CN109331620A - A kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium compound desulfurizing process - Google Patents
A kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium compound desulfurizing process Download PDFInfo
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- CN109331620A CN109331620A CN201810711104.1A CN201810711104A CN109331620A CN 109331620 A CN109331620 A CN 109331620A CN 201810711104 A CN201810711104 A CN 201810711104A CN 109331620 A CN109331620 A CN 109331620A
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- pump
- desulfurization
- magnesium
- calcium
- gypsum
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 180
- 239000011777 magnesium Substances 0.000 title claims abstract description 88
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011575 calcium Substances 0.000 title claims abstract description 72
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 66
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 34
- 150000002681 magnesium compounds Chemical class 0.000 title claims abstract description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 128
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 113
- 230000023556 desulfurization Effects 0.000 claims abstract description 104
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 76
- 239000010440 gypsum Substances 0.000 claims abstract description 75
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 72
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000292 calcium oxide Substances 0.000 claims abstract description 50
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 44
- 230000008929 regeneration Effects 0.000 claims abstract description 41
- 238000011069 regeneration method Methods 0.000 claims abstract description 41
- 239000003546 flue gas Substances 0.000 claims abstract description 37
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 33
- 238000005516 engineering process Methods 0.000 claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 16
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 16
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000010459 dolomite Substances 0.000 claims abstract description 7
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 99
- 235000012255 calcium oxide Nutrition 0.000 claims description 49
- 239000000706 filtrate Substances 0.000 claims description 40
- 230000009719 regenerative response Effects 0.000 claims description 37
- 239000002002 slurry Substances 0.000 claims description 29
- 238000003860 storage Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- 229910052925 anhydrite Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910052564 epsomite Inorganic materials 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000004579 marble Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 6
- 238000007373 indentation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000007789 gas Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000032696 parturition Effects 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical group [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/464—Sulfates of Ca from gases containing sulfur oxides
-
- 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
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- 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
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/608—Sulfates
-
- 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)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
A kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium compound desulfurizing process, belong to coal-fired flue gas desulfurization technical field, which is combined with lime (CaO) and calcined dolomite in powder (CaOMgO) or magnesia (MgO) for raw material；The sulfur removal technology high-efficiency desulfurization simultaneously, complete the effective regeneration conversion cycles of desulfurization product, under the premise of realizing waste residue, wastewater zero discharge realize desulfidation tail gas qualified discharge, make the SO in the MgO and flue gas in desulfurizing agent2Reaction forms magnesium sulfate (MgSO4), make the CaO and desulfurization product MgSO in desulfurizing agent4It is converted into chemical grade gypsum outside tower, while regenerating active magnesium hydroxide [Mg (OH)2], gypsum returns to desulphurization system circulation desulfurization for papermaking, the raw material of building materials, magnesium hydroxide.It the composite can be widely applied to the upgrading of calcium method, magnesium processes and double alkali method desulfurizing technology.
Description
Technical field
The invention belongs to coal-fired flue gas desulfurization technical fields, multiple more particularly to a kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium
Close sulfur removal technology.
Background technique
Increasing with China to air quality environmental protection control dynamics, the requirement to coal-fired flue gas desulfurization is higher and higher, no
Require nothing more than the sulfur dioxide (SO in flue gas2) it can not enter day, also require that desulfurization product waste water does not enter ground and waste residue is not formed
Secondary pollution, while realizing the comprehensive utilization of waste water, waste residue.
It was verified that traditional sulfur method has been difficult to meet SO2The requirement of minimum discharge needs de- to conventional wet
Sulphur technique improves.
It is wet desulfurizing process that China's coal-fired flue gas desulfurization is most commonly used at present, and most representative method has calcium method de-
Sulphur, magnesium processes desulfurization and double alkali method desulfurizing.And there are different defects, it is more difficult to adapt to mesh because of its process characteristic difference in three kinds of methods
Preceding environmental requirement.
For calcium method desulfurization, because of the wide and cheap feature in its technology maturation, desulfurizing agent source, be China traditionally
The sulfur method that is widely used simultaneously continues up so far.But being also accumulated from problems causes the technique unsuitable
Modern environmental requirement, wherein most fatal defect is that desulfurized gypsum amount is of poor quality greatly, it is difficult to as effective byproduct trans-utilization,
Cause the total amount of annual 1.4 hundred million tons of calcium method desulfurized gypsum or more to increase, it has to occupy the stockpiling of a large amount of soils, formed to weather,
The secondary pollution of soil, plant and human health.
For magnesium processes desulfurization, because of the features such as its technology theory is scientific, desulphurization reaction speed is fast, desulfuration efficiency is high, become
Technical maturity is only below the process of calcium method desulfurization, avoids that pipeline blockage existing for calcium method, smoke temperature be too low, flue gas with water
With there are secondarily polluted water a series of problems.High but there are desulfurizing agent prices, the high problem of operating cost, there is also desulfurization
The defect that by-product Adlerika concentration is low, condensing crystallizing is high at 7 water magnesium sulfate energy consumptions, especially desulfurization product magnesium sulfate is one
The liquid of kind colorless and odorless is easy to discharge escape environmental protection supervision privately and forms hidden danger.
For double alkali method desulfurizing, because its technique has desulfuration efficiency is high, gas liquid ratio is small, is not likely to produce fouling blockage equipment etc.
