CN113457387A - Method for recovering mercury from sulfur-containing and mercury-containing flue gas - Google Patents
Method for recovering mercury from sulfur-containing and mercury-containing flue gas Download PDFInfo
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Abstract
The invention relates to a method for recovering mercury from sulfur-containing and mercury-containing flue gas, which mainly utilizes a two-stage coupled wet-type electric dust and mist removing device, and comprises the following specific steps: the first step is as follows: carrying out primary treatment on the non-ferrous smelting raw flue gas by a wet washing device; the second step is that: introducing the preliminarily treated flue gas into a first-stage wet electric demister; the third step: then, the mercury-containing sulfuric acid fog drops remaining in the flue gas are subjected to advanced treatment by using a second-stage wet electric demister, mercury in the treated flue gas is efficiently trapped, and acid making treatment or further desulfurization purification is performed; the fourth step: and collecting the mercury-containing sulfuric acid liquid collected by the two-stage wet electric demister, and carrying out vulcanization treatment by using hydrogen sulfide gas to obtain mercury sulfide precipitate for resource recovery. Compared with the prior art, the method can fully recycle the mercury and the sulfur oxides in the flue gas, and prevent the problems of secondary pollution of the mercury and the like.
Description
Technical Field
The invention belongs to the field of environmental protection, mainly aims at the recovery of mercury in flue gas, and relates to a method for efficiently recovering mercury from sulfur-containing mercury-containing wet flue gas in the field of non-ferrous metal metallurgy.
Background
With the continuous improvement of the environmental protection standard of China, the emission standard for controlling the heavy metal in the non-ferrous metal smelting flue gas is also provided. As the biggest mercury emitting country in the world, China faces severe performance pressure. The mercury emission proportion of the non-ferrous metal smelting flue gas is high, the mercury concentration is high, and SO is generated2The concentration is high, and the existing flue gas mercury control technology process cannot meet the increasingly strict emission standard. Therefore, research on flue gas mercury removal and recovery technology in the non-ferrous metal smelting industry is urgently needed. At present, most of the mercury in the flue gas is industrially treated by adsorbing with an adsorbent and then collecting the mercury-adsorbed particles by combining with a downstream electric dust remover or a bag-type dust remover. Although the method can effectively remove mercury, the method is difficult to recycle the removed mercury. And after a part of the mercury is oxidized into divalent mercury by adding an oxidant, the divalent mercury is absorbed and removed by combining the action of a desulfurizing agent in wet desulphurization, but because reducing components exist in the absorption liquid, part of the divalent mercury can be reduced into the mercury again, so that the mercury removal efficiency is reduced.
Chinese patent CN112237822A discloses a technology for adsorbing mercury by taking a cobalt sulfide/porous carbon composite material as an adsorbing material, which is mainly used under the condition of non-ferrous smelting smoke with the temperature of less than 50 ℃. Heating the cobalt sulfide/porous carbon composite material after absorbing elemental mercury to more than 200 ℃ to carry out demercuration treatment, and recovering volatilized mercury vapor through condensation; the cobalt sulfide/porous carbon composite material after demercuration treatment can be directly returned to be used for adsorbing nonferrous metallurgyElemental mercury in the refinery-off gas. Chinese patent CN110433630A discloses a process for deep purification and recovery of mercury in flue gas from lead-zinc smelting, which comprises adding polymer nano-material demercuration agent KH into a first-stage high-efficiency washing demercuration tower and a second-stage deep washing demercuration tower, controlling certain process conditions to realize deep purification of mercury and washing off dust and other heavy metals in the flue gas, further purifying the flue gas by using a gas cooling tower, dynamic waves and electric demisting, and treating the flue gas to obtain treated flue gas in which Hg is in the flue gas<0.03mg/Nm3The mercury content in the sulfuric acid for preparing acid from flue gas is less than 0.0005 percent, but the technical method has the problems that the adsorption material is easy to poison and inactivate, the cost is high, secondary pollution is easy to cause in the system operation process and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for recovering mercury from sulfur-containing and mercury-containing flue gas, which has high resource utilization rate and no secondary pollution.
