CN109364723B - Method for reducing sulfur trioxide in non-ferrous smelting flue gas into sulfur dioxide - Google Patents
Method for reducing sulfur trioxide in non-ferrous smelting flue gas into sulfur dioxide Download PDFInfo
- Publication number
- CN109364723B CN109364723B CN201811319203.1A CN201811319203A CN109364723B CN 109364723 B CN109364723 B CN 109364723B CN 201811319203 A CN201811319203 A CN 201811319203A CN 109364723 B CN109364723 B CN 109364723B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- flue gas
- trioxide
- reduction
- sulfur dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- B01D53/74—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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
-
- 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
- B01D2258/025—Other waste gases from metallurgy plants
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a method for reducing sulfur trioxide in nonferrous smelting flue gas into sulfur dioxide. The method takes molten sulfur or elemental sulfur as a reducing agent, and the molten sulfur or elemental sulfur is pressurized and sprayed into a reaction tower, so that atomized sulfur droplets are in full contact reaction with sulfur trioxide in flue gas, and the sulfur trioxide is completely reduced into sulfur dioxide.
Description
Technical Field
The invention relates to a method for treating nonferrous smelting flue gas, in particular to a method for reducing sulfur trioxide in the nonferrous smelting flue gas into sulfur dioxide by utilizing liquid sulfur so as to reduce the generation of waste acid, belonging to the technical field of nonferrous metallurgy flue gas treatment.
Background
The sulfur dioxide flue gas produced in the processes of nonferrous smelting roasting, smelting and pyrite roasting for acid making usually contains certain dust particles, fluorine, chlorine and other impurities, so that in order to ensure the quality of a sulfuric acid product, the flue gas needs to be washed and purified, namely, the flue gas is washed and purified by using water as a washing medium and adopting a dynamic wave washing system. During washing and purification, dust particles, fluorine and chlorine in the flue gas are captured by water, meanwhile, sulfur trioxide is dissolved in the water to form sulfuric acid, and a sulfuric acid solution containing impurities such as fluorine and chlorine is obtained along with the washing, namely the waste acid. The contaminated acid mainly contains sulfuric acid (50-200g/L), fluorine (500-.
Because the polluted acid has high impurity content and low valuable component content, the polluted acid is difficult to be utilized, and the polluted acid is mainly treated by a lime neutralization method at present. However, a large amount of waste water and waste residues are generated in the lime neutralization process, particularly the neutralized gypsum residues are generated, the impurity content and the water content are high, and specific stockpiling management is required, so that enterprises bear huge cost and environmental protection pressure.
In addition to lime neutralization, researchers also develop a comprehensive utilization process of waste acid, the core of which is to separate fluorine, chlorine and arsenic impurities and recover sulfuric acid in the waste acid, such as a waste acid distillation process, and the process utilizes the characteristic that hydrogen fluoride and hydrogen chloride are easy to volatilize and adopts an evaporation concentration process, so that not only are fluorine and chlorine impurities removed, but also high-concentration sulfuric acid can be obtained. In addition to evaporation and concentration, treatment processes such as reverse osmosis membrane and electrodialysis have also been proposed. Although most of impurities can be removed by the processes, the purity of the obtained sulfuric acid is still low, the requirement of industrial sulfuric acid products cannot be met, and the treatment cost is high, so that the processes are difficult to be applied industrially.
Therefore, the method for removing the sulfur trioxide in the flue gas is a method capable of effectively reducing the generation of the waste acid. In the prior art, Chinese patent (application number 201711276876.9) discloses a method for eliminating sulfur trioxide in flue gas, and particularly discloses spraying H into flue gas2S is used for eliminating sulfur trioxide in the flue gas. Although it is sulfur trioxide, due to H2S is highly reducing and preferentially reacts with oxygen when injected into the flue, which causes H to form2The consumption of S is large. Second, H2S not only can react with SO3Reacting, optionally preferentially with oxygen and SO2Reaction of H2The S consumption is further increased, and the treatment cost is also increased. In addition, due to H2S is an unconventional medicament, has fewer sources, and is a flammable and explosive gas with high toxicity, so that the implementation of the technology faces higher safety and environmental risks. Therefore, the comprehensive utilization research of the waste acid is still to be perfected, and the development of an effective method for treating the waste acid is urgently needed in the industry.
