CN105854569B - Method for completely removing SO2 in flue gas and cooperatively producing gypsum whiskers - Google Patents
Method for completely removing SO2 in flue gas and cooperatively producing gypsum whiskers Download PDFInfo
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- CN105854569B CN105854569B CN201610408725.3A CN201610408725A CN105854569B CN 105854569 B CN105854569 B CN 105854569B CN 201610408725 A CN201610408725 A CN 201610408725A CN 105854569 B CN105854569 B CN 105854569B
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- Prior art keywords
- gypsum
- flue gas
- whisker
- manganous hydroxide
- crystal whisker
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- 239000010440 gypsum Substances 0.000 title claims abstract description 59
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000003546 flue gas Substances 0.000 title claims abstract description 48
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 70
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 46
- 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 44
- 230000023556 desulfurization Effects 0.000 claims abstract description 38
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 21
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 18
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 18
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 18
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000013067 intermediate product Substances 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 52
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- 239000012452 mother liquor Substances 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010413 mother solution Substances 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 230000009719 regenerative response Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 238000010009 beating Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 239000002803 fossil fuel Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 3
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000004571 lime Substances 0.000 abstract description 3
- 235000019738 Limestone Nutrition 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 7
- 239000006028 limestone Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000011505 plaster Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 hydrogen Manganese oxide Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 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
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- LZMCUTZPLPUFMB-UHFFFAOYSA-L dihydroxy(oxo)manganese Chemical class O[Mn](O)=O LZMCUTZPLPUFMB-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- LPHFLPKXBKBHRW-UHFFFAOYSA-L magnesium;hydrogen sulfite Chemical compound [Mg+2].OS([O-])=O.OS([O-])=O LPHFLPKXBKBHRW-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Treating Waste Gases (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for completely removing SO2 in flue gas and cooperatively producing gypsum whiskers. The method comprises the steps that manganese hydroxide serves as a desulfurizing agent to be recycled in the desulfurizing process; a desulfurization product manganese sulfate aqueous solution reacts with a subsequent intermediate product calcium nitrate to generate the gypsum whiskers and a manganese nitrate aqueous solution; alkali regenerants of lime and the like are added into the manganese nitrate aqueous solution, and manganese hydroxide and a calcium nitrate aqueous solution are generated; new generated manganese hydroxide is filtered and washed and reenters a desulfurizing tower for flue gas desulfurization; the calcium nitrate aqueous solution returns back to the gypsum whisker manufacturing process. Due to the fact that the absorption product manganous sulfite can be rapidly oxidized into manganese sulfate after air is introduced, the removing efficiency of SO2 in the flue gas can reach 100%. Due to the fact that filtration operation is conducted on the manganese sulfate solution, it is guaranteed that the byproduct gypsum whiskers have high qualities that the appearance is snowy white, the whiteness is larger than or equal to 95%, the length-diameter ratio is larger than or equal to 50, and the chemical composition is larger than or equal to 99%. According to the method, the raw materials are wide in source, the process is easy and convenient to operate, waste water is not produced, and the method is suitable for desulfuration of various fossil fuel combustion exhaust gases.
Description
Technical field
The invention belongs to sulfur dioxide SO2Removal technology field, and in particular to a kind of to remove SO in flue gas completely2Coproduction
The method of crystal whisker of gypsum.
Background technology
After the Fossil fuel Jing high-temp combustions such as coal, oil, natural gas, in flue gas, contain sulfur dioxide SO2Acid
Matter, causes considerable damage to air and environment for human survival for many years.
The widely used lime/gypsum method (calcium method) of domestic large power plant, be using limestone/lime as desulfurizing agent, can
By the sulfur dioxide SO in flue gas2Removal efficiency reaches 90-95%, and product is desulfurated plaster, due in the limestone mine of various places
Containing more chemical impurity, these impurity are transferred completely in desulfurated plaster, reduce desulfurated plaster effective ingredient and exploitation value
Value.By the use of desulfurated plaster as cement additire or low side construction material, more location is then to pile up or discharge to Some Enterprises, into
For enterprise and the burden of society.Calcium method selects acid in calcium sulfite to avoid calcium sulfate scaling is formed in desulfurizing tower in addition
Operation in solution range, this causes desulfuration efficiency to be difficult to continue to improve.
