CN110735054A - Method for producing furnace charge by manganese carbonate ore and application thereof - Google Patents
Method for producing furnace charge by manganese carbonate ore and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
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Abstract
The invention relates to a method for producing burden by manganese carbonate ore, which comprises the following steps: A. grinding manganese carbonate ores into powder, pulping, adding acid, stirring and leaching, then adjusting the pH value to 6.0-6.4, removing impurities, and carrying out solid-liquid separation after filter pressing to obtain a manganese sulfate solution and a filter pressing block A; B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; adding alkali into the supernatant at the temperature of 38-42 ℃, stirring and adjusting the pH to 8.5-9, performing solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and performing filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution; C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; and sintering the manganese hydroxide filter pressing block C to obtain furnace charge. The method can effectively remove harmful impurities in the manganese ore, enrich manganese elements, improve the ore dressing efficiency, reduce the production cost and avoid environmental pollution.
Description
Technical Field
The invention belongs to the technical field of ore pretreatment by using agglomeration, briquetting, bonding and granulation methods, and particularly relates to a method for producing furnace burden by using manganese carbonate ore and application thereof.
Background
At present, the beneficiation methods are divided into two types, namely physical beneficiation and chemical beneficiation, wherein the physical beneficiation comprises a magnetic separation method, a gravity separation method, an electrostatic separation method, a friction beneficiation method, a particle size beneficiation method, a shape beneficiation method, a beneficiation method and the like, and the chemical beneficiation comprises a flotation method, a roasting method, a leaching method and the like. However, the method generally has the defects of poor ore dressing effect on manganese ores, limited manganese enrichment and harmful impurity removal effect, unobvious phosphorus removal effect, great environmental pollution, low manganese recovery rate, large amount of waste residues and high cost. The leaching rule is good in manganese-rich phosphorus removal and impurity removal effects, but the consumption of auxiliary materials such as acid and ammonia water is large, and the cost is high.
The manganese content of manganese carbonate ore in China is low, about 7-15%, and along with the fact that high-quality manganese-rich ore resources are increasingly deficient, imported high-quality ores such as Australian ore and the like must be imported to make up for the supplement of manganese ore resources in China, so that the processing cost of manganese ore and manganese in China is higher and lower, and the profit margin is smaller and smaller. The manganese carbonate ores in China are mainly sedimentary manganese carbonate ores, main manganese ores of the sedimentary manganese carbonate ores are rhodochrosite, calciumdinite, manganese-containing calcite, ferromanganese ore and the like, gangue contains silicate and carbonate minerals, and is often accompanied by impurities such as sulfur, iron and the like, the components are relatively complex, the embedding particle size of the manganese ores is as small as several microns, the manganese ores are not easy to dissociate and are often difficult to obtain higher concentrate grade. At present, the mineral separation method of manganese carbonate ore comprises strong magnetic separation, dense medium mineral separation, flotation and the like. However, the manganese content in manganese carbonate ores in China is low, so that the beneficiation effect is not ideal, the enrichment degree of manganese is not high, and the content of harmful impurities such as phosphorus in the selected ores is high.
Disclosure of Invention
In view of the above, the present invention provides methods for producing burden from manganese carbonate ore.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the method for producing furnace charge by manganese carbonate ore comprises the following steps:
grinding manganese carbonate ores into powder, pulping, adding acid, stirring and leaching, then adjusting the pH value to 6.0-6.4, removing impurities, and carrying out solid-liquid separation after filter pressing to obtain a manganese sulfate solution and a filter pressing block A;
B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; adding alkali into the supernatant at the temperature of 38-42 ℃, stirring and adjusting the pH to 8.5-9, performing solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and performing filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution;
C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; and sintering the manganese hydroxide filter pressing block C to obtain furnace charge.
In the scheme of the invention, the adjustment can be carried out according to different raw materials, if manganese oxide ore is contained in manganese carbonate ore, sulfur dioxide gas is introduced into the slurried solution, and the amount of the sulfur dioxide is 1-1.3 times of the amount of manganese substance contained in the manganese carbonate ore.
