CN102815750B - Method for preparing manganese sulfate by using manganese dioxide ore pulp to absorb sulfur dioxide in flue gases - Google Patents
Method for preparing manganese sulfate by using manganese dioxide ore pulp to absorb sulfur dioxide in flue gases Download PDFInfo
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- CN102815750B CN102815750B CN201210322223.0A CN201210322223A CN102815750B CN 102815750 B CN102815750 B CN 102815750B CN 201210322223 A CN201210322223 A CN 201210322223A CN 102815750 B CN102815750 B CN 102815750B
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 56
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 34
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 34
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 34
- 239000003546 flue gas Substances 0.000 title claims abstract description 32
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims description 43
- 238000010521 absorption reaction Methods 0.000 claims abstract description 113
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 239000007788 liquid Substances 0.000 claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 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 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 38
- 229910052748 manganese Inorganic materials 0.000 claims description 36
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 24
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 claims description 23
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 12
- 235000010755 mineral Nutrition 0.000 claims description 12
- 239000011707 mineral Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 10
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000779 smoke Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011800 void material Substances 0.000 claims description 5
- 238000005367 electrostatic precipitation Methods 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000011362 coarse particle Substances 0.000 claims description 2
- 238000000247 postprecipitation Methods 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 65
- 239000000047 product Substances 0.000 abstract description 13
- 229910052742 iron Inorganic materials 0.000 abstract description 12
- 238000006477 desulfuration reaction Methods 0.000 abstract description 11
- 230000023556 desulfurization Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000009102 absorption Effects 0.000 description 65
- 206010001497 Agitation Diseases 0.000 description 33
- 238000013019 agitation Methods 0.000 description 33
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000012546 transfer Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000013589 supplement Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 239000011790 ferrous sulphate Substances 0.000 description 7
- 235000003891 ferrous sulphate Nutrition 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 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 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229940075933 dithionate Drugs 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008676 import Effects 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004094 preconcentration Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for preparing manganese sulfate by using a manganese dioxide ore pulp to absorb sulfur dioxide in flue gases. The method includes following steps of subjecting manganese dioxide ore to wet ball milling and grading to obtain an initial ore pulp, and smashing the initial ore pulp through a vertical type stirring mill to obtain a reaction ore pulp; adding a manganese sulfate solution containing Fe<3+> and/or Fe<2+> to the obtained reaction ore pulp, then subjecting the reaction ore pulp and the high temperature flue gases containing the sulfur dioxide to absorption reaction with the reaction temperature controlled between 90 DEG C and 95 DEG C; and subjecting reaction products obtained after the absorption reaction to solid-liquid separation, iron removing and heavy metal removing, and then performing ordinary pressure concentration and crystallization to obtain the manganese sulfate monohydrate, wherein particle sizes of ore materials in the initial ore pulp are smaller than 149 mu m, and particle sizes of 90% of the ore materials in the reaction ore pulp below 50 mu m. The method for preparing the manganese sulfate by using the manganese dioxide ore pulp to absorb the sulfur dioxide in the flue gases has the advantages of being energy-saving, environment-friendly, high in resource utilization rate, high in product additional value, good in flue gas desulfurization effects, continuous and thorough in reaction, low in costs and the like.
Description
Technical field
The invention belongs to the interleaving techniques field of hydrometallurgy and environmental protection and energy saving, relate in particular to a kind of method of producing technical grade manganese salt with higher-grade natural manganese dioxide ore pulp and smoke reaction.
Background technology
Solid manganese sulfate monohydrate is important industrial chemicals, can be used as fertilizer and fodder additives, is also the basic material of nearly all manganese goods, and only domestic annual requirement, just more than 1,000,000 tons, is gone back a large amount of for export to other countries.The domestic enterprise that has a lot of production solid manganese sulfate monohydrates, this is also one of traditional product of Chinese manganese goods.
Rhodochrosite can be for the production of manganous sulfate, but due to rhodochrosite general with calcium carbonate, magnesiumcarbonate symbiosis, seldom have both at home and abroad enterprise's employing rhodochrosite acid-soluble come extracting sulfuric acid manganese, generally all adopt the acid-soluble production manganous sulfate of dioxide ore for manganese reducing roasting.Another kind method is to react with pyrite and produce manganous sulfate with pyrolusite.Adopt reduction roasting method, investment is large, energy consumption is high, and roasting reduction produces a large amount of CO and CO
2gas, serious environment pollution, domestic now progressively superseded.React the enterprise that produces solid manganese sulfate monohydrate with pyrolusite with pyrite and increase gradually, two ore deposit methods need to consume curing iron ore, the vitriol oil, and production process waste residue amount is large, and manganese resource recovery is low, deficiency in economic performance.In addition, no matter be to adopt reduction roasting method or two ore deposit methods, the manganese sulfate solution concentration that domestic production technique makes is lower, and production process need to consume the energy and carry out pre-concentration, and this has also increased energy consumption greatly, runs counter to the development trend of current low-carbon environment-friendly.
