CN113521979B - Method for trapping mercury from sulfur-containing mercury-containing flue gas through chlorselenomel deposition - Google Patents
Method for trapping mercury from sulfur-containing mercury-containing flue gas through chlorselenomel deposition Download PDFInfo
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- CN113521979B CN113521979B CN202110923109.2A CN202110923109A CN113521979B CN 113521979 B CN113521979 B CN 113521979B CN 202110923109 A CN202110923109 A CN 202110923109A CN 113521979 B CN113521979 B CN 113521979B
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- flue gas
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- selenium
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000003546 flue gas Substances 0.000 title claims abstract description 119
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008021 deposition Effects 0.000 title claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 13
- 239000011593 sulfur Substances 0.000 title claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 58
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 38
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 chlorseleno-mercury Chemical compound 0.000 claims abstract description 20
- 238000003723 Smelting Methods 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 14
- 239000000428 dust Substances 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 10
- 239000003595 mist Substances 0.000 claims abstract description 10
- 239000002918 waste heat Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 5
- 230000006698 induction Effects 0.000 claims abstract description 5
- 229940100892 mercury compound Drugs 0.000 claims abstract description 4
- 239000011669 selenium Substances 0.000 claims description 23
- 229910052711 selenium Inorganic materials 0.000 claims description 22
- 229940091258 selenium supplement Drugs 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229960001471 sodium selenite Drugs 0.000 claims description 3
- 239000011781 sodium selenite Substances 0.000 claims description 3
- 235000015921 sodium selenite Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 230000003750 conditioning effect Effects 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 17
- 238000000151 deposition Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 229910052815 sulfur oxide Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000005496 tempering Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940074994 mercuric sulfate Drugs 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- UONOSZUBLNXHGW-UHFFFAOYSA-L mercury(2+);sulfite Chemical compound [Hg+2].[O-]S([O-])=O UONOSZUBLNXHGW-UHFFFAOYSA-L 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- YQMLDSWXEQOSPP-UHFFFAOYSA-N selanylidenemercury Chemical compound [Hg]=[Se] YQMLDSWXEQOSPP-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- 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
-
- 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
-
- 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
- B01D53/81—Solid phase processes
-
- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/50—Inorganic acids
- B01D2251/502—Hydrochloric acid
-
- 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
Abstract
The invention relates to a method for trapping mercury from sulfur-containing mercury-containing flue gas by chlorseleno-mercury deposition, which comprises the following steps: (1) Spraying a certain amount of water mist into the nonferrous smelting raw flue gas after dust removal and waste heat recovery, so that the temperature of the nonferrous smelting raw flue gas is reduced to be near a dew point, selenium dioxide in the flue gas is reduced to active elemental selenium capable of rapidly reacting with mercury in the flue gas under the combined action of sulfur dioxide and water vapor, and a chloroselenium mercury compound easy to deposit is generated under the action of HCl in the flue gas; (2) And then, enabling the flue gas to be in contact with a matrix material, and accelerating the generation and deposition of the chlorine selenium mercury through the surface induction effect of the flue gas, so that the mercury in the flue gas is trapped on the surface of the matrix. Compared with the prior art, the method can realize the efficient collection and recovery of mercury in the semi-dry state of the flue gas, and avoid the problems of secondary pollution such as recovery rate reduction and cross-medium transfer caused by excessive entry into a downstream washing waste acid or acid making system.
Description
Technical Field
The invention belongs to the field of environmental protection, and mainly aims at removing and recycling mercury in industrial waste gas, and relates to a method and a matrix material for trapping mercury from sulfur-containing mercury-containing flue gas through chlorselenomel deposition.
