CN110607452A - Comprehensive utilization method of iron ore sintering smoke dust leaching solution - Google Patents
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Abstract
The invention discloses a comprehensive utilization method of an iron ore sintering smoke dust ash leaching solution, belonging to the technical field of industrial waste treatment. The method comprises the steps of leaching iron ore sintering smoke dust by water, and separating to obtain leaching solution and leaching residues; adding sodium oxalate into the leaching solution for precipitation, washing, drying and calcining to obtain a bismuth trioxide product, and carrying out sodium chromate precipitation reaction on the bismuth precipitation filtrate to obtain a lead chromate product; extracting the lead-separating filtrate by adopting a P507+ sulfonated kerosene organic phase, back extracting by using a sulfuric acid solution, and carrying out hydrothermal treatment to obtain a calcium sulfate whisker product; purifying the organic phase raffinate water solution, and carrying out two-stage conversion reaction to obtain potassium sulfate and industrial sodium chloride products; the method has the advantages of simple process equipment, easy and safe operation, realization of the high-efficiency recycling of potassium, sodium, calcium, lead, bismuth and other elements in the sintering dust, improvement of the additional value of raw materials, realization of the resource utilization of the sintering dust, waste recycle, reduction of environmental pollution and good industrial popularization and application prospect.
Description
Technical Field
The invention belongs to the field of research on utilization of industrial wastes in the metallurgical industry, and particularly relates to a comprehensive utilization method of an iron ore sintering smoke dust ash leaching solution.
Background
Calcium sulfate whisker, i.e., gypsum whisker, refers to calcium sulfate (Ca)SO4) Fibrous monocrystals, classified as anhydrous calcium sulfate (CaSO)4) Whiskers, calcium sulfate hemihydrate (CaSO)4·0.5H2O) whiskers and calcium sulfate dihydrate (CaSO)4·2H2O) whiskers. The calcium sulfate whisker has excellent physical and chemical properties and mechanical properties of high temperature resistance, acid and alkali resistance, chemical corrosion resistance, good electrical insulation, high strength, good toughness and compatibility, easy surface treatment and the like, and is widely used as a novel functional material in the manufacture of products such as plastics, rubber, adhesives, friction materials, coatings, paints, heat insulation materials, light building materials and the like. Compared with other inorganic whiskers, the calcium sulfate whiskers are a green non-metallic environment-friendly material with the lowest toxicity.
Potassium sulfate (chemical formula K)2SO4) The compound is a compound generated by combining sulfate ions and potassium ions, is soluble in water, insoluble in alcohol, acetone and carbon disulfide, has low hygroscopicity, is not easy to agglomerate, contains about 50 percent of effective potassium, is a common chemical fertilizer, is very suitable for preparing a mixed fertilizer, is widely applied to various soils and various crops, and is particularly widely applied to chlorine-repellent crops. In addition, potassium sulfate is also used in glass, dye, perfume, medicine and other industry.
Lead chromate C.I. pigment yellow 34, molecular formula PbCrO4The inorganic yellow pigment has excellent light resistance, heat resistance, water resistance, solvent resistance and acid and alkali resistance. Can be used for coloring various thermoplastic and thermosetting plastics, and can be used for making paint and ink, making watercolor, oil color, paper and rubber coloring, etc.
The iron ore sintering smoke dust is collected by a dust collecting system in the iron ore raw material sintering process of iron and steel enterprisesThe industrial waste comprises the following main components: k2O 20～35%，Na2O 5~8%，Cl 25～35%，Pb 5~12%，Fe 15～25%，CaO 7～12%，Al2O30.1 to 1.5%, MgO 0.4 to 1.5%, Bi 0.8 to 1.5%. The main components show that the sintering smoke dust contains various valuable elements such as potassium, sodium, lead, calcium, bismuth and the like, mainly exists in the form of chloride, and can be comprehensively recycled as secondary resources.
