CN114917700A - Method for desulfurizing and decarbonizing flue gas by using electrolytic manganese ammonium sulfate double salt - Google Patents
Method for desulfurizing and decarbonizing flue gas by using electrolytic manganese ammonium sulfate double salt Download PDFInfo
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
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Abstract
A process for desulfurizing and decarbonizing fume by use of the compound salt of electrolytic manganese ammonium sulfate includes dissolving, regulating pH value with ammonia water, sequentially loading it in absorption tower to absorb carbon dioxide and sulfur dioxide in industrial fume, respectively generating manganese carbonate, ammonium sulfate and basic magnesium carbonate, depositing them in ammonium sulfate solution, solid-liquid separation, washing with water, baking and packing. The magnesium-removed liquid is concentrated, crystallized, solid-liquid separated and packed to obtain the ammonium magnesium sulfate compound fertilizer, the mother liquid returns to the concentration crystallizer for circulation, and the condensate of the crystallizer returns to the previous working section to dissolve ammonium sulfate double salt. The process has the advantages of low investment on equipment, high desulfurization and decarburization efficiency, suitability for desulfurization and decarburization of tail gas of industrial kilns such as thermal power around an electrolytic manganese production base, cement and the like, realization of the aim of carbon neutralization, effective recovery of ammonium, magnesium and sulfur resources in the electrolytic manganese production process and realization of the technical effect of 'one arrow and two carves'.
Description
Technical Field
The invention relates to the field of chemical production, in particular to a method for desulfurizing and decarbonizing flue gas by using electrolytic manganese ammonium sulfate double salt.
Background
Ammonium sulfate double salt crystals are produced by 1.2 tons per ton of manganese metal, and the annual production amount is more than 120 million tons. A large amount of ammonium sulfate double salt crystals are stockpiled in a slag field, so that the land is occupied, the construction cost and the management cost of the slag field are increased, the risk of environmental pollution is caused, the bottleneck for restricting the strategic development of enterprises is realized, meanwhile, huge economic value is also reserved, and an effective way for properly treating the ammonium sulfate double salt crystals is not provided at present. Therefore, how to comprehensively utilize the waste residues in the slag yard not only protects the environment, changes waste into valuable and recycles, but also makes the development of recycling economy an urgent requirement for sustainable development, and is a problem to be solved urgently by enterprises.
Disclosure of Invention
In order to solve the technical problems in the prior art, it is necessary to provide a method for desulfurizing and decarbonizing flue gas by using an electrolytic manganese ammonium sulfate double salt. A method for desulfurizing and decarbonizing flue gas by utilizing electrolytic manganese ammonium sulfate double salt is characterized by comprising the following steps:
(1) flue gas washing: the flue gas is in countercurrent contact with water sprayed out of the flue gas washing device through the flue gas washing device to remove dust in the flue gas, and the flue gas discharged from the flue gas washing device is obtained;
(2) preparing manganese carbonate: dissolving electrolytic manganese ammonium sulfate double salt and adding ammonia water to adjust the pH value to obtain a standard electrolytic manganese ammonium sulfate double salt solution, placing the standard electrolytic manganese ammonium sulfate double salt solution in a manganese carbonate preparation device, allowing flue gas discharged from a flue gas washing device to enter the manganese carbonate preparation device to perform countercurrent contact reaction with the standard electrolytic manganese ammonium sulfate double salt solution sprayed by the manganese carbonate preparation device, and then performing solid-liquid separation to obtain a supernatant after reaction of prepared manganese carbonate and prepared manganese carbonate, and allowing the flue gas discharged from the flue gas washing device to pass through the manganese carbonate preparation device to obtain flue gas discharged from the manganese carbonate preparation device;
(3) preparing basic magnesium carbonate: adding ammonia water into the supernatant obtained after the reaction of preparing the manganese carbonate to adjust the pH value, pumping the supernatant from a basic magnesium carbonate preparation device, carrying out countercurrent contact reaction with the flue gas discharged from the manganese carbonate preparation device, and carrying out solid-liquid separation to obtain the supernatant obtained after the reaction of preparing the basic magnesium carbonate and preparing the basic magnesium carbonate, wherein the flue gas discharged from the manganese carbonate preparation device passes through the basic magnesium carbonate preparation device to obtain the flue gas discharged from the basic magnesium carbonate preparation device;
(4) preparing magnesium ammonium sulfate: and (3) treating the flue gas out of the basic magnesium carbonate preparation device by a demisting device, then discharging the flue gas into the atmosphere, and sending the supernatant obtained after the reaction of preparing the basic magnesium carbonate into an evaporation crystallizer for evaporation and crystallization to separate out the ammonium magnesium sulfate.
