AU2021104221A4 - Method for improving desulfurization efficiency of electrolytic manganese ore/slag slurry - Google Patents
Method for improving desulfurization efficiency of electrolytic manganese ore/slag slurry Download PDFInfo
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- AU2021104221A4 AU2021104221A4 AU2021104221A AU2021104221A AU2021104221A4 AU 2021104221 A4 AU2021104221 A4 AU 2021104221A4 AU 2021104221 A AU2021104221 A AU 2021104221A AU 2021104221 A AU2021104221 A AU 2021104221A AU 2021104221 A4 AU2021104221 A4 AU 2021104221A4
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- electrolytic manganese
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- manganese ore
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- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 126
- 239000011572 manganese Substances 0.000 title claims abstract description 126
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002893 slag Substances 0.000 title claims abstract description 110
- 239000002002 slurry Substances 0.000 title claims abstract description 97
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 64
- 230000023556 desulfurization Effects 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 47
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 104
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003546 flue gas Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 47
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004064 recycling Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 4
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 4
- 239000011028 pyrite Substances 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 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 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 12
- 238000002386 leaching Methods 0.000 abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- 239000012066 reaction slurry Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000007613 slurry method Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali 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
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/73—After-treatment of removed components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present disclosure discloses a method for improving desulfurization efficiency of an electrolytic
manganese ore/slag slurry, where a new composite electrolytic manganese ore/slag slurry is prepared by
adding a certain amount of liquid ammonia and an ore powder of other type to an electrolytic
manganese ore/slag slurry. A flue gas containing sulfur dioxide is contacted in a reaction device
with the new composite electrolytic manganese ore/slag slurry for dispersion, thereby removing
sulfur dioxide in the flue gas. In the present disclosure, a multi-stage recycling of
desulfurization slurry is realized, which improves the desulfurization efficiency while saving the cost.
The ammonia addition process is adjusted forward to combine with the electrolytic manganese slurry for
desulfurization, so that the desulfurization effect of electrolytic manganese ore/slag slurry may be enhanced,
and the acid leaching solution after desulfurization may also be directly used for electrolysis
without adding electrolyte. The present disclosure increases the concentration of transition metal ions such
as Mn and Fe in the reaction slurry by using the manganese oxide ore, manganese carbonate
ore, pyrite, and the like as a promoter, enhancing the catalytic oxidation ability of system to convert
sulfur dioxide into an acid. The present disclosure has a short process flow, a desirable
desulfurization effect, and a notable economic benefit.
Description
[01] The present disclosure relates to the technical field of the treatment of sulfur-containing flue gas and the recycling of the electrolytic manganese ore/slag, in particular to a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry.
[02] As an important metallurgical and chemical raw material, manganese is mainly used in the fields of steel industry, national defense industry, chemical industry, light industry, building materials industry, electronics, agriculture and animal husbandry, medicine and environmental protection, and the like. China is rich in manganese ore resources, and 213 manganese mining areas with a total of 566 million tons of retained reserves are discovered to be distributed in 23 provinces, municipalities and autonomous regions. However, the reserves of poor manganese ore and slag account for 93.6% of the country's total reserves, which have a relatively low average grade of about 20% and are not fully utilized. As a by-product of industrial electrolysis of manganese, electrolytic manganese slag is a solid waste produced by acid leaching of manganese ore powder with sulfuric acid. However, China is mainly distributed with manganese ores with a relatively low average grade, where 3-10 tons of manganese slag will be discharged for producing 1 ton of electrolytic manganese, and the annual output of slag is about 10 million tons. On the one hand, the waste residue from acid leaching has a complex composition and a large discharge amount, and will seriously pollute the environment if being placed without necessary disposal. On the other hand, as a secondary resource, electrolytic manganese slag contains a relatively high amount of manganese, iron, aluminum and other elements, and may be used as a mixed material for cement production, a concrete admixture, an ash brick, a roadbed and a pavement material, and the like. Therefore, it is of great significance to realize the maximum recycling of electrolytic manganese slag. At present, extensive research has been carried out on the recycling of electrolytic manganese slag. Chinese patent application (CN 110482612A) discloses that an electrolytic manganese anode slag is calcined in a high-temperature calciner, a flue gas produced is absorbed by a modified manganese ore slurry, and the absorption slurry is further recovered by a manganese leaching process. However, this disclosure requires a high-temperature calcination and a high cost.
