CN112080642A - Method for comprehensively recycling desulfurized gypsum slag and waste magnesium-chromium refractory bricks through synergistic treatment - Google Patents
Method for comprehensively recycling desulfurized gypsum slag and waste magnesium-chromium refractory bricks through synergistic treatment Download PDFInfo
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- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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Abstract
The invention discloses a method for comprehensively recovering desulfurized gypsum slag and waste magnesium-chromium refractory bricks by synergistic treatment, which comprises the following steps: 1) reselecting and recovering precious metals; 2) leaching the chromium by using chloride to recover chromium; 3) reducing and roasting calcium sulfide; 4) preparing gas from calcium sulfide; 5) recovering iron by goethite method; 6) evaporating and crystallizing to recover magnesium. The leaching agent of the invention adopts hydrochloric acid and ferric chloride for leaching, and introduces Fe3+The oxidant improves the potential of the leaching system to promote the leaching of Sb, so that the leaching rate of Sb in the invention reaches about 92 percent, and the leaching rate of Pb and Bi is more than 98 percent, thereby greatly improving the leaching rate of Sb, Pb and Bi. More particularly, the hydrochloric acid and ferric chloride method of the invention can obtain chromium product Cr2O3The content is more than or equal to 45 percent, the content of impurity metals such as Cu, Ag, Sb, Pb, Bi and the like is less than 1 percent, and the quality of chromium products and the leaching rate of valuable metals are greatly improved.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a method for comprehensively recycling desulfurized gypsum slag and waste magnesium-chromium refractory bricks through synergistic treatment.
Background
The magnesium-chromium refractory brick is widely applied to high-temperature industries such as nonferrous smelting and the like due to the excellent slag resistance, and no other refractory material can replace the magnesium-chromium refractory brick at present. With the increasing of the non-ferrous metal output in China, the demand of the magnesium-chromium refractory material is increased day by day, the conditions in the non-ferrous smelting furnace are complex, the working surface of the refractory material in the furnace is directly contacted with various oxide slag, metal melt and sulfide melt, sulfur dioxide and other gases can be generated in the smelting process, and the whole smelting furnace is a complex system with interaction of solid, liquid and gas phases, so the non-ferrous smelting refractory material has short service life and quick replacement frequency. Domestic and foreign researches show that the damage of the refractory material in the using process is mainly caused by three effects of chemical factors, thermodynamic factors, mechanical factors and the like, the three factors are not single effects, the interaction directly causes the working surface of the refractory material to be corroded and damaged, the service life of the magnesium-chromium refractory bricks is short in severe using environment, and therefore the number of the waste magnesium-chromium refractory bricks is increasing. The annual production of refractory materials all over the world is about 3500-4000 ten thousand tons, and 30-40% of refractory materials are lost in the using process, so that the annual production of waste refractory materials all over the world can reach 2800 ten thousand tons. The raw material grade for smelting non-ferrous metal is relatively low, and a large amount of alkaline slag is generated in the smelting process, so the magnesium-chromium refractory brick with good alkaline slag resistance is an essential refractory material for a smelting furnace. However, because the environment in the smelting furnace is complex, the working surface of the refractory material in the furnace is directly contacted with various oxide slag, metal melt and sulfide melt, and the service life of the magnesium-chromium refractory material for nonferrous smelting is generally 3-6 months under the influence of three functions of chemical factors, thermodynamic factors, mechanical factors and the like. According to statistics, the non-ferrous metal smelting industry of China generates about 400 million tons of waste magnesia-chrome bricks every year, at present, the waste magnesia-chrome bricks are mainly processed in modes of landfill disposal, smelting after manual selection, building materials and the like in the industry, the comprehensive utilization rate of resources is low, and secondary pollution can be generated.
Flue gas desulfurization gypsum, FGD gypsum for short, commonly called desulfurization gypsum, is mainly characterized in that wet desulfurization process is adopted for combustion of boilers of thermal power plants, smelting plants and large-scale enterprises to treat SO2The gas reacts with the lime slurry under the strong oxidation condition to generate industrial byproducts which are mostly white and gray yellow in color, and the industrial byproducts mainly comprise calcium sulfate dihydrate and also contain calcium carbonate, calcium sulfite and other impurities. The main chemical reaction is as shown in the formula
CaO+SO2+0.5O2+2H2O→CaSO4·2H2O
In recent years, with the improvement of environmental protection requirements and rapid economic development of countries in the world, the amount of industrial by-product gypsum is gradually increased year by year. Comprehensive utilization of industrial by-product gypsumThe method reduces the mining of natural gypsum, enables the economic energy to be developed continuously, and has very important significance for protecting the global ecological environment. The desulfurized gypsum is an important component in industrial byproduct gypsum as a sintered flue gas desulfurization product, and the discharged desulfurized gypsum in China can reach 1 x 10 in about 20208And more than ton. The method is particularly important for China, because the industrial starting of China is relatively late, the foundation is relatively weak, the extensive and rapid economic development mode has great influence on the ecological environment of China, and the related industrial byproduct gypsum utilization technology and equipment are not effectively developed and utilized.
