CN111111419B - Method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2Method for producing manganese sulfate solution - Google Patents
Method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2Method for producing manganese sulfate solution Download PDFInfo
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Abstract
The invention provides a method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2The method for preparing the manganese sulfate solution mainly comprises the following process steps: high concentration of SO2Flue gas enters from the first stage tower section of the multi-stage spray tower, desulfurization slurry enters from the last stage tower section of the multi-stage spray tower, and meanwhile, continuous grading feeding is carried out on all stages of tower sections to control the pH value and the manganese-iron ratio of the desulfurization slurry in each stage of tower section to be in a proper range, the desulfurization slurry and the flue gas reversely flow among all stages of tower sections of the multi-stage spray tower, and the desulfurization slurry is circularly sprayed in each stage of tower section of the multi-stage spray tower to carry out contact reaction with the flue gas entering from the lower part of the tower section, SO that SO in the flue gas is removed2Leaching manganese in the manganese carbonate ore; the manganese sulfate solution product is discharged from the first-stage tower section, and the flue gas after full desulfurization is discharged from the last-stage tower section. The method utilizes ferromanganese to carry out concerted catalytic desulfurization and has SO2High oxidation efficiency and low production cost.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy and flue gas sulfur resource pollution treatment, and relates to a method for removing high-concentration SO in flue gas by using manganese carbonate ore2A method for preparing a manganese sulfate solution.
Background
The manganese ore slurry flue gas desulfurization technology is rapidly developed in the last decade, and the technology utilizes manganese oxide and SO in natural manganese ore2SO by redox reactions2Removing the manganese sulfate from the flue gas, and oxidizing to obtain a manganese sulfate solution. Compared with the traditional desulfurization technology, the manganese ore desulfurization technology effectively solves the problems of sulfur resource waste, difficulty in treatment of desulfurization wastewater and waste residues and the like, and simultaneously effectively combines the atmospheric pollution control with the manganese metallurgy technology, thereby providing a new direction for the clean production development of the electrolytic manganese industry. However, in the existing report of the technology of controlling the desulfurization of manganese ore slurry and recycling, manganese oxide ore is mainly used as a desulfurizing agent. Manganese carbonate ore is used as the main manganese ore resource in China, and high-quality utilization of manganese carbonate ore is imperative as the consumption of manganese oxide ore is completely depleted.
Manganese carbonate ore generally has the characteristic of high iron content, and is not suitable for being directly used in the metallurgical industry. The utilization of low-grade manganese carbonate ore has been receiving attention from researchers in various countries. CN108031255A discloses a method for removing sulfur dioxide in flue gas by manganese carbonate ore and preparing manganese sulfate solution, wherein the flue gas containing sulfur dioxide is introduced into an absorption device added with manganese carbonate ore slurry for reaction to obtain slurry and discharged flue gasAnd then introducing oxidizing gas into the slurry for post-oxidation treatment, filtering, removing filter residues, and removing impurities from the filtrate to obtain a manganese sulfate solution. However, because manganese carbonate has a certain buffering effect in the desulfurization solution, the pH value of the desulfurization slurry is maintained in the range of 4.5-6.5 in the reaction process. The higher pH of the slurry leads on the one hand to SO during the desulfurization process2Has a low oxidation efficiency and a large proportion of SO2The sulfurous acid/sulfite exists in the desulfurization solution in the form of sulfurous acid/sulfite radical, and special re-aeration oxidation treatment is needed, so that the investment and operation cost are high; on the other hand, Mn2+Hydrolyzed to MnO2The amount of the catalyst is increased, so that the production amount and the concentration of the by-product manganese dithionate in the desulfurization solution are increased. In addition, existing manganese carbonate-based desulfurization techniques still mainly aim at lower SO2The concentration of manganese sulfate in final desulfurization liquid is low after the concentration flue gas is treated, and large-scale high-value utilization is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2Method for preparing manganese sulfate solution to solve SO existing in prior art2The oxidation efficiency is low, the production cost is overhigh due to the special oxidation treatment, and the SO is increased2The oxidation efficiency is reduced, and the production cost is reduced.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows.
