CN109364723A - A kind of method that sulfur trioxide is reduced to sulfur dioxide in Flue Gas of Nonferrous Smelting - Google Patents

A kind of method that sulfur trioxide is reduced to sulfur dioxide in Flue Gas of Nonferrous Smelting Download PDF

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CN109364723A
CN109364723A CN201811319203.1A CN201811319203A CN109364723A CN 109364723 A CN109364723 A CN 109364723A CN 201811319203 A CN201811319203 A CN 201811319203A CN 109364723 A CN109364723 A CN 109364723A
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flue gas
sulfur
sulphur
sulfur trioxide
reduced
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CN109364723B (en
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李玉虎
李云
徐志峰
曹才放
田磊
严康
马艳丽
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Jiangxi University of Science and Technology
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    • 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

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Abstract

The present invention relates to the methods that sulfur trioxide in a kind of Flue Gas of Nonferrous Smelting is reduced to sulfur dioxide.This method is to melt sulphur or elemental sulfur as reducing agent, it is pressurizeed and is sprayed into reaction tower, so that the sulphur drop of atomization comes into full contact with the sulfur trioxide in flue gas and reacts, to which sulfur trioxide is thoroughly reduced to sulfur dioxide, this method can form a large amount of waste acids because sulfur trioxide dissolves in the process to avoid relieving haperacidity flue gas washing, the yield of sulfuric acid is improved simultaneously, and sulphur reducing agent reduction selectivity is good, utilization rate is high, it is at low cost, have many advantages, such as technical process it is simple, without special equipment requires, economical and environmentally friendly high efficiency, industrial application prospect are good.

Description

A kind of method that sulfur trioxide is reduced to sulfur dioxide in Flue Gas of Nonferrous Smelting
Technical field
The present invention relates to a kind of processing methods of Flue Gas of Nonferrous Smelting, in particular to utilize Molten sulphur by nonferrous smelting cigarette Sulfur trioxide is reduced to sulfur dioxide in gas, and the method to reduce waste acid generation belongs to non-ferrous metallurgy fume treatment technology Field.
Background technique
The sulfur dioxide flue gas of nonferrous smelting roasting, melting and pyrite roasting acid manufacturing processes output often contains certain The impurity such as grit, fluorine, chlorine, thus the quality to ensure sulfuric acid product, need washing, purifying to handle, i.e., are that washing is situated between with water Matter carries out washing, purifying to flue gas using dynamic wave scrubbing system.When washing, purifying, grit, fluorine, chlorine in flue gas are caught by water Collection, while sulfur trioxide is dissolved in water and forms sulfuric acid, with the progress of washing, obtains the sulfuric acid solution of the impurity such as fluorine-containing, chlorine, as Waste acid.Main sulfur acid (50-200g/L), fluorine (500-2000mg/L), the chlorine (1000-4000mg/L), arsenic (100- of waste acid 1500mg/L) and a small amount of valuable metal.
Since waste acid impurity content is high, valuable content is low, thus it is difficult to be utilized, it is current mainly to be neutralized using lime Method processing.However, producing a large amount of waste water and waste residue in lime N-process, the generation of gypsum tailings is especially neutralized, it is miscellaneous Matter content height, aqueous height, need specific stockpiling to manage, so that huge cost and environmental protection pressure are born by enterprise.
Other than lime neutralisation, researcher also develops waste acid comprehensive utilization process, and core is separation fluorine chlorine Arsenic impurities recycle the sulfuric acid in waste acid, such as waste acid distillation technique, are easy to the characteristic volatilized using hydrogen fluoride, hydrogen chloride, use Evaporating and concentrating process not only removes fluorine, chlorine impurity, also can get high-concentration sulfuric acid.Other than being concentrated by evaporation, some scholars are proposed The treatment process such as reverse osmosis membrane, electrodialysis.Although these techniques can remove most of impurity, gained sulfuric acid purity still compared with It is low, it is unable to reach industrial sulphuric acid product requirement, and processing cost is higher, thus be difficult to by industrial application.