Advantage also becomes using a kind of very more sulfur removal technologies, when especially dealing with inspection, as long as to add in doctor solution caustic soda or
Person's soda ash will be quickly obtained ideal desulfurization effect, deep to be welcome by enterprise.But this technique theoretically exists
Defect, because the solubility of calcium sulfate is greater than the solubility of calcium hydroxide when sodium sulphate caused by desulfurization is regenerated with calcium oxide,
Its regenerative response is difficult to complete, and there may be enough sodium hydroxides to meet desulfurization needs in production practice, to
Reach desulfurization purpose, most producers must be forced to use the higher soda ash of price or caustic soda carries out " single alkali " desulfurization.Its result
It is that sodium sulphate caused by desulfurization (saltcake) high slat-containing wastewater is discharged, seriously polluted underground water.
It is clear that double alkali method desulfurizing technology is because its theory and practice is there are the reference of gap deficiency, calcium method and magnesium processes are then
It is necessary to continue innovation and development.Must especially equipment be carried out to the huge calcium method of storage, magnesium processes and double alkali method desulfurizing technology
Adaptive Technology transformation, it is theoretical using new desulfurization under the premise of retaining its desulphurization plant, new using new desulfurizing agent and customization
Desulphurization production technology push desulfurization industry transition and upgrade regenerate development, meet increasingly strict environmental requirement.
Summary of the invention
The object of the present invention is to provide a kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium sulfur removal technologies, and the desulfurizing agent is with lime
(CaO) and calcined dolomite in powder (CaOMgO) or magnesia (MgO) are raw material, according to a certain percentage with require to be combined；It should
Sulfur removal technology is served as theme using calcium and magnesium composite desulfurizing agent as desulfurizing agent with wet desulfurizing process, according to certain desulfurization theory and behaviour
Make condition, under the premise of high-efficiency desulfurization, complete the effective regeneration conversion cycles of desulfurization product, realizes waste residue, wastewater zero discharge
Under the premise of realize desulfidation tail gas qualified discharge, make the sulfur dioxide (SO in the MgO and flue gas in desulfurizing agent2) reaction formation
Magnesium sulfate (MgSO4), make the CaO and desulfurization product magnesium sulfate (MgSO in desulfurizing agent4) chemical grade gypsum is converted into outside tower, together
When regenerate active magnesium hydroxide [Mg (OH)2], for gypsum for papermaking, the raw material of building materials, magnesium hydroxide returns to desulphurization system, real
Existing benign industrial cycle.
The present invention realizes that the technical solution of above-mentioned purpose is: a kind of calcium and magnesium composite desulfurizing agent is by quick lime (CaO) and white
Marble ash (CaO.MgO) or magnesia (MgO) are raw material, and mixed preparing is through crushing in proportion, and main component is with matter
Measure percentage (below such as without mark, by quality very in terms of): CaO=75-85%, MgO=15-25% contain a small amount of machine
Tool impurity is ignored, 90% or more 75 μm of percent of pass of fineness, and wherein MgO ingredient also can be selected other magnesium materials that contain and cooperate, than
Such as low-grade magnesium sulfate (MgSO4·7H2O), magnesium hydroxide [Mg (OH)2] or the manufactured magnesia unslacked of magnesite calcining etc..
Desulfurizing agent as described above, when the use of calcined dolomite in powder (CaO.MgO) being raw material, the firing temperature control of calcined dolomite in powder
System is advisable at 800-900 DEG C.
Desulfurizing agent as described above, when the use of magnesia being raw material, the firing temperature of magnesia is advisable with 900 DEG C of <.
The various solid products of magnesium sulfate can be used when the use of magnesium sulfate being raw material in desulfurizing agent as described above, can also
Directly use certain density magnesium sulfate solution, such as the Adlerika of 10% concentrations above.
Matching used there are also calcium and magnesium compound desulfurizing process with above-mentioned desulfurizing agent, desulphurization mechanism is as follows:
Utilize Mg (OH) in desulfurization feed liquid2With SO in flue gas2Reaction generates magnesium sulfite, then through O2Oxidation obtains MgSO4It is molten
Liquid, MgSO4Solution and calcium and magnesium reactive desulfurizing agent generate calcium sulfate (gypsum) and magnesium hydroxide [Mg (OH)2] regeneration slurry, the slurry
It returns to desulphurization system and carries out desulfurization, Mg (OH) in slurry2With SO2Reaction generates MgSO4And dissolve, and calcium sulfate (CaSO4) do not join
It is retained in desulfurization slurry with reacting, is filtered and separate calcium sulfate with Adlerika, obtain the higher gypsum product of purity,
Magnesium sulfate filtered fluid and calcium and magnesium desulfurizing agent are got back the mixed slurry of calcium sulfate and magnesium hydroxide through regenerative response, through adding water to adjust
Desulphurization system is sent to after concentration, completes the closed cycle of flue gas desulfurization.Reaction equation is as follows:
Desulphurization reaction: CaSO4·Mg(OH)2+SO2=CaSO4+MgSO3+H2O
Oxidation reaction: 2MgSO3+O2=2MgSO4
Regenerative response: CaOMgO+MgSO4+2H2O=CaSO4+2Mg(OH)2
Based on the compound desulfurization principle of above-mentioned calcium and magnesium, it is compound that purpose to realize the present invention forms a kind of most basic calcium and magnesium
Sulfur removal technology:
A kind of calcium and magnesium compound desulfurizing process, by regeneration reactor, desulfurization shurry pump, desulfurization liquid storage tank, filter pump, filtrate
Pump, gypsum filter, magnesium sulfate reservoir, belt feeder, first grade desulfurizing tower, first grade desulfurizing liquid circulating tank, primary cycle pump group at,
Adlerika after gypsum filter filters gypsum is squeezed into regeneration reactor through filtrate pump, puts into calcium under stirring
Regenerative response occurs for magnesium composite desulfurizing agent, generates CaSO4With Mg (OH)2Two kinds of precipitating slurries and a small amount of unconverted CaO and few
The MgSO of amount4, after the completion of regenerative response, suitable quantity of water is added and sizes mixing, through desulfurization material pulp pumping to first grade desulfurizing liquid circulating tank, through one
Grade circulating pump squeezes into the SO in first grade desulfurizing tower absorption flue gas2, circulation fluid completion liquid is pumped through primary cycle again squeezes into doctor solution storage
Tank is pressed into gypsum filter through filter pump, and filter cake is delivered to final gypsum product heap through belt feeder, and filtrate is stored in for Adlerika
Magnesium sulfate reservoir send to regeneration reactor and calcium and magnesium composite desulfurizing agent again through filtrate pump and regenerative response occurs, in cycles,
Form industrial cycle.
