CN106377993B - SO in pyrolusite slurry desorption flue gas 2 And method and device for recycling thereof - Google Patents
SO in pyrolusite slurry desorption flue gas 2 And method and device for recycling thereof Download PDFInfo
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- CN106377993B CN106377993B CN201610926562.8A CN201610926562A CN106377993B CN 106377993 B CN106377993 B CN 106377993B CN 201610926562 A CN201610926562 A CN 201610926562A CN 106377993 B CN106377993 B CN 106377993B
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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Abstract
The invention discloses a method for removing SO in flue gas by pyrolusite 2 And its resource utilization method and device, wet grinding pyrolusite with ball mill, adding water, regulating pH value to obtain pyrolusite pulp, mixing with SO-containing material 2 The flue gas is subjected to reverse contact reaction desulfurization in a desulfurizing tower, the flue gas is defogged and then enters the next working procedure, the circulating ore pulp flow is subjected to vacuum filtration, pH adjustment by lime and then filtration, filtrate pH adjustment sedimentation tank sedimentation, vacuum evaporation crystallization solid-liquid separation and filtrate carbonization solid-liquid separation; the invention uses manganese ore pulp to remove SO in the flue gas 2 At the same time SO 2 The manganese sulfate and manganese carbonate react with manganese dioxide in manganese ore to generate manganese sulfate, and the manganese sulfate monohydrate and the manganese carbonate with high added value are obtained through the processes of purification, evaporative crystallization, mother liquor carbonization and the like, SO that SO in flue gas is treated 2 Treating, preventing secondary pollution of flue gas, generating high added value product, and solving SO 2 And obtains economic benefit.
Description
Technical Field
The invention relates to a method for removing SO in flue gas by pyrolusite 2 And a method and a device for recycling the raw ore, thereby achieving the purpose of controlling pollution by the raw ore and simultaneously obtaining products with high added value, and belonging to the technical field of environmental protection.
Background
The flue gas desulfurization method is classified according to the phase of the desulfurizing agent, and can be broadly classified into two types, dry desulfurization and wet desulfurization. The current technological process of flue gas desulfurization at home and abroad exceeds 200, and the process and the matched equipment thereof have industrial application value of more than ten. The wet desulfurization is simple in operation, low in cost and most commonly used. In the wet desulfurization technology, the lime-limestone method is the most mature at present, and has the advantages of high desulfurization efficiency (the desulfurization rate is more than 90%), low cost of absorbent and wide source, but has complex system, large investment and energy consumption, low application value of production waste residue and easy secondary pollution; although byproducts of an ammonia water absorption method (an ammonia acid method) can be used as fertilizers, ammonia volatilization loss is accompanied during desulfurization, and the byproducts are limited by an ammonia source; other sodium methods or double-alkali methods have the same high cost, the utilization value of byproducts is not great, enterprises are under great pressure economically, and along with the perfection of environmental regulations, new desulfurization processes and equipment are being sought.
Rich manganese resource in ChinaThe manganese ore pulp is used for removing sulfur dioxide in the flue gas, SO that the environmental pollution is eliminated, and the SO can be recycled 2 Meanwhile, the additional value of pyrolusite is improved, and enterprises can obtain additional economic benefits.
The invention uses manganese ore pulp to remove SO in the flue gas 2 At the same time propose SO 2 A method and a device for purifying and separating products after reacting with pyrolusite and further producing manganese sulfate and manganese carbonate with high added value.
The invention is characterized in that: (1) Taking manganese ore pulp as a desulfurizing agent for SO in flue gas 2 Treating, preventing secondary pollution of the flue gas, and achieving the purpose of treating pollution by waste; (2) In the desulfurization process, the desulfurized slurry is filtered by a vacuum filter through a slurry pump, is heated in a purifying tank, is added with lime to adjust the pH value, is filtered to remove manganese dithionate, is added with ammonia water and clarified sediment through a neutralizing tank, is filtered to remove other metal impurities, and is subjected to vacuum evaporation crystallization, is separated by a centrifugal machine when the clear solution is hot, and is dried by microwaves to obtain manganese sulfate monohydrate; adding sodium carbonate into the evaporated mother liquor in a carbonization tank to generate manganese carbonate precipitation, separating by a centrifugal machine, and drying a filter cake by microwaves to obtain manganese carbonate; (3) Manganese ore pulp is used as a desulfurizing agent, SO that the operation cost is low, and SO is removed 2 And simultaneously, resource utilization is developed.