Disclosure of Invention
Aiming at the defects of large consumption of reducing agent, poor reduction selectivity, high cost and the like in the process of removing sulfur trioxide from nonferrous smelting flue gas in the prior art, the invention aims to provide a method for reducing sulfur trioxide in nonferrous smelting flue gas by using sulfur as a reducing agent, wherein simple substance sulfur has good reduction selectivity on sulfur trioxide, high reduction efficiency, easy recovery and reuse of sulfur, low consumption and contribution to industrial production.
In order to achieve the technical purpose, the invention provides a method for reducing sulfur trioxide in non-ferrous smelting flue gas into sulfur dioxide.
In a preferred embodiment, the temperature of the molten liquid sulfur is 120 ℃ to 205 ℃. The molten liquid sulfur can keep better fluidity in the preferred temperature range, is beneficial to atomization, and can improve the reactivity of the sulfur and the sulfur trioxide in the temperature range.
In the preferable scheme, the sulfur trioxide concentration of the nonferrous smelting flue gas is more than 0.02%, and the flue gas temperature is more than 60 ℃. The temperature of the flue gas is preferably 80-402 ℃.
In a preferred scheme, the non-ferrous smelting flue gas is sulfur dioxide flue gas generated in the roasting of non-ferrous metal sulfide ores (such as the roasting of non-ferrous metal sulfide ores such as copper, lead, zinc, tin, antimony, cobalt, nickel, gold and the like), a smelting process and/or sulfur dioxide flue gas generated in an acid making process of pyrite raw materials.
In the preferred scheme, the flow ratio of the molten liquid sulfur to the nonferrous smelting flue gas is 100kg/h (0.5-1.5) m3/h。
In a preferable scheme, the atomization pressure of the molten liquid sulfur is 3-8 bar. Through adjusting the atomization pressure scope, can control the liquid sulphur degree of atomization of melting, through adjusting the liquid sulphur of melting in proper granularity scope to improve the area of contact with the flue gas, improve reaction efficiency.
In a preferable scheme, the retention time in the nonferrous smelting flue gas reduction tower is not less than 25 s.
In a preferred embodiment, the unreacted molten liquid sulfur is recovered from the bottom of the reduction column and recycled.
The technical scheme of the invention is mainly provided for solving the technical problems in the process of reducing and removing sulfur trioxide in nonferrous smelting flue gas. Although the existing technology for reducing sulfur trioxide by using hydrogen sulfide can reduce or eliminate the content of sulfur trioxide in flue gas, the reduction selectivity is poor, partial sulfur dioxide is also reduced, the consumption of a reducing agent is large, and the cost is high. The sulfur is selected as the reducing agent to reduce the sulfur trioxide, the reducibility of elemental sulfur is weaker than that of hydrogen sulfide, and the elemental sulfur only reacts with the sulfur trioxide in the flue gas, so that the elemental sulfur can be selected to selectively reduce and treat the sulfur trioxide, and the sulfur trioxide in the flue gas is reduced or eliminated. However, because the concentration of sulfur trioxide in the flue gas is low, if sulfur is directly used for reduction, the reduction efficiency is low and the reduction effect is poor due to a small gas-solid reaction interface. The technical scheme of the invention melts the sulfur into liquid, and the liquid sulfur forms particles in an atomization mode, thereby strengthening the contact between the sulfur particles and sulfur trioxide in the flue gas and promoting the reduction reaction under the conditions of proper temperature and the like. The test result shows that the reduction rate of sulfur trioxide is as high as 95%, good effect is obtained, and the sulfur can be recycled and reused.
The invention effectively reduces the concentration of sulfur trioxide in the nonferrous smelting flue gas by strengthening the front-end reduction, thereby thoroughly eliminating the generation of waste acid and simultaneously not reducing the yield of sulfuric acid.