Sulfur removal technology as described above, SO in flue gas2Absorption using multistage absorption or can be referred to as multistage de-
Sulphur can obtain more preferably desulphurization circulating assimilation effect.
Sulfur removal technology as described above, Preferable scheme is that the second level calcium and magnesium is multiple using second level calcium and magnesium compound desulfurizing process
Sulfur removal technology is closed, by regeneration reactor, desulfurization shurry pump, desulfurization liquid storage tank, filter pump, filtrate pump, gypsum filter, magnesium sulfate
Reservoir, belt feeder, two-grade desulfurizing tower, two-grade desulfurizing liquid circulating tank, secondary cycle pump, first grade desulfurizing tower, first grade desulfurizing liquid follow
Ring tank, primary cycle pump group are at the Adlerika after gypsum filter filters gypsum squeezes into regeneration reactor through filtrate pump
In, calcium and magnesium composite desulfurizing agent is put under stirring, regenerative response occurs, generate CaSO4With Mg (OH)2Two kinds of precipitating slurries and
A small amount of unconverted CaO and a small amount of MgSO4, after the completion of regenerative response, suitable quantity of water is added and sizes mixing, extremely through desulfurization material pulp pumping
Two-grade desulfurizing liquid circulating tank squeezes into the SO in two-grade desulfurizing tower absorption flue gas through secondary cycle pump2, doctor solution completion liquid is again through two
Grade circulating pump squeezes into first grade desulfurizing liquid circulating tank, squeezes into first grade desulfurizing tower through primary cycle pump and carries out desulfurization, primary cycle desulfurization
After liquid circulation completes desulfurization, magnesium sulfate completion liquid is returned into desulfurization liquid storage tank through primary cycle pump, is pressed into gypsum through filter pump
Filter, filter cake are delivered to final gypsum product heap through belt feeder, and filtrate is that Adlerika is stored in magnesium sulfate reservoir, through filtering
Liquid pump, which is sent again to regeneration reactor and calcium and magnesium composite desulfurizing agent, occurs regenerative response, in cycles, forms industrial cycle.
Regenerative response operation as described above, the Adlerika after filtering gypsum squeeze into regeneration reactor through filtrate pump
In, calcium and magnesium composite desulfurizing agent is put under stirring, regenerative response occurs, generate CaSO4With Mg (OH)2Two kinds of precipitating slurries,
Because the MgO in desulfurizing agent does not react with magnesium sulfate, therefore in regenerative response operation without being included in the input amount of MgO,
Investment ratio presses MgSO4Total amount and CaO total amount equimolar determine the input quantity of two kinds of materials than calculating.Because of solid-liquid conversion reaction
Relatively slow, the reaction time should react 3 hours or more under stirring, and conversion reaction has occurred for 90% or more CaO.Obtained material
Slurry is CaSO4、Mg(OH)2With a small amount of unconverted CaO and a small amount of MgSO4Composition, pH value >=9, regenerative response are completed
Afterwards, suitable quantity of water is added, content of MgO of sizing mixing into slurries is controlled at 3-5% (w/w), is then sent for desulphurization system.
The optimum efficiency of desulfurization operations as described above, desulfurization operations should be: gas liquid ratio is small, operation power consumption is few,
Sorbent utilization is high, desulfuration efficiency is high, SO2Removal efficiency should be greater than 95%, to obtain this effect, two-step desulfurization be selected to compare
Properly.
First grade desulfurizing as described above, the control of doctor solution pH value operate between 5-6, the slant acidity doctor solution energy of low pH value
Guarantee desulfurizing agent Mg (OH)2Dissolution is complete as far as possible, to reduce Mg in gypsum (OH)2Be mingled with residual, improve gypsum qualitt.
Two-grade desulfurizing as described above is that will affect desulfuration efficiency based on low pH value solution-operated, is further added by second level thus
Desulfurization operations, doctor solution pH value control in >=7 slight alkali environment, are more advantageous to flue gas SO2It absorbs completely, with small gas-liquid
Than obtaining higher desulfuration efficiency.
Two-grade desulfurizing as described above, when the control of doctor solution pH value is in >=7 slight alkali environment, Mg in doctor solution
(OH)2Dissolution not exclusively, can send to first grade desulfurizing and continue to convert.