It therefore, is a kind of method that waste acid generation can be effectively reduced by the removing of sulfur trioxide in flue gas.The prior art In, Chinese patent (application No. is 201711276876.9) discloses a kind of method of middle sulfur trioxide that removes smoke, specific public It is opened to spray into H in flue gas2S is come the technology for the middle sulfur trioxide that removes smoke.Although its sulfur trioxide, due to H2S is reproducibility It is relatively strong, when spraying into flue, preferentially reacted with oxygen, this makes H2The consumption of S is larger.Secondly, H2S not only can be with SO3Instead Answer, can also preferentially with oxygen and SO2Reaction, causes H2S consumption further increases, and processing cost also increases accordingly.Further, since H2S is unconventional class medicament, source is less, and more it is essential that it belongs to gas that is inflammable and explosive and having severe toxicity, this makes The implementation of this technology faces biggish safety and environmental risk.Therefore, it is still left to be desired for the comprehensive utilizating research of waste acid, Industry needs the effective ways of exploitation and control waste acid.
Summary of the invention
For in the prior art, in Flue Gas of Nonferrous Smelting sulfur trioxide subtractive process, reducing agent consumption is big, reduction selection Property it is poor, it is at high cost the defects of, the purpose of the invention is to provide it is a kind of using sulphur as reducing agent restore nonferrous smelting cigarette The method of sulfur trioxide in gas, elemental sulfur are good to sulfur trioxide reduction selectivity, and reduction efficiency is high, and sulphur is easily recycled repetition and makes With consumption is low, is conducive to industrialized production.
In order to achieve the above technical purposes, the present invention provides sulfur trioxides in a kind of Flue Gas of Nonferrous Smelting to be reduced to dioxy Change the method for sulphur, this method is to spray into fused solution sulphur in reduction tower from reduction tower top by spray pattern, and by restoring Tower lower part is passed through the Flue Gas of Nonferrous Smelting counter current contacting reaction in reduction tower, so that sulfur trioxide is reduced in Flue Gas of Nonferrous Smelting Sulfur dioxide.
Preferred scheme, the temperature of the fused solution sulphur are 120 DEG C~205 DEG C.Fused solution sulphur is in preferred temperature Preferable mobility can be kept in range, is conducive to be atomized, and sulphur and sulfur trioxide can be improved within this temperature range Reactivity.
Preferred scheme, the sulfur trioxide concentration of the Flue Gas of Nonferrous Smelting are greater than 0.02%, and flue-gas temperature is greater than 60 DEG C. Flue-gas temperature is preferably at 80~402 DEG C.
Preferred scheme, the Flue Gas of Nonferrous Smelting be nonferrous metal sulfide mineral roasting (such as copper, lead, zinc, tin, antimony, The roasting of the nonferrous metal sulfide minerals such as cobalt, nickel, gold), sulfur dioxide flue gas and/or pyritic material caused by fusion process Sulfur dioxide flue gas caused by acid manufacturing processes.
The flow-rate ratio of preferred scheme, fused solution sulphur and Flue Gas of Nonferrous Smelting is 100kg/h:(0.5~1.5) m3/h。
Preferred scheme, the atomizing pressure of the fused solution sulphur are 3~8bar.It, can by adjusting atomizing pressure range To control fused solution sulphur fogging degree, by adjusting fused solution sulphur in appropriate particle size range, connect with improving with flue gas Contacting surface product, improves reaction efficiency.
Preferred scheme, the residence time that the Flue Gas of Nonferrous Smelting restores in tower are no less than 25s.
Preferred scheme recycles unreacted fused solution sulphur from reduction tower bottom, and is recycled.
Technical solution of the present invention is primarily directed to skill existing for sulfur trioxide reduction subtractive process in Flue Gas of Nonferrous Smelting Art problem and propose.Although the technology of existing vulcanization hydrogen reduction sulfur trioxide can reduce or eliminate the sulfur trioxide in flue gas Content, but restore poor selectivity, part sulfur dioxide is also reduced, and reducing agent consumption is big, at high cost.The present invention selects sulphur Sulphur restores sulfur trioxide as reducing agent, and the reproducibility of elemental sulfur is weaker with respect to the reproducibility of hydrogen sulfide, only and in flue gas Sulfur trioxide reaction, thus selection elemental sulfur can be considered and carry out selective reduction processing sulfur trioxide, it reduces or eliminates in flue gas Sulfur trioxide.But due in flue gas sulfur trioxide concentration it is lower, restored if directlying adopt sulphur, due to gas-solid Reaction interface is small, will lead to that reduction efficiency is low, reduction effect is poor.Technical solution of the present invention at liquid, and passes through sulfur melting Atomizing type makes liquid-state sulfur form particle, strengthens the contact of drusen and sulfur trioxide in flue gas, and in temperature appropriate Promote the progress of reduction reaction Deng under the conditions of.Test result shows that the reduction rate of sulfur trioxide is up to 95%, achieves good Effect, and sulphur can be recycled and be reused.