High by desulfurizing agent desulfuration efficiency of magnesium oxide (magnesium processes), investment is less than calcium method with operating cost rate, can be by flue gas
Middle sulfur dioxide removal more than 98%, desulfurization product are magnesium sulfite, become magnesium sulfate Jing after air oxidation, purify, evaporate back
Receive magnesium sulfate and can be used for feedstuff, fertilizer industry.As magnesium ore resources and magnesium sulfate market capacity are limited, promoting the use of for magnesium processes is received
To many restrictions, desulfurization magnesium liquid is simply directly discharged by some places.
Desulfurization product magnesium sulfite is pyrolyzed into into magnesium oxide and sulfur dioxide, dioxy is collected in magnesium oxide cyclic absorption desulfurization
Change sulfur or make sulphuric acid, built many set process units abroad, China successfully introduces, ruuning situation is good, but
As pyrolysis, acid-making process are complicated, sulfuric acid product economic worth is not high, and construction unit is difficult to obtain distinct economic.In addition
Magnesium processes are selected in the range of the acid solution of magnesium bisulfite stable existence to avoid magnesium sulfite solid is formed in desulfurizing tower
Operated, desulfuration efficiency is also difficult to continue to improve.
Other are various with SO2For the physics of product objective, chemical absorption process, it is difficult to solve to absorb, desorbing this pair of phases
The efficiency index of mutually interdependent and contradiction, it is impossible to accomplish both to fully absorb and economical rationality.
CN102794101 discloses a kind of limestone desulfurization coproduction crystal whisker of gypsum technique, it is characterized in that with limestone to inhale
Agent is received, ammonium sulfate is process absorbent, and desulfurization slurry Jing air oxidations are directly translated into crystal whisker of gypsum.Due to being not provided with impurity
Separating measure, causes the chemical impurity in limestone to be transferred completely in crystal whisker of gypsum product, badly influences crystal whisker of gypsum product
Quality, purposes and selling price.
CN103908882 discloses the formulation absorption agent with limestone as main component and SO is absorbed in desulfurizing tower2And NOX,
Then electrolytically generated N is carried out to absorbing liquid2With sulfate radical co-production calcium sulfate crystal whiskers.The method simultaneous SO_2 and NO removal, flow process are succinct,
Impurity removal operation, all dirt brought containing limestone in the calcium sulfate crystal whiskers of coproduction, quality and purposes are not provided with equally
It is limited, while oxide is produced in the way of being electrolysed promotes SO2And NOXAbsorb, cost of energy is difficult to reduce.
In order to improve atmosphere quality, many places propose flue gas minimum discharge all on the basis of national standard
Require.Chemically analyze in principle, the above method is all difficult to minimum discharge requirement.
Increasing enterprise carries out denitrating flue gas using SCR catalysis methods, to avoid the catalyst poisoning failure of costliness,
These devices also are intended to desulfuration efficiency, and the higher the better.Therefore, a kind of raw material sources of market in urgent need extensively, small investment, operating cost
Low, desulfurized effect is good, stable, resource utilization is high, can remove sulfur dioxide of flue gases SO completely2Produce Gao Pin simultaneously
The new cleanproduction process method of matter and high added value side-product.
The content of the invention
Sulphite is produced easily in gas absorbing device for calcium method present in prior art, magnesium processes desulfurization technology solid
The problem of body, it is an object of the invention to provide one kind removes SO in flue gas completely2The method of coproduction crystal whisker of gypsum, i.e., thoroughly
Removing sulfur dioxide in flue gas SO2, and desulfurization product is changed into the production process of high-quality crystal whisker of gypsum.It is applied to coal, stone
The flue gas that oil, natural gas Fossil fuel are produced after burning in fixed burner needs to remove sulfur dioxide SO therein2
All industries and field.
The technical scheme that the present invention takes is：
It is a kind of to remove SO in flue gas completely2The method of coproduction crystal whisker of gypsum, specifically includes following steps：
Desulfurization：Flue gas is passed through in desulfurizing tower, manganous hydroxide is recycled as desulfurizing agent, in absorption from flue gas
SO2；
Crystal whisker of gypsum processed：Desulfurization product manganous sulfite generates manganese sulfate Jing after air oxidation, manganese sulfate water after filtering
Solution generates crystal whisker of gypsum and manganese nitrate aqueous solution with the reaction of follow-up intermediate product calcium nitrate aqueous solution；
Manganous hydroxide regenerates：Reacted with whisker mother solution manganese nitrate aqueous solution using the alkali reclaim such as calcium oxide agent, generate hydrogen
Manganese oxide and calcium nitrate aqueous solution；
Circulation desulfurization：The manganous hydroxide Jing of generation is filtered, reenter desulfurizing tower after washing carries out flue gas desulfurization；Nitric acid
Calcium aqueous solution returns crystal whisker of gypsum manufacturing process.
