CN113663450A - Deep purification process for industrial silicon smelting flue gas - Google Patents
Deep purification process for industrial silicon smelting flue gas Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
-
- 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
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- 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 process for deeply purifying industrial silicon smelting flue gas, which solves the problems of complicated existing process route, long processing line, serious unorganized emission and incapability of synchronously processing multiple gaseous pollutants such as sulfur, nitrate and dust and the like by using a negative pressure type dry electric filter tower and using a high-efficiency absorbent for purification on the basis of the existing process for treating the industrial silicon smelting flue gas; after the improvement, the treatment efficiency of the existing treatment process can be greatly improved, the treatment cost is reduced, the deep purification of gaseous pollutants such as sulfur, nitrate and dust is realized, and the method has a very strong industrial application prospect.
Description
Technical Field
The invention belongs to the field of flue gas purification, and particularly relates to a process for deeply purifying industrial silicon smelting flue gas.
Background
The yield of industrial silicon in China in 2019 is 260 ten thousand t, and about 300 ten thousand t in 2020. Is so largeThe production volume also brings a large amount of industrial silicon smelting flue gas. At present, the domestic silicon smelting flue gas mostly adopts a positive pressure bag type dust removal mode, the purification efficiency of particles in the flue gas is limited, and SO in the flue gas is2、NOxThe core problem that harmful gases cannot be effectively treated is more prominent: 1. at present, the commonly used bag type dust collector collects the particulate matters in the flue gas through a fiber filtering and dust removing mechanism, thereby realizing the purification of the flue gas, but the purification degree is relatively limited, and the concentration of the particulate matters in the purified flue gas is generally 50mg/m3(ii) a 2. Although the flue gas desulfurization engineering is gradually implemented for industrial silicon smelting enterprises, the treatment effect is not obvious, and the SO in the flue gas is gradually replaced by the silicon coal, the oil coke and the like along with the gradual replacement of the charcoal reducing agent in the smelting process2The emission amount will be further increased; 3. at the present stage, part of enterprises do not implement flue gas denitration engineering yet, so that NO in smelting flue gasxDirectly discharged into the atmospheric environment, and according to the investigation of partial silicon smelting enterprises, the concentration of NOx in the discharged smelting flue gas exceeds 100mg/m3As O3The negative impact on the environment of one of the precursors of (1) is not negligible;
SO in the present smelting flue gas2The content far exceeds the emission standard limit value of the national standard (GB 28666 and 2012), and the research and development of the silicon smelting flue gas desulfurization and denitrification technology are imperative. But because the silicon smelting flue gas has high dust characteristics, a plurality of denitration technologies cannot be used. If make solid catalyst deactivation very easily with the higher dust of conventional denitration technology, if denitration flue gas temperature can not reach the technological requirement again after the dust removal for silicon smelting flue gas denitration becomes an industry difficult problem, and at present the enterprise has installed desulphurization unit additional mostly, does not install denitrification facility additional, leads to the cost higher if newly-built denitrification facility again, increases enterprise's operation burden. In order to solve the problems, the invention can realize synchronous removal of the sulfur, the nitrate and the dust only by simple modification based on the production process of the existing industrial silicon smelting plant, improve the problems of serious unorganized emission and the like of enterprises, save huge capital cost and operation cost for upgrading and modifying the flue gas purification technology of the enterprises, and particularly save the cost for smelting in futureThe important direction of industrial technology upgrading.
Disclosure of Invention
Aiming at the problems that the prior silicon smelting flue gas treatment process mostly adopts positive pressure type dust removal, the unorganized emission is serious, the treatment process is backward, and the synchronous treatment of sulfur, nitrate and other multi-gaseous pollutants cannot be realized, the invention provides the process for deeply purifying the industrial silicon smelting flue gas, the process is simply upgraded and reformed on the basis of the original treatment process, the process principle is that an electric filtration dust removal technology and a high-efficiency liquid phase absorption catalysis technology are coupled, the aim of integrally and efficiently removing the sulfur, nitrate and other multi-pollutants in the industrial waste gas is fulfilled, and the treatment efficiency of the process can be greatly improved.