[03] Sulfur dioxide is one of the most common air pollutants. The burning of a sulfur-containing petroleum, coal and natural gas, the smelting and calcining of a sulfide ore, and the processing and production of various sulfur-containing raw materials may produce sulfur dioxide. The resulting acid rain pollution will lead to the acidification of a soil and water system, endanger the growth of animals and plants, severely damage the ecological environment, and bring huge economic losses to various countries. As the largest producer and consumer of coal in the world, China has a coal employment accounting for 75% of the total energy, and coal-fired flue gas discharge is the main source of sulfur dioxide pollution in China. At present, the main approaches to control sulfur dioxide include fuel desulfurization, combustion desulfurization and flue gas desulfurization, etc. Among them, the flue gas desulfurization is considered to be the most effective approach to control sulfur dioxide, mainly including a wet method, a semi-dry method, a dry method, and the like. As the most important and widely used method for purifying sulfur dioxide in flue gas, the wet method technology accounts for about 80% of the total treatment capacity, such as a limestone (lime)-gypsum method, a double-alkali method, a magnesium oxide method, an ammonia method, a seawater washing method and an ore slurry method, etc. The limestone-gypsum method has a large occupied area, and the by-product of gypsum has a high yield but a limited market and a low quality, and is easy to block the pipelines; the seawater washing method has geographical limitations and the risk of secondary pollution after being discharged to the sea. Therefore, it is of great significance to seek an efficient and economically beneficial treatment method of flue gas containing sulfur dioxide to control the air pollution. The ore slurry method is to mix a raw ore/slag with a particle size with a liquid such as water at a proportion, and contact sulfur dioxide with a concentration in a flue gas. The metal in the slurry is leached under acidic conditions, and the sulfur dioxide is absorbed by the slurry. This process effectively removes sulfur dioxide in the flue gas and recovers valuable metals by acid leaching, and the separated solid mixture may realize effective recycling after treatment. The use of electrolytic manganese ore/slag slurry for desulfurization may realize the recycling of valuable metals in the electrolytic manganese ore/slag, and remove sulfur dioxide from flue gas during acid leaching, so as to achieve the purpose of "treating waste with waste". At present, the electrolytic manganese ore/slag slurry method is used for desulfurization and acid leaching of valuable metal solutions, and metal manganese may be prepared by electrolysis. In order to promote the efficiency of electrolysis, aqua ammonia is mostly added as an electrolyte to the leached metal solution. Aqua ammonia is an alkaline substance, and currently the aqua ammonia-based desulfurization is also a common desulfurization method. Therefore, if the aqua ammonia addition process is adjusted forward to combine with the electrolytic manganese slurry for desulfurization, the desulfurization effect of electrolytic manganese ore/slag slurry may be enhanced. In addition, the acid leaching solution after desulfurization may also be directly used for electrolysis, without adding electrolyte. Chinese patent application (CN 205152076U) relates to an electrolytic manganese slag recycling system designed for treating an electrolytic manganese slag with a finely powdered form and a relatively high moisture. This system has a complicated operation, and has only a desulfurization efficiency of about 60% if no additional reducing agent is added. Chinese patent application (CN 105217580A) utilizes an electrolytic manganese slag to prepare sulfuric acid by the high-temperature desulfurization and enrichment of a flue gas. This disclosure requires, however, a relatively high temperature and a high cost. None of the above patent applications involve the enhanced desulfurization process as mentioned above.
[04] In view of the shortcomings in prior art regarding the sulfur-containing flue gas treatment and the recycling of electrolytic manganese ore/slag, the present disclosure aims to propose a new method for improving the desulfurization efficiency of an electrolytic manganese ore/slag slurry. The method realizes the combination of the flue gas desulfurization and the recycling of electrolytic manganese ore/slag, improves desulfurization efficiency and manganese resource utilization, and has a potential application prospect.
[05] The present disclosure provides a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry. A certain amount of liquid ammonia and an ore powder of other type are added to an electrolytic manganese ore/slag slurry according to a sulfur dioxide content in a flue gas to prepare a new composite electrolytic manganese ore/slag slurry, which is pumped into a reaction device. The flue gas containing sulfur dioxide contacts with the new composite electrolytic manganese ore/slag slurry in the reaction device for dispersion, thereby removing sulfur dioxide from the flue gas. The manganese sulfate solution generated by the oxidation-reduction reaction of sulfur dioxide with the electrolytic manganese ore/slag and the ore powder of other type may be purified to prepare a manganese sulfate product, and further to produce electrolytic manganese. On the one hand, ammonia is a desirable alkaline absorbent of sulfur dioxide, where ammonia and sulfur dioxide react through a gas-liquid contact to generate ammonium sulfite. The addition of a certain amount of liquid ammonia to the electrolytic manganese ore/slag slurry may stabilize the pH value of the reaction system. On the other hand, a certain amount of the ore powder of other type is added to the above system. Since the transition metal elements such as Mn and Fe in the ore powders have desirable catalytic oxidation ability, it is beneficial to improve the desulfurization efficiency. After the reaction, the processes of such as solid-liquid separation, concentrating, crystallizing and drying are conducted to realize product recycling.
