CN103599813A - Molecular sieve based catalyst used for low-temperature SCR denitration and its preparation method - Google Patents
Molecular sieve based catalyst used for low-temperature SCR denitration and its preparation method Download PDFInfo
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Abstract
The invention relates to a low-temperature denitration SCR (selective catalytic reduction) catalyst, which includes a Cu modified molecular sieve carrier and one or more oxides of Ce, Zr, and Mn. The employed carrier is a Cu-SSZ-13 molecular sieve that is synthesized by a cheap template route and then undergoes modification. The catalyst provided by the invention has a nitrogen oxide removal rate up to 62-100% in the range of 100-250DEG C, and the low-temperature catalyst involved in the invention has good sulfur-resisting capacity.
Description
Technical field
Molecular sieve of the present invention field, provides a kind of molecular sieve based catalyst for low temperature SCR denitration and preparation method thereof.
Background technology
Be accompanied by the continuous growth of energy-consuming, the coal-burning boiler of take is main stationary source, and internal combustion engine of motor vehicle to be main moving source increasing to the amount of discharging nitrogen oxide (NOx) in atmosphere.Nitrogen oxide (NOx) is one of pollution main in atmospheric environment, can form photochemical fog, produce acid rain, acid mist, can also damage the ozone layer, huge to environmental hazard, more health is had to harm, can cause respiratory disease, the pollution of therefore controlling and administering nitrogen oxide is the study hotspot of international scope always.
Ammonia selective catalytic reduction (selective catalytic reduction, SCR), because its efficient feature and ripe technical development become the denitration technology of current main flow, and the key problem of this technology is exactly the catalyst of development efficient stable.At present the catalyst in using is more widely mainly to take TiO2 as carrier, the middle high temperature catalyst of the component such as a certain amount of V2O5, WO3 or MoO3 in load, and general operation temperature is 350 ℃ of left and right.In the denitrating flue gas application for stationary source, in order to meet the requirement of operating temperature, generally by SCR catalyst arrangement before deduster, but because fly ash content in flue gas is high, easily make beds stop up, and in flue gas, sulfur content is also higher, easily makes catalyst poisoning inactivation.Component vanadium in catalyst is poisonous in addition, unfavorable to ecological environment and health.For the discharge of nitrogen oxide in exhaust gas from diesel vehicle in moving source, SCR technology and relevant catalyst are being that tool is promising aspect this.The current domestic denitrating catalyst that there is no large-scale production, owing to containing a large amount of oxygen in exhaust gas from diesel vehicle, operation operating mode is also more complicated, in Cold Start, having a large amount of NOx produces, for these features, require the catalyst adopting to have wider warm window, traditional vanadium tungsten titanium catalyst and the three-way catalyst of gasoline car all can not meet the purification requirement of NOx in exhaust gas from diesel vehicle.
The focus of research is exploitation low-temperature SCR technology at present, and low-temperature SCR technology can reduce denitrating flue gas cost.If low-temperature SCR reaction temperature can be reduced to 100-200 ℃, just SCR reactor can be placed on after desulfurizing dust-collector, dwindle reactor volume and reduce denitration cost.Employing, without the catalyst of vanadium, just can solve catalyst toxicity problem.Therefore, how to develop the low temperature catalyst that is applicable to low-temperature zone, realize the high-activity high-selectivity of catalyst in low-temperature range, determined that can low temperature SCR denitration technology be widely used.
In order to develop low-temperature SCR technology, researcher has carried out a series of research.Developed at present a small amount of low-temperature SCR catalyst, the main MnOx/CeO2 catalyst series that adopts coprecipitation, sol-gel process, infusion process to prepare, by adding auxiliary agent, improve the anti-sulphur ability of catalyst water resistant, the patent application that application number is CN101879452A discloses a kind of preparation method who is applied to the compound simple oxide catalyst of low-temperature denitration.This catalyst be take the oxide of manganese and cerium and is basis, by adding other metal oxides, as auxiliary agent, obtained active good low-temperature denitration catalyst, but simple composite oxide specific area is lower, selectively also poor to what react, temperature slightly high (>150 ℃) can produce a large amount of accessory substances, and the selective of N2 obviously declines.While entering middle warm area (>250 ℃), the activity of catalyst starts to decline.
