CN102794101B - Technology for co-producing gypsum crystal whisker by using imestone desulfuration - Google Patents
Technology for co-producing gypsum crystal whisker by using imestone desulfuration Download PDFInfo
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- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 41
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 39
- 238000005516 engineering process Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 50
- 235000019738 Limestone Nutrition 0.000 claims abstract description 42
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 14
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 28
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- 239000007921 spray Substances 0.000 claims description 9
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- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 2
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- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 2
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
The invention provides a technology for co-producing gypsum crystal whisker by using imestone desulfuration, which is characterized by comprising the following steps of: taking limestone (calcium carbonate) as an absorbent, taking ammonium sulfate as a process absorbent, entering flue gas into the middle of an absorbing tower to carry out countercurrent contact mass transfer with absorption liquid, discharging from the top of the tower, circulating most serous fluid at the bottom of the tower in the absorbing tower, transporting small part of serous fluid for crystal whisker operation, centrifugally separating prepared crystal whisker, and transporting a fluid phase for limestone pulping, wherein the solid phase is the gypsum crystal whisker. The technology has the benefit effects that the desulfuration absorption tower is high in desulfuration efficiency, the desulfuration efficiency is more than or equal to 97%; the absorption tower is high in operation flexibility, and stable to operate; the desulfuration and partial denitration can be carried out at the same time; and denitration slag is the gypsum crystal whisker, the length-diameter ratio of the crystal whisker is 10-80, and the technology is relatively high in product value.
Description
Technical field
The invention belongs to boiler exhaust gas processes and new chemical materials preparation field.The present invention relates to a kind of method of removing sulfur dioxide in flue gas coproduction crystal whisker of gypsum.
Background technology
The energy resource structure of China more than 90% is usingd fire coal as power, and burning coal all can produce SO
2, wherein maximum with power plant emission amount, by SO
2be Acid Rain Pollution hazard area due to main oneself account for approximately 40% of area, oneself reaches the therefore annual and economic loss that causes in the whole nation and exceeds 100 billion.
At present, in the world the method for flue gas desulfurization oneself reach kind more than 100, the method for industrial application also approximately has 20 kinds.Wherein Wet Flue Gas Desulfurization Technique application accounts for 85% left and right of whole industrialization desulfurizer, and Wet Limestone/lime method accounts for approximately 80% of wet method, in current technology, occupies an leading position.This technology blasts air in the slurries on absorption tower, with lime stone, washs flue gas, forces to make CaSO
3be oxidized to CaSO
4(gypsum).
Lime/gypsum method Patents is as follows:
CN99113914 discloses a kind of lime/gypsum method flue gas desulfurization technique, the steps include: (1) dedusting, (2) desulfurization, and (3) make the mixed liquor containing gypsum crystallization body, (4) dehydration by-product gypsum.Wherein desulfurization is that flue gas after dedusting is entered to desulfurizing tower after booster fan warp let-off humidification cooler again, in tower, through porous plate bubbling flue gas after desulfurization, make secondary desulfuration again through spray liquid, after purifying, flue gas enters chimney again after tower top gas-liquid separator separates after then flue gas heater makes.
CN1923338 discloses a kind of flue gas desulfurization technique, a kind of fume desulfurizing process with enhancement limestone method particularly, be mainly used in air contaminant treatment, Prevention Technique field, comprise: lime stone and additive are inputted respectively to digestion reactor, at digestion reactor sodalime stone and additive, mix and react with water generating absorption slurries; To absorb slurries input absorption tower, sulfur-containing smoke gas enters absorption tower, and after absorption slurry reaction, purifying smoke is discharged absorption tower; The absorption slurries that absorbed sulfur dioxide recycle or go post processing from discharge bottom, absorption tower.
Above-mentioned limestone/gypsum method, accessory substance gypsum is generally abandoned as refuse, to environmental protection, causes certain pressure.
That calcium sulfate crystal whiskers is divided into is anhydrous, three kinds of Ban Shui, two water, and wherein anhydrous calcium sulfate whisker intensity is the highest.Dihydrate gypsum whiskers does not have the humidification of whisker when surpassing 110 ℃ of uses, and prospects for commercial application is little; Anhydrous and hemihydrate calcium sulfate crystal whisker has higher intensity and use value.
Calcium sulfate crystal whiskers has good mechanical property, good compatibility, good flatness, regenerability is good, toxicity is low, low cost of manufacture, increase constituent element, friction material, the environmental project that is mainly used in papermaking, composite filtered, asphalt modification, and the adhesive force, temperature tolerance and the insulating properties that improve coating and paint, and price is only 1/200th～300 of silicon carbide whisker, has the very strong market competitiveness.Calcium sulfate crystal whiskers belongs to the gypsum series product of high-performance, high added value, take its good sexual valence when environmental-protecting performance as it, won wide market prospects, market potential is huge.
Calcium sulfate crystal whiskers Patents is as follows:
CN101550602 discloses a kind of CaSO4 whisker that desulfurated plaster is raw material and preparation method thereof of take.Its technical scheme is: first desulfurated plaster, water and medium crystallization agent are fully mixed, form suspension, wherein: desulfurated plaster mass concentration is 1～8%, medium crystallization agent mass concentration is 5～20%; At normal pressure, 100～128 ℃ and stir speed (S.S.), be under 120～210r/min condition again, or above-mentioned suspension is stirred 1～3 hour, add the calcium sulfate crystal whiskers of suspension quality 0.5～1% as crystal seed, react 1～3 hour, add modifier, or above-mentioned suspension is stirred 3～8 hours, directly add modifier, the addition of modifier be suspension quality O.4～1%, stir 0.5～1 hour; Then through suction filtration, washing and three sections dry, can obtain three kinds of dissimilar calcium sulfate crystal whiskers.
CN101311337 discloses a kind of method of utilizing desulfurized gesso of flue gas to prepare calcium sulfate crystal whiskers, comprise size mixing, the processing step such as high temperature crystallization, dry, covering with paint.The method utilizes desulfurized gesso of flue gas for raw material, and production cost is low, and technological process is short, has saved plaster of paris ore deposit, effectively alleviates the problem of desulfurized gesso of flue gas contaminated environment.Product purity reaches more than 98%, can be used as moderate strength filler, also can replace asbestos as friction material, construction material, insulation material etc., also can partly replace glass fibre, and the organic high molecular compound such as resin, rubber, plastics has good describing property.
CN1598083 the present invention is a kind of preparation method of calcium sulfate crystal whiskers, it is raw material that gypsum (CaSO42H20) and water are take in whole production, through raw material preparation, synthetic reaction, dehydrate and an operation such as refining and edulcoration, the effective content that it is characterized in that selected raw material gypsum reaches more than 95, whiteness is more than 90%, mix and make gypsum slip with running water, after fully emulsified, add in reactor and make it that chemical reaction occur, and then enter into later operation.The calcium sulfate crystal whiskers properties of product of utilizing this method to produce are good, with low cost, can extensive uses in every profession and trade, there are wide market prospects.
The preparation method of these calcium sulfate crystal whiskers exists flow process complicated, needs special production equipment, the shortcomings such as production cost height.
Summary of the invention
The object of the present invention is to provide a kind of method of removing sulfur dioxide from flue gas, and sweetening process is become to the production process of high value added product---by-product calcium sulfate crystal whiskers.
Method of the present invention is that to take lime stone (calcium carbonate) be absorbent, take ammonium sulfate as process absorbent, flue gas enters and absorption liquid counter current contacting mass transfer at middle part, absorption tower, from tower top, leave, at the bottom of tower, most of slurries circulate in absorption tower, and small part slurries send whisker preparation, and the whisker making is through centrifugation, liquid phase is sent limestone pulping, and solid phase is crystal whisker of gypsum.
Its concrete steps are:
The absorption of a, sulfur dioxide and the generation of calcium sulfate
Flue gas enters desulfuration absorbing tower middle part, and with the loop slurry counter current contacting from the spray of top, in tower, in slurries, the concentration of ammonium sulfate is 20～40%, and air is blasted to desulfurizing tower lower groove body with oxidation fan; By spray washing, sulfur dioxide, dust in flue gas are removed, then through the washing of tower top fresh water (FW), purifying smoke leaves absorption system and send chimney, and desulfurizing tower lower groove body part slurries are discharged and sent crystal whisker of gypsum preparation vessel by slush pump;
The preparation of b, crystal whisker of gypsum
Slurries in whisker preparation vessel are through whisker slurries pumping filter, and filtering solid phase is that crystal whisker of gypsum send postprocessing working procedures; Filtrate is collected in filtrate receiver, then by filtrate pumping lime stone slurry preparation vessel; At the technique water washing filter cake for scrubbing section of guipure filter, cleaning solution is collected in washing liquid bath, realizes cleaning solution circulate by technique water pump, and part cleaning solution send the demist of desulfuration absorbing tower top;
The preparation of c, lime stone slurry
In limestone slurry liquid bath, add lime stone, and from separation circuit pressing filtering liquid and the liquid slurrying of eddy flow top, by lime stone slurry, be pumped into desulfuration absorbing tower.
The present invention be embodied in following some: (1) take lime stone (calcium carbonate) is absorbent, take ammonium sulfate as process absorbent, ammonium sulfate concentrations 20～40% (mass fraction), flue gas and spray liquid counter current contacting, through top fresh water (FW) demist, leave absorption tower again, at the bottom of absorption tower, establish oxidation fan, force to make CaSO
3be oxidized to CaSO
4(gypsum), then send whisker to become elongated slot.(2) sweetening process and whisker are prepared integratedly, and whisker preparation is only established a whisker and become elongated slot, and gypsum slurries becomes in elongated slot to be incubated crystallization at whisker, is further converted to calcium sulfate crystal whiskers.(3) separation circuit adopts guipure filter, sets up two sections separately, one section of filtration, and first wash, filtered fluid and cleaning solution separate collection, filtered fluid send lime stone slurry preparation, and cleaning solution send desulfuration absorbing tower top demister, filters solid formation and send drying process.(4) drying process adopts the drying machine of heated air source, is dried and can obtains anhydrous gypsum whisker.(5) technique of the present invention is applicable to take the process that calcium carbide mud is absorbent.
Accompanying drawing explanation
Accompanying drawing 1 is the schematic diagram of embodiment 1
Accompanying drawing 2 is embodiment 1 gained crystal whisker of gypsum design sketch
The specific embodiment
Example 1 smoke treatment flow 200000Nm
3/ h.
In Fig. 1, desulfuration absorbing tower 1, circulating pump 2, slush pump 3, whisker preparation vessel 4, whisker slush pump 5, guipure filter 6, filtrate receiver 7, filtrate pump 8, lime stone slurry preparation vessel 9, limestone slurry liquid pump 10, oxidation fan 11, vavuum pump 12, washing liquid bath 13, technique water pump 14; Lime stone (calcium carbonate) A, oxidation air B, flue gas C, purifying smoke D, crystal whisker of gypsum E, discharging waste gas F, fresh water (FW) G.
Flow is 200000Nm
3/ h, temperature is that first the flue gas C of 150 ℃ enters desulfuration absorbing tower 1 middle part, contacts with the circulation fluid from the spray of top, and in circulation fluid, the concentration of ammonium sulfate is 33% (mass fraction), and tower prime cement liquid is realized circulation by slush pump 2, and recycle slurry liquid measure is 480m
3/ h; Lime stone A throws absorption tower into limestone slurry liquid pump 10 make 5% (mass fraction) liquid slurry in lime stone slurry preparation vessel 9 after, pass through spray washing, sulfur dioxide, dust in flue gas are removed, then through 50 ℃ of washings washings of tower top, purifying smoke D leaves absorption system and send chimney.Approximately 60 ℃ of desulfurizing tower lower groove body slurry temperatures, flow is 50m
3the slurries of/h are squeezed into whisker preparation vessel 4 by slush pump 3, are incubated standing 72h in whisker preparation vessel 4.
Slurries in whisker preparation vessel 4 send guipure filter 6 through whisker slush pump 5, and filtering solid phase is that crystal whisker of gypsum D send postprocessing working procedures; Filtrate is collected in filtrate receiver 7, then send lime stone slurry preparation vessel 9 by filtrate pump 8; At the fresh water (FW) G washing leaching cake for scrubbing section of guipure filter 6, cleaning solution is collected in washing liquid bath 13, realizes cleaning solution circulate by technique water pump 14, and part cleaning solution send desulfuration absorbing tower 1 top demist.
The lime stone E that adds 720Kg/h in limestone slurry liquid bath 9, with from separation circuit pressing filtering liquid, with the liquid slurrying of eddy flow top, in slurries, calcium carbonate content is 5%, by limestone slurry liquid pump 10, sends into desulfuration absorbing tower 1.
The effect that this example 1 can reach: (1) desulfurization degree >=97%; (2) whisker draw ratio is 10～80, and by-product gypsum whisker design sketch is referring to accompanying drawing 2.
The invention has the beneficial effects as follows: desulfuration absorbing tower desulfuration efficiency is high, desulfurization degree >=97%; Absorption tower operating flexibility is large, stable operation; In the time of desulfurization, reach part denitration; Desulfurization slag is crystal whisker of gypsum, and whisker draw ratio is 10～80, has larger value of the product.
Claims (6)
1. a limestone desulfurization coproduction crystal whisker of gypsum technique, it is characterized in that: the lime stone (calcium carbonate) of take is absorbent, take ammonium sulfate as process absorbent, flue gas enters and absorption liquid counter current contacting mass transfer at middle part, absorption tower, from tower top, leaves, and at the bottom of tower, most of slurries circulate in absorption tower, small part slurries send whisker preparation, the whisker making is through centrifugation, and liquid phase is sent limestone pulping, and solid phase is crystal whisker of gypsum;
Its concrete steps are:
The absorption of a, sulfur dioxide and the generation of calcium sulfate
Flue gas enters desulfuration absorbing tower middle part, and with the loop slurry counter current contacting from the spray of top, in tower, in slurries, the concentration of ammonium sulfate is 20～40%, and air is blasted to desulfurizing tower lower groove body with oxidation fan; By spray washing, sulfur dioxide, dust in flue gas are removed, then through the washing of tower top fresh water (FW), purifying smoke leaves absorption system and send chimney, and desulfurizing tower lower groove body part slurries are discharged and sent crystal whisker of gypsum preparation vessel by slush pump;
The preparation of b, crystal whisker of gypsum
Slurries in whisker preparation vessel are through whisker slurries pumping filter, and filtering solid phase is that crystal whisker of gypsum send postprocessing working procedures; Filtrate is collected in filtrate receiver, then by filtrate pumping lime stone slurry preparation vessel; At the technique water washing filter cake for scrubbing section of guipure filter, cleaning solution is collected in washing liquid bath, realizes cleaning solution circulate by technique water pump, and part cleaning solution send the demist of desulfuration absorbing tower top;
The preparation of c, lime stone slurry
In limestone slurry liquid bath, add lime stone, and from separation circuit pressing filtering liquid and the liquid slurrying of eddy flow top, by lime stone slurry, be pumped into desulfuration absorbing tower.
2. limestone desulfurization coproduction crystal whisker of gypsum technique according to claim 1, it is characterized in that: the lime stone (calcium carbonate) of take is absorbent, take ammonium sulfate as process absorbent, ammonium sulfate concentrations 20～40% (mass fraction), flue gas and spray liquid counter current contacting, through top fresh water (FW) demist, leave absorption tower again, at the bottom of absorption tower, establish oxidation fan, force to make CaSO
3be oxidized to CaSO
4(gypsum), then send whisker to become elongated slot.
3. limestone desulfurization coproduction crystal whisker of gypsum technique according to claim 1, it is characterized in that: sweetening process and whisker are prepared integrated, whisker preparation is only established a whisker and is become elongated slot, and gypsum slurries becomes decrease temperature crystalline in elongated slot at whisker, is further converted to calcium sulfate crystal whiskers.
4. limestone desulfurization coproduction crystal whisker of gypsum technique according to claim 1, it is characterized in that: separation circuit adopts guipure filter, set up two sections separately, one section of filtration, first wash, filtered fluid and cleaning solution separate collection, filtered fluid send lime stone slurry preparation, cleaning solution send desulfuration absorbing tower top demister, filters solid formation and send drying process.
5. limestone desulfurization coproduction crystal whisker of gypsum technique according to claim 1, is characterized in that: drying process adopts the drying machine of heated air source, is dried and can obtains anhydrous gypsum whisker.
6. limestone desulfurization coproduction crystal whisker of gypsum technique according to claim 1, is characterized in that: described technique is applicable to take the process that calcium carbide mud is absorbent.
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| CN201210268591.1A CN102794101B (en) | 2012-07-25 | 2012-07-25 | Technology for co-producing gypsum crystal whisker by using imestone desulfuration |
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| CN103908882B (en) * | 2014-04-08 | 2016-05-11 | 淮南市明月环保科技有限责任公司 | A kind of calcium pyroborate of desulphurization denitration co-producing sulfuric acid simultaneously technique |
| CN106187594A (en) * | 2016-07-12 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of based on gardens desulfurated plaster changing alkali and preparation method thereof |
| CN106222748A (en) * | 2016-07-29 | 2016-12-14 | 西南科技大学 | A kind of continuous producing method of ultrafine gypsum |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311337A (en) * | 2008-04-25 | 2008-11-26 | 东北大学 | Process for preparing calcium sulphate whiskers by using flue gas desulfurization gypsum |
| CN102485323A (en) * | 2011-04-15 | 2012-06-06 | 安徽理工大学 | Rapid calcium desulphurization method for flue gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311337A (en) * | 2008-04-25 | 2008-11-26 | 东北大学 | Process for preparing calcium sulphate whiskers by using flue gas desulfurization gypsum |
| CN102485323A (en) * | 2011-04-15 | 2012-06-06 | 安徽理工大学 | Rapid calcium desulphurization method for flue gas |
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| CN102794101A (en) | 2012-11-28 |
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