The purpose of the invention can be realized by the following technical scheme: a method for recovering mercury from sulfur-containing and mercury-containing flue gas mainly utilizes a two-stage coupled wet-type electric dust and mist removing device, and comprises the following specific steps:
the first step is as follows: the non-ferrous smelting raw flue gas is subjected to primary treatment by a wet type washing device, and particulate matters and soluble heavy metal impurities in the flue gas are removed while the temperature of the flue gas is reduced; pollutants in the flue gas after the primary treatment mainly comprise sulfur dioxide and insoluble zero-valent mercury and contain certain water vapor;
the second step is that: introducing the flue gas subjected to the primary treatment into a first-stage wet electric demister, wherein the demister generates a large-space discharge plasma region under the action of higher pulse voltage to form a stronger oxidizing species, so that zero-valent mercury is quickly oxidized into divalent mercury; meanwhile, a part of sulfur dioxide is oxidized into sulfur trioxide and is quickly converted into sulfuric acid fine mist drops under the action of water vapor; because the generated sulfuric acid fine fog drops have good absorption effect on soluble bivalent mercury, the oxidized gaseous mercury can be quickly captured into the liquid drops, and part of fog drops can be partially captured in the pulse wet electric demister.
The third step: then, the mercury-containing sulfuric acid fog drops remaining in the flue gas are subjected to advanced treatment by using a second-stage wet electric demister, mercury in the treated flue gas is efficiently trapped, and acid making treatment or further desulfurization purification is performed;
the fourth step: and collecting the mercury-containing sulfuric acid liquid collected by the two-stage wet electric demister, and carrying out vulcanization treatment by using hydrogen sulfide gas to obtain mercury sulfide precipitate for resource recovery. The sulfuric acid after mercury removal can also be recycled. By the method, mercury and sulfur oxides in the flue gas can be fully recycled, and the problems of secondary pollution of mercury and the like are prevented.
Furthermore, the treated non-ferrous smelting raw flue gas is mercury-containing and sulfur oxide waste gas generated in the non-ferrous smelting industry, and the temperature after wet washing is 20-50 ℃ and the relative humidity is 80-120%.
The mercury in the flue gas after primary treatment mainly exists in the form of zero-valent mercury, and the concentration range of the mercury is 0.05-50mg/m3；SO2The concentration is 0.02-10%.
Furthermore, the first-stage wet electric demister is a pulse electrostatic demisting device, a high-voltage pulse power supply is used for supplying energy, the voltage peak value is 40-100kV, the wave crest width is 0.1-10 microseconds, and the rising front edge of the wave crest is less than 0.5 microseconds; the pulse repetition frequency is 50-500PPS (times/s).
Furthermore, the mist collecting pole used by the first-stage wet electric demister is of a cylindrical or regular hexagonal cylindrical structure, the material is conductive glass fiber reinforced plastic or stainless steel, the diameter or inscribed circle diameter is 200-6000 mm, and the effective length is 3000-6000 mm.
Furthermore, the second-stage wet electric demister is a conventional wet electric demister, the adopted high-voltage power supply is a direct-current power supply, and the voltage is 30-80 kV.
Furthermore, the effective residence time of the flue gas in the two-stage coupled wet-type electric dust removal fog device is 3-20 seconds, the oxidation efficiency of zero-valent mercury is more than 80%, and the concentration of sulfur dioxide which can be converted into sulfuric acid fog is 50-500mg/m3。
Further, the flue gas is subjected to two-stage wet electric removalAfter the treatment of the fog machine, the removal rate of the mercury in the flue gas is more than 80 percent, and the residual sulfuric acid fog is less than 5mg/m3。
Furthermore, the dosage of the hydrogen sulfide in the fourth step is 1.5 to 3 times of the molar quantity of the mercury to be precipitated.
And further, after solid-liquid separation, the mercury sulfide precipitate obtained in the fourth step is recycled as a resource, and the sulfuric acid after mercury removal is also recycled.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a method for efficiently recovering mercury from sulfur-containing mercury-containing wet flue gas in the field of non-ferrous metal metallurgy. Zero-valent mercury and a small amount of sulfur dioxide in the flue gas can be simultaneously oxidized by utilizing the stronger plasma discharge effect in the high-voltage pulse electrostatic demister, and the sulfuric acid fine mist drops converted after the sulfur trioxide obtained by oxidation is combined with water can absorb divalent mercury; carrying out vulcanization treatment on the obtained mercury-containing sulfuric acid by using hydrogen sulfide to obtain mercury sulfide precipitate with high purity, wherein the sulfuric acid after mercury removal can also be subjected to resource recovery; the method is suitable for recycling and resource utilization of mercury and sulfuric acid in industrial flue gas in the fields of energy, metallurgy, chemical industry and the like.