At present, the treatment process of the sintering smoke dust of the steel plant mainly comprises the steps of volatilizing and extracting metal elements such as lead, zinc and the like in slag after mixing with blast furnace gas mud, or returning to the sintering process, but the sintering capacity of a sintering machine is reduced by about 3 percent, the load of a blast furnace K, Na exceeds the standard, a gas pipeline is seriously corroded, and the like; or the raw material is added into a blast furnace to be used as raw material, and the special characteristics of the raw material can cause the corrosion of the furnace wall of the blast furnace, increase the energy consumption of ironmaking coal (coke), and the like; the method has the advantage that a large amount of valuable potassium, sodium, calcium, lead and other substances contained in the slag are not reasonably recycled and utilized. Patent documents CN102295301B and CN102134648B report a treatment method of leaching and sintering dust collection ash with an aqueous solution, separating, performing replacement and sodium carbonate precipitation on the leachate to remove impurities, evaporating and concentrating, cooling and crystallizing to obtain a potassium chloride product. Patent document CN107142378A discloses a method for extracting sintering smoke dust by water, precipitating the leaching solution with sodium chromate, separating to obtain lead chromate product, purifying the filtrate, evaporating, concentrating, and crystallizing to obtain potassium chloride product. Patent document CN103266227B discloses a method for extracting potassium chloride from sintered ash slag by leaching with an acidic thiourea solution, reducing the thiourea leachate with a reducing agent to obtain a metallic silver product, leaching the leachate obtained by water leaching separation, evaporating, concentrating, crystallizing, and separating to obtain a potassium chloride product. The method is characterized in that water solution is adopted to leach and sinter smoke dust, substances such as potassium, sodium, calcium, magnesium, lead and the like in raw materials are mainly in the form of chloride, a large amount of potassium, sodium and calcium and a small amount of lead and bismuth and the like enter a leaching solution in the leaching process to cause complex components of the leaching solution, the potassium chloride product is obtained by evaporation concentration and crystallization extraction of the purifying solutions such as sodium carbonate and the like in the above patents, but the leaching solution is purified by sodium carbonate and sodium is brought into the raw materials, so that a large amount of sodium chloride is contained in the solution, only about 70% of high-quality potassium chloride products can be obtained due to enrichment of the sodium chloride, the rest products are potassium-sodium mixtures, the potassium chloride content can only reach 60-70%, and the sodium is not effectively utilized; meanwhile, the purified slag of sodium carbonate and the like is not applied at all, so that the loss of calcium and carbonate is caused, and new waste slag is generated. Therefore, although various treatment methods are adopted for the treatment process of the sintering dust collection ash due to the difference of raw materials, the treatment process has many problems and defects.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a comprehensive utilization method of the iron ore sintering smoke dust ash leaching solution, and achieves the purpose of comprehensive and economic utilization of secondary resources.
The technical scheme adopted by the invention for solving the technical problems is as follows: a comprehensive utilization method of iron ore sintering smoke dust leaching solution comprises the following steps:
a. adding water and sintering smoke dust into a reactor according to the liquid-solid mass ratio of 1.0-2.0: 1, leaching the sintering smoke dust with water for 0.5-2.0 hours at room temperature under the condition of stirring speed of 300-500 rpm, and separating to obtain leaching solution and leaching residues;
b. and b, adding sodium oxalate with the theoretical amount of 100% according to the stoichiometric amount into the leaching solution obtained in the step a, carrying out precipitation reaction for 1.0-2.0 hours at the temperature of 60-90 ℃ and the stirring speed of 300-500 rpm, separating to obtain bismuth oxalate precipitates and filtrate, washing and drying the bismuth oxalate precipitates, and calcining the bismuth oxalate precipitates for 1.0 ~ 2.0.0 hours at the temperature of 600 ~ 800 ℃ to obtain a bismuth trioxide product.
c. And c, adding sodium chromate with the theoretical amount of 100-120% according to the lead content in the solution into the filtrate obtained in the step b, and performing precipitation reaction, separation and washing to obtain a lead chromate product and filtrate.
