CN105664692A - Method for deep removal of SO2 from flue gas by calcium-magnesium fusion technique and co-production of gypsum whisker - Google Patents
Method for deep removal of SO2 from flue gas by calcium-magnesium fusion technique and co-production of gypsum whisker Download PDFInfo
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- CN105664692A CN105664692A CN201610016801.6A CN201610016801A CN105664692A CN 105664692 A CN105664692 A CN 105664692A CN 201610016801 A CN201610016801 A CN 201610016801A CN 105664692 A CN105664692 A CN 105664692A
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- magnesium
- calcium
- gypsum
- flue gas
- whisker
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- 239000010440 gypsum Substances 0.000 title claims abstract description 56
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000003546 flue gas Substances 0.000 title claims abstract description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 title abstract 2
- 230000004927 fusion Effects 0.000 title abstract 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 73
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 50
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 50
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011777 magnesium Substances 0.000 claims abstract description 40
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 30
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000011575 calcium Substances 0.000 claims abstract description 28
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008929 regeneration Effects 0.000 claims abstract description 26
- 238000011069 regeneration method Methods 0.000 claims abstract description 26
- 230000023556 desulfurization Effects 0.000 claims abstract description 25
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 19
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 13
- 239000012065 filter cake Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 239000010413 mother solution Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000002250 absorbent Substances 0.000 claims abstract description 6
- 230000002745 absorbent Effects 0.000 claims abstract description 6
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 48
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 38
- 230000003009 desulfurizing effect Effects 0.000 claims description 34
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 17
- 238000007500 overflow downdraw method Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000010009 beating Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 230000009719 regenerative response Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 18
- 238000001914 filtration Methods 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 4
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000004571 lime Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 230000000295 complement effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000019738 Limestone Nutrition 0.000 description 7
- 239000006028 limestone Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000011505 plaster Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- -1 white residue Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D53/73—After-treatment of removed components
-
- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The invention discloses a method for deep removal of SO2 from flue gas by calcium-magnesium fusion technique and co-production of gypsum whisker. The method includes: using magnesium hydroxide as an absorbent for cyclic absorption removal of SO2 from flue gas; introducing air from the bottom of a desulfurization tower to oxidize desulfurization product magnesium sulfite into magnesium sulfate; filtering a magnesium sulfate solution, then reacting the filtrate with calcium nitrate generated by a subsequent magnesium hydroxide regeneration process to produce gypsum whisker, carrying out filtering, washing and drying to obtain a semi-hydrated gypsum whisker product; taking a magnesium nitrate solution as the whisker mother solution, adding lime into the magnesium nitrate solution to carry out magnesium precipitation reaction, and performing filtering to obtain a magnesium hydroxide filter cake and a calcium nitrate solution; washing the magnesium hydroxide filter cake, then returning the washed magnesium hydroxide filter cake to the desulfurization tower for cyclic removal of SO2 from flue gas, and returning the calcium nitrate solution to a gypsum whisker process. The method fuses calcium method and magnesium method desulfurization, makes the two complement each other's advantages, can reach a flue gas SO2 removal efficiency up to more than 98%, ensures the by-product gypsum whisker the high quality of a whiteness of more than or equal to 96% and chemical composition of more than or equal to 99%, thus saving natural resources and energy from the source.
Description
Technical field
The present invention relates to the flue gas produced after coal, oil, natural gas Fossil fuel burn in fixed burner to need to remove sulfur dioxide SO therein2Industry and technical field, be specifically related to SO in a kind of calcium and magnesium fusion method deep removal flue gas2The method of coproduction crystal whisker of gypsum.
Background technology
The Fossil fuels such as coal, oil, natural gas are after high-temp combustion, containing sulfur dioxide SO in flue gas2Acidic materials, cause considerable damage to air and environment for human survival for many years.
