CN116099349A - Synchronous desulfurization and denitrification method for modified manganese ores - Google Patents
Synchronous desulfurization and denitrification method for modified manganese ores Download PDFInfo
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- CN116099349A CN116099349A CN202310141775.XA CN202310141775A CN116099349A CN 116099349 A CN116099349 A CN 116099349A CN 202310141775 A CN202310141775 A CN 202310141775A CN 116099349 A CN116099349 A CN 116099349A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a method for synchronously desulfurizing and denitrating modified manganese ores, which comprises the following steps: calcining rhodochrosite to obtain a modified manganese material; crushing the modified manganese material; mixing the crushed modified manganese material with liquid to prepare slurry; and carrying out countercurrent contact reaction on the slurry and the calcined flue gas generated by the calcination desulfurization treatment of the manganese slag to realize desulfurization and denitration of the calcined flue gas and produce manganese sulfate. The beneficial effects of the invention are as follows: the process is reasonable, synchronous desulfurization and denitrification are realized, sulfur resources can be recycled to prepare manganese sulfate solution, the manganese sulfate solution can be recycled to the electrolytic manganese working section, the purpose of recycling the resources is achieved, and the effects of reducing cost and enhancing efficiency are realized.
Description
Technical Field
The invention relates to the field of metallurgy, in particular to a method for synchronously desulfurizing and denitrating modified manganese ores.
Background
At present, the manganese slag is mainly formed by adopting a high-temperature calcination desulfurization mode of a rotary kiln to form desulfurized manganese slag, and then the desulfurized manganese slag is used for preparing concrete or cement products and the like, and calcined flue gas contains a large amount of SO2 (sulfur dioxide) and NOx (nitrogen oxides), and because the two gases can form acid rain after entering the atmosphere, the harm to human environment is very great, and therefore, desulfurization and denitrification treatment is required to be carried out on the flue gas.
The traditional desulfurization and denitrification process is carried out by adopting an SCR (selective catalytic reduction) method, raw materials such as limestone, liquid ammonia and the like are needed in the method, so that the operation cost is high, and the generated waste residues cannot be utilized.
Disclosure of Invention
In order to solve the problems, the invention provides a method for synchronously desulfurizing and denitrating modified manganese ores.
The invention is realized by the following technical scheme:
the invention discloses a method for synchronously desulfurizing and denitrating modified manganese ores, which comprises the following steps:
calcining rhodochrosite to obtain a modified manganese material; in the process of producing carbon dioxide by calcining rhodochrosite, the ore is reamed to form a modified manganese ore material which takes micropores and mesopores as main materials and has macropores with a certain proportion;
crushing the modified manganese material;
mixing the crushed modified manganese material with liquid to prepare slurry;
carrying out countercurrent contact reaction on the slurry and calcined flue gas generated by the calcination desulfurization treatment of the manganese slag, consuming sulfur dioxide in the calcined flue gas, adsorbing oxynitride, realizing desulfurization and denitration of the calcined flue gas, and producing manganese sulfate; the treatment speed of the smoke amount can reach 10Nm 3 And/h, the concentration of sulfur dioxide in the flue gas is reduced to below 2.5 percent, no x The content is reduced to 400-600mg/Nm 3 。
Further, the calcination of the rhodochrosite is carried out in a rotary kiln at a temperature of 500-800 ℃.
Further, the crushed granularity of the modified manganese material is controlled to be 100-mesh sieving rate of 95%.
Further, the crushed modified manganese material is mixed with water or anolyte, and the pulp concentration of the slurrying liquid is 10-15%.
Further, the countercurrent contact reaction is a process of enabling slurry to flow downwards from top to bottom in a reaction container, enabling calcination flue gas to flow upwards from bottom to top, and fully contacting and reacting the slurry and the calcination flue gas in the reaction container to consume sulfur dioxide in the calcination flue gas and generate manganese sulfate.
