CN106622356B - A kind of copper modified molecular screen selective reduction catalyst and its preparation method and application - Google Patents
A kind of copper modified molecular screen selective reduction catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of copper modified molecular screen selective reduction catalysts and its preparation method and application, using the eutectic molecular sieve of SSZ-13 molecular sieve and Analcime molecular sieve as catalyst substrates component, copper ion is as active component, copper ion mole is 2.0~5.0 times of eutectic molecular sieve saturation exchange capacity, and copper ion weight accounts for the 0.03~20% of the modified eutectic molecular sieve total weight of copper；It is coated on porous regular material after the modified eutectic molecular sieve of copper and binder formation slurries using infusion process and catalyst is made；Eutectic molecular sieve is by silicon source, silicon source, sodium source, H2O, SSZ-13 molecular sieve seed, template R are raw material, are prepared after crystallization, filtering, drying, roasting；Silicon source, silicon source, sodium source, H2O, the molar ratio of R is 20~250:1:5~70:100~10000:3~150, SSZ-13 molecular sieve seed and SiO2Weight ratio is 0.02~0.2:1.Copper modified molecular screen selective reduction catalyst of the invention has excellent selective reduction ability, and have good hydrothermal stability mainly for the treatment of in the exhaust treatment system containing NOx air-flow in low temperature range.
Description
Technical field
The present invention relates to a kind of selective catalytic reduction catalysts (SCR) and preparation method thereof, which is used for tail gas
In processing system；More particularly to a kind of copper modified molecular screen selective reduction catalyst, the catalyst is for containing nitrogen oxides
(NOx) it in the exhaust treatment system of air-flow, is specifically for use in and contains nitrogen oxides (NOx) air-flow in the presence of oxygen
In exhaust treatment system.
Background technique
Lean-combustion engine (such as diesel engine and gasoline engine) can provide good fuel economy for user,
And operation is realized by controlling the ratio of high air/fuel under the conditions of fuel rare (lean-burn), can discharge the gas of low amounts
Body hydrocarbon (HC) and carbon monoxide (CO).However, lean-combustion engine is easy to produce more rows for containing nitrogen oxides (NOx) tail gas
It puts, and also comprising the up to oxygen (O2) of 15 volume % in tail gas；Since the high NOx conversion of content is usually required rich in also
It can just be carried out under conditions of former agent, it is difficult to effectively reduce the discharge of its from this kind of motor exhaust.Usually in lean-burn (lean
Burning it under the conditions of), needs the NOx conversion in exhaust stream using the special operation measure for reducing NOx into harmless components.
Therefore, a kind of higher selective reduction of activity (SCR) catalyst is handled when exhaust gas discharges very in SCR method
It is important.Currently, usually SCR catalyst is usually to have crystal knot using zeolite as what carrier, load SCR activity component were prepared
The molecular sieve of structure；Zeolite is the silicon aluminate crystal material with quite regular pore size, such as β zeolite, Y zeolite, X boiling
Stone, faujasite, modenite, erionite, ZSM-5, ZSM-8, ZSM-11, ZSM-12 zeolite etc., these zeolites can with Cu,
The metal exchanges or zeolite itself such as Fe, Mn, Ag, V, Ti, Co contain the metals such as some Cu, Fe.But it is above-mentioned known
Metal-modified zeolite catalyst can only be in relatively narrow temperature region model during ammine selectivity catalytic reduction nitrous oxides
The interior purification for carrying out nitrogen oxides is enclosed, does not all have the NOx purifying property of high activity at 300 DEG C or less, hydrothermal stability is poor, low
Activity is lower under the conditions of temperature.
These low activity of molecular sieve catalysts are to convert condition in dramatic temperature since framework of molecular sieve structural stability is poor
Under cause structure to destroy, metal active constituent be easy aggregation, reduce the dispersion degree at metal ion activity center.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the deficiencies in the prior art, and provide a kind of modified point of copper
Son sieve selective reduction catalyst, the catalyst have excellent selective reduction in low temperature to the wider temperature range of high temperature
Ability, under cryogenic catalytic activity still with higher, and the catalyst have good hydrothermal stability.
The second object of the present invention is to provide a kind of preparation method of above-mentioned catalyst, prepare with SSZ-13 type molecule
After the eutectic molecular sieve of sieve and Analcime type molecular sieve structure, by introducing Cu in ion exchange normal direction eutectic molecular sieve, use
Cu is modified eutectic molecular sieve, and modified catalyst has good hydrothermal stability, and more appropriate cellular structure is conducive to
The diffusion of NOx molecule enhances the attachment of metal copper ion, reduces it by hydrothermal and generates a possibility that assembling.
The third object of the present invention is to provide a kind of application of above-mentioned catalyst.
To achieve the goals above, the present invention adopts the following technical scheme: a kind of copper modified molecular screen selective reduction is urged
Agent, using the eutectic molecular sieve with SSZ-13 type molecular sieve and Analcime type molecular sieve structure as the matrix group of catalyst
Point, the modified eutectic molecular sieve of copper is obtained after introducing active component copper ion, is carried on porous regular material to form catalysis
Agent, the load capacity of the porous regular material are 180~260g/L；The mole of the copper ion is that eutectic molecular sieve is full
With 2.0~5.0 times of exchange capacity；The SSZ-13/Analcime eutectic molecular sieve is by silicon source, silicon source, sodium source, deionized water
(H2O), SSZ-13 molecular sieve seed, template R are raw material, are prepared after crystallization, filtering, drying and roasting；It is described
Silicon source, silicon source, sodium source, H2O, the molar ratio of template R is 20~250:1:5~70:100~10000:3~150, wherein
Silicon source: silicon source: the molar ratio of sodium source refers to respective oxide S iO2:Al2O3:Na2The molar ratio of O；The SSZ-13 points
Son sieve crystal seed and SiO2Weight ratio be 0.02~0.2:1.
In above-mentioned technical proposal, the mole of the copper ion be preferably eutectic molecular sieve saturation exchange capacity 2.0~
4.0 again.
In above-mentioned technical proposal, the weight of the copper ion account for the modified eutectic molecular sieve overall weight of copper 0.03~
20%, preferably 0.2~15%, preferably 0.5~10%, further preferably 1.0-8.0%, further preferably 1.5-
5.0%, further preferably 2.0-4.0%, further preferably 2.5-3.5%, further preferably 2.7-3.3%, into one
Step is preferably 2.9-3.1%.
In above-mentioned technical proposal, the silicon source, silicon source, sodium source, H2O, the molar ratio of template R is preferably 20~150:
1:8~68:130~4500:3~150；The SSZ-13 molecular sieve seed and SiO2Weight ratio be preferably 0.02~0.1:
1。
In above-mentioned technical proposal, the silicon source is sodium metaaluminate, sodium aluminate, SB powder, aluminum sulfate, boehmite, isopropyl
Any one in aluminium alcoholates, preferably sodium metaaluminate, sodium aluminate, SB powder, boehmite, any one in aluminium isopropoxide.