The application of catalyst carrier can increase the specific area of catalyst, pore volume, heat endurance and mechanical strength.Common carrier has TiO2, SiO2, Al2O3, active carbon, zeolite etc.TiO2 has a large amount of acid sites positions, is conducive to the absorption of NH3, but its specific area and pore volume are not enough.There is a large amount of hydroxyl groups on Al2O3 surface, be conducive to NO and be oxidized into NO2, can improve reaction rate, but sulfur resistance is poor, authorize and disclose a kind of catalyst and preparation method of the SCR denitration for boiler low-temperature fume for the national inventing patent of CN100473456C public number, take active carbon as carrier, with the infusion process oxide of Supported Manganese and cerium in the above.This catalyst is used NACF as carrier, has larger surface area, the high adsorption capacity to gaseous material, but its shortcoming is that water resistant ability is poor, and mechanical strength is not enough, and catalyst is easy-formation not.
In sum, still there is certain problem in the research and development of low-temperature SCR catalyst at present.Find applicable catalyst based catalyst carrier and need further research and development.
Summary of the invention
The first object of the present invention is to provide a kind of molecular sieve based catalyst for low temperature SCR denitration, by use, adopt the synthetic zeolite molecular sieve of specific process as carrier, this kind of carrier has excellent low-temperature SCR activity than traditional zeolite molecular sieve carrier, by supported active oxide component, prepared high activity, the low temperature catalyst of high stability; In addition, the present invention also provides a kind of preparation method of above-mentioned catalyst.
For realizing the first object, the present invention adopts following technical scheme:
For a molecular sieve based catalyst for low temperature SCR denitration, comprise the molecular sieve carrier of Cu modification and be selected from one or more oxides in Ce, Zr, tri-kinds of elements of Mn.
One or more oxides that are selected from Ce, Zr, tri-kinds of elements of Mn described in the present invention refer to CeO
2, ZrO
2and MnO
2in one or more, preferred CeO wherein
2-ZrO
2-MnO
2composite oxides.
It should be noted that, although the present invention limits molecular sieve based catalyst with the form of oxide and consumption, but it will be understood by those skilled in the art that, it is only the conventional means of this area herein, do not represent Ce, Zr, the raw material of tri-kinds of elements of Mn is confined to oxide, other forms, as contain Ce, Zr, the salt of tri-kinds of elements of Mn (Ce after salt calcining, Zr, tri-kinds of elements of Mn are all that the form with oxide exists) etc., may be used to prepare the raw material of molecular sieve based catalyst, those skilled in the art can understand and be selected, the present invention is not particularly limited this.
The molecular sieve carrier of Cu modification of the present invention makes by specific process, there is abundant micropore canals structure and high-specific surface area, after being applied in the molecular sieve based catalyst described in the application, make catalyst itself there is optionally advantage of high nitrogen.
As one embodiment of the present invention (A method), the molecular sieve carrier of described Cu modification is prepared by following methods:
Take cupric ammine complex as structure directing agent and Tong Yuan, add ,Lv source, silicon source and aqueous slkali, molecular sieve is at Na
2o:Al
2o
3: SiO
2: H
2o: synthetic in the aqueous precursor gel system that cupric ammine complex molar ratio is 3.1～3.8:1.0:10～35:200:2.0～3.0 presoma stirring is put into hydrothermal reaction kettle crystallization at 120-150 ℃, product is filtered, cleaned, obtains Cu-SSZ-13 after dry, roasting.
Wherein, described cupric ammine complex is Cu-TEPA.
Wherein, described silicon source is oxide containing silicon and silicate, is preferably silicate, Ludox, ethyl orthosilicate, deposition of silica and clay, more preferably Ludox; Described aluminium source is trivalent aluminium oxide or aluminate, is preferably sodium metaaluminate, aluminium oxide or aluminium hydroxide; Aqueous slkali is NaOH.Preferably described silicon source is that Ludox, described aluminium source are that sodium metaaluminate aqueous slkali is NaOH.
As another embodiment of the present invention (B method), the molecular sieve carrier of described Cu modification is prepared by following methods:
Described method is included under crystallization condition following raw materials according material is contacted in water, obtains molecular sieve crystal:
(1) at least one silicon source;
(2) at least one aluminium source;
(3) at least one alkali metal compound;
(4) as the choline cation of structure directing agent;
(5) hydroxide ion;
By prepared molecular sieve crystal and copper nitrate, copper sulphate or copper acetate solution ion-exchange 4-8h at 40-80 ℃, then carry out vacuum rotary steam, at 80-120 ℃, be dried afterwards 8-12h, 500-600 ℃ of roasting 4-8h in Muffle furnace, obtains the molecular sieve carrier Cu-SSZ-13 of Cu modification.
Concrete grammar is as follows:
A) mixture of preparatory response:
Comprising (1) at least one tetravalence silicon source; (2) at least one trivalent aluminium source; (3) at least one alkali metal compound; (4) as the choline cation of unique structure directing agent (SDA); (5) form a large amount of hydroxide ions of strong alkali environment; (6) for impelling raw mixture to form the water of the presoma of collosol and gel.
