CN110983029A - Method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag - Google Patents

Method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag Download PDF

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CN110983029A
CN110983029A CN201911127934.0A CN201911127934A CN110983029A CN 110983029 A CN110983029 A CN 110983029A CN 201911127934 A CN201911127934 A CN 201911127934A CN 110983029 A CN110983029 A CN 110983029A
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韩俊伟
刘维
覃文庆
张添富
焦芬
杨聪仁
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Central South University
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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
    • C22B1/02—Roasting processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
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    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
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    • B03D1/00—Flotation
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    • 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
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

The invention discloses a method for the synergistic vulcanization roasting of lead-zinc smelting slag and gypsum slag, which comprises the steps of mixing the lead-zinc smelting slag, the gypsum slag and a carbonaceous reducing agent, carrying out reduction vulcanization roasting, utilizing the gypsum slag as a vulcanizing agent to directionally convert lead, zinc and other heavy metals in the lead-zinc smelting slag into metal sulfides easy to be separated by flotation, reacting calcium in the gypsum slag with iron and silicon compounds in the lead-zinc smelting slag to generate calcium ferrite and calcium silicate compounds, and using the calcium ferrite and the calcium silicate compounds as building materials and cement for manufacturing, wherein arsenic in the gypsum slag is volatilized and enriched in smoke dust for recovery. The method has the advantages of low energy consumption and environmental friendliness, can solve the problem of environmental pollution caused by the treatment of the existing gypsum slag and lead-zinc smelting slag, and has good popularization and application prospects.

Description

Method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag
Technical Field
The invention relates to a method for cooperatively treating lead-zinc smelting slag and gypsum slag, in particular to a method for directionally converting heavy metals such as lead, zinc and the like in the lead-zinc smelting slag into metal sulfides easy to float and recover by adopting the gypsum slag as a vulcanizing agent through a reduction vulcanization roasting method, and belongs to the technical field of non-ferrous metal beneficiation and metallurgy.
Background
China is a large country for lead and zinc production and consumption, and the metal yield of lead and zinc in 2015 is 398.9 ten thousand and 621.7 thousand respectively, which account for more than 40% of the total world yield. At present, 85 percent of zinc in China is prepared by a process of 'boiling roasting-two-stage leaching-purification impurity removal-electrodeposition', and because zinc ferrite generated in the process of boiling roasting is difficult to dissolve out in the leaching process, a large amount of zinc ferrite slag containing 18 to 25 percent of zinc and 35 to 45 percent of iron is generated; at present, the slag is volatilized mainly by a rotary kiln, the leached slag is mixed with reducing agents such as coke, the temperature of furnace gas in the furnace is controlled to be 1100-1300 ℃, volatile metals such as zinc, indium, gallium and the like are volatilized in a steam mode, secondary oxidation is carried out in a dust collection system, enrichment and recovery are carried out, and the volatilization rate of zinc is as high as 90-95 percent; at present, 90% of lead capacity in the world is obtained by a pyrometallurgical lead smelting process, a large amount of water-quenched slag, rough smelting scum and precious metal smelting waste slag which are rich in valuable metals such as lead, zinc, silver and the like are produced in the pyrometallurgical lead smelting process, and the treatment method of the lead smelting slag mainly comprises a rotary kiln method, a fuming method, an Osmant method, a smelting method and the like at present, the pyrometallurgical process has high volatilization rate of the valuable metals such as lead, zinc, indium and the like, but coal-fired flue gas contains a large amount of low-concentration SO2 gas, the flue gas emission can generate great harm to human health and environment, the dust collection operation pressure is large, the energy consumption is high, the cost is high, and in addition, the hardness of the kiln slag is large. According to estimation, the lead smelting system discharges 0.71 ten thousand of waste slag when producing 1 ten thousand of lead and 0.96 ten thousand of waste slag when producing 1 ten thousand of zinc. According to the conversion of the metal yield of lead and zinc, about 283.23 million tons of lead smelting waste slag, about 596.86 million tons of zinc smelting waste slag and the total slag amount is up to 880 million tons in 2015. However, the development of the lead-zinc recycling industry in China is far behind that in developed countries, and particularly recycled zinc is in the starting stage. The data of the national statistical bureau show that the general comprehensive utilization rate of solid waste is less than 63% and the comprehensive utilization rate of hazardous waste is less than 57% in 2014. By this calculation, the total stockpiling amount of the wastes produced by lead-zinc smelting in our country over the years is tens of millions of tons. The lead-zinc smelting process can generate a large amount of acidic waste water in the acid making stage of flue gas desulfurization and the electrolytic solution purification section, and the acidic waste water is treated by a lime neutralization method, so that a large amount of gypsum slag can be generated, the main component of the gypsum slag is calcium sulfate dihydrate, and in addition, toxic and harmful components such as lead, zinc, chromium, arsenic and the like are contained, the waste slag belongs to typical dangerous solid waste, and the stockpiling treatment is mainly adopted at present.
