobalt nickel sulfide is reduced into alloy, the copper cobalt nickel sulfide and the alloy are continuously gathered and settled in the smelting slag, and finally a metal matte phase is formed and gathered in a depleted furnace bottom and separated from the depleted slag phase, wherein the metal matte phase mainly comprises iron sulfide, copper sulfide, nickel sulfide and cobalt sulfide, and the depleted slag phase mainly comprises fayalite, gavite and wollastonite.
Preferably, the step S3 further includes: sending the metal matte phase to a value metal recovery system; discharging the depleted slag phase through a slag tap of the depletion furnace, wherein the depleted slag phase can be used as a building material or a roadbed raw material.
It is understood that the metal matte phase may be tapped off through a siphon; the specific process is as follows: and after the operations of heat preservation and standing are finished, discharging the separated lower-layer metal matte phase from a siphon port, and then discharging the upper-layer slag depletion phase from a slag discharge port, wherein the slag depletion phase and the metal matte phase are molten during discharging.
Specifically, the valuable metal recovery system can be a pyrometallurgical converting system, the metal matte phase is sent into the pyrometallurgical converting system for smelting, a spray gun is used for spraying high-pressure and high-speed industrial pure oxygen or air to melt, so that impurities are oxidized into scum and gas (such as sulfur dioxide) is separated or escaped, and purer valuable metal is obtained, and the purpose of recovering the valuable metal is further realized; the metal matte phase may also be used to further recover valuable metals via a wet leaching system.
To facilitate a further understanding of the invention by those skilled in the art, reference will now be made to the following examples:
example 1
Taking matte blowing slag of a certain domestic plant, wherein the slag comprises the following components in percentage by weight: cu 4.05, fe 39.03, pb 0.33, zn 2.80, as 0.31, siO 2 21.65, caO 2.56, ag 10.58g/t and Au 5.15g/t, and is marked as smelting slag A;
taking domestic desulfurization gypsum solid waste of a certain factory, wherein CaSO in the desulfurization gypsum solid waste 4 ·2H 2 The mass fraction of O is more than 95 percent and is marked as gypsum solid waste A;
the metallurgical coke of a certain domestic iron works is taken, and the composition (wt%) of the metallurgical coke is as follows: fixed carbon 84.25, volatile 4.89, ash 10.86; wherein, the sulfur and nitrogen elements in the volatile component (wt%) are: s1.59, N0.79, and is marked as reductant A.
According to the invention, the rich SO is utilized 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste comprises the following operations:
taking 500g of smelting slag A as a reference, uniformly mixing 15% by mass of gypsum solid waste A and 8% by mass of reducing agent A (both are mass fractions relative to the smelting slag A), briquetting, granulating, mixing with 500g of smelting slag A, and filling into a crucible; then the crucible is placed in a depletion furnace, after the temperature is raised and kept constant to 1350 ℃, SO of 0.2L/min is blown into the melt in the crucible 2 And (4) keeping the temperature and standing for 1.5h after the gas is exhausted for 1h to obtain a metal matte phase and a depleted slag phase.
Through determination and calculation: in the matte phase of the present embodiment, the recovery rates of copper, lead, zinc, gold and silver can respectively reach 95.1%, 89.4%, 78.5%, 99.2% and 98.8%.
Example 2
Taking certain domestic copper sulphide ore smelting slag, wherein the chemical composition (wt%) of the smelting slag is as follows: cu 1.7, co 0.15, ni 0.08, fe 35.45, siO 2 32.56、CaO 3.56、Al 2 O 3 4.12, 11.92g/t of Ag and 27.73g/t of Au, and recording as smelting slag B;
taking phosphogypsum of a certain chemical plant in China, wherein CaSO in the phosphogypsum (dry basis) 4 ·2H 2 The mass fraction of O is more than 96 percent and is marked as gypsum solid waste B;
the metallurgical coke of a certain domestic iron works is taken, and the chemical composition (wt%) of the metallurgical coke is as follows: fixed carbon 87.45, volatile 4.89, ash 7.66; wherein, the components (wt%) of sulfur and nitrogen in the volatile component are as follows: s0.95 and N0.56, and marked as reducing agent B.
According to the invention, the rich SO is utilized 2 Smoke and gypsum solid waste synergistic dilution smelting methodThe slag smelting method comprises the following operations:
uniformly mixing 12% by mass of gypsum solid waste B and 10% by mass of reducing agent B (both are mass fractions relative to the smelting slag B) on the basis of 500g of the smelting slag B, briquetting, granulating, mixing with 500g of the smelting slag B, and filling into a crucible; then the crucible is placed in a depletion furnace, the temperature of the depletion furnace is raised and kept constant to 1250 ℃, and then 0.3L/min SO is blown into the melt in the crucible 2 And (3) keeping the temperature and standing for 2 hours after the gas is exhausted for 50 minutes to obtain a metal matte phase and a depleted slag phase.
