CN106606924A - Desulphurization method and apparatus for sulfur-containing tail gas from rotary volatilizing kiln - Google Patents
Desulphurization method and apparatus for sulfur-containing tail gas from rotary volatilizing kiln Download PDFInfo
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- CN106606924A CN106606924A CN201510686932.0A CN201510686932A CN106606924A CN 106606924 A CN106606924 A CN 106606924A CN 201510686932 A CN201510686932 A CN 201510686932A CN 106606924 A CN106606924 A CN 106606924A
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Abstract
The invention specifically relates to a desulphurization method and apparatus for sulfur-containing tail gas from a rotary volatilizing kiln, belonging to the field of desulphurization of a rotary volatilizing kiln used in nonferrous lead-zinc metallurgy. The method comprises the following concrete steps: subjecting sulfur-containing tail gas to heat energy recovery; then washing and cooling the flue gas; and removing sulfur dioxide in the flue gas by using a hydrogen peroxide method. Thus, the content of sulfur dioxide in discharged flue gas can be reduced to 20 mg/Nm<3> or below; and recoverable dilute sulphuric acid is by-produced and returned to a production apparatus for usage.
Description
Technical field
The present invention relates to the environmental technology field of lead-zinc smelting enterprise, specifically zinc abstraction leached mud Jing turn round the sulfur method and device of the sulfur-containing smoke gas that Rotary Kiln roasting is volatilized.
Background technology
Sulfur dioxide is the main pollution factor in atmosphere pollution, and the discharge of sulfur dioxide can cause acid rain to cause to be acidified and corrode water body, crops, environment, building etc., cause huge economic loss.In nonferrous smelting industry, lead-zinc smelting is equally also accompanied by sulfur dioxide pollution, considerable influence is caused to environment, lead zinc industry pollutant emission standard has formulated strict emission standards for sulfur dioxide to discharge, it is both the significant challenge to industry and enterprise, while and the improved opportunity of environmental protection of enterprise measure.
In lead-zinc smelting enterprise, high-grade zinc concentrate typically takes first roasting to obtain Zinc Oxide, then leaches again and obtains zinc sulfate, is electrolysed zinc product by electrolysis production.Contain part lead zinc valuable element in leached mud after Zinc Oxide leaching, to realize innoxious recovery or the comprehensive utilization of valuable element, typically it is mixed into bunker coal and is turning round high-temperature roasting in Rotary Kiln, the valuable elements such as the lead zinc in ore deposit are evaporate in flue gas, then is reclaimed by follow-up cooling, dedusting way of recycling.While roasting, the element sulphur in ore deposit generates sulfur dioxide and evaporate in flue gas.This part titanium dioxide chalcogen low-concentration sulfur dioxide, about 5000mg/Nm3, temperature 200-260 DEG C, if directly emptying without processing, it will cause problem of environmental pollution, and cause the waste of heat energy.The sodium alkali of conventional, calcium method, magnesium oxide method etc., the outstanding problem for existing is that desulfuration efficiency is not good enough, the Sulphur ressource that wastes in tail gas and and generate three new waste products, there is very big limitation in here application, and desulfuration efficiency is also not fully up to expectations.
The content of the invention
It is an object of the invention to provide nonferrous metallurgy revolution Rotary Kiln sulfur-containing smoke gas sulfur method and device.The method carries out energy recovery and desulfurization integrated treatment to turning round Rotary Kiln sulfur-containing smoke gas first.
Particularly, the present invention is employed the following technical solutions：
A kind of revolution Rotary Kiln sulfur-containing tail gas desulfurizer, including heat-energy recovering apparatus 1, washing temperature-reducing tower 2 and desulfurizing tower 4, wherein wash temperature-reducing tower 2 and washing cooling liquid circulation line is driven by washing cooling pump 3, desulfurizing tower 4 is by 5 driving cycle pipeline of desulfurization pump, desulfurizing tower is hydrogen peroxide desulfurizing tower, wherein desulfurization hydrogen peroxide is supplied into desulfurizing tower from hydrogen peroxide storage tank 7 by dioxygen water pump 6, desulfurizing tower has diluted acid export pipeline for the dilute sulfuric acid produced in sweetening process is supplied to lower procedure, it is characterized in that, regulator 9 is equiped with desulfurizing tower also, wherein regulator can be used in the initial driving of tail gas desulfurization device or driving and parking, the hydrogen peroxide of new addition is made to contact with stabilizer and the Stabilization of agent of playing stably, reach the stably new Undec purpose of hydrogen peroxide for adding.
