CN114505323B - Harmless treatment method and equipment for electrolytic manganese slag - Google Patents
Harmless treatment method and equipment for electrolytic manganese slag Download PDFInfo
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- CN114505323B CN114505323B CN202210231195.5A CN202210231195A CN114505323B CN 114505323 B CN114505323 B CN 114505323B CN 202210231195 A CN202210231195 A CN 202210231195A CN 114505323 B CN114505323 B CN 114505323B
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 130
- 239000011572 manganese Substances 0.000 title claims abstract description 130
- 239000002893 slag Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000003756 stirring Methods 0.000 claims abstract description 181
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 145
- 238000005406 washing Methods 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000003825 pressing Methods 0.000 claims abstract description 55
- 230000029087 digestion Effects 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 48
- 238000011085 pressure filtration Methods 0.000 claims abstract description 25
- 239000004576 sand Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 53
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- 230000032683 aging Effects 0.000 claims description 24
- 239000002699 waste material Substances 0.000 claims description 17
- 235000012255 calcium oxide Nutrition 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000012257 stirred material Substances 0.000 claims description 8
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 4
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 abstract description 3
- 229940099596 manganese sulfate Drugs 0.000 abstract description 3
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 3
- 239000011702 manganese sulphate Substances 0.000 abstract description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 description 25
- 239000000706 filtrate Substances 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 239000010865 sewage Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000012856 packing Methods 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a harmless treatment method and equipment for electrolytic manganese slag. The water content of the electrolytic manganese slag after washing, stirring and primary pressure filtration is about 15%, the residual soluble sulfate (about 30-60%) in the washed manganese slag is eliminated through digestion, stirring, and meanwhile, overflowed ammonia gas is recovered; after digestion and stirring, the water content of the manganese slag is about 100%, the water content of the manganese slag after secondary filter pressing can reach about 20%, and the residual soluble sulfate (about 20-40%) after the primary digestion reaction is removed through mixing and stirring, and meanwhile overflowed ammonia gas is recovered; and dry fine sand is added in the mixing and stirring process to increase the friction force of the manganese slag, so that the problem of manganese slag bonding equipment is solved. The method effectively removes a large amount of ammonium sulfate and soluble manganese sulfate remained in the electrolytic manganese slag, the water content of the manganese slag mixture after three times of stirring is about 10%, and the ammonium salt removal rate can reach more than 90%.
Description
Technical Field
The invention relates to the field of resource utilization of electrolytic manganese slag, in particular to a harmless treatment method and equipment for electrolytic manganese slag.
Background
The electrolytic manganese slag is a type II solid waste in general industrial solid waste, has fine particles, no magnetism, no toxicity and difficult water dissolution, and the manganese slag has about 2/3 particles smaller than 100 mu m. The manganese slag after filter pressing in an electrolysis plant is agglomerated (the water content is generally 13-16%), and the viscosity is high. The electrolyte slag is weakly acidic (pH is generally 4-6), has high sulfur content, exists in various forms, and mainly exists in the form of soluble sulfate (ammonium sulfate, magnesium sulfate, residual manganese sulfate and the like, which account for about 6-10%) except that most of sulfate exists in the form of dihydrate gypsum (accounting for about 15-18%). In the aqueous solution, the content of ammonia nitrogen in the manganese slag is very high, and when water is added and stirred, irritant gas (ammonia gas) is emitted, and besides, the manganese slag also contains trace heavy metal ions and the like.
In a long time, the main treatment method of the harmful solid wastes such as manganese slag in China is safe landfill or stockpiling, the landfill and stockpiling are not long-term strategies, and a large amount of manganese slag which is needed to be treated urgently exists in the domestic electrolytic manganese factories at present. Therefore, the polluted wastes such as manganese slag and the like must be treated scientifically and safely so as to achieve the purposes of protecting the environment and fully utilizing the resources. At present, the treatment of manganese slag at home and abroad is mainly solidification or stabilization treatment and resource utilization. Guangxi is a great saving of manganese ore resources, more electrolytic manganese enterprises exist, and urgent demands are made on the treatment of electrolytic manganese residues at present. The resource utilization of the electrolytic manganese slag is beneficial to improving the digestion and absorption of solid waste and the industrialized transformation and upgrading, and has great significance on environmental safety.
