CN105688647A - Method for dry desulfurization and demercuration of sintering flue gas containing mercury by means of low-grade pyrolusite - Google Patents
Method for dry desulfurization and demercuration of sintering flue gas containing mercury by means of low-grade pyrolusite Download PDFInfo
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- 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
- B01D53/81—Solid phase processes
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- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- 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
- B01D53/508—Sulfur oxides by treating the gases with solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- 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
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/12—Methods and means for introducing reactants
- B01D2259/128—Solid reactants
Abstract
The invention discloses a method for dry desulfurization and demercuration of sintering flue gas containing mercury by means of low-grade pyrolusite. The method comprises the steps that 1, the low-grade pyrolusite is obtained and placed in a reactor; 2, dedusting is conducted on the sintering flue gas to remove dust containing sulfur and mercury in the sintering flue gas, then the dedusted sintering flue gas with the temperature of 100-200 DEG C is introduced into the reactor at the flow rate of 1-8 L/min to enable the sintering flue gas to make contact with the low-grade pyrolusite, SO2 in the sintering flue gas reacts with the low-grade pyrolusite to achieve desulfurization, and residual mercury in the sintering flue gas is adsorbed by pyrolusite to achieve demercuration; 3, the sintering flue gas subjected to desulfurization and demercuration is directly discharged through an exhaust port of the reactor. The method has the advantages that desulfurization and demercuration cost is low, desulfurization and demercuration efficiency is high, the process is simple, and the recovery rate of byproducts is high.
Description
Technical field
The present invention relates to a kind of a kind of method sintering flue gas dry desulfurizing demercuration, the particularly low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration。
Background technology
The SO of current China2Discharge capacity has occupied the first in the world, and China has had become as big Acid Rain Zone, the world the 3rd, every year because acid rain loss is exceeded 100 billion, and sinters the SO in flue gas2Being one of main source causing acid rain, meanwhile, air is caused severe contamination by some mercurous sintering flue gases especially。But it is main for being still flue gas desulfurization in a wet process both at home and abroad at present, and wet method accounts for 85%, and (desulfurization technology in a wet process is such as Japan of major country, and wet method accounts for 98%；The U.S. accounts for 92%；Germany accounts for 90%。), it is common to employing is limestone-gypsum method and sodium alkali etc., but the investment of the method and operating cost are high, the easy fouling and clogging of system, and desulfuration byproduct price is low, and waste residue using value is little, easily causes secondary pollution, and economic benefit is inconspicuous。Along with various countries are more strict to environmental requirement, and the development of science and technology and research are constantly deeply, and the wet method of parts of traditional is substituted by novel wet method, semidry method and dry desulfurizing process gradually。And the mode of flue gas demercuration mainly have burning before demercuration, burning in demercuration and burning after demercuration three kinds。Demercuration in comparing before burning and burning, after burning, demercuration is a kind of effective and feasible coal-fired flue gas mercury removal approach。Researcheres propose the control technology of various hydrargyrum, mainly have cleaner demercuration technology, adsorbent demercuration technology, catalytic oxidation technologies, wet process of FGD (FGD) device demercuration technology, solution absorption method demercuration technology and some other demercuration technology。At present, but without a ripe Mercury vacancy technology, it is in flue gas, spray into activated carbon granule demercuration closest to wide variety of technology, before FF or ESP, spray into activated carbon or modified activated carbon can efficiently control the discharge of gas mercury, but owing to activated carbon is expensive, it is restricted in popularization and application。Due to the easy blocked inactivation of wet method class adsorbent, the regeneration difficulty of adsorbent, causing cost to increase, dry method will more be favored。