The deep purification process of the industrial silicon smelting flue gas comprises the steps that the industrial silicon smelting flue gas is discharged from an industrial furnace and enters a cooling system, the cooled gas enters a pre-dedusting system, large-particle dust is primarily separated, the flue gas is introduced into a dry type electric filter tower through an induced draft fan in a negative pressure mode, particles are charged in the dry type electric filter tower through a discharging effect, part of strong oxides generated in the discharging process can oxidize and remove harmful substances in the flue gas, the dry type electric filter tower removes the particles and the harmful substances in the flue gas through filtering cloth and an electric field effect, the flue gas flowing out of the dry type electric filter tower enters an absorption tower, the absorption tower sprays an absorbent through a spraying system to deeply purify the sulfur and nitrate harmful substances in the flue gas, and finally the flue gas is demisted and discharged through a demister.
The cooling of the cooling system is direct cooling or indirect cooling, the direct cooling comprises evaporative cooling and spray cooling, and the indirect cooling comprises water jacket cooling, surface cooling and waste heat boiler cooling.
The temperature of the flue gas cooled by the cooling system is 50-500 ℃, if evaporative cooling, spray cooling and other methods are adopted, the cooling liquid can be water, ammonia water with concentration of 15%, seawater and the like, and the humidity of the cooled flue gas is 0.1-5%.
The pre-dedusting system is a dedusting system with low operation cost and large particle removal capacity, and the pre-dedusting system is a cyclone dust collector, a gravity dust collector or a filter cartridge dust collector.
The dry-type electric filter tower comprises more than one dust removal unit, the dust removal unit comprises a shell, an anode and a cathode, the anode is a hollow cylindrical cage body with micropores formed by longitudinally and transversely overlapping and welding longitudinal ribs and support rings or a hollow cylinder with micropores, and filter cloth is loaded on the anode; more than one cathode electrode is arranged around the anode electrode, and the anode electrode and the cathode electrode are respectively connected with a power supply, wherein the air inlet mode is negative pressure type air inlet, air is inlet from the side surface of the dry electric filter tower, and air is outlet from the upper part of the anode electrode; the vertical ribs, the support ring and the hollow cylinder with the micropores are made of high-temperature resistant materials, the cathode electrode is one of a needle electrode, a double-area columnar electrode, a central bone-shaped electrode and a linear electrode, a double-area semi-bone-shaped electrode and a conical grid-shaped electrode, and the structure of the dry electric filter tower is the same as that of the dry electric filter dust removal device in the application No. 201911124719.5.
The anode electrode is RuO2Electrode, IrO2Electrode, SnO2Electrode, PbO2Electrode, Ti/SnO2Composite electrode, Ti/PbO2The electrode comprises one of a composite electrode, a BDD electrode, a magnesium-aluminum alloy electrode and a molybdenum-chromium alloy, and the selection of the electrode materials ensures that more strong oxide substances can be generated in the discharge process.
The discharge power supply is a high-voltage direct-current power supply or a pulse power supply, the voltage is 30 kV-100 kV, and whether the discharge power supply is electrified or not can be controlled according to the use condition; the strong oxide substances generated by the discharge are mainly OH free radicals, ozone, high-energy plasma and other substances.
The absorbent in the absorption tower is lime milk solution, or at normal temperature, 20-22% by mass of one or more of dimethyl sulfoxide, sulfolane and dibenzyl sulfoxide, and 20-22% by mass of one or more of N-hexane, N-heptane, N-methylpyrrolidone and carbon tetrachloride; 20-22% of propylene glycol phenyl ether and/or n-propanol, 6-8% of span and 6-8% of tween by mass percent are mixed and stirred for 2 hours, and then 20-22% of water or/and ammonia water by mass percent are added, and the mixture is continuously stirred for 3-4 hours to prepare the high-performance high-temperature-resistant medium.
The filter cloth on the anode electrode can be common filter cloth or special filter cloth, such as electric filter cloth, metal filter cloth, filter cloth with catalytic function and catalytic material attached on the surface, and the filter cloth can be prepared by the method in the electrochemical synergistic liquid phase catalytic sulfur-nitrate dust integrated purification method and device.