[06] The present disclosure provides a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry, specifically including the following steps: (1) preparing, in a ratio, a new composite electrolytic manganese ore/slag slurry including an electrolytic manganese ore/slag slurry, liquid ammonia and an ore powder of other type according to a content of sulfur dioxide in a flue gas; (2) pumping the new composite electrolytic manganese ore/slag slurry obtained in step (1) into an absorption reaction device, and contacting with the flue gas containing sulfur dioxide for dispersion to remove sulfur dioxide in the flue gas; (3) subjecting a reaction product obtained in step (2) to a solid-liquid separation, purifying, then concentrating, crystallizing and drying to realize product recycling.
[07] In some embodiments, the flue gas in step (1) may be one or a mixture of two selected from the group consisting of a metal smelting tail gas and an environmental set smoke flue gas.
[08] In some embodiments, the electrolytic manganese ore/slag slurry in step (1) may be prepared by mixing an electrolytic manganese ore/slag and water in a solid-to-liquid mass ratio of 1:(6-10).
[09] In some embodiments, the electrolytic manganese ore/slag and the ore powder of other type in step (1) may both be crushed, ground and sieved, with a particle size of < 0.18 mm (80 mesh).
[10] In some embodiments, the ore powder of other type in step (1) may be one or more selected from the group consisting of a manganese oxide ore powder, a manganese carbonate ore powder, a pyrite powder, a red mud powder, a phosphorus ore powder, a magnesium ore powder, a lead-zinc ore powder and a copper ore powder, with a total amount of 4% to 21% of the mass of the electrolytic manganese ore/slag.
[11] In some embodiments, the reaction device in step (2) may be composed of an one-stage absorption reaction device or multi-stage absorption reaction devices, each absorption reaction device may be equipped independently with a circulation pump and a circulation pool for slurry absorption, and the flue gas containing sulfur dioxide may be introduced from a first-stage absorption reaction device and discharged from a last-stage absorption reaction device.
[12] In some embodiments, in the absorption reaction device in step (2), a reaction temperature may be within a range of 20-60°C, and the new composite electrolytic manganese ore/slag slurry may have a pH value of 4.0-6.5, being adjusted by liquid ammonia during the reaction.
[13] In some embodiments, sulfur dioxide in the flue gas in step (2) may have a concentration of no more than 3,000 mg/m 3 .
[14] In some embodiments, the flue gas in step (2) may have a retention time of 5-30 s.
[15] In some embodiments, after the reaction in step (3), manganese sulfate and ferric sulfate may be obtained via treatment, being further used as an electrolyte in a process of electrolytic manganese.
[16] The beneficial effects of the present disclosure are as follows:
[17] (1) The present disclosure employs a new composite electrolytic manganese ore/slag slurry prepared from an electrolytic manganese ore/slag slurry, liquid ammonia and an ore powder of other type to remove sulfur dioxide in a flue gas, where the removal efficiency of sulfur dioxide is greater than 90%. The desulfurization efficiency of the composite electrolytic manganese ore/slag slurry is superior to that of a single ore slurry.
[18] (2) In the present disclosure, a multi-stage recycling of desulfurization slurry during reaction is realized, which improves the desulfurization efficiency while saving the cost.
[19] (3) The present disclosure uses liquid ammonia as an auxiliary absorbent of sulfur dioxide and a pH stabilizer. At present, the electrolytic manganese ore/slag slurry method is used for desulfurization and acid leaching of valuable metal solutions, and metal manganese may be prepared
A by electrolysis. In order to promote the efficiency of electrolysis, aqua ammonia is mostly added as an electrolyte to the leached metal solution. Aqua ammonia is an alkaline substance, and currently the aqua ammonia-based desulfurization is also a common desulfurization method. Therefore, if the aqua ammonia addition process is adjusted forward to combine with the electrolytic manganese slurry for desulfurization, the desulfurization effect of electrolytic manganese ore/slag slurry may be enhanced. In addition, the acid leaching solution after desulfurization may also be directly used for electrolysis, without adding electrolyte.
