CN105664692B - SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method2The method of coproduction crystal whisker of gypsum - Google Patents
SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method2The method of coproduction crystal whisker of gypsum Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/00—Reactants
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- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a kind of calcium and magnesium fusion methods, and SO in flue gas is removed in depth2The method of coproduction crystal whisker of gypsum uses magnesium hydroxide as the SO in absorbent cyclic absorption removing flue gas2；Desulfurizing tower bottom is passed through air, and desulfurization product magnesium sulfite is oxidized to magnesium sulfate；Adlerika is filtered, is allowed to react generation crystal whisker of gypsum with the calcium nitrate that subsequent magnesium hydrate regeneration process generates, is filtered, washed and dries, obtains semi-hydrated gypsum crystal whisker products；Whisker mother liquor is magnesium nitrate solution, and lime is added into magnesium nitrate solution and carries out magnesium sinking reaction, magnesium hydroxide filter cake and calcium nitrate solution is obtained by filtration；SO in desulfurizing tower circularly removing flue gas is returned after magnesium hydroxide Washing of Filter Cake2, calcium nitrate solution return crystal whisker of gypsum process.Calcium method, magnesium processes desulfurization are merged, the two is made to have complementary advantages, SO in flue gas2Removal efficiency ensure that the high-quality that there is by-product crystal whisker of gypsum whiteness to be greater than >=96%, chemical composition >=99% up to 98% or more.Natural resources and energy have been saved from source.
Description
Technical field
The flue gas generated after burning in fixed burner the present invention relates to coal, petroleum, natural gas fossil fuel needs
Remove sulfur dioxide SO therein2Industry and technical field, and in particular to flue gas is removed in depth in a kind of calcium and magnesium fusion method
Middle SO2The method of coproduction crystal whisker of gypsum.
Background technique
The fossil fuels such as coal, petroleum, natural gas contain sulfur dioxide SO after high-temp combustion in flue gas2Acid
Matter causes considerable damage to atmosphere and environment for human survival for many years.
The lime/gypsum method (calcium method) that domestic large power plant is widely used, be using limestone/lime as desulfurizing agent, can
By the sulfur dioxide SO in flue gas2Removal efficiency reaches 90-95%, and product is desulfurized gypsum, due in the limestone mine of various regions
Containing more chemical impurity, these impurity are transferred completely into desulfurized gypsum, reduce desulfurized gypsum effective component and exploitation value
Value.Using desulfurized gypsum as cement additive or low side construction material, more location is then accumulation or discharges Some Enterprises, at
For the burden of enterprise and society.In addition calcium method easily forms calcium sulfate scaling in desulfurizing tower, brings to safety and stability production many
Trouble.
It is that desulfurizing agent desulfuration efficiency is high with magnesia (magnesium processes), investment and operating cost rate are lower than calcium method, can make flue gas
Middle sulfur dioxide removal rate reaches 95% or more, and desulfurization product is magnesium sulfite, becomes magnesium sulfate after air oxidation, purify,
Evaporation recycling magnesium sulfate can be used for feed, fertilizer industry.Since magnesium ore resources and magnesium sulfate market capacity are limited, the popularization of magnesium processes
Using much being limited, some places are simply by desulfurization magnesium liquid direct emission.
By the pyrolysis of desulfurization product magnesium sulfite at magnesia and sulfur dioxide, dioxy is collected in magnesia cyclic absorption desulfurization
Changing sulphur and sulfuric acid is made, has built more set process units in foreign countries, China successfully introduces, and operating condition is good, but by
Complicated in pyrolysis, acid-making process, sulfuric acid product economic value is not high, and construction unit is difficult to obtain distinct economic.
CN102794101 discloses a kind of limestone desulfurization coproduction crystal whisker of gypsum technique, it is characterized in that being to inhale with lime stone
Agent is received, ammonium sulfate is process absorbent, and desulfurization slurry is directly translated into crystal whisker of gypsum through air oxidation.Due to not set impurity
Separating measure causes the chemical impurity in lime stone to be transferred completely into crystal whisker of gypsum product, seriously affects crystal whisker of gypsum production
Quality, purposes and selling price.
CN103908882 is disclosed absorbs SO with lime stone formulation absorption agent as main component in desulfurizing tower2And NOX,
Then carrying out electrolysis to absorbing liquid makes NOXGenerate N2With sulfate radical co-production calcium sulfate crystal whiskers.The method process simultaneous SO_2 and NO removal,
Process is succinct, same not set impurity removal process, contains lime stone bring all dirt, matter in the calcium sulfate crystal whiskers of coproduction
Amount and purposes are limited, while generating oxide in a manner of electrolysis and nitrogen oxide gas is promoted to absorb, and cost of energy is difficult to decrease.