The spraying system in the absorption tower can be provided with multistage spraying according to actual treatment conditions, and a demisting device is arranged at the top of the absorption tower.
The temperature of the flue gas discharged after the treatment by the method is 10-50 ℃, and the temperature of SO2The concentration is 1-35 mg/Nm3，NOxThe concentration is 1-50 mg/Nm3The concentration of the particulate matter is 1-5 mg/Nm3。
The invention has the innovation points and the technical effects that:
compared with the prior art, the invention improves the prior art, can effectively improve the purification efficiency of the traditional process after being improved, reduce the treatment cost and realize the integrated and deep purification of the multiple pollutants such as the sulfur, the nitrate dust and the like; has strong industrial application prospect.
Drawings
FIG. 1 is a schematic view of the process of the present invention;
in the figure: 1-industrial furnace, 2-cooling system, 3-pre-dedusting system, 4-dry electric filter tower, 5-induced draft fan, 6-absorption tower, 7-spraying system and 8-demister.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples, without limiting the scope of the invention.
Example 1: as shown in figure 1, industrial flue gas discharged from a silicon smelting plant is discharged from an industrial furnace 1, enters a cooling system 2 and is subjected to air surface cooling, the temperature of the flue gas is reduced from 1000 ℃ to 500 ℃, and SO in the flue gas is reduced at the moment2The concentration is 1200mg/Nm3NOx concentration of 300mg/Nm3The concentration of the particles is 6000mg/Nm3(ii) a Then enters pre-dedustingThe system 3 removes dust through primary cyclone, removes the bigger particulate matter at first, each pollutant concentration change in the flue gas is not big at this moment; and then the smoke is introduced into a dry-type electric filter tower 4 by a draught fan 5 in a negative pressure mode, wherein the structure of the dry-type electric filter tower 4 is the same as that of a dry-type electric filter dust removal device in the application No. 201911124719.5, the dry-type electric filter dust removal device comprises 2 dust removal units, each dust removal unit comprises a shell, an anode electrode and a cathode electrode, and each dust removal unit is a cage-shaped piece formed by vertically and horizontally overlapping and welding longitudinal ribs and support rings and is Ti/SnO2The composite electrode is characterized in that a cloth bag is attached to the outer part of the cage-shaped part, the cloth bag is a conventional nylon cloth bag, 4 negative electrodes are arranged around a positive electrode, an air outlet of the device is communicated with an inner cavity of the positive electrode, the negative electrode (corona electrode) of the device is a central bone-shaped electrode, a high-voltage direct-current power supply is adopted, and the voltage is 60 kV; the concentration of the particulate matters in the flue gas is reduced to 200mg/Nm after treatment3When the temperature is reduced to about 270 ℃, other parameters are unchanged, and the flue gas enters a subsequent absorption tower 6; the spraying liquid of the spraying system 7 of the absorption tower 6 is lime milk solution, and two-stage spraying is adopted; demisting the flue gas treated by the absorption tower 6 by a demister 8 and then discharging the flue gas, wherein the temperature of the discharged flue gas is 50 ℃, and SO2The concentration is 35mg/Nm3，NOxThe concentration is 50mg/Nm3The concentration of the particulate matter is 5mg/Nm3。
Example 2: industrial flue gas discharged from a silicon smelting plant is discharged from an industrial furnace 1 and then enters a cooling system 2, the cooling system adopts spray cooling, cooling liquid is ammonia water with the concentration of 15%, the temperature of the cooled flue gas is reduced from 1200 ℃ to 300 ℃, and SO in the flue gas is reduced at the moment2The concentration is 500mg/Nm3NOx concentration of 150mg/Nm3The concentration of the particulate matter is 4000mg/Nm3(ii) a Then the flue gas enters a pre-dust removal system 3 for gravity dust removal, and larger particles are removed firstly, and the concentration of each pollutant in the flue gas is not changed greatly; then the flue gas is introduced into a dry type electric filter tower 4 by a draught fan 5 in a negative pressure mode, wherein the dry type electric filter tower 4 comprises 3 dust removing units, each dust removing unit comprises a shell, an anode electrode and a cathode electrode, the anode electrode is a BDD electrode which is a cage-shaped piece formed by vertically and horizontally overlapping and welding longitudinal ribs and supporting rings, metal filter cloth is attached to the outer part of the cage-shaped piece, 2 cathode electrodes are arranged around the anode electrode, and an air outlet of the device and the inner part of the anode electrode are provided with a plurality