On the other hand, thermal power generation at home in supply of electric power in the highest flight, thermal power generation coal-fired process can produce a large amount of SO
2gas, new power plant construction is all equipped with Large Lime stone-lime desulfurization device at present, and to meet the environmental requirement day by day improving, this also becomes the environmental protection cost that domestic firepower electrical plant must drop into, particularly in Sichuan, the high sulphur coal producing region such as Chongqing, Guizhou, its environment protection desulphurization cost of bearing is more very.
In prior art, have a small amount of document to be mentioned to flue gas desulfurization and manganous sulfate are produced to the art breading technology that dual purpose combines, but all there is such or such technological deficiency in these methods.These existing art breading are mainly divided into two kinds: one is with Manganse Dioxide dry powder high temperature desulfurizing in reaction bed, use fixed-bed reactor, moving-burden bed reactor or fluidized-bed reactor no matter be, this is all similar with the process of Manganse Dioxide reducing roasting, its defect is that capital cost of reactor is large, floor space is large, operational condition is poor, and fixed-bed reactor need periodical operation, labour intensity is large, also needs ball milling to absorb material after reaction, dissolve, technical process is long again; This class treatment process also rests on laboratory stage or pilot scale stage at present at home, does not realize suitability for industrialized production; Another kind method is wet desulphurization, the tray column, tubulent contact tower, packing tower, jet blistering tower etc. that adopt porous repeatedly the conventional absorption column of gas of chemical industry as reactor, the flue gas that contains sulfurous gas enters from tower pucking, Manganse Dioxide raw material from tower top adverse current and, assimilation effect is fine, after absorbing, sulfur dioxide gas body burden is even lower than dry desulfurization, but the Manganse Dioxide ore pulp in these class methods can progressively stop up after operation for some time in tower, gas channel constantly dwindles in tower, so affect technique for a long time, continue to carry out.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, a kind of method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese that provide energy-conserving and environment-protective, resource utilization is high, added value of product is high, flue gas desulfurization is effective, reaction is continuous thoroughly, cost is low.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, comprises the following steps:
(1) ore grinding
By dioxide ore for manganese first carry out wet ball grinding, classification obtains initial ore pulp, the object that mineral aggregate granularity in initial ore pulp is less than 149 μ m(ball millings, classification is exactly the mineral aggregate that is less than 149 μ m obtaining after ball milling in order to isolate), initial ore pulp is pulverized through vertical mixing mill again, obtain reacting ore pulp (being thin ore pulp), reaction ore pulp Mineral Material granularity 90% is preferably below 50 μ m; Because follow-up Manganse Dioxide and sulfurous gas absorption reaction are three-phase gas-liquid-solid redox reaction, the factors such as membrane mass transfer, liquid film mass transfer, solid interior mass transfer and redox processes transfer transport of being bullied affect, square being inversely proportional to of chemical reaction velocity and solid particle size, therefore, natural manganese dioxide ore deposit to be ground into below 50 μ m, make solid particulate have enough little particle diameter, enough large specific surface areas, so that Manganse Dioxide can react in the short period of time with sulfurous gas, reach the object of desulfurization; Visible, can improve dioxide ore for manganese particle mass transfer ability by the ore grinding of this step, improve the reaction efficiency of follow-up absorption reaction, Reaction time shorten;
(2) absorption reaction
In reaction ore pulp obtained above, add containing Fe
3+and/or Fe
2+manganese sulfate solution, then make to react ore pulp (reaction ore pulp also can be described as " absorption ore pulp " in absorption reaction process) and carry out absorption reaction with the high-temperature flue gas containing sulfurous gas, temperature of reaction is controlled at 90 DEG C～95 DEG C; Absorption reaction preferably carries out in the absorption tower of void tower pattern, reaction ore pulp available pump input absorption tower, absorption tower is preferably the void tower of one or three grades of series connection, the high-temperature gas that contains sulfurous gas enters from tower pucking, at the bottom of tower, be all equipped with absorption liquid agitated pool, absorption liquid flows into bottom agitated pool after absorbing, then returns to this absorption tower with pump; By adopting the absorption tower of void tower pattern, can eliminate the possibility that manganese ore slurry absorption reaction process results in blockage, unobstructedly in tower do not stop up, move more safe and reliable; In addition after ore grinding the mineral aggregate grain diameter overwhelming majority lower than 50 μ m, this has increased liquid-solid reaction area, shorten the distance of reactant at solid inner transmission matter, the contact that can further strengthen gas-liquid by controlling the spraying intensity on absorption tower, sulfur dioxide gas is fully dissolved in reaction ore pulp, by controlling the pH value of reaction process between 3～3.5, can ensure better the solubleness of sulfurous gas in absorption ore pulp; In addition, in reaction ore pulp, retain a certain amount of Fe
3+, Fe
2+, not only can promote sulfurous gas and Manganse Dioxide direct reaction, and can pass through medium Fe
3+, Fe
2+reaction, fast reaction speed (Fe
2+with MnO
2liquid-solid reaction, Fe
3+gas liquid reaction), the principal reaction formula of absorption reaction process is as follows:
SO
2+MnO
2=MnSO
4；
H
2SO
3+MnO
2=MnSO
4+H
2O；
2H
2O+SO
2+?2Fe
3+=SO
4 2-+2Fe
2++4H
+；
4H
++2Fe
2++MnO
2=2Fe
3++Mn
2++2H
2O；
Above-mentioned several reactions are generally carried out in absorption reaction process simultaneously, and can accelerate Manganse Dioxide and dissolve generation manganous sulfate, in addition, the K of a large amount of iron and the stripping of Manganse Dioxide ore pulp
+, Na
+in the absorption reaction process of 90 DEG C～95 DEG C, can form insoluble sulfuric acid ferripotassium vanadium and sulfuric acid ferrisodium vanadium, part forms Fe (OH)
3precipitate and remove;
(3) purify condensing crystal: the reaction product after above-mentioned absorption reaction is completed, after solid-liquid separation, deironing and heavy metal, then is carried out normal pressure condensing crystal, obtains manganese sulfate monohydrate.
