CN104437529A - SCR catalyst for efficiently oxidizing elemental mercury and preparation method of SCR catalyst - Google Patents
SCR catalyst for efficiently oxidizing elemental mercury and preparation method of SCR catalyst Download PDFInfo
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Abstract
The invention discloses an SCR catalyst for efficiently oxidizing elemental mercury and a preparation method of the SCR catalyst. The catalyst is composed of three parts including an active component, an adjuvant and a carrier, wherein the active component is a mixture of CuCl2 and V2O5; the adjuvant is WO3; the carrier is TiO2; the mass of the catalyst is measured on the basis of the mass of the carrier; the masses of the active component and the adjuvant respectively account for 1-10% and 1-8% of the mass of the carrier; and the mass ratio of CuCl2 to V2O5 in the active component is (1-10):10. The SCR catalyst has the beneficial effects that the dependency on the content of Cl in smoke is relatively low, so that the relatively high denitration efficiency is ensured, and meanwhile the elemental mercury can be efficiently oxidized; the two active components CuCl2 and V2O5 are effectively proportioned, so that the catalytic oxidation efficiency of the catalyst to the elemental mercury is greatly increased; and the preparation method of the SCR catalyst disclosed by the invention is an impregnation method which is simple in step, easily-controlled in reaction process and good in stability.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, be specifically related to a kind of SCR catalyst for efficient oxidation Elemental Mercury and preparation method thereof, belong to catalyst technical field.
Background technology
Mercury is a global pollutant, and it is by atmospheric propagation, and mobility is very strong, after sedimentation, is further converted to methyl mercury, thus works the mischief to human health and environment.
In mankind's activity, combustion of fossil fuel is the largest source of mercury emissions.According to statistics, the mercury that the front coal-burning power plant of u. s. mesh discharges every year reaches 48t, accounts for 1/3rd of mankind's activity discharge mercury total amount; Dirty anti-department of China environmental protection portion cuts down be studied mainly relating to mercury industry mercury emissions inventory and mercury; report shows; within 2007, China's thermoelectricity mercury emission is 138.5 tons; establishment group is based on the technology path of Collaborative Control; calculating thermoelectricity mercury generation in 2007 is 205 tons, and according to current installed capacity prediction of the development trend, by 2010; thermal power plant's mercury generation is 257 tons, is respectively 359 tons and 431 tons to 2015 and the year two thousand twenty.
So taking measures to control the coal-fired mercury produced becomes the focus paid close attention to various countries.In February, 2009, executive council of United Nations Environment Programme reaches an agreement with regard to setting up a binding mechanism.The mercury quantity of discharging in environment due to China is considerable, and State Council pays much attention to mercury pollution preventing and controlling.In " General Office of the State Council forwards the departments such as Environmental Protection Department about the notice strengthening Heavy Metal Pollution job guide suggestion " that within 2009, issue, mercury pollution control is classified as focus.In " heavy metal pollution integrated control " the 12 " planning " of State Council in 2011 reply and " planning of " 12 " key area atmosphere pollution groupcontrol " worked out, all arrangement is done to coal-burning power plant's Mercury In The Air emission control work.The inside explicitly points out: " carry out coal-burning power plant's Mercury In The Air discharge work in a deep going way, actively push forward mercury pollution Collaborative Control, the key industry Mercury In The Air emission inventories such as establishment fire coal, non-ferrous metal, cement, incineration of waste, study and define control way ".For controlling the discharge of thermal power plant's mercury, support work of honouring an agreement, the discharge adding mercury in " fossil-fuel power plant atmospheric pollutant emission standard " promulgated in July, 2011 is restricted to 0.03mg/m
3, execution from 1 day January in 2015.
The form of Mercury In Coal Combustion Flue Gas mainly contains three kinds, i.e. Elemental Mercury (Hg
0), bivalent mercury (Hg
2+, comprise mercury oxide HgO and mercury chloride HgCl
2deng compound) and particle mercury (Hg
p).Hg
pbe adsorbed in flying dust in flue gas and dust, cleaner (electrostatic precipitator ESP and filtration dust catcher FF) can be passed through and remove.Hg
2+soluble in water, can be removed by wet absorption method.The Hg of atomic state
0water insoluble, volatile, be present in gaseous form in flue gas, dedusting and wet absorption equipment are difficult to Direct Acquisition, almost all can be discharged in atmospheric environment with flue gas.Therefore, for coal-fired flue gas mercury removal, its difficult point to solve Hg
0remove problem.
