CN102716736A - Composite catalyst capable of depriving nitre and mercury simultaneously and preparation method thereof - Google Patents
Composite catalyst capable of depriving nitre and mercury simultaneously and preparation method thereof Download PDFInfo
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- CN102716736A CN102716736A CN2012102210679A CN201210221067A CN102716736A CN 102716736 A CN102716736 A CN 102716736A CN 2012102210679 A CN2012102210679 A CN 2012102210679A CN 201210221067 A CN201210221067 A CN 201210221067A CN 102716736 A CN102716736 A CN 102716736A
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Abstract
The invention relates to a composite catalyst capable of depriving nitre and mercury simultaneously and a preparation method thereof, belongs to the technical field of air pollution control, and is used for depriving fire coal smoke nitric oxide and elementary substance mercury. The catalyst comprises an active component and a carrier, the active component is CeO2 and ZrO2, molar ratio of Ce and Zr is 1/0.1-1, the carrier is one or a plurality of kinds of honeycomb ceramics, a molecular sieve, a ceramic plate, activated carbon fibers, a silica gel carrier, kieselguhr, metal alloy and a filter bag. Quality of the carrier serves as a standard, and the content of the active component of the catalyst is 5%-30%. The composite catalyst further comprises an assistant which is one of or any combination of two of oxides of W, Cu, Fe, Ti and Ni. Quality of the carrier serves as a standard, and the content of the assistant is 0%-15%.
Description
Technical field
What the present invention relates to is composite catalyst of a kind of while denitration demercuration and preparation method thereof, belongs to the air pollution control technique field, is used to remove coal-fired flue-gas nitrogen oxide and simple substance mercury.
Background technology
Mercury is a kind ofly to have permanent cumulative noxious material in vivo with in the food chain, possibly cause serious diseases such as hepatitis, ephritis, hematuria.Research shows that mercury compound can also get in the fetus body through placenta, thereby has a strong impact on the health of fetus.Mercury since its high volatility, the time of staying for a long time and characteristics such as the bioaccumulation effect is remarkable as priority pollutants.China's coal-fired flue-gas is topmost mercury emissions source, and in considerable time from now on, China will be difficult to change for the main energy sources consumption structure with coal.Therefore, alleviating and control coal-fired mercury emissions is one of major measure of control mercury pollution.The discharge standard that China has set up fire coal boiler fume mercury in " thermal power plant's atmosphere pollutants emission standards " of in July, 2011 promulgation in (GB13223-2011), the emission limit set to nitrogen oxide has proposed more strict requirement simultaneously.
Improvement for mercury in the flue gas both at home and abroad also is in the starting stage, does not also have ripe technology at present, is mostly to adopt active carbon adsorption to remove, and operating cost is high, brings huge economic pressures can for the operation of domestic coal fired power plant.
To distribute be that mercury with which kind of form exists to the form of mercury in the flue gas, and the removal of mercury efficient of mercury emissions control technology is had very big influence.Mercury mainly exists with chemical combination attitude form in the fire coal, and in common fire box temperature scope, the compound of mercury is in the thermally labile state, resolves into heat-staple Hg
0Therefore under furnace high-temperature, nearly all mercury all is transformed into nonvalent mercury in the fire coal, and is present in the high-temperature flue gas with gaseous form.Hg
PBecause it is particle shape, can effectively be caught Hg by cleaner
2+Soluble in water and easy on the particle, can be removed by the pollutant control appliance of routine, for example wet flue gas desulfurization device, inertial dust separator, electrostatic precipitator (ESP) or sack cleaner.The form difference of gaseous mercury is very big in the power-plant flue gas, Hg in the gas phase mercury
0With Hg
2+Ratio greatly about about 7:3.Hg
0Because highly volatile and be insoluble in water, therefore existing smoke pollution treating apparatus is to Hg
0Removal efficient lower, if do not add ancillary method, most nonvalent mercury will directly be entered in the atmosphere.
It is thus clear that, the complexity of mercury pollution control in the coal fired power plant flue gas, the form that depends primarily on mercury distributes, and is promptly closely related with its morphological feature in flue gas.How to make Hg
0The maximized Hg that is transformed into
2+Become and utilize existing pollutant control device to remove the emphasis and the difficult point of mercury.