Although adopted various measures to reduce as far as possible the generation of side reaction in technique scheme of the present invention, the reaction process of above-mentioned sulfurous gas and Manganse Dioxide still inevitably has side reaction and occurs, and its main side reaction is as follows: MnO
2+ 2SO
2=MnS
2o
6, in this manganese sulfate monohydrate product that makes to produce, can contain a small amount of (1%～2%) manganous dithionate, due to dithionic acid root and polythionate different in kind, in solution, various strong oxidizers all can not make it oxidation.External report has employing Na
2cO
3precipitation, forms Na
2s
2o
4remove, but operational path is long, the finished product Na
2sO
4added value is low.Consider manganous dithionate solid thermal poor stability, the manganese sulfate monohydrate solid of therefore producing can toast 1.5h～2h in the time of 140 DEG C, to slough manganous dithionate, ensures quality and the purity of product; The sulfur dioxide gas producing when baking can all return to first grade absorption tower, can be to environment.
The above-mentioned method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, described dioxide ore for manganese is preferably containing Mn and measures the natural manganese dioxide ore more than 40%.
The above-mentioned method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, in described step (1), preferably, the coarse particles mineral aggregate of ball milling, classification postprecipitation can return to described wet ball grinding step and proceed follow-up technological process.
The above-mentioned method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, in described step (2), the manganous sulfate concentration in the manganese sulfate solution of interpolation is preferably 130g/L～150g/L, Fe
3+and/or Fe
2+concentration be preferably 4g/L～5g/L; Add containing Fe
3+and/or Fe
2+manganese sulfate solution after, the pH value of described reaction ore pulp is preferably controlled at 3～3.5.In product after described absorption reaction completes, the concentration of manganous sulfate is preferably 300g/L～320g/L.
The above-mentioned method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, in described step (2), preferably, reaction ore pulp is to be gone forward side by side and reached 90 DEG C～95 DEG C of the required temperature of reaction after the heat exchange of promoting the circulation of qi liquid by the heat of continuous absorption high-temperature flue gas.Described high-temperature flue gas preferably after electrostatic precipitation temperature up to 140 DEG C～boiler smoke of 160 DEG C.
The above-mentioned method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, after described absorption reaction completes, the pH value of reaction product, generally 2.5～3.5, generally remains the Fe of 4g/L～5g/L in reaction product
2+and Fe
3+, therefore, reaction product, after solid-liquid separation, generally need to be carried out deironing operation.The concrete steps of described deironing are preferably: with Mn content more than 40%, the granularity natural pyrolusite that is less than 50 μ m adds to and in the reaction solution after solid-liquid separation, carries out iron removal by oxidation; In order to ensure the oxidation capacity of Manganse Dioxide, iron removal should be carried out at acidic conditions, therefore can first with acid (sulfuric acid), the pH value of reaction solution be adjusted to 1.5～2.0, and Manganse Dioxide should be excessive simultaneously, just can reach so better de-ferrous effect; Steam heating to 90 DEG C again～95 DEG C is carried out stirring reaction, and the principal reaction formula in stirring reaction process is as follows:
4H
++2Fe
2++MnO
2=2Fe
3++Mn
2++2H
2O；
After stirring reaction 40min～50min, detect and determine in solution there is no Fe through fast qualitative
2+add again a small amount of reduction manganese monoxide, because manganese monoxide is basic oxide, (the present invention does not adopt conventional neutralizing agent calcium oxide to have antacid ability, significantly to reduce the calcium contents in product), add in manganese monoxide and after make the pH value of reaction solution reach 5.2～5.6, the reaction formula of neutralization reaction is as follows:
H
2SO
4+MnO=MnSO
4+H
2O；
Obtain manganese sulfate solution and the ferromanganese slag after deironing finally by solid-liquid separation.Detect with Atomic Absorption Spectroscopy AAS, in the manganese sulfate solution after deironing, iron level is no more than 2ppm, residual excessive Manganse Dioxide and the reduction manganese monoxide that not exclusively dissolves in ferromanganese slag, and ferromanganese slag adds and can return to aforementioned absorption reaction step after dilute sulphuric acid and prepare burden.
In the process with Manganse Dioxide ore pulp sulfur dioxide absorption, follow the dissolving of manganese, Cu in ore
2+, Co
2+, Ni
2+, Zn
2+, Pb
2+also be partly dissolved, though the content of these heavy metals is not high, if do not remove, may make product can not meet specification of quality.Therefore, after deironing, manganese sulfate solution needs further to remove beavy metal impurity wherein.Because above-mentioned iron removal is transferred to 5.2～5.6 by the pH value of manganese sulfate solution, now only need add the barium sulphide of 20 times of amounts of heavy metal content, after stirring reaction, filtration, can obtain clarifying qualified manganese sulfate solution.
