CN108940239B - Method for controlling fine particles and heavy metals in coal-fired power plants based on modified attapulgite - Google Patents
Method for controlling fine particles and heavy metals in coal-fired power plants based on modified attapulgite Download PDFInfo
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Abstract
本发明公开了一种基于改性凹凸棒控制燃煤电厂细颗粒物及重金属的方法，按照燃煤量与改性凹凸棒粉末质量比（43000‑50000）：1的方式，在燃烧有煤的炉膛中喷入改性凹凸棒粉末；并按照电除尘前的烟气量（标态、湿基，6%O2,单位：m3/s）与改性凹凸棒液体体积比（5000000‑8000000）:1方式，在电除尘通道中喷洒改性凹凸棒液体；所述的改性凹凸棒粉末为采用浓度为3.5‑3.9mol/L硫酸进行酸改性；所述的改性凹凸棒液体采用改性凹凸棒粉末分散在去离子水溶液中，制得悬浮液，并将悬浮液置于60‑70℃，按质量比1：60加入酸性增稠剂制得。该基于改性凹凸棒控制燃煤电厂细颗粒物及重金属的方法可以减少燃煤电厂在燃烧时产生的细颗粒物及重金属。The invention discloses a method for controlling fine particles and heavy metals in a coal-fired power plant based on modified attapulgite rods. The modified attapulgite powder was sprayed into the middle; and the volume ratio of the flue gas (standard state, wet basis, 6% O 2 , unit: m 3 /s) to the modified attapulgite liquid (5000000‑8000000) before electrostatic precipitator 1 method, spraying modified attapulgite liquid in the electrostatic precipitator channel; described modified attapulgite powder is acid-modified by adopting concentration of 3.5-3.9mol/L sulfuric acid; described modified attapulgite liquid adopts modified attapulgite liquid. The attapulgite powder is dispersed in a deionized aqueous solution to obtain a suspension, and the suspension is placed at 60-70°C, and an acidic thickener is added at a mass ratio of 1:60 to obtain the suspension. The method for controlling fine particles and heavy metals in a coal-fired power plant based on the modified attapulgite can reduce the fine particles and heavy metals produced by the coal-fired power plant during combustion.
Description
Technical Field
The invention particularly relates to a method for controlling fine particles and heavy metals of a coal-fired power plant based on modified attapulgite.
Background
The large amount of pollutants (such as sulfur oxides, nitrogen oxides, fine particulate matters, heavy metals and the like) emitted by coal-fired power plants causes great harm to the atmospheric environment and human health. After the coal-fired flue gas is subjected to dust removal and limestone gypsum wet desulphurization, most of dust and heavy metals can be removed, but fine particles and heavy metals with considerable mass and taking mercury, lead, chromium, cadmium and the like as main elements still exist in the flue gas discharged into the atmosphere.
The existing control technology for fine particulate matter emission mainly comprises electric agglomeration, sound agglomeration, magnetic agglomeration, thermal agglomeration, turbulent (boundary layer) flow agglomeration, chemical agglomeration and the like. Among them, the method of capturing submicron particles using an adsorbent is called chemical agglomeration, and the agglomeration mechanism thereof is mainly physical adsorption and chemical reaction. At present, the research contents of the chemical agglomeration method adopted by fire coal fine particles at home and abroad mainly focus on the influence of common adsorbents such as kaolinite, bauxite and the like on the particle agglomeration and the removal of one or more heavy metals, and the research of the chemical agglomeration trapping by using a novel agglomerating agent is not much. The search for an economic and effective agglomerating agent is the key to promoting the agglomeration and the trapping of the particulate matters by a physical and chemical agglomeration method.
Attapulgite, also known as attapulgite or palygorskite, is a water-containing magnesium-rich aluminosilicate clay ore with a layered chain structure. The crystal is rod-like, fibrous, needle-like clay mineral, i.e. two layers of silica tetrahedron and one layer of aluminous octahedron, and has standard chemical formula of Mg5Si8O20(HO)2(OH2)4·4H2O, but actually the chemical composition is SiO2、MgO、Al2O3Mainly contains a certain amount of Fe2O3、MnO、TiO2And the like. The attapulgite has a plurality of special physicochemical properties such as adsorptivity, rheology, catalysis, ion exchange, plasticity and the like because of the unique layer chain crystal structure of the attapulgite. These characteristics of the attapulgiteThe attapulgite is widely applied to the fields of petroleum, chemical industry, medicine, environmental protection, printing and the like. Its large comparative area and its adsorption centers present on the surface make it suitable for use in the control of coal-fired fine particulate matter.