At present, the method of the demercuration studied mainly concentrates on two aspects, one is sorbent injection technology (Sorbent Injection), utilize adsorbent by the mercury absorption in flue gas on the sorbent, adsorbent is collected again by equipment such as dedustings, in flue gas, spraying into absorbent charcoal powder body, flying dust powder and calcium base class compound powder etc. as adopted, realizing the object of demercuration; Be on the other hand utilize based on existing air pollution control device (mainly comprising deduster, denitrification apparatus and desulfurizer) while demercuration method (Co-benefit Mercury Removal).Though sorbent injection technology has higher demercuration efficiency, its cost is very high, and the cost as adopted flue to spray into acticarbon demercuration is about 8-10 ten thousand dollars/kilogram, and in addition, adsorbent subsequent treatment is difficult, easily causes secondary pollution if deal with improperly.The method of existing pollution control device demercuration is utilized to have relatively large advantage on the one hand at this.Electrostatic precipitator (ESP) is installed as main Air Pollution Control equipment by coal-burning power plant of China more than 95%, controls the discharge of particle on a small quantity with sack cleaner.In recent years, almost all flue gas desulfurization device (FGD) has been installed by power plant, and desulfurizer (WFGD) is main in a wet process.Increasing power plant has installed or has planned to install flue gas denitrification equipment, mainly SCR (SCR) technology.These Air Pollution Control equipment in the application of power plant, control NOx, SOx, granular material discharged while, also can the transformation rule of change mercury in flue gas in various degree and the emission performance of power plant's mercury.
EPA (EPA) and USDOE (DOE) field test data show, for power plant's (typical air pollution control device of this Ye Shi China Installation in Plant) of installing electric cleaner (ESP) and WFGD, according to the difference of coal-fired kind, to the removal efficiency of mercury in the scope of 0%-74%, the main cause that removal efficiency is not high is that WFGD can only remove Hg soluble in water
2+, and the Hg in flue gas can not be removed
0.
SCR denitration device, more than 350 DEG C reaction temperature and SCR denitration effect under, by adding NH
3be N the NOx conversion in flue gas
2and H
2o, makes the NOx in flue gas remove.In this course, SCR denitration has participated in the oxidation reaction of mercury simultaneously, Elemental Mercury under the effect of SCR denitration, with the Cl in flue gas
2and O
2reaction generates Hg
2+, make Hg
0content decline, Hg
2+content rise.SCR denitration system does not remove Hg, and Main Function is by the Hg in flue gas
0be oxidized to Hg
2+, increase Hg in flue gas
2+ratio.The potential Elemental Mercury catalytic oxidation ability of SCR catalyst makes to utilize the existing pollutant catabolic gene equipment of coal fired power plant to become possibility to the control realizing mercury in flue gas disposal of pollutants, utilizes SCR denitration device to realize Hg
0to Hg
2+forms Transformation, and then utilize follow-up WFGD desulphurization plant to carry out Hg
2+washing remove.Existing pollutant catabolic gene equipment is utilized to realize controlling coal-fired flue-gas mercury emissions without the need to increasing extra control appliance at coal fired power plant, be a kind of low cost control technology, but the key of this technology how before WFGD import, to utilize SCR catalyst farthest to realize Hg
0to Hg
2+forms Transformation.
Vanadium system SCR catalyst (V
2o
5-WO
3/ TiO
2) be current range of application SCR denitration the most widely, wherein, V
2o
5be the activated centre that catalytic reaction is carried out, there is efficient and good anti-poisoning performance.Vanadium system SCR catalyst has very large fluctuations to the catalytic oxidation efficiency of Hg0 by the restriction of various condition.Such as the content of coal, ammonia spraying amount and HCl all can have influence on the efficiency of SCR catalytic oxidation Elemental Mercury.