The above-mentioned method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, in described step (2) containing Fe
3+and/or Fe
2+manganese sulfate solution preferably adopt dilute sulphuric acid to dissolve ferromanganese slag after above-mentioned deironing to obtain, this is fully reclaimed manganese resource, also can make to react ore pulp and contain enough Fe
2+and/or Fe
3+carry out to suppress side reaction.Therefore, required Fe in the absorption ore pulp of technique scheme of the present invention
3+, Fe
2+do not need to supplement in addition.
The above-mentioned method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, in described step (2), adds containing Fe
3+and/or Fe
2+manganese sulfate solution after, reaction ore pulp be preferably controlled at 3.0～3.5 in the pH of initial reaction stage value.
The above-mentioned method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, before described absorption reaction, the initial solid content of reaction ore pulp is preferably 10%～12%, after absorption reaction completes, because higher-grade Manganse Dioxide is dissolved in absorption liquid, the solid content in reaction product can be controlled in below 3%.
Compared with prior art, the invention has the advantages that:
(1) consider thermal power generation corporations move continuously enterprise, except planned maintenance, generally can not stop, therefore flue gas desulfurization course must with thermal power generation corporations' synchronous operation; The present invention adopts the absorption agent of higher-grade (containing manganese more than 40%) dioxide ore for manganese as flue gas desulfurization, manganese content is high, consumption is few, in flue gas desulfurization sprinkle liquid, contain solid few, after absorbing dissolving, solid content is lower, the requirement of means of flue gas desulfurization of power plant be can not only meet, and industrialization, serialization production easily realized.
(2) between Manganse Dioxide of the present invention and sulfurous gas, belong to gas-solid-liquid redox reaction, reaction normal Gibbs free energy reaches Δ G °=﹣ 207.08KJ/mol in the time of 298K, and reaction equilibrium constant is K °=1.88 × 10
36, SO
2equilibrium partial pressure is 5.39 × 10
-32pa, this chemical reaction carries out very thoroughly.In addition, the present invention preferably adopts the measures such as flue gas and three grades of absorptions of ore pulp adverse current, multi-stage spray, absorption ore pulp continuous circulation, make to absorb chemical reaction and undertaken by the balance direction of expecting as far as possible, the sulfurous gas in flue gas can reach the degree lower than 100mg/ standard cube after absorbing.
(3) natural manganese dioxide ore deposit (such as pyrolusite) inevitably impurity such as iron content, aluminium, calcium, magnesium, silicon, in boiler smoke, except remaining oxygen, nitrogen, water vapor, carbonic acid gas, carbon monoxide, sulfurous gas, also contain sulphur trioxide, nitrogen protoxide, nitrogen peroxide etc.; Therefore, Manganse Dioxide and sulfurous gas also have numerous side reactions and occur except main reaction, and the present invention improves the batching before absorption reaction by optimization, makes the pH value of reacting ore pulp be transferred to 3～3.5, adds in addition the Fe of 4g/L～5g/L in ore pulp
2+, Fe
3+, at utmost to ensure the carrying out of main reaction; In addition, Manganse Dioxide ore pulp also possesses NO, NO in the flue gas of absorption
2effect, NO, NO in flue gas after three grades of sprays are processed
2reduced more than 80%, fine dusts is also absorbed simultaneously, make dust in power-plant flue gas, particularly fine dusts still less, and Manganse Dioxide transformation efficiency can reach more than 90%, and flue gas can qualified discharge.
(4) aspect the utilizing of the energy, the present invention makes full use of flue gas heat, with flue gas heat heating absorption ore pulp, makes ore pulp reach reaction temperature required, reduces flue gas heat to airborne release, has also saved ore pulp and has heated required heat.In addition, the present invention adopts solid-liquid separation fore portion manganese sulfate solution to return to the mode of preparation absorption ore pulp, produces high-concentration sulfuric acid manganese, before condensing crystal, needn't carry out pre-concentration to manganese sulfate solution, directly normal pressure condensing crystal, produces manganese sulfate monohydrate solid, energy efficient.
(5) aspect resources conservation, the present invention fully recycles manganous sulfate production process deferrization process and leaves ferromanganese slag, more than making reaction system electropotential maintenance 500mV, and control pH value in reaction, adopt above three measures not only effectively to suppress side reaction generation, and having improved the rate of recovery of manganese resource, whole technological process manganese resource recovery reaches more than 90%.Because Manganse Dioxide and sulfurous gas speed of response are slower than Wingdale and sulfurous gas speed of response, the present invention, by adopting three grades of series connection to absorb, can strengthen gas-liquid-solid three-phase duration of contact, to ensure Manganse Dioxide transformation efficiency, absorption rate of sulfur dioxide.
