CN1313199C - Method for preparing coal burning fume mercury-removing adsorbent - Google Patents
Method for preparing coal burning fume mercury-removing adsorbent Download PDFInfo
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- CN1313199C CN1313199C CNB2004100734834A CN200410073483A CN1313199C CN 1313199 C CN1313199 C CN 1313199C CN B2004100734834 A CNB2004100734834 A CN B2004100734834A CN 200410073483 A CN200410073483 A CN 200410073483A CN 1313199 C CN1313199 C CN 1313199C
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003245 coal Substances 0.000 title description 22
- 239000003517 fume Substances 0.000 title 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 91
- 239000003546 flue gas Substances 0.000 claims abstract description 72
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 67
- 150000002696 manganese Chemical class 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 229910052902 vermiculite Inorganic materials 0.000 claims description 5
- 239000010455 vermiculite Substances 0.000 claims description 5
- 235000019354 vermiculite Nutrition 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 241001474374 Blennius Species 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 235000012054 meals Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000428 dust Substances 0.000 description 10
- 230000007613 environmental effect Effects 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 6
- 239000010881 fly ash Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- LBVGBJMIMFRUSV-UHFFFAOYSA-N [C].[Hg] Chemical compound [C].[Hg] LBVGBJMIMFRUSV-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- MWRBNPKJOOWZPW-GPADLTIESA-N 1,2-di-[(9E)-octadecenoyl]-sn-glycero-3-phosphoethanolamine Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCN)OC(=O)CCCCCCC\C=C\CCCCCCCC MWRBNPKJOOWZPW-GPADLTIESA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- -1 coal-fired boilers Chemical compound 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种燃煤烟气除汞吸附剂的制备方法。它向水中加入水总量1-2%的硫酸使水溶液呈现酸性，加入七价锰盐固体或溶液，搅拌，使七价锰盐溶解，加入酸性二价锰盐溶液，同时进行搅拌，加入颗粒状吸附剂，继续搅拌30-40分钟，在80-100℃加热干燥为固体状态，研磨成粉状即可，其中七价锰盐、二价锰盐和颗粒状吸附剂的添加量之比为1∶1-2∶35-50。本发明的优点是：1)利用本方法制备的吸附剂可以全面控制燃煤电站烟气中汞的三种形态，并将其转化为惰性化合物；2)可以在烟道上直接向烟气喷加，操作较为方便；3)本方法工艺简单实用，易于推广；4)可与燃煤电站现有污染物控制装置结合进行汞排放控制，既降低了初期投入，也节约了运行成本。The invention discloses a preparation method of an adsorbent for removing mercury from coal-fired flue gas. It adds sulfuric acid with 1-2% of the total amount of water in the water to make the aqueous solution acidic, adds heptavalent manganese salt solid or solution, stirs to dissolve the heptavalent manganese salt, adds acidic divalent manganese salt solution, stirs at the same time, and adds particles Shaped adsorbent, continue to stir for 30-40 minutes, heat and dry at 80-100°C to a solid state, and grind it into powder. The ratio of the amount of heptavalent manganese salt, divalent manganese salt and granular adsorbent is 1:1-2:35-50. The advantages of the present invention are: 1) the adsorbent prepared by the method can fully control the three forms of mercury in the flue gas of coal-fired power stations and convert them into inert compounds; 2) it can be directly sprayed on the flue gas , the operation is more convenient; 3) the method is simple and practical, and easy to popularize; 4) it can be combined with the existing pollutant control device of the coal-fired power station for mercury emission control, which not only reduces the initial investment, but also saves the operating cost.
Description
Technical Field
The invention relates to a preparation method of a coal-fired flue gas mercury removal adsorbent.