Background
Mercury has the characteristics of long-distance migration, high biological enrichment, high toxicity and the like, and is one of the pollutants which are important attention worldwide. The official working of the 'water about mercury' convention aims at cutting off the emission source of mercury globally, limiting the regional circulation of mercury-containing products and prescribing the atmospheric mercury emission control for important industries such as coal-fired power plants, industrial boilers, nonferrous metal smelting, cement production and the like. As the largest mercury discharge country, coal-fired power generation and nonferrous metal smelting are the main mercury discharge sources in China, and the mercury emission reduction pressure is huge. With the increasing concern of air pollution in recent years, the most stringent ultra-low emission standard is formed in the coal-fired power generation industry, and the control technology of sulfur oxides, nitrogen oxides and particulate matters is upgraded and reformed, and meanwhile, mercury is synchronously and efficiently removed in the ultra-low emission technology. However, the emission characteristics of mercury in the nonferrous smelting industry are completely different from those of the coal-fired power generation industry, and ores taking metal sulfides as main components release a large amount of SO (sulfur oxides) in the high-temperature roasting process 2 Contaminants such as particulate matter and heavy metals, and part of the particulate matter and the easily-dissolved contaminants (SO) can be removed by utilizing pollution control equipment such as dust collection, wet washing and the like in the process of downstream migration of flue gas 3 Selenium, chlorine, etc.), and purifying to obtain a purified product containing high concentration SO 2 (in general>4 percent of flue gas is used for preparing sulfuric acid through a two-to-two-absorption process, SO that SO in the flue gas is realized 2 And the efficient purification of large amounts of conventional pollutants such as particulate matter and the utilization of sulfur resources. But mercury in flue gas is mainly zero-valent mercury (Hg) 0 ) Because of high stability and low solubility, the upstream flue gas is needed to be intercepted and trapped in the acid making process along with the flue gas, so that the treatment difficulty of the polluted acid is reduced, and the quality of the sulfuric acid product is improved.
Patent ZL201310277066.0 discloses a method for recycling gaseous zero-valent mercury and sulfur dioxide from nonferrous metal smelting flue gas, which uses mercury sulfate, ferric sulfate and sulfuric acid as main components to prepare a composite absorption liquid, utilizes an absorption tower to efficiently absorb the zero-valent mercury in the flue gas, converts the zero-valent mercury into mercury sulfite, and utilizes the reaction of the ferric sulfate and the sulfur dioxide to generate sulfuric acid. The generated mercuric sulfite is decomposed into elemental mercury and mercuric sulfate by a recovery device. Compared with the prior art, the invention can improve the absorption efficiency of zero-valent mercury in flue gas, reduce the usage amount of the absorbent and realize the recovery of zero-valent mercury. Meanwhile, the sulfuric acid can be recovered through absorbing sulfur dioxide, and Hg (hydrogen peroxide) by sulfur dioxide can be reduced 2+ The total recovery rate of zero-valent mercury is improved, so that the method is very suitable for controlling the emission of flue gas mercury with higher sulfur dioxide concentration. However, the method requires a separate mercury removal device and a corresponding solution, has high cost, gradually loses mercury removal efficiency with the reduction of the concentration of the solution, and is difficult to be applied to complex flue gas.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for trapping mercury from sulfur-containing mercury-containing flue gas through chlorselenomel deposition.
The aim of the invention can be achieved by the following technical scheme: a method for capturing mercury from sulfur-containing mercury-containing flue gas by chlorselenomel deposition, comprising the steps of:
(1) Spraying a certain amount of water mist into the nonferrous smelting raw flue gas after dust removal and waste heat recovery, so that the temperature of the nonferrous smelting raw flue gas is reduced to be near a dew point, selenium dioxide in the flue gas is reduced to active elemental selenium capable of rapidly reacting with mercury in the flue gas under the combined action of sulfur dioxide and water vapor, and a chloroselenium mercury compound easy to deposit is generated under the action of HCl in the flue gas;
(2) And then, enabling the flue gas to be in contact with a matrix material, and accelerating the generation and deposition of the chlorine selenium mercury through the surface induction effect of the flue gas, so that the mercury in the flue gas is trapped on the surface of the matrix.
Further, the nonferrous smelting raw flue gas contains mercury, oxysulfide, selenium dioxide and hydrogen chloride;
the temperature of the flue gas after upstream flue gas dust removal and waste heat recovery is reduced to below 250 ℃, mercury in the flue gas mainly exists in the form of zero-valent mercury, and the concentration range of the mercury in the flue gas is 0.1-50mg/m 3 ，SO 2 The concentration is in the range of 0.2% -5%, seO 2 The concentration is 100-2000mg/m 3 HCl concentration of 20-500mg/m 3 。
Further, spraying water mist into the flue gas in the step (1) to uniformly spray the water into the flue gas by using a high-efficiency atomizing nozzle, so that the temperature of the flue gas is reduced to a degree which is 5-10 ℃ higher than the dew point temperature of the flue gas;
the water sprayed into the water mist is process water or acid waste water without particles, and the water spraying amount is used for reducing the temperature of the flue gas to the vicinity of the dew point.
