CN106622356A - Copper modified molecular sieve selective reduction catalyst, preparation method and applications thereof - Google Patents
Copper modified molecular sieve selective reduction catalyst, preparation method and applications thereof Download PDFInfo
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Abstract
The present invention discloses a copper modified molecular sieve selective reduction catalyst, a preparation method and applications thereof. According to the present invention, the eutectic molecular sieve of a SSZ-13 molecular sieve and an Analcime molecular sieve is used as a catalyst matrix component, copper ion is adopted as an active component, the molar amount of the copper ion is 2.0-5.0 times the saturation exchange capacity of the eutectic molecular sieve, and the copper ion accounts for 0.03-20% of the total weight of the copper modified eutectic molecular sieve; after the copper modified eutectic molecular sieve and a binder form a slurry, a porous regular material is coated with the slurry by using an impregnating method to prepare the catalyst; the eutectic molecular sieve is prepared by adopting a silicon source, an aluminum source, a sodium source, H2O, SSZ-13 molecular sieve crystal seed and a templating agent R as raw materials through crystallization, filtration, drying and calcination, wherein a molar ratio of the silicon source to the aluminum source to the sodium source to the H2O to the R is 20-250:1:5-70:100-10000:3-150, and a weight ratio of the SSZ-13 molecular sieve crystal seed to the SiO2 is 0.02-0.2:1; and the copper modified molecular sieve selective reduction catalyst is mainly used for treating the tail gas treatment system containing the NOx gas stream, has excellent selective reducing ability in the low temperature range, and has good hydrothermal stability.
Description
Technical field
The present invention relates to a kind of selective catalytic reduction catalysts (SCR) and preparation method thereof, the catalyst is for vent gas treatment
In system；Specifically related to a kind of copper modified molecular screen selective reduction catalyst, the catalyst is used to contain nitrogen oxides (NOx)
In the exhaust treatment system of air-flow, the tail gas containing nitrogen oxides (NOx) air-flow in the presence of oxygen is specifically for use in
In processing system.
Background technology
Lean-combustion engine (such as diesel engine and gasoline engine) can provide good fuel economy for user, and
Operation is realized by the ratio of the high air/fuel of control under the conditions of fuel rare (lean-burn), the carburet hydrogen of low amounts can be discharged
And carbon monoxide (CO) (HC).However, lean-combustion engine easily produces more rows containing nitrogen oxides (NOx) tail gas
Put, and the also oxygen (O2) comprising up to 15 volumes % in tail gas；Because the high NOx conversion of content generally needs be rich in
Just can carry out under conditions of reducing agent, it is difficult to effectively reduce it from the discharge of this kind of motor exhaust.Generally in lean-burn (lean
Burning under the conditions of), need the operation measure for using special reduction NOx by the NOx conversion in exhaust stream into harmless components.
Therefore, a kind of higher selective reduction (SCR) catalyst of activity is very heavy when SCR method processes waste gas discharge
Will.At present, usual SCR catalyst be typically with zeolite as carrier, load SCR activity component be prepared from crystal
The molecular sieve of structure；Zeolite be have quite regular pore size silicon aluminate crystal material, such as β zeolites, Y zeolites,
X zeolites, faujasite, modenite, erionite, ZSM-5, ZSM-8, ZSM-11, ZSM-12 zeolite etc., these
Zeolite can be with the metal exchange such as Cu, Fe, Mn, Ag, V, Ti, Co, or zeolite itself contains some Cu, Fe
Deng metal.But, above-mentioned known metal-modified zeolite catalyst during ammine selectivity catalytic reduction nitrous oxides only
The purification of nitrogen oxides can be carried out in the range of narrower temperature province, not with highly active NOx purifications below 300 DEG C
Performance, hydrothermal stability is poor, and activity is relatively low under cryogenic conditions.
It is, because framework of molecular sieve structural stability is poor, to cause under the conditions of dramatic temperature conversion that these activity of molecular sieve catalysts are low
Structure is destroyed, and metal active constituent is easily assembled, and reduces the decentralization at metal ion activity center.
The content of the invention
The technical problem to be solved is to be directed to the deficiencies in the prior art, and provides a kind of copper modified molecules screening
Selecting property reducing catalyst, the catalyst has excellent selective reduction ability within the scope of the low temperature temperature wider to high temperature,
Still there is higher catalysis activity under cryogenic conditions, and the catalyst has 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 types molecular sieve and
After the eutectic molecular sieve of Analcime type molecular sieve structures, by introducing Cu in ion exchange normal direction eutectic molecular sieve, changed with Cu
Property eutectic molecular sieve, modified catalyst has good hydrothermal stability, more suitable pore passage structure, beneficial to NOx point
The diffusion of son, strengthens the attachment of metal copper ion, reduces it and receives possibility that is hydrothermal and producing aggregation.
The third object of the present invention is to provide a kind of application of above-mentioned catalyst.
To achieve these goals, the present invention is adopted the following technical scheme that：A kind of copper modified molecular screen selective reduction catalyst,
Using the eutectic molecular sieve with SSZ-13 types molecular sieve and Analcime type molecular sieve structures as the matrix components of catalyst, draw
Enter to be obtained after active component copper ion the modified eutectic molecular sieve of copper, be carried on the regular material of porous so as to form catalyst, it is described
The regular material of porous load capacity be 180～260g/L；The mole of described copper ion is eutectic molecular sieve saturation exchange capacity
2.0～5.0 times；Described SSZ-13/Analcime eutectic molecular sieves are by silicon source, silicon source, sodium source, deionized water (H2O)、SSZ-13
Molecular sieve seed, template R are raw material, are prepared from after crystallization, filtration, drying and roasting；Described silicon source, aluminium
Source, sodium source, H2O, the mol ratio of template R are 20～250:1:5～70:100～10000:3～150, wherein silicon source：Silicon source：
The mol ratio of sodium source refers to respective oxide S iO2:Al2O3:Na2The mol ratio of O；Described SSZ-13 molecular sieve seeds with
SiO2Weight ratio be 0.02～0.2:1.
In above-mentioned technical proposal, the mole of described copper ion is preferably 2.0～4.0 times of eutectic molecular sieve saturation exchange capacity.
In above-mentioned technical proposal, the weight of described copper ion accounts for the 0.03～20% of the modified eutectic molecular sieve overall weight of copper, preferably
For 0.2～15%, preferably 0.5～10%, more preferably 1.0-8.0%, more preferably 1.5-5.0%, further preferably
For 2.0-4.0%, more preferably more preferably 2.5-3.5%, more preferably 2.7-3.3%, 2.9-3.1%.
In above-mentioned technical proposal, described silicon source, silicon source, sodium source, H2O, the mol ratio of template R are preferably
20～150:1:8～68:130～4500:3～150；Described SSZ-13 molecular sieve seeds and SiO2Weight ratio preferably 0.02～0.1:1.
In above-mentioned technical proposal, described silicon source is sodium metaaluminate, sodium aluminate, SB powder, aluminum sulfate, boehmite, isopropanol
Any one in any one in aluminium, preferably sodium metaaluminate, sodium aluminate, SB powder, boehmite, aluminium isopropoxide.
