CN106377993A - Method and device for removing SO2 in smoke gas by pyrolusite slurry and resource utilization - Google Patents
Method and device for removing SO2 in smoke gas by pyrolusite slurry and resource utilization Download PDFInfo
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- CN106377993A CN106377993A CN201610926562.8A CN201610926562A CN106377993A CN 106377993 A CN106377993 A CN 106377993A CN 201610926562 A CN201610926562 A CN 201610926562A CN 106377993 A CN106377993 A CN 106377993A
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- pump
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- flue gas
- pyrolusite
- filter
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- 239000002002 slurry Substances 0.000 title claims abstract description 59
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000779 smoke Substances 0.000 title abstract 7
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 36
- 230000023556 desulfurization Effects 0.000 claims abstract description 34
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 31
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000000746 purification Methods 0.000 claims abstract description 19
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 18
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 18
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 18
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 18
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 7
- 239000004571 lime Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000001238 wet grinding Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 68
- 239000003546 flue gas Substances 0.000 claims description 59
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 48
- 229910021529 ammonia Inorganic materials 0.000 claims description 35
- 238000006386 neutralization reaction Methods 0.000 claims description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 239000007921 spray Substances 0.000 claims description 22
- 238000005352 clarification Methods 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000003860 storage Methods 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 17
- 238000004062 sedimentation Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 238000010000 carbonizing Methods 0.000 claims description 14
- 239000012452 mother liquor Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000013589 supplement Substances 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 3
- 210000002966 serum Anatomy 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 2
- 238000002425 crystallisation Methods 0.000 abstract 2
- 230000008025 crystallization Effects 0.000 abstract 2
- 230000029219 regulation of pH Effects 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract 1
- 238000006479 redox reaction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 16
- 229940075933 dithionate Drugs 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229940099596 manganese sulfate Drugs 0.000 description 6
- 235000007079 manganese sulphate Nutrition 0.000 description 6
- 239000011702 manganese sulphate Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003517 fume Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002699 waste material 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
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- 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
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a Method and device for removing SO2 in smoke gas by pyrolusite slurry and resource utilization. Pyrolusite is subjected to wet milling with water added by a ball mill and pH value regulation to prepare pyrolusite slurry; the pyrolusite slurry performs inverse contact reaction with SO2-containing smoke gas in a desulfurizing tower for desulfurization; the smoke gas is subjected to defogging, and then enters the next work procedure; the ore slurry circulation flow process comprises the steps of vacuum filtering, filtering after pH regulation by lime, pH regulation of filter liquid and precipitation in a precipitation pool, vacuum evaporative crystallization and solid-liquid separation, and filter liquid carbonization solid-liquid separation. The pyrolusite slurry is used for removing SO2 in the smoke gas; meanwhile, the SO2 takes oxidation-reduction reaction with manganese dioxide in the pyrolusite to generate manganous sulfate; through the processes of purification, evaporative crystallization, mother liquid carbonization and the like, manganese sulfate monohydrate and manganese carbonate with high added values can be obtained; the SO2 in the smoke gas is controlled; the secondary pollution of the smoke gas is prevented; meanwhile, high-added-value products are generated; meanwhile, the SO2 control problem is solved; the economic benefits are obtained.
Description
Technical field
The present invention relates to SO in a kind of pyrolusite removing flue gas2And its method and device of recycling, reach with former
The purpose of ore deposit pollution treatment, obtains high value-added product simultaneously, belongs to environmental protection technical field.
Background technology
Fume desulphurization method presses the thing phase classification of desulfurizing agent, is broadly divided into dry desulfurization and wet desulphurization two class.At present
Flue gas desulfurization skill technological process kind more than 200 both at home and abroad, has the technique of industrial application value and its corollary equipment only ten
Remaining kind.Wet desulphurization is simple to operate, low cost, the most commonly used.Although lime-limestone-based process is current in Wet Flue Gas Desulfurization Technique
Technology is the most ripe, and this technique desulfuration efficiency height (desulfurization degree more than 90%), absorbent are inexpensive and originate wide, but its system is multiple
Miscellaneous, investment and energy consumption are big, produce waste residue using value less, easily cause secondary pollution；Ammonia absorption method (sour method) accessory substance
Though can be used as fertilizer, with ammonia loss by volatilization during desulfurization, and limited by ammonia source again；Other sodium methods or Dual alkali cost are same
Height, by-product utilization is worth also less, and enterprise is economically under great stress, perfect with environmental regulation, finds new
Sulfur removal technology and equipment, imperative.
