CN115159470A - Method for preparing sulfuric acid and manganese sulfate in linkage manner by adopting sulfur - Google Patents
Method for preparing sulfuric acid and manganese sulfate in linkage manner by adopting sulfur Download PDFInfo
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- CN115159470A CN115159470A CN202210924685.3A CN202210924685A CN115159470A CN 115159470 A CN115159470 A CN 115159470A CN 202210924685 A CN202210924685 A CN 202210924685A CN 115159470 A CN115159470 A CN 115159470A
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Abstract
The invention belongs to the technical field of metallurgy, and discloses a method for preparing manganese sulfate by preparing sulfuric acid from sulfur in a linkage manner. Firstly, preparing liquid refined sulfur, atomizing and then burning to obtain sulfur incinerator gas, and controlling a part of sulfur incinerator gas to sequentially carry out primary conversion, primary absorption, secondary conversion and secondary absorption to obtain a sulfuric acid product; reacting the residual part of the sulfur-burning furnace gas with slurry prepared by mixing manganese ore and filter-pressing filtrate to generate manganese sulfate crude liquid, and then carrying out a series of treatments to obtain a battery-grade manganese sulfate product and a feed-grade manganese sulfate product. The invention has simple process, little environmental pollution and SO 2 The conversion rate is higher, the heat energy recovery utilization rate is high, and the investment, the operation cost and the production cost are lower than those of the pyrite-based sulphuric acid.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for preparing manganese sulfate by preparing sulfuric acid from sulfur in a linkage manner.
Background
Manganese sulfate is an important basic inorganic salt product and an important trace element fertilizer, and is widely applied to various industries such as chemical industry, agriculture, medicine, light industry and the like. Nearly 80% of manganese products worldwide are prepared by using manganese sulfate or electrolytic manganese sulfate solution as a basic raw material, so the demand of the manganese sulfate product is high. The domestic process for preparing manganese sulfate mainly comprises the following steps: 1. coal roasting-sulfuric acid leaching method: the method is most widely applied at present, but has the problems of high energy consumption, poor operation conditions, environmental pollution and the like, and is not suitable for low-grade pyrolusite; 2. two-ore reduction acid leaching method: the method has simple flow structure, easy technical operation and low production cost, but the chemical mechanism of the reaction is not completely and uniformly recognized at home, so the method has the problems of more complex reaction control, poor production condition, inconvenient actual operation and the like, and cannot be widely applied in industry; 3. two-ore roasting and acid leaching method: the method needs to leach the material after high-temperature roasting, and although the manganese leaching rate is high, the method has the disadvantages of high energy consumption, high cost, poor high-temperature working environment and easy environmental pollution caused in the roasting process.
Aiming at the defects in the prior art, the invention provides a production process for producing manganese sulfate by linkage production of sulfuric acid, which is used for preparing acid-SO from the existing sulfur 2 The reduction leaching method is improved, and the waste heat of the sulfur-based acid preparation and the reducibility of sulfur dioxide are utilized to produce sulfuric acid and manganese sulfate. The process technology has the advantages of less manganese sulfate slag, low energy consumption, no waste water discharge and advanced production technology, and the slag can be used as a building product raw material. The process avoids high-temperature roasting, improves operating environment, reduces raw material consumption, makes full use of sulfur dioxide reducibility, and simplifies one-step leachingThe investment, operation cost and production cost of the process are lower than those of the process for preparing acid by pyrite. In the acid making process, the sulfuric acid is produced by adopting a two-conversion and two-absorption process, the conversion rate of sulfur dioxide is higher, the pollution to the environment is lower, and the advanced level of domestic clean production can be reached.