Disclosure of Invention
The invention aims to provide a method for removing SO in flue gas by manganese ore pulp 2 The method for recycling the same comprises the following specific steps:
(1) Wet grinding pyrolusite by using a ball mill, sieving with a 200-mesh sieve, adding water to prepare pyrolusite pulp, wherein the solid content of the pyrolusite pulp is 18-22%, and regulating the pH value of the pyrolusite pulp to be 3.5-4.5;
(2) The flue gas with higher temperature firstly enters a waste heat exchanger to generate low-pressure steam for evaporation process, the flue gas enters a desulfurizing tower from the lower part after being cooled, the soft manganese ore pulp prepared in the step (1) is pumped to the desulfurizing tower to spray, the flue gas and the sprayed manganese ore pulp are in reverse contact reaction, the flue gas is discharged from a flue gas outlet after being desulfurized, the flue gas enters the next process or is directly emptied after passing through a demister, the slurry is circularly sprayed and is replaced and supplemented while being sprayed, the process is continuously carried out, the recycled slurry is mainly manganese sulfate, secondly ferric sulfate, small amount of calcium, magnesium, iron and aluminum and small amount of heavy metal ions are contained, and the manganese dithionate generated in the desulfurizing process is also contained, and the slurry is subjected to vacuum filtration;
(3) Adding lime into the filtrate obtained by filtering in the step (2) to adjust the pH value to 4.5-5, heating to 70-80 ℃ by using steam to decompose manganese dithionate, standing for precipitation, and filtering the precipitate to obtain purified filtrate;
(4) Pouring the purified filtrate obtained in the step (3) into a neutralization tank, adding ammonia water, adjusting the pH value to be 5-5.5, enabling calcium, magnesium, iron, aluminum and a small amount of heavy metal ions to generate hydroxide precipitate, placing the neutralization solution into a clarification and sedimentation tank, clarifying the precipitate, and further filtering the precipitate by a steaming filter to obtain clear liquid;
(5) Performing vacuum evaporation crystallization on the clear solution obtained in the step (4) by using a vacuum evaporator, wherein the vacuum degree is 0.07-0.08 MPa, the temperature is 70-80 ℃, the mass percent concentration of the manganese sulfate monohydrate is concentrated to 38-40%, centrifugal separation is performed while the manganese sulfate monohydrate is hot, and filter residues are dried to obtain the manganese sulfate monohydrate;
(6) And (5) adding sodium carbonate into the filtrate obtained by separation in the step (5) after cooling, generating manganese carbonate precipitate, carrying out solid-liquid separation, drying filter residues to obtain manganese carbonate, heating the separated filtrate by direct steam in an ammonia distillation tower, controlling the outlet temperature of a separator by a mixture of ammonia and steam, and returning ammonia to a neutralization tank for recycling.
And (3) controlling the outlet temperature of the separator to be 80-95 ℃ in the step (6).
Another object of the invention is to provide the method for removing SO in flue gas by manganese ore pulp 2 And a device for recycling, comprising a pressurizing blower 1, a desulfurizing tower 2, a demister 3, a slurry pump I4, a circulating pump 5, a slurry mixing tank 6, a desulfurizing slurry storage tank 7, a slurry pump II8, a vacuum filter I9, a receiving tank I10, a vacuum pump I11, a purifying tank 12, a screw pump 13, a filter press 14, a neutralizing tank 15, a clarifying sedimentation tank 16, a slurry pump III17, a vacuum filter II18, a receiving tank II19, a vacuum pump II20, a vacuum evaporator 21, a centrifuge I22, a clean liquid pump 23, a carbonization tank 24, a centrifuge II25 and a mother liquorA liquid tank 26, an ammonia pump 27, an ammonia distillation tower 28, a separator 29, a dryer I30 and a dryer II31;
