CN101306304A - Desulfurizing method using soda waste liquid and calcium carbide waste residue - Google Patents
Desulfurizing method using soda waste liquid and calcium carbide waste residue Download PDFInfo
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- CN101306304A CN101306304A CNA2008101293729A CN200810129372A CN101306304A CN 101306304 A CN101306304 A CN 101306304A CN A2008101293729 A CNA2008101293729 A CN A2008101293729A CN 200810129372 A CN200810129372 A CN 200810129372A CN 101306304 A CN101306304 A CN 101306304A
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- cacl
- caso
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- soda ash
- slag
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Abstract
The invention discloses a method for removing SO2 by utilizing soda ash waste liquid and carbide waste slag. CaCl2 in the soda ash waste liquid is utilized to react with the SO2 in flue gas, white CaSO3 settlement is generated, HCl is released and dissolved in water to form hydrochloric acid with very low concentration; Ca(OH)2 in the carbide waste slag is used for neutralizing HCl and generating CaCl2 and water, and CaCl2 is recycled. The desulphurization process mainly consumes Ca(OH)2 in the carbide waste slag. If no local soda ash waste liquid, calcium chloride dehydrate (CaCl2*2HO) produced by the soda ash waste liquid can be purchased for preparing CaCl2 solution. The carbide waste slag can be replaced by lime. The process is characterized by one high, two low and three points of environmental protection. The process firstly has high desulphurization rate, secondly has low fixed-asset investment and low running costs and thirdly utilizes the waste liquid and the waste slag to reduce the environmental pollution. Compared with all prior desulphurization processes, the process has great advantages.
Description
Technical field:
The invention belongs to chemical field, be specially the wet chemical sulfur removal technology.
Background technology:
In recent years, country had strengthened discharge standard has been formulated in the supervision of atmospheric environment and improvement, as " industrial furnace dust emission standard ", " power plant atmosphere pollutants emission standards ", " standard for atmosphere environment quality " etc.In these standards to the SO in the soot emissions
2Content has been done strict regulation.The strict law enforcement of each department environmental administration, enterprise's rectification of being rectified and improved by time limit or stop production of the discharging that exceeds standard, not up to standard must closing.Various under these circumstances sulfur removal technologies arise at the historic moment.These sulfur removal technology majorities are the wet chemistry desulfurization, as caustic lye of soda desulfurization, the desulfurization of soda ash liquid, the ammonia process of desulfurization, calcium hydroxide desulfurization etc.Also introduced and worked out " limestone/gypsum wet desulphurization technology ", " electron beam ammonia-process desulfurization technique " and " activated carbon catalysis adsorption desulfurize technology " etc. in recent years.Various sulfur removal technologies cut both ways, the existing simple small investment of wet chemistry sulfur removal technology, but operating cost is very big; " limestone/gypsum desulfurization " investment of introducing is huge, and general enterprise can't bear.
Need work out the simple small investment of a kind of not only technology now, and the sulfur removal technology route that operating cost is low, desulfurization degree is high.
The present invention's process route that comes to this.
Summary of the invention:
In ammonia-soda process soda ash was produced, 1 ton of soda ash of every production was discharged 10m
3Waste liquid contains 10%CaCl in the waste liquid
2, in polyvinyl chloride (hereinafter to be referred as PVC) was produced, 1 ton of PVC of every production discharged and contains 50%Ca (OH)
2Carbide slag more than 3 tons.Waste soda ash solution and calcium carbide waste slag major part all do not have to utilize, and are discharged to gully or sea, severe contamination environment.
The present invention utilizes the CaCl in the waste soda ash solution just
2With the Ca (OH) in the calcium carbide waste slag
2Remove the SO in the flue gas
2If the locality does not have waste soda ash solution and carbide slag, can buy the calcium chloride dihydrate (CaCl that produces by waste soda ash solution
22H
2O) be mixed with CaCl
2Solution.Carbide slag can replace with lime.
Fig. 1 is asked for an interview in technological process of the present invention.