2. The invention mainly utilizes a two-stage coupling wet-type electric dedusting fog device to recover mercury from sulfur-containing mercury-containing flue gas, the two-stage coupling wet-type electric dedusting fog device is connected in series in front and back, the first stage can achieve better discharging effect through a pulse power supply and is beneficial to the oxidation of substances such as charge and mercury, and the second stage is used for removing the substances on the basis of the first stage, so that the same strength of the first stage is not required to be maintained, energy can be saved, zero-valent mercury and a small amount of sulfur dioxide in the flue gas can be simultaneously oxidized by utilizing the stronger plasma discharging action in a high-voltage pulse electrostatic demister, and sulfuric acid fine mist drops converted after the sulfur trioxide obtained by oxidation is combined with water can absorb divalent mercury.
3. And (3) carrying out vulcanization treatment on the obtained mercury-containing sulfuric acid by using hydrogen sulfide, wherein the hydrogen sulfide can vulcanize mercury in the mercury-containing sulfuric acid to generate a mercury sulfide precipitate, which is beneficial to separation and removal of mercury, so that the mercury sulfide precipitate with high purity is obtained, and the sulfuric acid after mercury removal can also be recycled.
4. The method is suitable for recycling and resource utilization of mercury and sulfuric acid in industrial wet flue gas in the fields of energy, metallurgy, chemical industry and the like.
Drawings
FIG. 1 is a flow chart of the process for recovering mercury from sulfur-containing and mercury-containing flue gas according to the present invention.
The notation in the figure is:
1-a first stage wet electric demister; 2-high voltage discharge electrodes; 3-an insulator box; 4-a second stage wet electric demister; 5-sulfuric acid liquid with high-concentration mercury, 6-pulse high-voltage power supply, 7-high-voltage power supply, I-wet washing device, II-two-stage coupling wet electric dust and mist removing device and III-polluted acid purifying and filtering system.
Detailed Description
The invention is described in detail below with reference to specific figures and examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
As shown in fig. 1, the device for recovering mercury from sulfur-containing and mercury-containing flue gas comprises a wet scrubbing device I, a two-stage coupling wet electric dust and mist removing device II and a contaminated acid purifying and filtering system III which are connected in series in sequence.
Wherein the wet-type electric dust and fog removal device II of two-stage coupling includes first order wet electric defroster 1 and second level wet electric defroster 4, is equipped with high-pressure discharge electrode 2 in the first order wet electric defroster 1, and its top is equipped with insulator case 3, and connects pulse high voltage power supply 6, also is equipped with high-pressure discharge electrode in the second level wet electric defroster 4, and the top also is equipped with insulator case 3, connects a high voltage power supply 7.
The method for recovering mercury from sulfur-containing and mercury-containing flue gas by adopting the device mainly comprises the following steps:
the first step is as follows: the non-ferrous smelting raw flue gas S01 is subjected to primary treatment by a wet washing device I, the temperature after wet washing is 20-50 ℃, the relative humidity is 80-120%, and the flue gas is reducedAnd at the same time of temperature, removing the particulate matters and soluble heavy metal impurities in the flue gas. Pollutants in the flue gas after the primary treatment mainly comprise sulfur dioxide and insoluble zero-valent mercury and contain certain water vapor; the concentration range of the zero-valent mercury is 0.05-50mg/m3；SO2The concentration is 0.02-5%.
