CN105107518A - Synergetic denitration and demercuration catalyst for coal-fired power plant flue gas and preparation method thereof - Google Patents
Synergetic denitration and demercuration catalyst for coal-fired power plant flue gas and preparation method thereof Download PDFInfo
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- CN105107518A CN105107518A CN201510557006.3A CN201510557006A CN105107518A CN 105107518 A CN105107518 A CN 105107518A CN 201510557006 A CN201510557006 A CN 201510557006A CN 105107518 A CN105107518 A CN 105107518A
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Abstract
The invention belongs to the technical fields of novel catalytic materials, environmental protection and atmosphere pollution control, and relates to a synergetic denitration and demercuration catalyst for coal-fired power plant flue gas and a preparation method of the synergetic denitration and demercuration catalyst. The catalyst powder consists of compound metal oxide active components supported on titanium dioxide and a binder. The required compound catalyst is obtained by vacuum extrusion of powder to be honeycomb-shaped, as well as drying, calcination and activation. The developed catalyst is utilized for catalytic oxidation of elemental mercury while removing nitrogen oxides, so as to convert the elemental mercury into mercury in an oxidation state, and then the removal of mercury is achieved by combining with existing electrostatic dust removal and wet desulfurization equipment. The synergetic denitration and demercuration catalyst achieves the simultaneous removal of NOx and Hg<0> under the premise of not increasing a flue gas purification device, so that the transformation of the existing device is achieved, a lot of cost is saved, the pollution to the atmosphere is reduced, and the synergetic denitration and demercuration catalyst has relatively high industrial application value.
Description
Technical field
The invention belongs to new catalytic material, environmental protection and technical field of air pollution control, relate to a kind of honeycombed catalyst of working in coordination with denitration demercuration for coal-fired plant flue gas.This catalyst powder is made up of the composite metal oxide (active component) of titanium dichloride load and binding agent.Powder becomes cellular, dry, calcining and activating through vacuum press, obtains required composite catalyst.Catalytic oxidation Elemental Mercury while utilizing the catalyst removal oxynitrides developed, makes it change into oxidation state mercury, then realizes removing of mercury in conjunction with existing electrostatic precipitation and wet desulphurization equipment.Under the prerequisite not increasing smoke eliminator, realize NO
xand Hg
0while remove, not only realize saving great amount of cost to the transformation of existing apparatus, and decrease the pollution to air, there is stronger industrial application value.
Background technology
Coal-fired mercury pollution is the another large pollution problem in recent years after coal-fired sulphur and nitrogen oxides pollution, and wherein coal-burning power plant is topmost mercury emissions pollution sources.China's energy is based on coal, and the average mercury content of coal is 0.22mg/kg.Because China controls still to be in the starting stage to mercury content in coal-fired plant flue gas, therefore the mercury pollution of coal-burning power plant is particularly serious.Heavy metal pollution integrated control " 12 " planning explicitly calls for the heavy metals emissions such as mercury in 2015 to cut down 15% than 2007.Fossil-fuel power plant atmospheric pollutant emission standard requires that mercury and mercuric compounds discharge capacity controlled at 0.03mg/m by coal-burning boiler from 1 day January in 2015
3below.Therefore, mercury control technical research is carried out significant for improving China's environmental quality.
The existence form of Mercury In Coal Combustion Flue Gas has Elemental Mercury (Hg
0), bivalent mercury (Hg
2+) and particle mercury (Hg
p) three kinds.Under the high temperature of coal-burning boiler, most mercury is all broken down into Elemental Mercury and is present in a gaseous form in flue gas.Gaseous state bivalent mercury is easily molten gives water, easily catch by wet scrubbing system and remove; Particle mercury is easily by removals such as electric cleaners; And Elemental Mercury volatility is high and be insoluble in water, being relatively stable form, is the Focal point and difficult point of mercury in flue gas Environmental capacity.Therefore, research and development flue gas demercuration technique and catalyst thereof will become the focus of research at present.