the pressure air blower 1 is connected with the lower part of the desulfurizing tower 2, the bottom of the desulfurizing tower 2 is provided with a material containing box, the upper part is provided with a spraying device, the material containing box is connected with the circulating pump 5, the circulating pump 5 is connected with the spraying device, the top of the desulfurizing tower 2 is provided with a flue gas outlet, the flue gas outlet is connected with the demister 3, the material containing box at the bottom of the desulfurizing tower 2 is also connected with a slurry pump I4, the slurry pump I4 is connected with a slurry regulating tank 6, the material containing box at the bottom of the desulfurizing tower 2 is also connected with a desulfurizing slurry storage tank 7, the desulfurizing slurry storage tank 7 is connected with a vacuum filter I9 through a slurry pump II8, the vacuum filter I9 is connected with a receiving tank I10, the top of the receiving tank I10 is connected with a vacuum pump I11, the bottom of the receiving tank I10 is connected with a purifying tank 12, the bottom of the purifying tank 12 is connected with a filter press 14 through a screw pump 13, the filter press 14 is connected with a middle tank 15, the middle tank 15 is connected with a settling tank 16, the settling tank 16 is connected with a vacuum filter III 18 through a slurry pump III17, the vacuum filter II18 is connected with a receiving tank II19, the top of the receiving tank II19 is connected with a vacuum pump II20, the bottom of the receiving tank II19 is sequentially connected with a vacuum evaporator 21, a centrifuge I22 is sequentially with a centrifuge I22 is connected with a centrifugal machine 31 and a supernatant fluid 25 in turn, a supernatant fluid 25 is sequentially separated from a dryer 25 is concentrated by a dryer 25, and the supernatant fluid is sequentially dried by a 25, and the supernatant fluid is sequentially concentrated by a 25, and the supernatant is sequentially concentrated in the supernatant is sequentially in the tank is sequentially connected with the supernatant fluid is sequentially and the supernatant fluid is sequentially concentrated by the supernatant fluid is sequentially by the pump 25.
The clarifying sedimentation tank 16 is internally provided with honeycomb sloping plate packing.
Stirring paddles are arranged in the slurry mixing tank 6, the desulfurization slurry storage tank 7, the purification tank 12, the neutralization tank 15 and the carbonization tank 24.
The ammonia-containing steam with the ammonia concentration increased by about 10% by the separator 29 is returned to the neutralization tank 15 for recycling.
The invention has the advantages that:
1. pyrolusite is used as desulfurizing agent to treat SO in fume 2 The treatment is carried out, the secondary pollution of the flue gas is prevented, the purpose of treating pollution by waste is realized, and the purpose of environmental protection is realized.
2. In the desulfurization process, manganese dioxide in pyrolusite is simultaneously utilized in a recycling way to generate additional valueHigher manganese sulfate monohydrate and manganese carbonate, and removing SO 2 Meanwhile, pyrolusite resources are fully utilized, the utilization of the pyrolusite resources is made full use of, and the purpose of resource utilization is achieved.
3. The invention takes manganese ore as the desulfurizing agent, and has low running cost; meanwhile, the resource utilization is developed, the high added value manganese sulfate monohydrate and manganese carbonate are produced through the desulfurization product, the obvious economic benefit of enterprises is improved, and 1 ton of SO is recovered 2 Can obtain 3000-3500 yuan, does not cost for environmental pollution treatment, and has good economic benefit.
Drawings
FIG. 1 is a schematic view of the structure of the device according to the present invention;
in the figure, 1-a pressurized blower; 2-a desulfurizing tower; 3-a demister; 4-slurry pump I; 5-a circulation pump; 6-a size mixing tank; 7-a desulfurization slurry storage tank; 8-slurry pump II; 9-a vacuum filter I; 10-receiving tank I; 11-a vacuum pump I; 12-a purifying tank; 13-a screw pump; 14-a filter press; 15-a neutralization tank; 16-clarifying a sedimentation tank; 17-slurry pump III; 18-a vacuum filter II; 19-receiving tank II; 20-a vacuum pump II; 21-a vacuum evaporator; 22-centrifuge I; 23-a clear liquid pump; 24-carbonization groove; 25-centrifuge II; 26-mother liquor tank; 27-an ammonia pump; 28-an ammonia still; 29-a contractor; 30-a dryer I; 31-dryer II.
Detailed Description
The invention will now be described in further detail with reference to the drawings and to specific examples.