The method comprises the steps of taking manganese carbonate ore as a main desulfurizer, adding an iron-containing auxiliary agent for ore blending, blending with electrolytic anolyte to obtain desulfurization slurry for continuous multistage countercurrent desulfurization and manganese leaching in a multistage spray tower, feeding and supplementing the desulfurization slurry to each stage of the multistage spray tower in a grading independent and continuous manner in the process of desulfurization and manganese leaching by adopting the multistage spray tower, and controlling the pH value, ferromanganese concentration and ferromanganese mass ratio of the desulfurization slurry of each stage of the multistage spray tower to enable each stage of the tower to perform desulfurization and leaching reactions under the optimal working condition. SO (SO)2The removal is mainly completed by a ferro-manganese catalytic system formed in the desulfurization slurry, and the ferrous auxiliary agent can be generated after slurry preparationFe3+，Fe3+Adding Mn2+Oxidized to Mn with higher oxidation activity3+Unstable Mn3+The rapid catalytic oxidation of sulfurous acid in the desulfurization slurry can be achieved by accelerating electron transfer. Fe produced by reduction2+Is oxidized into Fe again under the action of dissolved oxygen3+Thereby forming a closed loop and forming a ferromanganese synergetic catalytic system with stable activity. Meanwhile, based on the graded continuous feeding supplement of the desulfurization slurry, the pH value of the desulfurization slurry in the desulfurization process can be controlled to be rapidly reduced to below 5, and Mn in the reaction system under the condition of the pH value2+By passing
The hydrolytic oxidation process of (a) is significantly inhibited, thereby reducing incomplete oxidation of manganese dioxide with sulfur dioxide to form manganese dithionate by-product. Along with the continuation of desulfurization process, the pH value of desulfurization thick liquid constantly reduces, replenishes manganese carbonate ore thick liquid to this moment in the desulfurization system in succession, with the stable value of pH value control between 2~5, under the prerequisite of guaranteeing desulfurization efficiency, realizes continuously effectively reducing the generation of dithionite manganese. Further, Fe3+Has certain catalytic oxidation activity on dithionic acid, and can further oxidize and decompose a small amount of generated manganese dithionate to achieve the aim of eliminating the manganese dithionate.
The method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2A method of preparing a manganese sulfate solution, comprising the steps of:
(1) slurry preparation
Preparing desulfurization slurry for feeding of a final-stage tower section: fully mixing electrolytic manganese anolyte and mixed mineral powder according to the liquid-solid weight ratio of (15-20): 1 to prepare desulfurization slurry, or fully mixing water and mixed mineral powder according to the liquid-solid weight ratio of (15-20): 1 and adjusting the pH value to 2-5 by using sulfuric acid to prepare desulfurization slurry;
preparing desulfurization slurry for graded feeding: fully mixing the electrolytic manganese anolyte with the mixed mineral powder to prepare desulfurization slurry, or fully mixing water with the mixed mineral powder and adjusting the pH value to 2-5 with sulfuric acid to prepare desulfurization slurry;
the mixed mineral powder is obtained by mixing manganese carbonate mineral powder and an iron-containing auxiliary agent, and the iron content of the mixed mineral powder is 2-8 wt.%;
(2) desulfurization and leaching
Desulfurizing and leaching by adopting a multi-stage spray tower to obtain high-concentration SO2The method comprises the steps of (1) enabling flue gas to enter from a first-stage tower section of a multi-stage spray tower, enabling the prepared desulfurization slurry to enter from a last-stage tower section of the multi-stage spray tower, meanwhile, continuously adding the desulfurization slurry prepared in the step (1) into a slurry pool arranged at the bottom of each-stage tower section of the multi-stage spray tower for graded feeding, controlling the pH value of the desulfurization slurry in each-stage tower section to be 2-5 and the manganese-iron mass ratio to be (8-15): 1, enabling the desulfurization slurry and the flue gas to flow reversely between each-stage tower section of the multi-stage spray tower, enabling the desulfurization slurry to be circularly sprayed in each-stage tower section of the multi-stage spray tower to be in contact reaction with the flue gas entering from the lower part of the tower section, and2and leaching manganese in manganese carbonate ore, wherein the contact reaction temperature is 40-70 ℃, and the liquid-gas ratio of the desulfurization slurry to the flue gas is (20-30) L:1m3(ii) a The desulfurized slurry is fully leached in the tower section of the current stage, then enters the tower section of the previous stage, and is discharged from the tower section of the first stage to obtain a manganese sulfate solution product; fully removing SO from flue gas in the tower section of the stage2Then enters the next stage of tower section until SO2The content reaches the standard and is discharged from the final stage tower section.