Through determination and calculation: in the matte phase of the present embodiment, the recovery rates of copper, cobalt, nickel, gold and silver can respectively reach 93.14%, 92.21%, 89.45%, 98.5% and 97.4%.
Example 3
Taking certain domestic cobalt matte blowing slag, wherein the chemical composition (wt%) of the slag is as follows: cu 5.32, co 1.45, ni 1.09, fe 47.56, S0.34, siO 2 27.23, caO 2.56, au 184g/t and Ag 289g/t. Marking as smelting slag C;
taking titanium gypsum from a certain domestic plant, wherein the titanium gypsum comprises the following chemical components in percentage by weight: caO 35.2, SO 3 38.4，Fe 2 O 3 12.4， SiO 2 4.5，TiO 2 2.59, recording as gypsum solid waste C;
the pulverized coal of a certain domestic iron works is prepared from the following chemical components in percentage by weight: fixed carbon 78.25; wherein, the hydrogen, sulfur and nitrogen elements in the pulverized coal comprise the following components in percentage by weight: h6.12, S2.45, N0.56, noted as reductant C.
According to the invention, the rich SO is utilized 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste comprises the following specific steps:
uniformly mixing 23 mass percent of gypsum solid waste C and 16 mass percent of reducing agent C (both mass fractions relative to the smelting slag C) by taking 500g of the smelting slag C as a reference, uniformly mixing the gypsum solid waste C with 500g of the smelting slag C, placing the mixture into a crucible, placing the crucible into a dilution furnace, heating the crucible to 1200 ℃, and blowing 0.8L/min of N into a melt in the crucible 2 -SO 2 (N 2 :SO 2 0.6 l to simulate SO-rich 2 SO in flue gas 2 25% strength) of the mixtureSynthesizing gas for 80min, and then keeping the temperature and standing for 2.5h to obtain a metal sulfonium phase and a depleted slag phase.
Through measurement and calculation, the recovery rates of copper, cobalt, nickel, gold and silver in the metal matte phase of the embodiment can respectively reach 90.45%, 91.34%, 87.56%, 98.5% and 96.8%.
Example 4
Mixing smelting slag A, B and C according to the mass ratio of 1; mixing the gypsum solid waste B and the gypsum solid waste C according to the mass ratio of 1; mixing the reducing agents A and B according to the mass ratio of 1;
according to the invention, the rich SO is utilized 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste comprises the following specific steps:
uniformly mixing 28% of mixed gypsum solid waste and 20% of mixed reducing agent (both the mass fractions of the mixed gypsum solid waste and the mixed reducing agent relative to the mixed smelting slag) by taking 600g of mixed smelting slag as a reference, uniformly mixing the mixed gypsum solid waste and the mixed reducing agent with 600g of mixed smelting slag, and placing the mixture in a crucible; the crucible is put into a depletion furnace, the temperature is raised and is constant to 1400 ℃, and 1L/min of N is blown into the melt in the crucible 2 -SO 2 (N 2 :SO 2 0.9 l to simulate SO rich 2 SO in flue gas 2 The concentration is 10%), and then the mixed gas is kept warm and kept stand for 3 hours, so that a metal sulfonium phase and a depleted slag phase are obtained; wherein the cooled metal matte and the depleted slag are shown in figure 2.
Through measurement and calculation, the recovery rates of copper, cobalt, nickel, gold and silver in the matte phase of the embodiment can respectively reach 93.94%, 93.57%, 90.15%, 97.5% and 98.8%.
Example 5
Mixing smelting slag A and C according to a mass ratio of 1; simultaneously mixing the gypsum solid waste A and the gypsum solid waste C according to the mass ratio of 1; mixing the reducing agents A and C in a mass ratio of 1;
according to the invention 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste comprises the following operations:
put what into the crucible500g of mixed smelting slag, and the temperature of a depletion furnace is raised and kept constant to 1150 ℃, and then N of 1.2L/min is added 2 -SO 2 (N 2 :SO 2 1.0, 0.2l to simulate SO-rich 2 SO in flue gas 2 The concentration is 16.7 percent), mixed gypsum solid waste with the mass fraction of 25 percent and mixed reducing agent with the mass fraction of 18 percent (both relative to the mass fraction of the mixed smelting slag) are blown into the smelting slag melt by taking the mixed gas as a carrier, the air blowing time is 100min, and the mixture is kept warm and kept stand for 2.5h, so that a metal matte phase and a depleted slag phase are obtained.
Through measurement and calculation, the recovery rates of copper, cobalt, nickel, gold and silver can respectively reach 92.45%, 92.85%, 91.56%, 96.42% and 97.87%.