Disclosure of Invention
In view of the above, the invention provides a method for preparing manganese sulfate by using sulfur and sulfuric acid in a linkage manner, so as to solve the problems of high energy consumption, large environmental pollution and difficult operation of the traditional manganese sulfate preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing sulfuric acid from sulfur and preparing manganese sulfate in a linkage manner comprises the following steps:
1) Mixing the molten sulfur heated to be molten with a filter aid, and filtering to obtain liquid refined sulfur;
2) Atomizing liquid refined sulfur, mixing the atomized liquid refined sulfur with air, and combusting to obtain sulfur incinerator gas;
3) Sequentially carrying out primary conversion, primary absorption, secondary conversion and secondary absorption on part of sulfur incinerator gas to obtain absorption liquid and absorption tail gas, wherein the absorption liquid is a sulfuric acid product;
4) Mixing manganese ore and filter-pressing filtrate to obtain slurry;
5) Introducing the residual part of sulfur incinerator gas and absorption tail gas in the step 3) into 2-time crystallization mother liquor and three-time rinsing liquor, carrying out acid leaching, mixing the residual gas after acid leaching with slurry for intermediate leaching, and reacting to generate manganese sulfate crude liquid;
6) Mixing sodium sulfide with the crude manganese sulfate solution, and reacting to obtain manganese sulfate;
7) Carrying out primary crystallization on manganese sulfate, carrying out crystal-liquid separation after crystallization to obtain crystals and mother liquor, sending the mother liquor to a feed-grade evaporation crystallization process, sending the crystals into a dissolving tank for primary dissolution, adopting 3 crystallization mother liquor as a dissolution solution, sequentially sending the crystals into 2, 3 and 4 crystallization processes after dissolution, sending the 2 crystallization mother liquor to the preparation step 5) for production, respectively returning the 3 and 4 crystallization mother liquors to the 1 and 2 dissolving tanks, adding steam condensate water into the 3 crystallization crystals for dissolution, and sending the crystals into 4 crystallization after dissolution, wherein the 4 crystallization crystals are a battery-grade manganese sulfate product; the heat required by the crystal drying is provided by heating air through a heat exchanger by steam generated by a waste heat boiler;
8) Evaporating and crystallizing the mother liquor to obtain a manganese sulfate crystallization liquid, wherein a heat source is waste heat boiler steam, condensed water obtained after steam condensation is reused in a boiler, and evaporated condensed water is reused in crystallization, dissolution, leaching and rinsing processes for 3 times;
centrifuging the manganese sulfate crystal liquid, and continuously evaporating and crystallizing the obtained liquid; and combining the manganese sulfate crystals obtained twice, and drying to obtain a manganese sulfate crystal feed grade manganese sulfate product.
Preferably, the ratio of the addition amount of the filter aid to the filtration area in the step 1) is 0.6 to 1.5kg/m 2 ；
The filter aid is diatomite;
the mixing temperature is 125-135 ℃.
Preferably, the volume content of sulfur dioxide in the sulfur incinerator gas obtained in the step 2) is 10-10.5%.
Preferably, the volume ratio of the part of sulfur-burning furnace gas in the step 3) to the rest of sulfur-burning furnace gas in the step 5) is 1:0 to 3.
Preferably, the first conversion in the step 3) enters a first section of catalyst layer of the converter at the temperature of 415-420 ℃ for conversion to generate sulfur trioxide, the temperature of a first section of outlet of the converter is 600-610 ℃, the sulfur trioxide enters a high-temperature superheater for heat exchange, the temperature of the first section of outlet of the converter is reduced to 452-458 ℃, the sulfur trioxide enters a second section of catalyst layer of the converter for conversion, the temperature of a second section of outlet of the converter is 515-518 ℃, and the sulfur trioxide enters a hot heat exchanger for heat exchange; after the temperature is reduced to 438-442 ℃, the mixture enters a third section of catalyst layer of the converter for conversion, and the temperature of an outlet of the third section of the converter is 450-455 ℃;
the first absorption temperature is 170-190 ℃, the absorption liquid is concentrated sulfuric acid, the mass concentration of the absorption liquid is 98%, and the temperature of the sulfur incinerator gas after absorption is 75-80 ℃;
the second conversion is that the temperature of the sulfur incinerator gas absorbed for the first time is raised to 410-420 ℃, and the sulfur incinerator gas enters a fourth section catalyst layer of the converter, and the temperature of an outlet of the fourth section of the converter is 440-450 ℃;
the second absorption temperature is 155-165 ℃, the absorption liquid is concentrated sulfuric acid, and the mass concentration of the absorption liquid is 98%;
the catalyst of the catalyst layer is vanadium pentoxide.
Preferably, the particle size of the manganese ore in the step 4) is 10-1000 μm;
the mass ratio of the manganese ore to the filter pressing filtrate in the step 4) is 1:1 to 10.
Preferably, the acid leaching temperature in the step 5) is 60-100 ℃, and the acid leaching time is 1-24 h; the middle immersion temperature is 60-100 ℃, and the middle immersion time is 1-24 h.
Preferably, the mass ratio of the sodium sulfide to the manganese sulfate crude liquid in the step 6) is 1: 1000-10000, and the reaction time is 1-24 h.
Preferably, the crystallization time in the step 7) is independently 1.8-2.2 h.
Preferably, the crystallization time in the step 8) is independently 1.8-2.2 h.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
compared with the coal roasting-sulfuric acid leaching method and the two-ore reduction acid leaching method, the method has the advantages of simple process, small environmental pollution, high heat energy recovery and utilization rate, and lower investment, operation cost and production cost compared with the pyrite acid preparation method. Compared with the roasting and acid leaching method of two ores, the process avoids high-temperature roasting, improves the operation environment and reduces the consumption of raw materials. For the purification production of sulfuric acid, the invention adopts a two-conversion two-absorption and acid-washing production process, compared with a one-conversion one-absorption process, SO 2 The conversion rate is higher, the pollution is lower, and the advanced level of domestic clean production can be achieved. The process technology for producing the manganese sulfate slag is less, the slag can be used as a building product raw material, the energy consumption is low, no wastewater is discharged, the production technology is advanced, and better economic benefit can be brought to enterprises.