Manganese oxide ore is mainly composed of manganese durite (the main component is mMnO. MnO)2·H2O), pyrolusite (MnO as main component)2) Manganese bioxide (Mn as the main component)2O2·H2O), permanganic acid ore (MnO as main component)2·H2O), brown manganese ore (Mn as main component)2O3) And black manganese ore (Mn as the main component)3O4) And square manganese ore (MnO as main component), gangue is mainly silicate mineral, and carbonate ore mercury ore powder dryer is often accompanied with pig iron, phosphorus, nickel, cobalt and other components
The method can effectively remove harmful impurities (such as phosphorus, sulfur and the like) in the manganese ore, enriches the manganese element, enables the manganese element to become furnace burden for producing manganese alloy, improves the ore dressing efficiency, reduces the production cost and avoids environmental pollution.
The grinding in the step A is to grind into powder with 80-100 meshes.
And step , the slurrying degree in the step A is that the content of the divalent manganese ions in the slurried solution is 25-40 g/L.
The slurrying refers to mixing the ore with water.
And step , in the step A, keeping the temperature of the slurried solution at 50-60 ℃ in the acid adding process, wherein the acid is concentrated sulfuric acid, the adding amount of the acid is 50-75g/L of the concentration of sulfuric acid in the added solution, the stirring linear velocity is 20-30m/s in the adding process, and carbon dioxide generated by the reaction is recovered.
And step , stirring and leaching for 2.5-5 h.
And step , the alkali in the step B is ammonia water solution, and the stirring linear speed is 20-30 m/s.
Step , the sintering temperature in step C is 1400-1700 ℃.
And , adding the washing water obtained in the step C into an ammonium sulfate solution, slowly adding quicklime under stirring at the temperature of less than or equal to 90 ℃, recovering the generated ammonia gas with water to obtain an ammonia water solution, performing pressure filtration on the solution after reaction, performing solid-liquid separation to obtain a calcium sulfate filter cake and water, standing the water, removing impurities, and recycling.
And , adding quicklime for 2-3h, and recovering ammonia gas with water.
, the method also includes the step of using the obtained ammonia solution to adjust the pH value of the solution.
And , adding calcium lime in the amount to complete the ammonium sulfate reaction.
, washing the filter pressing block A, filter pressing to obtain filter pressing block and solution, homogenizing the filter pressing block and the calcium sulfate filter pressing block, regulating the content of calcium, magnesium, silicon, aluminum and iron in the mixture according to production requirements, homogenizing, adding coal powder, and calcining to obtain the cement additive.
, separating powder and gas generated during calcination, adding the powder into a rotary furnace for cyclic calcination, using the gas sulfur dioxide to produce sulfuric acid, and recovering the tail gas from sulfuric acid production with calcium hydroxide or manganese dioxide.
The method recovers high-value elements such as sulfur, nitrogen, manganese and the like in the slag, and uses silicon, iron, calcium and aluminum in the slag for producing cement additives or manganese-making raw materials, thereby changing waste into valuable, reducing pollution and realizing the recovery and reutilization of resources.
The method produces cement additive or manganese raw material while processing waste residue, so that ammonium sulfate and sulfuric acid are recycled, and production cost is reduced.
And , calcining at a temperature of more than or equal to 1200 ℃ and less than 1450 ℃.
, further comprising the following steps of standing the solution obtained by washing the filter pressing block A with water, cooling, removing the precipitate to obtain supernatant, then adjusting the pH value to 9-10, standing, carrying out filter pressing and solid-liquid separation, wherein the filter pressing block is used for the slurrying process of the step A, the pH value of the solution is adjusted to 6.5-7.5, and the solution is used as water for washing slag for recycling.
The method recycles ammonium sulfate and water, and reduces production cost while treating waste residues.
The invention has the beneficial effects that:
(1) the method can effectively remove harmful impurities (such as phosphorus, sulfur and the like) in the manganese ore, enriches the manganese element, enables the manganese element to become furnace burden for producing manganese alloy, improves the ore dressing efficiency, reduces the production cost and avoids environmental pollution.
(2) The method produces cement additive or manganese raw material while treating waste residue, and reduces production cost.
(3) The method recycles ammonium sulfate, sulfuric acid and water, and reduces production cost while treating waste residues.