of air holesThe cavities are communicated, a cathode electrode (corona electrode) of the device adopts a needle electrode, a power supply is a pulse power supply, and the voltage is 80 kV; the concentration of the particulate matters in the flue gas is reduced to 100mg/Nm after treatment3Cooling to about 150 ℃ to obtain SO2The concentration is 200mg/Nm3NOx concentration of 80mg/Nm3Entering a subsequent absorption tower 6 and adopting primary spraying; the absorbent in the absorption tower 6 is prepared by mixing and stirring 22 mass percent of dimethyl sulfoxide, 22 mass percent of N-methyl pyrrolidone, 22 mass percent of propylene glycol phenyl ether, 6 mass percent of span and 6 mass percent of tween for 2 hours at normal temperature, adding 22 mass percent of water, and continuing stirring for 3 hours; demisting the flue gas treated by the absorption tower 6 by a demister 8 and then discharging the flue gas, wherein the temperature of the discharged flue gas is 30 ℃, and SO2The concentration is 15mg/Nm3，NOxThe concentration is 30mg/Nm3The concentration of the particulate matter is 3mg/Nm3。
Example 3: industrial flue gas discharged from a silicon smelting factory is discharged from an industrial furnace 1 and enters a cooling system 2, the cooling system adopts sleeve cooling, cooling liquid water in the sleeve is cooled, the temperature of the cooled flue gas is reduced from 1200 ℃ to 200 ℃, and SO in the flue gas is reduced at the moment2The concentration is 1500mg/Nm3NOx concentration 250mg/Nm3The concentration of the particulate matter is 8000mg/Nm3(ii) a (ii) a Then the flue gas enters a pre-dust removal system 3 to be subjected to dust removal by a filter cylinder, so that larger particles are removed, and the concentration of each pollutant in the flue gas is not changed greatly; then the flue gas is introduced into a modified dry-type electric filter tower 4 by a draught fan 5 in a negative pressure mode, wherein the dry-type electric filter tower comprises 2 dust removing units, each dust removing unit comprises a shell, an anode, a cathode and filter cloth, the anode is a cage-shaped member formed by longitudinally and transversely overlapping and welding longitudinal ribs and support rings and is IrO2An electrode, a filter cloth with catalytic function is attached to the outside of the cage-shaped member, and the catalytic material loaded on the filter cloth is CeO2-TiO2(ii) a 4 cathode electrodes are arranged around the anode electrode, the air outlet of the device is communicated with the inner cavity of the anode electrode, the cathode electrode (corona electrode) of the device adopts a double-area half-bone electrode, the power supply is a high-voltage direct-current power supply, and the voltage is 100 kV; the concentration of the treated flue gas particulate matter is reduced to 50mg/Nm3, the temperature is reduced to about 100 ℃, and SO is added2The concentration is 100mg/Nm3NOx concentration of 50mg/Nm3Entering a subsequent absorption tower 6 and adopting primary spraying; the absorbent in the absorption tower 6 is prepared by mixing and stirring a mixture of dimethyl sulfoxide and dibenzyl sulfoxide (1: 1) with the mass percentage of 21%, n-heptane with the mass percentage of 21%, propylene glycol phenyl ether and n-propanol (1: 1) with the mass percentage of 20%, span with the mass percentage of 8% and tween with the mass percentage of 8% for 2 hours at normal temperature, adding ammonia water with the mass percentage of 22%, and continuously stirring for 3 hours; demisting the flue gas treated by the absorption tower 6 by a demister 8 and then discharging the flue gas, wherein the temperature of the discharged flue gas is 20 ℃, and SO2The concentration is 10mg/Nm3NOx concentration of 10mg/Nm3The concentration of the particulate matter is 2mg/Nm3。
Claims (10)
1. A process for deeply purifying industrial silicon smelting flue gas is characterized by comprising the following steps: the industrial silicon smelting flue gas is discharged from the industrial furnace (1) and enters the cooling system (2), the cooled gas enters the pre-dedusting system (3), after the large particle dust is primarily separated, the flue gas is introduced into a dry type electric filter tower (4) by a draught fan (5) in a negative pressure mode, the particles are charged in the dry electric filter tower (4) through the discharge effect, the strong oxide generated in the discharge process can oxidize and remove the harmful substances in the smoke, the dry electric filter tower (4) filters through the filter cloth and the electric field effect, particulate matters and harmful substances in the flue gas are removed, the flue gas flowing out of the dry type electric filtering tower (4) enters an absorption tower (6), the absorption tower (6) sprays an absorbent through a spraying system (7), the poisonous and harmful substances of sulfur and nitrate in the flue gas are deeply purified, and finally the flue gas is demisted by a demister (8) and then discharged.