At present, denitration demercuration catalyst patent is less simultaneously for domestic relevant flue gas.In the existing patent, be (CN102218266) with TiO
2Be supporter, with V
2O
5Be the catalyst of active component, catalytic activity is high, and weak point is that the catalyst cost is expensive and poisonous.(CN102294248) be with TiO
2Be carrier, with MnO
2-Fe
2O
3Be the catalyst of active component, catalytic activity is high, but this catalyst activity temperature window is not high, has limited it in Industrial Application.Therefore develop the cheap O composite metallic oxide catalyst of a kind of environment-friendly high-efficiency and become problem oh to be solved.
Summary of the invention
The present invention is directed to above-mentioned weak point, composite catalyst of a kind of while denitration demercuration and preparation method thereof is provided, is a kind ofly to have denitration simultaneously and take off the composite catalyst of performance, with NO
xSCR (being called for short SCR) becomes N
2, simultaneously with Hg
0Be oxidized to Hg
2+, need not to establish in addition mercury removal device, also need not to add oxidant, utilize existing apparatus to accomplish denitration and demercuration reaction to greatest extent.
Composite catalyst of a kind of while denitration demercuration of the present invention and preparation method thereof is to take following technical scheme to realize: a kind of composite catalyst of while denitration demercuration is characterized in that: comprise active component and carrier, said active component is CeO
2And ZrO
2, Ce/Zr mol ratio 1:0.1 ~ 1 wherein, said carrier is one or more of ceramic honey comb, molecular sieve, ceramic wafer, NACF, silica-gel carrier, diatomite, metal alloy, filter bag.
Quality with carrier is a benchmark, and said catalyst activity components contents is 5% ~ 30%.
The composite catalyst of a kind of while denitration demercuration of the present invention also comprises auxiliary agent, and said auxiliary agent is one or more the combination in any in the oxide of W, Cu, Fe and Ti.Quality with carrier is a benchmark, and the content of said auxiliary agent is 0 ~ 15%.
The present invention also provides the method for preparing composite catalyst of above-mentioned while denitration demercuration, adopts the equi-volume impregnating preparation.Its concrete steps are following:
(1) with carrier impregnation for use is 5 ~ 20% HNO to the quality percentage composition
3In solution or the HCl solution, place heating and constantly boiling 5 ~ 15min on the resistance furnace, be washed with distilled water to pH=5 ~ 7 after the cooling naturally, it is for use to put into the dry 24 ~ 48h of 60 ~ 100 ℃ of baking ovens;
(2) get catalyst activity component presoma: solubility cerium salt and solubility zirconates; Wherein the mol ratio of cerium zr element is 1:0.1 ~ 1; Be dissolved in volume and equal in the deionized water of carrier total pore volume,, make it to dissolve fully with magnetic stirrer 2 ~ 10min;
(3) carrier impregnation that step (1) is obtained is in the active component precursor solution that step (2) obtains; Leave standstill 15 ~ 120min; In 60 ~ 100 ℃ of down dry 2 ~ 10h, put into the Muffle furnace roasting again, sintering temperature is 350 ~ 800 ℃; Roasting time is controlled at 2 ~ 10h, promptly accomplishes Preparation of catalysts after the cooling naturally.
Cerium precursor solubility cerium salt described in the step (2) is one or more any mixture in cerous nitrate, cerous acetate or the cerium chloride.Zirconium precursor body solubility zirconates is one or more any mixture in zirconium chloride, zirconium oxychloride, zirconyl nitrate or the zirconium nitrate.
The present invention provides a kind of method for preparing composite catalyst of while denitration demercuration in addition, and its step is following:
(1) with carrier impregnation for use is 5 ~ 20% HNO to the quality percentage composition
3In solution or the HCl solution, place heating and constantly boiling 5 ~ 15min on the resistance furnace, be washed with distilled water to pH=5 ~ 7 after the cooling naturally, it is for use to put into the dry 24 ~ 48h of 60 ~ 100 ℃ of baking ovens;
(2) get catalyst activity component presoma: solubility cerium salt and solubility zirconates; Ce/Zr mol ratio 1:0.1 ~ 1 wherein; The presoma of auxiliary agent: soluble tungsten salt, soluble copper salt, soluble ferric iron salt, solubility titanium salt; Be dissolved in the deionized water that volume equals the carrier total pore volume by certain element mol ratio,, make it to dissolve fully with magnetic stirrer 5 ~ 20min;
(3) carrier impregnation that step (1) is obtained leaves standstill 15 ~ 120min in the mixed solution that step (2) obtains, in 60 ~ 100 ℃ of down dry 2 ~ 10h; Put into the Muffle furnace roasting again; Sintering temperature is 350 ~ 800 ℃, and roasting time is controlled at 2 ~ 10h, promptly accomplishes Preparation of catalysts after the cooling naturally.
