CN101708431B - Advanced treatment method of sulfur dioxide in sulfuric acid tail gas - Google Patents
Advanced treatment method of sulfur dioxide in sulfuric acid tail gas Download PDFInfo
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- CN101708431B CN101708431B CN2009102163271A CN200910216327A CN101708431B CN 101708431 B CN101708431 B CN 101708431B CN 2009102163271 A CN2009102163271 A CN 2009102163271A CN 200910216327 A CN200910216327 A CN 200910216327A CN 101708431 B CN101708431 B CN 101708431B
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- sulfuric acid
- tail gas
- sulfur dioxide
- acid tail
- treatment method
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Abstract
The invention discloses an advanced treatment method of sulfur dioxide in sulfuric acid tail gas, which mainly comprises the following steps of: (1) humidity quenching and tempering treatment, sending the sulfuric acid gas generated during a sulfuric acid production process to a quenching and tempering tower, and adjusting the relative humidity of the sulfuric acid tail gas to be not larger than 20 percent through adding steam or spraying water; (2) desulfuration treatment, sending the humidity quenching and tempering treated sulfuric acid tail gas to a desulfuration tower, enabling the sulfuric acid tail gas to flow through a catalyst bed layer for converting sulfur dioxide, oxygen and water in the sulfuric acid gas into the sulfuric acid under catalytic oxidation action of the catalyst, wherein the desulfuration operating temperature is not less than 50 DEG C, returning the obtained sulfuric acid solution to a sulfuric acid production system or directly taken the obtained sulfuric acid solution as a product, and exhausting the tail gas which is desulfuration-treated and meets design requirements of advanced treatment. The advanced treatment method of the sulfur dioxide in the sulfuric acid tail gas has the advantages of low resource consumption and operating cost, simple process, high desulfuration efficiency and adaptability, adaptability of recycling economy development, and the like.
Description
Technical field
The present invention relates to chemical industry sulfur dioxide in sulfuric acid tail gas recoverying and utilizing method, more particularly, relate to a kind of method that removes low-concentration sulfur dioxide in waste gas with catalytic oxidation.
Background technology
Swift and violent in Chinese sulfuric acid industrial development in recent years, pollutant discharge amount continues to increase.The exhausted air quantity that China in 2007 sulfuric acid industry year discharges is 1,223 hundred million m
3, account for 4.0% of chemical industry discharge capacity; SO
2Approximately 100,000 tons of total emission volumns, account for 0.4% of national discharge capacity, accounts for chemical industry SO
29.0% of total emission volumn is larger SO
2Emission source.Sulphuric acid production enterprises generally adopts in double conversion double absorption technique or one and turns on a suction technique and connect the tail gas desulfur technology at present, and the tail gas desulfur technology that adopts can make sulfuric acid industry tail gas SO
2Concentration of emission reach existing enterprise's emission limit, but Chinese environmental protection section is in " sulfuric acid industry pollutant emission standard " (exposure draft) of in July, 09 issue, to sulfuric-acid production tail gas SO
2Concentration of emission have higher requirement, emission limit is decided to be to 350mg/m
3, this has also proposed new demand to the sulphuric acid tail-gas deep treatment technology, and the tail gas desulfur technology of prior art is difficult to the requirement that reaches new.
The method that the China sulfuric acid industry is processed for sulphuric acid tail-gas deep has a variety of, comprises ammonia-acid system, soda processes, Citrate Buffer etc.
In publication number CN 101422693A, disclose a kind of sulphuric acid tail-gas deep desulfurization method, this method, take double-absorption technique sulfuric-acid production tail gas as processing object, adopts ammonia process to remove the SO in tail gas
2, namely with sulfuric acid tail gas and ammoniacal liquor, directly touch and remove the SO in tail gas
2, sulfur dioxide concentration in sulfuric acid tail gas can be down to 100mg/m
3Below.This method need consume a large amount of ammonia, is only applicable to the enterprise in ammonia source, and the risk that in technological process, a plurality of process procedures exist ammonia to leak.
In publication number CN1165051, disclose a kind of flue gas desulfurization technique, this method utilizes NaOH to absorb the sulfur dioxide in gas, generates sodium sulfite, and then utilizes calcium hydroxide regeneration, regenerates NaOH and recycles.This method does not make the sulphur resource in sulfuric acid tail gas effectively be recycled, and a large amount of calcium sulfites of appended product, not only can not directly utilize, and also needs huge slag tip or landfill pond to stack or landfill, can cause secondary pollution.In addition, because the NaOH as absorbent is to be come by calcium hydroxide regeneration, a large amount of Ca of introducing
2+, make in absorption equipment the calcium fouling easily occurs, affect system-wide continuous and steady operation.