d. C, adding sulfonated kerosene with the concentration of P507 being 20 ~ 30% into the filtrate obtained in the step c as an organic phase for extraction, and separating after extraction to obtain an extraction organic phase containing calcium and magnesium and a raffinate aqueous solution;
e. c, back extracting the calcium-magnesium-containing extracted organic phase obtained in the step d at room temperature by using 50-100 g/l of sulfuric acid solution according to the volume ratio of the organic phase to the water phase of 2: 1, and separating after back extraction to obtain a water phase containing calcium sulfate precipitate and a back extraction organic phase; e, returning the back extraction organic phase to the step e for recycling, and filtering and washing a calcium sulfate-containing water phase system to obtain calcium sulfate dihydrate;
f. the solid calcium sulfate dihydrate obtained in the step (e) is mixed according to the solid-liquid ratio of 1: 8-12, adding water, pulping, transferring to a hydrothermal reaction kettle, heating to 150-180 ℃, carrying out hydrothermal treatment for 3-6 h, cooling, separating to obtain a precipitated calcium filtrate and a calcium sulfate whisker solid material, and washing and drying the calcium sulfate whisker solid material to obtain a calcium sulfate whisker product; returning the precipitated calcium filtrate to the step for recycling the dihydrate calcium sulfate slurry;
g. adding 1-3% of activated clay and 2-5% of activated carbon into the raffinate aqueous solution obtained in the step d, stirring and reacting for 0.5-1.0 hour at room temperature, and filtering after reaction to obtain colorless transparent filtrate;
h. g, taking a part of the colorless transparent filtrate obtained in the step g, adding sodium sulfate according to a certain proportion, stirring at normal temperature to perform a first-stage conversion reaction, performing solid-liquid separation on a reaction product to obtain an intermediate product of glaserite 1 precipitate, evaporating and concentrating a liquid phase under normal pressure to separate out sodium chloride, and then separating at an evaporation temperature to obtain an industrial sodium chloride product; and (4) separating the mother liquor, cooling, crystallizing and separating to obtain the glaserite 2. And g, mixing the glaserite 1 and the glaserite 2, mixing with part of the filtrate obtained in the step g according to a certain proportion, carrying out a second-stage conversion reaction at normal temperature, carrying out solid-liquid separation to obtain a potassium sulfate product, and returning the mother liquor to the first-stage conversion for recycling.
In the step c, the reaction temperature is room temperature, the stirring speed is 200-400 rpm, and the reaction time is 0.5-1.0 h.
In the step d, the volume ratio of the extracted organic phase to the aqueous phase is 1: 1, stirring is needed for extraction, the stirring speed is 300-500 rpm, the extraction time is 10-30 minutes, and the extraction temperature is 40-70 ℃.
In the step h, the adding proportion of sodium sulfate is determined according to the potassium content and K in the filtrate+，Na+//SO2- 4，Cl-，H2And determining an O system phase diagram.
The invention has the beneficial effects that: the invention adopts water to leach the sintering smoke dust, leaching solution and leaching slag are obtained by separation, and the leaching solution is processed step by step to obtain products such as bismuth trioxide, lead chromate, calcium sulfate crystal whisker, sodium chloride, potassium sulfate and the like. The method has the advantages of simple process equipment, easy and safe operation, realization of the high-efficiency recycling of potassium, sodium, calcium, lead, bismuth and other elements in the sintering dust, improvement of the additional value of raw materials, realization of the resource utilization of the sintering dust, waste recycle, reduction of environmental pollution and good industrial popularization and application prospect.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The smoke dust used as the raw material in the embodiment of the invention comprises the following main component indexes: k2O 20.15%，Na2O 5.02%，Cl 29.37%，Pb 4.86%，Fe 27.32%，CaO8.43%，Al2O3 0.17%，MgO 0.58%，Bi 0.96%。
Example 1
a. Adding water and sintering smoke dust into a reactor according to the liquid-solid mass ratio of 2.0: 1, leaching the sintering smoke dust for 1.0 hour at room temperature under the condition of stirring speed of 300rpm, and separating to obtain leaching solution and leaching residues;
b. b, adding sodium oxalate with the theoretical amount of 100% according to the stoichiometric amount according to the content of bismuth in the leaching solution obtained in the step a, carrying out precipitation reaction for 1.5 hours at the temperature of 80 ℃ and the stirring speed of 300rpm, and separating to obtain bismuth oxalate precipitate and filtrate; and washing, drying and calcining the bismuth oxalate precipitate at 800 ℃ for 1.0 hour to obtain a bismuth trioxide product.
