CN104437471A - Denitration catalyst and preparation method thereof - Google Patents
Denitration catalyst and preparation method thereof Download PDFInfo
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- CN104437471A CN104437471A CN201410611728.8A CN201410611728A CN104437471A CN 104437471 A CN104437471 A CN 104437471A CN 201410611728 A CN201410611728 A CN 201410611728A CN 104437471 A CN104437471 A CN 104437471A
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Abstract
The invention provides a denitration catalyst and a preparation method thereof. The preparation method comprises the following steps: mixing a manganese compound, a rare earth compound and a zirconium compound with a co-melting mixture; and carrying out a solvent thermal reaction to obtain the denitration catalyst. The co-melting mixture comprises a potassium nitrate-potassium hydroxide co-melting mixture, a sodium nitrite-potassium nitrate co-melting mixture, a neopentyl glycol-tetramethyl ammonium bromide co-melting mixture or a sodium hydroxide-potassium hydroxide co-melting mixture. The denitration catalyst prepared by the preparation method has a relatively high specific surface area and has a relatively high denitration rate. The denitration catalyst is good in low-temperature activity, can keep a good nitric oxide removing rate and water-resisting and sulfur-resisting performance in flue gas at 100-250 DEG C, is relatively high in N2 selectivity and is long in service life. According to the preparation method, no template agent is added in a preparation process, and the problems that high-temperature calcining is needed when the template agent is removed at the later period and the like are solved; and the synthetic method is simple, is low in energy consumption and cost and is environmentally friendly.
Description
Technical field
The invention belongs to catalyst technical field, particularly relate to a kind of denitrating catalyst and preparation method thereof.
Background technology
The NO of mankind's activity discharge
xmore than 90% from fossil fuel combustion process such as coals.During the high-temp combustion such as thermal power plant, Industrial Boiler, containing a large amount of NO in the flue gas of discharge
x, participate in the N in the air of burning
2and O
2also NO can be generated
x.NO
xone is that harm humans is healthy, and two is that it can form acid rain and may under sunlight irradiates, a series of photochemical reaction occur with hydrocarbon and form photochemical fog thus cause the series of environmental problems such as greenhouse effects.The NO wherein discharged
xin more than 90% be NO, so how to reduce the NO of stationary source discharge
xit is the importance that atmospheric environment is administered.
At numerous stationary source NO
xin removal methods, because removal efficiency is high, cost performance is relatively high, ammonia selective catalytic reduction (NH
3-SCR) become the optimization technique of generating plant flue gas denitration.But the V-W-Ti catalyst series of business application, reaction temperature generally needs to control at 573K ~ 673K.For avoiding Repeat-heating flue gas, before just SCR device must being placed in desulfurization and dedusting, and dust in flue gas and SO
2, can block and covering catalyst avtive spot, cause catalyst poisoning, greatly shorten catalyst life.If after SCR is placed in desulfation dust-extraction device, because flue-gas temperature after desulfurization and dedusting is general all lower than 433K, therefore exploitation low temperature (<423K) SCR catalyst is very necessary.
Research finds that the specific area of low-temperature SCR catalyst has material impact to its activity, because which determine reactant NH
3with the adsorbance of NO at catalyst surface, and then affect denitration rate.B.Shen etal.Powder Technology.2014, reports the Mn prepared with calcination in 253:152-157
2ce
5o
xspecific area is 34.7m
2g
-1, be 23% 220 DEG C of denitration rates.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of denitrating catalyst and preparation method thereof, denitrating catalyst provided by the invention has higher denitration rate.
The invention provides a kind of preparation method of denitrating catalyst, comprise the following steps:
To mix with eutectic mixture containing manganese compound, rare earth compound, zirconium compounds, and carry out solvent thermal reaction, obtain denitrating catalyst;
Described eutectic mixture comprises potassium nitrate-potassium hydroxide eutectic mixture, natrium nitrosum-potassium nitrate eutectic mixture, neopentyl glycol-4 bromide eutectic mixture or NaOH-potassium hydroxide eutectic mixture.
Preferably, in described potassium nitrate-potassium hydroxide eutectic mixture, the mass ratio of potassium nitrate and potassium hydroxide is (35 ~ 40): (60 ~ 65);
In described natrium nitrosum-potassium nitrate eutectic mixture, the mass ratio of potassium nitrate and potassium hydroxide is (40 ~ 45): (50 ~ 55).