Large quantifier elimination shows, in coal, the content of chlorine element has considerable influence to flue gas by the transformation of mercury shape after SCR system, and in coal, content of Cl element is higher, and it is higher that SCR exports bivalent mercury concentration, is more conducive to downstream wet FGD system removing mercury.Field test data shows, in the power plant of the high Cl bituminous coal of burning, SCR device can up to 90% to the oxidation efficiency of mercury; And using the power plant of low Cl subbituminous coal burning ub-bituminous coal, in SCR device, the oxidation efficiency of mercury is lower than 30%.
In view of in China's coal, Cl content is generally on the low side, and the present invention is intended to find a kind of demercuration catalyst low to Cl content dependence in flue gas.
Summary of the invention
The object of the present invention is to provide a kind of lower to Cl content dependence in flue gas, can the SCR catalyst of efficient oxidation Elemental Mercury while ensureing higher denitration efficiency, and the preparation method of this catalyst.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
For a SCR catalyst for efficient oxidation Elemental Mercury, it is characterized in that, by active component, auxiliary agent and carrier three part form, wherein:
Foregoing active component is: CuCl
2and V
2o
5mixture;
Aforesaid builders is: WO
3;
Aforementioned bearer is: TiO
2.
The aforesaid SCR catalyst for efficient oxidation Elemental Mercury, is characterized in that, catalyst quality take carrier quality as benchmark, and the quality of active component accounts for the 1%-10% of carrier quality, and the quality of auxiliary agent accounts for the 1%-8% of carrier quality.
The aforesaid SCR catalyst for efficient oxidation Elemental Mercury, is characterized in that, in foregoing active component, and CuCl
2with V
2o
5mass ratio be 1-10:10.
The aforesaid SCR catalyst for efficient oxidation Elemental Mercury, it is characterized in that, preparation process is as follows:
(1), ammonium paratungstate and ammonium metavanadate are dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate mixed solution;
(2), by titania powder join in the mixed solution of step (1) gained, after fully stirring, ultrasonic immersing 1-3 hour;
(3), by the impregnation product of step (2) gained be placed in drying box dry, be then placed in Muffle furnace roasting, grind after roasting, cross 80 mesh sieves;
(4), the calcined product of step (3) gained is placed in CuCl
2in solution, after fully stirring, ultrasonic immersing 1-3 hour;
(5), by the impregnation product of step (4) gained be placed in drying box again dry, be then placed in Muffle furnace roasting again;
(6), the calcined product of step (5) gained is carried out grinding sieve, get 40-60 object part, namely required catalyst.
The aforesaid SCR catalyst for efficient oxidation Elemental Mercury, is characterized in that, in step (3) and step (5), the temperature of drying box is 100-120 DEG C, and drying time is 1-2 hour.
The aforesaid SCR catalyst for efficient oxidation Elemental Mercury, is characterized in that, in step (3) and step (5), sintering temperature is 400-650 DEG C, and roasting time is 2-4 hour.
Usefulness of the present invention is:
1, SCR catalyst of the present invention is lower to Cl content dependence in flue gas, while ensureing higher denitration efficiency, and can efficient oxidation Elemental Mercury;
2, two kinds of active component CuCl
2and V
2o
5effective proportioning, substantially increase the catalytic oxidation efficiency of catalyst to Elemental Mercury;
3, the preparation method of SCR catalyst of the present invention, adopts infusion process, and step is simple, and course of reaction easily controls, good stability;
4, adopt infusion process of the present invention to prepare and the catalyst that comes, have temperature window large, active high, to features such as HCl dependence are weak.
Detailed description of the invention
Below in conjunction with specific embodiment, concrete introduction is done to the present invention.
First catalyst of the present invention is introduced.
Catalyst of the present invention by active component, auxiliary agent and carrier three part form, wherein, active component is CuCl
2and V
2o
5mixture, auxiliary agent is WO
3, carrier is TiO
2.Catalyst quality take carrier quality as benchmark, and the quality of active component accounts for the 1%-10% of carrier quality, and the quality of auxiliary agent accounts for the 1-8% of carrier quality.In active component, CuCl
2with V
2o
5mass ratio be 1-10:10.