China's promoter manganese enriches, distributed more widely, cheap, removes the sulfur dioxide in flue gas using manganese ore slurry, both disappeared
Except environmental pollution, and resourcebility utilizes SO2, improve pyrolusite added value, enterprise can obtain additional economic benefit simultaneously.
The present invention utilizes manganese ore slurry to remove the SO in flue gas2, SO is proposed simultaneously2Purifying with the reacted product of pyrolusite
Separate, produce the manganese sulfate of high added value and the method and approach of manganese carbonate and apparatus further.
It is characteristic of the invention that：(1) using manganese ore slurry as desulfurizing agent, to the SO in flue gas2Administered, prevented flue gas
Secondary pollution, realizes with the purpose of useless pollution treatment；(2) in sweetening process, the slurries after desulfurization pass through stock pump to vacuum filter
Filter, then in purification tank heating, plus lime adjust pH, be filtered to remove manganous dithionate, then by neutralization chamber ammonification water and
Clarification precipitation, filtration remove other metal impurities, obtain manganese sulfate clear liquid, and clear liquid carries out vacuum evaporating crystalization, while hot with being centrifuged
Machine separates, and obtains manganese sulfate monohydrate with microwave drying；Evaporation Mother liquor is passed through to add soda ash in carbonizing trough, produces manganese carbonate precipitation,
Separated with centrifuge, filter cake obtains manganese carbonate through microwave drying；(3) using manganese ore slurry as desulfurizing agent, operating cost is low, removes SO2
Carry out recycling simultaneously.
Content of the invention
It is an object of the invention to provide SO in a kind of manganese ore slurry removing flue gas2And its method for recycling, specifically
Step is as follows：
(1) pyrolusite is utilized ball mill wet-milling, cross 200 mesh sieves, add water and make pyrolusite pulp, pyrolusite pulp solid content is
18～22%, adjusting pyrolusite pulp pH value is 3.5～4.5；
(2) the higher flue gas of temperature initially enters afterheat heat exchanger and produces low-pressure steam for evaporization process use, after cooling
Flue gas enters from desulfurizing tower bottom, and the pyrolusite pulp that step (1) is obtained is evacuated to desulfurizing tower and is sprayed, the manganese of flue gas and spray
The reverse haptoreaction of ore pulp, after flue gas desulfurization from exhanst gas outlet out, after demister, flue gas enters subsequent processing or directly arranges
Sky, slurries, through circulated sprinkling, carry out slurries and change supplement, technique is carried out continuously, in the slurries after circulation predominantly in spray
Manganese sulfate, next to that ferric sulfate, also contains a small amount of calcium, magnesium, iron, aluminium and a small amount of heavy metal ion, also contains desulfurization
The manganous dithionate generating in journey, slurries carry out vacuum filter；
(3) it is 4.5～5 that the filtrate that step (2) is filtrated to get adds lime to adjust pH value, then with being steam heated to 70～80
DEG C, so that manganous dithionate is decomposed, staticly settle, sediment is filtered, obtain purifying filter liquor；
(4) purifying filter liquor of step (3) is poured in neutralization chamber, add ammoniacal liquor, adjustment pH value be 5～5.5, make calcium, magnesium,
Iron, aluminium and a small amount of heavy metal ion generate hydroxide precipitation, and neutralizer is put in clarification sedimentation basin, precipitation clarification,
And filtered further with steaming empty filter, obtain clear liquid；
(5) clear liquid of step (4) is carried out vacuum evaporating crystalization with cold boiler, vacuum is 0.07～0.08MPa,
Temperature is 70～80 DEG C, and manganese sulfate monohydrate mass percent concentration is concentrated into 38～40%, is centrifuged while hot, and filter residue is done
Manganese sulfate monohydrate is obtained after dry；
(6) the separating obtained filtrate of step (5) after cooling, adds soda ash, produces manganese carbonate precipitation, carries out separation of solid and liquid,
Filter residue and drying obtains manganese carbonate, and separating filtrate uses the mixture of direct steam heating, ammonia and steam through dephlegmator in ammonia still,
Control dephlegmator outlet temperature, ammonia returns neutralization chamber and recycles.