Example 6
Mixing the smelting slag B and the smelting slag C according to a mass ratio of 1; simultaneously mixing the gypsum solid waste B and the gypsum solid waste C according to a mass ratio of 1; mixing the reducing agents A and B in a mass ratio of 1;
according to the invention 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste comprises the following operations:
500g of mixed smelting slag is put into a crucible, and a dilution furnace is heated to 1250 ℃ and is heated by N of 1.1L/min 2 -O 2 -SO 2 (N 2 :O 2 :SO 2 0.25 2 SO in flue gas 2 The concentration is 31.8 percent), the mixed gas is taken as a carrier, 10 percent of mixed gypsum solid waste and 14 percent of mixed reducing agent (both relative to the mixed smelting slag) are blown into the melt in the crucible of the shaft furnace, the air blowing time is 70min, and the mixture is kept warm and kept stand for 1.5h, thus obtaining the metal matte phase and the depleted slag phase.
Through measurement and calculation, the recovery rates of copper, cobalt, nickel, gold and silver can respectively reach 91.58%, 93.47%, 92.63%, 95.75% and 96.52%.
In the above technical solutions of the present invention, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention, equivalent structural changes made by using the contents of the description and the drawings of the present invention, or direct/indirect applications in other related technical fields, are included in the scope of the present invention.
Claims (10)
1. Use rich SO 2 The method for diluting the smelting slag by the synergy of the flue gas and the gypsum solid waste is characterized by comprising the following steps:
s1, placing solid or liquid smelting slag in a dilution furnace, and then heating the temperature in the dilution furnace to 1150-1450 ℃; adding a carbonaceous reducing agent and gypsum solid waste into the dilution furnace before or after temperature rise;
s2, blowing SO into the dilution furnace after the temperature rise is finished 2 To stir said smelting slag in a molten state; in the blowing-in process, the temperature in the furnace is 1150-1450 ℃;
s3, after the blowing-in operation is finished, keeping the temperature in the furnace of the depletion furnace for 1.5 to 4 hours to obtain a metal matte phase and a depletion slag phase; in the heat preservation process, the temperature in the furnace is 1150-1450 ℃.
2. The method of synergistic depletion of smelting slag according to claim 1, characterized in that the smelting slag comprises one or more of copper sulphide ore smelting slag, cobalt sulphide ore smelting slag, nickel sulphide ore smelting slag, matte blowing slag, cobalt matte blowing slag, nickel matte blowing slag, laterite reduction smelting slag and copper oxide reduction smelting slag.
3. The method for the synergistic depletion of smelting slag according to claim 1, characterized in that the depletion furnace comprises one of electric furnace, reverberatory furnace, converter, bottom-blown furnace, top-blown furnace, side-blown furnace and slow-cooling slag ladle.
4. Method for the synergistic depletion of smelting slag according to claim 1, characterized in that said SO is 2 The sources of (a) include: oxidizing and desulfurizing sulfide ore to obtain rich SO 2 Flue gas;
wherein the sulphide ore comprises one or more of copper sulphide ore, cobalt sulphide ore, nickel sulphide ore, lead sulphide ore and zinc sulphide ore.
5. Method for the synergistic depletion of smelting slag according to claim 4, characterized in that said SO enrichment is performed 2 The blowing speed of the flue gas is 0.2-1.2L/min, and the SO is enriched 2 The blowing-in time of the flue gas is 50-100 min, and the SO is enriched 2 SO in flue gas 2 The concentration is 6-35%.
6. The method of co-depletion of smelting slag according to claim 1, characterized in that the carbonaceous reductant comprises one or more of coke, pulverized coal and natural gas;
the total adding amount of the carbonaceous reducing agent is 6-25% of the mass of the smelting slag.
7. The method for synergistic depletion of smelting slag according to claim 1, characterized in that the gypsum solid waste comprises one or more of desulfurized gypsum, phosphogypsum, citric gypsum, fluorgypsum, salt gypsum, monosodium glutamate gypsum, glauber's salt gypsum, copper gypsum and titanium gypsum;
the total addition of the gypsum solid waste accounts for 8-35% of the mass of the smelting slag.
8. The method for the synergistic depletion of smelting slag according to claim 1, characterized in that the process of adding the carbonaceous reductant and the gypsum solid waste in the depletion furnace before the temperature rise comprises: and uniformly mixing the carbonaceous reducing agent and the gypsum solid waste, and adding the mixture and the smelting slag into the depletion furnace.
9. The method for the synergistic depletion of smelting slag according to claim 1, characterized in that the process of adding the carbonaceous reductant and the gypsum solid waste to the depletion furnace after said raising the temperature comprises: with SO 2 Blowing the carbonaceous reducing agent and the gypsum solid waste into the depletion furnace for carriers.
10. Method for the synergistic depletion of smelting slag according to claim 1, characterized in that said step S3 further comprises: sending the metal matte phase to a value metal recovery system; and discharging the depleted slag phase through a slag tap of the depletion furnace.
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