Some existing patents and researches mainly focus on the two aspects of valuable metal recovery and refractory material regeneration of waste refractory bricks, while desulfurization gypsum utilization mainly focuses on low-added-value utilization modes such as cement and the like, and a technology for harmless and resource comprehensive recycling of the whole process is lacked.
Disclosure of Invention
The invention aims to provide a method for cooperatively treating and comprehensively recycling desulfurized gypsum slag and waste magnesium-chromium refractory bricks, which has the advantages of high comprehensive utilization rate, good economic benefit, no secondary pollution and strong applicability.
The invention discloses a method for comprehensively recovering desulfurized gypsum slag and waste magnesium-chromium refractory bricks through synergistic treatment, which comprises the following steps:
1) and (3) reselecting and recovering precious metals: crushing and grinding the waste magnesium-chromium refractory bricks, and then performing gravity separation by using a table concentrator to obtain gravity concentrate and gravity tailings, wherein the gravity concentrate is used for recovering precious metal silver;
2) and (3) leaching and recovering chromium by using chloride: leaching the gravity tailings in the step 1), wherein a solution containing chloride salt and hydrochloric acid is adopted as a leaching agent in the leaching process; after leaching, obtaining leaching slag and leaching liquid; the leached slag mainly contains ferrochrome which can be used as a chromite product;
3) reducing and roasting calcium sulfide: uniformly mixing the desulfurized gypsum slag and a reducing agent according to a certain proportion, then placing the material in a vacuum reduction furnace for drying and dehydration, and then heating for reduction, vulcanization and roasting to reduce the material into calcium sulfide;
4) preparing gas from calcium sulfide: mixing water and the calcium sulfide in the step 3) in a solid-liquid generator, and carrying out precipitation reaction on the leachate in the step 2) to recover impurity metals by using hydrogen sulfide gas generated by the solid-liquid generator; calcium oxide generated in the solid-liquid generator can be used as a calcium oxide product;
5) recovering iron by a goethite method: recovering iron from the leachate from which the impurity metals are removed in the step 4) by adopting a goethite method; obtaining an iron product and a leachate after iron removal;
6) evaporating and crystallizing to recover magnesium: evaporating and crystallizing the leachate after iron removal in the step 5) to recover magnesium.
In the step 1), the waste magnesium-chromium refractory bricks are crushed to be less than 3mm, then the waste magnesium-chromium refractory bricks are ground until the fineness is minus 0.074mm, and the fineness accounts for 60-70%, and a shaking table is adopted for gravity separation, namely a coarse sweeping and a fine closed-loop process.
In the step 2), the concentration of hydrochloric acid in the leaching agent is 4-5 mol/L, the chloride salt is ferric chloride, and the mass percentage of the ferric chloride in the leaching agent is 2-5%; the liquid-solid ratio (mass ratio) in the leaching process is (5-7) to 1; the leaching temperature is 60-80 ℃, the leaching time is 1.0-2.0 h, and the stirring intensity is 400-500 r/min.
In the step 3), the reducing agent is a carbonaceous reducing agent, and the mass ratio of the desulfurized gypsum residue to the reducing agent is 100: 15-30; the reduction and vulcanization temperature is 850-1150 ℃, and the reaction time is 30-120 min; the carbonaceous reducing agent is one or more of pulverized coal, coke, charcoal and anthracite.
In the step 4), calcium sulfide in the roasted product is finely ground to 0.1mm accounting for 85%, hydrogen sulfide is prepared by adopting an aqueous solution, the reaction time is 30-60 min, hydrogen sulfide gas is used for removing impurity metals in the waste refractory brick leaching solution, and the generated calcareous solution can be returned to be used in the smelting desulfurization process.