c. And c, adding sodium chromate with the theoretical amount of 120% according to the stoichiometric amount into the filtrate obtained in the step b according to the content of lead in the solution, carrying out precipitation reaction for 1.0h under the stirring condition of 300rpm at room temperature, and separating and washing to obtain a lead chromate product and filtrate.
d. C, adding sulfonated kerosene with the concentration of 20 percent P507 into the filtrate obtained in the step c as an organic phase, extracting for 15min under the conditions of the stirring speed of 300rpm and the temperature of 50 ℃, and separating after extraction to obtain an extracted organic phase containing calcium and magnesium and a raffinate aqueous solution;
e. c, back extracting the calcium-magnesium-containing extracted organic phase obtained in the step d at room temperature by using 50g/l of sulfuric acid solution according to the volume ratio of the organic phase to the water phase of 2: 1, and separating after back extraction to obtain a water phase containing calcium sulfate precipitate and a back extraction organic phase; filtering and washing the calcium sulfate-containing water-phase system to obtain calcium sulfate dihydrate;
f. the solid calcium sulfate dihydrate obtained in the step (e) is mixed according to the solid-liquid ratio of 1: 12, adding water, pulping, transferring into a hydrothermal reaction kettle, heating to 170 ℃, carrying out hydrothermal treatment for 3h, cooling, separating to obtain precipitated calcium filtrate and calcium sulfate whisker solid materials, and washing and drying the calcium sulfate whisker solid materials to obtain calcium sulfate whisker products;
g. d, adding 3% of activated clay and 2% of activated carbon into the raffinate aqueous solution obtained in the step d, stirring and reacting for 0.5 hour at room temperature, and filtering after reaction to obtain colorless transparent filtrate;
h. g, taking a part of the colorless transparent filtrate obtained in the step g, adding sodium sulfate according to a certain proportion, stirring at normal temperature to perform a first-stage conversion reaction, performing solid-liquid separation on a reaction product to obtain an intermediate product of glaserite 1 precipitate, evaporating and concentrating a liquid phase under normal pressure to separate out sodium chloride, and then separating at an evaporation temperature to obtain an industrial sodium chloride product; and (4) separating the mother liquor, cooling, crystallizing and separating to obtain the glaserite 2. And g, mixing the glaserite 1 and the glaserite 2, mixing with part of the filtrate obtained in the step g according to a certain proportion, carrying out a second-stage conversion reaction at normal temperature, carrying out solid-liquid separation to obtain a potassium sulfate product, and returning the mother liquor to the first-stage conversion for recycling.
The bismuth trioxide product of this example was analyzed to be yellow in appearance, Bi2O3The content is 98.32%; the lead chromate product has light yellow appearance and PbCrO4The content is 94.78%; the calcium sulfate whisker product is white in appearance and CaSO4The content is 99.02%, the average diameter is 4 mu m, the average length is 525 mu m, and the length-diameter ratio is 131; the NaCl content of the industrial sodium chloride product is 94.26 percent, and the calcium and magnesium content is 0.52 percent; potassium sulfate product K2The O content is 46.82 percent, and the chlorine (Cl) content is 2.16 percent;
example 2
a. Adding water and sintering smoke dust into a reactor according to the liquid-solid mass ratio of 1.0: 1, leaching the sintering smoke dust for 2.0 hours at room temperature under the condition of stirring speed of 500rpm, and separating to obtain leaching solution and leaching residues;
b. b, adding sodium oxalate with the theoretical amount of 100% according to the stoichiometric amount according to the content of bismuth in the leaching solution obtained in the step a, carrying out precipitation reaction for 1.0 hour at the temperature of 60 ℃ and the stirring speed of 500rpm, and separating to obtain bismuth oxalate precipitate and filtrate; and washing, drying and calcining the bismuth oxalate precipitate at 600 ℃ for 2.0 hours to obtain a bismuth trioxide product.