The naturally produced attapulgite is accompanied by minerals such as montmorillonite, kaolinite, hydromica, quartz, carbonate and the like. Proper acid treatment can play roles in dredging pore channels, removing carbonate and impurities, increasing the number of active adsorption sites and the like. On the other hand, due to cation exchangeability of attapulgite, H with smaller radius+Can replace the attapulgite interlayer part K+、Na+、Ca2+And Mg2+Plasma, increasing the empty volume.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel modified attapulgite clay which has the physical and chemical modification to promote the capture of fine particles and heavy metals so as to achieve the aim of reducing the fine particles and heavy metals discharged by a coal-fired power plant.
The purpose of the invention is realized by the following technical scheme.
A method for controlling fine particles and heavy metals of a coal-fired power plant based on modified attapulgite comprises the following steps of: 1, spraying modified attapulgite powder into a hearth of a coal-fired power plant; according to the flue gas amount (standard state, wet basis, 6% O) before electric precipitation2The unit: m is3The volume ratio of the modified attapulgite liquid to the modified attapulgite liquid (5000000-;
the modified attapulgite powder is subjected to acid activation by adopting sulfuric acid with the concentration of 3.5-3.9 mol/L;
the modified attapulgite liquid is prepared by dispersing modified attapulgite powder in a deionized water solution to prepare a suspension, and placing the suspension at 60-70 ℃ according to a mass ratio of 1: 60 adding an acidic thickening agent.
Further, the process flow of the coal-fired power plant is as follows: the method comprises the following steps of combustion of a hearth, spraying of modified attapulgite powder, SCR denitration, spraying of modified attapulgite liquid, electric precipitation, limestone and gypsum wet desulphurization and chimney discharge.
Further, the preparation of the modified attapulgite powder comprises the following steps:
(1) grinding attapulgite, sieving to 2-4mm, and mixing with deionized water according to the weight ratio of (5-15): 150 to form suspended slurry, fully dispersing the suspended slurry through ultrasonic treatment, treating the upper suspension in a centrifuge of 3000r/min for 5-10min, standing and vacuumizing;
(2) placing attapulgite solution in a container, adding 3.5-3.9mol/L sulfuric acid for acid activation, performing ultrasonic treatment for 10-20min, standing, and vacuum filtering;
(3) placing the acid-activated attapulgite in a container, adding vinyltriethoxysilane at a ratio of 1:100 for modification, controlling the temperature at 65-75 deg.C, performing ultrasonic treatment for 10-20min, filtering, mechanically stirring for 3 hr, oven drying, pulverizing, and sieving to 2-4 mm.
Further, the modified attapulgite powder is prepared from the following components in a mass ratio of 1: 50000 is sprayed into the hearth burning anthracite.
Further, the modified attapulgite powder is prepared from the following components in a mass ratio of 1: 48000 it is injected into the hearth of a furnace burning bituminous coal.
Further, the modified attapulgite powder is prepared from the following components in a mass ratio of 1: 43000 spraying into the hearth of burning brown coal.
The invention has the beneficial effects that:
(1) the acid activation treatment can partially depolymerize the rod crystal beam of the attapulgite, change the specific surface area of the attapulgite and remove mineral impurities such as carbonate and the like. At the same time H+Can replace Mg contained in the attapulgite2+、Al3+And Fe3+The metal ions improve the cation exchangeability of the attapulgite and the adsorbability thereof.
(2) The limestone gypsum wet desulphurization slurry has larger influence on the desulphurization efficiency by chloride ions and nitrate ions, the formula uses sulfuric acid as modified acid, so that new pollution can not be generated, the influence on the desulphurization efficiency by the chloride ions and the nitrate ions in the conventional modified acid hydrochloric acid and nitric acid can be avoided, and the quality of gypsum can be improved by using the attapulgite modified by the sulfuric acid.
