CN114504944A - Composite desulfurizer for low-concentration sulfur dioxide flue gas desulfurization and application thereof - Google Patents
Composite desulfurizer for low-concentration sulfur dioxide flue gas desulfurization and application thereof Download PDFInfo
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000003546 flue gas Substances 0.000 title claims abstract description 54
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 43
- 230000023556 desulfurization Effects 0.000 title claims abstract description 43
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000003860 storage Methods 0.000 claims description 33
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000428 dust Substances 0.000 claims description 13
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000000779 smoke Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003610 charcoal Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a composite desulfurizer for low-concentration sulfur dioxide flue gas desulfurization and application thereof, belonging to the technical field of flue gas desulfurization. The composite desulfurizer provided by the invention comprises 10-87 wt% of sodium bicarbonate, 10-87 wt% of sodium carbonate and 3-20 wt% of simple substance carbon particles; the desulfurization method adopting the composite desulfurizer calculates the mass of sulfur dioxide to be removed according to the flow rate of flue gas and the concentration of sulfur dioxide in unit time, and the amount of the composite desulfurizer added in unit time is 2-4 times of the amount of the sulfur dioxide to be removed; the method for adding the composite desulfurizer is to mix the composite desulfurizer into the electrolytic anode scrap raw material 1-6 times in unit time. The invention provides a system for desulfurizing by using the composite desulfurizer, which completes the compound mixing and quantitative feeding of the composite desulfurizer by arranging a blanking assembly. By adopting the composite desulfurizer and the system equipment provided by the invention, twice desulfurization is realized, the desulfurization efficiency is obviously improved, and the consumption of the desulfurizer is reduced; low cost, simple operation and convenient realization.
Description
Technical Field
The invention belongs to the technical field of flue gas desulfurization, and particularly relates to a composite desulfurizer for low-concentration sulfur dioxide flue gas desulfurization.
Background
The scrap copper shaft furnace is characterized in that a copper raw material (mainly electrolytic anode scrap) is added into a hearth of the shaft furnace through a hopper, a winch and other equipment, a natural gas burner at the lower side of a shaft furnace body of the shaft furnace continuously burns natural gas to release heat, and the copper raw material at the root of a material pile is gradually melted into copper liquid. Along with the continuous melting of the copper raw material at the root of the material pile and the continuous and cyclic operation of feeding, the material pile formed by the copper material accumulation in the hearth always maintains a certain height. The feeding speed is matched with the material melting speed, so that the height of the material pile is maintained in a specified range.
The combustion of natural gas at the bottom of the shaft furnace produces flue gases. A certain amount of copper sulfate particles are attached to the surface of the electrolytic anode scrap and decomposed to generate SO at the temperature of over 800 DEG C2The gas flows from bottom to top along with the flue gas along the inner gap of the copper raw material pile and enters the flue of the shaft furnace. Compared with other copper metallurgical furnaces, the heat exchange time of the copper raw material of the scrap copper shaft furnace and the flue gas is long and reaches 1-3 h; the temperature of the flue gas in the shaft furnace is distributed in a gradient manner and is gradually reduced from 1200 ℃ near a natural gas burner to 100 ℃ at the inlet of a flue of the shaft furnace; the flue gas flow is small, the content of sulfur dioxide is low, and the total amount is small; according to the calculation of the limit working condition, the maximum smoke gas amount of the shaft furnace is 7000m3The maximum concentration of sulfur dioxide in the flue gas is 200mg/m3The total amount of sulfur dioxide in the flue gas is only 1.4 kg/h; the flue gas is relatively clean, and the main components except a small amount of sulfur dioxide and particles are carbon dioxide and water vapor.
At present, according to the latest domestic standard, the content of sulfur dioxide in the flue gas is reduced to be lower than 100mg/m by the special emission limit value of the regenerated copper pollutants3. Therefore, the sulfur dioxide content in the flue gas of the shaft furnace may face the risk of exceeding the standard, and further measures are needed to remove the sulfur dioxide. Theoretically, the existing tail gas desulfurization technologies (such as sodium-alkali tail gas desulfurization, active coke tail gas desulfurization, ionic liquid desulfurization and the like) can be applied to shaft furnace flue gas desulfurization, but the total amount of the shaft furnace flue gas sulfur dioxide is very small, and the required maximum desulfurization capacity is only 0.7 kg/h. The prior tail gas desulfurization technology used for shaft furnace flue gas desulfurization can generate overhigh investment and operation cost, and the economical efficiency of the desulfurization process is extremely undesirable. Therefore, a technical process which can meet the requirement of removing low-concentration sulfur dioxide in shaft furnace flue gas and is economical and environment-friendly is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a composite desulfurizer for desulfurizing low-concentration sulfur dioxide flue gas and application thereof, and is realized by the following technology.