Further, in the step (1), when the temperature of the flue gas is reduced to the vicinity of the dew point, the selenium dioxide in the flue gas is rapidly reduced into active elemental selenium by sulfur dioxide, and the reduction rate of the selenium dioxide is more than 10%; by the combined action of the mercury and HCl in the flue gas, the gas-phase zero-valent mercury is converted into the chloroselenate mercury, and the gas-phase conversion rate of the mercury can reach 5-20%.
Further, the matrix material in the step (2) is a metal oxide or a porous material;
the metal oxide comprises aluminum oxide, zinc oxide, titanium dioxide or ferric oxide;
the porous material is activated carbon or silicon dioxide.
Further, the contact mode of the flue gas and the matrix material in the step (2) is as follows:
the matrix material is directly sprayed into the flue gas in 100-300 mesh powder form, and the concentration of the matrix material sprayed into the flue gas is 5-50g/m 3 Downstream is provided with a bagCollecting by a dust collector.
Or preparing the matrix material into spherical or columnar particles with the diameter of 2-10mm, contacting the spherical or columnar particles with the flue gas in a fixed bed or moving bed mode, wherein the space velocity (namely, the volume of gas which can be treated in 1 hour per cubic meter of the adsorbent) is 2000-20000h -1 。
Further, in the step (2), the flue gas mercury is promoted to be further converted into the chlorine selenium mercury through the surface induction effect of the matrix material, and the total conversion efficiency is more than 80%.
When selenium dioxide or HCl in the flue gas is insufficient, the surface of the matrix material is modified, the content of chlorine or selenium element on the surface is increased, and the phenomena of escape and secondary pollution caused by directly spraying the substances into the flue gas are avoided.
Further, when the concentration of selenium dioxide in the flue gas itself is lower than 200mg/m 3 When the method is used, 5-20% sodium selenite solution is used for carrying out impregnation modification on a matrix material, so that the material is loaded with 1-5% selenium, and the material can be used after being dried in the air according to the mass of elemental selenium;
when the HCl concentration in the flue gas is lower than 50mg/m 3 When in use, 5-10% sodium chloride solution is used for impregnating and modifying the matrix material, so that the material is loaded with 0.5-2% chlorine, and the matrix material can be used after being dried in the air based on the mass of elemental chlorine.
Further, when the mercury chlorselenate on the surface of the matrix material is accumulated to a certain amount (when the deposition amount of the mercury chlorselenate on the matrix material reaches more than 50g/kg, the part of the matrix material is required to be taken out and regenerated), the part of the matrix material is taken out from the flue gas, the regenerated mercury and selenium are respectively collected and recovered by a condensation method by using a heating regeneration method, and the regenerated matrix material can be recycled after surface tempering modification.
Furthermore, the substrate material deposited with the chlorine selenium mercury is treated by a heating regeneration method, the substrate is heated to 300-400 ℃ when nitrogen is used for protection, high-concentration zero-valent mercury and selenium simple substance gas are obtained, the zero-valent mercury and selenium simple substance product can be respectively recovered through gradual cooling, condensation and adsorption, and the regenerated substrate material can be recycled after being cooled and properly quenched and tempered.
Compared with the prior art, the invention has the following advantages:
1) The invention provides a method for reducing selenium dioxide into active elemental selenium with high-efficiency mercury trapping capability by properly spraying and humidifying sulfur dioxide in flue gas after upstream dust removal of nonferrous smelting flue gas, and forming chloroselenomel mercury under the combined action of chlorine in flue gas, and then depositing the chloroselenomel mercury on the surface of a contacted substrate, so that the high-efficiency mercury trapping and recycling can be realized in a flue gas semi-dry state, and the problems of secondary pollution such as reduction of recycling rate and cross-medium transfer caused by excessive entry of the mercury into a downstream waste acid washing or acid making system are avoided.