At present, the utilization of the solid waste of the manganese slag is mainly applied to wall materials, building materials and the like, and as the manganese slag contains certain heavy metal ions, ammonia nitrogen and other harmful components, harmless pretreatment is needed before the application, so that the harmless treatment of the recycled and regenerated products can be ensured, and the problem of bonding equipment exists in the stirring process of the manganese slag. The invention designs a harmless treatment method and related equipment for electrolytic manganese slag aiming at the current harmless treatment requirement of manganese slag.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a harmless treatment method and equipment for electrolytic manganese slag.
The implementation mode of the invention is as follows: the harmless treatment method of the electrolytic manganese slag comprises the following steps: (1) washing and stirring: adding water into manganese slag obtained by filter pressing in an electrolytic manganese plant for washing and stirring, and conveying ammonia gas generated in the washing and stirring process to an ammonia gas treatment system for treatment; (2) primary filter pressing: carrying out filter pressing on the manganese slag after washing and stirring with water to separate solid from liquid, wherein the separated waste liquid is directly used for an electrolytic manganic acid leaching process, and the separated manganese slag is transmitted to the next process; (3) digestion and stirring: adding quicklime and water into the manganese slag subjected to primary pressure filtration, stirring, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the addition amount of the quicklime is 4-6% of the mass of the manganese slag, the addition amount of the water is 100-200% of the mass of the manganese slag, and the stirring time is 20-30 min; (4) secondary filter pressing: carrying out secondary filter pressing on the manganese slag mixture after digestion and stirring to separate solid from liquid, treating the separated wastewater to reach the standard, recycling the wastewater, and conveying the separated waste slag to the next working procedure; (5) mixing and stirring: mixing and stirring the waste residues subjected to secondary filter pressing with dry fine sand for 20-30 min, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the addition amount of the dry fine sand is 5-10% of the mass of manganese slag; (6) And (3) conveying the mixed and stirred materials to an ageing warehouse, and ageing to obtain harmless manganese slag materials. Through water washing, stirring and primary pressure filtration, solid, liquid and gas of electrolytic manganese slag are separated, waste water is directly used for an electrolytic manganic acid leaching process, waste gas enters an ammonia gas treatment system, and manganese slag enters a digestion and stirring process; the aim of digestion and stirring is to eliminate most of soluble sulfate and ammonia contained in the manganese slag after water washing; the purpose of mixing and stirring is to remove the residual soluble sulfate after digestion and stirring; the purpose of adding dry fine sand in the mixing and stirring process is to consume a part of water and increase the friction force of the manganese slag so as to solve the problem of manganese slag bonding equipment. After digestion stirring and mixing stirring, the water content of the manganese slag mixture is about 10%, the ammonium salt removal rate can reach more than 90%, and the homogenization effect of the manganese slag mixture is improved by stacking and ageing the mixed and stirred materials, and meanwhile, the residual trace ammonia gas can be eliminated. The electrolytic manganese slag can be applied to sintered or non-sintered products after harmless treatment.
Further, the waste water separated by the secondary pressure filtration is subjected to neutralization precipitation treatment by lime. Because part of ammonia gas generated after the first stirring is dissolved in water, the filtrate after the filter pressing contains a certain amount of soluble sulfate, quick lime is utilized for neutralization and precipitation, the waste water treatment reaches the standard and can be used for an electrolytic manganic acid leaching process, and the generated precipitated slag can be directly used for making bricks.
Further, the fineness modulus of the dry fine sand is 1.6-2.2, and the average grain diameter is 0.25-0.35 mm.