In embodiments above, regulator is made the hydrogen peroxide of new addition be contacted with stabilizer and the Stabilization of agent of playing stably, reaches the Undec purpose of hydrogen peroxide of stably new addition when effect is to can be used in the initial driving of tail gas desulfurization device or driving and parking.In one case, regulator is a pipeline, and pipeline tapping is connected with stabilizer source in circulating slot, the pipeline other end.When needing, stabilizer source is added to stabilizer in circulating slot by the pipeline tapping, and the stabilizer for being added is contacted with hydrogen peroxide and reaches stable purpose.In another case, accommodate in regulator for preventing the stabilizer of decomposing hydrogen dioxide solution, when needing, regulator is opened so that stabilizer is discharged in circulating slot.Both of which is stabilizer release, reaches stabilizer and contacts with hydrogen peroxide.The stabilizer for working in this way can be liquid or solid-state, such as stabiliser solution or graininess stabilizer.
Stabilizer can adopt the various reagents for being prevented from decomposing hydrogen dioxide solution.In general, hydrogen peroxide is more stable under faintly acid and neutrallty condition, and activates in the basic conditions, can fast decoupled in the presence of heavy metal ion.What is adopted in being related to the field of hydrogen peroxide application can prevent hydrogen peroxide from uncontrolledly decomposing added reagent to be referred to as hydrogen peroxide stabilizer.The type of hydrogen peroxide stabilizer has various, for example absorbent-type, chelating type or mixed type etc., they can with by heavy metal ion by adsorb and chelate etc. mode isolate, it is to avoid on dioxygen aquatic products affect.Conventional hydrogen peroxide stabilizer also has the type such as siliceous or not siliceous.Siliceous stabilizer includes such as silicate such as sodium silicate, magnesium silicate stabilizer, and they have excellent absorbability, have good physical and chemical adsorption characteristic to metal ion, so as to reduce the catalytic action of metal ion.Not siliceous stabilizer includes the types such as such as soap.Also macromolecule stabilizer, they form large scale structure by forming macromolecule network structure, with very strong adsorption, and can be obtained by surface modification and adsorb well isolation effect.Some conventional small molecule chelators are also conventional hydrogen peroxide stabilizer, and they are coordinated with macromolecule, it is possible to obtain good stabilized hydrogen peroxide effect.Chelating type stabilizer is generally multivalence organic acid or its salt, such as carboxylate, phosphonate etc..
In another embodiment, stabilizer is to adopt the stabilizer being fixed on carrier or stabilizer to be macromolecule solid-state stabilizer, such as waterglass and polyacrylamide amine stabiliser in itself.In this case, stabilizer is contained in regulator, and regulator is when needed in open kenel or always in open kenel so that when needing, dioxygen water energy is contacted with stabilizer, reaches the Undec purpose of Stabilizing Hydrogen Peroxide.
Hydrogen peroxide stabilizer can be buied from suppliers, such as purchased from the ST-1/2 stabilizers of Jiangsu Cheng Tian Environmental Protection Technology Co., Ltd, it is also possible to which oneself is prepared, and carrys out Stabilizing Hydrogen Peroxide as chelating agen for example with EDTA.
Regulator is arranged in desulfuration absorbing tower, is buried in absorbing liquid, after allocating hydrogen peroxide solution into, plays the purpose that Stabilizing Hydrogen Peroxide does not decompose in initial driving circulating slot.During driving, the stabilizer in regulator is prepared into solution simultaneously with the hydrogen peroxide for first entering into devulcanizer or was inserted before hydrogen peroxide, play a part of Stabilizing Hydrogen Peroxide preparation solution.And stabilizer, without addition in addition, or can also add after operation a period of time as circulating in devulcanizer for liquid is circulated, to ensure stabilizer concentration certain in circulating again by always.
Desulfuration absorbing tower can be form commonly used in the art, for example the apparatus-form such as void tower, packed tower, can be absorbed using one or more levels desulfurization according to practical situation.