Drawings
FIG. 1 is a flow chart of the present invention for preparing manganese sulfate by using sulfur and sulfuric acid in a linkage manner.
Detailed Description
A method for preparing sulfuric acid from sulfur and preparing manganese sulfate in a linkage manner comprises the following steps:
1) Mixing the molten sulfur heated to be molten with a filter aid, and filtering to obtain liquid refined sulfur;
2) Atomizing liquid refined sulfur, mixing the atomized liquid refined sulfur with air, and combusting to obtain sulfur incinerator gas;
3) Sequentially carrying out primary conversion, primary absorption, secondary conversion and secondary absorption on part of sulfur incinerator gas to obtain absorption liquid and absorption tail gas, wherein the absorption liquid is a sulfuric acid product;
4) Mixing manganese ore with filter-pressing filtrate to obtain slurry;
5) Introducing the residual part of sulfur incinerator gas and absorption tail gas in the step 3) into 2-time crystallization mother liquor and three-time rinsing liquor, carrying out acid leaching, mixing the residual gas after acid leaching with slurry for intermediate leaching, and reacting to generate manganese sulfate crude liquid;
6) Mixing sodium sulfide and manganese sulfate crude liquid, and reacting to obtain manganese sulfate;
7) Carrying out primary crystallization on manganese sulfate, carrying out crystal-liquid separation after crystallization to obtain crystals and mother liquor, sending the mother liquor to a feed-grade evaporation crystallization process, sending the crystals into a dissolving tank for primary dissolution, adopting 3 crystallization mother liquor as a dissolution solution, sequentially sending the crystals into 2, 3 and 4 crystallization processes after dissolution, sending the 2 crystallization mother liquor to the preparation step 5) for production, respectively returning the 3 and 4 crystallization mother liquors to the 1 and 2 dissolving tanks, adding steam condensate water into the 3 crystallization crystals for dissolution, and sending the crystals into 4 crystallization after dissolution, wherein the 4 crystallization crystals are a battery-grade manganese sulfate product; the heat required by the crystal drying is provided by heating air through a heat exchanger by steam generated by a waste heat boiler;
8) Evaporating and crystallizing the mother liquor to obtain a manganese sulfate crystallization liquid, wherein a heat source is waste heat boiler steam, condensed water obtained after steam condensation is reused in a boiler, and evaporated condensed water is reused in crystallization, dissolution, leaching and rinsing processes for 3 times;
centrifuging the manganese sulfate crystal liquid, and continuously evaporating and crystallizing the obtained liquid; and combining the manganese sulfate crystals obtained twice, and drying to obtain the manganese sulfate crystal feed-grade manganese sulfate product.
In the present invention, the ratio of the amount of the filter aid added to the filtration area in the step 1) to the filtration area is 0.6 to 1.5kg/m 2 Preferably 0.8 to 1.2kg/m 2 More preferably 1kg/m 2 ；
The filter aid is diatomite;
the mixing temperature is 125 to 135 ℃, preferably 128 to 132 ℃, and more preferably 130 ℃.
In the invention, the volume content of sulfur dioxide in the sulfur incinerator gas obtained in the step 2) is 10-10.5%, preferably 10.1-10.3, and more preferably 10.2.
In the invention, the volume ratio of the part of sulfur-burning furnace gas in the step 3) to the rest of sulfur-burning furnace gas in the step 5) is 1:0 to 3, preferably 1:0.5 to 2.5, more preferably 1:2.
in the invention, the first conversion in the step 3) enters a first section catalyst layer of a converter for conversion at 415-420 ℃ to generate sulfur trioxide, the temperature of a first section outlet of the converter is 600-610 ℃, the first section outlet of the converter enters a high-temperature superheater for heat exchange, the temperature of the first section outlet of the converter is reduced to 452-458 ℃ and then enters a second section catalyst layer of the converter for conversion, the temperature of a second section outlet of the converter is 515-518 ℃, and the second section outlet of the converter enters a heat exchanger for heat exchange; after the temperature is reduced to 438-442 ℃, the mixture enters a third section of catalyst layer of the converter for conversion, and the temperature of a third section of outlet of the converter is 450-455 ℃;
the first absorption temperature is 170-190 ℃, preferably 175-185 ℃, and more preferably 180 ℃; the absorption liquid is concentrated sulfuric acid, the mass concentration of the absorption liquid is 98%, and the temperature of the sulfur incinerator gas after absorption is 75-80 ℃, preferably 76-78 ℃, and more preferably 77 ℃;
the second conversion is to heat the sulfur incinerator gas absorbed for the first time to 410-420 ℃, preferably 412-418 ℃, and more preferably 415 ℃; entering a fourth section catalyst layer of the converter, wherein the outlet temperature of the fourth section of the converter is 440-450 ℃, preferably 442-446 ℃, and further preferably 445 ℃;
the secondary absorption temperature is 155-165 ℃, preferably 158-162 ℃, and more preferably 160 ℃; the absorption liquid is concentrated sulfuric acid, and the mass concentration of the absorption liquid is 98%;
the catalyst of the catalyst layer is vanadium pentoxide.
