CN113041838A - Method for cooperatively removing low-concentration sulfur dioxide and mercury in smelting flue gas - Google Patents
Method for cooperatively removing low-concentration sulfur dioxide and mercury in smelting flue gas Download PDFInfo
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- CN113041838A CN113041838A CN202110491190.1A CN202110491190A CN113041838A CN 113041838 A CN113041838 A CN 113041838A CN 202110491190 A CN202110491190 A CN 202110491190A CN 113041838 A CN113041838 A CN 113041838A
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 74
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003546 flue gas Substances 0.000 title claims abstract description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000003723 Smelting Methods 0.000 title claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000011574 phosphorus Substances 0.000 claims abstract description 51
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- 239000010452 phosphate Substances 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 27
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000002195 synergetic effect Effects 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 10
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002367 phosphate rock Substances 0.000 claims description 14
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 14
- 239000012990 dithiocarbamate Substances 0.000 claims description 11
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 229940077441 fluorapatite Drugs 0.000 claims description 2
- 229910052587 fluorapatite Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006477 desulfuration reaction Methods 0.000 abstract description 13
- 230000023556 desulfurization Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 229910000474 mercury oxide Inorganic materials 0.000 abstract 1
- 230000008569 process Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910010139 Li2MnTiO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner, and belongs to the field of industrial waste gas purification and solid waste recycling. Phosphorus tailings containing Mg2+、Al2+And Fe3+The transition metal ions with catalytic oxidation effect are added into the calcined phosphate tailings and MnO2Mixing, mixing with water to obtain phosphorus ore slurry, introducing flue gas containing low-concentration sulfur dioxide and mercury into the phosphorus ore slurry, and adding water into the mixture to remove mercury and sulfur dioxide0Are respectively catalytically oxidized into sulfuric acid and Hg2+(ii) a As the reaction proceeds, ascorbic acid and H are added to the slurry as the pH of the slurry drops to between 2 and 52O2Further improving the efficiency of desulfurization and demercuration and inhibiting Hg in the slurry2+Reducing and releasing. The method comprisesOnly improves the capability of the phosphorus tailings for synergistically removing low-concentration sulfur dioxide and mercury, and can inhibit Hg in slurry2+Reducing and releasing to ensure that the efficiency of cooperatively removing low-concentration sulfur dioxide from the phosphate tailings is over 98 percent, the efficiency of removing mercury is over 95 percent, and Hg is2+The reduction rate of (2) is 3% or less.
Description
Technical Field
The invention relates to a method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner, and belongs to the field of industrial waste gas purification and solid waste recycling.
Background
The smelting flue gas contains toxic and harmful substances such as sulfur dioxide, mercury and the like. The emission of sulfur dioxide into the atmosphere is not only harmful to human health, but also can cause serious damage to the ecological environment. For most smelters, high-concentration sulfur dioxide flue gas is usually converted into sulfuric acid by a contact method, the process is developed and mature, but a small amount of sulfur dioxide and mercury still exist in tail gas after acid making. The low-concentration sulfur dioxide flue gas cannot be directly used in the acid making process, only can be purified, and at present, lime method and ammonia method are generally adopted at home and abroad, so that the problems of secondary pollution and the like exist. The mercury in the flue gas has three forms, namely oxidized mercury (Hg)2+) Particulate mercury and elemental mercury (Hg)0). The mercury in oxidation state and particle state can be removed by dust removal, wet washing or adsorption method, while the elementary mercury not only has high content, about 80% of the total mercury in the flue gas, but also has stable property and is difficult to dissolve in water, and is easy to form global mercury pollution by long-distance transportation in the atmosphere, and the mercury is difficult to be effectively removed by conventional wet washing and chemical precipitation, which is the difficult point of flue gas demercuration. The adsorption method is the most mature flue gas demercuration technology at present, but the cost is too high, and large-scale industrialization is difficult to realize. At present, for removing sulfur dioxide and mercury in smelting flue gas, a limestone/gypsum method desulfurization and an adsorption method demercuration method are mostly adopted for graded serial removal, so that a process system is complex, the occupied area is large, and the operation cost is high. Therefore, the efficient and economic synergistic removal of the low-concentration sulfur dioxide and mercury in the smelting flue gas has important research value.