In the study of the present invention, the inventors found that the pH value is controlled to be in an appropriate range and the ferromanganese mass ratio of the desulfurization slurry is controlled to be in an appropriate range, so that not only the desulfurization efficiency can be improved, but also the generation of manganese dithionate can be suppressed, and therefore, in the step (2) of the above method, it is necessary to control the pH value of the desulfurization slurry in each stage of the tower section to be in a range of 2 to 5, and preferably, the pH value of the desulfurization slurry in each stage of the tower section to be in a range of 3 to 4.5. Meanwhile, the mass ratio of ferromanganese of the desulfurization slurry in each stage of tower section needs to be controlled within the range of (8-15): 1. The control of the pH value of the desulfurization slurry and the control of the ferromanganese mass ratio mainly come from the step-by-step independent continuous feeding, so that each step of tower section is subjected to desulfurization and leaching reaction under the optimal working condition.
In step (2) of the above process, according toControlling the pH value of the desulfurization slurry in the next-stage tower section to be not less than that of the desulfurization slurry in the previous-stage tower section according to the direction from the first-stage tower section to the last-stage tower section; and controlling the ferromanganese mass ratio of the desulfurized slurry in the next tower section to be not more than the ferromanganese mass ratio of the desulfurized slurry in the previous tower section according to the direction from the first tower section to the last tower section. The tower sections at all levels specifically control the pH value and the ferromanganese mass ratio of the desulfurization slurry within a certain range, and the pH value and the ferromanganese mass ratio are mainly equal to those of SO in actually treated flue gas2The concentration of (A) is related, and the specific application is mainly based on the actual SO in the flue gas2Is determined. Because the compositions of the desulfurization slurry in each stage of tower section are different, in order to realize the accurate control of the pH value and the ferromanganese mass ratio of the desulfurization slurry in each stage of tower section, the solid content and the ferromanganese mass ratio of the desulfurization slurry continuously added into the slurry pool arranged at the bottom of each stage of tower section are different, and the specific composition of the desulfurization slurry fed in stages needs to be selected and controlled according to the actual composition condition of the desulfurization slurry in each stage of tower section during specific application.
In the step (2) of the method, the solid content of the desulfurization slurry in each stage of the tower section is preferably controlled to be 2-7%, and the total liquid-solid weight ratio of the desulfurization slurry in the multi-stage spray tower is preferably (2-4): 1.
In the step (2) of the method, the desulfurization slurry is circularly sprayed in each stage of the multi-stage spray tower, the circulation time of the desulfurization slurry in each stage of the spray tower is determined according to the concentration of sulfur dioxide in the flue gas, the total reaction time of the desulfurization slurry in the step (2) adopting the multi-stage spray tower is 1-4 h, and the further preferable total reaction time is 2-3 h. The circulating spraying of the desulfurization slurry in each stage of the tower section of the multi-stage spray tower is realized by the matching of a slurry pool and a circulating pump which are positioned at the bottom of the tower section, a spray head and a connecting pipe fitting which are positioned at the top of the tower section. Because all be equipped with the circulating pump at each level of tower section of multistage spray column, consequently the circulation of desulfurization thick liquid has sufficient pressure, and the shower nozzle that the desulfurization thick liquid sprayed and adopted can be the spiral-flow type shower nozzle, and the shower nozzle is difficult for blockking up, is favorable to guaranteeing multistage spray column long-term safe operation.