2) The mercury capturing method can realize the efficient capture of mercury in the semi-dry state of the flue gas, and avoid the problems of secondary pollution such as the reduction of recovery rate and the transfer of cross media caused by the excessive entry of the mercury into a downstream washing waste acid or acid making system;
3) The matrix material tempering method is simple, low in energy consumption and capable of realizing experimental mass production;
4) After the matrix material is used, selenium and mercury resources can be recovered through heating regeneration, and the matrix material can be recycled.
Drawings
Fig. 1 is a process flow diagram of a method of capturing mercury from sulfur-containing mercury-containing flue gas by chlorseleno mercury deposition in accordance with the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
As shown in fig. 1, a method and a matrix material for capturing mercury from sulfur-containing mercury-containing flue gas by chlorselenomel deposition mainly comprise the following steps:
the first step: after dust removal and waste heat recovery of the nonferrous smelting raw flue gas I101 by the dust remover 1, spraying a certain amount of water mist I102 into the flue gas I, and reducing the temperature of the flue gas to be near a dew point (the temperature of the flue gas can be reduced to be below 250 ℃ or the temperature of the flue gas is reduced to be 5-10 ℃ higher than the dew point temperature of the flue gas), so that selenium dioxide in the flue gas is reduced to active elemental selenium capable of rapidly reacting with mercury in the flue gas under the combined action of sulfur dioxide and water vapor, and the reduction rate of the selenium dioxide can reach more than 10%; under the action of HCl in the flue gas, active elemental selenium generates a chloroselenium mercury compound which is easy to deposit; the gas phase zero-valent mercury is converted into chlorine selenium mercury, and the conversion rate of mercury can reach 5-20%;
the nonferrous smelting raw flue gas I101 is mercury-containing and oxysulfide-containing waste gas generated by the nonferrous metal smelting industry, and simultaneously contains a certain amount of selenium dioxide and hydrogen chloride. The temperature of the flue gas is reduced to the vicinity of the dew point through upstream flue gas dust removal and waste heat recovery. The mercury in the flue gas mainly exists in the form of zero-valent mercury, and the concentration range of the mercury in the flue gas is 0.1-50mg/m 3 ；SO 2 The concentration ranges from 0.2% to 5%. SeO (SeO) 2 The concentration is 100-2000mg/m 3 HCl concentration of 20-500mg/m 3 。
The water mist I102 is uniformly sprayed into the flue gas through the high-efficiency atomizing nozzle, so that the temperature of the flue gas is reduced to the degree that the temperature is 5-10 ℃ higher than the dew point temperature. The water used may be process water or acidic wastewater free of particulate matter.
And a second step of: the matrix material 2 which is favorable for depositing elemental selenium or mercury selenide is used in the downstream flue gas, and the generation and deposition of the chlorine selenium mercury are accelerated through the surface induction effect, so that the mercury in the flue gas is trapped on the surface of the matrix;
the matrix material is metal oxide such as aluminum oxide, zinc oxide, titanium dioxide and ferric oxide, or porous material such as active carbon and silicon dioxide. Can be directly sprayed into the flue gas in 100-300 meshes of powder or prepared into spherical or columnar particles with the diameter of 2-10mm, and is contacted with the flue gas in a fixed bed or moving bed mode;
the matrix material is powder or granule. When the matrix is in powder form, the concentration of the matrix sprayed into the flue gas is 5-50g/m 3 Downstream is provided with a bag type dust collector for collection; when the matrix is a granule, it is usedThe flue gas is treated in a fixed bed or moving bed mode, and the space velocity (namely, the volume of gas which can be treated in 1 hour per cubic meter of the adsorbent) is 2000-20000 hours -1 When the deposition amount of the chlorine selenium mercury on the matrix material reaches more than 50g/kg, the part of the matrix material needs to be taken out and regenerated.
And a third step of: when selenium dioxide or HCl in the flue gas is insufficient, the surface of the matrix can be continuously modified, the content of chlorine or selenium element on the surface of the matrix is increased, and escape and secondary pollution caused by directly spraying the substances into the flue gas are avoided;
the insufficient selenium dioxide refers to when the concentration of selenium dioxide in the flue gas is lower than 200mg/m 3 When the selenium-enriched and heat-modified substrate material is needed, the substrate material is subjected to impregnation modification by using 5-20% sodium selenite solution, so that the substrate material is loaded with 1-5% selenium (based on the mass of elemental selenium), and the substrate material can be used after being dried.