(4) When 6.8-7.0 tons of ore with 9.97-10.87% of manganese, 1.75-1.77% of phosphorus and 2-2.5% of sulfur is consumed by the method, about 1 ton of furnace charge for producing high-carbon ferromanganese or silicon-manganese alloy and 6.7-6.9 tons of cement additive can be prepared when 700 ℃ or 1600 ℃ of electricity is consumed. The obtained furnace charge contains 65.41-65.76% of manganese element, 0.07% of phosphorus element and 0.01% of sulfur element.
Detailed Description
The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
Example 1
The method for producing furnace charge by using manganese carbonate ore without manganese oxide ore comprises the following steps:
A. the method comprises the steps of detecting the content of a manganese element in manganese carbonate ores without manganese oxide ores (detecting the content of the manganese element in the ores according to a ferrous sulfate titration method in GB/T1506-2016 manganese ore manganese content determination potentiometric titration method and ferrous sulfate titration method), measuring the content of the manganese element in the ores to be 9.97%, detecting the content of the phosphorus element in the ores according to GB/T1515-2002 manganese ore phosphorus content determination phosphomolybdic blue spectrophotometry, measuring the content of the phosphorus element in the ores to be 1.75%, measuring the content of the manganese oxide in the ores according to GB/T6609.11-2004 aluminum oxide chemical analysis method and physical property measurement method flame atomic absorption spectrometry to be manganese oxide content, measuring the content of the sulfur element in the ores to be 0.20%, adding water, grinding into 80-mesh powder (the content of the manganese oxide in the GB/T14949.9-1994 manganese ore chemical analysis method sulfur content determination method), adding acid ions, stirring, removing, pulping, adding a pulping, adding an acid ion, pulping, adding a slurry, performing filtration, and filter pressing at a temperature of 60g, adding a pulping temperature of 60.5 ℃ after pulping, adding a pulping temperature of 60g of sulfuric acid ions, and pulping, adding a pressure filtration, and adding a pulping temperature of 60g of a filter pressing solution to obtain a pulping solution, and a pulping process, adding a pulping temperature of pulping process, wherein the pulping process;
B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; adding an ammonia water solution into the supernatant at the temperature of 38 ℃ and under the stirring of the linear velocity of 25m/s to adjust the pH to 8.6, carrying out solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11.5, and carrying out filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution;
C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; adding 10% of coke into a manganese hydroxide filter pressing block C, and sintering at 1100 ℃ to obtain a furnace charge (detecting the manganese content in the furnace charge according to GB/T8654.7-1988 manganese metal chemical analysis method potentiometric titration method to measure the manganese content to obtain 65.41%, detecting the phosphorus content in the furnace charge according to Sb-P-Mo-blue spectrophotometry in GB/T223.59-2008 steel and alloy phosphorus content determination Bi-P-Mo-blue spectrophotometry to obtain 0.07%, detecting the sulfur content in the furnace charge according to GB/T ferromanganese and blast furnace ferromanganese chemical analysis method infrared absorption to obtain 0.01%);
D. c, adding the washing water obtained in the step C into an ammonium sulfate solution, slowly adding quicklime (the amount is that the ammonium sulfate in the ammonium sulfate solution can be completely reacted) at the temperature of 40 ℃ under the stirring condition that the linear speed is 10m/s, recovering the generated ammonia gas with water after 2h to obtain an ammonia water solution, performing solid-liquid separation after filter pressing of the solution after reaction to obtain a calcium sulfate filter pressing block and water, and standing the water to remove impurities and then recycling;
E. washing a filter pressing block A with water, then carrying out filter pressing to obtain a filter pressing block and a solution, homogenizing the filter pressing block and a calcium sulfate filter pressing block, adjusting the contents of calcium, magnesium, silicon, aluminum and iron in the mixture according to the production requirement of portland cement, adding pulverized coal after homogenization, calcining at 1500 ℃ to obtain a cement additive, separating powder and gas generated in the calcining process, adding the powder into a rotary furnace for cyclic calcination, using gas sulfur dioxide for preparing sulfuric acid, using calcium hydroxide for preparing tail gas of the sulfuric acid, and using the recovered mixture as the cement additive;
F. and C, standing the solution obtained by washing the filter pressing block obtained in the step A with water, cooling, removing the precipitate to obtain a supernatant, adjusting the pH to 9.2, standing, performing filter pressing and solid-liquid separation, wherein the filter pressing block is used for the slurrying process in the step A, and the solution is adjusted to the pH of 7.3 and is used as water for washing slag for recycling.