The second step is that: introducing the flue gas S02 subjected to the primary treatment into a first-stage wet electric demister 1, wherein the demister generates a large-space discharge plasma region under the action of higher pulse voltage to form a stronger oxidizing species, so that zero-valent mercury is quickly oxidized into divalent mercury; meanwhile, a part of sulfur dioxide can be oxidized into sulfur trioxide, and the sulfur trioxide is quickly converted into sulfuric acid fine mist drops under the action of water vapor. Because the generated sulfuric acid fine fog drops have good absorption effect on soluble bivalent mercury, the oxidized gaseous mercury can be quickly captured into the liquid drops, and part of fog drops can be partially captured in the pulse wet electric demister. First order wet electricity defroster 1 is pulse static defogging device, and the receipts fog that uses is drum or regular hexagon barreled structure, and the material is electrically conductive glass steel or stainless steel material, and diameter or inscribed circle diameter are 200 and give first place to with extra care 400mm, and effective length 3000 gives first place to with extra care 6000 mm. The high-voltage pulse power supply supplies energy, the voltage peak value is 40-100kV, the wave crest width is 0.1-10 microseconds, and the rising front edge of the wave crest is less than 0.5 microseconds; the pulse repetition frequency is 50-500PPS (times/s).
The third step: and then the residual mercury-containing sulfuric acid fog drops in the flue gas are treated by using a second-stage wet electric demister 4. Mercury in the treated flue gas is efficiently captured, and acid making treatment or deep desulfurization purification can be performed; the cleaned flue gas S03 exits the top of the second stage wet electric mist eliminator 4. The second-stage wet electric demister 4 is a conventional wet electric demisting device, and has the same structure as the first-stage wet electric demister, but the adopted high-voltage power supply is a direct-current power supply, and the voltage is 30-80 kV.
The effective residence time of the flue gas in the two-stage wet electric demister is 3-20 seconds, the oxidation efficiency of zero-valent mercury is more than 80%, and the concentration of sulfur dioxide converted into sulfuric acid mist is 50-500mg/m3。
The fourth step: and (3) conveying the sulfuric acid liquid 5 (collected at the bottom of the two-stage wet electric demister) with high concentration mercury collected by the two-stage wet electric to a contaminated acid purification and filtration system III, and carrying out vulcanization treatment by using hydrogen sulfide gas S04 to obtain mercury sulfide precipitate S05 with high purity, and carrying out resource recovery. The sulfuric acid S06 after mercury removal can also be recycled. By the method, mercury and sulfur oxides in the flue gas can be fully recycled, and the problems of secondary pollution of mercury and the like are prevented.
Examples of devices and processes using the above are as follows:
example 1
This embodiment adopts a contact circle diameter to be 300mm regular hexagon's stainless steel pipeline as containing sulphur mercury flue gas pulse electrostatic defogging device and regard as the wet electric defroster of first order, and the wet electric defroster of second order is a contact circle diameter to be 300mm regular hexagon's electrically conductive glass steel tube, and the total effective length 3000mm of device, the wet electric defroster of first order, the wet electric defroster length of second order are 1500mm respectively, and the flue gas volume of the former flue gas of pending colored smelting is about 200Nm3H, SO in flue gas2Has a concentration of about 100mg/m3The mercury concentration is 0.1mg/m3And the top of the first-stage wet electric demister and the top of the second-stage wet electric demister are connected with a high-voltage discharge electrode and are provided with an air heating device simultaneously, so that the top water vapor condensation is prevented from generating short circuit.
The specific treatment method comprises the following steps:
the first step is as follows: the method comprises the following steps of carrying out primary treatment on non-ferrous smelting raw flue gas by a wet washing device, carrying out wet and wet washing at the temperature of 30 ℃ and the relative humidity of 100%, and removing particulate matters and soluble heavy metal impurities in the flue gas while reducing the temperature of the flue gas.
The second step is that: introducing the preliminarily treated flue gas into a first-stage wet electric demister, and adjusting a high-voltage pulse power supply to supply energy, wherein the voltage peak value is 60kV, the peak width is 5 microseconds, and the rising front edge of the peak is less than 0.5 microseconds; the pulse repetition frequency is 100PPS (times/s). Rapidly oxidizing zero-valent mercury into divalent mercury; meanwhile, a part of sulfur dioxide can be oxidized into sulfur trioxide, and the sulfur trioxide is quickly converted into sulfuric acid fine mist drops under the action of water vapor.
The third step: then, the residual mercury-containing sulfuric acid fog drops in the flue gas are treated by using a second-stage wet electric demister, the high-voltage power supply voltage of the second-stage wet electric demister is controlled to be 50kV, mercury in the treated flue gas is efficiently captured, and acid making treatment or deep desulfurization purification can be carried out;
the effective residence time of the flue gas in the two stages of wet electric demisters is 10 seconds respectively.