c. And c, adding sodium chromate with the theoretical amount of 100% according to the stoichiometric amount into the filtrate obtained in the step b according to the content of lead in the solution, carrying out precipitation reaction for 0.75h under the stirring condition of 200rpm at room temperature, and separating and washing to obtain a lead chromate product and filtrate.
d. C, adding sulfonated kerosene with the concentration of 30 percent P507 into the filtrate obtained in the step c as an organic phase, extracting for 20min at the stirring speed of 400rpm and the temperature of 60 ℃, and separating after extraction to obtain an extracted organic phase containing calcium and magnesium and a raffinate aqueous solution;
e. c, back extracting the calcium-magnesium-containing extracted organic phase obtained in the step d at room temperature by using 100g/L sulfuric acid solution according to the volume ratio of the organic phase to the water phase of 2: 1, and separating after back extraction to obtain a water phase containing calcium sulfate precipitate and a back extraction organic phase; filtering and washing the calcium sulfate-containing water-phase system to obtain calcium sulfate dihydrate;
f. the solid calcium sulfate dihydrate obtained in the step (e) is mixed according to the solid-liquid ratio of 1: 8, adding water, mixing the slurry, transferring the slurry into a hydrothermal reaction kettle, heating to 150 ℃, carrying out hydrothermal treatment for 6 hours, cooling, separating to obtain precipitated calcium filtrate and calcium sulfate whisker solid materials, and washing and drying the calcium sulfate whisker solid materials to obtain calcium sulfate whisker products;
g. d, adding 1% of activated clay and 5% of activated carbon into the raffinate aqueous solution obtained in the step d, stirring and reacting for 1.0 hour at room temperature, and filtering after reaction to obtain colorless transparent filtrate;
h. g, taking a part of the colorless transparent filtrate obtained in the step g, adding sodium sulfate according to a certain proportion, stirring at normal temperature to perform a first-stage conversion reaction, performing solid-liquid separation on a reaction product to obtain an intermediate product of glaserite 1 precipitate, evaporating and concentrating a liquid phase under normal pressure to separate out sodium chloride, and then separating at an evaporation temperature to obtain an industrial sodium chloride product; and (4) separating the mother liquor, cooling, crystallizing and separating to obtain the glaserite 2. And g, mixing the glaserite 1 and the glaserite 2, mixing with part of the filtrate obtained in the step g according to a certain proportion, carrying out a second-stage conversion reaction at normal temperature, carrying out solid-liquid separation to obtain a potassium sulfate product, and returning the mother liquor to the first-stage conversion for recycling.
The bismuth trioxide product of this example was analyzed to be yellow in appearance, Bi2O3The content is 97.63%; the lead chromate product has light yellow appearance and PbCrO4The content is 95.37%; the calcium sulfate whisker product is white in appearance and CaSO4The content is 99.35%, the average diameter is 6 mu m, the average length is 774 mu m, and the length-diameter ratio is 129; the NaCl content of the industrial sodium chloride product is 93.87 percent, and the calcium and magnesium content is 0.47 percent; potassium sulfate product K2The O content was 45.73%, and the chlorine (Cl) content was 2.27%;
example 3
a. Adding water and sintering smoke dust into a reactor according to the liquid-solid mass ratio of 1.5: 1, leaching the sintering smoke dust for 0.5 hour at room temperature under the condition of stirring speed of 400rpm, and separating to obtain leaching solution and leaching residues;
b. b, adding sodium oxalate with the theoretical amount of 100% according to the stoichiometric amount according to the content of bismuth in the leaching solution obtained in the step a, carrying out precipitation reaction for 2.0 hours at the temperature of 90 ℃ and the stirring speed of 400rpm, and separating to obtain bismuth oxalate precipitate and filtrate; and washing, drying and calcining the bismuth oxalate precipitate at 700 ℃ for 1.5 hours to obtain a bismuth trioxide product.