According to the method, 1 ton of furnace charge (about 3900 yuan/ton) capable of being used for producing high-carbon ferromanganese and 6.8 tons of cement additive (about 320 yuan/ton) are prepared for each 700 DEG of electricity consumption (about 0.41 yuan/ton) for each 7.0 tons of ore. The content of manganese element is increased from 9.97% to 65.41%, the content of phosphorus element is reduced from 1.75% to 0.07%, and the content of sulfur element is reduced from 0.20% to 0.01%.
Example 2
The method for producing the furnace charge by using the mixed ore of manganese oxide ore and manganese carbonate ore comprises the following steps:
A. the method comprises the steps of (1) detecting the content of a manganese element in a mixed ore of manganese oxide ore and manganese carbonate ore (according to a ferrous sulfate titration method in GB/T1506-2016 manganese ore manganese content determination potentiometric titration method and ferrous sulfate titration method), measuring the content of the manganese element in the mixed ore to be 10.13%, detecting the content of the phosphorus element in the mixed ore according to a phosphomolybdic blue spectrophotometry method for measuring the phosphorus content of GB/T1515-2002 manganese ore, measuring the content of the phosphorus element in the mixed ore to be 1.76%, measuring the content of manganese oxide in the mixed ore according to a GB/T6609.11-2004 manganese oxide chemical analysis method and a physical property measurement method flame atomic absorption spectrometry to be manganese oxide content, measuring the content of manganese oxide in the mixed ore to be 3.76%, measuring the content of the sulfur element in the mixed ore according to GB/T14949.9-1994, grinding the mixed ore to be mixed ore into 90 mesh powder, adding water, grinding the mixed ore into a slurrying solution, adjusting the content of the slurry of the manganese oxide ore to be 40.5 g, adding a slurry of a sulfur ions, adding a slurry solution, adjusting the slurry concentration of a slurry-like, adding a slurry-like gas, and a slurry-like, and adding a slurry-like slurry-;
B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; adding an ammonia water solution into the supernatant at the temperature of 38 ℃ and the linear velocity of 30m/s under stirring to adjust the pH to 8.5, carrying out solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and carrying out filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution;
C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; adding coke with the mass of 6 percent into a manganese hydroxide filter pressing block C, and sintering at the temperature of 800 ℃ to obtain a furnace charge (the manganese content in the furnace charge is detected according to GB/T8654.7-1988 manganese metal chemical analysis method potentiometric titration method to measure the manganese content, and the manganese content in the furnace charge is measured to be 65.51 percent; the phosphorus content in the furnace charge is measured according to Sb-P-Mo-blue spectrophotometry in GB/T223.59-2008 steel and iron and alloy phosphorus content determination Bi-P-Mo-blue spectrophotometry and Sb-P-Mo-blue spectrophotometry, and the phosphorus content in the ore is measured to be 0.068 percent; and the sulfur content in the furnace charge is measured according to GB/T ferromanganese and blast furnace ferromanganese chemical analysis method infrared absorption method, and the sulfur content in the furnace charge is measured to be 0.01 percent);
D. c, adding the washing water obtained in the step C into an ammonium sulfate solution, slowly adding quicklime (the amount is that the ammonium sulfate in the ammonium sulfate solution can be completely reacted) at the temperature of 90 ℃ under the stirring condition that the linear speed is 20m/s, recovering the generated ammonia gas with water after 3h to obtain an ammonia water solution, performing solid-liquid separation after filter pressing of the solution after reaction to obtain a calcium sulfate filter pressing block and water, and standing the water to remove impurities and then recycling;
E. washing a filter pressing block A with water, then carrying out filter pressing to obtain a filter pressing block and a solution, homogenizing the filter pressing block and a calcium sulfate filter pressing block, adjusting the content of calcium, magnesium, silicon, aluminum and iron in the mixture according to the production requirement of slag portland cement, adding pulverized coal after homogenization, calcining at the temperature of 1449 ℃, separating powder and gas generated in the calcining process, adding the powder into a rotary furnace for cyclic calcination, using gas sulfur dioxide for preparing sulfuric acid, using calcium hydroxide for tail gas for preparing the sulfuric acid, and using the recovered mixture as a cement additive;
F. and (3) standing the solution obtained after the filter pressing block A is washed by water, cooling, removing the precipitate to obtain a supernatant, then adjusting the pH to 9.6, standing, and performing filter pressing solid-liquid separation, wherein the filter pressing block is used for the slurrying procedure in the step A, and the solution is adjusted to the pH of 6.8 and is used as water for washing slag for recycling.
