CN101565191B - Method for preparing anhydrous sodium sulfite by circularly absorbing sulfur dioxide in exhaust gas - Google Patents

Method for preparing anhydrous sodium sulfite by circularly absorbing sulfur dioxide in exhaust gas Download PDF

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Publication number
CN101565191B
CN101565191B CN2009100435676A CN200910043567A CN101565191B CN 101565191 B CN101565191 B CN 101565191B CN 2009100435676 A CN2009100435676 A CN 2009100435676A CN 200910043567 A CN200910043567 A CN 200910043567A CN 101565191 B CN101565191 B CN 101565191B
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reaction
exhaust gas
sulfur dioxide
sodium
thickener
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CN101565191A (en
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冯延林
刘仁和
黄建华
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HUNAN YONKER ENVIRONMENTAL GROUP
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HUNAN YONKER ENVIRONMENTAL GROUP
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Abstract

The invention relates to a method for preparing anhydrous sodium sulfite by circularly absorbing sulfur dioxide in exhaust gas, comprising the following steps: the exhaust gas containing the sulfur dioxide is pre-washed and re-dedusted, subsequently enters a spray tower so that the sulfur dioxide is absorbed and sodium bisulfite solution is generated; subsequently the sodium bisufite solution reacts with a sodium hydroxide solution to generate sodium sulfite and separates out crystals; the crystals are thickened by a thickener and the mother liquor is removed by centrifuging; the mother liquorand the overflow liquid overflowing out of the upper part of the thickener return to the spray tower and absorb the sulfur dioxide in the exhaust gas; the above steps are circularly conducted to prepare the anhydrous sodium sulfite product. The method adopts a reaction salting-out crystallization process, has short production process flow, low energy consumption and low cost; the absorbing and reaction crystallization system runs circularly and completely closely and generates no wastewater or waste slag; and the method is applicable to the SO2 exhaust gas treatment of various industrial furnaces and coal burning boilers in the industries such as metallurgy, steel, petrifaction, medicals and the like, and can recycle and utilize the SO2 exhaust gas contained in various furnaces.

