CN111020175A - Method for comprehensively recycling zinc-rich gypsum slag resources - Google Patents
Method for comprehensively recycling zinc-rich gypsum slag resources Download PDFInfo
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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
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- C22B1/02—Roasting processes
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Abstract
The invention discloses a method for comprehensively recovering zinc-rich gypsum residue resources, which comprises the steps of carrying out reduction, vulcanization and roasting on zinc-rich gypsum residue and a carbonaceous reducing agent to obtain a roasted product containing calcium sulfide and zinc sulfide, carrying out neutralization reaction on the roasted product and zinc smelting waste acid, recovering hydrogen sulfide gas, and obtaining secondary gypsum residue and neutralized liquid; and recovering zinc sulfide concentrate from the secondary gypsum slag by a flotation method, and carrying out reduction roasting on flotation tailings to obtain a calcium sulfide product. The method can effectively realize the comprehensive recycling of calcium, zinc and sulfur resources in the zinc-rich gypsum slag, and the whole process has no secondary waste slag, low energy consumption, environmental protection and good popularization and application prospects.
Description
Technical Field
The invention relates to a method for comprehensively recovering zinc-rich gypsum residues, in particular to a method for comprehensively recovering zinc and sulfur resources in zinc-rich gypsum residues by combining reduction vulcanization roasting and flotation, belonging to the technical field of non-ferrous metal beneficiation and metallurgy.
Background
China is a big country for zinc production and consumption, the zinc metal yield in 2015 in China is 621.7 ten thousand t, which accounts for more than 40% of the total world yield, and at present, 85% of zinc in China adopts a process of 'boiling roasting-two-stage leaching-purification and impurity removal-electrodeposition'. In the boiling roasting stage, a large amount of zinc-containing dust is accompanied with SO2The flue gas enters a flue, and SO is used for meeting the acid making requirement2The flue gas is washed and purified to remove harmful components such as zinc, arsenic, dust and the like, so that a large amount of zinc-containing acidic wastewater (polluted acid) can be produced; in the electrodeposition working section, a large amount of zinc-rich waste acid and acidic wastewater are generated in the operation of an electrodeposition tank and a purified liquid tank, the back washing process and the ground washing process of an electrolytic plant; because the lime neutralization method has simple process and low cost, the waste acid is treated by the lime neutralization method; the lime neutralization method is to adopt lime or dolomite as a neutralizer, and to precipitate harmful substances such as zinc, arsenic and the like in waste acid into gypsum residue while neutralizing the waste acid. The gypsum residue has high heavy metal content and belongs to typical dangerous solid waste.
Aiming at the resource characteristics of the waste acid neutralization slag, a great deal of research is carried out on the resource utilization and harmless disposal of the waste acid neutralization slag in China. At present, the treatment methods of the waste acid neutralization slag mainly comprise a rotary kiln volatilization method, a hydrothermal vulcanization method, a harmless method and the like. The rotary kiln volatilizing method is the most common gypsum slag treating method in China, and is characterized by that after the gypsum is mixed with a certain proportion of silicon dioxide and powdered coal, the mixture is reduced and volatilized at high temp. of 1200 deg.C-1400 deg.C, SO that the heavy metals of zinc, lead and copper and arsenic in the gypsum slag are volatilized and concentrated in the smoke dust, and the volatilization rate of heavy metals and arsenic is high, and the kiln slag can be used as building material after high-temp. activation, but its energy consumption is high, working environment is poor, and SO in the smoke gas is rich in trace elements2The concentration is low, and the requirement of acid making is difficult to meet.
The hydrothermal vulcanization method is a technology for realizing high-efficiency vulcanization of heavy metals in neutralized slag by utilizing a dissolution recrystallization mechanism under a hydrothermal condition. The Chinese patent CN 201010183293 adopts sulfur as a vulcanizing agent, the sulfur is added in an amount of 12-20%, the reaction is carried out for 1.5-4.5 h at the temperature of 160-240 ℃ in an autoclave, the vulcanization rate of zinc in neutralized slag is higher than 90%, but the zinc sulfide particles obtained by hydrothermal vulcanization are fine, the flotation recovery effect of the zinc sulfide is poor, in addition, the hydrothermal vulcanization method needs an expensive high-pressure reaction kettle, sulfur needs to be added as the vulcanizing agent, and the equipment investment and the operation cost are high.
The harmless disposal method mainly comprises cement curing, plastic material curing, glass curing and the like, and although the curing and stabilizing technology can effectively reduce the toxic degree of heavy metals in gypsum slag, the valuable metals cannot be recovered.
A large amount of zinc-rich gypsum slag is produced by lead-zinc smelting plants in China every year, but at present, no economic, green and feasible resource utilization treatment method exists, so that an environment-friendly, efficient and economic method for comprehensively recycling zinc-rich gypsum slag resources is developed, and the method is an important guarantee for realizing green, clean and sustainable development of the lead-zinc smelting industry.