Further, the equipment adopted by the electrolytic manganese slag innocent treatment method is characterized by comprising water washing stirring equipment, primary filter pressing equipment, a filtrate recovery tank, digestion stirring equipment, secondary filter pressing equipment, a sewage treatment system, mixing stirring equipment, an ammonia gas treatment system and an aging warehouse, wherein the upper ends of the water washing stirring equipment, the digestion stirring equipment and the mixing stirring equipment are connected with the ammonia gas treatment system through air pipes; the lower end of the washing stirring device is connected with primary filter pressing equipment through a transmission pipeline, and the primary filter pressing equipment is connected to a filtrate recovery tank and digestion stirring equipment through a transmission pipeline respectively; the bottom of the digestion stirring equipment is connected with the secondary pressure filtration equipment through a transmission pipeline; the secondary pressure filtration equipment is connected with the mixing and stirring equipment and the sewage treatment system through transmission pipelines respectively; the mixing and stirring equipment is connected with the ageing warehouse through a transmission belt. The process for harmless treatment of electrolytic manganese slag by using the equipment comprises the following steps: (1) washing and stirring: putting manganese slag obtained by filter pressing in an electrolytic manganese factory into water washing stirring equipment, adding water to carry out water washing stirring, and conveying ammonia gas generated in the water washing stirring process to an ammonia gas treatment system for treatment; (2) primary filter pressing: the manganese slag and the waste liquid after washing and stirring enter primary filter pressing equipment through a transmission pipeline to be subjected to filter pressing, so that solid-liquid separation is carried out, the separated waste liquid enters a filtrate recovery tank to be recovered and can be directly used for electrolytic manganese from an acid leaching process, and the separated manganese slag enters digestion and stirring equipment through the transmission pipeline; (3) digestion and stirring: adding quicklime and water into digestion stirring equipment, stirring, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the addition amount of the quicklime is 4-6% of the mass of manganese slag, the addition amount of the water is 100-200% of the mass of manganese slag, and the stirring time is 20-30 min; (4) secondary filter pressing: the mixture after digestion and stirring enters secondary pressure filtration equipment through a transmission pipeline to carry out secondary pressure filtration, so that solid and liquid are separated, the separated filtrate is discharged after reaching the standard through treatment of a sewage treatment system, and the separated filter residues are transmitted to the mixing and stirring equipment; (5) mixing and stirring: adding dry fine sand into mixing stirring equipment, stirring for 20-30 min, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the adding amount of the dry fine sand is 5-10% of the mass of manganese slag; (6) And conveying the mixed and stirred materials to an ageing warehouse through a conveying belt, and ageing to obtain harmless manganese slag materials.
Further, the washing stirring equipment, the digestion stirring equipment and the mixing stirring equipment are all in a fully-closed state, and a negative pressure system is arranged on an air pipe connected with the washing stirring equipment, the digestion stirring equipment and the mixing stirring equipment. Through totally enclosed mode and negative pressure system, prevent the leakage of ammonia.
Furthermore, the mixing and stirring equipment is a horizontal coulter type stirrer, and the horizontal coulter type stirrer can effectively reduce material adhesion equipment and improve stirring efficiency due to high performance.
Further, the ammonia gas treatment system comprises a buffer tank, a vacuum unit, an ammonia gas absorption tower, a filler tower, a mother solution storage tank and an acid washing tower; an air inlet of the buffer tank is connected with the water washing stirring equipment, the digestion stirring equipment and the mixing stirring equipment through air pipes respectively; the air outlet of the buffer tank is connected with the air inlet of the vacuum unit; a condenser is arranged in the vacuum unit, and an air outlet of the vacuum unit is connected with an air inlet of the ammonia absorption tower; the gas outlet of the ammonia absorption tower is connected with the gas inlet of the packing tower; the gas outlet of the packing tower is connected with the gas inlet of the pickling tower, and the liquid outlet of the packing tower is connected to the mother liquid storage tank. The ammonia treatment system is used for treating ammonia, and comprises the following steps: (1) Ammonia generated in the water washing stirring equipment, the digestion stirring equipment and the mixing stirring equipment firstly enters the buffer tank, liquid ammonia enters the bottom of the buffer tank under the action of gravity, the ammonia enters the vacuum unit through the air outlet of the buffer tank, and the condenser of the vacuum unit can prevent heat release in the ammonia absorption process so as to reduce the air extraction efficiency; (2) Ammonia enters an ammonia absorption tower after passing through a vacuum unit, and is thermally released with water to be condensed; (3) After passing through the ammonia absorption tower, ammonia enters a packing tower, the absorbed ammonia is converted into ammonia water, the ammonia water enters a mother solution storage tank under the action of gravity, and the unabsorbed ammonia enters an acid washing tower; (4) Ammonia entering the acid washing tower is washed by dilute sulfuric acid and then discharged after reaching the standard.