A large amount of lead-zinc smelting slag and gypsum slag are produced by a lead-zinc smelting plant every year, but no economic, green and feasible scheme for cooperatively treating the lead-zinc smelting slag and the gypsum slag exists at present, so that the development of the process for cooperatively treating the lead-zinc smelting slag and the gypsum has important significance for simplifying the existing lead-zinc recovery process, solving the problems of gypsum slag stockpiling and green and economic recovery of valuable metals of the lead-zinc smelting slag, and is an important guarantee for realizing green, clean and sustainable development of the lead-zinc smelting industry.
Disclosure of Invention
The method aims to solve the problems of high energy consumption, serious environmental pollution, difficult kiln slag disposal and dangerous solid waste stockpiling of gypsum slag in the traditional pyrogenic process treatment process of lead-zinc smelting slag; the invention aims to provide a clean and efficient method for cooperatively treating lead-zinc smelting slag and gypsum slag, the method adopts the gypsum slag as a vulcanizing agent, heavy metal oxides such as lead, zinc and the like in the lead-zinc smelting slag and the gypsum slag are selectively converted into sulfides which are easy to recover through flotation through reduction, vulcanization and roasting, silicon, calcium, iron and the like are converted into low-melting-point compounds such as calcium ferrite, calcium silicate and the like, and arsenic is volatilized and enriched in smoke dust; calcium ferrite, calcium silicate and the like are enriched in flotation tailings and can be used as raw materials and building materials for manufacturing cement; the sulfur in the gypsum slag is converted in the reduction vulcanization roasting processIs fixed as metal sulfide, SO that SO is avoided2Release of (1); arsenic is volatilized and enriched in smoke dust, so that clean treatment of gypsum slag and comprehensive recovery of lead-zinc smelting slag resources are realized.
In order to achieve the technical purpose, the invention provides a method for the synergistic vulcanization roasting of lead-zinc smelting slag and gypsum slag, which comprises the steps of mixing the lead-zinc smelting slag, the gypsum slag and a carbonaceous reducing agent, and carrying out reduction vulcanization roasting at the temperature of 650-1050 ℃ in a protective atmosphere to obtain a roasted product containing lead sulfide, zinc sulfide, calcium silicate and calcium ferrite.