Therefore, a kind of raw material sources of market in urgent need extensively, small investment, operating cost is low, desulfurization effect is good, it is stable,
Resource utilization is high, can efficient removal sulfur dioxide of flue gases SO2The clear of high-quality and high added value byproduct is produced simultaneously
Clean production new technique method.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a kind of calcium and magnesium fusion methods, and cigarette is removed in depth
SO in road gas2The method of coproduction crystal whisker of gypsum.
The technical scheme adopted by the invention is as follows:
SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method2The method of coproduction crystal whisker of gypsum specifically includes following step
It is rapid:
Flue gas is passed through desulfurizing tower, and magnesium hydroxide is used to remove sulfur dioxide SO therein as absorbent cyclic absorption2；
Desulfurizing tower bottom is passed through air, and desulfurization product magnesium sulfite is oxidized to magnesium sulfate；Adlerika is filtered, is allowed to and subsequent hydrogen-oxygen
Change the calcium nitrate reaction that magnesium step for regeneration generates and generate crystal whisker of gypsum, is filtered, washed and dries, obtains the production of semi-hydrated gypsum whisker
Product；Whisker mother liquor is magnesium nitrate solution, and lime is added into magnesium nitrate solution and carries out magnesium sinking reaction, and magnesium hydroxide filter is obtained by filtration
Cake and calcium nitrate solution；SO in desulfurizing tower circularly removing flue gas is returned after magnesium hydroxide Washing of Filter Cake2, calcium nitrate solution return
Crystal whisker of gypsum process.
Further, the magnesium hydroxide of the circular regeneration and desulfurizing tower tower bottom slurry are passed through desulfurizing tower after being mixed with beating
Sulfur dioxide SO in absorption from flue gas2。
Further, the lime is anti-using the calcium oxide of 1-20% or the suspension and crystal whisker of gypsum mother liquor of calcium hydroxide
It should carry out the regenerative operation of magnesium hydroxide.
Further, the lime using 1-20% calcium oxide or calcium hydroxide suspension to magnesium nitrate solution into
The regenerative response of row magnesium hydroxide is atmospheric operation, and temperature is 40-85 DEG C, calcium/magnesium (mole)≤1.
Further, the concentration of the desulfurization product magnesium sulfate is 5-30%, and calcium nitrate solution concentration is 5-30%, the two
The reaction that reaction generates crystal whisker of gypsum is atmospheric operation, and temperature is 98-120 DEG C.
Further, the whiteness of the crystal whisker of gypsum is greater than >=95%, draw ratio >=50, chemical composition >=99%.
SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method2The preparation facilities of coproduction crystal whisker of gypsum, including desulfurizing tower, crystalline substance
Palpus reactor and magnesium hydrate regeneration device, the desulfurization tower bottom are connected to mother liquor tank, and mother liquor tank passes through silicon slag filter and whisker
Reactor connection, whisker reactor are connected with magnesium hydrate regeneration device by whisker filter, are passed through in magnesium hydrate regeneration device
Lime, magnesium hydrate regeneration device lower end are provided with magnesium hydroxide filter, and it is anti-that the filtrate in magnesium hydroxide filter enters whisker
Device is answered, the magnesium hydroxide being obtained by filtration in magnesium hydroxide filter is discharged into mother liquor tank.
The invention has the benefit that
The invention discloses one kind using lime as raw material, using magnesia as cycle operation medium, to combustion of fossil fuel cigarette
Road gas carries out carrying out high-quality crystal whisker of gypsum circulation manufacture new process while deep desulfuration, merges calcium method, magnesium processes advantage
It is integrated, realizes flue gas high-efficiency desulfurization, and sweetening process is become the production process of high-quality crystal whisker of gypsum.Flue gas is passed through
Desulfurizing tower removes sulfur dioxide SO therein as absorbent cyclic absorption using magnesium hydroxide2.Desulfurizing tower bottom is passed through air,
Desulfurization product magnesium sulfite is oxidized to magnesium sulfate.Adlerika is filtered, is allowed to generate with subsequent magnesium hydrate regeneration process
Calcium nitrate reaction generate crystal whisker of gypsum；It is filtered, washed and dries, obtain whiteness >=96%, the high-quality half of draw ratio >=50
Water crystal whisker of gypsum product.Whisker mother liquor is magnesium nitrate solution, and it is anti-that lime/calcium hydroxide progress magnesium sinking is added into magnesium nitrate solution
It answers, magnesium hydroxide filter cake and calcium nitrate solution is obtained by filtration.Desulfurizing tower circularly removing flue is returned after magnesium hydroxide Washing of Filter Cake
SO in gas2, calcium nitrate solution return crystal whisker of gypsum process.