The concentration that sulfur trioxide in Flue Gas of Nonferrous Smelting is effectively reduced by strengthening front end reduction in the present invention, to thoroughly disappear Except the generation of waste acid, while the yield of sulfuric acid will not be reduced.
The method that sulfur trioxide in Flue Gas of Nonferrous Smelting is reduced to sulfur dioxide by the present invention, detailed process is as follows: first will Sulphur or elemental sulfur melting are liquid sulfur, and the temperature for controlling liquid sulfur is 120~205 DEG C, are then atomized and spray into reaction tower It is interior, it is ensured that sulphur drop comes into full contact with the sulfur trioxide in flue gas, so that sulfur trioxide is reduced to sulfur dioxide, thus shows Writing reduces the waste acid for having Flue Gas of Nonferrous Smelting to generate in washing, and improves the utilization rate of sulphur, is allowed to be converted into sulfuric acid as far as possible.
Reduction reaction process of the invention carries out in reduction tower, and reduction tower structure is as shown in Figure 1, include tower body, tower body Internal upper part is equipped with atomizer and exhanst gas outlet, and tower body lower part is equipped with flue gas access tube, and tower bottom is equipped with a sulphur recovery room, sulphur Heating device is equipped in sulphur recovery room, sulphur recovery outdoor is equipped with circulating line and circulating pump, circulating line and sulphur recovery Room and the connection of tower body internal upper part atomizer.Sulphur first after the melting of sulphur recovery heating indoor, is pumped into tower body by circulating pump Top, to inside lower penetrating tower body after being atomized by atomizer, the Molten sulphur particle after atomization and the cigarette from tower body lower part The Flue Gas of Nonferrous Smelting counter current contacting reaction that gas access tube imports.
Sulphur of the invention is melted by heating devices heat, can be in routine when controlling liquid sulfur temperature less than 135 DEG C Melting operation is carried out under atmosphere；When controlling liquid sulfur temperature greater than in 135 DEG C, melting operation is preferably carried out in an inert atmosphere.
The sulphur that the present invention uses, sulfur content need to be greater than 90%.
Compared with prior art, technical solution of the present invention has the advantage that
1) present invention process is simple, at low cost, is easy to industrial applications.
2) sulphur or elemental sulfur needed for the present invention are from a wealth of sources, are easily obtained, and use process will not introduce new impurity.
3) present invention is using sulphur as reducing agent, and reduction selectivity is good, and consumption is low, and excessive sulphur can be recovered and follow Ring uses, and improves the utilization rate of sulphur.
4) sulfur trioxide reduction rate of the present invention is high, can not only reduce waste acid output, sulfur trioxide in sulfur dioxide flue gas Content can be down to 0.02% hereinafter, waste acid yield is down to 20% hereinafter, sulphuric acid output also can be improved, and have preferable economic valence Value.
5) present invention is environmental-friendly, and no exhaust gas, waste water, waste residue generate.
Detailed description of the invention
Fig. 1 is that non-ferrous metal metallurgy flue gas restores tower structure simplified schematic diagram.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the model of the claims in the present invention protection It encloses.