In the preferred scheme, the mass ratio of the gypsum slag, the lead-zinc smelting slag and the carbonaceous reducing agent is 100: 50-100: 15 to 50. More preferably 100: 50-80: 20-30; when the quality of the lead-zinc smelting slag is higher than 100% of that of the gypsum slag, the vulcanizing agent is excessive in the reaction process, so that a large amount of iron sulfide is generated, and selective vulcanization of heavy metals such as lead, zinc and the like is not facilitated; when the mass of the lead-zinc smelting slag is lower than 50% of that of the gypsum slag, the dosage of vulcanizing agent gypsum is insufficient, a sufficient sulfur source cannot be provided for vulcanizing heavy metals such as lead and zinc, and the vulcanization of the lead and zinc heavy metals is insufficient. When the quality of the carbonaceous reducing agent is higher than 50% of that of the gypsum slag, the reducing atmosphere strength of the reaction system is high, a large amount of lead-zinc heavy metal is reduced into metal simple substances, and the metal simple substances are volatilized and lost, in addition, a large amount of carbonaceous reducing agent remains in a roasting product, a large amount of flotation reagents are consumed in a flotation stage, and the subsequent flotation separation is not facilitated; when the mass of the carbonaceous reducing agent is less than 15 percent of the mass of the gypsum slag, the oxygen potential of the reaction system is high, the vulcanization of lead and zinc heavy metals is not facilitated, and SO can be introduced2And (4) overflowing of gas.
Preferably, the lead-zinc smelting slag comprises at least one of zinc ferrite slag, lead smelting water-quenched slag and steel mill smoke.
Preferably, the gypsum slag comprises at least one of desulfurized gypsum slag and waste acid neutralization slag.
In a preferred embodiment, the carbonaceous reducing agent includes at least one of coke, coke powder, charcoal, and anthracite. More preferably at least one of coke and coke powder. The particle size of the carbonaceous reducing agent meets the requirement that the mass of the particle size fraction is less than 5mm, and the content of the carbonaceous reducing agent is not less than 80 percent.
In the preferable scheme, the temperature of the reduction, vulcanization and roasting is 700-1000 ℃, and the time is 1-3 h.
In a preferred embodiment, the reduction-sulfidation roasting is carried out in a steel belt furnace.
The technical scheme of the invention adopts the desulfurized gypsum slag and the waste acid neutralization slag produced in the lead-zinc smelting process as the vulcanizing agents, and realizes the reduction and vulcanization synergistic treatment with the lead-zinc smelting slag under the action of the carbonaceous reducing agent. The gypsum slag is used as the vulcanizing agent, so that the cost of the vulcanizing agent is reduced, the purpose of treating wastes with wastes is achieved while realizing harmlessness and recycling of the gypsum slag, and when the gypsum slag is used as the vulcanizing agent, calcium in the gypsum slag and a silicon-iron component in lead-zinc smelting slag can generate a low-melting-point compound, so that the formation of a liquid phase is facilitated, the growth of lead-zinc sulfide grains is promoted, the selectivity of a vulcanizing process is facilitated, and oxides of silicon, iron and calcium can be used as building materials and cement materials after being subjected to high-temperature cremation.
The invention mainly utilizes sulfur in the gypsum slag as a vulcanizing agent in the reduction and vulcanization processes of the lead-zinc smelting slag and the gypsum slag, realizes the vulcanization conversion of lead, zinc and other heavy metals in the gypsum slag and the lead-zinc smelting slag under the carbon reduction condition, activates oxides of silicon and iron, reduces and volatilizes arsenic, releases no sulfur oxide in the whole reaction process, and comprises the following main chemical reactions:
1、ZnO+CaSO4+2C＝ZnS+CaO+2CO2(g)；
2、Zn(OH)2+CaSO4+2C＝ZnS+CaO+2CO2(g)+H2O(g)；
3、ZnSiO3+CaSO4+2C＝ZnS+CaSiO3+2CO2(g)；
4、ZnFe2O4+CaSO4+2C＝ZnS+CaO·Fe2O3+2CO2(g)；
5、PbO+CaSO4+2C＝PbS+CaO+2CO2(g)；
6、Pb(OH)2+CaSO4+2C＝PbS+CaO+2CO2(g)+H2O(g)；
7、CaSO4+2C＝CaS+2CO2(g)；
8、CaSO4+2.25C+1.5Fe2O3＝CaO·Fe2O3+FeS+2.25CO2(g)。
compared with the prior art, the invention has the beneficial effects that:
1) the technical scheme of the invention can match lead-zinc smelting slag which is abundantly existed in the existing lead-zinc nonferrous metallurgy industry with desulfurized gypsum slag or arsenic-containing neutralized slag, lead-zinc valuable metals in the slag are converted into lead-zinc sulfide through reduction auto-vulcanization roasting, arsenic in the slag is reduced, volatilized and enriched in smoke dust, compounds of calcium, silicon and iron are converted into calcium silicate and calcium ferrite, and lead, lead and zinc sulfide in the obtained reduction vulcanization roasting slag are easy to recover by adopting a conventional flotation method; after reduction, vulcanization and roasting, the vulcanization rates of zinc and lead are respectively over 93 percent and 89 percent, the fixation rate of sulfur is over 95 percent, and the volatilization rate of arsenic is over 97 percent; the gangue in the slag can be used for producing building materials and cement due to high-temperature roasting; the sulfur in the slag is basically fixed in the form of metal sulfide, rather than being volatilized into the flue gas, SO that the SO in the roasting process is eliminated2Pollution, arsenic in the slag is enriched in smoke dust, so that subsequent recovery and disposal are facilitated, and clean cooperative disposal of gypsum slag and lead-zinc smelting slag and comprehensive recovery of valuable metals can be realized.
2) The technical scheme of the invention has the advantages of mild process conditions, low energy consumption, environmental protection and simple operation, and is beneficial to industrial production.
Drawings
FIG. 1 is a temperature-Gibbs free energy diagram of the relevant reaction during the calcination process of the present invention.
FIG. 2 XRD pattern of reduction-sulfidation-calcined product.
Detailed Description
The present disclosure is further illustrated by the following specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
The vulcanizing agent used in the embodiment is gypsum neutralization slag produced by electrolytic cleaning solution of a certain zinc plant, the specific components of the gypsum neutralization slag are shown in table 1, and the neutralization slag mainly comprises dihydrate and calcium sulfate and contains 2.38% of arsenic;
TABLE 1 Main chemical composition of the neutralized slag/%)
Figure BDA0002277441090000041
Figure BDA0002277441090000051
The lead-zinc smelting slag used in the embodiment is acidic leaching slag, the specific components of which are shown in table 2, and zinc in the zinc leaching slag is mainly present in the form of zinc ferrite;
TABLE 2 major chemical composition/% of zinc ferrite slag
Figure BDA0002277441090000052
A method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag comprises the following specific steps:
(1) respectively mixing the above 1000kg of gypsum residue, 800kg of zinc leaching residue and 300kg of coke with 80% of granularity less than 5mm (mass ratio is 100:80: 30);
(2) placing the uniformly mixed sample on a steel belt furnace material distributor, controlling the feeding amount of the material distributor and the running speed of a steel belt to ensure that the thickness of a material layer is 10-15 mm, introducing nitrogen into the steel belt furnace as a protective gas during roasting, setting the roasting temperature to 950 ℃, and controlling the running speed of the steel belt to ensure that the sample stays in a furnace body for 1 hour;
(3) cooling the roasted sample to room temperature under the protection of nitrogen, sampling and analyzing the contents of arsenic, sulfur and lead-zinc sulfide in the sample, and calculating the volatilization rate of arsenic, the fixation rate of sulfur and the vulcanization rate of a lead-zinc compound;
TABLE 3 chemical analysis of reduced sulfided calcine/%)
Figure BDA0002277441090000053
The above data show that after reduction sulfidation roasting, the volatilization rate of arsenic is 98.5%, the fixation rate of sulfur is 96.7%, and the sulfidation rates of lead and zinc are 89.3% and 93.2%, respectively, the zinc and lead in the roasted product are substantially present in the form of sulfide, and the compounds of iron and silicon are mainly present in the form of calcium ferrite and calcium silicate, so that lead and zinc can be easily recovered by the conventional flotation method.