2. The process for deep purification of industrial silicon smelting flue gas according to claim 1, which is characterized in that: the cooling of the cooling system is direct cooling or indirect cooling, the direct cooling comprises evaporative cooling and spray cooling, and the indirect cooling comprises water jacket cooling, surface cooling and waste heat boiler cooling.
3. The process for deep purification of industrial silicon smelting flue gas according to claim 1, which is characterized in that: the temperature of the gas cooled by the cooling system is 50-500 ℃, and the humidity of the flue gas is 0.1-5%.
4. The process for deep purification of industrial silicon smelting flue gas according to claim 1, which is characterized in that: the pre-dedusting system is a dedusting system with low operation cost and large particle removal capacity, and the pre-dedusting system is a cyclone dust collector, a gravity dust collector or a filter cartridge dust collector.
5. The process for deep purification of industrial silicon smelting flue gas according to claim 1, which is characterized in that: the dry-type electric filter tower comprises more than one dust removal unit, the dust removal unit comprises a shell, an anode and a cathode, the anode is a hollow cylindrical cage body with micropores formed by longitudinally and transversely overlapping and welding longitudinal ribs and support rings or a hollow cylinder with micropores, and filter cloth is loaded on the anode; more than one cathode electrode is arranged around the anode electrode, and the anode electrode and the cathode electrode are respectively connected with a power supply, wherein the air inlet mode is negative pressure type air inlet, air is inlet from the side surface of the dry electric filter tower, and air is outlet from the upper part of the anode electrode.
6. The process for deep purification of industrial silicon smelting flue gas according to claim 5, which is characterized in that: the anode electrode is RuO2Electrode, IrO2Electrode, SnO2Electrode, PbO2Electrode, Ti/SnO2Composite electrode, Ti/PbO2One of a composite electrode, a BDD electrode, a magnesium-aluminum alloy electrode and a molybdenum-chromium alloy electrode.
7. The process for deep purification of industrial silicon smelting flue gas according to claim 5, which is characterized in that: the power supply is a high-voltage direct-current power supply or a pulse power supply, and the voltage is 30 kV-100 kV.
8. The process for deep purification of industrial silicon smelting flue gas according to claim 5, which is characterized in that: the anode electrode is provided with filter cloth which is common filter cloth, electric filter cloth, metal filter cloth or filter cloth coated with catalyst.
9. The process for deep purification of industrial silicon smelting flue gas according to claim 1, which is characterized in that: the absorbent is lime milk solution, or at normal temperature, 20-22% by mass of one or more of dimethyl sulfoxide, sulfolane and dibenzyl sulfoxide, 20-22% by mass of one or more of N-hexane, N-heptane, N-methylpyrrolidone and carbon tetrachloride, 20-22% by mass of propylene glycol phenyl ether and/or N-propanol, 6-8% by mass of span and 6-8% by mass of tween are mixed and stirred for 2 hours, 20-22% by mass of water or/and ammonia water are added, and the mixture is continuously stirred for 3-4 hours to obtain the absorbent.
10. The process for deep purification of industrial silicon smelting flue gas according to claim 1, which is characterized in that: the spraying system is provided with multistage spraying.
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