Elemental mercury oxidation, for controlling the discharge of nitrogen oxide in fire coal boiler fume and Elemental Mercury, specifically being become bivalent mercury, without the need to setting up other demercuration equipment, utilizing existing pollutant catabolic gene to equip demercuration by catalyst of the present invention.Its Catalysis Principles is as follows:
In catalytic oxidation process, the Hg in flue gas
0be adsorbed on catalyst surface, with CuCl
2in Cl atomic reaction generate HgCl
2, meanwhile CuCl
2be reduced into CuCl.React HCl and O in the CuCl and flue gas generated
2reaction, by intermediate product Cu
2oCl
2, be finally oxidized to CuCl
2.In whole course of reaction, CuCl
2play the effect of catalyst, reaction equation is as follows:
Hg(0)+2CuCl
2→HgCl
2+2CuCl
Cu
2OCl
2+2HCl→2CuCl
2+H
2O
Net reaction:
Next the preparation method of catalyst of the present invention is introduced.
When preparing catalyst of the present invention, with ammonium paratungstate as WO
3presoma, with ammonium metavanadate as V
2o
5presoma.
Embodiment 1
(1), get 1g dissolving oxalic acid in 20ml deionized water, take 0.3459g ammonium paratungstate and 0.0763g ammonium metavanadate is dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate solution.
(2), by 5g titania powder add in step (1) gained mixed solution, after fully stirring, ultrasonic immersing 2 hours.
(3), by step (2) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 3 hours, grinding, cross 80 mesh sieves.
(4) 0.0274g CuCl, is taken
2be dissolved in 10ml deionized water, step (3) gained calcined product is placed in CuCl
2in solution, after fully stirring, ultrasonic immersing 2 hours.
(5), by step (4) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 4 hours.
(6), step (5) gained calcined product is carried out grinding sieve, get 40-60 object part, namely required catalyst.
In this catalyst, the mass content of each component is: 1wt% V
2o
5-5wt%WO
3-0.5wt% CuCl
2/ TiO
2.
This catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment.Simulated flue gas is 6% oxygen, 12% carbon dioxide, 600ppm sulfur dioxide, 200ppm nitric oxide, 200ppm ammonia, 15 μ g/m
3hg
0, nitrogen is balanced gas, and total gas couette is 15L/min, and reaction temperature is 350 degrees Celsius, and catalyst loading amount is 500mg.Recording this catalyst to the oxidation efficiency of Elemental Mercury is 79%.
Embodiment 2
(1), get 1g dissolving oxalic acid in 20ml deionized water, take 0.3459g ammonium paratungstate and 0.0763g ammonium metavanadate is dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate solution.
(2), by 5g titania powder add in step (1) gained mixed solution, after fully stirring, ultrasonic immersing 2 hours.
(3), by step (2) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 3 hours, grinding, cross 80 mesh sieves.
(4) 0.0411g CuCl, is taken
2be dissolved in 10ml deionized water, step (3) gained calcined product is placed in CuCl
2in solution, after fully stirring, ultrasonic immersing 2 hours.
(5), by step (4) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 4 hours.
(6), step (5) gained calcined product is carried out grinding sieve, get 40-60 object part, namely required catalyst.
In this catalyst, the mass content of each component is: 1wt% V
2o
5-5wt%WO
3-0.75wt% CuCl
2/ TiO
2.
This catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment.Simulated flue gas is 6% oxygen, 12% carbon dioxide, 600ppm sulfur dioxide, 200ppm nitric oxide, 200ppm ammonia, 15 μ g/m
3hg
0, nitrogen is balanced gas, and total gas couette is 15L/min, and reaction temperature is 350 degrees Celsius, and catalyst loading amount is 500mg.Recording this catalyst to the oxidation efficiency of Elemental Mercury is 87%.
Embodiment 3
(1), get 1g dissolving oxalic acid in 20ml deionized water, take 0.3459g ammonium paratungstate and 0.0763g ammonium metavanadate is dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate solution.
