CN100346865C - Method for removing mercury for flue gas by using sulfo-halogen compound-supported modified adsorbent - Google Patents
Method for removing mercury for flue gas by using sulfo-halogen compound-supported modified adsorbent Download PDFInfo
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003463 adsorbent Substances 0.000 title claims description 70
- 239000003546 flue gas Substances 0.000 title claims description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 51
- 229910052736 halogen Inorganic materials 0.000 title claims description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 62
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000010881 fly ash Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 14
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 73
- 229910052717 sulfur Inorganic materials 0.000 claims description 59
- 239000011593 sulfur Substances 0.000 claims description 59
- -1 sulfur halide compound Chemical class 0.000 claims description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 30
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- 230000008016 vaporization Effects 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- SISAYUDTHCIGLM-UHFFFAOYSA-N bromine dioxide Chemical compound O=Br=O SISAYUDTHCIGLM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910018503 SF6 Inorganic materials 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 2
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 2
- JMPVZWBJWHQJDD-UHFFFAOYSA-N sulfur tetrachloride Chemical compound ClS(Cl)(Cl)Cl JMPVZWBJWHQJDD-UHFFFAOYSA-N 0.000 claims description 2
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 claims description 2
- 150000005311 thiohalides Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 125000005843 halogen group Chemical group 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 2
- 125000004434 sulfur atom Chemical group 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 11
- 239000000779 smoke Substances 0.000 abstract 5
- 230000000694 effects Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 5
- JIRDGEGGAWJQHQ-UHFFFAOYSA-N disulfur dibromide Chemical compound BrSSBr JIRDGEGGAWJQHQ-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 150000002019 disulfides Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical group [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a method for removing mercury in smoke gas by modified adsorption agents which contain sulfo-halogen compounds. Compounds which contain sulfur atoms and halogen atoms or precursors thereof are used as modifiers which are used for the load modification of adsorption agents, surface mercury absorption characteristics of the adsorption agents are changed, weight percentage of load capacity of sulfo-halogen compounds on the adsorption agents is from 0.01 to 10%, modified adsorption agents are filled or directly sprayed into smoke gas and contact the smoke gas, and the modified adsorption agents are directly used for removing mercury in the smoke gas. The capacity of adsorbing simple substance mercury in the smoke gas of the modified adsorption agents of the present invention is obviously increased, and adsorbed simple substance mercury is finally converted into stable mercury sulfide, and secondary pollution of the mercury is solved. Because the sulfo-halogen compounds can be easily loaded on the adsorption agents, the requirement of specific surface areas of the adsorption agents is low, and therefore, the selection range of the adsorption agents is widened, and modified fly ash or cheap inorganic substances can be used as adsorption agents for removing mercury.
Description
Technical Field
The invention relates to a method for removing mercury from flue gas by using a sulfur halide compound loaded modified adsorbent, which is characterized in that mercury removing adsorbent is modified to efficiently remove mercury in different forms in coal-fired flue gas and convert the mercury into stable mercury sulfide, so that mercury in flue gas is thoroughly treated.
Background
Mercury has a strong physiological toxicity and, despite its low concentration in flue gases, causes considerable environmental damage. The mercury emission control standard of a thermal power plant is officially issued in 3 months in 2005 in the united states, and other countries will officially release relevant standards. As the mercury content in the coal of China is generally higher and the using amount of the coal is huge, China becomes the country which is most seriously polluted by mercury in the world. Therefore, it is very urgent to enhance the control of mercury pollution during the burning of coal and garbage.
The mercury in the flue gas is mainly granular mercury (Hg)p) Gaseous divalent mercury (Hg)2+) And gaseous elemental mercury (Hg)0) The three forms of the mercury-free fuel gas have a very close relationship between the proportion of each component and the content of halogen (mainly chlorine) in the fuel coal, and the lower the chlorine element is, the higher the proportion of elemental mercury in the flue gas is. Particulate mercury can generally be removed by dust removal devices; gaseous divalent mercury, mostly in the form of vapor of mercury compounds, is readily adsorbed by most sorbents, or by wet desulfurization systems. The elemental mercury is difficult to treat even though the mercury is generally adopted at home and abroadThe activated carbon flue gas injection technology (ACI) is not ideal in the removal of elemental mercury, and the consumption of activated carbon is too high, which affects the reutilization of fly ash. By using the wet-type desulfurization device, only the divalent mercury in the flue gas can be removed, but the mercury is removed0There was little removal. Attempts have also been made to use catalytic oxidation to oxidize Hg in flue gas0The element mercury, however, sulfur dioxide in the flue gas has a toxic effect on the catalyst, so that it is difficult to find a catalyst which can be stably used for a long time, and in addition, the method needs to additionally add a catalytic conversion unit, so that the complexity and investment cost of a flue gas purification system are increased, and the method is greatly limited in practical application.