Description

Sulfurous gas is produced the method for sodium sulphite anhydrous 99.3 in a kind of absorption waste gas that circulates
Technical field
The present invention relates to a kind of production method of sodium sulphite anhydrous 99.3, be specifically related to a kind of the circulation and absorb the method that sulfurous gas in the waste gas is produced sodium sulphite anhydrous 99.3.
Background technology
Entered since 21st century, maximum in the world population is just being carried with the ecotope of most fragile in history in China, is carrying the most unprecedented in history resource consumption and economic activity, is faced with the most outstanding in history ecotope challenge.Contradiction between population and resource, Economic development and the ecotope has become the maximum restraining factors of China's Modernization development.Keep Sustainable development, just must reduce pollution and enforcement recycling economy environment.And SO 2Be one of main atmospheric polluting material of face of mankind nowadays, its existence has all caused harm to a certain degree to aspects such as natural ecological environment, human health, industrial and agricultural production, buildings and materials, once takes place more than 10 times and SO in modern age on the human history 2Pollute relevant major disaster.
Traditional sodium hydroxide absorption process is that the sulfurous gas that sodium hydroxide solution directly adds in the absorption tower absorption waste gas is generated metabisulfite solution, from the absorption tower, take out absorption liquid through evaporation concentration, crystallization goes out S-WAT, crystal solution makes crystallization separate with mother liquor by filtration, and the mother liquor Returning evaporimeter is evaporative crystallization again.Traditional sodium hydroxide absorption process long flow path, investment is big, and production process need consume steam, S-WAT production cost height.
Summary of the invention
The technical problem to be solved in the present invention is, defective at existing sodium hydroxide absorption process existence, propose a kind of the circulation and absorb the method that sulfurous gas in the waste gas is produced sodium sulphite anhydrous 99.3, it adopts reacting salt precipitation and crystallization technology to make the crystallization of solid water-free S-WAT, the technological process of production is short, energy consumption is low, cost is low, and absorption, reactive crystallization system adopt totally-enclosed circular flow, and no waste water, waste residue produce;
Technical scheme of the present invention is, described circulation absorbs sulfurous gas in the waste gas and produces the method for sodium sulphite anhydrous 99.3 and comprise the steps:
(1) will contain SO 2Waste gas by washing, dedusting purified;
(2) contain SO after the purification 2Waste gas in spray absorber, contact the SO in the gas with absorption liquid 2Be absorbed to generate that to contain mass concentration be 20%~35%NaHSO 3, 2%~10%Na 2SO 3, 0%~9%Na 2SO 4Mixing solutions, mixing solutions pH value 5~6; Adding concentration simultaneously in spray absorber is the antioxidant of absorption liquid total amount 0.14 ‰~0.2 ‰, stops sodium bisulfite and S-WAT to be oxidized to sodium sulfate effectively;
Described absorption liquid is 20%~25%Na for containing mass concentration 2SO 3, 0%~4%NaHSO 3, 0%~9%Na 2SO 4, the solution of pH value 6.5~7.5;
Described antioxidant is the mixture of Ursol D, Resorcinol, ethylenediamine tetraacetic acid (EDTA) monomer or described material;
(3) mixing solutions that obtains through step (2) and mass concentration are 40%~50% caustic soda soln reaction, the pH value of control reaction end is 6.5~7.5, make sodium bisulfite and caustic soda complete reaction in the mixing solutions, the temperature of controlling reaction solution then is between 36~90 ℃, and the S-WAT that reaction is generated becomes crystallization and separates out;
(4) above-mentioned crystal solution being thickened to the quality solid content in thickener is 25%~50%, and the centrifugal mother liquor that removes gets the sodium sulphite anhydrous 99.3 solid; Mother liquor and thickener overflowing liquid all return as step (2) absorption liquid after mixing; And so forth, forming circulation absorbs.
The method of the invention is by suitable process conditions in the control absorption tower, the material that changes the absorption tower liquid effluent is formed, the content of sodium bisulfite in the liquid effluent of control absorption tower, in reaction crystalizer, add the sodium hydroxide solution and the absorption tower liquid effluent generation chemical reaction of suitable concn and generate S-WAT, utilize S-WAT and the sodium bisulfite dissolubility difference under temperature of reaction, separate out the sodium sulphite anhydrous 99.3 crystallization voluntarily, again through obtaining the crystallization suspension that concentration is higher and particle is bigger after the thickener thickening, crystallization suspension is sent into whizzer and is removed mother liquor, just obtains the crystallization of solid water-free S-WAT.
In order to understand the know-why of foregoing invention better, the present invention provides the chemical equation of absorption reaction: (referring to accompanying drawing 1)
In prewashing tower 6:
HCl(g)→HCl(aq)
HF(g)→HF(aq)
SO 3(g)+H 2O→H 2SO 4(aq)
In spray absorber 14:
SO 2(g)+H 2O→H 2SO 3(aq)
H 2SO 3(aq)+Na 2SO 3→2NaHSO 3
Na 2SO 3+ 1/2O 2→ Na 2SO 4(this reaction needs to suppress)
NaHSO 3+ 1/2O 2→ NaHSO 4(this reaction needs to suppress)
In reaction crystalizer 19:
NaHSO 3+NaOH→Na 2SO 3+H 2O
NaHSO 4+NaOH→Na 2SO 4+H 2O
Remove SO 2The total reaction equation:
SO 2+2NaOH→Na 2SO 3+H 2O
From above-mentioned chemical equation as can be known, the hydrogenchloride in the waste gas, hydrogen fluoride, sulphur trioxide obtain removing in through Venturi prewashing tower 6, mainly finish the absorption and the reaction of sulfurous gas and generate sodium sulfite solution in spray absorber 14.
The solubleness of sodium bisulfite is along with the rising of temperature constantly increases, and constantly reduce with the reduction of temperature, and the rising along with temperature when temperature reaches more than 34.5 ℃ of the solubleness of S-WAT constantly reduces, and can not generate Na 2SO 37H 2O, and when temperature was lower than 34.5 ℃, its solubleness constantly reduced along with the reduction of temperature, and generate Na 2SO 37H 2O.Therefore, thereby the acceptance condition by control spray absorber 14 is controlled the sodium bisulfite of the proper ratio of discharging spray absorber 14 bottoms and the saturated solution of S-WAT, after this saturated solution enters reaction crystalizer 19, sodium bisulfite wherein rapidly and the sodium hydroxide generation S-WAT that reacts, by control reaction temperature and caustic soda concentration, can make that S-WAT reaches supersaturation in the reaction solution, thereby separate out the sodium sulphite anhydrous 99.3 crystallization automatically, be with original S-WAT production method difference: it is directly to add alkali lye the absorption tower liquid effluent is made near saturated sodium sulfite solution in the absorption tower that original S-WAT is made, remove impurity such as flue dust then after filtration and make scavenging solution, scavenging solution is sent into separated out the S-WAT crystallization after the vacuum evaporating crystalization device concentrates with the steam indirect heating again.The present invention need just can not realize the crystallization of S-WAT by the evaporation concentration mode, has not only shortened the S-WAT Production Flow Chart, and has saved a large amount of energy consumptions in the production process.