In the step (2) of the method, the multistage spray tower can be designed with multistage spray from bottom to topThe spray tower has an integral structure of tower sections, and the stage number of the specific spray tower is determined by the inlet flue gas SO2Comprehensively determining the concentration, the quality of manganese carbonate ore and various factors of a pulp preparation process. The number of tower sections of the multi-stage spray tower is generally 3-5, if SO in the flue gas2When the concentration is higher, the number of tower sections of the multi-stage spray tower can be increased, but with the increase of the number of tower sections, the equipment structure becomes complicated, and the equipment cost is increased, so that the number of the tower sections of the multi-stage spray tower is not more than 7. The method provided by the invention can be used for removing SO2The concentration is not less than 10000mg/m3Is also suitable for removing SO2The concentration is up to 150000-200000 mg/m3High concentration of SO2The flue gas can be used for treating SO with lower concentration by adjusting the process parameters2Flue gas.
In the step (2) of the method, the temperature of the desulfurization slurry is preferably 40-70 ℃, and the temperature of the flue gas is preferably 80-150 ℃.
In the method, the iron-containing auxiliary is mainly used for providing iron and manganese in the pyrolusite to construct a ferromanganese synergistic catalytic oxidation system, and SO in the flue gas is removed through the ferromanganese synergistic catalytic oxidation2The iron-containing auxiliary is derived from iron ore or high-iron waste slag, but is not limited to iron ore and high-iron waste slag or iron ore. In the step (1), the manganese carbonate ore powder and the iron-containing auxiliary agent are preferably mixed according to the proportion of 3-5 wt.% of iron content to prepare mixed ore powder through ore blending. In order to realize resource recycling of iron and reduce production cost, a manganese sulfate solution product discharged from the first-stage tower section is subjected to filtration-impurity removal-refiltering treatment, and iron-containing slag obtained by secondary filtration is returned to the step (1) for preparing desulfurization slurry.
In the step (2) of the method, the content of manganese sulfate in a manganese sulfate solution product discharged from the first-stage tower section is not lower than 120g/L, the content of a by-product manganese dithionate is not higher than 1.6g/L, and the manganese sulfate solution product can be directly used for producing manganese sulfate or electrolytic manganese metal after purification and impurity removal. In the above method, the manganese content of the manganese carbonate ore used for preparing the manganese carbonate powder is at least 20%.
In the step (1) of the method, the manganese carbonate mineral powder is manganese carbonate mineral powder which is sieved by a 100-mesh sieve, and the iron-containing auxiliary agent can also be powder iron-containing auxiliary agent which is sieved by a 100-mesh sieve.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial technical effects:
1. the invention aims at the existing method that the high-concentration SO is contained2The method provided by the invention uses a multi-stage spray tower as reaction equipment, uses electrolytic manganese anolyte, manganese carbonate mineral powder and iron-containing auxiliary agent to prepare slurry, controls the desulfurization slurry in each stage of tower section to have proper reaction pH value and manganese-iron mass ratio by means of multi-stage desulfurization, graded continuous feeding and the like, and realizes SO in flue gas2The method can effectively remove manganese in manganese carbonate ore and leach manganese in manganese carbonate ore, effectively inhibit the generation of by-product manganese dithionate, realize the recycling of iron, and realize SO in flue gas2Realizes the utilization of manganese carbonate ore while reaching the standard, is a novel high-concentration SO with the advantages of energy conservation, environmental protection, high utilization rate of the effective components of the manganese carbonate ore, good flue gas desulfurization effect, low production and operation cost and the like2A wet method waste gas desulfurization technology combining flue gas desulfurization and resource utilization.
2. According to the method, manganese carbonate ore is used as a main desulfurizer, and the manganese carbonate ore is wide in source, low in cost and easy to obtain; meanwhile, the manganese-iron catalytic system is reasonably constructed by utilizing the self-contained iron and the added iron-containing auxiliary agent in the manganese carbonate ore, the removal of sulfur dioxide and the oxidation conversion efficiency are high by utilizing the manganese-iron to carry out the catalytic desulfurization, and the desulfurization slurry does not need to be subjected to aeration treatment, so that the investment and the operation production cost are greatly reduced; in addition, the iron-containing auxiliary agent can be returned to the slurry preparation section for recycling after the manganese sulfate solution product is filtered, which is also beneficial to reducing the production cost. Solves the problem that the prior technology for desulfurizing by adopting manganese carbonate ore needs special oxidation post-treatment to cause overhigh production cost.