In above-mentioned technical proposal, the silicon source be chromatographic silica gel, silica solution, sodium metasilicate, white carbon black, ethyl orthosilicate,
Any one in silicic acid, preferably chromatographic silica gel, white carbon black, ethyl orthosilicate, any one in sodium metasilicate.
In above-mentioned technical proposal, the R is organic amine template, including two class organic amine template of R1 and R2；It is described
Organic amine template be by R1 and two class organic amine template of R2 according to R1:R2=4~10:1 molar ratio at it is mixed
Shuttering agent；The R1 class organic amine template is N, N, N- trimethyl -1- adamantane ammonium hydroxide, benzyl trimethyl hydrogen-oxygen
Change any one in ammonium；The R2 class organic amine template is to replace alkyl phosphonium hydroxide piperidines；The substitution alkylaryl hydroxide
Change piperidine template agent is N, N- dimethyl -3,5- dimethyl hydrogen oxyl, the oxidation of N- ethyl-N-methyl -2,6- dimethyl hydrogen
Piperidines, N, N- dimethyl -2- (2- ethoxy)-dimethyl hydrogen oxyl, N, N- dimethyl -2- ethyl-dimethyl hydroxide
Piperidines, N, N- diethyl -2,6- dimethyl hydrogen oxyl, N, N- dimethyl -2,6- dimethyl hydrogen oxyl, N- ethyl -
Any one in N- propyl -2,6- dimethyl hydrogen oxyl or two kinds or more the mixing being mixed in any proportion
Object.
In above-mentioned technical proposal, the porous regular material is that porous honeycomb flows through the regular material of type, is selected from violet
Green stone, alph-alumine, silicon carbide, aluminium titanates, silicon nitride, zirconium oxide, mullite, spodumene, alumina-silica magnesia
Or any one in zirconium silicate；Preferably cordierite.
The present invention also provides a kind of preparation methods of above-mentioned copper modified molecular screen selective reduction catalyst, including following step
It is rapid:
(1) prepare eutectic molecular sieve: silicon source, silicon source, sodium source, deionized water, SSZ-13 molecular sieve seed, template R are pressed
After the ratio mixing, 20~144h of crystallization under conditions of self-generated pressure and crystallization temperature are 100~200 DEG C, then
SSZ-13/Analcime eutectic molecular sieve is obtained after filtering, drying and roasting；The temperature of the drying is 100~150
DEG C, drying time is 12~48h, and the maturing temperature is 450~650 DEG C, and calcining time is 3~20h；
(2) it prepares hydrogen type molecular sieve: the SSZ-13/Analcime eutectic molecular sieve that step (1) obtains is put into ammonium salt water
After ammonium ion exchange 1~3 time is carried out in solution under the conditions of 70~100 DEG C, dry 12~48h under the conditions of 105~120 DEG C,
Then hydrogen type molecular sieve is obtained after roasting 2~10h under the conditions of 450~650 DEG C；
(3) copper modified hydrogen molecular sieve: the hydrogen type molecular sieve that step (2) obtains is added in copper salt solution, in room
It is modified to carry out copper by 24~72h of stirring under the conditions of temperature~100 DEG C, is dried in vacuo 12~48h after filtering under the conditions of 50~100 DEG C,
Repeat above-mentioned modification, filtering, after process of vacuum drying 0~3 time, by the sample after drying under the conditions of normal atmosphere pressure in
After roasting 3~5h at 450~600 DEG C, the modified eutectic molecular sieve of the copper is obtained；
(4) copper for obtaining step (3) is modified eutectic molecular sieve and colloidal silicon dioxide according to the weight of 2.0~5.0:1
After mixing, deionized water is added and is prepared into catalyst slurry, copper modified molecular screen and colloidal silicon dioxide in catalyst slurry
Total solid content be 35.0~55.0wt%；By infusion process, the catalyst slurry is coated according to the load capacity
In on the porous regular material, blowing extra slurry droplet off with compressed air, dry 12 under the conditions of 105~120 DEG C~
Then 48h roasts 2~10h under the conditions of 450~650 DEG C, is prepared into copper modified molecular screen SCR catalyst.
In above-mentioned technical proposal, crystallization temperature described in step (1) is preferably 150~200 DEG C；The crystallization time
Preferably 24~100h, further preferably 48~100h；The temperature of the drying is preferably 105~120 DEG C.
In above-mentioned technical proposal, in step (2), the ammonium salt aqueous solution is ammonium nitrate, ammonium sulfate, ammonium chloride or carbonic acid
The aqueous solution of hydrogen ammonium, the concentration of ammonium ion are 1.0mol/L；Ammonium salt aqueous solution is more preferably the water of ammonium nitrate or ammonium chloride
Solution；Preferably 80~100 DEG C of the ammonium ion exchange.
In above-mentioned technical proposal, in step (3), the copper salt solution is copper nitrate, copper chloride, copper acetate or sulfuric acid
The aqueous solution of copper, the concentration of copper ion is 0.1~1.5mol/L in copper salt solution；The copper salt solution is further preferred
For the aqueous solution of copper nitrate, copper chloride or copper sulphate.
The present invention also provides a kind of application of above-mentioned copper modified molecular screen selective reduction catalyst, which is mainly used
Contain nitrogen oxides (NO in processingx) air-flow exhaust treatment system in；The tail gas stream is gone back other than containing nitrogen oxides
It include oxygen, ammonia and/urea.
Usually using in selective exposure reduction (SCR) system of reducing agent (urea or NH3 etc.), it is anti-that several chemistry occur
It answers:
NO and NH3 are reacted with oxygen, and NO is reduced to nitrogen, as shown in Equation 1:
4NO+4NH3+O2→4N 2+6H2O (1)；
In addition, the non-selective reaction of oxygen can also occur for NO and NH3, further consumes NH3 or generates secondary product,
It is as shown in Equation 2:
4NH3+5NO2→4NO+6H2O (2)；
NO2 and NH3 present in nitrogen oxides (NOx) air-flow, then carried out by formula 3:
3NO2+4NH3→(7/2)N2+6H2O (3)；
And reacting between NH3 and NO and NO 2 then carries out according to formula 4:
NO+NO2+2NH3→2N 2+3H2O (4)。
React the reaction speed of (1), (3) and (4) due to reaction temperature and the type of catalyst used are different greatly not
Together, the speed of reaction (4) usually reacts 2~10 times of the speed of (1), (3).
In SCR selective reduction system, in order to improve the NOx detergent power under low temperature, it is necessary to so that formula (4) is anti-
It should go on smoothly, rather than the reaction of formula (1) is occupied an leading position.By improving the plot ratio of NO2 in gas, can make under low temperature
So that the reaction of formula (4) is occupied an leading position.
And under 150~300 DEG C of cryogenic conditions, copper has excellent adsorption capacity to NO, and makes the oxidability of NO
Stronger, the oxidation reaction of NO is indicated by formula 5:
NO+1/2O2→NO2 (5)。
In above-mentioned technical proposal, contain NO using catalyst treatment of the inventionxAir-flow when, NO2Content be at most
NOx80%, NO of weight2Content be preferably NOxThe 0.01~70% of weight, further preferably NOxThe 0.01 of weight~
60%, further preferably NOxThe 0.015~55% of weight, further preferably NOxThe 0.02~50% of weight.