Further, using the manganous hydroxide of circular regeneration as desulfurizing agent, manganous hydroxide and bottom of towe in the sulfur removal technology
Desulfurizing tower is passed through after slurry mixing beating and absorbs the sulfur dioxide SO in flue gas2。
Further, the manganous hydroxide regenerative response neutral and alkali regenerative agent is the calcium oxide or calcium hydroxide of 1-20%
Suspension.
Further, the manganous hydroxide regenerative response is atmospheric operation, and temperature is 40-85 DEG C, the mol ratio of calcium/manganese≤
1。
Further, the desulfurization product manganese sulfate concentration is 5-30%, and calcium nitrate aqueous solution concentration is 5-30%, the two
It is atmospheric operation that reaction generates the reaction of crystal whisker of gypsum, and temperature is 98-120 DEG C.
Further, in the crystal whisker of gypsum technique processed, obtained crystal whisker of gypsum outward appearance is snow-white, whiteness more than >=95%, it is long
Footpath is than >=50, chemical composition >=99%.
It is a kind of to remove SO in flue gas completely2The device of coproduction crystal whisker of gypsum, including desulfurizing tower, whisker reactor and hydrogen-oxygen
Change manganese regenerator, the desulfurization tower bottom connects mother liquor tank, and mother liquor tank passes through white residue filter and whisker reactor connects, whisker
Reactor passes through whisker filter and manganous hydroxide regenerator connects, and the alkali reclaims such as calcium oxide are passed through in manganous hydroxide regenerator
Agent, manganous hydroxide regenerator lower end are provided with manganous hydroxide filter, and the filtrate in manganous hydroxide filter is reacted into whisker
Device, the manganous hydroxide being filtrated to get in manganous hydroxide filter enter mother liquor tank.
Beneficial effects of the present invention are：
The invention discloses one kind is with Calx as raw material, with manganous hydroxide to circulate working media, to combustion of fossil fuel
The sulfur dioxide SO of flue gas2Carry out while removing completely, carrying out the new process of high-quality crystal whisker of gypsum circulation manufacture.
Flue gas is passed through desulfurizing tower, using manganous hydroxide aqueous solution as absorbent absorbing and removing sulfur dioxide SO therein2.Desulfurization
Bottom of towe is passed through air, and desulfurization product manganous sulfite is oxidized to manganese sulfate at any time.Manganese sulfate solution is filtered, is allowed to and follow-up hydrogen-oxygen
Change the calcium nitrate reaction generation crystal whisker of gypsum that manganese step for regeneration is produced；Filter, wash and dry, obtain whiteness >=95%, major diameter
High-quality semi-hydrated gypsum crystal whisker products than >=50.Whisker mother solution is manganese nitrate solution.Calx/hydrogen is added in manganese nitrate solution
Calcium oxide carries out heavy manganese reaction, is filtrated to get manganous hydroxide filter cake and calcium nitrate solution.Return after manganous hydroxide filter cake is scrubbed
SO in desulfurizing tower circularly removing flue gas2, calcium nitrate solution return crystal whisker of gypsum operation.
Due to manganous hydroxide activity it is high, absorption product manganous sulfite be passed through after air can rapid oxidation into manganese sulfate, so
SO in flue gas can be made2Removal efficiency is up to 100%.Due to implementing filter operation to manganese sulfate solution, it is ensured that byproduct rock
Cream whisker has whiteness more than >=95%, high-quality of chemical composition >=99%.With Calx as raw material, it is to avoid manganese oxide raw material
The shortcoming of limited source；With manganous hydroxide as working media, it is to avoid calcium method, magnesium processes desulfurization technology are easily in gas absorbing device
The trouble of sulphite solid is produced, while producing high-quality crystal whisker of gypsum.This method is produced without waste water, it is adaptable to variousization
The desulfurization of stone fuel combustion waste gas.
This method fusion calcium method, manganese method desulfurization, make the two have complementary advantages, while producing high-quality crystal whisker of gypsum.Compare
In the generation and utilization of present desulfurated plaster, only crystal whisker of gypsum can be dried into less energy and can be used for papermaking, build
The upgrading raw material in the fields such as material, has not only expanded side-product purposes, improves subsequent product quality, can save from source
About natural resourcess and energy, preferably substitute the excavation of natural gypsum ore deposit and avoid human resourcess, the energy for thus bringing
Waste and environmental pollution and destruction.This method is produced without waste water, it is adaptable to the desulfurization of various fossil fuel combustion waste gas.