Example 1
As shown in a first graph, the SO in the flue gas is removed by manganese ore pulp 2 The recycling device comprises a pressurizing blower 1, a desulfurizing tower 2, a demister 3, a slurry pump I4, a circulating pump 5, a slurry mixing tank 6, a desulfurizing slurry storage tank 7, a slurry pump II8, a vacuum filter I9, a receiving tank I10, a vacuum pump I11, a purifying tank 12, a screw pump 13, a filter press 14, a neutralizing tank 15, a clarifying sedimentation tank 16, a slurry pump III17, a vacuum filter II18, a receiving tank II19, a vacuum pump II20, a vacuum evaporator 21, a centrifuge I22, a clean liquid pump 23, a carbonization tank 24, a centrifuge II25, a mother liquor tank 26, an ammonia pump 27, an ammonia still 28, a separator 29, a dryer I30 and a dryer II31; the pressurizing blower 1 is connected with the lower part of the desulfurizing tower 2, and the bottom of the desulfurizing tower 2The device comprises a material containing box, a spraying device is arranged on the upper portion of the material containing box, the material containing box is connected with a circulating pump 5, the circulating pump 5 is connected with the spraying device, three rows of spraying devices are arranged at different heights, 5 spray heads are arranged in each row, a flue gas outlet is arranged at the top of a desulfurizing tower 2, the flue gas outlet is connected with a demister 3, a slurry pump I4 is further connected with the material containing box at the bottom of the desulfurizing tower 2, the slurry pump I4 is connected with a size mixing tank 6, the material containing box at the bottom of the desulfurizing tower 2 is further connected with a desulfurizing slurry storage tank 7, the desulfurizing slurry storage tank 7 is connected with a vacuum filter I9 through a slurry pump II8, the vacuum filter I9 is connected with a receiving tank I10, the top of the receiving tank I10 is connected with a vacuum pump 11, the bottom of the vacuum filter I9 is connected with a purifying tank 12, the bottom of the purifying tank 12 is connected with a filter press 14 through a screw pump 13, the filter press 14 is connected with a middle and tank 15, the middle and bottom of the purifying tank 15 is connected with a settling tank 16, honeycomb sloping plate filler is arranged in the settling tank 16, the settling tank 16 is connected with a vacuum filter II18 through a slurry pump III17, the vacuum II18 is connected with a receiving tank II19, the top of the receiving tank II19 is connected with a vacuum pump II19, the bottom of the vacuum filter II19 is sequentially connected with a vacuum centrifuge 21, the bottom of the receiving tank I22 is sequentially connected with a centrifugal machine I22, the centrifugal machine I is sequentially connected with a dry machine I25 and a dry machine II is sequentially connected with a dry machine 25, a dry pump 25 and a dry tank 25, a 25 and a 13 is sequentially connected with a dry tank 25, a 25 and a 13, a 25 is sequentially connected with a 25 and a 25 is sequentially and a 25 to a 25 of the respective dry tank are sequentially connected with a 25 are respectively and a 13.
The device is used for removing SO in the flue gas from manganese ore pulp 2 The method for recycling the same comprises the following specific steps:
(1) Wet grinding pyrolusite by using a ball mill, sieving with a 200-mesh sieve, adding water into a slurry mixing tank 6 to prepare pyrolusite slurry, wherein the solid content of the pyrolusite slurry is 20%, and regulating the pH value of the pyrolusite slurry to be 3.5;
(2) The flue gas is anode calcined flue gas, and the flue gas volume is 60000Nm 3 /h, SO in flue gas 2 The content of the extract is 3000mg/Nm 3 The average temperature is 220 ℃ and the emission of flue gas SO is required 2 Less than 100mg/Nm 3 The flue gas with higher temperature firstly enters a waste heat exchanger to generate low-pressure steam for evaporation process, and the cooled flue gas enters from the lower part of a desulfurizing tower 2 through a pressurizing blower 1Feeding, pumping the soft manganese ore pulp prepared in the step (1) to a desulfurizing tower 2 by using a circulating pump 5, spraying by using a spraying device, wherein the spraying device is provided with three rows of 5 spray heads at different heights, the flue gas and the sprayed manganese ore pulp are in reverse contact reaction, the flue gas is desulfurized and then comes out from a flue gas outlet, and after passing through a demister 5, the flue gas SO is discharged 2 The content was 90mg/Nm 3 Discharging after reaching standards, directly discharging, circularly spraying slurry, continuously spraying while discharging and supplementing the slurry, wherein the circulated slurry mainly comprises manganese sulfate, ferric sulfate, a small amount of calcium, magnesium, iron and aluminum, a small amount of heavy metal ions, manganese dithionate generated in the desulfurization process, and the slurry is stored in a desulfurization slurry storage tank 7, pumped to a vacuum filter I9 by a slurry pump II8 for vacuum filtration, and filtrate obtained by filtration enters a receiving tank I10;