(3) The adopted vinyl triethoxy silane is matched with modification, so that a molecular bridge can be erected between the interfaces of the inorganic filler and the organic high polymer matrix material, two materials with different properties are coupled together, the functions of strengthening and improving the performance are achieved, and the adsorbability of the material is greatly improved by matching with a mechanical stirring mode.
(4) The discharge of fine particles and heavy metals is efficiently reduced by spraying the modified attapulgite powder in a combustion boiler and spraying the modified attapulgite liquid before electric precipitation. The modified attapulgite is used as a strong adsorbent and has physical and chemical reactions at the position of the modified attapulgite, thereby increasing the particle size of particles and reducing the output of fine particles, and the particles coated with gaseous heavy metals can be removed by devices such as electric precipitation, limestone-gypsum wet desulphurization and the like.
(5) The attapulgite has the advantages of abundant reserves, proper price, simple preparation, easy realization of large-scale production, capability of increasing the quality of byproduct gypsum, good environmental protection benefit and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A method for controlling fine particles and heavy metals of a coal-fired power plant based on modified attapulgite comprises the following steps of mixing the coal-fired amount with modified attapulgite powder in a mass ratio of 50000: 1, spraying modified attapulgite powder into a hearth burning anthracite; according to the flue gas amount (standard state, wet basis, 6% O) before electric precipitation2The unit: m is3/s) and the volume ratio of the modified attapulgite liquid is 8000000:1, spraying the modified attapulgite liquid in the electric precipitation channel;
the preparation method of the modified attapulgite powder comprises the following steps:
(1) grinding attapulgite, crushing, sieving to 4mm, and mixing with deionized water according to the weight ratio of 5: 150 to form suspended slurry, fully dispersing the suspended slurry through ultrasonic treatment, treating the upper suspension in a centrifuge of 3000r/min for 10min, standing and vacuumizing;
(2) placing the attapulgite solution in a container, adding 3.9mol/L sulfuric acid for acid activation, performing ultrasonic treatment for 10min, standing, and vacuum filtering;
(3) placing the acid-activated attapulgite in a container, adding vinyltriethoxysilane at a ratio of 1:100 for modification, controlling the temperature at 75 deg.C, performing ultrasonic treatment for 20min, filtering, mechanically stirring for 3 hr, oven drying, pulverizing, and sieving to 2-4 mm.
The modified attapulgite liquid is prepared by dispersing modified attapulgite powder in a deionized water solution to prepare a suspension, and placing the suspension at 70 ℃ according to a mass ratio of 1: 60 adding an acidic thickening agent.
The process flow of the coal-fired power plant is as follows: the method comprises the following steps of combustion of a hearth, spraying of modified attapulgite powder, SCR denitration, spraying of modified attapulgite liquid, electric precipitation, limestone and gypsum wet desulphurization and chimney discharge.
Example 2
A method for controlling fine particles and heavy metals of a coal-fired power plant based on modified attapulgite comprises the following steps of mixing the coal-fired amount with the modified attapulgite powder by mass ratio of 48000: 1, spraying modified attapulgite powder into a hearth burning bituminous coal; according to the flue gas amount (standard state, wet basis, 6% O) before electric precipitation2The unit: m is3/s) and the volume ratio of the modified attapulgite liquid is 6500000:1, spraying the modified attapulgite liquid in the electric precipitation channel;
the preparation method of the modified attapulgite powder comprises the following steps:
(1) grinding attapulgite, crushing, sieving to 2mm, and mixing with deionized water according to the weight ratio of 15: 150 to form suspended slurry, fully dispersing the suspended slurry through ultrasonic treatment, treating the upper suspension in a centrifuge of 3000r/min for 5min, standing and vacuumizing;
(2) placing attapulgite solution in a container, adding 3.5mol/L sulfuric acid for acid activation, performing ultrasonic treatment for 20min, standing, and vacuum filtering;
(3) placing the acid-activated attapulgite in a container, adding vinyltriethoxysilane at a ratio of 1:100 for modification, controlling the temperature at 65 deg.C, performing ultrasonic treatment for 20min, filtering, mechanically stirring for 3 hr, oven drying, pulverizing, and sieving to 2-4 mm.