The lime/gypsum method (calcium method) that domestic large power plant is widely used, is using limestone/lime as desulfurizing agent, can by the sulfur dioxide SO in flue gas2Removal efficiency reaches 90-95%, and product is desulfurated plaster, and owing to containing more chemical impurity in the limestone mine of various places, these impurity are transferred completely in desulfurated plaster, reduce desulfurated plaster effective ingredient and value. Some Enterprises utilizes desulfurated plaster as cement additire or low side construction material, and more location is then pile up or discharge, becomes enterprise and the burden of society. Additionally calcium method is easily formed calcium sulfate scaling in desulfurizing tower, produces to safety and stability and brings many troubles.
High with magnesium oxide (magnesium processes) for desulfurizing agent desulfuration efficiency, investment and operating cost rate are lower than calcium method, sulfur dioxide of flue gases removal efficiency can be made to reach more than 95%, desulfurization product is magnesium sulfite, becoming magnesium sulfate after air oxidation, purification, evaporation are reclaimed magnesium sulfate and be can be used for feedstuff, fertilizer industry. Owing to magnesium ore resources and magnesium sulfate market capacity are limited, the popularization of magnesium processes adopts and is subject to many restrictions, and desulfurization magnesium liquid is simply directly discharged by some place.
Desulfurization product magnesium sulfite pyrolysis is become magnesium oxide and sulfur dioxide, magnesium oxide cyclic absorption desulfurization, collect sulfur dioxide and make sulphuric acid, build many sets process units abroad, China successfully introduces, and ruuning situation is good, but due to pyrolysis, acid-making process complexity, sulfuric acid product economic worth 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, with limestone for absorbent, ammonium sulfate is process absorbent, and through air oxidation, desulfurization slurry is directly translated into crystal whisker of gypsum.Owing to being not provided with magazins' layout measure, cause the chemical impurity in limestone to be transferred completely in crystal whisker of gypsum product, badly influence crystal whisker of gypsum product quality, purposes and selling price.
CN103908882 disclose with limestone be main component formulation absorption agent in desulfurizing tower, absorb SO2And NOX, then absorption liquid is carried out electrolysis and makes NOXGenerate N2With sulfate radical co-production calcium sulfate crystal whiskers. This method flow process simultaneous SO_2 and NO removal, flow process is succinct, is not provided with impurity removal operation equally, the all dirt brought containing limestone in the calcium sulfate crystal whiskers of coproduction, quality and purposes are limited, produce oxide simultaneously and promote that nitrogen oxide gas absorbs in the way of electrolysis, and cost of energy is difficult to reduce.
Therefore, market in urgent need one raw material sources are extensively, small investment, operating cost are low, desulfurized effect good, stable, resource utilization is high, can efficient removal sulfur dioxide of flue gases SO2Produce the new cleanproduction process method of high-quality and high added value side-product simultaneously.
Summary of the invention
For problems of the prior art, it is an object of the invention to provide SO in a kind of calcium and magnesium fusion method deep removal flue gas2The method of coproduction crystal whisker of gypsum.
The technical scheme that the present invention takes is:
SO in a kind of calcium and magnesium fusion method deep removal flue gas2The method of coproduction crystal whisker of gypsum, specifically includes following steps:
Flue gas passes into desulfurizing tower, uses magnesium hydroxide to remove sulfur dioxide SO therein as absorbent cyclic absorption2; Pass into air at the bottom of desulfurizing tower, desulfurization product magnesium sulfite is oxidized to magnesium sulfate; Filter Adlerika, so as to follow-up magnesium hydrate regeneration operation produce calcium nitrate react generate crystal whisker of gypsum, filter, wash and dry, obtain semi-hydrated gypsum crystal whisker products; Whisker mother solution is magnesium nitrate solution, adds Calx and carries out magnesium sinking reaction, be filtrated to get magnesium hydroxide filter cake and calcium nitrate solution in magnesium nitrate solution; SO in desulfurizing tower circularly removing flue gas is returned after magnesium hydroxide Cake Wash2, calcium nitrate solution returns crystal whisker of gypsum operation.