c. And c, adding sodium chromate with the theoretical amount of 110% according to the stoichiometric amount into the filtrate obtained in the step b according to the content of lead in the solution, carrying out precipitation reaction for 0.5h under the stirring condition of 400rpm at room temperature, and separating and washing to obtain a lead chromate product and filtrate.
d. C, adding sulfonated kerosene with the concentration of 24 percent P507 into the filtrate obtained in the step c as an organic phase, extracting for 10min at the stirring speed of 500rpm and the temperature of 70 ℃, and separating after extraction to obtain an extracted organic phase containing calcium and magnesium and a raffinate aqueous solution;
e. c, back extracting the calcium-magnesium-containing extracted organic phase obtained in the step d at room temperature by using 70g/L sulfuric acid solution according to the volume ratio of the organic phase to the water phase of 2: 1, and separating after back extraction to obtain a water phase containing calcium sulfate precipitate and a back extraction organic phase; filtering and washing the calcium sulfate-containing water-phase system to obtain calcium sulfate dihydrate;
f. the solid calcium sulfate dihydrate obtained in the step (e) is mixed according to the solid-liquid ratio of 1: 10, adding water, mixing slurry, transferring to a hydrothermal reaction kettle, heating to 180 ℃, carrying out hydrothermal treatment for 4 hours, cooling, separating to obtain a precipitated calcium filtrate and a calcium sulfate whisker solid material, and washing and drying the calcium sulfate whisker solid material to obtain a calcium sulfate whisker product;
g. d, adding 2% of activated clay and 4% of activated carbon into the raffinate aqueous solution obtained in the step d, stirring and reacting for 0.75 hour at room temperature, and filtering after reaction to obtain colorless transparent filtrate;
h. g, taking a part of the colorless transparent filtrate obtained in the step g, adding sodium sulfate according to a certain proportion, stirring at normal temperature to perform a first-stage conversion reaction, performing solid-liquid separation on a reaction product to obtain an intermediate product of glaserite 1 precipitate, evaporating and concentrating a liquid phase under normal pressure to separate out sodium chloride, and then separating at an evaporation temperature to obtain an industrial sodium chloride product; and (4) separating the mother liquor, cooling, crystallizing and separating to obtain the glaserite 2. And g, mixing the glaserite 1 and the glaserite 2, mixing with part of the filtrate obtained in the step g according to a certain proportion, carrying out a second-stage conversion reaction at normal temperature, carrying out solid-liquid separation to obtain a potassium sulfate product, and returning the mother liquor to the first-stage conversion for recycling.
The bismuth trioxide product of this example was analyzed to be yellow in appearance, Bi2O3The content is 97.94%; the lead chromate product has light yellow appearance and PbCrO4The content is 95.86 percent; the calcium sulfate whisker product is white in appearance and CaSO4The content is 99.18%, the average diameter is 5 mu m, the average length is 585 mu m, and the length-diameter ratio is 117; the NaCl content of the industrial sodium chloride product is 93.45 percent, and the calcium and magnesium content is 0.54 percent; potassium sulfate product K2The O content was 47.16%, the chlorine (Cl) content was 1.92%;
example 4
a. Adding water and sintering smoke dust into a reactor according to the liquid-solid mass ratio of 1.8: 1, leaching the sintering smoke dust for 1.5 hours at room temperature and the stirring speed of 450rpm, and separating to obtain leaching solution and leaching residues;
b. b, adding sodium oxalate with the theoretical amount of 100% according to the stoichiometric amount according to the content of bismuth in the leaching solution obtained in the step a, carrying out precipitation reaction for 1.5 hours at the temperature of 70 ℃ and the stirring speed of 350rpm, and separating to obtain bismuth oxalate precipitate and filtrate; and washing, drying and calcining the bismuth oxalate precipitate at 750 ℃ for 1.0 hour to obtain a bismuth trioxide product.