The fourth step: and (3) conveying the sulfuric acid liquid with high-concentration mercury collected by the two stages of wet electricity to a contaminated acid purification and filtration system, and carrying out vulcanization treatment by utilizing hydrogen sulfide gas to obtain mercury sulfide precipitate with high purity for resource recovery. The sulfuric acid after mercury removal can also be recycled.
The result shows that during different discharge voltages of the two-stage high-voltage power supply, the oxidation rate of mercury can be calculated through the concentration of zero-valent mercury at the flue gas inlet and the flue gas outlet of the electric defogging device, and when the discharge of the first-stage pulse power supply is 60kV, the conversion efficiency of mercury is about 60 percent; at a second stage high voltage discharge of 50kV, the mercury conversion efficiency was about 85%, SO2The conversion efficiency of the sulfuric acid mist reaches more than 80 percent, and the concentration of the sulfuric acid mist is about 105mg/m3。
Example 2
This embodiment adopts a contact circle diameter to be 300mm regular hexagon's stainless steel pipeline as the first order of sulphur containing mercury flue gas pulse electrostatic defogging device, and the wet electric defogging device of second grade is a contact circle diameter to be 300mm regular hexagon's electrically conductive glass steel tube, and the total effective length 3000mm of device, first, second grade are 1500mm respectively, and the amount of flue gas is about 200Nm3H, SO in flue gas2Has a concentration of about 200mg/m3The mercury concentration is 0.1mg/m3The top of the defogging device is connected with a high-voltage discharge electrode and is provided with an air heating device to prevent the top moisture from condensing and generating short circuit.
The specific treatment method comprises the following steps:
the first step is as follows: the method comprises the following steps of carrying out primary treatment on non-ferrous smelting raw flue gas by a wet washing device, carrying out wet and wet washing at the temperature of 45 ℃ and the relative humidity of 110%, and removing particulate matters and soluble heavy metal impurities in the flue gas while reducing the temperature of the flue gas.
The second step is that: introducing the preliminarily treated flue gas into a first-stage wet electric demister, and adjusting a high-voltage pulse power supply to supply energy, wherein the voltage peak value is 70kV, the peak width is 6 microseconds, and the rising front edge of the peak is less than 0.5 microseconds; the pulse repetition frequency is 300PPS (times/s). Rapidly oxidizing zero-valent mercury into divalent mercury; meanwhile, a part of sulfur dioxide can be oxidized into sulfur trioxide, and the sulfur trioxide is quickly converted into sulfuric acid fine mist drops under the action of water vapor.
The third step: then, the residual mercury-containing sulfuric acid fog drops in the flue gas are treated by using a second-stage wet electric demister, the high-voltage power supply voltage of the second-stage wet electric demister is controlled to be 50kV, mercury in the treated flue gas is efficiently captured, and acid making treatment or deep desulfurization purification can be carried out;
the effective residence time of the flue gas in the two stages of wet electric demisters is 15 seconds respectively.
The fourth step: and (3) conveying the sulfuric acid liquid with high-concentration mercury collected by the two stages of wet electricity to a contaminated acid purification and filtration system, and carrying out vulcanization treatment by utilizing hydrogen sulfide gas to obtain mercury sulfide precipitate with high purity for resource recovery. The sulfuric acid after mercury removal can also be recycled.
The result shows that during different discharge voltages of the two-stage high-voltage power supply, the oxidation rate of mercury can be calculated through the concentration of zero-valent mercury at the flue gas inlet and the flue gas outlet of the electric defogging device, and when the discharge of the first-stage pulse power supply is 70kV, the conversion efficiency of mercury is about 65%; at a second stage high voltage discharge of 50kV, the mercury conversion efficiency was about 92%, SO2The conversion efficiency of the catalyst reaches more than 83 percent, and the concentration of the sulfuric acid mist is about 230mg/m3。
Example 3
This embodiment adopts a contact circle diameter to be 300mm regular hexagon's stainless steel pipeline as the first order of sulphur containing mercury flue gas pulse electrostatic defogging device, and the wet electric defogging device of second grade is a contact circle diameter to be 300mm regular hexagon's electrically conductive glass steel tube, and the total effective length 3000mm of device, first, second grade are 1500mm respectively, and the amount of flue gas is about 200Nm3H, SO in flue gas2Has a concentration of about 100mg/m3The mercury concentration is 0.1mg/m3The top of the defogging device is connected with a high-voltage discharge electrode and is provided with an air heating device to prevent the top moisture from condensing and generating short circuit.