[20] (4) The present disclosure does not require an additional acid leaching solution, but rather promotes the leaching of metal elements in the electrolytic manganese ore/slag slurry and ores and produces sulfuric acid by dissolving sulfur dioxide in the flue gas into the ore slurry, thereby realizing "treating waste with waste".
[21] (5) The present disclosure increases the concentration of transition metal ions such as Mn and Fe in the reaction slurry by using the manganese oxide ore, manganese carbonate ore, pyrite, and the like as a promoter, enhancing the catalytic oxidation ability of system to convert sulfur dioxide into an acid.
[22] (6) The present disclosure has a high desulfurization efficiency, a simple process and a low cost, and realizes the recycling of resources such as the electrolytic manganese ore/slag, metal ore and sulfur dioxide. The manganese sulfate, ferric sulfate and the like obtained after reaction and treatment may be further used as an electrolyte in the process of electrolytic manganese, so as to realize the recycling of reaction products.
[23] (7) The present disclosure has a short process flow, a desirable desulfurization effect, and a notable economic benefit.
[24] The present disclosure is further described below in combination with embodiments, and is not to be limited in any way. Any modification or replacement based on the teachings of the present disclosure falls within the protection scope of the present disclosure.
[25] Example 1
[26] The example describes a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry, and the specific steps are as follows:
[27] (1) An electrolytic manganese ore/slag and a manganese oxide ore were crushed, ground and sieved to a particle size of 200 mesh. The electrolytic manganese ore/slag was uniformly mixed with water in a solid-liquid mass ratio of 1:6 to prepare an electrolytic manganese ore/slag slurry. Liquid ammonia and the manganese oxide ore powder were added to the electrolytic manganese ore/slag slurry (the ore powder was added at 4% of the mass of the electrolytic manganese ore/slag powder) and mixed uniformly to prepare a new composite electrolytic manganese ore/slag slurry.
[28] (2) The new composite electrolytic manganese ore/slag slurry obtained in step (1) was pumped into an absorption reaction device, and was contacted with a flue gas having a sulfur dioxide concentration of 3,000 mg/m3 for dispersion. The slurry was adjusted to have a pH of 6.5, the reaction was conducted at a temperature of 20°C, and the flue gas had a retention time of 5 s. The reaction device was composed of an one-stage absorption reaction device or multi-stage absorption reaction devices, and each absorption reaction device was equipped independently with a circulation pump and a circulation pool for slurry absorption. The flue gas containing sulfur dioxide was introduced from a first-stage absorption reaction device and discharged from a last-stage absorption reaction device, and the excess slurry was collected.
[29] (3) The final reaction slurry obtained in step (2) was subjected to solid-liquid separation and purified, followed by concentrated, crystallized and dried to realize product recycling.
[30] In this example, the gas after desulfurization had a sulfur dioxide concentration of 99mg/m 3
, and the desulfurization efficiency was 96.7%, complying with GB-26132-2010.
[31] Example 2
[32] The example describes a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry, and the specific steps are as follows:
[33] (1) An electrolytic manganese ore/slag and a manganese oxide ore were crushed, ground and sieved to a particle size of 200 mesh. The electrolytic manganese ore/slag powder was uniformly mixed with water in a solid-liquid mass ratio of 1:7 to prepare an electrolytic manganese ore/slag slurry. Liquid ammonia and the manganese oxide ore powder were added to the electrolytic manganese ore/slag slurry (where the ore powder was added at 10% of the mass of the electrolytic manganese ore/slag powder) and mixed uniformly to prepare a new composite electrolytic manganese ore/slag slurry.
[34] (2) The new composite electrolytic manganese ore/slag slurry obtained in step (1) was pumped into an absorption reaction device, and was contacted with a flue gas having a sulfur dioxide concentration of 2960 mg/m3 for dispersion. The slurry pH was adjusted to have a pH of 6.0, the reaction was conducted at a temperature of 30°C, and the flue gas had a retention time of 10 s. The reaction device was composed of an one-stage absorption reaction device or multi-stage absorption reaction devices, and each absorption reaction device was equipped independently with a circulation pump and a circulation pool for slurry absorption. The flue gas containing sulfur dioxide was introduced from a first-stage absorption reaction device and discharged from a last-stage absorption reaction device, and the excess slurry was collected.
[35] (3) The final reaction slurry obtained in step (2) was subjected to solid-liquid separation and purified, followed by concentrated, crystallized, and dried to realize product recycling.