c. And c, adding sodium chromate with the theoretical amount of 105% according to the stoichiometric amount into the filtrate obtained in the step b according to the content of lead in the solution, carrying out precipitation reaction for 1.0h under the stirring condition of 350rpm at room temperature, and separating and washing to obtain a lead chromate product and filtrate.
d. C, adding sulfonated kerosene with the concentration of 27 percent P507 into the filtrate obtained in the step c as an organic phase, extracting for 30min at the stirring speed of 400rpm and the temperature of 40 ℃, and separating after extraction to obtain an extracted organic phase containing calcium and magnesium and a raffinate aqueous solution;
e. c, back extracting the calcium-magnesium-containing extracted organic phase obtained in the step d at room temperature by using 80g/L sulfuric acid solution according to the volume ratio of the organic phase to the water phase of 2: 1, and separating after back extraction to obtain a water phase containing calcium sulfate precipitate and a back extraction organic phase; filtering and washing the calcium sulfate-containing water-phase system to obtain calcium sulfate dihydrate;
f. the solid calcium sulfate dihydrate obtained in the step (e) is mixed according to the solid-liquid ratio of 1: adding water, mixing the slurry, transferring the slurry into a hydrothermal reaction kettle, heating the hydrothermal reaction kettle to 160 ℃, carrying out hydrothermal treatment for 5 hours, cooling, separating to obtain precipitated calcium filtrate and calcium sulfate whisker solid materials, and washing and drying the calcium sulfate whisker solid materials to obtain calcium sulfate whisker products;
g. d, adding 1.5 percent of activated clay and 3 percent of activated carbon into the raffinate aqueous solution obtained in the step d, stirring and reacting for 1.0 hour at room temperature, and filtering after reaction to obtain colorless transparent filtrate;
h. g, taking a part of the colorless transparent filtrate obtained in the step g, adding sodium sulfate according to a certain proportion, stirring at normal temperature to perform a first-stage conversion reaction, performing solid-liquid separation on a reaction product to obtain an intermediate product of glaserite 1 precipitate, evaporating and concentrating a liquid phase under normal pressure to separate out sodium chloride, and then separating at an evaporation temperature to obtain an industrial sodium chloride product; and (4) separating the mother liquor, cooling, crystallizing and separating to obtain the glaserite 2. And g, mixing the glaserite 1 and the glaserite 2, mixing with part of the filtrate obtained in the step g according to a certain proportion, carrying out a second-stage conversion reaction at normal temperature, carrying out solid-liquid separation to obtain a potassium sulfate product, and returning the mother liquor to the first-stage conversion for recycling.
The bismuth trioxide product of this example was analyzed to be yellow in appearance, Bi2O3The content is 98.26%; the lead chromate product has light yellow appearance and PbCrO4The content is 94.92%; the calcium sulfate whisker product is white in appearance and CaSO4The content is 99.35%, the average diameter is 6 mu m, the average length is 762 mu m, and the length-diameter ratio is 127; the NaCl content of the industrial sodium chloride product is 94.38 percent, and the calcium and magnesium content is 0.48 percent; potassium sulfate product K2The O content was 46.35% and the chlorine (Cl) content was 2.34%.