Embodiment 1:
2200Kg sulphur (sulfur-bearing 95.4%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 170 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 5.5 ± 0.2bar, and atomization flow is 120kg/h.After atomization is stablized, titanium dioxide is opened Sulphur flue gas (CSO2For 12.4-13.8%, CSO3It is 242-255 DEG C for 0.64-0.69%, temperature) conveying switch, into reaction tower Flue gas is imported, control flue gas flow is 1.8 ± 0.1 ten thousand m3/ h so that residence time of the flue gas in reaction tower is greater than 30s.Fortune During row, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, the outlet of reduction tower Sulfur trioxide in flue gas concentration is only 0.015%, and reduction rate is up to 97.24%, while sulfur dioxide concentration is improved to 12.9- 14.4%, the quantum of output of waste acid is by 14.2m before3/ h is reduced to 1.4m3/ h, waste acid reduction are obvious.
Comparative example 1:
2200Kg sulphur (sulfur-bearing 95.4%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 170 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 1.5 ± 0.2bar, and atomization flow is 120kg/h.After atomization is stablized, titanium dioxide is opened Sulphur flue gas (CSO2For 12.4-13.8%, CSO3It is 242-255 DEG C for 0.64-0.69%, temperature) conveying switch, into reaction tower Flue gas is imported, control flue gas flow is 1.8 ± 0.1 ten thousand m3/ h so that residence time of the flue gas in reaction tower is greater than 30s.Fortune During row, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, the outlet of reduction tower Sulfur trioxide in flue gas concentration is 0.137%, reduction rate 78.4%, while sulfur dioxide concentration is improved to 12.7-14.1%, dirty The quantum of output of acid is by 14.2m before3/ h is reduced to 4.1m3/ h, waste acid decrease.
Comparative example 1 the difference from embodiment 1 is that: 1 atomizing pressure of comparative example is lower, only 1.5 ± 0.2bar, and implements Example 1 is then up to 5.5 ± 0.2bar, this difference causes the two to have larger difference to the reduction efficiency of sulfur trioxide.This is because When atomizing pressure is lower, gained sulphur liquid droplet size is larger, so that gas-liquid reaction interface is reduced, to reduce sulfur trioxide Reduction efficiency.Thus, for the completion reduction for guaranteeing sulfur trioxide, should try to improve reduction reaction interface as far as possible.
Embodiment 2:
2860Kg sulphur (sulfur-bearing 91.6%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 135 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 6.5 ± 0.2bar, and atomization flow is 60kg/h.After atomization is stablized, sulfur dioxide is opened Flue gas (CSO2For 20.4-22.1%, CSO3It is 116-132 DEG C for 0.86-0.94%, temperature) conveying switch, it is led into reaction tower Enter flue gas, control flue gas flow is 0.6 ± 0.1 ten thousand m3/ h so that residence time of the flue gas in reaction tower is greater than 75s.Operation In the process, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, and reduction tower exports cigarette Gas sulfur trioxide concentration is only 0.018%, and reduction rate is up to 97.81%, while sulfur dioxide concentration is improved to 21.1- 22.6%, the quantum of output of waste acid is by 8.4m before3/ h is reduced to 0.9m3/ h, waste acid reduction are obvious.
Comparative example 2:
2860Kg sulphur (sulfur-bearing 91.6%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 135 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 6.5 ± 0.2bar, and atomization flow is 60kg/h.After atomization is stablized, sulfur dioxide is opened Flue gas (CSO2For 20.4-22.1%, CSO3It is 48-53 DEG C for 0.86-0.94%, temperature) conveying switch, it is imported into reaction tower Flue gas, control flue gas flow are 0.6 ± 0.1 ten thousand m3/ h so that residence time of the flue gas in reaction tower is greater than 75s.It ran Cheng Zhong needs regular replenishment sulphur, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, and restores tower exiting flue gas Sulfur trioxide concentration is still up to 0.485%, and reduction rate is only 54.2%, while sulfur dioxide concentration is improved to 20.9-22.1%, The quantum of output of waste acid is by 8.4m before3/ h is reduced to 6.4m3/ h, waste acid yield decrease.
Comparative example 2 the difference from example 2 is that: the flue-gas temperature of comparative example 2 is lower compared with embodiment 2, this both makes Effect there are notable differences.This is because when the temperature is low, kinetics of reduction is poor, so that reduction reaction speed drops Low, on the other hand, flue-gas temperature is too low, so that the sulphur droplet surface of atomization is easy to be condensed into solid sulphur.Opposite liquid sulfur The reaction efficiency of sulphur, solid sulphur and sulfur trioxide is lower, this causes the sulfur trioxide in flue gas to be difficult to effectively be restored.Cause And to strengthen the reduction of sulfur trioxide, it should be ensured that flue-gas temperature is not less than 60 DEG C, so that it is carried out in the form of gas-liquid reaction Reduction reaction.