Cerium precursor solubility cerium salt described in the step (2) is selected one or more any mixture in cerous nitrate, cerous acetate or the cerium chloride for use.Zirconium precursor body solubility zirconates is selected one or more any mixture in zirconium chloride, zirconium oxychloride zirconyl nitrate or the zirconium nitrate for use; Tungsten presoma soluble tungsten salt is selected ammonium metatungstate for use; The presoma soluble ferric iron salt of iron is selected the thing in ferric nitrate, ferric acetate or the iron chloride for use; The presoma solubility titanium salt of titanium is selected titanium tetrachloride or one or more any mixing of butyl titanate for use; The presoma soluble copper salt of copper is selected one or more any mixing of Schweinfurt green, copper chloride or copper nitrate for use.
The composite catalyst of a kind of while denitration demercuration of the present invention compared with prior art, the method for preparing composite catalyst of the present invention preparation is simple, active temperature windows broad and to the environment non-secondary pollution, in middle temperature coal-fired flue-gas and higher SO
2Under the concentration, can be efficiently, Reduction of NO stably
x, the highest removal efficiency reaches 97%, simultaneously catalytic oxidation Hg
0, highest oxidation efficient reaches 95%.
The composite catalyst of a kind of while denitration demercuration of the present invention is a kind ofly to have denitration simultaneously and take off the composite catalyst of performance, with NO
xSCR (being called for short SCR) becomes N
2, simultaneously with Hg
0Be oxidized to Hg
2+, need not to establish in addition mercury removal device, also need not to add oxidant, utilize existing apparatus to accomplish denitration and demercuration reaction to greatest extent.
The invention discloses this Preparation of catalysts method, adopt infusion process.Catalyst of the present invention has the active window of higher activity, selectivity and broad, and abominable operating condition is had stronger adaptability, and is simple to operate.Mounted flue gas SCR capable of using (SCR) denitrification apparatus, wet desulphurization (Wet-FGD) device and dust arrester are removed mercury in practical application, reduce the cost that mercury removal device is set separately.
The specific embodiment
Instance 1
Raw material calculates:
Weighing carrier quality, the water absorption rate of mensuration carrier is 8% of a carrier quality according to catalytic activity group quality, calculates the addition of active component presoma.
The concrete operations step:
(1) honeycomb ceramic carrier being impregnated into the quality percentage composition is 5% HNO
3In the solution, place heating and constantly boiling 5min on the resistance furnace, be washed with distilled water to pH=5 after the cooling naturally, it is for use to put into 60 ℃ of dry 24h of baking oven;
(2) get catalyst activity component presoma: cerous nitrate and zirconium oxychloride, wherein the mol ratio of Ce/Zr element is 1:1, is dissolved in volume and equals to use magnetic stirrer 2min in the deionized water of carrier total pore volume, makes it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 15min in the active component precursor solution that step (2) obtains, in 60 ℃ of dry 2h down; Put into the Muffle furnace roasting again; Sintering temperature is 550 ℃, and roasting time is 6h, promptly accomplishes Preparation of catalysts after the cooling naturally.
Get a certain amount of catalyst and place analogue reactor, it is 200 ~ 400 ℃ that reaction temperature is set; HCl, SO in the flue gas
2, NO, NH
3, O
2Concentration be respectively 20ppm, 500ppm, 500ppm, 500ppm, 5%; Reaction compartment speed is 3000 ~ 10000h
-1, test result shows: when temperature was 350 ℃, the denitration rate was 91%, and the gaseous elemental mercury oxygenation efficiency is 83.3%.
Instance 2
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 8% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 2% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) honeycomb ceramic carrier being impregnated into the quality percentage composition is 5% HNO
3In the solution, place heating and constantly boiling 8min on the resistance furnace, be washed with distilled water to pH=5 after the cooling naturally, it is for use to put into 70 ℃ of dry 30h of baking oven;
(2) get catalyst activity component presoma: cerous acetate and zirconium chloride; Wherein the mol ratio of the element of Ce/Zr is 1:0.5, the presoma of auxiliary agent: ammonium metatungstate all is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 20min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (2) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 300 ℃, the denitration rate was 95.6%, and the oxygenation efficiency of gaseous elemental mercury is 92.1%.