The phosphate tailings are produced and processed from raw oresThe by-products that remain. According to statistics, nearly 1000 ten thousand tons of phosphorus tailings are generated in China every year in recent years. P in these phosphate tailings2O5The content is low, the content of harmful impurities such as magnesium, calcium and the like is high, and the harmful impurities cannot be effectively developed and utilized and are accumulated in a large quantity, so that not only is the waste of land and mineral resources caused, but also the ecological environment is polluted. It has now been found that Mn2+、Fe3+、Cu2+、Al3+、Mg2+The transition metal ions have a certain catalytic oxidation effect. The phosphorus tailings contain Fe3+、Mg2+、Al3 +The transition metal ions are a potential secondary resource. The phosphate tailings are optimized and regulated to cooperatively remove SO in the flue gas2And Hg0Not only can fully utilize the phosphorus tailings as resources, but also can ensure that SO in the flue gas is utilized2And Hg0Effectively controlled, thereby achieving the purpose of treating wastes with processes of wastes against one another.
The patent No. 201611052373.9 'A method for desulfurizing and dearsenifying mercury by using slurry of tailings of copper smelting plant' proposes the use of tailings of copper smelting plant and H2O2The slurry prepared by the method and water is used for desulfurization and dearsenification of mercury, the method has low mercury removal efficiency, and H2O2The utilization rate is low, and only about 10 percent of H is contained in the slurry system2O2Decomposed, decomposed H2O2About 70% of the total are converted to O2Only about 15% of the radicals are converted into hydroxyl radicals; and Hg is present in the slurry2+The reduction is released again. Patent application No. 201611191914.6 entitled "A Li2MnTiO4Method for flue gas desulfurization and demercuration treatment' proposes to use Li2MnTiO4The mercury-free smoke gas is added into soft manganese ore powder to synergistically remove sulfur dioxide and mercury in smoke gas, and the method can effectively remove Hg0Oxidation to Hg2+However, Hg is converted by transition metal ions contained in the desulfurizing agent2+Reduction to Hg0Re-release to cause Hg in the outlet flue gas0The concentration of (c) increases. The above patents only consider how to efficiently remove Hg0Catalytic oxidation to Hg2+But are not effective in inhibiting Hg2+Reduction to Hg0To resumeRe-release, resulting in Hg in the outlet flue gas0The concentration increases and the mercury removal efficiency decreases. The invention mainly solves the problem of how to efficiently remove Hg in smoke0Catalytic oxidation to Hg2+And how to effectively suppress Hg in the slurry2+Reducing and releasing. The phosphate tailings mainly contain Fe3+、Mg2+、Al3+Transition metal ions of equal size, lack of Mn2+. In the invention, MnO is added2Adding into phosphate tailings, Mn2+Generates synergistic effect with Mg, Al, Fe and other ions, and can effectively remove Hg0Catalytic oxidation to Hg2+(ii) a After reacting for a period of time, the generated sulfuric acid largely leaches transition metal ions in the phosphate tailings, and ascorbic acid and H are added2O2At this time, there is about 60% of H2O2Decomposed, decomposed H2O2Only 10% of them are converted to O280% are converted to hydroxyl radicals, leaving H2O2Generate a large amount of hydroxyl free radicals, and can increase Hg0Catalytic oxidation to Hg2+While effectively inhibiting Hg in the slurry2+Reducing and releasing. Therefore, compared with the above patent, the invention has the following advantages: firstly, the invention can effectively inhibit Hg2+Reducing and releasing; the invention has higher efficiency of synergistic desulfurization and demercuration, H2O2The utilization rate of (2) is higher.