B), in the process of heating crystallization, make precursor mixture have time enough crystallization to go out to have the SSZ-13 Si-Al molecular sieve of microcellular structure.
C) with copper source, SSZ-13 Si-Al molecular sieve is carried out to modification, obtain the molecular sieve carrier of Cu modification.
Wherein, described tetravalence silicon source includes but not limited to oxide containing silicon and silicate, is preferably silicate, Ludox, ethyl orthosilicate, deposition of silica and clay, more preferably Ludox.
Wherein, described trivalent aluminium source is trivalent aluminium oxide or aluminate, is preferably sodium metaaluminate, aluminium oxide or aluminium hydroxide.
Described alkali metal compound is compounds containing sodium, preferably NaOH or sodium chloride, more preferably NaOH.
Wherein, described choline cation is bursine and Choline Chloride, preferably Choline Chloride.
Preparation method of the present invention, wherein the mol ratio in water and tetravalence silicon source is that 3:1 is to 15:1.
It is silica alumina ratio that the mol ratio in tetravalence silicon source and trivalent aluminium source is greater than 3(), be preferably 50 or higher.
In order to optimize whole synthetic method, inventor, on the basis of lot of experiments research, likens following preferably restriction to the mole dosage of each raw material:
Preferred:
The preparation method of above-mentioned Cu modified molecular screen, get the raw materials ready after end, reactant mixture is carried out to heating crystallization, wherein, reaction temperature remains on 100 ℃-200 ℃, minimum 4 days of crystallization process, product crystalline solid is dried 8-12 hour at 90 ℃-150 ℃ after washing, and then in Muffle furnace, 500-600 ℃ of calcining obtains SSZ-13 molecular sieve crystal for 6-10 hour.Preferable reaction temperature remains on 140 ℃, crystallization process 5-35 days, and product crystalline solid is dried 10-11 hour at 120 ℃ after washing, and then in Muffle furnace, 550 ℃ of calcinings obtain SSZ-13 molecular sieve crystal for 8 hours.
By prepared molecular sieve crystal and copper nitrate, copper sulphate or copper acetate solution ion-exchange 4-8h at 40-80 ℃, then carry out vacuum rotary steam, at 80-120 ℃, be dried afterwards 8-12h, 500-600 ℃ of roasting 4-8h in Muffle furnace, obtains the molecular sieve carrier Cu-SSZ-13 of Cu modification.
Except the given above-mentioned preferred embodiment (effect is better) of the present invention, those skilled in the art also can select the SSZ-13 molecular sieve carrier of disclosed other Cu modifications of prior art to realize the present invention, prepare the molecular sieve based catalyst for low temperature SCR denitration.
In catalyst of the present invention, when the oxide of selecting to contain one or both elements in Mn, Zr, Ce and molecular sieve carrier Kaolinite Preparation of Catalyst, the mol ratio of Mn, Zr, Ce and Cu is respectively (0-50): (10-15), (0-20): (10-15), (0-50): (10-15).
In catalyst of the present invention, the preferred CeO of described oxide
2-ZrO
2-MnO
2ternary compound oxides, in these composite oxides, the mol ratio of Mn, Zr, Ce and Cu is (30-50): (5-10): (30-50): (10-15).Under this amount ranges, contribute to catalyst low-temperature activity, the raising of the selective and sulfur resistance of nitrogen.
Further, in described catalyst, the mass ratio of molecular sieve carrier and oxide is 0.3-15, and Cu accounts for the 5-10wt% of molecular sieve supported weight, preferably 4-7wt%.
In addition, the present invention also provides the preparation method of above-mentioned molecular screen base low-temperature selective catalytic reduction of ammonia denitrating catalyst, and described method specifically comprises:
Step (1): the molecular sieve carrier of preparation Cu modification;
Step (2): one or more oxides in the molecular sieve carrier of Cu modification and Ce, Zr, tri-kinds of elements of Mn are at room temperature fully uniformly mixed to formation turbid solution with deionized water, the mole dosage of water be total amount of metal mole 80-120 doubly;
Step (3): ammonium carbonate is dissolved in to deionized water, be made into the sal volatile of 0.5-1.2M, then with the speed of 1-2ml/min, be added drop-wise in the turbid solution that step (2) configured, form precipitation, at room temperature continue to stir 1-3 hour, the consumption of added ammonium carbonate is 1.5-2.5 times of slaine mole;
Step (4): the solution system that step (3) is obtained is put into supersonic wave cleaning machine ultrasonic immersing 1～3 hour, filtering and washing;
Step (5): by the filter cake obtaining in step (4) dry 10-24 hour in the baking oven of 80-120 ℃, then at 500-600 ℃ roasting 4-8 hour, obtain MOx-Cu/SSZ-13 catalyst, M is one or more in Ce, Zr, tri-kinds of elements of Mn.