Further, the magnesium hydroxide of described circular regeneration mixes the sulfur dioxide SO passing in desulfurizing tower absorption from flue gas after making beating with desulfurizing tower tower prime cement material2。
Further, described Calx adopts the calcium oxide of 1-20% or the suspension of calcium hydroxide to react, with crystal whisker of gypsum mother solution, the regenerative operation carrying out magnesium hydroxide.
Further, described Calx adopts the regenerative response that magnesium nitrate solution is carried out magnesium hydroxide by the calcium oxide of 1-20% or the suspension of calcium hydroxide to be atmospheric operation, and temperature is 40-85 DEG C, calcium/magnesium (mole)≤1.
Further, the concentration of described desulfurization product magnesium sulfate is 5-30%, and calcium nitrate solution concentration is 5-30%, and it is atmospheric operation that the two reaction generates the reaction of crystal whisker of gypsum, and temperature is 98-120 DEG C.
Further, the whiteness of described crystal whisker of gypsum more than >=95%, draw ratio >=50, chemical composition >=99%.
SO in a kind of calcium and magnesium fusion method deep removal flue gas2The preparation facilities of coproduction crystal whisker of gypsum, including desulfurizing tower, whisker reactor and magnesium hydrate regeneration device, mother liquor tank is connected bottom described desulfurizing tower, mother liquor tank is connected by white residue filter and whisker reactor, whisker reactor is connected by whisker filter and magnesium hydrate regeneration device, Calx is passed in magnesium hydrate regeneration device, magnesium hydrate regeneration device lower end is provided with magnesium hydroxide filter, filtrate in magnesium hydroxide filter enters whisker reactor, and the magnesium hydroxide being filtrated to get in magnesium hydroxide filter enters mother liquor tank.
The invention have the benefit that
The invention discloses a kind of with Calx be raw material, with magnesium oxide for periodic duty medium, carry out the circulation of high-quality crystal whisker of gypsum while combustion of fossil fuel flue gas is carried out deep desulfuration and manufacture new process, merge calcium method, magnesium processes advantage is integrated, realize flue gas high-efficiency desulfurization, and sweetening process is become the production process of high-quality crystal whisker of gypsum.Flue gas passes into desulfurizing tower, adopts magnesium hydroxide to remove sulfur dioxide SO therein as absorbent cyclic absorption2. Pass into air at the bottom of desulfurizing tower, desulfurization product magnesium sulfite is oxidized to magnesium sulfate. Filter Adlerika, so as to follow-up magnesium hydrate regeneration operation produce calcium nitrate react generate crystal whisker of gypsum; Filter, wash and dry, obtain whiteness >=96%, the high-quality semi-hydrated gypsum crystal whisker products of draw ratio >=50. Whisker mother solution is magnesium nitrate solution, adds Calx/calcium hydroxide and carries out magnesium sinking reaction, be filtrated to get magnesium hydroxide filter cake and calcium nitrate solution in magnesium nitrate solution. SO in desulfurizing tower circularly removing flue gas is returned after magnesium hydroxide Cake Wash2, calcium nitrate solution returns crystal whisker of gypsum operation.
Owing to magnesium hydroxide activity is high, SO in flue gas can be made2Removal efficiency reaches more than 98%. Owing to Adlerika is implemented filter operation, it is ensured that by-product crystal whisker of gypsum have whiteness more than >=96%, the high-quality of chemical composition >=99%. With Calx for raw material, it is to avoid the shortcoming that magnesia FGD raw material sources are limited; With magnesium for working media, improve desulfuration efficiency, avoid calcium method desulfurization simultaneously in gas absorbing device, easily produce calcium sulfate scale layer. This method merges calcium method, magnesium processes desulfurization, makes the two have complementary advantages, produces high-quality crystal whisker of gypsum simultaneously. Generation and employing compared to present desulfurated plaster, only with a small amount of energy, crystal whisker of gypsum can be dried into the upgrading raw material that can be used in the field such as papermaking, building materials, not only expand purposes, improve subsequent product quality, natural resources and energy can be saved from source, substituted the excavation in natural gypsum ore deposit better and avoid human resources, energy dissipation and environmental pollution and the destruction thus brought. This method produces without waste water, it is adaptable to the desulfurization of various fossil fuel combustion waste gas.