Embodiment 3:
2450Kg sulphur (sulfur-bearing 92.6%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 185 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 4.0 ± 0.2bar, and atomization flow is 210kg/h.After atomization is stablized, titanium dioxide is opened Sulphur flue gas (CSO2For 15.6-17.1%, CSO3It is 296-307 DEG C for 0.66-0.75%, temperature) conveying switch, into reaction tower Flue gas is imported, control flue gas flow is 2.5 ± 0.1 ten thousand m3/ h so that residence time of the flue gas in reaction tower is greater than 36s.Fortune During row, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, the outlet of reduction tower Sulfur trioxide in flue gas concentration is only 0.016%, and reduction rate is up to 97.15%, while sulfur dioxide concentration is improved to 16.2- 17.5%, the quantum of output of waste acid is by 19.6m before3/ h is reduced to 2.2m3/ h, waste acid reduction are obvious.
Embodiment 4:
2280Kg sulphur (sulfur-bearing 95.4%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 125 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 7.5 ± 0.2bar, and atomization flow is 210kg/h.After atomization is stablized, titanium dioxide is opened Sulphur flue gas (CSO2For 26.6-27.4%, CSO3It is 346-358 DEG C for 0.0.89-1.06%, temperature) conveying switch, to reaction tower Interior importing flue gas, control flue gas flow are 1.3 ± 0.1 ten thousand m3/ h so that residence time of the flue gas in reaction tower is greater than 56s. In operational process, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, and reduction tower goes out Mouth sulfur trioxide in flue gas concentration is only 0.012, and reduction rate is up to 98.45%, while sulfur dioxide concentration is improved to 27.5- 28.1%, the quantum of output of waste acid is by 13.4m before3/ h is reduced to 1.5m3/ h, waste acid reduction are obvious.
Embodiment 5:
1960Kg sulphur (sulfur-bearing 99.4%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 155 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 7 ± 0.2bar, and atomization flow is 80kg/h.After atomization is stablized, sulfur dioxide cigarette is opened Gas (CSO2For 9.2-9.8%, CSO3It is 220-226 DEG C for 0.45-0.51%, temperature) conveying switch, cigarette is imported into reaction tower Gas, control flue gas flow are 1.5 ± 0.1 ten thousand m3/ h so that residence time of the flue gas in reaction tower is greater than 42s.Operational process In, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, and restores tower exiting flue gas three Sulfur oxide concentration is only 0.018%, and reduction rate is up to 96.08%, while sulfur dioxide concentration is improved to 9.6-10.2%, waste acid Quantum of output by 8.2m before3/ h is reduced to 0.9m3/ h, waste acid reduction are obvious.
Embodiment 6:
2450Kg sulphur (sulfur-bearing 96.5%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 175 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 6.5 ± 0.2bar, and atomization flow is 75kg/h.After atomization is stablized, sulfur dioxide is opened Flue gas (CSO2For 15.6-16.4%, CSO3It is 84-102 DEG C for 0.52-0.74%, temperature) conveying switch, it is imported into reaction tower Flue gas, control flue gas flow are ten thousand m of 0.9-1.23/ h so that residence time of the flue gas in reaction tower is greater than 64s.Operational process In, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, and restores tower exiting flue gas three Sulfur oxide concentration is only 0.018%, and reduction rate is up to 96.64%, while sulfur dioxide concentration is improved to 16.1-16.9%, dirty The quantum of output of acid is by 7.4m before3/ h is reduced to 0.8m3/ h, waste acid reduction are obvious.