Instance 3
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 10% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 2% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) molecular sieve carrier being impregnated into the quality percentage composition is in 5% the HCl solution, places heating and constantly boiling 8min on the resistance furnace, is washed with distilled water to pH=5 after cooling off naturally, and it is for use to put into 70 ℃ of dry 30h of baking oven;
(2) get catalyst activity component presoma: cerium chloride and zirconium nitrate; Wherein the mol ratio of the element of Ce/Zr is 1:0.5, the presoma of auxiliary agent: Schweinfurt green all is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 4min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (2) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 350 ℃, the denitration rate was 94.7%, and the oxygenation efficiency of gaseous elemental mercury is 90.2%.
Instance 4
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 20% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 5% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) diatomite support being impregnated into the quality percentage composition is in 10% the HCl solution, places heating and constantly boiling 15min on the resistance furnace, is washed with distilled water to pH=6 after cooling off naturally, and it is for use to put into 90 ℃ of dry 10h of baking oven;
(3) get catalyst activity component presoma: cerous nitrate and zirconyl nitrate; Wherein the mol ratio of the element of Ce/Zr is 1:0.1, the presoma of auxiliary agent: copper chloride all is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 8min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (4) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 350 ℃, the denitration rate was 87.2%, and the oxygenation efficiency of gaseous elemental mercury is 85.9%.
Instance 5
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 30% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 2% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) with the ceramic wafer carrier impregnation is 5% HNO to the quality percentage composition
3In the solution, place heating and constantly boiling 15min on the resistance furnace, be washed with distilled water to pH=7 after the cooling naturally, it is for use to put into 100 ℃ of dry 8h of baking oven;
(2) get catalyst activity component presoma: cerous sulfate and zirconium oxychloride; Wherein the mol ratio of the element of Ce/Zr is 1:0.1, the presoma of auxiliary agent: ferric nitrate is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 8min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (2) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 250 ℃, the denitration rate was 95.2%, and the oxygenation efficiency of gaseous elemental mercury is 90.5%.
Instance 6
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 10% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 2% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) be in 5% the HCl solution to the quality percentage composition with the nickel alumin(i)um alloy carrier impregnation, place heating and constantly boiling 6min on the resistance furnace, be washed with distilled water to pH=7 after cooling off naturally, it is for use to put into 60 ℃ of dry 48h of baking oven;
(2) get catalyst activity component presoma: cerous acetate and zirconium nitrate; Wherein the mol ratio of the element of Ce/Zr is 1:0.1, the presoma of auxiliary agent: titanium tetrachloride all is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 8min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (2) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 300 ℃, the denitration rate was 90.1%, and the oxygenation efficiency of gaseous elemental mercury is 84.5%.
Instance 7
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 14% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 3% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) NACF being impregnated into the quality percentage composition is 10% HNO
3In the solution, place heating and constantly boiling 6min on the resistance furnace, be washed with distilled water to pH=7 after the cooling naturally, it is for use to put into 80 ℃ of dry 48h of baking oven;
(2) get catalyst activity component presoma: cerous nitrate and zirconium oxychloride; Wherein the mol ratio of the element of Ce/Zr is 1:0.1; The presoma of auxiliary agent: ferric acetate, copper nitrate, wherein the element mol ratio of Fe/Cu is 1:1:1, is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 4min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (2) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 300 ℃, the denitration rate was 97.3%, and the oxygenation efficiency of gaseous elemental mercury is 96.5%.
Instance 8
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 30% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 2% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) silica-gel carrier being impregnated into the quality percentage composition is 10% HNO
3In the solution, place heating and constantly boiling 6min on the resistance furnace, be washed with distilled water to pH=7 after the cooling naturally, it is for use to put into 80 ℃ of dry 48h of baking oven;
(2) get catalyst activity component presoma: cerous nitrate and zirconium oxychloride; Wherein the mol ratio of the element of Ce/Zr is 1:0.1; The presoma of auxiliary agent: iron chloride, copper chloride, wherein the element mol ratio of Fe/Cu is 1:1, all is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 4min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (2) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 300 ℃, the denitration rate was 97.3%, and the oxygenation efficiency of gaseous elemental mercury is 96.5%.
