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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Abstract
The present invention discloses a method for preparing coal burning fume mercury-removing adsorbents. 1 to 2% of sulfuric acid of water total amount is added in water so that water solution is acidic; a heptavalent manganese salt solid or solution is added and stirred so that heptavalent manganese salt is dissolved; acidic divalent manganese salt solution is added and stirred simultaneously; a granular adsorbent is added and continuously stirred for 30 to 40 minutes; the granular adsorbent is heated and dried at 80 to 100 DEG C into a solid; the solid is ground into powder, wherein the addition quantity rate of the heptavalent manganese salt, divalent manganese salt and the granular adsorbent is 1 to (1 to 2) to (35 to 50). The present invention has the advantages that an adsorbent prepared by the method comprehensively controls three forms of mercury in fume of a coal burning power plant and converts the mercury into an inert compound; the adsorbent is directly sprayed and added to the fume on a flue; the operation is convenient; the method has simple and practical technology and easy popularization; the adsorbent can be combined with the existing pollutant control device of the coal burning power plant for discharge control over the mercury; the adsorbent reduces initial investment and also saves operation 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101301602B (en) * | 2008-01-18 | 2010-07-21 | 昆明理工大学 | Method for preparing gaseous mercury absorbing and purifying agent |
| 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 |
| 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 |
| 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 |
| 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 |
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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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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