Embodiment 7:
2680Kg sulphur (sulfur-bearing 95.7%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 196 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 3.6 ± 0.2bar, and atomization flow is 100kg/h.After atomization is stablized, titanium dioxide is opened Sulphur flue gas (CSO2For 22.8-24.9%, CSO3It is 154-171 DEG C for 0.77-0.82%, temperature) conveying switch, into reaction tower Flue gas is imported, control flue gas flow is ten thousand m of 1.1-1.33/ h so that residence time of the flue gas in reaction tower is greater than 60s.Operation In the process, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, and reduction tower exports cigarette Gas sulfur trioxide concentration is only 0.017%, and reduction rate is up to 97.27%, while sulfur dioxide concentration is improved to 22.5- 25.4%, the quantum of output of waste acid is by 17.7m before3/ h is reduced to 1.4m3/ h, waste acid reduction are obvious.
Embodiment 8:
2140Kg sulphur (sulfur-bearing 99.1%) is added in sulfur melting groove, opens heater switch, slowly heats up, make sulphur gradually Fusing, control liquid sulfur temperature are 148 ± 2 DEG C.After sulphur is completely dissolved, it is transported in reduction tower with high-pressure pump, warp Nozzle atomization is mist, and atomizing pressure is 5.0 ± 0.2bar, and atomization flow is 360kg/h.After atomization is stablized, titanium dioxide is opened Sulphur flue gas (CSO2For 29.6-33.4%, CSO3It is 384-402 DEG C for 1.28-1.44%, temperature) conveying switch, into reaction tower Flue gas is imported, control flue gas flow is 2.5 ± 0.1 ten thousand m3/ h so that residence time of the flue gas in reaction tower is greater than 45s.Fortune During row, regular replenishment sulphur is needed, to maintain sulfur melting groove liquid-state sulfur liquid level to be greater than 0.5m.Experiment measures, the outlet of reduction tower Sulfur trioxide in flue gas concentration is only 0.012%, and reduction rate is up to 98.85%, while sulfur dioxide concentration is improved to 31.8- 33.9%, the quantum of output of waste acid is by 36.3m before3/ h is reduced to 4.4m3/ h, waste acid reduction are obvious.

Claims (8)

1. a kind of method that sulfur trioxide is reduced to sulfur dioxide in Flue Gas of Nonferrous Smelting, it is characterised in that: by fused solution sulphur It is sprayed into reduction tower by spray pattern from reduction tower top, with the Flue Gas of Nonferrous Smelting being passed through by reduction tower lower part in reduction tower Counter current contacting reaction, so that sulfur trioxide is reduced to sulfur dioxide in Flue Gas of Nonferrous Smelting.
2. the method that sulfur trioxide is reduced to sulfur dioxide in a kind of Flue Gas of Nonferrous Smelting according to claim 1, special Sign is: the temperature of the fused solution sulphur is 120 DEG C~205 DEG C.
3. the method that sulfur trioxide is reduced to sulfur dioxide in a kind of Flue Gas of Nonferrous Smelting according to claim 1, special Sign is: the sulfur trioxide concentration of the Flue Gas of Nonferrous Smelting is greater than 0.02%, and flue-gas temperature is greater than 60 DEG C.
4. the method that sulfur trioxide is reduced to sulfur dioxide in a kind of Flue Gas of Nonferrous Smelting according to claim 3, special Sign is: the Flue Gas of Nonferrous Smelting is the roasting of nonferrous metal sulfide mineral, sulfur dioxide flue gas caused by fusion process, And/or sulfur dioxide flue gas caused by pyritic material acid manufacturing processes.
5. sulfur trioxide is reduced to sulfur dioxide in a kind of Flue Gas of Nonferrous Smelting according to any one of claims 1 to 4 Method, it is characterised in that: the flow-rate ratio of fused solution sulphur and flue gas is 100kg/h:(0.5~1.5) m3/h。
6. the method that sulfur trioxide is reduced to sulfur dioxide in a kind of Flue Gas of Nonferrous Smelting according to claim 1, special Sign is: the atomizing pressure of the fused solution sulphur is 3~8bar.
7. the method that sulfur trioxide is reduced to sulfur dioxide in a kind of Flue Gas of Nonferrous Smelting according to claim 1, special Sign is: the residence time in the Flue Gas of Nonferrous Smelting reduction tower is no less than 25s.
8. the method that sulfur trioxide is reduced to sulfur dioxide in a kind of Flue Gas of Nonferrous Smelting according to claim 1, special Sign is: recycling unreacted fused solution sulphur from reduction tower bottom, and is recycled.
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