Copper modified molecular screen selective reduction catalyst of the present invention, in low temperature to the wider temperature range of high temperature
With excellent selective reduction ability, can realize to NO in the rangexPurification；And the catalyst has good
Hydrothermal stability, after being subjected to hydro-thermal endurance test, purify NO under catalyst low temperature of the present inventionxPerformance than copper be supported on β and
SCR catalyst performance after the hydrothermal aging formed on ZSM-5 molecular sieve is more excellent.
Detailed description of the invention
Fig. 1: the XRD diagram of the modified eutectic molecular sieve of copper prepared by the embodiment of the present invention 1；
Fig. 2: the XRD diagram of the modified SSZ-13 molecular sieve of copper prepared by comparative example 1 of the present invention；
Fig. 3: the XRD diagram of copper modified beta molecular sieve prepared by comparative example 2 of the present invention；
Fig. 4: the XRD diagram of ZSM-5 molecular sieve prepared by comparative example 3 of the present invention；
Fig. 5: scanning electron microscope (SEM) figure of the modified eutectic molecular sieve of copper prepared by the embodiment of the present invention 2；
Specific embodiment
The specific embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold:
Embodiment 1:
A kind of copper modified molecular screen selective reduction catalyst, is prepared by following methods:
(1) eutectic molecular sieve is prepared: by 1.673g NaAlO2(fine chemistry industry research institute is recovered in purity 99%, Tianjin)
It is added in 120.06g deionized water, after stirring 0.5h, the N that the mass fraction of 30.00g is 25%, N, N- front three fund is added dropwise
Rigid alkane aqueous ammonium (R1) and 1.05g N, N- dimethyl -3,5- dimethyl hydrogen oxyl (R2), add again after being sufficiently stirred
Enter 3.690g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.), stirs 0.5h, add 69.761g silicon
Acid sodium aqueous solution (modulus nSiO2/nNa2O is 3.35, concentration 249.6g/L, specific gravity 1.26g/ml), 2~3h is stirred, sufficiently
0.691g SSZ-13 crystal seed is added after being stirred, is fitted into the steel bomb of polytetrafluoroethyllining lining, it is brilliant at 170 DEG C
Change 72h；After the reaction was completed, product is washed with deionized, roasts 12h at 580 DEG C after dry 12h at 120 DEG C and is divided
Son sieve solid powder；
The molar ratio of raw material are as follows: Na2O:Al2O3: SiO2: H2O:R1:R2 is 8.0:1.0:23.0:667.0:3.549:
0.591；
(2) prepare hydrogen type molecular sieve: it is molten that the molecular sieve solid powder 10g for taking step (1) to obtain is added to 1000mL ammonium nitrate
In liquid (1.0mol/L), 12h is exchanged under 80 DEG C of water bath conditions, sufficiently washs and filters；Then above-mentioned ammonium ion is repeated to exchange 3 times
Afterwards, 48h is dried at 105 DEG C obtain Hydrogen SSZ-13/ANA eutectic molecular sieve in 500 DEG C of roasting 8h；
(3) copper modified hydrogen molecular sieve: the molecular sieve 10g for taking step (2) to synthesize is added to 78.68ml concentration and is
Cu (the NO of 0.2mol/L3)2In 3H2O aqueous solution；Dust technology is added dropwise into above-mentioned solution and adjusts its pH to 2.8, stirs evenly
It is placed in heatproof container, and is put into togerther in the drier with pressure reducing valve afterwards；The pressure in drier is extracted into vacuum pump
After 10Torr or less, room temperature carries out 1 hour degassing process, then after 90 DEG C of Conditions Temperatures are 12 hours dry, after drying
Sample under the conditions of normal atmosphere pressure in 500 DEG C roasting temperature 4 hours；Then it is classified, is obtained with the sieve of 40 mesh
To the modified eutectic molecular sieve of the copper, the modified eutectic molecular sieve of the copper of icp analysis preparation, copper (II) ion accounts for the modified eutectic of copper
The 2.5% of molecular sieve total weight, i.e. copper load capacity are 2.5wt%, and the XRD diagram of the molecular sieve is as shown in Figure 1；
(4) the copper modified molecular screen for taking 15g step (3) to obtain, (silica contains with the commercially available colloidal silicon dioxide of 6.71g
Amount be 20%wt) and 16.90g deionized water be uniformly mixed and be fabricated to the catalyst slurry that solid content is 42wt%, and will be catalyzed
Agent slurries are coated on the regular material of cordierite honeycomb (#300cpsi, diameter 21mm, length 20mm) by infusion process, are used
Compressed air blows extra slurry droplet off, and drying 24 hours at 110 DEG C is prepared into copper after roasting 2h under the conditions of 500 DEG C and changes
Property molecular sieve SCR catalyst, the load capacity on regular material is that (quality of regular material weight gain is divided by regular after roasting by 227g/L
Spatial volume occupied by material, the calculation method of other embodiments is with embodiment 1)；The catalyst is labeled as CCG-SCR-
1。
Embodiment 2:
A kind of copper modified molecular screen selective reduction catalyst, is prepared by following methods:
(1) eutectic molecular sieve is prepared: by 1.457g SB powder (German Sasol company, Al2O3% >=70%) it is added to
In 1008.00g deionized water, after stirring 0.5h, the benzyltrimethylammonium hydroxide that the mass fraction of 395.13g is 40% is added dropwise
Methanol solution (R1) and 25.89g N- ethyl-N-methyl -2,6- dimethyl hydrogen oxyl (R2), after being sufficiently stirred again
It is added 30.82g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.), stirs 0.5h, add 122.62g
White carbon black (SiO2% >=70%), 2~3h is stirred, the SSZ-13 molecular sieve seed of 7.21g is added after being thoroughly mixed, is packed into
In the steel bomb of polytetrafluoroethyllining lining, the crystallization 144h at 155 DEG C；After the reaction was completed, product is washed with deionized water
It washs sufficiently, roasts 12h at 580 DEG C after drying for 24 hours at 105 DEG C and obtain molecular sieve solid powder；
The molar ratio of raw material are as follows: Na2O:Al2O3: SiO2: H2O:R1:R2 is 68.0:1.0:200.0:5600.0:94.5:
13.5；
(2) prepare hydrogen type molecular sieve: it is molten that the molecular sieve solid powder 15g for taking step (1) to obtain is added to 1500mL ammonium nitrate
It in liquid (1.0mol/L), is exchanged for 24 hours under 85 DEG C of water bath conditions, sufficiently washs and filter, then repeat above-mentioned ammonium ion exchange 3
Secondary, dry 36h obtains Hydrogen SSZ-13/Analcime eutectic molecular sieve in 550 DEG C of roasting 4h at 110 DEG C；
(3) copper modified hydrogen molecular sieve: the molecular sieve 15g for taking step (2) to synthesize is added to 51.22ml concentration and is
The CuCl of 0.5mol/L2·2H2In O aqueous solution；Dust technology is added dropwise into above-mentioned solution and adjusts its pH to 2.9, stirs evenly postposition
Enter in heatproof container, and is put into togerther in the drier with pressure reducing valve；The pressure in drier is extracted into vacuum pump
After 10Torr or less, room temperature carries out 1 hour degassing process, and then after 80 DEG C 20 hours dry, the sample after drying is existed
Under the conditions of normal atmosphere pressure in 550 DEG C roasting temperature 3 hours；Then it is classified, is obtained described with the sieve of 40 mesh
Copper modified molecular screen, the modified eutectic molecular sieve of the copper of icp analysis preparation, copper (II) ion account for the modified eutectic molecular sieve total weight of copper
3.1%, i.e. copper load capacity is 3.1wt%, and the SEM figure of the copper modified molecular screen is as shown in Figure 5；
(4) the copper modified molecular screen for taking 15g step (3) to obtain, with the commercially available silica solution of 4.72g (silica quality content
It is uniformly mixed for 20wt%) and 10.67g deionized water and is fabricated to solid content and is the catalyst slurry of 52.0wt%, and led to
It crosses infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with compression
Air blows extra slurry droplet off, drying 20 hours at 120 DEG C, is prepared into modified point of copper after 3h is roasted under the conditions of 500 DEG C
Son sieves SCR catalyst, and the load capacity on regular material is 219g/L, is denoted as CCG-SCR-2.