In the step 5), the specific process conditions of the iron recovered by the goethite method are as follows: maintaining the pH value to 3.5-4.0, using 15-20% of hydrogen peroxide (relative to the mass percentage of the leachate without impurity metals), reacting at 75-85 ℃ for 3-4 h; and filtering after leaching, wherein leaching slag is goethite, and leaching liquid is basically magnesium-containing solution.
In the step 6), the specific process for recovering magnesium by evaporation crystallization comprises the following steps: and (3) slowly adding magnesium hydroxide into the leachate after iron removal to adjust the pH value of the magnesium-containing solution to 7.0-7.5, and finally, cooling through evaporative crystallization to recover the magnesium metal.
The principle of the invention is as follows:
the waste refractory bricks of precious metal smelting furnaces for silver smelting, lead smelting and the like contain a large amount of precious metals such as Ag, Pb and the like, and have huge potential economic value. The components of the refractory brick are mainly periclase and chromium spinel, and the density difference between the precious metal and the refractory brick matrix is large, so the precious metal can be firstly recovered through table concentrator gravity separation, and the precious metal is enriched and recovered in gravity separation concentrate.
The gravity separation tailings also contain a small amount of impurity metals such as Pb, Bi, Sb, Cu, Ag and the like besides the refractory brick matrix. Wherein chromium is mainly in the form of chromite and spinel is difficult to dissolve in acid, periclase is easy to dissolve in acid, and impurity metals are mainly in the form of simple substance and oxide and are easy to dissolve in acid solution with high chloride ion concentration. Therefore, the separation of chromium, magnesium and impurity metals can be realized by adopting a chloridized acid leaching process, so that chromium can be selectively enriched and recovered. The chloride adopts ferric chloride, so that on one hand, the leaching of Cu and Ag can be promoted by improving the concentration of chloride ions, and on the other hand, Fe is introduced3+The oxidant improves the potential of a leaching system to promote the leaching of Sb. Hydrochloric acid and ferric chloride are used as a leaching agent, so that the leaching rate of magnesium and impurity metals can be higher, chromium is difficult to leach, the leaching slag is enriched, and the content of the impurity metals is low, so that the leaching slag can be recycled as a chromium product.
The leaching solution mainly contains Mg and Cl, Fe and a small amount of impurity metal ions such as Pb, Bi, Sb, Cu, Ag and the like. These metal ions are all susceptible to reaction with hydrogen sulfide to form sulfide precipitates. The desulfurized gypsum slag is reduced into calcium sulfide through carbon-carbon heat, the calcium sulfide reacts with water to produce hydrogen sulfide and CaO, the hydrogen sulfide can be used for selectively precipitating precious metals in leachate, and the generated calcium oxide product can be recycled and returned to be used in the flue gas desulfurization process of a smelting plant, so that the two wastes can be cooperatively treated, and the main reactions of the two wastes are as follows:
CaSO4+2C＝CaS+2CO2
CaS+H2O＝CaO+H2S↑
Me2++H2S＝MeS↓+2H+
the solution precipitated by hydrogen sulfide gas contains no impurity ions basically, only magnesium and iron are left, and the goethite method is used for recovering iron, and the main reactions are as follows: fe3++2H2O＝FeOOH↓+3H+. Adjusting the pH value of the iron-removing leachate to about 7.0 by using magnesium hydroxide, and finally evaporating and crystallizing to obtain a magnesium chloride product.
The invention has the beneficial effects that:
1) the invention firstly adopts the gravity separation process to recover the precious metal silver, avoids the problem that a great amount of silver exists in the leachate in the later leaching process and is difficult to separate from other metals, has mature recovery process and lower cost, and reduces the pressure of subsequent treatment.
2) The leaching agent of the invention adopts hydrochloric acid and ferric chloride for leaching, and introduces Fe3+The oxidant improves the potential of the leaching system to promote the leaching of Sb, so that the leaching rate of Sb in the invention reaches about 92 percent, and the leaching rate of Pb and Bi is more than 98 percent, thereby greatly improving the leaching rate of Sb, Pb and Bi. More particularly, the hydrochloric acid and ferric chloride method of the invention can obtain chromium product Cr2O3The content is more than or equal to 45 percent, the content of impurity metals such as Cu, Ag, Sb, Pb, Bi and the like is less than 1 percent, and the quality of chromium products and the leaching rate of valuable metals are greatly improved.
3) This patent adopts the H that desulfurization gypsum sediment reduction roasting vulcanization precipitation method produced2S, removing impurity metals in the leachate by using the gas, wherein the impurity removal rate is high, and the calcium oxide solution can return to the smelting desulfurization process without secondary pollution; furthermore, the method of the invention realizes the recycling of the two wastes simultaneously, and has very remarkable effect.