China's low-grade pyrolusite aboundresources, domestic scholars is starched desulfuration demercuration for low-grade pyrolusite and has been carried out substantial amounts of research, but low-grade pyrolusite slurry desulfuration demercuration exists problems。Main manifestations is following several situation, and gas-liquid-solid phase reaction is sufficiently complex, and desulfurization degree is difficult to control to, and in low-grade pyrolusite slurry, impurity can react with intermediate product and be unfavorable for desulfurization, by-product manganous dithionate (MnS2O6) decomposition can produce SO2Secondary pollution problem, meanwhile, the space on low-grade pyrolusite surface is easily resulted in blockage by the dust granules in sintering flue gas, reduces the adsorption efficiency to hydrargyrum。Up to now, rarely has the relevant open report to low-grade pyrolusite dry flue gas desulphurization demercuration both at home and abroad。
Summary of the invention
It is an object of the invention to, it is provided that a kind of low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration。The present invention has the advantages that desulfuration demercuration cost is low, desulfuration demercuration efficiency high, technique is simple, by-product recovery rate is high。
Technical scheme: a kind of low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, comprises the steps:
(1) take low-grade pyrolusite, low-grade pyrolusite is put in reactor；
(2) sintering flue gas is first carried out dust removal process, remove the mercurous dust of sulfur-bearing in sintering flue gas, then the temperature after dedusting is passed in reactor at the sintering flue gas of 100-200 DEG C with the flow velocity of 1-8L/min, make sintering flue gas contact with low-grade pyrolusite, sinter the SO in flue gas2React with low-grade pyrolusite, complete desulfurization；Meanwhile, in sintering flue gas, remaining hydrargyrum is adsorbed by pyrolusite, completes demercuration；
(3) the sintering flue gas after desulfuration demercuration is directly discharged from the air vent of reactor。
The aforesaid low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, described dust removal process is to be passed in sack cleaner or electrostatic precipitator by sintering flue gas。
The aforesaid low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, in described step (1), low-grade pyrolusite also needs to pulverize when using, and obtains low-grade pyrolusite powder, and the size of low-grade pyrolusite powder is 60-180 order。
The aforesaid low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, the size of described low-grade pyrolusite powder is 140-160 order。
The aforesaid low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, in described step (2), it is 3-4L/min that sintering flue gas passes into the flow velocity in reactor。
The aforesaid low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, in described step (2), the temperature of sintering flue gas controls at 110-130 DEG C。
The aforesaid low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, described reactor is fixed bed reactors or fluidized-bed reactor。
The aforesaid low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, by described step (2), SO2The solid reactant being obtained by reacting with low-grade pyrolusite puts into normal-temperature water immersion, and filters。
Beneficial effects of the present invention:
(1) present invention is by making full use of China's low-grade pyrolusite, directly utilizes low-grade pyrolusite and is sintered flue gas dry desulfurizing demercuration, greatly reduces desulfuration demercuration cost；
(2) present invention is carried out dust removal process also by before passing into reactor at sintering flue gas, first the sulfur in dust and hydrargyrum are removed, simultaneously, it is to avoid in sintering flue gas, space to the covering on low-grade pyrolusite surface and is resulted in blockage and reduces SO by dust2With the response area of low-grade pyrolusite, further increase the efficiency of desulfurization, and promoted that the hydrargyrum in sintering flue gas enters in the space on pyrolusite surface, improve demercuration efficiency；
(3) present invention is by pulverizing low-grade pyrolusite, adds the specific surface area of low-grade pyrolusite powder, increases sintering flue gas and the contact area of low-grade pyrolusite powder, too increases the porosity on the surface of low-grade pyrolusite powder simultaneously, make SO2It is easier to contact with the surface of low-grade pyrolusite powder, improve the efficiency of desulfurization, also promote the pyrolusite powder adsorption effect to hydrargyrum, simultaneously, the flow velocity of desulfurization reactor is passed into by controlling sintering flue gas, avoid flow velocity to be blown away by low-grade pyrolusite powder too soon, also avoid causing response speed slow too slowly and affecting desulfuration efficiency；