Since magnesium hydroxide activity is high, SO in flue gas can be made2Removal efficiency is up to 98% or more.Due to Adlerika
Filter operation is implemented, ensure that the high-quality that there is by-product crystal whisker of gypsum whiteness to be greater than >=96%, chemical composition >=99%.
Using lime as raw material, the limited disadvantage of magnesia FGD raw material sources is avoided；Using magnesium as working media, desulfurization effect is improved
Rate, while avoiding the desulfurization of calcium method and generating calcium sulfate scale layer easily in gas absorbing device.It is de- that this method merges calcium method, magnesium processes
Sulphur makes the two have complementary advantages, while generating the crystal whisker of gypsum of high quality.Compared to the generation and use of present desulfurized gypsum,
Crystal whisker of gypsum only can be dried into the upgrading raw material that can be used in fields such as papermaking, building materials with a small amount of energy, no
Purposes has only been expanded, subsequent product quality is improved, natural resources and energy can have been saved from source, preferably substitution day
The excavation of right Gypsum Mine and avoid thus bring human resources, energy dissipation and environmental pollution and destruction.This method is without useless
Water generates, the desulfurization suitable for various fossil fuel combustion waste gas.
Detailed description of the invention
Fig. 1 is the process flow chart that the preparation facilities of SO2 coproduction crystal whisker of gypsum in flue gas is removed in the present invention.
Wherein, 1, desulfurizing tower；2, mother liquor tank；3, silicon slag filter；4, whisker filter；5, whisker reactor；6, hydrogen-oxygen
Change magnesium filter；7, magnesium hydrate regeneration device.
Specific embodiment
As shown in Figure 1, SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method2The preparation facilities of coproduction crystal whisker of gypsum, packet
Desulfurizing tower, whisker reactor and magnesium hydrate regeneration device are included, the desulfurization tower bottom is connected to mother liquor tank, and mother liquor tank passes through silicon slag mistake
Filter is connected with whisker reactor, and whisker reactor is connected by whisker filter with magnesium hydrate regeneration device, and magnesium hydroxide is again
It is passed through lime in raw device, magnesium hydrate regeneration device lower end is provided with magnesium hydroxide filter, the filtrate in magnesium hydroxide filter
Into whisker reactor, the magnesium hydroxide being obtained by filtration in magnesium hydroxide filter is discharged into mother liquor tank.
Specifically used process are as follows: flue gas is introduced into desulfurizing tower desulfurization, and the flue gas of desulfurization enters lower section in desulfurizing tower
Mother liquor tank is passed through magnesium hydroxide as desulfurizing agent in mother liquor tank, makes desulfuration efficiency up to 98% or more；Mother liquor tank is filtered by silicon slag
The ingredients such as desilication slag are removed in machine filtering, and filtrate enters in whisker reactor and lime reaction, and whisker reactor passes through whisker filter
Filtering collects solid whisker, filters resulting filtrate and enter magnesium hydrate regeneration device, be passed through lime in magnesium hydrate regeneration device,
It is reacted using calcium oxide/calcium hydroxide with circulatory mediator magnesium nitrate in magnesium hydrate regeneration process, generates magnesium hydroxide and nitric acid
Calcium aqueous solution；Newly-generated magnesium hydroxide reenters after being filtered, washed through magnesium hydroxide filter and carries out cigarette in mother liquor tank
Road desulfurization；Magnesium hydroxide filter filters resulting calcium nitrate aqueous solution and enters whisker reactor, circular response；Magnesium hydroxide
The magnesium hydroxide being obtained by filtration in filter is discharged into mother liquor tank.
SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method2The method of coproduction crystal whisker of gypsum, specifically comprises the following steps:
(1) desulfurization: using lime as raw material, using magnesium hydroxide as cyclic absorption medium, magnesium hydroxide and desulfurizing tower tower bottom are starched
Material is passed through in desulfurizing tower after being mixed with beating, and flue gas is contacted with magnesium hydroxide circulating absorption solution, sulfur dioxide absorption SO2Become
Magnesium sulfite generates magnesium sulfate soluble easily in water with the air reaction being passed through in the mother liquor tank of absorb the bottom of the tower；
(2) it prepares crystal whisker of gypsum: extracting the magnesium sulfate that mother liquor trench bottom concentration reaches 5-30%, filtered with silicon slag filter
It preheats later, the calcium nitrate solution generated with magnesium hydrate regeneration process is in whisker reactor to mix at a temperature of 98-120 DEG C
It closes, mix products are crystal whisker of gypsum product after the washed drying of filter cake by the filtering of whisker filter, drying；
(3) magnesium hydrate regeneration: filtering resulting filtrate by whisker filter is magnesium nitrate solution, by magnesium nitrate solution
It is stirred to react in magnesium hydrate regeneration device 2-4 hours for the lime suspension of 1-30% in 40-85 DEG C of temperature range with concentration,
Obtain magnesium magma；
(4) magnesium hydroxide recycles: magnesium magma being filtered by magnesium hydroxide filter machine, filtrate is calcium nitrate
Solution is passed through whisker reactor manufacture crystal whisker of gypsum, and filter cake is regeneration magnesium hydroxide, returns to dioxy in desulfurizing tower absorption from flue gas
Change sulphur SO2。
To have the principles of chemistry and implementation to desulfurization of the invention, crystal whisker of gypsum manufacture and magnesium hydrate regeneration
Further to understand, spy is described as follows:
Embodiment 1
Desulfurization tower packing high 2000mm, Mg (OH)2Slurry concentration 2%, is passed through containing SO by 50 DEG C of operation temperature21.2% mould
Quasi- mixed gas 100L/min, liquid-gas ratio (L/G)=1.5, measurement tower export SO2Concentration 138PPM, desulfuration efficiency 98.85%.
It is gradually added into magnesium hydroxide into 10L slurry and keeps Mg (OH)2When slurry concentration about 1-2%, 15h, add Mg (OH)21200g is surveyed
It measures tower and exports SO2Concentration 152PPM, desulfuration efficiency 98.73%.Desulphurization mother solution is taken, blowing air oxidation, filtering obtain MgSO4Solution,
Survey concentration 1.62mol/L.Take MgSO4Calcium nitrate Ca (the NO of solution 1L and 2.0mol/L3)2Aqueous solution 810mL is heated to 98 DEG C,
It is added in 5000ml reactor together, insulation reaction 30min, heat preservation is filtered, washed, and 105 DEG C dry to obtain semi-hydrated gypsum whisker 216
Gram.Survey whisker whiteness 96%, draw ratio 60.Whisker mother liquor 2200ml is collected, Mg (NO is surveyed3)2Concentration 0.73mol/L.Take 20%Ca
(OH)2Thick liquid 600g, under the conditions of 45 DEG C with the Mg (NO of 2200ml concentration 0.73mol/L3)2Solution reaction obtains Mg
(OH)2Suspension.Suspension, water washing filter cake are filtered, obtains magnesium hydroxide filter cake 169g (water content 44%), merging filtrate,
Wash water 3200ml is evaporated to 800ml, surveys calcium nitrate Ca (NO3)2800ml prepares subsequent cycle manufacture crystal whisker of gypsum and uses.Hydrogen-oxygen
Change magnesium wet cake and returns to the use of desulfurizing tower circulation desulfurization.
Embodiment 2
Into desulfurizing tower flue-gas flow rate 12000NM3/ h, SO21.03%, temperature is 150 DEG C, is passed through in the middle part of desulfurizing tower, with from
The circulation fluid counter current contacting that top is sprayed, magnesium sulfate concentration 1.2mol/L, Mg (OH) in circulation fluid2Slurry concentration 1-2%,
50 DEG C of operation temperature, liquid-gas ratio (L/G)=1.5, measurement tower exports SO2Concentration 118PPM, desulfuration efficiency 98.85%.
Desulphurization mother solution 10L after air oxidation, filtering are taken, is pale powder gram after filter residue drying；Filtrate surveys MgSO4Concentration
For 1.22mol/L.Take the calcium nitrate Ca (NO for being adjusted to 2.0mol/L3)2Aqueous solution 6.1L is heated to 100 DEG C, 20L is added together
In reactor, insulated and stirred reacts 30min, is filtered, washed, 105 DEG C dry to obtain 1645 grams of semi-hydrated gypsum whisker.Survey whisker whiteness
96%, average aspect ratio 75, chemical composition 99%.
Crystal whisker of gypsum mother liquor 16L is received, Mg (NO is surveyed3)2Concentration 0.74mol/L.CaO680g is taken, adds water 2L, is made into hydroxide
Calcium suspension 2680g, under the conditions of 65 DEG C with the Mg (NO of 16L concentration 0.74mol/L3)2Solution reaction obtains Mg (OH)2It is outstanding
Turbid.Suspension, water washing filter cake are filtered, obtains magnesium hydroxide filter cake 1260g (water content 48%), merging filtrate, wash water 20L,
It is evaporated to 6.0L, surveys Ca (NO3)2Concentration 1.95mol/L returns to crystal whisker of gypsum manufacturing process.