Drawings
FIG. 1 is a process flow diagram of the present invention.
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. The process flow diagram of the present invention is shown in fig. 1, which shows an embodiment.
Example 1
The desulfurized gypsum slag and the waste magnesium-chromium refractory bricks of the smelting furnace used in the embodiment are from a large zinc smelting plant in the continent, and the specific components are shown in tables 1 and 2 respectively, the desulfurized gypsum slag mainly comprises calcium sulfate dihydrate, and the content of the calcium sulfate dihydrate is 96.77%.
TABLE 1 main chemical composition/% of desulfurized gypsum residue
TABLE 2 main chemical composition/% of waste magnesium-chromium refractory bricks
A method for cooperatively treating desulfurized gypsum slag of a smelting furnace and waste magnesium-chromium refractory bricks comprises the following specific steps:
(1) the waste magnesium-chromium refractory brick is adopted to carry out primary-scanning-primary-fine table separation operation under the condition that the grinding fineness is-0.074 mm and accounts for 70%, and gravity concentrate is filtered and dried to obtain silver concentrate.
Reselection index/percentage of waste magnesia-chrome brick
(2) The gravity tailings are leached and reacted for 1.5 hours under the conditions that the concentration of hydrochloric acid is 4mol/L, the liquid-solid ratio is 7:1, the addition amount of ferric chloride is 4%, the leaching temperature is 70 ℃, and the stirring strength is 500r/min, and leached residue chromite is obtained by filtering and drying.
Grade and index of leached slag
Index comparison of leached slag and chromium concentrate
(3) The desulfurized gypsum slag and a carbonaceous reducing agent (pulverized coal adopted in the embodiment) are uniformly mixed according to a certain ratio (5:1), then the materials are uniformly distributed on a steel belt of a steel belt furnace through a distributing machine, and the materials are subjected to reduction vulcanization roasting for 2 hours at the roasting temperature of 1100 ℃ under the nitrogen protection atmosphere. The conversion of calcium sulfide was 96%. Placing the roasted product calcium sulfide and water in a reaction kettle, introducing the generated gas into the leachate, returning the calcareous solution to be used in the smelting desulfurization process, wherein the reaction time is 1h, and the impurity removal rate is as follows:
(4) adjusting the pH value of the leachate to 4.0 by using magnesium hydroxide, dropwise adding 15% hydrogen peroxide at 85 ℃ for reacting for 4 hours, filtering and drying to obtain goethite slag. XRF analysis shows that the obtained iron slag has 57.78% of Fe grade and higher Fe grade, and can be used as an iron-making raw material after being processed, and can also be used for preparing ferric chloride, iron powder and the like, thereby realizing the circulation of iron in the whole process.
(5) Evaporating and crystallizing the leachate after iron removal to obtain magnesium chloride, wherein the obtained magnesium chloride is magnesium chloride hexahydrate (MgCl)2·6H2O), the crystallinity is higher, the quality of the finally prepared magnesium chloride is better, and the magnesium chloride can be used as industrial magnesium chloride.
The data show that the comprehensive recovery of resources such as silver, iron, calcium, sulfur, chromium, magnesium and the like can be realized through the cooperative treatment of the desulfurized gypsum slag and the waste magnesium-chromium refractory bricks, no secondary pollution is caused, and the substances produced in the process are efficiently and cleanly utilized.
Claims (7)
1. A method for comprehensively recovering desulfurized gypsum slag and waste magnesium-chromium refractory bricks by synergistic treatment comprises the following steps:
1) and (3) reselecting and recovering precious metals: crushing and grinding the waste magnesium-chromium refractory bricks, and then performing gravity separation by using a table concentrator to obtain gravity concentrate and gravity tailings, wherein the gravity concentrate is used for recovering precious metal silver;
2) and (3) leaching and recovering chromium by using chloride: leaching the gravity tailings in the step 1), wherein a solution containing chloride salt and hydrochloric acid is adopted as a leaching agent in the leaching process; after leaching, obtaining leaching slag and leaching liquid; the leached slag mainly contains ferrochrome which can be used as a chromite product;
3) reducing and roasting calcium sulfide: uniformly mixing the desulfurized gypsum slag and a reducing agent according to a certain proportion, then placing the material in a vacuum reduction furnace for drying and dehydration, and then heating for reduction, vulcanization and roasting to reduce the material into calcium sulfide;
4) preparing gas from calcium sulfide: mixing water and the calcium sulfide in the step 3) in a solid-liquid generator, and carrying out precipitation reaction on the leachate in the step 2) of the hydrogen sulfide gas generated by the solid-liquid generator to recover impurity metals; calcium oxide generated in the solid-liquid generator can be used as a calcium oxide product;
5) recovering iron by a goethite method: recovering iron from the leachate from which the impurity metals are removed in the step 4) by adopting a goethite method; obtaining an iron product and a leachate after iron removal;
6) evaporating and crystallizing to recover magnesium: evaporating and crystallizing the leachate after iron removal in the step 5) to recover magnesium.