(4) compared with existing Wet Flue Gas Desulfurization Technique, the low-grade pyrolusite powder of pulverizing only need to be put into reactor and react can realize desulfuration demercuration with the sintering flue gas after dedusting by the present invention, and technique is simpler；
(5) the low-grade pyrolusite powder of the present invention and SO2Forming solid reactant after reaction, only need to be put into by this solid reactant and soak in normal-temperature water and filter, can be reclaimed by the by-product (manganese sulfate) of desulfurization, the response rate is higher。
For further illustrating beneficial effects of the present invention, applicant has done following experiment:
Experimental example 1
Adopt the low-grade pyrolusite 20g of 80-120 order, put into fixing desulfurization reactor, will containing SO2Concentration provides Elemental Mercury initial concentration to be maintained at 50 μm/m for 3000ppm with by hydrargyrum osmos tube3Import flue gas pass in desulfurizing tower reactor, control flue gas flow is 4L/min, and smoke reaction temperature controls at 120 DEG C。SO in the flue gas of exit is detected by flue gas analyzer2Concentration is 272mg/m3, desulfuration efficiency can reach 74%；Elemental mercury concentration measured by hydrargyrum in-line analyzer is 21.3 μm/m3, demercuration efficiency is 57.4%。
Experimental example 2
Adopt the low-grade pyrolusite 20g of 80-120 order, put into fixing desulfurization reactor, will containing SO2Concentration provides Elemental Mercury initial concentration to be maintained at 50 μm/m for 3000ppm with by hydrargyrum osmos tube3Import flue gas carry out dust removal process, then pass in desulfurizing tower tower reactor, control flue gas flow is 4L/min, and smoke reaction temperature controls at 120 DEG C。SO in the flue gas of exit is detected by flue gas analyzer2Concentration is 272mg/m3, desulfuration efficiency can reach 74%；Elemental mercury concentration measured by hydrargyrum in-line analyzer is 16.65 μm/m3, demercuration efficiency is 66.7%。
Example 1-2 is it can be seen that when other experiment conditions are consistent, the desulfuration demercuration efficiency of the sintering flue gas after removing dust process all increases by experiment, and particularly demercuration efficiency has brought up to 66.7% from 57.4%, improve 9.3%。
Experimental example 3
Adopt the low-grade pyrolusite 15g of 60-80 order, put into fixing desulfurization reactor, will containing SO2The sintering flue gas that concentration is 3000ppm passes in desulfurizing tower tower reactor, and control flue gas flow is 3L/min, and smoke reaction temperature controls at 120 DEG C。
SO in the flue gas of exit is detected by flue gas analyzer2Concentration 303mg/m3, desulfuration efficiency can reach 71%。
Experimental example 4
Adopt the low-grade pyrolusite 15g of 80-100 order, put into fixing desulfurization reactor, will containing SO2The sintering flue gas that concentration is 3000ppm passes in desulfurizing tower tower reactor, and control flue gas flow is 3L/min, and smoke reaction temperature controls at 120 DEG C。
SO in the flue gas of exit is detected by flue gas analyzer2Concentration 272mg/m3, lower than 300mg/m3, desulfuration efficiency can reach 74%。
Experimental example 5
Adopt the low-grade pyrolusite 15g of 100-120 order, put into fixing desulfurization reactor, will containing SO2The sintering flue gas that concentration is 3000ppm passes in desulfurizing tower tower reactor, and control flue gas flow is 3L/min, and smoke reaction temperature controls at 120 DEG C。
SO in the flue gas of exit is detected by flue gas analyzer2Concentration 251mg/m3, lower than 300mg/m3, desulfuration efficiency can reach 76%。
Experimental example 6
Adopt the low-grade pyrolusite 15g of 120-140 order, put into fixing desulfurization reactor, will containing SO2The sintering flue gas that concentration is 3000ppm passes in desulfurizing tower tower reactor, and control flue gas flow is 3L/min, and smoke reaction temperature controls at 120 DEG C。
SO in the flue gas of exit is detected by flue gas analyzer2Concentration 241g/m3, lower than 300mg/m3, desulfuration efficiency can reach 77%。
Experimental example 7
Adopt the low-grade pyrolusite 15g of 140-160 order, put into fixing desulfurization reactor, will containing SO2The sintering flue gas that concentration is 3000ppm passes in desulfurizing tower tower reactor, and control flue gas flow is 3L/min, and smoke reaction temperature controls at 120 DEG C。
SO in the flue gas of exit is detected by flue gas analyzer2Concentration 230mg/m3, lower than 300mg/m3, desulfuration efficiency can reach 78%。
Experimental example 8