Background
Mercury is not a necessary substance for living activities of organisms, but has strong and lasting toxicity to higher organisms, the research on mercury pollution in various countries is very important, and the source of environmental mercury pollution is mainly artificial mercury pollution. Mercury is one of trace heavy metal elements in coal, mercury escaping from coal worldwide every year due to massive combustion of coal accounts for a large part of mercury released by human activities, and the average mercury content in the coal is in the range of 0.12-0.28 mg/kg according to statistics of environmental protection organization of New Jersey (NJ DEPE) (1993). China is a large energy consumption country, and in the total energy consumption of China, coal accounts for over 75 percent, and over 80 percent of coal is used for direct combustion, particularly in power stations, industrial boilers and civil boilers. According to statistics, the accumulated emission of mercury to the atmosphere in the coal burning industry of China reaches 2493.8 tons since 1978 to 1995. The annual average rate of increase in mercury emissions was 4.8%. At present, coal-fired mercury pollution, particularly mercury discharge in coal-fired power plant boilers and environmental harmfulness have attracted attention from countries all over the world. China is a large energy consumption country, the raw coal yield of 1989 is more than 10 x 108 tons, and in the total energy consumption of China, coal accounts for more than 75%, and more than 80% of coal is used for direct combustion, particularly in power stations, industrial boilers and civil boilers. According to statistics, the accumulated emission of mercury to the atmosphere in the coal burning industry of China reaches 2493.8 tons since 1978 to 1995. The annual average rate of increase in mercury emissions was 4.8%. This figure will also grow as the economy develops. At present, coal-fired mercury pollution, particularly mercury discharge in coal-fired power plant boilers and environmental harmfulness have attracted attention from countries all over the world. However, with the further research, the pollution problem is solved.
With SO2Compared with the research on the control of pollutants such as NOx, the research on coal-fired mercury separation and treatment methods and mercury treatment adsorbents developed at home and abroad at present starts later. Until the 90 s of the twentieth century, many scholars began to attach attention and research. In 1990, the American Congress passed a revised air purification code. According to this amendment, the united states Environmental Protection Agency (EPA) has evaluated the emissions of hazardous pollutants (HAP) from fossil-fueled power plants, and has written a report on the sources of mercury emissions, methods of controlling emissions, and health effects to congress. Since then, the relevant scholars and research institutes in the united states have argued that the research on mercury emissions from coal fired power plants has begun problematically, and that the heat waves for studying mercury emissions have emerged.
At present, from the general view of the developed countries on the control of the emission of pollutants in flue gas, the environmental protection requirement is higher and higher, and the control content is finer and finer. To accommodate these stringent regulations, a new batch of coal-fired flue gas demercuration processes, new devices, and corresponding sorbents should be developed in succession. The research aiming at the coal-fired flue gas mercury-controlling adsorbent is approximately as follows by integrating domestic and foreign documents:
and the mercury in the flue gas is removed by adsorption by using activated carbon as an adsorbent. The garbage incinerator adopts the activated carbon adsorption and cloth bag dust removal technology for controlling the emission of heavy metal mercury, and the mercury removal efficiency of more than 90 percent can be obtained by selecting a proper carbon-mercury (C/Hg) ratio due to higher mercury concentration. For the mercury removal of flue gas of a coal-fired power plant boiler, the mercury concentration is low, the mercury removal efficiency is poor, the carbon mercury (C/Hg) ratio is properly increased, the mercury removal efficiency can reach more than 30%, but the method has high cost and is difficult to bear by a coal-fired power plant.
With calcium-based adsorbents (CaO, Ca (OH)2、CaCO3、CaSO4·2H2O) to remove mercury. In experiments carried out in simulation of coal-fired flue gas, it was found that Ca (OH)2For HgCl2The adsorption efficiency of the mercury can reach 85 percent, but the mercury can not adsorb the mercury (Hg) in the mercury0) Only at SO2In the presence of 18% Hg0Can be removed. Alkaline adsorbents like CaO also adsorb HgCl very well2，SO2When present, to Hg0The removal rate of (D) was 35%. At present, the calcium-based adsorbent is still in a laboratory research stage and is not used in industrial practice, and the method only treats Hg in flue gas of a coal power station boiler2+Has higher removal rate to Hg in the flue gas of the coal-fired power station boiler0The removal effect is not significant.
Zeolite materials are used as adsorbents for industrial boilers to control mercury emissions. One has added a known amount of elemental mercury (Hg) to the coal combustion flue gas0) The experiment shows that the zeolite can adsorb Hg at high temperatureand low temperature0And Hg2+. The zeolite material is still under research, the engineering application is still immature, and the efficiency of removing mercury from the flue gas of the coal-fired power station boiler is still to be improved.
The fly ash is used as an adsorbent to remove mercury in the flue gas. The fly ash generated by the fire coal can absorb mercury in flue gas, the fly ash with high carbon content is very beneficial to mercury adsorption, but scientists think that the carbon content of the fly ash is greatly increased, and the mercury adsorption capacity of the fly ash cannot be correspondingly improved. Furthermore, fly ash with high carbon content has low resistivity, which reduces the dust removal efficiency of the ESP. However, in general, the removal rate of the total mercury in the flue gas of the coal-fired power station boiler by the adsorbents is too low to popularize and apply.