Description of the drawings
Fig. 1 for the present invention in remove SO in flue gas completely2The process chart of coproduction crystal whisker of gypsum.
Wherein, wherein, 1, desulfurizing tower；2nd, mother liquor tank；3rd, white residue filter；4th, whisker filter；5th, whisker reactor；6、
Manganous hydroxide filter；, 7, manganous hydroxide regenerator.
Specific embodiment
The principles of chemistry and implementation to make desulfurization, crystal whisker of gypsum manufacture and manganous hydroxide regeneration to the present invention have
Further to understand, spy is described as follows：
Embodiment 1
It is a kind of to remove SO in flue gas completely2The method of coproduction crystal whisker of gypsum, specifically includes following steps：
Desulfurization：Flue gas is passed through in desulfurizing tower, manganous hydroxide is recycled as desulfurizing agent, in absorption from flue gas
SO2；
Crystal whisker of gypsum processed：Desulfurization product manganese sulfate generates Gypsum Fibrosum with the calcium nitrate aqueous solution reaction for generating subsequent reactions generation
Whisker and manganese nitrate aqueous solution；
Manganous hydroxide regenerates：Reacted with whisker mother solution manganese nitrate using the alkali reclaim such as calcium oxide agent, generate manganous hydroxide
And calcium nitrate aqueous solution；
Circulation desulfurization：The manganous hydroxide Jing of generation is filtered, reenter desulfurizing tower after washing carries out flue gas desulfurization；Nitric acid
Calcium aqueous solution returns crystal whisker of gypsum manufacturing process.
Further, using the manganous hydroxide of circular regeneration as desulfurizing agent, manganous hydroxide and bottom of towe in the sulfur removal technology
Desulfurizing tower is passed through after slurry mixing beating and absorbs the sulfur dioxide SO in flue gas2。
Further, the desulfurization product manganese sulfate concentration is 5-30%, and calcium nitrate aqueous solution concentration is 5-30%, the two
It is atmospheric operation that reaction generates the reaction of crystal whisker of gypsum, and temperature is 98-120 DEG C.
Further, in the crystal whisker of gypsum technique processed, obtained crystal whisker of gypsum outward appearance is snow-white, whiteness more than >=95%, it is long
Footpath is than >=50, chemical composition >=99%.
Further, the manganous hydroxide regenerative response neutral and alkali regenerative agent is the calcium oxide or calcium hydroxide of 1-20%
Suspension.
Further, the manganous hydroxide regenerative response is atmospheric operation, and temperature is 40-85 DEG C, the mol ratio of calcium/manganese≤
1。
The technical scheme in the present invention is further illustrated with reference to process chart：
As shown in figure 1, with Calx as raw material, with manganous hydroxide as cyclic absorption medium, in desulfurizing tower 1, flue gas with
Manganous hydroxide circulating absorption solution is contacted, and absorbs wherein sulfur dioxide SO2Become manganous sulfite, in the mother liquor tank 2 for absorbing tower bottom
In, manganese sulfate soluble in water is generated with the air reaction being passed through；The manganese sulfate that circulatory pool bottom concentration reaches 5-30% is extracted,
With white residue filter 3 filter after preheat, with manganous hydroxide regenerative process produce calcium nitrate solution in whisker reactor 5 with
Mix at a temperature of 98-120 DEG C, whiteness is produced more than >=95%, crystal whisker of gypsum of chemical composition >=99%.By whisker filter
4 filter, drying, are high-quality crystal whisker of gypsum product after the scrubbed drying of filter cake；Filtrate is manganese nitrate solution, by manganese nitrate solution
In 40-85 DEG C of temperature range, stirring reaction 2-4 in manganous hydroxide regenerator 7 is little with the Calx suspension that concentration is 1-30%
When, obtain manganous hydroxide suspension；Manganous hydroxide suspension is passed through manganous hydroxide filter 6 to filter, filtrate is that calcium nitrate is molten
Liquid returns manufacture crystal whisker of gypsum, and filter cake is regeneration manganous hydroxide, returns 1 absorbing sulfur dioxide in flue SO of desulfurizing tower2；Whole mistake
Journey non-wastewater discharge.