Step (6) is described to control dephlegmator outlet temperature to be 80～95 DEG C.
Another object of the present invention is to providing SO in described manganese ore slurry removing flue gas2With the device of recycling, wrap
Include pressurization blower 1, desulfurizing tower 2, demister 3, stock pump I4, circulating pump 5, surge tank 6, desulfurization slurry storage tank 7, stock pump II8, vacuum
Filter I9, dump tank I10, vavuum pump I11, purification tank 12, screw pump 13, filter press 14, neutralization chamber 15, clarification sedimentation basin
16th, stock pump III17, vacuum filter II18, dump tank II19, vavuum pump II20, cold boiler 21, centrifuge I22, clear liquid
Pump 23, carbonizing trough 24, centrifuge II25, mother liquor tank 26, ammonia pump 27, ammonia still 28, dephlegmator 29, drying machine I30, drying machine
II31；
Pressurization blower 1 is connected with desulfurizing tower 2 bottom, and desulfurizing tower 2 bottom is provided with material box, and top is provided with spray equipment,
Material box is connected with circulating pump 5, and circulating pump 5 is connected with spray equipment, and desulfurizing tower 2 top is provided with exhanst gas outlet, exhanst gas outlet with
Demister 3 connects, and desulfurizing tower 2 bottom material box is also connected with stock pump I 4, and stock pump I 4 connects surge tank 6, desulfurizing tower 2 bottom charge
Case is also starched storage tank 7 with desulfurization and is connected, and desulfurization slurry storage tank 7 is connected with vacuum filter I 9 by stock pump II 8, vacuum filter I
9 connection dump tanks I 10, dump tank I 10 top is connected with vavuum pump I 11, and dump tank I 10 bottom connects purification tank 12, only
Change groove 12 bottom and filter press 14 is connected by screw pump 13, filter press 14 connects neutralization chamber 15, neutralization chamber 15 bottom connects clarification
Sedimentation basin 16, clarification sedimentation basin 16 connects vacuum filter II 18 by stock pump III 17, and vacuum filter II 18 connects acceptance
Groove II 19, dump tank II 19 top is connected with vavuum pump II 20, dump tank II 19 bottom be sequentially connected cold boiler 21,
Centrifuge I 22, centrifuge I 22 are connected with drying machine II 31 and clear liquid pump 23 respectively, clear liquid pump 23 be sequentially connected carbonizing trough 24,
Centrifuge II 25, centrifuge II 25 connect drying machine I 30 and mother liquor tank 26 respectively, mother liquor tank 26 be sequentially connected ammonia pump 27,
Ammonia still 28, dephlegmator 29, dephlegmator 29 is connected with neutralization chamber 15.
It is provided with honeycomb inclined plate packing in described clarification sedimentation basin 16.
It is equipped with paddle inside described surge tank 6, desulfurization slurry storage tank 7, purification tank 12, neutralization chamber 15, carbonizing trough 24.
It is back to neutralization chamber 15 through the steam containing ammonia that dephlegmator 29 raising ammonia density reaches 10% about to recycle.
Advantages of the present invention：
1. using pyrolusite as desulfurizing agent, to the SO in flue gas2Administered, prevented the secondary pollution of flue gas, realize with
The purpose of useless pollution treatment, realizes the purpose of environmental protection.
2., in sweetening process, the manganese dioxide in recycling pyrolusite generates the higher water sulphur of added value simultaneously
Sour manganese and manganese carbonate, remove SO2While take full advantage of pyrolusite resource, make the best use of everything it is achieved that the mesh of recycling
's.
3., using manganese ore as desulfurizing agent, operating cost is low for the present invention；Carry out recycling simultaneously, given birth to by desulfurization product
Produce high added value manganese sulfate monohydrate and manganese carbonate, improving enterprise has obvious economic benefit, reclaims 1 ton of SO2, can make a profit 3000～
3500 yuan, environmental pollution improvement does not spend, and has good economic benefit.