At present, the mercury pollution control technology is applied to the industry of garbage incinerators abroad, and China does not have an industrial device special for removing mercury in flue gas. In view of the low mercury concentration and the high removal difficulty in the coal-fired flue gas, the technology in the field is in the industrial test and the pilot plant stage abroad, and is not popularized on a large scale. With increasingly stringent environmental requirements, the pollution control of heavy metals, especially mercury, from coal combustion is a matter of course. The preparation method of the adsorbent disclosed by the patent provides a foundation for occasions for controlling mercury emission in flue gas, such as coal-fired boilers, waste incineration boilers and some chemical manufacturers needing tail gas treatment, can be applied in a large scale after the coal-fired mercury pollution emission control standards come out at home and abroad, the mercury emission of coal-fired power station boilers iscontrolled in 2004 in the United states, and China will come out of corresponding environmental protection standards in the near future.
Disclosure of Invention
The invention aims to provide a preparation method of a coal-fired flue gas mercury removal adsorbent.
Adding sulfuric acid accounting for 1-2% of the total amount of water into water to enable the water solution to be acidic, adding heptavalent manganese salt solid or solution, stirring to enable heptavalent manganese salt to be dissolved, adding acidic divalent manganese salt solution, stirring simultaneously, adding granular adsorbent, continuously stirring for 30-40 minutes, heating and drying at 80-100 ℃ to be in a solid state, and grinding into powder, wherein the adding amount ratio of the heptavalent manganese salt, the divalent manganese salt and the granular adsorbent is 1: 1-2: 35-50. The heptavalent manganese salt is potassium permanganate. The divalent manganese salt is manganese sulfate, manganese chloride or manganese nitrate. The adsorbent is one or a mixture of activated carbon, ore or biomass. The ores are as follows: montmorillonite, vermiculite, zeolite or activated clay. The biomass is as follows: seaweed meal or biomass-derived carbon.
The invention has the advantages that:
1) the adsorbent prepared by the method can comprehensively control three forms (gaseous zero-valent mercury, gaseous divalent mercury and granular mercury) of mercury in the flue gas of the coal-fired power plant and convert the three forms into inert compounds;
2) the flue gas can be directly sprayed on the flue, so that the operation is more convenient;
3) the method has simple and practical process and easy popularization;
4) the mercury discharge control device can be combined with the existing pollutant control devices of the coal-fired power plant, such as a wet desulphurization device, a dry desulphurization device and a semi-dry desulphurization device, thereby not only reducing the initial investment, but also saving the operation cost.
Detailed Description
The invention relates to a method for preparing an adsorbent for removing mercury in flue gas by an active manganese dioxide impregnation method. The method comprises the following steps:
at normal temperature, adding sulfuric acid which is more than 1 percent of the total amount of water into the water to enable the water solution to be acidic, adding solid or solution of heptavalent manganese salt, stirring to enable the heptavalent manganese salt to be completely dissolved, adding acidic manganous salt solution, stirring simultaneously, adding granular adsorbent, and when the heptavalent manganese salt is potassium permanganate and the manganous salt is manganese nitrate, adding the ratio of the potassium permanganate, the manganous salt and the active carbon is 1: 1.104: 40. Adding adsorbent, stirring for 30 min, heating at 80 deg.C or above to dry to solid state, and grinding into powder.
Example 1
2000ml of deionized water is taken and 20ml of concentrated H is added2SO427.6 g of KMnO were added4Stirred to be completely dissolved, and 94 g of 50% Mn (NO) is added3)2Adding 1000 g of active carbon slowly, stirring for 30 minutes, drying in an oven at 100 ℃, and grinding into powder for use. For a coal fired boiler, the flue gas production is about 6X 105Nm3H, the total mercury content in the flue gas produced is about 3.8 mug/Nm3. When the temperature of the flue gas is 150 ℃, the MnO-passed flue gas is sprayed into the flue gas2The modified activated carbon adsorbent is impregnated, and the injection amount is C/Hg 12000, so that the mercury in the single substance state in the flue gas is converted into Hg2MnO2So as to be solidified, the adsorption process is a stronger chemical adsorption process, and new compound Hg is generated after the adsorption2MnO2：
The mercury is in a low-price state in the compound, and electrons are transferred from the mercury to manganese in the compound, so that the mercury and the manganese are strongly combined. Then all the particulate matters are collected by cloth bag dust removal equipment, 26% of the total collected amount is sent back to the flue through a material returning device, and the content of total mercury in the flue gas after the dust remover is reduced to 0.34-0.36 mu g/Nm3And the total removal efficiency of mercury in the flue gas is higher than 90%.