Disclosure of Invention
The invention aims to provide a method for effectively comprehensively recovering and treating metal resources and sulfur resources in zinc-rich gypsum slag, which is economic, feasible and environment-friendly and is a method for cleaning and treating the zinc-rich gypsum slag by combining selection and metallurgy.
In order to realize the technical purpose, the invention provides a method for comprehensively recovering zinc-rich gypsum residue resources, which comprises the following steps:
1) putting the zinc-rich gypsum slag and a carbonaceous reducing agent into a protective atmosphere, and carrying out reduction vulcanization roasting at 650-850 ℃ to obtain a reduction vulcanization roasted product;
2) performing neutralization reaction on the reduction vulcanization roasting product and zinc smelting waste acid to obtain hydrogen sulfide gas, secondary gypsum slag and neutralized liquid;
3) recovering zinc sulfide from the secondary gypsum slag through flotation to obtain zinc sulfide concentrate and tailings;
4) and (4) carrying out reduction roasting on the tailings to obtain a calcium sulfide product.
In a preferable scheme, the mass of the carbonaceous reducing agent is 10-20% of that of the zinc-rich gypsum slag.
In a more preferable scheme, the zinc content in the zinc-rich gypsum slag is 5-20% by mass. The mass percent of iron in the zinc-rich gypsum slag is less than 10 percent, and if the mass percent of iron is too high, a large amount of Ca which is difficult to dissolve can be caused2Fe2S2O3And (4) generating the compound.
In a more preferable scheme, the granularity of the carbonaceous reducing agent is such that the mass percentage content of the carbonaceous reducing agent with the particle size of less than 1mm is more than 80%. Carbonaceous reducing agents are reducing agents commonly used in the art, such as coke, biomass char, and the like.
In a preferable scheme, the temperature of the reduction, vulcanization and roasting is 700-800 ℃, and the time is 0.5-2.5 h.
In a preferred embodiment, the neutralization reaction conditions are as follows: the method is carried out in a sealed reaction kettle, the liquid-solid ratio of the reduction vulcanization roasting product to the zinc smelting waste acid is 3-6 mL:1g, and the neutralization reaction time is 10-60 min. By adopting the closed reaction kettle, the H generated by the reaction can be reacted2And S gas is completely collected, no hydrogen sulfide gas leaks in the whole reaction process, and the obtained hydrogen sulfide gas is used as a vulcanizing agent or a raw material for sulfur production.
In a preferable scheme, the concentration of the zinc smelting waste acid is less than 90 g/L. The over-high acidity of zinc smelting waste acid can cause the dissolution of zinc sulfide, and the separation of the zinc sulfide and secondary gypsum can not be realized.
In a preferred scheme, the flotation process comprises flotation decarburization and then flotation of zinc sulfide. In order to avoid the adsorption of the carbonaceous reducing agent to the flotation reagent during flotation, flotation decarburization is carried out preferentially during flotation, and then zinc sulfide is floated. The flotation decarburization process is a common process in the flotation field.
In a more preferable scheme, the collecting agent adopted for floating the zinc sulfide is at least one of butyl xanthate, butyl ammonium blackate or ethyl sulfur nitrogen.
In the preferred scheme, the reduction vulcanization roasting is carried out in a steel belt furnace, the materials do not need to be granulated and pelletized in the roasting process, the processing capacity is high, and continuous roasting can be realized.
In a preferred scheme, the flotation tailings are mainly gypsum components, calcium sulfate can be converted into calcium sulfide through conventional reduction roasting, and the calcium sulfide can be used as a vulcanizing agent or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide.
The method for comprehensively recovering the zinc-rich gypsum residue resource comprises the following specific steps:
1) uniformly mixing the zinc-rich gypsum slag and a carbonaceous reducing agent in a certain proportion, then uniformly arranging the material on a steel belt of a steel belt furnace by a material distributor, carrying out reduction vulcanization roasting on the material at the roasting temperature of 650-850 ℃ for 0.5-5 h under the protection of nitrogen, reacting zinc oxide in the gypsum slag with calcium sulfate under the action of the carbonaceous reducing agent to be reduced and vulcanized into zinc sulfide, and reducing excessive calcium sulfate in the gypsum slag into calcium sulfide; the main reactions that occur during reduction-sulfidation roasting are as follows:
ZnO+CaSO4+2C＝ZnS+CaCO3+CO2
CaSO4+2C＝CaS+2CO2
2) performing neutralization reaction on the roasted product and zinc smelting waste acid in a closed reaction kettle to obtain hydrogen sulfide gas, secondary gypsum slag and neutralized liquid;
the main reactions taking place during neutralization are as follows:
CaS+H2SO4＝CaSO4+H2S
CaS+ZnSO4＝ZnS+CaSO4
H2S+ZnSO4＝ZnS+H2SO4
CaCO3+H2SO4＝CaSO4+H2O+CO2
3) recovering zinc sulfide in the secondary gypsum slag by adopting a flotation method to obtain zinc sulfide concentrate and tailings; in the flotation process, MIBC is used as a foaming agent, residual carbonaceous reducing agent in slag is roughly separated and removed, then flotation is carried out under natural pH, sodium hexametaphosphate is used as a dispersing agent, copper sulfate is used as an activating agent, and butyl xanthate, butyl ammonium blackant or ethion nitrogen and the like are used as collecting agents, and zinc sulfide concentrate is recovered by flotation.