Embodiment 2
It is a kind of to remove SO in flue gas completely2The device of coproduction crystal whisker of gypsum, including desulfurizing tower, whisker reactor and hydrogen-oxygen
Change manganese regenerator, the desulfurization tower bottom connects mother liquor tank, and mother liquor tank passes through white residue filter and whisker reactor connects, whisker
Reactor passes through whisker filter and manganous hydroxide regenerator connects, and alkali reclaim agent, hydrogen-oxygen are passed through in manganous hydroxide regenerator
Change manganese regenerator lower end and be provided with manganous hydroxide filter, the filtrate in manganous hydroxide filter enters whisker reactor, hydrogen-oxygen
The manganous hydroxide being filtrated to get in changing manganese filter enters mother liquor tank.
Specifically used process is：Flue gas is introduced into desulfurizing tower desulfurization, and doctor solution enters the mother liquor tank of lower section, in mother liquor tank
Air is passed through as oxidant, the manganous sulfite in doctor solution is oxidized to into manganese sulfate in time, desulfuration efficiency is made up to 100%；It is female
Liquid bath is filtered by white residue filter, goes the compositions such as desilication slag, filtrate to enter in whisker reactor and calcium nitrate reaction, and whisker is anti-
Answer device to filter by whisker filter, collect solid whisker, the filtrate for filtering gained enters manganous hydroxide regenerator, manganous hydroxide
Alkali reclaim agent is passed through in regenerator, in manganous hydroxide regenerative process using calcium oxide/calcium hydroxide and circulatory mediator manganese nitrate
Reaction, generates manganous hydroxide and calcium nitrate aqueous solution；Newly-generated manganous hydroxide Jing manganous hydroxides filter is filtered, after washing
Flue gas desulfurization is carried out in reentering mother liquor tank；The calcium nitrate aqueous solution that manganous hydroxide filter filters gained is anti-into whisker
Answer device, circular response.
Embodiment 3
150mL1%Mn (OH) is added in 250mL absorption bottles2Aqueous suspension is placed in 50 DEG C of waters bath with thermostatic control, with 1.2L/min
Speed be passed through simulation mixed gas to absorption bottle, simulation mixed gas consist of SO20.2%PPM, O26.0%th, N215.0%.
Absorption process supplements Mn (OH)2Solid so as to be not consumed and finish, at the same determine liquid phase sulfate radical and inferior sulfate radical content and
SO in tail gas2Content, as soak time extends, in liquid phase, sulfate ion concentration runs up to 20%, and inferior sulfate radical content is then
Stablize 0.03% or so, SO in tail gas2Content is not measured always, desulfuration efficiency 100%.
Embodiment 4
Desulfurizing tower filler floor height 1.2m, diameter 50mm, enter tower flue gas flow 300L/h, and flue gas contains SO20.4%th, O26.0%th,
N215.0%, temperature is 50 DEG C, is passed through desulfurization tower bottom, with the circulating absorption solution counter current contacting sprayed from top, circulation
Liquid 3L, wherein containing Mn (OH)2Concentration 0.5-2%, liquid-gas ratio (L/G)=2-5, holds to circulating absorption solution and blast in tank air
120L/h.As absorption process is carried out continuously, holds to absorbing liquid and be continuously added in tank Mn (OH)2, maintain that its 0.5-2%'s is dense
Degree is until wherein Mn2+2mol/L is reached, is gone out2, desulfuration efficiency 100%.
Desulphurization mother solution is filtered, after filtrate dilution adjustment, MnSO is surveyed4Concentration is 1.22mol/L.1L is taken, is separately taken and is adjusted to
Calcium nitrate Ca (the NO of 2.0mol/L3)2Aqueous solution 0.61L, is heated to 100 DEG C, in adding 2.0L reactors together, insulated and stirred
Reaction 30min, filters, washs, and 105 DEG C dry to obtain 164.5 grams of semi-hydrated gypsum whisker.Survey whisker whiteness 96%, average aspect ratio
60, chemical composition 99%.
Crystal whisker of gypsum mother solution 1.6L is received, Mn (NO are surveyed3)2Concentration 0.74mol/L.CaO68.0g is taken, add water 200mL, is made into hydrogen
Calcium oxide suspension 268g, the Mn (NO under 65 DEG C of stirring conditions with 1.6L concentration 0.74mol/L3)2Solution reaction, obtains Mn
(OH)2Suspension.Suspension, water washing filter cake are filtered, manganous hydroxide filter cake 243g (water content 56%) is obtained, merging filtrate,
Wash water 2L, is evaporated to 0.6L, surveys Ca (NO3)2Concentration 1.97mol/L, returns crystal whisker of gypsum manufacturing process.