Two-grade desulfurizing as described above, operating method are as follows:
The doctor solution obtained by regenerative response is pumped into two-grade desulfurizing liquid circulating tank through regeneration, and slurry passes through under stirring
Secondary cycle pump squeeze into two-grade desulfurizing tower top, doctor solution is sprayed into fine drop downlink through atomizer, with come from bottom uplink
Flue gas inversely contact, the SO in flue gas2By Mg (OH)2It absorbs, in O2Under the action of generate MgSO4Complete desulphurization reaction.Second level
SO in desulfurization fume2Removal efficiency can reach 95% or more, SO in the flue gas of discharge2Drop to 30mg/M3Below.
Two-grade desulfurizing as described above is squeezed into when two-grade desulfurizing circulation fluid pH value≤7 by adjusting throttle valve a part
In first grade desulfurizing circulating tank, first grade desulfurizing tower top is squeezed into through first grade desulfurizing liquid circulating pump, is sprayed under fine drop through atomizer
Row is inversely contacted with the flue gas from tower bottom, remaining Mg (OH) in doctor solution2Absorb SO in flue gas2, in O2Under the action of
Generate MgSO4, first grade desulfurizing circulation fluid pH value control between 5-6, SO is reacted in flue gas2Removal efficiency reaches 60% or more.Desulfurization
When liquid pH value is down to 5 or less, a part of doctor solution is sent into desulfurization liquid storage tank by adjusting throttle valve.
That work in sweetening process is Mg in slurry (OH)2.It is complete to magnesium sulfate solution by calcium and magnesium composite desulfurizing agent
At the regenerating transformed obtained nascent state Mg (OH) of reaction2Partial size is smaller, and chemical activity is very high, is conducive to SO in flue gas2Suction
It receives, CaSO in doctor solution4It is not involved in reaction, is generated in desulphurization system without precipitation reaction, therefore equipment scaling blocking can be reduced
The generation of phenomenon finally also has the complete MgO of the lower unreacted of a small amount of chemical activity and is present in slurry, with gypsum mistake
Remain among gypsum after filter, in addition the MgSO of gypsum absorption4, will cause small part Mg (OH)2Loss.
It is separated by filtration gypsum operation as described above, doctor solution slurry is through filter pump injection gypsum filtering in desulfurization liquid storage tank
Machine, filtrate MgSO4Aqueous solution water conservancy diversion enters in magnesium sulfate filtrate tanks slot, after gypsum filter presses full gypsum filter cake, opens
Filter unloads gypsum filter cake, stores through belt conveyer to gypsum.The main component of gypsum is CaSO4·2H2O, separately
There are a small amount of unreacted CaO, MgO and MgSO4Absorption residual, the gypsum can be sent to and do construction material.
Desulfurization operations as described above, while in production because of desulfurization, flue gas can generate evaporation to doctor solution, can lead to
Cross the use concentration that supplement industrial water keeps doctor solution.According to the amount for the magnesia for taking magnesium ion loss out of, select calcium and magnesium multiple
The component ratio of MgO in mixture, to keep Mg (OH) in doctor solution operational process2Effective content, also can be selected washable mistake
Filter washes gypsum filter cake, reduces gypsum filter cake to MgSO4Adsorption loss, to obtain purer plastering.
To SO in certain industry flue gases2Content is lower or allows SO2The higher desulfurizing item of concentration of emission, also can be selected
First grade desulfurizing technique reduces the power consumption in desulfurization operation, reduces desulfurization operation cost.
In view of application environment of the invention and technique handling characteristics, with calcium method, the magnesium processes and to Dual alkali in wet desulphurization
It compares, in addition to process route and the operating condition of the technological principle of the desulfurizing agent, foundation that use, use are different, uses
Unit and operating method have no significant difference in itself, or even most of technological equipment can be real by simple transformation
Now equipment aspect is general.That is, calcium method, magnesium processes and Dual alkali can be implemented under the premise of retaining existing equipment state
Process and technology innovation and the purpose of the present invention is achieved that using calcium and magnesium composite desulfurizing agent.In other words: thoroughly changing tradition
Sulfur removal technology is difficult to meet the situation of modern environmental requirement, it is necessary to implement innovation transformation, but out-and-out transformation is unrealistic
, and perform the operation the method is characterized in that system hardware is maintained to focus on implementation " changing core " simultaneously, make traditional desulfurization equipment in the present invention
Soul breaks into new life under dominating.
The invention has the advantages that being used for magnesium sulfate desulfurization regeneration using calcium and magnesium composite material and technique, keeping
On the basis of magnesium processes high-efficiency desulfurization effect, the outer Efficient Conversion of calcium oxide tower is realized into the technical guarantee of chemical grade gypsum；It realizes
Doctor solution whole closed circulation uses；Realize the advantage of calcium method and magnesium processes during desulfurizing agent is shared, technique intercommunication is dissolved each other
It is complementary.This regenerates for current a wide range of calcium method, the technological change of magnesium processes and double alkali method desulfurizing under the premise of not injuring muscles and bones
It is of great significance.
Detailed description of the invention
With reference to the accompanying drawings and embodiments, the invention will be further described.