In Fig. 1 circulatory pool (3), put into the CaCl that has configured
2Solution, solution concentration is according to SO in the flue gas
2The size decision of content and desulfurization degree can also can be generally about 15% more than 20% below 10%.
In Fig. 1 neutralization pond, put into the lime slurry that modulates.
Desulphurization reaction mainly carries out in desulfurizing tower.Adorn two layers of filler in the desulfurizing tower (see figure 3).
Show by Fig. 1, contain SO
2Flue gas enter from desulfurizing tower gas approach (A), discharge from top exhanst gas outlet (B).CaCl in the circulatory pool (3)
2Solution is sent into desulfurizing tower top, CaCl with centrifugal pump (2)
2Solution contacts with flue gas adverse current, reaction rapidly, the SO in the flue gas
2Be dissolved in CaCl
2Solution and water generate sulfurous acid (H
2SO
3), sulfurous acid and CaCl
2Reaction generates white calcium sulfite (CaSO
3) precipitation, generate HCl simultaneously.According to the henry's law of gas equilbrium solubility in liquid, HCl mainly is dissolved in the solution, forms the very low hydrochloric acid of concentration.
The key reaction formula is as follows:
SO
2+H
2O＝H
2SO
3……………………………(1)
H
2SO
3+CaCl
2＝CaSO
3↓+2HCl………………(2)
CaCl after the desulfurization
2Solution comes out to enter neutralization pond (5) by the desulfurizing tower bottom.In neutralization pond, hydrochloric acid that concentration is very low and Ca (OH)
2Neutralization reaction takes place, and regenerates CaCl
2, the key reaction formula is as follows:
Ca(OH)
2+2HCl＝CaCl
2+2H
2O……………(3)
The liquid of neutralization pond (5) middle and upper part is put into depositing reservoir (4) by mozzle (7), in depositing reservoir (4), and CaSO
3Major part precipitates, and clear liquid flows into circulatory pool through mozzle (6), restarts desulfurization.
Sediment in the depositing reservoir mainly is CaSO
3, CaSO
3Very easily be oxidized to CaSO
4, by air hose (8) air is blasted depositing reservoir (4), with CaSO
3Be oxidized to CaSO
4, become gypsum (CaSO
42H
2O).Every certain hour the gypsum taking-up is given the cement plant or is processed as plastering.
Key reaction formula: CaSO
3+
1/
2O
2=CaSO
4
The invention has the beneficial effects as follows:
1, desulfurization degree height.Find out H from reaction equation (2)
2SO
3With CaCl
2That reaction generates is CaSO
3White precipitate, reaction speed is fast, and it is more thorough that reaction is carried out.
2, technology, equipment are simple, small investment.Reduce investment in fixed assets more than 90% than " limestone/gypsum wet desulphurization ".
3, operating cost is low.This sulfur removal technology is in running, and calcium chloride can be regenerated, and is recycling, and some get final product a small amount of supplemental.What in fact mainly consume is calcium hydroxide.As calculated, take off 1 ton of SO in theory
2Consume 1.16 tons of Ca (OH)
2, being converted into the lime that contains CaO 60% is 1.46 tons.As use carbide slag, whenever take off 1 ton of SO
2Can consume and contain 50%Ca (OH)
22.32 tons of carbide slags, can generate 2.69 tons in gypsum.Through measuring and calculating, this law reduces desulphurization cost about 80% than NaOH desulfurization.
4, simple to operate.Because of this technology doctor solution is a solution, do not stop up, do not scab.With Ca (OH)
2Also can direct desulfurization, because of Ca (OH)
2Be emulsion, contain the part solid content, stop up easily, scab.
Description of drawings:
Fig. 1 is desulfurization process figure.1 is desulfurizing tower among the figure, and 2 is centrifugal pump, and 3 is circulatory pool, and 4 is depositing reservoir, and 5 is neutralization pond, and 6,7 is mozzle, and 8 is the air hose that comes from air blast.