(2), by 5g titania powder add in step (1) gained mixed solution, after fully stirring, ultrasonic immersing 2 hours.
(3), by step (2) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 3 hours, grinding, cross 80 mesh sieves.
(4) 0.0548g CuCl, is taken
2be dissolved in 10ml deionized water, step (3) gained calcined product is placed in CuCl
2in solution, after fully stirring, ultrasonic immersing 2 hours.
(5), by step (4) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 4 hours.
(6), step (5) gained calcined product is carried out grinding sieve, get 40-60 object part, namely required catalyst.
In this catalyst, the mass content of each component is: 1wt% V
2o
5-5wt% WO
3-1wt%CuCl
2/ TiO
2.
This catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment.Simulated flue gas is 6% oxygen, 12% carbon dioxide, 600ppm sulfur dioxide, 200ppm nitric oxide, 200ppm ammonia, 15 μ g/m
3hg
0, nitrogen is balanced gas, and total gas couette is 15L/min, and reaction temperature is 350 degrees Celsius, and catalyst loading amount is 500mg.Recording this catalyst to the oxidation efficiency of Elemental Mercury is 98%.
Embodiment 4
(1), get 1g dissolving oxalic acid in 20ml deionized water, take 0.3459g ammonium paratungstate and 0.0763g ammonium metavanadate is dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate solution.
(2), by 5g titania powder add in step (1) gained mixed solution, after fully stirring, ultrasonic immersing 2 hours.
(3), by step (2) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 3 hours, grinding, cross 80 mesh sieves.
(4) 0.0055g CuCl, is taken
2be dissolved in 10ml deionized water, step (3) gained calcined product is placed in CuCl
2in solution, after fully stirring, ultrasonic immersing 2 hours.
(5), by step (4) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 4 hours.
(6), step (5) gained calcined product is carried out grinding sieve, get 40-60 object part, namely required catalyst.
In this catalyst, the mass content of each component is: 1wt% V
2o
5-5wt%WO
3-0.1wt% CuCl
2/ TiO
2.
This catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment.Simulated flue gas is 6% oxygen, 12% carbon dioxide, 600ppm sulfur dioxide, 200ppm nitric oxide, 200ppm ammonia, 15 μ g/m
3hg
0, nitrogen is balanced gas, and total gas couette is 15L/min, and reaction temperature is 350 degrees Celsius, and catalyst loading amount is 500mg.Recording this catalyst to the oxidation efficiency of Elemental Mercury is 68%.
Embodiment 5
(1), get 1g dissolving oxalic acid in 20ml deionized water, take 0.0692g ammonium paratungstate and 0.3052g ammonium metavanadate is dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate solution.
(2), by 5g titania powder add in step (1) gained mixed solution, after fully stirring, ultrasonic immersing 2 hours.
(3), by step (2) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 3 hours, grinding, cross 80 mesh sieves.
(4) 0.0548g CuCl, is taken
2be dissolved in 10ml deionized water, step (3) gained calcined product is placed in CuCl
2in solution, after fully stirring, ultrasonic immersing 2 hours.
(5), by step (4) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 4 hours.
(6), step (5) gained calcined product is carried out grinding sieve, get 40-60 object part, namely required catalyst.
In this catalyst, the mass content of each component is: 4wt% V
2o
5-1wt% WO
3-1wt%CuCl
2/ TiO
2.
This catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment.Simulated flue gas is 6% oxygen, 12% carbon dioxide, 600ppm sulfur dioxide, 200ppm nitric oxide, 200ppm ammonia, 15 μ g/m
3hg
0, nitrogen is balanced gas, and total gas couette is 15L/min, and reaction temperature is 350 degrees Celsius, and catalyst loading amount is 500mg.Recording this catalyst to the oxidation efficiency of Elemental Mercury is 88%.
Embodiment 6
(1), get 1g dissolving oxalic acid in 20ml deionized water, take 0.5534g ammonium paratungstate and 0.5341g ammonium metavanadate is dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate solution.
(2), by 5g titania powder add in step (1) gained mixed solution, after fully stirring, ultrasonic immersing 2 hours.