Adopt the low-grade pyrolusite 15g of 160-180 order, put into fixing desulfurization reactor, will containing SO2The sintering flue gas that concentration is 3000ppm passes in desulfurizing tower tower reactor, and control flue gas flow is 3L/min, and smoke reaction temperature controls at 120 DEG C。
SO in the flue gas of exit is detected by flue gas analyzer2Concentration 253mg/m3, lower than 300mg/m3, desulfuration efficiency reaches 76%。
From experimental example 3-8 it can be seen that work as the weight of low-grade pyrolusite, the type of desulfurization reactor, SO in flue gas2Content, when the condition such as the flow of flue gas and reaction temperature is all consistent, along with the granularity of low-grade pyrolusite powder is increasingly thinner, desulfuration efficiency is more and more higher, this is because low-grade pyrolusite powder is more thin, with SO in flue gas2The specific surface area of reaction is just increasing, improves desulfuration efficiency；After the order number of low-grade pyrolusite powder is more than 14-160, desulfuration efficiency begins to decline, this is because the flue gas passed into has certain flow velocity, flue gas can take away a part of low-grade pyrolusite powder, decrease the quantity of the low-grade pyrolusite powder participating in reaction, thus affecting the efficiency of desulfurization；Therefore, from the result of experimental example 1-6 it can be seen that the desulfuration efficiency tool of sintering flue gas is had a certain impact by the order number of low-grade pyrolusite powder, when order number desulfuration efficiency when 140-160 is best。
Detailed description of the invention
Embodiments of the invention
Embodiment 1:
The method of a kind of low-grade pyrolusite sintering flue gas dry desulfurizing, comprises the steps:
(1) low-grade pyrolusite is taken；
(2) low-grade pyrolusite in step (1) is put in fixing bed desulfurization reactor；
(3) temperature is passed into electrostatic precipitator at the sintering flue gas of 110-130 DEG C and carry out dedusting, then pass in fixing bed desulfurization reactor with the flow velocity of 3-4L/min, make sintering flue gas contact with low-grade pyrolusite powder, SO therein2React with low-grade pyrolusite, complete desulfurization；
(4) the sintering flue gas after desulfurization is directly discharged from the air vent of desulfurization reactor。
Embodiment 2:
The method of a kind of low-grade pyrolusite sintering flue gas dry desulfurizing, comprises the steps:
(1) take low-grade pyrolusite, be milled to 140-160 order, obtain low-grade pyrolusite powder；
(2) the low-grade pyrolusite powder obtained in step (1) is put in fixing bed desulfurization reactor；
(3) temperature is passed into electrostatic precipitator at the sintering flue gas of 100-110 DEG C and carry out dedusting, then pass in fixing bed desulfurization reactor with the flow velocity of 1-2L/min, make sintering flue gas contact with low-grade pyrolusite powder, SO therein2React with low-grade pyrolusite, complete desulfurization, SO2The solid product obtained after reacting with low-grade pyrolusite is put into normal-temperature water and is soaked, and obtains manganese sulfate；
(4) the sintering flue gas after desulfurization is directly discharged from the air vent of desulfurization reactor。
Embodiment 3:
The method of a kind of low-grade pyrolusite sintering flue gas dry desulfurizing, comprises the steps:
(1) take low-grade pyrolusite, be milled to 60-100 order, obtain low-grade pyrolusite powder；
(2) the low-grade pyrolusite powder obtained in step (1) is put in fluid-bed sweetening reactor；
(3) temperature is passed into sack cleaner at the sintering flue gas of 130-140 DEG C and carry out dedusting, then pass in fluid-bed sweetening reactor with the flow velocity of 2-3L/min, make sintering flue gas contact with low-grade pyrolusite powder, SO therein2React with low-grade pyrolusite, complete desulfurization, SO2The solid product obtained after reacting with low-grade pyrolusite is put into normal-temperature water and is soaked, and obtains manganese sulfate；
(4) the sintering flue gas after desulfurization is directly discharged from the air vent of desulfurization reactor。
Embodiment 4:
The method of a kind of low-grade pyrolusite sintering flue gas dry desulfurizing, comprises the steps:
(1) take low-grade pyrolusite, be milled to 100-140 order, obtain low-grade pyrolusite powder；
(2) the low-grade pyrolusite powder obtained in step (1) is put in fluid-bed sweetening reactor；
(3) temperature is first passed into sack cleaner at the sintering flue gas of 130-140 DEG C and carry out dedusting, then pass in fluid-bed sweetening reactor with the flow velocity of 4-5L/min, make sintering flue gas contact with low-grade pyrolusite powder, SO therein2React with low-grade pyrolusite, complete desulfurization, SO2The solid product obtained after reacting with low-grade pyrolusite is put into normal-temperature water and is soaked, and obtains manganese sulfate；