Brief description
Fig. 1 is the structural representation of device of the present invention；
In figure, 1- pressurization blower；2- desulfurizing tower；3- demister；4- stock pump I；5- circulating pump；6- surge tank；7- desulfurization
Slurry storage tank；8- stock pump II；9- vacuum filter I；10- dump tank I；11- vavuum pump I；12- purification tank；13- screw pump；14- presses
Filter；15- neutralization chamber；16- clarifies sedimentation basin；17- stock pump III；18- vacuum filter II；19- dump tank II；20- vavuum pump
II；21- cold boiler；22- centrifuge I；23- clear liquid pump；24- carbonizing trough；25- centrifuge II；26- mother liquor tank；27- ammonia
Pump；28- ammonia still；29- dephlegmator；30- drying machine I；31- drying machine II.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is described in further detail.
Embodiment 1
As shown in figure, SO in a kind of manganese ore slurry removing flue gas2And its device of recycling, including pressurization blower
1st, desulfurizing tower 2, demister 3, stock pump I4, circulating pump 5, surge tank 6, desulfurization are starched storage tank 7, stock pump II8, vacuum filter I9, are connect
Groove I10, vavuum pump I11, purification tank 12, screw pump 13, filter press 14, neutralization chamber 15, clarification sedimentation basin 16, stock pump III17,
Vacuum filter II18, dump tank II19, vavuum pump II20, cold boiler 21, centrifuge I22, clear liquid pump 23, carbonizing trough
24th, centrifuge II25, mother liquor tank 26, ammonia pump 27, ammonia still 28, dephlegmator 29, drying machine I30, drying machine II31；Pressurization drum
Blower fan 1 is connected with desulfurizing tower 2 bottom, and desulfurizing tower 2 bottom is provided with material box, and top is provided with spray equipment, material box and circulating pump 5
Connect, circulating pump 5 is connected with spray equipment, and spray equipment is provided with three rows in differing heights, often arrange 5 shower nozzles, desulfurizing tower 2 top
It is provided with exhanst gas outlet, exhanst gas outlet is connected with demister 3, desulfurizing tower 2 bottom material box is also connected with stock pump I 4, stock pump I 4 connects
Surge tank 6, desulfurizing tower 2 bottom material box is also starched storage tank 7 with desulfurization and is connected, and desulfurization slurry storage tank 7 passes through stock pump II 8 and vacuum mistake
Filter I 9 connects, and vacuum filter I 9 connects dump tank I 10, and dump tank I 10 top is connected with vavuum pump 11, and bottom connects
Purification tank 12, purification tank 12 bottom connects filter press 14 by screw pump 13, and filter press 14 connects neutralization chamber 15, neutralization chamber 15 bottom
Portion connects clarification sedimentation basin 16, is provided with honeycomb inclined plate packing in clarification sedimentation basin 16, and clarification sedimentation basin 16 passes through stock pump III 17 even
Connect vacuum filter II 18, vacuum filter II 18 connects dump tank II 19, dump tank II 19 top and vavuum pump II20
Connect, dump tank II 19 bottom is sequentially connected cold boiler 21, centrifuge I22, and centrifuge I22 is connected with drying machine respectively
II31 and clear liquid pump 23, clear liquid pump 23 is sequentially connected carbonizing trough 24, centrifuge II25, and centrifuge II 25 connects drying machine respectively
II 30 and mother liquor tank 26, mother liquor tank 26 is sequentially connected ammonia pump 27, ammonia still 28, dephlegmator 29, dephlegmator 29 and neutralization chamber 15
Connect, inside surge tank 6, desulfurization slurry storage tank 7, purification tank 12, neutralization chamber 15, carbonizing trough 24, be equipped with paddle.