(3), by step (2) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 3 hours, grinding, cross 80 mesh sieves.
(4) 0.1644g CuCl, is taken
2be dissolved in 10ml deionized water, step (3) gained calcined product is placed in CuCl
2in solution, after fully stirring, ultrasonic immersing 2 hours.
(5), by step (4) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 4 hours.
(6), step (5) gained calcined product is carried out grinding sieve, get 40-60 object part, namely required catalyst.
In this catalyst, the mass content of each component is: 7wt% V
2o
5-8wt% WO
3-3wt%CuCl
2/ TiO
2.
This catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment.Simulated flue gas is 6% oxygen, 12% carbon dioxide, 600ppm sulfur dioxide, 200ppm nitric oxide, 200ppm ammonia, 15 μ g/m
3hg
0, nitrogen is balanced gas, and total gas couette is 15L/min, and reaction temperature is 350 degrees Celsius, and catalyst loading amount is 500mg.Recording this catalyst to the oxidation efficiency of Elemental Mercury is 74%.
Embodiment 7
(1), get 1g dissolving oxalic acid in 20ml deionized water, take 0.3459g ammonium paratungstate and 0.0763g ammonium metavanadate is dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate solution.
(2), by 5g titania powder add in step (1) gained mixed solution, after fully stirring, ultrasonic immersing 2 hours.
(3), by step (2) gained impregnation product be placed in drying box 100 DEG C of dryings 2 hours, be then placed in Muffle furnace roasting, temperature 550 DEG C, roasting time 4 hours, grinding, cross 40-60 mesh sieve, the catalyst that gained part is namely required.
In this catalyst, the mass content of each component is: 1wt% V
2o
5-5wt% WO
3/ TiO
2.
This catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment.Simulated flue gas is 6% oxygen, 12% carbon dioxide, 600ppm sulfur dioxide, 200ppm nitric oxide, 200ppm ammonia, 15 μ g/m
3hg
0, nitrogen is balanced gas, and total gas couette is 15L/min, and reaction temperature is 350 degrees Celsius, and catalyst loading amount is 500mg.Recording this catalyst to the oxidation efficiency of Elemental Mercury is 7%.
From embodiment 1-6: add CuCl in the catalyst
2after active component, this catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment, under experimental result shows that catalyst accounts for the 1%-10% of carrier quality in active component quality, the quality of auxiliary agent accounts for the condition of the 1%-8% of carrier quality, the catalytic oxidation efficiency of this catalyst to Elemental Mercury in flue gas reaches 68%-98%.
From embodiment 7: do not add CuCl
2the catalyst of active component, this catalyst is placed in fixed bed reactors and carries out demercuration efficiency simulated experiment, under experimental result shows that catalyst accounts for 1% of carrier quality in active component quality, the quality of auxiliary agent accounts for the condition of 5% of carrier quality, the catalytic oxidation efficiency of this catalyst to Elemental Mercury in flue gas is 7%, and effect is far below interpolation CuCl
2the catalyst of active component.
It should be noted that, above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops in protection scope of the present invention.
Claims (6)
1., for the SCR catalyst of efficient oxidation Elemental Mercury, it is characterized in that, by active component, auxiliary agent and carrier three part form, wherein:
Described active component is: CuCl
2and V
2o
5mixture;
Described auxiliary agent is: WO
3;
Described carrier is: TiO
2.
2. the SCR catalyst for efficient oxidation Elemental Mercury according to claim 1, is characterized in that, catalyst quality take carrier quality as benchmark, and the quality of active component accounts for the 1%-10% of carrier quality, and the quality of auxiliary agent accounts for the 1%-8% of carrier quality.
3. the SCR catalyst for efficient oxidation Elemental Mercury according to claim 1 and 2, is characterized in that, in described active component, and CuCl
2with V
2o
5mass ratio be 1-10:10.
