CN103203171A - Technology for removing SO2 in smoke through recovery method - Google Patents

Technology for removing SO2 in smoke through recovery method Download PDF

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Publication number
CN103203171A
CN103203171A CN2012100079902A CN201210007990A CN103203171A CN 103203171 A CN103203171 A CN 103203171A CN 2012100079902 A CN2012100079902 A CN 2012100079902A CN 201210007990 A CN201210007990 A CN 201210007990A CN 103203171 A CN103203171 A CN 103203171A
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China
Prior art keywords
flue gas
tower
technology
desulfurization
removes
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Pending
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CN2012100079902A
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Chinese (zh)
Inventor
童华
杨姝
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Priority to CN2012100079902A priority Critical patent/CN103203171A/en
Publication of CN103203171A publication Critical patent/CN103203171A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a technology for removing SO2 in a smoke through a recovery method. Zinc sulfite reacts with SO2 in the smoke in an aqueous solution in a desulfurization tower as a desulfurization agent to generate a soluble zinc salt in order to absorb SO2 in the smoke and purify the smoke. A rich solution after SO2 absorption is heated to generate ZnSO3 and release SO2. The regenerated ZnSO3 is reused for the SO2 absorption, and released SO2 is trapped and recovered, and is used for producing sulfuric acid or an industrial SO2 gas in order to realize resource recovery.