Instance 9
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 30% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 10% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) gets catalyst activity component presoma: cerous nitrate and zirconium oxychloride; Wherein the mol ratio of the element of Ce/Zr is 1:0.1; The presoma of auxiliary agent: ammonium metatungstate, ferric nitrate, wherein the element mol ratio of W/Fe is 1:1, is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 1h, make it to dissolve fully; Dry 8 ~ 24h in 60 ℃ ~ 120 ℃ air dry ovens puts into 350 ℃ ~ 800 ℃ Muffle furnace roasting 8 ~ 24h more again, grinds back 120 orders ~ 200 orders and sieves and make catalyst fines;
(2) according to the carrier quality, the powder that takes by weighing preparation in the step (1) adds solvent in container, be made into the solution of mass percentage concentration 5%, this solution is put into Ultrasound Instrument carry out making the catalyst aaerosol solution after the ultrasonic dispersion of 40min;
(3) filter bag is tiled on the suction funnel, the suspension that step (2) is prepared evenly falls on this filter bag, opens the suction filtration that the suction filtration vavuum pump carries out 120min simultaneously, again with this filter bag in the dry 10h of 80 ℃ of air dry ovens, promptly accomplish Preparation of catalysts.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 300 ℃, the denitration rate was 90.2%, and the oxygenation efficiency of gaseous elemental mercury is 93.5%.
Instance 10
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 10% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 5% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) honeycomb ceramic carrier being impregnated into the quality percentage composition is in 5% the HCl solution, places heating and constantly boiling 6min on the resistance furnace, is washed with distilled water to pH=7 after cooling off naturally, and it is for use to put into 60 ℃ of dry 48h of baking oven;
(2) get catalyst activity component presoma: zirconyl nitrate, zirconium chloride and cerous acetate; Wherein the mol ratio of the element of Ce/Zr is 1:0.1; The presoma of auxiliary agent: butyl titanate, ammonium metatungstate, copper chloride, wherein the element mol ratio of Ti/W/Cu is 1:1:0.1, all is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 8min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (2) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 300 ℃, the denitration rate was 98.3%, and the oxygenation efficiency of gaseous elemental mercury is 97.4%.
Instance 11
Raw material calculates:
Weighing carrier quality, the total pore volume of mensuration carrier is 15% of a carrier quality according to catalytic activity group quality, the auxiliary agent quality is 10% of a carrier quality, calculates the addition of active component presoma and auxiliary agent precursor respectively.
The concrete operations step:
(1) honeycomb ceramic carrier being impregnated into the quality percentage composition is in 5% the HCl solution, places heating and constantly boiling 6min on the resistance furnace, is washed with distilled water to pH=7 after cooling off naturally, and it is for use to put into 60 ℃ of dry 48h of baking oven;
(2) get catalyst activity component presoma: cerous acetate, cerous nitrate and zirconyl nitrate; Wherein the mol ratio of the element of Ce/Zr is 1:0.1; The presoma of auxiliary agent: butyl titanate, titanium tetrachloride, ammonium metatungstate, copper chloride, copper nitrate, wherein the element mol ratio of Ti/W/Cu is 1:1:0.1, all is dissolved in volume and equals in the deionized water of carrier total pore volume; Use magnetic stirrer 8min, make it to dissolve fully;
(3) carrier impregnation that step (1) is obtained leaves standstill 30min in the mixed solution that step (2) obtains, in 70 ℃ of dry 4h down, put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, and roasting time is controlled at 5h, promptly accomplishes Preparation of catalysts after cooling off naturally.
Utilize the activity rating apparatus and method among the embodiment 1, the result that flue gas is detected shows: when reaction temperature was 300 ℃, the denitration rate was 91.8%, and the oxygenation efficiency of gaseous elemental mercury is 90.6%.
Claims (8)
1. composite catalyst of denitration demercuration simultaneously, it is characterized in that: this catalyst comprises active component and carrier, said active component is CeO
2And ZrO
2, Ce/Zr mol ratio 1:0.1 ~ 1 wherein, said carrier is one or more in ceramic honey comb, molecular sieve, ceramic wafer, NACF, silica-gel carrier, diatomite, metal alloy, the filter bag.
2. according to right 1 described composite catalyst, it is characterized in that: the quality with carrier is a benchmark, and said catalyst activity components contents is 5% ~ 30%.