4) Uniformly mixing the tailings and a reducing agent, returning to reduction roasting, and carrying out reduction roasting at 650-850 ℃ for 60-180 min by taking coke powder as a carbonaceous reducing agent; the calcium sulfide obtained by secondary roasting can be used as a vulcanizing agent or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide.
The key point of the comprehensive recovery process of the zinc-rich gypsum residue resource is that firstly, the sulfur element contained in the gypsum residue is used as a vulcanizing agent to realize the conversion of zinc oxide in the gypsum residue under the action of a carbonaceous reducing agent, so that the zinc oxide is reduced and vulcanized into zinc sulfide, and meanwhile, the carbonaceous reducing agent reduces the residual calcium sulfate in the gypsum residue into calcium sulfide, thereby realizing the high-efficiency fixation of sulfur and the high-efficiency vulcanization of zinc. The roasted product mainly comprises calcium sulfide and zinc sulfide, and the calcium sulfide can be used as a vulcanizing agent and a neutralizing agent to react with zinc smelting waste acid, so that the vulcanization precipitation of heavy metals in the waste acid, the neutralization of waste acid and the activation of the zinc sulfide in the roasted product are realized; and recovering zinc sulfide in the neutralized secondary gypsum slag by adopting a flotation method to obtain zinc sulfide concentrate and secondary gypsum tailings, directly returning the obtained zinc sulfide concentrate to a zinc smelting system, returning the obtained secondary gypsum slag to a reduction roasting system to synthesize calcium sulfide, and using the obtained calcium sulfide as a vulcanizing agent or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide. The process can efficiently convert sulfur in the gypsum slag into zinc sulfide and calcium sulfide to be fixed in the reduction, vulcanization and roasting processes, thereby avoiding SO2Release of (1); the primary roasting product and the zinc smelting waste acid are subjected to neutralization reaction, so that the neutralization of the waste acid, the vulcanization and precipitation of zinc heavy metal ions and the recovery of sulfur resources are realized (H)2S gas) and simultaneously realizes activation of zinc sulfide, which facilitates flotation recovery. Compared with the traditional rotary kiln volatilization method, the process has the advantages of low reaction temperature, low consumption of reducing agent, low energy consumption, no waste generation and the like.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) book (I)The technical scheme of the invention can convert zinc oxide in the gypsum slag into zinc sulfide efficiently by reducing and auto-vulcanizing roasting the zinc-containing gypsum slag which is abundantly existed in the existing zinc nonferrous metallurgy industry, the vulcanization conversion rate of the zinc is more than 95 percent, the sulfur in the slag is fixed efficiently in the form of zinc sulfide and calcium sulfide, the fixation rate of the sulfur is more than 97 percent, and the whole process basically has no SO2And (4) releasing.
2) According to the technical scheme, zinc smelting waste acid can be treated simultaneously, recovery of zinc in the waste acid can be realized, reduction and vulcanization roasting products are used as a neutralizing agent and a vulcanizing agent for waste acid treatment, sulfur in gypsum residues is collected in a hydrogen sulfide mode in the process, and zinc sulfide in the reduction and roasting products is activated through acid washing so as to be easy to recover through a flotation method.
3) The technical scheme of the invention has the advantages of mild process conditions, low energy consumption, environmental protection, simple operation, no waste gas and waste residue, and contribution to industrial production.
Drawings
FIG. 1 shows the process of the present invention.
FIG. 2 XRD pattern of reduction-sulfidation-calcined product.
Fig. 3 XRD pattern of flotation concentrate.
FIG. 4 is an XRD pattern of a calcined product of comparative example 1.
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 zinc-containing gypsum slag used in this example is from a large zinc smeltery in Oizhou, and the specific components are shown in Table 1, the main components of the neutralized slag are dihydrate, calcium sulfate and zinc hydroxide, the content of calcium sulfate dihydrate is 65.6%, and the content of zinc hydroxide is 18.3%.
TABLE 1 Main chemical composition of the neutralized slag/%)
The zinc smelting waste acid used in this example is from zinc smelting plant of heng-heng, Hunan, and its specific composition is shown in Table 2.