Demercuration technology ripe in the market comprises charcoal absorption demercuration and spray bromine oxidation demercuration technology, and cost of investment is very high; Due to Hg
2+water-soluble, flue gas by after wet desulfurizer (WFGD), Hg
2+removal efficiency can reach 90%, but Hg
0clearance be almost 0, for this reason can by various oxidizing process, first by Hg
ooxidation, then be combined with WFGD, high mercury clearance can be reached.But current SCR denitration is to Hg
0have oxidation, but oxygenation efficiency is lower, needs to supplement HCl in flue gas, cause the corrosion of equipment, influential system safe operation.For this reason on the basis of denitrating catalyst, the oxidability that the collaborative denitration demercuration catalyst of exploitation realizes mercury becomes the emphasis of research at present.
Following known technology, all comes with some shortcomings:
Chinese patent CN104415766A discloses a kind of coal fired power plant flue gas demercuration denitration composite catalyst and preparation method thereof, the composite catalyst of this invention has higher clearance rate to oxynitrides pernicious gas and mercury, but complicated process of preparation, need to carry out repeatedly modification to diatomite, need to introduce plasticizer and borate glass etc., cost is higher simultaneously.
The while that Chinese patent CN103657636A disclosing a kind of, the board-like Catalysts and its preparation method of denitration demercuration, is coated in active component on skeleton, can realize NO
xand Hg
0remove, but catalyst lacks stable, and run under high-speed, active component easily comes off.
Chinese patent CN103480371A discloses a kind of denitration demercuration Catalysts and its preparation method and application, contact by mixing with hydrogen peroxide containing ruthenium material, titanium based denitration catalyst, by dry for the mixture after contact or moist after carry out roasting, gained catalyst is than in the NO of the titanium based denitration catalyst of simple function
xremoval efficiency significantly improves, and Hg
0oxygenation efficiency is very high.But this patent adopts noble metal catalyst, and cost is higher, and has high requirement to flue gas by pure cleanliness, easily poisoning at high temperature denitration demercuration reacting middle catalyst, to severe operating condition bad adaptability.
The ferromanganese composite oxide catalysts and preparation method thereof of denitration demercuration while that Chinese patent 102294248A disclosing a kind of.This catalyst activity component is MnO
2and Fe
2o
3, its Acclimation temperature window is wider, can be improved the anti-poisoning performance of catalyst, to severe operating condition, there is stronger adaptability, but this patent does not relate to the shaping of catalyst, consider bed pressure drop and equipment requirement, this catalyst is difficult to directly apply in existing equipment for denitrifying flue gas.In addition, the denitration demercuration efficiency of catalyst needs to be improved further.
Summary of the invention
The present invention is directed to the strict control of national standard to mercury and mercuric compounds discharge capacity, and do not have can remove NO in flue gas effectively simultaneously at present
xand Hg
0catalyst, the invention provides a kind of honeycombed catalyst of working in coordination with denitration demercuration for coal-fired plant flue gas, under the prerequisite not increasing smoke eliminator, realize NO
xand Hg
0while remove, not only saved the improvement cost to existing apparatus, and decreased the pollution to air, there is stronger industrial application value.
Technical scheme of the present invention: a kind of coal-fired plant flue gas works in coordination with denitration demercuration catalyst, it is the powder be made up of active component and binding agent that this coal-fired plant flue gas works in coordination with denitration demercuration catalyst, is cellular composite catalyst, and its hole density is 2-4 hole/cm
2, extrude pressure for 1000-2000KN, the sectional dimension of cellular powder is 150mmx150mm, length 500-2000mm;
Described active component is the composite metal oxide of titanium dichloride load, and described composite metal oxide is V
2o
5, WO
3, CeO
2, CuO, ZrO
2, MnO
2in one or more mixing, its mass fraction is 0% ~ 10% of cellular composite catalyst; Binding agent addition accounts for the 2-7% of cellular composite catalyst quality.