Fig. 1 is a kind of process flow chart of calcium and magnesium compound desulfurizing process of the invention
Fig. 2 is a kind of another process flow chart of calcium and magnesium compound desulfurizing process of the invention
In figure, 1- regeneration reactor, 2- desulfurization shurry pump, 3- desulfurization liquid storage tank, 4- filter pump, 5- filtrate pump, 6- gypsum
Filter, 7- magnesium sulfate washing lotion behaviour, 8- belt feeder, 9- two-grade desulfurizing tower, 10- two-grade desulfurizing liquid circulating tank, 11- secondary cycle
Pump, 12- first grade desulfurizing tower, 13- first grade desulfurizing liquid circulating tank, 14- primary cycle pump
Specific embodiment
Embodiment 1: as seen from Figure 1, a kind of calcium and magnesium compound desulfurizing process, by regeneration reactor 1, desulfurization shurry pump 2, desulfurization
Liquid storage tank 3, filter pump 4, filtrate pump 5, gypsum filter 6, magnesium sulfate reservoir 7, belt feeder 8, first grade desulfurizing tower 12, level-one are de-
Sulphur liquid circulating tank 13,14 composition of primary cycle pump.Adlerika after gypsum filter 6 filters gypsum is beaten through filtrate pump 5
Enter in regeneration reactor 1, calcium and magnesium composite desulfurizing agent is put under stirring, regenerative response occurs, foundation squeezes into regeneration reactor
The concentration and volume of Adlerika calculate the total amount of magnesium sulfate in 1, according still further to MgSO4Total amount and CaO total amount equimolar ratio
The demand of CaO is calculated, the last content according to CaO in desulfurizing agent determines the additional amount of desulfurizing agent, reacts 3 under stirring
Hour, make 90% or more CaO that conversion reaction occur；Generate CaSO4With Mg (OH)2Two kinds of precipitating slurries and a small amount of unconverted
CaO and a small amount of MgSO4, after the completion of regenerative response, suitable quantity of water, content of MgO control of sizing mixing into slurries is added in pH value >=9
System is sent through desulfurization shurry pump 2 to first grade desulfurizing liquid circulating tank 13 at 3-5% (w/w), squeezes into first grade desulfurizing through primary cycle pump 14
Tower 12 absorbs the SO in flue gas2, circulation fluid completes liquid and 14 squeezes into desulfurization liquid storage tank 3 through primary cycle pump again, be pressed into through filter pump 4
Gypsum filter 6, filter cake are delivered to final gypsum product heap through belt feeder 8, and filtrate is that Adlerika is stored in magnesium sulfate reservoir
7, it send regeneration reactor 1 and calcium and magnesium composite desulfurizing agent that regenerative response occurs again through filtrate pump 5, in cycles, forms industry and follow
Ring.
Embodiment 2: from Figure 2 it can be seen that a kind of calcium and magnesium compound desulfurizing process, by regeneration reactor 1, desulfurization shurry pump 2, desulfurization
Liquid storage tank 3, filter pump 4, filtrate pump 5, gypsum filter 6, magnesium sulfate reservoir 7, belt feeder 8, two-grade desulfurizing tower 9, second level are de-
Sulphur liquid circulating tank 10, secondary cycle pump 11, first grade desulfurizing tower 12, first grade desulfurizing liquid circulating tank 13,14 composition of primary cycle pump, warp
Adlerika after the filtering gypsum of gypsum filter 6 is squeezed into regeneration reactor 1 through filtrate pump 5, is put under stirring
Regenerative response occurs for calcium and magnesium composite desulfurizing agent, calculates according to the concentration and volume for squeezing into Adlerika in regeneration reactor 1
The total amount of magnesium sulfate, according still further to MgSO4The demand of total amount and CaO total amount equimolar than calculating CaO, it is last according in desulfurizing agent
The content of CaO determines the additional amount of desulfurizing agent, react 3 hours under stirring or more, convert 90% or more CaO
Reaction；Generate CaSO4With Mg (OH)2Two kinds of precipitating slurries and a small amount of unconverted CaO and a small amount of MgSO4, regenerative response is complete
Cheng Hou, pH value >=9 are added suitable quantity of water and size mixing, and send through desulfurization shurry pump 2 to two-grade desulfurizing liquid circulating tank 10, it is de- to control second level
The SO in the absorption flue gas of two-grade desulfurizing tower 9 is squeezed into through secondary cycle pump 11 in sulphur liquid pH value >=72, circulation fluid completion liquid is again through second level
Circulating pump 11 squeezes into first grade desulfurizing liquid circulating tank 13, controls first grade desulfurizing liquid pH value between 5-6, squeezes into through primary cycle pump 14
First grade desulfurizing tower 12 carries out desulfurization, after the completion of primary cycle doctor solution circulation desulfurization, completes magnesium sulfate through primary cycle pump 14
Liquid returns to desulfurization liquid storage tank 3, is pressed into gypsum filter 6 through filter pump 4, and filter cake is delivered to final gypsum product heap through belt feeder 8, filters
Liquid is that Adlerika is stored in magnesium sulfate reservoir 7, send regeneration reactor 1 and the compound desulfurization of calcium and magnesium again through filtrate pump 5
Regenerative response occurs for agent, in cycles, forms industrial cycle.