Carry out SO in manganese ore slurry removing flue gas using said apparatus2And its method for recycling, comprise the following steps that：
(1) pyrolusite is utilized ball mill wet-milling, cross 200 mesh sieves, add water in surge tank 6 and make pyrolusite pulp, soft manganese
Ore pulp solid content is 20%, and adjusting pyrolusite pulp pH value is 3.5；
(2) flue gas calcines flue gas, exhaust gas volumn 60000Nm for anode3/ h, SO in flue gas2Content is 3000mg/Nm3, averagely
220 DEG C of temperature is it is desirable to discharge flue gas SO2Less than 100mg/Nm3, it is low that the higher flue gas of temperature initially enters afterheat heat exchanger generation
Pressure steam uses for evaporization process, and after cooling, the pressurized air blast of flue gas 1 enters from desulfurizing tower 2 bottom, and step (1) is obtained
Pyrolusite pulp circulating pump 5 is evacuated to desulfurizing tower 2 and is sprayed with spray equipment, and spray equipment is provided with three rows in differing heights, often
5 shower nozzles of row, flue gas and the reverse haptoreaction of manganese ore slurry spraying, after flue gas desulfurization from exhanst gas outlet out, through demister 5
Afterwards, flue gas SO2Content is 90mg/Nm3, discharge up to standard, directly empty, serum recycle spray, carry out in spray slurries discharge and
Supplement, technique is carried out continuously, in the slurries after circulation, be mainly manganese sulfate, next to that ferric sulfate, also contain a small amount of calcium, magnesium,
Iron, aluminium and a small amount of heavy metal ion, also containing the manganous dithionate generating in sweetening process, slurry storage starches storage in desulfurization
In groove 7, it is evacuated to vacuum filter I9 through stock pump II8 and carries out vacuum filter, be filtrated to get filtrate and enter dump tank I10；
(3) filtrate that step (2) is filtrated to get enters purification tank 12 from dump tank I10, and purification tank 12 is provided with paddle,
Add lime to adjust slurry pH value to 5 while stirring, then be steam heated to 80 DEG C with what fume afterheat produced, make manganous dithionate
Decompose, slurries are evacuated to filter press 14 through screw pump 13, sediment is filtered, obtain purifying filter liquor and enter neutralization chamber 15；
(4) by step (3) neutralization chamber 15 purifying filter liquor add ammoniacal liquor, adjustment pH value be 5, make calcium, magnesium, iron, aluminium with
And a small amount of heavy metal ion generates hydroxide precipitation, neutralizer is put in clarification sedimentation basin 16, is filled out using honeycomb swash plate
Expect to carry out precipitation clarification, and with stock pump III17, liquid is evacuated to vacuum filter II18 to filter further, obtain clear liquid entrance and connect
Groove II19；
(5) clear liquid in step (4) dump tank II19 is carried out vacuum evaporating crystalization through cold boiler 21, be evaporated in vacuo
The vacuum of device 21 is 0.08MPa, and temperature is 80 DEG C, and manganese sulfate monohydrate mass percentage concentration is concentrated into 38%, while hot through centrifugation
Machine I22 is centrifuged, and filter residue drying machine II31 obtains manganese sulfate monohydrate after being dried, annual production manganese sulfate monohydrate 2000
About ton；
(6) step (5) centrifugation gained filtrate after cooling, enters through clear liquid pump 23 after carbonizing trough 24 and adds soda ash,
Produce manganese carbonate precipitation, centrifuge II25 centrifugation carries out separation of solid and liquid, and filter residue drying machine I30 is dried to obtain manganese carbonate, filtrate
Enter mother liquor tank 26, be evacuated in ammonia still 28 through ammonia pump 27, the steam heating being produced with direct fume afterheat, ammonia and steam
Mixture, through dephlegmator 29, controls 80 DEG C of dephlegmator 29 exit gas temperature, and ammonia density reaches 10% about and is back to neutralization chamber 15
Recycle, annual 2100 tons about of manganese carbonate of production.