[36] In this example, the gas after desulfurization in this example has a sulfur dioxide concentration of 52mg/m 3, and the desulfurization efficiency was 98.2%,complying with
GB-26132-2010.
[37] Example 3
[38] The example describes a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry, and the specific steps are as follows:
[39] (1) An electrolytic manganese ore/slag and a manganese oxide ore were crushed, ground and sieved to a particle size of 180 mesh. The electrolytic manganese ore/slag was uniformly mixed with water in a solid-liquid mass ratio of 1:8 to prepare an electrolytic manganese ore/slag slurry. Liquid ammonia and the manganese oxide ore powder were added to the electrolytic manganese ore/slag slurry (the ore powder was added at 15% of the mass of the electrolytic manganese ore/slag powder) and mixed uniformly to prepare a new composite electrolytic manganese ore/slag slurry.
[40] (2) The new composite electrolytic manganese ore/slag slurry obtained in step (1) was pumped into an absorption reaction device, and was contacted with a flue gas having a sulfur dioxide concentration of 2820 mg/m3 for dispersion. The slurry was adjusted to have a pH of 5.5, the reaction was conducted at a temperature of 35°C, and the flue gas had a retention time of 12 s. The reaction device was composed of an one-stage absorption reaction device or multi-stage absorption reaction devices, and each absorption reaction device was equipped independently with a circulation pump and a circulation pool for slurry absorption. The flue gas containing sulfur dioxide was introduced from a first-stage absorption reaction device and discharged from a last-stage absorption reaction device, and the excess slurry was collected.
[41] (3) The final reaction slurry obtained in step (2) was subjected to solid-liquid separation and purified, followed by concentrated, crystallized and dried to realize product recycling.
[42] In this example, the gas after desulfurization had a sulfur dioxide concentration of 67mg/m 3
, and the desulfurization efficiency was 97.6%, complying with GB-26132-2010.
[43] Example 4
[44] The example describes a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry, and the specific steps are as follows:
[45] (1) An electrolytic manganese ore/slag and a manganese oxide ore were crushed, ground and sieved to a particle size of 180 mesh. The electrolytic manganese ore/slag was uniformly mixed with water in a solid-liquid mass ratio of 1:9 to prepare an electrolytic manganese ore/slag slurry. Liquid ammonia and the manganese oxide ore powder were added to the electrolytic manganese ore/slag slurry (the ore powder was added at 18% of the mass of the electrolytic manganese ore/slag powder) and mixed uniformly to prepare a new composite electrolytic manganese ore/slag slurry.
[46] (2) The new composite electrolytic manganese ore/slag slurry obtained in step (1) was pumped into an absorption reaction device, and was contacted with a flue gas having a sulfur dioxide concentration of 2913 mg/m3 for dispersion. The slurry was adjusted to have a pH of 5.0, the reaction was conducted at a temperature of 40°C, and the flue gas had a retention time of 15 s. The reaction device was composed of an one-stage absorption reaction device or multi-stage absorption reaction devices, and each absorption reaction device was equipped independently with a circulation pump and a circulation pool for slurry absorption. The flue gas containing sulfur dioxide was introduced from a first-stage absorption reaction device and discharged from a last-stage absorption reaction device, and the excess slurry was collected.
[47] (3) The final reaction slurry obtained in step (2) was subjected to solid-liquid separation and purified, followed by concentrated, crystallized and dried to realize product recycling.
[48] In this example, the gas after desulfurization had a sulfur dioxide concentration of 67mg/m 3
, and the desulfurization efficiency was 97.6%, complying with GB-26132-2010.
[49] Example 5
[50] The example describes a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry, and the specific steps are as follows:
[51] (1) An electrolytic manganese ore/slag and a manganese oxide ore were crushed, ground and sieved to a particle size of 80 mesh. The electrolytic manganese ore/slag was uniformly mixed with water in a solid-liquid mass ratio of 1:10 to prepare an electrolytic manganese ore/slag slurry. Liquid ammonia and the manganese oxide ore powder were added to the electrolytic manganese ore/slag slurry (the ore powder was added at 19% of the mass of the electrolytic manganese ore/slag powder) and mixed uniformly to prepare a new composite electrolytic manganese ore/slag slurry.