TABLE 2 Zinc smelting contaminated acid principal component/(mg/L)
A method for comprehensively recovering zinc-rich gypsum residue resources comprises the following specific steps:
(1) taking 3000kg of the naturally air-dried gypsum slag and 450kg of coke powder with the granularity of 80% and less than 1mm, uniformly mixing the uniformly mixed material on a steel belt of a steel belt furnace through a material distributor, ensuring the thickness of a material layer to be 10-20 cm by controlling the feeding amount of the material distributor and the belt speed of the steel belt furnace, introducing nitrogen, controlling the running speed and the furnace temperature of the steel belt to enable the material to be heated at the constant temperature of 750 ℃ for 90min, cooling a roasting sample to the room temperature, and taking out; the results of chemical analysis show that the content of zinc sulfide in the roasted sample is 26.3%, the vulcanization rate of zinc is 96.82%, the content of sulfur is 19.12%, the fixation rate of sulfur is 98.32%, the roasted products mainly comprise calcium sulfide, calcium carbonate and zinc sulfide, and the XRD pattern of the roasted product is shown in figure 2.
(2) Collecting the above calcined sample 250kg and 1000L (L/S-4/1) of the above zinc smelting waste acid at 1.5m3Stirring and reacting for 30min in the closed reaction kettle, storing a hydrogen sulfide gas collection part generated in the reaction process, raising the pH of waste acid to 6.0 after the reaction is finished, and respectively reducing the concentrations of zinc, copper, fluorine, arsenic and cadmium ions in the filtered filtrate to 5mg/L, 1mg/L, 50mg/L, 6mg/L and 10mg/L, wherein the water content of the filter residue is 18.5%.
(3) Taking 300kg of filter residue, controlling the concentration of the ore pulp to be 35%, firstly adopting MIBC as a foaming agent, roughly selecting residual carbonaceous reducing agent in the removed filter residue, then carrying out flotation under natural pH, taking sodium hexametaphosphate as a dispersing agent, taking the dosage of 1000g/t, taking copper sulfate as an activating agent, taking the dosage of 400g/t, taking butyl xanthate and butyl ammonium black as collecting agents, taking the dosage of butyl ammonium black plus butyl xanthate 150g/t plus 150g/t, carrying out one-step rough two-step fine two-step sweep in the flotation process, obtaining 56% of zinc in zinc sulfide concentrate through a closed circuit test, wherein the recovery rate of zinc is 93%, the XRD (X diffraction diagram) of the zinc sulfide concentrate is shown in figure 3, and the main component of tailings is gypsum.
(4) And (2) uniformly mixing 200kg of filter residue with 20kg of coke powder with the granularity of 85% and less than 1mm, carrying out reduction roasting at 800 ℃ for 120min, cooling the roasted product to room temperature, taking out the roasted product, and analyzing the roasted product to obtain a sulfur content of 26.2%, a sulfur fixation rate of 97.6% and a calcium sulfide content of 68.7%, wherein the roasted product can be used as a vulcanizing agent for treating waste acid or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide.
The data show that the calcium sulfide slag obtained after reduction roasting can be used as a neutralizer and a vulcanizing agent for waste acid treatment, can effectively neutralize waste acid in the waste acid, and has high removal rate for heavy metal and fluoride ions in the waste acid; the floatability of the neutralized gypsum slag zinc sulfide is better, the comprehensive recovery rate of zinc is 92.3%, and the zinc concentrate obtained by flotation meets the zinc smelting requirement and can be directly returned to a zinc smelting system; after the tailings are reduced and roasted, the obtained roasted product has high calcium sulfide content and can be used as a vulcanizing agent for treating waste acid or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide.
Comparative example 1
The zinc-containing gypsum slag used in this example is from a large zinc smeltery in Oizhou, and the specific components are shown in Table 1, and the waste acid from zinc smelting in Henan Heyang, and the specific components are shown in Table 2.
A method for comprehensively recovering zinc-rich gypsum residue resources comprises the following specific steps:
(1) taking 3000kg of the naturally air-dried gypsum slag and 750kg of coke powder with the granularity of 80% and less than 1mm, uniformly mixing the uniformly mixed material on a steel belt of a steel belt furnace through a material distributor, ensuring the thickness of a material layer to be 10-20 cm by controlling the feeding amount of the material distributor and the belt speed of the steel belt furnace, introducing nitrogen, controlling the running speed and the furnace temperature of the steel belt to heat the material at the constant temperature of 950 ℃ for 180min, cooling a roasted sample to the room temperature, and taking out; the results of chemical analysis show that the content of zinc sulfide in the roasted sample is 8.3%, the vulcanization rate of zinc is 65.73%, the content of sulfur is 26.15%, the fixation rate of sulfur is 87.5%, and due to high roasting temperature, the dosage of the reducing agent is large, 85.7% of zinc is reducedBecomes metallic zinc and is lost, and the calcium sulfide and the iron oxide in the gypsum residue generate insoluble compound Ca2Fe2S2O3The roasted product is mainly CaS and Ca2Fe2S2O3The XRD patterns of ZnS and FeO, the calcination product are shown in FIG. 4.