In above-mentioned technical proposal, described silicon source is chromatographic silica gel, Ludox, sodium metasilicate, white carbon, tetraethyl orthosilicate, silicon
Any one in any one in acid, preferably chromatographic silica gel, white carbon, tetraethyl orthosilicate, sodium metasilicate.
In above-mentioned technical proposal, described R is organic amine template, including R1 and the class organic amine templates of R2 two；Described
Organic amine template is according to R1 by R1 and the class organic amine templates of R2 two：R2=4～10:1 molar ratio into mixing
Template；Described R1 classes organic amine template be N, N, N- trimethyl -1- adamantane ammonium hydroxide, benzyl trimethyl hydroxide
In ammonium any one；Described R2 classes organic amine template is replacement alkyl phosphonium hydroxide piperidines；Described replacement alkyl phosphonium hydroxide
Piperidine template agent be N, N- dimethyl -3,5- dimethyl hydrogen oxyls, N- ethyl-N-methyl -2,6- dimethyl hydrogen oxyls,
N, N- dimethyl -2- (2- ethoxys)-dimethyl hydrogen oxyl, N, N- dimethyl -2- ethyl-dimethyl diisopropylimidazoliniums, N, N-
Diethyl -2,6- dimethyl hydrogen oxyls, N, N- dimethyl -2,6- dimethyl hydrogen oxyls, N- ethyl-N- propyl group -2,6- two
Any one in methyl diisopropylimidazolinium, or the mixture that two kinds and the above are mixed with arbitrary proportion.
In above-mentioned technical proposal, the regular material of described porous flows through the regular material of type for the cellular of porous, selected from cordierite, α-
Alumina, carborundum, aluminium titanates, silicon nitride, zirconium oxide, mullite, spodumene, alumina-silica magnesia or silicon
Any one in sour zirconium；Preferably cordierite.
The present invention also provides a kind of preparation method of above-mentioned copper modified molecular screen selective reduction catalyst, comprises the following steps：
(1) eutectic molecular sieve is prepared：Silicon source, silicon source, sodium source, deionized water, SSZ-13 molecular sieve seeds, template R
After according to described ratio mixing, 20～144h of crystallization, Ran Houjing under conditions of self-generated pressure and crystallization temperature are for 100～200 DEG C
SSZ-13/Analcime eutectic molecular sieves are obtained after filtration, drying and roasting；The temperature of described drying is 100～150 DEG C,
Drying time is 12～48h, and described sintering temperature is 450～650 DEG C, and roasting time is 3～20h；
(2) hydrogen type molecular sieve is prepared：The SSZ-13/Analcime eutectic molecular sieves that step (1) is obtained are put into ammonium salt water-soluble
Carry out under the conditions of 70～100 DEG C after ammonium ion exchanges 1～3 time, 12～48h, Ran Houyu being dried under the conditions of 105～120 DEG C in liquid
Hydrogen type molecular sieve is obtained under the conditions of 450～650 DEG C after 2～10h of roasting；
(3) copper modified hydrogen molecular sieve：The hydrogen type molecular sieve that step (2) is obtained is added in copper salt solution, in room temperature
Under the conditions of～100 DEG C stir 24～72h carry out copper be modified, after filtration under the conditions of 50～100 DEG C be vacuum dried 12～48h, in repetition
State it is modified, filter, after process of vacuum drying 0～3 time, by dried sample under the conditions of normal atmosphere pressure in 450～600 DEG C
After 3～5h of lower roasting, the modified eutectic molecular sieve of described copper is obtained；
(4) the modified eutectic molecular sieve of the copper for obtaining step (3) and cataloid are according to 2.0～5.0:1 weight is than mixing
Afterwards, deionized water is added to be prepared into catalyst slurry, copper modified molecular screen contains admittedly with the total of cataloid in catalyst slurry
Measure as 35.0～55.0wt%；By infusion process, described catalyst slurry is coated on into described porous according to described load capacity
On regular material, with compressed air unnecessary slurry droplet is blown off, 12～48h, Ran Houyu are dried under the conditions of 105～120 DEG C
2～10h of roasting under the conditions of 450～650 DEG C, is prepared into copper modified molecular screen SCR catalyst.
In above-mentioned technical proposal, the crystallization temperature described in step (1) is preferably 150～200 DEG C；Described crystallization time is preferred
For 24～100h, more preferably 48～100h；The temperature of described drying is preferably 105～120 DEG C.
In above-mentioned technical proposal, in step (2), described ammonium salt aqueous solution is ammonium nitrate, ammonium sulfate, ammonium chloride or bicarbonate
The aqueous solution of ammonium, the concentration of ammonium ion is 1.0mol/L；Ammonium salt aqueous solution is more preferably the aqueous solution of ammonium nitrate or ammonium chloride；
Described ammonium ion is exchanged and is preferably 80～100 DEG C.
In above-mentioned technical proposal, in step (3), described copper salt solution is copper nitrate, copper chloride, copper acetate or copper sulphate
The aqueous solution, in copper salt solution the concentration of copper ion be 0.1～1.5mol/L；Described copper salt solution is more preferably nitre
The aqueous solution of sour copper, copper chloride or copper sulphate.
The present invention also provides a kind of application of above-mentioned copper modified molecular screen selective reduction catalyst, the catalyst mainly for the treatment of
Containing nitrogen oxides (NOx) air-flow exhaust treatment system in；Described tail gas stream also includes in addition to containing nitrogen oxides
Oxygen, ammonia and/urea.
During the selective exposure of reducing agent (urea or NH3 etc.) reduction (SCR) system is usually used, there are several chemical reactions：
NO and NH3 and oxygen reaction, are reduced to nitrogen, as shown in Equation 1 by NO：
4NO+4NH3+O2→4N 2+6H2O (1)；
Additionally, NO and NH3 can also occur the non-selective reaction of oxygen, further consume NH3 or generate secondary product,
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 the reaction between NH3 and NO and NO 2 is then carried out according to formula 4：
NO+NO2+2NH3→2N 2+3H2O (4)。
The reaction speed of reaction (1), (3) and (4) is varied considerably because reaction temperature is different with the species of the catalyst for using,
The speed of reaction (4) usually react (1), 2～10 times of the speed of (3).
In SCR selective reduction systems, in order to improve low temperature under NOx detergent powers, it is necessary to so that formula (4) is anti-
Should be smoothed out, rather than the reaction of formula (1) is occupied an leading position.The plot ratio of NO2, can make low in by improving gas
Temperature is lower to cause the reaction of formula (4) to occupy an leading position.
And under 150～300 DEG C of cryogenic conditions, copper has excellent adsorption capacity to NO, and make the oxidability of NO more
By force, the oxidation reaction of NO is represented by formula 5：
NO+1/2O2→NO2 (5)。
In above-mentioned technical proposal, using the catalyst treatment of the present invention NO is containedxAir-flow when, NO2Content be at most NOx
80%, NO of weight2Content be preferably NOxThe 0.01～70% of weight, more preferably NOxThe 0.01～60% of weight,
More preferably NOxThe 0.015～55% of weight, more preferably NOxThe 0.02～50% of weight.