The composite desulfurizer for desulfurizing low-concentration sulfur dioxide flue gas comprises 10-87 wt% of sodium bicarbonate, 10-87 wt% of sodium carbonate and 3-20 wt% of simple substance carbon particles.
In the composite desulfurizing agent, the elemental carbon particles refer to all industrial raw material particles composed of elemental carbon, such as activated carbon, charcoal or graphite particles. Generally, when the shaft furnace works, the electrolytic anode scrap raw material is fed for 15 to 20 times within 1h, and about 1 ton of the electrolytic anode scrap raw material is fed each time. The total amount of the electrolytic anode scrap raw materials (about 15-20 tons) added within 1h is weighed according to the proportion, and then the composite desulfurizer is mixed with the electrolytic anode scrap raw materials in batches and added to the top of a material pile of the shaft furnace.
With the operation of melting materials (melting the electrolytic anode scrap raw material), because the composite desulfurizer and the electrolytic anode scrap raw material are mixed relatively uniformly, the temperature of the composite desulfurizer and the electrolytic anode scrap raw material cannot be rapidly raised due to high-temperature heat exchange in a hearth, and the thermal decomposition process of sodium bicarbonate in the composite desulfurizer is relatively slow. The temperature of the contacted flue gas is continuously increased along with the continuous downward movement of the material pile; when the temperature of the flue gas reaches 150-500 ℃, based on the principle of a sodium bicarbonate desulfurization method (experimental research on sodium bicarbonate dry desulfurization, Beijing university of industry, 2020), NaHCO (NaHCO)3After the particles are sprayed into the front end pipeline of the bag type dust collector, the temperature of the flue gas (130-3Initial decomposition temperature (about 37 ℃), NaHCO3With SO2The reaction takes place, see the following equations (1) to (4). Meanwhile, under the action of the Venturi tube, the airflow in the pipeline moves more violently, the movement of molecules and particles is accelerated, and the NaHCO is intensified3Collisions between solid particles cause the rate of their decomposition to increase.
2NaHCO3+SO2→Na2SO3+2CO2+H2O (1)
2NaHCO3→Na2CO3+H2O+CO2 (2)
Na2CO3+SO2→Na2SO3+CO2 (3)
Na2SO3+12O2→Na2SO4 (4)
Sodium bicarbonate in the desulfurizer reacts with sulfur dioxide in the flue gas to generate Na2SO3、Na2SO4And carrying out first desulfurization. For a certain batch of the added composite desulfurizer, the first desulfurization process is completed within about 1 h. When the temperature of the flue gas reaches 850-2SO3And carrying out secondary desulfurization. Na produced in the above two desulfurization processes2SO3The reaction is continued to generate suspended particles of sodium sulfate, and the suspended particles enter a bag type dust collector along with the flue gas, and the time for the second desulfurization is about 1-2 h. The sulfur dioxide in the flue gas of the shaft furnace is removed twice in the hearth, thereby improving the desulfurization efficiency. The simple substance carbon particles in the desulfurizer react with oxygen in the flue gas to generate CO2And sulfur dioxide in the flue gas is prevented from reacting with oxygen to generate sulfur trioxide.
Preferably, the composite desulfurizing agent comprises 60 wt% of sodium bicarbonate, 35 wt% of sodium carbonate and 5 wt% of elementary carbon particles.
Preferably, the total alkali content of the sodium bicarbonate is NaHCO3Not less than 99.0 percent, and the granularity is 600-1500 meshes; the total alkali amount of the sodium carbonate is NaCO on a dry basis3Not less than 98.0 percent), and the granularity is 600-1500 meshes; the content of fixed carbon in the simple substance carbon particles is not less than 75%, and the particle size is 5-200 mm.
The invention also provides a desulfurization method using the composite desulfurizer, which comprises the steps of uniformly mixing the sodium bicarbonate, the sodium carbonate and the simple substance carbon particles according to the weight percentage to prepare the composite desulfurizer, mixing the composite desulfurizer with the electrolytic anode scrap raw material, and adding the mixture into a hearth of the scrap copper shaft furnace.
Preferably, in the desulfurization method, the mass of the sulfur dioxide to be removed in unit time is calculated according to the flow rate and the sulfur dioxide concentration of the flue gas in unit time (generally, 1h can be taken as the standard), and the mass of the compound desulfurizer added in unit time is 2-4 times of the calculated mass of the sulfur dioxide to be removed; the method for adding the composite desulfurizer is to mix the composite desulfurizer into the electrolytic anode scrap raw material 1-6 times in unit time.