(2) Collecting the above calcined sample 250kg and 1000L (L/S-4/1) of the above zinc smelting waste acid at 1.5m3Stirring and reacting for 60min in a closed reaction kettle, storing a hydrogen sulfide gas collection part generated in the reaction process, raising the pH of waste acid to 4.0 after the reaction is finished, respectively reducing the concentrations of zinc, copper, fluorine, arsenic and cadmium ions in the filtered filtrate to 30mg/L, 2mg/L, 80mg/L, 7mg/L and 14mg/L, and leading the water content of filter residue to be 18.5 percent due to the indissolvable compound Ca in the roasted product2Fe2S2O3The content is high, and the sulfuration effect and the neutralization effect are poor until the reduction roasting product neutralizes the waste acid.
(3) Taking 300kg of filter residue, controlling the concentration of ore pulp to be 35%, carrying out flotation under natural pH, taking sodium hexametaphosphate as a dispersing agent, taking 1000g/t, taking copper sulfate as an activating agent, taking 400g/t, taking butyl xanthate and butyl ammonium black as collecting agents, taking 150g/t +150g/t of butyl ammonium black and butyl xanthate, carrying out flotation flow by coarse and fine two-pass, obtaining zinc sulfide concentrate containing 23.5% of zinc by a closed-loop test, wherein the recovery rate of zinc is 87.4%, because the carbonaceous reducing agent is not removed in advance before flotation, and zinc is volatilized during roasting, the zinc content of the zinc sulfide concentrate is low, and the main components of tailings are gypsum and Ca, the smelting requirement cannot be met, and the tailings contain the main components of gypsum and Ca2Fe2S2O3。
(4) Mixing 200kg of the above residue with 20kg of coke powder with particle size of 85% less than 1mm, reducing and roasting at 650 deg.C for 240min, cooling the roasted product to room temperature, taking out, and analyzing the roasted product to obtain the sulfur content of 15.8%, sulfur fixation rate of 98.8%, calcium sulfide content of 45.3%, and tailings containing a large amount of high temperature heat-resistant compound Ca2Fe2S2O3Resulting in a reduced calcine product with a low calcium sulfide content.
The above data indicate that too high a reduction temperature and too much reductant use can result in volatilization of zinc sulfide, SO2Release and high temperature resistant compound Ca2Fe2S2O3Generating; during flotation, the carbonaceous reducing agent in the slag is not removed in advance, so that the flotation agent is adsorbed, and zinc concentrate cannot meet the smelting requirement easily.
Example 2
The zinc-containing gypsum slag used in the example is from a large zinc smeltery of Yunnan Qujing, and the specific components of the zinc-containing gypsum slag are shown in Table 3, wherein the main components of the neutralized slag comprise dihydrate, calcium sulfate and zinc hydroxide, the content of the dihydrate calcium sulfate is 87.5%, and the content of the zinc hydroxide is 8.63%.
TABLE 3 Main chemical composition of the neutralized slag/%)
The waste acid from zinc smelting in Chenzhou, Hunan province comes from zinc smelting plant, and the specific components are shown in Table 4.
TABLE 4 Zinc smelting contaminated acid principal component/(mg/L)
A method for comprehensively recovering zinc-rich gypsum residue resources comprises the following specific steps:
(1) taking 3000kg of the naturally air-dried gypsum slag and 300kg of wood carbon powder with the granularity of 80% and less than 1mm, uniformly mixing the uniformly mixed material on a steel belt of a steel belt furnace through a material distributor, ensuring the thickness of a material layer to be 10-20 cm by controlling the feeding amount of the material distributor and the belt speed of the steel belt furnace, introducing nitrogen, controlling the running speed and the furnace temperature of the steel belt to enable the material to be heated at the constant temperature of 650 ℃ for 240min, cooling a roasting sample to the room temperature, and taking out; the results of chemical analysis show that the content of zinc sulfide in the roasted sample is 15.4%, the vulcanization rate of zinc is 98.65%, the content of sulfur is 24.6%, the fixation rate of sulfur is 98.76%, and the roasted products mainly comprise calcium sulfide, calcium carbonate, zinc sulfide and ferrous sulfide.
(2) Taking the above roasted sample 250kg and 1.5m3(L/S-6/1) the above-mentioned zinc smelting sludgeAcid at 2m3Stirring and reacting for 60min in the closed reaction kettle, storing a hydrogen sulfide gas collection part generated in the reaction process, raising the pH of waste acid to 6.5 after the reaction is finished, respectively reducing the concentrations of zinc, copper, fluorine, arsenic and cadmium ions in the filtered filtrate to 8mg/L, 1mg/L, 15mg/L, 7mg/L and 5mg/L, and enabling the water content of filter residue to be 20.6%.