3. According to the invention, the pH value and the ferromanganese mass ratio of the desulfurization slurry in each stage of tower section are accurately controlled in a multi-stage desulfurization and stage-by-stage feeding mode, the generation of the manganese dithionate is effectively controlled while high-efficiency desulfurization is ensured, the concentration of the manganese dithionate in a manganese sulfate solution product discharged from the first stage of tower section is not more than 1.6g/L, and the concentration of the manganese sulfate can reach 164g/L or more.
4. The method disclosed by the invention is simple in process, easy to control the reaction process, low in production cost and easy to realize large-scale industrial production, and can greatly improve the utilization rate of manganese carbonate ore resources while realizing the resource utilization of sulfur in the flue gas.
Drawings
FIG. 1 is a schematic process flow diagram of the process of the present invention.
Detailed Description
The following examples are provided to remove high-concentration SO in flue gas by using manganese carbonate ore2The process for the preparation of manganese sulphate solution is described in detail. It should be noted that the embodiments are only used for further illustration of the present invention, and should not be construed as limiting the scope of the present invention, and the person skilled in the art should make some insubstantial modifications and adjustments to the embodiments based on the above disclosure without inventive step, and should still fall within the scope of the present invention.
Example 1
The manganese carbonate ore used in this example was produced from garna, and the composition analysis of the manganese carbonate ore is shown in table 1. The iron-containing auxiliary agent is iron ore. Manganese carbonate ore slurry is prepared by using electrolytic manganese anolyte, the concentration of manganese sulfate in the electrolytic manganese anolyte is 39.8g/L, and the acid concentration is 34 g/L. The flue gas is simulated by laboratory, and the specific composition is 5% of SO212% oxygen, the balance being nitrogen.
TABLE 1 analysis of manganese carbonate ore composition
The method comprises the following specific steps:
(1) slurry preparation
Firstly, manganese carbonate ore is crushed and sieved by a 100-mesh sieve to obtain manganese carbonate mineral powder, and an iron-containing auxiliary agent is crushed and sieved by a 100-mesh sieve.
Preparing desulfurization slurry for feeding of a final-stage tower section: mixing manganese carbonate mineral powder with an iron-containing auxiliary agent to obtain mixed mineral powder, wherein the iron content in the mixed mineral powder is 3 wt.%, and fully mixing electrolytic manganese anolyte with the mixed mineral powder according to the liquid-solid weight ratio of 15:1 to prepare desulfurization slurry.
Preparing desulfurization slurry for graded feeding: mixing manganese carbonate mineral powder with an iron-containing auxiliary agent to obtain mixed mineral powder, wherein the iron content in the mixed mineral powder is 2-8 wt%, and fully mixing electrolytic manganese anolyte with the mixed mineral powder to prepare desulfurization slurry; because the compositions of the desulfurization slurry in each stage of tower section are different, in order to realize the accurate control of the pH value and the ferromanganese mass ratio of the desulfurization slurry in each stage of tower section, the solid content and the ferromanganese mass ratio of the desulfurization slurry continuously added into the slurry pool arranged at the bottom of each stage of tower section are different, and the specific composition of the desulfurization slurry fed in stages needs to be determined according to the actual composition condition of the desulfurization slurry in each stage of tower section, the target pH value and the ferromanganese mass ratio and the solid content requirement of the desulfurization slurry in each stage of tower section during specific application.