In order to control, form the more stable catalyst of quality, the present invention has made restriction to mixing speed step (3) Suo Shu, is specially 200-300r/min.
Adopt above-mentioned preparation scheme, the present invention can access high-quality low-temperature selective catalytic reduction of ammonia denitrating catalyst, described catalyst has higher low temperature active, selective with nitrogen, molecular sieve based catalyst of the present invention is for the purification to nitrogen oxide within the scope of 100-200 ℃, its efficiency reaches 62-100%, has good selective in the temperature range of experiment.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the SSZ-13 sieve sample prepared of embodiment 1 (A);
Fig. 2 is the XRD spectra of the SSZ-13 sieve sample prepared of embodiment 1 (B);
Fig. 3 is the XRD spectra of the SSZ-13 sieve sample prepared of embodiment 2 (A);
Fig. 4 is the XRD spectra of the SSZ-13 sieve sample prepared of embodiment 2 (B);
Fig. 5 is the catalyst of the embodiment 9 preparation anti-sulphur effect experimental result schematic diagram under different temperatures;
Fig. 6 is the catalyst of the embodiment 9 preparation anti-sulphur effect of the long period experimental result schematic diagram at 140 ℃ of temperature.
The specific embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
In following examples, chemical reagent used is commercial goods.
Embodiment 1
0.492 gram of sodium metaaluminate (aluminium source) and 3.6 grams of dissolution of sodium hydroxide, in 15.8 grams of deionized waters, are stirred and make it to dissolve completely.To in mixture, add 2.3 grams of Choline Chlorides, stir and make it to dissolve completely for 15 minutes.Under rapid stirring condition, slowly drip 18 grams of LUDOX-AS-40 Ludox (silicon source).
At room temperature stir one hour, last colloid is divided into two parts (A and B), and A and B have transferred to respectively in teflon-lined stainless steel autoclave, puts into the baking oven of 140 ℃ and keeps 4 days (for A) and 6 days (for B).
Product washs by deionized water, collect after filtration, in vacuum drying chamber, at 100 ℃, be dried 12 hours, then in Muffle furnace, 550 ℃ of calcinings remove structure directing agent for 8 hours, obtain SSZ-13 molecular sieve, wherein the XRD spectra of A, two groups of SSZ-13 molecular sieves of preparing of B is shown in Fig. 1 and Fig. 2.
With copper source copper nitrate, above-mentioned SSZ-13 molecular sieve is carried out to modification, obtain copper content and be the molecular sieve carrier (Cu-SSZ-13 molecular sieve carrier) of 5% Cu modification.
Embodiment 2
0.853 gram of sodium metaaluminate (aluminium source) and 3.0 grams of dissolution of sodium hydroxide, in 15.8 grams of deionized waters, are stirred and make it to dissolve completely.To in mixture, add 1.8 grams of Choline Chlorides, stir and make it to dissolve completely for 15 minutes.Under rapid stirring condition, slowly drip 17.25 grams of LUDOX-AS-40 cabosils (silicon source).
At room temperature stir one hour, last colloid is divided into two parts (A and B), and A and B have transferred to respectively in teflon-lined stainless steel autoclave, puts into the baking oven (for A) of 130 ℃ and 150 ℃ (for B) and keeps 6 days.
Product washs by deionized water, collect after filtration, at 100 ℃ of vacuum drying chambers dry 12 hours, then in Muffle furnace, at 550 ℃, calcine and within 8 hours, remove structure directing agent, obtain SSZ-13 molecular sieve, wherein the XRD spectra of A, two groups of SSZ-13 molecular sieves of preparing of B is shown in Fig. 3 and Fig. 4.
With copper source copper sulphate, above-mentioned SSZ-13 molecular sieve is carried out to modification, obtain copper content and be the molecular sieve carrier (Cu-SSZ-13 molecular sieve carrier) of 7% Cu modification.
Embodiment 3
Compare with embodiment 1, distinctive points is only, in the present embodiment, the concrete selection of each raw material of molecular sieve crystal and mole dosage, than different, are specially:
In the present embodiment, tetravalence silicon source is sodium metasilicate, and trivalent aluminium source is boehmite, and alkali metal compound is NaOH, and hydroxide ion provides with NaOH form.