Preferably, (4) evaporating and crystallizing in an evaporative crystallizer in the preparation of the ammonium magnesium sulfate, separating the ammonium magnesium sulfate, recycling distilled water and free ammonium, wherein the distilled water and the free ammonium are recycled, the distilled water and the free ammonium are in countercurrent contact with cold water for condensation, and the condensed ammonia water returns to the step (2) of preparing the manganese carbonate to dissolve the electrolytic manganese ammonium sulfate double salt for recycling.
Preferably, (1) flue gas CO in flue gas washing 2 Concentration of 8-15%, SO 2 The concentration is 1-3%.
Preferably, (2) the pH value of the standard electrolytic manganese double salt solution in the preparation of the manganese carbonate is 6.5-7.
Preferably, (3) adding ammonia water into the supernatant after the reaction for preparing the manganese carbonate in the preparation of the basic magnesium carbonate to adjust the pH value to 9-12.
Preferably, (4) basic carbon is generated in preparation of magnesium ammonium sulfateFlue gas CO of magnesium preparation device 2 ＜1％，SO 2 ≤100ppm。
Preferably, the chemical reaction equation in (2) is CO 2 +MnSO 4 +2NH 3 OH＝MnCO 3 +(NH 4 ) 2 SO 4 +1/2O 2 。
Preferably, the chemical reaction equation in (3) is 4CO 2 +5MgSO 4 +10NH 3 OH+2.5H 2 O＝(MgCO 3 ) 4 .Mg(OH)2.5H 2 O+5(NH 4 ) 2 SO 4 +2.5O 2 。
Preferably, the SO in the flue gas is absorbed 2 Has the chemical reaction equation of SO 2 +2NH 3 OH＝(NH 4 ) 2 SO 4 。
According to the technical scheme, the method for desulfurizing and decarbonizing the flue gas by using the electrolytic manganese ammonium sulfate double salt is a novel technology invented in experimental research combining the aim of realizing carbon neutralization advocated by the state in the research on resource utilization of the electrolytic manganese ammonium sulfate slag. The principle is that electrolytic manganese ammonium sulfate double salt is dissolved, ammonia water is used for regulating the PH value, the electrolytic manganese ammonium sulfate double salt and the ammonia water are sequentially injected into an absorption tower to absorb sulfur dioxide and carbon dioxide in industrial flue gas, ammonium sulfate, manganese carbonate and basic magnesium carbonate are respectively generated and precipitated from the ammonium sulfate solution, and the products of the manganese carbonate and the basic magnesium carbonate are obtained after solid-liquid separation, water washing, drying and packaging. The magnesium-removed liquid is concentrated, crystallized, solid-liquid separated and packed to obtain the ammonium magnesium sulfate compound fertilizer, the mother liquid returns to the concentration crystallizer for circulation, and the condensate of the crystallizer returns to the previous working section to dissolve ammonium sulfate double salt. The process equipment has low investment and high desulfurization and decarburization efficiency, is suitable for desulfurization and decarburization of tail gas of industrial kilns such as thermal power around an electrolytic manganese production base, cement and the like, realizes the aim of carbon neutralization, can effectively recover ammonium, magnesium and sulfur resources in the electrolytic manganese production process, and realizes the technical effect of 'one-arrow double-carving'. The content of the agricultural magnesium ammonium sulfate is more than or equal to 95 percent; the water content is less than or equal to 4.4 percent; the main element (N) is more than or equal to 20 percent; the medium element components (Mg, S and Ca) are more than or equal to 25 percent; the trace elements (Mn and Fe) are more than or equal to 1 percent; harmful heavy metals (Pb is less than 0.005 percent, Cd is less than 0.005 percent, AS is less than 0.005 percent, Hg is less than 0.005 percent, Cr is less than 0.005 percent, manganese carbonate is more than or equal to 95 percent, and the impurity content in basic magnesium carbonate is less than 0.1 percent, so that the product meets the national and industrial standards.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
The main component of the electrolytic manganese ammonium sulfate double salt comprises MnSO 4 About 10%, MgSO 4 About 32%; (NH) 4 ) 2 SO 4 About 38%; the remainder being water of crystallization. The flue gas from the outlet of the kiln induced draft fan or the industrial flue gas contains CO 2 About 8-15%, SO 2 About 1-3%, as shown in figure 1, the flue gas from the outlet of the induced draft fan of the kiln is contacted with the circulating water sprayed from the top of the tower through the flue gas washing tower in a countercurrent manner to wash away the micro dust in the flue gas, the flue gas is discharged from the bottom of the tower into a settling pond to settle, the supernatant is recycled, and the base solution is periodically pumped into a filter press for filter pressing and discharging by a slurry pump. The purpose of this step is to wash the tiny dust in the industrial flue gas, need make up water when washing for the first time, when circulating and carrying out this workshop section and washing, can utilize the supernatant fluid after this workshop section sedimentation tank subsides repeatedly, do not cause the wasting of resources, the industrial flue gas that this workshop section washed cleanly gets into next workshop section and is used for preparing manganese carbonate.