The method for reducing sulfur trioxide in nonferrous smelting flue gas into sulfur dioxide comprises the following specific processes: firstly, melting sulfur or elemental sulfur into liquid sulfur, controlling the temperature of the liquid sulfur to be 120-205 ℃, and then atomizing and spraying the liquid sulfur into a reaction tower to ensure that sulfur droplets are fully contacted with sulfur trioxide in flue gas, so that the sulfur trioxide is reduced into sulfur dioxide, thereby obviously reducing waste acid generated by colored smelting flue gas during washing, improving the utilization rate of the sulfur, and converting the sulfur into sulfuric acid as far as possible.
The reduction reaction process of the invention is carried out in a reduction tower, the structure of which is shown in figure 1 and comprises a tower body, the upper part in the tower body is provided with an atomizing nozzle and a flue gas outlet, the lower part of the tower body is provided with a flue gas inlet pipe, the bottom of the tower is provided with a sulfur recovery chamber, the sulfur recovery chamber is internally provided with a heating device, the outside of the sulfur recovery chamber is provided with a circulating pipeline and a circulating pump, and the circulating pipeline is connected with the sulfur recovery chamber and the atomizing nozzle at the upper part in the tower. After being heated and melted in the sulfur recovery chamber, sulfur is pumped into the upper part of the tower body by the circulating pump, atomized by the atomizing nozzle and sprayed into the tower body, and atomized liquid sulfur particles are in countercurrent contact reaction with nonferrous smelting flue gas introduced from the flue gas inlet pipe at the lower part of the tower body.
The sulfur is heated and melted by the heating device, and when the temperature of the liquid sulfur is controlled to be less than 135 ℃, the melting operation can be carried out in the conventional atmosphere; when the temperature of the liquid sulfur is controlled to be higher than 135 ℃, the melting operation is preferably carried out in an inert atmosphere.
The sulfur content of the sulfur adopted by the invention is required to be more than 90 percent.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1) the invention has simple process and low cost and is easy for industrialized application.
2) The sulfur or elemental sulfur required by the invention has wide source and is easy to obtain, and no new impurity is introduced in the using process.
3) The invention adopts sulfur as a reducing agent, has good reduction selectivity and low consumption, and the excessive sulfur can be recycled, thereby improving the utilization rate of the sulfur.
4) The sulfur trioxide reduction rate of the invention is high, which not only can reduce the output of waste acid, the content of sulfur trioxide in sulfur dioxide flue gas can be reduced to below 0.02%, the output of waste acid can be reduced to below 20%, but also can improve the output of sulfuric acid, and has better economic value.
5) The invention is environment-friendly, and does not generate waste gas, waste water and waste residue.
Drawings
FIG. 1 is a schematic diagram of a non-ferrous metal smelting flue gas reduction tower structure.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention as claimed.
Example 1:
2200Kg of sulfur (containing 95.4% of sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 170 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 5.5 +/-0.2 bar, and the atomization flow is 120 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO212.4-13.8% of CSO30.64-0.69 percent and the temperature of 242-3And/h, so that the residence time of the flue gas in the reaction tower is more than 30 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the sulfur trioxide concentration of the flue gas at the outlet of the reduction tower is only 0.015 percent, the reduction rate is as high as 97.24 percent, the sulfur dioxide concentration is increased to 12.9 to 14.4 percent, and the output of the waste acid is 14.2m from the previous output3The reaction time/h is reduced to 1.4m3And h, the waste acid reduction effect is obvious.
Comparative example 1:
2200Kg of sulfur (containing 95.4% of sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 170 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 1.5 +/-0.2 bar, and the atomization flow is 120 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO212.4-13.8% of CSO30.64-0.69 percent and the temperature of 242-3And/h, so that the residence time of the flue gas in the reaction tower is more than 30 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the concentration of sulfur trioxide in the outlet flue gas of the reduction tower is 0.137 percent, the reduction rate is 78.4 percent, and meanwhile, the sulfur trioxide concentration in the outlet flue gas of the reduction tower isThe concentration of sulfur dioxide is increased to 12.7-14.1%, and the yield of waste acid is increased from 14.2m3The reaction time/h is reduced to 4.1m3And/h, the waste acid is reduced.