(3) Taking 300kg of filter residue, controlling the concentration of the ore pulp to be 35%, firstly adopting MIBC as a foaming agent, roughly selecting residual carbonaceous reducing agent in the removed filter residue, then carrying out flotation under natural pH, taking sodium hexametaphosphate as a dispersing agent, taking the dosage of 800g/t, taking copper sulfate as an activating agent, taking the dosage of 600g/t, taking butyl xanthate and butyl ammonium black as collecting agents, taking the dosage of 100g/t +100g/t of butyl ammonium black and butyl xanthate, carrying out a rough three-fine two-pass flotation process, obtaining a zinc sulfide concentrate containing 45.6% of zinc by a closed-loop test, wherein the recovery rate of zinc is 94.4%, and the main component of tailings is gypsum.
(4) And (2) uniformly mixing 200kg of filter residue with 40kg of coke powder with the granularity of 80% and less than 1mm, carrying out reduction roasting at 850 ℃ for 120min, cooling the roasted product to room temperature, taking out the roasted product, and analyzing the roasted product to obtain the product with the sulfur content of 38.4%, the sulfur fixation rate of 98.2% and the calcium sulfide content of 73.5%, wherein the calcium sulfide content of the roasted product is high, and the roasted product can be used as a vulcanizing agent for waste acid treatment or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide.
The results show that after reduction roasting, the sulfur in the gypsum slag is efficiently fixed in the forms of calcium sulfide, zinc sulfide and the like, and insoluble compounds Ca are avoided in the roasting process2Fe2S2O3The calcium sulfide content in the roasted product is high, and the calcium sulfide has strong capability of removing heavy metal and fluorine ions as a vulcanizing agent in the waste acid neutralization process. The floatability of zinc sulfide in the neutralization slag is good, the comprehensive recovery rate of zinc is 93.2%, and zinc concentrate obtained by flotation meets the zinc smelting requirement and can be directly returned to a zinc smelting system; after the tailings are reduced and roasted, the obtained roasted product has high calcium sulfide content and can be used as a vulcanizing agent for treating waste acid or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide.
Comparative example 2
The zinc-containing gypsum slag used in this example is from a large zinc smelting plant of yunnan qujing, and the specific components thereof are shown in table 3, and the zinc smelting waste acid used is from a zinc smelting plant of chenzhou, Hunan, and the specific components thereof are shown in table 4.
A method for comprehensively recovering zinc-rich gypsum residue resources comprises the following specific steps:
(1) taking 3000kg of the naturally air-dried gypsum slag and 200kg of wood carbon powder with the granularity of 80% and less than 1mm, uniformly mixing the uniformly mixed material on a steel belt of a steel belt furnace through a material distributor, ensuring the thickness of a material layer to be 10-20 cm by controlling the feeding amount of the material distributor and the belt speed of the steel belt furnace, introducing nitrogen, controlling the running speed and the furnace temperature of the steel belt to enable the material to be heated at constant temperature of 850 ℃ for 25min, cooling a roasting sample to room temperature, and taking out; the results of chemical analysis show that the content of zinc sulfide in the roasted sample is 10.3%, the vulcanization rate of zinc is 82.35%, the content of sulfur is 26.7%, and the fixation rate of sulfur is 98.76%.
(2) Collecting the above roasted sample 200kg and 1.4m3(L/S-7/1) the zinc smelting waste acid is 2m3Stirring and reacting for 60min in the closed reaction kettle, storing a hydrogen sulfide gas collection part generated in the reaction process, raising the pH value of waste acid to 2.0 after the reaction is finished, respectively reducing the concentrations of zinc, copper, fluorine, arsenic and cadmium ions in the filtered filtrate to 26mg/L, 1mg/L, 35mg/L, 15mg/L and 8mg/L, and leading the water content of filter residue to be 17.3 percent.
(3) Taking 300kg of filter residue, controlling the concentration of the ore pulp to be 35%, firstly adopting MIBC as a foaming agent, roughly selecting residual carbonaceous reducing agent in the removed filter residue, then carrying out flotation under natural pH, taking sodium hexametaphosphate as a dispersing agent, taking the dosage of 800g/t, taking copper sulfate as an activating agent, taking the dosage of 600g/t, taking butyl xanthate and butyl ammonium black as collecting agents, taking the dosage of 100g/t +100g/t of butyl ammonium black and butyl xanthate, carrying out a rough three-fine two-pass flotation process, obtaining zinc sulfide concentrate containing 28.9% of zinc by a closed-loop test, wherein the recovery rate of zinc is 87.4%, and the main component of tailings is gypsum.
(4) And (3) uniformly mixing 200kg of filter residue with 40kg of coke powder with the granularity of 80% and less than 1mm, reducing and roasting at 600 ℃ for 240min, cooling the roasted product to room temperature, taking out the roasted product, and analyzing the roasted product to obtain the product with the sulfur content of 24.6%, the sulfur fixation rate of 99.5% and the calcium sulfide content of 36.5%.