Further, the mother liquor storage tank is connected with an ammonia storage tank, and a one-way air valve is arranged at the joint of the mother liquor storage tank and the ammonia storage tank.
The invention has the beneficial effects that: (1) The method and the equipment are designed according to the properties of the electrolytic manganese slag, and the water content of the electrolytic manganese slag after water washing and stirring and one-time pressure filtration is about 15 percent, so that the aim of digestion and stirring is to eliminate most of soluble sulfate (about 30-60 percent) and ammonia contained in the manganese slag after water washing. (2) After digestion and stirring, the water content of the manganese slag is about 100%, secondary pressure filtration is needed, the water content of the manganese slag after pressure filtration can reach about 20%, the soluble sulfate (about 20-40%) remained after the primary digestion reaction is removed through mixing and stirring, and in the mixing and stirring process, a part of water is consumed through adding dry fine sand, so that the friction force of the manganese slag is increased, and the problem of manganese slag bonding equipment is solved. (3) In the design of an ammonia gas treatment system, a cooling water washing and acid washing method is adopted to treat ammonia gas, 5 ten thousand tons of manganese slag are treated per year, 10 tons of manganese slag are treated per hour, the content of soluble sulfate in the manganese slag is about 6 percent, the sulfate is assumed to be ammonium sulfate, the amount of ammonia gas discharged under the theoretical condition is calculated to be about 150kg, and the discharged ammonia gas is 197635L/h (which is reduced to 197 m) 3 And/h), the ammonia can be efficiently treated by adopting a water washing and acid washing mode. (4) The waste water after secondary filter pressing contains a certain amount of soluble sulfate, quick lime is utilized for neutralization and precipitation, the waste water after reaching the standard can be used in an electrolytic manganic acid leaching process, and the generated precipitation slag can be directly used for making bricks. (5) All stirring processes are carried out under the fully-closed condition, and meanwhile, generated ammonia is conveyed to an ammonia treatment system by adopting negative pressure, so that leakage of the ammonia can be effectively prevented. (6) And the mixed and stirred materials are piled up in an ageing warehouse for ageing, so that the homogenization rate of lime and manganese slag is effectively improved. The invention effectively solves the problems of a great deal of ammonium sulfate and soluble manganese sulfate remained in electrolytic manganese slag through water washing stirring, digestion stirring, third stirring and twice pressure filtration, and the manganese slag mixture after three times stirring containsThe water rate is about 10%, and the ammonium salt removal rate can reach more than 90%.
Drawings
FIG. 1 is a process flow of an electrolytic manganese slag harmless treatment method.
FIG. 2 is a diagram of equipment used in the method for harmless treatment of electrolytic manganese slag.
FIG. 3 is a block diagram of an ammonia gas treatment system of equipment used in the method for harmless treatment of electrolytic manganese slag.
Wherein, 1, washing the stirring equipment; 2. primary filter pressing equipment; 3. a filtrate recovery tank; 4. digestion stirring equipment; 5. secondary pressure filtration equipment; 6. a sewage treatment system; 7. mixing and stirring equipment; 8. an ammonia gas treatment system; 81. a buffer tank; 82. a vacuum unit; 83. an ammonia absorption tower; 84. a packed tower; 85. a mother liquor storage tank; 851. a one-way air valve; 86. an ammonia gas storage tank; 87. a pickling tower; 9. a negative pressure system; 10. and (5) aging the warehouse.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to fig. 1-3, but it should be understood that the scope of the present invention is not limited by the specific embodiments.