Further, the chemical reaction during the calcination of the rhodochrosite is as follows:
further, the chemical reaction of the countercurrent contact reaction is as follows:
MnO 2 +SO 2 →MnSO 4 。
further, the reaction vessel is a packed tower; the packing tower comprises a tower body, wherein the upper end of the tower body is a calcination flue gas outlet, and the lower end of the tower body is a slurry outlet; the inside of the tower body is sequentially provided with a liquid distributor, a first-stage filler, a liquid redistributor, a second-stage filler and a slurry collector from top to bottom; the liquid distributor is connected with the slurry inlet pipe in a fitting way; a flue gas inlet pipe is arranged between the secondary filler and the slurry collector; slurry is introduced into the slurry inlet pipe, and the flue gas inlet pipe is introduced with the calcination flue gas generated by the manganese slag calcination desulfurization treatment.
Further, the manganese sulfate generated by the countercurrent contact reaction is recycled to the electrolytic manganese liquid preparation section for preparing the manganese sulfate neutral liquid.
The invention has the beneficial effects that: the process is reasonable, synchronous desulfurization and denitrification are realized, sulfur resources can be recycled to prepare manganese sulfate solution, the manganese sulfate solution can be recycled to the electrolytic manganese working section, the purpose of recycling the resources is achieved, and the effects of reducing cost and enhancing efficiency are realized.
Drawings
Fig. 1: the flow diagram of the invention;
fig. 2: the structure of the reaction vessel is schematically shown;
in the figure: 1-tower body, 2-slurry inlet pipe, 3-liquid distributor, 4-first-stage filler, 5-liquid redistributor, 6-second-stage filler, 7-flue gas inlet pipe and 8-slurry collector.
Detailed Description
The invention is further described with reference to the drawings and detailed description which follow:
examples: as shown in fig. 1-2, the method for synchronously desulfurizing and denitrating the modified manganese ore comprises the following steps:
calcining rhodochrosite to obtain a modified manganese material; in the process of producing carbon dioxide by calcining rhodochrosite, the ore is reamed to form a modified manganese ore material which takes micropores and mesopores as main materials and has macropores with a certain proportion;
crushing the modified manganese material;
mixing the crushed modified manganese material with liquid to prepare slurry;
carrying out countercurrent contact reaction on the slurry and calcined flue gas generated by the calcination desulfurization treatment of the manganese slag, consuming sulfur dioxide in the calcined flue gas, adsorbing oxynitride, realizing desulfurization and denitration of the calcined flue gas, and producing manganese sulfate; the treatment speed of the smoke amount can reach 10Nm 3 And/h, the concentration of sulfur dioxide in the flue gas is reduced to below 2.5 percent, no x The content is reduced to 400-600mg/Nm 3 。
Further, the calcination of the rhodochrosite is carried out in a rotary kiln at a temperature of 500-800 ℃.
Further, the crushed granularity of the modified manganese material is controlled to be 100-mesh sieving rate of 95%.
Further, the crushed modified manganese material is mixed with water or anolyte, and the pulp concentration of the slurrying liquid is 10-15%.
Further, the countercurrent contact reaction is a process of enabling slurry to flow downwards from top to bottom in a reaction container, enabling calcination flue gas to flow upwards from bottom to top, and fully contacting and reacting the slurry and the calcination flue gas in the reaction container to consume sulfur dioxide in the calcination flue gas and generate manganese sulfate.
Further, the chemical reaction during the calcination of the rhodochrosite is as follows:
further, the chemical reaction of the countercurrent contact reaction is as follows:
MnO 2 +SO 2 →MnSO 4 。
further, the reaction vessel is a packed tower; the packing tower comprises a tower body 1, wherein the upper end of the tower body 1 is a calcination flue gas outlet, and the lower end of the tower body is a slurry outlet; the inside of the tower body 1 is sequentially provided with a liquid distributor 3, a first-stage filler 4, a liquid redistributor 5, a second-stage filler 6 and a slurry collector 8 from top to bottom; the liquid distributor 3 is assembled and connected with the slurry inlet pipe 2; a flue gas inlet pipe 7 is arranged between the secondary filler 6 and the slurry collector 8; slurry is introduced into the slurry inlet pipe 2, and the flue gas inlet pipe 7 is introduced with the calcination flue gas generated by the manganese slag calcination desulfurization treatment.