The above is not limitation of the present invention, it should be pointed out that：For those skilled in the art come
Say, on the premise of without departing from essential scope of the present invention, some changes, remodeling, addition can also be made or replaced, these improvement
Also protection scope of the present invention is should be regarded as with retouching.
Claims (7)
1. one kind removes SO in flue gas completely2The method of coproduction crystal whisker of gypsum, it is characterised in that specifically include following steps：
Desulfurization：Flue gas is passed through in desulfurizing tower, using manganous hydroxide as desulfurizing agent, the SO in cyclic absorption flue gas2；
Crystal whisker of gypsum processed：Become manganese sulfate solution after desulfurization product manganous sulfite Jing air oxidations；Filter manganese sulfate water-soluble
Liquid simultaneously generates crystal whisker of gypsum and manganese nitrate aqueous solution with the reaction of follow-up intermediate product calcium nitrate aqueous solution；
Manganous hydroxide regenerates：Reacted with whisker mother solution manganese nitrate using alkali reclaim agent, generate manganous hydroxide and calcium nitrate is water-soluble
Liquid；
Circulation desulfurization：The manganous hydroxide Jing of generation is filtered, reenter desulfurizing tower after washing carries out flue gas desulfurization；Calcium nitrate water
Solution returns crystal whisker of gypsum manufacturing process.
2. it is a kind of according to claim 1 to remove SO in flue gas completely2The method of coproduction crystal whisker of gypsum, it is characterised in that institute
State in sulfur removal technology using the manganous hydroxide of circular regeneration as desulfurizing agent, manganous hydroxide is passed through after being mixed beating with bottom of towe slurry
Desulfurizing tower absorbs the sulfur dioxide SO in flue gas2。
3. it is a kind of according to claim 1 to remove SO in flue gas completely2The method of coproduction crystal whisker of gypsum, it is characterised in that institute
State the suspension of calcium oxide or calcium hydroxide that manganous hydroxide regenerative response neutral and alkali regenerative agent is 1-20%.
4. it is a kind of according to claim 1 to remove SO in flue gas completely2The method of coproduction crystal whisker of gypsum, it is characterised in that institute
It is atmospheric operation to state manganous hydroxide regenerative response, and temperature is 40-85 DEG C, mol ratio≤1 of calcium/manganese.
5. it is a kind of according to claim 1 to remove SO in flue gas completely2The method of coproduction crystal whisker of gypsum, it is characterised in that institute
It is 5-30% to state desulfurization product manganese sulfate concentration, and calcium nitrate aqueous solution concentration is 5-30%, and the two reaction generates crystal whisker of gypsum
React for atmospheric operation, temperature is 98-120 DEG C.
6. it is a kind of according to claim 1 to remove SO in flue gas completely2The method of coproduction crystal whisker of gypsum, it is characterised in that institute
State snow-white obtained crystal whisker of gypsum outward appearance in crystal whisker of gypsum technique processed, whiteness >=95%, draw ratio >=50, semi-hydrated gypsum whisker >=
99%.
7. one kind removes SO in flue gas completely2The device of coproduction crystal whisker of gypsum, it is characterised in that including desulfurizing tower, whisker reaction
Device and manganous hydroxide regenerator, the desulfurization tower bottom connect mother liquor tank, and mother liquor tank passes through white residue filter and whisker reactor
Connection, whisker reactor passes through whisker filter and manganous hydroxide regenerator connects, and is passed through alkalescence again in manganous hydroxide regenerator
Raw agent, manganous hydroxide regenerator lower end are provided with manganous hydroxide filter, and it is anti-that the filtrate in manganous hydroxide filter enters whisker
Device, the manganous hydroxide being filtrated to get in manganous hydroxide filter is answered to enter mother liquor tank.
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| CN1565709A (en) * | 2003-06-27 | 2005-01-19 | 北京紫光威肯环境工程有限公司（中美合资） | Technique for catalytic oxidating desulfurizing products of flue gas |
| CN101190399A (en) * | 2006-11-20 | 2008-06-04 | 张西涛 | Magnesium oxide slurry method desulfurization system |
| CN101574617B (en) * | 2009-06-12 | 2012-02-01 | 四川大学 | Synchronous desulphrization and denitration method of flue gas pyrolusite pulp for reclamation |
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