Description

A kind of absorption method removes SO in the flue gas 2Technology
Technical field
The present invention relates to remove the technical field of sulfur in smoke, particularly a kind of wet desulfurizing process of making desulfurizing agent absorption sulfur dioxide in flue gas with zinc sulfite.
Background technology
SO in the atmospheric environment 2The acid deposition of gas and formation thereof is one of great environmental problem of face of mankind nowadays.Reduce sulfur dioxide (SO2) emissions, the protection environment is extremely urgent.All the time, human is to reduce these toxic gas discharge capacitys to carry out unremitting effort.Country has also formulated relevant policies and the standard limit of smog release that atmospheric environment is administered, wherein to flue gas SO 2Discharge standard also made strict regulations.Flue gas desulfurization technique can be divided into the method for abandoning and absorption method two big classes generally.Most widely used flue gas desulfurization technique is desulfurization method of limestone-gypsum technology at present.This technological process is complicated, the disposable use of desulfurizing agent.SO in the flue gas 2Change into calcium sulfite or calcium sulfate etc. by gaseous contaminant through desulfurization and be fixed, but the desulfurization product gypsum is abandoned disposal mostly because of the quality problems sales resistance, finally forms secondary pollution.Therefore, these technologies do not realize SO on the one hand 2Resource circulation is utilized, and a large amount of desulfurizing agents of sweetening process consumption produce secondary pollution on the other hand, and the desulphurization cost height is not really realized the purpose of cleaner production.
This patent proposes a kind of absorption method flue gas and removes SO 2Technology, not only desulfurizing agent can be recycled, and operating cost is low, can also make the SO in the flue gas 2Become the valuable raw material of industry by pollutant, realize the flue gas desulfurization course of cleaning.
Summary of the invention:
The present invention is directed to the problems referred to above a kind of technology of utilizing zinc sulfite to purify sulfur dioxide in flue gas for desulfurizing agent is provided.This technology is used the SO in the zinc sulfite slurries absorption flue gas 2, and make by heating and to have absorbed SO 2Rich solution resolve, discharge the SO of higher degree 2Gas, the zinc sulfite slurries recover to absorb SO simultaneously 2Ability, capable of circulation for flue gas SO 2Absorb.The SO that parsing discharges 2Be made into different proportion, or for the preparation of high-quality sulfuric acid, perhaps for the preparation of industrial SO 2, the comprehensive reutilization of realization sulphur resource.
Fig. 1 is seen in technological process of the present invention.
Put into the ZnSO that has prepared in the slurry ingredients pond (4) in Fig. 1 3Slurries, its concentration is according to SO in the flue gas 2Content and the requirement of desulfurization degree determined that excursion is 1%-35%.
By shown in Figure 1, enter desulfurizing tower through the flue gas after the dedusting from desulfurizing tower (1) import A, with the ZnSO that sends into circulating pump in the desulfurizing tower 3The slurries contact, the SO in the flue gas 2Enter the zinc sulfite slurries by the gas-liquid membrane mass transfer, generate H with the water reaction 2SO 3, H 2SO 3With ZnSO 3Reaction generates the zinc salt (Zn (HSO of solubility 3) 2).Contain SO 2Rich solution discharged by the desulfurizing tower bottom, pump into Analytic Tower (2).
The rich solution of being sent here by desulfurizing tower (1) enters Analytic Tower (2), through being heated to temperature 35-95 ℃, makes the zine hydrosulfite in the solution resolve into zinc sulfite and sulfur dioxide.The zinc sulfite slurries that regeneration obtains after decomposing are used for SO again by being pumped back in the dosing chamber (4) 2Absorb, do not have desulfurization product and waste water to discharge the secondary pollution that produces.Product after the decomposition is that sulfur dioxide and steam feed condensing tower (3), captures through the high concentration SO behind the condensing tower (3) 2, realize the resource circulation utilization.Condensate liquid is back to Analytic Tower (2), not waste discharge.
The SO that traps 2Can be as required or the gas that is made into 10-20% for the preparation of high-quality sulfuric acid, or purify and obtain 99% industrial SO 2Gas.
Key reaction in desulfurizing tower and the Analytic Tower is as follows:
Desulphurization reaction: SO 2+ H 2O+ZnSO 3=Zn (HSO 3) 2
Regenerative response: Zn (HSO 3) 2=ZnSO 3+ SO 2↑+H 2O
The invention has the beneficial effects as follows:
1, this reaction desulfuration is swift in response, and can accomplish the desulfuration efficiency more than 96%.
2, sweetening process non flouling behaviour: zinc sulfite and sulfur dioxide reactant aqueous solution, desulphurization reaction is at solid zinc sulfite and H 2SO 3Carry out between the solution, desulfurization product is the zinc salt of solubility.Therefore sweetening process is by solid-state process to liquid state, does not have scale problems in the absorption tower, so be conducive to the stable operation of desulphurization system.
3, the SO in the recyclable flue gas of the present invention 2, reclaim as useful resources, prevented and treated secondary pollution, abandoning method than the desulfurization product of technologies such as desulfurization method of limestone-gypsum more has the society and economy meaning.
4, desulfurization operation expense of the present invention is low: the desulfurizing agent that uses in sweetening process is zinc sulfite, and the repeated use of can regenerating, so sorbent consumption is few, and operating cost is low.
5, the related desulfurization rich solution of this patent can decompose at lower temperature and discharges sulfur dioxide, thereby the power consumption of desulfurizing agent regenerative process is lower, has the social effect of energy-saving and emission-reduction.
Description of drawings
Fig. 1 is the process flow diagram that utilizes the zinc sulfite wet desulphurization.1 is desulfurizing tower among the figure, and A is the desulfurizing tower gas approach, and B is the desulfurizing tower exhanst gas outlet, and 2 is Analytic Tower, and 3 is condensing tower, and 4 is the slurries pond.
The specific embodiment
Described in detail below in conjunction with the inventive method of embodiment.
Case study on implementation 1
The absorption reaction technological process of present embodiment as shown in Figure 1.Desulfurizing tower (1) is the spray column of diameter 200mm, and Analytic Tower (2) is the magnetic agitation still formula Analytic Tower of 50L.Flue gas is finished SO by entering desulfurizing tower from desulfurizing tower (1) lower inlet A with the zinc sulfite slurries counter current contacting of sending into circulating pump in the desulfurizing tower 2Absorb, rich solution is discharged by the desulfurizing tower bottom and is entered slurries pond (4).After sorbent consumption arrived to a certain degree, rich solution was also sent into Analytic Tower (2) by shunting and is carried out SO 2Resolve and absorbent regeneration.The flue gas that does not contain dust, flow are 300m 3/ h, SO 2Concentration is 2000mg/m 3, oxygen content 5%.Liquid-gas ratio is 12 o'clock in 20 ℃ of temperature, desulfurizing tower, after the zinc sulfite slurries of service property (quality) percentage 8% are handled, and SO in the purified gas 2Content is 220mg/m 3, desulfuration efficiency 89%.After 45 ℃, 1h were resolved, the zinc sulfite in the sample analysis rich solution has 93% or more regenerated through Analytic Tower.Allocate air in the regeneration gas into, formation contains SO 2Be 12% gas.Regenerative process is negative-pressure operation.
Case study on implementation 2
SO in the flue gas 2Concentration is 8000mg/m 3, adopting process is with case 1, is after 18% the zinc sulfite solution-treated through desulfurizing tower absorption liquid concentration of slurry, the SO in the purified gas 2Content is 700mg/m 3, desulfuration efficiency reaches 92%, and through 60 ℃ of Analytic Towers, after the 1h heating, the zinc sulfite in the rich solution has regeneration more than 92%, SO in the regeneration gas 2Content is 95%, and the regeneration rate of recovery of absorption liquid zinc sulfite reaches 92%.
Above embodiment has proved that desulfurizing agent provided by the present invention can effectively remove sulfur in smoke, and the rich solution that absorbs sulfur dioxide after heating can effectively be regenerated, and regeneration of absorption solution efficient height, has realized the recycling of desulfurizing agent preferably.