Embodiment 3: a kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium compound desulfurizing process, calcium and magnesium composite desulfurizing agent are by giving birth to
Lime (CaO) and calcined dolomite in powder (CaO.MgO) are raw material, by CaO=85%, MgO=15% ratio mixed preparing and through crushing
It forms, ignores containing a small amount of mechanical admixture, 90% or more 75 μm of percent of pass of fineness；The sulfur removal technology uses secondary desulfuration work
Skill, the Adlerika after gypsum filter filters gypsum is squeezed into regeneration reactor 1 through filtrate pump 5, under stirring
It puts into calcium and magnesium composite desulfurizing agent and regenerative response occurs, generate CaSO4With Mg (OH)2Two kinds of precipitating slurries and a small amount of unconverted CaO
And a small amount of MgSO4, after the completion of regenerative response, suitable quantity of water is added and sizes mixing, doctor solution pH value > 7 is controlled, through desulfurization shurry pump 2
It send to two-grade desulfurizing liquid circulating tank 10, squeezes into the SO in the absorption flue gas of two-grade desulfurizing tower 9 through secondary cycle pump 112, due to second level
Desulfurization operations are carried out in slight alkali environment, SO in flue gas2Obtain desirable absorption, SO in desulfidation tail gas2Content is very low,
It is emptied from two-grade desulfurizing tower；Two-grade desulfurizing tower circulation fluid completes liquid because sweetening process carries out consuming part magnesium hydroxide, alkali
Property be in attenuation trend, pH value < 7 is 11 to squeeze into first grade desulfurizing through secondary cycle pump again it will be apparent that this is recycled and completes liquid
Liquid circulating tank 13 is mixed with the desulphurization circulating liquid of first grade desulfurizing liquid pH value 5-6, squeezes into first grade desulfurizing tower 12 through primary cycle pump 14
Desulfurization is carried out, therefore is carried out under mildly acidic conditions on desulfurization environmental complex, magnesium hydroxide has obtained good dissolution,
With the SO in flue gas being more than 60%2Desulfurization absorbing reaction occurs, remaining SO less than 40%2Flue gas is transferred to the relaying of two-grade desulfurizing tower 9
Continue and thoroughly removed in slight alkali environment, after the completion of primary cycle doctor solution circulation, desulphurization circulating completes the hydrogen in liquid
It is converted into magnesia amplitude peak magnesium sulfate, magnesium sulfate completion liquid is returned into desulfurization liquid storage tank 3 through primary cycle pump 14,
It is pressed into gypsum filter 6 through filter pump 4, filter cake is delivered to final gypsum product heap through belt feeder 8, and filtrate is stored in for Adlerika
In magnesium sulfate reservoir 7, send regeneration reactor 1 and calcium and magnesium composite desulfurizing agent that regenerative response, Zhou Erfu occurs again through filtrate pump 5
Begin, forms industrial cycle.
Embodiment 4: a kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium compound desulfurizing process, calcium and magnesium composite desulfurizing agent are by giving birth to
Lime (CaO) and light burnt powder (MgO) are raw material, and by CaO=85%, MgO=15% ratio mixed preparing is simultaneously crushed, and is contained
There is a small amount of mechanical admixture to ignore, 90% or more 75 μm of percent of pass of fineness, in order to enhance MgO activity and reduce the life in MgO
Expect impurity, need to select calcination temperature lower than 900 DEG C and the thorough light burnt powder of calcining be desulfurizing agent ingredient；The sulfur removal technology uses
Secondary desulfuration technique, the Adlerika after gypsum filter filters gypsum are squeezed into regeneration reactor 1 through filtrate pump 5,
Calcium and magnesium composite desulfurizing agent is put under stirring, regenerative response occurs, generate CaSO4With Mg (OH)2Two kinds of precipitating slurries and a small amount of
Unconverted CaO and a small amount of MgSO4, after the completion of regenerative response, suitable quantity of water is added and sizes mixing, control doctor solution pH value >=7, warp
Desulfurization shurry pump 2 send desulfurization slurry (desulphurization circulating liquid) respectively to two-grade desulfurizing liquid circulating tank 10 and first grade desulfurizing liquid circulating tank
In 13；It send to the desulphurization circulating liquid of two-grade desulfurizing liquid circulating tank 10, squeezes into two-grade desulfurizing tower 9 through secondary cycle pump 11 and absorb flue gas
In SO2, since two-grade desulfurizing operation is carried out in slight alkali environment, SO in flue gas2Desirable absorption is obtained, is taken off
SO in sulphur tail gas2Content is very low, empties from two-grade desulfurizing tower 9, and 9 circulation fluid of second level desulfurizing tower is completed liquid and pumped again through secondary cycle
11 squeeze into first grade desulfurizing liquid circulating tank 13, mix with the desulphurization circulating liquid of first grade desulfurizing liquid pH value 5-6, pump 14 dozens through primary cycle
Enter first grade desulfurizing tower 12 and carries out desulfurization；It send to the desulphurization circulating liquid of first grade desulfurizing liquid circulating tank 13, is used for because it has meta-alkalescence
The pH value loss of first grade desulfurizing tower 12 and the desulfurization burden of balance first grade desulfurizing tower 12 are adjusted, desulfurization slurry (desulphurization circulating is increased
Liquid) filling into for first grade desulfurizing liquid circulating tank 13 can be improved by the magnesium hydroxide content of first grade desulfurizing liquid circulating tank 13 and improves it
PH value, while also increasing the load of first grade desulfurizing, reduce the desulfurization load of two-grade desulfurizing tower 9 and improving desulfuration efficiency；
Being appropriately carried out desulfurization slurry (desulphurization circulating liquid) can be such that first grade desulfurizing generally keeps filling into for first grade desulfurizing liquid circulating tank 13
Faintly acid, it can meet magnesium hydroxide and obtained good dissolution, also can satisfy and the SO that in flue gas is more than 60%2Occur
Desulfurization absorbing reaction, maintenance system carry out in a metastable operating environment, remain in two-grade desulfurizing tower 9 into
SO of the row less than 40%2The processing task of flue gas, it is ensured that desulfurization effect；After the completion of primary cycle doctor solution circulation, desulphurization circulating
It is converted into magnesium sulfate with completing the magnesium hydroxide amplitude peak in liquid, returns to magnesium sulfate completion liquid through primary cycle pump 14
Desulfurization liquid storage tank 3 is pressed into gypsum filter 6 through filter pump 4, and filter cake is delivered to final gypsum product heap through belt feeder 8, and filtrate is sulfuric acid
Magnesium solution is stored in magnesium sulfate liquid storage behaviour 7, send regeneration reactor 1 and calcium and magnesium composite desulfurizing agent to occur again again through filtrate pump 5
Raw reaction forms industrial cycle in cycles.