The results show that the reduction and vulcanization time is too short, and the roasting temperature is too low, so that the reduction of calcium sulfate and the vulcanization and transformation of zinc are not facilitated.
Example 3
The zinc-containing gypsum slag used in this example is from a large zinc smelter in Otsuma, and the specific components are shown in Table 1,
the used zinc smelting waste acid comes from a zinc smelting plant of Henan Hengyang, and the specific components of the zinc smelting waste acid are shown in Table 2.
A method for comprehensively recovering zinc-rich gypsum residue resources comprises the following specific steps:
(1) taking 3000kg of the naturally air-dried gypsum slag and 600kg of coke powder with the granularity of 80% and less than 1mm, uniformly mixing the uniformly mixed material on a steel belt of a steel belt furnace through a material distributor, ensuring the thickness of a material layer to be 10-20 cm by controlling the feeding amount of the material distributor and the belt speed of the steel belt furnace, introducing nitrogen, controlling the running speed and the furnace temperature of the steel belt to enable the material to be heated at a constant temperature of 850 ℃ for 60min, cooling a roasting sample to the room temperature, and taking out; the results of chemical analysis show that the content of zinc sulfide in the roasted sample is 34.5%, the vulcanization rate of zinc is 97.3%, the content of sulfur is 28.14%, the fixation rate of sulfur is 97.4%, and the roasted products mainly comprise calcium sulfide, calcium carbonate and zinc sulfide.
(2) Collecting the above calcined sample 250kg and 750L (L/S ═ 3/1), and mixing the above zinc smelting waste acid at 1.5m3Stirring and reacting for 60min in the closed reaction kettle, storing a hydrogen sulfide gas collection part generated in the reaction process, raising the pH of waste acid to 6.8 after the reaction is finished, and respectively reducing the concentrations of zinc, copper, fluorine, arsenic and cadmium ions in the filtered filtrate to 2mg/L, 0.5mg/L, 17mg/L, 5mg/L and 3mg/L, wherein the water content of filter residue is 21.2%.
(3) Taking 300kg of filter residue, controlling the concentration of ore pulp to be 35%, firstly adopting MIBC as a foaming agent, roughly selecting residual carbonaceous reducing agent in the removed filter residue, then carrying out flotation under natural pH, taking sodium hexametaphosphate as a dispersing agent, taking the dosage of 1000g/t, taking copper sulfate as an activating agent, taking the dosage of 400g/t, taking butyl xanthate and butyl ammonium black as collecting agents, taking the dosage of butyl ammonium black plus butyl xanthate as 150g/t plus 150g/t, carrying out one-step rough two-step fine two-step sweep in the flotation process, obtaining zinc sulfide concentrate containing 61%, zinc recovery rate being 92%, and main components of tailings being gypsum through a closed-loop test.
(4) And (2) uniformly mixing 200kg of filter residue with 20kg of coke powder with the granularity of 85% and less than 1mm, reducing and roasting at 650 ℃ for 240min, cooling the roasted product to room temperature, taking out the roasted product, and analyzing the roasted product to obtain a sulfur content of 17.2%, a sulfur fixation rate of 99.2% and a calcium sulfide content of 53.5%, wherein the roasted product can be used as a vulcanizing agent for treating waste acid or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide.
The data show that the calcium sulfide slag obtained after reduction roasting can be used as a neutralizer and a vulcanizing agent for waste acid treatment, can effectively neutralize waste acid in the waste acid, and has high removal rate for heavy metal and fluoride ions in the waste acid; the floatability of the neutralized gypsum slag zinc sulfide is good, the comprehensive recovery rate of zinc is 91%, and the zinc concentrate obtained by flotation meets the zinc smelting requirement and can be directly returned to a zinc smelting system; after the tailings are reduced and roasted, the obtained roasted product has high calcium sulfide content and can be used as a vulcanizing agent for treating waste acid or a raw material for synthesizing thiourea, light calcium carbonate and hydrogen sulfide.
Comparative example 3
The zinc-containing gypsum slag used in this example is from a large zinc smelter in Otsuma, and the specific components are shown in Table 1,
the used zinc smelting waste acid comes from a zinc smelting plant of Henan Hengyang, and the specific components of the zinc smelting waste acid are shown in Table 2.
A method for comprehensively recovering zinc-rich gypsum residue resources comprises the following specific steps:
(1) taking 3000kg of the naturally air-dried gypsum slag and 600kg of coke powder with the granularity of 80% and less than 1mm, uniformly mixing the uniformly mixed material on a steel belt of a steel belt furnace through a material distributor, ensuring the thickness of a material layer to be 10-20 cm by controlling the feeding amount of the material distributor and the belt speed of the steel belt furnace, introducing nitrogen, controlling the running speed and the furnace temperature of the steel belt to enable the material to be heated at a constant temperature of 850 ℃ for 60min, cooling a roasting sample to the room temperature, and taking out; the results of chemical analysis show that the content of zinc sulfide in the roasted sample is 34.5%, the vulcanization rate of zinc is 97.3%, the content of sulfur is 28.14%, the fixation rate of sulfur is 97.4%, and the roasted products mainly comprise calcium sulfide, calcium carbonate and zinc sulfide.