Embodiment 4
Compare with embodiment 1, distinctive points is only, in the present embodiment, the concrete selection of each raw material of molecular sieve crystal and mole dosage, than different, are specially:
In the present embodiment, tetravalence silicon source is Ludox, and trivalent aluminium source is aluminium oxide, and alkali metal compound is sodium chloride, and hydroxide ion provides with ammoniacal liquor form.
Sodium metaaluminate 0.471g and NaOH 0.250g are dissolved in 10ml deionized water, and it is dissolved completely, then add 0.841g TEPA, getting 0.998g cupric sulfate pentahydrate joins in above-mentioned solution, stir after 1 hour, be added dropwise to the Ludox of 4ml40wt%, mixture was stirred after 3 hours, put into hydrothermal reaction kettle, at 140 ℃, react 4 days, the product deionized water washing obtaining, collects after filtration, at 100 ℃ of vacuum drying chambers dry 12 hours, obtain Cu-SSZ-13 molecular sieve.
Embodiment 6
Sodium metaaluminate 0.471g and NaOH 0.250g are dissolved in 10ml deionized water, and it is dissolved completely, then add 0.841g TEPA, getting 0.998g cupric sulfate pentahydrate joins in above-mentioned solution, stir after 1 hour, be added dropwise to the Ludox of 4ml40wt%, mixture was stirred after 3 hours, put into hydrothermal reaction kettle, at 150 ℃, react 4 days, the product deionized water washing obtaining, collects after filtration, at 100 ℃ of vacuum drying chambers dry 12 hours, obtain Cu-SSZ-13 molecular sieve.
Embodiment 7
Sodium metaaluminate 0.471g and NaOH 0.250g are dissolved in 10ml deionized water, and it is dissolved completely, then add 0.841g TEPA, getting 0.998g cupric sulfate pentahydrate joins in above-mentioned solution, stir after 1 hour, be added dropwise to the Ludox of 4ml40wt%, mixture was stirred after 3 hours, put into hydrothermal reaction kettle, at 120 ℃, react 4 days, the product deionized water washing obtaining, collects after filtration, at 100 ℃ of vacuum drying chambers dry 12 hours, obtain Cu-SSZ-13 molecular sieve.
Embodiment 8
A kind of molecular screen base low-temperature denitration catalyst preparation method is as follows:
1) preparation of carrier
The 4g Cu-SSZ-13 molecular sieve carrier (referring to embodiment 5-7) that the copper content that adopts A method to prepare is about to 10wt.% and 1M ammonium nitrate solution 400ml were 80 ℃ of stirred in water bath 12 hours, products therefrom suction filtration, washing, in 100 ℃ of baking ovens, be dried 12 hours, again product is put into 550 ℃ of Muffle furnace roastings 8 hours, obtained the Cu-SSZ-13 carrier that required copper content is about 6.5wt%.
2) load of catalyst
Step 1: get the 1.8g molecular sieve carrier and the 0.902g cerous nitrate that prepare, 0.600g50wt% manganese nitrate solution, 0.101g zirconium chloride is at room temperature fully uniformly mixed formation turbid solution with the deionized water of 100 times of moles.
Step 2: 0.85g ammonium carbonate is dissolved in to deionized water, is made into the sal volatile of 1M, be then added drop-wise in the turbid solution that step 1 configured with the speed of 1ml/min, form precipitation, at room temperature continue to stir 2 hours.
Step 3: gained slurries in step 2 are put into supersonic wave cleaning machine ultrasonic immersing 1 hour, then filtering and washing.
Step 4: by the filter cake obtaining in step 3 in the baking oven of 100 ℃ dry 12 hours, then put into Muffle furnace roasting 6 hours at 550 ℃, obtain MOx-Cu/SSZ-13 catalyst.
The active testing condition of this catalyst is: the NO of 1000ppm, the NH of 1000ppm
3, 6% O
2mix, using argon gas He as carrier gas, the 40-60 order particle that loaded catalyst is 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is about 50000/h.At 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 200 ℃, 250 ℃ 9 temperature, the conversion ratio of catalytic reduction of NOx sees attached list one.
A kind of molecular screen base low-temperature denitration catalyst preparation method is as follows:
1) preparation of carrier
The 4g Cu-SSZ-13 molecular sieve carrier (referring to embodiment 5-7) that the copper content that adopts A method to prepare is about to 10wt.% and 1M ammonium nitrate solution 400ml were 80 ℃ of stirred in water bath 12 hours, exchange twice, products therefrom suction filtration, washing, in 100 ℃ of baking ovens, be dried 12 hours, again product is put into 550 ℃ of Muffle furnace roastings 8 hours, obtained the Cu-SSZ-13 carrier that required copper content is about 5wt%.