(3) The filtrate obtained by filtering in the step (2) enters a purifying tank 12 from a receiving tank I10, the purifying tank 12 is provided with a stirring paddle, lime is added while stirring to adjust the pH value of slurry to 5, steam generated by waste heat of flue gas is heated to 80 ℃ to decompose manganese dithionate, the slurry is pumped to a filter press 14 through a screw pump 13, and sediment is filtered to obtain purified filtrate, and the purified filtrate enters a neutralizing tank 15;
(4) Adding ammonia water into the purified filtrate in the neutralization tank 15 in the step (3), adjusting the pH value to be 5, enabling calcium, magnesium, iron, aluminum and a small amount of heavy metal ions to generate hydroxide precipitate, placing the neutralization solution into a clarification and sedimentation tank 16, carrying out precipitation and clarification by using honeycomb sloping plate filler, pumping the liquid into a vacuum filter II18 by using a slurry pump III17, filtering the liquid to obtain clear liquid, and feeding the clear liquid into a receiving tank II19;
(5) Carrying out vacuum evaporation crystallization on clear liquid in the receiving tank II19 in the step (4) through a vacuum evaporator 21, wherein the vacuum degree of the vacuum evaporator 21 is 0.08MPa, the temperature is 80 ℃, the mass percentage concentration of manganese sulfate monohydrate is concentrated to 38%, centrifugal separation is carried out on the clear liquid while the clear liquid is hot through a centrifugal machine I22, and manganese sulfate monohydrate is obtained after filter residues are dried through a dryer II31, so that about 2000 tons of manganese sulfate monohydrate is produced each year;
(6) And (3) cooling the filtrate obtained by centrifugal separation in the step (5), adding sodium carbonate after entering a carbonization tank 24 through a clear liquid pump 23 to generate manganese carbonate precipitate, centrifuging by a centrifugal machine II25 to perform solid-liquid separation, drying filter residues by a dryer I30 to obtain manganese carbonate, pumping the filtrate into a mother liquor tank 26, pumping the filtrate into an ammonia distillation tower 28 through an ammonia pump 27, heating by using steam generated by direct flue gas waste heat, heating a mixture of ammonia and steam through a separator 29, controlling the temperature of flue gas at an outlet of the separator 29 to 80 ℃, returning the ammonia concentration to about 10% to a neutralization tank 15 for recycling, and producing about 2100 tons of manganese carbonate each year.
Example 2
The manganese ore pulp in this example removes SO from flue gas 2 The method for recycling the waste water is the same as that of the embodiment 1 except that two rows of spraying devices are arranged, and each row of spraying devices is provided with 7 spraying heads, and the specific steps are as follows:
(1) Wet grinding pyrolusite by using a ball mill, sieving with a 200-mesh sieve, adding water into a slurry mixing tank 6 to prepare pyrolusite slurry, wherein the solid content of the pyrolusite slurry is 22%, and regulating the pH value of the pyrolusite slurry to be 4;
(2) The flue gas is the flue gas of a boiler of a power plant, and the flue gas volume is 100000Nm 3 /h, SO in flue gas 2 The content is 2000mg/Nm 3 The average temperature is 120 ℃, and the flue gas SO is required to be discharged 2 Less than 400mg/Nm 3 The flue gas with higher temperature firstly enters a waste heat exchanger to generate low-pressure steam for evaporation process, the cooled flue gas enters from the lower part of a desulfurizing tower 2 through a pressurizing blower 1, the soft manganese ore pulp prepared in the step (1) is pumped to the desulfurizing tower 2 through a circulating pump 5 and sprayed through a spraying device, the flue gas and the sprayed manganese ore pulp are in reverse contact reaction, the flue gas is desulfurized and then comes out from a flue gas outlet, and SO in the flue gas passes through a demister 5 2 Is absorbed and removed SO 2 SO from the flue gas 2 The content of the extract is 300mg/Nm 3 The flue gas is discharged after reaching standards, the flue gas is directly discharged, slurry is discharged and replenished through circulating spraying, the process is continuously carried out, the circulating slurry is mainly manganese sulfate, then is ferric sulfate, contains a small amount of calcium, magnesium, iron and aluminum, a small amount of heavy metal ions, further contains manganese dithionate generated in the desulfurization process, the slurry is stored in a desulfurization slurry storage tank 7, is pumped to a vacuum filter I9 through a slurry pump II8 for vacuum filtration, and filtrate obtained through filtration enters a receiving tank I10;