Copper modified molecular screen selective reduction catalyst of the present invention, has excellent within the scope of the low temperature temperature wider to high temperature
Different selective reduction ability, can be capable of achieving to NO within the rangexPurification；And the catalyst has good hydro-thermal
Stability, after undergoing hydro-thermal long duration test, under catalyst low temperature of the present invention NO is purifiedxPerformance be supported on β and ZSM-5 than copper
SCR catalyst performance after the hydrothermal aging formed on molecular sieve is more excellent.
Description of the drawings
Fig. 1：The XRD of the modified eutectic molecular sieve of copper prepared by the embodiment of the present invention 1；
Fig. 2：The XRD of the modified SSZ-13 molecular sieves of copper prepared by comparative example of the present invention 1；
Fig. 3：The XRD of copper modified beta molecular sieve prepared by comparative example of the present invention 2；
Fig. 4：The XRD of ZSM-5 molecular sieve prepared by comparative example of the present invention 3；
Fig. 5：ESEM (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 to description below：
Embodiment 1：
A kind of copper modified molecular screen selective reduction catalyst, is prepared from by following methods：
(1) eutectic molecular sieve is prepared：By 1.673g NaAlO2(purity 99%, Tianjin recovery fine chemistry industry research institute) adds
Enter in 120.06g deionized waters, stirring 0.5h after, be added dropwise 30.00g mass fraction be 25% N, N, N- front three fund
Just alkane aqueous ammonium (R1) and 1.05g N, N- dimethyl -3,5- dimethyl hydrogen oxyls (R2), add Jing after being sufficiently stirred for
3.690g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.), stir 0.5h, add 69.761g
Sodium silicate aqueous solution (modulus nSiO2/nNa2O is 3.35, and concentration is 249.6g/L, and proportion is 1.26g/ml), 2～3h is stirred,
0.691g SSZ-13 crystal seeds are added after being thoroughly mixed, in being fitted into teflon-lined steel bomb, at 170 DEG C
Crystallization 72h；After the completion of reaction, product is washed with deionized, 12h roasting 12h at 580 DEG C is dried at 120 DEG C and is obtained
To molecular sieve solid powder；
The mol ratio of raw material is：Na2O：Al2O3：SiO2：H2O：R1：R2 is 8.0：1.0：23.0：667.0：3.549：
0.591；
(2) hydrogen type molecular sieve is prepared：Taking the molecular sieve solid powder 10g that step (1) obtains, to be added to 1000mL ammonium nitrate molten
In liquid (1.0mol/L), 12h is exchanged under 80 DEG C of water bath conditions, fully wash and filter；Then repeat above-mentioned ammonium ion to exchange
After 3 times, 48h is dried at 105 DEG C, in 500 DEG C of roasting 8h, obtains Hydrogen SSZ-13/ANA eutectic molecular sieves；
(3) copper modified hydrogen molecular sieve：The molecular sieve 10g for taking step (2) synthesis is added to 78.68ml concentration for 0.2mol/L
Cu (NO3)2In the 3H2O aqueous solution；Dust technology is added dropwise in above-mentioned solution and adjusts its pH to 2.8, inserted after stirring
In heatproof container, and it is put into together in the drier with pressure-reducing valve；With vavuum pump by the pressure in drier be extracted into 10Torr with
After lower, room temperature carries out the degassing process of 1 hour, then after 90 DEG C of Conditions Temperatures are dried 12 hours, by dried sample
In 500 DEG C of roasting temperatures 4 hours under the conditions of normal atmosphere pressure；Then it is classified with the screen cloth of 40 mesh, is obtained described
The modified eutectic molecular sieve of copper, the modified eutectic molecular sieve of copper prepared by icp analysis, it is total that copper (II) ion accounts for the modified eutectic molecular sieve of copper
The 2.5% of weight, i.e. copper load capacity are 2.5wt%, and the XRD of the molecular sieve is as shown in Figure 1；
(4) the copper modified molecular screen that 15g steps (3) are obtained is taken, (silica contains with the commercially available cataloids of 6.71g
Measure as 20%wt) and 16.90g deionized waters be well mixed be fabricated to solid content be 42wt% catalyst slurry, and will catalysis
Agent slurries are coated on the cellular regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system by infusion process,
Unnecessary slurry droplet being blown off with compressed air, being dried 24 hours at 110 DEG C, after roasting 2h under the conditions of 500 DEG C copper is prepared into
Modified molecular screen SCR catalyst, the load capacity on regular material is that (quality of regular material weightening is divided by rule after roasting for 227g/L
Spatial volume occupied by whole timber material, the computational methods of other embodiment are 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 from by following methods：
(1) eutectic molecular sieve is prepared：By 1.457g SB powder (German Sasol companies, Al2O3% >=70%) be added to 1008.00g
In deionized water, after stirring 0.5h, the mass fraction that 395.13g is added dropwise is that the methyl alcohol of 40% benzyltrimethylammonium hydroxide is molten
Liquid (R1) and 25.89g N- ethyl-N-methyl -2,6- dimethyl hydrogen oxyls (R2) adds 30.82g Jing after being sufficiently stirred for
NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.), stirs 0.5h, adds 122.62g white carbons
(SiO2% >=70%), 2～3h is stirred, the SSZ-13 molecular sieve seeds of 7.21g are added after being thoroughly mixed, load poly- four
In the steel bomb of PVF liner, crystallization 144h at 155 DEG C；After the completion of reaction, product is washed with deionized and is filled
Point, 24h roasting 12h at 580 DEG C are dried at 105 DEG C and obtain molecular sieve solid powder；
The mol ratio of raw material is：Na2O：Al2O3：SiO2：H2O：R1：R2 is 68.0：1.0：200.0：5600.0：94.5：
13.5；
(2) hydrogen type molecular sieve is prepared：Taking the molecular sieve solid powder 15g that step (1) obtains, to be added to 1500mL ammonium nitrate molten
In liquid (1.0mol/L), 24h is exchanged under 85 DEG C of water bath conditions, fully wash and filter, then repeated above-mentioned ammonium ion and exchange
3 times, 36h is dried at 110 DEG C, in 550 DEG C of roasting 4h, obtains Hydrogen SSZ-13/Analcime eutectic molecular sieves；
(3) copper modified hydrogen molecular sieve：The molecular sieve 15g for taking step (2) synthesis is added to 51.22ml concentration for 0.5mol/L
CuCl2·2H2In the O aqueous solution；Dust technology is added dropwise in above-mentioned solution and adjusts its pH to 2.9, inserted after stirring heat-resisting
In container, and it is put into together in the drier with pressure-reducing valve；The pressure in drier is extracted into after below 10Torr with vavuum pump,
Room temperature carries out the degassing process of 1 hour, then after 80 DEG C of dryings 20 hours, by dried sample in normal atmosphere pressure
Under the conditions of in 550 DEG C of roasting temperatures 3 hours；Then it is classified with the screen cloth of 40 mesh, is obtained described copper modified molecular screen,
The modified eutectic molecular sieve of copper prepared by icp analysis, copper (II) ion accounts for the 3.1% of the modified eutectic molecular sieve gross weight of copper, i.e. copper load
Measure as 3.1wt%, the SEM figures of the copper modified molecular screen are as shown in Figure 5；
(4) the copper modified molecular screen that 15g steps (3) are obtained is taken, with the commercially available Ludox of 4.72g (silica quality content
For 20wt%) and 10.67g deionized waters be well mixed the catalyst slurry for being fabricated to that solid content is 52.0wt%, and led to
Cross infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, use
Compressed air blows unnecessary slurry droplet off, is dried 20 hours at 120 DEG C, is prepared into copper after roasting 3h under the conditions of 500 DEG C and changes
Property molecular sieve SCR catalyst, the load capacity on regular material be 219g/L, be designated as CCG-SCR-2.