2. The method for cooperatively treating and comprehensively recovering the desulfurized gypsum slag and the waste magnesium-chromium refractory bricks according to claim 1, wherein in the step 1), the waste magnesium-chromium refractory bricks are crushed to be less than 3mm, then are ground until the fineness is-0.074 mm, and accounts for 60-70%, and a shaking table is adopted for gravity separation, namely a coarse sweeping and a fine sweeping closed-loop process.
3. The method for cooperatively treating and comprehensively recycling the desulfurized gypsum slag and the waste magnesium-chromium refractory bricks according to claim 1, wherein in the step 2), the concentration of hydrochloric acid in a leaching agent is 4-5 mol/L, chloride salt is ferric chloride, and the mass percent of the ferric chloride in the leaching agent is 2-5%; the liquid-solid ratio in the leaching process is (5-7) to 1; the leaching temperature is 60-80 ℃, the leaching time is 1.0-2.0 h, and the stirring intensity is 400-500 r/min.
4. The method for cooperatively treating and comprehensively recycling the desulfurized gypsum slag and the waste magnesium-chromium refractory bricks according to claim 1, wherein in the step 3), the reducing agent is a carbonaceous reducing agent, and the mass ratio of the desulfurized gypsum slag to the reducing agent is 100: 15-30; the reduction and vulcanization temperature is 850-1150 ℃, and the reaction time is 30-120 min; the carbonaceous reducing agent is one or more of pulverized coal, coke, charcoal and anthracite.
5. The method for cooperatively treating and comprehensively recycling the desulfurized gypsum slag and the waste magnesium-chromium refractory bricks according to claim 1, wherein in the step 4), calcium sulfide in the roasted product is finely ground to 0.1mm accounting for 85%, an aqueous solution is adopted for hydrogen sulfide preparation, the reaction time is 30-60 min, hydrogen sulfide gas is used for removing impurity metals in the leachate of the waste refractory bricks, and the calcareous solution can be returned for the desulfurization smelting process.
6. The method for the cooperative treatment and comprehensive recovery of the desulfurized gypsum slag and the waste magnesium-chromium refractory bricks according to claim 1, wherein in the step 5), the specific process conditions of the iron recovered by the goethite method are as follows: maintaining the pH value to 3.5-4.0, the using amount of hydrogen peroxide to be 15-20%, the reaction temperature to be 75-85 ℃ and the reaction time to be 3-4 h; and filtering after leaching, wherein leaching slag is goethite, and leaching liquid is basically magnesium-containing solution.
7. The method for the comprehensive recovery of the desulfurized gypsum slag and the waste magnesium-chromium refractory bricks through the synergistic treatment according to claim 1, wherein in the step 6), the specific process for recovering magnesium through evaporative crystallization is as follows: and (3) slowly adding magnesium hydroxide into the leachate after iron removal to adjust the pH value of the magnesium-containing solution to 7.0-7.5, and finally, cooling through evaporative crystallization to recover the magnesium metal.
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| CN118099495A (en) * | 2023-09-28 | 2024-05-28 | 斯瑞尔环境科技股份有限公司 | Method for preparing iron-chromium electrolyte by leaching carbon ferrochromium with ferric trichloride |
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| CN107716088A (en) * | 2017-09-29 | 2018-02-23 | 中南大学 | A kind of method for handling discarded magchrome refractory |
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| CN111020175A (en) * | 2019-11-18 | 2020-04-17 | 中南大学 | Method for comprehensively recycling zinc-rich gypsum slag resources |
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| CN118099495A (en) * | 2023-09-28 | 2024-05-28 | 斯瑞尔环境科技股份有限公司 | Method for preparing iron-chromium electrolyte by leaching carbon ferrochromium with ferric trichloride |
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