A is the desulfurizing tower gas approach, and B is the desulfurizing tower exhanst gas outlet.
Fig. 2 is the sulfur removal technology layout of equipment.1 is desulfurizing tower among the figure, and 2 is centrifugal pump, and 3 is circulatory pool, and 4 is depositing reservoir, and 5 is neutralization pond, and 6,7 is mozzle, and 8 is the air hose that comes from air blast.
A is the desulfurizing tower gas approach, and B is an exhanst gas outlet.
Absolute altitude unit is a rice, and other dimensional units is a millimeter.
Fig. 3 is a desulfurizing tower.1 is tower body among the figure, and 2 is shower nozzle, and 3,4 is packing layer, and A is a gas approach, and B is an exhanst gas outlet, and C is the doctor solution import, and D is the doctor solution outlet.
The specific embodiment:
At first make a desulfurizing tower according to the structure of Fig. 3.Tower height H=5m, diameter d=2.5m, filler floor height h=0.5m.Filler is porcelain ring, PVC ball or iron filings.
The layout of desulfurizing tower by Fig. 2 fixed.
Press the layout of Fig. 2, with concrete for making circulatory pool (2m * 2m * 1.6m), depositing reservoir (3m * 3m * 1.1m) and neutralization pond (2m * 2m * 1.1m).
Pump and pipeline are pressed Fig. 2 and are installed.
With the 15%CaCl for preparing
2Solution is put into circulatory pool (3), and the milk of lime that modulates is put into neutralization pond (5).
Start centrifugal pump, with the CaCl of circulatory pool
2Solution is sent into desulfurizing tower, moves to open gas approach after 5～10 minutes and cut down, and flue gas enters desulfurizing tower from A, and desulfurization work begins to carry out.
Claims (4)
1, a kind of method of utilizing waste soda ash solution and calcium carbide waste slag to remove sulfur dioxide is characterized in that: the SO in the flue gas
2Be dissolved in CaCl
2Solution and water reaction generate H
2SO
3, H
2SO
3With CaCl
2Reaction generates white CaSO
3Precipitation is emitted HCl, and HCl is dissolved in the solution immediately, generates the very low hydrochloric acid of concentration; [mainly contain Ca (OH) with carbide slag
2] in and hydrochloric acid generate CaCl
2And water, CaCl
2Recycling; Blowing air makes CaSO
3Be oxidized to CaSO
4, the gypsum (CaSO of generation
42H
2O) further be processed into plastering or give the cement plant and use.
Key reaction is: SO
2+ H
2O=H
2SO
3H
2SO
3+ CaCl
2=CaSO
3↓+2HCl
2HCl+Ca(OH)
2＝CaCl
2+2H
2O CaSO
3+1/2O
2＝CaSO
4。
2, according to right 1 described a kind of method of utilizing waste soda ash solution and calcium carbide waste slag to remove sulfur dioxide, it is characterized in that: because SO in the various furnace gases
2The change in concentration amplitude very big, so CaCl
2Concentration can be lower than 10%, also can be higher than 20%, be about 15% generally speaking.
3, according to right 1 described a kind of method of utilizing waste soda ash solution and calcium carbide waste slag to remove sulfur dioxide, it is characterized in that: if the locality does not have waste soda ash solution, can buy the calcium chloride dihydrate of producing by waste soda ash solution, preparation CaCl
2Solution; Calcium carbide waste slag can replace with lime.