Claims (9)
1. a kind of calcium and magnesium composite desulfurizing agent is original by quick lime (CaO) and calcined dolomite in powder (CaO.MgO) or magnesia (MgO)
Material, mixed preparing is through crushing in proportion, it is characterised in that: its main component calculates CaO=75- by percentage to the quality
85%, MgO=15-25% ignore containing a small amount of mechanical admixture, 90% or more 75 μm of percent of pass of fineness.
2. desulfurizing agent according to claim 1, it is characterised in that: wherein MgO ingredient also can be selected other matches containing magnesium material
It closes, such as low-grade magnesium sulfate (MgSO4·7H2O), magnesium hydroxide [Mg (OH)2] or the manufactured magnesia unslacked of magnesite calcining
Deng.
3. desulfurizing agent according to claim 1, it is characterised in that: white when the use of calcined dolomite in powder (CaO.MgO) being raw material
The firing temperature of marble ash is controlled at 800-900 DEG C；When the use of magnesia being raw material, 900 DEG C of the firing temperature < of magnesia.
4. a kind of calcium and magnesium compound desulfurizing process, by regeneration reactor, desulfurization shurry pump, desulfurization liquid storage tank, filter pump, filtrate pump,
Gypsum filter, magnesium sulfate reservoir, belt feeder, first grade desulfurizing tower, first grade desulfurizing liquid circulating tank, primary cycle pump group are at warp
Adlerika after gypsum filter filtering gypsum is squeezed into regeneration reactor through filtrate pump, puts into calcium and magnesium under stirring
Regenerative response occurs for composite desulfurizing agent, generates CaSO4With Mg (OH)2Two kinds of precipitating slurries and a small amount of unconverted CaO and a small amount of
MgSO4, after the completion of regenerative response, suitable quantity of water is added and sizes mixing, through desulfurization material pulp pumping to first grade desulfurizing liquid circulating tank, through level-one
Circulating pump squeezes into the SO in first grade desulfurizing tower absorption flue gas2, circulation fluid completion liquid is pumped through primary cycle again squeezes into desulfurization liquid storage tank,
It is pressed into gypsum filter through filter pump, filter cake is delivered to final gypsum product heap through belt feeder, and filtrate is that Adlerika is stored in sulphur
Sour magnesium reservoir send to regeneration reactor and calcium and magnesium composite desulfurizing agent again through filtrate pump and regenerative response, in cycles, shape occurs
At industrial cycle.
5. according to sulfur removal technology described in entitlement requests 4, using second level calcium and magnesium compound desulfurizing process, the compound desulfurization of second level calcium and magnesium
Technique, by regeneration reactor, desulfurization shurry pump, desulfurization liquid storage tank, filter pump, filtrate pump, gypsum filter, magnesium sulfate liquid storage
Slot, belt feeder, two-grade desulfurizing tower, two-grade desulfurizing liquid circulating tank, secondary cycle pump, first grade desulfurizing tower, first grade desulfurizing liquid circulating tank,
Primary cycle pump group at, through gypsum filter filter gypsum after Adlerika squeezed into regeneration reactor through filtrate pump,
Calcium and magnesium composite desulfurizing agent is put under stirring, regenerative response occurs, generate CaSO4With Mg (OH)2Two kinds of precipitating slurries and a small amount of
Unconverted CaO and a small amount of MgSO4, after the completion of regenerative response, suitable quantity of water is added and sizes mixing, through desulfurization material pulp pumping to second level
Doctor solution circulating tank squeezes into the SO in two-grade desulfurizing tower absorption flue gas through secondary cycle pump2, doctor solution complete liquid followed again through second level
Ring pump squeezes into first grade desulfurizing liquid circulating tank, squeezes into first grade desulfurizing tower through primary cycle pump and carries out desulfurization, primary cycle doctor solution follows
After ring completes desulfurization, magnesium sulfate completion liquid is returned into desulfurization liquid storage tank through primary cycle pump, through filter pump indentation gypsum filtering
Machine, filter cake are delivered to final gypsum product heap through belt feeder, and filtrate is that Adlerika is stored in magnesium sulfate reservoir, through filtrate pump
It is sent again to regeneration reactor and calcium and magnesium composite desulfurizing agent and regenerative response occurs, in cycles, form industrial cycle.