In sum, utilize higher-grade natural manganese dioxide ore pulp sulfur dioxide absorption to produce high-concentration sulfuric acid manganese, thermal power generation corporations can no longer use limestone desulfurization, there is denitration simultaneously and reduce fine dusts ability, reduce thermal power generation corporations' environmental burden, improve sweetening effectiveness, but also can produce technical grade manganese sulfate monohydrate byproduct, this has improved thermal power generation corporations greatly, particularly the economic benefit of burning high sulfur coal electricity power enterprise and environmental benefit.The manganous sulfate that the present invention produces uses recycle-water slurrying completely, and insufficient section supplements tap water, and solution, through atmospheric evaporation, is made solid, does not have solution to stay, not outer row's trade effluent; Production process is both without sulfuric acid, and also without pyrite, the cost that saves material, is one production technique cheaply.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention's Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese.
embodiment
Below in conjunction with Figure of description and specific embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
embodiment 1:
The raw material manganese dioxide ore (abbreviation manganese ore) that the present embodiment adopts is by Brazilian import, and according to the analysis result information of Central South University's modern analysis and test center ICP-AES, the element component content in this manganese ore is analyzed as follows shown in table 1.
The component content analytical table of table 1: embodiment 1 Raw Manganse Dioxide manganese ore
| Element | Content μ g/g(is except %) | Element | Content μ g/g(is except %) | Element | Content μ g/g(is except %) |
| Mn | 42.60% | Ca | 5.9 | S | 197.6 |
| Hg | 50 | In | 20 | As | 10.1 |
| Se | 20 | Au | 1 | Mo | 2.4 |
| Sn | 513.3 | B | 8.1 | P | 1120 |
| Zn | 20 | Pt | 1 | K | 9200 |
| Sb | 34.2 | Mg | 2181 | Na | 2300 |
| Ce | 383.7 | V | 2.7 | Fe | 6% |
| Pb | 342 | Al | 4% |
The high-temperature flue gas raw material of using in the present embodiment is the boiler smoke of temperature up to 146 DEG C after electrostatic precipitation, and its component content is as shown in table 2 below.
The compositional data analytical table of boiler smoke in table 2: embodiment 1
| Project | Temperature | SO 2Concentration | N 2 | O 2 | ＮO | ＮO 2 |
| Data results | 146℃ | 12000mg/ Nm 3 | 82% | 6.2% | 620 mg/ Nm 3 | 240 mg/ Nm 3 |
As shown in Figure 1, the method for the above-mentioned dioxide ore for manganese absorption boiler of a kind of use sulfur dioxide in flue gas extracting sulfuric acid manganese, comprises the following steps:
(1) ore grinding: import Brazil manganese dioxide ore largest particle particle diameter of the present embodiment is no more than 4mm, manganese dioxide ore is first directly poured in ball mill and by the solid-to-liquid ratio of 1: 1.5 and added water and carry out wet ball grinding, after wet ball grinding, utilize grading machine to carry out stage treatment, regulate grading machine flashboard height, make to contain the initial ore pulp overflow that is less than 149 μ m mineral aggregates and enter the moisturizing again of QHJM vertical mixing mill, making solid content is 40%.Initial ore pulp is pulverized 45min through vertical mixing mill again, obtains reacting ore pulp, and through BT-9300HT type laser fineness gage testing graininess, reaction ore pulp Mineral Material granularity 91.04% is less than 50 μ m.
(2) batching: reaction ore pulp obtained above is added in agitation vat to the effective volume 2m of agitation vat
3;
In one-level agitation vat, add 310L reaction ore pulp, and supplementary 1.6m
3the manganese sulfate solution of sulfur acid manganese 150g/L, takes 10.5kg ferrous sulfate (FeSO
47H
2o) after water-soluble, pour in one-level agitation vat, take 10.5kg ferric sulfate (Fe
2(SO
4)
3-9H
2o) after water-soluble, pour one-level agitation vat into, start agitator, add the 600mL vitriol oil;
In secondary agitation vat, add 320L reaction ore pulp, then supplement 1.6m
3the manganese sulfate solution of sulfur acid manganese 140g/L, takes respectively 10.5kg ferrous sulfate and ferric sulfate and pours secondary agitation vat into after water-soluble, starts agitator, adds the 600ml vitriol oil;
In three grades of agitation vats, add 340L reaction ore pulp, then supplement 1.6m
3the manganese sulfate solution of sulfur acid manganese 130g/L, takes respectively 10.5kg ferrous sulfate and ferric sulfate and pours three grades of agitation vats into after water-soluble, starts agitator, adds the 600ml vitriol oil.