In a preferred embodiment, regulator is the device for adding stabilizer in circulating slot, for adding solid-state or liquid stabilizer in circulating slot.
Further, the regulator is the passage or the container for accommodating stabilizer connected with stabilizer source.
In a further preferred embodiment, regulator is provided in the device of the receiving stabilizer of circulating slot, stabilizer accommodated in which is solid state stability agent, solid state stability agent is fixed in regulator, when needing hydrogen peroxide to contact with stabilizer, regulator is in open kenel or regulator is persistently in open kenel, contacts with stabilizer in order to hydrogen peroxide.
Additionally preferably, restorer 8 being additionally provided with diluted acid export pipeline, being equiped with reducing agent in the restorer, the dilute sulfuric acid for being exported before into lower procedure first contacted to carry out reduction treatment to the dilute sulfuric acid product with the reducing agent in restorer.
The dilute sulfuric acid separated before discharge preferably entered restorer and is processed.Restorer device is arranged on dilute sulfuric acid pipeline, is accommodated for decomposing in by-product dilute sulfuric acid the reducing agent of remaining hydrogen peroxide, for playing a role when dilute sulfuric acid is transported by pipeline, to reach the purpose of the hydrogen peroxide remained in decomposition dilute sulfuric acid in restorer device.Restorer for accommodating reducing agent is the container that non-metallic material makes, and inside is filled with the reducing agent material that can decompose remaining hydrogen peroxide in dilute sulfuric acid, is equipped with liquid inlet, liquid outlet and gas discharge outlet；Dilute sulfuric acid containing remaining hydrogen peroxide is entered from liquid inlet, is sprayed above the reducing agent of internal filling, and remaining hydrogen peroxide is broken down into water and oxygen and empties from gas discharge outlet, and liquid is discharged from liquid outlet.Decomposing hydrogen dioxide solution is and foregoing Stabilization opposite effect, as long as therefore the reagent of decomposing hydrogen dioxide solution can be accelerated to can be used as reducing agent used herein, preferably through fixed catalyst, such as metal-oxide bed, for example with Solid Bed made by the material comprising manganese dioxide-catalyst, the reducing agent can also be buied from businessman, the reducing agent buied can be the reducing agent that present invention effect is reached with various principles, such as purchased from the ST-1 reducing agents of Jiangsu Cheng Tian Environmental Protection Technology Co., Ltd.
Invention additionally discloses a kind of revolution Rotary Kiln sulfur-containing tail gas sulfur method, it is characterised in that the method comprising the steps of：1）Energy recovery, the revolution Rotary Kiln sulfur-containing smoke gas for 200-280 DEG C, using heat-energy recovering apparatus recovered flue gas heat, by-product low-pressure steam reclaims the energy；2）Washing cooling, in washing temperature-reducing tower, flue-gas temperature is decreased below into 40 DEG C using circulating cleaning solution, the heat of circulating cleaning solution accumulation removes heat by the way of directly cooling or recirculated water are cooled down indirectly, reduce temperature still to circulate to less than 35 DEG C, then as cleaning mixture reduction revolution Rotary Kiln sulfur-containing smoke gas；3）Desulfurization, the flue gas of 40 DEG C after the washing cooling produced during hydrogen peroxide is adopted in desulphurization plant to above-mentioned steps carries out desulfurization, wherein hydrogen peroxide concentration is 0.01-10%, produced dilute sulfuric acid concentration is maintained at 0-30%, and desulfurized step was further included before flue gas is entered in desulfurizing tower, hydrogen peroxide circulated sprinkling is filled with desulfurizing tower, the hydrogen peroxide of circulated sprinkling and smoke contacts scrubbing CO_2, produced dilute acid concentration accumulates self-loopa cleaning mixture when to a certain extent and discharges, the hydrogen peroxide being wherein filled with is contacted with the stabilizer included in the regulator being arranged in tower in cyclic process.
Preferably, before the diluted acid of discharge continues operation after entering, the restorer being arranged on discharge line can be first passed through, contacts reduction treatment to be carried out to diluted acid with the reducing agent accommodated in which.In treated dilute sulfuric acid, the content of hydrogen peroxide can be close to even up to zero, i.e., can not detect completely.
Beneficial effect：It is of the invention compared with existing sulfur removal technology, the recovered flue gas energy of can classifying：I.e. abundant recovered flue gas heat energy and synthetical recovery Sulphur ressource, by-product sulphuric acid, finally realizes the resource reclaim and deep desulfuration of revolution volatilization kiln exhaust gas.
Description of the drawings
Fig. 1 is the revolution Rotary Kiln sulfur-containing smoke gas desulphurization plant schematic diagram of the present invention.
In figure：1 heat-energy recovering apparatus, 2 washing temperature-reducing towers, 3 washing cooling pumps, 4 desulfurizing towers, 5 desulfurization pumps, 6 dioxygen water pumps, 7 hydrogen peroxide storage tanks, 8 restorers, 9 regulators.
Specific embodiment
Of the invention to pass through to turn round Rotary Kiln sulfur-containing smoke gas distribution process, the recovered steam energy, reduction flue-gas temperature, the sulfur dioxide finally adopted in peroxide passivation removing flue gas, the utilizable dilute sulfuric acid of recovery supply zinc abstraction sulphuric acid plant or electrolysis unit.
Energy recovery.For the ring collection flue gas higher than 200 DEG C, energy recovery has very big value.It is preferred that adopting heat-energy recovering apparatus recovered flue gas heat, the byproduct steam energy.Heat-energy recovering apparatus more preferably adopt heat pipe boiler, reduce cold end corrosion；According to the use requirement of steam, the steam energy of 0.2MPa-0.6MPa can be produced, and after recovered steam, flue-gas temperature is reduced to 130 DEG C -160 DEG C.
Washing cooling.Flue-gas temperature using washing temperature-reducing tower, is decreased below 40 DEG C using circulating cleaning solution by 130 DEG C -160 DEG C of revolution Rotary Kiln sulfur-containing smoke gas again.The heat of circulating cleaning solution accumulation removes heat by the way of direct cooling or recirculated water are cooled down indirectly, reduces temperature and still circulates to less than 35 DEG C, then as cleaning mixture reduction revolution Rotary Kiln sulfur-containing smoke gas.
Hydrogen peroxide desulfurization.Revolution Rotary Kiln sulfur-containing smoke gas are after energy recovery and washing cooling are processed, then adopt in desulfurizing tower, carry out desulfurization using peroxide passivation sulfur removal technology, and in sulfur-containing tail gas, sulfur dioxide sulfur-bearing can be reduced to 20mg/Nm3Hereinafter, while having reclaimed the dilute sulfuric acid of the 25-30% of by-product.The dilute sulfuric acid of this partial desulfurization by-product is all returned to zinc abstraction sulfuric acid apparatus or electrolysis unit is used.
As described above, the energy recovery, washing cooling and peroxide passivation desulfurization through revolution Rotary Kiln sulfur-containing smoke gas, has reclaimed steam energy, has realized the depth reduction of discharging of sulfur dioxide, reclaims the dilute sulfuric acid of by-product and comprehensively utilized.
Specifically, the technical solution used in the present invention is as follows：
Revolution Rotary Kiln sulfur-containing smoke gas sulfur method and device, it is characterised in that the method comprising the steps of：
Step one, energy recovery.Revolution Rotary Kiln sulfur-containing smoke gas for 200-280 DEG C, the such as roasting of zinc abstraction leached mud turn round Rotary Kiln sulfur-containing smoke gas, and using heat-energy recovering apparatus recovered flue gas heat, by-product low-pressure steam reclaims the energy, more preferably using heat pipe boiler, reduce cold end corrosion；
Step 2, washing cooling.In washing temperature-reducing tower, flue-gas temperature is decreased below into 40 DEG C using circulating cleaning solution.The heat of circulating cleaning solution accumulation removes heat by the way of direct cooling or recirculated water are cooled down indirectly, reduces temperature and still circulates to less than 35 DEG C, then as cleaning mixture reduction revolution Rotary Kiln sulfur-containing smoke gas.Scrubbing tower can be various tower equipments that void tower, packed tower etc. can realize this function.