Technique effect of the present invention comprises:
A. adopted reacting salt precipitation and crystallization technology, the technological process of production is short, energy consumption is low, cost is low.
B. absorption, reactive crystallization system adopt totally-enclosed circular flow, and no waste water, waste residue produce;
C. be applicable to the various Industrial Stoves of industries such as metallurgy, iron and steel, petrochemical industry, medicine and the SO of coal firing boiler 2Waste gas pollution control and treatment can realize that various kilns contain SO 2The recycling of waste gas.
Description of drawings
Fig. 1 is a basic flowsheet of coal preparation, in the drawings:
The former waste gas butterfly valve of 1-, the 2-booster fan,
3-bypass butterfly valve, 4-sprays water pump,
The 5-waste water pump, 6-Venturi prewashing tower,
7-circulation suspension system, 8-circulation levitated pump,
The 9-mist eliminator, the 10-spraying layer,
11-absorption tower thermometer, 12-absorption tower PH meter,
13-absorption tower densometer, the 14-spray absorber,
15-absorption tower recycle pump, 16-absorption tower overboard pump,
17-reaction crystalizer thermometer, 18-reaction crystalizer PH meter,
The 19-reaction crystalizer, 20-thickener densometer,
The 21-thickener, the 22-mixer.,
The 23-centrifuge, 24-caustic soda variable valve,
25-caustic soda fresh feed pump, 26-caustic soda groove.
Embodiment
Below in conjunction with accompanying drawing the present invention is made and to further specify.
Referring to accompanying drawing 1, implement technology of the present invention and mainly comprise following system: waste gas system, absorption system, reactive crystallization dewatering system.
A, waste gas system: by containing SO behind cloth bag or the electric precipitation 2Hot waste gas 1. (temperature is greater than 80 ℃) after booster fan 2 boosts, enter Venturi prewashing tower 6, the water jet of sufficient amount is set in the throat of Venturi prewashing tower 6,2. spray water takes from the supernatant liquor in Venturi prewashing tower 6 slurries ponds, by sending into Venturi prewashing tower 6 trunnion portions after 4 pressurizations of spray water pump, 4 flow controls of spray water pump are at 0.2~3.0L/m 3In the scope.Waste gas removes flue dust, HCl, HF, SO after 1. passing through Venturi prewashing tower 6 3The flue dust that washs accumulates in the Venturi prewashing tower 6 bottom stock tanks, for preventing the deposition of Venturi prewashing tower 6 bottom flue dust, in Venturi prewashing tower 6 bottom stock tanks, circulation suspension system 7 is set, under the effect of circulation levitated pump 8, suck Venturi prewashing tower 6 slurries pond supernatant liquors and inject prewashing tower 6, impact the slurries of Venturi prewashing tower 6 bottoms and make it to suspend dust deposition bottom preventing.3. the bottom slurries deliver to Waste Water Treatment by waste water pump 5.4. enter spray absorber 14 through the waste gas of rough purification,, remove SO wherein with 6. counter current contact of the absorption liquid of spraying layer 10 ejections 2, capture drop after absorption tower 14 top chimneys enter in the atmosphere through mist eliminator 9 again.
B, absorption system: absorption system is to reclaim SO in the waste gas 2Core system, have SO 2Functions such as spray absorption, reaction, demist.Be provided with Duo Tai absorption tower recycle pump 15 in spray absorber 14 bottoms, every recycle pump 15 corresponding one deck spraying layers 10, every layer of spraying layer 10 is provided with the nozzle of suitable quantity.Waste gas 4. in spray absorber 14 with from 6. counter current contact of the absorption liquid of spraying layer 10 nozzles ejections, value by thermometers 11 in the control spray absorber 14 between 36~55 ℃, the pH value of absorption tower pH meter 12 is between 5~6, in the scope of liquid specific gravity 1.35~1.5 of absorption tower densometer 13, promote absorption liquid 6. to absorb the 4. middle SO of waste gas 2, SO 2Generate sodium bisulfite with the reaction of S-WAT in the absorption liquid, make that containing mass concentration in the liquid effluent is 20%~35%NaHSO 3, 2%~10%Na 2SO 3, 0%~9%Na 2SO 4Add the antioxidant A that concentration is absorption liquid total amount 0.14 ‰~0.2 ‰ (Ursol D, Resorcinol, ethylenediamine tetraacetic acid (EDTA) monomer or its mixture) every day in spray absorber 14 simultaneously, stops sodium bisulfite and S-WAT to be oxidized to sodium sulfate effectively.
C, reactive crystallization dewatering system: 7. absorption tower, the bottom liquid effluent of spray absorber 14 delivers to reaction crystalizer 19 through absorption tower overboard pump 16, and 7. the absorption tower liquid effluent is 40%~50% caustic soda soln with the concentration of regulating metering through variable valve 24 in reaction crystalizer 19 Chemical reaction takes place, and the pH value by control reaction crystalizer pH meter 18 makes sodium bisulfite and the caustic soda soln of absorption tower liquid effluent in 7. in 6.5~7.5 scopes Complete reaction generates S-WAT, and because of the difference of sodium bisulfite and S-WAT dissolution characteristics, under 36 ℃~90 ℃ temperature of reaction, the S-WAT crystal is separated out voluntarily because of reaching supersaturation.8. crystal solution sends into thickener 21, mixer. 22 is installed in thickener 21, specific gravity value by monitoring thickener densometer 20 in 1.40~1.60 scopes and the rotating speed of controlling mixer. 22 between 2~20 rev/mins, promote reaction product further crystallization stiff 8., after thickener underflow solid content 10. reaches between the solid content 25%~50%, open the underflow valve of thickener 21,10. underflow is put into whizzer 23 remove mother liquor, obtain the crystallization of solid water-free S-WAT.The mother liquor that 9. overflow of thickener 21 throws away with whizzer 23 (containing mass concentration is 20%~25%Na to mix the back 2SO 3, 0%~4%NaHSO 3, 0%~9%Na 2SO 4, pH value 6.5~7.5) return spray absorber 14 as absorption agent to waste gas 1. in SO 2Absorption circulates.

Claims (1)

1. one kind circulates and absorbs the method that sulfurous gas in the waste gas is produced sodium sulphite anhydrous 99.3, it is characterized in that, comprises the steps:
(1) will contain SO 2Waste gas by washing, dedusting purified;
(2) contain SO after the purification 2Waste gas in spray absorber, contact the SO in the gas with absorption liquid 2Be absorbed to generate that to contain mass concentration be 20%~35%NaHSO 3, 2%~10%Na 2SO 3, 0%~9%Na 2SO 4Mixing solutions, mixing solutions pH value 5~6, adding consumption simultaneously in spray absorber is the antioxidant of absorption liquid total amount 0.14 ‰~0.2 ‰, stops sodium bisulfite and S-WAT to be oxidized to sodium sulfate effectively;
Described absorption liquid is 20%~25%Na for containing mass concentration 2SO 3, 0%~4%NaHSO 3, 0%~9%Na 2SO 4, the solution of pH value 6.5~7.5;
Described antioxidant is the mixture of Ursol D, Resorcinol, ethylenediamine tetraacetic acid (EDTA) monomer or described material;
(3) mixing solutions that obtains through step (2) and mass concentration are 40%~50% caustic soda soln reaction, the pH value of control reaction end is 6.5~7.5, make sodium bisulfite and caustic soda complete reaction in the mixing solutions, the temperature of controlling reaction solution then is between 36~90 ℃, and the S-WAT that reaction is generated becomes crystallization and separates out;
(4) above-mentioned crystal solution being thickened to the quality solid content in thickener is 25%~50%, and the centrifugal mother liquor that removes gets the sodium sulphite anhydrous 99.3 solid; Mother liquor and thickener overflowing liquid all return as step (2) absorption liquid after mixing; And so forth, forming circulation absorbs.
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CN102583452A (en) * 2011-01-07 2012-07-18 北京柯兰富尔过滤技术有限公司 Method and equipment for directly producing sodium sulfite by using sulfuric acid-containing gas
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CN102887533A (en) * 2012-09-28 2013-01-23 天津中科化工有限公司 Method for producing anhydrous Na2SO3 by using alkali-containing waste mother liquor
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CN109316964A (en) * 2018-11-15 2019-02-12 中石化炼化工程(集团)股份有限公司 A kind of method of catalytic cracking flue gas desulfurization recycling sodium sulfite
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