The specific treatment method comprises the following steps:
the first step is as follows: the method comprises the following steps of carrying out primary treatment on non-ferrous smelting raw flue gas by a wet washing device, carrying out wet and wet washing at the temperature of 20 ℃ and the relative humidity of 120%, and removing particulate matters and soluble heavy metal impurities in the flue gas while reducing the temperature of the flue gas.
The second step is that: introducing the preliminarily treated flue gas into a first-stage wet electric demister, and adjusting a high-voltage pulse power supply to supply energy, wherein the voltage peak value is 80kV, the peak width is 0.1 microsecond, and the rising front edge of the peak is less than 0.5 microsecond; the pulse repetition frequency was 50PPS (times/s). Rapidly oxidizing zero-valent mercury into divalent mercury; meanwhile, a part of sulfur dioxide can be oxidized into sulfur trioxide, and the sulfur trioxide is quickly converted into sulfuric acid fine mist drops under the action of water vapor.
The third step: then, the residual mercury-containing sulfuric acid fog drops in the flue gas are treated by using the second-stage wet electric demister, the high-voltage power supply voltage of the second-stage wet electric demister 4 is controlled to be 50kV, mercury in the treated flue gas is efficiently captured, and acid making treatment or deep desulfurization purification can be carried out;
the effective residence time of the flue gas in the two stages of wet electric demisters is 20 seconds respectively.
The fourth step: and (3) conveying the sulfuric acid liquid with high-concentration mercury collected by the two stages of wet electricity to a contaminated acid purification and filtration system, and carrying out vulcanization treatment by utilizing hydrogen sulfide gas to obtain mercury sulfide precipitate with high purity for resource recovery. The sulfuric acid S06 after mercury removal can also be recycled.
The result shows that during different discharge voltages of the two-stage high-voltage power supply, the oxidation rate of mercury can be calculated through the concentration of zero-valent mercury at the flue gas inlet and the flue gas outlet of the electric defogging device, and when the discharge of the first-stage pulse power supply is 80kV, the conversion efficiency of mercury is about 71 percent; at a second stage high voltage discharge of 50kV, the mercury conversion efficiency was about 88%, SO2The conversion efficiency of the sulfuric acid mist reaches more than 85 percent, and the concentration of the sulfuric acid mist is about 115mg/m3。
Example 4
This embodiment adopts a contact circle diameter to be 300mm regular hexagon's stainless steel pipeline as the first order of sulphur containing mercury flue gas pulse electrostatic defogging device, and the wet electric defogging device of second grade is a contact circle diameter to be 300mm regular hexagon's electrically conductive glass steel tube, and the total effective length 3000mm of device, first, second grade are 1500mm respectively, and the amount of flue gas is about 200Nm3H, SO in flue gas2Has a concentration of about 100mg/m3The mercury concentration is 0.1mg/m3The top of the defogging device is connected with a high-voltage discharge electrode and is provided with an air heating device to prevent the top moisture from condensing and generating short circuit.
The specific treatment method comprises the following steps:
the first step is as follows: the non-ferrous smelting raw flue gas is subjected to primary treatment by a wet washing device, the temperature after wet and wet washing is 50 ℃, the relative humidity is 80%, and particulate matters and soluble heavy metal impurities in the flue gas are removed while the temperature of the flue gas is reduced.
The second step is that: introducing the preliminarily treated flue gas into a first-stage wet electric demister, and adjusting a high-voltage pulse power supply to supply energy, wherein the voltage peak value is 70kV, the peak width is 10 microseconds, and the rising front edge of the peak is less than 0.5 microseconds; the pulse repetition frequency was 500PPS (times/s). Rapidly oxidizing zero-valent mercury into divalent mercury; meanwhile, a part of sulfur dioxide can be oxidized into sulfur trioxide, and the sulfur trioxide is quickly converted into sulfuric acid fine mist drops under the action of water vapor.