Example 1:
the equipment adopted by the electrolytic manganese slag harmless treatment method is shown in figure 2, and comprises a water washing stirring equipment 1, a primary filter pressing equipment 2, a filtrate recovery tank 3, a digestion stirring equipment 4, a secondary filter pressing equipment 5, a sewage treatment system 6, a mixing stirring equipment 7, an ammonia gas treatment system 8 and an ageing warehouse 10, wherein the upper ends of the water washing stirring equipment 1, the digestion stirring equipment 4 and the mixing stirring equipment 7 are connected with the ammonia gas treatment system 8 through air pipes; the lower end of the washing stirring device 1 is connected with a primary filter pressing device 2 through a transmission pipeline, and the primary filter pressing device 2 is connected to a filtrate recovery tank 3 and a digestion stirring device 4 through the transmission pipeline respectively; the bottom of the digestion stirring equipment 4 is connected with a secondary pressure filtration equipment 5 through a transmission pipeline; the secondary pressure filtration equipment 5 is connected with the mixing and stirring equipment 7 and the sewage treatment system 6 through transmission pipelines respectively; the mixing and stirring device 7 is connected with an ageing warehouse 10 through a conveying belt.
As shown in fig. 1, the harmless treatment method of the electrolytic manganese slag comprises the following steps: (1) washing and stirring: putting manganese slag obtained by filter pressing in an electrolytic manganese factory into washing stirring equipment 1, adding water to carry out washing stirring, and conveying ammonia generated in the washing stirring process to an ammonia treatment system 8 for treatment; (2) primary filter pressing: the manganese slag and the waste liquid after washing and stirring enter primary filter pressing equipment 2 through a transmission pipeline to be subjected to filter pressing, so that solid-liquid separation is carried out, the separated waste liquid enters a filtrate recovery tank 3 to be recovered and can be directly used for electrolytic manganese from an acid leaching process, and the separated manganese slag enters digestion stirring equipment 4 through the transmission pipeline; (3) digestion and stirring: adding quicklime and water into the digestion stirring equipment 4, stirring, and conveying ammonia generated in the stirring process to an ammonia treatment system 8 for treatment, wherein the addition amount of the quicklime is 4% of the mass of manganese slag, the addition amount of the water is 100% of the mass of manganese slag, and the stirring time is 30min; (4) secondary filter pressing: the mixture after digestion and stirring enters secondary pressure filtration equipment 5 through a transmission pipeline to carry out secondary pressure filtration, so that solid and liquid are separated, the separated filtrate is treated and recycled by a sewage treatment system 6, and the separated filter residues are transmitted to mixing and stirring equipment 7; (5) mixing and stirring: adding dry fine sand into a mixing and stirring device 7, stirring for 20min, and conveying ammonia generated in the stirring process to an ammonia treatment system 8 for treatment, wherein the adding amount of the dry fine sand is 5% of the mass of manganese slag; (6) And conveying the mixed and stirred materials to an ageing warehouse 10 through a conveying belt, and ageing to obtain harmless manganese slag materials.
In the method, most of soluble sulfate and ammonia gas contained in the manganese slag after water washing are eliminated through digestion and stirring; the residual soluble sulfate after digestion stirring is removed through mixing and stirring, and part of water is consumed through adding dry fine sand in the mixing and stirring, and meanwhile, the friction force of the manganese slag is increased, so that the problem of manganese slag bonding equipment is solved. The electrolytic manganese slag can be applied to sintered or non-sintered products after harmless treatment.