Dissolving the electrolytic manganese ammonium sulfate double salt and adding ammonia water to adjust the pH value to 6.5-7 to obtainThe standard electrolytic manganese double salt solution is placed on a manganese carbonate carbonization tower, the flue gas discharged from a flue gas washing tower enters the manganese carbonate carbonization tower from the bottom to react with the standard electrolytic manganese double salt solution sprayed on the top of the tower in a countercurrent contact manner to generate manganese carbonate precipitate, the manganese carbonate precipitate is discharged from the bottom of the tower to a manganese carbonate thickener for concentration, the concentrated solution is discharged from the bottom of the thickener to a vacuum belt filter for filtration, is washed, is sent to a manganese carbonate dryer for drying at the temperature of 200 ℃, and is packaged by a packaging machine for sale. The separated supernatant in the section enters the next section for further reaction, and the reacted flue gas in the section also enters the next section for continuous reaction, wherein the reaction in the section mainly aims at using CO in the industrial flue gas 2 With MnSO in standard electrolytic manganese ammonium sulfate double salt solution 4 、NH 3 The OH reaction is used for preparing manganese carbonate and absorbing CO in the flue gas 2 The effect of the invention is embodied, not only CO in the flue gas is removed 2 Manganese carbonate is also prepared.
Adding ammonia water into the supernatant separated in the upper working section to adjust the pH value to 9-12, filtering by a ceramic filter, pumping into the top of a basic magnesium carbonate carbonization tower, and making countercurrent contact with flue gas from a manganese carbonate carbonization tower to further absorb CO in tail gas 2 、SO 2 And pumping the generated basic magnesium carbonate precipitate and ammonium sulfate solution into a basic magnesium carbonate thickener from the bottom of the tower, filtering and washing the concentrated solution by a vacuum belt filter, and then sending the filtered and washed concentrated solution into a dryer to be dried, packaged and sold at the temperature of 120 ℃. Tail gas after decarburization and desulfurization, CO 2 ＜1％；SO 2 Less than or equal to 100ppm is discharged into the atmosphere through an electric demister. The main purpose of the reaction in the section is to further absorb sulfur dioxide and carbon dioxide in the industrial flue gas, generate basic magnesium carbonate and further remove CO in the industrial flue gas 2 、SO 2 And at the moment, the industrial flue gas reaches the emission standard, is discharged into the atmosphere after passing through the electric demister, and reacts to generate the basic magnesium carbonate while completely purifying the industrial flue gas.
Filtering the supernatant after separating the basic magnesium carbonate by a ceramic filter, sending the filtered supernatant into a multi-effect evaporation crystallizer for evaporation crystallization, and centrifugally separating by a centrifugal machine to obtain the magnesium ammonium sulfate agricultural chemical fertilizer, and packaging and selling the magnesium ammonium sulfate agricultural chemical fertilizer. Distilled water and free ammonium enter a condensation tower from the tower bottom to be in countercurrent contact with 5-degree cold water from a water chiller for condensation, and condensed weak ammonia water returns to the air-floating ammonium sulfate double salt dissolving tank of the front section for recycling. In the working section, ammonia water and sulfur dioxide in the first two working sections react to generate ammonium sulfate, in the working section, the main component of the supernatant liquid after the separation of the basic magnesium carbonate is an ammonium sulfate solution containing certain magnesium sulfate, and the ammonium sulfate solution containing certain magnesium sulfate is evaporated and crystallized to obtain the ammonium sulfate magnesium compound fertilizer.
Example (b):
the working process comprises the following steps: flue gas at an outlet of a draught fan of the furnace kiln and supplementing water enter a flue gas washing tower through a heat exchanger, the heat exchanger conducts heat transfer on an evaporation crystallizer, the flue gas is in countercurrent contact with water sprayed on the top of the tower through the flue gas washing tower to wash away tiny dust in the flue gas, the flue gas is discharged into a sedimentation tank from the bottom of the tower to be settled, supernatant liquid is recycled in the flue gas washing tower after being filtered, and bottom liquid is periodically pumped into a filter press for filter pressing and discharging through a slurry pump.