2) load of catalyst
Step 1: get the 1.2g molecular sieve carrier and the 1.809g cerous nitrate that prepare, 1.190g50wt% manganese nitrate solution, 0.198g zirconium chloride is at room temperature fully uniformly mixed formation turbid solution with the deionized water of 80 times of moles.
Step 2: 1.70g ammonium carbonate is dissolved in to deionized water, is made into the sal volatile of 0.5M, be then added drop-wise in the turbid solution that step 1 configured with the speed of 2ml/min, form precipitation, at room temperature continue to stir 2 hours.
Step 3: gained slurries in step 2 are put into supersonic wave cleaning machine ultrasonic immersing 1 hour, then filtering and washing.
Step 4: by the filter cake obtaining in step 3 in the baking oven of 80 ℃ dry 10 hours, then put into Muffle furnace roasting 8 hours at 500 ℃, obtain MOx-Cu/SSZ-13 catalyst.
The active testing condition of this catalyst is: the NO of 1000ppm, the NH3 of 1000ppm, 6% O
2mix, using helium He as carrier gas, the 40-60 order particle that loaded catalyst is 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is～50000-1.At 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 200 ℃, 250 ℃ nine temperature, the conversion ratio of catalytic reduction of NOx sees attached list one.
This catalyst is carried out to the experiment of SO2 resistance, test condition is: the NO of 1000ppm, and the NH3 of 1000ppm, 6% O2 mixes, and usings helium He as carrier gas, in addition, is mixing the SO2 that wherein adds 100ppm.Loaded catalyst is the 40-60 order particle of 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is about 50000/h.。40 ℃～250 ℃ its activity of temperature range build-in test.Its activity the results are shown in accompanying drawing 5.
As can be seen from Figure 5, SO
2add for 100 ℃ of following NOx conversion ratios and have certain influence, than there is no SO
2situation slightly reduce, and when temperature is during higher than 100 ℃, SO
2on the almost not impact of NOx conversion ratio, when more than 160 ℃, there is on the contrary certain facilitation.
At 140 ℃, this catalyst is carried out to long period stability test, test condition is: the NO of 1000ppm, the NH of 1000ppm
3, 6% O
2mix, using helium He as carrier gas, the 40-60 order particle that loaded catalyst is 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is～50000
-1.Under fixing probe temperature, successively pass into and remove the SO of 100ppm
2.Its activity change the results are shown in accompanying drawing 6.
In Fig. 6, can find out, reducing has slowly appearred in the activity that passes into SO2 rear catalyst, within the testing time conversion ratio of NOx only reduced～2%, and after removal SO2, activity is gone up to some extent, illustrates that this catalyst has stronger anti-SO
2ability.
A kind of molecular screen base low-temperature denitration catalyst preparation method is as follows:
1) preparation of carrier
To adopt B method to prepare 1.9g SSZ-13 molecular sieve (referring to embodiment 1-4) mixes with 0.678g copper nitrate, add 50ml deionized water, at 80 ℃, stir 12 hours, gained slurries vacuum rotary steam is gone out after moisture and obtained product, dry after 12 hours in 100 ℃ of baking ovens, in the Muffle furnace of 550 ℃, roasting is 6 hours, obtains required carrier.
2) load of catalyst
Step 1: get the 1.2g molecular sieve carrier and the 1.809g cerous nitrate that prepare, 1.190g50Wt% manganese nitrate solution, 0.198g zirconium chloride is at room temperature fully uniformly mixed formation turbid solution with the deionized water of 120 times of moles.
Step 2: 1.70g ammonium carbonate is dissolved in to deionized water, is made into the sal volatile of 1.2M, be then added drop-wise in the turbid solution that step 1 configured with the speed of 1.5ml/min, form precipitation, at room temperature continue to stir 3 hours.
Step 3: gained slurries in step 2 are put into supersonic wave cleaning machine ultrasonic immersing 3 hours, then filtering and washing.
Step 4: by the filter cake obtaining in step 3 in the baking oven of 120 ℃ dry 10 hours, then put into Muffle furnace roasting 4 hours at 600 ℃, obtain MOx-Cu/SSZ-13 catalyst.
The active testing condition of this catalyst is: the NO of 1000ppm, the NH of 1000ppm
3, 6% O
2mix, using argon Ar as carrier gas, the 40-60 order particle that loaded catalyst is 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is about 50000/h.At 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 200 ℃, 250 ℃ nine temperature, the conversion ratio of catalytic reduction of NOx sees attached list one.