In addition, there have been attempts to collect mercury in flue gas by a recovery method, but it is difficult to realize the method because the mercury concentration in flue gas is too low and the flue gas composition is too complicated. In addition, in the currently explored mercury control method, whether the activated carbon adsorption method or the wet absorption method is used for directly transferring mercury in flue gas into fly ash or desulfurization byproducts, and the safety and stability of the mercury in the substances are not considered. In fact, most of the trapped mercury exists in soluble mercury salt, and is easy to be leached by rainwater to cause secondary pollution and the like.
In addition, in order to improve the adsorption capacity of the adsorbent for elemental mercury in flue gas, the adsorbent can be modified by using a proper chemical treatment method. Among them, a method of modifying the adsorbent by supporting it with a halogen molecule is most concerned. However, if the halogen molecules are directly used to modify the adsorbent, although the modified adsorbent has a good chemical adsorption effect on the elemental mercury at low temperature, the halogen molecules loaded on the adsorbent are easily lost at higher flue gas temperature (generally above 120 ℃), and the expected effect cannot be achieved. Meanwhile, elemental mercury adsorbed on the adsorbent is oxidized into soluble mercury halide, and the compounds are easy to volatilize or be leached by water, so that secondary pollution is caused. In addition, when elemental sulfur (sulfur) is used as a load to modify the adsorbent, although the adsorbed elemental mercury can be converted into stable mercury sulfide, the sulfur has poor reactivity, and the modified adsorbent still has a slow adsorption rate on the elemental mercury, so that the actual use requirement cannot be met.
Disclosure of Invention
The invention aims to provide a method for removing mercury from flue gas by using a sulfur halide compound loaded modified adsorbent, aiming at overcoming the defects of the existing mercury pollution control technology, and the method can obviously improve the adsorption effect on elemental mercury in the flue gas, reduce the using amount of the adsorbent and avoid secondary pollution to the environment.
In order to achieve the purpose, in the technical scheme of the invention, a compound containing sulfur and halogen atoms or a precursor thereof is used as a modifier to carry out load modification on the adsorbent, so that the adsorption capacity of the modified adsorbent on elemental mercury in flue gas is remarkably improved, and the adsorbed mercury is finally converted into stable mercury sulfide. Firstly, heating and vaporizing a sulfur halide compound or a precursor thereof, and contacting the sulfur halide compound with an adsorbent to load the sulfur halide compound on the surface of the adsorbent in an adsorption mode, so that the surface mercury adsorption characteristic of the adsorbent is changed, the loading amount of the sulfur halide compound on the adsorption is 0.01-10% by weight, and the modified adsorbent is contacted with flue gas in a filling mode or a mode of directly spraying the modified adsorbent into the flue gas and is directly used for removing mercury from the flue gas.
Research finds that the chemical modification of the adsorbent by using a compound (or a precursor thereof) containing sulfur and halogen atoms simultaneously can combine the characteristics of halogen molecules and sulfur: the method not only can quickly adsorb the elemental mercury in the flue gas onto the modified adsorbent, but also can convert the mercury into stable mercury sulfide. In addition, such substances are easily supported on the adsorbent and are not easily lost at high temperatures. Furthermore, some of the sulfur halide compounds themselves have a high oxidizing activity towards elemental mercury. The oxidation of elemental mercury and the stabilization of mercury by a sulfur halide compound can be represented by the following two equations:
Hg+SmXn(loaded on adsorbent) → HgS, HgX2(occurring on adsorbents) (1)
HgX2+SmXn(Supported on adsorbent) + H2O (steam) → HgS + HX + Others (2)
Wherein S ismXnRepresents a thiohalogen compound (m is the number of sulfur atoms in the molecule and is usually 1 to 3; and n is the number of halogen atoms and is usually 2 or 4). In reaction (1), SmXnEquivalent to oxidative chemisorption of elemental mercury with simultaneous formation of HgS and HgX2. While reaction (2) is carried out in the presence of water vapor (e.g. in flue gas or natural air), SmXnHydrolyzing with water vapor to produce S2-And sulfur (also with a small amount of sulfate radical), in the presence of S2-And sulfur reduction of HgX2Converted into HgS.