Comparative example 1
The specific components of the vulcanizing agent used in the present example are shown in table 1, and the lead-zinc smelting slag used in the present example is acid leaching slag, the specific components of which are shown in table 2.
A method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag comprises the following specific steps:
(1) respectively mixing the above 1000kg of gypsum residue, 800kg of zinc leaching residue and 300kg of coke with 80% of granularity less than 5mm (mass ratio is 100:80: 30);
(2) placing the uniformly mixed sample on a steel belt furnace material distributor, controlling the feeding amount of the material distributor and the running speed of a steel belt to ensure that the thickness of a material layer is 10-15 mm, introducing nitrogen into the steel belt furnace as a protective gas during roasting, setting the roasting temperature to be 600 ℃, and controlling the running speed of the steel belt to ensure that the sample stays in a furnace body for 3 hours;
(3) cooling the roasted sample to room temperature under the protection of nitrogen, sampling and analyzing the contents of arsenic, sulfur and lead-zinc sulfide in the sample, and calculating the volatilization rate of arsenic, the fixation rate of sulfur and the vulcanization rate of a lead-zinc compound;
TABLE 4 chemical analysis of reduced sulfided calcine/%)
Figure BDA0002277441090000061
The data show that zinc and lead are difficult to be vulcanized and converted due to low reduction temperature, arsenic is difficult to volatilize, calcium in a roasting product mainly exists in a form of calcium sulfate, most of zinc still exists in a form of zinc ferrite, and the vulcanization rate of lead and zinc is low, so that the subsequent flotation is not facilitated.
Example 2
The vulcanizing agent used in the embodiment is desulfurized gypsum slag produced in the acid making and washing process of flue gas of a certain zinc smelting plant, the specific components of the desulfurized gypsum slag are shown in table 5, and the main components of the neutralized slag are dihydrate and calcium sulfate, and the arsenic content is 0.18%;
TABLE 5 main chemical composition/% of desulfurized gypsum residue
Figure BDA0002277441090000062
The water quenching slag used in the embodiment is obtained by water quenching and quenching zinc-containing slag produced in a blast furnace reduction smelting process of a certain fire lead-smelting plant in Henan, the slag is in a glass state, a sample is crushed into fine powder with the particle size of 80% being less than 0.1mm for later use, the specific components of the water quenching slag are shown in Table 6, zinc in the water quenching slag is mainly formed by zinc silicate and zinc ferrite, and lead is mainly formed by metallic lead and lead oxide;
TABLE 6 main chemical composition/% of water-quenched slag
Figure BDA0002277441090000063
Figure BDA0002277441090000071
A method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag comprises the following specific steps:
(1) respectively mixing the above 1000kg of gypsum residue, 500kg of zinc leaching residue and 150kg of coke with 80% of granularity smaller than 5mm (mass ratio is 100:50: 15);
(2) placing the uniformly mixed sample on a steel belt furnace material distributor, controlling the feeding amount of the material distributor and the running speed of a steel belt so that the thickness of a material layer is 10-15 mm, introducing nitrogen into the steel belt furnace as a protective gas during roasting, setting the roasting temperature at 750 ℃, and controlling the running speed of the steel belt so that the sample stays in a furnace body for 3 hours;
(3) cooling the roasted sample to room temperature under the protection of nitrogen, sampling and analyzing the contents of arsenic, sulfur and lead-zinc sulfide in the sample, and calculating the volatilization rate of arsenic, the fixation rate of sulfur and the vulcanization rate of a lead-zinc compound;
TABLE 7 chemical analysis of reduced sulfided calcine/%)
Figure BDA0002277441090000072
The above data show that after reduction sulfidation roasting, the volatilization rate of arsenic is 91.2%, the fixation rate of sulfur is 97.2%, and the sulfidation rates of lead and zinc are 94.5% and 92.7%, respectively, the zinc and lead in the roasted product exist substantially in the form of sulfide, and the compounds of iron and silicon mainly exist in the form of calcium ferrite, calcium silicate and a small amount of ferrous sulfide, so that lead and zinc can be easily recovered by the conventional flotation method.