Embodiment 3：
A kind of copper modified molecular screen selective reduction catalyst, is prepared from by following methods：
(1) eutectic molecular sieve is prepared：By 6.732g Al2(SO4)318H2O (Chemical Reagent Co., Ltd., Sinopharm Group, purity
>=99%) be added in 180.00g deionized waters, 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- ethoxys)-dimethyl hydrogen oxyl (R2), Jing
8.51g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.) are added after being sufficiently stirred for, 0.5h is stirred,
Add 30.65g chromatographic silica gels (Qingdao Marine Chemical Co., Ltd., SiO2% >=98%), 2～3h is stirred, it is sufficiently stirred for mixing
2.40g SSZ-13 crystal seeds, in being fitted into teflon-lined steel bomb, crystallization 120h at 165 DEG C are added after conjunction；
After the completion of reaction, product is washed with deionized, be dried at 110 DEG C 36h roasting 12h at 580 DEG C obtain molecular sieve consolidate
Body powder；
The mol ratio of raw material is：Na2O：Al2O3：SiO2：H2O：R1：R2 is 18.0：1.0：50.0：1000.0：13.991：
2.798；
(2) hydrogen type molecular sieve is prepared：Taking the molecular sieve solid powder 30g that step (1) obtains, to be added to 3000mL ammonium nitrate molten
In liquid (1.0mol/L), 20h is exchanged under 90 DEG C of water bath conditions, fully wash and filter, then repeated above-mentioned ammonium ion and exchange
2 times, 24h is dried at 115 DEG C, in 550 DEG C of roasting 3h, obtains Hydrogen SSZ-13/Analcime eutectic molecular sieves；
(3) copper modified hydrogen molecular sieve：The molecular sieve 30g for taking step (2) synthesis is added to 34.23ml concentration for 0.8mol/L
Cu SO4In the aqueous solution；Dust technology is added dropwise in above-mentioned solution and adjusts its pH to 3.0, heatproof container is inserted after stirring
In, and be put into together in the drier with pressure-reducing valve；The pressure in drier is extracted into after below 10Torr with vavuum pump, room
Temperature carries out the degassing process of 1 hour, then after 70 DEG C of dryings 24 hours, by dried sample in normal atmosphere pressure bar
In 550 DEG C of roasting temperatures 3 hours under part；Then it is classified with the screen cloth of 40 mesh, is obtained described copper modified molecular screen,
The modified eutectic molecular sieve of catalyst copper prepared by icp analysis, copper (II) ion accounts for the 2.9% of the modified eutectic molecular sieve gross weight of copper, i.e.,
Copper load capacity is 2.9wt%；
(4) the copper modified molecular screen that 15g steps (3) are obtained is taken, with the commercially available Ludox of 6.34g (silica quality content
For 20wt%) and 23.79g deionized waters be well mixed the catalyst slurry for being fabricated to that solid content is 36.0wt%, and led to
Cross infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, use
Compressed air blows unnecessary slurry droplet off, is dried 20 hours at 120 DEG C, is prepared into copper after roasting 3h under the conditions of 500 DEG C and changes
Property molecular sieve SCR catalyst, the load capacity on regular material be 234g/L, be designated as CCG-SCR-3.
Embodiment 4：
A kind of copper modified molecular screen selective reduction catalyst, is prepared from by following methods：
(1) eutectic molecular sieve is prepared：4.168g aluminium isopropoxides (purity >=98%) are added in 126.00g deionized waters,
After stirring 0.5h, the mass fraction that 148.79g is added dropwise is 25% N, N, N- trimethyl adamantane aqueous ammonium (R1) and 7.76g
N, N- dimethyl -2- ethyl-dimethyl diisopropylimidazoliniums (R2), add Jing after being sufficiently stirred for 12.98g NaOH (purity 96%,
Tianjin Kermel Chemical Reagent Co., Ltd.), 0.5h is stirred, add 170.07g silester (Chinese medicines group chemical reagent
Co., Ltd, purity >=98%), 2～3h is stirred, 1.92g SSZ-13 crystal seeds are added after being thoroughly mixed, load polytetrafluoro
In the steel bomb of ethene liner, in 175 DEG C of crystallization 72h；After the completion of reaction, product is washed with deionized, 120 DEG C
Under be dried 40h roasting 12h at 580 DEG C and obtain molecular sieve solid powder；
The mol ratio of raw material is：Na2O：Al2O3：SiO2：H2O：R1：R2 is 28.0：1.0：80.0：700.0：17.6：
4.4；
(2) hydrogen type molecular sieve is prepared：Taking the molecular sieve solid powder 50g that step (1) obtains, to be added to 5000mL ammonium nitrate molten
In liquid (1.0mol/L), 12h is exchanged under 95 DEG C of water bath conditions, fully wash and filter, then repeated above-mentioned ammonium ion and exchange
2 times, 12h is dried at 120 DEG C, in 600 DEG C of roasting 2.5h, obtains Hydrogen SSZ-13/Analcime eutectic molecular sieves；
(3) copper modified hydrogen molecular sieve：The molecular sieve 50g for taking step (2) synthesis is added to 57.94ml concentration for 1.1mol/L
Cu (NO3)2·3H2In the O aqueous solution；Dust technology is added dropwise in above-mentioned solution and adjusts its pH to 2.8, inserted after stirring resistance to
In heat container, and it is put into together in the drier with pressure-reducing valve；The pressure in drier is extracted into below 10Torr with vavuum pump
Afterwards, room temperature carries out the degassing process of 1 hour, then after 60 DEG C of dryings 36 hours, by dried sample in normal atmosphere
In 500 DEG C of roasting temperatures 5 hours under pressure conditions；Then it is classified with the screen cloth of 40 mesh, is obtained modified point of described copper
Son sieve, in the modified eutectic molecular sieve of copper prepared by icp analysis, copper (II) ion accounts for the 2.7% of the modified eutectic molecular sieve gross weight of copper,
I.e. copper load capacity is 2.7wt%；
(4) the copper modified molecular screen that 15g steps (3) are obtained is taken, with the commercially available Ludox of 5.27g (silica quality content
For 20wt%) and 8.96g deionized waters be well mixed the catalyst slurry for being fabricated to that solid content is 55.0wt%, and passed through
Infusion process is coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with pressure
Contracting air blows unnecessary slurry droplet off, is dried 24 hours at 120 DEG C, copper is prepared into after roasting 5h under the conditions of 500 DEG C and is modified
Molecular sieve SCR catalyst, the load capacity on regular material is 216g/L, is designated as CCG-SCR-4.