Therefore, if the adsorbent can be properly modified to adsorb mercury with different forms and convert the adsorbed mercury into stable mercury sulfide, the method is an ideal flue gas purification way.
The method of the invention is concretely as follows:
1. the thiohalide compound or a thiohalide compound precursor is used for carrying modification on the adsorbent, so that the weight percentage of the thiohalide compound carrying capacity on the adsorbent is 0.01-10%. Wherein,
a) when the sulfur halide is used for modification, the sulfur halide is heated and vaporized, the gas flow containing the sulfur halide vapor is quickly introduced into an adsorption container filled with an adsorbent, and the sulfur halide in the gas flow is loaded on the adsorbent through adsorption by continuous mixing.
b) When the precursor of the sulfur halide compound is used for modification, the precursor containing sulfur is heated and vaporized, so that the weight percentage of the sulfur loading on the adsorbent is within 5 percent; and heating and vaporizing the halogen-containing precursor to load the halogen-containing precursor on a sulfur-containing adsorbent, wherein the load is within 5 weight percent, and the sulfur and halogen precursor adsorbed on the adsorbent is converted into a sulfur halide compound through reaction.
2. The loaded modified adsorbent is used for adsorbing mercury in the flue gas, and the adsorbent is contacted with the flue gas in a filling type or directly sprayed into the flue gas, so that elemental mercury and mercury in other forms in the flue gas are adsorbed by the modified adsorbent and are gradually converted into mercury sulfide, and the mercury in the flue gas is completely removed. When the filling type is adopted, the thickness of the adsorbent filling layer is 1-200 mm; when the form of directly spraying flue gas is adopted, the volume ratio of the adsorbent sprayed into the flue gas to the flue gas is 10-2000mg/m3。
The sulfur halide compound is one or more of disulfide difluoride, sulfur tetrafluoride, sulfur hexafluoride, disulfide dichloride, sulfur tetrachloride, disulfide dibromide and disulfide diiodide.
In the precursor of the sulfur halide compound, the sulfur-containing precursor is sulfur, metal sulfide and polysulfide; the halogen-containing precursor is the simple substance of fluorine, chlorine, bromine and iodine or the oxide with more than zero valence thereof, such as hypochlorous acid, chlorine dioxide, bromine dioxide, hypochlorous acid, hypobromous acid, halogen acid, perhalogen acid and the like; one or more of them are used.
The adsorbent comprises one or more of coal fly ash, different types of activated carbon, ceramic-carbon composite materials, ceramic materials, clay, alumina, sepiolite, volcanic ash and the like.
The invention is characterized in that:
1) after the adsorbent is subjected to load modification by the method, the adsorption capacity and the adsorption rate of elemental mercury are remarkably increased, so that the using amount of the adsorbent in the flue gas treatment process is remarkably reduced;
2) the adsorbed elemental mercury is quickly oxidized to finally form stable mercury sulfide, so that the possibility of secondary pollution to the environment is reduced;
3) the adopted sulfur halide compound is easy to load on the adsorbent, and the requirement on the specific surface area of the adsorbent is not high, so that the selection range of the adsorbent is widened, and the modified fly ash or cheap inorganic substances can be used as the mercury removal adsorbent.
Drawings
Fig. 1 is a graph showing the adsorption removal effect of elemental mercury by using different activated carbons in example 1.
In FIG. 1, 1#: the adsorption curve of the active carbon modified by disulfide dichloride to elemental mercury; 2#: the adsorption curve of the sulfur-modified activated carbon to the elemental mercury; 0#: adsorption curve of unmodified activated carbon to elemental mercury.
Detailed Description
The technical solution of the present invention is further described below by specific examples. The following examples are not to be construed as limiting the invention.
Example 1 (active carbon supporting disulfide dichloride)
The load method comprises the following steps: 5mL of disulfide dichloride (> 98% analytically pure) were taken and placed in a 50mL glass evaporation flask. The vaporization bottle volume of 2/3 was immersed in an oil bath, which was used to control the vaporization bottle temperature. 100g of 120-mesh active carbon with the granularity of 100-. One port of the flask was equipped with a stirrer, and the other two ports were used as an inlet and an exhaust for sulfur dichloride vapor, respectively. The air outlet of the vaporization bottle is connected with the air inlet of the adsorption bottle.