Comparative example 1 differs from example 1 in that: comparative example 1 has a lower atomization pressure of only 1.5 + -0.2 bar, whereas example 1 has a high atomization pressure of 5.5 + -0.2 bar, which results in a large difference in the reduction efficiency of the two to sulfur trioxide. This is because when the atomization pressure is low, the resulting sulfur droplet size is large, so that the gas-liquid reaction interface is reduced, thereby reducing the reduction efficiency of sulfur trioxide. Therefore, in order to ensure the complete reduction of sulfur trioxide, the reduction reaction interface should be improved as much as possible.
Example 2:
2860Kg of sulfur (containing 91.6 percent of sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 135 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 6.5 +/-0.2 bar, and the atomization flow is 60 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO220.4-22.1% of CSO30.86-0.94 percent and the temperature of 116-3And/h, so that the residence time of the flue gas in the reaction tower is more than 75 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the sulfur trioxide concentration of the flue gas at the outlet of the reduction tower is only 0.018%, the reduction rate is as high as 97.81%, the sulfur dioxide concentration is increased to 21.1-22.6%, and the output of the waste acid is increased from the previous 8.4m3Reduction of the reaction time/h to 0.9m3And h, the waste acid reduction effect is obvious.
Comparative example 2:
2860Kg of sulfur (containing 91.6 percent of sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 135 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 6.5 +/-0.2 bar, and the atomization flow is 60 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO220.4-22.1% of CSO30.86-0.94 percent and the temperature of 48-53 ℃), introducing flue gas into the reaction tower, and controlling the flow rate of the flue gas to be 0.6 +/-0.1 ten thousand meters3And/h, so that the residence time of the flue gas in the reaction tower is more than 75 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the sulfur trioxide concentration of the flue gas at the outlet of the reduction tower is still as high as 0.485%, the reduction rate is only 54.2%, the sulfur dioxide concentration is increased to 20.9-22.1%, and the output of the waste acid is 8.4m3The reaction time/h is reduced to 6.4m3The output of the waste acid is reduced.
Comparative example 2 differs from example 2 in that: the smoke temperature of comparative example 2 is lower than that of example 2, which makes the effect of the two obviously different. This is because when the temperature is low, the reduction reaction kinetics is poor, so that the reduction reaction speed is reduced, and on the other hand, the flue gas temperature is too low, so that the atomized sulfur liquid droplets are easy to condense into solid sulfur on the surface. The reaction efficiency of solid sulfur and sulfur trioxide is relatively low compared to liquid sulfur, which results in the difficulty of effective reduction of sulfur trioxide in flue gas. Thus, in order to enhance the reduction of sulfur trioxide, it is ensured that the temperature of the flue gas is not lower than 60 ℃ so that it undergoes a reduction reaction in the form of a gas-liquid reaction.
Example 3:
2450Kg of sulfur (containing 92.6% of sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 185 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 4.0 +/-0.2 bar, and the atomization flow is 210 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO215.6-17.1% of CSO30.66-0.75 percent and 296 plus 307 ℃) of the temperature, and introducing flue gas into the reaction tower, controlling the flow rate of the flue gas to be 2.5 +/-0.1 ten thousand m3And/h, so that the residence time of the flue gas in the reaction tower is more than 36 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the concentration of sulfur trioxide in the flue gas at the outlet of the reduction tower is only 0.016 percent, the reduction rate is as high as 97.15 percent, and meanwhile, the sulfur trioxide concentration in the flue gas at the outlet of the reduction tower is only 0.016 percentThe concentration of sulfur dioxide is increased to 16.2-17.5%, and the yield of waste acid is increased from the previous 19.6m3Reduction of the reaction time/h to 2.2m3And h, the waste acid reduction effect is obvious.