The modified attapulgite liquid is prepared by dispersing modified attapulgite powder in a deionized water solution to prepare a suspension, and placing the suspension at 60 ℃ according to a mass ratio of 1: 60 adding an acidic thickening agent.
The process flow of the coal-fired power plant is as follows: the method comprises the following steps of combustion of a hearth, spraying of modified attapulgite powder, SCR denitration, spraying of modified attapulgite liquid, electric precipitation, limestone and gypsum wet desulphurization and chimney discharge.
Example 3
A method for controlling fine particles and heavy metals of a coal-fired power plant based on modified attapulgite comprises the following steps of mixing the amount of combustion coal with the modified attapulgite powder by mass ratio of 43000: 1, spraying modified attapulgite powder into a hearth burning lignite; according to the flue gas amount (standard state, wet basis, 6% O) before electric precipitation2The unit: m is3The volume ratio of the modified attapulgite liquid to the modified attapulgite liquid is 5000000:1, and the modified attapulgite liquid is sprayed in an electric precipitation channel;
the preparation method of the modified attapulgite powder comprises the following steps:
(1) grinding and crushing attapulgite, sieving to 3mm, and mixing with deionized water according to the weight ratio of 10: 150 to form suspended slurry, fully dispersing the suspended slurry through ultrasonic treatment, treating the upper suspension in a centrifuge of 3000r/min for 7min, standing and vacuumizing;
(2) placing the attapulgite solution in a container, adding 3.7mol/L sulfuric acid for acid activation, performing ultrasonic treatment for 15min, standing, and vacuum filtering;
(3) placing the acid-activated attapulgite in a container, adding vinyltriethoxysilane at a ratio of 1:100 for modification, controlling the temperature at 60 deg.C, performing ultrasonic treatment for 20min, filtering, mechanically stirring for 3 hr, oven drying, pulverizing, and sieving to 2-4 mm.
The modified attapulgite liquid is prepared by dispersing modified attapulgite powder in a deionized water solution to prepare a suspension, and placing the suspension at 60 ℃ according to a mass ratio of 1: 60 adding an acidic thickening agent.
The process flow of the coal-fired power plant is as follows: the method comprises the following steps of combustion of a hearth, spraying of modified attapulgite powder, SCR denitration, spraying of modified attapulgite liquid, electric precipitation, limestone and gypsum wet desulphurization and chimney discharge.
Comparative example
The existing attapulgite surface modification treatment method specifically comprises the steps of firstly calcining attapulgite, then mixing ethanol and water according to the weight ratio of 1:13 to prepare a treatment solution, immersing the calcined attapulgite into the treatment solution, carrying out ultrasonic dispersion treatment for 30min, then filtering out, and drying.
Examples of the experiments
The same batch of attapulgite is selected as an experimental raw material, and then modified by the methods corresponding to the above examples 1, 2, 3 and comparative examples, wherein the modified attapulgite powder is sprayed into a hearth and the modified attapulgite liquid is sprayed into an electric precipitation channel in the examples 1, 2 and 3, the modified attapulgite powder is only sprayed into the hearth in the comparative examples, the mass concentration of fine particulate matters is calculated by using a fine particulate matter sampler, the particles are collected by using a load-bearing particulate matter sampler, and the heavy metal content in the fine particulate matters is analyzed by ICP-MS test, and the specific comparative data are shown in the following table.
The modified attapulgite powder and the modified attapulgite liquid prepared by the scheme can obviously reduce fine particles, the mass concentration of the modified attapulgite powder and the modified attapulgite liquid is reduced by 56-64%, and meanwhile, the concentration of heavy metals such As As, Pb and the like in the fine particles can be reduced by 62-72%, so that the effect is obviously better compared with the use of the existing modified attapulgite in a coal-fired power plant.