Embodiment 11
A kind of molecular screen base low-temperature denitration catalyst preparation method is as follows:
1) preparation of carrier
To adopt B method to prepare 1.9g SSZ-13 molecular sieve (referring to embodiment 1-4) mixes with 0.678g copper nitrate, add 50ml deionized water, at 80 ℃, stir 12 hours, gained slurries vacuum rotary steam is gone out after moisture and obtained product, dry after 12 hours in 100 ℃ of baking ovens, in the Muffle furnace of 550 ℃, roasting is 6 hours, obtains required carrier.
2) load of catalyst
Step 1: get the 0.6g molecular sieve carrier and the 1.809g cerous nitrate that prepare, 1.190g50wt% manganese nitrate solution, 0.198g zirconium chloride is at room temperature fully uniformly mixed formation turbid solution with the deionized water of 100 times of moles.
Step 2: 1.70g ammonium carbonate is dissolved in to deionized water, is made into the sal volatile of 1M, be then added drop-wise in the turbid solution that step 1 configured with the speed of 1ml/min, form precipitation, at room temperature continue to stir 2 hours.
Step 3: gained slurries in step 2 are put into supersonic wave cleaning machine ultrasonic immersing 2 hours, then filtering and washing.
Step 4: by the filter cake obtaining in step 3 in the baking oven of 100 ℃ dry 12 hours, then put into Muffle furnace roasting 6 hours at 550 ℃, obtain MOx-Cu/SSZ-13 catalyst.
The active testing condition of this catalyst is: the NO of 1000ppm, the NH of 1000ppm
3, 6% O
2mix, using helium He as carrier gas, the 40-60 order particle that loaded catalyst is 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is about 50000/h.At 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 200 ℃, 250 ℃ nine temperature, the conversion ratio of catalytic reduction of NOx sees attached list one.
Control group
Comparative example 1
The copper content that adopts A method to prepare is about to the 4g Cu-SSZ-13 molecular sieve of 10Wt.% and 1M ammonium nitrate solution 400ml 80 ℃ of stirred in water bath 12 hours, products therefrom suction filtration, washing, in 100 ℃ of baking ovens, be dried 12 hours, again product is put into 550 ℃ of Muffle furnace roastings 8 hours, obtained the Cu-SSZ-13 that required copper content is about 6.5Wt%.This sample is carried out to catalytic activity test.
The active testing condition of this catalyst is: the NO of 1000ppm, the NH of 1000ppm
3, 6% O
2mix, using helium He as carrier gas, the 40-60 order particle that loaded catalyst is 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is about 50000/h.At 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 200 ℃, 250 ℃ nine temperature, the conversion ratio of catalytic reduction of NOx sees attached list one.
Comparative example 2
To adopt B method to prepare 1.9g SSZ-13 molecular sieve mixes with 0.678g copper nitrate, add 50ml deionized water, at 80 ℃, stir 12 hours, gained slurries vacuum rotary steam is gone out after moisture and obtained product, dry after 12 hours in 100 ℃ of baking ovens, in the Muffle furnace of 550 ℃, roasting is 6 hours, obtains the Cu-SSZ-13 that required copper content is 5Wt%.This sample is carried out to catalytic activity test.
The active testing condition of this catalyst is: the NO of 1000ppm, the NH of 1000ppm
3, 6% O
2mix, using argon Ar as carrier gas, the 40-60 order particle that loaded catalyst is 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is about 50000/h.At 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 200 ℃, 250 ℃ nine temperature, the conversion ratio of catalytic reduction of NOx sees attached list one.
Comparative example 3
Step 1: get 5.427g cerous nitrate, 3.580g50wt% manganese nitrate solution, 0.583g zirconium chloride is at room temperature fully uniformly mixed formation turbid solution with the deionized water of 100 times of moles.
Step 2: 5.00g ammonium carbonate is dissolved in to deionized water, is made into the sal volatile of 1M, be then added drop-wise in the turbid solution that step 1 configured with the speed of 1ml/min, form precipitation, at room temperature continue to stir 3 hours.
Step 3: gained slurries in step 2 are put into supersonic wave cleaning machine ultrasonic immersing 3 hours, then filtering and washing.
Step 4: by the filter cake obtaining in step 3 in the baking oven of 100 ℃ dry 12 hours, then put into Muffle furnace roasting 6 hours at 550 ℃, obtain MnZrCeOx catalyst.This sample is carried out to catalytic activity test.