Based on the composite desulfurizer, the invention also provides a system capable of being used for low-concentration sulfur dioxide flue gas desulfurization, which comprises a furnace body, bucket type lifting equipment, a blanking assembly, a flue and a bag type dust remover, wherein the top of the bucket type lifting equipment corresponds to a charging opening at the top of the furnace body, the top of the furnace body is connected with one end of the flue, and the other end of the flue is connected with the bag type dust remover;
the blanking assembly comprises a first storage bin, a second storage bin, a third storage bin, a mixing bin and a discharging pipe, wherein sodium bicarbonate, sodium carbonate and simple substance carbon particles are respectively placed in the first storage bin, the second storage bin and the third storage bin, the first storage bin, the second storage bin and the third storage bin are respectively connected with the mixing bin through pipelines, 3 pipelines are respectively provided with a solid flow control valve, the discharging pipe is connected with a discharging port of the mixing bin, and the discharging pipe is provided with the solid flow control valve; and preparing and storing the composite desulfurizer in the mixing bin, wherein the pipe orifice of the discharge pipe corresponds to the hopper of the bucket type lifting equipment.
In the system, a first storage bin, a second storage bin and a third storage bin are respectively used for storing sodium bicarbonate, sodium carbonate and simple substance carbon particles; the solid flow control valve on the pipeline is used for controlling the dosage proportion of the sodium bicarbonate, the sodium carbonate and the simple substance carbon particles; the mixing bin is used for uniformly mixing the sodium bicarbonate, the sodium carbonate and the simple substance carbon particles to prepare the composite desulfurizer; the mixed composite desulfurizer is added into a hopper in proportion through a solid flow control valve on a discharge pipe, is mixed with the electrolytic anode scrap raw material in the hopper in a mechanical or manual mode, and finally is added into the shaft furnace through a bucket type lifting device. Desulfurization product Na2SO3、Na2SO4The smoke is carried by the smoke and sent into the bag-type dust collector, and the smoke and other particulate matters in the smoke are filtered and enter the cigarette ash so as to be separated from the smoke. Finally, the sulfur dioxide content is less than 100mg/m3Smoke passing cigaretteThe chimney is emptied. An on-line flue gas analyzer is arranged on the chimney and used for detecting the sulfur dioxide content of the discharged tail gas.
Compared with the prior art, the invention has the advantages that:
1. the contact time of the composite desulfurizer and the flue gas in the hearth is as long as 1-3h, and the desulfurization efficiency is obviously improved and the consumption of the desulfurizer is reduced by two-time desulfurization;
2. the composite desulfurizer is a solid raw material, and the dry desulfurization does not generate desulfurization waste liquid and does not need subsequent treatment; the desulfurization product is collected by a subsequent bag-type dust collector, so that secondary environmental pollution is avoided;
3. the composite desulfurizer can be prepared by self, and the raw materials of the composite desulfurizer have wide sources and low price; additional equipment facilities do not need to be added, occupied space of new equipment does not need to be added, and the cost is low; the operation process is simple and convenient to realize, the sulfur dioxide content of the discharged tail gas is detected according to an online flue gas analyzer near a chimney, the using amount of the desulfurizer can be adjusted in time, and the response speed is high.
Drawings
Fig. 1 is a schematic structural diagram of a system for desulfurizing a low-concentration sulfur dioxide flue gas provided by the invention.
In the figure: 1. a furnace body; 2. a bucket elevator; 3. a flue; 4. a bag type dust collector; 5. a first storage bin; 6. a second storage bin; 7. a third storage bin; 8. a mixing bin; 9. a discharge pipe; 10. a pipeline; 11. a solids flow control valve; 12. a chimney; 13. an on-line flue gas analyzer.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood 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 system for low-concentration sulfur dioxide flue gas desulfurization used in the following examples and comparative examples, as shown in fig. 1, comprises a furnace body 1, a bucket elevator 2, a blanking assembly, a flue 3, and a bag-type dust collector 4, wherein the top of the bucket elevator 2 corresponds to a top charging port of the furnace body 1, the top of the furnace body 1 is connected with one end of the flue 3, and the other end of the flue 4 is connected with the bag-type dust collector 4;
the blanking assembly comprises a first storage bin 5, a second storage bin 6, a third storage bin 7, a mixing bin 8 and a discharge pipe 9, wherein sodium bicarbonate, sodium carbonate and simple substance carbon particles are respectively placed in the first storage bin 5, the second storage bin 6 and the third storage bin 7, the first storage bin 5, the second storage bin 6 and the third storage bin 7 are respectively connected with the mixing bin 8 through pipelines 10, 3 pipelines 10 are respectively provided with a solid flow control valve 11, the discharge pipe 9 is connected with a discharge port of the mixing bin 8, and the discharge pipe 9 is provided with the solid flow control valve 11; and a composite desulfurizer is prepared and stored in the mixing bin 8, and the pipe orifice of the discharge pipe 9 corresponds to the hopper of the bucket type lifting equipment 2.