In the present invention, the particle size of the manganese ore in the step 4) is 10 to 1000 μm, preferably 50 to 800 μm, more preferably 100 to 600 μm, and still more preferably 300 μm;
the mass ratio of the manganese ore to the filter pressing filtrate in the step 4) is 1:1 to 10, preferably 1:2 to 8, more preferably 1:6;
the filter-pressing filtrate in the step 4) is a filter-pressing product obtained by mixing the middle leaching residues and the rinsing liquid, and is replaced by acid liquor in the first operation, wherein the pH value of the acid liquor is preferably 2-4, and the acid liquor comprises sulfuric acid solution.
In the invention, the acid leaching temperature in the step 5) is 60-100 ℃, preferably 70-90 ℃, and further preferably 80 ℃; the acid leaching time is 1-24 h, preferably 6-20 h, and more preferably 12h; the preferred medium immersion temperature is 70-90 ℃, and the further preferred medium immersion temperature is 80 ℃; the medium leaching time is 1-24 h, and the acid leaching time is 1-24 h, preferably 6-20 h, and more preferably 12h.
In the present invention, the purpose of the acid leaching is that sulfur dioxide reacts more thoroughly with manganese dioxide under acidic conditions, enabling more tetravalent manganese to be converted into divalent manganese, which is more soluble under acidic conditions.
In the invention, the mass ratio of the sodium sulfide to the manganese sulfate crude liquid in the step 6) is 1:1000 to 10000, preferably 1:3000 to 8000, more preferably 1:5000; the reaction time is 1 to 24 hours, preferably 6 to 20 hours, and more preferably 12 hours.
In the present invention, the crystallization time in the step 7) is independently 1.8 to 2.2 hours, preferably 1.9 to 2.1 hours, and more preferably 2 hours.
In the present invention, the crystallization time in the step 8) is independently 1.8 to 2.2 hours, preferably 1.9 to 2.1 hours, and more preferably 2 hours.
In the invention, a flow chart of preparing manganese sulfate by linkage of sulfuric acid prepared from sulfur is shown in figure 1.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Heating sulfur (molten) to 125 deg.C and diatomite (with a ratio to the filtration area of 1 kg/m) 2 ) Mixing, and filtering with liquid sulfur filter pump to remove impurity particles such as sand grains to obtain liquid refined sulfur;
mechanically atomizing liquid refined sulfur, spraying the atomized liquid refined sulfur into a sulfur incinerator, mixing the atomized liquid refined sulfur with air, and burning the mixture to obtain sulfur incinerator gas; mixing dry air with sulfur in sulfur incinerator to produce SO content of 10.5% 2 The furnace gas enters a fire tube type waste heat boiler to be cooled, and the temperature is reduced from 1000 ℃ to 415 ℃;
50 percent of sulfur incinerator gas enters a first section catalyst layer of the converter for conversion, and is partially converted into SO under the action of the catalyst 3 The temperature of an outlet at the first section of the converter is increased to 607 ℃, the gas enters a high-temperature superheater for heat exchange, the temperature of the gas cooled by the high-temperature superheater is reduced to 455 ℃, the gas enters a catalyst layer at the second section of the converter for conversion, the temperature of the flue gas at the second section of the converter is increased to 516 ℃, and the gas enters a heat exchanger for heat exchange. And the temperature of the gas cooled by the hot heat exchanger is reduced to 440 ℃, the gas enters a third section of catalyst layer of the converter for conversion, the temperature of the mixed flue gas at the three section outlet of the converter is increased to 453 ℃, the mixed flue gas sequentially passes through the cold heat exchanger and the medium temperature economizer, and the gas is sent into an absorption tower for primary absorption after being cooled to 180 ℃.