(3) absorption reaction: the absorption reaction of the present embodiment carries out in absorption tower, reaction ore pulp available pump input absorption tower, absorption tower is the void tower of one or three grades of series connection, the absorption tower structure of three series connection is identical, the scum dredger that double-layer nylon-6 make is arranged on each absorption tower topmost, six layers of spraying layer are arranged in lower end, and the liquid-gas ratio of spray flux is generally 34.4L/m
3, the high-temperature gas that contains sulfurous gas enters from tower pucking, downward-sloping 7 ° of blast orifice, and air-flow lift velocity general control in tower is 2m/s; Every grade of absorption tower configures separately 1000Pa, 1200m
3/ h blower fan, is all equipped with at the bottom of tower and absorbs flowsheet of slurry agitation pond, and the reaction ore pulp in every first grade absorption tower is to be inputted by the agitation vat pumping of corresponding one-level, flows into bottom agitated pool after absorption reaction, then returns in absorption tower with pump;
Although the structure on three grades of absorption towers is identical, function difference; Boiler gas in first grade absorption tower is the denseest containing sulfurous gas, and after one-level absorbs, sulfur dioxide concentration significantly declines, and enters secondary and absorbs, and after secondary absorbs, sulfur dioxide concentration reduces again, then enters three grades of absorption towers; Absorption ore pulp in the agitated pool of bottom, three absorption towers is also different, in the agitated pool of bottom, three grades of absorption towers, absorbing ore pulp is to input from mixer pump, higher containing manganese dioxide concentration, the just reaction pulp solids good surface activity of preparation, sulfur dioxide absorption ability is strong, but in tower, sulfur dioxide concentration is low, must be with the strong reaction ore pulp of receptivity, fully sulfur dioxide absorption gas, makes the gaseous sulfur dioxide content meet the requirement of environmental protection discharging; Under three grades of absorption towers, completing three grades of ore pulps after absorption reaction transfers to and in the agitated pool under two-level absorption tower, proceeds secondary and absorb, in like manner, under two-level absorption tower, completing ore pulp after secondary absorption reaction transfers to and in the agitated pool under first grade absorption tower, proceeds one-level and absorb, under first grade absorption tower, in agitated pool, absorbing ore pulp Manganse Dioxide content reduces, but in tower, sulfur dioxide gas body burden is the highest, still can meet reaction requirement; General through 4h～4.5h self-circulation, in the agitated pool of first grade absorption tower, absorb ore pulp from the dark brown garnet that progressively becomes, illustrate that one-level absorption reaction approaches terminal, when in chemical examination slag, manganese content is no more than 1.25%, transfer to chemical combination bucket and process absorbing ore pulp (being reaction product) under first grade absorption tower, under two-level absorption tower, absorb ore pulp and transfer to agitated pool under first grade absorption tower, under three grades of absorption towers, absorb ore pulp and transfer to agitated pool under two-level absorption tower, absorption reaction carries out uninterruptedly continuously; Absorb and can make to react the MnO in ore pulp through three grades of absorption towers
2absorb completely;
According to the reaction principle of above-mentioned absorption reaction equipment, open respectively the pump upper lock gate of one-level agitation vat, secondary agitation vat, three grades of agitation vats, by the reaction ore pulp pumping input absorption tower after batching, make itself and the boiler smoke containing sulfurous gas carry out absorption reaction, start the spray pump in first grade absorption tower, two-level absorption tower, three grades of absorption towers, observe in spray, foam removal, stirring and absorption tower liquid level normally after, slowly start the other pipe closer door of flue, observe gas meter and gaseous tension, when gas flow is stabilized in 1200Nm simultaneously
3/ h, pressure, in the time of 1000Pa, stop regulating, and absorption reaction starts to carry out, every pH value of 20min survey, SO
2concentration and slurry temperature; When absorption reaction, slurry temperature is controlled at 90 DEG C～95 DEG C; After 4h, in one-level agitation vat, ore pulp starts to change color, after 5h, become garnet, after 6h, shift out the processing of carrying out subsequent step, absorption ore pulp in secondary agitation vat moves in one-level agitation vat, absorption ore pulp in three grades of agitation vats moves in secondary agitation vat, and three grades of agitation vats separately supplement new preparation ore pulp; After absorption reaction starts, only need three grades of reaction ore pulps that agitation vat is required of preparation, no longer add ferrous sulfate and ferric sulfate, can directly supplement Fe with the ferromanganese slag reclaiming in follow-up deironing step
2+, Fe
3+, by the supplementary manganous sulfate concentration of supernatant liquid of one-level agitation vat.
(4) deironing: after above-mentioned absorption reaction completes, the pH value of the reaction product that one-level agitation vat is discharged is generally 2.5～3.5, and reaction product can reach 300g/L～320g/L in the concentration of manganous sulfate after solid-liquid separation, owing to generally remaining the Fe of 4g/L～5g/L in reaction product
2+and Fe
3+, therefore need to carry out deironing operation, the concrete steps of deironing are: use Mn content more than 40%, the natural pyrolusite that granularity is less than 50 μ m adds to and in the reaction solution after solid-liquid separation, carries out iron removal by oxidation, the addition of natural pyrolusite pulp is 2 times of left and right of iron-holder in reaction solution, the pH value of reaction solution is first adjusted to 1.5～2.0 with sulfuric acid, steam heating to 90 DEG C again～95 DEG C is carried out stirring reaction (mixing speed is 63r/min), after stirring reaction 40min～50min, the manganese monoxide neutralization with reduction makes the pH value of reaction solution reach 5.2～5.6 again, obtain manganese sulfate solution and the ferromanganese slag after deironing finally by solid-liquid separation, with the ferromanganese slag after dilute sulphuric acid dissolving deironing, obtain containing Fe
3+and/or Fe
2+manganese sulfate solution, should be containing Fe
3+and/or Fe
2+manganese sulfate solution can be used as the replenishment of ingredients in three grades of agitation vats of above-mentioned steps.