When the device works, the slurry enters the tower body 1 from the slurry inlet pipe 2, is distributed to the first-stage filler 4 through the liquid distributor 3 and is distributed to the second-stage filler 6 through the liquid redistributor 5 in sequence, so that the slurry fully contacts and reacts with the calcination flue gas entering from the bottom of the tower body 1; sulfur dioxide in the calcined flue gas is consumed, and after the oxynitride is adsorbed, the oxygen-nitrogen compound reaches the emission standard and is discharged from the top of the tower body 1; manganese dioxide in the slurry reacts with sulfur dioxide to produce manganese sulfate slurry, and the manganese sulfate slurry is collected by a slurry collector 8 and discharged.
Further, the manganese sulfate generated by the countercurrent contact reaction is recycled to the electrolytic manganese liquid preparation section for preparing the manganese sulfate neutral liquid.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (9)
1. The method for synchronously desulfurizing and denitrating the modified manganese ore is characterized by comprising the following steps of:
calcining rhodochrosite to obtain a modified manganese material;
crushing the modified manganese material;
mixing the crushed modified manganese material with liquid to prepare slurry;
and carrying out countercurrent contact reaction on the slurry and the calcined flue gas generated by the calcination desulfurization treatment of the manganese slag to realize desulfurization and denitration of the calcined flue gas and produce manganese sulfate.
2. The method for synchronously desulfurizing and denitrating modified manganese ore as claimed in claim 1, wherein the method comprises the following steps: the temperature of the rhodochrosite during calcination is 500-800 ℃, and the rhodochrosite is carried out in a rotary kiln.
3. The method for synchronously desulfurizing and denitrating modified manganese ore as claimed in claim 1, wherein the method comprises the following steps: the granularity of the modified manganese material is controlled to be 100-mesh sieving rate of 95%.
4. The method for synchronously desulfurizing and denitrating modified manganese ore as claimed in claim 1, wherein the method comprises the following steps: the crushed modified manganese material is mixed with water or anolyte, and the pulp concentration of the slurrying liquid is 10-15%.
5. The method for synchronously desulfurizing and denitrating modified manganese ore as claimed in claim 1, wherein the method comprises the following steps: the countercurrent contact reaction is a process of enabling slurry to flow downwards from top to bottom in a reaction container, enabling calcination flue gas to flow upwards from bottom to top, and fully contacting and reacting the slurry and the calcination flue gas in the reaction container to consume sulfur dioxide in the calcination flue gas and generate manganese sulfate.
6. A modified manganese ore as defined in claim 2The method for desulfurizing and denitrating in steps is characterized by comprising the following steps: the chemical reaction during calcining the rhodochrosite is as follows:
7. the method for synchronously desulfurizing and denitrating modified manganese ore as claimed in claim 5, wherein the method comprises the following steps: the chemical reaction of the countercurrent contact reaction is as follows: mnO (MnO) 2 +SO 2 →MnSO 4 。
8. The method for synchronously desulfurizing and denitrating modified manganese ore according to claim 5 or 7, which is characterized by comprising the following steps: the reaction vessel is a packed tower; the packing tower comprises a tower body (1), wherein the upper end of the tower body (1) is a calcination flue gas outlet, and the lower end of the tower body is a slurry outlet; the inside of the tower body (1) is sequentially provided with a liquid distributor (3), a first-stage filler (4), a liquid redistributor (5), a second-stage filler (6) and a slurry collector (8) from top to bottom; the liquid distributor (3) is assembled and connected with the slurry inlet pipe (2); a flue gas inlet pipe (7) is arranged between the secondary filler (6) and the slurry collector (8); slurry liquid is introduced into the slurry inlet pipe (2), and calcined smoke generated by the calcination and desulfurization treatment of manganese slag is introduced into the smoke inlet pipe (7).
9. The method for synchronously desulfurizing and denitrating modified manganese ore as claimed in claim 1, wherein the method comprises the following steps: and recycling the manganese sulfate generated by the countercurrent contact reaction to an electrolytic manganese liquid preparation section for preparing manganese sulfate neutral liquid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310141775.XA CN116099349A (en) | 2023-02-20 | 2023-02-20 | Synchronous desulfurization and denitrification method for modified manganese ores |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310141775.XA CN116099349A (en) | 2023-02-20 | 2023-02-20 | Synchronous desulfurization and denitrification method for modified manganese ores |
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| CN116099349A true CN116099349A (en) | 2023-05-12 |
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