In publication number CN 1899668A, disclose a kind of method that adopts phosphate ore pulp catalytic oxidative desulfurization low-concentration sulfur dioxide, this method can be processed the sulfuric acid tail gas of sulfur dioxide concentration≤3%, and sulfur dioxide concentration in sulfuric acid tail gas is down to≤300mg/m
3.But this method only is suitable for having the phosphorous chemical industry enterprise of phosphoric acid production facility, has certain application limitation.
In publication number CN1391975A, disclose a kind of sodium chloride that utilizes and administered the method that contains sulfur dioxide flue gas, sulfur-containing smoke gas is content of sulfur dioxide≤20～300ppm after the method is processed.But this method needs electrolytic sodium chloride to produce NaOH, and power consumption is high, operating cost is high.
Present widely used sulphuric acid tail-gas deep desulfurization technology is the Wet technique take absorption process as principle, be that sulfuric acid tail gas directly contacts the sulfur dioxide in absorbing and removing tail gas with the liquid as desulfurizing agent by gas-liquid, the common issue with that this method exists has: 1, due to the problem of absorption process vapor liquid equilibrium, when processing low concentration sulphur dioxide flue gas, because mass transfer force is little, cause desulfuration efficiency not high; 2, the desulfurization material cost is high or be subjected to source restriction, and use is restricted; 3, low, the high humidity of the gas temperature after processing, serious to the exhaust emissions equipment corrosion of carbon steel material, the equipment use cost is high.As adopting the equipment of corrosion-resistant material, the device fabrication cost is high.
Summary of the invention
The defect that exists for the sulphuric acid tail-gas deep processing method of prior art, can not meet the environmental standard of gas washing in SA production emission increasingly stringent, purpose of the present invention aims to provide a kind of new advanced treatment method of sulfur dioxide in sulfuric acid tail gas, the environmental pollution that brings with sulfur dioxide in the reduce with control sulfuric acid tail gas.
Sulphuric acid tail-gas deep processing method provided by the invention, its thought is to adopt the catalyst with catalysis, utilize oxygen and heat in sulfuric acid tail gas, sulfur dioxide in the catalytic oxidation sulfuric acid tail gas, make sulfur dioxide concentration in sulfuric acid tail gas be down to the deep desulfuration designing requirement, simultaneous reactions generates byproduct H
2SO
4, the sulfuric acid of generation can return to process system, in processing procedure unharmful substance entered environment.
Sulphuric acid tail-gas deep processing method provided by the invention comprises following treatment step:
(1) humidity modifier treatment, send the sulfuric acid tail gas that the sulfuric acid production process process produces into tempering tower, by adding steam or shower water, the relative humidity of sulfuric acid tail gas is adjusted to and is not more than 20%;
(2) desulfurization is processed, sulfuric acid tail gas after the humidity modifier treatment is sent into to desulfurizing tower, make its beds of flowing through, sulfur dioxide under the catalysed oxidn of catalyst in sulfuric acid tail gas, oxygen and water are converted to sulfuric acid, the desulfurization operations temperature is 50 ℃～150 ℃, the sulfuric acid solution that obtains returns to sulfuric acid production system or, directly as product, through desulfurization, processes sulfur dioxide mass body volume concentrations and be not more than 100mg/Nm
3Exhaust emissions.
In technique scheme, the humidity of sulfuric acid tail gas should not be adjusted to excessive, as long as humidity can meet the catalytic oxidation needs of catalyst to sulfur dioxide in sulfuric acid tail gas, it is unhelpful being adjusted into humidity excessive, not only to use a large amount of steam or water, increase the production run cost, and emission humidity is excessive, the corrosion of exhaust emissions equipment can increase, therefore be adjusted to should not be greater than 20% for the relative humidity of sulfuric acid tail gas, further should not, greater than 10%, preferably the relative humidity of sulfuric acid tail gas be adjusted to 3～6%.