Accompanying drawing explanation
Fig. 1 removes the process chart of the preparation facilities of SO2 coproduction crystal whisker of gypsum in flue gas in the present invention.
Wherein, 1, desulfurizing tower; 2, mother liquor tank; 3, white residue filter; 4, whisker filter; 5, whisker reactor; 6, magnesium hydroxide filter; 7, magnesium hydrate regeneration device.
Detailed description of the invention
As it is shown in figure 1, SO in a kind of calcium and magnesium fusion method deep removal flue gas2The preparation facilities of coproduction crystal whisker of gypsum, including desulfurizing tower, whisker reactor and magnesium hydrate regeneration device, mother liquor tank is connected bottom described desulfurizing tower, mother liquor tank is connected by white residue filter and whisker reactor, whisker reactor is connected by whisker filter and magnesium hydrate regeneration device, Calx is passed in magnesium hydrate regeneration device, magnesium hydrate regeneration device lower end is provided with magnesium hydroxide filter, filtrate in magnesium hydroxide filter enters whisker reactor, and the magnesium hydroxide being filtrated to get in magnesium hydroxide filter enters mother liquor tank.
Specifically used process is: flue gas is introduced into desulfurizing tower desulfurization, and the flue gas of desulfurization in desulfurizing tower enters the mother liquor tank of lower section, passes into magnesium hydroxide as desulfurizing agent, make desulfuration efficiency reach more than 98% in mother liquor tank; Mother liquor tank is filtered by white residue filter, remove the compositions such as white residue, filtrate enters in whisker reactor and lime reaction, whisker reactor is filtered by whisker filter, collecting solid whisker, the filtrate filtering gained enters magnesium hydrate regeneration device, passes into Calx in magnesium hydrate regeneration device, adopt calcium oxide/calcium hydroxide to react with circulatory mediator magnesium nitrate in magnesium hydrate regeneration process, generate magnesium hydroxide and calcium nitrate aqueous solution;Newly-generated magnesium hydroxide reenters after the filtration of magnesium hydroxide filter, washing and carries out flue gas desulfurization in mother liquor tank; Magnesium hydroxide filter filters the calcium nitrate aqueous solution of gained and enters whisker reactor, circular response; The magnesium hydroxide being filtrated to get in magnesium hydroxide filter enters mother liquor tank.
SO in a kind of calcium and magnesium fusion method deep removal flue gas2The method of coproduction crystal whisker of gypsum, specifically includes following steps:
(1) desulfurization: with Calx for raw material, with magnesium hydroxide for cyclic absorption medium, magnesium hydroxide passes in desulfurizing tower mix making beating with desulfurizing tower tower prime cement material after, and flue gas contacts with magnesium hydroxide circulating absorption solution, sulfur dioxide absorption SO2Become magnesium sulfite, in the mother liquor tank bottom absorption tower, generate magnesium sulfate soluble in water with the air reaction passed into;
(2) crystal whisker of gypsum is prepared: extract concentration bottom mother liquor tank and reach the magnesium sulfate of 5-30%, preheating after filtering with white residue filter, with magnesium hydrate regeneration process produce calcium nitrate solution in whisker reactor to mix at 98-120 DEG C of temperature, mix products is filtered by whisker filter, dries, and is crystal whisker of gypsum product after the scrubbed drying of filter cake;
(3) magnesium hydrate regeneration: the filtrate being filtered gained by whisker filter is magnesium nitrate solution, by magnesium nitrate solution and concentration be the Calx suspension of 1-30% in 40-85 DEG C of temperature range stirring reaction 2-4 hour in magnesium hydrate regeneration device, obtain magnesium magma;