Claims (6)

1. described flue gas desulfurization technique comprises the following steps of carrying out successively: contain SO 2Flue gas enter desulfurizing tower from the desulfurizing tower bottom, finish SO with the zinc sulfite solution counter current contacting of sending into circulating pump 2Absorption reaction purifies the flue gas emptying, contains SO after the desulfurization 2Rich solution be pumped to Analytic Tower and carry out parse operation, finish slurries after the parsing and be pumped to the slurries pond and recycle, separate gassing through behind the condenser, collect the SO of higher degree 2Key reaction is:
Absorption reaction: SO 2+ H 2O+ZnSO 3=Zn (HSO 3) 2
Regenerative response: Zn (HSO 3) 2=ZnSO 3+ SO 2↑+H 2O
2. a kind of SO in the flue gas that removes according to claim 1 2Technology, wherein said flue gas desulfurization technique also comprises: using before desulfurization slurry carries out smoke absorption, make flue gas through dust-removing flue, to remove the most of dust in the flue gas.
3. a kind of SO in the flue gas that removes according to claim 1 2Technology, wherein desulfurization absorbent is ZnSO 3, with ZnSO 3With H 2O is made into the slurries of 1%-35% concentration.
4. a kind of SO in the flue gas that removes according to claim 1 2Technology, it is characterized in that: desulphurization system has the pairing of desulfurizing tower and Analytic Tower to use.
5. a kind of SO in the flue gas that removes according to claim 1 2Technology, the desulfurizing tower type is spray column, plate column, packed tower, bubble tower etc.
6. a kind of SO in the flue gas that removes according to claim 1 2Technology, Analytic Tower adopts heating to resolve regeneration sulfurous acid doctor solution, resolution temperature is 35-95 ℃.
CN2012100079902A 2012-01-12 2012-01-12 Technology for removing SO2 in smoke through recovery method Pending CN103203171A (en)

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CN2012100079902A CN103203171A (en) 2012-01-12 2012-01-12 Technology for removing SO2 in smoke through recovery method

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106310881A (en) * 2016-10-26 2017-01-11 成都华西堂环保科技有限公司 Regenerable cyclic absorption flue gas desulfurization technology
CN106916945A (en) * 2017-03-14 2017-07-04 云南罗平锌电股份有限公司 The method that valuable metal is reclaimed in the integrated treatment of a kind of low germanium zinc-oxide calcine of high ferro and zinc sulfite

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Publication number Priority date Publication date Assignee Title
CN1351898A (en) * 2001-11-02 2002-06-05 童志权 Process for treating waste gas containing SO2
CN101920159A (en) * 2010-09-10 2010-12-22 北京金源化学集团有限公司 Method for removing and reclaiming sulfur dioxide from gas by low power consumption renewable absorbent
CN102008886A (en) * 2010-11-22 2011-04-13 浙江双屿实业有限公司 Zinc oxide wet turbulent washing flue gas desulfurization device and process
CN102068876A (en) * 2009-11-20 2011-05-25 北京化工大学 Flue gas desulfurization process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1351898A (en) * 2001-11-02 2002-06-05 童志权 Process for treating waste gas containing SO2
CN102068876A (en) * 2009-11-20 2011-05-25 北京化工大学 Flue gas desulfurization process
CN101920159A (en) * 2010-09-10 2010-12-22 北京金源化学集团有限公司 Method for removing and reclaiming sulfur dioxide from gas by low power consumption renewable absorbent
CN102008886A (en) * 2010-11-22 2011-04-13 浙江双屿实业有限公司 Zinc oxide wet turbulent washing flue gas desulfurization device and process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
南相莉等: "锌灰吸收低浓度二氧化硫的研究", 《中国环境科学学会学术年会论文集 2011 》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106310881A (en) * 2016-10-26 2017-01-11 成都华西堂环保科技有限公司 Regenerable cyclic absorption flue gas desulfurization technology
CN106916945A (en) * 2017-03-14 2017-07-04 云南罗平锌电股份有限公司 The method that valuable metal is reclaimed in the integrated treatment of a kind of low germanium zinc-oxide calcine of high ferro and zinc sulfite
CN106916945B (en) * 2017-03-14 2019-02-26 云南罗平锌电股份有限公司 A kind of method of the integrated treatment recycling valuable metal of the low germanium zinc-oxide calcine of high-speed rail and zinc sulfite

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