Example 2
2000ml of deionized water is taken and 20ml of concentrated H is added2SO427.6 g of KMnO were added4Stirred to be completely dissolved, and 94 g of 50% Mn (NO) is added3)2Slowly adding 1000 g of vermiculite fine powder, continuously stirring for 30 minutes, drying in an oven at 100 ℃, and then grinding into powder for use. For a coal fired boiler, the flue gas production is about 6X 105Nm3H, the total mercury content in the flue gas produced is about 4.2 mug/Nm3. When the temperature of the flue gas is 150 ℃, the MnO-passed flue gas is sprayed into the flue gas2Dipping modified vermiculite, spraying amount isvermiculite/mercury 16000, converting mercury in single substance state in flue gas into Hg2MnO2And is cured. Then all the particulate matter is dedusted by a cloth bagCollecting by equipment, returning 30% of the total collected amount to the flue through a material returning device, and reducing the content of total mercury in the flue gas after the dust remover to 0.38-0.41 mug/Nm3And the total removal efficiency of mercury in the flue gas is higher than 90%.
Example 3
2000ml of deionized water is taken and 20ml of concentrated H is added2SO431.6 g of KMnO were added4Stirring to completely dissolve the components, adding 45.3 g of MnSO4Adding 1000 g of active carbon slowly, stirring for 30 minutes, drying in an oven at 100 ℃, and grinding into powder for use. For a coal fired boiler, the flue gas production is about 6X 105Nm3H, the total mercury content in the flue gas produced is about 3.5 mug/Nm3. When the temperature of the flue gas is 150 ℃, the MnO-passed flue gas is sprayed into the flue gas2The spraying amount of the impregnated and modified activated carbon adsorbent is C/Hg 13000, so that the mercury in the single substance state in the flue gas is converted into Hg2MnO2And is cured. Then all the particulate matters are collected by cloth bag dust removal equipment, 26% of the total collected amount is sent back to the flue through a material returning device, and the content of total mercury in the flue gas after the dust remover is reduced to 0.33-0.35 mu g/Nm3And the total removal efficiency of mercury in the flue gas is higher than 90%.
Example 4
2000ml of deionized water is taken and 20ml of concentrated H is added2SO431.6 g of KMnO were added4Stirring to dissolve completely, adding 37.8 g MnCl2Adding 1000 g of active carbon slowly, stirring for 30 minutes, drying in an oven at 100 ℃, and grinding into powder for use. For a coal fired boiler, the flue gas production is about 6X 105Nm3H, the total mercury content in the flue gas produced is about 3.9 mug/Nm3. When the temperature of the flue gas is 150 ℃, the MnO-passed flue gas is sprayed into the flue gas2The modified activated carbon adsorbent is impregnated, the injection amount is C/Hg 14000, so that the mercury in the single substance state in the flue gas is converted into Hg2MnO2And is cured. Then all the particulate matters are collected by cloth bag dust removal equipment, 26% of the total collected amount is sent back to the flue through a material returning device, and the content of total mercury in the flue gas after the dust remover is reduced to 0.36-0.38 mu g/Nm3And the total removal efficiency of mercury in the flue gas is higher than 90%.
Example 5
2000ml of deionized water is taken and 20ml of concentrated H is added2SO431.6 g of KMnO were added4Stirring to dissolve completely, adding 37.8 g MnCl2Adding 1000 g of vermiculite slowly, stirring for 30 minutes, drying in an oven at 100 ℃, and grinding into powder for use. For a coal fired boiler, the flue gas production is about 6X 105Nm3H, the total mercury content in the flue gas produced is about 3.9 mug/Nm3. When the temperature of the flue gas is 150 ℃, the MnO-passed flue gas is sprayed into the flue gas2The modified activated carbon adsorbent is impregnated, the injection amount is C/Hg 14000, so that the mercury in the single substance state in the flue gas is converted into Hg2MnO2And is cured. Then all the particulate matters are collected by cloth bag dustremoval equipment, 26% of the total collected amount is sent back to the flue through a material returning device, and the content of total mercury in the flue gas after the dust remover is reduced to 0.34-0.36 mu g/Nm3And the total removal efficiency of mercury in the flue gas is higher than 90%.