The smoke outlet of the bag type dust collector 4 is connected with a chimney 12, and an online smoke analyzer 13 is arranged in the chimney 12.
The total alkali content of sodium bicarbonate is NaHCO, used as a composite desulphurizing agent in the following examples and comparative examples3Not less than 99.0 percent, and the granularity is 600-1500 meshes; the total alkali amount of the sodium carbonate is NaCO on a dry basis3Not less than 98.0 percent), and the granularity is 600-1500 meshes; in order to save cost, the selected simple substance carbon particles are charcoal particles, wherein the content of fixed carbon is about 75 percent, and the particle size is 5-200 mm.
Example 1
The composite desulfurizer provided by the embodiment comprises 60 wt% of sodium bicarbonate, 35 wt% of sodium carbonate and 5 wt% of charcoal.
Example 2
The composite desulfurizer provided by the embodiment comprises 87 wt% of sodium bicarbonate, 10 wt% of sodium carbonate and 3 wt% of charcoal.
Example 3
The composite desulfurizer provided by the embodiment comprises 10 wt% of sodium bicarbonate, 87 wt% of sodium carbonate and 3 wt% of charcoal.
Example 4
The composite desulfurizing agent provided by the embodiment comprises 50.53 wt% of sodium bicarbonate, 29.47 wt% of sodium carbonate and 20 wt% of charcoal. I.e. the ratio of sodium bicarbonate to sodium carbonate is the same as in example 1
Comparative example 1
The composite desulfurizing agent provided in this example is composed of 87 wt% of sodium bicarbonate and 13 wt% of charcoal.
Comparative example 2
The composite desulfurizer provided by the embodiment comprises 87 wt% of sodium carbonate and 13 wt% of charcoal.
Comparative example 3
The composite desulfurizing agent provided in this example is composed of 63.16 wt% of sodium bicarbonate and 36.84 wt% of sodium carbonate. I.e., the ratio of the amounts of sodium bicarbonate and sodium carbonate used was the same as in example 1.
Application example
The desulfurization test of scrap copper shaft furnace flue gas was carried out using the composite desulfurizing agents of examples 1 to 4 and comparative examples 1 to 3. The electrolytic anode scrap raw material in the experimental shaft furnace is derived from an anode copper plate remained after electrolysis of a large nonferrous metal metallurgy Limited liability company and is divided into a small anode scrap and a large anode scrap;
length × width × thickness of the small residual electrode: (785. + -.10) mmX (760. + -.10) mmX (37. + -.5) (mm); each block has a single weight of 19.3-34.7 kg;
length x width x thickness of large anode scrap: (1000. + -.10) mm X (960. + -.10) mm X (45. + -.5) (mm); each block has a single weight of 38.7-69.6 kg. The used shaft furnace is designed and manufactured by the institute of design of the subordinate of the large nonferrous metal metallurgy Limited liability company, the specification is 25t/h, and the height of a material pile is 8.1 m.
The specific process of charging and melting materials in the shaft furnace is as follows:
(1) feeding: the electrolytic anode scrap raw material is loaded into the hopper, is transported to the top of the shaft furnace through the electric winch, and then is added into the hearth from the charging hole through the tilting hopper, falls to the top of the material pile, and the height of the material pile is increased. Feeding materials once every 3min, wherein the feeding amount of the anode scrap raw materials is 1 ton each time; the material pile is formed by stacking electrolysis anode scrap raw materials added into a shaft furnace
(2) The 'material melting': after the shaft furnace is started, a natural gas burner at the lower side part of the furnace body continuously operates, the natural gas is continuously combusted to provide heat, the copper raw material at the root of the material pile is gradually melted into copper liquid, and the height of the material pile is gradually reduced; the charging speed is controlled to be matched with the speed of material melting operation, so that the height of a material pile is kept dynamically and stably all the time during the production period of the shaft furnace, the maintaining time is consistent with the production period of the shaft furnace, and the height is generally selected and determined from 15 to 60 days;
(3) the smoke quantity of the shaft furnace measured by a flowmeter is about 6000m3When the sulfur dioxide content is over 180mg/m, the sulfur dioxide content is measured by an on-line flue gas analyzer (forcibly installed by environmental protection departments) arranged in the chimney3；
(4) Selecting any one of the composite desulfurizer in the examples 1-4 and the comparative examples 1-3, wherein the input amount is temporarily 3 kg/h; uniformly dividing the composite desulfurizer put in every hour into 3 parts, mixing the 3 parts with the electrolytic anode scrap raw material in the hopper every 20 minutes, and putting the mixture into a hearth from the top of the shaft furnace; the composite desulphurizing agent of each example or comparative example is cyclically repeated for 3 hours according to the process;
(5) the sulfur dioxide concentration in the flue gas during the use of any of the composite desulfurizing agents of examples 1 to 4 and comparative examples 1 to 3 was measured by an on-line flue gas analyzer (forcibly installed by environmental protection agency) installed in a chimney as shown in the following table.