Example 2:
as shown in fig. 1, the harmless treatment method of the electrolytic manganese slag comprises the following steps: (1) washing and stirring: adding water into manganese slag obtained by filter pressing in an electrolytic manganese plant for washing and stirring, and conveying ammonia gas generated in the washing and stirring process to an ammonia gas treatment system for treatment; (2) primary filter pressing: carrying out filter pressing on the manganese slag after washing and stirring with water to separate solid from liquid, wherein the separated waste liquid is directly used for an electrolytic manganic acid leaching process, and the separated manganese slag is transmitted to the next process; (3) digestion and stirring: adding quicklime and water into the manganese slag subjected to primary pressure filtration, stirring, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the addition amount of the quicklime is 6% of the mass of the manganese slag, the addition amount of the water is 200% of the mass of the manganese slag, and the stirring time is 20min; (4) secondary filter pressing: carrying out secondary filter pressing on the manganese slag mixture after digestion and stirring to separate solid from liquid, treating the separated wastewater to reach the standard, recycling the wastewater, and conveying the separated waste slag to the next working procedure; (5) mixing and stirring: mixing and stirring the waste residues subjected to secondary filter pressing with dry fine sand for 30min, and conveying ammonia gas generated in the stirring process to an ammonia gas treatment system for treatment, wherein the addition amount of the dry fine sand is 10% of the mass of manganese slag, the fineness modulus of the dry fine sand is 1.6-2.2, and the average particle size is 0.25-0.35 mm; (6) And (3) conveying the mixed and stirred materials to an ageing warehouse, and ageing to obtain harmless manganese slag materials.
In the embodiment, the equipment adopted in the electrolytic manganese slag harmless treatment method is shown in fig. 2, and comprises a water washing stirring equipment 1, a primary filter pressing equipment 2, a filtrate recovery tank 3, a digestion stirring equipment 4, a secondary filter pressing equipment 5, a sewage treatment system 6, a mixing stirring equipment 7, an ammonia treatment system 8 and an ageing warehouse 10, wherein the upper ends of the water washing stirring equipment 1, the digestion stirring equipment 4 and the mixing stirring equipment 7 are connected with the ammonia treatment system 8 through air pipes; the lower end of the washing stirring device 1 is connected with a primary filter pressing device 2 through a transmission pipeline, and the primary filter pressing device 2 is connected to a filtrate recovery tank 3 and a digestion stirring device 4 through the transmission pipeline respectively; the bottom of the digestion stirring equipment 4 is connected with a secondary pressure filtration equipment 5 through a transmission pipeline; the secondary pressure filtration equipment 5 is connected with the mixing and stirring equipment 7 and the sewage treatment system 6 through transmission pipelines respectively; the mixing and stirring equipment 7 is connected with the ageing warehouse 10 through a transmission belt; the mixing and stirring equipment 7 is a horizontal coulter type stirrer, and the horizontal coulter type stirrer can effectively reduce material adhesion equipment and improve stirring efficiency due to high performance.
Example 3:
as shown in fig. 1, the harmless treatment method of the electrolytic manganese slag comprises the following steps: (1) washing and stirring: adding water into manganese slag obtained by filter pressing in an electrolytic manganese plant for washing and stirring, and conveying ammonia gas generated in the washing and stirring process to an ammonia gas treatment system for treatment; (2) primary filter pressing: carrying out filter pressing on the manganese slag after washing and stirring with water to separate solid from liquid, wherein the separated waste liquid is directly used for an electrolytic manganic acid leaching process, and the separated manganese slag is transmitted to the next process; (3) digestion and stirring: adding quicklime and water into the manganese slag subjected to primary pressure filtration, stirring, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the addition amount of the quicklime is 5% of the mass of the manganese slag, the addition amount of the water is 150% of the mass of the manganese slag, and the stirring time is 25min; (4) secondary filter pressing: carrying out secondary filter pressing on the manganese slag mixture after digestion and stirring to separate solid from liquid, carrying out neutralization precipitation treatment on separated wastewater by lime, recycling the wastewater after reaching the standard, and conveying the separated waste slag to the next working procedure; (5) mixing and stirring: mixing and stirring the waste residues subjected to secondary filter pressing with dry fine sand for 25min, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the addition amount of the dry fine sand is 8% of the mass of the manganese slag; (6) And (3) conveying the mixed and stirred materials to an ageing warehouse, and ageing to obtain harmless manganese slag materials.