The shortage of HCl refers to when the concentration of HCl in the flue gas is lower than 50mg/m 3 When the method is used, the surface of the matrix material is required to be subjected to chlorination, tempering and modification, the matrix material is subjected to impregnation modification by using 5-10% sodium chloride solution, so that the material is loaded with 0.5-2% chlorine (based on the mass of elemental chlorine), and the matrix material can be used after being dried in the air.
Fourth step: when the chlorine selenium mercury on the surface of the matrix material is accumulated to a certain amount, the chlorine selenium mercury is taken out from the flue gas, and the regenerated mercury and selenium are respectively collected and recovered by a condensation method by utilizing a heating regeneration method. The regenerated matrix material is subjected to surface tempering modification. Can be recycled. By the method, the mercury and selenium in the flue gas can be fully recycled, and the problems of secondary pollution of mercury and the like are prevented. The residual flue gas enters a washing system 4 for preparing acid.
The heating regeneration method is to heat the substrate material deposited with the chlorine selenium mercury 3 to 300-400 ℃ when nitrogen is used for protection, obtain high-concentration zero-valent mercury and selenium simple substance gas, and respectively recover the zero-valent mercury and selenium simple substance products through gradual cooling, condensation and adsorption. The regenerated matrix material 2 can be recycled after being cooled and properly modified.
Example 1
A preparation method of a selenium-enriched quenched and tempered matrix material and a mercury capturing experiment comprise the following steps:
1) Na was disposed in an amount of 0,0.1,0.25,0.5,1mol/L 2 SeO 3 A solution;
2) 100g of Al with a diameter of 1-2mm is weighed 2 O 3 Adding 75mL of the solution into the pellets respectively, carrying out ultrasonic treatment for 1h, and drying at 80 ℃ for 12h to obtain a selenium-enriched material;
3) Weighing 0.5g of material in a 10mm quartz reaction tube, and controlling the inlet Hg 0 The concentration is 1.2mg/m 3 ,SO 2 Concentration is 5%, H 2 O content is 4%, O 2 10% of the total flow is 300mL/min, and the reaction temperature is 80 ℃;
4) When HCl is not added, along with NaSeO 3 Load ratio increases, hg 0 The removal efficiency of 3h is 5%,23%,36%,48% and 67% respectively;
5) When 100ppm HCl is added, with NaSeO 3 Load ratio increases, hg 0 The removal efficiency of 3h of (2) was 12%,55%,78%,83%,96%, respectively.
Example 2
A preparation method of a chlorination quenched and tempered matrix material and a mercury capturing experiment comprise the following steps:
1) Preparing NaCl solution of 0,0.1,0.25,0.5 and 1 mol/L;
2) 100g of Al with a diameter of 1-2mm is weighed 2 O 3 Adding 75mL of the solution into the pellets respectively, carrying out ultrasonic treatment for 1h, and drying at 80 ℃ for 12h to obtain a chlorination material;
3) Weighing 0.5g of material in a 10mm quartz reaction tube, and controlling the inlet Hg 0 The concentration is 1.2mg/m 3 ,SO 2 Concentration is 5%, H 2 O content is 4%, O 2 10% of the total flow is 300mL/min, and the reaction temperature is 80 ℃;
4) When not adding SeO 2 Hg at the time of 0 The removal efficiency of 3h of (2) is lower than 10%
5) When 300mg/m is added 3 SeO 2 In the case of increasing the NaCl loading ratio, hg was added 0 The removal efficiency of 3h of (2) was 46%,68%,79%, respectively，88％，97％。
Example 3
A preparation method of a matrix material for simultaneously increasing selenium, chlorine and hardening and tempering and a mercury capture experiment comprise the following steps:
1) Respectively weighing 0.01mol NaSeO 3 ,0.0075mol NaSeO 3 +0.0025mol NaCl，0.005mol NaSeO 3 +0.005mol NaCl，0.0025mol NaSeO 3 +0.0075mol NaCl,0.01mol NaCl, adding 15mL deionized water, and dissolving by ultrasonic wave;
2) Respectively weighing 2 g of Al with the diameter of 1-2mm 2 O 3 Adding the pellets into the solution, carrying out ultrasonic treatment for 1h, and drying at 80 ℃ for 12h to obtain a selenium-enriched and chlorine-enriched material;
3) Weighing 0.5g of material in a 10mm quartz reaction tube, and controlling the inlet Hg 0 The concentration is 1.2mg/m 3 ,H 2 O content is 4%, O 2 10% of the total flow is 300mL/min, and the reaction temperature is 80 ℃;
4) When no SO is added 2 Hg at the time of 0 The removal efficiency of (C) is lower than 5%
5) When 5000ppm SO is added 2 In the case of increasing Se/Cl ratio, hg 0 The removal efficiency of 3h of (2) was 53%,68%,85%,99%,30%, respectively.