Comparative example 2
The vulcanizing agents used in this example were shown in Table 5 in terms of the main components, and the water-granulated slag used was shown in Table 6 in terms of the specific components.
A method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag comprises the following specific steps:
(1) respectively mixing the above 1000kg of gypsum residue, 500kg of zinc leaching residue and 100kg of coke with a particle size of 60% less than 10mm (mass ratio of 100:50: 10);
(2) placing the uniformly mixed sample on a steel belt furnace material distributor, controlling the feeding amount of the material distributor and the running speed of a steel belt to ensure that the thickness of a material layer is 10-15 mm, introducing nitrogen into the steel belt furnace as a protective gas during roasting, setting the roasting temperature to be 1100 ℃, and controlling the running speed of the steel belt to ensure that the sample stays in a furnace body for 2 hours;
(3) cooling the roasted sample to room temperature under the protection of nitrogen, sampling and analyzing the contents of arsenic, sulfur and lead-zinc sulfide in the sample, and calculating the volatilization rate of arsenic, the fixation rate of sulfur and the vulcanization rate of a lead-zinc compound;
TABLE 8 chemical analysis of reduced sulfurized roast products%
Figure BDA0002277441090000081
The data show that the lead and zinc are greatly reduced into metal to be volatilized and lost due to coarse granularity of the reducing agent, low proportioning of the reducing agent and overhigh roasting temperature, and in addition, calcium sulfate is decomposed to release SO2 due to high oxygen potential, SO that the fixation rate of sulfur is low. The zinc in the roasted product exists mainly in the form of marmatite and akermanite, and the iron exists mainly in the form of pyrrhotite and calcium ferrite.
Example 3
The vulcanizing agent used in the embodiment is desulfurized gypsum slag produced in the acid making and washing process of flue gas of a certain zinc smelting plant, the specific components of the desulfurized gypsum slag are shown in Table 4, the zinc-containing smoke dust of the steel plant used in the embodiment is blast furnace dust produced by a certain steel plant in Hunan, the granularity of the material is 75% and is less than 0.074mm, the material is fine and can be directly used, the specific components of the material are shown in Table 9, and the material zinc mainly exists in the forms of zinc oxide, zinc silicate and zinc ferrite, and iron hematite, iron silicate and ferroferric oxide;
TABLE 9 Main chemical composition/% of Steel plant Smoke dust
Figure BDA0002277441090000082
A method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag comprises the following specific steps:
(1) respectively mixing the 1000kg of gypsum slag, 750kg of zinc leaching slag and 250kg of anthracite with the granularity of 80 percent and less than 5mm (the mass ratio is 100:75: 25);
(2) placing the uniformly mixed sample on a steel belt furnace material distributor, controlling the feeding amount of the material distributor and the running speed of a steel belt to ensure that the thickness of a material layer is 5-10 mm, introducing nitrogen into the steel belt furnace as a protective gas during roasting, setting the roasting temperature to be 850 ℃, and controlling the running speed of the steel belt to ensure that the sample stays in a furnace body for 1.5 hours;
(3) cooling the roasted sample to room temperature under the protection of nitrogen, sampling and analyzing the contents of arsenic, sulfur and lead-zinc sulfide in the sample, and calculating the volatilization rate of arsenic, the fixation rate of sulfur and the vulcanization rate of a lead-zinc compound;
TABLE 10 chemical analysis of reduced sulfided calcine/%)
Figure BDA0002277441090000091
The above data show that after reduction-sulfidation roasting, the volatilization rate of arsenic is 93.2%, the fixation rate of sulfur is 98.1%, and the sulfidation rates of lead and zinc are 90.5% and 95.7%, respectively, zinc and lead in the roasted product exist substantially in the form of sulfide, and compounds of iron and silicon mainly exist in the form of calcium ferrite, calcium silicate and a small amount of ferrous oxide, so that lead and zinc can be easily recovered by a conventional flotation method.