Embodiment 2
SO in manganese ore slurry removing flue gas described in the present embodiment2And its method for recycling, using device and embodiment 1
Except arranging two row's spray equipments, often outside 7 shower nozzles of row's setting, other all sames, comprise the following steps that：
(1) pyrolusite is utilized ball mill wet-milling, cross 200 mesh sieves, add water in surge tank 6 and make pyrolusite pulp, soft manganese
Ore pulp solid content is 22%, and adjusting pyrolusite pulp pH value is 4；
(2) flue gas is boiler of power plant flue gas, exhaust gas volumn 100000Nm3/ h, SO in flue gas2Content is 2000mg/Nm3, averagely
120 DEG C of temperature is it is desirable to discharge flue gas SO2Less than 400mg/Nm3, it is low that the higher flue gas of temperature initially enters afterheat heat exchanger generation
Pressure steam uses for evaporization process, and after cooling, the pressurized air blast of flue gas 1 enters from desulfurizing tower 2 bottom, and step (1) is obtained
Pyrolusite pulp circulating pump 5 is evacuated to desulfurizing tower 2 and is sprayed with spray equipment, and flue gas is inversely contacted instead with the manganese ore slurry of spray
Should, after flue gas desulfurization from exhanst gas outlet out, SO in flue gas after demister 52Absorbed, removed SO2Flue gas SO afterwards2Contain
Measure as 300mg/Nm3, flue gas discharge up to standard, directly empty, slurries, through circulated sprinkling, carry out slurries discharge and benefit in spray
Fill, technique is carried out continuously, in the slurries after circulation, be mainly manganese sulfate, next to that ferric sulfate, also contain a small amount of calcium, magnesium, iron,
Aluminium and a small amount of heavy metal ion, also containing the manganous dithionate generating in sweetening process, slurry storage starches storage tank 7 in desulfurization
Interior, it is evacuated to vacuum filter I9 through stock pump II8 and carries out vacuum filter, be filtrated to get filtrate and enter dump tank I10；
(3) filtrate that step (2) is filtrated to get enters purification tank 12 from dump tank I10, and purification tank 12 is provided with paddle,
Add lime to adjust slurry pH value to 4.5 while stirring, then with being steam heated to 70 DEG C, make manganous dithionate decomposition, slurries warp
Screw pump 13 is evacuated to filter press 14, and sediment is filtered, and obtains purifying filter liquor and enters neutralization chamber 15；
(4) purifying filter liquor in step (3) neutralization chamber 15 is added ammoniacal liquor, adjustment pH value is 5.5, makes calcium, magnesium, iron, aluminium
And a small amount of heavy metal ion generates hydroxide precipitation, neutralizer is put in clarification sedimentation basin 16, using honeycomb swash plate
Filler carries out the precipitation clarification of long period, and with stock pump III17, liquid is evacuated to vacuum filter II18 and filters further, obtains
Obtain clear liquid and enter dump tank II19；
(5) clear liquid in step (4) dump tank II19 is carried out vacuum evaporating crystalization through cold boiler 21, be evaporated in vacuo
The vacuum of device 21 is 0.07MPa, and temperature is 70 DEG C, and manganese sulfate monohydrate concentration is concentrated into 39%, carries out through centrifuge I22 while hot
Centrifugation, filter residue drying machine II31 obtains manganese sulfate monohydrate after being dried, annual 180 tons about of manganese sulfate monohydrate of production；
(6) step (5) centrifugation gained filtrate after cooling, enters through clear liquid pump 23 after carbonizing trough 24 and adds soda ash,
Produce manganese carbonate precipitation, centrifuge II25 centrifugation carries out separation of solid and liquid, and filter residue drying machine I30 is dried to obtain manganese carbonate, filtrate
Enter mother liquor tank 26, be evacuated in ammonia still 28 through ammonia pump 27, the steam heating being produced with direct fume afterheat, ammonia and steam
Mixture through dephlegmator 29, controls 90 DEG C of dephlegmator 29 exit gas temperature, and ammonia density reaches 10% about and is back to neutralization chamber and follows
Ring uses, annual 1900 tons about of manganese carbonate of production.