The heating power supply of the oil bath is switched on, the temperature of the vaporization bottle is kept at about 120 ℃, the disulfide dichloride is continuously vaporized, and the vapor is led into the absorption bottle. The stirrer in the adsorption bottle continuously stirs the activated carbon at the rotating speed of 100 r/min, so that the activated carbon is well mixed with the disulfide dichloride steam and is quickly adsorbed by the activated carbon. When the adsorption time is 10 minutes, the loading rate of the disulfide dichloride on the activated carbon is about 1 percent.
The heating of the vaporization bottle is stopped, and the activated carbon loaded with disulfide dichloride is used for carrying out an adsorption experiment of elemental mercury and compared with the activated carbon not loaded with disulfide dichloride, and the method is as follows:
weighing 0.02g of activated carbon with the disulfide dichloride loading rate of 1%, placing the activated carbon into a U-shaped glass tube with the diameter of 6mm and the length of 100mm, and blocking two ends with quartz wool to form an activated carbon adsorption layer, wherein the thickness of the activated carbon adsorption layer is about 2 mm; an oil bath heating device is adopted for heating, and the temperature of the adsorption layer is controlled to be 140 ℃. Preparing mercury-containing simulated waste gas by using mercury permeation tube and flowing air to make the elemental mercury concentration in the gas be 90 microgram/m3. When the airflow continuously passes through the activated carbon adsorption layer at the flow rate of 200ml/min, the concentration of the elemental mercury in the adsorbed gas is measured, and the removal effect of the adsorption layer on the elemental mercury is determined. Similarly, a comparative experiment was also conducted using activated carbon not loaded with a thiohalide compound and activated carbon loaded with 1% sulfur, and the amounts of activated carbon used were each 0.02 g. When the temperature of the adsorption layer is 140 ℃, the adsorption result of different activated carbons on elemental mercury in the gas flow is shown in fig. 1.
As can be seen from FIG. 1, disulfide dichloride-loaded activated carbon (1)#) The adsorption effect on the elementary mercury is the best, and the removal rate of the elementary mercury is always kept above 90% within 50 minutes after adsorption is started. And activated carbon (0) not loaded with other substances#) The effect is poor, and when the adsorption time is 10 minutes, the removal efficiency of the elemental mercury is reduced to about 20%. Although activated carbon (2) carrying sulfur#) The adsorption performance of the carbon material is slightly improved, but the effect is far lower than that of the active carbon loaded with the disulfide dichloride.
Example 2
The dibromide disulfide was vaporized at 200 ℃ by a loading method similar to that of example 1, and the activated carbon powder was fumigated and loaded with the vapor thereof, so that the amount of dibromide loaded on the activated carbon was about 0.5%. The main experimental conditions for the adsorption experiment of mercury-containing gas were the same as in example 1, except that 0.02g of activated carbon was weighed as an adsorbent.
The result shows that the active carbon loaded with the dibrominated disulfide has better adsorption effect on the elemental mercury, and when the adsorption time is 100 minutes, the removal rate of the elemental mercury is still more than 92%.
Example 3
The sulfur and the dibrominated disulfide are respectively vaporized at the temperature of 200 ℃ by adopting a loading method similar to that of the example 1, and are respectively loaded on different coal fly ash, and the loading amount is about 0.5 percent. 0.1g of the modified adsorbent was weighed so that the thickness of the adsorption layer was about 2 mm. The experimental conditions for the adsorption of mercury-containing gas were the same as in example 1.
The result shows that the fly ash loaded with the dibrominated disulfide has good adsorption effect on the elemental mercury, and when the adsorption time is 30 minutes, the removal rate of the elemental mercury is still over 85%. In the same situation, when the fly ash loaded with sulfur or the fly ash not loaded with any substance is used, the adsorption effect on the elemental mercury is poor, and when the adsorption time is 5 minutes, the removal rate of the elemental mercury is reduced to below 20%.
Example 4 (precursor load)
A similar procedure was followed as in example 1, except that the supporting materials used were sulfur and bromine, precursors of a sulfur-chlorine-bromine compound. Firstly, sulfur is vaporized at 200 ℃, and is loaded on fly ash through fumigation, so that the loading capacity of the sulfur on the fly ash is about 0.5 percent; then, the single bromine is vaporized at the temperature of 40 ℃, and the fly ash carrying the sulfur is fumigated and loaded, so that the loading amount of the bromine is about 1 percent. As a result, it was found that elemental bromine was easily adsorbed on the sulfur-loaded fly ash, and the reaction to form disulfur dibromide occurred rapidly. However, fly ash not loaded with sulfur has a weak adsorption capacity for elemental bromine and will be lost quickly at a slightly higher temperature.