(4) the sintering flue gas after desulfurization is directly discharged from the air vent of desulfurization reactor。
Embodiment 5:
The method of a kind of low-grade pyrolusite sintering flue gas dry desulfurizing, comprises the steps:
(1) low-grade pyrolusite is milled to 160-180 order, obtains low-grade pyrolusite powder；
(2) the low-grade pyrolusite powder obtained in step (1) is put in fluid-bed sweetening reactor；
(3) temperature is passed in fluid-bed sweetening reactor with the flow velocity of 4-6L/min at the sintering flue gas of 140-170 DEG C, make sintering flue gas contact with low-grade pyrolusite powder, SO therein2React with low-grade pyrolusite, complete desulfurization, SO2The solid product obtained after reacting with low-grade pyrolusite is put into normal-temperature water and is soaked, and obtains manganese sulfate；
(4) the sintering flue gas after desulfurization is directly discharged from the air vent of desulfurization reactor。
Embodiment 6:
The method of a kind of low-grade pyrolusite sintering flue gas dry desulfurizing, comprises the steps:
(1) low-grade pyrolusite is taken；
(2) low-grade pyrolusite in step (1) is put in fluid-bed sweetening reactor；
(3) temperature is passed in fluid-bed sweetening reactor with the flow velocity of 6-8L/min at the sintering flue gas of 170-200 DEG C, make sintering flue gas contact with low-grade pyrolusite powder, SO therein2React with low-grade pyrolusite, complete desulfurization；
(4) the sintering flue gas after desulfurization is directly discharged from the air vent of desulfurization reactor。
Claims (8)
1. one kind by the low-grade pyrolusite method to mercurous sintering flue gas dry desulfurizing demercuration, it is characterised in that: comprise the steps:
(1) take low-grade pyrolusite, low-grade pyrolusite is put in reactor；
(2) sintering flue gas is first carried out dust removal process, remove the mercurous dust of sulfur-bearing in sintering flue gas, then the temperature after dedusting is passed in reactor at the sintering flue gas of 100-200 DEG C with the flow velocity of 1-8L/min, make sintering flue gas contact with low-grade pyrolusite, sinter the SO in flue gas2React with low-grade pyrolusite, complete desulfurization；Meanwhile, in sintering flue gas, remaining hydrargyrum is adsorbed by low-grade pyrolusite, completes demercuration；
(3) the sintering flue gas after desulfuration demercuration is directly discharged from the air vent of reactor。
2. the low-grade pyrolusite according to claim 1 method to mercurous sintering flue gas dry desulfurizing demercuration, it is characterised in that: described dust removal process is to be passed in sack cleaner or electrostatic precipitator by sintering flue gas。
3. the low-grade pyrolusite according to claim 1 method to mercurous sintering flue gas dry desulfurizing demercuration, it is characterized in that: in described step (1), low-grade pyrolusite also needs to pulverize when using, obtaining low-grade pyrolusite powder, the size of low-grade pyrolusite powder is 60-180 order。
4. the low-grade pyrolusite according to claim 3 method to mercurous sintering flue gas dry desulfurizing demercuration, it is characterised in that: the size of described low-grade pyrolusite powder is 140-160 order。
5. the low-grade pyrolusite according to claim 1 method to mercurous sintering flue gas dry desulfurizing demercuration, it is characterised in that: in described step (2), it is 3-4L/min that sintering flue gas passes into the flow velocity in reactor。
6. the low-grade pyrolusite according to claim 1 method to mercurous sintering flue gas dry desulfurizing demercuration, it is characterised in that: in described step (2), the temperature of sintering flue gas controls at 110-130 DEG C。
7. the low-grade pyrolusite according to claim 1 method to mercurous sintering flue gas dry desulfurizing demercuration, it is characterised in that: described reactor is fixed bed reactors or fluidized-bed reactor。
8. the low-grade pyrolusite according to claim 1 method to mercurous sintering flue gas dry desulfurizing demercuration, it is characterised in that: by described step (2), SO2The solid reactant being obtained by reacting with low-grade pyrolusite puts into normal-temperature water immersion, and filters。
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| CN106582252A (en) * | 2016-12-21 | 2017-04-26 | 贵州大学 | Novel flue gas desulfurization and demercuration agent and preparation method thereof |
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| CN106582494A (en) * | 2016-12-22 | 2017-04-26 | 贵州大学 | Method for preparing flue gas sulfur and mercury removal agent using manganese aluminate as raw material |
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