4. the SCR catalyst for efficient oxidation Elemental Mercury according to claim 1,2 or 3, it is characterized in that, preparation process is as follows:
(1), ammonium paratungstate and ammonium metavanadate are dissolved in oxalic acid solution, add thermal agitation, obtain ammonium paratungstate and ammonium metavanadate mixed solution;
(2), by titania powder join in the mixed solution of step (1) gained, after fully stirring, ultrasonic immersing 1-3 hour;
(3), by the impregnation product of step (2) gained be placed in drying box dry, be then placed in Muffle furnace roasting, grind after roasting, cross 80 mesh sieves;
(4), the calcined product of step (3) gained is placed in CuCl
2in solution, after fully stirring, ultrasonic immersing 1-3 hour;
(5), by the impregnation product of step (4) gained be placed in drying box again dry, be then placed in Muffle furnace roasting again;
(6), the calcined product of step (5) gained is carried out grinding sieve, get 40-60 object part, namely required catalyst.
5. the SCR catalyst for efficient oxidation Elemental Mercury according to claim 4, is characterized in that, in step (3) and step (5), the temperature of drying box is 100-120 DEG C, and drying time is 1-2 hour.
6. the SCR catalyst for efficient oxidation Elemental Mercury according to claim 4 or 5, is characterized in that, in step (3) and step (5), sintering temperature is 400-650 DEG C, and roasting time is 2-4 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815700A (en) * | 2015-04-16 | 2015-08-05 | 宜兴国电精辉环保设备有限公司 | Wear-resistant enhancement solution with cooperative mercury removal function and application of enhancement solution |
| CN104888806A (en) * | 2015-05-07 | 2015-09-09 | 中国华能集团清洁能源技术研究院有限公司 | Regeneration method for inactivated TiV-based honeycomb denitration catalyst having combined denitration and demercuration modification function |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020065131A (en) * | 2001-02-05 | 2002-08-13 | 코오롱건설주식회사 | Catalyst for removing nitrogen oxide using clinoptilolite |
| CN102366722A (en) * | 2011-11-21 | 2012-03-07 | 国电科学技术研究院 | Denitrition catalyst with mercury removal effect and its preparation method |
| CN102716736A (en) * | 2012-06-29 | 2012-10-10 | 南京工业大学 | Composite catalyst for simultaneously denitrifying and removing mercury and preparation method thereof |
| CN103537306A (en) * | 2013-10-16 | 2014-01-29 | 涿州西热环保催化剂有限公司 | Selective catalytic reduction (SCR) catalyst with zero-valent mercury oxidation performance and preparation method thereof |
-
2014
- 2014-12-05 CN CN201410734208.6A patent/CN104437529A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020065131A (en) * | 2001-02-05 | 2002-08-13 | 코오롱건설주식회사 | Catalyst for removing nitrogen oxide using clinoptilolite |
| CN102366722A (en) * | 2011-11-21 | 2012-03-07 | 国电科学技术研究院 | Denitrition catalyst with mercury removal effect and its preparation method |
| CN102716736A (en) * | 2012-06-29 | 2012-10-10 | 南京工业大学 | Composite catalyst for simultaneously denitrifying and removing mercury and preparation method thereof |
| CN103537306A (en) * | 2013-10-16 | 2014-01-29 | 涿州西热环保催化剂有限公司 | Selective catalytic reduction (SCR) catalyst with zero-valent mercury oxidation performance and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815700A (en) * | 2015-04-16 | 2015-08-05 | 宜兴国电精辉环保设备有限公司 | Wear-resistant enhancement solution with cooperative mercury removal function and application of enhancement solution |
| CN104815700B (en) * | 2015-04-16 | 2017-08-08 | 宜兴国电精辉环保设备有限公司 | With the wear-resistant enhancing liquid of collaboration demercuration and its application |
| CN104888806A (en) * | 2015-05-07 | 2015-09-09 | 中国华能集团清洁能源技术研究院有限公司 | Regeneration method for inactivated TiV-based honeycomb denitration catalyst having combined denitration and demercuration modification function |
| CN104888806B (en) * | 2015-05-07 | 2018-11-09 | 中国华能集团清洁能源技术研究院有限公司 | A kind of regeneration method that inactivation vanadium titanium-based Faveolate denitration catalyst combined denitration demercuration is modified |
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