According to the method, every 700 degrees of electricity (about 0.41 yuan/degree) is consumed for every 6.8 tons of ores, and 1 ton of furnace charge (about 3900 yuan/ton) capable of producing high-carbon ferromanganese and 6.7 tons of cement additive (about 320 yuan/ton) are prepared. The content of manganese element is increased from 10.13% to 65.51%, the content of phosphorus element is reduced from 1.76% to 0.07%, and the content of sulfur element is reduced from 0.25% to 0.01%.
Example 3
The method for producing the furnace charge by using the mixed ore of manganese oxide ore and manganese carbonate ore comprises the following steps:
A. detecting the content of manganese element in a mixed ore of manganese oxide ore and manganese carbonate ore (detecting the content of manganese element in the mixed ore according to a ferrous sulfate titration method in GB/T1506-2016 manganese ore manganese content determination potentiometric titration method and ferrous sulfate titration method), measuring the content of manganese element in the mixed ore to be 10.47%, detecting the content of phosphorus element in the mixed ore according to a phosphomolybdic blue spectrophotometry method for measuring the content of phosphorus in GB/T1515-2002 manganese ore phosphorus, measuring the content of phosphorus element in the mixed ore to be 1.77%, measuring the content of manganese oxide in the mixed ore according to a GB/T6609.11-2004 manganese oxide chemical analysis method and a physical property measurement method flame atomic absorption spectrometry, measuring the content of manganese oxide in the mixed ore to be 4.34%, measuring the content of manganese oxide in the mixed ore according to GB/T6609.11-2004 aluminum oxide chemical analysis method and a physical property measurement method of flame atomic absorption spectrometry, measuring the content of sulfur element in the mixed ore, measuring the content of the sulfur element in the mixed ore to be 0.23%, grinding into 90-mesh powder, adding water, adding slurry, adjusting the slurry concentration of the slurry and the slurry of the slurry, adding the slurry of the manganese oxide ore to be 40.6.6.6.40.3 g of the slurry, adding the slurry;
B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; adding an ammonia water solution into the supernatant at the temperature of 40 ℃ and under the stirring of the linear velocity of 28m/s to adjust the pH to 8.8, carrying out solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and carrying out filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution;
C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; adding 5% of coke into a manganese hydroxide filter pressing block C, sintering at 900 ℃ to obtain a furnace charge (the manganese content in the furnace charge is detected according to a potentiometric titration method for measuring manganese content of GB/T8654.7-1988 manganese metal chemical analysis method), the manganese content in the ore is measured to be 65.76%, the phosphorus content in the furnace charge is measured according to an antimony-phosphorus-molybdenum blue spectrophotometry method in GB/T223.59-2008 steel and alloy phosphorus content determination bismuth-phosphorus-molybdenum blue spectrophotometry and antimony-phosphorus-molybdenum blue spectrophotometry method, the phosphorus content in the furnace charge is measured to be 0.07%, and the sulfur content in the furnace charge is measured according to a GB/T ferromanganese and blast furnace ferromanganese chemical analysis method, the sulfur content in the furnace charge is measured, and the sulfur content in the furnace charge is measured to be 0.01%);
D. c, adding the washing water obtained in the step C into an ammonium sulfate solution, slowly adding quicklime (the amount is that the ammonium sulfate in the ammonium sulfate solution can be completely reacted) under stirring at room temperature at a linear speed of 15m/s, recovering generated ammonia gas with water after 2.5h to obtain an ammonia water solution, performing solid-liquid separation after filter pressing of the solution after reaction to obtain a calcium sulfate filter pressing block and water, and standing the water for impurity removal and then recycling;
E. washing a filter pressing block A with water, then carrying out filter pressing to obtain a filter pressing block and a solution, homogenizing the filter pressing block and a calcium sulfate filter pressing block, adjusting the contents of calcium, magnesium, silicon, aluminum and iron in the mixture according to the production requirement of ordinary portland cement, adding pulverized coal after homogenization, calcining at 1350 ℃, separating powder and gas generated in the calcining process, adding the powder into a rotary furnace for cyclic calcination, recycling gas sulfur dioxide for preparing sulfuric acid, recycling tail gas for preparing the sulfuric acid by using manganese dioxide, and using the recycled mixture as a manganese preparation raw material;
F. and (3) standing the solution obtained after the filter pressing block A is washed by water, cooling, removing the precipitate to obtain a supernatant, then adjusting the pH to 9, standing, performing filter pressing and solid-liquid separation, wherein the filter pressing block is used for the slurrying procedure in the step A, and the solution is adjusted to the pH of 7.5 and is recycled as the water for washing slag.