(2) Desulfurization and leaching
Adopts a multi-stage spray tower consisting of five-stage tower sections to carry out desulfurization and leaching of manganese in manganese carbonate ore, and high-concentration SO2Flue gas enters from a first-stage tower section, the prepared desulfurization slurry in the step (1) enters from a fifth-stage tower section of a multi-stage spray tower, meanwhile, slurry pools with feed ports are arranged at the bottoms of the tower sections of the multi-stage spray tower, the desulfurization slurry prepared in the step (1) is continuously added into the slurry pools arranged at the bottoms of the tower sections of the stages for graded feeding, so that the pH values of the desulfurization slurry from the first-stage tower section to the fifth-stage tower section are controlled to be about 2.0, 2.5, 3, 3.5 and 4 in sequence, the manganese-iron ratio in the desulfurization slurry is controlled to be about 15:1, 12:1, 10:1 and 10:1 in sequence, the solid content of the desulfurization slurry in the tower sections of the stages is controlled to be 2-7%, the desulfurization slurry and the flue gas reversely flow between the tower sections of the multi-stage spray tower, and the desulfurization slurry is lifted to a spray head by virtue of a slurry circulating pump arranged at the tower sections of the stages so that the desulfurization slurry and the desulfurization slurry are, contact reaction is carried out with flue gas entering from the lower part of the tower section to remove SO in the flue gas2And is impregnated withDischarging manganese in the manganese carbonate ore, and controlling the temperature of the desulfurization slurry and the temperature of the flue gas to maintain the contact reaction temperature between 40 and 70 ℃, wherein the liquid-gas ratio of the desulfurization slurry to the flue gas is 26L:1m3(ii) a The desulfurized slurry is fully leached in the tower section of the current stage, then enters the tower section of the previous stage, and is discharged from the tower section of the first stage to obtain a manganese sulfate solution product; fully removing SO from flue gas in the tower section of the stage2Then enters the next tower section and is finally discharged by the fifth tower section.
And (3) in the step (2), a multi-stage spray tower consisting of five-stage tower sections is adopted to carry out desulfurization and leaching, and the total reaction time is controlled to be about 1-2 h.
In the embodiment, after desulfurization is performed by the multi-stage spray tower composed of the five-stage tower section, the flue gas SO at the outlet of the fifth-stage tower section2The concentration is less than 200mg/m3The emission can reach the standard; the desulfurization slurry discharged from the first-stage tower section is a manganese sulfate solution product, the concentration of manganese sulfate in the manganese sulfate solution product is 164g/L, the concentration of sulfuric acid is 22g/L, the concentration of sulfurous acid is 3g/L, and the concentration of manganese dithionate is 1.4 g/L. The manganese sulfate solution product is subjected to filtration, impurity removal and secondary filtration treatment, and then purified and impurity removed, and can be directly used for producing manganese sulfate or electrolytic manganese metal, and iron-containing slag obtained after secondary filtration is returned to the step (1) for preparing desulfurization slurry.
Example 2
Manganese carbonate ore used in this example was produced in Guangxi, and the composition analysis of manganese carbonate ore is shown in Table 2. The iron-containing auxiliary agent adopts high-iron waste slag. Manganese carbonate ore slurry is prepared by using electrolytic manganese anolyte, the concentration of manganese sulfate in the electrolytic manganese anolyte is 39.8g/L, and the acid concentration is 34 g/L. The flue gas is simulated by laboratory, and the specific composition is 7% of SO212% oxygen, the balance being nitrogen.
TABLE 2 analysis of manganese carbonate ore composition
The method comprises the following specific steps:
(1) slurry preparation
Firstly, manganese carbonate ore is crushed and sieved by a 100-mesh sieve to obtain manganese carbonate mineral powder, and an iron-containing auxiliary agent is crushed and sieved by a 100-mesh sieve.
Preparing desulfurization slurry for feeding of a final-stage tower section: mixing manganese carbonate mineral powder with an iron-containing auxiliary agent to obtain mixed mineral powder, wherein the iron content in the mixed mineral powder is 5 wt.%, and fully mixing electrolytic manganese anolyte with the mixed mineral powder according to the liquid-solid weight ratio of 15:1 to prepare desulfurization slurry.
Preparing a desulfurization slurry for staged feeding: mixing manganese carbonate mineral powder with an iron-containing auxiliary agent to obtain mixed mineral powder, wherein the iron content in the mixed mineral powder is 2-8 wt%, and fully mixing electrolytic manganese anolyte with the mixed mineral powder to prepare desulfurization slurry; because the compositions of the desulfurization slurry in each stage of tower section are different, in order to realize the accurate control of the pH value and the ferromanganese mass ratio of the desulfurization slurry in each stage of tower section, the solid content and the ferromanganese mass ratio of the desulfurization slurry continuously added into the slurry pool arranged at the bottom of each stage of tower section are different, and the specific composition of the desulfurization slurry fed in stages needs to be determined according to the actual composition condition of the desulfurization slurry in each stage of tower section, the target pH value and the ferromanganese mass ratio and the solid content requirement of the desulfurization slurry in each stage of tower section during specific application.