The invention has the beneficial effects that: (1) the acid activation treatment can partially depolymerize the rod crystal beam of the attapulgite, change the specific surface area of the attapulgite and remove mineral impurities such as carbonate and the like. At the same time H+Can replace Mg contained in the attapulgite2+、Al3+And Fe3+The metal ions improve the cation exchangeability of the attapulgite and the adsorbability thereof. (2) The limestone gypsum wet desulphurization slurry has larger influence on the desulphurization efficiency by chloride ions and nitrate ions, the formula uses sulfuric acid as modified acid, so that new pollution can not be generated, the influence on the desulphurization efficiency by the chloride ions and the nitrate ions in the conventional modified acid hydrochloric acid and nitric acid can be avoided, and the quality of gypsum can be improved by using the attapulgite modified by the sulfuric acid. (3) The adopted vinyl triethoxy silane is matched with modification, so that a molecular bridge can be erected between the interfaces of the inorganic filler and the organic high polymer matrix material, two materials with different properties are coupled together, the functions of strengthening and improving the performance are achieved, and the adsorbability of the material is greatly improved by matching with a mechanical stirring mode. (4) The discharge of fine particles and heavy metals is efficiently reduced by spraying the modified attapulgite powder in a combustion boiler and spraying the modified attapulgite liquid before electric precipitation. The modified attapulgite is used as a strong adsorbent and has physical and chemical reactions at the position of the modified attapulgite, thereby increasing the particle size of particles and reducing the output of fine particles, and the particles coated with gaseous heavy metals can be removed by devices such as electric precipitation, limestone-gypsum wet desulphurization and the like. (5) The attapulgite has the advantages of abundant reserves, proper price, simple preparation, easy realization of large-scale production, capability of increasing the quality of byproduct gypsum, good environmental protection benefit and the like.
What has been described above is a specific embodiment of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (6)
1. Control fine particles of coal-fired power plant based on modified attapulgiteA method for producing a heavy metal, characterized by: according to the mass ratio of the coal burning quantity to the modified attapulgite powder (43000-: 1, spraying modified attapulgite powder into a hearth of a coal-fired power plant; according to the flue gas amount (standard state, wet basis, 6% O) before electric precipitation2The unit: m 3/s) and the volume ratio (5000000-;
the modified attapulgite powder is subjected to acid modification by adopting sulfuric acid with the concentration of 3.5-3.9 mol/L;
the modified attapulgite liquid is prepared by dispersing modified attapulgite powder in a deionized water solution to prepare a suspension, placing the suspension at 60-70 ℃, and adding vinyl triethoxysilane according to the mass ratio of 1:100 for modification.
2. The method for controlling fine particulate matter and heavy metals of a coal-fired power plant based on modified attapulgite of claim 1, wherein the process flow of the coal-fired power plant is as follows: the method comprises the following steps of combustion of a hearth, spraying of modified attapulgite powder, SCR denitration, spraying of modified attapulgite liquid, electric precipitation, limestone and gypsum wet desulphurization and chimney discharge.
3. The method for controlling fine particulate matter and heavy metals of a coal-fired power plant based on modified attapulgite of claim 1, which is characterized in that: the modified attapulgite powder comprises the following components in percentage by mass 1: 50000 is sprayed into the hearth burning anthracite.
4. The method for controlling fine particulate matter and heavy metals of a coal-fired power plant based on modified attapulgite of claim 1, which is characterized in that: the modified attapulgite powder comprises the following components in percentage by mass 1: 48000 it is injected into the hearth of a furnace burning bituminous coal.
5. The method for controlling fine particulate matter and heavy metals of a coal-fired power plant based on modified attapulgite of claim 1, which is characterized in that: the modified attapulgite powder comprises the following components in percentage by mass 1: 43000 spraying into the hearth of burning brown coal.
6. The method for controlling fine particulate matter and heavy metals of a coal-fired power plant based on modified attapulgite according to any one of claims 1 to 5, characterized in that the preparation of the modified attapulgite powder comprises the following steps: (1) grinding attapulgite, sieving to 2-4mm, and mixing with deionized water according to the weight ratio of (5-15): 150 to form suspended slurry, fully dispersing the suspended slurry through ultrasonic treatment, treating the upper suspension in a centrifuge of 3000r/min for 5-10min, standing and vacuumizing;
(2) placing attapulgite solution in a container, adding 3.5-3.9mol/L sulfuric acid for acid activation, performing ultrasonic treatment for 10-20min, standing, and vacuum filtering;
(3) placing the acid-activated attapulgite in a container, adding vinyltriethoxysilane at a ratio of 1:100 for modification, controlling the temperature at 65-75 deg.C, performing ultrasonic treatment for 10-20min, filtering, mechanically stirring for 3 hr, oven drying, pulverizing, and sieving to 2-4 mm.
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