[52] (2) The new composite electrolytic manganese ore/slag slurry obtained in step (1) was pumped into an absorption reaction device, and was contacted with a flue gas having a sulfur dioxide concentration of 2357 mg/m3 for dispersion. The slurry was adjusted to have a pH of 4.5, the reaction was conducted at a temperature of 50°C, and the flue gas had a retention time of 20 s. The reaction device was composed of an one-stage absorption reaction device or multi-stage absorption reaction devices, and each absorption reaction device was equipped independently with a circulation pump and a circulation pool for slurry absorption. The flue gas containing sulfur dioxide was introduced from a first-stage absorption reaction device and discharged from a last-stage absorption reaction device, and the excess slurry was collected.
[53] (3) The final reaction slurry obtained in step (2) was subjected to solid-liquid separation and purified, followed by concentrated, crystallized and dried to realize product recycling.
[54] In this example, the gas after desulfurization had a sulfur dioxide concentration of 70mg/m 3 ,
and the desulfurization efficiency was 97.0%, complying with GB-26132-2010.
[55] Example 6
[56] The example describes a method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry, and the specific steps are as follows:
[57] (1) An electrolytic manganese ore/slag and a manganese oxide ore were crushed, ground and sieved to a particle size of 80 mesh. The electrolytic manganese ore/slag was uniformly mixed with
Q water in a solid-liquid mass ratio of 1:10 to prepare an electrolytic manganese ore/slag slurry. Liquid ammonia and the manganese oxide ore powder were added to the electrolytic manganese ore/slag slurry (the ore powder was added at 21% of the mass of the electrolytic manganese ore/slag powder) and mixed uniformly to prepare a new composite electrolytic manganese ore/slag slurry.
[58] (2) The new composite electrolytic manganese ore/slag slurry obtained in step (1) was pumped into an absorption reaction device, and was contacted with a flue gas having a sulfur dioxide concentration of 2466 mg/m3 for dispersion. The slurry was adjusted to have a pH of 4.0, the reaction was conducted at a temperature of 60°C, and the flue gas had a retention time of 30 s. The reaction device was composed of an one-stage absorption reaction device or multi-stage absorption reaction devices, and each absorption reaction device was equipped independently with a circulation pump and a circulation pool for slurry absorption. The flue gas containing sulfur dioxide was introduced from a first-stage absorption reaction device and discharged from a last-stage absorption reaction device, and the excess slurry was collected.
[59] (3) The final reaction slurry obtained in step (2) was subjected to solid-liquid separation and purified, followed by concentrated, crystallized and dried to realize product recycling.
[60] In this example, the gas after desulfurization had a sulfur dioxide concentration of 98mg/m 3
, and the desulfurization efficiency was 96.0%, complying with GB-26132-2010.
Claims (5)
1. A method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry, specifically comprising the following steps:
(1) preparing a composite electrolytic manganese ore/slag slurry comprising an electrolytic manganese ore/slag slurry, liquid ammonia and an ore powder of other type according to a content of sulfur dioxide in a flue gas;
(2) pumping the composite electrolytic manganese ore/slag slurry obtained in step (1) into an absorption reaction device, and contacting with the flue gas containing sulfur dioxide for dispersion to remove sulfur dioxide in the flue gas;
(3) subjecting a reaction product obtained in step (2) to a solid-liquid separation, purifying, then concentrating, crystallizing and drying to realize product recycling.
2. The method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry according to claim 1, wherein the electrolytic manganese ore/slag slurry in step (1) is prepared by mixing an electrolytic manganese ore/slag and water in a solid-to-liquid mass ratio of 1:(6-10).
3. The method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry according to claim 1, wherein the ore powder of other type in step (1) is one or more selected from the group consisting of a manganese oxide ore powder, a manganese carbonate ore powder, a pyrite powder, a red mud powder, a phosphorus ore powder, a magnesium ore powder, a lead-zinc ore powder and a copper ore powder, with a total amount of 4% to 21% of the mass of the electrolytic manganese ore/slag.
4. The method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry according to claim 1, wherein the composite electrolytic manganese ore/slag slurry in the absorption reaction device in step (2) has a pH value of 4.0-6.5 and a temperature of 20-60°C during the reaction.
5. The method for improving desulfurization efficiency of an electrolytic manganese ore/slag slurry according to claim 1, wherein after the reaction in step (3), manganese sulfate and ferric sulfate are obtained via treatment, being further used as an electrolyte in a process of electrolytic manganese.
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| CN114749008B (en) * | 2022-05-16 | 2023-12-15 | 昆明理工大学 | MgCl utilization 2 Strengthening dealkalization and SO absorption of red mud 2 And method for utilizing ore pulp |
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