(5) removing heavy metals: the manganese sulfate solution after deironing adds the barium sulphide of 20 times of amounts of heavy metal content again, stirs 40min～45min, can remove the heavy metal in solution, obtains qualified manganese sulfate solution after solid-liquid separation.
(6) condensing crystal: the manganese sulfate solution atmospheric steam heating obtaining is carried out to condensing crystal, centrifugation, obtain manganese sulfate monohydrate, mother liquor can return to iron removal step.
According to above-mentioned technological operation of the present invention, may residual manganous dithionate in crystallization, such product can slowly release sulfur dioxide gas (MnS storing, in transportation
2o
6=MnSO
4+ SO
2 ↑), affect user's safe handling.Therefore, manganese sulfate monohydrate obtained above after 105 DEG C of dewatered dryings, can be again through 140 DEG C of baking 1.5h～2h, allow the abundant thermolysis of manganous dithionate, to slough residual manganous dithionate.
The product in each stage in the present embodiment is detected to analysis:
1. after absorption reaction completes, will in first grade absorption tower, absorb residue after solid-liquid separation on ore pulp through secondary washing, sampling drying detects analysis, wherein containing manganese 1.2%, iron content 24%;
2. the product sample of producing after condensing crystal is analyzed, result is as shown in table 3 below:
In table 3: embodiment 1, final product compositional data is analyzed
| Project | Analytical results | Project | Analytical results |
| Mn | 32.3% | Cu | 1.1ppm |
| Ca | 119ppm | Pb | 6.8ppm |
| Mg | 154ppm | Co | 4.6ppm |
| K | 18.5ppm | Ni | 4.3ppm |
| Na | 37.7ppm | Zn | 5.2ppm |
| Fe | 4ppm | Moisture content | 0.1% |
3. after three grades of absorptions, the content of sulfur dioxide in tail gas is 240mg/Nm
3.
embodiment 2:
The raw material manganese dioxide ore that the present embodiment adopts is by Gabon's import, and according to the analysis result information of Central South University's modern analysis and test center ICP-AES, the element component content in this manganese ore is analyzed as follows shown in table 4.
The component content analytical table of table 4: embodiment 2 Raw manganese dioxide ores
| Element | Content μ g/g(is except %) | Element | Content μ g/g(is except %) | Element | Content μ g/g(is except %) |
| Mn | 46% | Cd | 5 | S | 649.3 |
| Hg | 5 | In | 20 | As | 6 |
| Se | 20 | Au | 1 | Mo | 24 |
| Sn | 22.7 | B | 17.1 | P | 1120 |
| Zn | 25 | Pt | 1 | K | 9400 |
| Sb | 20 | Mg | 1% | Na | 3400 |
| Ce | 100 | V | 335.8 | Fe | 6.30% |
| Pb | 22.2 | Al | 4.30% |
The high-temperature flue gas raw material of using in the present embodiment be in embodiment 1 after electrostatic precipitation the boiler smoke of temperature up to 146 DEG C, its component content is as above shown in table 2.
As shown in Figure 1, the method for the above-mentioned dioxide ore for manganese absorption boiler of a kind of use sulfur dioxide in flue gas extracting sulfuric acid manganese, comprises the following steps:
(1) ore grinding: the import manganese dioxide ore largest particle particle diameter of the present embodiment is no more than 3mm, this manganese ore is first directly poured in ball mill and by the solid-to-liquid ratio of 1: 1.5 and added water and carry out wet ball grinding, after wet ball grinding, utilize grading machine to carry out stage treatment, regulate grading machine flashboard height, making to contain the initial ore pulp overflow that is less than 149 μ m mineral aggregates enters QHJM vertical mixing mill make up water to make solid content is 40%, initial ore pulp is pulverized 45min through vertical mixing mill again, obtain reacting ore pulp, through BT-9300HT type laser fineness gage testing graininess, reaction ore pulp Mineral Material granularity 93.31% is less than 50 μ m.
(2) batching: reaction ore pulp obtained above is added in agitation vat to the effective volume 2m of agitation vat
3;
In one-level agitation vat, add 310L reaction ore pulp, and supplementary 1.6m
3the manganese sulfate solution of sulfur acid manganese 150g/L, takes 10.5kg ferrous sulfate and pours in one-level agitation vat after water-soluble, takes 10.5kg ferric sulfate and pours one-level agitation vat into after water-soluble, starts agitator, adds the 600mL vitriol oil;
In secondary agitation vat, add 320L reaction ore pulp, then supplement 1.6m
3the manganese sulfate solution of sulfur acid manganese 140g/L, takes respectively 10.5kg ferrous sulfate and ferric sulfate and pours secondary agitation vat into after water-soluble, starts agitator, adds the 600ml vitriol oil;
In three grades of agitation vats, add 340L reaction ore pulp, then supplement 1.6m
3the manganese sulfate solution of sulfur acid manganese 130g/L, takes respectively 10.5kg ferrous sulfate and ferric sulfate and pours three grades of agitation vats into after water-soluble, starts agitator, adds the 600ml vitriol oil.