The preparation method of described active component take titanium dioxide as carrier, one or more metal nitrate in V, W, Ce, Cu, Zr, Mn is metal precursor, ammoniacal liquor, NaOH or sodium carbonate are precipitating reagent, adjust ph is 8-12, at 20-160 DEG C, deposition sedimentation reaction 10-36h, after filtration, washs, 60-120 DEG C of drying, roasting 5-15h at 400-600 DEG C, obtains the active component that coal-fired plant flue gas works in coordination with denitration demercuration catalyst.
Described coal-fired plant flue gas works in coordination with the preparation method of denitration demercuration catalyst, active component and binding agent are prepared powder by batch mixer, powder being joined vacuum-extruder carries out being squeezed into cellular again, cellular powder is placed in steam drying stove, at 30-80 DEG C of dry 5-50h, then in electric furnace, at 350-800 DEG C, calcine 2-20h, obtain coal-fired plant flue gas and work in coordination with denitration demercuration catalyst.
The invention provides the honeycombed catalyst that a kind of coal-fired plant flue gas works in coordination with denitration demercuration, this catalyst reaches 98% to the removal efficiency of oxynitrides under typical coal-fired plant flue gas composition, and the oxygenation efficiency of Elemental Mercury reaches 96%.In addition, this catalyst long service life, cheap.In denitration demercuration reactor, adopt stage casing ammonia-gas spraying device, there is wider active window, to severe operating condition, there is stronger adaptability, simple to operate, be applicable to industrialization large-scale production.
Accompanying drawing explanation
Accompanying drawing is process flow diagram of the present invention.
In figure: 1 boiler; 2 collaborative denitration demercuration reactors; 3 electrostatic precipitators; 4 wet desulphurization devices;
5 smoke evacuation systems.
Detailed description of the invention
The specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing and technical scheme.
Embodiment 1Ce-Cu-V-W-TiO
2the preparation of the active component of composite catalyst
Take titanium dioxide as carrier, V, W, Ce, Cu metal nitrate is metal precursor, and ammoniacal liquor is precipitating reagent, adjust ph is 10, carry out at 30 DEG C deposition sedimentation reaction 10h, after filtration, washing and 120 DEG C of dryings, at 600 DEG C, roasting 5h, obtains Ce-Cu-V-W-TiO
2the active component of composite catalyst.
Embodiment 2Ce-Mn-V-W-TiO
2the preparation of the active component of composite catalyst
Take titanium dioxide as carrier, V, W, Ce, Mn metal nitrate is metal precursor, and sodium carbonate is precipitating reagent, adjust ph is 10, carry out at 160 DEG C deposition sedimentation reaction 36h, after filtration, washing and 60 DEG C of dryings, at 400 DEG C, roasting 15h, obtains Ce-Mn-V-W-TiO
2the active component of composite catalyst.
The cellular Ce-Cu-V-W-TiO of embodiment 3
2the preparation of composite catalyst
Active component prepared by embodiment 1 and binding agent are prepared powder by batch mixer, and wherein binding agent addition accounts for 2% of gross weight; Powder being joined vacuum-extruder carries out being squeezed into cellular, and hole density is 2 holes/cm
2, extrude pressure for 1000KN, the sectional dimension of cellular powder is 150mmx150mm, length 2000mm; Cellular powder is placed in steam drying stove, at 80 DEG C of dry 5h, then in electric furnace, at 800 DEG C, calcines 2h, obtain cellular Ce-Cu-V-W-TiO
2composite catalyst.
The cellular Ce-Mn-V-W-TiO of embodiment 4
2the preparation of composite catalyst
Active component prepared by embodiment 2 and binding agent are prepared powder by batch mixer, and wherein binding agent addition accounts for 7% of gross weight; Powder being joined vacuum-extruder carries out being squeezed into cellular, and hole density is 4 holes/cm
2, extrude pressure for 2000KN, the sectional dimension of cellular powder is 150mmx150mm, length 500mm; Cellular powder is placed in steam drying stove, at 30 DEG C of dry 50h, then in electric furnace, at 350 DEG C, calcines 20h, obtain cellular Ce-Mn-V-W-TiO
2composite catalyst.