(2) Desulfurization and leaching
Adopts a multi-stage spray tower consisting of six stages of tower sections to carry out desulfurization and leaching manganese in manganese carbonate ore, and high-concentration SO2The flue gas enters from the first stage tower section, the desulfurization slurry prepared in the step (1) enters from the sixth stage tower section of the multi-stage spray tower, meanwhile, slurry pools with feed ports are arranged at the bottoms of all the tower sections of the multi-stage spray tower, the desulfurization slurry prepared in the step (1) is continuously added into the slurry pool arranged at the bottom of each tower section for graded feeding, controlling the pH values of the desulfurization slurry from the first-stage tower section to the sixth-stage tower section to be about 2.0, 2.5, 3, 3.5, 4 and 4 in sequence, controlling the manganese-iron ratio in the desulfurization slurry to be about 15:1, 12:1, 10:1 and 9:1 in sequence, controlling the solid content of the desulfurization slurry in each stage of tower section to be 2-7%, enabling the desulfurization slurry and the flue gas to reversely flow between each stage of tower section of the multi-stage spray tower, and the desulfurization slurry is lifted to the spray head by the slurry circulating pump arranged at each stage of the tower section to be desulfurized.The slurry is circularly sprayed in each stage of tower section and is in contact reaction with the flue gas entering from the lower part of the tower section to remove SO in the flue gas2And leaching manganese in the manganese carbonate ore, and controlling the temperature of the desulfurization slurry and the temperature of the flue gas to maintain the contact reaction temperature between 40 and 70 ℃, wherein the liquid-gas ratio of the desulfurization slurry to the flue gas is 30L:1m3(ii) a The desulfurized slurry is fully leached in the tower section of the current stage, then enters the tower section of the previous stage, and is discharged from the tower section of the first stage to obtain a manganese sulfate solution product; fully removing SO from flue gas in the tower section of the stage2Then enters the next-stage tower section and is finally discharged by the sixth-stage tower section.
And (3) in the step (2), a multi-stage spray tower consisting of five-stage tower sections is adopted to carry out desulfurization and leaching, and the total reaction time is controlled to be about 2-3 h.
In this embodiment, after desulfurization is performed by the multi-stage spray tower composed of six stages of tower sections, flue gas SO at the outlet of the sixth stage of tower section2The concentration is less than 200mg/m3The emission can reach the standard; the desulfurization slurry discharged from the first-stage tower section is a manganese sulfate solution product, the concentration of manganese sulfate in the manganese sulfate solution product is 181g/L, the concentration of sulfuric acid is 27g/L, the concentration of sulfurous acid is 2.8g/L, and the concentration of manganese dithionate is 1.6 g/L. The manganese sulfate solution product is subjected to filtration, impurity removal and secondary filtration treatment, and then purified and impurity removed, and can be directly used for producing manganese sulfate or electrolytic manganese metal, and iron-containing slag obtained after secondary filtration is returned to the step (1) for preparing desulfurization slurry.