The above is not limitation of the present invention, it should be pointed out that: those skilled in the art are come
It says, under the premise of not departing from essential scope of the present invention, several variations, modifications, additions or substitutions can also be made, these improvement
It also should be regarded as protection scope of the present invention with retouching.
Claims (4)
1. SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method2The method of coproduction crystal whisker of gypsum, which is characterized in that specifically include
Following steps:
Flue gas is passed through desulfurizing tower, and magnesium hydroxide is used to remove sulfur dioxide SO therein as absorbent cyclic absorption2；Desulfurization
Tower bottom is passed through air, and desulfurization product magnesium sulfite is oxidized to magnesium sulfate；Adlerika is filtered, is allowed to and subsequent magnesium hydroxide
The calcium nitrate reaction that step for regeneration generates generates crystal whisker of gypsum, is filtered, washed and dries, obtains semi-hydrated gypsum crystal whisker products；It is brilliant
Must mother liquor be magnesium nitrate solution, into magnesium nitrate solution be added lime carry out magnesium sinking reaction, be obtained by filtration magnesium hydroxide filter cake and
Calcium nitrate solution；SO in desulfurizing tower circularly removing flue gas is returned after magnesium hydroxide Washing of Filter Cake2, calcium nitrate solution return gypsum
Whisker process；
The magnesium hydroxide and desulfurizing tower tower bottom slurry of the circular regeneration are passed through in desulfurizing tower absorption from flue gas after being mixed with beating
Sulfur dioxide SO2；
The whiteness of the crystal whisker of gypsum is greater than >=95%, draw ratio >=50, chemical composition >=99%；
SO in flue gas is removed in depth in above-mentioned calcium and magnesium fusion method2The preparation facilities of coproduction crystal whisker of gypsum, including desulfurizing tower, whisker are anti-
Device and magnesium hydrate regeneration device are answered, the desulfurization tower bottom is connected to mother liquor tank, and mother liquor tank is reacted by silicon slag filter and whisker
Device connection, whisker reactor are connected by whisker filter with magnesium hydrate regeneration device, are passed through lime in magnesium hydrate regeneration device,
Magnesium hydrate regeneration device lower end is provided with magnesium hydroxide filter, and the filtrate in magnesium hydroxide filter enters whisker reactor,
The magnesium hydroxide being obtained by filtration in magnesium hydroxide filter is discharged into mother liquor tank.
2. SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method according to claim 12The method of coproduction crystal whisker of gypsum,
It is characterized in that, the lime reacts progress with crystal whisker of gypsum mother liquor using the calcium oxide of 1-20% or the suspension of calcium hydroxide
The regenerative operation of magnesium hydroxide.
3. SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method according to claim 22The method of coproduction crystal whisker of gypsum,
It is characterized in that, the lime carries out hydroxide to magnesium nitrate solution using the calcium oxide of 1-20% or the suspension of calcium hydroxide
The regenerative response of magnesium is atmospheric operation, and temperature is 40-85 DEG C, calcium/magnesium (mole)≤1.
4. SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method according to claim 12The method of coproduction crystal whisker of gypsum,
It is characterized in that, the concentration of the desulfurization product magnesium sulfate is 5-30%, calcium nitrate solution concentration is 5-30%, and the two reaction generates
The reaction of crystal whisker of gypsum is atmospheric operation, and temperature is 98-120 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846440A (en) * | 2015-05-29 | 2015-08-19 | 昆明冶金研究院 | Method for preparing high-purity calcium sulfate dihydrate crystal whisker by using metallurgic flue gas desulfurization gypsum recrystallization process |
| CN104959012A (en) * | 2015-04-17 | 2015-10-07 | 熊天渝 | Magnesium-calcium based wet method desulphurization system and method for removing sulfur dioxide in flue gas and producing gypsum |
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| CN104959012A (en) * | 2015-04-17 | 2015-10-07 | 熊天渝 | Magnesium-calcium based wet method desulphurization system and method for removing sulfur dioxide in flue gas and producing gypsum |
| CN104846440A (en) * | 2015-05-29 | 2015-08-19 | 昆明冶金研究院 | Method for preparing high-purity calcium sulfate dihydrate crystal whisker by using metallurgic flue gas desulfurization gypsum recrystallization process |
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