(4) magnesium hydroxide circulation: filtered by magnesium hydroxide filter machine by magnesium magma, filtrate is that calcium nitrate solution passes into whisker reactor manufacture crystal whisker of gypsum, and filter cake is regenerated hydrogen magnesium oxide, returns sulfur dioxide SO in desulfurizing tower absorption from flue gas2。
The principles of chemistry and implementation for making the desulfurization to the present invention, crystal whisker of gypsum manufacture and magnesium hydrate regeneration have further understanding, and special explanation is as follows:
Embodiment 1
Desulfurizing tower filler height 2000mm, Mg (OH)2Slurry concentration 2%, operates temperature 50 C, passes into containing SO2The simulation mixing gas 100L/min of 1.2%, liquid-gas ratio (L/G)=1.5, measure tower outlet SO2Concentration 138PPM, desulfuration efficiency 98.85%. In 10L slip, it is gradually added into magnesium hydroxide keeps Mg (OH)2When slurry concentration is about 1-2%, 15h, add Mg (OH)21200g, measures tower outlet SO2Concentration 152PPM, desulfuration efficiency 98.73%. Take desulphurization mother solution, blowing air oxidation, filtration, obtain MgSO4Solution, surveys concentration 1.62mol/L. Take MgSO4Calcium nitrate Ca (the NO of solution 1L and 2.0mol/L3)2Aqueous solution 810mL, heating, to 98 DEG C, adds in 5000ml reactor, insulation reaction 30min together, and insulation is filtered, washing, dries to obtain semi-hydrated gypsum whisker 216 grams for 105 DEG C. Survey whisker whiteness 96%, draw ratio 60. Collect whisker mother solution 2200ml, survey Mg (NO3)2Concentration 0.73mol/L. Take 20%Ca (OH)2Thick liquid 600g, with the Mg (NO of 2200ml concentration 0.73mol/L under 45 DEG C of conditions3)2Solution reaction, obtains Mg (OH)2Suspension. Filter suspension, water washing filter cake, obtain magnesium hydroxide filter cake 169g (water content 44%), merging filtrate, wash water 3200ml, be evaporated to 800ml, survey calcium nitrate Ca (NO3)2800ml, prepares subsequent cycle and manufactures crystal whisker of gypsum employing. Magnesium hydroxide wet cake returns desulfurizing tower circulation desulfurization and adopts.
Embodiment 2
Enter desulfurizing tower flue-gas flow rate 12000NM3/ h, SO21.03%, temperature is 150 DEG C, passes in the middle part of desulfurizing tower, with the circulation fluid counter current contacting sprayed from top, magnesium sulfate concentration 1.2mol/L, Mg (OH) in circulation fluid2Slurry concentration 1-2%, operates temperature 50 C, liquid-gas ratio (L/G)=1.5, measures tower outlet SO2Concentration 118PPM, desulfuration efficiency 98.85%.
Taking desulphurization mother solution 10L, filtration after air oxidation, filtering residue is pale powder gram after drying; Filtrate surveys MgSO4Concentration is 1.22mol/L. Take the calcium nitrate Ca (NO being adjusted to 2.0mol/L3)2Aqueous solution 6.1L, heating, to 100 DEG C, adds in 20L reactor together, insulated and stirred reaction 30min, filters, washs, dries to obtain semi-hydrated gypsum whisker 1645 grams for 105 DEG C. Survey whisker whiteness 96%, average aspect ratio 75, chemical composition 99%.
Receive crystal whisker of gypsum mother solution 16L, survey Mg (NO3)2Concentration 0.74mol/L. Taking CaO680g, add water 2L, is made into calcium hydroxide suspension 2680g, with the Mg (NO of 16L concentration 0.74mol/L under 65 DEG C of conditions3)2Solution reaction, obtains Mg (OH)2Suspension. Filter suspension, water washing filter cake, obtain magnesium hydroxide filter cake 1260g (water content 48%), merging filtrate, wash water 20L, be evaporated to 6.0L, survey Ca (NO3)2Concentration 1.95mol/L, returns crystal whisker of gypsum manufacturing process.