Disclosure of Invention
The invention aims to provide a method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner, wherein the phosphorus tailings mainly contain Mg2+、Al2+And Fe3+The transition metal ions with catalytic oxidation effect are added into the calcined phosphate tailings and MnO2Mixing, mixing with water to obtain phosphorus ore slurry, introducing the flue gas containing low-concentration sulfur dioxide and mercury into the phosphorus ore slurry for reaction, and adding ascorbic acid and H into the phosphorus ore slurry when pH value of the phosphorus ore slurry is reduced to 2-52O2Further improving the efficiency of desulfurization and demercuration. Final sulfur dioxide and Hg0Are respectively catalytically oxidized into sulfuric acid and Hg2+Thereby realizing the purpose of synergistic desulfurization and demercuration.
The invention is realized by the following technical scheme:
(1) crushing and grinding the phosphate tailings, and then calcining;
(2) MnO of2Adding the phosphorus tailings into the calcined phosphorus tailings powder, and mixing the phosphorus tailings powder with water to prepare phosphorus ore pulp;
(3) introducing flue gas containing low-concentration sulfur dioxide and mercury into phosphorite slurry, and adding ascorbic acid and H into the phosphorite slurry along with the reaction when the pH value of the phosphorite slurry is reduced to 2-52O2Carrying out reaction;
(4) after the reaction is finished, filtering the phosphorus tailing slurry, and adding Dithiocarbamate (DTCR) into the filtrate to ensure that Hg is absorbed2+Precipitate to inhibit its reduction and re-release.
Preferably, in the step (1) of the present invention, the phosphate tailings are composed of fluorapatite and dolomite, and the transition metal ion Mg in the phosphate tailings2+、Al2+And Fe3+The total content is 10-30%.
Preferably, in the step (1) of the invention, the phosphate tailings are crushed and ground to a particle size of 100-400 meshes, the calcination temperature is 800-1000 ℃, and the calcination time is 80-140 min.
Preferably, MnO in the step (2) of the present invention2The mass ratio of the added MnO (relative to the phosphate tailings) is 5-15 percent2The solid-liquid mass ratio of the mixture of the phosphate tailings and the water is 3-10%.
Preferably, the flow rate of the gas in the step (3) of the invention is 300-3The concentration of mercury is 30-50ug/m3The oxygen content is 2-20%, the removal rate of sulfur dioxide is more than or equal to 98%, the removal rate of mercury is more than or equal to 95%, and Hg in the slurry2+The reduction rate is less than or equal to 3 percent.
Preferably, the ascorbic acid is added in the step (3) in the invention in an amount of 0.01-2% by volume of the slurry, and H2O2In a concentration of 10% to 30%, H2O2The addition amount of (B) is 0.01-5% of the slurry volume.
Preferably, the dithio-ammonia is used in step (4) of the present inventionCarbamate (DTCR) salts such as Dithiocarbamates (DTCR) and Hg2+Is added in a stoichiometric ratio of 1: 1 to 5: 1.
The invention has the advantages and beneficial effects that:
(1) the phosphorus tailings are solid wastes, and the invention utilizes the phosphorus tailings to remove sulfur dioxide and mercury in the smelting flue gas in a synergic manner, thereby achieving the purpose of treating wastes with processes of wastes against one another and having high removal efficiency.
(2) The traditional desulfurization and demercuration method adopts a graded series connection method to remove mercury independently, the occupied area is large, the system is complex, the method combines a wet desulfurization system to remove mercury cooperatively, the occupied area is small, the system is simple, and the economic benefit is obvious.
(3) The invention calcines the phosphorus tailings, not only improves the reaction activity of the phosphorus tailings slurry, but also increases the surface porosity, obviously increases the specific surface area of the phosphorus tailings slurry, and effectively improves the desulfurization and demercuration performance of the phosphorus tailings slurry.