4, according to right 1 described a kind of method of utilizing waste soda ash solution and calcium carbide waste slag to remove sulfur dioxide, it is characterized in that: the capital equipment of desulfurization has desulfurizing tower (1), centrifugal pump (2), circulatory pool (3), sedimentation basin (4) and neutralization pond (5); Desulfurization process is: the CaCl in the circulatory pool (3)
2Solution is delivered to the top of desulfurizing tower (1), CaCl with pump (2)
2Solution and the SO that contains that comes in from tower bottom
2Flue gas adverse current contact, reaction generates white CaSO rapidly
3Precipitation is emitted HCl, generates the very hydrochloric acid at the end of concentration; Reacted CaCl
2Solution is emitted from desulfurizing tower (1) bottom, flows into neutralization pond (5), CaCl in neutralization pond
2Ca (OH) in watery hydrochloric acid in the solution (HCl) and the pond
2Reaction generates CaCl
2And water, CaCl
2Recycling; The clear liquid on neutralization pond (5) top is put into sedimentation basin (4) from mozzle (7), in sedimentation basin (4), CaSO
3Precipitate, the air of coming in by air hose (8) is with CaSO
3Be oxidized to CaSO
4, with gypsum (CaSO
42H
2O) form is taken out; By mozzle (6) clear liquid on sedimentation basin top is put into circulatory pool (3), restart desulfurization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101293729A CN101306304A (en) | 2008-06-26 | 2008-06-26 | Desulfurizing method using soda waste liquid and calcium carbide waste residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101293729A CN101306304A (en) | 2008-06-26 | 2008-06-26 | Desulfurizing method using soda waste liquid and calcium carbide waste residue |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101306304A true CN101306304A (en) | 2008-11-19 |
Family
ID=40123117
Family Applications (1)
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|---|---|---|---|
| CNA2008101293729A Pending CN101306304A (en) | 2008-06-26 | 2008-06-26 | Desulfurizing method using soda waste liquid and calcium carbide waste residue |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830584A (en) * | 2010-04-30 | 2010-09-15 | 汪晋强 | Method for processing and forming distilled waste liquid of calcined soda with hydrochloric acid |
| CN104722189A (en) * | 2015-03-18 | 2015-06-24 | 徐宝东 | Flue gas desulfurization method |
| CN104857831A (en) * | 2015-05-29 | 2015-08-26 | 唐山三友化工股份有限公司 | Preparation device and method for alkali residue liquid desulfurizing agent |
| WO2017004923A1 (en) * | 2015-07-07 | 2017-01-12 | 沈阳化工大学 | Calcium carbonate/calcium hydrate-gypsum wet desulphurization and dedusting technique for flue gas |
| CN110395699A (en) * | 2019-07-31 | 2019-11-01 | 河南安赛机制玻璃钢实业有限公司 | The technique of calcium hydroxide desulfurization slag recycling sulfur dioxide by-product hygroscopic agent |
| CN110743351A (en) * | 2019-11-05 | 2020-02-04 | 唐山三孚硅业股份有限公司 | Tail gas treatment device and method by carbide slag slurry indirect circulation method |
-
2008
- 2008-06-26 CN CNA2008101293729A patent/CN101306304A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830584A (en) * | 2010-04-30 | 2010-09-15 | 汪晋强 | Method for processing and forming distilled waste liquid of calcined soda with hydrochloric acid |
| CN104722189A (en) * | 2015-03-18 | 2015-06-24 | 徐宝东 | Flue gas desulfurization method |
| CN104857831A (en) * | 2015-05-29 | 2015-08-26 | 唐山三友化工股份有限公司 | Preparation device and method for alkali residue liquid desulfurizing agent |
| WO2017004923A1 (en) * | 2015-07-07 | 2017-01-12 | 沈阳化工大学 | Calcium carbonate/calcium hydrate-gypsum wet desulphurization and dedusting technique for flue gas |
| CN110395699A (en) * | 2019-07-31 | 2019-11-01 | 河南安赛机制玻璃钢实业有限公司 | The technique of calcium hydroxide desulfurization slag recycling sulfur dioxide by-product hygroscopic agent |
| CN110743351A (en) * | 2019-11-05 | 2020-02-04 | 唐山三孚硅业股份有限公司 | Tail gas treatment device and method by carbide slag slurry indirect circulation method |
| CN110743351B (en) * | 2019-11-05 | 2022-06-24 | 唐山三孚硅业股份有限公司 | Tail gas treatment device and method by carbide slag slurry indirect circulation method |
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Open date: 20081119 |