The third step: then, the residual mercury-containing sulfuric acid fog drops in the flue gas are treated by using a second-stage wet electric demister, the high-voltage power supply voltage of the second-stage wet electric demister is controlled to be 60kV, mercury in the treated flue gas is efficiently captured, and acid making treatment or deep desulfurization purification can be carried out;
the effective residence time of the flue gas in the two stages of wet electric demisters is 3 seconds respectively.
The fourth step: and (3) conveying the sulfuric acid liquid with high-concentration mercury collected by the two stages of wet electricity to a contaminated acid purification and filtration system, and carrying out vulcanization treatment by utilizing hydrogen sulfide gas to obtain mercury sulfide precipitate with high purity for resource recovery. The sulfuric acid after mercury removal can also be recycled.
The result shows that during different discharge voltages of the two-stage high-voltage power supply, the oxidation rate of mercury can be calculated through the concentration of zero-valent mercury at the flue gas inlet and the flue gas outlet of the electric defogging device, and when the discharge of the first-stage pulse power supply is 70kV, the conversion efficiency of mercury is about 65%; at a second stage high voltage discharge of 60kV, the mercury conversion efficiency is about 90%, SO2The conversion efficiency of the catalyst reaches more than 85 percent, and the concentration of the sulfuric acid mist is about 117mg/m3。
Example 5
This embodiment adopts a contact circle diameter to be 300mm regular hexagon's stainless steel pipeline as the first order of sulphur containing mercury flue gas pulse electrostatic defogging device, and the wet electric defogging device of second grade is a contact circle diameter to be 300mm regular hexagon's electrically conductive glass steel tube, and the total effective length 3000mm of device, first, second grade are 1500mm respectively, and the amount of flue gas is about 200Nm3H, SO in flue gas2Has a concentration of about 100mg/m3The mercury concentration is 0.1mg/m3The top of the defogging device is connected with a high-voltage discharge electrode and is provided with an air heating device to prevent the top moisture from condensing and generating short circuit.
The specific treatment method comprises the following steps:
the first step is as follows: the non-ferrous smelting raw flue gas is subjected to primary treatment by a wet washing device, the temperature after wet and wet washing is 20-50 ℃, the relative humidity is 80-120%, and particulate matters and soluble heavy metal impurities in the flue gas are removed while the temperature of the flue gas is reduced.
The second step is that: introducing the preliminarily treated flue gas into a first-stage wet electric demister, and adjusting a high-voltage pulse power supply to supply energy, wherein the voltage peak value is 70kV, the peak width is 7 microseconds, and the rising front edge of the peak is less than 0.5 microseconds; the pulse repetition frequency is 100PPS (times/s). Rapidly oxidizing zero-valent mercury into divalent mercury; meanwhile, a part of sulfur dioxide can be oxidized into sulfur trioxide, and the sulfur trioxide is quickly converted into sulfuric acid fine mist drops under the action of water vapor.
The third step: then, the residual mercury-containing sulfuric acid fog drops in the flue gas are treated by using a second-stage wet electric demister, the high-voltage power supply voltage of the second-stage wet electric demister is controlled to be 70kV, mercury in the treated flue gas is efficiently captured, and acid making treatment or deep desulfurization purification can be carried out;
the effective residence time of the flue gas in the two stages of wet electric demisters is 8 seconds respectively.
The fourth step: and (3) conveying the sulfuric acid liquid with high-concentration mercury collected by the two stages of wet electricity to a contaminated acid purification and filtration system, and carrying out vulcanization treatment by utilizing hydrogen sulfide gas to obtain mercury sulfide precipitate with high purity for resource recovery. The sulfuric acid after mercury removal can also be recycled.