(4) The invention mixes the calcined phosphorus tailings and MnO2Mixing, preparing the mixture and water into slurry for synergistic desulfurization and demercuration, wherein Fe in the slurry3+And Mn2+Has synergistic effect, and improves the efficiency of the synergistic desulfurization and demercuration of the phosphorite slurry.
(5) The invention uses ascorbic acid and H2O2Added into the phosphorite slurry to generate a large amount of hydroxyl free radicals, thereby not only improving the efficiency of desulfurization and demercuration, but also inhibiting Hg in the phosphate tailing slurry2+The reduction is released again.
Detailed Description
The present invention is further described by the following specific examples, which are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation procedures are given, but the protection scope of the present invention is not limited to the following examples.
Example 1
In this example, the gas flow rate was 800ml/min, the reaction temperature was 25 ℃, and the concentration of sulfur dioxide in the flue gas was 1000mg/m3The concentration of mercury is 30ug/m3The oxygen content was 3%.
(1) Calcining the phosphate tailings with the granularity of 100 meshes at 800 ℃ for 100 min;
(2) MnO of2Adding the MnO into the calcined phosphorus tailings with the addition amount accounting for 5 percent of the mass of the phosphorus tailings2Preparing a slurry with the mixture of the phosphate tailings and water according to the solid-liquid mass ratio of 3%;
(3) introducing the flue gas into the phosphorus tailing slurry to remove sulfur dioxide and Hg0Are respectively catalytically oxidized into sulfuric acid and Hg2+Adding ascorbic acid and H into the phosphorite slurry when the pH value of the phosphorite slurry is reduced to 2-5 along with the reaction2O2Ascorbic acid added in an amount of 0.05% by volume of the slurry, H2O2In a concentration of 20%, H2O2The amount of (B) added was 0.5% by volume of the slurry.
(4) Filtering the phosphorus tailing slurry after the reaction is finished, and adding DTCR into the filtrate, wherein the DTCR is matched with Hg2+Is added in a stoichiometric ratio of 2: 1 to Hg2+Precipitate to inhibit its reduction and re-release.
By implementing the method, SO in the flue gas is discharged2≤20mg/m3Mercury is less than or equal to 1ug/m3Removal of Hg from the desulfurized and demercurated slurry2+The reduction rate is less than or equal to 3 percent.
Example 2
In this example, the gas flow rate was 600ml/min, the reaction temperature was 35 ℃, and the concentration of sulfur dioxide in the flue gas was 2000mg/m3The mercury concentration is 40ug/m3The oxygen content was 5%.
(1) Calcining the phosphate tailings with the granularity of 200 meshes at 900 ℃ for 120 min;
(2) MnO of2Adding the MnO into the calcined phosphorus tailings with the addition amount accounting for 10 percent of the mass of the phosphorus tailings2Preparing a slurry with the mixture of the phosphate tailings and water according to the solid-liquid mass ratio of 5%;
(3) introducing the flue gas into the phosphorus tailing slurry to remove sulfur dioxide and Hg0Are respectively catalytically oxidized into sulfuric acid and Hg2+Adding ascorbic acid and H into the phosphorite slurry when the pH value of the phosphorite slurry is reduced to 2-5 along with the reaction2O2Ascorbic acid added in an amount of 0.1% by volume of the slurry, H2O2In a concentration of 25%, H2O2Is added in an amount of 2% by volume of the slurry.
(4) Filtering the phosphorus tailing slurry after the reaction is finished, and adding DTCR into the filtrate, wherein the DTCR is matched with Hg2+Is added in an amount of 3: 1 to make Hg2+Precipitate to inhibit its reduction and re-release.
By implementing the method, SO in the flue gas is discharged2≤40mg/m3Mercury is less than or equal to 1ug/m3Removal of Hg from the desulfurized and demercurated slurry2+The reduction rate is less than or equal to 3 percent.