Embodiment 5：
A kind of copper modified molecular screen selective reduction catalyst, is prepared from by following methods：
(1) eutectic molecular sieve is prepared：By 1.359g boehmites (Shandong Aluminum Plant, purity >=75%) be added to 288.00g
In deionized water, stirring 0.5h after, be added dropwise 240.47g mass fraction be 25% N, N, N- trimethyl adamantane aqueous ammonium
(R1) and 7.33g N, N- diethyl -2,6- dimethyl hydrogen oxyls (R2), 17.03g NaOH are added Jing after being sufficiently stirred for
(purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.), stirs 0.5h, adds 303.31g water glass solution (moulds
Number nSiO2/nNa2O is 3.35, and concentration is 249.6g/L, and proportion is 1.26g/ml) 2～3h of stirring, add after being thoroughly mixed
Enter 1.20g SSZ-13 crystal seeds, in being fitted into teflon-lined steel bomb, crystallization 60h at 180 DEG C；React
Cheng Hou, product is washed with deionized, and 48h roasting 12h at 580 DEG C is dried at 115 DEG C and obtains molecular sieve solid powder；
The mol ratio of raw material is：Na2O：Al2O3：SiO2：H2O：R1：R2 is 36.0：1.0：100.0：1600.0：28.444：
3.556；
(2) hydrogen type molecular sieve is prepared：Take the molecular sieve solid powder 50g that step (1) obtains and be added to 5000mL ammonium nitrate
In solution (1.0mol/L), 8h is exchanged under 98 DEG C of water bath conditions, fully wash and filter, then repeated above-mentioned ammonium ion and exchange
2 times, 12h is dried at 120 DEG C, in 650 DEG C of roasting 2h, obtains Hydrogen SSZ-13/Analcime eutectic molecular sieves；
(3) copper modified hydrogen molecular sieve：The molecular sieve 50g for taking step (2) synthesis is added to 57.37ml concentration for 1.2mol/L
Cu (NO3)2·3H2In the O aqueous solution；Dust technology is added dropwise in above-mentioned solution and adjusts its pH to 2.8, inserted after stirring resistance to
In heat container, and it is put into together in the drier with pressure-reducing valve；The pressure in drier is extracted into below 10Torr with vavuum pump
Afterwards, room temperature carries out the degassing process of 1 hour, then after 55 DEG C of dryings 48 hours, by dried sample in normal atmosphere
In 550 DEG C of roasting temperatures 3 hours under pressure conditions；Then it is classified with the screen cloth of 40 mesh, is obtained modified point of described copper
Son sieve, the modified eutectic molecular sieve of copper prepared by icp analysis, copper (II) ion accounts for the 3.5% of the modified eutectic molecular sieve gross weight of copper, i.e.,
Copper load capacity is 3.5wt%；
(4) the copper modified molecular screen that 15g steps (3) are obtained is taken, with the commercially available Ludox of 3.68g (silica quality content
For 20wt%) and 21.67g deionized waters be well mixed the catalyst slurry for being fabricated to that solid content is 39.0wt%, and passed through
Infusion process is coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with pressure
Contracting air blows unnecessary slurry droplet off, is dried 24 hours at 120 DEG C, copper is prepared into after roasting 3h under the conditions of 550 DEG C and is modified
Molecular sieve SCR catalyst, the load capacity on regular material is 197g/L, to be designated as CCG-SCR-5.
Embodiment 6：
A kind of copper modified molecular screen selective reduction catalyst, is prepared from by following methods：
(1) eutectic molecular sieve is prepared：By 7.578g Al (NO3)3·9H2(purity 99%, Tianjin Ke Miou chemical reagent has O
Limit company) 648.00g deionized waters are added to, after stirring 0.5h, the mass fraction that 502.17g is added dropwise is 25% N, N, N-
Trimethyl adamantane aqueous ammonium (R1) and 11.7g N, N- dimethyl -2,6- dimethyl hydrogen oxyls (R2), Jing is fully stirred
23.12g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.) are added after mixing, 0.5h is stirred, then is added
Enter 91.97g white carbon (SiO2% >=98%), 2～3h is stirred, 8.11g SSZ-13 crystal seeds, dress are added after being thoroughly mixed
In entering teflon-lined steel bomb, crystallization 48h at 190 DEG C；After the completion of reaction, by product deionized water
Washing, is dried 12h roasting 12h at 580 DEG C and obtains molecular sieve solid powder at 120 DEG C；
The mol ratio of raw material is：Na2O：Al2O3：SiO2：H2O：R1：R2 is 51.0：1.0：150.0：3600.0：59.4：
6.6；
(2) hydrogen type molecular sieve is prepared：Take the molecular sieve solid powder 100g that step (1) obtains and be added to 10L ammonium nitrate solutions
(1.0mol/L) in, 8h is exchanged under 99 DEG C of water bath conditions, fully washs and filter, then repeated above-mentioned ammonium ion and exchange 2 times,
12h is dried at 120 DEG C, in 450 DEG C of roasting 10h, Hydrogen SSZ-13/Analcime eutectic molecular sieves is obtained；
(3) copper modified hydrogen molecular sieve：The molecular sieve 100g for taking step (2) synthesis is added to 44.06ml concentration for 1.5mol/L
CuCl2In the 2H2O aqueous solution；Dust technology is added dropwise in above-mentioned solution and adjusts its pH to 2.9, inserted after stirring heat-resisting
In container, and it is put into together in the drier with pressure-reducing valve；The pressure in drier is extracted into after below 10Torr with vavuum pump,
Room temperature carries out the degassing process of 1 hour, then after 95 DEG C of dryings 12 hours, by dried sample in normal atmosphere pressure
Under the conditions of in 600 DEG C of roasting temperatures 3 hours；Then it is classified with the screen cloth of 40 mesh, is obtained described copper modified molecular screen；
The modified eutectic molecular sieve of copper prepared by icp analysis, copper (II) ion accounts for the 2.1% of the modified eutectic molecular sieve gross weight of copper, i.e. copper load
Measure as 2.1wt%
(4) the copper modified molecular screen that 15g steps (3) are obtained is taken, with the commercially available Ludox of 5.42g (silica quality content
For 20wt%) and 15.32g deionized waters be well mixed the catalyst slurry for being fabricated to that solid content is 45.0wt%, and led to
Cross infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, use
Compressed air blows unnecessary slurry droplet off, is dried 24 hours at 120 DEG C, is prepared into copper after roasting 4h under the conditions of 500 DEG C and changes
Property molecular sieve SCR catalyst, the load capacity on regular material be 245g/L, to be designated 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 catalysts of copper, are prepared from by following methods：
(1) eutectic molecular sieve is prepared：By 1.46g SB powder (German Sasol companies, Al2O3% >=70%) be added to 1008.00g
In deionized water, stirring 0.5h after, be added dropwise 798.90g mass fraction be 25% N, N, N- trimethyl adamantane aqueous ammonium
(R1) 30.82g NaOH (purity 96%, Tianjin Kermel Chemical Reagent Co., Ltd.), are added Jing after being sufficiently stirred for,
Stirring 0.5h, adds 122.62g white carbon (SiO2% >=70%), 2～3h is stirred, 7.21g is added after being thoroughly mixed
SSZ-13 crystal seeds, in being fitted into teflon-lined steel bomb, crystallization 72h at 170 DEG C；After the completion of reaction, will
Product is washed with deionized, and 12h roasting 12h at 580 DEG C is dried at 120 DEG C and obtains molecular sieve solid powder；
The mol ratio of raw material is：Na2O：Al2O3：SiO2：H2O：R1 is 68.0：1.0：200.0：5600.0：108.0；
(2) hydrogen type molecular sieve is prepared：Taking the molecular sieve solid powder 15g that step (1) obtains, to be added to 1500mL ammonium nitrate molten