Preferably, in described neopentyl glycol-4 bromide eutectic mixture, the mass ratio of neopentyl glycol and 4 bromide is (40 ~ 43): (60 ~ 63);
In described NaOH-potassium hydroxide eutectic mixture, the mass ratio of NaOH and potassium hydroxide is (50 ~ 55): (45 ~ 50).
Preferably, the described manganese compound that contains comprises MnO
2and/or basic carbonate manganese.
Preferably, described zirconium compounds comprises zirconium nitrate, zirconium sulfate or zirconyl chloride.
Preferably, described rare earth compound comprises rare earth nitrades, rare earth sulfate or Rare Earths salt.
Preferably, described rare earth compound rare earth elements is cerium, praseodymium or terbium.
Preferably, the temperature of described solvent thermal reaction is 100 DEG C ~ 220 DEG C;
The time of described solvent thermal reaction is 12h ~ 96h.
Present invention also offers denitrating catalyst prepared by the preparation method described in a kind of technique scheme.
Preferably, the specific area of described denitrating catalyst is more than or equal to 200m
2/ g.
The invention provides a kind of preparation method of denitrating catalyst, comprise the following steps: will mix with eutectic mixture containing manganese compound, rare earth compound, zirconium compounds, and carry out solvent thermal reaction, obtain denitrating catalyst; Described eutectic mixture comprises potassium nitrate-potassium hydroxide eutectic mixture, natrium nitrosum-potassium nitrate eutectic mixture, neopentyl glycol-4 bromide eutectic mixture or NaOH-potassium hydroxide eutectic mixture.Denitrating catalyst prepared by preparation method provided by the invention has higher specific area, and then has higher denitration rate.The low temperature active of denitrating catalyst provided by the invention is good, can keep good removal of nitrogen oxide rate and water resistant resistance to SO_2, higher N in the flue gas of 100 DEG C ~ 250 DEG C
2selective, and the life-span is long.Preparation method provided by the invention does not add any template in preparation process, there is not the problem such as high-temperature calcination of later stage removing template, synthetic method is simple, energy consumption and cost is low, environmental friendliness.Experimental result shows: denitrating catalyst provided by the invention at 100 DEG C ~ 230 DEG C, denitration rate more than 80%, to N
2selective more than 80%.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the denitrating catalyst that the embodiment of the present invention 1 obtains;
Fig. 2 is the XRD spectra of the denitrating catalyst that the embodiment of the present invention 1 obtains;
Fig. 3 is the SEM figure of the denitrating catalyst that the embodiment of the present invention 2 obtains;
Fig. 4 is the XRD spectra of the denitrating catalyst that the embodiment of the present invention 2 obtains.
Detailed description of the invention
The invention provides a kind of preparation method of denitrating catalyst, comprise the following steps:
To mix with eutectic mixture containing manganese compound, rare earth compound, zirconium compounds, and carry out solvent thermal reaction, obtain denitrating catalyst;
Described eutectic mixture comprises potassium nitrate-potassium hydroxide eutectic mixture, natrium nitrosum-potassium nitrate eutectic mixture, neopentyl glycol-4 bromide eutectic mixture or NaOH-potassium hydroxide eutectic mixture.
Denitrating catalyst prepared by preparation method provided by the invention has higher specific area, makes it have higher denitration rate.The low temperature active of denitrating catalyst provided by the invention is good, can keep good removal of nitrogen oxide rate and water resistant resistance to SO_2, higher N in the flue gas of 100 DEG C ~ 250 DEG C
2selective, and the life-span is long.Preparation method provided by the invention does not add any template in preparation process, there is not the problem such as high-temperature calcination of later stage removing template, synthetic method is simple, energy consumption and cost is low, environmental friendliness.Experimental result shows: denitrating catalyst provided by the invention at 100 DEG C ~ 230 DEG C, denitration rate more than 80%, to N
2selective more than 80%.
In the present invention, the described manganese compound that contains preferably includes MnO
2or basic carbonate manganese.
The present invention does not have special restriction to the described source containing manganese compound, adopts its commercial goods or adopts technology of preparing scheme well known to those skilled in the art to prepare voluntarily.
In the present invention, the preparation method of described basic carbonate manganese preferably includes following steps:
Manganese salt solution and precipitant solution are reacted, is precipitated thing;
Described sediment is carried out successively wash and drying, obtain basic carbonate manganese.