Example 3
In this example, the gas flow rate was 400ml/min, the reaction temperature was 45 ℃ and the concentration of sulfur dioxide in the flue gas was 3000mg/m3The concentration of mercury is 50ug/m3The oxygen content was 10%.
(1) Calcining the phosphate tailings with the granularity of 300 meshes at 1000 ℃ for 140 min;
(2) MnO of2Adding the MnO into the calcined phosphorus tailings with the addition amount accounting for 8 percent of the mass of the phosphorus tailings2Preparing a slurry with the mixture of the phosphate tailings and water according to the solid-liquid mass ratio of 10%;
(3) introducing the flue gas into the phosphorus tailing slurry to remove sulfur dioxide and Hg0Are respectively catalytically oxidized into sulfuric acid and Hg2+Adding ascorbic acid and H into the phosphorite slurry when the pH value of the phosphorite slurry is reduced to 2-5 along with the reaction2O2Ascorbic acid added in an amount of 0.8% by volume of the slurry, H2O2Concentration of (3%) H2O2Is added in an amount of 4% by volume of the slurry.
(4) Filtering the phosphorus tailing slurry after the reaction is finished, and adding DTCR into the filtrate, wherein the DTCR is matched with Hg2+Is added in a stoichiometric ratio of 4: 1 to Hg2+Precipitate to inhibit its reduction and re-release.
By implementing the method, SO in the flue gas is discharged2≤50mg/m3Mercury is less than or equal to 2ug/m3To take offHg in sulfur demercuration slurry2+The reduction rate is less than or equal to 3 percent.
Claims (7)
1. A method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner is characterized by comprising the following steps:
(1) crushing and grinding the phosphate tailings, and then calcining;
(2) MnO of2Adding the phosphorus tailings into the calcined phosphorus tailings powder, and mixing the phosphorus tailings powder with water to prepare phosphorus ore pulp;
(3) introducing flue gas containing low-concentration sulfur dioxide and mercury into phosphorite slurry, and adding ascorbic acid and H into the phosphorite slurry along with the reaction when the pH value of the phosphorite slurry is reduced to 2-52O2Carrying out reaction;
(4) filtering the phosphorus tailing slurry after the reaction is finished, and adding dithiocarbamate DTCR into the filtrate to ensure that Hg is absorbed2+Precipitate to inhibit its reduction and re-release.
2. The method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner according to claim 1, wherein the method comprises the following steps: the phosphate tailings in the step (1) consist of fluorapatite and dolomite, and transition metal ions Mg in the phosphate tailings2+、Al2+And Fe3+The total content is 10-30%.
3. The method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner according to claim 1, wherein the method comprises the following steps: in the step (1), the phosphate tailings are crushed and ground to the granularity of 100-.
4. The method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner according to claim 1, wherein the method comprises the following steps: MnO in step (2)2MnO accounting for 5-15 percent of the mass of the phosphate tailings2The solid-liquid mass ratio of the mixture of the phosphate tailings and the water is 3-10%.
5. The method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner according to claim 1, wherein the method comprises the following steps: the flow rate of the gas in the step (3) is 800ml/min for 300-3The concentration of mercury is 30-50ug/m3The oxygen content is 2-15%, the removal rate of sulfur dioxide after the reaction is finished is more than or equal to 98%, the removal rate of mercury is more than or equal to 95%, and Hg in the slurry2+The reduction rate is less than or equal to 3 percent.
6. The method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner according to claim 1, wherein the method comprises the following steps: the addition amount of the ascorbic acid in the step (3) is 0.01-2% of the volume of the slurry, and H2O2In a concentration of 10% to 30%, H2O2The addition amount of (B) is 0.01-5% of the slurry volume.
7. The method for removing low-concentration sulfur dioxide and mercury in smelting flue gas by using phosphorus tailings in a synergistic manner according to claim 1, wherein the method comprises the following steps: DTCR in step (4) is determined as DTCR and Hg2+Is added in a stoichiometric ratio of 1: 1 to 5: 1.
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