Unabsorbed SO at 78 deg.C from one absorption tower 2 The gas is respectively in countercurrent heat exchange with high-temperature furnace gas at two-stage and three-stage outlets of the converter through a cold-heat exchanger and a hot-heat exchanger, the temperature is raised to 415 ℃, and the gas enters a catalyst layer at the fourth stage of the converter for carrying outThe second conversion, wherein the outlet temperature of the four sections of the converter is 445 ℃, the converted product enters a low-temperature superheater and a low-temperature economizer to recover heat energy, the temperature is reduced to 160 ℃, the converted product enters a second absorption tower to be subjected to second absorption, and absorption liquid is a sulfuric acid product, wherein the catalyst is vanadium pentoxide, and the absorption liquid is concentrated sulfuric acid with the mass fraction of 98%;
crushing manganese ore to 300 mu m, and mixing the crushed manganese ore with filter-pressing filtrate according to a mass volume ratio of 1:5, mixing to obtain slurry;
introducing the rest part of sulfur incinerator gas and absorption tail gas into 2 times of crystallization mother liquor and three times of rinsing liquor, carrying out acid leaching at 80 ℃ for 12h, mixing the residual gas after acid leaching and slurry, and carrying out acid leaching at 80 ℃ for 12h to react to generate manganese sulfate crude liquid;
mixing sodium sulfide and manganese sulfate crude liquid according to a mass ratio of 1:5000 mixing, and reacting for 12h to obtain manganese sulfate;
carrying out primary crystallization on manganese sulfate, carrying out crystal-liquid separation after crystallization is finished to obtain crystals and mother liquor, sending the mother liquor to a feed-grade evaporation crystallization process, sending the crystals into a dissolving tank for primary dissolution, adopting 3 times of crystallization mother liquor as a dissolution solution, sequentially sending the dissolved crystals into 2, 3 and 4 crystallization processes (the crystallization time is 2 hours), sending the 2 times of crystallization mother liquor to a preparation step 5) for production, respectively returning the 3 times of crystallization mother liquor and the 4 times of crystallization mother liquor into 1 time of dissolving tank and 2 times of dissolving tank, adding steam condensate water into the 3 times of crystallization crystals for dissolution, and then sending the crystals into 4 times of crystallization, wherein the 4 times of crystallization crystals are battery-grade manganese sulfate products; the heat required by the crystal drying is provided by heating air by steam generated by a waste heat boiler through a heat exchanger;
evaporating and crystallizing the mother liquor to obtain manganese sulfate crystallization liquid, wherein a heat source is waste heat boiler steam, condensed water obtained after steam condensation is reused in a boiler, and evaporated condensed water is reused in crystallization dissolving and leaching rinsing processes for 3 times (crystallization time is 2 hours); centrifuging the manganese sulfate crystal liquid, and continuously evaporating and crystallizing the obtained liquid; and combining the manganese sulfate crystals obtained twice, and drying to obtain the manganese sulfate crystal feed-grade manganese sulfate product.
ICP is adopted to analyze the manganese content in the leached slag, the manganese content in the leached slag is 0.37%, and the leaching rate of the manganese element is 98.86% according to the manganese content of the original manganese ore being 32.59%.
Example 2
Heating sulfur (molten) to 130 ℃ and diatomaceous earth (ratio of filtration area to total weight of diatomaceous earth: 1.5 kg/m) 2 ) Mixing, and filtering with liquid sulfur filter pump to remove impurity particles such as sand grains to obtain liquid refined sulfur;
mechanically atomizing liquid refined sulfur, spraying the atomized liquid refined sulfur into a sulfur incinerator, mixing the atomized liquid refined sulfur with air, and burning the mixture to obtain sulfur incinerator gas; mixing dry air with sulfur in sulfur incinerator to produce SO content of 10.5% 2 The furnace gas enters a fire tube type waste heat boiler to be cooled, and the temperature is reduced from 1000 ℃ to 415 ℃;
50 percent of sulfur incinerator gas enters a first section catalyst layer of the converter for conversion, and is partially converted into SO under the action of the catalyst 3 The temperature of an outlet at the first section of the converter is raised to 610 ℃, the gas enters a high-temperature superheater for heat exchange, the temperature of the gas cooled by the high-temperature superheater is lowered to 458 ℃ and then enters a catalyst layer at the second section of the converter for conversion, the temperature of the flue gas at the second section of the converter is raised to 518 ℃, and the flue gas enters a heat exchanger for heat exchange. And the temperature of the gas cooled by the hot heat exchanger is reduced to 442 ℃, and then the gas enters a third section of catalyst layer of the converter for conversion, the temperature of the mixed flue gas at an outlet of the third section of the converter is increased to 455 ℃, the mixed flue gas sequentially passes through the cold heat exchanger and the medium temperature economizer, and is cooled to 190 ℃, and then the gas is sent to an absorption tower for primary absorption.