Embodiment 3
SO in manganese ore slurry removing flue gas described in the present embodiment2And its method for recycling, using device and embodiment 1
Identical device, comprises the following steps that：
(1) pyrolusite is utilized ball mill wet-milling, cross 200 mesh sieves, add water in surge tank 6 and make pyrolusite pulp, soft manganese
Ore pulp solid content is 18%, and adjusting pyrolusite pulp pH value is 4.5；
(2) flue gas is sulfuric acid preparation factory flue gas, sulfuric acid tail gas treating capacity 200000Nm3/ h, double-absorption sulfuric acid apparatus
SO in tail gas2Content 650mg/Nm3, offgas outlet requirement SO2Content 100mg/Nm3Hereinafter, desulfuration efficiency more than 85%, temperature
Higher flue gas initially enters afterheat heat exchanger and produces low-pressure steam for evaporization process use, the pressurized air blast of flue gas after cooling
1 enters from desulfurizing tower 2 bottom, and the pyrolusite pulp that step (1) is obtained is evacuated to desulfurizing tower and is sprayed, the manganese ore of flue gas and spray
Starch reverse haptoreaction, after flue gas desulfurization from exhanst gas outlet out, SO in flue gas after demister 52Absorbed, removed SO2Afterwards
Flue gas SO2Content is 300mg/Nm3, flue gas is up to standard to be discharged into subsequent processing, and slurries, through circulated sprinkling, are carried out in spray
The discharge of slurries and supplement, technique is carried out continuously, and is mainly manganese sulfate, next to that ferric sulfate, also contains in the slurries after circulation
A small amount of calcium, magnesium, iron, aluminium and a small amount of heavy metal ion, also containing the manganous dithionate generating in sweetening process, slurries store up
Exist in desulfurization slurry storage tank 7, be evacuated to vacuum filter I9 through stock pump II8 and carry out vacuum filter, be filtrated to get filtrate and enter acceptance
Groove I10；
(3) filtrate that step (2) is filtrated to get enters purification tank 12 from dump tank I10, and purification tank 12 is provided with paddle,
Add lime to adjust slurry pH value to 4.5 while stirring, then with being steam heated to 75 DEG C, make manganous dithionate decomposition, slurries warp
Screw pump 13 is evacuated to filter press 14, and sediment is filtered, and obtains purifying filter liquor and enters neutralization chamber 15；
(4) by step (3) neutralization chamber 15 purifying filter liquor add ammoniacal liquor, adjustment pH value be 5, make calcium, magnesium, iron, aluminium with
And a small amount of heavy metal ion generates hydroxide precipitation, neutralizer is put in clarification sedimentation basin 16, is filled out using honeycomb swash plate
Expect to carry out precipitation clarification, and with stock pump III17, liquid is evacuated to vacuum filter II18 to filter further, obtain clear liquid entrance and connect
Groove II19；
(5) clear liquid in step (4) dump tank II19 is carried out vacuum evaporating crystalization through cold boiler 21, be evaporated in vacuo
The vacuum of device 21 is 0.08Mpa, and temperature is 75 DEG C, and manganese sulfate monohydrate mass percentage concentration is concentrated into 40%, while hot through centrifugation
Machine I22 is centrifuged, and filter residue drying machine II31 obtains manganese sulfate monohydrate after being dried, annual production manganese sulfate monohydrate 1800
About ton；
(6) step (5) centrifugation gained filtrate after cooling, enters through clear liquid pump 23 after carbonizing trough 24 and adds soda ash,
Produce manganese carbonate precipitation, centrifuge II25 centrifugation carries out separation of solid and liquid, and filter residue drying machine I30 is dried to obtain manganese carbonate, filtrate
Enter mother liquor tank 26, be evacuated in ammonia still 28 through ammonia pump 27, the steam heating being produced with direct fume afterheat, ammonia and steam
Mixture through dephlegmator 29, controls 95 DEG C of dephlegmator 29 exit gas temperature, and ammonia density reaches 10% about and is back to neutralization chamber and follows
Ring uses, annual 1500 tons about of manganese carbonate of production.
It should be appreciated that for those of ordinary skills, can be improved according to the above description or be converted,
Belong to the protection domain of claims of the present invention.
Claims (5)
1. SO in a kind of manganese ore slurry removing flue gas2And its method for recycling is it is characterised in that comprise the following steps that：
(1) by pyrolusite wet-milling, cross 200 mesh sieves, add water and make pyrolusite pulp, pyrolusite pulp solid content is 18～22%, adjusts
Pyrolusite pulp pH value is 3.5～4.5；
(2) after afterheat heat exchanger cooling, flue gas enters the higher flue gas of temperature from desulfurizing tower bottom, and step (1) is obtained
Pyrolusite pulp is evacuated to desulfurizing tower and is sprayed, the reverse haptoreaction of manganese ore slurry of flue gas and spray, goes out from flue gas after flue gas desulfurization
Mouth out, enters subsequent processing or directly empties, serum recycle sprays, carry out slurries in spray and change supplement, work after demisting
Skill is carried out continuously, and the slurries after circulation carry out vacuum filter；
(3) adding lime to adjust pH value in the filtrate that step (2) is filtrated to get is 4.5～5, is heated to 70～80 DEG C, will precipitate
Thing filters, and obtains purifying filter liquor；
(4) purifying filter liquor of step (3) is added ammoniacal liquor, adjustment pH value is 5～5.5, after precipitation clarification, vacuum filter, obtain
Clear liquid；
(5) clear liquid of step (4) is carried out vacuum evaporating crystalization, vacuum is 0.07～0.08MPa, temperature is 70～80 DEG C,
Manganese sulfate monohydrate mass percent concentration is concentrated into 38～40%, while hot centrifugation, obtains manganese sulfate monohydrate after filter residue and drying；
(6) the separating obtained filtrate of step (5) after cooling, adds soda ash, produces precipitation, carries out separation of solid and liquid, filter residue and drying obtains
To manganese carbonate, filtrate separates and controls dephlegmator outlet temperature, obtains ammonia return to step (4) and recycles.