TABLE 1 Sulfur dioxide concentration in flue gas
As can be seen from the above table, when the composite desulfurizing agent of examples 1 to 4 was used, the effect of removing sulfur dioxide in flue gas was remarkable. When the composite desulfurizing agent of example 1 was used, the desulfurizing effect was the best. When the composite desulfurizer is lack of sodium bicarbonate or sodium carbonate, the secondary removal of sulfur dioxide cannot be realized, so that the sulfur dioxide concentration in the flue gas is reduced to some extent, but the reduction degree is obviously lower than that of the composite desulfurizer of the embodiments 1-4; when charcoal particles are lacked, a large amount of sulfur trioxide is generated by sulfur dioxide and oxygen in the flue gas, so that the dew point of the flue gas is reduced, and the bag type dust collector is subjected to dewing to influence the normal operation; meanwhile, the fluidity of the slag of the shaft furnace is deteriorated, which affects the operation effect.
Claims (6)
1. The composite desulfurizer for low-concentration sulfur dioxide flue gas desulfurization is characterized by comprising 10-87 wt% of sodium bicarbonate, 10-87 wt% of sodium carbonate and 3-20 wt% of simple substance carbon particles.
2. The composite desulfurizer for desulfurization of low-concentration sulfur dioxide flue gas as recited in claim 1, comprising 60 wt% of sodium bicarbonate, 35 wt% of sodium carbonate and 5 wt% of elemental carbon particles.
3. The composite desulfurizer used for desulfurization of low concentration sulfur dioxide flue gas as recited in claim 1, wherein the total alkali amount of sodium bicarbonate is NaHCO3Not less than 99.0 percent, and the granularity is 600-1500 meshes; the total alkali amount of the sodium carbonate is NaCO on a dry basis3Not less than 98.0 percent), and the granularity is 600-1500 meshes; the content of fixed carbon in the simple substance carbon particles is not less than 75%, and the particle size is 5-200 mm.
4. A desulfurization method using the composite desulfurizer as claimed in claim 1, characterized in that the composite desulfurizer is prepared by uniformly mixing sodium bicarbonate, sodium carbonate and elementary carbon particles in percentage by weight, and the composite desulfurizer is mixed with the electrolytic anode scrap raw material and then added into the furnace chamber of the scrap copper shaft furnace.
5. The desulfurization method of the composite desulfurizing agent according to claim 4, wherein the mass of the sulfur dioxide to be removed per unit time is calculated according to the flow rate of the flue gas per unit time and the concentration of the sulfur dioxide, and the mass of the composite desulfurizing agent added per unit time is 2 to 4 times of the calculated mass of the sulfur dioxide to be removed; the method for adding the composite desulfurizer is to mix the composite desulfurizer into the electrolytic anode scrap raw material 1-6 times in unit time.
6. A system for low-concentration sulfur dioxide flue gas desulfurization is characterized by comprising a furnace body, a bucket type lifting device, a blanking assembly, a flue and a bag type dust collector, wherein the top of the bucket type lifting device corresponds to a charging port at the top of the furnace body, the top of the furnace body is connected with one end of the flue, and the other end of the flue is connected with the bag type dust collector;
the blanking assembly comprises a first storage bin, a second storage bin, a third storage bin, a mixing bin and a discharging pipe, wherein sodium bicarbonate, sodium carbonate and simple substance carbon particles are respectively placed in the first storage bin, the second storage bin and the third storage bin, the first storage bin, the second storage bin and the third storage bin are respectively connected with the mixing bin through pipelines, 3 pipelines are respectively provided with a solid flow control valve, the discharging pipe is connected with a discharging port of the mixing bin, and the discharging pipe is provided with the solid flow control valve; the composite desulfurizer as claimed in any one of claims 1 to 3 is prepared and stored in the mixing bin, and the pipe orifice of the discharge pipe corresponds to the hopper of the bucket elevator.
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