(2) Taking 300kg of the roasted product, controlling the concentration of the ore pulp to be 35%, firstly adopting pine oil as a foaming agent, roughly selecting residual carbonaceous reducing agent in deslagging, then performing flotation under natural pH, taking sodium hexametaphosphate as a dispersing agent, taking the dosage of 1000g/t, taking copper sulfate as an activating agent, taking the dosage of 400g/t, taking butyl xanthate and butyl ammonium black as collecting agents, taking the dosage of 150g/t +150g/t of butyl ammonium black and butyl xanthate, performing a flotation process of one-step coarse cleaning and two-step cleaning, obtaining 36.3% of zinc sulfide concentrate through a closed circuit test, wherein the zinc sulfide recovery rate is 65%, because a large amount of calcium sulfide exists in the roasted product, the ore pulp contains a large amount of calcium ions and sulfur ions due to dissolution of the calcium sulfide during flotation, and zinc sulfide in the roasted product is not subjected to acid cleaning, so that the hydrophobicity of the zinc sulfide is poor and the flotation is difficult; the main components of the tailings are calcium sulfide, zinc sulfide, calcium carbonate and calcium sulfate.
The data show that the roasted product is not subjected to acid treatment and direct flotation, so that the separation and enrichment of zinc are not facilitated, the dissolution of calcium sulfide in ore pulp and the adverse effect of an oxidant on tailing treatment in the flotation process also cause difficulty in recycling of flotation wastewater.
Claims (10)
1. A method for comprehensively recovering zinc-rich gypsum slag resources is characterized by comprising the following steps: the method comprises the following steps:
1) putting the zinc-rich gypsum slag and a carbonaceous reducing agent into a protective atmosphere, and carrying out reduction vulcanization roasting at 650-850 ℃ to obtain a reduction vulcanization roasted product;
2) performing neutralization reaction on the reduction vulcanization roasting product and zinc smelting waste acid to obtain hydrogen sulfide gas, secondary gypsum slag and neutralized liquid;
3) recovering zinc sulfide from the secondary gypsum slag through flotation to obtain zinc sulfide concentrate and tailings;
4) and (4) carrying out reduction roasting on the tailings to obtain a calcium sulfide product.
2. The method for comprehensively recycling the zinc-rich gypsum slag resource according to claim 1, which is characterized by comprising the following steps: the mass of the carbonaceous reducing agent is 10-20% of that of the zinc-rich gypsum slag.
3. The method for comprehensively recycling the zinc-rich gypsum slag resource according to claim 2, characterized by comprising the following steps: the zinc content of the zinc-rich gypsum slag is 5-20% by mass, and the iron content is less than 10% by mass.
4. The method for comprehensively recycling the zinc-rich gypsum slag resource according to claim 2, characterized by comprising the following steps: the granularity of the carbonaceous reducing agent meets the condition that the mass percentage content of the carbonaceous reducing agent with the particle size of less than 1mm is more than 80%.
5. The method for comprehensively recycling the zinc-rich gypsum slag resource according to any one of claims 1 to 4, characterized by comprising the following steps: the temperature of the reduction, vulcanization and roasting is 700-800 ℃, and the time is 0.5-2.5 h.
6. The method for comprehensively recycling the zinc-rich gypsum slag resource according to claim 5, characterized by comprising the following steps: the reduction vulcanization roasting is carried out in a steel belt furnace.
7. The method for comprehensively recycling the zinc-rich gypsum slag resource according to claim 1, which is characterized by comprising the following steps: the neutralization reaction conditions are as follows: the method is carried out in a sealed reaction kettle, the liquid-solid ratio of the reduction vulcanization roasting product to the zinc smelting waste acid is 3-6 mL:1g, and the neutralization reaction time is 10-60 min.
8. The method for comprehensively recycling the zinc-rich gypsum slag resource according to claim 7, characterized by comprising the following steps: the concentration of the zinc smelting waste acid is less than 90 g/L.
9. The method for comprehensively recycling the zinc-rich gypsum slag resource according to claim 1, which is characterized by comprising the following steps: the flotation process comprises the steps of flotation decarburization and then flotation of zinc sulfide.
10. The method for comprehensively recycling the zinc-rich gypsum slag resource according to claim 9, characterized by comprising the following steps: the collecting agent adopted by the flotation of the zinc sulfide is at least one of butyl xanthate, butyl ammonium blackate or ethyl sulfur nitrogen.
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