In technique scheme, the sulfuric acid tail gas after the humidity modifier treatment, preferably directly enter desulfurizing tower from tempering tower after out, makes the not obvious decline of its temperature.Because catalyst will utilize the heat that sulfuric acid tail gas carries to carry out catalytic oxidation to the sulfur dioxide in sulfuric acid tail gas, the sulfuric acid tail gas temperature is too low, the catalytic oxidation function of catalyst just can not be given full play to, therefore the desulfurization operations temperature can not be too low, should not be lower than 50 ℃, generally 50～150 ℃ of scopes, normally 60～120 ℃ of scopes, preferentially 70～90 ℃ of scopes.
Enter the sulfuric acid tail gas that tempering tower carries out the humidity modifier treatment, its temperature range is generally at 50～150 ℃.Adopt sulfuric acid tail gas directly to enter desulfurizing tower from tempering tower after out, can utilize the temperature of sulfuric acid tail gas itself, the scope that the interior desulfurization operations temperature of desulfurizing tower is being required.Be that method of the present invention can realize the desulfurization operations temperature in desulfurizing tower is controlled by the temperature that control enters the sulfuric acid tail gas of tempering tower.
Adopt method of the present invention, the tail gas of discharging after the beds desulfurization is processed, the sulfur dioxide mass body volume concentrations that it is contained, can make the content of sulfur dioxide in emission meet different sulfur dioxide in sulfuric acid tail gas advanced treating designing requirements, mass body volume concentrations discharging with different, can be controlled to be the mass body volume concentrations of emission sulfur dioxide to be not more than 100mg/Nm
3, be not more than 50mg/Nm
3, be not more than 10mg/Nm
3Or be not more than 5mg/Nm
3, even can make the sulfur dioxide in emission realize zero-emission.Certainly, according to the economy of limitation standard and production, also the mass body volume concentrations of emission sulfur dioxide can be controlled to be to 200mg/Nm
3, or larger.The time that in emission, the mass body volume concentrations of sulfur dioxide is regenerated by beds is controlled, beds carries out the control of recovery time and depends on again two aspects, the one, sulfur dioxide mass body volume concentrations requirement in emission, the 2nd, the catalytic amount that beds uses.In identical sulfur dioxide mass body volume concentrations requirement, the use amount of catalyst is large, and the time that beds need to be regenerated will be longer, otherwise can be shorter; Same catalyst amount, in emission, sulfur dioxide mass body volume concentrations requires to hang down, and namely concentration is larger, and the time that beds need to be regenerated will be longer, otherwise can be shorter.
The catalyst that removes sulfur dioxide in sulfuric acid tail gas that the present invention uses, by Sichuan University's country's flue gas desulfurization center Development and Production, sell towards the society, and the user is acquisition from here.
Sulphuric acid tail-gas deep processing method provided by the invention, modified by sulfuric acid tail gas being carried out to humidity, adopt the catalyst that has simultaneously the adsoption catalysis function, utilize oxygen and heat in sulfuric acid tail gas, sulfur dioxide gas Catalytic Oxygen in sulfuric acid tail gas is changed into to sulfuric acid, can make mass body volume concentrations in sulfuric acid tail gas be not more than 80000mg/Nm
3Sulfur dioxide be down to 100mg/Nm
3Below, the byproduct H that reaction generates
2SO
4Solution can return to sulfuric acid production system or, directly as product, in the sulphuric acid tail-gas deep processing procedure, in the unharmful substance entered environment, be a kind of sulphuric acid tail-gas deep processing method of green.
Compared with prior art, sun up gets up facture of the present invention, has the characteristics of following several aspects:
(1) the present invention is directed to not tractable low concentration SO in sulfuric acid tail gas
2, by the catalytic oxidation function of desulphurization catalyst, by the SO in sulfuric acid tail gas
2Remove, can be by the SO in emission
2Be controlled at 100mg/Nm
3Below, even can accomplish SO
2Zero-emission.
(2) the present invention is adaptable to sulfur dioxide concentration in sulfuric acid tail gas, sulfur dioxide volume mass content≤80000mg/Nm
3Sulfuric acid tail gas all can adopt method of the present invention to process, the easy meet the requirement of environmental protection of emission, do not produce secondary pollution.
(3) the present invention adopts desulphurization catalyst to process sulfur dioxide in sulfuric acid tail gas, after as the catalyst of desulfurizing agent, once dropping into, can use for a long time, and sweetening process does not need HTHP, small investment, and operating cost is low.