Unabsorbed SO from one absorption tower at a temperature of 80 DEG C 2 The gas is subjected to countercurrent heat exchange with high-temperature furnace gas at two-stage and three-stage outlets of the converter respectively through a cold-heat exchanger and a hot-heat exchanger, the temperature is raised to 420 ℃, the gas enters a fourth-stage catalyst layer of the converter for secondary conversion, the temperature at the four-stage outlet of the converter is 450 ℃, the gas enters a low-temperature superheater and a low-temperature economizer for recovering heat energy, the temperature is reduced to 165 ℃ and then enters a second absorption tower for secondary absorption, absorption liquid is a sulfuric acid product, wherein the catalyst is vanadium pentoxide, and the absorption liquid is concentrated sulfuric acid with the mass fraction of 98%;
crushing manganese ore to 100 mu m, and mixing the crushed manganese ore with filter pressing filtrate according to the mass-volume ratio of 1:2, mixing to obtain slurry;
introducing the rest part of sulfur incinerator gas and absorption tail gas into 2 times of crystallization mother liquor and three times of rinsing liquor, carrying out acid leaching for 5 hours at the temperature of 60 ℃, mixing the rest gas after acid leaching and slurry, and carrying out acid leaching for 5 hours at the temperature of 60 ℃ to react to generate manganese sulfate crude liquid;
mixing sodium sulfide and manganese sulfate crude liquid according to the mass ratio of 1:8000 mixing, reacting for 10h to obtain manganese sulfate;
carrying out primary crystallization on manganese sulfate, carrying out crystal-liquid separation after crystallization to obtain crystals and mother liquor, sending the mother liquor to a feed-grade evaporation crystallization process, sending the crystals into a dissolving tank for primary dissolution, adopting 3 crystallization mother liquor as a dissolution solution, sequentially sending the crystals into 2, 3 and 4 crystallization processes (the crystallization time is 2 hours) after dissolution, sending the 2 crystallization mother liquor to a preparation step 5) for production, respectively returning the 3 and 4 crystallization mother liquors to the 1 and 2 dissolving tanks, adding steam condensate water into the 3 crystallization crystals for dissolution, sending the crystals into 4 crystallization after dissolution, and obtaining battery-grade manganese sulfate products as the 4 crystallization crystals; the heat required by the crystal drying is provided by heating air by steam generated by a waste heat boiler through a heat exchanger;
evaporating and crystallizing the mother liquor to obtain manganese sulfate crystallization liquid, wherein a heat source is waste heat boiler steam, condensed water obtained after steam condensation is reused in a boiler, and evaporated condensed water is reused in crystallization, dissolution, leaching and rinsing processes for 3 times (crystallization time is 2 hours); centrifuging the manganese sulfate crystal liquid, and continuously evaporating and crystallizing the obtained liquid; and combining the manganese sulfate crystals obtained twice, and drying to obtain the manganese sulfate crystal feed-grade manganese sulfate product.
Example 3
Heating sulfur (molten) to 135 deg.C and diatomite (with a ratio of filter area of 0.6 kg/m) 2 ) Mixing, and filtering with liquid sulfur filter pump to remove impurity particles such as sand grains to obtain liquid refined sulfur;
mechanically atomizing liquid refined sulfur, spraying the atomized liquid refined sulfur into a sulfur incinerator, mixing the atomized liquid refined sulfur with air, and burning the mixture to obtain sulfur incinerator gas; mixing dry air with sulfur in sulfur incinerator to produce content of 10% SO 2 The furnace gas enters a fire tube type waste heat boiler to be cooledThe temperature is reduced from 1000 ℃ to 420 ℃;
25 percent of sulfur incinerator gas enters a first section catalyst layer of the converter for conversion, and is partially converted into SO under the action of the catalyst 3 The temperature of an outlet at the first section of the converter is raised to 600 ℃, the gas enters a high-temperature superheater for heat exchange, the temperature of the gas cooled by the high-temperature superheater is lowered to 452 ℃, the gas enters a catalyst layer at the second section of the converter for conversion, the temperature of the flue gas at the second section of the converter is raised to 515 ℃, and the gas enters a heat exchanger for heat exchange. And the temperature of the gas cooled by the hot heat exchanger is reduced to 438 ℃, the gas enters a third section of catalyst layer of the converter for conversion, the temperature of the mixed flue gas at the three section outlet of the converter is increased to 450 ℃, the mixed flue gas sequentially passes through the cold heat exchanger and the medium temperature economizer, and the gas is sent to an absorption tower for primary absorption after being cooled to 170 ℃.