Example 4:
2280Kg of sulfur (containing 95.4% of sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 125 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 7.5 +/-0.2 bar, and the atomization flow is 210 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO226.6-27.4% of CSO30.0.89-1.06 percent and 358 ℃ of temperature, introducing flue gas into the reaction tower, and controlling the flow rate of the flue gas to be 1.3 +/-0.1 ten thousand m3And h, so that the residence time of the flue gas in the reaction tower is more than 56 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the concentration of sulfur trioxide in the flue gas at the outlet of the reduction tower is only 0.012, the reduction rate is as high as 98.45%, the concentration of sulfur dioxide is increased to 27.5-28.1%, and the output of waste acid is 13.4m3The reaction time/h is reduced to 1.5m3And h, the waste acid reduction effect is obvious.
Example 5:
1960Kg of sulfur (containing 99.4% of sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 155 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 7 +/-0.2 bar, and the atomization flow is 80 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO29.2-9.8% of CSO30.45-0.51 percent and the temperature of 220-3And/h, so that the residence time of the flue gas in the reaction tower is more than 42 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the concentration of sulfur trioxide in the flue gas at the outlet of the reduction tower is only 0.018%, the reduction rate is as high as 96.08%, the concentration of sulfur dioxide is increased to 9.6-10.2%, and the waste acid isThe yield is from the previous 8.2m3Reduction of the reaction time/h to 0.9m3And h, the waste acid reduction effect is obvious.
Example 6:
2450Kg of sulfur (96.5% sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 175 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 6.5 +/-0.2 bar, and the atomization flow is 75 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO215.6-16.4% of CSO30.52-0.74 percent and 84-102 ℃ of temperature, introducing flue gas into the reaction tower, and controlling the flow rate of the flue gas to be 0.9-1.2 ten thousand m3And/h, so that the residence time of the flue gas in the reaction tower is more than 64 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the sulfur trioxide concentration of the flue gas at the outlet of the reduction tower is only 0.018%, the reduction rate is as high as 96.64%, the sulfur dioxide concentration is increased to 16.1-16.9%, and the output of the waste acid is 7.4m3The reaction time/h is reduced to 0.8m3And h, the waste acid reduction effect is obvious.
Example 7:
2680Kg of sulfur (containing 95.7 percent of sulfur) is added into the sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of the liquid sulfur is controlled to be 196 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 3.6 +/-0.2 bar, and the atomization flow is 100 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO222.8-24.9% of CSO30.77-0.82 percent and the temperature of 154-3And/h, so that the residence time of the flue gas in the reaction tower is more than 60 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the sulfur trioxide concentration of the flue gas at the outlet of the reduction tower is only 0.017 percent, the reduction rate is as high as 97.27 percent, meanwhile, the sulfur dioxide concentration is increased to 22.5 to 25.4 percent, and the output of the waste acid is 17.7m from the previous output3Reduction of h to1.4m3And h, the waste acid reduction effect is obvious.
Example 8:
2140Kg of sulfur (containing 99.1% of sulfur) is added into a sulfur melting tank, a heating switch is turned on, the temperature is slowly increased to gradually melt the sulfur, and the temperature of liquid sulfur is controlled to be 148 +/-2 ℃. After the sulfur is completely dissolved, the sulfur is conveyed into a reduction tower by a high-pressure pump and atomized into fog by a nozzle, the atomization pressure is 5.0 +/-0.2 bar, and the atomization flow is 360 kg/h. After the atomization is stable, sulfur dioxide flue gas (C) is startedSO229.6-33.4% of CSO31.28-1.44 percent and the temperature of 384-3And h, enabling the residence time of the flue gas in the reaction tower to be more than 45 s. In the operation process, the sulfur is required to be supplemented periodically so as to maintain the liquid sulfur liquid level of the sulfur melting tank to be more than 0.5 m. The experiment proves that the concentration of sulfur trioxide in the flue gas at the outlet of the reduction tower is only 0.012 percent, the reduction rate is as high as 98.85 percent, the concentration of sulfur dioxide is increased to 31.8 to 33.9 percent, and the output of waste acid is 36.3m from the previous value3The reaction time/h is reduced to 4.4m3And h, the waste acid reduction effect is obvious.