(4) the present invention can realize the recycling of form waste gas of sulfur dioxide, and byproduct sulfuric acid is important industrial chemical, is widely used, and economic worth is high.
(5) the present invention combines exhaust-gas treatment with sulfuric acid production process, and the sulfuric acid that reaction generates can return to sulfuric acid production system, whole process route closed cycle, and technological process is simple, small investment, energy consumption are low.
In brief, the present invention compared with prior art, have advantages of low in resources consumption, technique is simple, desulfuration efficiency is high, strong adaptability, operating cost are low, adapt to recycling economy development.
Method of the present invention, be not only applicable to the sulfur dioxide in sulfuric acid tail gas advanced treating, applicable to other tail gas or sulfur dioxide in flue gas, removes processing fully yet.
The specific embodiment
Below provide embodiments of the invention, and by embodiment, the present invention is further described specifically.Be necessary to be pointed out that at this; embodiment only is used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field can make some nonessential improvement and adjustment is implemented according to the content of the invention described above, but such enforcement should still belong to protection scope of the present invention.
Embodiment 1:
Processed sulfuric acid tail gas, tolerance are 30000Nm
3/ h, content of sulfur dioxide is 5000mg/Nm
3.the processing method of the present embodiment is: the sulfuric acid tail gas that temperature is 120 ℃ of left and right is sent into to tempering tower, the steam that passes into simultaneously the 0.2MPa left and right carries out modified to the sulfuric acid tail gas water capacity that enters tempering tower, the relative humidity of sulfuric acid tail gas is adjusted into to 6% left and right, sulfuric acid tail gas after humidity is modified enters desulfurizing tower by air-introduced machine, sulfuric acid tail gas is flowed through bed that desulphurization catalyst by Sichuan University country flue gas desulfurization center Development and Production forms, under the catalysed oxidn of catalyst, sulfur dioxide in sulfuric acid tail gas, oxygen and water are converted to sulfuric acid, the sulfuric acid solution that obtains returns to sulfuric acid production system, the mass body volume concentrations of controlling sulfur dioxide in emission is not more than 100mg/Nm
3.
Embodiment 2
Processed sulfuric acid tail gas, tolerance are 150000Nm
3/ h, content of sulfur dioxide is 1000mg/Nm
3.the processing method of the present embodiment is: the sulfuric acid tail gas that temperature is 60 ℃ of left and right is sent into to tempering tower, the steam that passes into simultaneously the 0.1MPa left and right carries out modified to sulfuric acid tail gas, the relative humidity of sulfuric acid tail gas is adjusted into to 3% left and right, sulfuric acid tail gas after modified enters desulfurizing tower by air-introduced machine, sulfuric acid tail gas is flowed through bed that desulphurization catalyst by Sichuan University country flue gas desulfurization center Development and Production forms, under the catalysed oxidn of catalyst, sulfur dioxide in sulfuric acid tail gas, oxygen and water are converted to sulfuric acid, the sulfuric acid solution that obtains returns to sulfuric acid production system, the mass body volume concentrations of controlling sulfur dioxide in emission is not more than 50mg/Nm
3.
Embodiment 3
Processed sulfuric acid tail gas, tolerance are 20000Nm
3/ h, content of sulfur dioxide is 3000mg/Nm
3.the processing method of the present embodiment is: the sulfuric acid tail gas that temperature is 90 ℃ of left and right is sent into to tempering tower, by shower water in tower, to the sulfuric acid tail gas water capacity that enters tempering tower, carry out modified, the relative humidity of sulfuric acid tail gas is adjusted into to 10% left and right, sulfuric acid tail gas after humidity is modified enters desulfurizing tower by air-introduced machine, sulfuric acid tail gas is flowed through bed that desulphurization catalyst by Sichuan University country flue gas desulfurization center Development and Production forms, under the catalysed oxidn of catalyst, sulfur dioxide in sulfuric acid tail gas, oxygen and water are converted to sulfuric acid, the sulfuric acid solution that obtains returns to sulfuric acid production system, the mass body volume concentrations of controlling sulfur dioxide in emission is not more than 10mg/Nm
3.