Embodiment 3:
A kind of copper modified molecular screen selective reduction catalyst, is prepared by following methods:
(1) eutectic molecular sieve is prepared: by 6.732g Al2(SO4)318H2O (Sinopharm Chemical Reagent Co., Ltd.,
Purity >=99%) it is added in 180.00g deionized water, after stirring 0.5h, the mass fraction that 1118.28g is added dropwise is 25%
N, N, N- trimethyl adamantane aqueous ammonium (R1) and 5.39g N, N- dimethyl -2- (2- ethoxy)-dimethyl hydrogen aoxidize piperazine
Pyridine (R2) adds 8.51g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.) after being sufficiently stirred, stirs
0.5h is mixed, 30.65g chromatographic silica gel (Qingdao Marine Chemical Co., Ltd., SiO are added2% >=98%), 2~3h is stirred, sufficiently
2.40g SSZ-13 crystal seed is added after being stirred, is fitted into the steel bomb of polytetrafluoroethyllining lining, the crystallization at 165 DEG C
120h；After the reaction was completed, product is washed with deionized, roasts 12h at 580 DEG C after dry 36h at 110 DEG C and obtains molecule
Sieve solid powder；
The molar ratio of raw material are as follows: Na2O:Al2O3: SiO2: H2O:R1:R2 is 18.0:1.0:50.0:1000.0:13.991:
2.798；
(2) prepare hydrogen type molecular sieve: it is molten that the molecular sieve solid powder 30g for taking step (1) to obtain is added to 3000mL ammonium nitrate
In liquid (1.0mol/L), 20h is exchanged under 90 DEG C of water bath conditions, sufficiently washs and filters, then repeats above-mentioned ammonium ion exchange 2
Secondary, drying for 24 hours, in 550 DEG C of roasting 3h, obtains Hydrogen SSZ-13/Analcime eutectic molecular sieve at 115 DEG C；
(3) copper modified hydrogen molecular sieve: the molecular sieve 30g for taking step (2) to synthesize is added to 34.23ml concentration and is
The Cu SO of 0.8mol/L4In aqueous solution；Dust technology is added dropwise into above-mentioned solution and adjusts its pH to 3.0, is placed in after mixing evenly resistance to
In heat container, and it is put into togerther in the drier with pressure reducing valve；With vacuum pump by the pressure in drier be extracted into 10Torr with
After lower, room temperature carries out 1 hour degassing process, then after 70 DEG C 24 hours dry, by the sample after drying in normal atmosphere
Under pressure conditions in 550 DEG C roasting temperature 3 hours；Then it is classified with the sieve of 40 mesh, obtains modified point of the copper
Son sieve, the modified eutectic molecular sieve of the catalyst copper of icp analysis preparation, copper (II) ion account for the modified eutectic molecular sieve total weight of copper
2.9%, i.e. copper load capacity is 2.9wt%；
(4) the copper modified molecular screen for taking 15g step (3) to obtain, with the commercially available silica solution of 6.34g (silica quality content
It is uniformly mixed for 20wt%) and 23.79g deionized water and is fabricated to solid content and is the catalyst slurry of 36.0wt%, and led to
It crosses infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with compression
Air blows extra slurry droplet off, drying 20 hours at 120 DEG C, is prepared into modified point of copper after 3h is roasted under the conditions of 500 DEG C
Son sieves SCR catalyst, and the load capacity on regular material is 234g/L, is denoted as CCG-SCR-3.
Embodiment 4:
A kind of copper modified molecular screen selective reduction catalyst, is prepared by following methods:
(1) it prepares eutectic molecular sieve: 4.168g aluminium isopropoxide (purity >=98%) is added to 126.00g deionized water
In, stir 0.5h after, be added dropwise 148.79g mass fraction be 25% N, N, N- trimethyl adamantane aqueous ammonium (R1) and
7.76g N, N- dimethyl -2- ethyl-dimethyl diisopropylimidazolinium (R2), it is (pure to add 12.98g NaOH after being sufficiently stirred
Degree 96%, Tianjin Kermel Chemical Reagent Co., Ltd.), 0.5h is stirred, 170.07g silester (Chinese medicines group is added
Chemical reagent Co., Ltd, purity >=98%), 2~3h is stirred, 1.92g SSZ-13 crystal seed, dress are added after being thoroughly mixed
Enter in the steel bomb of polytetrafluoroethyllining lining, in 175 DEG C of crystallization 72h；After the reaction was completed, product is washed with deionized water
It washs, roasts 12h at 580 DEG C after dry 40h at 120 DEG C and obtain molecular sieve solid powder；
The molar ratio of raw material are as follows: Na2O:Al2O3: SiO2: H2O:R1:R2 is 28.0:1.0:80.0:700.0:17.6:4.4；
(2) prepare hydrogen type molecular sieve: it is molten that the molecular sieve solid powder 50g for taking step (1) to obtain is added to 5000mL ammonium nitrate
In liquid (1.0mol/L), 12h is exchanged under 95 DEG C of water bath conditions, sufficiently washs and filters, then repeats above-mentioned ammonium ion exchange 2
Secondary, dry 12h obtains Hydrogen SSZ-13/Analcime eutectic molecular sieve in 600 DEG C of roasting 2.5h at 120 DEG C；
(3) copper modified hydrogen molecular sieve: the molecular sieve 50g for taking step (2) to synthesize is added to 57.94ml concentration and is
Cu (the NO of 1.1mol/L3)2·3H2In O aqueous solution；Dust technology is added dropwise into above-mentioned solution and adjusts its pH to 2.8, stirs evenly
It is placed in heatproof container, and is put into togerther in the drier with pressure reducing valve afterwards；The pressure in drier is extracted into vacuum pump
After 10Torr or less, room temperature carries out 1 hour degassing process, and then after 60 DEG C 36 hours dry, the sample after drying is existed
Under the conditions of normal atmosphere pressure in 500 DEG C roasting temperature 5 hours；Then it is classified, is obtained described with the sieve of 40 mesh
The copper of copper modified molecular screen, icp analysis preparation is modified in eutectic molecular sieve, and copper (II) ion accounts for the modified eutectic molecular sieve gross weight of copper
The 2.7% of amount, i.e. copper load capacity are 2.7wt%；
(4) the copper modified molecular screen for taking 15g step (3) to obtain, with the commercially available silica solution of 5.27g (silica quality content
It is uniformly mixed for 20wt%) and 8.96g deionized water and is fabricated to solid content and is the catalyst slurry of 55.0wt%, and passed through
Infusion process is coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, empty with compression
Extra slurry droplet is fallen in air-blowing, and drying 24 hours, is prepared into copper modified molecules after roasting 5h under the conditions of 500 DEG C at 120 DEG C
SCR catalyst is sieved, the load capacity on regular material is 216g/L, is denoted as CCG-SCR-4.