Step 3, desulfurization.Recycling comprising desulfurization and dilute sulfuric acid.The flue gas of 40 DEG C after the washing cooling produced during hydrogen peroxide is adopted in desulphurization plant to above-mentioned steps two carries out desulfurization.Desulfurizing tower can adopt packed tower, void tower etc. to be conducive to the safe and reliable equipment that efficient mass transfer absorbs.Hydrogen peroxide concentration can select 0.01-10%, more preferably preferred 0.01-1%, 0.01-0.1%.Dilute sulfuric acid concentration is positively retained at 0-30%, more preferably 25-30%.
, by the recovered steam energy step by step, cooling, the reduction of discharging of sulfur dioxide depth etc., by-product dilute sulfuric acid can be with reuse for the present invention.
The present invention is further described with example below in conjunction with the accompanying drawings.
Fig. 1 is the device flow chart of the present invention, illustrates to have marked the processing meanss and peroxide passivation desulfurizer of revolution Rotary Kiln sulfur-containing smoke gas in FIG.
Energy recovery：
The 200-280 DEG C of higher revolution Rotary Kiln sulfur-containing smoke gas of temperature initially enter heat-energy recovering apparatus, flue-gas temperature is reduced to 120-160 DEG C such as heat pipe boiler, flue gas heat passes to heat pipe boiler, then feedwater of conducting heat, and the logical steam pipe system of vapor of generation is transported to steam utilization point.
Washing cooling：
In washing temperature-reducing tower, sulfur-containing smoke gas enter wash tower bottoms, and flue-gas temperature is decreased below 40 DEG C by desulfurization pump operation.The heat of circulating cleaning solution accumulation removes heat using direct cooling mode, and after both circulating washing washing cooling, into cooling tower circulation temperature lowering, circulating cleaning solution after cooling tower cooling continues to use as washing cooling liquid.
Desulfurization：
Revolution Rotary Kiln sulfur-containing smoke gas after washing cooling, are the sulfur-containing smoke gas of satisfied vapor.After sulfur-containing smoke gas cooling, in desulfurization, Jing tower tops spray and lower circulation fluid washing scrubbing CO_2, with the prolongation of absorbing reaction time, when dilute acid concentration is accumulated to 25%, self-loopa washing also appropriateness discharge.It is with the carrying out of reaction, continuous to supplement hydrogen peroxide and water in right amount, to ensure the water balance of desulfurizer.
Specific embodiment：
Certain Lead-zinc Smelting Enterprises, according to the composition of Rotary Kiln sulfur-containing smoke gas,（1）Flue gas volatilization flue gas, tolerance 70000Nm3/h, 220 DEG C of temperature, dust-laden 30mg/Nm3, sulfur dioxide 5000mg/Nm3 during zinc leaching residue fired slags.
For（1）The flue-gas temperature of 220 DEG C of revolution volatilization kiln is higher, arranges heat pipe boiler, recovered flue gas heat energy, the saturated vapor of by-product 0.2-0.6MPa；
For（2）Sulfur-containing smoke gas after energy recovery, using circulation wash cooling mode, are cooled to flue gas less than 40 DEG C.
For（3）Washing cooling after sulfur-containing smoke gas, adopt hydrogen peroxide for sulfur dioxide absorption medium.Period supplements dioxygen water consumption and the consumption of water, keeps balance.
Embodiments of the present invention are described in detail above in conjunction with the drawings and specific embodiments, but the invention is not restricted to above-mentioned embodiment, in the ken that art those of ordinary skill possesses, can be making a variety of changes on the premise of without departing from present inventive concept.
Claims (7)
1. it is a kind of to turn round Rotary Kiln sulfur-containing tail gas desulfurizer, including heat-energy recovering apparatus, washing temperature-reducing tower and desulfurizing tower, wherein wash temperature-reducing tower washing cooling liquid circulation line is driven by cooling pump is washed, desulfurizing tower is by desulfurization pump driving cycle pipeline, desulfurizing tower is hydrogen peroxide desulfurizing tower, wherein desulfurization hydrogen peroxide is supplied into desulfurizing tower from hydrogen peroxide storage tank by dioxygen water pump, desulfurizing tower has diluted acid export pipeline for the dilute sulfuric acid produced in sweetening process is supplied to lower procedure, it is characterized in that, regulator is equiped with desulfurizing tower also, wherein regulator can be used in the initial driving of tail gas desulfurization device or driving and parking, the hydrogen peroxide of new addition is made to contact with stabilizer and the Stabilization of agent of playing stably, reach the stably new Undec purpose of hydrogen peroxide for adding.