The result shows that during different discharge voltages of the two-stage high-voltage power supply, the oxidation rate of mercury can be calculated through the concentration of zero-valent mercury at the flue gas inlet and the flue gas outlet of the electric defogging device, and when the discharge of the first-stage pulse power supply is 70kV, the conversion efficiency of mercury is about 65%; when the second stage high voltage discharge is 70kV, the conversion efficiency of mercury is about 91%, and SO2The conversion efficiency of the sulfuric acid mist reaches more than 85 percent, and the concentration of the sulfuric acid mist is about 115mg/m3。
Claims (10)
1. A method for recovering mercury from sulfur-containing and mercury-containing flue gas is characterized in that a two-stage coupling wet type electric dust and mist removing device is mainly utilized, and the specific method is as follows:
the first step is as follows: the non-ferrous smelting raw flue gas is subjected to primary treatment by a wet type washing device, and particulate matters and soluble heavy metal impurities in the flue gas are removed while the temperature of the flue gas is reduced;
the second step is that: introducing the flue gas subjected to the primary treatment into a first-stage wet electric demister, and quickly oxidizing zero-valent mercury into divalent mercury; meanwhile, a part of sulfur dioxide is oxidized into sulfur trioxide and is quickly converted into sulfuric acid fine mist drops under the action of water vapor;
the third step: then, the mercury-containing sulfuric acid fog drops remaining in the flue gas are subjected to advanced treatment by using a second-stage wet electric demister, mercury in the treated flue gas is efficiently trapped, and acid making treatment or further desulfurization purification is performed;
the fourth step: and collecting the mercury-containing sulfuric acid liquid collected by the two-stage wet electric demister, and carrying out vulcanization treatment by using hydrogen sulfide gas to obtain mercury sulfide precipitate for resource recovery.
2. The method of claim 1, wherein the non-ferrous metallurgy raw flue gas is mercury and sulfur oxide containing flue gas generated by non-ferrous metallurgy industry, and the temperature after wet scrubbing is 20-50 ℃ and the relative humidity is 80-120%.
3. The method of claim 1, wherein the mercury in the flue gas after the initial treatment is mainly in the form of zero-valent mercury, and the concentration of the mercury is in the range of 0.05-50mg/m3；SO2The concentration is 0.02-10%.
4. The method for recovering mercury from sulfur-containing and mercury-containing flue gas as claimed in claim 1, wherein the first stage wet electric demister is a pulsed electrostatic demister, and is powered by a high-voltage pulsed power supply, and has a voltage peak value of 40-100kV, a peak width of 0.1-10 microseconds, and a peak rising front of less than 0.5 microseconds; the pulse repetition frequency is 50-500PPS (times/s).
5. The method as claimed in claim 1, wherein the mist collecting device of the first stage wet electric mist eliminator is a cylindrical or hexagonal cylindrical structure made of conductive glass fiber reinforced plastic or stainless steel material, and has a diameter or inscribed circle diameter of 200-.
6. The method as claimed in claim 1, wherein the second stage wet demister is a conventional wet electric demister, and the high voltage power supply is a dc power supply with a voltage of 30-80 kV.
7. The method for recovering mercury from sulfur-containing and mercury-containing flue gas as claimed in claim 1,the effective residence time of the flue gas in the two-stage coupled wet-type electric dust and fog removing device is 3-20 seconds, the oxidation efficiency of zero-valent mercury is more than 80 percent, and the concentration of sulfur dioxide which can be converted into sulfuric acid fog is 50-500mg/m3。
8. The method for recovering mercury from sulfur-containing and mercury-containing flue gas as claimed in claim 1, wherein the flue gas is treated by two stages of wet electric demisters, the mercury removal rate of the flue gas is greater than 80%, and the residual sulfuric acid mist is less than 5mg/m3。
9. The method for recovering mercury from sulfur-containing and mercury-containing flue gas as claimed in claim 1, wherein the amount of hydrogen sulfide used in the fourth step is 1.5-3 times the molar amount of mercury to be precipitated.
10. The method for recovering mercury from sulfur-containing and mercury-containing flue gas as claimed in claim 1, wherein the mercury sulfide precipitate obtained in the fourth step is subjected to solid-liquid separation and then recovered as a resource, and the sulfuric acid after mercury removal is also subjected to resource utilization.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114082291A (en) * | 2021-11-18 | 2022-02-25 | 郑晓峰 | Equipment and method for recycling mercury in waste gas generated by metal smelting |
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| US4057423A (en) * | 1971-09-10 | 1977-11-08 | Mitsui Mining & Smelting Co., Ltd. | Method for the manufacture of mercury free sulfuric acid |
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