2. manganese ore slurry removes SO in flue gas according to claim 12And its method for recycling is it is characterised in that step
(6) described outlet temperature is 80～95 DEG C.
3. complete SO in claim 1 or manganese ore slurry removing flue gas described in 2 any one2With the device of the method for recycling,
It is characterized in that, including pressurization blower, desulfurizing tower, demister, stock pump I, circulating pump, surge tank, desulfurization slurry storage tank, stock pump
II, vacuum filter I, dump tank I, vavuum pump I, purification tank, screw pump, filter press, neutralization chamber, clarification sedimentation basin, stock pump
III, vacuum filter II, dump tank II, vavuum pump II, cold boiler, centrifuge I, clear liquid pump, carbonizing trough, centrifuge II,
Mother liquor tank, ammonia pump, ammonia still, dephlegmator, drying machine I, drying machine II；
Pressurization blower is connected with desulfurizing tower bottom, and desulfurization tower bottom is provided with material box, and top is provided with spray equipment, material box with
Circulating pump connects, and circulating pump is connected with spray equipment, and desulfurization top of tower exhanst gas outlet is connected with demister, desulfurization tower bottom charge
Case is also connected with stock pump I, and stock pump I connects surge tank, and desulfurization tower bottom material box is also connected with desulfurization slurry storage tank, and desulfurization slurry storage tank leads to
Cross stock pump II to be connected with vacuum filter I, vacuum filter I connects dump tank I, dump tank I is connected with vavuum pump I, dump tank I
Bottom connects purification tank, purifies trench bottom and connects filter press by screw pump, and filter press connects neutralization chamber, and neutralization trench bottom connects
Clarification sedimentation basin, clarification sedimentation basin connects vacuum filter II by stock pump III, and vacuum filter II connects dump tank II, accepts
Groove II is connected with vavuum pump II, and dump tank II bottom is sequentially connected cold boiler, centrifuge I, and centrifuge I is connected with drying respectively
Machine II and clear liquid pump, clear liquid pump is sequentially connected carbonizing trough, centrifuge II, and centrifuge II connects drying machine I and mother liquor tank respectively, female
Liquid bath is sequentially connected ammonia pump, ammonia still, dephlegmator, and dephlegmator is connected with neutralization chamber.
4. manganese ore slurry removes SO in flue gas according to claim 32With the device of recycling it is characterised in that described clear
It is provided with honeycomb inclined plate packing in clear sedimentation basin.
5. manganese ore slurry removes SO in flue gas according to claim 32With the device of recycling it is characterised in that described tune
It is equipped with paddle inside stock tank, desulfurization slurry storage tank, purification tank, neutralization chamber, carbonizing trough.
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| CN108103526A (en) * | 2017-11-13 | 2018-06-01 | 昆明理工大学 | A kind of method using electrolytic aluminium aluminium ash purifying electrolysis aluminium flue gas and recycling bauxite resource |
| CN110152476A (en) * | 2019-06-18 | 2019-08-23 | 合肥工业大学 | A kind of device and method of flue gas synchronized desulfuring and denitrifying |
| CN110152488A (en) * | 2019-04-28 | 2019-08-23 | 昆明理工大学 | SO in a kind of dry removal coke oven flue gas2Method |
| CN110255794A (en) * | 2019-07-02 | 2019-09-20 | 无锡翰思拓科技有限公司 | Soften desulfurization wastewater using ammonium hydroxide and recycles the Zero-discharge treating process of ammonium hydroxide |
| CN110357164A (en) * | 2019-07-08 | 2019-10-22 | 四川大学 | The method that manganese oxide ore pulp recycles high-efficiency flue gas desulfurization coupling manganese sulfate green purifying |
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