Claims (4)
1. A method for capturing mercury from sulfur-containing mercury-containing flue gas by chlorselenomel deposition, comprising the steps of:
(1) Spraying a certain amount of water mist into the non-ferrous smelting raw flue gas after dust removal and waste heat recovery, and uniformly spraying water into the flue gas by using a high-efficiency atomizing nozzle by spraying the water mist into the flue gas, so that the temperature of the flue gas is reduced to a degree which is 5-10 ℃ higher than the dew point temperature of the flue gas; selenium dioxide in the flue gas is reduced into active elemental selenium capable of reacting with mercury in the flue gas rapidly under the combined action of sulfur dioxide and water vapor, and a chloroselenium mercury compound easy to deposit is generated under the action of hydrogen chloride in the flue gas; the nonferrous smelting raw flue gas contains mercury, oxysulfide, selenium dioxide and hydrogen chloride;
temperature of flue gas after upstream flue gas dust removal and waste heat recoveryThe mercury in the flue gas is mainly in the form of zero-valent mercury, and the concentration of the mercury in the flue gas is in the range of 0.1-50mg/m 3 The concentration of selenium dioxide is 100-2000mg/m 3 The concentration of hydrogen chloride is 20-500mg/m 3 ；
(2) Then, the flue gas is contacted with a matrix material, wherein the matrix material is alumina, zinc oxide, titanium dioxide, ferric oxide, active carbon or silicon dioxide, and powder of 100-300 meshes is directly sprayed into the flue gas, or the matrix material is prepared into spherical or columnar particles with the diameter of 2-10mm, and the spherical or columnar particles are contacted with the flue gas in a fixed bed or moving bed mode, and the generation and deposition of mercury chloroselenate are accelerated through the surface induction effect of the spherical or columnar particles, so that mercury in the flue gas is trapped on the surface of the matrix;
when selenium dioxide or hydrogen chloride in the flue gas is insufficient, the surface of the matrix material is modified, the content of selenium or chlorine element on the surface of the matrix material is increased, and escape and secondary pollution caused by directly spraying the substances into the flue gas are avoided; when the concentration of selenium dioxide in the flue gas is lower than 200mg/m 3 When the method is used, the sodium selenite solution is used for carrying out impregnation modification on the matrix material, so that the matrix material is loaded with selenium, and the selenium-loaded matrix material can be used after being dried in the air;
when the concentration of hydrogen chloride in the flue gas is lower than 50mg/m 3 During the process, the matrix material is impregnated and modified by sodium chloride solution, so that the matrix material is loaded with chlorine, and the matrix material can be used after being dried.
2. The method for capturing mercury from sulfur-containing mercury-containing flue gas by chlorselenomel deposition according to claim 1, wherein the water used for spraying the water mist in step (1) is process water.
3. The method for capturing mercury from sulfur-containing mercury-containing flue gas by chlorselenomel deposition according to claim 1, wherein the water used for spraying the water mist in step (1) is acidic wastewater free of particulate matters.
4. The method for capturing mercury from sulfur-containing mercury-containing flue gas by means of chlorselenomel deposition according to claim 1, wherein when chlorselenomel on the surface of the matrix material is accumulated to a certain amount, the chlorselenomel is taken out from the flue gas, regenerated mercury and selenium are respectively collected and recovered by a condensation method by means of a heating regeneration method, and the regenerated matrix material can be recycled after surface conditioning modification.
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