Unabsorbed SO from one of the adsorption columns at a temperature of 75 DEG C 2 The gas is subjected to countercurrent heat exchange with high-temperature furnace gas at two-section and three-section outlets of the converter through a cold-heat exchanger and a hot-heat exchanger respectively, the temperature is increased to 410 ℃, the gas enters a fourth-section catalyst layer of the converter for secondary conversion, the temperature of the fourth-section outlet of the converter is 440 ℃, the gas enters a low-temperature superheater and a low-temperature economizer for recovering heat energy, the temperature is reduced to 155 ℃, the gas enters a second absorption tower for secondary absorption, absorption liquid is a sulfuric acid product, wherein the catalyst is vanadium pentoxide, and the absorption liquid is concentrated sulfuric acid with the mass fraction of 98%;
crushing manganese ore to 800 mu m, and mixing with filter-pressing filtrate according to a mass volume ratio of 1:7, mixing to obtain slurry;
introducing the rest part of sulfur incinerator gas and absorption tail gas into 2 times of crystallization mother liquor and three times of rinsing liquor, carrying out acid leaching at 100 ℃ for 12 hours, mixing the residual gas after acid leaching and slurry, and carrying out acid leaching at 100 ℃ for 10 hours to react to generate manganese sulfate crude liquid;
mixing sodium sulfide and manganese sulfate crude liquid according to a mass ratio of 1:2000, and reacting for 10 hours to obtain manganese sulfate;
carrying out primary crystallization on manganese sulfate, carrying out crystal-liquid separation after crystallization to obtain crystals and mother liquor, sending the mother liquor to a feed-grade evaporation crystallization process, sending the crystals into a dissolving tank for primary dissolution, adopting 3 crystallization mother liquor as a dissolution solution, sequentially sending the crystals into 2, 3 and 4 crystallization processes (the crystallization time is 2 hours) after dissolution, sending the 2 crystallization mother liquor to a preparation step 5) for production, respectively returning the 3 and 4 crystallization mother liquors to the 1 and 2 dissolving tanks, adding steam condensate water into the 3 crystallization crystals for dissolution, sending the crystals into 4 crystallization after dissolution, and obtaining battery-grade manganese sulfate products as the 4 crystallization crystals; the heat required by the crystal drying is provided by heating air by steam generated by a waste heat boiler through a heat exchanger;
evaporating and crystallizing the mother liquor to obtain manganese sulfate crystallization liquid, wherein a heat source is waste heat boiler steam, condensed water obtained after steam condensation is reused in a boiler, and evaporated condensed water is reused in crystallization dissolving and leaching rinsing processes for 3 times (crystallization time is 2 hours); centrifuging the manganese sulfate crystal liquid, and continuously evaporating and crystallizing the obtained liquid; and combining the manganese sulfate crystals obtained twice, and drying to obtain a manganese sulfate crystal feed grade manganese sulfate product.
In the present specification, the embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing manganese sulfate by using sulfur to prepare sulfuric acid in a linkage manner is characterized by comprising the following steps:
1) Mixing the molten sulfur heated to be molten with a filter aid, and filtering to obtain liquid refined sulfur;
2) Atomizing liquid refined sulfur, mixing the atomized liquid refined sulfur with air, and combusting to obtain sulfur incinerator gas;
3) Sequentially carrying out primary conversion, primary absorption, secondary conversion and secondary absorption on part of sulfur incinerator gas to obtain absorption liquid and absorption tail gas, wherein the absorption liquid is a sulfuric acid product;
4) Mixing manganese ore and filter-pressing filtrate to obtain slurry;
5) Introducing the residual part of sulfur incinerator gas and absorption tail gas in the step 3) into 2-time crystallization mother liquor and three-time rinsing liquor, carrying out acid leaching, mixing the residual gas after acid leaching with slurry for intermediate leaching, and reacting to generate manganese sulfate crude liquid;
6) Mixing sodium sulfide and manganese sulfate crude liquid, and reacting to obtain manganese sulfate;
7) Carrying out primary crystallization on manganese sulfate, carrying out crystal-liquid separation after crystallization to obtain crystals and mother liquor, sending the mother liquor to a feed-grade evaporation crystallization process, sending the crystals into a dissolving tank for primary dissolution, adopting 3 crystallization mother liquor as a dissolution solution, sequentially sending the crystals into 2, 3 and 4 crystallization processes after dissolution, sending the 2 crystallization mother liquor to the preparation step 5) for production, respectively returning the 3 and 4 crystallization mother liquors to the 1 and 2 dissolving tanks, adding steam condensate water into the 3 crystallization crystals for dissolution, and sending the crystals into 4 crystallization after dissolution, wherein the 4 crystallization crystals are a battery-grade manganese sulfate product; the heat required by the crystal drying is provided by heating air by steam generated by a waste heat boiler through a heat exchanger;
8) Evaporating and crystallizing the mother liquor to obtain a manganese sulfate crystallization liquid, wherein a heat source is waste heat boiler steam, condensed water obtained after steam condensation is reused in a boiler, and evaporated condensed water is reused in crystallization dissolving, leaching and rinsing processes for 3 times;
centrifuging the manganese sulfate crystal liquid, and continuously evaporating and crystallizing the obtained liquid; and combining the manganese sulfate crystals obtained twice, and drying to obtain the manganese sulfate crystal feed-grade manganese sulfate product.
2. The method for preparing the manganese sulfate by the linkage of the sulfuric acid preparation by the sulfur according to claim 1, wherein the ratio of the addition amount of the filter aid in the step 1) to the filter area is 0.6-1.5 kg/m 2 ；
The filter aid is diatomite;
the mixing temperature is 125-135 ℃.