According to the method, every 7.0 tons of ore is consumed, and every 1600 degrees of electricity is consumed (about 0.41 yuan/degree), so that 1 ton of furnace burden (about 3900 yuan/ton) capable of producing the silicon-manganese alloy and 6.9 tons of cement additive (about 320 yuan/ton) are prepared. The content of manganese element is increased from 10.47% to 65.76%, the content of phosphorus element is reduced from 1.77% to 0.07%, and the content of sulfur element is reduced from 0.23% to 0.01%.
Example 4
The method for producing furnace charge by using manganese carbonate ore without manganese oxide ore comprises the following steps:
A. the method comprises the steps of detecting the content of a manganese element in manganese carbonate ores without manganese oxide ores (detecting the content of the manganese element in the ores according to a ferrous sulfate titration method in GB/T1506-2016 manganese ore manganese content determination potentiometric titration method and ferrous sulfate titration method), detecting the content of the manganese element in the ores according to GB/T1515-2002 manganese ore phosphorus content determination phosphomolybdic blue spectrophotometry, detecting the content of the phosphorus element in the ores to be 1.75%, detecting the content of the manganese oxide in the ores according to GB/T6609.11-2004 aluminum oxide chemical analysis method and physical property determination method flame atomic absorption spectrometry to determine the content of the manganese oxide in the ores to be manganese oxide, determining that the ores do not contain manganese oxide, detecting the content of the sulfur element in the ores according to GB/T14949.9-1994 manganese ore chemical analysis method sulfur content, adding water to the content of the sulfur element in the ores, grinding the ores into 80-mesh powder (the slurry degree is the slurry content of manganese ions after the slurry is adjusted to be 60g/L, adding the slurry concentration of the slurry of the acid ions after the slurry is adjusted to be 27.2 g, adding the slurry concentration of the slurry solution after the slurry concentration is adjusted to be 27.2 g, and filter-pressing, adding the slurry concentration of the slurry solution after the slurry temperature is adjusted to be 27.2 g of the slurry concentration of the slurry after the slurry temperature of the slurry being adjusted to be;
B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; adding an ammonia water solution into the supernatant at the temperature of 42 ℃ and under the stirring of the linear velocity of 20m/s to adjust the pH to 9, carrying out solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and carrying out filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution;
C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; adding coke with the mass of 10 percent into a manganese hydroxide filter pressing block C, sintering at the temperature of 1000 ℃ to obtain furnace charge (detecting the manganese content in the furnace charge according to GB/T8654.7-1988 manganese metal chemical analysis method potentiometric titration method to measure the manganese content to obtain 65.63 percent of manganese in the ore), detecting the phosphorus content in the furnace charge according to Sb-P-Mo-blue spectrophotometry in GB/T223.59-2008 steel and alloy phosphorus content determination Bi-P-Mo-blue spectrophotometry and Sb-P-Mo-blue spectrophotometry to obtain 0.067 percent of phosphorus in the ore, detecting the sulfur content in the furnace charge according to GB/T ferromanganese and blast furnace ferromanganese chemical analysis method to obtain 0.01 percent of sulfur in the furnace charge);
D. c, adding the washing water obtained in the step C into an ammonium sulfate solution, slowly adding quicklime (the amount is that the ammonium sulfate in the ammonium sulfate solution can be completely reacted) at the temperature of 45 ℃ under the stirring condition that the linear speed is 18m/s, recovering the generated ammonia gas with water after 3h to obtain an ammonia water solution, performing solid-liquid separation after filter pressing of the solution after reaction to obtain a calcium sulfate filter pressing block and water, and standing the water to remove impurities and then recycling;
E. washing a filter pressing block A with water, then carrying out filter pressing to obtain a filter pressing block and a solution, homogenizing the filter pressing block and a calcium sulfate filter pressing block, adjusting the contents of calcium, magnesium, silicon, aluminum and iron in the mixture according to the production requirement of ordinary portland cement, adding pulverized coal after homogenization, calcining at 1400 ℃, separating powder and gas generated in the calcining process, adding the powder into a rotary furnace for cyclic calcination, recycling the gas sulfur dioxide for preparing sulfuric acid, recovering the tail gas for preparing the sulfuric acid by using calcium hydroxide, and using the recycled mixture as a cement additive;
F. and (3) standing the solution obtained by washing the filter pressing block A with water, cooling, removing the precipitate to obtain a supernatant, adjusting the pH to 10, standing, performing filter pressing and solid-liquid separation, wherein the filter pressing block is used for the slurrying process in the step A, and the solution is adjusted to the pH of 6.5 and is recycled as water for washing slag.