Claims (7)
1. A preparation method of a coal-fired flue gas mercury removal adsorbent is characterized by comprising the following steps: adding sulfuric acid with the total amount of 1-2% of water into water to make the water solution acidic, adding heptavalent manganese salt solid or solution, stirring to dissolve heptavalent manganese salt, adding acidic divalent manganese salt solution, stirring simultaneously, adding granular adsorbent, continuously stirring for 30-40 min, heating and drying at 80-100 deg.C to obtain solid state, and grinding into powder, wherein the addition ratio of heptavalent manganese salt, divalent manganese salt and granular adsorbent is 1: 1-2: 35-50.
2. The method for preparing the coal-fired flue gas mercury removal adsorbent according to claim 1, wherein the heptavalent manganese salt is potassium permanganate.
3. The method for preparing the coal-fired flue gas mercury removal adsorbent according to claim 1, wherein the divalent manganese salt is manganese sulfate, manganese chloride or manganese nitrate.
4. The method for preparing the coal-fired flue gas mercury removal adsorbent according to claim 1, wherein the adsorbent is one or a mixture of activated carbon, ore or biomass.
5. The method for preparing the coal-fired flue gas mercury removal adsorbent according to claim 4, wherein the ore is: montmorillonite, vermiculite, zeolite or activated clay.
6. The method for preparing the coal-fired flue gas mercury removal adsorbent according to claim 4, wherein the biomass is: seaweed meal or biomass-derived carbon.
7. The method for preparing the coal-fired flue gas mercury removal adsorbent according to claim 2, 3 or 4, characterized in that when the heptavalent manganese salt is potassium permanganate and the divalent manganese salt is manganese nitrate, the ratio of the addition amounts of the potassium permanganate, the divalent manganese salt and the activated carbon is 1: 1.104: 40.
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| CN101301602B (en) * | 2008-01-18 | 2010-07-21 | 昆明理工大学 | A kind of preparation method of gaseous elemental mercury adsorption and purification adsorbent |
| CN102277013B (en) * | 2010-09-26 | 2013-05-29 | 郑州裕昌有机硅化工有限公司 | Production method of active manganese dioxide for polysulfide sealant solidification |
| CN106000304A (en) * | 2016-05-31 | 2016-10-12 | 舒尔环保科技（合肥）有限公司 | Composite air purifying agent for purifying cigarette smoke |
| CN108940378B (en) * | 2018-07-17 | 2021-04-30 | 江苏中能电力设备有限公司 | Demercuration catalyst for flue gas and preparation method and application thereof |
| CN109224631A (en) * | 2018-09-28 | 2019-01-18 | 安徽元琛环保科技股份有限公司 | A kind of dedusting demercuration integration filtrate and preparation method thereof |
| CN109224829A (en) * | 2018-09-28 | 2019-01-18 | 安徽元琛环保科技股份有限公司 | A kind of preparation method of Mobyneb polytetrafluoroethylene fibre |
| CN110514485A (en) * | 2019-09-30 | 2019-11-29 | 福建省锅炉压力容器检验研究院 | A kind of stationary source mercury in flue gas sampling apparatus |
| CN114477698B (en) * | 2022-02-11 | 2023-01-03 | 江南大学 | Application of ferric chloride mediated cyanobacteria-based biochar in removing zero-valent mercury in flue gas |
| CN114522531B (en) * | 2022-02-23 | 2023-10-13 | 河北华硕化工助剂有限公司 | High-efficiency composite desulfurization and denitrification absorbent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4224676A1 (en) * | 1991-08-14 | 1993-02-18 | Veba Kraftwerke Ruhr | METHOD FOR SEPARATING MERCURY FROM SMOKE GASES |
| CN1290191A (en) * | 1998-01-12 | 2001-04-04 | 苏德-化学公司 | Adsorbent for a hydrocarbon stream and process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4224676A1 (en) * | 1991-08-14 | 1993-02-18 | Veba Kraftwerke Ruhr | METHOD FOR SEPARATING MERCURY FROM SMOKE GASES |
| CN1290191A (en) * | 1998-01-12 | 2001-04-04 | 苏德-化学公司 | Adsorbent for a hydrocarbon stream and process |
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