In liquid (1.0mol/L), 12h is exchanged under 80 DEG C of water bath conditions, fully wash and filter, then repeated above-mentioned ammonium ion and exchange
3 times, 12h is dried at 120 DEG C, in 550 DEG C of roasting 4h, obtains Hydrogen SSZ-13/Analcime eutectic molecular sieves；
(3) copper modified hydrogen molecular sieve：The molecular sieve 15g for taking step (2) synthesis is added to 21.24ml concentration for 1.0mol/L
Cu (NO3)2·3H2In the O aqueous solution；Dust technology is added dropwise in above-mentioned solution and adjusts its pH to 2.9, inserted after stirring resistance to
In heat container, and it is put into together in the drier with pressure-reducing valve；The pressure in drier is extracted into below 10Torr with vavuum pump
Afterwards, room temperature carries out the degassing process of 1 hour, then after 90 DEG C of dryings 24 hours, by dried sample in normal atmosphere
In 550 DEG C of roasting temperatures 3 hours under pressure conditions；Then it is classified with the screen cloth of 40 mesh, is obtained modified point of described copper
Son sieve, copper modified molecular screen prepared by icp analysis result, copper (II) ion accounts for the 3.0% of copper modified molecular screen gross weight, i.e. copper and bears
Carrying capacity is 3.0wt%, and the XRD of the molecular sieve is as shown in Figure 2；
(4) the copper modified molecular screen that 15g steps (3) are obtained is taken, with the commercially available Ludox of 3.25g (silica quality content
For 20wt%) and 19.01g deionized waters be well mixed the catalyst slurry for being fabricated to that solid content is 42.0wt%, and passed through
Infusion process is coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with pressure
Contracting air blows unnecessary slurry droplet off, is dried 24 hours at 110 DEG C, copper is prepared into after roasting 2h under the conditions of 500 DEG C and is modified
SCR catalyst, the load capacity on regular material is 230g/L, is labeled as CHA-SCR-1.
Comparative example 2：The modified beta-molecular sieve selective reduction catalyst of synthesis copper
A kind of modified beta-molecular sieve selective reduction catalyst of copper, is prepared from by following methods：
(1) the NaOH aqueous solution is added in cataloid (silica quality content is 30wt%), is sufficiently stirred for
Al (NO are added afterwards3)3The aqueous solution of the 9H2O aqueous solution and TEAOH (TEAOH contents 35wt%), it is anti-after being sufficiently stirred for
The mol ratio for answering mixture, raw material is：Na2O：Al2O3：SiO2：H2O：TEAOH is 21.0：1.0：300.0：4000.0：
150.0；
(2) above-mentioned reactant mixture is put into polytetrafluoroethylcontainer container, closed self-generated pressure heats 72h under the conditions of 155 DEG C；
Then be centrifuged, wash, 120 DEG C be dried 12h, roasting 4 hours removes mould at 550 DEG C under normal atmosphere pressure
Plate；With SiO in icp analysis product2：A12O3Mol ratio be 29：1, the XRD analysis products is with BEA type structures
Beta-molecular sieve, as shown in Figure 3；
(3) the beta-molecular sieve powder of 10g is added in 1000mL ammonium nitrate solutions (1.0mol/L), under the conditions of 80 DEG C
Process carries out ion exchange in 24 hours, fully washs and filters, and then repeats above-mentioned ammonium ion and exchanges 3 times, does at 120 DEG C
Dry 24h, after roasting 4 hours, hydrogenation synthesis β zeolite molecules are obtained at 550 DEG C by zeolite molecular sieve under normal atmosphere pressure
Sieve；
(4) 35g copper acetate (Cu are dissolved in 3500g deionized waters2(CH3COO)4·H2O) 35g, obtains pH for 2.8
Copper acetate (II) deionized water solution；In above-mentioned copper acetate (II) in the aqueous solution, hydrogenation synthesis zeolite molecular sieve 300g is added,
After stirring 2 hours at 80 DEG C, filtered, separation of solid and liquid；Hydrogenation synthesis zeolite molecular sieve after separation of solid and liquid is with 40 DEG C
3500g pure water is cleaned, and filtration is repeated and cleans, until the pH value of detergent remover is 6～7；Then, dry at 120 DEG C
Filter material 12h, roasting 2 hours at 550 DEG C；After being classified with the mesh screen of 40 mesh, the modified beta-molecular sieve of copper is obtained,
The XRD of the molecular sieve is as shown in Figure 3；The beta-molecular sieve that copper prepared by icp analysis is modified, copper (II) ion accounts for the modified β of copper
The 3.0% of molecular sieve gross weight, i.e. copper load capacity are 3.0wt%；
(5) the copper modified molecular screen that 15g steps (4) are obtained is taken, with the commercially available Ludox of 4.32g (silica quality content
For 20wt%) and 15.93g deionized waters be well mixed the catalyst slurry for being fabricated to that solid content is 45.0wt%, and passed through
Infusion process is coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with pressure
Contracting air blows unnecessary slurry droplet off, is dried 24 hours at 105 DEG C, copper is prepared into after roasting 2h under the conditions of 500 DEG C and is modified
SCR catalyst, the load capacity on regular material is 224g/L, is designated as BEA-SCR-2.
Comparative example 3：The modified ZSM-5 molecular sieve selective reduction catalyst of synthesis copper
A kind of modified ZSM-5 molecular sieve selective reduction catalyst of copper, is prepared from by following methods：
(1) in 800g sodium silicate aqueous solution (mass fractions：SiO226%th, Na2O 7.0%) in addition NaOH it is water-soluble
Liquid (5g NaOH is dissolved in 400g deionized waters and being prepared from), adds while stirring the hexahydrate (Al of 61g aluminum sulfate ten2
(SO4)3·16H2O) aqueous solution being formulated in 1.5kg deionized waters is dissolved in 1, the 3- dimethyl ureas of l0g, finally adds matter
Amount fraction is 5% sulfuric acid 1000g, obtains uniform primary gel；
(2) autoclave that the gel described in step 1 loads 5L is produced into self-generated pressure, under 200 revs/min of speed stirrings, 160 DEG C
Crystallization 72 hours, obtains MFI kinds crystalline substance zeolite molecular sieve；
(3) in 640g sodium silicate aqueous solution (mass fractions：SiO225%th, Na2O 8.0%) middle addition 1.75kg deionizations
Water, the hexahydrate (Al of 25g aluminum sulfate ten2(SO4)3·16H2O) and 35g sulfuric acid (mass fraction 97%), step (2) is continuously added
Two grades of gels are obtained after resulting MFI kinds crystalline substance zeolite molecular sieve 1.5kg stirrings；The autoclave that two grades of gels are put into 5L is produced
Self-generated pressure, crystallization is stirred at 150 DEG C, and 110 revs/min of mixing speed, process time are 45 hours；By the slurries mistake for obtaining
Filter, washing, after being dried 5 hours at a temperature of 120 DEG C product is obtained；With the icp analysis product, it is known that wherein SiO2：A12O3
Mol ratio be 80：1, the XRD analysis products is the ZSM-5 molecular sieve with MFI type structure, as shown in Figure 4；
(4) take drying ZSM-5 molecular sieve 10g and be added to the Cu (NO that 84.56ml concentration is 1.2mol/L3)23H2O water
In solution；The ion exchange of 3 hours is carried out at 70 DEG C, is then filtered, then washed with the water of 5 times of amounts, then at 120 DEG C
At a temperature of be dried 10 hours, roasting in 2 hours is then carried out at 550 DEG C, obtain Hydrogen ZSM-5 molecular sieve.