According to the method, every 7.0 tons of ore is consumed, and every 1600 degrees of electricity is consumed (about 0.41 yuan/degree), so that 1 ton of furnace burden (about 3900 yuan/ton) capable of producing the silicon-manganese alloy and 6.8 tons of cement additive (about 320 yuan/ton) are prepared. The content of manganese element is increased from 10.38% to 65.63%, the content of phosphorus element is reduced from 1.75% to 0.07%, and the content of sulfur element is reduced from 0.21% to 0.01%.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment contains independent technical solutions, and such description of the description is only for clarity, and those skilled in the art should take the description as as a whole, and the technical solutions in the respective embodiments may be combined appropriately to form other embodiments that those skilled in the art can understand.
Claims (9)
1. The method for producing furnace charge by manganese carbonate ore is characterized by comprising the following steps:
A. grinding manganese carbonate ores into powder, pulping, adding acid, stirring and leaching, then adjusting the pH value to 6.0-6.4, removing impurities, and carrying out solid-liquid separation after filter pressing to obtain a manganese sulfate solution and a filter pressing block A;
B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; adding alkali into the supernatant at the temperature of 38-42 ℃, stirring and adjusting the pH to 8.5-9, performing solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and performing filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution;
C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; and sintering the manganese hydroxide filter pressing block C to obtain furnace charge.
2. The method of claim 1, wherein the grinding in step a is grinding into 80-100 mesh powder.
3. The method according to claim 1 or 2, wherein the slurrying in step a is carried out to such an extent that the divalent manganese ion content in the slurried solution is 25-40 g/L.
4. The method according to claim 1, 2 or 3, wherein in the step A, the temperature of the solution after slurrying is kept at 50-80 ℃ during the acid adding process, the acid is concentrated sulfuric acid, the adding amount is 50-75g/L of sulfuric acid in the solution after adding, and the stirring linear speed during adding is 20-30 m/s.
5. The method of claim 1, 2, 3 or 4, wherein the base in step B is an aqueous ammonia solution and the stirring linear velocity is 20-30 m/s.
6. The method as claimed in claim 1, 2, 3, 4 or 5, wherein the sintering temperature in step C is 1400-1700 ℃.
7. The method of claim 1, 2, 3, 4, 5 or 6, further comprising the steps of: and C, adding the washing water obtained in the step C into an ammonium sulfate solution, stirring and adding quicklime at the temperature of less than or equal to 90 ℃, recovering the generated ammonia gas with water to obtain an ammonia water solution, carrying out filter pressing on the solution after reaction, carrying out solid-liquid separation to obtain a calcium sulfate filter pressing block and water, and standing the water for impurity removal and then recycling.
8. The method of claim 7, further comprising the steps of: and washing the filter pressing block A with water, then carrying out filter pressing to obtain a filter pressing block and a solution, homogenizing the filter pressing block and the calcium sulfate filter pressing block, adjusting the content of calcium, magnesium, silicon, aluminum and iron in the mixture according to production requirements, homogenizing, adding coal powder, and calcining to obtain the cement additive.
9. Use of the charge produced by the process of any one of claims 1 to 8, , in the production of manganese alloys.
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