3. The method for preparing the manganese sulfate by the linkage of the sulfuric acid and the sulfur according to claim 2, wherein the volume content of the sulfur dioxide in the sulfur incinerator gas obtained in the step 2) is 10-10.5%.
4. The method for preparing the manganese sulfate by the linkage of the sulfur and the sulfuric acid according to any one of claims 1 to 3, wherein the volume ratio of part of sulfur incinerator gas in the step 3) to the rest of sulfur incinerator gas in the step 5) is 1:0 to 3.
5. The method for preparing manganese sulfate by linkage of sulfuric acid and sulfur according to claim 4, wherein the first conversion in step 3) is carried out at 415-420 ℃ and then enters a first section of catalyst layer of a converter for conversion to generate sulfur trioxide, the temperature of a first section of outlet of the converter is 600-610 ℃, the first section of outlet enters a high temperature superheater for heat exchange, the temperature is reduced to 452-458 ℃ and then enters a second section of catalyst layer of the converter for conversion, the temperature of a second section of outlet of the converter is 515-518 ℃, and the second section of outlet enters a heat exchanger for heat exchange; after the temperature is reduced to 438-442 ℃, the mixture enters a third section of catalyst layer of the converter for conversion, and the temperature of an outlet of the third section of the converter is 450-455 ℃;
the first absorption temperature is 170-190 ℃, the absorption liquid is concentrated sulfuric acid, the mass concentration of the absorption liquid is 98%, and the temperature of the sulfur incinerator gas after absorption is 75-80 ℃;
the second conversion is that the temperature of the sulfur incinerator gas absorbed for the first time is raised to 410-420 ℃, and the sulfur incinerator gas enters a fourth section catalyst layer of the converter, and the temperature of an outlet of the fourth section of the converter is 440-450 ℃;
the second absorption temperature is 155-165 ℃, the absorption liquid is concentrated sulfuric acid, and the mass concentration of the absorption liquid is 98%;
the catalyst of the catalyst layer is vanadium pentoxide.
6. The method for preparing the manganese sulfate by linkage of the sulfuric acid prepared from the sulfur according to claim 5, wherein the particle size of the manganese ore in the step 4) is 10-1000 μm;
the mass ratio of the manganese ore to the filter pressing filtrate in the step 4) is 1:1 to 10.
7. The method for preparing the manganese sulfate by the linkage of the sulfuric acid prepared from the sulfur according to claim 5 or 6, wherein the acid leaching temperature in the step 5) is 60-100 ℃, and the acid leaching time is 1-24 h; the middle immersion temperature is 60-100 ℃, and the middle immersion time is 1-24 h.
8. The method for preparing manganese sulfate by linkage of sulfuric acid prepared from sulfur according to claim 7, wherein the mass ratio of sodium sulfide to manganese sulfate crude liquid in step 6) is 1: 1000-10000, and the reaction time is 1-24 h.
9. The method for preparing the manganese sulfate by the linkage of the sulfuric acid and the sulfur according to claim 8, wherein the crystallization time in the step 7) is 1.8-2.2 hours independently.
10. The method for preparing the manganese sulfate by the linkage of the sulfuric acid and the sulfur according to claim 9, wherein the crystallization time in the step 8) is 1.8-2.2 hours independently.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101837959A (en) * | 2010-05-14 | 2010-09-22 | 湖南省泸溪县金旭冶化有限责任公司 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
| CN101979130A (en) * | 2010-10-25 | 2011-02-23 | 四川大学 | Method for removing hydrogen sulfide from industrial gas in recycling way |
| CN107445209A (en) * | 2017-07-05 | 2017-12-08 | 四川大学 | Remove the method that manganous dithionate prepares saturation manganese sulfate slurries and manganese sulfate in pyrolusite pulp leachate |
| CN109987636A (en) * | 2019-05-05 | 2019-07-09 | 刘向东 | A kind of energy-saving new technology of manganese sulphate |
| CN110316704A (en) * | 2019-04-11 | 2019-10-11 | 湖北锦泽环保科技有限公司 | A kind of acid production with sulphur industrial tail gas technique of zero discharge |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837959A (en) * | 2010-05-14 | 2010-09-22 | 湖南省泸溪县金旭冶化有限责任公司 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
| CN101979130A (en) * | 2010-10-25 | 2011-02-23 | 四川大学 | Method for removing hydrogen sulfide from industrial gas in recycling way |
| CN107445209A (en) * | 2017-07-05 | 2017-12-08 | 四川大学 | Remove the method that manganous dithionate prepares saturation manganese sulfate slurries and manganese sulfate in pyrolusite pulp leachate |
| CN110316704A (en) * | 2019-04-11 | 2019-10-11 | 湖北锦泽环保科技有限公司 | A kind of acid production with sulphur industrial tail gas technique of zero discharge |
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