3. composite catalyst according to claim 1 is characterized in that: also comprise auxiliary agent, said auxiliary agent is one or more the combination in any in the oxide of W, Cu, Fe, Ti, Ni; Quality with carrier is a benchmark, and the content of said auxiliary agent is 0% ~ 15%.
4. the method for preparing composite catalyst of a kind of while denitration demercuration according to claim 1 is characterized in that: may further comprise the steps:
5 ~ 20% HNO with carrier impregnation for use to the quality percentage composition
3In solution or the HCl solution, place heating and constantly boiling 5 ~ 15min on the resistance furnace, be washed with distilled water to pH=5 ~ 7 after the cooling naturally, it is for use to put into the dry 24 ~ 48h of 60 ~ 100 ℃ of baking ovens;
Get catalyst activity component presoma: solubility cerium salt and solubility zirconates, wherein the mol ratio of cerium zr element is 1:0.1 ~ 1, is dissolved in volume and equals in the deionized water of carrier total pore volume, with magnetic stirrer 2 ~ 10min, makes it to dissolve fully;
The carrier impregnation that step (1) is obtained is in the active component precursor solution that step (2) obtains; Leave standstill 15 ~ 120min; In 60 ~ 100 ℃ of down dry 2 ~ 10h, put into the Muffle furnace roasting again, sintering temperature is 350 ~ 800 ℃; Roasting time is controlled at 2 ~ 10h, promptly accomplishes Preparation of catalysts after the cooling naturally.
5. method according to claim 4 is characterized in that: the cerium precursor solubility cerium salt described in the step (2) is selected one or more any mixture in cerous nitrate, cerous sulfate, cerous acetate or the cerium chloride for use; Zirconium precursor body solubility zirconates is selected one or more any mixture in zirconium chloride, zirconium oxychloride, zirconyl nitrate or the zirconium nitrate for use.
6. the method for preparing composite catalyst of claim 1 and 3 described a kind of while denitration demercurations, it is characterized in that: preparation process is following:
(1) with carrier impregnation for use is 5 ~ 20% HNO to the quality percentage composition
3In solution or the HCl solution, place heating and constantly boiling 5 ~ 15min on the resistance furnace, be washed with distilled water to pH=5 ~ 7 after the cooling naturally, it is for use to put into the dry 24 ~ 48h of 60 ~ 100 ℃ of baking ovens;
(2) get the presoma of said auxiliary agent: soluble tungsten salt, soluble copper salt, soluble ferric iron salt, solubility titanium salt; By certain element mol ratio; Be dissolved in the deionized water that volume equals the carrier total pore volume,, make it to dissolve fully with magnetic stirrer 2 ~ 10min;
(3) get catalyst activity component presoma: solubility cerium salt and solubility zirconates, wherein Ce/Zr mol ratio 1:0.1 ~ 1 is dissolved in volume and equals in the deionized water of carrier total pore volume, with magnetic stirrer 2 ~ 10min, makes it to dissolve fully;
(4) the auxiliary agent precursor solution that step (2) is obtained mixes with the active component precursor solution that step (3) obtains, and uses magnetic stirrer 10min, makes it to dissolve fully to leave standstill;
(5) carrier impregnation that step (1) is obtained leaves standstill 15 ~ 120min in the mixed solution that step (4) obtains, in 60 ~ 100 ℃ of down dry 2 ~ 10h; Put into the Muffle furnace roasting again; Sintering temperature is 350 ~ 800 ℃, and roasting time is controlled at 2 ~ 10h, promptly accomplishes Preparation of catalysts after the cooling naturally.
7. method for preparing composite catalyst according to claim 6 is characterized in that: the presoma soluble tungsten salt of the tungsten described in the step (2) is selected ammonium metatungstate for use; The presoma soluble ferric iron salt of iron is selected the thing in ferric nitrate, ferric acetate or the iron chloride for use; The presoma solubility titanium salt of titanium is selected titanium tetrachloride or one or both mixing of butyl titanate for use; The presoma soluble copper salt of copper is selected one or more any mixing of Schweinfurt green, copper chloride or copper nitrate for use.
8. method for preparing composite catalyst according to claim 6 is characterized in that: the cerium precursor solubility cerium salt described in the step (3) is one or more any mixture in cerous nitrate, cerous sulfate, cerous acetate or the cerium chloride; Zirconium precursor body solubility zirconates is one or more any mixture in zirconium chloride, zirconium oxychloride, zirconyl nitrate or the zirconium nitrate.
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