(3) absorption reaction: conversion unit, operation steps and the processing parameter that absorption reaction adopts and processing condition are identical with the step (3) in embodiment 1.
(4) deironing, removing heavy metals, condensing crystal: operation steps and technological parameter are identical with step (4)～(6) in embodiment 1.
The product in each stage in the present embodiment is detected to analysis:
1. after absorption reaction completes, will in first grade absorption tower, absorb residue after solid-liquid separation on ore pulp through secondary washing, sampling drying detects analysis, wherein containing manganese 1.3%, iron content 21%;
2. the final product sample of producing after condensing crystal is analyzed, result is as shown in table 5 below:
In table 5: embodiment 2, final product compositional data is analyzed
| Project | Analytical results | Project | Analytical results |
| Mn | 32.44% | Cu | 1.3ppm |
| Ca | 523ppm | Pb | 8ppm |
| Mg | 341ppm | Co | 4.8ppm |
| K | 8.2ppm | Ni | 6.6ppm |
| Na | 56ppm | Zn | 1.9ppm |
| Fe | 6.3ppm | Moisture content | 0.1% |
3. after three grades of absorptions, the content of sulfur dioxide in tail gas is 280mg/Nm
3.
Above embodiments of the invention further show: in the reaction product residue after the present invention absorbs completely, be no more than 1.3% containing insoluble manganese and soluble manganese total amount, meet the requirement of environmental protection makes again manganese resource be fully used, and whole process does not have discharge of wastewater.
Claims (6)
1. by a method for Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese, comprise the following steps:
(1) ore grinding: by dioxide ore for manganese first carry out wet ball grinding, classification obtains initial ore pulp, mineral aggregate granularity in initial ore pulp is less than 149 μ m, initial ore pulp is pulverized through vertical mixing mill again, obtains reacting ore pulp, and reaction ore pulp Mineral Material granularity 90% is below 50 μ m;
(2) absorption reaction: add containing Fe in reaction ore pulp obtained above
3+and Fe
2+manganese sulfate solution, then make to react ore pulp and carry out absorption reaction with the high-temperature flue gas containing sulfurous gas, temperature of reaction is controlled at 90 DEG C～95 DEG C; Absorption reaction carries out in the absorption tower of void tower pattern, reaction ore pulp available pump input absorption tower, the high-temperature flue gas that contains sulfurous gas enters from tower pucking, is all equipped with absorption liquid agitated pool at the bottom of tower, absorption liquid flows into bottom agitated pool after absorbing, then returns to this absorption tower with pump; Described reaction ore pulp is to be gone forward side by side and reached 90 DEG C～95 DEG C of the required temperature of reaction after the heat exchange of promoting the circulation of qi liquid by the heat of continuous absorption high-temperature flue gas; Manganous sulfate concentration in the manganese sulfate solution adding is 130g/L～150g/L, Fe
3+and Fe
2+concentration be 4g/L～5g/L; Add containing Fe
3+and Fe
2+manganese sulfate solution after, the pH value of described reaction ore pulp is controlled at 3～3.5; The initial solid content of reaction ore pulp is 10%～12% before described absorption reaction, after absorption reaction completes in reaction product solid content below 3%;
(3) purify condensing crystal: the reaction product after above-mentioned absorption reaction is completed, after solid-liquid separation, deironing and heavy metal, then is carried out normal pressure condensing crystal, obtains manganese sulfate monohydrate.
2. the method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese according to claim 1, is characterized in that: described dioxide ore for manganese is to measure the natural manganese dioxide ore more than 40% containing Mn.
3. the method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese according to claim 1, it is characterized in that: in described step (1), the coarse particles mineral aggregate of ball milling, classification postprecipitation returns to described wet ball grinding step and proceeds follow-up technological process.
4. the method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese according to claim 1, is characterized in that: described high-temperature flue gas be after electrostatic precipitation temperature up to 140 DEG C～boiler smoke of 160 DEG C.
5. the method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese according to claim 1, it is characterized in that, the concrete steps of described deironing are: with manganese content more than 40%, granularity is less than the natural manganese dioxide breeze of 50 μ m and reaction product that pH value is adjusted to after 1.5～2.0 is carried out stirring reaction, steam heating to 90 DEG C～95 DEG C, after stirring reaction 40min～50min, make the pH value of reaction solution reach 5.2～5.6 with the neutralization of reduction manganese monoxide again, obtain manganese sulfate solution and the ferromanganese slag after deironing finally by solid-liquid separation.
6. the method with Manganse Dioxide ore pulp absorbing sulfur dioxide in flue extracting sulfuric acid manganese according to claim 5, is characterized in that: in described step (2) containing Fe
3+and Fe
2+manganese sulfate solution be to adopt dilute sulphuric acid to obtain after dissolving described ferromanganese slag.
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| CN105272386B (en) * | 2015-10-30 | 2018-11-02 | 灵丘县兴光矿业发展有限责任公司 | A method of utilizing the production potash magnesium sulphate fertilizer of dedusting ash containing manganese and manganese sulfate |
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| CN115522053B (en) * | 2022-08-23 | 2023-07-25 | 郴州金铖环保科技有限公司 | Method for recovering tin, tungsten and manganese from wolframite leaching slag |
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