(3) The filtrate obtained by filtering in the step (2) enters a purifying tank 12 from a receiving tank I10, the purifying tank 12 is provided with a stirring paddle, lime is added while stirring to adjust the pH value of slurry to 4.5, steam is used for heating to 70 ℃ to decompose manganese dithionate, the slurry is pumped to a filter press 14 through a screw pump 13, and sediment is filtered to obtain purified filtrate, and the purified filtrate enters a neutralizing tank 15;
(4) Adding ammonia water into the purified filtrate in the neutralization tank 15 in the step (3), adjusting the pH value to 5.5, enabling calcium, magnesium, iron, aluminum and a small amount of heavy metal ions to generate hydroxide precipitate, placing the neutralized liquid into a clarification and sedimentation tank 16, carrying out long-time sedimentation and clarification by using honeycomb sloping plate filler, pumping the liquid into a vacuum filter II18 by using a slurry pump III17, further filtering, and obtaining clear liquid to enter a receiving tank II19;
(5) Carrying out vacuum evaporation crystallization on clear liquid in the receiving tank II19 in the step (4) through a vacuum evaporator 21, wherein the vacuum degree of the vacuum evaporator 21 is 0.07MPa, the temperature is 70 ℃, the concentration of manganese sulfate monohydrate is concentrated to 39%, centrifugal separation is carried out on the clear liquid while the clear liquid is hot through a centrifugal machine I22, and filter residues are dried through a dryer II31 to obtain manganese sulfate monohydrate, and 180 tons of manganese sulfate monohydrate are produced each year;
(6) And (3) cooling the filtrate obtained by centrifugal separation in the step (5), adding sodium carbonate after entering a carbonization tank 24 through a clear liquid pump 23 to generate manganese carbonate precipitate, centrifuging by a centrifuge II25 to perform solid-liquid separation, drying filter residues by a dryer I30 to obtain manganese carbonate, pumping the filtrate into a mother liquor tank 26, pumping the filtrate into an ammonia distillation tower 28 through an ammonia pump 27, heating by using steam generated by direct flue gas waste heat, and recycling the mixture of ammonia and steam through a separator 29, wherein the flue gas temperature at an outlet of the separator 29 is controlled to be 90 ℃, and the ammonia concentration reaches about 10% and returns to a neutralization tank for recycling, thereby producing about 1900 tons of manganese carbonate each year.
Example 3
The manganese ore pulp in this example removes SO from flue gas 2 The same device as in example 1 is adopted, and the specific steps are as follows:
(1) Wet grinding pyrolusite by using a ball mill, sieving with a 200-mesh sieve, adding water into a slurry mixing tank 6 to prepare pyrolusite slurry, wherein the solid content of the pyrolusite slurry is 18%, and regulating the pH value of the pyrolusite slurry to be 4.5;
(2) Preparation of sulfuric acid from flue gasTreatment capacity of factory flue gas and sulfuric acid tail gas is 200000Nm 3 And/h, converting SO in tail gas of two-rotation two-absorption sulfuric acid device 2 The content of 650mg/Nm 3 The tail gas outlet requires SO 2 The content was 100mg/Nm 3 The flue gas with high temperature firstly enters a waste heat exchanger to generate low-pressure steam for evaporation process, the cooled flue gas enters from the lower part of a desulfurizing tower 2 through a pressurizing blower 1, the pyrolusite pulp prepared in the step (1) is pumped into the desulfurizing tower to spray, the flue gas and the sprayed manganese ore pulp are in reverse contact reaction, the flue gas is discharged from a flue gas outlet after desulfurization, and SO in the flue gas after passing through a demister 5 2 Is absorbed and removed SO 2 SO from the flue gas 2 The content of the extract is 300mg/Nm 3 The flue gas is discharged after reaching standards and enters the next working procedure, the slurry is discharged and replenished while being sprayed, the process is continuously carried out, the recycled slurry is mainly manganese sulfate, then is ferric sulfate, contains a small amount of calcium, magnesium, iron and aluminum and a small amount of heavy metal ions, also contains manganese dithionate generated in the desulfurization process, the slurry is stored in a desulfurization slurry storage tank 7, is pumped to a vacuum filter I9 through a slurry pump II8 for vacuum filtration, and filtrate obtained by filtration enters a receiving tank I10;