Claims (4)
1. A comprehensive utilization method of iron ore sintering smoke dust leaching solution is characterized by comprising the following steps:
a. adding water and sintering smoke dust into a reactor according to the liquid-solid mass ratio of 1.0-2.0: 1, leaching the sintering smoke dust with water for 0.5-2.0 hours at room temperature under the condition of stirring speed of 300-500 rpm, and separating to obtain leaching solution and leaching residues;
b. b, adding sodium oxalate with the theoretical amount of 100% according to the stoichiometric amount into the leaching solution obtained in the step a, carrying out precipitation reaction for 1.0-2.0 hours at the temperature of 60-90 ℃ and the stirring speed of 300-500 rpm, separating to obtain bismuth oxalate precipitate and filtrate, washing and drying the bismuth oxalate precipitate, and calcining the bismuth oxalate precipitate for 1.0 ~ 2.0.0 hours at the temperature of 600 ~ 800 ℃ to obtain a bismuth trioxide product;
c. b, adding sodium chromate with the theoretical amount of 100-120% according to the stoichiometric amount of lead in the filtrate obtained in the step b, carrying out precipitation reaction, separating and washing to obtain a lead chromate product and filtrate;
d. c, adding sulfonated kerosene with the concentration of P507 being 20 ~ 30% into the filtrate obtained in the step c as an organic phase for extraction, and separating after extraction to obtain an extraction organic phase containing calcium and magnesium and a raffinate aqueous solution;
e. c, back extracting the calcium-magnesium-containing extracted organic phase obtained in the step d at room temperature by using 50-100 g/l of sulfuric acid solution according to the volume ratio of the organic phase to the water phase of 2: 1, and separating after back extraction to obtain a water phase containing calcium sulfate precipitate and a back extraction organic phase; e, returning the back extraction organic phase to the step e for recycling, and filtering and washing a calcium sulfate-containing water phase system to obtain calcium sulfate dihydrate;
f. the solid calcium sulfate dihydrate obtained in the step (e) is mixed according to the solid-liquid ratio of 1: 8-12, adding water, pulping, transferring to a hydrothermal reaction kettle, heating to 150-180 ℃, carrying out hydrothermal treatment for 3-6 h, cooling, separating to obtain a precipitated calcium filtrate and a calcium sulfate whisker solid material, and washing and drying the calcium sulfate whisker solid material to obtain a calcium sulfate whisker product; returning the precipitated calcium filtrate to the step for recycling the dihydrate calcium sulfate slurry;
g. adding 1-3% of activated clay and 2-5% of activated carbon into the raffinate aqueous solution obtained in the step d, stirring and reacting for 0.5-1.0 hour at room temperature, and filtering after reaction to obtain colorless transparent filtrate;
h. g, taking a part of the colorless transparent filtrate obtained in the step g, adding sodium sulfate according to a certain proportion, stirring at normal temperature to perform a first-stage conversion reaction, performing solid-liquid separation on a reaction product to obtain an intermediate product of glaserite 1 precipitate, evaporating and concentrating a liquid phase under normal pressure to separate out sodium chloride, and then separating at an evaporation temperature to obtain an industrial sodium chloride product; and g, cooling and crystallizing the separated mother liquor, separating to obtain glaserite 2, mixing the glaserite 1 and the glaserite 2, mixing with part of the filtrate obtained in the step g according to a certain proportion, carrying out two-stage conversion reaction at normal temperature, carrying out solid-liquid separation to obtain a potassium sulfate product, and returning the mother liquor to the first-stage conversion for recycling.
2. The comprehensive utilization method of the iron ore sintering flue dust ash leaching solution according to claim 1, characterized in that: in the step c, the reaction temperature is room temperature, the stirring speed is 200-400 rpm, and the reaction time is 0.5-1.0 h.
3. The comprehensive utilization method of the iron ore sintering flue dust ash leaching solution according to claim 1, characterized in that: in the step d, the volume ratio of the extracted organic phase to the aqueous phase is 1: 1, stirring is needed for extraction, the stirring speed is 300-500 rpm, the extraction time is 10-30 minutes, and the extraction temperature is 40-70 ℃.
4. The comprehensive utilization method of the iron ore sintering flue dust ash leaching solution according to claim 1, characterized in that: in step h, the sodium sulfate is added according to the potassium content and K in the filtrate+，Na+//SO2- 4，Cl-，H2And determining an O system phase diagram.
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| CN113832347A (en) * | 2021-09-18 | 2021-12-24 | 青岛大学 | Method for enhancing arsenic leaching of coal by using organic additive |
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