The above is not limitation of the present invention; it is noted that, for those skilled in the art; under the premise without departing from essential scope of the present invention; can also making some changes, remodeling, interpolation or replacement, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (7)
1. SO in a calcium and magnesium fusion method deep removal flue gas2The method of coproduction crystal whisker of gypsum, it is characterised in that specifically include following steps:
Flue gas passes into desulfurizing tower, uses magnesium hydroxide to remove sulfur dioxide SO therein as absorbent cyclic absorption2; Pass into air at the bottom of desulfurizing tower, desulfurization product magnesium sulfite is oxidized to magnesium sulfate; Filter Adlerika, so as to follow-up magnesium hydrate regeneration operation produce calcium nitrate react generate crystal whisker of gypsum, filter, wash and dry, obtain semi-hydrated gypsum crystal whisker products; Whisker mother solution is magnesium nitrate solution, adds Calx and carries out magnesium sinking reaction, be filtrated to get magnesium hydroxide filter cake and calcium nitrate solution in magnesium nitrate solution; SO in desulfurizing tower circularly removing flue gas is returned after magnesium hydroxide Cake Wash2, calcium nitrate solution returns crystal whisker of gypsum operation.
2. SO in a kind of calcium and magnesium fusion method deep removal flue gas according to claim 12The method of coproduction crystal whisker of gypsum, it is characterised in that the magnesium hydroxide of described circular regeneration mixes the sulfur dioxide SO passing in desulfurizing tower absorption from flue gas after making beating with desulfurizing tower tower prime cement material2。
3. SO in a kind of calcium and magnesium fusion method deep removal flue gas according to claim 12The method of coproduction crystal whisker of gypsum, it is characterised in that described Calx adopts the calcium oxide of 1-20% or the suspension of calcium hydroxide to react, with crystal whisker of gypsum mother solution, the regenerative operation carrying out magnesium hydroxide.
4. SO in a kind of calcium and magnesium fusion method deep removal flue gas according to claim 32The method of coproduction crystal whisker of gypsum, it is characterised in that described Calx adopts the regenerative response that magnesium nitrate solution is carried out magnesium hydroxide by the calcium oxide of 1-20% or the suspension of calcium hydroxide to be atmospheric operation, and temperature is 40-85 DEG C, calcium/magnesium (mole)≤1.
5. SO in a kind of calcium and magnesium fusion method deep removal flue gas according to claim 12The method of coproduction crystal whisker of gypsum, it is characterised in that the concentration of described desulfurization product magnesium sulfate is 5-30%, calcium nitrate solution concentration is 5-30%, and it is atmospheric operation that the two reaction generates the reaction of crystal whisker of gypsum, and temperature is 98-120 DEG C.
6. SO in a kind of calcium and magnesium fusion method deep removal flue gas according to claim 1 or 52The method of coproduction crystal whisker of gypsum, it is characterised in that the whiteness of described crystal whisker of gypsum more than >=95%, draw ratio >=50, chemical composition >=99%.
7. SO in a calcium and magnesium fusion method deep removal flue gas2The preparation facilities of coproduction crystal whisker of gypsum, it is characterized in that, including desulfurizing tower, whisker reactor and magnesium hydrate regeneration device, mother liquor tank is connected bottom described desulfurizing tower, mother liquor tank is connected by white residue filter and whisker reactor, whisker reactor is connected by whisker filter and magnesium hydrate regeneration device, Calx is passed in magnesium hydrate regeneration device, magnesium hydrate regeneration device lower end is provided with magnesium hydroxide filter, filtrate in magnesium hydroxide filter enters whisker reactor, and the magnesium hydroxide being filtrated to get in magnesium hydroxide filter enters mother liquor tank.
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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 |
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| 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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