2. it is as claimed in claim 1 to turn round Rotary Kiln sulfur-containing tail gas desulfurizer, it is characterised in that regulator is the device for adding stabilizer in circulating slot, for adding solid-state or liquid stabilizer in circulating slot.
3. it is as claimed in claim 2 to turn round Rotary Kiln sulfur-containing tail gas desulfurizer, it is characterised in that the regulator is the passage or the container for accommodating stabilizer connected with stabilizer source.
4. it is as claimed in claim 1 to turn round Rotary Kiln sulfur-containing tail gas desulfurizer, it is characterized in that, regulator is provided in the device of the receiving stabilizer of circulating slot, stabilizer accommodated in which is solid state stability agent, solid state stability agent is fixed in regulator, when needing hydrogen peroxide to contact with stabilizer, regulator is in open kenel or regulator is persistently in open kenel, contacts with stabilizer in order to hydrogen peroxide.
5. it is as claimed in claim 1 to turn round Rotary Kiln sulfur-containing tail gas desulfurizer, it is characterized in that, restorer is additionally provided with diluted acid export pipeline, reducing agent is equiped with the restorer, and the dilute sulfuric acid for being exported before into lower procedure first contacted reduction treatment to be carried out to the dilute sulfuric acid product with the reducing agent in restorer.
6. it is a kind of to turn round Rotary Kiln sulfur-containing tail gas sulfur method, it is characterised in that to the method comprising the steps of：1）Energy recovery, the revolution Rotary Kiln sulfur-containing smoke gas for 200-280 DEG C, using heat-energy recovering apparatus recovered flue gas heat, by-product low-pressure steam reclaims the energy；2）Washing cooling, in washing temperature-reducing tower, flue-gas temperature is decreased below into 40 DEG C using circulating cleaning solution, the heat of circulating cleaning solution accumulation removes heat by the way of directly cooling or recirculated water are cooled down indirectly, reduce temperature still to circulate to less than 35 DEG C, then as cleaning mixture reduction revolution Rotary Kiln sulfur-containing smoke gas；3）Desulfurization, the flue gas of 40 DEG C after the washing cooling produced during hydrogen peroxide is adopted in desulphurization plant to above-mentioned steps carries out desulfurization, wherein hydrogen peroxide concentration is 0.01-10%, produced dilute sulfuric acid concentration is maintained at 0-30%, and desulfurized step was further included before flue gas is entered in desulfurizing tower, hydrogen peroxide circulated sprinkling is filled with desulfurizing tower, the hydrogen peroxide of circulated sprinkling and smoke contacts scrubbing CO_2, produced dilute acid concentration accumulates self-loopa cleaning mixture when to a certain extent and discharges, the hydrogen peroxide being wherein filled with is contacted with the stabilizer included in the regulator being arranged in tower in cyclic process.
7. it is as claimed in claim 6 to turn round Rotary Kiln sulfur-containing tail gas sulfur method, it is characterized in that, before the diluted acid of discharge continues operation after entering, the restorer being arranged on discharge line can be first passed through, contacts reduction treatment to be carried out to diluted acid with the reducing agent accommodated in which.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107469602A (en) * | 2017-08-07 | 2017-12-15 | 山东胜星化工有限公司 | One kind recovery sulfur-containing tail gas qualified discharge technology |
| CN107837651A (en) * | 2017-12-14 | 2018-03-27 | 四川龙蟒钛业股份有限公司 | Acid hydrolysis tail gas processing method in a kind of sulfuric acid method titanium pigment production |
| CN107983091A (en) * | 2017-12-14 | 2018-05-04 | 四川龙蟒钛业股份有限公司 | A kind of method of acid hydrolysis tail gas in titanium white waste acid processing sulfuric acid method titanium pigment production |
| CN112657331A (en) * | 2020-12-31 | 2021-04-16 | 成都达奇环境科技有限公司 | Flue gas desulfurization method and flue gas desulfurization equipment |
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| CN112657331A (en) * | 2020-12-31 | 2021-04-16 | 成都达奇环境科技有限公司 | Flue gas desulfurization method and flue gas desulfurization equipment |
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Application publication date: 20170503 |