Claims (6)
1. advanced treatment method of sulfur dioxide in sulfuric acid tail gas is characterized in that comprising following treatment step:
(1) humidity modifier treatment, send the sulfuric acid tail gas that the sulfuric acid production process process produces into tempering tower, by adding steam or shower water, the relative humidity of sulfuric acid tail gas is adjusted to and is not more than 20%;
(2) desulfurization is processed, sulfuric acid tail gas after the humidity modifier treatment is sent into to desulfurizing tower, make its beds of flowing through, sulfur dioxide under the catalysed oxidn of catalyst in sulfuric acid tail gas, oxygen and water are converted to sulfuric acid, the desulfurization operations temperature is 50 ℃～150 ℃, the sulfuric acid solution that obtains returns to sulfuric acid production system or, directly as product, through desulfurization, processes sulfur dioxide mass body volume concentrations and be not more than 100mg/Nm
3Exhaust emissions.
2. advanced treatment method of sulfur dioxide in sulfuric acid tail gas according to claim 1, is characterized in that the relative humidity of sulfuric acid tail gas is adjusted to and is not more than 10%.
3. advanced treatment method of sulfur dioxide in sulfuric acid tail gas according to claim 2, is characterized in that the relative humidity of sulfuric acid tail gas is adjusted to 3～6%.
4. according to claim 1 and 2 or 3 described advanced treatment method of sulfur dioxide in sulfuric acid tail gas, is characterized in that the sulfuric acid tail gas after the humidity modifier treatment directly enters desulfurizing tower from tempering tower after out, and the desulfurization operations temperature is 50～150 ℃.
5. advanced treatment method of sulfur dioxide in sulfuric acid tail gas according to claim 4, is characterized in that the desulfurization operations temperature is 60～120 ℃.
6. advanced treatment method of sulfur dioxide in sulfuric acid tail gas according to claim 5, is characterized in that the desulfurization operations temperature is 70～90 ℃.
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| CN2009102163271A CN101708431B (en) | 2009-11-25 | 2009-11-25 | Advanced treatment method of sulfur dioxide in sulfuric acid tail gas |
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| CN101708431B true CN101708431B (en) | 2013-11-20 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614775A (en) * | 2011-01-26 | 2012-08-01 | 四川大学 | Method for removing and recovering low concentration sulfur dioxide in industrial exhaust gas |
| CN102512905A (en) * | 2011-11-16 | 2012-06-27 | 瓮福（集团）有限责任公司 | Emission reduction method for tail gas in sulfuric acid production |
| CN102698596A (en) * | 2012-05-31 | 2012-10-03 | 杨秋良 | Method for preparing sulfuric acid by catalytically oxidizing low-concentration sulfur dioxide in baking flue gas |
| CN106621794B (en) * | 2016-09-21 | 2019-04-12 | 中国化学工程第六建设有限公司 | The processing method of coke oven tail gas sulfur dioxide |
| CN107930388A (en) * | 2017-12-01 | 2018-04-20 | 江苏新中金环保科技股份有限公司 | A kind of coke oven flue gas sulfur removal technology and coke oven flue gas desulphurization system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4213958A (en) * | 1977-11-14 | 1980-07-22 | Canadian Industries Limited | Production of sulphur trioxide, sulphuric acid and oleum |
| JP2003128402A (en) * | 2001-10-17 | 2003-05-08 | Sumitomo Metal Mining Co Ltd | Pump tank used in double contact-type equipment for manufacturing sulfuric acid |
| CN1930080A (en) * | 2004-03-12 | 2007-03-14 | 奥托昆普技术公司 | Process and plant for producing sulfuric acid |
| CN101134154A (en) * | 2007-09-13 | 2008-03-05 | 大连理工大学 | Technique of catalytic oxidation flue gas desulfurization and hydrocarbonylation by-product polymerization iron sulfate |
-
2009
- 2009-11-25 CN CN2009102163271A patent/CN101708431B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4213958A (en) * | 1977-11-14 | 1980-07-22 | Canadian Industries Limited | Production of sulphur trioxide, sulphuric acid and oleum |
| JP2003128402A (en) * | 2001-10-17 | 2003-05-08 | Sumitomo Metal Mining Co Ltd | Pump tank used in double contact-type equipment for manufacturing sulfuric acid |
| CN1930080A (en) * | 2004-03-12 | 2007-03-14 | 奥托昆普技术公司 | Process and plant for producing sulfuric acid |
| CN101134154A (en) * | 2007-09-13 | 2008-03-05 | 大连理工大学 | Technique of catalytic oxidation flue gas desulfurization and hydrocarbonylation by-product polymerization iron sulfate |
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