0.1g of the modified fly ash was weighed out, and an adsorption experiment was performed on the mercury-containing gas under the same conditions as in example 1 (the thickness of the packed layer was 2 mm). The result shows that when sulfur and elemental bromine are used as precursors to carry out stepwise modification, the obtained modified fly ash also has a good adsorption effect on elemental mercury, and when the adsorption time is 30 minutes, the removal rate of the elemental mercury is about 85%.
Example 5
The experiment was carried out in a simulated flue gas duct, a glass tube having an internal diameter of 30mm and a length of 500mm was placed vertically and heated electrically to maintain its temperature at 150 ℃. The simulated mercury-containing flue gas is configured to ensure that the concentration of elemental mercury in the gas flow is about 55 mu g/m3And the air flow flows through the glass tube from top to bottom, and the average flow rate of the air flow is 10m3And h, installing a small cyclone dust collector at the gas outlet of the glass tube.
500g of activated carbon with 1% of disulfide dichloride loading was obtained in a similar manner to example 1; the modified activated carbon was sprayed into the glass tube from the upper part thereof at a feed rate of 2g/h (the ratio of the content of activated carbon in the gas stream to the volume of the gas was 200 mg/m)3) So that the activated carbon is rapidly mixed with the air flow, and the activated carbon flowing out along with the air flow from the lower part of the glass tube is removed by the cyclone dust collector.
The results of measuring the elemental mercury concentration in the gas flow entering and exiting the glass tube under the above conditions show that the active carbon modified by the disulfide dichloride has high adsorption efficiency on the elemental mercury, and the average adsorption efficiency is more than 90%. However, when activated carbon not loaded with disulfide dichloride was used, the removal efficiency of elemental mercury was less than 30% under the same operating conditions.
Example 6
In a similar manner to example 1, disulfur dibromide was separately vaporized at a temperature of 200 ℃ and loaded on coal fly ash, with a loading of about 0.5%. The formulation conditions for the simulated flue gas were the same as in example 5.
Fly ash loaded with disulfur dibromide was injected into the glass tube from the upper part thereof at a feed rate of 6g/h (the ratio of the fly ash content to the gas volume in the gas stream was 600 mg/m)3) So that the air is rapidly mixed with the air flow,the activated carbon flowing out with the air flow from the lower part of the glass tube is removed by the cyclone dust collector.
The results of measuring the elemental mercury concentrations in the gas flows entering and exiting the glass tube under the above conditions show that the fly ash modified by the disulfur dibromide has high adsorption efficiency on the elemental mercury, and the average adsorption efficiency is more than 85%.
Example 7
Based on examples 1-6, the chemical conversion products after elemental mercury was adsorbed by the adsorbent were analyzed, and leaching analysis was performed on the mercury-containing products in the adsorbent using ethanol and concentrated sodium sulfide solution, respectively. As a result, the disulfide dichloride or the disulfide dibromide loaded on the fly ash can convert more than 60 percent of elementary mercury into mercury sulfide, the balance is mercury chloride or mercury bromide, and the sulfur halide compound has a good stable conversion effect on mercury. When the adsorbent is placed in natural air (the relative humidity is 30% -60%) for 2 days, the conversion rate of the mercuric sulfide is more than 70%.