(3) The filtrate obtained by filtering in the step (2) enters a purifying tank 12 from a receiving tank I10, the purifying tank 12 is provided with a stirring paddle, lime is added while stirring to adjust the pH value of slurry to 4.5, steam is used for heating to 75 ℃ to decompose manganese dithionate, the slurry is pumped to a filter press 14 through a screw pump 13, and sediment is filtered to obtain purified filtrate, and the purified filtrate enters a neutralizing tank 15;
(4) Adding ammonia water into the purified filtrate in the neutralization tank 15 in the step (3), adjusting the pH value to be 5, enabling calcium, magnesium, iron, aluminum and a small amount of heavy metal ions to generate hydroxide precipitate, placing the neutralization solution into a clarification and sedimentation tank 16, carrying out precipitation and clarification by using honeycomb sloping plate filler, pumping the liquid into a vacuum filter II18 by using a slurry pump III17, filtering the liquid to obtain clear liquid, and feeding the clear liquid into a receiving tank II19;
(5) Carrying out vacuum evaporation crystallization on clear liquid in the receiving tank II19 in the step (4) through a vacuum evaporator 21, wherein the vacuum degree of the vacuum evaporator 21 is 0.08Mpa, the temperature is 75 ℃, the mass percentage concentration of manganese sulfate monohydrate is concentrated to 40%, centrifugal separation is carried out on the clear liquid while the clear liquid is hot through a centrifugal machine I22, and the filter residues are dried through a dryer II31 to obtain manganese sulfate monohydrate, so that about 1800 tons of manganese sulfate monohydrate is produced each year;
(6) And (3) cooling the filtrate obtained by centrifugal separation in the step (5), adding sodium carbonate after entering a carbonization tank 24 through a clear liquid pump 23 to generate manganese carbonate precipitate, centrifuging by a centrifugal machine II25 to perform solid-liquid separation, drying filter residues by a dryer I30 to obtain manganese carbonate, pumping the filtrate into a mother liquor tank 26, pumping the filtrate into an ammonia distillation tower 28 through an ammonia pump 27, heating by using steam generated by direct flue gas waste heat, and recycling the mixture of ammonia and steam through a separator 29, wherein the flue gas temperature at the outlet of the separator 29 is controlled to be 95 ℃, the ammonia concentration reaches about 10%, and returning to a neutralization tank for recycling, thereby producing about 1500 tons of manganese carbonate each year.
It will be appreciated that modifications and variations of the present invention are possible to those skilled in the art from the above teachings, and are within the scope of the appended claims.
Claims (4)
1. Removal of SO in flue gas from manganese ore pulp 2 The method for recycling the same is characterized by comprising the following specific steps:
(1) Wet grinding pyrolusite, sieving with a 200-mesh sieve, adding water to prepare pyrolusite pulp, wherein the solid content of the pyrolusite pulp is 18-22%, and regulating the pH value of the pyrolusite pulp to be 3.5-4.5;
(2) Cooling the flue gas with higher temperature by a waste heat exchanger, then allowing the flue gas to enter from the lower part of a desulfurizing tower, pumping the soft manganese ore pulp prepared in the step (1) to the desulfurizing tower for spraying, allowing the flue gas to reversely contact and react with the sprayed manganese ore pulp, allowing the flue gas to exit from a flue gas outlet after desulfurization, allowing the flue gas to enter into the next working procedure or be directly emptied after demisting, allowing slurry to circularly spray, performing slurry replacement and supplement while spraying, allowing the process to continuously perform, and performing vacuum filtration on the recycled slurry;
(3) Adding lime into the filtrate obtained by filtering in the step (2) to adjust the pH value to 4.5-5, heating to 70-80 ℃, and filtering the precipitate to obtain purified filtrate;
(4) Adding ammonia water into the purified filtrate obtained in the step (3), adjusting the pH value to be 5-5.5, settling and clarifying, and carrying out vacuum filtration to obtain clear liquid;