Manganese salt solution and precipitant solution carry out being obtained by reacting sediment by the present invention.In the present invention, in described manganese salt solution, the molar concentration of manganese salt is preferably 0.45mol/L ~ 0.55mol/L, is more preferably 0.5mol/L.In the present invention, in described precipitant solution, the molar concentration of precipitating reagent is preferably 0.45mol/L ~ 0.55mol/L, is more preferably 0.5mol/L.
The order by merging of the present invention to described manganese salt solution and precipitant solution does not have special restriction, is preferably joined in described manganese salt by described precipitating reagent, more preferably described precipitant solution is joined in described manganese salt solution with the drop rate of 2 ~ 3/s.The present invention preferably carries out the mixing of manganese salt solution and precipitant solution under the condition stirred.After the present invention completes the mixing of manganese salt solution and precipitant solution, the mixed solution obtained is reacted, is precipitated thing.In the present invention, the temperature that described mixed solution carries out reacting is preferably 35 DEG C ~ 45 DEG C, is more preferably 40 DEG C; The time that described mixed solution carries out reacting is preferably 55min ~ 65min, is more preferably 60min.In the present invention, in described manganese salt solution, manganese salt is preferably one or more in manganese nitrate, manganese sulfate, manganese chloride and Organic Manganese salt; Be more preferably in manganese nitrate, manganese sulfate and manganese chloride one or more.In the present invention, the precipitating reagent in described precipitant solution is preferably NH
4hCO
3.In the present invention, the amount of substance of the precipitating reagent in manganese salt solution in manganese salt and precipitant solution is than being preferably (0.8 ~ 1.2): (2.3 ~ 2.8), be more preferably (0.9 ~ 1.1): (2.4 ~ 2.7), most preferably are 1.0:2.5.
After being precipitated thing, described sediment carries out washing and drying by the present invention successively, obtains basic carbonate manganese.After sediment preferably filters by the present invention, undertaken washing and drying by filtering the solid sediment obtained.The present invention does not have special restriction to described washing and dry method, adopts washing well known to those skilled in the art and dry technical scheme.The present invention preferably adopts deionized water and absolute ethyl alcohol to wash 3 ~ 5 times respectively.In the present invention, the temperature of described drying is preferably 70 DEG C ~ 80 DEG C, is more preferably 73 DEG C ~ 77 DEG C, most preferably is 75 DEG C; The time of described drying is preferably 2.5h ~ 3.5h, is more preferably 2.8h ~ 3.2h, most preferably is 3h.
In the present invention, described zirconium compounds preferably includes zirconium nitrate, zirconium sulfate or zirconyl chloride; More preferably Zr (NO is comprised
3)
45H
2o, Zr (SO
4)
24H
2o or ZrOCl
28H
2o.
In the present invention, described rare earth compound preferably includes rare earth nitrades, rare earth sulfate or Rare Earths salt; Rare earth element in described rare earth compound is preferably cerium, praseodymium or terbium; Be more preferably cerium.
In the present invention, described eutectic mixture comprises potassium nitrate-potassium hydroxide eutectic mixture, natrium nitrosum-potassium nitrate eutectic mixture, neopentyl glycol-4 bromide eutectic mixture or NaOH-potassium hydroxide eutectic mixture; Preferably include potassium nitrate-potassium hydroxide eutectic mixture, natrium nitrosum-potassium nitrate eutectic mixture or NaOH-potassium hydroxide eutectic mixture.In the present invention, in described potassium nitrate-potassium hydroxide eutectic mixture, the mass ratio of potassium nitrate and potassium hydroxide is preferably (35 ~ 40): (60 ~ 65), are more preferably (36 ~ 39): (61 ~ 64);
In described natrium nitrosum-potassium nitrate eutectic mixture, the mass ratio of potassium nitrate and potassium hydroxide is preferably (40 ~ 45): (50 ~ 55), are more preferably (41 ~ 44): (51 ~ 54);
In described neopentyl glycol-4 bromide eutectic mixture, the mass ratio of neopentyl glycol and 4 bromide is preferably (40 ~ 43): (60 ~ 63), are more preferably (41 ~ 42): (61 ~ 62);
In described NaOH-potassium hydroxide eutectic mixture, the mass ratio of NaOH and potassium hydroxide is preferably (50 ~ 55): (45 ~ 50), are more preferably (51 ~ 54): (46 ~ 49).
In the present invention, the described mol ratio containing manganese compound and rare earth compound is preferably 1.8 ~ 2.2:1, is more preferably 1.9 ~ 2.1:1, most preferably is 2:1; The described mass ratio containing manganese compound and eutectic mixture is preferably 1 ~ 8:100, is more preferably 1.5 ~ 7:100, most preferably is 1.3 ~ 6.8:100; The amount of substance of described zirconium compounds and rare earth compound, than being preferably 2.8 ~ 3.2:1, being more preferably 2.9 ~ 3.1:1, most preferably being 3:1.
The present invention is preferably placed in reaction vessel by described reacts containing manganese compound, rare earth compound, zirconium compounds and eutectic mixture; Preferred employing stainless steel cauldron well known to those skilled in the art reacts.The firing equipment of the present invention to reaction equation does not have special restriction, adopts firing equipment well known to those skilled in the art.In the present invention, described firing equipment preferably includes resistance furnace, Muffle furnace or baking oven.
The present invention mixes with eutectic mixture containing manganese compound, rare earth compound, zirconium compounds to make, and preferably contains manganese compound, zirconium compounds, rare earth compound and eutectic mixture pre-heat fusing in reaction vessel by described, then machinery mixing.In the present invention, the temperature of described pre-heat fusing is preferably 100 DEG C ~ 220 DEG C, is more preferably 120 DEG C ~ 200 DEG C; The time of described pre-heat fusing is preferably 20min ~ 60min, is more preferably 30min ~ 55min; The mode of described machinery mixing preferably stirs or rocks.
Complete described containing after manganese compound, rare earth compound, the mixing of zirconium compounds and eutectic mixture, the mixture obtained is carried out solvent thermal reaction by the present invention, obtains denitrating catalyst.In the present invention, the temperature that mixture carries out solvent thermal reaction is preferably 100 DEG C ~ 220 DEG C, is more preferably 120 DEG C ~ 200 DEG C; The time of described solvent thermal reaction is preferably 12h ~ 96h, is more preferably 24h ~ 80h, most preferably is 48h ~ 72h.
After completing the reaction of mixture, the product obtained preferably cools by the present invention.Product is preferably cooled to 10 DEG C ~ 35 DEG C by the present invention, is more preferably 15 DEG C ~ 30 DEG C, most preferably is 20 DEG C ~ 25 DEG C.
After completing cooling, cooled product preferably carries out filtering and washing by the present invention successively, obtains denitrating catalyst.The present invention preferably adopts centrifuge or pumping and filtering device to filter; When the present invention adopts centrifuge to filter, the rotating speed of centrifuge is preferably 1000rpm ~ 4000rpm; The present invention does not have special restriction to described pumping and filtering device, adopts pumping and filtering device well known to those skilled in the art.The present invention preferably adopts deionized water and absolute ethyl alcohol respectively to wash 3 ~ 5 times successively; Preferably by product washing to pH value be 7.
Present invention also offers denitrating catalyst prepared by the preparation method described in a kind of technique scheme.Denitrating catalyst provided by the invention comprises the oxide of manganese, the oxide of zirconium and rare earth oxide.In the present invention, the valence state of described rare earth oxide rare earth elements has+3 valencys and+4 valencys; In the present invention, the oxide of described manganese, the oxide of zirconium and rare earth oxide can be with independently oxide form existence in denitrating catalyst, also can exist with the form of composite oxides.
In the present invention, the oxide of described manganese can be specially Mn
2o
3, Mn
3o
4or MnO
2;
The oxide of described zirconium can be specially ZrO
2;
Described rare earth oxide can be Ce
2o
3, CeO
2, Pr
2o
3, PrO
2, Tb
2o
3or TbO
2.
In the present invention, described rare earth oxide not only can provide Lacking oxygen as carrier, enrich manganese valence in Mn oxide, as active component, can promote that NO is to NO again
2conversion, finally increase specific area and the Oxygen storage capacity of catalyst; Zirconium oxide can increase acid strength and the quantity of catalyst surface, contributes to the absorption of reacting gas, so the low-temperature catalytic activity of denitrating catalyst is improved.
The present invention adopts BET specific surface area method to carry out the test of specific area to the denitrating catalyst prepared.Test result shows: the specific area of denitrating catalyst prepared by preparation method provided by the invention is more than or equal to 200m
2/ g.
The present invention carries out the performance evaluation of catalyst to the denitrating catalyst prepared.In the present invention, the method of evaluating performance of described denitrating catalyst is: denitrating catalyst is carried out grinding screening, get 20 order ~ 60 object denitrating catalyst 0.5g and be placed in fixed bed quartz tube reactor, simulated flue gas is passed in reactor, carry out activity and selectivity test, test condition is: temperature is 100 DEG C ~ 250 DEG C, and air speed is 20000h
-1; When described simulated flue gas comprises N
2, O
2, NO and NH
3time, wherein NO volumetric concentration is 600ppm, NH
3volumetric concentration is 600ppm, O
2concentration is 3%, and Balance Air is nitrogen.Test result is: under 120 DEG C ~ 200 DEG C conditions, denitration rate is stabilized in more than 80%, to N
2selective more than 80%.
When described simulated flue gas comprises 500ppmSO
2, 3vol%H
2o, 600ppm NO, 600ppm NH
3and 3vol%O
2, when Balance Air is nitrogen, test result is: denitration rate when 220 DEG C is more than 78%.
The present invention adopts S-3000N30kV SEM to carry out SEM test to above-mentioned denitrating catalyst, and test result shows: denitrating catalyst provided by the invention has special controllable appearance.The present invention controls the pattern of product by changing reaction temperature, eutectic system and reaction time.
The present invention adopts D8 Advance polycrystal X ray diffractometer to carry out X-ray diffraction test to above-mentioned denitrating catalyst, and test result shows: denitrating catalyst provided by the invention comprises the oxide of manganese, the oxide of zirconium and rare earth oxide.
The invention provides a kind of preparation method of denitrating catalyst, comprise the following steps: will mix with eutectic mixture containing manganese compound, zirconium compounds, rare earth compound, and carry out solvent thermal reaction, obtain denitrating catalyst; Described eutectic mixture comprises potassium nitrate-potassium hydroxide eutectic mixture, natrium nitrosum-potassium nitrate eutectic mixture, neopentyl glycol-4 bromide eutectic mixture or NaOH-potassium hydroxide eutectic mixture.Denitrating catalyst prepared by preparation method provided by the invention has higher specific area, and then has higher denitration rate.The low temperature active of denitrating catalyst provided by the invention is good, can keep good removal of nitrogen oxide rate and water resistant resistance to SO_2, higher N in the flue gas of 100 DEG C ~ 250 DEG C
2selective, and the life-span is long.Preparation method provided by the invention is the hot method of a step chemical solvent, react at ambient pressure, in preparation process, do not add any template, there is not the problem such as high-temperature calcination of later stage removing template, synthetic method is simple, energy consumption and cost is low, environmental friendliness.Experimental result shows: the specific area of denitrating catalyst provided by the invention is more than or equal to 200m
2/ g; At 100 DEG C ~ 230 DEG C, denitration rate more than 80%, to N
2selective more than 80%.
Denitrating catalyst provided by the invention can be applicable to the NH of the nitrogen oxide in the discharging waste gas such as thermal power plant, Industrial Boiler
3sCR is removed.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of denitrating catalyst provided by the invention and preparation method thereof being described in detail, but they can not being interpreted as limiting the scope of the present invention.
Embodiment 1
(1) by 14.48g KNO
3mix as reaction dissolvent with 25.52g KOH;
(2) 6mmolMnO is got
2, 3mmol CeCl
37H
2o and 1mmol Zr (NO
3)
45H
2o is as reaction raw materials;
(3) reaction dissolvent in the reaction raw materials of above-mentioned steps (2) and above-mentioned steps (1) is inserted in polytetrafluoroethyllining lining reactor, add a cover and close that to insert temperature be in the constant temperature Muffle furnace of 200 DEG C, pre-heat fusing is after 30 minutes, open reactor, stir or rock the reaction dissolvent and reaction raw materials Homogeneous phase mixing that make molten state, again reactor is closed, and under the state of constant temperature 200 DEG C, continue heating 24h;
(4) reactor after isothermal reaction is cooled to room temperature;
(5) by product deionized water dissolving, then be the centrifuge of 4000 revs/min with rotating speed, then centrifuged deposit disperseed in deionized water again, repeat above-mentioned steps 4 times, until the pH value of product is 7, obtain denitrating catalyst.
The specific area that the present invention records the obtained denitrating catalyst of the present embodiment 1 according to BET method is 245.5m
2/ g.
The present invention carries out SEM test to the denitrating catalyst obtained, and as shown in Figure 1, Fig. 1 is the SEM figure of the denitrating catalyst that the embodiment of the present invention 1 obtains to test result, as can be seen from Figure 1: this catalyst has petal-shaped pattern.
The present invention carries out XRD analysis to the denitrating catalyst obtained, and as shown in Figure 2, Fig. 2 is the XRD spectra of the denitrating catalyst that the embodiment of the present invention 1 obtains to analysis result, as can be seen from Figure 2: catalyst activity component has CeO
2, ZrO
2, MnO
2, Mn
2o
3and Mn
3o
4.
The present invention carries out performance evaluation according to the denitrating catalyst that the evaluation technical proposal of denitrating catalyst described in technique scheme is obtained to the present embodiment, and test result is: under 120 DEG C ~ 200 DEG C conditions, denitration efficiency is stabilized in more than 90%, to N
2selective more than 90%; When there is SO in simulated flue gas
2time, denitration rate when 220 DEG C is more than 85%.
Embodiment 2
(1) by 8.1g NaNO
2with 9.9g KNO
3mixing is as reaction dissolvent;
(2) by manganese nitrate and precipitating reagent NH
4hCO
3be dissolved in respectively in deionized water, be made into the solution of 0.5mol/L.In the water bath with thermostatic control of 40 DEG C, while stirring by precipitating reagent NH
4hCO
3solution is added in manganese nitrate solution with the speed of 2/s, after dropwising, continue at 40 DEG C, be incubated 1h (total mol ratio that course of reaction controls manganese nitrate and precipitating reagent is 1.0: 2.5), gained sediment is filtered, 5 times are respectively washed respectively with deionized water and absolute ethyl alcohol, at 75 DEG C of dry 3h, obtain basic carbonate manganese;
Get 6mmol basic carbonate manganese, 3mmolCe (NO
3)
36H
2o and 1mmol ZrOCl
28H
2o is as reaction raw materials;
(3) reaction dissolvent in the reaction raw materials of above-mentioned steps (2) and above-mentioned steps (1) is inserted in polytetrafluoroethyllining lining reactor, add a cover and close that to insert temperature be in the constant temperature Muffle furnace of 140 DEG C, pre-heat fusing is after 30 minutes, open reactor, stir the reaction dissolvent and the reaction raw materials Homogeneous phase mixing that make molten state, again reactor is closed, and under the state of constant temperature 140 DEG C, continue heating 48h;
(4) reactor after isothermal reaction is cooled to room temperature;
(5) by product deionized water dissolving, be the centrifuge of 3000 revs/min again with rotating speed, then centrifuged deposit be dispersed in again in deionized water and absolute ethyl alcohol, repeat above-mentioned steps 4 times, until the pH value of product is 7, obtain denitrating catalyst.
The specific area that the present invention records the obtained denitrating catalyst of the present embodiment 2 according to BET method is 258.2m
2/ g.
The present invention carries out SEM test to the denitrating catalyst obtained, and as shown in Figure 3, Fig. 3 is the SEM figure of the denitrating catalyst that the embodiment of the present invention 2 obtains to test result, as can be seen from Figure 3: this catalyst is made up of the particle of synusia stacking.
The present invention carries out XRD analysis to the denitrating catalyst obtained, and as shown in Figure 4, Fig. 4 is the XRD spectra of the denitrating catalyst that the embodiment of the present invention 2 obtains to analysis result, as can be seen from Figure 4: this catalyst activity component has Ce
2zr
2o
7, MnO
2, Mn
2o
3and Mn
3o
4.
The present invention carries out performance evaluation according to the denitrating catalyst that the evaluation technical proposal of denitrating catalyst described in technique scheme is obtained to the present embodiment, and test result is: under 120 DEG C ~ 200 DEG C conditions, denitration efficiency is stabilized in more than 80%, to N
2selective more than 85%; When there is SO in simulated flue gas
2time, denitration rate when 220 DEG C is more than 80%.
Embodiment 3
(1) 10.3g NaOH and 9.7g KOH is mixed as reaction dissolvent;
(2) 6mmol MnO is got
2, 3mmol Ce (NO
3)
36H
2o and 1mmol Zr (SO
4)
24H
2o is as reaction raw materials;
(3) reaction dissolvent in the reaction raw materials of above-mentioned steps (2) and above-mentioned steps (1) is inserted in polytetrafluoroethyllining lining reactor, add a cover and close that to insert temperature be in the constant temperature Muffle furnace of 185 DEG C, pre-heat fusing is after 30 minutes, open reactor, stir the reaction dissolvent and the reaction raw materials Homogeneous phase mixing that make molten state, again reactor is closed, and under the state of constant temperature 185 DEG C, continue heating 48h;
(4) reactor after isothermal reaction is cooled to room temperature;
(5) by product deionized water dissolving, then be the centrifuge of 3000 revs/min with rotating speed, then centrifuged deposit disperseed in deionized water again, repeat above-mentioned steps 4 times, until the pH value of product is 7, obtain denitrating catalyst.
The specific area that the present invention records the obtained denitrating catalyst of the present embodiment 3 according to BET method is 262.4m
2/ g.
The present invention carries out performance evaluation according to the denitrating catalyst that the evaluation technical proposal of denitrating catalyst described in technique scheme is obtained to the present embodiment, and test result is: under 120 DEG C ~ 200 DEG C conditions, denitration rate is stabilized in more than 80%, to N
2selective more than 80%; When there is SO in simulated flue gas
2time, denitration rate when 220 DEG C is more than 78%.
Embodiment 4
(1) neopentyl glycol 7.2g, 4 bromide 10.8g are mixed as reaction dissolvent;
(2) by manganese nitrate and precipitating reagent NH
4hCO
3be dissolved in respectively in deionized water, be made into the solution of 0.5mol/L, in the water bath with thermostatic control of 40 DEG C, while stirring by precipitating reagent NH
4hCO
3solution is added drop-wise in manganese nitrate solution with the speed of 2/s, after dropwising, continue to be incubated 1h at 40 DEG C, total mol ratio that course of reaction controls manganese nitrate and precipitating reagent is 1.0:2.5, gained sediment is filtered, respectively wash 3 times with deionized water and absolute ethyl alcohol respectively, at 75 DEG C of dry 3h, obtain basic carbonate manganese;
Get 6mmol basic carbonate manganese, 3mmolCe (SO
4)
24H
2o and 1mmol Zr (NO
3)
45H
2o is as reaction raw materials;
(3) reaction dissolvent in the reaction raw materials of above-mentioned steps (2) and above-mentioned steps (1) is inserted in polytetrafluoroethyllining lining reactor, add a cover and close that to insert temperature be in the constant temperature Muffle furnace of 150 DEG C, pre-heat fusing is after 30 minutes, open reactor, rock the reaction dissolvent and reaction raw materials Homogeneous phase mixing that make molten state, again reactor is closed, and under the state of constant temperature 150 DEG C, continue heating 72h;
(4) reactor after isothermal reaction is cooled to room temperature;
(5) by product deionized water dissolving, then be the centrifuge of 4000 revs/min with rotating speed, then centrifuged deposit disperseed in deionized water again, repeat above-mentioned steps 4 times, until the pH value of product is 7, obtain denitrating catalyst.
The specific area that the present invention records the obtained denitrating catalyst of the present embodiment 4 according to BET method is 234.6m
2/ g.
The present invention carries out performance evaluation according to the denitrating catalyst that the evaluation technical proposal of denitrating catalyst described in technique scheme is obtained to the present embodiment 4, and test result is: under 120 DEG C ~ 200 DEG C conditions, denitration efficiency is stabilized in more than 85%, to N
2selective more than 80%; When there is SO in simulated flue gas
2time, denitration rate when 220 DEG C is more than 80%.
As seen from the above embodiment, the invention provides a kind of preparation method of denitrating catalyst, comprise the following steps: will mix with eutectic mixture containing manganese compound, rare earth compound, zirconium compounds, and carry out solvent thermal reaction, obtain denitrating catalyst; Described eutectic mixture comprises potassium nitrate-potassium hydroxide eutectic mixture, natrium nitrosum-potassium nitrate eutectic mixture, neopentyl glycol-4 bromide eutectic mixture or NaOH-potassium hydroxide eutectic mixture.Denitrating catalyst prepared by preparation method provided by the invention has higher specific area, and then has higher denitration rate.The low temperature active of denitrating catalyst provided by the invention is good, can keep good removal of nitrogen oxide rate and water resistant resistance to SO_2, higher N in the flue gas of 100 DEG C ~ 250 DEG C
2selective, and the life-span is long.Preparation method provided by the invention does not add any template in preparation process, there is not the problem such as high-temperature calcination of later stage removing template, synthetic method is simple, energy consumption and cost is low, environmental friendliness.Experimental result shows: the specific area of denitrating catalyst provided by the invention is more than or equal to 200m
2/ g; At 100 DEG C ~ 230 DEG C, denitration rate more than 80%, to N
2selective more than 80%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for denitrating catalyst, comprises the following steps:
To mix with eutectic mixture containing manganese compound, rare earth compound, zirconium compounds, and carry out solvent thermal reaction, obtain denitrating catalyst;
Described eutectic mixture comprises potassium nitrate-potassium hydroxide eutectic mixture, natrium nitrosum-potassium nitrate eutectic mixture, neopentyl glycol-4 bromide eutectic mixture or NaOH-potassium hydroxide eutectic mixture.
2. preparation method according to claim 1, is characterized in that, in described potassium nitrate-potassium hydroxide eutectic mixture, the mass ratio of potassium nitrate and potassium hydroxide is (35 ~ 40): (60 ~ 65);
In described natrium nitrosum-potassium nitrate eutectic mixture, the mass ratio of potassium nitrate and potassium hydroxide is (40 ~ 45): (50 ~ 55).
3. preparation method according to claim 1, is characterized in that, in described neopentyl glycol-4 bromide eutectic mixture, the mass ratio of neopentyl glycol and 4 bromide is (40 ~ 43): (60 ~ 63);
In described NaOH-potassium hydroxide eutectic mixture, the mass ratio of NaOH and potassium hydroxide is (50 ~ 55): (45 ~ 50).
4. preparation method according to claim 1, is characterized in that, the described manganese compound that contains comprises MnO
2and/or basic carbonate manganese.
5. preparation method according to claim 1, is characterized in that, described zirconium compounds comprises zirconium nitrate, zirconium sulfate or zirconyl chloride.
6. preparation method according to claim 1, is characterized in that, described rare earth compound comprises rare earth nitrades, rare earth sulfate or Rare Earths salt.
7. preparation method according to claim 1, is characterized in that, described rare earth compound rare earth elements is cerium, praseodymium or terbium.
8. preparation method according to claim 1, is characterized in that, the temperature of described solvent thermal reaction is 100 DEG C ~ 220 DEG C;
The time of described solvent thermal reaction is 12h ~ 96h.
9. denitrating catalyst prepared by the preparation method described in claim 1 ~ 8 any one.
10. denitrating catalyst according to claim 9, is characterized in that, the specific area of described denitrating catalyst is more than or equal to 200m
2/ g.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491304A (en) * | 2011-12-02 | 2012-06-13 | 罗绍华 | Method for preparing lithium iron phosphate in ionic eutectic mixture |
| CN103143345A (en) * | 2013-03-12 | 2013-06-12 | 合肥工业大学 | Composite catalyst for catalytically oxidizing nitrogen oxide and preparation method of composite catalyst |
| CN104043449A (en) * | 2014-07-09 | 2014-09-17 | 南京师范大学 | Novel low-temperature SCR (selective catalytic reduction) catalyst based on cubic-phase zirconia carrier and preparation method of novel low-temperature SCR catalyst |
-
2014
- 2014-11-04 CN CN201410611728.8A patent/CN104437471A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491304A (en) * | 2011-12-02 | 2012-06-13 | 罗绍华 | Method for preparing lithium iron phosphate in ionic eutectic mixture |
| CN103143345A (en) * | 2013-03-12 | 2013-06-12 | 合肥工业大学 | Composite catalyst for catalytically oxidizing nitrogen oxide and preparation method of composite catalyst |
| CN104043449A (en) * | 2014-07-09 | 2014-09-17 | 南京师范大学 | Novel low-temperature SCR (selective catalytic reduction) catalyst based on cubic-phase zirconia carrier and preparation method of novel low-temperature SCR catalyst |
Non-Patent Citations (3)
| Title |
|---|
| F. BONDIOLI ET AL.: "NANOSIZED CeO2 POWDERS OBTAINED BY FLUX METHOD", 《MATERIALS RESEARCH BULLETIN》, vol. 34, no. 1415, 31 December 1999 (1999-12-31), pages 2159 - 2166 * |
| KOUICHI NAKASHIMA ET AL.: "Preparation of BaZrO3 cubes by composite-hydroxide-mediated approach at low temperature", 《JOURNAL OF THE CERAMIC SOCIETY OF JAPAN》, vol. 119, no. 6, 31 December 2011 (2011-12-31), pages 532 - 534 * |
| 彭强等: "硝酸熔盐体系在能源利用中的研究进展", 《现代化工》, vol. 29, no. 6, 30 June 2009 (2009-06-30), pages 17 - 22 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569865A (en) * | 2020-06-03 | 2020-08-25 | 齐鲁工业大学 | Bio-based low-temperature denitration catalyst and preparation method thereof |
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