Claims (5)
1. A method for reducing sulfur trioxide in nonferrous smelting flue gas into sulfur dioxide is characterized by comprising the following steps: spraying molten liquid sulfur into a reduction tower from the upper part of the reduction tower in a spraying manner, and carrying out countercurrent contact reaction on the molten liquid sulfur and non-ferrous smelting flue gas introduced into the reduction tower from the lower part of the reduction tower so as to reduce sulfur trioxide in the non-ferrous smelting flue gas into sulfur dioxide; recovering unreacted molten liquid sulfur from the bottom of the reduction tower and recycling the sulfur;
the sulfur trioxide concentration of the nonferrous smelting flue gas is more than 0.02%, and the flue gas temperature is more than 60 ℃;
the atomization pressure of the molten liquid sulfur is 3-8 bar.
2. The method for reducing sulfur trioxide in nonferrous smelting flue gas to sulfur dioxide according to claim 1, characterized in that: the temperature of the molten liquid sulfur is 120-205 ℃.
3. The method for reducing sulfur trioxide in nonferrous smelting flue gas to sulfur dioxide according to claim 1, characterized in that: the non-ferrous smelting flue gas is sulfur dioxide flue gas generated in roasting and smelting processes of non-ferrous metal sulfide ores and/or sulfur dioxide flue gas generated in an acid making process of pyrite raw materials.
4. The method for reducing sulfur trioxide in nonferrous smelting flue gas to sulfur dioxide according to any one of claims 1 to 3, characterized in that: the flow ratio of the molten liquid sulfur to the flue gas is 100kg/h (0.5-1.5) m3/h。
5. The method for reducing sulfur trioxide in nonferrous smelting flue gas to sulfur dioxide according to claim 1, characterized in that: the retention time in the nonferrous smelting flue gas reduction tower is not less than 25 s.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811319203.1A CN109364723B (en) | 2018-11-07 | 2018-11-07 | Method for reducing sulfur trioxide in non-ferrous smelting flue gas into sulfur dioxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811319203.1A CN109364723B (en) | 2018-11-07 | 2018-11-07 | Method for reducing sulfur trioxide in non-ferrous smelting flue gas into sulfur dioxide |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109364723A CN109364723A (en) | 2019-02-22 |
CN109364723B true CN109364723B (en) | 2021-05-11 |
Family
ID=65383797
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811319203.1A Active CN109364723B (en) | 2018-11-07 | 2018-11-07 | Method for reducing sulfur trioxide in non-ferrous smelting flue gas into sulfur dioxide |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109364723B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111167274B (en) * | 2020-01-19 | 2021-11-12 | 中南大学 | Method for removing sulfur trioxide from smelting flue gas and removing device thereof |
CN111482066A (en) * | 2020-04-20 | 2020-08-04 | 青岛惠城环保科技股份有限公司 | SO in desorption high temperature flue gas3Method (2) |
CN115430279A (en) * | 2022-08-03 | 2022-12-06 | 云南铜业股份有限公司西南铜业分公司 | System for sulfur trioxide in desorption smelting flue gas |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5470556A (en) * | 1993-12-22 | 1995-11-28 | Shell Oil Company | Method for reduction of sulfur trioxide in flue gases |
CN1942706A (en) * | 2004-02-14 | 2007-04-04 | 布赖恩·S·希金斯 | Method for in-furnace regulation and control of so3 |
CN201537459U (en) * | 2009-11-10 | 2010-08-04 | 纳尔科摩博泰柯环保科技(上海)有限公司 | SO3 concentration controlling device |
CN203602358U (en) * | 2013-12-04 | 2014-05-21 | 山东凯盛新材料股份有限公司 | Device for producing liquid sulfur dioxide from sulfur trioxide and sulfur |
CN104291277A (en) * | 2014-09-26 | 2015-01-21 | 青岛奥盖克化工股份有限公司 | Environment-friendly production process for producing sulfuric acid by using waste sulfuric acid by virtue of sulfur reduction |