For example 3
The vulcanizing agent used in the present embodiment is desulfurized gypsum slag produced in the acid making and washing process of flue gas of a certain zinc smelting plant, and the specific components thereof are shown in table 4, and the zinc-containing smoke dust of the steel plant used in the present embodiment is blast furnace dust produced in a certain steel plant in south of Hunan province, and the specific components thereof are shown in table 10. A method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag comprises the following specific steps:
(1) respectively mixing the above 1000kg of gypsum residue, 1250kg of zinc leaching residue and 250kg of anthracite coal with 80% granularity less than 5mm (mass ratio is 100:125: 25);
(2) placing the uniformly mixed sample on a steel belt furnace material distributor, controlling the feeding amount of the material distributor and the running speed of a steel belt so that the thickness of a material layer is 5-10 mm, introducing nitrogen into the steel belt furnace as a protective gas during roasting, setting the roasting temperature to be 900 ℃, and controlling the running speed of the steel belt so that the sample stays in a furnace body for 2 hours;
(3) cooling the roasted sample to room temperature under the protection of nitrogen, sampling and analyzing the contents of arsenic, sulfur and lead-zinc sulfide in the sample, and calculating the volatilization rate of arsenic, the fixation rate of sulfur and the vulcanization rate of a lead-zinc compound;
TABLE 11 chemical analysis of reduced sulfided calcine/%)
Figure BDA0002277441090000092
Because the proportion of zinc leaching residues is too much, the vulcanizing agent is insufficient, and the punching and vulcanizing of zinc can not be ensured, so that part of zinc is reduced and volatilized to be lost, and the main components of a roasting product are sphalerite, calcium ferrite and ferroferric oxide.

Claims (7)

1. A method for the synergistic vulcanization roasting of lead-zinc smelting slag and gypsum slag is characterized by comprising the following steps: mixing the lead-zinc smelting slag, the gypsum slag and the carbonaceous reducing agent, and placing the mixture in a protective atmosphere to perform reduction, vulcanization and roasting at the temperature of 650-1050 ℃ to obtain a roasted product containing lead sulfide, zinc sulfide, calcium silicate and calcium ferrite.
2. The method for the synergic vulcanization roasting of lead-zinc smelting slag and gypsum slag as claimed in claim 1, characterized in that: the mass ratio of the gypsum slag, the lead-zinc smelting slag and the carbonaceous reducing agent is 100: 50-100: 15 to 50.
3. The method for the synergic vulcanization roasting of lead-zinc smelting slag and gypsum slag as claimed in claim 2, characterized in that: the lead-zinc smelting slag comprises at least one of zinc ferrite slag, lead smelting water-quenched slag and steel mill smoke dust.
4. The method for the synergic vulcanization roasting of lead-zinc smelting slag and gypsum slag as claimed in claim 2, characterized in that: the gypsum slag comprises at least one of desulfurized gypsum slag and waste acid neutralization slag.
5. The method for the synergic vulcanization roasting of lead-zinc smelting slag and gypsum slag as claimed in claim 2, characterized in that: the carbonaceous reducing agent comprises at least one of coke, coke powder, charcoal and anthracite.
6. The method for the synergic vulcanization roasting of lead-zinc smelting slag and gypsum slag according to any one of claims 1 to 5, characterized in that: the temperature of the reduction, vulcanization and roasting is 700-1000 ℃, and the time is 1-3 h.
7. The method for the synergic vulcanization roasting of lead-zinc smelting slag and gypsum slag as claimed in claim 6, characterized in that: the reduction vulcanization roasting is realized by a steel belt furnace.
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