Dissolving ammonium sulfate complex salt in an air-floating dissolving tank, adding 30% ammonia water to adjust the pH value to 6.5, allowing flue gas discharged from a flue gas washing tower to enter a manganese carbonate carbonization tower from the bottom to perform countercurrent contact reaction with an electrolytic manganese complex salt solution sprayed on the top of the tower to generate manganese carbonate precipitate, allowing the reacted flue gas to enter the next working section after being concentrated by a manganese carbonate thickener, allowing the supernatant to enter the next working section, filtering and washing the concentrated solution by a vacuum belt type filtering and washing machine, returning the filtrate to the air-floating ammonium sulfate dissolving tank for recycling in the working section, and drying the washed manganese carbonate by a manganese carbonate dryer, and packaging and selling.
Filtering the supernatant from the previous working section by a ceramic filter, adding 30% ammonia water to adjust the pH value to 10, allowing the supernatant to enter the working section for reaction to generate basic magnesium carbonate, pumping the basic magnesium carbonate into the top of a basic magnesium carbonate carbonization tower to be in countercurrent contact with flue gas from a manganese carbonate carbonization tower to generate basic magnesium carbonate precipitate and an ammonium sulfate solution, pumping the basic magnesium carbonate precipitate and the ammonium sulfate solution into a basic magnesium carbonate thickener from the bottom of the tower, allowing the concentrated supernatant to be used in the next working section, filtering and washing the concentrated solution by a vacuum belt type filtering and washing machine, returning the filtrate to a magnesium carbonate solution circulating pool for circulation in the working section for reaction, drying the washed basic magnesium carbonate by a basic magnesium carbonate dryer, and packaging for sale.
After the smoke in the upper working section is decarbonized and desulfurized, CO 2 ＜1％；SO 2 Less than or equal to 100ppm and is discharged into the atmosphere from the top of the tower through an electric demister. The liquid after gas-liquid separation by the electric demister enters a front section for recycling, supernatant liquid of the upper section is filtered by a ceramic filter and then is sent to an evaporation crystallizer for evaporation and crystallization, the evaporation crystallizer and a heat exchanger of the front section carry out heat transfer, heat transfer is carried out between an evaporation water condensation tower and the evaporation crystallizer, and a centrifuge centrifugally separates out the ammonium magnesium sulfate agricultural chemical fertilizer to be packaged and sold. The mother liquor returns to the concentration crystallizer for circulation. Make-up water is supplemented into the evaporation water condensing tower, the evaporation water condensing tower is connected with the sedimentation tank of the front section for circular supplement, distilled water and free ammonium enter the condensing tower from the tower bottom and are in countercurrent contact condensation with 5-degree cold water from a water cooler, and condensed dilute ammonia water returns to the air-floating ammonium sulfate double-salt dissolving tank of the front section for circular use.
The principle of the invention is as follows: the main component of the electrolytic manganese ammonium sulfate double salt is MnSO 4 About 10%; MgSO (MgSO) 4 About 32%; (NH) 4 )2SO 4 About 38%; the balance being water of crystallization. The principle of removing carbon dioxide and sulfur in flue gas by using the double salt is as follows:
1、CO 2 +MnSO 4 +2NH 3 OH＝MnCO 3 +(NH 4 ) 2 SO 4 +1/2O 2 and (4) precipitating and separating manganese carbonate.
2、4CO 2 +5MgSO 4 +10NH 3 OH+2.5H 2 O＝(MgCO 3 ) 4 .Mg(OH)2.5H 2 O+5(NH 4 ) 2 SO 4 +2.5O 2 And (4) precipitating and separating basic magnesium carbonate.
3、SO 2 +2NH 3 OH＝(NH 4 ) 2 SO 4 Ammonium sulfate solution containing certain magnesium sulfate is evaporated and crystallized to obtain the ammonium magnesium sulfate compound fertilizer.