(5) 35g copper acetate (Cu are dissolved in 3500g deionized waters2(CH3COO)4·H2O) 35g, obtains pH for 2.8
Copper acetate (II) deionized water solution；In above-mentioned copper acetate (II) in the aqueous solution, Hydrogen ZSM-5 zeolite molecular sieve 300g is added,
After stirring 2 hours at 80 DEG C, filtered, separation of solid and liquid；Hydrogenation synthesis zeolite molecular sieve after separation of solid and liquid is with 40 DEG C
3500g pure water is cleaned, and filtration is repeated and cleans, until the pH value of detergent remover is 6～7；Then, dry at 120 DEG C
Filter material 12h, roasting 2 hours at 550 DEG C；After being classified with the mesh screen of 40 mesh, modified ZSM-5 point of copper is obtained
Son sieve, the modified ZSM-5 molecular sieve of copper prepared by icp analysis, copper (II) ion accounts for the modified ZSM-5 molecular sieve gross weight of copper
2.90%, i.e., copper load capacity be 2.90wt%；
(6) the copper modified molecular screen that 15g steps (4) are obtained is taken, with the commercially available Ludox of 6.26g (silica quality content
For 20wt%) and 21.51g deionized waters be well mixed that to be fabricated to solid content be the catalyst slurry of 38.0 mass %, and led to
Cross infusion process to be coated on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, use
Compressed air blows unnecessary slurry droplet off, is dried 24 hours at 120 DEG C, is prepared into copper after roasting 2h under the conditions of 550 DEG C and changes
Property SCR catalyst, the load capacity on regular material be 241g/L, be designated as MFI-SCR-3.
Checking test one：
Catalyst obtained by the embodiment of the present invention 1～6 and comparative example 1～3 is used to process the tail of Diesel engine generation
Air-flow, catalyst property indices statistics is as shown in table 1；Relative to the concentration of catalyst upstream NO, under determining catalyst
The NO concentration of trip, calculates the purifying rate of NO, and operations index is as follows：
Space velocity SV：50000/h
Temperature：150℃、200℃、250℃、300℃.
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
The result that catalyst obtained by embodiment 1～6 and comparative example 1～3 purifies under the above parameters NOx is as shown in table 2：
Table 1：The index of the catalyst obtained by embodiment 1～6 and comparative example 1～3
Table 2：NO in catalyst treatment diesel motor exhaust stream obtained by embodiment 1～6 and comparative example 1～3xEffect compare
| Project | Catalyst | NOx removal (%) |
| 150℃ | 200℃ | 250℃ | 300℃ | ||
| Embodiment 1 | CCG-SCR-1 | 27.23 | 70.90 | 94.08 | 98.06 |
| Embodiment 2 | CCG-SCR-2 | 28.11 | 70.92 | 96.99 | 99.49 |
| Embodiment 3 | CCG-SCR-3 | 26.42 | 70.12 | 95.84 | 98.37 |
| Embodiment 4 | CCG-SCR-4 | 27.51 | 71.40 | 95.19 | 99.13 |
| Embodiment 5 | CCG-SCR-5 | 28.21 | 70.77 | 94.41 | 99.47 |
| Embodiment 6 | CCG-SCR-6 | 29.56 | 73.75 | 95.07 | 99.67 |
| Comparative example 1 | CHA-SCR-1 | 23.00 | 67.38 | 85.37 | 95.26 |
| Comparative example implements 2 | BEA-SCR-2 | 32.06 | 64.81 | 84.41 | 89.29 |
| Comparative example implements 3 | MFI-SCR-3 | 16.72 | 57.84 | 86.38 | 91.12 |
As shown in Table 2, the catalyst that prepared by the inventive method, the tail that Diesel engine is produced is processed when temperature is more than 200 DEG C
Nitrogen oxides in air-flow, the purifying rate of NO reaches more than 80%, hence it is evident that higher than the catalyst of comparative example.
Checking test two：
After checking test one terminates, used above-mentioned various catalyst are proceeded into durable process of hydro-thermal and is tested, hydro-thermal is durable
Processing the condition tested is：
Space velocity SV：30000/h
Temperature：700℃
Time：12 hours
Moisture concentration：10%
Oxygen concentration：10%
Nitrogen concentration：Balance
Various catalyst carry out after the durable process test of hydro-thermal, continuing to be used to process diesel engine as catalyst according to above-mentioned parameter
The tail gas stream that machine is produced, various operation indexs are identical with checking test one, and the result for processing nitrogen oxides is as shown in table 3：
Table 3：Catalyst treatment diesel motor exhaust stream obtained by embodiment 1～6 and comparative example 1～3 after hydro-thermal long duration test
Middle NOxEffect compare
| Project | Catalyst | NOx removal (%) |
| 150℃ | 200℃ | 250℃ | 300℃ | ||
| Embodiment 1 | CCG-SCR-1 | 17.25 | 60.21 | 87.68 | 99.20 |
| Embodiment 2 | CCG-SCR-2 | 20.17 | 61.07 | 84.62 | 98.12 |
| Embodiment 3 | CCG-SCR-3 | 17.62 | 59.83 | 84.39 | 96.09 |
| Embodiment 4 | CCG-SCR-4 | 16.79 | 57.66 | 82.26 | 99.50 |
| Embodiment 5 | CCG-SCR-5 | 17.58 | 59.80 | 84.02 | 98.29 |
| Embodiment 6 | CCG-SCR-6 | 18.95 | 59.12 | 84.64 | 99.17 |
| Comparative example 1 | CHA-SCR-1 | 15.76 | 54.44 | 75.47 | 83.82 |
| Comparative example 2 | BEA-SCR-1 | 14.08 | 41.55 | 64.08 | 70.42 |
| Comparative example 3 | MFI-SCR-2 | 16.20 | 30.28 | 35.21 | 45.07 |
As shown in Table 3, the catalyst that prepared by the inventive method, after the durable process test of hydro-thermal, continues to be used as catalyst
In the tail gas stream that Diesel engine is produced is processed, nitrogen oxides is processed in 150～300 DEG C, the purifying rate of NO is above contrast in fact
The catalyst of example is applied, nitrogen oxides in the tail gas stream that Diesel engine is produced, the purifying rate of NO are processed when temperature is more than 250 DEG C
Reach more than 80%；The above results illustrate that catalyst prepared by the inventive method has good hydrothermal stability.