The active testing condition of this catalyst is: the NO of 1000ppm, the NH of 1000ppm
3, 6% O
2mix, using argon Ar as carrier gas, the 40-60 order particle that loaded catalyst is 200mg, adopts fixed bed quartz tube reactor, and gas space velocity GHSV hourly is about 50000/h.At 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 200 ℃, 250 ℃ nine temperature, the conversion ratio of catalytic reduction of NOx sees attached list one.
Subordinate list one
The result of the test of recording in above table shows, the low-temperature space of catalyst of the present invention and middle warm area have greater catalytic performance simultaneously.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. for a molecular sieve based catalyst for low temperature SCR denitration, it is characterized in that: comprise the molecular sieve carrier of Cu modification and be selected from one or more oxides in Ce, Zr, tri-kinds of elements of Mn.
2. catalyst according to claim 1, is characterized in that: described one or more oxides that are selected from Ce, Zr, tri-kinds of elements of Mn are CeO
2, ZrO
2and MnO
2in one or more, preferred CeO
2-ZrO
2-MnO
2composite oxides.
3. catalyst according to claim 1, is characterized in that: the molecular sieve carrier of described Cu modification is prepared by following methods:
Take cupric ammine complex as structure directing agent and Tong Yuan, add ,Lv source, silicon source and aqueous slkali to form presoma, the presoma stirring is put into hydrothermal reaction kettle crystallization at 120-150 ℃, product is filtered, cleans, obtains after dry, roasting to the molecular sieve carrier Cu-SSZ-13 of Cu modification.
4. catalyst according to claim 3, is characterized in that: described cupric ammine complex is copper-TEPA.
5. catalyst according to claim 1, is characterized in that: the molecular sieve carrier of described Cu modification is prepared by following methods:
Described method is included under crystallization condition following raw materials according material is contacted in water, obtains molecular sieve crystal:
(1) at least one silicon source;
(2) at least one aluminium source;
(3) at least one alkali metal compound;
(4) as the choline cation of structure directing agent;
(5) hydroxide ion;
By prepared molecular sieve crystal and copper nitrate, copper sulphate or copper acetate solution ion-exchange 4-8h at 40-80 ℃, then carry out vacuum rotary steam, at 80-120 ℃, be dried afterwards 8-12h, 500-600 ℃ of roasting 4-8h in Muffle furnace, obtains the molecular sieve carrier Cu-SSZ-13 of Cu modification.
6. according to the catalyst described in claim 3 or 5, it is characterized in that: described silicon source is oxide containing silicon and silicate, is preferably silicate, Ludox, ethyl orthosilicate, deposition of silica and clay, more preferably Ludox; Described aluminium source is trivalent aluminium oxide or aluminate, is preferably sodium metaaluminate, aluminium oxide or aluminium hydroxide; Aqueous slkali is NaOH.
7. catalyst according to claim 1, is characterized in that: described CeO
2-ZrO
2-MnO
2composite oxides in, the mol ratio of Mn, Zr, Ce and Cu is followed successively by (30-55): (10-15), (5-10): (10-15), (25-50): (10-15).
8. catalyst according to claim 1, is characterized in that: in described catalyst, the mass ratio of molecular sieve carrier and oxide is 0.3-12:1, and Cu accounts for the 5-10wt% of molecular sieve supported weight, preferably 4-7wt%, more preferably 6.5wt%.
9. the preparation method of catalyst described in claim 1-8 any one, comprising:
Step (1): the molecular sieve carrier of preparation Cu modification;
Step (2): one or more oxides in the molecular sieve carrier of Cu modification and Ce, Zr, tri-kinds of elements of Mn are at room temperature fully uniformly mixed to formation turbid solution with deionized water, the mole dosage of water be total amount of metal mole 80-120 doubly;
Step (3): ammonium carbonate is dissolved in to deionized water, be made into the sal volatile of 0.5-1.2M, then with the speed of 1-2ml/min, be added drop-wise in the turbid solution that step (2) configured, form precipitation, at room temperature continue to stir 1-3 hour, the consumption of added ammonium carbonate is 1.5-2.5 times of slaine mole;
Step (4): the solution system that step (3) is obtained is put into supersonic wave cleaning machine ultrasonic immersing 1～3 hour, filtering and washing;
Step (5): by the filter cake obtaining in step (4) dry 10-24 hour in the baking oven of 80-120 ℃, then at 500-600 ℃ roasting 4-8 hour, obtain MOx-Cu/SSZ-13 catalyst, M is one or more in Ce, Zr, tri-kinds of elements of Mn.
10. preparation method according to claim 9, is characterized in that: in described step (3), mixing speed is 200-300r/min.
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