Claims (9)
1. A method for desulfurizing and decarbonizing flue gas by utilizing electrolytic manganese ammonium sulfate double salt is characterized by comprising the following steps:
(1) flue gas washing: the flue gas is in countercurrent contact with water sprayed out of the flue gas washing device through the flue gas washing device to remove the micro dust in the flue gas, so that the flue gas discharged from the flue gas washing device is obtained;
(2) preparing manganese carbonate: dissolving electrolytic manganese ammonium sulfate double salt and adding ammonia water to adjust the pH value to obtain a standard electrolytic manganese ammonium sulfate double salt solution, placing the standard electrolytic manganese ammonium sulfate double salt solution in a manganese carbonate preparation device, allowing the flue gas discharged from a flue gas washing device to enter the manganese carbonate preparation device to perform countercurrent contact reaction with the standard electrolytic manganese ammonium sulfate double salt solution sprayed by the manganese carbonate preparation device, and then performing solid-liquid separation to obtain a supernatant after the reaction of the prepared manganese carbonate and the prepared manganese carbonate, and allowing the flue gas discharged from the flue gas washing device to pass through the manganese carbonate preparation device to obtain the flue gas discharged from the manganese carbonate preparation device;
(3) preparing basic magnesium carbonate: adding ammonia water into the supernatant obtained after the reaction for preparing the manganese carbonate to adjust the pH value, pumping the supernatant into a basic magnesium carbonate preparation device, carrying out countercurrent contact reaction with the flue gas discharged from the manganese carbonate preparation device, and carrying out solid-liquid separation to obtain the supernatant obtained after the reaction for preparing the basic magnesium carbonate and preparing the basic magnesium carbonate, wherein the flue gas discharged from the manganese carbonate preparation device passes through the basic magnesium carbonate preparation device to obtain the flue gas discharged from the basic magnesium carbonate preparation device;
(4) preparing magnesium ammonium sulfate: and the flue gas discharged from the basic magnesium carbonate preparation device is treated by a demisting device and then discharged into the atmosphere, and the supernatant after the reaction of preparing the basic magnesium carbonate is sent to an evaporative crystallizer for evaporation and crystallization to separate out the ammonium magnesium sulfate.
2. The method for desulfurization and decarbonization of flue gas by using the electrolytic manganese ammonium sulfate double salt according to claim 1, characterized in that in the step (4), after evaporation crystallization in an evaporative crystallizer during preparation of ammonium magnesium sulfate, ammonium magnesium sulfate is separated, and distilled water and free ammonium are recycled, wherein the distilled water and the free ammonium are recycled, namely, the distilled water and the free ammonium are in countercurrent contact with cold water for condensation, and the condensed ammonia water is returned to the step (2) for dissolution of the electrolytic manganese ammonium sulfate double salt during preparation of manganese carbonate for recycling.
3. The method of claim 1, wherein the flue gas is desulfurized and decarbonized by using the electrolytic manganese ammonium sulfate double saltAnd (1) flue gas CO in flue gas scrubbing 2 Concentration of 8-15%, SO 2 The concentration is 1-3%.
4. The method for desulfurizing and decarbonizing flue gas by using the electrolytic manganese ammonium sulfate double salt as claimed in claim 1, wherein the ph value of the standard electrolytic manganese double salt solution in the step (2) of preparing the manganese carbonate is 6.5 to 7.
5. The method for desulfurizing and decarbonizing flue gas by using the electrolytic manganese ammonium sulfate double salt as claimed in claim 1, wherein the pH value of the supernatant obtained after the reaction for preparing the manganese carbonate in the (3) preparation of the basic magnesium carbonate is adjusted to 9-12 by adding ammonia water.
6. The method for desulfurizing and decarbonizing the flue gas by the electrolytic manganese ammonium sulfate double salt according to claim 1, wherein the flue gas CO of the device for preparing basic magnesium carbonate in the preparation of ammonium magnesium sulfate in (4) is discharged 2 ＜1％，SO 2 ≤100ppm。
7. The method for desulfurizing and decarbonizing flue gas by using the electrolytic manganese ammonium sulfate double salt as claimed in claim 1, wherein the chemical reaction equation in (2) is CO 2 +MnSO 4 +2NH 3 OH＝MnCO 3 +(NH 4 ) 2 SO 4 +1/2O 2 。
8. The method for desulfurizing and decarbonizing flue gas by using the electrolytic manganese ammonium sulfate double salt as claimed in claim 1, wherein the chemical reaction equation in (3) is 4CO 2 +5MgSO 4 +10NH 3 OH+2.5H 2 O＝(MgCO 3 ) 4 .Mg(OH)2.5H 2 O+5(NH 4 ) 2 SO 4 +2.5O 2 。
9. The method for desulfurizing and decarbonizing flue gas by using the electrolytic manganese ammonium sulfate double salt as claimed in claim 1, wherein SO in the flue gas is absorbed 2 The chemical reaction equation of (a) is SO 2 +2NH 3 OH＝(NH 4 ) 2 SO 4 。
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