Embodiment 5:
A kind of copper modified molecular screen selective reduction catalyst, is prepared by following methods:
(1) it prepares eutectic molecular sieve: 1.359g boehmite (Shandong Aluminum Plant, purity >=75%) is added to
In 288.00g deionized water, after stirring 0.5h, the N that the mass fraction of 240.47g is 25%, N, N- trimethyl adamantane is added dropwise
Aqueous ammonium (R1) and 7.33g N, N- diethyl -2,6- dimethyl hydrogen oxyl (R2), add after being sufficiently stirred
17.03g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.) stirs 0.5h, adds 303.31g water glass
Glass solution (modulus nSiO2/nNa2O is 3.35, concentration 249.6g/L, specific gravity 1.26g/ml) 2~3h of stirring, it is sufficiently stirred
1.20g SSZ-13 crystal seed is added after mixing, is fitted into the steel bomb of polytetrafluoroethyllining lining, the crystallization 60h at 180 DEG C；
After the reaction was completed, product is washed with deionized, roasting 12h at 115 DEG C after dry 48h at 580 DEG C, to obtain molecular sieve solid
Body powder；
The molar ratio of raw material are as follows: Na2O:Al2O3: SiO2: H2O:R1:R2 is 36.0:1.0:100.0:1600.0:28.444:
3.556；
(2) prepare hydrogen type molecular sieve: it is molten that the molecular sieve solid powder 50g for taking step (1) to obtain is added to 5000mL ammonium nitrate
In liquid (1.0mol/L), 8h is exchanged under 98 DEG C of water bath conditions, sufficiently washs and filters, then repeated above-mentioned ammonium ion and exchange 2 times,
Dry 12h obtains Hydrogen SSZ-13/Analcime eutectic molecular sieve in 650 DEG C of roasting 2h at 120 DEG C；
(3) copper modified hydrogen molecular sieve: the molecular sieve 50g for taking step (2) to synthesize is added to 57.37ml concentration and is
Cu (the NO of 1.2mol/L3)2·3H2In O aqueous solution；Dust technology is added dropwise into above-mentioned solution and adjusts its pH to 2.8, stirs evenly
It is placed in heatproof container, and is put into togerther in the drier with pressure reducing valve afterwards；The pressure in drier is extracted into vacuum pump
After 10Torr or less, room temperature carries out 1 hour degassing process, and then after 55 DEG C 48 hours dry, the sample after drying is existed
Under the conditions of normal atmosphere pressure in 550 DEG C roasting temperature 3 hours；Then it is classified, is obtained described with the sieve of 40 mesh
Copper modified molecular screen, the modified eutectic molecular sieve of the copper of icp analysis preparation, copper (II) ion account for the modified eutectic molecular sieve total weight of copper
3.5%, i.e., copper load capacity be 3.5wt%；
(4) the copper modified molecular screen for taking 15g step (3) to obtain, with the commercially available silica solution of 3.68g (silica quality content
It is uniformly mixed for 20wt%) and 21.67g deionized water and is fabricated to solid content and is the catalyst slurry of 39.0wt%, and led to
It crosses infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with compression
Air blows extra slurry droplet off, drying 24 hours at 120 DEG C, is prepared into modified point of copper after 3h is roasted under the conditions of 550 DEG C
Son sieves SCR catalyst, and the load capacity on regular material is 197g/L, to be denoted as CCG-SCR-5.
Embodiment 6:
A kind of copper modified molecular screen selective reduction catalyst, is prepared by following methods:
(1) eutectic molecular sieve is prepared: by 7.578g Al (NO3)3·9H2O (purity 99%, the close europeanized examination of Tianjin section
Agent Co., Ltd) it is added in 648.00g deionized water, after stirring 0.5h, the N that the mass fraction of 502.17g is 25% is added dropwise,
N, N- trimethyl adamantane aqueous ammonium (R1) and 11.7g N, N- dimethyl -2,6- dimethyl hydrogen oxyl (R2), through filling
It is added 23.12g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.) after dividing stirring, stirs 0.5h, then
91.97g white carbon black (SiO is added2% >=98%), 2~3h is stirred, 8.11g SSZ-13 crystal seed is added after being thoroughly mixed,
It is fitted into the steel bomb of polytetrafluoroethyllining lining, the crystallization 48h at 190 DEG C；After the reaction was completed, by product deionized water
It washs, roasts 12h at 580 DEG C after dry 12h at 120 DEG C and obtain molecular sieve solid powder；
The molar ratio of raw material are as follows: Na2O:Al2O3: SiO2: H2O:R1:R2 is 51.0:1.0:150.0:3600.0:59.4:
6.6；
(2) prepare hydrogen type molecular sieve: the molecular sieve solid powder 100g for taking step (1) to obtain is added to 10L ammonium nitrate solution
In (1.0mol/L), 8h is exchanged under 99 DEG C of water bath conditions, sufficiently washs and filters, then repeated above-mentioned ammonium ion and exchange 2 times, in
Dry 12h obtains Hydrogen SSZ-13/Analcime eutectic molecular sieve in 450 DEG C of roasting 10h at 120 DEG C；
(3) copper modified hydrogen molecular sieve: the molecular sieve 100g for taking step (2) to synthesize is added to 44.06ml concentration and is
The CuCl of 1.5mol/L2In 2H2O aqueous solution；Dust technology is added dropwise into above-mentioned solution and adjusts its pH to 2.9, after mixing evenly
It is placed in heatproof container, and is put into togerther in the drier with pressure reducing valve；The pressure in drier is extracted into vacuum pump
After 10Torr or less, room temperature carries out 1 hour degassing process, and then after 95 DEG C 12 hours dry, the sample after drying is existed
Under the conditions of normal atmosphere pressure in 600 DEG C roasting temperature 3 hours；Then it is classified, is obtained described with the sieve of 40 mesh
Copper modified molecular screen；The modified eutectic molecular sieve of the copper of icp analysis preparation, copper (II) ion account for the modified eutectic molecular sieve total weight of copper
2.1%, i.e., copper load capacity be 2.1wt%
(4) the copper modified molecular screen for taking 15g step (3) to obtain, with the commercially available silica solution of 5.42g (silica quality content
It is uniformly mixed for 20wt%) and 15.32g deionized water and is fabricated to solid content and is the catalyst slurry of 45.0wt%, and led to
It crosses infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with compression
Air blows extra slurry droplet off, drying 24 hours at 120 DEG C, is prepared into modified point of copper after 4h is roasted under the conditions of 500 DEG C
Son sieves SCR catalyst, and the load capacity on regular material is 245g/L, to be denoted as CCG-SCR-6.
Comparative example 1: the modified SSZ-13 molecular sieve selective reduction catalyst of copper
A kind of modified SSZ-13 molecular sieve selective reduction catalyst of copper, is prepared by following methods:
(1) eutectic molecular sieve is prepared: by 1.46g SB powder (German Sasol company, Al2O3% >=70%) it is added to
In 1008.00g deionized water, after stirring 0.5h, the N that the mass fraction of 798.90g is 25%, N, N- trimethyl adamantane is added dropwise
Aqueous ammonium (R1), 30.82g NaOH is added after being sufficiently stirred, and (purity 96%, Tianjin Ke Miou chemical reagent are limited
Company), 0.5h is stirred, 122.62g white carbon black (SiO is added2% >=70%), 2~3h is stirred, is added after being thoroughly mixed
7.21g SSZ-13 crystal seed, is fitted into the steel bomb of polytetrafluoroethyllining lining, the crystallization 72h at 170 DEG C；Reaction is completed
Afterwards, product is washed with deionized, roasts 12h at 580 DEG C after dry 12h at 120 DEG C and obtains molecular sieve solid powder；
The molar ratio of raw material are as follows: Na2O:Al2O3: SiO2: H2O:R1 is 68.0:1.0:200.0:5600.0:108.0；
(2) prepare hydrogen type molecular sieve: it is molten that the molecular sieve solid powder 15g for taking step (1) to obtain is added to 1500mL ammonium nitrate
In liquid (1.0mol/L), 12h is exchanged under 80 DEG C of water bath conditions, sufficiently washs and filters, then repeats above-mentioned ammonium ion exchange 3
Secondary, dry 12h obtains Hydrogen SSZ-13/Analcime eutectic molecular sieve in 550 DEG C of roasting 4h at 120 DEG C；
(3) copper modified hydrogen molecular sieve: the molecular sieve 15g for taking step (2) to synthesize is added to 21.24ml concentration and is
Cu (the NO of 1.0mol/L3)2·3H2In O aqueous solution；Dust technology is added dropwise into above-mentioned solution and adjusts its pH to 2.9, stirs evenly
It is placed in heatproof container, and is put into togerther in the drier with pressure reducing valve afterwards；The pressure in drier is extracted into vacuum pump
After 10Torr or less, room temperature carries out 1 hour degassing process, and then after 90 DEG C 24 hours dry, the sample after drying is existed
Under the conditions of normal atmosphere pressure in 550 DEG C roasting temperature 3 hours；Then it is classified, is obtained described with the sieve of 40 mesh
Copper modified molecular screen, the copper modified molecular screen of icp analysis result preparation, copper (II) ion account for copper modified molecular screen total weight
3.0%, i.e. copper load capacity is 3.0wt%, and the XRD diagram of the molecular sieve is as shown in Figure 2；
(4) the copper modified molecular screen for taking 15g step (3) to obtain, with the commercially available silica solution of 3.25g (silica quality content
It is uniformly mixed for 20wt%) and 19.01g deionized water and is fabricated to solid content and is the catalyst slurry of 42.0wt%, and led to
It crosses infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with compression
Air blows extra slurry droplet off, drying 24 hours at 110 DEG C, is prepared into the modified SCR of copper after 2h is roasted under the conditions of 500 DEG C
Catalyst, the load capacity on regular material are 230g/L, are labeled as CHA-SCR-1.
Comparative example 2: the modified beta-molecular sieve selective reduction catalyst of synthesis copper
A kind of beta-molecular sieve selective reduction catalyst that copper is modified, is prepared by following methods:
(1) NaOH aqueous solution is added in colloidal silicon dioxide (silica quality content is 30wt%), is sufficiently stirred
Al (NO is added afterwards3)3The aqueous solution of 9H2O aqueous solution and TEAOH (TEAOH content 35wt%), the reaction after being sufficiently stirred are mixed
Close object, the molar ratio of raw material are as follows: Na2O:Al2O3: SiO2: H2O:TEAOH is 21.0:1.0:300.0:4000.0:150.0；
(2) above-mentioned reaction mixture is put into polytetrafluoroethylcontainer container, closed self-generated pressure, is heated under the conditions of 155 DEG C
72h；Then it is centrifuged, washs, 120 DEG C of dry 12h, roasting 4 hours and remove at 550 DEG C under normal atmosphere pressure
Template；With SiO in icp analysis product2: A12O3Molar ratio be 29:1, the XRD analysis product is the β point with BEA type structure
Son sieve, as shown in Figure 3；
(3) the beta-molecular sieve powder of 10g is added in 1000mL ammonium nitrate solution (1.0mol/L), under the conditions of 80 DEG C at
24 hours progress ion exchanges are managed, sufficiently washs and filters, above-mentioned ammonium ion is then repeated and exchanges 3 times, it is dry at 120 DEG C
For 24 hours, after zeolite molecular sieve being roasted 4 hours at 550 DEG C under normal atmosphere pressure, hydrogenation synthesis beta-zeolite molecular sieve is obtained；
(4) 35g copper acetate (Cu is dissolved in 3500g deionized water2(CH3COO)4·H2O) 35g, obtaining pH is 2.8
Copper acetate (II) deionized water solution；In above-mentioned copper acetate (II) from aqueous solution, hydrogenation synthesis zeolite molecular sieve 300g is added,
It after being stirred 2 hours at 80 DEG C, is filtered, is separated by solid-liquid separation；Hydrogenation synthesis zeolite molecular sieve after separation of solid and liquid is with 40 DEG C
3500g pure water is cleaned, and filtering and cleaning is repeated, until the pH value of detergent remover is 6~7；Then, it was dried at 120 DEG C
Screening matter 12h is roasted 2 hours at 550 DEG C；After being classified with the mesh screen of 40 mesh, the modified beta-molecular sieve of copper, this point are obtained
The XRD diagram of son sieve is as shown in Figure 3；The modified beta-molecular sieve of the copper of icp analysis preparation, copper (II) ion account for the modified beta-molecular sieve of copper
The 3.0% of total weight, i.e. copper load capacity are 3.0wt%；
(5) the copper modified molecular screen for taking 15g step (4) to obtain, with the commercially available silica solution of 4.32g (silica quality content
It is uniformly mixed for 20wt%) and 15.93g deionized water and is fabricated to solid content and is the catalyst slurry of 45.0wt%, and led to
It crosses infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with compression
Air blows extra slurry droplet off, drying 24 hours at 105 DEG C, is prepared into the modified SCR of copper after 2h is roasted under the conditions of 500 DEG C
Catalyst, the load capacity on regular material is 224g/L, is denoted as BEA-SCR-2.
Comparative example 3: the modified ZSM-5 molecular sieve selective reduction catalyst of synthesis copper
A kind of ZSM-5 molecular sieve selective reduction catalyst that copper is modified, is prepared by following methods:
(1) in 800g sodium silicate aqueous solution (mass fraction: SiO226%, Na2O 7.0%) in addition sodium hydroxide it is water-soluble
Liquid (5g sodium hydroxide, which is dissolved in 400g deionized water, to be prepared) adds ten hexahydrate (Al of 61g aluminum sulfate while stirring2
(SO4)3·16H2O it) is dissolved in the aqueous solution being formulated in 1.5kg deionized water with 1, the 3- dimethyl urea of l0g, is finally added
Adding mass fraction is 5% sulfuric acid 1000g, obtains uniform primary gel；
(2) autoclave that gel described in step 1 is packed into 5L is generated into self-generated pressure, under 200 revs/min of speed stirrings,
160 DEG C crystallization 72 hours, obtain MFI kind crystalline substance zeolite molecular sieve；
(3) in 640g sodium silicate aqueous solution (mass fraction: SiO225%, Na2O 8.0%) in be added 1.75kg deionization
Water, ten hexahydrate (Al of 25g aluminum sulfate2(SO4)3·16H2O) and 35g sulfuric acid (mass fraction 97%), step is continuously added
(2) second level gel is obtained after obtained MFI kind crystalline substance zeolite molecular sieve 1.5kg stirring；Second level gel is put into the autoclave of 5L
Self-generated pressure is generated, in 150 DEG C of stirring crystallization, 110 revs/min of mixing speed, processing time are 45 hours；The slurries that will be obtained
Filtering, washing obtain product after 5 hours dry at a temperature of 120 DEG C；With the icp analysis product, it is known that wherein SiO2: A12O3
Molar ratio be 80:1, the XRD analysis product is the ZSM-5 molecular sieve with MFI type structure, as shown in Figure 4；
(4) drying ZSM-5 molecular sieve 10g is taken to be added to the Cu (NO that 84.56ml concentration is 1.2mol/L3)23H2O water
In solution；The ion exchange that 3 hours are carried out at 70 DEG C, is then filtered, then the water measured with 5 times is washed, then in 120 DEG C of temperature
Degree is lower 10 hours dry, then carries out roasting for 2 hours at 550 DEG C, obtains Hydrogen ZSM-5 molecular sieve.
(5) 35g copper acetate (Cu is dissolved in 3500g deionized water2(CH3COO)4·H2O) 35g, obtaining pH is 2.8
Copper acetate (II) deionized water solution；In above-mentioned copper acetate (II) from aqueous solution, Hydrogen ZSM-5 zeolite molecular sieve is added
300g is filtered after stirring 2 hours at 80 DEG C, is separated by solid-liquid separation；Hydrogenation synthesis zeolite molecular sieve after separation of solid and liquid is with 40
DEG C 3500g pure water clean, filtering and cleaning is repeated, until detergent remover pH value be 6~7；Then, it is dried at 120 DEG C
Dry filter material 12h is roasted 2 hours at 550 DEG C；After being classified with the mesh screen of 40 mesh, the modified ZSM-5 molecule of copper is obtained
Sieve, the modified ZSM-5 molecular sieve of the copper of icp analysis preparation, copper (II) ion account for the modified ZSM-5 molecular sieve total weight of copper
2.90%, i.e. copper load capacity is 2.90wt%；
(6) the copper modified molecular screen for taking 15g step (4) to obtain, with the commercially available silica solution of 6.26g (silica quality content
Be uniformly mixed for 20wt%) and 21.51g deionized water and be fabricated to the catalyst slurry that solid content is 38.0 mass %, and by its
It is coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system by infusion process, with pressure
Contracting air blows extra slurry droplet off, and drying 24 hours at 120 DEG C is prepared into copper after roasting 2h under the conditions of 550 DEG C and is modified
SCR catalyst, the load capacity on regular material is 241g/L, is denoted as MFI-SCR-3.
Verification test one:
It is used for the obtained catalyst of the embodiment of the present invention 1~6 and comparative example 1~3 to handle diesel engine
The tail gas stream of generation, catalyst performance indexes statistics are as shown in table 1；Relative to the concentration of catalyst upstream NO, measurement is urged
The NO concentration in agent downstream calculates the purifying rate of NO, and operations index is as follows:
Space velocity SV:50000/h
Temperature: 150 DEG C, 200 DEG C, 250 DEG C, 300 DEG C.
Nitric oxide concentration: 500ppm
Ammonia density: 500ppm
Propane concentration: 100ppm
Carbonomonoxide concentration: 50ppm
Oxygen concentration: 10%
Gas concentration lwevel: 10%
Moisture concentration: 10%
Nitrogen concentration: balance
Examples 1 to 6 and the obtained catalyst of comparative example 1~3 purify the result such as table of NOx under the above parameters
Shown in 2:
Table 1: the index of Examples 1 to 6 and the obtained catalyst of comparative example 1~3
Table 2: NO in catalyst treatment diesel motor exhaust stream obtained by Examples 1 to 6 and comparative example 1~3x's
Effect compares
As shown in Table 2, the catalyst of the method for the present invention preparation, when temperature is greater than 200 DEG C, processing diesel engine is generated
Tail gas stream in nitrogen oxides, the purifying rate of NO reaches 80% or more, hence it is evident that higher than the catalyst of comparative example.
Verification test two:
After verification test one, used above-mentioned various catalyst are continued into the durable processing of hydro-thermal and are tested, water
The condition of thermal endurance processing test are as follows:
Space velocity SV:30000/h
Temperature: 700 DEG C
Time: 12 hours
Moisture concentration: 10%
Oxygen concentration: 10%
Nitrogen concentration: balance
After various catalyst carry out the durable processing test of hydro-thermal according to above-mentioned parameter, continue as catalyst for handling bavin
The tail gas stream that oil turbine generates, various operation indexs are identical as verification test one, handle result such as 3 institute of table of nitrogen oxides
Show:
Table 3: the hair of catalyst treatment diesel oil obtained by the Examples 1 to 6 and comparative example 1~3 after hydro-thermal endurance test
NO in motivation tail gas streamxEffect compare
As shown in Table 3, the catalyst of the method for the present invention preparation continues after the durable processing test of hydro-thermal as catalysis
Agent is used to handle the tail gas stream of diesel engine generation, nitrogen oxides is handled in 150~300 DEG C, the purifying rate of NO is above
The catalyst of comparative example, the nitrogen oxides in the tail gas stream of processing diesel engine generation when temperature is greater than 250 DEG C, NO's
Purifying rate reaches 80% or more；The above results illustrate that the catalyst of the method for the present invention preparation has good hydrothermal stability.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (13)
1. a kind of copper modified molecular screen selective reduction catalyst, which is characterized in that with SSZ-13 type molecular sieve and
Matrix components of the eutectic molecular sieve of Analcime type molecular sieve structure as catalyst obtain after introducing active component copper ion
Copper is modified eutectic molecular sieve, is carried on porous regular material to form catalyst, the load of the porous regular material
Amount is 180~260g/L；The mole of the copper ion is 2.0~5.0 times of eutectic molecular sieve saturation exchange capacity；Described
SSZ-13/Analcime eutectic molecular sieve is by silicon source, silicon source, sodium source, H2O, SSZ-13 molecular sieve seed, template R are raw material,
It is prepared after crystallization, filtering, drying and roasting；The silicon source, silicon source, sodium source, H2O, the molar ratio of template R is
20~250:1:5~70:100~10000:3~150, wherein silicon source: silicon source: the molar ratio of sodium source refers to respective oxidation
Object SiO2:Al2O3:Na2The molar ratio of O；Oxide S iO in the SSZ-13 molecular sieve seed and silicon source2Weight ratio be
0.02~0.2:1；
The template R is organic amine template, including two class organic amine template of R1 and R2, organic amine template be R1 and
Two class organic amine template of R2 according to R1:R2=4~10:1 molar ratio at mixed templates；The R1 class template
Agent is N, N, any one in N- trimethyl -1- adamantane ammonium hydroxide, benzyltrimethylammonium hydroxide；The R2 template
To replace alkyl phosphonium hydroxide piperidines；The substitution alkyl phosphonium hydroxide piperidine template agent is N, N- dimethyl -3,5- dimethyl hydrogen
Oxyl, N- ethyl-N-methyl -2,6- dimethyl hydrogen oxyl, N, N- dimethyl -2- (2- ethoxy)-dimethyl hydrogen
Oxyl, N, N- dimethyl -2- ethyl-dimethyl diisopropylimidazolinium, N, N- diethyl -2,6- dimethyl hydrogen oxyl,
It is any one in N, N- dimethyl -2,6- dimethyl hydrogen oxyl, N- ethyl-N- propyl -2,6- dimethyl hydrogen oxyl
Kind or two kinds or more the mixtures being mixed in any proportion.
2. catalyst according to claim 1, which is characterized in that the weight of the copper ion accounts for the modified eutectic molecule of copper
Sieve the 0.03~20% of overall weight.
3. catalyst according to claim 2, which is characterized in that the mole of the copper ion is full for eutectic molecular sieve
With 2.0~4.0 times of exchange capacity, the weight of copper ion accounts for the 0.2~15% of the modified eutectic molecular sieve overall weight of copper.
4. catalyst according to claim 1, which is characterized in that the silicon source, silicon source, sodium source, H2O, template R
Molar ratio is 20~150:1:8~68:130~4500:3~150；Oxide in the SSZ-13 molecular sieve seed and silicon source
SiO2Weight ratio be 0.02~0.1:1.
5. catalyst according to claim 1, which is characterized in that the silicon source be sodium metaaluminate, sodium aluminate, SB powder,
Aluminum sulfate, boehmite, any one in aluminium isopropoxide；The silicon source is chromatographic silica gel, silica solution, sodium metasilicate, hard charcoal
Any one in black, ethyl orthosilicate, silicic acid.
6. catalyst according to claim 4, which is characterized in that the silicon source be sodium metaaluminate, sodium aluminate, SB powder,
Any one in boehmite, aluminium isopropoxide；The silicon source is chromatographic silica gel, in white carbon black, ethyl orthosilicate, sodium metasilicate
Any one.
7. catalyst according to claim 1, which is characterized in that the porous regular material is porous honeycomb stream
The regular material of type is crossed, cordierite, alph-alumine, silicon carbide, aluminium titanates, silicon nitride, zirconium oxide, mullite, spodumene, oxidation are selected from
Any one in aluminium-silica-magnesia or zirconium silicate.
8. catalyst according to claim 7, which is characterized in that the porous regular material is cordierite.
9. the preparation method of any one of claim 1~8 catalyst, which comprises the following steps:
(1) prepare eutectic molecular sieve: silicon source, silicon source, sodium source, deionized water, SSZ-13 molecular sieve seed, template R are according to institute
After the ratio mixing stated, then 20~144h of crystallization under conditions of self-generated pressure and crystallization temperature are 100~200 DEG C passes through
SSZ-13/Analcime eutectic molecular sieve is obtained after filtering, drying and roasting；The temperature of the drying is 100~150 DEG C,
Drying time is 12~48h, and the maturing temperature is 450~650 DEG C, and calcining time is 3~20h；
(2) it prepares hydrogen type molecular sieve: the SSZ-13/Analcime eutectic molecular sieve that step (1) obtains is put into ammonium salt aqueous solution
In carried out under the conditions of 70~100 DEG C after ammonium ion exchanges 1~3 time, dry 12~48h under the conditions of 105~120 DEG C, then
Hydrogen type molecular sieve is obtained after roasting 2~10h under the conditions of 450~650 DEG C；
(3) copper modified hydrogen molecular sieve: the hydrogen type molecular sieve that step (2) obtains is added in copper salt solution, room temperature~
It is modified that 24~72h progress copper is stirred under the conditions of 100 DEG C, is dried in vacuo 12~48h after filtering under the conditions of 50~100 DEG C, is repeated
Above-mentioned modification, filtering, after process of vacuum drying 0~3 time, by the sample after drying under the conditions of normal atmosphere pressure in 450~
After roasting 3~5h at 600 DEG C, the modified eutectic molecular sieve of the copper is obtained；
(4) the modified eutectic molecular sieve of the copper for obtaining step (3) and colloidal silicon dioxide are mixed according to the weight ratio of 2.0~5.0:1
After conjunction, deionized water is added and is prepared into catalyst slurry, copper modified molecular screen and colloidal silicon dioxide is total in catalyst slurry
Solid content is 35.0~55.0wt%；By infusion process, the catalyst slurry is coated on institute according to the load capacity
On the porous regular material stated, extra slurry droplet is blown off with compressed air, 12~48h of drying under the conditions of 105~120 DEG C,
Then 2~10h is roasted under the conditions of 450~650 DEG C, is prepared into copper modified molecular screen SCR catalyst.
10. according to the method described in claim 9, it is characterized in that, crystallization temperature described in step (1) is 150~200
DEG C, crystallization time is 24~100h；The temperature of the drying is 105~120 DEG C；In step (2), the ammonium salt aqueous solution
For the aqueous solution of ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium hydrogen carbonate, the concentration of ammonium ion is 1.0mol/L, ammonium ion exchange temperature
Degree is 80~100 DEG C；In step (3), the copper salt solution is the water-soluble of copper nitrate, copper chloride, copper acetate or copper sulphate
Liquid, the concentration of copper ion is 0.1~1.5mol/L in copper salt solution.
11. according to the method described in claim 10, it is characterized in that, crystallization time described in step (1) is 48~144h；
Ammonium salt aqueous solution described in step (2) is the aqueous solution of ammonium nitrate or ammonium chloride；In step (3), the copper salt solution
For the aqueous solution of copper nitrate, copper chloride or copper sulphate.
12. the application of any one of claim 1~8 catalyst, which is characterized in that the catalyst contains for handling
NOxIn the exhaust treatment system of air-flow.
13. application according to claim 12, which is characterized in that described contains NOxAir-flow, in addition to including nitrogen oxides,
Also contain oxygen, ammonia or urea, wherein NO2Content be at most NOxThe 80% of weight.
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