Claims (4)
1. A method for removing mercury from flue gas by using a sulfur halide compound loaded modified adsorbent is characterized by comprising the following steps:
1) carrying out load modification on the adsorbent by using a thiohalide compound or a thiohalide compound precursor to ensure that the weight percentage of the load of the thiohalide compound on the adsorbent is 0.01-10%; wherein, a) when the sulfur halide compound is used for modification, the sulfur halide compound is heated and vaporized, the gas flow containing the sulfur halide compound vapor is introduced into an adsorption container filled with an adsorbent, and the sulfur halide compound in the gas flow is loaded on the adsorbent through adsorption by continuous mixing; b) when the precursor of the sulfur halide compound is used for modification, the precursor containing sulfur is heated and vaporized, so that the weight percentage of the sulfur loading on the adsorbent is within 5 percent; heating and vaporizing the halogen-containing precursor to load the halogen-containing precursor on a sulfur-containing adsorbent, wherein the load amount is within 5% by weight, and the sulfur and halogen precursor adsorbed on the adsorbent is converted into a sulfur halide compound through reaction;
2) the loaded modified adsorbent is used for adsorbing mercury in the flue gas, and the adsorbent is contacted with the flue gas in a filling type or directly sprayed into the flue gas, so that elemental mercury in the flue gas is adsorbed by the modified adsorbent and is gradually converted into mercury sulfide, and the mercury in the flue gas is removed; when the filling type is adopted, the thickness of the adsorbent filling layer is 1-200 mm; when the form of directly spraying flue gas is adopted, the volume ratio of the adsorbent sprayed into the flue gas to the flue gas is 10-2000mg/m3。
2. The method for removing mercury from flue gas by using the thiohalide-supported modified adsorbent according to claim 1, wherein the thiohalide is one or more of disulfide difluoride, sulfur tetrafluoride, sulfur hexafluoride, disulfide dichloride, sulfur tetrachloride, disulfide dibromide, and disulfide diiodide.
3. The method for removing mercury from flue gas by using the sulfur halide compound-supported modified adsorbent according to claim 1, wherein the sulfur-containing precursor of the sulfur halide compound is one or more of sulfur, metal sulfide and polysulfide; the halogen-containing precursor of the sulfur halide compound is the simple substance of fluorine, chlorine, bromine and iodine or the oxide of the simple substance with more than zero valence, and comprises one or more of hypochlorous acid, chlorine dioxide, bromine dioxide, hypochlorous acid, hypobromous acid, halogen acid and high halogen acid.
4. The method for removing mercury from flue gas by using the thiohalide compound-loaded modified adsorbent according to claim 1, wherein the adsorbent is one or more of coal fly ash, activated carbon, ceramic-carbon composite materials, ceramic materials, clay, alumina, sepiolite and volcanic ash.
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| CN101406794B (en) * | 2008-11-13 | 2012-08-22 | 上海交通大学 | Method for preparing exhaust gas mercury-removing reagent from modification of waste desulfurizing agent |
| CN102698771A (en) * | 2012-06-01 | 2012-10-03 | 江苏和亿昌环保工程科技有限公司 | Catalyst for removing mercury from flue gas and preparation method of same |
| CN102980175B (en) * | 2012-11-29 | 2015-11-18 | 广东电网公司电力科学研究院 | Reduce the device and method of Elemental Mercury discharge capacity in coal combustion |
| US9827551B2 (en) * | 2015-02-27 | 2017-11-28 | W. L. Gore & Associates, Inc. | Flue gas purification system and process using a sorbent polymer composite material |
| AU2016343711A1 (en) * | 2015-10-30 | 2018-03-29 | Amcol International Corporation | Improved method of making a mercury sorbent |
| CN105854544A (en) * | 2016-05-24 | 2016-08-17 | 南京华电节能环保设备有限公司 | Exhaust gas mercury-removal purification method |
| CN107159088B (en) * | 2017-05-12 | 2020-04-14 | 中科京投环境科技江苏有限公司 | Mercury-containing material with lasting adsorption performance |
| EP3950111A4 (en) * | 2019-03-27 | 2022-11-30 | Eneos Corporation | Hydrogen gas supplier and hydrogen gas supply method |
| CN110586023B (en) * | 2019-09-20 | 2021-06-04 | 中国科学院地球化学研究所 | Sulfur-modified chalcopyrite adsorbing material, preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005125261A (en) * | 2003-10-24 | 2005-05-19 | Mitsubishi Heavy Ind Ltd | Method and device for removing mercury in boiler exhaust gas |
| CN1698931A (en) * | 2005-04-07 | 2005-11-23 | 上海交通大学 | Flue gas hydrargyrum-removing method by catalytic oxidation |
| US20060057044A1 (en) * | 2004-04-09 | 2006-03-16 | Shih-Ger Chang | Method for scavenging mercury |
-
2006
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060057044A1 (en) * | 2004-04-09 | 2006-03-16 | Shih-Ger Chang | Method for scavenging mercury |
| CN1698931A (en) * | 2005-04-07 | 2005-11-23 | 上海交通大学 | Flue gas hydrargyrum-removing method by catalytic oxidation |
Non-Patent Citations (1)
| Title |
|---|
| 活性碳吸附烟气中气态汞的试验研究 任建莉，周劲松，骆仲泱等.中国电机工程学报，第24卷第2期 2004 * |
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