CN108211711A (en) * | 2017-12-06 | 2018-06-29 | 中国恩菲工程技术有限公司 | Remove smoke the method for middle sulfur trioxide |
-
2018
- 2018-11-07 CN CN201811319203.1A patent/CN109364723B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5470556A (en) * | 1993-12-22 | 1995-11-28 | Shell Oil Company | Method for reduction of sulfur trioxide in flue gases |
CN1942706A (en) * | 2004-02-14 | 2007-04-04 | 布赖恩·S·希金斯 | Method for in-furnace regulation and control of so3 |
CN201537459U (en) * | 2009-11-10 | 2010-08-04 | 纳尔科摩博泰柯环保科技(上海)有限公司 | SO3 concentration controlling device |
CN203602358U (en) * | 2013-12-04 | 2014-05-21 | 山东凯盛新材料股份有限公司 | Device for producing liquid sulfur dioxide from sulfur trioxide and sulfur |
CN104291277A (en) * | 2014-09-26 | 2015-01-21 | 青岛奥盖克化工股份有限公司 | Environment-friendly production process for producing sulfuric acid by using waste sulfuric acid by virtue of sulfur reduction |
CN108211711A (en) * | 2017-12-06 | 2018-06-29 | 中国恩菲工程技术有限公司 | Remove smoke the method for middle sulfur trioxide |
Also Published As
Publication number | Publication date |
---|---|
CN109364723A (en) | 2019-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109364723B (en) | Method for reducing sulfur trioxide in non-ferrous smelting flue gas into sulfur dioxide | |
US4163043A (en) | Process for removing H2 S and CO2 from gases and regenerating the adsorbing solution | |
CN109364735B (en) | Method for reducing sulfur trioxide in nonferrous smelting flue gas by using metal sulfide | |
CN110563021A (en) | method and device for harmlessly treating and recycling basic copper chloride | |
CN105819607A (en) | Equipment and method for treating acid-containing waste water | |
WO2014096545A1 (en) | Method and apparatus for acid granulation of matte | |
AU2013366352A1 (en) | Method and apparatus for acid granulation of matte | |
CN110116991B (en) | Recovery process for purifying waste acid by making acid from smelting flue gas | |
CN105505480A (en) | Desulfurization purification system applicable to coke oven gas | |
EP0016290B1 (en) | Continuous process for the removal of sulphur dioxide from waste gases, and hydrogen and sulphuric acid produced thereby | |
US4465655A (en) | Process for the purification of exhaust gases containing sulfuryl fluoride | |
CN210595295U (en) | Device for harmless treatment and recovery of basic copper chloride | |
CN103014338A (en) | Method for processing poor organic phase after solvent extraction indium extracting | |
CA2749907C (en) | Process for recovering metals in the form of metal chlorides or mixed metal chlorides from slag waste materials | |
CN106868319B (en) | A method of obtaining high purity tellurium from the immersion liquid of alkali containing arsenic | |
CN114735659B (en) | Method for recovering tellurium from low-temperature pressurized leaching solution of copper anode slime | |
CN108179290B (en) | A method of it being enriched with mercury from sour mud | |
CN105542873A (en) | A purification process system for coke oven gas | |
CN214915926U (en) | Device for continuously decyanating cyanoacetic acid aqueous solution | |
CN109019530B (en) | Sewage acid treatment and recovery system and treatment and recovery method thereof | |
US3966891A (en) | Process for manufacturing sulfur from a solution of sodium sulfite | |
TW201708100A (en) | Process for recycling use of waste acids capable of producing high purity sulfuric acid that meets requirements of the semiconductor industry and can be used by the semiconductor industry from waste acids which fail to meet requirements of the semiconductor industry | |
US4041142A (en) | Method for removing sulfur oxide from waste gases and recovering elemental sulfur | |
CN114408870B (en) | Method for regenerating copper sulfide waste agent | |
CN113620257B (en) | Method for recovering tellurium and selenium from copper anode slime smelting flue gas |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |