CN101676205A - Co-production technology of sodium silicate, sodium bisulfite and gypsum whisker with mirabilite method - Google Patents
Co-production technology of sodium silicate, sodium bisulfite and gypsum whisker with mirabilite method Download PDFInfo
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- CN101676205A CN101676205A CN200810151017A CN200810151017A CN101676205A CN 101676205 A CN101676205 A CN 101676205A CN 200810151017 A CN200810151017 A CN 200810151017A CN 200810151017 A CN200810151017 A CN 200810151017A CN 101676205 A CN101676205 A CN 101676205A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to a co-production technology of three inorganic chemical products, in particular to a co-production technology of sodium silicate, sodium bisulfite and gypsum whisker with a mirabilite method. The invention has the technical characteristics of: mixing thenardite with silica sand in proportion; putting into a calcinator to calcinate into a sodium silicate product under the flame at the temperature of 1150-1400 DEG C; discharging SO2 gas; adsorbing SO2 with lime milk to obtain sodium bisulfite solution; reacting with mirabilite under the participation of gypsum whisker tocontrol the reaction conditions to be optimal; and meanwhile obtaining sodium bisulfite and gypsum whisker products.
Description
(1) technical field
The invention belongs to the inorganic chemical product production technology, is mirabilite method water glass, sodium bisulfite and gypsum crystal whisker co-production technology specifically
(2) technical background
At Chuan Xi, in the saltcake place of production, Pucheng county, see among the peoplely to substitute soda ash (or caustic soda) and silica sand mixed sintering water glass with thenardite, discharge a large amount of SO
2Gas pollutes greatly, also wastes the sulphur resource---because of with etc. kilomol contain Na
2O meter, rough saltcake cost only soda ash (or caustic soda) 1/10, very cause lower, huge economic interests make this destruction environment, the behavior of waste resource tired prohibit more than.
Can find be recyclable SO
2Gas has been controlled pollution, obtains high value added product again, stop above-mentioned phenomenon with economic interests equally? Appoint the argumentation of the relevant saltcake legal system sodium bisulfite of work " inorganic salt technology " to point out through the USSR (Union of Soviet Socialist Republics) ripple, add that the patent application (application number 2008100181317) of the existing gypsum combinations palpus of this invention people has just become the present patent application content, look into beyond example.
Through testing and calculating: the water glass of 1.5 tons of moduluses 1.25 of every product, consume 0.9 ton of silica sand (considering under the reactivity) approximately, 1.8 tons of thenardites (pure meter is considered under the high sulphur coal with low price) can comprehensively reclaim SO
2, 1.2 tons of coproduction sodium bisulfites produce 0.75 ton of crystal whisker of gypsum simultaneously, consume about 0.8 ton of average sulfur-bearing＞3.25% calorific value 〉=6,000 kilocalories/kilogram coal, and comparing with former technology only increases by 0.5 ton of unslaked lime, and over one hundred degree electric energy is several artificial.And after the reform, only 1.2 tons of sodium bisulfite explant prices of fecund are 3600 yuan, and it is many to be higher than 2100 yuan of 1.5 tons of water glass valencys of former main product, and only this item can be full of big profit.
The maximum characteristics of the present invention are that technology is simple, and technology is that tradition is novel again, the saving energy, lowering energy consumption and reducing pollutants discharge trinity.After implementing also large-scale production, will force existing water glass production to be eliminated voluntarily.Sodium bisulfite and processed goods are because of having enough market and profit during Jie, to become major product, coproduction water glass, crystal whisker of gypsum can significantly be made a price reduction, be convenient to be widely used in building material industry, 1,100 times of expansions of market capacity meeting, for such as bastard coal coal dust alkali gelatin construction material large-scale application, eliminate expensive obstacle, then meaning is especially great.
(3) summary of the invention
1, improves existing mirabilite method water glass and produce and reclaim SO
2: existing mirabilite method water glass is produced, because of SO
2Pollute heavyly, belong to illegal production, how with reverberatory furnace or short formula rotary kiln, small scale, power consumption is high, week screwing off production with the environmental protection supervision.The improvement back is pollution-free to disclose scale operation, with rotary kiln or the cyclone stove continuous production of growing up, makes thermal source with artificial water-gas in 1.05 times burnings of oxygen supply coefficient, and burning method tradition is superfluous.Because of coming out of the stove exhaust temperature between 850～1100 ℃, after the cyclone dedusting, the attached producing steam of serial connection heat pipe-type heat recovery boiler, make simultaneously tail gas reduce to≤200 ℃, this installs recyclable overall heat consumption 30% above heat energy, the air-washer of connecting again, Venturi tube, Pi Bodita, spray column etc. all can, wash water is controlled at 50 ℃～70 ℃ for well, and adding 0.03～0.05% Resorcinol (ammonium) class or alcohols in the water has anti-oxidantly, alleviates SO
2Be oxidized to SO
3Effect, but SO in the eccysis tail gas
3, NO
xAnd dust, be cooled to simultaneously between 50 ℃～70 ℃, gas washing cooling, wash water heats up naturally simultaneously, and circulating water pool must be prevented acid etching, installs refrigerating unit additional, and it is too high that wash water＞70 ℃ are contained steam by gas washing, and the reduction of enfleurage meeting concentration is bad again for following step milk of lime.Wash gas and be connected in series three grades of SO again
2The absorption tower, counter-current absorption SO
2To discharging purpose up to standard.Contain SO
2Washing gas is reflected under the strong basicity with last two-stage milk of lime and carries out reaction formula SO
2+ Ca (OH)
2→ CaSO
3+ H
2O or SO
2+ CaCO
3→ CaSO
3+ CO
2↑ produce sulfurous acid calcium powder slurry (water-soluble little), sampling is observed as seen with SO
3Absorption is carried out, and PH＞13 are reduced to neutrality gradually, when entering the SO that is connected with the gas washing tower
2During absorber portion, washed dense SO in the gas
2React with calcium sulfite: SO
2+ CaSO
3+ H
2O → Ca (HSO
3)
2, because of water-soluble big, the muddy CaSO of calcium bisulfite
3It is limpid that liquid becomes gradually, and the control solution PH can be prevented CO at 5～6
2Be absorbed, to observing liquid near limpid, when not too muddy, PH=5 can think and finish near reaction, emits smart filter, and filtering water insoluble slag obtains sodium bisulfite liquid.SO
2Absorption is thermopositive reaction, should install refrigerating unit additional, the control slurries 30～35 ℃ for well, adding milk of lime contains Ca (OH)
2Should be at 10～12%, (USSR (Union of Soviet Socialist Republics) is that milk of lime mixes adding at twice with saltcake, produce concentration of sodium bisulphite up to 36%, and attached product gypsum poor quality is different with the object of the invention, can not shine to do).
2, refining sodium sulphate liquid: saltcake adds water and becomes 360g/L concentration the most suitable, surveys to contain Ca
2+, Mg
2+, Fe
3+, Fe
2+, Mn
2+The equal size total mole number adds up 2 times of Na of mole
2CO
3, check weighing metal and arsenic molar content add 1.2 times of Na of total amount simultaneously
2S (or H
2S or NaHS) and flocculation agent a small amount of, gelatin 15～20g/m
3Stir evenly and be heated to 50～60 ℃ and leave standstill 24h, get supernatant liquor, cross fine filting machine, make Ca
2+, Mg
2+, Fe
3+, Fe
2+, Mn
2+Deng with carbonate deposition, heavy metal and arsenic with sulfide precipitation, Al
3+, H
2SiO
3Also hydrolytic precipitation simultaneously by filtering, adds sulfuric acid again and transfers between PH3.5～4, makes excessive adding soda ash Na
2CO among the S
2, H
2S overflows, the alkali that the reburns PH=7 that neutralizes, refining sodium sulphate liquid.
3, replacement(metathesis)reaction: with above-mentioned Ca (HSO
3)
2Filtrate and refining sodium sulphate liquid are with content mol ratio Ca (HSO
3)
2: Na
2SO
4=1.05: 1 ratio, being preheating to respectively closely boils pumps into reactor simultaneously with volume pump again, Na before adding
2SO
4Add the high-quality dehydrated gyp-whisker of its weight 2～4% in the liquid and make crystal type promoting reagent (crystal seed), pump into reactor, open stirrer, (n=80～120r/min) stir simultaneously, is warmed up to rapidly between 140～145 ℃ middling speed, gauge pressure maintains 0.2～0.22Mpa, stir 1h and permitted, leave standstill 2～3h, (reactor is little hurries up, the big prolongation point of reactor), reaction is finished, and blowing is crossed whizzer, leaches whisker, after＞70 ℃ of heat water-spraying's rinsings are clean, after drying while hot,, get the dehydrated gyp-whisker at once with 200～300 ℃ of warm air dryings.Pay special attention to: contain the free-water whisker under＜58 ℃ and can slowly become to contain the crystal water crystal whisker of gypsum, just bad.
4, produce sodium bisulfite: make the bisulfite mother liquid of sodium according to above-mentioned requirements, concentration is between 180～220g/L, and low how wash brilliant water concentration, can add micro-filtration+collecting and filtering apparatus and will wash brilliant water concentration and bring up to and contain NaHSO
3More than 20%, mix with female water, filtrate can return washes crystalline substance.This method obvious energy conservation, economical and practical.After directly concentrated, the crystallization of multiple-effect of female water, the centrifugation, isotonic solution is washed crystalline substance, and 250～300 ℃ of following dryings are made general industry level product.If palpus food, pharmacopeia level, analytical pure are answered the revulcanization removing heavy-metal once, after the smart filter, cross 751 chelating resins, ion-exchange, at Ca
2+Before penetrating, effluent liquid is pure NaHSO
3Liquid, reconcentration, dynamic crystallization, the centrifugal crystal that gets, dehydrated alcohol is washed crystalline substance, can obtain analytical pure NaHSO
3Product.
Claims (4)
1, improves existing mirabilite method water glass and produce and reclaim SO
2: existing mirabilite method water glass is produced, because of SO
2Pollute heavyly, belong to illegal production, how with reverberatory furnace or short formula rotary kiln, small scale, power consumption is high, week screwing off production with the environmental protection supervision.The improvement back is pollution-free to disclose scale operation, with rotary kiln or the cyclone stove continuous production of growing up, makes thermal source with artificial water-gas in 1.05 times burnings of oxygen supply coefficient, and burning method tradition is superfluous.Because of coming out of the stove exhaust temperature between 850～1100 ℃, after the cyclone dedusting, the attached producing steam of serial connection heat pipe-type heat recovery boiler, make simultaneously tail gas reduce to≤200 ℃, this installs recyclable overall heat consumption 30% above heat energy, the air-washer of connecting again, Venturi tube, Pi Bodita, spray column etc. all can, wash water is controlled at 50 ℃～70 ℃ for well, and adding 0.03～0.05% Resorcinol (ammonium) class or alcohols in the water has anti-oxidantly, alleviates SO
2Be oxidized to SO
3Effect, but SO in the eccysis tail gas
3, NO
xAnd dust, be cooled to simultaneously between 50 ℃～70 ℃, gas washing cooling, wash water heats up naturally simultaneously, and circulating water pool must be prevented acid etching, installs refrigerating unit additional, and it is too high that wash water＞70 ℃ are contained steam by gas washing, and the reduction of enfleurage meeting concentration is bad again for following step milk of lime.Wash gas and be connected in series three grades of SO again
2The absorption tower, counter-current absorption SO
2To discharging purpose up to standard.Contain SO
2Washing gas is reflected under the strong basicity with last two-stage milk of lime and carries out reaction formula SO
2+ Ca (OH)
2→ CaSO
3+ H
2O or SO
2+ CaCO
3→ CaSO
3+ CO
2↑ produce sulfurous acid calcium powder slurry (water-soluble little), sampling is observed as seen with SO
3Absorption is carried out, and PH＞13 are reduced to neutrality gradually, when entering the SO that is connected with the gas washing tower
2During absorber portion, washed dense SO in the gas
2React with calcium sulfite: SO
2+ CaSO
3+ H
2O → Ca (HSO
3)
2, because of water-soluble big, the muddy CaSO of calcium bisulfite
3It is limpid that liquid becomes gradually, and the control solution PH can be prevented CO at 5～6
2Be absorbed, to observing liquid near limpid, when not too muddy, PH=5 can think and finish near reaction, emits smart filter, and filtering water insoluble slag obtains sodium bisulfite liquid.SO
2Absorption is thermopositive reaction, should install refrigerating unit additional, the control slurries 30～35 ℃ for well, adding milk of lime contains Ca (OH)
2Should be at 10～12%, (USSR (Union of Soviet Socialist Republics) is that milk of lime mixes adding at twice with saltcake, produce concentration of sodium bisulphite up to 36%, and attached product gypsum poor quality is different with the object of the invention, can not shine to do).
2, refining sodium sulphate liquid: saltcake adds water and becomes 360g/L concentration the most suitable, surveys to contain Ca
2+, Mg
2+, Fe
3+, Fe
2+, Mn
2+The equal size total mole number adds up 2 times of Na of mole
2CO
3, check weighing metal and arsenic molar content add 1.2 times of Na of total amount simultaneously
2S (or H
2S or NaHS) and flocculation agent a small amount of, gelatin 15～20g/m
3Stir evenly and be heated to 50～60 ℃ and leave standstill 24h, get supernatant liquor, cross fine filting machine, make Ca
2+, Mg
2+, Fe
3+, Fe
2+, Mn
2+Deng with carbonate deposition, heavy metal and arsenic with sulfide precipitation, Al
3+, H
2SiO
3Also hydrolytic precipitation simultaneously by filtering, adds sulfuric acid again and transfers between PH3.5～4, makes excessive adding soda ash Na
2CO among the S
2, H
2S overflows, the alkali that the reburns PH=7 that neutralizes, refining sodium sulphate liquid.
3, replacement(metathesis)reaction: with above-mentioned Ca (HSO
3)
2Filtrate and refining sodium sulphate liquid are with content mol ratio Ca (HSO
3)
2: Na
2SO
4=1.05: 1 ratio, being preheating to respectively closely boils pumps into reactor simultaneously with volume pump again, Na before adding
2SO
4Add the high-quality dehydrated gyp-whisker of its weight 2～4% in the liquid and make crystal type promoting reagent (crystal seed), pump into reactor, open stirrer, (n=80～120r/min) stir simultaneously, is warmed up to rapidly between 140～145 ℃ middling speed, gauge pressure maintains 0.2～0.22Mpa, stir 1h and permitted, leave standstill 2～3h, (reactor is little hurries up, the big prolongation point of reactor), reaction is finished, and blowing is crossed whizzer, leaches whisker, after＞70 ℃ of heat water-spraying's rinsings are clean, after drying while hot,, get the dehydrated gyp-whisker at once with 200～300 ℃ of warm air dryings.Pay special attention to: contain the free-water whisker under＜58 ℃ and can slowly become to contain the crystal water crystal whisker of gypsum, just bad.
4, produce sodium bisulfite: make the bisulfite mother liquid of sodium according to above-mentioned requirements, concentration is between 180～220g/L, and low how wash brilliant water concentration, can add micro-filtration+collecting and filtering apparatus and will wash brilliant water concentration and bring up to and contain NaHSO
3More than 20%, mix with female water, filtrate can return washes crystalline substance.This method obvious energy conservation, economical and practical.After directly concentrated, the crystallization of multiple-effect of female water, the centrifugation, isotonic solution is washed crystalline substance, and 250～300 ℃ of following dryings are made general industry level product.If palpus food, pharmacopeia level, analytical pure are answered the revulcanization removing heavy-metal once, after the smart filter, cross 751 chelating resins, ion-exchange, at Ca
2+Before penetrating, effluent liquid is pure NaHSO
3Liquid, reconcentration, dynamic crystallization, the centrifugal crystal that gets, dehydrated alcohol is washed crystalline substance, can obtain analytical pure NaHSO
3Product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810151017A CN101676205A (en) | 2008-09-18 | 2008-09-18 | Co-production technology of sodium silicate, sodium bisulfite and gypsum whisker with mirabilite method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810151017A CN101676205A (en) | 2008-09-18 | 2008-09-18 | Co-production technology of sodium silicate, sodium bisulfite and gypsum whisker with mirabilite method |
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| Publication Number | Publication Date |
|---|---|
| CN101676205A true CN101676205A (en) | 2010-03-24 |
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ID=42028947
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810151017A Pending CN101676205A (en) | 2008-09-18 | 2008-09-18 | Co-production technology of sodium silicate, sodium bisulfite and gypsum whisker with mirabilite method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811701A (en) * | 2010-04-10 | 2010-08-25 | 湖南新恒光科技有限公司 | Environment-friendly production process for preparing white carbon black and sodium sulfite by adopting sodium sulfate |
| CN104790041A (en) * | 2015-04-13 | 2015-07-22 | 四川理工学院 | Method for preparing semi-hydrated gypsum whisker from mirabilite and calcium solution |
| CN104894650A (en) * | 2015-05-31 | 2015-09-09 | 四川理工学院 | Method for preparing calcium sulfate dihydrate whisker from mirabilite and calcium water |
| CN106219577A (en) * | 2016-08-09 | 2016-12-14 | 石河子大学 | A kind of method utilizing smoke-gas wet desulfurization intermediate product calcium sulfite to prepare sodium sulfite |
| CN109734106A (en) * | 2019-03-22 | 2019-05-10 | 石河子大学 | A method of high concentration solution of sodium bisulfite is prepared using trade waste |
| CN110002472A (en) * | 2019-02-21 | 2019-07-12 | 武汉青江化工黄冈有限公司 | The industrial method of by-product sodium sulphate continuous production sodium hydrogensulfite |
| CN110975613A (en) * | 2019-12-04 | 2020-04-10 | 沈阳环境科学研究院 | Regeneration method of sodium-alkali desulfurizing agent |
-
2008
- 2008-09-18 CN CN200810151017A patent/CN101676205A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811701A (en) * | 2010-04-10 | 2010-08-25 | 湖南新恒光科技有限公司 | Environment-friendly production process for preparing white carbon black and sodium sulfite by adopting sodium sulfate |
| CN101811701B (en) * | 2010-04-10 | 2011-08-03 | 湖南新恒光科技有限公司 | Environment-friendly production process for preparing white carbon black and sodium sulfite by adopting sodium sulfate |
| CN104790041A (en) * | 2015-04-13 | 2015-07-22 | 四川理工学院 | Method for preparing semi-hydrated gypsum whisker from mirabilite and calcium solution |
| CN104790041B (en) * | 2015-04-13 | 2017-04-19 | 四川理工学院 | Method for preparing semi-hydrated gypsum whisker from mirabilite and calcium solution |
| CN104894650A (en) * | 2015-05-31 | 2015-09-09 | 四川理工学院 | Method for preparing calcium sulfate dihydrate whisker from mirabilite and calcium water |
| CN104894650B (en) * | 2015-05-31 | 2017-08-25 | 四川理工学院 | A kind of method for preparing Dihydrate gypsum whiskers with saltcake and calcium water |
| CN106219577A (en) * | 2016-08-09 | 2016-12-14 | 石河子大学 | A kind of method utilizing smoke-gas wet desulfurization intermediate product calcium sulfite to prepare sodium sulfite |
| CN110002472A (en) * | 2019-02-21 | 2019-07-12 | 武汉青江化工黄冈有限公司 | The industrial method of by-product sodium sulphate continuous production sodium hydrogensulfite |
| CN109734106A (en) * | 2019-03-22 | 2019-05-10 | 石河子大学 | A method of high concentration solution of sodium bisulfite is prepared using trade waste |
| CN109734106B (en) * | 2019-03-22 | 2022-01-18 | 石河子大学 | Method for preparing high-concentration sodium bisulfite solution by using industrial waste |
| CN110975613A (en) * | 2019-12-04 | 2020-04-10 | 沈阳环境科学研究院 | Regeneration method of sodium-alkali desulfurizing agent |
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Open date: 20100324 |