As shown in fig. 2 and 3, the equipment adopted by the electrolytic manganese slag harmless treatment method comprises a water washing stirring equipment 1, a primary filter pressing equipment 2, a filtrate recovery tank 3, a digestion stirring equipment 4, a secondary filter pressing equipment 5, a sewage treatment system 6, a mixing stirring equipment 7, an ammonia treatment system 8 and an ageing warehouse 10; the lower end of the washing stirring device 1 is connected with a primary filter pressing device 2 through a transmission pipeline, and the primary filter pressing device 2 is connected to a filtrate recovery tank 3 and a digestion stirring device 4 through the transmission pipeline respectively; the bottom of the digestion stirring equipment 4 is connected with a secondary pressure filtration equipment 5 through a transmission pipeline; the secondary pressure filtration equipment 5 is connected with the mixing and stirring equipment 7 and the sewage treatment system 6 through transmission pipelines respectively; the mixing and stirring equipment 7 is connected with the ageing warehouse 10 through a transmission belt; the ammonia gas treatment system 8 comprises a buffer tank 81, a vacuum unit 82, an ammonia gas absorption tower 83, a packing tower 84, a mother liquor storage tank 85 and an acid washing tower 87; the air inlet of the buffer tank 81 is respectively connected with the washing stirring equipment 1, the digestion stirring equipment 4 and the mixing stirring equipment 7 through air pipes; the air outlet of the buffer tank 81 is connected with the air inlet of the vacuum unit 82; a condenser is arranged in the vacuum unit 82, and an air outlet of the vacuum unit 82 is connected with an air inlet of an ammonia absorption tower 83; the gas outlet of the ammonia absorption tower 83 is connected with the gas inlet of the packed tower 84; the air outlet of the packed column 84 is connected with the air inlet of the pickling column 87, and the liquid outlet of the packed column 84 is connected to the mother liquid storage tank 85.
Example 4:
as shown in fig. 1 to 3, on the basis of embodiment 3, the washing stirring device 1, the digestion stirring device 4 and the mixing stirring device 7 are all in a fully closed state, and a negative pressure system 9 is installed on an air pipe connected with the washing stirring device 1, the digestion stirring device 4 and the mixing stirring device 7 by the ammonia gas treatment system 8. By means of the fully closed mode and the negative pressure system 9, leakage of ammonia gas is prevented.
Example 5:
as shown in fig. 1 to 3, on the basis of embodiment 3, an ammonia gas storage tank 86 is connected to the mother liquid storage tank 85, and a unidirectional air valve 851 is provided at the connection between the mother liquid storage tank 85 and the ammonia gas storage tank 86.
Claims (3)
1. The harmless treatment method of the electrolytic manganese slag is characterized by comprising the following steps of: (1) washing and stirring: adding water into manganese slag obtained by filter pressing in an electrolytic manganese plant for washing and stirring, and conveying ammonia gas generated in the washing and stirring process to an ammonia gas treatment system for treatment; (2) primary filter pressing: carrying out filter pressing on the manganese slag after washing and stirring with water to separate solid from liquid, wherein the separated waste liquid is directly used for an electrolytic manganic acid leaching process, and the separated manganese slag is transmitted to the next process; (3) digestion and stirring: adding quicklime and water into the manganese slag subjected to primary pressure filtration, stirring, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the addition amount of the quicklime is 4-6% of the mass of the manganese slag, the addition amount of the water is 100-200% of the mass of the manganese slag, and the stirring time is 20-30 min; (4) secondary filter pressing: carrying out secondary filter pressing on the manganese slag mixture after digestion and stirring to separate solid from liquid, treating the separated wastewater to reach the standard, recycling the wastewater, and conveying the separated waste slag to the next working procedure; (5) mixing and stirring: mixing and stirring the waste residues subjected to secondary filter pressing with dry fine sand for 20-30 min, and conveying ammonia generated in the stirring process to an ammonia treatment system for treatment, wherein the addition amount of the dry fine sand is 5-10% of the mass of manganese slag; (6) And (3) conveying the mixed and stirred materials to an ageing warehouse, and ageing to obtain harmless manganese slag materials which are used for preparing sintered or non-sintered products.
2. The method for harmless treatment of electrolytic manganese slag according to claim 1, wherein the secondary pressure filtration separated waste water is subjected to neutralization precipitation treatment by lime.
3. The method for harmless treatment of electrolytic manganese slag according to claim 1, wherein the fineness modulus of the dry fine sand is 1.6-2.2 and the average particle diameter is 0.25-0.35 mm.
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