Examples detailed above is technology design to illustrate the invention and technical characterstic, can not limit protection model of the invention with this
Enclose.Equivalent transformation or modification that all essence of the invention is done, all should be included within the scope of the present invention.
Claims (13)
1. a kind of copper modified molecular screen selective reduction catalyst, it is characterised in that with SSZ-13 types molecular sieve and
The eutectic molecular sieve of Analcime type molecular sieve structures to be introduced and obtain copper after active component copper ion as the matrix components of catalyst
Modified eutectic molecular sieve, is carried on the regular material of porous so as to form catalyst, and the load capacity of the regular material of described porous is
180～260g/L；The mole of described copper ion is 2.0～5.0 times of eutectic molecular sieve saturation exchange capacity；Described
SSZ-13/Analcime eutectic molecular sieves are by silicon source, silicon source, sodium source, H2O, SSZ-13 molecular sieve seed, template R are
Raw material, is prepared from after crystallization, filtration, drying and roasting；Described silicon source, silicon source, sodium source, H2O, template R
Mol ratio be 20～250:1:5～70:100～10000:3～150, wherein silicon source：Silicon source：The mol ratio of sodium source refers to respective
Oxide S iO2:Al2O3:Na2The mol ratio of O；Described SSZ-13 molecular sieve seeds and SiO2Weight ratio be 0.02～0.2:1.
2. catalyst according to claim 1, it is characterised in that the weight of described copper ion accounts for the modified eutectic molecule of copper
The 0.03～20% of sieve overall weight.
3. catalyst according to claim 2, it is characterised in that the mole of described 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, it is characterised in that described silicon source, silicon source, sodium source, H2O, template
The mol ratio of agent R is 20～150:1:8～68:130～4500:3～150；Described SSZ-13 molecular sieve seeds and SiO2Weight ratio
For 0.02～0.1:1.
5. catalyst according to claim 1, it is characterised in that described silicon source is sodium metaaluminate, sodium aluminate, SB
Any one in powder, aluminum sulfate, boehmite, aluminium isopropoxide；Described silicon source be chromatographic silica gel, Ludox, sodium metasilicate,
Any one in white carbon, tetraethyl orthosilicate, silicic acid；Described template R is organic amine template, including R1 and R2
Two class organic amine templates, organic amine template is R1 and the class organic amine templates of R2 two according to R1：R2=4～10:1 rubs
The mixed templates that your ratio is configured to；Described R1 class templates agent be N, N, N- trimethyl -1- adamantane ammonium hydroxide, benzyl three
In ammonium hydroxide any one；Described R2 templates are replacement alkyl phosphonium hydroxide piperidines；Described replacement alkylaryl hydroxide
It is N to change piperidine template agent, N- dimethyl -3,5- dimethyl hydrogen oxyls, N- ethyl-N-methyl -2,6- dimethyl hydrogen oxyls,
N, N- dimethyl -2- (2- ethoxys)-dimethyl hydrogen oxyl, N, N- dimethyl -2- ethyl-dimethyl diisopropylimidazoliniums, N, N-
Diethyl -2,6- dimethyl hydrogen oxyls, N, N- dimethyl -2,6- dimethyl hydrogen oxyls, N- ethyl-N- propyl group -2,6- two
Any one in methyl diisopropylimidazolinium, or the mixture that two kinds and the above are mixed with arbitrary proportion.
6. catalyst according to claim 4, it is characterised in that described silicon source is sodium metaaluminate, sodium aluminate, SB
Any one in powder, boehmite, aluminium isopropoxide；Described silicon source is chromatographic silica gel, white carbon, tetraethyl orthosilicate, silicon
Any one in sour sodium.
7. catalyst according to claim 1, it is characterised in that the regular material of described porous for porous cellular stream
Cross the regular material of type, selected from cordierite, alph-alumine, carborundum, aluminium titanates, silicon nitride, zirconium oxide, mullite, spodumene,
Any one in alumina-silica magnesia or zirconium silicate.
8. catalyst according to claim 7, it is characterised in that the regular material of described porous is cordierite.
9. the preparation method of catalyst described in any one of claim 1～8, it is characterised in that comprise the following steps：
(1) eutectic molecular sieve is prepared：Silicon source, silicon source, sodium source, deionized water, SSZ-13 molecular sieve seeds, template R
After according to described ratio mixing, 20～144h of crystallization, Ran Houjing under conditions of self-generated pressure and crystallization temperature are for 100～200 DEG C
SSZ-13/Analcime eutectic molecular sieves are obtained after filtration, drying and roasting；The temperature of described drying is 100～150 DEG C,
Drying time is 12～48h, and described sintering temperature is 450～650 DEG C, and roasting time is 3～20h；
(2) hydrogen type molecular sieve is prepared：The SSZ-13/Analcime eutectic molecular sieves that step (1) is obtained are put into ammonium salt water-soluble
Carry out under the conditions of 70～100 DEG C after ammonium ion exchanges 1～3 time, 12～48h, Ran Houyu being dried under the conditions of 105～120 DEG C in liquid
Hydrogen type molecular sieve is obtained under the conditions of 450～650 DEG C after 2～10h of roasting；
(3) copper modified hydrogen molecular sieve：The hydrogen type molecular sieve that step (2) is obtained is added in copper salt solution, in room temperature
Under the conditions of～100 DEG C stir 24～72h carry out copper be modified, after filtration under the conditions of 50～100 DEG C be vacuum dried 12～48h, in repetition
State it is modified, filter, after process of vacuum drying 0～3 time, by dried sample under the conditions of normal atmosphere pressure in 450～600 DEG C
After 3～5h of lower roasting, the modified eutectic molecular sieve of described copper is obtained；
(4) the modified eutectic molecular sieve of the copper for obtaining step (3) and cataloid are according to 2.0～5.0:1 weight is than mixing
Afterwards, deionized water is added to be prepared into catalyst slurry, copper modified molecular screen contains admittedly with the total of cataloid in catalyst slurry
Measure as 35.0～55.0wt%；By infusion process, described catalyst slurry is coated on into described porous according to described load capacity
On regular material, with compressed air unnecessary slurry droplet is blown off, 12～48h, Ran Houyu are dried under the conditions of 105～120 DEG C
2～10h of roasting under the conditions of 450～650 DEG C, is prepared into copper modified molecular screen SCR catalyst.
10. method according to claim 9, it is characterised in that the crystallization temperature described in step (1) is 150～200 DEG C,
Crystallization time is 24～100h；The temperature of described drying is 105～120 DEG C；In step (2), described ammonium salt aqueous solution is
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
For 80～100 DEG C；In step (3), described 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. methods according to claim 10, it is characterised in that the 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), described mantoquita is water-soluble
Liquid is the aqueous solution of copper nitrate, copper chloride or copper sulphate.
The application of catalyst described in 12. any one of claim 1～8, it is characterised in that described catalyst mainly for the treatment of
Containing NOxIn the exhaust treatment system of air-flow.
13. applications according to claim 12, it is characterised in that described contains NOxAir-flow, except including nitrogen oxygen
Compound, also containing oxygen, ammonia and/urea, wherein NO2Content be at most NOxThe 80% of weight.
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