(5) Carrying out vacuum evaporation crystallization on the clear liquid obtained in the step (4), wherein the vacuum degree is 0.07-0.08 MPa, the temperature is 70-80 ℃, the mass percent concentration of the manganese sulfate monohydrate is concentrated to 38-40%, and the manganese sulfate monohydrate is obtained after centrifugal separation while the manganese sulfate monohydrate is hot and filter residues are dried;
(6) Adding sodium carbonate into the filtrate obtained by the separation in the step (5) after cooling, generating precipitate, performing solid-liquid separation, drying filter residues to obtain manganese carbonate, controlling the outlet temperature of a separator by the separation of the filtrate, and returning the obtained ammonia gas to the step (4) for recycling;
the manganese ore pulp removes SO in the flue gas 2 And the device of the recycling method comprises a pressurizing blower, a desulfurizing tower, a demister, a slurry pump I, a circulating pump, a slurry mixing tank, a desulfurizing slurry storage tank, a slurry pump II, a vacuum filter I, a receiving tank I, a vacuum pump I, a purifying tank, a screw pump, a filter press, a neutralizing tank, a clarifying sedimentation tank, a slurry pump III, a vacuum filter II, a receiving tank II, a vacuum pump II, a vacuum evaporator, a centrifuge I, a clear liquid pump, a carbonization tank, a centrifuge II, a mother liquid tank, an ammonia pump, an ammonia distillation tower, a separator, a dryer I and a dryer II;
the pressurized blower is connected with the lower part of the desulfurizing tower, the bottom of the desulfurizing tower is provided with a material containing tank, the upper part of the desulfurizing tower is provided with a spraying device, the material containing tank is connected with a circulating pump, the circulating pump is connected with a spraying device, a flue gas outlet at the top of the desulfurizing tower is connected with a demister, the material containing tank at the bottom of the desulfurizing tower is also connected with a slurry pump I, the slurry pump I is connected with a slurry pump I through the slurry pump II, the vacuum filter I is connected with a receiving tank I, the receiving tank I is connected with a vacuum pump I, the bottom of the receiving tank I is connected with a purifying tank, the bottom of the purifying tank is connected with a filter press through a screw pump, the filter press is connected with a neutralization tank, the neutralization tank is connected with a clarification sedimentation tank, the clarification sedimentation tank is connected with a vacuum filter II through the slurry pump III, the vacuum filter II is connected with a vacuum evaporator and a centrifuge I sequentially, the centrifuge I is connected with a dryer II and a cleaning pump sequentially, the carbonization tank and the centrifuge II are sequentially connected with a mother liquor tank respectively, the centrifuge II is connected with an ammonia centrifuge, an ammonia pump, an ammonia separator, a separator and a distillation tank are sequentially connected with a distillation tank.
2. The method for removing SO from flue gas by manganese ore pulp according to claim 1 2 And a method for recycling the same, which is characterized in that the outlet temperature in the step (6) is 80-95 ℃.
3. The method for removing SO from flue gas by manganese ore pulp according to claim 1 2 The method for recycling the waste water is characterized in that a honeycomb sloping plate filler is arranged in the clarification and sedimentation tank.
4. The method for removing SO from flue gas by manganese ore pulp according to claim 1 2 The method for recycling the desulfurization slurry is characterized in that stirring paddles are arranged in the slurry mixing tank, the desulfurization slurry storage tank, the purification tank, the neutralization tank and the carbonization tank.
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| CN108103526B (en) * | 2017-11-13 | 2019-09-27 | 昆明理工大学 | A method of utilizing electrolytic aluminium aluminium ash purifying electrolysis aluminium flue gas and recycling bauxite resource |
| CN110152488B (en) * | 2019-04-28 | 2021-12-03 | 昆明理工大学 | Dry method for removing SO in coke oven flue gas2Method (2) |
| CN110152476B (en) * | 2019-06-18 | 2021-12-21 | 合肥工业大学 | Device and method for synchronous desulfurization and denitrification of flue gas |
| CN110255794A (en) * | 2019-07-02 | 2019-09-20 | 无锡翰思拓科技有限公司 | Soften desulfurization wastewater using ammonium hydroxide and recycles the Zero-discharge treating process of ammonium hydroxide |
| CN110357164B (en) * | 2019-07-08 | 2022-03-15 | 四川大学 | Method for green purification of manganese oxide ore slurry by coupling circulating efficient flue gas desulfurization with manganese sulfate |
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