6. sulfur removal technology according to claim 4 or 5, it is characterised in that: the sulfuric acid after gypsum filter filters gypsum
Magnesium solution is squeezed into regeneration reactor through filtrate pump, calcium and magnesium composite desulfurizing agent is put under stirring, regenerative response occurs, raw
At CaSO4With Mg (OH)2Two kinds of precipitating slurries, investment ratio press MgSO4Total amount and CaO total amount equimolar are two kinds more determining than calculating
The input quantity of material；It is reacted 3 hours or more under stirring, conversion reaction has occurred for 90% or more CaO；Obtained material
Slurry is CaSO4、Mg(OH)2With a small amount of unconverted CaO and a small amount of MgSO4Composition, pH value >=9, regenerative response are completed
Afterwards, suitable quantity of water is added, content of MgO of sizing mixing into slurries is controlled at 3-5% (w/w), is then sent for desulphurization system.
7. sulfur removal technology according to claim 5, it is characterised in that: the first grade desulfurizing, the control of doctor solution pH value exist
It is operated between 5-6；The two-grade desulfurizing, doctor solution pH value control in >=7 slight alkali environment.
8. sulfur removal technology according to claim 4, by regeneration reactor (1), desulfurization shurry pump (2), desulfurization liquid storage tank
(3), filter pump (4), filtrate pump (5), gypsum filter (6), magnesium sulfate reservoir (7), belt feeder (8), first grade desulfurizing tower
(12), first grade desulfurizing liquid circulating tank (13), primary cycle pump (14) composition, the sulfuric acid after gypsum filter (6) filter gypsum
Magnesium solution is squeezed into regeneration reactor (1) through filtrate pump (5), calcium and magnesium composite desulfurizing agent is put under stirring, regeneration occurs instead
It answers, the total amount of magnesium sulfate is calculated according to the concentration and volume for squeezing into Adlerika in regeneration reactor (1), according still further to
MgSO4The demand of total amount and CaO total amount equimolar than calculating CaO, the last content according to CaO in desulfurizing agent determine desulfurizing agent
Additional amount, under stirring react 3 hours, make 90% or more CaO occur conversion reaction；Generate CaSO4With Mg (OH)2
Two kinds of precipitating slurries and a small amount of unconverted CaO and a small amount of MgSO4, after the completion of regenerative response, pH value >=9 are added suitable
Water is measured, content of MgO of sizing mixing into slurries is controlled at 3-5% (w/w), sent through desulfurization shurry pump (2) to first grade desulfurizing liquid circulating tank
(13), the SO in first grade desulfurizing tower (12) absorption flue gas is squeezed into through primary cycle pump (14)2, circulation fluid complete liquid followed again through level-one
Ring pump (14) squeezes into desulfurization liquid storage tank (3), is pressed into gypsum filter (6) through filter pump (4), filter cake is delivered to through belt feeder (8)
Final gypsum product heap, filtrate are that Adlerika is stored in magnesium sulfate reservoir (7), send regeneration reactor again through filtrate pump (5)
(1) regenerative response occurs with calcium and magnesium composite desulfurizing agent, in cycles, forms industrial cycle.
9. sulfur removal technology according to claim 5, it is characterised in that: the sulfuric acid after gypsum filter (6) filter gypsum
Magnesium solution is squeezed into regeneration reactor (1) through filtrate pump (5), calcium and magnesium composite desulfurizing agent is put under stirring, regeneration occurs instead
It answers, the total amount of magnesium sulfate is calculated according to the concentration and volume for squeezing into Adlerika in regeneration reactor (1), according still further to
MgSO4The demand of total amount and CaO total amount equimolar than calculating CaO, the last content according to CaO in desulfurizing agent determine desulfurizing agent
Additional amount, react 3 hours or more under stirring, make 90% or more CaO that conversion reaction occur；Generate CaSO4And Mg
(OH)2Two kinds of precipitating slurries and a small amount of unconverted CaO and a small amount of MgSO4, after the completion of regenerative response, pH value >=9 add
Enter suitable quantity of water to size mixing, send through desulfurization shurry pump (2) to two-grade desulfurizing liquid circulating tank (10), controls two-grade desulfurizing liquid pH value >=7, warp
Secondary cycle pump (11) squeezes into the SO in two-grade desulfurizing tower (9) absorption flue gas2, circulation fluid completion liquid is again through secondary cycle pump (11)
First grade desulfurizing liquid circulating tank (13) is squeezed into, controls first grade desulfurizing liquid pH value between 5-6, squeezes into level-one through primary cycle pump (14)
Desulfurizing tower (12) carries out desulfurization, after the completion of primary cycle doctor solution circulation desulfurization, completes magnesium sulfate through primary cycle pump (14)
Liquid returns to desulfurization liquid storage tank (3), is pressed into gypsum filter (6) through filter pump (4), filter cake is delivered to gypsum through belt feeder (8)
Finished product heap, filtrate are that Adlerika is stored in magnesium sulfate reservoir (7), send regeneration reactor (1) again through filtrate pump (5)
Regenerative response occurs with calcium and magnesium composite desulfurizing agent, in cycles, forms industrial cycle.
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| CN111701436A (en) * | 2020-06-23 | 2020-09-25 | 湖北真诚纸业有限公司 | Novel dual-alkali desulfurization method |
| CN116002741A (en) * | 2023-01-03 | 2023-04-25 | 大唐环境产业集团股份有限公司 | Quality improvement method for desulfurized gypsum |
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| CN111701436A (en) * | 2020-06-23 | 2020-09-25 | 湖北真诚纸业有限公司 | Novel dual-alkali desulfurization method |
| CN116002741A (en) * | 2023-01-03 | 2023-04-25 | 大唐环境产业集团股份有限公司 | Quality improvement method for desulfurized gypsum |
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