The embodiments described above are intended to assist those skilled in the art in better understanding the present invention, and it is to be understood that the scope of the present invention is not limited to such specifically recited and described embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (8)
1. Method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2The method for preparing the manganese sulfate solution is characterized by comprising the following steps of:
(1) slurry preparation
Preparing desulfurization slurry for feeding of a final-stage tower section: fully mixing electrolytic manganese anolyte and mixed mineral powder according to the liquid-solid weight ratio of (15-20): 1 to prepare desulfurization slurry, or fully mixing water and mixed mineral powder according to the liquid-solid weight ratio of (15-20): 1 and adjusting the pH value to 2-5 by using sulfuric acid to prepare desulfurization slurry;
preparing desulfurization slurry for graded feeding: fully mixing the electrolytic manganese anolyte with the mixed mineral powder to prepare desulfurization slurry, or fully mixing water with the mixed mineral powder and adjusting the pH value to 2-5 with sulfuric acid to prepare desulfurization slurry;
the mixed mineral powder is obtained by mixing manganese carbonate mineral powder and an iron-containing auxiliary agent, and the iron content of the mixed mineral powder is 2-8 wt.%; the manganese content of manganese carbonate ore used for preparing manganese carbonate powder is at least 20%;
(2) desulfurization and leaching
Desulfurizing and leaching by adopting a multi-stage spray tower to obtain high-concentration SO2The method comprises the steps of (1) enabling flue gas to enter from a first-stage tower section of a multi-stage spray tower, enabling the prepared desulfurization slurry to enter from a last-stage tower section of the multi-stage spray tower, meanwhile, continuously adding the desulfurization slurry prepared in the step (1) into a slurry pool arranged at the bottom of each-stage tower section of the multi-stage spray tower for graded feeding, controlling the pH value of the desulfurization slurry in each-stage tower section to be 2-5 and the manganese-iron mass ratio to be (8-15): 1, enabling the desulfurization slurry and the flue gas to flow reversely between each-stage tower section of the multi-stage spray tower, enabling the desulfurization slurry to be circularly sprayed in each-stage tower section of the multi-stage spray tower to be in contact reaction with the flue gas entering from the lower part of the tower section, and2and leaching manganese in manganese carbonate ore, wherein the contact reaction temperature is 40-70 ℃, and the liquid-gas ratio of the desulfurization slurry to the flue gas is (20-30) L:1m3(ii) a The desulfurized slurry is fully leached in the tower section of the current stage, then enters the tower section of the previous stage, and is discharged from the tower section of the first stage to obtain a manganese sulfate solution product; fully removing SO from flue gas in the tower section of the stage2Then enters the next stage of tower section until SO2The content reaches the standard and is discharged from the last stage tower section;
in the step (2), controlling the pH value of the desulfurization slurry in the next-stage tower section not to be less than that of the desulfurization slurry in the previous-stage tower section according to the direction from the first-stage tower section to the last-stage tower section; and controlling the mass ratio of ferromanganese in the desulfurized slurry in the next tower section to be not more than the mass ratio of ferromanganese in the desulfurized slurry in the last tower section according to the direction from the first tower section to the last tower section.
2. The method for removing high-concentration SO in flue gas by using manganese carbonate ore according to claim 12The method for preparing the manganese sulfate solution is characterized in that the solid content of the desulfurization slurry of each stage of tower section is controlled to be 2% -7% in the step (2).
3. The method for removing high-concentration SO in flue gas by using manganese carbonate ore according to claim 12The method for preparing the manganese sulfate solution is characterized in that in the step (2), the total liquid-solid weight ratio of desulfurization slurry in the multistage spray tower is controlled to be (2-4) to 1.
4. The method for removing high-concentration SO in flue gas by using manganese carbonate ore according to claim 12The method for preparing the manganese sulfate solution is characterized in that the total reaction time of desulfurization and leaching in the step (2) by adopting a multi-stage spray tower is 1-4 h.
5. The method for removing high-concentration SO in flue gas by using manganese carbonate ore according to claim 12The method for preparing the manganese sulfate solution is characterized in that the number of tower section stages of the multi-stage spray tower adopted in the step (2) is 3-7.
6. The method for removing high-concentration SO in flue gas by using manganese carbonate ore according to claim 12The method for preparing the manganese sulfate solution is characterized in that in the step (2), the temperature of the desulfurization slurry is 40-70 ℃, and the temperature of flue gas is 80-150 ℃.
7. The method for removing high-concentration SO in flue gas by using manganese carbonate ore according to claim 12The method for preparing the manganese sulfate solution is characterized in that the iron-containing auxiliary comprises iron ore and high-iron waste residue.
8. The method for removing high-concentration SO in flue gas by using manganese carbonate ore according to claim 12The method for preparing the manganese sulfate solution is characterized in that in the step (2), the content of manganese sulfate in a manganese sulfate solution product discharged from the first-stage tower section is not lower than 120g/L, and the manganese sulfate solution product can be directly used for producing manganese sulfate or electrolytic manganese metal after purification and impurity removal.
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