The cellular Ce-Cu-V-W-TiO of embodiment 5
2the collaborative denitration demercuration performance test of composite catalyst
With the cellular Ce-Cu-V-W-TiO prepared by embodiment 3
2for catalyst, at 350 DEG C, void tower flow velocity 5m/s, flow velocity 7m/s, air speed 30001/h in catalyst pores, face velocity is under 7m/h condition, the denitration demercuration performance under the simulation coal-fired plant flue gas composition of detecting catalyst shown in table 1, finds NO
xremoval efficiency be the removal efficiency of 98.5%, Hg be 98.3%.
Coal-fired plant flue gas component simulated by table 1.
| Flue gas composition | Ratio |
| CO 2 | 12％ |
| O 2 | 4.5％ |
| N 2 | 74.0％ |
| SO 2 | 0-0.1％ |
| H 2O | 8％ |
| NO | 0.2％ |
| NH 3 | 0.2％ |
| HCl | 10-50ppm |
| Hg | 100mg/Nm 3 |
The cellular Ce-Mn-V-W-TiO of embodiment 6
2the collaborative denitration demercuration performance test of composite catalyst
With the cellular Ce-Mn-V-W-TiO prepared by embodiment 4
2for catalyst, at 350 DEG C, void tower flow velocity 4m/s, flow velocity 6m/s, air speed 40001/h in catalyst pores, face velocity is under 12m/h condition, the denitration demercuration performance under the simulation coal-fired plant flue gas composition of detecting catalyst shown in table 1, finds NO
xremoval efficiency be the removal efficiency of 97.8%, Hg be 98.6%.
Claims (3)
1. coal-fired plant flue gas works in coordination with a denitration demercuration catalyst, it is characterized in that, it is the powder be made up of active component and binding agent that this coal-fired plant flue gas works in coordination with denitration demercuration catalyst, is cellular composite catalyst, and its hole density is 2-4 hole/cm
2, extrude pressure for 1000-2000KN, the sectional dimension of cellular powder is 150mmx150mm, length 500-2000mm;
Described active component is the composite metal oxide of titanium dichloride load, and described composite metal oxide is V
2o
5, WO
3, CeO
2, CuO, ZrO
2, MnO
2in one or more mixing, its mass fraction is 0% ~ 10% of cellular composite catalyst; Binding agent addition accounts for the 2-7% of cellular composite catalyst quality.
2. coal-fired plant flue gas according to claim 1 works in coordination with denitration demercuration catalyst, it is characterized in that, the preparation method of described active component take titanium dioxide as carrier, one or more metal nitrate in V, W, Ce, Cu, Zr, Mn is metal precursor, ammoniacal liquor, NaOH or sodium carbonate are precipitating reagent, adjust ph is 8-12, deposition sedimentation reaction 10-36h at 20-160 DEG C, after filtration, wash, 60-120 DEG C of drying, roasting 5-15h at 400-600 DEG C, obtains the active component that coal-fired plant flue gas works in coordination with denitration demercuration catalyst.
3. coal-fired plant flue gas according to claim 1 and 2 works in coordination with the preparation method of denitration demercuration catalyst, it is characterized in that, active component and binding agent are prepared powder by batch mixer, powder being joined vacuum-extruder carries out being squeezed into cellular again, cellular powder is placed in steam drying stove, at 30-80 DEG C of dry 5-50h, then in electric furnace, calcine 2-20h at 350-800 DEG C, obtain coal-fired plant flue gas and work in coordination with denitration demercuration catalyst.
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| CN105944662A (en) * | 2016-05-15 | 2016-09-21 | 清华大学 | Catalytic adsorbent for demercuration and denitration of flue gas in coal-fired power plant |
| CN106178856A (en) * | 2016-09-08 | 2016-12-07 | 淄博正邦知识产权企划有限公司 | A kind of desulfurization denitrification agent and the method to air cleaning thereof |
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